CN102093535A - Method for preparing microporous polyurethane elastomer - Google Patents
Method for preparing microporous polyurethane elastomer Download PDFInfo
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Abstract
The invention relates to a method for preparing a microporous polyurethane elastomer, in particular to a microporous polyurethane elastomer which is prepared through a foaming reaction that a chain extender containing a mixture of water, a high molecular weight polyalcohol, a catalyst and a foam stabilizer is stirred and blended into a mixed prepolymer prepared by stirring and blending a prepolymer containing a terminal isocyanate group and prepared by reacting a polyalcohol and 1,5-naphthalene-diisocyanate (NDI) and 3,3'-dimethyl-4,4'-diphenyldiisocyanate (TODI). The invention aims to improve the processability and the storage stability of the NDI and effectively reduce the cost of raw materials of the NDI while keeping the excellent performance of the NDI. The product prepared by the method is mainly used for bearing high-strength damping elements of dynamic fatigue, such as buffering and shock-absorbing elements of traffic tools, such as vehicles and the like, bridge shock-absorbing blocks and the like.
Description
Technical field
The present invention relates to a kind of preparation method of microporous polyurethane elastomer.
Background technology
For the polyurethane elastomer with microvoid structure, its vibration damping, impact absorbency excellence, the angle that the kinetic characteristic during from high loading, weather resistance, damping characteristic are little consider, how used as the auxiliary spring of automobile suspension system etc.Especially, for the microporous polyurethane elastomer based on NDI, its anti-Flexural fatigue excellence is used for the auxiliary spring position of requirement weather resistance more.Yet NDI compares with other diisocyanate cpd, the cost of material height, fusing point height (127 ℃), the trend of distillation is quite big, and the problem of the labour hygiene aspect that causes thus forces needs to increase the industry expenditure, and because rich reactive, thereby there is unworkable problem.Though NDI is through the prefabricated prepolymer that obtains, can store for some time, but must in three or four hours, further react, otherwise can cause side reaction being exposed to the high temperature relevant with melting operation, cause the decline of nco index and the increase of viscosity at last, the elastomeric character that makes thus is rapid deterioration also.
Automobile is owing to the alternating bending distortion causes the material self-heating with the Breakage Mechanism of auxiliary spring, and the temperature of this moment reduces the physical property of material, and produces partial crackle.Therefore, even the auxiliary spring of excellent in te pins of durability must have the character that physical property does not also reduce under hot environment with material, need have the higher-dimension structure of the polyurethane molecular chain of firm crosslinking structure to this.Yet, vulcabond, high molecular weight diol and chainextender (low molecular weight diols or water) are mixed together (single stage method) or vulcabond and high molecular weight diol are reacted modulate prepolymer after, re-use low molecular weight diols or water and carry out among the so existing preparation method of chain extending reaction (prepolymer method), use the aromatic diisocyanate except that NDI can not realize above-mentioned higher-dimension structure with polyurethane molecular chain of firm crosslinking structure.
Chinese patent CN1982351A discloses a kind of NDI base polyurethane micropore method for producing elastomers on 06 20th, 2007.This preparation method comprises the steps: the preparation of (1) performed polymer: excessive polyisocyanates and polyvalent alcohol react under 120-140 ℃ of condition, form the performed polymer of end-NCO base; (2) cast: performed polymer and chain extender component are mixed in proportion, react the feed liquid implantation temperature and be in 80-95 ℃ the mould, the demoulding behind the precuring; (3) post curing: the goods after the demoulding were in 110 ℃ of post curing 13-16 hours.Though this preparation method can obtain the micro-pore elastomer of excellent performance, the storage time that can't avoid the NDI performed polymer is short, and the production cycle is long, the raw materials cost height, and machinery equipment requires high defective.
Summary of the invention
Above-mentioned deficiency at prior art, technical problem to be solved by this invention is to provide a kind of performance in the excellence that keeps NDI to have to improve its processing characteristics and stability in storage simultaneously, and can effectively reduce the preparation method of the microcellular polyurethane elastomer of raw materials cost.Product by the inventive method preparation is mainly as the high-strength damping element that bears dynamic fatigue, as the bumper and absorbing shock element of the vehicles such as automobile and bridge snubber block etc.
In order to solve technical problem of the present invention, the present invention is in the prepolymer that contains terminal isocyanate group that polyvalent alcohol and NDI reaction is obtained, adding TODI mixes, mix the whipping agent of the mixture that comprises high molecular weight diol that water, number-average molecular weight Mn are 1000-3000, amines catalyst, suds-stabilizing agent then, carry out foamable reaction and prepare microporous polyurethane elastomer.Specifically comprise the steps: excessive N DI and polyol reaction, forming the terminal isocyanate group weight percentage is the prepolymer of 5%-13%; Prepolymer mixes with TODI, stir and obtain mixed prepolymer; Mixed prepolymer mixes, stirs with chain extender component, carry out foamable reaction after, carry out post curing treatment again and obtain microporous polyurethane elastomer.
Preferably, among the preparation method of the above-mentioned microporous polyurethane elastomer of the present invention, the mol ratio of polyvalent alcohol, NDI and TODI three's active group is 1: 2: (0.5-6), the terminal isocyanate group weight percentage is 6%-9%.
Preferably, among the preparation method of the above-mentioned microporous polyurethane elastomer of the present invention, it is that 2-3, hydroxyl value are that 30-150mgKOH/g, number-average molecular weight Mn are polyester adipate system, polycaprolactone system, polytetrahydrofuran copolyether system, polycarbonate-based, the polyetherester copolymer system of 500-4000 that polyvalent alcohol is selected from functionality, and perhaps above-mentioned two or more mixes the mixing system polyvalent alcohol that forms; More preferably the number-average molecular weight of polyvalent alcohol is 1000-3000, and hydroxyl value is 40-100mgKOH/g.
Preferably, among the preparation method of the above-mentioned microporous polyurethane elastomer of the present invention, the mixture that chain extender component is made up of water, dibasic alcohol, catalyzer and suds-stabilizing agent.The prepolymer that contains terminal isocyanate group with respect to per 100 weight parts, chain extender component comprises: the water of 0.1-4.0 weight part, 0.5-60 parts by weight average molecular weight Mn are that high molecular dibasic alcohol or the 0.1-4.0 weight part molecular weight of 1000-3000 is the low molecular weight diol of 48-200, and the siloxane foams stablizer of 0.1-2.0 weight part.Low molecular weight diols is selected from ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol and glycol ether; High molecular weight diol is selected from polyethyleneglycol adipate, polyoxyethylene glycol butyleneglycol adipic acid ester, polytetramethylene glycol and polycarbonate diol.
Preferably, among the preparation method of the above-mentioned microporous polyurethane elastomer of the present invention, catalyzer is the mixture of triethylene diamine and two (dimethylaminoethyl) ethers.
Preferably, among the preparation method of the above-mentioned microporous polyurethane elastomer of the present invention, post curing treatment carried out under 100-140 ℃ temperature 10-20 hour.
Preferably, among the preparation method of the above-mentioned microporous polyurethane elastomer of the present invention, polyvalent alcohol and NDI react under 125 ℃-130 ℃ temperature, form the terminal prepolymer that contains isocyanate group, add TODI in pre-polymerization, be cooled to 60-70 ℃, mixing, stirring obtain mixed prepolymer.
The microporous polyurethane elastomer of the method for the application of the invention preparation can play the effect of following excellence: used the microporous polyurethane elastomer of the TODI of low price, easy handling as diisocyanate cpd, reduced NDI storing temp and storage cycle effectively, also can obtain and be the microporous polyurethane elastomer that elastomerics that the basis forms has equal rerum natura characteristic with the high NDI of cost of material.
Specifically, in the compressive strength test method of general elastomeric material, under the atmosphere of room temperature and 100 ℃, survey the Static Compression characteristic, and the variation of the dynamic bearing capacity under identical compression stroke, compression frequency and same number, obtain static bearing capacity under the high temperature and keep more than 80% of bearing capacity under the normal temperature atmosphere, with the variation of bearing capacity under the dynamic fatigue below 20%, characteristic such as illustrate under the high temperature atmosphere that physical property reduces under little and the high loading that kinetic characteristic is good, weather resistance and damping characteristic are little.This is because in the preparation method's of microporous polyurethane elastomer of the present invention foamable gel reaction process, at first relative with the concentration that in polyurethane prepolymer, exists higher by the high water of reactive behavior, low-molecular-weight glycol, the comparatively faster TODI diisocyanate monomer of speed of response reacts the urea groups hard segment is generated, react the biuret groups that forms branched structure with relative higher isocyanate terminated NDI prepolymer afterwards with activity, thereby making hard segment and the soft crosslinking structure that connects section formation higher-dimension, physicals is higher thus.Therefore use low price, TODI that reactive behavior is lower to add the stability in storage that can effectively improve NDI in the NDI prepolymer, make the processing singularity of NDI be improved, the performance of the excellence that equally also obtains NDI and had.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment are interpreted as only being used to the present invention is described and are not used in restriction protection scope of the present invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalences change and modify and fall into claim of the present invention institute restricted portion equally.
In the preferred embodiment provided by the invention, long chain diol with terminal active hydrogens, and number-average molecular weight is 500-4000, preferred 1000-3000, hydroxyl value is 30-150mgKOH/g, preferred 40-100mgKOH/g get final product, and there is no particular limitation, can use polyester adipate system, polycaprolactone system, polytetrahydrofuran copolyether system, polycarbonate-based, polyetherester copolymer to be or said mixture is a polyvalent alcohol.
In the preferred embodiment provided by the invention, mixture as the vulcabond of hard section part, NDI can be with 1 mole active ingredient OH with respect to polyvalent alcohol, isocyanate group NCO be more than 1 mole and below 4 moles, preferred 2 moles of such ratios use.When the usage quantity of vulcabond composition than above-mentioned amount after a little while, can not form the prepolymer that contains terminal isocyanate group, on the other hand, when using with the many ratios of above-mentioned amount, the NDI monomer of free state is more, can influence the storage characteristics and the processibility of performed polymer.Cooling stages in the NDI pre-polymerization, add the TODI monomer fast, its NCO be more than 0.5 mole and below 6 moles, the preferred such ratio of 1-2 mole, make that the weight percentage of isocyanate group is between the 5%-13%, preferred 6%-9%, elite 8.5% uses.Because improve the weight percentage of the isocyanate group of prepolymer by the TODI monomer, reduce its storing temp and temperature of reaction, be lower than the mol ratio of above-mentioned TODI, the weight percentage of the isocyanate group of prepolymer is low, prepolymer and chainextender metering difficulty, and poor processability is higher than the maximum mol ratio of above-mentioned TODI, is difficult to form resemble the firm higher-dimension crosslinking structure of NDI forming.
In the preferred embodiment provided by the invention, use polyvalent alcohol and NDI, add the TODI of above-mentioned amount then, be cooled to 60-70 ℃ generating prepolymer about the about 15min of reaction under 125 ℃-130 ℃ the temperature.
In the preferred embodiment provided by the invention, as chainextender, the prepolymer that contains terminal isocyanate group with respect to per 100 weight parts, can make water 0.1-4.0 weight part, preferred 0.5-2.0 weight part, molecular weight is that the low molecular weight diols 0.1-4.0 weight part of 48-200, preferred 62-160, preferred 0.5-2.0 weight part and number-average molecular weight Mn are the high molecular weight diol 0.5-60 weight part of 1000-3000, preferred 1500-2000, preferred 10-50 weight part.Lower molecular weight can make spent glycol, propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycol ether etc., high molecular weight diol can use polyethyleneglycol adipate, polyoxyethylene glycol butyleneglycol adipic acid ester, polytetramethylene glycol, polycarbonate diol etc. in addition.
In the preferred embodiment provided by the invention, together determine the composition of microvoid structure with chainextender, siloxane foams stablizer etc. are being that the ratio of 0.1-2.0 weight part, preferred 0.5-1.0 weight part is used with respect to per 100 weight part prepolymers generally.Amine such as triethylene diamine and two (dimethylaminoethyl) ethers and organo-metallic classes such as stannous octoate, dibutyl tin laurate participate in reaction as the catalyzer of polyurethane reaction in addition, can also can suitably cooperate filler, antioxidant and anti-hydrolysis stabilizer etc. as required.
In the preferred embodiment provided by the invention, be blended in the NDI/TODI mixed prepolymer of generation, carry out casting by columniform mould and carry out polyurethane reaction by auxiliary agents such as chainextender, suds-stabilizing agent, catalyzer.Preferred after the demoulding in the post curing of carrying out under 100-140 ℃ the temperature about 10-20 hour, obtain microporous polyurethane elastomer spring goods thus.
