CN112322230A - Polyvinyl acetate emulsion adhesive with excellent water resistance and preparation method thereof - Google Patents
Polyvinyl acetate emulsion adhesive with excellent water resistance and preparation method thereof Download PDFInfo
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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
- 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
- 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
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a polyvinyl acetate emulsion adhesive with excellent water resistance and a preparation method thereof. The emulsion provided by the invention has good weather resistance, heat resistance and wear resistance, especially has excellent water resistance, can realize industrial production, and has the advantages of simple equipment, stable production, safety and environmental protection.
Description
Technical Field
The invention relates to the technical field of high-molecular emulsion polymerization, in particular to a polyvinyl acetate emulsion adhesive with excellent water resistance and a preparation method thereof.
Technical Field
White latex, abbreviated as PVAC emulsion, whose chemical name is polyvinyl acetate adhesive, is a milky thick liquid prepared by synthesizing vinyl acetate from acetic acid and ethylene, adding titanium white powder, light calcium carbonate, talcum powder and other powder materials, and polymerizing the emulsion. The white latex can be cured at normal temperature, has high curing speed and high bonding strength, and the bonding layer has good toughness and durability and is not easy to age, thereby being one of the adhesive varieties with the widest application and the largest using amount at present. The white latex is prepared by emulsion polymerization with water as a dispersion medium, is a water-based environment-friendly adhesive, and has the characteristics of good film forming property, good dilute alkali resistance, convenient use, low price, no organic solvent and the like. Due to the low softening point, in addition to the use of PVA as a protective colloid during manufacture, PVA has a great number of hydrophilic hydroxyl groups, so that the PVA has good hydrophilicity, and the PVA has fatal weaknesses: the performance in the aspects of water resistance and the like is poor. Therefore, how to improve the water resistance of polyvinyl acetate emulsion has been the focus of discussion and research of researchers at home and abroad.
Patent CN201810604903.9 discloses a white latex with improved water resistance, which has the advantages of good cohesiveness, short curing time, excellent water resistance and difficult glue failure in a humid environment. However, the filler proportion in the production process of the white latex is too large, the requirement of stable production in mass production is difficult to meet, and meanwhile, the formula contains N-hydroxymethyl acrylamide, so that the monomer is easy to generate a gel phenomenon in the production process, and the requirements on mass production control and equipment are improved.
Patent CN201310454274.3 discloses a powdery white latex and a preparation method thereof, wherein the powdery white latex has simple preparation method and high storage stability, but the water resistance of the adhesive is still poor, and the requirement of the current market on the water-resistant white latex is difficult to meet.
Disclosure of Invention
Based on the problems of the prior art, the invention aims to provide a polyvinyl acetate emulsion adhesive with excellent water resistance and a preparation method thereof, so that the polyvinyl acetate emulsion adhesive can be stably produced industrially, and the requirement on the water resistance of white latex is met.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyvinyl acetate emulsion adhesive with excellent water resistance is characterized in that: the adhesive comprises the following raw materials in parts by weight: 15-25 parts of protective colloid, 315-375 parts of modified protective colloid solution, 150-200 parts of reaction monomer, 100-150 parts of modified monomer, 3-8 parts of initiator, 0.5-1.5 parts of reactive emulsifier, 20-30 parts of plasticizer, 3-6 parts of pH regulator and 300-350 parts of deionized water.
Preferably, the modified protective colloid solution is a protective colloid solution obtained by modifying polyvinyl alcohol 17-99 through an acetalization reaction, and the solid content of the solution is 8-16%.
Preferably, the protective colloid is at least one of hydroxyethyl cellulose, polymethyl cellulose and polyvinyl alcohol; the polymerization degree of the polyvinyl alcohol is 500-2000, and the alcoholysis degree of the polyvinyl alcohol is 88-99%.
Preferably, the reactive monomer is vinyl acetate.
Preferably, the modified monomer is vinyl versatate.
Preferably, the initiator is at least one of ammonium persulfate, hydrogen peroxide and potassium persulfate.
Preferably, the reactive emulsifier is at least one of polyoxyethylene vinyl methyl ether, acrylamide isopropyl sodium sulfonate and double-bond-containing alcohol ether sulfosuccinate sodium salt.
Preferably, the plasticizer is at least one of dibutyl phthalate, diethyl phthalate and di (2-ethylhexyl) phthalate.
Preferably, the pH regulator is at least one of sodium acetate, sodium bicarbonate and sodium citrate.
The preparation method of the polyvinyl acetate emulsion adhesive with excellent water resistance comprises the following steps:
1) adding 280-320 parts of deionized water into a three-neck flask, heating to 80-90 ℃, adding 15-25 parts of protective colloid under a stirring state, continuously stirring until the protective colloid is completely dissolved, cooling to 60-70 ℃, and adding 315-375 parts of modified protective colloid solution for later use;
2) weighing 3-8 parts of initiator, and dissolving in 20-30 parts of deionized water for later use; weighing 100-150 parts of modified monomer and 150-200 parts of reaction monomer for later use;
3) adding 8-12 parts of initiator aqueous solution completely dissolved and 0.5-1.5 parts of reactive emulsifier into the three-neck flask subjected to cooling in the step 1), then adding 8-10 parts of modified monomer and 50-70 parts of reactive monomer, and performing seed emulsion polymerization at the reaction temperature of 75-85 ℃ for 25-35 minutes;
4) keeping the constant temperature of the three-neck flask at 75-85 ℃, then mixing the remaining modified monomer and reaction monomer, gradually dropwise adding the mixture into the three-neck flask for emulsion polymerization, wherein the dropwise adding time is 4-6 hours, and adding the remaining initiator aqueous solution once every 0.5 hour in the dropwise adding process, and the adding amount of each time is equal;
5) and after the dropwise addition is finished, cooling to 35-45 ℃, adding 3-6 parts of pH regulator to regulate the pH of the emulsion to 5-6, adding 20-30 parts of plasticizer, and uniformly stirring to complete emulsion polymerization to obtain a polyvinyl acetate emulsion adhesive product.
The invention has the beneficial effects that:
1. in the formulation system of the present invention: through acetalization modification of PVA, a six-membered ring is formed between adjacent hydroxyl groups in a molecule, so that the formation of a hydrogen bond is damaged, the mechanical winding among PVA molecules is reduced, and the stability and the water resistance of the emulsion are improved; vinyl acetate and vinyl versatate are copolymerized and modified, and the water resistance of the emulsion is greatly improved by utilizing the hydrophobic property of the vinyl versatate; the residual emulsifier in the polymerization product can influence the water resistance, chemical corrosion resistance and physical and mechanical properties of the adhesive film, the emulsifier molecules in the adhesive film migrate to the surface to cause the surface of the adhesive film to swell when meeting water or being heated to cause 'blooming' and 'whitening', the reactive emulsifier polyoxyethylene vinyl methyl ether is used in the invention, the latex is not condensed due to the molecule migration, and the use amount is proper, so that the reaction activity can be improved, the film forming speed can be accelerated, and the water resistance of the adhesive film can be improved.
2. The emulsion provided by the invention has good weather resistance, heat resistance and wear resistance, especially has excellent water resistance, can realize industrial production, and has the advantages of simple equipment, stable production, safety and environmental protection.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The modified protective colloid solution used in the following examples is a protective colloid solution obtained by modifying polyvinyl alcohol 17-99 through an acetalization reaction, and the preparation method specifically comprises the following steps:
(1) adding 17-99 parts of polyvinyl alcohol and 77 parts of water in parts by weight into a reaction kettle in sequence, heating to 90-95 ℃, continuously stirring, condensing and refluxing until the polyvinyl alcohol and the water are completely dissolved;
(2) cooling the solution to 75-85 ℃, adjusting the pH value of the system to 1.5-2.5 by using hydrochloric acid, adding 5 parts of glyoxal, and reacting for 0.5-2.0h under the condition of heat preservation;
(3) and (3) supplementing water into the solution in the step (2), then adjusting the pH value of the system to 7.0-8.0 by using alkali liquor, cooling and discharging to obtain a modified protective colloid solution with the solid content of 10%.
Example 1
The polyvinyl acetate emulsion adhesive with excellent water resistance of the embodiment comprises the following raw materials in parts by weight: 15 parts of protective colloid, 315 parts of modified protective colloid solution, 150 parts of reaction monomer, 100 parts of modified monomer, 3 parts of initiator, 0.5 part of reactive emulsifier, 20 parts of plasticizer, 3 parts of pH regulator and 300 parts of deionized water.
Specifically, the raw materials used in this example are: the protective colloid is polyvinyl alcohol (degree of polymerization is 500, and degree of alcoholysis is 88%); the reaction monomer is vinyl acetate; the modified monomer is vinyl versatate; the initiator is ammonium persulfate; the reactive emulsifier is polyoxyethylene vinyl methyl ether; the plasticizer is dibutyl phthalate; the pH regulator is sodium acetate.
The preparation method of the polyvinyl acetate emulsion adhesive comprises the following steps:
1) adding 280 parts of deionized water into a three-neck flask, heating to 90 ℃, adding 15 parts of protective colloid under a stirring state, continuously stirring until the protective colloid is completely dissolved, cooling to 60 ℃, and adding 315 parts of modified protective colloid solution for later use;
2) weighing 3 parts of initiator, and dissolving in 20 parts of deionized water for later use; weighing 100 parts of modified monomer and 150 parts of reaction monomer for later use;
3) adding 8 parts of initiator aqueous solution completely dissolved and 0.5 part of reactive emulsifier into the three-neck flask subjected to cooling in the step 1), adding 8 parts of modified monomer and 50 parts of reaction monomer, and performing seed emulsion polymerization at the reaction temperature of 80 ℃ for 35 minutes;
4) keeping the constant temperature of the three-neck flask at 80 ℃, then mixing the remaining modified monomer and reaction monomer, and gradually dropwise adding the mixture into the three-neck flask for emulsion polymerization, wherein the dropwise adding time is 6 hours, and the remaining initiator aqueous solution is added at intervals of 0.5h in the dropwise adding process, and the adding amount is equal each time;
5) and after the dropwise addition is finished, cooling to 35 ℃, adding 3 parts of pH regulator to regulate the pH of the emulsion to 6, adding 20 parts of plasticizer, and uniformly stirring to finish emulsion polymerization to obtain a polyvinyl acetate emulsion adhesive product.
The viscosity, bonding strength and water resistance of the finished emulsion obtained in step 5) were measured, and the results are shown in table 1.
Example 2
The polyvinyl acetate emulsion adhesive with excellent water resistance of the embodiment comprises the following raw materials in parts by weight: 25 parts of protective colloid, 375 parts of modified protective colloid solution, 200 parts of reaction monomer, 150 parts of modified monomer, 8 parts of initiator, 1.5 parts of reactive emulsifier, 30 parts of plasticizer, 6 parts of pH regulator and 350 parts of deionized water.
Specifically, the raw materials used in this example are: the protective colloid is hydroxyethyl cellulose; the reaction monomer is vinyl acetate; the modified monomer is vinyl versatate; the initiator is potassium persulfate; the reactive emulsifier is acrylamide isopropyl sodium sulfonate; the plasticizer is diethyl phthalate; the pH regulator is sodium bicarbonate.
The preparation method of the polyvinyl acetate emulsion adhesive comprises the following steps:
1) adding 320 parts of deionized water into a three-neck flask, heating to 90 ℃, adding 25 parts of protective colloid under a stirring state, continuously stirring until the protective colloid is completely dissolved, cooling to 70 ℃, and adding 375 parts of modified protective colloid solution for later use;
2) weighing 8 parts of initiator, and dissolving the initiator in 30 parts of deionized water for later use; weighing 150 parts of modified monomer and 200 parts of reaction monomer for later use;
3) adding 12 parts of initiator aqueous solution completely dissolved and 1.5 parts of reactive emulsifier into the three-neck flask subjected to cooling in the step 1), then adding 10 parts of modified monomer and 70 parts of reactive monomer, and performing seed emulsion polymerization at the reaction temperature of 85 ℃ for 35 minutes;
4) keeping the constant temperature of the three-neck flask at 85 ℃, then mixing the remaining modified monomer and reaction monomer, and gradually dropwise adding the mixture into the three-neck flask for emulsion polymerization, wherein the dropwise adding time is 5 hours, and the remaining initiator aqueous solution is added at intervals of 0.5h in the dropwise adding process, and the adding amount is equal each time;
5) and after the dropwise addition is finished, cooling to 45 ℃, adding 6 parts of pH regulator to regulate the pH of the emulsion to 6, adding 30 parts of plasticizer, and uniformly stirring to finish emulsion polymerization to obtain the polyvinyl acetate emulsion adhesive product.
The viscosity, bonding strength and water resistance of the finished emulsion obtained in step 5) were measured, and the results are shown in table 1.
Example 3
The polyvinyl acetate emulsion adhesive with excellent water resistance of the embodiment comprises the following raw materials in parts by weight: 25 parts of protective colloid, 315 parts of modified protective colloid solution, 150 parts of reaction monomer, 150 parts of modified monomer, 6 parts of initiator, 1 part of reactive emulsifier, 20 parts of plasticizer, 6 parts of pH regulator and 320 parts of deionized water.
Specifically, the raw materials used in this example are: the protective colloid is polymethyl cellulose; the reaction monomer is vinyl acetate; the modified monomer is vinyl versatate; the initiator is hydrogen peroxide; the reactive emulsifier is polyoxyethylene vinyl methyl ether; the plasticizer is di (2-ethylhexyl) phthalate; the pH regulator is sodium citrate.
The preparation method of the polyvinyl acetate emulsion adhesive comprises the following steps:
1) adding 300 parts of deionized water into a three-neck flask, heating to 90 ℃, adding 25 parts of protective colloid under a stirring state, continuously stirring until the protective colloid is completely dissolved, cooling to 60 ℃, and adding 315 parts of modified protective colloid solution for later use;
2) weighing 6 parts of initiator, and dissolving in 20 parts of deionized water for later use; weighing 150 parts of modified monomer and 150 parts of reaction monomer for later use;
3) adding 10 parts of initiator aqueous solution completely dissolved and 1 part of reactive emulsifier into the three-neck flask subjected to cooling in the step 1), then adding 10 parts of modified monomer and 50 parts of reactive monomer, and performing seed emulsion polymerization at the reaction temperature of 82 ℃ for 30 minutes;
4) keeping the constant temperature of the three-neck flask at 82 ℃, then mixing the remaining modified monomer and reaction monomer, and gradually dropwise adding the mixture into the three-neck flask for emulsion polymerization, wherein the dropwise adding time is 5 hours, and the remaining initiator aqueous solution is added at intervals of 0.5h in the dropwise adding process, and the adding amount is equal each time;
5) and after the dropwise addition is finished, cooling to 40 ℃, adding 6 parts of pH regulator to regulate the pH of the emulsion to 5.5, adding 20 parts of plasticizer, and uniformly stirring to finish emulsion polymerization to obtain a polyvinyl acetate emulsion adhesive product.
The viscosity, bonding strength and water resistance of the finished emulsion obtained in step 5) were measured, and the results are shown in table 1.
Example 4
The polyvinyl acetate emulsion adhesive with excellent water resistance of the embodiment comprises the following raw materials in parts by weight: 20 parts of protective colloid, 340 parts of modified protective colloid solution, 180 parts of reaction monomer, 120 parts of modified monomer, 5 parts of initiator, 1 part of reactive emulsifier, 25 parts of plasticizer, 5 parts of pH regulator and 350 parts of deionized water.
Specifically, the raw materials used in this example are: the protective colloid is polyvinyl alcohol (the polymerization degree is 2400, and the alcoholysis degree is 88%); the reaction monomer is vinyl acetate; the modified monomer is vinyl versatate; the initiator is ammonium persulfate; the reactive emulsifier is polyoxyethylene vinyl methyl ether; the plasticizer is di (2-ethylhexyl) phthalate; the pH regulator is sodium citrate.
The preparation method of the polyvinyl acetate emulsion adhesive comprises the following steps:
1) adding 330 parts of deionized water into a three-neck flask, heating to 90 ℃, adding 20 parts of protective colloid under stirring, continuously stirring until the protective colloid is completely dissolved, cooling to 65 ℃, and adding 340 parts of modified protective colloid solution for later use;
2) weighing 5 parts of initiator, and dissolving the initiator in 20 parts of deionized water for later use; weighing 120 parts of modified monomer and 180 parts of reaction monomer for later use;
3) adding 8 parts of initiator aqueous solution completely dissolved and 1 part of reactive emulsifier into the three-neck flask subjected to cooling in the step 1), and then adding 10 parts of modified monomer and 50 parts of reactive monomer to perform seed emulsion polymerization, wherein the reaction temperature is 80 ℃ and the reaction time is 35 minutes;
4) keeping the constant temperature of the three-neck flask at 80 ℃, then mixing the remaining modified monomer and reaction monomer, and gradually dropwise adding the mixture into the three-neck flask for emulsion polymerization, wherein the dropwise adding time is 6 hours, and the remaining initiator aqueous solution is added at intervals of 0.5h in the dropwise adding process, and the adding amount is equal each time;
5) and after the dropwise addition is finished, cooling to 45 ℃, adding 5 parts of pH regulator to regulate the pH of the emulsion to 5, adding 25 parts of plasticizer, and uniformly stirring to finish emulsion polymerization to obtain the polyvinyl acetate emulsion adhesive product.
The viscosity, bonding strength and water resistance of the finished emulsion obtained in step 5) were measured, and the results are shown in table 1.
Example 5
The polyvinyl acetate emulsion adhesive with excellent water resistance of the embodiment comprises the following raw materials in parts by weight: 25 parts of protective colloid, 375 parts of modified protective colloid solution, 150 parts of reaction monomer, 100 parts of modified monomer, 3 parts of initiator, 1 part of reactive emulsifier, 30 parts of plasticizer, 6 parts of pH regulator and 350 parts of deionized water.
Specifically, the raw materials used in this example are: the protective colloid is polyvinyl alcohol (the polymerization degree is 1700 and the alcoholysis degree is 88%); the reaction monomer is vinyl acetate; the modified monomer is vinyl versatate; the initiator is potassium persulfate; the reactive emulsifier is polyoxyethylene vinyl methyl ether; the plasticizer is dibutyl phthalate; the pH regulator is sodium citrate.
The preparation method of the polyvinyl acetate emulsion adhesive comprises the following steps:
1) adding 320 parts of deionized water into a three-neck flask, heating to 90 ℃, adding 25 parts of protective colloid under a stirring state, continuously stirring until the protective colloid is completely dissolved, cooling to 70 ℃, and adding 375 parts of modified protective colloid solution for later use;
2) weighing 3 parts of initiator, and dissolving in 30 parts of deionized water for later use; weighing 100 parts of modified monomer and 150 parts of reaction monomer for later use;
3) adding 10 parts of initiator aqueous solution completely dissolved and 1 part of reactive emulsifier into the three-neck flask subjected to cooling in the step 1), then adding 10 parts of modified monomer and 60 parts of reactive monomer, and performing seed emulsion polymerization at the reaction temperature of 82 ℃ for 30 minutes;
4) keeping the constant temperature of the three-neck flask at 82 ℃, then mixing the remaining modified monomer and reaction monomer, and gradually dropwise adding the mixture into the three-neck flask for emulsion polymerization, wherein the dropwise adding time is 5 hours, and the remaining initiator aqueous solution is added at intervals of 0.5h in the dropwise adding process, and the adding amount is equal each time;
5) and after the dropwise addition is finished, cooling to 40 ℃, adding 6 parts of pH regulator to regulate the pH of the emulsion to 6, adding 30 parts of plasticizer, and uniformly stirring to finish emulsion polymerization to obtain the polyvinyl acetate emulsion adhesive product.
The viscosity, bonding strength and water resistance of the finished emulsion obtained in step 5) were measured, and the results are shown in table 1.
Example 6
The polyvinyl acetate emulsion adhesive with excellent water resistance of the embodiment comprises the following raw materials in parts by weight: 15 parts of protective colloid, 315 parts of modified protective colloid solution, 170 parts of reaction monomer, 150 parts of modified monomer, 7 parts of initiator, 1.5 parts of reactive emulsifier, 20 parts of plasticizer, 6 parts of pH regulator and 330 parts of deionized water.
Specifically, the raw materials used in this example are: the protective colloid is hydroxyethyl cellulose; the reaction monomer is vinyl acetate; the modified monomer is vinyl versatate; the initiator is ammonium persulfate; the reactive emulsifier is acrylamide isopropyl sodium sulfonate; the plasticizer is dibutyl phthalate; the pH regulator is sodium acetate.
The preparation method of the polyvinyl acetate emulsion adhesive comprises the following steps:
1) adding 300 parts of deionized water into a three-neck flask, heating to 90 ℃, adding 15 parts of protective colloid under stirring, continuously stirring until the protective colloid is completely dissolved, cooling to 60 ℃, and adding 315 parts of modified protective colloid solution for later use;
2) weighing 7 parts of initiator, and dissolving in 30 parts of deionized water for later use; weighing 150 parts of modified monomer and 170 parts of reaction monomer for later use;
3) adding 10 parts of initiator aqueous solution completely dissolved and 1.5 parts of reactive emulsifier into the three-neck flask subjected to cooling in the step 1), then adding 10 parts of modified monomer and 70 parts of reactive monomer, and performing seed emulsion polymerization at the reaction temperature of 80 ℃ for 35 minutes;
4) keeping the constant temperature of the three-neck flask at 80 ℃, then mixing the remaining modified monomer and reaction monomer, and gradually dropwise adding the mixture into the three-neck flask for emulsion polymerization, wherein the dropwise adding time is 6 hours, and the remaining initiator aqueous solution is added at intervals of 0.5h in the dropwise adding process, and the adding amount is equal each time;
5) and after the dropwise addition is finished, cooling to 40 ℃, adding 6 parts of pH regulator to regulate the pH of the emulsion to 6, adding 20 parts of plasticizer, and uniformly stirring to finish emulsion polymerization to obtain the polyvinyl acetate emulsion adhesive product.
The viscosity, bonding strength and water resistance of the finished emulsion obtained in step 5) were measured, and the results are shown in table 1.
The white latex provided in each of the above examples was tested for viscosity and adhesion strength and water resistance according to the test methods in GB-T11175-2002 synthetic resin emulsion test method.
The method for measuring the bonding strength comprises the following steps: 2 birch boards of 2.5cm multiplied by 2.5cm are taken, the surfaces of the boards are cleaned to be clean, and a line is drawn at a position 0.5cm away from one end of each board. Taking 0.0500-0.0520g of finished emulsion, uniformly coating the emulsion on a flat front panel with the other end of 2.5cm multiplied by 2.0cm, not coating the emulsion on the other panel, lapping 2 blocks, placing the panel in a clamp with fixed pressure, and standing the panel for 24 hours at room temperature. And (4) removing the pressure, putting the bonded wood board on a press machine to be pressed open, measuring the reading and recording.
The test method of the water resistance is as follows: soaking the dried bonding wood chips in water at 80 ℃, and measuring the glue opening time; the number of test repetitions was 5.
TABLE 1 test results of examples
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A polyvinyl acetate emulsion adhesive with excellent water resistance is characterized in that: the adhesive comprises the following raw materials in parts by weight: 15-25 parts of protective colloid, 315-375 parts of modified protective colloid solution, 150-200 parts of reaction monomer, 100-150 parts of modified monomer, 3-8 parts of initiator, 0.5-1.5 parts of reactive emulsifier, 20-30 parts of plasticizer, 3-6 parts of pH regulator and 300-350 parts of deionized water.
2. The polyvinyl acetate emulsion adhesive excellent in water resistance according to claim 1, characterized in that: the modified protective colloid solution is a protective colloid solution obtained by modifying polyvinyl alcohol 17-99 through an acetal reaction, and the solid content of the solution is 8-16%.
3. The polyvinyl acetate emulsion adhesive excellent in water resistance according to claim 1, characterized in that: the protective colloid is at least one of hydroxyethyl cellulose, polymethyl cellulose and polyvinyl alcohol; the polymerization degree of the polyvinyl alcohol is 500-2000, and the alcoholysis degree of the polyvinyl alcohol is 88-99%.
4. The polyvinyl acetate emulsion adhesive excellent in water resistance according to claim 1, characterized in that: the reaction monomer is vinyl acetate.
5. The polyvinyl acetate emulsion adhesive excellent in water resistance according to claim 1, characterized in that: the modified monomer is vinyl versatate.
6. The polyvinyl acetate emulsion adhesive excellent in water resistance according to claim 1, characterized in that: the initiator is at least one of ammonium persulfate, hydrogen peroxide and potassium persulfate.
7. The polyvinyl acetate emulsion adhesive excellent in water resistance according to claim 1, characterized in that: the reactive emulsifier is at least one of polyoxyethylene vinyl methyl ether, acrylamide isopropyl sodium sulfonate and double-bond-containing alcohol ether sulfosuccinate sodium salt.
8. The polyvinyl acetate emulsion adhesive excellent in water resistance according to claim 1, characterized in that: the plasticizer is at least one of dibutyl phthalate, diethyl phthalate and di (2-ethylhexyl) phthalate.
9. The polyvinyl acetate emulsion adhesive excellent in water resistance according to claim 1, characterized in that: the pH regulator is at least one of sodium acetate, sodium bicarbonate and sodium citrate.
10. A method for preparing the polyvinyl acetate emulsion adhesive with excellent water resistance according to any one of claims 1 to 9, which is characterized by comprising the following steps:
1) adding 280-320 parts of deionized water into a three-neck flask, heating to 80-90 ℃, adding 15-25 parts of protective colloid under a stirring state, continuously stirring until the protective colloid is completely dissolved, cooling to 60-70 ℃, and adding 315-375 parts of modified protective colloid solution for later use;
2) weighing 3-8 parts of initiator, and dissolving in 20-30 parts of deionized water for later use; weighing 100-150 parts of modified monomer and 150-200 parts of reaction monomer for later use;
3) adding 8-12 parts of initiator aqueous solution completely dissolved and 0.5-1.5 parts of reactive emulsifier into the three-neck flask subjected to cooling in the step 1), then adding 8-10 parts of modified monomer and 50-70 parts of reactive monomer, and performing seed emulsion polymerization at the reaction temperature of 75-85 ℃ for 25-35 minutes;
4) keeping the constant temperature of the three-neck flask at 75-85 ℃, then mixing the remaining modified monomer and reaction monomer, gradually dropwise adding the mixture into the three-neck flask for emulsion polymerization, wherein the dropwise adding time is 4-6 hours, and adding the remaining initiator aqueous solution once every 0.5 hour in the dropwise adding process, and the adding amount of each time is equal;
5) and after the dropwise addition is finished, cooling to 35-45 ℃, adding 3-6 parts of pH regulator to regulate the pH of the emulsion to 5-6, adding 20-30 parts of plasticizer, and uniformly stirring to complete emulsion polymerization to obtain a polyvinyl acetate emulsion adhesive product.
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| CN (1) | CN112322230A (en) |
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| CN113930192A (en) * | 2021-10-26 | 2022-01-14 | 汇胜包装科技有限公司 | Large-diameter paper tube adhesive and preparation method thereof |
| CN113943392A (en) * | 2021-10-01 | 2022-01-18 | 顶立新材料科技有限公司 | Water-resistant cold-resistant polyvinyl acetate emulsion and preparation method thereof |
| CN115819808A (en) * | 2023-01-10 | 2023-03-21 | 安徽皖维花山新材料有限责任公司 | Water-resistant redispersible latex powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174013A (en) * | 2021-05-14 | 2021-07-27 | 深圳市中仁能源科技有限公司 | Cationic vinyl acetate emulsion for glass fiber felt yarn and preparation method thereof |
| CN113943392A (en) * | 2021-10-01 | 2022-01-18 | 顶立新材料科技有限公司 | Water-resistant cold-resistant polyvinyl acetate emulsion and preparation method thereof |
| CN113930192A (en) * | 2021-10-26 | 2022-01-14 | 汇胜包装科技有限公司 | Large-diameter paper tube adhesive and preparation method thereof |
| CN113930192B (en) * | 2021-10-26 | 2023-03-31 | 汇胜包装科技有限公司 | Large-diameter paper tube adhesive and preparation method thereof |
| CN115819808A (en) * | 2023-01-10 | 2023-03-21 | 安徽皖维花山新材料有限责任公司 | Water-resistant redispersible latex powder and preparation method thereof |
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