CN110872362A - Vinyl acetate-ethylene copolymer emulsion and preparation method thereof - Google Patents
Vinyl acetate-ethylene copolymer emulsion and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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Abstract
The invention belongs to the technical field of vinyl acetate-ethylene copolymer emulsion, and particularly relates to vinyl acetate-ethylene copolymer emulsion. The vinyl acetate-ethylene copolymer emulsion is prepared from raw materials including a vinyl acetate monomer, an ethylene monomer and a protective colloid; the protective colloid is carboxyl modified polyvinyl alcohol or a composition of the carboxyl modified polyvinyl alcohol and the polyvinyl alcohol. The vinyl acetate-ethylene copolymer emulsion has the advantages of good rheological property, high bonding strength to wood, good water resistance and the like.
Description
Technical Field
The invention belongs to the technical field of vinyl acetate-ethylene copolymer emulsion, and particularly relates to vinyl acetate-ethylene copolymer emulsion and a preparation method thereof.
Background
Vinyl acetate-ethylene copolymer emulsion (VAE emulsion for short) is a water dispersion type emulsion with excellent performance and wide application, ethylene monomer is introduced into the emulsion as an internal plasticizer of a copolymer to soften a high molecular main chain, simultaneously, the glass transition temperature and the minimum film forming temperature of the emulsion are reduced due to the internal plasticizing effect of ethylene, and the polarity of acetyl of VAE molecules enables the copolymer to contain a large amount of fillers and various additives, so that the performance of the VAE emulsion can be improved, and the VAE emulsion is widely applied to the fields of buildings, coatings, adhesives, packaging, textiles, wood processing and the like.
In recent years, the requirements of the market on the bonding strength and the water resistance of wood are higher and higher, in the compounding field, the machine speed of a compounding machine is higher and higher, the rheological property of common VAE emulsion is poorer, the viscosity is rapidly reduced along with the increase of the rotating speed, and the emulsion cannot be normally attached to the surface of a material, so that 'glue flying' with different degrees is caused in the compounding process.
Disclosure of Invention
In view of the above, the present invention is directed to a vinyl acetate-ethylene copolymer emulsion. The vinyl acetate-ethylene copolymer emulsion has good rheological property.
The parts are parts by mass unless otherwise specified.
In order to achieve the purpose, the technical scheme of the invention is as follows:
vinyl acetate-ethylene copolymer emulsion is prepared from raw materials including vinyl acetate monomers, ethylene monomers and protective colloid; the protective colloid is carboxyl modified polyvinyl alcohol or a composition of the carboxyl modified polyvinyl alcohol and the polyvinyl alcohol.
Furthermore, the alcoholysis degree of the carboxyl modified polyvinyl alcohol is 80-95%, the polymerization degree is 300-3000, and the carboxyl content is 0.1-5%.
Further, the mass ratio of the carboxyl modified polyvinyl alcohol to the vinyl acetate monomer is 0.05:1-0.2: 1.
Further, the mass ratio of the carboxyl modified polyvinyl alcohol to the vinyl acetate monomer is 0.07:1-0.15: 1.
Further, the alcoholysis degree of the polyvinyl alcohol is 80-99%, and the polymerization degree is 3000-300-one.
Further, the mass ratio of the polyvinyl alcohol to the vinyl acetate monomer is 0:1-0.1: 1.
Further, the mass ratio of the polyvinyl alcohol to the vinyl acetate monomer is 0:1-0.05: 1.
Further, the mass ratio of the ethylene monomer to the vinyl acetate monomer is 0.05:1-0.15: 1.
Further, the mass ratio of the ethylene monomer to the vinyl acetate monomer is 0.08:1-0.12: 1.
Further, the raw materials of the emulsion also comprise a pH regulator, an initiator and deionized water.
Further, the pH regulator is one or more of sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium hydrogen phosphate and sodium dihydrogen phosphate.
Further, the dosage of the pH regulator is 0.1-0.3% of the mass of the vinyl acetate monomer.
Further, the initiator is a thermal decomposition initiator or a redox initiator.
Further, the thermal decomposition initiator is a potassium persulfate solution or an ammonium persulfate solution, and the redox initiator is a tartrate-hydrogen peroxide solution or a persulfate-bisulfite solution.
Further, the initiator is potassium persulfate solution or tartrate-hydrogen peroxide solution.
Further, the dosage of the initiator is 0.2-0.6% of the mass of the solute contained in the initiator solution.
Further, the dosage of the deionized water is 1-1.4 times of the mass of the vinyl acetate monomer.
The invention also aims to protect the preparation method of the vinyl acetate-ethylene copolymer emulsion, which comprises the following steps:
mixing a protective colloid, a pH regulator and deionized water, dissolving in an autoclave, cooling to below 60 ℃, adding an initial vinyl acetate monomer, adding ethylene, boosting the pressure to 0.5-4MPa, then dropwise adding an initial initiator, heating to 60-80 ℃, dropwise adding a continuous initiator and the rest of vinyl acetate monomer after the initial vinyl acetate monomer reacts, stopping the ethylene after the continuous vinyl acetate monomer is dropwise added, continuously dropwise adding the rest of initiator, heating the reaction system after the rest of initiator is dropwise added to 82-88 ℃ for reaction for 1-2 hours, and cooling the reaction system to 20-50 ℃ to obtain the vinyl acetate-ethylene copolymer emulsion;
the initial vinyl acetate monomer accounts for 5-20% of the total amount of the vinyl acetate monomer;
the initial initiator accounts for 20-40% of the total amount of the initiator;
the continuous initiator accounts for 30-55% of the total amount of the initiator.
Further, the temperature of mixing and dissolving is 80-95 ℃, and the time is 0.5-2 h.
Further, the temperature of mixing and dissolving is 85-95 ℃, and the time is 1-1.5 h.
Further, the initial vinyl acetate monomer accounts for 8% -12% of the total amount of the vinyl acetate monomer; the initial initiator accounts for 25% -35% of the total amount of the initiator; the continuous initiator accounts for 35-50% of the total amount of the initiator.
Further, dripping the initial initiator for 5-10 min, and heating to 60-80 deg.C.
Further, mixing protective colloid, pH regulator and deionized water, dissolving in a high-pressure kettle, cooling to below 60 deg.C, adding initial vinyl acetate monomer, adding ethylene, and increasing pressure to 1-3 MPa.
Further, a continuous initiator and the residual vinyl acetate monomer are dripped to react for 1 to 4 hours at the temperature of between 70 and 85 ℃.
Further, a continuous initiator and the residual vinyl acetate monomer are dripped to react for 2 to 3 hours at the temperature of 75 to 80 ℃.
Further, the dropping time of the remaining initiator is 10 to 30 minutes.
Further, cooling the reaction system to 20-40 ℃ to obtain the vinyl acetate-ethylene copolymer emulsion.
The invention has the beneficial effects that:
according to the inventionThe vinyl acetate-ethylene copolymer emulsion has good rheological property, and the rheological property is more than 3500s-1Rheology over 3500s-1Then the rapid reduction of viscosity and the 'spin coating' occur; the composite machine is used in the composite field, the speed of the composite machine can be improved, and the production efficiency is improved.
The vinyl acetate-ethylene copolymer emulsion has high bonding strength.
The vinyl acetate-ethylene copolymer emulsion has good water resistance.
The vinyl acetate-ethylene copolymer emulsion adhesive film is soft.
The vinyl acetate-ethylene copolymer emulsion has dry compression shear strength of 9.8-10.5MPa and wet compression shear strength of 2.9-3.6 MPa.
The vinyl acetate-ethylene copolymer emulsion has the advantages of wide raw material source, low price, no great change of the existing production process, improvement of the quality of the existing vinyl acetate-ethylene copolymer emulsion product, negligible increased cost, convenient industrial implementation and wide application prospect.
Drawings
FIG. 1 is a rheological profile of the vinyl acetate-ethylene copolymer emulsion prepared in example 1;
FIG. 2 is a graph showing the rheology profile of the vinyl acetate-ethylene copolymer emulsion obtained in example 2;
FIG. 3 is a graph showing the rheology profile of the vinyl acetate-ethylene copolymer emulsion obtained in example 3;
FIG. 4 is a graph showing the rheology profile of the vinyl acetate-ethylene copolymer emulsion obtained in example 4;
FIG. 5 is a graph showing the rheology profile of the vinyl acetate-ethylene copolymer emulsion obtained in example 5;
FIG. 6 is a rheological graph of the vinyl acetate-ethylene copolymer emulsion obtained in comparative example 1.
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.
Example 1
The preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following specific steps:
3570.0 parts of deionized water is added into a high-pressure reaction kettle, 250.0 parts of SG-182 (carboxyl modified PVA) and 2.9 parts of sodium bicarbonate are added under stirring, the temperature is raised to 80 ℃, the mixture is dissolved for 2.0 hours, then the temperature is lowered to 65 ℃, 147.0 parts of initial vinyl acetate monomer is added, 281 parts of ethylene is added, the pressure is raised to 2.0MPa, 73.5 parts of deionized water and 5.8 parts of potassium persulfate are used for preparing initiator solution, 15.9 parts of potassium persulfate initiator solution is dropwise added into the high-pressure reaction kettle at constant speed within 10 minutes, after the temperature is raised to 70 ℃, 2793.0 parts of vinyl acetate and 23.8 parts of prepared potassium persulfate initiator solution are dropwise added for reaction for 4 hours, 39.6 parts of residual potassium persulfate initiator solution are uniformly added within 10 minutes, the temperature is kept at 82 ℃ for 1 hour, after the temperature is lowered to 20 ℃, the ethylene pressure is removed, and the ethylene is filtered and discharged, thus obtaining the vinyl acetate-ethylene copolymer.
Example 2
The preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following specific steps:
2940.0 parts of deionized water is added into a high-pressure reaction kettle, 147.0 parts of SG-182 (carboxyl modified PVA), 147.0 parts of PVA1799 and 8.8 parts of potassium bicarbonate are added under stirring, the temperature is raised to 95 ℃, the mixture is dissolved for 1.0 hour, the temperature is reduced to 60 ℃, 588.0 parts of vinyl acetate monomer is added, 327 parts of ethylene is added, the pressure is raised to 2.5MPa, 588.0 parts of deionized water and 17.6 parts of ammonium persulfate are used for preparing initiator solution, 242.2 parts of ammonium persulfate initiator solution is dropwise added into the high-pressure reaction kettle at a constant speed within 5min, after the temperature is raised to 85 ℃, 2352.0 parts of vinyl acetate and 333.1 parts of prepared ammonium persulfate initiator solution are dropwise added for reaction for 1 hour, 30.3 parts of residual ammonium persulfate initiator solution are uniformly added within 30 minutes, the temperature is maintained at 88 ℃ for 1.5 hours, after the temperature is reduced to 50 ℃, the ethylene pressure is removed, and the ethylene-ethylene copolymer emulsion is obtained after filtration and.
Example 3
The preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following specific steps:
4195.0 parts of deionized water is added into a high-pressure reaction kettle, 210.0 parts of SG-182 (carboxyl modified PVA), 70.0 parts of PVA1799 and 7.0 parts of potassium hydrogen phosphate are added under stirring, the temperature is raised to 90 ℃, after the mixture is dissolved for 1.5 hours, the temperature is lowered to 65 ℃, 302.4 parts of vinyl acetate monomer is added, 272 parts of ethylene is added, the pressure is raised to 2.0MPa, 236.6 parts of deionized water and 8.2 parts of sodium tartrate, 219.6 parts of deionized water and 24.8 parts of hydrogen peroxide (the mass fraction of the hydrogen peroxide is 27.5 percent) are respectively used for preparing sodium tartrate solution and hydrogen peroxide solution, 49.0 parts of sodium tartrate solution and 49.0 parts of hydrogen peroxide solution are respectively added into the high-pressure reaction kettle in a uniform-speed manner within 10min, 2217.6 parts of vinyl acetate and 120.0 parts of prepared sodium tartrate solution and 120.0 parts of hydrogen peroxide solution are added after the temperature is raised to 70 ℃, reacting for 3 hours, adding 75.8 parts of the residual sodium tartrate solution and 75.4 parts of the residual hydrogen peroxide solution (respectively adding the sodium tartrate solution and the hydrogen peroxide solution from different tanks) at constant speed within 15 minutes, preserving the temperature for 2 hours at 85 ℃, cooling to 30 ℃, removing the ethylene pressure, filtering and discharging to obtain the vinyl acetate-ethylene copolymer emulsion.
Example 4
The preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following specific steps:
adding 3570.0 parts of deionized water into an autoclave, adding 200.0 parts of SG-182 (carboxyl modified PVA), 94.0 parts of PVA 0588 and 7.0 parts of disodium hydrogen phosphate while stirring, heating to 95 ℃, dissolving for 0.5 hour, cooling to 60 ℃, adding 294.0 parts of vinyl acetate monomer, adding 364 parts of ethylene, boosting to 3.0MPa, preparing potassium persulfate initiator solution and sodium bisulfite initiator solution by using 210.0 parts of deionized water, 10.8 parts of potassium persulfate, 210.0 parts of deionized water and 4.2 parts of sodium bisulfite respectively, and adding 66.3 parts of potassium persulfate initiator solution and 64.3 parts of sodium bisulfite initiator solution into the autoclave respectively; after the reaction temperature rises to 80 ℃, 2646.0 parts of vinyl acetate are dripped, 110.4 parts of prepared potassium persulfate initiator solution and 107.1 parts of prepared sodium bisulfite initiator solution are respectively dripped, the reaction is carried out for 3 hours, the rest 44.2 parts of potassium persulfate initiator solution and 42.8 parts of sodium bisulfite initiator solution are added at constant speed within 20 minutes, the temperature is kept at 85 ℃ for 1 hour, the ethylene pressure is removed after the temperature is reduced to 30 ℃, and the vinyl acetate-ethylene copolymer emulsion is obtained after filtration and discharging.
Example 5
The preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following specific steps:
3570.0 parts of deionized water is added into a high-pressure reaction kettle, 147.0 parts of SG-182 (carboxyl modified PVA), 147.0 parts of PVA1799, 2.0 parts of sodium bicarbonate, 1.0 part of potassium bicarbonate, 1.0 part of sodium acetate, 1.5 parts of potassium hydrogen phosphate and 1.0 part of disodium hydrogen phosphate are added under stirring, the temperature is raised to 88 ℃, the temperature is reduced to 60 ℃ after 1.5 hours of dissolution, 210.0 parts of vinyl acetate monomer is added, 320 parts of ethylene is added and the pressure is raised to 2.5Mpa, 210.0 parts of deionized water and 8.4 parts of ammonium persulfate are used for preparing initiator solution, 65.5 parts of ammonium persulfate initiator solution are added into the high-pressure reaction kettle, after the temperature is raised to 80 ℃, 2730.0 parts of vinyl acetate and 76.5 parts of prepared ammonium persulfate initiator solution are added at constant speed for reaction for 3 hours, the rest of ammonium persulfate initiator solution is added within 15 minutes, the temperature is preserved for 1.5 hours at 85 ℃, then the temperature is reduced to 30 ℃, the ethylene pressure is removed, thus obtaining the carboxylated VAE emulsion.
Comparative example 1
The preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following specific steps:
adding 3500.0 parts of deionized water into a high-pressure reaction kettle, adding 125.0 parts of PVA 1788 and 125.0 parts of PVA 0588 under stirring, heating to 85 ℃, dissolving for 1.0 hour, cooling to 55 ℃, adding 210.0 parts of vinyl acetate monomer, adding 330 parts of ethylene, boosting to 2.5MPa, and preparing an initiator solution by using 210.0 parts of deionized water and 8.4 parts of potassium persulfate; adding 65.5 parts of initiator solution into a high-pressure reaction kettle, after the reaction temperature rises to 80 ℃, dropwise adding 2730.0 parts of vinyl acetate and 76.5 parts of prepared initiator solution, reacting for 3 hours, adding the rest potassium persulfate initiator solution at constant speed within 15 minutes, keeping the temperature at 85 ℃ for 1 hour, cooling to 30 ℃, removing the ethylene pressure, filtering and discharging 77 parts of sodium bicarbonate solution with the mass fraction of 9%, thus obtaining the vinyl acetate-ethylene copolymer emulsion.
Performance testing
The vinyl acetate-ethylene copolymer emulsions prepared in examples 1 to 5 and comparative example 1 were subjected to performance tests in terms of rheological properties, dry compressive shear strength of wood, wet compressive shear strength of wood, ethylene content, and the like, and the results are shown in table 1 and fig. 1 to 6;
the rheological property testing method comprises the following steps: the determination is carried out by adopting an AR-G2 rheometer, the test type adopts a continuous slope method, the water bath equilibrium temperature is 25 ℃, the angular speed is set to be 0-250rad/s, the duration is 5min, the sampling delay time is 5s, and the rotation is stopped when the viscosity of the emulsion is rapidly reduced;
the dry compressive shear strength of the wood is measured according to GB/T17517-1998 adhesive compressive shear strength test method;
the test method of the wet compression shear strength of the wood comprises the following steps: the wood chips which are bonded and dried for 72h at the normal temperature are placed in water at the normal temperature for soaking for 24h, and then the determination is carried out according to GB/T17517-1998 adhesive compression shear strength test method;
the ethylene content was determined in accordance with GB/T27573-2011 vinyl acetate-ethylene copolymer emulsion.
Table 1 results of performance testing
As is clear from Table 1, the vinyl acetate-ethylene copolymer emulsions obtained in examples 1 to 5 had higher dry compressive shear strength and wet compressive shear strength than the conventional vinyl acetate-ethylene copolymer emulsions and improved water resistance when they were used for bonding wood.
The rheological profiles of the vinyl acetate-ethylene copolymer emulsions obtained in examples 1 to 5 are shown in FIG. 1, FIG. 2, FIG. 3, FIG. 4 and FIG. 5, respectively, and the rheological profile of the vinyl acetate-ethylene copolymer emulsion obtained in comparative example 1 is shown in FIG. 6.
As can be seen from FIGS. 1 to 5, the vinyl acetate-ethylene copolymer emulsions prepared in examples 1 to 5 had a rheology of more than 3500s-1Rheology over 3500s-1The viscosity is reduced sharply and the glue is spun off. As can be seen from FIG. 6, the vinyl acetate-ethylene copolymer emulsion obtained in comparative example 1 was obtained at 2000s-1A sharp decrease in viscosity and "whirl coating" begins to occur below. Thus, the rheological property of the vinyl acetate-ethylene copolymer emulsion is obviously improved.
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 (18)
1. The vinyl acetate-ethylene copolymer emulsion is characterized by being prepared from raw materials including a vinyl acetate monomer, an ethylene monomer and a protective colloid; the protective colloid is carboxyl modified polyvinyl alcohol or a composition of the carboxyl modified polyvinyl alcohol and the polyvinyl alcohol.
2. The vinyl acetate-ethylene copolymer emulsion as claimed in claim 1, wherein the alcoholysis degree of the carboxyl-modified polyvinyl alcohol is 80-95%, the polymerization degree is 300-3000, and the carboxyl content is 0.1-5%.
3. The vinyl acetate-ethylene copolymer emulsion according to claim 1 or 2, wherein the mass ratio of the carboxyl-modified polyvinyl alcohol to the vinyl acetate monomer is from 0.05:1 to 0.2: 1.
4. The vinyl acetate-ethylene copolymer emulsion according to claim 3, wherein the mass ratio of the carboxyl-modified polyvinyl alcohol to the vinyl acetate monomer is from 0.07:1 to 0.15: 1.
5. The vinyl acetate-ethylene copolymer emulsion as recited in claim 1, 2, 3 or 4, wherein said polyvinyl alcohol has a degree of alcoholysis of 80% to 99% and a degree of polymerization of 300-3000.
6. The vinyl acetate-ethylene copolymer emulsion according to claim 1, 2, 3, 4 or 5, wherein the mass ratio of the polyvinyl alcohol to the vinyl acetate monomer is 0:1 to 0.1: 1.
7. The vinyl acetate-ethylene copolymer emulsion according to claim 6, wherein the mass ratio of the polyvinyl alcohol to the vinyl acetate monomer is 0:1 to 0.05: 1.
8. The vinyl acetate-ethylene copolymer emulsion according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the mass ratio of the ethylene monomer to the vinyl acetate monomer is from 0.05:1 to 0.15: 1.
9. The vinyl acetate-ethylene copolymer emulsion according to claim 8, wherein the mass ratio of the ethylene monomer to the vinyl acetate monomer is from 0.08:1 to 0.12: 1.
10. The vinyl acetate-ethylene copolymer emulsion of claim 1, 2, 3, 4, 5, 6, 7, 8 or 9 wherein the raw materials of the emulsion further comprise a pH adjuster, an initiator and deionized water.
11. The vinyl acetate-ethylene copolymer emulsion according to claim 10, wherein the pH adjuster is one or more of sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium hydrogen phosphate, and sodium dihydrogen phosphate.
12. The vinyl acetate-ethylene copolymer emulsion according to claim 10 or 11, wherein the amount of the pH adjuster is 0.1% to 0.3% by mass of the vinyl acetate monomer.
13. The vinyl acetate-ethylene copolymer emulsion according to claim 10, 11 or 12, wherein the initiator is a thermal decomposition initiator or a redox initiator.
14. The vinyl acetate-ethylene copolymer emulsion according to claim 13, wherein the thermal decomposition initiator is a potassium persulfate solution or an ammonium persulfate solution, and the redox initiator is a tartrate-hydrogen peroxide solution or a persulfate-hydrogen sulfite solution.
15. The vinyl acetate-ethylene copolymer emulsion according to claim 14, wherein the initiator is potassium persulfate solution or tartrate-hydrogen peroxide solution.
16. The vinyl acetate-ethylene copolymer emulsion according to claim 10, 11, 12, 13, 14 or 15, wherein the amount of the initiator is 0.2 to 0.6% by mass of the solute contained in the initiator solution based on the vinyl acetate monomer.
17. The vinyl acetate-ethylene copolymer emulsion according to claim 10, 11, 12, 13, 14, 15 or 16, wherein the amount of deionized water is 1 to 1.4 times the mass of the vinyl acetate monomer.
18. The method for preparing a vinyl acetate-ethylene copolymer emulsion according to any one of claims 1 to 17, comprising the steps of:
mixing a protective colloid, a pH regulator and deionized water, dissolving in an autoclave, cooling to below 60 ℃, adding an initial vinyl acetate monomer, adding ethylene, boosting the pressure to 0.5-4MPa, dropwise adding an initial initiator, heating to 60-90 ℃, dropwise adding a continuous initiator and the rest of vinyl acetate monomer after the initial vinyl acetate monomer reacts, stopping the ethylene after the continuous vinyl acetate monomer is dropwise added, continuously dropwise adding the rest of initiator, heating the reaction system after the rest of initiator is dropwise added to 82-88 ℃ for reaction for 1-2 hours, and cooling the reaction system to 20-50 ℃ to obtain the vinyl acetate-ethylene copolymer emulsion;
the initial vinyl acetate monomer accounts for 5-20% of the total amount of the vinyl acetate monomer;
the initial initiator accounts for 20-40% of the total amount of the initiator;
the continuous initiator accounts for 30-55% of the total amount of the initiator.
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| CN113956387A (en) * | 2021-11-02 | 2022-01-21 | 安徽皖维高新材料股份有限公司 | Copolymerization modified polyvinyl alcohol and preparation method thereof |
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