JPH02255720A - Fluorine-containing brominated polyarylate - Google Patents
Fluorine-containing brominated polyarylateInfo
- Publication number
- JPH02255720A JPH02255720A JP7943889A JP7943889A JPH02255720A JP H02255720 A JPH02255720 A JP H02255720A JP 7943889 A JP7943889 A JP 7943889A JP 7943889 A JP7943889 A JP 7943889A JP H02255720 A JPH02255720 A JP H02255720A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- fluorine
- tables
- formula
- represented
- 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
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000011737 fluorine Substances 0.000 title claims abstract description 19
- 229920001230 polyarylate Polymers 0.000 title abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 4
- BVWILPZRADBDPQ-UHFFFAOYSA-N carbonochloridoyl carbonochloridate Chemical compound ClC(=O)OC(Cl)=O BVWILPZRADBDPQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical group C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 polyoxyethylene nonylphenyl ether Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LQQIOXIIZZGWOR-UHFFFAOYSA-N C1(=C(C(=C(C(=C1F)F)F)C(=O)Cl)OC(=C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)C(=O)Cl Chemical compound C1(=C(C(=C(C(=C1F)F)F)C(=O)Cl)OC(=C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)C(=O)Cl LQQIOXIIZZGWOR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- VPCOEYXZVJRDCX-UHFFFAOYSA-N imino-methyl-oxidophosphanium Chemical compound C[P+](=N)[O-] VPCOEYXZVJRDCX-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
この発明は、新規な多機能性含フツ素ポリ臭化アリレー
トおよびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel multifunctional fluorinated polybrominated arylate and a method for producing the same.
従来の技術
従来から種々の機能性ポリマーが開発されているが、な
かでも、優れた撥水撥油性、耐薬品性および防汚性等の
特性を有する含フツ素ポリマーお、）：び漫れた耐熱性
、難燃性および耐候性等の特性を有するボリアリレート
は種々の分野において繊維等の素材、フィルム、グレー
］・もしくはパイプ等の成形材もしくは成形品等として
汎用されている。Conventional technology Various functional polymers have been developed in the past, and among them, fluorine-containing polymers with excellent properties such as water and oil repellency, chemical resistance, and stain resistance. Polyarylates, which have properties such as heat resistance, flame retardance, and weather resistance, are widely used in various fields as materials such as fibers, films, molding materials and molded products such as pipes.
また、含臭素化合物、例えばテトラブロムビスフェノー
ルＡ、トリス（２，３−ジブロモプロピル）イソシアヌ
レート等は優れた難燃性と特有の反応性を有するので、
エポキシ樹脂やウレタン樹脂等の原料および各種のプラ
スチック製品（例えば、フィルム、プレート、シート等
）の難燃剤として汎用されているだけでなく、反応性の
ある機能性材料としても利用されている。In addition, bromine-containing compounds such as tetrabromobisphenol A and tris(2,3-dibromopropyl)isocyanurate have excellent flame retardancy and unique reactivity.
It is widely used not only as a raw material for epoxy resins and urethane resins and as a flame retardant for various plastic products (e.g., films, plates, sheets, etc.), but also as a reactive functional material.
発明が解決しようとする課題
この発明は、この種の含フツ素ポリマー、ボリアリレー
トおよび含臭素化合物の有する優れた諸特性を兼有する
新規な多機能性含フツ素ポリ臭化アリレートを提供する
ためになされたものである。Problems to be Solved by the Invention The purpose of the present invention is to provide a novel multifunctional fluorinated polybrominated arylate that has all the excellent properties of this type of fluorinated polymer, polyarylate, and brominated compound. This is what was done.
課題を解決するための手段
即ち本発明は、下記の一般式（Ｉ）、（ＩＩ）、（ＩＩ
）および（■）：
（式中、Ｒｆはパーフルオロアルケニル基Ｃ１Ｆｌｌも
しくはＣ，Ｆ、アを示し、ＸはＣ（ＣＨ３）！、Ｃ（Ｃ
Ｆ３）２、ＳＯ２、Ｏ，ＣＨｚ、ＣＯまたは単結合を示
す）
で表わされる構造単位から成る分子量２０００以上の含
フツ素ポリ臭化アリレートおよびその製造方法に関する
。Means for solving the problem, that is, the present invention, is based on the following general formulas (I), (II), (II
) and (■): (wherein, Rf represents a perfluoroalkenyl group C1Fll or C,F, a, and X represents C(CH3)!, C(C
F3) The present invention relates to a fluorine-containing polybrominated arylate having a molecular weight of 2000 or more and consisting of a structural unit represented by F3)2, SO2, O, CHz, CO or a single bond, and a method for producing the same.
式（Ｉ）およびＣＩｌ’ｌ）において、Ｒｆはパーフル
オロアルケニル基Ｃ＊ＦｌｒもしくはＣｓＦ＋ｙを示し
、また、式（Ｉ）〜（ＴＶ）において、ＸはＣ（ＣＨｓ
）ｘ、Ｃ（ＣＦ ３）！、Ｓ０２、Ｏ，ＣＨ２、ＣＯま
たは単結合を示す。In formulas (I) and CIl'l), Rf represents a perfluoroalkenyl group C*Flr or CsF+y, and in formulas (I) to (TV), X represents C(CHs
) x, C (CF 3)! , S02, O, CH2, CO or a single bond.
構造単位（１）は、例えば−最大（Ｖ）：（式中、Ｒｆ
は前記と同意義である）
で表わされるパーフルオロアルケニルオキシジカルボン
酸ジクロリドと一般式（■）：
（Ｖ）は高収率で得られる。The structural unit (1) is, for example, -maximum (V): (in the formula, Rf
has the same meaning as above) and the perfluoroalkenyloxydicarboxylic acid dichloride represented by the general formula (■): (V) can be obtained in high yield.
また、構造単位（１１）は例えば−最大（■）：（式中
、Ｘは前記と同意義である）
で表わされる臭素化ビスフェノール類との縮合反応によ
って誘導される。Further, the structural unit (11) is derived, for example, by a condensation reaction with a brominated bisphenol represented by -maximum (■): (wherein X has the same meaning as above).
式（Ｖ）で表わされるパーフルオロアルケニルオキシイ
ソフタル酸ジクロリドは、例えば特開昭５２−８９６３
０号公報に記載されているｐ−パーフルオロアルケニル
オキシ安息香酸の製造法に準拠して調製することができ
る。即ち、例えば、５−ヒドロキシイソフタル酸および
ヘキサフルオロプロペンの二量体もしくは二量体を過剰
のアミンの存在下で反応させることによって生成するパ
ーフルオロアルケニルオキシイソフタル酸に、例えば塩
化チオニルを反応させることによって化合物で表わされ
る芳香族ジカルボン酸ジクロリド、例えばテレフタル酸
ジクロリドおよび／またはイソフタル酸ジクロリドと上
記−最大（■）で表わされる臭素化ビスフェノール類と
の縮合反応によって誘導される。Perfluoroalkenyloxyisophthalic acid dichloride represented by formula (V) is disclosed in, for example, JP-A-52-8963.
It can be prepared according to the method for producing p-perfluoroalkenyloxybenzoic acid described in Publication No. 0. That is, for example, by reacting thionyl chloride with perfluoroalkenyloxyisophthalic acid, which is produced by reacting a dimer or dimer of 5-hydroxyisophthalic acid and hexafluoropropene in the presence of an excess of amine. It is derived by the condensation reaction of an aromatic dicarboxylic acid dichloride represented by the compound, such as terephthalic acid dichloride and/or isophthalic acid dichloride, and a brominated bisphenol represented by the maximum (■) above.
さらにまた、構造単位（Ｉ［Ｉ）および（ＩＶ）は、例
えば前記の一般式（Ｖ）で表わされるパーフルオロアル
ケニルオキシジカルボン酸ジクロリドまたは一般式（Ｖ
ｌ）で表わされる芳香族ジカルボン酸ジクロリドを一般
式（■）：
（式中、Ｘは前記と同意義である）
で表わされるビスフェノール類と縮合反応させることに
よって誘導される。Furthermore, the structural units (I[I) and (IV) may be, for example, perfluoroalkenyloxydicarboxylic acid dichloride represented by the general formula (V) or the general formula (V
It is derived by condensation reaction of aromatic dicarboxylic acid dichloride represented by 1) with bisphenols represented by general formula (■): (wherein, X has the same meaning as above).
本発明による含７ツ素ポリ臭化アリレートは上記の構造
単位（Ｉ）〜（ＩＶ）が規則的または不規則的に配列し
たポリマー構造を有する。The heptadium-containing polybrominated arylate according to the present invention has a polymer structure in which the above structural units (I) to (IV) are regularly or irregularly arranged.
各構造単位の含有割合は特に限定的ではないが、構造単
位（Ｉ）は少なくとも１重量％、好ましくは５重量％以
上にする。構造単位（Ｉ）が１重量％以下になると、含
フッ素に起因する撥水性や摺動性並びに含臭素に起因す
る優れた難燃性や特有の反応性を有するボリアリレート
が得難くなる本発明による含フツ素ポリ臭化アリレート
の有する優れた緒特性は、構造単位（１）〜（ＩＶ）の
含有量を適宜選定することによって調整することができ
る。Although the content ratio of each structural unit is not particularly limited, the content of structural unit (I) is at least 1% by weight, preferably 5% by weight or more. When the content of the structural unit (I) is 1% by weight or less, it becomes difficult to obtain a polyarylate having water repellency and sliding properties due to the fluorine content, as well as excellent flame retardancy and unique reactivity due to the bromine content. The excellent properties of the fluorine-containing polybrominated arylate can be adjusted by appropriately selecting the content of structural units (1) to (IV).
また、このような含フツ素ポリ臭化アリレートの分子量
は通常２０００以上であり、２０００以下になるとポリ
マーとしての機械的特性、熱的特性等が失われる。Further, the molecular weight of such a fluorine-containing polybrominated arylate is usually 2,000 or more, and when it is less than 2,000, the mechanical properties, thermal properties, etc. as a polymer are lost.
本発明による含フツ素ポリ臭化アリレートの製造方法は
特に限定的ではないが、好適な製法は、−［、（Ｖ）で
表わされるパーフルオロアルケニルオキシジカルボン酸
ジクロリドまたはこれと一般式（Ｖｌ）で表わされる芳
香族ジカルボン酸ジクロリドとの混合物を脱酸剤の存在
下で、−最大（■）で表わされる臭素化ビスフェノール
類および一般式（■）で表わされるビスフェノール類と
反応させる方法である。Although the method for producing the fluorine-containing polybrominated arylate according to the present invention is not particularly limited, a preferred method is to use a perfluoroalkenyloxydicarboxylic acid dichloride represented by -[, (V) or a combination of this and the general formula (Vl). This is a method in which a mixture with an aromatic dicarboxylic acid dichloride represented by is reacted with a brominated bisphenol represented by -maximum (■) and a bisphenol represented by the general formula (■) in the presence of a deoxidizing agent.
臭素化ビスフェノール類（■）およびビスフェノール類
（■）としては次の化合物が例示される：脱酸剤は縮合
反応で生成する塩化水素を中和するＩ；めに使用するも
ので、アルカリ金属もしくはアルカリ土類金属の水酸化
物、第三級アミン等が例示されるが、界面重合法の場合
には水酸化ナトリウムや水酸化カリウム等のアルカリ金
属の水酸化物が好適であり、溶液重合法の場合にはトリ
エチルアミンやピリジン等の第三級アミンが好ましい。The following compounds are exemplified as brominated bisphenols (■) and bisphenols (■): Deoxidizing agents are used to neutralize hydrogen chloride generated in the condensation reaction, and are Examples include alkaline earth metal hydroxides and tertiary amines, but alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are suitable for interfacial polymerization, while solution polymerization In this case, tertiary amines such as triethylamine and pyridine are preferred.
また、−最大（Ｖｌ）で表わされる化合物を混用する場
合、例えばテレフタル酸ジクロリドとイソフタル酸ジク
ロリドを混用する場合、これらの成分の使用割合は特に
限定的ではない。Further, when using a mixture of compounds represented by -maximum (Vl), for example when using a mixture of terephthalic acid dichloride and isophthalic acid dichloride, the proportions of these components to be used are not particularly limited.
上記の反応は界面重合法によっておこなうのが好ましく
、これによって高重合度の含フツ素ポリ臭化アリレート
が得られる。The above reaction is preferably carried out by an interfacial polymerization method, whereby a fluorine-containing polybrominated arylate having a high degree of polymerization can be obtained.
該界面重合法においては、水に不溶性の有機溶媒、例え
ば含ハロゲン溶媒、炭化水素系溶媒、芳香族系溶媒、ケ
トン系溶媒等（特にジクロロメタン、クロロホルム、ｌ
、２−ジクロロエタン等）含塩素溶媒が好ましい）に前
記のパーフルオロアルケニルオキシイソフタル酸ジクロ
リドまたは該パーフルオロアルケニルオキシイソフタル
酸ジクロリドと前記の芳香族ジカルボン酸ジクロリドと
の混合物を溶解させた溶液を前記の脱酸剤の存在下にお
いて化合物（■）および（■）との混合水溶液と接触さ
せ、該両溶液の界面において反応をおこなう。In the interfacial polymerization method, water-insoluble organic solvents such as halogen-containing solvents, hydrocarbon solvents, aromatic solvents, ketone solvents, etc. (particularly dichloromethane, chloroform, l
A solution prepared by dissolving the perfluoroalkenyloxyisophthalic acid dichloride or a mixture of the perfluoroalkenyloxyisophthalic acid dichloride and the aromatic dicarboxylic acid dichloride in It is brought into contact with a mixed aqueous solution of compounds (■) and (■) in the presence of a deoxidizing agent, and a reaction occurs at the interface between the two solutions.
この界面重合法においては、第四級アンモニウム塩や界
面活性剤等の反応系に存在させて重合度をさらに高めて
もよい。In this interfacial polymerization method, a quaternary ammonium salt, a surfactant, or the like may be present in the reaction system to further increase the degree of polymerization.
第四級アンモニウム塩としてはテトラエチルアンモニウ
ムクロリド、テトラエチルアンモニウムプロミド、テト
ラプロピルアンモニウムクロリド、テトラプロピルアン
モニウムプロミド、テトラブチルアンモニウムクロリド
、テトラブチルアンモニウムプロミド等が例示される。Examples of the quaternary ammonium salt include tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium bromide.
また、界面活性剤としては各種の中性界面活性剤が使用
できるが、ポリオキシエチレンノニルフェニルエーテル
、ポリオキシエチレンアルキルエーテル、ポリオキシエ
チレンパーフルオロアルキルエーテル等が好適である。Further, as the surfactant, various neutral surfactants can be used, and polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene perfluoroalkyl ether, etc. are suitable.
上記反応は界面重合法のほかに有機溶媒中での溶液重合
法によっておこなってもよい。有機溶媒は特に限定的で
はなく、前記の七ツマー類を溶解させる活性水素不合溶
媒であれば使用可能であるが、非プロトン性アミド系溶
媒、例えばジメチルホルムアミド、ジメチルアセトアミ
ド、Ｎ−メチルピロリドン、ヘキサメチルホスホリルア
ミドまたはジメチルホルホギシド等が好適である。The above reaction may be carried out by a solution polymerization method in an organic solvent in addition to an interfacial polymerization method. The organic solvent is not particularly limited, and any active hydrogen-unmixed solvent that can dissolve the above-mentioned heptamers can be used, but aprotic amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamers can be used. Methylphosphorylamide or dimethylphorophyde is preferred.
本発明による含フツ素ボリアリレートは上記の方法のほ
かに、例えば、パーフルオロアルケニルオキシイソフタ
ル酸または該パーフルオロアルケニルオキシイソフタル
酸と芳香族ジカルボン酸（例えばテレフタル酸やイソフ
タル酸等）との混合物、または該ジカルボン酸のジエス
テル（例えばジメチルエステルまたはジエチルエステル
等）を化合物（■）および（■）との混合物と高温溶融
状態で反応させる溶融重合法によって製造してもよい。In addition to the above methods, the fluorine-containing polyarylate according to the present invention can be produced by, for example, perfluoroalkenyloxyisophthalic acid or a mixture of the perfluoroalkenyloxyisophthalic acid and an aromatic dicarboxylic acid (such as terephthalic acid or isophthalic acid). Alternatively, it may be produced by a melt polymerization method in which a diester of the dicarboxylic acid (for example, dimethyl ester or diethyl ester) is reacted with a mixture of compounds (■) and (■) in a high-temperature molten state.
さらにまた、比較的高分子量の含フツ素ボリアリレート
が得られる製法として、塩化チオニルとピリジンとの反
応生成物に例えば、パーフルオロアルケニルオキシイソ
フタル酸、または該パーフルオロアルケニルオキシイソ
フタル酸と芳香族ジカルボン酸（例えば、テレフタル酸
、イソフタル酸等）との混合物を反応させ、生成物を化
合物（■）および（■）との混合物と反応させる方法が
挙げられる［ジャーナル・オブ・ポリマー・サイエンス
（Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒ ５ｃ
ｉｅｒ＋ｃｅ）：ポリマー−ケミストリー・エデイジョ
ン（Ｐｏｌｙｍｅｒ Ｃｈｅｍｉｓ −ｔｒｙ Ｅ
ｄｉｔｉｏｎ）、第２４巻、第９７頁〜第１０２頁およ
び第１６９７頁〜第１７０１頁（１９８６年）参照］。Furthermore, as a production method for obtaining a relatively high molecular weight fluorine-containing polyarylate, for example, perfluoroalkenyloxyisophthalic acid is added to the reaction product of thionyl chloride and pyridine, or perfluoroalkenyloxyisophthalic acid and aromatic dicarboxylic acid are added to the reaction product of thionyl chloride and pyridine. Examples include a method of reacting a mixture with an acid (for example, terephthalic acid, isophthalic acid, etc.) and reacting the product with a mixture of compounds (■) and (■) [Journal of Polymer Science Polymer 5c
ier+ce): Polymer Chemis-try E
24, pp. 97-102 and pp. 1697-1701 (1986)].
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
テトラブロムビスフェノールＡ５４．４９（０，１０モ
ル）、水酸化ナトリウム８．０ｙ（０，２０モル）およ
びテトラブチルアンモニウムプロミド０．５ｇを水１０
００ｍ＋２に溶解させた溶液を撹拌装置を備えた反応容
器内へ入れ、該水溶液中へ、パーフルオロノネニルオキ
シイソフタル酸ジクロリド６４゜９ｇ（０，１０モル）
をクロロホルム１５００−に溶解させた溶液を撹拌下で
添加し、添加終了後、撹拌をさらに４時間続行した。Example 1 54.49 (0.10 mol) of tetrabromo bisphenol A, 8.0 y (0.20 mol) of sodium hydroxide and 0.5 g of tetrabutylammonium bromide were added to 10 g of water.
00m+2 was put into a reaction vessel equipped with a stirring device, and 64°9 g (0.10 mol) of perfluorononenyloxyisophthalic acid dichloride was added into the aqueous solution.
A solution of 1,500 ml of chloroform was added under stirring, and after the addition was complete, stirring was continued for an additional 4 hours.
反応混合物を分液漏斗に移し、室温で一夜放置し、クロ
ロホルム層を分液し、約５０％のクロロホルムを留去さ
せた残部を撹拌下でメタノール約２０００ＭＱ中へ添加
した。析出した固体を分離し、メタノールと水を用いて
数回洗浄した後、乾燥処理に付すことによって含フツ素
臭素化ボリアリレート（１）を１０１．０９得ｔ；（収
率９０．０％）。The reaction mixture was transferred to a separatory funnel, left overnight at room temperature, the chloroform layer was separated, and the residue from which about 50% of the chloroform had been distilled off was added to about 2000 MQ of methanol under stirring. The precipitated solid was separated, washed several times with methanol and water, and then subjected to drying treatment to obtain 101.09 tons of fluorine-containing brominated polyarylate (1); (yield 90.0%) .
生成物（１）の物性を表−１に示す。The physical properties of product (1) are shown in Table-1.
実施例２〜９
表−２に示す配合処方により、実施例１の手順に準拠し
て含フツ素ポリ臭化アリレート（２）〜（９）を調製し
た。Examples 2 to 9 Fluorine-containing polybrominated arylates (2) to (9) were prepared according to the procedure of Example 1 using the formulations shown in Table 2.
生成物（２）〜（９）の物性を表−１に示す。Table 1 shows the physical properties of products (2) to (9).
表−１ ２）テトラクロルエタンを溶媒とし、 ３０．０°Ｃで測定 した値。Table-1 2) Using tetrachloroethane as a solvent, Measured at 30.0°C value.
発明の効果
本発明による含フツ素ポリ臭化アリレートは従来の含フ
ツ素ポリマー、ボリアリレートおよび含臭素化合物の有
する優れた緒特性、例えば撥水撥油性、耐薬品性、防汚
性、耐熱性、難燃性、耐候性および特有の反応性等を有
するので、種々の分野において各種の素材、シート、フ
ィルム、成形材、成形品等の原料として汎用できるだけ
でなく、繊維、フィルム、成形品、種々のプラスチック
および壁面等の表面改質剤やコーティング剤として利用
でき、特に、電気電子の分野において多機能性を有する
フィルムや成形品の原料および表面改質剤やコーティン
グ剤等の処理剤として有用である。Effects of the Invention The fluorine-containing polybrominated arylate according to the present invention has excellent properties that conventional fluorine-containing polymers, polyarylates, and bromine-containing compounds have, such as water and oil repellency, chemical resistance, stain resistance, and heat resistance. , has flame retardancy, weather resistance, and unique reactivity, so it can be used not only as a raw material for various materials, sheets, films, molding materials, and molded products in various fields, but also as a raw material for fibers, films, molded products, Can be used as a surface modifier and coating agent for various plastics and walls, and is particularly useful as a raw material for multifunctional films and molded products in the electrical and electronic fields, and as a processing agent for surface modifiers and coatings. It is.
また、この種の含フツ素ポリ臭化アリレートは特定の条
件下で含臭素に起因して特有の反応性を示すので、さら
に高次の機能性官能基を導入したポリマーの有用な製造
原料となる。In addition, this type of fluorine-containing polybrominated arylate exhibits unique reactivity under specific conditions due to its bromine content, so it is a useful raw material for producing polymers with higher-order functional groups introduced. Become.
Claims (1)
V）：▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） ▲数式、化学式、表等があります▼（III） ▲数式、化学式、表等があります▼（IV） （式中、Ｒｆはパーフルオロアルケニル基Ｃ＿６Ｆ＿１
＿１もしくはＣ＿９Ｆ＿１＿７を示し、ＸはＣ（ＣＨ＿
３）＿２、Ｃ（ＣＦ＿３）＿２、ＳＯ＿２、Ｏ、ＣＨ＿
２、ＣＯまたは単結合を示す） で表わされる構造単位から成る分子量２０００以上の含
フッ素ポリ臭化アリレート。 ２、一般式（Ｖ）： ▲数式、化学式、表等があります▼（Ｖ） （式中、Ｒｆは前記と同意義である） で表わされるパーフルオロアルケニルオキシジカルボン
酸ジクロリド、または 該パーフルオロアルケニルオキシジカルボン酸ジクロリ
ドと一般式（VI）： ▲数式、化学式、表等があります▼（VI） で表わされる芳香族ジカルボン酸ジクロリドとの混合物
を脱酸剤の存在下で、 一般式（VII）： ▲数式、化学式、表等があります▼（VII） （式中、Ｘは前記と同意義である） で表わされる臭素化ビスフェノール類および一般式（V
III）： ▲数式、化学式、表等があります▼（VIII） （式中、Ｘは前記と同意義である） で表わされるビスフェノール類と反応させることを特徴
とする、請求項１記載の含フッ素ポリ臭化アリレートの
製造方法。[Claims] 1. The following general formulas (I), (II), (III) and (I
V): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ Mathematical formulas, chemical formulas, tables, etc. Yes▼(IV) (In the formula, Rf is a perfluoroalkenyl group C_6F_1
_1 or C_9F_1_7, X is C(CH_
3)_2, C(CF_3)_2, SO_2, O, CH_
2, CO or a single bond) A fluorine-containing polybrominated arylate having a molecular weight of 2000 or more and consisting of a structural unit represented by: 2. General formula (V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, Rf has the same meaning as above) Perfluoroalkenyloxydicarboxylic acid dichloride, or the perfluoroalkenyl A mixture of oxydicarboxylic acid dichloride and aromatic dicarboxylic acid dichloride represented by general formula (VI): ▼Mathematical formulas, chemical formulas, tables, etc.▼ (VI) In the presence of a deoxidizing agent, general formula (VII): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Brominated bisphenols represented by (VII) (in the formula, X has the same meaning as above) and the general formula (V
III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VIII) (wherein, X has the same meaning as above) The fluorine-containing compound according to claim 1, characterized in that it is reacted with a bisphenol represented by: Method for producing polybrominated arylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1079438A JP2711279B2 (en) | 1989-03-30 | 1989-03-30 | Fluorine-containing polybrominated arylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1079438A JP2711279B2 (en) | 1989-03-30 | 1989-03-30 | Fluorine-containing polybrominated arylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02255720A true JPH02255720A (en) | 1990-10-16 |
| JP2711279B2 JP2711279B2 (en) | 1998-02-10 |
Family
ID=13689884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1079438A Expired - Fee Related JP2711279B2 (en) | 1989-03-30 | 1989-03-30 | Fluorine-containing polybrominated arylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2711279B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49131298A (en) * | 1973-04-23 | 1974-12-16 | ||
| JPS5184892A (en) * | 1975-01-21 | 1976-07-24 | Unitika Ltd | NANNENSEIHOKOZOKUHORIESUTERUKYOJUGOTAINOSEIZOHO |
| JPS6416828A (en) * | 1987-07-09 | 1989-01-20 | Neos Kk | Fluorine-containing polyarylate and production thereof |
-
1989
- 1989-03-30 JP JP1079438A patent/JP2711279B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49131298A (en) * | 1973-04-23 | 1974-12-16 | ||
| JPS5184892A (en) * | 1975-01-21 | 1976-07-24 | Unitika Ltd | NANNENSEIHOKOZOKUHORIESUTERUKYOJUGOTAINOSEIZOHO |
| JPS6416828A (en) * | 1987-07-09 | 1989-01-20 | Neos Kk | Fluorine-containing polyarylate and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2711279B2 (en) | 1998-02-10 |
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