JPS6354410A - Production of fluorinated vinyl copolymer - Google Patents
Production of fluorinated vinyl copolymerInfo
- Publication number
- JPS6354410A JPS6354410A JP19687686A JP19687686A JPS6354410A JP S6354410 A JPS6354410 A JP S6354410A JP 19687686 A JP19687686 A JP 19687686A JP 19687686 A JP19687686 A JP 19687686A JP S6354410 A JPS6354410 A JP S6354410A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- group
- acrylate
- meth
- polymerizable monomer
- 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.)
- Granted
Links
- 229920006163 vinyl copolymer Polymers 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 14
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- -1 alkyl vinyl ether Chemical compound 0.000 abstract description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 239000004711 α-olefin Substances 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 abstract description 3
- 229920001567 vinyl ester resin Polymers 0.000 abstract description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 abstract description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 239000005871 repellent Substances 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- CMVNWVONJDMTSH-UHFFFAOYSA-N 7-bromo-2-methyl-1h-quinazolin-4-one Chemical compound C1=CC(Br)=CC2=NC(C)=NC(O)=C21 CMVNWVONJDMTSH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HEJZJSIRBLOWPD-WCWDXBQESA-N didodecyl (e)-but-2-enedioate Chemical compound CCCCCCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCCCCCC HEJZJSIRBLOWPD-WCWDXBQESA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-L malate(2-) Chemical compound [O-]C(=O)C(O)CC([O-])=O BJEPYKJPYRNKOW-UHFFFAOYSA-L 0.000 description 1
- 150000004701 malic acid derivatives Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([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
- 238000003756 stirring Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、フッ素含有ビニル共重合体の溶液重合による
製造方法に関する。フッ素含有ビニル共重合体は、油性
化粧品、家具・自動車などのワックス類、更には、樹脂
類等の油溶性物質に配合或いは塗布することにより、そ
の表面にＩＢ水・ｔｎ油性、非粘着性、高潤滑性等を付
与するものとして好適に使用される。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a fluorine-containing vinyl copolymer by solution polymerization. Fluorine-containing vinyl copolymers can be blended with or applied to oil-soluble substances such as oil-based cosmetics, waxes for furniture and automobiles, and even resins to provide IB water/tn oil, non-adhesive, and It is suitably used as something that imparts high lubricity.
フッ素系ビニル共重合体は、従来から繊維等のｉａ水・
溌油処理剤として、水分散体や溶液の型で使用されてき
た。Fluorinated vinyl copolymers have traditionally been used for IA water, fibers, etc.
It has been used as an oil repellent treatment agent in the form of an aqueous dispersion or solution.
これら撥水・撥油剤の製造法として、一般的には以下の
ものが知られている。水分散体の例としては、特開昭５
５−９６１９号公報に記載されているように、フルオロ
アルキル基含有モノマー、ステアリル（メタ）アクリレ
ート及び第３成分モノマーを乳化重合する方法が挙げら
れている。The following methods are generally known as methods for producing these water and oil repellents. Examples of water dispersions include JP-A No. 5
As described in Japanese Patent No. 5-9619, a method is mentioned in which a fluoroalkyl group-containing monomer, stearyl (meth)acrylate, and a third component monomer are emulsion polymerized.
更に、溶液重合の例としては、特開昭５８−１１８８８
２号公報に記載されているように、ポリフルオロアルキ
ル基を含むモノマーとＣａ ” Ｃａ。の分岐アルキル
メタクリレート及び架橋性モノマーを溶液重合する場合
の好適な溶剤として、トリクロロトリフルオロエタン、
テトラクロロジフルオロエタンなどのハロゲン系溶剤が
挙げられている。Furthermore, as an example of solution polymerization, JP-A-58-11888
As described in Publication No. 2, trichlorotrifluoroethane, trichlorotrifluoroethane,
Halogenated solvents such as tetrachlorodifluoroethane are mentioned.
これら従来のｔａ水・撥油剤を油溶性物質に配合する場
合には、水分散体では混和性に問題があり、溶液型では
混和性は問題ないが、トリクロロトリフルオロエタンな
どの特殊なハロゲン系溶剤を使用するため、安全性・価
格の面から好ましくない。When blending these conventional TA water and oil repellents with oil-soluble substances, there is a problem with miscibility in water dispersion, and there is no miscibility problem in solution type, but special halogen-based agents such as trichlorotrifluoroethane Since it uses a solvent, it is unfavorable in terms of safety and cost.
そこで、従来の川水・撥油剤のこのような欠点を解決し
、油溶性物質の表面改質に適したフッ素含有共重合体溶
液が望まれている。Therefore, there is a need for a fluorine-containing copolymer solution that overcomes these drawbacks of conventional river water and oil repellents and is suitable for surface modification of oil-soluble substances.
本発明者らは、上記の問題点を解決する方法として、フ
ッ素含有共重合の非フツ素単量体及び重合溶媒に着目し
、種々検討を行った結果、非フツ素単量体としてフルオ
ロアルキル基を有する単量体と共重合し得る、炭素数８
以上のアルキル基を１つ以上有する単量体を選択し、更
に重合溶媒として脂肪族炭化水素を使用すると均一溶液
重合できることを見出した。この方法で製造されたフッ
素含有ビニル共重合体溶液は、脂肪族炭化水素を使用し
ており、安全性が高く低コストで効果の大きい表面改質
剤として好適である。As a method to solve the above problems, the present inventors focused on non-fluorine monomers and polymerization solvents for fluorine-containing copolymerization, and as a result of various studies, found that fluoroalkyl 8 carbon atoms that can be copolymerized with a monomer having a group
It has been found that homogeneous solution polymerization can be carried out by selecting a monomer having one or more of the above alkyl groups and further using an aliphatic hydrocarbon as a polymerization solvent. The fluorine-containing vinyl copolymer solution produced by this method uses aliphatic hydrocarbons, and is suitable as a highly safe, low-cost, and highly effective surface modifier.
即ち本発明は、フルオロアルキル基を有する重合性単量
体（Ａ） １０〜８０重量％、及び炭素数８以上のアル
キル基を１つ以上有する化合物（Ｂ）９０〜２０重量％
を、炭素数５以上の脂肪族炭化水素を溶媒として溶液重
合により共重合せしめることを特徴とするフッ素含有ビ
ニル共重合体の製造方法を提供するものである。That is, the present invention comprises 10 to 80% by weight of a polymerizable monomer (A) having a fluoroalkyl group, and 90 to 20% by weight of a compound (B) having one or more alkyl groups having 8 or more carbon atoms.
The present invention provides a method for producing a fluorine-containing vinyl copolymer, which comprises copolymerizing the following by solution polymerization using an aliphatic hydrocarbon having 5 or more carbon atoms as a solvent.
本発明の製造法において好ましい単量体の組み合わせは
、フルオロアルキル基を有する重合性単量体（Ａ）とし
てフルオロアルキル（メタ）アクリレート１０〜８０重
量％、炭素数８以上のアルキル基を１つ以上有する（Ａ
）と共重合し得る化合物（Ｂ）として炭素数８以上のア
ルキル基を有するアルキル（メタ）アクリレート９０〜
２０重量％が挙げられる。A preferred combination of monomers in the production method of the present invention is 10 to 80% by weight of fluoroalkyl (meth)acrylate as the polymerizable monomer (A) having a fluoroalkyl group, and one alkyl group having 8 or more carbon atoms. or more (A
) as a compound (B) copolymerizable with alkyl (meth)acrylate having an alkyl group having 8 or more carbon atoms 90 to
20% by weight is mentioned.
本発明に用いられるフルオロアルキル基を有する重合性
単量体（Ａ）としては、ポリフルオロアルキル基及びパ
ーフルオロアルキル基を有する（メタ）アクリレート、
ビニルエステル、ビニルエーテル、マレート、フマレー
ト、α−オレフィンなどの公知の化合物を挙げることが
できる。更に好ましいフルオロアルキル基としては、炭
素数４以上のポリフルオロアルキル基又はパーフルオロ
アルキル基が挙げられる。As the polymerizable monomer (A) having a fluoroalkyl group used in the present invention, (meth)acrylate having a polyfluoroalkyl group and a perfluoroalkyl group,
Known compounds such as vinyl esters, vinyl ethers, malates, fumarates, and α-olefins can be mentioned. More preferred fluoroalkyl groups include polyfluoroalkyl groups and perfluoroalkyl groups having 4 or more carbon atoms.
これらの化合物の例としては、例えば
ＣＨｔ＝ＣＨＣＯｚＣｔＨａＣｈＦＩｓ、ＣＨｔ−ＣＨ
ＣＯ□Ｃ！Ｈ４Ｃ１ＦＩ、。Examples of these compounds include, for example, CHt=CHCOzCtHaChFIs, CHt-CH
CO□C! H4C1FI,.
Ｃ１ｈ−ＣＨＣＯｔＣＪ＊Ｃ＋。Ｆｔｒ、 ＣＨｚ−Ｃ
（ＣＨｓ）ＣＯｔＣａ＊ＣｂＦｓｓ。C1h-CHCOtCJ*C+. Ftr, Chz-C
(CHs)COtCa*CbFss.
Ｃ１，−Ｃ（Ｃｌｈ）ＣＯｔＣ！Ｈ，ＣｌＦｌ叩、
ＣＦｌｔＣＨＯＣＯＣｔＨオＣ１Ｐ１ｔ＋ＣＨｚ−ＣＨ
ＯＣｔＨｔＣ１Ｆ＋ｔｌＣｓＦ＋ｔＣｔＨ＊０ＣＯＣＨ
ｆＣＨＣＯＯＣｔＨａＣｓＦ＋ｔ。C1,-C(Clh)COtC! H, ClFl hit,
CFltCHOCOCtHoC1P1t+CHz-CH
OCtHtC1F+tlCsF+tCtH*0COCH
fCHCOOCtHaCsF+t.
Ｃ＊Ｆ ＋ ｔｃＨ＝ｃＨｔなどが挙げられる。Examples include C*F + tcH=cHt.
本発明の（Ａ）と共重合し得る炭素数８以上のアルキル
基を１つ以上有する化合物（Ｂ）としては、（メタ）ア
クリル酸エステル、アルキルビニルエステル、アルキル
ビニルエーテル、アルキルマレート及びフマレート、α
−オレフィンなどが挙げられる。これらの化合物（Ｂ）
の具体例としては、オクチルアクリレート、オクチルメ
タクリレート、ラウリルアクリレート、ラウリルメタク
リレート、ステアリルアクリレート、ステアリルメタク
リレート、ベヘニルアクリレート、ベヘニルメタクリレ
ート、２−エチルへキシルアクリレート、２−エチルへ
キシルメタクリレート、ラウリン酸ビニル、ステアリン
酸ビニル、ステアリルビニルエーテル、ジラウリルマレ
ート、ジラウリルフマレート、１−オクタデセンなどが
挙げられる。Compounds (B) having one or more alkyl groups having 8 or more carbon atoms that can be copolymerized with (A) of the present invention include (meth)acrylic esters, alkyl vinyl esters, alkyl vinyl ethers, alkyl maleates, and fumarates; α
-Olefins, etc. These compounds (B)
Specific examples include octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, vinyl laurate, stearic acid. Examples include vinyl, stearyl vinyl ether, dilauryl malate, dilauryl fumarate, and 1-octadecene.
更にこれら（Ａ）及び（Ｂ）以外に、生成共重合体の脂
肪族炭化水素への溶解性及び油性物質の表面改質能に悪
影響を及ぼさない範囲で第３の単量体を共重合させるこ
とも可能である。Furthermore, in addition to these (A) and (B), a third monomer is copolymerized within a range that does not adversely affect the solubility of the resulting copolymer in aliphatic hydrocarbons and the surface modification ability of oily substances. It is also possible.
本発明の製造法においては、フルオロアルキル基を有す
る重合性単量体（Ａ）を１０〜８０重量％、炭素数８以
上のアルキル基を１つ以上有する（Ａ）と共重合し得る
化合物（Ｂ）を９０〜２０１ｉ１１％の割合で共重合す
る。フルオロアルキル基を有する重合性単量体（＾）の
量が８０重量％を越えると脂肪族炭化水素に溶解せず、
１０重量％未満になるとフッ素の効果が発現しなくなり
好ましくない。In the production method of the present invention, 10 to 80% by weight of a polymerizable monomer (A) having a fluoroalkyl group and a compound copolymerizable with (A) having one or more alkyl groups having 8 or more carbon atoms ( B) is copolymerized at a ratio of 90 to 201i11%. If the amount of the polymerizable monomer (^) having a fluoroalkyl group exceeds 80% by weight, it will not dissolve in aliphatic hydrocarbons,
If it is less than 10% by weight, the effect of fluorine will not be expressed, which is not preferable.
本発明の重合溶媒として用いる脂肪族炭化水素として炭
素数５以上の直鎖、分岐及び環状の脂肪族炭化水素が好
ましい、炭素数５未満の脂肪族炭化水素では沸点が低く
、取扱上好ましくない、これらの好ましい脂肪族炭化水
素の例としては、例えばｎ−へブタン、ｎ−ヘキサン、
ｎ−オクタン、シクロヘキサン、メチルシクロヘキサン
、シクロペンクン、メチルシクロペンタン、イソパラフ
ィン系炭化水素油（例えば出光石油化学■製ＩＰソルベ
ント）、流動パラフィンなどが挙げられる。As the aliphatic hydrocarbon used as the polymerization solvent of the present invention, linear, branched, and cyclic aliphatic hydrocarbons having 5 or more carbon atoms are preferred; aliphatic hydrocarbons having less than 5 carbon atoms have a low boiling point and are not preferred in terms of handling. Examples of these preferred aliphatic hydrocarbons include, for example, n-hebutane, n-hexane,
Examples include n-octane, cyclohexane, methylcyclohexane, cyclopenkune, methylcyclopentane, isoparaffinic hydrocarbon oil (for example, IP solvent manufactured by Idemitsu Petrochemical Co., Ltd.), liquid paraffin, and the like.
脂肪族炭化水素中に芳香族炭化水素が混入すると、本発
明のフッ素含有ビニル共重合体の溶解性が低下し、重合
系が不均一となり好ましくない、しかしながら、芳香族
炭化水素の混入量が１０％以下であれば問題ない。When aromatic hydrocarbons are mixed into aliphatic hydrocarbons, the solubility of the fluorine-containing vinyl copolymer of the present invention decreases and the polymerization system becomes non-uniform, which is undesirable. There is no problem if it is less than %.
本発明のフッ素含有ビニル共重合体の製造方法では、通
常のラジカル重合に使用されるアゾ系及び過酸化物系の
ラジカル重合開始剤を使用することができる。In the method for producing a fluorine-containing vinyl copolymer of the present invention, azo-based and peroxide-based radical polymerization initiators used in ordinary radical polymerization can be used.
以下実施例によって本発明を具体的に説明するが、本発
明はこれらの実施例のみに限定されるものではない。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited only to these Examples.
実施例Ｉ
Ｃｌ１ｚ−Ｃ（Ｃ）Ｉｓ）Ｃｏ意ＣｔＨ＊ＣｓＦ＋ｔ
（以下ＦＭＡと称する） ２０．０ｇ 、ラウリルメタ
クリレ−）３０．０ｇ 。Example I Cl1z-C(C)Is)CoCtH*CsF+t
(hereinafter referred to as FMA) 20.0 g, lauryl methacrylate) 30.0 g.
ｎ−ヘキサン５０．０ｇ及び２．２゛−アゾビス（２，
４−ジメチルバレロニトリル）０．３２ｇを３００ｃｃ
４つロフラスコに入れ、攪拌下で溶解及び窒素置換し
た後、窒素雰囲気下で６０〜６５℃にて５時間、更にリ
フラックス下で０．５時間重合を行った０重合は終始均
一系で進行した。50.0 g of n-hexane and 2.2゛-azobis(2,
4-dimethylvaleronitrile) 0.32g to 300cc
After putting 4 pieces in a flask and dissolving them under stirring and purging them with nitrogen, polymerization was carried out at 60 to 65°C for 5 hours under a nitrogen atmosphere, and then for 0.5 hours under reflux. The polymerization proceeded homogeneously from beginning to end. did.
上記共重合体の溶液の一部を取り、エタノールを沈殿剤
として共重合体を沈殿させ、乾燥後単離することにより
重合率を求めると９７％の重合率であった。また、重合
平均分子量は６．７万（ポリスチレン換算）であった。A portion of the copolymer solution was taken, the copolymer was precipitated using ethanol as a precipitant, and the copolymer was dried and isolated to determine the polymerization rate, and the polymerization rate was 97%. Moreover, the polymerization average molecular weight was 67,000 (in terms of polystyrene).
実施例２〜５
ラウリルメタクリレートの代わりに種々のアルキルメタ
クリレートを使用すること、及びｎ−ヘキサンの代わり
に種々の脂肪族炭化水素を使用する以外は実施例１と同
様の方法で共重合を実施した。結果を表−１に示した。Examples 2-5 Copolymerizations were carried out in the same manner as in Example 1, except that various alkyl methacrylates were used in place of lauryl methacrylate, and various aliphatic hydrocarbons were used in place of n-hexane. . The results are shown in Table-1.
表−１より、本発明の方法によりフッ素含有ビニル共重
合体の製造を行うと均一な共重合体溶液が得られる。Table 1 shows that when a fluorine-containing vinyl copolymer is produced by the method of the present invention, a uniform copolymer solution can be obtained.
比較例１〜２
表−１に示したＦＭＡの量、及びアルキルメタクリレー
トの種類及び量、更に脂肪族炭化水素の種類以外は実施
例１と同様の方法で共重合を実施した。結果を表−１に
示した。Comparative Examples 1 to 2 Copolymerization was carried out in the same manner as in Example 1 except for the amount of FMA, the type and amount of alkyl methacrylate, and the type of aliphatic hydrocarbon shown in Table 1. The results are shown in Table-1.
表−１よりＦＭＡＯ量が本発明の範囲よりも多くなると
、本発明の脂肪族炭化水素を溶媒として使用すると重合
系が白濁し、不均一となり好ましくない。Table 1 shows that when the amount of FMAO exceeds the range of the present invention, the polymerization system becomes cloudy and non-uniform when the aliphatic hydrocarbon of the present invention is used as a solvent, which is not preferable.
また、ＦＭＡとアルキルメタクリレートの比率及びアル
キルメタクリレートのアルキル基が本発明の範囲内であ
っても、トルエン等の芳香族炭化水素を溶媒として共重
合を行うと、重合系が白濁、不均一となり、組成や分子
量分布の不均一性が生じてきて好ましくない。Furthermore, even if the ratio of FMA to alkyl methacrylate and the alkyl group of the alkyl methacrylate are within the range of the present invention, if copolymerization is carried out using an aromatic hydrocarbon such as toluene as a solvent, the polymerization system will become cloudy and non-uniform. Non-uniformity in composition and molecular weight distribution occurs, which is undesirable.
以上の実施例及び比較例の結果より、本発明の方法によ
りフッ素含有ビニル共重合体を製造すると、安全性が高
く、安価な溶媒を使用しても容易に均一なフッ素含有ビ
ニル共重合体溶液を製造することが可能となった。From the results of the above Examples and Comparative Examples, it is clear that when a fluorine-containing vinyl copolymer is produced by the method of the present invention, the fluorine-containing vinyl copolymer solution is highly safe and easily uniform even when using an inexpensive solvent. It became possible to manufacture.
手続十甫正占岨発） 昭和６１年１０月１３日Procedures Jufu Zhengzhan) October 13, 1985
Claims (1)
０〜８０重量％、及び炭素数８以上のアルキル基を１つ
以上有する化合物（Ｂ）９０〜２０重量％を、炭素数５
以上の脂肪族炭化水素を溶媒として溶液重合により共重
合せしめることを特徴とするフッ素含有ビニル共重合体
の製造方法。 ２ フルオロアルキル基を有する重合性単量体がフルオ
ロアルキル（メタ）アクリレートである特許請求の範囲
第１項記載の製造方法。 ３ 炭素数８以上のアルキル基を１つ以上有する化合物
がアルキル（メタ）アクリレートである特許請求の範囲
第１項記載の製造方法。[Claims] 1. Polymerizable monomer (A) having a fluoroalkyl group 1
0 to 80% by weight, and 90 to 20% by weight of the compound (B) having one or more alkyl groups having 8 or more carbon atoms,
A method for producing a fluorine-containing vinyl copolymer, which comprises copolymerizing by solution polymerization using the above aliphatic hydrocarbon as a solvent. 2. The manufacturing method according to claim 1, wherein the polymerizable monomer having a fluoroalkyl group is a fluoroalkyl (meth)acrylate. 3. The manufacturing method according to claim 1, wherein the compound having one or more alkyl groups having 8 or more carbon atoms is an alkyl (meth)acrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61196876A JPH0651764B2 (en) | 1986-08-22 | 1986-08-22 | Process for producing fluorine-containing vinyl copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61196876A JPH0651764B2 (en) | 1986-08-22 | 1986-08-22 | Process for producing fluorine-containing vinyl copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6354410A true JPS6354410A (en) | 1988-03-08 |
| JPH0651764B2 JPH0651764B2 (en) | 1994-07-06 |
Family
ID=16365120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61196876A Expired - Lifetime JPH0651764B2 (en) | 1986-08-22 | 1986-08-22 | Process for producing fluorine-containing vinyl copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0651764B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01153784A (en) * | 1987-12-11 | 1989-06-15 | Daikin Ind Ltd | Water and oil repellent and composition thereof |
| US5288825A (en) * | 1990-03-29 | 1994-02-22 | Mitsubishi Rayon Company Ltd. | Fluoroacrylic polymer having lubricating effect and thermoplastic resin composition comprising same |
| US5349019A (en) * | 1988-12-24 | 1994-09-20 | Hoechst | New copolymers, mixtures thereof with poly(meth)acrylate esters and the use thereof for improving the cold fluidity of crude oils |
| US6193791B1 (en) | 1999-09-24 | 2001-02-27 | 3M Innovative Properties Company | Polish composition and method of use |
| US6451717B1 (en) | 1999-12-14 | 2002-09-17 | E. I. Du Pont De Nemours And Company | Highly durable oil/water repellents for textiles |
| JP2012017438A (en) * | 2010-07-09 | 2012-01-26 | Noda Screen:Kk | Fluorine-based copolymer, method for producing the same and coating agent |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5723662A (en) * | 1980-06-03 | 1982-02-06 | Ugine Kuhlmann | Material and method for protecting material against stain and dirt |
| JPS60184513A (en) * | 1984-03-02 | 1985-09-20 | Showa Denko Kk | Production of graft polymer |
| JPS60228588A (en) * | 1984-04-27 | 1985-11-13 | Nippon Oil & Fats Co Ltd | Aerosol type water-and oil-repellent composition |
| JPS60228574A (en) * | 1984-04-27 | 1985-11-13 | Nippon Oil & Fats Co Ltd | Coating compositon |
| JPS60238311A (en) * | 1984-05-10 | 1985-11-27 | Sunstar Giken Kk | Fluorine-containing acrylic resin and elastic finish structure of exterior wall having said resin as top layer |
| JPS61209286A (en) * | 1985-03-13 | 1986-09-17 | Nippon Oil & Fats Co Ltd | Water and oil repellent |
-
1986
- 1986-08-22 JP JP61196876A patent/JPH0651764B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5723662A (en) * | 1980-06-03 | 1982-02-06 | Ugine Kuhlmann | Material and method for protecting material against stain and dirt |
| JPS60184513A (en) * | 1984-03-02 | 1985-09-20 | Showa Denko Kk | Production of graft polymer |
| JPS60228588A (en) * | 1984-04-27 | 1985-11-13 | Nippon Oil & Fats Co Ltd | Aerosol type water-and oil-repellent composition |
| JPS60228574A (en) * | 1984-04-27 | 1985-11-13 | Nippon Oil & Fats Co Ltd | Coating compositon |
| JPS60238311A (en) * | 1984-05-10 | 1985-11-27 | Sunstar Giken Kk | Fluorine-containing acrylic resin and elastic finish structure of exterior wall having said resin as top layer |
| JPS61209286A (en) * | 1985-03-13 | 1986-09-17 | Nippon Oil & Fats Co Ltd | Water and oil repellent |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01153784A (en) * | 1987-12-11 | 1989-06-15 | Daikin Ind Ltd | Water and oil repellent and composition thereof |
| JPH0465113B2 (en) * | 1987-12-11 | 1992-10-19 | Daikin Ind Ltd | |
| US5349019A (en) * | 1988-12-24 | 1994-09-20 | Hoechst | New copolymers, mixtures thereof with poly(meth)acrylate esters and the use thereof for improving the cold fluidity of crude oils |
| US5288825A (en) * | 1990-03-29 | 1994-02-22 | Mitsubishi Rayon Company Ltd. | Fluoroacrylic polymer having lubricating effect and thermoplastic resin composition comprising same |
| US6193791B1 (en) | 1999-09-24 | 2001-02-27 | 3M Innovative Properties Company | Polish composition and method of use |
| WO2001023487A1 (en) * | 1999-09-24 | 2001-04-05 | 3M Innovative Properties Company | Polish composition and method of use |
| US6451717B1 (en) | 1999-12-14 | 2002-09-17 | E. I. Du Pont De Nemours And Company | Highly durable oil/water repellents for textiles |
| JP2012017438A (en) * | 2010-07-09 | 2012-01-26 | Noda Screen:Kk | Fluorine-based copolymer, method for producing the same and coating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0651764B2 (en) | 1994-07-06 |
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