CN107236418A - The preparation method of the water-based acrylic resin of epoxy resin modification - Google Patents
The preparation method of the water-based acrylic resin of epoxy resin modification Download PDFInfo
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- CN107236418A CN107236418A CN201710580893.5A CN201710580893A CN107236418A CN 107236418 A CN107236418 A CN 107236418A CN 201710580893 A CN201710580893 A CN 201710580893A CN 107236418 A CN107236418 A CN 107236418A
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- water
- epoxy resin
- based acrylic
- acrylic resin
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- 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
- 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
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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 invention discloses a kind of preparation method of the water-based acrylic resin of epoxy resin modification, mix monomer and epoxy resin that it is made up of acrylic acid, styrene, Isobutyl methacrylate, methyl acrylate and hydroxy acrylic acid, react under initiator effect and obtain.The present invention is by the preferably synthetic technique of many experiments, and the water-based acrylic resin coating of the epoxy resin modification prepared can largely reduce VOC in coating, and the feature of environmental protection is strong.The water-based acrylic resin coating of the epoxy resin modification prepared has excellent adhesive force, and glossiness is good, and with excellent hardness and impact resistance, achieves extraordinary technique effect.
Description
Technical field
The present invention relates to a kind of coating, and in particular to a kind of system of the water-based acrylic resin of environmentally friendly epoxy resin modification
Preparation Method, belongs to technical field of polymer materials.
Background technology
In recent years, with the continuous enhancing of people's environmental consciousness, many countries have issued control VOC
(VOC) volatility in environmental regulation, research and development environment-friendly coating and application techniques, reduction coating material production and construction
Organic compound (VOC), it has also become the center of domestic and international most of coating and resin design work.Water paint because using water and
Hydrophilic solvent is used as diluent, it is possible to reduce control VOC (VOC) discharge, thus the weight as paint development
Want direction and study hotspot.But there is poor adhesive force in common water borne acrylic resin, gloss of film is not compared with solvent type resin
The shortcomings of high and impact resistance is poor.
The content of the invention
Goal of the invention：The purpose of the present invention is in view of the shortcomings of the prior art, by many experiments, to select epoxy resin pair
Water-based acrylic resin is modified, and can improve the shortcomings of water-based acrylic resin adhesive force is not good, gloss is not high.
Technical scheme, to realize object above, the technical solution adopted by the present invention is：
A kind of preparation method of the water-based acrylic resin of epoxy resin modification, it comprises the following steps：
(1) in the four-hole boiling flask equipped with agitator, condenser, thermometer and constant pressure funnel add reaction dissolvent and
Epoxy resin；
(2) acrylic monomers is mixed, then initiator is dissolved in mixing acrylic monomers；
(3) solvent in the four-hole boiling flask of step (1) is warming up to after backflow, mix monomer, 3 made from step (2) is added dropwise
~4h completion of dropping, maintains the reflux for reaction temperature, continues to react, initiator and solvent are added in interval, epoxy resin modification is made
Water-based acrylic resin.
Preferably, the preparation method of the water-based acrylic resin of above-described epoxy resin modification, it includes
Following steps：
(1) in the four-hole boiling flask equipped with agitator, condenser, thermometer and constant pressure funnel add reaction dissolvent and
Epoxy resin；
(2) acrylic monomers is mixed, then initiator is dissolved in mixing acrylic monomers；
(3) solvent in the four-hole boiling flask of step (1) is warming up to after backflow, mix monomer made from step (2) is added dropwise,
3~4h completion of dropping, maintains the reflux for reaction temperature, continues to react after 2h, then adds 1 part of initiator and 1 part of solvent every 1h, mends
After complete 3 parts of initiators and 3 parts of solvents, the water-based acrylic resin of epoxy resin modification is made.
Preferably, a kind of preparation method of the water-based acrylic resin of above-described epoxy resin modification, institute
The acrylic monomers stated includes acrylic acid, styrene, Isobutyl methacrylate, methyl acrylate and hydroxy-ethyl acrylate.
Preferably, the preparation method of the water-based acrylic resin of above-described a kind of epoxy resin modification, instead
It is butyl glycol ether and butanol to answer solvent.
Preferably, a kind of preparation method of the water-based acrylic resin of above-described epoxy resin modification, third
The weight percentage of olefin(e) acid is that the weight percentage of 3~8%, styrene is the weight of 5~10%, Isobutyl methacrylate
It is that the weight percentage of 10~15%, methyl acrylate is the weight hundred of 8~16%, acrylate monomers to measure percentage composition
Point content is that the weight percentage of 6~15%, epoxy resin is that the weight percentage of 5~10%, butyl glycol ether is 15
~16%, the weight percentage of butanol is that the weight percentage of 3~5%, initiator is 1~5%.
A kind of water-based acrylic resin coating of epoxy resin modification, it includes the ring described in any one of claims 1 to 3
The resin modified water-based acrylic resin of oxygen, dispersant, defoamer, wetting agent, pigment, levelling agent, dimethylethanolamine,
SM5717 amino resins, BCS (butyl glycol ether) and water.
Preferably, above-described a kind of water soluble acrylic acid amido coatings, it is by any one of claims 1 to 3
60 parts of the water-based acrylic resin of described epoxy resin modification, 0.5 part of dispersant, 0.2 part of defoamer, 0.2 part of wetting agent, face
25 parts of material, 0.2 part of levelling agent, 3.2 parts of dimethylethanolamine, 3 parts of butyl glycol ether, 12 parts of SM5717 amino resins, water 10.7
Part.
Beneficial effect：Compared to the prior art, the present invention has the following advantages：
The present invention obtains optimal raw material by many experiments screening and constitutes and match, and passes through the preferably synthetic work of many experiments
The optimum amount proportioning of skill and its each raw material, is modified to water-based acrylic resin using epoxy resin, can improve aqueous third
The shortcomings of olefin(e) acid resin adhesive force is not good, gloss is not high.Present invention experiment is found：There is no unsaturated double-bond in epoxy resin, but
The H on a-H and tertiary carbon on its ehter bond ortho position carbon atom is relatively active, and free radical can be formed in the presence of initiator,
It can be may occur from acrylicacidandesters class monomer under initiator effect by base polymerisation, the product ultimately formed is not connect
The mixture of the epoxy resin of branch, the acrylic resin being graft-polymerized and acrylic monomers copolymer.The asphalt mixtures modified by epoxy resin prepared
The water-based acrylic resin coating that fat is modified can largely reduce the purpose of VOC in coating, and the feature of environmental protection is strong.And the ring prepared
The resin modified water-based acrylic resin coating of oxygen has excellent adhesive force, and glossiness is good, and with excellent hardness and resistance to
Impact property, achieves extraordinary technique effect.
Found in building-up process of the present invention：The species of acrylic acid mix monomer and specific consumption composition, it is anti-with epoxy resin
The degree that should be modified has an important influence, and the species and specific consumption of different acrylic acid mix monomer are to adhesive force and gloss
Degree has important influence.
The present invention obtains the species and specific consumption of optimal acrylic acid mix monomer using many experiments screening.So as to
It can obviously improve the adhesive force and glossiness of water-based acrylic resin.
Embodiment
Embodiment 1
1st, a kind of preparation method of the water-based acrylic resin of epoxy resin modification, it comprises the following steps：
(1) table 1 below is added in the four-hole boiling flask equipped with agitator, condenser, thermometer and constant pressure funnel
Butyl glycol ether, butanol and epoxy resin 601R；
(2) table 1 is pressed by quantitative acrylic acid, styrene, Isobutyl methacrylate, methyl acrylate, acrylic acid hydroxyl second
Ester and initiator dibenzoyl peroxide (BPO) mixing, stir, in input addition funnel；
(3) solvent in flask is warming up to after backflow, the acrylic monomers and initiator of step (2) mixing is added dropwise, about
3.5h completion of dropping.Keeping temperature, continues to react after 2h, then adds 1 part of initiator and 1 part of butyl glycol ether solvent every 1h,
Mend after 3 parts of initiators and solvent, the water-based acrylic resin of slightly lurid epoxy resin modification is finally made.
The water-based acrylic resin raw material composition of the epoxy resin modification of table 1
Embodiment 2
1st, the raw material composition input of the water-based acrylic resin for the epoxy resin modification for preparing embodiment 1 and table 2
In preparing tank, stirred in sand mill, fineness is up to after 20 μm, and filtering is made paste resin, adds quantitative amino resins, water
Etc. being configured to water-borne acrylic coatings.The water-based acrylic resin formulation for coating material composition of the epoxy resin modification of table 2.
2nd, performance test, test knot are carried out to the water-based acrylic resin coating of obtained epoxy resin modification made above
It is really as shown in table 3 below：
The paint film property testing result of table 3
More than test result indicates that, the present invention prepare epoxy resin modification water-based acrylic resin coating tool
There is the good feature of environmental protection, and there is excellent adhesive force, glossiness and excellent hardness and impact resistance, and the feature of environmental protection
Can be good, achieve extraordinary technological progress.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of the water-based acrylic resin of epoxy resin modification, it is characterised in that it comprises the following steps：
(1) reaction dissolvent and epoxy are added in the four-hole boiling flask equipped with agitator, condenser, thermometer and constant pressure funnel
Resin；
(2) acrylic monomers is mixed, then initiator is dissolved in mixing acrylic monomers；
(3) solvent in the four-hole boiling flask of step (1) is warming up to after backflow, mix monomer, 3~4h made from step (2) is added dropwise
Completion of dropping, maintains the reflux for reaction temperature, continues to react, initiator and solvent are added in interval, the water of epoxy resin modification is made
Property acrylic resin.
2. a kind of preparation method of the water-based acrylic resin of epoxy resin modification, it is characterised in that it comprises the following steps：
(1) reaction dissolvent and epoxy are added in the four-hole boiling flask equipped with agitator, condenser, thermometer and constant pressure funnel
Resin；
(2) acrylic monomers is mixed, then initiator is dissolved in mixing acrylic monomers；
(3) solvent in the four-hole boiling flask of step (1) is warming up to after backflow, mix monomer made from step (2) is added dropwise, 3~
4h completion of dropping, maintains the reflux for reaction temperature, continues to react after 2h, then adds 1 part of initiator and 1 part of solvent every 1h, has mended 3
After part initiator and 3 parts of solvents, the water-based acrylic resin of epoxy resin modification is made.
3. a kind of preparation method of the water-based acrylic resin of epoxy resin modification according to claim 1 or 2, its feature
It is, described acrylic monomers includes acrylic acid, styrene, Isobutyl methacrylate, methyl acrylate and acrylic acid hydroxyl
Ethyl ester.
4. a kind of preparation method of the water-based acrylic resin of epoxy resin modification according to claim 3, its feature exists
In reaction dissolvent is butyl glycol ether and butanol.
5. a kind of preparation method of the water-based acrylic resin of epoxy resin modification according to claim 4, its feature exists
In the weight percentage that the weight percentage of, acrylic acid is 3~8%, styrene be 5~10%, isobutyl
The weight percentage of ester is that the weight percentage of 10~15%, methyl acrylate is 8~16%, acrylate monomers
Weight percentage is that the weight percentage of 6~15%, epoxy resin is that the weight percent of 5~10%, butyl glycol ether contains
Amount is that the weight percentage of 15~16%, butanol is that the weight percentage of 3~5%, initiator is 1~5%.
6. the water-based acrylic resin coating of a kind of epoxy resin modification, it is characterised in that it is any comprising claims 1 to 3
The water-based acrylic resin of epoxy resin modification described in, dispersant, defoamer, wetting agent, pigment, levelling agent, dimethyl
Monoethanolamine, SM5717 amino resins, butyl glycol ether and water.
7. a kind of water soluble acrylic acid amido coatings according to claim 4, it is characterised in that it is appointed by claims 1 to 3
60 parts of the water-based acrylic resin of epoxy resin modification described in one, 0.5 part of dispersant, 0.2 part of defoamer, wetting agent 0.2
Part, 25 parts of pigment, 0.2 part of levelling agent, 3.2 parts of dimethylethanolamine, 3 parts of butyl glycol ether, 12 parts of SM5717 amino resins, water
10.7 parts.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710580893.5A CN107236418A (en) | 2017-07-17 | 2017-07-17 | The preparation method of the water-based acrylic resin of epoxy resin modification |
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| CN201710580893.5A CN107236418A (en) | 2017-07-17 | 2017-07-17 | The preparation method of the water-based acrylic resin of epoxy resin modification |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180877A (en) * | 2018-09-19 | 2019-01-11 | 江苏三木化工股份有限公司 | Plastic paint waterborne epoxy modified acrylic resin and preparation method thereof |
| CN109370429A (en) * | 2018-11-26 | 2019-02-22 | 南昌科悦企业管理咨询有限公司 | A kind of counter body water paint and preparation method thereof |
| CN109438630A (en) * | 2018-09-19 | 2019-03-08 | 江苏三木化工股份有限公司 | Epoxy resin modified acrylic resin of traffic paint and preparation method thereof |
| CN109836865A (en) * | 2018-04-18 | 2019-06-04 | 上海振华重工（集团）常州油漆有限公司 | A kind of preparation method of aqueous amino-stoving varnish |
| CN110317026A (en) * | 2019-08-16 | 2019-10-11 | 佛山市德堡建材有限公司 | A kind of glue for tile |
| CN111171495A (en) * | 2020-01-20 | 2020-05-19 | 杭州烯创科技有限公司 | Graphene-modified waterborne acrylic acid-grafted epoxy resin and preparation method thereof |
| CN114316281A (en) * | 2021-12-17 | 2022-04-12 | 江苏三木化工股份有限公司 | Acrylic acid modified epoxy acrylate and preparation method thereof |
| CN115873505A (en) * | 2022-12-27 | 2023-03-31 | 江苏扬瑞新材料有限公司 | Water-based environment-friendly coating and preparation method thereof |
| CN116179021A (en) * | 2023-02-01 | 2023-05-30 | 上海攸彩新材料科技有限公司 | Water-resistant salt-fog-resistant water-based universal paint color paste and application thereof |
| CN116515358A (en) * | 2023-04-28 | 2023-08-01 | 深圳市深赛尔股份有限公司 | Preparation method of modified aqueous aluminum rolling paint and aqueous aluminum rolling-aqueous printing paint |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836865A (en) * | 2018-04-18 | 2019-06-04 | 上海振华重工（集团）常州油漆有限公司 | A kind of preparation method of aqueous amino-stoving varnish |
| CN109180877A (en) * | 2018-09-19 | 2019-01-11 | 江苏三木化工股份有限公司 | Plastic paint waterborne epoxy modified acrylic resin and preparation method thereof |
| CN109438630A (en) * | 2018-09-19 | 2019-03-08 | 江苏三木化工股份有限公司 | Epoxy resin modified acrylic resin of traffic paint and preparation method thereof |
| CN109370429A (en) * | 2018-11-26 | 2019-02-22 | 南昌科悦企业管理咨询有限公司 | A kind of counter body water paint and preparation method thereof |
| CN110317026A (en) * | 2019-08-16 | 2019-10-11 | 佛山市德堡建材有限公司 | A kind of glue for tile |
| CN111171495A (en) * | 2020-01-20 | 2020-05-19 | 杭州烯创科技有限公司 | Graphene-modified waterborne acrylic acid-grafted epoxy resin and preparation method thereof |
| CN114316281A (en) * | 2021-12-17 | 2022-04-12 | 江苏三木化工股份有限公司 | Acrylic acid modified epoxy acrylate and preparation method thereof |
| CN115873505A (en) * | 2022-12-27 | 2023-03-31 | 江苏扬瑞新材料有限公司 | Water-based environment-friendly coating and preparation method thereof |
| CN116179021A (en) * | 2023-02-01 | 2023-05-30 | 上海攸彩新材料科技有限公司 | Water-resistant salt-fog-resistant water-based universal paint color paste and application thereof |
| CN116179021B (en) * | 2023-02-01 | 2024-02-09 | 上海攸彩新材料科技有限公司 | Water-resistant salt-fog-resistant water-based universal paint color paste and application thereof |
| CN116515358A (en) * | 2023-04-28 | 2023-08-01 | 深圳市深赛尔股份有限公司 | Preparation method of modified aqueous aluminum rolling paint and aqueous aluminum rolling-aqueous printing paint |
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Application publication date: 20171010 |