Sulfonation chlorinated polyethylene

Pandey et al. have used ultrasonic velocity measurement to study compatibility of EPDM and acrylonitrile-butadiene rubber (NBR) blends at various blend ratios and in the presence of compa-tibilizers, namely chloro-sulfonated polyethylene (CSM) and chlorinated polyethylene (CM) [22]. They used an ultrasonic interferometer to measure sound velocity in solutions of the mbbers and then-blends. A plot of ultrasonic velocity versus composition of the blends is given in Eigure 11.1. Whereas the solution of the neat blends exhibits a wavy curve (with rise and fall), the curves for blends with compatibihzers (CSM and CM) are hnear. They resemble the curves for free energy change versus composition, where sinusoidal curves in the middle represent immiscibility and upper and lower curves stand for miscibihty. Similar curves are obtained for solutions containing 2 and 5 wt% of the blends. These results were confirmed by measurements with atomic force microscopy (AEM) and dynamic mechanical analysis as shown in Eigures 11.2 and 11.3. Substantial earher work on binary and ternary blends, particularly using EPDM and nitrile mbber, has been reported. 

FIGURE 11,1 Ultrasonic velocity versus acrylonitrile-butadiene mbber/ethylene-propylene-diene monomer (NBR-EPDM) blend composition (a) no compatibiUzer, (b) with chloro-sulfonated polyethylene (CSM), and (c) with chlorinated polyethylene (CM). (From Pandey, K.N., Setua, D.K., and Mathur, G.N., Polym. Eng. Set, 45, 1265, 2005.)... 

When two polymers interact or react with each other, they are likely to provide a compatible, even a miscible, blend. Epoxidized natural rubber (ENR) interacts with chloro-sulfonated polyethylene (Hypalon) and polyvinyl chloride (PVC) forming partially miscible and miscible blends, respectively, due to the reaction between chlorosulfonic acid group and chlorine with epoxy group of ENR. Chiu et al. have studied the blends of chlorinated polyethylene (CR) with ENR at blend ratios of 75 25, 50 50, and 25 75, as well as pure rubbers using sulfur (Sg), 2-mercapto-benzothiazole, and 2-benzothiazole disulfide as vulcanizing agents [32]. They have studied Mooney viscosity, scorch... 

MC MDI MEKP MF MMA MPEG MPF NBR NDI NR OPET OPP OSA PA PAEK PAI PAN PB PBAN PBI PBN PBS PBT PC PCD PCT PCTFE PE PEC PEG PEI PEK PEN PES PET PF PFA PI PIBI PMDI PMMA PMP PO PP PPA PPC PPO PPS PPSU Methyl cellulose Methylene diphenylene diisocyanate Methyl ethyl ketone peroxide Melamine formaldehyde Methyl methacrylate Polyethylene glycol monomethyl ether Melamine-phenol-formaldehyde Nitrile butyl rubber Naphthalene diisocyanate Natural rubber Oriented polyethylene terephthalate Oriented polypropylene Olefin-modified styrene-acrylonitrile Polyamide Poly(aryl ether-ketone) Poly(amide-imide) Polyacrylonitrile Polybutylene Poly(butadiene-acrylonitrile) Polybenzimidazole Polybutylene naphthalate Poly(butadiene-styrene) Poly(butylene terephthalate) Polycarbonate Polycarbodiimide Poly(cyclohexylene-dimethylene terephthalate) Polychlorotrifluoroethylene Polyethylene Chlorinated polyethylene Poly(ethylene glycol) Poly(ether-imide) Poly(ether-ketone) Polyethylene naphthalate Polyether sulfone Polyethylene terephthalate Phenol-formaldehyde copolymer Perfluoroalkoxy resin Polyimide Poly(isobutylene), Butyl rubber Polymeric methylene diphenylene diisocyanate Poly(methyl methacrylate) Poly(methylpentene) Polyolefins Polypropylene Polyphthalamide Chlorinated polypropylene Poly(phenylene oxide) Poly(phenylene sulfide) Poly(phenylene sulfone)... 