Embodiment
Use density to be 0.5g/cm
3Sheet form and automobile with auxiliary spring shape assess sample physicals respectively, sheet form is 200*100*50mm, cuts out then to cut open the shape that becomes to need and often test, its condition of molding is as follows:
Terminal isocyanate group prepolymer temperature: 60-100 ℃ (making comparisons)
Chain extender component temperature: 40-60 ℃
Die temperature: 50-90 ℃ (making comparisons)
Demould time: 15-20min
Post curing: 110 ℃, 16 hours
Embodiment 1
With number-average molecular weight Mn is 2000, hydroxyl value is 56mgKOH/g polyethyleneglycol adipate polyvalent alcohol 100 weight parts after carrying out fusion under 127 ℃, add 21 weight part NDI (active ingredient NCO/OH mol ratio is 2), after keeping this temperature 15min, obtain the polyurethane prepolymer of clear.Add 26.4 weight part TODI (the TODI/NDI mol ratio is 1) then, be cooled to 60 ℃, obtain transparent clarifying mixed prepolymer while stir.In addition, be 2000 at 60 ℃ of fused number-average molecular weight Mn, hydroxyl value is in polyethyleneglycol adipate polyvalent alcohol 100 weight parts of 56mgKOH/g, add entry 4 weight parts, suds-stabilizing agent 2 weight parts, catalyzer 0.3 weight part, they were mixed 2 hours, obtain chainextender.
Under the said temperature condition, mixed prepolymer is mixed, stirs with the part by weight of chainextender with 100: 50, carry out foamable reaction, carry out post curing treatment then and obtain the evaluation sample.
Embodiment 2
For embodiment 1, in the chainextender composition, use 1 of the water of 3 weight parts and 5 weight parts, the 4-butyleneglycol substitutes the water of 4 weight parts.
Comparative Examples I
With number-average molecular weight Mn is 2000, hydroxyl value is 56mgKOH/g polyethyleneglycol adipate polyvalent alcohol 100 weight parts after carrying out fusion under 120 ℃, add 52.8 weight part TODI (the NCO/OH mol ratio is 4), after keeping this temperature 30min, obtain the TODI prepolymer, be cooled to 60 ℃.In addition, be 2000 at 60 ℃ of fused number-average molecular weight Mn, hydroxyl value is in polyethyleneglycol adipate polyvalent alcohol 100 weight parts of 56mgKOH/g, add entry 3 weight parts, 1,4-butyleneglycol 5 weight parts, suds-stabilizing agent 2 weight parts, catalyzer 0.3 weight part, they were mixed 2 hours, obtain chainextender.
Under the said temperature condition, mixed prepolymer is mixed, stirs with the part by weight of chainextender with 100: 50, carry out foamable reaction, carry out post curing treatment then and obtain the evaluation sample.
Comparative Example II
With number-average molecular weight Mn is 2000, hydroxyl value is 56mgKOH/g polyethyleneglycol adipate polyvalent alcohol 100 weight parts after carrying out fusion under 80 ℃, add 50 weight part MDI (the NCO/OH mol ratio is 4), keep this temperature after 2 hours, obtain the MDI prepolymer, be cooled to 50 ℃.In addition, be 2000 at 60 ℃ of fused number-average molecular weight Mn, hydroxyl value is in polyethyleneglycol adipate polyvalent alcohol 100 weight parts of 56mgKOH/g, add entry 3 weight parts, 1,4-butyleneglycol 5 weight parts, suds-stabilizing agent 2 weight parts, catalyzer 0.3 weight part, they were mixed 2 hours, obtain chainextender.
Under the said temperature condition, mixed prepolymer is mixed, stirs with the part by weight of chainextender with 100: 40, carry out foamable reaction, carry out post curing treatment then and obtain the evaluation sample.
Comparative Example II I
With number-average molecular weight Mn is 2000, hydroxyl value is 56mgKOH/g polyethyleneglycol adipate polyvalent alcohol 100 weight parts after carrying out fusion under 127 ℃, add 21 weight part NDI (the NCO/OH mol ratio is 2), after keeping this temperature 15min, be cooled to 90 ℃ then rapidly, obtain the polyurethane prepolymer of clear.In addition, be 2000 at 60 ℃ of fused number-average molecular weight Mn, hydroxyl value is in polyethyleneglycol adipate polyvalent alcohol 100 weight parts of 56mgKOH/g, add entry 7 weight parts, suds-stabilizing agent 2 weight parts, catalyzer 0.3 weight part, they were mixed 2 hours, obtain chainextender.
Under the said temperature condition, mixed prepolymer is mixed, stirs with the part by weight of chainextender with 100: 10, carry out foamable reaction, carry out post curing treatment then and obtain the evaluation sample.
The test example
Viscosity under the prepolymer that use obtains in above embodiment and Comparative Examples is surveyed 60 ℃, write down each forming mould temperature, the evaluation that obtains sheet form by foaming is carried out tensile strength, tension set, tear strength and compression set with sample, use the evaluation of automobile auxiliary spring to carry out high low temperature static compression verification, the durability test of identical compression stroke in addition with sample.Test-results is as shown in table 1.
Tensile strength, tension set: corresponding to ASTM D412.
Tear strength: corresponding to ASTM D2262.
Static Compression set (Cs%) testing method: from test piece, take out 50 * 50 * 10mm peeling test block, measure test piece original height h
0With pad height h
240% of compression test piece height, aging 22hr in 80 ℃ baker places 2hr release again under the room temperature, measure aging back height h
1
Cs％＝(h
0-h
1)/(h
0-h
2)×100％。
The Static Compression characteristic: to 10KN, with the original height 85mm of sample is zero point all then with the speed precompressed sample of 50mm/min 3 times, and the 4th is compressed to 10KN at the same rate, the bearing capacity of record power one displacement curve and a certain position such as 65mm; Preheating is compressed to 10KN after 3 hours at the same rate in 100 ℃ environment then, the bearing capacity of record power one displacement curve and a certain position 65mm.
Dynamic fatigue testing method: measure goods original height h
0, with the compression stroke frequency, the circulation 100,000 times of 0-65mm (the original height 85mm of sample is zero point), 2HZ along the goods short transverse, survey height h after the goods fatigue
1, and the variation of the bearing capacity of the peak position before and after the dynamic fatigue.
ΔL＝h
0-h
1
Table 1
Claims (11)
1. the preparation method of a microporous polyurethane elastomer is characterized in that, excessive N DI and polyol reaction, and forming the terminal isocyanate group weight percentage is the prepolymer of 5%-13%; Prepolymer mixes with TODI, stir and obtain mixed prepolymer; Mixed prepolymer mixes, stirs with chain extender component, carry out foamable reaction after, carry out post curing treatment again and obtain microporous polyurethane elastomer.
2. the preparation method of microporous polyurethane elastomer according to claim 1 is characterized by, and the mol ratio of polyvalent alcohol, NDI and TODI three's active group is 1: 2: (0.5-6), the terminal isocyanate group weight percentage is 6%-9%.
3. the preparation method of microporous polyurethane elastomer according to claim 1 and 2, it is characterized by, it is that 2-3, hydroxyl value are that 30-150mgKOH/g, number-average molecular weight Mn are polyester adipate system, polycaprolactone system, polytetrahydrofuran copolyether system, polycarbonate-based, the polyetherester copolymer system of 500-4000 that polyvalent alcohol is selected from functionality, and perhaps above-mentioned two or more mixes the mixing system polyvalent alcohol that forms.
4. the preparation method of microporous polyurethane elastomer according to claim 3 is characterized by, and the number-average molecular weight of polyvalent alcohol is 1000-3000, and hydroxyl value is 40-100mgKOH/g.
5. the preparation method of microporous polyurethane elastomer according to claim 1 is characterized by, the mixture that chain extender component is made up of water, dibasic alcohol, catalyzer and suds-stabilizing agent.
6. the preparation method of microporous polyurethane elastomer according to claim 5, it is characterized by, the prepolymer that contains terminal isocyanate group with respect to per 100 weight parts, chain extender component comprises: the water of 0.1-4.0 weight part, 0.5-60 parts by weight average molecular weight Mn are that high molecular dibasic alcohol or the 0.1-4.0 weight part molecular weight of 1000-3000 is the low molecular weight diol of 48-200, and the siloxane foams stablizer of 0.1-2.0 weight part.
7. the preparation method of microporous polyurethane elastomer according to claim 6, it is characterized by, chain extender component comprises: 0.5-2.0 weight parts water, 0.5-2.0 weight part molecular weight are that low molecular weight diol or the 10-50 parts by weight average molecular weight Mn of 62-160 is the high molecular dibasic alcohol of 1500-2000.
8. according to the preparation method of claim 6 or 7 described microporous polyurethane elastomers, it is characterized by, low molecular weight diols is selected from ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol and glycol ether; High molecular weight diol is selected from polyethyleneglycol adipate, polyoxyethylene glycol butyleneglycol adipic acid ester, polytetramethylene glycol and polycarbonate diol.
9. the preparation method of microporous polyurethane elastomer according to claim 5 is characterized by, and catalyzer is the mixture of triethylene diamine and two (dimethylaminoethyl) ethers.
10. the preparation method of microporous polyurethane elastomer according to claim 1 is characterized by, and post curing treatment carried out under 100-140 ℃ temperature 10-20 hour.
11. the preparation method of microporous polyurethane elastomer according to claim 1, it is characterized by, polyvalent alcohol and NDI react under 125 ℃-130 ℃ temperature, form the terminal prepolymer that contains isocyanate group, in pre-polymerization, add TODI, be cooled to 60-70 ℃, mixing, stirring obtain mixed prepolymer.
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| CN102391468A (en) * | 2011-09-30 | 2012-03-28 | 南京金三力橡塑有限公司 | Preparation method of prepolymer based on 1, 5-naphthyl diisocyanate and stably stored |
| CN102956240A (en) * | 2011-08-26 | 2013-03-06 | 山内株式会社 | Stopper for magnetic head |
| CN104024298A (en) * | 2011-12-27 | 2014-09-03 | Skc株式会社 | Method for the preparation of microcellular polyurethane elastomers |
| CN104262583A (en) * | 2014-09-18 | 2015-01-07 | 东莞市吉鑫高分子科技有限公司 | Low-compression-deformation special microporous polyurethane elastomer and preparation method thereof |
| CN104311791A (en) * | 2014-11-18 | 2015-01-28 | 上海恩的爱化学科技有限公司 | Synthesis formula for NDI-based cellular polyurethane elastomer |
| CN104817683A (en) * | 2015-04-24 | 2015-08-05 | 黎明化工研究设计院有限责任公司 | Polyurethane elastomer and preparation method thereof |
| CN106608960A (en) * | 2015-10-22 | 2017-05-03 | 上海凯众材料科技股份有限公司 | Preparation method of polyurethane microporous elastomer |
| CN114935516A (en) * | 2022-04-28 | 2022-08-23 | 中国石油大学(华东) | Method for testing tensile property of metal material by adopting ball indentation method |
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| CN1400229A (en) * | 2002-08-30 | 2003-03-05 | 中国科学院广州化学研究所 | Polyurethane foam material and its preparation method |
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| CN102956240A (en) * | 2011-08-26 | 2013-03-06 | 山内株式会社 | Stopper for magnetic head |
| CN102956240B (en) * | 2011-08-26 | 2014-10-08 | 山内株式会社 | Stopper for magnetic head |
| CN102391468B (en) * | 2011-09-30 | 2013-04-10 | 南京金三力橡塑有限公司 | Preparation method of prepolymer based on 1, 5-naphthyl diisocyanate and stably stored |
| CN102391468A (en) * | 2011-09-30 | 2012-03-28 | 南京金三力橡塑有限公司 | Preparation method of prepolymer based on 1, 5-naphthyl diisocyanate and stably stored |
| CN104024298B (en) * | 2011-12-27 | 2016-09-21 | Skc株式会社 | The method preparing microcellular polyurethane elastomer |
| CN104024298A (en) * | 2011-12-27 | 2014-09-03 | Skc株式会社 | Method for the preparation of microcellular polyurethane elastomers |
| CN104262583A (en) * | 2014-09-18 | 2015-01-07 | 东莞市吉鑫高分子科技有限公司 | Low-compression-deformation special microporous polyurethane elastomer and preparation method thereof |
| CN104311791A (en) * | 2014-11-18 | 2015-01-28 | 上海恩的爱化学科技有限公司 | Synthesis formula for NDI-based cellular polyurethane elastomer |
| CN104817683A (en) * | 2015-04-24 | 2015-08-05 | 黎明化工研究设计院有限责任公司 | Polyurethane elastomer and preparation method thereof |
| CN104817683B (en) * | 2015-04-24 | 2018-03-09 | 黎明化工研究设计院有限责任公司 | A kind of polyurethane elastomer and preparation method thereof |
| CN106608960A (en) * | 2015-10-22 | 2017-05-03 | 上海凯众材料科技股份有限公司 | Preparation method of polyurethane microporous elastomer |
| CN106608960B (en) * | 2015-10-22 | 2021-01-05 | 上海凯众材料科技股份有限公司 | Preparation method of polyurethane microporous elastomer |
| CN114935516A (en) * | 2022-04-28 | 2022-08-23 | 中国石油大学(华东) | Method for testing tensile property of metal material by adopting ball indentation method |
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