CN112724335B - Matte organic silicon high-impact-resistance toughening agent and preparation method thereof - Google Patents
Matte organic silicon high-impact-resistance toughening agent and preparation method thereof Download PDFInfo
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- 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
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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Abstract
The invention relates to the technical field of toughening modification of engineering plastics, in particular to a matte organic silicon high-impact toughening agent and a preparation method thereof, wherein organic polysiloxane nuclear emulsion and acrylate rubber emulsion are used as main raw materials, shell monomer mixed liquid and an initiator B are added for emulsion polymerization reaction to prepare matte emulsion, and the matte organic silicon high-impact toughening agent obtained by demulsification and drying has the characteristics of low glass transition temperature and low-temperature impact resistance of organic silicon rubber, high temperature resistance, weather aging resistance, oil resistance, easy processing and the like of acrylate rubber; and after the matte organic silicon high-impact toughening agent is added when AS resin is adopted to produce ASA resin, the surface of the ASA resin becomes rugged and rough microscopically, when light irradiates on the surface of an ASA resin material, one part of light is absorbed and refracted into the material, and the other part of light generates diffuse reflection on a rough interface of the resin and the rubber, so that a matte effect can be achieved.
Description
Technical Field
The invention relates to the technical field of engineering plastic toughening modification, in particular to a matte organic silicon high-impact toughening agent and a preparation method thereof.
Background
ASA resin and ABS resin are commonly used engineering plastics, and have excellent mechanical properties, processability, electrical insulation and chemical resistance. The product can be widely used in automobile decoration, instrument and meter, electronic and electrical equipment shell, building material, etc.
When the material is used as an automotive interior part, the molded part has high glossiness, and the surface of the molded part is easy to shine, so that the overall design is attractive. On the other hand, long-time reflection of light can cause visual fatigue and influence the driving experience. The low-gloss surface is obtained by processing modes such as extinction polishing, matte spraying, fabric coating and the like on the surface of an ASA (acrylonitrile-butadiene-styrene) part or an ABS (acrylonitrile-butadiene-styrene) part, but the process flow is greatly prolonged, the production cost is increased, and the product competitiveness is influenced. Therefore, it is an important development to reduce the gloss of the material and to omit the matting post-treatment process.
At present, common flatting agents are inorganic flatting agents and organic flatting agents, and patent CN107652605A discloses that an ASA low-gloss material is prepared by using the inorganic flatting agents, and the common flatting agents are high in adding amount of the flatting agents, large in processing difficulty and large in influence on impact performance of products.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a matte organic silicon high-impact toughening agent, the obtained matte organic silicon high-impact toughening agent, namely organic silicon modified polyacrylate-shell monomer copolymer, has good impact strength, not only has good extinction effect, but also additionally provides high-impact effect, and the matte organic silicon high-impact toughening agent can not generate great influence on other properties of materials when being applied to preparation of ASA resin or ABS resin modification; the preparation method has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
The invention also aims to provide the matte organic silicon high-impact-resistant toughening agent, which is applied to the preparation of ASA resin or ABS resin for modification, does not generate great influence on other properties of the material, has less consumption, and not only has good light-eliminating effect, but also additionally provides high-impact-resistant effect.
The purpose of the invention is realized by the following technical scheme: a preparation method of a matte organic silicon high-impact-resistant toughening agent comprises the following steps:
synthesis of organopolysiloxane core emulsion:
(S1) mixing an organic siloxane monomer and a silane coupling agent according to a weight ratio of 100:0.5-15, and obtaining organic silicon mixed liquor;
(S2) adding the organic silicon mixed solution into an aqueous solution mixed with a catalyst and an emulsifier A, shearing at a high speed of 8000-12000rpm for 5-20min by using a homogenizer, and reacting at the temperature of 85-100 ℃ for 6-12h to obtain the organopolysiloxane nuclear emulsion; wherein the total mass of the organosiloxane monomer is 20-60% of the mass of water, the mass of the catalyst is 1-5% of the mass of the organosiloxane monomer, and the mass of the emulsifier A is 1-20% of the mass of the organosiloxane monomer;
synthesizing an acrylate rubber emulsion:
(A1) Uniformly mixing 30-50 parts by weight of acrylate monomers and 0.15-2.5 parts by weight of cross-linking agent, adding into 30-50 parts by weight of 0.1-2wt% emulsifier B-water solution, and dispersing to obtain an acrylate mixed solution; uniformly mixing 0.03-0.5 part by weight of initiator A, 0.03-1 part by weight of emulsifier C and 30-50 parts by weight of water to obtain a diluted water solution;
(A2) Continuously stirring and keeping the temperature at 70-85 ℃, adding the acrylate mixed solution into the diluted aqueous solution, and reacting for 2-3h to obtain the acrylate rubber emulsion;
synthesizing a matte emulsion:
uniformly mixing the organopolysiloxane core emulsion, the acrylate rubber emulsion and water, heating to 70-85 ℃, continuously stirring and adding a shell monomer mixed solution, then adding an initiator B, and continuously stirring and reacting for 3-4 hours to obtain the matte emulsion;
preparing a matte organic silicon high-impact toughening agent:
and carrying out spray drying treatment or coagulation, centrifugation, washing and drying treatment on the matte emulsion to obtain the matte organic silicon high-impact toughening agent.
The preparation method of the matte organosilicon high-impact toughening agent comprises the steps of taking an organopolysiloxane core emulsion and an acrylate rubber emulsion as main raw materials, adding a shell monomer mixed solution and an initiator B to carry out emulsion polymerization reaction to prepare a matte emulsion, and demulsifying and drying to obtain the matte organosilicon high-impact toughening agent which has the characteristics of low glass transition temperature and low-temperature impact strength of organosilicon rubber, high temperature resistance, weather aging resistance, oil resistance, easiness in processing and the like of acrylate rubber; after the matte organic silicon high-impact toughening agent is added when AS resin is adopted to produce ASA resin, due to certain difference in compatibility between organic silicon rubber and AS resin, organic silicon rubber tends to be enriched on the surface of the material in the processing process, so that the surface of the ASA resin becomes microscopically uneven and rough, when light irradiates on the surface of the ASA resin material, one part of light is absorbed and refracted into the material, and the other part of light generates diffuse reflection on the rough interface of the resin and the rubber, so that the detected and observed reflected light intensity is reduced and the glossiness is reduced, and the matte effect can be achieved without additionally adding a matting agent; the preparation method has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
Preferably, the emulsion particle size of the organopolysiloxane core emulsion is 300-1000nm, and the solid content is 20-60%; the emulsion particle size of the acrylate rubber emulsion is 200-500, and the solid content is 20-60%.
By adopting the technical scheme, the emulsion particle size of the organopolysiloxane core emulsion is controlled to be 300-1000nm, the emulsion particle size of the acrylate rubber emulsion is controlled to be 200-500, the phenomenon that the gloss effect is good due to the fact that the emulsion particle size is too small is avoided, the extinction effect of the matte organosilicon high-impact-resistant toughening agent is promoted, the emulsion particle size is controlled to be in a specific range, the prepared matte organosilicon high-impact-resistant toughening agent is applied to production of ASA resin, the filling effect is better, and the tensile strength and the impact strength of the ASA resin are better enhanced.
Preferably, the acrylate mixed solution is added in the step (A2) in a dropwise manner, and the dropwise addition lasts for 2-3 hours.
By adopting the technical scheme, the reaction is controlled to be carried out and the acrylic ester rubber emulsion with the emulsion particle size of 200-500 is obtained, so that the acrylic ester monomer is prevented from being scrapped due to implosion.
Preferably, in the step of synthesizing the matte emulsion, the ratio of the weight parts of the organopolysiloxane core emulsion, the acrylate rubber emulsion, the water, the initiator B and the shell monomer mixed solution is 10-30:30-50:10-30:0.03-0.6:30-60.
By adopting the technical scheme, the dosage of the organopolysiloxane nuclear emulsion and the acrylate rubber emulsion is controlled, the problems that the extinction effect and the impact property are poor due to too low dosage of the organopolysiloxane nuclear emulsion and the coloring property is poor due to too high dosage of the organopolysiloxane nuclear emulsion are avoided; the method avoids poor impact effect caused by too low acrylate rubber emulsion and poor extinction effect caused by too high acrylate rubber emulsion.
Preferably, the organosiloxane monomer is at least one of a phenyl siloxane monomer, a cyclic siloxane monomer and a vinyl siloxane monomer; the silane coupling agent is at least one of gamma-methacryloxypropyltrimethoxysilane, methyltriethoxysilane and vinyl trimethoxysilane.
By adopting the technical scheme, the organic siloxane monomer and the silane coupling agent are mixed, the dispersibility of the organic siloxane monomer is improved, and the organic siloxane monomer reacts under the action of the emulsifier A and the catalyst to form the organic polysiloxane nuclear emulsion, so that the matte organic silicon high-impact toughening agent is improved when being applied to the ASA resin material, and the impact strength of the ASA resin material is improved. Wherein the phenyl siloxane monomer is at least one of phenyl trimethoxy silane, methyl phenyl dimethoxy silane, vinyl phenyl dimethoxy silane and methyl diphenyl methoxy silane; the cyclic siloxane monomer is at least one of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decaphenylcyclopentasiloxane and trimethyltriethylcyclotrisiloxane; the vinyl siloxane monomer is at least one of vinyl trimethoxy silane, vinyl triethoxy silane, divinyl dimethoxy silane and p-vinyl phenyl ethyl methoxy silane.
Preferably, the catalyst is at least one of methanesulfonic acid, vinylsulfonic acid, benzenesulfonic acid, ethylbenzene sulfonic acid and dodecylbenzenesulfonic acid; the acrylic ester monomer is at least one of methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate and 2-ethylhexyl acrylate; the crosslinking agent is at least one of dicyclopentadienyl acrylate, allyl methacrylate, divinylbenzene, diallyl maleate, diallyl fumarate and triallyl cyanurate.
By adopting the technical scheme, the positive reaction rate of the organic silicon mixed solution is improved under the catalytic action of the catalyst; the acrylic ester monomer can improve the high-temperature resistance, weather aging resistance, oil resistance and easy processing performance of the ASA resin. The acrylic ester rubber emulsion obtained by adopting the cross-linking agent can improve the toughness and the aging resistance of the impact-resistant toughening agent. More preferably, the crosslinking agent is biscyclopentadienyl acrylate and divinylbenzene in a weight ratio of 3 to 5:1 and mixing.
Preferably, the emulsifier A is at least one of lauryl betaine, stearyl betaine, sodium laurate and sodium dodecyl benzene sulfonate; the emulsifier B is at least one of lauryl betaine, stearyl betaine, sodium laurate and sodium dodecyl benzene sulfonate; the emulsifier C is at least one of lauryl betaine, stearyl betaine, sodium laurate and sodium dodecyl benzene sulfonate; the initiator A and the initiator B are at least one of benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the shell monomer mixed solution is prepared by mixing a shell monomer and a molecular weight regulator according to a weight ratio of 9-11: 0.1-0.5.
By adopting the technical scheme, the shell monomer is controlled to polymerize into the shell, and the acrylate rubber and the organic silicon rubber are both in the shell, so that the physical property degradation caused by poor compatibility is avoided, and the high light and low diffuse reflectance of the formed product are also avoided.
Preferably, the shell monomer is at least one of styrene, methyl styrene, tert-butyl styrene, acrylonitrile, acrylic acid, maleic anhydride and methyl methacrylate; the molecular weight regulator is at least one of chloroform, n-hexyl mercaptan, n-octyl mercaptan, dodecyl mercaptan and terpene. More preferably, the shell monomer is styrene and acrylonitrile in a weight ratio of 7-8:2-3, mixing.
The other purpose of the invention is realized by the following technical scheme: a matte organic silicon high-impact toughening agent is prepared by adopting the preparation method of the matte organic silicon high-impact toughening agent.
The invention has the beneficial effects that: according to the preparation method of the matte organic silicon high-impact toughening agent, the obtained matte organic silicon high-impact toughening agent, namely the organic silicon modified polyacrylate-shell monomer copolymer, has good impact strength, not only has a good extinction effect, but also additionally provides a high-impact effect, and the matte organic silicon high-impact toughening agent can not generate great influence on other properties of materials when being applied to preparation of ASA resin or ABS resin modification; the preparation method has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
When the matte organic silicon high-impact-resistance toughening agent is applied to preparation of ASA resin or ABS resin for modification, other properties of the material cannot be greatly influenced, the using amount is small, the matte organic silicon high-impact-resistance toughening agent has a good light-eliminating effect, and a high-impact-resistance effect is additionally provided.
Drawings
FIG. 1 is an SEM photograph of an experimental group 1 of the present invention.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention.
Example 1
A preparation method of a matte organic silicon high-impact-resistant toughening agent comprises the following steps:
synthesis of organopolysiloxane core emulsion:
(S1) mixing an organic siloxane monomer and a silane coupling agent according to a weight ratio of 100:7, uniformly mixing to obtain an organic silicon mixed solution;
(S2) adding the organic silicon mixed solution into an aqueous solution mixed with a catalyst and an emulsifier A, shearing at a high speed of 10000rpm for 12min by using a homogenizer, and reacting at a temperature of 90 ℃ for 9h to obtain the organopolysiloxane nuclear emulsion; wherein the total mass of the organic siloxane monomer is 40% of the mass of water, the mass of the catalyst is 3% of the mass of the organic siloxane monomer, and the mass of the emulsifier A is 10% of the mass of the organic siloxane monomer;
synthesizing an acrylate rubber emulsion:
(A1) Uniformly mixing 40 parts by weight of acrylate monomer and 1.2 parts by weight of cross-linking agent, adding 40 parts by weight of 1wt% emulsifier B-water solution, and dispersing to obtain an acrylate mixed solution; uniformly mixing 0.3 part by weight of initiator A, 0.5 part by weight of emulsifier C and 40 parts by weight of water to obtain a diluted water solution;
(A2) Continuously stirring and keeping the temperature at 78 ℃, adding the acrylate mixed solution into the diluted aqueous solution, and reacting for 2.5 hours to obtain the acrylate rubber emulsion;
synthesizing a matte emulsion:
uniformly mixing the organopolysiloxane core emulsion, the acrylate rubber emulsion and water, heating to 78 ℃, continuously stirring, adding a shell monomer mixed solution, adding an initiator B, and continuously stirring for reaction for 3.5 hours to obtain the matte emulsion;
preparing a matte organic silicon high-impact toughening agent:
and (3) carrying out condensation, centrifugation, washing and drying treatment on the matte emulsion to obtain the matte organic silicon high-impact toughening agent.
The emulsion particle size of the organopolysiloxane core emulsion is 600nm, and the solid content is 40%; the acrylate rubber emulsion has the emulsion particle size of 350nm and the solid content of 40%.
And (3) adding the acrylic ester mixed solution in the step (A2) in a dropwise manner, wherein the dropwise adding time lasts for 2.5 hours.
In the step of synthesizing the matte emulsion, the ratio of the organic polysiloxane core emulsion, the acrylate rubber emulsion, the water, the initiator B and the shell monomer mixed solution in parts by weight is 20:40:20:0.3:45.
the silane coupling agent is vinyl trimethoxy silane; the organosiloxane monomer is octamethylcyclotetrasiloxane.
The catalyst is dodecyl benzene sulfonic acid; the acrylate monomer is butyl acrylate; the crosslinking agent is dicyclopentadienyl acrylate and divinylbenzene in a weight ratio of 4:1 and mixing.
The emulsifier A is sodium dodecyl benzene sulfonate; the emulsifier B is sodium dodecyl benzene sulfonate; the emulsifier C is sodium dodecyl benzene sulfonate; the initiator A and the initiator B are both potassium persulfate.
The shell monomer mixed solution is prepared by mixing a shell monomer and a molecular weight regulator according to the weight ratio of 10:0.3, and mixing.
The shell monomer is styrene and acrylonitrile according to a weight ratio of 7.5:2.5 mixing. The molecular weight regulator is dodecyl mercaptan.
Example 2
A preparation method of a matte organic silicon high-impact-resistant toughening agent comprises the following steps:
synthesis of organopolysiloxane core emulsion:
(S1) mixing an organic siloxane monomer and a silane coupling agent according to a weight ratio of 100:0.5, uniformly mixing to obtain an organic silicon mixed solution;
(S2) adding the organic silicon mixed solution into an aqueous solution mixed with a catalyst and an emulsifier A, shearing the mixture at a high speed of 8000rpm for 20min by using a homogenizer, and reacting the mixture at a temperature of 85 ℃ for 12h to obtain the organopolysiloxane nuclear emulsion; wherein the total mass of the organic siloxane monomer is 20% of the mass of water, the mass of the catalyst is 1% of the mass of the organic siloxane monomer, and the mass of the emulsifier A is 1% of the mass of the organic siloxane monomer;
synthesizing an acrylate rubber emulsion:
(A1) Uniformly mixing 30 parts by weight of acrylate monomers and 0.15 part by weight of cross-linking agent, adding 30 parts by weight of 0.1wt% emulsifier B-aqueous solution, and dispersing to obtain an acrylate mixed solution; uniformly mixing 0.03 part by weight of initiator A, 0.03 part by weight of emulsifier C and 30 parts by weight of water to obtain a diluted aqueous solution;
(A2) Continuously stirring and keeping the temperature at 70 ℃, adding the acrylate mixed solution into the diluted aqueous solution, and reacting for 2 hours to obtain the acrylate rubber emulsion;
and (3) synthesizing a matte emulsion:
uniformly mixing the organopolysiloxane core emulsion, the acrylate rubber emulsion and water, heating to 70 ℃, continuously stirring, adding a shell monomer mixed solution, adding an initiator B, and continuously stirring for reacting for 4 hours to obtain the matte emulsion;
preparing a matte organic silicon high-impact toughening agent:
and carrying out spray drying treatment on the matte emulsion to obtain the matte organic silicon high-impact toughening agent.
The emulsion particle size of the organopolysiloxane core emulsion is 300nm, and the solid content is 20%; the particle size of the acrylate rubber emulsion is 200nm, and the solid content is 20%.
The acrylic ester mixed solution is added in the step (A2) in a dropwise manner, and the dropwise adding time lasts for 2 hours.
In the step of synthesizing the matte emulsion, the ratio of the organic polysiloxane core emulsion, the acrylate rubber emulsion, the water, the initiator B and the shell monomer mixed solution in parts by weight is 10:30:10:0.03:30.
the organic siloxane monomer is phenyl siloxane monomer; the silane coupling agent is gamma-methacryloxypropyl trimethoxy silane. The phenyl siloxane monomer is phenyl trimethoxy silane.
The catalyst is ethyl benzene sulfonic acid; the acrylate monomer is ethyl methacrylate; the crosslinking agent is dicyclopentadienyl acrylate and divinylbenzene in a weight ratio of 3:1 and mixing.
The emulsifier A is lauryl betaine; the emulsifier B is sodium dodecyl benzene sulfonate; the emulsifier C is lauryl betaine; the initiator A and the initiator B are both sodium persulfate.
The shell monomer mixed solution is prepared by mixing a shell monomer and a molecular weight regulator according to the weight ratio of 9:0.1, and mixing.
The shell monomer is styrene and acrylonitrile according to a weight ratio of 7:2, mixing the components. The molecular weight regulator is n-octyl mercaptan.
Example 3
A preparation method of a matte organic silicon high-impact-resistant toughening agent comprises the following steps:
synthesis of organopolysiloxane core emulsion:
(S1) mixing an organic siloxane monomer and a silane coupling agent according to a weight ratio of 100:15, uniformly mixing to obtain an organic silicon mixed solution;
(S2) adding the organic silicon mixed solution into an aqueous solution mixed with a catalyst and an emulsifier A, shearing the mixture for 5min at a high speed of 12000rpm by using a homogenizer, and reacting the mixture for 6h at the temperature of 100 ℃ to obtain the organopolysiloxane nuclear emulsion; wherein the total mass of the organic siloxane monomer is 60% of the mass of water, the mass of the catalyst is 5% of the mass of the organic siloxane monomer, and the mass of the emulsifier A is 20% of the mass of the organic siloxane monomer;
synthesizing an acrylate rubber emulsion:
(A1) Uniformly mixing 50 parts by weight of acrylate monomers and 2.5 parts by weight of cross-linking agent, adding 50 parts by weight of 2wt% emulsifier B-water solution, and dispersing to obtain an acrylate mixed solution; uniformly mixing 0.5 part by weight of initiator A, 1 part by weight of emulsifier C and 50 parts by weight of water to obtain a diluted water solution;
(A2) Continuously stirring and keeping the temperature at 85 ℃, adding the acrylate mixed solution into the diluted aqueous solution, and reacting for 3 hours to obtain the acrylate rubber emulsion;
synthesizing a matte emulsion:
uniformly mixing the organopolysiloxane core emulsion, the acrylate rubber emulsion and water, heating to 85 ℃, continuously stirring, adding a shell monomer mixed solution, adding an initiator B, and continuously stirring for reaction for 3 hours to obtain the matte emulsion;
preparing a matte organic silicon high-impact toughening agent:
and (3) carrying out condensation, centrifugation, washing and drying treatment on the matte emulsion to obtain the matte organic silicon high-impact toughening agent.
The emulsion particle size of the organopolysiloxane core emulsion is 1000nm, and the solid content is 60%; the emulsion particle size of the acrylate rubber emulsion is 500nm, and the solid content is 60%.
And (3) adding the acrylic ester mixed solution in the step (A2) in a dropwise manner, wherein the dropwise adding time lasts for 3 hours.
In the step of synthesizing the matte emulsion, the ratio of the organic polysiloxane core emulsion, the acrylate rubber emulsion, the water, the initiator B and the shell monomer mixed solution in parts by weight is 30: 50:30:0.6: 60.
The organic siloxane monomer is vinyl siloxane monomer; the silane coupling agent is methyl triethoxysilane. The vinyl siloxane monomer is vinyl trimethoxy silane.
The catalyst is benzenesulfonic acid; the acrylate monomer is 2-ethylhexyl acrylate; the crosslinking agent is dicyclopentadienyl acrylate and divinylbenzene with the weight ratio of 5:1 and mixing.
The emulsifier A is sodium laurate; the emulsifier B is sodium laurate; the emulsifier C is lauryl betaine; the initiator A and the initiator B are both sodium persulfate.
The shell monomer mixed solution is prepared by mixing a shell monomer and a molecular weight regulator according to the weight ratio of 11: 0.5, and mixing.
The shell monomer is styrene and acrylonitrile according to a weight ratio of 8: 3, and mixing. The molecular weight regulator is terpene.
Example 4
A preparation method of a matte organic silicon high-impact-resistant toughening agent comprises the following steps:
synthesis of organopolysiloxane core emulsion:
(S1) mixing an organic siloxane monomer and a silane coupling agent according to a weight ratio of 100:5, uniformly mixing to obtain an organic silicon mixed solution;
(S2) adding the organic silicon mixed solution into an aqueous solution mixed with a catalyst and an emulsifier A, shearing the aqueous solution at a high speed of 11000rpm for 8min by using a homogenizer, and reacting the aqueous solution at the temperature of 95 ℃ for 10h to obtain the organopolysiloxane nuclear emulsion; wherein the total mass of the organic siloxane monomer is 30% of the mass of water, the mass of the catalyst is 4% of the mass of the organic siloxane monomer, and the mass of the emulsifier A is 5% of the mass of the organic siloxane monomer;
synthesizing an acrylate rubber emulsion:
(A1) Uniformly mixing 35 parts by weight of acrylate monomer and 1.5 parts by weight of cross-linking agent, adding 35 parts by weight of 1.5wt% emulsifier B-aqueous solution, and dispersing to obtain an acrylate mixed solution; uniformly mixing 0.1 part by weight of initiator A, 0.8 part by weight of emulsifier C and 35 parts by weight of water to obtain a diluted water solution;
(A2) Continuously stirring and keeping the temperature at 80 ℃, adding the acrylate mixed solution into the diluted aqueous solution, and reacting for 2.6 hours to obtain the acrylate rubber emulsion;
synthesizing a matte emulsion:
uniformly mixing the organopolysiloxane core emulsion, the acrylate rubber emulsion and water, heating to 80 ℃, continuously stirring, adding a shell monomer mixed solution, adding an initiator B, and continuously stirring for reaction for 3.6 hours to obtain the matte emulsion;
preparing a matte organic silicon high-impact toughening agent:
and (3) carrying out condensation, centrifugation, washing and drying treatment on the matte emulsion to obtain the matte organic silicon high-impact-resistance toughening agent.
The emulsion particle size of the organopolysiloxane core emulsion is 800nm, and the solid content is 30%; the acrylic ester rubber emulsion has the emulsion particle size of 400nm and the solid content of 35%.
And (3) adding the acrylic ester mixed solution in the step (A2) in a dropwise manner, wherein the dropwise adding time lasts for 2.8 hours.
In the step of synthesizing the matte emulsion, the ratio of the weight parts of the organopolysiloxane core emulsion, the acrylate rubber emulsion, the water, the initiator B and the shell monomer mixed solution is 15:45: 30:0.2:50.
the organic siloxane monomer is vinyl siloxane monomer; the silane coupling agent is vinyl trimethoxy silane. The vinyl siloxane monomer is vinyl triethoxysilane.
The catalyst is vinyl sulfonic acid; the acrylate monomer is cyclohexyl acrylate and ethyl methacrylate; the crosslinking agent is dicyclopentadienyl acrylate and divinylbenzene in a weight ratio of 4:1 and mixing.
The emulsifier A is sodium dodecyl benzene sulfonate; the emulsifier B is sodium dodecyl benzene sulfonate; the emulsifier C is sodium dodecyl benzene sulfonate; the initiator A and the initiator B are both ammonium persulfate.
The shell monomer mixed solution is prepared by mixing a shell monomer and a molecular weight regulator according to the weight ratio of 10:0.2 and mixing.
The shell monomer is prepared from styrene and acrylonitrile according to a weight ratio of 7.3:2.8 and mixing. The molecular weight regulator is dodecyl mercaptan.
Comparative example 1
This comparative example differs from example 1 in that:
the shell monomer is styrene.
Comparative example 2
This comparative example differs from example 1 in that:
the cross-linking agent is dicyclopentadienyl acrylate.
Comparative example 3
This comparative example differs from example 1 in that:
the weight ratio of the organopolysiloxane core emulsion to the acrylate rubber emulsion to the water to the initiator B to the shell monomer mixed solution is 35:25:20:0.3:45.
comparative example 4
This comparative example differs from example 1 in that:
the weight ratio of the organopolysiloxane core emulsion to the acrylate rubber emulsion to the water to the initiator B to the shell monomer mixed solution is 7:53:20:0.3:45.
comparative example 5
This comparative example differs from example 1 in that:
the shell monomer mixed solution does not contain a molecular weight regulator.
Comparative example 6
The toughening agent is a methyl methacrylate-butadiene-styrene terpolymer with the model of TH-21.
Example 5
Taking the toughening agents of the examples 1-4 and the comparative examples 1-6, mixing the following raw materials, and carrying out melt extrusion granulation by a double-screw extruder at 230-300 ℃ to prepare each group of ASA materials:
| component (parts by weight) | AS resin (weight average molecular weight 125000) | Thermal stabilizer IRGANOX245 | Toughening agent | Organic matting agent BMAT | Inorganic matting agent YN35 | Lubricant PETS |
| Experimental group 1 | 69 | 0.5 | 30 (toughener of example 1) | 0 | 0 | 0.5 |
| Experimental group 2 | 69 | 0.5 | 30 (toughening agent of example 2) | 0 | 0 | 0.5 |
| Experimental group 3 | 69 | 0.5 | 30 (toughener of example 3) | 0 | 0 | 0.5 |
| Experimental group 4 | 69 | 0.5 | 30 (toughening agent of example 4) | 0 | 0 | 0.5 |
| Comparative group 1 | 69 | 0.5 | 30 (toughener of comparative example 1) | 0 | 0 | 0.5 |
| Comparative group 2 | 69 | 0.5 | 30 (toughener of comparative example 2) | 0 | 0 | 0.5 |
| Comparative group 3 | 69 | 0.5 | 30 (toughener of comparative example 3) | 0 | 0 | 0.5 |
| Comparative group 4 | 69 | 0.5 | 30 (toughener of comparative example 4) | 0 | 0 | 0.5 |
| Comparative group 5 | 69 | 0.5 | 30 (toughener of comparative example 5) | 0 | 0 | 0.5 |
| Comparative group 6 | 69 | 0.5 | 30 (to forToughening agent of ratio 6) | 5 | 0 | 0.5 |
| Comparative group 7 | 69 | 0.5 | 30 (toughener of comparative example 6) | 0 | 20 | 0.5 |
I. The ASA materials of the above experimental groups 1 to 4 and comparative groups 1 to 7 were used for tensile strength, impact strength, melt index, softening temperature and gloss measurements according to the following methods:
tensile strength: preparing a class I sample according to the specification of ASTM-D638, testing the tensile strength of the class I sample at a tensile speed of 50mm/min in MPa;
impact strength: according to the regulation of GB/T1843-2008, the notch impact strength of the cantilever beam is tested according to the type A notch and the normal temperature, and the unit is KJ/m 2 ；
Melt index: the melt index was measured in g/10min at 220 ℃ per 10kg as specified in ASTM-D1238;
softening temperature: the Vicat softening temperature was measured according to ASTM-D1525, in units of;
gloss: testing the 60-degree specular gloss value according to the regulation of GB/T9754-2007;
the test results are shown in the following table:
| tensile strength | Impact strength | Melt index | Softening temperature | Degree of gloss | |
| Experimental group 1 | 40 | 17.8 | 7.5 | 117 | 23 |
| Experimental group 2 | 38 | 16.6 | 8 | 120 | 28 |
| Experimental group 3 | 43 | 18 | 7.1 | 115 | 20 |
| Experimental group 4 | 41 | 17.5 | 7.8 | 119 | 25 |
| Comparative group 1 | 37 | 16.1 | 8.2 | 123 | 24 |
| Comparative group 2 | 38 | 16.3 | 7.5 | 118 | 22 |
| Comparative group 3 | 42 | 15.9 | 8.3 | 120 | 20 |
| Comparative group 4 | 36 | 13.5 | 6.5 | 116 | 52 |
| Comparative group 5 | 35 | 15.7 | 7.4 | 117 | 25 |
| Comparative group 6 | 40 | 13.4 | 6.2 | 114 | 43 |
| Comparative group 7 | 32 | 11.2 | 6.1 | 109 | 36 |
As can be seen from the table, the matte organic silicon high-impact toughening agent provided by the invention has a reinforcing effect on ASA resin obtained by production and has a good extinction effect. Compared with the comparative group 1, the experimental group 1 adopts the shell monomers compounded in a specific proportion, and is more favorable for avoiding the deterioration of the physical properties caused by poor compatibility. Compared with the comparison group 2, the experiment group 1 adopts the crosslinking agent compounded in a specific proportion, and is more beneficial to improving the toughness and the aging resistance of the impact-resistant toughening agent. Compared with a comparison group 3 and a comparison group 4, the toughening agent obtained by compounding the organopolysiloxane core emulsion, the acrylate rubber emulsion, the water, the initiator B and the shell monomer mixed solution in a specific ratio in the experiment group 1 improves the impact property and the extinction effect of the ASA resin. Compared with the comparative group 5, the toughening agent obtained by compounding the organopolysiloxane core emulsion, the acrylate rubber emulsion, the water, the initiator B and the shell monomer mixed solution in a specific ratio in the experimental group 1 improves the impact property and the extinction effect of the ASA resin. Compared with a comparison group 6 and a comparison group 7, the specific toughening agent of the experiment group 1 can achieve the matte effect without adding a flatting agent, and the tensile property and the impact property of the ASA resin are improved.
II. The ASA material prepared in the above Experimental group 1 was used to prepare a type I sample according to the specification of ASTM-D638, and scanning and imaging the type I sample by using SEM to obtain a SEM topography, as shown in FIG. 1, it can be seen from FIG. 1 that the surface of the ASA material becomes uneven and rough.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (5)
1. A preparation method of a matte organic silicon high-impact-resistance toughening agent is characterized by comprising the following steps: synthesis of organopolysiloxane core emulsion:
(S1) mixing an organic siloxane monomer and a silane coupling agent according to a weight ratio of 100:0.5-15, and obtaining organic silicon mixed liquor;
(S2) adding the organic silicon mixed solution into an aqueous solution mixed with a catalyst and an emulsifier A, shearing at a high speed of 8000-12000rpm for 5-20min by using a homogenizer, and reacting at the temperature of 85-100 ℃ for 6-12h to obtain the organopolysiloxane nuclear emulsion; wherein the total mass of the organosiloxane monomer is 20-60% of the mass of water, the mass of the catalyst is 1-5% of the mass of the organosiloxane monomer, and the mass of the emulsifier A is 1-20% of the mass of the organosiloxane monomer;
synthesizing an acrylate rubber emulsion:
(A1) Uniformly mixing 30-50 parts by weight of acrylate monomers and 0.15-2.5 parts by weight of cross-linking agent, adding into 30-50 parts by weight of 0.1-2wt% emulsifier B-water solution, and dispersing to obtain an acrylate mixed solution; uniformly mixing 0.03-0.5 part by weight of initiator A, 0.03-1 part by weight of emulsifier C and 30-50 parts by weight of water to obtain a diluted water solution;
(A2) Continuously stirring and keeping the temperature at 70-85 ℃, adding the acrylate mixed solution into the diluted aqueous solution, and reacting for 2-3h to obtain the acrylate rubber emulsion;
synthesizing a matte emulsion:
uniformly mixing the organopolysiloxane core emulsion, the acrylate rubber emulsion and water, heating to 70-85 ℃, continuously stirring and adding a shell monomer mixed solution, then adding an initiator B, and continuously stirring and reacting for 3-4 hours to obtain the matte emulsion;
preparing a matte organic silicon high-impact toughening agent:
carrying out spray drying treatment or coagulation, centrifugation, washing and drying treatment on the matte emulsion to obtain the matte organic silicon high-impact-resistant toughening agent;
in the step of synthesizing the matte emulsion, the ratio of the organic polysiloxane core emulsion to the acrylate rubber emulsion to the water to the initiator B to the shell monomer mixed solution in parts by weight is 10-30:30-50:10-30:0.03-0.6:30-60 parts of;
the shell monomer mixed solution is prepared by mixing a shell monomer and a molecular weight regulator according to the weight ratio of 9-11: 0.1-0.5;
the molecular weight regulator is at least one of chloroform, n-hexyl mercaptan, n-octyl mercaptan, dodecyl mercaptan and terpene;
the catalyst is at least one of methanesulfonic acid, vinylsulfonic acid, benzenesulfonic acid, ethylbenzene sulfonic acid and dodecylbenzenesulfonic acid; the acrylic ester monomer is at least one of methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate and 2-ethylhexyl acrylate;
the emulsifier A is at least one of lauryl betaine, stearyl betaine, sodium laurate and sodium dodecyl benzene sulfonate; the emulsifier B is at least one of lauryl betaine, stearyl betaine, sodium laurate and sodium dodecyl benzene sulfonate; the emulsifier C is at least one of lauryl betaine, stearyl betaine, sodium laurate and sodium dodecyl benzene sulfonate; the initiator A and the initiator B are at least one of benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile and azobisisoheptonitrile;
the crosslinking agent is dicyclopentadienyl acrylate and divinylbenzene in a weight ratio of 3-5:1, mixing;
the shell monomer is styrene and acrylonitrile according to the weight ratio of 7-8:2-3, mixing.
2. The preparation method of the matte organic silicon high-impact toughening agent according to claim 1, characterized in that: the particle size of the emulsion of the organopolysiloxane core emulsion is 300-1000nm, and the solid content is 20-60%; the emulsion particle size of the acrylate rubber emulsion is 200-500nm, and the solid content is 20-60%.
3. The preparation method of the matte organic silicon high-impact toughening agent according to claim 1, characterized in that: and (3) adding the acrylate mixed solution in the step (A2) in a dropwise manner, wherein the dropwise addition lasts for 2-3h.
4. The preparation method of the matte organic silicon high-impact toughening agent according to claim 1, characterized in that: the organic siloxane monomer is at least one of phenyl siloxane monomer, cyclic siloxane monomer and vinyl siloxane monomer; the silane coupling agent is at least one of gamma-methacryloxypropyltrimethoxysilane, methyltriethoxysilane and vinyl trimethoxysilane.
5. A matte organic silicon high-impact-resistant toughening agent is characterized in that: prepared by the preparation method of the matte organic silicon high-impact toughening agent as claimed in any one of claims 1 to 4.
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