GB588833A - Preparation of linear polyesters - Google Patents
Preparation of linear polyestersInfo
- Publication number
- GB588833A GB588833A GB15948/44A GB1594844A GB588833A GB 588833 A GB588833 A GB 588833A GB 15948/44 A GB15948/44 A GB 15948/44A GB 1594844 A GB1594844 A GB 1594844A GB 588833 A GB588833 A GB 588833A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acid
- polyester
- zinc chloride
- glycol
- stabilized
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
In forming polyesters of high molecular weight (above 5000) and unit chain length of at least 7 from one or more dicarboxylic acids and one or more dihydric alcohols, the reaction is performed at 150-300 DEG C. preferably under reduced pressure in presence of less than .004 gm-mol./kgm. of polyester, of a compound selected from the group consisting of phosphorous acid, its alkyl or aryl esters or inorganic salts, and the alkyl or aryl esters of thio-phosphorous acid, said compound being added initially to the polyester-forming reactants or to a monomeric ester formed therefrom. Suitable dihydric alcohols are ethylene, trimethylene, propylene, butylene, hexylene, octylene, dodecylene, 2,2-dimethyl trimethylene, diethylene, or tetraethylene glycol, the cyclohexanediols, 1,2-di-b -hydroxyethyl benzene, di-b -hydroxyethoxybenzene, 2,2-(di-b -hydroxyethoxyphenyl) propane, xylylene glycols, b -thiodiglycol. The use of branched chain glycols gives polymers free from crystallinity. Suitable dicarboxylic acids are oxalic, succinic, glutaric, a -methyl glutaric, a - ethyl glutaric, adipic, b - methyl adipic, pimelic, suberic, azelaic, sebacic, brassilic, tetradecanedioic, paraphenylene diacetic, phthalic, terephthalic, hexahydroterephthalic, isophthalic, diglycollic, thiodibutyric or diphenic acid or 2,2-dicarbomethoxyphenyl propane. Unsaturated acids, e.g. maleic, fumaric, or dihydromuconic may be used particularly in mixtures. Acid anhydrides may be used, or a salt of the acid may be reacted with a dihalogen compound corresponding with the dihydric alcohol. Suitable stabilizers are triphenyl, tricresyl, tritert.-butylphenyl, trioctylphenyl, trinaphthyl, tri-, di- or mono-phenoxyethyl, tert.-butylphenoxyethyl, trimethyl, triethyl, tributyl, tricapryl, dibutyl, dioctyl, butyl, dodecyl, amyl, dicyclohexyl, benzyl, methylbenzyl, amyl phenyl, glycol, glyceryl, or methyl glyceryl phosphites, phosphorous acid, or inorganic salts thereof. The reaction may be initiated under reflux condenser, if desired with a solvent such as xylene, or high-boiling petroleum solvent to aid removal of water, and continued under reduced pressure. Acidic catalysts and an inert atmosphere may be employed. According to the examples: (1) a polyester from sebacic acid and ethylene glycol in presence of zinc chloride is stabilized with triamyl phosphite and compared with a similar one prepared without its use; (2) is similar to (1) with triphenyl phosphite as stabilizer; (3) a viscous liquid polyester is prepared from succinic acid, maleic anhydride, propylene glycol and ethylene glycol in presence of tricresyl phosphite. Mixed with sulphur and pigments it could be vulcanized to a rubbery solid; (4) is similar to (3), but uses zinc chloride as a catalyst and the initial refluxing is performed in presence of xylene; (5) and (6) are similar to (4); (7) a polyester from phthalic anhydride, sebacic acid, maleic anhydride and ethylene glycol in presence of zinc chloride is stabilized with triphenyl phosphite; (8) a polyester from succinic acid, sebacic acid, fumaric acid, ethylene glycol, and propylene glycol in presence of zinc chloride is stabilized with tricapryl phosphite; (9) a polyester from sebacic acid and 2,2-dimethyl trimethylene glycol in presence of zinc chloride is stabilized with triphenyl phosphite; (10) a polyester from sebacic acid, maleic anhydride, propylene glycol and ethylene glycol in presence of zinc chloride is stabilized with phosphorous acid. The products may be cured with agents such as benzoyl peroxide or butyl hydroperoxide to rubbery-like solids which are suitable for use in engine connections, for gaskets or diaphragms, for flexible tubing and couplings used in hydraulic lines in aircraft. Specifications 510,899 and 588,834 are referred to. The Specification as open to inspection under Sect. 91 includes the use of a trivalent phosphorus compound as the stabilizer and mentions alkylamine phosphites, arylamine phosphites, phosphorus trichloride, phosphorus trioxide, phosphorus bromide, phosphorus sulphide, esters of the form (RO)2PCl or (RO)PCl2, an aliphatic, aromatic, alicyclic or heterocyclic phosphine, including primary, secondary, tertiary or halogen substituted phosphines, phosphinous acid or its derivatives such as RPHO(OH), where R is a hydrocarbon radical. This subject-matter does not appear in the Specification as accepted.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US588833XA | 1943-10-15 | 1943-10-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB588833A true GB588833A (en) | 1947-06-04 |
Family
ID=22019500
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB15948/44A Expired GB588833A (en) | 1943-10-15 | 1944-08-21 | Preparation of linear polyesters |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB588833A (en) |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2612515A (en) * | 1949-10-22 | 1952-09-30 | Standard Oil Dev Co | Use of phosphites in esterification reactions of synthetic alcohols |
US2622071A (en) * | 1951-04-09 | 1952-12-16 | Gen Mills Inc | Esterification process |
US2698239A (en) * | 1951-01-20 | 1954-12-28 | Du Pont | Photographic films |
US2786076A (en) * | 1953-10-27 | 1957-03-19 | William F O'connor | Oxidation of phenanthrene to produce 2, 2'-diphenic acid and its esters |
DE1033898B (en) * | 1952-03-20 | 1958-07-10 | Atlas Powder Co | Process for the production of thermoplastic, powdery, hardenable polyester resins |
DE971836C (en) * | 1950-02-15 | 1959-04-09 | Ciba Geigy | Process for the preparation of p-aminobenzoic acid esters which are effective as infiltration anesthetics |
US2891930A (en) * | 1957-03-25 | 1959-06-23 | Eastman Kodak Co | Fiber-forming polyesters from trans-1, 4-cyclohexanedicarboxylic compounds and 1, 1-cyclohexane dimethanol |
US2921052A (en) * | 1955-08-17 | 1960-01-12 | Eastman Kodak Co | Polyesters of sulfonyldibenzoic acid and gem-dialkyl glycols |
US2938915A (en) * | 1956-01-06 | 1960-05-31 | Ciba Pharm Prod Inc | Production of natural aminoacid aryl esters with phosphorus aryl esters |
US2967854A (en) * | 1957-02-06 | 1961-01-10 | Diamond Alkali Co | P-xylylene diol polyesters |
US2974122A (en) * | 1956-05-18 | 1961-03-07 | British Celanese | Making high linear polyester with magnesium hypophosphite catalyst |
US2976266A (en) * | 1957-10-17 | 1961-03-21 | American Viscose Corp | Film-forming polyesters of bibenzoic acid |
US3010943A (en) * | 1957-01-09 | 1961-11-28 | Pittsburgh Plate Glass Co | Combinations of aryl sulfonic acids and triaryl phosphites as catalysts in preparation of polyesters |
US3010941A (en) * | 1958-08-29 | 1961-11-28 | Union Carbide Corp | Flame-resistant spirobi (meta-dioxane) phenolic compositions |
US3012988A (en) * | 1958-08-29 | 1961-12-12 | Union Carbide Corp | Phosphorus-containing spirobi(meta-dioxane) phenolic resins |
US3039999A (en) * | 1958-04-15 | 1962-06-19 | Celanese Corp | Hypophosphite color-forming inhibitor in polyester condensation |
US3043806A (en) * | 1956-03-20 | 1962-07-10 | Eastman Kodak Co | Linear polyesters from dimethylmalonic acid |
US3043808A (en) * | 1959-05-20 | 1962-07-10 | Eastman Kodak Co | Linear polyesters of dimethylmalonic acid and neopentyl glycol |
US3048564A (en) * | 1957-08-26 | 1962-08-07 | Du Pont | Process for preparing polyethylene terephthalate |
US3153005A (en) * | 1961-08-23 | 1964-10-13 | Westinghouse Electric Corp | Solid elastomeric polyester resinous molding compositions and electrical members insulated therewith |
US3171828A (en) * | 1955-11-23 | 1965-03-02 | Ici Ltd | Process for manufacturing polymeric polymethylene terephthalates |
US3194776A (en) * | 1957-06-03 | 1965-07-13 | Eastman Kodak Co | Polymeric plasticizers of polyesters of dimethylmalonic acid and a glycol |
US3226360A (en) * | 1959-05-12 | 1965-12-28 | Ici Ltd | Process of preparing linear copolyesters of phosphoric acid |
US3240744A (en) * | 1961-10-19 | 1966-03-15 | Pennsalt Chemicals Corp | Use of fusion aids in fluidized bed coating techniques |
US3340083A (en) * | 1963-05-06 | 1967-09-05 | Owens Corning Fiberglass Corp | Glass mat fibers bonded together by a polyester composition |
US3374201A (en) * | 1964-03-13 | 1968-03-19 | Goodyear Tire & Rubber | Polyesters from a mixture of different aromatic dicarboxylic acids |
US3390132A (en) * | 1964-05-27 | 1968-06-25 | Hercules Inc | Polyester resins |
US3421974A (en) * | 1964-09-18 | 1969-01-14 | Goodyear Tire & Rubber | Copolyesters of mixed phthalic acids,acyclic dicarboxylic acids and tetramethylene glycol |
US3423281A (en) * | 1964-03-10 | 1969-01-21 | Goodyear Tire & Rubber | Copolyesters of mixed phthalic acids,aliphatic dicarboxylic acids and tetramethylene glycol |
DE2307088A1 (en) * | 1973-02-14 | 1974-08-22 | Reichhold Albert Chemie Ag | PROCESS FOR THE PRODUCTION OF POLYCONDENSATION PRODUCTS CONTAINING ESTER GROUPS WITH IMPROVED PROPERTIES |
US6013756A (en) * | 1995-05-23 | 2000-01-11 | Karl Fischer Industrieanlagen Gmbh | Process for producing polyesters using titanium-containing catalyst-inhibitor combinations |
-
1944
- 1944-08-21 GB GB15948/44A patent/GB588833A/en not_active Expired
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2612515A (en) * | 1949-10-22 | 1952-09-30 | Standard Oil Dev Co | Use of phosphites in esterification reactions of synthetic alcohols |
DE971836C (en) * | 1950-02-15 | 1959-04-09 | Ciba Geigy | Process for the preparation of p-aminobenzoic acid esters which are effective as infiltration anesthetics |
US2698239A (en) * | 1951-01-20 | 1954-12-28 | Du Pont | Photographic films |
US2622071A (en) * | 1951-04-09 | 1952-12-16 | Gen Mills Inc | Esterification process |
DE1033898B (en) * | 1952-03-20 | 1958-07-10 | Atlas Powder Co | Process for the production of thermoplastic, powdery, hardenable polyester resins |
US2786076A (en) * | 1953-10-27 | 1957-03-19 | William F O'connor | Oxidation of phenanthrene to produce 2, 2'-diphenic acid and its esters |
US2921052A (en) * | 1955-08-17 | 1960-01-12 | Eastman Kodak Co | Polyesters of sulfonyldibenzoic acid and gem-dialkyl glycols |
US3171828A (en) * | 1955-11-23 | 1965-03-02 | Ici Ltd | Process for manufacturing polymeric polymethylene terephthalates |
US2938915A (en) * | 1956-01-06 | 1960-05-31 | Ciba Pharm Prod Inc | Production of natural aminoacid aryl esters with phosphorus aryl esters |
US3043806A (en) * | 1956-03-20 | 1962-07-10 | Eastman Kodak Co | Linear polyesters from dimethylmalonic acid |
US2974122A (en) * | 1956-05-18 | 1961-03-07 | British Celanese | Making high linear polyester with magnesium hypophosphite catalyst |
US3010943A (en) * | 1957-01-09 | 1961-11-28 | Pittsburgh Plate Glass Co | Combinations of aryl sulfonic acids and triaryl phosphites as catalysts in preparation of polyesters |
US2967854A (en) * | 1957-02-06 | 1961-01-10 | Diamond Alkali Co | P-xylylene diol polyesters |
US2891930A (en) * | 1957-03-25 | 1959-06-23 | Eastman Kodak Co | Fiber-forming polyesters from trans-1, 4-cyclohexanedicarboxylic compounds and 1, 1-cyclohexane dimethanol |
US3194776A (en) * | 1957-06-03 | 1965-07-13 | Eastman Kodak Co | Polymeric plasticizers of polyesters of dimethylmalonic acid and a glycol |
US3048564A (en) * | 1957-08-26 | 1962-08-07 | Du Pont | Process for preparing polyethylene terephthalate |
US2976266A (en) * | 1957-10-17 | 1961-03-21 | American Viscose Corp | Film-forming polyesters of bibenzoic acid |
US3039999A (en) * | 1958-04-15 | 1962-06-19 | Celanese Corp | Hypophosphite color-forming inhibitor in polyester condensation |
US3012988A (en) * | 1958-08-29 | 1961-12-12 | Union Carbide Corp | Phosphorus-containing spirobi(meta-dioxane) phenolic resins |
US3010941A (en) * | 1958-08-29 | 1961-11-28 | Union Carbide Corp | Flame-resistant spirobi (meta-dioxane) phenolic compositions |
US3226360A (en) * | 1959-05-12 | 1965-12-28 | Ici Ltd | Process of preparing linear copolyesters of phosphoric acid |
US3043808A (en) * | 1959-05-20 | 1962-07-10 | Eastman Kodak Co | Linear polyesters of dimethylmalonic acid and neopentyl glycol |
US3153005A (en) * | 1961-08-23 | 1964-10-13 | Westinghouse Electric Corp | Solid elastomeric polyester resinous molding compositions and electrical members insulated therewith |
US3240744A (en) * | 1961-10-19 | 1966-03-15 | Pennsalt Chemicals Corp | Use of fusion aids in fluidized bed coating techniques |
US3340083A (en) * | 1963-05-06 | 1967-09-05 | Owens Corning Fiberglass Corp | Glass mat fibers bonded together by a polyester composition |
US3423281A (en) * | 1964-03-10 | 1969-01-21 | Goodyear Tire & Rubber | Copolyesters of mixed phthalic acids,aliphatic dicarboxylic acids and tetramethylene glycol |
US3374201A (en) * | 1964-03-13 | 1968-03-19 | Goodyear Tire & Rubber | Polyesters from a mixture of different aromatic dicarboxylic acids |
US3390132A (en) * | 1964-05-27 | 1968-06-25 | Hercules Inc | Polyester resins |
US3421974A (en) * | 1964-09-18 | 1969-01-14 | Goodyear Tire & Rubber | Copolyesters of mixed phthalic acids,acyclic dicarboxylic acids and tetramethylene glycol |
DE2307088A1 (en) * | 1973-02-14 | 1974-08-22 | Reichhold Albert Chemie Ag | PROCESS FOR THE PRODUCTION OF POLYCONDENSATION PRODUCTS CONTAINING ESTER GROUPS WITH IMPROVED PROPERTIES |
US6013756A (en) * | 1995-05-23 | 2000-01-11 | Karl Fischer Industrieanlagen Gmbh | Process for producing polyesters using titanium-containing catalyst-inhibitor combinations |
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