JPH0573764B2 - - Google Patents
Info
- Publication number
- JPH0573764B2 JPH0573764B2 JP3218888A JP3218888A JPH0573764B2 JP H0573764 B2 JPH0573764 B2 JP H0573764B2 JP 3218888 A JP3218888 A JP 3218888A JP 3218888 A JP3218888 A JP 3218888A JP H0573764 B2 JPH0573764 B2 JP H0573764B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyvinylamine
- fluorine
- formula
- ultra
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 claims description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000010408 film Substances 0.000 description 37
- 239000010409 thin film Substances 0.000 description 15
- 238000012986 modification Methods 0.000 description 14
- 230000004048 modification Effects 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- -1 alkyl perfluoroalkyl carboxylate Chemical class 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000083 poly(allylamine) Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FJWSMXKFXFFEPV-UHFFFAOYSA-N prop-2-enamide;hydrochloride Chemical compound Cl.NC(=O)C=C FJWSMXKFXFFEPV-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
［技術分野］
本発明は新規な含フツ素高分子物質、その製造
方法及びそのラングミユアープロジエツト膜に関
するものである。
［従来技術］
長鎖のペルフルオロアルキル基で修飾した高分
子化合物は撥水撥油性、防塵性、耐食性などに優
れた性質を示し、表面改質材用として基板保護に
用いられている。また、酸素透過膜の素材として
も優れており、ペルフルオロアルキル基の酸素親
和性により、選択性の向上が成されている。
しかし、ペルフルオロアルキル基を導入した高
分子化合物はペルフルオロアルキル基の持つ撥水
撥油性により溶媒に溶け難く、膜素材としては扱
いにくい。つまり、表面改質材、基板保護材とし
て重要である超薄膜とすることが難しい。また、
撥水撥油性、酸素親和性などの機能基であるペル
フルオロアルキル基を高分子表面に配列制御する
ことは、表面改質材や酸素分離膜としての機能の
性能を高める上で重要であるが、表面への配列を
制御することは容易なことではない。
本発明者は、ポリアリルアミンをペルフルオロ
アルキル基で修飾し、この高分子を用いてラング
ミユアープロジエツト手法で分子配列を制御した
超薄膜を作成した［昭和62年特許願第1350号］。
しかし、ペルフルオロアルキル基の導入率が高い
と溶媒に不溶性となり、薄膜の作成ができないな
どの欠点を有していた。
［目的］
本発明者は、ペルフルオロアルキル基の疎水性
を利用した超薄膜の作成方法について鋭意研究を
重ね、ポリビニルアミンのアミノ基をアミド結合
でペルフルオロアルキル化して得られる高分子化
合物は、高いペルフルオロアルキル基の修飾率で
も可溶性であり、超薄膜材料として好適なもので
あることを見出し、本発明を完成するに至つた。
［構成］
本発明によれば、
[Technical Field] The present invention relates to a novel fluorine-containing polymeric substance, a method for producing the same, and a Langmuir project film thereof. [Prior Art] Polymer compounds modified with long-chain perfluoroalkyl groups exhibit excellent properties such as water and oil repellency, dustproofness, and corrosion resistance, and are used as surface-modifying materials to protect substrates. It is also excellent as a material for oxygen permeable membranes, and has improved selectivity due to the oxygen affinity of the perfluoroalkyl group. However, polymer compounds into which perfluoroalkyl groups have been introduced are difficult to dissolve in solvents due to the water and oil repellency of the perfluoroalkyl groups, making them difficult to use as membrane materials. In other words, it is difficult to form ultra-thin films, which are important as surface modification materials and substrate protection materials. Also,
Controlling the arrangement of perfluoroalkyl groups, which are functional groups such as water and oil repellency and oxygen affinity, on the surface of polymers is important for improving the performance of the polymer as a surface modification material and oxygen separation membrane. Controlling the arrangement on a surface is not easy. The present inventor modified polyallylamine with a perfluoroalkyl group and used this polymer to create an ultra-thin film with controlled molecular arrangement using the Langmuir project technique [Patent Application No. 1350, 1988].
However, when the rate of introduction of perfluoroalkyl groups is high, it becomes insoluble in solvents and has drawbacks such as the inability to form thin films. [Purpose] The present inventor has conducted extensive research on a method for creating ultra-thin films that utilizes the hydrophobicity of perfluoroalkyl groups, and has found that a polymer compound obtained by perfluoroalkylating the amino group of polyvinylamine with an amide bond has a high perfluorocarbon content. The present inventors discovered that the material is soluble even at the modification rate of the alkyl group and is suitable as an ultra-thin film material, leading to the completion of the present invention. [Configuration] According to the present invention,
【化】
（式中、Rfは炭素数６〜15のペルフルオロアル
キル基を示し、ｍは10〜1000の数を示し、ｎは０
＜ｎ＜0.7mを満たす数である。）で表わされる含
フツ素高分子化合物が提供される。
本発明による前記含フツ素高分子化合物は、下
記一般式（）で表わされるポリビニルアミン
と、一般式（）で表わされるペルフルオロアル
キルカルボン酸アルキルと次式によつて反応させ
ることによつて製造される。[Formula, Rf represents a perfluoroalkyl group having 6 to 15 carbon atoms, m represents a number from 10 to 1000, and n represents 0
The number satisfies <n<0.7m. ) is provided. The fluorine-containing polymer compound according to the present invention is produced by reacting polyvinylamine represented by the following general formula () with an alkyl perfluoroalkylcarboxylate represented by the general formula () according to the following formula. Ru.
【化】
（式中、Rf、ｍ及びｎは前記と同じ意味を持ち、
Ｒは炭素数１〜５のアルキル基を示す。）
前記反応で用いたポリビニルアミンは、アクリ
ルアミドを重合して平均分子量約7000のポリアク
リルアミドを合成し、これをホフマン分解でポリ
ビニルアミン塩酸塩とし、塩基により中和して得
た。
前記ポリビニルアミンの修飾反応は、反応溶媒
としてアルコール類を用い、反応温度として−10
℃〜50℃、好ましくは15℃〜30℃で実施すること
ができる。この反応を好ましく行なうには、ポリ
ビニルアミン塩酸塩を溶媒中で中和した溶液部、
又はポリビニルアミンを溶媒中に溶かして得られ
るポリビニルアミンの溶液に、ペルフルオロアル
キルカルボン酸アルキルを加える。加えるペルフ
ルオロアルキルカルボン酸アルキルの量を変える
ことにより、任意の割合でポリビニルアミンにペ
ルフルオロアシル化でペルフルオロアルキル基を
修飾できる。この場合、反応の進行と共に、ポリ
ビニルアミン中のアミノ基に対する修飾率（以
下、修飾率とする）が約70％以上と高い含フツ素
ポリビニルアミンは反応液からの析出が認められ
たが、それ以下の修飾率での含フツ素高分子の合
成反応は均一で進行した。数分から数時間の撹拌
後、反応溶液を濃縮、水洗して、得られた含フツ
素高分子化合物を乾燥する。得られた含フツ素高
分子はフツ素分析値、及びIRスペクトルにより
前記一般式（）で表わされる含フツ素ポリビニ
ルアミンであることが同定された。
本発明の修飾率が70％以下の含フツ素ポリビニ
ルアミンは、有機溶剤に溶け、水面上で容易に単
分子膜を形成するものであり、ラングミユアーブ
ロジエツト膜を作成できる。水面上にこの含フツ
素高分子を展開した時の表面圧−面積曲線（Ｆ−
Ａ曲線）の測定から、ポリビニルアミンへの修飾
率の減少によりペルフルオロアルキル基一つの占
める面積が大きくなつた超薄膜が作成できること
が分かる。
この超薄膜をガラス基板上に１層又は、多層を
すくいとり、この膜の膜厚及びｎ−アルカンに対
する臨界表面張力γc dyn／cmを求めた結果、ポ
リビニルアミンへの修飾率が37、18、９％の含フ
ツ素高分子LB膜は１層の膜のγc値が約16を示し、
３層の膜は約14の値を示した。また、56％修飾し
た高分子LB膜は約13のγc値を示した。この値は
先に述べたポリアリルアミンを修飾した含フツ素
高分子化合物のLB膜［昭和62年特許願第1350号］
よりも低い値であり、より膜表面が低表面エネル
ギー状態となつていて、撥水撥油性、防塵性など
の性質を示す優れた膜であることを示している。
これらのγc値はポリテトラフルオロエチレンの
γc値18.5よりも低く優れた値と言える。また、こ
の膜を熱処理するとγc値はポリビニルアミンへ
の修飾率の低いものではγc値で約２の増加が見
られるが、修飾率の高い高分子膜ではγc値の変
化は見られなかつた。
膜厚を次の２つの方法で測定した。つまり、タ
リステツプによる測定では膜厚１層当たり４〜６
Å、Ｘ線回折による測定では１層当たり６〜９Å
であつた。このことからこのポリビニルアミンを
含フツ素基で修飾した高分子LB膜は非常に薄い、
超薄膜であることが明らかとなつた。
［効果］
すなわち、本発明によればポリビニルアミンに
アミド結合で長鎖のペルフルオロアルキル基を導
入試薬であるペルフルオロアルキルカルボン酸ア
ルキルの量を任意に変えることにより修飾でき
る。ポリビニルアミン中のアミノ基に対する修飾
率が70％以下の含フツ素高分子は可溶性であり、
ラングミユアーブロジエツト法により超薄膜化す
ることができ、従来にない超薄膜表面改質物質と
して用いることができる。また、この超薄膜は１
層当たりの膜厚が10Å以内と非常に薄い膜であ
る。更に１つのペルフルオロアルキル基が占める
面積を制御できる膜であり、また、その表面は機
能基であるペルフルオロアルキル基が存在し、ポ
リテトラフルオロエチレンよりも優れた低表面エ
ネルギー性を示す。従来、ラングミユアーブロジ
エツト法により、含フツ素高分子を分子内や分子
間で配列制御したまま、１層の膜厚を10Å以内と
言うような超薄膜を作成した例はない。
なお、本明細書で言うラングミユアーブロジエ
ツト膜とは、従来よく知られているラングミユア
ーブロジエツト法により得られる単分子膜及び累
積膜を意味する。
［実施例］
次に本発明を実施例により、更に詳細に説明す
る。
実施例 １
ポリビニルアミン塩酸塩の合成
アクリルアミドを常法［高分子合成実験法
P.157、昭和37年（東京化学同人）］により合成し
た。但し、溶媒を30倍過剰に用い、重合開始剤と
して（NH4）2S2O8を10倍量用いることにより平
均分子量の小さいポリアクリルアミド
（Mw7100：粘土法［η］＝6.8×10-4M0.66より計
算）を得た。
更にポリアクリルアミドを常法［高分子論文
集、33、309（1976）］でホフマン分解しポリビニ
ルアミン塩酸塩を得た。
実施例 ２
ポリビニルアミンの修飾
メタノール7.5mlに金属ナトリウム0.06ｇを加
え、水素の発生がなくなつてから実施例１で合成
したポリビニルアミン塩酸塩0.11ｇを加え、蓋を
して撹拌する。析出した塩化ナトリウムを濾過し
て取り除き、瀘液にペルフルオロオクタン酸アル
キルをポリビニルアミン中のアミノ基に対して、
９、18、37、56、65％のモル比で加え、室温で４
時間撹拌した。この反応液は、均一で、そのまま
ラングミユアーブロジエツト膜作製の高分子溶液
の原液として使用できる、この溶液を減圧下で溶
媒を除去し、更に水洗して乾燥するとポリビニル
アミン中のアミノ基が９、18、37、56、65％ペル
フルオロアシル化した高分子が得られた。また、
74％のペルフルオロオクタン酸アルキルを用いる
と生成高分子の析出が認められた。これら高分子
のペルフルオロアルキル基の導入率はフツ素分析
により行ない、約１％の誤差範囲で計算値とそれ
ぞれ一致した。更に生成物は赤外吸収スペクトル
により1700cm-1にアミド結合の吸収が、1100〜
1300cm-1に炭素−フツ素結合の強い吸収が認めら
れたことにより確認された。
実施例 ３
ラングミユアーブロジエツト膜の作製
実施例２で合成した含フツ素高分子をそれぞれ
のペルフルオロアシル基の修飾率（Ｍ％）に対応
してPVAF(M)と略す。
ラングミユアーブロジエツト法において、
PVAF9、18、37、56のメタノール・ベンゼン希
薄混合溶液をそれぞれ調製し、これら溶液を17℃
の水面上にそれぞれ展開したときの表面圧−面積
の関係（Ｆ−Ａ曲線）を測定した結果を第１図に
示す。この結果により、膜中のペルフルオロアシ
ル基−分子の占める面積、つまり極限面積は
PVAF9、18、37、56の順にそれぞれ78、64、49、
30Å2の値を示した。
この水面上の超薄膜をガラス基板上に表面圧20
ｍＮ・ｍ-1で単分子膜及び累積膜として移しとつ
た。これらは透明な膜であつた。
実施例 ４
臨界表面張力γcの測定
実施例３でガラス基板上に移しとつた単分子膜
累積膜、更にこれらをメタノール処理した膜、熱
処理した膜について、ｎ−アルカンとの接触角を
測定し、Zismanプロツトから求めた臨界表面張
力γc値を最小二乗法で計算した。これらの結果
は表に示した。[C] (where Rf, m and n have the same meanings as above,
R represents an alkyl group having 1 to 5 carbon atoms. ) The polyvinylamine used in the above reaction was obtained by polymerizing acrylamide to synthesize polyacrylamide with an average molecular weight of about 7000, converting it into polyvinylamine hydrochloride by Huffmann decomposition, and neutralizing it with a base. In the modification reaction of polyvinylamine, alcohols are used as the reaction solvent, and the reaction temperature is -10
It can be carried out at a temperature of 15°C to 30°C, preferably 15°C to 30°C. To carry out this reaction preferably, a solution part in which polyvinylamine hydrochloride is neutralized in a solvent,
Alternatively, an alkyl perfluoroalkyl carboxylate is added to a solution of polyvinylamine obtained by dissolving polyvinylamine in a solvent. By changing the amount of alkyl perfluoroalkylcarboxylate added, the perfluoroalkyl group can be modified by perfluoroacylation on polyvinylamine in any proportion. In this case, as the reaction progressed, fluorine-containing polyvinylamine with a high modification rate of amino groups in polyvinylamine (hereinafter referred to as modification rate) of approximately 70% or more was observed to precipitate from the reaction solution; The synthesis reaction of fluorine-containing polymers at the following modification rates proceeded uniformly. After stirring for several minutes to several hours, the reaction solution is concentrated and washed with water, and the obtained fluorine-containing polymer compound is dried. The obtained fluorine-containing polymer was identified to be a fluorine-containing polyvinylamine represented by the above general formula () by the fluorine analysis value and the IR spectrum. The fluorine-containing polyvinylamine of the present invention having a modification rate of 70% or less is soluble in organic solvents and easily forms a monomolecular film on the surface of water, making it possible to create a Langmuir Blossom film. Surface pressure-area curve (F-
The measurement of curve A) shows that an ultra-thin film can be created in which the area occupied by one perfluoroalkyl group is increased by decreasing the modification rate of polyvinylamine. One layer or multiple layers of this ultra-thin film were scooped out onto a glass substrate, and the film thickness and critical surface tension γc dyn/cm for n-alkanes were determined. As a result, the modification rate to polyvinylamine was 37, 18, One layer of the 9% fluorine-containing polymer LB film has a γc value of approximately 16.
The three-layer membrane showed a value of about 14. Furthermore, the 56% modified polymer LB film showed a γc value of about 13. This value is based on the above-mentioned LB film of a fluorine-containing polymer compound modified with polyallylamine [Patent Application No. 1350 of 1988]
This value is lower than that of 100%, indicating that the film surface is in a lower surface energy state, and is an excellent film exhibiting properties such as water and oil repellency and dust resistance.
These γc values are lower than the γc value of polytetrafluoroethylene, which is 18.5, and can be said to be excellent values. Furthermore, when this film was heat-treated, the γc value increased by about 2 in the case of the film with a low modification rate to polyvinylamine, but no change in the γc value was observed in the polymer film with a high modification rate. Film thickness was measured using the following two methods. In other words, when measured using Talystep, there are 4 to 6 layers per film thickness.
Å, 6-9 Å per layer measured by X-ray diffraction
It was hot. This shows that this polymer LB film, which is made by modifying polyvinylamine with fluorine-containing groups, is extremely thin.
It became clear that it was an ultra-thin film. [Effect] That is, according to the present invention, a long-chain perfluoroalkyl group can be introduced into polyvinylamine through an amide bond by arbitrarily changing the amount of alkyl perfluoroalkylcarboxylate as a reagent. Fluorine-containing polymers with a modification rate of 70% or less for amino groups in polyvinylamine are soluble;
It can be made into an ultra-thin film using the Langmuir Blossom method, and can be used as an unprecedented ultra-thin surface-modifying substance. Moreover, this ultra-thin film has 1
It is a very thin film with a thickness of less than 10 Å per layer. Furthermore, it is a membrane in which the area occupied by one perfluoroalkyl group can be controlled, and the surface thereof has perfluoroalkyl groups, which are functional groups, and exhibits lower surface energy properties than polytetrafluoroethylene. Until now, there has been no example of creating an ultra-thin film with a single layer thickness of 10 Å or less using the Langmuir-Blodget method while controlling the arrangement of fluorine-containing polymers within and between molecules. In this specification, the term "Langmeur Blossom film" refers to a monomolecular film or a cumulative film obtained by the conventionally well-known Langmuir Blossom film. [Example] Next, the present invention will be explained in more detail with reference to Examples. Example 1 Synthesis of polyvinylamine hydrochloride Acrylamide was prepared using a conventional method [polymer synthesis experimental method]
P.157, 1968 (Tokyo Kagaku Dojin)]. However, by using a 30-fold excess of the solvent and a 10-fold excess of (NH 4 ) 2 S 2 O 8 as a polymerization initiator, polyacrylamide with a small average molecular weight (Mw7100: clay method [η] = 6.8×10 -4 (calculated from M 0.66 ) was obtained. Furthermore, polyvinylamine hydrochloride was obtained by Hofmann decomposition of the polyacrylamide by a conventional method [Kobunshi Ronshu, 33 , 309 (1976)]. Example 2 Modification of polyvinylamine 0.06 g of sodium metal is added to 7.5 ml of methanol, and after hydrogen is no longer generated, 0.11 g of polyvinylamine hydrochloride synthesized in Example 1 is added, and the mixture is covered with a lid and stirred. The precipitated sodium chloride was removed by filtration, and alkyl perfluorooctanoate was added to the filtrate for amino groups in polyvinylamine.
Add at molar ratios of 9, 18, 37, 56, and 65%, and add 4 at room temperature.
Stir for hours. This reaction solution is homogeneous and can be used as it is as a stock solution for the polymer solution for Langmiur Blossom film production.The solvent is removed from this solution under reduced pressure, and the amino groups in the polyvinylamine are removed by washing with water and drying. Polymers with perfluoroacylation of 9, 18, 37, 56, and 65% were obtained. Also,
When 74% alkyl perfluorooctanoate was used, precipitation of the produced polymer was observed. The introduction rates of perfluoroalkyl groups in these polymers were determined by fluorine analysis, and each agreed with the calculated values within an error range of about 1%. Furthermore, the infrared absorption spectrum of the product shows that the absorption of the amide bond is at 1700 cm -1 and the absorption of the amide bond is at 1100 cm -1.
This was confirmed by the observation of strong absorption of carbon-fluorine bonds at 1300 cm -1 . Example 3 Preparation of Langmuir-Blodget Membrane The fluorine-containing polymer synthesized in Example 2 is abbreviated as PVAF(M) corresponding to the modification rate (M%) of each perfluoroacyl group. In the Langmiur Blosget method,
Prepare methanol/benzene dilute mixed solutions of PVAF9, 18, 37, and 56, and heat these solutions at 17℃.
FIG. 1 shows the results of measuring the surface pressure-area relationship (FA curve) when each of the specimens was developed on the water surface. Based on this result, the area occupied by the perfluoroacyl group-molecule in the membrane, that is, the ultimate area, is
PVAF9, 18, 37, 56 respectively 78, 64, 49,
It showed a value of 30Å2 . This ultra-thin film on the water surface was placed on a glass substrate at a surface pressure of 20
It was transferred as a monomolecular film and a cumulative film at mN·m −1 . These were transparent films. Example 4 Measurement of critical surface tension γc The contact angle with n-alkane was measured for the monomolecular film stack transferred onto the glass substrate in Example 3, a film treated with methanol, and a film treated with heat. The critical surface tension γc value obtained from the Zisman plot was calculated using the least squares method. These results are shown in the table.
【表】
実施例 ５
膜厚の測定
実施例３で得たラングミユアーブロジエツト膜
の10層累積膜について、次の２つの方法で膜厚を
測定した。(1)タリステツプによる測定：薄膜を一
部剥し、膜との段差をタリステツプにより測定し
た結果、膜厚は薄く40〜60±20Åの値がPVAF9、
18、37、56の薄膜に付いて得られた。１層の膜厚
は前記膜厚の10分の１となる。(2)Ｘ線回折による
測定：銅のKα1、λ＝1.54050、40K、30ｍＡでＸ
線回折図を測定したところ、回折パターンが観測
された。これより膜厚をブラツグの式により求め
ると、PVAF9、18、37、56の値は60〜85Åとな
つた。１層の膜厚は前記膜厚の10分の１である。[Table] Example 5 Measurement of Film Thickness The film thickness of the 10-layer cumulative film of the Langmuir-Blodget film obtained in Example 3 was measured using the following two methods. (1) Measurement using Talystep: Part of the thin film was peeled off and the difference in level with the film was measured using Talystep. The results showed that the film was thin and had a value of 40 to 60 ± 20 Å.
Obtained for thin films 18, 37, and 56. The film thickness of one layer is one-tenth of the above film thickness. (2) Measurement by X-ray diffraction: Kα 1 of copper, λ = 1.54050, X at 40K, 30mA
When the line diffraction diagram was measured, a diffraction pattern was observed. When the film thickness was calculated from this using Bragg's formula, the values for PVAF9, 18, 37, and 56 were 60 to 85 Å. The film thickness of one layer is one-tenth of the above film thickness.
第１図は、本発明による含フツ素高分子ラング
ミユアーブロジエツト膜のＦ−Ａ曲線を示す。
FIG. 1 shows the F-A curve of the fluorine-containing polymer Langmeur Blossom film according to the present invention.
Claims (1)
【式】 （式中、Rfは炭素数６〜15のペルフルオロアル
キル基を示し、ｍは10〜1000の数を示し、ｎは０
＜ｎ＜0.7mを満たす数である。）で表わされる含
フツ素高分子化合物。 ２ 一般式
【式】 （式中、Rfは炭素数６〜15のペルフルオロアル
キル基を示し、ｍは10〜1000の数を示し、ｎは０
＜ｎ＜0.7mを満たす数である。）で表わされる含
フツ素高分子化合物を製造する方法において、 一般式【式】 （式中、ｍは前記と同じ意味を持つ。）で表わさ
れるポリビニルアミンと、 一般式【式】 （式中、Rfは前記と同じ意味を持ち、Ｒは炭素
数１〜５のアルキル基を示す。）で表わされるペ
ルフルオロアルキルカルボン酸アルキルと反応さ
せることを特徴とする方法。 ３ 一般式 【化】 （式中、Rfは炭素数６〜15のペルフルオロアル
キル基を示し、ｍは10〜1000の数を示し、ｎは０
＜ｎ＜0.7mを満たす数である。）で表わされるラ
ングミユアープロジエツト膜。[Claims] 1 General formula [Formula] (wherein, Rf represents a perfluoroalkyl group having 6 to 15 carbon atoms, m represents a number from 10 to 1000, and n represents 0
The number satisfies <n<0.7m. ) A fluorine-containing polymer compound represented by 2 General formula [Formula] (In the formula, Rf represents a perfluoroalkyl group having 6 to 15 carbon atoms, m represents a number from 10 to 1000, and n is 0
The number satisfies <n<0.7m. ), a polyvinylamine represented by the general formula [formula] (wherein m has the same meaning as above); , Rf has the same meaning as above, and R represents an alkyl group having 1 to 5 carbon atoms. 3 General formula
The number satisfies <n<0.7m. ) Langmuir project membrane.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3218888A JPH01207311A (en) | 1988-02-15 | 1988-02-15 | Polymeric compound containing fluorine, its production and polymer thin film therefrom |
| US07/306,987 US5001198A (en) | 1988-02-15 | 1989-02-06 | Fluorine-containing polymeric compound and a method for the preparation thereof |
| EP89301339A EP0329362B1 (en) | 1988-02-15 | 1989-02-13 | A fluorine-containing polymeric compound and a method for the preparation thereof |
| DE68914306T DE68914306T2 (en) | 1988-02-15 | 1989-02-13 | Fluorine-containing polymer compound and process for producing the same. |
| US07/608,239 US5071915A (en) | 1988-02-15 | 1990-11-02 | Fluorine-containing polymeric compound and a method for the preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3218888A JPH01207311A (en) | 1988-02-15 | 1988-02-15 | Polymeric compound containing fluorine, its production and polymer thin film therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01207311A JPH01207311A (en) | 1989-08-21 |
| JPH0573764B2 true JPH0573764B2 (en) | 1993-10-15 |
Family
ID=12351932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3218888A Granted JPH01207311A (en) | 1988-02-15 | 1988-02-15 | Polymeric compound containing fluorine, its production and polymer thin film therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01207311A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19630977A1 (en) * | 1996-07-31 | 1998-02-05 | Basf Ag | Water-soluble polymers and their use in cosmetic formulations |
| DE19636883A1 (en) * | 1996-09-11 | 1998-03-12 | Basf Ag | Insoluble, only slightly swellable polymers with modified amino groups, process for their preparation and their use |
| WO2009078313A1 (en) * | 2007-12-18 | 2009-06-25 | Asahi Glass Company, Limited | Surface modifier and article having coating film containing the same |
-
1988
- 1988-02-15 JP JP3218888A patent/JPH01207311A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01207311A (en) | 1989-08-21 |
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