GB856917A - Improvements in or relating to synthetic polyesters and products formed therefrom - Google Patents

Improvements in or relating to synthetic polyesters and products formed therefrom

Info

Publication number
GB856917A
GB856917A GB19927/58A GB1992758A GB856917A GB 856917 A GB856917 A GB 856917A GB 19927/58 A GB19927/58 A GB 19927/58A GB 1992758 A GB1992758 A GB 1992758A GB 856917 A GB856917 A GB 856917A
Authority
GB
United Kingdom
Prior art keywords
sodium
acid
potassium
lower alkyl
salt
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
Application number
GB19927/58A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of GB856917A publication Critical patent/GB856917A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/20Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen

Abstract

A film- or fibre-forming polyester having improved dye-affinity has a minor proportion of its structural units in the form of organic radicals containing carboxylate, phosphonate or sulphinate groups in the form of free acids or as metal salts, with the proviso that if said groups are only carboxylate groups, some at least of said structural units occur away from the end of the polymer chain. The major proportion of the structural units are preferably derived by reaction between a diester of a dicarboxylic acid and an aliphatic diol or diester of an aromatic diol or by polymerization of an alkyl ester of a monohydroxymonocarboxylic acid. Specified polyesters to be modified are polyethylene terephthalate, polytetramethylene terephthalate, polyethylene hexahydroterephthalate, polyethylene bibenzoate, poly (trans-1, 4-trans hexahydroxylyl) terephthalate, polyhexamethylene adipate, polyethylene sebacate and the polyesterification products of ethyl 4-(b -hydroxyethoxyl)-3-methylbenzoate or methyl p-(2-hydroxyethoxy) benzoate. The metal carboxylate groups may be introduced by including with the polyester forming components a compound of formula: <FORM:0856917/IV(a)/1> where n is a small integer, M is an atomic equivalent of a metal, -R- is an organic radical, -Z- and -Z1- are -O- or <FORM:0856917/IV(a)/2> , and -Y and -Y1 are -lower alkyl, -H or <FORM:0856917/IV(a)/3> lower alkyl; with the proviso that when -Z- or -Z1- is <FORM:0856917/IV(a)/4> , its attached terminal member -Y or -Y1 is lower alkyl, whereas when -Z -or -Z1- is -O-, its attached terminal member -Y or -Y1 is other than lower alkyl; and with the further proviso that when -Z- or -Z1- is -O- and is attached to a carbon atom of an aromatic ring, its attached terminal member -Y or -Y1 is <FORM:0856917/IV(a)/5> -lower alkyl. The metal carboxylate compound may be sodium dimethyl trimesate, lithium desoxycholate, dipotassium diphenyl-2, 4,2 1,41-tetracarboxylate or sodium monomethyl-4-hydroxyazelate. The free carboxyl groups may be p introduced by heating a melt of a linear polyester in which the end groups are predominantly hydroxyl with a dianhydride, e.g. pyromellitic, naphthalene-1, 4, 5, 8-tetracarboxylic, diphenyl-3, 4, 31, 41-tetracarboxylic, butane-1, 2, 3, 4-tetracarboxylic or 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride. The phosphonate groups may be introduced into the polyester by including with the polyester forming components a compound of formula: <FORM:0856917/IV(a)/6> where -Q1 is -OH, -OM or R111-(-Y1)r, Y and Y1 are -OH, <FORM:0856917/IV(a)/7> (lower alkyl) or <FORM:0856917/IV(a)/8> (lower alkyl), -M is one atomic equivalent of a metal, -R11- and -R111- are aliphatic, alicyclic or aromatic non-hetero polyvalent radicals, q is 1 or 2, r is 0 or 1; and the sum of q and r is 1 or 2; with the proviso that when r is zero, -Q is -R111-H and with the further proviso that whenever either of -Y- and -Y1- is joined to -R11- and -R111- by -O-, the carbon of -R11- and -R111- to which such attachment is made is saturated. The phosphonate may be a salt (preferably an alkali or alkaline earth salt) of 3, 5-dicarbomethoxybenzenephosphonic, 4-carbomethoxybenzenephosphonic, hydroxymethylphosphonic, 3-carboethoxypropanephosphonic 10-carboethoxydecane-phosphonic, bis-(hydroxymethyl)-phosphonic, 4-carbomethoxyphenyl-4-tolylphosphonic or phenyl carboethoxymethylphosphonic acid. The sulphinite groups may be introduced into the polyester by including with the polyester forming components a compound of formula: <FORM:0856917/IV(a)/9> where -M is an atomic equivalent of a metal, -R- is an organic radical, - Y is-OH, <FORM:0856917/IV(a)/100> (lower alkyl) or <FORM:0856917/IV(a)/111> (lower alkyl), with the proviso that when -Y is -OH it is attached to a saturated carbon atom, and -Y1 is -H or the same as -Y. The sulphinate may be a salt (preferably an alkali or alkaline earth salt) of 3, 4-dicarbomethoxybenzenesulphinic, m-carboethoxybenzenesulphinic, pcarbomethoxybenzenesulphinic, 2(b -carbomethoxyethyl)-benzene sulphinic, 5-acetoxynaphthalene-1-sulphinic or 6-acetoxynaphthalene-2-sulphinic acid. Polyesters containing free carboxyl, phosphonic or sulphinic groups may be made by treating polyesters containing the corresponding metal salts with hot dilute sulphuric acid. Polyesterification may be effected in the presence of a catalyst (e.g. a titanate ester, a salt of calcium, manganese or lanthanum or antimony oxide), a colour inhibitor (e.g. phosphoric acid or a salt or ester thereof), a pigment or a delusterant (e.g. titanium dioxide or barium carbonate). In examples polyesters were made by reacting (1)-(2) dimethyl terephthalate, ethylene glycol and either potassium dimethyl trimesate or potassium desoxycholate i.e. (HO)2C23H37 COOK; (3) dimethyl terephthalate, butanediol-1:4 and potassium diethyl trimesate; (4) dimethyl hexahydroterephthalate, ethylene glycol and potassium diethyl trimesate; (5) Methyl p-(2-hydroxyethoxy)-benzoate and potassium diethyl trimesate; (6) - (7) Polyethylene terephthalate flake or powder and pyromellitic dianhydride or any other of the previously specified dianhydrides; (8) - (11) dimethyl terephthalate, ethylene glycol and potassium bis-(hydroxymethyl) phosphonate, disodium 4 - carbomethoxybenzenephosphonate, sodium hydrogen 3, 5-dicarbomethoxybenzenephosphonate or disodium 3, 5-dicarbomethoxybenzenephosphonate; (12) dimethyl terephthalate ethylene glycol and sodium 3, 5-dicarbomethoxybenzenesulphinate.ALSO:Salts of carboxylic, phosphonic or sulphinic acids for use as modifying agents for film- or fibre-forming polyesters (see Group IV(a)) are made in examples as follows: (1) Potassium dimethyl trimesate is made by refluxing trimethyl trimesate with potassium hydroxide in the presence of methanol; the sodium salt is similarly prepared and the lead salt is made by treating the potassium salt with lead acetate; (8) Potassium bis-(hydroxymethyl) phosphonate is made by neutralising bis-(hydroxymethyl) phosphonic acid with an equivalent amount of potassium hydroxide; (9) disodium 4 - carbomethoxybenzenephosphonate, 4 - CH3OOCC6H4 P(O) (ONa)2 is made by titrating a solution of 4-carbomethoxy-benzenephosphonic acid in ethanol with sodium hydroxide; (10) Sodium hydrogen 3, 5-dicarbomethoxy-benzenephosphonate, 3, 5-(CH3OOC)2 C6H3P(O) (OONa) OH is made by mixing dimethyl 5-aminoisophthalate with hydrochloric acid and sodium fluoborate, adding sodium nitrate solution, washing and drying the resulting pasty mess, adding dioxane to it, then adding cuprous chloride and phosphorus trichloride and next adding water and evaporating the solvents. The product is dissolved in water, the solution adjusted to pH7 with sodium carbonate, ethanol added, the resulting precipitate filtered and dried, dissolved in warm hydrochloric acid and the solution filtered and cooled to yield 3, 5-dicarbomethoxybenzenephosphonic acid. This is dissolved in methanol and sodium methoxide added to form the desired product; (12) Sodium 3, 5-dicarbomethoxybenzenesulphinate <FORM:0856917/IV(b)/1> is made by heating sodium 3, 5-dicarbomethoxybenzenesulphonate with phosphorus oxychloride to produce 5-chlorosulpho-isophthalyl chloride. This is then added to a solution of sodium bisulphite and sodium hydroxide which is thereafter acidified with sulphuric acid and the product extracted with ether to form 3, 5-dicarboxybenzenesulphinic acid which is then esterified with methanol and the resulting ester treated with sodium carbonate to form the desired product.
GB19927/58A 1957-06-21 1958-06-20 Improvements in or relating to synthetic polyesters and products formed therefrom Expired GB856917A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US856917XA 1957-06-21 1957-06-21

Publications (1)

Publication Number Publication Date
GB856917A true GB856917A (en) 1960-12-21

Family

ID=22193318

Family Applications (1)

Application Number Title Priority Date Filing Date
GB19927/58A Expired GB856917A (en) 1957-06-21 1958-06-20 Improvements in or relating to synthetic polyesters and products formed therefrom

Country Status (1)

Country Link
GB (1) GB856917A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484339A (en) * 1966-05-02 1969-12-16 Eastman Kodak Co Blends of polyesters containing free carboxyl groups and laminate thereof
FR2070782A1 (en) * 1969-12-09 1971-09-17 Snia Viscosa Linear polyesters prepn
FR2362880A1 (en) * 1976-08-23 1978-03-24 Cassella Farbwerke Mainkur Ag BRANCHIFIED POLYESTERS USEABLE AS DYEING ADDICTS
EP0137359A2 (en) * 1983-09-26 1985-04-17 Bayer Ag Polyether esters, their production and their use in the treatment of textiles
US4640887A (en) * 1984-02-09 1987-02-03 Dainippon Ink And Chemicals, Inc. Photosensitive image-forming material comprised of carboxyl groups developable in aqueous alkaline base solutions
CN117431684A (en) * 2023-10-11 2024-01-23 广州汉德新材料股份有限公司 Manufacturing method of water-splashing-preventing ultrathin soft knitted leather fabric

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484339A (en) * 1966-05-02 1969-12-16 Eastman Kodak Co Blends of polyesters containing free carboxyl groups and laminate thereof
FR2070782A1 (en) * 1969-12-09 1971-09-17 Snia Viscosa Linear polyesters prepn
FR2362880A1 (en) * 1976-08-23 1978-03-24 Cassella Farbwerke Mainkur Ag BRANCHIFIED POLYESTERS USEABLE AS DYEING ADDICTS
EP0137359A2 (en) * 1983-09-26 1985-04-17 Bayer Ag Polyether esters, their production and their use in the treatment of textiles
EP0137359A3 (en) * 1983-09-26 1986-08-20 Bayer Ag Polyether esters, their production and their use in the treatment of textiles
US4640887A (en) * 1984-02-09 1987-02-03 Dainippon Ink And Chemicals, Inc. Photosensitive image-forming material comprised of carboxyl groups developable in aqueous alkaline base solutions
CN117431684A (en) * 2023-10-11 2024-01-23 广州汉德新材料股份有限公司 Manufacturing method of water-splashing-preventing ultrathin soft knitted leather fabric

Similar Documents

Publication Publication Date Title
US4127590A (en) Phosphorus-containing compounds
US2720502A (en) Organo-metallic titanium catalysts for the preparation of polyesters
US4157436A (en) Phosphorus-containing polyesters
US2727881A (en) Organo-titanium catalysts for the preparation of polyesters
US4033936A (en) Process for the manufacture of flame retarding linear polyesters
US2819247A (en) Flame-resistant polyester resinous compositions containing combined halogens and phosporus and process of preparation
US2593411A (en) Bis (4-beta-hydroxyalkoxyphenyl) sulfones and polyesters prepared therefrom
US3546180A (en) Polyesters containing disulfonamido compounds having improved dyeing properties
KR970701746A (en) Flame Retardant Polyester Copolymer (FLAME RETARDANT POLYESTER COPOLYMERS)
US4259222A (en) Linear saturated polyesters of phosphoric acid and halogenated diols as flame-retardant additives and coatings
GB981539A (en) Manufacture of light stable high molecular polyesters and/or polyamides
GB856917A (en) Improvements in or relating to synthetic polyesters and products formed therefrom
GB826248A (en) Improvements in or relating to synthetic polyesters and products formed therefrom
US4315847A (en) Linear saturated polyesters of phosphoric acid and halogenated diols as flame-retardant additives and coatings
US3031425A (en) Flame resistant polyester compositions containing antimony
US2720504A (en) Organo-metallic zirconium catalysts for the preparation of polyesters
US4315969A (en) Linear saturated polyesters of phosphoric acid and halogenated diols as flame-retardant additives and coatings
US3010945A (en) Polymerizing vinyl cyclic acetals with cobaltous salts of dicarboxylic acid half-esters
TWI481640B (en) Method for preparing polyester resin
US3624034A (en) Sulfophenoxy malonate compounds and cationic dyeable copolyesters containing same
US3446838A (en) Novel acids and esters derived from halogenated phenols
US3637910A (en) Process for the preparation of fiber-forming aromatic polyesters of low free carboxyl group contents
US2720505A (en) Tetra-alkyl lead catalysts for the preparation of polyesters
US2675411A (en) Bis(4-beta-hydroxyalkoxyphenyl) ketones and process of preparation
US3657193A (en) Polyesters containing dialkyl substituted sulfo-carboxylic acids