CN112708023A - Vinyl acetate-ethylene copolymer emulsion having excellent color developability and flame retardancy - Google Patents
Vinyl acetate-ethylene copolymer emulsion having excellent color developability and flame retardancy Download PDFInfo
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- CN112708023A CN112708023A CN201911019276.3A CN201911019276A CN112708023A CN 112708023 A CN112708023 A CN 112708023A CN 201911019276 A CN201911019276 A CN 201911019276A CN 112708023 A CN112708023 A CN 112708023A
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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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
Abstract
The invention belongs to the technical field of vinyl acetate copolymers, and particularly relates to a vinyl acetate-ethylene copolymer emulsion with excellent color development and flame retardance. The vinyl acetate-ethylene copolymer emulsion is prepared from raw materials including a monomer, an emulsifying system, a redox system and water, wherein the monomer comprises vinyl phosphoric acid and vinyl dimethyl phosphate. The vinyl acetate-ethylene copolymer emulsion has excellent color development and good flame retardant effect.
Description
Technical Field
The invention belongs to the technical field of polyvinyl acetate copolymers, and particularly relates to a vinyl acetate-ethylene copolymer emulsion with excellent color development and flame retardance.
Background
After the vinyl acetate-ethylene copolymer emulsion (also known as VAE emulsion or EVA emulsion) enters China from the end of the last 80 th century, the vinyl acetate-ethylene copolymer emulsion rapidly occupies the market of polyvinyl acetate emulsion, and the annual output continuously increases at a speed of 8-10%. The VAE emulsion is a polymer emulsion prepared by taking vinyl acetate and ethylene as main raw materials and adopting an emulsion polymerization mode (research on high-solid content vinyl acetate-ethylene copolymer emulsion, Wuhuiziang, adhesive bonding, No. 24, No. 4, page 15, left column, No. 1, lines 1-3, page 15, left column, No. 2, lines 1-3, published 2003, 12-31, modification and application of EVA emulsion, Zhang Xinya et al, rubber industry, No. 50, No. 6, page 379, abstract, lines 1-3, and published 2003, 12-31).
The vinyl acetate-ethylene copolymer emulsion is excellent in flexibility, toughness, stress cracking resistance and transparency. Compared with PVAc emulsion, the vinyl acetate-ethylene copolymer emulsion has lower film forming temperature and glass transition temperature, and good freeze-thaw resistance, acid and alkali resistance and storage stability. Meanwhile, the vinyl acetate-ethylene copolymer emulsion has good stability to oxygen, ozone and ultraviolet rays. The creep resistance of the vinyl acetate-ethylene copolymer emulsion adhesive film is better than that of a Polyacrylate (PA) emulsion adhesive film. The vinyl acetate-ethylene copolymer emulsion has low surface tension, good wettability and adhesiveness, and can be used for preparing adhesives with high adhesive strength. The vinyl acetate-ethylene copolymer emulsion adhesive film has better high temperature resistance (modification and application of EVA emulsion, Zhang Xinya et al, rubber industry, 50 th volume 6 of 2003, 3 rd page left column, 1 st section, 2-3 lines, 379 th left column, 2 nd section, 4-6 lines, 379 th left column, 3 rd section, 4-7 lines, 379 th left column, 4 th section, 1-2 lines, 379 th left column, 5 th sections, 1-3 lines and 379 th right column, 1 st section, 1-2 lines, 2003, 12 months and 31 days). Therefore, the vinyl acetate-ethylene copolymer emulsion is widely used in the fields of coatings, adhesives, cement modifiers, conductive materials, construction, packaging, textiles, automobiles, electronic components, and the like ("modification and application of EVA emulsion", zhangxinya, and the like, rubber industry, vol. 50, No. 6, page 379, left column, paragraph 2, lines 6 to 7, publication day 2003, 12 and 31 days in 2003; "research on the field of application of current vinyl acetate-ethylene (VAE) emulsion", china chemical trade, 10 th year in 2013, right column, page 81, 3, lines 1 to 4, and publication day 2013, 10 and 31 days in 2013).
However, the color development property (i.e. the compatibility of the emulsion and the color paste) of the existing vinyl acetate-ethylene copolymer emulsion is not good, and the color paste and the vinyl acetate-ethylene copolymer emulsion can form obvious color difference after being mixed and dried; and the existing vinyl acetate-ethylene copolymer emulsion has poor flame retardant property.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a vinyl acetate-ethylene copolymer emulsion having excellent color developability and flame retardancy.
