CN113773434A - Preparation method of low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion - Google Patents
Preparation method of low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion Download PDFInfo
- Publication number
- CN113773434A CN113773434A CN202110987616.2A CN202110987616A CN113773434A CN 113773434 A CN113773434 A CN 113773434A CN 202110987616 A CN202110987616 A CN 202110987616A CN 113773434 A CN113773434 A CN 113773434A
- Authority
- CN
- China
- Prior art keywords
- vinyl acetate
- reaction
- low
- reaction liquid
- solution
- 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.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 50
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229920001038 ethylene copolymer Polymers 0.000 title claims abstract description 33
- 239000007787 solid Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 239000000178 monomer Substances 0.000 claims abstract description 47
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007800 oxidant agent Substances 0.000 claims abstract description 31
- 230000001590 oxidative effect Effects 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- WDHSSYCZNMQRNF-UHFFFAOYSA-L ctk1a4617 Chemical compound [Zn+2].O=C.[O-]S[O-] WDHSSYCZNMQRNF-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 8
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004945 emulsification Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 43
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 25
- 239000005977 Ethylene Substances 0.000 claims description 25
- CAAIULQYGCAMCD-UHFFFAOYSA-L zinc;hydroxymethanesulfinate Chemical compound [Zn+2].OCS([O-])=O.OCS([O-])=O CAAIULQYGCAMCD-UHFFFAOYSA-L 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QGKLCGVVGGFZBS-UHFFFAOYSA-N formaldehyde;zinc Chemical compound [Zn].O=C QGKLCGVVGGFZBS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J131/00—Adhesives based on homopolymers or 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; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion, which comprises the following steps: (1) adding initial monomer vinyl acetate and a surfactant solution into a reactor for pre-emulsification, adding an oxidant hydrogen peroxide solution for initiating reaction, stirring for reaction, uniformly and sectionally adding continuous monomer vinyl acetate in the reaction process, adding a zinc sulfoxylate formaldehyde aqueous solution in the curing period, and finishing the reaction after the curing period is finished; (2) adding water, tert-butyl peroxybenzoate, sodium bicarbonate, adjusting the pH value of the reaction solution, adjusting the nonvolatile component content of the reaction solution by using a defoaming agent and the like, and vinyl acetate and the like, uniformly stirring, filtering and removing filter residues to obtain the low-viscosity low-solid vinyl acetate-ethylene copolymer emulsion GW-707A. The low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion GW-707A has better rheological property, maintains the low viscosity of the emulsion, reduces the solid content and ensures that the leveling property of the emulsion is more excellent.
Description
Technical Field
The invention relates to a preparation method of vinyl acetate-ethylene copolymer emulsion, in particular to a preparation method of low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion.
Background
Vinyl acetate-ethylene copolymer emulsion (namely VAE) introduces ethylene molecular chains into polyvinyl acetate molecules, so that acetyl groups generate discontinuity, the rotational freedom degree of a high molecular chain is increased, the space obstruction is small, the main chain of a high molecular chain becomes soft, and the rheological property is improved. Meanwhile, ethylene is used as an internal plasticizer of the copolymer, so that the VAE polymer has internal plasticization, and the plasticizer cannot migrate, thereby avoiding the aging of the polymer performance. The VAE emulsion not only has good stability to ultraviolet rays, but also has good acid and alkali resistance, and is widely applied to the fields of adhesives, waterproof coatings, interior decoration, outdoor heat preservation, carpets, non-woven fabrics, paper industry processing, cement modification and the like.
At present, vinyl acetate-ethylene copolymer emulsion products are in a plurality of types, and each type has unique performance advantages. The non-volatile matter of the prior vinyl acetate-ethylene copolymer emulsion of various brands is more than or equal to 54 percent, and the mechanical stability of the emulsion, no matter the emulsion is low in viscosity and high in solid content or high in viscosity and low in solid content, the film-forming hardness is high due to the high curing speed, the flexibility is insufficient, the smoothness is poor during construction, the ageing resistance is reduced, and the waterproof effect is poor. In the aspect of production control, the proportion of a reaction system formed by an initial surfactant, a vinyl acetate monomer and ethylene influences the viscosity and the solid content of the copolymerization emulsion; in order to obtain the low-solid low-viscosity copolymer emulsion, the ratio of vinyl acetate monomer to ethylene must be reduced, the initial surfactant is related to the balance of the whole system, the emulsion is exploded due to excessive use amount, and the emulsion breaking occurs in an emulsion system due to insufficient use amount, which becomes a difficulty of the production process.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention overcomes the production difficulty of reaction system balance, provides a preparation method of low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion, and prepares the vinyl acetate-ethylene copolymer emulsion GW-707A which has good rheological property, strong bonding force, good film forming flexibility, difficult after-tack and can be used in low-temperature areas. The invention makes up the defect that vinyl acetate-ethylene copolymer emulsion products have higher requirements on the flexibility of waterproof coatings, adhesive plates and textile coatings, and provides an emulsion raw material with better performance for adhesives and spray-coating.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a method for preparing a low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion comprises the following operation steps:
(1) adding initial monomer vinyl acetate and a surfactant solution into a closed reactor for pre-emulsification, continuously dropwise adding an oxidant hydrogen peroxide solution under the ethylene atmosphere and the pressure of 1.5-6.0MPa to initiate a reaction, stirring for reaction for 100-120min, uniformly and sectionally adding continuous monomer vinyl acetate in the reaction process, controlling the temperature to be 78-82 ℃ in the reaction process, after the continuous monomer vinyl acetate is completely added, enabling the reaction temperature to be lower than 77 ℃ and the adding rate of the oxidant hydrogen peroxide solution to be increased to 100%, enabling the product to enter a curing period, adding a zinc sulfoxylate formaldehyde (ZFS) aqueous solution in the curing period, improving the conversion rates of the monomer vinyl acetate (initial monomer vinyl acetate + continuous monomer vinyl acetate) and ethylene, and ending the reaction after the curing period;
(2) placing the reaction liquid obtained after the curing period in the step (1) in a flash evaporator to remove residual ethylene, adding deionized water to adjust the content of non-volatile components in the reaction liquid, adding tert-butyl peroxybenzoate to reduce the content of vinyl acetate in the reaction liquid, adding sodium bicarbonate to adjust the pH value of the reaction liquid, adding a defoaming agent to remove residual fine bubbles in the reaction liquid, uniformly stirring, filtering and removing filter residues to obtain the low-viscosity low-solid vinyl acetate-ethylene copolymer emulsion GW-707A.
Preferably, the surfactant solution in the step (1) is a mixed solution obtained by uniformly mixing deionized water, compound polyvinyl alcohol, octyl phenol polyoxyethylene ether and reducing agent zinc formaldehyde sulfoxylate and heating to 75-85 ℃; the mass ratio of deionized water, compound polyvinyl alcohol, octyl phenol polyoxyethylene ether and reducer zinc formaldehyde sulfoxylate in the surfactant solution is 275-283.3: 13.5-15.0: 1.67-1.94: 1.
preferably, the compound polyvinyl alcohol is prepared by mixing polyvinyl alcohol 05-88 and polyvinyl alcohol 17-88 according to the mass ratio of 11-12: 1-1.5.
Preferably, the mass percentage of the oxidant hydrogen peroxide in the step (1) is 1.2-2.0%, and the total mass of the oxidant hydrogen peroxide is 8.0-9.5% of the total mass of the monomer vinyl acetate added in the step (1) (initial monomer vinyl acetate and continuous monomer vinyl acetate).
Preferably, the ratio of the mass of the initial vinyl acetate to the total mass of the continuous monomeric vinyl acetate in step (1) is 2.0-2.4: 1.
Preferably, the continuous monomer vinyl acetate is added in three batches in the reaction process in the step (1), and the addition amount of each batch is equal; the specific adding time is that the reaction is added when the reaction is carried out for 10min, 30min and 50min, the adding time is 15min at each time interval, and then the adding is stopped for 5min and is continued.
Preferably, the mass percentage of the zinc sulfoxylate formaldehyde (ZFS) aqueous solution added in the curing period in the step (1) is 4-5%, and the ratio of the mass of the zinc sulfoxylate formaldehyde (ZFS) aqueous solution to the total mass of the vinyl acetate monomers (initial vinyl acetate monomer + continuous vinyl acetate monomer) is 0.75%.
Preferably, the addition amount of the tert-butyl peroxybenzoate is 0.15-0.3 kg per ton of the reaction solution in the step (2); the addition amount of the sodium bicarbonate is 1.5-2.2 kg per ton of the reaction liquid in the step (2); the addition amount of the defoaming agent is 1.5-2.0 kg per ton of the reaction liquid in the step (2); the addition amount of the deionized water is 30-50 kg per ton of the reaction liquid in the step (2).
Compared with the prior art, the invention has the following beneficial effects:
1) the low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion GW-707A has better rheological property, maintains the low viscosity of the emulsion, reduces the solid content and ensures that the leveling property of the emulsion is more excellent; the low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion GW-707A prepared by the invention has the characteristics of good rheological property, low solid content, low viscosity, high flexibility and good film forming property;
2) the low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion GW-707A makes up the defects of large film forming hardness and insufficient flexibility of the existing vinyl acetate-ethylene copolymer emulsion model due to high mechanical stability and high curing speed, and provides an emulsion raw material with better performance for the adhesive type and the spray type;
3) the invention optimizes the performance of the vinyl acetate-ethylene copolymer emulsion on the premise of not changing the raw material components of the original vinyl acetate-ethylene copolymer emulsion, has simple preparation process and is easy to realize industrialization.
Detailed Description
The following detailed description is to be read in connection with specific embodiments, but it should be understood that the scope of the invention is not limited to the specific embodiments. The raw materials and reagents used in the examples were all commercially available unless otherwise specified. The oxidant hydrogen peroxide solution used in the following examples is 150kg of hydrogen peroxide solution with a mass concentration of 35%, and the hydrogen peroxide solution is diluted to prepare a hydrogen peroxide solution with a mass concentration of 1.2-2.0%.
The vinyl acetate purity used in the following examples was 99.5%; wherein the initial monomer vinyl acetate and the continuous monomer vinyl acetate are the same substance, and the addition sequence is different, so the names are different; the monomer vinyl acetate described in the examples refers to the generic term of initial monomer vinyl acetate + continuous monomer vinyl acetate.
Example 1
A preparation method of a low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion comprises the following specific operation steps:
(1) 4500kg of monomeric vinyl acetate was received in a monomer batch tank; taking deionized water as a solvent, uniformly mixing 258kg of compound polyvinyl alcohol (obtained by mixing 05-88 and 17-88 of polyvinyl alcohol according to a mass ratio of 12: 1) with 31.2kg of octylphenol polyoxyethylene ether and 18kg of zinc sulfoxylate formaldehyde serving as a reducing agent in a container, and heating to 85 ℃ to prepare 5000-5100 kg of mixed solution, namely surfactant solution, for later use; the mass ratio of deionized water, compound polyvinyl alcohol, octyl phenol polyoxyethylene ether and reducer zinc formaldehyde sulfoxylate in the surfactant solution is 277.8-283.3: 14.3: 1.73: 1; then adding 150kg Zinc Formaldehyde Sulfoxylate (ZFS) and 2850kg deionized water into the post-addition tank to prepare a 5% zinc formaldehyde sulfoxylate aqueous solution for later use;
adding 2750kg of initial monomer vinyl acetate and 5000kg of the standby surfactant solution into a polymerization kettle with a stirrer and an external heat removal device for pre-emulsification, starting the stirrer and a circulating pump, heating to 50-60 ℃, stopping heating, introducing ethylene, boosting the pressure to 3.8MPa, dropwise adding 1.82% by mass of oxidant hydrogen peroxide solution to initiate reaction, stirring for 100min, adding continuous monomer vinyl acetate (the continuous vinyl acetate is added in three batches, the adding amount of each batch is equal, the adding time is 10min, 30min and 50min after the reaction, the adding time is 15min at each time interval, stopping adding for 5min, and continuing adding) 1250kg, wherein the ratio of the mass of the initial vinyl acetate to the mass of the continuous monomer vinyl acetate is 2.2:1, heat is released during the reaction, and the reaction temperature is finally controlled to be 78-82 ℃ for reaction, cooling by using circulating cooling water of a reactor heat exchanger when the reaction is overheated, continuously adding ethylene, boosting the pressure to 5.9MPa, stopping adding the ethylene, setting the pressure of the reactor to be 1.8MPa when the reaction time reaches 70min, automatically controlling the adding rate of an oxidant by an oxidant feeding pump according to the reaction temperature, adjusting the rate of adding the oxidant to be 100% when the reaction time reaches 100min, adding the oxidant to be 14min, controlling the total adding amount of a hydrogen peroxide solution with the mass percentage of 1.82% to be 320-380 kg (namely the total adding amount of the hydrogen peroxide is 8.0-9.5% of the total mass of the monomer vinyl acetate added in the step (1)), after finishing adding the hydrogen peroxide solution of the oxidant, controlling the reaction temperature to be lower than 77 ℃ and the adding rate of the hydrogen peroxide solution of the oxidant to be 100%, then generating the mixture to enter a curing period, and adding 29.2kg of the standby zinc sulfoxylate formaldehyde (ZFS) aqueous solution with the mass percentage of 5% in the curing period, the mass ratio of the zinc sulfoxylate formaldehyde (ZFS) aqueous solution to the total mass of the monomer vinyl acetate is 0.75 percent, the conversion rate of the monomer vinyl acetate and the ethylene is improved, and the reaction is finished after the curing period is finished;
(2) placing the reaction liquid obtained after the curing period in the step (1) in a flash evaporator to remove residual ethylene, adding 45kg of deionized water into each ton of the reaction liquid to adjust the content of non-volatile components in the reaction liquid, adding 0.15kg of tert-butyl peroxybenzoate into each ton of the reaction liquid to reduce the content of vinyl acetate in the reaction liquid, adding 1.8kg of sodium bicarbonate into each ton of the reaction liquid to adjust the pH value of the reaction liquid, adding 1.5kg of defoaming agent into each ton of the reaction liquid to remove residual fine bubbles in the reaction liquid, stirring uniformly, filtering and removing filter residues to obtain the low-viscosity low-solid vinyl acetate-ethylene copolymer emulsion GW-707A.
Example 2
A preparation method of a low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion comprises the following operation steps:
(1) 4500kg of monomeric vinyl acetate was received in a monomer batch tank; taking deionized water as a solvent, and uniformly mixing 243kg of compound polyvinyl alcohol (obtained by mixing 05-88 parts of polyvinyl alcohol and 17-88 parts of polyvinyl alcohol according to a mass ratio of 111.5) with 30kg of octyl phenol polyoxyethylene ether and 18kg of zinc formaldehyde sulfoxylate serving as a reducing agent in a container, and heating to 75 ℃ to prepare 4950-5000 kg of mixed solution, namely surfactant solution, for later use; the mass ratio of deionized water, compound polyvinyl alcohol, octyl phenol polyoxyethylene ether and reducer zinc formaldehyde in the surfactant solution is 275-277.8: 13.5: 1.67-1.94: 1; then adding 120kg Zinc Formaldehyde Sulfoxylate (ZFS) and 2880kg deionized water into the post-addition tank to prepare a 4% zinc formaldehyde sulfoxylate aqueous solution for later use;
adding 2800kg of initial monomer vinyl acetate and 5000kg of the standby surfactant solution into a polymerization kettle with a stirrer and an external heat removal device for pre-emulsification, starting the stirrer and a circulating pump, heating to 50-60 ℃, stopping heating, introducing ethylene, boosting the pressure to 1.5MPa, dropwise adding an oxidant hydrogen peroxide solution with the mass percentage of 1.2% to initiate reaction, stirring for reaction for 116min, beginning to add continuous monomer vinyl acetate (the continuous vinyl acetate is added in three batches, the adding amount of each batch is equal, the adding time is 10min, 30min and 50min after the reaction, the adding time is 15min at each time interval, stopping adding for 5min, and continuing to add) 1400kg, wherein the ratio of the mass of the initial vinyl acetate to the mass of the continuous monomer vinyl acetate is 2.0:1, heat is released in the reaction process, and the reaction temperature is finally controlled to react at 78-82 ℃, cooling by using circulating cooling water of a reactor heat exchanger when the reaction is overheated, continuously adding ethylene, boosting the pressure to 5.9MPa, stopping adding the ethylene, setting the pressure of the reactor to be 1.8MPa when the reaction time reaches 70min, automatically controlling the adding rate of an oxidant by an oxidant feeding pump according to the reaction temperature, adjusting the rate of adding the oxidant to be 100% when the reaction time reaches 116min, adding the oxidant to be 14min, controlling the total adding amount of a hydrogen peroxide solution with the mass percentage of 1.2% to be 336-399 kg (namely the total adding amount of the hydrogen peroxide to be 8.0-9.5% of the total mass of the monomer vinyl acetate added in the step (1)), after finishing adding the hydrogen peroxide solution of the oxidant, controlling the reaction temperature to be lower than 77 ℃ and the adding rate of the hydrogen peroxide solution of the oxidant to be 100%, then generating the mixture to enter a curing period, and adding 31.5kg of the standby zinc sulfoxylate formaldehyde (ZFS) aqueous solution with the mass percentage of 4% in the curing period, the mass ratio of the zinc sulfoxylate formaldehyde (ZFS) aqueous solution to the total mass of the monomer vinyl acetate is 0.75 percent, the conversion rate of the monomer vinyl acetate and the ethylene is improved, and the reaction is finished after the curing period is finished;
(2) and (2) placing the reaction liquid obtained after the curing period in the step (1) in a flash evaporator to remove residual ethylene, adding 30kg of deionized water into each ton of the reaction liquid to adjust the content of non-volatile components in the reaction liquid, adding 0.3kg of tert-butyl peroxybenzoate into each ton of the reaction liquid to reduce the content of vinyl acetate in the reaction liquid, adding 1.5kg of sodium bicarbonate into each ton of the reaction liquid to adjust the pH value of the reaction liquid, adding 1.8kg of defoaming agent into each ton of the reaction liquid to remove residual fine bubbles in the reaction liquid, stirring uniformly, and filtering to remove filter residues to obtain the low-viscosity low-solid vinyl acetate-ethylene copolymer emulsion GW-707A.
Example 3
A preparation method of a low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion comprises the following operation steps:
(1) 4500kg of monomeric vinyl acetate was received in a monomer batch tank; taking deionized water as a solvent, uniformly mixing 270kg of compound polyvinyl alcohol (obtained by mixing 05-88 and 17-88 of polyvinyl alcohol according to a mass ratio of 12: 1) with 34.92kg of octyl phenol polyoxyethylene ether and 18kg of zinc sulfoxylate formaldehyde serving as a reducing agent in a container, and heating to 80 ℃ to prepare 5005-5045 kg of mixed solution, namely surfactant solution, for later use; the mass ratio of deionized water, compound polyvinyl alcohol, octyl phenol polyoxyethylene ether and reducer zinc formaldehyde in the surfactant solution is 278-280: 15.0: 1.94: 1; then adding 150kg Zinc Formaldehyde Sulfoxylate (ZFS) and 2850kg deionized water into the post-addition tank to prepare a 5% zinc formaldehyde sulfoxylate aqueous solution for later use;
adding 2880kg of initial monomer vinyl acetate and 5000kg of the standby surfactant solution into a polymerization kettle with a stirrer and an external heat removal device for pre-emulsification, starting the stirrer and a circulating pump, heating to 50-60 ℃, stopping heating, introducing ethylene, boosting the pressure to 6.0MPa, dropwise adding an oxidant hydrogen peroxide solution with the mass percentage of 2.0% to initiate reaction, stirring for 120min, beginning to add continuous monomer vinyl acetate (the continuous vinyl acetate is added in three batches, the adding amount of each batch is equal, the adding time is 10min, 30min and 50min, the adding time is 15min in each time interval, stopping adding for 5min, and continuing adding) 1200kg of initial vinyl acetate, the mass ratio of the initial vinyl acetate to the continuous monomer vinyl acetate is 2.4:1, releasing heat in the reaction process, and finally controlling the reaction temperature to be 78-82 ℃ for reaction, cooling by using circulating cooling water of a reactor heat exchanger when the reaction is overheated, continuously adding ethylene, boosting the pressure to 5.9MPa, stopping adding the ethylene, setting the pressure of the reactor to be 1.8MPa when the reaction time reaches 70min, automatically controlling the adding rate of an oxidant by an oxidant feeding pump according to the reaction temperature, adjusting the rate of adding the oxidant to be 100% when the reaction time reaches 120min, adding the oxidant to be 14min, controlling the total adding amount of a hydrogen peroxide solution with the mass percentage of 2.0% to be 326-387.6 kg (namely the total adding mass of the hydrogen peroxide is 8.0-9.5% of the total mass of the monomer vinyl acetate added in the step (1)), after finishing adding the hydrogen peroxide solution as the oxidant, controlling the reaction temperature to be lower than 77 ℃ and the adding rate of the hydrogen peroxide solution as the oxidant to be increased to be 100%, then producing to enter a curing period, and adding 30.6kg of the standby zinc sulfoxylate formaldehyde (ZFS) aqueous solution with the mass percentage of 5% in the curing period, the mass ratio of the zinc sulfoxylate formaldehyde (ZFS) aqueous solution to the total mass of the monomer vinyl acetate is 0.75 percent, the conversion rate of the monomer vinyl acetate and the ethylene is improved, and the reaction is finished after the curing period is finished; (ii) a
(2) Placing the reaction liquid obtained after the curing period in the step (1) in a flash evaporator to remove residual ethylene, adding 50kg of deionized water into each ton of the reaction liquid to adjust the content of non-volatile components in the reaction liquid, adding 0.25kg of tert-butyl peroxybenzoate into each ton of the reaction liquid to reduce the content of vinyl acetate in the reaction liquid, adding 2.0kg of sodium bicarbonate into each ton of the reaction liquid to adjust the pH value of the reaction liquid, adding 2.0kg of defoaming agent into each ton of the reaction liquid to remove residual fine bubbles in the reaction liquid, stirring uniformly, filtering and removing filter residues to obtain the low-viscosity low-solid vinyl acetate-ethylene copolymer emulsion GW-707A.
The comparison table of the low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion GW-707A prepared by the method and the conventional GW-707 shows the test results of important quality performance indexes of the emulsion in the following table 1:
TABLE 1
The quality performance test results of the low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion GW-707A prepared by the invention are shown in the table 2:
TABLE 2
| Analysis item | Index (I) |
| Appearance of the product | White homogeneous emulsion |
| pH value | 4～6 |
| Non-volatile matter,% | 45.0-50.0 |
| Content of ethylene% | 16±2％ |
| Viscosity (25 ℃), mPa.s | 800～1000 |
| Residual monomer content% | ≤0.1 |
| Dilution stability,% of | ≤2.0 |
| Particle size, μm | ≤0.8 |
| Tensile strength, MPa | 5.25 |
| Elongation at break,% | 612 |
As can be seen from the data in Table 1, the ratio of the low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion GW-707A to the conventional GW-707 is lower, the softness of the product after film forming is better, the rheological property is obviously better than that of the conventional GW-707, the leveling property is better, and the low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion GW-707 is suitable for being used as a spray coating of textiles and paper industry; as can be seen from the data in Table 2, GW-707A belongs to low-viscosity low-solid-content emulsion, has good rheological property, good tensile strength and elongation at break and ideal soft and moist performance, and can meet the industrial requirements of more waterproof coatings, adhesives and textile coatings.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (8)
1. A preparation method of a low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion is characterized by comprising the following operation steps:
(1) adding initial monomer vinyl acetate and a surfactant solution into a reactor for pre-emulsification, continuously adding an oxidant hydrogen peroxide solution under the conditions of an ethylene atmosphere and a pressure of 1.5-6.0MPa to initiate a reaction, stirring for reaction for 100-120min, uniformly and sectionally adding continuous monomer vinyl acetate in the reaction process, controlling the temperature to be 78-82 ℃ in the reaction process, after the continuous monomer vinyl acetate is completely added, enabling the reaction temperature to be lower than 77 ℃ and the adding rate of the oxidant hydrogen peroxide solution to be increased to 100%, enabling the production to enter a curing period, adding a zinc sulfoxylate formaldehyde aqueous solution in the curing period, and ending the reaction after the curing period;
(2) and (2) placing the reaction liquid obtained after the curing period in the step (1) in a flash evaporator to remove residual ethylene, adding water to adjust the content of non-volatile components in the reaction liquid, adding tert-butyl peroxybenzoate to reduce the content of vinyl acetate in the reaction liquid, adding sodium bicarbonate to adjust the pH value of the reaction liquid, adding an antifoaming agent to remove residual fine bubbles in the reaction liquid, uniformly stirring, filtering and removing filter residues to obtain the low-viscosity low-solid vinyl acetate-ethylene copolymer emulsion GW-707A.
2. The method of claim 1, wherein: the surfactant solution in the step (1) is a mixed solution obtained by uniformly mixing water, compound polyvinyl alcohol, octyl phenol polyoxyethylene ether and a reducing agent zinc formaldehyde sulfoxylate and heating to 75-85 ℃; the mass ratio of water in the surfactant solution, the compound polyvinyl alcohol, the octyl phenol polyoxyethylene ether and the reducer zinc formaldehyde sulfoxylate is 275-283.3: 13.5-15.0: 1.67-1.94: 1.
3. the method of claim 2, wherein: the compound polyvinyl alcohol is prepared by mixing polyvinyl alcohol 05-88 and polyvinyl alcohol 17-88 according to the mass ratio of 11-12: 1-1.5.
4. The method of claim 1, wherein: in the step (1), the mass percentage of the oxidant hydrogen peroxide is 1.2-2.0%, and the total mass of the oxidant hydrogen peroxide is 8.0-9.5% of the total mass of the monomer vinyl acetate added in the step (1).
5. The method of claim 1, wherein: the mass ratio of the initial vinyl acetate to the total mass of the continuous monomer vinyl acetate in the step (1) is 2.0-2.4: 1.
6. The method of claim 1, wherein: adding continuous monomer vinyl acetate in three batches in the reaction process in the step (1), wherein the adding amount of each batch is equal; the specific adding time is that the reaction is added when the reaction is carried out for 10min, 30min and 50min, the adding time is 15min at each time interval, and then the adding is stopped for 5min and is continued.
7. The method of claim 1, wherein: the mass percentage of the zinc sulfoxylate formaldehyde aqueous solution added in the curing period in the step (1) is 4-5%, and the mass ratio of the zinc sulfoxylate formaldehyde (ZFS) aqueous solution to the total mass of the monomer vinyl acetate is 0.75%.
8. The method of claim 1, wherein: the addition amount of the tert-butyl peroxybenzoate is 0.15-0.3 kg per ton of the reaction solution in the step (2); the addition amount of the sodium bicarbonate is 1.5-2.2 kg per ton of the reaction liquid in the step (2); the addition amount of the defoaming agent is 1.5-2.0 kg per ton of the reaction liquid in the step (2); the addition amount of the deionized water is 30-50 kg per ton of the reaction liquid in the step (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110987616.2A CN113773434A (en) | 2021-08-26 | 2021-08-26 | Preparation method of low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110987616.2A CN113773434A (en) | 2021-08-26 | 2021-08-26 | Preparation method of low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113773434A true CN113773434A (en) | 2021-12-10 |
Family
ID=78839484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110987616.2A Pending CN113773434A (en) | 2021-08-26 | 2021-08-26 | Preparation method of low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113773434A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030858A (en) * | 2009-09-30 | 2011-04-27 | 中国石油化工集团公司 | Vinyl acetate-ethylene copolymer emulsion (VAE emulsion) and synthesis method thereof |
| CN109575311A (en) * | 2018-11-27 | 2019-04-05 | 广西广维化工有限责任公司 | A kind of preparation method of vinyl copolymer emulsion |
-
2021
- 2021-08-26 CN CN202110987616.2A patent/CN113773434A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030858A (en) * | 2009-09-30 | 2011-04-27 | 中国石油化工集团公司 | Vinyl acetate-ethylene copolymer emulsion (VAE emulsion) and synthesis method thereof |
| CN109575311A (en) * | 2018-11-27 | 2019-04-05 | 广西广维化工有限责任公司 | A kind of preparation method of vinyl copolymer emulsion |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109575311B (en) | Preparation method of vinyl acetate-ethylene copolymer emulsion | |
| CN107118650B (en) | Silica sol/polyacrylate emulsion containing hydroxyl-amino resin baking varnish and preparation method thereof | |
| CN102372885A (en) | High viscosity polyvinyl acetate emulsion and preparation method thereof | |
| CN106866895A (en) | A kind of high-performance poly carboxylic acid series water reducer and preparation method thereof | |
| CN112266439B (en) | Ammonia-free waterproof emulsion and preparation method thereof | |
| EP2847290B1 (en) | Use of copolymers as tackifiers for adhesives | |
| CN106398372A (en) | High-molecular copolymer dispersant for paint and preparation method thereof | |
| CN108251047B (en) | Preparation method of composite starch adhesive | |
| CN106854251B (en) | High-solid-content polyvinyl acetate emulsion and preparation method thereof | |
| CN112708140B (en) | Early-strength cement dispersion polymer and preparation method thereof | |
| CN113773434A (en) | Preparation method of low-solid low-viscosity vinyl acetate-ethylene copolymer emulsion | |
| CN110330592B (en) | Preparation method of polyacrylamide for fragrant adhesive | |
| CN102532389B (en) | Poly-vinyl versatate-vinyl acetate-ethylene emulsion and emulsion polymerization preparation method | |
| CN111647115A (en) | Polycarboxylate superplasticizer mother liquor and preparation method thereof, and polycarboxylate superplasticizer and preparation method thereof | |
| CN113717312A (en) | Preparation method of vinyl acetate-ethylene copolymer emulsion with low free formaldehyde | |
| CN108440693B (en) | High-melt-index resin and preparation method thereof | |
| CN101186662B (en) | Initiator for ultra-low Mooney fluororubber production and polymerization, and preparation method thereof | |
| CN112708141B (en) | Slump-retaining cement dispersion polymer and preparation method thereof | |
| CN112812312B (en) | High workability cement dispersion polymer and preparation method thereof | |
| CN112708142B (en) | Hydration regulation type cement dispersion polymer and preparation method thereof | |
| RU2753761C1 (en) | Fast-setting polymer for dispersing cement and method for its production | |
| CN114014997B (en) | Normal-temperature synthesis method of polycarboxylate superplasticizer with polyether macromonomer as raw material | |
| KR100462452B1 (en) | method of manufacturing the concrete admixture | |
| CN114478892A (en) | Non-ammonia phenyl propyl emulsion and preparation method and application thereof | |
| CN117866134A (en) | Vinyl chloride suspension polymerization dispersing agent with defoaming function and preparation method and application thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211210 |