CN111995728B - Non-polar modified TPU (thermoplastic polyurethane) for shoe material and preparation method thereof - Google Patents
Non-polar modified TPU (thermoplastic polyurethane) for shoe material and preparation method thereof Download PDFInfo
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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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
Abstract
The invention belongs to the technical field of thermoplastic polyurethane, and particularly relates to a non-polar modified TPU (thermoplastic polyurethane) for shoe materials and a preparation method thereof. The TPU comprises the following raw materials in parts by weight: 20-40 parts of diisocyanate, 20-30 parts of dihydric alcohol with a non-polar side chain, 30-50 parts of polyester polyol, 5-10 parts of a chain extender, 0.1-0.5 part of an antioxidant and 0.5-1 part of a catalyst; the invention introduces the dimer alcohol with nonpolar side chain, takes the dimer alcohol and the polyester polyol as soft segments to react with diisocyanate and micromolecule chain extender, and simultaneously uses the fast forming process of premixing the dimer alcohol, the polyester polyol and the chain extender to prepare the TPU, which not only has the advantages of excellent wear resistance, good mechanical strength and excellent oil resistance and oxygen resistance of the polyurethane elastomer, but also has excellent hydrolytic stability, low-temperature performance, processing fluidity and elasticity, and can avoid the problems of precipitation, smell and the like caused by adding the plasticizer.
Description
Technical Field
The invention belongs to the technical field of thermoplastic polyurethane, and particularly relates to a non-polar modified TPU (thermoplastic polyurethane) for shoe materials and a preparation method thereof.
Background
Running and outdoor exercises become a body-building mode which gets hotter and hotter, and hydrolysis resistance, low-temperature performance and elasticity are important indexes for measuring shoe material products. Thermoplastic polyurethane elastomer (TPU) is a high molecular synthetic material with excellent performance, has the elasticity of rubber and the hardness of plastic, and also has good mechanical property and rebound resilience, and is widely applied to shoe material products. However, the TPU contains more strong polar groups (such as ester groups, ether groups, urethane groups, urea groups, biuret groups and allophanate groups) in the molecule, and the polarity endows the TPU with excellent performances in all aspects, and simultaneously, the defects of side reactions and degradation caused by easy precipitation of non-polar additives and easy water absorption of the strong polar groups are caused due to polarity incompatibility.
Patent CN 111057208A relates to a polyolefin polyol modified thermoplastic polyurethane elastomer and a preparation method thereof, wherein nonpolar modification is performed on polyurethane by using nonpolar polyolefin polyol, and the obtained modified TPU has the advantages of excellent wear resistance, high hardness, high elasticity, excellent oil resistance and excellent oxygen resistance of the thermoplastic polyurethane elastomer, and also has the characteristics of excellent low-temperature performance, excellent hydrolysis resistance and small dynamic heat generation of polyolefin rubber. However, the polyolefin polyol with hydroxyl groups at the ends is modified, and the solubility parameters of soft and hard segments have large difference, so that the phase separation degree is too large, the mechanical property is poor, and the polyolefin polyol is difficult to apply to the field of shoe materials.
With the widespread use of TPU in the field of footwear materials, this goal is usually achieved by adding plasticizers and blending with other materials in order to achieve better processing flowability and flexibility. However, there are disadvantages in that these methods result in the TPU material having poor mechanical strength, a strong odor and poor yellowing resistance. The preparation and performance research of thermoplastic polyurethane with diol as soft segment mentions that starting from the structure of the soft segment, bio-based diol with a non-polar side chain is introduced into the soft segment, MDI and BDO are used as hard segments to synthesize a novel thermoplastic polyurethane PDU, the soft segment part of the PDU is completely composed of the diol, the soft segment content of 40 percent is that each property of the PDU reaches a better state, and the performance of improving or reducing the content of the soft segment is influenced, thereby greatly limiting the adjustable range of the hardness of the product and further influencing the application range of the product.
According to the invention, the nonpolar chain segment, the alkane side chain and the polyol are introduced into the polyurethane and mixed, so that the polyurethane has an internal plasticization effect, the low-temperature performance, the processing fluidity and the elasticity of the material can be effectively improved, the surface energy of the polyurethane material can be reduced, the water adsorption of the material can be reduced, the contact angle of the polyurethane can be increased, and the processability, the hydrolysis resistance and the elasticity of the polyurethane can be comprehensively improved on the basis of ensuring the excellent mechanical performance of the TPU.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, and the non-polar modified TPU for the shoe material is provided, which not only has the advantages of excellent wear resistance, good mechanical strength and excellent oil resistance and oxygen resistance of the thermoplastic polyurethane elastomer, but also has excellent hydrolytic stability, low-temperature performance, processing fluidity and elasticity; the invention also provides a simple and feasible preparation method.
The invention prepares the non-polar modified TPU for shoe materials by introducing the dimer alcohol with non-polar side chains, taking the dimer alcohol and the polyester polyol as soft segments to react with diisocyanate and a micromolecule chain extender, and simultaneously using the fast forming process of pre-mixing the dimer alcohol, the polyester polyol and the chain extender.
The invention relates to a non-polar modified TPU for shoe materials, which comprises the following raw materials in parts by weight:
the dihydric alcohol with the nonpolar side chain is 2-hexyl-3-octyl-4, 5-dihydroxyoctyl cyclohexane (dihydric alcohol).
The diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimethylhexamethylene diisocyanate.
The polyester polyol is one or more of polyethylene glycol adipate polyol, polybutylene adipate polyol, poly epsilon-caprolactone polyol, polycarbonate polyol or polyhexamethylene adipate polyol.
The chain extender is one or more than one of ethylene glycol, 1, 4-butanediol or 1, 6-hexanediol.
The antioxidant is one or more of antioxidant 1010, antioxidant 1024 or antioxidant 264.
The catalyst is one or two of dibutyltin dilaurate or stannous octoate.
The invention relates to a preparation method of nonpolar modified TPU for shoe materials, which comprises the following steps:
(1) mixing dihydric alcohol with a non-polar side chain, polyester polyol and a chain extender, adding an antioxidant, and stirring at 80-110 ℃ to obtain a premix;
(2) adding diisocyanate and a catalyst into a storage tank A, adding the premix into a storage tank B, dehydrating in vacuum under the stirring condition, and pumping and injecting into a double-screw extruder;
(3) reacting in a double-screw extruder at the temperature of 110-190 ℃, and granulating to obtain TPU granules.
In the step (2), the stirring speed is 400-800 r/min; the vacuum dehydration temperature is 90-120 ℃.
In the step (3), the temperature of the feeding section of the double-screw extruder is 110-.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the common TPU, the hydrolysis retention rate of the TPU prepared by the invention can be improved by about 65 percent.
2. The invention effectively improves the hydrolytic stability and low-temperature performance of the polyurethane material due to the introduction of the nonpolar side chain, and the glass transition temperature is reduced by about 5 ℃ compared with the common TPU.
3. The addition of the non-polar side chain also plays a role in plasticization, the processing fluidity of the product can be effectively improved, the outflow temperature of the same hard segment can be reduced by about 5 ℃ under the condition of not adding the plasticizer, so that the processing temperature of the product is reduced, the rebound can be improved by about 5 percent, and the problems of precipitation, smell and the like caused by the addition of the plasticizer can be avoided.
Detailed Description
The present invention will be further described with reference to the following examples.
All the raw materials used in the examples are commercially available unless otherwise specified.
Example 1
The non-polar modified TPU for the shoe material is prepared from the following raw materials in parts by mass:
the preparation method comprises the following steps:
(1) mixing glycol, polyethylene glycol adipate polyol and 1, 4-butanediol, then adding an antioxidant 1010, and fully stirring at 90 ℃ to obtain a premix;
(2) adding 4,4' -diphenylmethane diisocyanate and a stannous octoate catalyst into a storage tank A, adding the premix into a storage tank B, stirring at the speed of 500r/min, performing vacuum dehydration at 110 ℃, and pumping into a double-screw extruder;
(3) reacting in a double-screw extruder at 120 ℃, and granulating to obtain TPU particles; wherein the temperature of the feeding section of the double-screw extruder is 110 ℃, the temperature of the mixing section is 130 ℃, the temperature of the extrusion section is 170 ℃, and the temperature of the machine head is 150 ℃.
