CN114426628A - Vinyl acetate-ethylene copolymer emulsion with excellent water resistance and preparation method thereof - Google Patents
Vinyl acetate-ethylene copolymer emulsion with excellent water resistance 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
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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
- 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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- C09J131/04—Homopolymers or copolymers of vinyl acetate
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Abstract
The invention belongs to the technical field of vinyl acetate, and particularly relates to a vinyl acetate-ethylene copolymer emulsion with excellent water resistance. The vinyl acetate-ethylene copolymer emulsion is prepared from raw materials including a monomer, an emulsifier, a protective colloid, a modified protective colloid, alcohols and an initiation system, wherein the monomer comprises glycidyl methacrylate. The vinyl acetate-ethylene copolymer emulsion adhesive film has low water absorption rate and excellent water resistance.
Description
Technical Field
The invention belongs to the technical field of vinyl acetate, and particularly relates to a vinyl acetate-ethylene copolymer emulsion with excellent water resistance and a preparation method thereof.
Background
The VAE emulsion is also called vinyl acetate-ethylene copolymer emulsion, EVA emulsion and the like, and is a high molecular polymer (called vinyl acetate, vinyl acetate and the like) copolymerized by using vinyl acetate and ethylene as basic raw materials (the research on environment-friendly modification of the VAE emulsion progresses, Zhanghua, medium and small-sized enterprise management and science and technology, the 8 th stage in 2017, the 1 st section and the 2 th lines in the left column of the 92 page, the 4 th and 25 th days in 2017, the research on the organosiloxane modified VAE emulsion, Sun Yan, bonding, the 10 th stage in 2013, the 1 st section and the 1 st line in the left column of the 59 page, and the 10 th and 30 th days in 2013).
The vinyl acetate-ethylene copolymer emulsion has the advantages of permanent flexibility, good adhesive property, acid and alkali resistance, ultraviolet aging resistance, fast curing, high temperature resistance, easy modification, good environmental protection performance and the like (the VAE emulsion environmental modification research progress, the tension changes, the management and science and technology of small and medium enterprises, the 8 th stage in 2017, the 1 st paragraph 2-3 line in the left column of page 92, the 4 th month 25 day in 2017; the application of the VAE emulsion tends to diversification; Lvkangheliang, Chinese chemical industry report, 2004, the 3 rd paragraph 2-3 line in the left column, the 9 th month 11 day in 2004; "the compound modification research of the VAE emulsion", the dimension, the Beijing university treatise 2001, the 4 rd paragraph 1 st line to the 5 th paragraph 1 line, the 12 th month 31 day in 2001).
At present, the vinyl acetate-ethylene copolymer emulsion is widely applied to the fields of composite packaging materials, cigarettes, modification of building cement mortar, building waterproofing, coatings, non-woven fabrics, paper coatings, wood processing, electrostatic flocking, carpet back glue, automobile decoration, shoe materials, leather, rubber and the like ("novel VAE emulsion and application thereof in adhesives", Liu Bing Pong and the like, Chinese adhesives, No. 14, No. 7, No. 1, No. 3, on the left column of the 24 page, No. 7, No. 31, in 2005; "VAE emulsion application tends to diversification", Chinese Lourg, Chinese chemical industry newspaper, 2004, No. 2, No. 1, No. 5, in the left column, and No. 9, No. 11, in 2004).
However, the existing vinyl acetate-ethylene copolymer emulsion can not meet the application requirements of the fields with higher water resistance requirements such as wood bonding, interior wall coating and the like.
Disclosure of Invention
In view of the above, the present invention aims to provide a vinyl acetate-ethylene copolymer emulsion which can meet the application requirements of the fields with high water resistance requirements, such as wood bonding, interior wall coating, etc.
The parts are parts by mass unless otherwise specified.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the vinyl acetate-ethylene copolymer emulsion is prepared from raw materials including a monomer, an emulsifier, a protective colloid, a modified protective colloid, alcohols and an initiating system, wherein the monomer comprises glycidyl methacrylate.
Further, the monomers also include vinyl acetate and ethylene.
Further, the monomer comprises 35-55 parts of vinyl acetate, 1-3 parts of glycidyl methacrylate and a proper amount of ethylene in parts by mass.
