Poly polyepichlorohydrin

Epichlorohydrin Elastomers without AGE. ECH homopolymer, polyepichlorohydrin [24969-06-0] (1), and ECH—EO copolymer, poly(epichlorohydrin- (9-ethylene oxide) [24969-10-6] (2), are linear and amorphous. Because it is unsymmetrical, ECH monomer can polymerize in the head-to-head, tail-to-tail, or head-to-tail fashion. The commercial polymer is 97—99% head-to-tail, and has been shown to be stereorandom and atactic (15—17). Only low degrees of crystallinity are present in commercial ECH homopolymers the amorphous product is preferred. 

These results suggest that poly[(chloromethyl)thiirane] (PCMT, 4) should be substantially more reactive than polyepichlorohydrin... 

The poly(ether/amide) thin film composite membrane (PA-100) was developed by Riley et al., and is similar to the NS-101 membranes in structure and fabrication method 101 102). The membrane was prepared by depositing a thin layer of an aqueous solution of the adduct of polyepichlorohydrin with ethylenediamine, in place of an aqueous polyethyleneimine solution on the finely porous surface of a polysulfone support membrane and subsequently contacting the poly(ether/amide) layer with a water immiscible solution of isophthaloyl chloride. Water fluxes of 1400 16001/m2 xday and salt rejection greater than 98% have been attained with a 0.5% sodium chloride feed at an applied pressure of 28 kg/cm2. Limitations of this membrane include its poor chemical stability, temperature limitations, and associated flux decline due to compaction. 

VC/Polyepichlorohydrin and VC/Poly (epichlorohydrin-co-ethylene oxide) Graft Copolymers. Graft copolymers of this type with high backbone-polymer content should be useful PVC additives. 

VC/Polyepichlorohydrin and VC/Poly(epichlorohydrin-co-ethylene oxide) Graft Copolymers. Alloys of PVC and graft copolymers of this type with high backbone-polymer content give interesting results in the field of bottle blowing (12). The combination of transparency and impact strength that can be realized with these compositions should enable them to penetrate into the field covered at present by PVC-MBS mixtures. 

A number of chlorinated poly(ethers) have practical uses. A common compound from this group is polyepichlorohydrin, [-CH(CH2CI)CH20-]n. Polyepichlorohydrin has practical applications as an elastomer and is used in copolymers with propylene oxide, ethylene oxide, allyl glycidyl ether (1-allyloxy-2,3-epoxypropane), etc. Another example is poly oxy[2,2 -bis(chloromethyl)-1,3-propandiyl] or poly[oxy-1,3-(2,2 -dichloromethyl)propylene], CAS 25323-58-4, which can be used as inert lining material for chemical plant equipment, as adhesive, coating material, etc. This macromolecule can be prepared starting with pentaerythritol in the sequence of reactions shown below ... 

Polyepichlorohydrin pyrolysate is a complex mixture of compounds, somehow similar to that obtained by the pyrolysis of poly(ethylene oxide). The breaking of the C-O bonds is probably easier than that of C-C bonds. However, C-C bonds are more frequently cleaved in pyrolysis of polyepichlorohydrin than in that of poly(propylene oxide). The elimination of HCI (4.7% in the pyrogram) further complicates the pyrogram of this polymer. 

Figure 2.4. Schematic illustrations of repeat units of several of the polymers listed in Table 2.2. (a) Poly(thiocarbonyl fluoride), (b) Poly(glycolic acid), (c) Polyepichlorohydrin. (d) Poly(maleic anhydride), (e) Poly(N-methyl glutarimide). (f) Poly(N-phenyl maleimide). (g) Poly[3,5-(4-phenyl-1,2,4-triazole)-1,4-phenylene]. (h) Phenoxy resin, (i) Poly(oxy-1,4-phenylene-oxy-1,4-phenylene-carbonyl-l,4-phenylene). (j) Udel. (k) Victrex. (1) Tori on. (m) Ultem. (n) Resin F.

Nether >s 1 for polyoxymethylene, polyepichlorohydrin (see Figure 2.4) and poly(vinyl ethyl ether), and 2 for Ultem (see Figure 2.4) and poly(vinyl butyral) (see Figure 2.9). Note that only (-0-) linkages between two carbon atoms will be counted as ether linkages. If there are silicon atoms on one or both sides of the oxygen atom, the linkage is not counted in Nether. For example, Nether=0 for poly(dimethyl siloxane). 

