JPS6315923B2 - - Google Patents
Info
- Publication number
- JPS6315923B2 JPS6315923B2 JP19603881A JP19603881A JPS6315923B2 JP S6315923 B2 JPS6315923 B2 JP S6315923B2 JP 19603881 A JP19603881 A JP 19603881A JP 19603881 A JP19603881 A JP 19603881A JP S6315923 B2 JPS6315923 B2 JP S6315923B2
- Authority
- JP
- Japan
- Prior art keywords
- saponified
- saponification
- medium
- reactor
- eva
- 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.)
- Expired
Links
- 238000007127 saponification reaction Methods 0.000 claims description 81
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 62
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000008187 granular material Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 75
- 239000002609 medium Substances 0.000 description 65
- 239000000047 product Substances 0.000 description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000008188 pellet Substances 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 32
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 28
- 235000019441 ethanol Nutrition 0.000 description 26
- 239000000843 powder Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 18
- 235000011121 sodium hydroxide Nutrition 0.000 description 16
- 239000000155 melt Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 150000001340 alkali metals Chemical class 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012737 fresh medium Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 methanol Chemical compound 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 230000000242 pagocytic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical class OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005048 flame photometry Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は流動層方式で、低級アルコール媒体
中、特定の条件下にエチレン−酢酸ビニル共重合
体をケン化する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for saponifying ethylene-vinyl acetate copolymers in a fluidized bed system in a lower alcohol medium under specific conditions.
一般に、エチレン−酢酸ビニル共重合体ケン化
物(以下、EVAケン化物と略記)は、その原料
樹脂であるエチレン−酢酸ビニル共重合体(以
下、EVAと略記)に比べ、融点、硬度、抗張力、
曲げ強度、曲げ剛性度等が高く、また耐溶剤性、
耐摩耗性、耐気体透過性に優れるという特長を有
している。さらに、金属をはじめ各種無機ならび
に有機基材との接着性に優れており、粉体塗料等
の被覆剤、繊維接着剤、あるいは各種の積層接着
剤等として広く用いられている。 In general, saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as saponified EVA) has a higher melting point, hardness, tensile strength,
High bending strength, bending rigidity, etc., and solvent resistance.
It has the features of excellent wear resistance and gas permeation resistance. Furthermore, it has excellent adhesion to various inorganic and organic substrates including metals, and is widely used as coating agents such as powder coatings, fiber adhesives, and various lamination adhesives.
このようなEVAケン化物の製造法として、従
来、たとえば原料樹脂であるEVAをトルエンや
キシレンなどの良溶媒とメタノールなどのアルコ
ールとの混合溶媒に溶解し、均一溶液系でアルカ
リケン化したのち、貪溶媒を加えてケン化物を析
出させ、粉体として回収する方法が知られてい
る。しかし、この方法では反応後にケン化物を析
出させるのにメタノール等の多量の貪溶媒が必要
であるばかりではなく、さらにケン化物を分離、
洗浄、乾燥する工程が非常に煩雑であるため、経
済的には決して有利な方法ではない。一方、この
改良方法として、メタノールなどの、低級アルコ
ール中で粉末、粒状あるいはペレツト状のEVA
をこれらが相互に融着を起こさない条件下に原形
を維持しながらケン化する方法(たとえば、特公
昭44−27902号公報、特開昭48−102893号公報、
特開昭51−126291号公報、特開昭53−85888号公
報)が数多く提案されている。この方法の利点
は、原料EVAの形態を保つたまま、すなわち粒
状やペレツト状のケン化物が直接に回収できるこ
とである。このように、粒状やペレツト状でケン
化する方法は、反応後のケン化物の洗浄、分離お
よび乾燥工程における操作が容易であるため、工
業的に有利な方法として一般に推奨されている。 Conventionally, the method for manufacturing such EVA saponified products is to dissolve EVA, which is a raw material resin, in a mixed solvent of a good solvent such as toluene or xylene and an alcohol such as methanol, and then perform alkali saponification in a homogeneous solution system. A method is known in which a saponified product is precipitated by adding a phagocytic solvent and recovered as a powder. However, this method not only requires a large amount of phagocytic solvent such as methanol to precipitate the saponified product after the reaction, but also separates the saponified product.
Since the washing and drying steps are very complicated, it is not an economically advantageous method. On the other hand, as an improvement method, EVA powder, granules, or pellets are prepared in a lower alcohol such as methanol.
A method of saponifying them while maintaining their original shapes under conditions that do not cause them to fuse with each other (for example, Japanese Patent Publication No. 44-27902, Japanese Patent Application Laid-open No. 102893-1989,
There have been many proposals (Japanese Unexamined Patent Application Publication No. 126291/1982, No. 85888/1983). The advantage of this method is that the saponified product in the form of granules or pellets can be directly recovered while preserving the form of the raw material EVA. As described above, the method of saponifying the saponified product in the form of granules or pellets is generally recommended as an industrially advantageous method because the saponified product after the reaction can be easily washed, separated, and dried.
しかしながら、従来のケン化反応は一般に撹拌
槽を用い、機械的撹拌下にケン化する方式で行な
われている。この撹拌槽方式においては、次のよ
うな欠点ないしは問題点がある。 However, conventional saponification reactions are generally carried out using a stirring tank and saponification under mechanical stirring. This stirring tank system has the following drawbacks or problems.
(1) 粒状EVAをアルコール媒体中に分散させる
ためには多量の媒体とある程度強い撹拌が必要
である。(1) In order to disperse granular EVA in an alcoholic medium, a large amount of medium and a certain degree of strong stirring are required.
(2) この結果、ケン化反応および洗浄中に、アル
コール溶媒によつて膨潤し、柔弱となつた粒状
物が撹拌翼や槽壁と接触する際に、あるいは粒
子同志の強い衝突によつて、その粒子表面が磨
砕されるため、微粉状のケン化物が生成しやす
い。この傾向は酢酸ビニル含有量の高いEVA
を用い、ケン化率を高くするほど著しい。(2) As a result, during the saponification reaction and washing, when the granules swell with the alcohol solvent and become soft come into contact with the stirring blades or tank walls, or due to strong collisions between particles, Since the particle surface is ground, fine powder saponified products are likely to be produced. This tendency is due to EVA with high vinyl acetate content.
The saponification rate increases as the saponification rate increases.
(3) アルコール媒体中に分散した微粉状ケン化物
の分離、回収が困難である。このため、ケン化
物の収率が低下する。(3) It is difficult to separate and recover the fine powder saponified material dispersed in the alcohol medium. For this reason, the yield of saponified products decreases.
(4) アルコール媒体中に微粉状のケン化物が混入
するため媒体の回収率が悪い。(4) The recovery rate of the medium is poor because fine powder saponified substances are mixed into the alcohol medium.
(5) 槽壁に微粉状のケン化物が付着するため、運
転回数と共に伝熱係数が次第に低下する。(5) As fine powder saponified substances adhere to the tank wall, the heat transfer coefficient gradually decreases as the number of operations increases.
本発明者らは、上記のような欠点を改良すべく
鋭意検討を進めてきた結果、流動層方式の反応器
を用い、特定の条件下にケン化することによつて
その欠点を一挙に解決しうる方法を見い出し、本
発明を完成するに至つた。 The inventors of the present invention have carried out intensive studies to improve the above-mentioned drawbacks, and as a result, they have solved the drawbacks at once by using a fluidized bed reactor and saponifying under specific conditions. We have discovered a possible method and completed the present invention.
ここで、本発明の流動層方式によるEVAのケ
ン化および洗浄方法の特徴は、アルコール媒体を
反応器の下部から上部に連続的に循環供給する方
法において、その媒体の流量を制御してEVAペ
レツトを特定の層膨張率(定義は後述する)とな
るように流動化させるところにある。 Here, the feature of the EVA saponification and cleaning method using the fluidized bed method of the present invention is that the alcohol medium is continuously circulated from the bottom to the top of the reactor, and the flow rate of the medium is controlled to form EVA pellets. The process is to fluidize the material so that it has a specific layer expansion rate (the definition will be explained later).
この方法を従来の撹拌槽方式と比較すると次の
ような特長が挙げられる。 Comparing this method with the conventional stirring tank method, the following features can be cited.
(1) 流動層へ供給する媒体の液量を制御すること
により、粒状EVAを媒体中に流動化させる程
度の動力を与えればよい。したがつて、撹拌槽
による機械的撹拌よりも動力が小さい。(1) By controlling the amount of medium supplied to the fluidized bed, it is sufficient to apply enough power to fluidize the granular EVA into the medium. Therefore, the power is lower than mechanical stirring using a stirring tank.
(2) 強力な機械的撹拌がないために粒子の磨砕が
なく、微粉状のケン化物が生成しない。このた
め、ケン化物の収率が高い。(2) Since there is no strong mechanical stirring, there is no grinding of particles and no fine powder saponified products are generated. Therefore, the yield of saponified products is high.
(3) 媒体中に微粉状のケン化物がないので、ケン
化物と媒体の分離および回収が容易である。(3) Since there are no finely divided saponified substances in the medium, it is easy to separate and recover the saponified substances and the medium.
(4) 媒体中の固形分濃度を高くしうるので、反応
器の単位容積あたりのケン化物の生産性が高
い。(4) Since the solid content concentration in the medium can be increased, the productivity of saponified products per unit volume of the reactor is high.
上記のように、数多くの利点があるが、殊に本
発明の方法では微粉末状のケン化物が生成しない
ところが大きな特長である。 As mentioned above, the method of the present invention has many advantages, but a particularly great feature is that the method of the present invention does not produce fine powder saponified products.
以下に、本発明の実施態様について詳細に説明
する。 Embodiments of the present invention will be described in detail below.
本発明は、粒状エチレン−酢酸ビニル共重合を
炭素数1〜5の中から選ばれる1種または2種以
上の低級アルコール媒体中で、該粒状共重合体が
相互に融着しない温度においてアルカリケン化、
ならびに場合により引続いて該粒状ケン化物を洗
浄する方法において、該媒体を循環させながら層
膨張率が1.1〜3.0の範囲に制御されているところ
の流動層方式によることからなるエチレン−酢酸
ビニル共重合体ケン化物の製造法に関するもので
ある。 The present invention processes granular ethylene-vinyl acetate copolymerization in an alkaline hydroxide medium at a temperature at which the granular copolymers do not fuse together in one or more lower alcohol medium selected from 1 to 5 carbon atoms. transformation,
and, optionally, a method for subsequently washing the granular saponified material, using a fluidized bed method in which the bed expansion coefficient is controlled within the range of 1.1 to 3.0 while circulating the medium. This invention relates to a method for producing a saponified polymer.
本発明において、原料樹脂として用いられる
EVAは、酢酸ビニルの含有量が一般には10〜50
重量%の範囲であるが、とくに20〜45重量%のも
のが好ましい。また、該EVAのメルトインデツ
クスは5〜500のものが好ましい。なお、原料樹
脂として、EVAのほかにエチレンおよび酢酸ビ
ニルと共重合可能なモノマー、たとえばプロピレ
ン、ブテン−1、スチレン等の不飽和炭化水素、
(メタ)アクリル酸や(メタ)アクリル酸メチル
などの不飽和カルボン酸およびその誘導体等を10
重量%程度以下共重合させたものも使用できる。
これらのEVAおよびエチレン共重合体に含まれ
る未反応の酢酸ビニルモノマー量は、ケン化反応
中のケン化物の着色を防止する観点からは、1重
量%以下とすることが望ましい。 In the present invention, used as raw material resin
EVA generally has a vinyl acetate content of 10 to 50.
Although the range is by weight, 20 to 45 weight % is particularly preferred. Further, the melt index of the EVA is preferably 5 to 500. In addition to EVA, raw material resins include monomers copolymerizable with ethylene and vinyl acetate, such as unsaturated hydrocarbons such as propylene, butene-1, and styrene.
Unsaturated carboxylic acids and their derivatives, such as (meth)acrylic acid and methyl (meth)acrylate, etc.
It is also possible to use a copolymerized product of about % by weight or less.
The amount of unreacted vinyl acetate monomer contained in these EVA and ethylene copolymers is desirably 1% by weight or less from the viewpoint of preventing coloring of the saponified product during the saponification reaction.
本発明で用いられる上記原料EVAの形状は、
一般にはスクリユー押出機等によつて造粒して得
られるペレツト状のものやそれをさらに冷凍粉砕
等にて粉砕された粒状のものである。その粒状物
のメジアン径(累積重量分布曲線において、累積
値が50%のときの粒径)は一般に0.5〜7mmのも
のが使用されるが、とくに2〜5mmのものが好適
である。 The shape of the raw material EVA used in the present invention is as follows:
In general, these are pellets obtained by granulation using a screw extruder or the like, or granules obtained by further pulverizing the pellets by freeze-pulverization or the like. The median diameter of the granules (particle diameter when the cumulative value is 50% in the cumulative weight distribution curve) is generally 0.5 to 7 mm, but 2 to 5 mm is particularly preferred.
ケン化反応は上記の粒状EVAを原料とし、流
動層式反応器にて低級アルコール媒体中、層膨張
率1.1〜3.0の範囲内で行なわれる。流動層として
は円錐型、円筒型等種々の形状のものが使用でき
るが、とくに円筒型のものが好ましい。また、反
応型の上層部から媒体循環系へかけてのペレツト
の流出を防止するためには下層部よりも上層部の
口径を大きくすることが望ましい。ここで、本発
明において定義される層膨張率は次式によつて表
わされた値である。 The saponification reaction is carried out using the above granular EVA as a raw material in a lower alcohol medium in a fluidized bed reactor at a bed expansion rate of 1.1 to 3.0. The fluidized bed can have various shapes such as a conical shape and a cylindrical shape, but a cylindrical shape is particularly preferred. Further, in order to prevent the pellets from flowing out from the upper layer of the reaction mold to the medium circulation system, it is desirable to make the diameter of the upper layer larger than that of the lower layer. Here, the layer expansion coefficient defined in the present invention is a value expressed by the following equation.
層膨張率=V1/Vo
ただし、
Vo:アルコール媒体中において、ケン化反応ま
たは洗浄中のある時間tにおいて、媒体の循環
を停止し、粒子を沈降させたときの粒子層の占
める見かけの体積。 Bed expansion coefficient = V 1 /Vo where Vo: Apparent volume occupied by the particle layer when the circulation of the medium is stopped and the particles are allowed to settle in an alcoholic medium at a certain time t during saponification reaction or washing. .
V1:アルコール媒体中において、ケン化反応ま
たは洗浄中のある問間tにおいて、現に流動状
態にあるときの粒子層の占める見かけの体積。V 1 : Apparent volume occupied by a particle layer when it is in a fluid state during a certain interval t during a saponification reaction or washing in an alcoholic medium.
ここで、Voの値はケン化反応の進行と共に変
化する。その理由は反応系の成分および組成が変
化するためである。すなわち、ケン化反応の進行
に伴ないEVAケン化物とアルコール媒体あるい
はケン化反応によつて副生する低級アルコールの
酢酸エステルとの親和性の増大によるペレツトの
体積膨張が、また一方ではEVAの脱酢酸基によ
る体積の収縮等が同時に起こるからである。一般
には、Voの値は反応中期までは次第に大きくな
り、反応末期(完全ケン化時)には小さくなつて
ほぼ反応開始時の値に近くなる傾向がある。 Here, the value of Vo changes as the saponification reaction progresses. The reason is that the components and composition of the reaction system change. In other words, as the saponification reaction progresses, the volume of the pellet expands due to an increase in the affinity between the saponified EVA and the alcohol medium or the acetate ester of the lower alcohol produced as a by-product of the saponification reaction. This is because volume contraction and the like due to acetic acid groups occur simultaneously. In general, the value of Vo increases gradually until the middle stage of the reaction, and at the end of the reaction (at the time of complete saponification) it tends to decrease and become close to the value at the beginning of the reaction.
流動層内における層膨張率は、アルコール媒体
の流量、すなわち流動層内を通過する媒体の線速
度を制御することによつて前記の範囲内に容易に
制御しうる。この際に、層膨張率が1.1未満であ
るとペレツトの流動化が十分に起こらず、系内の
混合性が悪いため反応器の上層部と下層部あるい
は器壁部と内部とで温度差を生じたり、またアル
カリの濃度分布を生じてケン化反応が不均質とな
る。一方、層膨張率が3.0を越えると、単位反応
容積あたりのケン化物の生産性が悪くなるばかり
でなく、流動化のために必要以上の動力を与える
ことにもなり、エネルギー的にみても得策でな
い。このため層膨張率は1.1〜3.0の範囲にする必
要があり、好ましくは1.2〜2.5の範囲である。な
お、ペレツトの流動化を促す程度の補助的な攪拌
機を流動層に取付けることは差支えない。 The bed expansion rate in the fluidized bed can be easily controlled within the above range by controlling the flow rate of the alcohol medium, that is, the linear velocity of the medium passing through the fluidized bed. At this time, if the bed expansion coefficient is less than 1.1, fluidization of the pellets will not occur sufficiently and the mixing properties in the system will be poor, resulting in a temperature difference between the upper and lower parts of the reactor or between the wall and the inside of the reactor. In addition, the saponification reaction becomes heterogeneous due to the alkali concentration distribution. On the other hand, if the bed expansion coefficient exceeds 3.0, not only will the productivity of the saponified product per unit reaction volume deteriorate, but also more power than necessary for fluidization will be applied, which is not a good idea from an energy standpoint. Not. Therefore, the layer expansion coefficient needs to be in the range of 1.1 to 3.0, preferably in the range of 1.2 to 2.5. Note that an auxiliary agitator may be attached to the fluidized bed to promote fluidization of the pellets.
ケン化反応において使用される媒体は、メチル
アルコール、エチルアルコール、n−プロピルア
ルコール、イソプロピルアルコール、n−ブタノ
ール、n−ペンタノールのような炭素数1〜5の
低級アルコールである。これらは1種類を単独
に、または2種類以上を混合して使用することが
できる。また、ケン化反応は一般にアルカリ物質
の存在下に行なわれるが、とくにナトリウムおよ
びカリウムの水酸化物およびアルコラートの中か
ら選ばれるアルカリ物質の存在下にケン化するこ
とが望ましい。 The medium used in the saponification reaction is a lower alcohol having 1 to 5 carbon atoms, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, and n-pentanol. These can be used singly or in combination of two or more. The saponification reaction is generally carried out in the presence of an alkaline substance, but it is particularly desirable to carry out the saponification in the presence of an alkaline substance selected from sodium and potassium hydroxides and alcoholates.
本発明における粒状EVAのケン化反応は、該
粒子が相互に融着しない温度で行なわれる。この
温度は該EVAの酢酸ビニル含有量が高くなるほ
ど、また分子量が低くなるほど低くする必要があ
るが、通常、ケン化反応開始時の温度は30〜80℃
である。ケン化反応の進行に伴なつてケン物の融
点が上昇するため、融着温度は高くなる。ケン化
反応は一定温度で行なつてもよいが、この場合に
は長時間を要するため、上記のケン化物の融点上
昇を利用して段階的または連続的に昇温すると効
率よくケン化することができる。この際、反応系
への熱の供給は、ジヤケツト付流動層式反応器を
用いるか、あるいは外部熱交換器により循環アル
コール媒体を加熱することによつて行なわれる。
ケン化反応は一般に窒素雰囲気中で常圧または加
圧下で行なわれる。ケン化反応に際して添加され
るアルカリ物質の添加量は反応によつて得られる
EVAケン化物のケン化率に対応した量とすれば
よいが、一般には原料EVAに含まれる酢酸ビニ
ルの0.1〜1.5モル当量程度である。ケン化速度は
アルカリ物質の添加量が多くなるほど速くなる。
この場合、酢酸ビニルに対するアルカリ物質の添
加量が多くなるほど反応によつて副生する酢酸塩
の量が増加するが、これとは逆に低級アルコール
の酢酸エステルの生成量は減少する。これらの副
生物は蒸留によつてアルコール媒体から分離回収
することができる。ここで、アルカリ物質はあら
かじめアルコール溶液として添加することが望ま
しい。このアルカリ物質はケン化反応に際して一
括添加するか、あるいは反応中に分割添加または
連続添加することができる。また、ケン化反応に
おいて用いられるアルコール媒体は反応途中でそ
の一部または全量を反応系から抜き出し、その一
部または全量を新鮮な媒体と置き替えることがで
きる。この操作は1回または2回以上にわたつて
行なうことができる。 The saponification reaction of granular EVA in the present invention is carried out at a temperature at which the particles do not fuse together. This temperature needs to be lowered as the vinyl acetate content of the EVA increases and as the molecular weight decreases, but the temperature at the start of the saponification reaction is usually 30 to 80°C.
It is. As the saponification reaction progresses, the melting point of the saponified substance increases, so the fusion temperature increases. The saponification reaction may be carried out at a constant temperature, but in this case it takes a long time, so saponification can be carried out efficiently by raising the temperature stepwise or continuously by taking advantage of the rise in the melting point of the saponified product. Can be done. In this case, heat is supplied to the reaction system by using a jacketed fluidized bed reactor or by heating the circulating alcohol medium with an external heat exchanger.
The saponification reaction is generally carried out in a nitrogen atmosphere under normal pressure or increased pressure. The amount of alkaline substance added during the saponification reaction is obtained by the reaction.
The amount may be set in accordance with the saponification rate of the EVA saponified product, but is generally about 0.1 to 1.5 molar equivalent of vinyl acetate contained in the raw material EVA. The rate of saponification increases as the amount of alkaline substance added increases.
In this case, as the amount of the alkaline substance added to vinyl acetate increases, the amount of acetate produced by the reaction increases, but on the contrary, the amount of lower alcohol acetate produced decreases. These by-products can be separated and recovered from the alcoholic medium by distillation. Here, it is desirable to add the alkaline substance in advance as an alcohol solution. This alkaline substance can be added all at once during the saponification reaction, or can be added in portions or continuously during the reaction. Further, part or all of the alcohol medium used in the saponification reaction can be extracted from the reaction system during the reaction, and part or all of the alcohol medium can be replaced with fresh medium. This operation can be performed once or more than once.
この場合、アルコール媒体に添加されるアルカ
リ物質は各媒体の置換の都度、任意の量に変える
ことができる。このように反応媒体を1回または
数回に分割して新鮮なものに置き替えることによ
り、系内の副生物の蓄積がなくなり、反応が効果
的に進行する。また、アルカリ含有媒体を反応中
に取り替えると少量のアルカリ物質の添加で効率
よくケン化できる。さらに、この方法によれば反
応系内の媒体量は少量でよいため、単位反応器容
積あたりのケン化物の生産性が高くなること、ま
たケン化反応後のケン化物に含まれる酢酸塩等を
除去するための洗浄が容易であることなど数多く
の利点がある。 In this case, the amount of alkaline substance added to the alcohol medium can be changed to any desired amount each time each medium is replaced. By dividing the reaction medium once or several times and replacing it with fresh medium, the accumulation of by-products in the system is eliminated and the reaction proceeds effectively. Furthermore, if the alkali-containing medium is replaced during the reaction, saponification can be achieved efficiently with the addition of a small amount of alkaline substance. Furthermore, since this method requires only a small amount of medium in the reaction system, the productivity of the saponified product per unit reactor volume is increased, and acetate, etc. contained in the saponified product after the saponification reaction is reduced. It has many advantages, including ease of cleaning for removal.
ケン化反応によつて得られるEVAケン化物の
ケン化率は使用目的によるが、一般には50%以
上、好ましくは80%以上である。このケン化率は
反応条件によつて容易に制御しうる。なお、ケン
化反応によつて得られるケン化物の着色を防止す
る目的で反応系に公知の着色防止剤、たとえばヒ
ドラジンおよびその誘導体、アンモニアおよびそ
の誘導体、シアン酢酸エステル類、ケトンまたは
アルデヒド類等を添加することができる。また、
ペレツトの融着を防止する目的でアルコール媒体
に可溶な界面活性剤や分散安定剤を添加すること
もできる。 The saponification rate of the saponified EVA product obtained by the saponification reaction depends on the purpose of use, but is generally 50% or more, preferably 80% or more. This saponification rate can be easily controlled by changing the reaction conditions. In addition, in order to prevent coloring of the saponified product obtained by the saponification reaction, known coloring inhibitors such as hydrazine and its derivatives, ammonia and its derivatives, cyanacetic acid esters, ketones or aldehydes, etc. are added to the reaction system. Can be added. Also,
A surfactant or dispersion stabilizer soluble in the alcohol medium may also be added for the purpose of preventing pellet fusion.
上記のように、本発明におけるケン化は実質的
には流動層式反応器で行なわれるが、これに先だ
つてあらかじめ別の撹拌機付調合槽で所定量のア
ルカリ含有アルコール溶液に粒状EVAを加えた
分散液を調合し、この分散液を流動層に移すこと
ができる。この場合、該調合槽において、EVA
ケン化物が機械的撹拌下においても微粉末を生成
しないような低ケン化率領域まで予備的にケン化
することも可能である。 As mentioned above, saponification in the present invention is substantially carried out in a fluidized bed reactor, but prior to this, granular EVA is added to a predetermined amount of alkali-containing alcohol solution in a separate mixing tank equipped with a stirrer. A dispersion can be prepared and this dispersion can be transferred to a fluidized bed. In this case, in the mixing tank, EVA
It is also possible to preliminarily saponify to a low saponification rate region where the saponified product does not produce fine powder even under mechanical stirring.
該流動層式反応器にてケン化反応が終了したな
らば、ケン化物は別の装置に移送して洗浄、分離
および乾燥を行なつてもよいが、これらの操作を
該流動層式反応器にて継続して行なうこともでき
る。すなわち、ケン化反応終了後、該流動層内で
ケン化物を静置過し、アルコール媒体を分離し
たのち、引続きアルコール媒体にて洗浄すること
ができる。洗浄は1回または2回以上行なうこと
ができるが、ケン化物に含まれる未反応のアルカ
リ物質や副生した酢酸塩に由来するアルカリ金属
の含有量が0.5重量%以下、とくに0.2重量%程度
以下となるまで洗浄することが望ましい。洗浄温
度は一般に常温から80℃の範囲が適当であるが、
加温下に洗浄する方が効果が大である。なお、洗
浄に際してケン化物中のアルカリ金属の含有量を
低減させる目的で少量の無機酸、または有機酸を
添加することができる。このようにして、接着
性、耐侯性等に優れたケン化物が得られる。洗浄
後、ケン化物はアルコール媒体と分離したのち、
加熱空気あるいは窒素等の気流下で乾燥すること
ができる。乾燥はケン化物中のアルコール媒体の
含有量が0.5%程度以下となるまで行なうことが
望ましい。また、乾燥は上記の方法以外に、たと
えばロータリードライヤー、パドルドライヤーあ
るいはベント付押出機等、他の設備を用いて常圧
下または減圧下に行なうこともできる。 Once the saponification reaction is completed in the fluidized bed reactor, the saponified product may be transferred to another device for washing, separation, and drying, but these operations are performed in the fluidized bed reactor. You can also continue to do so. That is, after the saponification reaction is completed, the saponified product is allowed to stand in the fluidized bed to separate the alcohol medium, and then it can be washed with the alcohol medium. Washing can be carried out once or twice or more, but if the content of alkali metals derived from unreacted alkali substances contained in the saponified product or acetates produced as by-products is 0.5% by weight or less, particularly 0.2% by weight or less It is desirable to wash the product until it becomes . The appropriate cleaning temperature is generally between room temperature and 80°C.
Washing under heating is more effective. In addition, a small amount of inorganic acid or organic acid can be added for the purpose of reducing the content of alkali metal in the saponified product during washing. In this way, a saponified product with excellent adhesiveness, weather resistance, etc. can be obtained. After washing, the saponified product is separated from the alcohol medium, and then
It can be dried under a stream of heated air or nitrogen. It is desirable that drying be carried out until the content of the alcohol medium in the saponified product is about 0.5% or less. In addition to the method described above, drying can also be carried out using other equipment such as a rotary dryer, paddle dryer, or vented extruder under normal pressure or reduced pressure.
このようにして製造されるケン化物に対し、必
要に応じ、酸化防止剤、光安定剤、熱安定剤、無
機系または有機系着色剤、防錆剤、架橋剤、発泡
剤、滑剤、可塑剤、造刻剤、表面平滑剤、表面光
沢改良剤、螢光剤、無機または有機充填剤、高分
子化合物等、各種の無機または有機の添加剤もし
くは充填剤を添加することができる。なおこれら
の添加剤もしくは充填剤は原料EVAの製造工程、
ケン化物の製造工程あるいはその後の加工工程に
おいても添加しうる。 For the saponified product produced in this way, antioxidants, light stabilizers, heat stabilizers, inorganic or organic colorants, rust preventives, crosslinking agents, foaming agents, lubricants, and plasticizers are added as necessary. Various inorganic or organic additives or fillers can be added, such as engraving agents, surface smoothing agents, surface gloss improvers, fluorescent agents, inorganic or organic fillers, and polymer compounds. These additives or fillers are used in the manufacturing process of the raw material EVA,
It can also be added during the saponified product manufacturing process or subsequent processing steps.
本発明の方法によつて製造されるEVAケン化
物は、とくに粉体塗料および繊維接着剤として有
用であるが、このほか各種の無機または有機基材
の接着剤として使用できる。また、包装材料や各
種成形品としても広く使用できる。 The saponified EVA produced by the method of the present invention is particularly useful as a powder coating and a fiber adhesive, but can also be used as an adhesive for various inorganic or organic substrates. It can also be widely used as packaging materials and various molded products.
以下に本発明を実施例でもつて説明するが、本
発明はこれによつて限定されるものではない。 The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.
なお、本発明において示されるEVAおよびそ
のケン化物についての各測定値はそれぞれ次の方
法によつて求めたものである。 The measured values for EVA and its saponified products shown in the present invention were determined by the following methods.
(1) 酢酸ビニル含有量およびケン化率 JIS−K−6730に準拠して求めた。(1) Vinyl acetate content and saponification rate It was determined in accordance with JIS-K-6730.
(2) アルカリ金属含有量
JIS−K−0102−1974に準拠し、炎光光度法
により求めた。(2) Alkali metal content Determined by flame photometry in accordance with JIS-K-0102-1974.
(3) メルトインデツクス
JIS−K−6760に準拠し2.16Kgの荷重下に190
℃で測定した。測定値の単位はg/10minであ
る。(3) Melt index: 190 under a load of 2.16 kg according to JIS-K-6760
Measured at °C. The unit of measurement value is g/10min.
(4) 揮発分
EVAケン化物ペレツトを空気中、常圧下で
105℃の温度で2時間加熱したときの減量を、
加熱前のケン化物の重量を除した値を百分率で
表わした。(4) Volatile content: EVA saponified pellets in air under normal pressure.
The weight loss when heated at 105℃ for 2 hours is
The value obtained by dividing the weight of the saponified material before heating was expressed as a percentage.
(5) メジアン径
JIS標準篩を用い、粒径に対する累積重量分
布曲線を求め、これより累積分布が50重量%と
なる粒径で表わした。(5) Median diameter Using a JIS standard sieve, a cumulative weight distribution curve with respect to particle size was determined, and from this, the particle size was expressed as the particle size at which the cumulative distribution was 50% by weight.
実施例 1
流動層式反応器として、内径130mmφ、長さ
1500mmのガラス管の下部に16メツシユのステンレ
ススチール製の金網を内装した装置を用いた。こ
れにメジアン径3.2mm、メルトインデツクス60、
酢酸ビニル含有量42重量%のEVAペレツト4.0Kg
を仕込んだのち器内を窒素で置換し、あらかじめ
20のジヤケツト付撹拌槽にて予熱した水酸化ナ
トリウムのメチルアルコール溶液(該EVA中の
酢酸ビニルに対して0.2モル当量の水酸化ナトリ
ウムを含有)12.0Kgをポンプにて反応器の下部よ
り供給し、反応器の上部(媒体の出口に16メツシ
ユのステンレス金網取付け)から再び該20の撹
拌槽に戻して循環させた。このようにして、反応
器内のペレツトの層膨張率が1.4〜1.5となるよう
に循環媒体の流量を制御し、ペレツトを流動化さ
せながら40℃で6時間ケン化を行なつた。このと
きのEVAのケン化率は55%であつた。Example 1 As a fluidized bed reactor, inner diameter 130mmφ, length
A device with a 16-mesh stainless steel wire mesh installed at the bottom of a 1500 mm glass tube was used. This has a median diameter of 3.2mm, a melt index of 60,
4.0Kg of EVA pellets with vinyl acetate content of 42% by weight
After charging, replace the inside of the vessel with nitrogen, and
12.0 kg of a methyl alcohol solution of sodium hydroxide (containing 0.2 molar equivalent of sodium hydroxide to the vinyl acetate in the EVA), which had been preheated in a stirring tank with a jacket, was supplied from the bottom of the reactor using a pump. Then, the medium was returned to the 20 stirring tanks from the upper part of the reactor (a 16-mesh stainless wire mesh was attached to the medium outlet) and circulated. In this way, the flow rate of the circulating medium was controlled so that the bed expansion coefficient of the pellets in the reactor was 1.4 to 1.5, and saponification was carried out at 40 DEG C. for 6 hours while fluidizing the pellets. The saponification rate of EVA at this time was 55%.
つぎに、反応器の下部より反応に用いた媒体を
全量抜き出したのち、該20の撹拌槽に新たに調
整した水酸化ナトリウムのメチルアルコール溶液
(該EVAケン化物中の未反応酢酸ビニルに対して
1.2モル当量の水酸化ナトリウムを含有)を12.0
Kg仕込み、ポンプで循環させながら反応器内のペ
レツトの層膨張率が1.4〜1.5となるようにして60
℃で10時間ケン化を行なつた。反応後、上記と同
様にして媒体を全量抜き出したのち、メチルアル
コール12.0Kgを仕込み、反応器内のペレツトの層
膨張率が1.4となる条件下に60℃で2時間洗浄し
た。以下、この洗浄操作を1回繰り返した。ケン
化反応および洗浄を通じて回収された媒体は透明
であり、粉末状のケン化物の生成は全く認められ
なかつた。 Next, after removing the entire amount of the medium used in the reaction from the bottom of the reactor, a freshly prepared methyl alcohol solution of sodium hydroxide (relative to unreacted vinyl acetate in the EVA saponification product) was added to the 20 stirring tanks.
12.0 (contains 1.2 molar equivalents of sodium hydroxide)
Kg, and while circulating with a pump, keep the bed expansion coefficient of the pellets in the reactor at 1.4 to 1.5.
Saponification was carried out at ℃ for 10 hours. After the reaction, the entire amount of the medium was extracted in the same manner as above, and then 12.0 kg of methyl alcohol was charged and the pellets in the reactor were washed at 60° C. for 2 hours under conditions such that the layer expansion coefficient was 1.4. Thereafter, this washing operation was repeated once. The medium recovered through the saponification reaction and washing was transparent, and no powdery saponified product was observed.
ケン化物を洗浄後、反応器内から取り出し真空
乾燥器にて揮発分の含有量が0.2重量%となるま
で70℃で乾燥した。この結果、メルトインデツク
ス25、ケン化率98.6%、アルカリ金属含有量0.06
重量%のEVAケン化物を得た。 After washing the saponified product, it was taken out from the reactor and dried at 70°C in a vacuum dryer until the content of volatile matter was 0.2% by weight. As a result, the melt index was 25, the saponification rate was 98.6%, and the alkali metal content was 0.06.
A saponified EVA product of % by weight was obtained.
実施例 2
実施例1において、水酸化ナトリウムの添加量
をEVA中の酢酸ビニルに対して0.5モル当量とし
た以外は、実施例1と同一条件下にケン化反応を
開始した。40℃で3時間反応後、実施例1と同様
にして反応系内の媒体を全量抜き出した。このと
きのEVAのケン化率は60%であつた。ついで該
EVAケン化物中の未反応酢酸ビニルに対して1.0
モル当量の水酸化ナトリウムを含有するメチルア
ルコール溶液を仕込み、実施例1と同一条件下に
60℃で6時間ケン化を行なつた。反応後、実施例
1と同一条件下にEVAケン化物をメチルアルコ
ールで洗浄したのち乾燥した。Example 2 A saponification reaction was started under the same conditions as in Example 1, except that the amount of sodium hydroxide added was 0.5 molar equivalent to the vinyl acetate in EVA. After reacting at 40°C for 3 hours, the entire amount of the medium in the reaction system was extracted in the same manner as in Example 1. The saponification rate of EVA at this time was 60%. Then the corresponding
1.0 for unreacted vinyl acetate in EVA saponification product
A methyl alcohol solution containing a molar equivalent of sodium hydroxide was charged and the mixture was heated under the same conditions as in Example 1.
Saponification was carried out at 60°C for 6 hours. After the reaction, the saponified EVA product was washed with methyl alcohol under the same conditions as in Example 1, and then dried.
ケン化反応および洗浄を通じて粉末状のケン化
物の生成は全く認められなかつた。得られたケン
化物のメルトインデツクスは32.、ケン化率は
98.9%、アルカリ金属含有量は0.07重量%であつ
た。 No formation of saponified powder was observed during the saponification reaction and washing. The melt index of the obtained saponified product was 32., and the saponification rate was
98.9%, and the alkali metal content was 0.07% by weight.
実施例 3
実施例1で用いた流動層式反応器にメジアン径
3.5mmメルトインデツクス300、酢酸ビニル含有量
28重量%のEVAペレツト4.0Kgを仕込んだのち、
実施例1と同様にして該原料EVA中の酢酸ビニ
ルに対して0.2モル当量の水酸化ナトリウムを含
有するメチルアルコール溶液を循環させながら、
反応器内のペレツトの層膨張率を1.7〜1.9の範囲
に保持しながら50℃で7時間ケン化した。このと
きのケン化率は30%であつた。ついで、実施例1
と同様にして反応系内から媒体を全量抜き出した
のち、該ケン化物中の未反応酢酸ビニルに対して
1.0モル当量の水酸化ナトリウムを含有するメチ
ルアルコール溶液を仕込み、反応器内のペレツト
の層膨張率を1.5〜1.7の範囲に保持しながら60℃
で10時間ケン化した。以下、実施例1の方法を繰
り返し、EVAケン化物の洗浄および乾燥を行な
つた。Example 3 The fluidized bed reactor used in Example 1 had a median diameter of
3.5mm melt index 300, vinyl acetate content
After charging 4.0kg of 28% EVA pellets,
While circulating a methyl alcohol solution containing 0.2 molar equivalent of sodium hydroxide to the vinyl acetate in the raw material EVA in the same manner as in Example 1,
The pellets in the reactor were saponified at 50° C. for 7 hours while maintaining the bed expansion coefficient within the range of 1.7 to 1.9. The saponification rate at this time was 30%. Next, Example 1
After removing the entire amount of the medium from the reaction system in the same manner as above, the unreacted vinyl acetate in the saponified product is
A methyl alcohol solution containing 1.0 molar equivalent of sodium hydroxide was charged, and the pellets in the reactor were heated at 60°C while maintaining the layer expansion coefficient in the range of 1.5 to 1.7.
It was saponified for 10 hours. Thereafter, the method of Example 1 was repeated to wash and dry the saponified EVA product.
ケン化反応および洗浄を通じて粉末状のケン化
物の生成は全く認められなかつた。得られたケン
化物のメルトインデツクスは160、ケン化率は
92.0%、ナトリウム含有量は0.03重量%であつ
た。 No formation of saponified powder was observed during the saponification reaction and washing. The melt index of the saponified product obtained was 160, and the saponification rate was
92.0%, and the sodium content was 0.03% by weight.
実施例 4
流動層式反応器として、内径250mmφ、長さ
2000mmのステンレススチール製の耐圧装置を用い
た。この装置の下部には口径1mmのステンレスス
チール製の多孔板が水平面に対して50゜の角度に
傾斜させて内装してあり、その傾斜多孔板の下辺
側壁部にはペレツト抜き出し用の1.5インチのピ
ストンバルブが取付けられている。また、この反
応器の上部は内角30゜で上開きとなり、内径30mm
φのステンレスチール製の円筒に接続されてい
る。その円筒の側壁には媒体の出口パイプが取付
られており、またその頭部には原料仕込み口があ
る。媒体は外部熱交換器で加熱され、ポンプにて
反応器底部から供給し、循環されるようになつて
いる。また、反応器の円筒には内部を観察するた
めの耐圧ガラス製の覗き窓が取付けられている。Example 4 As a fluidized bed reactor, inner diameter 250mmφ, length
A 2000mm stainless steel pressure-resistant device was used. At the bottom of this device, a perforated plate made of stainless steel with a diameter of 1 mm is installed at an angle of 50° with respect to the horizontal plane. A piston valve is installed. In addition, the top of this reactor opens upward with an internal angle of 30°, and has an internal diameter of 30 mm.
Connected to a φ stainless steel cylinder. A medium outlet pipe is attached to the side wall of the cylinder, and a raw material inlet is provided at the head of the cylinder. The medium is heated by an external heat exchanger, supplied from the bottom of the reactor by a pump, and circulated. Additionally, a viewing window made of pressure-resistant glass is attached to the cylinder of the reactor for observing the inside.
この反応器に、あらかじめ200の撹拌機付調
合槽で調合し、40℃に予熱したEVAペレツト/
水酸化ナトリウム含有メチルアルコール溶液(重
量比1/3)の混合物を反応器の頭部から仕込ん
だ。ここで用いたEVAペレツトはメジアン径3.5
mm、メルトインデツクス70、酢酸ビニル含有量43
重量%のものである。また水酸化ナトリウムは該
原料EVA中の酢酸ビニルに対して0.2モル当量添
加した。なお、以下のケン化および洗浄は窒素雰
囲気下に行なつた。 In this reactor, EVA pellets/
A mixture of sodium hydroxide-containing methyl alcohol solution (1/3 weight ratio) was charged from the top of the reactor. The EVA pellets used here had a median diameter of 3.5
mm, melt index 70, vinyl acetate content 43
% by weight. Further, sodium hydroxide was added in an amount of 0.2 molar equivalent to vinyl acetate in the raw material EVA. Note that the following saponification and cleaning were performed under a nitrogen atmosphere.
この反応器に仕込んだ媒体をポンプで循環させ
ながら外部熱交換器で加熱し、反応器内の温度を
40℃、またペレツトの層膨張率を1.5〜1.7に保持
して5時間ケン化を行なつた。このときのEVA
のケン化率は57%であつた。 The medium charged in this reactor is circulated by a pump and heated by an external heat exchanger to maintain the temperature inside the reactor.
Saponification was carried out for 5 hours at 40°C and while maintaining the layer expansion coefficient of the pellets at 1.5 to 1.7. EVA at this time
The saponification rate was 57%.
ついで、反応器の底部から反応に用いた媒体の
全量を抜き出したのち、新たに該EVAケン化物
中の未反応酢酸ビニルに対して1.0モル当量の水
酸化ナトリウムを含有するメチルアルコール溶液
(あらかじめ調合槽にて70℃に予熱されたもの)
を上記と同量仕込み、ポンプで循環させながら反
応器内のペレツトの層膨張率が1.5〜1.7となるよ
うにして70℃、ゲージ圧力0.5Kg/cm2下に7時間
ケン化した。反応後、上記と同様にして媒体の全
量を抜き取つたのち、60℃に予熱したメチルアル
コールを仕込んでペレツトの層膨張率を1.4〜1.5
に保持して60℃で2時間洗浄した。以下、この洗
浄操作を1回繰り返した。ケン化反応および洗浄
を通じて粉末状のケン化物の生成は全く認められ
なかつた。 Next, after extracting the entire amount of the medium used in the reaction from the bottom of the reactor, a new methyl alcohol solution (prepared Preheated to 70℃ in a tank)
The same amount of pellets as above was charged, and the pellets were saponified for 7 hours at 70° C. and under a gauge pressure of 0.5 kg/cm 2 while circulating with a pump so that the layer expansion coefficient of the pellets in the reactor was 1.5 to 1.7. After the reaction, remove the entire amount of the medium in the same manner as above, and then add methyl alcohol preheated to 60°C to adjust the layer expansion coefficient of the pellets to 1.4 to 1.5.
and washed at 60°C for 2 hours. Thereafter, this washing operation was repeated once. No formation of saponified powder was observed during the saponification reaction and washing.
洗浄後、反応器内から媒体を抜き出したのち、
引続いて反応器の底部より90℃に加熱した窒素を
送り込みながら8時間乾燥した。この結果、メル
トインデツクス31、ケン化率98.7%、アルカリ金
属含有量0.05重量%、揮発分0.3重量%のケン化
物を得た。 After cleaning, after removing the medium from the reactor,
Subsequently, the reactor was dried for 8 hours while supplying nitrogen heated to 90° C. from the bottom of the reactor. As a result, a saponified product was obtained with a melt index of 31, a saponification rate of 98.7%, an alkali metal content of 0.05% by weight, and a volatile content of 0.3% by weight.
実施例 5
実施例4の反応器を用い、実施例4と同様にし
てEVAペレツト/水酸化ナトリウム含有メチル
アルコール溶液の重量比が1/3からなる混合物
(あらかじめ80℃に加熱)を反応器に仕込んだ。
ここで、EVAとしてメジアン径3.7mm、メルトイ
ンデツクス150、酢酸ビニル含有量35重量%のも
のを用いた。また、水酸化ナトリウムは該原料
EVA中の酢酸ビニルに対し、1.15モル当量添加
した。反応器に仕込んだ媒体を実施例4と同様に
して循環させ、反応器内の温度を75℃、またペレ
ツトの層膨張率を1.9〜2.1に保持して7時間ケン
化を行なつた。反応中の器内のゲージ圧力は0.8
Kg/cm2であつた。ついで、反応に用いた媒体の全
量を抜き出したのち、洗浄用のメチルアルコール
を仕込み、ペレツトの層膨張率を1.2〜1.4に保持
して70℃で2時間洗浄した。以下、この洗浄操作
を1回繰り返した。ケン化反応および洗浄を通じ
て粉末状のケン化物の生成は全く認められなかつ
た。Example 5 Using the reactor of Example 4, a mixture of EVA pellets/methyl alcohol solution containing sodium hydroxide in a weight ratio of 1/3 (heated in advance to 80°C) was introduced into the reactor in the same manner as in Example 4. I prepared it.
Here, the EVA used had a median diameter of 3.7 mm, a melt index of 150, and a vinyl acetate content of 35% by weight. In addition, sodium hydroxide is
It was added in an amount of 1.15 molar equivalents to vinyl acetate in EVA. The medium charged in the reactor was circulated in the same manner as in Example 4, and saponification was carried out for 7 hours while maintaining the temperature inside the reactor at 75°C and the bed expansion coefficient of the pellets at 1.9 to 2.1. Gauge pressure inside the vessel during reaction is 0.8
It was Kg/ cm2 . Then, after the entire amount of the medium used in the reaction was extracted, methyl alcohol for washing was added, and the pellets were washed at 70°C for 2 hours while maintaining the layer expansion coefficient at 1.2 to 1.4. Thereafter, this washing operation was repeated once. No formation of saponified powder was observed during the saponification reaction and washing.
以下、実施例4と同様にして乾燥した結果、メ
ルトインデツクス60、ケン化率99.2%、アルカリ
金属含有量0.04重量%、揮発分0.3重量%のケン
化物を得た。 After drying in the same manner as in Example 4, a saponified product was obtained with a melt index of 60, a saponification rate of 99.2%, an alkali metal content of 0.04% by weight, and a volatile content of 0.3% by weight.
実施例 6
実施例5において、EVAとしてメジアン径3.2
mm、メルトインデツクス65、酢酸ビニル含有量44
重量%のEVAを用い、ケン化を70℃で0.5Kg/cm2
のゲージ圧力下に9時間行なつた以外は実施例5
の方法を繰り返した。この結果、メルトインデツ
クス36、ケン化率99.2%、アルカリ金属含有量
0.11重量%、揮発分0.3重量%のケン化物を得た。
また、ケン化および洗浄を通じて粉末状のケン化
物の生成は全く認められなかつた。Example 6 In Example 5, the median diameter as EVA was 3.2.
mm, melt index 65, vinyl acetate content 44
Saponification using wt% EVA at 70℃ 0.5Kg/ cm2
Example 5 except that the test was carried out for 9 hours under the gauge pressure of
The method was repeated. As a result, the melt index is 36, the saponification rate is 99.2%, and the alkali metal content is
A saponified product was obtained with a content of 0.11% by weight and a volatile content of 0.3% by weight.
Furthermore, no formation of powdery saponified products was observed during saponification and washing.
実施例 7
実施例4において、ケン化および洗浄工程にお
けるペレツトの層膨張率を1.2〜1.3に変えた以外
は実施例4の方法を繰り返した。この結果、メル
トインデツクス32、ケン化率98.6%、アルカリ金
属含有量0.05重量%、揮発分0.3重量%のケン化
物を得た。また、ケン化および洗浄を通じて粉末
状のケン化物の生成は全く認められなかつた。Example 7 The method of Example 4 was repeated except that the rate of bed expansion of the pellets during the saponification and washing steps was varied from 1.2 to 1.3. As a result, a saponified product was obtained with a melt index of 32, a saponification rate of 98.6%, an alkali metal content of 0.05% by weight, and a volatile content of 0.3% by weight. Furthermore, no formation of powdery saponified products was observed during saponification and washing.
実施例 8
実施例5において、ケン化反応の媒体としてメ
チルアルコール/イソプロピルアルコールの重量
比8/2の混合物を用いた以外は実施例5の方法
を繰り返した。ケン化反応および洗浄を通じて粉
末状のケン化物の生成は全く認められなかつた。
また、得られたケン化物のメルトインデツクスは
62、ケン化率は99.7%、アルカリ金属含有量は
0.04重量%であつた。Example 8 The method of Example 5 was repeated except that in Example 5, an 8/2 weight ratio mixture of methyl alcohol/isopropyl alcohol was used as the medium for the saponification reaction. No formation of saponified powder was observed during the saponification reaction and washing.
In addition, the melt index of the saponified product obtained is
62, saponification rate is 99.7%, alkali metal content is
It was 0.04% by weight.
実施例 9
実施例4の反応器を用い、実施例4と同様にし
て粒状EVA/ナトリウムメチラート含有メチル
アルコール溶液の重量比が1/2からなる混合物
(あらかじめ80℃に加熱)を反応器に仕込んだ。
ここで、粒状EVAとしてメジアン径1.4mm、メル
トインデツクス120、酢酸ビニル含有量30重量%
のものを用いた。また、ナトリウムメチラートは
該原料EVA中の酢酸ビニルに対し0.2モル当量添
加した。反応器内の媒体を実施例4と同様にして
循環させ、反応器内の温度を70℃、また粒子の層
膨張率を1.2〜1.3に保持して3時間ケン化を行な
つた。このときのケン化率は62%であつた。つい
で反応器の底部から反応に用いた媒体を全量抜き
出したのち、新たに該EVAケン化物中の未反応
酢酸ビニルに対して1.2モル当量のナトウムメチ
ラール含有メチルアルコール溶液(あらかじめ80
℃に加熱)を仕込み、反応器内の温度を80℃、ま
た粒子の層膨張率を1.2〜1.3に保持して5時間ケ
ン化した。反応後、上記と同様にして媒体を全量
抜き出したのち、70℃に予熱したメチルアルコー
ルを仕込み、粒子の層膨張率を1.2〜1.3に保持
し、70℃で1時間洗浄した。以下、この洗浄操作
を1回繰り返した。ケン化反応および洗浄を通じ
て微粉状のケン化物の生成は全く認められなかつ
た。Example 9 Using the reactor of Example 4, a mixture consisting of granular EVA/methyl alcohol solution containing sodium methylate in a weight ratio of 1/2 (heated in advance to 80°C) was introduced into the reactor in the same manner as in Example 4. I prepared it.
Here, as granular EVA, the median diameter is 1.4 mm, the melt index is 120, and the vinyl acetate content is 30% by weight.
I used the one from Further, sodium methylate was added in an amount of 0.2 molar equivalent to vinyl acetate in the raw material EVA. The medium in the reactor was circulated in the same manner as in Example 4, and saponification was carried out for 3 hours while maintaining the temperature in the reactor at 70° C. and the layer expansion coefficient of the particles at 1.2 to 1.3. The saponification rate at this time was 62%. Next, after removing the entire amount of the medium used for the reaction from the bottom of the reactor, a new methyl alcohol solution containing 1.2 molar equivalent of sodium methylalium (80%
The reactor was saponified for 5 hours while maintaining the temperature inside the reactor at 80°C and the layer expansion coefficient of the particles at 1.2 to 1.3. After the reaction, the entire amount of the medium was extracted in the same manner as above, and then methyl alcohol preheated to 70°C was charged to maintain the layer expansion coefficient of the particles at 1.2 to 1.3, and the particles were washed at 70°C for 1 hour. Thereafter, this washing operation was repeated once. No formation of fine powder saponified products was observed during the saponification reaction and washing.
洗浄後、反応器から媒体およびケン化物を取り
出したのち、ベント付50mmφのスクリユー押出機
にて180℃でケン化物を押出し、ケン化物に含ま
れる媒体をベント部から減圧下に除去した。得ら
れたケン化物のメルトインデツクスは50、ケン化
率は98.8%、アルカリ金属含有量は0.04重量%、
揮発分は0.2重量%であつた。 After washing, the medium and saponified product were taken out from the reactor, and then the saponified product was extruded at 180°C using a screw extruder with a diameter of 50 mm equipped with a vent, and the medium contained in the saponified product was removed from the vent section under reduced pressure. The obtained saponified product had a melt index of 50, a saponification rate of 98.8%, an alkali metal content of 0.04% by weight,
The volatile content was 0.2% by weight.
比較例 1
内容積100のジヤケツト付ステンレススチー
ル製の反応器に水酸化ナトリウム含有(原料
EVA中の酢酸ビニルに対して0.2倍モル)メチル
アルコール溶液300重量部を仕込み、フアンター
ビン翼にて150rpmの撹拌下に実施例1で用いた
と同じのメジアン径3.2mm、メルトインデツクス
60、酢酸ビニル含有量42重量%のEVAペレツト
100重量部を加えた。窒素雰囲気下、この混合物
を40℃に加熱して6時間ケン化を行なつたのち、
反応器内の媒体のみを全量抜き出した。回収媒体
は微粉末状のケン化物で白濁していた。つぎに、
新たに調製した水酸化ナトリウム含有(該EVA
ケン化物中の未反応酢酸ビニルに対して1.2モル
当量)メチルアルコール溶液300重量部を反応器
に仕込み、150rpmの撹拌下に60℃で10時間ケン
化した。反応後、媒体を抜き出したところ微粉末
状のケン化物で著しく白濁していた。このケン化
時に生成した微粉末状ケン化物の量は、全ケン化
物に対して3重量%であつた。引続いて、反応器
に300重量部のメチルアルコールを加え、150rpm
の撹拌下に60℃で2時間づつ繰り返して洗浄し
た。この洗浄液はいずれも著しく白濁しており、
その中に含まれる微粉末状のケン化物の合計量は
全ケン化物に対して5重量%であつた。なお、回
収されたケン化物ペレツトのメルトインデツクス
は32、またケン化率は98.7%であつた。反応器か
らケン化物を回収後、反応器内を点検したところ
器壁に微粉状のケン化物が薄膜状に付着してお
り、そのまま繰り返して運転した場合は付着物が
推積して伝熱係数が次第に低下した。Comparative Example 1 A stainless steel reactor with an inner volume of 100 mm and a jacket containing sodium hydroxide (raw material
Add 300 parts by weight of methyl alcohol solution (0.2 times the mole of vinyl acetate in EVA) and stir with a fan turbine blade at 150 rpm to obtain the same median diameter of 3.2 mm and melt index as used in Example 1.
60, EVA pellets with vinyl acetate content of 42% by weight
100 parts by weight were added. After heating this mixture to 40°C under a nitrogen atmosphere and saponifying it for 6 hours,
Only the medium in the reactor was completely extracted. The recovery medium was cloudy with finely powdered saponified substances. next,
Freshly prepared sodium hydroxide containing (the EVA
300 parts by weight of a methyl alcohol solution (1.2 molar equivalent to unreacted vinyl acetate in the saponified product) was charged into a reactor and saponified at 60°C for 10 hours with stirring at 150 rpm. After the reaction, when the medium was taken out, it was found to be extremely cloudy due to finely powdered saponified substances. The amount of fine powder saponified material produced during this saponification was 3% by weight based on the total saponified material. Subsequently, 300 parts by weight of methyl alcohol was added to the reactor and the speed was increased at 150 rpm.
Washing was repeated at 60° C. for 2 hours each time under stirring. All of these cleaning solutions are extremely cloudy,
The total amount of finely powdered saponified materials contained therein was 5% by weight based on the total saponified materials. The recovered saponified pellets had a melt index of 32 and a saponification rate of 98.7%. After collecting the saponified material from the reactor, we inspected the inside of the reactor and found that a thin film of finely powdered saponified material had adhered to the wall of the reactor.If the operation was continued as it was, the deposits would be estimated to cause a decrease in the heat transfer coefficient. gradually decreased.
比較例 2
比較例1で用いた反応器に水酸化ナトリウム含
有(原料EVA中の酢酸ビニルに対して1.15倍モ
ル当量)メチルアルコール溶液300重量部を仕込
み、200rpmの撹拌下に実施例5で用いたと同じ
のメジアン径3.7mm、メルトインデツクス150、酢
酸ビニル含有量35重量%のEVAペレツト100重量
部を加えた。窒素雰囲気下、この混合物を80℃に
加熱して7時間ケン化した。反応後、反応器から
媒体のみを抜き出したところ、媒体は微粉状のケ
ン化物が分散して白濁していた。この微粉状のケ
ン化物の量は全ケン化物に対して2重量%であつ
た。引続いて、反応器に300重量部のメチルアル
コールを加え、200rpmの撹拌下に70℃で2時間
づつ2回繰り返して洗浄した。この洗浄液は著し
く白濁しておりその中に含まれる微粉状ケン化物
の量は全ケン化物に対して4重量%であつた。反
応器からケン化物を回収後、反応器内を点検した
ところ、器壁全面に微粉末のケン化物が薄膜状に
付着していた。なお、回収されたケン化物ペレツ
トのメルトインデツクスは63、ケン化率は99.1%
であつた。Comparative Example 2 300 parts by weight of a methyl alcohol solution containing sodium hydroxide (1.15 times the molar equivalent to vinyl acetate in the raw material EVA) was charged into the reactor used in Comparative Example 1, and the solution used in Example 5 was charged with stirring at 200 rpm. 100 parts by weight of EVA pellets having the same median diameter of 3.7 mm, melt index of 150, and vinyl acetate content of 35% by weight were added. The mixture was heated to 80° C. and saponified for 7 hours under a nitrogen atmosphere. After the reaction, when only the medium was extracted from the reactor, the medium was cloudy with finely powdered saponified substances dispersed therein. The amount of this fine powder saponified material was 2% by weight based on the total saponified material. Subsequently, 300 parts by weight of methyl alcohol was added to the reactor, and the reactor was washed twice for 2 hours at 70° C. with stirring at 200 rpm. This cleaning solution was extremely cloudy, and the amount of fine powder saponified matter contained therein was 4% by weight based on the total saponified matter. After collecting the saponified material from the reactor, the interior of the reactor was inspected and a thin film of finely powdered saponified material was found to have adhered to the entire wall of the reactor. The melt index of the recovered saponified pellets was 63, and the saponification rate was 99.1%.
It was hot.
Claims (1)
1〜5の中から選ばれる1種または2種以上の低
級アルコール媒体中で該粒状共重合体が相互に融
着しない温度においてアルカリケン化、ならびに
場合により引続いて該粒状ケン化物を洗浄する方
法において、該媒体を循環させながら層膨張率が
1.1〜3.0の範囲に制御されているところの流動層
方式によることを特徴とするエチレン−酢酸ビニ
ル共重合体ケン化物の製造法。1. Alkali saponification of the granular ethylene-vinyl acetate copolymer in one or more lower alcohol medium selected from 1 to 5 carbon atoms at a temperature at which the granular copolymer does not fuse with each other; Optionally, in the method of subsequently washing the saponified granules, the layer expansion rate is increased while circulating the medium.
1. A method for producing a saponified ethylene-vinyl acetate copolymer, characterized by using a fluidized bed method in which the copolymer content is controlled within a range of 1.1 to 3.0.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19603881A JPS5896603A (en) | 1981-12-04 | 1981-12-04 | Manufacture of ethylene-vinyl acetate copolymer saponified product |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19603881A JPS5896603A (en) | 1981-12-04 | 1981-12-04 | Manufacture of ethylene-vinyl acetate copolymer saponified product |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5896603A JPS5896603A (en) | 1983-06-08 |
JPS6315923B2 true JPS6315923B2 (en) | 1988-04-06 |
Family
ID=16351159
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP19603881A Granted JPS5896603A (en) | 1981-12-04 | 1981-12-04 | Manufacture of ethylene-vinyl acetate copolymer saponified product |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5896603A (en) |
-
1981
- 1981-12-04 JP JP19603881A patent/JPS5896603A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5896603A (en) | 1983-06-08 |
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