CN114044876A - Hybrid TPU capable of being crystallized quickly and having low refractive index and preparation method thereof - Google Patents
Hybrid TPU capable of being crystallized quickly and having low refractive index and preparation method thereof Download PDFInfo
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- CN114044876A CN114044876A CN202111303144.0A CN202111303144A CN114044876A CN 114044876 A CN114044876 A CN 114044876A CN 202111303144 A CN202111303144 A CN 202111303144A CN 114044876 A CN114044876 A CN 114044876A
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- tpu
- refractive index
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- low refractive
- polymer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 50
- 239000004005 microsphere Substances 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 25
- 150000002009 diols Chemical class 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 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 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000539 dimer Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- -1 polyoxytetramethylene Polymers 0.000 claims description 7
- 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 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- JRLZYKZRJOLHIJ-UHFFFAOYSA-N 2-prop-1-enoxyoxolane Chemical group O1C(CCC1)OC=CC JRLZYKZRJOLHIJ-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- NUHSROFQTUXZQQ-UHFFFAOYSA-N isopentenyl diphosphate Chemical compound CC(=C)CCO[P@](O)(=O)OP(O)(O)=O NUHSROFQTUXZQQ-UHFFFAOYSA-N 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
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 abstract description 37
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 37
- 239000011521 glass Substances 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 6
- 230000004313 glare Effects 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002077 nanosphere Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- 241000756137 Hemerocallis Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
- C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Abstract
The invention discloses a hybrid TPU (thermoplastic polyurethane) with rapid crystallization and low refractive index and a preparation method thereof, wherein (1) high-carbon alcohol is modified on the surface of a prepared hollow silicon dioxide nano microsphere; (2) under the protection of nitrogen and heating, adding isocyanate (MDI), hollow silica nano microspheres and a catalyst into a reactor to prepare a hollow silica microsphere hybrid TPU prepolymer, wherein the isocyanate accounts for 20-60 wt%; the TPU of the invention has the refractive index reduced to about 1.45, has low refractive index, can filter various glare, veiling glare, refracted light, reflected light, scattered light and the like in front of an automobile when being applied to automobile strong-grade glass, and reduces fatigue feeling caused by long-time driving; in addition, the hollow silicon dioxide nano microspheres have surface crystallizable and plastifiable properties, the processing difficulty of the polymer is not increased, the crystallization rate of the polymer is improved, the molding time of the product is shortened, and the processing and manufacturing cost can be saved.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a hybrid TPU (thermoplastic polyurethane) capable of being crystallized quickly and having a low refractive index and a preparation method thereof.
Background
The refractive index of a material is one of the basic optical parameters of a material to measure the propagation speed of light in a medium relative to that of light in air. Since the two media have different refractive indices, the propagation velocity of light propagating in the two media changes, which can be received by the human eye or by a light detector in the form of optical interference.
The reflectivity of the front windshield of a common automobile is 1.3-1.4, the front windshield or the glass laminated film is used, the refractive index range of the TPU is 1.51-1.57 which is far higher than that of the glass, so that various harmful light rays such as glare, stray light, refracted light, reflected light, scattered light and the like in front of the automobile are difficult to filter, the visual acuity, the color contrast, the visual field definition and the visual comfort are reduced, and the fatigue caused by long-time driving is increased; in addition, when driving at night, the image of the instrument panel is reflected on the front windshield or the rearview mirror, driving sight is influenced, and potential safety hazards exist.
The SiO2 material is used as a transparent material with low dielectric constant, the reflectivity of SiO2 in a 550nm wave band is 1.45-1.46, the material has excellent low reflectivity and stable chemical characteristics, is rich in source and low in cost, and becomes the most used material in the application of the antireflection film. Compared with the hybrid polyurethane prepared by directly doping the polyurethane particles into SiO2 powder, the hybrid polyurethane prepared by mixing and reacting the surface modified SiO2 and isocyanate in a liquid state can be uniformly dispersed better without agglomeration and caking, the problem of powder dispersion can be solved, the isocyanate is used as a cross-linking agent and is cross-linked with the SiO2 particles to form a net structure, the three-dimensional net structure improves the cross-linking density and the crystallization speed among the particles and between the particles and a glass substrate, and the hybrid polyurethane has excellent mechanical property, optical property and rapid crystallization property.