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 monomers, an emulsifying system, a redox system and water, wherein the monomers include vinyl phosphoric acid and vinyl dimethyl phosphate.
The vinyl acetate-ethylene copolymer emulsion prepared from the raw materials comprising monomers (the monomers comprise vinyl phosphoric acid and vinyl dimethyl phosphate), an emulsifying system, an oxidation-reduction system and water has excellent color development, and the color paste and the vinyl acetate-ethylene copolymer emulsion are mixed and then are dried without forming obvious color difference; and the prepared vinyl acetate-ethylene copolymer emulsion has excellent flame retardance.
In order to further improve the color development and the flame retardance of the vinyl acetate-ethylene copolymer emulsion, the mass ratio of the vinyl dimethyl phosphate to the vinyl phosphoric acid is 2:1-5: 1.
The inventor unexpectedly discovers in the research process that the mass ratio of the vinyl dimethyl phosphate to the vinyl phosphoric acid is 2:1-5:1, so that the color development and the flame retardant property of the vinyl acetate-ethylene copolymer emulsion can be obviously improved.
Further, the monomers also include vinyl acetate and ethylene.
Further, the monomer comprises, by mass, 15-50 parts of vinyl acetate, 5-15 parts of ethylene, 10-30 parts of vinyl dimethyl phosphate and 5-10 parts of vinyl phosphoric acid.
Further, the redox system includes an oxidizing agent and a reducing agent.
Further, the mass ratio of the oxidizing agent to the reducing agent is 0.05-3: 0.05-3.
Further, the oxidizing agent comprises an oil-soluble oxidizing agent.
In the research process, the inventor finds that if the selection of the oxidant is not proper, the color development of the vinyl acetate-ethylene copolymer emulsion is poor, the flame retardant effect is poor, and the content of filter residue is too much.
Further, the oil-soluble oxidizing agent includes tert-butyl hydroperoxide or tert-butyl peroxybenzoate.
Further, the reducing agent comprises potassium tartrate, sodium erythorbate, vitamin C or zinc formaldehyde sulfoxylate.
Further, the reducing agent comprises sodium erythorbate or vitamin C.
Further, the emulsifying system comprises a protective colloid and an emulsifier.
Further, the protective colloid comprises one or more of polyvinyl alcohol and hydroxyethyl cellulose.
Further, the protective colloid comprises polyvinyl alcohol.
Further, the emulsifier is a nonionic emulsifier.
Further, the nonionic emulsifier comprises one or more of nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and isomeric tridecyl polyoxyethylene ether.
Further, the nonionic emulsifier comprises fatty alcohol-polyoxyethylene ether or isomeric tridecyl polyoxyethylene ether.
Further, the mass ratio of the protective colloid to the emulsifier is 0.5-4.
Further, the water is deionized water.
Further, the vinyl acetate-ethylene copolymer emulsion is prepared from raw materials including 15-50 parts of vinyl acetate, 5-15 parts of ethylene, 5-10 parts of vinyl phosphoric acid, 10-30 parts of vinyl dimethyl phosphate, 0.8-5 parts of an emulsifying system, 0.05-0.3 part of an oxidizing agent, 0.05-0.3 part of a reducing agent and 45-60 parts of water.
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
Preparation of oxidizing and reducing agent solutions: preparing an oxidant solution in an oxidant tank, and preparing a reducing agent solution in a reducing agent tank;
preparation of protective colloid solution: sequentially adding water and protective colloid into a dissolving tank under the stirring state, heating to 80-95 ℃, preserving heat for 60-120min at the temperature, and then cooling to 30-60 ℃ for later use;
B. feeding production
Under the stirring state, adding water, protective colloid solution and emulsifier into a reaction kettle, uniformly stirring, adding a mixed monomer of vinyl acetate, vinyl phosphoric acid and vinyl dimethyl phosphate accounting for 30-60% of the total monomer amount, and then heating and boosting pressure;
when the temperature is raised to 50-60 ℃ and the pressure reaches 2.0-3.5MPa, pumping a reducing agent accounting for 10-40% of the total amount of the reducing agent into the reaction kettle, then simultaneously adding an oxidizing agent and the reducing agent into the reaction kettle at the speed of 5.0-8.0kg/min, and when the temperature in the reaction kettle reaches 55-65 ℃, reducing the speed of the oxidizing agent and the reducing agent 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 residual mixed monomer of vinyl acetate, vinyl phosphoric acid and vinyl dimethyl phosphate is added for 60-90min, and the ethylene is closed after the mixed monomer is added;
adding the rest of the oxidant and the reducer in 15-45min, then reducing to normal pressure, cooling to normal temperature, filtering, and discharging to obtain the final product.
The invention also aims to protect the application of the monomer containing the vinyl phosphoric acid and the vinyl dimethyl phosphate in improving the color development and the flame retardance of the vinyl acetate-ethylene copolymer emulsion.
In the invention, the color development refers to the compatibility of the emulsion and the color paste.
In the present invention, the flame retardancy refers to the property of a substance to significantly delay the spread of flame.
Further, the mass ratio of the vinyl dimethyl phosphate to the vinyl phosphoric acid is 2:1-5: 1.
Further, the monomers also include vinyl acetate and ethylene.
Further, the mass ratio of the vinyl acetate to the ethylene to the vinyl phosphoric acid to the vinyl dimethyl phosphate is 15-50:5-15:5-10: 10-30.
The invention has the beneficial effects that:
the vinyl acetate-ethylene copolymer emulsion has excellent color development, and after being mixed with the vinyl acetate-ethylene copolymer emulsion, the color paste cannot form obvious color difference after being dried.
The flame retardant property of the vinyl acetate-ethylene copolymer emulsion is obviously improved.
The vinyl acetate-ethylene copolymer emulsion of the present invention has a low residue content.
The vinyl acetate-ethylene copolymer emulsion has improved color development performance and flame retardance, and has no reduced performance in other aspects such as bonding performance.
The invention solves the problem of poor flame retardant property of the existing vinyl acetate-ethylene copolymer emulsion.
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. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
The vinyl acetate-ethylene copolymer emulsion is prepared from the following raw materials in parts by mass:
monomer (b): 15 parts of vinyl acetate, 10 parts of ethylene, 10 parts of vinyl phosphoric acid and 20 parts of vinyl dimethyl phosphate;
0.4 part of non-ionic emulsifier 15-s-40,
3 parts of protective colloid (wherein 0.5 part of the protective colloid is PVA0588, 1.5 parts of the protective colloid is PVA1788, and 1 part of the protective colloid is PVA1799),
0.1 part of oxidant tert-butyl hydroperoxide,
0.1 part of reducing agent vitamin C,
and 55 parts of deionized water.
The vinyl acetate-ethylene copolymer emulsion is prepared according to the following steps:
A. raw material preparation
Preparation of oxidizing and reducing agent solutions: 10 parts of water are added into an oxidizing agent tank and a reducing agent tank respectively, 0.1 part of oxidizing agent tert-butyl hydroperoxide is added into the oxidizing agent tank, 0.1 part of reducing agent vitamin C is added into the reducing agent tank, and the mixture is stirred to be dissolved.
Preparation of protective colloid solution: under the stirring state, 30 parts of water and 0.5 part of PVA0588, 1.5 parts of PVA1788 and 1 part of PVA1799 protective colloid are sequentially added into a dissolving tank, then the temperature is raised to 80-95 ℃, the temperature is kept for 60-120min at the temperature, and then the temperature is lowered to 30-60 ℃ for standby.
B. Feeding production
Under the stirring state, adding water, dissolved protective colloid solution and non-ionic emulsifier 15-S-40 into a reaction kettle, uniformly stirring, adding mixed monomers of vinyl acetate, vinyl phosphoric acid and vinyl dimethyl phosphate accounting for 50% of the total amount of the monomers, and then heating and boosting pressure;
when the temperature is raised to 55 ℃ and the pressure reaches 3.0MPa, pumping a reducing agent accounting for 10-40% of the total amount of the reducing agent into the reaction kettle, then simultaneously adding an oxidizing agent and the reducing agent into the reaction kettle at the speed of 5.0kg/min, and when the temperature in the reaction kettle reaches 60 ℃, reducing the speed of the oxidizing agent and the reducing agent to 1.5 kg/min;
when the temperature in the kettle reaches 80 ℃, the ethylene pressure is increased to 5.8MPa, then the residual mixed monomer of vinyl acetate, vinyl phosphoric acid and vinyl dimethyl phosphate is added within 90min, and the ethylene is closed after the mixed monomer is added;
adding the rest of the oxidant and the reducer for 15-45min, then reducing to normal pressure, cooling to normal temperature, filtering, discharging to obtain the vinyl acetate-ethylene copolymer emulsion.
Comparative example 1
The vinyl acetate-ethylene copolymer emulsion is prepared from the following raw materials:
40 parts of vinyl acetate, 15 parts of ethylene, 0.4 part of non-ionic emulsifier 15-s-40, 3 parts of protective colloid (wherein 0.5 part of PVA0588, 1.5 parts of PVA1788 and 1 part of PVA1799), 0.1 part of oxidant tert-butyl hydroperoxide, 0.1 part of reducing agent vitamin C and 55 parts of deionized water; all in parts by mass.
The vinyl acetate-ethylene copolymer emulsion is prepared by the following steps:
A. raw material preparation
Preparation of oxidizing and reducing agent solutions: 10 parts of water are added into an oxidizing agent tank and a reducing agent tank respectively, 0.1 part of oxidizing agent tert-butyl hydroperoxide is added into the oxidizing agent tank, 0.1 part of reducing agent vitamin C is added into the reducing agent tank, and the mixture is stirred to be dissolved.
Preparation of protective colloid solution: under the stirring state, adding 30 parts of water and 0.5 part of PVA0588, 1.5 parts of PVA1788 and 1 part of PVA1799 protective colloid into a dissolving tank in turn, then heating to 80-95 ℃, preserving heat for 60-120min at the temperature, and cooling to 30-60 ℃ for later use.
B. Feeding production
Under the stirring state, adding water, dissolved protective colloid solution and non-ionic emulsifier 15-S-40 into a reaction kettle, uniformly stirring, adding vinyl acetate monomer accounting for 50% of the total monomer amount, and then heating and boosting pressure; when the temperature is raised to 55 ℃ and the pressure reaches 3.0MPa, pumping a reducing agent accounting for 10-40% of the total amount of the reducing agent into the reaction kettle, then simultaneously adding an oxidizing agent and the reducing agent into the reaction kettle at the speed of 5.0kg/min, and when the temperature in the reaction kettle reaches 60 ℃, reducing the speed of the oxidizing agent and the reducing agent to 1.5 kg/min;
when the temperature in the kettle reaches 80 ℃, the ethylene pressure is increased to 5.8MPa, then the residual vinyl acetate monomer is added within 90min, and the ethylene is closed after the mixed monomer is added;
and (3) finishing adding the rest oxidant and the rest reducer at a constant speed within 15-45min, then reducing to normal pressure, reducing to normal temperature, filtering, and discharging to obtain the vinyl acetate-ethylene copolymer emulsion.
Comparative example 2
The vinyl acetate-ethylene copolymer emulsion is prepared from the following raw materials:
20 parts of vinyl acetate, 6 parts of ethylene, 30 parts of vinyl dimethyl phosphate, 0.4 part of non-ionic emulsifier 15-s-40, 3 parts of protective colloid (wherein 0.5 part of PVA0588, 1.5 parts of PVA1788 and 1 part of PVA1799), 0.1 part of oxidant tert-butyl hydroperoxide, 0.1 part of reducing agent vitamin C and 55 parts of deionized water; all in parts by mass.
The vinyl acetate-ethylene copolymer emulsion is prepared by the following steps:
A. raw material preparation
Preparation of oxidizing and reducing agent solutions: 10 parts of water are added into an oxidizing agent tank and a reducing agent tank respectively, 0.1 part of oxidizing agent tert-butyl hydroperoxide is added into the oxidizing agent tank, 0.1 part of reducing agent vitamin C is added into the reducing agent tank, and the mixture is stirred to be dissolved.
Preparation of protective colloid solution: under the stirring state, 30 parts of water and 0.5 part of PVA0588, 1.5 parts of PVA1788 and 1 part of PVA1799 protective colloid are sequentially added into a dissolving tank, then the temperature is raised to 80-95 ℃, the temperature is kept for 60-120min at the temperature, and then the temperature is lowered to 30-60 ℃ for standby.
B. Feeding production
Under the stirring state, adding water, dissolved protective colloid solution and non-ionic emulsifier 15-S-40 into a reaction kettle, uniformly stirring, adding a mixed monomer of vinyl acetate and vinyl dimethyl phosphate accounting for 50% of the total monomer amount, and then heating and boosting pressure;
when the temperature is raised to 55 ℃ and the pressure reaches 2.0MPa, pumping a reducing agent accounting for 10-40% of the total amount of the reducing agent into the reaction kettle, then simultaneously adding an oxidizing agent and the reducing agent into the reaction kettle at the speed of 5.0kg/min, and when the temperature in the reaction kettle reaches 60 ℃, reducing the speed of the oxidizing agent and the reducing agent to 1.5 kg/min;
when the temperature in the kettle reaches 80 ℃, the ethylene pressure is increased to 5.8MPa, then the residual mixed monomer of vinyl acetate and vinyl dimethyl phosphate is added within 90min, and the ethylene is closed after the mixed monomer is added;
and (3) finishing adding the rest oxidant and the rest reducer at a constant speed within 15-45min, then reducing to normal pressure, reducing to normal temperature, filtering, and discharging to obtain the vinyl acetate-ethylene copolymer emulsion.
Comparative example 3
The vinyl acetate-ethylene copolymer emulsion is prepared from the following raw materials in parts by mass:
monomer (b): 15 parts of vinyl acetate, 10 parts of ethylene, 10 parts of vinyl phosphoric acid and 20 parts of vinyl dimethyl phosphate;
0.4 part of non-ionic emulsifier 15-s-40,
3 parts of protective colloid (wherein 0.5 part of the protective colloid is PVA0588, 1.5 parts of the protective colloid is PVA1788, and 1 part of the protective colloid is PVA1799),
0.1 part of oxidant hydrogen peroxide,
0.1 part of reducing agent vitamin C,
and 55 parts of deionized water.
The vinyl acetate-ethylene copolymer emulsion is prepared according to the following steps:
A. raw material preparation
Preparation of oxidizing and reducing agent solutions: 10 parts of water are respectively added into an oxidant tank and a reducing agent tank, 0.1 part of hydrogen peroxide is added into the oxidant tank, 0.1 part of reducing agent vitamin C is added into the reducing agent tank, and the mixture is stirred to be dissolved.
Preparation of protective colloid solution: under the stirring state, 30 parts of water and 0.5 part of PVA0588, 1.5 parts of PVA1788 and 1 part of PVA1799 protective colloid are sequentially added into a dissolving tank, then the temperature is raised to 80-95 ℃, the temperature is kept for 60-120min at the temperature, and then the temperature is lowered to 30-60 ℃ for standby.
B. Feeding production
Under the stirring state, adding water, dissolved protective colloid solution and non-ionic emulsifier 15-S-40 into a reaction kettle, uniformly stirring, adding mixed monomers of vinyl acetate, vinyl phosphoric acid and vinyl dimethyl phosphate accounting for 50% of the total amount of the monomers, and then heating and boosting pressure;
when the temperature is raised to 55 ℃ and the pressure reaches 3.0MPa, pumping a reducing agent accounting for 10-40% of the total amount of the reducing agent into the reaction kettle, then simultaneously adding an oxidizing agent and the reducing agent into the reaction kettle at the speed of 5.0kg/min, and when the temperature in the reaction kettle reaches 60 ℃, reducing the speed of the oxidizing agent and the reducing agent to 1.5 kg/min;
when the temperature in the kettle reaches 80 ℃, the ethylene pressure is increased to 5.8MPa, then the residual mixed monomer of vinyl acetate, vinyl phosphoric acid and vinyl dimethyl phosphate is added within 90min, and the ethylene is closed after the mixed monomer is added;
adding the rest of the oxidant and the reducer for 15-45min, then reducing to normal pressure, cooling to normal temperature, filtering, discharging to obtain the vinyl acetate-ethylene copolymer emulsion.
Performance detection
The appearance, solid content, viscosity, adhesive strength, residue content, color developability, and Limiting Oxygen Index (LOI) of the ethylene-vinyl acetate-ethylene copolymer emulsions prepared in example 1 and comparative examples 1 to 3 were as shown in table 1;
the appearance detection method comprises the following steps: and (4) carrying out visual observation.
The solid content detection method comprises the following steps: the solid content of the sample is measured by a drying weight reduction method at a certain temperature, and the solid content is calculated according to the following formula:
in the formula: m is0Weighing the bottle mass, g; m is1-sample before drying plus the mass of the weighing flask, g; m is2The dried sample is weighed into a weighing bottle, g.
The viscosity detection method comprises the following steps: keeping the temperature of the sample at 25 ℃ for 1 hour, and measuring the viscosity of the emulsion by using a Brookfield viscometer, selecting a No. 3 rotor and 60 revolutions per minute;
the detection method of the bonding strength comprises the following steps: respectively coating the fully stirred samples on the adhesive surfaces of the two test pieces, wherein the adhesive area is 25mm multiplied by 25mm, and the adhesive amount is 100g/m2. Laminating the test pieces to obtain a sample, laminating for no more than 10min, applying pressure of 0.49-0.98mPa to the adhesive surface at room temperature of 23 + -2 deg.C and relative humidity of 60-70%, and assemblingFor 24h, the pressure was released and left for 48h under the same ambient conditions. Placing the prepared sample in a clamp of a testing machine, and enabling the applied forces to be parallel to each other; the moving speed of the sample holder is 5 +/-1 mm/min, a testing machine is started, and the breaking strength of the sample when the glued joint part is damaged by force is recorded;
the detection method of the Limiting Oxygen Index (LOI) comprises the following steps: candle burning test method;
the detection method of the filter residue content comprises the following steps: weighing about 100.0g of sample, pouring the sample into a 120-mesh sample sieve with constant weight, washing with distilled water until the distilled water is not turbid, putting into an oven, and drying at 135 +/-2 ℃ until the weight is constant (about 2 h). Taken out, cooled to room temperature in a dryer and weighed. The residue was calculated as follows:
in the formula: m is0-sample sieve mass, g; m is1-mass of sample plus sizing screen, g, before drying; m is2The mass of the dried sample plus the sizing screen, g;
the color developability detection method comprises the following steps: the color-developing property is the compatibility of color paste and emulsion, 10g of color paste is added into 100g of emulsion by adopting a finger grinding method, the mixture is uniformly coated on a cement board or a glass board, when the mixture is about to be condensed, the surface layer part of the coating is ground by fingers, and whether obvious color difference exists or not is observed after the mixture is dried (visual inspection).
Table 1 results of performance testing
| Performance index | Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Appearance of the product | White emulsion | White emulsion | White emulsion | White emulsion |
| Solids content/% | 55.0 | 54.8 | 54.5 | 53.4 |
| viscosity/(mPa.s) | 960 | 870 | 920 | 420 |
| Adhesive strength/MPa | 8.8 | 8.2 | 8.4 | 6.1 |
| Amount of filter residue/%) | 0.015 | 0.026 | 0.021 | 0.23 |
| Color development property | Good taste | Difference (D) | Difference (D) | Difference (D) |
| Limiting Oxygen Index (LOI) | 27.6 | 20.2 | 27.8 | 20.7 |
As is clear from Table 1, the vinyl acetate-ethylene copolymer emulsion of example 1 is excellent in color developability and excellent in flame retardancy. Therefore, the vinyl acetate-ethylene copolymer emulsion disclosed by the invention is excellent in color development and good in flame retardant property.
As can be seen from Table 1, the vinyl acetate-ethylene copolymer emulsion of example 1 is significantly improved in color development and flame retardancy as compared with comparative example 1, and the adhesion strength is similar. Thus, the vinyl acetate-ethylene copolymer emulsion of the present invention has improved color developability and flame retardancy without degrading the properties such as adhesive strength.
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 (16)
1. The vinyl acetate-ethylene copolymer emulsion is characterized by being prepared from raw materials including monomers, an emulsifying system, a redox system and water, wherein the monomers include vinyl phosphoric acid and vinyl dimethyl phosphate.
2. The vinyl acetate-ethylene copolymer emulsion according to claim 1, wherein the mass ratio of dimethyl vinylphosphate to vinylphosphoric acid is 2:1 to 5: 1.
3. The vinyl acetate-ethylene copolymer emulsion according to claim 1 or 2, wherein the monomers further comprise vinyl acetate and ethylene.
4. The vinyl acetate-ethylene copolymer emulsion according to claim 3, wherein the monomer comprises, in parts by mass, 15 to 50 parts of vinyl acetate, 5 to 15 parts of ethylene, 5 to 10 parts of vinyl phosphoric acid, and 10 to 30 parts of dimethyl vinyl phosphate.
5. The vinyl acetate-ethylene copolymer emulsion according to any of claims 1 to 4, wherein the redox system comprises an oxidizing agent and a reducing agent.
6. The vinyl acetate-ethylene copolymer emulsion according to claim 5, wherein the mass ratio of the oxidizing agent to the reducing agent is 0.05-3: 0.05-3.
7. The vinyl acetate-ethylene copolymer emulsion according to claim 5 or 6, wherein the oxidizing agent comprises an oil-soluble oxidizing agent.
8. The vinyl acetate-ethylene copolymer emulsion according to claim 7, wherein the oil-soluble oxidizing agent comprises t-butyl hydroperoxide or t-butyl peroxybenzoate.
9. The vinyl acetate-ethylene copolymer emulsion according to claim 7 or 8, wherein the reducing agent comprises potassium tartrate, sodium erythorbate, ascorbic acid, or zinc formaldehyde sulfoxylate.
10. The vinyl acetate-ethylene copolymer emulsion of claim 9 wherein the reducing agent comprises sodium erythorbate or vitamin C.
11. The vinyl acetate-ethylene copolymer emulsion according to any one of claims 1 to 10, which is prepared from raw materials comprising 15 to 50 parts of vinyl acetate, 5 to 15 parts of ethylene, 5 to 10 parts of vinyl phosphoric acid, 10 to 30 parts of dimethyl vinyl phosphate, 0.8 to 5 parts of an emulsifying system, 0.05 to 0.3 part of an oxidizing agent, 0.05 to 0.3 part of a reducing agent and 45 to 60 parts of water.
12. The method for preparing a vinyl acetate-ethylene copolymer emulsion according to any one of claims 1 to 11, comprising the steps of:
A. raw material preparation
Preparation of oxidizing and reducing agent solutions: preparing an oxidant solution in an oxidant tank, and preparing a reducing agent solution in a reducing agent tank;
preparation of protective colloid solution: sequentially adding water and protective colloid into a dissolving tank under the stirring state, heating to 80-95 ℃, preserving heat for 60-120min at the temperature, and then cooling to 30-60 ℃ for later use;
B. feeding production
Under the stirring state, adding water, protective colloid solution and emulsifier into a reaction kettle, uniformly stirring, adding a mixed monomer of vinyl acetate, vinyl phosphoric acid and vinyl dimethyl phosphate, wherein the total amount of the mixed monomer is 30-60% of the total amount of the monomers, and then heating and boosting the pressure;
when the temperature is raised to 50-60 ℃ and the pressure reaches 2.0-3.5MPa, pumping a reducing agent accounting for 10-40% of the total amount of the reducing agent into the reaction kettle, then simultaneously adding an oxidizing agent and the reducing agent into the reaction kettle at the speed of 5.0-8.0kg/min, and when the temperature in the reaction kettle reaches 55-65 ℃, reducing the speed of the oxidizing agent and the reducing agent 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 residual mixed monomer of vinyl acetate, vinyl phosphoric acid and vinyl dimethyl phosphate is added for 60-90min, and the ethylene is closed after the mixed monomer is added;
adding the rest of the oxidant and the reducer in 15-45min, then reducing to normal pressure, cooling to normal temperature, filtering, and discharging to obtain the final product.
13. The use of monomers comprising vinyl phosphoric acid and dimethyl vinyl phosphate for improving the color development and flame retardancy of vinyl acetate-ethylene copolymer emulsions.
14. Use according to claim 13, wherein the mass ratio of dimethyl vinylphosphate to vinylphosphonic acid is from 2:1 to 5: 1.
15. Use according to claim 13 or 14, wherein the monomers further comprise vinyl acetate and ethylene.
16. The use of claim 15, wherein the mass ratio of vinyl acetate, ethylene, vinyl phosphoric acid and dimethyl vinyl phosphate is 15-50:5-15:5-10: 10-30.
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