JPH01306674A - Fluorine-containing phenolic fiber - Google Patents
Fluorine-containing phenolic fiberInfo
- Publication number
- JPH01306674A JPH01306674A JP13816188A JP13816188A JPH01306674A JP H01306674 A JPH01306674 A JP H01306674A JP 13816188 A JP13816188 A JP 13816188A JP 13816188 A JP13816188 A JP 13816188A JP H01306674 A JPH01306674 A JP H01306674A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- tables
- fluorine
- formula
- mathematical
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 48
- 239000011737 fluorine Substances 0.000 title claims abstract description 48
- 229920006282 Phenolic fiber Polymers 0.000 title claims abstract description 34
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000835 fiber Substances 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 30
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004185 ester group Chemical group 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 8
- -1 perfluoroalkyl chloride Chemical compound 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000003373 anti-fouling effect Effects 0.000 abstract description 6
- 230000003068 static effect Effects 0.000 abstract description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- PBVZTJDHQVIHFR-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F PBVZTJDHQVIHFR-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は、撥水性、防汚性（非付着性）、耐薬品性、
耐熱性および摺動性（低摩擦耐摩耗性）等の多様な特性
を有する機能性含フッ素フェノール繊維およびその製造
方法に関する。[Detailed description of the invention] Industrial application field This invention has water repellency, antifouling property (non-stick property), chemical resistance,
The present invention relates to functional fluorine-containing phenolic fibers having various properties such as heat resistance and sliding properties (low friction and abrasion resistance), and a method for producing the same.
発明の概要
この発明は、フェノール繊維において、フェノール性−
〇Ｈの少なくとも一部を含フッ素置換基によって置換さ
せることによって、フェノール繊維の特性を改良するよ
うにしたものである。Summary of the Invention This invention provides phenolic fibers with phenolic
The characteristics of the phenol fiber are improved by substituting at least a portion of 〇H with a fluorine-containing substituent.
従来の技術
フェノール繊維は防火性、断熱性、電気絶縁性および耐
摩擦摩耗性等に優れているばかりでなく、軽量でしかも
各種の樹脂やゴム等に対する親和性が優れているので、
難燃ケーブル、防炎シート、耐熱膜、ガスケット材、摩
擦材、摺動材等とじて従来から使用されている。Conventional technology Phenol fibers not only have excellent fire retardant properties, heat insulation properties, electrical insulation properties, and friction and wear resistance, but also are lightweight and have excellent affinity for various resins and rubbers.
It has been traditionally used for flame-retardant cables, flame-retardant sheets, heat-resistant films, gasket materials, friction materials, sliding materials, etc.
しかしながら、フェノール繊維にはフェノール性水酸基
が存在するために耐水性や耐薬品性が劣るという欠点が
あるだけでなく、防汚性や摺動性等の表面特性も劣ると
いう難点がある。However, due to the presence of phenolic hydroxyl groups, phenolic fibers not only have poor water resistance and chemical resistance, but also have poor surface properties such as antifouling properties and sliding properties.
発明が解決しようとする課題
この発明は、フェノール繊維のこのような問題点を解決
し、多様な特性を有する機能性フェノール繊維を提供す
るためになされたものである。Problems to be Solved by the Invention The present invention was made in order to solve these problems of phenolic fibers and to provide functional phenolic fibers having various properties.
課題を解決するための手段
即ち本発明は、基材フェノール繊維のフェノール性−〇
Ｈの少なくとも一部が一般式（■）：（式中、ｎは１−
１ｏの数を示す）
で表わされるパーフルオロアルケニロキシ基、一般式（
ＩＩ）：
（式中、ｎは１〜ｌＯの数を示す）
で表わされる含フッ素エステル置換基または一般式（■
）ニ
ーＱＣ（ＣＨ，）ｍ−Ｃｎ’Ｆ２ｎ’＋＋ （
ＩＩＩ）■
○
（式中、ｍは０、ｌまたは２の数、好ましくは０または
２の数を示し、ｎ′は１〜８の数を示す）で表わされる
含フッ素エステル置換基によって置換されたことを特徴
とする含フッ素フェノール繊維およびこれらの製造方法
に関する。Means for solving the problem, that is, the present invention provides that at least a part of the phenolic -〇H of the base phenolic fiber has the general formula (■): (where n is 1-
perfluoroalkenyloxy group represented by the general formula (indicating the number of 1o)
II): (wherein, n represents the number from 1 to 1O) or a fluorine-containing ester substituent represented by the general formula (■
) Knee QC(CH,)m-Cn'F2n'++ (
III) Substituted with a fluorine-containing ester substituent represented by ■○ (wherein m is a number of 0, l or 2, preferably 0 or 2, and n' is a number of 1 to 8) The present invention relates to fluorine-containing phenolic fibers and methods for producing them.
本発明に使用する基材フェノール繊維は、自体公知のフ
ェノール樹脂、例えばフェノール、タレシーツ呟 キシ
レノールおよびレゾルシン等のフェノール類とホルムア
ルデヒド、アセトアルデヒドおよびフルフラール等のア
ルデヒド類とを適宜付加縮合させて得られるフェノール
樹脂を公知の方法によって紡糸したものを適宜使用すれ
ばよい。The base phenolic fiber used in the present invention is a phenolic resin known per se, such as a phenol resin obtained by appropriately adding and condensing phenols such as phenol, xylenol, and resorcin with aldehydes such as formaldehyde, acetaldehyde, and furfural. What is necessary is just to use what is spun by a well-known method suitably.
本発明による含フッ素フェノール繊維は、このような基
材フェノール繊維のフェノール性水酸基の少なくとも一
部が上記の一般式（Ｉ）〜（ＩＩＩ）のいずれかで表わ
される含フッ素基で置換された繊維であり、以下、これ
ら３種の含フッ素フェノール繊維について順次説明する
。The fluorine-containing phenolic fiber according to the present invention is a fiber in which at least a part of the phenolic hydroxyl groups of such a base phenol fiber is substituted with a fluorine-containing group represented by any one of the above general formulas (I) to (III). Hereinafter, these three types of fluorine-containing phenolic fibers will be sequentially explained.
一般式（Ｉ）において、ｎは１−１０、好ましくは１〜
６の数を示す。In general formula (I), n is 1-10, preferably 1-10
Shows the number 6.
式（Ｉ）中のパーフルオロアルケニロキシ基として特に
好適なものはヘキサフルオロプロペンモジくはテトラフ
ルオロエチレンのオリゴマー残基を有するものである。Particularly suitable perfluoroalkenyloxy groups in formula (I) are those having an oligomeric residue of hexafluoropropene module or tetrafluoroethylene.
このようなオリゴマー残基としては、次式（ａ）〜（ｅ
）で表わされるものが例示される：（ｂ）
（ｃ）
（ｄ）
（ｅ）
上記パーフルオロアルケニロキシ基によるフェノール性
水酸基の置換率は含フッ素フェノール繊維の使用目的等
に応じて適宜選定すればよく、特に限定的ではなく、こ
の置換率を調節することによって含フッ素フェノール繊
維の撥水性、防汚性、摺動性および耐熱性等の特性を適
宜調整することができる。As such oligomer residues, the following formulas (a) to (e
) are exemplified: (b) (c) (d) (e) The substitution rate of the phenolic hydroxyl group by the above perfluoroalkenyloxy group is appropriately selected depending on the purpose of use of the fluorine-containing phenolic fiber. There is no particular limitation, and by adjusting this substitution rate, the properties of the fluorine-containing phenol fibers, such as water repellency, antifouling properties, sliding properties, and heat resistance, can be adjusted as appropriate.
上記の本発明による含フッ素フェノール繊維の製造方法
は特に限定的ではないが、好適な製法は、前記の基材フ
ェノール繊維および一般式（１’）：％式％
（式中、ｎは１−１０の数を示ｔ）
で表わされるパーフルオロアルケンを塩基性触媒の存在
下で反応させることを特徴とする方法である。Although the method for producing the fluorine-containing phenolic fiber according to the present invention is not particularly limited, a preferred production method uses the base phenol fiber and the general formula (1'): % formula % (where n is 1- This method is characterized by reacting a perfluoroalkene represented by the number t) in the presence of a basic catalyst.
特に好適なパーフルオロアルケア ハ次式（ａ’ ）〜
（ｅ′）で表わされるヘキサフルオロプロペンもしくは
テトラフルオロエチレンのオリゴマーである：（ａ′）
（ｂ′）
（Ｃ′）
（ｄ′）
（ｅ′）
上記の基材フェノール繊維と一般式（■″）で表わされ
るパーフルオロアルケンとの反応割合は反応成分の種類
や所望のフッ素化率等に応じて適宜選定すればよく、特
に限定的ではない。Particularly suitable perfluoroarchea The following formula (a') ~
It is an oligomer of hexafluoropropene or tetrafluoroethylene represented by (e'): (a') (b') (C') (d') (e') The above base phenol fiber and the general formula (■ The reaction ratio with the perfluoroalkene represented by ``) may be appropriately selected depending on the type of reaction components, the desired fluorination rate, etc., and is not particularly limited.
塩基性触媒としてはトリメチルアミンやトリエチルアミ
ン等の３級アミン、炭酸ナトリウムや炭酸カリウム等の
無機塩基性塩類、ピリジンおよびＮ、Ｎ−ジメチルアニ
リン等が例示されるが、特にトリメチルアミンあるいは
トリエチルアミン等の３級アミンが好ましい。Examples of basic catalysts include tertiary amines such as trimethylamine and triethylamine, inorganic basic salts such as sodium carbonate and potassium carbonate, pyridine and N,N-dimethylaniline, and in particular tertiary amines such as trimethylamine and triethylamine. is preferred.
塩基性触媒の使用量も特に限定的ではないが、通常は反
応当量程度使用する。The amount of the basic catalyst used is also not particularly limited, but it is usually used in an amount equivalent to the reaction.
上記の反応は通常は有機溶媒中で行なう。有機溶媒とし
てはアセトニトリル、ジメチルホルムアミド、ジメチル
スルホキサイド、Ｎ−メチルピロリドン、ジグリムおよ
びトリグルム等の極性溶媒のほか、ベンゼン、トルエン
、キシレン、エーテル、テトラヒドロフランおよびアセ
トン等が例示されるが、膨潤性や溶解性の小さな基材フ
ェノール繊維を使用する場合にはジメチルホルムアミド
やジメチルスルホキサイド等の極性溶媒を選択する。The above reaction is usually carried out in an organic solvent. Examples of organic solvents include polar solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, diglyme, and triglyme, as well as benzene, toluene, xylene, ether, tetrahydrofuran, and acetone. When using phenol fiber as a base material with low solubility, a polar solvent such as dimethylformamide or dimethyl sulfoxide is selected.
反応温度も反応成分の種類によって左右され、特に限定
的ではないが、通常は０−１００°Ｃである。The reaction temperature also depends on the type of reaction components and is usually 0-100°C, although it is not particularly limited.
上記の反応によって得られる含フッ素フェノール繊維は
、その赤外線吸収スペクトルが１１００〜１３００ｃｍ
−’付近にＣ−Ｆ伸縮振動に由来する特性吸収を示すの
で、これによって容易に同定することかできる。The fluorine-containing phenol fiber obtained by the above reaction has an infrared absorption spectrum of 1100 to 1300 cm.
Since it exhibits a characteristic absorption derived from C-F stretching vibration near -', it can be easily identified based on this.
一般式（１）において、ｎは前記と同意義である。In general formula (1), n has the same meaning as above.
式＜ ｎ ）中のパーフルオロアルケニロキシ基として
特に好適なものはへキサフルオロプロペンもしくはテト
ラフルオロエチレンのオリゴマー残基を有するものであ
る。Particularly suitable perfluoroalkenyloxy groups in the formula <n) are those having oligomeric residues of hexafluoropropene or tetrafluoroethylene.
このようなオリゴマー残基としては、前記の式（ａ）〜
（ｅ）で表わさ、れるものが例示される。Such oligomer residues include the formulas (a) to
The one represented by (e) is exemplified.
上記の含フッ素エステル置換基によるフェノール性水酸
基の置換率も含フッ素フェノール繊維の使用目的等に応
じて適宜選定すればよく、特に限定的ではなく、この置
換率を調節することによって含フッ素フェノール繊維の
撥水性、防汚性、摺動性および耐熱性等の特性を適宜調
整することができる。The substitution rate of the phenolic hydroxyl group by the above-mentioned fluorine-containing ester substituent may be appropriately selected depending on the purpose of use of the fluorine-containing phenol fiber, and is not particularly limited. Properties such as water repellency, antifouling properties, sliding properties, and heat resistance can be adjusted as appropriate.
上記の本発明による含フッ素フェノール繊維の製造方法
は特に限定的ではないが、好適な製法は、前記の基材フ
ェノール繊維および一般式（ＩＩ”）：（式中、ｎは１
〜ＩＯの数を示す）
で表わされるｐ−パーフルオロアルケニロキシ塩化ベン
ゾイルを塩基性触媒の存在下で反応させることを特徴と
する方法である。Although the method for producing the fluorine-containing phenolic fiber according to the present invention is not particularly limited, a preferred method includes using the base phenol fiber and the general formula (II''): (where n is 1
This method is characterized by reacting p-perfluoroalkenyloxybenzoyl chloride represented by the following formula (indicating the number of ~IO) in the presence of a basic catalyst.
特に好適なｐ−置換塩化ベンゾイルは、ｐ−パーフルオ
ロアルケニロキシ基が前記の（ａ）〜（ｅ）のいずれか
によって表わされるヘキサフルオロプロペンもしくはテ
トラフルオロエチレンのオリゴマー残基を有する化合物
である。Particularly preferred p-substituted benzoyl chlorides are compounds in which the p-perfluoroalkenyloxy group has an oligomeric residue of hexafluoropropene or tetrafluoroethylene represented by any of (a) to (e) above. .
上記の基材フェノール繊維と一般式（ＩＩ″）で表わさ
れるｐ−パーフルオロアルケニロキシ塩化ベンゾイルと
の反応割合は反応成分の種類や所望のフッ素化率等に応
じて適宜選定すればよく、特に限定的ではない。The reaction ratio between the above-mentioned base phenol fiber and p-perfluoroalkenyloxybenzoyl chloride represented by the general formula (II'') may be appropriately selected depending on the type of reaction components, desired fluorination rate, etc. It is not particularly limited.
塩基性触媒としては、前記のトリメチルアミン等を適宜
使用すればよく、その使用量も特に限定的ではないが、
通常は反応当量程度使用する。As the basic catalyst, the above-mentioned trimethylamine etc. may be used as appropriate, and the amount used is not particularly limited, but
Usually, about the reaction equivalent amount is used.
上記の反応は通常は有機溶媒中で行なう。有機溶媒とし
ては、前記のアセトニトリル等を適宜使用すればよいが
、膨潤性や溶解性の小さな基材フ工ノール繊維を使用す
る場合には、ジメチルホルムアミドやジメチルスルホキ
サイド等の極性溶媒を選択する。The above reaction is usually carried out in an organic solvent. As the organic solvent, the above-mentioned acetonitrile etc. may be used as appropriate, but when using phenol fiber as a base material with low swelling and solubility, select a polar solvent such as dimethylformamide or dimethyl sulfoxide. do.
反応温度も反応成分の種類によって左右され、特に限定
的ではないが、通常は０−１００℃である。The reaction temperature also depends on the type of reaction components and is usually 0-100°C, although it is not particularly limited.
上記の反応によって得られる含フッ素フェノール繊維は
、前記のように、ｒＲスペクトルによって容易に同定す
ることができる。The fluorine-containing phenol fiber obtained by the above reaction can be easily identified by the rR spectrum, as described above.
式（ＩＩＩ）において、ｍは０．１または２の数、好ま
しくは０または２の数を示し、ｎ′は１〜８の数を示す
。In formula (III), m represents a number of 0.1 or 2, preferably 0 or 2, and n' represents a number of 1 to 8.
式（１）中のパーフルオロアルキル基−Ｃｎ’ Ｆ２ｎ
’ ＋ ＋として特に好適なものとしては、次のものが
例示されるニ
ーＣＦ、、−ＣＦ２ＣＦユ、 ＣＦ ２ＣＦ ２ＣＦ
ｓ、Ｆ２ＣＦ３
ＣＦ （ＣＦ ３）２、−Ｃ−ＣＦ、ＣＦ。Perfluoroalkyl group -Cn'F2n in formula (1)
' ++ Particularly suitable examples include the following: CF, -CF2CF, CF 2CF 2CF
s, F2CF3CF (CF3)2, -C-CF, CF.
ＣＦ。C.F.
上記の含フッ素エステル置換基によるフェノール性水酸
基の置換率も前記のように、含フッ素フェノール繊維の
使用目的等に応じて適宜選定すればよく、特に限定的で
はなく、この置換率を調節することによって含フッ素フ
ェノール繊維の撥水性、防汚性、摺動性および耐熱性等
の特性を適宜調整することができる。The substitution rate of the phenolic hydroxyl group by the above-mentioned fluorine-containing ester substituent may be appropriately selected depending on the purpose of use of the fluorine-containing phenol fiber, as described above, and is not particularly limited, and this substitution rate may be adjusted. The properties of the fluorine-containing phenol fibers, such as water repellency, antifouling properties, sliding properties, and heat resistance, can be adjusted as appropriate.
上記の本発明による含フッ素フェノール繊維の製造方法
は特に限定的ではないが、好適な製法は、前述の基材フ
ェノール繊維に塩基性触媒の存在下で一般式（Ｉ［［’
）：
Ｃｎ’ Ｆ ２ｎ’ ＋＋ ・（ＣＨ２）ｍｃ ＯＣｌ
２（ＩＩＩ’）（式中、ｍおよびｎ′は前記と同意義で
ある）で表わされるパーフルオロアルキリルクロライド
を反応させるか、または該基材フェノール繊維に無触媒
下で一般式（ＩＩＩ”）：
（式中、ｍおよびｎ′は前記と同意義である）で表わさ
れるパーフルオロアルキリツクアンハイドライドを反応
させる方法である。The method for producing the fluorine-containing phenolic fiber according to the present invention is not particularly limited, but a preferred method is to apply the general formula (I[['
): Cn' F 2n' ++ ・(CH2)mc OCl
2(III') (wherein m and n' have the same meanings as above), or the base phenol fiber is reacted with the general formula (III') without a catalyst. ): (wherein m and n' have the same meanings as above) is a method of reacting a perfluoroalkyl anhydride.
上記の基材フェノール繊維と一般式（■′）で表わされ
るバーフルオロアルキリルクロライドまたは一般式（Ｉ
ＩＩ”）で表わされるパーフルオロアルキリツクアンハ
イドライドとの反応割合は反応成分の種類や所望のフン
素化率等に応じて適宜選定すればよく、特に限定的では
ない。The above base material phenol fiber and the barfluoroalkyl chloride represented by the general formula (■') or the general formula (I
The reaction ratio with the perfluoroalkyl anhydride represented by II'' may be appropriately selected depending on the type of reaction components, the desired fluorination rate, etc., and is not particularly limited.
塩基性触媒としては、前記のトリメチルアミン等を適宜
使用すればよく、その使用量も特に限定的ではないが、
通常は反応当量程度使用する。As the basic catalyst, the above-mentioned trimethylamine etc. may be used as appropriate, and the amount used is not particularly limited, but
Usually, about the reaction equivalent amount is used.
上記の反応は通常は有機溶媒中で行なう。有機溶媒とし
ては、前記のアセトニトリル等を適宜使用すればよいが
、膨潤性や溶解性の小さな基材フェノール繊維を使用す
る場合には、ジメチルホルムアミドやジメチルスルホキ
サイド等の極性溶媒を選択する。The above reaction is usually carried out in an organic solvent. As the organic solvent, the above-mentioned acetonitrile or the like may be used as appropriate, but when using a base phenol fiber with low swelling or solubility, a polar solvent such as dimethylformamide or dimethyl sulfoxide is selected.
反応温度も反応成分の種類によって左右され、特に限定
的ではないが、通常は０〜１００′Ｃであ上記の反応に
よって得られる含フッ素フェノール繊維は、前記のよう
にＩＲスペクトルによって容易に同定することができる
。The reaction temperature also depends on the type of reaction components, and is usually 0 to 100'C, although it is not particularly limited.The fluorine-containing phenol fiber obtained by the above reaction can be easily identified by the IR spectrum as described above. be able to.
本発明による上記の含フッ素フェノール繊維は、モノフ
ィラメント、連続フィラメントヤーン、短繊維、長繊維
、フィブリッド、繊維編織布、抄紙、不織布等として使
用されるほか、ＦＲＰ（繊維強化プラスチック）および
その表面改質材、難燃性カーテンクロス、ブレーキ材等
としても使用することができ、さらにまた、各繊維単独
、他の繊維との混紡、混繊、プラスチック素材、エラス
トマー、塗料コート剤や接着剤等の高分子物質への混合
分散材や積層材等として利用してもよい。The above-mentioned fluorine-containing phenolic fiber according to the present invention can be used as monofilament, continuous filament yarn, short fiber, long fiber, fibrid, fiber knitted fabric, paper making, nonwoven fabric, etc., as well as for FRP (fiber reinforced plastic) and its surface modification. It can be used as material, flame-retardant curtain cloth, brake material, etc. Furthermore, each fiber can be used alone, blended with other fibers, blended fibers, plastic materials, elastomers, paint coating agents, adhesives, etc. It may also be used as a mixed/dispersed material for molecular substances, a laminated material, etc.
実施例
以下、本発明を実施例によって説明するが、性能は次の
方法により評価したものである。EXAMPLES Hereinafter, the present invention will be explained by examples, and the performance was evaluated by the following method.
（１）撥水性： ＪＩＳ Ｌ−１０９２に拠った。(1) Water repellency: Based on JIS L-1092.
（２）摩擦係数： ＡＳＴＭ Ｄ−１８９５に拠っｔこ
。(2) Coefficient of friction: Based on ASTM D-1895.
実施例１
滴下漏斗、温度計、撹拌機および還流冷却器を備えた反
応容器（３Ｑ）内にＤＭＦ ｉｆｆ、フェノールクロス
８９ｇおよびトリエチルアミン１０．０ｇを入れ、撹拌
下でヘキサフルオロプロペンダイマー３０．０９を徐々
に滴下し、反応を約８０’Ｃ！において２時間行なった
。Example 1 DMF if, 89 g of phenol cloth and 10.0 g of triethylamine were placed in a reaction vessel (3Q) equipped with a dropping funnel, thermometer, stirrer and reflux condenser, and 30.09 g of hexafluoropropene dimer was added under stirring. Gradually drop the reaction at about 80'C! The test was carried out for 2 hours.
反応生成物を吸引濾過処理に付した後、アセトンおよび
水を用いて十分洗浄することによって本発明による含フ
ッ素フェノール繊維を９８．０９を得た。After the reaction product was subjected to suction filtration treatment, it was thoroughly washed with acetone and water to obtain 98.09 fluorine-containing phenol fibers according to the present invention.
生成物の確認は、ＩＲスペクトルにおける３５００ｃｆ
’付近の−ＯＨ伸縮振動吸引の減少および１１００１０
０＝１３００’付近のＣ−Ｆ伸縮振動吸引の生成によっ
て行なった（フェノール性−〇Ｈの含フッ素基による置
換率：約２〜ＩＯ％）。Confirmation of product is 3500cf in IR spectrum
-OH stretching vibration suction reduction near ' and 110010
This was carried out by generating C-F stretching vibration attraction near 0=1300' (substitution rate of phenolic -○H with fluorine-containing group: about 2 to IO%).
実施例２
滴下漏斗、温度計、撹拌機および還流冷却器を備えた、
反応容器（３Ｑ）内にＤＭＦＩＱ、！−リエチルアミン
６．０ｇおよびフェノールクロス８４ｇを入れ、撹拌下
でｐ−パーフルオロノネニロキシ塩化ベンゾイル３０．
０９を徐々に滴下し、反応を約８０℃で２時間行なった
。Example 2 Equipped with dropping funnel, thermometer, stirrer and reflux condenser.
DMFIQ in the reaction vessel (3Q)! - Add 6.0 g of ethylamine and 84 g of phenol cloth, and under stirring, 30.0 g of p-perfluorononenyloxybenzoyl chloride.
09 was gradually added dropwise, and the reaction was carried out at about 80° C. for 2 hours.
反応生成物を吸引濾過処理に付した後、アセトンおよび
水を用いて十分に洗浄することによって、本発明による
含フッ素フェノール繊維を９４．０ｇ得た。After the reaction product was subjected to suction filtration treatment, it was sufficiently washed with acetone and water to obtain 94.0 g of fluorine-containing phenol fiber according to the present invention.
生成物の確認は実施例１と同様に行なった（フェノール
性−〇Ｈの含フッ素基による置換率： １〜５％）。The product was confirmed in the same manner as in Example 1 (substitution rate of phenolic -○H with fluorine-containing group: 1 to 5%).
実施例３
滴下漏斗、温度計、撹拌機および還流冷却器を備えた反
応容器（５００ｍｆｆ）内にＤＭＦ２００＋＋＋（１、
トリエチルアミン０．６ｇおよびフェノール繊維ｌｏｇ
を入れ、撹拌下で２．２．３．３−テトラヒドロトリデ
カフルオロノナン酸クロライド２９とＤＭＦ２９との混
合液を徐々に滴下し、反応を８０°Ｃで２時間行なった
。Example 3 DMF 200+++ (1,
Triethylamine 0.6g and phenolic fiber log
A mixture of 2.2.3.3-tetrahydrotridecafluorononanoic acid chloride 29 and DMF 29 was gradually added dropwise under stirring, and the reaction was carried out at 80°C for 2 hours.
反応生成物をアセトンおよび水を用いて十分洗浄するこ
とによって含フッ素フェノール繊維を１１．２ｇ得た。The reaction product was sufficiently washed with acetone and water to obtain 11.2 g of fluorine-containing phenol fiber.
生成物の確認は、ＩＲスペクトルにおける３５００ｃｍ
−’付近の−ＯＨ伸縮振動吸引の減少および１１００〜
１３００ｃｍ−’付近のＣ−Ｆ伸１１振動吸引と１７０
０ｃＣ’付近のカルボニル基の特性吸引の生成によって
行なった（フェノール性−〇Ｈの含フッ素基による置換
率： １〜ｌＯ％）。Confirmation of the product is at 3500 cm in the IR spectrum.
-Reduction of -OH stretching vibration suction around -' and 1100 ~
C-F extension 11 vibration suction near 1300cm-' and 170
This was carried out by generating a characteristic attraction of a carbonyl group near 0cC' (substitution rate of phenolic -○H with a fluorine-containing group: 1 to 10%).
実施例４
含フッ素化合物としてトリフルオロ無水酢酸３０．０９
使用し、かつ、触媒を使用しない以外は実施例２と同様
の手順によって含フッ素フェノール繊維を１０２ｇ得た
（フェノール性−〇Ｈの含フッ素基による置換率： １
〜２０％）。Example 4 Trifluoroacetic anhydride as fluorine-containing compound 30.09
102 g of fluorine-containing phenol fibers were obtained by the same procedure as in Example 2 except that no catalyst was used (substitution rate of phenolic -〇H with fluorine-containing groups: 1
~20%).
得られたフェノールクロスの撥水、撥油性および静摩擦
係数、動摩擦係数を第１表に示した。Table 1 shows the water repellency, oil repellency, static friction coefficient, and dynamic friction coefficient of the obtained phenol cloth.
（以下、余白）
第１表
発明の効果
本発明の方法によりフェノール繊維に優れた撥水性を付
与することができるばかりでなく、静摩擦係数、動摩擦
係数の低下もみられ、フェノール繊維の表面特性も改善
される。(Hereinafter, blank space) Table 1 Effects of the Invention The method of the present invention not only makes it possible to impart excellent water repellency to phenolic fibers, but also reduces the coefficient of static friction and dynamic friction, and improves the surface properties of phenolic fibers. be done.
Claims (1)
とも一部が一般式（ I ）： ▲数式、化学式、表等があります▼（ I ） （式中、ｎは１〜１０の数を示す） で表わされるパーフルオロアルケニロキシ基によって置
換されたことを特徴とする含フッ素フェノール繊維。 ２、パーフルオロアルケニロキシ基が次式（ａ）〜（ｅ
）のいずれかによって表わされるヘキサフルオロプロペ
ンもしくはテトラフルオロエチレンのオリゴマー残基を
有する請求項１記載の含フッ素フエノール繊維： ▲数式、化学式、表等があります▼ （ａ） ▲数式、化学式、表等があります▼ （ｂ） ▲数式、化学式、表等があります▼ （ｃ） ▲数式、化学式、表等があります▼ （ｄ） ▲数式、化学式、表等があります▼ （ｅ） ３、基材フェノール繊維および一般式（ I ′）： ▲数式、化学式、表等があります▼（ I ′） （式中、ｎは１〜１０の数を示す） で表わされるパーフルオロアルケンを塩基性触媒の存在
下で反応させることを特徴とする請求項１もしくは２に
記載された含フッ素フェノール繊維の製造方法。 ４、パーフルオロアルケンが次式（ａ′）〜（ｅ′）の
いずれかによって表わされるヘキサフルオロプロペンも
しくはテトラフルオロエチレンのオリゴマーである請求
項３記載の含フッ素フェノール繊維の製造方法： ▲数式、化学式、表等があります▼ （ａ′） ▲数式、化学式、表等があります▼ （ｂ′） ▲数式、化学式、表等があります▼ （ｃ′） ▲数式、化学式、表等があります▼ （ｄ′） ▲数式、化学式、表等があります▼ （ｅ′） ５、基材フェノール繊維のフェノール性−ＯＨの少なく
とも一部が一般式（II）： ▲数式、化学式、表等があります▼（II） （式中、ｎは１〜１０の数を示す） で表わされる含フッ素エステル置換基によって置換され
たことを特徴とする含フッ素フェノール繊維。 ６、含フッ素エステル置換基が次式（ａ）〜（ｅ）のい
ずれかによって表わされるヘキサフルオロプロペンもし
くはテトラフルオロエチレンのオリゴマー残基を有する
請求項５記載の含フッ素フエノール繊維： ▲数式、化学式、表等があります▼ （ａ） ▲数式、化学式、表等があります▼ （ｂ） ▲数式、化学式、表等があります▼ （ｃ） ▲数式、化学式、表等があります▼ （ｄ） ▲数式、化学式、表等があります▼ （ｅ） ７、基材フェノール繊維および一般式（II′）：▲数式
、化学式、表等があります▼（II） （式中、ｎは１〜１０の数を示す） で表わされるｐ−パーフルオロアルケニロキシ塩化ベン
ゾイルを塩基性触媒の存在下で反応させることを特徴と
する、請求項５または６に記載された含フッ素フェノー
ル繊維の製造方法。 ８、ｐ−パーフルオロアルケニロキシ基が次式（ａ）〜
（ｅ）のいずれかによって表わされるヘキサフルオロプ
ロペンもしくはテトラフルオロエチレンのオリゴマー残
基を有する請求項７記載の製造方法： ▲数式、化学式、表等があります▼ （ａ） ▲数式、化学式、表等があります▼ （ｂ） ▲数式、化学式、表等があります▼ （ｃ） ▲数式、化学式、表等があります▼ （ｄ） ▲数式、化学式、表等があります▼ （ｅ） ９、基材フェノール繊維のフェノール性−ＯＨの少なく
とも一部が一般式（III）： ▲数式、化学式、表等があります▼（III） （式中、ｍは０、１または２の数を示し、ｎ′は１〜８
の数を示す） で表わされる含フッ素エステル置換基によって置換され
たことを特徴とする含フッ素フェノール繊維。 １０、基材フェノール繊維および一般式（III′）：Ｃ
＿ｎ＿′Ｆ＿２＿ｎ＿′＿＋＿１（ＣＨ＿２）＿ｍＣＯ
Ｃｌ（III′）（式中、ｍは０、１または２の数を示し
、ｎ′は１〜８の数を示す） で表わされるパーフルオロアルキリルクロライドを塩基
性触媒の存在下で反応させることを特徴とする、請求項
９に記載された含フッ素フェノール繊維の製造方法。 １１、基材フェノール繊維および一般式（III″）：▲
数式、化学式、表等があります▼（III″） （式中、ｍは０、１または２の数を示し、ｎ′は１〜８
の数を示す） で表わされるパーフルオロアルキリックアンハイドライ
ドを反応させることを特徴とする、請求項１０に記載さ
れた含フッ素フェノール繊維の製造方法。[Claims] 1. At least a part of the phenolic -OH of the base phenolic fiber has the general formula (I): ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (wherein, n is 1 to 10 A fluorine-containing phenolic fiber characterized in that it is substituted with a perfluoroalkenyloxy group represented by (indicating the number of ). 2. The perfluoroalkenyloxy group has the following formulas (a) to (e
) The fluorine-containing phenolic fiber according to claim 1, which has an oligomer residue of hexafluoropropene or tetrafluoroethylene represented by any of the following: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (a) ▲Mathematical formulas, chemical formulas, tables, etc. There are ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (e) 3. Base material phenol Fibers and general formula (I'): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I') (In the formula, n represents a number from 1 to 10) Perfluoroalkene represented by the following is prepared in the presence of a basic catalyst. The method for producing a fluorine-containing phenolic fiber according to claim 1 or 2, characterized in that the reaction is carried out in the following manner. 4. The method for producing a fluorine-containing phenolic fiber according to claim 3, wherein the perfluoroalkene is an oligomer of hexafluoropropene or tetrafluoroethylene represented by any one of the following formulas (a') to (e'): ▲ Formula, There are chemical formulas, tables, etc. ▼ (a') ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b') ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c') ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( d') ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (e') 5. At least a part of the phenolic -OH of the base phenolic fiber is the general formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ( II) A fluorine-containing phenol fiber substituted with a fluorine-containing ester substituent represented by (wherein n represents a number from 1 to 10). 6. The fluorine-containing phenolic fiber according to claim 5, wherein the fluorine-containing ester substituent has an oligomer residue of hexafluoropropene or tetrafluoroethylene represented by any of the following formulas (a) to (e): ▲Mathematical formula, chemical formula , tables, etc. ▼ (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d) ▲ Mathematical formulas , chemical formulas, tables, etc. ▼ (e) 7. Base material phenolic fiber and general formula (II'): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, n is a number from 1 to 10. 7. The method for producing a fluorine-containing phenol fiber according to claim 5 or 6, characterized in that p-perfluoroalkenyloxybenzoyl chloride represented by the following formula is reacted in the presence of a basic catalyst. 8, p-perfluoroalkenyloxy group has the following formula (a) ~
The manufacturing method according to claim 7, which has an oligomer residue of hexafluoropropene or tetrafluoroethylene represented by any of (e): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (a) ▲Mathematical formulas, chemical formulas, tables, etc. There are ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (e) 9. Base material phenol At least a part of the phenolic -OH of the fiber has the general formula (III): ▲Mathematical formula, chemical formula, table, etc. ▼(III) (In the formula, m represents the number 0, 1 or 2, and n' is 1 ~8
A fluorine-containing phenolic fiber characterized by being substituted with a fluorine-containing ester substituent represented by 10, base material phenolic fiber and general formula (III'): C
_n_′F_2_n_′_+_1(CH_2)_mCO
Reacting perfluoroalkyl chloride represented by Cl(III') (in the formula, m represents a number of 0, 1 or 2, and n' represents a number from 1 to 8) in the presence of a basic catalyst. The method for producing a fluorine-containing phenolic fiber according to claim 9. 11. Base material phenolic fiber and general formula (III″): ▲
There are mathematical formulas, chemical formulas, tables, etc.▼(III'') (In the formula, m represents the number 0, 1 or 2, and n' is 1 to 8.
11. The method for producing a fluorine-containing phenol fiber according to claim 10, which comprises reacting a perfluoroalkyl anhydride represented by the following formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13816188A JPH01306674A (en) | 1988-06-03 | 1988-06-03 | Fluorine-containing phenolic fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13816188A JPH01306674A (en) | 1988-06-03 | 1988-06-03 | Fluorine-containing phenolic fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01306674A true JPH01306674A (en) | 1989-12-11 |
Family
ID=15215448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13816188A Pending JPH01306674A (en) | 1988-06-03 | 1988-06-03 | Fluorine-containing phenolic fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01306674A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001052536A (en) * | 1999-06-01 | 2001-02-23 | Showa Electric Wire & Cable Co Ltd | Middle and tip drawing low-friction sheath cable |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4971300A (en) * | 1972-11-17 | 1974-07-10 | ||
| JPS5846176A (en) * | 1981-09-10 | 1983-03-17 | 帝人株式会社 | Water and oil repellent process of polyamide synthetic fiber |
-
1988
- 1988-06-03 JP JP13816188A patent/JPH01306674A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4971300A (en) * | 1972-11-17 | 1974-07-10 | ||
| JPS5846176A (en) * | 1981-09-10 | 1983-03-17 | 帝人株式会社 | Water and oil repellent process of polyamide synthetic fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001052536A (en) * | 1999-06-01 | 2001-02-23 | Showa Electric Wire & Cable Co Ltd | Middle and tip drawing low-friction sheath cable |
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