CN104193958A - High-hardness high-resilience thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
High-hardness high-resilience thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN104193958A CN104193958A CN201410480069.9A CN201410480069A CN104193958A CN 104193958 A CN104193958 A CN 104193958A CN 201410480069 A CN201410480069 A CN 201410480069A CN 104193958 A CN104193958 A CN 104193958A
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- thermoplastic elastomer
- thermoplastic polyurethane
- polyurethane thermoplastic
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 44
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 44
- 229920001971 elastomer Polymers 0.000 title claims abstract description 34
- 239000000806 elastomer Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 4
- 229920002635 polyurethane Polymers 0.000 claims description 13
- 239000004814 polyurethane Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 5
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 4
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 3
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims 11
- 239000003112 inhibitor Substances 0.000 claims 3
- 230000003647 oxidation Effects 0.000 claims 3
- 238000007254 oxidation reaction Methods 0.000 claims 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims 1
- 229940067597 azelate Drugs 0.000 claims 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 4
- 238000003490 calendering Methods 0.000 abstract description 2
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001896 polybutyrate Polymers 0.000 description 5
- IXQBIOPGDNZYNA-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC=C1C1=CC=CC=C1C Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1C1=CC=CC=C1C IXQBIOPGDNZYNA-UHFFFAOYSA-N 0.000 description 3
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 small molecule diol Chemical class 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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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
-
- 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
-
- 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
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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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4283—Hydroxycarboxylic acid or ester
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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
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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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- 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
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Abstract
本发明涉及一种高硬度高回弹热塑性聚氨酯弹性体及其制备方法。所述热塑性聚氨酯弹性体按重量份数包括以下成分：聚酯多元醇32～55；二异氰酸酯46～60；扩链剂15～33；抗氧剂2～5.5。将所述成分按配方量混合，在挤出机中进行聚合得到高硬度高回弹热塑性聚氨酯弹性体。本发明所述的热塑性聚氨酯弹性体具有优异的硬度和回弹性能，加工性能也比较良好，可以挤出、注塑、压延或吹塑成各种制品。The present invention relates to a high-hardness and high-resilience thermoplastic polyurethane elastomer and a preparation method thereof. The thermoplastic polyurethane elastomer comprises the following components by weight: 32-55 parts of polyester polyol; 46-60 parts of diisocyanate; 15-33 parts of chain extender; and 2-5.5 parts of antioxidant. The components are mixed according to the formula amount and polymerized in an extruder to obtain the high-hardness and high-resilience thermoplastic polyurethane elastomer. The thermoplastic polyurethane elastomer of the present invention has excellent hardness and resilience, and also has relatively good processing performance, and can be extruded, injection molded, calendered or blow molded into various products.
Description
技术领域technical field
本发明涉及热塑性聚氨酯制备技术领域，具体涉及一种高硬度高回弹热塑性聚氨酯弹性体及其制备方法。The invention relates to the technical field of thermoplastic polyurethane preparation, in particular to a thermoplastic polyurethane elastomer with high hardness and high resilience and a preparation method thereof.
背景技术Background technique
热塑性聚氨酯弹性体(TPU)是一种(AB)n型嵌段线性或有少量支化、交联的高分子材料。TPU的硬度范围相当宽，从邵A60～邵D80并且在整个硬度范围内具有高弹性；TPU在很宽的温度范围内(-40～120℃)具有良好的柔性；TPU还有良好的耐天候性，极优的耐高能射线性能，并且它的耐磨性、抗撕裂性、绕曲强度都是优良的；拉伸强度高，伸长率大，长期压缩永久变形率低等都是TPU的显著优点，但是当TPU的硬度高到一定值后(邵D50～80)，其加工性能就将变差，这也大大限制了高硬度TPU的应用，所以开发出加工性能优异的高硬度TPU日趋成为研究中的热点。Thermoplastic polyurethane elastomer (TPU) is a polymer material with (AB) n-type block linear or a small amount of branching and cross-linking. The hardness range of TPU is quite wide, from Shao A60 to Shao D80 and has high elasticity throughout the hardness range; TPU has good flexibility in a wide temperature range (-40 ~ 120 ° C); TPU also has good weather resistance Excellent resistance to high-energy rays, and its abrasion resistance, tear resistance, and bending strength are excellent; high tensile strength, high elongation, and low long-term compression set rate are all TPU. However, when the hardness of TPU reaches a certain value (Shao D50~80), its processing performance will become poor, which greatly limits the application of high hardness TPU, so the development of high hardness TPU with excellent processing performance increasingly becoming a research hotspot.
另外，现有的热塑性聚氨酯弹性体的回弹性能也无法满足某些应用领域的回弹性要求。例如轮滑鞋轮等。In addition, the resilience properties of existing thermoplastic polyurethane elastomers cannot meet the resilience requirements of some application fields. Such as roller skate wheels and so on.
CN 103130981A公开了一种高硬度热塑性聚氨酯弹性体及其制备方法。A组份包括大分子二元醇16.03～26.56份，小分子二元醇16.03～26.56份，二异氰酸酯46.88～67.94份；B组份包括扩链剂8.34～19.02份，抗氧剂0.7～1份。其中大分子二元醇与小分子二元醇的份数相同，且A组份与B组份之和为100份，OH基团与NCO基团的摩尔比为0.98。CN 103130981A discloses a high-hardness thermoplastic polyurethane elastomer and a preparation method thereof. Component A includes 16.03-26.56 parts of macromolecular diol, 16.03-26.56 parts of small molecule diol, 46.88-67.94 parts of diisocyanate; component B includes 8.34-19.02 parts of chain extender and 0.7-1 part of antioxidant . Wherein the number of parts of the macromolecular diol and the small molecule diol is the same, and the sum of the A component and the B component is 100 parts, and the molar ratio of the OH group to the NCO group is 0.98.
现有聚氨酯材料存在硬度低，回弹性差的问题，急需一种硬度较高但不影响加工性能、回弹性高的热塑性聚氨酯弹性体。Existing polyurethane materials have the problems of low hardness and poor resilience, and there is an urgent need for a thermoplastic polyurethane elastomer with high hardness that does not affect processing performance and high resilience.
发明内容Contents of the invention
本发明的目的在于针对现有聚氨酯材料的不足，提供一种高硬度高回弹热塑性聚氨酯弹性体。The object of the present invention is to provide a thermoplastic polyurethane elastomer with high hardness and high resilience aiming at the deficiencies of existing polyurethane materials.
为达此目的，本发明采用以下技术方案：For reaching this purpose, the present invention adopts following technical scheme:
一种高硬度高回弹热塑性聚氨酯弹性体，所述热塑性聚氨酯弹性体按重量份数包括以下成分：A high-hardness and high-resilience thermoplastic polyurethane elastomer, said thermoplastic polyurethane elastomer comprises the following components in parts by weight:
所述聚酯多元醇的重量份数可选择32.02～54.9，35～50，38.7～48.6，39～46，42.5～44，43等，皆可用于实施本发明。The parts by weight of the polyester polyol can be selected from 32.02 to 54.9, 35 to 50, 38.7 to 48.6, 39 to 46, 42.5 to 44, 43, etc., all of which can be used to implement the present invention.
所述二异氰酸酯的重量份数可选择46.03～59.8，48～56，50.7～55，53等，皆可用于实施本发明。The parts by weight of the diisocyanate can be selected from 46.03 to 59.8, 48 to 56, 50.7 to 55, 53, etc., all of which can be used to implement the present invention.
所述扩链剂的重量份数可选择15.02～32.8，15.4～30，18～28.6，20～26.4，22.3等，皆可用于实施本发明。The parts by weight of the chain extender can be selected from 15.02 to 32.8, 15.4 to 30, 18 to 28.6, 20 to 26.4, 22.3, etc., all of which can be used to implement the present invention.
所述抗氧剂的重量份数可选择2.01～5.48，2.3～5.1，2.5～4.8，3～4.2，3.7等，皆可用于实施本发明。The parts by weight of the antioxidant can be selected from 2.01 to 5.48, 2.3 to 5.1, 2.5 to 4.8, 3 to 4.2, 3.7, etc., all of which can be used to implement the present invention.
所述聚酯多元醇为聚己二酸酯、聚壬二酸酯、聚丁酸酯或聚碳酸酯中的一种或至少两种的混合物。典型但非限制性的例子包括但不限于：聚己二酸酯，聚壬二酸酯，聚丁酸酯，聚碳酸酯，聚己二酸酯和聚壬二酸酯，聚丁酸酯和聚碳酸酯，聚己二酸酯、聚壬二酸酯和聚丁酸酯，聚己二酸酯、聚壬二酸酯、聚丁酸酯和聚碳酸酯等。The polyester polyol is one or a mixture of at least two of polyadipate, polyazelate, polybutyrate or polycarbonate. Typical but non-limiting examples include, but are not limited to: polyadipate, polyazelate, polybutyrate, polycarbonate, polyadipate and polyazelate, polybutyrate and Polycarbonate, polyadipate, polyazelate and polybutyrate, polyadipate, polyazelate, polybutyrate and polycarbonate, etc.
所述二异氰酸酯包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、苯二亚甲基二异氰酸酯、3,3’-二甲基-4,4-联苯二异氰酸酯、三苯基甲烷三异氰酸酯或对苯二异氰酸酯中的一种或至少两种的混合物。典型但非限制性的例子包括但不限于：甲苯二异氰酸酯，二苯基甲烷二异氰酸酯，1,5-萘二异氰酸酯，苯二亚甲基二异氰酸酯，3,3’-二甲基-4,4-联苯二异氰酸酯，苯二亚甲基二异氰酸酯和3,3’-二甲基-4,4-联苯二异氰酸酯，三苯基甲烷三异氰酸酯和对苯二异氰酸酯，甲苯二异氰酸酯、二苯基甲烷二异氰酸酯和1,5-萘二异氰酸酯，1,5-萘二异氰酸酯、苯二亚甲基二异氰酸酯、对苯二异氰酸酯和二苯基甲烷二异氰酸酯等，皆可用于实施本发明。The diisocyanates include toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4-biphenyl diisocyanate, One or a mixture of at least two of triphenylmethane triisocyanate or p-phenylene diisocyanate. Typical but non-limiting examples include, but are not limited to: toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4, 4-biphenyl diisocyanate, xylylene diisocyanate and 3,3'-dimethyl-4,4-biphenyl diisocyanate, triphenylmethane triisocyanate and p-phenylene diisocyanate, toluene diisocyanate, di Phenylmethane diisocyanate and 1,5-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate and diphenylmethane diisocyanate, etc., can be used in the practice of the present invention.
所述扩链剂包含以下化合物：OH-(CH2)x-OH，其中x为5至26的整数。The chain extender includes the following compound: OH—(CH 2 ) x —OH, wherein x is an integer from 5 to 26.
所述抗氧剂为抗氧剂264、抗氧剂1010、抗氧剂1076、抗氧剂Tinuvin770、抗氧剂TPP或抗氧剂TNP中的一种或至少两种的混合物。典型但非限制性的例子包括但不限于：抗氧剂264，抗氧剂1010，抗氧剂1076，抗氧剂Tinuvin770、抗氧剂TPP和抗氧剂TNP，抗氧剂1010和抗氧剂1076，抗氧剂TPP、抗氧剂TNP、抗氧剂264和抗氧剂1010等，皆可用于实施本发明。The antioxidant is one or a mixture of at least two of antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant Tinuvin770, antioxidant TPP or antioxidant TNP. Typical but non-limiting examples include, but are not limited to: Antioxidant 264, Antioxidant 1010, Antioxidant 1076, Antioxidant Tinuvin770, Antioxidant TPP and Antioxidant TNP, Antioxidant 1010 and Antioxidant 1076, antioxidant TPP, antioxidant TNP, antioxidant 264 and antioxidant 1010 etc., all can be used for implementing the present invention.
作为本发明优选的技术方案，所述热塑性聚氨酯弹性体按重量份数包括以下成分：As a preferred technical solution of the present invention, the thermoplastic polyurethane elastomer comprises the following components in parts by weight:
所述扩链剂包含以下化合物：OH-(CH2)x-OH，其中x为10至15的整数。The chain extender includes the following compound: OH—(CH 2 ) x —OH, wherein x is an integer from 10 to 15.
作为本发明最优选的技术方案，所述热塑性聚氨酯弹性体按重量份数包括以下成分：As the most preferred technical solution of the present invention, the thermoplastic polyurethane elastomer comprises the following components in parts by weight:
所述扩链剂包含以下化合物：OH-(CH2)12-OH。The chain extender includes the following compound: OH-(CH 2 ) 12 -OH.
本发明所述的“包括”，意指其除所述组分外，还可以包括其他组分，这些其他组分赋予所述热塑性聚氨酯弹性体不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。The "comprising" in the present invention means that besides the above-mentioned components, other components may also be included, and these other components endow the thermoplastic polyurethane elastomer with different characteristics. In addition, the "comprising" in the present invention can also be replaced with the closed "for" or "consisting of".
除了上述确定组分，本发明TPU弹性体还可以任选包含多种添加剂、颜料、染料、填料、润滑剂、紫外线吸收剂、蜡、增稠剂等，可以本领域技术人员已知的常规量使用。通常使用的添加剂赋予热塑性聚氨酯弹性体所需性质。In addition to the above-mentioned determined components, the TPU elastomer of the present invention can also optionally contain various additives, pigments, dyes, fillers, lubricants, ultraviolet absorbers, waxes, thickeners, etc., which can be conventional amounts known to those skilled in the art use. Commonly used additives impart the desired properties to thermoplastic polyurethane elastomers.
一种所述的热塑性聚氨酯弹性体的制备方法，所述制备方法将所述成分按配方量混合，在挤出机中进行聚合得到高硬度高回弹热塑性聚氨酯弹性体。A preparation method of the thermoplastic polyurethane elastomer, the preparation method is to mix the ingredients according to the formula, and polymerize in an extruder to obtain a high hardness and high resilience thermoplastic polyurethane elastomer.
本发明热塑性聚氨酯(TPU)弹性体可以挤出为任何所需最终产物或形式，或可以冷却、制粒或造粒用于储存或以大块运输。挤出后可以立即以其它方式处理挤出物，以得到所需最终产品。The thermoplastic polyurethane (TPU) elastomers of the present invention can be extruded into any desired end product or form, or can be cooled, pelletized or pelletized for storage or shipped in bulk. Immediately after extrusion the extrudate may be otherwise processed to obtain the desired end product.
与已有技术方案相比，本发明具有以下有益效果：Compared with the prior art solutions, the present invention has the following beneficial effects:
本发明所述的热塑性聚氨酯弹性体具有优异的硬度和回弹性能，加工性能也比较良好，可以挤出、注塑、压延或吹塑成各种制品。The thermoplastic polyurethane elastomer of the present invention has excellent hardness and rebound performance, and relatively good processing performance, and can be extruded, injected, calendered or blow-molded into various products.
下面对本发明进一步详细说明。但下述的实例仅仅是本发明的简易例子，并不代表或限制本发明的权利保护范围，本发明的保护范围以权利要求书为准。The present invention will be further described in detail below. However, the following examples are only simple examples of the present invention, and do not represent or limit the protection scope of the present invention, and the protection scope of the present invention shall be determined by the claims.
具体实施方式Detailed ways
下面通过具体实施方式来进一步说明本发明的技术方案。The technical solutions of the present invention will be further described below through specific embodiments.
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：For better illustrating the present invention, facilitate understanding technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
实施例1Example 1
一种高硬度高回弹热塑性聚氨酯弹性体，所述热塑性聚氨酯弹性体按重量份数包括以下成分：A high-hardness and high-resilience thermoplastic polyurethane elastomer, said thermoplastic polyurethane elastomer comprises the following components in parts by weight:
所述扩链剂包含以下化合物：OH-(CH2)5-OH。The chain extender includes the following compound: OH-(CH 2 ) 5 -OH.
将所述成分按配方量混合，在挤出机中进行聚合得到高硬度高回弹热塑性聚氨酯弹性体。The ingredients are mixed according to the formulation amount, and polymerized in an extruder to obtain a thermoplastic polyurethane elastomer with high hardness and high resilience.
实施例2Example 2
一种高硬度高回弹热塑性聚氨酯弹性体，所述热塑性聚氨酯弹性体按重量份数包括以下成分：A high-hardness and high-resilience thermoplastic polyurethane elastomer, said thermoplastic polyurethane elastomer comprises the following components in parts by weight:
所述扩链剂包含以下化合物：OH-(CH2)26-OH。The chain extender includes the following compound: OH—(CH 2 ) 26 -OH.
其制备方法同实施例1。Its preparation method is with embodiment 1.
实施例3Example 3
一种高硬度高回弹热塑性聚氨酯弹性体，所述热塑性聚氨酯弹性体按重量份数包括以下成分：A high-hardness and high-resilience thermoplastic polyurethane elastomer, said thermoplastic polyurethane elastomer comprises the following components in parts by weight:
所述扩链剂包含以下化合物：OH-(CH2)10-OH。The chain extender includes the following compound: OH—(CH 2 ) 10 —OH.
其制备方法同实施例1。Its preparation method is with embodiment 1.
实施例4Example 4
一种高硬度高回弹热塑性聚氨酯弹性体，所述热塑性聚氨酯弹性体按重量份数包括以下成分：A high-hardness and high-resilience thermoplastic polyurethane elastomer, said thermoplastic polyurethane elastomer comprises the following components in parts by weight:
所述扩链剂包含以下化合物：OH-(CH2)15-OH。The chain extender includes the following compound: OH—(CH 2 ) 15 -OH.
其制备方法同实施例1。Its preparation method is with embodiment 1.
实施例5Example 5
一种高硬度高回弹热塑性聚氨酯弹性体，所述热塑性聚氨酯弹性体按重量份数包括以下成分：A high-hardness and high-resilience thermoplastic polyurethane elastomer, said thermoplastic polyurethane elastomer comprises the following components in parts by weight:
所述扩链剂包含以下化合物：OH-(CH2)12-OH。The chain extender includes the following compound: OH-(CH 2 ) 12 -OH.
其制备方法同实施例1。Its preparation method is with embodiment 1.
对比例1Comparative example 1
将CN 103130981A中公开的实施例1作为本发明的对比例1。The embodiment 1 disclosed in CN 103130981A is used as comparative example 1 of the present invention.
对比例2Comparative example 2
将CN 103130981A中公开的实施例2作为本发明的对比例1。The embodiment 2 disclosed in CN 103130981A is used as comparative example 1 of the present invention.
将本发明实施例1-5和对比例1-2的硬度和回弹性测试结果在表1中进行对比。The hardness and resilience test results of Examples 1-5 of the present invention and Comparative Examples 1-2 are compared in Table 1.
表1各实施例和对比例的性能对比表The performance contrast table of each embodiment of table 1 and comparative example
申请人声明，所属技术领域的技术人员在上述实施例的基础上，将上述实施例某组分的具体含量点值，与发明内容部分的技术方案相组合，从而产生的新的数值范围，也是本发明的记载范围之一，本申请为使说明书简明，不再罗列这些数值范围。The applicant declares that on the basis of the above-mentioned examples, those skilled in the art combine the specific content point value of a certain component in the above-mentioned examples with the technical solution in the summary of the invention to generate a new numerical range, which is also It is one of the description ranges of the present invention. In order to make the description concise, the present application does not list these numerical ranges any more.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.
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