JPH03243609A - Polymeric compound having modified fluorine-containing group, its production and polymer thin film composed thereof - Google Patents
Polymeric compound having modified fluorine-containing group, its production and polymer thin film composed thereofInfo
- Publication number
- JPH03243609A JPH03243609A JP3925890A JP3925890A JPH03243609A JP H03243609 A JPH03243609 A JP H03243609A JP 3925890 A JP3925890 A JP 3925890A JP 3925890 A JP3925890 A JP 3925890A JP H03243609 A JPH03243609 A JP H03243609A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- polymer compound
- fluorine
- containing polymer
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000010409 thin film Substances 0.000 title abstract description 22
- 125000001153 fluoro group Chemical class F* 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000005270 trialkylamine group Chemical group 0.000 claims abstract description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 36
- 239000011737 fluorine Substances 0.000 claims description 36
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 229920002125 Sokalan® Polymers 0.000 abstract description 18
- 239000004584 polyacrylic acid Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 description 26
- 230000004048 modification Effects 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 150000002221 fluorine Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- ABFPKTQEQNICFT-UHFFFAOYSA-M 2-chloro-1-methylpyridin-1-ium;iodide Chemical compound [I-].C[N+]1=CC=CC=C1Cl ABFPKTQEQNICFT-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は新規な含フツ素高分子化合物、その製造方法及
びそのラングミュア−ブロジェット膜に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel fluorine-containing polymer compound, a method for producing the same, and a Langmuir-Blodgett film thereof.
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、耐食性等に優れた性質を示し、
表面改質用として基板保護に用いられでいる。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酸素透過の選択性の向上が成さ
れている。Polymer compounds modified with long-chain perfluoroalkyl groups exhibit excellent properties such as water and oil repellency, dust resistance, and corrosion resistance.
It is used for surface modification and protection of substrates. It is also excellent as a material for oxygen permeable membranes, and the oxygen permeation selectivity is improved due to the oxygen affinity of the perfluoroalkyl group.
しかし、ペルフルオロアルキル基を導入した高分子化合
物はベルフロオロアルキル基の持つ撥水撥油性により溶
媒に溶は難く、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、酸素親和性等の機能基
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。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. In addition, 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 surface modification materials and oxygen separation membranes. However, controlling the arrangement on the surface is not easy.
本発明者らは、ポリアリルアミン又はポリビニルアミン
にアミド結合等の共有結合によりペルフルオロアルキル
基を修飾し、この高分子を用いてラングミュア−プロジ
ェット手法で分子配列を制御した超薄膜を作成した〔特
開昭６３−１７０４０５号、特開昭６４−４６０８号、
特開平１−２０７３１１号、特開平１−２０７３１２号
、特願昭６３−２１６０２８号、特願平１−５２６５５
号〕。The present inventors modified polyallylamine or polyvinylamine with a perfluoroalkyl group through a covalent bond such as an amide bond, and used this polymer to create an ultra-thin film with controlled molecular arrangement using the Langmuir-Prodgett method. JP-A-63-170405, JP-A-64-4608,
JP-A-1-207311, JP-A-1-207312, JP-A-63-216028, JP-A-1-52655
issue〕.
しかしこれらはすへてアミン系の高分子であるため、酸
性物質の存在下では高分子中のアミノ基が反応してしま
うなど、その適用範囲は制限される。このため、適用範
囲の広く、また、さらに優れた機能を持つ超薄膜材料の
開発が望まれている。However, since these are all amine-based polymers, their range of application is limited because the amino groups in the polymers react in the presence of acidic substances. Therefore, it is desired to develop ultra-thin film materials that have a wide range of applications and even better functionality.
本発明者らは、ベルフ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、ポリアク
リル酸のカルボキシル基の一部又はすへてをアミド結合
により１，１−ジヒドロペルフルオロアルキル基で修飾
して得られる高分子化合物は超薄膜材料として好適なも
のであることを見いだし、本発明を完成するに至った。The present inventors have conducted extensive research on a method for creating ultra-thin films that utilizes the hydrophobicity of perfluoroalkyl groups, and have determined that a part or all of the carboxyl groups of polyacrylic acid can be converted into 1,1-dihydroperfluorocarbons by amide bonding. The present inventors have discovered that a polymer compound obtained by modifying with an alkyl group is suitable as an ultra-thin film material, and have completed the present invention.
本発明は、超薄膜材料として好適なかつ酸性物質と反応
しない含フツ素高分子化合物、その製造方法及びそのラ
ングミュア−プロジェット膜を提供することをその課題
とする。An object of the present invention is to provide a fluorine-containing polymer compound that is suitable as an ultra-thin film material and does not react with acidic substances, a method for producing the same, and a Langmuir-Prodgett film thereof.
本発明によれば、一般式。 According to the invention, the general formula.
市 ＣＨ。city CH.
ｆ
（式中、Ｒ８は炭素数６〜１５のペルフルオロアルキル
基を示し、ｍは１０−１０００００の数を示し、ｎは０
（ｎ≦■を満たす数である）
で表わされる含フツ素高分子化合物、その製造方法及び
そのラングミュアブロジェット膜が提供される。f (wherein, R8 represents a perfluoroalkyl group having 6 to 15 carbon atoms, m represents a number of 10 to 100,000, and n is 0
A fluorine-containing polymer compound represented by the formula (n≦■), a method for producing the same, and a Langmuir-Blodgett film thereof are provided.
本発明による前記含フツ素高分子化合物は、下記に示一
般式（ＩＩ）で表わされるポリアクリル酸と、一般式（
ＩＩＩ）で表わされる１、１−ジヒドロペルフルオロア
ルキルアミンとを、一般式（ＩＶ）で表ねされるヨウ化
ｌ−アルキル−２−へロピリジニウムと一般式（Ｖ）で
表わされるトリアルキルアミンの存在下、次式によって
反応させることにより製造される。The fluorine-containing polymer compound according to the present invention comprises a polyacrylic acid represented by the general formula (II) shown below, and a general formula (
1,1-dihydroperfluoroalkylamine represented by III), 1-alkyl-2-heropyridinium iodide represented by general formula (IV), and trialkylamine represented by general formula (V). It is produced by reacting according to the following formula in the presence of
（■） （ｍ） （ＩＶ）
（Ｖ）但し、前記式中、Ｒ８、ｍ、 ｎ、 Ｒ，
、Ｒ２、Ｒ７、Ｒ４は前記と同一の意味を有する。Ｘは
塩素又は臭素を示す。(■) (m) (IV)
(V) However, in the above formula, R8, m, n, R,
, R2, R7 and R4 have the same meanings as above. X represents chlorine or bromine.
前記ポリアクリル酸の修飾反応は、反応溶媒としてＮ、
Ｎ−ジメチルホルムアミドを用い１反応部度として１０
℃〜８０℃、好ましくは３０℃〜６０℃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、ポリアクリ
ル酸のＮ、Ｎ−ジメチルホルムアミド溶液中に１．１−
ジヒドロペルフルオロアルキルアミン、トリアルキルア
ミン、及びヨウ化１〜アルキル−２ハロピリジウムを加
える。この場合、加える１、１−ジヒドロペルフルオロ
アルキルアミンの量を変えることにより、任意の割合で
ポリアクリル酸にアミド結合を介して１，１−ジヒドロ
ペルフルオロアルキル基を修飾できる。数時間の撹拌後
、反応溶液を濃縮、精製して、含フツ素高分子化合物を
得る。The modification reaction of polyacrylic acid is performed using N as a reaction solvent,
Using N-dimethylformamide, 1 reaction site is 10
It can be carried out at a temperature of 30°C to 60°C, preferably 30°C to 60°C. To carry out this reaction preferably, 1.1-
Add dihydroperfluoroalkylamine, trialkylamine, and 1-alkyl-2 halopyridium iodide. In this case, by changing the amount of 1,1-dihydroperfluoroalkylamine added, it is possible to modify the 1,1-dihydroperfluoroalkyl group in polyacrylic acid via an amide bond in any ratio. After stirring for several hours, the reaction solution is concentrated and purified to obtain a fluorine-containing polymer compound.
得られた含フツ素高分子化合物はフッ素分析及びＩＲス
ペクトルにより前記一般式（１）で表わされる含フツ素
ポリアクリル酸であることが同定された。The obtained fluorine-containing polymer compound was identified by fluorine analysis and IR spectrum to be a fluorine-containing polyacrylic acid represented by the general formula (1).
また、この含フツ素高分子化合物は、下式で表されるよ
うに、前記一般式（ｎ）で表されるポリアクリル酸と塩
化チオニルとの反応ののち、前記一般式（ｍ）で表され
る１、１−ジヒドロペルフルオロアルキルアミンを、一
般式（Ｖ）で表わされるトリアルキルアミンの存在下反
応させ、さらにアルカリ水溶液、次いで希酸で処理する
ことによっても製造することができる。Further, as shown in the following formula, this fluorine-containing polymer compound is obtained by reacting polyacrylic acid represented by the general formula (n) with thionyl chloride, and then producing the fluorine-containing polymer compound represented by the general formula (m). It can also be produced by reacting the 1,1-dihydroperfluoroalkylamine represented by formula (V) in the presence of a trialkylamine represented by general formula (V), and further treating with an aqueous alkaline solution and then with a dilute acid.
（ＩＩ）
但し、前記式中、Ｒ，、ｍ、ｎ、 Ｒ，、Ｒ１及びＲ４
は前記と同一の意味を有する。(II) However, in the above formula, R,, m, n, R,, R1 and R4
has the same meaning as above.
本発明の含フツ素高分子化合物は有機溶剤に溶け、この
希薄溶液を純水上に展開することで容易に単分子膜を形
成し、ラングミュア−プロジェット膜を作成できる。純
水上にこの含フツ素高分子を展開した時の表面圧−占有
面積曲線（Ｆ−Ａ曲線）の測定から、修飾率の増加によ
り１．１−ジヒドロペルフルオロアルキル基−つの占め
る面積が小さくなった超薄膜が作成できることが分かる
。特に、修飾率３０％以上の高分子化合物では、１．１
−ジヒドロペルフルオロアルキル基−つの占める面積、
すなわち極限面積はペルフルオロアルキル基の断面積で
ある２８人２よりも小さい値を示しでおり、これより、
１．１−ジヒドロペルフルオロアルキル基が重なった配
列をもった超薄膜となることが分かった。The fluorine-containing polymer compound of the present invention is dissolved in an organic solvent, and by spreading this dilute solution on pure water, a monomolecular film can be easily formed, and a Langmuir-Prodgett film can be created. Measurement of the surface pressure-occupied area curve (F-A curve) when this fluorine-containing polymer was spread on pure water revealed that as the modification rate increased, the area occupied by the 1,1-dihydroperfluoroalkyl group became smaller. It can be seen that an ultra-thin film can be created. In particular, for polymer compounds with a modification rate of 30% or more, 1.1
- dihydroperfluoroalkyl group - area occupied by
In other words, the limit area shows a value smaller than 28 people 2, which is the cross-sectional area of the perfluoroalkyl group, and from this,
It was found that an ultra-thin film having an arrangement in which 1.1-dihydroperfluoroalkyl groups overlapped was formed.
また、この含フツ素高分子化合物はその希薄溶液を金属
塩水溶液上に展開することで、容易に金属イオンを含む
単分子膜を形成し、ラングミュア−ブロジェット膜を作
成できる。この場合、金属イオンとしてはカルボキシル
基と水不溶性の塩を形成し得るものであればよく、この
ような金属イオンとしては、カルシウムや、バリウム、
カドミウム等の多価金属塩由来の金属イオンを挙げるこ
とができる。この金属は、含フツ素高分子化合物のカル
ボキシル基に結合する。金属塩水溶液上にこの含フツ素
高分子化合物を展開した時のＦ−Ａ曲線の測定から、純
水上に展開した場合と同様に、修飾率の増加により極限
面積が小さくなった超薄膜が作成できることが分かる。Further, by spreading a dilute solution of this fluorine-containing polymer compound on an aqueous metal salt solution, a monomolecular film containing metal ions can be easily formed, and a Langmuir-Blodgett film can be created. In this case, the metal ion may be any metal ion that can form a water-insoluble salt with the carboxyl group, and examples of such metal ions include calcium, barium,
Mention may be made of metal ions derived from polyvalent metal salts such as cadmium. This metal binds to the carboxyl group of the fluorine-containing polymer compound. From the measurement of the F-A curve when this fluorine-containing polymer compound was spread on a metal salt aqueous solution, it was found that an ultra-thin film with a smaller ultimate area due to an increase in the modification rate was obtained, similar to when it was spread on pure water. It turns out that you can create one.
この際、修飾率が４％と低い高分子化合物では純水上に
展開した場合と比べて小さい極限面積を示し、修飾率が
２０％以上の高分子化合物では同じ極限面積を示した。At this time, polymer compounds with a low modification rate of 4% showed a smaller limit area than when developed on pure water, and polymer compounds with a modification rate of 20% or more showed the same limit area.
さらに、修飾率が２０％以下の高分子では、純水上に展
開した場合と比べてＦ−Ａ曲線の立ち上がり方が急にな
り、崩壊圧が低くなる傾向を示した。Furthermore, for polymers with a modification rate of 20% or less, the rise of the FA curve becomes steeper and the collapse pressure tends to be lower than when developed on pure water.
この超薄膜をガラス基板上に一層又は多層ですくいとり
、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。その結果、純水上に展
開した場合は、ポリアクリル酸の修飾率が５．２０．３
１％の含フツ素高分子化合物のＬＢ膜はγＣ値がそれぞ
れ約１６．１５．１７を示した。これらの値はポリテト
ラフルオロエチレンのγＣ値１８．５より小さく、表面
エネルギーの低い、撥水撥油性、防塵性等の性質を示す
優れた膜であると言える。This ultra-thin film was scooped out in one layer or in multiple layers onto a glass substrate, and the film thickness and critical surface tension γc (dyn/cm) for n-alkanes were determined. As a result, when developed on pure water, the modification rate of polyacrylic acid was 5.20.3.
The LB films made of 1% fluorine-containing polymer compound showed γC values of about 16, 15, and 17, respectively. These values are smaller than the γC value of polytetrafluoroethylene, which is 18.5, and it can be said that the film exhibits excellent properties such as low surface energy, water and oil repellency, and dust resistance.
また、金属塩上に展開したＬＢ膜はやや大きいγＣ値を
示す傾向があり、カルシウム塩水溶液上に展開した場合
、ポリアクリル酸の修飾率が５．２０．３１％の含フツ
素高分子化合物のＬＢ膜はｙｃ値がそれぞれ約１９．１
７．１７を示した。これらの値もポリテトラフルオロエ
チレンのγＣ値１８．５と同程度あるいはこれより小さ
く、表面エネルギーの低い、優れた膜であると言える。In addition, LB films developed on metal salts tend to show a somewhat large γC value, and when developed on calcium salt aqueous solutions, LB films developed on metal salts exhibit a fluorine-containing polymer compound with a polyacrylic acid modification rate of 5.20.31%. The LB films have a yc value of approximately 19.1, respectively.
It showed 7.17. These values are also comparable to or smaller than the γC value of polytetrafluoroethylene, which is 18.5, and can be said to be an excellent film with low surface energy.
膜厚をタリステップ及びＸ線回折により測定したところ
、修飾率２０％以下の含フツ素高分子化合物の超薄膜は
一層当り約１０〜４０人であるが、修飾率３０％の含フ
ッ速高分子化合物の超薄膜は一層当り約２００Å以上と
なり、１．１−ジヒドロペルフルオロアルコキシフェニ
ル基の重なりにより、厚くなったと言える。When the film thickness was measured by Talystep and X-ray diffraction, an ultra-thin film of a fluorine-containing polymer compound with a modification rate of 20% or less was about 10 to 40 layers per layer, but a film with a modification rate of 30% and a high polymer compound containing fluorine The ultra-thin film of the molecular compound was about 200 Å or more per layer, and it can be said that it became thicker due to the overlap of the 1,1-dihydroperfluoroalkoxyphenyl groups.
また、本発明の含フツ素高分子化合物は修飾率が高いと
溶媒に溶けないが、加熱すると軟化し、製膜できる。こ
の膜は、ポリテトラフルオロエチレンよりもＹＣ値が低
く、優れた低表面エネルギー性を示す。とくに、修飾率
が高いほどγＣ値は低く、より優れた低表面エネルギー
性を示している。Further, the fluorine-containing polymer compound of the present invention is not soluble in a solvent when the modification rate is high, but it becomes soft when heated and can be formed into a film. This film has a lower YC value than polytetrafluoroethylene and exhibits excellent low surface energy properties. In particular, the higher the modification rate, the lower the γC value, indicating better low surface energy properties.
すなわち、本発明によれば、ポリアクリル酸にアミド結
合を介して１，１−ジヒドロペルフルオロアルキル基を
、導入試薬である１、１−ジヒドロペルフルオロアルキ
ルアミンの量を任意に変えることにより種々の割合で修
飾できる。この含フツ素高分子化合物は可溶性であり、
ラングミュア−プロジェッ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、この含フツ素高分子化合物の溶液を
金属塩水溶液上に展開することにより、金属塩を取り込
んだ従来にないタイプの高分子化合物の超薄膜を得るこ
とができる。この超薄膜の性状は一つの１．１−ジヒド
ロペルフルオロアルキル基の占める面積を１，１−ジヒ
ドロペルフルオロアルキル基のポリアクリル酸への修飾
率及びＬＢ膜を展開する際の水層中の金属塩の有無によ
り制御できる。That is, according to the present invention, a 1,1-dihydroperfluoroalkyl group is introduced into polyacrylic acid via an amide bond in various proportions by arbitrarily changing the amount of 1,1-dihydroperfluoroalkylamine, which is an introduction reagent. It can be modified with This fluorine-containing polymer compound is soluble,
It can be made into an ultra-thin film by the Langmuir-Prodgett method, and can be used as an unprecedented ultra-thin surface-modifying substance. Further, by spreading this solution of the fluorine-containing polymer compound on an aqueous metal salt solution, an ultra-thin film of an unprecedented type of polymer compound incorporating a metal salt can be obtained. The properties of this ultra-thin film are determined by the area occupied by one 1,1-dihydroperfluoroalkyl group, the modification rate of the 1,1-dihydroperfluoroalkyl group with polyacrylic acid, and the metal salt in the water layer when developing the LB film. It can be controlled by the presence or absence of
これらの膜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優れた低
表面エネルギー性を示す。さらに、１．１−ジヒドロペ
ルフルオロアルキル基のポリアクリル酸への修飾率及び
水層中の金属塩の有無を変えることによりこの膜の表面
状態を制御することができる。The surfaces of these films contain perfluoroalkyl functional groups and exhibit lower surface energy properties than polytetrafluoroethylene. Furthermore, the surface condition of this membrane can be controlled by changing the modification rate of 1,1-dihydroperfluoroalkyl groups to polyacrylic acid and the presence or absence of metal salts in the water layer.
従来、含フッ素基を共有結合でポリアクリル酸に修飾し
、ラングミュア−プロジェット法により分子内や分子間
で配列の制御された機能性の高分子化合物の超薄膜を作
製した例はなく、金属塩水溶液上に含フツ素高分子化合
物を展開した金属塩を含んだＬ８膜を得た例もない。Until now, there has been no example of modifying polyacrylic acid with a fluorine-containing group through covalent bonds and using the Langmuir-Prodgett method to create an ultra-thin film of a functional polymer compound with a controlled arrangement within or between molecules. There is also no example of obtaining an L8 film containing a metal salt by developing a fluorine-containing polymer compound on an aqueous salt solution.
本発明でラングミュア−ブロジェット膜素材として適用
し得る含フツ素高分子化合物は前記一般式（１）におい
て、ｎ／ｍ≦０．４を満たしたものである・なお、本明
細書で言うラングミュア−プロジェット膜とは、従来よ
く知られているラングミュア−プロジェット法により得
られる単分子膜及び累積膜を意味する。In the present invention, the fluorine-containing polymer compound that can be applied as a Langmuir-Blodgett membrane material is one that satisfies n/m≦0.4 in the general formula (1). - Prodgett film means a monomolecular film and a cumulative film obtained by the conventionally well-known Langmuir-Prodgett method.
次に本発明を実施例により更に詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例１
窒素雰囲気下、ポリアクリル酸（平均分子量：約４５０
０００）４３５■をＮ、Ｎ−ジメチルホルムアミド（Ｄ
ＭＦ）３０−に溶かした溶液に、１．１−ジヒドロペル
フルオロオクチルアミン１２０ＩＩＩｇとトリブチルア
ミン１３６■をＤＭＦ３−に溶かして加え、さらにヨウ
化１−メチル−２−クロロピリジニウム９３■をＤＭＦ
３−に溶かして加え、５０℃で５時間撹拌した。この溶
液を減圧下で溶媒除去し、残滓をメタノール５ＩＩ１１
２に溶かした後ジエチルエーテル５０Ｅ１１２を加えて
、析出した高分子化合物を濾取した。さらにメタノール
５ｄとジエチルエーテル５０−による再沈及びメタノー
ル５−と５％塩酸５０ｍＱによる再沈を行い、水洗して
乾燥すると、ポリアクリル酸中４％のカルボキシル基に
アミド結合で１．１−ジヒドロペルフルオロオクチル基
が修飾された高分子化合物が得られた。得られた高分子
化合物は赤外吸収スペクトルにより、アミド結合：１６
８６．１５５５（！Ｄ−１、炭素−フッ素結合＝１３０
０〜１１００ａｎ−’の強い吸収が認められたことによ
り確認された。また、フルオロアルキル基の修飾率はフ
ッ素分析値１３．８％より求めた。Example 1 Under a nitrogen atmosphere, polyacrylic acid (average molecular weight: about 450
000) 435■ to N,N-dimethylformamide (D
MF) 120III g of 1,1-dihydroperfluorooctylamine and 136 μg of tributylamine dissolved in DMF3- were added to the solution dissolved in DMF30-, and 93 μg of 1-methyl-2-chloropyridinium iodide was added in DMF.
3- and stirred at 50°C for 5 hours. The solvent was removed from this solution under reduced pressure and the residue was dissolved in methanol 5II11
2, diethyl ether 50E112 was added thereto, and the precipitated polymer compound was collected by filtration. Furthermore, reprecipitation with methanol 5d and diethyl ether 50- and reprecipitation with methanol 5- and 50 mQ of 5% hydrochloric acid was performed, and when washed with water and dried, 1,1-dihydro A polymer compound modified with perfluorooctyl groups was obtained. The obtained polymer compound was determined by infrared absorption spectrum to have an amide bond of 16
86.1555 (!D-1, carbon-fluorine bond = 130
This was confirmed by the observation of strong absorption of 0 to 1100 an-'. Further, the modification rate of the fluoroalkyl group was determined from the fluorine analysis value of 13.8%.
同様の方法で、１，１−ジヒドロペルフルオロオクチル
アミンを用い、ポリアクリル酸のカルボキシル基に対し
て、５．２０．４０．６０．８０．１００％で反応を行
いそれぞれ修飾率４．２０．４０．６２．８１．１００
％の高分子化合物を得た。これらのペルフルオロアルキ
ル基の修飾率はすへてフッ素分析値より求めた。なお、
修飾率６０％以上の高分子化合物の合成では必要に応じ
て反応時間を長くした。また、修飾率８０％以上の場合
には１反応後、溶媒を除去したのち、残滓をジメチルス
ルホキシド・５％塩酸（１：１０）、ＤＭＦ・ジエチル
エーテル（１：１０）、さら熱メタノールで洗うことに
より高分子化合物を単離精製した。In a similar manner, 1,1-dihydroperfluorooctylamine was used to react the carboxyl group of polyacrylic acid at a modification rate of 5.20.40.60.80.100%, respectively, with a modification rate of 4.20.40%. .62.81.100
% of polymer compound was obtained. The modification rate of these perfluoroalkyl groups was determined from the fluorine analysis values. In addition,
When synthesizing a polymer compound with a modification rate of 60% or more, the reaction time was increased as necessary. If the modification rate is 80% or more, after one reaction, remove the solvent and wash the residue with dimethyl sulfoxide/5% hydrochloric acid (1:10), DMF/diethyl ether (1:10), and hot methanol. The polymer compound was isolated and purified by this method.
また、修飾率４０％の高分子化合物からエタノールを用
いて可溶成分を抽出することにより修飾率３１％の高分
子化合物（フッ素分析値４６．７％）を得た。Further, by extracting soluble components from a polymer compound with a modification rate of 40% using ethanol, a polymer compound with a modification rate of 31% (fluorine analysis value 46.7%) was obtained.
実施例２
塩化カルシウム管を取り付けた反応容器中でポリアクリ
ル酸（平均分子量：約４５００００） １８６■を塩化
チオニル５７２に溶かし、Ｎ、Ｎ−ジメチルホルムアミ
ド（ＤＭＦ）１滴を加えて７時間加熱還流した。減圧下
、未反応塩化チオニルを除去した後、０ＭＦ２０−を加
えて溶解し、さらにトリエチルアミン２５４■と１，１
−ジヒドロペルフルオロオクチルアミン２０２■をそれ
ぞれＤＭＦｌｄずつに溶かして加え、１日撹拌した。Example 2 Polyacrylic acid (average molecular weight: approximately 450,000) 186 µm was dissolved in thionyl chloride 572 in a reaction vessel equipped with a calcium chloride tube, 1 drop of N,N-dimethylformamide (DMF) was added, and the mixture was heated under reflux for 7 hours. did. After removing unreacted thionyl chloride under reduced pressure, 0MF20- was added and dissolved, and triethylamine 254 and 1,1
202 μl of -dihydroperfluorooctylamine was dissolved in DMFld and stirred for 1 day.
減圧下、溶媒を除去した後、２規定水酸化ナトリウム水
溶液２０−を加えて１日撹拌した。濃塩酸を加えて酸性
とし、析出した高分子化合物を水洗、次いでメタノール
・５％塩酸（１：１０）、メタノール・ジエチルエーテ
ル（１：１０）で洗うことによりポリアクリル酸中２０
％のカルボキシル基にアミド結合を介して１．１−ジヒ
ドロペルフルオロオクチル基が修飾された高分子化合物
（フッ素分析値３８．１％）が得られた。After removing the solvent under reduced pressure, a 2N aqueous solution of sodium hydroxide (20°C) was added and stirred for 1 day. The precipitated polymer compound was acidified by adding concentrated hydrochloric acid and washed with water, then with methanol/5% hydrochloric acid (1:10) and methanol/diethyl ether (1:10) to dissolve the precipitated polymer compound in polyacrylic acid.
% of carboxyl groups were modified with 1,1-dihydroperfluorooctyl groups via amide bonds (fluorine analysis value: 38.1%).
実施例３
（ラングミュア−プロジェット膜の作製）実施例１で合
成した各種含フツ素高分子化合物（を１，１−ジヒドロ
ペルフルオロアルキル基の修飾率（Ｍ％）に対応したＰ
ＡＡＣＦ（Ｍ）と略す）を用い、ラングミュア−プロジ
ェット法により、以下のようにしてそのＬＢ膜を作製し
た。Example 3 (Preparation of Langmuir-Prodgett membrane) Various fluorine-containing polymer compounds synthesized in Example 1 were mixed with P corresponding to the modification rate (M%) of 1,1-dihydroperfluoroalkyl groups.
Using AACF (abbreviated as M)), the LB film was produced by the Langmuir-Prodgett method as follows.
ＰＡＡＣＦ５．２０．３１のエタノール・ベンゼン希薄
混合溶液をそれぞれ調整し、これらの溶液を１７℃の純
水上にそれぞれ展開してＬＢ膜を形成し、その表面圧−
占有面積の関係（Ｆ−Ａ曲線）を測定した。その結果を
第１図に示す。この結果より、膜中のペルフルオロアル
キル基−分子の占める面積、つまり掻限面積はＰＡＡＣ
Ｆ４．２０．３１の順にそれぞれ６６．３９．５人２の
値を示した。A dilute mixed solution of ethanol and benzene of PAACF5.20.31 was prepared, and each of these solutions was spread on pure water at 17°C to form an LB film, and its surface pressure -
The occupied area relationship (FA curve) was measured. The results are shown in FIG. From this result, the area occupied by the perfluoroalkyl group-molecule in the membrane, that is, the limited area is PAAC
In the order of F4, 20, and 31, the values were 66, 39, and 2 for each person.
この水面上の超薄膜をガラス基板上に表面圧２０聰Ｎ−
ｒＩ−”で単分子膜及び累積膜として移しとった。This ultra-thin film on the water surface was placed on a glass substrate at a surface pressure of 20 N-
rI-'' was transferred as a monolayer and a cumulative film.
これらは透明な膜であった。These were transparent membranes.
実施例４
（金属塩を含むラングミュア−プロジェット膜の作製）
実施例１で合成したＰＡＡＣＦ５．２０．３１のエタノ
ール・ベンゼン希薄混合溶液をそれぞれ調製し、これら
の溶液を１７℃の、緩衝剤として炭酸水素カリウムを含
む塩化カルシウム水溶液（塩化カルシウム濃度：４．Ｏ
Ｘ １０−’＋ｏＱ ｌ−’、炭酸水素カリウム濃度：
４．ＯＸ １０−’ｍｏＱ１−’）上にそれぞれ展開し
てＬＢ膜を形成し、そのＦ−Ａ曲線を測定した。その結
果を第２図に示す。この結果より、極限面積はＰＡＡＣ
Ｆ４．２０．３１の順にそれぞれ９６．３９．５人２の
値を示した。Example 4 (Preparation of Langmuir-Prodgett membrane containing metal salt) Dilute mixed solutions of ethanol and benzene of PAACF5.20.31 synthesized in Example 1 were prepared, and these solutions were incubated at 17°C as a buffer. Calcium chloride aqueous solution containing potassium hydrogen carbonate (calcium chloride concentration: 4.0
X 10-'+oQ l-', potassium hydrogen carbonate concentration:
4. OX 10-'moQ1-') to form an LB film, and its FA curve was measured. The results are shown in FIG. From this result, the limit area is PAAC
In the order of F4, 20, and 31, the values were 96, 39, and 2 people, respectively.
この水面上の超薄膜をガラス基板上に表面圧２０ＩＩＮ
−Ｉｌｌ−１で単分子膜及び累積膜として移しとった。This ultra-thin film on the water surface was placed on a glass substrate at a surface pressure of 20 IIN.
- Ill-1 was transferred as a monolayer and a cumulative film.
これらは透明な膜であった。These were transparent membranes.
実施例５
（プレス膜の作製）
実施例１で合成したＰＡＡＣＦ４０．６２．８１．１０
０を基板上で加熱し軟化点で加圧することにより膜を得
ることかできた、
実施例６
（臨界表面張力γＣの測定）
実施例３．４及び５で得た膜について、ｎ−アルカンと
の接触角を測定し、Ｚｉｓｍａｎプロットから求めた臨
界表面張力γＣ値を最小二乗法で計算した。Example 5 (Preparation of pressed membrane) PAACF40.62.81.10 synthesized in Example 1
Example 6 (Measurement of critical surface tension γC) For the films obtained in Examples 3.4 and 5, a film was obtained by heating 0 on a substrate and pressurizing it at its softening point. The contact angle was measured, and the critical surface tension γC value obtained from the Zisman plot was calculated using the least squares method.
これらの結果を第１表に示した。These results are shown in Table 1.
実施例７
（膜厚の測定）
実施例３及び４で得たラングミュア−プロジェット膜に
ついて、次の二つの方法で膜厚を測定した。Example 7 (Measurement of film thickness) The film thickness of the Langmuir-Prodgett films obtained in Examples 3 and 4 was measured using the following two methods.
（１）タリステップによる測定
薄膜を一部剥し、膜との段差をタリステソプにより測定
した。その結果１層の膜厚は、純水上に展開したラング
ミュア−プロジェット膜（実施例３）では、ＰＡＡＣＦ
４．２０．３１の順にそれぞれ２７〜３９．９〜１２．
１８０〜２８０人、塩化カルシウム水溶液上に展開した
ラングミュア−プロジェット膜（実施例４）では、ＰＡ
ＡＣＦ４．２０．３１の順にそれぞれ２６〜４０．１０
〜１８，２４０〜４４０人の値が得られた。(1) Measurement using Talystep A part of the thin film was peeled off, and the difference in level between the thin film and the film was measured using Talystep. As a result, the film thickness of one layer was PAACF
27-39.9-12.4, 20.31, respectively.
In the Langmuir-Prodgett membrane developed on an aqueous calcium chloride solution (Example 4), PA
ACF4.20.31 respectively 26 to 40.10
Values of ~18,240 to 440 people were obtained.
（２）Ｘ線回折による測定
銅（７）Ｋａ、、 λ＝１．５４０５０．４０Ｋｖ、
３０ｍＡ （７）条件テ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ッグの
式より求めると、１層の膜厚は、純水上に展開したラン
グミュア−プロジェット膜では、ＰＡＡＣＦ４．２ｏ、
３１の順にそれぞれ約３２．１６，２２０人、塩化カル
シウム水溶液上に展開したラングミュア−プロジェット
膜では、ＰＡＡＣＦ４．２０．３１の順にそれぞれ約３
５．１８．２９０人の値が得られた。(2) Measured copper by X-ray diffraction (7) Ka, λ=1.54050.40Kv,
30mA (7) Conditions When measuring the X-ray diffraction pattern,
A diffraction pattern was observed. From this, the film thickness is calculated from Bragg's formula, and the film thickness of one layer is PAACF4.2o for Langmuir-Progett film developed on pure water.
For the Langmuir-Prodgett membrane developed on an aqueous calcium chloride solution, approximately 32,16,220 people each appeared in the order of PAACF4, 20, and 31.
Values for 5.18.290 people were obtained.
０３層03 layer
図面は本発明による含フツ素高分子化合物のラングミュ
ア−ブロジェット膜のＦ−Ａ曲線を示すもので、第１図
は純水上に展開した時のＦ−Ａ曲線、第２図は塩化カル
シウム塩水溶液上に展開した時のＦ−へ曲線である。The drawings show the F-A curve of the Langmuir-Blodgett membrane of the fluorine-containing polymer compound according to the present invention. It is a curve to F- when developed on a salt aqueous solution.
Claims (5)
ル基を示し、ｍは１０〜１０００００の数を示し、ｎは
０＜ｎ≦ｍを満たす数である） で表わされる含フッ素高分子化合物。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_f represents a perfluoroalkyl group having 6 to 15 carbon atoms, m represents a number from 10 to 100,000, and n represents 0<n≦m A fluorine-containing polymer compound represented by
ル基を示し、ｍは１０〜１０００００の数を示し、ｎは
０＜ｎ≦ｍを満たす数である） で表わされる含フッ素高分子化合物を製造する方法にお
いて、一般式 ▲数式、化学式、表等があります▼ （式中、ｍは前記と同じ意味を持つ） で表わされるポリアクリル酸と、一般式 Ｒ＿ｆＣＨ＿２ＮＨ＿２ （式中、Ｒ＿ｆは前記と同じ意味を持つ） で表わされる１，１−ジヒドロペルフルオロアルキルア
ミンとを、一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿１は炭素数１〜５のアルキル基を示し、Ｘ
は塩素又は臭素を示す） で表わされるヨウ化１−アルキル−２−ハロピリジニウ
ムと、一般式 Ｒ＿２Ｒ＿３Ｒ＿４Ｎ （式中、Ｒ＿２、Ｒ＿３、Ｒ＿４は炭素数２〜６のアル
キル基を示す） で表されるトリアルキルアミンの存在下で反応させるこ
とを特徴とする方法。(2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_f represents a perfluoroalkyl group having 6 to 15 carbon atoms, m represents a number from 10 to 100,000, and n represents 0<n≦m In the method of manufacturing a fluorine-containing polymer compound represented by the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (where m has the same meaning as above) An acid and a 1,1-dihydroperfluoroalkylamine represented by the general formula R_fCH_2NH_2 (wherein R_f has the same meaning as above) can be expressed by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R_1 represents an alkyl group having 1 to 5 carbon atoms, and X
represents chlorine or bromine) and 1-alkyl-2-halopyridinium iodide represented by the general formula R_2R_3R_4N (wherein R_2, R_3, R_4 represent an alkyl group having 2 to 6 carbon atoms) A method characterized by carrying out the reaction in the presence of a trialkylamine.
ル基を示し、ｍは１０〜１０００００の数を示し、ｎは
０＜ｎ≦ｍを満たす数である） で表わされる含フッ素高分子化合物を製造する方法にお
いて、一般式 ▲数式、化学式、表等があります▼ （式中、ｍは前記と同じ意味を持つ） で表わされるポリアクリル酸と塩化チオニルとの反応に
より得られる高分子化合物と、一般式Ｒ＿ｆＣＨ＿２Ｎ
Ｈ＿２ （式中、Ｒ＿ｆは前記と同じ意味を持つ） で表わされる１，１−ジヒドロペルフルオロアルキルア
ミンとを、一般式 Ｒ＿２Ｒ＿３Ｒ＿４Ｎ （式中、Ｒ＿２、Ｒ＿３、Ｒ＿４は炭素数２〜６のアル
キル基を示す） で表されるトリアルキルアミンの存在下で反応させるこ
とを特徴とする方法。(3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. In the method of manufacturing a fluorine-containing polymer compound represented by the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (where m has the same meaning as above) A polymer compound obtained by the reaction of an acid and thionyl chloride and a general formula R_fCH_2N
1,1-dihydroperfluoroalkylamine represented by H_2 (in the formula, R_f has the same meaning as above), and a 1,1-dihydroperfluoroalkylamine represented by the general formula R_2R_3R_4N (in the formula, R_2, R_3, R_4 represent an alkyl group having 2 to 6 carbon atoms). A method characterized by carrying out the reaction in the presence of a trialkylamine represented by:
ル基を示し、ｍは１０〜１０００００の数を示し、ｎは
０＜ｎ≦０．４ｍを満たす数である） で表わされる含フッ素高分子化合物からなるラングミュ
アーブロジェット膜。(4) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_f represents a perfluoroalkyl group having 6 to 15 carbon atoms, m represents a number from 10 to 100,000, and n represents 0<n≦0 A Langmuir-Blodgett film made of a fluorine-containing polymer compound represented by:
ル基を示し、ｍは１０〜１０００００の数を示し、ｎは
０＜ｎ≦０．４ｍを満たす数である） で表わされる含フッ素高分子化合物を多価金属塩水溶液
上に展開することにより作製されるラングミュアーブロ
ジェット膜。(5) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_f represents a perfluoroalkyl group having 6 to 15 carbon atoms, m represents a number from 10 to 100,000, and n represents 0<n≦0 A Langmuir-Blodgett membrane produced by developing a fluorine-containing polymer compound represented by (the number satisfies .4 m) on an aqueous solution of a polyvalent metal salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3925890A JPH0662721B2 (en) | 1990-02-20 | 1990-02-20 | Polymer compound modified with fluorine-containing group, method for producing the same and polymer thin film thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3925890A JPH0662721B2 (en) | 1990-02-20 | 1990-02-20 | Polymer compound modified with fluorine-containing group, method for producing the same and polymer thin film thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03243609A true JPH03243609A (en) | 1991-10-30 |
| JPH0662721B2 JPH0662721B2 (en) | 1994-08-17 |
Family
ID=12548119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3925890A Expired - Lifetime JPH0662721B2 (en) | 1990-02-20 | 1990-02-20 | Polymer compound modified with fluorine-containing group, method for producing the same and polymer thin film thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0662721B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005270925A (en) * | 2004-03-26 | 2005-10-06 | Chisso Corp | Microchannel system |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4484106B2 (en) * | 2004-12-14 | 2010-06-16 | 独立行政法人産業技術総合研究所 | Organic thin film body having nano-structured linear groove or spiral groove and method for producing the same |
-
1990
- 1990-02-20 JP JP3925890A patent/JPH0662721B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005270925A (en) * | 2004-03-26 | 2005-10-06 | Chisso Corp | Microchannel system |
| JP4645053B2 (en) * | 2004-03-26 | 2011-03-09 | チッソ株式会社 | Micro channel system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0662721B2 (en) | 1994-08-17 |
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