JP2009062434A - Method for producing polyvinyl alcohol-based resin having 1,2-diol structure in side chain - Google Patents

Method for producing polyvinyl alcohol-based resin having 1,2-diol structure in side chain

Info

Publication number
JP2009062434A
JP2009062434A JP2007230348A JP2007230348A JP2009062434A JP 2009062434 A JP2009062434 A JP 2009062434A JP 2007230348 A JP2007230348 A JP 2007230348A JP 2007230348 A JP2007230348 A JP 2007230348A JP 2009062434 A JP2009062434 A JP 2009062434A
Authority
JP
Grant status
Application
Patent type
Prior art keywords
monomers
polymerization
chain
polyvinyl
alcohol
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.)
Granted
Application number
JP2007230348A
Other languages
Japanese (ja)
Other versions
JP5235364B2 (en )
Inventor
Hidehiro Kuroki
Munetoshi Tomita
Yoshihito Yamauchi
宗利 冨田
芳仁 山内
英博 黒木
Original Assignee
Nippon Synthetic Chem Ind Co Ltd:The
日本合成化学工業株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date

Links

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyvinyl alcohol resin which is small in a polymerization degree distribution and a modification degree distribution and contains a 1,2-diol structure in a side chain.
SOLUTION: Vinyl ester monomers and monomers expressed by general formula (1) are copolymerized in the presence of a polymerization catalyst in a solvent, wherein the monomers are continuously or intermittently added to the polymerization system and then the obtained copolymer is saponified.
COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、側鎖に1,2−ジオール構造を有するポリビニルアルコール系樹脂の製造方法に関し、さらに詳しくは、重合度分布および側鎖1,2−ジオール構造の含有量の分布、すなわち変性度分布が小さい側鎖に1,2−ジオール構造を有するポリビニルアルコール系樹脂を得ることができる製造方法に関する。 The present invention relates to a method for producing a polyvinyl alcohol-based resin having a 1,2-diol structure in a side chain, more specifically, the polymerization degree distribution and distribution of the content of side chain 1,2-diol structure, that is modified size distribution It relates to a manufacturing method capable of obtaining a polyvinyl alcohol-based resin having a 1,2-diol structure in a small side chain.

従来より、ポリビニルアルコール系樹脂(以下、ポリビニルアルコールをPVAと略記する。)は、その優れた水溶性、界面特性、皮膜特性(造膜性、強度、耐油性等)、等を利用して、分散剤、乳化剤、懸濁剤、繊維加工剤、紙加工剤、バインダー、接着剤、フィルム等に広く用いられている。 Conventionally, a polyvinyl alcohol-based resin (hereinafter, polyvinyl alcohol is abbreviated as PVA.), The excellent water solubility, interface characteristic, film characteristic (film formability, strength, oil resistance, etc.), etc. by utilizing, dispersing agents, emulsifiers, suspending agents, fiber processing agents, paper processing agents, binders, adhesives, are widely used in the film.
かかるPVA系樹脂においては、その使用目的や求められる特性に応じて種々の変性品が開発されており、例えば、共重合等によって種々の官能基が側鎖に導入された変性PVA系樹脂が開発、上市されている。 In such PVA-based resin, its use according to the purpose and properties sought various modified products has been developed, for example, a copolymer such as various functional groups developed modified PVA-based resin introduced into the side chain by , it is commercially available. 中でも、側鎖に1,2−ジオール構造を有するPVA系樹脂は、高ケン化度であっても溶解しやすく、水溶液の粘度安定性が高い、水溶液の発泡性が小さい、熱分解温度よりもはるかに低温で安定して溶融成形することが可能、といった、従来のPVA系樹脂では問題とされていた部分が解消された新規PVA系樹脂として、その応用が期待されている。 Of these, PVA-based resin having a 1,2-diol structure in a side chain, easily dissolved even at high saponification degree, a higher viscosity stability of the aqueous solution, effervescent aqueous solution is less than the thermal decomposition temperature much can be stably melt-molded at a low temperature, such as a conventional novel PVA resin portions which has been a problem persists in PVA-based resin, its application is expected.

かかる側鎖に1,2−ジオール構造を有するPVA系樹脂の製造方法としては、ビニルエステル系単量体とビニルエチレンカーボネートあるいは2,2−ジアルキル−4−ビニル−1,3−ジオキソランから得られる共重合体をケン化し、脱酢酸あるいは脱アセタール化する方法(例えば、特許文献1参照。)、およびビニルエステル系単量体と3,4−ジアセトキシ−1−ブテンから得られる共重合体をケン化する方法(例えば、特許文献2参照。)などが知られている。 As a method for producing PVA-based resin having a 1,2-diol structure in such a side chain, obtained from vinyl ester monomer and vinyl ethylene carbonate or 2,2-dialkyl-4-vinyl-1,3-dioxolane the copolymer was saponified, a method for removing acid or deacetalization (e.g., see Patent Document 1.), and vinyl ester monomer and 3,4-diacetoxy-1-Ken a copolymer obtained from butene method (e.g., see Patent Document 2.) for reduction and the like are known. 特に、3,4−ジアセトキシ−1−ブテンはビニルエステル系単量体との共重合性に優れる点や、製造時の副生物がビニルエステル系単量体として多用される酢酸ビニルに由来する構造単位から生じるものと同一であり、その回収や後処理に特別な装置や工程を設ける必要が無い点などから、好ましく用いられる共重合単量体である。 In particular, 3,4-diacetoxy-1-butene is derived and the viewpoint of excellent copolymerizability with vinyl ester monomers, the vinyl acetate by-product during manufacturing is frequently used as a vinyl ester monomer structure They are identical to those resulting from the unit, and the like that the recovery or special apparatus or process point is not necessary to provide a post-processing, preferably the comonomer used.

この、ビニルエステル系単量体と3,4−ジアセトキシ−1−ブテンを共重合させる方法として、かかる特許文献2には、滴下重合、さらにHANNA法に基づく方法が好ましいと記載されている。 This, as a method of copolymerizing a vinyl ester monomer and 3,4-diacetoxy-1-butene, in such Patent Document 2, dropping polymerization, are described further methods based on HANNA method is preferred. さらに、特許文献3の実施例には、かかるHANNA法を用いた滴下重合の具体例が開示されており、これは、重合初期に酢酸ビニルを全量反応缶に投入し、その後、3,4−ジアセトキシ−1−ブテンを重合系内の両単量体の比率が常に一定となるように両単量体の消費量をシミュレーションした結果に基づいて滴下して共重合させるものである。 Further, in Examples of Patent Document 3, such are specific examples of the dropping polymerization using a HANNA method is disclosed, which is polymerized initially charged vinyl acetate to a total volume of a reaction vessel, then, 3,4 the ratio of both monomers of the diacetoxy-1-butene in the polymerization system is always intended to be copolymerized dropwise based on the result of simulation of consumption as Ryotan monomer becomes constant.

