GB2140436A - Polyurethane and method of producing same - Google Patents
Polyurethane and method of producing same Download PDFInfo
- Publication number
- GB2140436A GB2140436A GB08402048A GB8402048A GB2140436A GB 2140436 A GB2140436 A GB 2140436A GB 08402048 A GB08402048 A GB 08402048A GB 8402048 A GB8402048 A GB 8402048A GB 2140436 A GB2140436 A GB 2140436A
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- GB
- United Kingdom
- Prior art keywords
- molecular weight
- average molecular
- polyurethane
- polycaprolactone polyol
- weight
- 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.)
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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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a polyurethane comprising (a) organic diisocyanate units and (b) polycaprolactone polyol units having a narrow molecular weight distribution in which the ratio of the weight average molecular weight to the number average molecular weight is in the range of from 1.1 to 2.0 and the average molecular weight is 500 to 5,000, the units (a) and (b) being connected linearly through urethane linkages. The invention also provides a process for producing such polyurethanes.
Description
1 GB 2 140 436 A 1
SPECIFICATION
Lactone polymer and polyurethane obtained therefrom The present invention relates to a lactone polymer, especially a lactone polymer having a narrow molecular 5 weight distribution, and a process forthe preparation thereof. Moreover, the invention relates to a polyurethane and a process forthe preparation thereof. More particularly, the invention relates to a polyurethane wh i ich is excellent in elastic recovery and has a very good operation adaptability because of a low viscosity thereof, and a process for the preparation thereof. The polyurethane is obtained from diisocyanate and the before mentioned lactone polymer. The lactone polymer having a molecular weight of 10 500 to 5,000 is very valuable as a starting material to be used for manufacture of polyurethanes, paints and the like.
Conventional lactone polymers having a molecular weight of 500 to 5,000, however, have a broad molecularweight distribution and the ratio of the weight average molecularweight to the number average molecular weight is in the range of from 2.5 to 3.5. When such polymers are actually used, various problems 15 are caused by this broad molecular weight distribution.
We made researches on molecular weight distributions of conventional lactone polymers by gel permeation chromatography (hereinafter referred to as "GPC"), and found that if the molecular weight distribution is appropriately adjusted, lactone polymers giving practically very excellent characteristics can be obtained. We have now completed the present invention based on this finding.
More specifically, in accordance with the present invention, there are provided a lactone polymer having a narrow molecular weight distribution, which is characterized in that the ratio of the weight average molecular weight to the number average molecular weight is in the range of from 1.1 to 2.0 and the molecular weight is 500 to 5,000, and a process for the preparation of such lactone polymer.
By the term "lactone polymer" used in the present invention is meant a polymer obtained by subjecting 25 e-caprolactone to ring-opening polymerization in the presence of an initiator containing an active hydrogen atom. As the initiator, there can be used polyhydric alcohols such as diols and triols and polyvalent amines.
As the diol, there can be mentioned ethylene glycol, propylene glycol, diethylene glycol, 1,4-butylene glycol, 1,6-hexane diol and neopentyl glycol. As the triol, there can be listed glycerin and trimethylol-propane. Other polyhydric alcohols include pentaerythritol, acrylic polyols, styrene/allyl alcohol copolymers and polymeric 30 resins having hydroxyl groups such as polyester-polyols, epoxy resins, polyether polyols and cellulose derivatives. The polyvalent amines include ethylene diamine, diethylene triamine and ethanol amine. Moreover aromatic polyamines may be used here.
By the term "molecular weight'used in the present invention is meant a value calculated from the hydroxyl value of the lactone polymer according to the following formula:
Molecularweight = [hydroxyl value] x [NI x 1000 56.0 The hydroxyl value is determined according tothe method of JIS K-1557 6.4. In the aboveformula, N represents the number of functional groups of the initiator.
The molecular weight of the lactone polymer of the present invention is 500 to 5,000.
As is apparent from the foregoing description, the amount of the polymerization initiator necessary for 45 obtaining a predetermined molecular weight can be defined according to the above calculation formula.
The ratio of the weight-average molecular weight P1w to the numberaverage molecular weightW[n, that is, the molecular weight distribution, is determined by GPC.
2 GB 2 140 436 A 2 Apparatus:
Solvent:
Temperature:
Columns:
Detector:
Model LC-3A manufactured by Shimazu Seisakusho tetra hydrofu ran, 1 mt/min room temperature HSG-PRE (one), HSG-20 (one, HSG-1 5 (three) HSG-10 (one) (each being supplied by Shimazu Seisakusho) Shodex RI SEA 1 (supplied by Showa Denko) The ratio of the weight average molecular weight to the number average molecular weight is in the range of from 1.1 to 2.0.
The process for the preparation of the polymer of the present invention will now be described.
In the preparation process according to the present invention, a stannous halide such as stannous chloride, stannous bromide or stannous iodide is used as a catalyst. The amount used of the catalyst is 0.1 to 20 50 ppm based on the total weight of E-caprolactone. If the amount of the catalyst used is smaller than 0.1 ppm, polymerization is not advanced, and if the amount of the catalyst used is larger than 50 ppm, it becomes difficult to obtain a polymer having a narrow molecular weight. The reaction temperature is ordinarily 100 to 230'C and preferably 120 to 190'C.
Since a known catalyst, TBT (tetrabutyl titanate), contributions not only to ring-opening polymerization but 25 also to ester exchange reaction, use of this catalyst results in production of a polymer having a broad molecular weight distribution.
The lactone polymer of the present invention has a narrower molecular weight distribution than the conventional lactone polymer and also has a lower viscosity and a slightly lower melting point than those of the conventional polymer.
Since the molecular weight distribution of the lactone polymer of the present invention is narrow, it is very valuable as a starting material to be used for manufacture of urethane elastomers, urethane adhesives, urethane paints and polyurethanes.
For example, when the polymer of the present invention is used in the field of spandex fibres, there can be provided products excellent inelastic recovery characteristics. Furthermore, there can be provided a 35 high-solid paint as a polyol component of a two-pack type urethane paint.
Polyurethanes having a linear structure have heretofore been synthesized by reacting a polyol having hydroxyl groups on both the molecular ends, an organic diisocyanate and a chain extender having a relatively low molecular weight such as a diol or diamine. As the polyol having hydroxyl groups on both the molecule ends, there are used polyester type polyols and polyether type polyols. As the polyester type polyol, there are ordinarily used a polyester polyol synthesized from ethylene glycol or 1,4-butylene glycol and adipic acid and a polycaprolactone polyol prepared from E- caprolactone. The conventional polycapro lactone polyol is defective in that it is inferiorto polyether type polyols, especially polytetra methyl e n e glycol (PTMG), in elastic recovery. Accordingly, the conventional polycaprolactone polyof cannot be used in the fields where a high elastic recovery is required. When polyester type polyols are used for the synthesis of 45 urethane prepolymers to be used for casting or urethane type adhesives, their operation adaptability is bad because of a high viscosity, and if the viscosity is reduced so as to improve the operation adaptability, the characteristics of the resulting polyurethanes are degraded.
We made researches with a view to eliminating these defects of conventional polycaprolactone type polyurethanes, and we found that a polyurethane prepared by using a polycaprolactone polyol having a narrow molecular weight distribution has an excellent elastic recovery not observed in the conventional products and it has a lower viscosity than those of the conventional products and a highly improved operation adaptability in the synthesis of prepolymers and urethane type adhesives. We have now completed the present invention based on this finding.
More specifically, the present invention relates to a polyurethane prepared by reacting an organic diisocyanate with a compound containing at least two active hydrogen atoms in the molecule, wherein a polycaprolactone polyol having a narrow molecular weight distribution in which the ratio of the weight average molecular weight to the number average molecular weight is in the range of from 1.1 to 2.0 and the average molecular weight is 500 to 5,000, is used as the active hydrogen atom-containing compound, and a 3 GB 2 140 436 A 3 process forthe preparation thereof.
As the organic diisocyanate that is used in the present invention, there can be mentioned, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-di phenyl methane diisocyanate, tolidine dlisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and 1,5-naphthalene diisocyanate. As the chain extender that is used in carrying out the present invention, there are preferably used ethylene glycol, propylene glycol, 1,4-butylene glycol and 1,6-hexamethylene diol. Furthermore, there can be used ethylene diamine, propylene diamine and hydrazine.
For preparing the polyurethane of the present invention, there is preferably adopted a prepolymer process comprising reacting a polyol with an excessive amount of an organic isocyanate to form an isocyanateterminated prepolymer and then reacting the formed prepolymer with a chain extender such as a diol or 10 diamine. As the solvent to be used for the preparation of a solution type polyurethane, such as urethane adhesive, there can be used ordinary solvents such as toluene, ethyl acetate, methylethyl ketone and dimethylformamide.
The polycaprolactone type polyurethane of the present invention is superior to the conventional products inelastic recovery and has a low viscosity and a good operation adaptability. This is due to the fact that the 15 molecular distribution of the polycaprolactone polyol is narrow and in the range of from 1.1 to 2.0.
The polyurethane of the present invention can be used very advantageously for manufacture of a spandex products, adhesives, artificial leathers and paints.
The present invention will now be described in detail with reference to the following Examples and Comparative Examples that by no means limit the scope of the invention. In these Examples, all "parts" are 20 by weight.
Examples 1 through 4 and Comparative Examples 1 through 3 [Polymer Having Molecular Weight of 20001 A three-neck separable f lask having a capacity of 1 litre was charged with 969g (8.5 moles) of E-caprolactone, 31 g (0.5 mole) of ethylene glycol and a predetermined amount of a catalyst (see Table). A thermometer, a condenser and a nitrogen-introducing tube were attached to the flask, and reaction was carried out at a predetermined temperature in a nitrogen gas atmosphere. When the content of E-caprolactone measured by gas chromatography was lower than 0.5%, the reaction was stopped, and the reaction product was cooled and withdrawn.
Example 5 and Comparative Example 4 Polymer Having Molecular Weight of 1250 Procedures of the foregoing Examples were repeated in the same manner except that 5949 (5.2 moles) of 35 F--caprolactone and 31g (0.5 mole) of ethylene glycol were charged.
4 GB 2 140 436 A 4 TABLE Reaction Conditions Molecular Catalyst TempeTime Melting Viscosity 5 Example No. Weight (Ppm) rature rC) (hours) 70w[M-n Point rC) (cps, at 750C) Comparative 2000 TBT, 10 170 7-8 2.98 49-50 350 Example 1
Comparative 2000 d itto 200 1.5 2.83 10 Example 2
Comparative 2000 ditto 140 14 2.58 Example 3 15
Example 1 2000 SnC'2, 5 170 5.5 1.76 45-46 204 Example 2 2000 d itto 140 34.0 1.61 Example 3 2000 SnC02,20 140 3 1.54 20 Example4 2000 ditto 130 16 1.55 Comparative 1250 TBT, 10 170 7-8 2.55 45-47 160 25 Example 4
Example 5 1250 SnCIC2, 5 170 6.5 1.51 37-39 91 Note 30 The melting point was measured by a melting point measuring device Model MP supplied by Yanagimoto Seisakusho. The viscosity was measured by a B- type rotary viscometer. The molecular weight distribution MwiM-n was determined according to the GPC method.
Synthesis Example 6 A four-neckflask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a condenser was charged with 1938 parts of E-captrolactone, 62 parts of ethylene glycol and 0.01 part of stannous chloride, and reaction was carried out at 17WC for 5.5 hours to obtain a polycaprolactone polyol having a hydroxyl value of 56.2 KOH mglg (the unit will be omitted hereinafter), an acid value of 0.27 KOH mglg (the unit will be omitted hereinafter), a viscosity of 204 cps at75'C and a molecular weight distribution of 1.73.
Example 7
Physical properties of a polyurethane elastomer prepared by reacting 200 parts of the polycaprolactone polyoi obtained in Synthesis Example 6 which had a molecular distribution of 1.73, with 75 parts of 4,4'-diphenyl methane diisocyanate at 80'C for 1 hour and subjecting the reaction product to addition 45 polymerization with 12 parts of 1,4-butylene glycol as the chain extender, were as follows:- 100%Modulus 300% Modulus Tensile strength Elongation Elastic recovery JIS Hardness A K g/CM2 90 Kg /CM2 392 Kg/cM2 565% 65% 80 w_ GB 2 140 436 A 5 The elastic recovery means the elasticity recovery ratio (20'C) determined by stretching the sample by 300%, allowing the sample to stand still for 10 minutes from release of stretching and making calculation according to the following formula:Elastic recovery = (1 - _ e) X 100 le inwhich,e stands for the distance between standard lines before stretching and t- standsforthe distance between standard lines after stretching and releasing.
Synthesis Example 8 In the same manner as described in Synthesis Example 6, reaction was carried out at 13WC for 16 hours by using 1938 parts of E-caprolactone, 62 parts of ethylene glycol and 0.02 part of stannous chloride to obtain a polycaprolactone polyol having a hydroxyl value of 56.2, an acid value of 0.20, a viscosity of 151 cps at 75'C 15 and a molecular weight distribution of 1.45.
