Preparation method of anti-yellowing home decoration beauty glue

Abstract

The invention provides a method for preparing an anti-yellowing home improvement beauty glue, belonging to the technical field of beauty glue. The preparation method comprises the steps of modifying polydimethylsiloxane, compounding, nanoparticle treatment, functionalization, and mixing. The modified polydimethylsiloxane step comprises the following steps: adding α,ω-dihydroxy polydimethylsiloxane to xylene, stirring under a nitrogen atmosphere, adding a modifier, and stirring at 76-80°C for 3.0-3.5 hours to obtain the modified polydimethylsiloxane. The modifier is 2,2,6,6-tetramethylpiperidinol, isophorone diisocyanate, and dibutyltin dilaurate, and the mixture is heated at 56-60°C for 1.8-2.2 hours under a nitrogen atmosphere to obtain the modified polydimethylsiloxane. The beauty glue prepared by the preparation method has good and long-lasting anti-yellowing performance, high strength, and excellent strength retention performance in high temperature and humid environments.

Description

Technical Field

[0001] The invention belongs to the technical field of cosmetic glue, and particularly relates to a method for preparing an anti-yellowing cosmetic glue for home decoration. Background Art

[0002] Beauty glue, also known as glass glue and silicone, is mainly used to enhance the stability and sense of lines of the decoration surface. In the field of home decoration, beauty glue is an indispensable material. It is widely used in filling and beautifying tile gaps, door and window gaps, kitchen and bathroom edges and other parts. It can not only effectively prevent dust, water vapor, insects, etc. from entering the gaps, and play a role in waterproofing, moisture-proofing, and insect-proofing, but also can extend the service life of the decoration by improving the aesthetics of the home; and, when the temperature changes and the expansion and contraction of building materials cause the size of the gap to change, the beauty glue has good toughness, which can ensure the durability of the sealing effect.

[0003] However, during use, traditional home decoration beauty glue is prone to yellowing under the influence of environmental factors such as light, oxygen, humidity and temperature changes, which seriously affects the aesthetics of home decoration, especially in light-colored or white decoration scenes. This is more obvious, thereby reducing the effectiveness of the beauty glue and shortening its service life.

[0004] In order to solve the problem of yellowing of home improvement beauty glue, the existing technology mainly adopts the following methods:

[0005] One is to add UV absorbers and antioxidants, which can delay yellowing to a certain extent. However, as time goes by, the UV absorbers and antioxidants will gradually lose their effectiveness, thereby weakening the anti-yellowing effect. In addition, the addition of UV absorbers and antioxidants will also reduce the mechanical properties of the colloid.

[0006] The second method is to use physical barrier, by applying an anti-yellowing coating on the surface of the beauty glue, which can delay the yellowing effect in a short time. However, in high temperature and high humidity environments, the coating is easy to fall off, resulting in unstable anti-yellowing effect.

[0007] The third method is to use nanomaterial composites. Nanomaterials are added to reduce ultraviolet erosion through light scattering. However, the dispersion of nanomaterials is poor, their compatibility with the resin matrix is ​​poor, and the interfacial bonding force is weak, which causes the colloid to easily crack, have uneven strength and poor weather resistance.

[0008] CN117511480A discloses a yellowing-resistant, mildew-proof, and antibacterial polyurea cosmetic glue and a preparation method thereof, comprising preparing a transparent semi-finished product, adding polyurea, alkoxy-terminated ethyl polydimethylsiloxane, polydimethylsilicone, white carbon black, a water scavenger, and a cross-linking agent into a high-speed disperser, adding a yellowing-resistant and heat-insulating material to obtain a yellowing-resistant, mildew-proof, and high-temperature-resistant cosmetic glue solvent semi-finished product, adding an antibacterial material, and pouring an adsorbent, a thickener, and an anti-cracking agent to prepare a cosmetic glue material capable of adsorbing harmful substances, thereby obtaining the yellowing-resistant, mildew-proof, and antibacterial polyurea cosmetic glue; wherein the light-resistant and heat-insulating material is polycarbonate and polyurethane;

[0009] This patent mainly involves mixing polyurea with yellowing-resistant insulation materials such as polycarbonate and polyurethane. Polyurea itself has good high-temperature resistance, and combined with polycarbonate, it can enhance the high-temperature strength of the beauty glue, thereby reducing degradation and yellowing under high temperatures; however, the beauty glue prepared by this method will still degrade under long-term ultraviolet irradiation, and has poor resistance to moisture and heat, and poor strength retention in a humid and hot environment. Summary of the Invention

[0010] In order to solve the technical problems existing in the prior art, the present invention provides a method for preparing an anti-yellowing home improvement beauty glue, which has good and long-lasting anti-yellowing performance, high strength, and excellent strength retention performance in high temperature and humid hot environments.

[0011] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0012] The present invention provides a method for preparing an anti-yellowing home improvement beauty glue, comprising the steps of modified polydimethylsiloxane, compounding, nanoparticle treatment, functionalization, and mixing, specifically as follows:

[0013] 1. Modified polydimethylsiloxane

[0014] α,ω-dihydroxypolydimethylsiloxane is added to xylene, and under a nitrogen atmosphere, the temperature is raised to 76-80°C, and the mixture is stirred at 200-220 rpm for 28-32 minutes. After the stirring is completed, a modifier is added at a rate of 0.06-0.15 g / min. After the addition is completed, the mixture is kept warm and stirred at 76-80°C for 3.0-3.5 hours, and then washed and dried to obtain a modified polydimethylsiloxane.

