1AAA, Exp Data On Tacticity PVAc APV, Docslide - Us - Stereochemistry-Of-Polyvinyl-Alcohol PDF

Stereochemistry of Poly (vinyl Alcohol)
K . FUJII
Kuraray Company Limited
P.O. Box 35,2045.1 Aoeyana.
Sakazu. Kurashiki. Okayama. Japan
I . Introduction . . . . . . . . . . . . . . . . . . . . . . 432
I1. Recent Progress in the Preparation of Stereoregular PVA . . . . . . 433
A. Vinyl Ethers as the Starting Monomer . . . . . . . . . . . 433
1. Vinyl Benzyl Ether . . . . . . . . . . . . . . . . . 433
2. Vinyl t-Butyl Ether . . . . . . . . . . . . . . . . . 435
3. Vinyl Trimethylsilyl Ether . . . . . . . . . . . . . . 438
B. Vinyl Esters as the Starting Monomer . . . . . . . . . . . . 439
C . Divinyl Monomers as the Starting Monomer . . . . . . . . . 442
1. Divinyl Acetals . . . . . . . . . . . . . . . . . . 443
2. Divinyl Carbonate . . . . . . . . . . . . . . . . . 444
3. Divinyloxydimethylsilane . . . . . . . . . . . . . . . 446
D . Low-Molecular-Weight Model Compounds . . . . . . . . . . 447
111. Stereoregularity and Crystallizability of PVA and Esters . . . . . . . 449
A . PVA . . . . . . . . . . . . . . . . . . . . . . . 449
B. Poly(viny1Acetate) . . . . . . . . . . . . . . . . . . 457
C. Poly(viny1 Formate) . . . . . . . . . . . . . . . . . . 457
D . Poly(viny1 Trifluoroacetate) . . . . . . . . . . . . . . . 464
IV . Spectroscopic Studies . . . . . . . . . . . . . . . . . . . 467
A . High-Resolution NMR Spectra . . . . . . . . . . . . . . 467
1. Poly(viny1Acetate) . . . . . . . . . . . . . . . . . 467
2. PVA . . . . . . . . . . . . . . . . . . . . . . 471
3. Poly(viny1Trifluoroacetate) . . . . . . . . . . . . . . 473
4. Poly(viny1 Formate) . . . . . . . . . . . . . . . . . 476
5 . Poly(viny1 Formal) . . . . . . . . . . . . . . . . . 476
B. Infrared Spectrum . . . . . . . . . . . . . . . . . . 478
1. PVA . . . . . . . . . . . . . . . . . . . . . . 478
2. Poly(viny1 Acetate) . . . . . . . . . . . . . . . . . 486
3. Poly(viny1 Formate) . . . . . . . . . . . . . . . . . 486
4. Poly(viny1 Trifluoroacetate) . . . . . . . . . . . . . . 490
5. Poly(viny1 Formal) . . . . . . . . . . . . . . . . . 490
6. Poly(viny1 Acetoacetal) . . . . . . . . . . . . . . . . 490
V . Microtacticity and Chemical Reactions of PVA . . . . . . . . . . 490
A . Reaction with Aldehyde . . . . . . . . . . . . . . . . 491
43 I
432 FUJI1
1. Hydrolysis of Poly(viny1Acetal) . . . . . . . . . . . . 491

2. Acetalization of PVA . . . . . . . . . . . . . . . . 493
3. Reaction Equilibrium . . . . . . . . . . . . . . . . 495
B. Esterification and Hydrolysis of Esters . . . . . . . . . . . 496
1 . Hydrolysis of Poly(viny1 Acetate) . . . . . . . . . . . . 496
2. Esterification of PVA . . . . . . . . . . . . . . . . 499
C. Miscellaneous Reactions . . . . . . . . . . . . . . . . 500
1. Reaction with Boric Acid or Borax . . . . . . . . . . . 500
2. Triphenylmethylation . . . . . . . . . . . . . . . . 500
3. Reaction with 8-Butyraldehyde Sulfonic Acid . . . . . . . . 501
VI. Tacticity and Physical Properties of PVA . . . . . . . . . . . . 501
A . Solid Properties . . . . . . . . . . . . . . . . . . . 501
1. Crystal Structure . . . . . . . . . . . . . . . . . . 501
2. Crystallinity, Water Resistance, and Tacticity . . . . . . . . 502
3. Crystallization from Solutions . . . . . . . . . . . . . 508
4. Glass Temperature and Melting Point . . . . . . . . . . 511
5. Dynamic Viscoelasticity . . . . . . . . . . . . . . . 513
B. Solution Properties . . . . . . . . . . . . . . . . . . 513
1. Gelation of Aqueous Solutions . . . . . . . . . . . . . 513
2. Coloration with Iodine . . . . . . . . . . . . . . . . 514
3. Stability of Aqueous DMSO Solutions . . . . . . . . . . 515
4. Fractionation by Foaming . . . . . . . . . . . . . . 516
5 . Mechanical DenaturationofAqueous Solutions . . . . . . . 518
C. Steric Conformation . . . . . . . . . . . . . . . . . . 519
D . Other Properties . . . . . . . . . . . . . . . . . . . 520
VII . Structure and Properties of PVA Derived from Vinyl Acetate . . . . . 521
A. Effect of Polymerization Conditions of Vinyl Acetate on Properties of
Derived PVA . . . . . . . . . . . . . . . . . . . 521
B. Various Structural Irregularities . . . . . . . . . . . . . . 527
1 . 1,2-Glycol Structure . . . . . . . . . . . . . . . . . 527
2. LongBranching . . . . . . . . . . . . . . . . . . 528
3 . Short Branching . . . . . . . . . . . . . . . . . . 530
VIII . Concluding Remarks . . . . . . . . . . . . . . . . . . . 531
References . . . . . . . . . . . . . . . . . . . . . . . 532
I. INTRODUCTION
Poly(viny1 alcohol) (PVA) holds a unique position in the field of

polymer stereochemistry. Its high crystalline nature has been noted
since the early days of polymer science (1). Three different steric con-
figurations, which accidentally coincide with isotactic (2). atactic (3).
and syndiotactic (4) structures. had been postulated to account for the
POLY(VIPU’YL ALCOHOL) 433
X-ray fiber diagram of PVA before these structures were designated by
Natta et al. (5).
The discovery of stereoregulated polymerization (6,7) evoked great
interest in the preparation and characterization of stereoregular PVA.
The problem has been studied intensely particularly in Japan, because
of its industrial potential. Attempts to prepare stereoregular PVA
resulted in some success, which opened the door to advanced stereo-
chemical investigation of PVA. It is the purpose of this paper to review
recent developments in the stereochemistry of PVA.
11. RECENT PROGRESS IN THE PREPARATION OF

STEREOREGULAR PVA
A. Vinyl Ethers as the Starting Monomer

Until recently PVA was obtained only from polymers of vinyl esters,
but the lack of reactivity of vinyl esters with ionic initiators and the
successful preparation of isotactic poly(viny1 alkyl ethers) (7) led to the
use of vinyl ethers as the starting monomer for producing PVA.
Early Russian papers (8) claimed that PVA was obtained by treating
poly(viny1 ethers) with sodium ethylate. This is quite unlikely in view
of the stability of such ether linkages to basic attack (9), and in fact this
result has never been reproduced in other laboratories (10,ll).The first
successful transformation to PVA was achieved by Murahashi, Sano,
and Ryutani (12) with hydrogen bromide treatment.
1. Vinyl Benzyl Ether

Murahashi, Sano, and Ryutani chose vinyl benzyl ether as the starting
monomer and obtained a water-soluble PVA by treating a cationically
prepared polymer with hydrogen bromide (12). They proceeded to
obtain an isotactic polymer by the proliferous polymerization tech-
nique applied to vinyl alkyl ethers by Schildknecht et al. (7). The
polymer gave a water-insoluble product when treated with hydrogen
bromide (13),but acetylation of a similar polymer with acetic anhydride
and stannic chloride and subsequent alkaline hydrolysis gave a water-
soluble PVA (14). It was later disclosed that the insolubility was due
to oxidation of the benzyl ether bond of the polymer to give a benzoate
434 FUJI1
BF, . OEt,
(-CH2---.CH-)" (--CH2-CH-),
CHz=YH 0
I
0
I
OH
4
( 4 H2-CH-),
II
0
I
c=o
I
bond, which is resistant to hydrogen bromide but can be removed by

alkaline treatment (15). Successful preparation of isotactic PVA was
deduced from elemental analysis and infrared data (16). It was verified
by transformation to poly(viny1 formate) (17), which showed an X-ray
fiber pattern similar to that of isotactic polystyrene (18).
The effect of the conditions of polymerization of vinyl benzyl ether
on polymer structures was studied by Murahashi et al. (15) in detail.
The monomer, benzyl ether, was also easily oxidized by air to form
ethyl benzoate, which greatly reduced the stereoregularity of the
TABLE 1
Tacticities of Poly(viny1 Benzyl Ether) (21a)
. ~~
Tacticity in triad
From benzyl methylene From acetoxymethyl

Polymerization signals of PVBE" signals of derived PVAc'
- ~
Solvent Temp("C) I(%) H(%) S(%) I(%) H(?o) S(%)
Toluene - 78 86 10 4 89 8 3
Nitroethane - 78 69 24 7 63 27 10
a PVBE = poly(viny1benzyl ether)

' PVAc = poly(viny1 acetate).
POLY(VINYL ALCOHOL) 435
-CH,O-
a-proton
I
2.80 5.68 5.80 5.92
I
8.40
7;
Fig. I . NMR spectrum of poly(v1nyl benzyl ether) obtained in toluene at -78 C
with BF, . OEt, catalyst (21a).
resulting polymer (15). Use of a Ziegler catalyst (AlEt, + TiCl,) gave

a harder product than the polymers obtained with other cationic
initiators (19), but this was found to be due to the formation of vinyl
alcohol units in the polymer by reaction of the benzyl ether bond with
TiCl, (20). In the high-resolution nuclear magnetic resonance spectrum
of poly(viny1 benzyl ether), the side chain methylene signal was a
triplet that seemed to correspond to the isotactic ( I ) , heterotactic ( H ) ,
and syndiotactic ( S ) triad in the order of increasing field strength (21).
The isotacticity increased as the polymerization temperature and
monomer concentration were lowered. Tacticity was also influenced
by the polarity of the polymerization medium, as in the cationic poly-
merization of vinyl alkyl ethers (22), but to a lesser extent (21).
2. Vinyl t-Butyl Ether

In an attempt to attain easier polymer transformation and greater
stereoregularity, vinyl t-butyl ether was employed by two research
groups (1 7,23). Predominantly isotactic polymers were produced by
436 FUJI1
polymerization with boron trifluoride etherate in nonpolar media, and

atactic polymers were obtained with stannic chloride in polar media
B F 3 - OEI2 H Br
tCH,-CH+, _____I tCH2-CH )),,
CH2=7H
I
0
I
0
I
I
OH
I
c (CH,), I
c-0
I
CH,
such as ethyl bromide (1 7) or methylene chloride (23). As expected, the
transformation was easier than in benzyl ether, but hydrogen bromide
treatment often gave water-insoluble products while the acetylation
method (14) invariably led to water-soluble PVA (17,24). The mecha-
TABLE I1
Tacticities of Poly(viny1t-Butyl Ether) Prepared in a Toluene-Nitroethane Solvent (128)
Tacticity determined from methyl signdl of

derived poly(viny1 acetate)
__
Toluene (vol %) Nitroethane (vol 2,) Triads ("o) Didds" ( ' I < ) )
____ ___ ~ -
I H S I s
~ _ _ _ __
100 0 59 30 I1 14 26
80 20 44 38 18 63 31
60 40 22 46 32 55 45
40 60 19 47 34 425 515
20 80 18 48 34 42 58
0 100 lb 48 34 42 58
' Calculated from triads as i = I + f H and s = S + fH.

0 25 50 75 100
Vol % of EtNO, in toluene-
Et NO, mixture
Fig. 2. Effect of polar solvent o n the stereoregularity of poly(viny1 t-but$ ether)
(22). [ M , ] = 0.376 M ; [BF, . OEtJ = 5.lmM: polymerization temperature, - 78'C.
nism of acetylation seemed to be different in the two ethers. Unlike the

case of benzyl ether, a large part of the t-butyl ether group was first
cleaved by acid to a hydroxyl group and then acetylated (24). Gelation
of the reaction mixture was observed in this case, but on standing
overnight all hydroxyl groups were acetylated and a homogeneous
solution was obtained (25).
Higashimura et al. studied the effect of polymerization conditions
on polymer tacticity and observed a further increase in syndiotacticity
with polymerization in nitroethane (22,26). The presence of the penul-
timate effect was confirmed for the homogeneous system (27).
PVA samples derived from this monomer have been used as the
reference sample in many studies of the stereoregularity of PVA. The
monomer is difficult to prepare by the Reppe process but can easily be
obtained by transetherification between t-butyl alcohol and vinyl ethers
such as benzyl (25), 2-chloroethyl (28), and 2-n-butoxyethyl ether (29).
438 FUJI1
3 . Vinyl Trimethylsilyl Ether

The synthesis of PVA samples with a wider range of tacticity was
made possible by the use of vinyl trimethylsilyl ether (vinyloxytri-
methylsilane). This monomer was first synthesized by Russian workers
(30) and was applied to PVA synthesis by Murahashi, Nozakura, and
Sumi (31). The monomer was prepared by reacting mercuridiacetal-
dehyde with trimethylchlorosilane and was polymerized with cationic
CH --CH
,-0I
- Lewis acid
+CH,<H+,,
I
- CH,OH
+CH,CH j,
I
0 OH
initiators. The polymer was converted to PVA by methanolysis imme-

diately after polymerization. Although polymerization with ethyl
aluminum dichloride in toluene gave a polymer of 91% isotacticity
(in the diad), stannic chloride in nitroethane led to 74% syndiotac-
TABLE 111
Estimation of Tacticities of Various Poly(viny1 Acetate) by NMR (33)
Triads Diadsb
PoJymeri- (%) (",,)
Expt Monomer" Catalyst Solvent zation ~~ ~ ~ - -
temp( C ) I H S I s
VOSi EtAlCl, Toluene -95 86 10 4 91 9

t-BuVE BF, . OEt, Toluene -78 79 17 4 87 13
VOSi Et AICl, CH,Cl,-toluene -78 46 34 20 63 37
(1:l)
4 VAc Radical Commercial 32 46 22 55 45
5 VOSi Et AICI, C H ,CI,-t oluene -78 33 41 26 53 47
(3:l)
6 VTFAc Radical 25 48 27 49 51
7 VOSi EtAICI, CH,CI, -78 24 45 31 46 54
8 VOSi SnCI, CH,CI, -78 23 44 33 45 55
9 VOSi SnCI, EtNO, -95 1 1 43 46 32 68
10 VOSi SnCI, EtNO, -78 6 40 54 26 74
a
VOSi = vinyl trimethylsilyl ether; t-BuVE = t-butyl vinyl ether;
VAc = vinyl acetate; VTFAc = vinyl trifluoroacetate.
Calculated from triads.
ticity, which is the highest value so far obtained for PVA (32). As in
the case of vinyl t-butyl ether (17,26) the chain length of the resulting
polymer sharply decreased when the polymerization was carried out
in polar media (32,33).Various properties of stereoregular PVA samples
derived from the silyl ether were investigated by Murahashi et al.
(34- 35).
Recently a new method of preparing vinyl trialkylsilyl ether has been
filed in patent applications together with PVA synthesis by polymeri-
zation and subsequent alcoholysis or hydrolysis (36,37). Acetaldehyde
was reacted with trialkylchlorosilane in the presence of zinc chloride
and t-amine in this synthesis.
Matsumura, Nozakura, and Murahashi (38) also studied PVA
synthesis from vinyl triisopropylsilyl ether and deduced from the
infrared and NMR data that highly heterotactic polymers were formed.
N o details have yet been published concerning this interesting work.
B. Vinyl Esters as the Starting Monomer

Various vinyl esters have been studied to examine the effects of ester
substituents on stereoregulation. Early investigations seem to have
been handicapped by limited means of studying polymer tacticity.
Since vinyl esters d o not respond to ionic or coordinated catalysts,
only free-radical polymerization has been studied.
The first evidence that clearly showed the effects of ester substituents
on PVA properties was presented by Haas, Emerson, and Schuler (39).
They found that polymers of vinyl trifluoroacetate exhibited crystalline
type fiber patterns and that the derived PVA was less soluble in water
than PVA obtained from vinyl acetate. However, poly(viny1 acetate)
obtained from that PVA gave an amorphous X-ray pattern. Fordham
(40) tried to interpret the steric control in free-radical propagation in
terms of steric and electrostatic interactions between substituents in the
polymer chain. In the case of vinyl haloacetate the stereoregulation was
assumed to occur in the order
CF,COO > CC1,COO > CC1,HCOO > CClH,COO
on the basis of the X-ray crystallinity of the polymers and the water
resistance of PVA derived from them (41). The repeat distance, 4.8 A,
of poly(viny1 trifluoroacetate) was assumed to show a syndiotactic
440 FUJI1
structure (41), although Chatani et al. (42) had shown that the polymer
obtained by trifluoroacetylation of PVA derived from vinyl acetate
also gave a similar X-ray appearance. Ito, Noma, and Sakurada (43)
found that the 1,2-glycol content of PVA derived from the fluoro-
acetate was 1.05 mole % compared with 1.8 mole % of PVA from vinyl
acetate at a polymerization temperature of 60°C. A recent development
of NMR spectroscopy revealed a slight increase in syndiotacticity in
fluoroacetate (32).* The greater water resistance of this PVA may be
due to its higher syndiotacticity and lower 1,2-glycol content.
Following the work by Haas et al. various vinyl esters were studied.
Vinyl benzoate was found to give PVA of smaller 1,2-glycol content
(1.2 mole %, 60°C) (45), but the PVA was much less water-resistant
(46). Imai et al. (47,48) found that the clouding rate of aqueous di-
methyl sulfoxide solutions of PVA and coloration with aqueous iodine
solutions indicated the structural regularity of the polymer as effectively
as water resistance. They studied PVA samples obtained from various
vinyl esters, using these parameters, and found structural regularity to
occur in the following order; 2-ethylbutyrate and trifluoroacetate >
n-butyrate > propionate and monochloroacetate > formate > acetate
> benzoate (at a polymerization temperature of 60°C) (46). A study
with 2-ethylbutyrate showed that branching from the a-carbon pro-
vided a large steric effect. Little difference was observed between PVA
obtained from vinyl acetate and that from vinyl ethyl oxalate (49).
Little was known about vinyl formate until its interesting polymeri-
zation behavior among vinyl esters was noted. lnteraction between
formyl groups by hydrogen bonding seemed to be important in this
monomer. Bulk polymerization yielded PVA with the highest water
resistance and least 1,2-glycol content ;the 1,2-glycol content increased
when polymerization was conducted in polar media (50,51). Poly(viny1
formate) prepared at low temperatures was crystallizable and gave an
identity period, 5 A, which suggested that the configuration of regular
sequences was syndiotactic (52-54). The derived PVA was more water-
resistant than PVA from vinyl acetate (54-56). Solid-state polymeriza-
* A slight increase in syndiotacticity in poly(viny1 trifluoroacetate) was also reported

by Kamey and Field (44),but tacticity was estimated on the basis of doubtful assignments
that were not made by a logical process. Therefore it is improper to cite here (see Section
IV).
tion of vinyl formate gave polymers that showed another crystalline
type of X-ray pattern. A stereoblock nature was deduced for the poly-
mers from X-ray and infrared data, and from their solubility (57).
Ramey, Lini, and Statton (58) studied the NMR spectra of poly(viny1
formate) samples prepared at 0-60°C and observed a slight increase of
syndiotacticity at low temperatures. The temperature dependence of
TABLE IV
Tacticities of Various Poly(viny1 Formates) Determined from the Methyl Proton
Signals of Derived Poly(viny1 Acetate) (59)
Triad (observed) Diad (calculated) Heterotactic

