CN104231221A - High-temperature-resistant thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
High-temperature-resistant thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN104231221A CN104231221A CN201410479983.1A CN201410479983A CN104231221A CN 104231221 A CN104231221 A CN 104231221A CN 201410479983 A CN201410479983 A CN 201410479983A CN 104231221 A CN104231221 A CN 104231221A
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- polyurethane elastomer
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- 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
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- 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
- C08G18/61—Polysiloxanes
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- 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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- 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
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a high-temperature-resistant thermoplastic polyurethane elastomer and a preparation method thereof. The thermoplastic polyurethane elastomer comprises components in parts by weight as follows: 45-62 parts of polyester polyol, 5-12 parts of hydroxyl silicone oil, 35-50 parts of diisocyanate, 10-30 parts of a chain extender, 0.3-1 part of aromatic diamine and 0.5-1.3 parts of bisphenol A. The preparation method comprises steps as follows: Step 1), the polyester polyol and the hydroxyl silicone oil are mixed, heated and then subjected to vacuum dehydration; Step 2), the diisocyanate and the material obtained in Step 1) are pre-polymerized to obtain a pre-polymer; Step 3), the aromatic diamine and the bisphenol A are added into the chain extender to form a mixed chain extender, and the mixed chain extender and the pre-polymer are evenly mixed; Step 4), the material obtained in Step 3) is vulcanized and cured to obtain the high-temperature-resistant thermoplastic polyurethane elastomer. According to the elastomer and the preparation method, the hydroxyl silicone oil is adopted to replace part of polyester polyol, and the aromatic diamine and the bisphenol A are adopted to replace part of butanediol to be used as the chain extender, so that soft segments containing silica groups as well as hard segments containing urea structures and aromatic rings are introduced on molecular chains of the elastomer to improve the heat resistance of the polyurethane elastomer.
Description
Technical field
The present invention relates to polyurethane elastomer preparing technical field, be specifically related to a kind of high-temperature-resistant thermoplastic polyurethane elastomer and preparation method thereof.
Background technology
Thermoplastic elastomer due to its excellent extension at break, rebound resilience, wear resistance, weathering resistance and the processing molding method more superior than cast polyurethane, and obtain applying more and more widely.Particularly due to the fast development of polyurethane industries among others, promote that again the production capacity of raw material producer constantly expands, and makes cost constantly decline, thus promote the application and development of new wheel polyurethane products.
Polyurethane Thermoplastic Elastomer is generally the linear polymeric formed as chainextender by dibasic alcohol, and due to the hydrogen bond between its molecule less, therefore fusing point is lower, and it is shaping to carry out melt-processed, as injection moulding, extrudes, blown film, the processing molding methods such as spinning.In contrast by the urethane of diamines as chainextender, although linear molecule long-chain can be formed, owing to forming urea key segment, stronger interaction force is had between having divided, often form crosslinking structure, therefore often fusing point is higher, and usually fusing point is higher than its decomposition temperature.Although therefore to be formed as chainextender with diamines and there is good rebound resilience, wear resistance and thermotolerance containing the urethane of urea structure, due to cannot melt-processed, therefore there is no the commercial thermoplastic polyurethane containing urea structure up to now; Also become one of focus of International Academic research and industrial enterprise's research and development simultaneously.
The present invention is directed to the problem of the Polyurethane Thermoplastic Elastomer resistance to elevated temperatures deficiency existed in prior art, provide a kind of formula and preparation method of novel Polyurethane Thermoplastic Elastomer.
Summary of the invention
The object of the present invention is to provide a kind of high-temperature-resistant thermoplastic polyurethane elastomer and preparation method thereof.
For reaching this object, the present invention by the following technical solutions:
A kind of high-temperature-resistant thermoplastic polyurethane elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
The parts by weight of described polyester polyol can select 45.02 ~ 61.8,48 ~ 60,52.3 ~ 59.8,54 ~ 56,55.3 etc., all can be used for implementing the present invention.
The parts by weight of described hydroxy silicon oil can select 5.01 ~ 11.7,5.4 ~ 10,6.2 ~ 9.2,7 ~ 8.5,7.6 etc., all can be used for implementing the present invention.
The parts by weight of described vulcabond can select 35.02 ~ 49.6,38 ~ 44,39.7 ~ 41.3,40.8 etc., all can be used for implementing the present invention.
The parts by weight of described chainextender can select 10.02 ~ 29.6,12 ~ 27.4,16.4 ~ 25,19 ~ 23.8,21.3 etc., all can be used for implementing the present invention.
