CN111100219A - Preparation method of low-VOC vinyl acetate-ethylene copolymer emulsion - Google Patents
Preparation method of low-VOC vinyl acetate-ethylene copolymer emulsion Download PDFInfo
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- CN111100219A CN111100219A CN201811249282.3A CN201811249282A CN111100219A CN 111100219 A CN111100219 A CN 111100219A CN 201811249282 A CN201811249282 A CN 201811249282A CN 111100219 A CN111100219 A CN 111100219A
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Abstract
The invention belongs to the technical field of vinyl acetate-ethylene copolymer emulsion, and particularly relates to a preparation method of low-VOC vinyl acetate-ethylene copolymer emulsion, which comprises the following steps: and (3) carrying out reduced pressure distillation on the vinyl acetate-ethylene copolymer emulsion obtained by the defoaming process, and then adding the reducing agent solution and the oxidant solution into different tanks respectively. The method improves the treatment efficiency of the residual monomer; the time consumption of the vinyl acetate-ethylene copolymer emulsion treatment process is greatly shortened, and the production cost is reduced; the stability of the vinyl acetate-ethylene copolymer emulsion is not influenced; when the method is used for treating the vinyl acetate-ethylene copolymer emulsion, the VOC removal rate in the vinyl acetate-ethylene copolymer emulsion reaches 99.14-99.29%.
Description
Technical Field
The invention belongs to the technical field of vinyl acetate-ethylene copolymer emulsion, and particularly relates to a preparation method of low-VOC vinyl acetate-ethylene copolymer emulsion.
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 therefore, the vinyl acetate-ethylene copolymer emulsion is widely applied to the fields of buildings, packaging, toys, home furnishings, automobiles, coatings, adhesives, textiles, electronic accessories and the like.
The VAE emulsion is formed by copolymerizing vinyl acetate and ethylene, and inevitably contains volatile organic compounds (VOC for short in English) such as benzene, aldehyde, ketone, acid, residual vinyl acetate monomer and the like. Most of these volatile organics are volatile, giving the emulsion a unique odor. With the enhancement of environmental awareness, people put forward more strict requirements on the content of volatile organic compounds in chemical products.
To reduce the VOC content in chemical products, CN101354213A removed the synthetic rubber solvent (i.e., volatile components) using a twin-screw vented extruder having 5 vacuum vents, each vent connected to a vacuum pump. CN101429044A adds amino-terminated polyether with high boiling point (250 ℃) into polyacrylate emulsion, and utilizes the reaction of the amino-terminated polyether with acrylate monomer to reduce the residual acrylate monomer in the polyacrylate emulsion. CN101544866A selects film forming base material (VAE emulsion) and a plurality of auxiliary products with low odor and ultra-low VOC to obtain the high-performance environment-friendly paint with odor purification and ultra-low VOC. CN104418959A adding 2-3 wt% organic solvent, 10-13 wt% water and 0.02-0.03 wt% initiator into VAE emulsion, high temperature (85-95 deg.C) distilling and nitrogen purging to make residual monomer removing rate in VAE emulsion reach 99%, and effectively reducing benzene content. CN103450409A reduced styrene-acrylic emulsion odor and VOC content (less than 500ppm) by adding natural olefins CN106397641A utilized hot nitrogen and steam to remove VOC from polymer powder. CN105199624A firstly shapes the carpet back glue, then changes the film-spraying proportion to improve the VOC of the car carpet. CN105169730A preheats the acrylic emulsion and removes VOC by hot steam and nitrogen. CN106883326A reduces the residual monomer content of polyvinyl acetate emulsion to 100ppm through two oxidation-reduction reactions, and effectively controls the content of impurities (acetone and tertiary n-butyl alcohol). US6365709B1, US6696519B2 disclose methods for treating ethylenically unsaturated monomers in aqueous polymers and the oxidizing and reducing agents used. EP0650977B1 first reduced the residual monomer to 1500-6000ppm by means of a redox initiator and then treated the residual monomer to 5-500ppm by physical means (steam, negative pressure). EP1024152B1 first reduced the VOC to 1500-6000ppm by means of redox initiators and then reduced the VOC to 15-50ppm by physical means (steam). US6096858B1 first removes residual monomers using a redox initiator and then reduces the VOC content of the polymer to less than 100ppm using an inert gas.
The above-mentioned methods for reducing VOC of emulsions can be divided into the following three categories: firstly, a chemical method, which utilizes polymerization reaction to reduce the content of unsaturated monomers (mostly residual monomers) in emulsion; and secondly, a physical method, namely heating or negative pressure is utilized to enable the emulsion to be in a boiling state, and then gases such as air, water vapor, nitrogen and the like are utilized to remove VOC in the emulsion. And thirdly, continuously using a chemical method and a physical method. In the above patent, CN101429044A, CN103450409A, CN106883326A, US6365709B1 and US6696519B2 are chemical methods, and CN101354213A, CN106397641A and CN105169730A are physical methods; CN104418959A, EP0650977B1 and EP1024152B1 use both chemical and physical methods.
The 3 methods in the above patent all have corresponding defects, wherein the chemical method is only effective for unsaturated volatile matters (such as vinyl acetate), and has no removal effect for saturated volatile matters (such as methanol, n-butanol and ethyl acetate). The physical method has a removal effect on saturated volatile matters, but needs the emulsion to be in a boiling state for a long time to promote VOC volatilization, not only is the time consumed, but also a large amount of waste water and waste gas are generated, and the stability of the emulsion is easily influenced by the addition of high-temperature steam. This makes the process suitable only for emulsions with good high temperature stability. In the continuous use of the chemical method and the physical method, the latter physical method reduces the chemical removal effect due to the removal of the oxidizing agent and the reducing agent, and in order to avoid this, either the chemical treatment time is prolonged as much as possible or the amounts of the oxidizing agent and the reducing agent are increased, thereby prolonging the process time and increasing the production cost.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a low VOC vinyl acetate-ethylene copolymer emulsion, which has a good VOC removing effect, not only on unsaturated volatile substances (such as vinyl acetate), but also on saturated volatile substances (such as methanol, n-butanol, and ethyl acetate); the high-temperature stability of the vinyl acetate-ethylene copolymer emulsion is not influenced; simple process and low production cost.
The parts are parts by mass unless otherwise specified.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the preparation method of the low VOC vinyl acetate-ethylene copolymer emulsion comprises the following steps: and (3) carrying out reduced pressure distillation on the vinyl acetate-ethylene copolymer emulsion obtained by the defoaming process, and then adding the reducing agent solution and the oxidant solution into different tanks respectively.
The inventor unexpectedly finds that the method can obviously reduce the VOC content in the vinyl acetate-ethylene copolymer emulsion.
Further, the VOC content in the low-VOC vinyl acetate-ethylene copolymer emulsion is less than 35 ppm.
In order to further reduce the VOC content in the vinyl acetate-ethylene copolymer emulsion, the vacuum degree of the reduced pressure distillation is-0.06-0.08 MPa, and the time is 10-20 min.
In order to further reduce the VOC content in the vinyl acetate-ethylene copolymer emulsion, the reducing agent is 1-3 of sulfur compounds with the sulfur atom valence of-2-4, erythorbate and tartrate.
In order to further reduce the VOC content in the vinyl acetate-ethylene copolymer emulsion, the reducing agent is any one of zinc formaldehyde sulfoxylate, sodium erythorbate, sodium metabisulfite, sodium bisulfate and potassium tartrate.
Further, the mass ratio of the deionized water to the reducing agent in the reducing agent solution is as follows: 5-10:0.01-0.02.
Further, the dosage of the reducing agent solution is 0.01-0.02% of the mass of the vinyl acetate-ethylene copolymer emulsion as the reducing agent contained in the solution.
In order to further reduce the VOC content in the vinyl acetate-ethylene copolymer emulsion, the oxidant is 1-2 of inorganic peroxide and organic peroxide.
Further, the oxidant is 1-3 of persulfate, hydrogen peroxide and tert-butyl hydroperoxide.
Further, the mass ratio of the deionized water to the oxidant in the oxidant solution is as follows: 5-10:0.01-0.04.
Further, the dosage of the oxidant solution is 0.01-0.04% of the mass of the ethylene-vinyl acetate copolymer emulsion as the oxidant contained in the solution.
Further, the method comprises the following steps:
A. preparing raw materials: respectively preparing an oxidant solution and a reducing agent solution;
B. and (3) reduced pressure distillation: distilling the vinyl acetate-ethylene copolymer emulsion obtained from the defoaming process under reduced pressure, adjusting the pressure to normal pressure, and placing the vinyl acetate-ethylene copolymer emulsion in a storage tank;
c, removing: starting the storage tank to stir, simultaneously respectively dripping the oxidant solution and the reducing agent solution into the vinyl acetate-ethylene copolymer emulsion from different tanks, and filtering and discharging after 10-30min after the oxidant solution and the reducing agent solution are completely dripped.
The method can obviously reduce the VOC content in the vinyl acetate-ethylene copolymer emulsion.
The method can improve the treatment efficiency of residual monomers.
The invention has the beneficial effects that:
the method improves the treatment efficiency of residual monomers, and the treatment efficiency of vinyl acetate monomers can reach 99.53-99.76%.
When the method is used for treating the vinyl acetate-ethylene copolymer emulsion, the VOC removal rate in the vinyl acetate-ethylene copolymer emulsion reaches 99.14-99.29%.
The method can greatly shorten the time consumption of the vinyl acetate-ethylene copolymer emulsion treatment process, thereby reducing the production cost.
The method is effective for unsaturated volatile (such as vinyl acetate) and saturated volatile (such as methanol, n-butanol, and ethyl acetate).
The method does not influence the high-temperature stability of the vinyl acetate-ethylene copolymer emulsion, and the high-temperature stability of the vinyl acetate-ethylene copolymer emulsion is not changed before and after the treatment by the method.
The method has simple production process and low production cost.
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
A low VOC VAE emulsion is prepared by the following steps:
A. respectively preparing an oxidant solution and a reducing agent solution; adding 5 parts of deionized water and 0.01 part of sodium formaldehyde sulfoxylate into the tank A, and stirring for dissolving; 5 parts of deionized water and 0.01 part of ammonium persulfate are added into the tank B and stirred for dissolution;
B. and (3) reduced pressure distillation: adding VAE emulsion obtained from the defoaming process into a container, setting the vacuum degree of the container to be-0.06 MPa, vacuumizing for 10min, raising the pressure of the container to normal pressure, and pumping the emulsion into a storage tank C;
C. removing: and starting the storage tank C for stirring, respectively and simultaneously dripping an ammonium persulfate solution from the tank A and a sodium formaldehyde sulfoxylate solution from the tank B into 100 parts of VAE emulsion, dripping the oxidant and the reducing agent simultaneously after 1h, and filtering and discharging the emulsion after 10 min.
Example 2
A low VOC VAE emulsion is prepared by the following steps:
A. preparing raw materials: respectively preparing an oxidant solution and a reducing agent solution; adding 7 parts of deionized water and 0.01 part of sodium erythorbate into the tank A, and stirring for dissolving; adding 7 parts of deionized water and 0.02 part of hydrogen peroxide into the tank B, and stirring for dissolving;
B. and (3) reduced pressure distillation: adding VAE emulsion obtained from the defoaming process into a container, setting the vacuum degree of the container to be-0.07 MPa, vacuumizing for 15min, raising the pressure of the container to normal pressure, and pumping the emulsion into a storage tank C;
C. removing: and starting the storage tank C for stirring, respectively and simultaneously dripping sodium erythorbate solution from the tank A and hydrogen peroxide solution from the tank B into 100 parts of VAE emulsion, dripping the oxidant and the reducing agent simultaneously after 1 hour, filtering the emulsion after 10 minutes, and discharging.
Example 3
A low VOC VAE emulsion is prepared by the following steps:
A. preparing raw materials: respectively preparing an oxidant solution and a reducing agent solution; adding 10 parts of deionized water and 0.02 part of potassium tartrate into the tank A, and stirring for dissolving; adding 10 parts of deionized water and 0.03 part of tert-butyl hydroperoxide into the tank B, and stirring for dissolving;
B. and (3) reduced pressure distillation: adding VAE emulsion obtained from the defoaming process into a container, setting the vacuum degree of the container to be-0.08 MPa, vacuumizing for 20min, raising the pressure of the container to normal pressure, and pumping the emulsion into a storage tank C;
C. removing: and starting the storage tank C for stirring, respectively and simultaneously dripping potassium tartrate solution from the tank A and tert-butyl hydroperoxide solution from the tank B into 100 parts of VAE emulsion, dripping the oxidant and the reductant simultaneously after 0.5h, filtering the emulsion after 20min, and discharging.
Example 4
A low VOC VAE emulsion is prepared by the following steps:
A. preparing raw materials: respectively preparing an oxidant solution and a reducing agent solution; adding 5 parts of deionized water and 0.02 part of sodium metabisulfite into the tank A, and stirring for dissolving; adding 8 parts of deionized water, 0.02 part of hydrogen peroxide and 0.02 part of tert-butyl hydroperoxide into the tank B, and stirring for dissolving;
B. and (3) reduced pressure distillation: adding VAE emulsion obtained from the defoaming process into a container, setting the vacuum degree of the container to be-0.07 MPa, vacuumizing for 15min, raising the pressure of the container to normal pressure, and pumping the emulsion into a storage tank C;
C. removing: and starting the storage tank C for stirring, respectively and simultaneously dripping sodium metabisulfite solution from the tank A and hydrogen peroxide and tert-butyl hydrogen peroxide solution from the tank B into 100 parts of VAE emulsion, dripping the oxidant and the reducing agent simultaneously after 0.5h, filtering the emulsion after 20min, and discharging.
Example 5
A low VOC VAE emulsion is prepared by the following steps:
A. preparing raw materials: respectively preparing an oxidant solution and a reducing agent solution; adding 8 parts of deionized water and 0.02 part of sodium bisulfite into the tank A, and stirring for dissolving; adding 8 parts of deionized water and 0.04 part of sodium persulfate into the tank B, and stirring for dissolving;
B. and (3) reduced pressure distillation: adding VAE emulsion obtained from the defoaming process into a container, setting the vacuum degree of the container to be-0.08 MPa, vacuumizing for 15min, raising the pressure of the container to normal pressure, and pumping the emulsion into a storage tank C;
C. removing: and starting the storage tank C for stirring, respectively and simultaneously dripping sodium bisulfite solution from the tank A and sodium persulfate solution from the tank B into 100 parts of VAE emulsion, dripping the oxidant and the reducer simultaneously after 0.5h, filtering the emulsion after 30min, and discharging.
Performance detection
The results of examining the VOC content and vinyl acetate content and the content of saturated volatile matters such as methanol, n-butanol, ethyl acetate in the VAE emulsion obtained by the defoaming process in examples 1 to 5 and the VAE emulsion obtained by filtering and discharging are shown in table 1;
wherein, the VOC content is detected according to a determination method of the total volatile organic matter content in GB 18583-2008 indoor decoration and decoration material adhesive hazardous substance limit;
the content of vinyl acetate was measured in accordance with the method described in appendix A, which is a measure of the residual vinyl acetate in GB/T27573-2011 vinyl acetate-ethylene copolymer emulsion;
the content of the methanol is detected according to GB/T5009.266-2016 methanol in food determination;
detecting the content of the n-butanol according to a detection method of the content of the n-butanol in GB/T5009.48-2003 analytical method of the hygienic standards of distilled liquor and prepared liquor;
detecting the content of ethyl acetate according to a method for determining ethyl acetate in GB/T10345-2007 white spirit analysis method;
the detection method of the high-temperature stability comprises the following steps: and (3) after the emulsion is placed for 2 weeks at the temperature of 50 ℃, observing whether the emulsion has agglomeration and caking phenomena, and if the emulsion does not have agglomeration and caking, the high-temperature stability of the emulsion is normal.
TABLE 1 Performance test results
As can be seen from Table 1, the removal rate of VOC can reach 99.14-99.29%, the removal rate of vinyl acetate can reach 99.53-99.76%, methanol, n-butyl alcohol and ethyl acetate in the vinyl acetate-ethylene emulsion can be removed remarkably, and the high-temperature stability of the vinyl acetate-ethylene copolymer emulsion is not changed before and after the treatment by the method. Therefore, the method disclosed by the invention has high treatment efficiency on VOC, is effective on unsaturated volatile matters (such as vinyl acetate), has a good removal effect on saturated volatile matters (such as methanol, n-butyl alcohol and ethyl acetate), and does not influence the stability of the vinyl acetate-ethylene copolymer emulsion.
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 (12)
1. The preparation method of the low VOC vinyl acetate-ethylene copolymer emulsion is characterized by comprising the following steps: and (3) carrying out reduced pressure distillation on the vinyl acetate-ethylene copolymer emulsion obtained by the defoaming process, and then adding the reducing agent solution and the oxidant solution into different tanks respectively.
2. The method of claim 1, wherein the low VOC vinyl acetate-ethylene copolymer emulsion has a VOC content of less than 35 ppm.
3. The method according to claim 1 or 2, wherein the vacuum degree of the reduced pressure distillation is-0.08 to-0.06 MPa, and the time is 10 to 20 min.
4. The method according to claim 1, 2 or 3, wherein the reducing agent is 1 to 3 of a sulfur compound having a sulfur atom valence of-2 to 4, an erythorbate salt and a tartrate salt.
5. The method according to claim 4, wherein the reducing agent is any one of zinc formaldehyde sulfoxylate, sodium erythorbate, sodium metabisulfite, sodium bisulfate, and potassium tartrate.
6. The preparation method according to claim 1, 2, 3, 4 or 5, wherein the mass ratio of the deionized water to the reducing agent in the reducing agent solution is: 5-10:0.01-0.02.
7. The production method according to claim 1, 2, 3, 4, 5 or 6, wherein the amount of the reducing agent solution is 0.01 to 0.02% by mass of the reducing agent contained in the solution, based on the vinyl acetate-ethylene copolymer emulsion.
8. The production method according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the oxidizing agent is 1 to 2 kinds of inorganic peroxides and organic peroxides.
9. The method according to claim 8, wherein the oxidizing agent is 1 to 3 of persulfate, hydrogen peroxide, and t-butyl hydroperoxide.
10. The method according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the mass ratio of the deionized water to the oxidant in the oxidant solution is: 5-10:0.01-0.04.
11. The method according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein the amount of the oxidant solution is 0.01 to 0.04% by mass of the ethylene acetate-ethylene copolymer emulsion as the oxidant contained in the solution.
12. The method of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, comprising the steps of:
A. preparing raw materials: respectively preparing an oxidant solution and a reducing agent solution;
B. and (3) reduced pressure distillation: distilling the vinyl acetate-ethylene copolymer emulsion obtained from the defoaming process under reduced pressure, adjusting the pressure to normal pressure, and placing the vinyl acetate-ethylene copolymer emulsion in a storage tank;
c, removing: starting the storage tank to stir, respectively dripping the oxidant solution and the reducing agent solution into the vinyl acetate-ethylene copolymer emulsion from different tanks, filtering after 10-30min after the oxidant solution and the reducing agent solution are completely dripped, and discharging.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114426624A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Low-odor vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
| CN114426622A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Method for reducing VOC content in vinyl acetate-ethylene copolymer emulsion |
| CN115991809A (en) * | 2021-10-19 | 2023-04-21 | 中国石油化工股份有限公司 | Preparation method of ethylene-vinyl acetate copolymer emulsion |
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| JP2005146194A (en) * | 2003-11-19 | 2005-06-09 | Sumitomo Chemical Co Ltd | Manufacturing method of ethylene-vinyl acetate copolymer emulsion |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426624A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Low-odor vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
| CN114426622A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Method for reducing VOC content in vinyl acetate-ethylene copolymer emulsion |
| CN115991809A (en) * | 2021-10-19 | 2023-04-21 | 中国石油化工股份有限公司 | Preparation method of ethylene-vinyl acetate copolymer emulsion |
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