Scribd Logo
Upload

Welcome to Scribd!

  • PVAc, APV, Heat Capacities, jpcrd215 PDF

    Uploaded by

    FaroikDahmchi
    5 views35 pages

    Original Title

    PVAc,APV,heat capacities,jpcrd215.pdf

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Report this Document

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    5 views35 pages

    PVAc, APV, Heat Capacities, jpcrd215 PDF

    Uploaded by

    FaroikDahmchi

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    of 35
    Heat Capacity and Other Thermodynamic Properties of Linear Macromolecules. VII. Other Carbon Backbone Polymers Umesh Gaur, Brent B. Wunderlich, and Bernhard Wunderlich Department of Chemistry, RonerlaerPoltachnic Institute, Troy, New York 12181 The heat capacity of poly-I-butene, poly-I-pentene, poly-I-hexene, polyisobutylene, poly(4-methyI-1-pentene), polybutadiene, cis-1,4-poly(2-methylbutadiene} polyeyclopen- tne, poly(vinyl fluoride), poly(vinylidene fworide), polytrifuorvcthylene, pulytetualluer- ethylene, poly(vinyl chloride), poly(vinylidene chloride}, polychlorotrifluoroethylene, poly(vinyl aleohol, poly(vinyl acetate}, poly(a-methylstyrene}, poly(o-methylstyrene}, po- Iy(acchlornstyrene) and a series of poly(vinyl enznateje i roviowed an the hacie af &? ‘measurements reported in the literature. A set of recommended data has been derived for ‘each polymer. Entropy and enthalpy functions have been calculated for poly-I-hexene, polyisobutylene,ci-1, 4-poly(2-methylbutadiene), poly(vinyl chloride), and poly(a-meth- ylstyrene) This paper is seventh in a series which will ultimately cover all heat eapacity ‘measurements on linear macromolecules. Key words cuthalyy, cate, fusion, gla Wansition, Halygented puyol eapaiys neat ‘macromolecule; plyalkenes; polybenzoates polystyrene; vinyl polymers; vinylidene polymers. Contents Pe Pee 1. Introduction 313, Conclusions ot 2, Heat Capacity of Other Caron Backbone Pay 4, References a mers 31 2.1, Introduction. 31 22. Recommended Heat Capacity Data and ‘Thermodynamic Functions. 4 Ust of Tables Poly-I-butene. 34 Table 1. Crystal structures and thermal properties of Poly-I-pentene 36 various vinyl polymers 32 Poly-I-hexene. 37 Table 2. Heat capacity measurements of poly-1-bu- Polyisobutylene. cy AME sn Poty(uncthiylt-pe 2 table 3. Recommended heat capacity data f 1, 4Polybutadiene 41 crystalline poly-I-butene below the glass cis-1, 4Poly(2-methylbutadiene)... 41 ‘AraNSitiON wee 35 Palgeyclapentone 43° rable 4, Recommcintal heat capacity Uta in 1001 Poly(vinyl fluoride). _ ten poly-I-butene 35 >. Polyivinylidene uoride) 45. Table 5. Heat capacity measurements of poly-l-pen- Polytrituoroethyene num tene « . Polytetrafluoroethylene. Table 6. Recommended heat capacity data for poly- 3. Polytvinyl chloride)... [-pentene below the lass transition 36 Polytvinylidene chloride). $2 Table 7. Recommended heat capacity data for mol- . Polychlorotrifuoroethylene nana. 54 ten poy-l-pentene 3 Polyvinyl alcohol) 54 Table 8 Heat capacity measurements of poly-i-hex- 7. Polytvinyl acetate). 56 ene. 7 Polyla-methystyrene). ~ $8 Table 9, Revounendad thermodynamic data for 9. Polyo-methylstyrene) and 7 ‘amorphous poly-t-hexene 38 Polylo-chlorostyrene) Table 10, Heat capacity measurements of polyisobu- 2.2.20. Polyvinyl benzoate. © wine 8 @ 1987 he US Sereary ofComec ontettotte Unie Sats, THE 11+ Recommended thermedynamicdataforpo- ‘This copyright is ase to the American Insite of Physics andthe lyisobutylene fanscee Gaon See Table 12 Heat capacity measurements of poly Reprints aval rom ACS; se Repent List at back fe. smethyl-t-pentene} 40 (0047-2680/83/010020-35/$07.00 29 4. Phys. Chem. Ret. Data, Vol 12, No.1, 1983, 90 Table 13. Table 14. Table 15. Table Table 17. Table 18. ‘Tehle 10 Table 20. Table 21. Table 22. Table 23. Table 24 Table 25. Table 26 ‘Table 27 Table 28 Table 28 Table 20 Table 31. Table 32. ‘Table 33. ‘Table 34 ‘Table 35. Table 36. Table 37. Table 38. Table 38 GAUR, WUNDERLICH, AND WUNDERLICH Recommended heat capacity data for poly(4-methyl-I-pentene) below the glass transition. Heat capacity measurements tadiene. eee eee Heat capacity of two 1,4-polybutadienes... 