JPS6236408A - Production of polyhydroxycarboxylic acid - Google Patents
Production of polyhydroxycarboxylic acidInfo
- Publication number
- JPS6236408A JPS6236408A JP17524885A JP17524885A JPS6236408A JP S6236408 A JPS6236408 A JP S6236408A JP 17524885 A JP17524885 A JP 17524885A JP 17524885 A JP17524885 A JP 17524885A JP S6236408 A JPS6236408 A JP S6236408A
- Authority
- JP
- Japan
- Prior art keywords
- allyl alcohol
- acid
- acrylic acid
- radical
- parts
- 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
Links
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はカルボキシレート基とヒドロキシル基とｔ−有
するポリオキシカルボン酸の製造方法に関し、開始剤と
して過酸化水素を仕込みモノマーの合計量に対し１０−
３０重量％添加することにより仕込みモノマーのほとん
ど全てを反応させ、モノマー回収が不要であるポリオキ
シカルボン酸の製造方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing a polyoxycarboxylic acid having a carboxylate group, a hydroxyl group, and t-containing hydrogen peroxide as an initiator. 10-
It relates to a method for producing polyoxycarboxylic acid in which almost all of the charged monomers are reacted by adding 30% by weight, and monomer recovery is not necessary.
さらに詳しくは、本発明はアリルアルコールとアクリル
酸またはメタクリル酸を共重合させる際に、ラジカル開
始剤として過酸化水素をアリルアルコールとアクリル酸
またはメタクリル酸の合計モノマーに対して１０〜５０
重量％添加することｔ−特徴とする未反応モノマーの回
収の不要なポリオキシカルボン酸の製造方法に関する。More specifically, in the present invention, when copolymerizing allyl alcohol and acrylic acid or methacrylic acid, hydrogen peroxide is used as a radical initiator in an amount of 10 to 50% based on the total monomers of allyl alcohol and acrylic acid or methacrylic acid.
The present invention relates to a method for producing a polyoxycarboxylic acid, which does not require recovery of unreacted monomers, and is characterized by adding t-% by weight.
アリルアルコールとアクリル酸またはメタクリル酸とを
ラジカル重合させて得たポリオキシカルボン酸は主成分
として一般式
（式中、Ａは水素、１価又は多価金属、特にアルカリ金
属殊にナトリウム原子又はアンモニウムを表わし、Ｒ１
はメチル基、殊に水素原子全表わす）の繰り返し単位か
ら構成されている。Polyoxycarboxylic acid obtained by radical polymerization of allyl alcohol and acrylic acid or methacrylic acid has the general formula (where A is hydrogen, a monovalent or polyvalent metal, especially an alkali metal, especially a sodium atom or an ammonium atom) as a main component. and R1
is composed of repeating units of methyl groups, especially hydrogen atoms (representing all hydrogen atoms).
（従来、ポリオキシカルボン酸という言葉で習慣上アル
カリ塩と遊離酸又はそれらの混合物を総称している。本
発明においても特にことわらない限フポリオキシカルボ
ン酸という言葉を同じ意味で使うことにする。）その製
造方法としては、特公昭５７−３９２４６号公報による
とアリルアルコールと（メタ）アクリル酸を過酸化ベン
ゾイル、アゾビスイソブチロニトリル等のラジカル開始
剤を用いてラジカル重合させた後、水酸化アルカリを加
え、中和およびケン化し、この反応液から蒸留によシ未
反応アリルアルコールを回収し所定の濃度のポリオキシ
カルボン酸を得ている。従って、この方法では反応粗液
中から未反応のアリルアルコールを回収する操作が必要
であり、この未反応アリルアルコールの回収は製造装置
および操作を煩雑にするとともにコストアップにもつな
がり大きな問題となっている。(Conventionally, the term polyoxycarboxylic acid has customarily been used to collectively refer to alkali salts, free acids, or mixtures thereof. In the present invention, unless otherwise specified, the term polyoxycarboxylic acid will be used interchangeably. According to Japanese Patent Publication No. 57-39246, the manufacturing method is to radically polymerize allyl alcohol and (meth)acrylic acid using a radical initiator such as benzoyl peroxide or azobisisobutyronitrile. , alkali hydroxide is added, neutralized and saponified, and unreacted allyl alcohol is recovered from this reaction solution by distillation to obtain polyoxycarboxylic acid at a predetermined concentration. Therefore, this method requires an operation to recover unreacted allyl alcohol from the reaction crude liquid, and recovery of this unreacted allyl alcohol complicates the production equipment and operations, and also increases costs, which poses a major problem. ing.
〔問題点を解決するための手段］
そこで本発明者らは未反応モノマーの回収の不要なポリ
オキシカルボン酸の製造方法を得んと鋭意検討した結果
、アリルアルコールとアクリル酸またはメタクリル酸と
全ラジカル共重合させる際に、ラジカル開始剤として過
酸化水素ｔアリルアルコールとアクリル酸またはメタク
リル酸の合計モノマーに対して１０へ５０７４Ｊ％龜加
することにより、未反応上ツマ−の存在しない、すなわ
ち未反応モノマーの回収の不要なポリオキシカルボン酸
が製造できること金兄い出し、本発明を完成させ九。[Means for Solving the Problems] Therefore, the present inventors conducted extensive studies to find a method for producing polyoxycarboxylic acid that does not require recovery of unreacted monomers. During radical copolymerization, by adding 10 to 5074 J% of the total monomers of hydrogen peroxide, allyl alcohol, and acrylic acid or methacrylic acid as a radical initiator, it is possible to eliminate the presence of unreacted polymers. It was discovered that polyoxycarboxylic acid could be produced without the need to recover reaction monomers, and the present invention was completed.
本発明で用いるラジカル重合の方法としてはラジカル開
始剤として過酸化水素？用いる方法であり、過酸化水素
の使用量は１０〜５０重量％、好ましくは１２〜２０重
貢％添加するのが望ましい。The radical polymerization method used in the present invention uses hydrogen peroxide as a radical initiator. According to the method used, it is desirable to add hydrogen peroxide in an amount of 10 to 50% by weight, preferably 12 to 20% by weight.
共重合反応の媒体としては水が作業性等の面から判断し
て最も適しており、その添加量は生成するポリオキシカ
ルボン酸のアルカリ塩の浴解などを考慮して定めること
もできるがこれに限定されるものではない。Water is the most suitable medium for the copolymerization reaction from the viewpoint of workability, etc., and the amount of water added can be determined by taking into consideration the bath dissolution of the alkali salt of the polyoxycarboxylic acid to be produced. It is not limited to.
共重合反応は原則的にはバッチ式又は連続式のいずれで
も行ない得る。反応温度は４０へ１００℃が一般的であ
り、反応時間は反応温度および過酸化水素の使用量に影
響されるが一般には４−１０時間である。In principle, the copolymerization reaction can be carried out either batchwise or continuously. The reaction temperature is generally 40 to 100°C, and the reaction time is generally 4 to 10 hours, although it is influenced by the reaction temperature and the amount of hydrogen peroxide used.
ラジカル重合におけるアクリル酸ま友はメタクリル酸の
アリルアルコールに対する仕込モル比は得られる重合物
および更にそれから水酸化アルカリとの反応によって得
られるポリオキシカルボン酸の性質に大きな影響を及ぼ
す。例えばポリオキシカルボン酸のアルカリ塩のカルボ
中シレート基のヒドロキシル基に対するそル比が２Ｓ５
であるポリオキシカルボン酸は最高のカルシウムイオン
封鎖能力全厚える。ま几水溶性に影響を与えない他のモ
ノマー例えばアクリルアミド、アクリルアミンなども必
要に応じて用いることもできる。In radical polymerization, the molar ratio of methacrylic acid to allyl alcohol has a great effect on the properties of the resulting polymer and the polyoxycarboxylic acid obtained by reaction with alkali hydroxide. For example, the ratio of sylate groups to hydroxyl groups in the carboxylic acid of an alkali salt of polyoxycarboxylic acid is 2S5
Polyoxycarboxylic acids have the highest calcium ion sequestering ability throughout the entire range. Other monomers that do not affect the water solubility, such as acrylamide and acrylamine, can also be used if necessary.
本発明による生成物は洗剤のビルダー、スクール付着防
止剤などに使用できる。The products according to the invention can be used as builders for detergents, anti-fouling agents, etc.
以下実施例によって本発明を説明するが、これらによっ
て本発明を限定するものではない。The present invention will be explained below with reference to Examples, but the present invention is not limited to these.
なお例中、部、％は重量基準を示す。In the examples, parts and % are based on weight.
実施例１
攪拌器、温度計、還流冷却器、滴下ロートおよびＮ２導
入管を付し几２１５ツロセパラブルフラスコにアリルア
ルコール５８部、水２５０！、６０％過酸化水素水１５
０部を入れＮ２置換を行ないつつ内容物の温度を９０℃
まで上昇させあ次に内容物の温度を９０±５℃に保ちな
がらアクリルｒＲ２８８部を３時間で滴下し、その温度
でさらに２時間熟成した。Example 1 In a 215-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and N2 inlet tube, 58 parts of allyl alcohol and 250 parts of water were placed. , 60% hydrogen peroxide solution 15
0 part was added and the temperature of the contents was raised to 90℃ while performing N2 substitution.
Then, while maintaining the temperature of the contents at 90±5° C., 288 parts of acrylic rR was added dropwise over 3 hours, and the mixture was further aged at that temperature for 2 hours.
上記共重合反り液に２５％水酸化ナトリウム水溶液６４
０部を加え、７０℃で２時間中和およびケン化反応ｔお
こなつ九。25% sodium hydroxide aqueous solution 64 to the above copolymerization liquid
Add 0 parts and conduct neutralization and saponification reaction at 70°C for 2 hours.
この反応粗液中のアリルアルコール量およびアクリル酸
量を分析し九らアリルアルコールが９ｐｐｍ、アクリル
酸が６６ ｐｐｒｒｒでありそれぞれほとんど反応して
いることが判明し、未反応モノマーの回収の必要はなか
った。The amount of allyl alcohol and acrylic acid in this reaction crude liquid was analyzed and it was found that 9 ppm of allyl alcohol and 66 pprrr of acrylic acid were mostly reacted, so there was no need to recover unreacted monomers. Ta.
実施例２
攪拌器、温度計、還流冷却器、滴下ロート及びＮ２４人
管を付した２４５ツロセパラプルフラスコにアリルアル
コール５８部、水１２９部、６０％過酸化水素水１００
部を入れＮ２置換を行ないつつ内容物の温度上９０℃ま
で上昇させ九次に内容物の温度ｔ−９０±５℃に保ちな
がらアクリルｒＲ２１６部ｔ−３時間で滴下し、その温
度で更に２時間熟成した。上記共重合反応液に２５％水
酸化ナトリウム水浴液４８０部を加え、７０℃で２時間
中和及びケン化反応金行つ友。Example 2 58 parts of allyl alcohol, 129 parts of water, and 100 parts of 60% hydrogen peroxide solution were added to a 245-turosene parallel flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and N24 tube.
216 parts of acrylic rR was added dropwise at t-3 hours while the temperature of the contents was maintained at t-90±5°C. Time aged. 480 parts of a 25% sodium hydroxide water bath solution was added to the above copolymerization reaction solution, and a neutralization and saponification reaction was carried out at 70°C for 2 hours.
この反応粗液中のアリルアルコールおよびアクリルｅｔ
分析したらアリルアルコールが１８ｐｐｍ ｓアクリル
酸が１２７ ｐｐｍでありそれぞれほとんど反応してい
ることがわかり未反応モノマーの回収の必要はなかった
。Allyl alcohol and acrylic acid in this reaction crude liquid
Analysis revealed that allyl alcohol was 18 ppm and acrylic acid was 127 ppm, indicating that almost all of them had reacted, and there was no need to recover unreacted monomers.
比較例１
実施例１と同様の反応器にアリルアルコール５２２部、
水２１１．５部、６０％過酸化水素水６０部を仕込み、
Ｎ２気°流中で９０℃に加熱し九次に内容物の温度ｔ−
９０±５℃に保ちながらアクリル酸５２４部を５時間で
滴下し、その温度でさらに２時間熟成した。Comparative Example 1 In a reactor similar to Example 1, 522 parts of allyl alcohol,
Prepare 211.5 parts of water and 60 parts of 60% hydrogen peroxide solution,
Heated to 90°C in a N2 stream and then lowered the temperature of the contents to t-
While maintaining the temperature at 90±5° C., 524 parts of acrylic acid was added dropwise over 5 hours, and the mixture was further aged at that temperature for 2 hours.
上記共重合反応液に２５％水酸化ナトリウム水浴液７２
０部を加え７０℃で２時間中和およびケン化反応をおこ
なった。Add 72% sodium hydroxide water bath solution to the above copolymerization reaction solution.
0 part was added and neutralization and saponification reactions were carried out at 70°C for 2 hours.
この反応粗液中のアリルアルコールおよ０’７クリル酸
を分析したところアリルアルコールが１７．５ ｗｚ％
、アクリル酸が４８ ｐｐｍでアリルアルコールは仕込
んだ童の５９．１％しか反応しておらず、未反応アリル
アルコールの回収が必要であった。Analysis of allyl alcohol and 0'7 acrylic acid in this reaction crude liquid revealed that allyl alcohol was 17.5 wz%.
, acrylic acid was 48 ppm, and only 59.1% of the allyl alcohol reacted with the sample, making it necessary to recover unreacted allyl alcohol.
Claims (1)
ラジカル共重合させる際に、ラジカル開始剤として過酸
化水素をアリルアルコールとアクリル酸またはメタクリ
ル酸の合計モノマーに対して１０〜３０重量％添加する
ことを特徴とするポリオキシカルボン酸の製造方法。When radical copolymerizing allyl alcohol and acrylic acid or methacrylic acid, hydrogen peroxide is added as a radical initiator in an amount of 10 to 30% by weight based on the total monomers of allyl alcohol and acrylic acid or methacrylic acid. A method for producing polyoxycarboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17524885A JPS6236408A (en) | 1985-08-09 | 1985-08-09 | Production of polyhydroxycarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17524885A JPS6236408A (en) | 1985-08-09 | 1985-08-09 | Production of polyhydroxycarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6236408A true JPS6236408A (en) | 1987-02-17 |
| JPH0535726B2 JPH0535726B2 (en) | 1993-05-27 |
Family
ID=15992849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17524885A Granted JPS6236408A (en) | 1985-08-09 | 1985-08-09 | Production of polyhydroxycarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6236408A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523851A (en) * | 1978-08-09 | 1980-02-20 | Hitachi Ltd | Air conditioner |
| JPS5739246A (en) * | 1980-08-15 | 1982-03-04 | Teijin Ltd | Production of extensible fabric having cotton like feeling |
| JPS5869206A (en) * | 1981-10-20 | 1983-04-25 | Nippon Paint Co Ltd | Production of hydroxyl group-terminated acrylic polymer |
-
1985
- 1985-08-09 JP JP17524885A patent/JPS6236408A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523851A (en) * | 1978-08-09 | 1980-02-20 | Hitachi Ltd | Air conditioner |
| JPS5739246A (en) * | 1980-08-15 | 1982-03-04 | Teijin Ltd | Production of extensible fabric having cotton like feeling |
| JPS5869206A (en) * | 1981-10-20 | 1983-04-25 | Nippon Paint Co Ltd | Production of hydroxyl group-terminated acrylic polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0535726B2 (en) | 1993-05-27 |
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