CN1876691A - Ethene-ethenol copolymer extrusion manufacture method - Google Patents
Ethene-ethenol copolymer extrusion manufacture method Download PDFInfo
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- CN1876691A CN1876691A CNA2005100499788A CN200510049978A CN1876691A CN 1876691 A CN1876691 A CN 1876691A CN A2005100499788 A CNA2005100499788 A CN A2005100499788A CN 200510049978 A CN200510049978 A CN 200510049978A CN 1876691 A CN1876691 A CN 1876691A
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Abstract
The invention relates the reaction extrusion preparing method for ethylene-vinyl alcohol copolymer, comprising the following characters: on the one end of the extrusion machine there is feed inlet, the part is molten zone, the other part is reaction zone, there is basic catalyst feed inlet and organic alcohol feed inlet, between molten zone and reaction zone there is devolatization zone, on the devolatization zone there is exhaust port, acetic acid ethyenyl content is 28-60%, the molten index is 1-30g/10min, the reaction temperature is 150-210Deg.C, the rate of organic alcohol and acetic acid ethyenyl is 0.5-3.0, the rate of basic catalyst and acetic acid ethyenyl is 0.1-0.5, the export of bolt extrusion machine is granulated and washed, then separate it, and get the ethylene-vinyl alcohol copolymer.
Description
Technical field
The present invention relates to a kind of ethylene-vinyl alcohol copolymer method for manufacturing technical field.
Background technology
Ethylene-vinyl alcohol copolymer abbreviates EVOH as, with polyvinyl dichloride (PVDC) and polyamide (PA) and be called three big barrier resins in the world.EVOH contains 20～40% ethene and 60～80% vinyl alcohol usually, therefore has the resistance oxygen of polyvinyl alcohol and the characteristics of poly workability concurrently.The EVOH gas barrier property is bigger approximately 100 times than PA, and is bigger approximately 10000 times than PP and PE.Gas barrier properties descended when the EVOH defective was high humidity, so common internal layer or gas-barrier layer as multilayer complex films.In recent years, along with the progress of society makes the human consumer higher to the requirement of barrier package, wish that not only food is fresher, can also keep product genuine and high-quality, it is high to the barrier requirement to resemble some food, require wrapping material that fragrance is had high barrier as coffee package, and some is to the oxygen sensitive product, additive in its wrapping material is high to the requirement of oxygen gas barrier, as the vitamin products that people know, this just promotes developing material merchant and investigators to go to seek advanced more wrapping material and development plan.And EVOH is a most typical oxygen barrier material in the high-barrier packaging material that is using at present, also is a kind of polymkeric substance best to oxygen-barrier property in the superpolymer.As the gas-barrier layer of gas barrier multilayer complex films, EVOH is the highest gas barrier material in fields such as packing that is applied in luxury food, medicine, electronic product.According to statistics, the global consumption of EVOH2003 is 100,000 tons/year, and consumption increase rate remains on more than 10% always in recent years.
Industrial production EVOH resin can be divided into EVA polymerization, EVA alcoholysis two steps.Traditional technology is to be solvent with the trimethyl carbinol, is ethene and vinyl acetate copolymerization, remove the trimethyl carbinol after, through super-dry, be the saponification reaction that solvent carries out EVA with methyl alcohol again, saponification deg requires up to (mole number) more than 99%.Method for saponification has homogeneous phase saponification method, heterogeneous saponification method at present.Homogeneous phase method for saponification principal character is that EVA is dissolved in the methyl alcohol, and then the alkali that adding is used as catalyzer in the EVA methanol solution, carry out saponification reaction at a certain temperature, usually, for the EVA saponification deg is reached more than 99%, also need saponified EVA resin is carried out the secondary saponification under the higher temperature in the aqueous solution of alkali.The homogeneous phase saponification method need use a large amount of solvents, and, contain a large amount of impurity such as sodium-acetate in the final saponification resultant, need a large amount of water to wash.Heterogeneous saponification method is that EVA constitutes suspension with particle or powder type in a kind of non-solvent, or is suspended in a kind of non-solvent with fused EVA drop form.
