CN116987376A - Thermoplastic elastomer for photochromic automobile protective film and preparation method thereof - Google Patents
Thermoplastic elastomer for photochromic automobile protective film and preparation method thereof Download PDFInfo
- Publication number
- CN116987376A CN116987376A CN202311239519.0A CN202311239519A CN116987376A CN 116987376 A CN116987376 A CN 116987376A CN 202311239519 A CN202311239519 A CN 202311239519A CN 116987376 A CN116987376 A CN 116987376A
- Authority
- CN
- China
- Prior art keywords
- thermoplastic elastomer
- protective film
- photochromic material
- photochromic
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 49
- 230000001681 protective effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 89
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 42
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 42
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 44
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 31
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 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 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 11
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 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 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 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 3
- 239000006172 buffering agent Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 15
- 239000006185 dispersion Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- 238000005406 washing Methods 0.000 description 28
- 239000007788 liquid Substances 0.000 description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 9
- 238000005469 granulation Methods 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- -1 PMMA modified MoO Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2258—Oxides; Hydroxides of metals of tungsten
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention relates to the technical field of high polymer materials, and provides a thermoplastic elastomer for a photochromic automobile protective film and a preparation method thereof. The thermoplastic elastomer for the photochromic automobile protective film comprises the following components in parts by mass: 100 parts of TPU, 5-15 parts of inorganic photochromic material, 1-3 parts of lubricant and 0.5-1.5 parts of antioxidant; the inorganic photochromic material comprises a silane coupling agent modified inorganic photochromic material and a PMMA modified inorganic photochromic material; the preparation method of the thermoplastic elastomer for the photochromic automobile protective film comprises the steps of mixing and melting the components in parts by mass, and extruding and granulating to obtain the thermoplastic elastomer for the photochromic automobile protective film. By the technical scheme, the problems of poor compatibility of the inorganic photochromic material and the high polymer material and uneven dispersion in the high polymer material in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a thermoplastic elastomer for a photochromic automobile protective film and a preparation method thereof.
Background
Along with the development of science and technology and the improvement of living standard of people, automobiles are gradually popular in the life of people, the demands of people on automobile protective films are gradually changed from practicability into diversity and functionality, and a photochromic film is a functional material capable of reversibly changing color along with the change of external illumination, can meet the demands of people on diversity and functionality, and is widely applied to the field of automobile protective films.
At present, the photochromic automobile protective film is prepared by coating a photochromic substance on the surface of a base film, and the problems of low rate of color change reaction, short color change duration, poor thermal stability, easy detachment of photochromic powder and the like exist in the process by utilizing the principle that the color of the photochromic substance is reversibly changed after the photochromic substance absorbs visible light and ultraviolet light under the irradiation of sunlight. Therefore, more preparation processes are used in actual production, namely, photochromic substances and high polymer materials are physically blended and then molded to prepare the photochromic automobile protective film.
Photochromic substances can be classified into organic photochromic materials and inorganic photochromic materials, and inorganic photochromic materials have many characteristics superior to organic photochromic materials, such as rapid rate of color change reaction, strong aging resistance, long duration of color change, good thermal stability, etc., but inorganic photochromic materials are usually metal oxides such as tungsten oxide (WO 3 ) Molybdenum trioxide (MoO) 3 ) And the like, the compatibility of the metal oxide and the high polymer material and the dispersibility of the metal oxide in the high polymer material are technical problems which are difficult to solve, and when the compatibility of the inorganic photochromic material and the high polymer material is poor and the dispersion in the high polymer material is uneven, the light transmittance and the mechanical strength of the automobile protective film are reduced.
Disclosure of Invention
The invention provides a thermoplastic elastomer for a photochromic automobile protective film and a preparation method thereof, which solve the problems of poor compatibility of inorganic photochromic materials and high polymer materials and uneven dispersion in the high polymer materials in the related technology.
The technical scheme of the invention is as follows:
the thermoplastic elastomer for the photochromic automobile protective film comprises the following components in parts by mass: 100 parts of TPU, 5-15 parts of inorganic photochromic material, 1-3 parts of lubricant and 0.5-1.5 parts of antioxidant;
the inorganic photochromic material comprises a silane coupling agent modified inorganic photochromic material and a PMMA modified inorganic photochromic material.
As a further technical scheme, the mass ratio of the silane coupling agent modified inorganic photochromic material to the PMMA modified inorganic photochromic material is 1:0.25-1.5.
As a further technical scheme, the mass ratio of the silane coupling agent modified inorganic photochromic material to the PMMA modified inorganic photochromic material is 3:2.
As a further technical scheme, the silane coupling agent modified inorganic photochromic material is prepared by the following method: adding the ethanol-water solution of the silane coupling agent into the inorganic photochromic material while stirring, continuously stirring, separating and drying to obtain the silane coupling agent modified inorganic photochromic material.
As a further technical scheme, the mass concentration of the silane coupling agent in the ethanol-water solution of the silane coupling agent is 5-10%.
As a further technical scheme, the mass ratio of the inorganic photochromic material to the silane coupling agent is 20:1.
As a further technical scheme, the silane coupling agent modified inorganic photochromic material comprises one or more of KH560 modified inorganic photochromic material, KH550 modified inorganic photochromic material and KH570 modified inorganic photochromic material.
As a further technical scheme, the silane coupling agent modified inorganic photochromic material comprises one or more of KH560 modified inorganic photochromic material and KH550 modified inorganic photochromic material.
As a further technical scheme, the silane coupling agent modified inorganic photochromic material is KH560 modified inorganic photochromic material.
As a further technical scheme, the preparation method of the PMMA modified inorganic photochromic material comprises the following steps:
s1, adding an ethanol-water solution of a coupling agent into an inorganic photochromic material while stirring, continuously stirring, separating and drying to obtain a double bond modified inorganic photochromic material;
s2, mixing the double bond modified inorganic photochromic material obtained in the step S1 with an emulsifying agent, a buffering agent, an initiator and water, heating, adding MMA, and reacting to obtain the PMMA modified inorganic photochromic material.
As a further technical scheme, the coupling agent in S1 comprises one or two of triacetoxy vinyl silane and vinyl methyl silicon (glycol) diacetate.
As a further technical scheme, the coupling agent in the S1 is triacetoxy vinyl silane.
As a further technical scheme, the mass ratio of the inorganic photochromic material to the coupling agent in the S1 is 20:1.
As a further technical scheme, the lubricant comprises one or more of methyl silicone oil, ethyl silicone oil and benzyl silicone oil;
the antioxidant comprises one or more of antioxidant 1010, antioxidant 264 and antioxidant 1076.
As a further technical scheme, the inorganic photochromic material comprises WO 3 、MoO 3 One or more of them.
The invention also provides a preparation method of the thermoplastic elastomer for the photochromic automobile protective film, which comprises the steps of mixing and melting the components in parts by mass, and extruding and granulating to obtain the thermoplastic elastomer for the photochromic automobile protective film.
The invention also provides an application of the thermoplastic elastomer for the photochromic automobile protective film or the thermoplastic elastomer for the photochromic automobile protective film prepared by the preparation method in the automobile protective film.
The working principle and the beneficial effects of the invention are as follows:
1. according to the invention, the silane coupling agent is used for modifying the inorganic photochromic material and the PMMA modified inorganic photochromic material to be matched, so that the aggregation of the inorganic photochromic material is eliminated, the inorganic photochromic material is uniformly dispersed into the high polymer material, the compatibility of the inorganic photochromic material and the high polymer material is improved, and the tensile strength and the light transmittance of the thermoplastic elastomer are improved.
2. According to the invention, KH560 modified inorganic photochromic material and PMMA modified inorganic photochromic material with the mass ratio of 1:0.25-1.5 are used, so that the tensile strength and the light transmittance of the thermoplastic elastomer are further improved.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a graph of water contact angle measurements of films made from the thermoplastic elastomer material of example 1 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The volume ratio of ethanol to water in the ethanol-water solution in the following examples and comparative examples was 1:1.
Example 1
S1, preparation of KH560 modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% KH560 ethanol-water solution, stirring at 30deg.C for 24 hr, separating solid and liquid, washing with ethanol solution for 2 times, and drying to obtain KH560 modified WO 3 ，WO 3 The mass ratio of KH560 is 20:1;
s2, preparing PMMA modified WO 3 : WO is incorporated into 3 Placing into a stirrer, stirring while addingAdding 8wt% of ethanol-water solution of triacetoxy vinyl silane, stirring at 30deg.C for 24 hr, separating solid and liquid, washing with ethanol solution for 2 times, and drying to obtain triacetoxy vinyl silane modified WO 3 ，WO 3 The mass ratio of the catalyst to the triacetoxy vinylsilane is 20:1; 10g of triacetoxyvinylsilane modified WO 3 Putting 0.5g of sodium dodecyl benzene sulfonate, 3g of sodium bicarbonate, 0.5g of ammonium persulfate and 1L of water into a three-neck flask, heating to 75 ℃, adding 20g of MMA to react for 5 hours, cooling at room temperature, performing solid-liquid separation, washing, and drying to obtain PMMA modified WO 3 ；
S3, modifying 100 parts of TPU and 6 parts of KH560 into WO 3 PMMA modified WO 4 parts 3 Mixing 2 parts of methyl silicone oil and 1 part of antioxidant 1010 uniformly in a mixer, transferring into a double-screw extruder, and carrying out melt extrusion and granulation at 190 ℃ to obtain the thermoplastic elastomer material.
Example 2
S1, preparation of KH560 modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% KH560 ethanol-water solution, stirring at 30deg.C for 24 hr, separating solid and liquid, washing with ethanol solution for 2 times, and drying to obtain KH560 modified WO 3 ，WO 3 The mass ratio of KH560 is 20:1;
s2, preparing PMMA modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% of ethanol-water solution of triacetoxy vinyl silane, stirring at 30deg.C for 24 hr, separating solid from liquid, washing with ethanol solution for 2 times, and drying to obtain triacetoxy vinyl silane modified WO 3 ，WO 3 The mass ratio of the catalyst to the triacetoxy vinylsilane is 20:1; 10g of triacetoxyvinylsilane modified WO 3 Putting 0.5g of sodium dodecyl benzene sulfonate, 3g of sodium bicarbonate, 0.5g of ammonium persulfate and 1L of water into a three-neck flask, heating to 75 ℃, adding 20g of MMA to react for 5 hours, cooling at room temperature, performing solid-liquid separation, washing, and drying to obtain PMMA modified WO 3 ；
S3, modifying 100 parts of TPU and 8 parts of KH560 into WO 3 2 parts of PMMA modified WO 3 Mixing 2 parts of methyl silicone oil and 1 part of antioxidant 1010 uniformly in a mixer, and transferring to double snailsIn a rod extruder, the thermoplastic elastomer material is obtained by melt extrusion and pelletization at 190 ℃.
Example 3
S1, preparation of KH560 modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% KH560 ethanol-water solution, stirring at 30deg.C for 24 hr, separating solid and liquid, washing with ethanol solution for 2 times, and drying to obtain KH560 modified WO 3 ，WO 3 The mass ratio of KH560 is 20:1;
s2, preparing PMMA modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% of ethanol-water solution of triacetoxy vinyl silane, stirring at 30deg.C for 24 hr, separating solid from liquid, washing with ethanol solution for 2 times, and drying to obtain triacetoxy vinyl silane modified WO 3 ，WO 3 The mass ratio of the catalyst to the triacetoxy vinylsilane is 20:1; 10g of triacetoxyvinylsilane modified WO 3 Putting 0.5g of sodium dodecyl benzene sulfonate, 3g of sodium bicarbonate, 0.5g of ammonium persulfate and 1L of water into a three-neck flask, heating to 75 ℃, adding 20g of MMA to react for 5 hours, cooling at room temperature, performing solid-liquid separation, washing, and drying to obtain PMMA modified WO 3 ；
S3, modifying 100 parts of TPU and 4 parts of KH560 into WO 3 PMMA modified WO 6 parts 3 Mixing 2 parts of methyl silicone oil and 1 part of antioxidant 1010 uniformly in a mixer, transferring into a double-screw extruder, and carrying out melt extrusion and granulation at 190 ℃ to obtain the thermoplastic elastomer material.
Example 4
S1, preparation of KH550 modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% KH550 ethanol-water solution, stirring at 30deg.C for 24 hr, separating solid and liquid, washing with ethanol solution for 2 times, and drying to obtain KH550 modified WO 3 ，WO 3 The mass ratio of KH550 to KH550 is 20:1;
s2, preparing PMMA modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% of ethanol-water solution of triacetoxy vinyl silane, stirring at 30deg.C for 24 hr, separating solid from liquid, washing with ethanol solution for 2 times, and drying to obtain triacetoxy vinyl silane modified WO 3 ，WO 3 The mass ratio of the catalyst to the triacetoxy vinylsilane is 20:1; 10g of triacetoxyvinylsilane modified WO 3 Putting 0.5g of sodium dodecyl benzene sulfonate, 3g of sodium bicarbonate, 0.5g of ammonium persulfate and 1L of water into a three-neck flask, heating to 75 ℃, adding 20g of MMA to react for 5 hours, cooling at room temperature, performing solid-liquid separation, washing, and drying to obtain PMMA modified WO 3 ；
S3, modifying 100 parts of TPU and 6 parts of KH550 into WO 3 PMMA modified WO 4 parts 3 Mixing 2 parts of methyl silicone oil and 1 part of antioxidant 1010 uniformly in a mixer, transferring into a double-screw extruder, and carrying out melt extrusion and granulation at 190 ℃ to obtain the thermoplastic elastomer material.
Example 5
S1, preparation of KH570 modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% KH570 ethanol-water solution, stirring at 30deg.C for 24 hr, separating solid and liquid, washing with ethanol solution for 2 times, and drying to obtain KH570 modified WO 3 ，WO 3 The mass ratio of KH570 to KH570 is 20:1;
s2, preparing PMMA modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% of ethanol-water solution of triacetoxy vinyl silane, stirring at 30deg.C for 24 hr, separating solid from liquid, washing with ethanol solution for 2 times, and drying to obtain triacetoxy vinyl silane modified WO 3 ，WO 3 The mass ratio of the catalyst to the triacetoxy vinylsilane is 20:1; 10g of triacetoxyvinylsilane modified WO 3 Putting 0.5g of sodium dodecyl benzene sulfonate, 3g of sodium bicarbonate, 0.5g of ammonium persulfate and 1L of water into a three-neck flask, heating to 75 ℃, adding 20g of MMA to react for 5 hours, cooling at room temperature, performing solid-liquid separation, washing, and drying to obtain PMMA modified WO 3 ；
S3, modifying 100 parts of TPU and 6 parts of KH570 into WO 3 PMMA modified WO 4 parts 3 Mixing 2 parts of methyl silicone oil and 1 part of antioxidant 1010 uniformly in a mixer, transferring into a double-screw extruder, and carrying out melt extrusion and granulation at 190 ℃ to obtain the thermoplastic elastomer material.
Example 6
S1, preparing KH560Modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% KH560 ethanol-water solution, stirring at 30deg.C for 24 hr, separating solid and liquid, washing with ethanol solution for 2 times, and drying to obtain KH560 modified WO 3 ，WO 3 The mass ratio of KH560 is 20:1;
s2, preparing PMMA modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding ethanol-water solution of 8wt% vinyl methyl silicon (glycol) diacetate, stirring at 30deg.C for 24 hr, separating solid and liquid, washing with ethanol solution for 2 times, and drying to obtain vinyl methyl silicon (glycol) diacetate modified WO 3 ，WO 3 The mass ratio of the vinyl methyl silicon (glycol) diacetate to the vinyl methyl silicon (glycol) diacetate is 20:1; 10g of vinyl methyl silicon (diol) diacetate modified WO 3 Putting 0.5g of sodium dodecyl benzene sulfonate, 3g of sodium bicarbonate, 0.5g of ammonium persulfate and 1L of water into a three-neck flask, heating to 75 ℃, adding 20g of MMA to react for 5 hours, cooling at room temperature, performing solid-liquid separation, washing, and drying to obtain PMMA modified WO 3 ；
S3, modifying 100 parts of TPU and 6 parts of KH560 into WO 3 PMMA modified WO 4 parts 3 Mixing 2 parts of methyl silicone oil and 1 part of antioxidant 1010 uniformly in a mixer, transferring into a double-screw extruder, and carrying out melt extrusion and granulation at 190 ℃ to obtain the thermoplastic elastomer material.
Example 7
S1, preparing KH560 modified MoO 3 : moO is carried out 3 Adding into a stirrer, stirring while adding 5wt% KH560 ethanol-water solution, stirring at 30deg.C for 24 hr, separating solid and liquid, washing with ethanol solution for 2 times, and drying to obtain KH560 modified MoO 3 ，MoO 3 The mass ratio of KH560 is 20:1;
s2, preparing PMMA modified MoO 3 : moO is carried out 3 Adding into a stirrer, stirring while adding 5wt% of ethanol-water solution of triacetoxy vinyl silane, stirring at 30deg.C for 24 hr, separating solid from liquid, washing with ethanol solution for 2 times, and drying to obtain triacetoxy vinyl silane modified MoO 3 ，MoO 3 The mass ratio of the catalyst to the triacetoxy vinylsilane is 20:1; 10g of triacetoxyvinylsilane modified MoO 3 Putting 0.5g of sodium dodecyl benzene sulfonate, 3g of sodium bicarbonate, 0.5g of ammonium persulfate and 1L of water into a three-neck flask, heating to 75 ℃, adding 20g of MMA to react for 5 hours, cooling at room temperature, performing solid-liquid separation, washing, and drying to obtain PMMA modified MoO 3 ；
S3, modifying 100 parts of TPU and 3 parts of KH560 into MoO 3 2 parts of PMMA modified MoO 3 Mixing 1 part of ethyl silicone oil and 0.5 part of antioxidant 1076 uniformly in a mixer, transferring into a double-screw extruder, and carrying out melt extrusion and granulation at 190 ℃ to obtain the thermoplastic elastomer material.
Example 8
S1, preparation of KH560 modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 10wt% KH560 ethanol-water solution, stirring at 30deg.C for 24 hr, separating solid and liquid, washing with ethanol solution for 2 times, and drying to obtain KH560 modified WO 3 ，WO 3 The mass ratio of KH560 is 20:1;
s2, preparing PMMA modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 10wt% of ethanol-water solution of triacetoxy vinyl silane, stirring at 30deg.C for 24 hr, separating solid from liquid, washing with ethanol solution for 2 times, and drying to obtain triacetoxy vinyl silane modified WO 3 ，WO 3 The mass ratio of the catalyst to the triacetoxy vinylsilane is 20:1; 10g of triacetoxyvinylsilane modified WO 3 Putting 0.5g of sodium dodecyl benzene sulfonate, 3g of sodium bicarbonate, 0.5g of ammonium persulfate and 1L of water into a three-neck flask, heating to 75 ℃, adding 20g of MMA to react for 5 hours, cooling at room temperature, performing solid-liquid separation, washing, and drying to obtain PMMA modified WO 3 ；
S3, modifying 100 parts of TPU and 9 parts of KH560 into WO 3 PMMA modified WO 6 parts 3 Mixing 3 parts of benzyl silicone oil and 1.5 parts of antioxidant 264 uniformly in a mixer, transferring into a double-screw extruder, carrying out melt extrusion at 190 ℃, and granulating to obtain the thermoplastic elastomer material.
Comparative example 1
S1, preparation of KH560 modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% KH560 ethanol-water solution, stirring at 30deg.C for 24After h, solid-liquid separation, washing 2 times with ethanol solution, drying to obtain KH560 modified WO 3 ，WO 3 The mass ratio of KH560 is 20:1;
s2, 100 parts of TPU and 10 parts of KH560 are modified to WO 3 Mixing 2 parts of methyl silicone oil and 1 part of antioxidant 1010 uniformly in a mixer, transferring into a double-screw extruder, and carrying out melt extrusion and granulation at 190 ℃ to obtain the thermoplastic elastomer material.
Comparative example 2
S1, preparing PMMA modified WO 3 : WO is incorporated into 3 Adding into a stirrer, stirring while adding 8wt% of ethanol-water solution of triacetoxy vinyl silane, stirring at 30deg.C for 24 hr, separating solid from liquid, washing with ethanol solution for 2 times, and drying to obtain triacetoxy vinyl silane modified WO 3 ，WO 3 The mass ratio of the catalyst to the triacetoxy vinylsilane is 20:1; 10g of triacetoxyvinylsilane modified WO 3 Putting 0.5g of sodium dodecyl benzene sulfonate, 3g of sodium bicarbonate, 0.5g of ammonium persulfate and 1L of water into a three-neck flask, heating to 75 ℃, adding 20g of MMA to react for 5 hours, cooling at room temperature, performing solid-liquid separation, washing, and drying to obtain PMMA modified WO 3 ；
S2, modifying 100 parts of TPU and 10 parts of PMMA to WO 3 Mixing 2 parts of methyl silicone oil and 1 part of antioxidant 1010 uniformly in a mixer, transferring into a double-screw extruder, and carrying out melt extrusion and granulation at 190 ℃ to obtain the thermoplastic elastomer material.
Comparative example 3
100 parts of TPU, 10 parts of WO 3 Mixing 2 parts of methyl silicone oil and 1 part of antioxidant 1010 uniformly in a mixer, transferring into a double-screw extruder, and carrying out melt extrusion and granulation at 190 ℃ to obtain the thermoplastic elastomer material.
Performance test:
(1) The thermoplastic elastomer materials obtained in examples 1 to 8 and comparative examples 1 to 3 were referred to GB/T1040.1-2018 "determination of Plastic tensile Properties part 1: testing tensile strength by a method of general rule;
(2) The thermoplastic elastomer materials obtained in examples 1 to 8 and comparative examples 1 to 3 were hot-pressed into films 1mm thick, and the transmittance was measured by using an ultraviolet-visible near-infrared spectrophotometer Cary 5000, and calculated according to the following formula;
light transmittance T (%) = (T) 555 ＋T 700 ＋T 900 ）÷3
The results are recorded in table 1.
TABLE 1 tensile Strength and light transmittance of thermoplastic elastomer materials
As can be seen from Table 1, the thermoplastic elastomer material provided by the invention has tensile strength of more than 50.2MPa, light transmittance of more than 74.6%, and good mechanical strength and light transmittance.
Example 1 KH560 modified WO used in example 1 compared with comparative examples 1 to 3 3 And PMMA modified WO 3 KH560 modified WO in comparative example 1 3 Modification of WO with PMMA in comparative example 2 3 No WO is available in comparative example 3 3 The tensile strength and transmittance of the modified thermoplastic elastomer material obtained in example 1 were higher than those of comparative examples 1 to 3, indicating that WO was modified with KH560 3 And PMMA modified WO 3 The inorganic photochromic material can be uniformly dispersed into the high polymer material by matching, and meanwhile, the compatibility of the inorganic photochromic material and the high polymer material is improved, so that the tensile strength and the light transmittance of the thermoplastic elastomer are greatly improved.
The thermoplastic elastomer material obtained in example 1 was hot-pressed into a film having a thickness of 1mm, and the water contact angle was measured by a water contact angle tester, and the measurement results are shown in FIG. 1.
As can be seen from fig. 1, the water contact angle of the thermoplastic elastomer material provided in embodiment 1 of the present invention reaches 117.2 °, and the water contact angle of the thermoplastic elastomer material obtained in other embodiments is similar to that of embodiment 1, so that the thermoplastic elastomer materials obtained in embodiments 1 to 8 of the present invention can achieve a good self-cleaning effect when applied to an automobile protective film during rain washing.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The thermoplastic elastomer for the photochromic automobile protective film is characterized by comprising the following components in parts by mass: 100 parts of TPU, 5-15 parts of inorganic photochromic material, 1-3 parts of lubricant and 0.5-1.5 parts of antioxidant;
the inorganic photochromic material comprises a silane coupling agent modified inorganic photochromic material and a PMMA modified inorganic photochromic material.
2. The thermoplastic elastomer for a photochromic automobile protective film according to claim 1, wherein the mass ratio of the silane coupling agent modified inorganic photochromic material to the PMMA modified inorganic photochromic material is 1:0.25-1.5.
3. The thermoplastic elastomer for a photochromic automobile protective film according to claim 1, wherein said silane coupling agent modified inorganic photochromic material is prepared by the following method: adding the ethanol-water solution of the silane coupling agent into the inorganic photochromic material while stirring, continuously stirring, separating and drying to obtain the silane coupling agent modified inorganic photochromic material.
4. The thermoplastic elastomer for a photochromic automotive protective film according to claim 3, wherein the mass concentration of the silane coupling agent in the ethanol-water solution of the silane coupling agent is 5 to 10%.
5. The thermoplastic elastomer for a photochromic automobile protective film according to claim 1, wherein said silane coupling agent modified inorganic photochromic material comprises one or more of KH560 modified inorganic photochromic material, KH550 modified inorganic photochromic material, KH570 modified inorganic photochromic material.
6. The thermoplastic elastomer for a photochromic automobile protective film according to claim 1, wherein said method for preparing a PMMA modified inorganic photochromic material comprises the steps of:
s1, adding an ethanol-water solution of a coupling agent into an inorganic photochromic material while stirring, continuously stirring, separating and drying to obtain a double bond modified inorganic photochromic material;
s2, mixing the double bond modified inorganic photochromic material obtained in the step S1 with an emulsifying agent, a buffering agent, an initiator and water, heating, adding MMA, and reacting to obtain the PMMA modified inorganic photochromic material.
7. The thermoplastic elastomer for a photochromic automotive protective film of claim 6 wherein the coupling agent in S1 comprises one or both of triacetoxy vinyl silane, vinyl methyl silicon (diol) diacetate.
8. The thermoplastic elastomer for a photochromic automobile protective film according to claim 1, wherein said lubricant comprises one or more of methyl silicone oil, ethyl silicone oil, benzyl silicone oil;
the antioxidant comprises one or more of antioxidant 1010, antioxidant 264 and antioxidant 1076.
9. The method for producing a thermoplastic elastomer for a photochromic automotive protective film according to any one of claims 1 to 8, wherein the thermoplastic elastomer for a photochromic automotive protective film is obtained by mixing and melting the components in parts by mass and then extruding and granulating the mixture.
10. The thermoplastic elastomer for a photochromic automobile protective film according to any one of claims 1 to 8 or the use of the thermoplastic elastomer for a photochromic automobile protective film prepared by the preparation method according to claim 9 in an automobile protective film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311239519.0A CN116987376B (en) | 2023-09-25 | 2023-09-25 | Thermoplastic elastomer for photochromic automobile protective film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311239519.0A CN116987376B (en) | 2023-09-25 | 2023-09-25 | Thermoplastic elastomer for photochromic automobile protective film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116987376A true CN116987376A (en) | 2023-11-03 |
| CN116987376B CN116987376B (en) | 2023-12-08 |
Family
ID=88525085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311239519.0A Active CN116987376B (en) | 2023-09-25 | 2023-09-25 | Thermoplastic elastomer for photochromic automobile protective film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116987376B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040138382A1 (en) * | 2001-01-29 | 2004-07-15 | Rodenstock Gmbh | Photochromic plastic object |
| CN109370561A (en) * | 2018-10-19 | 2019-02-22 | 如皋福大工程技术研究院有限公司 | A kind of phototropic compound polyurethane material with anti-ultraviolet function |
| CN110615904A (en) * | 2019-10-10 | 2019-12-27 | 立方米(厦门)光学科技有限公司 | Photochromic plate and manufacturing process thereof |
| CN112341798A (en) * | 2020-11-30 | 2021-02-09 | 山东一诺威聚氨酯股份有限公司 | Wear-resistant and ultraviolet aging-resistant polyurethane intelligent color-changing composite material and preparation method thereof |
| CN113861468A (en) * | 2021-10-11 | 2021-12-31 | 中国科学技术大学先进技术研究院 | Preparation method of photochromic tungsten oxide film and photochromic product |
-
2023
- 2023-09-25 CN CN202311239519.0A patent/CN116987376B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040138382A1 (en) * | 2001-01-29 | 2004-07-15 | Rodenstock Gmbh | Photochromic plastic object |
| CN109370561A (en) * | 2018-10-19 | 2019-02-22 | 如皋福大工程技术研究院有限公司 | A kind of phototropic compound polyurethane material with anti-ultraviolet function |
| CN110615904A (en) * | 2019-10-10 | 2019-12-27 | 立方米(厦门)光学科技有限公司 | Photochromic plate and manufacturing process thereof |
| CN112341798A (en) * | 2020-11-30 | 2021-02-09 | 山东一诺威聚氨酯股份有限公司 | Wear-resistant and ultraviolet aging-resistant polyurethane intelligent color-changing composite material and preparation method thereof |
| CN113861468A (en) * | 2021-10-11 | 2021-12-31 | 中国科学技术大学先进技术研究院 | Preparation method of photochromic tungsten oxide film and photochromic product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116987376B (en) | 2023-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105793332B (en) | Polyphenylene sulfide particulate | |
| CN102816399B (en) | PVDF (polyvinylidene fluoride) film modified with nano-titanium dioxide and preparation method for PVDA film | |
| CN116987376B (en) | Thermoplastic elastomer for photochromic automobile protective film and preparation method thereof | |
| CN111718450A (en) | Organic-inorganic electrically polarized particle and preparation method and application thereof | |
| CN105218987B (en) | A kind of blend film containing Graphene and preparation method thereof | |
| CN113234291B (en) | Polystyrene carbon black master batch and preparation method thereof | |
| CN107418053B (en) | Inorganic-organic hybrid microsphere anti-bonding master batch | |
| CN111253657B (en) | Conductive crosslinked polyethylene composite material and preparation method thereof | |
| CN110724373B (en) | PC/ABS alloy with no pockmark, high weather resistance, high black and bright and spraying-free effect and preparation method thereof | |
| CN104497405A (en) | Master-batch for EVA coating of solar photovoltaic component, preparation method of master-batch and preparation method of corresponding EVA coating | |
| CN105086466B (en) | The preparation method of acid and alkali-resistance molded silicon rubber | |
| CN112111137A (en) | Spraying-free material and preparation method and application thereof | |
| JP2009202561A (en) | Precursor for press working, and method of manufacturing the same | |
| CN113402776A (en) | Preparation method of nano silicon-based powder for improving resin fluidity | |
| CN110606986B (en) | Silicone rubber cross-linking agent, and preparation method and application thereof | |
| CN105622817B (en) | The method that body in-situ polymerization prepares EVA/ graphene composite materials | |
| CN110527287B (en) | Polyamide color master batch and preparation method thereof | |
| CN117304678B (en) | Thermoplastic elastomer for automobile protective film capable of rapidly dissipating heat and preparation method thereof | |
| JP3791223B2 (en) | Ethylene / tetrafluoroethylene copolymer composition | |
| CN113201157A (en) | TiO22Grafted polymethyl methacrylate ultraviolet light absorption film and preparation method thereof | |
| CN112920748A (en) | High ultraviolet light transmittance acrylic pressure-sensitive adhesive and preparation method thereof | |
| EP2581405A1 (en) | Copolymer nanocomposite | |
| CN112831147A (en) | Color-changing particle and preparation method thereof | |
| CN105061979B (en) | Flexural anti-compression high polymer material and preparation method thereof | |
| CN110343350B (en) | Preparation method of PVA composite material with shape memory function |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |