CN110590984A - Preparation method of acrylic resin for flexible plastic - Google Patents
Preparation method of acrylic resin for flexible plastic Download PDFInfo
- Publication number
- CN110590984A CN110590984A CN201910627253.4A CN201910627253A CN110590984A CN 110590984 A CN110590984 A CN 110590984A CN 201910627253 A CN201910627253 A CN 201910627253A CN 110590984 A CN110590984 A CN 110590984A
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- China
- Prior art keywords
- resin
- caprolactone
- acrylic resin
- maintaining
- hours
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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
- C08F220/16—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
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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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
Abstract
The invention discloses acrylic resin for flexible plastics, which is acrylic acid modified by caprolactone, and the synthesis method comprises the following steps: (1) firstly putting caprolactone and hydroxyethyl acrylate with equal molar ratio into a reaction kettle, introducing N2 for protection, starting stirring, and heating to 140-150 ℃ to maintain the temperature; (2) adding a proper amount of organic tin catalyst, maintaining for 5 hours at the temperature, cooling and obtaining an intermediate B. The invention has the beneficial effects that: 1. caprolactone groups are introduced into the acrylic resin, and the flexibility, the impact strength, the hardness and the like of the coating film can be improved to different degrees according to different types and different reaction amounts. At the same time, they can make the polymer have good hydrolysis resistance, chemical resistance and compatibility. And can be crosslinked with melamine formaldehyde resin, isocyanate, epoxy resin and other curing agents capable of reacting with hydroxyl.
Description
Technical Field
The invention belongs to the field of resin, and particularly relates to acrylic resin for flexible plastic.
Background
The acrylic resin is a very important variety in coating resin, has strong controllability of a synthesis process, excellent weather resistance and pigment dispersibility, and has increasingly large specific gravity in the coating resin. The acrylic resins currently available on the market are three types: 1. the thermosetting acrylic resin which can be baked and crosslinked with amino resin, 2, hydroxyl acrylic amino resin which reacts with NCO, and 3, thermoplastic acrylic resin which is formed by solvent volatilization.
With the more and more widespread use of plastic products, the market has higher and higher requirements on the protection of plastic coatings. With the high development of electronic products and high-performance plastic products, the demand of flexible plastics is increased greatly, but plastic coatings on the market mainly aim at the surface protection of high-hardness plastics, and the flexible plastics require high ductility and flexibility and do not crack when being bent. Such products are now less available.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the acrylic resin for the flexible plastic.
The invention is realized by the following technical scheme:
the acrylic resin for flexible plastic is acrylic acid modified by caprolactone, and the synthesis method comprises the following steps:
(1) firstly putting caprolactone and hydroxyethyl acrylate with equal molar ratio into a reaction kettle, introducing N2 for protection, starting stirring, and heating to 140-150 ℃ to maintain the temperature;
(2) adding a proper amount of organic tin catalyst, maintaining for 5 hours at the temperature, cooling to obtain an intermediate B;
(3) putting a proper amount of the intermediate B, methyl (meth) acrylate, butyl methacrylate, styrene, hydroxyethyl acrylate, acrylic acid and an initiator into a head tank, safely dissolving and uniformly stirring;
(4) adding a proper amount of dimethylbenzene into a reaction kettle, heating to 130 +/-2 ℃, dropwise adding the monomers of the head tank into the reaction kettle at a constant speed for 3 hours, maintaining for 1 hour, adding an initiator, maintaining for 2 hours, detecting the acid value and viscosity of the resin, diluting the resin with dimethylbenzene until the resin is qualified, cooling and packaging the resin until the required solid content is obtained.
Wherein, the contents of all reactants are (percentage):
compared with the prior art, the invention has the beneficial effects that:
1. caprolactone groups are introduced into the acrylic resin, and the flexibility, the impact strength, the hardness and the like of the coating film can be improved to different degrees according to different types and different reaction amounts. At the same time, they can make the polymer have good hydrolysis resistance, chemical resistance and compatibility. And can perform crosslinking action with melamine formaldehyde resin, isocyanate, epoxy resin and other curing agents capable of reacting with hydroxyl;
2. a semi-finished product process is adopted in the synthesis process, so that caprolactone groups can be effectively and completely added into a resin mechanism, and the amount of residual monomers is reduced to the minimum;
3. the common method for utilizing caprolactone is to add partial oligomer, but the caprolactone polymer in the market has too great uniqueness and low molecular weight.
The invention adopts self synthesis, partial isomers and other products in the semi-finished product can react in further polymerization, the waste of resources is reduced, and the mechanism is diversified. According to the invention, a special flexible monomer is introduced into the acrylic resin for modification through grafting, and the reaction with a substrate material is increased by increasing the molecular weight of the resin and increasing special groups on resin branched chains, so that the flexibility and ductility of the resin are improved, and a paint film of the acrylic resin has better substrate adhesion, paint film compactness and flexibility.
Detailed Description
The following detailed description of embodiments of the invention, but the invention can be practiced in many different ways, as defined and covered by the claims.
Example 1:
(1) firstly putting caprolactone and hydroxyethyl acrylate with equal molar ratio into a reaction kettle, introducing N2 for protection, starting stirring, and heating to 140-150 ℃ to maintain the temperature;
(2) adding a proper amount of organic tin catalyst, maintaining for 5 hours at the temperature, cooling to obtain an intermediate B;
(3) putting 10% of intermediate B, 8% of methyl (meth) acrylate, 25% of butyl methacrylate, 9% of styrene, 9.5% of hydroxyethyl acrylate, 0.8% of acrylic acid and 3% of initiator into an overhead tank for safe dissolution and uniform stirring;
(4) adding 35% dimethylbenzene into a reaction kettle, heating to 130 +/-2 ℃, dropwise adding the monomer of the head tank into the reaction kettle at a constant speed for 3 hours, maintaining for 1 hour, adding an initiator, maintaining for 2 hours, detecting the acid value and viscosity of the resin, diluting the resin with dimethylbenzene until the resin is qualified, cooling and packaging the resin until the required solid content is obtained.
Example 2:
(1) firstly putting caprolactone and hydroxyethyl acrylate with equal molar ratio into a reaction kettle, introducing N2 for protection, starting stirring, and heating to 140-150 ℃ to maintain the temperature;
(2) adding a proper amount of organic tin catalyst, maintaining for 5 hours at the temperature, cooling to obtain an intermediate B;
(3) putting 15% of intermediate B, 8.2% of methyl (meth) acrylate, 22% of butyl methacrylate, 10% of styrene, 8% of hydroxyethyl acrylate, 1.3% of acrylic acid and 2.5% of initiator into an overhead tank for safe dissolution and uniform stirring;
(4) adding 33% dimethylbenzene into a reaction kettle, heating to 130 +/-2 ℃, dropwise adding the monomer of the head tank into the reaction kettle at a constant speed for 3 hours, maintaining for 1 hour, adding an initiator, maintaining for 2 hours, detecting the acid value and viscosity of the resin, diluting the resin with dimethylbenzene until the resin is qualified, cooling and packaging the resin until the required solid content is obtained.
In summary, the present invention is only a preferred embodiment, and not intended to limit the scope of the invention, and all equivalent changes and modifications in the shape, structure, characteristics and spirit of the present invention described in the claims should be included in the scope of the present invention.
Claims (2)
1. A preparation method of acrylic resin for flexible plastics is characterized by comprising the following steps: the method comprises the following steps:
(1) firstly putting caprolactone and hydroxyethyl acrylate with equal molar ratio into a reaction kettle, introducing N2 for protection, starting stirring, and heating to 140-150 ℃ to maintain the temperature;
(2) adding a proper amount of organic tin catalyst, maintaining for 5 hours at the temperature, cooling to obtain an intermediate B;
(3) putting a proper amount of the intermediate B, methyl (meth) acrylate, butyl methacrylate, styrene, hydroxyethyl acrylate, acrylic acid and an initiator into a head tank, safely dissolving and uniformly stirring;
(4) adding a proper amount of dimethylbenzene into a reaction kettle, heating to 130 +/-2 ℃, dropwise adding the monomers of the head tank into the reaction kettle at a constant speed for 3 hours, maintaining for 1 hour, adding an initiator, maintaining for 2 hours, detecting the acid value and viscosity of the resin, diluting the resin with dimethylbenzene until the resin is qualified, cooling and packaging the resin until the required solid content is obtained.
2. The acrylic resin for flexible plastics according to claim 1, wherein: wherein, the contents of all reactants are (percentage):
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910627253.4A CN110590984A (en) | 2019-07-12 | 2019-07-12 | Preparation method of acrylic resin for flexible plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910627253.4A CN110590984A (en) | 2019-07-12 | 2019-07-12 | Preparation method of acrylic resin for flexible plastic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110590984A true CN110590984A (en) | 2019-12-20 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910627253.4A Pending CN110590984A (en) | 2019-07-12 | 2019-07-12 | Preparation method of acrylic resin for flexible plastic |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457443A (en) * | 2020-11-25 | 2021-03-09 | 武汉双虎涂料有限公司 | Acrylic resin for automobile varnish and preparation method thereof |
| CN113999567A (en) * | 2021-11-30 | 2022-02-01 | 业成科技（成都）有限公司 | Ink and optical assembly |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001151998A (en) * | 1999-11-30 | 2001-06-05 | Daicel Chem Ind Ltd | Method of producing lactone modified reactive monomer composition with reduced lactone chain |
-
2019
- 2019-07-12 CN CN201910627253.4A patent/CN110590984A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001151998A (en) * | 1999-11-30 | 2001-06-05 | Daicel Chem Ind Ltd | Method of producing lactone modified reactive monomer composition with reduced lactone chain |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457443A (en) * | 2020-11-25 | 2021-03-09 | 武汉双虎涂料有限公司 | Acrylic resin for automobile varnish and preparation method thereof |
| CN113999567A (en) * | 2021-11-30 | 2022-02-01 | 业成科技（成都）有限公司 | Ink and optical assembly |
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Application publication date: 20191220 |