CN103865251A - Thermoplastic polyurethane elastomer injection molding composition and injection molding product thereof - Google Patents
Thermoplastic polyurethane elastomer injection molding composition and injection molding product thereof Download PDFInfo
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- CN103865251A CN103865251A CN201210537396.4A CN201210537396A CN103865251A CN 103865251 A CN103865251 A CN 103865251A CN 201210537396 A CN201210537396 A CN 201210537396A CN 103865251 A CN103865251 A CN 103865251A
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Abstract
The present invention discloses a thermoplastic polyurethane elastomer injection molding composition and an injection molding product thereof. The composition contains two or a plurality of thermoplastic polyurethane elastomer polymers having a number-average molecular weight of 55000-105000, wherein the content of one of the thermoplastic polyurethane elastomer polymers is 50-80 wt%, and the total content of the remaining thermoplastic polyurethane elastomer polymer is 20-50 wt%. According to the present invention, compared with the single-component thermoplastic polyurethane elastomer polymer, the composition has characteristics of good melt processing property, effectively shortened injection molding cycle, maintaining of all excellent performances of the thermoplastic polyurethane elastomer, and wide application prospect.
Description
Technical field
The present invention relates to a kind of Polyurethane Thermoplastic Elastomer (TPU) injection moulding composition and preparation method thereof, especially relate to a kind of Polyurethane Thermoplastic Elastomer injection moulding composition that is easy to the demoulding and preparation method thereof.
Background technology
Polyurethane Thermoplastic Elastomer polymkeric substance is a kind of to be made up of soft segment and rigid chain segment, has at low temperatures caoutchouc elasticity, high molecular synthetic material that again can plasticizing forming when rising temperature.Polyurethane Thermoplastic Elastomer polymkeric substance has excellent low temperature resistant, shock-resistant, resistant to chemical media and the characteristic such as wear-resisting, in a lot of fields as footwear material, health care, vehicle material etc. are widely used.
Injection moulding is one of main machining method of Polyurethane Thermoplastic Elastomer polymkeric substance; but the polarity of Polyurethane Thermoplastic Elastomer polymer molecular chain is strong, melt viscosity is high, microphase-separated is slow, crystallization while not exclusively causing in injection moulding some thin-gage goods with complicated shape as mobile phone protective cover, wrist-watch strap, usually there will be moulding slowly, the phenomenon of excessive cycle, thereby cause, production efficiency is low, increase of investment.Therefore, shortening injection molding cycle is the key problem in technology that further expands Polyurethane Thermoplastic Elastomer polymer application field.
At some other hemicrystalline material as polyamide (PA), in polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), the normal method of adding crystallization nucleating agent that adopts is to increase crystallization rate and the degree of crystallinity of material, thereby shorten material injection moulding demould time, but the application of crystallization nucleating agent in Polyurethane Thermoplastic Elastomer polymkeric substance and the report that release property is improved thereof are fewer, [the Freitag C such as Freitag, et al.PolymerEngineering and Science, 2011, 10:931] once reported and in Polyurethane Thermoplastic Elastomer polymer melt, added Organic Sodium Salt nucleator
clariant company of NaV101(Germany) can improve the degree of crystallinity of Polyurethane Thermoplastic Elastomer polymkeric substance, but do not studied its impact on injection molding cycle.
Adopting other polymkeric substance and the polymerization of Polyurethane Thermoplastic Elastomer polymer in situ or blending and modifying is the another method of shortening heat plastic polyurethane elastomer polymer demould time.N. the graceful grade of bohr [Chinese patent: CN1733817A] adds dystectic polybutylene terephthalate (PBT) in the process of synthetic soft thermoplastic polyurethane elastomers polymkeric substance.Correlation data shows, the existence of high-melting-point PBT is the demould time of shortening heat plastic polyurethane elastomer polymer effectively.Huarng R.J etc. [United States Patent (USP): US 5977268] have reported the also injection molding cycle of shortening heat plastic polyurethane elastomer polymer preferably of modified terpene resin that adds lower molecular weight, high softening-point in Polyurethane Thermoplastic Elastomer polymkeric substance injection moulding process.But the introducing of other polymkeric substance often also may cause the change of some other performance (as transparency, lower temperature resistance and oil-proofness etc.) of Polyurethane Thermoplastic Elastomer polymkeric substance.
