CN105884965A - Flexible acrylic resin - Google Patents
Flexible acrylic resin Download PDFInfo
- Publication number
- CN105884965A CN105884965A CN201610405617.0A CN201610405617A CN105884965A CN 105884965 A CN105884965 A CN 105884965A CN 201610405617 A CN201610405617 A CN 201610405617A CN 105884965 A CN105884965 A CN 105884965A
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- CN
- China
- Prior art keywords
- butyl
- peroxide
- monomer
- flexible acrylic
- acrylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
-
- 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
Abstract
The invention discloses flexible acrylic resin. The flexible acrylic resin is formed by carrying out a copolymerization reaction on hard monomers with the glass-transition temperature higher than 25 DEG C and soft monomers with the glass-transition temperature lower than 25 DEG C according to the mass ratio of 15:85 to 40:60. The soft monomers are selected from at least one of n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate and ethoxyethyl methacrylate. The hard monomers are selected from at least one of methyl methacrylate, hydroxyethyl methylacrylate, isobutyl methacrylate, tert-butyl methacrylate and styrene. The glass-transition temperature of the acrylic resin ranges from 20 DEG C to 40 DEG C, the weight-average molecular weight ranges from 50,000 to 400,000, moderate adhesive force and good toughness are achieved, extremely good coating flexibility is achieved, and the requirements for the use performance of printing ink and paint can be met.
Description
Technical field
The present invention relates to polymeric material field, particularly relates to a kind of Flexible acrylic.
Background technology
Acrylic resin refers to acrylic acid and/or methacrylic acid series unsaturated compound as monomer, anti-by radical polymerization
The family macromolecule fluoropolymer resin that should prepare, has excellent mechanical performance and weatherability, is widely used in coating, ink, builds
Build, the field such as aviation.Select different monomer ratios, the acrylic resin of various different performance can be prepared.
Summary of the invention
The invention aims to provide a kind of existing moderate adhesive force to have again higher toughness, there is fabulous film flexibility simultaneously
Acrylic resin, to meet the use demand of ink and coating.
It is an object of the invention to be achieved through the following technical solutions:
A kind of Flexible acrylic, described Flexible acrylic be by the glass transition temperature hard monomer higher than 25 DEG C with
Glass transition temperature is 15: 85～40: 60 to carry out copolyreaction and form less than the soft or hard monomer of 25 DEG C in mass ratio；Described flexibility
The glass transition temperature of acrylic resin is 20～40 DEG C, and weight average molecular weight is 50,000 to 400,000.
Add initiator and molecular weight regulator during reaction, be simultaneously introduced dichloromethane and stearic acid, the flowing of resin can be improved
Property and release property, the consumption of described initiator is the 0.01～10% of monomer total amount by mass percentage, described molecular-weight adjusting
The consumption of agent is that the 0.01～10% of monomer total amount, described dichloromethane and stearic consumption are by quality hundred by mass percentage
Proportion by subtraction is calculated as the 0.01-0.5% of monomer total amount.
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
At least one in base acrylic acid methyl ester., ethyl methacrylate, Tert-butyl Methacrylate, styrene.
Above-mentioned Flexible acrylic, it is preferred that described soft monomer selected from n-BMA, acrylic acid methyl ester.,
At least one in n-butyl acrylate, ethoxyethyl methacrylates；Described hard monomer selected from methyl methacrylate,
At least one in styrene.
Above-mentioned Flexible acrylic, wherein, described copolyreaction is suspension polymerization, bulk polymerization or solution
Polyreaction.
Above-mentioned Flexible acrylic, wherein, the initiator used by copolyreaction selects peroxide compound and/or azo
At least one in compound.
Described peroxide compound selected from benzoyl peroxide, peroxidized t-butyl perbenzoate, cumyl peroxide, Isosorbide-5-Nitrae-
Peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, dilauroyl peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate,
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.
Above-mentioned Flexible acrylic, it is preferred that the initiator used by copolyreaction selects benzoyl peroxide, peroxidating ten
Two acyls, Isosorbide-5-Nitrae-peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, di-isopropyl peroxydicarbonate, the peroxidating 2 ethyl hexanoic acid tert-butyl ester, idol
At least one in nitrogen bis-isobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).
Above-mentioned Flexible acrylic, it is preferred that the consumption of described initiator be by mass percentage monomer total amount 0.05～
5.0%.
Above-mentioned Flexible acrylic, wherein, the molecular weight regulator used by copolyreaction selects lauryl mercaptan, isobutyl
At least one in base mercaptan, α-methyl styrene.
Above-mentioned Flexible acrylic, it is preferred that the consumption of described molecular weight regulator is that monomer is total by mass percentage
The 0.05～5.0% of amount.
In sum, owing to have employed technique scheme, the present invention compared with prior art, has the advantages that
The glass transition temperature of Flexible acrylic that the present invention provides is 20～40 DEG C, weight average molecular weight be 50,000 to
400,000, there is moderate adhesive force and preferable toughness, and it is flexible to have splendid film.The flexible acrylic acid tree that the present invention provides
Fat can be dissolved in nonpolar varsol, it is also possible to is dissolved in the ketone of polarity, esters, ether solvent, can use suspension polymerisation
Or polymerisation in bulk is prepared as hard resin, it is possible to use polymerisation in solution to be prepared as liquid resin, there is stronger practicality and industry
Change promotional value.
Detailed description of the invention
Below by specific embodiment, the present invention is further described in detail.
Embodiment 1
Process for suspension polymerization is used to carry out copolyreaction.
Soft monomer: n-BMA 65 mass parts, ethoxyethyl methacrylates 5 mass parts.
Hard monomer: methyl methacrylate 20 mass parts；Styrene 10 mass parts.
Initiator: using benzoyl peroxide, the complex of Isosorbide-5-Nitrae-peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, consumption is monomer total amount
0.175 mass parts.
Molecular weight regulator: using lauryl mercaptan and α-methyl styrene and the compound of dimer thereof, consumption is that monomer is total
0.25 mass parts of amount.
Dichloromethane and stearic acid: 0.08 mass parts.
After tested, resulting polymers: the glass transition temperature of acrylic resin is 30 DEG C, weight average molecular weight is 210,000.
Embodiment 2
Bulk technique is used to carry out copolyreaction.
Soft monomer: n-BMA 70 mass parts；Ethoxyethyl methacrylates 5 mass parts.
Hard monomer: methyl methacrylate 25 mass parts.
Initiator: use lauroyl peroxide, Isosorbide-5-Nitrae-peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, 1,1-di-tert-butyl peroxide-3,3,
5-trimethyl-cyclohexane, the complex of the peroxidating 2 ethyl hexanoic acid tert-butyl ester, total consumption is 0.13 mass parts of monomer total amount.
Molecular weight regulator: using lauryl mercaptan and α-methyl styrene and the compound of dimer thereof, total consumption is monomer
0.3 mass parts of total amount.
Dichloromethane and stearic acid: 0.25 mass parts.
After tested, resulting polymers: the glass transition temperature of acrylic resin is 32 DEG C, weight average molecular weight is 180,000.
Embodiment 3
Solution polymerization process is used to carry out copolyreaction.
Soft monomer: methacrylic acid positive fourth 65 mass parts；Butyl acrylate 5 mass parts.
Hard monomer: methyl methacrylate 30 mass parts.
Initiator: using azodiisobutyronitrile, consumption is 0.8 mass parts of monomer total amount.
Molecular weight regulator: using iso-butyl mercaptan, consumption is 0.2 mass parts of monomer total amount.
Dichloromethane and stearic acid: 0.15 mass parts.
Use dimethylbenzene and ethyl acetate be by volume 3: 1 mixed solvents formed as polymer solvent, make consolidating of reaction system
Content is 45%.
After tested, resulting polymers: the glass transition temperature of acrylic resin is 35 DEG C, weight average molecular weight is 230,000.
Embodiment described above is merely to illustrate technological thought and the feature of the present invention, its object is to make the technology in this area
Personnel will appreciate that present disclosure and implement according to this, it is impossible to only limit the scope of the claims of the present invention with the present embodiment, the most all
The equal change made according to disclosed spirit or modification, still fall in the scope of the claims of the present invention.
Claims (8)
1. a Flexible acrylic, it is characterised in that described Flexible acrylic 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 in mass ratio 15: 85～40: 60 carry out copolyreaction and
Become；The glass transition temperature of described Flexible acrylic is 20～40 DEG C, and weight average molecular weight is 50,000 to 400,000；
Adding initiator and molecular weight regulator during reaction, be simultaneously introduced dichloromethane and stearic acid, the consumption of described initiator is pressed
Mass percent is calculated as the 0.01～10% of monomer total amount, and the consumption of described molecular weight regulator is that monomer is total by mass percentage
The 0.01～10% of amount, described dichloromethane and stearic consumption are the 0.01-0.5% of monomer total amount by mass percentage；
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
At least one in base acrylic acid methyl ester., ethyl methacrylate, Tert-butyl Methacrylate, styrene.
2. Flexible acrylic as claimed in claim 1, it is characterised in that described soft monomer selected from n-BMA,
At least one in acrylic acid methyl ester., n-butyl acrylate, ethoxyethyl methacrylates；Described hard monomer is selected from methyl
At least one in acrylic acid methyl ester., styrene.
3. Flexible acrylic as claimed in claim 1, it is characterised in that described copolyreaction is suspension polymerization, basis
Body polyreaction or solution polymerization.
4. Flexible acrylic as claimed in claim 3, it is characterised in that the initiator used by copolyreaction selects peroxide
At least one in compound and/or azo compound；
Described peroxide compound selected from benzoyl peroxide, peroxidized t-butyl perbenzoate, cumyl peroxide, Isosorbide-5-Nitrae-
Peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, dilauroyl peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate,
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. Flexible acrylic as claimed in claim 4, it is characterised in that the initiator used by copolyreaction selects benzoyl peroxide
Formyl, dilauroyl peroxide, Isosorbide-5-Nitrae-peroxide cyclohexyl dicarboxylic acid di tert butyl carbonate, di-isopropyl peroxydicarbonate, peroxidating 2-ethyl
At least one in hecanoic acid t-butyl ester, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).
6. the Flexible acrylic as described in claim 1 or 4 or 5, it is characterised in that the consumption of described initiator presses quality hundred
Proportion by subtraction is calculated as the 0.05～5.0% of monomer total amount.
7. Flexible acrylic as claimed in claim 3, it is characterised in that the molecular weight regulator used by copolyreaction selects ten
At least one in dialkyl group mercaptan, iso-butyl mercaptan, α-methyl styrene.
8. Flexible acrylic as claimed in claim 7, it is characterised in that the consumption of described molecular weight regulator presses quality hundred
Proportion by subtraction is calculated as the 0.05～5.0% of monomer total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610405617.0A CN105884965A (en) | 2016-06-12 | 2016-06-12 | Flexible acrylic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610405617.0A CN105884965A (en) | 2016-06-12 | 2016-06-12 | Flexible acrylic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105884965A true CN105884965A (en) | 2016-08-24 |
Family
ID=56729009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610405617.0A Pending CN105884965A (en) | 2016-06-12 | 2016-06-12 | Flexible acrylic resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105884965A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543348A (en) * | 2016-11-22 | 2017-03-29 | 博立尔化工（扬州）有限公司 | A kind of acrylic resin with environment-friendlyplasticizer plasticizer with excellent compatibility |
| CN106674433A (en) * | 2016-11-25 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3d printing powder and preparation method thereof |
| CN110894256A (en) * | 2018-09-12 | 2020-03-20 | 上海昶法新材料有限公司 | Styrene derivative copolymer sizing agent and preparation method thereof |
| 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 |
|---|---|---|---|---|
| CN101903175A (en) * | 2007-12-20 | 2010-12-01 | Lg化学株式会社 | Multi-layered acrylic retardation film and fabrication method thereof |
| CN101990645A (en) * | 2008-01-23 | 2011-03-23 | Lg化学株式会社 | Retardation film, fabrication method thereof, and liquid crystal display comprising the same |
| CN103204969A (en) * | 2013-02-04 | 2013-07-17 | 海洋化工研究院有限公司 | Low-abrasion antifouling resin and transparent luminescent antifouling coating composition containing resin |
-
2016
- 2016-06-12 CN CN201610405617.0A patent/CN105884965A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101903175A (en) * | 2007-12-20 | 2010-12-01 | Lg化学株式会社 | Multi-layered acrylic retardation film and fabrication method thereof |
| CN101990645A (en) * | 2008-01-23 | 2011-03-23 | Lg化学株式会社 | Retardation film, fabrication method thereof, and liquid crystal display comprising the same |
| CN103204969A (en) * | 2013-02-04 | 2013-07-17 | 海洋化工研究院有限公司 | Low-abrasion antifouling resin and transparent luminescent antifouling coating composition containing resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543348A (en) * | 2016-11-22 | 2017-03-29 | 博立尔化工（扬州）有限公司 | A kind of acrylic resin with environment-friendlyplasticizer plasticizer with excellent compatibility |
| CN106674433A (en) * | 2016-11-25 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3d printing powder and preparation method thereof |
| CN110894256A (en) * | 2018-09-12 | 2020-03-20 | 上海昶法新材料有限公司 | Styrene derivative copolymer sizing agent and preparation method thereof |
| CN110894256B (en) * | 2018-09-12 | 2022-03-18 | 上海昶法新材料有限公司 | Styrene derivative copolymer sizing agent and preparation method thereof |
| 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: 20160824 |