CN108623758A - A kind of aqueous amino-stoving varnish epoxy modified acrylic resin and preparation method thereof - Google Patents
A kind of aqueous amino-stoving varnish epoxy modified acrylic resin and preparation method thereof Download PDFInfo
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- CN108623758A CN108623758A CN201810483636.4A CN201810483636A CN108623758A CN 108623758 A CN108623758 A CN 108623758A CN 201810483636 A CN201810483636 A CN 201810483636A CN 108623758 A CN108623758 A CN 108623758A
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- CN
- China
- Prior art keywords
- epoxy
- modified acrylic
- acrylic resin
- resin
- stoving varnish
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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
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
-
- 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
- C09D7/20—Diluents or solvents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of aqueous amino-stoving varnish epoxy modified acrylic resins and preparation method thereof.The present invention is introduced into methyl acrylamide monomer when synthesizing epoxy is acrylic resin modified and carries out ring-opening reaction to the epoxy group in epoxy resin, it accesses in resin backbone together, coordinate methacrylate, styrene, methacrylic acid hydroxy ester, methacrylic acid, initiator, using propylene glycol monomethyl ether, dipropylene glycol methyl ether as solvent, resinous acid value is controlled, the epoxy modified acrylic resin of aqueous amino-stoving varnish is prepared into.The present invention uses one-step synthesis method epoxy modified acrylic resin, and synthesis technology more preferably control, produces and is more convenient；The dosage that the present invention passes through control Methacrylamide, it can accomplish the complete open loop of epoxy resin, during preparing coating in the later stage, it is avoided that on resin that the epoxy group containing non-open loop and amine neutralizer react, avoid gained coating returns thick, gelatinization phenomenon generation.
Description
Technical field
The present invention relates to a kind of resins, specifically more particularly to a kind of aqueous amino-stoving varnish epoxy-modified acrylic acid
Resin and preparation method thereof.
Background technology
With the exhaustion of petroleum resources, the pollution of plus environmental, coating industry is all sent out to more environmentally friendly, safer direction
Exhibition, energy-saving and emission-reduction, the oily discharge for changing water, reducing VOC in coating to the greatest extent have been very urgent.It is prepared by epoxy modified acrylic resin
Amino-stoving varnish in many base materials such as galvanized sheet, magnesium alloy, on glass base material, it is increased any adhesive force need not to be carried out
Pretreatment procedure all has excellent adhesive force, compact in paint film, chemical-resistant.
Invention content
The present invention has synthesized a kind of aqueous amino-stoving varnish with epoxy-modified acrylic acid tree using easy resin syntheses processes
Fat.
The present invention is implemented by the following technical programs：
A kind of aqueous amino-stoving varnish epoxy modified acrylic resin, is made of the composition of raw materials of following parts by weight：
The initiator is the composite initiator being made of dibenzoyl peroxide and peroxidized t-butyl perbenzoate.
The epoxide equivalent of the epoxy resin is 185-190.
A kind of aqueous amino-stoving varnish epoxy modified acrylic resin, includes the following steps：
A, epoxy resin, the propylene glycol monomethyl ether of 80-85% and dipropylene glycol methyl ether are put into reaction kettle, is passed through N2 protections
And stirring is opened, be warming up to 118 ± 2 DEG C and maintains this temperature；
B, by methacrylate, styrene, methacrylic acid hydroxy ester, methacrylic acid, 75-80% initiator and
It dissolves safely, stir evenly in Methacrylamide input head tank；
C, the monomer in step b head tanks is at the uniform velocity added dropwise in reaction kettle and is maintained in 3-3.3h at 118 ± 2 DEG C
Remaining initiator is dissolved in remaining propylene glycol monomethyl ether, and is added dropwise in reaction kettle in 30-40min by 2h, after being added dropwise to complete
2h is maintained at 118 ± 2 DEG C again, resinous acid value and viscosity is detected, is filtered and packaged after qualified.
Compared with prior art, the beneficial effects of the invention are as follows：
Epoxy resin and Methacrylamide are introduced in resin of the present invention, are increased resin dryness and adhesive force, are increased
The crosslink density of later stage paint film, the paint film prepared using resin of the present invention have better hardness, scratch resistance, chemicals-resistant
Property, adhesive force show very outstanding on some special substrates such as galvanized sheet, magnesium alloy, glass；The present invention uses a step
Method synthesizing epoxy is acrylic resin modified, and synthesis technology more preferably controls, it is more convenient to produce；Later stage painting is prepared using resin of the present invention
Material all can substitute solvent with water and be diluted for coating preparation, coating application, and energy-saving and emission-reduction reduce VOC emission, reduce to ring
The pollution in border；The present invention can accomplish the complete open loop of epoxy resin by the dosage of control Methacrylamide, prepare and apply in the later stage
During material, it is avoided that on resin that the epoxy group containing non-open loop and amine neutralizer react, avoids gained coating
Return thick, gelatinization phenomenon generation.
Specific implementation mode
It is described in detail with reference to embodiment is most further to the present invention：
Embodiment 1：
By in 5 parts of epoxy resin, 9.6 parts of propylene glycol monomethyl ethers and 6 parts of dipropylene glycol methyl ether input reaction kettles, it is passed through N2 protections
And stirring is opened, be warming up to 118 DEG C and maintains this temperature；By 36 parts of methacrylates, 14 parts of styrene, 15 parts of metering systems
It dissolves safely, stir in sour hydroxy ester, 5.5 methacrylic acids, 2 parts of initiators and 3.5 parts of Methacrylamide input head tanks
Uniformly；The monomer in head tank is at the uniform velocity added dropwise in 3h in reaction kettle and is maintained 2h at 118 DEG C, by remaining 0.5 part
Initiator is dissolved in remaining 2.4 parts of propylene glycol monomethyl ethers, and is added dropwise in reaction kettle in 40min, and rear reaction kettle is added dropwise to complete
Temperature maintains 2h at 118 DEG C again, detects resinous acid value and viscosity, is filtered and packaged after qualified, resin solid acid value 60mgKOH/
g。
Embodiment 2：
By in 4 parts of epoxy resin, 11.2 parts of propylene glycol monomethyl ethers and 7 parts of dipropylene glycol methyl ether input reaction kettles, it is passed through N2 guarantors
Stirring is protected and opened, be warming up to 120 DEG C and maintains this temperature；By 37 parts of methacrylates, 15 parts of styrene, 14 parts of methyl-props
It dissolves safely, stir in olefin(e) acid hydroxy ester, 4 parts of methacrylic acids, 2 parts of initiators and 2.5 parts of Methacrylamide input head tanks
It mixes uniformly；The monomer in head tank is at the uniform velocity added dropwise in 3h in reaction kettle and is maintained 2h at 120 DEG C, by remaining 0.5
Part initiator is dissolved in remaining 2.8 parts of propylene glycol monomethyl ethers, and is added dropwise in reaction kettle in 30min, is reacted after being added dropwise to complete
Kettle maintains 2h at 120 DEG C again, detects resinous acid value and viscosity, is filtered and packaged after qualified, resin solid acid value 60mgKOH/g.
Embodiment 3：
By in 7 parts of epoxy resin, 9.6 parts of propylene glycol monomethyl ethers and 6 parts of dipropylene glycol methyl ether input reaction kettles, it is passed through N2 protections
And stirring is opened, be warming up to 116 DEG C and maintains this temperature；By 35 parts of methacrylates, 13 parts of styrene, 14 parts of metering systems
It dissolves safely, stir in sour hydroxy ester, 6 parts of methacrylic acids, 3.2 parts of initiators and 3 parts of Methacrylamide input head tanks
Uniformly；The monomer in head tank is at the uniform velocity added dropwise in 3.3h in reaction kettle and is maintained 2h at 118 DEG C, by remaining 0.8
Part initiator is dissolved in remaining 2.4 parts of propylene glycol monomethyl ethers, and is added dropwise in reaction kettle in 40min, is existed again after being added dropwise to complete
2h is maintained at 116 DEG C, is detected resinous acid value and viscosity, is filtered and packaged after qualified, resin solid acid value 60mgKOH/g.
Initiator uses the composite initiator being made of dibenzoyl peroxide and peroxidized t-butyl perbenzoate, the two
Mixed proportion is convertible.
The present invention is introduced into methyl acrylamide monomer when synthesizing epoxy is acrylic resin modified to the ring in epoxy resin
Oxygen groups carry out ring-opening reaction, access in resin backbone together, cooperation methacrylate, styrene, methacrylic acid hydroxyl
Ester, methacrylic acid, initiator control resinous acid value, are prepared into aqueous using propylene glycol monomethyl ether, dipropylene glycol methyl ether as solvent
The epoxy modified acrylic resin of amino-stoving varnish.
The active hydrogen contained in synthetic raw material Methacrylamide of the present invention is easy to and epoxy resin epoxide epoxy group group
It reacts to obtain-OH groups, the carbon double bond contained in molecule is easier to occur with other methacrylate-based monomers
Raolical polymerizable, to be readily available the epoxy modified acrylic resin containing more-OH groups；Methacrylamide
In contain 2 active hydrogens, can theoretically react to obtain 2-OH groups with epoxy resin epoxide epoxy group group completely, but anti-
Presence of the later stage due to space steric effect is answered, generally only 1 active hydrogen reacts with epoxy resin, to which-NH- is protected
It is left behind, this group also improves a lot to adhesive force during preparing paint film in the later stage.
As long as controlling the dosage of methacrylic acid, resin solid 45~80mgKOH/g of acid value is controlled, in later stage coating system
Resin is neutralized by 7.5~8.5 alkaline system of pH value by amine neutralizer during standby, can be diluted with water completely and prepare water
Property amino-stoving varnish.
