CN117551242B - Preparation method of impact modifier ACM resin - Google Patents
Preparation method of impact modifier ACM resin Download PDFInfo
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- CN117551242B CN117551242B CN202410026638.6A CN202410026638A CN117551242B CN 117551242 B CN117551242 B CN 117551242B CN 202410026638 A CN202410026638 A CN 202410026638A CN 117551242 B CN117551242 B CN 117551242B
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- 239000011347 resin Substances 0.000 title claims abstract description 88
- 229920005989 resin Polymers 0.000 title claims abstract description 88
- 239000004609 Impact Modifier Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 146
- 238000003756 stirring Methods 0.000 claims abstract description 116
- 239000008367 deionised water Substances 0.000 claims abstract description 51
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004816 latex Substances 0.000 claims abstract description 25
- 229920000126 latex Polymers 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 119
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 62
- 239000005543 nano-size silicon particle Substances 0.000 claims description 37
- 235000012239 silicon dioxide Nutrition 0.000 claims description 37
- 239000007908 nanoemulsion Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 29
- 235000019441 ethanol Nutrition 0.000 claims description 28
- 239000011787 zinc oxide Substances 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 19
- 239000001509 sodium citrate Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 230000010355 oscillation Effects 0.000 claims description 15
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 14
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000004246 zinc acetate Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 11
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 10
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 9
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 7
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- -1 nanoemulsifier Chemical compound 0.000 claims description 3
- JKJJSJJGBZXUQV-UHFFFAOYSA-N methyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OC JKJJSJJGBZXUQV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 56
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 56
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000035939 shock Effects 0.000 abstract description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 11
- 230000009467 reduction Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a preparation method of an impact modifier ACM resin, which belongs to the technical field of ACM resins, and comprises the following steps: preparing seed latex, primary grafting, secondary grafting and post-treatment; the preparation method comprises the steps of preparing seed latex, adding ethyl acrylate, allyl methacrylate, a nanoemulsifier and deionized water into a reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 40-50 ℃, stirring, and using 60 Carrying out irradiation by a Co irradiation source, and obtaining seed latex after the irradiation is finished; the ACM resin prepared by the invention has excellent oil resistance, ozone resistance, chemical corrosion resistance and weather resistance, and can improve the normal-temperature shock resistance and low-temperature resistance of polyvinyl chlorideImpact properties, and does not affect the transparency and flowability of polyvinyl chloride.
Description
Technical Field
The invention relates to the technical field of ACM (acrylic acid) resin, in particular to a preparation method of an impact modifier ACM resin.
Background
Impact modifiers are chemicals that improve the low temperature embrittlement defect of polymeric materials, imparting them with higher toughness. The impact modifier is mainly used in the processing of polyvinyl chloride, and is used for improving the processing performance and the impact strength. The traditional impact modifier mainly comprises Chlorinated Polyethylene (CPE), methyl methacrylate-butadiene-styrene copolymer (MBS) and acrylonitrile-butadiene-styrene copolymer (ABS), acrylic ester copolymer (ACR), acrylonitrile-butadiene random copolymer (NBR), and along with the development of the impact modifier industry, the requirements of the impact modifier are higher and higher, and the traditional impact modifier is difficult to meet the requirements of oil resistance, ozone resistance, chemical corrosion resistance and weather resistance while improving the normal-temperature impact resistance and the low-temperature impact resistance.
The polyacrylate elastomer (ACM) resin is an excellent plastic modifier, has the elasticity and toughness of rubber, has better low-temperature resistance, can improve the low-temperature impact resistance of polyvinyl chloride, has oil resistance, ozone resistance, chemical corrosion resistance and weather resistance, and is often used as an impact modifier for processing the polyvinyl chloride.
At present, the preparation method of the ACM resin mainly comprises a solution polymerization method, a suspension polymerization method and an emulsion polymerization method. Wherein the solution polymerization method is to make ethylene-acrylic ester in BF 3 In the presence of halogenated hydrocarbon as solvent, ethylene-acrylic ester copolymer is formed, but the method requires high-temperature and high-pressure production environment and consumes large energy; the suspension polymerization method is to prepare the suspension polymerization method by taking ethylene-acrylic ester-vinyl acetate as a monomer, but the method is difficult to effectively control and adjust parameters such as particle size, dispersity, polymerization degree and the like, and the quality of a product is easy to be unstable; emulsion polymerization is the main method for producing ACM resin at present, and the method uses simple equipment and is easy to implement.
However, in the production of ACM by emulsion polymerization, there are the following problems: first, many auxiliaries such as emulsifiers, initiators, molecular weight regulators, etc. are used in emulsion polymerization, and the auxiliaries are difficult to completely remove from the produced ACM resin, and the existence of the auxiliaries can influence the elasticity and toughness of the ACM resin and also influence the low temperature resistance, oil resistance, ozone resistance, chemical corrosion resistance and weather resistance of the ACM resin; the main chain of the ACM resin is a saturated carbon chain, the side group is a polar ester group, the more the carbon number on the side group is, the stronger the low-temperature resistance and fluidity of the ACM resin are, the improvement effect on the low-temperature shock resistance of the polyvinyl chloride is large, the influence on the fluidity of the polyvinyl chloride is small, but the oil resistance of the ACM resin is poor, so that the prepared ACM resin is difficult to simultaneously meet the low-temperature resistance, the fluidity and the oil resistance; the ACM resin produced by emulsion polymerization has a large amount of auxiliary agent residues, and can also influence the transparency of the polyvinyl chloride after being added into the polyvinyl chloride.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of an impact modifier ACM resin, and the prepared ACM resin has excellent oil resistance, ozone resistance, chemical corrosion resistance and weather resistance, can improve the normal-temperature impact resistance and low-temperature impact resistance of polyvinyl chloride, and can not influence the transparency and fluidity of the polyvinyl chloride.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of an impact modifier ACM resin comprises the following steps: preparing seed latex, primary grafting, secondary grafting and post-treatment;
the preparation method comprises the steps of preparing seed latex, adding ethyl acrylate, allyl methacrylate, a nanoemulsifier and deionized water into a reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 40-50 ℃, controlling the stirring speed to 200-400rpm, stirring for 20-40min, and using 60 The Co irradiation source is used for irradiation, the irradiation time is controlled to be 5-6h, the total irradiation dose is 50-60KGy, heating and stirring are stopped after the irradiation is finished, and the seed latex is obtained after the material is poured;
in the preparation of the seed latex, the mass ratio of the ethyl acrylate to the allyl methacrylate to the nanoemulsifier to the deionized water is 70-80:1-1.5:2-2.5:250-280;
adding seed latex, a nanoemulsion, ethyl acrylate, allyl methacrylate and deionized water into a reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 60-70 ℃, controlling the stirring speed to 200-400rpm, and stirring for 20-40min to obtain the final product 60 The Co irradiation source is used for irradiation, the irradiation time is controlled to be 3-4 hours, the total irradiation dose is 30-40KGy, heating and stirring are stopped after the irradiation is finished, and the material is poured to obtain a primary graft;
in the primary grafting, the mass ratio of the seed latex to the nanoemulsion to the ethyl acrylate to the allyl methacrylate to the deionized water is 50-55:2-2.5:150-160:1.6-1.8:150-170;
the secondary grafting is carried out by adding primary graft, first nanometer emulsifier, methyl ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate and deionized water into reactor, sealing reactor, replacing air in reactor with nitrogen, controlling reactor temperature to 70-80 degree, controlling stirring speed to 200-400rpm, stirring for 20-40min, and using 60 Co irradiationThe source performs primary irradiation, the primary irradiation time is controlled to be 2-2.5h, the total primary irradiation dose is 20-25KGy, then a second part of nanoemulsion and modified nano silicon dioxide are added, and the continuous use is performed 60 Performing secondary irradiation by using a Co irradiation source, controlling the secondary irradiation time to be 1.5-2h, controlling the total secondary irradiation dose to be 15-20KGy, stopping heating and stirring after the secondary irradiation is finished, and pouring to obtain a secondary graft;
in the secondary grafting, the mass ratio of the first graft, the first part of the nanoemulsion, the ethyl methacrylate, the butyl acrylate, the hydroxyethyl methacrylate, the deionized water, the second part of the nanoemulsion and the modified nano silicon dioxide is 200-220:1-1.5:8-9:0.8-1:1.5-2:30-40:0.4-0.5:1.4-1.5;
the preparation method of the modified nano silicon dioxide comprises the steps of adding gamma-methacryloxypropyl trimethoxy silane, glacial acetic acid, nano silicon dioxide, deionized water and absolute ethyl alcohol into a reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, then controlling the temperature of the reaction kettle to 65-70 ℃, controlling the stirring speed to 100-200rpm, stirring for 3-4 hours, centrifuging, controlling the rotating speed during centrifuging to 9000-10000rpm for 20-25 minutes, using deionized water to clean sediment for 3-4 times after the centrifuging, and drying at 80-90 ℃ after the cleaning is finished to obtain the modified nano silicon dioxide;
in the preparation of the modified nano silicon dioxide, the mass ratio of the gamma-methacryloxypropyl trimethoxy silane to the glacial acetic acid to the nano silicon dioxide to the deionized water to the absolute ethyl alcohol is 9-10:0.5-0.6:100-110:200-220:120-150;
the particle size of the nano silicon dioxide is 20-30nm;
the preparation method of the nanoemulsion comprises the following steps: preparing hydrophilic nano zinc oxide and grafting;
the preparation method comprises the steps of preparing hydrophilic nano zinc oxide, adding zinc acetate dihydrate and absolute ethyl alcohol into a reaction kettle, controlling the temperature of the reaction kettle to be 30-50 ℃, controlling the stirring speed to be 100-200rpm, and stirring for 20-50min to obtain an ethanol solution of zinc acetate; adding sodium hydroxide and absolute ethyl alcohol into a reaction kettle, controlling the temperature of the reaction kettle to be 30-50 ℃, controlling the stirring speed to be 100-200rpm, and stirring for 20-50min to obtain an ethanol solution of sodium hydroxide; adding an ethanol solution of zinc acetate and an ethanol solution of sodium hydroxide into a reaction kettle, controlling the temperature of the reaction kettle to be 30-50 ℃, controlling the stirring speed to be 100-200rpm, stirring for 10-30min, adding a sodium citrate aqueous solution, continuously stirring for 10-30min, increasing the temperature of the reaction kettle to be 120-130 ℃, increasing the stirring speed to be 200-300rpm, continuously stirring for 13-15h, centrifuging, controlling the rotating speed during centrifuging to be 9000-10000rpm for 10-15min, washing a precipitate with deionized water for 3-4 times after centrifuging, and drying at 110-120 ℃ after washing to obtain hydrophilic nano zinc oxide;
in the preparation of the hydrophilic nano zinc oxide, the mass ratio of zinc acetate dihydrate to absolute ethyl alcohol in the ethanol solution of the zinc acetate is 18-20:4000-4200;
the mass ratio of the sodium hydroxide to the absolute ethyl alcohol in the ethanol solution of the sodium hydroxide is 0.9-1:4000-4200;
the mass ratio of the zinc acetate dihydrate in the ethanol solution of the zinc acetate to the sodium hydroxide in the ethanol solution of the sodium hydroxide to the sodium citrate aqueous solution is 18-20:0.9-1:20-25;
the preparation method of the sodium citrate aqueous solution comprises the steps of adding sodium citrate dihydrate and deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 30-50 ℃, controlling the stirring speed to 100-200rpm, and stirring for 10-30min to obtain the sodium citrate aqueous solution;
in the preparation of the sodium citrate aqueous solution, the mass ratio of the sodium citrate dihydrate to the deionized water is 0.45-0.5:20-25;
the grafting is carried out by mixing hydrophilic nano zinc oxide and absolute ethyl alcohol, then carrying out ultrasonic oscillation, controlling the frequency of ultrasonic oscillation to be 20-30KHz, and the time to be 40-60min, and obtaining zinc oxide dispersion after ultrasonic oscillation is finished; adding zinc oxide dispersion into a reaction kettle, controlling the temperature of the reaction kettle to 60-65 ℃, controlling the stirring speed to 200-400rpm, adding isopropyl tri (dioctyl pyrophosphoryl) titanate into the reaction kettle, stirring for 10-11h, dropwise adding 1-bromo-n-dodecane, adding diethylaminoethyl methacrylate after the dropwise adding is finished, continuously stirring for 10-11h, centrifuging, controlling the rotating speed during centrifuging to 9000-10000rpm for 10-15min, washing precipitate 3-4 times by using absolute ethyl alcohol after the centrifuging is finished, and drying at 80-90 ℃ after the washing is finished to obtain a nanoemulsion;
in the grafting, the mass ratio of the hydrophilic nano zinc oxide to the absolute ethyl alcohol to the isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate to the 1-bromo-n-dodecane to the diethylaminoethyl methacrylate is 5-5.5:200-250:0.4-0.5:4-4.2:0.4-0.5;
the dropping speed of the 1-bromo-n-dodecane is 0.8-1g/min;
and (3) performing post-treatment, namely demulsifying, centrifuging, cleaning and drying the secondary grafts to obtain the impact modifier ACM resin.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the impact modifier ACM resin can improve the normal-temperature impact resistance of the polyvinyl chloride, and the impact strength of the polyvinyl chloride at 23 ℃ can reach 45.4-46.9KJ/m after the impact modifier ACM resin is added into the polyvinyl chloride 2 ；
(2) The impact modifier ACM resin prepared by the preparation method of the impact modifier ACM resin can improve the low-temperature impact resistance of polyvinyl chloride, and the impact strength of the polyvinyl chloride at the temperature of minus 40 ℃ can reach 19.1-19.8KJ/m after the impact modifier ACM resin prepared by the preparation method is added into the polyvinyl chloride 2 ；
(3) According to the preparation method of the impact modifier ACM resin, the prepared impact modifier ACM resin does not influence the transparency of polyvinyl chloride, and after the impact modifier ACM resin is added into the polyvinyl chloride, the light transmittance of the polyvinyl chloride is 87.8-88.2%, and the haze is 5.0-5.2%;
(4) According to the preparation method of the impact modifier ACM resin, the prepared impact modifier ACM resin does not influence the fluidity of the polyvinyl chloride, and after the impact modifier ACM resin is added into the polyvinyl chloride, the melt flow rate (190 ℃ C., 21.6 kg) of the polyvinyl chloride is 6.7-6.8g/10min;
(5) The impact modifier ACM resin prepared by the preparation method of the impact modifier ACM resin has excellent oil resistance, is completely soaked in No. 30 engine oil, is continuously soaked for 7d at 50 ℃, and is then added into polyvinyl chloride, wherein the impact strength reduction rate of the polyvinyl chloride at 23 ℃ is 6.1-6.4%, and the impact strength reduction rate at-40 ℃ is 7.5-7.7%;
(6) The impact modifier ACM resin prepared by the preparation method of the impact modifier ACM resin has excellent ozone resistance, the impact modifier ACM resin prepared by the preparation method is placed in an ozone environment for ozone treatment, the concentration of ozone is controlled to be 100pphm, the ozone treatment is continuously carried out for 7d at 40 ℃, then the ozone treatment is added into polyvinyl chloride, the impact strength reduction rate of the polyvinyl chloride at 23 ℃ is 3.4-3.5%, and the impact strength reduction rate at-40 ℃ is 3.8-4.0%;
(7) The impact modifier ACM resin prepared by the preparation method of the impact modifier ACM resin has excellent chemical corrosion resistance, is completely soaked in 10 mass percent hydrochloric acid aqueous solution, is continuously soaked for 7d at 40 ℃, and then is added into polyvinyl chloride, wherein the reduction rate of the impact strength of the polyvinyl chloride at 23 ℃ is 0.4-0.6%, and the reduction rate of the impact strength of the polyvinyl chloride at-40 ℃ is 0.4-0.7%; the impact modifier ACM resin prepared by the invention is fully soaked in 10% sodium hydroxide aqueous solution at 40 ℃ for 7d, then is added into polyvinyl chloride, the impact strength reduction rate of the polyvinyl chloride at 23 ℃ is 0.2-0.3%, and the impact strength reduction rate at-40 ℃ is 0.2-0.4%;
(8) The impact modifier ACM resin prepared by the preparation method of the impact modifier ACM resin has excellent weather resistance, is placed at 50 ℃ for 30d, is placed at-40 ℃ for 30d, is added into polyvinyl chloride, and has an impact strength reduction rate of 0.8-0.9% at 23 ℃ and an impact strength reduction rate of 0.9-1.1% at-40 ℃.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A preparation method of an impact modifier ACM resin specifically comprises the following steps:
1. preparing seed latex: 70g of ethyl acrylate, 1g of allyl methacrylate, 2g of nanoemulsifier and 250g of deionized water are added into a reaction kettle, the reaction kettle is closed, nitrogen is used for replacing air in the reaction kettle, then the temperature of the reaction kettle is controlled to 40 ℃, the stirring speed is controlled to 200rpm, and after stirring for 20min, the reaction kettle is used 60 The Co irradiation source irradiates, the irradiation time is controlled to be 5 hours, the total irradiation dose is 50KGy, and after the irradiation is finished, heating and stirring are stopped, and the seed latex is obtained after the material is poured;
the preparation method of the nanoemulsion comprises the following steps:
(1) Preparing hydrophilic nano zinc oxide: adding 18g of zinc acetate dihydrate and 4000g of absolute ethyl alcohol into a reaction kettle, controlling the temperature of the reaction kettle to 30 ℃, controlling the stirring speed to 100rpm, and stirring for 20min to obtain an ethanol solution of zinc acetate; adding 0.9g of sodium hydroxide and 4000g of absolute ethyl alcohol into a reaction kettle, controlling the temperature of the reaction kettle to 30 ℃, controlling the stirring speed to 100rpm, and stirring for 20min to obtain an ethanol solution of sodium hydroxide; adding an ethanol solution of zinc acetate and an ethanol solution of sodium hydroxide into a reaction kettle, controlling the temperature of the reaction kettle to 30 ℃, controlling the stirring speed to 100rpm, stirring for 10min, adding 20g of sodium citrate aqueous solution, continuously stirring for 10min, increasing the temperature of the reaction kettle to 120 ℃, increasing the stirring speed to 200rpm, continuously stirring for 13h, centrifuging, controlling the rotating speed during centrifuging to 9000rpm for 10min, cleaning the precipitate 3 times by using deionized water after centrifuging, using 50g of deionized water for each cleaning, and drying at 110 ℃ after cleaning to obtain hydrophilic nano zinc oxide;
the preparation method of the sodium citrate aqueous solution comprises the following steps: adding 0.45g of sodium citrate dihydrate and 20g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 30 ℃, controlling the stirring speed to 100rpm, and stirring for 10min to obtain a sodium citrate aqueous solution;
(2) Grafting: mixing 5g of hydrophilic nano zinc oxide and 200g of absolute ethyl alcohol, performing ultrasonic oscillation, controlling the frequency of ultrasonic oscillation to be 20KHz and the time to be 40min, and obtaining a zinc oxide dispersion after ultrasonic oscillation is finished; adding zinc oxide dispersion into a reaction kettle, controlling the temperature of the reaction kettle to 60 ℃, controlling the stirring speed to 200rpm, adding 0.4g isopropyl tri (dioctyl pyrophosphoryl) titanate into the reaction kettle, stirring for 10 hours, dropwise adding 4g 1-bromo-n-dodecane, controlling the dropwise adding speed to be 0.8g/min, adding 0.4g diethylaminoethyl methacrylate after the dropwise adding is finished, continuously stirring for 10 hours, centrifuging, controlling the rotating speed during the centrifuging to be 9000rpm, controlling the time to be 10 minutes, washing the precipitate 3 times by using absolute ethyl alcohol after the centrifuging is finished, using 30g absolute ethyl alcohol for each washing, and drying at 80 ℃ after the washing is finished to obtain a nano emulsifier;
2. and (3) primary grafting: 50g of the seed latex prepared in step 1, 2g of the nanoemulsion prepared in step 1, 150g of ethyl acrylate, 1.6g of allyl methacrylate and 150g of deionized water are added into a reaction kettle, the reaction kettle is closed, the air in the kettle is replaced by nitrogen, then the temperature of the reaction kettle is controlled to 60 ℃, the stirring speed is controlled to 200rpm, and after stirring for 20min, the mixture is used 60 The Co irradiation source irradiates, the irradiation time is controlled to be 3 hours, the total irradiation dose is 30KGy, heating and stirring are stopped after the irradiation is finished, and the material is poured to obtain a primary graft;
3. and (3) secondary grafting: 200g of the primary graft prepared in the step 2, 1g of the nanoemulsion prepared in the step 1, 8g of ethyl methacrylate, 0.8g of butyl acrylate, 1.5g of hydroxyethyl methacrylate and 30g of deionized water are added into a reaction kettle, the reaction kettle is closed, the air in the reaction kettle is replaced by nitrogen, then the temperature of the reaction kettle is controlled to 70 ℃, the stirring speed is controlled to 200rpm, and after stirring for 20min, the reaction kettle is used 60 The Co irradiation source is subjected to primary irradiation, the primary irradiation time is controlled to be 2 hours, the total primary irradiation dose is 20KGy, and then 0.4g of the nano-emulsifier prepared in the step 1 is added,1.4g of modified nano silicon dioxide and continuously used 60 Performing secondary irradiation by using a Co irradiation source, controlling the secondary irradiation time to be 1.5h, controlling the total secondary irradiation dose to be 15KGy, stopping heating and stirring after the secondary irradiation is finished, and pouring to obtain a secondary graft;
the preparation method of the modified nano silicon dioxide comprises the following steps: adding 9g of gamma-methacryloxypropyl trimethoxysilane, 0.5g of glacial acetic acid, 100g of nano silicon dioxide, 200g of deionized water and 120g of absolute ethyl alcohol into a reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 65 ℃, controlling the stirring speed to 100rpm, after stirring for 3 hours, centrifuging, controlling the rotating speed during centrifuging to 9000rpm, controlling the time to 20min, using deionized water to clean sediment for 3 times after centrifuging, using 300g of deionized water for each cleaning, and drying at 80 ℃ after cleaning to obtain modified nano silicon dioxide;
the particle size of the nano silicon dioxide is 20nm;
4. post-treatment: and demulsifying, centrifuging, cleaning and drying the secondary graft to obtain the impact modifier ACM resin.
Example 2
A preparation method of an impact modifier ACM resin specifically comprises the following steps:
1. preparing seed latex: 75g of ethyl acrylate, 1.2g of allyl methacrylate, 2.2g of nano-emulsifier and 260g of deionized water are added into a reaction kettle, the reaction kettle is closed, nitrogen is used for replacing air in the reaction kettle, then the temperature of the reaction kettle is controlled to 45 ℃, the stirring speed is controlled to 300rpm, and after stirring for 30min, the reaction kettle is used for 60 The Co irradiation source irradiates, the irradiation time is controlled to be 5.5 hours, the total irradiation dose is 55KGy, and after the irradiation is finished, heating and stirring are stopped, and the seed latex is obtained after the material is poured;
the preparation method of the nanoemulsion comprises the following steps:
(1) Preparing hydrophilic nano zinc oxide: adding 19g of zinc acetate dihydrate and 4100g of absolute ethyl alcohol into a reaction kettle, controlling the temperature of the reaction kettle to 40 ℃, controlling the stirring speed to 150rpm, and stirring for 30min to obtain an ethanol solution of zinc acetate; adding 0.9g of sodium hydroxide and 4100g of absolute ethyl alcohol into a reaction kettle, controlling the temperature of the reaction kettle to 40 ℃, controlling the stirring speed to 150rpm, and stirring for 30min to obtain an ethanol solution of sodium hydroxide; adding an ethanol solution of zinc acetate and an ethanol solution of sodium hydroxide into a reaction kettle, controlling the temperature of the reaction kettle to 40 ℃, controlling the stirring speed to 150rpm, stirring for 20min, adding 22g of sodium citrate aqueous solution, continuously stirring for 20min, increasing the temperature of the reaction kettle to 125 ℃, increasing the stirring speed to 250rpm, continuously stirring for 14h, centrifuging, controlling the rotating speed during centrifuging to 9500rpm for 12min, cleaning the precipitate with deionized water for 4 times after centrifuging, using 80g of deionized water for each cleaning, and drying at 115 ℃ after cleaning to obtain hydrophilic nano zinc oxide;
the preparation method of the sodium citrate aqueous solution comprises the following steps: adding 0.48g of sodium citrate dihydrate and 22g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 40 ℃, controlling the stirring speed to 150rpm, and stirring for 20min to obtain a sodium citrate aqueous solution;
(2) Grafting: mixing 5.2g of hydrophilic nano zinc oxide and 220g of absolute ethyl alcohol, and then carrying out ultrasonic oscillation, wherein the frequency of ultrasonic oscillation is controlled to be 25KHz, the time is 50min, and the ultrasonic oscillation is finished to obtain zinc oxide dispersion liquid; adding zinc oxide dispersion into a reaction kettle, controlling the temperature of the reaction kettle to 62 ℃, controlling the stirring speed to 300rpm, adding 0.45g of isopropyl tri (dioctyl pyrophosphoryl) titanate into the reaction kettle, stirring for 10.5h, dropwise adding 4.1g of 1-bromo-n-dodecane, controlling the dropwise adding speed to be 0.9g/min, adding 0.45g of diethylaminoethyl methacrylate after the dropwise adding is finished, continuously stirring for 10.5h, centrifuging, controlling the rotating speed during centrifuging to be 9500rpm, controlling the time to be 12min, washing a precipitate 3 times by using absolute ethanol after the centrifuging is finished, using 40g of absolute ethanol for each washing, and drying at 85 ℃ after the washing is finished to obtain a nano emulsifier;
2. and (3) primary grafting: 52g of the seed latex prepared in step 1, 2.2g of the nanoemulsion prepared in step 1, 155g of ethyl acrylate, 1.7g of allyl methacrylate and 160g of deionized water are added into a reaction kettle, the reaction kettle is closed, and the air in the kettle is replaced by nitrogen, and thenThen the temperature of the reaction kettle is controlled to 65 ℃, the stirring speed is controlled to 300rpm, and the reaction kettle is used after stirring for 30min 60 The Co irradiation source irradiates, the irradiation time is controlled to be 3.5 hours, the total irradiation dose is 35KGy, heating and stirring are stopped after the irradiation is finished, and the material is poured to obtain a primary graft;
3. and (3) secondary grafting: 210g of the primary graft prepared in step 2, 1.2g of the nanoemulsion prepared in step 1, 8.5g of ethyl methacrylate, 0.9g of butyl acrylate, 1.8g of hydroxyethyl methacrylate and 35g of deionized water are added into a reaction kettle, the reaction kettle is closed, the air in the kettle is replaced by nitrogen, then the temperature of the reaction kettle is controlled to 75 ℃, the stirring speed is controlled to 300rpm, and after stirring for 30min, the reaction kettle is used 60 Performing primary irradiation by Co irradiation source, controlling primary irradiation time to be 2h, controlling total primary irradiation dose to be 20KGy, then adding 0.45g of nano-emulsifier prepared in step 1 and 1.45g of modified nano-silica, and continuing to use 60 Performing secondary irradiation by using a Co irradiation source, controlling the secondary irradiation time to be 2 hours, controlling the total dose of the secondary irradiation to be 20KGy, stopping heating and stirring after the secondary irradiation is finished, and pouring to obtain a secondary graft;
the preparation method of the modified nano silicon dioxide comprises the following steps: adding 9.5g of gamma-methacryloxypropyl trimethoxy silane, 0.55g of glacial acetic acid, 105g of nano silicon dioxide, 210g of deionized water and 130g of absolute ethyl alcohol into a reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 65 ℃, controlling the stirring speed to 150rpm, stirring for 3.5 hours, centrifuging, controlling the rotating speed during centrifuging to 9500rpm for 22 minutes, using deionized water to clean sediment for 3 times after the centrifuging, using 400g of deionized water for each cleaning, and drying at 85 ℃ after the cleaning is finished to obtain modified nano silicon dioxide;
the particle size of the nano silicon dioxide is 20nm;
4. post-treatment: and demulsifying, centrifuging, cleaning and drying the secondary graft to obtain the impact modifier ACM resin.
Example 3
A preparation method of an impact modifier ACM resin specifically comprises the following steps:
1. preparing seed latex: adding 80g of ethyl acrylate, 1.5g of allyl methacrylate, 2.5g of nano-emulsifier and 280g of deionized water into a reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 50 ℃, controlling the stirring speed to 400rpm, stirring for 40min, and using 60 The Co irradiation source irradiates, the irradiation time is controlled to be 6 hours, the total irradiation dose is 60KGy, and after the irradiation is finished, heating and stirring are stopped, and the seed latex is obtained after the material is poured;
the preparation method of the nanoemulsion comprises the following steps:
(1) Preparing hydrophilic nano zinc oxide: adding 20g of zinc acetate dihydrate and 4200g of absolute ethyl alcohol into a reaction kettle, controlling the temperature of the reaction kettle to 50 ℃, controlling the stirring speed to 200rpm, and stirring for 50min to obtain an ethanol solution of zinc acetate; adding 1g of sodium hydroxide and 4200g of absolute ethyl alcohol into a reaction kettle, controlling the temperature of the reaction kettle to 50 ℃, controlling the stirring speed to 200rpm, and stirring for 50min to obtain an ethanol solution of sodium hydroxide; adding an ethanol solution of zinc acetate and an ethanol solution of sodium hydroxide into a reaction kettle, controlling the temperature of the reaction kettle to 50 ℃, controlling the stirring speed to 200rpm, stirring for 30min, adding 25g of sodium citrate aqueous solution, continuously stirring for 30min, increasing the temperature of the reaction kettle to 130 ℃, increasing the stirring speed to 300rpm, continuously stirring for 15h, centrifuging, controlling the rotating speed during centrifuging to 10000rpm for 15min, cleaning the precipitate with deionized water for 4 times after centrifuging, using 100g of deionized water for each cleaning, and drying at 120 ℃ after cleaning to obtain hydrophilic nano zinc oxide;
the preparation method of the sodium citrate aqueous solution comprises the following steps: adding 0.5g of sodium citrate dihydrate and 25g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 50 ℃, controlling the stirring speed to 200rpm, and stirring for 30min to obtain a sodium citrate aqueous solution;
(2) Grafting: mixing 5.5g of hydrophilic nano zinc oxide and 250g of absolute ethyl alcohol, and then carrying out ultrasonic oscillation, wherein the frequency of ultrasonic oscillation is controlled to be 30KHz, the time is 60min, and the ultrasonic oscillation is finished to obtain zinc oxide dispersion liquid; adding zinc oxide dispersion into a reaction kettle, controlling the temperature of the reaction kettle to 65 ℃, controlling the stirring speed to 400rpm, adding 0.5g isopropyl tri (dioctyl pyrophosphoryl) titanate into the reaction kettle, stirring for 11h, dropwise adding 4.2g 1-bromo-n-dodecane, controlling the dropwise adding speed to be 1g/min, adding 0.5g diethylaminoethyl methacrylate after the dropwise adding is finished, continuing stirring for 11h, centrifuging, controlling the rotating speed during centrifuging to be 10000rpm, controlling the time to be 15min, washing the precipitate with absolute ethyl alcohol for 4 times after the centrifuging is finished, using 50g absolute ethyl alcohol for each washing, and drying at 90 ℃ after the washing is finished to obtain a nanoemulsion;
2. and (3) primary grafting: 55g of the seed latex prepared in step 1, 2.5g of the nanoemulsion prepared in step 1, 160g of ethyl acrylate, 1.8g of allyl methacrylate and 170g of deionized water are added into a reaction kettle, the reaction kettle is closed, the air in the reaction kettle is replaced by nitrogen, then the temperature of the reaction kettle is controlled to 70 ℃, the stirring speed is controlled to 400rpm, and after stirring for 40min, the mixture is used 60 The Co irradiation source irradiates, the irradiation time is controlled to be 4 hours, the total irradiation dose is 40KGy, heating and stirring are stopped after the irradiation is finished, and the material is poured to obtain a primary graft;
3. and (3) secondary grafting: 220g of the first graft prepared in step 2, 1.5g of the nanoemulsion prepared in step 1, 9g of ethyl methacrylate, 1g of butyl acrylate, 2g of hydroxyethyl methacrylate and 40g of deionized water are added into a reaction kettle, the reaction kettle is closed, the air in the reaction kettle is replaced by nitrogen, then the temperature of the reaction kettle is controlled to 80 ℃, the stirring speed is controlled to 400rpm, and after stirring for 40min, the reaction kettle is used 60 Performing primary irradiation by using a Co irradiation source, controlling the primary irradiation time to be 2.5h, controlling the total primary irradiation dose to be 25KGy, then adding 0.5g of the nanoemulsion prepared in the step 1 and 1.5g of modified nano silicon dioxide, and continuously using 60 Performing secondary irradiation by using a Co irradiation source, controlling the secondary irradiation time to be 2 hours, controlling the total dose of the secondary irradiation to be 20KGy, stopping heating and stirring after the secondary irradiation is finished, and pouring to obtain a secondary graft;
the preparation method of the modified nano silicon dioxide comprises the following steps: adding 10g of gamma-methacryloxypropyl trimethoxysilane, 0.6g of glacial acetic acid, 110g of nano silicon dioxide, 220g of deionized water and 150g of absolute ethyl alcohol into a reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 70 ℃, controlling the stirring speed to 200rpm, after stirring for 4 hours, centrifuging, controlling the rotating speed during centrifuging to 10000rpm, controlling the time to 25 minutes, using deionized water to clean the precipitate for 4 times after centrifuging, using 500g of deionized water for each cleaning, and drying at 90 ℃ after cleaning to obtain modified nano silicon dioxide;
the particle size of the nano silicon dioxide is 30nm;
4. post-treatment: and demulsifying, centrifuging, cleaning and drying the secondary graft to obtain the impact modifier ACM resin.
Comparative example 1
The preparation of the impact modifier ACM resin described in example 2 was used, except that: the equal amount of the nanoemulsion used in the step 1 of preparing seed latex, the step 2 of first grafting and the step 3 of second grafting is replaced by sodium dodecyl benzene sulfonate.
Comparative example 2
The preparation of the impact modifier ACM resin described in example 2 was used, except that: in the step 3, the addition of hydroxyethyl methacrylate before primary irradiation, a nanoemulsion before secondary irradiation and modified nano silicon dioxide is omitted, and meanwhile, the step 3, namely, the step of secondary grafting is changed into the steps of:
210g of the primary graft prepared in the step 2, 1.2g of the nanoemulsion prepared in the step 1, 8.5g of ethyl methacrylate, 0.9g of butyl acrylate and 35g of deionized water are added into a reaction kettle, the reaction kettle is closed, the air in the reaction kettle is replaced by nitrogen, then the temperature of the reaction kettle is controlled to 75 ℃, the stirring speed is controlled to 300rpm, and after stirring for 30min, the reaction kettle is used 60 And (3) irradiating by using a Co irradiation source, controlling the irradiation time to be 2 hours, controlling the total irradiation dose to be 20KGy, stopping heating and stirring after the irradiation is finished, and pouring to obtain the secondary graft.
Test example 1
The impact modifier ACM resins prepared in examples 1-3 and comparative examples 1-2 were each added to polyvinyl chloride to prepare polyvinyl chloride test specimens, and the specific preparation method is as follows:
1000g of polyvinyl chloride resin, 80g of impact modifier ACM resin, 15g of calcium stearate and 2g of polyethylene wax are added into a high-speed stirrer to be stirred, and then extrusion molding is carried out in a double-screw extruder to obtain a test sample;
then, the polyvinyl chloride test specimen was tested for impact strength at 23 ℃, impact strength at-40 ℃, light transmittance, haze, and melt flow rate, and in order to serve as a blank, the polyvinyl chloride resin used in the preparation of the test specimen was also tested for impact strength at 23 ℃, impact strength at-40 ℃, light transmittance, haze, and melt flow rate, as follows:
from the above results, it can be seen that by using a nanoemulsion as an emulsifier in the preparation of the impact modifier ACM, the impact strength at 23 ℃, impact strength at-40 ℃, light transmittance, melt flow rate, and haze of the polyvinyl chloride test specimen prepared from the impact modifier ACM can be improved; by adding hydroxyethyl methacrylate and modified nano silicon dioxide in the secondary grafting step, the impact strength, the light transmittance and the melt flow rate of a polyvinyl chloride test sample prepared from an impact modifier ACM at-40 ℃ can be improved, and the haze can be reduced;
the preparation method of the nanoemulsion comprises the steps of introducing long-chain alkane by adding bromododecane after modifying the surface of hydrophilic zinc oxide by using a coupling agent, then introducing a small amount of diethylaminoethyl methacrylate, and introducing reactive amino to obtain the nanoemulsion with the reactive amino, wherein the nanoemulsion can participate in the reaction while realizing emulsification, the hydrophilic nano zinc oxide is bonded into the impact modifier ACM resin, the light transmittance of the hydrophilic nano zinc oxide is high, the compatibility with the polyvinyl chloride resin is good, the compatibility between the impact modifier ACM resin and the polyvinyl chloride resin can be improved after the impact modifier ACM resin is added, the influence on the light transmittance and the haze of the polyvinyl chloride resin can be reduced, the interface energy can be reduced by the nano effect of the hydrophilic nano zinc oxide, and the influence of the interface of the ACM resin and the polyvinyl chloride resin on the light transmittance and the haze can be avoided; in addition, the influence of the residual emulsifying agent on the performance of the impact modifier ACM resin can be avoided;
in the secondary grafting step, hydroxyethyl methacrylate and modified nano silicon dioxide are added, firstly, hydroxyethyl methacrylate can be grafted to obtain a side group with active hydroxyl, then after the modified nano silicon dioxide is added, the active hydroxyl can be bonded with the modified nano silicon dioxide, the reaction activity of the side group can be reduced after bonding, and the bonded modified nano silicon dioxide can form a nano layer on the surface of ACM resin, so that the fluidity of the ACM resin in polyvinyl chloride is improved, the grafting density is also improved, the low temperature resistance of the ACM resin is improved, in addition, the compatibility of the ACM resin and the polyvinyl chloride is improved, and the influence on the light transmittance and the haze of the polyvinyl chloride is avoided.
Test example 2
The impact modifier ACM resins prepared in examples 1 to 3 and comparative examples 1 to 2 were completely immersed in No. 30 engine oil, respectively, continuously immersed at 50℃for 7d, and then after preparing a polyvinyl chloride test sample according to the method of test example 1, the impact strength of the polyvinyl chloride test sample at 23℃and the impact strength at-40℃were tested, and the decrease rate of the impact strength after comparison with the impact strength at 23℃and the impact strength at-40℃measured in test example 1 was calculated as follows:
test example 3
The impact modifier ACM resins prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to ozone treatment in an ozone atmosphere, the concentration of ozone was controlled to be 100pphm, ozone treatment was continued at 40℃for 7d, and then after a polyvinyl chloride test specimen was prepared in the same manner as in test example 1, the impact strength at 23℃and the impact strength at-40℃of the polyvinyl chloride test specimen were tested, and the decrease rate of the impact strength after comparison with the impact strength at 23℃and the impact strength at-40℃measured in test example 1 was calculated as follows:
test example 4
The impact modifier ACM resins prepared in examples 1 to 3 and comparative examples 1 to 2 were completely immersed in 10% aqueous hydrochloric acid at a mass concentration, respectively, and continuously immersed at 40℃for 7d, and then after a polyvinyl chloride test specimen was prepared in accordance with the method of test example 1, the impact strength of the polyvinyl chloride test specimen at 23℃and the impact strength at-40℃were tested, and the impact strength decrease rate after comparison with the impact strength at 23℃and the impact strength at-40℃measured in test example 1 was calculated as follows:
test example 5
The impact modifier ACM resins prepared in examples 1 to 3 and comparative examples 1 to 2 were completely immersed in 10% aqueous sodium hydroxide solution at a mass concentration, respectively, and continuously immersed at 40℃for 7 days, and then after preparing a polyvinyl chloride test specimen according to the method of test example 1, the impact strength of the polyvinyl chloride test specimen at 23℃and the impact strength at-40℃were tested, and the impact strength decrease rate after comparison with the impact strength at 23℃and the impact strength at-40℃measured in test example 1 was calculated as follows:
test example 6
The impact modifier ACM resins prepared in examples 1 to 3 and comparative examples 1 to 2 were respectively left to stand at 50℃for 30d, left to stand at-40℃for 30d, and then after a polyvinyl chloride test specimen was prepared in accordance with the method of test example 1, the impact resistance of the polyvinyl chloride test specimen at 23℃and the impact resistance at-40℃were tested, and the decrease rate of the impact resistance after comparison with the impact resistance at 23℃and the impact resistance at-40℃measured in test example 1 was calculated as follows:
from test examples 2 to 6, it can be seen that oil resistance, ozone resistance, chemical resistance, weather resistance can be improved by using a nanoemulsion as an emulsifier in the preparation of the impact modifier ACM, and adding hydroxyethyl methacrylate and modified nanosilica in the secondary grafting step;
the nano-emulsifier has the advantages that the oil resistance, the ozone resistance, the chemical corrosion resistance and the weather resistance of the ACM resin are improved, the emulsification effect can be improved by using the reactive nano-emulsifier to replace the conventional emulsifier, meanwhile, zinc oxide is bonded to the ACM resin, the influence of the conventional emulsifier residue on the molecular chain structure of the ACM resin can be avoided, and the oil resistance, the ozone resistance, the chemical corrosion resistance and the weather resistance of the ACM resin are improved;
the density of the lateral group of the hydroxyethyl methacrylate and the modified nano silicon dioxide is increased, so that the low temperature resistance and the fluidity of the ACM resin are improved; the molecular structure of the ACM resin is more compact by grafting by using hydroxyethyl methacrylate and then adding modified nano silicon dioxide for bonding, so that the oil resistance, ozone resistance, chemical corrosion resistance and weather resistance are improved.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for preparing an impact modifier ACM resin, comprising the steps of: preparing seed latex, primary grafting, secondary grafting and post-treatment;
the preparation method comprises the steps of preparing seed latex, adding ethyl acrylate, allyl methacrylate, a nanoemulsifier and deionized water into a reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 40-50 ℃, stirring, and using 60 Carrying out irradiation by a Co irradiation source, and obtaining seed latex after the irradiation is finished;
adding seed latex, a nanoemulsion, ethyl acrylate, allyl methacrylate and deionized water into a reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 60-70 ℃, stirring, and using 60 Carrying out irradiation by a Co irradiation source, and obtaining a primary graft after the irradiation is finished;
the secondary grafting is carried out by adding primary graft, first part of nano-emulsifier, methyl ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate and deionized water into reactor, sealing reactor, replacing air in reactor with nitrogen, controlling temperature of reactor to 70-80 degree, stirring, and using 60 Carrying out primary irradiation by Co irradiation source, then adding a second part of nanoemulsion and modified nano silicon dioxide, and continuing to use 60 Carrying out secondary irradiation by a Co irradiation source, and obtaining a secondary graft after the secondary irradiation is finished;
the preparation method of the nanoemulsion comprises the following steps: preparing hydrophilic nano zinc oxide and grafting;
the preparation method comprises the steps of preparing hydrophilic nano zinc oxide, adding zinc acetate dihydrate and absolute ethyl alcohol into a reaction kettle, controlling the temperature of the reaction kettle to 30-50 ℃, and stirring to obtain an ethanol solution of zinc acetate; adding sodium hydroxide and absolute ethyl alcohol into a reaction kettle, controlling the temperature of the reaction kettle to 30-50 ℃, and stirring to obtain an ethanol solution of sodium hydroxide; adding an ethanol solution of zinc acetate and an ethanol solution of sodium hydroxide into a reaction kettle, controlling the temperature of the reaction kettle to be 30-50 ℃, stirring, adding a sodium citrate aqueous solution, continuously stirring, increasing the temperature of the reaction kettle to be 120-130 ℃, stirring, centrifuging, cleaning and drying a precipitate to obtain hydrophilic nano zinc oxide;
the grafting is carried out, after the hydrophilic nano zinc oxide and absolute ethyl alcohol are mixed, ultrasonic oscillation is carried out, and the ultrasonic oscillation is finished to obtain zinc oxide dispersion liquid; adding zinc oxide dispersion into a reaction kettle, controlling the temperature of the reaction kettle to 60-65 ℃, then adding isopropyl tri (dioctyl pyrophosphoryloxy) titanate into the reaction kettle, stirring, dropwise adding 1-bromo-n-dodecane, adding diethylaminoethyl methacrylate after the dropwise adding is finished, continuing stirring, centrifuging, cleaning and drying the precipitate to obtain the nanoemulsion.
2. The method for preparing an impact modifier ACM resin according to claim 1, wherein the mass ratio of ethyl acrylate, allyl methacrylate, nanoemulsifier, deionized water in the seed latex is 70-80:1-1.5:2-2.5:250-280;
the irradiation time is 5-6h, and the total irradiation dose is 50-60KGy.
3. The method for preparing an impact modifier ACM resin according to claim 1, wherein in the one grafting, the mass ratio of seed latex, nanoemulsifier, ethyl acrylate, allyl methacrylate, deionized water is 50-55:2-2.5:150-160:1.6-1.8:150-170;
the irradiation time is 3-4h, and the total irradiation dose is 30-40KGy.
4. The method for preparing an impact modifier ACM resin according to claim 1, wherein in the secondary grafting, the mass ratio of the primary graft, the first part of nanoemulsion, ethyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, deionized water, the second part of nanoemulsion, and modified nano-silica is 200-220:1-1.5:8-9:0.8-1:1.5-2:30-40:0.4-0.5:1.4-1.5;
the primary irradiation time is 2-2.5h, and the total primary irradiation dose is 20-25KGy;
the secondary irradiation time is 1.5-2h, and the total secondary irradiation dose is 15-20KGy.
5. The method for preparing the impact modifier ACM resin according to claim 1, wherein the preparation method of the modified nano silicon dioxide is characterized in that gamma-methacryloxypropyl trimethoxy silane, glacial acetic acid, nano silicon dioxide, deionized water and absolute ethyl alcohol are added into a reaction kettle, the reaction kettle is closed, nitrogen is used for replacing air in the reaction kettle, then the temperature of the reaction kettle is controlled to 65-70 ℃, stirring, centrifuging, controlling centrifuging, cleaning and drying sediment to obtain the modified nano silicon dioxide;
in the preparation of the modified nano silicon dioxide, the mass ratio of the gamma-methacryloxypropyl trimethoxy silane to the glacial acetic acid to the nano silicon dioxide to the deionized water to the absolute ethyl alcohol is 9-10:0.5-0.6:100-110:200-220:120-150;
the particle size of the nano silicon dioxide is 20-30nm.
6. The method for preparing an impact modifier ACM resin according to claim 1, wherein in the preparation of the hydrophilic nano zinc oxide, a mass ratio of zinc acetate dihydrate to absolute ethanol in the ethanol solution of zinc acetate is 18-20:4000-4200;
the mass ratio of the sodium hydroxide to the absolute ethyl alcohol in the ethanol solution of the sodium hydroxide is 0.9-1:4000-4200;
the mass ratio of the zinc acetate dihydrate in the ethanol solution of the zinc acetate to the sodium hydroxide in the ethanol solution of the sodium hydroxide to the sodium citrate aqueous solution is 18-20:0.9-1:20-25;
the preparation method of the sodium citrate aqueous solution comprises the steps of adding sodium citrate dihydrate and deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 30-50 ℃, and stirring to obtain the sodium citrate aqueous solution;
in the preparation of the sodium citrate aqueous solution, the mass ratio of the sodium citrate dihydrate to the deionized water is 0.45-0.5:20-25.
7. The method for preparing an impact modifier ACM resin according to claim 1, wherein in the grafting, the mass ratio of hydrophilic nano zinc oxide, absolute ethyl alcohol, isopropyl tri (dioctyl pyrophosphoryloxy) titanate, 1-bromo-n-dodecane, diethylaminoethyl methacrylate is 5-5.5:200-250:0.4-0.5:4-4.2:0.4-0.5;
the dropping speed of the 1-bromo-n-dodecane is 0.8-1g/min;
the frequency of the ultrasonic oscillation is 20-30KHz, and the time is 40-60min.
8. The method for preparing an impact modifier ACM resin according to claim 1, wherein the post-treatment comprises demulsification, centrifugation, washing and drying of the secondary grafts to obtain the impact modifier ACM resin.
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