JPH09202812A - Production of aliphatic polyvinyl ester and polyvinyl alcohol - Google Patents
Production of aliphatic polyvinyl ester and polyvinyl alcoholInfo
- Publication number
- JPH09202812A JPH09202812A JP9947196A JP9947196A JPH09202812A JP H09202812 A JPH09202812 A JP H09202812A JP 9947196 A JP9947196 A JP 9947196A JP 9947196 A JP9947196 A JP 9947196A JP H09202812 A JPH09202812 A JP H09202812A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- aliphatic
- ester
- polyvinyl
- pva
- 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
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
- C08F18/00—Homopolymers and 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
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
- C08F18/08—Vinyl acetate
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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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)
- General Chemical & Material Sciences (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は脂肪族ポリビニルエ
ステルおよびこれを用いたポリビニルアルコールの製造
方法に関するものである。TECHNICAL FIELD The present invention relates to an aliphatic polyvinyl ester and a method for producing polyvinyl alcohol using the same.
【０００２】[0002]
【従来の技術】従来、工業的には脂肪族ポリビニルエス
テルは溶液重合、エマルジョン重合、懸濁重合等の重合
法等により製造され、またポリビニルアルコール（以
下、ＰＶＡと略記する）はそれらを酸またはアルカリ触
媒で鹸化して製造されている。なかでも、脂肪族ポリビ
ニルエステルおよびＰＶＡの一般的な製造方法として
は、アルコールを溶媒とした脂肪族ビニルエステルの溶
液重合でポリビニルエステルを得た後、アルカリ触媒で
鹸化してＰＶＡを得る方法が主として採用されている
が、これらの重合度は脂肪族ビニルエステルとアルコ−
ル類との配合比および重合反応率でコントロ−ルされて
いる。すなわち、高重合度のものは脂肪族ビニルエステ
ルの配合比を高く、低重合度のものは脂肪族ビニルエス
テルの配合比を低くして製造している。BACKGROUND OF THE INVENTION Conventionally, aliphatic polyvinyl esters are industrially produced by polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, etc., and polyvinyl alcohol (hereinafter abbreviated as PVA) uses acid or acid It is produced by saponification with an alkali catalyst. Among them, a general method for producing an aliphatic polyvinyl ester and PVA is mainly a method of obtaining a polyvinyl ester by solution polymerization of an aliphatic vinyl ester using alcohol as a solvent and then saponifying with an alkali catalyst to obtain PVA. Although adopted, the degree of polymerization of these is different from that of aliphatic vinyl ester and alcohol.
It is controlled by the compounding ratio with the polymer and the polymerization reaction rate. That is, those having a high degree of polymerization have a high blending ratio of the aliphatic vinyl ester, and those having a low degree of polymerization have a low blending ratio of the aliphatic vinyl ester.
【０００３】従って低重合度の脂肪族ポリビニルエステ
ルまたはＰＶＡの製造においては、生産性が低下した
り、使用触媒を多くする必要があるためコストアップに
なったり、着色等の品質低下が起こるという問題点があ
った。Therefore, in the production of an aliphatic polyvinyl ester or PVA having a low degree of polymerization, there is a problem that the productivity is lowered, the cost is increased because it is necessary to increase the amount of catalyst used, and the quality such as coloring is deteriorated. There was a point.
【０００４】次に、重合溶媒として連鎖移動定数が２０
×１０-4以上であるアルコ−ル（例えばエタノ−ル、イ
ソプロパノ−ル等）を用いることによって低重合度ＰＶ
Ａを製造する方法が、特開昭５１−８７５９４号公報で
提案されている。しかしながら、メタノ−ル以外の溶媒
を工業的に使用するにあたっては、現行のＰＶＡ製造設
備以外に溶剤回収等の新たな設備が必要となり、ＰＶＡ
の製造コストを著しく高めることになる。Next, a chain transfer constant of 20 is used as a polymerization solvent.
A low polymerization degree PV can be obtained by using an alcohol (for example, ethanol, isopropanol, etc.) having a density of × 10 -4 or more.
A method of producing A has been proposed in Japanese Patent Laid-Open No. 51-87594. However, when industrially using a solvent other than methanol, new equipment such as solvent recovery is required in addition to the existing PVA production equipment, and PVA is used.
Will significantly increase the manufacturing cost.
【０００５】また、重合系に連鎖移動剤を添加すると、
重合度が著しく低下することはよく知られている。例え
ば、連鎖移動剤としてメルカプタン類を用いる方法が特
公平１−４００４３号公報で開示されている。しかしな
がら、通常のＰＶＡ製造設備を用いて製造する場合、少
量のメルカプタン類でも重合系に大きく影響するため、
回収溶剤への混入を避ける必要があり、そのための設備
が必要であると同時に、メルカプタン類特有の強烈な悪
臭が製品に付くという問題点があった。その他にも連鎖
移動剤としてアルデヒド類やハロゲン化炭化水素等を用
いる方法があるが、重合あるいは鹸化時に着色が生じ、
白色のＰＶＡが得られない等の問題点があった。When a chain transfer agent is added to the polymerization system,
It is well known that the degree of polymerization is significantly reduced. For example, a method using mercaptans as a chain transfer agent is disclosed in Japanese Patent Publication No. 1-40043. However, when it is produced using a normal PVA production facility, even a small amount of mercaptans greatly affects the polymerization system.
There is a problem that it is necessary to avoid mixing in the recovered solvent, equipment for that purpose is required, and at the same time, a strong odor peculiar to mercaptans is attached to the product. Other methods include the use of aldehydes and halogenated hydrocarbons as chain transfer agents, but coloring occurs during polymerization or saponification,
There was a problem that white PVA could not be obtained.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、かかる現状
に鑑み、着色や臭気等の品質への悪影響を及ぼすことな
く、工業的に有利な条件で種々の低重合度の脂肪族ポリ
ビニルエステルおよびＰＶＡを製造する方法を提供しよ
うとするものである。SUMMARY OF THE INVENTION In view of the above situation, the present invention provides aliphatic polyvinyl esters having various low polymerization degrees under industrially advantageous conditions without adversely affecting the quality such as coloring and odor. It is an object of the present invention to provide a method for producing PVA.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、脂肪族ビ
ニルエステルの重合系にアリルスルホン酸、メタリルス
ルホン酸またはそれらの塩類を添加することにより、添
加量に応じて重合度が低下すること、すなわちアリルス
ルホン酸、メタリルスルホン酸またはそれらの塩類が連
鎖移動剤として有効に作用することを見いだし、本発明
に到達した。すなわち、本発明は、脂肪族ビニルエステ
ルの重合において、連鎖移動剤としてアリルスルホン
酸、メタリルスルホン酸またはそれらの塩類を脂肪族ビ
ニルエステルに対して０．０５〜１．０モル％添加する
ことを特徴とする脂肪族ポリビニルエステルの製造方法
および前記脂肪族ポリビニルエステルを鹸化することを
特徴とするＰＶＡの製造方法である。The present inventors have added allylsulfonic acid, methallylsulfonic acid or salts thereof to a polymerization system of an aliphatic vinyl ester, whereby the degree of polymerization is lowered depending on the addition amount. That is, the present invention has been accomplished by discovering that allyl sulfonic acid, methallyl sulfonic acid or salts thereof act effectively as a chain transfer agent. That is, in the present invention, in the polymerization of an aliphatic vinyl ester, allylsulfonic acid, methallylsulfonic acid or their salts are added as a chain transfer agent in an amount of 0.05 to 1.0 mol% based on the aliphatic vinyl ester. And a method for producing PVA, which comprises saponifying the aliphatic polyvinyl ester.
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明で使用される脂肪族ビニルエステルとしては、各
種のものが使用され、例えばギ酸ビニル、酢酸ビニル、
プロピオン酸ビニル、ピバリン酸ビニル、ステアリン酸
ビニル等の公知の脂肪族ビニルエステルを挙げることが
できるが、工業的には特に酢酸ビニルが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
As the aliphatic vinyl ester used in the present invention, various ones are used, for example, vinyl formate, vinyl acetate,
Known aliphatic vinyl esters such as vinyl propionate, vinyl pivalate, vinyl stearate and the like can be mentioned, but vinyl acetate is particularly preferable industrially.
【０００９】脂肪族ビニルエステルは、各種の重合方法
により重合することができ、例えば溶液重合、乳化重
合、懸濁重合等の公知の方法で重合することができる。
脂肪族ビニルエステルを工業的に溶液重合する場合に
は、溶媒としてはメタノ−ル等が使用され、重合開始剤
としては、アゾ系化合物、過酸化物等のラジカル重合開
始剤が使用され、重合温度６０℃前後で重合することが
できる。また、重合方式としては、バッチ重合、連続重
合のいずれの方式を採用することもできる。The aliphatic vinyl ester can be polymerized by various polymerization methods, for example, known methods such as solution polymerization, emulsion polymerization and suspension polymerization.
When industrially solution-polymerizing an aliphatic vinyl ester, methanol or the like is used as a solvent, an azo compound, a radical polymerization initiator such as a peroxide is used as a polymerization initiator, and polymerization is performed. Polymerization can be carried out at a temperature of around 60 ° C. Further, as the polymerization system, either batch polymerization or continuous polymerization can be adopted.
【００１０】本発明において使用する連鎖移動剤は、ア
リルスルホン酸、メタリルスルホン酸またはそれらの塩
類である。前記塩類としては、ソ−ダ塩、カリウム塩、
アンモニウム塩等を挙げることができ、中でもアリルス
ルホン酸ソ−ダ、メタリルスルホン酸ソ−ダが好適であ
る。その添加方法としては各種の方法を使用することが
でき、必要に応じて一括添加、逐次分割、または連続添
加の方法をとることができる。アリルスルホン酸、メタ
リルスルホン酸ソ−ダまたはそれらの塩類の添加量は、
好ましくは脂肪族ビニルエステルに対し０．０５〜１．
０モル％、さらに好ましくは０．１〜０．７モル％であ
る。使用量が０．０５モル％より少ないと、連鎖移動効
果が小さいので好ましくなく、一方、使用量が１．０モ
ル％を超えると、得られるポリビニルエステルやＰＶＡ
の吸湿性が増すなど、本来の特性を損なってしまうた
め、好ましくない。The chain transfer agent used in the present invention is allylsulfonic acid, methallylsulfonic acid or salts thereof. Examples of the salts include soda salt, potassium salt,
Examples thereof include ammonium salts, and among them, allyl sulfonic acid soda and methallyl sulfonic acid soda are preferable. Various methods can be used as the addition method, and a method of batch addition, sequential division, or continuous addition can be taken as necessary. The addition amount of allyl sulfonic acid, methallyl sulfonic acid soda or their salts is
Preferably 0.05 to 1.
It is 0 mol%, more preferably 0.1 to 0.7 mol%. When the amount used is less than 0.05 mol%, the chain transfer effect is small, which is not preferable. On the other hand, when the amount used exceeds 1.0 mol%, the obtained polyvinyl ester or PVA is obtained.
It is not preferable because the original characteristics such as the increased hygroscopicity of are impaired.
【００１１】本発明の脂肪族ビニルエステルの重合に際
し、脂肪族ビニルエステルと共重合可能な単量体、例え
ばエチレン、プロピレン、イソブテン等のα−オレフィ
ン、アクリル酸、メタクリル酸、クロトン酸、マレイン
酸、イタコン酸、無水マレイン酸等の不飽和酸類あるい
はその塩あるいはモノまたはジアルキルエステル、アク
リロニトリル、メタクリロニトリル類、アクリルアミ
ド、メタクリルアミド類、ビニルエ−テル類、塩化ビニ
ル、塩化ビニリデン、ビニルスルホン酸あるいはその塩
等を少量存在させることも可能であるIn the polymerization of the aliphatic vinyl ester of the present invention, monomers copolymerizable with the aliphatic vinyl ester, for example, α-olefins such as ethylene, propylene and isobutene, acrylic acid, methacrylic acid, crotonic acid, maleic acid. , Itaconic acid, unsaturated acids such as maleic anhydride or salts thereof or mono- or dialkyl esters, acrylonitrile, methacrylonitriles, acrylamide, methacrylamide, vinyl ethers, vinyl chloride, vinylidene chloride, vinyl sulfonic acid or the like It is also possible to have a small amount of salt, etc.
【００１２】本発明のＰＶＡは、得られたポリビニルエ
ステルを鹸化、粉砕、乾燥して得られる。鹸化方法とし
ては各種の方法が採用されるが、特にポリビニルエステ
ルのアルコ−ル溶液を水酸化ナトリウム、水酸化カリウ
ム等のアルカリを触媒として鹸化することが望ましい。The PVA of the present invention is obtained by saponifying, pulverizing and drying the obtained polyvinyl ester. Although various methods are adopted as the saponification method, it is particularly preferable to saponify the polyvinyl ester alcohol solution with an alkali such as sodium hydroxide or potassium hydroxide as a catalyst.
【００１３】本発明の方法により脂肪族ビニルエステル
の重合を行うことによって、着色や悪臭等の品質への悪
影響を及ぼすことなく、工業的に有利な条件で種々の低
重合度の脂肪族ポリビニルエステルおよびＰＶＡを製造
することができる。By polymerizing an aliphatic vinyl ester by the method of the present invention, an aliphatic polyvinyl ester having various low polymerization degrees under industrially advantageous conditions can be obtained without adversely affecting the quality such as coloring and malodor. And PVA can be produced.
【００１４】[0014]
【実施例】以下に、本発明を実施例により具体的に説明
する。The present invention will be described below in more detail with reference to examples.
【００１５】実施例１ 酢酸ビニル７９．４重量部、メタノ−ル２０．１重量
部、アリルスルホン酸ソ−ダ０．５３重量部（酢酸ビニ
ル１００モル％に対して０．４モル％）の混合溶液に重
合開始剤としてアゾビスイソブチロニトリルを０．０３
重量部（酢酸ビニル１００重量部に対して）加え、６０
℃で５時間重合した。重合収率は６６％で平均重合度は
５７０であった。酢酸ビニルを除去した後、得られたポ
リ酢酸ビニルをアルカリ鹸化してＰＶＡを得た。このＰ
ＶＡの白度は良好であり、臭気も感じられなかった。Example 1 79.4 parts by weight of vinyl acetate, 20.1 parts by weight of methanol, and 0.53 parts by weight of sodium allylsulfonate (0.4 mol% based on 100 mol% of vinyl acetate). Azobisisobutyronitrile was added to the mixed solution in an amount of 0.03 as a polymerization initiator.
60 parts by weight (based on 100 parts by weight of vinyl acetate)
Polymerization was carried out at ℃ for 5 hours. The polymerization yield was 66% and the average degree of polymerization was 570. After removing the vinyl acetate, the obtained polyvinyl acetate was alkali-saponified to obtain PVA. This P
The whiteness of VA was good and no odor was felt.
【００１６】実施例２ アリルスルホン酸ソ−ダを０．２７重量部（酢酸ビニル
１００モル％に対して０．２モル％）添加した以外は、
実施例１と同様の方法で重合、鹸化を行った。結果は表
１に示すように、ポリ酢酸ビニルの重合収率は６７％で
平均重合度は８６０であり、実施例１の場合と比べてア
リルスルホン酸ソ−ダの添加量の減少に伴い平均重合度
の異なるものが得られた。また、得られたＰＶＡの白度
は良好であり、臭気も感じられなかった。Example 2 Except that 0.27 part by weight of sodium allylsulfonate (0.2 mol% based on 100 mol% of vinyl acetate) was added.
Polymerization and saponification were carried out in the same manner as in Example 1. As shown in Table 1, the polymerization yield of polyvinyl acetate was 67% and the average degree of polymerization was 860. As compared with the case of Example 1, the average amount of sodium allylsulfonate was decreased as the addition amount was decreased. Those having different degrees of polymerization were obtained. Further, the whiteness of the obtained PVA was good and no odor was felt.
【００１７】実施例３ 酢酸ビニル６５．２重量部、メタノ−ル３４．３重量
部、アリルスルホン酸ソ−ダ０．４４重量部（酢酸ビニ
ル１００モル％に対して０．４モル％）の混合溶液に重
合開始剤としてアゾビスジメチルバレロニトリルを０．
０４重量部（酢酸ビニル１００重量部に対して）加えて
６０℃で５時間重合を行った。結果は表１に示すよう
に、重合収率は８８％で平均重合度は４１０であった。
酢酸ビニルを除去した後、得られたポリ酢酸ビニルをア
ルカリ鹸化してＰＶＡを得た。このＰＶＡの白度は良好
であり、臭気も感じられなかった。Example 3 65.2 parts by weight of vinyl acetate, 34.3 parts by weight of methanol, and 0.44 parts by weight of soda allylsulfonate (0.4 mol% based on 100 mol% of vinyl acetate). Azobisdimethylvaleronitrile as a polymerization initiator was added to the mixed solution in an amount of 0.
04 parts by weight (based on 100 parts by weight of vinyl acetate) were added and polymerization was carried out at 60 ° C. for 5 hours. As shown in Table 1, the result was that the polymerization yield was 88% and the average degree of polymerization was 410.
After removing the vinyl acetate, the obtained polyvinyl acetate was alkali-saponified to obtain PVA. The whiteness of this PVA was good and no odor was felt.
【００１８】実施例４ アリルスルホン酸ソ−ダを０．２２重量部（酢酸ビニル
１００モル％に対して０．２モル％）添加した以外は、
実施例３と同様の方法で重合、鹸化を行った。結果は表
１に示すように、ポリ酢酸ビニルの重合収率は８８％で
平均重合度は５９０であり、実施例３の場合と比べてア
リルスルホン酸ソ−ダの添加量の減少に伴い平均重合度
の異なるものが得られた。また、得られたＰＶＡの白度
は良好であり、臭気も感じられなかった。Example 4 Except that 0.22 parts by weight of sodium allylsulfonate (0.2 mol% based on 100 mol% of vinyl acetate) was added,
Polymerization and saponification were carried out in the same manner as in Example 3. As shown in Table 1, the polymerization yield of polyvinyl acetate was 88% and the average degree of polymerization was 590. The average degree of polymerization was decreased as the addition amount of sodium allylsulfonate was decreased as compared with the case of Example 3. Those having different degrees of polymerization were obtained. Further, the whiteness of the obtained PVA was good and no odor was felt.
【００１９】実施例５ 一段式連続重合装置において、酢酸ビニル７２．０重量
部、メタノ−ル２７．８重量部、アリルスルホン酸ソ−
ダ０．３６重量部（酢酸ビニル１００モル％に対して
０．３モル％）、アゾビスジメチルバレロニトリル０．
０４重量部（酢酸ビニル１００重量部に対して）を連続
的に還流状態の反応器中に導入し、液量を一定に保ちな
がら反応器外に抜き出し、収率を８４％に保った。結果
は表１に示すように、重合収率は８４％で平均重合度は
１７０であった。得られたポリ酢酸ビニルをアルカリ鹸
化してＰＶＡを得た。このＰＶＡの白度は良好であり、
臭気も感じられなかった。Example 5 In a single-stage continuous polymerization apparatus, 72.0 parts by weight of vinyl acetate, 27.8 parts by weight of methanol and sodium allylic sulfonate were used.
0.36 parts by weight (0.3 mol% relative to 100 mol% of vinyl acetate), azobisdimethylvaleronitrile 0.1.
04 parts by weight (relative to 100 parts by weight of vinyl acetate) were continuously introduced into the reactor in the reflux state, and the liquid was withdrawn at a constant rate, and the yield was kept at 84%. As a result, as shown in Table 1, the polymerization yield was 84%, and the average degree of polymerization was 170. The obtained polyvinyl acetate was alkali-saponified to obtain PVA. The whiteness of this PVA is good,
No odor was felt.
【００２０】実施例６ アリルスルホン酸ソ−ダを０．１２重量部（酢酸ビニル
１００モル％に対して０．１モル％）添加した以外は、
実施例５と同様の方法で重合、鹸化を行った。結果は表
１に示すように、ポリ酢酸ビニルの重合収率は８４％で
平均重合度は３００であり、実施例５の場合と比べてア
リルスルホン酸ソ−ダの添加量の減少に伴い平均重合度
の異なるものが得られた。また、得られたＰＶＡの白度
は良好であり、臭気も感じられなかった。Example 6 Except that 0.12 parts by weight of sodium allylsulfonate (0.1 mol% based on 100 mol% of vinyl acetate) was added,
Polymerization and saponification were carried out in the same manner as in Example 5. As shown in Table 1, the polymerization yield of polyvinyl acetate was 84% and the average degree of polymerization was 300. The average polymerization degree was decreased as the addition amount of sodium allylsulfonate was decreased as compared with the case of Example 5. Those having different degrees of polymerization were obtained. Further, the whiteness of the obtained PVA was good and no odor was felt.
【００２１】実施例７ アリルスルホン酸ソ−ダをメタリルスルホン酸ソ−ダに
代えて０．２４重量部（酢酸ビニル１００モル％に対し
て０．２モル％）添加した以外は、実施例４と同様の方
法で重合、鹸化を行った。結果は表１に示すように、ポ
リ酢酸ビニルの重合収率は８４％で平均重合度は４６０
であった。得られたＰＶＡの白度は良好であり、臭気も
感じられなかった。Example 7 Example 2 was repeated except that 0.24 parts by weight (0.2 mol% based on 100 mol% of vinyl acetate) was added in place of soda methallylsulfonate soda. Polymerization and saponification were carried out in the same manner as in 4. As shown in Table 1, the polymerization yield of polyvinyl acetate is 84% and the average degree of polymerization is 460.
Met. The whiteness of the obtained PVA was good and no odor was felt.
【００２２】比較例１ アリルスルホン酸ソ−ダを添加しない以外は、実施例１
と同様の方法で重合、鹸化を行った。結果は表１に示す
ように、重合収率は６７％で平均重合度は１７８０であ
り、低重合度のものは得られなかった。Comparative Example 1 Example 1 except that no allyl sulfonate soda was added.
Polymerization and saponification were performed in the same manner as in. As shown in Table 1, the polymerization yield was 67%, the average degree of polymerization was 1780, and no low degree of polymerization was obtained.
【００２３】比較例２ アリルスルホン酸ソ−ダを２．００重量部（酢酸ビニル
１００モル％に対して１．５モル％）添加した以外は、
実施例１と同様の方法で重合、鹸化を行った。結果は表
１に示すように、ポリ酢酸ビニルの重合収率は６５％で
平均重合度は１６０であり、また得られたＰＶＡは無臭
であったが、淡黄色であり、吸湿性が大きかった。Comparative Example 2 Except that 2.00 parts by weight of sodium allylsulfonate (1.5 mol% relative to 100 mol% of vinyl acetate) was added.
Polymerization and saponification were carried out in the same manner as in Example 1. As shown in Table 1, the polymerization yield of polyvinyl acetate was 65%, the average degree of polymerization was 160, and the obtained PVA was odorless, but it was pale yellow and had a high hygroscopicity. .
【００２４】比較例３ 実施例１と同じ重合度のＰＶＡを得るため酢酸ビニル４
５．０重量部、メタノ−ル５５．０重量部の混合溶液に
重合開始剤としてアゾビスイソブチロニトリルを０．１
５重量部（酢酸ビニル１００重量部に対して）を加え、
６０℃で５時間重合を行った。結果は表１に示すよう
に、重合収率は９０％で平均重合度は５７０であった。
酢酸ビニルを除去した後、得られたポリ酢酸ビニルをア
ルカリ鹸化してＰＶＡを得た。このＰＶＡは無臭であっ
たが、黄色であった。Comparative Example 3 Vinyl acetate 4 was used to obtain PVA with the same degree of polymerization as in Example 1.
To a mixed solution of 5.0 parts by weight and 55.0 parts by weight of methanol, 0.1% of azobisisobutyronitrile was added as a polymerization initiator.
Add 5 parts by weight (based on 100 parts by weight of vinyl acetate),
Polymerization was carried out at 60 ° C. for 5 hours. As a result, as shown in Table 1, the polymerization yield was 90% and the average degree of polymerization was 570.
After removing the vinyl acetate, the obtained polyvinyl acetate was alkali-saponified to obtain PVA. This PVA was odorless but yellow.
【００２５】比較例４ 一段式連続重合装置において、酢酸ビニル８０．０重量
部、メタノ−ル１９．５重量部、ｎ−ドデシルメルカプ
タン０．５０重量部、アゾビスイソブチロニトリル０．
０４重量部（酢酸ビニル１００重量部に対して）を連続
的に還流状態の反応器中に導入し、液量を一定に保ちな
がら反応器外に抜き出し、収率を７０％に保った。結果
は表１に示すように、重合収率は７０％で平均重合度は
１９０であった。得られたポリ酢酸ビニルをアルカリ鹸
化してＰＶＡを得た。このＰＶＡの白度は良好であった
が、メルカプタン臭がした。Comparative Example 4 In a one-stage continuous polymerization apparatus, 80.0 parts by weight of vinyl acetate, 19.5 parts by weight of methanol, 0.50 parts by weight of n-dodecyl mercaptan, and azobisisobutyronitrile of 0.
04 parts by weight (relative to 100 parts by weight of vinyl acetate) were continuously introduced into the reactor in the reflux state, and the liquid was kept constant and withdrawn from the reactor to keep the yield at 70%. As a result, as shown in Table 1, the polymerization yield was 70% and the average degree of polymerization was 190. The obtained polyvinyl acetate was alkali-saponified to obtain PVA. The whiteness of this PVA was good, but it had a mercaptan odor.
【００２６】[0026]
【表１】 [Table 1]
【００２７】参考例 アリルスルホン酸ソーダの連鎖移動効果を見るために、
実施例１と実施例２、比較例１における重合度の値か
ら、下式を用いてアリルスルホン酸ソーダの連鎖移動定
数Ｃｘを算出した。 １／Ｐ＝１／Ｐ0 ＋Ｃｘ〔Ｘ〕／〔Ｍ〕 ただし、Ｐ＝重合度、Ｐ0 ＝連鎖移動剤がない場合の重
合度、Ｃｘ＝連鎖移動定数、〔Ｘ〕＝連鎖移動剤濃度、
〔Ｍ〕＝モノマー濃度である。得られた連鎖移動定数Ｃ
ｘは０．３であり、これはモノマー、メタノールの連鎖
移動定数が２×１０-4であることを考慮すると、極めて
大きな値であり、アリルスルホン酸ソーダが連鎖移動剤
として有効に作用していることを示している。Reference Example To see the chain transfer effect of sodium allylsulfonate,
From the values of the degree of polymerization in Example 1, Example 2 and Comparative Example 1, the chain transfer constant Cx of sodium allylsulfonate was calculated using the following formula. 1 / P = 1 / P 0 + Cx [X] / [M] However, P = degree of polymerization, the polymerization degree in the absence of P 0 = chain transfer agent, Cx = chain transfer constant, [X] = concentration of chain transfer agent ,
[M] = monomer concentration. Obtained chain transfer constant C
x is 0.3, which is an extremely large value in view of the fact that the chain transfer constant of the monomer and methanol is 2 × 10 −4 , and sodium allylsulfonate effectively acts as a chain transfer agent. It indicates that
【００２８】[0028]
【発明の効果】本発明によれば、悪臭や着色等の品質へ
の悪影響を及ぼすことなく工業的に有利な条件で種々の
低重合度の脂肪族ポリビニルエステルおよびＰＶＡを製
造することができる。そしてこれらは従来のＰＶＡと同
様に取り扱うことができ、塗料、接着剤、乳化分散剤、
繊維加工剤、フィルム、バインダ−等に有用なものであ
る。EFFECTS OF THE INVENTION According to the present invention, various low polymerization degree aliphatic polyvinyl esters and PVA can be produced under industrially advantageous conditions without adversely affecting the quality such as odor and coloring. And these can be handled in the same way as conventional PVA, paint, adhesive, emulsifying dispersant,
It is useful as a fiber processing agent, a film, a binder and the like.
Claims (2)
連鎖移動剤としてアリルスルホン酸、メタリルスルホン
酸またはそれらの塩類を脂肪族ビニルエステルに対して
０．０５〜１．０モル％添加することを特徴とする脂肪
族ポリビニルエステルの製造方法。1. In the polymerization of an aliphatic vinyl ester,
A method for producing an aliphatic polyvinyl ester, which comprises adding allylsulfonic acid, methallylsulfonic acid or salts thereof as a chain transfer agent in an amount of 0.05 to 1.0 mol% with respect to the aliphatic vinyl ester.
ルを鹸化することを特徴とするポリビニルアルコールの
製造方法。2. A method for producing polyvinyl alcohol, which comprises saponifying the aliphatic polyvinyl ester according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9947196A JPH09202812A (en) | 1995-11-21 | 1996-03-29 | Production of aliphatic polyvinyl ester and polyvinyl alcohol |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32528295 | 1995-11-21 | ||
| JP7-325282 | 1995-11-21 | ||
| JP9947196A JPH09202812A (en) | 1995-11-21 | 1996-03-29 | Production of aliphatic polyvinyl ester and polyvinyl alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09202812A true JPH09202812A (en) | 1997-08-05 |
Family
ID=26440606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9947196A Pending JPH09202812A (en) | 1995-11-21 | 1996-03-29 | Production of aliphatic polyvinyl ester and polyvinyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09202812A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0987280A2 (en) * | 1998-09-18 | 2000-03-22 | Air Products And Chemicals, Inc. | Sulfonate-terminated oligomers of vinyl esters and their vinyl alcohol oligomer derivatives |
| WO2007141182A2 (en) * | 2006-06-07 | 2007-12-13 | Basf Se | Utilization of vinyl acetate sulfonate copolymers as solubilizers for compounds with low solubility in water |
| WO2017121120A1 (en) * | 2016-01-11 | 2017-07-20 | 重庆云天化瀚恩新材料开发有限公司 | Polyvinyl alcohol, preparation method therefor, and polyvinyl alcohol film |
| US11091574B2 (en) | 2016-05-31 | 2021-08-17 | Kuraray Co., Ltd. | Method for producing vinyl alcohol polymers |
| CN113603815A (en) * | 2021-08-25 | 2021-11-05 | 云南唯益新材料有限公司 | Preparation method of polyvinyl alcohol with low polymerization degree |
-
1996
- 1996-03-29 JP JP9947196A patent/JPH09202812A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0987280A2 (en) * | 1998-09-18 | 2000-03-22 | Air Products And Chemicals, Inc. | Sulfonate-terminated oligomers of vinyl esters and their vinyl alcohol oligomer derivatives |
| EP0987280A3 (en) * | 1998-09-18 | 2000-07-26 | Air Products And Chemicals, Inc. | Sulfonate-terminated oligomers of vinyl esters and their vinyl alcohol oligomer derivatives |
| WO2007141182A2 (en) * | 2006-06-07 | 2007-12-13 | Basf Se | Utilization of vinyl acetate sulfonate copolymers as solubilizers for compounds with low solubility in water |
| WO2007141182A3 (en) * | 2006-06-07 | 2008-05-08 | Basf Se | Utilization of vinyl acetate sulfonate copolymers as solubilizers for compounds with low solubility in water |
| WO2017121120A1 (en) * | 2016-01-11 | 2017-07-20 | 重庆云天化瀚恩新材料开发有限公司 | Polyvinyl alcohol, preparation method therefor, and polyvinyl alcohol film |
| US11091574B2 (en) | 2016-05-31 | 2021-08-17 | Kuraray Co., Ltd. | Method for producing vinyl alcohol polymers |
| CN113603815A (en) * | 2021-08-25 | 2021-11-05 | 云南唯益新材料有限公司 | Preparation method of polyvinyl alcohol with low polymerization degree |
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