Polymerization
temp ("C) index
I(%) H(%) S(%) i(%) s(%)
In bulk and methyl formate

120 24 41 29 47.5 52.5 0.94
60 22 48 30 46 54 0.97
0 21 48 31 45 55 0.97
- 78 16 46 38 39 61 0.97
In n-butyraldehyde
60 20 48 32 44 56 0.97
In the solid state

- 78 30 40 30 50 50 0.80
~~ ~ ~~ ~~~
tacticitv was studied in the range of -78 to 12PC by converting

poly(vinyl formate) samples to poly(viny1 acetates), which were sub-
jected to NMR analysis (59). It was confirmed that the increased
syndiotacticity in vinyl formate obtained by lowering the temperature
was comparable to that produced by polymerization of vinyl chloride
(60). The polymer prepared by solid-state polymerization was slightly
more isotactic and is ideally atactic in the diad, but the heterotactic
index (61) calculated from the triad data showed deviation from unity,
suggesting the presence of some stereoblock nature in the polymer.
The swelling behavior of the derived PVA in water suggested stereo-
blockade rather than the presence of two or more stereoregular poly-
mers (62).
Murahashi et al. (63,64) studied the tacticities of various vinyl ester
polymers by measuring the infrared absorbance, D,, 6/D850, of PVA
442 FUJI1
TABLE V
Activation Parameters for Radical Polymerization of
Vinyl Esters, CH,=CHOCOR
-
-. --
R H , - H, s, - s, Ref
(cal/mole) (cal/deg mole)
65 f 55 0.3 k 0.2 64
60 k 20 0.1 f 0.1 64
75 k 20 *
0.1 0.1 64
165 k 40 0.4 rt 0.2 64
270 k 60 0.5 k 0.2 64
160 & 30 0.5 i 0.1 64
270 75 0.6 & 0.3 64
670 & 50 *
1.8 0.2 64
390 k 20 1.0 & 0.1 64
280 f 20 0.30 f 0.1 59
(32,65). As shown in Table V, the length of alkyl substituents has little

effect on the enthalpy term in the following equation (66):
However, branching from the a-carbon clearly contributes to the steric

effect. The polar effect is also evident in the haloacetate series. Con-
sequently trichloroacetate shows the highest difference in activation
enthalpy, but unfortunately the monomer was difficult to polymerize
at low temperatures. A relatively large temperature effect of vinyl
formate is noteworthy. The polymerization medium showed different
effects, depending on the monomer employed. As in vinyl formate (50),
bulk polymerization was favorable in vinyl trifluoroacetate (64). In the
case of vinyl trimethylacetate, polymerization in diethyl ether was the
most favorable, and 68% syndiotacticity (in diad) was obtained at
-78’)C (64).
C. Divinyl Monomers as the Starting Monomer

PVA may also be obtained from cyclic polymers of appropriate
divinyloxy compounds, and alternating intra- and intermolecular
propagation would lead to some stereocontrol. Three types of mo-
nomers have been studied, but in no case was the exclusive occurrence
of cyclization to form 6-membered rings observed, and the derived
polyols were rich in irregular structures.
1. Divinyl Acetals
A number of divinyl acetals and ketals have been studied.* In most
cases cationic polymerization gave cross-linked, insoluble products
while free-radical polymerization gave soluble polymers. Divinyl
formal has been investigated most intensively, but reports do not
agree as to the solubility of the resulting polymers (68-72). Besides
CH, CH,
/I /I
CH CH
I I
0, o
, cation t mostly insoluble product
-CH
\,CH/ \ z
CH
/I
’ -C H
\,CH-CH
-CH CH-
,-0I
CH I
I
HX-0-CH=CH
0 0 2
R
I
!
H R
1
-CH,-CH
I
OH
L
* They are reviewed by Cooper (67)

444 FUJI1
polymerization conditions such as temperature, solvent, and conver-

sion, various factors such as the purity of the monomer or conditions
of polymer isolation may have to be taken into account to explain this
discrepancy.
Conversion of the polymers to PVA by acid hydrolysis has been
attempted, and the resulting polymers were mostly characterized by
their infrared spectra and elemental analyses. The amounts of 5-mem-
bered rings and of uncyclized units were estimated from the 1,2-glycol
content of the resulting polyol and from the degree of unsaturation in
the original polymer, respectively. Minoura and Mitoh (72) found
16-18 mole % of 1,2-glycol in divinyl formal, and Arbuzova et al. (73)
reported 23% of 5-membered rings and 5% of uncyclized units in
polymers of divinyl formal and n-butyral. The exact structures of the
remaining units have not been fully elucidated. Matsoyan (68) showed
the presence of 1,3-glycol by oxidation of the polyol to oxalic acid,
but no quantitative data were given for this analysis. The presence of
a substantial amount of 1,2-glycol means that the same amount of
1,4-glycol occurs in the polymer chain. Therefore the structures of the
resulting polyols seem to be substantially different from those of au-
thentic PVA. Other experimental findings support this view. Sakurada
et al. (74) studied the acetalization of polyols obtained from divinyl
butyral and found very poor reactivity compared with PVA derived
from vinyl acetate. (In one example the degree of acetalization was
5.3% while the PVA derived from vinyl acetate was acetalized to
53.8% .) Recently the formation of pendant formyl groups by proton
transfer during the free-radical polymerization of divinyl formal was
proposed (75). The infrared spectrum of poly(diviny1 formal) (72) differs
significantly from those of poly(viny1 formals) derived from PVA
samples of different tacticities (76). A similar spectral difference was
observed in acetoacetals. Introduction of vinyl alcohol units into the
poly(diviny1 acetoacetal) chain, by copolymerization with vinyl acetate
and subsequent alkaline hydrolysis, did not affect the difference (77).
In conclusion, the structures of the polyols obtained from divinyl
acetals differ considerably from the regular PVA structure.
2. Diuinyl Carbonate
The chemistry of divinyl carbonate has been established by Mura-
hashi et al. (78-80). Because appropriate methods of characterization
C H 2 CH,
I/ I/
CH C H
I I
4C/O
I/
0
1%
-CH,
\
CH-CH
l i
*\ C/O
I/
0
/I
0 L
i 1
X H , CH CH2
\CH
p
, ~ 1
CH CH I - -CH i
OH OH!,
i l
OH O H
I
i,
have been developed for poly(diviny1 carbonate), its structure is much

better known than those of polymers of divinyl acetals.
Monomer carbonate was prepared by reaction of mercuridiacetal-
dehyde with phosgene in tetrahydrofuran, with the polymerization
carried out in bulk or in solution with free-radical initiators (78). Two
C=O stretching bands were observed. On the basis of the infrared
spectra of various model carbonates, the 1810 cm-' band was assigned
to 5-membered cyclic carbonate, and the 1760 cm-' band to 6-mem-
bered cyclic carbonate and pendant vinyl carbonate. The relative
amounts of 5- and 6-membered rings and of 1,2-addition were esti-
mated from the intensities of the two bands and of the c=C stretching
band at 1660 cm- (78). A substantial amount of pendant unsaturation
was present, and the amount of the insoluble fraction increased with
conversion. A large quantity of 5-membered cyclic carbonate was also
446 FUJI1
TABLE VI
Polymerization and Polymer Structure of Divinyl Carbonate at Various Monomer
Concentrations in Benzene (78)”
Expt 1 2 3 4
Monomer concentration
(% by vol) 70 50 30 10
Time (min)
Conversion (%)*
Soluble and insoluble parts (%)

1.2-addition (%)
0.9
~
52
12.2
10.0
72
---
0.5
56
77
13.9
10.9
69 59
112
0.4
11.1
8.4
52
1080
14.7
0.0 14.0
- ~
6-Membered ring (%) ~ 12 31 18 25 27 - -
5-Membered ring (%) ~ 16 13 13 16 21 - -
a Conditions: 60 f 0.05”C; [BPO] = 0.5 mole 7; of monomer.

’ Polymerization was stopped at the first appearance of gelation.
present, and as estimated by the infrared method, it showed good

agreement with the 1,2-glycol content in the derived polyol. The forma-
tion of 5-membered carbonate was favored at higher temperatures.
The parameters of copolymerization reactivity, Q- and e-values, were
determined from copolymerization with p-chlorostyrene and vinyl ac-
etate (80). The reactivity of divinyl carbonate (Q = 0.035 and e = -0.26)
was similar to that of vinyl acetate (Q = 0.026 and e = -0.22). Copo-
lymerization of these two monomers provides a good means of pre-
paring PVA samples containing various amounts of 1,2-glycol.
3. Divinyloxydimethylsilane
Polymerization of divinyloxydimethylsilane and conversion of the
polymers to PVA were also studied by Murahashi et al. (81,82). This
monomer showed quite different behavior in free-radical and cationic
polymerization. While radical initiation gave 5- and 6-membered
cyclizations as well as pendant vinyloxy groups (82), cationic poly-
merization proceeded mainly through 1,Zaddition and gave PVA with
a minor amount of 1,2-glycol (81). NMR analysis of the acetylated
products showed no separation of the acetoxy proton signal for the
radical products because of the high 1,2-glycol content. The tacticity
of the cationic polymer product was little influenced by polymeriza-
CH, CH,
/I II
CH
<i'H I
cation
~ / \
CH, CH,
-CH, ,CH,
\
-CH,--CH-
I 0y
/ \
o TH
0
\i'
/ \
6" 0
I
I
(CH,),SiOCH=CH;
CH, CH3 CH, CH,
i I
-c1\ !
IH
OH
,cq,
CH
OH
1 -CH2
\
CH-CH
I
OH
I
OH
,CH,-
Y
-CH,<H
I
OH
I
> 0
I
(CH,),-SiOCH=CH
tion conditions; I = 0.39-0.45, H = 0.40-0.45, and S = 0.15-0.19.

Degrees of polymerization were relatively low, ranging from 50 to 150
as PVA. Another characteristic of this PVA was its weak absorbance
at 916cm-': D,,,/D,,, = 0.11-0.15) (81).
D. Low-Molecular-Weight Model Compounds

High polymers exhibit a number of characteristics of practical and
theoretical interest, arising from their high molecular weights. At the
448 FUJI1
same time some ambiguity is often inevitable in studying their structures

and properties because of limitations related to their macromolecular
nature. It is thus advantageous to study model compounds of low
molecular weight in order to minimize these limitations. Dimer and
trimer models of PVA, separated into diastereoisomers, have con-
tributed greatly to the stereochemical investigation of the polymer.
Nagai et al. (83-85) separated the meso and dl isomers of pentane-
2,4-diol by elution chromatography of their sodium borate complex.
Only the /3-diol, which was eluted faster, was obtained as crystals.
Nagai et al. deduced that the a- and /3-diols corresponded to the meso
and dl isomers, respectively, from infrared examination of their hydro-
gen bonding states, and that assignment was later verified by NMR
analysis of the diols (86). This was the first case in which dimer models
of vinyl polymers were separated into diasteieoisomers. Although
preparative gas chromatography has become a useful tool for sepa-
rating such isomers, such elution techniques still are convenient for
large-scale separation and for the separation of compounds with high
boiling points.
Heptane-2,4,6-triol was synthesized by Miyake and Kominami (87)
by hydrogenation of diacetylacetone. The trio1 was separated into
three isomers, which were found to correspond to syndiotactic, het-
erotactic, and isotactic triols by the elution method (88,89). This was
the first case in which the trimer models of vinyl polymers were sep-
arated into three stereoisomeric forms.
H OH H
I I I
Syndiotact ic CH ,--C-CH,-C--CH,-Cl-CH
I I I
OH H OH
H H OH
I I I
Heterotactic CH,-CLCH2-CCH,-C-CH3
I I I
OH OH H
H H H
I I I
Isotactic CH,-C-CH,-C-CH,-C-CH3
I I I
OH OH OH
The isotactic and syndiotactic triols were obtained as crystals melting

at 67°C and 89"C, respectively. Separation of the three isomers of
2,4,6-triacetoxyheptane, by repeated fractionation through an 80-plate
distillation column, was reported by a Czechoslovak group (90).
Starting from these models, various ester and acetal models were
prepared and used to study polymer structures. They are borate (83,84),
formate (88), acetate (85,89,90), trifluoroacetate (9 I), formal (92), and
acetoacetal (93).
Progress in the synthesis of stereoregular PVA has recently been
reviewed by Murahashi and Nozakura (94-96).
111. STEREOREGULARITY A N D CRYSTALLIZABILITY OF

PVA A N D ESTERS
The relationship of poly(viny1 acetate) to PVA is of particular interest

with regard to the structure and crystallinity of polymers. Poly(viny1
acetate) and PVA are interconvertible, and no isomerization seems to
occur in the steric structure of the polymer main chain during polymer
transformation. The fact that PVA is a typical crystalline polymer
while its acetate has never been crystallized drew attention to the
stereochemical structure of the polymers and still provides an appro-
priate example of structure-crystallinity relationships in vinyl poly-
mers. The results of investigations on tacticity-crystallizabity relations
in PVA and its esters are summarized in this section.
A. PVA
An X-ray fiber pattern of PVA was first reported by Halle and

Hofmann (1) as early as in 1935, and the fiber identity period, then
thought to be 2.57 A, was attributed to each monomeric vinyl alcohol
450 FUJI1
Fig. 3. Fiber patterns of conventional poly(viny1 acetate) (left) and PVA (right)
unit. No pa-rticular attention was paid to the steric structure of the

polymer. An extended zigzag conformation of the isotactic PVA mol-
ecule was assumed by Mooney (2) to account for the X-ray fiber
diagram. B u m (3) reported results of his substantial examinations of
the X-ray diffraction of PVA in a short communication, and suggested
that the randomness of the steric arrangement of hydroxyl substit-
uents caused poly(viny1 acetate) to be noncrystallizable whereas PVA
was crystallizable regardless of its stereoregularity because of the small
size of the hydroxyl groups. The crystallinity of copolymers of ethylene
and vinyl alcohol was presented as evidence supporting this view (97).
Sakurada and Fuchino (98,99) had suggested the possibility that the
highly crystalline nature of PVA was due to its regular stereostructure
and that poly(viny1 acetate) was not crystallizable because the bulky
side groups interfered with the regular interchain forces required for
crystallization. They thought that alternation of d and 1 isomeric
forms along the polymer chain (syndiotactic model) was preferable to
Mooney’s model, and that some explanation might be found for the
identity period of 2.52 A. Later Sakurada et al. (4) and Kakinoki (100)
postulated a model in which two syndiotactic zigzag chains in a unit
POLY (VINY L ALCOHOL) 45 1
Fig. 4. Single crystals of conventional atactic PVA (102).
cell were shifted by 2.5 A toward each other in the chain direction, as
in Bunn’s model (3).
Various experimental findings revealed that the conventional PVA
obtained from vinyl acetate is atactic. Several poly(viny1 formates) that
showed different crystalline forms, depending on tacticity, gave one
type of X-ray pattern on hydrolysis (101). Polymer single crystals were
obtained from the conventional atactic PVA (102,103). These results
clearly showed that Bunn’s view on the stereostructure of conventional
PVA was correct.
Isotactic-rich PVA samples obtained from poly(viny1 ethers) (isotac-
ticity was up to 80% of the diads) did not show any new type of crystal-
linity based on the isotactic structure (16,102), but gave reflections
similar to those of the conventional atactic PVA. Heat treatment
produced very low crystallinity, and the polymers readily dissolved
in water. Murahashi et al. (34-35) studied PVA samples of higher
isotacticities (up to 90% of the diads). They found that new infrared
absorption appeared at 1160 cm-’ and that the melting point of PVA,
measured by differential thermal analysis, showed a minimum at 80%
452 FUJI1
Fig. 5
POLY( VINYL ALCOHOL) 453
Fig. 5. (contd.)
454 FUJI1
Fig. 5. Fiber patterns of poly(viny1 alcohol) samples derived from (u) isotactic-rich
and ( h ) syndiotactic-rich poly(viny1 formate) by heterogeneous hydrolysis. Figures on
page 452, poly(viny1 formate); figures on page 453, poly(viny1 alcohol) produced by
heterogeneous hydrolysis; figures above, poly(viny1 alcohol) after heat treatment at
200°C (101).
isotacticity. The PVA samples became less readily soluble when