Further, the emulsifier comprises a nonionic emulsifier.
Further, the nonionic emulsifier comprises one or more of nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and isomeric tridecyl polyoxyethylene ether and oleyl alcohol polyoxyethylene ether.
Further, the nonionic emulsifier comprises fatty alcohol-polyoxyethylene ether or isomeric tridecyl polyoxyethylene ether.
Further, the protective colloid includes any one or more of polyvinyl alcohol (PVA) and hydroxyethyl cellulose.
Further, the protective colloid comprises preferably polyvinyl alcohol.
Further, the modified protective colloid comprises carboxyl modified polyvinyl alcohol.
Further, the alcohols include one or more of ethanol, ethylene glycol, and glycerol.
Further, the alcohol includes glycerol.
Further, the mass ratio of the modified protective colloid to the alcohols is 0.3-0.7: 0.5-2.
Further, the modified protective colloid comprises carboxyl modified polyvinyl alcohol.
Further, the initiating system includes an oxidizing agent and a reducing agent.
Further, the oxidizing agent includes potassium persulfate, sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide, or t-butyl peroxybenzoate.
Further, the oxidizing agent comprises tert-butyl hydroperoxide.
Further, the reducing agent comprises potassium tartrate, sodium erythorbate, vitamin C or zinc formaldehyde sulfoxylate.
Further, the reducing agent comprises sodium erythorbate and vitamin C.
Further, the vinyl acetate-ethylene copolymer emulsion is prepared from raw materials including, by mass, 35-55 parts of vinyl acetate, 1-3 parts of glycidyl methacrylate, a proper amount of ethylene, 0.3-0.7 part of an emulsifier, 1-4 parts of a protective colloid, 0.3-0.7 part of a modified protective colloid, 0.5-2 parts of alcohols and 0.1-0.6 part of an initiating system.
The invention also aims to protect the preparation method of the vinyl acetate-ethylene copolymer emulsion, which comprises the following steps:
A. raw material preparation
Preparing an initiating system emulsion: respectively preparing an oxidant solution and a reducing agent solution in an oxidant tank and a reducing agent tank;
preparing a protective colloid solution: sequentially adding water and protective colloid into the dissolving tank under stirring, heating to 90-95 deg.C, maintaining the temperature for 100-120min, and cooling to 50-60 deg.C;
preparing a modified protective colloid solution: sequentially adding water and the modified protective colloid into the dissolving tank under stirring, heating to 90-95 deg.C, maintaining the temperature for 100-120min, cooling to 50-60 deg.C, adding alcohol, and stirring;
preparing a mixed monomer: uniformly mixing vinyl acetate and glycidyl methacrylate under stirring;
B. feeding production
Adding a protective colloid solution, a modified protective colloid solution and an emulsifier into a reaction kettle, uniformly stirring, adding a mixed monomer accounting for 50-88% of the total amount, and heating and boosting pressure;
when the temperature is raised to 50-60 ℃ and the pressure reaches 2.0-3.5MPa, pumping reducing agent solution accounting for 10-40% of the total amount into the reaction kettle, then simultaneously dripping oxidant solution and reducing agent solution into the reaction kettle at the speed of 5.0-10.0kg/min, and when the temperature in the reaction kettle reaches 55-65 ℃, reducing the speed of the oxidant solution and the reducing agent solution to 1.0-3.0 kg/min;
when the temperature in the kettle reaches 75-80 ℃, the ethylene pressure is increased to 4.0-6.0MPa, then the rest mixed monomer is added within 60-120min, and the ethylene is closed after the mixed monomer is added;
adding the rest oxidant solution and the rest reducing agent solution at the rate of 4.0-8.0kg/min, then reducing to normal pressure, cooling to normal temperature, filtering and discharging.
The invention also aims to protect the application of the vinyl acetate-ethylene copolymer emulsion in wood bonding and interior wall coatings.
The invention has the beneficial effects that:
the vinyl acetate-ethylene copolymer emulsion adhesive film disclosed by the invention is low in water absorption rate and excellent in water resistance.
The vinyl acetate-ethylene copolymer emulsion has good water resistance and good initial viscosity.
The preparation method is simple and easy to implement, convenient and quick, and is beneficial to realizing industrial production;
Detailed Description
The examples are provided for better illustration of the present invention, but the present invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
The following appearance, mass fraction of non-volatile matter, viscosity, pH and dilution stability were measured according to the method of detection of the corresponding index in GB/T27573-2011 vinyl acetate-ethylene copolymer emulsion;
the following method for detecting mechanical stability is as follows: filtering the emulsion by using a 120-mesh filter screen, dispersing the emulsion for 30min at the rotating speed of 3000 r/min by using a high-speed dispersion machine, and filtering by using a 120-mesh filter screen, wherein if the emulsion is broken or more filter residues are left, the mechanical stability of the emulsion cannot pass;
the following initial viscosity detection method is as follows: starting a vacuum pump to pump vacuum, after the vacuum degree meets the requirement, flatly paving a piece of kraft paper (26.8 multiplied by 19.3cm) on a vacuum plate, uniformly coating a sample on the kraft paper by using a wet film preparation device (0.1mm), paving a piece of kraft paper again, and starting timing; then, slowly tearing the upper kraft paper layer and the lower kraft paper layer from one end of the kraft paper, stopping timing when the kraft paper is torn to be fluffed, performing a parallel test, and reporting the recorded time, wherein the shorter the time, the better the initial viscosity of the emulsion;
the following water absorption rate detection method comprises the following steps: soaking the dried adhesive film (with the mass of M0) with water at room temperature for 24h, quickly wiping off the water on the surface of the adhesive film, and weighing (with the mass of M1); then calculating the water absorption according to the following formula (the larger the water absorption is, the poorer the water resistance of the adhesive film is;
water absorption rate is (M1-M0)/M0 × 100%;
in the formula: m0 and M1 are the mass of the glue film before and after soaking respectively, and the unit is g.
The following carboxyl-modified polyvinyl alcohol was SG-182 modified polyvinyl alcohol purchased from Chongqing Chuanyuan chemical Co., Ltd.
Example 1
The vinyl acetate-ethylene copolymer emulsion is prepared by the following raw materials according to the following steps:
A. raw material preparation
Preparing an initiating system emulsion: adding 3 parts of deionized water and 0.1 part of oxidant tert-butyl hydroperoxide into an oxidant tank, and stirring to dissolve to obtain an oxidant solution; adding 3 parts of deionized water and 0.1 part of reducing agent vitamin C into a reducing agent tank, and stirring to dissolve to obtain a reducing agent solution;
preparing a protective colloid solution: under the stirring state, sequentially adding 20 parts of deionized water, 1 part of PVA0588, 0.5 part of PVA1788 and 1 part of PVA1799 into a dissolving tank, then heating to 90-95 ℃, preserving heat for 100-120min at the temperature, and then cooling to 50-60 ℃ for later use;
preparing a modified protective colloid solution: under the stirring state, sequentially adding 10 parts of deionized water and 0.5 part of carboxyl modified polyvinyl alcohol into a dissolving tank, then heating to 90-95 ℃, preserving heat for 100-120min, cooling to 50-60 ℃, adding 2 parts of glycerol, and uniformly stirring;
preparing a mixed monomer: uniformly mixing 45 parts of vinyl acetate and 2 parts of glycidyl methacrylate under stirring;
B. feeding production
Under the stirring state, adding the prepared protective colloid solution, the prepared modified protective colloid solution and 0.4 part of non-ionic emulsifier 15-s-30 into a reaction kettle, stirring uniformly, adding 31 parts of mixed monomer, heating and boosting;
pumping reducing agent solution accounting for 40 percent of the total amount into the reaction kettle when the temperature is raised to 55 ℃ and the pressure reaches 3.0MPa, then simultaneously adding oxidant solution and reducing agent solution into the reaction kettle at the speed of 5.0kg/min, and reducing the speed of the oxidant solution and the reducing agent solution to 1.5kg/min when the temperature in the reaction kettle reaches 63 ℃;
when the temperature in the kettle reaches 80 ℃, the ethylene pressure is increased to 5.8MPa, then the rest 16 parts of mixed monomer are added at a constant speed within 90min, and the ethylene is closed after the mixed monomer is added;
adding the rest oxidant solution and the rest reducing agent solution at the speed of 8.0kg/min, then reducing to normal pressure, reducing to normal temperature, filtering and discharging.