PB PBI PBMA PBO PBT(H) PBTP PC PCHMA PCTFE PDAP PDMS PE PEHD PELD PEMD PEC PEEK PEG PEI PEK PEN PEO PES PET PF PI PIB PMA PMMA PMI PMP POB POM PP PPE PPP PPPE PPQ PPS PPSU PS PSU PTFE PTMT PU PUR Poly(n.butylene) Poly(benzimidazole) Poly(n.butyl methacrylate) Poly(benzoxazole) Poly(benzthiazole) Poly(butylene glycol terephthalate) Polycarbonate Poly(cyclohexyl methacrylate) Poly(chloro-trifluoro ethylene) Poly(diallyl phthalate) Poly(dimethyl siloxane) Polyethylene High density polyethylene Low density polyethylene Medium density polyethylene Chlorinated polyethylene Poly-ether-ether ketone poly(ethylene glycol) Poly-ether-imide Poly-ether ketone Poly(ethylene-2,6-naphthalene dicarboxylate) Poly(ethylene oxide) Poly-ether sulfone Poly(ethylene terephthalate) Phenol formaldehyde resin Polyimide Polyisobutylene Poly(methyl acrylate) Poly(methyl methacrylate) Poly(methacryl imide) Poly(methylpentene) Poly(hydroxy-benzoate) Polyoxymethylene = polyacetal = polyformaldehyde Polypropylene Poly (2,6-dimethyl-l,4-phenylene ether) = Poly(phenylene oxide) Polyp araphenylene Poly(2,6-diphenyl-l,4-phenylene ether) Poly(phenyl quinoxaline) Polyphenylene sulfide, polysulfide Polyphenylene sulfone Polystyrene Polysulfone Poly(tetrafluoroethylene) Poly(tetramethylene terephthalate) Polyurethane Polyurethane rubber... 

A second family of ionic elastomers based on the sulfonation of chlorinated polyethylene was also introduced in the early 1950 s by E. I. du Pont de Nemours Co., Inc. Curing these materials with various metal oxides gives rise to a combination of ionic and covalent crosslinks, and these elastomers are commercially available under the trade name Hypalon. 

Further modification of polyethylene is possible by chemical substitution of hydrogen atoms this occurs preferentially at the tertiary carbons of a branching point and primarily involves chlorination, sulfonation, phosphorylination, and intermediate combinations. (See chlorinated polyethylene chlorosulfonated polyethylene phosphorylated polyethylene ionomer.)... 

Thus, use of polyolefins against chlorine, polyethylenes and polyisobutylenes against aldrin, poly(methyl methacrylates) against sodium alklbenzenesulfonates, and poly(styrene sulfonates) against cadmium chloride, though possible, is not advantageous for amelioration except where local availability may compensate. 

To this category belong PP blends with 4-6wt.% of either chloro-sulfonated polyethylene (CSR), or chlorinated polyethylene (CPE). These blends show good processability and mechanical properties. In 1990, PP blends with CSR and ultra-low density polyethylene (ULDPE) were first partially vulcanized then dispersed within a thermoplastic CSR. The alloys showed good processability, hot-weld strength, interplay adhesion and crack resistance. 

The word ionomer dates back to 1965, but materials of this type had been synthesized and investigated long before. Examples of early work include the investigation of Littman and Marvel in 1930, synthesis of an elastomer based on butadiene and acrylic acid in the early 1930 s, and the appearance in the 1950 s of du Font s Hypalon (sulfonated, chlorinated, and cross-linked polyethylene) [29]. 

Beside the compounds in which the characteristic constituents are polyolefins, other products also may be employed for insulation and jackets. These include crosslinked compounds and constituted from chloro-sulfonated polyethylene (CP insulation and jackets for wires and cables used for deep wall submersible pumps subjected to 60, 90, and 105°C) chlorinated polyethylene (CPE Insulation and jackets for wires subjected to 90°C) ethylene-propylene-diene monomer (EDPM)... 

Additional examples of the application of the Flory EOS to polymer blends include polystyrene/poly(vinyl methyl ether) [15,20,21], oligomeric polystyrene/polybutadiene [22], ethylene-vinyl acetate/chlorinated polyethylene [23], poly(e-caprolactone)/PVC [24], poly-(ether sulfone)/poly(ethylene oxide) [25]. 

Poly(vinyl alcohol) Polyacrolein Poly(acrylic acid) Poly(vinyl alkyl ethers) Poly(vinyl methyl ketone) Polymethylene Chlorinated polyethylene Chlorosulfonated polyethylene Polyacrylonitrile Sulfonated polystyrene Poly(ethylene oxide) Poly(ethylene terephthalate)... 

In all the compositions, the DCP-cured blends showed better properties than the corresponding unvulcanized samples. Choudhary et al. [30] further demonstrated the use of EPDM, chlorinated PE, chlorosulfo-nated PE, maleic anhydride modified polyethylene, and blends of epoxidized natural rubber-sulfonated EPDM as compatibilizers in NR-LDPE (low-density PE) blends. 

