CN106699958A - Method for polymerizing acrylate organic silicon on titanium dioxide surface - Google Patents

Method for polymerizing acrylate organic silicon on titanium dioxide surface Download PDF

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CN106699958A
CN106699958A CN201611254030.0A CN201611254030A CN106699958A CN 106699958 A CN106699958 A CN 106699958A CN 201611254030 A CN201611254030 A CN 201611254030A CN 106699958 A CN106699958 A CN 106699958A
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parts
slurry
titanium dioxide
water
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CN106699958B (en
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王彦华
夏浙安
陈建定
章圣苗
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East China 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3669—Treatment with low-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3676—Treatment with macro-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

The invention relates to a method for polymerizing acrylate organic silicon on a titanium dioxide surface. The method is characterized by comprising the following steps: carrying out surface modification on TiO2 by using a cationic monomer, carrying out pre-emulsification on a monomer mixture composed of 15 parts of methyl methacrylate, 15 parts of butyl acrylate, 10 parts of vinyltriethoxysilane and 5 parts of alpha-methacrylic acid with 80 parts of water, 1 part of initiator ammonium persulfate and 2 parts of emulsifier to obtain a pre-emulsified mixed monomer emulsion; and heating the TiO2 slurry to 80 DEG C, adding 0.3 part of initiator ammonium persulfate, initiating the reaction for 5 minutes, slowly adding the pre-emulsified mixed monomer emulsion into the TiO2 slurry within 2-5 hours, and keeping the temperature at DEG C to carry out thermostatic reaction for 1 hour, thereby obtaining the polyacrylate-organic-silicon-coated TiO2 slurry.

Description

A kind of method that use acrylate organosilicon is polymerized in titanium dioxide surface
Technical field
The present invention relates to a kind of method that use acrylate organosilicon is polymerized in titanium dioxide surface.
Background technology
Titanium dioxide can be divided into rutile-type, Detitanium-ore-type and plate titanium-type three types, wherein plate from crystal structure The more difficult acquisition of titanium-type titanium dioxide, it is uncommon in actual applications.Rutile-type belongs to tetragonal crystal system.There is a titanium at lattice center Atom, there is 6 oxygen atoms around titanium atom, there is 3 titanium atoms around oxygen atom.Rutile unit cell contains two titanium dioxides Titanium molecule, lattice is small and tight, is most stable of in three kinds of crystal formations.Also, the density and refractive index of rutile-type are also relatively Greatly.Detitanium-ore-type also belongs to tetragonal crystal system.Titanium atom is located at octahedral center, is surround by 6 oxygen atoms, and two of which oxygen is former Sub is closer to the distance, so occurring in the octahedral form for distorting.Detitanium-ore-type is very stable at low temperature, about at 650 DEG C Start stabilization and the conversion of crystal formation, its conversion process receives temperature, if add additive and add the factor shadows such as which kind of additive Ring.Optical property is one of most important characteristic of titanium dioxide, because the optical property of titanium dioxide has closely with its performance Relation, such as refractive index, covering power, scattering force, weatherability, these are all embodying for optical property.
Coatings industry is the first large user of titanium dioxide, and titanium dioxide major part is consumed by coatings industry.Titanium dioxide Titanium is most important pigment in coating material production, and its effect is not only to cover and decorate, it is often more important that can improve coating Physical and chemical performance, strengthens chemical stability, improves covering power, reducing power, anticorrosive property, fast light and weatherability, strengthens the machine of film Tool intensity and adhesive force, prevent from ftractureing and come off, and prevent ultraviolet and moisture from passing through, and extend the service life of object.
At 70-100 nanometers, its particle surface contains substantial amounts of hydroxyl to the particle size range of pigmentary titanium dioxide, it is easy to send out Raw to reunite, the covering power of titanium dioxide can be greatly affected after reunion.So, titanium dioxide will carry out younger before Thin grinding, adds a certain amount of dispersant in process of lapping, it is therefore an objective to separate titanium dioxide granule, such titanium dioxide hides Lid ability can just obtain bigger performance.In addition, titanium dioxide surface is very sensitive to environment, a small amount of impurity may be caused Scattered particle is reunited again, and the use scope of titanium dioxide is widely, and use occasion varies, slightly Will result in scattered particle accidentally to reunite again, so necessary coat one layer of protection in titanium dioxide surface Layer, titanium dioxide granule is kept apart, it is to avoid the reunion of titanium dioxide granule, the covering power of titanium dioxide is obtained bigger Play.
The present invention mainly coats acrylate Organosiliconcopolymere in titanium dioxide surface, is applied in water paint. Titanium dioxide surface polymer overmold except can reduce reunion, to greatest extent play titanium dioxide covering power in addition to, also Some other benefits, summarize with advantages below：
（1）The reunion of titanium dioxide can be prevented, it is kept monodisperse status, strengthen its covering power, improve titanium dioxide Utilization rate.
（2）It is easy to use, titania slurry is mixed with emulsion and adds other auxiliary agents, by two when reduction is used The step of dry powder dispersion of titanium oxide is into slurry, and titanium dioxide is it may happen that reunite, it is impossible to effectively dispersion.
（3）Titanium dioxide transported with dry powder, used, but transported with slurry, used, it is to avoid The generation of titanium dioxide dust, can play the effect of environmental protection, and the loss of raw material can be reduced again.
（4）Compatibility after titanium dioxide surface polymer overmold with emulsion is more preferable, can improve the performance of coating.
In order that polymer covering layer can preferably be combined with titanium dioxide surface, the present invention first with the sun with double bond from Sub- monomer is modified to titanium dioxide surface, and modified mechanism is：Titanium dioxide surface is per se with substantial amounts of negative electrical charge, band Cationic monomer one end of double bond carries positive charge, and titanium dioxide surface is adsorbed onto by charge effect, and the other end contains insatiable hunger Titanium dioxide surface is also stayed in the group of double bond vinyl, then is triggered and acrylate, vinyl with initiator ammonium persulfate Silane copolymer, finally obtained the titanium dioxide of Surface coating polyacrylate organosilicon.
The content of the invention
A kind of method that use acrylate organosilicon is polymerized in titanium dioxide surface, it is characterised in that：First to TiO2Enter Row surface is modified, by weight by 300 parts of TiO2Powder is added in 1000 parts of water, starts agitator stirring, makes TiO2Powder It is dispersed in water, adds 1.5 parts of dispersants, the TiO that will be obtained2Slurry carries out high speed dispersion on high speed dispersor, obtains To monodispersed TiO2Slurry；3 parts of cationic monomers, plus 20 parts of absolute ethyl alcohol dilutions are weighed, by the second containing cationic monomer Alcoholic solution is slowly dropped to TiO2In slurry, stir 30 minutes, obtain surface through the modifies finely dispersed TiO of cation mono2 Slurry；
Will be by 15 parts of methyl methacrylate, 15 parts of butyl acrylate, 10 parts of VTES and Alpha-Methyl third 5 parts of mix monomers of composition of olefin(e) acid carry out pre-emulsification with 80 parts of water, 1 part of initiator ammonium persulfate, 2 parts of emulsifying agent, obtain pre- breast Change mix monomer emulsion；
By above-mentioned TiO2Slurry is heated to 80 DEG C, adds 0.3 part of initiator ammonium persulfate, and initiation reaction 5 minutes then will be pre- The mix monomer emulsion for having emulsified is slowly added into above-mentioned TiO2In slurry, add time control at 2-5 hours, addition is finished 85 DEG C of maintenance isothermal reaction 1 hour, obtains TiO of the surface through polyacrylate silicone covering afterwards2Slurry；
Described cationic monomer be MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, Acrylic acid N, N- dimethylamino ethyl ester it is therein one or more；
Described emulsifying agent is NPE ammonium sulfate；
Described TiO2Powder is anatase pigmentary TiO2；
Described dispersant is PAA.
Specific embodiment
Embodiment 1
First to TiO2Carry out surface to be modified, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, and startup is stirred Device stirring is mixed, makes TiO2Powder is dispersed in water, adds 1.5kg dispersants, the TiO that will be obtained2Slurry is in high speed dispersor On carry out high speed dispersion, obtain monodispersed TiO2Slurry；3kg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides are weighed, plus 20kg absolute ethyl alcohols are diluted, and the ethanol solution containing cationic monomer is slowly dropped into TiO2In slurry, stir 30 minutes, obtain To surface through the modifies finely dispersed TiO of cation mono2Slurry；Will be by the kg of methyl methacrylate 15, butyl acrylate The mix monomer and water 80kg, initiator mistake of 15 kg, the kg of VTES 10 and α-methacrylic acid 5kg compositions Ammonium sulfate 1kg, emulsifying agent NPE ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer emulsion；Will Above-mentioned TiO2Slurry is heated to 80 DEG C, adds 0.3kg initiator ammonium persulfates, and initiation reaction 5 minutes is then good by pre-emulsification Mix monomer emulsion be slowly added into above-mentioned TiO2In slurry, add time control at 2 hours, addition maintains 85 after finishing DEG C isothermal reaction 1 hour, obtains the coated TiO in surface2Slurry.
Embodiment 2
First to TiO2Carry out surface to be modified, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, and startup is stirred Device stirring is mixed, makes TiO2Powder is dispersed in water, adds 1.5kg dispersants, the TiO that will be obtained2Slurry is in high speed dispersor On carry out high speed dispersion, obtain monodispersed TiO2Slurry；Weigh 3kg acrylyl oxy-ethyl-trimethyl salmiacs, plus 20kg without Water-ethanol is diluted, and the ethanol solution containing cationic monomer is slowly dropped into TiO2In slurry, stir 30 minutes, obtain surface Through the modifies finely dispersed TiO of cation mono2Slurry；Will by the kg of methyl methacrylate 15, the kg of butyl acrylate 15, The mix monomer and water 80kg, initiator ammonium persulfate of the kg of VTES 10 and α-methacrylic acid 5kg compositions 1kg, emulsifying agent NPE ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer emulsion；Will be above-mentioned TiO2Slurry is heated to 80 DEG C, adds 0.3kg initiator ammonium persulfates, initiation reaction 5 minutes, then by mixing that pre-emulsification is good Monomer emulsions are slowly added into above-mentioned TiO2In slurry, time control is added at 5 hours, addition maintains 85 DEG C of constant temperature after finishing Reaction 1 hour, obtains the coated TiO in surface2Slurry.
Embodiment 3
First to TiO2Carry out surface to be modified, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, and startup is stirred Device stirring is mixed, makes TiO2Powder is dispersed in water, adds 1.5kg dispersants, the TiO that will be obtained2Slurry is in high speed dispersor On carry out high speed dispersion, obtain monodispersed TiO2Slurry；Weigh 3kg acrylic acid N, N- dimethylamino ethyl ester, plus 20kg without Water-ethanol is diluted, and the ethanol solution containing cationic monomer is slowly dropped into TiO2In slurry, stir 30 minutes, obtain surface Through the modifies finely dispersed TiO of cation mono2Slurry；Will by the kg of methyl methacrylate 15, the kg of butyl acrylate 15, The mix monomer and water 80kg, initiator ammonium persulfate of the kg of VTES 10 and α-methacrylic acid 5kg compositions 1kg, emulsifying agent NPE ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer emulsion；Will be above-mentioned TiO2Slurry is heated to 80 DEG C, adds 0.3kg initiator ammonium persulfates, initiation reaction 5 minutes, then by mixing that pre-emulsification is good Monomer emulsions are slowly added into above-mentioned TiO2In slurry, time control is added at 3 hours, addition maintains 85 DEG C of constant temperature after finishing Reaction 1 hour, obtains the coated TiO in surface2Slurry.
Embodiment 4
First to TiO2Carry out surface to be modified, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, and startup is stirred Device stirring is mixed, makes TiO2Powder is dispersed in water, adds 1.5kg dispersants, the TiO that will be obtained2Slurry is in high speed dispersor On carry out high speed dispersion, obtain monodispersed TiO2Slurry；3kg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides are weighed, plus 20kg absolute ethyl alcohols are diluted, and the ethanol solution containing cationic monomer is slowly dropped into TiO2In slurry, stir 30 minutes, obtain To surface through the modifies finely dispersed TiO of cation mono2Slurry；Will be by the kg of methyl methacrylate 15, butyl acrylate The mix monomer and water 80kg, initiator mistake of 15 kg, the kg of VTES 10 and α-methacrylic acid 5kg compositions Ammonium sulfate 1kg, emulsifying agent NPE ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer emulsion；Will Above-mentioned TiO2Slurry is heated to 80 DEG C, adds 0.3kg initiator ammonium persulfates, and initiation reaction 5 minutes is then good by pre-emulsification Mix monomer emulsion be slowly added into above-mentioned TiO2In slurry, add time control at 4 hours, addition maintains 85 after finishing DEG C isothermal reaction 1 hour, obtains the coated TiO in surface2Slurry.
Embodiment 5
First to TiO2Carry out surface to be modified, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, and startup is stirred Device stirring is mixed, makes TiO2Powder is dispersed in water, adds 1.5kg dispersants, the TiO that will be obtained2Slurry is in high speed dispersor On carry out high speed dispersion, obtain monodispersed TiO2Slurry；Weigh 3kg acrylyl oxy-ethyl-trimethyl salmiacs, plus 20kg without Water-ethanol is diluted, and the ethanol solution containing cationic monomer is slowly dropped into TiO2In slurry, stir 30 minutes, obtain surface Through the modifies finely dispersed TiO of cation mono2Slurry；Will by the kg of methyl methacrylate 15, the kg of butyl acrylate 15, The mix monomer and water 80kg, initiator ammonium persulfate of the kg of VTES 10 and α-methacrylic acid 5kg compositions 1kg, emulsifying agent NPE ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer emulsion；Will be above-mentioned TiO2Slurry is heated to 80 DEG C, adds 0.3kg initiator ammonium persulfates, initiation reaction 5 minutes, then by mixing that pre-emulsification is good Monomer emulsions are slowly added into above-mentioned TiO2In slurry, time control is added at 4.5 hours, addition maintains 85 DEG C of perseverances after finishing Temperature reaction 1 hour, obtains the coated TiO in surface2Slurry.
Embodiment 6
First to TiO2Carry out surface to be modified, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, and startup is stirred Device stirring is mixed, makes TiO2Powder is dispersed in water, adds 1.5kg dispersants, the TiO that will be obtained2Slurry is in high speed dispersor On carry out high speed dispersion, obtain monodispersed TiO2Slurry；Weigh 3kg acrylic acid N, N- dimethylamino ethyl ester, plus 20kg without Water-ethanol is diluted, and the ethanol solution containing cationic monomer is slowly dropped into TiO2In slurry, stir 30 minutes, obtain surface Through the modifies finely dispersed TiO of cation mono2Slurry；Will by the kg of methyl methacrylate 15, the kg of butyl acrylate 15, The mix monomer and water 80kg, initiator ammonium persulfate of the kg of VTES 10 and α-methacrylic acid 5kg compositions 1kg, emulsifying agent NPE ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer emulsion；Will be above-mentioned TiO2Slurry is heated to 80 DEG C, adds 0.3kg initiator ammonium persulfates, initiation reaction 5 minutes, then by mixing that pre-emulsification is good Monomer emulsions are slowly added into above-mentioned TiO2In slurry, time control is added at 3.5 hours, addition maintains 85 DEG C of perseverances after finishing Temperature reaction 1 hour, obtains the coated TiO in surface2Slurry.

Claims (1)

1. a kind of method that use acrylate organosilicon is polymerized in titanium dioxide surface, it is characterised in that：First to TiO2Carry out table Face is modified, by weight by 300 parts of TiO2Powder is added in 1000 parts of water, starts agitator stirring, makes TiO2Powder is uniform It is dispersed in water, adds 1.5 parts of dispersants, the TiO that will be obtained2Slurry carries out high speed dispersion on high speed dispersor, obtains list Scattered TiO2Slurry；3 parts of cationic monomers, plus 20 parts of absolute ethyl alcohol dilutions are weighed, the ethanol containing cationic monomer is molten Liquid is slowly dropped to TiO2In slurry, stir 30 minutes, obtain surface through the modifies finely dispersed TiO of cation mono2Slurry Material；
Will be by 15 parts of methyl methacrylate, 15 parts of butyl acrylate, 10 parts of VTES and Alpha-Methyl third 5 parts of mix monomers of composition of olefin(e) acid carry out pre-emulsification with 80 parts of water, 1 part of initiator ammonium persulfate, 2 parts of emulsifying agent, obtain pre- breast Change mix monomer emulsion；
By above-mentioned TiO2Slurry is heated to 80 DEG C, adds 0.3 part of initiator ammonium persulfate, and initiation reaction 5 minutes then will be pre- The mix monomer emulsion for having emulsified is slowly added into above-mentioned TiO2In slurry, add time control at 2-5 hours, addition is finished 85 DEG C of maintenance isothermal reaction 1 hour, obtains TiO of the surface through polyacrylate silicone covering afterwards2Slurry；
Described cationic monomer be MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, Acrylic acid N, N- dimethylamino ethyl ester it is therein one or more；
Described emulsifying agent is NPE ammonium sulfate；
Described TiO2Powder is anatase pigmentary TiO2；
Described dispersant is PAA.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111533920A (en) * 2020-05-11 2020-08-14 张中明 Polyacrylate graftTiO2Modified polylactic acid antibacterial material and preparation method thereof
CN113583503A (en) * 2021-08-27 2021-11-02 河南佰利联新材料有限公司 Hybrid slurry, preparation method thereof and coating
CN114410131A (en) * 2021-12-14 2022-04-29 河南河大纳米材料工程研究中心有限公司 Water-phase instant titanium dioxide material and preparation method and application thereof
CN114621607A (en) * 2020-12-11 2022-06-14 中信钛业股份有限公司 Preparation method of special titanium dioxide pigment for high-temperature-resistant general engineering plastics

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1955218A (en) * 2006-10-27 2007-05-02 四川大学 Preparation method of ultraviolet light stabilizer
WO2009110848A1 (en) * 2008-03-04 2009-09-11 Agency For Science, Technology And Research Low shrinkage multifunctional ssq resins
WO2009141057A1 (en) * 2008-05-23 2009-11-26 Merck Patent Gmbh Polymerisation method for producing core-shell particles
CN102558412A (en) * 2012-02-10 2012-07-11 北京理工大学 Preparation method of high-strength titanium dioxide nano-grade composite hydrogel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1955218A (en) * 2006-10-27 2007-05-02 四川大学 Preparation method of ultraviolet light stabilizer
WO2009110848A1 (en) * 2008-03-04 2009-09-11 Agency For Science, Technology And Research Low shrinkage multifunctional ssq resins
WO2009141057A1 (en) * 2008-05-23 2009-11-26 Merck Patent Gmbh Polymerisation method for producing core-shell particles
CN102558412A (en) * 2012-02-10 2012-07-11 北京理工大学 Preparation method of high-strength titanium dioxide nano-grade composite hydrogel

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111533920A (en) * 2020-05-11 2020-08-14 张中明 Polyacrylate graftTiO2Modified polylactic acid antibacterial material and preparation method thereof
CN114621607A (en) * 2020-12-11 2022-06-14 中信钛业股份有限公司 Preparation method of special titanium dioxide pigment for high-temperature-resistant general engineering plastics
CN114621607B (en) * 2020-12-11 2023-06-06 中信钛业股份有限公司 Preparation method of high-temperature-resistant special titanium dioxide pigment for general engineering plastics
CN113583503A (en) * 2021-08-27 2021-11-02 河南佰利联新材料有限公司 Hybrid slurry, preparation method thereof and coating
CN113583503B (en) * 2021-08-27 2022-12-30 河南佰利联新材料有限公司 Hybrid slurry, preparation method thereof and coating
CN114410131A (en) * 2021-12-14 2022-04-29 河南河大纳米材料工程研究中心有限公司 Water-phase instant titanium dioxide material and preparation method and application thereof

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