Anhydride-Styrene Copolymer Patents

Preparation procedure PRODUCTION PROCEDURE United States 2,286,062 1942 DuPont 

Production procedures United States 2,345,013 1944 Socony-Vacuum Oil 

Preparation procedure United States 2,606,891 1952 Rohm Haas 

Preparation procedure United States 3,085,994 1963 Sinclair Research 

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A.2. Maleic Anhydride-Styrene Copolymer Patents A.3. Olefin-MA Copolymer Patents... 

Carboxylic elastomers have also been prepared by the addition of a carboxyl-bearing molecule such as thioglycollie acid, maleic anhydride, or acrylic acid to rubber in solvent, on the mill, or in latex. The preparation of a carboxylic polymer from a butadiene-acrylonitrile copolymer in an internal or Banbury mixer has been mentioned in the adhesives patent literature. The carboxylation of vulcanized natural rubber and of butadiene-styrene copolymers, including reclaimed stocks of these elastomers, by treatment with maleic an-... 

A variety of trichloroethylene copolymers have been reported, none with apparent commercial significance. The alternating copolymer with vinyl acetate has been patented as an adhesive (11) and as a flame retardant (12,13). Copolymerization with 1,3-butadiene and its homologues has been reported (14—16). Other comonomers include acrylonitrile (17), isobutyl vinyl ether (18), maleic anhydride (19), and styrene (20). 

P. Schilling. Polyamine condensates of styrene-maleic anhydride copolymers as corrosion inhibitors. Patent US 5391636,1995. 

Attempts have been made over time to improve the physical properties of novolacs. The use of phenol formaldehyde resins prepared in alkaline medium in photoresist compositions is mentioned in a Kalle Co. AG patent. The use of polyvinyl ethers in combination with novolacs to impart stickiness and plasticization action to the latter was patented by Christensen. Steinhoff, Isaacson, and Roelants of the Shipley Company mention the use of vinyl ethers in a patent on roller coating. Lower alkyl polyvinyl ethers, such as methyl, ethyl, butyl, and isobutyl, are added to novolac resins to improve coating flexibility and adhesion to metal surfaces as well as to improve resistance to mildly alkaline solutions. The use of styrene, methyl styrene, and styrene-maleic anhydride copolymers in combination with novolac was mentioned in several patents of both Shipley and Kalle Co. AG. When novolac is copolymerized with maleic anhydride, a resin that is readily soluble in alkaline solutions is obtained. ... 

Limited information exists in the literature, however, on the homo- or copolymerization of vinyl ethylene carbonate, 1 (VEC or 4-ethenyl-l,3-dioxolane-2-one) for the preparation of cyclic carbonate functional polymers. A few comments regarding polymerization of VEC are given in an early patent [9], In the only reported study of the copolymerization behavior of VEC, Asahara, Seno, and Imai described the copolymerization of VEC with vinyl acetate, styrene, and maleic anhydride and determined reactivity ratios [10. Their results indicated that VEC would copolymerize well with vinyl acetate, but in copolymerizations with styrene, little VEC could be incorporated into the copolymer. VEC appeared to copolymerize with maleic anhydride, however the compositions of the copolymers was not reported. Our goal was to further explore the use of VEC in the synthesis of cyclic carbonate functional polymers. 

In a sense, the styrene-butadiene block copolymers, SB or SBS, (first reported in 1956) constituted the next stage of PS modification. The triblock styrene-diene thermoplastic elastomers were patented in 1962, and soon incorporated in blends with PS, PP, LDPE, HDPE, PPE, PET, PBT, or PC, either as impact modifiers or compatibilizers [Bull and Holden, 1977]. In the 1977-78 patents (applications in 1976) it was disclosed that selective hydrogenation of these copolymers leads to new materials, with properties particularly attractive for polymer blends. For example, blending hydrogenated-SBS, or SEES, generated phase co-continuity in blends with PP, PA, PC, PBT, PES, etc. [Gergen et al., 1987]. More recent modification of these copolymers involved incorporation of acidic or acid-anhydride moieties. 

A Monsanto patent by Lavengood [38] reported on the free radical copolymerization of styrene (S), acrylonitrile (AN) and maleic anhydride (MA) and the use of these terpolymers in the reactive compatibilization of PA6/ABS blends. Indeed, the amine end groups of nylon react with the MA groups of the terpolymer with formation of a graft copolymer at the interface. 

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