Polycarbonic esters Polycarbonates

Polycaprolactone diol Polycaprolate Polycarbamic esters Polycarbonate... 

Acrylic ESTER POLYMERS Acrylonitrile POLYMERS Cellulose esters). Engineering plastics (qv) such as acetal resins (qv), polyamides (qv), polycarbonate (qv), polyesters (qv), and poly(phenylene sulfide), and advanced materials such as Hquid crystal polymers, polysulfone, and polyetheretherketone are used in high performance appHcations they are processed at higher temperatures than their commodity counterparts (see Polymers containing sulfur). 

Solubility and Solvent Resistance. The majority of polycarbonates are prepared in methylene chloride solution. Chloroform, i7j -l,2-dichloroethylene, yy -tetrachloroethane, and methylene chloride are the preferred solvents for polycarbonates. The polymer is soluble in chlorobenzene or o-dichlorobenzene when warm, but crystallization may occur at lower temperatures. Methylene chloride is most commonly used because of the high solubiUty of the polymer (350 g/L at 25°C), and because this solvent has low flammabiUty and toxicity. Nonhalogenated solvents include tetrahydrofuran, dioxane, pyridine, and cresols. Hydrocarbons (qv) and aUphatic alcohols, esters (see Esters, organic), or ketones (qv) do not dissolve polycarbonates. Acetone (qv) promotes rapid crystallization of the normally amorphous polymer, and causes catastrophic failure of stressed polycarbonate parts. 

Noncrystalline aromatic polycarbonates (qv) and polyesters (polyarylates) and alloys of polycarbonate with other thermoplastics are considered elsewhere, as are aHphatic polyesters derived from natural or biological sources such as poly(3-hydroxybutyrate), poly(glycoHde), or poly(lactide) these, too, are separately covered (see Polymers, environmentally degradable Sutures). Thermoplastic elastomers derived from poly(ester—ether) block copolymers such as PBT/PTMEG-T [82662-36-0] and known by commercial names such as Hytrel and Riteflex are included here in the section on poly(butylene terephthalate). Specific polymers are dealt with largely in order of volume, which puts PET first by virtue of its enormous market volume in bottie resin. 

Eyeglass frames made of cellulose acetate plasticized with diglycerol esters do not exhibit opaqueness at the frame-lens junction with polycarbonate plastic lenses (146,147). 

Fig. 1. Engineering resins cost vs annual volume (11) (HDT, °C) A, polyetheretherketone (288) B, polyamideimide (>270) C, polyarylether sulfone (170- >200) D, polyimide (190) E, amorphous nylons (124) F, poly(phenylene sulfide) (>260) G, polyarylates (170) H, crystalline nylons (90—220) I, polycarbonate (130) J, midrange poly(phenylene oxide) alloy (107—150) K, polyphthalate esters (180—260) and L, acetal resins (110—140).

Polypropylene has a chemical resistance about the same as that of polyethylene, but it can be used at 120°C (250°F). Polycarbonate is a relatively high-temperature plastic. It can be used up to 150°C (300°F). Resistance to mineral acids is good. Strong alkalies slowly decompose it, but mild alkalies do not. It is partially soluble in aromatic solvents and soluble in chlorinated hydrocarbons. Polyphenylene oxide has good resistance to ahphatic solvents, acids, and bases but poor resistance to esters, ketones, and aromatic or chlorinated solvents. 

By reaction of polyhydroxy compounds with a carbonic acid derivative, a series of related polymers may be produced with carbonate (—0 C0 0—) linkages, the polymers being referred to as polycarbonates. Carbonic acid, C0(0H)2, itself does not exist in the free state but by means of ester exchange Figure 20.1) (1) and phosgenation techniques (II) it is possible to produce useful products. 

In 1930 Carothers and Natta prepared a number of aliphatic polycarbonates using ester-interchange reactions. These materials had a low melting point, were easily hydrolysed and did not achieve commercial significance. 

The chemical resistance of polyester materials is well recognised to be limited because of the comparative ease of hydrolysis of the ester groups. Whereas this ease of hydrolysis was also observed in aliphatic polycarbonates produced by... 

Unless the hydroxyl groups have such proximity that cyclisation takes place, polycarbonates will normally be produced whenever phosgene or a carbonate ester is reacted with a polyhydroxy compound. This means that a very large range of polycarbonate resins are possible and in fact many hundreds have been prepared. 

Aliphatic polycarbonates have few characteristics which make them potentially valuable materials but study of various aromatic polycarbonates is instructive even if not of immediate commercial significance. Although bisphenol A polycarbonates still show the best all-round properties other carbonic ester polymers have been prepared which are outstandingly good in one or two specific properties. For example, some materials have better heat resistance, some have better resistance to hydrolysis, some have greater solvent resistance whilst others are less permeable to gases. 

There has also been active interest in blends of PBT with other polymers. These include blends with PMMA and polyether-ester rubbers and blends with a silicone/polycarbonate block copolymer. 

Where transparency is required, a range of polymers is available. Polystyrene is the least expensive but polymethylmethacrylate has an outstanding high light transmission combined with excellent weathering properties. Also to be considered are the polycarbonates, glass-clear polyamides, SAN, butadiene-styrene block copolymers, MBS polymers, plasticised PVC, ionomers and cellulose esters such as cellulose acetate. 

All of the eommereial alkyl eyanoaerylate monomers are low-viseosity liquids, and for some applications this can be an advantage. However, there are instances where a viseous liquid or a gel adhesive would be preferred, sueh as for application to a vertical surface or on porous substrates. A variety of viscosity control agents, depending upon the desired properties, have been added to increase the viscosity of instant adhesives [21]. The materials, which have been utilized, include polymethyl methacrylate, hydrophobic silica, hydrophobic alumina, treated quartz, polyethyl cyanoacrylate, cellulose esters, polycarbonates, and carbon black. For example, the addition of 5-10% of amorphous, non-crystalline, fumed silica to ethyl cyanoacrylate changes the monomer viscosity from a 2-cps liquid to a gelled material [22]. Because of the sensitivity of cyanoacrylate esters to basic materials, some additives require treatment with an acid to prevent premature gelation of the product. 

Cellulose Esters Epoxy Resins Lignins Polystyrene Poly (2-vinyl pyridine) Polyvinyl Chloride Polymethyl methacrylate Polyphenylene Oxide Phenolics Polycarbonate Polyvinyl Acetate, etc. Polyvinyl butyral SBR rubber, etc., etc. 

Nearly all of the polymers produced by step-growth polymerization contain heteroatoms and/or aromatic rings in the backbone. One exception is polymers produced from acyclic diene metathesis (ADMET) polymerization.22 Hydrocarbon polymers with carbon-carbon double bonds are readily produced using ADMET polymerization techniques. Polyesters, polycarbonates, polyamides, and polyurethanes can be produced from aliphatic monomers with appropriate functional groups (Fig. 1.1). In these aliphatic polymers, the concentration of the linking groups (ester, carbonate, amide, or urethane) in the backbone greatly influences the physical properties. 

Many random copolyesters and polyester-polycarbonates have also been prepared by ester interchange reactions in the molten state. Thus, poly(ethylene terephthalate-co -isophthalates) can be obtained by simple melt blending of PET and poly(ethylene isophthalate) (PEI) homopolyesters at 270°C. The copolymer changes gradually from a block type at the beginning of reaction to a random-type... 

Lipase is an enzyme which catalyzes the hydrolysis of fatty acid esters normally in an aqueous environment in living systems. However, hpases are sometimes stable in organic solvents and can be used as catalyst for esterifications and transesterifications. By utihzing such catalytic specificities of lipase, functional aliphatic polyesters have been synthesized by various polymerization modes. Typical reaction types of hpase-catalyzed polymerization leading to polyesters are summarized in Scheme 1. Lipase-catalyzed polymerizations also produced polycarbonates and polyphosphates. 

While additive analysis of polyamides is usually carried out by dissolution in HFIP and hydrolysis in 6N HC1, polyphthalamides (PPAs) are quite insoluble in many solvents and very resistant to hydrolysis. The highly thermally stable PPAs can be adequately hydrolysed by means of high pressure microwave acid digestion (at 140-180 °C) in 10 mL Teflon vessels. This procedure allows simultaneous analysis of polymer composition and additives [643]. Also the polymer, oligomer and additive composition of polycarbonates can be examined after hydrolysis. However, it is necessary to optimise the reaction conditions in order to avoid degradation of bisphenol A. In the procedures for the analysis of dialkyltin stabilisers in PVC, described by Udris [644], in some instances the methods can be put on a quantitative basis, e.g. the GC determination of alcohols produced by hydrolysis of ester groups. 

Whereas the tensile strength was not a sensitive function of the monomer structure, the tensile modulus (Young s Modulus) was clearly related to the monomer structure. This is expected since the tensile modulus is a measure of the polymer s resistance to deformation and is related to the "stiffness" of a polymeric material. The highest tensile modulus (22,000 kg/cm2,2.2 GPa) was measured for poly(BPA iminocarbonate). Replacement of BPA by Dat-Tyr-Hex reduced the tensile modulus significantly. This observation can possibly be attributed to the presence of the long hexyl ester pendent chain in Dat-Tyr-Hex. Generally, the polyiminocarbonates were somewhat "stiffer" than the corresponding polycarbonates. Thus, the tensile moduli of poly(Dat-Tyr-Hex iminocarbonate) and poly(Dat-Tyr-Hex carbonate) were 16,300 kg/cm2 (1.6 GPa) and 13,900 kg/cm2 (1.3 GPa) respectively. 

The reaction of CDI with a single mole of alcohol yields imidazole-iV-carboxyl-ates,t229H231] which by reaction with a second mole of alcohol lead to carbonic esters. With bifunctional alcohols CDI yields polycarbonic esters.[1-, C232]... 

Bottenbruch, L. (ed) Engineering Thermoplastics Polycarbonates, Polyacetals, Polyesters, Cellulose Esters. (1996) Hanser Gardner Publications, Cincinnati,... 

---