41 Hleat capacity measurements of 14 poly(2-methylbutadiene) Recommended thermodynamic data amorphouscis-,4-poly(2-methylbutadiene). 42 Recoinmende fica capacity dat for amor phous polyeyclopentene below the glass fansitON en s Bannmmendod heat capacity data foe mal ten polyeyclopentene Heat capacity measurements of poly(vinyl fluoride). Recommended heat capacity data for poly- (vinyl uoride) below the glass transition Heat capacity measurements of polyvinyl ‘ene nore} Recommended heat eapacity daa for poly- (vinylidene fluoride) below the glass transi- a a “ tion 46, ‘Heat. capacity measurements. of -polytri- fuoroethylene 46 ‘Recommended heat capacity data for poly- tifluoroethylene below the glass transition..47 ‘Heat capacity measurements of polytetra- fluoroethylene sno “Eat capacity of polyteratuoroethylene at ow temperatures Heatcapacty varios poltaraoreth yyenee Heat capacity of measurements of poly- (vinyl chloride. Heat capacity investieations on polvivinvl chloride) not included in this study ...... 51 Recommended thermodynamic data for amorphous poly(vinyl chloride) 48 48 49 50 “Heat capacity measurements of polychloro- trifluoroethylene Recommended heat capacity data for po- lychlorotrifluoroethylene below the glass transiti = A Heat capacity measurements of poly(vinyl alcohol} Recommended heat capacity data for poly- (inyL abet) on Heat capacity measurements of polyiy| acetate) Recommended heat capacity data for amor phous poly(vinyl acetate). 35 36 4 Phys. Chem. Ret. Data Vo. 12, No. 1, 1983, Table 40. Table 41. ‘Table 42. Table 43. Table 44 Table 45. Table 46. Table 47. Table 48. Table 49. Heat capacity measurements of poly(ee ‘methylstyrene) 37 Recommended thermodynamic data. for amorphous poly(a-methylstyrene) cron 58 Recommended heat capacity data for po- ‘ylomethytyrene) and polyoehorstyr- p-isopropylbenzoate) Fiat eopacity meacurements petert-butylbenzoate Recommended heat capacity data for poly- {vinyl benzoatels below the sass trasition..61 ‘Recommended heat capacity data for mol- ten polyvinyl benzoates 6 Heatcapacity change atthe lass transition 62 List of Tables Deposited in PAPS* Table Al. Heat capacity of poly-l-butene below the lass Wasition TableA2 Heat capacity of various poly-l-butenes above the lass transition ‘Table A3. Heat capacity of various molten paty-l- Dutenes Table A4, Heat capacity of various poly-l-pentenes below the glass transition Table AS. Heat capacity of various poly-l-pentenes above the gla transition Table A6. Heat capacity of various molten poly-1- Table AT. Heat capacity of various poly-1-hexens Table AB, Heat capacity of various polyisobutylenes Table AS. Heat capacity of various poly(A methyl 1 pentene)s below the elas transition Table A10. Heat capacity of various poly(4-methyl-1- pentenels above the glass transition Table All. Heat capacity of molten poly(4-metyl- pentene) ‘Table A12. Heat capacity of various cis-,¢-poly(2- ‘methylbutadiene}s Table A13. Heat capacity of poly(vinyl uoride) Table Al4, Heat capacity of poly(vinylidene fluoride) ‘Table A15. Heat capacity of various polytrifuorocth ylenes Table A16, Heat capacity of various poly(vinyl chlor- idels "See AIP document no. PAPS JPCRD-12-0029-32 fr 32 pages of data tabs Order by PAP nomex and jornal ference rom the Amero Tasttat of Pie A inry Publication Service, 335 Bast 4th Sect, [New York, NY. 10017 The pice i $1.50 far a microfiche o $5.0 for Mhotocopis, Airmail i ditional. Thie materi lo appear ia Curren Diyece Mieraform, the monthly mean eitton ft complete wt af |oumal published by AIP on frames following the joural arte ‘THERMODYNAMIC PROPERTIES OF POLYMER ef Table ALT. Heat capacity of various polyvinylidene chlorides Heat capacity of various polychlorotri- Auoroethylene ‘Heat capacity of various poly(vinyl aleo- hol)s ‘Table A20, Heat capacity of various poly(a-methyl styrene) Table AIB. ‘Table AI. List of Figures Figure 1. Recommended heat capacity data for paly-1- butene, poly-L-pentene, and poly-I-hexene... 35 Figure 2. Recommended heat capacity data for polyi- sobutylene, poly(#-methyl-I-pentene}, cis, 1. Intreduetion ‘This is thesoventhpaperina series of discusions on the heat capacity of linear macromolecules. In the previous pa $F tne heat capacity of selenium, polyetylene, poly propiiene, polystyrene, and series of polyoxides and acrylic polymers were analyzed. In this paper al the remaining car- fan becthone polymere on which heat capacity date are available are analyzed. These are poly-I-butene, poly-I-pen- tene, poly-t-hexene, polysobutylene, poly¢-methyl-1-pea- tene}, polybutadiene, ct-1, 4-poly(2 methylbutadiene, poly exclopentene, polyvinyl florida, polyvinylidene Nuoride), polytriftuorocthylene, polytetraforoethylene, poly(vinyl chloride), poy(vinylidene chloride), polychlorotifuoroeth- lene, polyvinyl alcobol), polyvinyl accate,pob(o-meth- Yylstyrene}, polylo-methylstyrene}, polyfo-chlorostyrene}, anda series of poly(vinyl benzoate) Inthe subsequent publi- cations. the analysis ofthe heat capacity of polyamides, po- en 4-poly(2methylbutadiene, and polyeycto pentene .. S Figure 3. Recommended heat capacity data for poly. (vinyl fuoride, polyvinylidene fluoride) po- Iytefluoroethylene, and polytetrafluoroeth- slene : Recommended heat capacity data for poly- (vinyl chloride), and polychlorotrfivoroeth- ylene.. ee ‘Recommended heat capacity data for poly- (iy atcotot and polyfvingl acetate, 56 ‘Recommended heat capacity data for plyla- rethylstyrene) eet sa Recommended heat capacity data for poly- (vinyl benzoate}, poly(vinyl-p-ethyl-beazo- ate), polyvinyl-p-sopropylbenzoate), and poly(vinyl-p-tert-butylbenzoate) nin OL 39 45 Figure 4 32 Figure 5. Figureé, Figure 7 Iyesters, and linear macromolecules with hetero atoms and aromatic groups in their main and sidechains willbe report- ed. 2.Heat Capacity of Other Garbon-Backbone Polymers 2.1. Introduction Heat capacity analyses of carbon backbone polymers with large numbers of measurements available in the ltera- turehave been reported earlier. These include polyethylene,* polypropylene,® polystyrene,* and acrylic polymers.® All ‘other carbon backbone polymers with fewer datasets avail- able are analyzed in this paper. The repeating unit, formula ‘weight, crystal structure, density, melting temperature, heat offusion, and glas transition temperature of these polymers, ae listed in Table 1."* ‘4 Phys. Chem. Ret. Dat, Vol 12,No 1, 1903, 92 GAUR, WUNDERLICH, AND WUNDERLICH choi HE, Be 4. Phys. Chem. Ref, Data, Vol 12,No. 1, 1989 BES A wath ats g ob ‘THERMODYNAMIC PROPERTIES OF POLYMERS 93 se og 'S) REE TS calthrt alte ryote Ptah oa eae kane a tage She ea Bea nite tan oe hanes ys Bin ER ; "ay = 34 (GAUR, WUNDERLICH, AND WUNDERLICH Bayi ¢ reayiosert oe 22. Recommended Heat Capacity Data and ‘Thermodynamic Functions: 221. Poly-t-butene ‘Three invectigation:® ©! have been reported in the Ti terature on the heat capacity measurements of poly-I-bu- tene, Allthe measurements meet our standards of acceptable {ncmat prapertin of vanes vist polmoc-Cntined 9 RE To data (discussed in Ret. 1). Details of these investigations are given ir Table 2: Heat capacities of four semicrystalline sam- ples of various crystal forms and a molten sample have been ‘measured from 22 to 630 K. ‘The data on theve samples are given in Tables Al to.A3. ‘Tables Al to A3 have been deposited with the Physics Auxil- iary Publication Service of the American Institute of Phy- able 2, tas capacity maseranents of ote: tute - = ” (Sleieed cer tatat ina dessa? a ie * cus Ooi Se poder ad ws 488 en Fraction 0 unum) canats of aprociately 4.Phve. Chem. Ref. Data. Vol 12.No. 1.1982 ‘THERMODYNAMIC PROPERTIES OF POLYMERS: 39 __notan ptzc:bureas! 3 iar oes me sic. Since the heat capacity data reported are for various a ‘crystal types and the data on these semicrystalline samples cee overlap over avery limited temperature range 250 t0 330K), the calculation of the heat capacity of crystalline and amor- coe hou poly--butene from the erytalinity extrapolations ne ee | ims ‘PRE "ive cane may contain wore sisnificant fleures than justified 100 200-300 400500” 600 Temperature (K) Pho: Mosman a capa ea x ot -bHLEE FEE p> ‘ostene (PPE, and poly--herene (PH using the two phase model was not attempted. Recommend- cd data for the heat capacity of semicrystalline poly-I-bu- {ene w" = 0.44) from 0 K tothe glass transition temperature (249 K) and of molten poly-1-butene from 249 to 630 K only have been derived, ‘The heat capacity data on cample 9 aro talon ao the recommended data from 0 to 210 K. The heat capacity val- -4.Phvs. Chem. Ret, Data. Vol. 12. No, 1.1983 36 ‘us from 220 to 240 K are somewhat higher, because they are associated with the beginning of the glass transition. The recommended data from 220 tothe glass transition tempera- ture 249 K were determined by linearly extrapolating the data below 220 K. The heat capacity values from 180 to 210 K were curve fitted into the equation G, = 0.3272 T + 3.066 Fmot~! K-" 0 ‘The rms deviation was 0.196, The recommended values forthe heat capacities of poly-I-butene below the glass tran- sition are listed in Table 3 and plotted in Fig. 1 ‘The recommended data on heat capacity of molten poly-I-butene were determined by eurve iting the data on samples 10 1, and 13 from 390 to 630 K into the equation G, =0.1843 T+ 61.73 Fmol=! K-' 2 ‘The ems deviation was 0.7%. Equation (2) was used to calculate the heat capacity of molten poly-I-butene from 249 to 630 K. These values ae listed in Table 4 and plotted in Fig 1. 2.22. Poly-t-pentene nly one investigation“ has been reported in the litera- ture which deals with the heat capacity of poly-I-pentene. ‘The investigation meets our standards of acceptable data (discussed in Ref. 1), Details ofthis investigation are given in Table 5. Heat capacities of an amorphous atactic and two GAUR, WUNDERLICH, AND WUNDERLICH semicrystalline isotactic samples have been reported from 200 to 460 K. The data on these samples are given in Tables ‘A410 A6, These tables have been deposited with the Physics ‘Auxiliary Publication Service of the American Institute of Physics Below the glass transition temperature, the heat capac ity of amorphous atactic and semicrystalline isotactic sam- ples are in fair agreement. Thus the heat capacity just below te glass ausition (empetatuce is largely independent of crystallinity. To derive the recommended data from 200 K, to the glass transition temperature (233 Ki}, the data on all the three samples were curve fitted into the equation G, =0.296 + 28.7 Jmol" K! 8 ‘Therms deviation was 2.19%. Heat capacity values from 200 10 233 K calculated from Eq, (3) are listed in Table 6 aod plotted in Fig. 1. ‘The recommended data on heat capacity of molten poly-L-pentene were determined by curve fitting the data on the atactc sample above T, and the isotactic samples above Tr (Table A6) into the equation G— 0.298 74. $6.14 Fol“ K-* “ ‘Therms deviation was 0.79%. Equation (4) was used tocalcu- late the heat capacity of molten poly-1-pentene from 233 to 479 K. These values arc listed in Table 7 and plotted in Fig. AE oe astactie, oem 1 a \1.Phvs. Chem. Ret, Data, Vol. 12, No.1, 1983 oy-tepntene blew the glans easision ‘THERMODYNAMIC PROPERTIES OF POLYMERS: 7 Only one investigation» has been reported in the li- a tise eel terature which deals with the hea eapacityofpoly-1-hexene. amr sche investigation meets our standards of acceptable data kee (discussed in Ref. 1) Details ofthis investigation are given in a Table8. The heat capacity of quenched. amorphous sample ate has been measured from 20 to 290 K. The sample was then uss cooled slowly at 0.15 K h~' and the heat capacity was re- as ‘measured from 35 to 250 K. An anomalous behavior just mes ‘outside the error limits was observed at 80 K. The data on so both the samples are given in Table A7. Table A7 fas been ra deposited with the Physics Auxiliary Publication Service of ee the American Tnstitute of Physics, Heat capacity data on the on quenched and slowly cooled samples agree within 0.3%, ex- v8. cept inthe temperature range from 60 to 100 K. a ‘The heat capacity data on sample 1 are taken as the co recommended data from 0 to 190 K. The heat capacity val- ann ues at 200 to 210 K are somewhat higher, because they are ae =a associated with the beginning of the glass transition, The =e ae ata from 200 to 223 KZ) were determined by linearly an os ‘extrapolating the data below 200 K. The heat capacity val ae a ‘ues from 170 to 190 K were curve fitted into the equation we usa G, =0.5645 7 — 0.8067 J mot" K~* 0 wy mes ‘Terms deviation was 0.1%. The recommended data on the one heat capacity ofamorphous poly-I-hexene arelstedin Table so 9 and plotted in Fig. 1. one ‘The recommended data on the heat capacity of molten, oo poly-I-hexene were determined by curve fitting the data on ae on ‘ors yucnsbead aid slowly covkad samples above the glass fie wit transition into the equation G, =03101 T 4.61.65 3 mol~! K" 6 ‘The rms deviation was 0.6%. Equation (6) was used tocaleu- late the heat capacity of molten poly-I-hexene from 223 to 290 K. These values are listed in Table 9 and plotted in Fig. ra useltieg ny teen sour of date and date sreetent. The a, Ao n8so00 4 Phys. Cher. Ret, Data, Vol 12,No 1, 1968 38 GAUR, WUNDERLICH, AND WUNDERLICH Toe 6, aeconanded ternotrnanic dts for aarous ns.) 0.2 maa “ne eatie Glo ust ws sn. 4 Phys. Chem. Ref, Data, Vol. 12, No. 1, 1988 Enthalpy and entropy of amorphous poy-I-hexene ‘were calculated from 0 10300 K by numerically integrating ‘the heat capacity data, These thermodynamics functions are listed in Table 9 224 Patyleobutyone ‘Two investigations'™"® have been reported in the litera- ture on the heat capacity measurements of polyisobutylene. ‘Both the measurements meet our standards of acceptable data (discussed in Re. 1, Details ofthese investigations are siven in Table 10. The heat capacity data for atactic, amor- phous samples have been reported from 14 to 380 K. The data on these samples are given in Table AB. Table AB has ‘been deposited with the Physics Auxiliary Publication Ser- vice ofthe American Institute of Physics. Heat capacity data ssoociated with somewhat larger e110r limits have also been reported by Egorov and Kilesso"* on an uncharacterized "Mr rn hea cpa dao ample of higher molecular weight (Sample 32) are taken as recommended data from 15 to 180K. The heat capacity values from 190 to 200 K are somewhat higher, because they are associated ‘ith the beginning ofthe glass transition. The recommended data from 190 to 200 K were determined by linearly extrapo- lating the data below the glass transition. The recommended ‘data frou 160 ty 180 KC were curve ited into the equation 6, = 03125 74 1.8823 mol“! K-!. ” ‘The rms deviation was 0.1%. The recommended values for the heat capacity of glassy, amorphous polyisobutylene are “isted in Table 11 and plotted in Fig. 2. “Thc swommunded data on the heat capacity of molten polyisobutylene were determined by curve fitting the data on sample 32 from 210 to 380 K into the equation 6, = 02446 7-4 36.71 Jmol~ K-*. “6 ‘The rms deviation is below 0.3%. Equation (8) was used to evaluate the heat capacity of maton polyicoburylone from 200 to 380 K. These values are listed in Table 11 and plotted in Fig. 2. _ SBE ceria ‘THERMODYNAMIC PROPERTIES OF POLYMERS 39 Enthalpy and entropy of amorphous polyisobutylene were calculated from 0 to 380 K bv numerically intezrating the heat capacity data. These thermodynamic functions are listed in Table 11 100300300, Temperature (i) Fic. 2 Recommended hat capacity data for plyscburylene (PIB), pol rmethyLLpentee) (PAMIP, ci, 4-poly2-metyloutadiene) (F2MDD yam ply gehyentene (PER ‘00 2.25, Poly(4methykt-pentene) ‘Two investigations'®® have been reported in the litera- ‘ture on the heat capacity measurements on poly(¢-methyl-1- pentene). Both the investigations mect our standards of ac- ceptable data (discussed in Ref. 1). Details of these investigations arc given in Table 12. Heat capaciti of four samples of crystallinity from 0.28 to 0.65 have been mea- sured over a temperature range of 85 to $40 K. The data on these samples are given in Tables A9 to A11. Tables A9 to ‘ALI have been deposited with the Physics Auxiliary Publi- cation Service ofthe American Institute of Physics. ‘Below the glass transition temperature, the heat capac- ity has very limited dependence on the crystalinity. The rec- ‘ommended data on the heat capacity of poly(4-methyl-1- pentene) below the glass transition were determined by curve Sitting the data on samples , 6,7, and 8 from 80 0290 K into the equation 6, SeenlO158047(In TP —7 SSRN TP + 12.468{In 7} — 18.862] Jmol! K" ° ‘Therms deviation was0.5%. Equation 9} was used tocaleu- late the recommended values from 80 to 303 K. These data are listed in Table 13 and plotted in Fiz. 2. ‘Above the glass transition the heat capacity data (Table A10) are available for samples of very similar crystallinity only. The data are in quite good agreement, but cannot be ‘extrapolated with respect to crystaimty to determine the hheat capacity of completely crystalline and amorphous poly(4-methyl-I-pentenes. ‘The heat capacity data for molten poly(t-methyl-I-pen- tene) (Table AI) are available over avery limited tempera- ture range (520 to 540 K), Since the heat capacity-tempera- ture slove is not well established. it would not be very ‘accurate to extrapolate the molten heat capacity values ”* have been reported inthe li- {erature which deal with the heat capacity of polychlorotri- fluoroethylene. All the measurements which meet our stan-

    You might also like