In conclusion only presently preferred embodiments of the present invention, is not used for limiting the scope of implementation of the present invention, it is all according to
The equivalent changes and modifications carried out by shape, construction, feature and spirit described in scope of the invention as claimed should all be included in this
In the right of invention.
Claims (4)
1. a kind of aqueous amino-stoving varnish epoxy modified acrylic resin, it is characterised in that:By the composition of raw materials of following parts by weight
Composition：
2. a kind of aqueous amino-stoving varnish epoxy modified acrylic resin according to claim 1, it is characterised in that:It is described
Initiator is the composite initiator being made of dibenzoyl peroxide and peroxidized t-butyl perbenzoate.
3. a kind of aqueous amino-stoving varnish epoxy modified acrylic resin according to claim 1, it is characterised in that:It is described
The epoxide equivalent of epoxy resin is 185-190.
4. a kind of preparation method of aqueous amino-stoving varnish epoxy modified acrylic resin, it is characterised in that：Include the following steps：
A, epoxy resin, the propylene glycol monomethyl ether of 80-85% and dipropylene glycol methyl ether are put into reaction kettle, is passed through N2 and protects and open
Stirring is opened, be warming up to 118 ± 2 DEG C and maintains this temperature；
B, by methacrylate, the initiator and methyl of styrene, methacrylic acid hydroxy ester, methacrylic acid, 75-80%
It dissolves safely, stir evenly in acrylamide input head tank；
C, the monomer in step b head tanks is at the uniform velocity added dropwise in 3-3.3h in reaction kettle and is maintained 2h at 118 ± 2 DEG C,
Remaining initiator is dissolved in remaining propylene glycol monomethyl ether, and is added dropwise in reaction kettle in 30-40min, after being added dropwise to complete again
2h is maintained at 118 ± 2 DEG C, is detected resinous acid value and viscosity, is filtered and packaged after qualified.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810483636.4A CN108623758A (en) | 2018-05-19 | 2018-05-19 | A kind of aqueous amino-stoving varnish epoxy modified acrylic resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810483636.4A CN108623758A (en) | 2018-05-19 | 2018-05-19 | A kind of aqueous amino-stoving varnish epoxy modified acrylic resin and preparation method thereof |
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| CN108623758A true CN108623758A (en) | 2018-10-09 |
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| CN201810483636.4A Pending CN108623758A (en) | 2018-05-19 | 2018-05-19 | A kind of aqueous amino-stoving varnish epoxy modified acrylic resin and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575181A (en) * | 2018-11-22 | 2019-04-05 | 韶关市合众化工有限公司 | It is a kind of for preparing the preparation method of coating plated item baking vanish acrylic resin |
| CN109824837A (en) * | 2018-12-28 | 2019-05-31 | 广东省石油与精细化工研究院 | A kind of aqueous anti-fouling type metal baking finish of high-strength and high ductility and preparation method thereof |
| CN115232263A (en) * | 2022-08-05 | 2022-10-25 | 黄山联固新材料科技有限公司 | Preparation method of acrylic polyol dispersion |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009066588A1 (en) * | 2007-11-19 | 2009-05-28 | Arakawa Chemical Industries, Ltd. | Aqueous resin composition for coating, and aqueous coating |
| CN103467748A (en) * | 2013-08-13 | 2013-12-25 | 嘉兴市清河高力绝缘有限公司 | Preparation method for waterborne acrylic acid modified epoxy ester emulsion and its amino baking varnish |
| CN107118311A (en) * | 2017-06-08 | 2017-09-01 | 华伦纳路新材料有限公司 | A kind of epoxy modified acrylic resin and preparation method thereof |
-
2018
- 2018-05-19 CN CN201810483636.4A patent/CN108623758A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009066588A1 (en) * | 2007-11-19 | 2009-05-28 | Arakawa Chemical Industries, Ltd. | Aqueous resin composition for coating, and aqueous coating |
| CN103467748A (en) * | 2013-08-13 | 2013-12-25 | 嘉兴市清河高力绝缘有限公司 | Preparation method for waterborne acrylic acid modified epoxy ester emulsion and its amino baking varnish |
| CN107118311A (en) * | 2017-06-08 | 2017-09-01 | 华伦纳路新材料有限公司 | A kind of epoxy modified acrylic resin and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575181A (en) * | 2018-11-22 | 2019-04-05 | 韶关市合众化工有限公司 | It is a kind of for preparing the preparation method of coating plated item baking vanish acrylic resin |
| CN109824837A (en) * | 2018-12-28 | 2019-05-31 | 广东省石油与精细化工研究院 | A kind of aqueous anti-fouling type metal baking finish of high-strength and high ductility and preparation method thereof |
| CN109824837B (en) * | 2018-12-28 | 2021-08-03 | 广东省石油与精细化工研究院 | High-strength high-toughness water-based antifouling metal baking paint and preparation method thereof |
| CN115232263A (en) * | 2022-08-05 | 2022-10-25 | 黄山联固新材料科技有限公司 | Preparation method of acrylic polyol dispersion |
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Application publication date: 20181009 |