JPH0826098B2 - Method for producing fluoropolymer - Google Patents
Method for producing fluoropolymerInfo
- Publication number
- JPH0826098B2 JPH0826098B2 JP15129389A JP15129389A JPH0826098B2 JP H0826098 B2 JPH0826098 B2 JP H0826098B2 JP 15129389 A JP15129389 A JP 15129389A JP 15129389 A JP15129389 A JP 15129389A JP H0826098 B2 JPH0826098 B2 JP H0826098B2
- Authority
- JP
- Japan
- Prior art keywords
- ccl
- fluoropolymer
- polymerization
- fluoroolefin
- 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.)
- Expired - Fee Related
Links
- 229920002313 fluoropolymer Polymers 0.000 title claims description 19
- 239000004811 fluoropolymer Substances 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- JGZVUTYDEVUNMK-UHFFFAOYSA-N 5-carboxy-2',7'-dichlorofluorescein Chemical compound C12=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C2C21OC(=O)C1=CC(C(=O)O)=CC=C21 JGZVUTYDEVUNMK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- -1 CF 3 CF = CFCl Chemical compound 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 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】 産業上の利用分野 本発明は含フッ素重合体の新規な製造方法に関するも
のである。さらに詳しくいえば、本発明は、環境破壊を
もたらすことの少ない重合媒体を用いて耐熱性、耐溶剤
性、耐薬品性などの良好な含フッ素重合体を効率よく製
造する方法に関するものである。TECHNICAL FIELD The present invention relates to a novel method for producing a fluoropolymer. More specifically, the present invention relates to a method for efficiently producing a fluoropolymer having good heat resistance, solvent resistance, chemical resistance and the like by using a polymerization medium that causes less environmental damage.
従来の技術 近年、含フッ素重合体は、耐熱性、耐溶剤性、耐薬品
性などに優れた高分子材料であることから、その特徴を
生かして種々の用途に利用されている。2. Description of the Related Art In recent years, a fluoropolymer is a polymer material having excellent heat resistance, solvent resistance, chemical resistance, and the like, and is utilized for various purposes by making use of its characteristics.
このような含フッ素重合体の製造方法としては、従来
溶液重合法や溶液懸濁重合法が知られており、そして、
その重合媒体としては、クロロフルオロカーボンなどの
不活性溶媒が、高分子量の含フッ素重合体を与えること
や重合速度などの点から、通常用いられている。該クロ
ロフルオロカーボンの具体例としては、トリクロロフル
オロメタン、ジクロロジフルオロメタン、トリクロロト
リフルオロエタン、ジクロロテトラフルオロエタンなど
が例示できるが、取り扱いの点からトリクロロトリフル
オロエタンが主に用いられている。As a method for producing such a fluoropolymer, a solution polymerization method and a solution suspension polymerization method are conventionally known, and
As the polymerization medium, an inert solvent such as chlorofluorocarbon is usually used from the viewpoint of giving a high molecular weight fluoropolymer and the polymerization rate. Specific examples of the chlorofluorocarbon include trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane and the like, but trichlorotrifluoroethane is mainly used from the viewpoint of handling.
ところで、近年、オゾン層破壊が地球規模の環境破壊
問題として国際的に取り上げられ、その原因物質として
クロロフルオロカーボンが指摘され、世界的に全廃の方
向に向っている。このため含フッ素重合体を製造する際
に用いるクロロフルオロカーボンの使用を停止する必要
が生じてきている。By the way, in recent years, ozone layer depletion has been internationally taken up as a global environmental destruction problem, and chlorofluorocarbon has been pointed out as a causative substance thereof, and it is heading for global abolition. For this reason, it has become necessary to stop the use of chlorofluorocarbons used in producing the fluoropolymer.
このクロロフルオロカーボンの代替品としては、水素
原子を含むヒドロクロロフルオロカーボンが、小さなオ
ゾン破壊係数を有するため提案されている。しかしなが
ら、従来、Ｃ−Ｈ結合を有する物質は、フルオロオレフ
ィンに対して連鎖移動性を示すことが知られており、水
素原子を含むヒドロクロロフルオロカーボンを、高分子
量の含フッ素重合体の製造の際に重合媒体として使用す
ることは困難であると考えられていた。実際に、Ｃ−Ｈ
結合を有する種々の溶媒が、含フッ素重合体の重合媒体
として検討されているが、高分子量の含フッ素重合体が
得られること、取り扱いやすいこと及び重合速度が十分
に速いことなどの点で有用な溶媒は見出されていないの
が実情である。As an alternative to this chlorofluorocarbon, a hydrochlorofluorocarbon containing a hydrogen atom has been proposed because of its low ozone depletion potential. However, conventionally, it has been known that a substance having a C—H bond exhibits chain transfer property to a fluoroolefin, and a hydrochlorofluorocarbon containing a hydrogen atom is added to the fluoroolefin in the production of a high molecular weight fluoropolymer. It has been considered difficult to use as a polymerization medium. Actually C-H
Various solvents having a bond have been studied as a polymerization medium for a fluoropolymer, but useful in that a high molecular weight fluoropolymer can be obtained, easy handling, and a sufficiently high polymerization rate. The reality is that no suitable solvent has been found.
発明が解決しようとする課題 本発明は、このような事情のもとで、重合速度が速く
て、含フッ素重合体の分子量を十分に高めることがで
き、かつオゾン破壊係数の大きなクロロフルオロカーボ
ンを使用することなく耐熱性、耐溶剤性、耐薬品性に優
れる含フッ素重合体を効率よく製造する方法を提供する
ことを目的としてなされたものである。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Under the circumstances, the present invention uses a chlorofluorocarbon that has a high polymerization rate, can sufficiently increase the molecular weight of the fluoropolymer, and has a large ozone depletion coefficient. The present invention has been made for the purpose of providing a method for efficiently producing a fluoropolymer having excellent heat resistance, solvent resistance and chemical resistance.
課題を解決するための手段 本発明者らは、前記目的を達成するために鋭意研究を
重ねた結果、特定の構造のＣ−Ｈ結合を有するヒドロハ
ロフルオロカーボンは連鎖移動性が小さいことに着目
し、このものを含有する溶媒を重合媒体として用いるこ
とにより、その目的を達成しうることを見出し、この知
見に基づいて本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have noticed that hydrohalofluorocarbons having a C—H bond having a specific structure have a small chain transfer property. It was found that the object can be achieved by using a solvent containing this as a polymerization medium, and the present invention has been completed based on this finding.
すなわち、本発明は、重合媒体中において、フルオロ
オレフィンを主体とする原料単量体に、ラジカル開始剤
を作用させてフルオロオレフィン単位を主構成単位とし
て含有する含フッ素重合体を製造するに当り、該重合媒
体として、一般式 CH3R …（Ｉ） （式中のＲは少なくともフッ素原子１個を含むパーハロ
メチル基又はパーハロエチル基である）で表わされる化
合物を含有する溶媒を用いることを特徴とする含フッ素
重合体の製造方法を提供するものである。That is, the present invention, in the polymerization medium, in producing a fluoropolymer containing a fluoroolefin unit as a main constitutional unit by causing a radical initiator to act on a raw material monomer mainly containing fluoroolefin, As the polymerization medium, a solvent containing a compound represented by the general formula CH 3 R ... (I) (wherein R is a perhalomethyl group or a perhaloethyl group containing at least one fluorine atom) is used. The present invention provides a method for producing a fluoropolymer.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明方法において用いられるフルオロオレフィン
は、分子中に少なくとも１個のフッ素原子を有するオレ
フィンであって、好ましいものとしては、重合性及び得
られる重合体の性質の点から、炭素数２又は３のフルオ
ロオレフィンが好適である。The fluoroolefin used in the method of the present invention is an olefin having at least one fluorine atom in the molecule, and is preferably one having 2 or 3 carbon atoms in view of polymerizability and properties of the obtained polymer. Fluoroolefins are preferred.
このようなフルオロオレフィンの具体例としては、CF
2＝CF2、CHF＝CF2、CH2＝CF2、CH2＝CHF、CClF＝CF2、C
HCl＝CF2、CCl2＝CF2、CClF＝CClF、CHF＝CCl2、CH2＝C
ClF、CCl2＝CClFなどのフルオロエチレン系、CF3CF＝CF
2、CF3CF＝CHF、CF3CH＝CF2、CF3CF＝CH2、CF3CF＝CH
F、CHF2CF＝CHF、CF3CH＝CH2、CH3CF＝CF2、CH3CH＝C
F2、CH3CF＝CH2、CF2ClCF＝CF2、CF3CCl＝CF2、CF3CF＝
CFCl、CF2ClCCl＝CF2、CF2ClCF＝CFCl、CFCl2CF＝CF2、
CF3CCl＝CClF、CF3CCl＝CCl2、CClF2CF＝CCl2、CCl3CF
＝CF2、CF2ClCCl＝CCl2、CFCl2CCl＝CCl2、CF3CF＝CHC
l、CClF2CF＝CHCl、CF3CCl＝CHCl、CHF2CCl＝CCl2、CF2
ClCH＝CCl2、CF2ClCCl＝CHCl、CCl3CF＝CHCl、CF2lCF＝
CF2、CF2BrCH＝CF2、CF3CBr＝CHBr、CF2ClCBr＝CH2、CH
2BrCF＝CCl2、CF3CBr＝CH2、CF2CH＝CHBr、CF2BrCH＝CH
F、CF2BrCF＝CF2などのフルオロプロペン系、CF3CF2CF
＝CF2、CF3CF＝CFCF3、CF3CH＝CFCF3、CF2＝CFCF2CH
F2、CF3CF2CF＝CH2、CF3CH＝CHCF3、CF2＝CFCF2CH3、CF
2＝CFCH2CH3、CF3CH2CH＝CH2、CF3CH＝CHCH3、CF2＝CHC
H2CH3、CH3CF2CH＝CH2、CFH2CH＝CHCFH2、CH3CF2CH＝CH
2、CH2＝CFCH2CH3、CF3(CF2)2CF＝CF2、CF3(CF2)3CF＝C
F2などの炭素数４以上のフルオロオレフィン化合物を挙
げることができるが、これらの中でフルオロエチレン化
合物及びフルオロプロペン化合物が好ましく、特にテト
ラフルオロエチレン（CF2＝CF2）、ビニリデンフルオリ
ド（CH2＝CF2）及びヘキサフルオロプロピレン（CF2＝C
FCF3）が好適である。これらのフルオロオレフィンは、
それぞれ単独で用いてもよいし、２種以上を組み合わせ
て用いてもよい。Specific examples of such fluoroolefins include CF
2 = CF 2 , CHF = CF 2 , CH 2 = CF 2 , CH 2 = CHF, CClF = CF 2 , C
HCl = CF 2 , CCl 2 = CF 2 , CClF = CClF, CHF = CCl 2 , CH 2 = C
Fluoroethylene series such as ClF, CCl 2 = CClF, CF 3 CF = CF
2 , CF 3 CF = CHF, CF 3 CH = CF 2 , CF 3 CF = CH 2 , CF 3 CF = CH
F, CHF 2 CF = CHF, CF 3 CH = CH 2 , CH 3 CF = CF 2 , CH 3 CH = C
F 2 , CH 3 CF = CH 2 , CF 2 ClCF = CF 2 , CF 3 CCl = CF 2 , CF 3 CF =
CFCl, CF 2 ClCCl = CF 2 , CF 2 ClCF = CFCl, CFCl 2 CF = CF 2 ,
CF 3 CCl = CClF, CF 3 CCl = CCl 2 , CClF 2 CF = CCl 2 , CCl 3 CF
= CF 2 , CF 2 ClCCl = CCl 2 , CFCl 2 CCl = CCl 2 , CF 3 CF = CHC
l, CClF 2 CF = CHCl, CF 3 CCl = CHCl, CHF 2 CCl = CCl 2 , CF 2
ClCH = CCl 2 , CF 2 ClCCl = CHCl, CCl 3 CF = CHCl, CF 2 lCF =
CF 2 , CF 2 BrCH = CF 2 , CF 3 CBr = CHBr, CF 2 ClCBr = CH 2 , CH
2 BrCF = CCl 2 , CF 3 CBr = CH 2 , CF 2 CH = CHBr, CF 2 BrCH = CH
F, CF 2 Br CF = fluoro propene system such as CF 2 , CF 3 CF 2 CF
= CF 2 , CF 3 CF = CFCF 3 , CF 3 CH = CFCF 3 , CF 2 = CFCF 2 CH
F 2 , CF 3 CF 2 CF = CH 2 , CF 3 CH = CHCF 3 , CF 2 = CFCF 2 CH 3 , CF
2 = CFCH 2 CH 3 , CF 3 CH 2 CH = CH 2 , CF 3 CH = CHCH 3 , CF 2 = CHC
H 2 CH 3 , CH 3 CF 2 CH = CH 2 , CFH 2 CH = CH CFH 2 , CH 3 CF 2 CH = CH
2 , CH 2 = CFCH 2 CH 3 , CF 3 (CF 2 ) 2 CF = CF 2 , CF 3 (CF 2 ) 3 CF = C
Fluoroolefin compounds having 4 or more carbon atoms such as F 2 can be mentioned, and among these, fluoroethylene compounds and fluoropropene compounds are preferable, and particularly tetrafluoroethylene (CF 2 = CF 2 ), vinylidene fluoride (CH 2 2 = CF 2 ) and hexafluoropropylene (CF 2 = C
FCF 3 ) is preferred. These fluoroolefins are
Each may be used alone, or two or more kinds may be used in combination.
本発明においては、重合媒体として、一般式 CH3R …（Ｉ） （Ｒは前記と同じ意味をもつ） で表わされる化合物を含有する溶媒を用いることが必要
である。In the present invention, it is necessary to use a solvent containing a compound represented by the general formula CH 3 R ... (I) (R has the same meaning as described above) as the polymerization medium.
前記一般式（Ｉ）で表わされる化合物は水素原子を含
むので、オゾン破壊係数は小さくて、環境破壊をもたら
すことが少なく、その使用に問題がない上、フルオロオ
レフィンに対する連鎖移動性が小さいので、このものを
重合媒体に用いることにより、重合速度が速くなり、得
られる含フッ素重合体の分子量を高めることができる。Since the compound represented by the general formula (I) contains a hydrogen atom, it has a small ozone depletion potential, causes little environmental damage, has no problem in its use, and has a small chain transfer property to fluoroolefins. By using this as a polymerization medium, the polymerization rate is increased, and the molecular weight of the obtained fluoropolymer can be increased.
前記一般式（Ｉ）で表わされる化合物の具体例として
は、CH3CCl2F、CH3CClF2、CH3CF3などのエタン系、CH3C
F2CF3、CH3CF2CF2Cl、CH3CF2CFCl2、CH3CFClCF3、CH3CF
ClCF2Cl、CH3CF2CFCl2などのプロパン系のものを挙げる
ことができるが、取り扱いの簡便さ、入手の容易などの
点からCH3CCl2Fが好適である。これらはそれぞれ単独で
用いてもよいし、２種以上を混合して用いてもよい。Specific examples of the compound represented by the general formula (I) include ethane-based compounds such as CH 3 CCl 2 F, CH 3 CClF 2 and CH 3 CF 3 , CH 3 C
F 2 CF 3 , CH 3 CF 2 CF 2 Cl, CH 3 CF 2 CFCl 2 , CH 3 CFClCF 3 , CH 3 CF
Examples thereof include propane-based compounds such as ClCF 2 Cl and CH 3 CF 2 CFCl 2, but CH 3 CCl 2 F is preferable from the viewpoints of easy handling and easy availability. These may be used alone or in combination of two or more.
前記一般式（Ｉ）で表わされる化合物がフルオロオレ
フィンに対して連鎖移動性が小さいのは、次のように説
明することができる。すなわち、 −CH2F−、−CHClF、−CHF2などのハロ置換メチル基に
含まれる水素原子は、フルオロオレフィンに対して著し
い連鎖移動性を示すのに対し、該一般式（Ｉ）における
メチル基（−CH3）中の水素原子は連鎖移動性が小さい
からである。It can be explained as follows that the compound represented by the general formula (I) has a small chain transfer property to a fluoroolefin. That is, a hydrogen atom contained in a halo-substituted methyl group such as —CH 2 F—, —CHClF, and —CHF 2 exhibits a remarkable chain transfer property with respect to a fluoroolefin, while a hydrogen atom in the general formula (I) is hydrogen atom in the radicals (-CH 3) is because a small chain transfer property.
前記一般式（Ｉ）で表わされる化合物におけるＲは、
炭素数１又は２の少なくともフッ素原子１個を含むパー
ハロアルキル基であることが必要であり、このＲが炭素
数３以上のものでは、取り扱いの簡便性が失われるし、
フッ素原子を含まないパーハロアルキル基、例えば−CC
l3、−CCl2CCl3などの基であるものはフルオロオレフィ
ンに対して著しい連鎖移動性を示し、本発明の目的が達
せられない。R in the compound represented by the general formula (I) is
It is necessary to be a perhaloalkyl group having 1 or 2 carbon atoms and containing at least one fluorine atom, and if R is 3 or more carbon atoms, convenience of handling is lost,
Perhaloalkyl groups containing no fluorine atoms, for example -CC
l 3, those groups such as -CCl 2 CCl 3 shows significant chain transfer towards fluoroolefin, can not be achieved an object of the present invention.
本発明においては、重合媒体として、前記一般式
（Ｉ）で表わされる化合物に、水などの不活性溶媒を含
有させて用いることもできる。In the present invention, the compound represented by the general formula (I) may be used as a polymerization medium in which an inert solvent such as water is contained.
本発明方法においては、重合型式として溶液重合法及
び溶液懸濁重合法のいずれの形式も用いることができる
し、また使用するラジカル重合開始剤は重合形式に応じ
て従来慣用されているものの中から適宜選ぶことができ
る。In the method of the present invention, either a solution polymerization method or a solution suspension polymerization method can be used as the polymerization type, and the radical polymerization initiator to be used is selected from those conventionally used depending on the polymerization method. It can be selected appropriately.
本発明方法においては、重合反応は回分式、半連続
式、連続式のいずれでも実施することができる。この
際、重合反応温度は、通常−10〜150℃、好ましくは40
〜100℃の範囲で選ばれ、また、圧力については特に制
限はなく、例えば回分式の場合、自然発生圧力下での操
作が可能である。さらに、重合時間は反応温度やフルオ
ロオレフィン、重合媒体の種類などに左右され、一概に
定めることができないが、例えば回分式の場合、通常４
〜24時間程度である。In the method of the present invention, the polymerization reaction can be carried out batchwise, semi-continuously or continuously. At this time, the polymerization reaction temperature is usually −10 to 150 ° C., preferably 40.
The pressure is selected in the range of -100 ° C, and the pressure is not particularly limited. For example, in the case of a batch type, it is possible to operate under a naturally occurring pressure. Further, the polymerization time depends on the reaction temperature, the fluoroolefin, the type of the polymerization medium, etc., and cannot be determined unconditionally.
~ 24 hours.
本発明方法により得られた含フッ素重合体は高分子量
であるので、耐熱性、耐溶剤性、耐薬品性に優れ、含フ
ッ素エラストマーの場合、ポリアミン化合物、ポリヒド
ロキシド化合物などの加硫剤を用いて加硫することによ
り、加熱定着ロール、バルブ、リング、パッキン、ガス
ケットなどに好適な優れた弾性体を得ることができる
し、フッ素樹脂の場合電線の絶縁材、管及び弁などの耐
化学薬品性ライニング材、耐化学薬品性容器、粘着防止
性ふた、シュートライナーなどとして有用である。Since the fluoropolymer obtained by the method of the present invention has a high molecular weight, it is excellent in heat resistance, solvent resistance, and chemical resistance. In the case of a fluoroelastomer, a vulcanizing agent such as a polyamine compound and a polyhydroxide compound is used. It can be vulcanized to obtain an excellent elastic material suitable for heat fixing rolls, valves, rings, packings, gaskets, etc. It is useful as a chemical lining material, chemical resistant container, anti-stick lid, shoot liner, etc.
発明の効果 本発明によると、フルオロオレフィンに対する連鎖移
動性の小さい特定構造のＣ−Ｈ結合を有するヒドロハロ
フルオロカーボンを含む溶媒を重合媒体として用いるこ
とにより、フルオロオレフィンの重合速度が高められ、
耐熱性、耐溶剤性、耐薬品性などに優れた含フッ素重合
体を容易に得ることができる。また、該ヒドロハロフル
オロカーボンはオゾン破壊係数が小さいので、環境破壊
をもたらすことが少ないという長所を有しており、本発
明方法は工業的価値の高い方法といえる。EFFECTS OF THE INVENTION According to the present invention, by using a solvent containing a hydrohalofluorocarbon having a C—H bond having a specific structure having a small chain transfer property to a fluoroolefin as a polymerization medium, the polymerization rate of the fluoroolefin can be increased,
A fluoropolymer having excellent heat resistance, solvent resistance, chemical resistance and the like can be easily obtained. Further, since the hydrohalofluorocarbon has a small ozone depletion coefficient, it has an advantage that it does not cause environmental damage, and thus the method of the present invention can be said to have a high industrial value.
実施例 次に、実施例により本発明をさらに詳細に説明する
が、本発明はこれらの例によってなんら限定されるもの
ではない 実施例 電磁誘導式かきまぜ機を備えた内容積約１のオート
クレーブを窒素ガスで十分に掃気し、減圧N2充てんを３
回繰り返して、窒素置換したのち、減圧状態で、脱酸素
した純水317g、溶媒としての1,1−ジクロロ−１−フル
オロエタン（以下フロンR141bという）90.7ml及び懸濁
安定剤としてのメチルセルロース（粘度50cp）0.32gを
仕込み、600rpmでかきまぜながら、温度50℃に保った。
次いで、ビニリデンフルオリド（以下VdFと略記する）2
7.9重量％、ヘキサフルオロプロピレン（以下HFPと略記
する）64.6重量％、及びテトラフルオロエチレン（以下
TFEと略記する）7.5重量％から成る混合モノマーを仕込
みガスとして13kg/cm2Ｇとなるまで仕込んだ。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example An autoclave having an internal volume of about 1 and equipped with an electromagnetic induction type agitator is filled with nitrogen. Sufficiently scavenged with gas and filled with decompressed N 2 to 3
Repeatedly, after nitrogen substitution, 317 g of deoxygenated pure water under reduced pressure, 90.7 ml of 1,1-dichloro-1-fluoroethane (hereinafter referred to as Freon R141b) as a solvent, and methyl cellulose as a suspension stabilizer ( A viscosity of 50 cp) 0.32 g was charged, and the temperature was kept at 50 ° C while stirring at 600 rpm.
Next, vinylidene fluoride (hereinafter abbreviated as VdF) 2
7.9% by weight, hexafluoropropylene (hereinafter abbreviated as HFP) 64.6% by weight, and tetrafluoroethylene (hereinafter
A mixed monomer composed of 7.5% by weight (abbreviated as TFE) was charged as a charging gas to 13 kg / cm 2 G.
次に開始剤として、ジイソプロピルパーオキシカーボ
ネート５重量％を含有したフロンR141b溶液5.72gを仕込
み重合を開始させた。重合により圧力が12.5kg/cm2Ｇま
で低下するので、VdF52.8重量％、HFP25.4重量％、TFE2
1.8重量％から成る混合モノマーを追添ガスとして追添
し再び圧力を13kg/cm2Ｇに戻した。このような操作を繰
り返し、８時間重合反応を行った。重合反応終了後残存
する混合モノマーを掃気し、得られた懸濁液を遠心分離
機で脱水し、十分水洗したのち、100℃で真空乾燥して
約140gのエラストマーを得た。得られた含フッ素エラス
トマーを19FNMRにより分析したところ、VdF単位53.5重
量％、HFP単位23.8重量％、TFE単位22.7重量％であり、
メチルエチルケトン中35℃で測定した極限粘度数は、15
2ml/gであった。なお、フロンR141bのオゾン破壊係数、
温室効果係数は、それぞれ0.05以下及び0.1以下であ
る。Then, 5.72 g of a Freon R141b solution containing 5% by weight of diisopropyl peroxycarbonate was charged as an initiator to start the polymerization. Since the pressure drops to 12.5 kg / cm 2 G due to polymerization, VdF52.8% by weight, HFP25.4% by weight, TFE2
A mixed monomer of 1.8% by weight was added as an additional gas, and the pressure was returned to 13 kg / cm 2 G again. The above operation was repeated to carry out a polymerization reaction for 8 hours. After the completion of the polymerization reaction, the mixed monomer remaining was scavenged, the resulting suspension was dehydrated with a centrifuge, thoroughly washed with water, and then vacuum dried at 100 ° C. to obtain about 140 g of an elastomer. When the obtained fluorine-containing elastomer was analyzed by 19 FNMR, it was found that the VdF unit was 53.5% by weight, the HFP unit was 23.8% by weight, and the TFE unit was 22.7% by weight.
