CN103059260B - Method for preparing thermoplastic polyurethane elastomers by polyurethane sole raw liquor isocyanate components - Google Patents
Method for preparing thermoplastic polyurethane elastomers by polyurethane sole raw liquor isocyanate components Download PDFInfo
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- CN103059260B CN103059260B CN201210527091.5A CN201210527091A CN103059260B CN 103059260 B CN103059260 B CN 103059260B CN 201210527091 A CN201210527091 A CN 201210527091A CN 103059260 B CN103059260 B CN 103059260B
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Abstract
The invention discloses a method for preparing thermoplastic polyurethane elastomers by polyurethane sole raw liquor isocyanate components. The method comprises the following steps of (1) stirring, heating a polyester or polyether type oligomer compound with active hydroxyl; vacuumizing and dehydrating, keeping the temperature between 80 and 100 DEG C, adding additives, and stirring to uniformly disperse the additives to obtain a mixture I; (2) preheating small molecule dihydric alcohol to a temperature of between 80 and 100 DEG C, and preheating the sole raw liquor isocyanate components to temperature of between 40 and 60 DEG C; and (3) uniformly mixing the small molecule dihydric alcohol and the sole raw liquor isocyanate components in step (2) with the mixture I in step (1) respectively; and performing post-processing granulation to obtain the thermoplastic polyurethane elastomers. According to the method, the thermoplastic polyurethane elastomers are prepared by the expired or unexpired sole raw liquor isocyanate components, so that waste materials are utilized, and the pollution is reduced. The obtained thermoplastic polyurethane elastomers have the advantages of higher strength, good melting performance, high heat resistance and ultraviolet resistance and wide application range.
Description
Technical field
The present invention relates to a kind of thermoplastic polyurethane method for producing elastomers, be specifically related to one and utilize soles system isocyanate component to prepare the elastomeric method of thermoplastic polyurethane.
Background technology
State of Shi Xie sparetime university of China, footwear output has accounted for more than 60% of global total amount, and export volume accounts for more than 50% of global article of footwear total trade volume, one of first three large commodity having become China's export.The rapid growth of footwear output, also the development of related industries has been pulled, wherein polyurethane sole materials is because having the features such as comfortable, light, anti-skidding, good springiness, intensity are high, flexible resistance good, wear-resisting, oil resistance is good, be subject to the favor of people, development is swift and violent, at present only the annual production of China's Mainland polyurethane shoe-sole stoste just reaches more than 350,000 tons, has become the footwear macromolecular material of running neck and neck with the material such as polyvinyl chloride (PVC), ethene one acetate ethylene copolymer (EVA), thermoplastic elastomer (TPR).
The preparation of polyurethane shoe-sole stoste adopts prepolymer method or semi-prepolymer method more, generally can be made into two-pack or three components, and in two-pack, component A is made up of some polyesters, chainextender, foam stabilizer and whipping agent etc.; B component is the ending isocyanate prepolymer (Isocyanate prepolymers body) that some polyesters polyvalent alcohol and isocyanate reaction obtain; In three components, component C is catalyzer, also can be added in component A, be then two-pack stoste.
Although polyurethane shoe-sole has the plurality of advantages such as good, the excellent feel of flexible resistance, cohesiveness are good, the B component (isocyanate component) of polyurethane shoe-sole stoste premixed systems has that shelf characteric is unstable, the shortcoming of validity period short (being generally 3 months).Its reason is the B component of polyurethane shoe-sole stoste premixed systems is by pure MDI(4,4-diphenylmethanediisocyanate) be the semi-prepolymer that main isocyanate prepolymer composition and oligomer polyol are synthesized, hold NCO(isocyanate group containing a large amount of unreacted monomer MDI and unreacted activity).NCO group very easily reacts with (as in air) water in environment, and MDI goes back pole autohemagglutination except Yi Yushui reacts.Shelf-time has been grown, and the micro-moisture brought into when the autohemagglutination of MDI and NCO and packaging reacts, and cause the NCO group content of B component to reduce, active centre when causing at the bottom of shoemaking is departed from, and serious even loses activity, and can not use completely.
The problem that storage period, short strip was come, economically row, also not too obvious when exporting vigorous.Because now the sale of soles system is also very fast with use, substantially there is not the problem exceeding the time limit to deposit.But in descending in economy, that outlet is not smooth period, will carry out product obsolescence because of short strip storage period and lose efficacy, to soles system manufacture and usage, enterprise causes no small loss.And with the method for the expired soles system B component of pre-treatment mostly be burn or bury, environment is also polluted.
Summary of the invention
Technical problem to be solved by this invention is, thering is provided a kind of utilizes expired or not out of date soles system to prepare the elastomeric method of thermoplastic polyether urethane, the isocyanate component of expired soles system being turned waste into wealth, stopping the environmental pollution that the isocyanate component because processing soles system causes.
Technical scheme of the present invention:
For solving the problems of the technologies described above, the present invention uses soles system isocyanate component to prepare the method for Polyurethane Thermoplastic Elastomer, mainly utilize polyurethane shoe-sole stoste isocyanate component and there is the polyester of activity hydroxy or polyether-type oligomer compounds, small molecules dibasic alcohol, auxiliary agent carry out being mixed with and obtain described Polyurethane Thermoplastic Elastomer, specifically comprise the steps:
(1), under abundant stirring condition, will polyester or the heating of polyether-type oligomer compounds of activity hydroxy be had, at 90-120 DEG C, vacuumize dehydration, 80-100 DEG C is maintained the temperature at after dehydration, and add auxiliary agent, fully stir and auxiliary agent is uniformly dispersed, obtain mixture I;
(2), simultaneously, small molecules dibasic alcohol is preheated to 80-100 DEG C, soles system isocyanate component is preheated to 40-60 DEG C;
(3), by the small molecules dibasic alcohol through thermal pretreatment in step (2), soles system isocyanate component respectively Homogeneous phase mixing to step (1) gained mixture I, obtain mixture II, then obtain Polyurethane Thermoplastic Elastomer through aftertreatment granulation.
Further, the described polyester with activity hydroxy is containing two activity hydroxies, the equal relative molecular mass of number is the polyester glycol of 1000,2000,1500,1800,3000 or 4000, the described polyether-type oligomer compounds with activity hydroxy is containing two activity hydroxies, the equal relative molecular mass of number is the polyoxytrimethylene ether glycol of 1000,2000,1500,1800,3000,4000, and preferably the equal relative molecular mass of number is the PTMG of 1000,2000,1500,1800.
Further, described polyester glycol is the hexanodioic acid system polyester glycol that hexanodioic acid and ethylene glycol, BDO, 1,6-hexylene glycol, methyl propanediol, glycol ether or neopentyl glycol are synthesized; Or the mixture of hexanodioic acid system polyester and phthalic anhydride system polyester glycol, in its mixture, the content of phthalic anhydride system polyester glycol is 0 ~ 40%, preferably 0 ~ 20%, more preferably 0 ~ 10%, described phthalic anhydride system polyester glycol refers to by phthalic anhydride and the polyester glycol synthesized with ethylene glycol, BDO, 1,6-hexylene glycol, methyl propanediol, glycol ether or neopentyl glycol, the polyester that preferred phthalic anhydride and ethylene glycol, BDO, glycol ether or neopentyl glycol are synthesized.
Further, described small molecules dibasic alcohol is 1,4-butyleneglycol, ethylene glycol, 1, ammediol, glycol ether, 1, one in 6-hexylene glycol, methyl propanediol, neopentyl glycol, quinhydrones two (2-hydroxyethyl) ether, simple dihydroxy-benzene double hydroxyethyl ether or 1,3 butylene glycol, is preferably ethylene glycol, 1, one in 4-butyleneglycol or 1,6-hexylene glycol.
Further, described auxiliary agent is the one in oxidation inhibitor, photostabilizer or lubricant.
Further, described oxidation inhibitor is the mixed thing of part kind antioxidant and phosphite ester kind antioxidant of being obstructed, the mass ratio of part kind antioxidant and phosphite ester kind antioxidant of being obstructed is 5:1-1:2, be preferably 2:1-1:1, wherein, Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, the mixture of one or more in 2,6 di tert butyl 4 methyl phenol; Phosphite ester kind antioxidant is tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two [2-methyl-4,6-bis-(1,1'-dimethyl ethyl) phenol] ethyl ester, four (2,4-di-tert-butyl-phenyl-4,4'-xenyl) mixture of one or more in biphosphonate; The quality of the add-on of oxidation inhibitor is the 0.2-2% of formula total mass, preferred 0.5-1.5%.
Further, described photostabilizer is UV light absorber, is Octabenzone, ESCALOL 567,2-(2'-hydroxyl-3', 5'-diamyl phenyl) benzotriazole, 2-(2
, -hydroxyl-5
, -aminomethyl phenyl) benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorinated benzotriazole, the special octyl phenyl of 2-(2'-hydroxyl-5'-) benzotriazole, 2,2'-methylene support-bis-(6-benzotriazole-4 tertiary octyl phenyl phenol), two (1,2,2,6,6-pentamethyl--4-piperidyl) SA ester, two-2,2,6, the mixed thing of one or more in 6-tetramethyl piperidine alcohol ester, the quality of the add-on of this photostabilizer is the 0.1-1% of formula total mass, preferred 0.2-0.5%.
Further, described lubricant is the one in stearate, amine hydroxybenzene, N, N'-ethylenebisstearamide, montanin wax, preferred brown coal-E wax, and the quality of the add-on of this lubricant is the 0.05-5% of formula total mass, preferred 0.1-2%.
Further, also catalyzer is added when adding auxiliary agent in described step (1), described catalyzer is the one in stannous octoate, dibutyl tin dilaurate, tetrabutyl titanate, titanium isopropylate or organo-bismuth, the sub-tin of preferably octanoic acid and organo-bismuth, the quality of the add-on of this catalyzer is the 0-0.05% of formula total mass, preferred 0.001-0.01%.
Further, the described aftertreatment granulation of step (3) refers to that mixture II being added continuously temperature range controls in the twin screw extruder of 150-230 DEG C, and extruded material, through cooling and dicing under water, obtains Polyurethane Thermoplastic Elastomer product;
Or, by mixture II note on the stainless steel conveyor belt scribbling tetrafluoroethylene, sending into is connected with in the drying tunnel of nitrogen, keep conveyor belt temperature at 120-125 DEG C, the material solidified by drying tunnel is after fragmentation, use twin screw extruder extruding pelletization at 140-180 DEG C again, obtain Polyurethane Thermoplastic Elastomer product;
Or, mixture II is poured into and scribbles in the stainless steel charging tray of tetrafluoroethylene, be placed with in the baking oven of nitrogen protection, dry 4 hours at 140-150 DEG C, be broken into particle after cooling, obtain Polyurethane Thermoplastic Elastomer product.
Described polyurethane shoe-sole stoste isocyanate component (B component) can be not out of date or expired; This soles system B component is the semi-prepolymer containing reactive isocyanate groups (-NCO group) synthesized by aromatic diisocyanate and polyester polyol.Wherein vulcabond is aromatic, based on MDI, can be MDI or MDI and TDI-100, one of them mixture of TDI-80, TDI-65, MDI-50, the mixture of preferred MDI or MDI and TDI-65.Described TDI-100 refers to 2,4 toluene diisocyanate, and TDI-80 refers to 2, the ratio of 4-tolylene diisocyanate and 2,6-tolylene diisocyanate is the mixture of 80:20, and TDI-65 refers to 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate ratio are the mixture of 65:35.MDI refers to 4,4-'-diphenylmethane diisocyanate, and MDI-50 refers to that the ratio of 4,4-'-diphenylmethane diisocyanate and 2,4-'-diphenylmethane diisocyanate is the mixture of 50:50.Other several vulcabond except MDI, massfraction shared in this isocyanate component is 0-10%, preferentially selects 0-5%.
The present invention utilizes expired or not out of date soles system B component (isocyanate component), add polymerized polyalcohol, small molecules diol chain-extension agent, rational production technique (such as twin screw extrusion process) is adopted to prepare Polyurethane Thermoplastic Elastomer (TPU), expired polyurethane shoe-sole stoste isocyanate component can not only be made to turn waste into wealth, also stopped the environmental pollution caused because processing expired isocyanate component.Thermoplastic polyurethane elastomerics prepared by the present invention has higher intensity, good melting behaviour, good heat-resisting and ultraviolet-resistant performance, can be used as elastomerics, coating resin, tackiness agent, ink adhesive resin, fabric coating resin etc., specifically can be used for sole, electric wire foreskin and sheath, gas dynamic tube, castor, sealing-ring goods etc., product performance are excellent, have the value applied.
Embodiment
embodiments of the invention 1:
Equivalent is the soles system B material (polyester polyol being 2000 by MDI and the equal relative molecular mass Mn of number synthesizes) of 220:
5.136kg;
Poly-hexanodioic acid-ethylene glycol-glycol ether ester (Mn2000):
4kg;
BDO:
0.812kg;
Antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester):
52g;
Brown coal-E wax (montanic acid ester type waxes): 30g.
Under abundant stirring condition, under poly-hexanodioic acid-ethylene glycol-glycol ether ester is heated to the temperature of 90 DEG C-120 DEG C (optimal selection 105 DEG C-110 DEG C, the speed making to vacuumize dehydration is fast, and dehydrating effect is good simultaneously) vacuumize dehydration.Maintain the temperature at 80-100 DEG C after processed, and add antioxidant 1010, fully stir and make it be uniformly dispersed.1.4-butyleneglycol is also preheating to 80-100 DEG C simultaneously; soles system B used material is preheating to 40-60 DEG C; then first by 1; 4-butyleneglycol to be added in poly-hexanodioic acid-ethylene glycol-glycol ether ester abundant stir about 3 minutes; maintain the temperature at 90-110 DEG C; the pure soles system B material being preheating to 40-60 DEG C is added; violent stirring about 1 minute; then pour into and scribble in the stainless steel charging tray of tetrafluoroethylene; be placed with in the baking oven of nitrogen protection; dry 4 hours at 140-150 DEG C, be broken into particle after cooling, obtain product.
Product performance are as follows:
Hardness (Shao A) 90;
Shock elasticity/% 33;
100% stress at definite elongation/MPa 6.9;
300% stress at definite elongation/MPa 11.5;
Tensile strength/MPa 40;
Tensile yield/% 660;
Tear strength N/mm 105.
embodiments of the invention 2:
Equivalent is the soles system B material (polyester polyol being 1000 by MDI and Mn synthesizes) of 200
80.25kg;
Poly-hexanodioic acid-glycol ester (Mn is 1000)
1.825kg;
BDO
17.925kg;
Antioxidant 1010
1kg;
ESCALOL 567 300g
.
Under abundant stirring condition, under polyester or polyether glycol being heated to the temperature of 90 DEG C-120 DEG C (optimal selection 105 DEG C-110 DEG C) vacuumize dehydration.Maintain the temperature at 80-100 DEG C after processed, and add auxiliary agent, fully stir and make it be uniformly dispersed.Simultaneously by small molecules glycol as 1.4-butyleneglycol is also preheating to 80-100 DEG C, diisocyanate component is preheating to 40-60 DEG C, then other is divided to squeeze in high-speed mixing head with precision metering pump, rotor intense mixing through high speed rotating is even, noting to send into the stainless steel conveyor belt scribbling tetrafluoroethylene is connected with in the drying tunnel of nitrogen, and keep conveyor belt temperature at 120-125 DEG C, the material solidified by drying tunnel is after fragmentation, use screw extrusion press extruding pelletization at 140-180 DEG C again, obtain product.
Product performance are as follows:
Hardness (Shao A) 90;
Shock elasticity/% 26;
100% stress at definite elongation/MPa 8.7;
300% stress at definite elongation/MPa 13.4;
Tensile strength/MPa 42;
Tensile yield/% 560;
Tear strength N/mm 125.
embodiments of the invention 3:
Equivalent is the soles system B material (polyester polyol being 2000 by MDI and the equal relative molecular mass Mn of number synthesizes) of 220
513.6kg;
Poly-hexanodioic acid-BDO ester (Mn2000)
400kg;
BDO
81.2kg;
Antioxidant 1010
6kg.
Under abundant stirring condition, under poly-hexanodioic acid-BDO ester is heated to the temperature of 90 DEG C-120 DEG C (optimal selection 105 DEG C-110 DEG C) vacuumize dehydration.Maintain the temperature at 80-100 DEG C after processed, and add oxidation inhibitor, fully stir and make it be uniformly dispersed.1.4-butyleneglycol is also preheating to 80-100 DEG C simultaneously, soles system is preheating to 40-60 DEG C, then other is divided to squeeze in high-speed mixing head with precision metering pump, rotor intense mixing through high speed rotating is even, add continuously in twin screw extruder, twin screw extruder temperature controls 150-230 DEG C of scope.The material extruded is product through cooling and dicing under water.
Product performance are as follows:
Hardness (Shao A) 90;
Shock elasticity/% 35;
100% stress at definite elongation/MPa 9.5;
300% stress at definite elongation/MPa 13.5;
Tensile strength/MPa 42;
Tensile yield/% 650;
Tear strength N/mm 130.
embodiments of the invention 4:
Contrast sample
MDI 64.27kg；
Poly-hexanodioic acid-glycol ester (Mn is 2000) 117.0kg;
BDO 18.08kg;
Antioxidant 1010 2.9kg.
Under abundant stirring condition, under poly-hexanodioic acid-glycol ester is heated to the temperature of 90 DEG C-120 DEG C (optimal selection 105 DEG C-110 DEG C) vacuumize dehydration.Maintain the temperature at 80-100 DEG C after processed, and add oxidation inhibitor, fully stir and make it be uniformly dispersed.1.4-butyleneglycol is also preheating to 80-100 DEG C simultaneously, MDI is preheating to 40-60 DEG C, then other is divided to squeeze in high-speed mixing head with precision metering pump, rotor intense mixing through high speed rotating is even, add continuously in twin screw extruder, twin screw extruder temperature controls 150-230 DEG C of scope.The material extruded is product through cooling and dicing under water.
Product performance are as follows:
Hardness (Shao A) 90;
Shock elasticity/% 30;
100% stress at definite elongation/MPa 9;
300% stress at definite elongation/MPa 12.5;
Tensile strength/MPa 40;
Tensile yield/% 600;
Tear strength N/mm 135.
In the present invention, generally all can add appropriate oxidation inhibitor in the preparation, and other such as photostabilizer, lubricants, and the interpolation of catalyzer, all can select according to real needs, and be not limited to several additives that the present invention limits.
Claims (10)
1. the method using soles system isocyanate component to prepare Polyurethane Thermoplastic Elastomer, it is characterized in that the method utilize polyurethane shoe-sole stoste isocyanate component and there is the polyester of activity hydroxy or polyether-type oligomer compounds, small molecules dibasic alcohol, auxiliary agent carry out being mixed with and obtain described Polyurethane Thermoplastic Elastomer, specifically comprise the steps:
(1), under abundant stirring condition, will polyester or the heating of polyether-type oligomer compounds of activity hydroxy be had, at 90-120 DEG C, vacuumize dehydration, 80-100 DEG C is maintained the temperature at after dehydration, and add auxiliary agent, fully stir and auxiliary agent is uniformly dispersed, obtain mixture I;
(2), simultaneously, small molecules dibasic alcohol is preheated to 80-100 DEG C, soles system isocyanate component is preheated to 40-60 DEG C:
(3), by I in the small molecules dibasic alcohol through thermal pretreatment in step (2), soles system isocyanate component respectively Homogeneous phase mixing to step (1) gained mixture, obtain mixtures II, then obtain Polyurethane Thermoplastic Elastomer through aftertreatment granulation.
2. the use soles system isocyanate component according to claim l prepares the method for Polyurethane Thermoplastic Elastomer, it is characterized in that: described in there is activity hydroxy polyester for containing two activity hydroxies, the equal relative molecular mass of number is the polyester glycol of 1000,2000,1500,1800,3000 or 4000, the described polyether-type oligomer compounds with activity hydroxy is containing two activity hydroxies, and the equal relative molecular mass of number is the polyoxytrimethylene ether glycol of 1000,2000,1500,1800,3000,4000.
3. use soles system isocyanate component according to claim 2 prepares the method for Polyurethane Thermoplastic Elastomer, it is characterized in that: described polyester glycol is hexanodioic acid and ethylene glycol, l, the hexanodioic acid system polyester glycol of 4-butyleneglycol, l, 6-hexylene glycol, methyl propanediol, glycol ether or neopentyl glycol synthesis; Or the mixture of hexanodioic acid system polyester and phthalic anhydride system polyester glycol, and the content of phthalic anhydride system polyester glycol is 0 ~ 40% in mixture, described phthalic anhydride system polyester glycol refers to by phthalic anhydride and ethylene glycol, l, the polyester glycol of 4-butyleneglycol, l, 6-hexylene glycol, methyl propanediol, glycol ether or neopentyl glycol synthesis.
4. the use soles system isocyanate component according to claim l prepares the method for Polyurethane Thermoplastic Elastomer, it is characterized in that: described small molecules dibasic alcohol is l, 4-butyleneglycol, ethylene glycol, l, ammediol, glycol ether, l, one in 6-hexylene glycol, methyl propanediol, neopentyl glycol, quinhydrones two (2-hydroxyethyl) ether, Resorcinol double hydroxyethyl ether or l, 3-butyleneglycol.
5. the use soles system isocyanate component according to claim l prepares the method for Polyurethane Thermoplastic Elastomer, it is characterized in that: described auxiliary agent is one or more in oxidation inhibitor, photostabilizer or lubricant.
6. use soles system isocyanate component according to claim 5 prepares the method for Polyurethane Thermoplastic Elastomer, it is characterized in that: described oxidation inhibitor is the mixed thing that Hinered phenols antioxidant and phosphorous acid esters disturb oxygen agent, the mass ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant is 5:1-1:2, wherein, Hinered phenols antioxidant is four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, 2, the mixture of one or more in 6-di-tert-butyl-4-methy phenol, phosphite ester kind antioxidant is tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, two [2-methyl-4, 6-bis-(1, l '-dimethyl ethyl) phenol] ethyl ester, four (2, 4-di-tert-butyl-phenyl-4, 4 '-xenyl) mixture of one or more in biphosphonate, the quality of the add-on of oxidation inhibitor is the 0.2-2% of formula total mass.
7. use soles system isocyanate component according to claim 5 prepares the method for Polyurethane Thermoplastic Elastomer, it is characterized in that: described photostabilizer is UV light absorber, for Octabenzone, ESCALOL 567, 2-(2 '-hydroxyl-3 ', 5 '-diamyl phenyl) benzotriazole, 2-(2-hydroxyl-5'-aminomethyl phenyl) benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorinated benzotriazole, 2-(2 '-hydroxyl-5 '-Te octyl phenyl) benzotriazole, 2, 2 '-methylene support-bis-(tertiary octyl phenyl phenol of 6-benzotriazole-4), two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) sebate, two-2, 2, 6, the mixed thing of one or more in 6-tetramethyl piperidine alcohol ester, the quality of the add-on of this photostabilizer is the 0.1-1% of formula total mass.
8. use soles system isocyanate component according to claim 5 prepares the method for Polyurethane Thermoplastic Elastomer, it is characterized in that: described lubricant is stearate, amine hydroxybenzene, N, N, one in-ethylenebisstearamide, montanin wax, the quality of the add-on of this lubricant is the 0.05-5% of formula total mass.
9. the use soles system isocyanate component according to claim l prepares the method for Polyurethane Thermoplastic Elastomer, it is characterized in that: when adding auxiliary agent in described step (1), also add catalyzer, described catalyzer is the one in stannous octoate, dibutyl tin dilaurate, tetrabutyl titanate, titanium isopropylate or organo-bismuth, and the quality of the add-on of this catalyzer is the 0-0.05% of formula total mass.
10. the use soles system isocyanate component according to claim l prepares the method for Polyurethane Thermoplastic Elastomer, it is characterized in that:
The described aftertreatment granulation of step (3) refers to that mixtures II being added continuously temperature range controls in the twin screw extruder of 150-230 DEG C, and extruded material, through cooling and dicing under water, obtains Polyurethane Thermoplastic Elastomer product;
Or, being noted by mixtures II scribbles on the stainless steel conveyor belt of tetrafluoroethylene, sending into is connected with in the drying tunnel of nitrogen, keep conveyor belt temperature at 120-125 DEG C, the material solidified by drying tunnel is after fragmentation, use twin screw extruder extruding pelletization at 140-180 DEG C again, obtain Polyurethane Thermoplastic Elastomer product;
Or, mixtures II is poured into and scribbles in the stainless steel charging tray of tetrafluoroethylene, be placed with in the baking oven of nitrogen protection, dry 4 hours at 140-150 DEG C, be broken into particle after cooling, obtain Polyurethane Thermoplastic Elastomer product.
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| CN105669929A (en) * | 2016-03-21 | 2016-06-15 | 美瑞新材料股份有限公司 | Engineering thermoplastic polyurethane elastomer and preparation method thereof |
| CN108659196A (en) * | 2018-03-27 | 2018-10-16 | 中科宏德（北京）科技发展有限公司 | A kind of thermoplastic polyurethane elastomer and preparation method thereof |
| CN109232854A (en) * | 2018-06-19 | 2019-01-18 | 旭川化学（昆山）有限公司 | A kind of production technology of low-density high abrasion polyurethane sole materials |
| CN110041490A (en) * | 2019-04-28 | 2019-07-23 | 东莞华工佛塑新材料有限公司 | A kind of preparation method and application of polyurethane elastomer sole material |
| CN111875857A (en) * | 2020-07-14 | 2020-11-03 | 林扬发 | Polyether sole |
| CN116425945B (en) * | 2023-05-15 | 2024-02-06 | 东莞华工佛塑新材料有限公司 | Polyurethane elastomer glazed-drop sole and preparation method thereof |
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| CN103059260A (en) | 2013-04-24 |
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