CN1986592A - Method for raising mechanical performace of microporous polyether-type polyurethane elastomer - Google Patents
Method for raising mechanical performace of microporous polyether-type polyurethane elastomer Download PDFInfo
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- CN1986592A CN1986592A CN 200510062183 CN200510062183A CN1986592A CN 1986592 A CN1986592 A CN 1986592A CN 200510062183 CN200510062183 CN 200510062183 CN 200510062183 A CN200510062183 A CN 200510062183A CN 1986592 A CN1986592 A CN 1986592A
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Abstract
The present invention discloses method of raising mechanical performance of microporous polyether-type polyurethane elastomer. The present invention prepares microporous polyether-type polyurethane elastomer through the following steps: mixing polyether polyol, small molecular weight diamine chain expander, catalyst, bubble homogenizing agent and foaming agent through stirring to form the first component; mixing polyether polyol, isocyanate and side reaction inhibitor at 60-80 deg.c to react for 2-3 hr, vacuum debubbling and cooling to obtain the second component; mixing two components and molding to obtain the microporous polyether-type polyurethane elastomer. The microporous polyether-type polyurethane elastomer has high mechanical performance.
Description
Technical field
The present invention relates to improve a kind of method of microporous polyether-type polyurethane elastomer and the microporous polyether-type polyurethane elastomer for preparing according to this method.
Background technology
Urethane is a kind of Multifunction macromolecular material, combines the premium properties of rubber and plastics, is one of the synthetic materials of tool development prospect in the world today, is widely used in every field such as synthon, shoe-making industry, automotive industry, medicine equipment.
Shoe-making industry has become an important industry of consumption polyurethane product at present.Chinese population is numerous, and the polyurethane in use for shoes starting material have wide development space, in particular for producing the microporous polyurethane elastomer of sole.The microporous polyurethane elastomer that is used for sole mainly contains two kinds, i.e. polyester type and polyether-type.At present mainly based on PAUR, be because the physical and mechanical properties of PAUR is good, can satisfy different processing needs, but this type of urethane is because low-temperature performance and hydrolytic resistance are poor, facile hydrolysis and easily go mouldy, process also more complicated has limited its application in some aspects to a great extent.And polyether(poly)urethane exactly has many PAUR advantage can't be obtained, as: hydrolysis, anti-mildew become, low-temperature flexibility, the anti-flexing fatigue of excellence.In addition, polyether(poly)urethane stoste normal temperature is liquid down, and viscosity is low, and is easy to operate, and the foaming wide ranges is convenient to control.In the area of awful weather,, cold district big as rainfall amount and moist working space just have the irreplaceable effect of PAUR sole at the bottom of the polyether type polyurethane shoes.But for fear of the poor mechanical property of polyether(poly)urethane, the present polyether(poly)urethane of China is mainly used in and is used for the not too high sandals of production machinery performance requriements, slippers, playshoes.And the U.S., Japan, Korea S, polyether-type and PAUR sole have half share.We can say as long as improve the popularization that mechanical performace of microporous polyether-type polyurethane elastomer just can promote polyether(poly)urethane effectively effectively.Domestic research to polyether(poly)urethane at present is quite extensive, but especially tensile strength and elongation still are not significantly improved on mechanical property.
Publication number is the preparation method that the patent of invention of CN1189499C discloses a kind of polyether type polyurethane shoes bottom material, make whipping agent with water, utilize DMC catalysts synthetic novel high-activity, low-unsaturated polyether polyatomic alcohol and adopt part to contain the small molecules properties-correcting agent of active hydrogen and polyol blends component through thorough mixing, cast, foaming, the demoulding, made microporous polyurethane elastomer, make this material in tensile strength, tear strength, elongation, performances such as tension set are improved significantly, and are also demonstrating stronger advantage aspect low temperature brittleness performance and the resistance to deflection energy.
" elastomerics " 2003 the 1st phase 33-37 pages or leaves, Liu Ling, Kang Maoqing, Zhang Zhixin, Wang Xinkui have introduced reaction system, reaction principle and the use properties of polyether-urethane microcellular elastomer shoe sole in " polyether-urethane microcellular elastomer shoe sole " literary composition, in this paper, mention the polyamine compounds and make chainextender, but because-NH
2With-the NCO speed of response is quite fast, makes gelation rate and expansion rate in the Sole moulding process be difficult to balance, causes the Flow of Goods and Materials time short.And contain the stronger urea groups of polarity in the polyurethane molecular of amine chain extension, and cause the hardness of micro-pore elastomer higher, so the author thinks that amine chain extender is unsuitable for doing sole, industrial widely used chainextender is an aliphatic polyol.
Summary of the invention
The invention provides a kind of method that improves mechanical performace of microporous polyether-type polyurethane elastomer, prescription and employing small molecules diamine chain stretching agent by adjusting synthesis of polyurethane make the main physical properties of polyether-type micro-pore elastomer such as tensile strength, elongation etc. be significantly improved.
A kind of method that improves mechanical performace of microporous polyether-type polyurethane elastomer comprises:
1.A the preparation of group component: polyether glycol, polyether polyol, small molecules diamine chain stretching agent, tertiary amines or tin class catalyzer, silicone based foam stabilizer, water/pneumatogen are pressed column weight amount proportioning: polyether glycol: polyether polyol: small molecules diamine chain stretching agent: tertiary amines or tin class catalyzer: silicone based foam stabilizer: water/pneumatogen=70～90: 30～10: 5～30: 0.2～10: 0.5～2.5: 0.01～5, after placing the container thorough mixing evenly, discharging again, sealing is preserved;
2.B the preparation of group component: polyether glycol, isocyanic ester and auxiliary agent are pressed column weight amount proportioning: polyether glycol: isocyanic ester=40～60: 60～40, add an amount of side reaction hold back agent, 60～80 ℃ of reactions 2～3 hours, the vacuum removal bubble, naturally cooling, discharging, analyze free-NCO content, sealing is preserved;
3. the preparation of microporous polyether-type polyurethane elastomer: make A group component temperature maintain 30～35 ℃, make B group component temperature maintain 40～45 ℃, by the mole number of the active hydrogen of A component and B component-ratio of the mole number of NCO is 100: 100, with two component thorough mixing, it is molded to inject mould.
Polyether glycol in the preparation of described A component can be selected polyether polyol with high activity for use, polyether polyol with high activity is the polyether glycol of the ultra-high molecular weight low-unsaturation-degree of bimetallic complex catalyst polycoordination of the prior art, and molecular weight is 2000～6000, functionality is 2.0 or 3.0, degree of unsaturation is less than the polyether glycol of 0.005meq/g.Existing in the market the sale is as accailm-2220, the accailm-4220 of U.S. ARCO company, accailm-6220 etc.
Described small molecules diamine chain stretching agent is selected from aromatic diamine, and the ortho position of amido is replaced by electron-withdrawing group.
Described small molecules diamine chain stretching agent is 3,3 '-dichloro-4,4,4 '-diphenylmethyl phenylenediamine (MOCA), 3,5-diformazan sulfenyl tolylene diamine (DMTDA) or 3,5-diethyl toluene diamine (DETDA).
According to the microporous polyether-type polyurethane elastomer of method for preparing, this micro-pore elastomer can be used for material for sole of shoe and is particularly useful for athletic shoe sole.
It is that vinyl monomer and trihydroxy-polyether glycol carry out graft reaction and form with vinyl cyanide, vinylbenzene etc. that polyether polyol is selected for use of the prior art, and this material is commercially available.
Remaining common polyether glycol, silicone based foam stabilizer, water/pneumatogen, tertiary amines or tin class catalyzer, isocyanic ester all adopt the commercially available raw material commonly used of preparation polyether-polyurethane elastomer material, and the side reaction hold back agent that is used to prepare the B component adopts modal phosphoric acid.
The present invention selects suitable polyether glycol and polyether polyol, excellent rate elongation and lower temperature resistance is provided, by adjusting the composition of each raw material, chainextender selects for use amido to be connected on above the phenyl ring and the ortho position of amido is generally replaced to limit its active small molecules two amine chainextenders by halogen or other electron-withdrawing group, overcome amine chain extender and be not suitable for the prejudice in the material for sole of shoe preparation, used, adopt small molecules amine chainextender to replace general glycols chainextender, and satisfy other performance requriements of processing requirement and finished product in the process, as cream time, the demoulding time, feel, rebound performances etc. make the polyether-type micro-pore elastomer that makes at 0.55g/cm
3Compact density under tensile strength greater than 5.0MPa, elongation has solved the problem of mechanical performace of microporous polyether-type polyurethane elastomer difference greater than 300%.
Embodiment
Come with the production instance of polyurethane sole materials below that the present invention is further elaborated, but do not limit the scope of the invention.
Embodiment 1
Metering by weight ratio takes by weighing each constitutive material of A group component: molecular weight is 2000～6000 polyether polyol with high activity 88 weight parts, polyether polyol 12 weight parts, 3,3 '-two chloro-4,4 '-after diphenylmethyl phenylenediamine (MOCA) 12 weight parts, tertiary amine catalyst 2 weight parts, silicone based foam stabilizer 0.2 weight part, water 0.045 weight part place the container thorough mixing evenly, discharging again, sealing is preserved;
Metering by weight ratio takes by weighing each constitutive material of B group component: polyether glycol 53 weight parts, isocyanic ester 47 weight parts, and phosphoric acid was an amount of, 60～80 ℃ of reactions 2～3 hours, the vacuum removal bubble, naturally free-NCO content is analyzed in cooling, discharging, and sealing is preserved;
Make A group component temperature maintain 30～35 ℃, make B group component temperature maintain 40～45 ℃, with A, B group component thorough mixing, it is molded to inject mould.
The product that makes is carried out Mechanics Performance Testing, and the result is as follows:
Physicals: density 0.548g/cm
3, tensile strength 5.56Mpa, elongation 376%.
Embodiment 2
Metering by weight ratio takes by weighing each constitutive material of A group component: molecular weight is 2000～6000 polyether polyol with high activity 90 weight parts, polyether polyol 10 weight parts, 3, after 5-diformazan sulfenyl tolylene diamine (DMTDA) 12.5 weight parts, tertiary amine catalyst 2 weight parts, silicone based foam stabilizer 0.2 weight part, water 0.045 weight part place the container thorough mixing evenly, discharging again, sealing is preserved.
Metering by weight ratio takes by weighing each constitutive material of B group component: polyether glycol 53 weight parts, isocyanic ester 60 weight parts, and phosphoric acid was an amount of, 60～80 ℃ of reactions 2～3 hours, the vacuum removal bubble, naturally free-NCO content is analyzed in cooling, discharging, and sealing is preserved;
Make A group component temperature maintain 30～35 ℃, make B group component temperature maintain 40～45 ℃, with A, B group component thorough mixing, it is molded to inject mould.
The product that makes is carried out performance test, and the result is as follows:
Physicals: density 0.554g/cm
3, tensile strength 6.17Mpa, elongation 372%.
Embodiment 3
Metering by weight ratio takes by weighing each constitutive material of A group component: polyether polyol with high activity 87 weight parts, polyether glycol 13 weight parts, 3, after 5-diethyl toluene diamine (DETDA) 13.8 weight parts, tertiary amine catalyst 2.3 weight parts, silicone based foam stabilizer 0.2 weight part, water 0.045 weight part place the container thorough mixing evenly, discharging again, sealing is preserved.
Metering by weight ratio takes by weighing each constitutive material of B group component: polyether glycol 40 weight parts, isocyanic ester 60 weight parts, and phosphoric acid was an amount of, 60～80 ℃ of reactions 2～3 hours, the vacuum removal bubble, naturally free-NCO content is analyzed in cooling, discharging, and sealing is preserved;
Make A group component temperature maintenance at 30～35 ℃, make B group component temperature maintain 40～45 ℃, with A, B group component thorough mixing, it is molded to inject mould.
The product that makes is carried out performance test, and the result is as follows:
Physicals: density 0.550g/cm
3, tensile strength 5.62Mpa, elongation 320%.
Guaranteeing to change polyether polyol with high activity into common polyether glycol with under the situation of amine chain extender, as following embodiment, the mechanical property of the urethane ester micro-pore elastomer that obtains is still more satisfactory.
Common polyether glycol can be selected from Tianjin the 3rd petrochemicals, and product are called TED-28, TEP-240.
Embodiment 4
Metering by weight ratio takes by weighing each constitutive material of A group component: common polyether glycol 88 weight parts, polyether polyol 12 weight parts, 3,3 '-two chloro-4,4 '-after diphenylmethyl phenylenediamine (MOCA) 13 weight parts, tertiary amine catalyst 2.2 weight parts, silicone based foam stabilizer 0.2 weight part, water 0.045 weight part place the container thorough mixing evenly, discharging again, sealing is preserved;
Metering by weight ratio takes by weighing each constitutive material of B component: polyether glycol 40 weight parts, isocyanic ester 60 weight parts, and phosphoric acid was an amount of, 60～80 ℃ of reactions 2～3 hours, the vacuum removal bubble, naturally free-NCO content is analyzed in cooling, discharging, and sealing is preserved;
Make A group component temperature maintenance at 30～35 ℃, make B group component temperature maintain 40～45 ℃, with A, B group component thorough mixing, it is molded to inject mould.
The product that makes is carried out performance test, and the result is as follows:
Physicals: density 0.554g/cm
3, tensile strength 5.21Mpa, elongation 551%.
Said products is as material for sole of shoe, has lightweight, resiliency is good, and mechanical property is good, keeps stability and long-acting wearing quality under hot and humid condition.
Claims (7)
1. method that improves mechanical performace of microporous polyether-type polyurethane elastomer comprises:
(1) preparation of A component:
Each raw material of A component is pressed the row weight part place container, thorough mixing discharging after 2～4 hours, sealing is preserved;
Polyether glycol 70～90 weight parts
Polyether polyol 30～10 weight parts
Small molecules diamine chain stretching agent 5～30 weight parts
Tertiary amines or tin class catalyzer 0.2～10 weight part
Silicone based foam stabilizer 0.5～2.5 weight part
Water/pneumatogen 0.01～5 weight part
(2) preparation of B component:
Each raw material of B component is pressed the row weight part reacted 2～3 hours under 60～80 ℃ of conditions, the vacuum removal bubble is cooled to 40～45 ℃, discharging, analyzes free-NCO content, and sealing is preserved;
Isocyanic ester 40～60 weight parts
Polyether glycol 60～40 weight parts
The side reaction hold back agent is an amount of
(3) preparation of microporous polyether-type polyurethane elastomer: make the A component temperature maintain 35～40 ℃, the B component temperature maintains 40～45 ℃, by the mole number of the active hydrogen of A component and B component-ratio of the mole number of NCO is 100: 100, with two component thorough mixing, it is molded to inject mould.
2. the method for raising mechanical performace of microporous polyether-type polyurethane elastomer according to claim 1 is characterized in that: the polyether glycol in the preparation of described A component is selected polyether polyol with high activity or common polyether glycol for use.
3. the method for raising mechanical performace of microporous polyether-type polyurethane elastomer according to claim 2 is characterized in that: described small molecules diamine chain stretching agent is selected from aromatic diamine.
4. the method for the mechanical property of raising microporous polyether-type polyurethane elastomer according to claim 3 is characterized in that: there is the electron-withdrawing group substituting group at the ortho position of described small molecules diamine chain stretching agent amido.
5. according to the method for claim 3 or 4 described raising mechanical performace of microporous polyether-type polyurethane elastomer, it is characterized in that: described small molecules diamine chain stretching agent be 3,3 '-two chloro-4,4 '-diphenylmethyl phenylenediamine, 3,5-diformazan sulfenyl tolylene diamine or 3, the 5-diethyl toluene diamine.
6. according to the microporous polyether-type polyurethane elastomer of the arbitrary described method preparation of claim 1-5.
7. microporous polyether-type polyurethane elastomer according to claim 6 is as the application of material for sole of shoe.
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| CN 200510062183 CN1986592A (en) | 2005-12-23 | 2005-12-23 | Method for raising mechanical performace of microporous polyether-type polyurethane elastomer |
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Cited By (11)
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|---|---|---|---|---|
| WO2010115567A1 (en) | 2009-04-10 | 2010-10-14 | Bayer Materialscience Ag | Polyurethane microcellular elastomer, method for preparing same and use thereof |
| CN101328254B (en) * | 2008-07-29 | 2011-04-06 | 浙江华峰新材料股份有限公司 | Polyester type polyurethane micropore elastomer added with low cost polycarbonate polyatomic alcohol and preparation thereof |
| CN101486788B (en) * | 2008-12-30 | 2011-09-14 | 浙江华峰新材料股份有限公司 | Low density high hardness polyurethane micropore elastomer and preparation thereof |
| CN101486834B (en) * | 2008-12-30 | 2012-06-27 | 浙江华峰新材料股份有限公司 | High performance nano polyurethane micropore elastomer composite material and preparation thereof |
| WO2013091271A1 (en) * | 2011-12-23 | 2013-06-27 | 山东东大一诺威聚氨酯有限公司 | Microporous polyurethane elastomer composition with excellent dynamic performance and method for preparing same |
| CN103467974A (en) * | 2013-09-06 | 2013-12-25 | 重庆杰博科技有限公司 | Enhanced polyurethane microcellular elastomer composite material and preparation method thereof |
| CN103483533A (en) * | 2013-09-23 | 2014-01-01 | 句容市睿远科技有限公司 | Elastomer for damping backing plate of high-speed rail and preparation method thereof |
| CN105693970A (en) * | 2016-01-29 | 2016-06-22 | 大连固瑞聚氨酯股份有限公司 | Polyether-type microporous hard polyurethane shoe sole combination raw solution and polyurethane shoe sole |
| CN109096460A (en) * | 2018-08-08 | 2018-12-28 | 山东诺威聚氨酯股份有限公司 | Polyurethane elastomer and preparation method thereof for making foaming shoe material |
| CN110746923A (en) * | 2019-06-21 | 2020-02-04 | 南京威邦新材料有限公司 | Flame-retardant heat-resistant double-component polyurethane lawn gum for artificial lawn |
| CN112279997A (en) * | 2020-10-26 | 2021-01-29 | 温州志途鞋业有限公司 | Sole and preparation method thereof |
-
2005
- 2005-12-23 CN CN 200510062183 patent/CN1986592A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101328254B (en) * | 2008-07-29 | 2011-04-06 | 浙江华峰新材料股份有限公司 | Polyester type polyurethane micropore elastomer added with low cost polycarbonate polyatomic alcohol and preparation thereof |
| CN101486788B (en) * | 2008-12-30 | 2011-09-14 | 浙江华峰新材料股份有限公司 | Low density high hardness polyurethane micropore elastomer and preparation thereof |
| CN101486834B (en) * | 2008-12-30 | 2012-06-27 | 浙江华峰新材料股份有限公司 | High performance nano polyurethane micropore elastomer composite material and preparation thereof |
| WO2010115567A1 (en) | 2009-04-10 | 2010-10-14 | Bayer Materialscience Ag | Polyurethane microcellular elastomer, method for preparing same and use thereof |
| DE112010001561T5 (en) | 2009-04-10 | 2012-09-13 | Bayer Materialscience Aktiengesellschaft | Microcellular polyurethane elastomer, process for its preparation and use thereof |
| WO2013091271A1 (en) * | 2011-12-23 | 2013-06-27 | 山东东大一诺威聚氨酯有限公司 | Microporous polyurethane elastomer composition with excellent dynamic performance and method for preparing same |
| CN103467974A (en) * | 2013-09-06 | 2013-12-25 | 重庆杰博科技有限公司 | Enhanced polyurethane microcellular elastomer composite material and preparation method thereof |
| CN103483533A (en) * | 2013-09-23 | 2014-01-01 | 句容市睿远科技有限公司 | Elastomer for damping backing plate of high-speed rail and preparation method thereof |
| CN105693970A (en) * | 2016-01-29 | 2016-06-22 | 大连固瑞聚氨酯股份有限公司 | Polyether-type microporous hard polyurethane shoe sole combination raw solution and polyurethane shoe sole |
| CN109096460A (en) * | 2018-08-08 | 2018-12-28 | 山东诺威聚氨酯股份有限公司 | Polyurethane elastomer and preparation method thereof for making foaming shoe material |
| CN109096460B (en) * | 2018-08-08 | 2021-04-16 | 山东一诺威聚氨酯股份有限公司 | Polyurethane elastomer for manufacturing foamed shoe material and preparation method thereof |
| CN110746923A (en) * | 2019-06-21 | 2020-02-04 | 南京威邦新材料有限公司 | Flame-retardant heat-resistant double-component polyurethane lawn gum for artificial lawn |
| CN112279997A (en) * | 2020-10-26 | 2021-01-29 | 温州志途鞋业有限公司 | Sole and preparation method thereof |
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