The composition that the polymer blending of different properties Polyurethane Thermoplastic Elastomer is formed often has reasonable processibility, Chinese patent CN102197060A once reported and will after different sorts Polyurethane Thermoplastic Elastomer combination of polymers, apply for melt, this composition can demonstrate the process window wider than independent component, thereby be more conducive to the carrying out of melt coating procedure, but do not report its application in injection moulding field.
Therefore, in this area, urgently need the character such as a kind of transparency, lower temperature resistance and oil-proofness to keep good, and the Polyurethane Thermoplastic Elastomer injection moulding composition that is easy to the demoulding of energy shortening injection molding cycle.
Summary of the invention
The object of the present invention is to provide a kind of Polyurethane Thermoplastic Elastomer injection moulding composition that is easy to the demoulding and preparation method thereof.
It is 55000-105000 Polyurethane Thermoplastic Elastomer polymkeric substance that Polyurethane Thermoplastic Elastomer injection moulding composition of the present invention comprises two or more number-average molecular weights, wherein a kind of content of Polyurethane Thermoplastic Elastomer polymkeric substance is 50 ~ 80 % by weight, the total content of all the other Polyurethane Thermoplastic Elastomer polymkeric substance is 20 ~ 50 % by weight, taking the gross weight of this Polyurethane Thermoplastic Elastomer injection moulding composition as benchmark.
The preparation method of Polyurethane Thermoplastic Elastomer injection moulding composition of the present invention comprises the steps:
(1) the Polyurethane Thermoplastic Elastomer polymkeric substance (TPU) that synthetic two or more number-average molecular weight is 55000-105000 respectively is also a granulated into pellet form, then prepared TPU is dried to 2 ~ 5 hours at 100-120 DEG C;
(2) example takes respectively above dried TPU and is uniformly mixed to form polyurethane elastomer injection moulding composition in mass ratio.
Polyurethane Thermoplastic Elastomer injection moulding composition of the present invention has good processibility, in the time carrying out injection molding, can shorten cooling time, thereby improves its release property.
Embodiment
One preferred embodiment in, a kind of Polyurethane Thermoplastic Elastomer polymkeric substance that Polyurethane Thermoplastic Elastomer injection moulding composition of the present invention comprises 50 ~ 70 % by weight and remaining Polyurethane Thermoplastic Elastomer polymkeric substance of 30 ~ 50 % by weight, taking the gross weight of this Polyurethane Thermoplastic Elastomer injection moulding composition as benchmark.
In a preferred embodiment, a kind of Polyurethane Thermoplastic Elastomer polymkeric substance that Polyurethane Thermoplastic Elastomer injection moulding composition of the present invention comprises 50 ~ 60 % by weight and remaining Polyurethane Thermoplastic Elastomer polymkeric substance of 40 ~ 50 % by weight, taking the gross weight of this Polyurethane Thermoplastic Elastomer injection moulding composition as benchmark.
Polyurethane Thermoplastic Elastomer polymkeric substance of the present invention can be the Polyurethane Thermoplastic Elastomer polymkeric substance of any type, but is preferably polyester type or polyether-type Polyurethane Thermoplastic Elastomer polymkeric substance.
The Polyurethane Thermoplastic Elastomer polymkeric substance that in the present invention, Polyurethane Thermoplastic Elastomer polymkeric substance used is preferably mainly prepared under known catalyst action by linear macromolecule polyester or polyether Glycols and organic diisocyanate and short chain chainextender.Described polyether Glycols or the number-average molecular weight of polyester diol are 500-5000 dalton, are preferably 500-3000 dalton, more preferably 1000-2000 dalton.
In the present invention, polyester diol used is the polycondensation product of small molecules di-carboxylic acid and small molecules dibasic alcohol.Applicable di-carboxylic acid can be aliphatic, alicyclic or aromatic di-carboxylic acid, and it conventionally contains and adds up to 4 to 12 carbon atoms, is preferably and contains 4-10 carbon atom, more preferably contains 4-8 carbon atom.Applicable di-carboxylic acid can be for example succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecandioic acid, m-phthalic acid, terephthalic acid or cyclohexane dicarboxylic acid etc., be preferably two butyric acid, hexanodioic acid, suberic acid or their mixture, more preferably hexanodioic acid.Above-mentioned di-carboxylic acid also can use its derivative, as acid anhydrides or carboxylicesters.
Applicable dibasic alcohol can be aliphatic, aromatic dibasic alcohol or their mixture.It conventionally contains and adds up to 2 to 12 carbon atoms, is preferably and contains 2-6 carbon atom.
The example of suitable dibasic alcohol comprises ethylene glycol, 1,2-PD, 1,3-PD, 1,3 butyleneglycol, Isosorbide-5-Nitrae butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 2，2-dimethyl-1，3-propanediol, 1,4-cyclohexanedimethanol, decamethylene-glycol, 1,12 pairs of alcohol of 12-or their mixture; Preferably include ethylene glycol, butyleneglycol or hexylene glycol or their mixture.
Polyester diol used in the present invention can be prepared with polycondensation as known in the art.
In the present invention, polyester polyol used also comprises the polycondensation product of various aliphatics lactones and the reaction product of dibasic alcohol, as the reaction product of polycaprolactone and dibasic alcohol.
Polyester diol used in the present invention also comprises the PCDL of being prepared by carbonic ether and diol reaction.
In the present invention, polyether Glycols used is made by open loop of epoxy compound polymerization under existing as initiator and catalyzer containing active hydrogen compounds.Conventionally epoxy compounds contains 2-6 carbon atom; can be for example the polyoxyethylene glycol forming by oxyethane and glycol reaction, react the polypropylene glycol that forms by propylene oxide with propylene glycol, react by propylene oxide and oxyethane gathering (propylene glycol-ethylene glycol) or reacting the PTMG forming by tetrahydrofuran ring opening polymerization of forming with propylene glycol.
The present invention can also use copolyether, and typical copolyether comprises the copolyreaction product of tetrahydrofuran (THF) and oxyethane or tetrahydrofuran (THF) and propylene oxide.
Preferred polyether Glycols is for example PTMG dibasic alcohol.
The organic diisocyanate that is applicable to prepare the Polyurethane Thermoplastic Elastomer polymkeric substance in the present invention can be for example aromatic diisocyanate or aliphatics/alicyclic diisocyanate or its mixture, preferably aromatic diisocyanate.
Above-mentioned aromatic diisocyanate is for example selected from diphenylmethanediisocyanate (MDI), xylylene diisocyanate (XDI), 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate (TODI), phenylene-1,4-isocyanic ester (PPDI), tolylene diisocyanate (TDI) and naphthalene-1, one or more in 5-vulcabond (NDI); Aliphatics/alicyclic diisocyanate is selected from one or more in hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), isophorone diisocyanate (IPDI), Isosorbide-5-Nitrae-cyclohexyl-vulcabond (CHDI);
In the present invention, organic diisocyanate is preferably aromatic diisocyanate, specifically be selected from diphenylmethanediisocyanate (MDI), m-xylylene diisocyanate (XDI), phenylene-1,4-vulcabond (PPDI) and naphthalene-1, one or more in 5-vulcabond (NDI); Organic diisocyanate of the present invention is diphenylmethanediisocyanate (MDI) more preferably.
Be applicable to prepare the chainextender of the Polyurethane Thermoplastic Elastomer polymkeric substance in the present invention for containing having an appointment 2 to approximately 10 carbon atoms, preferably contain the aliphatic dihydroxy alcohol of 2-6; Specifically be selected from ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, BDO, 1, one or more in 6-hexylene glycol, 1,3 butylene glycol, 1,5-PD and neopentyl glycol; More preferably BDO of chainextender of the present invention.
The catalyzer that is applicable to prepare the Polyurethane Thermoplastic Elastomer polymkeric substance in the present invention is selected from one or more in organic acid salt or inorganic acid salt or its Organometallic derivatives and the trimethylamine of bismuth, tin, titanium, iron, antimony, cobalt, aluminium, thorium, zinc, nickel, cerium, molybdenum, vanadium, manganese and zirconium; Preferred catalyzer is organometallic compound, particularly preferably is organic metal salt or its combination of tin, bismuth, zinc and titanium.
The Polyurethane Thermoplastic Elastomer polymkeric substance that is applicable to prepare in the present invention adopts the ordinary method in this area to be prepared, as prepolymer method, conveyer belt or twin screw reaction extrusion molding.The present invention preferably adopts the preparation of twin screw reaction extrusion molding.Relevant twin screw reaction extrusion molding is produced the details of TPU can be referring to technical literature, for example, and polyurethane elastomer handbook (second edition), Chemical Industry Press, 2012:295; WangQueensland state, China Synthetic Rubber Industry, 1985,4::287; Chinese patent: CN1563133A etc.
Be applicable to the durometer level of two or more Polyurethane Thermoplastic Elastomer polymkeric substance of preparing Polyurethane Thermoplastic Elastomer injection moulding composition of the present invention at Shao Shi 70A-Shao Shi 100A, be preferably Shao Shi 75A-Shao Shi 95A, more preferably Shao Shi 80A-Shao Shi 90A.
One preferred embodiment in, the number-average molecular weight of Polyurethane Thermoplastic Elastomer injection moulding composition of the present invention two or more Polyurethane Thermoplastic Elastomer polymkeric substance used is 60000-100000.
Polyurethane Thermoplastic Elastomer injection moulding composition of the present invention can also comprise other raw material as known in the art and chemical assistant except above-mentioned Polyurethane Thermoplastic Elastomer polymkeric substance, as oxidation inhibitor, lubricant and anti ultraviolet agent etc.
Evenly mix with solid form by the method that Polyurethane Thermoplastic Elastomer injection moulding composition of the present invention the is prepared injecting products dried granules that can to comprise two or more number-average molecular weights be 55000-105000 Polyurethane Thermoplastic Elastomer polymkeric substance, and the mixture of gained is carried out to injection moulding with injection moulding machine.
For example comprise the injecting products of routine in this area with injecting products prepared by Polyurethane Thermoplastic Elastomer injection moulding composition of the present invention, as mobile phone protective cover and wrist-watch strap etc.
Compared with more existing technology, owing to not introducing polymkeric substance or the additive of other types in thermoplastic urethane elastomer composition in the present invention, other aspect characteristics of Polyurethane Thermoplastic Elastomer body do not reduce, therefore thermoplastic urethane elastomer composition of the present invention, in improving preferably injection moulding release property shortening injection molding cycle, still can keep original performance of its other side.And implementation method of the present invention is simple, without changing the original production formula of Polyurethane Thermoplastic Elastomer and technique, avoid increasing substantially production cost, have a good application prospect.
Embodiment
Following examples are only for further illustrating the present invention, are not violating under purport of the present invention, and the present invention should be not limited to the content that following examples are specifically expressed.
Testing method
Testing method and instrument used in following examples are as shown in the table:
Table 1
| Test event | Testing method and instrument |
| Shore hardness | GB/T2411-2008, durometer |
| Number-average molecular weight | Gel permeation chromatography (GPC) |
| Injection molding cycle | Injection moulding machine computer carries demonstration |
Preparation Example
React extrusion molding according to the method described in Chinese patent application CN1563133A by twin screw and produced following six kinds of independent Polyurethane Thermoplastic Elastomer (TPU) polymkeric substance.
TPU-1# is a kind of polyester type TPU, it is 2000 daltonian poly-hexanodioic acid-1 by number-average molecular weight, 4-butanediol ester glycol (PBA 2000), 1,4-butyleneglycol (BDO) and diphenylmethanediisocyanate (MDI) reaction make, its Shore A hardness is 85, and number-average molecular weight is 100000 dalton.
TPU-2# is a kind of polyester type TPU, it is 2000 daltonian poly-hexanodioic acid-1 by number-average molecular weight, 4-butanediol ester glycol (PBA 2000), 1,4-butyleneglycol (BDO) and diphenylmethanediisocyanate (MDI) reaction make, its Shore A hardness is 85, and number-average molecular weight is 80000 dalton.
TPU-3# is a kind of polyester type TPU, it is 1500 daltonian poly-hexanodioic acid-1 by number-average molecular weight, 4-butanediol ester glycol (PBA 1000), 1,4-butyleneglycol (BDO) and diphenylmethanediisocyanate (MDI) reaction make, its Shore A hardness is 85, and number-average molecular weight is 90000 dalton.
TPU-4# is a kind of polyester type TPU, it is 1000 daltonian polyethylene glycol adipate glycol (PEA 1000), 1 by number-average molecular weight, 4-butyleneglycol (BDO) and diphenylmethanediisocyanate (MDI) reaction make, its Shore A hardness is 85, and number-average molecular weight is 60000 dalton.
TPU-5# is a kind of polyether-type TPU, it is 2000 daltonian PTMG (PTMEG 2000), 1 by number-average molecular weight, 4-butyleneglycol (BDO) and diphenylmethanediisocyanate (MDI) reaction make, its Shore A hardness is 85, and number-average molecular weight is 90000 dalton.
TPU-6# is a kind of polyether-type TPU, it is 2000 daltonian PTMG (PTMEG 2000), 1 by number-average molecular weight, 4-butyleneglycol (BDO) and diphenylmethanediisocyanate (MDI) reaction make, its Shore A hardness is 85, and number-average molecular weight is 55000 dalton.
TPU-7# is a kind of polyether-type TPU, it is 1000 daltonian PTMG (PTMEG 1000), 1 by number-average molecular weight, 4-butyleneglycol (BDO) and diphenylmethanediisocyanate (MDI) reaction make, its Shore A hardness is 85, and number-average molecular weight is 60000 dalton.
Embodiment 1-9 and comparative example 1-4
By above seven kinds of dry different thermoplastic polyurethane elastomer polymeric aggregates according to shown in table 2 weight ratio weigh, and evenly mix, formed the raw mixture of following each embodiment and comparative example.
Table 2
By above different embodiment and comparative example at injection moulding machine (CJ80-E, Zhen De plastics machinery Co., Ltd., Factory) middle the same terms (injection temperature: 180-220 DEG C, injection pressure: 40-60bar) the circular print (diameter=100 millimeter) of lower injection moulding 3 mm thick, according to can be voluntarily passing judgment on the excellent degree of release property from mould needed injection cycle time that comes off from starting to be injected into print.Its result as shown below.
Table 3
As can be seen from Table 3, the Polyurethane Thermoplastic Elastomer injection moulding composition of embodiment 1-9 has shown shorter injection cycle, has shown good release property.% in the time that two kinds of Polyurethane Thermoplastic Elastomer polymkeric substance all account for 50 weight left and right of Polyurethane Thermoplastic Elastomer injection moulding composition gross weight, the release property displaying is best.Embodiment 2 is with embodiment 5 compared with comparative example 1-2, and injection cycle has shortened about 35%; Embodiment 8 is with embodiment 9 compared with comparative example 3-4, and injection cycle has shortened about 36%.
Claims (10)
1. a Polyurethane Thermoplastic Elastomer injection moulding composition, it is characterized in that, it is 55000-105000 Polyurethane Thermoplastic Elastomer polymkeric substance that said composition comprises two or more number-average molecular weights, wherein a kind of content of Polyurethane Thermoplastic Elastomer polymkeric substance is 50 ~ 80 % by weight, the total content of all the other Polyurethane Thermoplastic Elastomer polymkeric substance is 20 ~ 50 % by weight, taking the gross weight of this Polyurethane Thermoplastic Elastomer injection moulding composition as benchmark.
2. Polyurethane Thermoplastic Elastomer injection moulding composition according to claim 1, it is characterized in that, a kind of Polyurethane Thermoplastic Elastomer polymkeric substance of these injection moulding composition 50 ~ 70 % by weight and remaining Polyurethane Thermoplastic Elastomer polymkeric substance of 30 ~ 50 % by weight, taking the gross weight of this Polyurethane Thermoplastic Elastomer injection moulding composition as benchmark.
3. Polyurethane Thermoplastic Elastomer injection moulding composition according to claim 1 and 2, is characterized in that, the number-average molecular weight of described two or more Polyurethane Thermoplastic Elastomer polymkeric substance is 60000-100000.
4. Polyurethane Thermoplastic Elastomer injection moulding composition according to claim 1 and 2, is characterized in that, the durometer level of described two or more Polyurethane Thermoplastic Elastomer polymkeric substance is at Shao Shi 70A-Shao Shi 100A.
5. Polyurethane Thermoplastic Elastomer injection moulding composition according to claim 1 and 2, it is characterized in that, described two or more Polyurethane Thermoplastic Elastomer polymkeric substance are polyether-type Polyurethane Thermoplastic Elastomer polymkeric substance or polyester type Polyurethane Thermoplastic Elastomer polymkeric substance.
6. Polyurethane Thermoplastic Elastomer injection moulding composition according to claim 5, it is characterized in that, described polyether-type or polyester type Polyurethane Thermoplastic Elastomer are that the daltonian polyether Glycols of 500-5000 or polyester diol and organic diisocyanate and chainextender are made by number-average molecular weight.
7. Polyurethane Thermoplastic Elastomer injection moulding composition according to claim 6, is characterized in that, described organic diisocyanate is selected from aromatic diisocyanate or aliphatics/alicyclic diisocyanate or its combination.
8. Polyurethane Thermoplastic Elastomer injection moulding composition according to claim 6, is characterized in that, described chainextender is C
2-6alkane glycol.
9. Polyurethane Thermoplastic Elastomer injection moulding composition according to claim 6, is characterized in that, described polyester diol contains C
4-8aliphatic dicarboxylic acid copolymerization units and C
2-6alkane glycol copolymerization units, described polyether Glycols comprises PTMG.
10. the injecting products making with the Polyurethane Thermoplastic Elastomer injection moulding composition described in any one in claim 1-9.
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| CN105504222A (en) * | 2015-12-31 | 2016-04-20 | 山东一诺威聚氨酯股份有限公司 | Dedicated TPU material for high-transparency mobile phone shell jacket and preparation method thereof |
| CN106147206A (en) * | 2016-07-26 | 2016-11-23 | 福建师范大学泉港石化研究院 | A kind of yellowing-resistant antibacterial mobile phone shell sheath and preparation method thereof |
| CN107383325A (en) * | 2017-06-28 | 2017-11-24 | 苏州奥斯汀新材料科技有限公司 | A kind of high transparency method for preparing thermoplastic polyurethane elastomer |
| CN112322027A (en) * | 2020-11-17 | 2021-02-05 | 美瑞新材料股份有限公司 | High-strength matte thermoplastic polyurethane elastomer composition and preparation and application thereof |
| CN113208326A (en) * | 2021-04-28 | 2021-08-06 | 何惠玲 | Edge banding strip for furniture and preparation method thereof |
| CN113667290A (en) * | 2021-08-11 | 2021-11-19 | 沈阳化工大学 | Method for improving mechanical property of TPU (thermoplastic polyurethane) through physical blending adjustment of microphase separation structure |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504222A (en) * | 2015-12-31 | 2016-04-20 | 山东一诺威聚氨酯股份有限公司 | Dedicated TPU material for high-transparency mobile phone shell jacket and preparation method thereof |
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| CN106147206A (en) * | 2016-07-26 | 2016-11-23 | 福建师范大学泉港石化研究院 | A kind of yellowing-resistant antibacterial mobile phone shell sheath and preparation method thereof |
| CN106147206B (en) * | 2016-07-26 | 2018-10-30 | 福建师范大学泉港石化研究院 | A kind of yellowing-resistant antibacterial mobile phone shell sheath and preparation method thereof |
| CN107383325A (en) * | 2017-06-28 | 2017-11-24 | 苏州奥斯汀新材料科技有限公司 | A kind of high transparency method for preparing thermoplastic polyurethane elastomer |
| CN107383325B (en) * | 2017-06-28 | 2020-02-07 | 苏州奥斯汀新材料科技有限公司 | Preparation method of high-transparency thermoplastic polyurethane elastomer |
| CN112322027A (en) * | 2020-11-17 | 2021-02-05 | 美瑞新材料股份有限公司 | High-strength matte thermoplastic polyurethane elastomer composition and preparation and application thereof |
| CN113208326A (en) * | 2021-04-28 | 2021-08-06 | 何惠玲 | Edge banding strip for furniture and preparation method thereof |
| CN113667290A (en) * | 2021-08-11 | 2021-11-19 | 沈阳化工大学 | Method for improving mechanical property of TPU (thermoplastic polyurethane) through physical blending adjustment of microphase separation structure |
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Application publication date: 20140618 |