CN119177032A - Preparation method of ultra-stable brush-shaped organic silicon microsphere coated modified pigment - Google Patents
Preparation method of ultra-stable brush-shaped organic silicon microsphere coated modified pigment Download PDFInfo
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- 239000000049 pigment Substances 0.000 title claims abstract description 142
- 239000004005 microsphere Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 14
- 239000010703 silicon Substances 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 78
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000005303 weighing Methods 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000005855 radiation Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 15
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 claims description 8
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 8
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 8
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 238000010559 graft polymerization reaction Methods 0.000 claims description 7
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 229960003351 prussian blue Drugs 0.000 claims description 7
- 239000013225 prussian blue Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 77
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920000578 graft copolymer Polymers 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960005191 ferric oxide Drugs 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
- C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
-
- 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
- C09C1/22—Compounds of iron
- C09C1/26—Iron blues
-
- 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
- C09C3/12—Treatment with organosilicon compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a preparation method of an ultra-stable brush-shaped organosilicon microsphere coated modified pigment, which comprises the steps of weighing raw materials, preparing a pre-emulsified mixed solution, preparing a composite pigment of an organosilicon resin coated pigment and preparing the brush-shaped organosilicon microsphere coated modified pigment; the invention has simple process and easy operation, the brush-shaped composite pigment particles can be endowed with diversified functionalities such as antibacterial property, specific adsorption resistance and the like by selecting or combining the grafting monomers, the hydrophilic groups rich in the grafted polymer chains can further improve the stability of the composite pigment particles, the organic silicon resin layer with various excellent performances such as UV radiation resistance, corrosion resistance and the like can also improve the performance of the coated pigment under a specific application system, and the brush-shaped composite pigment particles prepared by the method have wide application prospects in the fields of industrial products such as high-quality functional coatings and the like.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a preparation method of an ultra-stable brush-shaped organosilicon microsphere coated modified pigment.
Background
Pigment is often added and dispersed in various application systems such as paint, plastic, rubber and the like as a colorant, and compared with the pigment, the pigment has the advantages of more varieties, strong tinting strength, wide color spectrum, no toxicity or low toxicity and the like, but along with the gradual improvement of requirements of various aspects such as consumer markets, industry transformation and upgrading and the like, the application performance of the pigment under a specific system and the like are required to be optimized and improved, and the particle size and distribution of the pigment, the crystal form or the polarity of the pigment surface and the like can be changed by physical or chemical means by the pigment modification technology so as to achieve the purpose of changing and improving the pigment performance. Currently, there are two main types of techniques for modifying pigments, one is a pigment coating technique for coating pigment particles into microspheres by physical adsorption or chemical bonding, and the other is a surface modification technique for treating the surfaces of pigment particles.
The brush-shaped microsphere is a nano spherical polymer brush with a core-shell structure, which is formed by connecting a polymer chain with the surface of a spherical core in a higher grafting density, the organosilicon has the characteristics of low surface tension, high and low temperature resistance, corrosion resistance and the like, the brush-shaped organosilicon microsphere is used for coating modified pigment, has the advantages of high stability and easy functionalization, the grafted polymer chain can prevent agglomeration and sedimentation among the composite pigment particles through steric hindrance, electrostatic interaction and the like, so that the stability of the pigment particles can be further improved, the sources of grafting monomers forming a brush-shaped structure on the surfaces of the composite pigment particles are rich, and the grafted polymer chain can endow the coated pigment with various functions of antibiosis, antifouling and the like by selecting or combining according to requirements.
In the prior art, the research on coating modified pigments with silicones has mainly focused on the following aspects:
(1) The excellent performance of organic silicon is utilized to improve polyurethane or acrylic resin and the like, so as to coat pigment particles;
(2) Coating and modifying the pigment by using pure organic silicon resin;
(3) The surface modification of the organosilicon coated pigment particles is continued, if the surface is provided with reactive double bonds, graft polymerization modification can be continued, and chemical bonding can be carried out with other functional materials after a layer of silane coupling agent is modified;
However, since the organosilicon material is a hydrophobic material with low surface energy, agglomeration and sedimentation are easy to occur among composite pigment particles after coating pigment, so that the composite pigment particles have the defect of poor stability, and the traditional modified pigment coating process also has the problems of complex flow, difficult operation and low universality, and a pigment modification preparation method with controllable and uniform particle size, strong functionality and good universality is needed to be obtained by simple operation in industry, so the invention provides a preparation method of the ultra-stable brush-shaped organosilicon microsphere coated modified pigment, which is used for solving the problems in the prior art.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a preparation method of an ultra-stable brush-shaped organosilicon microsphere coated modified pigment, which solves the problems of poor stability of composite pigment particles, complex process, difficult operation and low universality existing in the existing technology of coating modified pigment by organosilicon.
In order to achieve the aim, the invention is realized by the following technical scheme that the preparation method of the ultra-stable brush-shaped organosilicon microsphere coated modified pigment comprises the following steps:
Firstly, weighing pigment, reaction monomer, surfactant, auxiliary stabilizer, deionized water and hydrolysis-condensation catalyst according to the mass ratio of 1:13:0.5-2.5:0.5:180-250:50 for standby, and pre-emulsifying the raw materials except the hydrolysis-condensation catalyst by using an ultrasonic cell crusher;
Transferring the pre-emulsified mixed solution into a three-neck flask, heating in an oil bath kettle, dropwise adding a hydrolysis-condensation catalyst into the mixed solution at a constant speed after heating to a preset temperature, and preparing the composite pigment emulsion with the surface coated with the organic silicon by miniemulsion polymerization;
And thirdly, weighing the composite pigment emulsion (calculated by the mass of solids contained in the emulsion) and the initiator according to the mass ratio of 40:1, taking the composite pigment emulsion and the initiator as raw materials for standby, mixing the weighed composite pigment emulsion and the initiator, adding a grafting monomer, and preparing the hairbrush-shaped composite pigment by a surface direct initiated grafting polymerization method, namely the hairbrush-shaped organosilicon microsphere coating modified and functionalized pigment.
The pigment is selected from one of phthalocyanine blue, prussian blue, phthalocyanine green, lead-chromium green, iron oxide red or composite titanium red, and the reaction monomer is selected from one or more of methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane or vinyltrimethoxysilane.
The further improvement is that in the first step, the surfactant is selected from one of sodium dodecyl sulfate, cetyl trimethyl ammonium bromide or alkylphenol ethoxylates, and the auxiliary stabilizer is selected from one of n-hexadecane or cyclohexane.
The further improvement is that in the first step, the hydrolysis-condensation catalyst is selected from one of aqueous hydrochloric acid solution or ammonia water, wherein the concentration of the aqueous hydrochloric acid solution is 1.0wt% and the concentration of the ammonia water is 3.0wt%.
The method is further improved in the second step, after the temperature is raised to 45-70 ℃ by heating in the oil bath, a hydrolysis-condensation catalyst is added dropwise, and the dropping speed of the hydrolysis-condensation catalyst is 0.3-1.0 mL/min.
The preparation method is characterized by further improving the technical scheme that in the third step, the initiator is a thermal initiator, and is specifically selected from one of potassium persulfate or dibenzoyl peroxide, and the specific step of preparing the brush-shaped composite pigment through the thermal initiator is that firstly, the weighed composite pigment emulsion and the potassium persulfate are poured into a three-neck flask to be uniformly mixed, then the three-neck flask is placed into an oil bath pot, heated to 70 ℃ under the protection of nitrogen and stabilized for 10min, and then 1.6 g-3.2 g of grafted monomer is dropwise added into the three-neck flask at a constant speed, and the brush-shaped composite pigment is obtained through a surface direct thermal initiation graft polymerization method.
The further improvement is that the grafting monomer is selected from one of acrylic acid monomer or hydroxyethyl acrylamide functional monomer, and the dripping speed of the grafting monomer is 0.3-1.0 mL/min.
The method is characterized by further improving the technical scheme that in the third step, the initiator is a photoinitiator, and is specifically selected from one of benzophenone or azodiisobutyronitrile, and the specific step of preparing the brush-shaped composite pigment by the photoinitiator is that firstly, the weighed composite pigment emulsion and benzophenone are poured into a photoreactor, 0.8 g-2.4 g of grafting monomer is added and mixed and stirred, then an ultraviolet radiation lamp is started under the protection of nitrogen to irradiate the mixed solution, and the brush-shaped composite pigment is obtained by a surface direct photoinitiated graft polymerization method.
The invention has the beneficial effects that the composite pigment of the organic silicon resin coated pigment is prepared by a miniemulsion polymerization method, then the functional monomer is initiated to graft polymerize under the initiation action of the visible light/thermal initiator to obtain the brush-shaped composite pigment particles, the particle size of the brush-shaped composite pigment particles can be controlled by controlling the addition amount of the functional monomer, the whole preparation process is simple in process and easy to operate, the brush-shaped composite pigment particles can be endowed with diversified functionalities such as antibacterial property, specific adsorption resistance and the like by selecting or combining the grafting monomers, the stability of the composite pigment particles can be further improved by the hydrophilic groups rich in the grafted polymer chains, the performance of the coated pigment under a specific application system can be improved by the organic silicon resin layer with various excellent performances such as UV radiation resistance, corrosion resistance and the like, and the brush-shaped composite pigment particles prepared by the method have wide application prospects in the industrial product fields such as high-quality functional paint and the like.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of an ultra-stable brush-shaped organosilicon microsphere coated modified pigment;
FIG. 2 is a graph showing the results of the distribution of the strength and hydrodynamic diameter of composite pigment particles and brush-like composite pigment particles in an embodiment of the present invention;
FIG. 3 is a comparative schematic diagram of the storage stability of brush-like polyhydroxyethyl acrylamide composite pigment particles, brush-like polyacrylic acid composite pigment particles, and composite pigment particles in an example of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention relates to a preparation method of an ultra-stable brush-shaped organic silicon microsphere coated modified pigment, wherein the pigment in raw materials is selected from one of phthalocyanine blue, prussian blue, phthalocyanine green, lead chrome green, ferric oxide red or composite titanium red, prussian blue is selected in the following examples, a reaction monomer is selected from one or more of methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane or vinyltrimethoxysilane, a composition of methyltrimethoxysilane, phenyltrimethoxysilane and methylphenyldimethoxysilane is selected in the following examples, a surfactant is selected from one of sodium dodecyl sulfate, cetyl trimethylammonium bromide or alkylphenol ethoxylate, sodium dodecyl sulfate is selected in the following examples, an auxiliary stabilizer is selected from one of n-hexadecane or cyclohexane, the following examples are selected from n-hexadecane, a hydrolysis-condensation catalyst is selected from one of aqueous hydrochloric acid solution or aqueous ammonia, the concentration of the aqueous hydrochloric acid solution is 1.0wt%, the concentration of the aqueous ammonia solution of the aqueous ammonia is 3.0wt%, and the following examples are selected from 1.0wt% aqueous hydrochloric acid solution.
Example 1
Referring to fig. 1, the embodiment provides a preparation method of an ultra-stable brush-shaped organosilicon microsphere coated modified pigment, which comprises the following steps:
Step one, preparing a composite pigment of an organosilicon resin coated pigment
Accurately weighing 0.2g of Prussian blue Pigment (PB) and 0.05g of Sodium Dodecyl Sulfate (SDS) by adopting a precise weighing instrument, transferring into a 50mL beaker A, adding 18.5g of deionized water, then placing the beaker A into an ice water bath, starting an ultrasonic cell breaker to ultrasonically disperse the mixed solution in the beaker A for 2 minutes at 150W power to obtain a pre-dispersed pigment solution, accurately weighing 0.68g of methyltrimethoxysilane (MTMS), 0.91g of Phenyltrimethoxysilane (PTMS), 0.99g of methylphenyldimethoxysilane (MPDMS), 0.1g of n-Hexadecane (HD) and 0.05g of Sodium Dodecyl Sulfate (SDS), transferring into a 50mL beaker B, adding 18.5g of deionized water, then placing the beaker B into the ice water bath, starting an ultrasonic cell breaker to pre-emulsify the mixed solution in the beaker B for 2 minutes at 150W power, obtaining a pre-emulsified monomer solution, then mixing the pre-dispersed pigment solution and the pre-emulsified monomer solution in the ice water bath, simultaneously starting the ultrasonic cell breaker to pre-emulsify the mixed solution at 150W power for 2 minutes, transferring into a three-mL of the water bath to a fine emulsion, heating the mixed solution at a temperature of 10 ℃ for a mechanical stirring method, heating the mixed solution at a temperature of 0.1 ℃ to a fine stirring solution of the water bath of which is prepared by a fine stirring solution of the solution is heated at a temperature of 0.5 ℃ of 45-60-mL, dropwise stirring solution, and a surface of the solution is prepared by a fine stirring method;
The particle size of the prepared composite pigment particles was measured by a laser particle sizer, and the results were that the particle size of the prepared composite pigment particles was 257nm and the particle size distribution was 0.18 when 0.1gSDS was added (this example), that the particle size of the prepared composite pigment particles was 211nm and the particle size distribution was 0.10 when 0.3gSDS was added, and that the particle size of the prepared composite pigment particles was 198nm and the particle size distribution was 0.18 when 0.5gSDS was added;
Step two, preparing brush-shaped organosilicon microsphere coated modified pigment
Accurately weighing 50g (containing 0.8g of solid mass) of the prepared composite pigment ion emulsion coated with organic silicon on the surface and 0.02g of potassium persulfate (KPS) by adopting a precise weighing instrument, transferring the emulsion into a 100mL three-neck flask, mechanically stirring uniformly, then placing the three-neck flask into an oil bath pot, heating to 70 ℃ under the protection of nitrogen, stabilizing for 10min, and then dropwise adding 1.6 g-3.2 g of Acrylic Acid (AA) monomer at the speed of 0.3-1.0 mL/min by adopting a 5mL syringe, wherein the dropwise adding speed of the embodiment is 0.5mL/min, and obtaining the brush-shaped polyacrylic acid composite pigment by adopting a surface direct thermal initiated graft polymerization method;
The particle size of brush-shaped composite pigment particles with rich carboxylic acid groups on the surface is measured by a laser particle sizer through a direct thermal initiation method under different acrylic acid monomer addition amounts, and the result is that the particle size of brush-shaped composite pigment particles prepared by adding 1.6g of acrylic acid is 252nm, the particle size of brush-shaped composite pigment particles prepared by adding 2.4g of acrylic acid is 485nm, and the particle size of brush-shaped composite pigment particles prepared by adding 3.2g of acrylic acid is 686nm.
Example two
Referring to fig. 1, the embodiment provides a preparation method of an ultra-stable brush-shaped organosilicon microsphere coated modified pigment, which comprises the following steps:
Step one, preparing a composite pigment of an organosilicon resin coated pigment
Accurately weighing 0.2g Prussian blue Pigment (PB) and 0.15g Sodium Dodecyl Sulfate (SDS) by adopting a precise weighing instrument, transferring the Prussian blue Pigment (PB) and the 0.15g Sodium Dodecyl Sulfate (SDS) into a 50mL beaker A, adding 18.4g deionized water, then placing the beaker A into an ice water bath, starting an ultrasonic cell breaker to ultrasonically disperse the mixed solution in the beaker A for 2 minutes at 150W power to obtain a pre-dispersed pigment solution, accurately weighing 0.68g methyltrimethoxysilane (MTMS), 0.91g Phenyltrimethoxysilane (PTMS), 0.99g methylphenyldimethoxysilane (MPDMS), 0.1g n-Hexadecane (HD) and 0.15g Sodium Dodecyl Sulfate (SDS), transferring the mixture into a 50mL beaker B, adding 18.4g deionized water, then placing the beaker B into the ice water bath, starting the ultrasonic cell breaker to pre-emulsify the mixed solution in the beaker B for 2 minutes at 150W power, obtaining a pre-emulsified monomer solution, mixing the pre-dispersed pigment solution and the pre-emulsified monomer solution in the ice bath, simultaneously starting the ultrasonic cell breaker to heat the mixed solution at 150W power to a temperature of the water bath for 2 ℃ for 10 minutes, heating the mixed solution by a mechanical stirring method of dropwise adding the mixed solution to the solution at a temperature of 0.1 ℃ to a fine stirring solution of the solution of hydrochloric acid solution of which is heated to a fine stirring solution of the water solution of the 10-phase of 60-60 mL kettle and a fine emulsion;
The particle size of the prepared composite pigment particles was measured by a laser particle sizer, and the results were that the particle size of the prepared composite pigment particles was 257nm and the particle size distribution was 0.18 when 0.1gSDS was added, that of the prepared composite pigment particles was 211nm and the particle size distribution was 0.10 when 0.3gSDS was added (this example), that of the prepared composite pigment particles was 198nm and the particle size distribution was 0.18 when 0.5gSDS was added;
Step two, preparing brush-shaped organosilicon microsphere coated modified pigment
Accurately weighing 50g (containing 0.8g of solid mass) of pigment emulsion with the surface coated with organic silicon and 0.02g of benzophenone prepared in the first step by adopting a precise weighing instrument, transferring the pigment emulsion into a photoreactor, simultaneously adding 0.8 g-2.4 g of hydroxyethyl acrylamide (HEAA) functional monomer into the photoreactor, mixing and stirring, then starting a 175W ultraviolet radiation lamp under the protection of nitrogen to irradiate the mixed solution, and obtaining the brush-shaped polyhydroxyethyl acrylamide composite pigment by a surface direct photoinitiated graft polymerization method;
the particle diameters of the brush-shaped composite pigment particles prepared by a direct photoinitiation method under different amounts of the monomers of hydroxyethyl acrylamide were measured by a laser particle sizer, and the results were that the particle diameter of the brush-shaped composite pigment particles prepared by adding 0.8g of hydroxyethyl acrylamide was 213nm, the particle diameter of the brush-shaped composite pigment particles prepared by adding 1.6g of hydroxyethyl acrylamide was 325nm, and the particle diameter of the brush-shaped composite pigment particles prepared by adding 2.4g of hydroxyethyl acrylamide was 390nm.
The results of the distribution of the strength (density) and hydrodynamic diameter (Hydrodynamic diameter) of the composite pigment particles and the brush-shaped composite pigment particles are shown in fig. 2, wherein (a) in fig. 2 represents the composite pigment particles, (b) in fig. 2 represents the brush-shaped polyacrylic acid composite pigment particles, and (c) in fig. 2 represents the brush-shaped polyhydroxyethyl acrylamide composite pigment particles.
The brush-like polyhydroxyethyl acrylamide composite pigment particles, brush-like polyacrylic acid composite pigment particles, and composite pigment particles shown in fig. 3 are compared in storage stability, wherein (a) in fig. 3 represents the composite pigment particles, (b) in fig. 3 represents the brush-like polyacrylic acid composite pigment particles, and (c) in fig. 3 represents the brush-like polyhydroxyethyl acrylamide composite pigment particles.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. The preparation method of the ultra-stable brush-shaped organosilicon microsphere coated modified pigment is characterized by comprising the following steps of:
Firstly, weighing pigment, reaction monomer, surfactant, auxiliary stabilizer, deionized water and hydrolysis-condensation catalyst according to the mass ratio of 1:13:0.5-2.5:0.5:180-250:50 for standby, and pre-emulsifying the raw materials except the hydrolysis-condensation catalyst by using an ultrasonic cell crusher;
Transferring the pre-emulsified mixed solution into a three-neck flask, heating in an oil bath kettle, dropwise adding a hydrolysis-condensation catalyst into the mixed solution at a constant speed after heating to a preset temperature, and preparing the composite pigment emulsion with the surface coated with the organic silicon by miniemulsion polymerization;
And thirdly, weighing the composite pigment emulsion and the initiator according to the mass ratio of 40:1 as raw materials for standby, wherein the mass ratio is the ratio of the solid mass to the initiator mass in the composite pigment emulsion, mixing the weighed composite pigment emulsion and the initiator, adding a grafting monomer, and preparing the hairbrush-shaped composite pigment by a surface direct initiated grafting polymerization method, namely the hairbrush-shaped organosilicon microsphere coating modified and functionalized pigment.
2. The method for preparing the ultra-stable brush-shaped organosilicon microsphere coated modified pigment according to claim 1, wherein in the first step, the pigment is selected from one of phthalocyanine blue, prussian blue, phthalocyanine green, lead chrome green, iron oxide red or composite titanium red, and the reaction monomer is selected from one or more of methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane or vinyltrimethoxysilane.
3. The method for preparing a modified pigment coated with ultra-stable brush-like silicone microspheres according to claim 1, wherein in the first step, the surfactant is selected from one of sodium dodecyl sulfate, cetyltrimethylammonium bromide or alkylphenol ethoxylates, and the co-stabilizer is selected from one of n-hexadecane or cyclohexane.
4. The method for preparing a modified pigment coated with ultra-stable brush-shaped silicone microspheres according to claim 1, wherein in the first step, the hydrolysis-condensation catalyst is selected from one of aqueous hydrochloric acid solution or aqueous ammonia, wherein the concentration of the aqueous hydrochloric acid solution is 1.0wt% and the concentration of the aqueous ammonia is 3.0wt%.
5. The method for preparing the ultra-stable brush-shaped organosilicon microsphere coated modified pigment according to claim 1, wherein in the second step, the hydrolysis-condensation catalyst is added dropwise after the oil bath is heated to 45-70 ℃, and the dropping speed of the hydrolysis-condensation catalyst is 0.3-1.0 mL/min.
6. The preparation method of the ultra-stable brush-shaped organic silicon microsphere coated modified pigment according to claim 1, wherein in the third step, the initiator is a thermal initiator, and is specifically selected from one of potassium persulfate or dibenzoyl peroxide, and the specific step of preparing the brush-shaped composite pigment by the thermal initiator is that firstly, the weighed composite pigment emulsion and the potassium persulfate are poured into a three-neck flask to be uniformly mixed, then the three-neck flask is placed into an oil bath pot, heated to 70 ℃ under the protection of nitrogen and stabilized for 10min, and then 1.6 g-3.2 g of grafted monomer is dropwise added into the three-neck flask at a constant speed, and the brush-shaped composite pigment is obtained by a surface direct thermal initiation graft polymerization method.
7. The method for preparing the coating modified pigment of the ultra-stable brush-shaped organic silicon microsphere, as set forth in claim 6, wherein the grafting monomer is one of an acrylic acid monomer and a hydroxyethyl acrylamide functional monomer, and the dripping speed of the grafting monomer is 0.3-1.0 mL/min.
8. The method for preparing the brush-shaped composite pigment by using the ultra-stable brush-shaped organosilicon microsphere coated modified pigment according to claim 1, wherein in the third step, the initiator is a photoinitiator, and is specifically selected from one of benzophenone or azodiisobutyronitrile, and the specific step of preparing the brush-shaped composite pigment by using the photoinitiator is that firstly, the weighed composite pigment emulsion and benzophenone are poured into a photoreactor, 0.8 g-2.4 g of grafting monomer are added at the same time, mixing and stirring are carried out, then an ultraviolet radiation lamp is started under the protection of nitrogen to irradiate the mixed solution, and the brush-shaped composite pigment is obtained by a surface direct photoinitiation graft polymerization method.
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