JPH03103409A - Preparation of poly(alpha-fluoroacrylate ester) - Google Patents
Preparation of poly(alpha-fluoroacrylate ester)Info
- Publication number
- JPH03103409A JPH03103409A JP24033189A JP24033189A JPH03103409A JP H03103409 A JPH03103409 A JP H03103409A JP 24033189 A JP24033189 A JP 24033189A JP 24033189 A JP24033189 A JP 24033189A JP H03103409 A JPH03103409 A JP H03103409A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- alpha
- acid ester
- polymer
- poly
- 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
- -1 poly(alpha-fluoroacrylate ester Chemical class 0.000 title claims abstract description 18
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 8
- 239000005871 repellent Substances 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000012567 medical material Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000002940 repellent Effects 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- TYCFGHUTYSLISP-UHFFFAOYSA-N 2-fluoroprop-2-enoic acid Chemical compound OC(=O)C(F)=C TYCFGHUTYSLISP-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910013391 LizN Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- NIXOIRLDFIPNLJ-UHFFFAOYSA-M magnesium;benzene;bromide Chemical compound [Mg+2].[Br-].C1=CC=[C-]C=C1 NIXOIRLDFIPNLJ-UHFFFAOYSA-M 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- ZTZJVAOTIOAZGZ-UHFFFAOYSA-N methyl 2-fluoroacrylate Chemical group COC(=O)C(F)=C ZTZJVAOTIOAZGZ-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003752 zinc compounds Chemical class 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】
本発明は、α−フルオロアクリル酸エステルおよび／ま
たはα−フルオロアクリル酸フルオロエステルをア二オ
ン重合することにより重合体を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer by anionically polymerizing α-fluoroacrylic acid ester and/or α-fluoroacrylic acid fluoroester.
従来よりα−フルオロアクリル酸のフルオロアルキルエ
ステルおよびアルキルエステルの単独重合体および共重
合体は、耐熱性に優れていること、フィルムが強靭であ
り、可撓性に優れていること、屈折率が低いことなどの
特徴を生かして、光学繊維のクラッド材、光ディスク基
盤用材料、撥水撥油材、医用材料などとしての用途が検
討されている。Homopolymers and copolymers of fluoroalkyl esters and alkyl esters of α-fluoroacrylic acid have traditionally had excellent heat resistance, strong and flexible films, and low refractive index. Taking advantage of its characteristics such as low thickness, it is being considered for use as a cladding material for optical fibers, a material for optical disc substrates, water and oil repellent materials, medical materials, etc.
これら重合体の製造は、従来いずれもアゾビスイソブチ
口ニトリルなどの熱重合開始剤或いはペンゾインイソブ
チルエーテルなどの光重合開始剤を用いたラジカル重合
により行われている。These polymers have conventionally been produced by radical polymerization using a thermal polymerization initiator such as azobisisobutylene nitrile or a photopolymerization initiator such as penzoin isobutyl ether.
一方、例えばメチルメタクリレートなどの炭化水素（メ
タ）アクリル酸エステルは、ラジカル重合以外にも、ｎ
−プチルリチウム（ｎ−ＢｕＬｉ）やＰｈＭｇＢｒによ
りアニオン重合することが知られている。On the other hand, hydrocarbon (meth)acrylic acid esters such as methyl methacrylate can be used in addition to radical polymerization.
- It is known that anionic polymerization occurs with butyl lithium (n-BuLi) and PhMgBr.
しかしながら、これらの重合開始剤をα−フルオロアク
リル酸エステルの重合反応に適用した場合には、該エス
テルがメチルα−フルオロアクリレートであっても重合
しない。However, when these polymerization initiators are applied to the polymerization reaction of α-fluoroacrylic acid ester, even if the ester is methyl α-fluoroacrylate, the polymerization does not occur.
本発明者は、鋭意検討を重ねた結果、従来アニオン重合
開始剤としては反応性が低いとされていた有機亜鉛系化
合物、有機アルミニウム系化合物およびアートコンプレ
ックスが、高い収率でα一フルオロアクリル酸エステル
および／またはα一フルオロアクリル酸フルオロエステ
ルからポリマ一を生成することを見出した。As a result of extensive studies, the present inventors have discovered that organozinc compounds, organoaluminum compounds, and art complexes, which were conventionally considered to have low reactivity as anionic polymerization initiators, can be used in α-fluoroacrylic acid in high yields. It has been found that polymers can be produced from esters and/or alpha-fluoroacrylic acid fluoroesters.
