CN109517102B - Vinyl acetate-acrylate-ethylene multi-component copolymer emulsion and preparation method thereof - Google Patents
Vinyl acetate-acrylate-ethylene multi-component copolymer emulsion and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- 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
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Abstract
The invention relates to the field of emulsion polymerization, and discloses a vinyl acetate-acrylate-ethylene multi-component copolymer emulsion and a preparation method thereof, wherein the method comprises the following steps: under the condition of emulsion polymerization, (1) in the presence of an oxidation-reduction initiation system, carrying out a first polymerization reaction on part of mixed monomers containing a vinyl acetate monomer and an acrylate monomer and a vinyl monomer, wherein in the oxidation-reduction initiation system, an oxidizing agent is tert-butyl hydroperoxide, and a reducing agent is zinc sulfoxylate formaldehyde and/or sodium formaldehyde sulfoxylate; (2) adding an ethylene monomer and the rest of the mixed monomer into the system after the first polymerization reaction to perform a second polymerization reaction; wherein, in the second polymerization reaction, tert-butyl peroxybenzoate is added into the reaction system. The content of the acrylate in the copolymer emulsion obtained by the method is obviously higher than that of the acrylate in the common modified VAE in the prior art, and the copolymer emulsion has good bonding strength.
Description
Technical Field
The invention relates to the field of emulsion polymerization, in particular to a method for preparing vinyl acetate-acrylate-ethylene multi-component copolymer emulsion and the vinyl acetate-acrylate-ethylene multi-component copolymer emulsion prepared by the method.
Background
The vinyl acetate-ethylene copolymer (VAE) emulsion adhesive has wide bonding range and good water resistance, and compared with a solvent adhesive, the water-based adhesive is more environment-friendly, and the proportion of the water-based adhesive in the adhesive is increased year by year.
The traditional VAE emulsion has higher glass transition temperature, insufficient low-temperature flexibility and insufficient adhesive force on non-polar materials such as Polyethylene (PE) films, polypropylene (PP) films and the like; the pressure-sensitive acrylate emulsion has good adhesion to non-polar materials, but tends to have low cohesion and low adhesion strength.
U.S. air products company application U.S. patent application No. US5872181A discloses the use of vinyl acetate, ethylene and a small amount of acrylic acid monomer for copolymerization to produce a high ethylene content, low glass transition temperature modified VAE emulsion for the bonding of difficult-to-bond surfaces. And discloses that the obtained copolymer has a vinyl acetate content of 50 to 80% by weight, an ethylene content of 15 to 45% by weight, and an acrylic acid content of 0 to 30% by weight. However, the preparation process disclosed in this prior art requires high reaction pressures and long reaction times.
The re-dispersible latex powder produced by Iretay corporation of America ELOTEX FLOWKIT51 and the like is rubber powder made of polymers based on vinyl acetate, ethylene, methyl methacrylate and the like, and is suitable for cement-based systems, such as self-leveling floor materials. The glass transition temperature is high and the affinity for non-polar materials is insufficient.
In the production of VAE emulsion, by introducing acrylate soft monomer with low glass transition temperature for copolymerization modification, the multi-component copolymerization VAE emulsion with good adhesion to non-polar materials can be obtained only by maintaining excellent adhesion performance and mechanical strength of VAE, obtaining good low-temperature flexibility and improving elongation. However, since reactivity ratios of acrylate monomers to vinyl acetate and ethylene are greatly different, it is difficult to emulsion-polymerize ethylene and vinyl acetate with high efficiency by using a high proportion of acrylate monomers.
Disclosure of Invention
The invention aims to overcome the defect that the multi-component copolymerization VAE emulsion obtained in the prior art has poor bonding effect on non-polar materials, and provides a novel preparation method of vinyl acetate-acrylate-ethylene multi-component copolymer emulsion with high bonding strength.
The inventors of the present invention found in their studies that in the preparation of a vinyl acetate-acrylate-ethylene multi-copolymer emulsion, by adding t-butyl hydroperoxide as an oxidizing agent and zinc sulfoxylate formaldehyde and/or sodium formaldehyde sulfoxylate as a reducing agent in a prepolymerization process (first polymerization reaction); and when tert-butyl peroxybenzoate is added in the subsequent polymerization process (second polymerization reaction), the conversion rate of the monomer can be obviously improved, and the vinyl acetate-acrylate-ethylene multi-component copolymer emulsion with good bonding effect on non-polar materials can be obtained. Accordingly, the inventors have completed the technical solution of the present invention.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a vinyl acetate-acrylate-ethylene multi-copolymer emulsion, the method comprising: under the condition of emulsion polymerization reaction,
(1) in the presence of an oxidation-reduction initiation system, carrying out a first polymerization reaction on part of mixed monomers containing a vinyl acetate monomer and an acrylate monomer and a vinyl monomer, wherein in the oxidation-reduction initiation system, an oxidant is tert-butyl hydroperoxide, and a reducing agent is zinc sulfoxylate formaldehyde and/or sodium formaldehyde sulfoxylate;
(2) adding an ethylene monomer and the rest of the mixed monomer into the system after the first polymerization reaction to perform a second polymerization reaction;
wherein, in the second polymerization reaction, tert-butyl peroxybenzoate is added into the reaction system.
In a second aspect, the present invention provides a vinyl acetate-acrylate-ethylene multi-component copolymer emulsion prepared by the method of the first aspect.
Compared with common modified VAE and acrylate emulsion, the adhesion of the vinyl acetate-acrylate-ethylene multi-component copolymer emulsion to non-polar packaging materials such as BOPP and PET (polyethylene terephthalate) is obviously improved; specifically, the bonding strength of the vinyl acetate-acrylate-ethylene multi-component copolymer emulsion provided by the invention to BOPP is more than 20N/25 mm; preferably, the bonding strength of the vinyl acetate-acrylate-ethylene multi-component copolymer emulsion provided by the invention to BOPP is more than 40N/25 mm.
In addition, the content of the acrylic ester in the vinyl acetate-acrylic ester-ethylene multi-component copolymer emulsion obtained by the method is obviously higher than that of the acrylic ester in the common modified VAE in the prior art, so that the copolymer emulsion has good bonding strength.
The preparation method of the invention can reduce the residual amount of the monomer in the emulsion polymerization reaction.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously described, a first aspect of the present invention provides a method for preparing a vinyl acetate-acrylate-ethylene multi-copolymer emulsion, the method comprising: under the condition of emulsion polymerization reaction,
(1) in the presence of an oxidation-reduction initiation system, carrying out a first polymerization reaction on part of mixed monomers containing vinyl acetate monomers and acrylate monomers and vinyl monomers, wherein in the oxidation-reduction initiation system, an oxidant is tert-butyl hydroperoxide (TBHP), and a reducing agent is zinc sulfoxylate formaldehyde (rongalite, ZFS) and/or sodium formaldehyde sulfoxylate (rongalite);
(2) adding an ethylene monomer and the rest of the mixed monomer into the system after the first polymerization reaction to perform a second polymerization reaction;
wherein, in the second polymerization reaction, tert-butyl peroxybenzoate is added into the reaction system.
According to the method for preparing the vinyl acetate-acrylate-ethylene multi-component copolymer emulsion, the single-kettle conversion rate of the monomer can be improved by introducing the specific redox initiator in the emulsion polymerization process, and the performance of the obtained copolymer emulsion product is excellent. In addition, the specific initiation system provided by the invention has high production efficiency.
According to a preferred embodiment, the amount of the vinyl acetate monomer is 40 to 70 wt%, the amount of the acrylate monomer is 25 to 35 wt%, and the amount of the ethylene monomer is 5 to 30 wt% in the emulsion polymerization, based on the total amount of the vinyl acetate monomer, the acrylate monomer, and the ethylene monomer.
According to another more preferred embodiment, the vinyl acetate monomer is used in an amount of 50 to 55 wt%, the acrylate monomer is used in an amount of 30 to 35 wt%, and the ethylene monomer is used in an amount of 14 to 15 wt% in the emulsion polymerization, based on the total amount of the vinyl acetate monomer, the acrylate monomer, and the ethylene monomer.
Preferably, in the first polymerization reaction, the amount of the reducing agent is 0.2 to 0.6 wt%, and the amount of the oxidizing agent is 0.02 to 0.2 wt%, based on the total amount of the vinyl acetate monomer, the acrylate monomer, and the ethylene monomer. The inventor of the present invention has found that when the amount of the reducing agent is controlled within the range of 0.2 to 0.6 wt%, the deterioration of the copolymer emulsion obtained can be significantly prevented, and the strength, water resistance and other properties of the film obtained from the copolymer emulsion can be made superior. And when the dosage of the oxidant is controlled within the range of 0.02-0.2 wt%, the emulsion viscosity and the bonding strength of the obtained polymer emulsion are obviously better.
Preferably, the tert-butyl peroxybenzoate is used in the second polymerization reaction in an amount of 0.01 to 0.2 wt% based on the total amount of the vinyl acetate monomer, the acrylate monomer, and the ethylene monomer. Similarly, when the dosage of the tert-butyl peroxybenzoate is controlled within the range of 0.01-0.2 wt%, the emulsion viscosity and the bonding strength of the obtained polymer emulsion are obviously better.
Additives such as a pH buffer, for example, sodium bicarbonate, sodium acetate (trihydrate) may also be added to the emulsion polymerization reaction of the present invention. Preferably, the pH buffer is used in an amount of 0.2 to 0.6 wt% based on the total amount of the vinyl acetate monomer, the acrylate monomer, and the vinyl monomer.
According to a preferred embodiment, the emulsion polymerization is carried out in the presence of a nonionic emulsifier which is a mixture of at least one substance selected from the group consisting of polyvinyl alcohol and hydroxyethyl cellulose with at least one substance selected from the group consisting of branched alcohol ethers, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters and polyoxyethylene alkyl phenol ethers and an anionic emulsifier selected from the group consisting of alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ethers disulfonates, polyoxyethylene alkyl sulfates and sodium tert-alkyl phenol ether sulfosuccinates (MOS). More preferably, the nonionic emulsifier is a mixture of polyvinyl alcohol and a branched alcohol ether EFS-4070 (preferably with EO number of 40), or a mixture of polyvinyl alcohol and polyoxyethylene alkylphenol ether CO-897 (with EO number of 30-40).
In the present invention, "emulsion polymerization" includes the "first polymerization" and the "second polymerization".
Preferably, the amount of the nonionic emulsifier is 2 to 10 wt% and the amount of the anionic emulsifier is 2 to 4 wt% based on the total amount of the vinyl acetate monomer, the acrylate monomer and the vinyl monomer.
Preferably, the polymerization degree of the polyvinyl alcohol is 200-2600, and the alcoholysis degree is 86-90%; more preferably, the polymerization degree of the polyvinyl alcohol is 300 to 1700. In the present invention, two or more polyvinyl alcohols having different degrees of polymerization and/or alcoholysis may also be used to prepare the copolymer emulsion.
Preferably, the amount of the polyvinyl alcohol and/or the hydroxyethyl cellulose is 4 to 7% by weight based on the total amount of the vinyl acetate monomer, the acrylate monomer and the vinyl monomer. When the amount of the polyvinyl alcohol and/or the hydroxyethyl cellulose is limited to be within the range of 4-7 wt%, the viscosity and the adhesive force of the copolymer emulsion prepared by the method are excellent.
Preferably, the acrylate monomer is selected from at least one of isooctyl acrylate, vinyl laurate, vinyl versatate, and (meth) acrylic acids such as 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, and ethyl (meth) acrylate.
Particularly preferably, the acrylate monomer is isooctyl acrylate (preferably 2-ethylhexyl acrylate), and the inventors of the present invention found that the reactivity ratio of isooctyl acrylate is much higher than that of vinyl acetate, so that the difference of reactivity is relatively large. When the isooctyl acrylate monomer and the vinyl acetate monomer are mixed and added into the emulsion polymerization reaction system in a non-one-time adding mode, the condition that monomer blocks in a polymerization product are not uniform due to excessive monomers can be avoided.
Preferably, the weight ratio of the mixed monomers in the first polymerization reaction and the second polymerization reaction is 1: (2-5).
Preferably, the temperature of the emulsion polymerization reaction is 60-120 ℃. This means that the temperature of both the first polymerization reaction and the second polymerization reaction is preferably in the range of 60 to 120 ℃.
Preferably, the time of the first polymerization reaction is 1.5-8 h, and the time of the second polymerization reaction is 1.5-6 h. The timing starting point of the first polymerization reaction is when the vinyl acetate monomer, the acrylate monomer and the ethylene monomer simultaneously exist in the reaction system, the timing end point of the first polymerization reaction is coincided with the timing starting point of the second polymerization reaction, the timing starting point of the second polymerization reaction is when tert-butyl peroxybenzoate is started to be added, and the timing end point of the second polymerization reaction is a time point of reaction quenching (or a time point of actively reducing temperature to release pressure and discharge).
Preferably, in the first polymerization reaction, the adding mode of the oxidizing agent is a non-one-time adding mode; more preferably, in the first polymerization reaction, the oxidizing agent is added to the first polymerization reaction system in a uniform-speed dropwise adding manner or in a batch adding manner. Preferably, the dropping speed of the oxidizing agent is controlled so that the duration between the initial dropping time and the end dropping time of the oxidizing agent accounts for 1/5-1 of the time of the first polymerization reaction.
Preferably, in the second polymerization reaction, the tert-butyl peroxybenzoate is added in a non-one-time manner; more preferably, the tert-butyl peroxybenzoate is added into the second polymerization reaction system in a uniform dropwise manner or in a batch manner. Preferably, the dropping speed of the tert-butyl peroxybenzoate is controlled so that the duration from the beginning to the end of the dropping of the tert-butyl peroxybenzoate accounts for 1/5-1 of the time of the second polymerization reaction.
The tert-butyl peroxybenzoate is an oil-soluble substance, and in order to ensure a uniform reaction, the tert-butyl peroxybenzoate is preferably mixed with the mixed monomer and then added into the second polymerization reaction system.
The foregoing process of the present invention can be accomplished by, for example, a tank reactor and a batch emulsion polymerization process.
The water used in the emulsion polymerization reaction of the present invention may be deionized water, and the amount of water used is not particularly limited, and may be determined by those skilled in the art according to the amount of water conventionally used in emulsion polymerization reactions.
The pressure of the emulsion polymerization reaction of the present invention may be, for example, 5 to 6 MPa.
As mentioned above, the second aspect of the present invention provides the vinyl acetate-acrylate-ethylene multi-copolymer emulsion prepared by the method of the first aspect.
Preferably, the copolymer emulsion provided by the invention has a solid content of more than 54 wt%, an emulsion viscosity of 1000-9000 mpa.s and a glass transition temperature of-32 ℃ to-15 ℃.
Compared with the prior art, the method provided by the invention and the copolymer emulsion obtained by the method also have the following specific advantages:
1. the invention adopts a specific oxidant-reducing agent combination as an initiating system, and introduces tert-butyl peroxybenzoate in the middle and later stages of emulsion polymerization reaction, thereby ensuring that three monomers with large reactivity ratio difference are uniformly polymerized, improving the single kettle conversion rate of the monomers, and ensuring that the content of residual monomers in the single kettle is less than 1 weight percent before the later-stage preparation;
2. the vinyl acetate-acrylate-ethylene multi-component copolymer emulsion obtained by the method has excellent performance;
3. the vinyl acetate-acrylate-ethylene multi-component copolymer emulsion obtained by the method has high content of structural units formed by acrylate monomers;
4. the vinyl acetate-acrylate-ethylene multi-component copolymer emulsion has higher cohesive force and good and wide adhesion, the adhesion to non-polar packaging materials such as BOPP and PET is obviously improved compared with the adhesion to common modified VAE and acrylate emulsion, and the adhesion strength to BOPP is more than 20N/25mm, preferably more than 40N/25 mm.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
The viscosity of the following copolymer emulsion was measured by means of an NDJ-1 rotary viscometer (Brookfield type viscometer); residual monomer content was determined by headspace gas chromatography; the glass transition temperature is measured by a Differential Scanning Calorimetry (DSC) method; the adhesive strength was determined by the 180 DEG peel strength test method of GB/T2792-1998 pressure-sensitive adhesive tape.
Each portion below represents 1 kg.
Example 1
Dissolving 6 parts of polyvinyl alcohol BP-17 (alcoholysis degree of 88 percent and polymerization degree of 1700)), 1 part of polyvinyl alcohol BP05 (alcoholysis degree of 88 percent and polymerization degree of 500), 4 parts of MOS (metal oxide semiconductor), 4 parts of EFS-4070, 0.5 part of sodium acetate and 0.6 part of ZFS (reducing agent) in 95 parts of deionized water to prepare a water phase, and adding the water phase into a high-pressure kettle; then 30 parts of mixed monomer of vinyl acetate and isooctyl acrylate (weight ratio is 6: 4) is added; introducing ethylene to replace air in the kettle, and then pressurizing to 5MPa by using ethylene; starting stirring, and heating the materials to 70 ℃ by using jacket water of the reaction kettle; 15 parts of tert-butyl hydroperoxide aqueous solution with the concentration of 1 weight percent is added into the reaction kettle at a constant speed by a high-pressure metering pump, the addition is controlled to be completed within 4 hours, and the reaction temperature is controlled not to exceed 90 ℃. After the addition of the aqueous solution of tert-butyl hydroperoxide is finished for 0.5h, ethylene is supplemented until the reaction pressure is 6MPa (the total amount of ethylene monomers is 17 parts), 70 parts of the rest mixed monomer is added into the reaction kettle by a high-pressure metering pump, and the addition is controlled to be finished for 3 h. After the remaining mixed monomer was added for 2 hours, 0.1 part of t-butyl peroxybenzoate was added to the mixed monomer, and added to the emulsion polymerization reaction system together with the mixed monomer. After the residual mixed monomer is added, the temperature is kept for 0.5h, the reaction system is cooled to below 40 ℃, the pressure is released, and the material is discharged.
As a result, the obtained copolymer emulsion had a viscosity of 8600mpa.s, a solid content of 55.87 wt%, a residual monomer content of 0.28 wt%, a pH value of 4.27, a glass transition temperature of-30 ℃ and an adhesive strength to corona-treated BOPP of more than 40N/25 mm.
Example 2
This example was carried out in a similar manner to example 1, except that 6 parts of polyvinyl alcohol BP-17 was replaced by 4 parts of polyvinyl alcohol BP-17, 1 part of polyvinyl alcohol BP05 was replaced by 3 parts of polyvinyl alcohol BP05, and the reaction initiation temperature was changed from 70 ℃ in example 1 to 90 ℃.
The rest is the same as in example 1.
As a result, the copolymer emulsion obtained in this example had a viscosity of 3500mpa.s, a solid content of 55.70% by weight, a residual monomer content of 0.72% by weight, a pH value of 4.81, a glass transition temperature of-31 ℃ and an adhesive strength to corona-treated BOPP of more than 40N/25 mm.
Example 3
This example was carried out in a similar manner to example 1, except that the weight ratio of vinyl acetate to isooctyl acrylate in the mixed monomers of this example was 5: 2.
the rest is the same as in example 1.
As a result, the copolymer emulsion obtained in this example had a viscosity of 4600mpa.s, a solid content of 55.40 wt%, a residual monomer content of 0.62 wt%, a pH value of 4.92, a glass transition temperature of-22 ℃ and a BOPP adhesion strength to corona treatment of more than 26N/25 mm.
Comparative example 1
This comparative example was conducted in a similar manner to example 2, except that it was conducted without adding tert-butyl peroxybenzoate 2 hours after the addition of the remaining mixed monomer.
The rest is the same as in example 2.
As a result, the copolymer emulsion obtained in this comparative example had a viscosity of 1500mpa.s, a solid content of 50.45% by weight, a residual monomer content of 5.25% by weight, a low ethylene consumption, a high residual reaction pressure, and a BOPP adhesion strength to corona treatment of less than 20N/25 mm.
From the results of the above examples, it can be seen that the copolymer emulsion obtained by the method provided by the present invention has high acrylate content and good adhesive strength.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A method of making a vinyl acetate-acrylate-ethylene multipolymer emulsion comprising: under the condition of emulsion polymerization reaction,
(1) in the presence of an oxidation-reduction initiation system, carrying out a first polymerization reaction on part of mixed monomers containing a vinyl acetate monomer and an acrylate monomer and a vinyl monomer, wherein in the oxidation-reduction initiation system, an oxidant is tert-butyl hydroperoxide, and a reducing agent is zinc sulfoxylate formaldehyde and/or sodium formaldehyde sulfoxylate;
(2) adding an ethylene monomer and the rest of the mixed monomer into the system after the first polymerization reaction to perform a second polymerization reaction;
wherein, in the second polymerization reaction, tert-butyl peroxybenzoate is added into the reaction system;
based on the total amount of the vinyl acetate monomer, the acrylate monomer and the ethylene monomer, the amount of the tert-butyl peroxybenzoate in the second polymerization reaction is 0.01-0.2 wt%;
the weight ratio of the mixed monomers in the first polymerization reaction and the second polymerization reaction is 1: (2-5).
2. The method according to claim 1, wherein the vinyl acetate monomer is used in an amount of 40 to 70 wt%, the acrylate monomer is used in an amount of 25 to 35 wt%, and the ethylene monomer is used in an amount of 5 to 30 wt% in the emulsion polymerization, based on the total amount of the vinyl acetate monomer, the acrylate monomer, and the ethylene monomer.
3. The method according to claim 2, wherein the vinyl acetate monomer is used in an amount of 50 to 55 wt%, the acrylate monomer is used in an amount of 30 to 35 wt%, and the ethylene monomer is used in an amount of 14 to 15 wt% in the emulsion polymerization.
4. The method according to any one of claims 1 to 3, wherein the reducing agent is used in an amount of 0.2 to 0.6 wt% and the oxidizing agent is used in an amount of 0.02 to 0.2 wt% in the first polymerization reaction, based on the total amount of the vinyl acetate monomer, the acrylate monomer, and the ethylene monomer.
5. The process according to claim 1, wherein the emulsion polymerization is carried out in the presence of a nonionic emulsifier which is a mixture of at least one member selected from the group consisting of polyvinyl alcohol and hydroxyethyl cellulose and at least one member selected from the group consisting of branched alcohol ethers, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters and polyoxyethylene alkylphenol ethers and an anionic emulsifier selected from the group consisting of alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ethers disulfonates, polyoxyethylene alkyl sulfates and sodium tert-alkylphenol ether sulfosuccinates.
6. The method according to claim 5, wherein the nonionic emulsifier is used in an amount of 2 to 10% by weight and the anionic emulsifier is used in an amount of 2 to 4% by weight, based on the total amount of the vinyl acetate monomer, the acrylate ester monomer and the vinyl monomer.
7. The method according to claim 5 or 6, wherein the polyvinyl alcohol has a degree of polymerization of 200 to 2600 and a degree of alcoholysis of 86 to 90%.
8. The method according to claim 7, wherein the degree of polymerization of the polyvinyl alcohol is 300 to 1700.
9. The method of claim 1, wherein the acrylate monomer is selected from at least one of isooctyl acrylate, vinyl laurate, vinyl versatate, and (meth) acrylic acid.
10. The method according to claim 9, wherein the (meth) acrylic acid is at least one of 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, and ethyl (meth) acrylate.
11. The process of claim 1, wherein the emulsion polymerization temperature is 60 to 120 ℃.
12. The process according to claim 1 or 11, wherein the time for the first polymerization reaction is 1.5 to 8 hours and the time for the second polymerization reaction is 1.5 to 6 hours.
13. A vinyl acetate-acrylate-ethylene multi-copolymer emulsion prepared by the method of any one of claims 1 to 12.
14. The copolymer emulsion of claim 13, wherein the copolymer emulsion has a solids content of > 54% by weight, an emulsion viscosity of 1000 to 9000mpa.s, and a glass transition temperature of-32 ℃ to-15 ℃.
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| CN112126002B (en) * | 2020-09-10 | 2022-05-10 | 珠海展辰新材料股份有限公司 | Water-based acrylic resin, preparation method thereof and amino baking varnish |
| CN115991843A (en) * | 2021-10-20 | 2023-04-21 | 中国石油化工股份有限公司 | Sagging-resistant VAE emulsion and preparation method thereof |
| CN115991811A (en) * | 2021-10-20 | 2023-04-21 | 中国石油化工股份有限公司 | Anti-sagging ethylene-vinyl acetate copolymer and preparation method thereof |
| CN115677892B (en) * | 2022-09-29 | 2023-08-29 | 云南正邦科技有限公司 | Ethylene-vinyl acetate-acrylic terpolymer and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61174279A (en) * | 1985-01-29 | 1986-08-05 | Aika Kogyo Kk | Vinyl acetate resin emulsion adhesive |
| EP3176187A1 (en) * | 2015-12-02 | 2017-06-07 | Organik Kimya Sanayi Ve Tic. A.S. | Formaldehyde-free thermally curable polymers |
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