The parts by weight of described aromatic diamine can select 0.31 ~ 0.96,0.4 ~ 0.86,0.43 ~ 0.72,0.53 ~ 0.7,0.6 ~ 0.67,0.62 etc., all can be used for implementing the present invention.
The parts by weight of described dihydroxyphenyl propane can select 0.51 ~ 1.28,0.54 ~ 1.18,0.7 ~ 1.02,0.84 ~ 0.94,0.9 etc., all can be used for implementing the present invention.
Described polyester polyol is the mixture of a kind of in polyester adipate, poly-azelate, poly-butyric ester or polycarbonate or at least two kinds.Typical but non-limiting example comprises: polyester adipate, poly-azelate, poly-butyric ester, polycarbonate, polyester adipate and poly-azelate, poly-butyric ester and polycarbonate, polyester adipate, poly-azelate and poly-butyric ester, polyester adipate, poly-azelate, poly-butyric ester and polycarbonate etc.
Described vulcabond comprises tolylene diisocyanate, 2,4-tolylene diisocyanate, diphenylmethanediisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 3,3 '-dimethyl-4, the mixture of a kind of in 4-biphenyl diisocyanate, triphenylmethane triisocyanate or PPDI or at least two kinds, preferred 2,4 toluene diisocyanate.Typical but non-limiting example comprises: tolylene diisocyanate, diphenylmethanediisocyanate, 2, 4-tolylene diisocyanate, 1, 5-naphthalene diisocyanate, 2, 4-tolylene diisocyanate and xylylene diisocyanate, 3, 3 '-dimethyl-4, 4-biphenyl diisocyanate, xylylene diisocyanate and 3, 3 '-dimethyl-4, 4-biphenyl diisocyanate, triphenylmethane triisocyanate and PPDI, tolylene diisocyanate, 2, 4-tolylene diisocyanate, diphenylmethanediisocyanate and 1, 5-naphthalene diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, PPDI and diphenylmethanediisocyanate etc., all can be used for implementing the present invention.
Described chainextender is BDO.
As the preferred technical solution of the present invention, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
As the most preferred technical scheme of the present invention, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described Polyurethane Thermoplastic Elastomer different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... composition ".
A kind of described method for preparing thermoplastic polyurethane elastomer, said method comprising the steps of:
1) by polyester polyol and the dehydration of hydroxy silicon oil Hybrid Heating final vacuum;
2) by vulcabond and step 1) the material pre-polymerization that obtains obtains performed polymer;
3) aromatic diamine and dihydroxyphenyl propane are added in chainextender form mixed chain extender, mixed chain extender and performed polymer are mixed;
4) by step 3) the material sulfuration that obtains, obtain high-temperature-resistant thermoplastic polyurethane elastomer after slaking.
Compared with prior art scheme, the present invention has following beneficial effect:
The present invention adopts hydroxy silicon oil to replace a part of polyester polyol, aromatic diamine and dihydroxyphenyl propane replace part butyleneglycol as chainextender, make on elastomeric molecular chain, introduce siliceous oxygen groups soft section, the hard section containing urea structure and aromatic nucleus, to improve the thermotolerance of polyurethane elastomer.
The present invention is described in more detail below.But following example is only simple and easy example of the present invention, and do not represent or limit the scope of the present invention, protection scope of the present invention is as the criterion with claims.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
A kind of high-temperature-resistant thermoplastic polyurethane elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
1) by polyester polyol and the dehydration of hydroxy silicon oil Hybrid Heating final vacuum;
2) by vulcabond and step 1) the material pre-polymerization that obtains obtains performed polymer;
3) aromatic diamine and dihydroxyphenyl propane are added in chainextender form mixed chain extender, mixed chain extender and performed polymer are mixed;
4) by step 3) the material sulfuration that obtains, obtain high-temperature-resistant thermoplastic polyurethane elastomer after slaking.
Embodiment 2
A kind of high-temperature-resistant thermoplastic polyurethane elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Its preparation method is with embodiment 1.
Embodiment 3
A kind of high-temperature-resistant thermoplastic polyurethane elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Its preparation method is with embodiment 1.
Embodiment 4
A kind of high-temperature-resistant thermoplastic polyurethane elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Its preparation method is with embodiment 1.
Embodiment 5
A kind of high-temperature-resistant thermoplastic polyurethane elastomer, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
Its preparation method is with embodiment 1.
