MBS (methyl methacrylate-butadiene-styrene) as well as preparation method and application thereof

Abstract

The invention provides MBS (methyl methacrylate-butadiene-styrene) as well as a preparation method and application thereof. The novel MBS modifier composition is prepared from the following raw materials: a butadiene component containing a diene group, alkyl (meth) acrylate, a vinyl aromatic monomer and a monomer containing an alkenyl group. The preparation method comprises the following steps: preparing a diene-containing rubber core polymer, adding an olefine aldehyde-containing component to prepare a grafted copolymer to form a core-shell structure, and carrying out demulsification and flocculation on an emulsion. The MBS solves the problem that optical performance and mechanical performance of an existing impact modifier cannot be balanced, and the method can improve the optical performance of the MBS on the premise that the mechanical performance is not obviously influenced.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to MBS, its preparation method, and its applications. Background Technology

[0002] Butadiene-methyl methacrylate-styrene (MBS) copolymer, as an excellent impact modifier, is frequently added to engineering plastics such as PC (PC / ABS), PVC, PLA, epoxy resins, PBT / PET, and PVC. Specific applications include home appliances, automobiles, medical devices, 3D printing, epoxy adhesives, and PVC sheets and pipes.

[0003] During use, the main focus is on its mechanical and optical properties. In the PC field, flame retardancy is also a concern. Because MBS contains unsaturated double bonds resulting from incomplete butadiene polymerization, it is easily oxidized, leading to a decline in performance (such as yellowing or a decrease in flame retardancy). Butadiene is also a key factor affecting mechanical properties, making it impossible to balance its mechanical and optical properties.

[0004] Currently, the optical properties of MBS are improved by adding antioxidants. Patent EP0044159 uses hindered phenols and auxiliary antioxidants to improve thermal oxidation stability. Patent US4379876A specifically mentions the use of hindered phenols and thioesters to increase thermal stability. Patents US4957954A, CN1079800C, and CN85104049A all repeatedly mention the use of antioxidants to improve thermal oxidation stability. However, excessive antioxidants can lead to a decrease in mechanical properties.

[0005] In summary, the problem of the inability to balance optical and mechanical properties in existing impact modifiers in this field urgently needs to be solved. Summary of the Invention

[0006] One of the objectives of this invention is to overcome the problem of the inability to balance optical and mechanical properties in existing impact modifiers, and to provide a novel MBS that can improve optical properties without significantly affecting mechanical properties.

[0007] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0008] A butadiene-methyl methacrylate-styrene MBS modifier composition, said modifier composition being prepared from raw materials comprising the following components:

[0009] Component A contains 30-90 wt% of at least one butadiene component containing a diene group, preferably 38.41-74.41 wt%.

[0010] Component B contains 1-50 wt% of at least one alkyl (meth)acrylate, preferably 4.85-44.21 wt%.

[0011] Component C contains 1-60 wt% of at least one vinyl aromatic monomer, preferably 4.93-53.3 wt%.

[0012] Component D contains at least one monomer containing an enaldehyde group at a concentration of 20-2000 ppm, preferably 97-981 ppm;

[0013] Based on the total mass of the modifier composition.

[0014] In this invention, a monomer containing an alkenal group is used, which can be grafted onto the MBS molecular chain through free radical polymerization. The alkenal group can form hydrogen bonds with functional plastics such as PVC and PC, which can improve the compatibility of MBS in engineering plastics and improve its impact resistance. The monomer containing an alkenal group used in this invention can preferentially react with oxygen or peroxide when the unsaturated double bonds on the molecular backbone are attacked by peroxide or oxygen, thus protecting the molecular backbone.

[0015] In one embodiment of the present invention, the butadiene component containing a diene group comprises a diene having 4-7 carbon atoms and / or one or more dienes having 4-7 carbon atoms whose hydrogen atoms are replaced by halogen elements, preferably one or more of 1,3-butadiene, isoprene, and chloroprene, more preferably 1,3-butadiene.

[0016] In one embodiment of the present invention, the (meth)acrylate alkyl ester comprises acrylates and methyl methacrylates of alkyl esters having 1 to 12 carbon atoms, and / or esters (meth)acrylates of alkyl groups having 1 to 22 carbon atoms and having hydroxyl groups; preferably, the acrylates and methyl methacrylates of alkyl esters having 1 to 12 carbon atoms comprise methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, and isooctyl methacrylate, preferably methyl methacrylate and / or n-butyl methacrylate; preferably, the esters (meth)acrylates (meth)acrylates of alkyl groups having 1 to 22 carbon atoms and having hydroxyl groups comprise 2-hydroxyethyl methacrylate and / or 4-hydroxybutyl methacrylate.

[0017] In one embodiment of the invention, the vinyl aromatic monomer comprises styrene and / or styrene in which at least one hydrogen atom is substituted by a C1-C8 alkyl group or a halogen, preferably one or more of styrene, 2-(n-butyl)styrene, 4-(n-butyl)styrene, 4-(n-decyl)styrene, divinylbenzene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, and dibromostyrene, more preferably styrene.

[0018] The above-mentioned butadiene containing diene groups, alkyl (meth)acrylates, vinyl aromatic monomers, and their dosages are common MBS schemes in this field.

[0019] In one embodiment of the present invention, the monomer containing an enaldehyde group comprises one or more enaldehyde monomers having 3-10 carbon atoms, preferably one or more of acrolein, methacrolein, 3-methyl-2-butenal, 2-butylacrolein, 3-ethoxyisobutenal, trans-cinnamaldehyde, tin aldehyde, and trans-2-pentenal, more preferably acrolein and / or methacrolein.

[0020] In one embodiment of the present invention, the modifier composition comprises the following auxiliary components:

[0021] Component E contains 0.01-2 wt% of an initiator, preferably 0.25-1.04 wt%.

[0022] Component F contains 0.2-5 wt% emulsifier, preferably 0.5-3 wt%.

[0023] Component G is a pH buffer at 0.01-1 wt%, preferably 0.02-0.14 wt%.

[0024] Based on the total mass of the modifier composition.

[0025] The above-mentioned additives and their dosages are commonly used in this field.

[0026] In one embodiment of the present invention, the initiator comprises one or more of a redox system formed by a thermally decomposable polymerization initiator, a peroxide, a reducing agent, a transition metal salt, and a chelating agent, preferably a redox system formed by a chelating agent; preferably, the thermally decomposable polymerization initiator comprises one or more of azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate; preferably, the peroxide comprises one or more of tert-butyl hydroperoxide, cumene hydroperoxide, terpene hydroperoxide, hydrogen peroxide, potassium persulfate, and ammonium persulfate; preferably, the reducing agent comprises one or more of sodium formaldehyde sulfoxylate, glucose, sodium metabisulfite, and sodium hydrosulfite; preferably, the transition metal salt comprises ferric(II) sulfate; preferably, the redox system formed by the chelating agent comprises disodium ethylenediaminetetraacetate and / or tetrasodium ethylenediaminetetraacetate.

[0027] In one embodiment of the present invention, the emulsifier comprises one or more of anionic surfactants, nonionic surfactants, anionic-nonionic surfactants, and cationic surfactants; preferably, the anionic surfactant comprises one or more of fatty acid salts, alkyl sulfates, alkylbenzene sulfonates, alkyl phosphates, and dialkyl sulfosuccinates; preferably, the nonionic surfactant comprises polyoxyethylene alkyl ethers and / or polyoxyethylene fatty acid esters; preferably, the anionic-nonionic surfactant comprises fatty alcohol ether phosphates and their salts, and / or sulfates; preferably, the cationic surfactant comprises one or more of sorbitol fatty acid esters, glycerol fatty acid esters, and alkylamine salts; preferably, the emulsifier comprises fatty acid salts and / or fatty alcohol ether phosphates and their salts.

[0028] In one embodiment of the present invention, the pH buffer comprises a water-soluble phosphate and / or carbonate, preferably one or more of sodium carbonate, sodium bicarbonate, potassium phosphate, potassium carbonate, potassium bicarbonate, and sodium dihydrogen phosphate, more preferably potassium phosphate.

[0029] Another object of the present invention is to provide a method for preparing a butadiene-methyl methacrylate-styrene MBS modifier composition.

[0030] A method for preparing a butadiene-methyl methacrylate-styrene MBS modifier composition, wherein the composition is the above-mentioned modifier composition, the method comprising the following steps:

[0031] A diene-based rubber core polymer was prepared, and an alkenyl aldehyde-containing component was added to prepare a graft copolymer to form a core-shell structure, which was then used to demulsify and flocculate the emulsion.

[0032] In one embodiment of the present invention, the reaction temperature for preparing the diene-based rubber core polymer is 50-70°C.

[0033] In one embodiment of the present invention, the reaction temperature for preparing the graft copolymer by adding the alkenyl component is 60-80°C.

[0034] In this invention, when preparing the grafted emulsion with the core-shell structure, it is necessary to remove VOCs from the rubber core emulsion and remove butadiene from the system. This operation is well known in the art.

[0035] Another object of the present invention is to provide an application of a butadiene-methyl methacrylate-styrene MBS modifier composition.

[0036] Application of a butadiene-methyl methacrylate-styrene MBS modifier composition, wherein the composition is the modifier composition described above, or a modifier composition prepared by the method described above, and the modifier composition is used as an impact modifier in polycarbonate plastics or polyvinyl chloride plastics.

[0037] Another object of the present invention is to provide an impact-resistant modified plastic.

[0038] An impact-modified plastic, wherein the plastic is composed of the above-described modifier composition or a modifier composition prepared by the above-described method, and the impact-modified plastic is an impact-modified polycarbonate plastic or an impact-modified polyvinyl chloride plastic containing the above-described impact modifier.

[0039] The novel impact modifier of this invention possesses excellent mechanical and optical properties. It can be mixed with polyvinyl chloride, polycarbonate, etc., to improve impact resistance without affecting transparency. It can be used in the automotive, home appliance, building materials, and pharmaceutical packaging industries.

[0040] Compared with the prior art, the beneficial effects of the present invention are mainly reflected in the following aspects:

[0041] 1. This invention uses monomers containing enaldehyde groups, which can improve their impact resistance. Monomers containing enaldehyde groups play a role in protecting the molecular backbone, resulting in superior anti-yellowing and impact resistance (10% improvement).

[0042] 2. Monomers containing alkenyl groups can be copolymerized well with butadiene, methyl methacrylate, and styrene;

[0043] 3. The production process of this invention is simple, easy to operate, and safe and non-toxic. Detailed Implementation

[0044] The following embodiments further illustrate the technical solutions provided by the present invention, but the present invention is not limited to the listed embodiments, and also includes any other known modifications within the scope of the present invention.

[0045] Butadiene: Wanhua Chemical Company, industrial grade, 99% purity;

[0046] Sodium oleate: Aladdin Chemical Reagent Company, reagent grade, 99% purity;

[0047] Acrolein: Aladdin Chemical Reagent Company, reagent grade, 99% purity;

[0048] Sulfuric acid: Aladdin Chemical Reagent Company, reagent grade, 99% purity;

[0049] MMA: Methyl methacrylate, Wanhua Chemical Company, industrial grade, 99% purity;

[0050] Tripotassium phosphate: Aladdin Chemical Reagent Company, reagent grade, 99% purity;

[0051] Acrolein: Sigma Chemicals, reagent grade, 99% purity;

[0052] Methacrolein: Sigma Chemicals, reagent grade, 99% purity;

[0053] Ferrous sulfate heptahydrate: Aladdin Chemical Reagent Company, reagent grade, 99% purity;

[0054] Disodium ethylenediaminetetraacetate: Aladdin Chemical Reagent Company, reagent grade, 99% purity;

[0055] Sodium polyoxyethylene alkyl ether phosphate RS-610-Na: Solvay Chemicals, industrial grade, 98% purity;

[0056] SFS: Sodium formaldehyde sulfoxylate, Aladdin Chemical Reagent Company, reagent grade, 99% purity;

[0057] CHP: Hydrogen peroxide isopropane, Aladdin Chemical Reagent Company, reagent grade, 99% purity;

[0058] Styrene, Wanhua Chemical Company, industrial grade, 99% purity;

[0059] BHP: tert-butyl hydrogen peroxide, Guangzhou Yuanchuang Chemical Co., Ltd., industrial grade, 99% purity;

[0060] IRGANOX 1076: BASF Chemicals, industrial grade, 99% purity;

[0061] Calcium chloride: Aladdin Chemical Reagent Co., Ltd., reagent grade, 99% purity.

[0062] Test equipment:

[0063] Haze meter: Hangzhou Caipu TH-110;

[0064] Desktop spectrophotometer: Hangzhou Caipu CS-820N;

[0065] Dart test machine: Industrial Physics Ray RanRR / FDT-A2.

[0066] Example 1

[0067] Preparation of butadiene-based rubber core polymer-1:

[0068] Add 710g of pure water, 0.8g of tripotassium phosphate, 0.008g of ferrous sulfate heptahydrate, 0.02g of disodium ethylenediaminetetraacetate (EDTA), and 4.2g of sodium oleate to a pressure-resistant polymerizer containing a mixer. While stirring, evacuate and replace the gas inside the pressure-resistant polymerizer with nitrogen to completely remove oxygen from the inside.

[0069] 380g of butadiene (Bd), 20g of styrene, 0.2g of sodium formaldehyde sulfoxylate (SFS), and 1g of isopropane hydroperoxide (CHP) were added to a pressure-resistant polymerizer. The reaction was carried out at 50°C, with 1.8g of sodium lactate added dropwise over 5 hours. After 11 hours of reaction, the system pressure was reduced to 0.2 MPaG, and the polymerization conversion rate was 98 wt%. After polymerization, unreacted butadiene monomer was removed using a vacuum diaphragm pump, yielding a polybutadiene rubber latex with a solid content of 36.5%.

[0070] Preparation of graft copolymer-1:

[0071] 140 g of the above-mentioned polybutadiene rubber latex was added to a reactor equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the temperature was raised to 60°C. 0.055 g of sodium formaldehyde sulfoxylate, 0.165 g of tert-butyl hydroperoxide, 0.0018 g of ferrous sulfate heptahydrate, and 0.0055 g of disodium ethylenediaminetetraacetate (EDTA) were added. (a) A pre-emulsion of 0.01 g of acrolein, 45 g of methyl methacrylate (MMA), 0.45 g of sodium oleate, and 13 g of water was added dropwise to the above reactor over 1 hour. (b) A pre-emulsion of 5 g of styrene, 0.05 g of sodium oleate, and 1.5 g of water was added dropwise to the above reactor over 0.5 hours. After the addition was complete, the mixture was kept at this temperature for 1.5 hours, cooled to 50°C, and discharged to obtain graft copolymer-1.

[0072] Flocculation:

[0073] After adding 2g of IRGANOX 1076 [octadecyl 3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate] as a phenolic antioxidant, the emulsion was added to 795g of a 0.15wt% dilute sulfuric acid aqueous solution within 1min. Subsequently, 5wt% sulfuric acid aqueous solution was added to adjust the pH value to below 1.5, and 10wt% sodium hydroxide aqueous solution was added to adjust the pH value to 7.0. The wet filter cake was obtained by filtration, washed with pure water until the conductivity was less than 50μS / cm, and dried in a fluidized bed until the moisture content was less than 1% to obtain the powder-packaged graft copolymer-1.

[0074] The physical properties of the prepared product are shown in Table 1.

[0075] Example 2

[0076] Preparation of butadiene-based rubber core polymer-2:

[0077] Add 710g of pure water, 0.11g of tripotassium phosphate, 0.03g of ferrous sulfate heptahydrate, 0.09g of disodium ethylenediaminetetraacetate (EDTA), and 0.028g of RS610-Na to a pressure-resistant polymerizer containing a mixer. While stirring, evacuate and replace the gas inside the pressure-resistant polymerizer with nitrogen to thoroughly remove oxygen from the polymerizer.

[0078] 400g of butadiene (Bd), 0.1g of sodium formaldehyde sulfoxylate (SFS), and 0.5g of isopropane hydroperoxide (CHP) were added to a pressure-resistant polymerizer. The reaction was carried out at 60°C, with 1.372g of oil RS610-Na added dropwise over 5 hours. After 11 hours of reaction, the system pressure was reduced to 0.2 MPaG, and the polymerization conversion rate was 98 wt%. After polymerization, unreacted butadiene monomer was removed using a vacuum diaphragm pump, yielding a polybutadiene rubber latex with a solid content of 36.2%.

[0079] Preparation of graft copolymer-2:

[0080] 210 g of the above-mentioned polybutadiene rubber latex was added to a reactor equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, the temperature was raised to 70°C, and 0.0054 g of sodium formaldehyde sulfoxylate, 0.0825 g of tert-butyl hydroperoxide, 0.0018 g of ferrous sulfate heptahydrate, and 0.09 g of disodium ethylenediaminetetraacetate (EDTA) were added. (a) A pre-emulsion of 0.05 g of acrolein, 20 g of methyl methacrylate (MMA), 0.2 g of sodium oleate, and 6 g of water was added dropwise to the above reactor over 1 hour. (b) A pre-emulsion of 5 g of styrene, 0.05 parts of sodium oleate, and 1.5 g of water was added dropwise to the above reactor over 0.5 hours. After the addition was complete, the temperature was maintained for 1.5 hours, then lowered to 50°C, and the material was discharged to obtain graft copolymer-2.

[0081] Flocculation:

[0082] After adding 2g of IRGANOX 1076 [octadecyl 3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate] as a phenolic antioxidant, the emulsion was added to 795g of a 0.05wt% dilute sulfuric acid aqueous solution within 1min. Subsequently, a 5% sulfuric acid aqueous solution was added to adjust the pH value to below 1.5, and a 10wt% sodium hydroxide aqueous solution was added to adjust the pH value to 7.0. The mixture was filtered to obtain a wet filter cake, which was washed with pure water until the conductivity was less than 50μS / cm. The wet filter cake was then dried in a fluidized bed until the moisture content was less than 1wt% to obtain the powder-packaged graft copolymer-2.

[0083] The physical properties of the prepared product are shown in Table 1.

[0084] Example 3

[0085] Preparation of butadiene-based rubber core polymer-3:

[0086] Add 710g of pure water, 1.2g of tripotassium phosphate, 0.067g of ferrous sulfate heptahydrate, 0.2g of disodium ethylenediaminetetraacetate (EDTA), and 10g of potassium oleate to a pressure-resistant polymerizer containing a mixer. While stirring, evacuate and replace the gas inside the pressure-resistant polymerizer with nitrogen to completely remove oxygen from the inside.

[0087] 320g of butadiene (Bd), 80g of styrene, 0.8g of sodium formaldehyde sulfoxylate (SFS), and 4g of isopropane hydroperoxide (CHP) were added to a pressure-resistant polymerizer. The reaction was carried out at 60°C, with 11.1g of potassium oil added dropwise over 6 hours. After 21 hours of reaction, the system pressure was reduced to 0.2 MPaG, and the polymerization conversion rate was 98 wt%. After polymerization, unreacted butadiene monomer was removed using a vacuum diaphragm pump, yielding a polybutadiene rubber latex with a solid content of 37.5%.

[0088] Preparation of graft copolymer-3:

[0089] 140 g of the above-mentioned polybutadiene rubber latex was added to a reactor equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, the temperature was raised to 80°C, and 0.11 g of sodium formaldehyde sulfoxylate, 0.33 g of tert-butyl hydroperoxide, 0.0018 g of ferrous sulfate heptahydrate, and 0.0055 g of disodium ethylenediaminetetraacetate (EDTA) were added. (a) A pre-emulsion of 0.01 g of acrolein, 5 g of butyl methacrylate (MMA), 0.08 g of sodium oleate, and 1.5 g of water was added dropwise to the above reactor over 0.5 h. (b) A pre-emulsion of 45 g of styrene, 0.45 g of sodium oleate, and 13.5 g of water was added dropwise to the above reactor over 0.5 h. After the addition was complete, the mixture was kept at the above temperature for 1.5 h, cooled to 50°C, and discharged to obtain graft copolymer-3.

[0090] Flocculation:

[0091] After adding 3g of IRGANOX 1076 [octadecyl 3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate] as a phenolic antioxidant, the emulsion was added to 795g of a 0.15wt% dilute sulfuric acid aqueous solution within 1min. Subsequently, 5wt% sulfuric acid aqueous solution was added to adjust the pH value to below 1.5, and 10wt% sodium hydroxide aqueous solution was added to adjust the pH value to 7.0. The mixture was filtered to obtain a wet filter cake, which was washed with pure water until the conductivity was less than 50μS / cm. The wet filter cake was dried in a fluidized bed until the moisture content was less than 1wt% to obtain the powder-packaged graft copolymer-3.

[0092] The physical properties of the prepared product are shown in Table 1.

[0093] Example 4

[0094] Preparation of butadiene-based rubber core polymer-4:

[0095] Add 710g of pure water, 0.8g of sodium bicarbonate, 0.033g of ferrous sulfate heptahydrate, 0.1g of disodium ethylenediaminetetraacetate (EDTA), and 5.88g of sodium oleate to a pressure-resistant polymerizer containing a mixer. While stirring, evacuate and replace the gas inside the pressure-resistant polymerizer with nitrogen to completely remove oxygen from the inside.

[0096] 380g of butadiene (Bd), 20g of α-methylstyrene, 0.2g of sodium formaldehyde sulfoxylate (SFS), and 1g of isopropane hydroperoxide (CHP) were added to a pressure-resistant polymerizer. The reaction was carried out at 60°C, with 0.12g of potassium oleate added dropwise over 3 hours. After 12 hours of reaction, the system pressure was reduced to 0.2 MPaG, and the polymerization conversion rate was 99 wt%. After polymerization, unreacted butadiene monomer was removed using a vacuum diaphragm pump, yielding a polybutadiene rubber latex with a solid content of 36.5%.

[0097] Preparation of graft copolymer-4:

[0098] 140 g of the above-mentioned polybutadiene rubber latex was added to a reactor equipped with a thermometer, a stirrer, a reflux cooler, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, the temperature was raised to 70°C, and 0.055 g of sodium formaldehyde sulfoxylate, 0.165 g of tert-butyl hydroperoxide, 0.0018 g of ferrous sulfate heptahydrate, and 0.0055 g of disodium ethylenediaminetetraacetate (EDTA) were added. (a) A pre-emulsion of 0.1 g of acrolein, 45 g of methyl methacrylate (MMA), 0.45 g of sodium oleate, and 13.5 g of water was added dropwise to the above reactor over 1.5 h. (b) A pre-emulsion of 5 g of styrene, 0.05 g of sodium oleate, and 1.5 g of water was added dropwise to the above reactor over 0.5 h. After the addition was complete, the mixture was kept at this temperature for 1.5 h, cooled to 50°C, and discharged to obtain graft copolymer-4.

[0099] Flocculation:

[0100] After adding 1g of IRGANOX 1076 [octadecyl 3(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate] as a phenolic antioxidant, the emulsion was added to 795g of a 0.15wt% dilute sulfuric acid aqueous solution within 1min. Subsequently, 5wt% sulfuric acid aqueous solution was added to adjust the pH value to below 1.5, and 10wt% sodium hydroxide aqueous solution was added to adjust the pH value to 7.0. The mixture was filtered to obtain a wet filter cake, which was washed with pure water until the conductivity was less than 50μS / cm. The wet filter cake was dried in a fluidized bed until the moisture content was less than 1wt% to obtain the powder-packaged graft copolymer-4.

[0101] The physical properties of the prepared product are shown in Table 1.

[0102] Comparative Example 1

[0103] Compared to Example 1, the only difference is that acrolein is not added when preparing the graft copolymer.

[0104] The above powders were used to prepare PVC products according to the following proportions: PVC (Hanwha-SG800): 100g, MBS powder (self-made graft copolymer): 5g, ACR powder (LG-PA912): 1g, PE wax (Mn: 3000): 1g, stearic acid: 1g, plasticizer DOP: 10g, organotin heat stabilizer (methyltin mercaptan): 3g. All the above materials were added to a high-speed mixer and stirred thoroughly at 60°C for 2 minutes. The mixture was then poured into a two-roll mill (front and rear rollers at 190°C, speed ratio 24:16, thickness 0.25mm) and milled for 5 minutes to obtain a smooth PVC product. The PVC product was cut into 6cm*6cm sheets, and its yellowness, transmittance, and haze were tested using a haze meter and spectrophotometer. When testing mechanical properties, the thickness of the open mill was adjusted to 0.12mm. Fifteen sheets of 18cm*18cm were taken and tested using a dart tester (height set to 60cm, darts of different weights were used to free-fall and impact the sheets, and the weight when the sheet broke was recorded).

[0105] The physical properties of the prepared product are shown in Table 1.

[0106] Performance tests are as follows:

[0107] Table 1

[0108]

[0109]

[0110] Those skilled in the art will understand that modifications or adjustments can be made to the present invention based on the teachings of this specification. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A butadiene-methyl methacrylate-styrene MBS modifier composition, characterized in that, The modifier composition is prepared from raw materials comprising the following components: Component A contains 30-90 wt% of at least one butadiene component containing a diene group, preferably 38.41-74.41 wt%. Component B contains 1-50 wt% of at least one alkyl (meth)acrylate, preferably 4.85-44.21 wt%. Component C contains 1-60 wt% of at least one vinyl aromatic monomer, preferably 4.93-53.3 wt%. Component D contains at least one monomer containing an enaldehyde group at a concentration of 20-2000 ppm, preferably 97-981 ppm; Based on the total mass of the modifier composition.

2. The composition according to claim 1, characterized in that, The butadiene component containing diene groups comprises a diene having 4-7 carbon atoms and / or one or more dienes having 4-7 carbon atoms whose hydrogen atoms are replaced by halogens, preferably one or more of 1,3-butadiene, isoprene, and chloroprene, more preferably 1,3-butadiene.

3. The composition according to claim 1 or 2, wherein the (meth)acrylate alkyl ester comprises acrylates of alkyl esters having 1 to 12 carbon atoms and methyl methacrylate, and / or alkyl esters having 1 to 22 carbon atoms and having hydroxyl groups (meth)acrylates; Preferably, the acrylate and methacrylate of alkyl esters having 1 to 12 carbon atoms include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, and isooctyl methacrylate, preferably methyl methacrylate and / or n-butyl acrylate; Preferably, the alkyl group having 1 to 22 carbon atoms, the ester (meth)acrylate having a hydroxyl group comprises 2-hydroxyethyl (meth)acrylate and / or 4-hydroxybutyl (meth)acrylate.

4. The composition according to any one of claims 1-3, characterized in that, The vinyl aromatic monomer comprises styrene and / or styrene in which at least one hydrogen atom is substituted by a C1-C8 alkyl group or a halogen, preferably styrene, 2-(n-butyl)styrene, 4-(n-butyl)styrene, 4-(n-decyl)styrene, divinylbenzene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, or more preferably styrene.

5. The composition according to any one of claims 1-4, characterized in that, The monomer containing an enaldehyde group comprises one or more enaldehyde monomers having 3-10 carbon atoms, preferably one or more of acrolein, methacrolein, 3-methyl-2-butenal, 2-butylacrolein, 3-ethoxyisobutenal, trans-cinnamaldehyde, tin aldehyde, and trans-2-pentenal, more preferably acrolein and / or methacrolein.

6. The composition according to any one of claims 1-5, characterized in that, The modifier composition comprises the following auxiliary components: Component E contains 0.01-2 wt% of an initiator, preferably 0.25-1.04 wt%. Component F contains 0.2-5 wt% emulsifier, preferably 0.5-3 wt%. Component G is a pH buffer at 0.01-1 wt%, preferably 0.02-0.14 wt%. Based on the total mass of the modifier composition.

7. The composition according to any one of claims 1-6, characterized in that, The initiator comprises one or more of the following: thermally decomposable polymerization initiators, peroxides, reducing agents, transition metal salts, and redox systems formed by chelating agents, preferably redox systems formed by chelating agents; Preferably, the thermally decomposable polymerization initiator comprises one or more of azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate; Preferably, the peroxide comprises one or more of tert-butyl hydroperoxide, cumene hydroperoxide, terpene hydroperoxide, hydrogen peroxide, potassium persulfate, and ammonium persulfate; Preferably, the reducing agent comprises one or more of sodium formaldehyde sulfoxylate, glucose, sodium metabisulfite, and sodium hydrosulfite; Preferably, the transition metal salt comprises ferric(II) sulfate; Preferably, the redox system formed by the chelating agent comprises disodium ethylenediaminetetraacetate and / or tetrasodium ethylenediaminetetraacetate.

8. The composition according to any one of claims 1-7, characterized in that, The emulsifier comprises one or more of anionic surfactants, nonionic surfactants, anionic-nonionic surfactants, and cationic surfactants; Preferably, the anionic surfactant comprises one or more of fatty acid salts, alkyl sulfates, alkylbenzene sulfonates, alkyl phosphates, and dialkyl sulfosuccinates; Preferably, the nonionic surfactant comprises polyoxyethylene alkyl ethers and / or polyoxyethylene fatty acid esters; Preferably, the anionic nonionic surfactant comprises fatty alcohol ether phosphates and their salts, and / or sulfates; Preferably, the cationic surfactant comprises one or more of sorbitol fatty acid esters, glycerol fatty acid esters, and alkylamine salts; Preferably, the emulsifier comprises fatty acid salts and / or fatty alcohol ether phosphates and their salts.

9. The composition according to any one of claims 1-8, characterized in that, The pH buffer comprises water-soluble phosphates and / or carbonates, preferably one or more of sodium carbonate, sodium bicarbonate, potassium phosphate, potassium carbonate, potassium bicarbonate, and sodium dihydrogen phosphate, more preferably potassium phosphate.

10. A method for preparing a butadiene-methyl methacrylate-styrene MBS modifier composition, wherein the composition is the modifier composition according to any one of claims 1-9, characterized in that, The method includes the following steps: A diene-based rubber core polymer was prepared, and an alkenyl aldehyde-containing component was added to prepare a graft copolymer to form a core-shell structure, which was then used to demulsify and flocculate the emulsion.

11. The method according to claim 10, characterized in that, The reaction temperature for preparing diene-based rubber core polymers is 50-70℃; And / or, the reaction temperature for preparing graft copolymers by adding components containing aldehydes is 60-80℃.

12. Application of a butadiene-methyl methacrylate-styrene MBS modifier composition, said composition being the modifier composition of any one of claims 1-9, or the modifier composition prepared by the method of claim 10 or 11, said modifier composition being used as an impact modifier in polycarbonate plastics or polyvinyl chloride plastics.

13. An impact-modified plastic, wherein the plastic is composed of a modifier composition according to any one of claims 1-9, or a modifier composition prepared by the method of claim 10 or 11, wherein the impact-modified plastic is an impact-modified polycarbonate plastic or an impact-modified polyvinyl chloride plastic containing the above-mentioned impact modifier.

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