CN103525080A - Production technology and application method of thermoplastic polyurethane elastomer - Google Patents
Production technology and application method of thermoplastic polyurethane elastomer Download PDFInfo
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Abstract
The invention provides a production method and an application method of a thermoplastic polyurethane elastomer. The thermoplastic polyurethane elastomer is mainly characterized by high flexibility, low-temperature resistance, hydrolysis resistance, flame retardance and electric insulation property and also has high mechanical property and is widely applied to aerospace, automobile production, electromechanical equipment, transmission equipment, textile fiber, adhesives, underwater cables, sealing components and the like; moreover, the formula, the production technology and the application method of the material are described in details according to the market needs, and particularly, the comprehensive performance and the hardness index 50+/-5 Shore A of the material are a new breakthrough of the thermoplastic polyurethane (TPU) elastomer.
Description
Technical field
The present invention relates to a kind of new chemical materials, and preparation method thereof with synthetic its molar weight proportioning of use field, especially first component and component B be crucial, the over-all properties of different its products of proportioning is different.
Background technology
The fast development of China's economy, the one, the energy is basis, the 2nd, industrial chemicals is indispensable as the intermediate of basic industry development, and needs derived product to be widely used, and excellent performance is stable, and accumulating is convenient, clean, the Elementary Chemical Industry raw material of environmental protection.The U.S., Germany, Japan are at the seventies, basic chemical industry raw material is just dropped into huge fund research and development, and achievement in research is applied to aerospace, electromechanical equipment, petrochemical complex, mine especially transmission apparatus and automobile manufacturing field, in above-mentioned field, contribution has been made in the scientific and technological and economic development in U.S., day, the Qian Mao，Wei world, the leading countries in the world of moral.
Nowadays the Chinese development of demand, development of world economy also be unable to do without the development of China's economic, under this background, we have developed by liquid chemical raw material, through chemical cessation reaction, reach excellent performance, stable, cleaning ambient, accumulating, application is convenient, and Polyurethane Thermoplastic Elastomer micelle is TPU efficiently, 25% left and right of TPUZhan world polyurethane elastomer total amount, and cumulative year after year, in the compacting elastomerics that global total amount in 2000 is 1,000,000 tons, TPU is approximately 220,000 tons, TPU is block polymer, by intermolecular hydrogen bond, form physical crosslinking, there is higher physical strength, thermoplastic polyurethane can be by the polymerization of body method of fusion or solution polymerization, commodity TPU is normally granular, can re-workability good, can adopt thermoplastics processing method, as: extrude, injection moulding, calendering, blowing, mold pressing etc., by TPU particle at comparatively high temps plasticizing forming, make goods or the composite product of different shape, that wherein with extrusion molding or injection moulding, applies is maximum, TPU main application has: aerospace, electromechanical equipment, trolley part, rubber roll, rubber cushion, electric wire, flexible pipe, film and spandex fiber, synthetic leather resin and tackiness agent etc.
Summary of the invention
Goal of the invention: the technical problem that will solve required for the present invention is the deficiency for thermoplastic elastomer, a kind of composition of improved Polyurethane Thermoplastic Elastomer is provided, said composition can be prepared hardness at the Polyurethane Thermoplastic Elastomer micelle TPU of 50 ± 5 Shao Shi A, and its excellent performance has good snappiness, wear resistance, low temperature resistant, hydrolysis etc.The present invention describes the basic recipe of thermoplastic urethane elastomer composition in detail, the using method of the production technique of Polyurethane Thermoplastic Elastomer micelle and Polyurethane Thermoplastic Elastomer micelle.
Technical scheme:
The present invention is that to solve the problems of the technologies described above adopted technical scheme as follows:
, said composition minute first, second two components package spare respectively.First component according to the mass fraction, is comprised of following component: 50-100 parts of polyether glycols; 5-30 parts of chain extension-crosslinking agent; 0-30 parts of tougheners; 0-6 parts of stablizers; 0-20 parts of defoamers; 0-5 parts of fire retardants; 0-30 parts of anti-electrostatic, low temperature resistant, hydrolysis agent; 0-100 parts of fillers.
Component B is isocyanic ester or compound isocyanic ester or its prepolymer, and the mass ratio of first component and component B is 5:1-1:1.
Above-mentioned thermoplastic urethane elastomer composition, wherein polyether glycol is Polyoxypropylene diol, polyoxypropylene polyol; Propylene oxide and ethylene oxide copolymer; Polymer polyatomic alcohol etc.
Above-mentioned thermoplastic urethane elastomer composition, its crosslinked chainextender is: ethylene glycol, Isosorbide-5-Nitrae one butyleneglycol, Viscotrol C, EL-303 etc.
Above-mentioned thermoplastic urethane elastomer composition, wherein stablizer is by oxidation inhibitor and UV light absorber is compound adds, and its oxidation inhibitor is: anti-aging agent-264, oxidation inhibitor-1010, UV light absorber is UV-327, UV-531, by antioxidant 1010 and UV light absorber UV-327, compound adding in TPU composition, addition is 1%-3%, through senile experiment, its ageing-resistant particular significant effect, preferably.
Above-mentioned thermoplastic urethane elastomer composition, wherein, anti-electrostatic, low temperature resistant, hydrolysis agent are refined caster oil, its add-on is 0-30 parts, preferably 3-10 parts; Its performance also can play crosslinked chain extension effect.
Above-mentioned thermoplastic urethane elastomer composition, wherein fire retardant is reactive flame retardant, as: Diethylene Glycol phosphoric acid ester; Three (polyoxygenated alkene) phosphoric acid ester; Three (polyoxygenated alkene) phosphorous acid ester; Preferred Diethylene Glycol phosphoric acid ester.
Above-mentioned thermoplastic urethane elastomer composition, wherein toughener has selected grafted polyether polyol also to claim 0-30 parts of polymer polyatomic alcohol EL-920, EL-943, EL-945, add-on.
Above-mentioned thermoplastic urethane elastomer composition, wherein filler is calcium carbonate, silicon-dioxide etc., and filling adding amount is 0-100 parts, and granularity is 180-1200 orders.
Above-mentioned thermoplastic urethane elastomer composition, wherein defoamer is 0-20 parts of silicane defoamer or CaO add-ons.
Above-mentioned thermoplastic urethane elastomer composition, wherein in component B, isocyanic ester is isophorone diisocyanate, tolylene diisocyanate or compound isocyanic ester, preferred isophorone diisocyanate, its add-on should be greater than compound isocyanic ester 50%, and product over-all properties is excellent especially.
The method of preparing above-mentioned TPU composition, comprises the following steps:
1, polyether TPU first component preparation method: first, by design proportioning, all treated qualified first component measuring is added in the lump in still and stirs and heat up, when still temperature rise to 100 ℃, start to vacuumize, overbottom pressure is that 400-667PA(vacuum meter approaches 0.098Mpa), 120 ℃ of insulations vacuumize 1-3 hours, analysis moisture≤0.05%, cooling discharge, standby after packing.
2, at 70 ℃---at 100 ℃, first isophorone diisocyanate (IPDI) is dissolved with tolylene diisocyanate (TDI) and make compound isocyanic ester by design proportioning, its proportioning is that IPDI:TDI=1:1-2:1 or IPDI and polyether glycol are made performed polymer, NCO% value is set within 3%-50%, standby as component B.
Above-mentioned polyether glycol molecular weight is 200-6000, and preferably dibasic alcohol or polyvalent alcohol, select according to over-all properties and the comprehensive cost setting of TPU.Generally select dibasic alcohol, molecular weight is between 400-3000, and the present invention selects dibasic alcohol and polyvalent alcohol and uses, molecular weight is between 500-6000, preferred molecular weight, between 1000-5000, has reduced cost, the raising of having got back of tensile strength and tear strength.
Preparation Polyurethane Thermoplastic Elastomer micelle production technique and method are as follows:
First, equipment is selected:
Select one of suitable casting molding machine, one of curing oven, one of cutting and grinding tablets press, pallet n, one of transfer equipment, one, drying machine; Because twin screw extruder is expensive, home equipment continous-stable is inadequate, therefore do not describe in detail.
Then, first, second two components are added respectively in casting molding machine basin, stir and heat up; first component temperature is controlled at 80-110 ℃, and component B temperature is controlled at 80-100 ℃, vacuum defoamation; set metering, mix and pour into a mould in the pallet of having got ready, in transfer equipment is sent into 100 ℃ of-130 ℃ of curing ovens; through slaking in 1-3 hours; be cooled to normal temperature, blob of viscose disk stripping, sends into pulverize in tablets press and cuts granulation; last drying and processing, verification test, packing are TPU micelle.
Claims (9)
1. a Polyurethane Thermoplastic Elastomer, said composition divides first, second two components for the ease of subsequent production, first component: 50-100 parts of polyether glycols, 5-30 parts of crosslinked chainextenders, 0-30 parts of tougheners, 0-6 parts of stablizers, 0-5 parts of fire retardants, 0-30 parts of anti-electrostatic, low temperature resistant, hydrolysis agent, 0-100 parts of fillers, 0-20 parts of defoamers; Component B is: isocyanic ester, compound isocyanic ester or its prepolymer; And the mass ratio of first component and component B is 5:1-1:1.
2. a kind of Polyurethane Thermoplastic Elastomer according to claim 1, its feature is that described polyether glycol is the rare dibasic alcohol of polyoxygenated third, the rare polyvalent alcohol of polyoxygenated third, propylene oxide and ethylene oxide copolymer, polymer polyatomic alcohol etc.
3. according to patent, require a kind of Polyurethane Thermoplastic Elastomer described in 1, it is characterized in that described isocyanic ester is isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI).
According to right require a kind of Polyurethane Thermoplastic Elastomer described in 1, the chain extension-crosslinking agent described in its feature is small molecules amount dibasic alcohol or small molecules weight polyalcohol class.
5. a kind of Polyurethane Thermoplastic Elastomer according to claim 1, its feature is that a kind of average functionality is 2.7 in described anti-electrostatic, low temperature resistant, hydrolysis agent, hydroxyl value is 163mgkoH/g, the Viscotrol C that plant seed squeezes.
6. a kind of Polyurethane Thermoplastic Elastomer according to claim 1, is characterized in that described stablizer, is by antioxidant and UV light absorber is compound adds.
7. a kind of technique for producing elastomer of thermoplastic polyurethane according to claim 1, is characterized in that the method adopts following steps preparation:
(1)by designing proportioning by the polyether glycol of metering, the auxiliary agents such as crosslinked chainextender, toughener, stablizer, defoamer, fire retardant, anti-electrostatic, low temperature resistant hydrolysis agent add in still in the lump, stir and heat up, vacuum hydro-extraction, after moisture is qualified, pack standby as first component;
(2)at a certain temperature, by quantitative isocyanic ester, comprise that isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI) package spare by proportioning fusing or its prepolymer is standby as component B.
8. the synthetic of a kind of Polyurethane Thermoplastic Elastomer according to claim 1 need adopt one of casting molding machine, be characterized in that proportioning is accurate, quantification stability, heat up accurately and reliably, mix, do not produce bubble, the high-speed mixing head of special construction, the first and second mixtures are poured in the steel disk or polytetrafluoroethyldisk disk that coat in advance releasing agent being loaded on conveying belt, through 100-130 ℃, after the interior slaking 1-3h of curing oven, cooling, from dish take out then granulation, after drying packing, both a kind of Polyurethane Thermoplastic Elastomer micelle; Or by high-speed mixing material, directly enter in two spiral shell mark forcing machines of 100 ℃ of left and right, through different segmentations humidity province, mediate and reaction, by head, extrude adhesive tape, carry out cooling, granulation, oven dry, packing.
9. the using method of a kind of Polyurethane Thermoplastic Elastomer micelle according to claim 8 is as follows:
(1) can adopt thermoplastics processing method, as: extrude, injection moulding, calendering, blowing, mold pressing etc., TPU particle, at comparatively high temps plasticizing forming, is made to the goods of different shape;
(2)also can, using it as properties-correcting agent, as the cheap additive such as polyvinyl chloride (PVC), polyoxymethylene (POM), make compatible polymkeric substance (alloy), that is: TPU-PVC alloy, TPU-POM alloy etc.;
Use TPU modified PVC, can improve the latter's wear resistance, snappiness, shock resistance, low temperature resistant, oil-proofness and adhesion property;
With TPU modification POM, be to strengthen POM snappiness, wear resistance, shock resistance and the performance such as low temperature resistant equally; Add suitable softening agent, when polyoxymethylene and TPU proportioning are 60:40, better effects if.
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104262563A (en) * | 2014-09-05 | 2015-01-07 | 常熟市中腾塑胶有限公司 | Plastic ground mat and preparation method thereof |
| CN104861642A (en) * | 2015-06-10 | 2015-08-26 | 上海北岗聚合物科技有限公司 | Low-hardness TPU for artificial leather and preparation method of low-hardness TPU |
| CN105176057A (en) * | 2015-09-22 | 2015-12-23 | 深圳市力信陆南橡塑五金有限公司 | Anti-static polyurethane (PU) elastomer and preparation method and application thereof |
| CN105336415A (en) * | 2015-10-30 | 2016-02-17 | 江苏中煤电缆有限公司 | Double-sheath structured degaussing cable |
| CN105367749A (en) * | 2015-12-22 | 2016-03-02 | 成都市新筑路桥机械股份有限公司 | Low-temperature casting material for extremely cold areas, and production method thereof |
| CN105542352A (en) * | 2016-01-28 | 2016-05-04 | 青岛新材料科技工业园发展有限公司 | Modified polyvinyl chloride door seal and preparation method thereof |
| CN106810791A (en) * | 2017-02-05 | 2017-06-09 | 合肥华凌股份有限公司 | Equipment, door seal, composite with chamber and preparation method thereof |
| CN106867233A (en) * | 2017-02-18 | 2017-06-20 | 河南工程学院 | A kind of heat resistant and wear resistant macromolecular material and preparation method thereof |
| CN107353390A (en) * | 2017-08-25 | 2017-11-17 | 广东元星工业新材料有限公司 | Preforming polyurethane and composite material of silicon carbide and preparation method thereof |
| CN107973912A (en) * | 2017-03-14 | 2018-05-01 | 昆山台益塑胶科技有限公司 | Polyformaldehyde-thermoplastic rubber's block copolymer production method |
| CN108314765A (en) * | 2017-12-18 | 2018-07-24 | 苏州浩洋聚氨酯科技有限公司 | A kind of antibacterial polyurethane synthetic material |
| CN109552468A (en) * | 2018-11-16 | 2019-04-02 | 厦门同欣源新材料科技有限公司 | A kind of saddle and its production technology |
| CN110144110A (en) * | 2018-02-11 | 2019-08-20 | 孙双林 | A kind of thermoplastic polyurethane material and preparation method thereof |
| CN110144114A (en) * | 2018-02-11 | 2019-08-20 | 孙双林 | A kind of composition and preparation method thereof |
| CN111040424A (en) * | 2019-12-11 | 2020-04-21 | 东莞市雄林新材料科技股份有限公司 | Transparency-controllable TPU (thermoplastic polyurethane) film and preparation method thereof |
| CN111961174A (en) * | 2017-01-17 | 2020-11-20 | 深圳市力信陆南实业有限公司 | Flame-retardant polyurethane high-performance rubber and preparation method thereof |
| CN113150242A (en) * | 2021-01-14 | 2021-07-23 | 福建大方睡眠科技股份有限公司 | Molded foaming type polyurethane bra mold cup and preparation method thereof |
| CN113512174A (en) * | 2021-06-02 | 2021-10-19 | 宁波宝亭生物科技有限公司 | Two-component polyurethane composition and preparation method and application thereof |
| CN114369226A (en) * | 2022-02-16 | 2022-04-19 | 广东安拓普聚合物科技有限公司 | Lightweight polyurethane elastomer and manufacturing method and application thereof |
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| CN104861642A (en) * | 2015-06-10 | 2015-08-26 | 上海北岗聚合物科技有限公司 | Low-hardness TPU for artificial leather and preparation method of low-hardness TPU |
| CN105176057B (en) * | 2015-09-22 | 2017-08-25 | 深圳市力信陆南橡塑五金有限公司 | Excellent power glue of antistatic and its preparation method and application |
| CN105176057A (en) * | 2015-09-22 | 2015-12-23 | 深圳市力信陆南橡塑五金有限公司 | Anti-static polyurethane (PU) elastomer and preparation method and application thereof |
| CN105336415A (en) * | 2015-10-30 | 2016-02-17 | 江苏中煤电缆有限公司 | Double-sheath structured degaussing cable |
| CN105367749A (en) * | 2015-12-22 | 2016-03-02 | 成都市新筑路桥机械股份有限公司 | Low-temperature casting material for extremely cold areas, and production method thereof |
| CN105367749B (en) * | 2015-12-22 | 2018-08-24 | 成都市新筑路桥机械股份有限公司 | A kind of cast cold material and its manufacturing method for extremely cold area |
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| CN111961174A (en) * | 2017-01-17 | 2020-11-20 | 深圳市力信陆南实业有限公司 | Flame-retardant polyurethane high-performance rubber and preparation method thereof |
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| CN106867233A (en) * | 2017-02-18 | 2017-06-20 | 河南工程学院 | A kind of heat resistant and wear resistant macromolecular material and preparation method thereof |
| CN107973912A (en) * | 2017-03-14 | 2018-05-01 | 昆山台益塑胶科技有限公司 | Polyformaldehyde-thermoplastic rubber's block copolymer production method |
| CN107353390A (en) * | 2017-08-25 | 2017-11-17 | 广东元星工业新材料有限公司 | Preforming polyurethane and composite material of silicon carbide and preparation method thereof |
| CN108314765A (en) * | 2017-12-18 | 2018-07-24 | 苏州浩洋聚氨酯科技有限公司 | A kind of antibacterial polyurethane synthetic material |
| CN110144110A (en) * | 2018-02-11 | 2019-08-20 | 孙双林 | A kind of thermoplastic polyurethane material and preparation method thereof |
| CN110144114A (en) * | 2018-02-11 | 2019-08-20 | 孙双林 | A kind of composition and preparation method thereof |
| CN109552468B (en) * | 2018-11-16 | 2020-10-16 | 厦门同欣源新材料科技有限公司 | Saddle and production process thereof |
| CN109552468A (en) * | 2018-11-16 | 2019-04-02 | 厦门同欣源新材料科技有限公司 | A kind of saddle and its production technology |
| CN111040424A (en) * | 2019-12-11 | 2020-04-21 | 东莞市雄林新材料科技股份有限公司 | Transparency-controllable TPU (thermoplastic polyurethane) film and preparation method thereof |
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| CN113150242A (en) * | 2021-01-14 | 2021-07-23 | 福建大方睡眠科技股份有限公司 | Molded foaming type polyurethane bra mold cup and preparation method thereof |
| CN113512174A (en) * | 2021-06-02 | 2021-10-19 | 宁波宝亭生物科技有限公司 | Two-component polyurethane composition and preparation method and application thereof |
| CN114369226A (en) * | 2022-02-16 | 2022-04-19 | 广东安拓普聚合物科技有限公司 | Lightweight polyurethane elastomer and manufacturing method and application thereof |
| CN114369226B (en) * | 2022-02-16 | 2022-09-13 | 广东安拓普聚合物科技有限公司 | Lightweight polyurethane elastomer and manufacturing method and application thereof |
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Application publication date: 20140122 |