CN106916263A - A kind of method of organic-silicon-modified automobile coating water-based acrylic resin - Google Patents
A kind of method of organic-silicon-modified automobile coating water-based acrylic resin Download PDFInfo
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- CN106916263A CN106916263A CN201710229840.9A CN201710229840A CN106916263A CN 106916263 A CN106916263 A CN 106916263A CN 201710229840 A CN201710229840 A CN 201710229840A CN 106916263 A CN106916263 A CN 106916263A
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- weight portions
- acrylic resin
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- water
- based acrylic
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to polymer field of new, mainly it is used to solve the problems, such as aqueous automobile paint resistance to acids and bases, water-resistance and corrosion-resistant difference in the prior art, its major programme is a kind of method that use sol-gal process prepares automobile coating water-based acrylic resin, is comprised the following steps：Step 1：The preparation of sol solution；Step 2：The preparation of single phase；Step 3：Sol solution is placed in reaction vessel, be added dropwise for single phase and enter into reaction system by Stress control in 1 3MPa, time for adding is 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 acids and bases, water-resistance and good corrosion resistance.
Description
Technical field
The present invention relates to polymer field of new, particularly a kind of organic-silicon-modified automobile coating water-based acrylic resin
Method.
Background technology
Earliest commercialization water paint is that occur in the thirties in 20th century.Compatibility and protection based on it to environment
Property, and there is save resources, 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, Britain's nineteen ninety-five water paint yield respectively
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 is various with naval stores type, and paint film mechanical performance is excellent, salt spray resistance is good, generally replaces oleoresin
It is applied to the protection of metal works.At present, main manufacturer has the companies such as BASF, Bayer, Lu Borun, Aksu.
Water-based acrylic resin passes through emulsion freedom by esters of acrylic acid and methyl acrylic ester and other olefinic type monomers
Base atmospheric pressure polymerization copolymerization is made, by from different resin structures, different formulas and different production technologies and solvent
Composition, can synthesize the acrylic resin of different type, different performance and different application occasion.The species of wherein hard soft monomer and match somebody with somebody
Than the main framework for determining resin, the key property after resin film forming is determined；Function monomer is used to improve the synthesis of resin
Performance.Although the method technological operation of this emulsion polymerization is simple, most prominent shortcoming is the water-base resin that synthesis is obtained
Molecular weight distribution it is wider, the monomer with polar functional group of residual is more, thus the resistance to acids and bases of resin, water-resistance and resistance to
Corrosivity is poor.
It is found through experiments that, automobile coating obtained by acrylic resin is prepared on solving using sol-gel process high pressure
When resistance to acids and bases, water-resistance and the corrosion-resistant stated, glossiness cannot obtain synchronous improvement again.
The content of the invention
It is an object of the invention to provide the organic-silicon-modified automobile coating that a kind of environmental resistance is strong, glossiness is good with aqueous third
The method of olefin(e) acid resin.
The present invention provide technical scheme be：A kind of method of organic-silicon-modified automobile coating water-based acrylic resin, its
It is characterised by：Comprise the following steps：
Step 1：The preparation of sol solution：By the tetraethyl orthosilicate of 0.5-1 weight portions and the hydrophobicity silicon of 1.5-2 weight portions
Alkane is added in the absolute ethyl alcohol of 35-45 weight portions, is warming up to 50 DEG C, and stirring reaction 3h, add 3-4 weight portions it is cloudy from
Sub- emulsifying agent, continues to stir until material is completely dissolved；
Step 2：The preparation of single phase：By the butyl methacrylate of 10-15 weight portions, the styrene of 3-5 weight portions, 5-
10 parts by weight of ethylene base trimethoxy siloxanes, the acrylic acid of 10-15 weight portions, the hydroxyethyl methacrylate second of 10-15 weight portions
Ester, the vinyl pyrrolidone of 5-10 weight portions, 2-5 weight portions tetramethyl divinyl disiloxane, 1-3 weight portion anion
Emulsifying agent, the initiator of 0.5-0.8 weight portions are well mixed and obtain single phase；
Step 3：Sol solution is placed in reaction vessel, be added dropwise for single phase and enter into instead by Stress control in 2-4MPa
Answer in system, time for adding is 1-2h, reaction temperature is controlled at 55-65 DEG C；
Step 4：The pH value of the mixture system obtained by pH adjusting agent regulating step 3 is 6-7.
In the method for above-mentioned organic-silicon-modified automobile coating water-based acrylic resin, described hydrophobic silane is first
Ethyl triethoxy silicane alkane or dimethyldiethoxysilane.
The beneficial effect of this programme is, by colloidal sol -- the presoma of gel obtains active group and as connection
Point, the temperature of preferably soft or hard monomer, function monomer and copolymerization, pressure and polymerization time, obtain structure and molecular weight is all controllable
Water-based acrylic resin.Its reason is analyzed, may be mainly under pressure the condition of hydro-thermal reaction (its actually) non-
Homogeneous Raolical polymerizable portions turn is homogeneous reaction, thus the speed of polymerisation is easily controlled, residual monomer
Quantity is reduced, thus resistance to acids and bases, water-resistance and corrosion resistance get a promotion after resin film forming.Carried using organic-silicon-modified simultaneously
Its glossiness high, and the influence in reaction under high pressure to resinous luster degree can be avoided by multi-functional organosilicon.
Specific embodiment
With reference to specific embodiment, technical scheme is described in further detail, but do not constitute it is right
Any limitation of the invention.
Embodiment 1：
A kind of method of organic-silicon-modified automobile coating water-based acrylic resin, comprises the following steps：
Step 1：The preparation of sol solution：By the tetraethyl orthosilicate of 0.8 weight portion and the dimethyl diethoxy of 1.8 weight portions
Base silane is added in the absolute ethyl alcohol of 40 weight portions, is warming up to 50 DEG C, and stirring reaction 3h, adds the ten of 3.5 weight portions
Dialkyl benzene sulfonic acids sodium, continues to stir until material is completely dissolved；
Step 2：The preparation of single phase：By the butyl methacrylate of 12 weight portions, the styrene of 4 weight portions, 8 weight portions
Vinyl trimethoxy siloxanes, the acrylic acid of 12 weight portions, the hydroxyethyl methacrylate of 13 weight portions, the second of 7 weight portions
Vinyl pyrrolidone, 2 weight portion tetramethyl divinyl disiloxanes, 2 weight portion neopelexes, 0.6 weight portion
Initiator well mixed obtain single phase；
Step 3：Sol solution is placed in reaction vessel, be added dropwise for single phase and enter into reaction by Stress control in 3MPa
In system, time for adding is 2h, and reaction temperature is controlled at 55 DEG C；
Step 4：The pH value of the mixture system obtained by ammoniacal liquor regulating step 3 is 6-7.
Embodiment 2
A kind of method of organic-silicon-modified automobile coating water-based acrylic resin, comprises the following steps：
Step 1：The preparation of sol solution：By the tetraethyl orthosilicate of 1 weight portion and the dimethyl diethoxy of 1.5 weight portions
Silane is added in the absolute ethyl alcohol of 35 weight portions, is warming up to 50 DEG C, and stirring reaction 3h, adds the dodecane of 3 weight portions
Base benzene sulfonic acid sodium salt, continues to stir until material is completely dissolved；
Step 2：The preparation of single phase：By the butyl methacrylate of 10 weight portions, the styrene of 3 weight portions, 10 weight
Part vinyl trimethoxy siloxanes, the acrylic acid of 10 weight portions, the hydroxyethyl methacrylate of 11 weight portions, 10 weight portions
Vinyl pyrrolidone, 3 weight portion tetramethyl divinyl disiloxanes, 3 weight portion neopelexes, 0.8 weight
The initiator of part is well mixed to obtain single phase；
Step 3：Sol solution is placed in reaction vessel, be added dropwise for single phase and enter into reaction by Stress control in 4MPa
In system, time for adding is 2h, and reaction temperature is controlled at 55 DEG C；
Step 4：The pH value of the mixture system obtained by ammoniacal liquor regulating step 3 is 6-7.
Embodiment 3
A kind of method of organic-silicon-modified automobile coating water-based acrylic resin, comprises the following steps：
Step 1：The preparation of sol solution：By the tetraethyl orthosilicate of 0.5 weight portion and the dimethyl diethoxy of 2 weight portions
Silane is added in the absolute ethyl alcohol of 45 weight portions, is warming up to 50 DEG C, and stirring reaction 3h, adds the dodecane of 4 weight portions
Base benzene sulfonic acid sodium salt, continues to stir until material is completely dissolved；
Step 2：The preparation of single phase：By the butyl methacrylate of 15 weight portions, the styrene of 5 weight portions, 5 weight portions
Vinyl trimethoxy siloxanes, the acrylic acid of 15 weight portions, the hydroxyethyl methacrylate of 15 weight portions, the second of 5 weight portions
Vinyl pyrrolidone, 4 weight portion tetramethyl divinyl disiloxanes, 1 weight portion neopelex, 0.5 weight portion
Initiator well mixed obtain single phase；
Step 3：Sol solution is placed in reaction vessel, be added dropwise for single phase and enter into reaction by Stress control in 2MPa
In system, time for adding is 2h, and reaction temperature is controlled at 60 DEG C；
Step 4：The pH value of the mixture system obtained by ammoniacal liquor regulating step 3 is 6-7.
Comparative example 1
It is substantially the same with embodiment 1, different places is that the composition of single phase is as follows：By the metering system of 12 weight portions
Acid butyl ester, the styrene of 4 weight portions, 10 parts by weight of ethylene base trimethoxy siloxanes, the acrylic acid of 12 weight portions, 13 weight portions
Hydroxyethyl methacrylate, the vinyl pyrrolidone of 7 weight portions, 2 weight portion neopelexes, 0.6 weight portion
Initiator well mixed obtain single phase.
By the product of embodiment 1-3 and comparative example 1, curing agent, levelling agent, dispersant and other necessary assistants and water
Be made uniform coating, specifically including 20 weight portion automobile coating water-based acrylic resins, the weight portion of waterborne curing agent 1,
The weight portion of levelling agent 2, other necessary assistants 1-2 weight portions, including defoamer, thickener, pigment etc., it is used other necessary assistants
Amount can be adjusted freely, and additionally including the deionized water of 12 weight portions, high-speed stirred is uniformly dispersed.
Coating is processed using conventional car paint spraying baking method, it is 100-110 microns to obtain thickness
Coating, coating hardness (GB/T1730-93) is more than 2H, and glossiness (GB/T9754) is 92-93% at 20 °, after soaking 24 hours,
Paint film is non-foaming and adhesive force is measured after 1 hour more than 2 grades, and surface drying time is less than 0.5h, does solid work the time less than 15h, 1000h
Salt spray resistance test does not fall off by the way that paint film is non-foaming, and 10d organic solvent-resistants (benzene, volatile oil) test does not take off by the way that paint film is non-foaming
Fall, 30d corrosion resistances (10% sodium hydroxide solution) test does not fall off by the way that paint film is non-foaming.
The data of comparative example 1 and the data of embodiment 1-3 are substantially the same, and different places are, glossiness (GB/ at 20 °
T9754) it is 89-90%.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (2)
1. a kind of method of organic-silicon-modified automobile coating water-based acrylic resin, it is characterised in that：Comprise the following steps：
Step 1：The preparation of sol solution：The hydrophobic silane of the tetraethyl orthosilicate of 0.5-1 weight portions and 1.5-2 weight portions is added
Enter in the absolute ethyl alcohol of 35-45 weight portions, be warming up to 50 DEG C, and stirring reaction 3h, add the anion breast of 3-4 weight portions
Agent, continues to stir until material is completely dissolved；
Step 2：The preparation of single phase：By the butyl methacrylate of 10-15 weight portions, the styrene of 3-5 weight portions, 5-10 weights
Amount part vinyl trimethoxy siloxanes, the acrylic acid of 10-15 weight portions, the hydroxyethyl methacrylate of 10-15 weight portions, 5-
The vinyl pyrrolidone of 10 weight portions, 2-5 weight portions tetramethyl divinyl disiloxane, 1-3 weight portions are anionic emulsifying
Agent, the initiator of 0.5-0.8 weight portions are well mixed and obtain single phase；
Step 3：Sol solution is placed in reaction vessel, be added dropwise for single phase and enter into reactant by Stress control in 2-4MPa
In system, time for adding is 1-2h, and reaction temperature is controlled at 55-65 DEG C；
Step 4：The pH value of the mixture system obtained by pH adjusting agent regulating step 3 is 6-7.
2. the method for organic-silicon-modified automobile coating water-based acrylic resin according to claim 1, it is characterised in that：Institute
The hydrophobic silane stated is MTES or dimethyldiethoxysilane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017100697052 | 2017-02-08 | ||
| CN201710069705 | 2017-02-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106916263A true CN106916263A (en) | 2017-07-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710229840.9A Pending CN106916263A (en) | 2017-02-08 | 2017-04-10 | A kind of method of organic-silicon-modified automobile coating water-based acrylic resin |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858076A (en) * | 2006-04-21 | 2006-11-08 | 浙江大学 | Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method |
| CN102731735A (en) * | 2012-06-05 | 2012-10-17 | 华南理工大学 | Organosilicon modified silica sol/polyacrylate composite emulsion and its preparation method |
| CN103059313A (en) * | 2012-12-17 | 2013-04-24 | 中山大桥化工集团有限公司 | Method for preparing organosilicon modified acrylic resin |
| CN104558450A (en) * | 2014-12-30 | 2015-04-29 | 北京金汇利应用化工制品有限公司 | Organic-inorganic compound modified water-based acrylic resin and preparation method thereof |
| CN106318091A (en) * | 2016-08-19 | 2017-01-11 | 北京金汇利应用化工制品有限公司 | Resin for novel waterborne double-component organic-inorganic hybrid coating and preparation method of resin |
-
2017
- 2017-04-10 CN CN201710229840.9A patent/CN106916263A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858076A (en) * | 2006-04-21 | 2006-11-08 | 浙江大学 | Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method |
| CN102731735A (en) * | 2012-06-05 | 2012-10-17 | 华南理工大学 | Organosilicon modified silica sol/polyacrylate composite emulsion and its preparation method |
| CN103059313A (en) * | 2012-12-17 | 2013-04-24 | 中山大桥化工集团有限公司 | Method for preparing organosilicon modified acrylic resin |
| CN104558450A (en) * | 2014-12-30 | 2015-04-29 | 北京金汇利应用化工制品有限公司 | Organic-inorganic compound modified water-based acrylic resin and preparation method thereof |
| CN106318091A (en) * | 2016-08-19 | 2017-01-11 | 北京金汇利应用化工制品有限公司 | Resin for novel waterborne double-component organic-inorganic hybrid coating and preparation method of resin |
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Application publication date: 20170704 |
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