CN106497462A - A kind of emulsifier-free water soluble acrylic acid ester pressure-sensitive and preparation method thereof - Google Patents
A kind of emulsifier-free water soluble acrylic acid ester pressure-sensitive and preparation method thereof Download PDFInfo
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- CN106497462A CN106497462A CN201610899378.9A CN201610899378A CN106497462A CN 106497462 A CN106497462 A CN 106497462A CN 201610899378 A CN201610899378 A CN 201610899378A CN 106497462 A CN106497462 A CN 106497462A
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- Prior art keywords
- acrylic acid
- emulsifier
- water soluble
- free water
- acid ester
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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 a kind of emulsifier-free water soluble acrylic acid ester pressure-sensitive, the pressure sensitive adhesive does not contain emulsifying agent, is added to react in solvent by monomer and obtains, and monomer is by constituting including following raw material：5～40wt% of polar monomer, 60～95wt% of conventional monomeric, solvent are alcohols.The pressure sensitive adhesive is alternately distributed in acrylate long-chain-segment by hydrophilic radical, and molecule chain end hydroxyl or carboxyl isopolarity group, and the acrylate polymer of preparation can occur self assembly in water, form the vesicle of Nano grade.The acrylate pressure-sensitive adhesive does not contain poisonous or contaminative solvent, though water-soluble pressuree-sentitive adhesive is without emulsifying agent, avoid small-molecular emulsifier during use causes the problem of pressure sensitive adhesive characteristic mutation to interfacial migration.
Description
Technical field
The present invention relates to pressure sensitive adhesive technical field, especially a kind of water soluble acrylic acid ester pressure-sensitive without emulsifying agent and its
Technology of preparing.
Background technology
Acrylate pressure-sensitive adhesive is with low cost with which, prepares simply, and excellent performance is applied widely.Current at present
Acrylate pressure-sensitive adhesive preparation method is divided into solvent method and emulsion method, and acrylate pressure-sensitive adhesive prepared by solvent method is using process
The middle gas that is substantial amounts of poisonous or having pollution to air that can volatilize, although there is no VOC emission in emulsion-type pressure-sensitive,
It is that small-molecular emulsifier can be to interface migration so as to affecting the life-time service stability of pressure sensitive adhesive in use for pressure sensitive adhesive.
Content of the invention
First purpose of the present invention is that oiliness pressure sensitive adhesive has VOC emission in order to solve during acrylate pressure-sensitive adhesive use
Contaminated air, emulsion-type pressure-sensitive small-molecular emulsifier can be to interface migrations so as to affecting the life-time service stability of pressure sensitive adhesive
Problem, there is provided water soluble acrylic acid ester pressure-sensitive of a kind of emulsifier-free and preparation method thereof.
Second object of the present invention is to provide a kind of preparation method of above-mentioned pressure sensitive adhesive.
The purpose of the present invention is by the following technical programs implementing：
A kind of emulsifier-free water soluble acrylic acid ester pressure-sensitive, without emulsifying agent, is obtained by reacting in monomer addition solvent, the list
Body is by constituting including following raw material：
5～40wt% of polar monomer,
60～95wt% of conventional monomeric,
The solvent is alcohols.
Further, the alcohols solvent includes methanol, ethanol, butanol.
Further, the polar monomer includes 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, acrylic acid, methyl-prop
Olefin(e) acid, Hydroxypropyl acrylate, Hydroxypropyl methacrylate.
Further, the conventional monomeric includes butyl acrylate, acrylic acid isooctyl, ethyl acrylate, acrylic acid first
Ester, methyl methacrylate, styrene, ethyl methacrylate.
The preparation method of above-mentioned emulsifier-free water soluble acrylic acid ester pressure-sensitive, comprises the steps：
（1）Solvent, conventional monomeric are added reactor, initiator, reaction after intensification, is added；
（2）To step（1）Deca polar monomer and initiator in the solution for obtaining, reaction；
（3）To step（2）Deca conventional monomeric and initiator in the solution for obtaining, reaction；
（4）To step（3）Deca polar monomer and initiator in the solution for obtaining, reaction.
Further, the step（4）Also include the step of distilling out solvent in reactor afterwards.
Further, step（1）And step（3）Middle conventional monomeric addition weight ratio is 1:1, step（2）And step（4）
Middle polar monomer addition weight ratio is 1:1；Step（1）, step（2）, step（3）And step（4）Middle initiator addition weight
Amount is than being 1:1:1:1.
Further, the solvent accounts for the 25%～100% of total monomer weight, and the initiator includes azodiisobutyronitrile
AIBN, dibenzoyl peroxide BPO, initiator account for the 0.1%～1% of total monomer weight.
Further, step（1）Initiator is added after being warming up to 60～80 DEG C, and the response time is 2～4h；Step（2）~
（4）Time for adding be 2～4h, the response time is 2～4h.
Beneficial effects of the present invention are：
1st, during use without or with a small amount of alcohols solvent, do not result in air pollution；
2nd, emulsifying agent is not contained, and pressure sensitive adhesive avoids small-molecular emulsifier in use can be to interface migration so as to affecting to press
The problem of the life-time service stability of quick glue；
3rd, pressure sensitive adhesive can carry out the imitated vesicle structure that self assembly obtains Nano grade in water, with excellent initial cohesiveness and late
Viscosity energy.
Description of the drawings
Fig. 1 carries out self assembly in water for a kind of emulsifier-free water soluble acrylic acid ester pressure-sensitive that the embodiment of the present invention is provided
Form the schematic diagram of imitated vesicle structure.
Specific embodiment
Hereinafter the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Raw material used by the present invention is market and can obtain product.
Embodiment 1
25g ethanol is weighed, 30g butyl acrylate adds reactor, is warming up to 78 DEG C, adds 0.1gAIBN, reacts 3h.Deca
20g 2-(Acryloyloxy)ethanols and 0.1gAIBN, time for adding 3h react 2h.Deca 30g butyl acrylate and 0.1gAIBN, Deca
Time 3h, reacts 2h.Deca 20g 2-(Acryloyloxy)ethanol and 0.1gAIBN, time for adding 3h react 2h.Vacuum distillation is gone out molten
Agent ethanol, obtains acrylate pressure sensitive adhesive.
Embodiment 2
40g ethanol is weighed, 30g butyl acrylate adds reactor, is warming up to 78 DEG C, adds 0.1gAIBN, reacts 3h.Deca
20g acrylic acid and 0.1gAIBN, time for adding 3h react 2h.Deca 30g butyl acrylate and 0.1gAIBN, time for adding 3h,
Reaction 2h.Deca 20g acrylic acid and 0.1gAIBN, time for adding 3h react 2h.Vacuum distillation is gone out etoh solvent, obtains propylene
Sour pressure sensitive adhesive.
Embodiment 3
60g ethanol is weighed, 40g butyl acrylate adds reactor, is warming up to 78 DEG C, adds 0.1gAIBN, reacts 3h.Deca
10g acrylic acid and 0.1gAIBN, time for adding 3h react 2h.Deca 40g butyl acrylate and 0.1gAIBN, time for adding 3h,
Reaction 2h.Deca 10g acrylic acid and 0.1gAIBN, time for adding 3h react 2h.Vacuum distillation is gone out etoh solvent, obtains propylene
Sour pressure sensitive adhesive.
Embodiment 4
25g methanol is weighed, 30g butyl acrylate adds reactor, is warming up to 65 DEG C, adds 0.1gAIBN, reacts 3h.Deca
20g 2-(Acryloyloxy)ethanols and 0.1gAIBN, time for adding 3h react 2h.Deca 30g butyl acrylate and 0.1gAIBN, Deca
Time 3h, reacts 2h.Deca 20g 2-(Acryloyloxy)ethanol and 0.1gAIBN, time for adding 3h react 2h.Vacuum distillation is gone out molten
Agent methanol, obtains acrylate pressure sensitive adhesive.
Embodiment 5
40g methanol is weighed, 30g butyl acrylate adds reactor, is warming up to 65 DEG C, adds 0.1gAIBN, reacts 3h.Deca
20g acrylic acid and 0.1gAIBN, time for adding 3h react 2h.Deca 30g butyl acrylate and 0.1gAIBN, time for adding 3h,
Reaction 2h.Deca 20g acrylic acid and 0.1gAIBN, time for adding 3h react 2h.Vacuum distillation is gone out solvent methanol, obtains propylene
Sour pressure sensitive adhesive.
Embodiment 6
60g methanol is weighed, 40g butyl acrylate adds reactor, is warming up to 65 DEG C, adds 0.1gAIBN, reacts 3h.Deca
10g acrylic acid and 0.1gAIBN, time for adding 3h react 2h.Deca 40g butyl acrylate and 0.1gAIBN, time for adding 3h,
Reaction 2h.Deca 10g acrylic acid and 0.1gAIBN, time for adding 3h react 2h.Vacuum distillation is gone out solvent methanol, obtains propylene
Sour pressure sensitive adhesive.
Embodiment 7
80g ethanol is weighed, 45g butyl acrylate adds reactor, is warming up to 62 DEG C, adds 0.2gAIBN, reacts 3h.Deca 5g
2-(Acryloyloxy)ethanol and 0.2gAIBN, time for adding 3h react 2h.Deca 45g butyl acrylate and 0.2gAIBN, time for adding
3h, reacts 2h.Deca 5g 2-(Acryloyloxy)ethanol and 0.2gAIBN, time for adding 3h react 2h.Vacuum distillation is gone out solvent second
Alcohol, obtains acrylate pressure sensitive adhesive.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, although with reference to aforementioned reality
Apply example to be described in detail the present invention, for a person skilled in the art, which still can be to aforementioned each enforcement
Technical scheme described in example is modified, or carries out equivalent to which part technical characteristic.All essences in the present invention
Within god and principle, any modification, equivalent substitution and improvements that is made etc. should be included within the scope of the present invention.
Claims (9)
1. a kind of emulsifier-free water soluble acrylic acid ester pressure-sensitive, it is characterised in that the pressure sensitive adhesive does not contain emulsifying agent, by monomer plus
Enter in solvent reaction to obtain, the monomer is by constituting including following raw material：
5～40wt% of polar monomer,
60～95wt% of conventional monomeric,
The solvent is alcohols.
2. emulsifier-free water soluble acrylic acid ester pressure-sensitive according to claim 1, it is characterised in that the alcohols solvent bag
Include methanol, ethanol, butanol.
3. emulsifier-free water soluble acrylic acid ester pressure-sensitive according to claim 1, it is characterised in that the polar monomer bag
Include 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, acrylic acid, methacrylic acid, Hydroxypropyl acrylate, methacrylic acid hydroxypropyl
Ester.
4. emulsifier-free water soluble acrylic acid ester pressure-sensitive according to claim 1, it is characterised in that the conventional monomeric bag
Include butyl acrylate, acrylic acid isooctyl, ethyl acrylate, acrylic acid methyl ester., methyl methacrylate, styrene, methyl-prop
Olefin(e) acid ethyl ester.
5. the preparation method of the emulsifier-free water soluble acrylic acid ester pressure-sensitive described in any one of claim 1-4, it is characterised in that
Comprise the steps：
（1）Solvent, conventional monomeric are added reactor, initiator, reaction after intensification, is added；
（2）To step（1）Deca polar monomer and initiator in the solution for obtaining, reaction；
（3）To step（2）Deca conventional monomeric and initiator in the solution for obtaining, reaction；
（4）To step（3）Deca polar monomer and initiator in the solution for obtaining, reaction.
6. the preparation method of emulsifier-free water soluble acrylic acid ester pressure-sensitive according to claim 5, it is characterised in that described
Step（4）Also include the step of distilling out solvent in reactor afterwards.
7. the preparation method of emulsifier-free water soluble acrylic acid ester pressure-sensitive according to claim 5, it is characterised in that step
（1）And step（3）Middle conventional monomeric addition weight ratio is 1:1, step（2）And step（4）Middle polar monomer addition weight
Than for 1:1；Step（1）, step（2）, step（3）And step（4）Middle initiator addition weight ratio is 1:1:1:1.
8. the preparation method of emulsifier-free water soluble acrylic acid ester pressure-sensitive according to claim 5, it is characterised in that described
Solvent accounts for the 25%～100% of total monomer weight, and the initiator includes azodiisobutyronitrile, dibenzoyl peroxide, initiator
Account for the 0.1%～1% of total monomer weight.
9. the preparation method of emulsifier-free water soluble acrylic acid ester pressure-sensitive according to claim 5, it is characterised in that step
（1）Initiator is added after being warming up to 60～80 DEG C, and the response time is 2～4h；Step（2）~（4）Time for adding be 2～
4h, response time are 2～4h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610899378.9A CN106497462B (en) | 2016-10-17 | 2016-10-17 | A kind of emulsifier-free water soluble acrylic acid ester pressure-sensitive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610899378.9A CN106497462B (en) | 2016-10-17 | 2016-10-17 | A kind of emulsifier-free water soluble acrylic acid ester pressure-sensitive and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106497462A true CN106497462A (en) | 2017-03-15 |
| CN106497462B CN106497462B (en) | 2018-09-07 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775942A (en) * | 2012-08-06 | 2012-11-14 | 滁州云林数码影像耗材有限公司 | Fluoroacrylate pressure sensitive adhesive, and preparation method thereof |
| CN103788902A (en) * | 2014-02-26 | 2014-05-14 | 钱锡平 | Alcohol-soluble compound adhesion agent and preparation method thereof |
| CN105218739A (en) * | 2015-10-28 | 2016-01-06 | 哈尔滨理工大学 | The preparation method of erasable type acrylate pressure-sensitive adhesive |
-
2016
- 2016-10-17 CN CN201610899378.9A patent/CN106497462B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775942A (en) * | 2012-08-06 | 2012-11-14 | 滁州云林数码影像耗材有限公司 | Fluoroacrylate pressure sensitive adhesive, and preparation method thereof |
| CN103788902A (en) * | 2014-02-26 | 2014-05-14 | 钱锡平 | Alcohol-soluble compound adhesion agent and preparation method thereof |
| CN105218739A (en) * | 2015-10-28 | 2016-01-06 | 哈尔滨理工大学 | The preparation method of erasable type acrylate pressure-sensitive adhesive |
Non-Patent Citations (1)
| Title |
|---|
| 王金山等: "高性能醇溶性复膜胶的研制", 《青岛科技大学学报》 * |
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| CN106497462B (en) | 2018-09-07 |
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Effective date of registration: 20201231 Address after: 224199 Industrial Park, Liuzhuang Town, Dafeng District, Yancheng City, Jiangsu Province Patentee after: JIANGSU YUANYUAN SHANFU DIGITAL PRINTING TECHNOLOGY Co.,Ltd. Address before: 214000 63 East Ring Road, Yuqi street, Huishan District, Wuxi, Jiangsu Patentee before: HARBIN INSTITUTE OF TECHNOLOGY WUXI Research Institute OF NEW MATERIALS Patentee before: WUXI HAITE NEW MATERIAL INSTITUTE Co.,Ltd. |