The intrinsic viscosity number measured at 35 ° C in methyl ethyl ketone is 15
It was 2 ml / g. The ozone depletion potential of CFC R141b,
The greenhouse effect coefficients are below 0.05 and below 0.1, respectively.
比較例１〜６ 次表に示す種類と量の溶媒を用い、実施例と同様にし
て含フッ素重合体を製造した。その結果を次表に示す。Comparative Examples 1 to 6 Fluorine-containing polymers were produced in the same manner as in Examples using the solvents of the types and amounts shown in the following table. The results are shown in the table below.
この表から明らかなように、本発明の方法によれば、
従来のトリフルオロエタン系溶媒を用いた場合に匹敵す
る収率で所望の含フッ素重合体を製造することができ、
しかもオゾン破壊効果、温室効果ははるかに低いことが
分る。 As is apparent from this table, according to the method of the present invention,
It is possible to produce a desired fluoropolymer with a yield comparable to that when a conventional trifluoroethane-based solvent is used,
Moreover, it is clear that the ozone depletion effect and greenhouse effect are much lower.
Claims (1)
を主体とする原料単量体に、ラジカル開始剤を作用させ
てフルオロオレフィン単位を主構成単位として含有する
含フッ素重合体を製造するに当り、該重合媒体として、
一般式 CH3R （式中のＲは少なくともフッ素原子１個を含むパーハロ
メチル基又はパーハロエチル基である）で表わされる化
合物を含有する溶媒を用いることを特徴とする含フッ素
重合体の製造方法。1. A method for producing a fluorine-containing polymer containing a fluoroolefin unit as a main constituent unit by reacting a raw material monomer mainly comprising a fluoroolefin with a radical initiator in a polymerization medium, As a polymerization medium,
A process for producing a fluoropolymer, which comprises using a solvent containing a compound represented by the general formula CH 3 R (wherein R is a perhalomethyl group or a perhaloethyl group containing at least one fluorine atom).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15129389A JPH0826098B2 (en) | 1989-06-14 | 1989-06-14 | Method for producing fluoropolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15129389A JPH0826098B2 (en) | 1989-06-14 | 1989-06-14 | Method for producing fluoropolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0317106A JPH0317106A (en) | 1991-01-25 |
| JPH0826098B2 true JPH0826098B2 (en) | 1996-03-13 |
Family
ID=15515517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15129389A Expired - Fee Related JPH0826098B2 (en) | 1989-06-14 | 1989-06-14 | Method for producing fluoropolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0826098B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06211933A (en) * | 1993-01-19 | 1994-08-02 | Daikin Ind Ltd | Method for producing fluoropolymer |
| EP0638596B1 (en) * | 1993-03-17 | 1999-10-06 | Asahi Glass Company Ltd. | Process for producing fluoropolymer |
| WO1994022930A1 (en) * | 1993-03-30 | 1994-10-13 | E.I. Du Pont De Nemours And Company | Process for producing fluoroelastomer |
| JP2985600B2 (en) * | 1993-09-24 | 1999-12-06 | ダイキン工業株式会社 | Method for producing low molecular weight polytetrafluoroethylene |
| JPH07118596A (en) * | 1993-10-25 | 1995-05-09 | Daikin Ind Ltd | Water / oil repellent composition and method for producing the same |
| US5552500A (en) * | 1995-04-24 | 1996-09-03 | E. I. Du Pont De Nemours And Company | Fluoroalkene/hydrochlorofluorocarbon telomers and their synthesis |
| DE19844188A1 (en) * | 1998-09-28 | 2000-03-30 | Bayer Ag | Process for the production of a rapidly cross-linkable fluororubber |
| JP2017183166A (en) * | 2016-03-31 | 2017-10-05 | 株式会社オートネットワーク技術研究所 | Insulation wire |
-
1989
- 1989-06-14 JP JP15129389A patent/JPH0826098B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0317106A (en) | 1991-01-25 |
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