isotacticity exceeded 80%. From these findings they deduced that
there might be a new structural order based on the highly isotactic
structure of these samples.
t
210%
15OoC
IOOOC
20oc
I 1 I
10 20 30
20,deq
Fig. 6 (a)
456 FUJI1
t
20 oc
210oc
18OoC
I50 OC
IOOOC
20%
I I I
10 20 30
2 8 , deg
Fig. 6. Effect of temperature on the X-ray diffraction patterns of ( a )atactic and ( h ) ISO-
tactic PVA (101).
POLY (VINY L ALCOHOL) 457
Syndiotactic-rich PVA samples were more difficult to prepare, and
no high-molecular-weight samples have been obtained to date. As in
isotactic-rich PVA, no difference has been observed in the crystal
structure of syndiotactic rich samples as compared with atactic PVA.
Although completely syndiotactic PVA has not been obtained, it is
interesting to speculate as to what type of fiber diagram it would show.
B. Poly(viny1 Acetate)
As was pointed out by Sakurada and Fuchino (98), the presence of
the acetate side group does not facilitate crystallization of the polymer,
and no crystallization has been observed in stereoregular poly(viny1
acetate). The isotactic-rich PVA (80% isotacticity) readily crystallized
as the formate but did not show any sign of crystallizability as the
acetate (52,101). Murahashi et al. (34-35) acetylated PVA samples of
90% isotacticity and of 74% syndiotacticity. Both acetates were amor-
phous, but the latter was insoluble in either methanol or acetone, unlike
isotactic or atactic poly(viny1 acetate), and dissolved in chloroform.
Ohyanagi and Matsumoto (104) found that the &temperature in ethyl
n-butyl ketone of poly(viny1 acetate) obtained from vinyl formate
polymerized at - 78°C (syndiotacticity = 61% and 1,2-glycol content
= 0.2 mole %) was lower by 3°C than that of a polymer of vinyl acetate
prepared at 60°C (syndiotacticity = 53% and 1,2-glycol content = 1.8
mole %). This seems to be consistent with the result of Murahashi et al.
As in the case of PVA, the crystallizability of more highly syndiotactic
poly(viny1 acetate) is an interesting but unsolved problem.
C. Poly(viny1 Formate)
The crystallizability of poly(viny1 formate) was shown to be very sensi-
tive to changes in tacticity. Syndiotactic-rich poly(viny1 formate) gave
a fiber pattern with an identity period of 5.0A (52-54). On the other
hand, isotactic-rich poly(viny1 formate) displayed a sharp X-ray fiber
pattern showing a rhombohedra1 unit cell with identity periods referred
to the hexagonal axes; a = b = 15.9bi and c = 6.55A (fiber period)
(52,102). The crystal structure was very similar to that of isotactic
polystyrene (1 8). Therefore the syndiotactic and isotactic poly(viny1
formate) molecules seemed to take the planar zigzag and 3, helical
458 FUJI1
Fig. 7. A fiber pattern of isotactic poly(viny1 forrnate) (101).
conformations, respectively. Density versus D,, 6/D850plots recorded

a minimum point at around D,,6/D,,0 = 0.2, showing crystallization
in the two respective stereoregular structures (101).
Syndiotactic-rich polymers were semicrystalline and seemed to have
a laterally ordered structure as in poly(viny1 trifluoroacetate) and
polyacrylonitrile (105). Only a sharp equatorial reflection at 26 = 13.5"
and a diffuse layer that showed an identity period of 5.0A (28 = 25")
were observed in the fiber pattern. A very weak, diffuse layer was
sometimes observed in the meridional direction when the specimens
were highly stretched (53,101). Murahashi et al. (34-35) converted a
PVA sample of 74% syndiotacticity to poly(viny1formate) and observed
an X-ray powder pattern in which three additional rings were seen at
26 = 20"17', 34"47', and 43"50'. No fiber pattern was obtained because
of a low degree of polymerization (DP) of the sample. Rosen et al. (54)
Fig. 8. A fiber pattern of syndiotactic-rich poly(viny1 formate) (101).

460 FUJI1
1.36
1.35
>\
.-
4-
In
C
al
0
1.34
1.33
0 0.1 0.2 Q3 0.4 0.5 0.6 0.7
D91S /D850
Fig. 9. Plot of density versus tacticity in poly(viny1 formate) (101).
reported a somewhat different result for the fiber pattern of poly(viny1

formate) prepared at 0°C. They observed three equatorial arcs with
d-spacings of 6.5 A (28 = 13.6", very strong), 3.74 A (23.8", weak), and
3.32a (25.9", weak), one set of diagonal arcs with d = 4.2A (21.2",
moderately weak) corresponding to an axial translation of 5.1 A, and
a diffuse meridional arc with d = 2.68 A. The presence of two kinds of
crystallites was assumed on the basis of these reflections. However, the
conditions used in preparing the polymers and sample specimens, as
well as the infrared spectrum reported for the polymer, suggest that
these samples were no more crystalline than those used in other studies
(34-35,53,102). Poly(viny1 formates) prepared in the temperature range
of -78" to 120°C showed no more than two reflections when subjected
to various treatments (106). Consequently the results obtained by
Rosen et al. remain in doubt. Some impurities in the polymer sample
or partial hydrolysis of the polymer might have caused the additional
reflections. A reflection that gave a set of diagonal arcs, which showed
a fiber period of 5.0 A, showed a spacing d = 3.6 A (28 = 25") (53,101),
so that the spacing d = 4.2 A reported for this ring by Rosen et al. may
have been a misreading.
POLY(VINYL ALCOHOL) 46 1
Crystallized state
----- Amorphous state
I I I I
10 15 20 25 30
2 8 , deg
Fig. 10. Scanning curves for syndiotactic-rich poly(viny1 formate) in the amorphous
and crystallized states (101).
An interesting finding in the crystallization of this type of poly(viny1

formate) was the appearance of the reflection at 26 = 13.5" in place of
the inner halo at approximately 26 = 16". The polymer gave two
amorphous rings in the amorphous state. The inner halo, which does
not exist in the X-ray pattern of the monomer, is called a "polymeriza-
tion ring" and presumably shows the lateral order in vinyl polymers
(107). The appearance of the crystalline peak with a reduction in the
intensity of the inner halo apparently signifies improvement of the
lateral order in the polymer.
The solid-state polymerization of vinyl formate presented a unique
case in which the derived polymer gave an X-ray pattern quite different
from those of the polymers obtained by conventional free-radical
polymerization in the liquid state (57). A reflection at 26 = 21'40 was
observed in the X-ray pattern of that polymer instead of the reflection
at 26 = 13.5" seen with the conventional polymers. The new reflection
was supposed to correspond to the (220) reflection of isotactic poly(viny1
formate). This is the strongest reflection and is present at 28 = 22'30
in the pattern of predominantly isotactic poly(viny1 formate). Different
spacings (d = 3.95 and 4.10A) were considered to be due to the dif-
ferent tacticities of the polymers. The NMR spectra revealed that the
462 FUJI1
increased isotacticity obtained with solid-state polymerization was only

a few per cent in the diad as compared with the ordinary free-radical
polymerization (see Section IIB). Evidently the X-ray pattern suggests
the presence of isotactic sequences beyond a certain length.
Another type of crystalline X-ray pattern was obtained from poly-
(vinyl formates) of low DPs prepared by polymerizing the monomer in
substantial amounts of aldehyde (52). The infrared spectra showed
intense crystallization-sensitive bands corresponding to the syndiotactic
structure (52). On the other hand, the importance of the low DP for
crystallization was also stressed (50). NMR analysis showed a slight
increase in syndiotacticity owing to use of the aldehyde medium, but
the stereostructure was still random. Attempts to prepare oriented
samples failed because of the low DP, but single, crystal-like platelets
Fig. 11. A fiber pattern of poly(viny1 formate) prepared by solid-state polymerization

(57).
Fig. 12. Single crystal-like platelets obtained from atactic poly(viny1 formate) of
low DP (107).
464 FUJI1
were prepared by precipitating the polymer from dilute solutions in

acetonitrile. An orthorhombic unit cell was deduced from the electron
diffraction pattern: a = 6.74 A, b = 8.78 A, and y = 90". No direct
information has yet been obtained regarding the identity period of the
c-axis (108).However, most reflections were concentrated on the equator,
leaving only a set of weak, nonequatorial reflections of d = 8.1 2 A and
4.06 A, and therefore the polymer seemed to be only laterally ordered
in spite of the formation of the single, crystal-like platelets. The chain
conformation of the polymer has not yet been elucidated (see Section
VIB3). The increased crystallizability in polymers of low D P is well
known. This effect is remarkable in semicrystalline polymers such as
poly(viny1 chloride) (109) or polyacrylonitrile (109a). With these poly-
mers increased crystallinity was observed in the X-ray pattern but no
essential change in crystal structure was encountered. Poly(viny1
formate) is unique is showing two completely different X-ray pat terns,
depending on DP. When vinyl formate was polymerized in n-butyral-
dehyde, reflections characteristic of a low D P appeared at about
D P = 80, but this borderline seemed to be affected by the structural
regularity of the polymer. It is noteworthy that a syndiotactic-rich
PVA of low DP (syndiotacticity = 74% and D P less than 30) did not
show these characteristic reflections but exhibited the pattern of a
high DP type in the form of formate (34-35).
D. Poly(viny1 Trifluoroacetate)
Another poly(viny1 ester) whose fiber pattern has been the subject of
discussion with regard to tacticity is poly(viny1 trifluoroacetate) (see
Section IIB). Chatani et al. (42,110) compared the X-ray fiber patterns
of three poly(viny1 trifluoroacetate) samples. Two samples were made
by polymerizing vinyl trifluoroacetate at 6 0 and -70 C. The third
sample was prepared by converting the conventional PVA derived
from vinyl acetate by esterification. All samples gave similar X-ray
patterns. The equatorial reflections were interpreted on the basis of
data for a doubly-oriented specimen, and an orthorhombic unit cell
was deduced. Three diffuse meridional reflections showed repeat dis-
tances of 4.8 A, 2.8 A, and 2.4 A. A long fiber period was required to
explain all the observed meridional reflections, but if the 4.8 A reflec-
tion, which was relatively sharp, was taken as showing the fiber period,
10 15 20 25
28, deg
Fig. 13. ( a ) A fiber pattern of poly(viny1 trifluoroacetate) prepared by polymerization
at 60°C (101). (6) Scanning curves for poly(viny1 trifluoroacetates) of different tacticities
(101).
466 FUJI1
the following unit cell dimensions were obtained: a = 9.54 A,

b = 12.44A, and c = 4.8 A. Bohn, Schaefgen, and Statton (105)
interpreted the structures of poly(viny1 trifluoroacetate) and poly-
acronitrile as “laterally ordered rather than well-developed three-
dimensional crystals.
Cooper, Johnston, and Vaughan (111) converted PVA samples
obtained from several vinyl esters polymerized at different temperatures
to poly(viny1 trifluoroacetates) and compared their crystallinities. A
strange result was obtained. The crystallinity was independent of the
starting vinyl ester monomer but was markedly influenced by poly-
merization temperature. On the other hand, the water solubility of PVA
was largely dependent on the monomer structure rather than poly-
merization temperature. This correlation of the crystallinity of poly(viny1
trifluoroacetate) and polymerization temperature of the original
polymer seems to be incorrect. The X-ray photographs of the trifluoro-
acetate samples claimed to be more crystalline show reflections char-
acteristic of PVA, and the intensities of these reflections increase at
lower polymerization temperatures of the original polymer (see ref 111).
The X-ray technique employed in this study required moistening of
poly(viny1 trifluoroacetate) powders to prepare sample specimens.
Poly(viny1 trifluoroacetate) as well as poly(viny1 formate) is very
susceptible to hydrolysis, and therefore this treatment may well have
caused hydrolysis of the sample.
Fuji et al. (101) investigated the X-ray patterns of poly(viny1 trifluo-
roacetates) of various tacticities. Only two peaks were observed in the
spectra obtained with an X-ray diffractometer on unstretched polymer
films. The intensity of the inner ring was higher in samples of higher
syndiotacticity. A clear difference was observed when the polymer
films were stretched. X-ray photographs suggested the occurrence of
crystallization together with orientation in the more syndiotactic
samples. An isotactic-rich sample showed poor orientation on stretch-
ing, and no additional equatorial reflections appeared. Hence the
lateral order in the polymer seemed to be related to the syndiotactic
structure. In conclusion, the crystallizability of poly(viny1 trifluoroace-
tate) is less sensitive to tacticity than that of poly(viny1 formate). The
laterally ordered structure seems to be favored in more syndiotactic
polymers. No crystal structure characteristic of the isotactic structure
has been observed.
IV. SPECTROSCOPIC STUDIES
A. High-Resolution NMR Spectra

I . Poly(viny1 Acetate)
Exact determination of the tacticity of PVA was made possible by
observation of the methyl proton signal of poly(viny1 acetate). Bovey
et al. (112) found that the methyl signal of poly(viny1 acetate) was a
triplet and suggested that this was due to three different steric environ-
ments, as in the methyl signals of poly(methy1 methacrylate) (113).
They suggested that the central peak might correspond to acetoxy
groups centered in the heterotactic triad sequence, but did not assign
the other two peaks. The ratio of the three peak areas for poly(viny1
acetate) prepared at 60°C was 0.23 (8.02~) :0.47 (8.042):0.30 (8.06~),
showing an almost ideal atactic structure. Ramey and Field (44,114)
attempted to convert isotactic poly(viny1 methyl ether) to PVA by
treating it with hydrogen iodide, and to correlate the spectra of PVA,
poly(viny1trifluoroacetate), and poly(viny1 acetate) on the basis of the
assigned spectrum of poly(viny1 methyl ether) (112,115). The three
three methyl signals of the acetate were assigned to syndiotactic,
heterotactic, and isotactic triads in the order of increasing field strength.
This assignment was later proved to be erroneous and was corrected
to the reverse order by two groups (32,116), who employed polymer
samples with a wide range of tacticities. The X-ray fiber patterns of
poly(viny1formate) (52) and the reactivity of PVA with aldehydes (117)
also clearly supported the assignment. In addition, the chemical shifts
of the acetoxy protons in the three stereoisomers of 2,4,6-triacetoxy-
heptane were consistent with the assignment of the polymer spectra
(116). Incomplete transformation of poly(viny1 methyl ether) to PVA
and insufficient stereoregularity of the polymer samples seem to have
been the cause of the earlier erroneous assignment.
Variations of chemical shifts due to different steric environments
are much smaller in poly(viny1 acetate) than in poly(methy1 meth-
acrylate) (113); since the three acetoxy signals largely overlapped,
determination of peak areas was difficult. Careful observation of the
spectra in methylene chloride solutions showed that the chemical shift
between isotactic and heterotactic peaks was 25% larger than that
between heterotactic and syndiotactic peaks at room temperature. In
468 FUJI1
I I
8.0 8.5 t
Fig. 14. NMR spectra of various poly(viny1 acetates) in methylene chloride at room
temperature. Polymers A and B were derived from vinyl r-butyl ether polymerized in
toluene and in a toluene-nitroethane (4: 1) mixture, respectively. Polymer C was the
conventional poly(viny1acetate) (same as polymer C of Fig. 15). Polymer D was derived
from vinyl formate polymerized at -78°C. These spectra are related to the data in Tables
I1 and IV. Only for polymer A is the spectrum in carbon tetrachloride at 110°Calso shown
(top). The spectrum is shifted slightly upfield to avoid overlapping (59).
addition, the syndiotactic peak was broader than the isotactic peak
(59). This dependence of line width on tacticity is the same as that
reported for poly(methy1methacrylate) (118,119).Therefore the isotactic
component may be overestimated if tacticity is estimated from relative
peak heights. This may be a reason for the discrepancies in values
2 2
-0
uw
2 -0
U
u
8 0
2u
s 2
2U
w 0- 28-
E 0
0w
2
2 -0
u
r8'0
0
0
z
2
$0
00 8- fJ
0
0
, E
I ,
1
1
470 FUJI1
reported for the tacticity of the conventional polymer prepared by

polymerization of vinyl acetate.
The methylene and methine proton signals were reported to be
insensitive to the steric structure of the polymer. This followed from
decoupling experiments using the double resonance technique (32,112).
Ramey and Field reported in an early communication (114) that the
methine proton gave a triplet, but this was not confirmed on re-exam-
ination (120). On the other hand, the signal of the methylene protons
was not considered to be stereosensitive in the first report (114) but
was interpreted as the overlapping of two triplets arising from the
meso (low-field) and dl (high-field) portions in the second communica-
tion (120). The methylene proton signal of poly(viny1 acetate-a-d,)
showed that this was not the case, and that the signal was an overlap
-
I I
8.0 8.5 T
Fig. 15. NMR spectra of atactic polymers of vinyl acetate and vinyl acetate-u-d,
(C-d,) (59).
of an AB quartet arising from the nonequivalent meso-methylene
protons and a singlet from the equivalent dl-methylene protons (59).
Besides the three acetoxy proton signals, a small hump was observed
at z = 7.98 in the spectrum of a poly(viny1 acetate) sample prepared
at 60°C. This hump was barely visible in a polymer prepared at - 78"C,
and therefore seems to be related to some irregularity in the polymer,
probably deviation from the head-to-tail structure (59).
Bovey et al. (112) reported that the methyl signal at the highest field
was a doublet, and assumed long-range coupling with a backbone
methine proton. DoskoCilova et al. (121) stated that a similar effect
was observed in the dimer model compound, dl-2,4-diacetoxypentane.
However, no such splitting was observed in the 100-MHz spectra of
the pure dimer model and poly(viny1 acetate) (59).
2. P V A
In contrast to the spectra of esters of PVA, most published results
on the spectra of PVA itself show good agreement in interpretation
with regard to the stereostructure of the polymer.
Differences in the methylene signals of PVA samples of different
tacticities were first noted by Danno and Hayakawa (122). Estimation
of tacticity by analysis of the methylene and methine proton signals
was attempted by Satoh et al. (86) and Tincher (123). The spin-spin
decoupling technique was also applied (32,44,59,124).
The methylene signal was interpreted as an overlap of two triplets,
assuming the meso-methylene protons to be equivalent (86,123,124).
This seems to be consistent with the results of the decoupling experi-
ments, which simplified the methylene signal to a doublet (32,44,59).
For isotactic-rich PVA in deuterium oxide solution a long-range effect
(tetrad) was deduced from the 100-MHz spectrum by Ramey and Lini
(120).However, careful observation of the methylene signal of PVA-cc-d,
at 100 MHz showed no sign of a longer-range effect under these condi-
tions (59).
The equivalence of the meso-methylene protons in poly(viny1
chloride) has been much debated (e.g., ref. 125). Shimanouchi, Tasumi,
and Abe (126) observed the spectra of 2,4-dichloropentane and 2,4,6-tri-
chloroheptane and showed that the chemical shift between two meso-
methylene protons was smaller in the trimer than in the dimer. They
deduced from this finding that the nonequivalence would keep
472 FUJI1
TABLE VIII
Chemical Shifts between Two meso-Methylene Protons in Dimer and Trimer Models of
Various Polymers"
Poly(viny1alcohol) Polystyrene Poly(viny1 chloride) Poly(viny1 acetate)

in D,O in CCl, in CCI, in CCI,
OH
1 0.15
OH C,H,
I 0.21
C,H,
1
c1
I 0.30 7 OAc
1 0.34
OAc
I
OH Cl
OH OH
~
c1
1 0.12 7 CI OAc
1 1 0.18
OAc
I
OAc
I
6,, is expressed in parts per million
decreasing as the chain length of the polymer increased. A comparison

of the spectra of the chloride models with those of PVA and poly(viny1
acetate) models suggested an interesting tendency with respect to this
problem (59). From the model spectra, the least nonequivalence was
predicted for PVA and the highest nonequivalence for poly(viny1
acetate). This is consistent with the observed polymer spectra.
The methine signal was interpreted as three overlapping quintets
(123), and an approximate estimation of tacticity was made by sep-
arating the three components (123,127). The signal was simplified to a
triplet by decoupling the j?-proton in solutions of deuterium oxide,
dimethyl sulfoxide, and phenol (32,44,124).
Good agreement was observed between the models and polymer
samples in line order with regard to tacticity. The dl-methylene signal
occurred at a higher field than the rneso-methylene signal, and the
- CH2 -
I
A normal
(a)
5.2 5.6 6.0 ‘I;
Fig. 16. Uncoupled methylene and methine proton signals of PVA. ( a ) Methylene
signal of PVA-a-d, in D,O at 100 MHz and 100°C (59). ( b ) Methine signal of PVA in
phenol at 56.4 MHz and 180°C. Normal (top) and uncoupled by the double resonance
technique (16).
methine signal was in the order of syndiotactic, heterotactic, isotactic

with increasing field strength (32,44,59,123,124).
3. Poly(viny1 Trguoroacetute)
Both the proton and fluorine signals of poly(viny1 trifluoroacetate)
have been studied. Ramey and Field (44) applied the decoupling
technique and observed the methine proton signal as a triplet. They
assigned the three peaks to isotactic, heterotactic, and syndiotactic
474 FUJI1
TABLE IX
Line Order of Proton Signals of PVA Derivatives in Polymers and in Models with
Regard to Tacticity (128)
Line Order
Polymer Solvent Signals
Model compounds Polymers
PVA
Poly(viny1 formate) (CD,),CO COH

CH3
Poly(viny1 acetate) CH2CIz CH 2

CH
Poly(viny1 trifluroracetate) (CD3),C0 CH,

CH
1 I I
0 50 100
cycles/sec
Fig. 17. Fluorine resonance. spectra of various poly(viny1 trifluoroacetates) in acetone
at 56.4 MHz and 25°C (28). Polymer A, isotactic-rich; B, atactic; C and D, syndiotactic-
rich.
triads, respectively, with increasing field strength. However, this was
based on the assignment of poly(viny1 methyl ether), with which
conversion to PVA and to poly(viny1 trifluoroacetate) was attempted ;
the polymer transformation seemed to be incomplete (see Section
IVA1). In addition, a study of the spectra of poly(viny1 acetate) based
on the correlation of poly(viny1 trifluoroacetate) and PVA led to an
erroneous assignment. Consequently the assignment of Ramey and
Field remains in doubt. The spectra of the trimer models would in-
dicate an opposite line order (128). In all other vinyl polymers the line
orders of the methylene and methine proton signals are the same with
regard to steric configuration. That is, i -+ s in the methylene proton
I
I
J
B--A
A
-1.60 -C
Fig. 18. Fluoromethyl resonance signals of various poly(viny1 trifluoroacetates) in
acetone at 94.1 MHz and room temperature. Polymer A , I = 0.59, H = 0.30. S = 0.1 1 ;
B, I = 0.24, H = 0.46, S = 0.30; C, I = 0.16. H = 0.46, S = 0.38, according to NMR
analysis of derived poly(viny1 acetates) (91).
476 FUJI1
and S 4 H + I in the methine proton with increasing field strength

(128), except for polystyrene, in which the substituents have a large
shielding effect. To determine with certainty whether the line order of
poly(viny1 trifluoroacetate) is another exception, the methine signal of
the polymer may have to be reexamined.
Three peaks were observed in the fluorine magnetic resonance
spectra of the polymer (28). From peak positions and relative intensities
for polymer samples of different tacticities, the three peaks were inter-
preted in terms of triad stereosequences and were assigned in the same
order as that for the methyl proton signals in poly(viny1 acetate). The
tacticities of various polymer samples estimated from relative areas of
the three trifluoromethyl signals were more syndiotactic than those
determined from the proton resonance spectra. However, the fluorine
resonance spectra obtained at 94.1 MHz revealed the presence of more
than four peaks (91), and the relative peak positions were different from
those seen previously at 56.4 MHz (28). The principal peak of the
polymer of the highest isotacticity did not correspond to the peak at
the lowest field, but to one of the two principal peaks of an atactic
sample. Moreover, the intensity ratios of the peaks were affected by
the solvent employed. The spectra could not be interpreted in terms
of triad stereosequences. Some long-range effect or other influences
may have to be considered in interpreting the spectra.
4 . Poly(viny1 Formnte)
Ramey, Lini, and Statton (58) studied the spectra of poly(viny1
formate) and reported that the methylene and methine protons were
not stereosensitive but that the formyl proton gave a triplet signal.
The three peaks were assigned to isotactic, heterotactic, and syndiotac-
tic stereosequences, respectively, with increasing field strength, on the
basis of the tacticities of PVA and poly(viny1 acetate) derived from
poly(viny1 formate). This line order is consistent with that expected
from the spectra of the trimer models (see Table IX).
5. Poly( vinyl Formal)

Two types of m-dioxane rings, cis- and trans-formals, are formed by
the reaction of PVA with formaldehyde (129,129a-c). The dioxymeth-
ylene proton signal was found to be useful in distinguishing these two
stereoisomeric formal rings in the spectra of poly(viny1 formal) (92).
0-CH2-0 CH C-Cy-C CH3 TMS
c-c-c-c-c-c-c
I I I
OH 0 0
L 1 CH2
OH
I
c-c -c-c-c-c-c
I
It t
, I
II *I I I
5 6 7 8 9 10
T.
Fig. 19. Dioxymethylene proton signals of formals of isotactic and syndiotactic hep-
tane-2,4,6-triol in dimethyl sulfoxide at 30°C (92).
Both in model compounds and in polymers, the dioxymethylene pro-

tons of cis-formal derived from the meso-diol portion gave an AB
quartet, while those of trans-formal derived from the dl-diol portion
were found to be equivalent because of rapid exchange between the
two chair forms, which are energetically equivalent or nearly so. This
is an exceptional case in which two stereoisomeric cyclized structures
in vinyl polymers are clearly distinguished by their NMR spectra.
In higher acetals of PVA, 1,3-dioxane rings become trisubstituted
and tend to take a triequatoriul form (in the case of cis-acetal) or a
diequatorial-axial form (in the case of trans-acetal) in preference to a
triaxial or a diaxial form. Therefore cis- and trans-acetals have not
been distinguished in the polymer spectra. Acetoacetals of meso- and
dl-pentane-2,4-diolhave been studied by Fujiwara and Fujiwara (130).
The spectra showed that both acetals were in the chair form and that
the methyl group in the C-2 position occupied an equatorial position
in both isomers.
478 FUJI1
Fig. 20. Dioxymethylene proton signals of poly(viny1 formals) in dimethyl sulfoxide

at 120°C. ( a ) From isotactic-rich, (b) syndiotactic-rich, and (c) conventional atactic
PVA (76).
B. Infrared Spectrum
1. P V A
A number of investigations have been made into the infrared spectrum
of PVA. Most studies were concerned with the 1141 cm-' band until
recently. Nagai and Sagane (131) found that the intensity of this band
was dependent on the crystallinity of the polymer. A linear relationship
was confirmed between the band intensity and the film density (132,133).
The band showed strong perpendicular dichroism (134), and was not
significantly affected by heterogeneous formalization after crystalliza-
tion or by deuteration of hydroxyl side groups (135-137). There has
been some discussion as to the origin of this band. A relationship to
the C 4 bond was deduced from the dichroic nature (134), and a
shift of the C 4 stretching vibration of the secondary alcohol at
1093 cm-' to 1141 cm-' by formation of a hydrogen bond was sug-
gested on the basis of the spectra of model alcohols (138). Assignment
to the C - 0 4 stretching vibration was made (139) on the assump
tion that an ether linkage had been formed by heat treatment, but this
was inconsistent with various experimental evidence and was later
corrected (140-142). Tadokoro, Seki, and Nitta (135,143) examined
doubly oriented films of PVA and showed that the direction of the
transition moment of the 1141 cm-' band was parallel to the plane
of the main chain zigzag. They deduced that the band was due mainly
to the symmetric C--C stretching mode related to the regular repeti-
tion of the trans conformation of the zigzag chain in the crystalline
region. The C 4 stretching mode of a portion of a chain, in which an
intramolecular hydrogen bond is formed between two neighboring
hydroxyl groups on the same side of the C 4 main chain, or its
association with the C--C stretching mode, has also been suggested
for this band on the basis of the spectra of model alcohols (83,84,142,
144).
All these discussions were based on the spectra of the conventional
atactic PVA and of the model compounds. As a result of the successful
preparation of stereoregular PVA, various spectral differences arising
from different stereostructures were found experimentally. They are
briefly summarized below.
The 1 / 4 1 cm- ' band. ( a ) In predominantly isotactic PVA samples,
the 1141 cm-' band was very weak and was not strengthened by heat
treatment (16,101). (b) In PVA samples derived from vinyl acetate, the
band intensity showed a slight increase as the polymerization tempera-
ture of vinyl acetate was lowered (145,146). (c) A further increase in
the band intensity was observed in PVA samples obtained from vinyl
formate polymerized at lower temperatures (55). ( d ) In syndiotactic-
rich PVA samples (syndiotacticity = 74%), the band intensity was
considerably high but heat treatment was not very effective, presumably
because of the low D P of the sample (34-35). (e) The band, which was
hardly observed at around 80% isotacticity, reappeared in the spectrum
of a highly isotactic PVA sample (isotacticity = 91 "/.) (34-35).
480 FUJI1
I085
I I I I 1 I I I 1
1600 1400 1200 1000 800
cm-q
Fig. 21. Infrared spectra of various PVA samples (34). PVA samples 1 and 10 were
derived from vinyl trimethylsilyl ether polymerized in toluene at -95'C and in nitro-
ethane at - 78"C,respectively. Sample 2 was derived from vinyl t-butyl ether polymerized
in toluene at -78 C . Sample 6 was derived from vinyl trifluoroacetate polymerized
in methyl acetate at 60°C (see Table 111).
The 9I6cm-' band. The 916cm-' band was hardly observed in
predominantly isotactic PVA samples (1 6), and the band intensity
increased with increasing syndiotactic content of the polymer (65).
The 1160 m i - ' band. In a highly isotactic PVA sample derived from
vinyl trimethylsilyl ether (isotacticity = 91%), a new band appeared
at 1160 cm- (34-35).
T h e 0-H stretching band. The 0-H stretching band, which
appears at 3321 cm-' and shows no dichroic nature in the spectrum
of atactic PVA, shifted to 3350 cm- and showed parallel dichroism
in predominantly isotactic PVA samples (16). (The 1440 cm-' band
associated with the 0-H diformation mode also showed a similar
dichroic nature.)
An increase in syndiotacticity seems to be favorable to the 1141 cm-'
band, but no conclusive evidence has been obtained on this point. The
vibrational direction of this band is parallel to the zigzag plane, and
therefore the anisotropic nature of the sample film should have a
marked effect on the band intensity. Orientation of the zigzag plane
parallel to the plane of the film is known to be favored in PVA samples
of relatively high syndiotacticities and low 1,2-glycol content (101).
Another remarkable spectral difference was observed for the
916cm-' band. The relation of this band to syndiotactic structure
was deduced from the spectra of PVA samples whose tacticities were
estimated by reactivity with aldehyde and by X-ray diffraction of the
corresponding poly(viny1 formate) samples (65). The correlation of
D,, 6/D850with NMR analytical results was studied independently by
two research groups (32,146), which proposed the following equations,
respectively.
Syndiotacticity (%) = (72.4 f 1.09)(D9,,/D,50)0~43".0°6
2s = 6O(D916/0850) + 7
%I = -78 (D916/D850) + 59
%H = 18.7 (D916/D850) + 34
It should be noted that this is a convenient but only semiquantitative
method. The 916cm-' band is largely affected by crystallization of
the polymer (65,83). In addition, it was suggested that the 916cm-'
band has a transition moment parallel to the zigzag plane (143), and
therefore the anisotropic nature of the sample specimen may influence
482 FUJI1
the band intensity. Measurement of the spectra of PVA solutions

may eliminate these problems, but unfortunately no suitable solvent
has been found to date. The length of syndiotactic sequences seems to
be important for the presence of the 916 cm-' band. The absorbance
ratio, D,,,/D,,,, was greatly decreased by the incorporation of a
minor amount of comonomer units, such as ethylene or vinyl acetate,
into P V A (148).
The 850cm-' band* was also affected by the stereoregularity of the
polymer. The presence of two absorption bands, at 849 and 835 cm-',
was elucidated by Tadokoro et al. (143) for a doubly oriented specimen.
In highly isotactic PVA samples the 835cm-' band was very weak
and the 849 cm-' band became sharp and strong (16,101).
The 916cm-' band was hardly observed in the spectra of highly
heterotactic PVA samples derived from divinyloxydimethylsilane or
vinyl triisopropylsilyl ether polymerized with cationic initiators.
Furthermore, the 849cm-' band was not sharp or strong as in the
isotactic PVA samples (81,96). On the basis of these findings, Mura-
hash and Nozakura (95)made an interesting calculation. They assumed
that the 916cm-' band was arising from the syndiotactic part while
'
the 850 cm- band was from the heterotactic and syndiotactic parts,
and, from NMR and infrared data, calculated the contributions
of these portions to the 850cm-' band as x = 1.53 and y = 0.74,
+
respectively, in the equation D,,,/D,,, = S/(xI y H ) . As shown in
Figure 22, the plot of D,,,/D,,, versus NMR data gave a good correla-
tion with the calculated contributions. This region awaits further
experimental and theoretical investigations.
The absorbance ratio, D, 16/Ds50, became less sensitive in isotactic-
rich PVA samples. On the other hand, the 1440cm-' band of atactic
'
PVA shifted to 1450 cm- and sharpened. Use of D1450/D,930,instead
of D,,,/D,,,,as a measure of tacticity was proposed for the isotactic-
rich region (34a).
Shimanouchi and Tasumi (149) calculated the normal vibrations for
isotactic and syndiotactic PVA, assuming the planar zigzag chain
structure for both stereoregular polymers. In this calculation the
* As described here, there are two or more absorption bands in this region. Therefore
it is difficult to express the band position by a single frequency. This is why an approx-
',
imate figure, 950 cm- was found to be convenient in expressing the absorbance ratio,
D91€,/D*50 (65).
483
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

0916 4 4 9
Fig. 22. Relationship of D,,,/D,,, to triad stereosequences (95).
symmetric vibrations of C O stretching plus skeletal vibrations and

of C 4 stretching for the syndiotactic model were at 1150 and
908 cm-', respectively. It is interesting that the former vibration was
calculated as 1156 cm-' for the isotactic model. This is consistent with
the appearance of a new band at 1160 cm-' in a highly isotactic PVA
sample (34-35). No C--O stretching vibration of the latter type can
exist for the isotactic model.
In addition to syntheses of various stereoregular PVA samples,
selective deuteration of the PVA main chain was recently achieved
( 150).
The 0-H stretching band, at around 3330 cm- ', showed some
parallel dichroism only in predominantly isotactic PVA samples, and
this was attributed to the presence of intramolecular hydrogen bond
sequences in the isotactic molecules (16). The 3330 cm-' band did not
show fine structures in the polymer spectra, however. An interesting
observation regarding the hydrogen bond in the polymer was made
on the first overtone 0-H stretching band in the near infrared region.
Zhurkov and Levin (151) examined the spectral change in the region
7700-5260cm-' (1.3-1.9 p) at temperatures between 20" and 150°C
484 FUJI1
and observed three 0-H stretching overtone bands at 7040, 6580,

and 6250cm-' (1.42, 1.52, and 1 . 6 ~ ) .On heating, the 7040cm-'
(1.42 p) band was intensified while the latter two bands were weakened.
v
I- PVA A-PVA
J
1.3
I
1.4 1
5
I I
1.6
I
1.7 P
I
1.3
-bI
1.4
1
1.5
I
1.6
I
1.7
Fig. 23. The first overtone 0 - H stretching bands of dimers, trimers, and polymers
of vinyl alcohol (88). I , H , and A mean isotactic, heterotactic, and atactic. respectively.
Diol is pentane-2,4-diol, and trio1 is heptane-2,4,6-triol.
I- Triol H- Triol
12.5
/
L
1.3
I
1.4
I
1.5
I
1.6
I
1.7 !J
I
1.3 I
- 1.5 1.6 I.:
Fig. 24. Effect of dilution with chloroform on the first overtone 0-H stretching bands
of isotactic and heterotactic heptane-2,4,6-triol at room temperature (88). Percentages
refer to the volume fraction of the trio1 in solution.
486 FUJI1
'
The 7040 Cm- (1.42 p) band was assigned to free hydroxyl groups,
) 6250 cm-' (1.6 p) bands to hydrogen-
and the 6580cm-' ( 1 . 5 2 ~ and
bonded hydroxyl groups on the basis of this finding. Glatt and Ellis
(152) studied the near infrared pleochroism of PVA, but no attention
was paid to these three bands. The spectra of this region of various
PVA and model compounds were studied by Kazusa et al. (153). As
seen from the spectra of model alcohols at different dilutions, three
bands, at 7090, 6710, and 6330cm-' (1.41, 1.49, and 1.58 p), can be
assigned to free, intramolecular hydrogen-bonded, and intermolecular
hydrogen-bonded hydroxyl groups, respectively. Apparently intra-
molecular hydrogen bonding is favored in isotactic molecules more
than in syndiotactic molecules. A similar difference was observed in
the polymer spectra.
2. Poly(viny1 Acetate)
Not much work has been done on the infrared spectrum of poly(viny1
acetate) with regard to the stereostructure of the polymer. In an early
paper (101) reversion of the relative intensities of two C--C stretching
bands at 2981 and 2937cm-' in a predominantly isotactic polymer
sample was reported, but this has never been reproduced (154). The
most remarkable spectral change was the appearance of the 1090 cm-'
band in isotactic-rich polymer samples in place of the 1124 cm-' band
present in the spectrum of conventional atactic poly(viny1 acetate)
(154). No definitive assignment has been given to these two bands.
They have a perpendicular dichroic nature (154,155), and the 1124 cm-
band was assigned by Stokr and Schneider (155) to C - 0 4 stretching
combined with C--C skeletal vibrations. Of the bands in the 1750-
1000 cm-' region, only the 1124 cm-' band was appreciably affected
by deuteration of the a-hydrogen of the polymer. In the spectrum of
poly(viny1 acetate-a-d,) the band shifted to higher frequencies and was
markedly intensified with a change in profile (154). This seemed to
suggest that the band was related to the skeletal vibrations. Interestingly,
similar spectral differences arising from stereostructures were also
observed in stereoisomeric dimer and trimer models (154).
3. Poly(viny1 Formate)
Poly(viny1 formate) has a number of bands related to the steric
structure of the polymer, and without exception they are sensitive to
PVAC-3
Dimer
1 Meso
PVAC-2
PVAC-1
1400 1200 1000 800

Frequency, cm-I
Fig. 25. Infrared spectra of poly(viny1 acetate) (PVAc) (left) and 2,4-diacetoxypentane
(right) (154). The D,,,/D,,, ratio of PVA was: 1, 0.02; 2, 0.25; 3, 0.57.
crystallization (52,101). The spectra of poly(viny1 formate) samples

obtained from vinyl t-butyl ether and formate were examined; the
bands at 1420, 1272, 1026, and 924cm-' were found to be related to
the syndiotactic structure, and those at 1345, 1310, 970, 824, and
809 cm-' to the isotactic structure. Murahashi et al. (34-35) studied
the spectra of more highly stereoregular poly(viny1 formate) samples
and made a similar observation. They also noted the slight shifts of
the 1440cm-' and 1380cm-' bands to higher frequencies in highly
isotactic polymer samples. The spectral differences that seem to cor-
respond to these shifts exist in the spectra of the dimer and trimer
compounds, that is, meso-pentane-2,4-diformate absorbed at 1463 and
488 FUJI1
1386cm-' whereas thedlisomer displayed bands at 1458 and 1383cm-'

(77). Murahashi et al. also observed weak absorption at 805 cm-' as
a shoulder of the 794cm-' band in a predominantly syndiotactic
sample.
The 1026 cm-' band was the one most sensitive to crystallization in
the spectra of poly(viny1 formate) samples prepared by free-radical
polymerization of the monomer (53). The band disappeared gradually
on heating, with no transition point. Crystallization could not be
effected by annealing, but was brought about by casting the polymer
solutions or by treating the polymer with borderline solvents. The
polymer solutions in various solveM*showed reversible gelation on
standing, and growth of the 1026cm-' band with gelation was ob-
I I I I I I 1
5000 3000 2000 1500 1000 900 800 700

Wave No., cm-l
Fig. 26. Infrared spectra of various poly(viny1 formates) (101,107). Polymers A, B,
and C were derived from vinyl t-butyl ether polymerized in toluene at - 7 8 T , in hexane
at - 7 8 T , and in ethyl bromide at - 5 0 T ,respectively. Polymers D and E were obtained
by polymerization of vinyl formate at 120" and - 78"C, respectively.
served in chloroform solutions. This suggests that the band is related

to the formation of the intermolecular order (77). The band showed
strong perpendicular dichroism (77).
Low-molecular-weight atactic poly(viny1 formate) was so highly
crystallizable as to form single crystal-like platelets (107). In the
crystallized state the polymer showed absorption characteristic of the
I I I
900 800 7 3
Wave No. (cm-l)
Fig 27. Infrared spectra of poly(viny1 formals) and their models (76).
490 FUJI1
',
syndiotactic structure, at 1420, 1272, and 924 cm- but only the
'
1026 cm- band shifted to lower frequencies to the extent of 10 cm- '.
At the same time, weak shoulders appeared at 824 and 809 cm- ',
which were characteristic of the isotactic structure. This seems to
suggest that the atactic polymer may have local conformations similar
to those of the partly crystallized isotactic polymer.
4 . Poly( vinyl Trguoroacetate)

'
Only the intensity of the 1010 cm- band was found to be dependent
on tacticity, but no further studies on this band were reported (91).
5. Poly(viny1 Formal)
When PVA was reacted with formaldehyde a number of new bands
appeared as a result of the formation of formal rings. Of these, two
bands, at 800 and 785 cm-', seemed to be related to cis- and trans-
formal rings, respectively (76). A linear relationship was confirmed
between the D,,,/D,,, and the translcis ratio determined by NMR
analysis. Similar spectral differences were also observed in formals of
diol and trio1 models.
6. Poly(viny1 Acetoacetal)
When various PVA samples were reacted with acetaldehyde, a
number of absorption bands related to the acetal formation appeared
(93). Of these, the bands at 1035,965, 830, and 795 cm-' seemed to be
associated with trans-acetal, and those at 1010 and 917 cm-', with
cis-acetal.
V. MICROTACTICITY AND CHEMICAL REACTIONS OF

PVA
The effect of tacticity on chemical reactions of PVA is one of the

interesting aspects of the stereochemistry of this polymer, because
PVA is highly versatile in chemical reactions. In fact, no other polymers
are being commercially produced on such a large scale by the entire
transformation of the polymer side chain. Furthermore, a number of
derivatives, such as various poly(viny1 acetals) and poly(viny1 cinna-
mate), are being produced from PVA by chemical reactions. In this
section two sets of reactions will mainly be described as representative
cases of mono- and bifunctional incorporation of hydroxyl groups of
PVA in reaction. These are acetylation and acetalization of the polymer
in combination with hydrolyses of the reaction products, esters and
acetals.
A. Reaction with Aldehyde
I . Hydrolysis of Poly(viny1 Acetal)
Both in model compounds and in polymers, a marked difference in
the rate of hydrolysis has been observed between cis- and trans-acetals
obtained from the meso- (isotactic) and dl- (syndiotactic) diol portions,
respectively. Acetoacetals of various PVA samples of different tacticities
were first subjected to acid hydrolysis (117). Hydroxylamine hydro-
chloride was added to the reaction system to consume all acetaldehyde
formed and to prevent a reverse reaction. Poly(viny1 acetal) obtained
from a predominantly isotactic PVA sample showed the lowest rate
of hydrolysis, and the rate increased with the syndiotactic content of
the original PVA. This result was consistent with that expected from
the conformational law. The acetal obtained from the meso-diol por-
tion may be considered to be a 4,6-cis derivative of 1,3-dioxane, and
that from the dl portion, to be a trans derivative (129). The cis-acetal
may take the diequatorial conformation preferentially over the diaxial
conformation and should be more stable than the trans-acetal, which
may take equatorial-axial or axial-equatorial forms. These conforma-
tions have been verified by NMR spectroscopic analysis of formals and
acetoacetals of pentane-2,4-diol (76,92,93,130).
As in the hydrolysis of poly(viny1 acetate) (156,157), the rate of
hydrolysis of poly(viny1 acetal) is known to be enhanced by the presence
of hydroxyl groups in the polymer chain, and a polymer sample with
the highest hydroxyl content showed the highest rate of hydrolysis
(a) Formal ring from isotactic portion

492 FUJI1
(b) Formal ring from syndiotactic portion
(158,159). If the reaction was to be affected by the neighboring hydroxyl

groups, three different factors had to be considered to account for the
rate difference observed: (a) the reactivity of the acetal ring, (b) the
effect of hydroxyl groups adjacent to the acetal ring, and (c) the hydroxyl
association effect. Of these, the reactivity of the acetal ring itself seemed
to be the most decisive factor, and this was confirmed using the model
compounds, cis- and trans-acetals of pentane-2,4-diol, which showed a
0 50 100 150 200

Time (min)
Fig 28. Hydrolysis of poly(viny1 acetals) derived from various PVA samples. The
D,,,/D,,, ratio of PVA was: A, 0.57; B, 0.35;C, 0.04; D, 0.02 ( I 17).
TABLE X
Rates of Hydrolysis of Model Formals at 60°C (160)
Rate of hydrolysis of formal,

Original polyol
'
k' + lo4 (kg mole- hr-')
meso-Pentane-2,4-dioI 0.22 f 0.05

I sot act ic hept ane-2,4,6-triol 0.16 f 0.05
dl-Pentane-2,4-diol 2.9 f 0.2

Syndiotactic heptane-2,4,6-triol 2.7 i 0.2
marked difference in rate of hydrolysis (93,117). In order to see the

effect of hydroxyl groups adjacent to the acetal ring the rates of hy-
drolysis of formals of pentane-2,4-diol were compared with those of
heptane-2,4,6-triol (160). In this model reaction, formals of the triol
did not show higher rates of hydrolysis than those of the diol. There-
fore the enhancement of the rate was characteristic of the polymer
reaction. Experimental data are still insufficient to account for the
rate acceleration, and a less microscopic explanation-an increase in
the affinity of the polymer molecule or polymer coil for water or the
catalyst-may have to be invoked. The third factor was proposed by
Smets and Petit (159) in order to explain the unusual dependence of
the kinetic scheme on polymer concentration in the acid-catalyzed
hydrolysis of poly(viny1 acetal). However, this has been disputed by
Sakurada et al. (161) on the basis of the improved rate measurements.
In either event, this may not an important factor in the hydrolysis of
highly acetalized PVA samples.
2. Acetalization of P V A
Acetal formation was observed quantitatively only in the reaction
of PVA with formaldehyde (160,162).This system has a great advantage
because cis- and trans-formals formed by the reaction are distinguish-
able both in models and in polymers by NMR analysis (76,102). In
the model reaction a marked difference in the rate of formalization
was found between the meso- and dl-diols, as was also the case in the
reverse reaction, hydrolysis. The isotactic and syndiotactic triols
showed a similar difference in reactivity. The rate of formalization of
the heterotactic triol was intermediate but was closer to that of the
494 FUJI1
TABLE XI
Rate Constants of Formalization of Diols, Triols, and PVA
at 60°C (160)
Compound Constant
Pentane-2,4-diol (kg mole-' h r - ' ) K, = 0.57 F 0.05

K, = +
0.10 0.05
Heptane-2,4,5-triol (kg mole- hr- ') K, = 0.75 0.02

K, = 0.45 & 0.04
Ks = 0.11 k 0.04
PVA (m-' hr-') K, = 0.11

K, = 0.029
TABLE XI1
Configuration of Formal Rings in Partially Formalized
Poly(viny1 Alcohol) (Conventional) (76)
Degree of formalization (mole %)

No. ofruns ~
Total cis-Formal trans-Formal
1 23.0 22.3 0.7

2 36.7 33.4 3.3
3 44.8 40.0 4.8
4 63.1 51.8 11.3
5 78.6 55.8 22.8
6 87.0 59.0 28.0
isotactic triol. In this reaction two types of formal rings were formed,
depending on the diol portion employed in the reaction. NMR analysis
showed that the cisltrans ratio changed with conversion, suggesting
the migration of trans-formal to cis. The initial ratio obtained by
extrapolation to zero time in the plot of cisltrans ratio versus reaction
time showed good agreement with the ratio of the rates of formaliza-
tion of meso- and dl-diols. This suggested that the rate-determining
step of the reaction was the ring-forming step rather than the hemi-
acetal-forming step, which had previously been deduced as rate-
iI
~~
0 5 10 15 20 25
Reaction time (hr)
Fig. 29. Changes of cisltrans ratio with time in the formalization of heterotactic
heptane-2.4,6-tiol at 60°C (160). An equimolar mixture of isotactic and syndiotactic
triols was used as a reference sample.
determing from kinetic data (163).These two steps are indistinguishable

kinetically because the second step, ring formation, occurs only intra-
molecularly.
3. Reaction Equilibrium
The rates of both acetalization and hydrolysis were much lower in
the polymers than in the low-molecular-weight model compounds.
This was interpreted in terms of a “polymer effect,” such as the steric
effect and the organophilic nature of the polymer backbone. These
reactions are reversible, and therefore the polymer effect was offset to
some extent by bringing them to equilibrium.
Three PVA samples of different tacticities were subjected to equi-
librium acetalization together with meso- and dl-pentane-2,4,-diol, and
the equilibrium constant was calculated for each sample (164). In order
to attain the appropriate reagent concentrations at equilibrium and to
avoid complications arising from the heterogeneity of the reaction
496 FUJI1
TABLE XI11
Tacticities of PVA Estimated from Reactivity with Aldehyde (164)and Determined
by NMR Analysis (59)
Tacticity
Polyol K" from reactivity from NMR
i S I S
~~
meso-Pentane-2,4-dioI 8700 1.00 0

PVA derived from vinyl t-butyl ether 3010 0.75 0.25 0.74 0.26
PVA derived from vinyl acetate 1140 0.47 0.53 0.46 0.54
PVA derived from vinyl formate 796 0.33 0.67 0.39 0.61
d/-Pentane-2,4-diol 370 0 1.oo
The equilibrium constant of formalization.
system, equilibrium hydrolyses of acetals were carried out in aqueous

dioxane solutions. Corrections were made for hydroxyl groups isolated
between two acetals in calculating the equilibrium constants of the
polymers. The polymer samples showed different reactivities, depend-
ing on their tacticities, but the calculated equilibrium constants fell
within a range between the constants of the meso- and dl-diols. Assuming
that the two diols represented ideally isotactic and syndiotactic PVAs,
the proportions of the two types of diol portions in the polymers were
calculated, These values, which correspond to tacticity in the diad, are
in fair agreement with tacticities obtained later by NMR analysis of
corresponding poly(viny1 acetate) samples (59).
Sakurada, Sakaguchi, and Shiiki (165) compared the acetalization
of three PVA samples derived from vinyl t-butyl ether, vinyl acetate,
and vinyl trifluoroacetate. The equilibrium constants calculated as
mentioned above were 3100 for the sample derived from the t-butyl
ether and 1440 for the other two samples.
B. Esterification and Hydrolysis of Esters

1. Hydrolysis of Poly(viny1 Acetate)
Both the alkali- and acid-catalyzed hydrolyses of poly(viny1 acetate)
are autocatalytic (156,157). Although no conclusive evidence has yet
been given to account for the mechanism of rate acceleration, an
POLY( VIN YL ALCOHOL) 497
increase in concentration of the catalyst because of its adsorption to
hydroxyl groups formed in the polymer chain by hydrolysis has been
assumed as a likely cause of the rate increase.* According to a calcula-
tion by Sakurada and Sakaguchi (167), the reaction curves could be
plausibly interpreted in terms of activation of acetyl groups adjacent
to the hydroxyl groups. If so, the steric configuration of the polymer
may exert some influence on the degree of acceleration. Thus alkaline
hydrolyses of various poly(viny1 acetates) have been studied in the
hope that differences in reaction behavior could result from different
stereoregularities. The results are briefly summarized below.
1. No difference in hydrolytic reactivity was observed in any of the
poly(viny1 acetate) samples derived from various vinyl esters
polymerized by the free-radical method (1 11,168,169).
2. Predominantly isotactic poly(viny1 acetate) samples, derived
from vinyl t-butyl ether, showed about the same initial rate and
a small degree of acceleration as compared to the atactic samples
mentioned above (168).
3. On the contrary, a lower initial rate and higher degree of accelera-
tion were claimed by Sakurada et al. (169) for a predominantly
isotactic sample from the same source.
4. Poly(viny1acetate) derived from vinyl formate polymerized in the
solid state showed a higher initial rate and less acceleration than
an atactic sample (168).
5. Acetylated products of polyols obtained by acid hydrolysis of
poly(diviny1 butyraI) showed a higher initial rate and less accel-
eration (170).
All published results are in good agreement with regard to the
reaction of poly(viny1 acetates) derived from poly(viny1 esters) prepared
by the free-radical method, such as acetate, benzoate, formate, and
trifluoroacetate. The tacticities of these samples ranged from s = 52%
to s = 61% (by NMR analysis), and similar tacticity differences were
detected by the acetalization behavior ( 1 17,165). Apparently the hy-
drolysis of poly(viny1 acetate) is less sensitive to the stereostructure of
the polymer. A difference in reactivity appeared only in polymers that
had isotactic sequences beyond a certain length in the chain. Results
* This problem has been intensively studied by Sakurada et al., and their work has
been reviewed by Sakaguchi (166).
498 FUJI1
0 20 40 60
Time, min
Fig 30. Time-conversion curves of alkaline hydrolysis of various poly(viny1 acetates)
and their model acetates in dioxane-water ( 3 : 1) at 30°C (77). Isotacticity : polymer 1.0.47;
2, 0.63; 3, 0.74, in the diad, according to NMR analysis.
2 and 4 above are inconsistent with No. 3. The discrepancy seems to

have arisen from the insufficient experimental data and different
methods of analysis of the reaction curve, and would be settled by
further studies.
One of difficulties encountered in studying hydrolysis of the polymer
is the effect of DP on the rate of the reaction. The rate of hydrolysis
of the acetate of the primary alcohol is much higher than that of the
secondary alcohol (171). Therefore the reaction is affected by the end
groups of the polymer, which are acetate of the primary alcohol when
the length of the polymer is shorter than 500. It was necessary to use
reference atactic polymers of low DP in studies of the hydrolysis of
poly(viny1 acetate) derived from vinyl formate polymerized in the solid
state (DP = 200-500) (169).
A syndiotactic structure was deduced for polyols derived from poly(di-
vinyl butyral), from the hydrolytic behavior of acetylated polyols (170),
but it was later suggested that the unusual hydrolytic behavior was due
to the large amount of head-to-head structure in the sample (172).
POLY(VINY L ALCOHOL) 499
TABLE XIV
Rates of Alkaline Hydrolysis of Poly(viny1 Acetates) and Their Model Compounds (77)
Acetate ko" mb
~~
Isopropyl acetate 0.765 0

1-2,4,6-Triacetoxyheptane 0.996 1.8
H-2,4,6-Triacetoxyheptane 0.854 2.0
S-2,4,6-Triacetoxyheptane 0.690 2.6
Isotactic-rich poly(viny1acetate) (i = 74%, DP = 1690) 0.116 70
Atactic poly(viny1acetate) ( i = 47%, DP = 1560) 0.109 120
~
* The initial rate constant (liter mole-' min-').

A parameter showing the degree of rate acceleration during the reaction according
to the empirical equations dx/dt = k(a - x ) ( b - x ) and k = k,(l + mx/a), where
a = initial concentration of the acetyl group, b = initial concentration of sodium hy-
droxide, and x = concentration of acetyl groups reacted in time t.
Alkaline hydrolyses of stereoisomers of 2,4-diacetoxypentane and

2,4,6-triacetoxyheptane were studied in dioxane-water (75 :25). As
shown in Table XIV, the isotactic models showed higher initial rates
and less acceleration than the syndiotactic models. The initial rates of
all models are considerably higher than those of poly(viny1 acetates),
suggesting greater steric hindrance in the polymer. This might be why
the difference in initial rate due to the steric structure of the model
was not observed in the polymer. The spatial distance between acetyl
and hydroxyl groups in the mem and dl portions has been discussed
with regard to the rate acceleration (169), but according to the NMR
analysis of 4-acetoxypentanol-2 (128) the stable conformation was T T
in the dl isomers and G T or T G in the meso isomers. Therefore the
lower acceleration observed in the isotactic models is consistent with
the NMR analysis.
Besides activation by adjacent hydroxyl groups, factors such as
decreased steric hindrance and increased affinity of the polymer
molecules for water or the catalyst (see Section VA1) may have to be
considered in analyzing the reaction curves of poly(viny1 acetate) as
in the hydrolysis of poly(viny1 acetal).
2. Esterijication of PVA
A considerable difference was observed in the rate of trifluoroacetyla-
tion between isotactic and syndiotactic molecules of both model
500 FUJI1
alcohols and PVA (173), isotactic molecules reacting more slowly than
syndiotactic molecules. NMR spectroscopic observations of the reac-
tion between trifluoroacetic acid and model alcohols showed that the
equilibrium degree of trifluoroacetylation was lowered by the presence
of neighboring hydroxyl groups, and that the isotactic configuration
was more effective than the syndiotactic in reducing the equilibrium
conversion. A similar steric effect was observed in the polymer reaction,
and predominantly isotactic PVA showed a lower equilibrium conver-
sion than atactic PVA samples. Although no conclusion has been
drawn from these experiments, the state of intramolecular hydrogen
bonding may be related to the different reactivities.
Although no differences in reactivity were found between isotactic
and syndiotactic molecules in a preliminary experiment on acetylation
of model alcohols (173), the rate of acetylation also decreased in the
order isopropyl alcohol > pentane-2,4-diol > heptane-2,4,6-triol. This
suggests that the effect of the stereostructures of PVA and model
alcohols on acetylation may require further investigation. Yulu et al.
(21a) recently made an interesting observation with regard to this
problem. They reported that acetylation of highly isotactic PVA
samples to poly(viny1 acetate) with acetic anhydride required heating
for a few days.
C. Miscellaneous Reactions
I . Reaction with Boric Acid or Borax
The addition of saccharide to aqueous solutions of boric acid or
borax is known to affect their pH (174). Sakurada, Sakaguchi, and
Shiiki (165) examined the effect of addition of various PVA samples
on the pH of the solutions. Only a predominantly isotactic PVA
sample had any effect slightly lowering the pH of both solutions. They
deduced that the isotactic structure was favorable to the reaction of
the diol portion with boric acid or borax.
2. Triphenylmethylation
Triphenylmethylation of PVA does not proceed to high conversions
because of the large steric hindrance caused by bulky triphenylmethyl
groups. Noma and Sawato (175) have shown that the maximum con-
version averaged 42.4% in reactions with triphenylchloromethane in
pyridine. This value is very close to a limiting conversion of 43.2%,
calculated by assuming that hydroxyl groups adjacent to triphenyl-
methyl ether group were not available for reaction (176). In order to see
the effect of tacticity on such a steric hindrance, the reaction was
studied in pyridine and in a pyridine-dimethyl sulfoxide mixture (177).
The reaction in pyridine gave a maximum conversion similar to that
found in a previous study, but the maximum conversion reached 56%
in the mixed solvent. No significant difference in maximum conversion
was observed between atactic and predominantly isotactic PVA (77).
3. Reaction with P-Butyraldehyde Sulfonic Acid

Sakaguchi (178) studied the reaction of b-butyraldehyde sulfonic
acid with three PVA samples derived from vinyl t-butyl ether, vinyl
acetate, and vinyl trifluoroacetate. When the reaction was carried out
in an aqueous solution, the maximum conversion, based on hydroxyl
groups of PVA, was 56-57% in all three samples. This value was close
to the theoretical value calculated by assuming that the hydroxyl group
adjacent to the acetal was not available for reaction because of possible
electrostatic repulsion. The conversion was further depressed in reac-
tions in aqueous sodium chloride solutions, and a predominantly
isotactic PVA sample derived from vinyl t-butyl ether showed a
higher conversion than the other two samples. No explanation was
given regarding the action of sodium chloride.
VI. TACTICITY AND PHYSICAL PROPERTIES OF PVA
A. Solid Properties
I . Crystal Structure
The crystal structure of atactic PVA has been studied by a number
of investigators, and the model proposed by Bunn ( 3 ) is now basically
accepted. There have been some changes in the parameters for mono-
clinic unit cell dimension as techniques of measuring X-ray diffractions
have been improved. Some representative data are given in Table XV.
No essential difference was found in the X-ray diffraction patterns
of various PVA samples with different tacticities, although the polymer
became much less crystallizable as the isotactic content increased. In
502 FUJI1
c-projection 6-projection
Fig. 31. Crystal structure of atactic PVA according to Bunn (3). Dotted lines show
hydrogen bonds.
TABLE XV
Unit Cell Dimensions of Conventional Atactic PVA
X-ray diffraction
Mooney (2) 7.82 2.52 5.60 90"
Bunn (3) 7.81 2.52 5.51 9 l"42'
Sakurada et al. (4) 7.83 2.52 5.53 87"(93")
Nitta et al. (179) 7.81 2.52 5.51 91"42'
Mochizuki (180) 7.805 & 0.010 2.533 f 0.001 5.485 f 0.007 92"10 f 2 0
Electron diffraction of single crystals

Tsuboi and
Mochizuki (102) 7.81 0.02 - 5.43 f 0.01 91"30 & 15'
an electron diffraction experiment on single crystals of various PVA

samples, a slight improvement in molecular packing in crystals was
noted in syndiotactic-rich PVA samples (181).
2. Crystallinity, Water Resistance, and Tacticity

The term "crystalline" has been often used for convenience, or
misused, in expressing the stereoregularity or crystallizability of PVA,
and this has caused some confusion in stereochemical investigations
POLY(VINY L ALCOHOL) 503
of PVA. Even atactic PVA is highly crystallizable. Films of PVA cast
from aqueous solutions usually show some crystallinity, estimated by
Sakurada et al. (182) as about 30% or higher according to a density
method. No amorphous state has been attained, since the quenching
technique was not applied successfully because of decomposition of
the polymer at its melting point. Recently Ambara et al. (183)suceeded
in preparing an amorphous (or nearly so) PVA sample by freeze-drying
an aqueous solution using liquid nitrogen. This sample showed very
poor crystallinity on X-ray and infrared examinations as predominantly
isotactic PVA. Its crystallinity was estimated to be 13% by the density
method.
Changes of crystallinity with tacticity were studied by Fujii et al.
(101) by measuring densities of PVA films cast from aqueous solutions
1.32
1.31
.-
tz
-3
In
C
f3
1.30
I .29
0 0.I 0.2 0.3 0.4 0.5 0.6 0.7
D916/0850
Fig. 32. Density-tacticity relationship in PVA (I01).
504 FUJI1
300
280
260
0
0
+-
.-05
a 240
W
.-
C
f
220
200
18C
20 40 60 80 100
Syndiotacticity in diad, %
Fig. 33. Changes of melting point of PVA with tacticity (94).
and crystallized by heat treatment at 200°C. The density showed an

increase with the infrared absorbance ratio, D,,,/D,,,, which was
used as a measure of syndiotacticity. Murahashi et a]. (34-35) found
a similar tacticity dependence but observed the appearance of a new
infrared absorption band at 1160 cm-' and an increase in melting
point in highly isotactic PVA samples. On the basis of these findings,
they deduced the presence of a new type of ordered structure in isotactic
PVA molecules. No X-ray or density studies have been performed on
these samples. In contrast with these observations, Kenney and Will-
cockson (147) compared four PVA samples subjected to various heat
treatments and concluded, mainly from density data, that the order of
crystallizabilities was atactic 2 syndiotactic-rich > isotactic-rich, with-
in the range of tacticities studied. According to their results, the in-
creased syndiotactic structure did not appear to lead to higher crystal-
linity. However, their density data on a syndiotactic-rich PVA sample
derived from vinyl trifluoroacetate polymerized at - 78°C may have
to be treated with reservations because the measured density decreased
in the order of heating temperature-150°C > 180°C > 21O"C--even
though the polymer had a higher melting point than other PVA
samples. Nagano, Fujita, and Nakatsuka (184) carried out experiments
similar to those of Kenney and Willcockson and reported that, under
given conditions within a heating temperature range of 100-180"C,
crystallization proceeded in the order syndiotactic-rich > atactic >
isotactic.
Different tacticities can lead to even higher differences in crystallinity
when crystallinity is measured by the X-ray or infrared method on
film specimens, but the anisotropic nature of the sample specimens
can seriously affect the results. Therefore the data obtained should be
treated with caution.
The water resistance of PVA is closely related to the tacticity and
crystallinity of the polymer. Higher crystallinity would lead to higher
TABLE XVI
Water Resistance of Two PVA Samples with Different Degrees of Crystallization (185)
Starting monomer Vinyl formate Vinyl acetate

Polymerization temperature ("C) - 60 120
D P of PVA 1600 1600
D9 1
6ID
i35 0 0.54 0.35
Heat treatment 100"C, 30 min 180"C, 5 min
Density 1.2909 1.3041
X-ray diffraction
(101) and (101) Strong Very strong
(200) Medium weak
(002) ~
Weak
(1 11) Weak Medium
Water resistance at 85°C
Swelling degree 2.06 z
Solubility (%) 22.85 100
water resistance for a given PVA sample, but different tacticities would
lead to more complex relations. A representative case was described
by Fujii et al. (185). Two PVA samples were compared: one derived
from vinyl acetate polymerized at 120"C, and the other from vinyl
506 FUJI1
16 20 24 16 20 24 16 20 24
28,deg
Fig. 34. Anisotropy in PVA film cast from aqueous solutions at 50°C and heated at
215°C (101).
formate polymerized at -60°C. Both samples had the same DP, 1600.
They were subjected to heat treatment at 180" and 100"C, respectively.
Heating at 100°C could not have much effect on crystallization. Con-
sequently the latter specimen was much less crystalline than the
former, as evidenced by the X-ray and density examinations, but the
latter was much more water-resistant than the former. These observa-
tions suggested that stereoregularity may have little effect on the
X-ray diffraction patterns of PVA within a certain tacticity range, but
that the syndiotactic configuration favors interchain hydrogen bonding
and hence would lead to higher water resistance. Similar conclusions
were reached by Kenney and Willcockson (147).
For the effect of tacticity on water resistance, Kenney and Willcock-
son (147) reported the following order : syndiotactic-rich % isotactic-
rich 9 atactic. This contrasts with all other published results (34-35,
95,101,184,185).Possibly this finding was due to cross-linking induced
in the isotactic-rich PVA samples during transformation from poly-
(vinyl t-butyl ether). Predominantly isotactic PVA is readily soluble in
water when free from cross-linking, and heat treatment is not effective
in rendering it water-resistant. Murahashi et al. (34-35) found that
POLY (VINY L ALCOHOL) 507
TABLE XVII
Solubilities of PVA in Water (35)
Isotacticity
Source DP . . Solubility
in diad (%)
Vinyl trimethylsilyl ether 2040 91 Insoluble in cold water, soluble at

100-110°C
Vinyl benzyl ether 2800 87 Soluble in cold water
Vinyl acetate 500 55 Insoluble in cold water, soluble at

100°C
Vinyl trifluoroacetate 3135 48 Insoluble in cold water, soluble at
100-1 10°C
Vinyl trimethylsilyl ether 30 26 Insoluble at 150"C, soluble at
160°C
highly isotactic PVA samples (s = 90%) were slightly less soluble in

water than other isotactic-rich PVA samples. A predominantly syn-
diotactic PVA sample was very water-resistant and insoluble in water
at 150°C in spite of its low D P (approximately 30), but dissolved at
160°C.
Fig. 35. Spherulites of atactic PVA (187).

508 FUJI1
3. Crystallization from Solutions

Atactic PVA can form single crystals when crystallized from various
polyol solutions (102,103,186). Triethylene glycol (102) is the solvent
most commonly used. Spherulites, which are common in crystalline
polymers but had not previously been observed in PVA, were recently
obtained by casting PVA solutions in this solvent (187).
The crystallization of syndiotactic-rich PVA samples derived from
vinyl formate and trifluoroacetate was compared with that of predom-
inantly isotactic PVA samples derived from vinyl t-butyl ether (181).
TABLE XVIlI
Properties of Single Crystals of Various PVA Samples (181)
Preparative conditions of parent polymer

s(%)y D,,,
Sample DP
Tempera- Medium
Monomer
ture (“C)
A Vinyl formate - 78 Methyl formate 300 61 -

B Vinyl acetate 60 Methanol 1730 53 0.23
C Vinyl acetate 60 DMSO 1160 53 0.00
D Vinyl t-butyl ether -78 Toluene 1000 26 0.00
Dissolution
Optimum dissolution Crystallization Cell constant Melting tempera-
Sample temperature temperature point ture in
(“C) C) r (“C) water
a m c ( 4 (“C)
A 270 195 7.78 5.43 239 105-110

B 250 195 7.80 5.44 236 105-110
C 235 185 7.84 5.48 227 98
D 170 130 7.84 - 195 20-60
___-._.__
Syndiotacticity in the diad.
The isotactic-rich PVA dissolved in triethylene glycol at a much lower

temperature and formed fibril-like precipitates 0 . 1 wide.
~ These pre-
cipitates showed a lower melting point and were readily soluble in
water.
(4
Fig. 36. Water resistance of single crystals of PVA. (a) Single crystals of atactic PVA
dipped in water at 80"C'for 30 min; (b) platelets obtained from isotactic-rich PVA;
(c) platelets (b) dipped in water at 20°C for 2 min.
510 FUJI1
Another interesting example of the crystallinity-water resistance-

tacticity relationships in P V A was provided by crystallization of a PVA
sample derived from vinyl formate polymerized in the solid state
(62,107).This polymer was supposed to have a stereoblock nature (see
(4
Fig. 37. Single crystals of PVA derived from vinyl formate polymerized in the solid
state. (a) Original; (b) dipped in water at 40°C for 1 min (107).
Section IIB). Crystallization of this PVA from a triethylene glycol
solution gave beautiful single crystals. These single crystals were
readily attacked by water at room temperature, whereas single crystals
of ordinary atactic PVA showed fair resistance to boiling water (Fig.
37).
Harris et al. (188) studied the crystallization-dissolution behavior in
polyol media of various PVA samples derived from vinyl formate,
acetate, trifluoroacetate, and t-butyl ether. The extrapolated dissolu-
tion temperature, (T&,, obtained from the dissolution-crystallization
temperature relationship was proposed as a characteristic property of
a given PVA sample independent of its handling history. A PVA
sample of higher syndiotactic structure exhibited the highest (Tm)a in
1,3-propanediol, but predominantly isotactic PVA samples displayed
(Tm)avalues higher than that of the atactic sample. This was inter-
preted as follows : once the crystal lattice of isotactic PVA has formed,
its stability is intermediate between those of the atactic and syndiotac-
tic-rich structures. Again these observations are inconsistent with those
of Tsuboi, Fuji, and Mochizuki (181). No details of the experimental
conditions of polymer transformation were given for the predominantly
isotactic poly(viny1 t-butyl ether) samples used by Kenney and Will-
cockson (147) and by Harris et al. (188), but the PVA samples obtained
showed unexplained behavior (see Section IIA2).
4 . Glass Temperature and Melting Point

The glass temperatures of syndiotactic-rich PVA samples derived
from vinyl formate were measured by the dilatometric method and
were compared with that of ordinary atactic PVA (189). Those PVA
samples showed higher glass temperatures than the atactic PVA (see
Table XIX). No further study has been made on PVA samples with a
wider range of tacticity.
Variations of the melting point of PVA with tacticity were first
studied by F u j i and Inoue (189), applying the temperature-elongation
method (190). The melting points of PVA samples derived from vinyl
formate polymerized at -78°C or -60°C were 25°C higher than that
of atactic PVA. Differential thermal analysis (DTA) has been used to
study the melting of PVA. Tubbs (191) reported that the DTA curves
of PVA derived from conventional poly(viny1 acetate) showed a min-
imum at around 228°C. According to Mochizuki et al. (192), the
512 FUJI1
TABLE XIX
Transition Points and Tacticities of PVA (189,192)
ant, C
Source of PVA
n. DTA
Vinyl formate ( - 78'C) 1000 61 92.0 265 246

Vinyl acetate ( - 40°C) 1900 53.5 88.0, 88.5 260 -
Vinyl acetate (60°C) 1600 53 85.5 246 221
Vinyl t-butyl ether ( - 7 8 ° C ) lo00 26 - - 215
Syndiotacticity in the diad
minimum point (melting point) was approximately 235°C for PVA

derived from vinyl acetate polymerized in methanol at 6 0 T , but the
position of the minimum point was dependent on the temperature and
solvent of polymerization of vinyl acetate (see Section VIIA). It was
also observed that the melting point became higher as the syndiotactic
content of the PVA increased. Sumi et al. (35) made a similar observa-
tion. A PVA sample of 74% syndiotacticity derived from vinyl tri-
methylsilyl ether was supposed to have the highest melting point,
286"C, in spite of its low DP. The melting point versus syndiotacticity
curve recorded a minimum at around 20% syndiotacticity, suggesting
the presence of a different type of order in highly isotactic PVA
molecules (see Sections IIIA and VIA2). Kenney and Willcockson
(147) reported the melting point of PVA of 74% isotacticity to be
235°C. This value was comparable to those obtained for PVA samples
of the conventional type by their DTA method but was considerably
higher than the 215-220°C obtained by other groups (35,192) for
similarly isotactic-rich PVA samples.
'
Observation of the 1141 cm- band (crystallization-sensitive) of
PVA is also useful in studying its melting behavior (193). Imai and
Kazusa (194) confirmed the variation of melting point with structural
regularity of PVA by this technique. Curves of D1141/D1093 versus
temperature showed a maximum at around 180°C for PVA samples
of the conventional type, and the melting point was determined by
extrapolation. The 1141 cm- band disappeared at lower temperatures
than melting points determined by DTA.
5. Dynamic Viscoelasticitj
Nagai and Takayanagi (195) studied the dynamic viscoelasticity of
three PVA samples derived from vinyl t-butyl ether (isotactic-rich
PVA, I-PVA), vinyl acetate (atactic PVA, A-PVA), and vinyl tri-
fluoroacetate (syndiotactic-rich PVA, S - PVA) in the temperature
range between - 150" and 230°C. The latter two PVA samples showed
I S-PVA
2 Q A-PVA
3 o 1-PVA
I I I I I I I I
-100 -50 0 50 100 150 200
Temperature (OC)
Fig. 38. Curves of temperature versus E and E" for various PVA samples (138 cycles/
sec) (195). Samples were heated at 207" (S-PVA), 210 (A-PVA), and 150°C (I-PVA).
similar viscoelastic dispersion characteristics. Two dispersions arising

from the amorphous region were observed, at 80°C (major) and 30°C
(secondary), at 138 cycles/sec. Two absorption bands in the crystalline
region were observed, and one, which appeared at high temperatures,
was clearly observed at around 200"C, especially in S-PVA. The
lower-temperature absorption band appeared at 130°C in A- PVA
and at 145°C in S-PVA. Crystalline absorption was not clearly
observed in I - P V A .
B. Solution Properties
1. Gelation of Aqueous Solutions
Concentrated aqueous solutions of PVA exhibit thermally reversible
gelation. Matsumoto and Ohyanagi (196) found that the gelling rate of
514 FUJI1
the solution was dependent on the temperature of polymerization of

the original poly(viny1 acetate). Though the gelling rate is affected by
various structural factors other than tacticity, and PVA samples of a
wider range of tacticity have not been studied in the same way, gelation
is clearly related to the tacticity of the polymer. Aqueous solutions of
predominantly isotactic PVA were stable, and no gelation was observed
after prolonged standing (77). The mechanism of gelation has not been
fully elucidated, but apparently it is associated with the formation of
some orders with intermolecular forces (probably hydrogen bonding)
that are favored in syndiotactic structure. Maeda, Kawai, and Kashi-
wagi (197) measured the apparent melting point of PVA gel, T,, and
obtained an experimental equation: log C = A H / R T , + K , where C is
the polymer concentration and K is a constant. In the conventional
(atactic) PVA AH was 8.8 kcalimole, which corresponds to one or two
hydrogen bonds. Go, Matsuzawa, and Nakamura (198) reported the
AH values of PVA samples derived from vinyl acetate, formate, and
trifluoracetate, to be 7.7, 10-12, and 20 kcal/mole, respectively.
2. Coloration with Iodine

Like amylose, PVA gives a characteristic blue color with iodine
(199,200). Imai and Matsumoto (48) found that the coloring ability of
PVA was sensitive to the preparative conditions used for the parent
poly(viny1 acetate). Although this ability was also affected by various
structural factors such as the chain length of the polymer and the
presence of foreign monomer units in the PVA chain, an additional
influence of structural regularity was also evident. 'Greater coloring
abilities were observed in PVA samples of higher water resistance.
It was deduced from these findings that the coloration was related to
the stereoregularity of the polymer. Absorption maxima were invariably
at 620 mp within the experimental conditions studied, and D620 was
used as a measure of stereoregularity. This method has been applied
to various PVA samples prepared under different conditions (54,55,201)
(see Section VII for the effect of other structural factors).
This conclusion was substantiated by the following experiment on
PVA samples of different tacticities (202). A PVA sample of 74%
isotacticity showed no absorption at around 620 mp, even at much
higher reagent concentrations, whereas PVA samples of high syn-
diotacticity showed intense coloration (55,202). Apparently the syn-
diotactic sequences in the polymer are incorporated into the coloration.
Kikkawa, Nozakura, and Murahashi (203) noted a similar tendency.
They also observed that in PVA samples of high isotacticity the absorp-
tion at 620mp disappeared and another absorption maximum ap-
peared, at 400-420 mp, but it was not disclosed if this absorption was
based on the isotactic structure of the polymer.
The origin of the coloration is not yet known. Zwick (204,205)
deduced the formation of a polyiodide chain enveloped in PVA helices
from his finding that the absorption maximum could be shifted con-
tinuously from 580 up to 700mp by the addition of boric acid. How-
ever, the situation does not seem so simple. The addition of boric acid
is known to increase the blue color of the PVA-iodine system (204),
but in the presence of a substantial amount of boric acid all PVA
samples examined showed intense coloration regardless of the tacticity
of the polymer, and no difference in the coloring ability was observed
(202). Therefore the use of boric acid does not help to distinguish the
microtacticities of PVA. As already mentioned, no shift of the absorp-
tion maximum was produced by changing the reaction variables in
the absence of boric acid (48), and hence the polyiodine theory cannot
be applied simply. Partial acetalization of PVA is also known to
promote the coloration of the polymer with iodine (207-210). Inter-
estingly, the isotactic portion of PVA reacts with boric acid or aldehyde
preferentially (164,165), and consequently is fixed in the T T conforma-
tion, which is not favored in aqueous media (211). This is the most
stable conformation for the syndiotactic PVA molecule in aqueous
solutions. These findings suggest possible spatial arrangements of the
PVA molecules in PVA-iodine complexes.
3. Stability of Aqueous DMSO Solutions

Imai and Maeda (47) 'found that solutions of PVA in dimethyl
sulfoxide (DMS0)-water mixtures were unstable and became turbid
on standing. The rate of growth of turbidity was measured for 3 g/liter
solutions of PVA in DMSO-water (60:40 by vol) at 30°C. The half-
time required to reach the equilibrated turbidity, t,,,, was used as a
measure of the rate. The rate was proportional to the 0.6 power of
DP of PVA, and therefore the reduced half-time, tl,2 . (DP)o.6 x
was employed in order to eliminate the effect of chain length. Like the
gelling rate and coloring ability with iodine, the clouding rate was
516 FUJI1
dependent on the structural regularity of PVA. PVA samples derived

from vinyl formate polymerized at low temperatures showed very short
half-times.
4 . Fractionation by Foaming
A unique method of polymer fractionation by foaming was devel-
oped by Imai and Matsumoto (212). A 1-2% aqueous solution of
PVA derived from ordinary poly(viny1 acetate) was placed in a
1-5-liter bottle and shaken for a certain time. A foam layer was formed
on the upper part of the solution during shaking. The solution was then
allowed to stand for more than 15 hr. During this time part of the foam
disintegrated back into the mixture. The remaining foam was collected,
and the residual mixture was heated and then subjected to the same
foaming procedure. The fractions of PVA thus obtained exhibited
considerable differences in coloring ability with iodine, but no appre-
ciable difference was observed in their DPs except for the remaining
fraction, which had a slightly lower DP. The 1,2-glycol content of the
PVA from the foam layer was slightly smaller than that of the original
0.6
0.4
u)
Q
0.2
0 1000 2000 3000 4000

PA
Fig. 39 (a).
IC
(b/
E 0-78OC
1
0-60°C
t?a t
Q 0-30°C
O 0T
3
0 3OoC
I VA0-78OC 0
00
0 6OoC
0 1000 2000 3000 4000
pa
Fig. 39. Coloration of various PVA samples with iodine. [ I , ] = 1 x M; [ K , ] =
=4x M ; [PVA] = 1.25 g/liter, 20"C, 24 hr. ( a ) PVA derived from vinyl acetate
(48); 0 polymerized at -4O"C;@, 30"C;n, 60°C; 0,lOO"C, (b)PVA derived from vinyl
formate polymerized in bulk or in methyl formate (55). Numbers denote polymerization
temperatures.
518 FUJI1
TABLE XX
Fraction of PVA by Foaming (212)”
PVA
Concn of Amount of Shaking Foam
Frac-
PVA solution time
tion
(giliter) (liter) (hr)
FI 9.54 1.o 2 1.7 2.7 8.46 1620 3.05

F2 - I .o 4 1.4 5.3 8.84 1730 2.94
F3 ~
1.o 8 1.3 10.9 9.06 1800 2.51
F4 0.9 24 1.5 34.3 9.57 1960 I .66
F5 - 24 0.6 7.1 8.92 I750 0.54
F6 - 0.8 24 0.5 2.2 8.25 I550 0.38
F7 4.55 0.8 50 0.4 2.1 7.48 1330 0.23
F8’ ll.Ob 0.3‘ 24 0.1 1.3 7.14 1410 0.10
F9 - 34.1 5.94 928 0.02
FO‘ - - 8.11 1510 1.11
The original polymer was poly(viny1 acetate) prepared at 0°C in methanol. Capacity
of bottle, 2 liters; amplitude of shaking, 10.8cm.
’ Shaken in a 1-liter bottle after concentration.
Original unfractionated PVA.
polymer, but the difference was too small to explain the difference in
coloring ability. Consequently it was supposed that PVA was frac-
tionated according to its stereoregularity. It was also disclosed that
fractionation was effected according to the differential stability of the
foam rather than the foaming capacity of PVA.
No appreciable difference in tacticity was observed among the PVA
fractions obtained by foaming on NMR examination (128,213). It seems
that this method of fractionation is effective in distinguishing the length
of the syndiotactic sequence in the polymer.
5. Mechanical Denaturation of Aqueous Solutions

PVA from aqueous solutions can be made to coagulate by shearing.
This phenomenon was considered to be a type of mechanical denatura-
tion similar to that observed in silk fibroin, and has been studied by
Go et al. (198,214-217) from various aspects. It was assumed that the
length of the syndiotactic sequence was an important factor in the
mechanical denaturation of the polymer.
C. Steric Conformation
A number of characteristic properties of PVA with regard to its
steric configuration have often been discussed in conjunction with
its peculiar chain conformation. Murahashi et al. (16) supposed that
the isotactic PVA molecule possessed a planar zigzag conformation
on the basis of the parallel dichroism of the 0-H stretching band
of the polymer. The near infrared spectra of various PVA samples aIso
showed a predominance of intramolecular hydrogen bonding in iso-
tactic-rich PVA samples as compared with atactic or syndiotactic-
rich PVAs (153). Sakurada, Nakajima, and Shibatani (218) studied
the temperature variation of unperturbed chain dimensions of three
PVA samples by thermoelastic measurements in ethylene glycol-water
TABLE XXI
Conformations of meso- and dl-Pentane-2,4-diol (Per Cent) at 40 C (21 1)
meso
Solvent
TT TG' + G-T TG- + G'T G-- + G++
CCI,
CH,CI,
- 70
- 90
-- 10
10
- 10
-0
-
-0
10
- 45 - 48 -7 -0
DMSO - 30 - 60 - 10 -0
D,O -5 - 70 - 2s -0
____-
dl
Solvent
TT (G'G') TG-(G-T) TG'(G+T)
CH,CI, 20 - 30 5-6 15 - 61 0-3
0 N
DMSO
- 60
- 53
-
-
13
16
-
- 16
13 -
-
13
16
520 FUJI1
mixtures. The degree of temperature dependence of the end-to-end

distance followed the order isotactic-rich > atactic > syndiotactic-
rich. The result was interpreted in terms of the steric configuration and
and conformations of the polymer chain. An extended zigzag form was
assumed for the isotactic PVA chain, while a rather skewed conforma-
tion was supposed to be more stable in the syndiotactic chain because
of possible intramolecular hydrogen bonding.
More direct information can be obtained for the conformation of
the model compounds, pentane-2P-diol and heptane-2,4,6-triol. In-
frared (83,90,219), near infrared (88,153), and NMR techniques (121,
21 1,220-223) have been applied. The NMR technique mainly measures
changes in the vicinal spin-spin coupling constant with conformation.
Fukuroi et al. (211) attempted to calculate the population of each con-
former (or rotational isomer) of pentane-2,4-diol in various solvents.
The accuracy of this type of analysis is still uncertain because of
the various assumptions it requires, but even so the results clearly
show the conformational characteristics of PVA molecules. It is note-
worthy that the solvent has a marked effect on conformation. Intra-
molecular hydrogen bonding is favored only in the absence of a polar
medium, and the conformations in aqueous or DMSO solutions are
close to those of the ordinary vinyl polymers.
D. Other Properties
Not much work has been reported concerning the practical applica-
tion of stereoregular PVA. The preparation of fibers from PVA samples
derived from vinyl acetate polymerized at relatively low temperatures
has been studied (224-226). These fibers showed improved water re-
sistance, but no improvements in mechanical properties were obtained.
Black and Cox (227) investigated the production of PVA fibers from
poly(viny1 trifluoroacetate). In order to avoid the difficulty of making
a spinning solution from PVA that was difficult to dissolve, the parent
poly(viny1 trifluoroacetate) was spun from an acetone solution into
water and the resulting fiber was stretched and hydrolyzed. The PVA
fiber was then subjected to various drawing processes. Fibers with
excellent water resistance were obtained by this technique. The highest
tenacity attained was 13.7 gldenier.
Thermogravimetric analysis curves of various PVA samples of dif-
POLY (VINYL ALCOHOL) 521
ferent tacticities were reported (35,147).However, the results were rather
complicated. and it seems difficult to draw a clear-cut conclusion from
them.
In PVA samples derived from vinyl acetate it was found that the
dependence of viscosity of the dilute aqueous solution on the shear
rate varied with the polymerization conditions of vinyl acetate (228).
No further investigation has been made on PVA samples of a wider
range of tacticities.
The possibility that the tacticity of PVA may influence the molecular
dimension of the derived poly(viny1 acetal) was pointed out by
Matsumoto (129). The cis-acetal ring derived from the isotactic diol
portion was supposed to give a more extended form than does the
trans-acetal ring. The dimension of poly(viny1 acetoacetal) was found
to increase when the original poly(viny1 acetate) was polymerized at
lower temperatures (129a). However. this temperature dependence
was reversed in the polymerization of vinyl formate (129b). Besides
tacticity, some other structural factos seem to be related to these ex-
perimental results. Recently Matsuda and Inagaki (129c) calculated
the statistical chain dimension of poly(viny1 acetal), assuming fully
acetalized molecules. The calculation predicted much larger chain
dimensions for the polymer derived from isotactic PVA. Experimental
confirmation of this theoretical expectation, aside from other structural
effects, has not been accomplished.
VII. STRUCTURE AND PROPERTIES OF PVA DERIVED

FROM VINYL ACETATE
In the preceding section various properties of PVA were interpreted

solely in terms of tacticity. Other structural problems, which were
not discussed in order to avoid confusion, will be discussed in this
section, with special emphasis on PVA derived from vinyl acetate.
A. Effect of Polymerization Conditions of Vinyl Acetate on

Properties of Derived PVA
The first paper to point out the effect of polymerization conditions
of vinyl acetate on PVA properties was presented by Ukida, Naito,
1
522 FUJI1
An
7."
3.8
2.8
F/
t
2.6
I- D-C'
0 Bulk
2-4 D-P
@ 5% methanol
2.2 ' I I I
0 30% methanol
I I I
Polymerization temperature (OC)

Fig. 40. Effect of polymerization conditions of vinyl acetate on the water resistance
of the derived PVA (145). The degree of swelling is the weight of water absorbed in one
part of PVA film of 0.2-mm thickness at 30°C.
and Kominami (144,229). They found that the degree of swelling in

water of PVA film cast from aqueous solution under certain conditions
was affected by polymerization variables such as temperature, con-
version, and solvent. They suggested that the variations in water re-
sistance might result from various degrees of branching in PVA,
and postulated the formation of short-chain branching, as in "high-
pressure polyethylene” (230). Their result was confirmed by Okamura
and Motoyama (231). who interpreted the effect of polymerization
temperature on water resistance in terms of the 1,2-glycol content of
the polymer. The effect of polymerization variables on PVA properties
was extensively studied by Imai et al. (46-48,145,232).
As mentioned above, various PVA properties such as coloration
with iodine (48) and clouding rate in aqueous DMSO solutions (47)
were used, in addition to the degree of swelling in water, to assess the
structural regularity of PVA. More than 20 solvents were studied in
order to see the effect of polymerization medium. The PVA properties
were significantly affected by the solvent employed, but little difference
was observed in the 1,2-glycol content of the polymer. Consequently
tacticity or some other structural regularity was proposed to cause
the difference in properties. The structural regularity of the resulting
polymer seemed to be governed by the dielectric constant of the
polymerization medium, with the exception of the contribution of
proton-donating solvents to hydrogen bonding.
Friedlander, Harris, and Pritchard (233) studied the effect of solvent
using amyl acetate, n-butyraldehyde, isobutyraldehyde, and methyl
ethyl ketone. The structural regularity of the resulting PVA was esti-
mated simply by the dissolution temperature in water or by (T,,)m
(188). Since no difference in tacticity was detected by NMR analysis
of these PVA samples, Friedlander et al. suggested that branching
was a major structural factor influencing the polymer’s properties.
The chain-transfer character of the solvent was assumed to contribute
to the production of more linear polymers. However. moderately
efficient transfer agents, such as acetonitrile and propylene carbonate,
gave less regular structures, and therefore structural regularity cannot
be associated with chain transfer. There is a minor discrepancy in the
reported effect of the ketonic solvent. According to Imai and Matsumoto
(46,232), acetone gave less regular PVA than did bulk polymerization.
O n the other hand, Friedlander, Harris, and Pritchard (233) assumed
that ketone, as well as the aldehyde medium, gave more regular PVA.
Alexandru, Oprisch, and Chiocanel (234) claimed to have produced
highly crystalline PVA by polymerizing vinyl acetate in acetone or
methyl ethyl ketone. These results can be interpreted as follows. PVA
prepared by polymerizing vinyl acetate in ketone may be readily
crystallizable in some cases because of its low DP, but its structural
FUJI1
I 31
ri
w 1-01
m NN
I l l
m rg rr
m N ri
vr VIP
VI IAb
I /
o\ o w
d d m
0 N 3
I I /
CI-
0 0 0
m mw
z
u
.., . .
2 s
u v
3.2 30 2900 3.8
60 1700 3.5
CH, . CHO - 0.3 - 1900 3.8-3.9 2.7-3.0

0.6 1300-1400 3.5-3.9 2.6-3.1
2.3 30 2800-3700 3.0-3.2 2.3-2.4

70 I000 1.9 -
2.0 30 1000- 1600 3.0-~3.5 24 28 1 I1

-d
w $
4
I .9 30 1100-1300 2.7- 2.9 109 110
CH, COOH 6.3 33 2100- 3000 2.7--2.9 I 07- I OX

2
4
r
CH,.OH 31 30 1100-2100 2.4-2.9 2.2 106 1 1 3 P
80 200--600 2.0-2.2 _- ..
0" 15 30 400.- 500 2.0- 2.1 w
9.8 70 300 0.97

Q-OH
~
Bulk 6.2 4.0- 4 3 - 2.6 - 1.1
" Dielcctric constant of solvent (CGS . esu)

' i,,,?(DP)" x (hr).
' Degree of swelling of PVA film (0.2 mm thick) at 30 C
526 FUJI1
i3
14
12
10
h
L 4
5 8
c0
X
I6
4 14 1 1
0 L a 9
1 4 -
I
I
l2
II 10
2
;3
I I I I I I
0 20 40 60
I /&
Fig. 41. A plot of dielectric constant of the polymerizing medium versus the reduced
clouding half-time of aqueous DMSO solutions of the derived PVA (46). Solvents:
1. DMSO; 2, ethylene carbonate; 3, acetonitrile; 4, acetic anhydride; 5. acetone; 6, ethyl
acetate; 7, diethyl carbonate; 8, benzene; 9. cyclohexane; 10, n-hexane; 11, acetic acid;
12, methanol; 13, cyclohexanol; 14. vinyl acetate (bulk).
regularity is slightly less than that of PVA obtained by bulk polymeri-

zation. Therefore PVA of similarly low DP. prepared by polymeriza-
tion in methanol or n-hexane, which favors a regular structure, would
have a more regular structure than polymers obtained in acetone or
methyl ethyl ketone. It has to be noted that the clouding rate in aqueous
DMSO solutions and coloration with iodine are very sensitive methods
of assessing the fine structure of PVA. The effect of DP on these prop-
erties is well known.
Aldehyde was the solvent that gave the most regular structure,
according to Imai and Matsumoto (46,232), but only a small amount
(0.3-0.6 %) was used in order to avoid excessive chain-transfer reaction.
Ishii et al. (234a) reported that the use of an aldehyde medium in the
polymerization of vinyl acetate seemed to decrease the 1,2-g1ycol
content of the PVA derived. A similar effect was reported for the poly-
merization of vinyl formate (106). In contrast to vinyl acetate polymer-
ization, the 1,2-glycol content of PVA obtained in aldehyde increased
with the polarity of the polymerization solvent ; bulk polymerization
led to the least 1,2-glycol content (50,51). Thus an aldehyde medium is
exceptional in minimizing 1,Zglycol.
The conditions of polymerization of vinyl acetate can exert consid-
erable influence on the properties of the resulting polymer. Various
structural factors affecting the properties of PVA are considered in
the following section.
B. Various Structural Irregularities

1. I,2-Glycol Structure
Deviation from the normal head-to-tail addition in the polymeriza-
tion of vinyl acetate gives rise to 1,2-glycol structure in the derived
PVA. The presence of 1,2-glycol in PVA was first detected by Flory
and Leutner (235) viscometrically by degradation with periodic acid.
Determinations of the amount of the periodic acid consumed by titra-
tion (236,237) and by polarography (238) also showed that the con-
ventional PVA derived from vinyl acetate polymerized at 60°C
contained approximately one and half 1,2-glycol bonds per 100monomer
units. The 1,2-glycol content decreased with polymerization tempera-
ture. Okamura and Motoyama (231) suggested that the change of
water resistance of PVA with polymerization temperature resulted
from the difference in 1,2-glycol content. Shibatani. Nakamura, and
Oyanagi (239) studied the properties of PVA samples derived from
vinyl t-butyl ether together with those of PVAs derived from vinyl
acetate in order to learn what structural factors might affect the prop-
erties of the latter. The PVA samples derived from vinyl t-butyl ether
contained no 1,2-glycol bonds, and their syndiotacticities varied from
59 % to 47.5 % according to the composition of the polymerization
medium. It was concluded that the 2 x increase in syndiotacticity
528 FUJI1
obtained by lowering the polymerization temperature of vinyl acetate

from 80°C to -78°C was insufficient to account for the improvement
in water resistance and coloring capacity with iodine. Shibatani et al.
also prepared PVA samples of different 1,2-glycol content by co-
polymerizing a small amount of divinyl carbonate or vinylene carbonate
with vinyl acetate and hydrolyzing the resulting copolymers. The
properties of these PVA samples were compared with those of PVAs
derived from vinyl acetate polymerized at different temperatures. A
good correlation was observed between the PVA properties and the
1,2-glycol content for all PVA samples examined. These results showed
that the 1,2-glycol content was the factor most influencing the prop-
erties of PVAs obtained at different polymerization temperatures.
This conclusion agreed with the opinion of Okamura and Motoyama
(231) but contradicted that of Friedlander, Harris, and Pritchard (233),
who considered the branching of PVA to be more important.
Still another structural factor has to be considered in order to ac-
count for the effect of the polymerization medium, which can exert
a large influence on PVA properties without appreciable changes in
1,2-glycol content and tacticity. According to Imai and Matsumoto
(46). “The solvent effect in the polymerization at 60°C can vary the
PVA properties in the range which corresponds to changing the poly-
merization temperature from - 78” to 120°C in bulk polymerization.”
The possibility that branching in PVA accounts for this solvent effect
must be considered.
2. Long Branching
Long branching is introduced into the PVA chain as a result of
abstraction of a- or P-protons from the main chain of poly(viny1
acetate) by free radicals. Wheeler, Lavin, and Crozier (240) estimated
the ratio of the rate constants of abstraction of the a-proton and acetyl
proton to be 0.5 at 70°C on the basis of kinetic analyses. This ratio
suggests the presence of considerable amount of main chain branches.
but the authors admitted that it could have at most only a qualitative
significance because of the experimental conditions employed. On
the other hand, the chain-transfer constants of various esters, de-
termined from extensive kinetic data by Matsumoto and Maeda (241),
clearly showed that chain transfer occurs nearly exclusively to the
acetate side chain in poly(viny1 acetate). Imoto, Ukida, and Kominami
(242) studied the polymerization of vinyl trimethyl acetate in the
presence of poly(viny1 acetate) in order to learn the position of the
branching point from poly(viny1 acetate). The isolated graft polymers
were hydrolyzed with methanolic sodium hydroxide. Only poly(viny1
acetate) was converted to PVA, the poly(viny1 trimethyl acetate)
moiety remaining intact. After removal of the poly(viny1 trimethyl
acetate) side branch by repeated extraction, the number of trimethyl
acetate units remaining in the PVA molecule was determined by in-
frared analysis. Assuming that the length of the main chain branch
was the same as that of the side chain branch, the ratio of the numbers
of both branches was estimated to be 1:40 at 60-70°C. This result
indicated that most branchings were formed from the side chains but
that the tertiary hydrogen atom also made a small contribution to
the branching.
Friedlander. Harris, and Pritchard (233) assumed that main chain
branching would occur 3 times as readily as side chain branching on
TABLE XXIII
Chain-Transfer Constants of Various Esters in Vinyl Acetate Polymerization at 60°C
Ester Formula ss x 104 Ref.
Methyl acetate CH,COOCH, 1.6 240

Ethyl acetate CH,COOCH,CH, 2.6 240
n-Propyl acetate CH,COOCH,CH,CH, 3.4 240
Isopropyl acetate CH,COOCH(CH,), 3.1 240
(Vinyl acetate 2.6) 240
t-Butyl acetate CH,COOC(CH,), 6.2 240
Methyl propionate CH,CH,COOCH, 23 240
Methyl n-butyrate CH,--CH,--CH,COOCH, 18 240
Methyl isobutyrate (CH,),CHCOOCH, 58 240
Dimethyl oxalate (COOCH,), 2.0 240
Isopropyl acetate CH,COOCH(CH,), 8 243"

(Vinyl acetate 2.5) 243"
Methyl acetate CH,COOCH, 2.5 243"
a Cited by Friedlander et al. (233)
the basis of the transfer constants of various esters reported by Clarke,

Howard, and Stockmayer (243). However, the transfer constants were
not properly chosen and therefore led to an improbable conclusion.
530 FUJI1
The formation of main chain branching requires the presence of

poly(viny1 acetate) as a chain-transfer agent and therefore is favored
at high polymerization conversions. This should increase the DP of
PVA with conversion, as was observed for poly(viny1 acetate) (244-246)
and for PVA derived from vinyl benzoate (45,247).This is not the case
for PVA derived from vinyl acetate, however (145,244). Variations in
the number of branches will also influence the PVA properties. In
PVA obtained by polymerization of vinyl acetate in methanol at
60°C, the water resistance and coloring capacity with iodine were
essentially independent of conversion. On the other hand, bulk poly-
merization at 60°C led to PVA properties that were slightly affected
by conversion (145,229), possibly because of the formation of long
branches. Ukida, Naito, and Kominami (229) attempted to charac-
terize the branched PVA according to the slope of a viscosity-concen-
tration plot, k , but Matsumoto and Imai (248) have shown that the
k-viscosity relationship was independent of the preparative conditions
of the parent poly(viny1 acetate).
It can be safely concluded that main chain branching occurs much
less frequently than side chain branching in the polymerization of
vinyl acetate. Consequently the amount of long chain branching must
be very small, if any, in PVA.
3. Short Branching
The formation of short branches by the intramolecular back-biting
mechanism has been established in the polymerization of ethylene
(230,249) and vinyl chloride (250,251). The presence of this type of
short branching has been suggested for vinyl acetate polymerization
(144,165,233,252),but to date no clear answer has been obtained for
this problem.
Nagai and Sagane (252) attempted to learn the degree of branching
in PVA by determining the amount of primary alcohol end groups.
They assumed that the primary alcohol gave a broad absorption at
1030cm-', changing the profile of the 1093cm-' band. With co-
polymers of vinyl alcohol and ally1 alcohol as references, the primary
alcohol content in PVA was estimated to be 2-4 mole "/d, which sug-
gested a considerable amount of branching.
The presence of such a high degree of branching will also influence
the hydrolytic behavior of poly(viny1 acetate) derived from PVA,
because the formation of one short branch will give rise to one primary
and one tertiary alocohol in the PVA chain (see Section VB1). However,
all poly(viny1acetate) samples derived from various vinyl esters showed
the same reactivity in alkali-catalyzed hydrolysis regardless of the
polymerization conditions of the parent polymers (1 11,168,169). This
suggests that the amount of short branching would be very small
(if any), in PVA.
According to Nakajima, Hamada, and Hayashi (253), the degree of
branching in poly(viny1chloride) is comparable to that of “high-pressure
polyethylene.” If the ease of forming the 6-membered transition state
and of abstracting the a-hydrogen and a-chlorine atoms in the polymers
is considered, this type of intramolecular reaction does not seem to
occur so readily in the polymerization of vinyl acetate.
Sakurada, Sakaguchi, and Shiiki (165) also considered that varia-
tions in the properties of PVA derived from vinyl acetate were due to
the different degrees of short branching in the polymer, and attempted
to correlate the dimensions of poly(viny1 acetals) with short branches
present in the original PVA.
Of the three structural factors described in this section, only short
branching is a probable explanation for the considerable effect of the
polymerization medium on PVA properties. Although the presence
of a large number of branches is rather unlikely in PVA, even a very
small number, such as one branch for every 100 monomer units,
may have a profound effect on the polymer properties.
VIII. CONCLUDING REMARKS
Recent developments in the study of the stereochemistry of PVA

have been reviewed from various aspects. Some overlapping resulted,
as tacticity and other structural factors of the polymer were summarized
in two separate sections. This was done in order to avoid unnecessary
complication and confusion in discussing structure-property relation-
ships, and to clarify the present situation.
Although much is left to be done in this area, it has already become
evident that PVA and its derivatives hold a unique and significant
position in the stereochemistry of polymers. Besides stereoregularity,
other structural factors await further examination. This problem has
532 FUJI1
been reviewed briefly above, For readers interested in pursuing the

subject further, the following review articles are recommended : on
the structure of PVA, Matsumoto et al. (129,254,255); on the stereo-
chemistry of free-radical polymerizations, Cooper (67); on the structure
of poly(viny1 acetal), Matsumoto and Fujii (93); and on stereoregular
PVA, Murahashi and Nozakura (94-96).
Acknowledgment
I wish to thank Professor S. Okamura of Kyoto University for his
continued interest and encouragement.
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1AAA, Exp Data On Tacticity PVAc APV, Docslide - Us - Stereochemistry-Of-Polyvinyl-Alcohol PDF

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Stereochemistry of Poly (vinyl Alcohol)

1. Hydrolysis of Poly(viny1Acetal) . . . . . . . . . . . . 491

Poly(viny1 alcohol) (PVA) holds a unique position in the field of

11. RECENT PROGRESS IN THE PREPARATION OF

A. Vinyl Ethers as the Starting Monomer

1. Vinyl Benzyl Ether

bond, which is resistant to hydrogen bromide but can be removed by

From benzyl methylene From acetoxymethyl

Solvent Temp("C) I(%) H(%) S(%) I(%) H(?o) S(%)

a PVBE = poly(viny1benzyl ether)

resulting polymer (15). Use of a Ziegler catalyst (AlEt, + TiCl,) gave

2. Vinyl t-Butyl Ether

polymerization with boron trifluoride etherate in nonpolar media, and

Tacticity determined from methyl signdl of

' Calculated from triads as i = I + f H and s = S + fH.

nism of acetylation seemed to be different in the two ethers. Unlike the

3 . Vinyl Trimethylsilyl Ether

initiators. The polymer was converted to PVA by methanolysis imme-

VOSi EtAlCl, Toluene -95 86 10 4 91 9

B. Vinyl Esters as the Starting Monomer

* A slight increase in syndiotacticity in poly(viny1 trifluoroacetate) was also reported

Triad (observed) Diad (calculated) Heterotactic

In bulk and methyl formate

In the solid state

tacticitv was studied in the range of -78 to 12PC by converting

(32,65). As shown in Table V, the length of alkyl substituents has little

However, branching from the a-carbon clearly contributes to the steric

C. Divinyl Monomers as the Starting Monomer

* They are reviewed by Cooper (67)

polymerization conditions such as temperature, solvent, and conver-

have been developed for poly(diviny1 carbonate), its structure is much

Soluble and insoluble parts (%)

6-Membered ring (%) ~ 12 31 18 25 27 - -

5-Membered ring (%) ~ 16 13 13 16 21 - -

a Conditions: 60 f 0.05”C; [BPO] = 0.5 mole 7; of monomer.

present, and as estimated by the infrared method, it showed good

tion conditions; I = 0.39-0.45, H = 0.40-0.45, and S = 0.15-0.19.

D. Low-Molecular-Weight Model Compounds

same time some ambiguity is often inevitable in studying their structures

The isotactic and syndiotactic triols were obtained as crystals melting

111. STEREOREGULARITY A N D CRYSTALLIZABILITY OF

The relationship of poly(viny1 acetate) to PVA is of particular interest

An X-ray fiber pattern of PVA was first reported by Halle and

unit. No pa-rticular attention was paid to the steric structure of the

Fig. 4. Single crystals of conventional atactic PVA (102).

isotacticity. The PVA samples became less readily soluble when

Fig. 7. A fiber pattern of isotactic poly(viny1 forrnate) (101).

conformations, respectively. Density versus D,, 6/D850plots recorded

Fig. 8. A fiber pattern of syndiotactic-rich poly(viny1 formate) (101).

reported a somewhat different result for the fiber pattern of poly(viny1

An interesting finding in the crystallization of this type of poly(viny1

increased isotacticity obtained with solid-state polymerization was only

Fig. 11. A fiber pattern of poly(viny1 formate) prepared by solid-state polymerization

were prepared by precipitating the polymer from dilute solutions in

the following unit cell dimensions were obtained: a = 9.54 A,

IV. SPECTROSCOPIC STUDIES

A. High-Resolution NMR Spectra

reported for the tacticity of the conventional polymer prepared by

Poly(viny1alcohol) Polystyrene Poly(viny1 chloride) Poly(viny1 acetate)

decreasing as the chain length of the polymer increased. A comparison

5.2 5.6 6.0 ‘I;

methine signal was in the order of syndiotactic, heterotactic, isotactic

Poly(viny1 formate) (CD,),CO COH