Preparation method of weather-resistant MBS (methyl methacrylate-butadiene-styrene) resin

Abstract

The invention relates to a preparation method of weather-resistant MBS resin. The preparation method comprises the following steps: step 1, preparing a nano polyacrylate composite emulsion; 2, adding the emulsion obtained in the step 1, styrene, butadiene, diisocyanate, phosphoric acid-tris (4-allyl-2-hydroxyphenyl) ester, tridecanol polyoxyethylene ether, hydroxylated nanoscale titanium dioxide and purified water into a sealed reactor, and reacting to obtain a polymerized emulsion; step 3, adding the polymerized emulsion obtained in the step 2, butadiene, styrene, methyl methacrylate, p-quinone dioxime, hexamethylenediamine, phosphoric acid-tris (4-allyl-2-hydroxyphenyl) ester, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate and hydroxylated nanoscale titanium dioxide into a sealed reactor for reaction; 4, after the reaction in the step 3 is completed, treatment is conducted, and the weather-resistant MBS resin is obtained. The weather-resistant MBS resin prepared by the preparation method disclosed by the invention is good in weather resistance, so that the outdoor service life of related materials added with the MBS resin is prolonged.

Description

Technical Field

[0001] The invention belongs to the field of MBS production, and specifically relates to a method for preparing weather-resistant MBS resin. Background Art

[0002] MBS resin has excellent impact toughness and high strength, while possessing the transparency and uniformity of styrene resin; it has good heat resistance, weather resistance and chemical resistance, and can withstand the erosion of various chemicals; it has low water absorption and hygroscopicity and high stability. At the same time, MBS resin has good processing performance and can be processed and formed by injection molding, extrusion, blow molding, etc., with high production efficiency, which can meet the needs of various complex application scenarios.

[0003] MBS resin is one of the indispensable varieties in the PVC impact modifier series. Generally speaking, among many impact modifiers, MBS resin has excellent compatibility with PVC, unique processing plasticization and transparency, which makes it more cost-effective. Therefore, its application is increasingly favored by plastic processing manufacturers.

[0004] The MBS resin industry is currently in its initial stages of rapid development, with a continuous stream of technological innovations. The industry is undergoing a transformation from fragmentation to concentration, and from low-end products to high-end products. As competition intensifies, it is expected that some technologically backward companies engaged in low-level competition will be eliminated, leading to an increase in industry concentration. Our company, one of the relatively latecomers to MBS resin research and development in China, has successfully developed several grades, including DL-872, DL-821, DL-56, and DL-58, which have been industrialized and have captured significant domestic market share, creating a positive economic environment. User experience indicates that these grades meet requirements for room-temperature impact resistance and processing plasticization. However, with international companies such as Kaneka Chemical of Japan and DowDuPont of the United States also constantly updating their products, new MBS products are entering the market, and the market response is also quite positive.

[0005] MBS resin is generally prepared by methyl acetate homopolymerization. The specific steps include emulsion polymerization of monomers such as styrene, butadiene, and methyl methacrylate, and controlling the properties and molecular structure of the resin by adjusting the reaction conditions. The weather resistance of MBS resin refers to the ability of various materials to withstand the test of climate when used outdoors, such as comprehensive damage caused by light, heat and cold, wind and rain, and bacteria. Weather resistance determination methods, such as various aging tests, simulate natural climatic conditions for testing. Weather resistance testing is an important means of screening formulas and optimizing product composition in the scientific research and production process, and is also an important part of product quality inspection. Traditional MBS resin contains unsaturated double bonds in its rubber phase, which is prone to aging under heat or sunlight, and its performance is greatly reduced. It is not suitable for outdoor application. In view of the above problems, there is an urgent need to develop weather-resistant MBS products to improve weather resistance. Summary of the Invention

[0006] The present invention provides a method for preparing a weather-resistant MBS resin, which is used to solve the defects in the prior art.

[0007] The present invention is achieved through the following technical solutions:

[0008] A method for preparing a weather-resistant MBS resin comprises the following steps:

[0009] Step 1: Add nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropyl phenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and purified water into a sealed reactor, increase the temperature and pressure to perform an emulsification reaction, and obtain an emulsion after the reaction is completed;

[0010] Step 2: adding the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-sized titanium dioxide, and purified water into a sealed reactor for polymerization reaction, and obtaining a polymer emulsion after the reaction is completed;

[0011] Step 3: adding the polymer emulsion obtained in step 2, butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate, and hydroxylated nano-sized titanium dioxide into a sealed reactor for reaction;

[0012] Step 4: After the reaction in step 3 is completed, the weather-resistant MBS resin is obtained by treatment.

[0013] The method for preparing a weather-resistant MBS resin as described above, wherein the preparation method of the nano-polyacrylate microsphere emulsion in step 1 is as follows: adding purified water to a sealed reactor, heating the mixture to 70-90° C. under nitrogen protection, stirring at a speed of 300-500 r / min, then adding polyacrylate and polyether polyester, stirring evenly, and then adding sodium dodecylbenzene sulfonate dropwise, continuing the reaction for 10-12 hours, stopping heating and stirring, and cooling to room temperature to obtain the nano-polyacrylate microsphere emulsion;

[0014] The mass ratio of the purified water, polyacrylate, polyether polyester and sodium dodecylbenzene sulfonate is: 100-120: 15-25: 1-2: 0.2-0.4.

[0015] In the above-mentioned method for preparing a weather-resistant MBS resin, the reaction in step 1 is carried out under nitrogen protection, the reaction temperature is 65-75°C, the reaction pressure is 1-1.5 MPa, the reaction time is 2-3 hours, and gamma rays are used for irradiation during the reaction process. The intensity of the gamma rays is 10-20 MeV, and the gamma ray irradiation time is 1-2 hours.

[0016] In the above-mentioned method for preparing a weather-resistant MBS resin, the mass ratio of the nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropylphenylphenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and purified water in step 1 is: 130-150: 10-20: 1-2: 0.5-1: 1-2: 6-12: 2-4: 200-300.

[0017] In the above-mentioned method for preparing a weather-resistant MBS resin, the reaction in step 2 is carried out under nitrogen protection, the reaction temperature is 70-80°C, the reaction pressure is 1-1.5 MPa, the reaction time is 3-5 hours, and gamma rays are used for irradiation during the reaction process. The intensity of the gamma rays is 20-40 MeV, and the gamma ray irradiation time is 2-3 hours.

[0018] In the above-mentioned method for preparing a weather-resistant MBS resin, in the step 2, the mass ratio of the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-scale titanium dioxide, and purified water is: 200-300: 20-30: 5-10: 0.6-0.8: 0.2-0.4: 0.6-0.8: 15-20: 100-140.

[0019] In the above-mentioned method for preparing a weather-resistant MBS resin, the reaction in step three is carried out under nitrogen protection, the reaction temperature is 60-70°C, the reaction pressure is 1-1.5 MPa, the reaction time is 4-6 hours, and gamma rays are used for irradiation during the reaction process. The intensity of the gamma rays is 20-30 MeV, and the gamma ray irradiation time is 3-4 hours.

[0020] In the above-mentioned method for preparing a weather-resistant MBS resin, the mass ratio of the polymer emulsion obtained in step 2 in step 3 to butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzenesulfonate and hydroxylated nano-scale titanium dioxide is: 400-500: 30-40: 20-30: 20-40: 0.5-1: 0.4-0.8: 0.2-0.4: 0.1-0.2: 0.1-0.2: 8-12.

[0021] The preparation method of the weather-resistant MBS resin described above comprises the following steps: adding nano-titanium dioxide to a sodium hydroxide solution with a pH of 11-13 and a mass 4-6 times that of the nano-titanium dioxide, and then reacting the solution at a temperature of 100-120° C. and a pressure of 1-1.5 MPa for 12-16 hours. After the reaction is completed, the solution is cooled, filtered, washed, and dried to obtain the hydroxylated nano-titanium dioxide, which has a particle size range of 30-50 nm.

[0022] According to the above-mentioned method for preparing a weather-resistant MBS resin, in the step 4, after the reaction in step 3 is completed, the weather-resistant MBS resin is obtained by demulsification, filtration, water washing, drying, crushing and packaging.