Therefore, by using the method for preparing hybrid hollow silica by using the patent CN107417973B organic-inorganic hybrid, firstly, hollow silica nano microspheres with the surface capable of crystallizing and plasticizing and containing high-carbon alcohol are prepared, and then, the hollow silica nano microspheres and isocyanate and the like are subjected to in-situ polymerization to prepare hybrid TPU, and a TPU composition with low refractive index, which is suitable for front windshield glass, glass laminated films and the like, is developed.
Disclosure of Invention
The invention aims to provide a hybrid TPU with rapid crystallization and low refractive index and a preparation method thereof, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: a hybrid TPU composition capable of being crystallized quickly and having a low refractive index is prepared by introducing hollow silica nanospheres into a small amount of chemically crosslinked molecular structures, wherein the surfaces of the hollow silica nanospheres are modified with high-carbon alcohol.
Preferably, the crystallization temperature of the hollow silica nanospheres is 50-150 ℃.
Preferably, the particle size of the hollow silicon dioxide nano microsphere is 0.05-3 μm.
A preparation method of a hybrid TPU composition with rapid crystallization and low refractive index comprises the following steps of (1) preparing hollow silicon dioxide nano microspheres, wherein the surfaces of the hollow silicon dioxide nano microspheres are modified with high-carbon alcohol;
(2) under the protection of nitrogen and heating, adding isocyanate (MDI), hollow silica nano microspheres and a catalyst into a reactor to prepare a hollow silica microsphere hybrid TPU prepolymer, wherein the isocyanate accounts for 20-60 wt%; the mass part of the hollow silica microspheres is 3-6%; the heating temperature is 80-100 ℃;
(3) under the protection of nitrogen and continuous heating, continuously stirring, continuously adding polyether or polyester dihydric alcohol and 1, 4-butanediol into the step (2), and reacting for 8-48 hours to prepare a TPU prepolymer with excessive NCO, wherein the mole number of the isocyanate group is equivalent to the total mole number of the high-carbon alcohol, the polyoxytetramethylene glycol and the 1, 4-butanediol; the mass portion of the polyether or polyester diol is 30-70%; the mass portion of the 1, 4-butanediol is 1-6%;
(4) adding a thermal initiator into the TPU prepolymer in the step (3) to react to prepare a hybrid TPU composition; the thermal initiator is 1-5% by weight.
Preferably, the isocyanate includes, but is not limited to, isophorone diisocyanate (IPDI), IPID dimer or polymer, Toluene Diisocyanate (TDI), TDI dimer or polymer, diphenylmethane diisocyanate (MDI), MDI dimer or polymer, dicyclohexylmethane-4, 4-diisocyanate (H12MI) I), H12MDI dimer or polymer, Hexamethylene Diisocyanate (HDI), HDI dimer or polymer, m-Xylylene Diisocyanate (XDI), dimer or polymer, hydrogenated xylylene diisocyanate HXDI, HXDI dimer or polymer.
Preferably, the polyether or polyester diol includes, but is not limited to, polyoxypropylene diol (PPG), polytetrahydrofuran diol (PTHF), polyoxytetramethylene diol (PTMG), tetrahydrofuran-oxypropylene copolyol, polyester diol, polycaprolactone polyol, polycarbonate diol.
Preferably, the thermal initiator comprises thermal initiation such as one or more of organic peroxides such as dibenzoyl peroxide, diisopropyl peroxydicarbonate (IPP), dicyclohexyl peroxydicarbonate (DCPD), Cumene Hydroperoxide (CHP), and azo compounds such as Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (AVBN).
Preferably, the preparation method of the hollow silica nanosphere with the surface modified with the higher alcohol comprises the following steps: 1) adding hollow silica nano microspheres into an organic solvent, and uniformly stirring;
2) adding a silane coupling agent into the dispersion liquid obtained in the step 1) under the protection of nitrogen, continuously stirring, and reacting for 8-48 hours at room temperature;
3) adding high-carbon alcohol into the dispersion liquid obtained in the step 2) under the protection of nitrogen, preserving the heat for 1-24 hours at the temperature of 20-80 ℃, cooling and drying to obtain the nano-silver-coated copper foil.
Compared with the prior art, the invention has the beneficial effects that: in the polyurethane adhesive, a-Si-O-group with a three-dimensional structure is introduced at the chain end of a TPU linear molecular chain, so that the wear resistance, the temperature resistance and the aging resistance of the TPU are optimized, the refractive index of the TPU is mainly reduced to about 1.45, the TPU has a low refractive index, and when the TPU is applied to automobile strong-grade glass, various glare, stray light, refracted light, reflected light, scattered light and the like in front of an automobile can be filtered, so that the visual acuity, the color contrast, the visual field definition and the visual comfort are improved, and the fatigue caused by long-time driving is reduced; in addition, when the automobile is driven at night, the phenomenon that the driving sight is influenced because the image of the instrument panel is reflected on the front windshield or the rearview mirror is avoided; in addition, the hollow silicon dioxide nano microspheres have surface crystallizable and plastifiable properties, the processing difficulty of the polymer is not increased, the crystallization rate of the polymer is improved, the molding time of the product is shortened, and the processing and manufacturing cost can be saved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: the hybrid TPU is prepared by introducing hollow silica nano-microspheres into a small amount of chemically crosslinked molecular structures, wherein the surfaces of the hollow silica nano-microspheres are modified with high-carbon alcohol.
In a preferred embodiment, the hollow silica nanospheres have the following structural formula:
wherein n is 16 to 48, and the mole number of the higher alcohol is preferably 2 or 4.
In a preferred embodiment, the particle size of the hollow silica nano microsphere is 0.5-2 μm.
A preparation method of the hybrid TPU composition capable of being crystallized quickly and having low refractive index further comprises the following steps:
(1) preparing hollow silicon dioxide nano microspheres according to the method disclosed in patent CN107417973B, wherein the surfaces of the hollow silicon dioxide nano microspheres are modified by high-carbon alcohol;
(2) under the protection of nitrogen and heating, adding isocyanate (MDI), hollow silica nano microspheres and a catalyst into a reactor to prepare a hollow silica microsphere hybrid TPU prepolymer, wherein the isocyanate accounts for 28-35% by weight; the mass part of the hollow silica microspheres is 4-6%; dripping 2-4 drops of the catalyst by using a suction pipe; the heating temperature is preferably 85-95 ℃; the specific structure of the hollow silicon dioxide nano microsphere hybridized TPU is as follows:
under the protection of nitrogen and continuous heating, continuously stirring, continuously adding polyether or polyester diol and 1, 4-butanediol into the step (2), and reacting for 24-36 hours to prepare a TPU prepolymer with excessive NCO, wherein the mole number of the isocyanate group is equivalent to the total mole number of the higher alcohol, the polyether or polyester diol and the 1, 4-butanediol; the mass portion of the polyether or polyester diol is 55-65%; the mass fraction of the 1, 4-butanediol is 2-4%; NCO is isocyanate group and is an important index for the quality of polyurethane products with a certain weight, and the specific structure of the TPU composition is as follows:
(4) adding a thermal initiator into the TPU prepolymer in the step (3) to react to prepare hybrid TPU particles; the thermal initiator is 1-3% by mass.
In a preferred embodiment, the polyisocyanate is toluene diisocyanate (MDI).
In a preferred embodiment, the polyether or polyester polyol is polyoxytetramethylene glycol or polycaprolactone glycol, and the molecular weight is 1000-4000.
In a preferred embodiment, the catalyst is a compound of dibutyltin dilaurate and triethylamine, and the mass ratio is 1.3: 1.
In a preferred embodiment, the initiator is a thermal initiator. The thermal initiator is azobisisobutyronitrile.
According to the invention, a-Si-O-group of the hollow silicon dioxide nano microsphere with a three-dimensional structure is introduced on a TPU linear molecular chain, so that the refractive index of the TPU is reduced to about 1.45 and the TPU has a low refractive index, besides the wear resistance, the temperature resistance and the aging resistance of the TPU are optimized; on the other hand, the hollow silicon dioxide nano microspheres have surface crystallizable and plastifiable properties, the processing difficulty of the polymer is not increased, the crystallization rate of the polymer is improved, the molding time of the product is shortened, and the processing and manufacturing cost can be saved.
The invention will now be further illustrated by reference to the following specific examples
The performance test methods of the samples prepared in examples and comparative examples are as follows:
wear resistance: the test is carried out according to the ASTM D4060 standard, and the smaller the number is, the better the wear resistance is represented;
solvent corrosion resistance: injection molding or pressing the sample into a sample piece of 10cm by 1 mm; and (2) filling corresponding ethanol (100%) and 95 # gasoline into a glass container, soaking the cut sample for 48 hours, and then testing the volume expansion rate, wherein the volume expansion rate is (expansion volume-initial volume)/100% of initial volume, and the large expansion rate indicates that the TPU product has poor solvent corrosion resistance.
Refractive index: the visible light spectrum range is 380 nm-780 nm; samples were prepared using glass as the substrate and tested according to the equipment and procedure of GB/T2680.
Gloss testing: test standards were followed by GBT 8807-.
Haze: the test was carried out according to the equipment and procedure of GB/T2410.
Elongation at break: the test was carried out according to the GB/T528 standard.
Melting point: the test was carried out according to the DSC method.
Crystallization temperature: the test was carried out according to the DSC method.
The ingredients of each component in examples 1-4 and comparative example 1 are shown in Table 1
Example 1 the preparation method is as follows:
(1) preparing hollow silicon dioxide nano microspheres according to the method disclosed in patent CN107417973B, wherein the surfaces of the hollow silicon dioxide nano microspheres are modified by high-carbon alcohol;
(2) adding 27.5 wt% of isocyanate (MDI), 2.8 wt% of hollow silicon dioxide nano microspheres, 0.3% of dibutyltin dilaurate and triethylamine catalyst into a reactor under the protection of nitrogen and heating (85-95 ℃), and preparing hollow silicon dioxide microsphere hybrid TPU;
(3) under the protection of nitrogen and with continuous heating (85-95 ℃), continuously stirring, adding 65 wt% of polyether diol (PTMEG3000) and 5.8 wt% of 1, 4-butanediol into the step (2), and reacting for 24-36 hours to prepare the TPU with excess NCO, wherein the mole number of the isocyanate groups is equivalent to the total mole number of the higher alcohol, the polyether or polyester diol and the 1, 4-butanediol.
Table 1:
MDI: diphenylmethane diisocyanate, wanhua chemistry;
PTMEG 3000: polytetramethylene ether glycol molecular weight 3000, korean PTG;
BDO: 1, 4-butanediol, alatin;
catalyst: dibutyltin dilaurate: daylily chemical industry, triethylamine: the quality ratio of the Hualu constant liter is 1.3: 1.
The resulting polyurethane compositions were subjected to performance tests according to the above performance standards, and the results are shown in Table 2.
Table 2:
as can be seen from Table 2, examples 1-5 have excellent optical properties, significantly reduced refractive index and haze, and significantly improved gloss, compared to comparative example 1 without hollow silica nanospheres; in comparison, the elongation at break is reduced due to the introduction of a three-dimensional Si-O structure, the elongation at break is obviously reduced along with the increase of the content of the hollow silica nano microspheres, the rigidity enhancement such as hardness and wear resistance are improved, and the melting point detected by a DSC method is increased due to the fact that the heat required by the melting of crystals is higher, which indicates that the crystallinity is higher, and meanwhile, the crystallization temperature is increased, which verifies that the crystallization speed is high. Meanwhile, the performance of ethanol resistance and 95 # gasoline is greatly improved compared with that of comparative example 1, and table 2 shows that when the content of the hollow silica microspheres is slightly higher, the embodiment 5 is more wear-resistant and corrosion-resistant, and the crystallinity is higher.
The ingredients of the components in examples 5-8 and comparative example 2 are shown in table 3.
Table 3:
wherein, PCL 1000: polycaprolactone diol, the rest being the same as in example 1-2.
The polyurethane compositions obtained in examples 6 to 10, comparative example 2, were also characterized using the above-mentioned criteria for characterization, the results of which are shown in Table 4:
table 4:
as can be seen from Table 4, in examples 6-10, compared with comparative example 2 without hollow silica nanospheres, the optical properties are excellent, the refractive index and haze are both significantly reduced, and the glossiness is significantly improved; in comparison, the elongation at break is reduced due to the introduction of a three-dimensional Si-0 structure, the elongation at break is obviously reduced along with the increase of the content of the hollow silicon dioxide nano microspheres, the rigidity enhancement such as hardness and wear resistance are improved, and the melting point detected by using a DSC method is increased due to the fact that the heat required by the melting of crystals is higher, which shows that the crystallinity is higher, and meanwhile, the crystallization temperature is increased to verify that the crystallization speed is high; meanwhile, the performance of ethanol resistance and 95 # gasoline is greatly improved compared with that of comparative example 1, and table 4 shows that when the content of the hollow silica microspheres is slightly higher, the embodiment 5 is more wear-resistant and corrosion-resistant, and the crystallinity is higher.
The above examples are provided to explain the embodiments of the present invention in detail, but the present invention is not limited to the above embodiments. Even if various changes are made to the present invention, it is still within the scope of the present invention if they fall within the scope of the claims of the present invention and their equivalents.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A rapidly crystallizable, low refractive index hybrid TPU composition characterized by: the hybrid TPU is prepared by introducing hollow silica nano-microspheres into a small amount of chemically crosslinked molecular structures, wherein the surfaces of the hollow silica nano-microspheres are modified with high-carbon alcohol.
2. A rapidly crystallizable, low refractive index hybrid TPU composition as described in claim 1 wherein: the crystallization temperature of the hollow silicon dioxide nano microspheres is 50-150 ℃.
3. A rapidly crystallizable, low refractive index hybrid TPU composition as described in claim 1 wherein: the particle size of the hollow silicon dioxide nano-microsphere is 0.05-3 mu m.
4. A process for preparing a rapidly crystallizable, low refractive index hybrid TPU composition as claimed in any one of claims 1-3, characterized by: (1) preparing hollow silicon dioxide nano microspheres, wherein the surfaces of the hollow silicon dioxide nano microspheres are modified with high-carbon alcohol;
(2) under the protection of nitrogen and heating, adding isocyanate (MDI), hollow silica nano microspheres and a catalyst into a reactor to prepare a hollow silica microsphere hybrid TPU prepolymer, wherein the isocyanate accounts for 20-60 wt%; the mass part of the hollow silica microspheres is 3-6%; the heating temperature is 80-100 ℃;
(3) under the protection of nitrogen and continuous heating, continuously stirring, continuously adding polyether or polyester dihydric alcohol and 1, 4-butanediol into the step (2), and reacting for 8-48 hours to prepare a TPU prepolymer with excessive NCO, wherein the mole number of the isocyanate group is equivalent to the total mole number of the high-carbon alcohol, the polyoxytetramethylene glycol and the 1, 4-butanediol; the mass portion of the polyether or polyester diol is 30-70%; the mass portion of the 1, 4-butanediol is 1-6%;
(4) adding a thermal initiator into the TPU prepolymer in the step (3) to react to prepare a hybrid TPU composition; the thermal initiator is 1-5% by weight.
5. The process of claim 4 for preparing a fast crystallizing, low refractive index hybrid TPU composition, wherein: the isocyanate includes, but is not limited to, isophorone diisocyanate (IPDI), IPID dimer or polymer, Toluene Diisocyanate (TDI), TDI dimer or polymer, diphenylmethane diisocyanate (MDI), MDI dimer or polymer, dicyclohexylmethane-4, 4-diisocyanate (H12MDI), H12MDI dimer or polymer, Hexamethylene Diisocyanate (HDI), HDI dimer or polymer, m-Xylylene Diisocyanate (XDI), dimer or polymer, hydrogenated xylylene diisocyanate HXDI, HXDI dimer or polymer.
6. The process of claim 4 for preparing a fast crystallizing, low refractive index hybrid TPU composition, wherein: the polyether or polyester diol includes, but is not limited to, polyoxypropylene diol (PPG), polytetrahydrofuran diol (PTHF), polyoxytetramethylene diol (PTMG), tetrahydrofuran-oxypropylene copolyol, polyester diol, polycaprolactone polyol, polycarbonate diol.
7. The process of claim 4 for preparing a fast crystallizing, low refractive index hybrid TPU composition, wherein: the thermal initiator includes one or more of thermal initiators such as organic peroxides such as dibenzoyl peroxide, diisopropyl peroxydicarbonate (IPP), dicyclohexyl peroxydicarbonate (DCPD), Cumene Hydroperoxide (CHP), and azo compounds such as Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (AVBN).
8. The process of claim 4 for preparing a fast crystallizing, low refractive index hybrid TPU composition, wherein: the preparation method of the hollow silicon dioxide nano microsphere with the surface modified with the higher alcohol comprises the following steps: 1) adding hollow silica nano microspheres into an organic solvent, and uniformly stirring;
2) adding a silane coupling agent into the dispersion liquid obtained in the step 1) under the protection of nitrogen, continuously stirring, and reacting for 8-48 hours at room temperature;
3) adding high-carbon alcohol into the dispersion liquid obtained in the step 2) under the protection of nitrogen, preserving the heat for 1-24 hours at the temperature of 20-80 ℃, cooling and drying to obtain the nano-silver-coated copper foil.
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