本発明で使用するα−フルオロアクリル酸エステルは、
一般式
Ｆ
１
ＣＨ２＝Ｃ−ＣＯＯＲ，
により表されるものである。The α-fluoroacrylic acid ester used in the present invention is
It is represented by the general formula F 1 CH2=C-COOR.
Ｒ，は、Ｃエ〜２ｏの基であることが好ましく、アルキ
ル基、シクロアルキル基、フエニル基又はＦを１原子以
上有するフルオロアルキル基であることがより好ましい
。R is preferably a C-2o group, more preferably an alkyl group, a cycloalkyl group, a phenyl group, or a fluoroalkyl group having one or more F atoms.
α−フルオロアクリル酸エステルとしては、具体的に
Ｃ Ｈ２ ＝Ｃ Ｆ Ｃ ０ ０ Ｃ Ｈ３ＣＨ２＝Ｃ
ＦＣＯＯＣＨ２ＣＨ３
Ｃ Ｈ ２ ＝ Ｃ Ｆ Ｃ Ｏ Ｏ Ｃ Ｈ （ Ｃ
Ｈ ａ ） ２（，Ｈ２ −ＣＦＣＯＯＣ１２Ｈ２５
ＣＨ２＝ＣＦＣＯＯ−Ｑ
ＣＨ２＝ＣＦＣＯＯ−Ｑ
などの炭化水素エステル、および
ＣＨ２＝ＣＦＣＯＯＣＨ２ｃＦ３
ＣＨ２＝ＣＦＣＯＯＣＨ２ＣＦ２ＣＦ２ＨＣＨ２−ＣＦ
ＣＯｏｃＨ２ｃＦ２ｃＦ３ＣＨ２ −ＣＦＣＯＯＣＨ２
Ｃ （ＣＦ３）２ ＨＣＨ２＝ＣＦＣＯＯＣＨ２゛Ｃ
Ｈ２Ｃ８Ｆ１７ＣＨ２ ＝ＣＦＣＯＯＣ （ＣＦ３ ）
ａＣＨ２＝ＣＦＣＯＯＣＨ２ＣＦ２ＣＦＨｃＦ３Ｃ１１
２＝ＣＩＩＣＯＯＣ（Ｃｌｌ ３） ２ ＣＦ２ ＣＰ
ｚ ＩＩなどのフルオロアルキルエステルが例示される
。Specifically, the α-fluoroacrylic acid ester is C H2 =C F C 0 0 C H3CH2=C
FCOOCH2CH3 C H 2 = C F C O O C H (C
H a ) Hydrocarbon esters such as 2(,H2 -CFCOOC12H25 CH2=CFCOO-Q CH2=CFCOO-Q, and CH2=CFCOOCH2cF3 CH2=CFCOOCH2CF2CF2HCH2-CF
COocH2cF2cF3CH2 -CFCOOCH2
C (CF3)2 HCH2=CFCOOCH2゛C
H2C8F17CH2 = CFCOOC (CF3)
aCH2=CFCOOCH2CF2CFHcF3C11
2=CIICOOC(Cll 3) 2 CF2 CP
Examples include fluoroalkyl esters such as z II.
これらの内でも、ＣＨ２−ＣＦＣＯＯＣＨ３およびＣＨ
２−ＣＦＣＯＯＣＨ２ＣＦ３がより好ましい。Among these, CH2-CFCOOCH3 and CH
2-CFCOOCH2CF3 is more preferred.
重合開始剤としては、有機亜鉛系化合物、有機アルミニ
ウム系化合物またアートコンプレックスが好ましい。As the polymerization initiator, an organic zinc compound, an organic aluminum compound, or an art complex is preferable.
有機亜鉛系重合開始剤としては、
（Ｃ２ Ｈ５）２ Ｚｎ１
Ｚｎ （ＯＣＨ３ ）２ （Ｃ２ Ｈ５ Ｚｎ
ＯＣＨ３ ）ｒ，などが例示される。As the organozinc polymerization initiator, (C2 H5)2 Zn1 Zn (OCH3)2 (C2 H5 Zn
OCH3)r, etc. are exemplified.
有機アルミニウム系重合開始剤としては、（Ｃ２ Ｈ５
）ａ Ａｌ、
（Ｃ２ Ｈｓ ）２ Ａ１ （ＮＣＣＨＣＯＯＣ２ Ｈ
ｓ ）、（Ｃ２ Ｈ ｓ ） ２ Ａｌ（Ｃｌｌ ３
０ＣＯＣＩＩＣＯＯＣＨ３ ）などが例示される。As the organic aluminum polymerization initiator, (C2 H5
)a Al, (C2 Hs )2 A1 (NCCHCOOC2 H
s ), (C2 H s ) 2 Al(Cll 3
0COCIICOOCH3) etc. are exemplified.
アートコンプレックスとしては
ＬｉＺｎ （Ｃａ Ｈ９ ）（Ｃ２ Ｈ５ ）２、Ｌｉ
Ａ１ （Ｃ４ Ｈ９）（Ｃ２ Ｈ５）ａなどが例示され
る。As an art complex, LiZn (Ca H9) (C2 H5)2, Li
Examples include A1 (C4 H9) (C2 H5) a.
これら重合開始剤は、通常モノマーあたり０．０１〜１
０モル％程度、より好ましくは０．１〜５モル％程度使
用する。These polymerization initiators are usually 0.01 to 1 per monomer.
It is used in an amount of about 0 mol%, more preferably about 0.1 to 5 mol%.
これら重合開始剤は、ｎ−へキサン、ｎ−へブタン、ベ
ンゼン、トルエンなどの希釈溶液として使用してもよい
。These polymerization initiators may be used as a dilute solution in n-hexane, n-hebutane, benzene, toluene, or the like.
重合溶媒としては、ベンゼン、トルエンのような芳香族
炭化水素、ジメチルエーテル、テトラヒトロフランのよ
うなエーテル化合物、ｎ−ヘキサン、ｎ−へブタンのよ
うな脂肪族炭化水素などが例示される。これらは通常の
ア二オン重合の場合と同様に水分、酸素などを除去して
使用する。Examples of the polymerization solvent include aromatic hydrocarbons such as benzene and toluene, ether compounds such as dimethyl ether and tetrahydrofuran, and aliphatic hydrocarbons such as n-hexane and n-hebutane. These are used after removing moisture, oxygen, etc., as in the case of normal anionic polymerization.
モノマーも、モレキュラシーブなどで脱水し、窒素置換
により脱酸素して用いる。The monomer is also used after being dehydrated using a molecular sieve or the like and deoxidized by nitrogen substitution.
重合は、完全に脱酸素および乾燥したガラスアンプル、
撹拌機付きオートクレープなどを使用して行うことが好
ましい。Polymerization is carried out in completely deoxidized and dried glass ampoules,
It is preferable to use an autoclave equipped with a stirrer or the like.
重合温度は−７８°Ｃ〜１００℃程度が好ましく、特に
−２０〜５０℃が好ましい。温度が低過ぎる場合には、
重合速度が遅くなり、高過ぎる場合には、副反応が多く
なり、分子量が低下する。The polymerization temperature is preferably about -78°C to 100°C, particularly preferably -20 to 50°C. If the temperature is too low,
The polymerization rate becomes slow, and if it is too high, side reactions increase and the molecular weight decreases.
重合の停止は、メタノール、エタノール、塩酸などのプ
ロトン性溶媒の少なくとも１種を添加することにより、
行なえば良い。The polymerization can be stopped by adding at least one protic solvent such as methanol, ethanol, or hydrochloric acid.
Just do it.
本発明方法により得られるポリマーは、撥水撥油剤、光
学材料、塗料材料、医用材料などとして有用である。Polymers obtained by the method of the present invention are useful as water and oil repellents, optical materials, coating materials, medical materials, and the like.
以下に実施例を示し、本発明の特徴とするところをより
一層明確にする。Examples will be shown below to further clarify the features of the present invention.
実施例１
５０ｃｃのガラスアンプルを乾燥・窒素置換した後、窒
素気流下に十分に乾燥・精製したジメチルエーテル（以
下ＤＭＥとする）１−Ｏｃｃ，Ｃ Ｈ ２ ＝ Ｃ Ｆ
Ｃ Ｏ Ｏ Ｃ Ｈ ３ （以下ＭＦＡとする）１
０ミリモル、及びＣ４ Ｈｇ Ｌ ｉと（Ｃ２ Ｈ５
）２ Ｚｎとを等モル混合して作ったＬｉＺｎ （Ｃ４
Ｈｇ ）（Ｃ２ Ｈ５ ）２ ０．２ミリモルを仕込
み、４０℃で７日間重合を行なった。Example 1 After drying and replacing a 50cc glass ampoule with nitrogen, dimethyl ether (hereinafter referred to as DME) 1-Occ, CH 2 = CF was sufficiently dried and purified under a nitrogen stream.
C O O C H 3 (hereinafter referred to as MFA) 1
0 mmol, and C4 Hg Li and (C2 H5
)2 LiZn (C4
0.2 mmol of Hg )(C2 H5 )2 was charged, and polymerization was carried out at 40°C for 7 days.
メタノールー塩酸を少量添加して、重合を停止した後、
３００ｃｃのメタノールを投入し、ポリマーを収率７４
．１％で得た。After stopping the polymerization by adding a small amount of methanol-hydrochloric acid,
300cc of methanol was added, and the yield of polymer was 74.
．． Obtained at 1%.
得られたボリマーのＩＨ−ＮＭＲによるとモノマーに存
在したビニル水素（５．３〜５．８ｐｐｍ）のピークが
消失しており、新たに２．４〜２．８ｐｐｍにメチレン
水素の吸収が現われた。According to IH-NMR of the obtained polymer, the peak of vinyl hydrogen (5.3 to 5.8 ppm) that existed in the monomer disappeared, and a new absorption of methylene hydrogen appeared at 2.4 to 2.8 ppm. .
実施例２
開始剤をＬｉＡ１ （Ｃ４Ｈ９）（Ｃ２Ｈ５）３、モ
ノマーをＣＨ２ ＝ＣＦＣＯＯＣＨ２ ＣＦ３ （以
下ＴＦＥＦＡとする）、溶媒をテトラヒドロフラン（以
下ＴＨＦとする）にそれぞれ変更する以外は実施例１と
同様の手法で重合を行ない、収率１１．６％でポリマー
を得た。Example 2 The same method as in Example 1 except that the initiator was changed to LiA1 (C4H9)(C2H5)3, the monomer was changed to CH2 = CFCOOCH2 CF3 (hereinafter referred to as TFEFA), and the solvent was changed to tetrahydrofuran (hereinafter referred to as THF). Polymerization was carried out to obtain a polymer with a yield of 11.6%.
このポリマーのＧＰＣを測定したところ、平均分子量２
万（ポリスチレン換算）であり、分子量分布はユニモー
ダルであった。When this polymer was measured by GPC, the average molecular weight was 2.
10,000 (polystyrene equivalent), and the molecular weight distribution was unimodal.
実施例３〜７
次表に示す材料を使用して実施例１に準じて重合を行な
い、それぞれポリマーを得た。Examples 3 to 7 Polymerization was carried out according to Example 1 using the materials shown in the following table to obtain polymers.
比較例１
重合開始剤をｎ−ＢｕＬｉに変える以外は実施例１と同
様の手法で重合を行なったが、ボリマーは得られなかっ
た。Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that the polymerization initiator was changed to n-BuLi, but no polymer was obtained.
比較例２
モノマーをＴＦＥＦＡに変える以外は比較例１と同様の
手法で重合を行なったが、ボリマーは得られなかった。Comparative Example 2 Polymerization was carried out in the same manner as in Comparative Example 1 except that the monomer was changed to TFEFA, but no polymer was obtained.
比較例３
開始剤をＣ２Ｈ５ＭｇＢｒに変える以外は比較例１及び
２と同様の手法で重合を行なったが、ＭＦＡ及びＴＦＥ
ＦＡの何れからもボリマーは得られなかった。Comparative Example 3 Polymerization was carried out in the same manner as Comparative Examples 1 and 2 except that the initiator was changed to C2H5MgBr, but MFA and TFE
No polymers were obtained from any of the FAs.
（以 上）(that's all)
Claims (3)
ェニル基又はＦを１原子以上有するフルオロアルキル基
を示す） で示されるα−フルオロアクリル酸エステルをアニオン
重合することを特徴とするポリ（α−フルオロアクリル
酸エステル）の製造方法。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R_1 represents an alkyl group, a cycloalkyl group, a phenyl group, or a fluoroalkyl group having one or more atoms of F) α-fluoroacrylic A method for producing poly(α-fluoroacrylic acid ester), which comprises anionically polymerizing an acid ester.
系であることを特徴とする特許請求の範囲第１項に記載
のポリ（α−フルオロアクリル酸エステル）の製造方法
。(2) The method for producing poly(α-fluoroacrylic acid ester) according to claim 1, wherein the polymerization initiator is an organozinc type or an organoaluminum type.
特徴とする特許請求の範囲第１項に記載のポリ（α−フ
ルオロアクリル酸エステル）の製造方法。(3) The method for producing poly(α-fluoroacrylic acid ester) according to claim 1, wherein the polymerization initiator is an art complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24033189A JPH03103409A (en) | 1989-09-16 | 1989-09-16 | Preparation of poly(alpha-fluoroacrylate ester) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24033189A JPH03103409A (en) | 1989-09-16 | 1989-09-16 | Preparation of poly(alpha-fluoroacrylate ester) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03103409A true JPH03103409A (en) | 1991-04-30 |
Family
ID=17057890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24033189A Pending JPH03103409A (en) | 1989-09-16 | 1989-09-16 | Preparation of poly(alpha-fluoroacrylate ester) |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03103409A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004096939A1 (en) * | 2003-05-02 | 2004-11-11 | Daikin Industries, Ltd. | Surface-treating agent comprising fluoropolymer |
| WO2005092937A1 (en) * | 2004-03-26 | 2005-10-06 | Daikin Industries, Ltd. | Fluorine-containing monomer, fluorine-containing polymer and surface treating agent |
| JPWO2007034818A1 (en) * | 2005-09-21 | 2009-03-26 | ダイキン工業株式会社 | Paper processing agent and paper processing method |
| JP2009191272A (en) * | 2003-05-02 | 2009-08-27 | Daikin Ind Ltd | Surface treating agent containing fluoropolymer |
| US7638575B2 (en) | 2004-03-26 | 2009-12-29 | Daikin Industries, Ltd. | Surface treating agent, fluorine-containing monomer and fluorine-containing polymer |
-
1989
- 1989-09-16 JP JP24033189A patent/JPH03103409A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004096939A1 (en) * | 2003-05-02 | 2004-11-11 | Daikin Industries, Ltd. | Surface-treating agent comprising fluoropolymer |
| JP2009191272A (en) * | 2003-05-02 | 2009-08-27 | Daikin Ind Ltd | Surface treating agent containing fluoropolymer |
| US7915337B2 (en) | 2003-05-02 | 2011-03-29 | Daikin Industries, Ltd. | Surface-treating agent comprising fluoropolymer |
| US9328455B2 (en) | 2003-05-02 | 2016-05-03 | Daikin Industries, Ltd. | Surface-treating agent comprising fluoropolymer |
| WO2005092937A1 (en) * | 2004-03-26 | 2005-10-06 | Daikin Industries, Ltd. | Fluorine-containing monomer, fluorine-containing polymer and surface treating agent |
| KR100840819B1 (en) * | 2004-03-26 | 2008-06-23 | 다이킨 고교 가부시키가이샤 | Fluorine-Containing Monomer, Fluorine-Containing Polymer and Surface Treating Agent |
| US7442829B2 (en) | 2004-03-26 | 2008-10-28 | Daikin Industries, Ltd. | Fluorine-containing monomer, fluorine-containing polymer and surface treating agent |
| US7638575B2 (en) | 2004-03-26 | 2009-12-29 | Daikin Industries, Ltd. | Surface treating agent, fluorine-containing monomer and fluorine-containing polymer |
| US8153756B2 (en) | 2004-03-26 | 2012-04-10 | Daikin Industries, Ltd. | Fluorine-containing monomer, fluorine-containing polymer and surface treating agent |
| JPWO2007034818A1 (en) * | 2005-09-21 | 2009-03-26 | ダイキン工業株式会社 | Paper processing agent and paper processing method |
| JP4656148B2 (en) * | 2005-09-21 | 2011-03-23 | ダイキン工業株式会社 | Paper processing agent and paper processing method |
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