CN117801212A - Thermoplastic polyurethane elastomer material and preparation method thereof - Google Patents
Thermoplastic polyurethane elastomer material and preparation method thereof Download PDFInfo
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- CN117801212A CN117801212A CN202311697696.3A CN202311697696A CN117801212A CN 117801212 A CN117801212 A CN 117801212A CN 202311697696 A CN202311697696 A CN 202311697696A CN 117801212 A CN117801212 A CN 117801212A
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- sulfur
- diisocyanate
- thermoplastic polyurethane
- polyurethane elastomer
- diol
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 49
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 46
- 229920001971 elastomer Polymers 0.000 title claims abstract description 40
- 239000000806 elastomer Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000002009 diols Chemical group 0.000 claims abstract description 48
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 48
- 239000011593 sulfur Substances 0.000 claims abstract description 48
- 239000004970 Chain extender Substances 0.000 claims abstract description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims abstract description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 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 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 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 3
- LTOVZUHVYHATET-UHFFFAOYSA-N 1,2-diisocyanatoethylcyclohexane Chemical compound O=C=NCC(N=C=O)C1CCCCC1 LTOVZUHVYHATET-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000001746 injection moulding Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- -1 polyol compounds Chemical class 0.000 description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 9
- 150000001718 carbodiimides Chemical class 0.000 description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XGKGITBBMXTKTE-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)disulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SSC1=CC=C(O)C=C1 XGKGITBBMXTKTE-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Abstract
The invention discloses a thermoplastic polyurethane elastomer material. The raw materials used for the thermoplastic polyurethane elastomer material comprise diisocyanate, sulfur-containing linear dihydric alcohol and sulfur-containing diol chain extender. Wherein, the sulfur-containing diol used in the sulfur-containing linear diol and the sulfur-containing diol chain extender are each preferably of the following structures:
Description
Technical Field
The invention relates to the field of thermoplastic polyurethane elastomers, in particular to a thermoplastic polyurethane elastomer material with high transparency, high refractive index and uniform refractive index, and a preparation method and application thereof.
Background
Thermoplastic polyurethane elastomer is applied in more and more industries and fields by virtue of the special performance advantages of high strength, high wear resistance, high weather resistance, excellent biocompatibility and the like, and is assisted with good hot working and repeated processing performance, so that the thermoplastic polyurethane elastomer is commonly used in daily work and life in various product styles such as pipes, sheets, films and the like.
The polyurethane material is applied to the optical field, the problem of low refractive index always exists, and the most common method for solving the problem at present is to introduce disulfide bond and other groups with high refractive index into the material, so that the purpose of improving the refractive index of the polyurethane material is achieved.
Chinese patent CN95115109.6 increases the refractive index of polyurethane materials by using sulfur-containing diisocyanates or sulfur-containing polyol compounds.
Chinese patent CN98107456.1 increases the refractive index of the material by using thiols of various structures, but thiols have unpleasant smell as raw materials themselves, and are all linear structures, and the overall transparency of the material is general.
However, the method has certain problems that the disulfide bond has low bond energy, and the bond is easy to break under the action of certain hot processing conditions or reducing agents, so that the molecular weight of the material is reduced, and the performance is reduced; meanwhile, the polyurethane material has excessively high microphase separation degree, and uneven distribution of soft and hard segment microphase areas easily causes uneven overall refractive index of the material.
Disclosure of Invention
The invention aims to provide a thermoplastic polyurethane elastomer material which has a larger refractive index and a uniform refractive index on the premise of ensuring that the material has higher transparency.
Another object of the present invention is to provide a method for preparing the thermoplastic polyurethane elastomer material.
According to the invention, a large number of polysulfide bonds and annular structures are introduced into the material, and effective components with similar structures exist in the soft and hard sections and are uniformly distributed in the material, so that the refraction uniformity of the whole material is improved; meanwhile, the existence of the annular structure can play a role in protecting sulfur-sulfur bonds, so that the molecular weight of the material is not obviously reduced due to breakage of disulfide bonds in the processing process, and the performance is rapidly deteriorated.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the thermoplastic polyurethane elastomer material comprises the following raw materials in percentage by mass:
(1) 20-80%, preferably 50-60% of sulfur-containing linear diols obtained by polycondensation of sulfur-containing diols and diacids;
(2) 15-70%, preferably 25-30% of diisocyanate;
(3) 5-30%, preferably 14-24% of a sulfur-containing diol chain extender;
the percentages are based on the total mass of the raw materials;
wherein, the structural general formulas of the sulfur-containing diol and the sulfur-containing diol chain extender in the sulfur-containing linear diol are as follows:
wherein the R group comprises a cyclic structure consisting of 4-6 carbon atoms, including cyclobutyl, cyclohexyl and phenyl, and n is a natural number from 1 to 3. For example, the sulfur-containing diol is selected from the group consisting of 3,3 '-dithiobicyclo butanol, 4' -dithiobicyclo hexanol, 4 '-dithiobisphenol, and 2,2' -trithiobicyclo hexanol.
In a specific embodiment, the sulfur-containing linear diol is obtained by alkyd polycondensation of a sulfur-containing diol and a diacid, wherein the molar ratio of sulfur-containing diol to diacid is from 1.0 to 1.6, wherein the diacid is selected from the group consisting of succinic acid, adipic acid, suberic acid, sebacic acid;
preferably, the number average molecular weight of the sulfur-containing linear diol is 500 to 4000g/mol, preferably 1000 to 2500g/mol.
In a specific embodiment, the diisocyanate is selected from aromatic and/or aliphatic diisocyanates; preferably, the aromatic diisocyanate is selected from one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), and Xylylene Diisocyanate (XDI), and the aliphatic diisocyanate is selected from one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), 1, 4-cyclohexyldimethylene diisocyanate (HXDI), and 1, 4-cyclohexane diisocyanate (CHDI).
In a specific embodiment, the isocyanate index of the system of the present invention is from 0.8 to 1.2, preferably from 0.95 to 1.05.
In a specific embodiment, the thermoplastic polyurethane elastomer material further comprises a catalyst, the catalyst being added in an amount of 1 to 200ppm based on the total mass of diisocyanate, sulfur-containing linear diol and sulfur-containing diol chain extender;
in a specific embodiment, the catalyst is selected from one or more of tertiary amines, organotin, organobismuth, organozinc, preferably both organotin and organotin.
In a specific embodiment, the thermoplastic polyurethane elastomer material further comprises a mixing aid, wherein the mixing aid comprises one or more of a light stabilizer, an antioxidant and a hydrolysis stabilizer, and the adding amount of the mixing aid is 2-5wt% based on the total mass of diisocyanate, sulfur-containing linear diol and sulfur-containing diol chain extender.
The method for preparing the thermoplastic polyurethane elastomer material comprises the following steps:
(1) Forming a thermoplastic polyurethane elastomer from diisocyanate, sulfur-containing linear diol, sulfur-containing diol chain extender, optional catalyst and mixing auxiliary agent through an extruder; preferably, the extruder temperature is set between 120-240 ℃;
(2) Cooling the thermoplastic polyurethane elastomer, crushing and granulating.
Compared with the prior art, the invention has the following beneficial effects:
1) The sulfur-containing diol has the advantages that the molecular chains contain a large number of cyclic structures, the steric hindrance effect is large, the close packing of the molecular chains is hindered, the crystallinity is reduced, the transparency of the material is improved, and meanwhile, the micro-phase separation degree of the material is reduced by the similar structure, so that the distribution of the cyclic structures and the polysulfide bonds in the material is more uniform, and the problem of uneven refractive index caused by the distribution difference is solved;
2) A large number of annular structures in the sulfur-containing chain extender are symmetrically distributed at two ends of a disulfide bond, so that a certain protection effect can be achieved, and the degradation of material performance caused by breakage of the disulfide bond is prevented.
Detailed Description
The following examples will further illustrate the method provided by the present invention for a better understanding of the technical solution of the present invention, but the present invention is not limited to the examples listed but should also include any other known modifications within the scope of the claims of the present invention.
The invention is further illustrated by the following more specific examples, which do not limit the scope of the invention in any way.
The sulfur-containing diols in the following examples or comparative examples were all purchased from Hong Kong Chemhere company.
| Name of the name | Purity of | Manufacturer' s |
| 3,3' -dithiobicyclo butanol | 95％ | Hong Kong Chemhere |
| 4,4' -dithio-cyclohexanol | 95％ | Hong Kong Chemhere |
| 4,4' -dithiobisphenol | 95％ | Hong Kong Chemhere |
| 2,2' -trithio-bicyclo hexanols | 95％ | Hong Kong Chemhere |
In the following examples or comparative examples, all the raw materials except for the sulfur-containing diol were universal standards, and no special supply company was required.
The catalyst addition amounts described in the following examples and comparative examples were based on the total mass of diisocyanate, sulfur-containing linear diol, sulfur-containing diol chain extender.
In the specific embodiment, "parts" are "parts by mass".
In the following examples and comparative examples, the sulfur-containing linear diol was prepared mainly by the polycondensation reaction of alkyd, and the reaction process steps were as follows:
at room temperature, adding sulfur-containing diol and diacid into a reaction kettle with the capacity of 20L according to the mol ratio of 1.6, adding tetrabutyl titanate with the total mass fraction of 0.5 percent of the raw materials, filling nitrogen atmosphere for protection, gradually heating the mixture to 210-240 ℃ under stirring, stirring and reacting for 10-14h at the temperature, removing excessive unreacted diol and generated moisture from the mixture under 400 mPa vacuum until the acid value of the mixture is tested to be less than 1mgKOH/g, and collecting the prepared sulfur-containing linear diol for standby.
Example 1
A thermoplastic polyurethane elastomer comprising the following components:
31.8 parts of dicyclohexylmethane diisocyanate;
50.0 parts of poly (3, 3' -dithiobicyclo-butanol ester) diol;
18.2 parts of 3,3' -dithiobicyclo butanol;
80ppm of dibutyltin dilaurate;
tetrabutyl titanate 20ppm;
1010.5 parts of antioxidant;
0.5 part of hydrolysis-resistant carbodiimide;
wherein the number average molecular weight of the poly (3, 3' -dithiobicyclo-butanol ester) glycol is 1500g/mol;
the preparation method of the thermoplastic polyurethane comprises the following steps:
(1) Adding the components into a heated extruder, wherein the temperature of each temperature zone of the extruder is set to 140-220 ℃, and reacting in the heated extruder by a one-step polymerization method to form a thermoplastic polyurethane elastomer;
(2) Cooling the thermoplastic polyurethane elastomer, crushing and granulating.
Example 2
A thermoplastic polyurethane elastomer comprising the following components:
29.4 parts of dicyclohexylmethane diisocyanate;
50.0 parts of poly (4, 4' -dithio-cyclohexanol) glycol;
20.6 parts of 4,4' -dithio-cyclohexanol;
80ppm of dibutyltin dilaurate;
tetrabutyl titanate 20ppm;
1010.5 parts of antioxidant;
0.5 part of hydrolysis-resistant carbodiimide;
wherein the number average molecular weight of the poly (4, 4' -dithio-cyclohexanol) ester diol is 1500g/mol;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Example 3
A thermoplastic polyurethane elastomer comprising the following components:
29.9 parts of dicyclohexylmethane diisocyanate;
50.0 parts of poly (adipic acid) -4,4' -dithiodiphenol ester diol;
20.1 parts of 4,4' -dithiodiphenol;
80ppm of dibutyltin dilaurate;
tetrabutyl titanate 20ppm;
1010.5 parts of antioxidant;
0.5 part of hydrolysis-resistant carbodiimide;
wherein the number average molecular weight of the poly (adipic acid-4, 4' -dithiodiphenol ester diol) is 1500g/mol;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Example 4
A thermoplastic polyurethane elastomer comprising the following components:
27.8 parts of dicyclohexylmethane diisocyanate;
50.0 parts of poly (2, 2' -trithio-cyclohexanol) adipate diol;
22.2 parts of 2,2' -trithio-cyclohexanol;
80ppm of dibutyltin dilaurate;
tetrabutyl titanate 20ppm;
1010.5 parts of antioxidant;
0.5 part of hydrolysis-resistant carbodiimide;
wherein the number average molecular weight of the poly (adipic acid-2, 2' -trithio-cyclohexanol) ester diol is 1500g/mol;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Example 5
A thermoplastic polyurethane elastomer comprising the following components:
29.4 parts of dicyclohexylmethane diisocyanate;
50.0 parts of poly (3, 3' -dithiobicyclo-butanol ester) diol;
20.6 parts of 4,4' -dithio-cyclohexanol;
80ppm of dibutyltin dilaurate;
tetrabutyl titanate 20ppm;
1010.5 parts of antioxidant;
0.5 part of hydrolysis-resistant carbodiimide;
wherein the number average molecular weight of the poly (3, 3' -dithiobicyclo-butanol ester) glycol is 1500g/mol;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Example 6
A thermoplastic polyurethane elastomer comprising the following components:
25.2 parts of dicyclohexylmethane diisocyanate;
60.0 parts of poly (4, 4' -dithio-cyclohexanol) glycol;
14.8 parts of 4,4' -dithio-cyclohexanol;
80ppm of dibutyltin dilaurate;
tetrabutyl titanate 20ppm;
1010.5 parts of antioxidant;
0.5 part of hydrolysis-resistant carbodiimide;
wherein the number average molecular weight of the poly (4, 4' -dithio-cyclohexanol) ester diol is 1500g/mol;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Example 7
A thermoplastic polyurethane elastomer comprising the following components:
28.7 parts of diphenylmethane diisocyanate;
50.0 parts of poly (4, 4' -dithio-cyclohexanol) glycol;
21.3 parts of 4,4' -dithio-cyclohexanol;
80ppm of dibutyltin dilaurate;
tetrabutyl titanate 20ppm;
1010.5 parts of antioxidant;
0.5 part of hydrolysis-resistant carbodiimide;
wherein the number average molecular weight of the poly (4, 4' -dithio-cyclohexanol) ester diol is 1500g/mol;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Comparative example 1
A thermoplastic polyurethane elastomer comprising the following components:
39.4 parts of dicyclohexylmethane diisocyanate;
50.0 parts of poly (4, 4' -dithio-cyclohexanol) glycol;
10.6 parts of 1, 4-butanediol;
80ppm of dibutyltin dilaurate;
tetrabutyl titanate 20ppm;
1010.5 parts of antioxidant;
0.5 part of hydrolysis-resistant carbodiimide;
wherein the number average molecular weight of the poly (4, 4' -dithio-cyclohexanol) ester diol is 1500g/mol;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Comparative example 2
A thermoplastic polyurethane elastomer comprising the following components:
29.4 parts of dicyclohexylmethane diisocyanate;
50.0 parts of polybutylene adipate glycol;
20.6 parts of 4,4' -dithio-cyclohexanol;
80ppm of dibutyltin dilaurate;
tetrabutyl titanate 20ppm;
1010.5 parts of antioxidant;
0.5 part of hydrolysis-resistant carbodiimide;
wherein the number average molecular weight of the polybutylene adipate diol is 1500g/mol;
the above thermoplastic polyurethane preparation method is the same as in example 1.
The products prepared in the above examples and comparative examples were subjected to performance tests.
Transmittance and haze: the test samples are all 2mm injection molding test pieces, and the test standard is ASTM D1003;
refractive index: the 2.0mm sample prepared by the injection molding process was tested using a DR-M2 Abbe refractometer manufactured by ATAGO company.
The test results are shown in the following table:
table 1 results of performance testing of examples and comparative products
| Numbering device | Transmittance/% | Haze/% | Refractive index |
| Example 1 | 91.9 | 2.1 | 1.639 |
| Example 2 | 91.2 | 1.9 | 1.648 |
| Example 3 | 91.6 | 1.8 | 1.651 |
| Example 4 | 91.6 | 1.1 | 1.663 |
| Example 5 | 90.1 | 2.4 | 1.641 |
| Example 6 | 90.5 | 2.3 | 1.635 |
| Example 7 | 89.1 | 2.4 | 1.630 |
| Comparative example 1 | 88.1 | 2.9 | 1.495 |
| Comparative example 2 | 88.3 | 2.6 | 1.521 |
The thermoplastic polyurethane elastomer prepared by the invention can be used as an extrusion film material and an injection molding sheet material in the field of optical materials due to the excellent transparency and refractive index, but is not limited to the field of optical materials.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (10)
1. The thermoplastic polyurethane elastomer material comprises the following raw materials in percentage by mass:
(1) 20-80%, preferably 50-60% of sulfur-containing linear diols obtained by polycondensation of sulfur-containing diols and diacids;
(2) 15-70%, preferably 25-30% of diisocyanate;
(3) 5-30%, preferably 14-24% of a sulfur-containing diol chain extender;
the percentages are based on the total mass of the raw materials;
wherein the structural general formulas of the sulfur-containing diol and the sulfur-containing diol chain extender are as follows:
wherein R is selected from cyclic structures consisting of 4-6 carbon atoms, preferably cyclobutyl, cyclohexyl, phenyl, n is a natural number from 1 to 3.
2. The thermoplastic polyurethane elastomer material according to claim 1, wherein the sulfur-containing diol and sulfur-containing diol chain extender is selected from the group consisting of 3,3 '-dithiobicyclo butanol, 4' -dithiobicyclo hexanol, 4 '-dithiobisphenol, and 2,2' -trithiobicyclo hexanol.
3. The thermoplastic polyurethane elastomer material according to claim 1, wherein the molar ratio of the sulfur-containing linear diol to the diacid is 1.0 to 1.6, wherein the diacid is selected from the group consisting of succinic acid, adipic acid, suberic acid, sebacic acid.
4. A thermoplastic polyurethane elastomer material according to claim 1 or 3, characterized in that the number average molecular weight of the sulfur-containing linear diol is 500 to 4000g/mol, preferably 1000 to 2500g/mol.
5. Thermoplastic polyurethane elastomer material according to claim 1, characterized in that the diisocyanate is selected from aromatic and/or aliphatic diisocyanates; preferably, the aromatic diisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, p-phenylene diisocyanate and xylylene diisocyanate, and the aliphatic diisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1, 4-cyclohexyldimethylene diisocyanate and 1, 4-cyclohexane diisocyanate.
6. Thermoplastic polyurethane elastomer material according to claim 1, characterized in that the isocyanate index is 0.8 to 1.2.
7. The thermoplastic polyurethane elastomer material according to claim 1, further comprising a catalyst, wherein the catalyst is added in an amount of 1 to 200ppm based on the total mass of diisocyanate, sulfur-containing linear diol and sulfur-containing diol chain extender;
preferably, the catalyst is selected from one or more of tertiary amines, organic titanium, organic tin, organic bismuth and organic zinc.
8. The thermoplastic polyurethane elastomer material according to claim 1, further comprising a mixing aid comprising one or more of a light stabilizer, an antioxidant, and a hydrolysis stabilizer, wherein the mixing aid is added in an amount of 2 to 5wt% based on the total mass of diisocyanate, sulfur-containing linear diol, and sulfur-containing diol chain extender.
9. The method for producing a thermoplastic polyurethane elastomer material according to any one of claims 1 to 8, comprising the steps of:
(1) Forming a thermoplastic polyurethane elastomer from diisocyanate, sulfur-containing linear diol, sulfur-containing diol chain extender, optional catalyst and mixing auxiliary agent through an extruder;
(2) Cooling the thermoplastic polyurethane elastomer, crushing and granulating.
10. The production method according to claim 9, wherein the extruder temperature is set to between 120 and 240 ℃.
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| CN202311697696.3A CN117801212A (en) | 2023-12-12 | 2023-12-12 | Thermoplastic polyurethane elastomer material and preparation method thereof |
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