Aging-resistant polyurethane glass laminated film for laminated glass and its processing technology

Abstract

The present invention relates to the technical field of polyurethane materials, and specifically to an aging-resistant polyurethane glass interlayer film for laminated glass and a processing technology thereof. Specifically, the process comprises the following steps: Step 1: reacting an olefinic halogen-containing compound with terminal hydrogen silicone oil, potassium phthalimide, hydrazine monohydrate, and dimethyl carbonate in sequence, followed by catalytic pyrolysis to obtain a curing agent; Step 2: modifying carbon black with a silane coupling agent, and then allowing titanium dioxide to grow in situ on the carbon black surface to obtain a carbon black / titanium dioxide composite material; finally, modifying the carbon black / titanium dioxide composite material with a silane coupling agent to obtain a modified filler; Step 3: weighing each raw material according to the formula, mixing them evenly in an internal mixer to obtain a mixed material, and finally, subjecting the mixed material to injection molding, curing, and aging to obtain an aging-resistant polyurethane glass interlayer film. The polyurethane glass interlayer film not only has improved aging resistance but also has enhanced mechanical properties, thus having better practicality.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyurethane materials, and in particular relates to an aging-resistant polyurethane glass interlayer film for laminated glass and a processing technology thereof. Background Art

[0002] Laminated glass is a composite glass product made of two or more pieces of glass with one or more layers of organic polymer interlayer sandwiched between them. After a special high-temperature pre-pressing (or vacuuming) and high-temperature and high-pressure process, the glass and the interlayer are permanently bonded together. It has the advantages of safety, explosion-proofing, noise reduction and sound insulation, and is widely used in construction, automobiles, security and other fields.

[0003] The most commonly used interlayer film for laminated glass is polyvinyl butyral (PVB), which offers excellent light transmission and impact resistance. Unlike standard glass, PVB effectively reduces the risk of glass fragments flying in impact accidents. However, PVB exhibits poor adhesion to organic glass and becomes brittle at low temperatures, further weakening its bond to the glass. Polyurethane elastomers offer improved bond strength, higher transparency, and greater resistance to impact deformation, as well as excellent adaptability to temperature fluctuations. They are considered a viable alternative to PVB and can be used as an interlayer film in laminated glass.

[0004] However, a large number of unsaturated bonds are often introduced into polyurethane elastomers during the synthesis process. Under the influence of factors such as light, temperature, oxygen and moisture, these unsaturated double bonds will break, generating new free radicals, and the free radicals will cross-link and react with each other. After aging, the molecular chains break into small molecular segments, causing changes in relative molecular mass, cross-linking degree and crystallinity, which in turn causes the material to soften, the surface to become sticky, and air gaps to form, seriously reducing the service life of polyurethane glass laminated film.

[0005] Currently, the most common industrial solution is to add small molecule antioxidants such as amines and phenols to the material. These small molecules primarily enhance the material's aging resistance by capturing hydrocarbon peroxide free radicals generated during oxidation reactions. However, these agents are highly toxic and volatile during use, often accumulating and forming bloom on the surface of polyurethane glass interlayer films, reducing their antioxidant effectiveness. Therefore, developing a novel polyurethane glass interlayer film with superior aging resistance is of great significance. Summary of the Invention

[0006] In view of the above problems existing in the prior art, the object of the present invention is to provide an aging-resistant polyurethane glass interlayer film for laminated glass and a processing technology thereof.

[0007] In order to solve the above problems, the technical solutions adopted by the present invention are as follows:

[0008] A process for processing an aging-resistant polyurethane glass laminated film for laminated glass comprises the following steps:

[0009] S1: reacting an olefinic halogen compound with a hydrogen-terminated silicone oil to obtain a modified silicone oil A; reacting the modified silicone oil A with potassium phthalimide, followed by hydrazinolysis, to obtain a modified silicone oil B; reacting the modified silicone oil B with dimethyl carbonate to obtain a modified silicone oil C; and catalytically pyrolyzing the reaction mixture to obtain a curing agent;

[0010] S2: modifying carbon black with a silane coupling agent, and then growing titanium dioxide in situ on the surface of the carbon black to obtain a carbon black / titanium dioxide composite material; and then modifying the carbon black / titanium dioxide composite material with a silane coupling agent to obtain a modified filler;

[0011] S3: mixing the raw materials of various components in an internal mixer to obtain a mixed material; and finally, performing injection molding, curing, and aging to obtain an aging-resistant polyurethane glass laminated film, wherein the raw materials include: polyurethane grafted acrylic emulsion, polyurethane prepolymer, the curing agent, the modified filler, and additives.

[0012] Optionally, the raw materials in S3 are calculated by weight as follows: 15-30 parts of polyurethane grafted acrylic emulsion, 60-80 parts of polyurethane prepolymer, 15-25 parts of curing agent, 3-8 parts of modified filler, 1-2 parts of antioxidant, and 1-2 parts of defoaming agent.

[0013] Optionally, the preparation method of the curing agent is specifically as follows:

[0014] Mix the olefinic halogen compound and the terminal hydrogen-containing silicone oil, add chloroplatinic acid, and react at 60-100°C for 2-4 hours to obtain modified silicone oil A;

[0015] Mix potassium phthalimide, modified silicone oil A, and anhydrous ethanol evenly, adjust the temperature to 40-60°C, react for 2-6 hours, then add hydrazine monohydrate, maintain the original temperature, react for 15-30 minutes, separate, and dry to obtain modified silicone oil B;

[0016] Modified silicone oil B, dimethyl carbonate, and catalyst 1 were mixed evenly, and reacted under nitrogen at 170-230°C and 1.0-5.3 MPa for 2-8 hours to obtain modified silicone oil C;

[0017] Add modified silicone oil C and catalyst 2 to dioctyl phthalate, react at 150-300°C and 1-3 MPa for 3-6 hours to obtain a curing agent.

[0018] Optionally, the olefinic halogen-containing compound includes any one of 1,2,3-trichloropropylene, 1,4-dichloro-2-butene, 1,4-dibromo-2-butene, and 1,6-dibromo-3-hexene.

[0019] Optionally, the volume ratio of the olefinic halogen-containing compound to the terminal hydrogen-containing silicone oil is (0.5~1):1; the mass ratio of the potassium phthalimide, modified silicone oil A, and hydrazine monohydrate is (0.5~0.8):1:(1.5~2.5); the mass ratio of the modified silicone oil B to dimethyl carbonate is 1:(8~10); the mass ratio of the modified silicone oil C to dioctyl phthalate is 1:(15~20).

[0020] Optionally, the preparation method of the modified filler is specifically as follows:

[0021] a. Add carbon black and γ-mercaptopropyltrioxysilane to benzophenone, disperse them by ultrasonication for 5-15 minutes, and irradiate them with 330-380 nm ultraviolet light for 10-30 minutes to obtain modified carbon black;

[0022] b. Add the modified carbon black to anhydrous ethanol, ultrasonically disperse for 5-15 minutes, then add ammonia water, mechanically stir for 30-60 minutes, and finally add tetraisobutyl titanate, continue stirring for 5-10 hours, and finally centrifuge, wash, dry, and grind to obtain a carbon black / titanium dioxide composite material;

[0023] c. Add the carbon black / titanium dioxide composite material and γ-aminopropyltriethoxysilane to anhydrous ethanol, mechanically stir for 1 to 3 hours, filter and dry to obtain a modified filler.

[0024] Optionally, in the preparation of the modified filler, the mass ratio of carbon black, γ-mercaptopropyltrioxysilane, and benzophenone in step a is (0.5~1):2:(0.8~1.2); the mass ratio of modified carbon black, ammonia water, and tetraisobutyl titanate in step b is 1:(8~10):(8~12); and the mass ratio of carbon black / titanium dioxide composite material, γ-aminopropyltriethoxysilane, and anhydrous ethanol in step c is 1:(1.8~2.5):(15~25).

[0025] Optionally, the catalyst 1 is any one of zinc carbonate, zinc oxide, and triphenyltin acetate; the catalyst 2 is any one of zinc powder, zinc acetate, and aluminum powder.

[0026] Optionally, S3 is specifically as follows: first, the polyurethane grafted acrylic emulsion and the modified filler are placed into an internal mixer at a temperature of 150-160°C, and the mixing is performed for 5-10 minutes. Then, the polyurethane prepolymer, curing agent, antioxidant, and defoaming agent are added, and the mixing is continued for 10-20 minutes to obtain a mixture; the mixture is injected into a mold, and after curing and maturation, an aging-resistant polyurethane glass laminated film is obtained.

[0027] The aging-resistant polyurethane glass laminated film is prepared according to the above processing technology.

[0028] Compared with the prior art, the present invention has the following beneficial effects: a curing agent is prepared, which not only cures polyurethane but also provides the polyurethane glass laminated film with excellent aging resistance; a carbon black / titanium dioxide composite material is further prepared, and the two are used synergistically as fillers to improve the aging resistance and the mechanical properties of the polyurethane glass laminated film; and finally, a silane coupling agent is used to modify the polyurethane glass laminated film and introduce amino groups to cross-link the polyurethane grafted acrylic emulsion, thereby forming a three-dimensional structure between the molecules in the polyurethane elastomer, thereby significantly improving the performance of the polyurethane glass laminated film, improving not only the aging resistance but also the mechanical properties, and having better practicality.

[0029] (1) The present application prepares a halogenated modified silicone oil A by reacting an olefinic halogen compound with a terminal hydrogenated silicone oil through a silylation reaction; then the modified silicone oil A is reacted through the Gabriel primary amine synthesis method to obtain a modified silicone oil B having an amino group. In this process, in order to avoid the electron-withdrawing effect of the carbonyl group and the steric hindrance of the hydrocarbon group from hindering the nucleophilic reaction during the reaction, a hydrazinolysis is further performed to promote the reaction; finally, the modified silicone oil B is reacted with dimethyl carbonate, and the modified silicone oil contains a large number of amino groups. The amino groups react with dimethyl carbonate to form a methoxycarbonylation reaction, and then the reaction is catalytically pyrolyzed, thereby introducing an isocyanate group into the silicone oil chain to obtain a silicone oil curing agent; while the curing agent has a curing effect, it can improve the aging resistance of the polyurethane glass laminated film;

[0030] (2) Grafting a silane coupling agent onto the surface of carbon black by a photochemical method to make its surface contain silicon-oxygen bonds, and then in situ growing titanium dioxide on its surface; the introduction of silicon-oxygen bonds on carbon black can improve the binding force between titanium dioxide and carbon black, and adding ammonia water to provide ammonium ions to make them adsorbed on carbon black, so that tetraisobutyl titanate hydrolyzes to produce negatively charged intermediate charges that are more easily adsorbed on the surface of carbon black, thereby promoting the growth of titanium dioxide on the surface of carbon black, and preparing a carbon black / titanium dioxide composite material. The two synergistically improve the aging resistance of polyurethane glass laminated film;

[0031] (3) This application uses a silane coupling agent to modify the carbon black / titanium dioxide composite material again and introduce amino groups; and further introduces a polyurethane grafted acrylic emulsion to cross-link with the amino groups on the modified filler, so that it forms a three-dimensional structure between the molecules in the polyurethane elastomer, thereby achieving a synergistic promotion of the performance of the polyurethane glass laminated film. On the one hand, its weather resistance and aging resistance are improved, and the service life of the polyurethane glass laminated film is extended; on the other hand, it can also improve its mechanical properties, heat resistance, and chemical resistance, so that it can meet the use requirements of different fields. DETAILED DESCRIPTION

[0032] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0033] It should be noted that the purchasers of all raw materials involved in the present invention include, without any special restrictions, the following examples:

[0034] The polyurethane grafted acrylic emulsion model is JZ-416 (Nanjing Jiazhong Chemical Technology Co., Ltd.), the polyurethane prepolymer model is HC-9975 (Wuhan Penglei Biotechnology Co., Ltd.), the antioxidant 1010 purity is 99% (Henan Tianfu Chemical Co., Ltd.), the defoamer is UNIQFOAM 280W silicone defoamer (Uka Chemical (Shanghai) Co., Ltd.), the purity of 1,2,3-trichloropropylene is 99.5% (Tianmen Hengchang Chemical Co., Ltd.), the terminal hydrogen silicone oil is 99.5% pure, CAS number: 70900-21-9, item number: 70900-21-9 (Hubei Yongkuo Technology Co., Ltd.), the purity of chloroplatinic acid is 99% (Henan Tianfu Chemical Co., Ltd.), the purity of potassium phthalimide is 98% (Jinan Shengqi Pharmaceutical Technology Co., Ltd.), and the purity of hydrazine monohydrate is 99% (Shanghai Dengchi International Trade Co., Ltd. Co., Ltd.), dimethyl carbonate with a purity of 99% (Henan Tianfu Chemical Co., Ltd.), carbon black with a purity of 99% and an average particle size of 20 nm (Hubei Yongkuo Technology Co., Ltd.), γ-mercaptopropyltrioxysilane with a purity of 99% (Henan Tianfu Chemical Co., Ltd.), γ-aminopropyltriethoxysilane with a purity of 98% (Zhengzhou Alpha Chemical Co., Ltd.), benzophenone with a purity of 99.5% (Hubei Jusheng Technology Co., Ltd.), and tetraisobutyl titanate with a purity of 99% (Shanghai Jinjinle Industrial Co., Ltd.); each portion in the examples is 10 g.

[0035] Example 1

[0036] A processing technology of aging-resistant polyurethane glass laminated film is as follows:

[0037] S1: 0.7 L of 1,2,3-trichloropropylene and 1 L of terminal hydrogenated silicone oil were added to a reactor, mechanically stirred and mixed until uniform, 68 mg of chloroplatinic acid was added as a catalyst, and the mixture was reacted at 80°C for 3 h to obtain modified silicone oil A;

[0038] Then, 28 parts of potassium phthalimide, 40 parts of modified silicone oil A, and 800 parts of anhydrous ethanol were added to the reactor, mechanically stirred and mixed uniformly, and the temperature was adjusted to 50°C. After reacting for 5 hours, 80 parts of hydrazine monohydrate were added, and the temperature was maintained at 50°C. The reaction was continued for 30 minutes. After separation and drying, modified silicone oil B was obtained;

[0039] Then, 40 parts of modified silicone oil B, 400 parts of dimethyl carbonate, and 1.2 parts of nano zinc oxide were added to the reactor, mechanically stirred, and reacted under nitrogen at 220°C and 3.8 MPa for 6 hours to obtain modified silicone oil C.

[0040] 40 parts of modified silicone oil C and 1.2 parts of zinc powder were added to 800 parts of dioctyl phthalate, and the mixture was reacted at 230° C. and 2.3 MPa for 5 hours to obtain a curing agent.

[0041] S2: a. Add 10 parts of carbon black and 25 parts of γ-mercaptopropyltrioxysilane to 12.5 parts of benzophenone, disperse the mixture by ultrasonication for 15 minutes, and irradiate the mixture with 354 nm ultraviolet light for 30 minutes to obtain modified carbon black;

[0042] b. Add 10 parts of modified carbon black to 500 parts of anhydrous ethanol, ultrasonically disperse for 15 minutes, then add 100 parts of 20wt% ammonia water, mechanically stir for 50 minutes, and finally add 100 parts of tetraisobutyl titanate, continue stirring for 8 hours, and finally centrifuge, wash, dry, and grind to obtain a carbon black / titanium dioxide composite material;

[0043] c. Add 10 parts of carbon black / titanium dioxide composite material and 20 parts of γ-aminopropyltriethoxysilane to 200 parts of anhydrous ethanol, mechanically stir for 2 hours, filter and dry to obtain a modified filler.

[0044] S3: Weigh 23 parts of polyurethane grafted acrylic emulsion, 70 parts of polyurethane prepolymer, 6 parts of modified filler, 23 parts of curing agent, 1.3 parts of antioxidant 1010, and 1.5 parts of UNIQFOAM 280W silicone defoamer;

[0045] The temperature of the internal mixer was adjusted to 160°C, and the polyurethane grafted acrylic emulsion and the modified filler were first added into the internal mixer. After internal mixing for 5 minutes, the polyurethane prepolymer, curing agent, antioxidant 1010, and UNIQFOAM 280W silicone defoaming agent were added, and the internal mixing was continued for 15 minutes to obtain a mixture. The mixture was then poured into a mold, cured at room temperature for 24 hours, and then placed in an oven at 70°C for aging for 36 hours to obtain an aging-resistant polyurethane glass laminated film.

[0046] The obtained aging-resistant polyurethane glass interlayer film is sandwiched between two layers of glass and hot-pressed to obtain laminated glass.

[0047] Example 2

[0048] A processing technology of aging-resistant polyurethane glass laminated film is as follows:

[0049] S1: 0.5 L of 1,2,3-trichloropropylene and 1 L of terminal hydrogenated silicone oil were added to a reactor, mechanically stirred and mixed uniformly, 60 mg of chloroplatinic acid was added as a catalyst, and the mixture was reacted at 80°C for 3 h to obtain modified silicone oil A;

[0050] Then, 20 parts of potassium phthalimide, 40 parts of modified silicone oil A, and 800 parts of anhydrous ethanol were added to the reactor, mechanically stirred and mixed uniformly, and the temperature was adjusted to 50°C. After reacting for 5 hours, 80 parts of hydrazine monohydrate were added, and the temperature was maintained at 50°C. The reaction was continued for 30 minutes. After separation and drying, modified silicone oil B was obtained;

[0051] Then, 40 parts of modified silicone oil B, 320 parts of dimethyl carbonate, and 1.2 parts of nano zinc oxide were added to the reactor, mechanically stirred, and reacted for 6 hours at 220°C and 3.8 MPa under a nitrogen environment to obtain modified silicone oil C.

[0052] 40 parts of modified silicone oil C and 1.2 parts of zinc powder were added to 800 parts of dioctyl phthalate, and the mixture was reacted at 230° C. and 2.3 MPa for 5 hours to obtain a curing agent.

[0053] S2: a. Add 10 parts of carbon black and 25 parts of γ-mercaptopropyltrioxysilane to 12.5 parts of benzophenone, disperse the mixture by ultrasonication for 15 minutes, and irradiate the mixture with 354 nm ultraviolet light for 30 minutes to obtain modified carbon black;

[0054] b. Add 10 parts of modified carbon black to 500 parts of anhydrous ethanol, ultrasonically disperse for 15 minutes, then add 90 parts of 20wt% ammonia water, mechanically stir for 60 minutes, and finally add 120 parts of tetraisobutyl titanate, continue stirring for 10 hours, and finally centrifuge, wash, dry, and grind to obtain a carbon black / titanium dioxide composite material;

[0055] c. Add 10 parts of carbon black / titanium dioxide composite material and 18 parts of γ-aminopropyltriethoxysilane to 180 parts of anhydrous ethanol, stir mechanically for 2 hours, filter and dry to obtain a modified filler.

[0056] S3: Weigh 23 parts of polyurethane grafted acrylic emulsion, 70 parts of polyurethane prepolymer, 6 parts of modified filler, 23 parts of curing agent, 1.3 parts of antioxidant 1010, and 1.5 parts of UNIQFOAM 280W silicone defoamer;

[0057] The temperature of the internal mixer was adjusted to 150°C, and the polyurethane grafted acrylic emulsion and the modified filler were first added into the internal mixer. After internal mixing for 8 minutes, the polyurethane prepolymer, curing agent, antioxidant 1010, and UNIQFOAM 280W silicone defoaming agent were added, and the internal mixing was continued for 15 minutes to obtain a mixture. The mixture was then poured into a mold, cured at room temperature for 24 hours, and then placed in an oven at 70°C for aging for 36 hours to obtain an aging-resistant polyurethane glass laminated film.

[0058] Example 3

[0059] A processing technology of aging-resistant polyurethane glass laminated film is as follows:

[0060] S1: 1 L of 1,4-dichloro-2-butene and 1 L of terminal hydrogenated silicone oil were added to a reactor, mechanically stirred and mixed uniformly, 80 mg of chloroplatinic acid was added as a catalyst, and the mixture was reacted at 80°C for 3 h to obtain modified silicone oil A;

[0061] Then, 32 parts of potassium phthalimide, 40 parts of modified silicone oil A, and 800 parts of anhydrous ethanol were added to the reactor, mechanically stirred and mixed uniformly, and the temperature was adjusted to 50°C. After reacting for 5 hours, 80 parts of hydrazine monohydrate were added, and the temperature was maintained at 50°C. The reaction was continued for 30 minutes. After separation and drying, modified silicone oil B was obtained;

[0062] Then, 40 parts of modified silicone oil B, 400 parts of dimethyl carbonate, and 1.2 parts of nano zinc oxide were added to the reactor, mechanically stirred, and reacted under nitrogen at 220°C and 3.8 MPa for 6 hours to obtain modified silicone oil C.

[0063] 40 parts of modified silicone oil C and 1.2 parts of zinc powder were added to 700 parts of dioctyl phthalate, and the mixture was reacted at 230° C. and 2.3 MPa for 5 hours to obtain a curing agent.

[0064] S2: a. Add 10 parts of carbon black and 25 parts of γ-mercaptopropyltrioxysilane to 12.5 parts of benzophenone, disperse the mixture by ultrasonication for 15 minutes, and irradiate the mixture with 380 nm ultraviolet light for 20 minutes to obtain modified carbon black;

[0065] b. Add 10 parts of modified carbon black to 500 parts of anhydrous ethanol, ultrasonically disperse for 15 minutes, then add 80 parts of 20wt% ammonia water, mechanically stir for 60 minutes, and finally add 100 parts of tetraisobutyl titanate, continue stirring for 5-10 hours, and finally centrifuge, wash, dry, and grind to obtain a carbon black / titanium dioxide composite material;

[0066] c. Add 10 parts of carbon black / titanium dioxide composite material and 25 parts of γ-aminopropyltriethoxysilane to 250 parts of anhydrous ethanol, mechanically stir for 2 hours, filter and dry to obtain a modified filler.

[0067] S3: Weigh 23 parts of polyurethane grafted acrylic emulsion, 70 parts of polyurethane prepolymer, 6 parts of modified filler, 23 parts of curing agent, 1.3 parts of antioxidant 1010, and 1.5 parts of UNIQFOAM 280W silicone defoamer;

[0068] The temperature of the internal mixer was adjusted to 160°C, and the polyurethane grafted acrylic emulsion and the modified filler were first added into the internal mixer. After internal mixing for 5 minutes, the polyurethane prepolymer, curing agent, antioxidant 1010, and UNIQFOAM 280W silicone defoaming agent were added, and the internal mixing was continued for 20 minutes to obtain a mixture. The mixture was then poured into a mold, cured at room temperature for 24 hours, and then placed in an oven at 70°C for aging for 36 hours to obtain an aging-resistant polyurethane glass laminated film.

[0069] Example 4

[0070] A processing technology of aging-resistant polyurethane glass laminated film is as follows:

[0071] S1: 0.7 L of 1,4-dibromo-2-butene and 1 L of terminal hydrogenated silicone oil were added to a reactor, mechanically stirred and mixed uniformly, 68 mg of chloroplatinic acid was added as a catalyst, and the mixture was reacted at 60°C for 4 h to obtain modified silicone oil A;

[0072] Then, 28 parts of potassium phthalimide, 40 parts of modified silicone oil A, and 800 parts of anhydrous ethanol were added to the reactor, mechanically stirred and mixed uniformly, and the temperature was adjusted to 60°C. After reacting for 2 hours, 100 parts of hydrazine monohydrate were added, and the temperature was maintained at about 60°C. The reaction was continued for 30 minutes. After separation and drying, modified silicone oil B was obtained;

[0073] Then, 40 parts of modified silicone oil B, 400 parts of dimethyl carbonate, and 1.2 parts of triphenyltin acetate were added to the reaction kettle, mechanically stirred, and reacted under nitrogen at 230°C and 1.5 MPa for 8 hours to obtain modified silicone oil C.

[0074] 40 parts of modified silicone oil C and 1.2 parts of aluminum powder were added to 750 parts of dioctyl phthalate, and the mixture was reacted at 290° C. and 1.4 MPa for 3 hours to obtain a curing agent.

[0075] S2: a. Add 10 parts of carbon black and 25 parts of γ-mercaptopropyltrioxysilane to 10 parts of benzophenone, disperse the mixture by ultrasonication for 15 minutes, and irradiate the mixture with 330 nm ultraviolet light for 15 minutes to obtain modified carbon black;

[0076] b. Add 10 parts of modified carbon black to 500 parts of anhydrous ethanol, ultrasonically disperse for 15 minutes, then add 100 parts of 20wt% ammonia water, mechanically stir for 60 minutes, and finally add 100 parts of tetraisobutyl titanate, continue stirring for 5-10 hours, and finally centrifuge, wash, dry and grind to obtain a carbon black / titanium dioxide composite material;

[0077] c. Add 10 parts of carbon black / titanium dioxide composite material and 20 parts of γ-aminopropyltriethoxysilane to 200 parts of anhydrous ethanol, mechanically stir for 2 hours, filter and dry to obtain a modified filler.

[0078] S3: Weigh 15 parts of polyurethane grafted acrylic emulsion, 80 parts of polyurethane prepolymer, 8 parts of modified filler, 25 parts of curing agent, 2 parts of antioxidant 1010, and 2 parts of UNIQFOAM 280W silicone defoamer;

[0079] The temperature of the internal mixer was adjusted to 160°C, and the polyurethane grafted acrylic emulsion and the modified filler were first added into the internal mixer. After internal mixing for 10 minutes, the polyurethane prepolymer, curing agent, antioxidant 1010, and UNIQFOAM 280W silicone defoaming agent were added, and the internal mixing was continued for 15 minutes to obtain a mixture. The mixture was then poured into a mold, cured at room temperature for 12 hours, and then placed in an oven at 80°C for aging for 36 hours to obtain an aging-resistant polyurethane glass laminated film.

[0080] Example 5

[0081] A processing technology of aging-resistant polyurethane glass laminated film is as follows:

[0082] S1: 0.7 L of 1,2,3-trichloropropylene and 1 L of terminal hydrogenated silicone oil were added to a reactor, mechanically stirred and mixed until uniform, 68 mg of chloroplatinic acid was added as a catalyst, and the mixture was reacted at 100°C for 2 h to obtain modified silicone oil A;

[0083] Then, 28 parts of potassium phthalimide, 40 parts of modified silicone oil A, and 800 parts of anhydrous ethanol were added to the reactor, mechanically stirred and mixed uniformly, and the temperature was adjusted to 45°C. After reacting for 6 hours, 70 parts of hydrazine monohydrate were added, and the temperature was maintained at about 45°C. The reaction was continued for 25 minutes. After separation and drying, modified silicone oil B was obtained;

[0084] Then, 40 parts of modified silicone oil B, 400 parts of dimethyl carbonate, and 1.2 parts of nano zinc oxide were added to the reactor, mechanically stirred, and reacted for 4 hours at 200°C and 5.0 MPa under a nitrogen environment to obtain modified silicone oil C.

[0085] 40 parts of modified silicone oil C and 1.2 parts of zinc powder were added to 600 parts of dioctyl phthalate, and the mixture was reacted at 160° C. and 2.7 MPa for 4 hours to obtain a curing agent.

[0086] S2: a. Add 10 parts of carbon black and 25 parts of γ-mercaptopropyltrioxysilane to 15.0 parts of benzophenone, disperse the mixture by ultrasonication for 15 minutes, and irradiate the mixture with 354 nm ultraviolet light for 30 minutes to obtain modified carbon black;

[0087] b. Add 10 parts of modified carbon black to 500 parts of anhydrous ethanol, ultrasonically disperse for 10 minutes, then add 100 parts of 20wt% ammonia water, mechanically stir for 40 minutes, and finally add 100 parts of tetraisobutyl titanate, continue stirring for 10 hours, and finally centrifuge, wash, dry, and grind to obtain a carbon black / titanium dioxide composite material;

[0088] c. Add 10 parts of carbon black / titanium dioxide composite material and 20 parts of γ-aminopropyltriethoxysilane to 200 parts of anhydrous ethanol, mechanically stir for 2 hours, filter and dry to obtain a modified filler.

[0089] S3: Weigh 30 parts of polyurethane grafted acrylic emulsion, 60 parts of polyurethane prepolymer, 5 parts of modified filler, 20 parts of curing agent, 1.8 parts of antioxidant 1010, and 1 part of UNIQFOAM 280W silicone defoamer;

[0090] The temperature of the internal mixer was adjusted to 160°C, and the polyurethane grafted acrylic emulsion and the modified filler were first added into the internal mixer. After internal mixing for 5 minutes, the polyurethane prepolymer, curing agent, antioxidant 1010, and UNIQFOAM 280W silicone defoaming agent were added, and the internal mixing was continued for 15 minutes to obtain a mixture. The mixture was then poured into a mold, cured at room temperature for 24 hours, and then placed in an oven at 60°C for aging for 48 hours to obtain an aging-resistant polyurethane glass laminated film.

[0091] Example 6

[0092] The difference between this embodiment and embodiment 1 is that:

[0093] S3: Weigh 23 parts of polyurethane grafted acrylic emulsion, 70 parts of polyurethane prepolymer, 6 parts of modified filler, 15 parts of curing agent, 1.3 parts of antioxidant 1010, and 1.5 parts of UNIQFOAM 280W silicone defoamer;

[0094] The temperature of the internal mixer was adjusted to 160°C, and the polyurethane grafted acrylic emulsion and the modified filler were first added into the internal mixer. After internal mixing for 5 minutes, the polyurethane prepolymer, curing agent, antioxidant 1010, and UNIQFOAM 280W silicone defoaming agent were added, and the internal mixing was continued for 15 minutes to obtain a mixture. The mixture was then poured into a mold, cured at room temperature for 24 hours, and then placed in an oven at 70°C for aging for 36 hours to obtain an aging-resistant polyurethane glass laminated film.

[0095] Example 7

[0096] The difference between this embodiment and embodiment 1 is that:

[0097] S3: Weigh 23 parts of polyurethane grafted acrylic emulsion, 70 parts of polyurethane prepolymer, 3 parts of modified filler, 23 parts of curing agent, 1.3 parts of antioxidant 1010, and 1.5 parts of UNIQFOAM 280W silicone defoamer;

[0098] The temperature of the internal mixer was adjusted to 160°C, and the polyurethane grafted acrylic emulsion and the modified filler were first added into the internal mixer. After internal mixing for 5 minutes, the polyurethane prepolymer, curing agent, antioxidant 1010, and UNIQFOAM 280W silicone defoaming agent were added, and the internal mixing was continued for 15 minutes to obtain a mixture. The mixture was then poured into a mold, cured at room temperature for 24 hours, and then placed in an oven at 70°C for aging for 36 hours to obtain an aging-resistant polyurethane glass laminated film.

[0099] Comparative Example 1

[0100] The difference between this comparative example and Example 1 is that no polyurethane grafted acrylic emulsion is added. Specifically:

[0101] S3: Weigh 70 parts of polyurethane prepolymer, 6 parts of modified filler, 23 parts of curing agent, 1.3 parts of antioxidant 1010, and 1.5 parts of UNIQFOAM 280W silicone defoamer;

[0102] The temperature of the internal mixer was adjusted to 160°C, and the modified filler, polyurethane prepolymer, curing agent, antioxidant 1010, and UNIQFOAM 280W silicone defoaming agent were added into the internal mixer, and the internal mixing was continued for 15 minutes to obtain a mixture. The mixture was then poured into a mold, cured at room temperature for 24 hours, and then placed in an oven at 70°C for aging for 36 hours to obtain an aging-resistant polyurethane glass laminated film.

[0103] Comparative Example 2

[0104] The difference between this comparative example and Example 1 is that the curing agent is replaced by polymethylene polyphenyl isocyanate, and terminal hydrogen silicone oil is added separately. Other differences are the same as in Example 1; specifically:

[0105] S3: Weigh 23 parts of polyurethane grafted acrylic emulsion, 70 parts of polyurethane prepolymer, 6 parts of modified filler, 18 parts of polymethylene polyphenyl isocyanate, 5 parts of terminal hydrogen silicone oil, 1.3 parts of antioxidant 1010, and 1.5 parts of UNIQFOAM 280W silicone defoamer;

[0106] The temperature of the internal mixer was adjusted to 160°C, and the polyurethane grafted acrylic emulsion and the modified filler were first added into the internal mixer. After internal mixing for 5 minutes, the polyurethane prepolymer, polymethylene polyphenyl isocyanate, antioxidant 1010, and UNIQFOAM 280W silicone defoamer were added, and the internal mixing was continued for 15 minutes to obtain a mixture. The mixture was then poured into a mold, cured at room temperature for 24 hours, and then placed in an oven at 70°C for aging for 36 hours to obtain an aging-resistant polyurethane glass laminated film.

[0107] Comparative Example 3

[0108] The difference between this comparative example and Example 1 is that only carbon black is used as a filler for modification to obtain a modified filler, and the rest is the same as Example 1; specifically:

[0109] S2: a. Add 10 parts of carbon black and 20 parts of γ-aminopropyltriethoxysilane to 200 parts of anhydrous ethanol, mechanically stir for 2 hours, filter and dry to obtain a modified filler.

[0110] Comparative Example 4

[0111] The difference between this comparative example and Example 1 is that no modified carbon black is added, and the other parts are the same as Example 4; specifically:

[0112] S2: a. To 500 parts of anhydrous ethanol, 100 parts of 20 wt% ammonia water were added, and the mixture was mechanically stirred for 50 min. Finally, 100 parts of tetraisobutyl titanate were added, and the mixture was stirred for 8 h. Finally, the mixture was centrifuged, washed, dried, and ground to obtain a titanium dioxide material.

[0113] b. Add 10 parts of titanium dioxide material and 20 parts of γ-aminopropyltriethoxysilane to 200 parts of anhydrous ethanol, mechanically stir for 2 hours, filter and dry to obtain a modified filler.

[0114] Comparative Example 5

[0115] The difference between this comparative example and Example 1 is that no modified filler is added, and the other parts are the same as Example 1; specifically:

[0116] S3: Weigh 23 parts of polyurethane grafted acrylic emulsion, 70 parts of polyurethane prepolymer, 23 parts of curing agent, 1.3 parts of antioxidant 1010, and 1.5 parts of UNIQFOAM 280W silicone defoamer;

[0117] The temperature of the internal mixer was adjusted to 160°C, and the polyurethane grafted acrylic emulsion and the modified filler were first added into the internal mixer. After internal mixing for 5 minutes, the polyurethane prepolymer, curing agent, antioxidant 1010, and UNIQFOAM 280W silicone defoaming agent were added, and the internal mixing was continued for 15 minutes to obtain a mixture. The mixture was then poured into a mold, cured at room temperature for 24 hours, and then placed in an oven at 70°C for aging for 36 hours to obtain an aging-resistant polyurethane glass laminated film.

[0118] Performance test: The aging resistance performance test of the aging-resistant polyurethane glass laminated films prepared in Examples 1 to 7 and Comparative Examples 1 to 5 was performed; the specific operation is as follows:

[0119] (1) Using a UHY-W universal prototype machine, the polyurethane glass laminated film prepared in each example was made into two equal-diameter dumbbell-shaped splines. One of the corresponding splines in each example was then aged. The aging method was as follows: one dumbbell-shaped sample from each example was placed on a sample rack in a UV aging chamber. The aging conditions were: temperature 50°C, light intensity 1w / m2, and UVA 340nm light source. After the sample was exposed to these conditions for 10 days, it was removed and placed in a standard environment for 3 hours for equilibrium.

[0120] (2) According to the test method of GB / T 528-2009, the tensile strength of the aged and unaged specimens of each example was tested using an AGX-V2 universal testing machine at a tensile speed of 100 mm / min.

[0121] The specific data are shown in Table 1 below:

[0122] Table 1

[0123]

[0124] Results Analysis: According to the data in Table 1, the examples of the present application have higher initial tensile strength than comparative examples 1 and 5, and their strength reduction rate after aging treatment is also lower. When the conventional curing agent in comparative example 2 replaces the curing agent prepared in the present application, even with the addition of end-hydrogenated silicone oil, its anti-aging ability is far inferior to that of the polyurethane glass laminated film of the examples of the present application. Moreover, the anti-aging ability of the polyurethane glass laminated film of the present application is stronger than that of comparative examples 3 and 4. This shows that the curing agent prepared by the present invention has an excellent curing effect on the polyurethane prepolymer and can significantly improve the aging resistance. The carbon black and titanium dioxide in the carbon black / titanium dioxide composite material synergistically improve the aging resistance of the polyurethane glass laminated film. In addition, the amino group of the modified filler and the carbon-carbon double bonds on the polyurethane grafted acrylic emulsion produce a cross-linked structure, forming a three-dimensional structure between the molecules in the polyurethane elastomer material. Finally, the polyurethane glass laminated film has excellent aging resistance and enhanced mechanical properties.

