GB1577605A

GB1577605A – Polyethylene terephthalates which crystallise rapidly and a process for their preparation
– Google Patents

GB1577605A – Polyethylene terephthalates which crystallise rapidly and a process for their preparation
– Google Patents
Polyethylene terephthalates which crystallise rapidly and a process for their preparation

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Publication number
GB1577605A

GB1577605A
GB5451/78A
GB545178A
GB1577605A
GB 1577605 A
GB1577605 A
GB 1577605A
GB 5451/78 A
GB5451/78 A
GB 5451/78A
GB 545178 A
GB545178 A
GB 545178A
GB 1577605 A
GB1577605 A
GB 1577605A
Authority
GB
United Kingdom
Prior art keywords
diol
acid
polyethylene terephthalate
copolyesters
mol
Prior art date
1977-02-14
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
GB5451/78A
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.)

Bayer AG

Original Assignee
Bayer AG
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.)
1977-02-14
Filing date
1978-02-10
Publication date
1980-10-29

1978-02-10
Application filed by Bayer AG
filed
Critical
Bayer AG

1980-10-29
Publication of GB1577605A
publication
Critical
patent/GB1577605A/en

Status
Expired
legal-status
Critical
Current

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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

C08G63/78—Preparation processes

C08G63/80—Solid-state polycondensation

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

C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds

C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds

C08G63/16—Dicarboxylic acids and dihydroxy compounds

C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings

C08G63/181—Acids containing aromatic rings

C08G63/183—Terephthalic acids

Description

PATENT SPECIFICATION
( 21) Application No 5451/78 ( 22) Filed 10 Feb 1978 ( 31) Convention Application No 2 706 123 ( 32) Filed 14 Feb 1977 in ( 33) Fed Rep of Germany (DE) ( 44) Complete Specification published 29 Oct 1980 ( 51) INT CL 3 C 08 G 63/76 ( 52) Index at acceptance C 3 R 3 D 13 3 D 2 A 3 D 2 E 3 N 1 3 P 7 C 3 Y B 262 B 263 B 270 B 284 G 220 G 315 G 320 H 255 ( 72) Inventors PETER BIER and RUDOLF BINSACK ( 11) ( 19) ( 54) POLYETHYLENE TEREPHTHALATES WHICH CRYSTALLISE RAPIDLY AND A PROCESS FOR THEIR PREPARATION ( 71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following
statement:-
The present invention relates to a process for the preparation of improved highly crystalline thermoplastic copolyesters which crystallise rapidly and are based on terephthalic acid radicals, ethylene glycol radicals and certain co-diol radicals.
Highly crystalline thermoplastic copolyesters which crystallise rapidly and which are based on terephthalic acid, ethylene glycol and certain co-diols are known DT-OS (German Published Specification) 2,507,674 relates to terephthalic acid copolyesters consisting of at least 90 mol %, relative to the dicarboxylic acid component, of terephthalic acid radicals, 90 to 99 5 mol %, relative to the diol component, of ethylene glycol radicals and 0 5 to 10 mol %, relative to the diol component, of co-diol radicals, characterised in that a) the co-diols employed carry two primary OH groups, b) these two OH groups are separated by 3 or 4 C atoms and c) the co-diols employed are either unsubstituted, monoalkyl-substituted or dialkyl-substituted, the alkyl groups carrying 2 or 3 C atoms and, in the case of substitution, the sum of the C atoms of the alkyl substituents being at least 4.
DT-OS (German Published Specification) 2,507,776 relates to terephthalic acid copolyesters consisting of at least 90 mol %, relative to the dicarboxylic acid component, of terephthalic acid radicals, 90 to 99 5 mol %, relative to the diol component, of ethylene glycol radicals and 0 5 to 10 mol % relative to the diol component, of co-diol radicals,, characterised in that a) the co-diols employed carry at least one secondary or tertiary OH group, b) the co-diols employed contain 4 to 10 C atoms and c) the two OH groups are separated by 3 to 4 C atoms.
These copolyesters can be moulded at mould temperatures between 110 and C, preferably at about i 200 C, and, under these conditions, permit a substantially shortened injection moulding cycle time, compared with conventional polyethylene terephthalates.
The copolyesters according to DT-OS (German Published Specification) 2,507,674 and 2,507,776 can be prepared in a manner which is in itself known by esterifying or transesterifying the dicarboxylic acids, preferably terephthalic acid alone, and/or the corresponding dimethyl esters with 1 05 to 2 4, preferably 1 1 to 1 4, mols of the diols, relative to I mol of the dicarboxylic acid component, in the presence of esterification and/or transesterification catalysts between 150 and 250 C (reaction step A) and subjecting the reaction products thus obtained to a polycondensation reaction under customary conditions, that is to say in the presence of esterification catalysts between 200 and 300 C under reduced pressure (< 1 mm Hg) (reaction step B). A particularly preferred embodiment consists in admixing the co-diols to the reaction mixture as late as possible, that is to say only after the reaction mixture of terephthalic acid, or of its ester-forming derivatives, with ethylene glycol to give bis( 2-hydroxyethyl) terephthalate has taken place, or, even more advantageously, only after a polyethylene terephthalate prepolymer which has a degree of polycondensation of more than 4 has formed Thereafter, the mixture can be subjected to a polycondensation reaction in the customary manner, as described above. It has now been found that copolyesters irn Le r-: 1 577 605 1,577,605 with very excellent crystallisation characteristics are obtained when the codiols are only incorporated into the molten homo(polyethylene terephthalate) when this has reached an intrinsic viscosity of at least 0.2 dl/g. The invention thus relates to a process for the preparation of improved highly crystalline thermoplastic copolyesters which crystallise rapidly and have an intrinsic viscosity of at least 0 4 dl/g and which consist of terephthalic acid, and optionally up to 10 mol %, relative to the terephthalic acid, of other dicarboxylic acids, as well as ethylene glycol and a codiol which is a C 3 to C 1 o branched or unbranched aliphatic diol in which the hydroxyl groups are separated by 3 or 4 C atoms and which (I) has at least one secondary or tertiary hydroxyl group or ( 2) carries two primary hydroxyl groups and is unsubstituted, monoalky 1-substituted or dialkyl-substituted, the sum of the C atoms of the substituents being at least 4, in the presence of trans-esterification catalysts, characterised in that 100 parts by weight of polyethylene terephthalate, which is free from co-diol radicals and has an intrinsic viscosity of at least 0 2 dl/g, and 0 23 to 9 1 parts by weight of co-diol are mixed, the mixture is homogenised in the melt and the solidified product is subjected to a solid phase post-condensation reaction. The invention further relates to copolyesters obtainable by this process. In each case, the intrinsic viscosity is measured at 25 C as a 0 5 %' strength by weight solution in a phenol/tetrachloroethane mixture (weight ratio 1:1). Examples of co-diols which correspond to the above conditions are 2-ethylhexane-l,3diol; 3-methylpentane-2,4-diol; 2methylpentane-2,4-diol; 2,2,4trimethylpentane-1,3-diol; 2,2diethylpropane I,3-diol; butane 1,4-diol; hexane-2,5-diol; propane-l,3-diol and butane-l,3-diol The positive action of the co-diol radicals on the rate of crystallisation of the polycondensates produced according to the process of the invention increases in the sequence indicated. In addition to terephthalic acid radicals, the polyesters produced according to the process of the invention can contain up to mol %, relative to the acid component, of radicals of other aromatic, aliphatic or cycloaliphatic dicarboxylic acids (or of their dimethyl esters), such as, for example, phthalic acid, isophthalic acid, naphthalene2,6-dicarboxylic acid, diphenyl-4,4 'dicarboxylic acid, adipic acid, sebacic acid or cyclohexanediacetic acid. The copolyesters produced according to the process of the invention crystallise considerably more rapidly than pure polyethylene terephthalate and possess a very high melting point, that is to say they possess a combination of properties which is highly desirable and has not been achieved by the terephthalic acid polyesters known hitherto. They can be moulded at mould temperatures between 110 and 150 C, preferably at about 120 C, and, under these conditions, permit a substantially shorter cycle time than conventional polyethylene terephthalates containing nucleating agents. The rate of crystallisation can be increased even further by the addition of nucleating agents. As a rule, the solid phase postcondensation reaction is carried out by heating the granular product, in the solid phase in vacuo or in a nitrogen stream, to a temperature which is 60-5 C below the melting point of the polymer. The process according to the invention can be carried out discontinuously in appropriate reaction equipment and mixing equipment The continuous procedure on screw machines is a particularly preferred form, the polyethylene terephthalate and co-diol being metered in together, or the codiol being added to the polyethylene terephthalate melt. Compared with the copolyesters according to DT-OS (German Published Specification) 2,507,776 and 2,507,674, the copolyesters prepared in this manner have the additional advantage that they crystallise even more rapidly As a rule, the start of crystallisation is about 4-6 C above the start of crystallisation of comparable copolyesters and 40 to about C above that of polyethylene terephthalate. The high crystallinity of the copolyesters, which ensures hardness, dimensional stability and stability of shape even at relatively high temperatures, is achieved more rapidly, and the mould dwell time in the injection cycle is therefore considerably shortened. Both the transesterification of the polyethylene terephthalate with the co-diol and the solid phase post-condensation reaction are accelerated by esterification catalysts, such as are described, for example, by R E Wilfang in J Polym Sci. 54, 385 ( 1961) They are employed in amounts of 0 001 to 0 2 %o by weight, relative to the dicarboxylic acid component. The catalysts can have already been used for the preparation of the polyethylene terephthalate and still be contained in these. In order to provide protection against thermo-oxidative degradation, the customary amounts, preferably 0 001 to 0.5 % by weight, relative to the non-filled n 1,577,605 and non-reinforced copolyesters, of stabilisers can be added to the copolyesters produced according to the process of the invention Suitable stabilisers are, for example, phenols and phenol derivatives, preferably sterically hindered phenols which contain alkyl substituents with 1 6 C atoms in both the o-positions relative to the phenolic hydroxyl group, amines, preferably secondary arylamines and their derivatives, phosphates and phosphites, preferably their aryl derivatives, quinones, copper salts of organic acids and addition compounds of copper-I halides with phosphites. The copolyesters obtained by the process of the invention can, of course, be reinforced with reinforcing materials. Metals, silicates, carbon and glass, mainly in the form of fibres, fabrics or mats, have proved suitable reinforcing materials Glass fibres are the preferred reinforcing material. In addition, inorganic and organic pigments, dyestuffs, lubricants and release agents, such as zinc stearate and UV absorbers can, of course, be added in the customary amounts if desired. In order to obtain flame-resistant products, 2 to 20 % by weight, relative to the moulding composition, of flameproofing agents which are in themselves known, such as, for example, halogen-containing compounds, elementary phosphorus or phosphorus compounds, phosphorusnitrogen compounds or antimony trioxide, or mixtures of these substances, preferably antimony trioxide, decabromodiphenyl ether and tetrabromobisphenol A polycarbonate, are added. The rate of crystallisation of the copolyesters obtained by the process of the invention can be further increased by the addition of 0 01 to 1 % by weight, relative to the non-filled and non-reinfoced copolyesters, of nucleating agents Suitable nucleating agents are compounds known to those skilled in the art, such as are described, for example, in KunststoffHandbuch (Plastics Handbook), volume VIII, "Polyester" ("Polyesters"), page 701, 1973, Carl Hanser Verlag, Munich. The copolyesters obtained by the process of the invention are excellent starting materials for the production of films and fibres, and preferably for the production of mouldings of all types by injection moulding Examples Examples The samples were characterised by their intrinsic viscosity and the thermodynamic data important for the melting and crystallisation characteristics, such as the fusion enthalpy (A Hm), melting point (Tm) and crystallisation point (To). The sooner the polymer crystallises out, at a constant rate of cooling and under otherwise identical experimental conditions, the higher is the rate of crystallisation; that is to say the supercooling a T = Tm Tc indicates when the rate of crystallisation reaches its maximum under the cooling conditions used. In the examples which follow, the parts given are parts by weight. Examples I to 5. parts of polyethylene terephthalate granules, with an intrinsic viscosity of 0 672 dl/g (measured at 25 C as a O 5 % stength by weight solution in a phenol/tetrachloroethane mixture in the weight ratio 1:1) are intimately mixed together with 0 23-9 1 parts of co-diol in a mixer and the mixture is then melted in a twin-screw extruder and homogenised in the melt at 260 'C The polyester melt is spun off through a water bath and granulated and the granules are subjected to a polycondensation reaction in a tumbler drier at 225 C in a stream of nitrogen. Comparison examples 6-10 5,826 g ( 30 mols) of dimethylterephthalate and 4,104 g ( 66 mols) of ethylene glycol are heated, in the presence of 4 6 g of calcium acetate, at 200 C in a 25 I autoclave for 2 hours, whilst stirring and passing nitrogen over, whereupon methanol distils off After the transesterification has ended, 36 ml of Ge O 2 solution ( 5 % strength by weight in ethylene glycol), 6 g of tris-nonyl phosphite and 13 2 to 524 6 g of co-diol are added The temperature is raised to 210 C and kept at this value for 2 hours Thereafter, the temperature is increased to 250 C in the course of a further hour and at the same time the apparatus is evacuated (< 1 0 mm Hg) Finally, the mixture is stirred for a further 2 hours at 250 C and under a pressure of less than 0 5 mm Hg The polyester melt is then spun off through a water bath and granulated and the granules are subjected to a polycondensation reaction in a tubler drier at 225 C in a stream of nitrogen. Examples 1-5 (Table I 1) described the copolyesters prepared by the process according to the invention The value of the supercooling for these products is about C lower than for the copolyesters prepared according to DT-OS (German Published Specification) 2,507,776 and 2,507,674 (Examples 6-10), that is to say the copolyesters prepared by the process The nature and amount of catalysts corresponds to that which are also contained in Examples 1-5 according to the invention in the polyethylene terephthalate (from its preparation). according to the invention crystallise more rapidly than those according to the state of the art Examples 11 and 12 give the corresponding data for pure polybutylene terephthalate and polyethylene terephthalate. TABLE 1 Co-diol Examples Type Amount 77 l A Hm (mol %) ldl/gl lcal/gl T m l Cl T C l c 1 1 2-Ethylhexane-1,3-diol 0 6 0 79 9 0 250 5 201 49 5 2 Butane-1,4-diol 4 0 78 9 2 257 5 201 5 56 0 3 2,2,4-Trimethylpentane-1,3-diol 5 0 78 9 4 256 200 56 0 4 2-Methylpentane-1,4-diol 5 0 81 9 6 258 201 57 0 3-Methylpentane-2,4-diol 5 0 80 9 0 255 202 53 0 6 2-Ethylhexane-1,3-diol 0 6 0 78 8 8 251 195 56 0 7 Butane-1,4-diol 4 0 77 8 9 256 193 5 62 5 8 2,2,4-Trimethylpentane-1,3-diol 5 0 80 9 0 256 196 60 0 9 2-Methylpentane-1,4-diol 5 0 81 9 2 258 197 61 0 3-Methylpentane-2,4-diol 5 0 81 8 9 255 196 5 58 5 11 Polybutylene terephthalate 0 87 9 2 226 173 53 0 12 Polyethylene terephthalate 0 72 7 8 255 152 103 0 The symbols used in the table have the following meanings: lvl intrinsic viscosity in phenol/tetrachloroethane 1:1, measured in an Ubbelohde capillary viscometer, polymer concentration: 0 5 g/dl, temperature C. A Hm: fusion enthalpy Tm: melting point T: crystallisation point, measured with a DSC 2 (Perkin Elmer) using a sample weight of about 10 mg and a heating and cooling rate of 20 C/minute. T -T m c l Cl t-' -.4 a,n 0 ' O t Jn 1,577,605 Claims (7) WHAT WE CLAIM IS:- I 1 A process for the production of a highly crystalline thermoplastic copolyester which crystallizes rapidly and has an intrinsic viscosity (at 25 C in a 1:1 phenol tetrachloroethane mixture) of at least 0 4 dl/g and which consists of terephthalic acid, and optionally up to 10 mol %, relative to the terephthalic acid, of ancther dicarboxylic acid, as well as ethylene glycol and a co-diol which is a C 3 to C 1 o branched or unbranched aliphatic diol in which the hydroxyl groups are separated by 3 or 4 carbon atoms and which ( 1) carries at least one secondary or tertiary hydroxyl group or ( 2) carries two primary hydroxyl groups and is unsubstituted, monoalkyl-substituted or dialkyl-substituted, the sum of the carbon atoms of the substituents being at least 4, in the presence of a transesterification catalyst, in which 100 parts by weight of a polyethylene terephthalate segment, which is free from co-diol radicals and has an intrinsic viscosity (at 25 C in a 1:1 phenol tetrachloroethane mixture) of at least 0 2 dl/g, and 023 to 9 1 parts by weight of codiol are mixed, the mixture is homogenized in the melt and the solidified product is subjected to a solid phase postcondensation reaction. 2 A process according to Claim 1, in which the co-diol is selected from 2ethylhexane 1,3-diol; 3-methylpentane-2,4diol; 2-methylpentane-2,4-diol; 2,2,4trimethylpentane-1,3-diol; 2,2diethylpropane 1,3-diol; butane-l,4-diol; hexane-2,5-diol; propane-l,3-diol and butane-I,3-diol. 3 A process according to Claim 1, in which the acid component contains up to 10 mol /o of an acid selected from phthalic acid, isophthalic acid, naphthalene-2,6dicarboxylic acid, diphenyl-4,4 'dicarboxylic acid, adipic acid, sebacic acid and cyclohexanediacetic acid. 4 A process according to claim I, when carried out substantially as hereinbefore described in any one of Examples 1 to 5. The process of Claim 1, wherein the polyethylene terephthalate segment is mixed with the co-diol in a screw machine, granules are formed from the machine and subject to a solid state post-condensation treatment by heating to a temperature which is 60-5 C below the melting point of the polymer under streaming nitrogen or reduced pressure. 6 The high crystalline thermoplastic copolyester produced by the process of any of the foregoing claims. 7 A thermoplastic copolyester as claimed in Claim 6, when reinforced by a metal, silicate, carbon or glass in the form of fibers, a fabric or a mat. For the Applicants, CARPMAELS & RANSFORD, Chartered Patent Agents, 43 Bloomsbury Square, London WCIA 2 RA. Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1980. Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained. GB5451/78A 1977-02-14 1978-02-10 Polyethylene terephthalates which crystallise rapidly and a process for their preparation Expired GB1577605A (en) Applications Claiming Priority (1) Application Number Priority Date Filing Date Title DE19772706123 DE2706123A1 (en) 1977-02-14 1977-02-14 FAST CRYSTALLIZING POLYAETHYLENE TEREPHTHALATES AND THE METHOD FOR THEIR PRODUCTION Publications (1) Publication Number Publication Date GB1577605A true GB1577605A (en) 1980-10-29 Family ID=6001111 Family Applications (1) Application Number Title Priority Date Filing Date GB5451/78A Expired GB1577605A (en) 1977-02-14 1978-02-10 Polyethylene terephthalates which crystallise rapidly and a process for their preparation Country Status (6) Country Link US (1) US4314928A (en) JP (1) JPS53101095A (en) DE (1) DE2706123A1 (en) FR (1) FR2380312A1 (en) GB (1) GB1577605A (en) IT (1) IT1104166B (en) Families Citing this family (5) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title DE2715932A1 (en) * 1977-04-09 1978-10-19 Bayer Ag FAST CRYSTALLIZING POLY (AETHYLENE / ALKYLENE) TEREPHTHALATE FR2482971A1 (en) * 1980-05-20 1981-11-27 Rhone Poulenc Ind POLYESTERS FOR FOOD PACKAGES AND PROCESS FOR OBTAINING THEM DE3112123A1 (en) 1981-03-27 1982-10-07 Basf Ag, 6700 Ludwigshafen STORAGE-STABLE DISPERSIONS OF AROMATIC POLYESTERS IN POLYHYDROXYL COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF FOR THE PRODUCTION OF CELLULAR POLYURETHANE AND / OR POLYISOCYANURATE ARTICLES, IF APPLICABLE DE69214686T2 (en) * 1991-02-28 1997-06-05 Agfa Gevaert Nv Process for the production of polyesters with improved thermo-oxidative stability US11111350B2 (en) 2017-10-26 2021-09-07 Wrh Technology, Llc Method for production of low density polyester foam and articles made thereof utilizing low I.V. polyester feedstock Family Cites Families (26) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title DD82803A (en) * BE551439A (en) * 1955-10-07 GB977104A (en) 1960-02-17 1964-12-02 Hoechst Ag Process for the manufacture of linear, aromatic fibre-forming polyesters NL131746C (en) 1960-07-11 DE1153897B (en) * 1960-10-15 1963-09-05 Hoechst Ag Use of mixed polyesters from terephthalic acid and diols for the production of films US3407112A (en) * 1963-04-09 1968-10-22 Du Pont Polyethylene terepthalate film and process of preparation thereof GB1118538A (en) 1965-11-08 1968-07-03 Goodyear Tire & Rubber Electrostatic printing materials containing polyesters CH465876A (en) * 1966-08-22 1968-11-30 Eastman Kodak Co Process for preparing a polyester US3532654A (en) * 1967-05-09 1970-10-06 Staley Mfg Co A E Polymeric composition GB1191499A (en) 1967-09-29 1970-05-13 Ici Ltd Production of Aromatic Polyesters GB1191490A (en) 1967-10-30 1970-05-13 Hydrocarbon Research Inc Hydrogenation of Fats and Oils GB1246448A (en) * 1967-11-27 1971-09-15 Ici Ltd Production of aromatic copolyesters DE1769035A1 (en) * 1968-03-23 1971-10-07 Hoechst Ag Thermoplastic polyester molding compounds DE1770044A1 (en) 1968-03-23 1971-09-23 Hoechst Ag Crystal clear, thermoplastic polyester-based molding compounds and process for their production US3498952A (en) * 1968-10-03 1970-03-03 Goodyear Tire & Rubber Polyester resins from 2-methyl-2-phenyl-1,3-propanediol FR2023326A1 (en) * 1968-10-25 1970-08-21 Huels Chemische Werke Ag DE2023527B2 (en) * 1970-05-14 1973-07-12 Farbwerke Hoechst AG, vormals Meister Lucius & Brüning, 6000 Frankfurt FIBERS AND FEDES MADE OF POLYAETHYLENE TEREPHTHALATE MODIFIED WITH 2.2DIMETHYLPROPANEDIOL-1,3 US3953394A (en) * 1971-11-15 1976-04-27 General Electric Company Polyester alloys and molding compositions containing the same US3926920A (en) * 1973-03-02 1975-12-16 Nat Starch Chem Corp Hot melt adhesive based on low viscosity heat stable copolyesters US3948859A (en) * 1974-06-06 1976-04-06 Eastman Kodak Company Copolyester hot-melt adhesives DE2507776C2 (en) * 1975-02-22 1983-09-22 Bayer Ag, 5090 Leverkusen Rapidly crystallizing poly (ethylene / alkylene) terephthalate US4136089A (en) * 1975-02-22 1979-01-23 Bayer Aktiengesellschaft Molded articles of crystalline poly (ethylene/alkylene) terephthalates which crystallize rapidly DE2507674A1 (en) * 1975-02-22 1976-09-09 Bayer Ag FAST CRYSTALLIZING POLY (AETHYLENE / ALKYLENE) TEREPHTHALATE US4069278A (en) * 1975-04-01 1978-01-17 General Electric Company Process of making a high melt viscosity block co-polyester DE2545720A1 (en) 1975-10-11 1977-04-21 Bayer Ag FAST CRYSTALLIZING BLOCK COPOLYESTER DE2715932A1 (en) * 1977-04-09 1978-10-19 Bayer Ag FAST CRYSTALLIZING POLY (AETHYLENE / ALKYLENE) TEREPHTHALATE 1977 1977-02-14 DE DE19772706123 patent/DE2706123A1/en active Granted 1978 1978-02-10 IT IT47999/78A patent/IT1104166B/en active 1978-02-10 GB GB5451/78A patent/GB1577605A/en not_active Expired 1978-02-13 JP JP1420778A patent/JPS53101095A/en active Granted 1978-02-14 FR FR7804151A patent/FR2380312A1/en active Granted 1980 1980-06-30 US US06/164,458 patent/US4314928A/en not_active Expired - Lifetime Also Published As Publication number Publication date IT7847999D0 (en) 1978-02-10 DE2706123A1 (en) 1978-08-17 DE2706123C2 (en) 1987-09-17 JPS53101095A (en) 1978-09-04 FR2380312B1 (en) 1984-12-14 IT1104166B (en) 1985-10-21 FR2380312A1 (en) 1978-09-08 US4314928A (en) 1982-02-09 JPS6147854B2 (en) 1986-10-21 Similar Documents Publication Publication Date Title CA1076739A (en) 1980-04-29 Poly(ethylene/alkylene) terephthalates which crystallise rapidly US4136089A (en) 1979-01-23 Molded articles of crystalline poly (ethylene/alkylene) terephthalates which crystallize rapidly US8586701B2 (en) 2013-11-19 Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol KR101543043B1 (en) 2015-08-07 2244--13- 14- process for the preparation of copolyesters based on 2244-tetramethyl-13-cyclobutanediol and 14-cyclohexanedimethanol US4086212A (en) 1978-04-25 Poly(ethylene/alkylene) terephthalates which crystallize rapidly US4617368A (en) 1986-10-14 Process for the production of colorless aromatic polyester and polyester carbonates MXPA01012459A (en) 2002-06-04 Low melt viscosity amorphous copolyesters with enhanced glass transition temperatures. US4207230A (en) 1980-06-10 Block copolyesters which crystallize rapidly JP2012512937A (en) 2012-06-07 A miscible blend of terephthalate polyesters containing 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethylcyclobutane-1,3-diol US4381379A (en) 1983-04-26 Polyester containing 2-methyl-1,3-propylene terephthalate units US4123454A (en) 1978-10-31 Thermoplastic copolyesters US3194794A (en) 1965-07-13 Process of preparing polymers of nuclearly polychlorinated aromatic dicarboxylic acids and diamines having at least 4 carbons US4223106A (en) 1980-09-16 Block copolyesters which crystallize rapidly US4314928A (en) 1982-02-09 Polyethylene terephthalates which crystallize rapidly and a process for their preparation US4171421A (en) 1979-10-16 Thermoplastic copolyesters CA1335680C (en) 1995-05-23 Flameproofed polyethylene terephthalate moulding compounds GB1569230A (en) 1980-06-11 Flame retardant compositions comprising block copolyesters of polybutylene terephthalate US4043981A (en) 1977-08-23 Copolyesters derived from ethoxylated 3,5-dibromo-4-hydroxybenzoic acid JPS59179557A (en) 1984-10-12 Aromatic polyester and polyester carbonate and manufacture JP2003012781A (en) 2003-01-15 Polybutylene terephthalate resin and molded article US3997510A (en) 1976-12-14 Flame-resistant, thermoplastic polyesters GB1591836A (en) 1981-06-24 Polyester compositions which crystallise rapidly EP0472366B1 (en) 1996-10-16 Crystalline wholly aromatic polyester, process for its production, resin composition containing it, and articles from the resin composition JP3626589B2 (en) 2005-03-09 Polyester block polymer US4289870A (en) 1981-09-15 2,2',6,6'-Tetramethylbiphenyl-4,4'-diol polyesters Legal Events Date Code Title Description 1981-01-14 PS Patent sealed [section 19, patents act 1949] 1994-10-05 PCNP Patent ceased through non-payment of renewal fee Effective date: 19940210
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