特開2002−284818号公報 JP 2002-284818 JP 特開2004−285143号公報 JP 2004-285143 JP 特開2006−312313号公報 JP 2006-312313 JP

かかる特許文献3の実施例に記載された製造法によると、良好な重合速度を保ちながら共重合反応が進行し、これによって得られた側鎖に1,2−ジオール構造を有するPVA系樹脂は、良好な溶融成形性を示し、例えば、積層体とした時にも良好な層間接着性、ガスバリヤ性、延伸性が得られるものであった。 According to have been the preparation described in the examples of such Patent Document 3, good keeping the polymerization rate copolymerization reaction proceeds, PVA-based resin having a 1,2-diol structure in a side chain obtained by this , it showed good melt moldability, e.g., laminates and the good interlayer adhesion even when was achieved, gas barrier property, stretchability is obtained.
しかしながら、かかる製造法によって得られた側鎖に1,2−ジオール構造を有するPVA系樹脂は、フィルムや繊維とした場合、その延伸時に破断や切断がおこりやすく、かかる点に関しては、まだまだ改善の余地があるものであった。 However, PVA-based resin having a 1,2-diol structure in a side chain obtained by such production method, when a film or fiber, the easily occur breakage or cut during stretching, for such points, for improvement It was those where there is room. フィルムや繊維などの場合、すこしでも弱点となりうる部分があると、そこから破断あるいは切断が生じるが、特許文献3の実施例の方法によって得られた側鎖に1,2−ジオール構造を有するPVA系樹脂の場合、重合度分布および変性度分布が広く、低重合度の部分や、低変性度のため高結晶性の部分が弱点になっているものと推測される。 For such films, fibers, PVA having when there is a portion can be a weak point even a little, but occurs broken or disconnected therefrom, a 1,2-diol structure in a side chain obtained by the method of Example of Patent Document 3 for system resin, a polymerization degree distribution and modification degree distribution is wide, low degree of polymerization of the partial or highly crystalline portion for low degree of modification is presumed to have become weak.
すなわち、本発明は、重合度分布および変性度分布が小さい側鎖1,2−ジオール構造含有PVA系樹脂の提供を目的とする。 That is, the present invention has an object to provide a polymerization degree distribution and modification degree distribution is small side chain 1,2-diol structure-containing PVA-based resin.

本発明者は、上記事情に鑑み鋭意検討した結果、ビニルエステル系単量体と一般式(1)で示される単量体を溶媒中、重合触媒の存在下で共重合させるにあたり、重合系中に前記単量体を連続的あるいは断続的に添加して共重合し、得られた共重合体をケン化して得られた側鎖に1,2−ジオール構造を有するポリビニルアルコール系樹脂によって上述の課題が解決されることを見出し、本発明を完成するに至った。 The present inventor has conducted intensive studies in view of the above circumstances, a monomer in a solvent represented by the vinyl ester monomer of the general formula (1), when are copolymerized in the presence of a polymerization catalyst, the polymerization system the monomer copolymerized continuously or intermittently added, the above by polyvinyl alcohol-based resin having the obtained copolymer in a side chain obtained by saponifying 1,2-diol structure It found that problems can be solved, leading to completion of the present invention.

[式中、R 1 、R 2及びR 3はそれぞれ独立して水素原子または有機基を示し、Xは単結合または結合鎖を示し、R 4 、R 5 、及びR 6はそれぞれ独立して水素原子または有機基を示し、R 7及びR 8はそれぞれ独立して水素原子またはR 9 −CO−(式中、R 9はアルキル基である)である。 [Wherein, R 1, R 2 and R 3 each independently represents a hydrogen atom or an organic group, X represents a single bond or a bonding chain, R 4, R 5, and R 6 each independently represents hydrogen indicates an atom or an organic group, a hydrogen atom or R 9 -CO- R 7 and R 8 are independently (wherein, R 9 is an alkyl group). ]

通常、ビニルエステル系単量体と他の単量体との共重合において、共重合成分がランダムに導入された共重合体を得る場合には両者の反応性比に基づいて系中の両単量体の存在比を一定に制御する方法が好ましく用いられ、その具体的な方法として、HANNA法に基づく滴下重合が行われる。 Usually, in the copolymerization of vinyl ester monomer with other monomers, both single in the system based on the reactivity ratio of the both in the case of the copolymerization component to obtain a copolymer which is introduced randomly method of controlling the abundance of dimers constant is preferably used, as a specific method, dropping polymerization based on HANNA method is performed. この場合、主成分であるビニルエステル系単量体を重合初期に一括投入し、少量成分である共重合単量体を滴下する方法が一般的である。 In this case, the vinyl ester monomer is a main component polymerized initially and mass loading, method of dropping a comonomer which is a minor component is common.

一方、本発明は側鎖に1,2−ジオール構造を有するPVA系樹脂の製造において、原料であるビニルエステル系単量体と、一般式(1)で示される単量体を共重合する際、両方とも重合系に連続的あるいは断続的に添加しながら重合することを最大の特徴とするものであって、かかる方法を採用することによって、重合度分布および変性度分布が小さい側鎖に1,2−ジオール構造を有するPVA系樹脂が得られたことを特徴とするものである。 On the other hand, the present invention is in the production of PVA-based resin having a 1,2-diol structure in a side chain, when copolymerized with vinyl ester monomer as a raw material, a monomer represented by the general formula (1) both been made to the maximum, characterized in that the polymerization continuously or with intermittent added to the polymerization system, by adopting such a method, is a small side chain polymerization degree distribution and modification degree distribution 1 , it is characterized in that the PVA-based resin having a 1,2-diol structure was obtained.

本発明の方法で得られた側鎖に1,2−ジオール構造を有するポリビニルアルコール系樹脂は、重合度分布および変性度分布が小さいことから、分子間の均一性が高く、フィルムや繊維等の高度な物性の均一性が要求される用途に極めて好適である。 Polyvinyl alcohol resin having a 1,2-diol structure in a side chain obtained by the method of the present invention, since the polymerization degree distribution and modification degree distribution is small, high uniformity between molecules, films and the like fibers it is very suitable for applications where uniformity of the advanced properties are required.

以下に記載する構成要件の説明は、本発明の実施態様の一例(代表例)であり、これらの内容に特定されるものではない。 Description of constituent features described below is an example embodiment of the present invention (representative example), but the invention is not specified to these contents.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.

本発明の側鎖に1,2−ジオール構造を有するPVA系樹脂の製造法は、ビニルエステル系単量体と、下記一般式(1)で表わされる単量体とを溶媒中、重合触媒の存在下で重合系中に連続的あるいは断続的に添加して共重合し、得られた共重合体をケン化するものであり、かかる方法によって得られたPVA系樹脂は、通常、側鎖1,2−ジオール構造単位を0.1〜20モル%程度含有し、残る部分は、通常のPVA系樹脂と同様、ビニルアルコール構造単位と若干量の酢酸ビニル構造単位からなる。 Preparation of the PVA-based resin having a 1,2-diol structure in a side chain of the present invention, a vinyl ester monomer, and a monomer represented by the following general formula (1) in a solvent, the polymerization catalyst continuously or intermittently copolymerized by adding into the polymerization system in the presence, which saponifying the resulting copolymer, PVA-based resin obtained by such methods is usually the side chain 1 contains about 0.1 to 20 mole% 1,2-diol structural units, the remainder is similar to the conventional PVA-based resin, a vinyl alcohol structural unit and some amount of vinyl acetate structural unit.

本発明で用いられるビニルエステル系単量体としては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、バーサチック酸ビニル等が挙げられるが、経済的にみて中でも酢酸ビニルが好ましく用いられる。 The vinyl ester monomer used in the present invention, vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate , vinylbenzoic acid, vinyl versatate, and the like, among which vinyl acetate is preferably used when viewed economically.

また、本発明で用いられる一般式(1)で表わされる単量体におけるR 1 〜R 3 、及びR 4 〜R 6は、すべて水素原子であることが望ましいが、樹脂特性を大幅に損なわない程度の量であれば有機基で置換されていてもよく、その有機基としては特に限定されないが、例えばメチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、tert−ブチル基等の炭素数1〜4のアルキル基が好ましく、必要に応じて、ハロゲン基、水酸基、エステル基、カルボン酸基、スルホン酸基等の置換基を有していてもよい。 Further, R 1 to R 3 in the monomer represented by the general formula (1) used in the present invention, and R 4 to R 6 is desirably are all hydrogen atom, does not impair resin properties significantly if the amount of the degree may be substituted with an organic group is not particularly restricted but includes organic groups such as methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, tert - it is preferably an alkyl group having 1 to 4 carbon atoms such as butyl group, optionally halogen group, a hydroxyl group, an ester group, a carboxylic acid group, which may have a substituent such as a sulfonic acid group.
また、一般式(1)で表わされる単量体中のXは代表的には単結合であり、熱安定性の点で単結合であるものが最も好ましいが、本発明の効果を阻害しない範囲であれば結合鎖であってもよく、かかる結合鎖としては特に限定されないが、アルキレン、アルケニレン、アルキニレン、フェニレン、ナフチレン等の炭化水素(これらの炭化水素はフッ素、塩素、臭素等のハロゲン等で置換されていても良い)の他、−O−、−(CH 2 O) m −、−(OCH 2m −、−(CH 2 O) m CH 2 −、−CO−、−COCO−、−CO(CH 2m CO−、−CO(C 64 )CO−、−S−、−CS−、−SO−、−SO 2 −、−NR−、−CONR−、−NRCO−、−CSNR−、−NRCS−、−NRNR−、−HPO 4 −、−Si(OR Further, X in the monomer in the represented by the general formula (1) is typically a single bond, but in terms of thermal stability and most preferred is a single bond, does not interfere with the effects of the present invention range may be a linking chain long, it is not particularly restricted but includes such a bonding chain, alkylene, alkenylene, alkynylene, phenylene, hydrocarbon (these hydrocarbons naphthylene fluorine, chlorine, a halogen such as bromine, etc. another may be substituted), -O -, - (CH 2 O) m -, - (OCH 2) m -, - (CH 2 O) m CH 2 -, - CO -, - COCO-, -CO (CH 2) m CO - , - CO (C 6 H 4) CO -, - S -, - CS -, - SO -, - SO 2 -, - NR -, - CONR -, - NRCO-, -CSNR -, - NRCS -, - NRNR -, - HPO 4 -, - Si (OR 2 −、−OSi(OR) 2 −、−OSi(OR) 2 O−、−Ti(OR) 2 −、−OTi(OR) 2 −、−OTi(OR) 2 O−、−Al(OR)−、−OAl(OR)−、−OAl(OR)O−、等(Rは各々独立して任意の置換基であり、水素原子、アルキル基が好ましく、またmは自然数である)が挙げられる。 2 -, - OSi (OR) 2 -, - OSi (OR) 2 O -, - Ti (OR) 2 -, - OTi (OR) 2 -, - OTi (OR) 2 O -, - Al (OR) -, - OAl (OR) -, - OAl (OR) O-, etc. (R is an optional substituent each independently, a hydrogen atom, an alkyl group are preferred, and m is a natural number) and the like . 中でも製造時あるいは使用時の安定性の点で炭素数6以下のアルキレン基、特にメチレン基が好ましい。 Among these manufacturing or during use when the stability alkylene group having 6 or less carbon atoms in terms of, in particular, methylene group is preferred.

なかでも、共重合反応性および工業的な取り扱い性に優れるという点から、R 1 〜R 6が水素、Xが単結合、R 7 〜R 8がR 9 −CO−であり、R 9がアルキル基である、3,4−ジアシロキシ−1−ブテンが好ましく、さらにそのなかでも特にR 9がメチル基である3,4−ジアセトキシ−1−ブテンが好ましく用いられる。 Among them, from the viewpoint of excellent copolymerization reactivity and industrial handling ability, R 1 to R 6 are hydrogens, X a single bond, R 7 to R 8 are R 9 -CO-, R 9 is alkyl is a group, 3,4-diacyloxy-1-butene are preferred, R 9 is preferably used is 3,4-diacetoxy-1-butene with a methyl group further among them.
なお、ビニルエステル系モノマーとして酢酸ビニルを用い、これと3,4−ジアセトキシ−1−ブテンを共重合させた際の各モノマーの反応性比は、r(酢酸ビニル)=0.710、r(3,4−ジアセトキシ−1−ブテン)=0.701、であり、これは特許文献1に記載の方法で用いられる単量体であるビニルエチレンカーボネートの場合の、r(酢酸ビニル)=0.85、r(ビニルエチレンカーボネート)=5.4、と比較して、3,4−ジアセトキシ−1−ブテンが酢酸ビニルとの共重合反応性に優れることを示すものである。 Incidentally, the vinyl acetate is used as the vinyl ester-based monomer, reactivity ratio of each monomer when copolymerized with this and 3,4-diacetoxy-1-butene, r (vinyl acetate) = 0.710, r ( 3,4-diacetoxy-1-butene) = 0.701, is, this is the case of vinyl ethylene carbonate is a monomer used in the method described in Patent Document 1, r (vinyl acetate) = 0. 85, r (vinyl ethylene carbonate) = 5.4, as compared with 3,4-diacetoxy-1-butene is an indication that the excellent copolymerization reactivity with vinyl acetate.

また、かかる3,4−ジアセトキシ−1−ブテンは、その共重合体をケン化する際に発生する副生物が、ビニルエステル系モノマーとして多用される酢酸ビニルに由来する構造単位からケン化時に副生する化合物と同一であり、その後処理に特別な装置や工程を設ける必要がない点も、工業的に大きな利点である。 Further, such 3,4-diacetoxy-1-butene, by-products generated during the saponification of the copolymer, the sub-structural unit derived from vinyl acetate frequently used as a vinyl ester-based monomer at the time of saponification it is identical to the compound of raw, even that there is no need to provide a special device or process to its after-treatment, is industrially great advantage.

なお、上記3,4−ジアセトキシ−1−ブテンは、例えば、WO00/24702に記載の1,3−ブタジエンを出発物質とした合成ルートで製造された製品や、USP5623086、USP6072079に記載の技術によるエポキシブテン誘導体を中間体として製造された製品を入手することができ、また試薬レベルではアクロス社の製品をそれぞれ市場から入手することができる。 The above 3,4-diacetoxy-1-butene, for example, WO00 / 24702 products and that of 1,3-butadiene according manufactured synthetic routes starting materials, the epoxy by the technique described in USP5623086, USP6072079 butene derivative can obtain products that are produced as intermediates, and in the reagent level can be obtained from Acros each market products. また、1,4−ブタンジオール製造工程中の副生成物として得られる3,4−ジアセトキシ−1−ブテンを利用することもできる。 It is also possible to utilize the 3,4-diacetoxy-1-butene obtained as a by-product in 1,4-butanediol production process.
また、1,4−ジアセトキシ−1−ブテンを塩化パラジウムなどの金属触媒を用いた公知の異性化反応によって3,4−ジアセトキシ−1−ブテンに変換して用いることもできる。 Moreover, 1,4-diacetoxy-1-butene can also be used by converting by known isomerization reaction using a metal catalyst such as palladium chloride 3,4-diacetoxy-1-butene.

また上述の単量体(ビニルエステル系単量体、一般式(1)で示される単量体)の他に、樹脂物性に大幅な影響を及ぼさない範囲であれば、これら以外の単量体を共重合してもよく、かかる単量体として、エチレンやプロピレン等のαーオレフィン;3−ブテン−1−オール、4−ペンテン−1−オール等のヒドロキシ基含有α−オレフィン類およびそのアシル化物などの誘導体;イタコン酸、マレイン酸、アクリル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;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、ジアセトンア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などの The monomers described above in addition to (vinyl ester monomer, a monomer represented by the general formula (1)), as long as it does not have a significant effect on resin properties, monomers other than those may be copolymerized, such as monomers, ethylene and α-olefins such as propylene, 3-buten-1-ol, 4-penten-1-hydroxy-group-containing α- olefins and their acylated such as ol derivatives such as: itaconic acid, maleic acid, unsaturated acids or salts or mono- or dialkyl ester such as acrylic acid; nitriles such acrylonitrile, methacrylonitrile, etc., acrylamide, methacrylamide, amides of diacetone acrylamide, ethylene sulfonic acid, allyl sulfonic acid, such as olefin sulfonic acid or its salt such as methallyl sulphonic acid 化合物、アルキルビニルエーテル類、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、ビニルエチレンカーボネート、2,2−ジアルキル−4−ビニル−1,3−ジオキソラン、グリセリンモノアリルエーテル、3,4−ジアセトキシ−1−ブテン、等のビニル化合物、酢酸イソプロペニル、1−メトキシビニルアセテート等の置換酢酸ビニル類、塩化ビニリデン、1,4−ジアセトキシ−2−ブテン、ビニレンカーボネート、等を挙げることができる。 Compounds, alkyl vinyl ethers, dimethylallyl vinyl ketone, N- vinylpyrrolidone, vinyl chloride, vinyl ethylene carbonate, 2,2-dialkyl-4-vinyl-1,3-dioxolane, glycerol monoallyl ether, 3,4-diacetoxy - 1-butene, vinyl etc. compounds, isopropenyl acetate, substituted vinyl acetate such as 1-methoxy-vinyl acetate, vinylidene chloride, 1,4-diacetoxy-2-butene, vinylene carbonate, and the like.

上記のビニルエステル系単量体と一般式(1)で表わされる単量体、さらには他の単量体を共重合するにあたっては溶液重合が用いられ、その際の溶媒としては、メタノール、エタノール、イソプロピルアルコール、n−プロパノール、ブタノール等の低級アルコールやアセトン、メチルエチルケトン等のケトン類等が好ましく用いられ、工業的には、メタノールが好適に使用される。 The monomer represented by the above vinyl ester-based monomer and the general formula (1), further is when copolymerizing another monomer solution polymerization is used, as the solvent in that case, methanol, ethanol , isopropyl alcohol, n- propanol, a lower alcohol or acetone butanol, methyl ethyl ketone, etc. and the like are preferably used, and industrially, methanol is preferably used.
溶媒の使用量は、目的とする共重合体の重合度に合わせて、溶媒の連鎖移動定数を考慮して適宜選択すればよく、例えば、溶媒がメタノールの時は、S(溶媒)/M(使用単量体の全量)=0.01〜10(重量比)、好ましくは0.03〜3(重量比)程度の範囲から選択される。 The amount of the solvent to be used, in accordance with the polymerization degree of the objective copolymer may be appropriately selected in consideration of the chain transfer constant of the solvent, for example, when the solvent is methanol, S (solvent) / M ( use monomer total) = 0.01 to 10 (weight ratio), preferably selected from the range of about 0.03 to 3 (weight ratio).

共重合に当たっては重合触媒が用いられ、かかる重合触媒としては、例えばアゾビスイソブチロニトリル、過酸化アセチル、過酸化ベンゾイル、過酸化ラウリル等の公知のラジカル重合触媒やアゾビスジメチルバレロニトリル、アゾビスメトキシジメチルバレロニトリル等の低温活性ラジカル重合触媒等が挙げられ、重合触媒の使用量は、コモノマーの種類や触媒の種類により異なり一概には決められないが、重合速度に応じて任意に選択される。 The In copolymerization polymerization catalyst is used, as such a polymerization catalyst, such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, known radical polymerization catalysts and azobisdimethylvaleronitrile such lauryl peroxide, azo include low temperature active radical polymerization catalysts such as bis methoxy dimethyl valeronitrile, the amount of the polymerization catalyst is not determined to flatly depends comonomer type and catalyst, optionally selected according to the polymerization rate that. 例えば、アゾイソブチロニトリルや過酸化アセチルを用いる場合、ビニルエステル系モノマーに対して0.01〜0.7モル%が好ましく、特には0.02〜0.5モル%が好ましい。 For example, when using azoisobutyronitrile or acetyl peroxide is preferably 0.01 to 0.7 mol% based on the vinyl ester-based monomer, particularly preferably 0.02 to 0.5 mol%.
また、共重合反応の反応温度は、使用する溶媒や圧力により30℃〜沸点程度で行われ、より具体的には、35〜150℃、好ましくは40〜75℃の範囲で行われる。 The reaction temperature of the copolymerization reaction is carried out at 30 ° C. ~ approximately the boiling point by solvent and pressure used, and more specifically, 35 to 150 ° C., preferably at the range of 40 to 75 ° C..

本発明で用いられるビニルエステル系単量体と一般式(1)で表わされる単量体との共重合は、溶媒および重合触媒の存在下、これらの単量体を両方とも重合系中に連続的あるいは断続的に添加して共重合することを特徴とするものである。 Copolymerization with a monomer represented by the vinyl ester monomer of the general formula used in the present invention (1) in the presence of a solvent and a polymerization catalyst, continuously during the polymerization system both of these monomers it is characterized in that the copolymerization manner or intermittently added.
かかる添加方法としては、ビニルエステル系単量体と一般式(1)で表わされる単量体をそれぞれ独立して重合系中に添加してもいいし、両者を予め混合した後、これを重合系中に添加してもいい。 Such addition method, You can either added monomer represented by the vinyl ester-based monomer and the general formula (1) in independently polymerization system, after mixing the two pre-polymerized this It also is added into the system. また、単量体はそのままで添加してもよいが、添加量を正確に制御するために溶液状としてもよく、その場合には、重合溶媒による溶液を用いることが好ましい。 Also, monomers may be added as is, the addition amount may be as a solution form in order to accurately control, in that case, it is preferable to use a solution by polymerization solvent.

重合系中への添加は、連続的に行っても、断続的におこなってもよく、その添加速度は特に制限されるものではないが、通常、全使用量の1〜25%/時間、特に2〜20%/時間の範囲が好ましく採用される。 The addition into the polymerization system, be carried out continuously, may be carried out intermittently, the addition rate but is not particularly limited, usually, 1% to 25% / hr of the total amount, in particular range of 2-20% / h is preferably employed. かかる添加速度が速すぎると目標とする粘度よりも高粘度となる傾向があり、逆に遅すぎると低粘度となる傾向がある。 When such addition rate is too fast tend to be higher viscosity than the targeted, tends to be too late to reverse the low viscosity. なお、かかる添加速度は、通常、等速で行われるが、系中の単量体の消費量や重合速度のモニター結果などから、途中で変えることも可能である。 Incidentally, such a rate of addition is usually carried out at a constant speed, and the like consumption and polymerization rate monitor result of the monomer in the system, it is also possible to vary the way. また、両単量体を独立して添加する場合には、その添加速度は各々設定することも可能であるが、通常は、同等のペースで添加し、開始時間と終了時間が同じになるように行われる。 Also, the case of adding independent both monomer While it is possible that addition rate to be set each, usually, added in equal pace, so that the start and end times are the same It is carried out.

かかる共重合に要する時間は、所望する重合度、変性量、使用する単量体の組み合わせなどによって一概には言えないが、通常、5〜30時間であり、その内訳は、触媒の投入から追加単量体を添加するまでの時間として0〜5時間、単量体の添加に要する時間として5〜25時間、その後、重合を完結させるための時間として0〜5時間、の範囲で行われる。 The time required for such copolymerization, the desired degree of polymerization, degree of modification, since it may vary depending on a combination of monomers used, generally 5 to 30 hours, added from the breakdown of introduction of catalyst 0-5 hours as the time until the addition of monomer, from 5 to 25 hours as the time required for the addition of the monomer, then 0-5 hours as the time to complete the polymerization is carried out in the range of.
また、本発明においては、単量体は重合系中に添加されて共重合されるが、使用する単量体の一部を重合初期に投入しておくことも好ましい実施態様であり、通常、全使用量の0〜70%、特に3〜60%、さらには5〜50%の単量体を重合初期に投入しておいてもよい。 In the present invention, the monomer is copolymerized is added to the polymerization system, is also a preferred embodiment that you put a part of the monomers used in the polymerization initial, usually, 0% to 70% of the total amount, in particular 3-60%, more may be previously charged into the polymerization initial 5 to 50% of the monomers.

重合終了は重合系からサンプリングした反応液中の重合体の量をモニターし、所望の重合率となった時点で判断すればよい。 Completion of the polymerization to monitor the amount of polymer in the reaction solution sampled from the polymerization system, it may be determined at the time when a desired polymerization rate. かかる重合終了時には、ラジカル重合において用いられる公知の重合禁止剤を反応系内に添加することが好ましく、かかる重合禁止剤としては、例えば、m−ジニトロベンゼン、アスコルビン酸、ベンゾキノン、α―メチルスチレンの二量体、p−メトキシフェノール等を挙げることができる。 Upon such completion of the polymerization, it is preferable to add a known polymerization inhibitor to be used in the radical polymerization in the reaction system, as such a polymerization inhibitor, for example, m- dinitrobenzene, ascorbic acid, benzoquinone, of α- methyl styrene dimers, mention may be made of p- methoxy phenol.

得られた共重合体は次いでケン化されるのであるが、かかるケン化にあたっては上記で得られた共重合体をアルコール等の溶媒に溶解し、アルカリ触媒又は酸触媒を用いて行われる。 While the resulting copolymer is then being saponified, the carrying such saponifying a copolymer obtained above is dissolved in a solvent such as an alcohol, it is carried out using an alkali catalyst or an acid catalyst. 代表的な溶媒としては、メタノール、エタノール、プロパノール、tert−ブタノール等が挙げられるが、メタノールが特に好ましく用いられる。 Representative solvents include methanol, ethanol, propanol, and tert- butanol, methanol is particularly preferably used. アルコール中の共重合体の濃度は系の粘度により適宜選択されるが、通常は10〜60重量%の範囲から選ばれる。 The concentration of the copolymer in the alcohol is suitably selected depending on the viscosity of the system, it is usually selected from the range of 10 to 60 wt%. ケン化に使用される触媒としては、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラート、リチウムメチラート等のアルカリ金属の水酸化物やアルコラートの如きアルカリ触媒、硫酸、塩酸、硝酸、メタスルフォン酸、ゼオライト、カチオン交換樹脂等の酸触媒が挙げられる。 The catalyst used in the saponification include sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, alkali metal hydroxides and alcoholates such as the alkaline catalyst, such as lithium methylate, sulfate, hydrochloric, nitric, Metasurufon acid, zeolites, include acid catalysts such as cation exchange resins.

かかるケン化触媒の使用量については、ケン化方法、目標とするケン化度等により適宜選択されるが、アルカリ触媒を使用する場合は通常、ビニルエステル系単量体及び式(1)で示される単量体化合物に由来する構造単位の合計量1モルに対して0.1〜30ミリモル、好ましくは2〜17ミリモルの割合が適当である。 The use amount of such a saponification catalyst, saponification method is appropriately selected according to the saponification degree or the like as a target, when using the alkali catalyst is typically represented by vinyl ester monomer and formula (1) 0.1 to 30 mmol with respect to 1 mol of the total amount of structural units derived from a monomer compound, and preferably from a rate of 2 to 17 millimoles.
また、ケン化反応の反応温度は特に限定されないが、10〜60℃が好ましく、より好ましくは20〜50℃である。 The reaction temperature of the saponification reaction is not particularly limited but is preferably from 10 to 60 ° C., more preferably from 20 to 50 ° C..

かくして、側鎖に1,2−ジオール構造を有する本発明のPVA系樹脂が得られるのであるが、本発明では、PVA系樹脂の平均重合度(JIS K6726に準拠して測定)は通常は100〜1000であり、特に200〜700、さらに300〜500のものが好ましく、かかる平均重合度が低すぎると例えばフィルムや繊維用途の場合、全体的な強度が不足する傾向があったり、接着剤やバインダー用途とする場合には接着強度等が不足する傾向にある。 Thus, although the PVA-based resin of the present invention having a 1,2-diol structure in a side chain is obtained in the present invention, (measured in accordance with JIS K6726) average polymerization degree of the PVA-based resin is usually 100 is 1000, in particular 200 to 700, more preferably has 300 to 500, when the when such average degree of polymerization is too low for example a film or fiber applications, or tended to be insufficient overall strength, Ya adhesive when the binder applications tends to be insufficient bonding strength. 逆に平均重合度が高すぎるものは、溶液重合の場合S/Mを小さくする必要があり、単量体の滴下速度を遅くしなければならず、工業的に困難で経済的にも不利である。 Conversely an average degree of polymerization is too high, it is necessary to reduce the case of solution polymerization S / M, it is necessary to slow down the dropping rate of the monomer, is industrially difficult and economically disadvantageous is there.

また、かかるPVA系樹脂のケン化度(JIS K6726に準拠して測定)は、通常60〜100%以上であり、特に70〜100モル%のものが好適で、かかるケン化度が低すぎると水溶性が低下する傾向にある。 Further, degree of saponification of such a PVA-based resin (measured in accordance with JIS K6726) is usually 60% to 100% or more, particularly preferably those of 70 to 100 mol%, when such a saponification degree is too low tends to water is lowered.

また、PVA系樹脂に含まれる側鎖1,2−ジオール構造の含有量は、通常は0.1〜20モル%であり、特に0.1〜15モル%、さらに0.1〜10モル%である。 The content of side chain 1,2-diol structure contained in the PVA-based resin is usually 0.1 to 20 mol%, in particular 0.1 to 15 mol%, further from 0.1 to 10 mol% it is. かかる含有量が少なすぎると、側鎖1,2−ジオール構造を導入した効果が得られにくくなる傾向があり、逆に多すぎると重合速度が低下したり、重合率が上がりにくくなる傾向がある。 When such content is too small, there tends to be difficult to obtain the effect of introducing a side chain 1,2-diol structure too much, the polymerization rate may decrease conversely, there is a tendency that the polymerization rate is less likely to rise .

なお、PVA系樹脂中の側鎖1,2−ジオール構造単位の含有率は、PVA系樹脂を完全にケン化したものの1 H−NMRスペクトル(溶媒:DMSO−d6、内部標準:テトラメチルシラン)から求めることができ、具体的には1,2−ジオール単位中の水酸基プロトン、メチンプロトン、およびメチレンプロトン、主鎖のメチレンプロトン、主鎖に連結する水酸基のプロトンなどに由来するピーク面積から算出すればよい。 Incidentally, the content of side chain 1,2-diol structural unit in the PVA-based resin, 1 H-NMR spectrum but was completely saponified PVA-based resin (solvent: DMSO-d6, internal standard: tetramethylsilane) it can be obtained from, specifically calculated from peak areas derived from 1,2-OH protons in the diol units, methine proton and methylene protons, methylene protons of main chain, such as the hydroxyl group of protons connected to the main chain do it.

かくして得られた本発明の側鎖に1,2−ジオール構造を有するPVA系樹脂は各種用途に使用することができ、以下具体例として次のものが挙げられる。 PVA-based resin having a 1,2-diol structure in a side chain of the present invention thus obtained can be used in various applications, it may be mentioned as specific examples of the following below.
(1)接着剤関係 木材、紙、アルミ箔、プラスチック等の接着剤、粘着剤、再湿剤、不織布用バインダー、石膏ボードや繊維板等の各種建材用バインダー、各種粉体造粒用バインダー、セメントやモルタル用添加剤、ホットメルト型接着力、感圧接着剤、アニオン性塗料の固着剤、偏光板用接着剤、水ビ接着剤、ハネムーン接着剤、等。 (1) an adhesive relationship wood, paper, aluminum foil, adhesive such as plastics, adhesives, re-wetting agents, nonwoven binders, various building materials for a binder such as gypsum board and fiber board, various powder granulating binders, additives for cement and mortar, hot-melt adhesion, pressure sensitive adhesives, fixing agents for anionic paints, adhesive for polarizing plate, Mizubi adhesives, honeymoon adhesives, etc.

(2)成形物関係 繊維、長繊維不織布、複合繊維、中空繊維用、フィルム(特に農薬、洗剤、洗濯用衣類、土木用添加剤、殺菌剤、染料、顔料等の物品包装用の易水溶性フィルム、シート、パイプ、チューブ、防漏膜、暫定皮膜、ケミカルレース用、水溶性繊維、複合繊維(中空繊維)用水溶性素材、等。 (2) molding relation fibers, long fiber nonwoven fabric, composite fibers, hollow fibers, films (in particular agrochemicals, detergents, laundry garments, civil additives, fungicides, dyes, readily water-soluble article packaging pigments films, sheets, pipes, tubes, Bomomaku, provisional coating for chemical lace, soluble fiber, composite fibers (hollow fibers) water-soluble material, etc.

(3)被覆剤関係 紙のクリアーコーティング剤、紙の顔料コーティング剤、紙のサイジング剤、繊維製品用サイズ剤、経糸糊剤、繊維加工剤、皮革仕上げ剤、塗料、防曇剤、金属腐食防止剤、亜鉛メッキ用光沢剤、帯電防止剤、導電剤、暫定塗料、等。 (3) clear coating material of the coating agent relationship paper, pigment coating agents for paper, paper sizing agents, textile for sizing, warp sizing agent, fiber processing agents, leather finishing agents, paints, defogging agent, anti-metal corrosion agents, zinc plating brighteners, antistatic agents, conductive agents, interim paints, etc.

(4)乳化剤関係 エチレン性不飽和化合物、ブタジエン性化合物、各種アクリル系モノマーの乳化重合用乳化剤、ポリオレフィン、ポリエステル樹脂等の疎水性樹脂、エポキシ樹脂、パラフィン、ビチューメン等の後乳化剤、等。 (4) emulsifier relationship ethylenically unsaturated compound, a butadiene compound, emulsifier for emulsion polymerization of various acrylic monomers, polyolefins, hydrophobic resin such as polyester resins, epoxy resins, paraffin, emulsifier after bitumen, etc., etc.

(5)懸濁剤関係 塗料、墨汁、水性カラー、接着剤等の顔料分散安定剤、塩化ビニル、塩化ビニリデン、スチレン、(メタ)アクリレート、酢酸ビニル等の各種ビニル化合物の懸濁重合用分散安定剤、等。 (5) suspension relation paints, India ink, aqueous color, the pigment dispersion stabilizers such as glue, vinyl chloride, vinylidene chloride, styrene, (meth) acrylate, for suspension polymerization dispersion stability of various vinyl compounds such as vinyl acetate agents, etc..

(6)増粘剤関係 各種水溶液やエマルジョンの増粘剤、等。 (6) thickener thickening relationship various aqueous and emulsion, etc..
(7)樹脂原料 ポリビニルアセタール系樹脂原料、感光性樹脂原料、等(8)その他 水中懸濁物及び溶存物の凝集剤、パルプ、スラリーの濾水性、土壌改良剤関係 (7) the resin material a polyvinyl acetal resin material, a photosensitive resin material, etc. (8) flocculant other water suspension and dissolved matter, pulp, freeness of the slurry, soil conditioners relationship

中でも、本発明の方法で得られた側鎖に1,2−ジオール構造を有するPVA系樹脂は、分子間の均一性が高いことから、フィルムや繊維などの高度に物性の均一性が要求される用途に好適である。 Of these, PVA-based resin having a 1,2-diol structure in a side chain obtained by the method of the present invention, because of high uniformity between molecules, uniformity of highly physical properties such as films or fibers are required it is suitable for that purpose.

以下に、本発明を実施例を挙げて説明するが、本発明はその要旨を超えない限り、実施例の記載に限定されるものではない。 Hereinafter, the present invention will be described by way of example, the present invention unless departing from the gist of the present invention is not limited to the description of Example.
尚、例中、「部」、「%」とあるのは、断りのない限り重量基準を意味する。 Incidentally, in the examples, "part", "%" means weight unless otherwise specified.

