CN115181223A - Low-gloss matte auxiliary agent, preparation method thereof and formed body - Google Patents
Low-gloss matte auxiliary agent, preparation method thereof and formed body Download PDFInfo
- Publication number
- CN115181223A CN115181223A CN202210975250.1A CN202210975250A CN115181223A CN 115181223 A CN115181223 A CN 115181223A CN 202210975250 A CN202210975250 A CN 202210975250A CN 115181223 A CN115181223 A CN 115181223A
- Authority
- CN
- China
- Prior art keywords
- low
- monomer
- auxiliary agent
- matte
- gloss
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- 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
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- 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
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Landscapes
- 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)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to the technical field of engineering plastic matte modification, in particular to a low-gloss matte auxiliary agent, a preparation method and a formed body thereof, wherein the preparation method of the low-gloss matte auxiliary agent comprises the steps of carrying out polycondensation on a cyclic siloxane monomer, a phenyl siloxane monomer, a vinyl siloxane monomer and an end-capping agent under the action of a catalyst to obtain a multifunctional organic silicon solution, and then carrying out graft copolymerization on the multifunctional organic silicon solution and a graft monomer in an organic solvent under the action of an initiator to obtain the low-gloss matte auxiliary agent which has an organic silicon chain segment to provide a matte effect and a resin chain segment to provide good affinity with a resin base material; the low-gloss matte auxiliary agent provides a good matte effect for the matte resin forming body, and can meet the matte requirement without adding unnecessary components which have great influence on other properties; the glossiness can be flexibly adjusted within a certain range.
Description
Technical Field
The invention relates to the technical field of engineering plastic matte modification, in particular to a low-gloss matte auxiliary agent, a preparation method thereof and a formed body.
Background
ASA resins and ABS resins are frequently used as engineering plastics. The mechanical property, the processing property, the electrical insulation property and the chemical resistance are excellent. 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 ABS (acrylonitrile butadiene styrene) workpiece, 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 adopting the inorganic flatting agents, and the common flatting agents have high addition amount of the flatting agents, large processing difficulty and large influence on the impact performance of products.
Patent CN104592666A discloses the preparation of low gloss materials using crosslinked styrene-acrylonitrile polymers as organic matting agents. The flatting agent is an additional component, and has high addition amount and poor effect.
Patent CN102382348B discloses that a polyolefin resin modified reactive matting agent is synthesized for ABS resin, which causes deterioration of physical properties due to poor compatibility.
Patent WO2009/011280 discloses a graft copolymer containing a composite rubber of polysiloxane and polyacrylate, which has a high gloss and a low diffuse reflectance of molded articles.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the preparation method of the low-gloss matte auxiliary agent, which is simple to operate, convenient to control, high in production efficiency, low in production cost and capable of being used for large-scale production; the ring-opening of the organosilicon cyclic monomer is condensed with the phenyl siloxane monomer and the vinyl siloxane monomer to form linear or branched organosilicon oil with a certain molecular weight through a catalyst, and then the monomer is grafted under a solvent system to form a monomer modified organosilicon polymer with a certain molecular weight.
The invention also aims to provide a low-gloss matte auxiliary agent which has a good extinction effect, is low in addition amount, convenient to process and small in influence on other physical properties of materials, and is suitable for the requirements of low-gloss matte modification of materials such as ABS, ASA, PC/ABS, PC/ASA and the like.
The invention also aims to provide a preparation method of the matte resin forming body, which is characterized in that the low-gloss matte auxiliary agent is added on the basis of the components of the existing formula, so that the extinction effect is improved, other components of the formula do not need to be changed, and the applicability is strong.
One of the purposes of the invention is realized by the following technical scheme: a preparation method of a low-gloss matte auxiliary agent comprises the following steps:
A. synthesis of multifunctional silicone solution:
a1, uniformly mixing a cyclic siloxane monomer, a phenyl siloxane monomer, a vinyl siloxane monomer and an end-capping reagent to obtain an organic silicon monomer mixed solution;
a2, adding a catalyst into the organic silicon monomer mixed solution, and reacting at the temperature of 85-100 ℃ for 6-12h to obtain transparent modified organic polysiloxane liquid;
a3, separating the catalyst from the transparent modified organopolysiloxane liquid to obtain a multifunctional organosilicon solution;
B. and (3) synthesizing a low-gloss matte auxiliary agent:
b1, uniformly mixing a grafting monomer, a molecular weight regulator and an initiator to obtain a mixed monomer solution;
b2, adding an organic solvent into the multifunctional organic silicon solution to obtain a multifunctional organic silicon mixed solution;
and B3, continuously adding the mixed monomer solution into the multifunctional organic silicon mixed solution for 1-3h at the temperature of 60-90 ℃, then keeping the temperature of 60-90 ℃ for 1-3h, and then carrying out vacuum separation on the organic solvent to obtain the low-gloss matte auxiliary agent.
