CN117510737A - ASA rubber powder, preparation method thereof and high-gloss ASA resin - Google Patents

ASA rubber powder, preparation method thereof and high-gloss ASA resin Download PDF

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CN117510737A
CN117510737A CN202311461790.9A CN202311461790A CN117510737A CN 117510737 A CN117510737 A CN 117510737A CN 202311461790 A CN202311461790 A CN 202311461790A CN 117510737 A CN117510737 A CN 117510737A
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core
asa
emulsion
rubber powder
mixing
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林润雄
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Qingdao University of Science and Technology
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Qingdao University of Science and Technology
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    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

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  • 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 belongs to the technical field of high polymer materials ， In particular to ASA rubber powder, a preparation method thereof and high-gloss ASA resin. The invention provides ASA rubber powder, which comprises a core and a shell coated on the surface of the core; the core is butyl acrylate-methacrylic acid copolymer or butyl acrylate-acrylic acid copolymer; the shell is a styrene-acrylonitrile-methacrylic acid copolymer or a styrene-acrylonitrile-acrylic acid copolymer. The invention uses acrylic acid or methacrylic acidAs a comonomer, the gloss of the core and the shell is improved; acrylic acid or methacrylic acid is used as a stronger polar monomer, so that the polarity of an ASA rubber powder core is enhanced, and the compatibility between the core and the shell is further enhanced; in addition, the acrylic acid or the methacrylic acid is used as an acid, which is favorable for increasing agglomeration of the core layer latex particles and increasing the impact of the rubber particles to improve the ASA rubber powder.

Description

ASA rubber powder, preparation method thereof and high-gloss ASA resin
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to ASA rubber powder, a preparation method thereof and high-gloss ASA resin.
Background
The ASA rubber powder is a terpolymer with a core-shell structure, which is synthesized by emulsion polymerization by taking Butyl Acrylate (BA), styrene (St) and Acrylonitrile (AN) as main reaction raw materials. The commercial ASA resin was prepared by blending the core-shell terpolymer ASA with a styrene-acrylonitrile copolymer (SAN) in a certain ratio.
ABS is a widely used thermoplastic general engineering plastic, and has excellent low temperature resistance, chemical corrosion resistance, electrical property and mechanical property. However, the polybutadiene rubber in the ABS has C=C unsaturated double bonds, so that the ABS resin is easy to be oxidized and decomposed outdoors, the service performance of the ABS resin in the outdoor environment is limited, and the outdoor service life is reduced. The ASA resin has a similar structure and morphology to ABS resin, but compared with ABS resin, the ASA resin uses polybutyl acrylate (BA) rubber instead of polybutadiene (BD) rubber in ABS resin, and does not have an unsaturated double bond of polybutadiene in a molecular chain of the ASA resin, so that the ASA resin has more excellent weather resistance than ABS resin, and thus the ASA resin can be used outdoors for a long period of time.
However, it is not enough that some ASA resins used in the fields of automobiles, electronic products, etc. have only excellent weather resistance, and good gloss and impact properties are also required. The existing method for improving the glossiness of ASA resin is to blend ASA with PMMA, but the method has limited improvement on the glossiness of the ASA resin, can reduce the impact resistance of the material, and limits the application of the ASA resin in the fields of automobiles, electronic products and the like. Therefore, finding an ASA resin material with good impact and glossiness is a problem to be solved in industry.
Disclosure of Invention
In view of the above, the invention provides a high-gloss ASA rubber powder and a preparation method thereof, wherein acrylic acid or methacrylic acid monomer is added in the preparation process of the ASA rubber powder to increase ASA high-gloss, and meanwhile, the addition of acrylic acid or methacrylic acid monomer is beneficial to the agglomeration and enlargement of core layer emulsion particles, increase of rubber particles and improve impact property.
In order to solve the technical problems, the invention provides ASA rubber powder, which comprises a core and a shell coated on the surface of the core, wherein the core is butyl acrylate-methacrylic acid copolymer or butyl acrylate-acrylic acid copolymer, and the shell is styrene-acrylonitrile-methacrylic acid copolymer or styrene-acrylonitrile-acrylic acid copolymer.
Preferably, the mass ratio of the core to the shell is 30-70:30-70.
The invention also provides a preparation method of the ASA rubber powder, which comprises the following steps:
first mixing butyl acrylate, a first acrylic compound, a cross-linking agent, a grafting agent, a first emulsifying agent, a first initiator, a chain transfer agent and water for first emulsion polymerization to obtain core latex; the effective component of the core latex is butyl acrylate-acrylic acid compound copolymer; the first acrylic compound is methacrylic acid or acrylic acid;
performing second emulsion polymerization on the core latex, styrene, acrylonitrile, a second acrylic compound, a second emulsifier, a molecular weight regulator, a second initiator, an oxidation-reduction initiation system activating component and water in a second mixing way to obtain ASA rubber powder; the second acrylic compound is methacrylic acid or acrylic acid.
Preferably, the first emulsion polymerization comprises the steps of:
mixing part of butyl acrylate, part of first acrylic acid compound, part of cross-linking agent, part of grafting agent, part of first emulsifying agent, part of first initiator, part of chain transfer agent and part of water for seed polymerization to obtain seed emulsion;
mixing the residual butyl acrylate, the residual first acrylic acid compound, the residual crosslinking agent, the residual grafting agent, the residual first emulsifying agent, the residual first initiator, the residual chain transfer agent and the residual water to obtain a first pre-emulsion;
and adding the first pre-emulsion into the seed emulsion to perform emulsion core polymerization to obtain core latex.
Preferably, the solid content of the core latex is 32-48%; the core latex particle size is greater than 300nm.
Preferably, the first emulsion polymerization comprises the following components in parts by weight:
the first emulsion polymerization reaction temperature is 69-71 ℃ and the time is 12-17 h.
Preferably, the second mixing comprises the steps of:
thirdly mixing styrene, acrylonitrile, a second acrylic compound, a second emulsifier, a molecular weight regulator, a second initiator, an oxidation-reduction initiation system activation component and water to obtain a second pre-emulsion;
fourth mixing the second pre-emulsion with the core latex.
Preferably, the second emulsion polymerization comprises the following components in parts by weight:
preferably, the second emulsion polymerization reaction temperature is 64-66 ℃ and the time is 5-7 h.
The invention also provides a high-gloss ASA resin, which comprises ASA rubber powder and a styrene-acrylonitrile copolymer, wherein the mass ratio of the styrene-acrylonitrile copolymer to the ASA rubber powder is 65-80:20-35;
the ASA rubber powder is prepared by the ASA rubber powder according to the technical scheme or the preparation method according to the technical scheme.
The invention provides ASA rubber powder, which comprises a core and a shell coated on the surface of the core, wherein the core is butyl acrylate-methacrylic acid copolymer or butyl acrylate-acrylic acid copolymer, and the shell is styrene-acrylonitrile-methacrylic acid copolymer or styrene-acrylonitrile-acrylic acid copolymer. Acrylic acid or methacrylic acid is used as a comonomer, so that the glossiness of the core and the shell is improved; meanwhile, acrylic acid or methacrylic acid is used as a stronger polar monomer, so that the polarity of an ASA rubber powder core is enhanced, and the compatibility of the core and the shell is further enhanced; in addition, the acrylic acid or the methacrylic acid is used as an acid, which is favorable for the agglomeration and enlargement of the latex particles of the nuclear layer, increases the rubber particles and improves the impact property of the ASA rubber powder.
Drawings
FIG. 1 is a particle size distribution diagram of the core latex 1 of example 1;
FIG. 2 is a particle size distribution diagram of the core latex 2 of example 2;
FIG. 3 is a particle size distribution diagram of the core latex 3 in comparative example 1.
Detailed Description
The invention provides ASA rubber powder, which comprises a core and a shell coated on the surface of the core, wherein the core is butyl acrylate-methacrylic acid copolymer or butyl acrylate-acrylic acid copolymer, and the shell is styrene-acrylonitrile-methacrylic acid copolymer or styrene-acrylonitrile-acrylic acid copolymer.
In the present invention, the mass ratio of the core to the shell is preferably 30 to 70:30 to 70, more preferably 60:40.
The invention provides a preparation method of ASA rubber powder, which comprises the following steps:
first mixing butyl acrylate, a first acrylic compound, a cross-linking agent, a grafting agent, a first emulsifying agent, a first initiator, a chain transfer agent and water for first emulsion polymerization to obtain core latex; the first acrylic compound is methacrylic acid or acrylic acid;
performing second emulsion polymerization on the core latex, styrene, acrylonitrile, a second acrylic compound, a second emulsifier, a molecular weight regulator, a second initiator, an oxidation-reduction initiation system activating component and water in a second mixing way to obtain ASA rubber powder; the second acrylic compound is methacrylic acid or acrylic acid.
The invention carries out first emulsion polymerization on first mixture of butyl acrylate, a first acrylic compound, a cross-linking agent, a grafting agent, a first emulsifying agent, a first initiator, a chain transfer agent and water to obtain core latex. In the present invention, the first acrylic compound is methacrylic acid or acrylic acid, preferably methacrylic acid. In the present invention, the crosslinking agent preferably includes one or more of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, 1, 3-propanediol diacrylate, etc., more preferably 1, 6-hexanediol diacrylate.
In the present invention, the grafting agent preferably includes allyl methacrylate.
In the present invention, the first emulsifier is preferably an anionic emulsifier; the anionic emulsifier preferably comprises one or more of rosin soap, stearic acid soap, oleic acid soap, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and more preferably sodium dodecyl sulfate. In the present invention, when the anionic emulsifier includes two or more of the above specific substances, the present invention has no particular requirement on the ratio of the amounts of the specific substances.
In the present invention, the first initiator is preferably a persulfate; the persulfate preferably includes one or more of potassium persulfate and ammonium persulfate, and more preferably potassium persulfate.
In the present invention, the ASA latex polymerization chain transfer agent preferably comprises dodecyl mercaptan.
In the present invention, the butyl acrylate, the first acrylic compound, is a first emulsion polymerized monomer.
In the invention, the mass parts of the material components in the first emulsion polymerization are preferably as follows: 20 to 41 parts of butyl acrylate, 0.5 to 5 parts of acrylic compound, 0.1 to 1.0 part of cross-linking agent, 0.1 to 1.0 part of grafting agent, 0.3 to 2 parts of first emulsifying agent, 0.1 to 1.0 part of first initiator, 0.1 to 0.8 part of chain transfer agent, 50 to 75 parts of water, more preferably 35 to 41 parts of butyl acrylate, 1 to 2 parts of acrylic compound, 0.2 to 0.5 part of cross-linking agent, 0.2 to 0.5 part of grafting agent, 0.5 to 1 part of first emulsifying agent, 0.2 to 0.5 part of first initiator, 0.1 to 0.3 part of chain transfer agent and 55 to 62 parts of water.
In the present invention, the core latex is an effective component of butyl acrylate-acrylic acid compound copolymer. In the present invention, the solid content of the core latex is preferably 32 to 48%, more preferably 38%. In the present invention, the core latex particle diameter is preferably greater than 300nm, more preferably 350 to 450nm. The invention limits the particle size of the core latex to increase the toughening capacity of the core, thereby enhancing the impact of ASA rubber powder. The invention has no special requirement on the mixing, so long as the mixing can be uniform. In the present invention, the first emulsion polymerization preferably comprises the steps of:
mixing part of butyl acrylate, part of first acrylic acid compound, part of cross-linking agent, part of grafting agent, part of first emulsifying agent, part of first initiator, part of chain transfer agent and part of water for seed polymerization to obtain seed emulsion;
sixth mixing residual butyl acrylate, residual first acrylic acid compound, residual cross-linking agent, residual grafting agent, residual first emulsifying agent, residual first initiator, residual chain transfer agent and residual water to obtain a first pre-emulsion;
and adding the first pre-emulsified liquid into the seed emulsion to carry out emulsion nuclear polymerization to obtain nuclear latex.
According to the invention, a part of butyl acrylate, a part of first acrylic compound, a part of cross-linking agent, a part of grafting agent, a part of first emulsifying agent, a part of first initiator, a part of chain transfer agent and a part of water are subjected to fifth mixing for seed polymerization, so that seed emulsion is obtained. In the present invention, the fifth mixing preferably includes the steps of:
seventh mixing part of water, part of the first emulsifier and part of the first initiator to obtain a first mixed solution;
and eighth mixing the first mixed solution, part of butyl acrylate, part of the first acrylic acid compound, part of the cross-linking agent, part of the grafting agent and part of the chain transfer agent.
The seventh mixing mode and the eighth mixing mode are not particularly required, and the seventh mixing mode and the eighth mixing mode can be uniformly mixed.
In the present invention, the seed polymerization time is preferably 1 to 2 hours; the seed polymerization temperature is preferably 69-71 ℃, more preferably 70 ℃; the seed polymerization is preferably carried out in a polymerization vessel. In the present invention, the seed polymerization is preferably performed under an inert atmosphere. In the present invention, the inert atmosphere preferably includes argon, nitrogen, more preferably nitrogen.
According to the invention, residual butyl acrylate, residual first acrylic compound, residual cross-linking agent, residual grafting agent, residual first emulsifying agent, residual first initiator, residual chain transfer agent and residual water are mixed in a sixth mode to obtain a first pre-emulsion. In the present invention, the sixth mixing preferably includes the steps of:
mixing the rest water, the rest first emulsifier and the rest first initiator for the ninth time to obtain a second mixed solution;
and mixing the second mixed solution with the rest of butyl acrylate, the rest of the first acrylic compound, the rest of the cross-linking agent, the rest of the grafting agent and the rest of the chain transfer agent in a tenth way to obtain a first pre-emulsion.
In the present invention, the ninth mixing is preferably performed under stirring, and the rotation speed of the stirring is not particularly limited as long as the stirring can be uniformly performed. In the present invention, the tenth mixing is preferably performed under stirring, and the stirring speed is preferably 800 to 2000r/min, more preferably 1000 to 1500r/min. In the present invention, it is preferable that the stirring speed of the tenth mixing is in the above range so that the first pre-emulsion is uniformly emulsified.
After the seed emulsion and the first pre-emulsion are obtained, the first pre-emulsion is dripped into the seed emulsion to carry out emulsion nuclear polymerization, so as to obtain the nuclear latex. The present invention preferably provides that the first emulsion polymerization is capable of increasing the particle size of the core latex in the above step. In the present invention, the mass ratio of the first pre-emulsion to the seed emulsion is preferably 5 to 25:75 to 95, more preferably 7 to 15:85 to 93. In the present invention, the dropping temperature is preferably 69 to 71 ℃, more preferably 70 ℃, and the dropping rate is preferably 1.2 to 1.8g/min, more preferably 1.35 to 1.55g/min. In the present invention, the dropping is preferably performed under an inert atmosphere. In the present invention, the inert atmosphere preferably includes argon, nitrogen, more preferably nitrogen.
In the present invention, the emulsion core polymerization time is preferably 13 to 15, more preferably 13 hours, and the emulsion core polymerization temperature is preferably 69 to 71 ℃, more preferably 70 ℃. The time for the emulsion core polymerization was calculated from the start of the drop of the first pre-emulsion.
In the present invention, the first emulsion polymerization temperature is preferably 69 to 71 ℃, more preferably 70 ℃; the first emulsion polymerization time is preferably 12 to 17 hours, more preferably 15 to 16 hours.
After the core latex is obtained, the invention carries out second emulsion polymerization on the core latex, styrene, acrylonitrile, a second acrylic compound, a second emulsifier, a molecular weight regulator, a second initiator, an oxidation-reduction initiation system activating component and water by second mixing, thus obtaining the ASA rubber powder. In the present invention, the second acrylic compound is methacrylic acid or acrylic acid, preferably methacrylic acid. In the present invention, the second emulsifier is preferably an anionic emulsifier; the anionic emulsifier preferably comprises one or more of rosin soap, stearic acid soap, oleic acid soap, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and the like, and more preferably sodium dodecyl sulfate.
In the present invention, the molecular weight regulator preferably includes dodecyl mercaptan.
In the present invention, the second initiator preferably includes a hydrogen peroxide-based initiator, and more preferably cumene hydroperoxide.
In the present invention, the oxidation-reduction initiation system activating component preferably includes sodium pyrophosphate, glucose and ferrous sulfate. In the present invention, the mass ratio of sodium pyrophosphate, glucose and ferrous sulfate is preferably 1 to 50:2 to 100:0.01 to 1, more preferably 1:2 to 3:0.01 to 0.05.
In the present invention, the styrene, acrylonitrile, and the second acrylic compound are the second emulsion polymerized monomers.
In the invention, the mass parts of the components of the materials in the second emulsion polymerization are preferably as follows: 15 to 35 parts of butyl acrylate-acrylic acid compound copolymer, 5 to 20 parts of styrene, 1 to 8 parts of acrylonitrile, 0.2 to 1.5 parts of acrylic acid compound, 0.05 to 1 part of second emulsifier, 0.01 to 0.8 part of molecular weight regulator, 0.01 to 0.8 part of second initiator, 0.03 to 1.5 parts of active component of redox system and 32 to 75 parts of water; more preferably 20 to 25 parts of butyl acrylate-acrylic acid compound copolymer, 10 to 15 parts of styrene, 2 to 5 parts of acrylonitrile, 0.3 to 0.6 part of acrylic acid compound, 0.05 to 0.5 part of second emulsifier, 0.1 to 0.5 part of molecular weight regulator, 0.1 to 0.5 part of second initiator, 0.2 to 0.5 part of redox system active component and 55 to 62 parts of water.
In the present invention, the second mixing preferably includes the steps of:
thirdly mixing styrene, acrylonitrile, a second acrylic compound, a second emulsifier, a molecular weight regulator, a second initiator, an oxidation-reduction initiation system activation component and water to obtain a second pre-emulsion;
fourth mixing the second pre-emulsion with the core latex.
The invention mixes the styrene, the acrylonitrile, the second acrylic compound, the second emulsifier, the molecular weight regulator, the second initiator, the oxidation-reduction initiation system activating component and the water for the third time to obtain the second pre-emulsion. The third mixing preferably comprises the steps of:
mixing water with a second emulsifier eleventh to obtain a third mixed solution;
the third mixed solution is mixed with the active component of the oxidation-reduction initiation system in a twelfth way to obtain a fourth mixed solution;
and mixing the fourth mixed solution with styrene, acrylonitrile, a second acrylic compound, a molecular weight regulator and a second initiator thirteenth to obtain a second pre-emulsion. In the present invention, the eleventh mixing is preferably performed under stirring, and the rotation speed of the stirring is not particularly limited as long as the stirring can be uniformly performed. In the present invention, the twelfth mixing is preferably performed under stirring, and the rotation speed of the stirring is not particularly limited as long as the stirring can be uniformly performed. In the present invention, the thirteenth mixing is preferably performed under stirring at a rotation speed of preferably 1000 to 2000r/min, more preferably 1300 to 1800r/min. In the present invention, the stirring speed of the thirteenth mixture is preferably in the above range so that the second pre-emulsion is uniformly emulsified.
After the second pre-emulsion is obtained, the present invention fourth mixes the second pre-emulsion with the core latex. In the present invention, the fourth mixing is preferably the dropping of the second pre-emulsified liquid into the core latex. In the present invention, the dropping rate is preferably 1.8 to 2.8g/min, more preferably 2.0 to 2.5g/min. In the present invention, the fourth mixing is preferably carried out in a polymerizer. The time for the emulsion core polymerization was calculated from the start of the drop of the first pre-emulsion. In the invention, the reaction is continued for 1-2 h after the dripping is completed. In the present invention, the dropping temperature is 64 to 66 ℃, more preferably 65 ℃.
In the present invention, the fourth mixing is preferably performed under an inert atmosphere. In the present invention, the inert atmosphere preferably includes argon, nitrogen, more preferably nitrogen.
In the present invention, the second emulsion polymerization temperature is preferably 64 to 66 ℃, more preferably 65 ℃; the second emulsion polymerization time is preferably 5 to 7 hours, more preferably 6 to 7.
In the invention, the second emulsion polymerization preferably further comprises the steps of diluting the second emulsion polymerization system, mixing with an antioxidant, and sequentially condensing and drying to obtain ASA rubber powder. In the present invention, the solid content after dilution is preferably 20% to 30%, more preferably 25%. In the present invention, the antioxidant is preferably an antioxidant 1067. In the present invention, the temperature of the dilution is preferably 78 to 82 ℃, more preferably 80 ℃; the temperature of the mixing is preferably 78 to 82 ℃, more preferably 80 ℃. In the present invention, the coagulation is preferably performed by adding a magnesium sulfate solution to the mixed system under stirring. The mass concentration of the magnesium sulfate solution is not limited in the present invention, but in the embodiment of the present invention, the mass concentration of the magnesium sulfate solution is preferably 15 to 25%, more preferably 20%. The coagulation time is not particularly limited as long as the polymer can be completely coagulated. The rotational speed of the stirring is not particularly limited in the present invention. In the present invention, the post-coagulation preferably further comprises washing the post-coagulation product. In the present invention, the washing solvent is preferably water, and the water is preferably deionized water. In the present invention, the washing is preferably performed until the pH of the washing solution after washing is 6 to 7. In the present invention, the drying is preferably a drying, and the temperature of the drying is preferably 75 to 85 ℃, more preferably 80 ℃. The drying time is preferably 2 to 5 hours, more preferably 3 to 4 hours.
The invention also provides a high-gloss ASA resin, which comprises ASA rubber powder and a styrene-acrylonitrile copolymer, wherein the mass ratio of the styrene-acrylonitrile copolymer to the ASA rubber powder is 65-80:20-35, preferably 65-75:25-35, and more preferably 70:30.
The ASA rubber powder is prepared by the ASA rubber powder according to the technical scheme or the preparation method according to the technical scheme.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Under nitrogen atmosphere, adding 500g of deionized water, 0.8g of sodium dodecyl sulfate and 0.5g of potassium persulfate into a 2000mL polymerization kettle, and uniformly stirring; 53.35g of butyl acrylate, 1.65g of methacrylic acid, 0.4g of 1, 6-hexanediol diacrylate, 0.4g of allyl methacrylate and 0.2g of dodecyl mercaptan are added, the mixture is stirred uniformly, and the temperature is raised to 70 ℃ for seed polymerization reaction for 2 hours, so as to obtain seed emulsion 1;
360g of deionized water, 7.45g of sodium dodecyl sulfate and 3.9g of potassium persulfate are added into a pre-emulsification kettle and stirred uniformly; 480.15g of butyl acrylate, 14.85g of methacrylic acid, 3.9g of 1, 6-hexanediol diacrylate, 4.5g of allyl methacrylate and 2.55g of dodecyl mercaptan are added, and stirred at a speed of 1200r/min, and the mixture is emulsified uniformly to obtain a first pre-emulsion 1;
dropwise adding the prepared first pre-emulsion 1 into the seed emulsion 1 at the dropwise adding rate of 1.4547g/min under the nitrogen atmosphere, and reacting for 3 hours at 70 ℃ after the dropwise adding to obtain the core latex 1 with the solid content of 38%;
adding 300g of deionized water, 1.12g of sodium dodecyl sulfate into a pre-emulsifying kettle, uniformly stirring, adding 1.12g of sodium pyrophosphate, 2.464g of anhydrous glucose and 0.0224g of ferrous sulfate, uniformly stirring, adding 162.96g of styrene, 54.32g of acrylonitrile, 6.72g of methacrylic acid, 2.24g of dodecyl mercaptan and 2.24g of cumene hydroperoxide, stirring at a rotating speed of 1500r/min, and uniformly emulsifying to obtain a second pre-emulsion 1;
884g of core latex 1 is added into a 2000mL polymerization kettle, the temperature is raised to 65 ℃, the second pre-emulsion 1 is dropwise added into the polymerization kettle at the dropwise adding rate of 2.2217g/min in the nitrogen atmosphere for 4 hours, and then the reaction is continued for 2 hours at 65 ℃ under the nitrogen atmosphere; diluting the emulsion obtained by the reaction to a solid content of 25%, and adding 2.8g of antioxidant 1067 at 80 ℃; gradually adding 40g of 20% magnesium sulfate solution under stirring until the polymer is completely coagulated; washing the coagulated product with deionized water until the pH value of the washing liquid is 7, and drying in an oven at 80 ℃ to obtain ASA-1.
Example 2
Under nitrogen atmosphere, adding 500g of deionized water, 0.8g of sodium dodecyl sulfate and 0.5g of potassium persulfate into a 2000mL polymerization kettle, and uniformly stirring; 51.7g of butyl acrylate, 3.3g of methacrylic acid, 0.4g of 1, 6-hexanediol diacrylate, 0.4g of allyl methacrylate and 0.2g of dodecyl mercaptan are added, the mixture is stirred uniformly, and the temperature is raised to 70 ℃ for seed polymerization reaction for 2 hours, so as to obtain seed emulsion 2;
360g of deionized water, 7.45g of sodium dodecyl sulfate and 3.9g of potassium persulfate are added into a pre-emulsification kettle and stirred uniformly; 465.3g of butyl acrylate, 29.7g of methacrylic acid, 3.9g of 1, 6-hexanediol diacrylate, 4.5g of allyl methacrylate and 2.55g of dodecyl mercaptan are added, stirred at a speed of 1200r/min and emulsified uniformly to obtain a first pre-emulsion 2;
dropwise adding the prepared first pre-emulsion 2 into the seed emulsion 2 at the dropwise adding rate of 1.4547g/min under the nitrogen atmosphere, and reacting for 3 hours at 70 ℃ after the dropwise adding to obtain the core latex 2 with the solid content of 38%;
adding 300g of deionized water, 1.12g of sodium dodecyl sulfate into a pre-emulsifying kettle, uniformly stirring, adding 1.12g of sodium pyrophosphate, 2.464g of anhydrous glucose and 0.0224g of ferrous sulfate, uniformly stirring, adding 157.92g of styrene, 52.64g of acrylonitrile, 13.44g of methacrylic acid, 2.24g of dodecyl mercaptan and 2.24g of cumene hydroperoxide, stirring at a rotating speed of 1500r/min, and uniformly emulsifying to obtain a second pre-emulsion 2;
884g of nuclear latex 2 with the solid content of 38% is added into a 2000mL polymerization kettle, the temperature is raised to 65 ℃, the second pre-emulsion 2 is dropwise added into the polymerization kettle at the dropwise adding rate of 2.2217g/min in the nitrogen atmosphere for 4 hours, and then the reaction is continued for 2 hours at 65 ℃ under the nitrogen atmosphere; diluting the emulsion obtained by the reaction to a solid content of 25%, and adding 2.8g of antioxidant 1067 at 80 ℃; gradually adding 40g of 20% magnesium sulfate solution under stirring until the polymer is completely coagulated; washing the coagulated product with deionized water until the pH value of the washing liquid is 7, and drying in an oven at 80 ℃ to obtain ASA-2.
Comparative example 1
Under nitrogen atmosphere, adding 500g of deionized water, 0.8g of sodium dodecyl sulfate and 0.5g of potassium persulfate into a 2000mL polymerization kettle, and uniformly stirring; 55g of butyl acrylate, 0.4g of 1, 6-hexanediol diacrylate and 0.2g of dodecyl mercaptan are added, the mixture is stirred uniformly, and the temperature is raised to 70 ℃ for seed polymerization reaction for 2 hours, so as to obtain seed emulsion 3;
360g of deionized water, 7.45g of sodium dodecyl sulfate and 3.9g of potassium persulfate are added into a pre-emulsification kettle and stirred uniformly; 495g of butyl acrylate, 3.9g of 1, 6-hexanediol diacrylate and 2.55g of dodecyl mercaptan are added, and the mixture is stirred at a rotating speed of 1200r/min and is emulsified uniformly to obtain a first pre-emulsion 3;
dropwise adding the prepared first pre-emulsion 3 into the seed emulsion 3 at the dropwise adding rate of 1.4547g/min under the nitrogen atmosphere, and reacting for 3 hours at 70 ℃ after the dropwise adding to obtain the core latex 3 with the solid content of 38%;
adding 300g of deionized water, 1.12g of sodium dodecyl sulfate into a pre-emulsifying kettle, uniformly stirring, adding 1.12g of sodium pyrophosphate, 2.464g of anhydrous glucose and 0.0224g of ferrous sulfate, uniformly stirring, adding 168g of styrene, 56g of acrylonitrile, 2.24g of dodecathiol and 2.24g of cumene hydroperoxide, and uniformly emulsifying to obtain a second pre-emulsion 3;
884g of nuclear latex 3 with the solid content of 38% is added into a 2000mL polymerization kettle, the temperature is raised to 65 ℃, the second pre-emulsion 3 is dropwise added into the polymerization kettle at the dropwise adding rate of 2.2217g/min in the nitrogen atmosphere for 4 hours, and then the reaction is continued for 2 hours at 65 ℃ under the nitrogen atmosphere; diluting the emulsion obtained by the reaction to a solid content of 25%, and adding 2.8g of antioxidant 1067 at 80 ℃; gradually adding 40g of 20% magnesium sulfate solution under stirring until the polymer is completely coagulated; washing the coagulated product with deionized water until the pH value of the washing liquid is 7, and drying in an oven at 80 ℃ to obtain ASA-3.
Comparative example 2
The core latex 3 in comparative example 1 was used as the core latex;
adding 300g of deionized water, 1.12g of sodium dodecyl sulfate into a pre-emulsifying kettle, uniformly stirring, adding 1.12g of sodium pyrophosphate, 2.464g of anhydrous glucose and 0.0224g of ferrous sulfate, uniformly stirring, adding 152.88g of styrene, 50.96g of acrylonitrile, 20.16g of methacrylic acid, 2.24g of dodecyl mercaptan and 2.24g of cumene hydroperoxide, stirring at a rotating speed of 1500r/min, and uniformly emulsifying to obtain a second pre-emulsion 4;
884g of nuclear latex 3 with the solid content of 38% is added into a 2000mL polymerization kettle, the temperature is raised to 65 ℃, the second pre-emulsion 4 is dropwise added into the polymerization kettle at the dropwise adding rate of 2.2217g/min in the nitrogen atmosphere, and then the reaction is continued for 2h at 65 ℃ under the nitrogen atmosphere; diluting the emulsion obtained by the reaction to a solid content of 25%, and adding 2.8g of antioxidant 1067 at 80 ℃; gradually adding 40g of 20% magnesium sulfate solution under stirring until the polymer is completely coagulated; washing the coagulated product with deionized water until the pH value of the washing liquid is 7, and drying in an oven at 80 ℃ to obtain ASA-4.
Test case
SAN and ASA-1 to ASA-4 are respectively and uniformly mixed according to the proportion of 70:30 (wt%) and added into a main feeder of a double-screw extruder, and after extrusion, water cooling and granulation are carried out. The process conditions for twin screw extrusion are shown in table 1.
The injection molding machine prepares test bars for performance testing. The tensile strength of ASA rubber powders prepared in examples 1-2 and comparative examples 1-2 is tested according to GB/T1040.2-2006; the ASA rubber powders prepared in examples 1-2 and comparative examples 1-2 were tested for bending properties according to GB/T9341-2008; the impact strength of ASA rubber powders prepared in examples 1-2 and comparative examples 1-2 was measured according to GB/T1043.1-2008; determining the gloss of ASA rubber powders prepared in examples 1-2 and comparative examples 1-2 according to D523; carrying out tensile and bending tests on ASA rubber powder prepared in examples 1-2 and comparative examples 1-2 by using a high-speed rail detection company universal tester GT-TCS-2000; measuring the melt index of the ASA rubber powder prepared in the examples 1-2 and the comparative examples 1-2 by using a high-speed rail detection company melt flow rate tester GT-7100-MI; the notch impact strength of the ASA rubber powder prepared in examples 1-2 and comparative examples 1-2 is measured by using a cantilever beam impact tester GT-HV2000A-C6W of a high-speed rail detection company; the Vicat softening points of ASA rubber powders prepared in examples 1-2 and comparative examples 1-2 were measured by using a Vicat deformation tester GTHV2000A-C5W of high-speed rail detection company. The results are shown in Table 2.
TABLE 1 Process conditions for twin screw extrusion
Table 2ASA performance test table
The mass percentages of the methacrylic acid in the cores of ASA-1 to ASA-4 are calculated according to the formula 1 and the mass percentages of the methacrylic acid in the shells of ASA-1 to ASA-4 are calculated according to the formula 2, and the results are as follows: ASA-1, core 3%, shell 3%; ASA-2, 6% of core and 6% of shell; ASA-3, core 0%, shell 0%; ASA-4, core 0%, shell 9%.
Wherein S is 1 Is the mass percent of the first acrylic compound in the core, W 1 W is the mass of the first acrylic compound 2 The mass of the butyl acrylate is the mass of the butyl acrylate;
wherein S is 2 Is the mass percent of the second acrylic compound in the shell, m 1 Is the mass of the second acrylic compound, m 2 Mass of styrene, m 3 Is the mass of acrylonitrile.
As can be seen from the data in Table 2, ASA-1, ASA-2 and ASA-4 contained methacrylic acid in the core and/or shell, and no methacrylic acid in either the ASA-3 core or shell. ASA-1, ASA-2, ASA-4 have higher gloss than ASA-3, so that the inclusion of methacrylic acid in the core and/or shell increases the gloss of the ASA resin; ASA-1, ASA-2 and ASA-4 with higher glossiness have no methacrylic acid in the core of ASA-4, have poor core-shell compatibility, lower impact property, lower melt index and poor processing property, and the core and the shell of ASA-1 and ASA-2 both contain a proper amount of methacrylic acid, have higher core-shell compatibility, higher impact property and glossiness, and have higher processing property.
As can be seen from the data in Table 2, the ASA resin provided by the invention has good impact property and glossiness, and also has good processability.
The particle size distribution diagrams of the core latices 1 to 3 prepared in examples 1 to 2 and comparative example 1 were determined using a laser particle sizer, zetasizer Nano ZS, malvern, UK, as shown in FIGS. 1 to 3.
As can be seen from FIGS. 1 to 3, the particle size of the core latex prepared by the present invention is greater than 300nm.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.

Claims (10)

1. An ASA rubber powder is characterized by comprising a core and a shell coated on the surface of the core;
the core is butyl acrylate-methacrylic acid copolymer or butyl acrylate-acrylic acid copolymer;
the shell is a styrene-acrylonitrile-methacrylic acid copolymer or a styrene-acrylonitrile-acrylic acid copolymer.
2. ASA powder according to claim 1, characterized in that the mass ratio of core to shell is 30-70:30-70.
3. The method for preparing the ASA rubber powder according to any one of claims 1 to 2, comprising the following steps:
first mixing butyl acrylate, a first acrylic compound, a cross-linking agent, a grafting agent, a first emulsifying agent, a first initiator, a chain transfer agent and water for first emulsion polymerization to obtain core latex; the effective component of the core latex is butyl acrylate-acrylic acid compound copolymer; the first acrylic compound is methacrylic acid or acrylic acid;
performing second emulsion polymerization on the core latex, styrene, acrylonitrile, a second acrylic compound, a second emulsifier, a molecular weight regulator, a second initiator, an oxidation-reduction initiation system activating component and water in a second mixing way to obtain ASA rubber powder; the second acrylic compound is methacrylic acid or acrylic acid.
4. A method of preparation according to claim 3, wherein the first emulsion polymerization comprises the steps of:
mixing part of butyl acrylate, part of first acrylic acid compound, part of cross-linking agent, part of grafting agent, part of first emulsifying agent, part of first initiator, part of chain transfer agent and part of water for seed polymerization to obtain seed emulsion;
mixing the residual butyl acrylate, the residual first acrylic acid compound, the residual crosslinking agent, the residual grafting agent, the residual first emulsifying agent, the residual first initiator, the residual chain transfer agent and the residual water to obtain a first pre-emulsion;
and adding the first pre-emulsion into the seed emulsion to perform emulsion core polymerization to obtain core latex.
5. The method according to claim 3 or 4, wherein the core latex has a solid content of 32 to 48%; the core latex particle size is greater than 300nm.
6. The preparation method according to claim 3 or 4, wherein the mass parts of the material components in the first emulsion polymerization are as follows:
the first emulsion polymerization reaction temperature is 69-71 ℃ and the time is 12-17 h.
7. A method of preparing according to claim 3, wherein the second mixing comprises the steps of:
thirdly mixing styrene, acrylonitrile, a second acrylic compound, a second emulsifier, a molecular weight regulator, a second initiator, an oxidation-reduction initiation system activation component and water to obtain a second pre-emulsion;
fourth mixing the second pre-emulsion with the core latex.
8. The preparation method according to claim 3 or 7, wherein the mass parts of the material components in the second emulsion polymerization are as follows:
9. the process according to claim 3, wherein the second emulsion polymerization is carried out at a temperature of 64 to 66℃for a period of 5 to 7 hours.
10. The high-gloss ASA resin is characterized by comprising ASA rubber powder and a styrene-acrylonitrile copolymer, wherein the mass ratio of the styrene-acrylonitrile copolymer to the ASA rubber powder is 65-80:20-35;
the ASA rubber powder is the ASA rubber powder of claim 1 or 2 or the ASA rubber powder prepared by the preparation method of any one of claims 3 to 9.
CN202311461790.9A 2023-11-06 2023-11-06 ASA rubber powder, preparation method thereof and high-gloss ASA resin Pending CN117510737A (en)

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