JPS63120732A - Aromatic polyether resin - Google Patents
Aromatic polyether resinInfo
- Publication number
- JPS63120732A JPS63120732A JP26661586A JP26661586A JPS63120732A JP S63120732 A JPS63120732 A JP S63120732A JP 26661586 A JP26661586 A JP 26661586A JP 26661586 A JP26661586 A JP 26661586A JP S63120732 A JPS63120732 A JP S63120732A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- polyether resin
- alkali metal
- aromatic polyether
- bisphenol
- 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
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 13
- 239000011347 resin Substances 0.000 title abstract description 22
- 229920005989 resin Polymers 0.000 title abstract description 22
- 239000004721 Polyphenylene oxide Substances 0.000 title description 20
- 229920000570 polyether Polymers 0.000 title description 20
- 239000002904 solvent Substances 0.000 abstract description 11
- 229930185605 Bisphenol Natural products 0.000 abstract description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 10
- 239000003960 organic solvent Substances 0.000 abstract description 8
- -1 benzo sulfone Chemical class 0.000 abstract description 7
- 229910000288 alkali metal carbonate Inorganic materials 0.000 abstract description 6
- 150000008041 alkali metal carbonates Chemical class 0.000 abstract description 6
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 abstract description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 4
- 239000012770 industrial material Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 150000003457 sulfones Chemical class 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 abstract 1
- 239000002966 varnish Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000000465 moulding Methods 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000034 method Methods 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- ANFPZWOICWAHOG-UHFFFAOYSA-N 1-(6,6-dichlorohexyl)pyrrolidin-2-one Chemical compound ClC(Cl)CCCCCN1CCCC1=O ANFPZWOICWAHOG-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、新規な芳香族ポリエーテル樹脂に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a novel aromatic polyether resin.
本発明のポリエーテルは、耐熱性に優れ、かつ成形性の
良い樹脂である。The polyether of the present invention is a resin with excellent heat resistance and good moldability.
従来よシ芳香族ポリエーテル樹脂は、引張シ強度、弾性
率、衝撃強度などの機械的性質、熱変形温度や熱分解な
どの熱的性質、絶縁性などの電気的性質、耐放射線性な
どにおいて、優れた性質を持つことが知られている。特
に特開昭５４−９０２９６号で公知のポリエーテルは、
その優れた性質から工業的な価値が期待されている。し
かしながら、このポリエーテル樹脂は有機溶剤に不溶で
あ）、そのために工業的な用途が限定されている。Traditionally, aromatic polyether resins have poor mechanical properties such as tensile strength, elastic modulus, and impact strength, thermal properties such as heat distortion temperature and thermal decomposition, electrical properties such as insulation, and radiation resistance. , is known to have excellent properties. In particular, the polyether known from JP-A No. 54-90296 is
Due to its excellent properties, it is expected to have industrial value. However, this polyether resin is insoluble in organic solvents, which limits its industrial use.
一般にグラスチックにおいては、成形性に関する評価が
極めて重要な位置を占めておシ、たとえそのものが本質
的に優れた性質を持っていても、成形性が悪いと、製品
を経済的に製造することができないばかりでなく、その
特性を充分に発揮することができない。In general, evaluation of moldability is extremely important for glass materials, and even if the material itself has inherently excellent properties, if the moldability is poor, it will be difficult to economically manufacture the product. Not only is it not possible to do so, but it is also not possible to fully demonstrate its characteristics.
グラスチックの成形は、加熱溶融状態から射出成形や押
出し成形によシ成形する方法と、溶液状態から紡糸、フ
ィルム成形を行なう方法、更に％溶液状態からコーティ
ング、塗装、接着を行なう成形加工に大別される。加熱
溶融状態からの成形には、軟化温度（又は溶融温度）が
重要でめシ、一方、溶液状態からの成形には、溶解性、
すなわち、取扱いが容易で安価な溶媒に樹脂が易溶であ
ることが望まれる。There are three methods for molding glass: injection molding or extrusion molding from a heated molten state, spinning and film forming from a solution state, and further molding processes such as coating, painting, and adhesion from a solution state. Separated. For molding from a heated molten state, the softening temperature (or melting temperature) is important; on the other hand, for molding from a solution state, solubility,
That is, it is desired that the resin be easily soluble in a solvent that is easy to handle and inexpensive.
本発明者らは、上記、公知の芳香族ポリエーテル樹脂の
欠点を克服し、しかもその優れた性質を維持するような
新しいポリマーの開発に努力１．り結果、９１９−ビフ
ェニルフルオレン基ヲ成分に持つ芳香族ポリエーテルが
各棟の有機溶媒に特異的に可溶であシ、しかも、優れた
耐熱性や強度を持つことを見出し、本発明を完成した。The present inventors have made efforts to develop a new polymer that overcomes the drawbacks of the above-mentioned known aromatic polyether resins while still maintaining its excellent properties.1. As a result, they discovered that the aromatic polyether having a 919-biphenylfluorene group as a component is specifically soluble in each organic solvent and has excellent heat resistance and strength, and completed the present invention. did.
すなわち、本発明は、 で表わされるポリエーテル樹脂である。That is, the present invention It is a polyether resin represented by
この芳香族ポリエーテル樹脂は、一般的に公知なポリエ
ーテル樹脂の製造方法により製造することができる。This aromatic polyether resin can be produced by a generally known polyether resin production method.
すなわち、ビスフェノールのアルカリ金属塩とベンゾス
ルホンシバライドとを適当な溶媒中で加熱することによ
って重合することができる。That is, the alkali metal salt of bisphenol and benzosulfone cybaride can be polymerized by heating in a suitable solvent.
本発明において、ビスフェノールとしては、９．９−ビ
ス（４−ヒドロキシフェニル）フルオレン、１，１．３
− ）ジメチル−３−（４’−ヒドロキシフェニル）−
５−インダノール、ヒドロキノン、４．４’−ジヒドロ
キシビフエニル、２．２’−ビス（４−ヒドロキシフェ
ニル）プロパン、２．２’−ビス（４−ヒドロキシフェ
ニル）ヘキサフルオログロパ／、４．４１−ジヒドロキ
シジフェニルスルホン、４．４’−ジヒドロキシベンゾ
フェノンなどが有効である。In the present invention, bisphenol includes 9,9-bis(4-hydroxyphenyl)fluorene, 1,1.3
-) dimethyl-3-(4'-hydroxyphenyl)-
5-indanol, hydroquinone, 4.4'-dihydroxybiphenyl, 2.2'-bis(4-hydroxyphenyl)propane, 2.2'-bis(4-hydroxyphenyl)hexafluoroglopa/, 4.41 -dihydroxydiphenylsulfone, 4,4'-dihydroxybenzophenone, etc. are effective.
またアルカリ金属塩としては、ナトリウム塩、カリウム
塩、カルシウム塩などが好ましい。このアルカリ金属塩
は、ビスフェノールと等量のアルカリ金属水酸化物、九
とえは、水酸化ナトリウム、水酸化カリウムを適当な溶
媒中で反応させて製造することができる。Moreover, as the alkali metal salt, sodium salt, potassium salt, calcium salt, etc. are preferable. This alkali metal salt can be produced by reacting bisphenol with an equivalent amount of an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, in an appropriate solvent.
本発明に用いられるベンゾスルホンシバライ）”ハ％
４１４’−ジクロロベンゾスルホン、４．４’−ジフ
ルオロベンゾスルホンである。また、本反応に用いられ
る重合溶媒としては、Ｎ−メチルピロリドン、Ｎ−ジク
ロヘキシルピロリド／、ジメチルスルホキシド、ジメチ
ルホルムアミド、ジメチルアセトアミド、スルホラン、
ジメチルスルホン、ジフェニルスルホン等の極性溶媒が
有効である。Benzosulfone used in the present invention
414'-dichlorobenzosulfone and 4,4'-difluorobenzosulfone. In addition, the polymerization solvent used in this reaction includes N-methylpyrrolidone, N-dichlorohexylpyrrolidone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, sulfolane,
Polar solvents such as dimethylsulfone and diphenylsulfone are effective.
！ｉ ビスフェノール、ベンゾスルホンシバ２イド、ア
ルカリ金属の炭酸塩を適当な溶媒中で反応させ、重合さ
せることも可能である。この時、アルカリ金属の炭酸塩
としては、ナトリウム及びカリウムの炭酸塩が好ましい
。また、アルカリ金属の炭酸塩は無水のものが好ましい
。! i It is also possible to react and polymerize bisphenol, benzosulfonic acid, and an alkali metal carbonate in a suitable solvent. At this time, the alkali metal carbonates are preferably sodium and potassium carbonates. Further, the alkali metal carbonate is preferably anhydrous.
アルカリ金属の炭酸塩は、ビスフェノール１モル当シ実
買的に２−１ニル量を仕込む事が好ましい。The alkali metal carbonate is preferably used in an amount of 2-1 nil per mole of bisphenol.
これよ）少ないと、重合が完結しない。また過剰であっ
ても、１合に対して好ましい効果はなく、むしろ、経済
的に不利益となる。ビスフェノールとベンゾスルホンシ
バライドは、実質的に等モル量仕込むことが大切である
。どちらかが過剰であると、高重合度の目的物を得るこ
とができない。この反応に用いる１合溶媒としては前述
の重合溶媒と同じものが可能である。この反応は、同一
の反応容器内で、次の二段階の反応が逐次進行するもの
と考えられる。すなわち、−段階として、ビスフェノー
ルとアルカリ金属の炭酸塩との反応により、ビスフェノ
ールのアルカリ金属塩が生成し、続いて、ビスフェノー
ルのアルカリ金属塩とベンゾスルホンシバライドとの重
縮合反応が進行する。一段階目の反応は、脱水を伴なう
平衡反応であるため、副生する水を系外に取シ出す方法
で反応を行なえば、よシ有利に反応を進めることが可能
である。If there is too little of this, polymerization will not be completed. Moreover, even if it is in excess, it will not have a favorable effect on 1 go, but will be economically disadvantageous. It is important that bisphenol and benzosulfone cybaride be added in substantially equimolar amounts. If either of them is in excess, the desired product with a high degree of polymerization cannot be obtained. The combined solvent used in this reaction may be the same as the polymerization solvent described above. In this reaction, the following two-stage reactions are considered to proceed sequentially in the same reaction vessel. That is, in the -step, an alkali metal salt of bisphenol is generated by the reaction of bisphenol and an alkali metal carbonate, and then a polycondensation reaction between the alkali metal salt of bisphenol and benzosulfone cybaride proceeds. Since the first stage reaction is an equilibrium reaction accompanied by dehydration, it is possible to proceed the reaction more favorably if the reaction is carried out in such a way that by-produced water is removed from the system.
このための方法として、水と共沸する有機溶媒を共存さ
せ、副生ずる水を除去する方法が有効である。共沸させ
る有機溶媒としては、ベンゼン、クロルベンゼン、トル
エン等（Ｄ 公知Ｏ溶媒が有効である。この反応は、ま
ず第一段階では、共沸溶媒と水が共沸する温度、すなわ
ち摂氏数十度から二百度の温度で水が共沸しなくなるま
で反応させ、続いて、よシ高い温度で重合反応が行なわ
れる。重合は、反応温度が高いほど、よυ有利に進行す
るが、実質的に重合溶媒の還流温度で反応させる。反応
は数時間で終了する。An effective method for this purpose is to coexist an organic solvent that is azeotropic with water and remove water as a by-product. As the organic solvent for the azeotrope, benzene, chlorobenzene, toluene, etc. (D) Known O solvents are effective. In the first step, this reaction is carried out at a temperature at which the azeotropic solvent and water azeotrope, that is, several tens of degrees Celsius. The reaction is carried out at a temperature between 300 and 200 degrees Celsius until water no longer azeotropes, and then the polymerization reaction is carried out at a higher temperature.The higher the reaction temperature, the more advantageously the polymerization proceeds, but substantially The reaction is carried out at the reflux temperature of the polymerization solvent.The reaction is completed in several hours.
このようにして得られた芳香族ポリエーテル樹脂は、熱
分解温度が５００℃以上と高い耐熱性を持つ、また、各
種の有機溶媒に可溶であり、これらの有機溶媒の溶液か
ら無色透明で強靭なフィルムを成形することができる。The aromatic polyether resin obtained in this way has high heat resistance with a thermal decomposition temperature of 500°C or higher, and is soluble in various organic solvents, and is colorless and transparent from a solution of these organic solvents. A strong film can be formed.
以下、実施例によって本発明をより詳しく説明するが、
これに限定されるものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
It is not limited to this.
（実施例−１）
窒素ガス導入口、ディーンスタークトラップｔＡｉ＊
ｔｏｏ ｔｙの三つロア２スコに９．９−ビス（４−ヒ
ドロキクフェニル）フルオレン（３，５０１）、４４’
−ジフルオロベンゾスルホン（２，５４Ｆ）、ｌ−メチ
ル−２−ピロリドン（１７ｄ）、トルエン（１４，４ｄ
）と充分に乾燥した無水炭酸カリウム（１，４９ｙ）を
採取する。(Example-1) Nitrogen gas inlet, Dean-Stark trap tAi*
9,9-bis(4-hydroxyphenyl)fluorene (3,501), 44'
-difluorobenzosulfone (2,54F), l-methyl-2-pyrrolidone (17d), toluene (14,4d)
) and sufficiently dried anhydrous potassium carbonate (1,49y) are collected.
窒素ガス気流下で攪拌しながら、徐々に加熱昇温する。The temperature is gradually increased while stirring under a nitrogen gas flow.
溶液の温度が上昇すると共にトルエンが還流を始める。As the temperature of the solution increases, the toluene begins to reflux.
反応によって副生する水を、トルエンと共沸させてディ
ーンスタークトラップで除去する。水を除去し終ったら
、内温を１６０〜１７０℃にまで上昇させ、６時間反応
を続ける。Water produced by the reaction is azeotroped with toluene and removed in a Dean-Stark trap. Once the water has been removed, the internal temperature is raised to 160-170°C and the reaction is continued for 6 hours.
反応終了後、溶液を大量の水中に投入して、ポリマーを
析出させた後、蒸留水、メタノールで洗浄し、乾燥させ
る。After the reaction is completed, the solution is poured into a large amount of water to precipitate the polymer, which is then washed with distilled water and methanol and dried.
収量５．６０ｇ収４９９．２ ％ ）ｓ Ｏｐ ｏ ｏ
７−ｒ−／ −ル中、５０℃での固有粘度は０．５０
（ｄＬ／ハであった。Yield 5.60g Yield 499.2%)s Op o o
Intrinsic viscosity at 50°C in 7-r-/-r is 0.50
(It was dL/ha.
元素分析および赤外分光分析の結果、以下の分子構造の
ポリエーテル樹脂であることを確認元素分析；ＯＨ
計算値（チ） ７８，７０ ４．２８実測値（％
） ７８，１２ ４．８０赤外雇吸収； １２４
０３−”（０−０〜Ｃ）、１：１９５ｆｉ−１，１２０
０偲（Ｂｏｘ）
熱的性質、溶解性について、（表−１）（ｆｉ−２）に
示す。As a result of elemental analysis and infrared spectroscopy, it was confirmed that it is a polyether resin with the following molecular structure.Elemental analysis: OH Calculated value (H) 78,70 4.28 Actual value (%
) 78,12 4.80 infrared absorption; 124
03-” (0-0~C), 1:195fi-1,120
0 (Box) Thermal properties and solubility are shown in (Table-1) (fi-2).
（実施例−２）
（実施例−１）と同じ方法で、９，９−ビス（４−ヒド
ロキクフェニル）フルオレン（ｓ 、７５ Ｆ ）、ヒ
ドロキノン（ａ、５ｓｐ）、４．４１−ジフルオロベン
ゾスルホン（２，５４Ｆ）、無水炭酸カリウム（１，４
９Ｆ）を、１−メチル−２−ピロリドン（１７ｄ）、ト
ルエン（１４、４ｔｘｔ ）中で反応させた。(Example-2) In the same manner as in (Example-1), 9,9-bis(4-hydroxyphenyl)fluorene (s, 75F), hydroquinone (a, 5sp), 4,41-difluorobenzo Sulfone (2,54F), anhydrous potassium carbonate (1,4
9F) was reacted in 1-methyl-2-pyrrolidone (17d) and toluene (14,4txt).
その結果、収量４．３９Ｆ（収＄９８．８チ）で、固有
粘度０ 、４８ （（ＬＬ／Ｆ ） （０−クロロフェ
ノール中、５０℃）のポリエーテル樹脂を得た。As a result, a polyether resin was obtained with a yield of 4.39 F (yield: $98.8) and an intrinsic viscosity of 0.48 ((LL/F) (in 0-chlorophenol, 50° C.).
元素分析と赤外分光分析の結果、以下の構造であること
を確認した。As a result of elemental analysis and infrared spectroscopy, the following structure was confirmed.
元素分析；ＯＨ
計算値（チ） ７３．９７ ４．５１実測値鴎）
門、０９ ４．６０
赤外線吸収ｉ １２４０ｃｍ （０−０−０）、１３９
５ｃ１ｎｓ！２００ｃ、 （Ｓｏ、）
（比較例−１）
（実施例−１）と同じ方法で、ヒドロキノン（１，ｌ０
ｊＥ）、４，４′−ジフルオロベンゾフェノン（２，鳳
８Ｆ）、無水炭酸カリウム（１，４９ｙ）を１−メチル
−２−ピロリドン（１７ｘｉ ）、トルエン（１４，４
ｍｊ）中で反応させた。Elemental analysis; OH Calculated value (H) 73.97 4.51 Actual value (O)
Gate, 09 4.60 Infrared absorption i 1240cm (0-0-0), 139
5c1ns! 200c, (So,) (Comparative Example-1) Hydroquinone (1,10
jE), 4,4'-difluorobenzophenone (2, 8F), anhydrous potassium carbonate (1,49y), 1-methyl-2-pyrrolidone (17xi), toluene (14,4
mj).
その結果、収ｔ ２．ｓ２ｙ （収′４９８％）で固Ｍ
粘度０．５０＜ｅＬＶｙ） ｃ硫酸中、５０℃）のポリ
エーテル樹脂を得た。As a result, the yield was reduced 2. Solid M with s2y (yield '498%)
A polyether resin with a viscosity of 0.50<eLVy) (in sulfuric acid at 50°C) was obtained.
元素分析と赤外分光分析の結果、以下の構造であること
を確認した。As a result of elemental analysis and infrared spectroscopy, the following structure was confirmed.
元素分析； ＯＢ Ｏ
計算値（＠ ７９．盈５ ４，２０ １６．６５実
測値（％） ７９．１８ ４，１６ １６，６６亦
外級吸収；１６う０信−１（ａ＝ｏ）、１２５０譚−’
（ｃ−ｏ−ｏ）（表−２）樹脂の溶解性
（実施例−１）、（実施例−２）で得られたポリエーテ
ル樹脂のテトラクロルエタン溶液から透明で強いフィル
ムを作ることができた。Elemental analysis; OB O Calculated value (@ 79. 5 4,20 16.65 Actual value (%) 79.18 4,16 16,66 亦Extraordinary absorption; 16 U0 Shin-1 (a=o), 1250 Tan-'
(c-o-o) (Table-2) Solubility of resin (Example-1), It is possible to make a transparent and strong film from the tetrachloroethane solution of the polyether resin obtained in (Example-2). did it.
（発明の効果）
本発明は、一般式（１）で表わされる新規な芳香族ポリ
エーテル樹脂に関する。従来、（比較例−１）に代衣さ
れる芳香族ポリエーテル樹脂はその浸れた熱的、機械的
、電機的性質やその他の優秀な性質によって、工業的素
材としての期待が大きいにもかかわらず、有機溶媒に対
して不溶であるために、用途が限定されていた。これに
対し、本発明の芳香族ポリエーテル樹脂は、各種の有機
ｍｔｓに特異的に可溶であシ、成形が容易で、しかも優
れた耐熱性、機械的特性を有する。このため、本発明の
芳香族ポリエーテル樹脂は、各種工業材料、特に、従来
不可能であった、フェス、塗料、接着、コーティング、
繊維等における価値が高い。(Effects of the Invention) The present invention relates to a novel aromatic polyether resin represented by general formula (1). Conventionally, the aromatic polyether resin used as a substitute for (Comparative Example-1) has high expectations as an industrial material due to its excellent thermal, mechanical, electrical properties, and other properties. First, it is insoluble in organic solvents, so its uses are limited. In contrast, the aromatic polyether resin of the present invention is specifically soluble in various organic mts, easy to mold, and has excellent heat resistance and mechanical properties. For this reason, the aromatic polyether resin of the present invention can be used for various industrial materials, especially for festivals, paints, adhesives, coatings, etc., which were previously impossible.
High value in textiles, etc.
Claims (1)
族基であり、Ｒのうち、少くとも１種は、９，９−ビフ
エニルフルオレン基から成る。ｎは１〜２００の整数を
示す。） で表わされるポリエーテル樹脂。[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is one type or two or more types of divalent aromatic group, and at least one type of R is , 9,9-biphenylfluorene group (n is an integer of 1 to 200).
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26661586A JPS63120732A (en) | 1986-11-11 | 1986-11-11 | Aromatic polyether resin |
| US07/115,914 US4806618A (en) | 1986-11-11 | 1987-11-02 | Aromatic polyethers having biphenylfluorene group |
| GB8726273A GB2197333B (en) | 1986-11-11 | 1987-11-10 | Aromatic polyethers having biphenylfluorene group |
| FR8715580A FR2606415A1 (en) | 1986-11-11 | 1987-11-10 | AROMATIC POLYETHERS HAVING A BIPHENYLFLUORENE GROUP |
| IT8722581A IT1232948B (en) | 1986-11-11 | 1987-11-10 | AROMATIC POLYETERS WITH DIPHENYLFLUORENE GROUP |
| DE19873738339 DE3738339A1 (en) | 1986-11-11 | 1987-11-11 | AROMATIC POLYETHER CONTAINING A BIPHENYLFLUORENE GROUP |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26661586A JPS63120732A (en) | 1986-11-11 | 1986-11-11 | Aromatic polyether resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63120732A true JPS63120732A (en) | 1988-05-25 |
Family
ID=17433273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26661586A Pending JPS63120732A (en) | 1986-11-11 | 1986-11-11 | Aromatic polyether resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63120732A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007125931A1 (en) * | 2006-04-25 | 2007-11-08 | Jsr Corporation | Aromatic compound having fluorene skeleton and polyarylene having sulfonic acid group |
-
1986
- 1986-11-11 JP JP26661586A patent/JPS63120732A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007125931A1 (en) * | 2006-04-25 | 2007-11-08 | Jsr Corporation | Aromatic compound having fluorene skeleton and polyarylene having sulfonic acid group |
| JP2007291243A (en) * | 2006-04-25 | 2007-11-08 | Jsr Corp | Aromatic compound having fluorene skeleton and polyarylene bearing sulfonic group |
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