The preparation method of the low-gloss matte auxiliary agent comprises the steps of carrying out polycondensation on a cyclic siloxane monomer, a phenyl siloxane monomer, a vinyl siloxane monomer and an end-capping agent under the action of a catalyst to obtain a multifunctional organic silicon solution, and then carrying out graft copolymerization on the multifunctional organic silicon solution and a graft monomer in an organic solvent under the action of an initiator to obtain the low-gloss matte auxiliary agent which has an organic silicon chain segment to provide a matte effect and a resin chain segment to provide good affinity with a resin base material.
Preferably, in the step A, the phenyl siloxane monomer, the vinyl siloxane monomer and the end-capping agent respectively account for 0.5 to 15 percent of the weight of the cyclic siloxane monomer; the catalyst accounts for 1-20% of the weight of the cyclic siloxane monomer.
Further, in the step B, the molecular weight regulator and the initiator respectively account for 0.5-5% of the weight ratio of the grafting monomer; the weight of the organic solvent is 0.5 to 3 times of the total mass of the multifunctional organic silicon solution; the weight ratio of the multifunctional organic silicon solution to the weight of the grafting monomer is 1-4.
By adopting the technical scheme, the ratio of the weight of the multifunctional organic silicon solution to the weight of the grafting monomer is controlled, the phenomenon that the extinction is not facilitated due to too low using amount of the multifunctional organic silicon solution is avoided, and the adverse effect on mechanical properties due to the compatibility and dispersion which are not facilitated due to too high using amount of the multifunctional organic silicon solution is also avoided.
<xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> At least one of methylheptvinylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane and methylheptenylcyclotetrasiloxane.
Preferably, the phenylsiloxane monomer is phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylmethoxysilane, methylphenyldimethoxysilane, ethylphenyldimethoxysilane, propylphenyldimethoxysilane, vinylphenyldimethoxysilane, propenylphenyldimethoxysilane, ethynylphenyldimethoxysilane, propynylphenyldimethoxysilane, methyldiphenylmethoxysilane, ethyldiphenylmethoxysilane, propyldiphenylmethoxysilane, vinyldiphenylmethoxysilane, propenyldiphenylmethoxysilane, ethynyldiphenylmethoxysilane, propynyldiphenylmethoxysilane, dimethylphenylmethoxysilane, diethylphenylmethoxysilane, dipropylphenylmethoxysilane, divinylphenylmethoxysilane, dipropenylmethoxysilane, diethynylphenylmethoxysilane, dipropynylphenylmethoxysilane, methylethylphenylmethoxysilane, methylpropylphenylmethoxysilane, ethylpropylphenylmethoxysilane, methylvinylphenylmethoxysilane, ethylpropenylphenylmethoxysilane, methylacetylphenylmethoxysilane, ethylpropynylphenylmethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, triphenylethoxysilane, methylphenyldiethoxysilane, ethylphenyldiethoxysilane, propylphenyldiethoxysilane, vinylphenyldiethoxysilane, propenylphenylethoxysilane, propenylphenyldiethoxysilane, allylphenyldiethoxysilane, ethynylphenyldiethoxysilane, ethylpropylphenylethoxysilane, diphenylethoxysilane, and methyl-diphenylethoxysilane, at least one of vinyldiphenylethoxysilane, propenyldiphenylethoxysilane, ethynyldiphenylethoxysilane, propynyldiphenylethoxysilane, dimethylphenylethoxysilane, diethylphenylethoxysilane, dipropylphenylethoxysilane, divinylphenylethoxysilane, dipropenylethoxysilane, diacetylphenylethoxysilane, dipropynylphenylethoxysilane, methylethylphenylethoxysilane, methylpropylphenylethoxysilane, ethylpropylphenylethoxysilane, methylvinylphenylethoxysilane, ethylpropenylphenylethoxysilane, methylacetylphenylethoxysilane, and ethylpropynylphenylethoxysilane.
<xnotran> , , , , , , , , , , , , , , , , , 2- ( ) , 2- ( ) ,3- ( ) ,3- ( ) , , , , , , , , , γ - , γ - , γ - , γ - , γ - , γ - , </xnotran> At least one of gamma-methacryloxypropylmethoxydiethylsilane, gamma-methacryloxypropyldimethoxyethylsilane, gamma-methacryloxypropylethoxydiethylsilane, gamma-methacryloxypropyldiethoxyethylsilane, and gamma-methacryloxypropyltriethoxysilane.
Preferably, the first and second liquid crystal materials are, the end-capping agents are 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane, hexamethyldisiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, hexaphenyldisiloxane, decamethyltetrasiloxane, decaphenyltetrasiloxane, 1,1,3,3-tetramethyl-1,3-diphenyldisiloxane and alpha, at least one of omega-divinyl silicone oil; the catalyst is sulfuric acid, acid clay or acid macroporous cation resin.
Preferably, the grafting monomer is a vinyl aromatic monomer and/or a comonomer; the molecular weight regulator is at least one of chloroform, carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, dimethyl xanthogen disulfide, diisopropyl xanthogen disulfide, terpene and alpha-methyl styrene dimer; the initiator is at least one of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate; the organic solvent is at least one of benzene, toluene, xylene, ethanol, methanol, ethyl acetate, acetone, carbon tetrachloride, diethyl ether, butanone, dichloromethane and trichloromethane.
Further, the vinyl aromatic monomer is at least one of styrene, methyl styrene and tert-butyl styrene, and the comonomer is at least one of acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, methyl methacrylate, ethyl methacrylate, phenyl maleimide, acrylamide and vinyl methyl ether.
The second purpose of the invention is realized by the following technical scheme: the low-gloss matte auxiliary agent is prepared by the preparation method of the low-gloss matte auxiliary agent.
The third purpose of the invention is realized by the following technical scheme: a method for producing a matte resin molded body, comprising the steps of:
(S1) taking the thermoplastic resin, the low-gloss matte auxiliary agent, the toughening agent, the lubricant and the antioxidant according to parts by weight for later use;
(S2) drying the prepared raw materials in an oven at 70-120 ℃ for 4-10h, and then feeding the dried raw materials into a high-speed mixer for premixing for 3-10 minutes to obtain a premix;
(S3) adding the premix into a double-screw extruder, carrying out melt extrusion at 230-300 ℃, and cooling and granulating to obtain a matte resin forming body;
the low-gloss matte auxiliary agent is prepared by adopting the preparation method of the low-gloss matte auxiliary agent.
The invention has the beneficial effects that:
1. according to the invention, through copolymerization modification of organosilicon and monomers, the low-gloss matte auxiliary agent has proper compatibility provided by resin, can be combined with a resin substrate more tightly, and has matte property given by organosilicon materials with lower surface tension.
2. The low-gloss matte auxiliary agent provides a good matte effect for the matte resin forming body, and can meet the matte requirement without adding unnecessary components which have great influence on other properties; the glossiness can be flexibly adjusted within a certain range. Because there is a certain difference in compatibility between the silicone chain and the resin, during the processing, the silicone matte auxiliary agent tends to be enriched on the surface of the material, so that the surface of the material becomes rugged and rough microscopically, when light irradiates on the surface of the material, a part of light is absorbed and refracted into the material, and the other light generates diffuse reflection on the rough interface of the resin and the rubber, so that the intensity of reflected light detected and observed is reduced, and the glossiness is reduced.
3. The low-gloss matte auxiliary agent is simple and convenient in synthesis process, economical and efficient.
4. The low-gloss matte auxiliary agent is widely used and has small influence on performance.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A preparation method of a low-gloss matte auxiliary agent comprises the following steps:
A. synthesis of multifunctional silicone solution:
a1, uniformly mixing a cyclic siloxane monomer, a phenyl siloxane monomer, a vinyl siloxane monomer and an end-capping reagent to obtain an organic silicon monomer mixed solution;
a2, adding a catalyst into the organic silicon monomer mixed solution, and reacting at the temperature of 90 ℃ for 9 hours to obtain transparent modified organic polysiloxane liquid;
a3, separating the catalyst from the transparent modified organopolysiloxane liquid to obtain a multifunctional organosilicon solution;
B. and (3) synthesizing a low-gloss matte auxiliary agent:
b1, uniformly mixing a grafting monomer, a molecular weight regulator and an initiator to obtain a mixed monomer solution;
b2, adding an organic solvent into the multifunctional organic silicon solution to obtain a multifunctional organic silicon mixed solution;
and B3, continuously adding the mixed monomer solution into the multifunctional organic silicon mixed solution for 2 hours at the temperature of 80 ℃, then keeping the temperature of 80 ℃ for 2 hours, and then carrying out vacuum separation on the organic solvent to obtain the low-gloss matte auxiliary agent.
In the step A, the phenyl siloxane monomer, the vinyl siloxane monomer and the end-capping agent respectively account for 6% of the weight ratio of the cyclic siloxane monomer; the catalyst accounts for 12% of the weight of the cyclic siloxane monomer.
In the step B, the molecular weight regulator and the initiator respectively account for 3 percent of the weight of the grafting monomer; the weight of the organic solvent is 2 times of the total mass of the multifunctional organosilicon solution; the weight ratio of the multifunctional silicone solution to the weight of the grafting monomer is 2.
The cyclic siloxane monomer is octamethylcyclotetrasiloxane.
The phenyl siloxane monomer is diphenyl dimethoxysilane.
The vinyl siloxane monomer is vinyl trimethoxy silane.
The end-capping agent is hexamethyldisiloxane; the catalyst is acidic macroporous cation resin.
The grafting monomer is formed by mixing styrene and acrylonitrile according to the weight ratio of 6; the molecular weight regulator is n-dodecyl mercaptan; the initiator is benzoyl peroxide; the organic solvent is xylene.
Example 2
A preparation method of a low-gloss matte auxiliary agent comprises the following steps:
A. synthesis of multifunctional silicone solution:
a1, uniformly mixing a cyclic siloxane monomer, a phenyl siloxane monomer, a vinyl siloxane monomer and an end-capping reagent to obtain an organic silicon monomer mixed solution;
a2, adding a catalyst into the organic silicon monomer mixed solution, and reacting at 85 ℃ for 6 hours to obtain transparent modified organic polysiloxane liquid;
a3, separating the catalyst from the transparent modified organopolysiloxane liquid to obtain a multifunctional organosilicon solution;
B. and (3) synthesizing a low-gloss matte auxiliary agent:
b1, uniformly mixing a grafting monomer, a molecular weight regulator and an initiator to obtain a mixed monomer solution;
b2, adding an organic solvent into the multifunctional organic silicon solution to obtain a multifunctional organic silicon mixed solution;
and B3, continuously adding the mixed monomer solution into the multifunctional organic silicon mixed solution for 1h at the temperature of 60 ℃, then keeping the temperature of 60 ℃ for 1h, and then carrying out vacuum separation on the organic solvent to obtain the low-gloss matte auxiliary agent.
In the step A, the phenyl siloxane monomer, the vinyl siloxane monomer and the end-capping agent respectively account for 1% of the weight of the cyclic siloxane monomer; the catalyst accounts for 1% of the weight of the cyclic siloxane monomer.
In the step B, the molecular weight regulator and the initiator respectively account for 1 percent of the weight of the grafting monomer; the weight of the organic solvent is 0.5 times of the total mass of the multifunctional organic silicon solution; the weight ratio of the multifunctional organosilicon solution to the weight of the grafting monomer is 1.
The cyclic siloxane monomer is hexamethylcyclotrisiloxane.
The phenyl siloxane monomer is phenyl trimethoxy silane.
The vinyl siloxane monomer is vinyl triethoxysilane.
The end-capping agent is decamethyltetrasiloxane; the catalyst is acid clay.
The grafting monomer is formed by mixing styrene and acrylonitrile according to the weight ratio of 6; the molecular weight regulator is n-dodecyl mercaptan; the initiator is tert-butyl hydroperoxide; the organic solvent is xylene.
Example 3
A preparation method of a low-gloss matte auxiliary agent comprises the following steps:
A. synthesis of multifunctional silicone solution:
a1, uniformly mixing a cyclic siloxane monomer, a phenyl siloxane monomer, a vinyl siloxane monomer and an end-capping reagent to obtain an organic silicon monomer mixed solution;
a2, adding a catalyst into the organic silicon monomer mixed solution, and reacting at the temperature of 100 ℃ for 12 hours to obtain transparent modified organic polysiloxane liquid;
a3, separating the catalyst from the transparent modified organopolysiloxane liquid to obtain a multifunctional organosilicon solution;
B. and (3) synthesizing a low-gloss matte auxiliary agent:
b1, uniformly mixing a grafting monomer, a molecular weight regulator and an initiator to obtain a mixed monomer solution;
b2, adding an organic solvent into the multifunctional organic silicon solution to obtain a multifunctional organic silicon mixed solution;
and B3, continuously adding the mixed monomer solution into the multifunctional organic silicon mixed solution for 3 hours at the temperature of 90 ℃, then keeping the temperature of 90 ℃ for 3 hours, and then carrying out vacuum separation on the organic solvent to obtain the low-gloss matte auxiliary agent.
In the step A, the phenyl siloxane monomer, the vinyl siloxane monomer and the end-capping agent respectively account for 15% of the weight ratio of the cyclic siloxane monomer; the catalyst accounts for 20% of the weight of the cyclic siloxane monomer.
In the step B, the molecular weight regulator and the initiator respectively account for 5% of the weight ratio of the grafting monomer; the weight of the organic solvent is 3 times of the total mass of the multifunctional organic silicon solution; the weight ratio of the multifunctional silicone solution to the weight of the grafting monomer is 4.
The cyclic siloxane monomer is octamethylcyclotetrasiloxane.
The phenyl siloxane monomer is phenyl trimethoxy silane.
The vinyl siloxane monomer is vinyl trimethoxy silane.
The end-capping agent is hexamethyldisiloxane; the catalyst is acidic macroporous cation resin.
The grafting monomer is formed by mixing styrene and acrylonitrile according to the weight ratio of 6; the molecular weight regulator is n-dodecyl mercaptan; the initiator is benzoyl peroxide; the organic solvent is xylene.
Example 4
A preparation method of a low-gloss matte auxiliary agent comprises the following steps:
A. synthesis of multifunctional silicone solution:
a1, uniformly mixing a cyclic siloxane monomer, a phenyl siloxane monomer, a vinyl siloxane monomer and an end-capping reagent to obtain an organic silicon monomer mixed solution;
a2, adding a catalyst into the organic silicon monomer mixed solution, and reacting at 880 ℃ for 10 hours to obtain transparent modified organic polysiloxane liquid;
a3, separating the catalyst from the transparent modified organopolysiloxane liquid to obtain a multifunctional organosilicon solution;
B. and (3) synthesizing a low-gloss matte auxiliary agent:
b1, uniformly mixing a grafting monomer, a molecular weight regulator and an initiator to obtain a mixed monomer solution;
b2, adding an organic solvent into the multifunctional organic silicon solution to obtain a multifunctional organic silicon mixed solution;
and B3, continuously adding the mixed monomer solution into the multifunctional organic silicon mixed solution for 2 hours at the temperature of 80 ℃, then keeping the temperature of 80 ℃ for 2 hours, and then carrying out vacuum separation on the organic solvent to obtain the low-gloss matte auxiliary agent.
In the step A, the phenyl siloxane monomer, the vinyl siloxane monomer and the end-capping agent respectively account for 8% of the weight ratio of the cyclic siloxane monomer; the catalyst accounts for 10% of the weight of the cyclic siloxane monomer.
In the step B, the molecular weight regulator and the initiator respectively account for 3 percent of the weight of the grafting monomer; the weight of the organic solvent is 2 times of the total mass of the multifunctional organic silicon solution; the weight ratio of the multifunctional silicone solution to the weight of the grafting monomer is 3.
The cyclic siloxane monomer is hexamethylcyclotrisiloxane.
The phenyl siloxane monomer is phenyl trimethoxy silane.
The vinyl siloxane monomer is vinyl trimethoxy silane.
The end-capping agent is hexamethyldisiloxane; the catalyst is acidic macroporous cation resin.
The grafting monomer is formed by mixing styrene and acrylonitrile according to the weight ratio of 6; the molecular weight regulator is n-dodecyl mercaptan; the initiator is benzoyl peroxide; the organic solvent is xylene.
Comparative example 1
A low gloss matte aid is the commercially available matting agent Blendex MAT (BMAT).
Comparative example 2
A low-gloss matte auxiliary agent is commercially available superfine talcum powder.
Comparative example 3
A low-gloss matte auxiliary agent, which is taken from the matte organic silicon high-impact toughening agent prepared in the embodiment 1 of the application number CN 202011588159.
Comparative example 4
This comparative example differs from example 1 in that:
the weight ratio of the multifunctional organosilicon solution to the weight of the grafting monomer is 1.
Comparative example 5
This comparative example differs from example 1 in that:
the weight ratio of the multifunctional silicone solution to the weight of the grafting monomer is 4.
Performance testing
The low-gloss matte auxiliary agents of examples 1-4 and comparative examples 1-5 are respectively used for preparing matte resin molded bodies, wherein the preparation method of the matte resin molded bodies comprises the following steps:
(S1) taking ABS resin AF366F, polycarbonate LXTY1609T-11H, AS resin PN-127L100, low-gloss matte auxiliary agent, toughening agent MBS, lubricant PETS and antioxidant 1010 according to parts by weight for later use;
(S2) drying the prepared raw materials in a 90 ℃ oven for 6 hours, and then feeding the dried raw materials into a high-speed mixer for premixing for 6 minutes to obtain a premix;
(S3) adding the premix into a double-screw extruder for melt extrusion, and cooling and granulating to obtain a matte resin forming body;
the processing temperature of each section of the double-screw extruder from the feeding section is respectively as follows: 230 ℃, 240 ℃, 250 ℃, 260 ℃, 250 ℃ of the head temperature and 360r/min of the screw rotation speed.
The weight parts of the components are shown in the following table 1:
the matte resin molded bodies of the experimental groups 1 to 5 and the comparative groups 1 to 5 were subjected to tensile strength, impact strength, melt index, softening temperature and gloss tests 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, wherein the unit is MPa;
impact strength: according to the regulation of GB/T18432008, the notch impact strength of a cantilever beam is tested at normal temperature by the type A notch, and the unit is kJ/m 2 ；
Melt index: according to the specification of ASTM D1238, the melt index is tested under the test condition of 220 ℃/10kg, and the unit is g/10min;
softening temperature: testing the Vicat softening temperature according to the specification of ASTM D1525, wherein the unit is;
gloss: testing the 60 DEG specular gloss value according to the regulations of GB/T9754-2007;
the test results are shown in table 2 below:
as can be seen from the above Table 2, the low gloss matte auxiliary agent adopted in the present application has better matte effect on the resin and less influence on the tensile strength and the impact strength as compared with the comparative example. Compared with the comparison group 3, the experiment group 1 can have equivalent gloss effect to the comparison group 3 by adding a smaller amount of the low-gloss matte auxiliary agent, the using amount is less, and the cost is lower.
The above-described embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A preparation method of a low-gloss matte auxiliary agent is characterized by comprising the following steps:
A. synthesis of multifunctional silicone solution:
a1, uniformly mixing a cyclic siloxane monomer, a phenyl siloxane monomer, a vinyl siloxane monomer and an end-capping reagent to obtain an organic silicon monomer mixed solution;
a2, adding a catalyst into the organic silicon monomer mixed solution, and reacting at the temperature of 85-100 ℃ for 6-12h to obtain transparent modified organic polysiloxane liquid;
a3, separating the catalyst from the transparent modified organopolysiloxane liquid to obtain a multifunctional organosilicon solution;
B. and (3) synthesizing a low-gloss matte auxiliary agent:
b1, uniformly mixing a grafting monomer, a molecular weight regulator and an initiator to obtain a mixed monomer solution;
b2, adding an organic solvent into the multifunctional organic silicon solution to obtain a multifunctional organic silicon mixed solution;
and B3, continuously adding the mixed monomer solution into the multifunctional organic silicon mixed solution for 1-3 hours at the temperature of 60-90 ℃, then keeping the temperature of 60-90 ℃ for 1-3 hours, and then carrying out vacuum separation on the organic solvent to obtain the low-gloss matte auxiliary agent.
2. The method for preparing the low-gloss matte auxiliary according to claim 1, wherein the method comprises the following steps: in the step A, the phenyl siloxane monomer, the vinyl siloxane monomer and the end-capping agent respectively account for 0.5-15% of the weight ratio of the cyclic siloxane monomer; the catalyst accounts for 1-20% of the weight of the cyclic siloxane monomer.
3. The method for preparing the low-gloss matte auxiliary according to claim 1, wherein the method comprises the following steps: in the step B, the molecular weight regulator and the initiator respectively account for 0.5-5% of the weight ratio of the grafting monomer; the weight of the organic solvent is 0.5 to 3 times of the total mass of the multifunctional organic silicon solution; the weight ratio of the multifunctional organic silicon solution to the weight of the grafting monomer is 1-4.
4. The method for preparing the low-gloss matte auxiliary according to claim 1, wherein the method comprises the following steps: <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> At least one of methylheptvinylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, and methylheptenylcyclotetrasiloxane.
5. The method for preparing the low-gloss matte auxiliary according to claim 1, wherein the method comprises the following steps: <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> At least one of propenyl diphenylethoxysilane, ethynyldiphenylethoxysilane, propynyl diphenylethoxysilane, dimethylphenylethoxysilane, diethylphenylethoxysilane, dipropylphenylethoxysilane, divinylphenylethoxysilane, dipropenylphenylethoxysilane, diacetylphenylethoxysilane, dipropynylphenylethoxysilane, methylethylphenylethoxysilane, methylpropylphenylethoxysilane, ethylpropylphenylethoxysilane, methylvinylphenylethoxysilane, ethylpropenylphenylethoxysilane, methylacetylphenylethoxysilane and ethylpropynyl phenylethoxysilane.
6. The method for preparing the low-gloss matte auxiliary according to claim 1, wherein the method comprises the following steps: <xnotran> , , , , , , , , , , , , , , , , 2- ( ) , 2- ( ) ,3- ( ) ,3- ( ) , , , , , , , , , γ - , γ - , γ - , γ - , γ - , γ - , </xnotran> At least one of gamma-methacryloxypropylmethoxydiethylsilane, gamma-methacryloxypropyldimethoxyethylsilane, gamma-methacryloxypropylethoxydiethylsilane, gamma-methacryloxypropyldiethoxyethylsilane, and gamma-methacryloxypropyltriethoxysilane.
7. The method for preparing the low-gloss matte auxiliary according to claim 1, wherein the method comprises the following steps: the end-capping agent is 1,1, 3-tetraphenyl-1, 3-divinyldisiloxane, hexamethyldisiloxane, 1,1, 3-tetramethyl-1, 3-divinyldisiloxane, hexaphenyldisiloxane, decamethyltetrasiloxane, decaphenyltetrasiloxane, 1,1, 3-tetramethyl-1, 3-diphenyldisiloxane and alpha, at least one of omega-divinyl silicone oil; the catalyst is sulfuric acid, acid clay or acid macroporous cation resin.
8. The method for preparing the low-gloss matte auxiliary according to claim 1, wherein the method comprises the following steps: the grafting monomer is a vinyl aromatic monomer and/or a comonomer; the molecular weight regulator is at least one of chloroform, carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, dimethyl xanthogen disulfide, diisopropyl xanthogen disulfide, terpene and alpha-methyl styrene dimer; the initiator is at least one of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate; the organic solvent is at least one of benzene, toluene, xylene, ethanol, methanol, ethyl acetate, acetone, carbon tetrachloride, diethyl ether, butanone, dichloromethane and trichloromethane.
9. A low-gloss matte auxiliary agent is characterized in that: the low-gloss matte auxiliary agent is prepared by the preparation method of any one of claims 1-8.
10. A method for producing a matte resin molded body, comprising the steps of:
(S1) taking thermoplastic resin, a low-gloss matte auxiliary agent, a toughening agent, a lubricant and an antioxidant according to parts by weight for later use;
(S2) drying the prepared raw materials in an oven at 70-120 ℃ for 4-10h, and then feeding the dried raw materials into a high-speed mixer for premixing for 3-10 minutes to obtain a premix;
(S3) adding the premix into a double-screw extruder, carrying out melt extrusion at 230-300 ℃, and cooling and granulating to obtain a matte resin forming body;
the low-gloss matte auxiliary agent is prepared by the preparation method of the low-gloss matte auxiliary agent according to any one of claims 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210975250.1A CN115181223B (en) | 2022-08-15 | 2022-08-15 | Low-gloss matte auxiliary agent, preparation method thereof and molded body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210975250.1A CN115181223B (en) | 2022-08-15 | 2022-08-15 | Low-gloss matte auxiliary agent, preparation method thereof and molded body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115181223A true CN115181223A (en) | 2022-10-14 |
| CN115181223B CN115181223B (en) | 2023-08-29 |
Family
ID=83523411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210975250.1A Active CN115181223B (en) | 2022-08-15 | 2022-08-15 | Low-gloss matte auxiliary agent, preparation method thereof and molded body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115181223B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115572107A (en) * | 2022-11-11 | 2023-01-06 | 亚士创能新材料(滁州)有限公司 | Temperature change resistant stone-like paint and preparation method and application thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4927880A (en) * | 1988-11-14 | 1990-05-22 | General Electric Company | Low gloss molded articles using polyorganosiloxane/polyvinyl-based graft polymers |
| CA2046469A1 (en) * | 1990-07-09 | 1992-01-10 | Tooru Katsumata | Low gloss polyacetal resin composition and molded article |
| JPH10265536A (en) * | 1997-03-25 | 1998-10-06 | Mitsubishi Rayon Co Ltd | Modified silicone-containing resin composition and cured article manufacture of the same |
| JP2000159782A (en) * | 1998-11-25 | 2000-06-13 | Shin Etsu Chem Co Ltd | Cyclotetrasiloxane having (meth)acryloxypropyl group, and production thereof |
| JP2005307073A (en) * | 2004-04-23 | 2005-11-04 | Mitsubishi Rayon Co Ltd | Graft copolymer, method for producing the same, and thermoplastic resin composition |
| JP2007302837A (en) * | 2006-05-15 | 2007-11-22 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition and molded product thereof |
| CN102432883A (en) * | 2011-09-09 | 2012-05-02 | 汕头市骏码凯撒有限公司 | Preparation method of phenyl-vinyl silicon oil |
| CN104693334A (en) * | 2013-12-04 | 2015-06-10 | 三星Sdi株式会社 | Styrene-based copolymer and thermoplastic resin composition including the same |
| US20150376392A1 (en) * | 2014-06-26 | 2015-12-31 | Samsung Sdi Co., Ltd. | Thermoplastic Resin Composition |
| KR20160001575A (en) * | 2014-06-27 | 2016-01-06 | 제일모직주식회사 | Styrenic copolymers and thermoplastic resin composition comprising thereof |
| CN105273116A (en) * | 2014-06-27 | 2016-01-27 | 三星Sdi株式会社 | Copolymers and thermoplastic resin composition comprising the same |
| CN107298827A (en) * | 2017-06-29 | 2017-10-27 | 上海金山锦湖日丽塑料有限公司 | Low gloss heat-resisting ABS resin and preparation method thereof |
| CN109280170A (en) * | 2018-09-17 | 2019-01-29 | 青岛科技大学 | A kind of functional polysiloxanes copolymer preparation method of phosphonitrile catalysis |
| CN112724335A (en) * | 2020-12-29 | 2021-04-30 | 铨盛聚碳科技股份有限公司 | Matte organic silicon high-impact-resistance toughening agent and preparation method thereof |
-
2022
- 2022-08-15 CN CN202210975250.1A patent/CN115181223B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4927880A (en) * | 1988-11-14 | 1990-05-22 | General Electric Company | Low gloss molded articles using polyorganosiloxane/polyvinyl-based graft polymers |
| CA2046469A1 (en) * | 1990-07-09 | 1992-01-10 | Tooru Katsumata | Low gloss polyacetal resin composition and molded article |
| JPH10265536A (en) * | 1997-03-25 | 1998-10-06 | Mitsubishi Rayon Co Ltd | Modified silicone-containing resin composition and cured article manufacture of the same |
| JP2000159782A (en) * | 1998-11-25 | 2000-06-13 | Shin Etsu Chem Co Ltd | Cyclotetrasiloxane having (meth)acryloxypropyl group, and production thereof |
| JP2005307073A (en) * | 2004-04-23 | 2005-11-04 | Mitsubishi Rayon Co Ltd | Graft copolymer, method for producing the same, and thermoplastic resin composition |
| JP2007302837A (en) * | 2006-05-15 | 2007-11-22 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition and molded product thereof |
| CN102432883A (en) * | 2011-09-09 | 2012-05-02 | 汕头市骏码凯撒有限公司 | Preparation method of phenyl-vinyl silicon oil |
| CN104693334A (en) * | 2013-12-04 | 2015-06-10 | 三星Sdi株式会社 | Styrene-based copolymer and thermoplastic resin composition including the same |
| US20150376392A1 (en) * | 2014-06-26 | 2015-12-31 | Samsung Sdi Co., Ltd. | Thermoplastic Resin Composition |
| KR20160001575A (en) * | 2014-06-27 | 2016-01-06 | 제일모직주식회사 | Styrenic copolymers and thermoplastic resin composition comprising thereof |
| CN105273116A (en) * | 2014-06-27 | 2016-01-27 | 三星Sdi株式会社 | Copolymers and thermoplastic resin composition comprising the same |
| CN107298827A (en) * | 2017-06-29 | 2017-10-27 | 上海金山锦湖日丽塑料有限公司 | Low gloss heat-resisting ABS resin and preparation method thereof |
| CN109280170A (en) * | 2018-09-17 | 2019-01-29 | 青岛科技大学 | A kind of functional polysiloxanes copolymer preparation method of phosphonitrile catalysis |
| CN112724335A (en) * | 2020-12-29 | 2021-04-30 | 铨盛聚碳科技股份有限公司 | Matte organic silicon high-impact-resistance toughening agent and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115572107A (en) * | 2022-11-11 | 2023-01-06 | 亚士创能新材料(滁州)有限公司 | Temperature change resistant stone-like paint and preparation method and application thereof |
| CN115572107B (en) * | 2022-11-11 | 2024-01-19 | 亚士创能新材料(滁州)有限公司 | Real stone paint for temperature-change-resistant construction and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115181223B (en) | 2023-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102782039B (en) | Thermoplastic resin composition for vehicle lamp housings | |
| US4885209A (en) | Thermoplastic silicon rubber graft polymers (II) | |
| KR102086537B1 (en) | Preparation method of modified acrylonitrile-butadiene-styrene resin and modified acrylonitrile-butadiene-styrene resin produced by thereof | |
| WO2009073247A1 (en) | Resinous compositions and articles made therefrom | |
| CN1326897C (en) | Rubber modified resin and thermoplastic resin composition containing the same | |
| EP1937773A2 (en) | Improved low gloss mass polymerized rubber-modified monovinylidene aromatic copolymer composition | |
| AU2005292448A1 (en) | Resinous composition with improved resistance to plate-out information | |
| WO2008075809A1 (en) | Composite of nylon polymer | |
| TWI789396B (en) | Graft copolymer containing polyorganosiloxane, graft copolymer, thermoplastic resin composition, and molded article | |
| JP2003534433A (en) | Weatherable polymer blends, their use and molded articles obtained therefrom | |
| WO2005108447A1 (en) | Improved mass polymerized rubber-modified monovinylidene aromatic copolymer composition | |
| CN112745616B (en) | Modified acrylic ester polymer composition | |
| US5047475A (en) | Delustered thermoplastic resin composition with good impact resistance | |
| US20090269531A1 (en) | Resinous compositions, articles made therefrom and process | |
| CN115181223A (en) | Low-gloss matte auxiliary agent, preparation method thereof and formed body | |
| CA1325487C (en) | Thermoplastic polymethacrylimide resin composition | |
| CN106519235A (en) | Polysiloxane crosslinking agent, vinyl grafted copolymer powder prepared by using crosslinking agent and preparation method of vinyl grafted copolymer powder | |
| CN111788241B (en) | Polyorganosiloxane-containing graft copolymer powder, resin composition using same, and molded article comprising same | |
| CN114085326A (en) | Graft crosslinking agent, preparation method thereof, impact modifier containing graft crosslinking agent and application of impact modifier | |
| JP7155777B2 (en) | Polyorganosiloxane-containing graft copolymer, thermoplastic resin composition and molded article | |
| KR0147781B1 (en) | Thermoplastic resin composition | |
| KR20000029738A (en) | Impact resistant thermoplastic moulding materials | |
| CN1260290C (en) | Polystyrene resin composition for chip plastic card | |
| KR20220053462A (en) | Thermoplastic resin composition, and molded product therefrom | |
| CN117597393A (en) | Thermoplastic resin composition, method for producing the same, and molded article produced using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |