公开(公告)号：US3427183A

公开(公告)日：1969-02-11

申请号：US3427183D

申请日：1965-04-13

Applicant: MONTEDISON SPA

Inventor： PORTOLANI AUGUSTO ,  GIULIO ENZO DI ,  MILANO MARIO

IPC: C08F255/02 ,  C09J151/06 ,  D06M15/28 ,  D06M15/46

CPC classification number: C08F255/02 ,  C08L2666/14 ,  C08L2666/28 ,  C09J151/06 ,  Y10S156/91 ,  C08F222/00

Abstract: Compositions for bonding elastomeric, amorphous, saturated copolymers of ethylene with an alpha-olefin to natural or synthetic fibres or articles made therefrom comprise graft polymers of grafting maleic acid on such copolymers, emulsified with water in the presence of a non-ionic and of an anionic surface-active agent to produce a latex, which is mixed with an aqueous dispersion of a phenolformaldehyde resin and matured. The article may be in the form of fabrics, yarns, cords or other manufactured textile articles, tyres, belt conveyers, drive belts made from, say, cotton, nylon, polyester or cellulose fibres. The copolymer may be ethylene with propylene or butene-1, or those disclosed in Specification 856,736 or 856,737. The grafting may be carried out in the presence of an organic peroxide. The non-ionic surfactant may be a polyoxyethylated alkyl phenol, or polyoxyethylated alcohols of formula R(OCH.R1CHR1)nOH where R is an alkyl group, R1 is hydrogen or an alkyl group, and n is 4 to 10. The anionic surfactant may be sodium lauryl sulphate, a sodium salt of a polyoxyethylated phenol, or sodium or potassium oleate, palmitate or steorate. The latex may be obtained by emulsifying an hydrocarbon solution containing the grafted copolymer with an aqueous solution of the surfactants and removing the hydrocarbon solvent from the emulsion say by distillation. A creaming agent such as carboxymethylcellulose may be present in the emulsion. The phenol formaldehyde resin may be a resorcinol-formaldehyde resin. The matured mixture may be applied by immersion, spreading or friction and the treated article dried under an air current. The vulcanizing agents such as organic peroxides, e.g. alpha, alpha1-bis (tert. butyl-peroxy) diisopropylbenzene may be incorporated in the copolymer, and the applied mix of copolymer and vulcanizing agent may contain free radical acceptors such as sulphur, reinforcing fillers, and other additives such as carbon black. In the examples a square rayon fabric is adhered to ethylene-propylene copolymer for the manufacture of tape.ALSO:An elastomeric, amorphous, saturated copolymer of ethylene with an alpha-olefin is bonded to a natural or synthetic fibre or an article made therefrom by grafting maleic acid on to the copolymer, emulsifying the resulting graft copolymer with water in the presence of a nonionic and of an anionic surface active agent to produce a latex, mixing the resulting latex with an aqueous dispersion of a phenol-formaldehyde resin, maturing the resulting mixture applying the matured mixture on to the natural or synthetic fibre or the article, applying a mixture of the copolymer with a vulcanizing agent on to the natural or synthetic fibre or the article to which the mature mixture has already been applied, and vulcanizing the natural or synthetic fibre or the article. The article may be in the form of fabrics, yarns, cords or other manufactured textile articles, tyres, belt conveyors, drive belts made from say cotton, nylon, polyester or cellulose fibres. The copolymer may be ethylene with propylene or butene-1, or those disclosed in Specification 856736 or 856737. The grafting may be carried out in the presence of an organic peroxide. The non-ionic surfactant may be a polyoxyethylated alkyl phenol, or polyoxyethylated alcohols of formula R(OCH.R\svCHR\sv)n OH where R is an alkyl group, R\sv is hydrogen or an alkyl group, and n is 4 to 10. The anionic surfactant may be sodium lauryl sulphate, a sodium salt of a polyoxyethylated phenol, or sodium or potassium oleate, palmitate or steorate. The latex may be obtained by emulsifying a hydrocarbon solution containing the grafted copolymer with an aqueous solution of the surfactants and removing the hydrocarbon solvent from the emulsion say by distillation. A creaming agent such as carboxymethylcellulose may be present in the emulsion. The phenol formaldehyde resin may be a resorcinol-formaldehyde resin. The matured mixture may be applied by immersion, spreading or friction and the treated article dried under an air current. The vulcanizing agents may be organic peroxides e.g. alpha, alpha\sv - bis (tert. butyl-peroxy) diisopropylbenzene. The applied mix of copolymer and vulcanizing agent may contain free radical acceptors such as sulphur, reinforcing fillers, and other additives such as carbon black. In the examples a square rayon fabric is adhered to ethylene-propylene copolymer for the manufacture of tape.ALSO:An elastomeric, amorphous, saturated copolymer of ethylene with an alpha-olefin is bonded to a natural or synthetic fibre or an article made therefrom by grafting maleic acid on to the copolymer, emulsifying the resulting graft copolymer with water in the presence of a non-ionic and of an anionic surface active agent to produce a latex, mixing the resulting latex with an aqueous dispersion of a phenolformaldehyde resin, maturing the resulting mixture applying the matured mixture on to the natural or synthetic fibre or the article, applying a mixture of the copolymer with a vulcanizing agent on to the natural or synthetic fibre or the article to which the mature mixture has already been applied, and vulcanizing the natural or synthetic fibre or the article. The article may be in the form of fabrics, yarns, cords or other manufactured textile articles, tyres, belt conveyors, drive belts made from say cotton, nylon, polyester or cellulose fibres. The copolymer may be ethylene with propylene or butene-1, those disclosed in Specification 856736 or 856737. The grafting may be carried out in the presence of an organic peroxide. The non-ionic surfactant may be a polyoxyethylated alkyl phenol, or polyoxyethylated alcohols of formula R(OCH.R\svCHR\sv)nOH where R is an alkyl group, R\sv is hydrogen or an alkyl group, and n is 4 to 10. The anionic surfactant may be sodium lauryl sulphate, a sodium salt of a polyoxyethylated phenol, or sodium or potassium oleate, palmitate or stearate. The latex may be obtained by emulsifying a hydrocarbon solution containing the grafted copolymer with an aqueous solution of the surfactants and removing the hydrocarbon solvent from the emulsion say by distillation. A creaming agent such as a carboxymethylcellulose may be present in the emulsion. The phenol formaldehyde resin may be a resorcinolformaldehyde resin. The matured mixture may be applied by immersion, spreading or friction and the treated article dried under an air current. The vulcanizing agents may be organic peroxides, e.g. alpha, alpha\sv-bis(tert. butylperoxy)diisopropylbenzene. The applied mix of copolymer and vulcanizing agent may contain free radical acceptors such as sulphur, reinforcing fillers, and other additives such as carbon black. In the Examples a square rayon fabric is adhered to ethylene-propylene copolymer for the manufacture of tape.

公开(公告)号：US3522120A

公开(公告)日：1970-07-28

申请号：US3522120D

申请日：1966-09-20

Applicant: MONTEDISON SPA

Inventor： GIANDINOTO GIAN VITTORIO ,  MILANO MARIO

IPC: C08J5/06 ,  B29H5/01 ,  B32B27/06

CPC classification number: C08J5/06 ,  C08J2323/02 ,  Y10S156/91 ,  Y10T428/3179

公开(公告)号：US3513057A

公开(公告)日：1970-05-19

申请号：US3513057D

申请日：1964-11-10

Applicant: MONTEDISON SPA

Inventor： FALCONE LUIGI ,  MILANO MARIO

IPC: C08J5/06 ,  C09J123/34 ,  D06M15/227 ,  C09J3/12 ,  C08D13/24

CPC classification number: C08J5/06 ,  C08J2323/02 ,  C08J2323/16 ,  C08L2666/16 ,  C09J123/34 ,  D06M15/227 ,  Y10S156/91 ,  Y10T428/2938 ,  Y10T428/2965 ,  Y10T428/2967 ,  Y10T428/2969 ,  Y10T428/2971 ,  Y10T428/31928 ,  Y10T428/31935 ,  Y10T442/2836 ,  Y10T442/2959

Abstract: A composition used in bonding natural and synthetic fibres to elastomeric saturated amorphous ethylene-alpha-olefine copolymers comprises an aqueous dispersion of a phenolaldehyde resin and of a chlorosulphonated ethylene-alpha-olefine copolymer containing a non-ionic surface active agent and an amonic surface active agent which has been adjusted to a pH of 7-8 after a maturing period of 4-80 hours. The composition may be prepared by mixing while agitating a hydrocarbon solvent solution containing 1-30% by weight of the chlorosulphonated copolymer with a solution in the same volume of water of a mixture of a nonionic surface active agent and an anionic surface active agent, adding a thickening agent, e.g. carboxymethylcellulose, to produce a skimming or enriched emulsion containing 1/2 to 2/3 of the original emulsifiers which is separated from the aqueous layer, separating the solvent from the enriched emulsion by distillation in a current of superheated steam, further concentrating the emulsion by evaporation of water up to a solid content of 20-30% by weight, adding the condensation product of the phenol, e.g. resorcinol, and formaldehyde or the phenol and formaldehyde together with a small amount of alkali to catalyse the condensation, to the emulsion and the adjusting the pH to 7-8 after a maturing period of 40-80 hours. The nonionic surface active agent may be a polyoxyethylated alkyl phenol produced from one mole of an alkyl phenol having an aliphatic chain containing 6-10 carbon atoms or a polyoxyethylated alcohol having the formula R(OCHR1CHR1)nOH in which R is an alkyl group, R1 is a hydrogen atom or alkyl group and n is an integer of 4-10 and the anionic surface active agent may be sodium lauryl sulphate, a sodium salt of a polyoxyethylated phenol sulphate or sodium or potassium oleate, palmitate or stearate. The hydrocarbon solvent for the chlorosulphonated copolymer may be pentane, hexane, heptane, benzene or toluene and boric acid and caustic soda which produce a mixture of boric acid and sodium borate may be added to buffer the composition to a pH of 7-8. The copolymers may be obtained by chlorosulphonating ethylene-alpha-olefine copolymers with gaseous mixtures of SO2 and chlorine, with chlorosulphonic acid or with sulphuryl chloride.ALSO:Natural and synthetic fibres and articles made therefrom, e.g viscose rayon, nylon and cotton fabrics, are bonded to elastomeric saturated amorphous ethylene/alpha-olefin copolymers by treating them with an aqueous dispersion of a phenol-aldehyde resin and of a chlorosulphonated ethylene-alpha-olefin copolymer containing a non-ionic surface active agent and an anionic surface-active agent, the pH of this resin-latex dispersion being adjusted to 7-8 after a maturing period of from 40-80 hours, applying to them a layer of a mix containing an ethylene/alpha olefin copolymer, a reinforcing filler and a vulcanization agent and then vulcanizing by heating to from 110 DEG to 220 DEG C. The treating composition may be prepared by mixing while agitating a hydrocarbon solvent solution containing 1-30% by weight of the chlorosulphonated copolymer with a solution in the same volume of water of a mixture of a non-ionic surface active agent and an anionic surface active agent, adding a thickening agent, e.g. carboxymethylcellulose, to produce a skimming or enriched emulsion containing 1/2 to 2/3 of the original emulsifiers which is separated from the aqueous layer, separating the solvent from the enriched emulsion by distillation in a current of super heated steam, further concentrating the emulsion by evaporation of water up to a solid content of 20-30% by weight, adding the condensation product of the phenol e.g. resorcinol, and formaldehyde or the phenol and formaldehyde together with a small amount of alkali to catalyse the condensation, to the emulsion and then adjusting the pH to 7-8 after a maturing period of 40-80 hours. The non-ionic surface active agent may be a polyoxyethylated alkylphenol produced from one mol of an alkylphenol having an aliphatic chain containing 6-10 carbon atoms or a polyoxyethylated alcohol having the formula R(OCHR\sv CHR\sv)nOH in which R is an alkyl group, R\sv is a hydrogen atom or alkyl group and n is an integer of 4-10 and the anionic surface active agent may be sodium lauryl sulphate, a sodium salt of a polyoxyethylated phenol sulphate or sodium or potassium oleate, palmitate or stearate. The hydrocarbon solvent for the chlorosulphonated copolymer may be pentane, hexane, heptane, benzene or toluene and boric acid and caustic soda which produce a mixture of boric acid and sodium borate may be added to the treating composition to buffer to pH to between 7 and 8. The aqueous dispersion may be applied to the fibres or articles by immersion, spreading or frictioning, dried and the ethylene/alpha olefin copolymer which may contain as vulcanising agents organic peroxides and sulphur, as reinforcing fillers carbon black or mineral fillers, and possibly other additives, applied and vulcanized.ALSO:Fabrics made from natural or synthetic fibres, e.g. viscose rayon, nylon and cotton, are bonded to elastomeric saturated amorphous ethylene/alpha-olefin copolymers by treating them with an aqueous dispersion of a phenolaldehyde resin and of a chlorosulphonated ehtylene-alpha-olefin copolymer containing a non-ionic surface active agent and an anionic surface-active agent, the pH of this resin-latex dispersion being adjusted to 7-8 after a maturing period of from 40-80 hours, applying to them a layer of a mix containing an ethylene/alpha olefin copolymer, a reinforcing filler and a vulcanization agent and then vulcanizing by heating to from 110 DEG to 220 DEG C. The treating composition may be prepared by mixing while agitating a hydrocarbon solvent solution containing 1-30% by weight of the chlorosulphonated copolymer with a solution in the same volume of water of a mixture of a non-ionic surface active agent and an anionic surface active agent, adding a thickening agent, e.g. carboxymethylcellulose, to produce a skimming or enriched emulsion containing 1/2 to 2/3 of the original emulsifiers which is separated from the aqueous layer, separating the solvent from the enriched emulsion by distillation in a current of super heated steam, further concentrating the emulsion by evaporation of water up to a solid content of 20-30% by weight, adding the condensation product of the phenol e.g. resorcinol and formaldehyde or, the phenol and formaldehyde together with a small amount of alkali to catalyse the condensation, to the emulsion and then adjusting the pH to 7-8 after a maturing period of 40-80 hours. The non-ionic surface active agent may be a polyoxyethylated alkylphenol produced from one mol of an alkylphenol having an aliphatic chain containing 6-10 carbon atoms or a polyoxyethylated alcohol having the formula R(OCHR'CHR')nOH in which R is an alkyl group, R' is a hydrogen atom or alkyl group and n is an integer of 4-10 and the anionic surface active agent may be sodium lauryl sulphate, a sodium salt of a polyoxyethylated phenol sulphate or sodium or potassium oleate, palmitate or stearate. The hydrocarbon solvent for the chlorosulphonated copolymer may be pentane, hexane, heptane, benzene or toluene and boric acid and caustic soda which produce a mixture of boric acid and sodium borate may be added to the treating composition to buffer to pH to between 7 and 8. The aqueous dispersion may be applied to the fabrics by immersion, spreading or frictioning, dried and the ethylene/alpha olefin copolymer which may contain as vulcanising agents organic peroxides and sulphur, as reinforcing fillers carbon black or mineral fillers, and possibly other additives applied and vulcanized.