JPH0356516A - Production of vinylidene fluoride-based copolymer - Google Patents
Production of vinylidene fluoride-based copolymerInfo
- Publication number
- JPH0356516A JPH0356516A JP1192178A JP19217889A JPH0356516A JP H0356516 A JPH0356516 A JP H0356516A JP 1192178 A JP1192178 A JP 1192178A JP 19217889 A JP19217889 A JP 19217889A JP H0356516 A JPH0356516 A JP H0356516A
- Authority
- JP
- Japan
- Prior art keywords
- vinylidene fluoride
- polymerization
- weight
- copolymer
- fluorine compound
- 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
- 229920001577 copolymer Polymers 0.000 title claims abstract description 22
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 15
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002033 PVDF binder Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 hexafluoropropylene, tetrafluoroethylene, methyl Chemical group 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- CRAUJMFFRKZIHN-UHFFFAOYSA-N CC=C.F.F.F Chemical compound CC=C.F.F.F CRAUJMFFRKZIHN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- WLOYYMYGUUIYAH-UHFFFAOYSA-N [H]C([H])(OOC([H])([H])C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F Chemical compound [H]C([H])(OOC([H])([H])C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F WLOYYMYGUUIYAH-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005804 perfluoroheptyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、フッ化ビニリデン系共重合体の製造方法に関
し、特に柔軟性、耐衝撃性及び耐寒性に優れたフッ化ビ
ニリデン系共重合体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 vinylidene fluoride copolymer, and in particular a vinylidene fluoride copolymer having excellent flexibility, impact resistance, and cold resistance. Relating to a manufacturing method.
ボリフッ化ビニリデンは、耐候性、耐蝕性、電気的特性
、加工性等に優れるため、多岐にわたる用途に使用され
ている。Polyvinylidene fluoride has excellent weather resistance, corrosion resistance, electrical properties, workability, etc., and is therefore used in a wide variety of applications.
しかし、ボリフッ化ビニリデンは結晶性が大きいため、
加工時の残留応力が大きく、経時においてストレスクラ
ックが生じ易く、また柔軟性に欠け、耐衝撃性、耐寒性
も他のフッ素系樹脂に比して劣っている。However, since polyvinylidene fluoride is highly crystalline,
It has large residual stress during processing, tends to cause stress cracks over time, lacks flexibility, and is inferior to other fluororesins in impact resistance and cold resistance.
そこで、柔軟性、耐衝撃性及び耐寒性を改良するために
、フン化ビニリデンと他の単量体、例えば、ヘキサフル
オ口プロピレン、テトラフルオロエチレン、メチルメタ
クリレート、プチルアクリレートなどとを共重合する方
法、あるいはポリフッ化ピニリデンにアクリル系樹脂等
を配合する方法などが提案されている。Therefore, in order to improve flexibility, impact resistance and cold resistance, a method of copolymerizing vinylidene fluoride with other monomers such as hexafluoropropylene, tetrafluoroethylene, methyl methacrylate, butyl acrylate, etc. Alternatively, a method has been proposed in which an acrylic resin or the like is blended with polypinylidene fluoride.
しかし、上記従来の方法によって得られるフッ化ビニリ
デンと他の単量体との共重合体は、柔軟性には優れるが
、融点が低下して使用可能な温度領域が低下したり、加
工性が悪化するという問題がある。However, although the copolymer of vinylidene fluoride and other monomers obtained by the above-mentioned conventional method has excellent flexibility, it has a low melting point, which reduces the usable temperature range, and has poor processability. The problem is that it gets worse.
またポリフッ化ビニリデンにアクリル系樹脂等を配合す
る方法によって得られるｍ戒物は、透明性、加工性及び
柔軟性には優れるが、耐候性及び耐薬品性が悪化する問
題があった。In addition, m-Kaimono obtained by blending polyvinylidene fluoride with an acrylic resin or the like has excellent transparency, processability, and flexibility, but has the problem of poor weather resistance and chemical resistance.
そこで本発明の目的は、ボリフッ化ビニリデンが本来有
する特性を損なわずに、柔軟性、耐衝撃性及び耐寒性に
優れるフッ化ビニリデン系共重合体を製造する方法を提
供することにある．〔課題を解決するための手段〕
本発明者らは上記の課題を解決する方法として？ッ化ビ
ニリデンと一般式ＣＩｌ■＝ＣＨ−Ｒｆで示されるフッ
素化合物との共重合体の製造方法について先に出願した
が（特願平０１−６２８５２）、本発明は、これをさら
に改良したものである。Therefore, an object of the present invention is to provide a method for producing a vinylidene fluoride copolymer that has excellent flexibility, impact resistance, and cold resistance without impairing the inherent properties of polyvinylidene fluoride. [Means for Solving the Problems] How did the present inventors solve the above problems? An application was previously filed for a method for producing a copolymer of vinylidene fluoride and a fluorine compound represented by the general formula CIl=CH-Rf (Japanese Patent Application No. 01-62852), but the present invention further improves this. It is.
本発明によれば、
（Ａ）フッ化ビニリデン ９９．９〜５０重量部、及び
、
（Ｂ）一般式（Ｉ）：
ＣＩ，雲ＣＨ−Ｒｆ （ １ ）〔式
中、Ｒｆは炭素原子数１〜１２のパーフルオロアルキル
基である〕
で表される重合性二重結合を有するフッ素化合物 ０．
１〜５０重量部、
（ここでＡ及びＢ成分の合計量を１００重量部とする．
）
を含む単量体混合物を、ラジカル重合開始剤の存在下に
共重合させることによってフン化ビニリデン系共重合体
を製造する方法において、該（Ｂ）或分の少なくとも３
０重量％は、重合反応率が７０％に達するまでに、逐次
又は連続的に重合系中に後添加されて重合が行われるこ
とを特徴とするフッ化ビニリデン系共重合体の製造方法
が提供される。According to the present invention, (A) 99.9 to 50 parts by weight of vinylidene fluoride, and (B) general formula (I): CI, cloud CH-Rf (1) [wherein, Rf is 1 carbon atom] -12 perfluoroalkyl groups] A fluorine compound having a polymerizable double bond represented by 0.
1 to 50 parts by weight (Here, the total amount of components A and B is 100 parts by weight.
) A method for producing a vinylidene fluoride copolymer by copolymerizing a monomer mixture containing (B) in the presence of a radical polymerization initiator, wherein at least 3
Provided is a method for producing a vinylidene fluoride copolymer, characterized in that 0% by weight is post-added into the polymerization system sequentially or continuously until the polymerization reaction rate reaches 70%. be done.
即ち、本発明において第１の特徴は、フッ化ビニリデン
と共重合させるべき重合性二重結合を有するフッ素化合
物（成分Ｂ）の少なくとも３０重量％、特に５０重量％
以上を、重合系中に後添加することである。That is, the first feature of the present invention is that at least 30% by weight, particularly 50% by weight of the fluorine compound (component B) having a polymerizable double bond to be copolymerized with vinylidene fluoride.
The above is post-added into the polymerization system.
尚、本発明において、後添加とは、重合開始後に添加す
ることを意味する。In the present invention, post-addition means addition after the start of polymerization.
本発明によれば、このように共重合させる単量体成分の
一部を後添加することによって、後述する実施例及び比
較例に示される通り、ボリフッ化ビニリデンの柔軟性、
耐衝撃性、耐寒性等の特性が改善されるのである。According to the present invention, by post-adding a part of the monomer component to be copolymerized, the flexibility of polyvinylidene fluoride can be improved, as shown in the Examples and Comparative Examples described later.
Properties such as impact resistance and cold resistance are improved.
後添加されるフッ素化合物の量が３０重量％よりも少な
くなると、最初から全量を仕込んだ場合とほとんど変わ
らず、後添加する効果が認められない。When the amount of the fluorine compound added later is less than 30% by weight, there is almost no difference from the case where the entire amount is added from the beginning, and the effect of the post-addition is not recognized.
本発明において第２の特徴は、フッ化ビニリデンと共重
合させるべき（Ｂ）ｔｃ分であるフッ素化合物の後添加
を、重合反応率が７０％に達するまでに行うこと、換言
すると、重合反応率が７０％に達するまでに（Ｂ）成分
の全量を重合系中に添加することである。The second feature of the present invention is that the post-addition of the (B) tc fluorine compound to be copolymerized with vinylidene fluoride is performed until the polymerization reaction rate reaches 70%, in other words, the polymerization reaction rate The entire amount of component (B) should be added to the polymerization system until the amount reaches 70%.
このフッ素化合物の後添加が、重合反応率が７０％を超
えた後においても行われる場合には、共重合反応に関与
するフッ化ビニリデンモノマー濃度が低く、均一な共重
合体が得られないため、かえって性能が低下する。If this post-addition of the fluorine compound is carried out even after the polymerization reaction rate exceeds 70%, the concentration of the vinylidene fluoride monomer involved in the copolymerization reaction will be low and a uniform copolymer will not be obtained. , on the contrary, the performance deteriorates.
また、このフッ素化合物の後添加は、重合反応率が少な
くとも３０％に達するまでは、実質的に完了しないよう
に行うことが望ましい。Further, it is desirable that the post-addition of the fluorine compound is not substantially completed until the polymerization reaction rate reaches at least 30%.
即ち、あまりに早く後添加が完了しても、後添加する意
味がなくなるからである。That is, even if the post-addition is completed too quickly, there is no point in post-adding.
（好適態様の説明）
星旦比且立艷
本発明で使用される単量体混合物は、
（Ａ）フッ化ビニリデン ９９．９〜５０重量部、特に
９９．５〜７帽１部、
及び、
（Ｂ）一般式（■）：
ＣＨ！＝ＣＨ−Ｒｒ （ １ ）〔式
中、Ｒｆは炭素原子数１〜１２のパーフルオロアルキル
基である〕
で表される重合性二重結合を有するフッ素化合物 ０．
１〜５０重量部、特に０．５〜３０重量部、
（ここでＡ及びＢ或分の合計量を１００重量部とする。(Description of preferred embodiments) The monomer mixture used in the present invention includes (A) 99.9 to 50 parts by weight of vinylidene fluoride, particularly 1 part of 99.5 to 7 parts by weight, and (B) General formula (■): CH! =CH-Rr (1) [In the formula, Rf is a perfluoroalkyl group having 1 to 12 carbon atoms] Fluorine compound having a polymerizable double bond represented by 0.
1 to 50 parts by weight, especially 0.5 to 30 parts by weight (here, the total amount of A and B is 100 parts by weight).
） を含有しているものである。) It contains.
単量体混合物中の（Ｂ）成分の配合量が０．１重量部未
満であると、得られる共重合体の柔軟性、耐衝撃性及び
耐寒性が改良されず、５０重量部を超えると耐候性、耐
蝕性、電気的特性等においてポリフッ化ビニリデンが本
来持つ優れた特長が損なわれてしまう．
この（Ｂ）成分であるフッ素化合物を表す前記一般式（
１）において、Ｒｆは炭素原子数１〜１２のパーフルオ
ロアルキル基であり、例えば、パーフルオロメチル基、
パーフルオロエチル基、パーフルオロブロビル基、バー
フルオロブチル基、パーフルオロペンチル基、バーフル
オロヘキシル基、バーフルオロヘプチル基、パーフルオ
ロオクチル基、バーフルオロドデシル基等が挙げられる
。この（Ｂ）ｔｃ分のフッ素化合物の具体例として、パ
ーフルオロメチルエチレン（三フッ化プロピレン）、パ
ーフルオロブチルエチレン、バーフルオロヘキシルエチ
レン、バーフルオロオクチルエチレン、パーフルオロド
デシルエチレン等が挙げられる．これらは１種単独でも
２種以上を組み合わせても用いられる。If the amount of component (B) in the monomer mixture is less than 0.1 parts by weight, the flexibility, impact resistance and cold resistance of the resulting copolymer will not be improved, and if it exceeds 50 parts by weight, Polyvinylidene fluoride's original excellent features such as weather resistance, corrosion resistance, and electrical properties will be lost. The above general formula (
In 1), Rf is a perfluoroalkyl group having 1 to 12 carbon atoms, for example, a perfluoromethyl group,
Examples include perfluoroethyl group, perfluorobrovyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorododecyl group, and the like. Specific examples of the fluorine compound having the tc (B) include perfluoromethylethylene (propylene trifluoride), perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorododecylethylene, and the like. These may be used alone or in combination of two or more.
本発明の方法において使用される単量体混合物は、本発
明の目的を損なわない範囲内において、前記（Ａ）のフ
ッ化ビニリデンと（Ｂ）のフッ素化合物の他に、フッ化
ビニリデン又は（Ｂ）のフッ素化合物と共重合可能な重
合性二重結合を有する他の単量体を含んでいてもよい。The monomer mixture used in the method of the present invention includes vinylidene fluoride or (B) in addition to the vinylidene fluoride (A) and the fluorine compound (B), within a range that does not impair the purpose of the present invention. ) may contain other monomers having a polymerizable double bond that can be copolymerized with the fluorine compound.
この他の単量体としては、例えば、テトラフルオロエチ
レン、ヘキサフルオ口プロピレン、クロロトリフルオロ
エチレン等のフッ素系単量体；エチレン、メチルメタク
リレート等が挙げられる。これらは、１種単独でも２種
以上を組み合わせても用いられる。Examples of other monomers include fluorine-based monomers such as tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene; ethylene, methyl methacrylate, and the like. These may be used alone or in combination of two or more.
一ジカル Ａ
用いられるラジカル重合開始剤としては、通常、フン化
ビニリデンの重合に使用されているものであれば、いず
れのものでもよい。例えば、ジｎブロビルパーオキシジ
カーボネート、ジイソプロピルパーオキシジカーボネー
ト、ヘプタフルオ口プチルパーオキシド、ｔ−プチルパ
ーオキシイソプチレート、インブチリルパーオキシド、
過硫酸アンモニウム、過硫酸カリウム等の有機又は無機
の過酸化物；α、α′−アゾビス（α、Ｔ′−ジメチル
バレロアξジン）塩酸塩等のアゾ化合物；レドックス系
重合開始剤などが挙げられる。これらは１種単独でも２
種以上を組み合わせても用いられる。Monoradical A The radical polymerization initiator used may be any one that is normally used in the polymerization of vinylidene fluoride. For example, di-n-brovyl peroxydicarbonate, diisopropyl peroxydicarbonate, heptafluorobutyl peroxide, t-butyl peroxyisoptylate, imbutyryl peroxide,
Examples include organic or inorganic peroxides such as ammonium persulfate and potassium persulfate; azo compounds such as α,α′-azobis(α,T′-dimethylvaleroaξzine) hydrochloride; redox polymerization initiators, etc. . Each of these alone has 2
It can also be used in combination of more than one species.
共１１え応
共重合反応の形式は特に限定されず、懸濁重合、乳化重
合、溶液重合、塊状重合等のいずれの形式によっても行
うことができる。The type of copolymerization reaction is not particularly limited, and any type of polymerization such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization can be used.
例えば、懸濁重合により共重合させる場合には、フッ化
ビニリデンをラジカル重合開始剤の存在下に懸濁重合さ
せる場合に行われる一般的な方法に準じて行えばよい。For example, when copolymerizing by suspension polymerization, it may be carried out according to a general method used when vinylidene fluoride is subjected to suspension polymerization in the presence of a radical polymerization initiator.
この場合に使用される懸濁剤としては、例えば、メチル
セルロース、ポリビニルアルコール等の水溶性高分子化
合物等が挙げられる。Examples of the suspending agent used in this case include water-soluble polymer compounds such as methylcellulose and polyvinyl alcohol.
また、得られる共重合体の分子量を調整するために、イ
ソブロビルアルコール、アセトン、１−ブチルアルコー
ル、イソペンタン等の連鎖移動剤を、あるいはリン酸二
ナトリウム等のｐＨ緩衝剤；苛性ソーダ等のｐＨ調整剤
などを使用することも任意である。In addition, in order to adjust the molecular weight of the resulting copolymer, a chain transfer agent such as isobrobyl alcohol, acetone, 1-butyl alcohol, isopentane, etc., or a pH buffer agent such as disodium phosphate; pH adjustment such as caustic soda may be added. The use of agents and the like is also optional.
さらに、懸濁重合又は乳化重合によって、本発明の共重
合体を製造する場合に、重合媒体として、一般的には水
が用いられるが、トリクロロトリフルオロエタン等の疎
水性ハロゲン化炭化水素系溶剤を併用することも任意で
ある。Furthermore, when producing the copolymer of the present invention by suspension polymerization or emulsion polymerization, water is generally used as the polymerization medium, but hydrophobic halogenated hydrocarbon solvents such as trichlorotrifluoroethane are also used. It is also optional to use them together.
共重合反応の重合条件としては、前述したように、一定
の時期に、一定量の（Ｂ）成分を後添加することを除け
ば、それ自体公知の条件が採用され、通常、重合温度は
Ｏ〜１００″Ｃ、重合時間は１〜５０時間とされる。As mentioned above, the polymerization conditions for the copolymerization reaction are those known per se, except for the post-addition of a certain amount of component (B) at a certain time, and the polymerization temperature is usually O ~100''C, and the polymerization time is 1 to 50 hours.
以下、実施例により本発明を詳細に説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
内容積１℃のステンレス製反応器にイオン交換水５ ０
０ｍｆｆｉ，メチルセルロース０．１ｇ，イソプロビ
ルバーオキシジカーボネー｝ ０． ５ ｇ及びトリク
ロロトリフルオロエタン１００ｇを仕込み、反応器内を
窒素置換した後、真空にした。Example 1 50 ml of ion-exchanged water was placed in a stainless steel reactor with an internal volume of 1°C.
0mffi, methylcellulose 0.1g, isoprobil baroxydicarbonate} 0. After charging 5 g and 100 g of trichlorotrifluoroethane, the inside of the reactor was purged with nitrogen and then evacuated.
次にフッ化ビニリデン９６ｇを仕込み、５０゜Ｃに加熱
して重合を開始させた。内温が５０゜Ｃに達した時点で
パーフルオロブチルエチレンＩｇを圧人し、さらに５時
間毎に１ｇずつ圧入して、合計４ｇを１５時間で圧入し
た。Next, 96 g of vinylidene fluoride was charged and heated to 50°C to initiate polymerization. When the internal temperature reached 50°C, perfluorobutylethylene Ig was injected, and 1 g was further injected every 5 hours, so that a total of 4 g was injected over 15 hours.
反応器内圧は当初３０ｋｇを示したが、重合を開始して
から２４時間後に内圧が１５ｋＧとなったところで、未
反応モノマーをパージし、反応混合物を反応器から取り
出し、冷却・脱水及び乾燥して白色粉末状の共重合体７
２ｇを得た。Initially, the internal pressure of the reactor was 30 kg, but 24 hours after the start of polymerization, the internal pressure reached 15 kG, and unreacted monomers were purged, and the reaction mixture was taken out of the reactor, cooled, dehydrated, and dried. White powder copolymer 7
2g was obtained.
得られた共重合体を熱プレスで厚さ１ｍｍの板状に戒形
し、ＪＩＳ Ｋ６７４５に準じて３０゜Ｃにおけるねじ
り剛性率を測定し、またＡＳＴＭ Ｄ２５６に準じてア
イゾッド衝撃強度を、ＪＩＳ Ｋ？２１６に準じて脆化
温度を測定した。結果を表−１に示す。The obtained copolymer was formed into a plate shape with a thickness of 1 mm by hot pressing, and the torsional rigidity at 30°C was measured according to JIS K6745, and the Izod impact strength was measured according to ASTM D256. ? The embrittlement temperature was measured according to 216. The results are shown in Table-1.
実施例２〜４
各例において、パーフルオロプチルエチレンの代わりに
、表−１に示すフッ素化合物を使用した以外は、実施例
１と同様にして共重合体を得、得られた共重合体のねじ
り剛性率、アイゾッド衝撃強度及び脆化温度を測定した
。結果を表−１に示す。Examples 2 to 4 In each example, a copolymer was obtained in the same manner as in Example 1, except that a fluorine compound shown in Table 1 was used instead of perfluoroptylethylene, and the resulting copolymer was Torsional rigidity, Izod impact strength and embrittlement temperature were measured. The results are shown in Table-1.
比較例１
ソルベイ社製のポリフッ化ビニリデン（ソーレフ１００
Ｂ）について、実施例１と同様にして、ねしり剛性率、
アイゾッド衝撃強度及び脆化温度を測定した．結果を表
−１に示す。Comparative Example 1 Polyvinylidene fluoride (Solef 100) manufactured by Solvay
Regarding B), in the same manner as in Example 1, torsional rigidity,
Izod impact strength and embrittlement temperature were measured. The results are shown in Table-1.
比較例２
パーフルオ口ブチルエチレンを全量最初から仕込んだ以
外は実施例１と同様にした。結果は表−１に示した．
比較例３
バーフルオロブチルエチレンを最初に３ｇ仕込み、重合
開始１５時間後に残りのＩｇを圧人した以外は実施例１
と同様にした。結果を表−１に示した。Comparative Example 2 The same procedure as Example 1 was carried out except that the entire amount of perfluorinated butyl ethylene was charged from the beginning. The results are shown in Table 1. Comparative Example 3 Example 1 except that 3 g of barfluorobutyl ethylene was initially charged and the remaining Ig was compressed 15 hours after the start of polymerization.
I did the same thing. The results are shown in Table-1.
比較例４
パーフルオロブチルエチレンを最初に１ｇ仕込み重合開
始２０時間後、内圧が１２ｋＧとなった時点（予備実験
で収率７５％であることを確認している）で残りの３ｇ
４圧入した以外は実施例１と同様に行なった。結果を表
−１に示した。Comparative Example 4 1 g of perfluorobutyl ethylene was initially charged, and 20 hours after the start of polymerization, the remaining 3 g was added when the internal pressure reached 12 kG (preliminary experiments confirmed that the yield was 75%).
The same procedure as in Example 1 was carried out except that 4 pieces were press-fitted. The results are shown in Table-1.
実施例５，６
内容積２１．のステンレス製反応器にイオン交換水ｉｌ
，メチルセルロース０．２ｇ，イソプロビルパーオキシ
ジカーボネート１ｇ１ トリクロロトリフルオ口エタン
１００ｇを仕込み、反応器内を窒素置換した後、真空に
した。Examples 5 and 6 Internal volume 21. ion-exchanged water in a stainless steel reactor
, 0.2 g of methyl cellulose, 1 g of isopropyl peroxydicarbonate, and 100 g of trichlorotrifluoroethane were charged, and the inside of the reactor was purged with nitrogen and then evacuated.
次にフッ化ビニリデン１８０ｇを仕込み、内温を４５゜
Ｃとして重合を開始した。内温を４５゜Ｃに達した時点
でパーフルオロメチルエチレン（三フッ化プロピレン）
２ｇを圧人し、以后１時間毎にｌｇずつ添加し、合計２
０ｇを仕込んだ。Next, 180 g of vinylidene fluoride was charged, the internal temperature was raised to 45°C, and polymerization was started. When the internal temperature reaches 45°C, add perfluoromethylethylene (propylene trifluoride).
Press down 2g and then add 1g every hour for a total of 2g.
0g was charged.
２４時間後に未反応モノマーをパージし、反応生成物を
脱水、乾燥して白色粉末状の共重合体１６０ｇを得た。After 24 hours, unreacted monomers were purged, and the reaction product was dehydrated and dried to obtain 160 g of a white powdery copolymer.
得られた共重合体の物性を実施例１と同様にして測定し
た。結果を表−２に示す。The physical properties of the obtained copolymer were measured in the same manner as in Example 1. The results are shown in Table-2.
実施例６
実施例５と同様にして重合を開始した。但しフッ化ビニ
リデンの仕込み量は１９８ｇとした。開始後２時間目に
パーフルオ口メチルエチレン１ｇを圧入し、さらに５時
間後に１ｇを圧大して重合した。結果を表−２に示した
。Example 6 Polymerization was started in the same manner as in Example 5. However, the amount of vinylidene fluoride charged was 198 g. Two hours after the start, 1 g of perfluorinated methyl ethylene was injected under pressure, and after another 5 hours, 1 g was added under pressure for polymerization. The results are shown in Table-2.
比較例５
パーフルオロメチルエチレン２ｇを最初から仕込んだ以
外は実施例６と同様にした。結果を表一２に示した。Comparative Example 5 The same procedure as Example 6 was carried out except that 2 g of perfluoromethylethylene was charged from the beginning. The results are shown in Table 2.
Claims (1)
ルキル基である〕 で表される重合性二重結合を有するフッ素化合物０．１
〜５０重量部、 （ここでＡ及びＢ成分の合計量を１００重量部とする。 ） を含む単量体混合物を、ラジカル重合開始剤の存在下に
共重合させることによってフッ化ビニリデン系共重合体
を製造する方法において、 該（Ｂ）成分の少なくとも３０重量％は、重合反応率が
７０％に達するまでに、逐次又は連続的に重合系中に後
添加されて重合が行われることを特徴とするフッ化ビニ
リデン系共重合体の製造方法。[Scope of Claims] (A) 99.9 to 50 parts by weight of vinylidene fluoride, and (B) General formula (I): CH_2=CH-R_f(I) [In the formula, R_f has 1 to 1 carbon atom] 12 perfluoroalkyl group] A fluorine compound having a polymerizable double bond represented by 0.1
~50 parts by weight, (here, the total amount of components A and B is 100 parts by weight) is copolymerized in the presence of a radical polymerization initiator to form a vinylidene fluoride copolymer. The method for producing a polymer is characterized in that at least 30% by weight of the component (B) is sequentially or continuously post-added into the polymerization system until the polymerization reaction rate reaches 70% to carry out the polymerization. A method for producing a vinylidene fluoride copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1192178A JPH0356516A (en) | 1989-07-25 | 1989-07-25 | Production of vinylidene fluoride-based copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1192178A JPH0356516A (en) | 1989-07-25 | 1989-07-25 | Production of vinylidene fluoride-based copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0356516A true JPH0356516A (en) | 1991-03-12 |
Family
ID=16286977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1192178A Pending JPH0356516A (en) | 1989-07-25 | 1989-07-25 | Production of vinylidene fluoride-based copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0356516A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004528451A (en) * | 2001-05-02 | 2004-09-16 | スリーエム イノベイティブ プロパティズ カンパニー | Emulsifier-free aqueous emulsion polymerization for producing fluoropolymers |
| WO2020017561A1 (en) * | 2018-07-20 | 2020-01-23 | 株式会社クレハ | Particulate vinylidene-fluoride-based polymer and method for producing particulate vinylidene-fluoride-based polymer |
-
1989
- 1989-07-25 JP JP1192178A patent/JPH0356516A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004528451A (en) * | 2001-05-02 | 2004-09-16 | スリーエム イノベイティブ プロパティズ カンパニー | Emulsifier-free aqueous emulsion polymerization for producing fluoropolymers |
| WO2020017561A1 (en) * | 2018-07-20 | 2020-01-23 | 株式会社クレハ | Particulate vinylidene-fluoride-based polymer and method for producing particulate vinylidene-fluoride-based polymer |
| JPWO2020017561A1 (en) * | 2018-07-20 | 2021-06-24 | 株式会社クレハ | A method for producing a particulate vinylidene fluoride-based polymer and a particulate vinylidene fluoride-based polymer. |
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