CN114507313A - Emulsion polymerization pressure-sensitive adhesive with ultralow emulsifier dosage and high water resistance and weather resistance and preparation method thereof - Google Patents
Emulsion polymerization pressure-sensitive adhesive with ultralow emulsifier dosage and high water resistance and weather resistance and preparation method thereof Download PDFInfo
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- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
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- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C—CHEMISTRY; METALLURGY
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- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
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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
- 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
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- 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
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- 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
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
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- 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
- C09J133/24—Homopolymers or copolymers of amides or imides
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- 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
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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Abstract
The invention discloses a high-water-resistant weather-resistant emulsion polymerization pressure-sensitive adhesive with ultralow emulsifier dosage, wherein emulsion polymerization is carried out in emulsion prepared from unsaturated monomers and water under the action of an emulsifier, a system of the pressure-sensitive adhesive mainly comprises four major components of the unsaturated monomers, the water, the emulsifier and a water-soluble initiator, and the unsaturated monomers comprise but are not limited to: one or more of acrylic acid, methacrylic acid, methyl methacrylate, styrene, vinyl acetate, butyl acrylate, isooctyl acrylate, acrylamide, and N-methyl acrylamide. The invention uses macromolecule obtained by emulsion polymerization, so the molecular weight is much higher than that of the oily solution polymerization method, and the performance is more excellent; in addition, because the ultra-low emulsifier emulsion polymerization which is almost soap-free polymerization is used, the obtained high molecular substance is comparable to oily high molecular substance in water resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-water-resistant weather-resistant emulsion polymerization pressure-sensitive adhesive with ultralow emulsifier dosage and a preparation method thereof.
Background
At present, pressure-sensitive adhesives used outdoors and in some humid environments are generally high-viscosity, high-strength and high-water-resistance oily pressure-sensitive adhesives, such as outdoor advertising posters, automobile coat film stickers, household bathroom hook stickers and the like.
The existing oily pressure-sensitive adhesive uses an organic solvent as a polymerization medium, is not environment-friendly, unsafe and uneconomical, and has high polymer performance, solution free radical polymerization, polymerization degree molecular weight which is not easy to be large, and certain performance aspects which are also deficient.
Therefore, the emulsion polymerization pressure-sensitive adhesive with ultralow emulsifier dosage and high water resistance and weather resistance and the preparation method thereof are provided for solving the problems.
Disclosure of Invention
The invention aims to provide an emulsion polymerization pressure-sensitive adhesive with ultralow emulsifier dosage and high water resistance and weather resistance and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the pressure-sensitive adhesive is prepared by polymerizing unsaturated monomers and water in emulsion prepared by the action of an emulsifier, wherein the system mainly comprises the four components of the unsaturated monomers, the water, the emulsifier and a water-soluble initiator;
the unsaturated monomers include, but are not limited to: one or more of acrylic acid, methacrylic acid, methyl methacrylate, styrene, vinyl acetate, butyl acrylate, isooctyl acrylate, acrylamide, and N-methyl acrylamide.
A process for preparing the ultra-low-dosage high-water-resistance weather-resistant pressure-sensitive emulsion polymerization adhesive includes such steps as preparing raw materials, heating for dissolving, synthesizing, cooling, regulating, detecting, filtering and packing. The production process takes about 8-10 h.
In a further embodiment, the a. stock: the liquid raw materials are automatically weighed and fed, and the solid raw materials are manually fed. The method comprises three parts: firstly, pumping monomer vinyl acetate, butyl acrylate, isooctyl acrylate and other monomer materials into a pre-emulsification kettle, starting stirring for pre-emulsification to obtain pre-emulsion, secondly, adding an initiator and process water into the initiator kettle, uniformly stirring, thirdly, adding an emulsifier, process water and the like into a polymerization kettle, and uniformly stirring.
In a further embodiment, the b. Heating the polymerization kettle to 80-86 ℃, preserving heat for 10-30 minutes, and stirring and mixing uniformly.
In a further embodiment, the c. synthesis reaction: and dropwise adding a small amount of pre-emulsion into a polymerization kettle from a pre-emulsion kettle, continuously heating, adding a priming initiator when the temperature is raised to 78-84 ℃, and carrying out a priming reaction. After the bottoming reaction is finished, the pre-emulsion is dripped to carry out synthetic reaction, the temperature is controlled to be 80-86 ℃, the time is about 4-6 hours, and cooling water is added into a jacket of a reaction kettle to control the reaction temperature to be 80-86 ℃ along with the reaction.
In a further embodiment, the d. After the polymerization reaction is finished, the temperature in the kettle is reduced to below 50 ℃ through the heat preservation process and the cooling, and the post-treatment agent is added for adjustment.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses macromolecule obtained by emulsion polymerization, so the molecular weight is much higher than that of the oily solution polymerization method, and the performance is more excellent; in addition, because the ultra-low emulsifier emulsion polymerization which is almost soap-free polymerization is used, the obtained high molecular substance is comparable to oily high molecular substance in water resistance. Therefore, the emulsion polymerization pressure-sensitive adhesive with the ultra-low emulsifier has the advantages of both the oil-based pressure-sensitive adhesive and the water-based pressure-sensitive adhesive: the water-based emulsion polymerization pressure-sensitive adhesive with ultralow emulsifier content and performance comparable to or superior to that of oily pressure-sensitive adhesive is obtained by a simple and environment-friendly method.
Drawings
FIG. 1 is a schematic diagram of a specific reaction equation of an emulsion polymerization pressure-sensitive adhesive with high water resistance and weather resistance and ultra-low emulsifier usage;
FIG. 2 is a process flow diagram of an emulsion polymerization pressure-sensitive adhesive with ultra-low emulsifier dosage and high water resistance and weather resistance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An ultra-low emulsifier high water-resistant weather-resistant emulsion polymerization pressure-sensitive adhesive, wherein the emulsion polymerization is carried out in emulsion prepared from unsaturated monomer and water under the action of emulsifier, the system mainly comprises four major components of unsaturated monomer, water, emulsifier and water-soluble initiator,
the unsaturated monomers include, but are not limited to: one or more of acrylic acid, methacrylic acid, methyl methacrylate, styrene, vinyl acetate, butyl acrylate, isooctyl acrylate, acrylamide, and N-methyl acrylamide.
The specific reaction scheme is schematically shown in FIG. 1 (the four unsaturated monomers are only schematic to include the above-mentioned plural species).
The technological process is a semi-continuous process and comprises the steps of material preparation, heating dissolution, synthesis reaction, cooling, adjustment, detection, filtration, packaging and the like. The production process needs 8-10 h.
The specific process operation steps are as follows:
A. preparing materials: the liquid raw materials are automatically weighed and fed, and the solid raw materials are manually fed. The method comprises three parts: firstly, pumping monomer vinyl acetate, butyl acrylate, isooctyl acrylate and other monomer materials into a pre-emulsification kettle, starting stirring for pre-emulsification to obtain pre-emulsion, secondly, adding an initiator and process water into the initiator kettle, uniformly stirring, thirdly, adding an emulsifier, the process water and the like into a polymerization kettle, and uniformly stirring;
B. heating for dissolving: heating the polymerization kettle to 80-86 ℃, preserving heat for 10-30 minutes, and stirring and mixing uniformly;
C. and (3) synthesis reaction: and dropwise adding a small amount of pre-emulsion into a polymerization kettle from a pre-emulsion kettle, continuously heating, adding a priming initiator when the temperature is raised to 78-84 ℃, and carrying out a priming reaction. After the bottoming reaction is finished, starting to dropwise add the pre-emulsion to perform a synthesis reaction, controlling the temperature to be 80-86 ℃, wherein the time is about 4-6 hours, and adding cooling water into a reaction kettle jacket to control the reaction temperature to be 80-86 ℃ along with the reaction;
D. and (3) cooling: after the polymerization reaction is finished, the temperature in the kettle is reduced to below 50 ℃ through the heat preservation process and the cooling, and post-treatment agents and the like are added for adjustment;
E. packaging and discharging: after the adjustment, the product is qualified by inspection, filtered, packaged and discharged.
The process flow is shown in FIG. 2 (which is a 50L pilot plant for emulsion polymerization).
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. An emulsion polymerization pressure-sensitive adhesive with ultralow emulsifier dosage and high water resistance and weather resistance is characterized in that: the emulsion polymerization is carried out in an emulsion prepared from unsaturated monomers and water under the action of an emulsifier, and the system mainly comprises the unsaturated monomers, the water, the emulsifier and a water-soluble initiator; the unsaturated monomers include, but are not limited to: one or more of acrylic acid, methacrylic acid, methyl methacrylate, styrene, vinyl acetate, butyl acrylate, isooctyl acrylate, acrylamide, and N-methyl acrylamide.
2. The preparation method of the emulsion polymerization pressure-sensitive adhesive with the ultra-low emulsifier dosage and the high water resistance and the weather resistance as claimed in claim 1, is characterized in that: comprises the processes of material preparation, heating dissolution, synthesis reaction, cooling, adjustment, detection, filtration, packaging and the like; the production process takes about 8-10 h.
3. The preparation method of the emulsion polymerization pressure-sensitive adhesive with ultra-low emulsifier dosage and high water resistance and weather resistance as claimed in claim 2, characterized in that: in the above-mentioned manner,
A. preparing materials: automatically weighing and feeding liquid raw materials, and manually feeding solid raw materials;
the method comprises three parts: firstly, pumping monomer vinyl acetate, butyl acrylate, isooctyl acrylate and other monomer materials into a pre-emulsification kettle, starting stirring for pre-emulsification to obtain pre-emulsion, secondly, adding an initiator and process water into the initiator kettle, uniformly stirring, thirdly, adding an emulsifier, process water and the like into a polymerization kettle, and uniformly stirring.
4. The preparation method of the emulsion polymerization pressure-sensitive adhesive with the ultra-low emulsifier dosage and the high water resistance and the weather resistance as claimed in claim 2, is characterized in that: in the above-mentioned manner,
B. heating for dissolving: heating the polymerization kettle to 80-86 ℃, preserving heat for 10-30 minutes, and stirring and mixing uniformly.
5. The preparation method of the emulsion polymerization pressure-sensitive adhesive with the ultra-low emulsifier dosage and the high water resistance and the weather resistance as claimed in claim 2, is characterized in that: in the above-mentioned manner,
C. and (3) synthesis reaction: dropwise adding a small amount of pre-emulsion into a polymerization kettle from a pre-emulsion kettle, continuously heating, adding a priming initiator when the temperature is raised to 78-84 ℃, and carrying out a priming reaction; after the bottoming reaction is finished, the pre-emulsion is dripped to carry out synthetic reaction, the temperature is controlled to be 80-86 ℃, the time is about 4-6 hours, and cooling water is added into a jacket of a reaction kettle to control the reaction temperature to be 80-86 ℃ along with the reaction.
6. The preparation method of the emulsion polymerization pressure-sensitive adhesive with the ultra-low emulsifier dosage and the high water resistance and the weather resistance as claimed in claim 2, is characterized in that: in the above-mentioned manner,
D. and (3) cooling: after the polymerization reaction is finished, the temperature in the kettle is reduced to below 50 ℃ through the heat preservation process and cooling, and a post-treatment agent and the like are added for adjustment.
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CN103320065A (en) * | 2013-06-17 | 2013-09-25 | 昆山韩保胶带科技有限公司 | Emulsion pressure-sensitive adhesive for protecting adhesive tape and preparation method thereof |
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CN103320065A (en) * | 2013-06-17 | 2013-09-25 | 昆山韩保胶带科技有限公司 | Emulsion pressure-sensitive adhesive for protecting adhesive tape and preparation method thereof |
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