Polymer primer and preparation method thereof

Abstract

The invention provides a polymer primer and a preparation method thereof, and belongs to the technical field of high polymer materials. The polymer primer comprises a polymer, a monomer, a functional auxiliary agent and the like, the adhesive force, the wear resistance and the water resistance of the primer are improved through multiple crosslinking modes of photo-initiation and moisture curing, and the polymer primer has wide application space and market value.

Description

Technical Field

[0001] The invention belongs to the field of polymer technology, and in particular relates to a polymer primer and a preparation method thereof. Background Art

[0002] In the production process of transportation equipment such as automobiles, buses, and trains, the glass installation process requires a layer of primer to be applied on the glass. After the primer is cured, glue is applied on the surface of the primer to ensure the firmness, reliability, and portability of the glass installation. In order to improve the safety and service life of the glass after installation, the adhesion, water resistance, wear resistance, and high temperature resistance of the primer are crucial.

[0003] At present, most of the glass primers used in the market are moisture-curing polyurethane primers modified by silane coupling agents. This type of primer has a fast surface drying time and excellent adhesion, but poor water resistance and limited heat resistance. Therefore, developing a glass primer that is water-resistant, heat-resistant, and highly reliable is of great significance for improving the safety, comfort, and environmental adaptability of vehicles such as automobiles. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a polymer primer and a preparation method thereof, wherein the primer has a simple preparation process and has excellent hydrolysis resistance, high temperature and high humidity resistance and good adhesion performance.

[0005] The present invention provides a polymer primer, which comprises the following raw materials in parts by mass: 100 parts of polyurethane prepolymer, 10-60 parts of acrylate monomer, 1-20 parts of photoinitiator, 0.01-13 parts of catalyst, 0.3-30 parts of graphene and its derivatives, 10-100 parts of carbon black, 2-30 parts of chain extender, 0.1-10 parts of antioxidant, 200-700 parts of solvent, 0.1-20 parts of other fillers, 5-30 parts of coupling agent; The prepolymer comprises the following raw materials: 100 parts of polymer polyol and 15-210 parts of isocyanate.

[0006] Preferably, the polyol is selected from one or more of polyethylene glycol propylene glycol adipate diol, sorbitol, polybutylene glycol, polyoxypropylene triol, polycaprolactone diol, castor oil polyol, polytetramethylene ether diol, polypropylene glycol adipate diol, polyethylene glycol, polyhexamethylene carbonate diol, and polytrimethylene ether glycol.

[0007] Preferably, the isocyanate is selected from one or more of hexamethylene diisocyanate, hexamethylene diisocyanate trimer, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate biuret, isophorone diisocyanate trimer, lysine diisocyanate, methylcyclohexyl diisocyanate, cyclohexane dimethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate trimer, toluene diisocyanate trimer, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate dimer and diphenylmethane diisocyanate dimer.

[0008] Preferably, the solvent is one or more of chloroform, ether, petroleum ether, toluene, ethyl acetate, methyl ethyl ketone, butyl acetate, dichloromethane, ethanol, methanol, acetone and xylene.

[0009] Preferably, the catalyst is selected from one or more of stannous octoate, triethylamine, dibutyltin diacetate, potassium acetate, lead isooctanoate, phenylmercuric acetate, dibutyltin dilaurate, tetrabutyl titanate, tetramethyldipropylenetriamine, tetramethylpropylenediamine, tetramethylhexanediamine, N-methylimidazole, N-methylmorpholine, 1,4-dimethylpiperazine, bismuth isooctanoate and triethylenediamine.

[0010] Preferably, the chain extender is selected from one or more of 1,4-butanediol, glycidyl allyl ether, trimethylolpropane, trimethylolethane, methyldiethanolamine, carbodiimide, 1,6-hexanediol, glycerol, diethylene glycol, triethylene glycol, triethanolamine, neopentyl glycol, 4,4'-methylenebis(2-chloroaniline), ethylenediamine, 1,4-cyclohexanediol, tetramethylhexanediamine and hydrogenated bisphenol A.

[0011] The antioxidant is selected from one or more of Irganox 5057, Irganox 1098, Irganox 1135, Irgastab PUR 70, MIANOX 1098, antioxidant 1010, antioxidant 5057, antioxidant 168, antioxidant 1076, B225 and BHT.

[0012] Preferably, the acrylic acid ester monomer is selected from two or more of methyl acrylate, ethyl acrylate, methyl 2-methacrylate, ethyl 2-methacrylate, butyl methacrylate, butyl acrylate, and hydroxyethyl methacrylate.

[0013] Preferably, the photoinitiator is selected from (2,4,6 (trimethylbenzoyl) diphenylphosphine oxide) (TPO), (2,4,6-trimethylbenzoylphosphonic acid ethyl ester) (TPO-L), (2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone) (907), (2-isopropylthioxanthone (2, 4 isomer mixture) (ITX), (1-hydroxy-cyclohexyl-phenyl ketone) (184), (2-hydroxy-2-methyl-1-phenyl-1-propanone) (1173), (benzoin dimethyl ether) (BD K), (methyl o-benzoylbenzoate) (OMBB), (benzophenone) (BP), (4-chlorobenzophenone) (CBP), (4-phenylbenzophenone) (PBZ), (2-phenylbenzyl-2-dimethylamino-1-(4-morpholinobenzylphenyl)butanone) (369), (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) (819), (benzoylformate mixture) (754), photoinitiator (2-hydroxy-2-methylformylphenyl)benzyl)-2-methyl-1-propanone) (127) One or more.

[0014] Preferably, the other fillers are selected from one or more of silicon dioxide, titanium dioxide, sodium silicate, zinc oxide and aluminum oxide; The graphene and its derivatives are selected from one or more of graphene oxide, single-layer graphene with a sheet diameter of less than 50 μm, graphene with 2 to 10 layers, and graphene with more than 10 layers; The carbon black is selected from one or more of ordinary carbon black, high-pigment carbon black with a mesh size greater than 1250, acetylene carbon black and high-wear-resistant furnace black.

[0015] Preferably, the coupling agent is selected from one or more of γ-aminopropyltriethoxysilane, titanate coupling agent, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, isocyanatepropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, isocyanatepropyltrimethoxysilane, γ-(2,3-epoxypropyl)propyltrimethoxysilane, anilinemethyltrimethoxysilane and γ-aminoethylaminopropyltrimethoxysilane.

[0016] The present invention provides a method for preparing the polymer primer described in the above technical solution, comprising the following steps: After vacuum dehydration of the polyol, add isocyanate at 60-90°C and react for 1-3 hours to obtain a polyurethane prepolymer; Add acrylate monomer, photoinitiator, chain extender, coupling agent, catalyst and solvent to the above polyurethane prepolymer, and stir at 60-90°C for 0.5-2 hours; Graphene and its derivatives, other fillers, carbon black, etc. are gradually added to the above-mentioned mixed solution, and after grinding and mixing for 1.5 to 5 hours, a polymer primer is obtained.

[0017] When using the primer prepared as above, it is applied to a clean and dry glass surface, and then immediately irradiated with ultraviolet light for 3-10 minutes; in this way, dual curing of ultraviolet light crosslinking and moisture curing is achieved, and the crosslinked structure gives the coating excellent water resistance and stability.

[0018] Compared with the prior art, the polymer primer provided by the present invention uses multiple crosslinking methods such as photoinitiation and moisture curing, that is, the molecular chains between the polymers are bonded and crosslinked to form a network structure, and the free radical polymerization and crosslinking of the acrylate monomers are initiated by light, so as to improve the strength, heat resistance, wear resistance, solvent resistance and other properties, and form more hydrogen bonds during the bonding process, thereby improving the adhesion of the primer; in addition, combined with the addition of other fillers, it can also protect the surface, increase the storage stability and service life of the system, which is superior to the prior art and has a wide range of application space and market value. DETAILED DESCRIPTION

[0019] The present invention provides a polymer primer, which comprises the following raw materials in parts by mass: 100 parts of polyurethane prepolymer, 10-60 parts of acrylate monomer, 1-20 parts of photoinitiator, 0.01-13 parts of catalyst, 0.3-30 parts of graphene and its derivatives, 10-100 parts of carbon black, 2-30 parts of chain extender, 0.1-10 parts of antioxidant, 200-700 parts of solvent, 0.1-20 parts of other fillers, 5-30 parts of coupling agent; The prepolymer comprises the following raw materials: 100 parts of polymer polyol and 15-210 parts of isocyanate.

[0020] The polyurethane primer provided by the present invention is prepared by spontaneously undergoing a crosslinking modification reaction in a photoinitiator under the irradiation of an ultraviolet lamp, so that it has excellent film-forming property, bonding strength, heat resistance and hydrolysis resistance.

[0021] The polymer primer provided by the present invention comprises 100 parts of polyurethane prepolymer, 10-60 parts of acrylate monomers, 1-20 parts of photoinitiator, 0.01-13 parts of catalyst, 0.3-30 parts of graphene and its derivatives, 10-100 parts of carbon black, 2-30 parts of chain extender, 0.1-10 parts of antioxidant, 200-700 parts of solvent, 0.1-20 parts of other fillers and 5-30 parts of coupling agent. The prepolymer comprises the following raw materials: 100 parts of polyol and 15-210 parts of isocyanate.

[0022] In the present invention, the polyol is used in an amount of 100 parts. The polymeric polyol is selected from one or more of polyethylene glycol propylene glycol adipate diol, sorbitol, polybutylene glycol, polyoxypropylene triol, polycaprolactone diol, castor oil polyol, polytetramethylene ether diol, polypropylene glycol adipate diol, polyethylene glycol, polyhexamethylene carbonate diol, and polytrimethylene ether diol.

[0023] In the present invention, the amount of the isocyanate is 15 to 210 parts, preferably 40 to 180 parts, and more preferably 50 to 150 parts; the isocyanate is selected from one or more of hexamethylene diisocyanate, hexamethylene diisocyanate trimer, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate biuret, isophorone diisocyanate trimer, lysine diisocyanate, methylcyclohexyl diisocyanate, cyclohexane dimethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate trimer, toluene diisocyanate trimer, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate dimer and diphenylmethane diisocyanate dimer.

[0024] In the present invention, the amount of the solvent is 200-700 parts, preferably 300-600 parts, more preferably 350-500 parts; the solvent is selected from one or more of chloroform, ether, petroleum ether, toluene, ethyl acetate, methyl ethyl ketone, butyl acetate, dichloromethane, ethanol, methanol, acetone and xylene.

[0025] In the present invention, the catalyst is used in an amount of 0.01 to 13 parts, preferably 0.02 to 12 parts, and more preferably 0.04 to 11 parts; the catalyst is selected from one or more of stannous octoate, triethylamine, dibutyltin diacetate, potassium acetate, lead isooctanoate, phenylmercuric acetate, dibutyltin dilaurate, tetrabutyl titanate, tetramethyldipropylenetriamine, tetramethylpropylenediamine, tetramethylhexanediamine, N-methylimidazole, N-methylmorpholine, 1,4-dimethylpiperazine, bismuth isooctanoate and triethylenediamine.

[0026] In the present invention, the amount of the chain extender is 2 to 30 parts, preferably 4 to 25 parts, and more preferably 5 to 22 parts; the chain extender is selected from one or more of 1,4-butanediol, glycidyl allyl ether, trimethylolpropane, trimethylolethane, methyldiethanolamine, carbodiimide, 1,6-hexanediol, glycerol, diethylene glycol, triethylene glycol, triethanolamine, neopentyl glycol, 4,4'-methylenebis(2-chloroaniline), ethylenediamine, 1,4-cyclohexanediol, tetramethylhexanediamine and hydrogenated bisphenol A.

[0027] In the present invention, the amount of the antioxidant is 2 to 30 parts, preferably 5 to 25 parts, and more preferably 8 to 20 parts; the antioxidant is selected from one or more of Irganox 5057, Irganox 1098, Irganox 1135, Irgastab PUR 70, MIANOX 1098, antioxidant 1010, antioxidant 5057, antioxidant 168, antioxidant 1076, B225 and BHT.

[0028] The amount of the acrylic acid ester monomer used in the present invention is 10 to 60 parts, preferably 15 to 55 parts, and more preferably 18 to 52 parts; the acrylic acid ester monomer is selected from two or more of methyl acrylate, ethyl acrylate, methyl 2-methacrylate, ethyl 2-methacrylate, butyl methacrylate, butyl acrylate, and hydroxyethyl methacrylate.

[0029] The amount of the photoinitiator provided by the present invention is 1 to 20 parts, preferably 2 to 18 parts, and more preferably 3 to 16 parts; the photoinitiator is selected from (2,4,6 (trimethylbenzoyl) diphenylphosphine oxide) (TPO), (2,4,6-trimethylbenzoylphosphonic acid ethyl ester) (TPO-L), (2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone) (907), (2-isopropylthioxanthone (2, 4 isomer mixture) (ITX), (1-hydroxy-cyclohexyl-phenyl ketone) (184), (2-hydroxy-2-methyl-1-phenyl-1-propanone One or more of (Benzoin dimethyl ether) (BDK), (Methyl o-benzoylbenzoate) (OMBB), (Benzophenone) (BP), (4-chlorobenzophenone) (CBP), (4-phenylbenzophenone) (PBZ), (2-phenylbenzyl-2-dimethylamino-1-(4-morpholinobenzylphenyl)butanone) (369), (Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) (819), (Mixture of benzoyl formate) (754), Photoinitiator (2-hydroxy-2-methylformylphenyl)benzyl)-2-methyl-1-propanone) (127).

[0030] The present invention provides 0.3 to 30 parts of graphene and its derivatives, preferably 0.4 to 25 parts, and more preferably 0.5 to 20 parts; the graphene and its derivatives are selected from one or more of graphene oxide, single-layer graphene with a sheet diameter of less than 50 μm, graphene with 2 to 10 layers, and graphene with more than 10 layers.

[0031] The present invention provides 10 to 100 parts of carbon black, preferably 20 to 90 parts of carbon black, and more preferably 25 to 80 parts of carbon black; the carbon black is selected from one or more of ordinary carbon black, high-pigment carbon black greater than 1250 mesh, acetylene carbon black and high-wear-resistant furnace black.

[0032] The other fillers provided by the present invention are 0.1 to 20 parts, preferably 0.5 to 15 parts, and more preferably 0.8 to 12 parts; the other fillers are selected from one or more of silicon dioxide, titanium dioxide, sodium silicate, zinc oxide and aluminum oxide.

[0033] The coupling agent provided by the present invention is 5 to 30 parts, preferably 6 to 28 parts, and more preferably 8 to 25 parts; the coupling agent is selected from one or more of γ-aminopropyl triethoxysilane, titanate coupling agent, γ-glycidyloxypropyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, isocyanate propyl triethoxysilane, γ-mercaptopropyl trimethoxysilane, isocyanate propyl trimethoxysilane, γ-(2,3-epoxypropyloxy)propyl trimethoxysilane, aniline methyl trimethoxysilane and γ-aminoethylaminopropyl trimethoxysilane.

[0034] The present invention also provides a method for preparing the polymer primer described in the above technical solution, comprising the following steps: After vacuum dehydration of the polyol, add isocyanate at 60-90°C and react for 1-3 hours to obtain a polyurethane prepolymer; Add acrylate monomer, photoinitiator, chain extender, coupling agent, catalyst, solvent to the above polyurethane prepolymer, and stir at 60-90°C for 0.5-2 hours; Graphene and its derivatives, other fillers, carbon black, etc. are gradually added into the above-mentioned mixed solution, and after grinding and mixing for 1.5 to 5 hours, a polymer primer is obtained.

[0035] The method comprises the following steps: vacuum dehydrating the polyol, adding isocyanate at a temperature of 60-90° C., and reacting for 1-3 hours to obtain a polyurethane prepolymer; specifically, the temperature for adding the isocyanate is 60° C., 65° C., 70° C., 75° C., 80° C., 85° C., and 90° C.; and the reaction time is 1 hour, 1.5 hours, 2 hours, 2.5 hours, and 3 hours.

[0036] According to the present invention, acrylate monomer, photoinitiator, chain extender, coupling agent, catalyst and solvent are added to the polyurethane prepolymer, and stirred at a temperature of 60-90° C. for 0.5-2 hours; specifically, the stirring temperature is 60° C., 65° C., 70° C., 75° C., 80° C., 85° C. and 90° C.; and the stirring time is 0.5 hour, 1 hour, 1.5 hours and 2 hours.

[0037] The present invention gradually adds graphene and its derivatives, other fillers, carbon black and the like into the mixed solution, grinds and mixes for 1.5 to 5 hours to obtain a polymer primer; specifically, the grinding and mixing time is 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5, 4 hours, 4.5 hours and 5 hours.

[0038] In order to further illustrate the present invention, a polyurethane adhesive and a preparation method thereof provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0039] Example 1 a. Preparation of prepolymer After vacuum dehydration of 100 parts of sorbitol, 50 parts of methylcyclohexyl diisocyanate were added at 60°C and reacted for 3 hours to obtain a polyurethane prepolymer; b. Preparation of primer 19 parts of butyl acrylate, 3 parts of (benzoyl formate mixture) (754), 22 parts of diethylene glycol, 25 parts of γ-aminopropyltriethoxysilane, 0.04 parts of phenylmercuric acetate, 350 parts of methyl ethyl ketone, and 8 parts of antioxidant 5057 are added to the above polyurethane prepolymer, and stirred at a temperature of 60-90°C for 0.5 hour; 2 parts of graphene with 2-10 layers, 0.8 parts of silicon dioxide, 25 parts of acetylene carbon black, etc. are gradually added to the above mixture, and after grinding and mixing for 1.5 hours, a polymer primer is obtained.

[0040] Example 2 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polyoxypropylene triol, 70 parts of p-phenylene diisocyanate were added at 70°C and reacted for 2 hours to obtain a polyurethane prepolymer; b. Preparation of primer 25 parts of methyl acrylate monomer, 5 parts of (methyl o-benzoylbenzoate) (OMBB), 8 parts of neopentyl glycol, 25 parts of γ-glycidyloxypropyltrimethoxysilane, 11 parts of tetrabutyl titanate, 500 parts of butyl acetate, and 10 parts of antioxidant 1010 are added to the above polyurethane prepolymer, and stirred at a temperature of 60-90°C for 0.5-2 hours; 29 parts of graphene with more than 10 layers, 3 parts of zinc oxide, 80 parts of high wear-resistant furnace black, etc. are gradually added to the above mixed solution, and after grinding and mixing for 5 hours, a polymer primer is obtained.

[0041] Example 3 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polyhexamethylene carbonate diol, 80 parts of 1,5-naphthalene diisocyanate were added at 90°C and reacted for 1 hour to obtain a polyurethane prepolymer; b. Preparation of primer 18 parts of methyl 2-methacrylate, 8 parts of (2-isopropylthioxanthone (2, 4 isomer mixture) (ITX), 16 parts of methyldiethanolamine, 16 parts of γ-aminopropyltriethoxysilane, 9 parts of N-methylimidazole, 400 parts of ether, and 9 parts of Irganox5057 were added to the above polyurethane prepolymer, and stirred at 60°C for 2 hours; 0.3 parts of graphene oxide, 6 parts of titanium dioxide, 75 parts of high-pigment carbon black greater than 1250 mesh, etc. were gradually added to the above mixture, and after grinding and mixing for 1.5 hours, a polymer primer was obtained.

[0042] Example 4 a. Preparation of prepolymer After vacuum dehydrating 100 parts of polytrimethylene ether glycol, 100 parts of lysine diisocyanate were added at 80°C and reacted for 2 hours to obtain a polyurethane prepolymer; b. Preparation of primer 52 parts of ethyl 2-methacrylate, 10 parts of (2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone) (907), 22 parts of 1,4-cyclohexanediol, 13 parts of γ-glycidyloxypropyltrimethoxysilane, 6 parts of triethylamine, 460 parts of acetone, and 20 parts of Irganox 1135 are added to the above polyurethane prepolymer, and stirred at a temperature of 60-90°C for 1.5 hours; 30 parts of graphene with 2-10 layers, 8 parts of sodium silicate, 66 parts of high-color carbon black with a mesh size greater than 1250, etc. are gradually added to the above mixture, and after grinding and mixing for 4 hours, a polymer primer is obtained.

[0043] Example 5 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polytetramethylene glycol, 110 parts of isophorone diisocyanate were added at 60°C and reacted for 3 hours to obtain a polyurethane prepolymer; b. Preparation of primer 55 parts of hydroxyethyl methacrylate, 12 parts of (benzoyl formate mixture) (754), 20 parts of trimethylolethane, 16 parts of titanate coupling agent, 4 parts of phenylmercuric acetate, 420 parts of acetone, and 17 parts of MIANOX 1098 are added to the above polyurethane prepolymer, and stirred at 80°C for 2 hours; 22 parts of graphene with more than 10 layers, 10 parts of aluminum oxide, 56 parts of acetylene carbon black, etc. are gradually added to the above mixture, and after grinding and mixing for 3 hours, a polymer primer is obtained.

[0044] Example 6 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polypropylene adipate diol, 180 parts of methylcyclohexyl diisocyanate were added at 70°C and reacted for 1 to 3 hours to obtain a polyurethane prepolymer; b. Preparation of primer 56 parts of 2-ethyl methacrylate, 11 parts of (2-isopropylthioxanthone (2, 4 isomer mixture) (ITX), 18 parts of triethanolamine, 17 parts of anilinemethyltrimethoxysilane, 7 parts of potassium acetate, 480 parts of toluene, and 18 parts of antioxidant 1076 were added to the above polyurethane prepolymer and stirred at 80°C for 1 hour; 1 part of graphene with more than 10 layers, 11 parts of sodium silicate, 67 parts of acetylene carbon black, etc. were gradually added to the above mixture, and after grinding and mixing for 3.5 hours, a polymer primer was obtained.

[0045] Example 7 a. Preparation of prepolymer After vacuum dehydration of 100 parts of castor oil polyol, 115 parts of lysine diisocyanate were added at 90°C and reacted for 3 hours to obtain a polyurethane prepolymer; b. Preparation of primer 51 parts of methyl 2-methacrylate, 16 parts of (benzoyl formate mixture) (754), 19 parts of hydrogenated bisphenol A, 10 parts of aniline methyl trimethoxy silane, 10 parts of N-methylimidazole, 460 parts of methanol, and 12 parts of Irganox 1135 are added to the above polyurethane prepolymer, and stirred at 80°C for 2 hours; 8 parts of graphene oxide, 12 parts of titanium dioxide, 76 parts of acetylene carbon black, etc. are gradually added to the above mixture, and after grinding and mixing for 1.5 to 5 hours, a polymer primer is obtained.

[0046] Example 8 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polyhexamethylene carbonate diol, 180 parts of hexamethylene diisocyanate trimer were added at 80°C and reacted for 1 hour to obtain a polyurethane prepolymer; b. Preparation of primer 46 parts of butyl methacrylate, 12 parts of (2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone) (907), 13 parts of glycidyl allyl ether, 8 parts of anilinemethyltrimethoxysilane, 2 parts of N-methylmorpholine, 380 parts of ethanol, and 14 parts of Irgastab PUR 70 were added to the above polyurethane prepolymer and stirred at 60°C for 0.5 hour; 6 parts of graphene with more than 10 layers, 0.8 parts of sodium silicate, 74 parts of ordinary carbon black, etc. were gradually added to the above mixed solution, and after grinding and mixing for 1.5 hours, a polymer primer was obtained.

[0047] Example 9 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polycaprolactone diol, 110 parts of hexamethylene diisocyanate biuret were added at 90°C and reacted for 3 hours to obtain a polyurethane prepolymer; b. Preparation of primer 40 parts of ethyl 2-methacrylate, 12 parts of (2-isopropylthioxanthone (2, 4 isomer mixture) (ITX), 15 parts of 4,4'-methylenebis (2-chloroaniline), 9 parts of isocyanate propyl triethoxysilane, 9 parts of 1,4-dimethylpiperazine, 450 parts of dichloromethane, and 17 parts of BHT were added to the above polyurethane prepolymer, and stirred at 90°C for 2 hours; 8 parts of graphene with more than 10 layers, 9 parts of silicon dioxide, 68 parts of ordinary carbon black, etc. were gradually added to the above mixture, and after grinding and mixing for 5 hours, a polymer primer was obtained.

[0048] Example 10 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polyhexamethylene carbonate diol, 200 parts of p-phenylene diisocyanate were added at 60°C and reacted for 1 hour to obtain a polyurethane prepolymer; b. Preparation of primer 38 parts of methyl acrylate, 8 parts of (2-hydroxy-2-methyl-1-phenyl-1-propanone) (1173), 6 parts of 1,4-cyclohexanediol, 19 parts of anilinemethyltrimethoxysilane, 10 parts of dibutyltin diacetate, 430 parts of dichloromethane, and 9 parts of Irganox 1135 were added to the above polyurethane prepolymer and stirred at 80°C for 1.5 hours; 28 parts of graphene oxide, 11 parts of titanium dioxide, 64 parts of high wear-resistant furnace black, etc. were gradually added to the above mixed solution, and after grinding and mixing for 3 hours, a polymer primer was obtained.

[0049] Embodiment 11 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polypropylene adipate diol, 160 parts of methylcyclohexyl diisocyanate were added at 75°C and reacted for 2.5 hours to obtain a polyurethane prepolymer; b. Preparation of primer 28 parts of ethyl acrylate, 10 parts of (2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone) (907), 8 parts of triethanolamine, 18 parts of γ-aminoethylaminopropyltrimethoxysilane, 7 parts of 1,4-dimethylpiperazine, 480 parts of ethyl acetate, and 19 parts of B225 were added to the above polyurethane prepolymer and stirred at 85°C for 1.5 hours; 24 parts of graphene with more than 10 layers, 12 parts of zinc oxide, 79 parts of high-color carbon black with a mesh size greater than 1250, etc. were gradually added to the above mixture, and after grinding and mixing for 3.5 hours, a polymer primer was obtained.

[0050] Example 12 a. Preparation of prepolymer After vacuum dehydration of 100 parts of tetrahydrofuran ether diol, 130 parts of lysine diisocyanate were added at 75°C and reacted for 2.5 hours to obtain a polyurethane prepolymer; b. Preparation of primer 36 parts of ethyl 2-methacrylate, 14 parts of (benzoyl formate mixture) (754), 13 parts of diethylene glycol, 16 parts of isocyanate propyl trimethoxy silane, 3 parts of dibutyltin diacetate, 350 parts of xylene, and 14 parts of Irganox 5057 are added to the above polyurethane prepolymer, and stirred at 85°C for 1.5 hours; 20 parts of single-layer graphene with a sheet diameter of less than 50 μm, 8 parts of aluminum oxide, 54 parts of acetylene carbon black, etc. are gradually added to the above mixed solution, and after grinding and mixing for 2.5 hours, a polymer primer is obtained.

[0051] Embodiment 13 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polybutylene glycol, 160 parts of hexamethylene diisocyanate trimer were added at 85°C and reacted for 2.5 hours to obtain a polyurethane prepolymer; b. Preparation of primer 30 parts of ethyl 2-methacrylate, 15 parts of (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) (819), 11 parts of diethylene glycol, 11 parts of isocyanatepropyltriethoxysilane, 8 parts of dibutyltin diacetate, 390 parts of petroleum ether, and 11 parts of antioxidant 1010 were added to the above polyurethane prepolymer and stirred at 75°C for 1.5 hours; 16 parts of graphene oxide, 6 parts of sodium silicate, 35 parts of high-pigment carbon black greater than 1250 mesh, etc. were gradually added to the above mixture, and after grinding and mixing for 3.5 hours, a polymer primer was obtained.

[0052] Embodiment 14 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polytrimethylene ether glycol, 120 parts of p-phenylene diisocyanate were added at a temperature of 60-90°C and reacted for 3 hours to obtain a polyurethane prepolymer; b. Preparation of primer 20 parts of hydroxyethyl methacrylate, 13 parts of (methyl o-benzoylbenzoate) (OMBB), 17 parts of neopentyl glycol, 20 parts of isocyanatepropyltrimethoxysilane, 9 parts of potassium acetate, 460 parts of dichloromethane, and 10 parts of Irganox 5057 were added to the above polyurethane prepolymer, and stirred at a temperature of 60-90°C for 1 hour; 12 parts of graphene with more than 10 layers, 3 parts of zinc oxide, 39 parts of high wear-resistant furnace black, etc. were gradually added to the above mixture, and after grinding and mixing for 3.5 hours, a polymer primer was obtained.

[0053] Embodiment 15 a. Preparation of prepolymer After vacuum dehydration of 100 parts of polyethylene glycol, 90 parts of toluene diisocyanate dimer were added at 80°C and reacted for 2.5 hours to obtain a polyurethane prepolymer; b. Preparation of primer 28 parts of butyl methacrylate, 9 parts of (4-phenylbenzophenone) (PBZ), 10 parts of trimethylolpropane, 25 parts of titanate coupling agent, 1 part of phenylmercuric acetate, 410 parts of xylene, and 20 parts of antioxidant 1076 were added to the above polyurethane prepolymer and stirred at 75°C for 1.5 hours; 10 parts of graphene with 2 to 10 layers, 4 parts of titanium dioxide, 48 parts of high-pigment carbon black with a mesh size greater than 1250, etc. were gradually added to the above mixture, and after grinding and mixing for 3 hours, a polymer primer was obtained.

[0054] Comparative Example 1 This comparative example uses Swiss sika Primer-206G+P primer with excellent performance in the same field.

[0055] Comparative Example 2 This comparative example uses the German Henkel TEROSON PU 8511 primer with excellent performance in the industry.

[0056] Blank example The glass is directly bonded to the sealant without any primer.

[0057] Application and performance testing of primer Wipe the glass surface clean with solvents such as ethyl acetate and acetone, and dry it; put a steel ball in the bottle of primer and shake it repeatedly until the steel ball inside hits the bottle wall crisply; take out the primer and apply it to the glass surface with a shoe polish brush in strips. Immediately after application, irradiate it with an ultraviolet lamp (wavelength 365nm, 25w or more) for 10 minutes to obtain a cured primer coating.

[0058] 1) Shear strength: According to the GB / T7124-2008 test method, 100mm×25mm glass is selected as the bonded substrate. The adhesive surface needs to be cleaned of oil and dust with solvents such as ethyl acetate and acetone, and then dried. Then, wipe the substrate surface with ethanol using an absorbent cotton ball. After standing for 5 minutes, use a brush to dip the shaken adhesive and evenly apply it on the substrate surface. The thickness is about 0.5mm. After standing for 5-10 minutes, use a glue gun to apply the sealant. The parallel overlap length of the two glass plates is 12.5mm, and the thickness of the sealant is about 3~4mm. Use a scraper to quickly wipe off the residual glue remaining around the sample. During the gluing process, ensure that there are no bubbles inside the glue. Place it under standard conditions (23℃, 50%RH), test the shear strength and failure form after curing for 7 days, and compare it with the blank sample without adhesive.

[0059] 2) Determination of surface drying time: According to GB / T1728-2020 standard, the finger touch method is used. Touch the surface of the adhesive lightly with your finger. If there is no adhesive sticking to your hand, the surface is considered dry.

[0060] 3) Hydrolysis resistance: After the prepared polymer primer bonding sample is cured, it is placed in water at 40°C for 72 hours to test its shear strength and failure form.

[0061] 4) High temperature and high humidity performance: After the prepared polymer primer bonding sample is cured, it is placed in an environment of 70±2°C, 90%-100%RH for 300 hours to test its shear strength and failure form. The polyurethane adhesives prepared in the above Examples 1 to 14 and Comparative Examples 1 to 2 were tested for shear strength, and the results are shown in Table 1 below, where the blank example is a sample without adhesive.

[0062] Table 1

[0063] In summary, the primer described in the present invention is prepared by multiple cross-linking reactions through photoinitiation and moisture curing, and has excellent adhesion, wear resistance and water resistance, which are better than the performance of similar products in the industry and have great practical application value.

[0064] As can be seen from the above embodiments, the present invention provides a polymer primer and a preparation method thereof, which includes the following raw materials by mass: 100 parts of polyurethane prepolymer, 10-60 parts of acrylate monomers, 1-20 parts of photoinitiators, 0.01-13 parts of catalysts, 0.3-30 parts of graphene and its derivatives, 10-100 parts of carbon black, 2-30 parts of chain extenders, 0.1-10 parts of antioxidants, 200-700 parts of solvents, 0.1-20 parts of other fillers, 5-30 parts of coupling agents; 100 parts of polymer polyols, 15-210 parts of isocyanates. The polymer primer provided by the present invention is cross-linked by two methods, namely, the molecular chains between polymers are mutually bonded and cross-linked to form a relatively stable molecule of a network structure. This reaction transforms linear or slightly branched macromolecules into a three-dimensional network structure, thereby improving the properties such as strength, heat resistance, wear resistance, and solvent resistance. In addition, more hydrogen bonds are formed during the bonding process, thereby improving the adhesion of the primer. In addition, the addition of inorganic fillers can not only fill the grooves on the substrate surface, but also protect the surface, replace the polymer to be oxidized, and increase the storage stability and service life of the system. The experimental results show that the surface drying time of the polyurethane primer is 2~3min; the shear strength under standard conditions is 5.5~6.5MPa, in the form of cohesive failure; after soaking in water for 72h at 40℃, the shear strength is 5.2~6.3MPa, in the form of cohesive failure; after being treated at 70±2℃, 90%~100%RH for 300h, the shear strength is 5.5~6.4MPa, in the form of cohesive failure.

[0065] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A polymer primer, comprising the following raw materials in parts by mass: 100 parts of polyurethane prepolymer, 10-60 parts of acrylate monomer, 1-20 parts of photoinitiator, 0.01-13 parts of catalyst, 0.3-30 parts of graphene and its derivatives, 10-100 parts of carbon black, 2-30 parts of chain extender, 0.1-10 parts of antioxidant, 200-700 parts of solvent, 0.1-20 parts of other fillers, 5-30 parts of coupling agent; Polyurethane prepolymers include: 100 parts of polymer polyol and 15-210 parts of isocyanate.

2. The polymer primer according to claim 1, characterized in that: The polymeric polyol is selected from one or more of polyethylene glycol propylene glycol adipate diol, sorbitol, polybutylene glycol, polyoxypropylene triol, polycaprolactone diol, castor oil polyol, polytetramethylene ether diol, polypropylene glycol adipate diol, polyethylene glycol, polyhexamethylene carbonate diol, and polytrimethylene ether diol; The isocyanate is selected from one or more of hexamethylene diisocyanate, hexamethylene diisocyanate trimer, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate biuret, isophorone diisocyanate trimer, lysine diisocyanate, methylcyclohexyl diisocyanate, cyclohexane dimethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate trimer, toluene diisocyanate trimer, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate dimer and diphenylmethane diisocyanate dimer.

3. The polymer primer according to claim 1, characterized in that The solvent is selected from one or more of chloroform, ethyl ether, petroleum ether, toluene, ethyl acetate, methyl ethyl ketone, butyl acetate, dichloromethane, ethanol, methanol, acetone and xylene.

4. The polymer primer according to claim 1, characterized in that The catalyst is selected from one or more of stannous octoate, triethylamine, dibutyltin diacetate, potassium acetate, lead isooctanoate, phenylmercuric acetate, dibutyltin dilaurate, tetrabutyl titanate, tetramethyldipropylenetriamine, tetramethylpropylenediamine, tetramethylhexanediamine, N-methylimidazole, N-methylmorpholine, 1,4-dimethylpiperazine, bismuth isooctanoate and triethylenediamine.

5. The polymer primer according to claim 1, characterized in that: The chain extender is selected from one or more of 1,4-butanediol, glycidyl allyl ether, trimethylolpropane, trimethylolethane, methyldiethanolamine, carbodiimide, 1,6-hexanediol, glycerol, diethylene glycol, triethylene glycol, triethanolamine, neopentyl glycol, 4,4'-methylenebis(2-chloroaniline), ethylenediamine, 1,4-cyclohexanediol, tetramethylhexanediamine and hydrogenated bisphenol A; The antioxidant is selected from one or more of Irganox 5057, Irganox 1098, Irganox 1135, Irgastab PUR 70, MIANOX 1098, antioxidant 1010, antioxidant 5057, antioxidant 168, antioxidant 1076, B225 and BHT.

6. The polymer primer according to claim 1, characterized in that The acrylic acid ester monomer is selected from two or more of methyl acrylate, ethyl acrylate, methyl 2-methacrylate, ethyl 2-methacrylate, butyl methacrylate, butyl acrylate, and hydroxyethyl methacrylate; The photoinitiator is selected from (2,4,6 (trimethylbenzoyl) diphenylphosphine oxide) (TPO), (2,4,6-trimethylbenzoylphosphonic acid ethyl ester) (TPO-L), (2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone) (907), (2-isopropylthioxanthone (2, 4 isomer mixture) (ITX), (1-hydroxy-cyclohexyl-phenyl ketone) (184), (2-hydroxy-2-methyl-1-phenyl-1-propanone) (1173), (benzoin dimethyl ether) (BDK) , (methyl o-benzoylbenzoate) (OMBB), (benzophenone) (BP), (4-chlorobenzophenone) (CBP), (4-phenylbenzophenone) (PBZ), (2-phenylbenzyl-2-dimethylamino-1-(4-morpholinobenzylphenyl)butanone) (369), (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) (819), (benzoylformate mixture) (754), photoinitiator (2-hydroxy-2-methylformylphenyl)benzyl)-2-methyl-1-propanone) (127) One or more.

7. The polymer primer according to claim 1, characterized in that The other fillers are selected from one or more of silicon dioxide, titanium dioxide, sodium silicate, zinc oxide and aluminum oxide; The graphene and its derivatives are selected from one or more of graphene oxide, single-layer graphene with a sheet diameter of less than 50 μm, graphene with 2 to 10 layers, and graphene with more than 10 layers.

8. The polymer primer according to claim 1, characterized in that The carbon black is selected from one or more of ordinary carbon black, high-pigment carbon black with a mesh size greater than 1250, acetylene carbon black and high-wear-resistant furnace black.

9. The polymer primer according to claim 1, characterized in that: The coupling agent is selected from one or more of γ-aminopropyltriethoxysilane, titanate coupling agent, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, isocyanatepropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, isocyanatepropyltrimethoxysilane, γ-(2,3-epoxypropyloxy)propyltrimethoxysilane, anilinemethyltrimethoxysilane and γ-aminoethylaminopropyltrimethoxysilane.

10. A method for preparing the polymer primer according to any one of claims 1 to 9, characterized in that: The following steps are involved: After vacuum dehydration of the polyol, add isocyanate at 60-90°C and react for 1-3 hours to obtain a polyurethane prepolymer; Add acrylate monomer, photoinitiator, chain extender, coupling agent, catalyst, antioxidant and solvent to the above polyurethane prepolymer, and stir at 60-90°C for 0.5-2 hours; Graphene and its derivatives, other fillers, carbon black, etc. are gradually added into the above-mentioned mixed solution, and after grinding and mixing for 1.5 to 5 hours, a polymer primer is obtained.

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