The 1950's, du pont company has obtained EVOH by copolymerization, alcoholysis reaction first.1972, Japanese Kuraray company then realized the suitability for industrialized production of EVOH resin the earliest, because production technology difficulty height, the Kuraray company and the Japanese synthetic chemistry two tame producers of Japan was only arranged in the world at present.Although China's recent two decades is studied producing of EVOH, EVOH is captured by external product in market basically entirely.Therefore, we should strengthen the research dynamics, strive for realizing early the production domesticization of EVOH resin.
Summary of the invention
Technical problem to be solved by this invention provides a kind of reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer, and its reaction times is short, production efficiency is high, do not need to use a large amount of organic solvents, reduces production costs greatly.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer, it is characterized in that: reactor adopts screw extrusion press, the charging opening that ethene-vinyl acetate copolymer is arranged in the position, an end of screw extrusion press, this screw extrusion press is melt region in this position, the opposite position of another of screw extrusion press is a conversion zone, be disposed with alkali catalyst charging opening and the organic pure charging opening that is used for alcoholysis, screw extrusion press is the devolatilization zone between melt region and conversion zone, this devolatilization zone is provided with venting port, therein ethylene-vinyl acetate copolymer is selected the ethene-vinyl acetate copolymer that contains vinyl acetate component 28-60% mass percent for use, melting index is (190 ℃ of 1-30g/10min, 2.16kg), temperature of reaction is controlled at 150～210 ℃, organic pure add-on makes organic alcohol/vinyl acetate mol ratio in 0.5～3.0 scope, alkali catalyst/vinyl acetate mol ratio is 0.1～0.5, the screw extrusion press outlet is through granulation and washing, pass through solid-liquid separation again, obtain ethylene-vinyl alcohol copolymer.
Useful is, described ethylene-vinyl alcohol copolymer is through reaction repeated expressing technique repeatedly, obtain the ethylene-vinyl alcohol copolymer of required saponification deg, it is with the polymkeric substance process granulation and the washing of the outlet acquisition of screw extrusion press, pass through solid-liquid separation again, and then the charging opening that joins screw extrusion press goes, and through repeatedly repeating alcoholysis process like this, makes the saponification deg of ethylene-vinyl alcohol copolymer satisfy our design requirements.
What be highly profitable is, described reactor residence time is controlled at the 2-10min scope, and the alcoholysis process multiplicity is controlled at 2～4 times, and to reach effective and rapid, effect reduces cost.
What be highly profitable is, described conversion zone is extruded direction along screw rod and is distributed with a plurality of alkali catalyst charging openings successively, impels organic alcohol to make full use of, and the major part that makes vacuum removal is the ester class.
Useful is, described organic alcohol is selected methyl alcohol or ethanol for use, concentration＞75%, and making the ester class of vacuum removal is methyl acetate or ethyl acetate, is more prone to make their volatilizations to remove.
Useful is, described alkali catalyst is selected sodium hydroxide or potassium hydroxide for use, and concentration 1-10M scope is with low cost, excellent catalytic effect.
Useful is that described temperature of reaction is controlled at 170～210 ℃, under the equal conditions, the EVA alcoholysis process can be obtained than higher saponification deg.
What be highly profitable is that described temperature of reaction is controlled at 190 ℃, under the equal conditions, makes the EVA alcoholysis process can obtain the highest saponification deg.
What be highly profitable is that described alkali catalyst/vinyl acetate mol ratio i.e. [OH]/[VA] mol ratio shows in the examples of implementation of optimizing 0.3, adopt this ratio to feed intake, under equal conditions, can obtain than higher saponification deg, simultaneously, avoid the product flavescence, darken.
Useful is that described organic alcohol/vinyl acetate mol ratio i.e. [MeOH]/[VA] mol ratio, can obtain than higher saponification deg under the equal conditions in 1～2 scope.
Compared with prior art, the invention has the advantages that: realize that on screw extrusion press alcoholysis reaction obtains EVOH, compare with existing processes, reaction extrusion process need not to use a large amount of organic solvents, reaction times is short, the production efficiency height, reduce production costs greatly, and the mobile and pure MeOH flow direction of EVA is to have formed adverse current, make EVA realize multistage saponification alcoholysis, improved pure utilization ratio, catalyzer is that multiple spot injects, impel organic alcohol to make full use of, the major part that makes vacuum removal is the ester class, especially adopts methyl alcohol or ethanol, making methyl acetate or ethyl acetate be more prone to volatilization removes, and reclaim by vacuum, and after remaining in sodium-acetate among the EVOH etc. and discharging through forcing machine, by granulation underwater and washing process, remove, particularly, by repetition alcoholysis process repeatedly, can obtain the EVOH product that we need saponification deg.
Description of drawings
Fig. 1 is the reaction extrusion manufacture method process schematic representation of ethylene-vinyl alcohol copolymer;
Fig. 2 is the influence graph of a relation of temperature of reaction to the EVA saponification deg;
Fig. 3 is the influence graph of a relation of alkali concn to the EVA saponification deg;
Fig. 4 is the influence graph of a relation of determining alcohol to the EVA saponification deg.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Anticipate as shown in the figure, the reaction extrusion manufacture method of this ethylene-vinyl alcohol copolymer, reactor has adopted twin screw extruder, the charging opening that ethene-vinyl acetate copolymer is arranged at the left end position of screw extrusion press, this screw extrusion press is melt region in this position, ethene-vinyl acetate copolymer in the hopper is in the above entered in the screw extrusion press by charging opening, and in this melt region, be melted, certainly, also can be the fused ethene-vinyl acetate copolymer directly to be added in the screw extrusion press by charging opening go, effect be the same.The right-hand member position of screw extrusion press is a conversion zone, be respectively arranged with alkali catalyst charging opening and the organic pure charging opening that is used for alcoholysis successively, screw extrusion press is the devolatilization zone between melt region and conversion zone, this devolatilization zone is provided with venting port, generally be to adopt vaccum exhaust outlet, and valve is installed, remove to help organic volatilization.Organic pure charging opening is arranged near on the extrusion position of screw extrusion press, it is connected with the top hopper that organic alcohol is housed by valve and pipeline, the alkali catalyst charging opening is arranged near on the position in devolatilization zone, it is connected with the top hopper that catalyzer is housed by valve and pipeline, and conversion zone transmits throughput direction along screw rod and is distributed with a plurality of such alkali catalyst charging openings successively.The screw extrusion press outlet is connected to underwater pelletizer or water ring tablets press; material is carried out granulation; particle particle maximum diameter＜5mm scope; and the washing process of can heating further; remove the acetate composition that remains in the ethylene-vinyl alcohol copolymer, washing temperature is 20-100 ℃ of scope.Pass through solid-liquid separation again, obtain granules of copolymer of ethylene-vinyl alcohol, waste water is by valve and pipeline place to go science and engineering skill.Certainly can suitably do some adjustment according to the production practical situation about granular size and washing temperature, be convenient to obtain optimal separating efficiency.
Above-mentioned processing parameter is that ethene-vinyl acetate copolymer is selected the ethene-vinyl acetate copolymer that contains vinyl acetate component 28-60% mass percent for use, melting index is (190 ℃ of 1-30g/10min, 2.16kg), temperature of reaction is controlled at 150～210 ℃, organic alcohol is selected methyl alcohol or ethanol for use, the organic pure add-on of concentration＞75% make organic alcohol/vinyl acetate mol ratio promptly the mol ratio of [MeOH] // [VA] in 0.5～3.0 scope, alkali catalyst is selected sodium hydroxide or potassium hydroxide for use, concentration 1-10M scope, alkali catalyst/vinyl acetate mol ratio is that [OH]/[VA] mol ratio is in 0.1～0.5 scope, the screw slenderness ratio of selecting twin screw extruder is in the 30-65 scope, rotating speed is in the 50-300rpm scope, making material is good at the reactor mean residence time of twin screw extruder in the 5-10min scope, certainly material is the saponification deg that can influence EVA at the mean residence time of reactor, but, by with middle multipolymer through reaction repeated expressing technique repeatedly, finally can obtain the ethylene-vinyl alcohol copolymer of required saponification deg, select preferable mean residence time, multiplicity can be controlled in 2～4 number scopes, improve reaction efficiency, reduce production costs.
In the reactor of twin screw extruder, there are following three reactions in base catalysis EVA alcoholysis:
1) esterification
2) direct saponification reaction
3) alcoholysis reaction
Above-mentioned EVA is an ethene-vinyl acetate copolymer, and MeOH is organic alcohol such as methyl alcohol or ethanol, and EVOH is an ethylene-vinyl alcohol copolymer, CH
3COOMe is ester such as ethyl acetate or methyl acetate, and NaOH is a catalyzer sodium hydroxide, CH
3COONa is a sodium-acetate.
The characteristics of reaction extrusion process are that the mobile and pure MeOH flow direction of EVA is to have formed adverse current, make EVA realize multistage saponification alcoholysis, have improved pure utilization ratio; Catalyst n aOH is that multiple spot injects, and impels organic pure MeOH to make full use of, and the major part that makes vacuum removal is ester class CH
3COOMe especially adopts methyl alcohol or ethanol, makes methyl acetate or ethyl acetate be more prone to volatilization and removes, and reclaim by vacuum, and remain in sodium-acetate CH among the EVOH
3COONa removes by granulation underwater and washing process after discharging through forcing machine, particularly, by repetition alcoholysis process repeatedly, can obtain the EVOH product that we need saponification deg.
Present embodiment has also been investigated the influence to alcoholysis reaction of temperature, alkali concn, determining alcohol.
The EVA that test is adopted is the product of French Atuofeina Corp, VA (vinyl acetate) content position 28%, melting index is 5, methyl alcohol and sodium hydroxide are chemically pure reagent, the mensuration of alcoholysis degree is pressed JIS K6730-1981 method and is measured, melting index is measured by GB/T3682-2000, and measuring temperature is 190 degree, and load is 2160 grams.
Fixing VA/MeOH mol ratio=1: 1, alkali/EVA mol ratio (i.e. the ratio of [OH]/[VA] mole)=0.2, screw speed 150rpm, the screw slenderness ratio of twin screw extruder is under 52 condition, measured the saponification reaction of passing through twin screw extruder under the differing temps, do temperature and saponification deg graph of a relation, see Fig. 2, the result shows that with the rising of temperature, saponification deg improves thereupon, but, the reasonable scope of temperature of reaction is at 170～210 ℃, preferably at 190 ℃, thereby can obtain the highest saponification deg.
In fixing [MeOH]/[VA] mol ratio is 1: 1, temperature is 190 ℃, screw speed 150rpm, the screw slenderness ratio of twin screw extruder is under 52 condition, change the NaOH consumption, investigating alkali/EVA mol ratio is the influence of [OH]/[VA] mol ratio to saponification reaction, the results are shown in Figure 3, and the result shows, saponification deg increases with the increase of alkali/EVA mol ratio and NaOH concentration, after [OH]/[VA] mol ratio surpasses 0.3, increase again, saponification deg improves also little, make the product jaundice on the contrary easily, darken, therefore reaching under the situation of high saponification deg, the NaOH consumption should reduce as far as possible.
Be under 0.2 the condition in fixing [OH]/[VA] mol ratio, investigate determining alcohol promptly [MeOH]/[VA] mol ratio the influence of saponification reaction be the results are shown in Figure 4, promptly [OH]/[VA] mol ratio is more appropriate in 1～2 scope to show alcohol/vinyl acetate mol ratio.
By repeatedly saponification, progressively alcoholysis is EVOH with EVA.
Saponification condition: [MeOH]/[VA] mol ratio=1: 1,190 ℃ of [OH]/[VA] mol ratio=0.3: 1 reaction extrusion temperatures, screw speed 200rpm, spiro rod length 52, reaction times 4min.
Secondary saponification condition: [MeOH]/[VA] mol ratio=2: 1,190 ℃ of [OH]/[VA] mol ratio=0.3: 1 reaction extrusion temperatures, screw speed 150rpm, spiro rod length 52, reaction times 5min.
Three saponification conditions: [MeOH]/[VA] mol ratio=3: 1,190 ℃ of [OH]/[VA] mol ratio=0.3: 1 reaction extrusion temperatures, screw speed 150rpm, spiro rod length 52, reaction times 5min.
The VA concentration determination is with reference to industry standard approach.
The performance of products obtained therefrom sees the following form:
| Outward appearance | Saponification deg (%) | Melt flow index (g/10min) | |
| EVOH after the saponification | Faint yellow | 50 | 4.5 |
| EVOH after the secondary saponification | Faint yellow | 85 | 4.2 |
| EVOH after three saponification | Faint yellow | 99 | 4.0 |
Claims (10)
1, a kind of reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer, it is characterized in that: reactor adopts screw extrusion press, the charging opening that ethene-vinyl acetate copolymer is arranged in the position, an end of screw extrusion press, this screw extrusion press is melt region in this position, the opposite position of another of screw extrusion press is a conversion zone, be disposed with alkali catalyst charging opening and the organic pure charging opening that is used for alcoholysis, screw extrusion press is the devolatilization zone between melt region and conversion zone, this devolatilization zone is provided with venting port, therein ethylene-vinyl acetate copolymer is selected the ethene-vinyl acetate copolymer that contains vinyl acetate component 28-60% mass percent for use, melting index is (190 ℃ of 1-30g/10min, 2.16kg), temperature of reaction is controlled at 150～210 ℃, organic pure add-on makes organic alcohol/vinyl acetate mol ratio in 0.5～3.0 scope, alkali catalyst/vinyl acetate mol ratio is 0.1～0.5, the screw extrusion press outlet is through granulation and washing, pass through solid-liquid separation again, obtain ethylene-vinyl alcohol copolymer.
2, the reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer according to claim 1 is characterized in that described ethylene-vinyl alcohol copolymer through reaction repeated expressing technique repeatedly, obtains the ethylene-vinyl alcohol copolymer of required saponification deg.
3, the reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer according to claim 1 is characterized in that described conversion zone is distributed with a plurality of alkali catalyst charging openings successively.
4, the reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer according to claim 1 is characterized in that described reactor residence time is controlled at the 3-10min scope, and multiplicity is controlled at 2～4 times.
5, the reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer according to claim 1 is characterized in that described organic alcohol selects methyl alcohol or ethanol for use, mass percent concentration＞75%.
6, the reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer according to claim 1 is characterized in that described alkali catalyst selects sodium hydroxide or potassium hydroxide for use, concentration 1-10M scope.
7, the reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer according to claim 1 is characterized in that described temperature of reaction is controlled at 170～210 ℃.
8, the reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer according to claim 7 is characterized in that described temperature of reaction is controlled at 190 ℃.
9, the reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer according to claim 1 is characterized in that described organic alcohol/vinyl acetate mol ratio is in 1～2 scope.
10, the reaction extrusion manufacture method of ethylene-vinyl alcohol copolymer according to claim 1 is characterized in that described alkali catalyst/vinyl acetate mol ratio is 0.3.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110316690A (en) * | 2019-06-11 | 2019-10-11 | 惠科股份有限公司 | Flexible device buffer layer and preparation method thereof and flexible device |
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| JP3689152B2 (en) * | 1995-07-28 | 2005-08-31 | 日本合成化学工業株式会社 | Resin composition and use thereof |
| US6686405B1 (en) * | 1999-07-23 | 2004-02-03 | Kuraray Co., Ltd. | Process for producing ethylene-vinyl alcohol copolymer resin, process for producing pellets and resin pellets |
| JP4864196B2 (en) * | 1999-11-18 | 2012-02-01 | 株式会社クラレ | Alkoxyl group-containing ethylene-vinyl acetate copolymer saponified product and molded product thereof |
| CA2399167C (en) * | 2001-09-03 | 2008-03-18 | Kuraray Co., Ltd. | Ethylene-vinyl alcohol copolymer composition, and powdery coating composition comprising it |
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| CN110316690A (en) * | 2019-06-11 | 2019-10-11 | 惠科股份有限公司 | Flexible device buffer layer and preparation method thereof and flexible device |
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