CN106065046A - A kind of alcohol-soluble acrylic resin - Google Patents
A kind of alcohol-soluble acrylic resin Download PDFInfo
- Publication number
- CN106065046A CN106065046A CN201610405651.8A CN201610405651A CN106065046A CN 106065046 A CN106065046 A CN 106065046A CN 201610405651 A CN201610405651 A CN 201610405651A CN 106065046 A CN106065046 A CN 106065046A
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- China
- Prior art keywords
- acrylic resin
- alcohol
- soluble acrylic
- peroxide
- monomer
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Classifications
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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
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a kind of alcohol-soluble acrylic resin, and described alcohol-soluble acrylic resin is to be 50: 50～90: 10 to be formed by free radicals copolymerization reaction in mass ratio by the glass transition temperature hard monomer higher than 25 DEG C and the glass transition temperature soft or hard monomer less than 25 DEG C；At least one in n-BMA, acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate, Isooctyl acrylate monomer, lauryl methacrylate, ethoxyethyl methacrylates of described soft monomer；At least one in methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, styrene of described hard monomer.The glass transition temperature of alcohol-soluble acrylic resin of the present invention is 25～45 DEG C, and weight average molecular weight is 30,000 to 100,000.The present invention has moderate adhesive force and preferable toughness, can be dissolved in the alcohols solvents such as ethanol, can meet the serviceability requirement of environment-friendly ink and environmental protection coating material.
Description
Technical field:
The present invention relates to polymeric material field, particularly relate to a kind of alcohol-soluble acrylic resin.
Technical background
Acrylic resin refers to acrylic acid and/or methacrylic acid series unsaturated compound as monomer, by freedom
Base polyreaction prepare a family macromolecule fluoropolymer resin, there is excellent mechanical performance and weatherability, be widely used in coating,
The fields such as ink, building, aviation.Select different monomer ratios, the acrylic resin of various different performance can be prepared.Typically
Acrylic resin need in use with organic solvent such as toluene, dimethylbenzene, butanone, Ketohexamethylene etc. dissolve, this kind solvent is not
But have volatile characteristic, and there is certain toxicity, develop a kind of can be with the acrylic acid tree of low toxicity or nontoxic solvent
Fat, on the one hand can improve environment, it can in addition contain reduce the murder by poisoning to operator.
Summary of the invention
The invention aims to solve the deficiencies in the prior art, it is provided that a kind of alcohol-soluble acrylic resin, can be complete
It is dissolved in the alcohols solvents such as ethanol, and the working environment of operator can be improved, reduce the health hazard to operator.
It is an object of the invention to be achieved through the following technical solutions:
A kind of alcohol-soluble acrylic resin, described alcohol-soluble acrylic resin is higher than 25 DEG C by glass transition temperature
Soft or hard monomer less than 25 DEG C of hard monomer and glass transition temperature be 50: 50～90: 10 by free radical altogether in mass ratio
Poly-reaction forms；The glass transition temperature of described alcohol-soluble acrylic resin is 25～45 DEG C, and weight average molecular weight is 30,000
To 100,000.
Add initiator and molecular weight regulator during reaction, be simultaneously introduced dichloromethane and stearic acid, resin can be improved
Mobility and release property, the consumption of described initiator is the 0.01～10% of monomer total amount by mass percentage, described point
The consumption of son amount regulator is the 0.01～10% of monomer total amount, described dichloromethane and stearic use by mass percentage
Amount is the 0.01-0.5% of monomer total amount by mass percentage.
Described soft monomer selected from n-BMA, acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate,
At least one in Isooctyl acrylate monomer, lauryl methacrylate, ethoxyethyl methacrylates；Described hard monomer choosing
From methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, hydroxyethyl methylacrylate, methacrylic acid
At least one in hydroxypropyl acrylate, styrene.
As further preferred version, described soft monomer is selected from ethyl acrylate, n-butyl acrylate at least
A kind of；Described hard monomer is selected from methyl methacrylate, isobutyl methacrylate, hydroxyethyl methylacrylate, styrene
In at least one.
