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Polyhydroxyalkanoates

Structure of poly-(R)-3-hydroxybutyrate (P3HB), a polyhydroxyalkanoate

Chemical structures of P3HB, PHV and their copolymer PHBV


Polyhydroxyalkanoates or PHAs are linear polyesters produced in nature by bacterial fermentation of
sugar or lipids. They are produced by the bacteria to store carbon and energy. More than 150 different
monomers can be combined within this family to give materials with extremely different properties. [1]
These plastics are biodegradeable and are used in the production of bioplastics.
They can be either thermoplastic or elastomeric materials, with melting points ranging from 40 to
180 °C.
The mechanical and biocompatibility of PHA can also be changed by blending, modifying the surface
or combining PHA with other polymers, enzymes and inorganic materials, making it possible for a
wider range of applications.[2]
Material properties
PHA polymers are thermoplastic, can be processed on conventional processing equipment, and are,
depending on their composition, ductile and more or less elastic. They differ in their properties
according to their chemical composition (homo-or copolyester, contained hydroxy fatty acids).
They are UV stable, in contrast to other bioplastics from polymers such as polylactic acid, partial ca.
temperatures up to 180 ° C, [1] and show a low permeation of water.
The crystallinity can lie in the range of a few to 70%.
Processability, impact strength and flexibility improves with a higher percentage of valerate in the
material.
PHB is similar in its material properties to polypropylene (PP), has a good resistance to moisture and
aroma barrier properties.
Polyhydroxybutyric acid synthesized from pure PHB is relatively brittle and stiff. PHB copolymers,
which may include other fatty acids such as beta-hydroxyvaleriate acid, may be elastic.
Applications

Structure of poly-3-hydroxyvalerateStructure of poly-4-hydroxybutyrate (P4HB)


(PHV)
A PHA copolymer called PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)) is less stiff and
tougher, and it may be used as packaging material.
In June 2005, a US company (Metabolix, Inc.) received the US Presidential Green Chemistry
Challenge Award (small business category) for their development and commercialisation of a cost-
effective method for manufacturing PHAs.
There are potential applications for PHA produced by micro-organisms[4] within the medical and
pharmaceutical industries, primarily due to their biodegradability.
Fixation and orthopaedic applications have included sutures, suture fasteners, meniscus repair devices,
rivets, tacks, staples, screws (including interference screws), bone plates and bone plating systems,
surgical mesh, repair patches, slings, cardiovascular patches, orthopedic pins (including bone.lling
augmentation material), adhesion barriers, stents, guided tissue repair/regeneration devices, articular
cartilage repair devices, nerve guides, tendon repair devices, atrial septal defect repair devices,
pericardial patches, bulking and filling agents, vein valves, bone marrow scaffolds, meniscus
regeneration devices, ligament and tendon grafts, ocular cell implants, spinal fusion cages, skin
substitutes, dural substitutes, bone graft substitutes, bone dowels, wound dressings, and hemostats.[5]
Polyketone
Polyketones are a family of high-performance thermoplastic polymers. The highly polar ketone groups
in the polymer backbone of these materials gives rise to a strong attraction between polymer chains,
which increases the material's melting point (255 degrees Celsius for Carilon). Such materials also
tend to resist solvents and have good mechanical properties. Unlike many other engineering plastics,
aliphatic polyketones such as Shell Chemicals' Carilon (where "R" in the diagram is an ethyl group)
are relatively easy to synthesize and can be derived from inexpensive monomers. Carilon is made with
a palladium(II) catalyst from ethylene and carbon monoxide. A small fraction of the ethylene is
generally replaced with propylene to reduce the melting point somewhat.
For a discussion of the silicon containing polymers originally thought to have analogous structures, see
silicone polymers.
Polyetherimide
Polyetherimide (PEI) is an amorphous, amber-to-transparent thermoplastic with characteristics
similar to the related plastic PEEK. Relative to PEEK, PEI is cheaper, but less temperature-resistant
and lower in impact strength.

Structure
The molecular formula of repeating unit of PEI is C37H24O6N2 and the molecular weight is 592 g/mol.

Properties
The glass transition temperature of PEI is 216 °C. Its amorphous density at 25 °C is 1.27 g/cc. It is
prone to stress cracking in chlorinated solvent
Polyethersulfone
Polyethersulfone (PES) is a heat-resistant, transparent, amber, non-crystalline engineering plastic
having the molecular structure of .
PES is a tough and rigid resin similar to conventional engineering plastics, such as polycarbonate, at
room temperature.
The greatest characteristic of PES is that it has by far better high-temperature properties than
conventional engineering plastics. Specifically, PES remains in satisfactory condition in long-term
continuous use without causing any dimensional change or physical deterioration at temperatures as
high as 200ºC.
Properties of PES:
(1) Heat resistance: Short-term heat resistance:
HDT is 200 to 210ºC, and flexural modulus does not decline at temperatures of up to
nearly 200ºC.(ASTM method)
Long-term heat resistance:
UL temperature index is 180ºC, and the half life period of tensile strength at 180ºC is 20
years. (Heat aging properties)
(2) Dimensional stability:
The coefficient of linear expansion remains constant at temperatures of up to nearly 200ºC.
(3) Creep resistance:
PES shows excellent creep resistance.
(4) Electrical properties:
PES shows excellent electrical properties, which are retained even in a high-temperature
range.
(5) Flame retardancy:
PES is certified for UL94-VO.
(6) Moldability:
Although PES is a high-temperature-resistant resin, it can be molded on common injection-
molding equipment.
Poly(lactic acid) or polylactide (PLA)
Poly(lactic acid) or polylactide (PLA) is a biodegradable, thermoplastic, aliphatic
polyester derived from renewable resources, such as corn starch (in the United States)
or sugarcanes (in the rest of world). Although PLA has been known for more than a
century, it has only been of commercial interest in recent years, in light of its
biodegradability. The name "polylactic acid" is to be used with caution, not complying
to standard nomenclatures (such as IUPAC) and potentially leading to ambiguity (PLA is
not a polyacid (polyelectrolyte), but rather a polyester)[citation needed].

The skeletal formula of poly(lactic acid)


Chemical and physical properties
Due to the chiral nature of lactic acid, several distinct forms of polylactide exist: poly-L-lactide
(PLLA) is the product resulting from polymerization of L,L-lactide (also known as L-lactide).
PLLA has a crystallinity of around 37%, a glass transition temperature between 60-65 °C, a melting
temperature between 173-178 °C and a tensile modulus between 2.7-16 GPa[1][2].
PLA has similar mechanical properties to PETE polymer, but has a significantly lower maximum
continuous use temperature.[3]
Polylactic acid can be processed like most thermoplastics into fiber (for example using conventional
melt spinning processes) and film. The melting temperature of PLLA can be increased 40-50 °C and
its heat deflection temperature can be increased from approximately 60°C to up to 190 °C by
physically blending the polymer with PDLA (poly-D-lactide). PDLA and PLLA form a highly
regular stereocomplex with increased crystallinity. The temperature stability is maximised when a
50:50 blend is used, but even at lower concentrations of 3-10% of PDLA, there is still a substantial
improvement. In the latter case, PDLA acts as a nucleating agent, thereby increasing the
crystallization rate. Biodegradation of PDLA is slower than for PLA due to the higher crystallinity of
PDLA. PDLA has the useful property of being optically transparent.
Applications

Stereocomplex blends of PDLA and PLLA have a wide range of applications, such as woven shirts
(ironability), microwavable trays, hot-fill applications and even engineering plastics (in this case, the
stereocomplex is blended with a rubber-like polymer such as ABS). Such blends also have good
form-stability and visual transparency, making them useful for low-end packaging applications.
Progress in biotechnology has resulted in the development of commercial production of the D
enantiomer form, something that was not possible until recently.[4]
PLA is currently used in a number of biomedical applications, such as sutures, stents, dialysis media
and drug delivery devices. It is also being evaluated as a material for tissue engineering. Because it
is biodegradable, it can also be employed in the preparation of bioplastic, useful for producing loose-
fill packaging, compost bags, food packaging, and disposable tableware. In the form of fibers and
non-woven textiles, PLA also has many potential uses, for example as upholstery, disposable
garments, awnings, feminine hygiene products, and nappies.
PLA has been used as the hydrophobic block of amphiphilic synthetic block copolymers used to
form the vesicle membrane of polymersomes.
PLA is a sustainable alternative to petrochemical-derived products, since the lactides from which it
is ultimately produced can be derived from the fermentation of agricultural by-products such as corn
starch[5] or other carbohydrate-rich substances like maize, sugar or wheat.
PLA is more expensive than many petroleum-derived commodity plastics, but its price has been
falling as production increases. The demand for corn is growing, both due to the use of corn for
bioethanol and for corn-dependent commodities, including PLA.
PLA has also been developed in the United Kingdom to serve as sandwich packaging.[6]
PLA has also been used in France to serve as the binder in Isonat Nat’isol, a hemp fiber building
insulation.
PLA is used for biodegradable and compostable disposable cups for cold beverages, the lining in
cups for hot beverages, deli containers and clamshells for food packaging.[7]
The pharmaceutical industry uses oligolactic acid (OLA - a shorter polymer of lactic acid) in
pressurized metered dose inhalers (pMDIs) as a surfactant. Studies have shown that on standing,
pMDIs without OLA will yield a much higher dose than intended as compared to those containing
OLA which delivers a fairly constant dosage [8].
PLA is used as a feedstock material in 3D printers such as Reprap[9] and Makerbot[10].
Polymethylpentene
Polymethylpentene (PMP) is a thermoplastic polymer of methylpentene monomer
units. It is used for gas permeable packaging, autoclavable medical and laboratory
equipment, microwave components, and cookware. It is commonly called TPX, which is
a trademark of Mitsui Chemicals.

Physical properties
Polymethylpentene melts at ≈ 235 °C. It has a very low density (0.84 g·cm³) and is transparent. It has
excellent chemical resistance, low moisture absorption, and exceptional acoustical and electrical
properties. Its properties are reasonably similar to those of other polyolefins, although it is more
brittle and more gas permeable.
Applications
Applications include sonar covers, speaker cones, ultrasonic transducer heads, and lightweight
structural parts. It is also FDA compliant for use in food processing machinery. Polymethylpentene
is often used in films and coatings for gas permeable packaging.
Because of its high melting point and good temperature stability, polymethylpentene is used for
autoclavable medical and laboratory equipment, microwave components, and cookware.
It is also often used in electrical components e.g. LED molds because it is an excellent electrical
insulator.
TPX is a hard solid material which can be mechanically shaped into various optical components like
lenses and windows. Also specifically TPX is used in CO2 laser pumped molecular lasers as output
window because it is transparent in the whole terahertz range and totally suppresses the ~10 µm
pump radiation.
In comparison to other materials being used for operating in THz range TPX shows excellent optical
properties with a wavelength independent refractive index of 1.460±0.005 between visible light and
100~GHz.
Polyphthalamide
Polyphthalamide (aka. PPA, High Performance Polyamide) is a thermoplastic synthetic resin of
the polyamide (nylon) family that is used to replace metals in high temperature automotive
applications, as the housing for high temperature electrical connectors and multiple other uses. It has
found a degree of favor for use in cutlery. Cold Steel has advertised the glass fibre reinforced series
as being stealthy (due to them not being detected by metal detectors and having no metallic
reflections) and, being made of "Grivory" (a trade name), stronger than previous models made of
"Zytel".
As a member of the nylon family, it is a semi-crystalline material composed from a diacid and a
diamine. However, the diacid portion contains at least 55% terephthalic acid (TPA) or isophthalic
acid (IPA). TPA or IPA are aromatic components which serve to raise the melting point, glass
transition temperature and generally improve chemical resistance vs. standard aliphatic nylon
polymers.
PPA is manufactured under trade names Zytel(r) HTN, Amodel and Grivory.
Acrylonitrile butadiene styrene
Acrylonitrile butadiene styrene (ABS) (chemical formula (C8H8)x· (C4H6)y·(C3H3N)z) is a common
thermoplastic. Its melting point is approximately 221°F (105°C).[1]
It is a copolymer made by polymerizing styrene and acrylonitrile in the presence of polybutadiene.
The proportions can vary from 15 to 35% acrylonitrile, 5 to 30% butadiene and 40 to 60% styrene.
The result is a long chain of polybutadiene criss-crossed with shorter chains of poly(styrene-co-
acrylonitrile). The nitrile groups from neighboring chains, being polar, attract each other and bind
the chains together, making ABS stronger than pure polystyrene. The styrene gives the plastic a
shiny, impervious surface. The butadiene, a rubbery substance, provides resilience even at low
temperatures. For the majority of applications, ABS can be used between −25 and 60 °C (-13 and
140 °F) as its mechanical properties vary with temperature. The properties are created by rubber
toughening, where fine particles of elastomer are distributed throughout the rigid matrix.
Production of 1 kg of ABS requires the equivalent of about 2 kg of petroleum for raw materials and
energy. It can also be recycled.[2]
Properties
ABS is derived from acrylonitrile, butadiene, and styrene and carbon. Acrylonitrile is a synthetic
monomer produced from propylene and ammonia; butadiene is a petroleum hydrocarbon obtained
from the C4 fraction of steam cracking; styrene monomer is made by dehydrogenation of ethyl
benzene — a hydrocarbon obtained in the reaction of ethylene and benzene.
The advantage of ABS is that this material combines the strength and rigidity of the acrylonitrile and
styrene polymers with the toughness of the polybutadiene rubber.
The most important mechanical properties of ABS are impact resistance and toughness. A variety of
modifications can be made to improve impact resistance, toughness, and heat resistance. The impact
resistance can be amplified by increasing the proportions of polybutadiene in relation to styrene and
also acrylonitrile, although this causes changes in other properties. Impact resistance does not fall off
rapidly at lower temperatures. Stability under load is excellent with limited loads. Thus, changing
the proportions of its components ABS can be prepared in different grades. Two major categories
could be ABS for extrusion and ABS for injection moulding, then high and medium impact
resistance. Generally ABS would have useful characteristics within a temperature range from 10 to
80 °C (50 to 176 °F).
The final properties will be influenced to some extent by the conditions under which the material is
processed to the final product. For example, molding at a high temperature improves the gloss and
heat resistance of the product whereas the highest impact resistance and strength are obtained by
molding at low temperature. Fibers (usually glass fibers) and additives can be mixed in the resin
pellets to make the final product strong and raise the operating range to as high as 80 °C (176 °F).
Pigments can also be added, as the raw material original color is translucent ivory to white. The
aging characteristics of the polymers are largely influenced by the polybutadiene content, and it is
normal to include antioxidants in the composition. Other factors include exposure to ultraviolet
radiation, for which additives are also available to protect against.
Even though ABS plastics are used largely for mechanical purposes, they also have electrical
properties that are fairly constant over a wide range of frequencies. These properties are little
affected by temperature and atmospheric humidity in the acceptable operating range of temperatures.
[3]