[0023] The advantages of the present invention are as follows: the weather resistance of the MBS resin is increased by adding butyl acrylate and adjusting the proportions of other components; at the same time, the present invention utilizes the excellent ultraviolet shielding performance of hydroxylated nano-grade titanium dioxide to improve the anti-discoloration and gloss retention properties of the MBS resin, effectively suppress the photodegradation reaction speed and degree of the MBS resin, and ultimately extend the outdoor service life of related materials added with the MBS resin; the present invention uses the preparation of acrylic ester latex polymerization to design submicroscopic particles of the MBS resin, so that the MBS resin has a typical core / shell structure, wherein the center of the particle is a rubber phase core with a low elastic modulus, and the outer layer is a grafted shell layer formed of styrene and methyl methacrylate with a high elastic modulus. The outer shell layer has good compatibility with PVC resin and can be uniformly dispersed in the PVC matrix in the PVC / MBS mixture to form an "island structure", fully exerting the function of the particle toughening agent, thereby increasing the weather resistance. DETAILED DESCRIPTION

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0025] Example 1

[0026] Step 1: Add nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropyl phenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and purified water into a sealed reactor, and carry out the reaction under nitrogen protection at a temperature of 75° C., a reaction pressure of 1.4 MPa, and a reaction time of 2 h. During the reaction, gamma rays are irradiated, the intensity of the gamma rays is 20 MeV, and the gamma ray irradiation time is 1 h. After the reaction is completed, an emulsion is obtained;

[0027] The mass ratio of nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropyl phenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and purified water is 150:20:2:1:1-2:12:4:300.

[0028] The preparation method of the nano-polyacrylate microsphere emulsion is as follows: adding purified water to a sealed reactor, heating to 90°C under nitrogen protection, stirring at a speed of 500 r / min, then adding polyacrylate and polyether polyester and stirring evenly, and then adding sodium dodecylbenzene sulfonate dropwise, continuing the reaction for 10 hours, stopping heating and stirring, and cooling to room temperature to obtain the nano-polyacrylate microsphere emulsion;

[0029] The mass ratio of purified water, polyacrylate, polyether polyester and sodium dodecylbenzene sulfonate is: 120:25:2:0.4;

[0030] Step 2: adding the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-scale titanium dioxide, and purified water into a sealed reactor under nitrogen protection, the reaction temperature is 80° C., the reaction pressure is 1.4 MPa, the reaction time is 3 hours, and gamma rays are used for irradiation during the reaction process, the gamma ray intensity is 40 MeV, and the gamma ray irradiation time is 2 hours. After the reaction is completed, a polymer emulsion is obtained;

[0031] The mass ratio of the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-scale titanium dioxide and purified water is 300:30:10:0.8:0.4:0.8:20:140;

[0032] Step 3: adding the polymer emulsion obtained in step 2, butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate, and hydroxylated nano-scale titanium dioxide into a sealed reactor under nitrogen protection, the reaction temperature is 70° C., the reaction pressure is 1.3 MPa, the reaction time is 4 h, and gamma rays are used for irradiation during the reaction process, the gamma ray intensity is 30 MeV, and the gamma ray irradiation time is 4 h;

[0033] The mass ratio of the polymer emulsion obtained in step 2 to butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate and hydroxylated nano-sized titanium dioxide is 500:40:30:40:1:0.8:0.4:0.2:0.2:12;

[0034] The preparation process of the hydroxylated nano-scale titanium dioxide is as follows: adding nano-scale titanium dioxide to a sodium hydroxide solution with a pH of 11 and a mass of 6 times that of the nano-scale titanium dioxide, and then reacting for 12 hours at a temperature of 120°C and a pressure of 1.5 MPa. After the reaction is completed, the hydroxylated nano-scale titanium dioxide is cooled, filtered, washed, and dried to obtain the hydroxylated nano-scale titanium dioxide with a particle size range of 30-50 nm.

[0035] Step 4: After the reaction in step 3 is completed, the emulsion is broken, filtered, washed with water, dried, and then crushed and packaged to obtain the weather-resistant MBS resin.

[0036] Example 2

[0037] Step 1: Add nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropyl phenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and purified water into a sealed reactor, and carry out the reaction under nitrogen protection at a temperature of 65° C., a reaction pressure of 1 MPa, and a reaction time of 3 hours. During the reaction, gamma rays are irradiated, the intensity of the gamma rays is 10 MeV, and the gamma ray irradiation time is 2 hours. After the reaction is completed, an emulsion is obtained;

[0038] The mass ratio of nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropylphenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and purified water is 130:10:1:0.5:1:6:2:200.

