JPH0220519A - Fluorinated polyether polyester - Google Patents
Fluorinated polyether polyesterInfo
- Publication number
- JPH0220519A JPH0220519A JP16938088A JP16938088A JPH0220519A JP H0220519 A JPH0220519 A JP H0220519A JP 16938088 A JP16938088 A JP 16938088A JP 16938088 A JP16938088 A JP 16938088A JP H0220519 A JPH0220519 A JP H0220519A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- polyether polyester
- general formula
- isophthalic acid
- 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
- 229920000728 polyester Polymers 0.000 title claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 13
- 229920000570 polyether Polymers 0.000 title claims abstract description 13
- -1 perfluorohexenyl Chemical group 0.000 claims abstract description 13
- 150000002009 diols Chemical class 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 3
- 239000003054 catalyst Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 3
- MMAAUSFMRQBXMO-UHFFFAOYSA-N 5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=CC(C(O)=O)=C1 MMAAUSFMRQBXMO-UHFFFAOYSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- RRPVUVFTFFPAND-UHFFFAOYSA-N 5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoronon-1-enoxy)benzene-1,3-dicarbonyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 RRPVUVFTFFPAND-UHFFFAOYSA-N 0.000 description 3
- ULSMOZVJXVYNDX-UHFFFAOYSA-N 5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoronon-1-enoxy)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=CC(C(O)=O)=C1 ULSMOZVJXVYNDX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 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
- YWXDVUMIAUCRQJ-UHFFFAOYSA-N 5-(1,2,3,3,4,4,5,5,6,6,6-undecafluorohex-1-enoxy)benzene-1,3-dicarbonyl chloride Chemical compound FC(=C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)F)OC=1C=C(C=C(C(=O)Cl)C1)C(=O)Cl YWXDVUMIAUCRQJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は、優れた耐久性、耐熱性、弾性および密着性
等の特性だけでなく、撥水撥油性や低摩擦耐摩耗性等の
特性を有する含フッ素ポリエーテ（ＪＲＩ
ルボリエステルに関する。[Detailed Description of the Invention] Industrial Application Field This invention has not only properties such as excellent durability, heat resistance, elasticity, and adhesion, but also properties such as water and oil repellency and low friction and wear resistance. Fluorine-containing polyether (related to JRI Ruboliester).
従来の技術
ポリエーテルポリエステルは耐久性、耐熱性、弾性およ
び密着性等の点で優れているので、従来から、例えば熱
可塑性ポリエステル系弾性樹脂、ポリエステル樹脂の接
着剤、帯電防止剤、コーティング剤等として汎用されて
いるが、撥水撥油性および潤滑性や摺動性等の特性が不
十分であるか、または欠けているために、その改良が要
請されている。Conventional Technology Polyether Polyester is excellent in terms of durability, heat resistance, elasticity, and adhesion, so it has traditionally been used as a thermoplastic polyester elastic resin, polyester resin adhesive, antistatic agent, coating agent, etc. However, since properties such as water and oil repellency, lubricity, and sliding properties are insufficient or lacking, improvements are required.
発明が解決しようとする課題
この発明は、このような要請に応え、優れた耐久性や密
着性等の固有の特性と共に、撥水撥油性や低摩擦耐摩耗
性等の特性を兼有するポリエーテルポリエステルを提供
するためになされたものである。Problems to be Solved by the Invention The present invention, in response to these demands, has developed a polyether that has unique properties such as excellent durability and adhesion, as well as properties such as water and oil repellency and low friction and abrasion resistance. This was done to provide polyester.
課題を解決するための手段
即ち、本発明は一般式［Ｉ］ ：
（式中、Ｒｆはペルフルオロへキセニル基Ｃａ Ｆ Ｉ
ｌモジくはペルフルオロノネニル基ＣｓＦ＋ｙを示し、
Ｒは水素原子もしくはメチル基を示し、ｎは２〜１４０
の数を示し、ｍは２以上の数を示す。）で表される含フ
ツ素ポリエーテルポリエステルおよびその製造方法に関
する。Means for solving the problem, that is, the present invention has the general formula [I]: (wherein, Rf is a perfluorohexenyl group Ca F I
1 represents a perfluorononenyl group CsF+y,
R represents a hydrogen atom or a methyl group, and n is 2 to 140
, and m represents a number of 2 or more. ) and a method for producing the same.
一般式［１］において、Ｒｆはペルフルオロへキセニル
基Ｃｓ Ｆ ｌ＋ マたはペルフルオロノネニル基Ｃ９
Ｆ１７は、例えばヘキサフルオロプロペンＣｓ Ｆ ｓ
のダイマーまたはトリマーから誘導される。In the general formula [1], Rf is a perfluorohexenyl group Cs F l+ or a perfluorononenyl group C9
F17 is, for example, hexafluoropropene Cs F s
derived from dimers or trimers of
このようなペルフルオロアルケニル基としては次の構造
式で表されるものが例示される：（ＣｓＦ＋＋：ダイマ
ー）
（Ｃ，Ｆ 、、： トリマー）
（Ｃ＊Ｆ＋ア：トリマー）
なお、この種の２価残基は分子量の異なる２種以上の残
基から構成されていてもよい。Examples of such perfluoroalkenyl groups include those represented by the following structural formula: (CsF++: dimer) (C,F , ,: trimer) (C*F+a: trimer) In addition, this type of 2 The valent residue may be composed of two or more types of residues having different molecular weights.
さらに、式［Ｉ］において、ｍは２以上の数、好ましく
は５〜１５０である。Furthermore, in formula [I], m is a number of 2 or more, preferably 5 to 150.
航記一般式［１１で表される含フツ素ポリエーテルポリ
エステルの製造方法は特に限定的ではないが、−威武［
■］ ：
また、式［Ｉ］において、Ｒは水素原子またはメチル基
を示し、ｎは２〜１４０の数を示す。即ち、式［Ｉ］中
の−（−ＣＨ２ＣＨ（Ｒ）０９７−はジエチレングリコ
ールもしくはポリエチレングリコールおよび／またはジ
プロピレングリコールもしくはポリプロピレングリコー
ルから誘導される２価残基、好ましくは平均分子量が３
００〜４０００のポリエチレングリコールおよび／また
はポリプロピレングリコールから誘導される２価残基を
示す。Although the method for producing the fluorine-containing polyether polyester represented by the general formula [11] is not particularly limited, -Yiwu [
[1]: In formula [I], R represents a hydrogen atom or a methyl group, and n represents a number from 2 to 140. That is, -(-CH2CH(R)097- in formula [I] is a divalent residue derived from diethylene glycol or polyethylene glycol and/or dipropylene glycol or polypropylene glycol, preferably an average molecular weight of 3
00 to 4000 indicating divalent residues derived from polyethylene glycol and/or polypropylene glycol.
（式中、Ｒｆはペルフルオロへキセニル基ｃ、Ｆ、。(In the formula, Rf is a perfluorohexenyl group c, F.
もしくはペルフルオロノネニル基Ｃ１Ｆ１７を示し、Ｘ
はヒドロキシル基、塩素原子、メトキシ基もしくはエト
キシ基を示す。）
で表される５−（ペルフルオロアルケニル）オキシイソ
フタル酸もしくはその誘導体および一般式［ｍ］：
（式中、Ｒは水素原子もしくはメチル基を示し、ｎは２
〜１４０の数を示す。）
で表されるジオールを反応させる製法が好適である。Or represents a perfluorononenyl group C1F17, X
represents a hydroxyl group, a chlorine atom, a methoxy group or an ethoxy group. ) 5-(perfluoroalkenyl)oxyisophthalic acid or its derivatives and general formula [m]: (wherein, R represents a hydrogen atom or a methyl group, and n represents 2
Indicates a number of ~140. ) A manufacturing method in which a diol represented by the following formula is reacted is suitable.
−ｆｉ式［１１］で表される５−（ペルフルオロアルケ
ニル）オキシイソフタル酸もしくはその誘導体は、例え
ば５−ヒドロキシイソフタル酸もしくはその誘導体にヘ
キサフルオロプロペンＣ，Ｆ、のダイマーまたはトリマ
ーを塩基性触媒の存在下で反応させることによって調製
することができる。-fi 5-(Perfluoroalkenyl)oxyisophthalic acid or its derivative represented by the formula [11] is obtained by adding a dimer or trimer of hexafluoropropene C, F to 5-hydroxyisophthalic acid or its derivative using a basic catalyst. It can be prepared by reacting in the presence of
式［■］においてＸがヒドロキシル基の場合、即ち、５
−（ペルフルオロへキセニルオキシ）イソフタル酸もし
くは５−（ペルフルオロノネニルオキシ）イソフタル酸
を式［１１［］で表されるジオールと反応させる場合に
は、通常、等モル量の同成分を酢酸亜鉛、酢酸カルシウ
ムまたは三酸化アンチモン等の触媒の存在下で反応させ
る。In the formula [■], when X is a hydroxyl group, that is, 5
When reacting -(perfluorohexenyloxy)isophthalic acid or 5-(perfluorononenyloxy)isophthalic acid with a diol represented by formula [11[], equimolar amounts of the same components are usually mixed with zinc acetate, acetic acid, The reaction is carried out in the presence of a catalyst such as calcium or antimony trioxide.
触媒の使用量は０．００５〜０．１重量％、好ましくは
０．Ｏ１〜０．０５重量％である。The amount of catalyst used is 0.005 to 0.1% by weight, preferably 0.005% to 0.1% by weight. O1 to 0.05% by weight.
この反応は、不活性ガス（例えば、Ｎ、ｆＩス、ｃｏ、
ガス等）の雰囲気での減圧下、１００〜３５０℃、好ま
しくは１５０〜３２０°Ｃで約５〜１５時間行う。This reaction is performed using an inert gas (e.g., N, fl, co,
The reaction is carried out at 100 to 350°C, preferably 150 to 320°C, for about 5 to 15 hours under reduced pressure in an atmosphere of (gas, etc.).
また、式［Ｉ［］においてＸが塩素原子の場合、即ち、
５−（ペルフルオロへキセニルオキシ）イソフタル酸塩
化物もしくは５−（ペルフルオロノネニルオキシ）イソ
フタル酸塩化物を式［Ｉ［［］で表されるジオールと反
応させる場合には、通常、等モル量の同成分を０〜３０
０°Ｃ１好ましくは０〜２００℃で常圧もしくは減圧下
において約１〜２５時間おこなう。この場合、所望によ
り、四塩化炭素やベンゼン等の不活性溶媒を反応溶媒と
して使用してもよく、また、ピリジンやトリエチルアミ
ン等の塩基性触媒を適宜使用してもよい。Moreover, when X is a chlorine atom in formula [I[], that is,
When 5-(perfluorohexenyloxy)isophthalic acid chloride or 5-(perfluorononenyloxy)isophthalic acid chloride is reacted with a diol represented by the formula [I[[], an equimolar amount of the same Ingredients 0-30
The reaction is carried out at 0° C., preferably from 0 to 200° C., under normal pressure or reduced pressure for about 1 to 25 hours. In this case, if desired, an inert solvent such as carbon tetrachloride or benzene may be used as a reaction solvent, and a basic catalyst such as pyridine or triethylamine may be used as appropriate.
さらにまた、式［１１１においてＸがメトキシ基もしく
はエトキシ基の場合、即ち、５−（ペルフルオロへキセ
ニルオキシ）イソフタル酸エステルもしくは５−（ペル
フルオロノネニルオキシ）イソフタル酸を式［１１１］
で表されるジオールと反応させるエステル交換反応の場
合には、等モル量の同成分を酢酸亜鉛、酢酸カルシウム
、酸酸化アンチモンまたは酸化チタン等の触媒の存在下
、不活性ガス（例えば、Ｎ２ガス、ＣＯ□ガス等）の雰
囲気での減圧下において、１００〜３５０℃、好ましく
は１５０〜３２０℃で約５〜１５時間行応をおこなう。Furthermore, when X in formula [111] is a methoxy group or an ethoxy group, that is, 5-(perfluorohexenyloxy)isophthalic acid ester or 5-(perfluorononenyloxy)isophthalic acid is represented by formula [111]
In the case of a transesterification reaction in which an equimolar amount of the same component is reacted with a diol represented by , CO□ gas, etc.) under reduced pressure in an atmosphere of 100 to 350°C, preferably 150 to 320°C, for about 5 to 15 hours.
触媒の使用量は、通常、０．００５〜０．１重量％、好
ましくは０．０１〜０．０５重量％である。The amount of catalyst used is usually 0.005 to 0.1% by weight, preferably 0.01 to 0.05% by weight.
上記の成分において、ジオール成分としては分子量の異
なった２種以上のポリエチレングリコールおよび／また
はポリプロピレングリコールを適宜併用してもよい。In the above components, two or more types of polyethylene glycol and/or polypropylene glycol having different molecular weights may be used in combination as appropriate as the diol component.
以下、本発明を実施例によって説明する。Hereinafter, the present invention will be explained by examples.
実施例１
撹拌機、温度計およびＮ２ガス導入管を備えた反応容器
内に５−（ペルフルオロノネニルオキシ）イソフタル酸
塩化物６４．９９およびジエチレングリコール１０．６
９を入れ、Ｎｔガス気流中、常圧下、１００〜１２０℃
で２時間加熱後、減圧下（２０〜３０ｍｍＨｇ）、
１５０〜ｌ ６０°０で２時間加熱し、さらに２ ｍｍ
Ｈｇで１５０〜１７０°Ｃの条件下で３時間加熱反応を
おこなうことによって含フツ素ポリエーテルポリエステ
ルＩａを７４．８ｇ得た。Example 1 64.99 g of 5-(perfluorononenyloxy)isophthalic acid chloride and 10.6 g of diethylene glycol in a reaction vessel equipped with a stirrer, thermometer and N2 gas inlet tube
9 and heated to 100-120°C under normal pressure in Nt gas flow.
After heating for 2 hours, under reduced pressure (20-30 mmHg),
150~l Heat at 60°0 for 2 hours, then 2 mm
74.8 g of fluorine-containing polyether polyester Ia was obtained by carrying out a heating reaction with Hg at 150 to 170°C for 3 hours.
ポリマー１ａの物性を表−１に示す。Table 1 shows the physical properties of Polymer 1a.
実施例２
撹拌機、温度計および冷却管を備えた反応容器内にポリ
エチレングリコール（平均分子量：４００）２０ｇ、ピ
リジン１６９および四塩化炭素５０ｍＱを入れた。一方
、５−（ペルフルオロノネニルオキシ）インフタル酸塩
化物３２．４ｇを四塩化炭素１５０ｍＱに溶解し、該溶
液を上記混合物へ滴下した。この場合、反応系は氷−水
浴を用いて冷却しＩこ。Example 2 20 g of polyethylene glycol (average molecular weight: 400), 169 ml of pyridine, and 50 mQ of carbon tetrachloride were placed in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube. On the other hand, 32.4 g of 5-(perfluorononenyloxy)inphthalic acid chloride was dissolved in 150 mQ of carbon tetrachloride, and the solution was added dropwise to the above mixture. In this case, the reaction system is cooled using an ice-water bath.
滴下終了後、常温において撹拌を１５時間おこない、さ
らに５０〜６０℃において５時間反応をおこなった。After completion of the dropwise addition, stirring was carried out at room temperature for 15 hours, and the reaction was further carried out at 50 to 60°C for 5 hours.
反応混合物を濾過処理に付し、濾液を減圧下での蒸発処
理に付して溶媒を除去することによって含フツ素ポリエ
ーテルポリエステルｒｂを４５．２９得た。The reaction mixture was filtered, and the filtrate was evaporated under reduced pressure to remove the solvent, yielding 45.29 fluorine-containing polyether polyester rb.
ポリマー１ｂの物性を表−Ｉに示す。The physical properties of Polymer 1b are shown in Table I.
実施例３
撹拌機、温度計およびＮ２ガス導入管を備えた反応容器
内に５−（ペルフルオロノネニルオキシ）イソフタル酸
１８．４ｇ ポリエチレングリコール（平均分子量：２
０００）６０ｇ、酢酸亜鉛０．１ｇおよびｍ−キシレン
２０ｍ（２を入れ、Ｎ２ガス気流中、常圧下、１４０〜
１５０℃で２０時間加熱撹拌をおこない、次いで、三酸
化アンチモン０．１９を加え、２０〜３０ｍｍＨｇで１
５０〜１７０°Ｃの条件下で１０時間加熱撹拌をおこな
った後、さらに２〜３ ｍｍＨｇで１７０〜１９０℃の
条件下で５時間加熱撹拌を行うことによって含フツ素ポ
リエーテルポリエステルＩｃを７７．３９得た。Example 3 18.4 g of 5-(perfluorononenyloxy)isophthalic acid polyethylene glycol (average molecular weight: 2
000) 60g, zinc acetate 0.1g and m-xylene 20m (2) in a N2 gas stream under normal pressure, 140~
Heat and stir at 150°C for 20 hours, then add 0.19% of antimony trioxide and stir at 20-30mmHg.
After heating and stirring at 50 to 170°C for 10 hours, the fluorine-containing polyether polyester Ic was heated and stirred for 5 hours at 2 to 3 mmHg and 170 to 190°C. I got 39.
ポリマーＩｃの物性を表−１に示す。Table 1 shows the physical properties of Polymer Ic.
実施例４
実施例１の場合ど同様の反応操作に従い、５−（ペルフ
ルオロノネニルオキシ）イソフタル酸塩化物とポリエチ
レングリコール（平均分子量：６０００）を出発原料と
して含フツ素ポリエーテルポリエステルＴｄを得た。Example 4 Following the same reaction procedure as in Example 1, fluorine-containing polyether polyester Td was obtained using 5-(perfluorononenyloxy)isophthalic acid chloride and polyethylene glycol (average molecular weight: 6000) as starting materials. .
ポリマー１ｄの物性を表−１に示す。Table 1 shows the physical properties of Polymer 1d.
表−１
発明の効果
本発明による含フツ素ポリエーテルポリエステルは優れ
た撥水撥油性、低摩擦耐摩耗性、耐久性、耐熱性、弾性
および密着性等の特性を有するので、高性能のポリエス
テル系のエラストマー、潤滑剤、離型剤、各種基材（フ
ィルム、繊維、紙、プラスチックス、ゴム等）の改質加
工仕上げ剤、帯電防止剤、ポリマー表面改質剤（例えば
、フィルム表面への潤滑性、撥水防汚性、防霧防曇性お
よび帯電防止性等の付与剤、磁気記録体表面への摺動性
付与剤等）等として有用である。Table 1 Effects of the Invention The fluorine-containing polyether polyester of the present invention has properties such as excellent water and oil repellency, low friction and abrasion resistance, durability, heat resistance, elasticity, and adhesion, making it a high-performance polyester. elastomers, lubricants, mold release agents, modification finishing agents for various base materials (films, fibers, paper, plastics, rubber, etc.), antistatic agents, polymer surface modifiers (e.g. It is useful as an agent for imparting lubricity, water-repellent and stain-proofing properties, fog-proofing and anti-fogging properties, antistatic properties, etc., an agent for imparting sliding properties to the surface of a magnetic recording medium, etc.
Claims (1)
＿１もしくはペルフルオロノネニル基Ｃ＿９Ｆ＿１＿７
を示し、Ｒは水素原子もしくはメチル基を示し、ｎは２
〜１４０の数を示し、ｍは２以上の数を示す。）で表さ
れる含フッ素ポリエーテルポリエステル。 ２、一般式［II］： ▲数式、化学式、表等があります▼［II］ （式中、Ｒｆはペルフルオロヘキセニル基Ｃ＿６Ｆ＿１
＿１もしくはペルフルオロノネニル基Ｃ＿９Ｆ＿１＿７
を示し、Ｘはヒドロキシル基、塩素原子、メトキシ基も
しくはエトキシ基を示す。） で表される５−（ペルフルオロアルケニル）オキシイソ
フタル酸もしくはその誘導体および 一般式［III］： ▲数式、化学式、表等があります▼［III］ （式中、Ｒは水素原子もしくはメチル基を示し、ｎは２
〜１４０の数を示す。） で表されるジオールを反応させることを特徴とする、一
般式［ I ］で表される含フッ素ポリエーテルポリエス
テルの製造方法。[Claims] 1. General formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, Rf is a perfluorohexenyl group C_6F_1
_1 or perfluorononenyl group C_9F_1_7
, R represents a hydrogen atom or a methyl group, and n represents 2
~140 is shown, and m shows a number of 2 or more. ) Fluorine-containing polyether polyester. 2. General formula [II]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (In the formula, Rf is a perfluorohexenyl group C_6F_1
_1 or perfluorononenyl group C_9F_1_7
and X represents a hydroxyl group, a chlorine atom, a methoxy group or an ethoxy group. ) 5-(Perfluoroalkenyl)oxyisophthalic acid or its derivatives and general formula [III]: ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [III] (In the formula, R represents a hydrogen atom or a methyl group. , n is 2
Indicates a number of ~140. ) A method for producing a fluorine-containing polyether polyester represented by the general formula [I], which comprises reacting a diol represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16938088A JP2592915B2 (en) | 1988-07-07 | 1988-07-07 | Fluorine-containing polyether polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16938088A JP2592915B2 (en) | 1988-07-07 | 1988-07-07 | Fluorine-containing polyether polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0220519A true JPH0220519A (en) | 1990-01-24 |
| JP2592915B2 JP2592915B2 (en) | 1997-03-19 |
Family
ID=15885527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16938088A Expired - Fee Related JP2592915B2 (en) | 1988-07-07 | 1988-07-07 | Fluorine-containing polyether polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2592915B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239509A (en) * | 2016-12-23 | 2018-07-03 | 上海理日化工新材料有限公司 | Polyether ester hot melt adhesive with good heat resistance and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103282569B (en) * | 2010-12-28 | 2015-11-25 | 纳幕尔杜邦公司 | The fabric obtained by fluorinated polyester blend yarn |
-
1988
- 1988-07-07 JP JP16938088A patent/JP2592915B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239509A (en) * | 2016-12-23 | 2018-07-03 | 上海理日化工新材料有限公司 | Polyether ester hot melt adhesive with good heat resistance and preparation method thereof |
| CN108239509B (en) * | 2016-12-23 | 2021-01-01 | 上海理日化工新材料有限公司 | Polyether ester hot melt adhesive with good heat resistance and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2592915B2 (en) | 1997-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2972598A (en) | Organosilicon salts and process for producing the same | |
| US5654450A (en) | Monomers mono-substituted fluorinated oxetane | |
| JP4354208B2 (en) | Additives for perfluoropolyether oil | |
| CN102574313B (en) | Mold release agent | |
| JP2016222859A (en) | Fluoropolyether group-containing polymer-modified silane | |
| JPH07103231B2 (en) | A process for producing aromatic polyesters with excellent stability by adding phosphite during production | |
| EP0250504B1 (en) | Fluorinated polyesters | |
| JPH0220519A (en) | Fluorinated polyether polyester | |
| US2789965A (en) | Polycarbonates from 4, 4'-bis-(beta-hydroxyethoxy)-biphenyl-bis | |
| US2741606A (en) | Fluosocyaurates | |
| ATE159959T1 (en) | METHOD FOR PRODUCING POLYESTER AND COMPOSITION THEREOF | |
| JPS61122293A (en) | Platinum complex and manufacture | |
| JPS62232439A (en) | Production of ester-containing organosilicone compound | |
| EP0173752B1 (en) | Process for producing melting-anisotropic, copolymerized polyester | |
| JPH0138788B2 (en) | ||
| US5936111A (en) | Fluorinated amide compounds with a phenyl-Si-unsaturated group | |
| JPH0273848A (en) | Liquid crystal compound, its manufacture, and its use as modifier for polycarbonate, polyester carbonate, and polyester | |
| JPH0395259A (en) | Resin composition | |
| JPS5959764A (en) | Heat-sensitive adhesive | |
| JP2699538B2 (en) | Method for producing fluorine-containing urethane compound | |
| US3254061A (en) | Preparation of linear poly | |
| US4115367A (en) | Perfluoroalkylene ether bibenzoxazole polymers | |
| JPS627715A (en) | Production of polyester, polyamide and polyketone | |
| JPH01129017A (en) | Production of polyurethane having crystallinity and diisocyanate suitable therefore | |
| US3206426A (en) | Hydroxy aryl esters of organic chloroformates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |