GB851936A - Improvements in or relating to polymeric products - Google Patents
Improvements in or relating to polymeric productsInfo
- Publication number
- GB851936A GB851936A GB22709/57A GB2270957A GB851936A GB 851936 A GB851936 A GB 851936A GB 22709/57 A GB22709/57 A GB 22709/57A GB 2270957 A GB2270957 A GB 2270957A GB 851936 A GB851936 A GB 851936A
- Authority
- GB
- United Kingdom
- Prior art keywords
- diisocyanate
- phenylene
- organic
- phospholine
- isocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/833—Chemically modified polymers by nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
Abstract
The invention comprises, as new substances, polymeric compounds of molecular weight at least 750 consisting essentially of more than two structural units of formula -R-N=C=N-(in which R is an organic bivalent or polyvalent radical) and obtainable by the intermolecular condensation of more than two molecules of organic di and poly-isocyanates with the elimination of carbon dioxide. Such compounds are obtained by contacting an organic di- or polyisocyanate with a catalyst consisting of a substituted phospholine of the formula: <FORM:0851936/IV(a)/1> or a substituted phospholidine of formula: <FORM:0851936/IV(a)/2> wherein R is lower alkyl and phenyl radical, R1 is a hydrogen atom or a lower alkyl or lower alkenyl radical, a, b, c and d each represent a hydrogen or halogen atom or a lower alkyl, lower alkenyl, phenyl or cyclohexyl group or represent polymethylene groups which, together with two adjacent carbon atoms in the heterocyclic ring, form a cyclo-aliphatic ring, and X is an oxygen or sulphur atom. The reaction may be effected in a solvent such as benzene, toluene, xylene, decahydronaphthalene, acetonitrile, nitromethane, 2-nitropropane, N-nitrosodimethylamine, methyl amyl ketone or anisole, at temperatures up to 300 DEG C. and preferably at 100 DEG -200 DEG C. As polyisocyanates there can be used tolylene, phenylene, methylene di (p-phenylene), 4,-chloro-1, 3-phenylene, 4, 41-biphenylene, 1, 5-naphthylene, polymethylene, 3, 31-dimethoxy-4, 41-biphenylene, cyclohexylene, 4, 41-methylene dicyclohexylene, 1, 5-tetrahydronaphthalene diisocyanates, m-(1-isocyanatoethyl)-phenyl isocyanate, 2, 4, 6-tri-isocyanato-toluene and pisocyanatophenyl-2, 4-diisocyanotophenyl ether. Mixtures can be used. Also suitable are polymers containing isocyanate groups, such as the reaction products of excess polyisocyanate with polymers containing terminal hydroxy, amino or carboxyl groups. Specified are polyisocyanate reaction products of polyalkylene ether glycols, polyalkylenearylene ether glycols, polyalkylene ether-thioether glycols, polyalkylene arylene ether thioether glycols, polyester glycols and polyhydrocarbon glycols. A reaction product of 3 mols of a diisocyanate with one mol of castor oil or one mol of a polyester of trimethylol propane, polytetramethylene ether glycol and adipic acid or of 4, 41-isopropylidene-diphenol with excess methylene di (p-phenylene) diisocyanate can also be used) The products can be formed as foams or elastomers (fibres, films, sheets) or be formed into coating compositions. The products, if linear, can be used with peroxides such as dicumyl or benzoyl peroxide. Polymers having -CH=CH2 terminated side chains (obtained from a mixture of an isocyanate-terminated reaction p product of diisocyanate and polyalkylene ether glycol and isocyanate-terminated reaction product of a glycol containing a side chain unsaturated group) can be cured with sulphur. The products can also be reacted with ammonia or mono amines to give a linear polymer containing a plurality of guanidine linkages or with a diamine to give a cross-linked product containing guanidine linkages. The guanidine polymers are suitable for making films and fibres. The polymers can be compounded with carbon black, clay, silica, talc, zinc and magnesium oxides, calcium and magnesium carbonate, titanium dioxide, plasticisers and organic and inorganic colouring agents. In typical Examples (1) 2, 4-tolylene diisocyanate is heated at 100 DEG C. with 3-methyl-1-phenyl-3-phospholine. The poly (2, 4-tolylenecarbodiimide) produced is moulded at 250 DEG -300 DEG C. 5-tert-butyl-2-methyl-1, 3-phenylene diisocyanate, 4, 41-oxydiphenylene diisocyanate, 2, 4, 6-trimethyl-1, 3-phenylene diisocyanate and durylene diisocyanate may be polymerized similarly; (12) polytetramethylene ether glycol is reacted with 2, 4-tolylene diisocyanate in a 2 : 1 molar ratio and the hydroxy-terminated polymer obtained is reacted with excess methylene-di (p-phenylene) diisocyanate. The product is (A) heated in xylene with 3-methyl-1-phenyl-3-phospholine to give a spinnable solution of polymer; (B) mixed with methylene di (p-phenylene) diisocyanate and heated with 1-ethyl-3-methyl-phospholine 1-oxide to give a polymer; or (C) the solution of polymer used in spinning in (A) is wet spun into a precipitating bath of bis (4-aminocyclohexyl) methane in hexane, cross-linking taking place by reaction of the carbodiimide linkages with the amine to form guanidine groups; (25) a mixture of isocyanate terminated polymers from 2, 4-tolylene diisocyanate and polytetramethylene glycol and 3-allyloxy-1, 2-propanedial, respectively is heated with 3-methyl-1-phenyl-3-phospholine 1-oxide. The product containing carbodiimide linkages and side chain allyloxymethyl groups is compounded with carbon black, 2, 21-dithiobisbenzothiazole, mercaptobenzthiazole, sulphur and zinc p-methoxydithiocarbamlate and moulded under heat and pressure; (27) a poly (2, 4-tolylenecarbodiimide) solution is poured into (A) aniline solution; (B) tert butylamine solution. The polyguanidine product of (B) is purified by solution in dilute hydrochloric acid and precipitation by ammonia and dissolved in dilute sulphuric acid to give a poly (guanidinium sulphate) solution. Specification 797,863 is referred to.ALSO:The invention comprises, as new substances, polymeric compounds (which may be cellular) of molecular weight at least 750 consisting essentially of more than two structural units of the formula-R-N=C=N-(in which R is an organic bivalent or polyvalent radical) and obtainable by the intermolecular condensation of more than two molecules of organic di-and polyisocyanates with the elimination of carbon dioxide. Such compounds are obtained by contacting an organic di-or poly-isocyanate with a catalyst consisting of a substituted phospholine of the formula <FORM:0851936/V/1> and <FORM:0851936/V/2> or a substituted phospholidine of formula <FORM:0851936/V/3> and <FORM:0851936/V/4> Included in di- and polyisoyanates are reaction products of polyisocyanates with polyethers and polyesters. The products can be reacted with ammonia or amines to give polymers containing guanidine linkages or can be cured with peroxides or (where CH=CH2 groups are present) with sulphur. Specification 797,863 is referred to.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US851936XA | 1956-07-30 | 1956-07-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB851936A true GB851936A (en) | 1960-10-19 |
Family
ID=22190057
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB22709/57A Expired GB851936A (en) | 1956-07-30 | 1957-07-17 | Improvements in or relating to polymeric products |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB851936A (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0121083A1 (en) * | 1983-02-24 | 1984-10-10 | Union Carbide Corporation | Low-temperature crosslinking of water-borne resins |
US4977219A (en) * | 1983-02-24 | 1990-12-11 | Union Carbide Chemicals And Plastics Company, Inc. | Low temperature crosslinking of water-borne resins |
US5498747A (en) * | 1994-05-12 | 1996-03-12 | Basf Aktiengesellschaft | Carbodiimides and/or oligomeric polycarbodiimides based on 1,3-bis (1-methyl-1-isocyanatoethyl)benzene, their preparation, and their use as hydrolysis stabilizers |
US5597942A (en) * | 1993-06-08 | 1997-01-28 | Basf Aktiengesellschaft | Carbodiimides and/or oligomeric polycarbodiimides based on 1 3-bis (1-methyl-1-isocyanatoethyl) benzene their use as hydrolysis stabilizers |
EP1445269A1 (en) * | 2003-02-10 | 2004-08-11 | Nitto Denko Corporation | Polycarbodiimide having high index of refraction and production method thereof |
EP1598383A1 (en) * | 2004-05-21 | 2005-11-23 | Nisshinbo Industries, Inc. | Thermosetting polycarbodiimide copolymer |
US7049001B2 (en) | 2000-01-11 | 2006-05-23 | Basf Aktiengesellschaft | Carbodiimides with carboxyl or carboxylate groups |
US7722965B2 (en) | 2003-12-26 | 2010-05-25 | Nitto Denko Corporation | Electroluminescence device, planar light source and display using the same |
US8076445B2 (en) | 2000-01-11 | 2011-12-13 | Robert Shane Porzio | Oligocarbodiimides for the formation of crosslinked latex films |
EP3945110A1 (en) | 2020-07-30 | 2022-02-02 | Clariant International Ltd | Flame retardant stabilizer combinations for flame-resistant polymers having improved resistance to hydrolysis and their use |
-
1957
- 1957-07-17 GB GB22709/57A patent/GB851936A/en not_active Expired
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4977219A (en) * | 1983-02-24 | 1990-12-11 | Union Carbide Chemicals And Plastics Company, Inc. | Low temperature crosslinking of water-borne resins |
EP0121083A1 (en) * | 1983-02-24 | 1984-10-10 | Union Carbide Corporation | Low-temperature crosslinking of water-borne resins |
US5597942A (en) * | 1993-06-08 | 1997-01-28 | Basf Aktiengesellschaft | Carbodiimides and/or oligomeric polycarbodiimides based on 1 3-bis (1-methyl-1-isocyanatoethyl) benzene their use as hydrolysis stabilizers |
US5498747A (en) * | 1994-05-12 | 1996-03-12 | Basf Aktiengesellschaft | Carbodiimides and/or oligomeric polycarbodiimides based on 1,3-bis (1-methyl-1-isocyanatoethyl)benzene, their preparation, and their use as hydrolysis stabilizers |
US5504241A (en) * | 1994-05-12 | 1996-04-02 | Basf Aktiengesellschaft | Carbodiimides and/or oligomeric polycarbodiimides based on 1,3-bis(1-methyl-1-isocyanatoethyl)benzene, their preparation, and their use as hydrolysis stabilizers |
US7049001B2 (en) | 2000-01-11 | 2006-05-23 | Basf Aktiengesellschaft | Carbodiimides with carboxyl or carboxylate groups |
US8076445B2 (en) | 2000-01-11 | 2011-12-13 | Robert Shane Porzio | Oligocarbodiimides for the formation of crosslinked latex films |
EP1445269A1 (en) * | 2003-02-10 | 2004-08-11 | Nitto Denko Corporation | Polycarbodiimide having high index of refraction and production method thereof |
US7722965B2 (en) | 2003-12-26 | 2010-05-25 | Nitto Denko Corporation | Electroluminescence device, planar light source and display using the same |
EP1598383A1 (en) * | 2004-05-21 | 2005-11-23 | Nisshinbo Industries, Inc. | Thermosetting polycarbodiimide copolymer |
CN100575378C (en) * | 2004-05-21 | 2009-12-30 | 日清纺织株式会社 | Thermosetting polycarbodiimide copolymer |
US7253246B2 (en) | 2004-05-21 | 2007-08-07 | Nisshinbo Industries, Inc. | Thermosetting polycarbodiimide copolymer |
EP3945110A1 (en) | 2020-07-30 | 2022-02-02 | Clariant International Ltd | Flame retardant stabilizer combinations for flame-resistant polymers having improved resistance to hydrolysis and their use |
WO2022023064A1 (en) | 2020-07-30 | 2022-02-03 | Clariant International Ltd | Flame retardant-stabilizer combinations for flame-retardant polymers having improved hydrolysis stability and use thereof |
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