JPH0234606A - Manufacture of vinylidene fluoride copolymer - Google Patents
Manufacture of vinylidene fluoride copolymerInfo
- Publication number
- JPH0234606A JPH0234606A JP18384188A JP18384188A JPH0234606A JP H0234606 A JPH0234606 A JP H0234606A JP 18384188 A JP18384188 A JP 18384188A JP 18384188 A JP18384188 A JP 18384188A JP H0234606 A JPH0234606 A JP H0234606A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- tables
- vinylidene fluoride
- group
- formula
- 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 description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims 1
- 150000003961 organosilicon compounds Chemical class 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 abstract 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 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
- -1 hexafluoropropylene, tetrafluoroethylene, methyl Chemical group 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UZUFPBIDKMEQEQ-UHFFFAOYSA-N perfluorononanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UZUFPBIDKMEQEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer 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
- 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 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- 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
系共重合体を製造する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a vinylidene fluoride copolymer, particularly for producing a vinylidene fluoride copolymer having excellent impact resistance and cold resistance. Regarding the method.
ポリフッ化ビニリデン（以下、ｒ ＰＶｄＦ Ｊと略す
ことがある）は、耐候性、耐蝕性、電気的特性及び加工
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 (hereinafter sometimes abbreviated as r PVdF J) has excellent weather resistance, corrosion resistance, electrical properties, processability, etc., and is therefore used in a wide variety of applications.
しかし、ＰＶｄＦ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ンクが生じ易
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。そこで、耐衝撃性及び耐寒
性を改良するため、フッ化ビニリデンと他の単量体、例
えばヘキサフルオロプロピレン、テトラフルオロエチレ
ン、メチルメタクリレート、ブチルアクリレートなどと
を共重合する方法、あるいはＰＶｄＦにアクリル系樹脂
等を配合する方法等が提案されている。However, due to its high crystallinity, PVdF has large residual stress during processing, tends to cause stress cranks over time, lacks flexibility, and has inferior impact resistance and cold resistance compared to other fluororesins. There is. Therefore, in order to improve impact resistance and cold resistance, a method of copolymerizing vinylidene fluoride with other monomers such as hexafluoropropylene, tetrafluoroethylene, methyl methacrylate, butyl acrylate, etc., or a method of copolymerizing PVdF with acrylic Methods of blending resins and the like have been proposed.
しかし、フッ化ビニリデンと他の単量体とを共重合する
上記従来の方法によって得られる共重合体は、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、加工性が悪化する問題がある。またＰＶｄＦに
アクリル系樹脂等を配合する方法によって得られる組成
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る。However, although copolymers obtained by the above-mentioned conventional method of copolymerizing vinylidene fluoride and other monomers have excellent flexibility, they have low melting points and a reduced usable temperature range. There is a problem that processability deteriorates. Further, a composition obtained by blending PVdF 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、ＰＶｄＦが本来持つ特長とと
もに、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。Therefore, an object of the present invention is to provide a method for producing a vinylidene fluoride copolymer that has excellent impact resistance and cold resistance as well as the inherent characteristics of PVdF.
本発明は、上記課題を解決するものとして、（Ａ）フッ
化ビニリデンを必須成分として含む重合性二重結合を有
する単量体と、
（Ｂ）一般式Ｎ）、（ＩＩ）、（ＩＩＩ）、（ＩＶ）及
び（Ｖ）：
〔式中、Ｒ１は水素原子又は炭素原子数１〜３のアルキ
ル基、Ｒ２は２価の有機基であり、Ｒ３、Ｒ４及びＲ５
は同−又は異なってもよく、炭素原子数１〜２０の１価
の炭化水素基、炭素原子数１〜３のアルコキシ基又は弐
：
（複数のＲ６は同−又は異なってもよく、炭素原子数１
〜２０の１価の炭化水素基、ｎは０〜１００の整数であ
り、ＲｔはＲｈと同じ意味を有するか、または下記式：
〔Ａは前記と同じ〕
（ここで、Ｒ６及びｎは前記のとおり
である。）
で表される基である。）〕
〔ここで、Ａは下記式：
％式％
前記と同じ）
で表される基である〕
ＣＨ＝ＣＨ（Ｉ［Ｉ ）
〔Ａは前記のとおり〕
υ
〔ここで、Ｒ１、Ｒ３、Ｒ４及びＲ５は前記−最大（Ｉ
）と同じ〕
で表される重合性二重結合を有する有機けい素化合物か
ら選ばれる少なくとも１種とを、（Ａ） ／（Ｂ）の重
量比が５０１５０〜９９／１である割合で、ラジカル重
合開始剤の存在下で反応させ、前記（Ａ）成分と（Ｂ）
成分を共重合させるフッ化ビニリデン系共重合体の製造
方法を提供するものである。The present invention solves the above problems by using (A) a monomer having a polymerizable double bond containing vinylidene fluoride as an essential component; , (IV) and (V): [wherein R1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R2 is a divalent organic group, and R3, R4 and R5
may be the same or different, a monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or Number 1
~20 monovalent hydrocarbon groups, n is an integer from 0 to 100, Rt has the same meaning as Rh, or the following formula:
[A is the same as above] (wherein R6 and n are as above). )] [Here, A is a group represented by the following formula: %Formula% Same as above] CH=CH(I [I ) [A is as above] υ [Here, R1, R3, R4 and R5 are -maximum (I
)] and at least one organosilicon compound having a polymerizable double bond represented by (A)/(B) in a weight ratio of 50,150 to 99/1 to form a radical. The above (A) component and (B) are reacted in the presence of a polymerization initiator.
The present invention provides a method for producing a vinylidene fluoride copolymer by copolymerizing components.
本発明の方法において（Ａ）成分として使用されるフッ
化ビニニリデンを必須成分として含む重合性二重結合を
有する単量体は、フッ化ビニリデン単独でもよいし、又
はフッ化ビニリデン及びフッ化ビニリデンと共重合可能
な重合性二重結合を有する他の単量体の単量体混合物で
もよい。フッ化ビニリデンと共重合可能な重合性二重結
合を有する他の単量体としては、例えば、テトラフルオ
ロエチレン、ヘキサフルオロプロピレン、クロロトリフ
ルオロエチレン等の他のフッ素系単量体；エチレン、メ
チルメタアクリレート等が挙げられる。The monomer having a polymerizable double bond containing vinylidene fluoride as an essential component used as component (A) in the method of the present invention may be vinylidene fluoride alone, or vinylidene fluoride and vinylidene fluoride. A monomer mixture of other monomers having copolymerizable polymerizable double bonds may also be used. Other monomers having polymerizable double bonds that can be copolymerized with vinylidene fluoride include, for example, other fluorine-based monomers such as tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene; ethylene, methyl Examples include methacrylate.
これらのフッ化ビニリデンと共重合可能な他の単量体は
、１種単独でも２種以上を組合わせて用いてもよい。These other monomers copolymerizable with vinylidene fluoride may be used alone or in combination of two or more.
本発明の方法で使用される（Ａ）成分であるフッ化ビニ
リデンを必須成分として含む単量体は、通常、フッ化ビ
ニリデンを５０重量％以上含むものである。The monomer containing vinylidene fluoride as an essential component, component (A), used in the method of the present invention usually contains 50% by weight or more of vinylidene fluoride.
本発明の方法において、（Ｂ）成分として使用される有
機けい素化合物は、前記−最大（Ｉ）、（ｎ）、（Ｉ［
［）、（ＩＶ）及び（Ｖ）で表されるものから選ばれる
少なくとも１種である。この−最大（Ｉ）、（ＩＩ）、
（ＩＩＩ）、（Ｉｔ／）及び（Ｖ）において、Ｒ１は水
素原子又は炭素原子数１〜３のアルキル基、例えばメチ
ル基、エチル基、プロピル基であり、Ｒ２は２価の有機
基、例えば、下記式：
％式％
（Ｒ’は炭素原子数１〜２０のアルキレン基又は式、：
Ｈ
ＣＨ２ＣＨＣＬ ＮＨＣｘＨｂ−
で表される基である。Ｒ１、Ｒ４及びＲ５は同−又は異
なってもよく、炭素原子数１〜２０の１価の炭化水素基
、例えば、メチル基、エチル基、プロピル基、ブチル基
、オクチル基、フェニル基等、炭素原子数１〜３のアル
コキシ基、例えば、メトキシ基、エトキシ基、プロポキ
シ基等、又は式：Ｓ−１：
（複数のＲｈは同−又は異なってもよく、炭素原子数１
〜２０の１価の炭化水素基、ｎはＯ〜１００の整数であ
り、Ｒ７はＲ６と同じ意味を有するか、又は下記式：
：
：
（ここで、Ｒｈ及びｎは前記のとおり
である。）
で表される基である。）
上記−最大（Ｉ）、（Ｉｔ）、（ＩＩＩ）、（ＩＶ）又
は（Ｖ）で表される有機けい素化合物の具体例として下
記式で表されるものが挙げられる。ただし、以下の式に
おいて、Ｍｅはメチル基、Ｅｔはエチル基、Ｐｒはプロ
ピル基、ｐｈはフェニル基を示す。In the method of the present invention, the organosilicon compounds used as component (B) include the above-mentioned maximum (I), (n), (I[
[), (IV) and (V). This - maximum (I), (II),
In (III), (It/) and (V), R1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, such as a methyl group, ethyl group, or propyl group, and R2 is a divalent organic group, such as , the following formula: %Formula% (R' is an alkylene group having 1 to 20 carbon atoms or a group represented by the formula: H CH2CHCL NHCxHb-. R1, R4 and R5 may be the same or different, Monovalent hydrocarbon groups having 1 to 20 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, octyl group, phenyl group, etc.; alkoxy groups having 1 to 3 carbon atoms, such as methoxy group; Ethoxy group, propoxy group, etc., or formula: S-1: (Plural Rhs may be the same or different, and have a carbon atom number of 1
~20 monovalent hydrocarbon group, n is an integer of O~100, R7 has the same meaning as R6, or the following formula: : : (where Rh and n are as described above). ) is a group represented by ) Specific examples of the organosilicon compounds represented by (I), (It), (III), (IV) or (V) above include those represented by the following formulas. However, in the following formula, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, and ph represents a phenyl group.
（ａ） 式（Ｉ）で表される有機けい素化合物Ｓ−４
：
Ｓ−５ニ
Ｓ−１１：
Ｓ−７：
５−１２：
Ｓ−８：
５−ｔＳ：
ｔ
Ｓ−９；
５−１４：
門ｅ
Ｓ−ｔＯ：
５−ｔＳ：
Ｓ
１６：
２２ニ
ーＯ５ｉＭｅ３）
Ｓ−１７：
Ｃ２Ｈ４−５ｉＭｅ＝
ら）
式
で表される有機けい素化合物
５−１９：
２０：
もの
５−２５：
２１：
で表されるもの
（Ｃ）
式（ＩＩ［）で表される有機けい素化合物５−２９：
ＩＣ＝ ＣＨ
において、
＾
で表されるもの
５−２６：
（ｅ）
式（Ｖ）で表される有機けい素化合物
Ｓ−３０＝
で表されるもの
（ｄ）
式
で表される有機けい素化合物
３１：
ｅ
で表されるもの
５−２８：
５−３２：
で表されるもの
本発明の方法は、前記（Ａ）成分と（Ｂ）成分を（Ａ）
／（Ｂ）の重量比が５０１５０〜９９／１である割合で
反応させて共重合させる方法である。（Ａ） ／（Ｂ）
の重量比が５０１５０未満であると得られる共重合体の
耐衝撃性及び耐寒性の改良効果が増大せず、ＰＶｄＦ本
来の特長が損なわれ、９９／ｌを超えると耐衝撃性及び
耐寒性が改良されない。(a) Organosilicon compound S-4 represented by formula (I)
: S-5 Ni S-11: S-7: 5-12: S-8: 5-tS: t S-9; 5-14: Gate e S-tO: 5-tS: S 16: 22 Ni O5iMe3 ) S-17: C2H4-5iMe= et al.) Organosilicon compound represented by the formula 5-19: 20: 5-25: 21: (C) Represented by the formula (II[) Organosilicon compound 5-29: IC=CH, represented by ^ 5-26: (e) Organosilicon compound represented by formula (V) S-30= (d) Organosilicon compound represented by the formula 31: e 5-28: 5-32: The method of the present invention combines the (A) component and (B) component into (A)
/(B) in a weight ratio of 50,150 to 99/1. (A) /(B)
If the weight ratio is less than 50150, the effect of improving the impact resistance and cold resistance of the resulting copolymer will not increase, and the original characteristics of PVdF will be impaired, and if it exceeds 99/l, the impact resistance and cold resistance will deteriorate. Not improved.
共重合は、通常、ラジカル重合開始剤の存在下で行われ
る。このラジカル重合開始剤としては、通常、フッ化ビ
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０例えば、ジロープロピルパーオキシジ
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、ヘプタフルオロブチルパーオキシド、ｔ−ブチルパ
ーオキシイソブチレート、過硫酸アンモルラム、過硫酸
カリウム等の有機及び無機の過酸化物；α、α′−アゾ
ビス（α 、ｌ−ジメチルバレロアミジン）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種でも２種以上組合わせても用いられる。Copolymerization is usually carried out in the presence of a radical polymerization initiator. This radical polymerization initiator may be any initiator as long as it is normally used in the polymerization of vinylidene fluoride. organic and inorganic peroxides such as oxide, t-butylperoxyisobutyrate, ammorum persulfate, potassium persulfate; azo compounds such as α,α′-azobis(α,l-dimethylvaleramidine) hydrochloride; Examples include redox polymerization initiators. These may be used alone or in combination of two or more.
この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。例えば、懸濁重合により共電゛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。また、得られる共重合体の分子
量を調整するために、イソプロピルアルコール、アセト
ン、イソペンタン等の連鎖移動剤を使用することも任意
である。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、水又
はトリクロロトリフルオロエチレン等の疎水性のフッ素
系化合物のいずれを使用することも任意である。The form of this copolymerization reaction is not particularly limited, and any form such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization can be used. For example, when carrying out coelectrification 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. Further, in order to adjust the molecular weight of the obtained copolymer, it is also optional to use a chain transfer agent such as isopropyl alcohol, acetone, isopentane, etc. Furthermore, when producing the copolymer of the present invention by suspension polymerization or emulsion polymerization, it is optional to use either water or a hydrophobic fluorine-based compound such as trichlorotrifluoroethylene as the polymerization medium. .
共重合反応の重合条件は、通常、重合温度２０〜１００
℃で重合時間１〜５０時間である。The polymerization conditions for the copolymerization reaction are usually a polymerization temperature of 20 to 100 ℃.
℃ and the polymerization time is 1 to 50 hours.
また、本発明の方法においては、（Ｂ）成分である有機
けい素化合物の重合器への仕込みは、これを全量、重合
の最初から仕込む方法あるいは重合率が５０％に達する
までに逐次、連続的又は数回に分けて添加する方法等、
いずれの方法によってもよい。In addition, in the method of the present invention, the organosilicon compound, which is component (B), can be charged into the polymerization vessel by charging the entire amount from the beginning of the polymerization, or sequentially and continuously until the polymerization rate reaches 50%. Methods such as adding target or dividing into several times, etc.
Any method may be used.
以下、実施例及び比較例を挙げて本発明の詳細な説明す
る。Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.
実施例１
内容積２１の重合器に、純水１１、メチルセルロース０
．４ｇ、イソプロピルアルコールＩＯｇ及びトリス（ト
リメチルシロキシ）メタクリルオキシプロピルシラン（
前記具体例で示したＳ −５） ４０ｇを仕込み、重合
系内を窒素置換した後、真空とし、フン化ビニリデン３
６０ｇを仕込んだ。その後、ジロープロビルオキシジカ
ーボネート４ｇをトリクロロトリフルオロエタン１２０
ｇに溶解してなる溶液を重合器内に圧入し、６０℃に昇
温して１０時間反応させた０次に、重合器内の未反応モ
ノマーをパージした後、反応生成物を重合器から取り出
し、冷却、脱水、乾燥して白色粉末状の共重合体３６０
ｇを得た。Example 1 In a polymerization vessel with an internal volume of 21, pure water 11 and methyl cellulose 0
．． 4g, isopropyl alcohol IOg and tris(trimethylsiloxy)methacryloxypropylsilane (
After charging 40 g of S-5) shown in the above specific example and replacing the inside of the polymerization system with nitrogen, vacuum was applied and vinylidene fluoride 3
60g was charged. Then, 4 g of diroprobyl oxydicarbonate was added to 120 g of trichlorotrifluoroethane.
The solution obtained by dissolving 1.g in 100 g was pressurized into a polymerization vessel, heated to 60°C, and reacted for 10 hours.Next, after purging unreacted monomers in the polymerization vessel, the reaction product was removed from the polymerization vessel. Take out, cool, dehydrate, and dry to obtain white powdery copolymer 360.
I got g.
得られた共重合体を、２０ｍｍφ押出機を用いてシリン
ダー温度１８０〜２００’Ｃ，ダイス温度２２０℃で溶
融して丸棒状に押出して冷却し、ペレタイザーでペレッ
ト状に切断した。The obtained copolymer was melted and extruded into a round bar using a 20 mmφ extruder at a cylinder temperature of 180 to 200'C and a die temperature of 220°C, cooled, and cut into pellets using a pelletizer.
次に、このペレ、フトを１５トン射出成形機を用いてシ
リンダー温度２３０〜２６０℃、金型温度４０℃で９０
Ｘ２２Ｘ４■の試験片に成形し、この試験片について、
ＡＳＴＭ−Ｄ２５６に準じてアイゾツト衝撃強度を、Ｊ
Ｉ Ｓ Ｋ７２１６にしたがって脆化温度を測定し
た。Next, the pellets and foam were molded using a 15-ton injection molding machine at a cylinder temperature of 230 to 260°C and a mold temperature of 40°C.
Formed into a test piece of X22X4■, about this test piece,
Izot impact strength according to ASTM-D256, J
The embrittlement temperature was measured according to IS K7216.
結果を表１に示す。The results are shown in Table 1.
比較例１
トリス（トリメチルシロキシ）メタクリルオキシプロピ
ルシラン（前記具体例で示した５−５）を使用しない以
外は実施例１と同様にして重合し、フッ化ビニリデンの
単独重合体を得た。Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that tris(trimethylsiloxy)methacryloxypropylsilane (5-5 shown in the above specific example) was not used to obtain a vinylidene fluoride homopolymer.
得られた重合体について、実施例１と同様にアイゾツト
衝撃強度及び脆化温度を測定した。The obtained polymer was measured for Izot impact strength and embrittlement temperature in the same manner as in Example 1.
結果を表１に示す。The results are shown in Table 1.
実施例２〜５
各側において、実施例１におけるトリス（トリメチルシ
ロキシ）メタクリルオキシプロビルシランの代わりに、
表１に示す有機けい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製造し、得られた共重合体か
ら試験片を作製してアイゾツト衝撃強度及び脆化温度を
測定した。Examples 2-5 On each side, instead of tris(trimethylsiloxy)methacryloxyprobylsilane in Example 1,
A copolymer was produced in the same manner as in Example 1, except that the organosilicon compounds shown in Table 1 were used, and test pieces were prepared from the obtained copolymer to measure Izot impact strength and embrittlement temperature. did.
結果を表１に示す。The results are shown in Table 1.
実施例６
内容積２１の重合器に、パーフロロオクチルカルボン酸
アンモニウム４ｇ１過硫酸アンモニウム２ｇ１イソペン
タン０．２ｇ及びトリス（トリメチルシロキシ）メタク
リルオキシプロピルシラン（前記具体例で示したＳ −
５） ８０ｇを仕込み、重合系内を窒素置換した後、真
空にした。フッ化ビニリデン１６０ｇを仕込んだ後、温
度８０″Ｃ１圧力４０ｋｇ／ｄで反応させた。圧力が降
下した時に、さらにフッ化ビニリデンを追加し、圧力を
４０ｋｇ／ｃｎｌに保持させる操作を、フッ化ビニリデ
ンの仕込み量が合計で３２０ｇになるまで操り返した後
、フン化ビニリデンの仕込みを停止した。その後、圧力
を１５ ｋｇ ／ｃｄまで降下させた。次に、重合器内
に残存する未反応モノマーをパージし、得られた反応生
成物を冷却して固形分濃度２４％のラテックスを得た。Example 6 In a polymerization vessel with an internal volume of 21, 4 g of ammonium perfluorooctylcarboxylate, 2 g of ammonium persulfate, 0.2 g of isopentane, and tris(trimethylsiloxy)methacryloxypropylsilane (S-
5) After charging 80 g and replacing the inside of the polymerization system with nitrogen, the system was evacuated. After charging 160 g of vinylidene fluoride, the reaction was carried out at a temperature of 80 cm and a pressure of 40 kg/d. When the pressure decreased, more vinylidene fluoride was added and the pressure was maintained at 40 kg/cnl. After repeating the procedure until the total amount of charged vinylidene fluoride was 320 g, the charging of vinylidene fluoride was stopped.Then, the pressure was lowered to 15 kg/cd.Next, unreacted monomers remaining in the polymerization vessel were removed. After purging, the resulting reaction product was cooled to obtain a latex with a solid content concentration of 24%.
このラテックスを塩析した後、脱水、乾燥して白色粉末
状の共重合体３２０ ｇを得た。After salting out this latex, it was dehydrated and dried to obtain 320 g of a white powdery copolymer.
得られた共重合体から実施例１と同様にして試験片を作
製してアイゾツト衝撃強度及び脆化温度を測定した。Test pieces were prepared from the obtained copolymer in the same manner as in Example 1, and the Izod impact strength and embrittlement temperature were measured.
結果を表２に示す。The results are shown in Table 2.
実施例７．８
各側において、トリス（トリメチルシロキシ）メタクリ
ルオキシプロピルシラン（Ｓ−５）及びフッ化ビニリデ
ンの使用量を表２に示す量に変えた以外は実施例６と同
様にして共重合体を製造し、アイゾツト衝撃強度及び脆
化温度を測定した。Example 7.8 Copolymerization was carried out in the same manner as in Example 6, except that on each side, the amounts of tris(trimethylsiloxy)methacryloxypropylsilane (S-5) and vinylidene fluoride used were changed to the amounts shown in Table 2. A composite was produced and the Izod impact strength and embrittlement temperature were measured.
結果を表２に示す。The results are shown in Table 2.
表２
実施例９
内容積ＩＮの重合器に、トリクロロトリフルオロエタン
６００ｇ、ジイソプロピルパーオキシジカーボネート２
ｇ、アセトン１０ｇ及び上記具体例において示したトリ
メトキシ・メタクリロキシプロピルシラン（Ｓ−６）２
０ｇを仕込み、重合系内を窒素置換した後、真空にした
。次に、ヘキサフルオロプロピレン４０ｇ及びフッ化ビ
ニリデン１４０ｇを仕込み、６０″Ｃで１０時間反応さ
せた。重合終了後、重合器内に残存する未反応モノマー
をパージし、生成した乳濁液を乾燥してトリクロロトリ
フルオロエタンを除去した後、得られた固形物を粉砕し
て白色微粉末状の共重合体１５０ｇを得た。Table 2 Example 9 In a polymerization vessel with an internal volume of IN, 600 g of trichlorotrifluoroethane and 2 diisopropyl peroxydicarbonate were added.
g, 10 g of acetone and trimethoxy methacryloxypropylsilane (S-6) 2 shown in the above specific example.
After charging 0 g and purging the inside of the polymerization system with nitrogen, the system was evacuated. Next, 40 g of hexafluoropropylene and 140 g of vinylidene fluoride were charged and reacted at 60"C for 10 hours. After the polymerization was completed, unreacted monomers remaining in the polymerization vessel were purged, and the resulting emulsion was dried. After removing trichlorotrifluoroethane, the resulting solid was pulverized to obtain 150 g of a white fine powder copolymer.
得られた共重合体から、実施例１と同様にして試験片を
作製し、この試験片についてアイゾツト衝撃強度を測定
したところ、試験片は破断しなかった。また脆化温度は
一５０°Ｃであった。A test piece was prepared from the obtained copolymer in the same manner as in Example 1, and when the Izod impact strength of this test piece was measured, the test piece did not break. The embrittlement temperature was -50°C.
本発明の方法によれば、耐衝撃性及び耐寒性に優れ、し
かもＰＶｄＦが本来有する特長を備えたフッ化ビニリデ
ン系共重合体を得ることができる。According to the method of the present invention, it is possible to obtain a vinylidene fluoride copolymer that has excellent impact resistance and cold resistance, and also has the characteristics inherent to PVdF.
代理人 弁理士 岩見谷 周志Agent Patent Attorney Shushi Iwamiya
Claims (1)
重結合を有する単量体と、 （Ｂ）一般式（ I ）、（II）、（III）、（IV）及び（
Ｖ）： ▲数式、化学式、表等があります▼（ I ） 〔式中、Ｒ＾１は水素原子又は炭素原子数１〜３のアル
キル基、Ｒ＾２は２価の有機基であり、Ｒ＾３、Ｒ＾４
及びＲ＾５は同一又は異なってもよく、炭素原子数１〜
２０の１価の炭化水素基、炭素原子数１〜３のアルコキ
シ基 又は式： ▲数式、化学式、表等があります▼ （複数のＲ＾６は同一又は異なってもよく、炭素原子数
１〜２０の１価の炭化水素基、 ｎは０〜１００の整数であり、Ｒ＾７はＲ＾６と同じ意
味を有するか、又は下記式： ▲数式、化学式、表等があります▼ （ここで、Ｒ＾６及びｎは前記のとおり である。） で表される基である。）〕 ▲数式、化学式、表等があります▼（II） 〔ここで、Ａは下記式： ▲数式、化学式、表等があります▼ （Ｒ＾２、Ｒ＾３、Ｒ＾４及びＲ＾５は 前記と同じ） で表される基である〕 ▲数式、化学式、表等があります▼（III） 〔Ａは前記のとおり〕 ▲数式、化学式、表等があります▼（IV） 〔Ａは前記と同じ〕 ▲数式、化学式、表等があります▼（Ｖ） 〔ここで、Ｒ＾２、Ｒ＾３、Ｒ＾４及びＲ＾５は前記一
般式（ I ）と同じ〕 で表される重合性二重結合を有する有機けい素化合物か
ら選ばれる少なくとも１種とを、（Ａ）／（Ｂ）の重量
比が５０／５０〜９９／１である割合で、ラジカル重合
開始剤の存在下で反応させ、前記（Ａ）成分と（Ｂ）成
分を共重合させるフッ化ビニリデン系共重合体の製造方
法。[Scope of Claims] (A) a monomer having a polymerizable double bond containing vinylidene fluoride as an essential component, (B) general formulas (I), (II), (III), (IV) and (
V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R^2 is a divalent organic group, and R ^3, R^4
and R^5 may be the same or different, and have a carbon atom number of 1 to
20 monovalent hydrocarbon groups, alkoxy groups with 1 to 3 carbon atoms, or formulas: ▲ Numerical formulas, chemical formulas, tables, etc. 20 monovalent hydrocarbon groups, n is an integer from 0 to 100, R^7 has the same meaning as R^6, or the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (where , R^6 and n are as described above.) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [Here, A is the following formula: ▲ Numerical formula, chemical formula , tables, etc. ▼ (R^2, R^3, R^4, and R^5 are the same as above) ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [A are as above] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) [A is the same as above] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) [Here, R^2, R^3, R^4 and R^5 are the same as the above general formula (I)] At least one organic silicon compound having a polymerizable double bond represented by A method for producing a vinylidene fluoride copolymer, which comprises reacting in the presence of a radical polymerization initiator and copolymerizing the components (A) and (B) at a ratio of 50/50 to 99/1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18384188A JPH0234606A (en) | 1988-07-22 | 1988-07-22 | Manufacture of vinylidene fluoride copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18384188A JPH0234606A (en) | 1988-07-22 | 1988-07-22 | Manufacture of vinylidene fluoride copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0234606A true JPH0234606A (en) | 1990-02-05 |
Family
ID=16142777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18384188A Pending JPH0234606A (en) | 1988-07-22 | 1988-07-22 | Manufacture of vinylidene fluoride copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0234606A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001207004A (en) * | 2000-01-28 | 2001-07-31 | Kanto Denka Kogyo Co Ltd | Resin composition |
| JP2009149905A (en) * | 1999-03-04 | 2009-07-09 | Kanto Denka Kogyo Co Ltd | Fluorine-containing copolymer solution and manufacturing method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6281409A (en) * | 1985-10-07 | 1987-04-14 | Dainippon Ink & Chem Inc | Production of hydrolyzable silyl group-containing fluoroolefin copolymer |
| JPS6327564A (en) * | 1986-07-18 | 1988-02-05 | Dainippon Ink & Chem Inc | Curable coating composition for electronic parts |
-
1988
- 1988-07-22 JP JP18384188A patent/JPH0234606A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6281409A (en) * | 1985-10-07 | 1987-04-14 | Dainippon Ink & Chem Inc | Production of hydrolyzable silyl group-containing fluoroolefin copolymer |
| JPS6327564A (en) * | 1986-07-18 | 1988-02-05 | Dainippon Ink & Chem Inc | Curable coating composition for electronic parts |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009149905A (en) * | 1999-03-04 | 2009-07-09 | Kanto Denka Kogyo Co Ltd | Fluorine-containing copolymer solution and manufacturing method thereof |
| JP2001207004A (en) * | 2000-01-28 | 2001-07-31 | Kanto Denka Kogyo Co Ltd | Resin composition |
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