[0015] The viscosity of the α,ω-dihydroxypolydimethylsiloxane at room temperature is 11000-13000 mPa·s;

[0016] The mass ratio of the α,ω-dihydroxypolydimethylsiloxane, xylene, and modifier is 12.0-13.0:500:3.5-4.0;

[0017] The preparation method of the modifier comprises the following steps: adding 2,2,6,6-tetramethylpiperidinol and isophorone diisocyanate to a reaction container, stirring the mixture uniformly under a nitrogen atmosphere, then adding dibutyltin dilaurate, raising the temperature to 56-60° C. at a rate of 0.8-1.2° C. / min, and stirring the mixture for 1.8-2.2 hours to obtain the modifier;

[0018] The mass ratio of the 2,2,6,6-tetramethylpiperidinol, isophorone diisocyanate and dibutyltin dilaurate is 32-37:48-52:0.22-0.26.

[0019] 2. Compound

[0020] Adding modified polydimethylsiloxane to a reaction vessel, and adding the mixed solution under a nitrogen atmosphere, controlling the addition rate of the mixed solution to 3.0-4.0 g / min, and controlling the stirring rate to 130-150 rpm. After the addition is completed, raising the temperature to 62-66° C. at a rate of 0.4-0.6° C. / min, and keeping the temperature at 160-180 rpm for 3.8-4.3 hours. After the reaction is completed, naturally cooling to room temperature, washing and drying to obtain a polydimethylsiloxane composite;

[0021] The mass ratio of the modified polydimethylsiloxane to the mixed liquid is 95-105:240-260;

[0022] The mixed solution is prepared by adding hydroxyethyl methacrylate and azobisisobutyronitrile to ethyl acetate, and stirring at 70-100 rpm for 28-35 minutes to obtain a mixed solution;

[0023] The mass ratio of the ethyl acetate, hydroxyethyl methacrylate and azobisisobutyronitrile is 240-260:6.0-6.5:0.6-0.8.

[0024] 3. Nanoparticle Treatment

[0025] (1) Nanoparticle pretreatment

[0026] Titanium dioxide and cerium oxide are added to xylene, stirred evenly, and then ball milled. The grinding balls are zirconium oxide balls, the ball-to-material ratio is 3-5:1, the ball milling time is 0.8-1.2 hours, the ball milling speed is 250-270 rpm, and the ball milling temperature is 38-42° C. After the ball milling is completed, oleic acid and succinic acid are added, stirred evenly, and kept stirring at 38-42° C. for 5.7-6.3 hours. After the stirring is completed, the mixture is filtered, washed, and dried to obtain acid-treated nanoparticles; the acid-treated nanoparticles are placed in a plasma treatment device, a mixed gas is introduced, and radio frequency plasma treatment is performed. The treatment power is controlled to 70-75 W, and the treatment time is 6.5-7.5 minutes. After the treatment is completed, the mixture is cooled in nitrogen to obtain pre-treated nanoparticles.

[0027] The particle size of the titanium dioxide is 130-150 nm;

[0028] The particle size of the cerium oxide is 100-120 nm;

[0029] The mass ratio of xylene, titanium dioxide, cerium oxide, oleic acid and succinic acid is 240-260:8-12:9-11:1.1-1.5:0.6-0.8;

[0030] The mixed gas is carbon dioxide and oxygen, and the volume ratio of carbon dioxide to oxygen is 1-1.3:1;

[0031] (2) Secondary processing

[0032] The pre-treated nanoparticles are added to N,N-dimethylformamide and stirred evenly, followed by addition of p-aminobenzoic acid and diethylenetriamine, and stirring at 150-170 rpm for 35-45 minutes. 4-dimethylaminopyridine and N,N'-dicyclohexylcarbodiimide are then added, and the temperature is raised to 40-45°C. The reaction is kept warm for 8.3-8.7 hours. After the reaction is completed, the mixture is filtered, washed, and dried to obtain secondary treated nanoparticles.

[0033] The mass ratio of the pre-treated nanoparticles, N,N-dimethylformamide, p-aminobenzoic acid, diethylenetriamine, 4-dimethylaminopyridine and N,N'-dicyclohexylcarbodiimide is 9.5-10.5:300:0.8-1.2:1.3-1.7:0.20-0.25:1.8-2.2.

[0034] 4. Functionalization

[0035] Adding a polydimethylsiloxane complex to N,N-dimethylformamide, stirring evenly, then adding the secondary treated nanoparticles, continuing to stir evenly, then raising the temperature to 60-65°C at a rate of 0.4-0.6°C / min, and keeping the temperature for reaction for 4.8-5.2 hours. After the reaction is completed, separating the solid, washing, and drying to obtain a functionalized complex;

[0036] The mass ratio of the N,N-dimethylformamide, the polydimethylsiloxane compound and the secondary treated nanoparticles is 400:18-22:4.4-4.8.

[0037] 5. Mixing

[0038] Add the functionalized complex to the reaction vessel, increase the temperature to 38-42° C., add dioctyl phthalate, continue stirring for 17-23 minutes, add calcium carbonate, leveling agent BYK-333, and antioxidant 1010, continue stirring until uniform, add kH560 silane coupling agent and dibutyltin dilaurate, and stir at room temperature at a stirring speed of 770-820 rpm for 9.8-10.5 hours. After the stirring is completed, vacuum degassing and packaging are performed to obtain the anti-yellowing home improvement beauty glue;

[0039] The mass ratio of the functionalized composite, dioctyl phthalate, calcium carbonate, leveling agent BYK-333, antioxidant 1010, kH560 silane coupling agent and dibutyltin dilaurate is 100:14-16:10.2-10.7:1.0-1.4:0.8-1.2:2.2-2.7:1.4-1.8.

[0040] Compared with the prior art, the present invention has achieved the following beneficial effects:

[0041] 1. The present invention adopts α, ω-dihydroxy polydimethylsiloxane as the cosmetic glue matrix. First, 2,2,6,6-tetramethylpiperidinol and isophorone diisocyanate are reacted to prepare a modifier. 2,2,6,6-tetramethylpiperidinol can long-term inhibit ultraviolet-induced free radical degradation. Then, the isocyanate group of the modifier reacts with the hydroxyl group of α, ω-dihydroxy polydimethylsiloxane, so that 2,2,6,6-tetramethylpiperidinol and α, ω-dihydroxy polydimethylsiloxane are firmly combined. The anti-yellowing ability of the beauty glue is enhanced while the strength performance and high-temperature stability are enhanced; in the compounding step, hydroxyethyl methacrylate is polymerized under the action of azobisisobutyronitrile to obtain polyhydroxyethyl methacrylate, which can form an interpenetrating network structure through interaction with α, ω-dihydroxypolydimethylsiloxane, thereby improving the cohesion of the material; the nanoparticles used are cerium oxide and titanium dioxide, both of which are excellent UV shielding agents. Succinic acid and long-chain oleic acid are first used to improve the dispersion performance of the nanoparticles and reduce the agglomeration between the particles. The compatibility with the organic matrix is ​​enhanced, and then carboxyl groups are introduced on the surface of the nanoparticles through plasma treatment, providing reactive sites for the subsequent secondary treatment step. In the secondary treatment step, p-aminobenzoic acid and diethylenetriamine are introduced, and the amino groups thereof undergo amidation reaction with the carboxyl groups of the secondary treated nanoparticles to form a stable organic-inorganic stable complex. The p-aminobenzoic acid has good ultraviolet absorption performance, further improving the anti-yellowing performance of the product and enhancing the stability of the product. In the functionalization step, the hydroxyl and isocyanate groups of α, ω-dihydroxy polydimethylsiloxane can interact with the amino and carboxyl groups of the secondary treated nanoparticles to obtain a functionalized complex with excellent stability, which can effectively inhibit the thermal motion of the polymer chain, improve the high temperature resistance of the product, inhibit the migration and agglomeration of the nanoparticles, and further improve the durability of the product. After the mixing step, under the joint action of various components, a home improvement beauty glue product with good and long-lasting anti-yellowing performance, high strength, and excellent stability is obtained.

[0042] 2. The anti-yellowing home improvement beauty glue prepared by the method of the present invention has a bonding strength of 4.25-4.31 MPa, a tensile strength of 5.68-5.77 MPa, and an elongation at break of 577-589%;

[0043] 3. The anti-yellowing home improvement beauty glue prepared by the method of the present invention is measured according to the method in GB / T 39294-2020 "Determination of discoloration (yellowing) performance of adhesives". The total color difference △E when the irradiation time is 168h * ab The total color difference △E is 1.04-1.08 when the irradiation time is 360h * ab is 1.17-1.24;

[0044] 4. The anti-yellowing home improvement glue prepared by the method of the present invention is used at a temperature of 35°C and an ultraviolet light intensity of 40W / cm 2 After irradiation for 15 days in the environment, the bonding strength is 4.15-4.25MPa, the tensile strength is 5.45-5.58MPa, and the elongation at break is 559-576%;

[0045] 5. The anti-yellowing home improvement beauty glue prepared by the method of the present invention has a bonding strength of 4.11-4.22 MPa, a tensile strength of 5.41-5.54 MPa, and an elongation at break of 553-573% after being left to stand for 15 days in an environment of temperature of 65°C and humidity of 80%. DETAILED DESCRIPTION

[0046] In order to more clearly understand the technical features, purposes and effects of the present invention, specific embodiments of the present invention are now described.

[0047] Example 1: Preparation method of anti-yellowing home improvement beauty glue

[0048] 1. Modified polydimethylsiloxane

[0049] 12.0 g of α, ω-dihydroxy polydimethylsiloxane was added to 500 g of xylene. Under a nitrogen atmosphere, the temperature was raised to 76° C. and stirred at 200 rpm for 28 min. After the stirring was completed, 3.5 g of a modifier was added at a rate of 0.06 g / min. After the addition was completed, the mixture was kept warm and stirred at 76° C. for 3.0 h, and then washed and dried to obtain a modified polydimethylsiloxane.

[0050] The viscosity of the α,ω-dihydroxypolydimethylsiloxane at room temperature is 11000 mPa·s;

[0051] The preparation method of the modifier comprises the following steps: adding 32 g of 2,2,6,6-tetramethylpiperidinol and 48 g of isophorone diisocyanate to a reaction container, stirring the mixture uniformly under a nitrogen atmosphere, then adding 0.22 g of dibutyltin dilaurate, raising the temperature to 56° C. at a rate of 0.8° C. / min, and stirring the mixture for 1.8 hours to obtain the modifier.

[0052] 2. Compound

[0053] 95 g of modified polydimethylsiloxane was added to the reaction vessel, and 240 g of the mixed solution was added under a nitrogen atmosphere at a rate of 3.0 g / min and a stirring rate of 130 rpm. After the addition was completed, the temperature was raised to 62° C. at a rate of 0.4° C. / min and kept at 160 rpm for 3.8 h. After the reaction was completed, the temperature was naturally lowered to room temperature, washed, and dried to obtain a polydimethylsiloxane composite.

[0054] The mixed solution was prepared by adding 6.0 g of hydroxyethyl methacrylate and 0.6 g of azobisisobutyronitrile to 240 g of ethyl acetate, and stirring the mixture at 70 rpm for 35 minutes to obtain a mixed solution.

[0055] 3. Nanoparticle Treatment

[0056] (1) Nanoparticle pretreatment

[0057] 8 g of titanium dioxide and 9 g of cerium oxide were added to 240 g of xylene, and the mixture was stirred evenly before ball milling. The grinding balls were zirconium oxide balls, the ball-to-material ratio was 3:1, the ball milling time was 0.8 h, the ball milling speed was 250 rpm, and the ball milling temperature was 38° C. After the ball milling was completed, 1.1 g of oleic acid and 0.6 g of succinic acid were added, and the mixture was stirred evenly. The mixture was kept stirred at 38° C. for 5.7 h. After the stirring was completed, the mixture was filtered, washed, and dried to obtain acid-treated nanoparticles. The acid-treated nanoparticles were placed in a plasma treatment device, and a mixed gas was introduced to perform radio frequency plasma treatment. The treatment power was controlled to 70 W, and the treatment time was 7.5 min. After the treatment was completed, the mixture was cooled in nitrogen to obtain pre-treated nanoparticles.

[0058] The particle size of the titanium dioxide is 130 nm;

[0059] The particle size of the cerium oxide is 100 nm;

[0060] The mixed gas is carbon dioxide and oxygen, and the volume ratio of carbon dioxide to oxygen is 1.2:1;

[0061] (2) Secondary processing

[0062] 9.5 g of pre-treated nanoparticles were added to 300 g of N, N-dimethylformamide and stirred evenly. Then, 0.8 g of p-aminobenzoic acid and 1.3 g of diethylenetriamine were added and stirred at 150 rpm for 35 min. Then, 0.20 g of 4-dimethylaminopyridine and 1.8 g of N, N'-dicyclohexylcarbodiimide were added. The temperature was raised to 40 ° C. and the reaction was kept warm for 8.3 h. After the reaction was completed, the mixture was filtered, washed and dried to obtain secondary treated nanoparticles.

[0063] 4. Functionalization

[0064] 18 g of polydimethylsiloxane complex was added to 400 g of N,N-dimethylformamide and stirred evenly. Then, 4.4 g of secondary treated nanoparticles were added and stirred evenly. The temperature was then raised to 60°C at a rate of 0.4°C / min and the reaction was kept warm for 5.2 hours. After the reaction was completed, the solid was separated, washed and dried to obtain a functionalized complex.

[0065] 5. Mixing

[0066] 100 g of the functionalized composite was added to the reaction vessel, the temperature was raised to 38 ° C, 14 g of dioctyl phthalate was added, and stirring was continued for 17 min. 10.2 g of calcium carbonate, 1.0 g of leveling agent BYK-333, and 0.8 g of antioxidant 1010 were added, and stirring was continued. Then, 2.2 g of kH560 silane coupling agent and 1.4 g of dibutyltin dilaurate were added, and the mixture was stirred at room temperature at a stirring speed of 770 rpm for 10.5 h. After stirring, vacuum degassing and packaging were performed to obtain an anti-yellowing home improvement beauty glue.

[0067] Example 2: Preparation method of anti-yellowing home improvement beauty glue

[0068] 1. Modified polydimethylsiloxane

[0069] 12.5 g of α, ω-dihydroxy polydimethylsiloxane was added to 500 g of xylene. Under a nitrogen atmosphere, the temperature was raised to 78° C. and stirred at 210 rpm for 30 min. After the stirring was completed, 3.7 g of a modifier was added at a rate of 0.1 g / min. After the addition was completed, the mixture was kept warm and stirred at 78° C. for 3.2 h, and then washed and dried to obtain a modified polydimethylsiloxane.

[0070] The viscosity of the α,ω-dihydroxypolydimethylsiloxane at room temperature is 12000 mPa·s;

[0071] The preparation method of the modifier is as follows: 35g of 2,2,6,6-tetramethylpiperidinol and 50g of isophorone diisocyanate are added to a reaction container, and the mixture is stirred evenly under a nitrogen atmosphere. Then, 0.24g of dibutyltin dilaurate is added, the temperature is increased to 58°C at a rate of 1.0°C / min, and the mixture is stirred for 2.0h to obtain the modifier.

[0072] 2. Compound

[0073] 100 g of modified polydimethylsiloxane was added to a reaction vessel, and 250 g of the mixed solution was added under a nitrogen atmosphere at a rate of 3.5 g / min and a stirring rate of 140 rpm. After the addition was completed, the temperature was raised to 64° C. at a rate of 0.5° C. / min and kept at 170 rpm for 4.0 h. After the reaction was completed, the temperature was naturally lowered to room temperature, washed, and dried to obtain a polydimethylsiloxane composite.

[0074] The mixed solution was prepared by adding 6.3 g of hydroxyethyl methacrylate and 0.7 g of azobisisobutyronitrile to 250 g of ethyl acetate, and stirring the mixture at 80 rpm for 30 minutes to obtain a mixed solution.

[0075] 3. Nanoparticle Treatment

[0076] (1) Nanoparticle pretreatment

[0077] 10 g of titanium dioxide and 10 g of cerium oxide were added to 250 g of xylene, and the mixture was stirred evenly before ball milling. The grinding balls were zirconium oxide balls, the ball-to-material ratio was 4:1, the ball milling time was 1.0 h, the ball milling speed was 260 rpm, and the ball milling temperature was 40° C. After the ball milling was completed, 1.3 g of oleic acid and 0.7 g of succinic acid were added, and the mixture was stirred evenly. The mixture was kept warm and stirred at 40° C. for 6.0 h. After the stirring was completed, the mixture was filtered, washed, and dried to obtain acid-treated nanoparticles. The acid-treated nanoparticles were placed in a plasma treatment device, and a mixed gas was introduced to perform radio frequency plasma treatment. The treatment power was controlled to 72 W, and the treatment time was 7.0 min. After the treatment was completed, the mixture was cooled in nitrogen to obtain pre-treated nanoparticles.

[0078] The particle size of the titanium dioxide is 140 nm;

[0079] The particle size of the cerium oxide is 110 nm;

[0080] The mixed gas is carbon dioxide and oxygen, and the volume ratio of carbon dioxide to oxygen is 1:1;

[0081] (2) Secondary processing

[0082] 10 g of pre-treated nanoparticles were added to 300 g of N, N-dimethylformamide and stirred evenly. Then, 1.0 g of p-aminobenzoic acid and 1.5 g of diethylenetriamine were added and stirred at 160 rpm for 40 min. Then, 0.23 g of 4-dimethylaminopyridine and 2.0 g of N, N'-dicyclohexylcarbodiimide were added. The temperature was raised to 42 ° C. and the reaction was kept warm for 8.5 h. After the reaction was completed, the mixture was filtered, washed and dried to obtain secondary treated nanoparticles.

[0083] 4. Functionalization

[0084] 20 g of polydimethylsiloxane complex was added to 400 g of N,N-dimethylformamide, and after stirring evenly, 4.6 g of secondary treated nanoparticles was added and continued to stir evenly. Then, the temperature was raised to 62 ° C at a rate of 0.5 ° C / min and kept for 5.0 h. After the reaction was completed, the solid was separated, washed and dried to obtain a functionalized complex.

[0085] 5. Mixing

[0086] 100 g of the functionalized composite was added to the reaction vessel, the temperature was raised to 40 ° C, 15 g of dioctyl phthalate was added, and stirring was continued for 20 min. 10.5 g of calcium carbonate, 1.2 g of leveling agent BYK-333, and 1.0 g of antioxidant 1010 were added. After continuing to stir evenly, 2.5 g of kH560 silane coupling agent and 1.6 g of dibutyltin dilaurate were added. The mixture was stirred at room temperature at a stirring speed of 800 rpm for 10.0 h. After the stirring was completed, vacuum degassing and packaging were performed to obtain an anti-yellowing home improvement beauty glue.

[0087] Example 3: Preparation method of anti-yellowing home improvement beauty glue

[0088] 1. Modified polydimethylsiloxane

[0089] 13.0 g of α, ω-dihydroxy polydimethylsiloxane was added to 500 g of xylene. Under a nitrogen atmosphere, the temperature was raised to 80° C. and stirred at 220 rpm for 32 min. After the stirring was completed, 4.0 g of a modifier was added at a rate of 0.15 g / min. After the addition was completed, the mixture was kept warm and stirred at 80° C. for 3.5 h, and then washed and dried to obtain a modified polydimethylsiloxane.

[0090] The viscosity of the α,ω-dihydroxypolydimethylsiloxane at room temperature is 13000 mPa·s;

[0091] The preparation method of the modifier comprises the following steps: adding 37 g of 2,2,6,6-tetramethylpiperidinol and 52 g of isophorone diisocyanate to a reaction container, stirring the mixture uniformly under a nitrogen atmosphere, then adding 0.26 g of dibutyltin dilaurate, raising the temperature to 60° C. at a rate of 1.2° C. / min, and stirring the mixture while maintaining the temperature for 2.2 hours to obtain the modifier.

[0092] 2. Compound

[0093] 105 g of modified polydimethylsiloxane was added to the reaction vessel, and 260 g of the mixed solution was added under a nitrogen atmosphere at a rate of 4.0 g / min and a stirring rate of 150 rpm. After the addition was completed, the temperature was raised to 66° C. at a rate of 0.6° C. / min and kept at 180 rpm for 4.3 h. After the reaction was completed, the temperature was naturally lowered to room temperature, washed, and dried to obtain a polydimethylsiloxane composite.

[0094] The mixed solution was prepared by adding 6.5 g of hydroxyethyl methacrylate and 0.8 g of azobisisobutyronitrile to 260 g of ethyl acetate, and stirring the mixture at 100 rpm for 28 minutes to obtain a mixed solution.

[0095] 3. Nanoparticle Treatment

[0096] (1) Nanoparticle pretreatment

[0097] 12 g of titanium dioxide and 11 g of cerium oxide were added to 260 g of xylene, and the mixture was stirred evenly before ball milling. The grinding balls were zirconium oxide balls, the ball-to-material ratio was 5:1, the ball milling time was 1.2 h, the ball milling speed was 270 rpm, and the ball milling temperature was 42° C. After the ball milling was completed, 1.5 g of oleic acid and 0.8 g of succinic acid were added, and the mixture was stirred evenly. The mixture was kept stirred at 42° C. for 6.3 h. After the stirring was completed, the mixture was filtered, washed, and dried to obtain acid-treated nanoparticles. The acid-treated nanoparticles were placed in a plasma treatment device, and a mixed gas was introduced to perform radio frequency plasma treatment. The treatment power was controlled to 75 W, and the treatment time was 6.5 min. After the treatment was completed, the mixture was cooled in nitrogen to obtain pre-treated nanoparticles.

[0098] The particle size of the titanium dioxide is 150 nm;

[0099] The particle size of the cerium oxide is 120 nm;

[0100] The mixed gas is carbon dioxide and oxygen, and the volume ratio of carbon dioxide to oxygen is 1.3:1;

[0101] (2) Secondary processing

[0102] 10.5 g of pre-treated nanoparticles were added to 300 g of N, N-dimethylformamide and stirred evenly. Then, 1.2 g of p-aminobenzoic acid and 1.7 g of diethylenetriamine were added and stirred at 170 rpm for 45 min. Then, 0.25 g of 4-dimethylaminopyridine and 2.2 g of N, N'-dicyclohexylcarbodiimide were added. The temperature was raised to 45 ° C. and the reaction was kept warm for 8.7 h. After the reaction was completed, the mixture was filtered, washed and dried to obtain secondary treated nanoparticles.

[0103] 4. Functionalization

[0104] 22 g of polydimethylsiloxane complex was added to 400 g of N,N-dimethylformamide, and after stirring evenly, 4.8 g of secondary treated nanoparticles was added and continued to stir evenly. Then, the temperature was raised to 65 ° C at a rate of 0.6 ° C / min and kept for 4.8 hours. After the reaction was completed, the solid was separated, washed and dried to obtain a functionalized complex.

[0105] 5. Mixing

[0106] 100 g of the functionalized composite was added to the reaction vessel, the temperature was raised to 42 ° C, 16 g of dioctyl phthalate was added, and stirring was continued for 23 min. 10.7 g of calcium carbonate, 1.4 g of leveling agent BYK-333, and 1.2 g of antioxidant 1010 were added, and stirring was continued. Then, 2.7 g of kH560 silane coupling agent and 1.8 g of dibutyltin dilaurate were added, and stirred at room temperature. The stirring speed was 820 rpm and the stirring time was 9.8 h. After the stirring was completed, vacuum degassing and packaging were performed to obtain the anti-yellowing home improvement beauty glue.

[0107] Comparative Example 2-1

[0108] 1. Modified polydimethylsiloxane

[0109] 12.5 g of α,ω-dihydroxypolydimethylsiloxane was added to 500 g of xylene. Under a nitrogen atmosphere, the temperature was raised to 78°C and stirred at 210 rpm for 30 min. After stirring, 3.7 g of 2,2,6,6-tetramethylpiperidinol was added. After stirring at 78°C for 3.2 h, the mixture was washed and dried to obtain modified polydimethylsiloxane.

[0110] The viscosity of the α,ω-dihydroxypolydimethylsiloxane at room temperature is 12000 mPa·s;

[0111] Omit step 2;

[0112] In step 4, the polydimethylsiloxane complex is replaced with an equal amount of the modified polydimethylsiloxane prepared in step 1 above;

[0113] The operations of steps 3 and 5 are exactly the same as those in Example 2.

[0114] Comparative Example 2-2

[0115] The operations of steps 1 and 2 are exactly the same as those in Example 2;

[0116] 3. Nanoparticle Treatment

[0117] To 250 g of xylene, 10 g of titanium dioxide and 10 g of cerium oxide were added, stirred evenly, and then ball-milled. Zirconia balls were used for the milling, the ball-to-material ratio was 4:1, the ball-milling time was 1.0 h, the ball-milling speed was 260 rpm, and the ball-milling temperature was 40°C. After the ball-milling, 1.3 g of oleic acid and 0.7 g of succinic acid were added, stirred evenly, and the mixture was kept warm and stirred at 40°C for 6.0 h. After the stirring was completed, the mixture was filtered, washed, and dried to obtain acid-treated nanoparticles.

[0118] In step 4, the secondary treated nanoparticles are replaced with an equal amount of the acid treated nanoparticles prepared in step 3 above;

[0119] In step 5, the kH560 silane coupling agent and dibutyltin dilaurate components were replaced with the functionalized composite in equal amounts.

[0120] Experimental testing

[0121] 1. Mechanical properties and anti-yellowing properties

[0122] The mechanical properties and anti-yellowing properties of the anti-yellowing home improvement beauty glue prepared by the methods of Examples 1-3, Comparative Example 2-1, and Comparative Example 2-2 were tested, and the specific results are as follows:

[0123]

[0124] The total color difference △E in the above table for 168h * ab It refers to the determination according to the method in GB / T 39294-2020 "Determination of discoloration (yellowing) properties of adhesives", where the irradiation time is 168h;

[0125] The total color difference △E in the above table over 360 hours * ab It refers to the measurement according to the method in GB / T 39294-2020 "Determination of discoloration (yellowing) properties of adhesives", where the irradiation time is 360h.

[0126] 2. UV radiation resistance

[0127] The anti-yellowing home improvement glue prepared by the methods of Examples 1-3, Comparative Example 2-1 and Comparative Example 2-2 was tested at a temperature of 35°C and an ultraviolet light intensity of 40W / cm 2 After irradiation for 15 days, the mechanical properties were tested again. The specific results are as follows:

[0128]

[0129] 3. High temperature and high humidity resistance

[0130] The anti-yellowing home improvement beauty glue prepared by the methods of Examples 1-3, Comparative Example 2-1, and Comparative Example 2-2 was left to stand for 15 days in an environment of temperature 65°C and humidity 80%, and the mechanical properties were tested again. The specific results are as follows:

[0131]

[0132] The present invention adopts α, ω-dihydroxy polydimethylsiloxane as the base of the beauty glue. First, 2,2,6,6-tetramethylpiperidinol and isophorone diisocyanate are reacted to prepare a modifier. 2,2,6,6-tetramethylpiperidinol can inhibit the free radical degradation caused by ultraviolet rays for a long time. Then, the isocyanate group of the modifier reacts with the hydroxyl group of α, ω-dihydroxy polydimethylsiloxane, so that 2,2,6,6-tetramethylpiperidinol and α, ω-dihydroxy polydimethylsiloxane are firmly combined, thereby improving the beauty effect. The anti-yellowing ability of the adhesive is improved while the strength performance and high-temperature stability are enhanced; in the compounding step, hydroxyethyl methacrylate is polymerized under the action of azobisisobutyronitrile to obtain polyhydroxyethyl methacrylate, which can form an interpenetrating network structure with α, ω-dihydroxypolydimethylsiloxane through interaction, thereby improving the cohesion of the material; the nanoparticles used are cerium oxide and titanium dioxide, both of which are excellent UV shielding agents. Succinic acid and long-chain oleic acid are first used to improve the dispersion performance of the nanoparticles, reduce the agglomeration between the particles, and increase Strong compatibility with the organic matrix, and then through plasma treatment, carboxyl groups are introduced on the surface of the nanoparticles, providing reactive sites for the subsequent secondary treatment step. In the secondary treatment step, p-aminobenzoic acid and diethylenetriamine are introduced, and the amino groups thereof undergo amidation reaction with the carboxyl groups of the secondary treated nanoparticles to form a stable organic-inorganic stable complex. P-aminobenzoic acid has good ultraviolet absorption performance, further improving the anti-yellowing performance of the product and enhancing the stability of the product; in the functionalization step, the hydroxyl and isocyanate groups of α, ω-dihydroxypolydimethylsiloxane can interact with the amino and carboxyl groups of the secondary treated nanoparticles to obtain a functionalized complex with excellent stability, which can effectively inhibit the thermal motion of the polymer chain, improve the high temperature resistance of the product, inhibit the migration and agglomeration of nanoparticles, and further improve the durability of the product. After the mixing step, under the joint action of various components, a home improvement beauty glue product with good and long-lasting anti-yellowing performance, high strength, and excellent stability is obtained.

[0133] Comparative Example 2-1 directly uses 2,2,6,6-tetramethylpiperidinol and α,ω-dihydroxypolydimethylsiloxane for mixed modification, and omits the compounding step, resulting in weak interaction between molecular chains, low strength, and inability to fully exert its anti-yellowing performance. Comparative Example 2-1 cannot form a stable cross-linked network structure, resulting in low mechanical property retention rate under ultraviolet irradiation and high temperature and humid heat environment; Comparative Example 2-2 retains the composite structure, but the nanoparticles are only treated with acid, the dispersibility of the nanoparticles is insufficient, and the interfacial binding ability with organic components such as α,ω-dihydroxypolydimethylsiloxane is poor, which reduces the mechanical properties. In addition, the treatment with p-aminobenzoic acid is omitted, the antioxidant synergistic effect is weak, thereby weakening the anti-yellowing performance. In the mixing step, the cross-linking agent and coupling agent are also omitted, thereby reducing the stability of the cosmetic glue.

[0134] Unless otherwise specified, all percentages used in the present invention are by mass.

[0135] 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 method for preparing an anti-yellowing home improvement beauty glue, characterized in that: It includes modified polydimethylsiloxane, compounding, nanoparticle treatment, functionalization and compounding steps; The modified polydimethylsiloxane step comprises: adding α, ω-dihydroxy polydimethylsiloxane into xylene, stirring under a nitrogen atmosphere, adding a modifier, and stirring at 76-80° C. for 3.0-3.5 hours to obtain the modified polydimethylsiloxane; The modifier is 2,2,6,6-tetramethylpiperidinol, isophorone diisocyanate and dibutyltin dilaurate, which are prepared by heating at 56-60°C for 1.8-2.2 hours under a nitrogen atmosphere; In the modifier, the mass ratio of the 2,2,6,6-tetramethylpiperidinol, isophorone diisocyanate and dibutyltin dilaurate is 32-37:48-52:0.22-0.26; The compounding step comprises adding modified polydimethylsiloxane to a reaction vessel, adding a mixed solution under a nitrogen atmosphere, and reacting at 62-66° C. for 3.8-4.3 hours to obtain a polydimethylsiloxane compound; The mixed solution is prepared by stirring ethyl acetate, hydroxyethyl methacrylate and azobisisobutyronitrile; The nanoparticle processing step includes nanoparticle pre-processing and secondary processing steps; The nanoparticle pretreatment steps include adding titanium dioxide and cerium oxide to xylene, stirring evenly, and then ball milling, using zirconium oxide balls, a ball-to-material ratio of 3-5:1, a ball milling time of 0.8-1.2 hours, a ball milling speed of 250-270 rpm, and a ball milling temperature of 38-42° C. After the ball milling is completed, oleic acid and succinic acid are added, stirring evenly, and then stirring at 38-42° C. for 5.7-6.3 hours. After the stirring is completed, filtering, washing, and drying to obtain acid-treated nanoparticles; placing the acid-treated nanoparticles in a plasma treatment device, introducing a mixed gas to perform radio frequency plasma treatment, controlling the treatment power to 70-75 W, and the treatment time to 6.5-7.5 minutes. After the treatment is completed, cooling in nitrogen to obtain pretreated nanoparticles; The secondary treatment step comprises adding the pre-treated nanoparticles to N,N-dimethylformamide, adding p-aminobenzoic acid and diethylenetriamine, stirring evenly, adding 4-dimethylaminopyridine and N,N'-dicyclohexylcarbodiimide, and reacting at 40-45°C for 8.3-8.7 hours to obtain the secondary treated nanoparticles; The functionalization step comprises adding a polydimethylsiloxane complex to N,N-dimethylformamide, stirring uniformly, adding the secondary treated nanoparticles, continuing to stir uniformly, and then raising the temperature to 60-65° C. at a rate of 0.4-0.6° C. / min, and keeping the temperature for reaction for 4.8-5.2 hours. After the reaction is completed, separating the solid matter, washing and drying it to obtain the functionalized complex; The mass ratio of the N,N-dimethylformamide, polydimethylsiloxane complex, and secondary treated nanoparticles is 400:18-22:4.4-4.8; The mixing step comprises adding the functionalized complex into a reaction container, raising the temperature to 38-42° C., adding dioctyl phthalate, continuing stirring for 17-23 minutes, adding calcium carbonate, a leveling agent BYK-333, and an antioxidant 1010, continuing to stir evenly, adding a kH560 silane coupling agent and dibutyltin dilaurate, stirring at room temperature at a stirring speed of 770-820 rpm and a stirring time of 9.8-10.5 hours. After the stirring is completed, vacuum degassing and packaging are performed to obtain the anti-yellowing home improvement beauty glue.

2. The method for preparing the anti-yellowing home improvement beauty glue according to claim 1, characterized in that: In the modified polydimethylsiloxane step, the viscosity of the α,ω-dihydroxy polydimethylsiloxane at room temperature is 11000-13000 mPa·s; The mass ratio of the α,ω-dihydroxypolydimethylsiloxane, xylene and modifier is 12.0-13.0:500:3.5-4.

0.

3. The method for preparing an anti-yellowing home improvement beauty glue according to claim 1, characterized in that: In the compounding step, the mass ratio of the modified polydimethylsiloxane to the mixed solution is 95-105:240-260; In the mixed solution, the mass ratio of ethyl acetate, hydroxyethyl methacrylate, and azobisisobutyronitrile is 240-260:6.0-6.5:0.6-0.

8.

4. The method for preparing an anti-yellowing home improvement beauty glue according to claim 1, characterized in that: In the nanoparticle pretreatment step, the particle size of the titanium dioxide is 130-150 nm; The particle size of the cerium oxide is 100-120 nm; The mass ratio of xylene, titanium dioxide, cerium oxide, oleic acid and succinic acid is 240-260:8-12:9-11:1.1-1.5:0.6-0.8; The mixed gas is carbon dioxide and oxygen, and the volume ratio of carbon dioxide to oxygen is 1-1.3:

1.

5. The method for preparing the anti-yellowing home improvement beauty glue according to claim 1, characterized in that: In the secondary treatment step, the mass ratio of the pre-treated nanoparticles, N,N-dimethylformamide, p-aminobenzoic acid, diethylenetriamine, 4-dimethylaminopyridine, and N,N'-dicyclohexylcarbodiimide is 9.5-10.5:300:0.8-1.2:1.3-1.7:0.20-0.25:1.8-2.

2.

6. The method for preparing the anti-yellowing home improvement beauty glue according to claim 1, characterized in that: The mass ratio of the functionalized composite, dioctyl phthalate, calcium carbonate, leveling agent BYK-333, antioxidant 1010, kH560 silane coupling agent and dibutyltin dilaurate is 100:14-16:10.2-10.7:1.0-1.4:0.8-1.2:2.2-2.7:1.4-1.8.

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