Polymer reaction chlorosulfonation

Kobayashi et al. reported sulfonation of poly(4-phenoxybenzoyl-1,4-phenylene) (PPBP) with sulfuric acid and compared the data with those of sulfonated PEEK. As reported, the authors employed sulfuric acid for the sulfonation reaction to avoid or at least minimize degradation of the polymer by chlorosulfonic acid or fuming sulfuric acid (Figure 27). 

Methylenebicyclo[2.2.1]hept-2-ene 36, by treatment with a mixture of chlorosulfonic acid and aluminium chloride as catalyst, suffered cationic polymerization to yield the polymer 37 (Equation 15). In this reaction, chlorosulfonic acid or aluminium chloride alone is not an effective catalyst. 

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). 

An example of a sulfite ester made from thionyl chloride is the commercial iasecticide endosulfan [115-29-7]. A stepwise reaction of thionyl chloride with two different alcohols yields the commercial miticide, propaigite [2312-35-8] (189). Thionyl chloride also has appHcations as a co-reactant ia sulfonations and chlorosulfonations. A patent describes the use of thionyl chloride ia the preparation of a key iatermediate, bis(4-chlorophenyl) sulfone [80-07-9] which is used to make a commercial polysulfone engineering thermoplastic (see Polymers CONTAINING SULFUR, POLYSULFONe) (190). The sulfone group is derived from chlorosulfonic acid the thionyl chloride may be considered a co-reactant which removes water (see Sulfolanes and sulfones). 

Unlike most elastomeric polymers, which are made by direct polymerization of monomers or comonomers, chlorosulfonated polyethylene, as the name implies, is made by chemical modification of a preformed thermoplastic polymer. The chlorination and chlorosulfonation reactions are usually carried out simultaneously but may be carried out ia stages. 

The next major bonded phase project was the development of the GBR resin, which stands for modified glucose bonded on both the backbone and the ring of basic PDVB gels. The manufacture of this product was ultimately achieved, as outlined later. The gel is first brominated, which places bromine atoms on both tertiary hydrogens of the PDVB. The brominated gel is then reacted with chlorosulfonic acid, and a specially treated reduced D-glucosamine is coupled to the gel. This process has the potential to covalently bond up to three sugar residues to each available divinylbenzene residue in the PDVB polymer. The exact reaction conditions used are proprietary however, the surface of the finished product is believed to look similar to Figs. 13.11 and 13.12. 

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... 

The most common way to modify aromatic polymers for application as a PEM is to employ electrophilic aromatic sulfonation. Aromatic polymers are easily sulfonated using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or sulfur trioxide (or complexs thereof). Postmodification reactions are usually restricted due to their lack of precise control over the degree and location of functionalization, the possibility of side reactions, or degradation of the polymer backbone. Regardless, this area of PEM synthesis has received much attention and may be the source of emerging products such as sulfonated Victrex poly (ether ether ketone). 

Exercise 29-6 Radical-induced chlorination of polyethene in the presence of sulfur dioxide produces a polymer with many chlorine and a few sulfonyl chlo-- ide (—S02CI) groups, substituted more or less randomly along the chains. Write suitable mechanisms for these substitution reactions. What kind of physical properties would you expect the chlorosulfonated polymer to have if substitution is carried to the point of having one substituent group to every 25 to 100 CH2 groups How may this polymer be cross-linked (A useful product of this general type is marketed under the name of Hypalon.)... 

A technology developed at Du Pont75 combines the use of reactive sites on the oligomers with the initiation reaction. The resulting family of acrylic structural adhesives has become popularly known as second generation acrylics. They consist essentially of solutions of chlorosulfonated polyethylene (Du Pont Hypalon ) in acrylic or methacrylic monomers. The chlorosulfonyl groups present on the polymer will react with... 

Cellulose sulfates are appealing water soluble polymers even at low DS. Cellulose sulfation, however, is complicated by serious chain degradative side reactions. Cellulose sulfation has been carried out using chlorosulfonic acid, sulfuric acid, or sulfur trioxide. At low degrees of substitution (DS 0.2 to 0.3), cellulose sulfates are used in oil well drilling, foodstuffs, cosmetics, and pharmaceuticals. The preparation of cellulose sulfates for symplex capsules can... 

Block polymers can also be chlorosulfonated (accompanied by some chlorination) and in turn hydrolyzed to the sodium salt (Reactions 38 and 39) (76). 

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