JPS61126053A - Aromatic fluorine-containing monomer - Google Patents
Aromatic fluorine-containing monomerInfo
- Publication number
- JPS61126053A JPS61126053A JP24454684A JP24454684A JPS61126053A JP S61126053 A JPS61126053 A JP S61126053A JP 24454684 A JP24454684 A JP 24454684A JP 24454684 A JP24454684 A JP 24454684A JP S61126053 A JPS61126053 A JP S61126053A
- Authority
- JP
- Japan
- Prior art keywords
- containing monomer
- aromatic fluorine
- fluorine
- aromatic
- present
- 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
Abstract
Description
【発明の詳細な説明】
本発明は重合性を有する新規な芳香族フッ素含有単量体
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel aromatic fluorine-containing monomer having polymerizability.
本発明の芳香族フッ素含有単量体はフッ素化された芳香
環を含有し、従来のフッ素含有単量体にない特徴を有す
るものである。本発明の芳香族フッ素含有単量体を用い
た重合体は、塗料、繊維処理剤、離型剤、樹脂改質剤、
光フアイバー保護剤、選択性透過膜等の用途に用いられ
て優れた効果を発揮するものである。The aromatic fluorine-containing monomer of the present invention contains a fluorinated aromatic ring and has characteristics not found in conventional fluorine-containing monomers. Polymers using the aromatic fluorine-containing monomer of the present invention can be used in coatings, fiber treatment agents, mold release agents, resin modifiers,
It exhibits excellent effects when used in applications such as optical fiber protectants and selectively permeable membranes.
従来、重合性を有するフッ素含有単量体はフッ素置換オ
レフィン類やフッ素置換アルキル基を有するアクリレー
ト又はメタクリレート類等多数知られており、これらを
用いた重合体は、その特性を利用して種々の用途に使用
されているが、一方では成形温度が高く、加工性が不充
分であることや密着性が悪いため、各種処理剤としての
耐久性が不充分であるなどの欠点を有しており、これら
の改良が望まれているものである。Conventionally, many polymerizable fluorine-containing monomers have been known, such as fluorine-substituted olefins and acrylates or methacrylates having fluorine-substituted alkyl groups, and polymers using these can be used in various ways by taking advantage of their properties. Although it is used for various purposes, it has disadvantages such as high molding temperature, insufficient processability, and poor adhesion, so it is not durable enough as a processing agent. , these improvements are desired.
本発明はこれらの問題を解決する一手段を提供するもの
である。The present invention provides a means to solve these problems.
本出願人は先にペンタフルオロベンゾニトリルの製造方
法を開発し出願したが、本発明者らは、このペンタフル
オロベンゾニトリルを公知の方法で加水分解して得られ
るペンタフルオロ安息香酸の用途について検討した結果
、取扱いが容易で、重合反応性及び他の単量体との共重
合性の良好な新規の芳香族フッ素含有単量体が得られる
ことを見い出し、本発明を完成した。The present applicant had previously developed and applied for a method for producing pentafluorobenzonitrile, and the present inventors have investigated the use of pentafluorobenzoic acid obtained by hydrolyzing this pentafluorobenzonitrile using a known method. As a result, it was discovered that a new aromatic fluorine-containing monomer that is easy to handle and has good polymerization reactivity and copolymerizability with other monomers can be obtained, and the present invention was completed.
即ち、本発明は一般式
で表わされる芳香族フッ素含有単量体を提供するもので
ある。That is, the present invention provides an aromatic fluorine-containing monomer represented by the general formula.
本発明の芳香族フッ素含有単量体の製造方法としては、
例えばペンタフルオロ安息香酸とグリシジルメタクリレ
ートとを付加反応させる方法が挙げられる。The method for producing the aromatic fluorine-containing monomer of the present invention includes:
For example, there is a method in which pentafluorobenzoic acid and glycidyl methacrylate are subjected to an addition reaction.
ペンタフルオロ安息香酸とグリシジルメタクリレートの
付加反応は以下のように行うことができる。即ち、ペン
タフルオロ安息香酸及びグリシジルメタクリレートを必
要に応じてメチル ″エテルケトン、トルエン等の溶媒
と混合し、撹拌下に加熱することにより、目的物である
芳香族フッ素含有単量体を得ることができる。反応温度
は普通４０〜１５０℃の温度で行われる。The addition reaction between pentafluorobenzoic acid and glycidyl methacrylate can be carried out as follows. That is, the target aromatic fluorine-containing monomer can be obtained by mixing pentafluorobenzoic acid and glycidyl methacrylate with a solvent such as methyl ether ketone or toluene as necessary and heating the mixture with stirring. The reaction temperature is generally 40 to 150°C.
反応に際しては、トリエチルアミン、塩化ベンジルトリ
エチルアンモニウム等の反応促進剤、ハイドロキノ／、
メトキノン等の重合抑制剤等を適宜使用すると効果的で
ある。During the reaction, a reaction accelerator such as triethylamine, benzyltriethylammonium chloride, hydroquino/,
It is effective to appropriately use a polymerization inhibitor such as methoquinone.
本発明の芳香族フッ素含有単量体は、溶媒を取シ除いて
精製した状態あるいは溶媒に溶解したままの状態で、必
要に応じて他の単量体成分と併用し、塊状重合、浴液重
合、乳化重合等従来公知の重合方法によって芳香族フッ
素含有重合体に変換されて、種々の用途に用いられる。The aromatic fluorine-containing monomer of the present invention can be purified by removing the solvent or dissolved in the solvent, and can be used in combination with other monomer components as necessary to carry out bulk polymerization, bath solution, etc. It is converted into an aromatic fluorine-containing polymer by conventionally known polymerization methods such as polymerization and emulsion polymerization, and is used for various purposes.
例えば、塗料、繊維処理剤、離型剤、樹脂改質剤、光フ
アイバー保護剤、選択性透過膜等に用いられて優れた性
能を発揮する。For example, it is used in paints, fiber treatment agents, mold release agents, resin modifiers, optical fiber protection agents, selectively permeable membranes, etc., and exhibits excellent performance.
以下に実施例をあげて本発明を具体的に説明するが、こ
れらにより本発明は何ら限定を受けるものではない。尚
、例中の部はすべて重量部を、チはすべて重量％を示す
ものとする。The present invention will be specifically explained below with reference to Examples, but the present invention is not limited in any way by these examples. In addition, all parts in the examples are parts by weight, and all ``chi'' are % by weight.
実施例１
温度計、還流冷却器、空気導入管および撹拌機を備えた
４ツロフラスコに、ペンタフルオロ安息香酸４２４部、
グリシジルメタクリレート２８４部、塩化ベンジルトリ
エチルアンモニウム９部、ハイドロキノン０．１４部及
びトルエン７０８部を装入し、９０℃に加熱して均一溶
液とした。空気を吹き込みながら反応温度を９０℃に維
持し、１０時間撹拌を続けた。Example 1 424 parts of pentafluorobenzoic acid,
284 parts of glycidyl methacrylate, 9 parts of benzyltriethylammonium chloride, 0.14 parts of hydroquinone, and 708 parts of toluene were charged and heated to 90°C to form a homogeneous solution. The reaction temperature was maintained at 90° C. while blowing air, and stirring was continued for 10 hours.
反応液の酸価は３．９でペンタフルオロ安息香酸の反応
率は９５％であった。反応終了後、２チ水酸化ナトリウ
ム水溶液１０００部を加えて振とう後静置し、２層に分
離したうちの油層を分液した。油層を脱イオン水で洗浄
したのち無水硫酸ナトリウムで乾燥後、減圧下でトルエ
ンを留去し、本発明の芳香族フッ素含有単量体６０２部
を得た。The acid value of the reaction solution was 3.9, and the reaction rate of pentafluorobenzoic acid was 95%. After the reaction was completed, 1000 parts of an aqueous solution of di-sodium hydroxide was added, and after shaking, the mixture was allowed to stand, and the oil layer was separated into two layers. After washing the oil layer with deionized water and drying over anhydrous sodium sulfate, toluene was distilled off under reduced pressure to obtain 602 parts of the aromatic fluorine-containing monomer of the present invention.
下記に得られた単量体の分析結果を示す。The analysis results of the obtained monomer are shown below.
■元素分析
Ｃ（支）） Ｈ（％） Ｆ悟）
分析値 ４７，５２ ３．０８ ２６．２１理論値 ４
７．４７ ３．１３ ２６．８２■ 赤外吸収スペクト
ル（ｎｅａ ｔ ）３４６０ ｃｍ−’ （’０−
Ｈ）１７４０ ｃｍ−’ （’Ｃ＝Ｏ）１６５０
ｃｍ”（νｃ＝ｃ ）
１５２５、１５００ ｃｔａ ’ （シＦ−ベンゼン核
ｃ＝ｃ ）尚、赤外吸収スペクトルは第１図に示す。■Elemental analysis C (support)) H (%) F Satoru) Analytical value 47,52 3.08 26.21 Theoretical value 4
7.47 3.13 26.82 ■ Infrared absorption spectrum (neat) 3460 cm-'('0-
H) 1740 cm-'('C=O) 1650
cm'' (vc=c) 1525, 1500 cta' (SiF-benzene nucleus c=c) The infrared absorption spectrum is shown in FIG.
■ ＩＨＮＭＲ（溶媒 ＣＤＣ１５，内部標準物質’Ｉ
’ＭＳ）δ＝２．０ＩＰＦＷ（ｓｉｎｇｌｅｔ、 ３
Ｈ）δ＝４．２２〜４．’１５ｐｐｍ （ｍｕＨｉｐｌ
ｅｔ、 ６Ｈ）δ＝５．８１ ｐｐｍ （ｓｉｎｇｌ
ｅｔ、 Ｉ Ｈ）δ＝６．１５ｐｐｍ （ｓｉｎｇｌ
ｅｔ、 ＩＨ）■ １９Ｆ ＮＭＲ（溶媒 ＣＤＣｌ
５ ｐ外部標準物質 トリフルオロ酢酸）
δ＝ ６２．１ ｐａｎ （ｍｕｌｔｉｐｌｅｔ、
２Ｈ）δ＝ −７２，６ＰＰｍ （ｍｕｌｔ １ｐｉ
ｅｔ、 Ｉ Ｈ）δ＝ −８４，８ｐｐｍ （ｍｕｌ
ｔｉｐｌｅｔ、 ２Ｈ）■ IHNMR (solvent CDC15, internal standard substance 'I'
'MS) δ=2.0IPFW(singlet, 3
H) δ=4.22-4. '15ppm (muHipl
et, 6H) δ=5.81 ppm (singl
et, IH) δ=6.15ppm (singl
et, IH) ■ 19F NMR (solvent CDCl
5 p external standard material trifluoroacetic acid) δ = 62.1 pan (multiplet,
2H) δ= -72,6PPm (mult 1pi
et, I H) δ = −84,8 ppm (mul
tiplet, 2H)
第１図は実施例１で得られた芳香族フッ素含有単量体の
赤外吸収スペクトル、第２図は実施例１で原料として使
用したペンタフルオロ安息香酸の赤外吸収スペクトル（
ＫＢｒ）、第３図は実施例１で原料として使用したグリ
シジルメタクリレートの赤外吸収スペクトル（ｎｅａｔ
）である。
手 続 補 正 書 （方式）昭和６０年４
月２４日Figure 1 shows the infrared absorption spectrum of the aromatic fluorine-containing monomer obtained in Example 1, and Figure 2 shows the infrared absorption spectrum of pentafluorobenzoic acid used as a raw material in Example 1 (
KBr), Figure 3 shows the infrared absorption spectrum (neat
). Procedures Amendment (Method) April 1985
24th of the month
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24454684A JPS61126053A (en) | 1984-11-21 | 1984-11-21 | Aromatic fluorine-containing monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24454684A JPS61126053A (en) | 1984-11-21 | 1984-11-21 | Aromatic fluorine-containing monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61126053A true JPS61126053A (en) | 1986-06-13 |
Family
ID=17120305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24454684A Pending JPS61126053A (en) | 1984-11-21 | 1984-11-21 | Aromatic fluorine-containing monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61126053A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01170607A (en) * | 1987-12-25 | 1989-07-05 | Sanyo Chem Ind Ltd | Modifying agent and modification |
-
1984
- 1984-11-21 JP JP24454684A patent/JPS61126053A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01170607A (en) * | 1987-12-25 | 1989-07-05 | Sanyo Chem Ind Ltd | Modifying agent and modification |
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