[0039] The preparation method of the nano-polyacrylate microsphere emulsion is as follows: adding purified water to a sealed reactor, heating to 70°C under nitrogen protection, stirring at a speed of 300 r / min, then adding polyacrylate and polyether polyester and stirring evenly, and then adding sodium dodecylbenzene sulfonate dropwise, continuing the reaction for 12 hours, stopping heating and stirring, and cooling to room temperature to obtain the nano-polyacrylate microsphere emulsion;

[0040] The mass ratio of purified water, polyacrylate, polyether polyester and sodium dodecylbenzene sulfonate is 100:15:1:0.2;

[0041] Step 2: adding the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-scale titanium dioxide, and purified water into a sealed reactor under nitrogen protection, the reaction temperature is 70° C., the reaction pressure is 1 MPa, the reaction time is 5 hours, and gamma rays are used for irradiation during the reaction process, the gamma ray intensity is 20 MeV, and the gamma ray irradiation time is 3 hours. After the reaction is completed, a polymer emulsion is obtained;

[0042] The mass ratio of the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-scale titanium dioxide and purified water is 200:20:5:0.6:0.2:0.6:15:100;

[0043] Step 3: adding the polymer emulsion obtained in step 2, butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate, and hydroxylated nano-scale titanium dioxide into a sealed reactor under nitrogen protection, the reaction temperature is 60° C., the reaction pressure is 1 MPa, the reaction time is 6 h, and gamma rays are used for irradiation during the reaction process, the gamma ray intensity is 20 MeV, and the gamma ray irradiation time is 4 h;

[0044] The mass ratio of the polymer emulsion obtained in step 2 to butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate and hydroxylated nano-sized titanium dioxide is: 400:30:20:20:0.5:0.4:0.2:0.1:0.1:8;

[0045] The preparation process of the hydroxylated nano-scale titanium dioxide is as follows: adding nano-scale titanium dioxide to a sodium hydroxide solution with a pH of 13 and a mass four times that of the nano-scale titanium dioxide, and then reacting the solution at a temperature of 100°C and a pressure of 1 MPa for 16 hours. After the reaction, the solution is cooled, filtered, washed, and dried to obtain the hydroxylated nano-scale titanium dioxide with a particle size range of 30-50 nm.

[0046] Step 4: After the reaction in step 3 is completed, the emulsion is broken, filtered, washed with water, dried, and then crushed and packaged to obtain the weather-resistant MBS resin.

[0047] Example 3

[0048] Step 1: Add nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropyl phenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and purified water into a sealed reactor, and carry out the reaction under nitrogen protection at a temperature of 70° C., a reaction pressure of 1.2 MPa, and a reaction time of 2.4 h. During the reaction, gamma rays are irradiated, the intensity of the gamma rays is 15 MeV, and the gamma ray irradiation time is 1.6 h. After the reaction is completed, an emulsion is obtained;

[0049] The mass ratio of nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropylphenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and purified water is 140:15:1.5:0.8:1.5:9:3:255;

[0050] The preparation method of the nano-polyacrylate microsphere emulsion is as follows: adding purified water to a sealed reactor, heating to 80°C under nitrogen protection, stirring at a speed of 400 r / min, then adding polyacrylate and polyether polyester and stirring evenly, and then adding sodium dodecylbenzene sulfonate dropwise, continuing the reaction for 11 hours, stopping heating and stirring, and cooling to room temperature to obtain the nano-polyacrylate microsphere emulsion;

[0051] The mass ratio of purified water, polyacrylate, polyether polyester and sodium dodecylbenzene sulfonate is: 110:20:1.5:0.3;

[0052] Step 2: adding the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-scale titanium dioxide, and purified water into a sealed reactor under nitrogen protection, the reaction temperature is 75° C., the reaction pressure is 1.2 MPa, the reaction time is 4 hours, and gamma rays are used for irradiation during the reaction process. The intensity of the gamma rays is 30 MeV, and the gamma ray irradiation time is 2.6 hours. After the reaction is completed, a polymer emulsion is obtained;

[0053] The mass ratio of the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-scale titanium dioxide and purified water is: 260:24:7:0.7:0.3:0.7:18:124;

[0054] Step 3: adding the polymer emulsion obtained in step 2, butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate, and hydroxylated nano-scale titanium dioxide into a sealed reactor under nitrogen protection, the reaction temperature is 65° C., the reaction pressure is 1.2 MPa, the reaction time is 5 h, and gamma rays are used for irradiation during the reaction process, the gamma ray intensity is 25 MeV, and the gamma ray irradiation time is 3.4 h;

[0055] The mass ratio of the polymer emulsion obtained in step 2 to butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate and hydroxylated nano-sized titanium dioxide is: 450:30-40:25:30:0.7:0.6:0.3:0.15:0.15:10;

[0056] The preparation process of the hydroxylated nano-scale titanium dioxide is as follows: adding nano-scale titanium dioxide to a sodium hydroxide solution with a pH of 12 of 5 times the mass of the nano-scale titanium dioxide, and then reacting for 14 hours at a temperature of 10°C and a pressure of 1.2 MPa. After the reaction is completed, cooling, filtering, washing, and drying are performed to obtain hydroxylated nano-scale titanium dioxide with a particle size range of 30-50 nm.

[0057] Step 4: After the reaction in step 3 is completed, the emulsion is broken, filtered, washed with water, dried, and then crushed and packaged to obtain the weather-resistant MBS resin.

[0058] Comparative Example 1

[0059] Step 1: Add nano-polyacrylate microsphere emulsion, lauryl alcohol polyoxyethylene ether, dibenzyl isopropylphenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and purified water into a sealed reactor, and carry out the reaction under nitrogen protection at a temperature of 70° C., a reaction pressure of 1.2 MPa, and a reaction time of 2.4 h. During the reaction, gamma rays are irradiated, the intensity of the gamma rays is 15 MeV, and the gamma ray irradiation time is 1.6 h. After the reaction is completed, an emulsion is obtained;

[0060] The mass ratio of nano-polyacrylate microsphere emulsion, lauryl alcohol polyoxyethylene ether, dibenzyl isopropylphenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and purified water is: 140:1.5:0.8:1.5:9:3:255;

[0061] The preparation method of the nano-polyacrylate microsphere emulsion is as follows: adding purified water to a sealed reactor, heating to 80°C under nitrogen protection, stirring at a speed of 400 r / min, then adding polyacrylate and polyether polyester and stirring evenly, and then adding sodium dodecylbenzene sulfonate dropwise, continuing the reaction for 11 hours, stopping heating and stirring, and cooling to room temperature to obtain the nano-polyacrylate microsphere emulsion;

[0062] The mass ratio of purified water, polyacrylate, polyether polyester and sodium dodecylbenzene sulfonate is: 110:20:1.5:0.3;

[0063] Step 2: adding the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-scale titanium dioxide, and purified water into a sealed reactor under nitrogen protection, the reaction temperature is 75° C., the reaction pressure is 1.2 MPa, the reaction time is 4 hours, and gamma rays are used for irradiation during the reaction process. The intensity of the gamma rays is 30 MeV, and the gamma ray irradiation time is 2.6 hours. After the reaction is completed, a polymer emulsion is obtained;

[0064] The mass ratio of the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-scale titanium dioxide and purified water is: 260:24:7:0.7:0.3:0.7:18:124;

[0065] Step 3: adding the polymer emulsion obtained in step 2, butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate, and hydroxylated nano-scale titanium dioxide into a sealed reactor under nitrogen protection, the reaction temperature is 65° C., the reaction pressure is 1.2 MPa, the reaction time is 5 h, and gamma rays are used for irradiation during the reaction process, the gamma ray intensity is 25 MeV, and the gamma ray irradiation time is 3.4 h;

[0066] The mass ratio of the polymer emulsion obtained in step 2 to butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate and hydroxylated nano-sized titanium dioxide is: 450:30-40:25:30:0.7:0.6:0.3:0.15:0.15:10;

[0067] The preparation process of the hydroxylated nano-scale titanium dioxide is as follows: adding nano-scale titanium dioxide to a sodium hydroxide solution with a pH of 12 of 5 times the mass of the nano-scale titanium dioxide, and then reacting for 14 hours at a temperature of 10°C and a pressure of 1.2 MPa. After the reaction is completed, cooling, filtering, washing, and drying are performed to obtain hydroxylated nano-scale titanium dioxide with a particle size range of 30-50 nm.

[0068] Step 4: After the reaction in step 3 is completed, the emulsion is broken, filtered, washed with water, dried, and then crushed and packaged to obtain MBS resin.

[0069] Comparative Example 2

[0070] Step 1: Add nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropyl phenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and purified water into a sealed reactor, and carry out the reaction under nitrogen protection at a temperature of 70° C., a reaction pressure of 1.2 MPa, and a reaction time of 2.4 h. During the reaction, gamma rays are irradiated, the intensity of the gamma rays is 15 MeV, and the gamma ray irradiation time is 1.6 h. After the reaction is completed, an emulsion is obtained;

[0071] The mass ratio of nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropylphenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and purified water is 140:15:1.5:0.8:1.5:9:3:255;

[0072] The preparation method of the nano-polyacrylate microsphere emulsion is as follows: adding purified water to a sealed reactor, heating to 80°C under nitrogen protection, stirring at a speed of 400 r / min, then adding polyacrylate and polyether polyester and stirring evenly, and then adding sodium dodecylbenzene sulfonate dropwise, continuing the reaction for 11 hours, stopping heating and stirring, and cooling to room temperature to obtain the nano-polyacrylate microsphere emulsion;

[0073] The mass ratio of purified water, polyacrylate, polyether polyester and sodium dodecylbenzene sulfonate is: 110:20:1.5:0.3;

[0074] Step 2: adding the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, and purified water into a sealed reactor under nitrogen protection, the reaction temperature is 75° C., the reaction pressure is 1.2 MPa, the reaction time is 4 hours, and gamma rays are used for irradiation during the reaction process. The intensity of the gamma rays is 30 MeV, and the gamma ray irradiation time is 2.6 hours. After the reaction is completed, a polymer emulsion is obtained;

[0075] The mass ratio of the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether and purified water is: 260:24:7:0.7:0.3:0.7:124;

[0076] Step 3: adding the polymer emulsion obtained in step 2, butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, and sodium methoxy fatty amide benzenesulfonate to a sealed reactor under nitrogen protection, the reaction temperature is 65° C., the reaction pressure is 1.2 MPa, the reaction time is 5 h, and gamma rays are used for irradiation during the reaction process, the gamma ray intensity is 25 MeV, and the gamma ray irradiation time is 3.4 h;

[0077] The mass ratio of the polymer emulsion obtained in step 2 to butadiene, styrene, methyl methacrylate, p-quinonedioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, and sodium methoxy fatty amide benzenesulfonate is: 450:30-40:25:30:0.7:0.6:0.3:0.15:0.15;

[0078] Step 4: After the reaction in step 3 is completed, the emulsion is broken, filtered, washed with water, dried, and then crushed and packaged to obtain MBS resin.

[0079] MBS / PVC composite materials were obtained by mixing the composite materials of Examples 1-3 and Comparative Examples 1-2 with the same PVC material at a 10% addition ratio, melt extruding, and granulating. The composite materials were then tested for impact resistance (tested according to the method of GB / T 1043.1-2008) and aging resistance (tested according to the method of GB / T 16422, by observing changes in appearance, mass, and mechanical properties before and after being placed in an aging test chamber to determine their aging resistance). The test results are shown in Table 1.

[0080]

[0081] Table 1

[0082] As can be seen from the data in Table 1, the MBS resins prepared in Examples 1-3 of the present invention, when used in combination with PVC materials, have similar impact resistance to those of Comparative Documents 1 and 2, but have significantly different anti-aging properties. The MBS resins prepared in the present invention have superior impact resistance to existing conventional products, and significantly improved anti-aging properties. Therefore, the MBS resins prepared in the present invention can effectively improve their anti-aging properties and thus their weather resistance, thereby ensuring their long-term and stable outdoor use.

[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A method for preparing a weather-resistant MBS resin, characterized in that: The steps include: Step 1: Add nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropyl phenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and purified water into a sealed reactor, increase the temperature and pressure to perform an emulsification reaction, and obtain an emulsion after the reaction is completed; Step 2: adding the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-sized titanium dioxide, and purified water into a sealed reactor for polymerization reaction, and obtaining a polymer emulsion after the reaction is completed; Step 3: adding the polymer emulsion obtained in step 2, butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzene sulfonate, and hydroxylated nano-sized titanium dioxide into a sealed reactor for reaction; Step 4: After the reaction in step 3 is completed, the weather-resistant MBS resin is obtained by treatment.

2. The method for preparing a weather-resistant MBS resin according to claim 1, wherein: The preparation method of the nano-polyacrylate microsphere emulsion in step 1 is as follows: adding purified water to a sealed reactor, heating to 70-90° C. under nitrogen protection, stirring at a speed of 300-500 r / min, then adding polyacrylate and polyether polyester and stirring evenly, and then adding sodium dodecylbenzene sulfonate dropwise, continuing the reaction for 10-12 hours, stopping heating and stirring, and cooling to room temperature to obtain the nano-polyacrylate microsphere emulsion; The mass ratio of the purified water, polyacrylate, polyether polyester and sodium dodecylbenzene sulfonate is: 100-120: 15-25: 1-2: 0.2-0.

4.

3. The method for preparing a weather-resistant MBS resin according to claim 1, wherein: The reaction in step 1 is carried out under nitrogen protection, the reaction temperature is 65-75°C, the reaction pressure is 1-1.5 MPa, the reaction time is 2-3 hours, and gamma rays are used for irradiation during the reaction process. The intensity of the gamma rays is 10-20 MeV, and the gamma ray irradiation time is 1-2 hours.

4. The method for preparing a weather-resistant MBS resin according to claim 1, wherein: The mass ratio of the nano-polyacrylate microsphere emulsion, butyl acrylate, lauryl alcohol polyoxyethylene ether, dibenzyl isopropylphenylphenol polyoxyethylene ether, sodium diisopropylnaphthalene sulfonate, allyl methacrylate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and purified water in the step 1 is: 130-150: 10-20: 1-2: 0.5-1: 1-2: 6-12: 2-4: 200-300.

5. The method for preparing a weather-resistant MBS resin according to claim 1, wherein: The reaction in step 2 is carried out under nitrogen protection, the reaction temperature is 70-80°C, the reaction pressure is 1-1.5 MPa, the reaction time is 3-5 hours, and gamma rays are used for irradiation during the reaction process. The intensity of the gamma rays is 20-40 MeV, and the gamma ray irradiation time is 2-3 hours.

6. The method for preparing a weather-resistant MBS resin according to claim 1, characterized in that: In the step 2, the mass ratio of the emulsion obtained in step 1, styrene, butadiene, diisocyanate, tris(4-allyl-2-hydroxyphenyl) phosphate, tridecanol polyoxyethylene ether, hydroxylated nano-scale titanium dioxide and purified water is: 200-300: 20-30: 5-10: 0.6-0.8: 0.2-0.4: 0.6-0.8: 15-20: 100-140.

7. The method for preparing a weather-resistant MBS resin according to claim 1, characterized in that: The reaction in step 3 is carried out under nitrogen protection, the reaction temperature is 60-70°C, the reaction pressure is 1-1.5 MPa, the reaction time is 4-6 hours, and gamma rays are used for irradiation during the reaction process. The intensity of the gamma rays is 20-30 MeV, and the gamma ray irradiation time is 3-4 hours.

8. The method for preparing a weather-resistant MBS resin according to claim 1, characterized in that: The mass ratio of the polymer emulsion obtained in step 2 in the step 3 to butadiene, styrene, methyl methacrylate, quinone dioxime, hexamethylenediamine, tris(4-allyl-2-hydroxyphenyl) phosphate, sodium cocoyl methyl taurate, sodium methoxy fatty amide benzenesulfonate and hydroxylated nano-scale titanium dioxide is: 400-500: 30-40: 20-30: 20-40: 0.5-1: 0.4-0.8: 0.2-0.4: 0.1-0.2: 0.1-0.2: 8-12.

9. The method for preparing a weather-resistant MBS resin according to claim 1, characterized in that: The preparation process of the hydroxylated nano-scale titanium dioxide is as follows: adding nano-scale titanium dioxide to a sodium hydroxide solution with a pH of 11-13 and a mass 4-6 times that of the nano-scale titanium dioxide, and then reacting at a temperature of 100-120°C and a pressure of 1-1.5 MPa for 12-16 hours. After the reaction is completed, cooling, filtering, washing, and drying are performed to obtain hydroxylated nano-scale titanium dioxide with a particle size range of 30-50 nm.

10. The method for preparing a weather-resistant MBS resin according to claim 1, characterized in that: After the reaction in step 3 in step 4 is completed, the emulsion is broken, filtered, washed with water, dried, and then crushed and packaged to obtain the weather-resistant MBS resin.

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