CN100365033C - Method for synthesizing high solid content vinyl acetate-ethylene copolymer emulsion - Google Patents
Method for synthesizing high solid content vinyl acetate-ethylene copolymer emulsion Download PDFInfo
- Publication number
- CN100365033C CN100365033C CNB2004100095065A CN200410009506A CN100365033C CN 100365033 C CN100365033 C CN 100365033C CN B2004100095065 A CNB2004100095065 A CN B2004100095065A CN 200410009506 A CN200410009506 A CN 200410009506A CN 100365033 C CN100365033 C CN 100365033C
- Authority
- CN
- China
- Prior art keywords
- vinyl acetate
- polyvinyl alcohol
- copolymer emulsion
- ethylene copolymer
- monomer
- 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
Abstract
The present invention relates to a synthetic method for synthesizing vinyl acetate-ethylene copolymer emulsion with high solid content. The method is characterized in that an annular tubular reaction apparatus existing in the prior art is used, a process for polymerizing emulsion by a continuous method is adopted, and the product of the present invention is prepared. The detail recipe and the detail preparing method are disclosed in the specification. The present invention has the advantages that the problem brought by the apparatus limitation of stirring and heat transferring effects, etc. in the intermittent synthesizing process used in the past is solved by using the continuous production method, only the polyvinyl alcohol is used as protective colloid without using emulsifying agents, and the problems that the primary viscous force is reduced and the bonding force of base material is weakened because of the introduction of the emulsifying agents are avoided. The present invention has the advantages of uniform and stable product quality, wide adjustable range of viscosity, high solidifying speed, good primary viscous force and high water-resistant bonding strength to wood, etc. The product of the present invention is used for bonding and packing industry for wood.
Description
Technical field
The present invention relates to the synthetic method of copolymer emulsion, specifically relate to the synthetic method of high solids content vinyl acetate-ethylene copolymer emulsion.
Background technology
Aqueous binder is than Solvent Adhesive, environmental protection more, and in use also than the relative saving energy of Hotmelt Adhesive, the proportion in tackiness agent increases year by year.But aqueous binder is because the water content height, and often bring curing speed slow, make shortcomings such as being increased, be difficult to satisfy quick bonding requirements by water content such as bonding timber.Therefore, it is very active to improve above-mentioned insufficient research work by the raising emulsion solid content in recent years.
Vinyl acetate-ethylene copolymer emulsion tackiness agent bonding in extensive range, water tolerance is good, by the method among the present invention, the solid content that improves vinyl acetate-ethylene copolymerization is to 65-70%, can obtain that curing speed is fast, bonding strength is high, the novel vinyl acetate-ethylene copolymerization emulsions of water-fast, fine heat-resisting performance.Many countries are very interesting to this project.As: U.S. Pat 5936020 has disclosed the polyvinyl alcohol of employing＞3% (polymerization degree is 100-500) and the emulsifying agent of 1-4% (the HLB value is 16.5-18.0); and the dispersion agent of 0.2-1% is produced the vinyl acetate-ethylene copolymerization emulsions of solid content 65-75% as the protection system.
U.S. Pat 4921898 has disclosed the polyvinyl alcohol of employing 2-4% (polymerization degree is 100-600) and the polyethenoxy ether class emulsifying agent of 1-4% is an emulsification protection system, produces the vinyl acetate-ethylene copolymerization emulsions of solid content 65-70%, viscosity＜3500mpa.s.
U.S. Pat 5110865 has disclosed employing 2.5-5.0% emulsifying dispersant, comprise the polyvinyl alcohol of 1.0-1.9% (polymerization degree is 300-1000) and the non-ionic polyoxyethylene ethers emulsifying agent of 1.0-3.0% (the HLB value is 1.5-17.5), produce the vinyl acetate-ethylene copolymerization emulsions of solid content 65-75%.