Nitrous oxide disappears at a high rate in the cases of both polyethylene and polyisobutylene, but no chemical addition to the polymer chain can proceed because the nitrous oxide changes simply to nitrogen and water during irradiation in the polymer solid phase. This behavior of nitrous oxide differs entirely from that of oxygen, chlorine, sulfur dioxide, etc., as an atmosphere during irradiation. In the case of these latter gases, the irradiated polymer should be oxidized, chlorinated, or sulfonated. 

The developed coating is a waterborne fire-protective composition consisting of a combination of intumescent organic and inorganic particles, an inorganic water glass, a water dispersion of chlorine-sulfonated polyethylene (CSPE) and pigments (or silicon dioxide). 

Many other types of ECP have been described. These include PS-block-PPO [61], boron containing PVA [62], polyethylene dioxythiophene/polystyrene sulfonate [65], PC-ABS composites [64], PEO composites [64], PEO complexes with sodium lanthanum tetrafluoride [63], chlorine substituted PANI [70], PVP-PVA coupled with potassium bromate [57], PANI-PA 6,6 composite films [72], talc-PPY composites [54], epoxy resin alpha-haematite nanorod composites [56], PP-montmorillonite composites [69], magnetite containing polymers [105], LDPE [27], PC-acrylonitrile-butadiene composites [106], sodium ion conducting PEO complexed with sodium lanthanum tetrafluoride [63], PVDE [107], PANI composites [108], PP novolac resins [109], dendrimers containing light switchable azobenzene [110],PVP/PVA [107] and PPY[111]. 

PMMA/PEO, polyethylene oxide PC/lithium salt of sulfonated polystyrene PS/polyphenylmethyl siloxane Chlorinated PE/chlorinated polybutadiene PS/carboxylated PPO PPO/poly(alpha-methylstyrene)... 

Sulfurylchloride is used as a chemical for selective chlorination of side chains of aromatics. Sulfurylchloride also sulfonates and dehydrates organic compounds. In the industry it is used as intermediate for the production of organics for colouring agent, for pesticides, for disinfection matters and for pharmaceutical products [13]. Sulfurylchloride is also used at the production of sulfonic acid and for the sulfochlorination of polyethylene. Sulfurylchloride is produced from sulfur dioxide and chloride... 

Some measurements of this property have been made in a range of electrically conducting polymers. These include epoxy resin/polyaniline-dodecylbenzene sulfonic acid blends [38], polystyrene-black polyphenylene oxide copolymers [38], semiconductor-based polypyrroles [33], titanocene polyesters [40], boron-containing polyvinyl alcohol [41], copper-filled epoxy resin [42], polyethylidene dioxy thiophene-polystyrene sulfonate, polyvinyl chloride, polyethylene oxide [43], polycarbonate/acrylonitrile-butadiene-styrene composites [44], polyethylene oxide complexes with sodium lanthanum tetra-fluoride [45], chlorine-substituted polyaniline [46], polyvinyl pyrolidine-polyvinyl alcohol coupled with potassium bromate tetrafluoromethane sulfonamide [47], doped polystyrene block polyethylene [38, 39], polypyrrole [48], polyaniline-polyamide composites [49], and polydimethyl siloxane-polypyrrole composites [50]. 

The chemical modification of homopolymers such as polyvinylchloride, polyethylene, poly(chloroalkylene sulfides), polysulfones,poly-chloromethylstyrene, polyisobutylene, polysodium acrylate, polyvinyl alcohol, polyvinyl chloroformate, sulfonated polystyrene block and graft copolymers such as poly(styrene-block-ethylene-co-butylene-block-styrene), poly(1,4-polybutadiene-block ethylene oxide), star chlorine-telechelic polyisobutylene, poly(lsobutylene-co-2,3-dimethy1-1,3-butadiene), poly(styrene-co-N-butylmethacrylate) cellulose, dex-tran and inulin, is described. 

Plasticizers are used in adhesive formulations, above all for elastification of the polymer films in emulsion-based adhesives and also for increasing wet tack. They are used, e.g., in homopolymer emulsion-based adhesives. Phthalate plasticizers are the most widely used, diisobutyl phthalate being especially important for emulsion-based adhesives. In addition to phthalate and adipate plasticizers epo)q and phenol sulfonic amide plasticizers are used in PVC plastisols. Besides ester plasticizers, mineral oils and also chlorinated low molecular mass polyethylenes and low molecular mass hydrocarbon resins are used in rubber adhesives. 

It is used in the production of chlorophenols or in side-chain chlorinations of aromatics, of sulfonic acids and the sulfochlorination of polyethylene. In lithium batteries it acts as liquid cathode. 

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