Copolymers, epoxides

Dodoxynol-11 Dodoxynol-12 Dodoxynol-14 EO/dimethylsiloxane/EO block copolymer EO/PO block polymer or copolymer Epoxidized linseed oil, butyl ester Epoxidized linseed oil, 2-ethylhexyl ester Epoxidized linseed oil, methyl ester Epoxidized soybean oil, butyl ester Epoxidized soybean oil, methyl ester... 

These monomers provide a means for introducing carboxyl groups into copolymers. In copolymers these acids can improve adhesion properties, improve freeze-thaw and mechanical stability of polymer dispersions, provide stability in alkalies (including ammonia), increase resistance to attack by oils, and provide reactive centers for cross-linking by divalent metal ions, diamines, or epoxides. 

Another type of soHd supetacid is based on perfluorinated resin sulfonic acid such as the acid form of Du Font s Nafion resin, a copolymer of a perfluorinated epoxide and vinylsulfonic acid or soHd, high molecular weight petfluotoalkanesulfonic acids such as petfluotodecanesulfonic acid, CF2(CF2)qS02H. Such sohd catalysts have been found efficient in many alkylations of aromatic hydrocarbons (225) and other Friedel-Crafts reactions (226). 

Such copolymers of oxygen have been prepared from styrene, a-methylstyrene, indene, ketenes, butadiene, isoprene, l,l-diphen5iethylene, methyl methacrjiate, methyl acrylate, acrylonitrile, and vinyl chloride (44,66,109). 1,3-Dienes, such as butadiene, yield randomly distributed 1,2- and 1,4-copolymers. Oxygen pressure and olefin stmcture are important factors in these reactions for example, other products, eg, carbonyl compounds, epoxides, etc, can form at low oxygen pressures. Polymers possessing dialkyl peroxide moieties in the polymer backbone have also been prepared by base-catalyzed condensations of di(hydroxy-/ f2 -alkyl) peroxides with dibasic acid chlorides or bis(chloroformates) (110). 

Propylene oxide can be copolymerized with other epoxides, such as ethylene oxide (qv) (25,29,30) or tetrahydrofiiran (31,32) to produce copolymer polyols. Copolymerization with anhydrides (33) or CO2 (34) results in polyesters and polycarbonates (qv), respectively. 

In 1957, it was discovered that organometaUic catalysts gave high mol wt polymers from epoxides (3). The commercially important, largely amorphous polyether elastomers developed as a result of this early work are polyepichlorohydrin (ECH) (4,5), ECH—ethylene oxide (EO) copolymer (6), ECH—aUyl glycidyl ether (AGE) copolymer (7,8), ECH—EO—AGE terpolymer (8), ECH—propylene oxide (PO)—AGE terpolymer (8,9), and PO—AGE copolymer (10,11). The American Society for Testing and Materials (ASTM) has designated these polymers as follows ... 

Low molecular weight liquid nitrile rubbers with vinyl, carboxyl or mercaptan reactive end groups have been used with acrylic adhesives, epoxide resins and polyesters. Japanese workers have produced interesting butadiene-acrylonitrile alternating copolymers using Ziegler-Natta-type catalysts that are capable of some degree of ciystallisation. 

The acetal polymers are probably never supplied for use without any additives being incorporated. As mentioned in Section 19.3.1 antioxidants of the phenol alkane type are present in both homopolymers and copolymers. Acid acceptors are also believed to be widely used to absorb traces of acidic materials which attack the acetal linkage. Epoxides, nitrogen compounds and basic salts have been successfully employed. 

Fig. 20. UV initiated cationic cure of epoxidized block copolymer in the presence of alcohol (Kraton Polymer s EKP-207 and L1203 inono-ol).

ATBN - amine terminated nitrile rubber X - Flory Huggins interaction parameter CPE - carboxylated polyethylene d - width at half height of the copolymer profile given by Kuhn statistical segment length DMAE - dimethyl amino ethanol r - interfacial tension reduction d - particle size reduction DSC - differential scanning calorimetry EMA - ethylene methyl acrylate copolymer ENR - epoxidized natural rubber EOR - ethylene olefin rubber EPDM - ethylene propylene diene monomer EPM - ethylene propylene monomer rubber EPR - ethylene propylene rubber EPR-g-SA - succinic anhydride grafted ethylene propylene rubber... 

Polyamides (nylons) The main types of nylon are oil and petrol resistant, but on the other hand susceptible to high water absorption and to hydrolysis. There are a few solvents such as phenol, cresol and formic acid. Special grades include a water-soluble nylon, amorphous copolymers and low molecular weight grades used in conjunction with epoxide resins. Transparent amorphous polyamides are also now available. 

The effect of a catalyst is important in cationic copolymerizations. Epoxides and /3-lactones form random copolymers only with trialkyl aluminum catalysts. Unusual sequence distributions were observed in the cationic copolymerization of epoxides or lactones using Lewis acids175-177) have been attributed to the di-... 

Anionic copolymerization of cyclic monomers occurs only between similar monomer pairs. Random copolymers are not formed between vinyl monomers and epoxides or lactones198 because the propagating species are very different. Thus, the success of the copolymerization of cyclic disulfide and nitropropylene was an exceptional case... 

Zinc carbonate reacts with epoxide to form zinc alkoxide, which in turn reacts with carbon dioxide to regenerate zinc carbonate. The most effective catalyst systems were the reaction products between diethylzinc and polyhydroxy compounds such as water or pdyhydric phenols243,244. This copolymer is interesting as a biodegradable elastomer248. ... 

An alternate way to make block copolymers involving PDMS blocks 124,125) is to have these chains fitted with epoxide functions at chain end, and to react them with a vinylic or dienic polymer carrying terminal COOH functions. Sequential addition of monomers has also been used, the ring opening polymerization of the cyclic trimer (D3) being initiated by the anionic site of a living polymer126). 

Puskas, J.E., Pattern, W.E., Wetmore, P.M., and Krukonis, A. Multiarm-star polyisobutylene-polystyrene thermoplastic elastomers from a novel multifunctional initiator, Polym. Mater. Set Eng., 82,42 3, 1999. Brister, L.B., Puskas, J.E., and Tzaras, E. Star-branched PIB/poly(p-t-bu-Styrene) block copolymers from a novel epoxide initiator, Polym. Prepr., 40, 141-142, 1999. 

For example, the block copolymers can be modified with a vinyl monomer [281 ]. In addition, diglycidyl ethers [282], that is, precondensates for epoxides, can be used as modifiers. Another possibility is modification with polyamines. 

A Japanese patent72) claims the synthesis of thermally stable copolymers by free-radical terpolymerization of dialkylstannyl dimethacrylates, glycidyl methacrylate and vinyl monomers (vinyl chloride, styrene, vinyl acetate, etc.). The products contain 0.5 to 30% tin and 0.05 to 7 % epoxide oxygen. 

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