ABS polymers are resistant to aqueous acids, alkalis, concentrated hydrochloric and phosphoric
acids, alcohols and animal, vegetable and mineral oils, but they are swollen by glacial acetic acid,
carbon tetrachloride and aromatic hydrocarbons and are attacked by concentrated sulfuric and nitric
acids. They are soluble in esters, ketones, and ethylene dichloride.
While the cost of producing ABS is roughly twice the cost of producing polystyrene, ABS is
considered superior for its hardness, gloss, toughness, and electrical insulation properties. It is
degraded (dissolved) when exposed to acetone.[4] ABS is flammable when it is exposed to high
temperatures, such as a wood fire. It will melt, boil, then burst spectacularly into intense, hot flames.
Applications

Black ABS plastic pipe (vertical, extreme right in photo) in use in a wet basement of a
paper mill, in Sault Ste. Marie, Ontario.
The list of applications for ABS is long and continuously growing. Its light weight and ability to be
injection molded and extruded make it useful in manufacturing products such as drain-waste-vent
(DWV) pipe systems, musical instruments (recorders and plastic clarinets), golf club heads (due to
its good shock absorbance), automotive trim components, enclosures for electrical and electronic
assemblies, protective headgear, whitewater canoes, buffer edging for furniture and joinery panels,
luggage and protective carrying cases, small kitchen appliances, and toys, including Lego bricks.[5]
ABS plastic ground down to an average diameter of less than 1 micrometer is used as the colorant in
some tattoo inks. Tattoo inks that use ABS are extremely vivid. This vividness is the most obvious
indicator that the ink contains ABS, as tattoo inks rarely list their ingredients.[6]
Spectralon
Spectralon is a fluoropolymer, which has the highest diffuse reflectance of any known material or
coating over the ultraviolet, visible, and near-infrared regions of the spectrum.[1] It exhibits highly
Lambertian behavior, and can be machined into a wide variety of shapes for the construction of
optical components such as calibration targets, integrating spheres, and optical pump cavities for
lasers.[1][2][3]
Characteristics
The material has a hardness roughly equal to that of high-density polyethylene and is thermally
stable to >350° C.[1] It is chemically inert to all but the most powerful bases such as sodium amide
and organo-sodium or lithium compounds. The material is extremely hydrophobic.[1] Gross
contamination of the material or marring of the optical surface can be remedied by sanding under a
stream of running water.[4] This surface refinishing both restores the original topography of the
surface and returns the material to its original reflectance. Weathering tests on the material show no
damage upon exposure to atmospheric UV flux. The material shows no sign of optical or physical
degradation after long-term immersion testing in sea water.
Spectralon's reflectance is generally >99% over a range from 400 to 1500 nm and >95% from 250 to
2500 nm.[1] However, grades are available with added carbon to achieve various gray scales.[5]
Surface or subsurface contamination may lower the reflectance at the extreme upper and lower ends
of the spectral range. The material is also highly lambertian at wavelengths from 257 nm to 10600
nm, although reflectivity decreases at wavelengths beyond the near infrared. Spectralon exhibits
absorbances at 2800 nm, then absorbs strongly (<20% reflectance) from 5400 to 8000 nm. Although
the diffused reflectance has been shown to increase overall laser efficiency, the material has a fairly
low damage threshold of 4 joules per square centimeter, limiting its use to lower powered
applications.[6]
The Lambertian reflectance arises from the material's surface and immediate subsurface structure.
The porous network of thermoplastic produces multiple reflections in the first few tenths of a
millimeter. Spectralon can partially depolarize the light it reflects, but this effect decreases at high
incidence angles.[7] Although it is extremely hydrophobic, this open structure readily absorbs non-
polar solvents, greases and oils. Impurities are difficult to remove from Spectralon; thus, the material
should be kept free from contaminants to maintain its reflectance properties.
Applications
Three grades of Spectralon reflectance material are available: optical grade, laser grade and space
grade. Optical-grade Spectralon is characterized by a high reflectance and Lambertian behavior.
Laser-grade Spectralon offers the same physical characteristics as optical-grade material but is a
different formulation of resin that gives enhanced performance when used in laser pump cavities.
Spectralon is used in a variety of "side pumped" lasers.[8] Space-grade Spectralon combines high
reflectance with an extremely lambertian reflectance profile and is used for terrestrial remote sensing
applications.
Spectralon's optical properties make it ideal as a reference surface in remote sensing. For instance, it
is used to obtain leaf reflectance and bidirectional reflectance distribution function (BRDF) in the
laboratory. It can also be applied to obtain vegetation fluorescence using the Fraunhofer lines [9].
Basically Spectralon allows removing the contributions in the emitted light that are not directly
linked to the surface (leaf) properties but to geometrical factors.
Polyethylenechlorinates
CPE is the standardized acronym for thermoplastic chlorinated polyethylene. CM is the standardized
acronym for elastomeric chlorinated polyethylene.
Chlorinated polyethylene is produced by chlorination of polyethylene and has the structure shown in
Figure 4.31.
Figure 4.31: Example of chlorinated polyethylene formula
Chlorine content could be as high as 70% by weight but the current grades have a chlorine content in
the 25% up to 42% range.
These resins can be used as:
• base thermoplastics for extruded, calendered, solution cast and injection-moulded parts and
goods
• elastomers after crosslinking
• modifying resins and additives for other polymers such as PVC, styrene-acrylonitrile,
ethylene polymers and copolymers, acrylics
Properties vary with chlorine content, crystallinity and molecular weight.
Applications as primary thermoplastics to produce flexible parts and products are, for example:
• wire and cable jacketing
• extruded profiles: gasketing, tubing
• moulded shapes: pipe fittings
• coated fabrics: extrusion of coated scrim for tarpaulins
• hose for chemical transfer and storage
CM are speciality elastomers that can be crosslinked either by curing agents or irradiation leading to
parts with fair flexibility, resistance to heat, oils and fuels, ignition, chemicals, low temperatures and
weathering.
Because of their resistance to automotive fluids CM are used for hoses, tubing, air ducts and wire
jacketing, tubes and covers for return side power steering hoses, single construction emission and
vacuum tubing, hose covers, large diameters and convoluted geometries required for air intake ducts
CPE has been used successfully in under-the-hood wire and cable-coating..

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