Comparative example 1
The vinyl acetate-ethylene copolymer emulsion is prepared by the following raw materials according to the following steps:
A. raw material preparation
Preparing an initiating system emulsion: adding 3 parts of deionized water and 0.1 part of oxidant tert-butyl hydroperoxide into an oxidant tank, and stirring to dissolve to obtain an oxidant solution; adding 3 parts of deionized water and 0.1 part of reducing agent vitamin C into a reducing agent tank, and stirring to dissolve to obtain a reducing agent solution;
preparing a protective colloid solution: under the stirring state, sequentially adding 20 parts of deionized water, 1 part of PVA0588, 0.5 part of PVA1788 and 1 part of PVA1799 into a dissolving tank, then heating to 90-95 ℃, preserving heat for 100-120min at the temperature, and then cooling to 50-60 ℃ for later use;
B. feeding production
Under the stirring state, adding the prepared protective colloid solution and 0.4 part of non-ionic emulsifier 15-s-30 into a reaction kettle, stirring uniformly, adding 30 parts of vinyl acetate monomer, and raising the temperature and the pressure;
pumping reducing agent solution accounting for 40 percent of the total amount into the reaction kettle when the temperature is raised to 55 ℃ and the pressure reaches 3.0MPa, then simultaneously adding oxidant solution and reducing agent solution into the reaction kettle at the speed of 5.0kg/min, and reducing the speed of the oxidant solution and the reducing agent solution to 1.5kg/min when the temperature in the reaction kettle reaches 63 ℃;
when the temperature in the kettle reaches 80 ℃, the ethylene pressure is increased to 5.8MPa, then 15 parts of vinyl acetate monomer is added at a constant speed within 90min, and the ethylene is closed after the vinyl acetate monomer is added;
adding the rest oxidant solution and the rest reducing agent solution at the speed of 8.0kg/min, then reducing to normal pressure, reducing to normal temperature, filtering and discharging.
Comparative example 2
The vinyl acetate-ethylene copolymer emulsion is prepared by the following raw materials according to the following steps:
A. raw material preparation
Preparing an initiating system emulsion: adding 3 parts of deionized water and 0.1 part of oxidant tert-butyl hydroperoxide into an oxidant tank, and stirring to dissolve to obtain an oxidant solution; adding 3 parts of deionized water and 0.1 part of reducing agent vitamin C into a reducing agent tank, and stirring to dissolve to obtain a reducing agent solution;
preparing a protective colloid solution: under the stirring state, sequentially adding 20 parts of deionized water, 1 part of PVA0588, 0.5 part of PVA1788 and 1 part of PVA1799 into a dissolving tank, then heating to 90-95 ℃, preserving heat for 100-120min at the temperature, and then cooling to 50-60 ℃ for later use;
preparing a modified protective colloid solution: under the stirring state, sequentially adding 10 parts of deionized water and 0.5 part of carboxyl modified polyvinyl alcohol into a dissolving tank, then heating to 90-95 ℃, preserving heat for 60-120min, and then cooling to 50-60 ℃, adding 2 parts of glycerol for later use;
preparing a mixed monomer: uniformly mixing 45 parts of vinyl acetate and 2 parts of hydroxyethyl acrylate under stirring;
B. feeding production
Under the stirring state, adding the prepared protective colloid solution, the prepared modified protective colloid solution and 0.4 part of non-ionic emulsifier 15-s-30 into a reaction kettle, stirring uniformly, adding 31 parts of mixed monomer, heating and boosting;
pumping reducing agent solution accounting for 40 percent of the total amount into the reaction kettle when the temperature is raised to 55 ℃ and the pressure reaches 3.0MPa, then simultaneously adding oxidant solution and reducing agent solution into the reaction kettle at the speed of 5.0kg/min, and reducing the speed of the oxidant solution and the reducing agent solution to 1.5kg/min when the temperature in the reaction kettle reaches 63 ℃;
when the temperature in the kettle reaches 80 ℃, the ethylene pressure is increased to 5.8MPa, then the rest 16 parts of mixed monomer are added at a constant speed within 90min, and the ethylene is closed after the mixed monomer is added;
adding the rest oxidant solution and the rest reducing agent solution at the speed of 8.0kg/min, then reducing to normal pressure, reducing to normal temperature, filtering and discharging.
Comparative example 3
The vinyl acetate-ethylene copolymer emulsion is prepared by the following raw materials according to the following steps:
A. raw material preparation
Preparing an initiating system emulsion: adding 3 parts of deionized water and 0.1 part of oxidant tert-butyl hydroperoxide into an oxidant tank, and stirring to dissolve to obtain an oxidant solution; adding 3 parts of deionized water and 0.1 part of reducing agent vitamin C into a reducing agent tank, and stirring to dissolve to obtain a reducing agent solution;
preparing a protective colloid solution: under the stirring state, sequentially adding 20 parts of deionized water, 1 part of PVA0588, 0.5 part of PVA1788 and 1 part of PVA1799 into a dissolving tank, then heating to 90-95 ℃, preserving heat for 100-120min at the temperature, and then cooling to 50-60 ℃ for later use;
preparing a modified protective colloid solution: under the stirring state, sequentially adding 10 parts of deionized water and 0.5 part of ethylene modified polyvinyl alcohol RS-2117 into a dissolving tank, then heating to 90-95 ℃, keeping the temperature for 100-120min, and then cooling to 50-60 ℃ and adding 2 parts of glycerol for later use;
preparing a mixed monomer: uniformly mixing 45 parts of vinyl acetate and 2 parts of glycidyl acrylate under stirring;
B. feeding production
Under the stirring state, adding the prepared protective colloid solution, the prepared modified protective colloid solution and 0.4 part of non-ionic emulsifier 15-s-30 into a reaction kettle, stirring uniformly, adding 31 parts of mixed monomer, heating and boosting;
pumping reducing agent solution accounting for 40 percent of the total amount into the reaction kettle when the temperature is raised to 55 ℃ and the pressure reaches 3.0MPa, then simultaneously adding oxidant solution and reducing agent solution into the reaction kettle at the speed of 5.0kg/min, and reducing the speed of the oxidant solution and the reducing agent solution to 1.5kg/min when the temperature in the reaction kettle reaches 63 ℃;
when the temperature in the kettle reaches 80 ℃, the ethylene pressure is increased to 5.8MPa, then the rest 16 parts of mixed monomer are added at a constant speed within 90min, and the ethylene is closed after the mixed monomer is added;
adding the rest oxidant solution and the rest reducing agent solution at the speed of 8.0kg/min, then reducing to normal pressure, reducing to normal temperature, filtering and discharging.
Comparative example 4
The vinyl acetate-ethylene copolymer emulsion is prepared by the following raw materials according to the following steps:
A. raw material preparation
Preparing an initiating system emulsion: adding 3 parts of deionized water and 0.1 part of oxidant tert-butyl hydroperoxide into an oxidant tank, and stirring to dissolve to obtain an oxidant solution; adding 3 parts of deionized water and 0.1 part of reducing agent vitamin C into a reducing agent tank, and stirring to dissolve to obtain a reducing agent solution;
preparing a protective colloid solution: under the stirring state, sequentially adding 20 parts of deionized water, 1 part of PVA0588, 0.5 part of PVA1788 and 1 part of PVA1799 into a dissolving tank, then heating to 90-95 ℃, preserving heat for 100-120min at the temperature, and then cooling to 50-60 ℃ for later use;
preparing a modified protective colloid solution: under the stirring state, sequentially adding 10 parts of deionized water and 0.5 part of carboxyl modified polyvinyl alcohol into a dissolving tank, then heating to 90-95 ℃, preserving heat for 100-120min, cooling to 50-60 ℃, adding 4 parts of glycerol, and uniformly stirring;
preparing a mixed monomer: uniformly mixing 45 parts of vinyl acetate and 2 parts of glycidyl methacrylate under stirring;
B. feeding production
Under the stirring state, adding the prepared protective colloid solution, the prepared modified protective colloid solution and 0.4 part of non-ionic emulsifier 15-s-30 into a reaction kettle, stirring uniformly, adding 31 parts of mixed monomer, heating and boosting;
pumping reducing agent solution accounting for 40 percent of the total amount into the reaction kettle when the temperature is raised to 55 ℃ and the pressure reaches 3.0MPa, then simultaneously adding oxidant solution and reducing agent solution into the reaction kettle at the speed of 5.0kg/min, and reducing the speed of the oxidant solution and the reducing agent solution to 1.5kg/min when the temperature in the reaction kettle reaches 63 ℃;
when the temperature in the kettle reaches 80 ℃, the ethylene pressure is increased to 5.8MPa, then the rest 16 parts of mixed monomer are added at a constant speed within 90min, and the ethylene is closed after the mixed monomer is added;
adding the rest oxidant solution and the rest reducing agent solution at a constant speed of 8.0kg/min, then reducing to normal pressure, cooling to normal temperature, filtering and discharging.
Comparative example 5
The vinyl acetate-ethylene copolymer emulsion is prepared by the following raw materials according to the following steps:
A. raw material preparation
Preparing an initiating system emulsion: adding 3 parts of deionized water and 0.1 part of oxidant tert-butyl hydroperoxide into an oxidant tank, and stirring to dissolve to obtain an oxidant solution; adding 3 parts of deionized water and 0.1 part of reducing agent vitamin C into a reducing agent tank, and stirring to dissolve to obtain a reducing agent solution;
preparing a protective colloid solution: under the stirring state, sequentially adding 20 parts of deionized water, 1 part of PVA0588, 0.5 part of PVA1788 and 1 part of PVA1799 into a dissolving tank, then heating to 90-95 ℃, preserving heat for 100-120min at the temperature, and then cooling to 50-60 ℃ for later use;
preparing a modified protective colloid solution: under the stirring state, sequentially adding 10 parts of deionized water and 0.5 part of carboxyl modified polyvinyl alcohol into a dissolving tank, then heating to 90-95 ℃, preserving heat for 100-120min, and then cooling to 50-60 ℃ for later use;
preparing a mixed monomer: uniformly mixing 45 parts of vinyl acetate and 2 parts of glycidyl methacrylate under stirring;
B. feeding production
Under the stirring state, adding the prepared protective colloid solution, the prepared modified protective colloid solution and 0.4 part of non-ionic emulsifier 15-s-30 into a reaction kettle, stirring uniformly, adding 31 parts of mixed monomer, heating and boosting;
pumping reducing agent solution accounting for 40 percent of the total amount into the reaction kettle when the temperature is raised to 55 ℃ and the pressure reaches 3.0MPa, then simultaneously adding oxidant solution and reducing agent solution into the reaction kettle at the speed of 5.0kg/min, and reducing the speed of the oxidant solution and the reducing agent solution to 1.5kg/min when the temperature in the reaction kettle reaches 63 ℃;
when the temperature in the kettle reaches 80 ℃, the ethylene pressure is increased to 5.8MPa, then the rest 16 parts of mixed monomer are added at a constant speed within 90min, and the ethylene is closed after the mixed monomer is added;
adding the rest oxidant solution and the rest reducing agent solution at a constant speed of 8.0kg/min, then reducing to normal pressure, cooling to normal temperature, filtering and discharging.
Performance detection
The vinyl acetate-ethylene copolymer emulsions obtained in example 1 and comparative examples 1 to 5 were subjected to tests for properties such as appearance, mass fraction of non-volatile matter, viscosity, pH, dilution stability, mechanical stability, initial tack and water absorption, and the results are shown in Table 1.
TABLE 1 Performance test results
Remarking: the shorter the initial tack, the better the initial tack.
As can be seen from table 1, the vinyl acetate-ethylene copolymer emulsion of example 1 was significantly reduced in water absorption as compared to comparative examples 1 to 5. This proves that the vinyl acetate-ethylene copolymer emulsion of the present invention is excellent in water resistance.
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 (10)
1. The vinyl acetate-ethylene copolymer emulsion is characterized by being prepared from raw materials including monomers, an emulsifier, a protective colloid, a modified protective colloid, alcohols and an initiating system, wherein the monomers include glycidyl methacrylate.
2. The vinyl acetate-ethylene copolymer emulsion of claim 1 wherein the monomers further comprise vinyl acetate and ethylene.
