CN113493536B - Vinyl acetate-ethylene copolymer emulsion for redispersible emulsion powder - Google Patents
Vinyl acetate-ethylene copolymer emulsion for redispersible emulsion powder Download PDFInfo
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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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2623—Polyvinylalcohols; Polyvinylacetates
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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
- C08F2/00—Processes of polymerisation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0057—Polymers chosen for their physico-chemical characteristics added as redispersable powders
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention belongs to the technical field of vinyl acetate copolymers, and particularly relates to a vinyl acetate-ethylene copolymer emulsion for redispersible emulsion powder. The vinyl acetate-ethylene copolymer emulsion has the colloidal particle content less than or equal to 0.5 mu m of 15-20 percent by volume percent. The vinyl acetate-ethylene copolymer emulsion has good stability.
Description
Technical Field
The invention belongs to the technical field of vinyl acetate copolymers, and particularly relates to a vinyl acetate-ethylene copolymer emulsion for redispersible emulsion powder.
Background
The vinyl acetate-ethylene copolymer emulsion is a polymer emulsion formed by copolymerizing vinyl acetate and ethylene as basic raw materials, and is abbreviated as VAE emulsion or EVA emulsion. Because of the excellent adhesion, permanent flexibility, good acid and alkali resistance and other properties, the vinyl acetate-ethylene copolymer emulsion has been widely used in the fields of adhesives, building materials, coatings, papermaking, fabric treatment, tobacco, packaging and the like since the early 1965. In particular, due to its low cost, vinyl acetate-ethylene copolymer emulsions have developed extremely rapidly in recent years, with market demands continuously increasing at 15% -20% (development of blend modified vinyl acetate-ethylene copolymer emulsions, "Xianming, shanxi building, volume 44, 10, page 93, left column, section 1, line 1-7, publication date 2018, month 4, 30).
The VAE redispersible emulsion powder is white powder of free-flowing ethylene-vinyl acetate copolymer which is formed by carrying out special treatment on VAE emulsion and then carrying out spray drying conversion, is easy to re-emulsify and disperse in water to be reduced into stable emulsion, and is fully mixed with cement, quartz sand and the like to prepare dry-mixed mortar on the basis of keeping the original characteristics of the VAE emulsion. Along with the rapid development of domestic dry-mixed mortar, the German Wake company timely introduces the VAE redispersible emulsion powder into China.
However, the existing vinyl acetate-ethylene copolymer emulsion as the base material of the redispersible emulsion powder has poor stability, and limits the application of the vinyl acetate-ethylene copolymer emulsion in the redispersible emulsion powder, thereby further limiting the application of the VAE redispersible emulsion powder in dry-mixed mortar.
Disclosure of Invention
In view of the above, the present invention aims to provide a vinyl acetate-ethylene copolymer emulsion having good stability.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the vinyl acetate-ethylene copolymer emulsion has a colloidal particle size of less than or equal to 0.5 μm and a content of 15-20% by volume.
The inventor unexpectedly found that the vinyl acetate-ethylene copolymer emulsion with the particle size less than or equal to 0.5 μm has good stability and the content of colloidal particles of 15-20% (in volume percent) in the research process.
Further, the solid content of the vinyl acetate-ethylene copolymer emulsion is 58% -62%, and the mass percentage is calculated.
Further, the viscosity of the vinyl acetate-ethylene copolymer emulsion at 25 ℃ is 1000-1500 mPas.
Further, the average particle diameter of the vinyl acetate-ethylene copolymer emulsion is 0.8-1.3 μm.
The second purpose of the invention is to protect the preparation method of the vinyl acetate-ethylene copolymer emulsion, which is prepared from raw materials including monomers, protective colloid, an initiating system and water, wherein the protective colloid is polyvinyl alcohol with the polymerization degree less than or equal to 500 and the alcoholysis degree of 86% -90%.
Further, the vinyl acetate-ethylene copolymer emulsion is prepared from the raw materials comprising, by mass, 54-98 parts of a monomer, 4.6-5.4 parts of a protective colloid, 0.25-0.35 part of an initiating system and 40-50 parts of water.
Further, the monomers include vinyl acetate and ethylene.
Further, the mass ratio of the vinyl acetate to the ethylene is 50-90:4-8.
Further, the initiating system includes an oxidizing agent and a reducing agent.
Further, the oxidizing agent is an oil-soluble oxidizing agent.
Further, the oil-soluble oxidant is tert-butyl hydroperoxide or tert-butyl peroxybenzoate.
Further, the reducing agent includes erythorbate and/or ascorbic acid.
Further, the mass ratio of the oxidant to the reducing agent is 0.15-0.2:0.1-0.15.
Further, a pH adjuster is included.
Further, the pH adjuster includes acetate or bicarbonate.
Further, the vinyl acetate-ethylene copolymer emulsion is prepared from the raw materials comprising, by mass, 54-98 parts of a monomer, 3.5-5 parts of a protective colloid, 0.25-0.35 part of an initiating system, 0.1-0.2 part of a pH regulator and 40-50 parts of water.
Further, the preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following steps:
mixing protective colloid accounting for 30-35% of the total amount with water to dissolve completely, adding vinyl acetate accounting for 40-50% of the total amount, stirring uniformly, adding ethylene to raise the pressure to 2.0-3.0MPa, heating to 60-70 ℃, adding an initiating system solution, heating to 75-80 ℃, adding the rest vinyl acetate and the rest protective colloid when the pressure is raised to 3.0-5.0MPa, controlling the temperature of a reaction kettle to 78-82 ℃, cutting off ethylene, preserving heat for 20-40min, cooling to 50-60 ℃, defoaming, filtering, cooling, adding a pH regulator, stirring uniformly, and discharging.
The inventor unexpectedly found in the research process that the stability of the prepared vinyl acetate-ethylene copolymer emulsion is good when the protective colloid is fed according to the mode of the invention.
Further, the preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following steps:
A. raw material preparation
Adding 0.15-0.2 part of oxidant and 3-5 parts of water into the tank a, stirring and dissolving to obtain an initiator solution;
adding 0.1-0.15 part of reducing agent and 3-5 parts of water into the tank b, stirring and dissolving to obtain a reducing agent solution;
adding 0.8-1.2 parts of protective colloid and 8-10 parts of water into the groove c, heating, stirring and dissolving to obtain protective colloid dripping liquid;
preparing a pH regulator solution by using a pH regulator and 2 parts of deionized water;
B. feeding production
Adding 3.8-4.2 parts of protective colloid and 18-24 parts of water into a reaction kettle, starting stirring, and heating after fully mixing to completely dissolve the protective colloid;
adding 20-45 parts of vinyl acetate after the kettle substrate material is completely dissolved, stirring uniformly, adding ethylene, and boosting the pressure to 2.0-3.0MPa;
pumping the solution in the tank a and the tank b when the temperature is increased to 60-70 ℃, dropwise adding the rest of the solution in the vinyl acetate and the tank c when the temperature in the reaction kettle reaches 75-80 ℃ and the pressure reaches 3.0-5.0MPa, and uniformly adding the rest of the solution in the vinyl acetate and the tank c within 120-150min, wherein the temperature of the reaction kettle is controlled at 78-82 ℃;
cutting off ethylene after the continuous vinyl acetate and the solution in the tank c are added, uniformly adding the residual solution in the tank a within 30-40min, uniformly dropwise adding the residual solution in the tank b 10min earlier than the residual solution in the tank a, preserving heat for 20-40min, cooling to 50-60 ℃, defoaming, filtering, cooling, adding the pH regulator solution, uniformly stirring, and discharging.
The invention has the beneficial effects that:
the vinyl acetate-ethylene copolymer emulsion has good stability, and the dilution stability is less than or equal to 1.6 percent.
The vinyl acetate-ethylene copolymer emulsion has high solid content, and can effectively reduce energy consumption when being used for producing redispersible emulsion powder.
The vinyl acetate-ethylene copolymer emulsion can reduce the addition amount of a later dispersing agent.
The vinyl acetate-ethylene copolymer emulsion can be well mixed with cement, and the obtained rubber powder has good dispersibility.
The preparation method of the invention has stable reaction.
Drawings
FIG. 1 is a graph showing the particle size distribution of a vinyl acetate-ethylene copolymer emulsion prepared in example 1;
FIG. 2 is a graph showing the particle size distribution of the vinyl acetate-ethylene copolymer emulsion prepared in example 2;
FIG. 3 is a graph showing the particle size distribution of the vinyl acetate-ethylene copolymer emulsion prepared in example 3;
FIG. 4 is a graph showing the particle size distribution of the vinyl acetate-ethylene copolymer emulsion prepared in example 4.
Detailed Description
The examples are presented for better illustration of the present invention, but are not intended to limit the scope of the present invention to the examples. Those skilled in the art will appreciate that various modifications and adaptations of the embodiments described above are possible in light of the above teachings and are intended to be within the scope of the invention.
Example 1
The vinyl acetate-ethylene copolymer emulsion is prepared by the following raw materials according to the following steps:
A. raw material preparation
Adding 0.15 part of tert-butyl hydroperoxide and 3 parts of deionized water into a tank a, and stirring and dissolving to obtain an initiator solution;
adding 0.15 part of sodium erythorbate and 5 parts of deionized water into the tank b, and stirring and dissolving to obtain a reducer solution;
adding 1.0 part of PVA0488 and 10 parts of deionized water into a groove c, heating, stirring and dissolving to obtain a protective colloid drop solution;
preparing a pH regulator solution by mixing 0.2 part of sodium acetate and 2 parts of deionized water in another container;
b feeding production
Adding 4.0 parts of PVA0488 and 18 parts of deionized water into a reaction kettle, starting stirring, and heating after full mixing to completely dissolve the PVA0488 and the deionized water;
after the kettle substrate material is completely dissolved, 30 parts of vinyl acetate is added, and after uniform stirring, ethylene is added to raise the pressure to 2.0MPa. Slowly pumping the solution in the tank a and the tank b when the temperature is increased to 65 ℃, and dropwise adding the residual solution in the vinyl acetate and the tank c when the temperature in the reaction kettle reaches 80 ℃ and the pressure reaches 4.0MPa, wherein the residual solution in the vinyl acetate and the tank c is uniformly added in 120 min;
after the reaction kettle temperature is controlled at 78-82 ℃, the residual vinyl acetate and the solution in the tank c are completely added, the ethylene is cut off, the residual solution in the tank a is completely added at a constant speed for 30min, the residual solution in the tank b is dropwise added at a constant speed for 10min earlier than the residual solution in the tank a, the temperature is kept for 40min, the temperature is reduced to 50-60 ℃, the temperature is reduced to normal temperature through defoaming, filtering and cooling, the pH regulator solution is added, and the mixture is uniformly stirred and discharged.
Example 2
The vinyl acetate-ethylene copolymer emulsion is prepared by the following raw materials according to the following steps:
A. raw material preparation
Adding 0.2 part of tert-butyl peroxybenzoate and 4 parts of deionized water into a tank a, and stirring and dissolving to obtain an initiator solution;
adding 0.1 part of ascorbic acid and 3 parts of deionized water into a tank b, and stirring and dissolving to obtain a reducer solution;
adding 1.2 parts of PVA0588 and 10 parts of deionized water into a tank c, heating, stirring and dissolving to obtain a protective colloid drop solution;
preparing a pH regulator solution by mixing 0.1 part of sodium bicarbonate and 2 parts of deionized water in another container;
B. feeding production
Adding 3.8 parts of PVA0588 and 24 parts of deionized water into a reaction kettle, starting stirring, and heating after full mixing to completely dissolve the PVA0588 and the deionized water;
after the kettle substrate material is completely dissolved, 45 parts of vinyl acetate is added, and after the mixture is stirred uniformly, ethylene is added to raise the pressure to 2.5MPa. Slowly pumping the solution in the tank a and the tank b when the temperature is raised to 70 ℃, dropwise adding the rest of the solution in the vinyl acetate and the tank c when the temperature in the reaction kettle reaches 80 ℃ and the pressure reaches 5.0MPa, and uniformly adding the rest of the solution in the vinyl acetate and the tank c for 130min, wherein the temperature of the reaction kettle is controlled at 78-82 ℃;
cutting off ethylene after the residual vinyl acetate and the solution in the tank c are added, dripping the residual solution in the tank a at a constant speed for 40min, adding the solution in the tank b at a constant speed which is 10min earlier than the solution in the tank a, preserving heat for 40min, cooling to 50-60 ℃, defoaming, filtering, cooling to normal temperature, adding the pH regulator solution, stirring uniformly, and discharging.
