JP2551088B2 - Process for producing polyether polymer having phenyl group in side chain - Google Patents
Process for producing polyether polymer having phenyl group in side chainInfo
- Publication number
- JP2551088B2 JP2551088B2 JP63048641A JP4864188A JP2551088B2 JP 2551088 B2 JP2551088 B2 JP 2551088B2 JP 63048641 A JP63048641 A JP 63048641A JP 4864188 A JP4864188 A JP 4864188A JP 2551088 B2 JP2551088 B2 JP 2551088B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- phenyl group
- side chain
- polyether polymer
- reaction
- 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.)
- Expired - Fee Related
Links
- 229920000570 polyether Polymers 0.000 title claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title description 9
- 238000000034 method Methods 0.000 title description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 8
- 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 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 239000004721 Polyphenylene oxide Substances 0.000 description 18
- 125000003118 aryl group Chemical group 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920006380 polyphenylene oxide Polymers 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 3
- 150000008046 alkali metal hydrides Chemical class 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- VCJZTATVUDMNLU-UHFFFAOYSA-N dibromomethylbenzene Chemical compound BrC(Br)C1=CC=CC=C1 VCJZTATVUDMNLU-UHFFFAOYSA-N 0.000 description 1
- JDZLOJYSBBLXQD-UHFFFAOYSA-N difluoromethylbenzene Chemical compound FC(F)C1=CC=CC=C1 JDZLOJYSBBLXQD-UHFFFAOYSA-N 0.000 description 1
- HIPNYJBGYFRVAY-UHFFFAOYSA-N diiodomethylbenzene Chemical compound IC(I)C1=CC=CC=C1 HIPNYJBGYFRVAY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- -1 α-methylbenzylidene Chemical group 0.000 description 1
Landscapes
- Polyethers (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はフェニル基を側鎖に有する新規なポリエーテ
ル重合体及びその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polyether polymer having a phenyl group in a side chain and a method for producing the same.
本発明のフェニル基を側鎖に有するポリエーテル重合
体は機械的強度、耐久性、耐熱性、耐湿性に優れるとと
もに極めて良好な透明性を有しているためにエンジニア
リング樹脂として様々な用途への応用が可能な高分子材
料であるが、とくに光学的に均質で複屈折が小さい特徴
を有しているため、光ファイバー、光学用レンズ、デジ
タルオーディオディスクあるいは光メモリーディスクな
どの光学材料用樹脂として有用である。The polyether polymer having a phenyl group in the side chain of the present invention is excellent in mechanical strength, durability, heat resistance, and moisture resistance, and also has extremely good transparency, so that it can be used in various applications as an engineering resin. Although it is a polymer material that can be applied, it is particularly useful as a resin for optical materials such as optical fibers, optical lenses, digital audio discs, optical memory discs, etc. because it has the characteristics of being optically homogeneous and having small birefringence. Is.
［従来の技術］ ポリエーテル化合物は機械的強度、耐久性及び耐熱性
に優れた高分子材料であり、エンジニアリング樹脂とし
て近年広く用いられている。[Prior Art] Polyether compounds are polymeric materials having excellent mechanical strength, durability, and heat resistance, and have been widely used in recent years as engineering resins.
例えば、ポリフェニレンオキシド（PPO）は高い熱変
形温度（193℃）及び低いぜい化温度（−170℃）を有
し、極めて広い温度範囲で使用できるエンジニアリング
プラスチックである。この樹脂とスチレン系樹脂とのブ
レンドあるいはグラフトによる変性PPOは成形性を改良
したものであり、PPOの特性を利用したバランスのとれ
た物性と様々なニーズに対応する豊富なグレードにより
エンジニアリング樹脂としての一角を占めている。ま
た、ポリスルホン（PS）、ポリエーテルスルホン（PE
S）、ポリエーテルケトン（PEK）、ポリエーテルエーテ
ルケトン（PEEK）等の芳香族ポリエーテル樹脂がエンジ
ニアリング樹脂として近年注目を集めている。For example, polyphenylene oxide (PPO) is an engineering plastic that has a high heat distortion temperature (193 ° C) and a low embrittlement temperature (-170 ° C) and can be used in a very wide temperature range. Modified PPO by blending or grafting this resin with styrene-based resin has improved moldability, and has a balanced physical property utilizing the properties of PPO and abundant grades corresponding to various needs, making it an engineering resin. It occupies a corner. In addition, polysulfone (PS), polyether sulfone (PE
Aromatic polyether resins such as S), polyetherketone (PEK), and polyetheretherketone (PEEK) have recently attracted attention as engineering resins.
これらの芳香族ポリエーテル樹脂は、高い耐熱性を有
する熱可塑性樹脂であり高温剛性、耐クリープ性、寸法
精度、耐湿性、電気的性質に優れた特性を示すため、高
性能エンジニアリングプラスチックとして各方面に幅広
い用途展開が期待されている。These aromatic polyether resins are thermoplastic resins with high heat resistance and exhibit excellent properties in high temperature rigidity, creep resistance, dimensional accuracy, moisture resistance, and electrical properties. It is expected to have a wide range of applications.
しかしながら、これらの芳香族ポリエーテル樹脂は主
鎖に芳香族環を有する構造のみのため、分極率の異方性
が大きい。そのためこれらの樹脂を光ファイバー、光学
用レンズ、デジタルオーディオディスクあるいは光メモ
リーディスクなどの光学材料用樹脂として用いるために
押し出し成形、射出成形等の通常の成形方法で成形した
場合、光学的異方性（複屈折）が大きくなるという問題
点を有している。However, these aromatic polyether resins have a large anisotropy of polarizability because they have only a structure having an aromatic ring in the main chain. Therefore, when these resins are used as a resin for optical materials such as optical fibers, optical lenses, digital audio discs or optical memory discs by extrusion molding, injection molding, or other ordinary molding methods, optical anisotropy ( It has a problem that the birefringence) becomes large.
以上のように様々なポリエーテル化合物が高性能エン
ジニアリングプラスチックとして期待されているが、良
好な透明性を持ちながら、耐熱性、耐久性、機械的強度
を有し、かつ光学的に均質で複屈折の小さな芳香族ポリ
エーテル樹脂は見出だされていないのが現状である。As mentioned above, various polyether compounds are expected as high-performance engineering plastics, but they have good transparency, heat resistance, durability, mechanical strength, and are optically homogeneous and birefringent. In the present situation, no small aromatic polyether resin has been found.
［発明が解決しようとする課題］ 本発明は、上に述べた従来の芳香族ポリエーテル樹脂
の特徴である耐熱性、耐湿性、機械的強度を有している
とともに、光学的に均質で複屈折の小さな芳香族ポリエ
ーテル樹脂を提供するものである。[Problems to be Solved by the Invention] The present invention has the heat resistance, moisture resistance, and mechanical strength that are the characteristics of the conventional aromatic polyether resins described above, and is optically homogeneous and complex. An aromatic polyether resin having a small refraction is provided.
［課題を解決するための手段］ 本発明者等は従来の芳香族ポリエーテル樹脂の特徴で
ある優れた耐熱性、耐久性、機械的強度を有するととも
に光学的に均質で複屈折の小さな芳香族ポリエーテル樹
脂を得るべく、鋭意検討を行った。[Means for Solving the Problems] The present inventors have found that an aromatic aromatic resin having excellent heat resistance, durability, mechanical strength, which is a characteristic of conventional aromatic polyether resins, and which is optically homogeneous and has a small birefringence. In order to obtain a polyether resin, earnest study was conducted.
その結果、側鎖にフェニル基を有するポリエーテル重
合体が従来の芳香族ポリエーテル樹脂の特徴である耐熱
性，耐湿性，機械的強度を有しているとともに、光学的
に均質で複屈折が小さいことを見い出し本発明の到達し
た。As a result, the polyether polymer having a phenyl group on the side chain has the heat resistance, moisture resistance, and mechanical strength that are the characteristics of conventional aromatic polyether resins, while being optically homogeneous and birefringent. The present invention has been reached by finding out that it is small.
即ち本発明は塩基存在下、一般式（２） （式中、Ａは を示す。） で表されるビスフェノールと 一般式（３） （式中、X,X′はそれぞれF,Cl,Br,Iを示す。） で表されるα，α−ジハロゲノトルエンとを反応させる
ことを特徴とする、繰り返し単位が一般式（１） （式中、Ａは を示す。） で表されるポリエーテル重合体の製造方法を提供するも
のである。That is, the present invention is a compound of formula (2) in the presence of a base. (In the formula, A is Indicates. ) And bisphenol represented by the general formula (3) (In the formula, X and X'represent F, Cl, Br and I respectively.) The repeating unit represented by the general formula (1) is characterized by reacting with α, α-dihalogenotoluene. (In the formula, A is Indicates. ) A method for producing a polyether polymer represented by
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
繰り返し単位が前記一般式（１）で表されるポリエー
テル重合体は、前記一般式（２）で表されるビスフェノ
ールと前記一般式（３）で表されるα，α−ジハロゲノ
トルエンとを塩基存在下、有機溶媒中で通常０〜200℃
の温度、好ましくは50〜100℃で10分〜48時間重合する
ことにより得られる。The polyether polymer in which the repeating unit is represented by the general formula (1) includes the bisphenol represented by the general formula (2) and the α, α-dihalogenotoluene represented by the general formula (3). In the presence of a base, usually in an organic solvent 0-200 ℃
At a temperature of 50 to 100 ° C. for 10 minutes to 48 hours.
本発明で用いられる有機溶媒としては、ポリエーテル
重合体を溶解し、本反応に関与しないものであればいず
れのものを用いてもよく、テトラヒドロフラン、ジオキ
サン、γ−ブチロラクトン、ジメトキシエタン、ベンゼ
ン、トルエン、キシレン、Ｎ−メチル−２−ピロリド
ン、1,3−ジメチル−２−イミダゾリジノン、N,N−ジメ
チルホルムアミド、ジメチルスルホキシドなどの有機溶
媒を用いることができるが、反応効率の点でＮ−メチル
−２−ピロリドン、1,3−ジメチル−２−イミダゾリジ
ノンなどの溶媒を用いることが好ましい。なお、必要に
応じて反応終了後、メチルクロライド、メチルブロマイ
ドなどのアルキルハライドを反応停止剤として加えても
良い。As the organic solvent used in the present invention, any solvent may be used as long as it dissolves the polyether polymer and does not participate in the present reaction, and tetrahydrofuran, dioxane, γ-butyrolactone, dimethoxyethane, benzene, toluene may be used. , Xylene, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylformamide, dimethylsulfoxide and the like can be used as an organic solvent, but N- It is preferable to use a solvent such as methyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidinone. If necessary, after completion of the reaction, an alkyl halide such as methyl chloride or methyl bromide may be added as a reaction terminator.
本反応の製造方法で用いる塩基としては、水酸化ナト
リウム、水酸化カリウムなどのアルカリ金属水酸化物、
水素化ナトリウム、水素化カリウムなどのアルカリ金属
水素化物、炭酸ナトリウム、炭酸カリウムなどのアルカ
リ金属炭酸化物、炭酸水素ナトリウム、炭酸水素カリウ
ムなどのアルカリ金属炭酸水素化物、メチルリチウム、
ｎ−ブチルリチウム、ｓ−ブチルリチウム、ｔ−ブチル
リチウム、フェニルリチウムなどの有機リチウム化合物
を例示することができる、反応効率の点でアルカリ金属
水酸化物あるいはアルカリ金属水素化物を用いることが
好ましい。これらの塩基は、前記一般式（２）で示され
るビスフェノールに対して通常２〜５当量用い、反応を
行う。As the base used in the production method of this reaction, sodium hydroxide, an alkali metal hydroxide such as potassium hydroxide,
Alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrides such as sodium hydrogen carbonate and potassium hydrogen carbonate, methyl lithium,
An organic lithium compound such as n-butyllithium, s-butyllithium, t-butyllithium, or phenyllithium can be exemplified, and it is preferable to use an alkali metal hydroxide or an alkali metal hydride from the viewpoint of reaction efficiency. These bases are usually used in an amount of 2 to 5 equivalents with respect to the bisphenol represented by the general formula (2) to carry out the reaction.
前記一般式（３）で表されるα，α−ジハロゲノトル
エンとしては、α，α−ジフルオロトルエン、α，α−
ジクロロトルエン、α，α−ジブロモトルエン、α，α
−ジヨードトルエンなどを例示することができる。Examples of the α, α-dihalogenotoluene represented by the general formula (3) include α, α-difluorotoluene, α, α-
Dichlorotoluene, α, α-dibromotoluene, α, α
Examples thereof include diiodotoluene.
これらのα，α−ジハロゲノトルエンを前記一般式
（２）で表されるビスフェノールに対し当量加え反応を
進行させる。An equivalent amount of these α, α-dihalogenotoluene is added to the bisphenol represented by the general formula (2) to allow the reaction to proceed.
以上述べた反応により、本発明の前記一般式（１）で
示される繰り返し単位からなるフェニル基を側鎖に有す
る芳香族ポリエーテル重合体を製造することができる。By the reaction described above, an aromatic polyether polymer having a phenyl group composed of the repeating unit represented by the general formula (1) of the present invention in the side chain can be produced.
本発明の製造方法でフェニル基を側鎖に有する芳香族
ポリエーテル樹脂を製造する際に、反応温度、反応時間
および加える塩基の量を調節することにより、前記一般
式（１）で示される繰り返し単位からなるポリエーテル
樹脂の分子量を任意に調節することができる。When the aromatic polyether resin having a phenyl group in the side chain is produced by the production method of the present invention, the reaction temperature, the reaction time, and the amount of the base to be added can be adjusted to obtain the repeating unit represented by the general formula (1). The molecular weight of the polyether resin composed of units can be arbitrarily adjusted.
また反応は、生成物の着色を抑えるために遮光条件下
で行うのがより好ましい。Further, the reaction is more preferably carried out under light-shielding conditions in order to suppress coloring of the product.
［発明の効果］ 本発明により得られる、フェニル基を側鎖に有する芳
香族ポリエーテル重合体は耐熱性、耐久性、機械的強度
に優れているとともに極めて良好な透明性を有している
ために、エンジニアリングプラスチックとして様々な用
途への応用が可能な高分子材料である。特に従来のポリ
エーテル樹脂と比べ光学的に均質で複屈折が小さいとい
う特徴を有しているため、光ファイバー、光学用レン
ズ、デジタルオーディオディスクあるいは光メモリ−デ
ィスクのどの光学材料用樹脂として有用である。[Effects of the Invention] The aromatic polyether polymer having a phenyl group in the side chain obtained by the present invention is excellent in heat resistance, durability, mechanical strength and has extremely good transparency. In addition, it is a polymer material that can be applied to various uses as engineering plastics. In particular, since it has the characteristics of being optically homogeneous and having a small birefringence as compared with conventional polyether resins, it is useful as a resin for optical materials such as optical fibers, optical lenses, digital audio discs or optical memory discs.
［実施例］ 以下、実施例により本発明をさらに詳細に説明する
が、本発明はこれら実施例にのみ限定されるものではな
い。[Examples] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例１ 4,4′−（α−メチルベンジリデン）ビスフェノール1
1.6g（0.04mol）、α，α−ジクロロトルエン6.4g（0.0
4mol）、水酸化ナトリウム6.4g（1.16mol）およびＮ−
メチル−２−ピロリドン40mlの混合溶液を撹拌しなが
ら、80℃において５時間反応を行った。反応終了後、生
成物をメタノール中に投入して重合体を回収した。Example 1 4,4 '-(α-methylbenzylidene) bisphenol 1
1.6 g (0.04 mol), α, α-dichlorotoluene 6.4 g (0.0
4 mol), sodium hydroxide 6.4 g (1.16 mol) and N-
While stirring a mixed solution of 40 ml of methyl-2-pyrrolidone, the reaction was carried out at 80 ° C. for 5 hours. After completion of the reaction, the product was put into methanol to collect the polymer.
得られた重合体を塩化メチレンに溶解し、不溶の塩を
濾過した後に、再びメタノール中に投入して精製した。
得られた白色固体を真空下40℃にて乾燥したところ収量
12.2gであった。The obtained polymer was dissolved in methylene chloride, the insoluble salt was filtered off, and the mixture was again poured into methanol for purification.
The yield of the obtained white solid was dried under vacuum at 40 ° C.
It was 12.2 g.
得られた重合体についてGPC測定を行ったところ、重
量平均分子量はポリスチレン換算値で4.3×104であっ
た。GPC measurement of the obtained polymer showed that the weight average molecular weight was 4.3 × 10 4 in terms of polystyrene.
また、生成物のIRおよび元素分析の結果は次のとおり
であった。The results of IR and elemental analysis of the product were as follows.
IRスペクトル（cm-1）:3056（ｍ）,3032（ｍ）,2976
（ｍ）,2937（ｗ）,1686（ｍ）,1605（ｓ）,1581
（ｓ）,1502（ｓ）,1444（ｍ）,1373（ｍ）,1244
（ｓ）,1213（ｓ）,1174（ｓ）,1119（ｍ）,999（ｓ）,
891（ｗ）,829（ｍ）,752（ｍ）,698（ｓ）,573（ｍ） 元素分析： Ｃ（％） Ｈ（％） 分析値 85.24 5.85 理論値 85.71 5.82 理論値は、4,4′−（α−メチルベンジリデン）ビス
フェノールとα，α−ジクロロトルエンが1:1で反応し
たと仮定して算出した。IR spectrum (cm -1 ): 3056 (m), 3032 (m), 2976
(M), 2937 (w), 1686 (m), 1605 (s), 1581
(S), 1502 (s), 1444 (m), 1373 (m), 1244
(S), 1213 (s), 1174 (s), 1119 (m), 999 (s),
891 (w), 829 (m), 752 (m), 698 (s), 573 (m) Elemental analysis: C (%) H (%) Analytical value 85.24 5.85 Theoretical value 85.71 5.82 Theoretical value is 4,4 It was calculated by assuming that the 1- (α-methylbenzylidene) bisphenol and α, α-dichlorotoluene reacted 1: 1.
また生成物の1H−NMRスペクトル（400MHz）を図１に
示す。The 1 H-NMR spectrum (400 MHz) of the product is shown in FIG.
以上の結果より、生成ポリマーは繰り返し単位が からなるフェニル基を側鎖に持つ芳香族ポリエーテル重
合体であることを確認した。From the above results, the repeating unit of the produced polymer Was confirmed to be an aromatic polyether polymer having a phenyl group in the side chain.
この重合体をシリンダー温度250℃、金型温度120℃の
条件下で厚さ1.2mm、直径120mmの円板に射出成形した。
得られた射出成形板の直径80mmの部分の複屈折を、日本
光学（株）製偏向顕微鏡にセナルモンコンペンセータを
付けて測定したところシングルパスで7nmであった。This polymer was injection molded into a disk having a thickness of 1.2 mm and a diameter of 120 mm under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 120 ° C.
The birefringence of the 80 mm diameter portion of the obtained injection-molded plate was measured by using a deflection microscope manufactured by Nihon Kogaku Co., Ltd. with a Senarmont compensator and found to be 7 nm in a single pass.
実施例２ 4,4′−（ｍ−フェニレンジイソプロピリデン）ビス
フェノール13.84g（0.04mol）、α，α−ジクロロトル
エン6.4g（0.04mol）、水酸化ナトリウム6.4g（1.16mo
l）およびＮ−メチル−２−ピロリドン40mlの混合溶液
を撹拌しながら、80℃において５時間反応を行った。反
応終了後、生成物をメタノール中に投入して重合体を回
収した。Example 2 13.4 g (0.04 mol) of 4,4 '-(m-phenylenediisopropylidene) bisphenol, 6.4 g (0.04 mol) of α, α-dichlorotoluene, 6.4 g of sodium hydroxide (1.16mo)
While stirring a mixed solution of l) and 40 ml of N-methyl-2-pyrrolidone, the reaction was carried out at 80 ° C. for 5 hours. After completion of the reaction, the product was put into methanol to collect the polymer.
得られた重合体を塩化メチレンに溶解し、不溶の塩を
濾過した後に、再びメタノール中に投入して精製した。
得られた白色固体を真空下40℃にて乾燥したところ収量
14.5gであった。The obtained polymer was dissolved in methylene chloride, the insoluble salt was filtered off, and the mixture was again poured into methanol for purification.
The yield of the obtained white solid was dried under vacuum at 40 ° C.
It was 14.5 g.
得られた重合体についてGPC測定を行ったところ、重
量平均分子量はポリスチレン換算値で8.5×104であっ
た。GPC measurement of the obtained polymer showed that the weight average molecular weight was 8.5 × 10 4 in terms of polystyrene.
また、生成物のIRおよび元素分析の結果は次のとおり
であった。The results of IR and elemental analysis of the product were as follows.
IRスペクトル（cm-1）:3061（ｍ）,3035（ｍ）,2964
（ｓ）,2929（ｍ）,2870（ｍ）,1689（ｍ）,1606
（ｓ）,1581（ｍ）,1506（ｓ）,1452（ｍ）,1417
（ｍ）,1361（ｍ）,1294（ｍ）,1242（ｓ）,1213
（ｓ）,1178（ｓ）,1062（ｍ）,1004（ｍ）,889（ｍ）,
829（ｓ）,797（ｍ）,748（ｗ）,708（ｓ）,696（ｓ）,
573（ｍ） 元素分析 Ｃ（％） Ｈ（％） 分析値 85.32 6.84 理論値 85.71 6.91 理論値は、4,4′−（ｍ−フェニレンジイソプロピリ
デン）ビスフェノールとα，α−ジクロロトルエンが1:
1で反応したと仮定して算出した。IR spectrum (cm -1 ): 3061 (m), 3035 (m), 2964
(S), 2929 (m), 2870 (m), 1689 (m), 1606
(S), 1581 (m), 1506 (s), 1452 (m), 1417
(M), 1361 (m), 1294 (m), 1242 (s), 1213
(S), 1178 (s), 1062 (m), 1004 (m), 889 (m),
829 (s), 797 (m), 748 (w), 708 (s), 696 (s),
573 (m) Elemental analysis C (%) H (%) Analytical value 85.32 6.84 Theoretical value 85.71 6.91 The theoretical value is 4,4 '-(m-phenylene diisopropylidene) bisphenol and α, α-dichlorotoluene 1:
It was calculated by assuming that the reaction occurred in 1.
また生成物の1H−NMRスペクトル（400MHz）を図２に
示す。The 1 H-NMR spectrum (400 MHz) of the product is shown in FIG.
以上の結果より、生成ポリマーは繰り返し単位が からなるフェニル基を側鎖に持つ芳香族ポリエーテル重
合体であることを確認した。From the above results, the repeating unit of the produced polymer Was confirmed to be an aromatic polyether polymer having a phenyl group in the side chain.
この重合体をシリンダー温度250℃、金型温度120℃の
条件下で厚さ1.2mm、直径120mmの円板に射出成形した。
得られた射出成形板の直径80mmの部分の複屈折を、日本
光学（株）製偏向顕微鏡にセナルモンコンペンセータを
付けて測定したところシングルパスで9nmであった。This polymer was injection molded into a disk having a thickness of 1.2 mm and a diameter of 120 mm under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 120 ° C.
The birefringence of a portion of the obtained injection-molded plate having a diameter of 80 mm was measured with a deflection microscope manufactured by Nihon Kogaku Co., Ltd. with a Senarmont compensator, and it was 9 nm in a single pass.
図１は、実施例１により合成された本発明の芳香族ポリ
エーテル重合体の1H−NMRスペクトルチャート（400MH
z）を、図２は実施例２により合成された本発明の芳香
族ポリエーテル重合体の1H−NMRスペクトルチャート（4
00−MHz）をそれぞれ示すFIG. 1 is a 1 H-NMR spectrum chart (400 MHz) of the aromatic polyether polymer of the present invention synthesized according to Example 1.
z), FIG. 2 is a 1 H-NMR spectrum chart (4) of the aromatic polyether polymer of the present invention synthesized according to Example 2.
00-MHz)
Claims (1)
ことを特徴とする、繰り返し単位が一般式（１） （式中、Ａは を示す。） で表されるポリエーテル重合体の製造方法。1. A compound represented by the general formula (2) in the presence of a base. (In the formula, A is Indicates. ) And bisphenol represented by the general formula (3) (In the formula, X and X'represent F, Cl, Br and I respectively.) The repeating unit represented by the general formula (1) is characterized by reacting with α, α-dihalogenotoluene. (In the formula, A is Indicates. ) A method for producing a polyether polymer represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63048641A JP2551088B2 (en) | 1988-03-03 | 1988-03-03 | Process for producing polyether polymer having phenyl group in side chain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63048641A JP2551088B2 (en) | 1988-03-03 | 1988-03-03 | Process for producing polyether polymer having phenyl group in side chain |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01223124A JPH01223124A (en) | 1989-09-06 |
| JP2551088B2 true JP2551088B2 (en) | 1996-11-06 |
Family
ID=12808996
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63048641A Expired - Fee Related JP2551088B2 (en) | 1988-03-03 | 1988-03-03 | Process for producing polyether polymer having phenyl group in side chain |
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| Country | Link |
|---|---|
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|---|---|---|---|---|
| JPH0653472B2 (en) * | 1986-05-30 | 1994-07-20 | 本田技研工業株式会社 | Optical axis adjustment device for motorcycles |
| JPH01126329A (en) * | 1987-11-11 | 1989-05-18 | Tosoh Corp | Resin for optical materials |
-
1988
- 1988-03-03 JP JP63048641A patent/JP2551088B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01223124A (en) | 1989-09-06 |
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