Example 2
The non-polar modified TPU for the shoe material is prepared from the following raw materials in parts by mass:
the preparation method comprises the following steps:
(1) mixing diol, poly butanediol adipate and 1, 4-butanediol, then adding an antioxidant 1024, and fully stirring at 100 ℃ to obtain a premix;
(2) adding hexamethylene diisocyanate and a stannous octoate catalyst into a storage tank A, adding the premix into a storage tank B, stirring at the speed of 400r/min, dehydrating in vacuum at the temperature of 110 ℃, and pumping and injecting into a double-screw extruder;
(3) reacting in a double-screw extruder at 130 ℃, and granulating to obtain TPU particles; wherein the temperature of the feeding section of the double-screw extruder is 120 ℃, the temperature of the mixing section is 150 ℃, the temperature of the extrusion section is 180 ℃, and the temperature of the machine head is 160 ℃.
Example 3
The non-polar modified TPU for the shoe material is prepared from the following raw materials in parts by mass:
the preparation method comprises the following steps:
(1) mixing glycol, poly butanediol adipate and 1, 6-hexanediol mixed chain extender, then adding an antioxidant 264, and fully stirring at 100 ℃ to obtain a premix;
(2) adding 4,4' -diphenylmethane diisocyanate and a stannous octoate catalyst into a storage tank A, adding the premix into a storage tank B, stirring at the speed of 600r/min, performing vacuum dehydration at 110 ℃, and pumping into a double-screw extruder;
(3) reacting in a double-screw extruder at 160 ℃, and granulating to obtain TPU particles; wherein the temperature of the feeding section of the double-screw extruder is 120 ℃, the temperature of the mixing section is 150 ℃, the temperature of the extrusion section is 180 ℃, and the temperature of the machine head is 160 ℃.
Comparative example 1
The non-polar modified TPU for the shoe material is prepared from the following raw materials in parts by mass:
the preparation method comprises the following steps:
(1) mixing polyethylene glycol adipate polyol with 1, 4-butanediol, adding an antioxidant 1010, and fully stirring at 90 ℃ to obtain a premix;
(2) adding 4,4' -diphenylmethane diisocyanate and a stannous octoate catalyst into a storage tank A, adding the premix into a storage tank B, stirring at the speed of 500r/min, performing vacuum dehydration at 110 ℃, and pumping into a double-screw extruder;
(3) reacting in a double-screw extruder at 120 ℃, and granulating to obtain TPU particles; wherein the temperature of the feeding section of the double-screw extruder is 110 ℃, the temperature of the mixing section is 130 ℃, the temperature of the extrusion section is 170 ℃, and the temperature of the machine head is 150 ℃.
Comparative example 2
The non-polar modified TPU for the shoe material is prepared from the following raw materials in parts by mass:
the preparation method comprises the following steps:
(1) mixing polybutylene adipate polyol with 1, 4-butanediol, then adding an antioxidant 1024, and fully stirring at 100 ℃ to obtain a premix;
(2) adding hexamethylene diisocyanate and a stannous octoate catalyst into a storage tank A, adding the premix into a storage tank B, stirring at the speed of 400r/min, dehydrating in vacuum at the temperature of 110 ℃, and pumping and injecting into a double-screw extruder;
(3) reacting in a double-screw extruder at 130 ℃, and granulating to obtain TPU particles; wherein the temperature of the feeding section of the double-screw extruder is 120 ℃, the temperature of the mixing section is 150 ℃, the temperature of the extrusion section is 180 ℃, and the temperature of the machine head is 160 ℃.
The TPU elastomer pellets obtained in examples 1 to 3 and comparative examples 1 to 2 were converted into test specimens by injection molding and tested for mechanical properties, hardness, poaching retention, glass transition temperature, impact resilience. Tensile strength, tear strength, Shore hardness and impact resilience were tested according to GB/T529-2009, GB/T531-1992 and GB 1681-1982, respectively. The boiling retention rate is the retention rate of tensile strength after boiling in water for 7 days at 80 ℃, the outflow temperature is tested by adopting a capillary rheometer reference instrument with the standard, and the test results are shown in tables 1 and 2.
TABLE 1 hardness and mechanical Property results for the products of examples 1-3 and comparative examples 1-2
TABLE 2 hydrolysis resistance and processability test results of the products of examples 1-3 and comparative examples 1-2
| Item | Outflow temperature (. degree. C.) | Water boiling retention (%) | Rebound (%) | Glass transition temperature (. degree. C.) |
| Example 1 | 170 | 92 | 52 | -41 |
| Example 2 | 176 | 95 | 48 | -32 |
| Example 3 | 188 | 98 | 35 | -29 |
| Comparative example 1 | 175 | 55 | 46 | -36 |
| Comparative example 2 | 182 | 58 | 42 | -25 |
The results in tables 1 and 2 show that the introduction of the bio-based diol-diol having a non-polar side chain to modify the TPU significantly reduces the glass transition temperature and the processing temperature of the material, improves the hydrolytic stability and the resilience performance, significantly reduces the comparative melting point of the same hard segment, and improves the processing fluidity of the product, while maintaining the excellent mechanical properties of the TPU.
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (7)
1. A non-polar modified TPU for shoe materials, characterized in that: the composite material comprises the following raw materials in parts by mass:
the dihydric alcohol with the nonpolar side chain is 2-hexyl-3-octyl-4, 5-dihydroxyoctyl cyclohexane;
the polyester polyol is one or more of polyethylene glycol adipate polyol, polybutylene adipate polyol, poly epsilon-caprolactone polyol, polycarbonate polyol or polyhexamethylene adipate polyol;
the preparation method of the non-polar modified TPU for the shoe material comprises the following steps:
(1) mixing dihydric alcohol with a non-polar side chain, polyester polyol and a chain extender, adding an antioxidant, and stirring at 80-110 ℃ to obtain a premix;
(2) adding diisocyanate and a catalyst into a storage tank A, adding the premix into a storage tank B, dehydrating in vacuum under the stirring condition, and pumping and injecting into a double-screw extruder;
(3) reacting in a double-screw extruder at the temperature of 110-190 ℃, and granulating to obtain TPU granules.
2. The non-polar modified TPU for shoe materials according to claim 1, characterized by: the diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimethylhexamethylene diisocyanate.
3. The non-polar modified TPU for shoe materials according to claim 1, characterized by: the chain extender is one or more than one of ethylene glycol, 1, 4-butanediol or 1, 6-hexanediol.
4. The non-polar modified TPU for shoe materials according to claim 1, characterized by: the antioxidant is one or more of antioxidant 1010, antioxidant 1024 or antioxidant 264.
5. The non-polar modified TPU for shoe materials according to claim 1, characterized by: the catalyst is one or two of dibutyltin dilaurate or stannous octoate.
6. The non-polar modified TPU for shoe materials according to claim 1, characterized by: in the step (2), the stirring speed is 400-800 r/min; the vacuum dehydration temperature is 90-120 ℃.
7. The non-polar modified TPU for shoe materials according to claim 1, characterized by: in the step (3), the temperature of the feeding section of the double-screw extruder is 110-.
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| CN112831150A (en) * | 2021-02-01 | 2021-05-25 | 陶相琴 | Preparation method of breathable sweat-absorbent EVA (ethylene-vinyl acetate copolymer) foamed shoe material |
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| JP2997307B2 (en) * | 1990-09-20 | 2000-01-11 | 旭化成工業株式会社 | Polyisocyanate |
| DE4420310A1 (en) * | 1994-06-10 | 1995-12-14 | Henkel Kgaa | Use of dimer diol in polyurethane moldings |
| JPH08269158A (en) * | 1995-03-28 | 1996-10-15 | Toagosei Co Ltd | Production of water-resistant polyurethane |
| US5864001A (en) * | 1996-10-16 | 1999-01-26 | Shell Oil Company | Polyurethanes made with polydiene diols, diisocyanates, and dimer diol chain extender |
| CN100439413C (en) * | 2003-04-25 | 2008-12-03 | 陶氏环球技术公司 | Vegetable oil based polyols and polyurethanes made therefrom |
| DE102005011448A1 (en) * | 2005-03-12 | 2006-09-21 | Bayer Materialscience Ag | Poly (urethancarbonat) polyols |
| JP2007250096A (en) * | 2006-03-16 | 2007-09-27 | Fujifilm Corp | Magnetic recording medium |
| WO2011074617A1 (en) * | 2009-12-17 | 2011-06-23 | 三菱化学株式会社 | Composition containing polycarbonate diol, process for production of same, polyurethane using same, and process for production tehreof |
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