JPS6146003B2 - - Google Patents
Info
- Publication number
- JPS6146003B2 JPS6146003B2 JP55147433A JP14743380A JPS6146003B2 JP S6146003 B2 JPS6146003 B2 JP S6146003B2 JP 55147433 A JP55147433 A JP 55147433A JP 14743380 A JP14743380 A JP 14743380A JP S6146003 B2 JPS6146003 B2 JP S6146003B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- surfactant
- fluorine
- polyperfluoroether
- latex
- 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.)
- Expired
Links
- 239000004094 surface-active agent Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- 150000007942 carboxylates Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- -1 alkali metal salt Chemical class 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 31
- 239000004816 latex Substances 0.000 description 21
- 229920000126 latex Polymers 0.000 description 21
- 229920001577 copolymer Polymers 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- FPDZOFFZSWSOSL-UHFFFAOYSA-N trifluoromethoxyethene Chemical compound FC(F)(F)OC=C FPDZOFFZSWSOSL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は、フツ素含有単量体の重合方法に関す
る。更に詳しくは、フルオロカーボン系界面活性
剤の存在下に行われるフツ素含有単量体の重合方
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing fluorine-containing monomers. More specifically, the present invention relates to a method for polymerizing a fluorine-containing monomer in the presence of a fluorocarbon surfactant.
フツ素含有単量体を乳化重合法、けん濁重合法
などによつてラジカル重合させる場合、一般に乳
化剤としてのフルオロカーボン系界面活性剤の存
在下で重合反応が行われる。通常用いられるフル
オロカーボン系界面活性剤は、例えば下記のよう
なパーフルオロアルキル基を有するカルボン酸塩
（特公昭36−11985号公報参照）またはスルホン酸
塩であり、塩の形としてはアルカリ金属塩または
アンモニウム塩が用いられる。 When fluorine-containing monomers are radically polymerized by emulsion polymerization, suspension polymerization, or the like, the polymerization reaction is generally carried out in the presence of a fluorocarbon surfactant as an emulsifier. Commonly used fluorocarbon surfactants are, for example, carboxylic acid salts (see Japanese Patent Publication No. 36-11985) or sulfonic acid salts having a perfluoroalkyl group as shown below, and in the form of salts, alkali metal salts or Ammonium salts are used.
CF3（CF2）8COONa；
CF3（CF2）8COONH4
しかしながら、これらの界面活性剤の存在下に
フツ素含有単量体のラジカル重合反応を行なう
と、得られる重合体ラテツクスの安定性が悪いば
かりではなく、重合速度も遅いという問題点がみ
られる。例えば、前記の如きカルボン酸塩を用い
た場合には、重合速度の点では問題がないもの
の、特に生成重合体ラテツクスの安定性に問題が
あり、実用的な濃度である固形分濃度35％程度で
もラテツクス状とはならず、クリーム状を呈する
ようになる。より広く用いられている前記の如き
スルホン酸塩の場合には、特に重合速度への影響
が大きく、界面活性剤を高濃度で用いたときに重
合速度の減少が著しい。また、生成する重合体ラ
テツクスはそれ自体安定であるが、それを塗料な
どに用いるために増粘剤を加えて粘度調節を行な
うと、フロツクの形成がみられるようになるの
で、その安定性も十分であるとはいえない。 CF 3 (CF 2 ) 8 COONa; CF 3 (CF 2 ) 8 COONH 4 However, when a radical polymerization reaction of a fluorine-containing monomer is carried out in the presence of these surfactants, there are problems in that not only the stability of the resulting polymer latex is poor, but also the polymerization rate is slow. For example, when using a carboxylate salt such as the one mentioned above, although there is no problem in terms of polymerization rate, there is a problem particularly in the stability of the produced polymer latex, and the solid content concentration is about 35%, which is a practical concentration. However, it does not become latex-like, but becomes cream-like. In the case of the more widely used sulfonic acid salts mentioned above, the influence on the polymerization rate is particularly large, and when the surfactant is used at a high concentration, the polymerization rate decreases markedly. Furthermore, the produced polymer latex is stable in itself, but if a thickener is added to adjust the viscosity for use in paints, flocs will form, and its stability will be affected. It cannot be said that it is sufficient.
本発明者は、これらの問題点の原因を解明し、
それによつて重合速度を低下させず、しかも安定
な重合体ラテツクスを形成し得るフルオロカーボ
ン系の界面活性剤を求めて、種々の検討を行なつ
た。まず、重合速度の点からは、前記カルボン酸
塩型の界面活性剤の場合には重合速度的には問題
がなく、不飽和結合を有する前記スルホン酸塩型
の界面活性剤の場合に問題があることから、界面
活性剤分子中の不飽和結合の存在が重合速度に悪
影響を及ぼしているのではないかと考えた。ま
た、前記カルボン酸塩型およびスルホン酸塩型の
界面活性剤は、いずれも十分に安定な重合体ラテ
ツクスを与えないが、その原因をフルオロカーボ
ン鎖の剛直性および長さの不十分性にあるものと
考えた。 The inventor has clarified the causes of these problems,
Various studies were conducted in search of a fluorocarbon surfactant that does not reduce the polymerization rate and can form a stable polymer latex. First, from the point of view of polymerization rate, there is no problem in terms of polymerization rate in the case of the carboxylate type surfactant, but there is a problem in the case of the sulfonate type surfactant having an unsaturated bond. Based on this, we thought that the presence of unsaturated bonds in surfactant molecules might have a negative effect on the polymerization rate. Furthermore, neither the carboxylate type nor the sulfonate type surfactants give sufficiently stable polymer latexes, but this may be due to insufficient rigidity and length of the fluorocarbon chains. I thought.
そして、このような考え方に基き、主鎖に不飽
和結合を有せず、フルオロカーボン鎖の長さも長
くかつ柔軟な構造を有するポリパーフルオロエー
テルカルボン酸のアルカリ金属塩またはアンモニ
ウム塩を選択し、これを界面活性剤に使用するこ
とにより、前記の如き本発明の課題が有効に解決
できることをここに見出した。 Based on this idea, we selected an alkali metal salt or ammonium salt of polyperfluoroether carboxylic acid that does not have unsaturated bonds in its main chain, has a long fluorocarbon chain, and has a flexible structure. It has now been discovered that the above-mentioned problems of the present invention can be effectively solved by using this as a surfactant.
従つて、本発明はフツ素含有単量体の重合方法
に係り、フツ素含有単量体の重合はポリパーフル
オロエーテルカルボン酸塩を界面活性剤に用いた
ラジカル重合反応によつて行われる。 Therefore, the present invention relates to a method for polymerizing a fluorine-containing monomer, and the polymerization of the fluorine-containing monomer is carried out by a radical polymerization reaction using a polyperfluoroether carboxylate as a surfactant.
アルキル金属塩またはアンモニウム塩の形で用
いられるポリパーフルオロエーテルカルボン酸と
しては、一般式
ＣoＦ2o+1−Ｏ（−ＣoＦ2o−Ｏ）−nＣo-1Ｆ2o-2COOH
で示されるものが用いられ、ここでｎは１〜４、
好ましくは２〜３、またｍは０〜12、好ましくは
５〜８であつて、ｎとｍとの和が少くとも２のも
のが一般に用いられる。カルボン酸塩の形成は、
重合反応系においても行なうことができ、反応系
にポリパーフルオロエーテルカルボン酸および例
えば炭酸ナトリウム、炭酸カリウム、炭酸アンモ
ニウム、水酸化ナトリウム、水酸化カリウム、ア
ンモニア水などの無機のアルカリ金属塩またはア
ンモニウム塩を共存させることによつても行なう
ことができる。このようにして形成されるポリパ
ーフルオロエーテルカルボン酸塩は、カルボン酸
塩基およびエーテル結合の存在による親水性の十
分な付与も考えられ、その使用割合としては一般
に重合系の水性媒体の重量に対し約0.01〜２％、
好ましくは約0.1〜１％の範囲にあることが望ま
しい。界面活性剤をこれ以上の割合で使用するこ
とは不経済で、また着色の原因ともなる。一方、
これ以下の割合では、安定なラテツクスを形成さ
せることができない。 Polyperfluoroether carboxylic acids used in the form of alkyl metal salts or ammonium salts have the general formula C o F 2o+1 -O(-C o F 2o -O)- n C o-1 F 2o-2 COOH The one shown is used, where n is 1 to 4,
Preferably, m is 2 to 3, and m is 0 to 12, preferably 5 to 8, and those in which the sum of n and m is at least 2 are generally used. The formation of carboxylic acid salts is
It can also be carried out in a polymerization reaction system, and the reaction system contains polyperfluoroether carboxylic acid and an inorganic alkali metal salt or ammonium salt such as sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide, aqueous ammonia, etc. This can also be done by coexisting. The polyperfluoroether carboxylate formed in this way is considered to have sufficient hydrophilicity due to the presence of carboxylic acid bases and ether bonds, and the proportion used is generally based on the weight of the aqueous medium in the polymerization system. Approximately 0.01~2%,
Preferably, it is in the range of about 0.1 to 1%. Using a surfactant in a proportion higher than this is uneconomical and also causes coloration. on the other hand,
If the ratio is lower than this, a stable latex cannot be formed.
このようなポリパーフルオロエーテルカルボン
酸塩を界面活性剤に用いてラジカル重合されるフ
ツ素含有単量体としては、例えばフツ化ビニリデ
ン、フツ化ビニル、テトラフルオロエチレン、ヘ
キサフルオロプロペン、トリフルオロクロルエチ
レン、ペンタフルオロプロペン、トリフルオロメ
チルビニルエーテルなどが挙げられ、これらのフ
ツ素含有単量体は単独重合またはこれら相互ある
いは他の重合性単量体との共重合反応に供するこ
とができる。 Fluorine-containing monomers that can be radically polymerized using such polyperfluoroether carboxylates as surfactants include, for example, vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, hexafluoropropene, and trifluorochloride. Examples include ethylene, pentafluoropropene, trifluoromethyl vinyl ether, and the like, and these fluorine-containing monomers can be subjected to homopolymerization or copolymerization with each other or with other polymerizable monomers.
重合反応は、適宜変更することは可能である
が、一般に次のような方法によつて行われる。イ
オン交換水を重合用水性媒体として用いて圧力反
応容器中に入れ、必要に応じて器内を窒素ガスな
どの不活性ガスで十分置換した後、ポリパーフル
オロエーテルカルボン酸、塩形成用の無機アルカ
リ金属塩またはアンモニウム塩、重合度を調節す
るためのクロロホルム、アセトン、四塩化炭素、
ヒドロキノンなどの連鎖移動剤およびフツ素含有
単量体を仕込み、水溶性ラジカル重合開始剤の存
在下で乳化重合またはけん濁重合せしめる。 Although the polymerization reaction can be modified as appropriate, it is generally carried out by the following method. Ion-exchanged water is used as an aqueous medium for polymerization and placed in a pressure reaction vessel, and if necessary, the interior of the vessel is sufficiently replaced with an inert gas such as nitrogen gas. Alkali metal salts or ammonium salts, chloroform, acetone, carbon tetrachloride to adjust the degree of polymerization,
A chain transfer agent such as hydroquinone and a fluorine-containing monomer are charged, and emulsion polymerization or suspension polymerization is carried out in the presence of a water-soluble radical polymerization initiator.
水溶性ラジカル重合開始剤としては、過硫酸ア
ンモニウム、過硫酸カリウム、過酸化水素など通
常使用されているものが使用され、これらの水溶
性過酸化物と亜硫酸塩その他の還元剤とが組合さ
れたレドツクス重合触媒系として用いることもで
きる。これらの開始剤は、水性媒体の重量に対し
約0.0001〜0.1％程度の割合で用いられる。 As the water-soluble radical polymerization initiator, commonly used ones such as ammonium persulfate, potassium persulfate, and hydrogen peroxide are used. It can also be used as a polymerization catalyst system. These initiators are used in a proportion of about 0.0001 to 0.1% based on the weight of the aqueous medium.
このような水溶性ラジカル重合開始剤の存在下
で行われる重合反応は、約１〜100Kg／cm2、好ま
しくは約10〜60Kg／cm2の重合圧力下で、約50〜
120℃、好ましくは約70〜90℃の重合温度で行わ
れるが、一般にレドツクス重合触媒系では低温側
で、また過酸化物触媒系では高温側で反応を行な
うことが好ましい。ポリパーフルオロエーテルカ
ルボン酸塩を界面活性剤に用いた本発明の重合反
応では、重合されるフツ素含有単量体の種類や他
の重合条件によつても異なるが、その重合時間は
約100〜180分間程度で十分であり、従来用いられ
ていたフルオロカーボン系界面活性剤使用の場合
よりも重合所要時間を著しく短縮せしめることが
できる。 The polymerization reaction carried out in the presence of such a water-soluble radical polymerization initiator is carried out under a polymerization pressure of about 1 to 100 Kg/cm 2 , preferably about 10 to 60 Kg/cm 2 , and at a polymerization pressure of about 50 to 100 Kg/cm 2 .
The polymerization is carried out at a temperature of 120 DEG C., preferably about 70 DEG to 90 DEG C., but it is generally preferred to carry out the reaction at a lower temperature for redox polymerization catalyst systems and at a higher temperature for peroxide catalyst systems. In the polymerization reaction of the present invention using polyperfluoroether carboxylate as a surfactant, the polymerization time is about 100%, although it varies depending on the type of fluorine-containing monomer to be polymerized and other polymerization conditions. About 180 minutes is sufficient, and the time required for polymerization can be significantly shortened compared to the case of using a conventionally used fluorocarbon surfactant.
本発明方法によつて得られるフツ素含有単量体
の重合体ラテツクスは、このように安定性の点で
著しくすぐれているため、そのままの状態である
いは増粘剤添加によつて増粘した状態で、塗料、
表面処理剤、離型剤などの用途に有効に使用する
ことができる。 The polymer latex of the fluorine-containing monomer obtained by the method of the present invention has such outstanding stability that it can be used as it is or in a state thickened by the addition of a thickener. So, paint,
It can be effectively used as a surface treatment agent, mold release agent, etc.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例
容量１のオートクレーブに、水530ml、次式
で示されるポリパーフルオロエーテルカルボン酸
（米国特許第3660315号明細書参照）
5.3ｇ（4.6ミリモル）、炭酸ナトリウム0.5ｇ、ク
ロロホルム８mlおよびヘキサフルオロプロペン85
ｇを仕込み、80℃に昇温させた後、過硫酸アンモ
ニウム2.6ｇを加え、フツ化ビニリデン262ｇを分
添（ゲージ圧40〜60Kg／cm2で圧入）し、120分間
重合させた。固形分濃度36.1％、粘度5cps（30
℃）の共重合体ラテツクス837ｇが得られ、この
結果重合率は88.5％となる。Example In an autoclave with a capacity of 1, 530 ml of water and polyperfluoroether carboxylic acid represented by the following formula (see US Pat. No. 3,660,315) 5.3 g (4.6 mmol), sodium carbonate 0.5 g, chloroform 8 ml and hexafluoropropene 85
After raising the temperature to 80° C., 2.6 g of ammonium persulfate was added, and 262 g of vinylidene fluoride was added in portions (injected at a gauge pressure of 40 to 60 kg/cm 2 ), followed by polymerization for 120 minutes. Solid content concentration 36.1%, viscosity 5cps (30
837 g of a copolymer latex with a temperature of 1.5 °C was obtained, resulting in a polymerization rate of 88.5%.
このようにして形成された共重合体ラテツクス
に、次式で示される界面活性剤
1.86ｇを加える。これに、ラテツクスの固形分に
対して0.7％のアクリル酸−アクリル酸メチル共
重合体を増粘剤として加えるとラテツクスの粘度
は42cps（30℃）となり、また0.2％のポリアクリ
ル酸を加えると20cps（30℃）となるが、いずれ
もフロツクの発生はみられなかつた。 A surfactant represented by the following formula is added to the copolymer latex thus formed. Add 1.86g. When 0.7% of acrylic acid-methyl acrylate copolymer is added as a thickener based on the solid content of the latex, the viscosity of the latex becomes 42 cps (30°C), and when 0.2% of polyacrylic acid is added as a thickener, the viscosity of the latex becomes 42 cps (30°C). 20cps (30℃), but no flocs were observed in either case.
比較例 １
容量１のオートクレーブに、水530ml、実施
例で生成共重合体ラテツクスに加えられた界面活
性剤1.87ｇ（４ミリモル）、クロロホルム８mlお
よびヘキサフルオロプロペン82ｇを仕込み、80℃
に昇温させた後、過硫酸アンモニウム2.6ｇを加
え、フツ化ビニリデン264ｇを分添し、310分間重
合させた。固形分濃度36.5％の共重合体ラテツク
ス820ｇが得られ、この結果重合率は83.4％とな
る。Comparative Example 1 In an autoclave with a capacity of 1, 530 ml of water, 1.87 g (4 mmol) of the surfactant added to the copolymer latex produced in the example, 8 ml of chloroform, and 82 g of hexafluoropropene were charged, and the mixture was heated at 80°C.
After raising the temperature to , 2.6 g of ammonium persulfate was added, and 264 g of vinylidene fluoride was added in portions, followed by polymerization for 310 minutes. 820 g of copolymer latex with a solid content concentration of 36.5% was obtained, resulting in a polymerization rate of 83.4%.
このようにして形成された共重合体ラテツクス
に、実施例と同様に同量の界面活性剤およびポリ
アクリル酸を加えると、フロツクが著しく発生す
るのが認められた。 When the same amounts of surfactant and polyacrylic acid were added to the copolymer latex thus formed as in the example, it was observed that flocs were significantly generated.
比較例 ２
容量１のオートクレーブに、水530ml、次式
で示される界面活性剤CF3（CF2）8COONH42.0ｇ
（４ミリモル）、クロロホルム８mlおよびヘキサフ
ルオロプロペン81ｇを仕込み、80℃に昇温させた
後、過硫酸アンモニウム2.6ｇを加え、フツ化ビ
ニリデン285ｇを分添し、185分間重合させた。固
形分濃度33.2％の共重合体ラテツクスが858ｇ得
られ、この結果重合率は89.7％となる。Comparative Example 2 In an autoclave with a capacity of 1, 530 ml of water and 2.0 g of surfactant CF 3 (CF 2 ) 8 COONH 4 represented by the following formula
(4 mmol), 8 ml of chloroform, and 81 g of hexafluoropropene were charged, the temperature was raised to 80°C, 2.6 g of ammonium persulfate was added, and 285 g of vinylidene fluoride was added in portions, followed by polymerization for 185 minutes. 858 g of copolymer latex with a solids concentration of 33.2% was obtained, resulting in a polymerization rate of 89.7%.
このようにして形成された共重合体ラテツクス
は、クリーム状を呈している。 The copolymer latex thus formed has a cream-like appearance.
以上の実施例および各比較例の対比から、次の
ようなことがいえる。即ち、ポリパーフルオロエ
ーテルカルボン酸塩を界面活性剤に用いることに
より、重合速度の上昇による重合所要時間の短
縮、生成共重合体ラテツクスを増粘してもフロツ
クを生じない程のラテツクスの安定性の確保など
が図られ、これに対して従来公知のパーフルオロ
スルホン酸塩またはパーフルオロカルボン酸塩系
の界面活性剤を用いた場合には、共重合体ラテツ
クスの増粘時にフロツクが発生したり、あるいは
生成共重合体ラテツクス自体がクリーム状を呈す
るなど、ラテツクスの安定性の点において著しく
欠けるものがある。 From the comparison between the above examples and each comparative example, the following can be said. In other words, by using polyperfluoroether carboxylate as a surfactant, the polymerization rate is increased to shorten the time required for polymerization, and the resulting copolymer latex has such stability that no flocs occur even when the copolymer latex is thickened. On the other hand, when conventionally known perfluorosulfonate or perfluorocarboxylate surfactants are used, flocs may occur when the copolymer latex thickens. In some cases, the resulting copolymer latex itself exhibits a cream-like appearance, resulting in a significant lack of stability in the latex.
Claims (1)
面活性剤に用いてラジカル重合反応を行なうこと
を特徴とするフツ素含有単量体の重合方法。 ２ ポリパーフルオロエーテルカルボン酸塩がア
ルカリ金属塩である特許請求の範囲第１項記載の
フツ素含有単量体の重合方法。 ３ ポリパーフルオロエーテルカルボン酸塩がア
ンモニウム塩である特許請求の範囲第１項記載の
フツ素含有単量体の重合方法。[Scope of Claims] 1. A method for polymerizing a fluorine-containing monomer, which comprises carrying out a radical polymerization reaction using a polyperfluoroether carboxylate as a surfactant. 2. The method for polymerizing a fluorine-containing monomer according to claim 1, wherein the polyperfluoroether carboxylate is an alkali metal salt. 3. The method for polymerizing a fluorine-containing monomer according to claim 1, wherein the polyperfluoroether carboxylate is an ammonium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14743380A JPS5770112A (en) | 1980-10-21 | 1980-10-21 | Polymerization of fluorine-containing monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14743380A JPS5770112A (en) | 1980-10-21 | 1980-10-21 | Polymerization of fluorine-containing monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5770112A JPS5770112A (en) | 1982-04-30 |
| JPS6146003B2 true JPS6146003B2 (en) | 1986-10-11 |
Family
ID=15430209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14743380A Granted JPS5770112A (en) | 1980-10-21 | 1980-10-21 | Polymerization of fluorine-containing monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5770112A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009069320A1 (en) | 2007-11-28 | 2009-06-04 | Unimatec Co., Ltd. | Process for producing fluoroelastomer |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI991516A1 (en) * | 1999-07-09 | 2001-01-09 | Ausimont Spa | SUMMARY OF THERMAL PROPESABLE PERHALOGENATED COPOLYMERS OF CHLOROTRIFLUOROETHYLENE |
| US7045571B2 (en) | 2001-05-21 | 2006-05-16 | 3M Innovative Properties Company | Emulsion polymerization of fluorinated monomers |
| US6923921B2 (en) | 2002-12-30 | 2005-08-02 | 3M Innovative Properties Company | Fluorinated polyether compositions |
| US7652115B2 (en) | 2003-09-08 | 2010-01-26 | 3M Innovative Properties Company | Fluorinated polyether isocyanate derived silane compositions |
| US7141537B2 (en) | 2003-10-30 | 2006-11-28 | 3M Innovative Properties Company | Mixture of fluorinated polyethers and use thereof as surfactant |
| US7803894B2 (en) | 2003-12-05 | 2010-09-28 | 3M Innovatie Properties Company | Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes |
| GB0514387D0 (en) * | 2005-07-15 | 2005-08-17 | 3M Innovative Properties Co | Aqueous emulsion polymerization of fluorinated monomers using a perfluoropolyether surfactant |
| EP1939223B1 (en) | 2005-10-20 | 2011-07-13 | Asahi Glass Company, Limited | Method for producing melt-moldable fluororesin |
| WO2008024601A1 (en) * | 2006-08-24 | 2008-02-28 | 3M Innovative Properties Company | Solvent slurry process for producing high solids fluoropolymers |
| JP2009215296A (en) * | 2008-03-07 | 2009-09-24 | Daikin Ind Ltd | Fluoroether alcohol, fluoroether carboxylate, and fluoroether carboxylic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51123790A (en) * | 1975-04-22 | 1976-10-28 | Asahi Denka Kogyo Kk | Surfactant |
-
1980
- 1980-10-21 JP JP14743380A patent/JPS5770112A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51123790A (en) * | 1975-04-22 | 1976-10-28 | Asahi Denka Kogyo Kk | Surfactant |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009069320A1 (en) | 2007-11-28 | 2009-06-04 | Unimatec Co., Ltd. | Process for producing fluoroelastomer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5770112A (en) | 1982-04-30 |
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