JPH11140136A - Method for polymerizing ethylene-vinyl acetate copolymer and method for producing saponified copolymer - Google Patents
Method for polymerizing ethylene-vinyl acetate copolymer and method for producing saponified copolymerInfo
- Publication number
- JPH11140136A JPH11140136A JP9320454A JP32045497A JPH11140136A JP H11140136 A JPH11140136 A JP H11140136A JP 9320454 A JP9320454 A JP 9320454A JP 32045497 A JP32045497 A JP 32045497A JP H11140136 A JPH11140136 A JP H11140136A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- ethylene
- acetate copolymer
- polymerization
- saponified
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
(57)【要約】
【課題】 エチレン−酢酸ビニル共重合体を重合するに
当たり、スケール付着が少ない重合法及び着色がなく、
かつフィッシュアイの少ないフィルムを得ることが可能
なエチレン−酢酸ビニル共重合体ケン化物の製造法を提
供する。
【解決手段】 クロトンアルデヒドの共存下、エチレン
と酢酸ビニルを溶媒中で共重合させてエチレン−酢酸ビ
ニル共重合体を製造し、必要に応じ更にケン化してエチ
レン−酢酸ビニル共重合体ケン化物を製造する。(57) [Problem] To polymerize an ethylene-vinyl acetate copolymer, there is no polymerization method with little scale adhesion and no coloring,
Provided is a method for producing a saponified ethylene-vinyl acetate copolymer capable of obtaining a film with less fish eyes. SOLUTION: In the coexistence of crotonaldehyde, ethylene and vinyl acetate are copolymerized in a solvent to produce an ethylene-vinyl acetate copolymer, and if necessary, further saponified to obtain a saponified ethylene-vinyl acetate copolymer. To manufacture.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、重合缶内にスケー
ル付着の少ないエチレン−酢酸ビニル共重合体の重合法
および着色が少なく、かつフィッシュアイの少ないフィ
ルムを得ることが可能な該共重合体のケン化物の製造法
に関する。FIELD OF THE INVENTION The present invention relates to a method for polymerizing an ethylene-vinyl acetate copolymer having less scale adhesion in a polymerization vessel and a copolymer capable of obtaining a film with less coloring and less fisheye. And a method for producing a saponified compound.
【０００２】[0002]
【従来の技術】エチレン−酢酸ビニル共重合体ケン化物
はガスバリアー性、機械的強度等の諸性質に優れている
ことから、フィルム、シート、容器、繊維等の各種用途
に多用されている。該ケン化物はエチレンと酢酸ビニル
を共重合し、次いでケン化することによって製造される
が、エチレン−酢酸ビニル共重合体の重合は、通常、ジ
ャケット及び還流コンデンサーのついた高圧の重合缶を
用いて、メタノール等のアルコール溶媒中に、原料であ
るエチレン及び酢酸ビニルを導入して行われる。2. Description of the Related Art Saponified ethylene-vinyl acetate copolymers are widely used in various applications such as films, sheets, containers and fibers because of their excellent properties such as gas barrier properties and mechanical strength. The saponified product is produced by copolymerizing ethylene and vinyl acetate, and then saponifying.The polymerization of the ethylene-vinyl acetate copolymer is usually carried out using a high-pressure polymerization vessel equipped with a jacket and a reflux condenser. Then, the raw material ethylene and vinyl acetate are introduced into an alcohol solvent such as methanol.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
方法でエチレン−酢酸ビニル共重合体の重合を行った場
合、重合缶内部にスケールが付着し易く、該スケールが
剥離して重合体中に混入すると、該重合体のケン化物を
フィルムにした時、フィッシュアイが多発し、品質の低
下を招くという問題が発生し、それ故スケール付着のな
い重合法が望まれているのである。However, when the ethylene-vinyl acetate copolymer is polymerized by the above-mentioned method, the scale easily adheres to the inside of the polymerization vessel, and the scale peels off and mixes into the polymer. Then, when a saponified product of the polymer is formed into a film, fish eyes frequently occur, which causes a problem of lowering the quality. Therefore, a polymerization method without scale adhesion is desired.
【０００４】[0004]
【課題を解決するための手段】本発明者は上記の問題を
解決するため鋭意研究を重ねた結果、クロトンアルデヒ
ドの共存下、溶媒中でエチレンと酢酸ビニルを共重合さ
せると、重合缶内部のスケール付着が少なく良好なエチ
レン−酢酸ビニル共重合体が得られ、又、該共重合体よ
り得られたケン化物は着色が少なく、該ケン化物をフィ
ルムにした時、フィッシュアイが少ないことを見出し本
発明を完成するに到った。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, when ethylene and vinyl acetate are copolymerized in a solvent in the presence of crotonaldehyde, the inside of the polymerization vessel becomes free. A good ethylene-vinyl acetate copolymer with little scale adhesion was obtained, and the saponified product obtained from the copolymer was less colored, and when the saponified product was made into a film, it was found that there was little fisheye. The present invention has been completed.
【０００５】[0005]
【発明の実施の形態】以下に本発明を詳細に説明する。
エチレンと酢酸ビニルの共重合は溶媒中での重合、すな
わち溶液重合法が実施される。エチレンと酢酸ビニルの
溶液重合法は、溶媒中で触媒の存在下に行われ、連続
式、回分式のいずれであっても良く、重合法に応じて適
宜条件が設定される。溶媒としては炭素数４以下のアル
コール又は炭素数４以下のアルコールを主とする混合溶
媒が用いられ、該アルコールとしては、メタノール、エ
タノール、プロパノール等が挙げられるが、好ましくは
メタノールが用いられ、溶媒量としては酢酸ビニル１０
０重量部に対して、１〜６０重量部が好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The copolymerization of ethylene and vinyl acetate is carried out in a solvent, that is, a solution polymerization method. The solution polymerization method of ethylene and vinyl acetate is performed in a solvent in the presence of a catalyst, and may be a continuous type or a batch type, and conditions are appropriately set according to the polymerization method. As the solvent, an alcohol having 4 or less carbon atoms or a mixed solvent mainly containing an alcohol having 4 or less carbon atoms is used. Examples of the alcohol include methanol, ethanol, and propanol, and preferably, methanol is used. The quantity is vinyl acetate 10
1 to 60 parts by weight relative to 0 parts by weight is preferred.
【０００６】触媒としては、ラジカル開始剤であれば特
に制限なく用いられるが、好ましくは２，２′−アゾビ
ス−（２，４−ジメチルバレロニトリル）、２，２′−
アゾビス−（２，４，４−トリメチルバレロニトリ
ル）、２，２′−アゾビスイソブチロニトリル、２，
２′−アゾビス−（４−メトキシ−２，４−ジメチルバ
レロニトリル）、２，２′−アゾビス−（２−メチルイ
ソブチラート）などのアゾ化合物、ｔ−ブチルパーオキ
シネオデカノエート、ｔ−ブチルパーピバレート、ｔ−
ブチルパーオキシ−２−エチルヘキノエートなどのアル
キルパーエステル類、ビス−（４−ｔ−ブチルシクロヘ
キシル）パーオキシ−ジ−カーボネート、ジ−シクロヘ
キシルパーオキシ−ジ−カーボネート、ビス（２−エチ
ルヘキシル）ジ−ｓｅｃ−ブチルパーオキシ−ジ−カー
ボネート、ジ−イソプロピルパーオキシ−ジ−カーボネ
ートなどのパーオキシ−ジ−カーボネート類、アセチル
パーオキシド、ベンゾイルパーオキシド、ラウロイルパ
ーオキシド、ジ−ラウロイルパーオキシド、ジ−デカノ
イルパーオキシド、ジ−オクタノイルパーオキシド、ジ
−プロピルパーオキシドなどのパーオキシド類などがあ
る。As the catalyst, any radical initiator can be used without any particular limitation. Preferably, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-
Azobis- (2,4,4-trimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,
Azo compounds such as 2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis- (2-methylisobutyrate), t-butylperoxy neodecanoate, t -Butyl perpivalate, t-
Alkyl peresters such as butylperoxy-2-ethylhexinoate, bis- (4-tert-butylcyclohexyl) peroxy-di-carbonate, di-cyclohexylperoxy-di-carbonate, bis (2-ethylhexyl) di -Sec-butylperoxy-di-carbonate, peroxy-di-carbonates such as di-isopropylperoxy-di-carbonate, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, di-lauroyl peroxide, di-deca There are peroxides such as noyl peroxide, di-octanoyl peroxide and di-propyl peroxide.
【０００７】触媒の使用量は、回分式の場合、酢酸ビニ
ル１００重量部に対して、０．００２〜０．１重量部が
好ましく、０．００２重量部未満では、触媒効率が悪く
重合時間が長くなったり、重合が進まない場合があり、
０．１重量部を越えると、重合の制御が困難となった
り、重合終了後も触媒が残存して後重合を起こすことが
あり好ましくない。連続式の場合、酢酸ビニル１００重
量部に対して、０．００２〜０．０６重量部が好まし
く、０．００２重量部未満では、触媒効率が悪く重合時
間が長くなったり、重合が進まない場合があり、０．０
６重量部を越えると、重合の制御が困難となったり、重
合終了後も触媒が残存して後重合を起こすことがあり好
ましくない。In the case of a batch system, the amount of the catalyst used is preferably 0.002 to 0.1 part by weight based on 100 parts by weight of vinyl acetate. It may become longer or the polymerization may not proceed,
If the amount exceeds 0.1 part by weight, it becomes difficult to control the polymerization, or the catalyst may remain even after the completion of the polymerization to cause post-polymerization. In the case of a continuous system, the amount is preferably 0.002 to 0.06 parts by weight based on 100 parts by weight of vinyl acetate. If the amount is less than 0.002 part by weight, the catalyst efficiency is poor and the polymerization time is long or the polymerization does not proceed. And 0.0
If the amount is more than 6 parts by weight, it is not preferable because control of polymerization becomes difficult, and after polymerization is completed, the catalyst may remain to cause post-polymerization.
【０００８】本発明では、エチレン−酢酸ビニル共重合
体を重合するに当たり、クロトンアルデヒドを共存させ
ることを最大の特徴とするのもので、クロトンアルデヒ
ドの量は０．０００１〜０．５ｐｐｍが好ましく、更に
は０．０００２〜０．００５ｐｐｍである。０．０００
１ｐｐｍ未満では重合の制御が困難となったり重合缶内
部にスケールの付着し易い傾向があり好ましくなく、
０．５ｐｐｍを越えると重合が抑制されて重合率が低く
なったり、又重合時間が長く必要となり、更に重合缶内
部にスケールの付着が見られる場合があり好ましくな
い。In the present invention, the most characteristic feature of the present invention is that crotonaldehyde coexists in the polymerization of the ethylene-vinyl acetate copolymer, and the amount of crotonaldehyde is preferably 0.0001 to 0.5 ppm. Furthermore, it is 0.0002 to 0.005 ppm. 0.000
If it is less than 1 ppm, it becomes difficult to control the polymerization or the scale tends to adhere to the inside of the polymerization vessel, which is not preferable.
If it exceeds 0.5 ppm, the polymerization is suppressed and the polymerization rate is lowered, and the polymerization time is required to be long. Further, there is a case where scale adheres to the inside of the polymerization vessel, which is not preferable.
【０００９】重合を行うに当たっては、酢酸ビニルと
クロトンアルデヒドを別々に、あるいはクロトンアルデ
ヒド含有量を予めコントロールした酢酸ビニルをアルコ
ール溶媒に溶解し、触媒を添加し、更にエチレンを高圧
下に仕込む方法、酢酸ビニルをアルコール溶媒に溶解
し、触媒及びクロトンアルデヒドを添加し、更にエチレ
ンを高圧下に仕込む方法等が実施される。In carrying out the polymerization, a method in which vinyl acetate and crotonaldehyde are separately separated or vinyl acetate whose crotonaldehyde content is previously controlled is dissolved in an alcohol solvent, a catalyst is added, and ethylene is further charged under high pressure; For example, a method in which vinyl acetate is dissolved in an alcohol solvent, a catalyst and crotonaldehyde are added, and ethylene is further charged under high pressure is used.
【００１０】重合温度として好ましくは４０〜８０℃、
更には５５〜７０℃である。該重合温度が４０℃未満で
は重合に長時間を要し、重合時間を短縮しようとすると
触媒が多量に必要となり、８０℃を越えると重合制御が
困難となり好ましくない。重合時間は、回分式の場合、
好ましくは４〜１０時間、更には６〜９時間である。該
重合時間が４時間未満では重合温度を高くしたり、触媒
量を多く設定しなければならず、重合制御が困難とな
り、１０時間を越えると生産性の面で問題があり好まし
くない。連続式の場合、重合缶内での平均滞留時間は２
〜８時間が好ましく、更には２〜６時間である。該滞留
時間が２時間未満では重合温度を高くしたり、触媒量を
多く設定しなければならず、重合制御が困難となり、８
時間を越えると生産性の面で問題があり好ましくない。The polymerization temperature is preferably 40 to 80 ° C.,
Further, the temperature is 55 to 70 ° C. If the polymerization temperature is lower than 40 ° C., a long time is required for the polymerization, and if the polymerization time is shortened, a large amount of a catalyst is required. The polymerization time is as follows:
Preferably, it is 4 to 10 hours, more preferably 6 to 9 hours. If the polymerization time is less than 4 hours, it is necessary to raise the polymerization temperature or set a large amount of the catalyst, and it is difficult to control the polymerization. If the polymerization time exceeds 10 hours, there is a problem in productivity, which is not preferable. In the case of the continuous type, the average residence time in the polymerization vessel is 2
-8 hours is preferable, and 2-6 hours is more preferable. If the residence time is less than 2 hours, it is necessary to raise the polymerization temperature or set a large amount of the catalyst, and it becomes difficult to control the polymerization.
If the time is exceeded, there is a problem in productivity, which is not preferable.
【００１１】重合率（酢酸ビニル）は生産性の面から重
合制御が可能な範囲で出来るだけ高く設定され、回分式
の場合、好ましくは２０〜９０％に設定される。該重合
率が２０％未満では工業的に生産性が悪く、未重合の酢
酸ビニルが多量に残存するという問題があり、９０％を
越えると重合制御が困難となり好ましくない。連続式の
場合、重合率は、好ましくは２０〜６０％に設定され
る。該重合率が２０％未満では工業的に生産性が悪く、
未重合の酢酸ビニルが多量に残存するという問題があ
り、６０％を越えると重合制御が困難となり好ましくな
い。The polymerization rate (vinyl acetate) is set as high as possible within the range where polymerization can be controlled from the viewpoint of productivity. In the case of a batch system, it is preferably set to 20 to 90%. If the polymerization rate is less than 20%, the productivity is industrially poor, and there is a problem that a large amount of unpolymerized vinyl acetate remains. If it exceeds 90%, the polymerization control becomes difficult, which is not preferable. In the case of a continuous type, the polymerization rate is preferably set to 20 to 60%. If the polymerization rate is less than 20%, industrial productivity is poor,
There is a problem that a large amount of unpolymerized vinyl acetate remains, and if it exceeds 60%, it becomes difficult to control the polymerization, which is not preferable.
【００１２】また、エチレン−酢酸ビニル共重合体中の
エチレン含有量は、重合缶内のエチレン圧等によりコン
トロールすることができ、かかる含有量としては１５〜
６０モル％が好ましく、更には２５〜５５モル％であ
る。該エチレン含有量が１５モル％未満では、エチレン
−酢酸ビニル共重合体をケン化して得られたケン化物を
溶融成形する場合、溶融成形性が低下すると共に、溶融
成形物の高湿時のガスバリヤー性が大きく低下し、６０
モル％を越えると、該ケン化物の溶融成形した場合、成
形物の機械的強度及びガスバリアー性が充分でなく好ま
しくない。Further, the ethylene content in the ethylene-vinyl acetate copolymer can be controlled by the ethylene pressure in the polymerization vessel and the like.
It is preferably 60 mol%, more preferably 25 to 55 mol%. When the ethylene content is less than 15 mol%, when the saponified product obtained by saponifying the ethylene-vinyl acetate copolymer is melt-molded, the melt-molding property is reduced and the gas of the molten molded product at the time of high humidity is reduced. The barrier properties are greatly reduced,
If it exceeds mol%, when the saponified product is melt-molded, the mechanical strength and gas barrier properties of the molded product are not sufficient, which is not preferable.
【００１３】この時のエチレン圧としては１５〜７５ｋ
ｇ／ｃｍ２に設定される。The ethylene pressure at this time is 15 to 75 k
g / cm 2 .
【００１４】又本発明において、エチレン−酢酸ビニル
共重合体の重合法はエチレン、酢酸ビニル以外に、これ
らと共重合可能なエチレン性不飽和単量体を共重合成分
として含有しても差し支えない。該単量体としては、例
えばプロピレン、イソブチレン、α−オクテン、α−ド
デセン、α−オクタデセン等のオレフィン類、アクリル
酸、メタクリル酸、クロトン酸、マレイン酸、無水マレ
イン酸、イタコン酸等の不飽和酸類あるいはその塩ある
いはモノ又はジアルキルエステル等、アクリロニトリ
ル、メタアクリロニトリル等のニトリル類、アクリルア
ミド、メタクリルアミド等のアミド類、エチレンスルホ
ン酸、アリルスルホン酸、メタアリルスルホン酸等のオ
レフィンスルホン酸あるいはその塩、アルキルビニルエ
ーテル類、Ｎ−アクリルアミドメチルトリメチルアンモ
ニウムクロライド、アリルトリメチルアンモニウムクロ
ライド、ジメチルアリルビニルケトン、Ｎ−ビニルピロ
リドン、塩化ビニル、塩化ビニリデン、ポリオキシエチ
レン（メタ）アリルエーテル、ポリオキシプロピレン
（メタ）アリルエーテルなどのポリオキシアルキレン
（メタ）アリルエーテル、ポリオキシエチレン（メタ）
アクリレート、ポリオキシプロピレン（メタ）アクリレ
ート等のポリオキシアルキレン（メタ）アクリレート、
ポリオキシエチレン（メタ）アクリルアミド、ポリオキ
シプロピレン（メタ）アクリルアミド等のポリオキシア
ルキレン（メタ）アクリルアミド、ポリオキシエチレン
（１−（メタ）アクリルアミド−１，１−ジメチルプロ
ピル）エステル、ポリオキシエチレンビニルエーテル、
ポリオキシプロピレンビニルエーテル、ポリオキシエチ
レンアリルアミン、ポリオキシプロピレンアリルアミ
ン、ポリオキシエチレンビニルアミン、ポリオキシプロ
ピレンビニルアミン等が挙げられる。In the present invention, in addition to ethylene and vinyl acetate, the ethylene-vinyl acetate copolymer may contain an ethylenically unsaturated monomer copolymerizable therewith as a copolymerization component. . Examples of the monomer include olefins such as propylene, isobutylene, α-octene, α-dodecene, and α-octadecene; and unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, and itaconic acid. Acids or salts or mono- or dialkyl esters thereof, acrylonitrile, nitriles such as methacrylonitrile, acrylamide, amides such as methacrylamide, ethylenesulfonic acid, allylsulfonic acid, olefinsulfonic acid such as methallylsulfonic acid or a salt thereof, Alkyl vinyl ethers, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallylvinylketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene Down (meth) polyoxyalkylene (meth) allyl ethers such as allyl ether, polyoxypropylene (meth) allyl ether, polyoxyethylene (meth)
Acrylates, polyoxyalkylene (meth) acrylates such as polyoxypropylene (meth) acrylate,
Polyoxyalkylene (meth) acrylamide such as polyoxyethylene (meth) acrylamide and polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether,
Examples thereof include polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, and polyoxypropylene vinylamine.
【００１５】かくして本発明の重合法でエチレン−酢酸
ビニル共重合体が得られるわけであるが、かかるエチレ
ン−酢酸ビニル共重合体は、接着剤、粘着剤、塗料、繊
維・織物の加工剤、紙・皮革の加工剤、各種材料のバイ
ンダー、セメント・モルタルの混和液等に利用される。Thus, an ethylene-vinyl acetate copolymer can be obtained by the polymerization method of the present invention. Such an ethylene-vinyl acetate copolymer can be used as an adhesive, a pressure-sensitive adhesive, a paint, a fiber / fabric processing agent, It is used as a processing agent for paper and leather, a binder for various materials, and a mixture of cement and mortar.
【００１６】上記の重合法で得られたエチレン−酢酸ビ
ニル共重合体は更にケン化され、エチレン−酢酸ビニル
共重合体ケン化物として用途拡大が可能であるが、かか
る方法で得られたエチレン−酢酸ビニル共重合体ケン化
物は着色がなく、またフィルムにした時フィッシュアイ
が少ないという顕著な効果が得られる。The ethylene-vinyl acetate copolymer obtained by the above-mentioned polymerization method is further saponified, and its use can be expanded as a saponified ethylene-vinyl acetate copolymer. The saponified vinyl acetate copolymer has no remarkable effect that it is not colored and has little fish eyes when formed into a film.
【００１７】かかるケン化反応は、通常、アルカリ触媒
の共存下に実施される。ケン化に当たっては、上記エチ
レン−酢酸ビニル共重合体を、アルコール（通常メタノ
ールが用いられる）又はアルコール含有媒体中に通常２
０〜６０重量％程度の濃度になる如く溶解し、アルカリ
触媒（通常水酸化ナトリウム、水酸化カリウムなどのア
ルカリ金属水酸化物が用いられる）を添加して４０〜１
４０℃の温度で反応せしめる。Such a saponification reaction is usually carried out in the presence of an alkali catalyst. In the saponification, the ethylene-vinyl acetate copolymer is usually added to an alcohol (usually methanol is used) or an alcohol-containing medium in an alcohol-containing medium.
It is dissolved to a concentration of about 0 to 60% by weight, and an alkali catalyst (usually an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like is used) is added thereto, and the solution is dissolved in an amount of 40 to 1%.
React at a temperature of 40 ° C.
【００１８】かかるケン化により得られるエチレン−酢
酸ビニル共重合体ケン化物の酢酸ビニル成分のケン化度
は８０〜１００モル％とすることが好ましく、更にはケ
ン化度９０〜１００モル％、特に９５〜１００モル％と
するのが有利である。ケン化度が８０モル％未満の場
合、該エチレン−酢酸ビニル共重合体ケン化物を溶融成
形する場合の熱安定性が悪くなると共に、得られた成形
物も機械的強度やガスバリアー性が大きく低下して好ま
しくない。The saponification degree of the vinyl acetate component of the saponified ethylene-vinyl acetate copolymer obtained by the saponification is preferably from 80 to 100 mol%, more preferably from 90 to 100 mol%, particularly preferably from 90 to 100 mol%. It is advantageously between 95 and 100 mol%. When the saponification degree is less than 80 mol%, the thermal stability when the ethylene-vinyl acetate copolymer saponified product is melt-molded is deteriorated, and the obtained molded product also has large mechanical strength and gas barrier properties. It is not preferable because it decreases.
【００１９】次に上記で得られたエチレン−酢酸ビニル
共重合体ケン化物のアルコール溶液はそのままでもよい
が、好ましくは、水を加えるだけか、水を加えて、更に
該ケン化物溶液を適宜濃度調整して、アルコール／水溶
液としてストランド製造用の溶液とする。Next, the alcohol solution of the saponified ethylene-vinyl acetate copolymer obtained above may be used as it is, but preferably, water is added or water is added. Adjust to make a solution for strand production as alcohol / water solution.
【００２０】次いで、エチレン−酢酸ビニル共重合体ケ
ン化物のアルコール／水溶液は、水又は水／アルコール
（混合）溶液等の凝固液中にストランド状に押し出して
析出させるのである。Next, the alcohol / aqueous solution of the saponified ethylene-vinyl acetate copolymer is extruded in the form of a strand into a coagulating liquid such as water or a water / alcohol (mixed) solution to precipitate.
【００２１】析出させたストランドは次に切断されてペ
レット状となり、次いで水洗される。水洗したペレット
は酸及び／又はそれらの塩類等の薬剤の水溶液で浸漬さ
せる等の方法で化学処理を行なうことが好ましく、かか
る薬剤としては、ギ酸、酢酸、アジピン酸、リン酸、ホ
ウ酸あるいはそれらの塩類等が挙げられ、より好ましく
は酢酸が用いられる。The deposited strand is then cut into pellets and then washed with water. The washed pellets are preferably subjected to a chemical treatment such as immersion in an aqueous solution of a chemical such as an acid and / or a salt thereof. Examples of such a chemical include formic acid, acetic acid, adipic acid, phosphoric acid, boric acid, and boric acid. And the like, and more preferably acetic acid.
【００２２】上記で得られたペレットは溶融成形されて
所望する成形物に成形されるのであるが、溶融成形に際
しての温度条件としては１６０〜２６０℃程度とするの
が望ましい。成形に際しては必要に応じガラス繊維、炭
素繊維などの補強材、フィラー、着色剤、ハイドロタル
サイトなどの安定剤、発泡剤、乾燥剤などの公知の添加
剤を適当量配合することもある。又、エチレン−酢酸ビ
ニル共重合体ケン化物には改質用の熱可塑性樹脂を適当
量配合することもできる。The pellets obtained above are melt-molded and formed into a desired molded product. The temperature condition for the melt molding is desirably about 160 to 260 ° C. At the time of molding, an appropriate amount of a known additive such as a reinforcing material such as glass fiber or carbon fiber, a filler, a coloring agent, a stabilizer such as hydrotalcite, a foaming agent, or a drying agent may be added as needed. The saponified ethylene-vinyl acetate copolymer may also contain a suitable amount of a modifying thermoplastic resin.
【００２３】溶融成形法としては射出成形法、圧縮成形
法、押出成形法など任意の成形法が採用できる。このう
ち押出成形法としてはＴ−ダイ法、中空成形法、パイプ
押出法、線条押出法、異形ダイ押出法、インフレーショ
ン法などが挙げられるが、エチレン−酢酸ビニル共重合
体ケン化物単独の成形物（フィルム、シート、テープ、
ボトル、パイプ、フィラメント、異型断面押出物など）
のみならず、エチレン−酢酸ビニル共重合体ケン化物層
と他の熱可塑性樹脂層との共押出成形も可能である。As the melt molding method, any molding method such as an injection molding method, a compression molding method and an extrusion molding method can be adopted. Examples of the extrusion molding method include a T-die method, a hollow molding method, a pipe extrusion method, a linear extrusion method, a deformed die extrusion method, an inflation method and the like, and a molding of a saponified ethylene-vinyl acetate copolymer alone. Objects (films, sheets, tapes,
Bottles, pipes, filaments, extruded shaped sections, etc.)
In addition, coextrusion molding of the saponified ethylene-vinyl acetate copolymer layer and another thermoplastic resin layer is also possible.
【００２４】[0024]
【実施例】以下、実施例を挙げて本発明を具体的に説明
する。尚、実施例中、「部」、「％」とあるのは、特に
断りのない限り重量基準である。The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified.
【００２５】実施例１ 内容量１０ｌで内部に冷却コイルをもつ撹拌機付き重合
缶を用いて以下の条件でエチレン−酢酸ビニル共重合体
を連続重合した。 酢酸ビニル供給量 １２９０ｇ／ｈｒ メタノール供給量 ２００ｇ／ｈｒ ベンゾイルパーオキサイド供給量 ２５０ｍｇ／ｈｒ クロトンアルデヒド供給量 ０．００２ｐｐｍ共存（全系に対して） 重合温度 ６７℃ エチレン圧 ４０ｋｇ／ｃｍ２ 平均滞留時間 ４ｈｒ この時得られたエチレン−酢酸ビニル共重合体のエチレ
ン含有量は３２モル％で、酢酸ビニルの重合率は３８％
であった。１０日間の連続運転後の重合缶内の内部には
スケールの付着は全く見られなかった。Example 1 An ethylene-vinyl acetate copolymer was continuously polymerized under the following conditions using a polymerization vessel equipped with a stirrer having a content of 10 l and having a cooling coil inside. Vinyl acetate supply 1290 g / hr Methanol supply 200 g / hr Benzoyl peroxide supply 250 mg / hr Crotonaldehyde supply 0.002 ppm Coexistence (based on the whole system) Polymerization temperature 67 ° C. Ethylene pressure 40 kg / cm 2 Average residence time 4 hr The ethylene content of the ethylene-vinyl acetate copolymer obtained at this time was 32 mol%, and the polymerization rate of vinyl acetate was 38%.
Met. After the continuous operation for 10 days, no scale adhesion was observed inside the polymerization can.
【００２６】上記エチレン−酢酸ビニル共重合体を５０
％含むメタノール溶液１００部に、該共重合体中の酢酸
ビニル基に対して０．０１７当量の水酸化ナトリウムを
含有するメタノール溶液１５０部を供給し、１２０〜１
３０℃、圧力４ｋｇ／ｃｍ2Ｇで、３０分間ケン化反応
を行った。得られたエチレン−酢酸ビニル共重合体ケン
化物（ケン化度９９．８モル％）のメタノール溶液の樹
脂分濃度は３０％であった。次に含水率６２．５％のメ
タノール水溶液６０部を、該エチレン−酢酸ビニル共重
合体ケン化物のメタノール溶液に共沸下で供給し、１０
０〜１１０℃、圧力３ｋｇ／ｃｍ2Ｇで、エチレン−酢
酸ビニル共重合体ケン化物のメタノール／水溶液中の樹
脂分濃度が４０％になるまでメタノールを留出させ、完
全透明なメタノール／水均一溶液を得た。The above ethylene-vinyl acetate copolymer was mixed with 50
% Of a methanol solution containing 0.017 equivalents of sodium hydroxide based on vinyl acetate groups in the copolymer is supplied to 100 parts of a methanol solution containing
A saponification reaction was performed at 30 ° C. and a pressure of 4 kg / cm 2 G for 30 minutes. The methanol content of the obtained saponified ethylene-vinyl acetate copolymer (saponification degree: 99.8 mol%) had a resin content of 30%. Next, 60 parts of an aqueous methanol solution having a water content of 62.5% was supplied azeotropically to the methanol solution of the saponified ethylene-vinyl acetate copolymer, and 10 parts
Methanol is distilled off at 0 to 110 ° C. and a pressure of 3 kg / cm 2 G until the concentration of the resin component in the methanol / aqueous solution of the saponified ethylene-vinyl acetate copolymer becomes 40%. A solution was obtained.
【００２７】続いて得られたエチレン−酢酸ビニル共重
合体ケン化物のメタノール／水溶液を、水／メタノール
溶液（重量比９５／５）よりなる５℃に維持された凝固
液槽に、内径０．４ｃｍ、長さ６．０ｃｍの円筒形状の
ノズルより、１０ｋｇ／時の速度でストランド状に押し
出し、凝固液槽の端部に付設された引き取りローラーに
より、凝固液中の滞留時間が３分となる様に生成ストラ
ンドを凝固液から引き出した。ここで該ノズル口は４個
あり、ストランド数は４本で実施した。該ストランドを
カッターで切断し、多孔性のペレットを得た。得られた
ペレットは形状が均一であり、変形物は全くなかった。
該ペレットを温度３０℃の水槽中で１時間水洗し、これ
を４回繰り返して、酢酸ナトリウムを除去後、更に温度
３０℃の酢酸水溶液中で１時間洗浄を行った後、乾燥し
て、エチレン−酢酸ビニル共重合体ケン化物（平均直径
３．２ｍｍ、平均長さ３．５ｍｍの円筒形状の半透明ペ
レット）を得た。Subsequently, the methanol / water solution of the saponified ethylene-vinyl acetate copolymer obtained was placed in a coagulation liquid tank containing a water / methanol solution (weight ratio: 95/5) maintained at 5 ° C. and having an inner diameter of 0.1%. It is extruded in the form of a strand from a cylindrical nozzle having a length of 4 cm and a length of 6.0 cm at a speed of 10 kg / hour, and a residence time in the coagulation liquid is 3 minutes by a take-off roller attached to an end of the coagulation liquid tank. The resulting strand was drawn from the coagulation liquid in the same manner. Here, there were four nozzle openings, and the number of strands was four. The strand was cut with a cutter to obtain a porous pellet. The obtained pellets were uniform in shape and had no deformation.
The pellet was washed with water in a water bath at a temperature of 30 ° C. for 1 hour, and this was repeated four times to remove sodium acetate. Then, the pellet was further washed in an aqueous acetic acid solution at a temperature of 30 ° C. for 1 hour, and then dried. -Saponified vinyl acetate copolymer (cylindrical translucent pellet having an average diameter of 3.2 mm and an average length of 3.5 mm) was obtained.
【００２８】得られたエチレン−酢酸ビニル共重合体ケ
ン化物を以下の様に評価した。 （１）ペレットの色相 ○・・・着色なし △・・・目視でやや黄色に着色 ×・・・目視で黄色に着色 次に上記で得られたケン化物を以下の条件で製膜し、得
られたフィルムのフィッシュアイを以下の様に評価し
た。 The saponified ethylene-vinyl acetate copolymer was evaluated as follows. (1) Hue of pellet ○: No coloring △: Coloring slightly yellow visually ×: Coloring yellow visually Next, the saponified product obtained above was formed into a film under the following conditions. The fish eyes of the obtained films were evaluated as follows.
【００２９】（フィッシュアイの測定条件）フィルム１
００ｃｍ２当たりのフィッシュアイの数を測定した。 ○・・・５個以下 △・・・６〜９個以下 ×・・・１０以上 結果を表１に示した。(Fish Eye Measurement Conditions) Film 1
The number of fish eyes per 00 cm 2 was measured.・ ・ ・: 5 or less Δ: 6 to 9 or less ×: 10 or more The results are shown in Table 1.
【００３０】実施例２ 実施例１でクロトンアルデヒドを０．００１ｐｐｍ共存
させた以外は同様に実施し、実施例１と同様に評価し
た。この時得られたエチレン−酢酸ビニル共重合体のエ
チレン含有量は３２モル％で、酢酸ビニルの重合率は３
６％であった。１０日間の連続運転後の重合缶内部には
スケールの付着は見られなかった。得られたエチレン−
酢酸ビニル共重合体を、実施例１と同様にしてケン化物
として、実施例１と同様に評価した。Example 2 The procedure of Example 1 was repeated, except that 0.001 ppm of crotonaldehyde was added, and the evaluation was performed in the same manner as in Example 1. The ethylene-vinyl acetate copolymer obtained at this time had an ethylene content of 32 mol% and a vinyl acetate conversion of 3
6%. No scale adhesion was observed inside the polymerization can after 10 days of continuous operation. The obtained ethylene
The vinyl acetate copolymer was saponified in the same manner as in Example 1 and evaluated in the same manner as in Example 1.
【００３１】比較例１ 実施例１において、クロトンアルデヒドを共存させなか
った以外は同様に実施して、実施例１と同様に評価し
た。この時得られたエチレン−酢酸ビニル共重合体のエ
チレン含量は３２モル％で、酢酸ビニルの重合率は４０
％であった。１０日間の連続運転後の重合缶内部にはス
ケールの付着が見られた。得られたエチレン−酢酸ビニ
ル共重合体を、実施例１と同様にしてケン化物として、
実施例１と同様に評価した。Comparative Example 1 The procedure of Example 1 was repeated, except that no crotonaldehyde was used, and the evaluation was performed in the same manner as in Example 1. The ethylene-vinyl acetate copolymer obtained at this time had an ethylene content of 32 mol% and a polymerization rate of vinyl acetate of 40%.
%Met. After the continuous operation for 10 days, adhesion of scale was observed inside the polymerization can. The obtained ethylene-vinyl acetate copolymer was converted into a saponified product in the same manner as in Example 1.
Evaluation was performed in the same manner as in Example 1.
【００３２】比較例２ 実施例１において、クロトンアルデヒドを５ｐｐｍ共存
させた以外は同様に実施して、実施例１と同様に評価し
た。この時得られたエチレン−酢酸ビニル共重合体のエ
チレン含有量は３２モル％で、酢酸ビニルの重合率は３
２％であった。１０日間の連続運転後の重合缶内部には
スケールの付着が少し見られた。得られたエチレン−酢
酸ビニル共重合体を、実施例１と同様にしてケン化物と
して、実施例１と同様に評価した。実施例１、２、比較
例１、２で得られたエチレン−酢酸ビニル共重合体ケン
化物の評価を表１に示した。Comparative Example 2 The procedure of Example 1 was repeated, except that 5 ppm of crotonaldehyde was used, and the same procedure as in Example 1 was performed. The ethylene-vinyl acetate copolymer obtained at this time had an ethylene content of 32 mol% and a vinyl acetate conversion of 3
2%. After the continuous operation for 10 days, some adhesion of scale was observed inside the polymerization can. The obtained ethylene-vinyl acetate copolymer was evaluated as a saponified product in the same manner as in Example 1. The evaluation of the saponified ethylene-vinyl acetate copolymer obtained in Examples 1 and 2 and Comparative Examples 1 and 2 is shown in Table 1.
【００３３】[0033]
【表１】 エチレン含有量 ケン化 ペレット フィッシュアイ （モル％） 度 の色相 （モル％） 実施例１ ３２ ９９．８ ○ ○ 実施例２ ３２ ９９．８ ○ ○ 比較例１ ３２ ９９．８ ○ ×比較例２ ３２ ９９．８ × × Table 1 Ethylene content Saponified pellet Fish eye (mol%) Hue (mol%) of degree Example 1 32 99.8 ○ ○ Example 2 32 99.8 ○ ○ Comparative Example 1 32 99.8 ○ × Comparative Example 2 32 99.8 XX
【００３４】[0034]
【発明の効果】本発明では、クロトンアルデヒドを共存
下エチレンと酢酸ビニルを溶媒中で共重合させるので、
重合缶内部のスケール付着が少なく、かかるエチレン−
酢酸ビニル共重合体から製造されるエチレン−酢酸ビニ
ル共重合体ケン化物は着色がなく、またかかるケン化物
から得られたフィルムはフィッシュアイが少ない。According to the present invention, ethylene and vinyl acetate are copolymerized in a solvent in the presence of crotonaldehyde.
There is little scale adhesion inside the polymerization can.
The saponified ethylene-vinyl acetate copolymer produced from the vinyl acetate copolymer has no coloring, and the film obtained from such a saponified product has few fish eyes.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｆ 210:02） ────────────────────────────────────────────────── ─── front page continued (51) Int.Cl 6 identifications FI C08F 210:. 02)
Claims (4)
と酢酸ビニルを溶媒中で共重合させることを特徴とする
エチレン−酢酸ビニル共重合体の重合法。1. A method for polymerizing an ethylene-vinyl acetate copolymer, wherein ethylene and vinyl acetate are copolymerized in a solvent in the presence of crotonaldehyde.
０．５ｐｐｍ共存させることを特徴とする請求項１記載
のエチレン−酢酸ビニル共重合体の重合法。2. A method for producing crotonaldehyde from 0.0001 to 0.0001.
2. The method according to claim 1, wherein 0.5 ppm is present.
ことを特徴とする請求項１あるいは２記載のエチレン−
酢酸ビニル共重合体の重合法。3. The ethylene solvent according to claim 1, wherein the solvent is an alcohol having 4 or less carbon atoms.
Polymerization method of vinyl acetate copolymer.
ン−酢酸ビニル共重合体を更にケン化することを特徴と
するエチレン−酢酸ビニル共重合体ケン化物の製造法。4. A process for producing a saponified ethylene-vinyl acetate copolymer, further comprising saponifying the ethylene-vinyl acetate copolymer obtained in any one of claims 1 to 3.
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|---|---|---|---|
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| Publication Number | Publication Date |
|---|---|
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| JP2002128807A (en) * | 2000-10-27 | 2002-05-09 | Nippon Synthetic Chem Ind Co Ltd:The | Method for producing ethylene-vinyl acetate copolymer |
| US6683148B2 (en) | 2000-06-06 | 2004-01-27 | Kuraray Co., Ltd. | Method for producing ethylene-vinyl acetate copolymer and saponified product thereof |
| WO2013146962A1 (en) * | 2012-03-28 | 2013-10-03 | 株式会社クラレ | Blow molded container, fuel container, and method for producing blow molded container |
| WO2013146961A1 (en) * | 2012-03-28 | 2013-10-03 | 株式会社クラレ | Resin composition containing ethylene-vinyl alcohol copolymer |
| WO2014192838A1 (en) * | 2013-05-29 | 2014-12-04 | 株式会社クラレ | Ethylene-vinyl alcohol copolymer-containing resin composition, film, laminate, packaging material, vacuum heat-insulating body, film production method, and laminate production method |
| JP2015006786A (en) * | 2013-05-29 | 2015-01-15 | 株式会社クラレ | Deposition film |
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