JPH0753631A - Production of saponified product of ethylene-vinyl acetate copolymer - Google Patents
Production of saponified product of ethylene-vinyl acetate copolymerInfo
- Publication number
- JPH0753631A JPH0753631A JP21898293A JP21898293A JPH0753631A JP H0753631 A JPH0753631 A JP H0753631A JP 21898293 A JP21898293 A JP 21898293A JP 21898293 A JP21898293 A JP 21898293A JP H0753631 A JPH0753631 A JP H0753631A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- acetate copolymer
- ethylene
- saponified
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【産業上の利用分野】本発明は、エチレン−酢酸ビニル
共重合体ケン化物の製造法の改良に関する。FIELD OF THE INVENTION The present invention relates to an improved method for producing a saponified ethylene-vinyl acetate copolymer.
【０００２】[0002]
【従来の技術】エチレン−酢酸ビニル共重合体（以下Ｅ
ＶＡという）をケン化してエチレン−酢酸ビニル共重合
体ケン化物を製造する方法としては、従来からＥＶＡを
ベンゼンやトルエン等に溶解してアルカリ触媒によって
ケン化させる均一ケン化法と、ＥＶＡを粒状又は粉末状
のまま、低級アルコ−ル等に分散させてケン化する不均
一ケン化法とがある。均一ケン化法でのケン化反応は比
較的容易に高ケン化率のケン化物を得ることが出来る
が、溶媒との分離、回収の必要があって工業的ではな
く、一方不均一ケン化法では高いケン化物を得る為に
は、通常オートクレーブ等を使用し、加圧下で反応させ
るか、比較的長時間反応させる等の方法を取る必要があ
り、工業的製造方法としてはいずれも難点があった。2. Description of the Related Art Ethylene-vinyl acetate copolymer (hereinafter referred to as E
As a method for producing a saponified product of an ethylene-vinyl acetate copolymer by saponifying (VA), a uniform saponification method in which EVA is dissolved in benzene, toluene or the like and saponified with an alkali catalyst, and EVA is granular Alternatively, there is a heterogeneous saponification method in which the powder is kept as it is and dispersed in a lower alcohol or the like for saponification. The saponification reaction by the homogeneous saponification method can easily obtain a saponified product with a high saponification rate, but it is not industrial because it needs to be separated from the solvent and recovered, while the heterogeneous saponification method In order to obtain a highly saponified product, it is usually necessary to use an autoclave or the like and carry out a reaction under pressure, or a reaction for a relatively long time, which is a disadvantage as an industrial production method. It was
【０００３】[0003]
【発明が解決しようとする課題】本発明者らは、工業的
に有利な不均一ケン化法において、オートクレーブ等を
必要とせず、工業的に容易にしかも高ケン化率の目的物
を製造する方法について鋭意研究、検討した結果、本発
明の方法を見出すに至った。DISCLOSURE OF THE INVENTION In the industrially advantageous heterogeneous saponification method, the present inventors do not need an autoclave or the like and can industrially easily produce a target product having a high saponification rate. As a result of earnest research and study on the method, the inventors have found the method of the present invention.
【０００４】[0004]
【課題を解決するための手段】本発明は、エチレン−酢
酸ビニル共重合体を有機溶媒中、金属アルコラ−トを用
いてケン化するに際し、アルカリ金属水酸化物の共存下
に行うことを特徴とするエチレン−酢酸ビニル共重合体
ケン化物の製造法である。本発明の特徴は、ケン化に当
たり、金属アルコラ−トとアルカリ金属水酸化物を併用
することにあり、かくして常圧・短時間で目的とする高
ケン化率のエチレン−酢酸ビニル共重合体ケン化物を工
業的に有利に製造することにある。従来から、ケン化に
当たり、アルカリ触媒として金属アルコラ−ト又はアル
カリ金属水酸化物をそれぞれ別々に用いることは知られ
ているが、これらを同時に併用使用する方法は知られて
いない。The present invention is characterized in that when an ethylene-vinyl acetate copolymer is saponified in an organic solvent using a metal alcoholate, it is carried out in the presence of an alkali metal hydroxide. Is a method for producing a saponified ethylene-vinyl acetate copolymer. A characteristic of the present invention is that a metal alcoholate and an alkali metal hydroxide are used in combination for saponification, and thus, a desired high saponification rate ethylene-vinyl acetate copolymer saponification is carried out under normal pressure and in a short time. To produce the compound industrially. It has been conventionally known that a metal alcoholate or an alkali metal hydroxide is separately used as an alkali catalyst for saponification, but a method of using these in combination is not known.
【０００５】以下、本発明についし詳しく説明する。本
発明に使用されるＥＶＡは高圧法、溶液法など従来知ら
れた方法によって容易に製造されるものが使用される。
本発明に好ましく用いられるＥＶＡは、酢酸ビニル含量
が約５〜80重量％、好ましくは10〜55重量％で、メルト
インデックス（ＡＳＴＭＤ−１２３８、以下「ＭＩ」と
いう）が 0.5〜500 、好ましくは５０〜３００の範囲の
ものを用いるときに本発明効果が最も顕著に発揮され
る。The present invention will be described in detail below. The EVA used in the present invention is one that is easily manufactured by a conventionally known method such as a high pressure method or a solution method.
EVA preferably used in the present invention has a vinyl acetate content of about 5 to 80% by weight, preferably 10 to 55% by weight, and a melt index (ASTMD-1238, hereinafter referred to as "MI") of 0.5 to 500, preferably 50. The effect of the present invention is most prominently exhibited when a material having a range of up to 300 is used.
【０００６】本発明に使用される有機溶媒としては、通
常低級アルコ−ルが好ましく用いられ、具体的にはメタ
ノ−ル、エタノ−ル、n −プロパノ−ル、イソプロパノ
−ル、n −ブタノ−ルなどがあげられ、これらは単独ま
たは混合使用される。該有機溶媒の使用量はＥＶＡに対
し０．５〜１０倍量、好ましくは１〜５倍量である。As the organic solvent used in the present invention, lower alcohol is usually preferably used. Specifically, methanol, ethanol, n-propanol, isopropanol and n-butanol are used. And the like, which may be used alone or as a mixture. The amount of the organic solvent used is 0.5 to 10 times, preferably 1 to 5 times the amount of EVA.
【０００７】本発明に使用される金属アルコラ−トとし
ては、ナトリウムメチラ−ト、カリウムメチラ−ト、ナ
トリウムエチラ−ト、カリウムエチラ−ト等であり、該
金属アルコラートの使用量はＥＶＡに対して１〜３０重
量％、好ましくは５〜２０重量％である。The metal alcoholate used in the present invention includes sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, etc. The amount of the metal alcoholate used is based on EVA. It is 1 to 30% by weight, preferably 5 to 20% by weight.
【０００８】本発明に使用されるアルカリ金属水酸化物
としては水酸化ナトリウム、水酸化カリウム、水酸化リ
チウム等である。ここに使用するアルカリ金属水酸化物
は金属アルコラ−ト触媒によるエステル交換反応で副生
する例えば、酢酸メチルを加水分解するために使用さ
れ、酢酸メチルを分解し、反応温度の低下を防ぎ、常に
一定の反応温度を保持することができ、高ケン化率の目
的物を製造するのに好都合となるものと考えられる。該
アルカリ金属水酸化物の使用量はＥＶＡ中の酢酸ビニル
に対して０．２〜０．９モルである。The alkali metal hydroxide used in the present invention is sodium hydroxide, potassium hydroxide, lithium hydroxide or the like. The alkali metal hydroxide used here is used as a by-product in the transesterification reaction with a metal alcoholate catalyst, for example, to hydrolyze methyl acetate, decomposes methyl acetate, and prevents a decrease in the reaction temperature. It is considered that a constant reaction temperature can be maintained, which is convenient for producing a target product having a high saponification rate. The amount of the alkali metal hydroxide used is 0.2 to 0.9 mol based on the vinyl acetate in EVA.
【０００９】本発明の方法においては、ケン化物の着色
防止のためにシアン酢酸エステルと水を併用使用するこ
とができる。使用するシアン酢酸エステルとしてはシア
ン酢酸メチルエステル、シアン酢酸エチルエステル、シ
アン酢酸プロピルエステル、シアン酢酸ブチルエステ
ル、シアン酢酸フェニルエステル等であり、特に経済的
な見地から、シアノ酢酸メチルエステル、シアノ酢酸エ
チルエステルが好ましい。これらシアン酢酸エステルの
類の添加量はケン化すべきＥＶＡに対し、０．０１〜１
０重量％、好ましくは０．０ ５〜５重量％である。ま
たシアン酢酸エステルと併用する水の量は金属アルコラ
−トに対して０．１倍〜０．００１倍で、好ましくは
０．０８倍〜０．００５倍である。In the method of the present invention, cyanoacetic acid ester and water can be used in combination for preventing discoloration of the saponified product. Examples of the cyanoacetic acid ester to be used include cyanoacetic acid methyl ester, cyanoacetic acid ethyl ester, cyanoacetic acid propyl ester, cyanoacetic acid butyl ester, cyanoacetic acid phenyl ester, and the like. Esters are preferred. The addition amount of these cyanacetic acid esters is 0.01 to 1 with respect to EVA to be saponified.
It is 0% by weight, preferably 0.05 to 5% by weight. The amount of water used in combination with cyanoacetate is 0.1 to 0.001 times, preferably 0.08 to 0.005 times the metal alcoholate.
【００１０】本発明の方法において、ケン化反応温度
は、４０〜１００℃、好ましくは５０〜８０℃で行われ
る。本発明においては、オートクレーブ等を必要とせ
ず、常温で実施できる。In the method of the present invention, the saponification reaction temperature is 40 to 100 ° C, preferably 50 to 80 ° C. The present invention does not require an autoclave or the like and can be carried out at room temperature.
【００１１】[0011]
【発明の効果】本発明によれば、オートクレーブ等を必
要とせず、工業的に容易にしかも高ケン化率の目的物を
製造することができる。EFFECTS OF THE INVENTION According to the present invention, the desired product having a high saponification rate can be produced industrially easily without the need for an autoclave or the like.
【００１２】[0012]
【実施例】以下、本発明を実施例により更に詳細に説明
するが本発明はこれに限定されるものではない。 実施例１ 攪拌機、冷却管、温度計を付した２リットルのフラスコ
に酢酸ビニル含量２８重量％（ＭＩ＝３００）のＥＶＡ
ペレット７００g 、メタノ−ル９５０g を仕込み、攪拌
下に水０．３g とシアン酢酸メチル４．７g を滴下した
後、１０分攪拌し、ナトリウムメチラ−トの２８％メタ
ノ−ル溶液１００g を滴下し、さらに苛性ソ−ダの７5.
０g を投入した後４０℃に昇温し、１時間保温した後、
７０℃に昇温し、１０時間保温し（保温終了還流温度
６８℃）、ペレットを水洗し、７０℃で３０時間乾燥し
た。得られたケン化物のケン化率は９9.３％で白度の高
い樹脂であった。EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 EVA having a vinyl acetate content of 28% by weight (MI = 300) was placed in a 2 liter flask equipped with a stirrer, a condenser and a thermometer.
700 g of pellets and 950 g of methanol were charged, 0.3 g of water and 4.7 g of methyl cyanoacetate were added dropwise with stirring, and then the mixture was stirred for 10 minutes, and 100 g of 28% methanol solution of sodium methylate was added dropwise. , More caustic soda 75.
After adding 0 g, the temperature was raised to 40 ° C and kept for 1 hour.
The temperature is raised to 70 ° C and kept warm for 10 hours.
68 ° C.), the pellets were washed with water and dried at 70 ° C. for 30 hours. The saponification rate of the obtained saponified product was 99.3%, which was a resin with high whiteness.
【００１３】なお、ケン化率は次式により計算した（以
下同じ）。 （Ａ）＝原料ＥＶＡ中のＶＡｃ重量％ （Ｂ）＝ケン化後の残存ＶＡｃ重量％ ケン化率％＝（Ａ）−（Ｂ）／（Ａ）× １００The saponification rate was calculated by the following formula (the same applies hereinafter). (A) = VAc weight% in raw material EVA (B) = Residual VAc weight% after saponification Saponification rate% = (A) − (B) / (A) × 100
【００１４】実施例２ 攪拌機、冷却管、温度計を付した２リットルのフラスコ
に酢酸ビニル含量２８重量％（ＭＩ＝１５０）のＥＶＡ
ペレット７００g 、メタノ−ル７９０g を仕込み、攪拌
下に水0.５g とシアン酢酸メチル１０g を滴下した後、
１０分間攪拌しナトリウムメチラ−トの２８％メタノ−
ル溶液１００g を滴下し、苛性ソ−ダの７５g を投入
し、溶解後５０℃で１時間保温、更に７０℃で９時間保
温し（保温終了還流温度 ６８℃）、その後、室温まで
冷した後エチレン−酢酸ビニル共重合体のケン化物を濾
別し、７９０g の水で1 回洗浄した後、７０℃で２０時
間乾燥し、ケン化率、９9.３％の白度の高いエチレン−
酢酸ビニル共重合体のケン化物を得た。Example 2 EVA having a vinyl acetate content of 28% by weight (MI = 150) was placed in a 2 liter flask equipped with a stirrer, a cooling tube and a thermometer.
700 g of pellets and 790 g of methanol were charged, and 0.5 g of water and 10 g of methyl cyanoacetate were added dropwise with stirring.
After stirring for 10 minutes, 28% methanol of sodium methylate
100 g of sodium chloride solution was added dropwise, and 75 g of caustic soda was added, and after dissolution, the temperature was kept at 50 ° C for 1 hour and further at 70 ° C for 9 hours (retaining temperature reflux temperature 68 ° C), and then cooled to room temperature. The saponified product of ethylene-vinyl acetate copolymer was filtered off, washed once with 790 g of water and dried at 70 ° C for 20 hours to obtain a highly white ethylene-containing product with a saponification rate of 99.3%.
A saponified product of vinyl acetate copolymer was obtained.
【００１５】実施例３〜７ 以下、実施例１〜２に準じて、ＥＶＡ、金属アルコラー
ト、アルカリ金属水酸化物の種類や量を変え、他は実施
例１〜２と同様にしてケン化物を製造した。結果を表−
１、−２に示す。また、本発明によらない場合を比較例
１〜４として同様に表−１、−２に示した。Examples 3 to 7 In the following, according to Examples 1 and 2, the kinds and amounts of EVA, metal alcoholate, and alkali metal hydroxide were changed, and the saponified product was obtained in the same manner as in Examples 1 and 2. Manufactured. Table of results
1 and -2. Further, the cases not according to the present invention are similarly shown in Tables 1 and 2 as Comparative Examples 1 to 4.
【００１６】なお、表中の記号は、以下の通りである。 *1ＭＡ＝シアン酢酸メチルの略称。 *2ＮａＯＣＨ3 ＝ NaOCH3 の28% メタノ-ル 溶液を使用し
た。 *3ＮａＯＨ＝フレ−ク状苛性ソ−ダを使用した。 *4ＭＩ＝メルトインデックス（ＡＳＴＭＤ−１２３８）The symbols in the table are as follows. * 1 MA = Abbreviation for methyl cyanate. * 2 NaOCH 3 = 28% methanol solution of NaOCH 3 was used. * 3 NaOH = flaky caustic soda was used. * 4 MI = melt index (ASTMD-1238)
【００１７】[0017]
【表−１】 [Table-1]
【００１８】[0018]
【表−２】 [Table-2]
Claims (6)
中、金属アルコラ−トを用いてケン化するに際し、アル
カリ金属水酸化物の共存下に行う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. An ethylene-vinyl acetate copolymer, which is characterized in that an ethylene-vinyl acetate copolymer is saponified in an organic solvent using a metal alcoholate in the presence of an alkali metal hydroxide. Method for producing combined saponified products.
ム、水酸化カリウム及び水酸化リチウムから選ばれる請
求項１に記載のエチレン−酢酸ビニル共重合体ケン化物
の製造法。2. The method for producing a saponified ethylene-vinyl acetate copolymer according to claim 1, wherein the alkali metal hydroxide is selected from sodium hydroxide, potassium hydroxide and lithium hydroxide.
酢酸ビニル共重合体中の酢酸ビニルに対して０．２〜
０．９モル比である請求項１〜請求項２のいずれかに記
載のエチレン−酢酸ビニル共重合体ケン化物の製造法。3. The amount of alkali metal hydroxide is ethylene-
0.2 to vinyl acetate in the vinyl acetate copolymer
The method for producing a saponified ethylene-vinyl acetate copolymer according to any one of claims 1 to 2, which has a 0.9 molar ratio.
求項１〜請求項４のいずれかに記載のエチレン−酢酸ビ
ニル共重合体ケン化物の製造法。4. The method for producing a saponified ethylene-vinyl acetate copolymer according to claim 1, wherein the organic solvent is selected from lower alcohols.
ト、カリウムメチラ−ト及びナトリウムエチラ−ト、カ
リウムエチラ−トから選ばれる請求項１〜請求項４のい
ずれかに記載のエチレン−酢酸ビニル共重合体ケン化物
の製造法。 【請求項５】エチレン−酢酸ビニル共重合体が、粒状又
は粉末状である請求項１〜請求項５のいずれかに記載の
エチレン−酢酸ビニル共重合体ケン化物の製造法。5. A metal alcoholate is sodium methylate.
A method for producing a saponified ethylene-vinyl acetate copolymer according to any one of claims 1 to 4, which is selected from the group consisting of potassium ether, potassium methylate, sodium ethylate and potassium ethylate. 5. The method for producing a saponified ethylene-vinyl acetate copolymer according to any one of claims 1 to 5, wherein the ethylene-vinyl acetate copolymer is in the form of particles or powder.
び水を共存させることを特徴とする請求項１〜請求項５
のいずれかに記載のエチレン−酢酸ビニル共重合体ケン
化物の製造法。 【０００１】6. The saponification is characterized in that cyanoacetic acid esters and water are allowed to coexist.
The method for producing a saponified ethylene-vinyl acetate copolymer according to any one of 1. [0001]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21898293A JPH0753631A (en) | 1993-08-10 | 1993-08-10 | Production of saponified product of ethylene-vinyl acetate copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21898293A JPH0753631A (en) | 1993-08-10 | 1993-08-10 | Production of saponified product of ethylene-vinyl acetate copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0753631A true JPH0753631A (en) | 1995-02-28 |
Family
ID=16728417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21898293A Pending JPH0753631A (en) | 1993-08-10 | 1993-08-10 | Production of saponified product of ethylene-vinyl acetate copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0753631A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069123A (en) * | 2000-08-31 | 2002-03-08 | Kuraray Co Ltd | Method for producing saponified ethylene-vinyl acetate copolymer |
| JP2011052234A (en) * | 2010-12-15 | 2011-03-17 | Kuraray Co Ltd | Method for producing pellet of partially saponified ethylene-vinyl acetate copolymer |
-
1993
- 1993-08-10 JP JP21898293A patent/JPH0753631A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069123A (en) * | 2000-08-31 | 2002-03-08 | Kuraray Co Ltd | Method for producing saponified ethylene-vinyl acetate copolymer |
| JP2011052234A (en) * | 2010-12-15 | 2011-03-17 | Kuraray Co Ltd | Method for producing pellet of partially saponified ethylene-vinyl acetate copolymer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB2026478A (en) | Process for producing alkali metal salts of aryl pyruvic acids | |
| JPH0753631A (en) | Production of saponified product of ethylene-vinyl acetate copolymer | |
| JPH0481975B2 (en) | ||
| JPH04234345A (en) | Process for producing organic ester and amide and catalyst system therefor | |
| JP3429810B2 (en) | Process for producing saponified ethylene-vinyl acetate copolymer | |
| WO1988005772A1 (en) | Process for preparing tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl)methane | |
| SU978723A3 (en) | Process for producing derivatives of substituted oxycyclohexahylacetic | |
| JP2002179611A (en) | Method for producing dicarboxylic acid compound | |
| US3865884A (en) | Preparation of orcinol | |
| CA2044309C (en) | Process for the preparation of aryl-substituted propionic acid esters | |
| JPWO2005095322A1 (en) | Process for producing 1,2-cis-2-fluorocyclopropane-1-carboxylic acid esters | |
| US5003068A (en) | Pyridazinone manufacture | |
| JP2721515B2 (en) | Method for producing α-substituted-γ-butyrolactones | |
| JPS6332068B2 (en) | ||
| EP0448775A2 (en) | Colorless grained alpha-form crystals of tetrakis [3-(3,5-Di-T-butyl-4-hydroxyphenyl)propionyloxymethyl]methane and process for its manufacture | |
| JPS61260086A (en) | Production of magnesium dialkoxide | |
| US2653157A (en) | p-amino-salicylic acid derivatives and their production | |
| JPH06157418A (en) | Reducing dehalogenation process | |
| US3217033A (en) | Process for preparing ortho substituted benzoic acid compounds | |
| JPH11279121A (en) | Production of alkyl beta-alkoxypropionate | |
| JPH0454177A (en) | Production of gamma-alkyl-gamma-lactone | |
| US3455999A (en) | Substituted malonic acid monohydrazides | |
| JPH0422895B2 (en) | ||
| JPS6372649A (en) | Production of 3,3',4,4'-biphenyltetracarboxylic acid | |
| JPH0232266B2 (en) | 22 * 44ETOKISHIFUENIRU ** 2MECHIRUPUROPIRUARUKOORUOYOBISONOSEIZOHO |