3. The vinyl acetate-ethylene copolymer emulsion according to claim 2, wherein the monomers comprise, by mass, 35 to 55 parts of vinyl acetate, 1 to 3 parts of glycidyl methacrylate, and an appropriate amount of ethylene.
4. The vinyl acetate-ethylene copolymer emulsion according to any of claims 1 to 3, wherein the modified protective colloid comprises a carboxyl-modified polyvinyl alcohol.
5. The vinyl acetate-ethylene copolymer emulsion according to any one of claims 1 to 4, wherein the emulsifier comprises a nonionic emulsifier.
6. The vinyl acetate-ethylene copolymer emulsion according to any one of claims 1 to 5, wherein the alcohol comprises one or more of ethanol, ethylene glycol and glycerol.
7. The vinyl acetate-ethylene copolymer emulsion of claim 6 wherein the alcohol comprises glycerol.
8. The vinyl acetate-ethylene copolymer emulsion according to any one of claims 2 to 7, wherein the mass ratio of the modified protective colloid to the alcohol is 0.3 to 0.7:0.5 to 2.
9. A process for preparing a vinyl acetate-ethylene copolymer emulsion according to any one of claims 1 to 8, comprising the steps of:
A. raw material preparation
Preparing an initiating system emulsion: respectively preparing an oxidant solution and a reducing agent solution in an oxidant tank and a reducing agent tank;
preparing a protective colloid solution: sequentially adding water and protective colloid into the dissolving tank under stirring, heating to 90-95 deg.C, maintaining the temperature for 100-120min, and cooling to 50-60 deg.C;
preparing a modified protective colloid solution: sequentially adding water and the modified protective colloid into the dissolving tank under stirring, heating to 90-95 deg.C, maintaining the temperature for 100-120min, cooling to 50-60 deg.C, adding alcohol, and stirring;
preparing a mixed monomer: uniformly mixing vinyl acetate and glycidyl methacrylate under stirring;
B. feeding production
Adding a protective colloid solution, a modified protective colloid solution and an emulsifier into a reaction kettle, uniformly stirring, adding a mixed monomer accounting for 50-88% of the total amount, and heating and boosting pressure;
when the temperature is raised to 50-60 ℃ and the pressure reaches 2.0-3.5MPa, pumping reducing agent solution accounting for 10-40% of the total amount into the reaction kettle, then simultaneously dripping oxidant solution and reducing agent solution into the reaction kettle at the speed of 5.0-10.0kg/min, and when the temperature in the reaction kettle reaches 55-65 ℃, reducing the speed of the oxidant solution and the reducing agent solution to 1.0-3.0 kg/min;
when the temperature in the kettle reaches 75-80 ℃, the ethylene pressure is increased to 4.0-6.0MPa, then the rest mixed monomer is added within 60-120min, and the ethylene is closed after the mixed monomer is added;
adding the rest oxidant solution and the rest reducing agent solution at the rate of 4.0-8.0kg/min, then reducing to normal pressure, cooling to normal temperature, filtering and discharging.
10. Use of the vinyl acetate-ethylene copolymer emulsion according to any one of claims 1 to 8 for wood bonding and interior wall coatings.
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| CN102892494A (en) * | 2010-07-14 | 2013-01-23 | 瓦克化学股份公司 | Semi-continuous method for emulsion polymerisation |
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| CN107075024A (en) * | 2014-10-30 | 2017-08-18 | 阿朗新科德国有限责任公司 | Include the curable compositions of the EVAc containing epoxy radicals |
| CN110461888A (en) * | 2017-02-17 | 2019-11-15 | 瓦克化学股份公司 | The purposes that aqueous polymer dispersion is bonded in high-molecular porous material interface |
| CN110872362A (en) * | 2018-08-31 | 2020-03-10 | 中国石油化工股份有限公司 | Vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
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| CN102695725A (en) * | 2010-07-14 | 2012-09-26 | 瓦克化学股份公司 | Process for continuous emulsion polymerization |
| CN102892494A (en) * | 2010-07-14 | 2013-01-23 | 瓦克化学股份公司 | Semi-continuous method for emulsion polymerisation |
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| CN107075024A (en) * | 2014-10-30 | 2017-08-18 | 阿朗新科德国有限责任公司 | Include the curable compositions of the EVAc containing epoxy radicals |
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