CN116854865A - Self-repairing scratch-resistant paint protective film and preparation method thereof - Google Patents
Self-repairing scratch-resistant paint protective film and preparation method thereof Download PDFInfo
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- CN116854865A CN116854865A CN202311134570.5A CN202311134570A CN116854865A CN 116854865 A CN116854865 A CN 116854865A CN 202311134570 A CN202311134570 A CN 202311134570A CN 116854865 A CN116854865 A CN 116854865A
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- Prior art keywords
- self
- protective film
- resistant paint
- repairing
- polyurethane
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- 239000003973 paint Substances 0.000 title claims abstract description 41
- 230000001681 protective effect Effects 0.000 title claims abstract description 37
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000004814 polyurethane Substances 0.000 claims abstract description 38
- 229920002635 polyurethane Polymers 0.000 claims abstract description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 23
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 9
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 125000001041 indolyl group Chemical group 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- PLVPPLCLBIEYEA-AATRIKPKSA-N (E)-3-(indol-3-yl)acrylic acid Chemical compound C1=CC=C2C(/C=C/C(=O)O)=CNC2=C1 PLVPPLCLBIEYEA-AATRIKPKSA-N 0.000 claims description 12
- PLVPPLCLBIEYEA-UHFFFAOYSA-N indoleacrylic acid Natural products C1=CC=C2C(C=CC(=O)O)=CNC2=C1 PLVPPLCLBIEYEA-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 claims description 9
- 229960001082 trimethoprim Drugs 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 229920005749 polyurethane resin Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
- C08G18/40—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
- C08G18/6666—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
- C08G18/6677—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 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a self-repairing scratch-resistant paint protective film and a preparation method thereof, and relates to the technical field of polyurethane and acrylic resin. Adopting trimethoyl alcohol as a chain extender, polymerizing polytetrahydrofuran glycol and polyisocyanate into hyperbranched polyurethane prepolymer, and introducing an acrylic resin chain segment containing indole rings into the hyperbranched polyurethane prepolymer. The self-repairing scratch-resistant paint protective film can be applied to aircraft, trains, automobiles or wind power blades, can be used as a self-repairing layer, can effectively resist scratches, improves the protective effect of paint and prolongs the service life, and has wide application prospect. In the process of preparing polyurethane, the trimellitic alcohol is used as a chain extender, so that the polyurethane can form a hyperbranched structure, the mechanical property of the whole molecule is more excellent, and in addition, the existence of benzene rings in the trimellitic alcohol enables the polyurethane molecule to have certain rigidity at the same time, so that the wear resistance of the polyurethane is further improved.
Description
Technical Field
The invention relates to the technical field of polyurethane and acrylic resin, in particular to a self-repairing scratch-resistant paint protective film and a preparation method thereof.
Background
The polyurethane material is prepared from raw materials such as isocyanate, polyether polyol or polyester polyol, a chain extender and the like, has the advantages of tear resistance, good processability and the like, and is widely applied. However, polyurethane is of a linear molecular structure and does not have self-repairing and scratch-resistant functions, so that when the polyurethane is used as a protective material for an aircraft, a helicopter, a high-speed railway or a wind power blade, a paint film is easily damaged due to collision or friction of external environments such as sand wind, branches and vehicles, and cracks of a coating structure are caused to be incapable of self-repairing, so that the protective effect and the service life of a paint surface are influenced.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a self-repairing scratch-resistant paint protective film and a preparation method thereof.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
a self-repairing scratch-resistant paint protective film is prepared by polymerizing polytetrahydrofuran glycol and polyisocyanate into hyperbranched polyurethane prepolymer by taking trimethoyl alcohol as a chain extender, and then introducing an acrylic resin chain segment containing indole rings into the hyperbranched polyurethane prepolymer.
The invention also discloses a preparation method of the self-repairing scratch-resistant paint protective film, which comprises the following steps:
(1) adding 50-70 parts by weight of polytetrahydrofuran glycol, 100-120 parts by weight of polyisocyanate and 1-10 parts by weight of dibutyltin dilaurate into a reaction kettle, heating to 60-90 ℃, stirring and reacting for 1-2 hours, cooling to 30-40 ℃, adding 20-60 parts by weight of trimethoprim alcohol, heating to 80-100 ℃, and continuing stirring and reacting for 1-3 hours to obtain hyperbranched polyurethane prepolymer;
(2) taking 30-40 parts of methacrylic acid, 12-16 parts of acrylamide, 21-26 parts of butyl acrylate, 5-14 parts of 3-indole acrylic acid, 0.5-3 parts of initiator and 50-100 parts of solvent, uniformly mixing to obtain a mixed solution, adding the obtained mixed solution into the hyperbranched polyurethane prepolymer obtained in the step (1) for a plurality of times, controlling the temperature of a reaction kettle to be not more than 105 ℃, and continuously stirring and reacting at 90-100 ℃ for 1-2 hours after the addition is completed to obtain an acrylic resin-polyurethane mixed solution;
(3) when the self-repairing scratch-resistant paint protective film is used, the acrylic resin-polyurethane mixed solution obtained in the step (2) is sprayed on a flat plate to form a film, and the film is dried for 1-2 hours to obtain the self-repairing scratch-resistant paint protective film.
Preferably, the polytetrahydrofuran diol is one or two of polytetrahydrofuran diol 1000, polytetrahydrofuran diol 2000, polytetrahydrofuran diol 250 or polytetrahydrofuran diol 650.
Preferably, the polyisocyanate is isophorone diisocyanate or hexamethylene diisocyanate.
Preferably, the initiator is benzoyl peroxide or azobisisobutyronitrile.
Preferably, the solvent is toluene or xylene.
Preferably, the drying temperature in step (3) is not more than 50 ℃, and the drying is generally carried out at room temperature. Tests show that the adhesive property of a paint film is easy to be influenced and curled after the paint film is dried at the temperature of more than 50 ℃.
Compared with the prior art, the invention has the following advantages:
the self-repairing scratch-resistant paint protective film can be applied to aircraft, trains, automobiles or wind power blades, can be used as a self-repairing layer, can effectively resist scratches, improves the protective effect of paint and prolongs the service life, and has wide application prospect.
In the process of preparing polyurethane, the trimellitic alcohol is used as a chain extender, so that on one hand, the trimellitic alcohol can enable the polyurethane to form a hyperbranched structure, the mechanical property of the whole molecule is more excellent, and on the other hand, the existence of benzene rings in the trimellitic alcohol enables the polyurethane molecule to have certain rigidity at the same time, and the wear resistance of the polyurethane molecule is further improved.
The acrylic resin is also added in the process of preparing polyurethane, the polymerization of the acrylic resin is carried out in a polyurethane mixed system, the acrylic resin can fill larger gaps generated between polyurethane crosslinking structures in the reaction process, a large number of groups such as carboxyl, carbonyl, amide and the like in the acrylic resin can form hydrogen bonds with nitrogen atoms and oxygen atoms of the polyurethane, and under the impact of external force, the polyurethane can quickly repair the material by the action of the hydrogen bonds after being scratched. In addition, 3-indole acrylic acid is added into the polyurethane material, so that the indole structure can improve the mechanical strength of the material, hydrogen bonds are easy to form, and the self-repairing rate of the material is greatly improved.
Drawings
FIG. 1 is a schematic illustration of the reaction scheme when the polyisocyanate is isophorone diisocyanate;
FIG. 2 is a schematic illustration of the reaction scheme when the polyisocyanate is hexamethylene diisocyanate.
Detailed Description
The invention aims to provide a self-repairing scratch-resistant paint protective film and a preparation method thereof, and the invention is further described below with reference to specific examples.
Example 1 a preparation method of a self-repairing scratch-resistant paint protective film, the reaction route of which is shown in fig. 1, specifically comprises the following steps:
(1) adding 1000 kg of polytetrahydrofuran glycol, 100kg of isophorone diisocyanate and 1kg of dibutyltin dilaurate into a reaction kettle, heating to 90 ℃, stirring for reacting for 2 hours, cooling to 30 ℃, adding 20kg of trimethoprim alcohol, heating to 100 ℃, and continuing stirring for reacting for 3 hours to obtain hyperbranched polyurethane prepolymer;
(2) taking 30kg of methacrylic acid, 12kg of acrylamide, 21kg of butyl acrylate, 5kg of 3-indoleacrylic acid, 0.5kg of benzoyl peroxide and 50kg of toluene, uniformly mixing to obtain a mixed solution, adding the obtained mixed solution into the hyperbranched polyurethane prepolymer obtained in the step (1) for 3 times, controlling the temperature of a reaction kettle to be not more than 105 ℃, and continuously stirring and reacting at 90 ℃ for 2 hours after the addition is finished to obtain an acrylic resin-polyurethane mixed solution;
(3) when in use, the acrylic resin-polyurethane mixed solution obtained in the step (2) is sprayed on a flat plate to prepare a film, and the film is dried for 1 hour to obtain the self-repairing scratch-resistant paint surface protective film.
Example 2 a method for preparing a self-repairing scratch-resistant paint protective film, the reaction route of which is shown in fig. 2, comprises the following steps:
(1) 2000 kg of polytetrahydrofuran glycol, 120kg of hexamethylene diisocyanate and 10kg of dibutyltin dilaurate are added into a reaction kettle, the temperature is raised to 60 ℃, stirring reaction is carried out for 1 hour, the temperature is reduced to 40 ℃, 60kg of trimethoprim alcohol is added, the temperature is raised to 80 ℃, stirring reaction is continued for 1 hour, and hyperbranched polyurethane prepolymer is obtained;
(2) taking 40kg of methacrylic acid, 16kg of acrylamide, 26kg of butyl acrylate, 14kg of 3-indoleacrylic acid, 3kg of azodiisobutyronitrile and 100kg of dimethylbenzene, uniformly mixing to obtain a mixed solution, adding the obtained mixed solution into the hyperbranched polyurethane prepolymer obtained in the step (1) for 6 times, controlling the temperature of a reaction kettle to be not more than 105 ℃, and continuously stirring and reacting at 100 ℃ for 1 hour after the addition is finished to obtain an acrylic resin-polyurethane mixed solution;
(3) when in use, the acrylic resin-polyurethane mixed solution obtained in the step (2) is sprayed on a flat plate to prepare a film, and the film is dried for 2 hours to obtain the self-repairing scratch-resistant paint surface protective film.
Example 3 a method for preparing a self-repairing scratch-resistant paint protective film, the reaction route of which is shown in fig. 1, comprises the following steps:
(1) adding 250 kg of polytetrahydrofuran glycol, 1000 kg of polytetrahydrofuran glycol, 105kg of isophorone diisocyanate and 3kg of dibutyltin dilaurate into a reaction kettle, heating to 70 ℃, stirring for reaction for 1.5 hours, cooling to 32 ℃, adding 30kg of trimethoprim alcohol, heating to 90 ℃, and continuing stirring for reaction for 2 hours to obtain hyperbranched polyurethane prepolymer;
(2) taking 32kg of methacrylic acid, 14kg of acrylamide, 22kg of butyl acrylate, 8kg of 3-indoleacrylic acid, 1kg of benzoyl peroxide and 60kg of toluene, uniformly mixing to obtain a mixed solution, adding the obtained mixed solution into the hyperbranched polyurethane prepolymer obtained in the step (1) for 4 times, controlling the temperature of a reaction kettle to be not more than 105 ℃, and continuously stirring and reacting at 95 ℃ for 1.5 hours after the addition is finished to obtain an acrylic resin-polyurethane mixed solution;
(3) when in use, the acrylic resin-polyurethane mixed solution obtained in the step (2) is sprayed on a flat plate to form a film, and the film is dried at 45 ℃ for 1.5 hours to obtain the self-repairing scratch-resistant paint protective film.
Example 4 a method for preparing a self-repairing scratch-resistant paint protective film, the reaction route of which is shown in fig. 2, comprises the following steps:
(1) adding 650-30 kg of polytetrahydrofuran glycol, 2000-35 kg of polytetrahydrofuran glycol, 110kg of hexamethylene diisocyanate and 6kg of dibutyltin dilaurate into a reaction kettle, heating to 80 ℃, stirring for reaction for 1.5 hours, cooling to 36 ℃, adding 40kg of trimethoprim alcohol, heating to 95 ℃, and continuing stirring for reaction for 1.5 hours to obtain hyperbranched polyurethane prepolymer;
(2) taking 38kg of methacrylic acid, 15kg of acrylamide, 24kg of butyl acrylate, 12kg of 3-indoleacrylic acid, 2kg of azodiisobutyronitrile and 90kg of dimethylbenzene, uniformly mixing to obtain a mixed solution, adding the obtained mixed solution into the hyperbranched polyurethane prepolymer obtained in the step (1) for 5 times, controlling the temperature of a reaction kettle to be not more than 105 ℃, and continuously stirring and reacting at 95 ℃ for 1.5 hours after the addition is finished to obtain an acrylic resin-polyurethane mixed solution;
(3) when in use, the acrylic resin-polyurethane mixed solution obtained in the step (2) is sprayed on a flat plate to form a film, and the film is dried for 1.5 hours at 40 ℃ to obtain the self-repairing scratch-resistant paint protective film.
Example 5 a method for preparing a self-repairing scratch-resistant paint protective film, the reaction route of which is shown in figure 1, comprises the following steps:
(1) 650 kg of polytetrahydrofuran glycol, 1000 kg of polytetrahydrofuran glycol, 115kg of isophorone diisocyanate and 6kg of dibutyltin dilaurate are added into a reaction kettle, the temperature is raised to 85 ℃, the stirring reaction is carried out for 1.5 hours, the temperature is reduced to 38 ℃, 30kg of trimethoprim alcohol is added, the temperature is raised to 85 ℃, and the stirring reaction is continued for 2 hours, so that hyperbranched polyurethane prepolymer is obtained;
(2) taking 35kg of methacrylic acid, 15kg of acrylamide, 25kg of butyl acrylate, 8kg of 3-indoleacrylic acid, 2kg of azodiisobutyronitrile and 80kg of dimethylbenzene, uniformly mixing to obtain a mixed solution, adding the obtained mixed solution into the hyperbranched polyurethane prepolymer obtained in the step (1) for 5 times, controlling the temperature of a reaction kettle to be not more than 105 ℃, and continuously stirring and reacting at 95 ℃ for 2 hours after the addition is finished to obtain an acrylic resin-polyurethane mixed solution;
(3) when in use, the acrylic resin-polyurethane mixed solution obtained in the step (2) is sprayed on a flat plate to form a film, and the film is dried for 1.5 hours at 50 ℃ to obtain the self-repairing scratch-resistant paint protective film.
The self-repairing and scratch-resistant paint protective films obtained in examples 1-5 were subjected to performance test, and the test results are shown in table 1, and the test method is as follows:
abrasion resistance: the smaller the number, the better the abrasion resistance is represented, tested according to ASTM D4060 standard.
Gloss test: the test standard was according to GBT 8807-1988.
Self-repairing performance: after scraping 10 times with sandpaper, the samples were left at 50 ℃ for 5 minutes for evaluation. More than 80% of scratches are repaired to be good, 50-80% of scratches are repaired to be medium, and less than 50% of scratches are repaired to be bad.
From the results shown in Table 1, the self-repairing and scratch-resistant paint protective film obtained by the invention has excellent wear resistance, scratch resistance, high light transmittance, good transparency and excellent self-repairing performance.
And (3) carrying out self-repairing performance test on the broken products of the examples 1-5, and preparing a dumbbell-shaped sample 4 from the acrylic resin-polyurethane mixed liquid obtained in the step (2) of the examples 1-5 according to GB/T528-1998 standard, wherein the test length is 10.0+/-0.5 mm and the test thickness is 1.0+/-0.1 mm. The tensile strength and elongation at break of the test pieces were obtained by tensile test, and then the fracture surfaces of the test pieces after being pulled out were rapidly and tightly butted and heated and solidified at different temperatures for 2 hours, and after being sufficiently cooled to room temperature, the test pieces were again stretched to measure the tensile strength and elongation at break, and the results are shown in Table 2.
As can be seen from the results in Table 2, the tensile strength recovery values before and after fracture of the samples obtained in examples 1 to 5 are 99% or more, the elongation recovery value at break is 98% or more, which indicates that the samples have high tensile strength and elasticity, have good scratch resistance after being prepared into paint films, and can realize high-integrity self-repair after fracture.
Comparative example 1 was identical to example 5 in both starting material and reaction conditions, except that benzyl alcohol was used in step (1) in place of the starting material, trimethoyl alcohol.
Comparative example 2 was identical to example 5 in both starting material and reaction conditions, except that 3-indoleacrylic acid was not added in step (2), and the amount of methacrylic acid was adjusted to 43kg.
Comparative example 3 was identical to example 5 in both starting material and reaction conditions, except that 3-indoleacrylic acid was not added in step (2), and the amount of butyl acrylate was adjusted to 33kg.
The paint films of comparative examples 1 to 3 were subjected to performance test, and the test results are shown in Table 3.
The test results of the samples of comparative examples 1 to 3 were shown in Table 4 by the method of Table 2.
As can be seen from the results in tables 3 and 4, in comparative example 1, since benzyl alcohol is used as a chain extender and no trimethoprim alcohol is used as a chain extender, the wear resistance and mechanical properties are greatly reduced, since the benzyl triol structure enables polyurethane to form a hyperbranched structure, the mechanical properties of the whole molecule are excellent, and meanwhile, the existence of benzene rings in the trimethoprim alcohol enables polyurethane molecules to have rigidity at the same time, so that the wear resistance of the polyurethane molecules is further improved. In comparative examples 2 to 3, the 3-indoleacrylic acid as a raw material is not added, and although the abrasion resistance is reduced less, the self-repairing and scratch resistance are reduced seriously, and the 3-indoleacrylic acid as a raw material can introduce an indole structure into polyurethane, so that the mechanical strength of the material is improved greatly, hydrogen bonds are formed easily, and the self-repairing rate of the material is improved greatly.
Claims (7)
1. A self-repairing scratch-resistant paint protective film is characterized in that: adopting trimethoyl alcohol as a chain extender, polymerizing polytetrahydrofuran glycol and polyisocyanate into hyperbranched polyurethane prepolymer, and introducing an acrylic resin chain segment containing indole rings into the hyperbranched polyurethane prepolymer.
2. The method for preparing the self-repairing scratch-resistant paint protective film as claimed in claim 1, which is characterized in that: the method comprises the following steps:
(1) adding 50-70 parts by weight of polytetrahydrofuran glycol, 100-120 parts by weight of polyisocyanate and 1-10 parts by weight of dibutyltin dilaurate into a reaction kettle, heating to 60-90 ℃, stirring and reacting for 1-2 hours, cooling to 30-40 ℃, adding 20-60 parts by weight of trimethoprim alcohol, heating to 80-100 ℃, and continuing stirring and reacting for 1-3 hours to obtain hyperbranched polyurethane prepolymer;
(2) taking 30-40 parts of methacrylic acid, 12-16 parts of acrylamide, 21-26 parts of butyl acrylate, 5-14 parts of 3-indole acrylic acid, 0.5-3 parts of initiator and 50-100 parts of solvent, uniformly mixing to obtain a mixed solution, adding the obtained mixed solution into the hyperbranched polyurethane prepolymer obtained in the step (1) for a plurality of times, controlling the temperature of a reaction kettle to be not more than 105 ℃, and continuously stirring and reacting at 90-100 ℃ for 1-2 hours after the addition is completed to obtain an acrylic resin-polyurethane mixed solution;
(3) when the self-repairing scratch-resistant paint protective film is used, the acrylic resin-polyurethane mixed solution obtained in the step (2) is sprayed on a flat plate to form a film, and the film is dried for 1-2 hours to obtain the self-repairing scratch-resistant paint protective film.
3. The method for preparing the self-repairing scratch-resistant paint protective film according to claim 2, which is characterized in that: the polytetrahydrofuran diol is one or two of polytetrahydrofuran diol 1000, polytetrahydrofuran diol 2000, polytetrahydrofuran diol 250 and polytetrahydrofuran diol 650.
4. The method for preparing the self-repairing scratch-resistant paint protective film according to claim 2, which is characterized in that: the polyisocyanate is isophorone diisocyanate or hexamethylene diisocyanate.
5. The method for preparing the self-repairing scratch-resistant paint protective film according to claim 2, which is characterized in that: the initiator is benzoyl peroxide or azobisisobutyronitrile.
6. The method for preparing the self-repairing scratch-resistant paint protective film according to claim 2, which is characterized in that: the solvent is toluene or xylene.
7. The method for preparing the self-repairing scratch-resistant paint protective film according to claim 2, which is characterized in that: the drying temperature in the step (3) is not more than 50 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015160866A (en) * | 2014-02-26 | 2015-09-07 | 日東電工株式会社 | Film having self-repairing property and production method of the same, and adhesive sheet using the film |
| CN113088176A (en) * | 2021-04-01 | 2021-07-09 | 南阳金牛彩印集团有限公司 | Self-repairing scratch-resistant polyurethane coating and preparation method thereof |
| WO2021232596A1 (en) * | 2020-05-21 | 2021-11-25 | 电子科技大学中山学院 | Thermal repair flexible transparent conductive film and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015160866A (en) * | 2014-02-26 | 2015-09-07 | 日東電工株式会社 | Film having self-repairing property and production method of the same, and adhesive sheet using the film |
| WO2021232596A1 (en) * | 2020-05-21 | 2021-11-25 | 电子科技大学中山学院 | Thermal repair flexible transparent conductive film and preparation method therefor |
| CN113088176A (en) * | 2021-04-01 | 2021-07-09 | 南阳金牛彩印集团有限公司 | Self-repairing scratch-resistant polyurethane coating and preparation method thereof |
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