[0125] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A processing technology for aging-resistant polyurethane glass interlayer film for laminated glass, characterized in that: The following steps are involved: S1: reacting an olefinic halogen compound with a hydrogen-terminated silicone oil to obtain modified silicone oil A; reacting modified silicone oil A with potassium phthalimide, followed by hydrazinolysis to obtain modified silicone oil B; reacting modified silicone oil B with dimethyl carbonate to obtain modified silicone oil C; After catalytic pyrolysis, a curing agent is obtained; S2: modifying carbon black with a silane coupling agent, and then growing titanium dioxide in situ on the surface of the carbon black to obtain a carbon black / titanium dioxide composite material; and then modifying the carbon black / titanium dioxide composite material with a silane coupling agent to obtain a modified filler; S3: mixing the raw materials of various components in an internal mixer to obtain a mixed material; and finally performing injection molding, curing, and aging to obtain an aging-resistant polyurethane glass laminated film, wherein the raw materials include: polyurethane grafted acrylic emulsion, polyurethane prepolymer, the curing agent, the modified filler, and additives; The raw materials in S3 are calculated by weight as follows: 15-30 parts of polyurethane grafted acrylic emulsion, 60-80 parts of polyurethane prepolymer, 15-25 parts of curing agent, 3-8 parts of modified filler, 1-2 parts of antioxidant, and 1-2 parts of defoaming agent; The preparation method of the curing agent is specifically as follows: Mix the olefinic halogen compound and the terminal hydrogen-containing silicone oil, add chloroplatinic acid, and react at 60-100°C for 2-4 hours to obtain modified silicone oil A; Mix potassium phthalimide, modified silicone oil A, and anhydrous ethanol evenly, adjust the temperature to 40-60°C, react for 2-6 hours, then add hydrazine monohydrate, maintain the original temperature, react for 15-30 minutes, separate, and dry to obtain modified silicone oil B; Modified silicone oil B, dimethyl carbonate, and catalyst 1 were mixed evenly, and reacted under nitrogen at 170-230°C and 1.0-5.3 MPa for 2-8 hours to obtain modified silicone oil C; Add modified silicone oil C and catalyst 2 to dioctyl phthalate, react at 150-300°C and 1-3 MPa for 3-6 hours to obtain a curing agent.

2. The processing technology of the aging-resistant polyurethane glass interlayer film for laminated glass according to claim 1, characterized in that: The olefinic halogen-containing compound includes any one of 1,2,3-trichloropropylene, 1,4-dichloro-2-butene, 1,4-dibromo-2-butene, and 1,6-dibromo-3-hexene.

3. The process for processing an aging-resistant polyurethane glass interlayer film for laminated glass according to claim 1, characterized in that: The volume ratio of the olefinic halogen-containing compound to the terminal hydrogen-containing silicone oil is (0.5~1):1; the mass ratio of the potassium phthalimide, modified silicone oil A, and hydrazine monohydrate is (0.5~0.8):1:(1.5~2.5); the mass ratio of the modified silicone oil B to dimethyl carbonate is 1:(8~10); the mass ratio of the modified silicone oil C to dioctyl phthalate is 1:(15~20).

4. The processing technology of the aging-resistant polyurethane glass interlayer film for laminated glass according to claim 1, characterized in that: The preparation method of the modified filler is specifically as follows: a. Add carbon black and γ-mercaptopropyltrioxysilane to benzophenone, disperse them by ultrasonication for 5-15 minutes, and irradiate them with 330-380 nm ultraviolet light for 10-30 minutes to obtain modified carbon black; b. Add the modified carbon black to anhydrous ethanol, ultrasonically disperse for 5-15 minutes, then add ammonia water, mechanically stir for 30-60 minutes, and finally add tetraisobutyl titanate, continue stirring for 5-10 hours, and finally centrifuge, wash, dry, and grind to obtain a carbon black / titanium dioxide composite material; c. Add the carbon black / titanium dioxide composite material and γ-aminopropyltriethoxysilane to anhydrous ethanol, mechanically stir for 1 to 3 hours, filter and dry to obtain a modified filler.

5. The process for processing an aging-resistant polyurethane glass laminated film for laminated glass according to claim 4, characterized in that: In the preparation of the modified filler, the mass ratio of carbon black, γ-mercaptopropyltrioxysilane, and benzophenone in step a is (0.5-1):2:(0.8-1.2); the mass ratio of modified carbon black, ammonia water, and tetraisobutyl titanate in step b is 1:(8-10):(8-12); and the mass ratio of carbon black / titanium dioxide composite material, γ-aminopropyltriethoxysilane, and anhydrous ethanol in step c is 1:(1.8-2.5):(15-25).

6. The process for processing an aging-resistant polyurethane glass laminated film for laminated glass according to claim 1, characterized in that: The catalyst 1 is any one of zinc carbonate, zinc oxide, and triphenyltin acetate; the catalyst 2 is any one of zinc powder, zinc acetate, and aluminum powder.

7. The process for processing an aging-resistant polyurethane glass laminated film for laminated glass according to claim 1, characterized in that: S3 is specifically as follows: firstly, the polyurethane grafted acrylic emulsion and the modified filler are placed into an internal mixer at a temperature of 150-160°C, and the mixture is mixed for 5-10 minutes; then, the polyurethane prepolymer, curing agent, antioxidant, and defoaming agent are added, and the mixing is continued for 10-20 minutes to obtain a mixture; the mixture is injected into a mold, and after curing and aging, an aging-resistant polyurethane glass laminated film is obtained.

8. An aging-resistant polyurethane glass laminated film prepared according to the processing process for an aging-resistant polyurethane glass laminated film for laminated glass according to any one of claims 1 to 6.

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