Kurihara and coworkers at Toray Industries prepared several aminated derivatives of polyepichlorohydrin, then formed composite polyamide membranes by interfacial reaction with isophthaloyl chloride.38 Polyepichlorohydrin was converted to polyepiiodohydrin, then reacted with either4-(aminomethyl)piperidine, 3-(methylamino)hexahydroazepine, or 3-(amino)hexahydroazepine. Also, poly-epiaminohydrin was prepared by reduction of the azide derivative of polyepiiodohydrin. Best salt rejections were obtained if the polymeric amine formulation contained a substantial proportion of the monomeric amines as coreactants in the interfacial reaction. In tests on 3.5% sodium chloride at 800 psi and 25 C, salt rejections of 99.5% at fluxes of 8 to 9 gfd were characteristic. A three-zone barrier layer was produced, consisting of a heat-crosslinked polyamine gel (as in NS-100), a polyamide layer incorporating both the polymeric... 

Particular problems arise from the use of polymer supports as there is insufficient information available about the detailed structure of the support and while novel support materials such as polyepichlorohydrin, chloro-methylated silicone, and poly(vinyl alcohol) have been used, these do not necessarily have a well defined structure. 

Quite recently, Gonin etal. [188, 208, 212] and Guichard [209] conducted a systematic study of factors influencing SH efficiency. In this work, SHG was measured for five polymers containing the NLO mesogenic groups 41 a polyacrylate 41 PA 3, a polymethacrylate 41 PMA 3, two copolyethers derived from polyepichlorohydrin 45 (a=0.8) and 45 (x=0.55) and a copolyether 46 derived from poly(3,3-bis(chlorometh-yl)oxetane). 

TTP), a Mlchlor s Ketone "EMKO", and an oxime dye Incorporated with a catalyst. The polymer coatings tested were polyvinylpyrrolidone (PVP), poly-methylmethacrylate (PMM), polyepichlorohydrin (PEH), and polyethylene maleate (PEM). Note that with the exception of the oxazlne dye, all other dyes show no color reversibility. However, all the polymers show reversibility to these vapors indicating physical adsorption predominates the vapor/film interaction. 

The upper right curves in Fig. 7.72 display data of solutions of two aliphatic polyesters with polyepichlorohydrin. A large K2 is needed in S to account for the negative deviation of the solution with poly(butylene adipate), PBA, while the solutions with poly(ethylene adipate), PEA, show little redistribution in the contact neighborhood (K2 => 0). The lower right curves demonstrate that solutions of poly(vinyl chloride) and poly(e-caprolactone) can be fitted with all equations. The rather large Kj and K2 must cancel, since Kj = Kj = 0 leads to the Gordon-Taylor... 

Figure 3.25 shows the changes of heat capacity with temperature for the polyepichlorohydrin (PECH)/poly(vinyl acetate) (PVAc) combination at different diffusion times. In the glass transition region, the heat capacity traces are different for the different diffusion times.However, it is difficult to draw out more detailed information from these traces. The dCp/dT curves, however, clearly showed that an interface is formed by thermal diffusion, (see Figure 3.26). This is shown by the increase in the dCp/dT signal between the two glass transitions. With increasing diffusion time, the concentration of the interface will change and its thickness will increase.

Figure 7.58 DMA curves for polyepichlorohydrin (PECH)-poly(methyl methacrylate) (FMMA) interpenetrating f)olymer networks (IPNs) with different compositions [44. PECHrPMMA mass ratio I, 100 0 II, 75 25 III, 65 35 IV, 50 50 V, 35 65 VI, 0 100...

N nonwoven, S single, O oriented, PAA polyacrylic acid, PVA polyvinyl alcohol, PEI polyethyleneimine, HCSA 10-camphorsulfonic acid, PAN/polyaniline, PEO poly(ethylene oxide), PDPA polydiphenylamine, PMMA polymethyl methacrylate, POT poly-o-toluidine, PS polystyrene, MWCNT multiwalled carbon nanotube, CB carbon black, PECH polyepichlorohydrin, PIB polyisobutylene, PVP polyvinylpyrrolidone, PAN polyacrylonitrile, VOC volatile organic... 

Figure 1 Polymer interpretation chart. PAI, polyamideimide PC, polycarbonate UP, unsaturated polyester PDAP, diarylate phtalate resin VC-VAc, vinyl chloride-vinyl acetate copolymer PVAc, polyvinyl acetate PVFM, polyvinyl formal PUR, polyurethane PA, polyamide PMA, methacrylate ester polymer EVA, ethylene-vinyl acetate copolymer PF, phenol resin EP, epoxide resin PS, polystyrene ABS, acrylonitrile-butadiene-styrene copolymer PPO, polyphenylene oxide P-SULFONE, poly-sulfone PA, polyamide UF, urea resin CN, nitrocellulose PVA, polyvinyl acetate MC, methyl cellulose MF, melamine resin PAN, polyacrylonitrile PVC, polyvinyl chloride PVF, polyvinyl fluoride CR, polychloroprene CHR, polyepichlorohydrin SI, polymethylsiloxane POM, polyoxy-methylene PTFE, polytetrafluoroethylene MOD-PP, modified PP EPT, ethylene-propylene terpolymer EPR, ethylene-propylene rubber PI, polyisoprene BR, butyl rubber PMP, poly(4-methyl pentene-1) PE, poly(ethylene) PB, poly(butene-l). (Adapted from Ref. 22, p. 50.)...

APTMOS 3-amino-propyl-trimethoxysilane, AuHFA fluoroalcohol-coated gold nanospheres, BBCB bisbenzocy-clobutene, BCB benzocyclobutene, CA cellulose acetate, CAB cellulose acetate-butyrate, CEE chloroethyl ether, DIMP diisopropyl methylphosphonate, DMMP dimethyl methylphosphonate, EPR epoxidized novolac, IPA isopropanol, OV-225 cyanopropyl methyl phenylmethyl silicone, OV-275 dicyanoallyl sihcone, PAAM polyallylamine hydrochloride, PAPPS propylaminopropyl polysiloxane, PDMS poly(dimethylsiloxane), PECH polyepichlorohydrin, PEG polyethylene glycol, PEI polyethyleneimine, PEO polyethylene oxide, PEVA polyethylene-co-vinyl acetate, PEUT poly(ether urethane), PHEMA poly(2-hydroxyethyl methacrylate), PIB polyisobutylene, PMMA poly(methyl methacrylate), PTMOS propyltrimethoxysilane, PVA polyvinyl alcohol, PVP polyvinylpyrrolidone, SXFA siloxanefluoroalcohol... 

Synthetic rubbers are produced as commodities. Polybutadiene, polybutylene, polychloroprene and polyepichlorohydrin are examples of elastomeric homopolymers. Copolymeric rubbers comprise poly-(butadiene-co-styrene), poly(butadiene-co-acryloni-trile), poly(ethylene-co-propylene-co-diene), and poly-(epichlorohydrin-co-ethylene oxide). The unsaturated group in the comonomer provides reactive sites for the crosslinking reactions. Copolymers combine resilience with resistance to chemical attack, or resilience in a larger temperature range, and thermoplastic-like properties. There are several studies in the literature describing the preparation of blends and composites of elastomers and conductive polymers. A description of some significant examples is given in this section. 

Further confirmation of the uniformly head-to-tail structure of HERCLOR H elastomer was obtained from its carbon-13 NMR spectrum. Since no literature spectra of polyepichlorohydrin were available for comparison, the carbon-13 NMR spectra of the poly-(propylene oxideD resulting from dechlorination with LAH were also examined. Published spectra of poly(propylene oxideD with detailed peak assignments are available. 

Figure 8 shows the carbon-13 NMR spectra of crystalline polyepichlorohydrin and the poly(propylene oxide) it yielded by dechlorination with LAH. The poly(propylene oxide) was also highly crystalline (m.p. 64 C. by DTA) and its carbon-13 NMR spectrum corresponds closely to that reported for the isotactic polymer. Thus, the single methylene peak at about 70.2 ppm. in the spectrum of crystalline polyepichlorohydrin is due to isotactic dyads. The poor resolution in this spectrum is due to low solubility of the crystalline polymer in the benzene solvent. No trace of the peaks due to polyepichlorohydrin are observable in the spectra of the poly(propylene oxide) obtained by dechlorination. In addition, the number of observable peaks does not increase as a result of the LAH treatment. This is further evidence that the dechlorination reaction results in smooth replacement of Cl with H without otherwise altering the structure of the polymer. 

Figure H. Carbon-13 NMR spectra of (A) crystalline polyepichlorohydrin and (B) the poly(pro-pylene oxide) obtained by dechlorination with LAH...

A procedure has been described for the determination of irregular head-to-head and tail-to-tail linkages in polyepichlorohydrin. This procedure involves dechlorination of the polymer with lithium aluminum hydride, cleavage of the resultant poly-(propylene oxide) with n-butyllithium, and analysis by gas chromatography to determine the relative amounts of the respective dipropylene glycols. 

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