CN106699958B - A method of it is polymerize in titanium dioxide surface with acrylate organosilicon - Google Patents

A method of it is polymerize in titanium dioxide surface with acrylate organosilicon Download PDF

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CN106699958B
CN106699958B CN201611254030.0A CN201611254030A CN106699958B CN 106699958 B CN106699958 B CN 106699958B CN 201611254030 A CN201611254030 A CN 201611254030A CN 106699958 B CN106699958 B CN 106699958B
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titanium dioxide
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CN106699958A (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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    • 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
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    • 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
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    • 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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    • 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
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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
    • C09C1/3676—Treatment with macro-molecular 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
    • 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
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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
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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    • 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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    • 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
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    • 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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Abstract

A method of it is polymerize in titanium dioxide surface with acrylate organosilicon, it is characterised in that：First with cationic monomer to TiO2Carry out surface modification, then by by 2 parts of 80 parts of 15 parts of methyl methacrylate, 15 parts of butyl acrylate, 5 parts of mix monomers formed of 10 parts of vinyltriethoxysilane and α methacrylic acids and water, 1 part of initiator ammonium persulfate, emulsifier progress pre-emulsifications, pre-emulsification mix monomer lotion is obtained；By above-mentioned TiO2Slurry is heated to 80 DEG C, and 0.3 part of initiator ammonium persulfate is added, then the good mix monomer lotion of pre-emulsification is slowly added into above-mentioned TiO by initiation reaction 5 minutes2In slurry, time control is added at 25 hours, 85 DEG C of maintenance isothermal reaction 1 hour, obtains TiO of the surface through polyacrylate silicone covering after addition2Slurry.

Description

A method of it is polymerize in titanium dioxide surface with acrylate organosilicon
Technical field
The present invention relates to a kind of methods being polymerize in titanium dioxide surface with acrylate organosilicon.
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 practical applications.Rutile-type category tetragonal crystal system.There are one titaniums at lattice center Atom has 6 oxygen atoms around titanium atom, there is 3 titanium atoms around oxygen atom.Rutile unit cell is containing there are two titanium dioxides Titanium molecule, lattice is small and close, is most stable of in three kinds of crystal forms.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 Son distance it is closer, so by distortion it is octahedral in the form of occur.Detitanium-ore-type is very stable at low temperature, about at 650 DEG C Start stabilization and the conversion of crystal form, conversion process is by temperature, if additive is added and the factors shadows such as which kind of additive are added It rings.Optical property is one of most important characteristic of titanium dioxide, because the optical property of titanium dioxide has closely with its performance Relationship, such as refractive index, covering power, scattering force, weatherability, these are all the concrete embodiments of optical property.
Coatings industry is the first large user of titanium dioxide, and titanium dioxide is largely consumed by coatings industry.Titanium dioxide Titanium is most important pigment in coating material production, and effect is not only to cover and decorate, it is often more important that can improve coating Physical and chemical performance enhances chemical stability, improves covering power, reducing power, anticorrosive property, fast light and weatherability, enhances the machine of film Tool intensity and adhesive force are prevented from cracking and be fallen off, and are prevented ultraviolet light and moisture from penetrating, are extended the service life of object.
For the particle size range of pigmentary titanium dioxide at 70-100 nanometers, particle surface contains a large amount of hydroxyl, it is easy to send out Raw to reunite, the covering power of titanium dioxide can be greatly affected after reunion.So to be carried out before titanium dioxide use younger A certain amount of dispersant is added in process of lapping in thin grinding, it is therefore an objective to so that titanium dioxide granule is separated, such titanium dioxide hides Lid ability can just obtain the performance of bigger.In addition, titanium dioxide surface is very sensitive to environment, a small amount of impurity may cause Scattered particle is reunited again, and the use scope of titanium dioxide is very extensive, and use occasion is multifarious, slightly It will result in scattered particle accidentally again to reunite, so it is necessary to coating one layer of protection in titanium dioxide surface Layer, titanium dioxide granule is kept apart, the reunion of titanium dioxide granule is avoided, the covering power of titanium dioxide is made to obtain bigger It plays.
The present invention mainly coats acrylate Organosiliconcopolymere in titanium dioxide surface, is applied in water paint. Titanium dioxide surface polymer overmold is other than it can reduce reunion, the covering power for playing titanium dioxide to greatest extent, also Some other benefits, to sum up haing the following advantages：
（1）The reunion that can prevent titanium dioxide makes it keep monodisperse status, enhances its covering power, improve dioxy Change the utilization rate of titanium.
（2）It is easy to use, titania slurry is mixed with lotion and adds other auxiliary agents, is reduced two when using The step of dry powder dispersion of titanium oxide is at slurry, and titanium dioxide may reunite, and cannot effectively disperse.
（3）Make titanium dioxide that need not be transported, be used with dry powder, but transported, used with slurry, avoids The generation of titanium dioxide dust, can play the effect of environmental protection and reduce the loss of raw material.
（4）It is more preferable with the compatibility of lotion after titanium dioxide surface polymer overmold, the performance of coating can be improved.
In order to enable polymer covering layer preferably to be combined with titanium dioxide surface, the present invention first with double bond sun from Sub- monomer is modified titanium dioxide surface, and modified mechanism is：Titanium dioxide surface is per se with a large amount of negative electrical charge, band Cationic monomer one end of double bond carries positive charge, is adsorbed onto titanium dioxide surface by charge effect, the other end contains insatiable hunger Titanium dioxide surface is also stayed in the group of double bond vinyl, then is caused and acrylate, vinyl with initiator ammonium persulfate Silane copolymer finally obtained the titanium dioxide of surface cladding polyacrylate organosilicon.
Invention content
A method of it is polymerize in titanium dioxide surface with acrylate organosilicon, it is characterised in that：First to TiO2Into Row surface is modified, by weight by 300 parts of TiO2Powder is added in 1000 parts of water, is started blender stirring, is made TiO2Powder It is evenly dispersed in water, be added 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 are weighed, add 20 parts of absolute ethyl alcohol dilutions, by the second containing cationic monomer Alcoholic solution is slowly dropped to TiO2In slurry, stirs 30 minutes, obtain surface through the modifies finely dispersed TiO of cation mono2 Slurry；
It will be by 15 parts of methyl methacrylate, 15 parts of butyl acrylate, 10 parts of vinyltriethoxysilane and α-first The mix monomer of 5 parts of compositions of base acrylic acid and 2 parts of 80 parts of water, 1 part of initiator ammonium persulfate, emulsifier progress pre-emulsifications, obtain Pre-emulsification mix monomer lotion；
By above-mentioned TiO2Slurry is heated to 80 DEG C, is added 0.3 part of initiator ammonium persulfate, initiation reaction 5 minutes, then The good mix monomer lotion of pre-emulsification is slowly added into above-mentioned TiO2In slurry, time control is added at 2-5 hours, is added After maintain 85 DEG C of isothermal reactions 1 hour, obtain TiO of the surface through polyacrylate silicone covering2Slurry；
The cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl chlorination Ammonium, acrylic acid N, N- dimethylamino ethyl ester are one such or two or more；
The emulsifier is nonylphenol polyoxyethylene ether ammonium sulfate；
The TiO2Powder is anatase pigmentary TiO2；
The dispersant is sodium acrylate.
Specific implementation mode
Embodiment 1
First to TiO2Surface modification is carried out, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, is opened Dynamic blender stirring, makes TiO2Powder is evenly dispersed in water, and 1.5kg dispersants, the TiO that will be obtained is added2Slurry is in high speed point It dissipates and carries out high speed dispersion on machine, obtain monodispersed TiO2Slurry；3kg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides are weighed, Add 20kg absolute ethyl alcohols to dilute, the ethanol solution containing cationic monomer is slowly dropped to TiO2In slurry, stir 30 minutes, Surface is obtained through the modifies finely dispersed TiO of cation mono2Slurry；It will be by 15 kg of methyl methacrylate, acrylic acid fourth The mix monomer and water 80kg, initiator of 15 kg of ester, 10 kg of vinyltriethoxysilane and α-methacrylic acid 5kg compositions Ammonium persulfate 1kg, emulsifier nonylphenol polyoxyethylene ether ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer lotion； By above-mentioned TiO2Slurry is heated to 80 DEG C, and 0.3kg initiator ammonium persulfates, initiation reaction 5 minutes, then by pre-emulsification is added Good mix monomer lotion is slowly added into above-mentioned TiO2In slurry, time control is added at 2 hours, is maintained after addition 85 DEG C of isothermal reactions 1 hour, obtain the coated TiO in surface2Slurry.
Embodiment 2
First to TiO2Surface modification is carried out, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, is opened Dynamic blender stirring, makes TiO2Powder is evenly dispersed in water, and 1.5kg dispersants, the TiO that will be obtained is added2Slurry is in high speed point It dissipates and carries out high speed dispersion on machine, obtain monodispersed TiO2Slurry；3kg acrylyl oxy-ethyl-trimethyl salmiacs are weighed, are added 20kg absolute ethyl alcohols dilute, and the ethanol solution containing cationic monomer is slowly dropped to TiO2In slurry, stirs 30 minutes, obtain To surface through the modifies finely dispersed TiO of cation mono2Slurry；It will be by 15 kg of methyl methacrylate, butyl acrylate The mix monomer and water 80kg, initiator mistake of 15 kg, 10 kg of vinyltriethoxysilane and α-methacrylic acid 5kg compositions Ammonium sulfate 1kg, emulsifier nonylphenol polyoxyethylene ether ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer lotion；It will Above-mentioned TiO2Slurry is heated to 80 DEG C, and 0.3kg initiator ammonium persulfates are added, and initiation reaction 5 minutes is then good by pre-emulsification Mix monomer lotion be slowly added into above-mentioned TiO2In slurry, time control is added at 5 hours, 85 are maintained after addition DEG C isothermal reaction 1 hour, obtains the coated TiO in surface2Slurry.
Embodiment 3
First to TiO2Surface modification is carried out, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, is opened Dynamic blender stirring, makes TiO2Powder is evenly dispersed in water, and 1.5kg dispersants, the TiO that will be obtained is added2Slurry is in high speed point It dissipates and carries out high speed dispersion on machine, obtain monodispersed TiO2Slurry；3kg acrylic acid N, N- dimethylamino ethyl ester is weighed, is added 20kg absolute ethyl alcohols dilute, and the ethanol solution containing cationic monomer is slowly dropped to TiO2In slurry, stirs 30 minutes, obtain To surface through the modifies finely dispersed TiO of cation mono2Slurry；It will be by 15 kg of methyl methacrylate, butyl acrylate The mix monomer and water 80kg, initiator mistake of 15 kg, 10 kg of vinyltriethoxysilane and α-methacrylic acid 5kg compositions Ammonium sulfate 1kg, emulsifier nonylphenol polyoxyethylene ether ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer lotion；It will Above-mentioned TiO2Slurry is heated to 80 DEG C, and 0.3kg initiator ammonium persulfates are added, and initiation reaction 5 minutes is then good by pre-emulsification Mix monomer lotion be slowly added into above-mentioned TiO2In slurry, time control is added at 3 hours, 85 are maintained after addition DEG C isothermal reaction 1 hour, obtains the coated TiO in surface2Slurry.
Embodiment 4
First to TiO2Surface modification is carried out, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, is opened Dynamic blender stirring, makes TiO2Powder is evenly dispersed in water, and 1.5kg dispersants, the TiO that will be obtained is added2Slurry is in high speed point It dissipates and carries out high speed dispersion on machine, obtain monodispersed TiO2Slurry；3kg MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides are weighed, Add 20kg absolute ethyl alcohols to dilute, the ethanol solution containing cationic monomer is slowly dropped to TiO2In slurry, stir 30 minutes, Surface is obtained through the modifies finely dispersed TiO of cation mono2Slurry；It will be by 15 kg of methyl methacrylate, acrylic acid fourth The mix monomer and water 80kg, initiator of 15 kg of ester, 10 kg of vinyltriethoxysilane and α-methacrylic acid 5kg compositions Ammonium persulfate 1kg, emulsifier nonylphenol polyoxyethylene ether ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer lotion； By above-mentioned TiO2Slurry is heated to 80 DEG C, and 0.3kg initiator ammonium persulfates, initiation reaction 5 minutes, then by pre-emulsification is added Good mix monomer lotion is slowly added into above-mentioned TiO2In slurry, time control is added at 4 hours, is maintained after addition 85 DEG C of isothermal reactions 1 hour, obtain the coated TiO in surface2Slurry.
Embodiment 5
First to TiO2Surface modification is carried out, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, is opened Dynamic blender stirring, makes TiO2Powder is evenly dispersed in water, and 1.5kg dispersants, the TiO that will be obtained is added2Slurry is in high speed point It dissipates and carries out high speed dispersion on machine, obtain monodispersed TiO2Slurry；3kg acrylyl oxy-ethyl-trimethyl salmiacs are weighed, are added 20kg absolute ethyl alcohols dilute, and the ethanol solution containing cationic monomer is slowly dropped to TiO2In slurry, stirs 30 minutes, obtain To surface through the modifies finely dispersed TiO of cation mono2Slurry；It will be by 15 kg of methyl methacrylate, butyl acrylate The mix monomer and water 80kg, initiator mistake of 15 kg, 10 kg of vinyltriethoxysilane and α-methacrylic acid 5kg compositions Ammonium sulfate 1kg, emulsifier nonylphenol polyoxyethylene ether ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer lotion；It will Above-mentioned TiO2Slurry is heated to 80 DEG C, and 0.3kg initiator ammonium persulfates are added, and initiation reaction 5 minutes is then good by pre-emulsification Mix monomer lotion be slowly added into above-mentioned TiO2In slurry, time control is added at 4.5 hours, is maintained after addition 85 DEG C of isothermal reactions 1 hour, obtain the coated TiO in surface2Slurry.
Embodiment 6
First to TiO2Surface modification is carried out, by 300kg anatase pigmentaries TiO2Powder is added in 1000kg water, is opened Dynamic blender stirring, makes TiO2Powder is evenly dispersed in water, and 1.5kg dispersants, the TiO that will be obtained is added2Slurry is in high speed point It dissipates and carries out high speed dispersion on machine, obtain monodispersed TiO2Slurry；3kg acrylic acid N, N- dimethylamino ethyl ester is weighed, is added 20kg absolute ethyl alcohols dilute, and the ethanol solution containing cationic monomer is slowly dropped to TiO2In slurry, stirs 30 minutes, obtain To surface through the modifies finely dispersed TiO of cation mono2Slurry；It will be by 15 kg of methyl methacrylate, butyl acrylate The mix monomer and water 80kg, initiator mistake of 15 kg, 10 kg of vinyltriethoxysilane and α-methacrylic acid 5kg compositions Ammonium sulfate 1kg, emulsifier nonylphenol polyoxyethylene ether ammonium sulfate 2kg carry out pre-emulsification, obtain pre-emulsification mix monomer lotion；It will Above-mentioned TiO2Slurry is heated to 80 DEG C, and 0.3kg initiator ammonium persulfates are added, and initiation reaction 5 minutes is then good by pre-emulsification Mix monomer lotion be slowly added into above-mentioned TiO2In slurry, time control is added at 3.5 hours, is maintained after addition 85 DEG C of isothermal reactions 1 hour, obtain the coated TiO in surface2Slurry.

Claims (1)

1. a kind of method being polymerize in titanium dioxide surface with acrylate organosilicon, 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, is started blender stirring, is made TiO2Powder is uniform It is dispersed in water, 1.5 parts of dispersants, the TiO that will be obtained is added2Slurry carries out high speed dispersion on high speed dispersor, obtains list The TiO of dispersion2Slurry；3 parts of cationic monomers are weighed, 20 parts of absolute ethyl alcohol dilutions are added, the ethyl alcohol containing cationic monomer is molten Liquid is slowly dropped to TiO2In slurry, stirs 30 minutes, obtain surface through the modifies finely dispersed TiO of cation mono2Slurry Material；
It will be by 15 parts of methyl methacrylate, 15 parts of butyl acrylate, 10 parts of vinyltriethoxysilane and Alpha-Methyl propylene The mix monomer of 5 parts of compositions of acid and 2 parts of 80 parts of water, 1 part of initiator ammonium persulfate, emulsifier progress pre-emulsifications, obtain pre-emulsification Mix monomer lotion；
By above-mentioned TiO2Slurry is heated to 80 DEG C, 0.3 part of initiator ammonium persulfate is added, initiation reaction 5 minutes then will be pre- The mix monomer lotion emulsified is slowly added into above-mentioned TiO2In slurry, time control is added at 2-5 hours, addition finishes 85 DEG C of maintenance isothermal reaction 1 hour afterwards, obtains TiO of the surface through polyacrylate silicone covering2Slurry；
The cationic monomer be MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, Acrylic acid N, N- dimethylamino ethyl ester is one such or two or more；
The emulsifier is nonylphenol polyoxyethylene ether ammonium sulfate；
The TiO2Powder is anatase pigmentary TiO2；
The dispersant is Sodium Polyacrylate.
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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
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
CN114410131B (en) * 2021-12-14 2023-06-06 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

Citations (2)

* 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
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011515513A (en) * 2008-03-04 2011-05-19 エージェンシー フォー サイエンス，テクノロジー アンド リサーチ Low shrinkage multifunctional SSQ resin
DE102008024868A1 (en) * 2008-05-23 2009-11-26 Merck Patent Gmbh Polymerization process for the production of core-shell particles

Patent Citations (2)

* 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
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

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