CN1057308C - Method for preparing heat resistant polyurethane elastomer - Google Patents
Method for preparing heat resistant polyurethane elastomer Download PDFInfo
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- CN1057308C CN1057308C CN97101134A CN97101134A CN1057308C CN 1057308 C CN1057308 C CN 1057308C CN 97101134 A CN97101134 A CN 97101134A CN 97101134 A CN97101134 A CN 97101134A CN 1057308 C CN1057308 C CN 1057308C
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- performed polymer
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- isocyanuric acid
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Abstract
The present invention relates to a method for preparing temperature resistant polyurethane elastomers. In the method, after isocyanate, dewatered dihydric alcohol and compounds of which the molecules simultaneously contain isocyanurate rings and active hydrogen directly react or react step by step to prepare prepolymers, chain extenders are added for chain extension, pouring and vulcanization for obtaining products. The method has the advantages that no catalysts or inhibitors are added in a reaction process to simplify the reaction process and avoid the generation of side reactions in a catalytic process, and also has the advantages of easy reaction control and cost reduction.
Description
The invention belongs to a kind of method for preparing heat resistant polyurethane elastomer.
To be a class constitute-(AB) n-type segmented copolymer by soft, hard section polyurethane elastomer (PUE), because it has high abrasion, oil resistant, low temperature resistant, hydrolysis, anti-aging, mildew-resistant and higher characteristics such as elasticity, makes its Application Areas very extensive.But its resistance toheat is relatively poor, and (ASTM-D-648) weighs with heat-drawn wire, only up to 80 ℃, that is to say, only has the performance of PUE when using below 80 ℃ just can be guaranteed.Yet in many practical matter, as the parts in the drill bit of oil field, the sth. made by twisting wheel on the textile manufacturing machine, special rubber roll and some high-pressure sealing ring in the Iron And Steel Industry, use temperature often surpasses 80 ℃, and common like this PUE just is difficult to be competent at, and uses also to be restricted.
In order to address these problems, people have adopted various approach to improve the thermally-stabilised qualitative of PUE.In heat resistance modified method commonly used, except that add the heat-resisting inorganics of part or with the refractory organics blend, mainly be on polyurethane backbone, to embed inorganic elements silicon, fluorine etc., can also introduce heat-resisting organic heterocyclic molecule, as isocyanuric acid ester, poly-oxazolidone, polyimide etc.
Isocyanurate ring is a heteroatoms six membered ring that thermostability is higher, its heat resisting temperature is above 200 ℃, usually by isocyanic ester trimerization and making under the effect of catalyzer, its shortcoming be in the polymerisate except that generating the tripolymer isocyanurate ring, also have dimer and carbodiimide by product to generate; In addition, when isocyanic ester is issued to needed extent of polymerization in the effect of catalyzer, in time add the inhibitor termination reaction, otherwise solidify too high causing of reactive polymeric degree.
The purpose of this invention is to provide a kind of without the elastomeric method of Preparation of catalysts heat resistant polyurethane.
The object of the present invention is achieved like this, and elder generation is by dehydration dibasic alcohol, isocyanic ester and contain isocyanurate ring simultaneously and compound bearing active hydrogen reaction generation performed polymer, adds chainextender again and must react goods, and its production method is as follows:
Method A:
1. consist of (equivalence ratio) by material
Isocyanic ester: dehydration dibasic alcohol: the proportioning that contains isocyanurate ring and compound bearing active hydrogen=1: 0.8: 0.1～1: 0.1: 0.8 adds in the reactor, under whipped state, is warming up to 80-90 ℃ of reaction 2-4 hour, makes performed polymer.
2. earlier performed polymer is warmed up to 80-90 ℃, consist of (equivalence ratio) by material then: isocyanate group in the performed polymer: chainextender=1: 0.85～1: 0.95, add chainextender under 80-90 ℃ of temperature, carry out chain extending reaction, through cast, sulfuration, obtain product.
Aforesaid isocyanic ester with contain isocyanurate ring and compound bearing active hydrogen, add reactor earlier, under whipped state, heat up, to 80-90 ℃ of temperature, react 0.5-1 hour, add diol reaction 1.5-3 hour of dewatering again, make performed polymer.
Aforesaid isocyanic ester, the dibasic alcohol and contain isocyanurate ring and compound bearing active hydrogen can add in the reactor simultaneously of dewatering under whipped state, were warming up to 80-90 ℃ of thermotonus 2-4 hour, made performed polymer.
Method B:
1. consist of (equivalence ratio) by material
The dehydration dibasic alcohol: isocyanic ester=0.8: 1～add reactor at 0.1: 1, under whipped state, be warming up under the 80-90 ℃ of temperature, reacted 2-4 hour, obtain performed polymer.
2. earlier performed polymer is warmed up to 80-90 ℃, consists of (equivalence ratio) by material then
Isocyanate group in the performed polymer: contain isocyanic acid urea ester ring compound bearing active hydrogen: chainextender=1: 0.8: 0.1～1: 0.1: 0.8, add in the reactor containing isocyanurate ring and compound bearing active hydrogen and chainextender, under 80-90 ℃ of temperature, stirring reaction 3-10 minute, obtain product through cast, sulfuration.
Aforesaid dehydration dibasic alcohol is the poly-epsilon-caprolactone dibasic alcohol, the polyethylene glycol adipate dibasic alcohol, poly-hexanodioic acid second/propylene glycol ester dibasic alcohol, polyoxytrimethylene ether glycol, PTMG, copolyether dibasic alcohol of producing by oxyethane, propylene oxide and tetrahydrofuran (THF) etc.
Aforesaid isocyanic ester is TDI-100, TDI-80, MDI, NDI, HDI etc.
Aforesaid chainextender comprises simple form and cross-linking type, and 3,3 ' 1 chloro-4 are arranged, 4 ' one ditan diamines (MOCA), 1,4 one butyleneglycols (BDO), hydroquinone two hydroxy ethyl ether (HQEE), glycerine, TriMethylolPropane(TMP) (TMP), 1,2,6 one hexanetriols and tetramethylolmethane etc.
Aforesaidly contain isocyanurate ring and compound bearing active hydrogen can be isocyanuric acid, isocyanuric acid three (beta-hydroxy) ester, isocyanuric acid three (beta-hydroxyethyl) ester, isocyanuric acid three (allyl group) ester, isocyanuric acid three (β-propyloic) ester etc.
The present invention has following advantage:
1. directly in elastomerics, introduced the good isocyanuric acid vinegar ring of heat resistance.
2. the content of isocyanuric acid vinegar ring can arbitrarily be controlled.
3. do not add catalyzer and inhibitor, simplified reaction process.
4. avoided the side reaction in the catalytic reaction process to generate.
5. cost reduces.
6. improved quality product.
Embodiments of the invention are as follows:
Embodiment 1:
(1) 50g TDI-100 and 6.8g isocyanuric acid three (beta-hydroxy) ester are added in the reactor, under whipped state, be warming up to 85 ℃, reacted 0.5 hour, add 147.1g dehydration poly-epsilon-caprolactone (M=1280) again, holding temperature is at 85 ℃ under whipped state, react and made performed polymer in 2.5 hours, the equivalence ratio of its reactant is TDI-100: isocyanuric acid three (beta-hydroxy) ester: dehydration 6-caprolactone=1: 0.2: 0.4
Performed polymer is through the deaeration post analysis, wherein isocyanate group (NCO) %=4.5%
(2) get performed polymer 120g, be heated to 83 ℃, add 15.4g fused MOCA chainextender again, under this temperature, stirred chain extending reaction 3 minutes, through cast, vulcanize product.
The equivalence ratio of its reactant is: in the performed polymer-NCO base: MOCA=1: 0.9
Embodiment 2
(1) 50gTDI-100 and 5g isocyanuric acid three (beta-hydroxyethyl) ester are added in the reactor, under whipped state, be warming up to 80 ℃, reacted 0.5 hour, add 172g dehydration PTMG (M=1000) again, under whipped state, keep 80 ℃ of reactions 3 hours, make performed polymer.The equivalence ratio of its reactant is TDI-100: isocyanuric acid three (beta-hydroxyethyl) ester: dehydration PTMG=1: 0.1: 0.6, performed polymer is through deaeration post analysis NCO%=3.1%.
(2) get performed polymer 125g, be heated to 85 ℃, add 10.7g fused MOCA chainextender again, under this temperature, stirred chain extending reaction 3.5 minutes, through cast, vulcanize product, the equivalence ratio of its reactant is performed polymer-NCO base: MOCA=1: 0.87.
Embodiment 3
(1) 60gMDI and 8.4g isocyanuric acid three (beta-hydroxyethyl) ester are added in the reactor, under whipped state, be warming up to 86 ℃, reacted 0.8 hour, add 72g dehydration polyethylene glycol adipate dibasic alcohol (M=996) again, keep under 83 ℃ of temperature at whipped state, reacted 2.5 hours, and made performed polymer.The equivalence ratio of its reactant is MDI: isocyanuric acid three (beta-hydroxyethyl) ester: ethylene glycol adipate(EGA) dibasic alcohol=1: 0.2: 0.3, performed polymer is through deaeration post analysis NCO%=7.0%.
(2) get performed polymer 120g, be heated to 80 ℃ and added 4g 1.4-butyleneglycol and 4g TriMethylolPropane(TMP) mixed chain extender chain extending reaction again 2.5 minutes, through cast, vulcanize product, the equivalence ratio of its reactant is in the performed polymer-the NCO base: 1.4-butyleneglycol: TriMethylolPropane(TMP)=1: 0.45: 0.45.
Embodiment 4
(1) add 50g TDI-100 and 115g dehydration PTMG (M=1000) and 6.8g isocyanuric acid three (beta-hydroxy) ester in the reactor simultaneously, under whipped state, be warming up to 85 ℃, keep reaction 3.5 hours, make performed polymer, its equivalence ratio is TDI-100: isocyanuric acid three (beta-hydroxy) ester: PTMG=1: 0.2: 0.4, performed polymer is through deaeration post analysis NCO%=5.5%.(2) get performed polymer 150g, be heated to 83 ℃ and add 24.4g fusion MOCA again, under this temperature, stirred chain extending reaction 3 minutes, through cast, vulcanize goods.The equivalence ratio of its reactant is in the performed polymer-NCO base: MOCA=1: 0.93.
Embodiment 5
(1) add 50gMDI, 10.4g isocyanuric acid three (beta-hydroxyethyl) ester and the poly-hexanodioic acid second/propylene glycol ester (M=1000) of 60g dehydration in the reactor simultaneously, under whipped state, be warming up to 87 ℃, keep reaction 3 hours, make performed polymer, the equivalence ratio of its reactant is MDI: isocyanuric acid three (beta-hydroxyethyl) ester: poly-hexanodioic acid second/propylene glycol ester=1: 0.3: 0.3, performed polymer is through deaeration post analysis NCO%=5.4%.
(2) get performed polymer 118g, be heated to 82 ℃, add 5.6g 1.4-butyleneglycol again, 0.7g TriMethylolPropane(TMP) mixed chain extender under this temperature, stirred chain extending reaction 2 minutes, through cast, vulcanize goods.In the equivalence ratio performed polymer of its reactant-and the NCO base: 1.4-butyleneglycol: TriMethylolPropane(TMP)=1: 0.8: 0.1
Embodiment 6
(1) 230g is dewatered polyethylene glycol adipate (M=2000) and 1008 2.4-TDI add reactor, under whipped state, be warming up to 85 ℃, react and made performed polymer in 3 hours, the equivalence ratio of its reactant is dehydration polyethylene glycol adipate: 2.4-TDI=0.2: 1, and performed polymer is through deaeration post analysis NCO%=11.3%.
(2) get above-mentioned performed polymer 100g and be heated to 80 ℃ after, add 9.2g isocyanuric acid and 5.4gMOCA chainextender simultaneously, stirring reaction is 5 minutes under 80 ℃ of temperature, through cast, vulcanize product.Its equivalence ratio is in the performed polymer-the NCO base: isocyanuric acid: MOCA=1: 0.8: 0.15.
Embodiment 7
Produce performed polymer by embodiment 6, and take by weighing after 120g is heated to 85 ℃, add 14.0g isocyanuric acid three (beta-hydroxyethyl) ester (THEIC) and 17.2g MOCA chainextender simultaneously, stirring reaction is 4 minutes under 85 ℃ of temperature, through cast, vulcanize goods.The equivalence ratio of its reactant is in the performed polymer-NCO base: THEIC: MOCA=1: 0.5: 0.4.
Embodiment 8
(1) 100g dehydration PTMG (M=1000) adds reactor with 50g MDI, is warming up to 83 ℃ under whipped state, reacts to make performed polymer in 2.5 hours.The equivalence ratio of its reactant is PTMG: MDI=0.5: 1, and NCO%=5.4% by analysis after the performed polymer deaeration.
(2) get performed polymer 130g and be heated to 87 ℃ after, add 5.9g isocyanuric acid three (beta-hydroxy) ester and 5.0g hydroquinone two hydroxy ethyl ether (HQEE) simultaneously, stirring reaction 3.5 minutes, through cast, vulcanize goods.The equivalence ratio of its reactant is in the performed polymer-NCO base: isocyanuric acid three (beta-hydroxy) ester: HQEE=1: 0.6: 0.3.
Claims (5)
1. method for preparing heat resistant polyurethane elastomer is characterized in that:
(1). consist of by the material equivalence ratio
Isocyanic ester: dehydration dibasic alcohol: the proportioning that contains isocyanurate ring and compound bearing active hydrogen=1: 0.8: 0.1～1: 0.1: 0.8 adds in the reactor, under whipped state, is warming up to 80-90 ℃, reacts 2-4 hour, makes performed polymer;
(2). earlier performed polymer is warmed up to 80-90 ℃, consists of by the material equivalence ratio then: isocyanate group in the performed polymer: chainextender=1: 0.85～1: 0.95, add chainextender and under 80-90 ℃ of temperature, carry out chain extending reaction, cast, sulfuration obtain product.
2. method for preparing heat resistant polyurethane elastomer according to claim 1, it is characterized in that earlier with described isocyanic ester with contain isocyanurate ring and compound bearing active hydrogen and add reactor, under whipped state, be warming up to 80-90 ℃, reacted 0.5-1 hour, add the dehydration diol reaction again 1.5-3 hour, and made performed polymer.
3. method for preparing polyurethane elastic body according to claim 1, it is characterized in that described isocyanic ester, dehydration dibasic alcohol and contain isocyanurate ring and compound bearing active hydrogen can add in the reactor simultaneously, under whipped state, be warming up to 80-90 ℃, react and made performed polymer in 2-4 hour.
4. method for preparing heat resistant polyurethane elastomer is characterized in that:
(1). consist of by the material equivalence ratio
The dehydration dibasic alcohol: isocyanic ester=0.8: 1～0.1: 1 adds reactor, under whipped state, is warming up to 80-90 ℃, reacts to obtain performed polymer in 2-4 hour.
(2). earlier performed polymer is warmed up to 80-90 ℃, consists of by the material equivalence ratio then
Isocyanate group in the performed polymer: contain isocyanic acid urea ester ring and compound bearing active hydrogen: chainextender=1: 0.8: 0.1～1: 0.1: 0.8, add in the reactor containing isocyanic ester ring and compound bearing active hydrogen and chainextender, under 80-90 ℃ of temperature, stirring reaction 3-10 minute, obtain product through cast, sulfuration.
5. according to any one described method for preparing heat resistant polyurethane elastomer in the claim 1,2,3 and 4, it is characterized in that describedly containing isocyanurate ring and compound bearing active hydrogen can be isocyanuric acid, isocyanuric acid three (beta-hydroxy) ester, isocyanuric acid three (beta-hydroxyethyl) ester, isocyanuric acid three (allyl group) ester, isocyanuric acid three (beta-hydroxyethyl) ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97101134A CN1057308C (en) | 1997-01-27 | 1997-01-27 | Method for preparing heat resistant polyurethane elastomer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97101134A CN1057308C (en) | 1997-01-27 | 1997-01-27 | Method for preparing heat resistant polyurethane elastomer |
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| CN1189509A CN1189509A (en) | 1998-08-05 |
| CN1057308C true CN1057308C (en) | 2000-10-11 |
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| CN97101134A Expired - Fee Related CN1057308C (en) | 1997-01-27 | 1997-01-27 | Method for preparing heat resistant polyurethane elastomer |
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| CN105131248A (en) * | 2015-09-08 | 2015-12-09 | 沈阳化工大学 | High-temperature-resistant robot crawler and preparation method thereof |
| CN107880243A (en) * | 2017-11-23 | 2018-04-06 | 广东元星工业新材料有限公司 | A kind of high heat-resistant high-performance polyurethane elastomer and preparation method thereof |
| CN111995725B (en) * | 2020-09-07 | 2022-02-11 | 江苏湘园化工有限公司 | Environment-friendly liquid polyurethane curing agent and application method thereof |
| CN112375205A (en) * | 2020-11-20 | 2021-02-19 | 南京艾德恒信科技有限公司 | Preparation method and application of high-strength polyurethane elastomer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801675A (en) * | 1986-06-28 | 1989-01-31 | Bayer Aktiengesellschaft | Process for the preparation of prepolymers containing isocyanate groups, the prepolymers obtainable by this process and their use as binders in one-component lacquers |
| US5021534A (en) * | 1987-11-11 | 1991-06-04 | Nippon Polyurethane Industry Co., Ltd. | Thermosetting urethane elastomer |
| JPH0337564B2 (en) * | 1984-07-20 | 1991-06-06 | Sanyo Chemical Ind Ltd | |
| JPH03273019A (en) * | 1990-03-23 | 1991-12-04 | Furukawa Electric Co Ltd:The | Castable flame-retarding urethane composition |
| JPH0543826A (en) * | 1991-08-19 | 1993-02-23 | Sanyo Chem Ind Ltd | Preparation of powdered urethane resin composition |
| US5565270A (en) * | 1994-04-25 | 1996-10-15 | Bayer Aktiengesellschaft | Process for the production of elastane filaments |
-
1997
- 1997-01-27 CN CN97101134A patent/CN1057308C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0337564B2 (en) * | 1984-07-20 | 1991-06-06 | Sanyo Chemical Ind Ltd | |
| US4801675A (en) * | 1986-06-28 | 1989-01-31 | Bayer Aktiengesellschaft | Process for the preparation of prepolymers containing isocyanate groups, the prepolymers obtainable by this process and their use as binders in one-component lacquers |
| US5021534A (en) * | 1987-11-11 | 1991-06-04 | Nippon Polyurethane Industry Co., Ltd. | Thermosetting urethane elastomer |
| EP0617066A2 (en) * | 1987-11-11 | 1994-09-28 | Nippon Polyurethane Industry Co. Ltd. | Thermosetting urethane elastomer |
| JPH03273019A (en) * | 1990-03-23 | 1991-12-04 | Furukawa Electric Co Ltd:The | Castable flame-retarding urethane composition |
| JPH0543826A (en) * | 1991-08-19 | 1993-02-23 | Sanyo Chem Ind Ltd | Preparation of powdered urethane resin composition |
| US5565270A (en) * | 1994-04-25 | 1996-10-15 | Bayer Aktiengesellschaft | Process for the production of elastane filaments |
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| CN1189509A (en) | 1998-08-05 |
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