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CN110003378A - A kind of preparation method of aqueous hybrid resin - Google Patents

A kind of preparation method of aqueous hybrid resin Download PDF

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Publication number
CN110003378A
CN110003378A CN201910177463.8A CN201910177463A CN110003378A CN 110003378 A CN110003378 A CN 110003378A CN 201910177463 A CN201910177463 A CN 201910177463A CN 110003378 A CN110003378 A CN 110003378A
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China
Prior art keywords
mixture
added
total content
hybrid resin
accounting
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CN201910177463.8A
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Chinese (zh)
Inventor
陈锦民
胡超基
姜笑君
胡寿基
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Jinhua Yitu New Materials Co Ltd
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Jinhua Yitu New Materials Co Ltd
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Priority to CN201910177463.8A priority Critical patent/CN110003378A/en
Publication of CN110003378A publication Critical patent/CN110003378A/en
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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
    • 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
    • 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
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (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
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to technical field of coatings more particularly to a kind of preparation methods of aqueous hybrid resin.It introduces the crosslinked group of organosilicon using some function monomers coupled hardness with softness such as glycidyl methacrylate, tertiary carbonic acid glycidyl esters, and with Nano silica sol, nanometer lithium metasilicate etc. is core, carries out function combination by the core-shell copolymerized scheme of shell of monomer.Step 1, addition deionized water accounts for total content 20 ~ 25% in reaction kettle, inorganic nano silica solution or modified Nano silicate account for total content 8 ~ 15%, cationic emulsifier is added in both aforementioned A mixture, so that cationic emulsifier is under conditions of the total amount specific gravity of mixture accounts for 3% ~ 5%, 3 mixture is warming up to 78 DEG C ~ 80 DEG C to react, radical initiator is added while reaction, in the B mixture that radical initiator is added to aforementioned 4, when content accounting 0.2 ~ 0.3% stops being added, using this as bottom material.

Description

A kind of preparation method of aqueous hybrid resin
Technical field
The present invention relates to technical field of coatings more particularly to a kind of preparation methods of aqueous hybrid resin.
Background technique
National policy and market are increasingly stringenter VOCs control, increasing to the cry of water paint.And with biography The solvent based coating of system is compared, and aqueous woodware paint is with its asepsis environment-protecting, odorlessness, volatilizable object are few, non-ignitable not quick-fried Gao An The advantages that full property, more and more attention has been paid to wherein be again nothing with fastest developing speed, kind is most with water-based acrylic resin woodcare paint Contamination type coating, but woodcare paint Water-borne modification problem perplexs always industry, it is emerging that hybrid material is that the 1980s starts A kind of new material risen.This kind of material is still without unified strict concept, it is considered that it is inorganic and organic principle is mutual In conjunction in conjunction with obtained a kind of material especially in microscopic dimensions.
However, traditional water soluble acrylic acid volatilizees there are dampening, and the time is long, and film forming is tired compared with traditional solvent based coating The disadvantages of difficulty, chemical resistance and high temperature resistant are relatively weak.Therefore, using hydridization when atom forms molecule, in order to enhance bonding Ability (keeps minimum energy after bonding then most stable), the group again of different types of atomic orbital similar in energy in same atom Close, formed energy, shape and the direction new atomic orbital different from original track (energy of this track all than no hydridization with Preceding energy wants low), improve the performance of water soluble acrylic acid.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of preparation method of aqueous hybrid resin, it Using some function monomers coupled hardness with softness such as glycidyl methacrylate, tertiary carbonic acid glycidyl ester, organosilicon is introduced Crosslinked group, with Nano silica sol, nanometer lithium metasilicate etc. is core, carries out functional group by the core-shell copolymerized scheme of shell of monomer It closes, obtained resin can be applied to bamboo and wood products, can also be applied to metallic paint, building coating.
A kind of preparation method of aqueous hybrid resin proposed by the present invention, comprising the following steps:
Step 1, addition deionized water accounts for total content 20 ~ 25%, inorganic nano silica solution or modified Nano silicate in reaction kettle Total content 8 ~ 15% is accounted for, cationic emulsifier is added in both aforementioned A mixture, so that cationic emulsifier is in mixture Total amount specific gravity account under conditions of 3% ~ 5%, 3 mixture is warming up to 78 DEG C ~ 80 DEG C and is reacted, reaction while add Enter radical initiator, in the B mixture that radical initiator is added to aforementioned 4, when content accounting 0.2 ~ 0.3% stops It is added, expects this as bottom.
Step 2 is warming up to 80 DEG C in another reaction kettle, in the state of high-speed stirred instill by total content 1 ~ 1.5% cationic emulsifier, 1 ~ 1.5% nonionic emulsifier of total content, with the mixing for accounting for 20 ~ 30% deionized water of total content composition Object instills glycidyl methacrylate, tertiary ethylene carbonate or new certain herbaceous plants with big flowers vinyl acetate), in glycidyl benzoate One or more of (accounting for total content 2% ~ 10%) production obtains C mixture, and said mixture carries out pre-emulsion, and maintaining reaction temperature In 80 ~ 85 DEG C of sections, rate of titration is controlled, pre-emulsion is instilled in 2.5 ~ 4 hours in the material of bottom, heat preservation is made to for 2 hours To D mixture.
Deionized water is added in final D mixture after step 3, reaction, and accounting 30 ~ 40%, adds stabilizer after addition, adds Enter rear accounting 0.3 ~ 0.5%, the mixture that above-mentioned steps are completed stirs 2 ~ 3 hours；
Step 4, after being cooled to 60 DEG C, by azo dicyclohexyl formonitrile HCN hydrochloride (VA044) aqueous solution of 0.5% concentration, slowly It instills, test unit residual quantity, the occurrence of test is to discharge after up to standard less than 100PPM and obtain the aqueous hybrid resin of finished product.
It is ammonium persulfate or potassium peroxydisulfate as the preferred radical initiator.
It is octadecyl ammonium chloride as the preferred cationic emulsifier.
As in the preferred step 1 inorganic nano silica solution or modified Nano silicate (8 ~ 15%) be added after also plus Enter the mixture of the one or both of modified Nano lithium metasilicate, modified Nano alumina silicate.
Preferably, 8% ~ 10% graphene oxide slurry can be added in the bottom material under high velocity agitation.
Compared with prior art, the present invention has the beneficial effects that this product because combine several particular monomers and Package copolymerization is carried out with extraordinary nano-inorganic substance, initiative has mixed three kinds of response type groups and a variety of functional groups, so that They have complementary advantages, and reach more preferably physical and chemical performance.
It uses some function monomers coupled hardness with softness such as glycidyl methacrylate, tertiary carbonic acid glycidyl ester, The crosslinked group for introducing organosilicon, with Nano silica sol, nanometer lithium metasilicate etc. is core, using monomer as the core-shell copolymerized scheme of shell Function combination is carried out, obtained resin can be applied to bamboo and wood products, can also be applied to metallic paint, building coating, as Basic material, broad application prospect will generate positive economic people's livelihood benefit.
Specific embodiment
Below by embodiment, preferred specific description is used as to technical solution of the present invention:
220 ~ 250g of deionized water is added in step 1 in a kettle, adds 10 ~ 20g of cationic emulsifier, is then warming up to 78℃.Addition radical initiator 2g, inorganic nano 60 ~ 80g of silica solution, inorganic nano silicon are molten in both aforementioned mixture Glue is the one or more of modified Nano lithium metasilicate, modified Nano alumina silicate, and 30g ~ 40g graphene oxide is added under high-speed stirred Slurry accounts for the 8% ~ 10% of total content ratio, expects as bottom, is warming up to 80 ~ 85 DEG C.
Step 2 is warming up to 80 DEG C in another reaction kettle, in the state of high-speed stirred, instill 10 ~ 30g sun from 80 ~ 120g methyl propenoic acid glycidyl is added in sub- emulsifier, 8g ~ 16g nonionic emulsifier, 150g ~ 200g deionized water Ester, 40g ~ 80g tertiary ethylene carbonate, 40 ~ 80g of methyl methacrylate, Isooctyl acrylate monomer 100g ~ 200g, deionized water water 200g ~ 300g is mixed object as pre-emulsion, and maintaining reaction temperature is in 80 ~ 85 DEG C of sections,
3, rate of titration is controlled, pre-emulsion is titrated in the material of bottom in 2.5 ~ 4 hours, keeps the temperature 2 hours.
4, after said mixture is cooled to 60 DEG C, by the azo dicyclohexyl formonitrile HCN hydrochloride (VA044) of 0.5% concentration Aqueous solution is slowly dropped into, and is eliminated residual except unreacted monomer；
5, after test unit residual quantity is less than 100PPM, filtering and discharging.
Embodiment 2:
Step 1, addition deionized water accounts for total content 20 ~ 25%, inorganic nano silica solution or modified Nano silicate in reaction kettle Total content 8 ~ 15% is accounted for, octadecyl ammonium chloride is added in both aforementioned A mixture, so that cationic emulsifier is mixing The total amount specific gravity of object accounts under conditions of 3% ~ 5%, and 3 mixture is warming up to 78 DEG C ~ 80 DEG C and is reacted, while reaction Ammonium sulfate or potassium peroxydisulfate is added, in the B mixture that radical initiator is added to aforementioned 4, when content accounting 0.2 ~ 0.3% stops being added, and expects this as bottom.
Step 2 is warming up to 80 DEG C in another reaction kettle, in the state of high-speed stirred instill by total content 1 ~ 1.5% cationic emulsifier, 1 ~ 1.5% nonionic emulsifier of total content, with the mixing for accounting for 20 ~ 30% deionized water of total content composition Object instills glycidyl methacrylate, tertiary ethylene carbonate or new certain herbaceous plants with big flowers vinyl acetate), in glycidyl benzoate One or more of (accounting for total content 2% ~ 10%) production obtains C mixture, and said mixture carries out pre-emulsion, and maintaining reaction temperature In 80 ~ 85 DEG C of sections, rate of titration is controlled, pre-emulsion is instilled in 2.5 ~ 4 hours in the material of bottom, heat preservation is made to for 2 hours To D mixture.
Deionized water is added in final D mixture after step 3, reaction, and accounting 30 ~ 40%, adds stabilizer after addition, adds Enter rear accounting 0.3 ~ 0.5%, the mixture that above-mentioned steps are completed stirs 2 ~ 3 hours；
Step 4, after being cooled to 60 DEG C, by azo dicyclohexyl formonitrile HCN hydrochloride (VA044) aqueous solution of 0.5% concentration, slowly It instills, test unit residual quantity, the occurrence of test is to discharge after up to standard less than 100PPM and obtain the aqueous hybrid resin of finished product.
As in the preferred step 1 inorganic nano silica solution or modified Nano silicate account for total content than 8 ~ 15%, add The mixture of the one or both of modified Nano lithium metasilicate, modified Nano alumina silicate is additionally added after entering.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.

Claims (5)

1. a kind of preparation method of aqueous hybrid resin, it is characterized in that: the following steps are included:
Step 1, addition deionized water accounts for total content 20 ~ 25%, inorganic nano silica solution or modified Nano silicate in reaction kettle Total content 8 ~ 15% is accounted for, cationic emulsifier is added in both aforementioned A mixture, so that cationic emulsifier is in mixture Total amount specific gravity account under conditions of 3% ~ 5%, 3 mixture is warming up to 78 DEG C ~ 80 DEG C and is reacted, reaction while add Enter radical initiator, in the B mixture that radical initiator is added to aforementioned 4, when content accounting 0.2 ~ 0.3% stops It is added, expects this as bottom；
Step 2 is warming up to 80 DEG C in another reaction kettle, is instilled in the state of high-speed stirred by 1 ~ 1.5% sun of total content Ionic emulsifying agent, 1 ~ 1.5% nonionic emulsifier of total content are instilled with the mixture for accounting for 20 ~ 30% deionized water of total content composition Glycidyl methacrylate, tertiary ethylene carbonate or new certain herbaceous plants with big flowers vinyl acetate), one of glycidyl benzoate or several Kind (accounting for total content 2% ~ 10%) production obtains C mixture, and said mixture carries out pre-emulsion, and maintaining reaction temperature is 80 ~ 85 DEG C section controls rate of titration, pre-emulsion is instilled in 2.5 ~ 4 hours in the material of bottom, keeps the temperature production in 2 hours and obtains D and mixes Object；
Deionized water is added in final D mixture after step 3, reaction, and accounting 30 ~ 40% after addition adds stabilizer, after addition Accounting 0.3 ~ 0.5%, the mixture that above-mentioned steps are completed stir 2 ~ 3 hours；
Step 4, after being cooled to 60 DEG C, by azo dicyclohexyl formonitrile HCN hydrochloride (VA044) aqueous solution of 0.5% concentration, slowly It instills, test unit residual quantity, the occurrence of test is to discharge after up to standard less than 100PPM and obtain the aqueous hybrid resin of finished product.
2. the preparation method of a kind of aqueous hybrid resin according to claim 1, it is characterized in that: the radical initiator For ammonium persulfate or potassium peroxydisulfate.
3. the preparation method of a kind of aqueous hybrid resin according to claim 1, it is characterized in that: the cationic emulsifier For octadecyl ammonium chloride.
4. the preparation method of a kind of aqueous hybrid resin according to claim 1, it is characterized in that: the nothing in the step 1 Machine Nano silica sol or modified Nano silicate (8 ~ 15%) are additionally added modified Nano lithium metasilicate, modified Nano alumina silicate after being added One or both mixture.
5. the preparation method of a kind of aqueous hybrid resin according to claim 1, it is characterized in that: bottom material can be in height Speed is added with stirring 8% ~ 10% graphene oxide slurry.
CN201910177463.8A 2019-03-09 2019-03-09 A kind of preparation method of aqueous hybrid resin Pending CN110003378A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116218313A (en) * 2022-09-08 2023-06-06 中华制漆（深圳）有限公司 Base paint emulsion for high-water-resistance high-weather-resistance multicolor paint and preparation method thereof

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CN105418820A (en) * 2015-12-23 2016-03-23 华南理工大学 Hydroxyl-containing styrene-acrylic polymer/SiO2 hybrid emulsion and its preparation method and application
CN108586657A (en) * 2018-05-29 2018-09-28 芜湖市元奎新材料科技有限公司 The acrylic emulsion of water paint

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CN105418820A (en) * 2015-12-23 2016-03-23 华南理工大学 Hydroxyl-containing styrene-acrylic polymer/SiO2 hybrid emulsion and its preparation method and application
CN108586657A (en) * 2018-05-29 2018-09-28 芜湖市元奎新材料科技有限公司 The acrylic emulsion of water paint

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CN116218313A (en) * 2022-09-08 2023-06-06 中华制漆（深圳）有限公司 Base paint emulsion for high-water-resistance high-weather-resistance multicolor paint and preparation method thereof
CN116218313B (en) * 2022-09-08 2024-04-19 中华制漆（深圳）有限公司 Base paint emulsion for high-water-resistance high-weather-resistance multicolor paint and preparation method thereof

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Application publication date: 20190712