実施例1 Example 1
還流冷却器、滴下漏斗、撹拌機を備えた反応缶に、酢酸ビニル10部(総使用量の10%)、、3,4−ジアセトキシ−1−ブテン1.6部(総使用量の10%)、メタノール30部(初期S/M=3.00)を仕込み、アゾビスイソブチロニトリルを0.24モル%(対酢酸ビニルの総使用量)投入し、撹拌しながら窒素気流下で温度を上昇させ、重合を開始した。 A reflux condenser, a dropping funnel, a dropping funnel, and a stirrer were, (10% of the total amount) 10 parts of vinyl acetate ,, 3,4-diacetoxy-1-butene 1.6 parts (total amount of 10% ), 30 parts of methanol were charged (initial S / M = 3.00), azobisisobutyronitrile 0.24 mol% (total amount of to vinyl acetate) were charged, the temperature in a nitrogen stream while stirring was elevated to the polymerization was initiated. その後、酢酸ビニル90部と3,4−ジアセトキシ−1−ブテン14.4部を9時間かけて滴下した(滴下速度=全単量体使用量の10%/時間)。 Then, 90 parts of vinyl acetate and 3,4-diacetoxy-1-butene 14.4 parts was added dropwise over nine hours (10% / hour addition rate = total monomer amount). 11.5時間後、酢酸ビニルの重合率が91.7%となったので、重合禁止剤としてm−ジニトロベンゼン10ppm(対酢酸ビニルの総使用量)を加え、重合を終了した。 After 11.5 hours, the polymerization rate of vinyl acetate so was 91.7% as a polymerization inhibitor m- dinitrobenzene 10 ppm (total amount of to vinyl acetate) was added to complete polymerization. 続いて、メタノール蒸気を吹き込む方法により未反応の酢酸ビニルモノマーを系外に除去し共重合体のメタノール溶液を得た。 Subsequently, to obtain a methanol solution of the removed copolymer unreacted vinyl acetate monomer out of the system by a method of blowing methanol vapor.
次いで、該溶液をメタノールで希釈して濃度50%に調整してニーダーに仕込み、溶液温度を40℃に保ちながら、水酸化ナトリウムの2%メタノール溶液を共重合体中の酢酸ビニル構造単位及び3,4−ジアセトキシ−1-ブテン構造単位の合計量1モルに対して12ミリモルとなる割合で加えてケン化を行った。 Then, charged into a kneader and the solution was adjusted to a concentration of 50% was diluted with methanol, while maintaining the solution temperature at 40 ° C., a vinyl acetate structural units in the copolymer with 2% methanol solution of sodium hydroxide and 3 It was saponified by the addition at a rate of 12 mmol with respect to 1 mol of the total amount of 4-diacetoxy-1-butene structural units. ケン化が進行すると共にケン化物が析出して、粒子状となった時点で濾別し、メタノールでよく洗浄して熱風乾燥機中で乾燥し、PVA系樹脂を得た。 Saponified product precipitated with the progress of saponification, filtered off when it becomes a particulate, well washed with methanol, and dried in a hot air drier to obtain a PVA-based resin.
得られたPVA系樹脂のケン化度は、残存する酢酸ビニル構造単位及び3,4−ジアセトキシ−1−ブテン構造単位のエステル部の加水分解に要するアルカリ消費量で分析を行ったところ99モル%であり、1,2−ジオール構造を含有する側鎖の含有量は、 1 H−NMR(内部標準:テトラメチルシラン、溶媒:DMSO−d6)で測定して算出したところ6.81モル%であった。 Saponification degree of the resulting PVA-based resin, a vinyl acetate structural units remaining and 3,4-diacetoxy-1 with an alkali consumption required for hydrolysis of the ester portion of the butene structural units was analyzed 99 mol% , and the content of side chain containing the 1,2-diol structure, 1 H-NMR (internal standard: tetramethylsilane, solvent: DMSO-d6) with 6.81 mol% was calculated by measuring at there were. 平均重合度はJIS K 6726に準拠して測定したところ、320であった。 When the average polymerization degree was measured according to JIS K 6726, was 320.
かかるPVA系樹脂の製造において、下記の評価を行った。 In the manufacture of such a PVA-based resin, the following evaluations were carried out. 結果を表1に示す。 The results are shown in Table 1.

(重合度分布) (Polymerization degree distribution)
滴下開始後、3時間後、6時間後、9時間後に重合系中のポリ酢酸ビニル系重合体をサンプリングし、これを完全にケン化してポリビニルアルコール系重合体とし、その4%水溶液の粘度をヘプラー粘度計にて20℃で測定した。 After the dropwise addition started, after 3 hours, 6 hours, in the polymerization system after 9 hours sampling the polyvinyl acetate-based polymer, a polyvinyl alcohol polymer is completely saponified to this, the viscosity of the 4% aqueous solution It was measured at 20 ℃ in a Hoppler viscometer. その結果を表1に示す。 The results are shown in Table 1.
(変性度分布) (Modification degree distribution)
同様にサンプリングしたポリ酢酸ビニル系重合体中の側鎖1,2−ジオール構造の含有量を1 H−NMRにて測定した。 It was measured by 1 H-NMR content similarly sampled polyvinyl acetate side chain 1,2-diol structure of the polymer. 結果を表1に示す。 The results are shown in Table 1.

※ばらつき(倍)=各測定値/最終製品の測定値 ※ variation (times) = each measurement value / final product of the measured values

PS粘度、変性度ともに各重合時間後にサンプリングしたものと最終製品との測定値差が小さいことから、重合の全期にわたって同等の重合度、変性度のものが生成しているものと推定され、よって最終製品内の重合度分布、変性度分布は小さいものと推定される。 PS viscosity, since the measured value difference between each polymerization those sampling times after the final product is small modification degree both equal degree of polymerization over all phases of the polymerization, those modification degree is presumed to be generated, Thus the polymerization degree distribution in the final product, modified distribution is estimated to be small.

比較例1 Comparative Example 1
実施例1において、3,4−ジアセトキシ−1−ブテンの全使用量を重合初期に投入し、酢酸ビニルのみを同様の条件で滴下した以外は実施例1と同様にして側鎖に1,2−ジオール構造を有するPVA系樹脂を作製し、同様に評価した。 In Example 1, was charged the entire amount of 3,4-diacetoxy-1-butene in the polymerization initial, except that dropwise vinyl acetate alone under the same conditions in the same manner as in Example 1 in a side chain 1,2 - to prepare a PVA-based resin having a diol structure, it was evaluated in the same manner. 結果を表2に示す。 The results are shown in Table 2.

※ばらつき(倍)=各測定値/最終製品の測定値 ※ variation (times) = each measurement value / final product of the measured values

PS粘度、変性度ともに各重合時間後にサンプリングしたものの測定値が大きく変化しており、重合の時期によって異なる重合度、変性度のものが生成しているものと推定され、よって、最終製品の重合度分布、変性度分布は大きいものと推定される。 PS viscosity is changing measured values ​​greatly but sampled after each polymerization time modification degree both different polymerization degree depending on the time of polymerization, those modification degree is presumed to be generated, thus, the polymerization of the final product degree distribution, modification degree distribution is estimated to be greater.

本発明の方法で得られた側鎖に1,2−ジオール構造を有するPVA系樹脂は、重合度分布および変性度分布が小さく、その結果、物性の均一性に優れており、フィルムや繊維などの用途に極めて好適である。 PVA-based resin having a 1,2-diol structure in a side chain obtained by the method of the present invention, the polymerization degree distribution and modification degree distribution is small, as a result, is excellent in uniformity of physical properties, films, fibers, etc. it is very suitable to the application.

Claims (2)

  1. ビニルエステル系単量体と一般式(1)で示される単量体を溶媒中、重合触媒の存在下で共重合させるにあたり、重合系中に前記単量体を連続的あるいは断続的に添加して共重合し、次いで得られた共重合体をケン化することを特徴とする側鎖に1,2−ジオール構造を有するポリビニルアルコール系樹脂の製造方法。 A monomer in a solvent represented by the vinyl ester monomer of the general formula (1), when are copolymerized in the presence of a polymerization catalyst, the monomer continuously or intermittently added to the polymerization system polymerized, and then the obtained copolymer production method of a polyvinyl alcohol-based resin having a 1,2-diol structure in a side chain, which comprises saponifying both Te.

    [式中、R 1 、R 2及びR 3はそれぞれ独立して水素原子または有機基を示し、Xは単結合または結合鎖を示し、R 4 、R 5 、及びR 6はそれぞれ独立して水素原子または有機基を示し、R 7及びR 8はそれぞれ独立して水素原子またはR 9 −CO−(式中、R 9はアルキル基である)である。 [Wherein, R 1, R 2 and R 3 each independently represents a hydrogen atom or an organic group, X represents a single bond or a bonding chain, R 4, R 5, and R 6 each independently represents hydrogen indicates an atom or an organic group, a hydrogen atom or R 9 -CO- R 7 and R 8 are independently (wherein, R 9 is an alkyl group). ]
  2. 請求項1記載の製造方法によって得られたことを特徴とする側鎖に1,2−ジオール構造を有するポリビニルアルコール系樹脂。 Polyvinyl alcohol resin having a 1,2-diol structure in a side chain, characterized in that billing has been produced by the process of claim 1 wherein.
JP2007230348A 2007-09-05 2007-09-05 The method of producing a polyvinyl alcohol-based resin having a 1,2-diol structure in a side chain Active JP5235364B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007230348A JP5235364B2 (en) 2007-09-05 2007-09-05 The method of producing a polyvinyl alcohol-based resin having a 1,2-diol structure in a side chain

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2007230348A JP5235364B2 (en) 2007-09-05 2007-09-05 The method of producing a polyvinyl alcohol-based resin having a 1,2-diol structure in a side chain

Publications (2)

Publication Number Publication Date
JP2009062434A true true JP2009062434A (en) 2009-03-26
JP5235364B2 JP5235364B2 (en) 2013-07-10

Family

ID=40557316

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2007230348A Active JP5235364B2 (en) 2007-09-05 2007-09-05 The method of producing a polyvinyl alcohol-based resin having a 1,2-diol structure in a side chain

Country Status (1)

Country Link
JP (1) JP5235364B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011016928A (en) * 2009-07-09 2011-01-27 Nippon Synthetic Chem Ind Co Ltd:The Aqueous dispersion
JP2012216723A (en) * 2011-04-01 2012-11-08 Nitta Haas Inc Polishing composition
WO2015099131A1 (en) * 2013-12-26 2015-07-02 日本合成化学工業株式会社 Drilling fluid adjustment agent and drilling fluid using same

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002284818A (en) * 2000-12-15 2002-10-03 Nippon Synthetic Chem Ind Co Ltd:The Novel vinyl alcohol resin and its use
JP2004285143A (en) * 2003-03-20 2004-10-14 Nippon Synthetic Chem Ind Co Ltd:The Polyvinyl alcohol-based resin having 1,2-glycol bonds in side chains and method for producing the same
WO2006018870A1 (en) * 2004-08-18 2006-02-23 The Nippon Synthetic Chemical Industry Co.,Ltd. Polyvinyl alcohol having 1,2-glycol bond in side chain and process for producing the same
JP2006089538A (en) * 2004-09-22 2006-04-06 Nippon Synthetic Chem Ind Co Ltd:The Polyvinyl alcohol-based resin for melt molding and method for producing the same, and its application
JP2006096846A (en) * 2004-09-29 2006-04-13 Nippon Synthetic Chem Ind Co Ltd:The Polyvinyl alcohol-based water-containing gel, method for producing the same, and adsorptive separating agent and method of adsorptive separation by using the same
JP2006312313A (en) * 2005-04-05 2006-11-16 Nippon Synthetic Chem Ind Co Ltd:The Laminated structure
JP2007031601A (en) * 2005-07-28 2007-02-08 Nippon Synthetic Chem Ind Co Ltd:The Hydrogel
JP2007126655A (en) * 2000-12-15 2007-05-24 Nippon Synthetic Chem Ind Co Ltd:The New vinyl alcohol-based resin and use thereof
WO2007091547A1 (en) * 2006-02-07 2007-08-16 The Nippon Synthetic Chemical Industry Co., Ltd. Water-soluble polyvinyl alcohol resin fiber and nonwoven fabrics made by using the same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002284818A (en) * 2000-12-15 2002-10-03 Nippon Synthetic Chem Ind Co Ltd:The Novel vinyl alcohol resin and its use
JP2007126655A (en) * 2000-12-15 2007-05-24 Nippon Synthetic Chem Ind Co Ltd:The New vinyl alcohol-based resin and use thereof
JP2004285143A (en) * 2003-03-20 2004-10-14 Nippon Synthetic Chem Ind Co Ltd:The Polyvinyl alcohol-based resin having 1,2-glycol bonds in side chains and method for producing the same
WO2006018870A1 (en) * 2004-08-18 2006-02-23 The Nippon Synthetic Chemical Industry Co.,Ltd. Polyvinyl alcohol having 1,2-glycol bond in side chain and process for producing the same
JP2006089538A (en) * 2004-09-22 2006-04-06 Nippon Synthetic Chem Ind Co Ltd:The Polyvinyl alcohol-based resin for melt molding and method for producing the same, and its application
JP2006096846A (en) * 2004-09-29 2006-04-13 Nippon Synthetic Chem Ind Co Ltd:The Polyvinyl alcohol-based water-containing gel, method for producing the same, and adsorptive separating agent and method of adsorptive separation by using the same
JP2006312313A (en) * 2005-04-05 2006-11-16 Nippon Synthetic Chem Ind Co Ltd:The Laminated structure
JP2007031601A (en) * 2005-07-28 2007-02-08 Nippon Synthetic Chem Ind Co Ltd:The Hydrogel
WO2007091547A1 (en) * 2006-02-07 2007-08-16 The Nippon Synthetic Chemical Industry Co., Ltd. Water-soluble polyvinyl alcohol resin fiber and nonwoven fabrics made by using the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011016928A (en) * 2009-07-09 2011-01-27 Nippon Synthetic Chem Ind Co Ltd:The Aqueous dispersion
JP2012216723A (en) * 2011-04-01 2012-11-08 Nitta Haas Inc Polishing composition
WO2015099131A1 (en) * 2013-12-26 2015-07-02 日本合成化学工業株式会社 Drilling fluid adjustment agent and drilling fluid using same
JP2015143356A (en) * 2013-12-26 2015-08-06 日本合成化学工業株式会社 Drilling fluid modifier and drilling fluid using the same

Also Published As

Publication number Publication date Type
JP5235364B2 (en) 2013-07-10 grant

Similar Documents

Publication Publication Date Title
US3541059A (en) Novel reaction products of glycidyl esters and alkali metal sulfite or bisulfite,and polymers thereof
US4044197A (en) Thermally self-cross-linkable ethylene/vinyl acetate copolymers
US2808381A (en) Resin-dextrin compositions and method of preparation
US20050070679A1 (en) Copolymerizable emulsifiers and emulsion polymerization processes using the same
JP2002284818A (en) Novel vinyl alcohol resin and its use
EP0124782A2 (en) Polymer having thiol end group, process for producing same, and block copolymer based on polymer having thiol end group
JP2006124682A (en) Aqueous emulsion and application thereof
JPH11140136A (en) Production of ethylene/vinyl acetate copolymer by polymerization and production of saponificate of copolymer
JP2004285143A (en) Polyvinyl alcohol-based resin having 1,2-glycol bonds in side chains and method for producing the same
JP2002241433A (en) Novel vinyl alcohol resin and its use
JP2003171522A (en) Resin composition
WO2006018870A1 (en) Polyvinyl alcohol having 1,2-glycol bond in side chain and process for producing the same
US5599870A (en) Aqueous emulsion
JP2004285144A (en) Aqueous emulsion
JP2003171423A (en) Polyvinyl alcohol-based resin and use thereof
US5367015A (en) Polyvinyl acetals having improved melt viscosity characteristics, processes for their preparation and their use
JP2013177576A (en) Hydroxymethyl group-containing vinyl alcohol-based polymer
JP2006104309A (en) Polyvinyl acetal resin
US20100261830A1 (en) Aqueous emulsion and production method thereof
US2537016A (en) Heteropolymers of vinyl aromatic compounds, alkyl acrylates, and alkyl half esters of ethylene dicarboxylic acids and process of preparing same
JP2001019720A (en) Vinyl alcohol based polymer
JP2006152206A (en) Polyvinyl alcohol-based resin and its use
CN1506383A (en) Dispersion stabilizing agent for suspension polymerization of vinyl compound and producing process thereof
JPH08319318A (en) Vinyl alcohol-based polymer
JP2004300193A (en) Aqueous emulsion

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20100819

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20111128

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20120110

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20120309

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20121016

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20121217

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20130326

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20130326

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20160405

Year of fee payment: 3

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250