Polyethylene chlorosulfonated

Linear polyethylene (high density) was introduced in the late 1950s, with the development of coordination catalysts. Chlorosulfonation of these base resins gave products that were superior to the eadier, low density types in both chemical resistance and mechanical properties and with distinct advantages in mbber processibiUty (6,7). 

Introduction of linear low density polyethylene in the 1970s and 1980s offered yet another design parameter, giving chlorosulfonated products with the advantages of linear types but with improved low temperature performance (8). 

Extension of the chlorosulfonation technology to base resins other than polyethylene, where value can be added, seems a logical next step. Polypropylene and ethylene copolymers containing additional functionaUty, ie, maleic anhydride graft, vinyl acetate, acrylic acid, etc, have been chlorinated and chlorosulfonated to broaden the appHcation base, particularly in coatings and adhesives (9,10). 

The combined worldwide market for this entire family of elastomers had grown to about 48,000 metric tons per year in 1991. 

These values assume chlorination in carbon tetrachloride solution under homogeneous conditions favoring random distribution of chlorine atoms along the chain. Viscous reaction conditions, faster chlorine addition rates, lower temperature conditions, etc, can lead to higher AH at equivalent chlorine levels because of more blocky chlorine distribution on the polymer chain. 

Chlorosulfonated polyethylene, CSP, was developed by Dupont to be used in vulcanized and non-vulcanized products. Unplasticized it is veiy flexible material and as such it is found in mar apphcations where it competes with plasticized PVC. Although plasticizers are not normally used, there are some exceptions. 

Antitack rubber suitable for manufacturing pneumatic tires is produced from combination of CSP and natural rabber. This composition used 3 wt% of an undisclosed plasticizer (process oil). A paper transport belt made from a blend of CSP and EPDM rabber used 3 phr of polyethylene glycol and 25 phr of dioctyl sebacate. A membrane obtained from blending CSP and chlorinated polyethylene contained 6 phr of tri-(2-etltylhexyl) phosphate.  

These cases suggest that the plasticizer may function as a compatibilizer of the polymer blend. In one case, a phosphate plasticizer was selected because it reduced mildew growth in conjunction with a common fungicide (Busan 11). 

Process oil, possibly dioctyl adipate or dioctyl sebacate, has been used in a transmission belt compound. It also produces a softening effect. In application of fluoroplastic additives, Dupont research gave formulation of vulcanized CSP which contained 20 phr of dioctyl sebacate. It is probable that some quantities of plasticizers can be found in CSP formulations, particularly in vulcanized products. 

The information given here for copolymers is much less material specific than it is for homopolymers because copolymers have a wide variety of chemical compositions and stmctures. The information is intended to show the importance of plasticizers in copolymers. Examples given also include some novel polymeric plasticizers that are copolymers themselves. 

Donskoi and co-workers [54] showed that each of the components of a chlorosulfonated polyethylene (CSPE) mix has its own influence on the fireproofing properties and chemical processes that occur. In this case, the thermal properties of the vulcanisates of CSPE were studied, and also the heat flows from the flame on the surface of the specimen. It was established that the thermooxidative breakdown of CSPE and vulcanisates based on it during heating under dynamic conditions, is a multi-stage process. The results of tests involving various fillers and plasticisers made it possible to create rubber-like, high-impact resistant materials. 

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Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

Many cellular plastics that have not reached significant commercial use have been introduced or their manufacture described in Hterature. Examples of such polymers are chlorinated or chlorosulfonated polyethylene, a copolymer of vinyUdene fluoride and hexafluoropropylene, polyamides (4), polytetrafluoroethylene (5), styrene—acrylonitrile copolymers (6,7), polyimides (8), and ethylene—propylene copolymers (9). 

Most elastomers can be made iato either opea-ceUed or closed-ceUed materials. Natural mbber, SBR, nitrile mbber, polychloroprene, chlorosulfonated polyethylene, ethylene—propylene terpolymers, butyl mbbers, and polyacrylates have been successfuUy used (4,111,112). 

The use of TAG as a curing agent continues to grow for polyolefins and olefin copolymer plastics and mbbers. Examples include polyethylene (109), chlorosulfonated polyethylene (110), polypropylene (111), ethylene—vinyl acetate (112), ethylene—propylene copolymer (113), acrylonitrile copolymers (114), and methylstyrene polymers (115). In ethylene—propylene copolymer mbber compositions. TAG has been used for injection molding of fenders (116). Unsaturated elastomers, such as EPDM, cross link with TAG by hydrogen abstraction and addition to double bonds in the presence of peroxyketal catalysts (117) (see Elastol rs, synthetic). 

At this point in the process, thermoplastic and chlorosulfonated polyethylene (CSPE) membranes are complete and are ready for packaging. In the case of ethylene—propylene—diene monomer (EPDM), the curing step occurs before the membrane is ready for packaging. The curing process is accomphshed by placing the membrane in a large vulcanizer where the material is heated under pressure to complete the cure. 

CSPE. Chlorosulfonated polyethylene (CSPE), a synthetic mbber manufactured by DuPont, is marketed under the name Hypalon. It can be produced as a self-curing elastomer designed to cure on the roof. The membrane is typically reinforced with polyester and is available in finished thicknesses of 0.75 to 1.5 mm. Because CSPE exhibits thermoplastic characteristics before it cures, it offers heat-weldable seams. After exposure on the roof, the membrane cures offering the toughness and mechanical set of a thermoset. The normal shelf life of the membrane for maintaining this thermoplastic characteristic is approximately six months. After the membrane is fully cured in the field, conventional adhesives are needed to make repairs. 

Natural mbber comes generally from southeast Asia. Synthetic mbbers are produced from monomers obtained from the cracking and refining of petroleum (qv). The most common monomers are styrene, butadiene, isobutylene, isoprene, ethylene, propylene, and acrylonitrile. There are numerous others for specialty elastomers which include acryUcs, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin, ethylene—acryUc, ethylene octene mbber, ethylene—propylene mbber, fluoroelastomers, polynorbomene, polysulftdes, siUcone, thermoplastic elastomers, urethanes, and ethylene—vinyl acetate. 

NR = natural mbbei SBR = styiene—butadiene mbbei EPDM = ethylene—piopjiene—diene monomer CSM = chlorosulfonated polyethylene and PE = polyethylene. 

Chlorosulfonated Polyethylene. This elastomer is made by the simultaneous chlorination and chlorosulfonation of polyethylene in an inert solvent. The resulting polymer is an odorless, colorless chip that is mixed and processed on conventional mbber equipment. The polymer typically contains 20-40% chlorine and 1% sulfur groups (see ElASTOL RS, SYNTHETIC-Cm OROSULFONATEDPOLYETHYLENE) (8). 

It is estimated that 27,000 t/yr of CSM have been commercially used in the United States. However, due to environmental problems in the manufacturing process, it has been necessary to develop a process that is much mote expensive. As a result many companies using CSM ate trying to replace the CSM with CPE or other elastomers. The result is a decline in the usage of this polymer. Chlorosulfonated polyethylene is sold under the trade name Hypalon (DuPont—Dow Company). 

Meta.1 Oxides. Halogen-containing elastomers such as polychloropreae and chlorosulfonated polyethylene are cross-linked by their reaction with metal oxides, typically ziac oxide. The metal oxide reacts with halogen groups ia the polymer to produce an active iatermediate which then reacts further to produce carbon—carbon cross-links. Ziac chloride is Hberated as a by-product and it serves as an autocatalyst for this reaction. Magnesium oxide is typically used with ZnCl to control the cure rate and minimize premature cross-linking (scorch). 

Isomer mixtures are generally obtained. Chlorosulfonation is used to produce chlorosulfonated polyethylene, a curable thermoplastic. Preformed sulfuryl chloride may also be used. 

Hypalon chlorosulfonated polyethylene good poor poor... 

Ozonc-rcsjstant elastomers which have no unsaturation are an exceUent choice when their physical properties suit the appHcation, for example, polyacrylates, polysulfides, siHcones, polyesters, and chlorosulfonated polyethylene (38). Such polymers are also used where high ozone concentrations are encountered. Elastomers with pendant, but not backbone, unsaturation are likewise ozone-resistant. Elastomers of this type are the ethylene—propylene—diene (EPDM) mbbers, which possess a weathering resistance that is not dependent on environmentally sensitive stabilizers. Other elastomers, such as butyl mbber (HR) with low double-bond content, are fairly resistant to ozone. As unsaturation increases, ozone resistance decreases. Chloroprene mbber (CR) is also quite ozone-resistant. 

Chlorosulfonated polyethylene. Ethylene—acrylic elastomers. Ethylene—propjiene—diene mbber, Eluorocarbon elastomers. 

Prior to butyl mbber, the known natural and synthetic elastomers had reactive sites at every monomer unit. Unlike natural mbber, polychloroprene, and polybutadiene, butyl mbber had widely spaced olefin sites with aHyUc hydrogens. This led to the principle of limited functionahty synthetic elastomers that was later appHed to other synthetic elastomers, eg, chlorosulfonated polyethylene, siUcone mbber, and ethylene—propylene terpolymers. 

These conclusions are further suppo] ted by expected physical properties of dried film of chlorosulfonated polyethylene from the different types of ... 

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