CN109651556B - Monodisperse vinyl acetate-ethylene copolymer emulsion and preparation method thereof - Google Patents
Monodisperse vinyl acetate-ethylene copolymer emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN109651556B CN109651556B CN201710940910.1A CN201710940910A CN109651556B CN 109651556 B CN109651556 B CN 109651556B CN 201710940910 A CN201710940910 A CN 201710940910A CN 109651556 B CN109651556 B CN 109651556B
- Authority
- CN
- China
- Prior art keywords
- vinyl acetate
- post
- parts
- ethylene copolymer
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 117
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229920001038 ethylene copolymer Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 17
- 238000004945 emulsification Methods 0.000 title claims description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000001590 oxidative effect Effects 0.000 claims abstract description 34
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- 239000000084 colloidal system Substances 0.000 claims abstract description 16
- 230000001681 protective effect Effects 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 230000000977 initiatory effect Effects 0.000 claims abstract description 10
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 49
- 229910021641 deionized water Inorganic materials 0.000 claims description 49
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 21
- 239000006172 buffering agent Substances 0.000 claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 16
- 239000007853 buffer solution Substances 0.000 claims description 15
- 238000012805 post-processing Methods 0.000 claims description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 13
- 239000000872 buffer Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- 229940072107 ascorbate Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 229940017705 formaldehyde sulfoxylate Drugs 0.000 claims description 5
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 claims description 5
- 229940095064 tartrate Drugs 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 3
- 238000006136 alcoholysis reaction Methods 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims 8
- 238000010790 dilution Methods 0.000 abstract description 7
- 239000012895 dilution Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 description 17
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 12
- 239000001632 sodium acetate Substances 0.000 description 12
- 235000017281 sodium acetate Nutrition 0.000 description 12
- 238000004806 packaging method and process Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 4
- 239000001472 potassium tartrate Substances 0.000 description 4
- 229940111695 potassium tartrate Drugs 0.000 description 4
- 235000011005 potassium tartrates Nutrition 0.000 description 4
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 4
- 235000010352 sodium erythorbate Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004320 sodium erythorbate Substances 0.000 description 3
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium erythorbate Chemical compound [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the technical field of vinyl acetate-ethylene copolymer emulsion, and particularly relates to monodisperse vinyl acetate-ethylene copolymer emulsion which is prepared from the following raw materials in parts by mass: prepared from raw materials including a monomer, an initiating system and an emulsifying system; the monomers are vinyl acetate, ethylene and seed emulsion; the initiation system comprises an oxidant and a reductant; the emulsifying system comprises an emulsifier and a protective colloid. The vinyl acetate-ethylene copolymer emulsion prepared by the invention has the appearance of white emulsion, the solid content of the white emulsion is more than or equal to 54.5%, the viscosity of the white emulsion is 500 and 2000mPa (25 ℃), the residual Vinyl Acetate (VAC) is less than 0.20%, the dilution stability is 1.10-1.50%, and the ethylene content is 14-16%.
Description
Technical Field
The invention belongs to the technical field of vinyl acetate-ethylene copolymer emulsion, and particularly relates to monodisperse vinyl acetate-ethylene copolymer emulsion and a preparation method thereof.
Background
Vinyl acetate-ethylene copolymer emulsion (VAE emulsion) 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 the main bond of a high polymer, 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 used in the fields of adhesives, coatings, fabric processing, buildings, packaging and the like.
Currently, as the customer feedback information is obtained from the VAE sales market, most of the commercial products have unstable quality and have problems in application. The analysis shows that the particle size of the emulsion is mostly polydisperse distribution, the particle size distribution is wider, the application performances of the emulsion such as the adhesion, the tensile strength, the rheological property, the water resistance, the dilution stability and the like are influenced to a certain extent, and the particle size distribution of the high-quality product is mostly monodisperse distribution. The monodisperse vinyl acetate-ethylene copolymer emulsion is a high-performance emulsion with the performance superior to that of a polydisperse emulsion, and the monodisperse emulsion has narrow particle size distribution, fine and uniform particles, strong wrapping capacity on filler particles, good bearing capacity and high glossiness, can obtain higher filler addition proportion, and does not reduce the water resistance and the flexibility of a product; the adhesive is easy to permeate among the constituent fibers of the fabric in the bonding of the textile, and has the advantage of being difficult to remove during washing and dry cleaning; meanwhile, the monodisperse emulsion has uniform particles and small specific surface area, and when defoaming is performed, some small particles with polarity are easy to remove, so that the odor of the emulsion is small, and the VOC content in the product is reduced. Therefore, with the change of market demand and the development of various performance requirements of the VAE, the VAE with better production performance and environmental protection more meets the requirements of people.
Disclosure of Invention
In view of the above, the present invention is directed to a monodisperse vinyl acetate-ethylene copolymer emulsion.
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 monodisperse vinyl acetate-ethylene copolymer emulsion is prepared from raw materials including a monomer, an initiating system and an emulsifying system; the monomers are vinyl acetate, ethylene and seed emulsion; the initiation system comprises an oxidant and a reductant; the emulsifying system comprises an emulsifier and a protective colloid.
Further, the seed emulsion is a vinyl acetate polymer emulsion with the particle size of 80-200 nm.
The vinyl acetate polymer emulsion is used as seed emulsion, so that the grafting rate of the reaction of the protective colloid and the monomer is improved, and the generated emulsion is more stable.
If the vinyl acetate polymer emulsion with the particle size of 80-200nm is selected as the seed emulsion to prepare the vinyl acetate-ethylene copolymer emulsion, the poly-dispersed vinyl acetate-ethylene copolymer emulsion with wider particle size distribution is obtained.
Further, the oxidant is one or a combination of more of hydrogen peroxide, potassium persulfate and ammonium persulfate.
Further, the reducing agent is one or a composition of more of formaldehyde sulfoxylate, ascorbate and tartrate.
Further, the emulsifier is one or a combination of more of octyl phenol polyoxyethylene ether, nonyl phenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
Further, the protective colloid is polyvinyl alcohol.
Further, the polyvinyl alcohol is prepared from PVA1788, PVA0588 and polyvinyl alcohol T according to the weight ratio of 4-5: 7-8: 7-9. The PVA1788, the PVA0588 and the polyvinyl alcohol T are combined together to be used as protective colloid, so that the viscosity, the solid content and the dilution stability of the obtained vinyl acetate-ethylene copolymer emulsion can be improved.
The polyvinyl alcohol T refers to polyvinyl alcohol with the polymerization degree of 1500-2000 and the alcoholysis degree of 90 (mol)% -99.5 (mol)%.
Further, the raw materials of the emulsion also comprise a pH regulator, a buffering agent, a post-processing auxiliary agent and deionized water, wherein the pH regulator and the buffering agent are bicarbonate, acetate or phosphate.
Further, the post-processing auxiliary agent comprises a post-processing auxiliary agent a and a post-processing auxiliary agent b.
Further, the post-processing auxiliary agent a is one or a combination of more of hydrogen peroxide, potassium persulfate and ammonium persulfate, and the post-processing auxiliary agent b is one or a combination of more of formaldehyde sulfoxylate and ascorbate tartrate.
Further, the feed additive is prepared from the following raw materials in parts by mass:
monomer (b): 33-35 parts of vinyl acetate, 14-16 parts of ethylene and 3-5 parts of seed emulsion;
an initiation system: 0.13-0.15 part of reducing agent and 0.26-0.30 part of oxidizing agent;
an emulsification system: 1.9-2.1 parts of protective colloid and 0.26-0.28 part of emulsifier;
pH regulator: 0.04-0.05 part;
buffering agent: 0.07-0.08 portion;
0.04-0.07 part of post-treatment auxiliary agent;
42.1 to 45.7 portions of deionized water.
Further, the preparation method comprises the following steps:
A. raw material preparation
A1. Preparing an emulsion solution system: adding 36-38 parts of deionized water and 1.9-2.1 parts of protective colloid into an emulsifier tank, stirring for 15-20 minutes at normal temperature, heating to 85 ℃ to completely dissolve the deionized water and the protective colloid, cooling to room temperature, and adding 0.26-0.28 part of emulsifier;
A2. preparing an initiator solution system: adding 4-5 parts of deionized water and 0.26-0.30 part of oxidant into an oxidant tank, and stirring to completely dissolve the deionized water and the oxidant to obtain an oxidation solution;
A3. preparing a buffer solution: weighing 0.07-0.08 part of buffering agent, placing the buffering agent in a buffering agent tank, adding 0.8-1 part of deionized water into the buffering agent tank, and stirring to completely dissolve the buffering agent;
A4. preparing a post-treatment solution: adding 0.01-0.03 part of post-treatment auxiliary agent a into 0.6-0.8 part of deionized water to obtain a post-treatment solution 1, and adding 0.01-0.02 part of post-treatment auxiliary agent b into 0.7-0.9 part of deionized water to obtain a post-treatment solution 2;
B. feeding production
Pumping the emulsified solution system into a reaction kettle, pumping 0.13-0.15 part of reducing agent, 3-5 parts of seed emulsion and 18-20 parts of vinyl acetate, and pumping 14-16 parts of ethylene into the reaction kettle; when the temperature reaches 54-62 ℃ and the pressure reaches 3.50-3.65MPa, adding an oxidizing solution containing 0.006-0.008 part of oxidant, clearing and fully cooling at 67-69 ℃; controlling the reaction and the adding speed of the rest oxidizing solution by a computer, continuously increasing the pressure of the reaction kettle to 5.58-5.96MPa, adding the rest vinyl acetate (the total dosage of the vinyl acetate is 33-35 parts), and simultaneously adding a buffer solution; entering a finishing period when the vinyl acetate feeding is finished, the temperature reaches 75-78 ℃, and the pressure reaches 1.50-1.52 MPa; defoaming, adding post-treatment solution (post-treatment solution 1 and post-treatment solution 2 are added from different tanks respectively) for post-treatment; after cooling, 0.04-0.05 part of pH regulator is added.
The invention has the beneficial effects that:
the vinyl acetate-ethylene copolymer emulsion is prepared from raw materials including a monomer of a seed emulsion, an initiating system and an emulsifying system, and the prepared vinyl acetate-ethylene copolymer emulsion is measured by a particle size analyzer, has narrow particle size distribution and only one peak and is monodisperse vinyl acetate-ethylene copolymer emulsion.
The monodisperse vinyl acetate-ethylene copolymer emulsion prepared by the invention does not adopt a traditional emulsifier method, and also does not adopt a membrane emulsification method and a micro-channel emulsification method. But is polymerized by adopting polyvinyl alcohol as protective colloid, selecting proper buffer solution and nonionic emulsifier and utilizing a new process combining seed emulsion polymerization and traditional emulsion polymerization. The method is easy to realize in industrial production, simple in production process, safe and reliable in production process, and less in emulsion residue amount in each kettle. The emulsion produced by the method has better stability, good reproducibility, and good safety and environmental protection.
The invention greatly reduces the amount of residual VAE monomer in the VAE emulsion, and the residual Vinyl Acetate (VAC) of the prepared vinyl acetate-ethylene copolymer emulsion is less than 0.20 percent.
The invention is suitable for a semi-continuous preparation process flow, is polymerized by adopting a new process combining seed emulsion and traditional emulsion polymerization, and shortens the batch reaction time of the whole process flow. The semi-continuous reaction characteristic and the external circulation heat dissipation device characteristic are brought into full play.
The invention improves the grafting rate of the reaction of the protective colloid and the monomer, and ensures that the generated emulsion is more stable and the dilution stability is 1.10-1.50%.
According to the invention, the buffer solution is added in successive stages, so that a hydration layer with moderate thickness is formed between the emulsion particles, the viscosity of the emulsion can be controlled (500 and 2000mPa ℃) (25 ℃)), and the storage stability is improved.
The emulsion obtained by the invention has narrow particle size distribution, high solid content (more than or equal to 54.5 percent) and high ethylene content (14-16 percent), has better flexibility and water resistance, can be used as a universal adhesive, and is widely applied to the manufacturing industries of paper processing, paint decoration, wood processing, non-woven fabrics, carpets and the like.
The vinyl acetate-ethylene copolymer emulsion residue obtained by the method is greatly reduced, the yield of the emulsion is increased, and the deslagging cost is reduced.
The vinyl acetate-ethylene copolymer emulsion obtained by the invention has small smell and low VOC total amount, and is green and environment-friendly.
The invention has wide raw material source and low price, does not greatly change the prior production process, improves the quality of the prior vinyl acetate-ethylene copolymer emulsion product, simultaneously has negligible increased cost, convenient industrial implementation and wide application prospect.
Drawings
FIG. 1 is a graph showing a particle size distribution of a vinyl acetate-ethylene copolymer emulsion obtained in example 1;
FIG. 2 is a graph showing a particle size distribution of a vinyl acetate-ethylene copolymer emulsion obtained in example 2;
FIG. 3 is a graph showing a distribution of particle sizes of a vinyl acetate-ethylene copolymer emulsion obtained in example 3;
FIG. 4 is a graph showing a distribution of particle sizes of a vinyl acetate-ethylene copolymer emulsion obtained in example 4;
FIG. 5 is a graph showing a distribution of particle diameters 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:
A. raw material preparation
A1: oxidant solution: adding 4 parts of deionized water and 0.28 part of hydrogen peroxide into an oxidant tank, and stirring to completely dissolve the deionized water and the hydrogen peroxide;
a2: buffer solution: weighing 0.07 part of sodium bicarbonate, placing the sodium bicarbonate in a buffer tank, adding 1 part of deionized water into the buffer tank, and stirring to completely dissolve the sodium bicarbonate;
a3: post-treatment solution: adding 0.03 part of hydrogen peroxide into 0.6 part of deionized water to obtain a post-treatment solution 1, and adding 0.02 part of rongalite into 0.7 part of deionized water to obtain a post-treatment solution 2; the two are respectively added in the production process of preparing and feeding materials;
B. feeding production
Adding 37 parts of deionized water, 0.4 part of PVA1788, 0.8 part of PVA0588 and 0.9 part of PVA1799 into a reaction kettle, stirring for 18 minutes at normal temperature, heating to 85 ℃ to completely dissolve the mixture, cooling to room temperature, adding 0.27 part of octylphenol polyoxyethylene ether, 0.14 part of rongalite, 4 parts of seed emulsion (vinyl acetate polymer emulsion with the particle size of 100 nm) and 19 parts of vinyl acetate, adding 15 parts of ethylene into the reaction kettle, adding an oxidation solution containing 0.006 part of hydrogen peroxide when the initial temperature reaches 54 ℃ and the pressure reaches 3.65MPa, and resetting and cooling completely at 67 ℃; controlling the reaction and the adding rate of the rest oxidizing solution by a computer, continuously increasing the pressure of the reaction kettle to 5.96MPa, continuously dropwise adding 16 parts of vinyl acetate, and simultaneously adding a buffer solution; entering a finishing period when the vinyl acetate feeding is finished and the temperature is 78 ℃ and the pressure is 1.52 MPa; defoaming, adding post-treatment solution (post-treatment solution 1 and post-treatment solution 2 are added from different tanks respectively) for post-treatment; and (3) after cooling, adding 0.04 part of pH regulator, discharging, filtering and packaging.
Example 2
The preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following specific steps:
A. raw material preparation
A1: oxidant solution: adding 5 parts of deionized water and 0.26 part of potassium persulfate into the oxidant tank, and stirring to completely dissolve the potassium persulfate;
a2: buffer solution: weighing 0.08 part of sodium acetate, placing the sodium acetate in a buffer tank, adding 0.8 part of deionized water into the buffer tank, and stirring to completely dissolve the sodium acetate;
a3: post-treatment solution: adding 0.03 part of potassium persulfate into 0.6 part of deionized water to obtain a post-treatment solution 1, and adding 0.02 part of potassium tartrate into 0.9 part of deionized water to obtain a post-treatment solution 2; the two are respectively added in the production process of preparing and feeding materials;
B. feeding production
Adding 36 parts of deionized water, 0.5 part of PVA1788, 0.7 part of PVA0588 and 0.8 part of PVA1995 into a reaction kettle, stirring for 20 minutes at normal temperature, heating to 85 ℃ to completely dissolve the PVA, cooling to room temperature, adding 0.28 part of nonylphenol polyoxyethylene ether, 0.13 part of potassium tartrate, 5 parts of seed emulsion (vinyl acetate polymer emulsion with the particle size of 200 nm), 20 parts of vinyl acetate, adding 16 parts of ethylene into the reaction kettle, adding an oxidizing solution containing 0.008 part of potassium persulfate when the initial temperature reaches 62 ℃ and the pressure reaches 3.5MPa, and resetting to 69 ℃ and cooling completely; controlling the reaction and the adding rate of the rest oxidizing solution by a computer, continuously increasing the pressure of the reaction kettle to 5.58MPa, continuously dropwise adding 13 parts of vinyl acetate, and simultaneously adding a buffer solution; entering a finishing period when the vinyl acetate feeding is finished and the temperature is 75 ℃ and the pressure is 1.5 MPa; defoaming, adding post-treatment solution (post-treatment solution 1 and post-treatment solution 2 are added from different tanks respectively) for post-treatment; and (3) after cooling, adding 0.04 part of pH regulator, discharging, filtering and packaging.
Example 3
The preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following specific steps:
A. raw material preparation
A1: oxidant solution: adding 4.2 parts of deionized water and 0.27 part of ammonium persulfate into the oxidant tank, and stirring to completely dissolve the deionized water and the ammonium persulfate;
a2: buffer solution: weighing 0.08 part of sodium acetate, placing the sodium acetate in a buffer tank, adding 0.8 part of deionized water into the buffer tank, and stirring to completely dissolve the sodium acetate;
a3: post-treatment solution: adding 0.01 part of ammonium persulfate into 0.8 part of deionized water to obtain a post-treatment solution 1, and adding 0.01 part of sodium erythorbate into 0.8 part of deionized water to obtain a post-treatment solution 2; the two are respectively added in the production process of preparing and feeding materials;
B. feeding production
Adding 38 parts of deionized water, 0.4 part of PVA1788, 0.8 part of PVA0588 and 0.7 part of PVA1899 into a reaction kettle, stirring for 15 minutes at normal temperature, heating to 85 ℃ to completely dissolve the PVA, cooling to room temperature, adding 0.26 part of fatty alcohol-polyoxyethylene ether, 0.15 part of sodium erythorbate, 3 parts of seed emulsion (vinyl acetate polymer emulsion with the particle size of 80 nm) and 18 parts of vinyl acetate, adding 14 parts of ethylene into the reaction kettle, adding an oxidizing solution containing 0.006 part of ammonium persulfate when the initial temperature reaches 56 ℃ and the pressure reaches 3.58MPa, and resetting and full cooling at 68 ℃; controlling the reaction and the adding rate of the rest oxidizing solution by a computer, continuously increasing the pressure of the reaction kettle to 5.77MPa, continuously dropwise adding 16 parts of vinyl acetate, and simultaneously adding a buffer solution; entering a finishing period when the vinyl acetate feeding is finished and the temperature is 76 ℃ and the pressure is 1.5 MPa; defoaming, adding post-treatment solution (post-treatment solution 1 and post-treatment solution 2 are added from different tanks respectively) for post-treatment; and (3) after cooling, adding 0.05 part of pH regulator, discharging, filtering and packaging.
Example 4
The preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following specific steps:
A. raw material preparation
A1: oxidant solution: adding 5 parts of deionized water, 0.09 part of ammonium persulfate, 0.09 part of potassium persulfate and 0.09 part of hydrogen peroxide into an oxidant tank, and stirring to completely dissolve the ammonium persulfate and the potassium persulfate;
a2: buffer solution: weighing 0.07 part of sodium acetate, placing the sodium acetate in a buffer tank, adding 0.9 part of deionized water into the buffer tank, and stirring to completely dissolve the sodium acetate;
a3: post-treatment solution: adding 0.01 part of ammonium persulfate, 0.01 part of potassium persulfate and 0.01 part of hydrogen peroxide into 0.6 part of deionized water to obtain a post-treatment solution 1, and adding 0.005 part of rongalite and 0.005 part of potassium tartrate into 0.8 part of deionized water to obtain a post-treatment solution 2; the two are respectively added in the production process of preparing and feeding materials;
B. feeding production
Adding 37 parts of deionized water, 0.4 part of PVA1788, 0.8 part of PVA0588 and 0.7 part of PVA1792 into a reaction kettle, stirring for 15 minutes at normal temperature, heating to 85 ℃ to completely dissolve the PVA, cooling to room temperature, adding 0.10 part of octyl phenol polyoxyethylene ether, 0.10 part of nonylphenol polyoxyethylene ether, 0.10 part of fatty alcohol polyoxyethylene ether, 0.05 part of white zinc oxide, 0.05 part of potassium tartrate, 0.05 part of sodium isoascorbate, 5 parts of seed emulsion (vinyl acetate polymer emulsion with the particle size of 150 nm), 19 parts of vinyl acetate, adding 14 parts of ethylene into the reaction kettle, adding an oxidizing solution containing 0.002 part of ammonium persulfate, 0.002 part of potassium persulfate and 0.002 part of hydrogen peroxide when the initial temperature reaches 56 ℃ and the pressure reaches 3.5MPa, and clearing and full cooling at 67 ℃; controlling the reaction and the adding rate of the rest oxidizing solution by a computer, continuously increasing the pressure of the reaction kettle to 5.82MPa, continuously dropwise adding 16 parts of vinyl acetate, and simultaneously adding a buffer solution; entering a finishing period when the vinyl acetate feeding is finished and the temperature is 77 ℃ and the pressure is 1.5 MPa; defoaming, adding post-treatment solution (post-treatment solution 1 and post-treatment solution 2 are added from different tanks respectively) for post-treatment; and (3) after cooling, adding 0.05 part of pH regulator, discharging, filtering and packaging.
Comparative example 1
The preparation method of the vinyl acetate-ethylene copolymer emulsion comprises the following specific steps:
A. raw material preparation
A1: oxidant solution: adding 4 parts of deionized water and 0.30 part of ammonium persulfate into an oxidant tank, and stirring to completely dissolve the deionized water and the ammonium persulfate;
a2: buffer solution: weighing 0.08 part of sodium acetate, placing the sodium acetate in a buffer tank, adding 1 part of deionized water into the buffer tank, and stirring to completely dissolve the sodium acetate;
a3: post-treatment solution: adding 0.03 part of ammonium persulfate into 0.6 part of deionized water to obtain a post-treatment solution 1, and adding 0.02 part of sodium erythorbate into 0.7 part of deionized water to obtain a post-treatment solution 2; the two are respectively added in the production process of preparing and feeding materials;
B. feeding production
Adding 37 parts of deionized water, 0.4 part of PVA1788, 0.8 part of PVA0588 and 0.9 part of PVA1799 into a reaction kettle, stirring for 15 minutes at normal temperature, heating to 85 ℃ to completely dissolve the PVA, cooling to room temperature, adding 0.27 part of octylphenol polyoxyethylene ether, 0.14 part of rongalite and 19 parts of vinyl acetate monomer, adding 15 parts of ethylene into the reaction kettle, adding 0.006 part of oxidizing solution containing hydrogen peroxide when the initial temperature reaches 54 ℃ and the pressure reaches 3.65MPa, and clearing and fully cooling at 68 ℃; controlling the reaction and the initiator adding rate by a computer, continuously increasing the pressure of the reaction kettle to 5.96MPa, and continuously dropwise adding the residual vinyl acetate; entering a finishing period when the vinyl acetate feeding is finished and the temperature is 78 ℃ and the pressure is 1.52 MPa; defoaming, adding post-treatment solution (post-treatment solution 1 and post-treatment solution 2 are added from different tanks respectively) for post-treatment; and (3) after cooling, adding 0.05 part of pH regulator, discharging, filtering and packaging.
Index testing
The vinyl acetate-ethylene copolymer emulsions prepared in examples 1 to 4 and comparative example 1 were subjected to index tests in terms of appearance, solid content, viscosity, particle size, ethylene content, residual vinyl acetate, dilution stability, and the like, respectively; the test results are shown in table 1:
wherein, the appearance is detected according to GB/T27573-2011 vinyl acetate-ethylene copolymer emulsion;
the solid content is measured according to GB/T1725-1979 coating solid content determination method; the measuring instrument is an HR83 type infrared moisture measuring instrument and a stainless steel weighing disc; the operating condition is standard temperature rise of 165 ℃;
the viscosity was measured according to GB/T27573-2011 vinyl acetate-ethylene copolymer emulsion;
the particle size is measured by a MasterSizer2000 laser particle size analyzer;
the ethylene content was determined according to GB/T27573-2011 vinyl acetate-ethylene copolymer emulsion;
the content of residual vinyl acetate was measured by headspace gas chromatography;
the measurement method of the dilution stability is as follows: (1) weighing 15 g of synthetic emulsion and 15 g of distilled water in a 100mL beaker, and uniformly stirring; (2) weighing 10mL centrifuge tube1Recording the weight m of the diluted emulsion poured into the tube2(about 10 grams); (3) placing the centrifuge tube into a centrifuge, centrifuging at 2600 rpm for 4min, taking out, inverting the centrifuge tube for 5min, wiping off the tube orifice, and weighing the precipitate in the centrifuge tube to obtain a weight m3. The dilution stability is calculated as:
the average of the two replicates was taken as the assay.
Table 1 results of performance testing
From the above data, it can be seen that the vinyl acetate-ethylene copolymer emulsions prepared in examples 1-4 had a white emulsion appearance, a solid content of 54.5% or more, a viscosity of 500 and 2000 mPa-.
The particle size distribution diagrams of the vinyl acetate-ethylene copolymer emulsions obtained in examples 1 to 4 are shown in FIG. 1, FIG. 2, FIG. 3 and FIG. 4, respectively, and the particle size distribution diagram of the vinyl acetate-ethylene copolymer emulsion obtained in comparative example 1 is shown in FIG. 5.
As can be seen from FIGS. 1 to 4, the vinyl acetate-ethylene copolymer emulsions obtained in examples 1 to 4 had a narrow particle size distribution with only one peak, and were monodisperse VAE emulsions.
As can be seen from FIG. 5, the vinyl acetate-ethylene copolymer emulsion obtained in comparative example 1, to which no seed emulsion was added, had a broad particle size distribution with a plurality of peaks, and was a polydisperse VAE 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 (13)
1. The monodisperse vinyl acetate-ethylene copolymer emulsion is characterized by being prepared from raw materials including a monomer, an initiating system and an emulsifying system; the monomer comprises vinyl acetate, ethylene and seed emulsion; the initiating system comprises an oxidizing agent and a reducing agent; the emulsifying system comprises an emulsifier and a protective colloid, and the seed emulsion is a vinyl acetate polymer emulsion with the particle size of 80-200 nm; the emulsifier is a composition of more than one of octyl phenol polyoxyethylene ether, nonyl phenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether; the protective colloid is polyvinyl alcohol.
2. The monodisperse vinyl acetate-ethylene copolymer emulsion according to claim 1, wherein the oxidant is one or a combination of hydrogen peroxide, potassium persulfate and ammonium persulfate.
3. The monodisperse vinyl acetate-ethylene copolymer emulsion according to claim 1 or 2, wherein the reducing agent is one or a combination of formaldehyde sulfoxylate, ascorbate and tartrate.
4. The monodisperse vinyl acetate-ethylene copolymer emulsion according to claim 1 or 2, wherein the polyvinyl alcohol is selected from the group consisting of PVA1788, PVA0588 and polyvinyl alcohol T according to a ratio of 4-5: 7-8:7-9, the polymerization degree of the polyvinyl alcohol T is 1700-2000, and the alcoholysis degree is 90-99.5% calculated by mol.
5. The monodisperse vinyl acetate-ethylene copolymer emulsion of claim 3 wherein the polyvinyl alcohol is selected from the group consisting of PVA1788, PVA0588 and polyvinyl alcohol T in a ratio of 4-5: 7-8:7-9, the polymerization degree of the polyvinyl alcohol T is 1700-2000, and the alcoholysis degree is 90-99.5% calculated by mol.
6. The monodisperse vinyl acetate-ethylene copolymer emulsion according to claim 1, 2 or 5, wherein the raw materials of the emulsion further comprise a pH regulator, a buffering agent, a post-processing aid and deionized water, wherein the pH regulator and the buffering agent are bicarbonate, acetate or phosphate, and the post-processing aid comprises a post-processing aid a and a post-processing aid b.
7. The monodisperse vinyl acetate-ethylene copolymer emulsion according to claim 3, wherein the raw materials of the emulsion further comprise a pH regulator, a buffering agent, a post-processing aid and deionized water, the pH regulator and the buffering agent are bicarbonate, acetate or phosphate, and the post-processing aid comprises a post-processing aid a and a post-processing aid b.
8. The monodisperse vinyl acetate-ethylene copolymer emulsion according to claim 4, wherein the raw materials of the emulsion further comprise a pH regulator, a buffer, a post-treatment auxiliary agent and deionized water, the pH regulator and the buffer are bicarbonate, acetate or phosphate, and the post-treatment auxiliary agent comprises a post-treatment auxiliary agent a and a post-treatment auxiliary agent b.
9. The monodisperse vinyl acetate-ethylene copolymer emulsion according to claim 6, wherein the post-treatment auxiliary agent a is one or a combination of hydrogen peroxide, potassium persulfate and ammonium persulfate, and the post-treatment auxiliary agent b is one or a combination of formaldehyde sulfoxylate, ascorbate and tartrate.
10. The monodisperse vinyl acetate-ethylene copolymer emulsion according to claim 7 or 8, wherein the post-treatment auxiliary agent a is one or a combination of hydrogen peroxide, potassium persulfate and ammonium persulfate, and the post-treatment auxiliary agent b is one or a combination of formaldehyde sulfoxylate, ascorbate and tartrate.
11. The monodisperse vinyl acetate-ethylene copolymer emulsion as claimed in claim 6, which is prepared from the following raw materials in parts by mass:
monomer (b): 33-35 parts of vinyl acetate, 14-16 parts of ethylene and 3-5 parts of seed emulsion;
an initiation system: 0.13-0.15 part of reducing agent and 0.26-0.30 part of oxidizing agent;
an emulsification system: 1.9-2.1 parts of protective colloid and 0.26-0.28 part of emulsifier;
pH regulator: 0.04-0.05 part;
buffering agent: 0.07-0.08 portion;
0.04-0.07 part of post-treatment auxiliary agent;
42.1 to 45.7 portions of deionized water.
12. The monodisperse vinyl acetate-ethylene copolymer emulsion according to any one of claims 7-9, which is prepared from the following raw materials in parts by mass:
monomer (b): 33-35 parts of vinyl acetate, 14-16 parts of ethylene and 3-5 parts of seed emulsion;
an initiation system: 0.13-0.15 part of reducing agent and 0.26-0.30 part of oxidizing agent;
an emulsification system: 1.9-2.1 parts of protective colloid and 0.26-0.28 part of emulsifier;
pH regulator: 0.04-0.05 part;
buffering agent: 0.07-0.08 portion;
0.04-0.07 part of post-treatment auxiliary agent;
42.1 to 45.7 portions of deionized water.
13. The method for preparing monodisperse vinyl acetate-ethylene copolymer emulsion as claimed in claim 10, which comprises the steps of:
A. raw material preparation
A1. Preparing an emulsion solution system: adding 36-38 parts of deionized water and 1.9-2.1 parts of protective colloid into an emulsifier tank, stirring for 15-20 minutes at normal temperature, heating to 85 ℃ to completely dissolve the deionized water and the protective colloid, cooling to room temperature, and adding 0.26-0.28 part of emulsifier;
A2. preparing an initiator solution system: adding 4-5 parts of deionized water and 0.26-0.30 part of oxidant into an oxidant tank, and stirring to completely dissolve the deionized water and the oxidant to obtain an oxidation solution;
A3. preparing a buffer solution: weighing 0.07-0.08 part of buffering agent, placing the buffering agent in a buffering agent tank, adding 0.8-1 part of deionized water into the buffering agent tank, and stirring to completely dissolve the buffering agent;
A4. preparing a post-treatment solution: adding 0.01-0.03 part of post-treatment auxiliary agent a into 0.6-0.8 part of deionized water, and adding 0.01-0.02 part of post-treatment auxiliary agent b into 0.7-0.9 part of deionized water;
B. feeding production
Pumping the emulsified solution system into a reaction kettle, pumping 0.13-0.15 part of reducing agent, 3-5 parts of seed emulsion and 18-20 parts of vinyl acetate, and pumping 14-16 parts of ethylene into the reaction kettle; when the temperature reaches 54-62 ℃ and the pressure reaches 3.50-3.65MPa, adding an oxidizing solution containing 0.006-0.008 part of oxidant, clearing and fully cooling at 67-69 ℃; controlling the reaction and the adding rate of the rest oxidizing solution by a computer, continuously increasing the pressure of the reaction kettle to 5.58-5.96MPa, adding the rest vinyl acetate, and simultaneously adding a buffer solution; entering a finishing period when the vinyl acetate feeding is finished, the temperature reaches 75-78 ℃, and the pressure reaches 1.50-1.52 MPa; defoaming to a defoaming tank, and adding a post-treatment solution for post-treatment; after cooling, adding 0.04-0.05 part of pH regulator;
the total dosage of the vinyl acetate is 33 to 35 portions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710940910.1A CN109651556B (en) | 2017-10-11 | 2017-10-11 | Monodisperse vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710940910.1A CN109651556B (en) | 2017-10-11 | 2017-10-11 | Monodisperse vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109651556A CN109651556A (en) | 2019-04-19 |
| CN109651556B true CN109651556B (en) | 2021-12-17 |
Family
ID=66108993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710940910.1A Active CN109651556B (en) | 2017-10-11 | 2017-10-11 | Monodisperse vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109651556B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708312A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Polymer cement waterproof paint and preparation method thereof |
| CN112708002B (en) * | 2019-10-24 | 2023-01-03 | 中国石油化工股份有限公司 | Vinyl acetate-ethylene copolymer emulsion having excellent compatibility with cement at high temperature |
| CN113493536B (en) * | 2020-03-19 | 2023-06-09 | 中国石油化工股份有限公司 | Vinyl acetate-ethylene copolymer emulsion for redispersible emulsion powder |
| CN115991799B (en) * | 2021-10-20 | 2025-03-21 | 中国石油化工股份有限公司 | Application of oil-soluble oxidants in improving the stability of vinyl acetate-ethylene copolymer emulsion |
| CN115991814A (en) * | 2021-10-20 | 2023-04-21 | 中国石油化工股份有限公司 | Application of increasing monomer concentration in micelle in increasing molecular weight of ethylene-vinyl acetate copolymer emulsion |
| CN114250645B (en) * | 2021-12-31 | 2022-11-22 | 东莞市天迪印刷有限公司 | High-strength easily-inked packaging paper and preparation method thereof |
| CN116023575B (en) * | 2022-12-20 | 2024-09-03 | 虹石(江苏)新材料科技有限公司 | High-water-resistance VAE emulsion and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0924229A1 (en) * | 1997-12-16 | 1999-06-23 | National Starch and Chemical Investment Holding Corporation | Ultra high solids vinyl acetate-ethylene and vinyl acetate homopolymer emulsions |
| EP1067147A2 (en) * | 1999-07-06 | 2001-01-10 | Air Products Polymers, L.P. | Vinyl acetate/ethylene high solids emulsions |
| CN102234351A (en) * | 2010-05-05 | 2011-11-09 | 张永昶 | Method for preparing vinyl acetate/acrylic emulsion with large particle size |
| CN102731709A (en) * | 2011-04-07 | 2012-10-17 | 中国石油化工集团公司 | Vinyl acetate-ethylene copolymer emulsion for wallpaper coating and preparation method thereof |
| CN104293245A (en) * | 2014-09-28 | 2015-01-21 | 广西大学 | Vinyl acetate wood adhesive and preparation method thereof |
-
2017
- 2017-10-11 CN CN201710940910.1A patent/CN109651556B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0924229A1 (en) * | 1997-12-16 | 1999-06-23 | National Starch and Chemical Investment Holding Corporation | Ultra high solids vinyl acetate-ethylene and vinyl acetate homopolymer emulsions |
| EP1067147A2 (en) * | 1999-07-06 | 2001-01-10 | Air Products Polymers, L.P. | Vinyl acetate/ethylene high solids emulsions |
| CN102234351A (en) * | 2010-05-05 | 2011-11-09 | 张永昶 | Method for preparing vinyl acetate/acrylic emulsion with large particle size |
| CN102731709A (en) * | 2011-04-07 | 2012-10-17 | 中国石油化工集团公司 | Vinyl acetate-ethylene copolymer emulsion for wallpaper coating and preparation method thereof |
| CN104293245A (en) * | 2014-09-28 | 2015-01-21 | 广西大学 | Vinyl acetate wood adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109651556A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109651556B (en) | Monodisperse vinyl acetate-ethylene copolymer emulsion and preparation method thereof | |
| EP2000485B1 (en) | Formaldehyde-free emulsion polymer dispersion composition including fully hydrolyzed polyvinyl alcohol as colloidal stabilizer provding improved heat resistance | |
| RU2472832C2 (en) | Heat resistant polymer dispersion obtained by emulsion polymerisation | |
| US3644262A (en) | Process for increasing the ethylene content of vinyl acetate-ethylene emulsion copolymers | |
| US20130131261A1 (en) | Process for Preparing Vinyl Acetate-Ethylene Copolymers by Means of Emulsion Polymerization | |
| EP2739694A1 (en) | Low formaldehyde vinyl ester/ethylene copolymer dispersions for use in adhesives | |
| EP3068806A1 (en) | Floor covering adhesive composition comprising a vinyl acetate-ethylene copolymer | |
| US9663678B2 (en) | Waterproofing coating compositions | |
| CN104558320B (en) | Polyvinyl acetate emulsion | |
| CN103270059A (en) | Polymers derived from itaconic acid | |
| US2892802A (en) | Medium for emulsion polymerization of ethylenically unsaturated monomers and method therefor and composition therefrom | |
| CN106854251B (en) | High-solid-content polyvinyl acetate emulsion and preparation method thereof | |
| US6616798B2 (en) | Process for preparing adhesives having improved adhesion | |
| CN103951790A (en) | Vinyl acetate emulsion and preparation process thereof | |
| CN111100235A (en) | Vinyl acetate-ethylene copolymer emulsion with high ethylene content and preparation method thereof | |
| WO2019126913A1 (en) | A method for preparing aqueous copolymer dispersions | |
| WO2018148929A1 (en) | Use of aqueous polymer dispersion for interfacial bonding between polymeric porous materials | |
| CN117624444A (en) | High-water-resistance monodisperse modified vinyl acetate-ethylene copolymer emulsion and preparation method thereof | |
| US9650507B2 (en) | Method for producing vinyl ester polymers having specifically settable dispersity and low polydispersity | |
| US5652289A (en) | Method for making an aqueous emulsion polymer | |
| CN112708004A (en) | Vinyl acetate-ethylene copolymer emulsion and preparation method thereof | |
| CN101824291A (en) | Vinyl acetate/aromatic vinyl ester copolymer binder resins | |
| CN109153753B (en) | An aqueous polymer dispersion for adhesives | |
| CN114426620B (en) | Vinyl acetate-ethylene copolymer emulsion and preparation method thereof | |
| CN113423796B (en) | Adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |