US4207230A
Expired / Lapsed
US
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Block copolyesters which crystallize rapidly
Assignee: Bayer AG
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Filing: 1978-02-03
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Granted: 1980-06-10
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Expires: 1998-02-03
Abstract
Abstract The current invention is concerned with block copolyesters of low glass transition temperature segments and ethylene glycol based polyester segments linked together by carboxylic acid ester groups and special diols, and a process for preparing these copolyesters. These copolyesters display molded resin properties similar to polyethylene terephthalate but crystallization behavior similar to polybutylene terephthalate, i.e. they have high strength and superior solvent resistance, but they also crystallize rapidly. They are made by subjecting low glass transition temperature (less than 0° C.) polymers with carboxyl, hydroxyl or reactive ester end groups to esterification or transesterification conditions with ethylene glycol based polyester segments having a minimum intrinsic viscosity of 0.2 dl/g and special diols having four to ten carbon atoms with 3 or 4 carbon atoms between the hydroxyl groups in the presence of appropriate catalysts. In a preferred embodiment, the three components are subject to melt homogenization in an extruder and the solidified extrudate is subject to a solid state polycondensation reaction.
Inventors
- 👤 Peter Bier
- 👤 Rudolf Binsack
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 21:16
CPC Classifications
C; C08; C08G; C08G63/00; C08G63/66; C08G63/668; C08G63/672; C08G63/02; C08G63/12; C08G63/16; C08G63/18; C08G63/181; C08G63/183; Y; Y10; Y10S; Y10S260/00; Y10S260/35
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
272 words
A rapidly crystallizing thermoplastic block copolyester which has an intrinsic viscosity of at least 0.4 dl/g (in 1:1 phenol/tetrachloroethane at 25° C.) and which consists essentially of the following structural units: ##STR3## in each case said structural units are bound into the copolyester chain via ##STR4## wherein R is the carboxyl free residue of an aromatic, cycloaliphatic or aliphatic dicarboxylic acid and at least 90 mol % of R is the residue of terephthalic acid, n is a polymerization degree sufficiently high to give the defined ethylene glycol based polyester segment an intrinsic viscosity of at least about 0.2 dl/g (in 1:1 phenol/tetrachloroethane at 25° C. and 0.5% strength), P is the reactive end group free residue of a polymer having: a glass transition temperature below about 0° C., reactive carboxyl, ester or hydroxyl end groups, and a molecular weight of about 400 to 1,000,000, and D is the hydroxyl residue of a codiol having: 4 to 10 carbon atoms, its hydroxyl groups separated by a 3 or 4 carbon atom branched or unbranched aliphatic residue, and either at least one secondary or tertiary hydroxyl group, or two primary hydroxyl groups on an unsubstituted, monoalkyl substituted or dialkyl substituted residue wherein the substituents, if any, have a total of at least 4 carbon atoms, said copolyester containing about 60 to 95 wt. % of structural units (A) and about 40 to 5 wt. % of structural units (B) based on the total weight of units (A) and (B) and about 10 to 0.5 mol % of structural units (C) based on the total mols of ethylene glycol residues in structural units (A).
Claim 2
Dependent Claim
272 words
A rapidly crystallizing thermoplastic block copolyester which has an intrinsic viscosity of at least 0.4 dl/g (in 1:1 phenol/tetrachloroethane at 25° C.) and which consists essentially of the following structural units: ##STR3## in each case said structural units are bound into the copolyester chain via ##STR4## wherein R is the carboxyl free residue of an aromatic, cycloaliphatic or aliphatic dicarboxylic acid and at least 90 mol % of R is the residue of terephthalic acid, n is a polymerization degree sufficiently high to give the defined ethylene glycol based polyester segment an intrinsic viscosity of at least about 0.2 dl/g (in 1:1 phenol/tetrachloroethane at 25° C. and 0.5% strength), P is the reactive end group free residue of a polymer having: a glass transition temperature below about 0° C., reactive carboxyl, ester or hydroxyl end groups, and a molecular weight of about 400 to 1,000,000, and D is the hydroxyl residue of a codiol having: 4 to 10 carbon atoms, its hydroxyl groups separated by a 3 or 4 carbon atom branched or unbranched aliphatic residue, and either at least one secondary or tertiary hydroxyl group, or two primary hydroxyl groups on an unsubstituted, monoalkyl substituted or dialkyl substituted residue wherein the substituents, if any, have a total of at least 4 carbon atoms, said copolyester containing about 60 to 95 wt. % of structural units (A) and about 40 to 5 wt. % of structural units (B) based on the total weight of units (A) and (B) and about 10 to 0.5 mol % of structural units (C) based on the total mols of ethylene glycol residues in structural units (A).
Claim 3
Dependent Claim
25 words
The block copolyester of claim 1 wherein structural units (A) are derived from ethyleneglycol based polyesters having molecular weights of between about 5,000 and 50,000.
Claim 4
Dependent Claim
50 words
The block copolyester of claim 1 wherein structural units (B) are the residues of either (i) linear or branched polyolefins obtained from 2 to 5 carbon atom olefines, or (ii) poly(alkylene oxide)-w,w'-diols) with molecular weights between about 400 and 100,000 and carbon to oxygen ratios of about 2.0 to 4.5.
Claim 5
Dependent Claim
47 words
The block copolyester of claim 3 wherein structural units (B) are the residues of either (i) polyethylene, or (ii) poly(ethylene oxide)-w,w'-diols with molecular weights between about 2,000 and 25,000, and the structural units (c) are residues of diols having at least one secondary or tertiary hydroxyl group.
Claim 6
Dependent Claim
31 words
The block copolyester of claim 3 wherein structural units (C) are the residues of diols selected from the groups consisting of 3-methyl pentane-2,4-diol; 2-methyl pentane-2,4-diol; 2,2,4 trimethyl pentane-1,3-diol; hexane-2,5-diol; and butane-1,3-diol.
Claim 7
Dependent Claim
18 words
The block copolyester of claim 3 wherein structural units R consist entirely of the residues of terephthalic acid.
Claim 8
Dependent Claim
40 words
The block copolyester of claim 3 wherein up to about 10 mol % of structural units R consist of the residues of dicarboxylic acids selected from the group consisting of C 6-14 aromatic, C 4-8 aliphatic and C 8-12 cycloaliphatic.
Claim 9
Dependent Claim
208 words
A process for the production of rapidly crystallizing thermoplastic block copolymers having intrinsic viscosities of at least about 0.4 dl/g (in 1:1 phenol/tetrachloroethane at 25° C.) comprising (1) mixing (A) about 60 to 95 wt. %, based on the weight of (A) and (B) of a homopolyethylene terephthalate with an intrinsic viscosity of at least about 0.2 dl/g (in 1:1 phenol/tetrachloroethane at 25° C.), with (B) about 40 to 5 wt. %, based on the weight of (A) and (B) of a polymer with reactive carboxyl, ester or hydroxyl end groups and a glass transition temperature of below about 0° C., and (C) about 10 to 0.5 mol %, based on the mols of ethylene glycol residues in (A), of a codiol having 4 to 10 carbon atoms, the OH groups of which are separated by aliphatic branched or unbranched groups of 3 or 4 carbon atoms, said diol having either (i) at least one secondary or tertiary OH group or (ii) two primary OH groups, in which case the diol is unsubstituted, monoalkyl substituted or dialkyl substituted, and the substituents, if any, have a total of at least 4 carbon atoms, 2. homogenizing the mixture in the form of a melt, 3. solidifying the homogenized melt, and
Claim 10
Dependent Claim
208 words
A process for the production of rapidly crystallizing thermoplastic block copolymers having intrinsic viscosities of at least about 0.4 dl/g (in 1:1 phenol/tetrachloroethane at 25° C.) comprising (1) mixing (A) about 60 to 95 wt. %, based on the weight of (A) and (B) of a homopolyethylene terephthalate with an intrinsic viscosity of at least about 0.2 dl/g (in 1:1 phenol/tetrachloroethane at 25° C.), with (B) about 40 to 5 wt. %, based on the weight of (A) and (B) of a polymer with reactive carboxyl, ester or hydroxyl end groups and a glass transition temperature of below about 0° C., and (C) about 10 to 0.5 mol %, based on the mols of ethylene glycol residues in (A), of a codiol having 4 to 10 carbon atoms, the OH groups of which are separated by aliphatic branched or unbranched groups of 3 or 4 carbon atoms, said diol having either (i) at least one secondary or tertiary OH group or (ii) two primary OH groups, in which case the diol is unsubstituted, monoalkyl substituted or dialkyl substituted, and the substituents, if any, have a total of at least 4 carbon atoms, 2. homogenizing the mixture in the form of a melt, 3. solidifying the homogenized melt, and
Claim 11
Dependent Claim
30 words
subjecting the solid so obtained to a polycondensation in vacuum or under streaming nitrogen at a temperature about 60° to 5° C. below the melting point of said homogenized mixture.
Claim 12
Dependent Claim
30 words
subjecting the solid so obtained to a polycondensation in vacuum or under streaming nitrogen at a temperature about 60° to 5° C. below the melting point of said homogenized mixture.
Claim 13
Dependent Claim
19 words
The process of claim 8 wherein said melt homogenization is conducted in the presence of esterification or transesterification catalysts.
Claim 14
Dependent Claim
18 words
The process of claim 9 wherein said melt homogenization is conducted at between about 150° and 250° C.
Claim 15
Dependent Claim
23 words
The process of claim 9 wherein the polycondensation is conducted at between about 200° and 300° C. in the presence of esterification catalysts.
Claim 16
Dependent Claim
31 words
The process of claim 9 wherein the catalysts are selected from the group consisting of acetates of zinc, manganese, cadmium and calcium, germanium compounds, boron compounds, antimony compounds and titanium compounds.
Claim 17
Dependent Claim
38 words
The process of claim 8 wherein the melt homogenization is conducted in a screw machine, the mixture is granulated and the granules are subject to polycondensation under a vacuum of less than 1 mm mercury or streaming nitrogen.
Claim 18
Dependent Claim
8 words
The product of the process of claim 8.
Claim 19
Dependent Claim
22 words
The block copolyester of claim 1 containing about 0.001 to 0.5 wt. % of a stabilizer comprising a phenol or phenol derivative.
Claim 20
Dependent Claim
47 words
A molding composition comprising the block copolyester of claim 15, reinforcing material, an effective amount of U. V. stabilizer, colorants selected from organic and inorganic pigments and dyestuffs, an effective amount of mold release agent, lubricant and about 2 to 20 wt. % of flame proofing agent.
Claim 21
Dependent Claim
13 words
A film, fiber or molding made from the block copolyester of claim 1.
Claim 22
Dependent Claim
20 words
A molding composition comprising the block copolyester of claim 1 and about 0.01 to 1 wt. % of nucleating agents.
Claim 23
Dependent Claim
22 words
The block copolyester of claim 1 containing up to about 1 mol %, based on the mols of R, of branching agent.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-06-10 | 1983-12-10 | 1984-06-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-06-10 | 1987-12-10 | 1988-06-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-06-10 | 1991-12-10 | 1992-06-10 | $7700.00 | Window Closed / Lapsed |