Measure the resistance to elevated temperatures of the Polyurethane Thermoplastic Elastomer of embodiment 1-5 in accordance with the following methods:
By sample drawing-off 100%, by 190 DEG C of hot air treatment 1 minute, then under high-temperature and high-pressure conditions, dispersed dye are used to dye.Dye from room temperature, after rising to 130 DEG C with 1.5 DEG C/min temperature, dye under keeping this temperature 60min.After dyeing terminates, ultimate strength (DS after use tension testing machine test dyeing keratin-fiber process
1) and ultimate strength (DS before treatment
2), and using the ratio of the two as ultimate strength conservation rate, conservation rate is higher, resistance to elevated temperatures is also more excellent.
Resistance to elevated temperatures (%)=100* (DS
1)/(DS
2)
The results of property recorded is as table 1.
The resistance to elevated temperatures test result of each embodiment of table 1
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Resistance to elevated temperatures | 69 | 68 | 72 | 71 | 76 |
| (％) | ? | ? | ? | ? | ? |
Applicant states, person of ordinary skill in the field is on the basis of above-described embodiment, by the concrete content point value of above-described embodiment component, combined with the technical scheme of summary of the invention part, thus the new numerical range produced, also be one of record scope of the present invention, the application, for making specification sheets simple and clear, no longer enumerates these numerical ranges.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (7)
1. a high-temperature-resistant thermoplastic polyurethane elastomer, is characterized in that, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
2. polyurethane elastomer as claimed in claim 1, is characterized in that, described polyester polyol is the mixture of a kind of in polyester adipate, poly-azelate, poly-butyric ester or polycarbonate or at least two kinds.
3. polyurethane elastomer as claimed in claim 1 or 2, it is characterized in that, described vulcabond comprises tolylene diisocyanate, 2,4-tolylene diisocyanate, diphenylmethanediisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 3, the mixture of a kind of in 3 '-dimethyl-4,4-biphenyl diisocyanate, triphenylmethane triisocyanate or PPDI or at least two kinds, preferred 2,4 toluene diisocyanate.
4. the polyurethane elastomer as described in one of claim 1-3, is characterized in that, described chainextender is BDO.
5. the polyurethane elastomer as described in one of claim 1-4, is characterized in that, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
6. the polyurethane elastomer as described in one of claim 1-5, is characterized in that, described Polyurethane Thermoplastic Elastomer comprises following composition by weight:
7. a method for preparing thermoplastic polyurethane elastomer as described in one of claim 1-6, is characterized in that, said method comprising the steps of:
1) by polyester polyol and the dehydration of hydroxy silicon oil Hybrid Heating final vacuum;
2) by vulcabond and step 1) the material pre-polymerization that obtains obtains performed polymer;
3) aromatic diamine and dihydroxyphenyl propane are added in chainextender form mixed chain extender, mixed chain extender and performed polymer are mixed;
4) by step 3) the material sulfuration that obtains, obtain high-temperature-resistant thermoplastic polyurethane elastomer after slaking.
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Cited By (14)
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| 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 |
| CN105885389A (en) * | 2016-06-08 | 2016-08-24 | 东莞市吉鑫高分子科技有限公司 | High-temperature-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN106243318A (en) * | 2016-07-28 | 2016-12-21 | 东莞市吉鑫高分子科技有限公司 | A kind of banburying calendering type Polyurethane Thermoplastic Elastomer and preparation method thereof |
| CN106380570A (en) * | 2016-09-30 | 2017-02-08 | 无锡市明盛强力风机有限公司 | TPU (Thermoplastic Polyurethanes) thin film and preparation method thereof |
| CN107446342A (en) * | 2017-06-30 | 2017-12-08 | 苏州奥斯汀新材料科技有限公司 | A kind of preparation method of low temperature-resistant thermoplastic polyurethane elastomer film |
| CN107501510A (en) * | 2017-09-08 | 2017-12-22 | 肇庆高新区恒泰信息服务有限公司 | A kind of low hardness polyurethane elastic body material |
| CN108003317A (en) * | 2017-12-22 | 2018-05-08 | 四川大学 | A kind of silicone elastomer and its preparation method and application |
| CN108034038A (en) * | 2017-12-26 | 2018-05-15 | 东莞市雄林新材料科技股份有限公司 | A kind of high abrasion TPU for cable jacket and preparation method thereof |
| CN110922562A (en) * | 2019-11-13 | 2020-03-27 | 东莞市雄林新材料科技股份有限公司 | High-light-transmittance TPU (thermoplastic polyurethane) film and preparation method thereof |
| CN111094378A (en) * | 2017-07-20 | 2020-05-01 | 巴斯夫欧洲公司 | Thermoplastic polyurethanes |
| CN111117543A (en) * | 2019-11-29 | 2020-05-08 | 江苏晟宏生态纺织科技有限公司 | Hot melt adhesive with far infrared function and preparation method thereof |
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