CN104017167A - Preparation method of heat-resistant polyester plastic polyurethane elastomer - Google Patents
Preparation method of heat-resistant polyester plastic polyurethane elastomer Download PDFInfo
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- CN104017167A CN104017167A CN201410265725.3A CN201410265725A CN104017167A CN 104017167 A CN104017167 A CN 104017167A CN 201410265725 A CN201410265725 A CN 201410265725A CN 104017167 A CN104017167 A CN 104017167A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a heat-resistant polyester plastic polyurethane elastomer, which comprises the following steps: 1) adding polyester polyol and a catalyst into a reaction kettle, and dehydrating under the conditions of heating and vacuum to obtain a component A; respectively heating 1,5-naphthyldiisocyanate and a chain extender, evenly mixing with the component A, and carrying out extrusion reaction with a double screw extruder to obtain a polyester polyurethane elastomer; and 2) blending an epoxy resin with the polyester polyurethane elastomer obtained in the step 1) to obtain a blend, and drying the blend at 80-150 DEG C under the pressure of -0.08 to -0.1 MPa for 4-24 hours to obtain the heat-resistant polyester thermoplastic polyurethane elastomer. The heat-resistant polyester thermoplastic polyurethane elastomer prepared by the method is mainly used in the field of application of TPU (thermoplastic polyurethane) at higher temperature.
Description
Technical field
The present invention relates to a kind of method for preparing thermoplastic polyurethane elastomer, relate in particular to a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer.
Background technology
Polyurethane Thermoplastic Elastomer (being called again TPU) novel material is called as " epoch-making novel high polymer material ", is one of our times six synthetic materials greatly with development prospect.
Polyurethane elastomer has the excellent properties such as good mechanical property, abrasion performance, oil resistant, tear-resistant, resistance to chemical attack, resistance to x radiation x, cohesiveness is good, but its use temperature is generally no more than 80 ℃, 100 ℃ of above material meeting softening transforms, mechanical property obviously weakens, Short-range Temperature is no more than 120 ℃, has seriously limited its widespread use.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of can be for the heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer using under higher temperature conditions.
For solving the problems of the technologies described above the technical solution adopted in the present invention, be: a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer, the steps include:
1) the elastomeric preparation of PAUR:
Polyester polyol, catalyzer are added in reactor, speed with 5～50 ℃/min is warming up to 100～200 ℃, intensification limit, limit vacuumizes, controlling reacting kettle inner pressure is that-0.08～-0.1MPa, temperature are 100～200 ℃ of dehydration 0.5～20h, then be cooled to 65～85 ℃, pass into nitrogen and remove vacuum, obtain A component;
After 1,5-naphthalene diisocyanate (NDI) is heated to respectively to 50-80 ℃ with chainextender, enter twin screw extruder with A component after casting molding machine mixes, in twin screw extruder, limit coronite is extruded, and forms PAUR elastomerics;
Described catalyzer account for polyester polyol total mass 0.01%～0.5%; Described 1, the mass ratio of 5-naphthalene diisocyanate and polyester polyol is 1:1-2; Described chainextender accounts for the 1%-10% of the total mass of vulcabond and polyester polyol;
2) Epoxy/Polyurethane is elastomer blended:
By epoxy resin and step 1) PAUR that obtains is elastomer blended, then blend is poured in the polytetrafluoroethyldisk disk of clean dried, be placed horizontally in vacuum drying oven, the temperature of controlling vacuum drying oven is that 80～150 ℃, pressure are-0.08～-0.1MPa, after dry 4～24h, take out, obtain heat-resistant polyester type Polyurethane Thermoplastic Elastomer;
Described epoxy resin accounts for 8%～12% of PAUR elastomerics quality.
Described polyester polyol is made through polycondensation by di-carboxylic acid and dibasic alcohol, and its number-average molecular weight is 1000～4000.
Described di-carboxylic acid is aliphatic dicarboxylic acid or aromatic binary carboxylic acid; Described dibasic alcohol is selected from ethylene glycol, BDO, 1,6-hexylene glycol, 2,2-methyl isophthalic acid, the mixture of a kind of in ammediol or any two kinds.
Described aliphatic dicarboxylic acid is selected from the mixture of a kind of in pentanedioic acid, hexanodioic acid, suberic acid and sebacic acid or any two kinds; Described aromatic binary carboxylic acid is selected from the mixture of a kind of in phthalic acid, m-phthalic acid, terephthalic acid or any two kinds.
Described catalyzer is organic tin catalyzer, is selected from the mixture of a kind of in stannous octoate, dibutyltin diacetate, dibutyl tin laurate or any two kinds.
Described chainextender is selected from BDO, 1,3-PD, Isosorbide-5-Nitrae-hexalin, neopentyl glycol, 1, the mixture of a kind of in 6-hexylene glycol or any two kinds.
Described is cosolvent blend, ultrasonic dispersion or Screw Extrusion by epoxy resin and the elastomer blended method of PAUR.
The invention has the beneficial effects as follows: adopt heat-resistant polyester type Polyurethane Thermoplastic Elastomer that preparation method of the present invention makes for the TPU Application Areas under comparatively high temps, be mainly to adopt following methods:
1) adopt resistance toheat good 1,5-naphthalene diisocyanate (NDI) is as hard section, NDI is owing to having aromatic naphthalene ring, molecular chain height is regular, with its synthetic polyurethane elastomer, have excellent dynamic property, resistance toheat is better than the polyurethane elastomer of TDI type, MDI type.
2) using the graft modification of epoxy resin as properties-correcting agent, epoxy resin and polyurethane reaction can introduce on molecular chain that internal cohesive energy is large, heat decomposition temperature is high, the organic heterocyclic group-oxazolidone of Heat stability is good, forming section reticulated structure, the resistance toheat of raising polyurethane elastomer.
The key technical indexes of the type Polyurethane Thermoplastic Elastomer obtaining by the present invention: tensile strength 38～48MPa; And conventional MDI type Polyurethane Thermoplastic Elastomer tensile strength < 35MPa.
Embodiment
Describe specific embodiment of the invention scheme below in detail.
Embodiment 1
In 2 liters of reactors, add the polyvalent alcohol 500g being formed by hexanodioic acid and the polycondensation of 1,6-hexylene glycol, add positive tetrabutyl titanate 2g, with the speed of 5 ℃/min, slowly heat up, intensification limit, limit is evacuated to vacuum tightness 0.04MPa, vacuum hydro-extraction 2h.Polyvalent alcohol 280g and 1,5-naphthalene diisocyanate 173g after dehydration and 2-methyl butyleneglycol 35g are heated to respectively to 50 ℃ and after casting molding machine mixing, enter twin screw extruder, in twin screw extruder, limit coronite is extruded.In the present embodiment, each district's set temperature of screw rod is as follows: 80 ℃, 120 ℃, 180 ℃, 200 ℃, 180 ℃, 150 ℃, it is 55 seconds that whole reaction finds time.
Add in the ultrasonic instrument that the above-mentioned elastomerics of 65gE-51 and 650g is 1200w at power and obtain heat-resistant thermoplastic polyurethane elastomer after ultrasonic dispersion 3min.
Embodiment 2
In 2 liters of reactors, add the polyvalent alcohol 500g being formed by suberic acid and BDO polycondensation, add positive tetrabutyl titanate 1.9g, speed with 5 ℃/min slowly heats up, intensification limit, limit is evacuated to vacuum tightness 0.04MPa, and simultaneous temperature rises to 220 ℃, reacts 1.5 hours at this temperature.
Polyvalent alcohol 300g and 1,5-naphthalene diisocyanate 190g after dehydration and 4-ethyl heptanediol 40g are heated to respectively to 50 ℃ and after casting molding machine mixing, enter twin screw extruder, in twin screw extruder, limit coronite is extruded.In the present embodiment, each district's set temperature of screw rod is as follows: 80 ℃, 120 ℃, 180 ℃, 200 ℃, 180 ℃, 150 ℃, it is 58 seconds that whole reaction finds time.
Add the above-mentioned elastomerics of 44gE-51 and 550g at appropriate solvent N, in dinethylformamide (DMF), with magnetic stirring apparatus, heat while stirring after 5min, be poured into the polytetrafluoroethyldisk disk of clean dried, be placed horizontally in 120 ℃ of vacuum drying ovens, keep vacuum tightness to be-0.09MPa, after 12h, take out, obtain heat-resistant polyester type Polyurethane Thermoplastic Elastomer.
Embodiment 3
In 2 liters of reactors, add by hexanodioic acid and 1, the polyvalent alcohol 500g that the polycondensation of 4-butyleneglycol forms, add titanium propanolate 2.1g, organobentonite 20g, speed with 6 ℃/min slowly heats up, intensification limit, limit is evacuated to vacuum tightness 0.045MPa, and simultaneous temperature rises to 210 ℃, reacts 2 hours at this temperature.
Above-mentioned reaction product 288g and 1,5-naphthalene diisocyanate 160g and 3-methyl hexylene glycol 43g are heated to respectively to 50 ℃ and after casting molding machine mixes, enter twin screw extruder, in twin screw extruder, limit coronite is extruded.In the present embodiment, each district's set temperature of screw rod is as follows: 80 ℃, 150 ℃, 190 ℃, 220 ℃, 180 ℃, 150 ℃, it is 45 seconds that whole reaction finds time.
By 72gE-51 and the above-mentioned elastomerics of 600g, limit coronite in twin screw extruder is extruded.In the present embodiment, each district's set temperature of twin screw is as follows: 90 ℃, 160 ℃, 190 ℃, 230 ℃, 190 ℃, 155 ℃, whole reaction finds time as 60s.Extrudate is poured into the polytetrafluoroethyldisk disk of clean dried, be placed horizontally in 100 ℃ of vacuum drying ovens, keep vacuum tightness to be-0.1MPa, after 8h, take out, obtain heat-resistant thermoplastic polyurethane elastomer.
Comparative example 1
In 2 liters of reactors, add the polyvalent alcohol 500g being formed by hexanodioic acid and the polycondensation of 1,6-hexylene glycol, add positive tetrabutyl titanate 2g, with the speed of 5 ℃/min, slowly heat up, intensification limit, limit is evacuated to vacuum tightness 0.04MPa, vacuum hydro-extraction 2h.Polyvalent alcohol 280g after dehydration is heated to respectively to 50 ℃ with MDI173g and 2-methyl butyleneglycol 35g and after casting molding machine mixes, enters twin screw extruder, in twin screw extruder, limit coronite is extruded.In the present embodiment, each district's set temperature of screw rod is as follows: 80 ℃, 120 ℃, 180 ℃, 200 ℃, 180 ℃, 150 ℃, it is 55 seconds that whole reaction finds time.
Tensile strength, unit elongation, tear strength measuring method: ISO37-2005.
The mechanical property of heat resistant type TPU under differing temps in MDI type PU elastomerics and embodiment 1
From upper table, at high temperature, the conservation rate of the hardness of heat resistant type polyurethane elastomer, tensile strength, elongation at break and tear strength is better than MDI type polyurethane elastomerics.
Claims (8)
1. a heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer, the steps include:
1) polyester polyol, catalyzer are added in reactor, speed with 5～50 ℃/min is warming up to 100～200 ℃, intensification limit, limit vacuumizes, controlling reacting kettle inner pressure is that-0.08～-0.1MPa, temperature are 100～200 ℃ of dehydration 0.5～20h, then be cooled to 65～85 ℃, pass into nitrogen and remove vacuum, obtain A component;
After 1,5-naphthalene diisocyanate, chainextender are heated to respectively to 50-80 ℃, mix with A component, then, by twin screw extruder extrusion reaction, obtain PAUR elastomerics;
Described catalyzer account for polyester polyol total mass 0.01%～0.5%; Described 1, the mass ratio of 5-naphthalene diisocyanate and polyester polyol is 1:1～2; Described chainextender accounts for the 1%-10% of the total mass of 1,5-naphthalene diisocyanate and polyester polyol;
2) by epoxy resin and step 1) PAUR that obtains elastomer blended blend, then blend being placed in to temperature and being 80～150 ℃, pressure is under-0.08～-0.1MPa condition, dry 4～24h, obtains heat-resistant polyester type Polyurethane Thermoplastic Elastomer;
Described epoxy resin accounts for 8%～12% of PAUR elastomerics quality.
2. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: described polyester polyol is made through polycondensation by di-carboxylic acid and dibasic alcohol, and its number-average molecular weight is 1000～4000.
3. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 2, is characterized in that: described di-carboxylic acid is aliphatic dicarboxylic acid or aromatic binary carboxylic acid; Described dibasic alcohol is selected from ethylene glycol, BDO, 1,6-hexylene glycol, 2,2-methyl isophthalic acid, the mixture of a kind of in ammediol or any two kinds.
4. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 3, is characterized in that: described aliphatic dicarboxylic acid is selected from the mixture of a kind of in pentanedioic acid, hexanodioic acid, suberic acid and sebacic acid or any two kinds; Described aromatic binary carboxylic acid is selected from the mixture of a kind of in phthalic acid, m-phthalic acid, terephthalic acid or any two kinds.
5. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: described catalyzer is organic tin catalyzer.
6. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 5, is characterized in that: described organic tin catalyzer is selected from the mixture of a kind of in stannous octoate, dibutyltin diacetate, dibutyl tin laurate or any two kinds.
7. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 1, it is characterized in that: described chainextender is selected from BDO, 1,3-PD, 1,4-hexalin, neopentyl glycol, 1, the mixture of a kind of in 6-hexylene glycol or any two kinds.
8. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: described is cosolvent blend, ultrasonic dispersion or Screw Extrusion by epoxy resin and the elastomer blended method of PAUR.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231204A (en) * | 2014-09-18 | 2014-12-24 | 东莞市吉鑫高分子科技有限公司 | Thermoplastic polyurethane elastomer for solar cells and preparation method of elastomer |
| CN104650319A (en) * | 2015-01-08 | 2015-05-27 | 大连理工大学 | Heat-resistant polyurethane thermoplastic elastomer and preparation method thereof |
| CN104804173A (en) * | 2015-05-18 | 2015-07-29 | 吴江市宏宇机械有限公司 | High-temperature-resistant polyurethane elastomer for mold resin and preparation method of polyurethane elastomer |
| CN105384908A (en) * | 2015-11-13 | 2016-03-09 | 成都多力多新材料有限公司 | Thermoplastic polyurethane elastomer and polyurethane prepolymer material and preparation method thereof |
| CN107880243A (en) * | 2017-11-23 | 2018-04-06 | 广东元星工业新材料有限公司 | A kind of high heat-resistant high-performance polyurethane elastomer and preparation method thereof |
| CN108192063A (en) * | 2017-12-28 | 2018-06-22 | 山东诺威聚氨酯股份有限公司 | High rigidity thermoplastic polyurethane elastomer and preparation method thereof |
| CN109111725A (en) * | 2018-07-20 | 2019-01-01 | 滁州市玉林聚氨酯有限公司 | A kind of preparation method of elastane |
| CN111410729A (en) * | 2020-04-24 | 2020-07-14 | 黎哲华 | High-heat-resistance flame-retardant phosphorus-nitrogen synergistic reaction type polyurethane material and preparation method thereof |
| CN112646355A (en) * | 2021-01-14 | 2021-04-13 | 江苏威久科技发展有限公司 | High-strength wear-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN115558281A (en) * | 2022-08-25 | 2023-01-03 | 浙江华峰热塑性聚氨酯有限公司 | High-hardness thermoplastic polyurethane copolymer and preparation method thereof |
| CN115926240A (en) * | 2022-07-25 | 2023-04-07 | 万华化学集团股份有限公司 | High-support thermoplastic polyurethane foam material and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231204A (en) * | 2014-09-18 | 2014-12-24 | 东莞市吉鑫高分子科技有限公司 | Thermoplastic polyurethane elastomer for solar cells and preparation method of elastomer |
| CN104231204B (en) * | 2014-09-18 | 2017-08-29 | 东莞市吉鑫高分子科技有限公司 | A kind of TPUE used for solar batteries and preparation method thereof |
| CN104650319A (en) * | 2015-01-08 | 2015-05-27 | 大连理工大学 | Heat-resistant polyurethane thermoplastic elastomer and preparation method thereof |
| CN104804173A (en) * | 2015-05-18 | 2015-07-29 | 吴江市宏宇机械有限公司 | High-temperature-resistant polyurethane elastomer for mold resin and preparation method of polyurethane elastomer |
| CN104804173B (en) * | 2015-05-18 | 2017-10-17 | 吴江市宏宇机械有限公司 | It is a kind of resistant to elevated temperatures for polyurethane elastomer of resin mould and preparation method thereof |
| CN105384908A (en) * | 2015-11-13 | 2016-03-09 | 成都多力多新材料有限公司 | Thermoplastic polyurethane elastomer and polyurethane prepolymer material and preparation method thereof |
| CN107880243A (en) * | 2017-11-23 | 2018-04-06 | 广东元星工业新材料有限公司 | A kind of high heat-resistant high-performance polyurethane elastomer and preparation method thereof |
| CN108192063A (en) * | 2017-12-28 | 2018-06-22 | 山东诺威聚氨酯股份有限公司 | High rigidity thermoplastic polyurethane elastomer and preparation method thereof |
| CN109111725A (en) * | 2018-07-20 | 2019-01-01 | 滁州市玉林聚氨酯有限公司 | A kind of preparation method of elastane |
| CN111410729A (en) * | 2020-04-24 | 2020-07-14 | 黎哲华 | High-heat-resistance flame-retardant phosphorus-nitrogen synergistic reaction type polyurethane material and preparation method thereof |
| CN112646355A (en) * | 2021-01-14 | 2021-04-13 | 江苏威久科技发展有限公司 | High-strength wear-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN115926240A (en) * | 2022-07-25 | 2023-04-07 | 万华化学集团股份有限公司 | High-support thermoplastic polyurethane foam material and preparation method thereof |
| CN115558281A (en) * | 2022-08-25 | 2023-01-03 | 浙江华峰热塑性聚氨酯有限公司 | High-hardness thermoplastic polyurethane copolymer and preparation method thereof |
| CN115558281B (en) * | 2022-08-25 | 2023-12-05 | 浙江华峰热塑性聚氨酯有限公司 | High-hardness thermoplastic polyurethane copolymer and preparation method thereof |
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