CN106905469B - A method of automobile coating water-based acrylic resin is prepared using sol-gel method - Google Patents
A method of automobile coating water-based acrylic resin is prepared using sol-gel method Download PDFInfo
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- CN106905469B CN106905469B CN201710229416.4A CN201710229416A CN106905469B CN 106905469 B CN106905469 B CN 106905469B CN 201710229416 A CN201710229416 A CN 201710229416A CN 106905469 B CN106905469 B CN 106905469B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- 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
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- 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
- C08K3/36—Silica
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to polymer field of new materials, mainly to solve the problems, such as aqueous automobile paint resistance to acid and alkali, water-resistance and corrosion-resistant poor in the prior art, its major programme is a kind of method for preparing automobile coating water-based acrylic resin using sol-gel method, comprising the following steps: step 1: the preparation of sol solution；Step 2: the preparation of monomer phase；Step 3: sol solution being placed in reaction vessel, pressure is controlled in 1-3MPa, and monomer is mutually added dropwise and is entered in reaction system, and time for adding 1-2h, reaction temperature is controlled at 60-80 DEG C；Step 4: the pH value of regulation system.Automobile coating of the invention water-based acrylic resin resistance to acid and alkali, water-resistance and good corrosion resistance.
Description
Technical field
It is especially a kind of that automobile coating is prepared with aqueous using sol-gel method the present invention relates to polymer field of new materials
The method of acrylic resin.
Background technique
Earliest commercialization water paint is that occur in the 1930s.Compatibility and protection based on it to environment
Property, and have the advantages that save resource, energy saving, water paint product is acceptable to the market soon, and gradually development expands.
Japan, U.S.'s water paint in 1986 account for the 18% and 22% of coating total sales volume respectively, Britain's nineteen ninety-five water paint yield
Account for the 64.5% of national coating total output.External water paint is mostly used for the industries such as building, automobile, woodenware, high-performance water
Property metallic paint naval stores type multiplicity, paint film mechanical performance is excellent, salt spray resistance is good, generally replaces oleoresin
Protection applied to metal works.Currently, main manufacturer has the companies such as BASF, Bayer, Lu Borun, Aksu.
Water-based acrylic resin passes through lotion freedom by esters of acrylic acid and methyl acrylic ester and other olefinic type monomers
The copolymerization of base atmospheric pressure polymerization is made, by selecting different resin structure, different formulas and different production technologies and solvent
Composition, can synthesize the acrylic resin of different type, different performance and different application.Wherein the type of hard soft monomer and match
Basic performance than the main framework for determining resin, after determining resin film forming；Function monomer is used to improve the synthesis of resin
Performance.It is most outstanding the disadvantage is that the water-base resin that synthesis obtains although the method technological operation of this emulsion polymerization is simple
Molecular weight distribution it is wider, the remaining monomer with polar functional group is more, thus the resistance to acid and alkali of resin, water-resistance and resistance to
Corrosivity is poor.
Summary of the invention
Sol-gel legal system is used the object of the present invention is to provide a kind of resistance to acid and alkali, water-resistance and good corrosion resistance
The method of standby automobile coating water-based acrylic resin.
Technical solution provided by the invention are as follows: a kind of that automobile coating water-based acrylic resin is prepared using sol-gel method
Method, comprising the following steps:
Step 1: the preparation of sol solution: by the hydrophobicity silicon of the ethyl orthosilicate of 0.5-1 parts by weight and 1.5-2 parts by weight
Alkane is added in the dehydrated alcohol of 35-45 parts by weight, is warming up to 50 DEG C, and be stirred to react 3h, add 3-4 parts by weight yin from
Sub- emulsifier continues stirring until material is completely dissolved；
Step 2: the preparation of monomer phase: by the methyl methacrylate of 15-20 parts by weight, 5-10 parts by weight styrene,
The acrylic acid of 10-15 parts by weight, the hydroxyethyl methacrylate of 10-15 parts by weight, 5-10 parts by weight vinyl pyrrolidone,
1-3 parts by weight anion emulsifier, 0.5-0.8 parts by weight initiator be uniformly mixed obtain monomer phase；
Step 3: sol solution being placed in reaction vessel, pressure is controlled in 1-3MPa, and monomer is mutually added dropwise and is entered instead
It answers in system, time for adding 1-2h, reaction temperature is controlled at 60-80 DEG C；
Step 4: the pH value of the mixture system obtained by pH adjusting agent regulating step 3 is 6-7.
In the above-mentioned method for preparing automobile coating water-based acrylic resin using sol-gel method, described is hydrophobic
Property silane be methyltriethoxysilane or dimethyl diethoxysilane.
Step 1 described in the method for automobile coating water-based acrylic resin is prepared using sol-gel method above-mentioned
It is neopelex with anion emulsifier used in step 2.
Initiator described in the method for automobile coating water-based acrylic resin is prepared using sol-gel method above-mentioned
For one of azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide.
In the above-mentioned method for preparing automobile coating water-based acrylic resin using sol-gel method, the pH tune
Section agent is ammonium hydroxide.
The beneficial effect of this programme is, passes through colloidal sol -- the presoma of gel obtains active group and as connection
Point, temperature, pressure and the polymerization time of preferably soft or hard monomer, function monomer and copolymerization, obtain structure and molecular weight is all controllable
Water-based acrylic resin.Its reason is analyzed, it may be non-mainly under pressure the condition of hydro-thermal reaction (its actually)
Homogeneous Raolical polymerizable portions turn is homogeneous reaction, thus the rate of polymerization reaction is easy to control, residual monomer
Quantity is reduced, thus resistance to acid and alkali, water-resistance and corrosion resistance get a promotion after resin film forming.
Specific embodiment
With reference to embodiment, technical solution of the present invention is described in further detail, but do not constituted pair
Any restrictions of the invention.
Embodiment 1:
A method of automobile coating water-based acrylic resin is prepared using sol-gel method, comprising the following steps:
Step 1: the preparation of sol solution: by the dimethyl diethoxy of the ethyl orthosilicate of 1 parts by weight and 1.7 parts by weight
Silane is added in the dehydrated alcohol of 40 parts by weight, is warming up to 50 DEG C, and be stirred to react 3h, adds the 12 of 3-4 parts by weight
Sodium alkyl benzene sulfonate continues stirring until material is completely dissolved；
Step 2: the preparation of monomer phase: by the methyl methacrylate of 17 parts by weight, the styrene of 7 parts by weight, 13 weight
Acrylic acid, the hydroxyethyl methacrylate of 13 parts by weight, the vinyl pyrrolidone of 8 parts by weight, 2 parts by weight dodecyls of part
Benzene sulfonic acid sodium salt, 0.8 parts by weight azobisisoheptonitrile be uniformly mixed obtain monomer phase；
Step 3: sol solution being placed in reaction vessel, pressure is controlled in 3MPa, and monomer is mutually added dropwise and enters reaction
In system, time for adding 2h, reaction temperature is controlled at 80 DEG C；
Step 4: the pH value of the mixture system obtained by ammonium hydroxide regulating step 3 is 6-7.
Embodiment 2
A method of automobile coating water-based acrylic resin is prepared using sol-gel method, comprising the following steps:
Step 1: the preparation of sol solution: by the methyltriethoxy silane of the ethyl orthosilicate of 0.6 parts by weight and 2 parts by weight
Alkane is added in the dehydrated alcohol of 35 parts by weight, is warming up to 50 DEG C, and be stirred to react 3h, adds the dodecyl of 3 parts by weight
Benzene sulfonic acid sodium salt continues stirring until material is completely dissolved；
Step 2: the preparation of monomer phase: by the methyl methacrylate of 15 parts by weight, the styrene of 5 parts by weight, 10 weight
Acrylic acid, the hydroxyethyl methacrylate of 15 parts by weight, the vinyl pyrrolidone of 5 parts by weight, 1 parts by weight dodecyl of part
Benzene sulfonic acid sodium salt, 0.5 parts by weight azodiisobutyronitrile be uniformly mixed obtain monomer phase；
Step 3: sol solution being placed in reaction vessel, pressure is controlled in 2MPa, and monomer is mutually added dropwise and enters reaction
In system, time for adding 2h, reaction temperature is controlled at 70 DEG C；
Step 4: the pH value of the mixture system obtained by ammonium hydroxide regulating step 3 is 6-7.
Embodiment 3
A method of automobile coating water-based acrylic resin is prepared using sol-gel method, comprising the following steps:
Step 1: the preparation of sol solution: by the methyltriethoxy silane of the ethyl orthosilicate of 1 parts by weight and 1.5 parts by weight
Alkane is added in the dehydrated alcohol of 45 parts by weight, is warming up to 50 DEG C, and be stirred to react 3h, adds the dodecyl of 4 parts by weight
Benzene sulfonic acid sodium salt continues stirring until material is completely dissolved；
Step 2: the preparation of monomer phase: by the methyl methacrylate of 20 parts by weight, the styrene of 10 parts by weight, 15 weight
Acrylic acid, the hydroxyethyl methacrylate of 10 parts by weight, the vinyl pyrrolidone of 5 parts by weight, 3 parts by weight dodecyls of part
Benzene sulfonic acid sodium salt, 0.5-0.8 parts by weight azodiisobutyronitrile be uniformly mixed obtain monomer phase；
Step 3: sol solution being placed in reaction vessel, pressure is controlled in 1-3MPa, and monomer is mutually added dropwise and is entered instead
It answers in system, time for adding 1-2h, reaction temperature is controlled at 60-80 DEG C；
Step 4: the pH value of the mixture system obtained by ammonium hydroxide regulating step 3 is 6-7.
The product of embodiment 1-3, curing agent, levelling agent, dispersing agent and other necessary assistants and water are made uniformly
Coating specifically includes 20 parts by weight automobile coating water-based acrylic resins, 1 parts by weight of waterborne curing agent, 2 weight of levelling agent
Part, other necessary assistants 1-2 parts by weight, other necessary assistants include defoaming agent, thickener, pigment etc., and dosage can be free
It adjusts, additionally includes the deionized water of 12 parts by weight, high-speed stirred is uniformly dispersed.
Coating is handled using conventional spraying baking method, obtains the coating with a thickness of 100-110 microns, coating
Hardness (GB/T1730-93) is greater than 2H, and after impregnating 24 hours, paint film is not blistering and adhesive force is measured after 1 hour greater than 2 grades,
Surface drying time is less than 0.5h, does solid work the time less than 15h, the test of 1000h salt spray resistance is not fallen off by the way that paint film is not blistering, and 10d is resistance to be had
Solvent (benzene, volatile oil) test is not fallen off by the way that paint film is not blistering, and 30d corrosion resistance (10% sodium hydroxide solution) test is logical
Cross that paint film is not blistering not to be fallen off.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (4)
1. a kind of method for preparing automobile coating water-based acrylic resin using sol-gel method, it is characterised in that: including following
Step:
Step 1: the preparation of sol solution: the hydrophobic silane of the ethyl orthosilicate of 0.5-1 parts by weight and 1.5-2 parts by weight being added
Enter into the dehydrated alcohol of 35-45 parts by weight, be warming up to 50 DEG C, and be stirred to react 3h, adds the anion cream of 3-4 parts by weight
Agent continues stirring until material is completely dissolved；
Step 2: the preparation of monomer phase: by the methyl methacrylate of 15-20 parts by weight, the styrene of 5-10 parts by weight, 10-15
The acrylic acid of parts by weight, the hydroxyethyl methacrylate of 10-15 parts by weight, the vinyl pyrrolidone of 5-10 parts by weight, 1-3 weight
Measure part anion emulsifier, the initiator of 0.5-0.8 parts by weight is uniformly mixed and obtains monomer phase；
Step 3: sol solution being placed in reaction vessel, pressure is controlled in 1-3MPa, and monomer is mutually added dropwise and enters reactant
In system, time for adding 1-2h, reaction temperature is controlled at 60-80 DEG C；
Step 4: the pH value of the mixture system obtained by pH adjusting agent regulating step 3 is 6-7；The hydrophobic silane is
Methyltriethoxysilane or dimethyl diethoxysilane.
2. the method according to claim 1 for preparing automobile coating water-based acrylic resin using sol-gel method, special
Sign is: anion emulsifier used in the step 1 and step 2 is neopelex.
3. the method according to claim 1 for preparing automobile coating water-based acrylic resin using sol-gel method, special
Sign is: the initiator is one of azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide.
4. the method according to claim 1 for preparing automobile coating water-based acrylic resin using sol-gel method, special
Sign is: the pH adjusting agent is ammonium hydroxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017100697086 | 2017-02-08 | ||
| CN201710069708 | 2017-02-08 |
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| CN106905469A CN106905469A (en) | 2017-06-30 |
| CN106905469B true CN106905469B (en) | 2019-03-05 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US940005A (en) * | 1909-04-24 | 1909-11-16 | Ontario Silver Company | Die-holder for drop-hammers. |
| GB1312034A (en) * | 1970-05-11 | 1973-04-04 | Du Pont | N-vinyl pyrrolidone copolymers and coating compositions thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094005A (en) * | 1976-05-21 | 1978-06-06 | Rockwell International Corporation | Magnetic bubble data transfer switch |
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2017
- 2017-04-10 CN CN201710229416.4A patent/CN106905469B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US940005A (en) * | 1909-04-24 | 1909-11-16 | Ontario Silver Company | Die-holder for drop-hammers. |
| GB1312034A (en) * | 1970-05-11 | 1973-04-04 | Du Pont | N-vinyl pyrrolidone copolymers and coating compositions thereof |
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| CN106905469A (en) | 2017-06-30 |
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