U.S. Pat 6001916 has disclosed the employing seed emulsion polymerization and has produced vinyl acetate-ethylene copolymerization emulsions, adds polyvinyl alcohol and nonionic emulsifying agent when polymerization, and solid content reaches more than 65%.
European patent EP 0929798A2 has disclosed the polyvinyl alcohol that adopts 2-8% and the 0.25-4.5% emulsifying agent of (epoxide group of 50-70 is contained in HLB value 〉=18.0), production high solids content vinyl acetate-ethylene copolymer.
Above technology all adopts intermittence type polymerization technology, press in the reactor at band and to realize letex polymerization, stirred, the equipment of heat-transfer effect etc. limits to, the vinyl acetate-ethylene copolymer viscosity controller of producing lower, be difficult under viscosity higher, guarantee to obtain higher ethylene content.Therefore, the vinyl acetate-ethylene copolymer emulsion of the adhesive property excellence of exploitation high solids content becomes the task of top priority.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, and provide a kind of annular tube type reaction unit of the prior art that utilizes, take the continuous processing emulsion polymerization technique, produce the method for the vinyl acetate-ethylene copolymer emulsion of high solids content, adhesive property excellence.
The object of the invention can realize by following measure: the method for vinyl acetate-ethylene copolymerization of the present invention; be by adopting annular tube type reaction unit and continuous processing emulsion polymerization technique and special polyvinyl alcohol protective colloid to make the vinyl acetate-ethylene copolymer of the adhesive property excellence of high solids content.
Adopt the ring canal reaction device of cubic capacity 2L to carry out the example explanation below, the endless tube diameter is 25mm in the example, and the cooling water jecket diameter of endless tube is 54mm, endless tube cubic capacity 2L, stainless steel, self-control.Form by the multistage jacket pipe, adopt union to connect, be convenient to installing/dismounting.Except certain smooth finish and the withstand voltage 15Mpa of reaching will be arranged, no particular requirement.That the endless tube of production equipment can be is square, ellipse and spiral pipe form, but more than the diameter 100mm, the endless tube volume can be more than 200 liters, no particular restriction.Concrete steps are carried out in the following order: (with reference to accompanying drawing 1)
1, polyvinyl alcohol by a certain percentage, buffer reagent, reductive agent and help reductive agent to be dissolved in the deionized water are mixed with water, inject reaction endless tube 3 continuously by high-pressure metering pump 1a, make it be full of reaction endless tube 3.Wherein: polyvinyl alcohol, buffer reagent, reductive agent and help the weight % of reductive agent to be respectively 8-12%, 0-2.5%, 0.5-2.5%, 0-0.15%, rest part is a deionized water;
2, open screw recycle pump 2, and regulate recycle pump 2 rotating speeds to 200-700 rev/min, adjust 1a to 40-160ml/ minute (water proportion is about 1.0) of water flow volume pump, use volume pump 1b and 1c then respectively in reactor loop 3, injected the monomer vinyl acetate between to for plastic (flow 60-240ml/ minute, monomer proportion is 0.9342) and oxygenant (flow 0.2-0.8ml/ minute, proportion about 1.0), the throughput ratio of water and monomer vinyl acetate between to for plastic is fixed on≤and 2/3; Valve 6 is pressed in the outlet of conditioned reaction device fully, makes system boost to 4-12MPa, and control reaction temperature 100-120 ℃, after reaction mass is warming up to design temperature automatically, open water coolant automatic temperature control system 5, realize temperature auto control;
3, temperature-stable is after set(ting)value, in reactor loop 3, feed ethene with 5-30g/ minute speed again, after half an hour, the continous way polyreaction reaches balance, control this moment monomer from inject endless tube 3 to from endless tube 3 effusive mean residence times at 5-20 minute, measure the index of the vinyl acetate-ethylene copolymerization emulsions that comes out from reactor by laxative remedy: receive above-mentioned emulsion after a certain amount of, under agitation, successively the interval is 15 minutes, to wherein adding the Oxidizing and Reducing Agents that is about product gross weight 0.02-0.04% respectively, record remaining monomer content and reduce to 0.5% when following after slaking, reaction reaches stable, can realize continuous production.
