CN102093535B - Method for preparing microporous polyurethane elastomer - Google Patents
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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 are excellent, and the kinetic characteristic during from high loading, weather resistance, the angle that damping characteristic is little consider, how used as the auxiliary spring of automobile suspension system etc.Especially, for take the microporous polyurethane elastomer of NDI as the basis, its anti-Flexural fatigue is excellent, multiplex auxiliary spring position in requiring weather resistance.Yet NDI compares with other diisocyanate cpd, and cost of material is high, fusing point high (127 ℃), the trend of distillation is quite large, 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.Although 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 at last the decline of nco index and the increase of viscosity, the elastomeric character that makes thus also sharply worsens.
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 local 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 to have the higher-dimension structure of the polyurethane molecular chain of firm crosslinking structure to this.Yet, after vulcabond, high molecular weight diol and chainextender (low molecular weight diols or water) are mixed together (single stage method) or make in advance vulcabond and high molecular weight diol react to modulate prepolymer, 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 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.Although 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, and raw materials cost is high, and machinery equipment requires high defective.
Summary of the invention
Above-mentioned deficiency for prior art, technical problem to be solved by this invention is to provide a kind of performance of the excellence keeping NDI to have to improve simultaneously its processing characteristics and stability in storage, 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, such as the bumper and absorbing shock element of the vehicles such as automobile and Bridge Seismic piece 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, then 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, carry out foamable reaction and prepare microporous polyurethane elastomer.Specifically comprise the steps: excessive NDI 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 again post curing treatment 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 comprised 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, BDO, 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 TODI of low price, easy handling as the microporous polyurethane elastomer of diisocyanate cpd, effectively reduce NDI storing temp and storage cycle, also can obtain the microporous polyurethane elastomer that has equal physical property characteristic with the elastomerics that forms as the basis take 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 Carrying 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%, the 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 higher by the high water of reactive behavior, low-molecular-weight glycol and the relative concentration that in polyurethane prepolymer, exists, the comparatively faster TODI diisocyanate monomer of speed of response reacts to make the urea groups hard segment to generate, form the biuret groups of branched structure afterwards with the relatively high isocyanate terminated NDI prepolymer reaction of activity, thereby making hard segment and the soft crosslinking structure that connects section formation higher-dimension, physicals is higher thus.Therefore but use low price, TODI that reactive behavior is lower to add the stability in storage of Effective Raise NDI in the NDI prepolymer, so that the processing singularity of NDI is improved, equally also obtain the performance of the excellence that NDI has.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment are interpreted as only being used for explanation the present invention 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 modification falls into claim limited range of the present invention 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 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 is lacked than above-mentioned amount, 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 affect storage characteristics and the processibility of performed polymer.Cooling stages in the NDI pre-polymerization, add fast the TODI monomer, its NCO be more than 0.5 mole and below 6 moles, the preferred such ratio of 1-2 mole so 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 under 125 ℃-130 ℃ temperature, to react and approximately generate prepolymer about 15min, then add the TODI of above-mentioned amount, be cooled to 60-70 ℃.
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 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 is 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 generally to use as the ratio of 0.1-2.0 weight part, preferred 0.5-1.0 weight part with respect to per 100 weight part prepolymers.The amine such as triethylene diamine and two (dimethylaminoethyl) ethers and the 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 resistant to hydrolysis stablizer etc. as required.
In the preferred embodiment provided by the invention, be blended in the NDI/TODI mixed prepolymer of generation by auxiliary agents such as chainextender, suds-stabilizing agent, catalyzer, carry out casting by columniform mould and carry out polyurethane reaction.Preferred in the post curing of carrying out under 100-140 ℃ the temperature about 10-20 hour after the demoulding, obtain thus microporous polyurethane elastomer spring goods.
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, then cuts out to cut open into the shape that needs 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 melting 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.Then add 26.4 weight part TODI (the TODI/NDI mol ratio is 1), be cooled to 60 ℃ while stir, obtain the mixed prepolymer of transparent clarification.In addition, be 2000 at the number-average molecular weight Mn of 60 ℃ of meltings, 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 are 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, then carry out post curing treatment and obtain the evaluation sample.
Embodiment 2
For embodiment 1, the BDO of the water of use 3 weight parts and 5 weight parts substitutes the water of 4 weight parts in the chainextender composition.
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 melting 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 the number-average molecular weight Mn of 60 ℃ of meltings, 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 are 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, then carry out post curing treatment 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 melting 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 the number-average molecular weight Mn of 60 ℃ of meltings, 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 are 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, then carry out post curing treatment 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 melting under 127 ℃, add 21 weight part NDI (the NCO/OH mol ratio is 2), after keeping this temperature 15min, then be cooled to rapidly 90 ℃, obtain the polyurethane prepolymer of clear.In addition, be 2000 at the number-average molecular weight Mn of 60 ℃ of meltings, 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 are 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, then carry out post curing treatment and obtain the evaluation sample.
Test example
Viscosity under the prepolymer that use obtains in above embodiment and Comparative Examples is surveyed 60 ℃, record the die temperature of each moulding, the evaluation that obtains sheet form by foaming is carried out tensile strength, tension set, tear strength and compression set with sample, use in addition the evaluation of automobile auxiliary spring to carry out high low temperature static compression verification, the durability test of identical compression stroke 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 again release of 2hr under the room temperature, height h after measurement is aging
1
Cs％＝(h
0-h
1)/(h
0-h
2)×100％。
The Static Compression characteristic: to 10KN, then all take the original height 85mm of sample as zero point, 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 with the speed precompressed sample of 50mm/min 3 times; Then preheating is compressed to 10KN after 3 hours at the same rate in 100 ℃ environment, the bearing capacity of record power one displacement curve and a certain position 65mm.
Dynamic fatigue testing method: measure goods original height h
0, be the frequency of 0-65mm (the original height 85mm of sample is zero point), 2HZ, circulation 100,000 times along the goods short transverse take compression stroke, survey afterwards height h of 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 (7)
1. the preparation method of a microporous polyurethane elastomer is characterized in that, excessive NDI and polyol reaction, and forming the terminal isocyanate group weight percentage is the prepolymer of 6%-9%; Prepolymer mixes with TODI, stir and obtain mixed prepolymer; Mixed prepolymer mixes, stirs with chain extender component, carry out foamable reaction after, carry out again post curing treatment and obtain microporous polyurethane elastomer, wherein:
The mol ratio of polyvalent alcohol, NDI and TODI three's active group is 1:2:(0.5-6);
The mixture that chain extender component is comprised 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;
Catalyzer is the mixture of triethylene diamine and two (dimethylaminoethyl) ethers.
2. the preparation method of microporous polyurethane elastomer according to claim 1, it is characterized by, it is that 2-3, hydroxyl value are that 30-150mgKOH/g, number-average molecular weight Mn are that the polyester adipate system of 500-4000, poly-own Inner ester are, the polytetrahydrofuran copolyether is, polycarbonate-based, polyetherester copolymer system that polyvalent alcohol is selected from functionality, perhaps the above-mentioned mixing system polyvalent alcohol that forms that mixes more than two kinds.
3. the preparation method of microporous polyurethane elastomer according to claim 2 is characterized by, and the number-average molecular weight of polyvalent alcohol is 1000-3000, and hydroxyl value is 40-100mgKOH/g.
4. the preparation method of microporous polyurethane elastomer according to claim 1, 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.
5. according to claim 1 or the preparation method of 4 described microporous polyurethane elastomers, it is characterized by, low molecular weight diols is selected from ethylene glycol, propylene glycol, BDO, 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.
6. 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.
7. 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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| 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 |
| KR101351432B1 (en) * | 2011-12-27 | 2014-01-15 | 에스케이씨 주식회사 | 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 |
| 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 |
| 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 |
| CN114935516B (en) * | 2022-04-28 | 2024-07-26 | 中国石油大学(华东) | Method for testing tensile property of metal material by ball indentation method |
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