Example 9
The polycaprolactone polyol having a molecular weight distribution of 1. 45, which was obtained in Synthesis Example 8, was reacted in the same manner according to the same recipe as in Example 7. 20 Physical properties of the obtained polyurethane elastomer were as follows:100%Modulus 300 % Modulus Tensile strength Elongation Elastic recovery JIS Hardness A 39 Kg /CM2 88 Kg/CM2 350 Kg /CM2 600% 80% 79 Comparative Example 5 35 In the same manner as described in Synthesis Example 6, reaction was carried out at 170'C for 6 hours by 35 using 1938 parts of e-caprolactone, 62 parts of ethylene glycol and 0.02 part of tetrabutyl titanate to obtain a polycaprolactone polyol having a hydroxyl value of 52.1, an acid value of 0.21, a viscosity of 350 cps at 75'C and a molecular weight distribution of 2.98. The so-obtained polycaprolcatone polyol was reacted in the same manner according to the same recipe as in Example 7. Physical properties of the obtained polyurethane elastomer were as follows:- % Modulus 300 % Modulus Tensile strength Elongation Elastic recovery JIS Hardness A 39 Kg/CM2 Kg/cM2 440 Kg/cM2 550% 40% Comparative Example 6 55 In the same manner as described in Synthesis Example 6, reaction was carried out at 130'C for 16 hours by 55 using 1938 parts of e-caprolactone, 62 parts of ethylene glycol and 0.02 part of tetrabutyl titanate to obtain a polycaprolactone polyol having a hydroxyl value of 56.2, an acid value of 0.22, a viscosity of 320 cps at 75'C and a molecular weight distribution of 2.58. The so-obtained polycaprolactone polyol was reacted in the same manner according to the same recipe as in Example 7. Physical properties of the obtained polyurethane elastomer were as follows:- 6 GB 2 140 436 A % Modulus 300%Modulus Tensile strength Elongation Elastic recovery JIS Hardness A Kg/cM2 93 Kg /CM2 430 Kg/cM2 550% 50% Example 10 A 4-neck flask equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing tube and a condenser was charged with 200 parts of the polycaprolactone polyol obtained in Synthetis Example 8, 15 which had a molecular distribution of 1.45,31.2 parts of neopentyl glycol, 101 parts of 4,4'-di phenyl methane diisocyanate and 635 parts of methylethyl ketone as the solvent, and 0.7 part of methanol was used as the reaction stopper. Reaction was conducted at 750C for 8 hours to obtain a polyurethane solution having a solid content of 35 % and a viscosity of 32,000 cps at 250C. The polyurethane solution was cast on a glass sheet and dried at 40oC overnight to obtain a transparent polyurethane film having the following physical 20 properties.
% Modulus 18 Kg/cM2 Tensile strength 160 Kg /CM2 25 Elongation 600% Elastic recovery 80% 30 Comparative Example 7 The polycaprolactone obtained in Comparative Example 5, which had a molecularweight distribution of 2.98, was reacted in the same manner according to the same recipe as in Example 10 to obtain a polyurethane solution having a solid content of 35 % and a viscosity of 48,000 at 2WC. Afilm prepared from this polyurethane solution had the following physical properties.
100%Modulus
Claims (3)
- Tensile strength Elongation Elastic recovery 18 Kg/cM2 Kg/cM2 580% 40% 1. A polyurethane comprising (a) organic diisocyanate units and (b) polycaprolactone polyol units having a narrow molecular weight distribution in which the ratio of the weight average molecular weight to the number average molecular weight is in the range of from 1.1 to 2.0 and the average molecular weight is 500 50 to 5,000, the units (a) and (b) being connected linearly through urethane, linkages.
- 2. A process as claimed in claim 1, and substantially as hereinbefore described with reference to anyone of Examples 1, 2 and
- 3.Printed in the UK for HMSO, D8818935, 10184, 7102. Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.2. A process for the preparation of polyurethanes which comprises reacting an organic diisocyanate with a compound containing at least two active hydrogen atoms in the molecule, wherein a polycaprolactone polyol having a narrow molecular weight distribution in which the ratio of the weight average molecular weight to the number average molecular weight is in the range of from 1. 1 to 2.0 and the average molecular 55 weight is 500 to 5,000, is used as the active hydrogen atom-containing compound.3. A polyurethane as claimed in claim 1 and substantially as hereinbefore described with reference to any one of Examples 7,9 and 10.4. A process as claimed in claim 2 and substantially as hereinbefore described with reference to anyone of Examples 7,9 and 10.6 z 7 GB 2 140 436 A 7 New claims or amendments to claims filed on 31 Jul 1984 Superseded claims 1 to 4 New or amended claims:- 1. A process for the preparation of a polyurethane, which comprises the step of reacting an organic diisocyanate and a chain extender with a polycaprolactone polyol in which the ratio of the weight average molecular weight to the number average molecular weight is in the range of from 1.1 to 2.0 and the average molecular weight (as hereinbefore defined) is from 500 to 5,000, said polycaprolactone polyol having been prepared by subjecting an epsilon-caprolactone to ring-opening polymerization in the presence of an initiator containing at least two active hydrogen atoms and as catalyst 0. 1 to 50 ppm based on the total weight of epsilon-caprolactone of stannous halide selected from stannous chloride, stannous bromide and stannous iodide, to form a polycaprolactone polyol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56028182A JPS57155230A (en) | 1981-02-27 | 1981-02-27 | Lactone polymer having narrow molecular weight distribution and its preparation |
| JP56069077A JPS57185313A (en) | 1981-05-08 | 1981-05-08 | Polyurethane and its preparation |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8402048D0 GB8402048D0 (en) | 1984-02-29 |
| GB2140436A true GB2140436A (en) | 1984-11-28 |
| GB2140436B GB2140436B (en) | 1985-06-05 |
Family
ID=26366224
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8205658A Expired GB2093853B (en) | 1981-02-27 | 1982-02-26 | Lactone polymer and polyurethane obtained therefrom |
| GB08402048A Expired GB2140436B (en) | 1981-02-27 | 1984-01-26 | Polyurethane and method of producing same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8205658A Expired GB2093853B (en) | 1981-02-27 | 1982-02-26 | Lactone polymer and polyurethane obtained therefrom |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE3207062C2 (en) |
| GB (2) | GB2093853B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63251415A (en) * | 1987-03-13 | 1988-10-18 | スウィフト アデシフ エスアー | Heat-meltable polymer used as adhesive, its production and application thereof to adhesion of surface of base material |
| EP0776921A3 (en) * | 1995-12-01 | 1997-08-13 | Hokushin Corp | Method for preparing amorphous polymer chains in elastomers |
| EP0783009A3 (en) * | 1995-12-01 | 1997-08-13 | Hokushin Corporation | Method for producing millable polyurethanes and polyurethane elastomers |
| US6008312A (en) * | 1995-12-01 | 1999-12-28 | Hokushin Corp | Method for producing millable polyurethanes and polyurethane elastomers |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1232285A (en) * | 1983-02-24 | 1988-02-02 | Linda A. Domeier | Polyester polyols and a process for their production |
| GB8324958D0 (en) * | 1983-09-17 | 1983-10-19 | Bio Kil Chemicals Ltd | Surface coating compositions |
| CN116478381B (en) * | 2023-04-19 | 2023-11-17 | 湖南聚仁化工新材料科技有限公司 | Bio-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1201909A (en) * | 1967-05-17 | 1970-08-12 | Laporte Chemical | Production of polyesters |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56149422A (en) * | 1980-04-23 | 1981-11-19 | Daicel Chem Ind Ltd | Preparation of lactone high-polymer |
-
1982
- 1982-02-26 GB GB8205658A patent/GB2093853B/en not_active Expired
- 1982-02-26 DE DE19823207062 patent/DE3207062C2/en not_active Expired - Fee Related
-
1984
- 1984-01-26 GB GB08402048A patent/GB2140436B/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1201909A (en) * | 1967-05-17 | 1970-08-12 | Laporte Chemical | Production of polyesters |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63251415A (en) * | 1987-03-13 | 1988-10-18 | スウィフト アデシフ エスアー | Heat-meltable polymer used as adhesive, its production and application thereof to adhesion of surface of base material |
| JPH0411596B2 (en) * | 1987-03-13 | 1992-02-28 | ||
| EP0776921A3 (en) * | 1995-12-01 | 1997-08-13 | Hokushin Corp | Method for preparing amorphous polymer chains in elastomers |
| EP0783009A3 (en) * | 1995-12-01 | 1997-08-13 | Hokushin Corporation | Method for producing millable polyurethanes and polyurethane elastomers |
| US6008312A (en) * | 1995-12-01 | 1999-12-28 | Hokushin Corp | Method for producing millable polyurethanes and polyurethane elastomers |
| US6103852A (en) * | 1995-12-01 | 2000-08-15 | Hokushin Corporation | Method for preparing amorphous polymer chains in elastomers |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2140436B (en) | 1985-06-05 |
| GB8402048D0 (en) | 1984-02-29 |
| DE3207062A1 (en) | 1982-09-16 |
| DE3207062C2 (en) | 1997-06-05 |
| GB2093853A (en) | 1982-09-08 |
| GB2093853B (en) | 1984-09-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20000226 |