In the vinyl acetate-ethylene copolymer emulsion of the present invention, the total solid content of copolymer emulsion is at 65-70%, and solid content is minimum to be 65%, and wherein the weight sum of monomer component vinyl acetate between to for plastic and ethene accounts for 62-66%.Vinyl acetate between to for plastic accounts for the 70-95% of multipolymer weight, and the ethene component accounts for 5-30%, and more preferably: vinyl acetate between to for plastic accounts for 80-90%, and ethylene content accounts for 10-20%; The polyvinyl alcohol that uses monomer weight 4-8% is as protective colloid; Wherein the low polymerization degree kind of polymerization degree 200-500, alcoholysis degree 86-89% accounts for the 50-90% of polyvinyl alcohol total amount, and the hydrophobic grouping modified polyvinyl alcohol accounts for the 10-50% of polyvinyl alcohol total amount.Initiator adopts the oxidation-reduction initiator system, for example can adopt zinc sulfate formaldehyde of hydrogen peroxide, zinc sulfate formaldehyde of tertbutyl peroxide, tertbutyl peroxide one Sodium Pyrosulfite, tertbutyl peroxide one sodium bisulphite formaldehyde.Wherein, tertbutyl peroxide one Sodium Pyrosulfite is an a pair of effect initiator preferably.Oxygenant, reductive agent consumption account for the 0.25-1.5% of monomer weight respectively; Buffer reagent adopts sodium bicarbonate, (three water) sodium-acetate, yellow soda ash, Sodium isooctanoate etc., and consumption is the 0-1.5% of monomer weight; Can use conducts such as ferrous sulfate to help reductive agent, consumption is the 0-0.1% of monomer weight.
Used polyvinyl alcohol comprises the kind of low polymerization degree (200-500) and the hydrophobic grouping modified polyvinyl alcohol kind of polymerizable medium degree (1000-1700) among the present invention.Hydrophobic grouping modified polyvinyl alcohol kind wherein comprises that ethene modified polyvinyl alcohol, diacetyl group modified polyvinyl alcohol etc. contain the kind of hydrophobic grouping; these special modified polyethylene alcohol are also given high solids content vinyl acetate-ethylene copolymerization excellent in water resistance and very high bonding strength when the excellent protection colloid action is provided.In the polyvinyl alcohol that uses among the present invention, preferably adopting (accounting for the 50-90% of the total consumption of polyvinyl alcohol) over half polymerization degree is that 200-500, alcoholysis degree are the kind of 86-89%, for example AIRVOL
205, AIRVOL
203, and the kinds such as polyvinyl alcohol 04-86 of Beijing Organic Chemical Plant, like this can be so that the water in the letex polymerization have lower viscosity, and make final product when high solids content, have lower viscosity.Simultaneously, in order to guarantee in the letex polymerization, as the polyvinyl alcohol of protective colloid the monomer of high density is had the good emulsifying protective capability, part adopts the polyvinyl alcohol kind of the partial alcoholysis of polymerizable medium degree (1400-1700).The present invention finds; adopt special hydrophobic grouping modified polyethylene alcohol kind; diacetyl group modified polyvinyl alcohol kind Z210, Z100, Z320 etc. as Japanese synthetic chemistry Co., Ltd.; and the ethene modified polyvinyl alcohol kind of Japanese Kuraray company; for example RS-1717, RS1713, RS-1113 etc.; can obtain double effects, emulsification provide protection preferably can be provided in polymerization, make vinyl acetate-ethylene copolymerization emulsions have higher water-fast bonding strength again.Percentage of grafting analysis revealed by Dichlorodiphenyl Acetate ethylene-vinyl copolymer emulsion; adopt above-mentioned specific groups modified polyethylene alcohol to do protective colloid; can make monomers such as vinyl acetate between to for plastic, ethene and polyvinyl alcohol molecular chain form more grafting, percentage of grafting can reach more than 60%.Promptly make polymer monomers and polyvinyl alcohol molecule form and both be insoluble to acetone equal solvent, water-fast again graftomer more than 60%.And the emulsion of the simple use emulsifying agent of contrast routine can find that its acetone insoluble matter seldom, and is almost all solvable, do not form grafting between emulsifying agent and monomer.During the simple conventional polyvinyl alcohol kind of using non-modified, also seldom form graftomer with monomer, water tolerance is lower than the vinyl acetate-ethylene copolymerization emulsions among the present invention.：
The average response residence time among the present invention be meant various materials in endless tube " from entering out " time of average experience, also be the average reaction time of monomer in endless tube.Reaction time length can influence indexs such as monomer conversion and output hourly.The reaction times weak point can make output, production efficiency increase, but monomer conversion is reduced; Otherwise trend is opposite.So must control suitable mean residence time, mean residence time scope of the present invention is 5-20 minute.Per minute flow size has determined reaction time length.Calculation formula is: reactor loop cumulative volume/each material flow sum.Water and monomeric flow range were respectively 40-160ml/ minute and 60-240ml/ minute among the present invention, and water and monomeric throughput ratio are fixed as 2/3, that is to say, when the water flow is 40ml/ minute, monomeric flow is that (the annular-pipe reactor volume was about 2000ml in 60ml/ minute,), this moment, mean residence time was annular-pipe reactor volume/each material flow sum, be convenience of calculation, ignore oxidizer flow rate and the gas shared volume of ethene mutually, mean residence time=2000/ this moment (40+60)=20 minute; And the water flow in the time of 160ml/ minute monomeric flow be 240ml/ minute, mean residence time=2000/ this moment (160+240)=5 minute.In this residence time scope, no matter flow is transferred fast the accent slowly, the material proportion of aqueous phase is constant, and this is to reach 65% for the solid content that makes product; Reach more than 65%, then the ratio of the two also is less than 2/3.PVA wherein, reductive agent etc. all have an optimum concentration range, exceed this scope and then can not get described high solids content vinyl acetate-ethylene copolymerization emulsions.
The present invention has following advantage compared to existing technology:
1, the present invention has adopted annular reactor and continuous processing emulsion polymerization technique technology, continuous production vinyl acetate-ethylene copolymerization emulsions, quality product stable homogeneous, the solid content height, the viscosity adjustable extent is wide, and curing speed is fast, and timber etc. is had very high water-fast cohesive strength; Solved in the intermittence type polymerization technology that in the past adopted because limited to by equipment such as stirrings, heat-transfer effect the problem that institute's vinyl acetate-ethylene copolymer viscosity controller of producing is lower, be difficult to assurance acquisition higher solids content under viscosity higher.
2, the present invention is a protective colloid with polyvinyl alcohol merely, does not use emulsifying agent just can guarantee enough dispersions, stabilising effect, has avoided the reduction of the initial bonding strength that the introducing because of emulsifying agent causes and to the weakening of polar substrates bonding force, and has simplified technology.
3, the used special modified polyethylene alcohol of invention when the excellent protection colloid action is provided, is also given high-content vinyl acetate-ethylene copolymerization emulsions excellent in water resistance and very high bonding strength.
Description of drawings
Fig. 1: the annular tube type reaction unit that uses in the prior art
Explanation among Fig. 1: 1, high pressure continuously feeding bull ram pump or diaphragm type juice amount pump (1a water volume pump, 1b vinyl acetate between to for plastic volume pump, 1c oxygenant volume pump); 2, high pressure screw recycle pump (can adopt single screw form or twin screw form, what adopt in the example of the present invention is Britain's Marshall public affairs (MARSHALLPUMPS) 3000 type list screw rod recycle pumps); 3, the reaction under high pressure endless tube (is made up of the multistage jacket pipe, is adopted union to connect, be convenient to installing/dismounting.That endless tube can be is square, ellipse and spiral pipe form); 4, the ethylene stream adjustable valve (is made up of ethene mass flowmeter, pneumatic adjusting valve and the controller that is attached thereto.The ethene mass flowmeter can adopt the MFC081 SMART model of KROHNE company, and pneumatic adjusting valve adopts the VSM type of Wuzhong, Jiangsu instrucment and meter plant, and controller adopts COMMANDER 300 types of ABB AB); 5, the water coolant automatic temperature control system (is controlled the cooling water inflow that feeds reaction endless tube 3 external jackets automatically by pneumatic adjusting valve and temperature controller, thereby is reached the purpose of automatic control reaction temperature.Pneumatic adjusting valve can adopt the pneumatic diaphragm control valve of Tianjin self-service instrument four factories, and model is 7MAP-16K, and temperature controller can adopt COMMANDER 300 types of ABB AB); 6, reactor outlet presses valve (to be contained in the endless tube discharge port, to be used to keep and control the pressure of reactive system fully.Can adopt needle valve or nitrogen pressure formula control valve, the latter such as Britain BASKERVILLE ﹠amp; 2500 types of LINDSAY company are pressed valve fully); 7, the water header tank that comprises polyvinyl alcohol, reductive agent, buffer reagent; 8, vinyl acetate between to for plastic is high-order poor; 9, oxygenant header tank; 10, ethene groove.
Embodiment
Enumerate four embodiment below, the present invention is further specified, but the present invention is not only limited to these embodiment.
Embodiment 1
Polyvinyl alcohol AIRVOL with 2.8Kg
203 (alcoholysis degrees 88%, the polymerization degree 300), 1.36Kg polyvinyl alcohol RS-1717 (Japanese Kuraray company, alcoholysis degree 92-94%, the polymerization degree 1700), 0.2Kg the Sodium isooctanoate buffer reagent, 0.3Kg the Sodium Pyrosulfite reductive agent and the ferrous sulfate of 0.05g help reductive agent to be dissolved in the deionized water of 35Kg, be mixed with water, by high-pressure metering pump 1a water is injected the reaction under high pressure endless tube 3 that volume is 2L continuously, after water is filled it up with reaction endless tube 3, open screw recycle pump 2, and regulate recycle pump 2 rotating speeds to 600 rev/min, adjust 1a to 60ml/ minute (water proportion is about 1.0) of water flow volume pump, in reactor loop 3, injected the monomer vinyl acetate between to for plastic (flow 90ml/ minute with volume pump 1b and 1c respectively then, monomer proportion is 0.9342, corrected flow is 84g/ minute) and initiator tertbutyl peroxide (flow 0.3ml/ minute), and valve 6 is pressed in the outlet of conditioned reaction device fully, make system boost to 7MPa, set 105 ℃ of temperature of reaction, after reaction mass is warming up to 105 ℃ automatically, open water coolant automatic temperature control system 5, realize temperature auto control.After temperature of reaction is stabilized in set(ting)value, in reactor loop 3, feed ethene with 18g/ minute speed again, after half an hour, the vinyl acetate-ethylene copolymerization emulsions index that mensuration is come out from reactor: receive above-mentioned emulsion after a certain amount of, under agitation, successively the interval is 15 minutes, to wherein adding oxygenant (tertbutyl peroxide respectively, every 10Kg emulsion adds 2.5g) and reductive agent (Sodium Pyrosulfite, every 10Kg emulsion adds 2.5g), after slaking, remaining monomer content is reduced to below 0.5%, and product touches the mark.In the present invention, do not carry out the preceding monomer conversion of slaking and reached 97%.
The water flow is 60ml/ minute among the embodiment, and monomeric flow is 90ml/ minute, and this moment, mean residence time was about 2000/ (60+90)=13.3 minute, within the scope of the present invention.
Embodiment 2
Synthetic identical with embodiment 1, just with polyvinyl alcohol AIRVOL
203 (alcoholysis degree 88%, the polymerization degree 300) are adjusted into 3.2Kg's, and polyvinyl alcohol RS-1717 replaces with RS-1113 (Japanese Kuraray company, alcoholysis degree 97.5-99%, 4% solution viscosity 16-22mpa.s), and weight is set at 115 ℃ for the 1.7Kg. temperature of reaction.
Embodiment 3
Synthetic identical with embodiment 1, just with polyvinyl alcohol AIRVOL
203 replace with AIRVOL
205 (alcoholysis degree 88% polymerization degree 500) replace with RS-1113 (Japanese Kuraray company, alcoholysis degree 97.5-99%, 4% solution viscosity 16-22mpa.s) with polyvinyl alcohol RS-1717.Temperature of reaction is 110 ℃.
Embodiment 4
Synthetic identical with embodiment 1, just with polyvinyl alcohol AIRVOL
203 replace with AIRVOL
205 (alcoholysis degree 88%, the polymerization degree 500) replace with RS-1713 (Japanese Kuraray company, alcoholysis degree 92-94%, 4% solution viscosity 15.5-21mpa..s) with polyvinyl alcohol RS-1717.Temperature of reaction is that the conventional index of gained emulsion in 115 ℃ of the foregoing descriptions is as shown in table 1 below:
Table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Solid content % | 65.5 | 65.2 | 65.0 | 65.4 |
| Ethylene content | 16.1％ | 16.1％ | 15.5％ | 16.4％ |
| Viscosity mpa.s | 7050 | 4980 | 6420 | 6820 |
| Remaining monomer | 0.2％ | 0.3％ | 0.3％ | 0.4％ |
| Shearing resistance N/mm 2 | 11.67 | 11.65 | 10.57 | 10.07 |
The solid content of final vinyl acetate-ethylene copolymerization emulsions is controlled at 65-70%, and viscosity is 4000-10000mpa.s.Contain the vinyl acetate between to for plastic of the 70-95% that has an appointment and the ethene of 5-30% in this vinyl acetate-ethylene copolymer.
Adopt identical gluing thickness, different paper, two paper of compare test reach the time that complete paper fibre is torn from being bonded together when peeling off mutually, promptly carry out the initial bonding strength test, can relatively compare the initial bonding strength level.Time, short more then initial bonding strength was good more.Can find out that from following table height the present invention contains vinyl acetate-ethylene copolymerization admittedly and can satisfy bonding requirements fast such as packaging industry better.
Table 2
| Tackiness agent | Initial bonding strength test (second) | ||
| ① | ② | ③ | |
| Commercially available common vinyl acetate-ethylene copolymerization (54.5%) | 22 | 17 | 23 |
| Commercial cigarettes glue 1# | 25 | 18 | 22 |
| Height contains vinyl acetate-ethylene copolymerization admittedly | 17 | 14 | 12 |
According to the present invention, adopt annular reactor and continuous processing emulsion polymerization technique, high solids content (solid content is not less than 65%) the vinyl acetate-ethylene copolymerization emulsions tackiness agent of producing, the quality stable homogeneous, the viscosity adjustable extent is wide, curing speed is fast, and initial bonding strength is good, and timber etc. is had very high water-fast bonding strength.
Product of the present invention is used for adhesive bonding of wood and packaging industry.
Claims (4)
1. the synthetic method of high solids content vinyl acetate-ethylene copolymer emulsion is used the annular tube type reaction unit, it is characterized in that adopting the continuous processing emulsion polymerization technique, and concrete steps are carried out in the following order:
(1), a certain proportion of polyvinyl alcohol, buffer reagent, reductive agent and help reductive agent to be dissolved in the deionized water, be mixed with water, water is injected the reaction endless tube continuously, wherein: polyvinyl alcohol, buffer reagent, reductive agent and help reductive agent to be respectively 8-12%, 0-2.5%, 0.5-2.5%, 0-0.15% at the weight % of aqueous phase, rest part is a deionized water;
(2), inject monomer vinyl acetate between to for plastic and oxygenant, the throughput ratio of water and monomer vinyl acetate between to for plastic is fixed on≤2/3, and control reaction temperature is 100-120 ℃, pressure is at 4-12MPa;
(3), then, feed ethene, the control mean residence time was at 5-20 minute, can be along with the continuous adding of raw material, the output vinyl acetate-ethylene copolymerization emulsions carries out maturation process continuously, to wherein adding the Oxidizing and Reducing Agents that accounts for product gross weight 0.02-0.04% respectively, after slaking, record remaining monomer content and reduce to 0.5% when following, promptly get product of the present invention.
2. the synthetic method of vinyl acetate-ethylene copolymer emulsion according to claim 1 is characterized in that in the vinyl acetate-ethylene copolymer emulsion, and the ethene component accounts for the 5-30% of multipolymer weight, and vinyl acetate between to for plastic accounts for 70-95%; The solid content of copolymer emulsion is between 65-70%; The polyvinyl alcohol that uses monomer weight 4-8% is as protective colloid; Initiator adopts the oxidation-reduction initiator system, and wherein, oxygenant, reductive agent consumption account for the 0.25-1.5% of monomer weight respectively; Buffer reagent adopts sodium bicarbonate, Sodium acetate trihydrate, yellow soda ash, Sodium isooctanoate, and consumption is the 0-1.5% of monomer weight; Can use ferrous sulfate is the 0-0.1% of monomer weight as helping reductive agent, consumption.
3. the synthetic method of vinyl acetate-ethylene copolymer emulsion according to claim 1 is characterized in that in the vinyl acetate-ethylene copolymer emulsion, and the ethene component accounts for the 10-20% of multipolymer weight, and vinyl acetate between to for plastic accounts for 80-90%, and solid content is minimum to be 65%.
4. the synthetic method of vinyl acetate-ethylene copolymer emulsion according to claim 1 and 2; in the polyvinyl alcohol protective colloid that it is characterized in that using; the low polymerization degree kind of polymerization degree 200-500, alcoholysis degree 86-89% accounts for the 50-90% of polyvinyl alcohol total amount, and the hydrophobic grouping modified polyvinyl alcohol accounts for the 10-50% of polyvinyl alcohol total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100095065A CN100365033C (en) | 2004-09-02 | 2004-09-02 | Method for synthesizing high solid content vinyl acetate-ethylene copolymer emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100095065A CN100365033C (en) | 2004-09-02 | 2004-09-02 | Method for synthesizing high solid content vinyl acetate-ethylene copolymer emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1603350A CN1603350A (en) | 2005-04-06 |
| CN100365033C true CN100365033C (en) | 2008-01-30 |
Family
ID=34662517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100095065A Active CN100365033C (en) | 2004-09-02 | 2004-09-02 | Method for synthesizing high solid content vinyl acetate-ethylene copolymer emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100365033C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101835941B (en) * | 2007-10-30 | 2011-07-20 | 广州爱奇实业有限公司 | An artificial turf and a method thereof |
| CN102603955A (en) * | 2012-03-19 | 2012-07-25 | 中国石油化工集团公司 | Method for preparing formaldehyde-free ethylene vinyl acetate emulsion |
| CN103897089B (en) * | 2014-04-01 | 2016-02-17 | 湖南省湘维有限公司 | Low viscous modified polyvinyl alcohol of a kind of crystalloid and preparation method thereof |
| CN106543339A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of method that employing low polymerization degree PVA prepares low-viscosity EVA emulsions |
| CN108818806B (en) * | 2018-04-24 | 2020-05-05 | 广州精点高分子材料制品有限公司 | Single-body entering type ceramic wood and manufacturing method thereof |
| CN110354771A (en) * | 2019-07-24 | 2019-10-22 | 沧州冀春新材料有限公司 | A kind of bottom feeding process applied to lotion processing |
| CN114426626B (en) * | 2020-10-15 | 2023-04-28 | 中国石油化工股份有限公司 | Vinyl acetate-ethylene copolymer emulsion for paper-plastic composite and preparation method thereof |
| CN114032051A (en) * | 2021-12-28 | 2022-02-11 | 贵阳银镒新材料科技有限公司 | Adhesive for packaging fine cigarettes and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0632067A2 (en) * | 1993-06-30 | 1995-01-04 | Bayer Ag | Process for préparing gel-free copolymers of ethylene-vinyl acetate with a high content of vinyl acetate and high mooney viscosity |
| CN1290711A (en) * | 1999-09-30 | 2001-04-11 | 住友化学工业株式会社 | Process for preparing aqueous emulsion of ethylene-acetoethylene ester compolymer |
-
2004
- 2004-09-02 CN CNB2004100095065A patent/CN100365033C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0632067A2 (en) * | 1993-06-30 | 1995-01-04 | Bayer Ag | Process for préparing gel-free copolymers of ethylene-vinyl acetate with a high content of vinyl acetate and high mooney viscosity |
| CN1290711A (en) * | 1999-09-30 | 2001-04-11 | 住友化学工业株式会社 | Process for preparing aqueous emulsion of ethylene-acetoethylene ester compolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1603350A (en) | 2005-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100365033C (en) | Method for synthesizing high solid content vinyl acetate-ethylene copolymer emulsion | |
| CN102030857B (en) | Vinyl acetate-ethylene copolymer emulsion as electrostatic spinning adhesive and synthesis method thereof | |
| CN102603955A (en) | Method for preparing formaldehyde-free ethylene vinyl acetate emulsion | |
| CN104031202A (en) | Polyacrylic acid printing ink resin and preparation method thereof | |
| CN109575311B (en) | Preparation method of vinyl acetate-ethylene copolymer emulsion | |
| CN103665241B (en) | A kind of Cationic ethylene-vinyl acetate copolymer emulsion and production method thereof | |
| CN103626910A (en) | Solid ethylene-vinyl acetate copolymer and preparation method thereof | |
| CN105237338A (en) | System and method for continuously synthesizing high-purity 3-chloro-1,2-propylene glycol | |
| CN102627744A (en) | Preparation method of ether amphoteric polycarboxylic acid water reducing agent | |
| CN114479354B (en) | Preparation method of porous carbon fiber/epoxy resin composite material | |
| CN103045136A (en) | Environment-friendly high-speed cigarette holder glue for cigarettes and preparation method thereof | |
| CN103665231B (en) | A kind of vinyl acetate-ethylene-tertiary ethylene carbonate copolymer emulsion and synthetic method | |
| CN106854251B (en) | High-solid-content polyvinyl acetate emulsion and preparation method thereof | |
| CN101314699B (en) | Water-based adhesion agent and preparation thereof | |
| CN1400269A (en) | Pressure sensitive polyacrylic adhesive and its prepn | |
| CN111484270A (en) | Ultra-long-distance concrete pumping agent | |
| CN113493536B (en) | Vinyl acetate-ethylene copolymer emulsion for redispersible emulsion powder | |
| CN207567151U (en) | A kind of propylene multistage polymerization device | |
| CN115569613A (en) | High-impact-resistance PVC resin production device and method | |
| CN103059779B (en) | Environment-friendly type lap joint port glue used for high speed cigarette making machine and preparation method thereof | |
| CN106753067A (en) | A kind of ultrahigh speed cigarette connects mouth glue and preparation method thereof | |
| CN102976658B (en) | Special additive for water-permeable concrete and preparation method of special additive | |
| CN101475784A (en) | Dual-component binder and preparation thereof | |
| CN207498308U (en) | A kind of device for producing polyvinyl alcohol | |
| CN208346075U (en) | Vinyl chloride vinyl acetate interpolymer paste resin production system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |