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公开(公告)号：DK117025B
公开(公告)日：1970-03-09
申请号：DK301965
申请日：1965-06-16
Applicant: STANDARD OIL CO
IPC: C08F220/42 , C08F265/08 , C08J5/18 , C08F47/14 , B29D7/24
Abstract: Solutions of a polymer of at least one a ,b -olefinically unsaturated nitrile monomer and a polyalkenyl monomer in a polar solvent are useful in making films. Preferably the nitrile monomer is acrylonitrile, methacrylonitrile, a -chloroacrylonitrile, crotononitrile or vinylidene cyanide. The polyakenyl monomer preferably contains at least two CH2=C= groups separated by at least one other group, e.g. allyl or methallyl esters of unsaturated carboxylic acids, polyacrylates, -methacrylates or -maleates, divinyl or di(meth)allyl ether, diallyl or triallyl compounds, dienes (non-conjugated), divinyl or trivinyl compounds, diisopropenylbenzene, tetra-allyl or -vinyl compounds, diallyl vinyl silane, tri(meth)acryloyl-perhydrotriazine, bisacrylamides, (meth)allyl-substituted methacrylamide and poly-allyl or -vinyl ethers of polyhydroxy compounds; these monomers are preferably used in proportions of 0.05-5 parts by weight per 100 parts of nitrile monomer. If desired, up to 5 to 15% by weight of the nitrile monomer can be replaced by one or more mono-alkenyl monomers copolymerizable therewith. Preferred solvents include a dimethyl formamide - ethylene carbonate mixture, and nitro-ethane. Also listed are other amides, thio-amides, cyano-amides, methyl pyrrolidone, butyrolactone, tetramethyloxamide, lactams, tetracyanopentane, dimethylcyanamide, N-formyl compounds, sulphones, nitromethane, ethylene cyanohydrin, nitriles, dimethylaminophosphine oxide and tetramethyl-methane-phosphonamide. Instead of the organic solvents, inorganic salt solution systems may be used. Aqueous solutions of (substituted) guanidine thiocyanate are also suitable as solvents. The film-forming polymers may be prepared by batch, bulk, solution or suspension polymerization techniques but preferably are made in an aqueous medium in the presence of a redox catalyst composed of a water-soluble peroxygen compound, e.g. a persulphate, and an oxidizable sulphur compound, e.g. sodium meta-bisulphite, as promoter. A mercaptan may also be present. Preferably the co-polymers are made in two steps, the first step comprising the co-polymerization of a portion of the a ,b -olefinically unsaturated nitrile and all of the polyalkenyl monomer to high conversion, the second step comprising polymerizing (e.g. to 70-100% conversion) the remainder of the nitrile monomer, which may be added all at once or in increments, on to or in the presence of the polymer "seed" thus formed in the first step. Emulsifiers, surface-active agents or dispersing agents may be used throughout both the seed step and the main polymerization step. Examples illustrate solutions, and preparation, of copolymers of acrylonitrile with butanediol divinyl ether, tetramethylene diacrylate or divinyl benzene, and a copolymer of methacrylonitrile with tetramethylene diacrylate.
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公开(公告)号：ZA7603432B
公开(公告)日：1977-05-25
申请号：ZA7603432
申请日：1976-06-09
Applicant: STANDARD OIL CO OHIO
CPC classification number: B29C47/92 , B29C47/0023 , B29C47/0026 , B29C47/20 , B29C47/22 , B29C47/28 , B29C47/86 , B29C47/862 , B29C2947/92209 , B29C2947/92409 , B29C2947/92704 , B29C2947/92904
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公开(公告)号：SE329720B
公开(公告)日：1970-10-19
申请号：SE799565
申请日：1965-06-16
Applicant: STANDARD OIL CO
IPC: C08F220/42 , C08F265/08 , C08J5/18 , B29D7/24
Abstract: Solutions of a polymer of at least one a ,b -olefinically unsaturated nitrile monomer and a polyalkenyl monomer in a polar solvent are useful in making films. Preferably the nitrile monomer is acrylonitrile, methacrylonitrile, a -chloroacrylonitrile, crotononitrile or vinylidene cyanide. The polyakenyl monomer preferably contains at least two CH2=C= groups separated by at least one other group, e.g. allyl or methallyl esters of unsaturated carboxylic acids, polyacrylates, -methacrylates or -maleates, divinyl or di(meth)allyl ether, diallyl or triallyl compounds, dienes (non-conjugated), divinyl or trivinyl compounds, diisopropenylbenzene, tetra-allyl or -vinyl compounds, diallyl vinyl silane, tri(meth)acryloyl-perhydrotriazine, bisacrylamides, (meth)allyl-substituted methacrylamide and poly-allyl or -vinyl ethers of polyhydroxy compounds; these monomers are preferably used in proportions of 0.05-5 parts by weight per 100 parts of nitrile monomer. If desired, up to 5 to 15% by weight of the nitrile monomer can be replaced by one or more mono-alkenyl monomers copolymerizable therewith. Preferred solvents include a dimethyl formamide - ethylene carbonate mixture, and nitro-ethane. Also listed are other amides, thio-amides, cyano-amides, methyl pyrrolidone, butyrolactone, tetramethyloxamide, lactams, tetracyanopentane, dimethylcyanamide, N-formyl compounds, sulphones, nitromethane, ethylene cyanohydrin, nitriles, dimethylaminophosphine oxide and tetramethyl-methane-phosphonamide. Instead of the organic solvents, inorganic salt solution systems may be used. Aqueous solutions of (substituted) guanidine thiocyanate are also suitable as solvents. The film-forming polymers may be prepared by batch, bulk, solution or suspension polymerization techniques but preferably are made in an aqueous medium in the presence of a redox catalyst composed of a water-soluble peroxygen compound, e.g. a persulphate, and an oxidizable sulphur compound, e.g. sodium meta-bisulphite, as promoter. A mercaptan may also be present. Preferably the co-polymers are made in two steps, the first step comprising the co-polymerization of a portion of the a ,b -olefinically unsaturated nitrile and all of the polyalkenyl monomer to high conversion, the second step comprising polymerizing (e.g. to 70-100% conversion) the remainder of the nitrile monomer, which may be added all at once or in increments, on to or in the presence of the polymer "seed" thus formed in the first step. Emulsifiers, surface-active agents or dispersing agents may be used throughout both the seed step and the main polymerization step. Examples illustrate solutions, and preparation, of copolymers of acrylonitrile with butanediol divinyl ether, tetramethylene diacrylate or divinyl benzene, and a copolymer of methacrylonitrile with tetramethylene diacrylate.
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Patent Agency Ranking
公开(公告)号：ZA764676B
公开(公告)日：1977-07-27
申请号：ZA764676
申请日：1976-08-03
Applicant: STANDARD OIL CO OHIO
IPC: B29C20060101 , B29D20060101 , B29C , B29D
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公开(公告)号：ZA7604676B
公开(公告)日：1977-07-27
申请号：ZA7604676
申请日：1976-08-03
Applicant: STANDARD OIL CO OHIO
IPC: B29C20060101 , B29D20060101 , B29C , B29D
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公开(公告)号：SE311756B
公开(公告)日：1969-06-23
申请号：SE314764
申请日：1964-03-13
Applicant: STANDARD OIL CO OHIO
IPC: C08F22/30 , C08F36/20 , C08F220/42 , C08F265/08 , C08F15/00
Abstract: Copolymers are made by copolymerizing an unsaturated nitrile and a polyalkenyl monomer until substantially all the monomers are converted to monomer, and then polymerizing additional unsaturated nitrile, which may be the same or different from that used in the first step, in the presence of the first-formed copolymer until a final conversion of 70-100% of monomers to polymer is obtained. Nitriles specified are acrylonitrile, methacrylonitrile, chloroacrylonitrile, crotononitrile and vinylidene cyanide. Polyalkenyl monomers specified are acrylic and methacrylic ester of polyhydric alcohols, allyl esters of unsaturated acids, allyl esters of polycarboxylic acids, non-conjugated diolefines, polyunsaturated ethers, polyunsaturated organometallic compounds of silicon, tin and germanium, polyunsaturated aromatic hydrocarbons, methylene-bis-acrylamide, and N-allyl and N-methallyl substituted acrylamides. The polymerization is preferably carried out in an aqueous medium having a pH of 2-8 in the presence of an emulsifier and a redox polymerization. The resulting copolymers may be formed into films from solution in polyacrylonitrile solvents, e.g. dimethylformamide. The examples describe the preparation of copolymers in aqueous media in the presence of a persulphate/metabisulphite catalyst, t-dodecyl mercaptan, and either sodium lauryl sulphate or a phosphate ester as emulsifier, the monomers employed being: (1) acrylonitrile and tetramethylene diacrylate, (2) acrylonitrile, methacrylonitrile and tetramethylene diacrylate, (3) methacrylonitrile and tetramethylene diacrylate, and (6) acrylonitrile with each of ethylene, triethylene and tetraethylene dimethacrylates, divinyl benzene, diallyl maleate, allyl acrylate and divinyl butanediol.
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公开(公告)号：SE330092B
公开(公告)日：1970-11-02
申请号：SE1055166
申请日：1966-08-03
Applicant: STANDARD OIL CO OHIO
Abstract: 1,162,225. Laminated synthetic resin films; seaming non-metallic sheet material. STANDARD OIL CO. 10 Aug., 1966 [11 Aug., 1965], No. 35799/66. Headings B5K and B5N. [Also in Divisions B2 and B8] A method of making a laminate comprises coating a surface of a biaxially orientated acrylonitrile polymer film consisting of an acrylonitrile homopolymer or of a copolymer of acrylonitrile with up to 5% by weight of at least one polyalkenyl monomer with an adhesive comprising (1) a mixture of a hydroxyl-terminated polyester and a polyisocyanate or (2) a blend of a copolymer of vinyl acetate and acrylic acid with a copolymer of ethylene and vinyl acetate, or (3) a polyurethane made by reacting 1: 6-hexamethylene diisocyanate and tolylene diisocyanate with trimethylol propane and a cellulose acetate-butyrate polymer having residual hydroxy groups, applying to the adhesive-coated surface of the acrylonitrile polymer film a film of a polyolefine which consists of a polymer of an alpha-olefine having the structure where R is hydrogen or C 1 to C 6 alkyl group; and bonding the two films together optionally with heat setting and/or curing of the adhesive during the bonding step. Many polyalkenyl monomers are disclosed. Specified polyolefines which may be melt-extruded into contact with the adhesive are the homo- and co-polymers of ethylene and propylene, polybutenes, polypentenes, polyheptenes and polyhexenes. The surfaces of the films may be pretreated, e.g. with a gaseous mixture of BF 3 and an oxidizing agent or an oxidizing agent or by the application thereto of flame or corona discharge prior to bonding. Articles, e.g. packages, may be made by the heat sealing of the polyolefine films and examples the folding and edge heat-sealing of laminates to form pouches. The laminates or the articles may be attached to foam layers or to woven or non-woven fabrics.
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