Example 3
The vinyl acetate-ethylene copolymer emulsion is prepared by the following raw materials according to the following steps:
A. raw material preparation
Adding 0.18 part of tert-butyl hydroperoxide and 3.5 parts of deionized water into a tank a, and stirring and dissolving to obtain an initiator solution;
adding 0.12 part of ascorbic acid and 5 parts of deionized water into a tank b, and stirring and dissolving to obtain a reducer solution;
adding 1.2 parts of PVA0388 and 10 parts of deionized water into a groove c, heating, stirring and dissolving to obtain a protective colloid drop solution;
preparing a pH regulator solution in another container from 0.15 part of sodium acetate and 2 parts of deionized water;
B. feeding production
Adding 4.2 parts of PVA0388 and 18 parts of deionized water into a reaction kettle, starting stirring, and heating after full mixing to completely dissolve the PVA0388 and the deionized water;
after the kettle substrate material is completely dissolved, 40 parts of vinyl acetate is added, and after the mixture is stirred uniformly, ethylene is added to raise the pressure to 3.0MPa. Slowly pumping the solution in the tank a and the tank b when the temperature is increased to 65 ℃, dropwise adding the rest of the solution in the vinyl acetate and the tank c when the temperature in the reaction kettle reaches 77 ℃ and the pressure reaches 4.5MPa, and uniformly adding the rest of the solution in the vinyl acetate and the tank c for 120min, wherein the temperature of the reaction kettle is controlled at 78-82 ℃;
cutting off ethylene after the addition of the residual vinyl acetate and the solution in the tank c is finished, dropwise adding the residual solution in the tank a at a constant speed for 35min, adding the solution in the tank b at a constant speed which is 10min earlier than the solution in the tank a, preserving heat for 30min, cooling to 50-60 ℃, defoaming, filtering, cooling to normal temperature, adding the pH regulator solution, stirring uniformly, and discharging.
Example 4
The vinyl acetate-ethylene copolymer emulsion is prepared by the following raw materials according to the following steps:
A. preparing raw materials.
Adding 0.16 part of tert-butyl peroxybenzoate and 5 parts of deionized water into a tank a, and stirring and dissolving to obtain an initiator solution;
adding 0.12 part of sodium erythorbate and 4 parts of deionized water into the tank b, and stirring and dissolving to obtain a reducer solution;
adding 1.1 parts of PVA0488 and 8 parts of deionized water into a groove c, heating, stirring and dissolving to obtain a protective colloid dropping liquid;
preparing a pH regulator solution by mixing 0.12 part of sodium bicarbonate and 2 parts of deionized water;
B. feeding production
Adding 3.9 parts of PVA0488 and 22 parts of deionized water into a reaction kettle, starting stirring, and heating after full mixing to completely dissolve the PVA0488 and the deionized water;
after the kettle substrate material is completely dissolved, 20 parts of vinyl acetate is added, and after the mixture is stirred uniformly, ethylene is added to raise the pressure to 2.0MPa. Slowly pumping the solution in the tank a and the tank b when the temperature is increased to 65 ℃, dropwise adding the rest of the solution in the vinyl acetate and the tank c when the temperature in the reaction kettle reaches 78 ℃ and the pressure reaches 4.0MPa, and uniformly adding the rest of the solution in the vinyl acetate and the tank c for 140min, wherein the temperature of the reaction kettle is controlled at 78-82 ℃;
cutting off ethylene after the continuous vinyl acetate and the solution in the tank c are added, dripping the rest solution in the tank a at a constant speed for 40min, adding the solution in the tank b at a constant speed which is 10min earlier than the solution in the tank a, preserving heat for 40min, cooling to 50-60 ℃, defoaming, filtering, cooling to normal temperature, adding the pH regulator solution, stirring uniformly, and discharging.
Performance detection
The appearance, glass transition temperature, solid content, viscosity (25 ℃ C.), dilution stability, average particle diameter, particle size distribution and residual vinyl acetate content of the vinyl acetate-ethylene copolymer emulsions prepared in examples 1 to 4 were examined, and the results are shown in Table 1 and FIGS. 1 to 4;
the appearance detection method comprises the following steps: visual observation;
the glass transition temperature is measured by a differential scanning calorimeter, and is specifically as follows: soaking the film with deionized water, taking out after 24 hr, naturally drying, and measuring in N with differential scanning calorimeter 2 Determining a DSC curve at a heating rate of 20 ℃/min under an atmosphere;
the method for detecting the solid content comprises the following steps: accurately weighing 2.0-3.0g of emulsion in a weighed weighing bottle, putting the emulsion into a constant temperature oven for drying to constant weight at 110-120 ℃, taking out the emulsion after drying, cooling to room temperature, and weighing; the solids content was then calculated as solids (%) = sample weight after constant temperature drying/emulsion weight x 100;
the viscosity detection method comprises the following steps: apparent viscosities at different shear rates were measured using an NDJ-type rotary viscometer at 25 ℃;
the method for detecting the dilution stability comprises the following steps: the sample was diluted with distilled water to a nonvolatile content of 3.0% by weight, and then the aqueous dispersion was placed in a 100mL stoppered cylinder, and after standing for 72 hours, the volume of the supernatant and the volume of the precipitated portion of the bottom layer were measured. The dilution stability is expressed by the volume fraction of the bottom sediment in 100mL of dilution liquid, the result is an integer, and the smaller the number is, the better the dilution stability of the emulsion is;
the detection method of the average particle size and the particle size distribution comprises the following steps: testing the particle size and distribution of the emulsion by using a MASTERSIZER 2000 type laser particle sizer, and calculating the volume of small particles through a distribution diagram;
the residual vinyl acetate content is detected according to the detection method of residual vinyl acetate content in GB/T27573-2011 vinyl acetate-ethylene copolymer emulsion.
TABLE 1 Performance test results
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 |
| Appearance of | White emulsion | White emulsion | White emulsion | White emulsion |
| Glass transition temperature/DEGC | 17.5 | 18.0 | 16.8 | 19.0 |
| Solids content/% | 60.3 | 59.9 | 60.9 | 59.5 |
| Viscosity (25 ℃ C.)/mPa.s | 1330 | 1175 | 1421 | 1208 |
| Dilution stability/% | 1.5 | 1.3 | 1.6 | 1.5 |
| Average particle diameter/. Mu.m | 1.052 | 1.211 | 1.003 | 0.922 |
| Residual vinyl acetate content/% | 0.11 | 0.15 | 0.18 | 0.15 |
As is clear from FIG. 1, the emulsion prepared in example 1 had a colloidal particle content of 19.08% (by volume) having a particle size of 0.5. Mu.m or less.
As is clear from FIG. 2, the emulsion prepared in example 2 has a colloidal particle content of 19.74% (by volume) having a particle size of 0.5. Mu.m or less.
As is clear from FIG. 3, the emulsion prepared in example 3 has a colloidal particle content of 19.26% (by volume) having a particle size of 0.5. Mu.m or less.
As is clear from FIG. 4, the content of colloidal particles having a particle diameter of 0.5 μm or less in the emulsion obtained in example 4 was 19.54% (by volume).
As is clear from Table 1, the dilution stability of the vinyl acetate-ethylene copolymer emulsions prepared in examples 1 to 4 was not more than 1.6%. From this, it was confirmed that the vinyl acetate-ethylene copolymer emulsion of the present invention has good stability.
The vinyl acetate-ethylene copolymer emulsion prepared in examples 1 to 4 was spray-dried to obtain redispersible emulsion powder, water was added to the redispersible emulsion powder to prepare a solution having a mass content of 30%, and the solution was poured into a petri dish, dried at room temperature (25 ℃) and observed for film formation.
After being observed, redispersible emulsion powder formed by the vinyl acetate-ethylene copolymer emulsion prepared in examples 1-4 is redispersed to form a complete and compact semitransparent film. Therefore, the redispersible emulsion powder formed by the vinyl acetate-ethylene copolymer emulsion has good dispersibility.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The vinyl acetate-ethylene copolymer emulsion is characterized in that the content of colloidal particles with the particle diameter less than or equal to 0.5 mu m is 15-20 percent by volume percent; the emulsion is prepared from raw materials including monomers, protective colloid, an initiating system and water, wherein the monomers are vinyl acetate and ethylene; the monomer content is 54-98 parts by mass; the protective colloid is polyvinyl alcohol with the polymerization degree less than or equal to 500 and the alcoholysis degree of 86-90 percent; the method comprises the following steps:
a. Raw material preparation
Adding 0.15-0.2 part of oxidant and 3-5 parts of water into the tank a, stirring and dissolving to obtain an initiator solution;
adding 0.1-0.15 part of reducing agent and 3-5 parts of water into the tank b, stirring and dissolving to obtain a reducing agent solution;
adding 0.8-1.2 parts of protective colloid and 8-10 parts of water into the groove c, heating, stirring and dissolving to obtain protective colloid dripping liquid; preparing a pH regulator solution by using a pH regulator and 2 parts of deionized water;
b, feeding production
Adding 3.8-4.2 parts of protective colloid and 18-24 parts of water into a reaction kettle, starting stirring, and heating after fully mixing to completely dissolve the protective colloid; adding 20-45 parts of vinyl acetate after the kettle substrate material is completely dissolved, stirring uniformly, adding ethylene, and boosting the pressure to 2.0-3.0MPa; pumping the solution in the tank a and the tank b when the temperature is increased to 60-70 ℃, dropwise adding the rest of the solution in the vinyl acetate and the tank c when the temperature in the reaction kettle reaches 75-80 ℃ and the pressure reaches 3.0-5.0MPa, and uniformly adding the rest of the solution in the vinyl acetate and the tank c within 120-150min, wherein the temperature of the reaction kettle is controlled at 78-82 ℃; cutting off ethylene after continuous vinyl acetate and solution in a tank c are added, uniformly adding the residual solution in a tank a within 30-40min, uniformly dropwise adding the residual solution in a tank b 10min earlier than the residual solution in the tank a, preserving heat for 20-40min, cooling to 50-60 ℃, defoaming, filtering, cooling, adding the pH regulator solution, uniformly stirring, and discharging;
the oxidant is tert-butyl hydroperoxide or tert-butyl peroxybenzoate; the reducing agent comprises erythorbate and/or ascorbic acid; the mass ratio of the vinyl acetate to the ethylene is 50-90:4-8.
2. The vinyl acetate-ethylene copolymer emulsion according to claim 1, wherein the solid content is 58% to 62% by mass.
3. Vinyl acetate-ethylene copolymer emulsion according to claim 1 or 2, characterized in that the viscosity at 25 ℃ is 1000-1500 mPa-s.
4. Vinyl acetate-ethylene copolymer emulsion according to claim 1 or 2, characterized in that the average particle size is 0.8-1.3 μm.
5. A vinyl acetate-ethylene copolymer emulsion according to claim 3 characterized in that the average particle size is 0.8-1.3 μm.
6. The method for preparing vinyl acetate-ethylene copolymer emulsion according to any one of claims 1 to 5, wherein the emulsion is prepared from raw materials including monomers, protective colloid, an initiating system and water, wherein the protective colloid is polyvinyl alcohol with polymerization degree less than or equal to 500 and alcoholysis degree of 86% -90%; the monomer is vinyl acetate and ethylene; the monomer content is 54-98 parts by mass; the method comprises the following steps:
a. Raw material preparation
Adding 0.15-0.2 part of oxidant and 3-5 parts of water into the tank a, stirring and dissolving to obtain an initiator solution;
adding 0.1-0.15 part of reducing agent and 3-5 parts of water into the tank b, stirring and dissolving to obtain a reducing agent solution;
adding 0.8-1.2 parts of protective colloid and 8-10 parts of water into the groove c, heating, stirring and dissolving to obtain protective colloid dripping liquid; preparing a pH regulator solution by using a pH regulator and 2 parts of deionized water;
b, feeding production
Adding 3.8-4.2 parts of protective colloid and 18-24 parts of water into a reaction kettle, starting stirring, and heating after fully mixing to completely dissolve the protective colloid; adding 20-45 parts of vinyl acetate after the kettle substrate material is completely dissolved, stirring uniformly, adding ethylene, and boosting the pressure to 2.0-3.0MPa; pumping the solution in the tank a and the tank b when the temperature is increased to 60-70 ℃, dropwise adding the rest of the solution in the vinyl acetate and the tank c when the temperature in the reaction kettle reaches 75-80 ℃ and the pressure reaches 3.0-5.0MPa, and uniformly adding the rest of the solution in the vinyl acetate and the tank c within 120-150min, wherein the temperature of the reaction kettle is controlled at 78-82 ℃; cutting off ethylene after continuous vinyl acetate and solution in a tank c are added, uniformly adding the residual solution in a tank a within 30-40min, uniformly dropwise adding the residual solution in a tank b 10min earlier than the residual solution in the tank a, preserving heat for 20-40min, cooling to 50-60 ℃, defoaming, filtering, cooling, adding the pH regulator solution, uniformly stirring, and discharging;
the oxidant is tert-butyl hydroperoxide or tert-butyl peroxybenzoate; the reducing agent comprises erythorbate and/or ascorbic acid; the mass ratio of the vinyl acetate to the ethylene is 50-90:4-8.
7. The method according to claim 6, wherein the mass ratio of the oxidizing agent to the reducing agent is 0.15-0.2:0.1-0.15.
8. The method of preparation according to claim 6 or 7, wherein the pH adjuster comprises acetate or bicarbonate.
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| US5143966A (en) * | 1990-11-07 | 1992-09-01 | Air Products And Chemicals, Inc. | Vinyl acetate/ethylene copolymer emulsions having improved wet tack properties |
| JPH09118723A (en) * | 1995-10-24 | 1997-05-06 | Denki Kagaku Kogyo Kk | Particulate polymer composition |
| CN1903894A (en) * | 2005-07-25 | 2007-01-31 | 丁武 | Ethylene-vinylacetate polymer EVA redispersible emulsoid powder and its preparation method |
| DE102006037317A1 (en) * | 2006-08-08 | 2008-02-14 | Celanese Emulsions Gmbh | Vinyl ester copolymer dispersions, process for their preparation and use |
| CN102372813B (en) * | 2010-08-24 | 2015-08-05 | 中国石油化工集团公司 | A kind of low viscosity vinyl acetate-ethylene copolymerization emulsions and preparation method and use thereof |
| CN106279493B (en) * | 2015-06-10 | 2019-02-26 | 中国石油化工集团公司 | A kind of high viscosity high solids content vinyl acetate-ethylene copolymerization emulsions and its production method |
| CN108219043A (en) * | 2016-12-21 | 2018-06-29 | 中国石化集团四川维尼纶厂 | A kind of preparation method of polyvinyl acetate emulsion |
| CN109651556B (en) * | 2017-10-11 | 2021-12-17 | 中国石油化工集团公司 | Monodisperse vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
| CN109575311B (en) * | 2018-11-27 | 2021-11-26 | 广西广维化工有限责任公司 | Preparation method of vinyl acetate-ethylene copolymer emulsion |
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