Above-mentioned alcohol-soluble acrylic resin, wherein, described free radicals copolymerization reaction uses suspension polymerization, body
Polyreaction or solution polymerization.
Above-mentioned alcohol-soluble acrylic resin, wherein, the initiator used by described free radicals copolymerization reaction selects peroxide
At least one in compounds and/or azo compound.
Described peroxide compound selected from benzoyl peroxide, peroxidized t-butyl perbenzoate, cumyl peroxide,
Dilauroyl peroxide, di-isopropyl peroxydicarbonate, Isosorbide-5-Nitrae-peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, peroxy dicarbonate bicyclo-
Own ester, 1,1-di-tert-butyl peroxide-3,3,5-trimethyl-cyclohexanes, di-t-butyl peroxide, tert-butyl hydroperoxide, peroxide
Change at least one in the 2 ethyl hexanoic acid tert-butyl ester.
Described azo compound is different selected from azodiisobutyronitrile, AMBN, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two
In butanoic acid dimethyl ester, azo isobutyl cyano group Methanamide, azo dicyclohexyl formonitrile HCN, azo-bis-iso-dimethyl at least one
Kind.
Further preferred version, the initiator used by copolyreaction select benzoyl peroxide, dilauroyl peroxide, 1,
4-peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, di-isopropyl peroxydicarbonate, the peroxidating 2 ethyl hexanoic acid tert-butyl ester, azo two are different
At least one in butyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).
Above-mentioned alcohol-soluble acrylic resin, it is preferred that the consumption of initiator is monomer total amount by mass percentage
0.05～5.0%.
Above-mentioned alcohol-soluble acrylic resin, wherein, the molecular weight regulator used by copolyreaction selects dodecyl sulfur
At least one in alcohol, iso-butyl mercaptan, α-methyl styrene and dimer thereof.
Above-mentioned alcohol-soluble acrylic resin, it is preferred that the consumption of described molecular weight regulator is by mass percentage
For monomer total amount 0.05～5.0%.
In sum, owing to have employed technique scheme, the present invention compared with prior art, has following useful effect
Really:
The glass transition temperature of the alcohol-soluble acrylic resin that the present invention provides is 25～45 DEG C, and weight average molecular weight is
30,000 to 100,000, there is moderate adhesive force and preferable toughness；The alcohols solvents such as ethanol can be dissolved in, suspension can be used poly-
Close or polymerisation in bulk be prepared as hard resin, it is possible to use polymerisation in solution be prepared as liquid resin, have stronger practicality and
Industrialized popularization value.
Detailed description of the invention
Below by specific embodiment, the present invention is further described in detail.
Embodiment 1
Bulk technique is used to carry out copolyreaction.
Soft monomer: ethyl acrylate 20 mass parts.
Hard monomer: methyl methacrylate 5 mass parts；Isobutyl methacrylate 70 mass parts；Hydroxyethyl methacrylate second
Ester 5 mass parts.
Initiator: use dilauroyl peroxide, Isosorbide-5-Nitrae-peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, peroxidating 2 ethyl hexanoic acid uncle
Butyl ester, 1,1-di-tert-butyl peroxide-3,3,5-trimethyl-cyclohexane composite initiators, consumption is 0.25 mass parts.
Molecular weight regulator: using lauryl mercaptan, consumption is 0.59 mass parts.
Dichloromethane and stearic acid: 0.1 mass parts.
After tested, resulting polymers: the glass transition temperature of acrylic resin is 33 DEG C, weight average molecular weight is 55,
000。
Embodiment 2
Process for suspension polymerization is used to carry out copolyreaction.
Soft monomer: n-butyl acrylate 10 mass parts；Acrylic acid methyl ester. 15 parts.
Hard monomer: ethyl methacrylate 25 mass parts；Isobutyl methacrylate 45 mass parts；Hydroxyethyl methacrylate second
Ester 5 mass parts.
Initiator uses dilauroyl peroxide, Isosorbide-5-Nitrae-peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate composite initiator, and total consumption is
0.3 mass parts.
Molecular weight regulator uses lauryl mercaptan and α-methyl styrene and dimer thereof to be 5: 1 formation in mass ratio
Compound, total consumption is 0.5 mass parts.
Dichloromethane and stearic acid: 0.2 mass parts.
After tested, resulting polymers: the glass transition temperature of acrylic resin is 31 DEG C, weight average molecular weight is 62,
000。
Embodiment 3
Solution polymerization process is used to carry out copolyreaction.
Soft monomer: ethyl acrylate 25 mass parts.
Hard monomer: methyl methacrylate 10 mass parts；Styrene 5 mass parts；Hydroxyethyl methylacrylate 5 mass parts；
Ethyl methacrylate 55 mass parts.
Initiator uses azodiisobutyronitrile, and consumption is 0.5 mass parts.
Molecular weight regulator uses iso-butyl mercaptan and α-methyl styrene and dimeric complex thereof, and consumption is 0.6
Mass parts；
Dichloromethane and stearic acid: 0.25 mass parts.
Using ethanol as solvent, the solid content making reaction system is 45%.
After tested, resulting polymers: the glass transition temperature of acrylic resin is 41 DEG C, weight average molecular weight is 48,
000。
Embodiment described above is merely to illustrate technological thought and the feature of the present invention, in its object is to make this area
Technical staff will appreciate that present disclosure and implement according to this, it is impossible to only limit the patent model of the present invention with the present embodiment
Enclose, the most all equal changes made according to disclosed spirit or modification, still fall in the scope of the claims of the present invention.
Claims (8)
1. an alcohol-soluble acrylic resin, it is characterised in that described alcohol-soluble acrylic resin is by glass transition temperature
Degree hard monomer and the glass transition temperature higher than the 25 DEG C soft or hard monomer less than 25 DEG C is 50: 50～90: 10 to lead in mass ratio
Cross free radicals copolymerization reaction to form；The glass transition temperature of described alcohol-soluble acrylic resin is 25～45 DEG C, Weight-average molecular
Amount is 30,000 to 100,000；
Add initiator and molecular weight regulator during reaction, be simultaneously introduced dichloromethane and stearic acid, the consumption of described initiator
Being the 0.01～10% of monomer total amount by mass percentage, the consumption of described molecular weight regulator is single by mass percentage
The 0.01～10% of body total amount, described dichloromethane and stearic consumption are the 0.01-of monomer total amount by mass percentage
0.5%；
Described soft monomer is selected from n-BMA, acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate, propylene
At least one in acid different monooctyl ester, lauryl methacrylate, ethoxyethyl methacrylates；Described hard monomer is selected from first
Base acrylic acid methyl ester., ethyl methacrylate, isobutyl methacrylate, hydroxyethyl methylacrylate, methacrylic acid hydroxypropyl
At least one in ester, styrene.
2. alcohol-soluble acrylic resin as claimed in claim 1, it is characterised in that described soft monomer is selected from acrylic acid second
At least one in ester, n-butyl acrylate；Described hard monomer selected from methyl methacrylate, isobutyl methacrylate,
At least one in hydroxyethyl methylacrylate, styrene.
3. alcohol-soluble acrylic resin as claimed in claim 1, it is characterised in that described free radicals copolymerization reaction uses outstanding
Floating polyreaction, bulk polymerization or solution polymerization.
4. alcohol-soluble acrylic resin as claimed in claim 3, it is characterised in that used by described free radicals copolymerization reaction
Initiator selects at least one in peroxide compound and/or azo compound；
Described peroxide compound is selected from benzoyl peroxide, peroxidized t-butyl perbenzoate, cumyl peroxide, peroxide
Change lauroyl, di-isopropyl peroxydicarbonate, Isosorbide-5-Nitrae-peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, peroxy dicarbonate two hexamethylene
Ester, 1,1-di-tert-butyl peroxide-3,3,5-trimethyl-cyclohexanes, di-t-butyl peroxide, tert-butyl hydroperoxide, peroxidating
At least one in the 2 ethyl hexanoic acid tert-butyl ester；
Described azo compound is selected from azodiisobutyronitrile, AMBN, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two isopropylformic acid.
At least one in dimethyl ester, azo isobutyl cyano group Methanamide, azo dicyclohexyl formonitrile HCN, azo-bis-iso-dimethyl.
5. alcohol-soluble acrylic resin as claimed in claim 4, it is characterised in that the initiator used by copolyreaction was selected
BP, dilauroyl peroxide, Isosorbide-5-Nitrae-peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, di-isopropyl peroxydicarbonate, peroxide
Change at least one in the 2 ethyl hexanoic acid tert-butyl ester, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).
6. alcohol-soluble acrylic resin as the most described in claim 1,4,5, it is characterised in that the consumption of initiator is by quality
Percentages is the 0.05～5.0% of monomer total amount.
7. alcohol-soluble acrylic resin as claimed in claim 3, it is characterised in that the molecular weight regulator used by copolyreaction
Select at least one in lauryl mercaptan, iso-butyl mercaptan, α-methyl styrene and dimer thereof.
8. alcohol-soluble acrylic resin as claimed in claim 7, it is characterised in that the consumption of described molecular weight regulator is pressed
Mass percent is calculated as the 0.05～5.0% of monomer total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610405651.8A CN106065046A (en) | 2016-06-12 | 2016-06-12 | A kind of alcohol-soluble acrylic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610405651.8A CN106065046A (en) | 2016-06-12 | 2016-06-12 | A kind of alcohol-soluble acrylic resin |
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| Publication Number | Publication Date |
|---|---|
| CN106065046A true CN106065046A (en) | 2016-11-02 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610405651.8A Pending CN106065046A (en) | 2016-06-12 | 2016-06-12 | A kind of alcohol-soluble acrylic resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343208A (en) * | 2019-06-11 | 2019-10-18 | 中山华明泰科技股份有限公司 | A kind of powder acrylic resin preparation method and application |
| CN112354305A (en) * | 2020-10-30 | 2021-02-12 | 南京捷立德环保科技有限公司 | Spraying device for dust removal |
| CN115216251A (en) * | 2021-12-26 | 2022-10-21 | 上海路嘉胶粘剂有限公司 | Water-based sealing adhesive and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084860A (en) * | 1992-09-30 | 1994-04-06 | 施振冰 | Acrylic ester polymer and the preparation and the application of the different molecular weight of regulating with the alpha-methyl styrene dimer |
| CN102219875A (en) * | 2010-01-22 | 2011-10-19 | 北京高盟新材料股份有限公司 | Alcohol-soluble resin composition, alcohol-soluble glazing agent and preparation method thereof |
| CN104311727A (en) * | 2014-11-06 | 2015-01-28 | 任婧 | Acrylic resin for transfer ink |
-
2016
- 2016-06-12 CN CN201610405651.8A patent/CN106065046A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084860A (en) * | 1992-09-30 | 1994-04-06 | 施振冰 | Acrylic ester polymer and the preparation and the application of the different molecular weight of regulating with the alpha-methyl styrene dimer |
| CN102219875A (en) * | 2010-01-22 | 2011-10-19 | 北京高盟新材料股份有限公司 | Alcohol-soluble resin composition, alcohol-soluble glazing agent and preparation method thereof |
| CN104311727A (en) * | 2014-11-06 | 2015-01-28 | 任婧 | Acrylic resin for transfer ink |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343208A (en) * | 2019-06-11 | 2019-10-18 | 中山华明泰科技股份有限公司 | A kind of powder acrylic resin preparation method and application |
| CN112354305A (en) * | 2020-10-30 | 2021-02-12 | 南京捷立德环保科技有限公司 | Spraying device for dust removal |
| CN115216251A (en) * | 2021-12-26 | 2022-10-21 | 上海路嘉胶粘剂有限公司 | Water-based sealing adhesive and preparation method and application thereof |
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Application publication date: 20161102 |