JPH07247314A - Production of mercapto-group-containing polymer - Google Patents
Production of mercapto-group-containing polymerInfo
- Publication number
- JPH07247314A JPH07247314A JP3872294A JP3872294A JPH07247314A JP H07247314 A JPH07247314 A JP H07247314A JP 3872294 A JP3872294 A JP 3872294A JP 3872294 A JP3872294 A JP 3872294A JP H07247314 A JPH07247314 A JP H07247314A
- Authority
- JP
- Japan
- Prior art keywords
- group
- containing polymer
- polymer
- compd
- reaction product
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- General 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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、メルカプト基含有ポ
リマーの製法に関するものである。更に詳しくは、分子
中に反応性の高いアミノ基とメルカプト基を有し、エポ
キシ樹脂硬化剤、キレート剤、防錆剤、金属表面処理
剤、酸化防止剤、加硫剤、シーリング剤等に有用なポリ
マーを簡便に製造する方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing a mercapto group-containing polymer. More specifically, it has a highly reactive amino group and mercapto group in the molecule and is useful as an epoxy resin curing agent, a chelating agent, a rust preventive, a metal surface treating agent, an antioxidant, a vulcanizing agent, a sealing agent, etc. The present invention relates to a method for easily producing a simple polymer.
【０００２】[0002]
【従来の技術】メルカプト化合物を合成する反応として
は、ハロゲン化物またはジアゾニウム化合物に硫化水素
ナトリウムを作用させる方法、グリニヤール試薬と硫黄
とを反応させる方法、炭素−炭素二重結合に硫化水素を
付加させる方法、有機スルホニルクロライドやジスルフ
ィドを還元する方法等が知られている。また、カルボキ
シル基含有ポリマーとエチレンサルファイドとを反応さ
せる方法も知られている。2. Description of the Related Art As a reaction for synthesizing a mercapto compound, a method of reacting a halide or a diazonium compound with sodium hydrogen sulfide, a method of reacting a Grignard reagent with sulfur, and adding hydrogen sulfide to a carbon-carbon double bond. Methods, methods of reducing organic sulfonyl chlorides and disulfides, and the like are known. Also known is a method of reacting a carboxyl group-containing polymer with ethylene sulfide.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前者の
方法をポリマーに適用する際、工業的にポリマー原料を
得ることが難しいという問題があり、後者の反応は、収
率が低く工業的に実用性があるとは言い難い。However, when the former method is applied to a polymer, there is a problem that it is difficult to industrially obtain a polymer raw material, and the latter reaction has a low yield and is industrially practical. It is hard to say that there is.
【０００４】[0004]
【課題を解決するための手段】上記の課題を解決するた
めにこの発明は、アジリジン化合物とチイラン化合物と
の反応生成物をカルボキシル基含有ポリマーと反応させ
ることを特徴とするメルカプト基含有ポリマーの製法を
提供する。In order to solve the above problems, the present invention provides a method for producing a mercapto group-containing polymer, which comprises reacting a reaction product of an aziridine compound and a thiirane compound with a carboxyl group-containing polymer. I will provide a.
【０００５】この発明において使用されるアジリジン化
合物は、一般式（１）：The aziridine compound used in the present invention has the general formula (1):
【０００６】[0006]
【化３】 [Chemical 3]
【０００７】（但し、一般式（１）において、Ｒ1、
Ｒ2、Ｒ3及びＲ4は水素原子または炭素数１〜４のアル
キル基を表し、それぞれ同一または異なっていても良
い。）で表されるものであり、代表的なものとして、エ
チレンイミン、プロピレンイミン、イソブチレンイミン
等が挙げられる。(However, in the general formula (1), R 1 ,
R 2 , R 3 and R 4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different. ), And representative examples thereof include ethyleneimine, propyleneimine, and isobutyleneimine.
【０００８】この発明において使用されるチイラン化合
物は、一般式（２）：The thiirane compound used in the present invention has the general formula (2):
【０００９】[0009]
【化４】 [Chemical 4]
【００１０】（但し、一般式（２）において、Ｒ5、
Ｒ6、Ｒ7及びＲ8は水素原子、アルキル基または芳香族
基を表し、それぞれ同一または異なっていても良い。）
で表されるものであり、代表的なものとして、エチレン
サルファイド、プロピレンサルファイド、イソブチレン
サルファイド、スチレンサルファイド等が挙げられる。(However, in the general formula (2), R 5 ,
R 6 , R 7 and R 8 represent a hydrogen atom, an alkyl group or an aromatic group, and may be the same or different. )
And ethylene sulfide, propylene sulfide, isobutylene sulfide, styrene sulfide, etc. are representative.
【００１１】上記のアジリジン化合物とチイラン化合物
の反応生成物（Ａ）を得る際には、トルエン、キシレ
ン、テトラヒドロフラン、ジオキサン、シクロヘキサン
等の溶媒を釜に仕込み、該溶媒中にアジリジン化合物と
チイラン化合物の一方または両方を滴下するか一括に添
加するかして、室温ないし１００℃程度の温度で反応さ
せれば良い。なお、反応生成物（Ａ）を得る反応を、模
式で表わすと、以下の通りである。When the reaction product (A) of the aziridine compound and the thiirane compound is obtained, a solvent such as toluene, xylene, tetrahydrofuran, dioxane or cyclohexane is charged into a kettle and the aziridine compound and the thiirane compound are added to the solvent. One or both of them may be dropped or added all at once, and the reaction may be performed at room temperature to about 100 ° C. The reaction for obtaining the reaction product (A) is schematically shown below.
【００１２】[0012]
【化５】 [Chemical 5]
【００１３】この発明において使用されるカルボキシル
基含有ポリマーは、ポリマー側鎖または末端にカルボキ
シル基又はその塩を有するポリマーであれば特に制限は
なく、例えば、ポリ（アクリル酸）、ポリ（アクリル酸
ソーダ）、ポリ（アクリル酸亜鉛）、アクリル酸とアク
リル酸メチル、アクリル酸エチル、アクリル酸ブチル、
アクリル酸２−エチルヘキシル、メタクリル酸メチル、
メタクリル酸ブチル、スチレン、アクリロニトリル、ア
クリルアミド、塩化ビニル等の共重合性モノマーの少な
くとも一種との共重合体、飽和ポリエステル樹脂、不飽
和ポリエステル樹脂、カルボキシル基変性ポリウレタン
樹脂等が挙げられる。これらのカルボキシル基含有ポリ
マー中のカルボキシル基の量は、酸価で５ないし１００
０ｍｇＫＯＨ／ｇ−ｓｏｌｉｄのものが好ましい。酸価
が５ｍｇＫＯＨ／ｇ−ｓｏｌｉｄ未満では、得られるメ
ルカプト基含有ポリマーのメルカプト基含有量が実質的
に不足し、メルカプト基の特性が発現しない傾向にあ
る。また酸価が１０００ｍｇＫＯＨ／ｇ−ｓｏｌｉｄを
超える場合は、メルカプト基を導入した際にカルボキシ
ル基含有ポリマーの特性が失われる傾向にある。The carboxyl group-containing polymer used in the present invention is not particularly limited as long as it has a carboxyl group or a salt thereof at the polymer side chain or terminal, and examples thereof include poly (acrylic acid) and poly (sodium acrylate). ), Poly (zinc acrylate), acrylic acid and methyl acrylate, ethyl acrylate, butyl acrylate,
2-ethylhexyl acrylate, methyl methacrylate,
Examples thereof include copolymers with at least one copolymerizable monomer such as butyl methacrylate, styrene, acrylonitrile, acrylamide, and vinyl chloride, saturated polyester resins, unsaturated polyester resins, and carboxyl group-modified polyurethane resins. The amount of the carboxyl group in these carboxyl group-containing polymers is 5 to 100 in terms of acid value.
Those having 0 mg KOH / g-solid are preferred. When the acid value is less than 5 mgKOH / g-solid, the mercapto group content of the obtained mercapto group-containing polymer is substantially insufficient, and the mercapto group characteristics tend not to be exhibited. When the acid value exceeds 1000 mgKOH / g-solid, the characteristics of the carboxyl group-containing polymer tend to be lost when the mercapto group is introduced.
【００１４】上記カルボキシル基含有ポリマーに反応生
成物（Ａ）を反応させる際には、例えばカルボキシル基
含有ポリマーのみまたは該ポリマーの水溶液や有機溶剤
溶液を釜に仕込み、反応生成物（Ａ）を滴下しながら、
室温〜１００℃程度の温度で反応させれば良い。なお、
反応生成物（Ａ）を得る反応を、模式で表わすと、以下
の通りである。When the reaction product (A) is reacted with the carboxyl group-containing polymer, for example, only the carboxyl group-containing polymer or an aqueous solution or organic solvent solution of the polymer is charged into a kettle and the reaction product (A) is dropped. while doing,
The reaction may be performed at a temperature of about room temperature to 100 ° C. In addition,
The reaction for obtaining the reaction product (A) is schematically shown below.
【００１５】[0015]
【化６】 [Chemical 6]
【００１６】ポリマーにアミノ基とメルカプト基が導入
されたことは、例えば赤外線吸光分析により、２５４０
ｃｍ-1付近のＳＨ基の吸収及び３３００ｃｍー1付近のＮ
Ｈ基の吸収により確認することができる。The fact that an amino group and a mercapto group have been introduced into the polymer can be confirmed by, for example, infrared absorption spectrometry.
Absorption of SH group near cm-1 and N near 3300 cm-1
It can be confirmed by the absorption of H group.
【００１７】[0017]
【作用】この発明は、分子中に反応性の高いアミノ基と
メルカプト基を有するポリマーを、アジリジン化合物と
チイラン化合物との反応生成物（Ａ）を利用し、簡便な
方法で製造する方法を提供する。得られたメルカプト基
含有ポリマーは、エポキシ樹脂硬化剤、キレート剤、防
錆剤、金属表面処理剤、酸化防止剤、加硫剤、シーリン
グ剤等に有用である。The present invention provides a method for producing a polymer having a highly reactive amino group and a mercapto group in a molecule by a simple method using a reaction product (A) of an aziridine compound and a thiirane compound. To do. The obtained mercapto group-containing polymer is useful as an epoxy resin curing agent, a chelating agent, a rust preventive, a metal surface treating agent, an antioxidant, a vulcanizing agent, a sealing agent and the like.
【００１８】[0018]
【実施例】以下、実施例および比較例を挙げてこの発明
を具体的に説明するが、この発明がこれらに限定される
ものではない。EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.
【００１９】実施例１ 攪拌機、還流冷却器、窒素導入管、温度計および滴下ロ
ートを備えたフラスコに、エチレンイミン１７０．７ｇ
及びシクロヘキサン２５０ｇを仕込み、窒素気流下混合
した。次いでエチレンサルファイド２３８．３ｇを仕込
み、徐々に加熱還流させ４時間反応させた。反応終了
後、減圧にて溶媒を除去し、透明液体の反応生成物
（１）３９８．１ｇを得た。得られた反応生成物（１）
は、赤外線吸光分析で２５４５ｃｍー1にＳＨ基の吸収が
認められ、又３３００ｃｍー1付近のＮＨ基の吸収がほと
んどないことより、メルカプトエチルアジリジンが得ら
れたことが判った。Example 1 170.7 g of ethyleneimine was placed in a flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube, a thermometer and a dropping funnel.
And 250 g of cyclohexane were charged and mixed under a nitrogen stream. Next, 238.3 g of ethylene sulfide was charged, and the mixture was gradually heated to reflux and reacted for 4 hours. After completion of the reaction, the solvent was removed under reduced pressure to obtain 398.1 g of a reaction product (1) as a transparent liquid. Obtained reaction product (1)
Infrared absorption analysis showed that the SH group had an absorption at 2545 cm-1, and the NH group at 3300 cm-1 had almost no absorption. Thus, it was found that mercaptoethylaziridine was obtained.
【００２０】攪拌機、還流冷却器、窒素導入管、温度計
および滴下ロートを備えた別のフラスコに、６５％ポリ
アクリル酸水溶液（アルドリッチ製、平均分子量約２０
００）７０ｇ及び脱イオン水２８．６ｇを仕込み、窒素
置換した。４０℃に加熱した後、反応生成物（１）３
５．６ｇを１時間かけて滴下し、反応させた。滴下終了
後１時間熟成して、濁った反応生成物溶液１３３．５ｇ
を得た。得られた生成物は赤外線吸光分析で２５４０ｃ
ｍ-1にＳＨ基の吸収、３２９０ｃｍー1にＮＨ基の吸収が
認められ、アミノ基とメルカプト基が導入されたことが
判った。In a separate flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel, a 65% polyacrylic acid aqueous solution (made by Aldrich, average molecular weight of about 20) was added.
00) 70 g and deionized water 28.6 g were charged and the atmosphere was replaced with nitrogen. After heating to 40 ° C., the reaction product (1) 3
5.6 g was added dropwise over 1 hour to react. Aged for 1 hour after completion of dropping, and 133.5 g of cloudy reaction product solution
Got The obtained product is 2540c by infrared absorption spectrometry.
Absorption of SH group at m-1 and absorption of NH group at 3290 cm-1 were observed, and it was found that amino group and mercapto group were introduced.
【００２１】比較例１ 攪拌機、還流冷却器、窒素導入管、温度計および滴下ロ
ートを備えたフラスコに、６５％ポリアクリル酸水溶液
（アルドリッチ製、平均分子量約２０００）７０ｇ及び
脱イオン水２８．６ｇを仕込み、窒素置換した。４０℃
に加熱した後、実施例１の反応生成物（１）と同モルに
相当するエチレンサルファイド２０．７ｇを１時間かけ
て滴下し、反応させた。滴下終了後１時間熟成して、ワ
ックス状の反応生成物溶液１１８．８ｇを得た。得られ
た生成物の赤外線吸光分析の結果、２５４０ｃｍ-1付近
に吸収はなく、メルカプト基はほとんど導入されていな
いことが判った。Comparative Example 1 In a flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel, 70 g of 65% polyacrylic acid aqueous solution (manufactured by Aldrich, average molecular weight of about 2000) and deionized water 28.6 g. Was charged and the atmosphere was replaced with nitrogen. 40 ° C
After heating to 2 ° C., 20.7 g of ethylene sulfide corresponding to the same mole as the reaction product (1) of Example 1 was added dropwise over 1 hour to cause a reaction. After completion of the dropping, the mixture was aged for 1 hour to obtain 118.8 g of a wax-like reaction product solution. As a result of infrared absorption analysis of the obtained product, it was found that there was no absorption around 2540 cm -1, and that almost no mercapto group was introduced.
【００２２】[0022]
【発明の効果】上記実施例及び比較例から明らかなよう
に、この発明の製法によれば、簡便にアミノ基とメルカ
プト基を有するポリマーを合成することができる。As is clear from the above Examples and Comparative Examples, according to the production method of the present invention, a polymer having an amino group and a mercapto group can be easily synthesized.
Claims (1)
は水素原子または炭素数１〜４のアルキル基を表し、そ
れぞれ同一または異なっていても良い。）で表されるア
ジリジン化合物と、一般式（２）： 【化２】 （但し、一般式（２）において、Ｒ5、Ｒ6、Ｒ7及びＲ8
は水素原子、アルキル基または芳香族基を表し、それぞ
れ同一または異なっていても良い。）で表されるチイラ
ン化合物との反応生成物（Ａ）を、カルボキシル基含有
ポリマーと反応させることを特徴とするメルカプト基含
有ポリマーの製法。1. General formula (1): (However, in the general formula (1), R 1 , R 2 , R 3 and R 4
Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different. ) And an aziridine compound represented by the general formula (2): (However, in the general formula (2), R 5 , R 6 , R 7 and R 8
Represents a hydrogen atom, an alkyl group or an aromatic group, and may be the same or different. ) The reaction product (A) with a thiirane compound represented by the formula (1) is reacted with a carboxyl group-containing polymer to produce a mercapto group-containing polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3872294A JPH07247314A (en) | 1994-03-09 | 1994-03-09 | Production of mercapto-group-containing polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3872294A JPH07247314A (en) | 1994-03-09 | 1994-03-09 | Production of mercapto-group-containing polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07247314A true JPH07247314A (en) | 1995-09-26 |
Family
ID=12533223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3872294A Pending JPH07247314A (en) | 1994-03-09 | 1994-03-09 | Production of mercapto-group-containing polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07247314A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007217482A (en) * | 2006-02-15 | 2007-08-30 | Tokuyama Corp | Polymer-coated inorganic particle |
| JP2009001808A (en) * | 2002-08-29 | 2009-01-08 | Nippon Shokubai Co Ltd | Sulfur-containing unsaturated carboxylic acid polymer and use thereof |
-
1994
- 1994-03-09 JP JP3872294A patent/JPH07247314A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009001808A (en) * | 2002-08-29 | 2009-01-08 | Nippon Shokubai Co Ltd | Sulfur-containing unsaturated carboxylic acid polymer and use thereof |
| JP2007217482A (en) * | 2006-02-15 | 2007-08-30 | Tokuyama Corp | Polymer-coated inorganic particle |
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