JPH0463811A - Copolymer having azomethine group in side chain - Google Patents
Copolymer having azomethine group in side chainInfo
- Publication number
- JPH0463811A JPH0463811A JP17455890A JP17455890A JPH0463811A JP H0463811 A JPH0463811 A JP H0463811A JP 17455890 A JP17455890 A JP 17455890A JP 17455890 A JP17455890 A JP 17455890A JP H0463811 A JPH0463811 A JP H0463811A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- group
- formula
- repeating units
- mol
- 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
- 229920001577 copolymer Polymers 0.000 title abstract description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 2
- 230000003287 optical effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000005693 optoelectronics Effects 0.000 abstract description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 abstract description 4
- 238000004891 communication Methods 0.000 abstract description 3
- 230000010365 information processing Effects 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- -1 aniline compound Chemical class 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012442 inert solvent Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ZYDGSCASWIIPQW-UHFFFAOYSA-N 4-[[4-(dimethylamino)phenyl]iminomethyl]phenol Chemical compound OC1=CC=C(C=NC2=CC=C(C=C2)N(C)C)C=C1 ZYDGSCASWIIPQW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000001641 gel filtration chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CFDRQRFAQCJPBZ-UHFFFAOYSA-N 1-chlorohexan-1-ol Chemical compound CCCCCC(O)Cl CFDRQRFAQCJPBZ-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000004702 methyl esters Chemical group 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、側鎖にアゾメチン基を有する共重合体に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a copolymer having an azomethine group in its side chain.
［従来の技術及び発明が解決しようとする課題］本発明
の共重合体は、文献未載の新規な共重合体であり、オプ
トエレクトロニクス分野に於ける各種デバイスとして有
用な高分子材料を提供することを目的とする。[Prior art and problems to be solved by the invention] The copolymer of the present invention is a novel copolymer that has not been described in any literature, and provides a polymeric material useful as various devices in the optoelectronics field. The purpose is to
［課題を解決するための手段］
本発明の共重合体は、次式（Ｉ）
←傭２−Ｃ←
ｃ＝ｏ （Ｉ）Ｒ２
［式（Ｉ）中、Ｒ１は水素原子又はメチル基を表わし、
Ｒ２はメチル基又はエチル基を表わす］で示される繰り
返し単位５〜７０モル％及び次式（ＩＩ ）
Ｒ３
←利１□−Ｃ←
Ｃ：０ （ＩＩ）ｏ ＋
−ｃｏ２ｈ−ｏ−ｏ−ＣＨ＝ Ｎ Ｇ 。[Means for Solving the Problems] The copolymer of the present invention has the following formula (I) ←2-C← c=o (I)R2 [In formula (I), R1 represents a hydrogen atom or a methyl group. Representation,
5 to 70 mol% of repeating units represented by R2 represents a methyl group or an ethyl group and the following formula (II)
-co2h-o-o-CH=NG.
（式中、Ｒ３は水素原子又はメチル基を表わし、Ｘは１
〜２０の整数を表わし、Ｄは電子供与基を表わす）で示
される繰り返し単位９５〜３０モル％からなり、数平均
分子量が１０００〜１００万であることを特徴とする。(In the formula, R3 represents a hydrogen atom or a methyl group, and X is 1
It consists of 95 to 30 mol% of repeating units represented by an integer of 20 to 20, and D represents an electron donating group, and is characterized by having a number average molecular weight of 1,000 to 1,000,000.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の共重合体は、前記式（１）で示される繰り返し
単位［以下、繰り返し単位（１）と５ｔう］及び式（Ｉ
Ｎで示される繰り返し単位［以下、繰り返し単位（ＩＮ
という］からなるポリ（メタ）アクリル系共重合体であ
る。The copolymer of the present invention comprises a repeating unit represented by the above formula (1) [hereinafter referred to as repeating unit (1) and 5t] and a formula (I
Repeating unit indicated by N [hereinafter, repeating unit (IN
It is a poly(meth)acrylic copolymer consisting of
繰り返し単位（Ｉ）と繰り返し単位（旧の組成比率は、
繰り返し単位（１）が５〜７０モル％、繰り返し単位（
１口が９５〜３０モル％であり、好ましくは繰り返し単
位（１）が５〜６０モル％、繰り返し単位（ＩＩ ）が
９５〜４０モル％、さらに好ましくは繰り返し単位（Ｉ
）が１０〜５０モル％、繰り返し単位（ＩＩ ）が９０
〜５０モル％である。Repeating unit (I) and repeating unit (old composition ratio is
5 to 70 mol% of repeating unit (1), repeating unit (
One mouth is 95 to 30 mol%, preferably repeating unit (1) is 5 to 60 mol%, repeating unit (II) is 95 to 40 mol%, and more preferably repeating unit (I) is 95 to 30 mol%.
) is 10 to 50 mol%, and the repeating unit (II) is 90
~50 mol%.
本発明の共重合体は、交互共重合体、ランダム共重合体
及びブロック共重合体のいずれであってもよい。The copolymer of the present invention may be any of an alternating copolymer, a random copolymer, and a block copolymer.
本発明の共重合体は、数平均分子量が
１０００〜１００万であり、好ましくは５０００〜７０
万、さらに好ましくは１万〜５０万である。The copolymer of the present invention has a number average molecular weight of 1,000 to 1,000,000, preferably 5,000 to 70,000.
10,000, more preferably 10,000 to 500,000.
前記式（Ｉ）中、Ｒ１は水素原子又はメチル基を表わし
、好ましくはメチル基である。In the formula (I), R1 represents a hydrogen atom or a methyl group, preferably a methyl group.
Ｒ２はメチル基又はエチル基を表わし、好ましくはメチ
ル基である。R2 represents a methyl group or an ethyl group, preferably a methyl group.
前記式（ｎ）中、Ｒ３は水素原子又はメチル基を表わし
、好ましくはメチル基である。In the formula (n), R3 represents a hydrogen atom or a methyl group, preferably a methyl group.
Ｘは、１〜２０の整数を表わし、好ましくは１〜１２で
あり、さらに好ましくは１〜８である。X represents an integer of 1 to 20, preferably 1 to 12, and more preferably 1 to 8.
Ｄで表わされる電子供与基とは、ハメット則において置
換基定数Ｏが負の置換基をいう。中でも０が−０２以下
のものが好ましい。The electron-donating group represented by D refers to a substituent whose substituent constant O is negative according to Hammett's rule. Among them, those in which 0 is −02 or less are preferable.
このような電子供与基としては、例えば、アミノ基、ジ
メチルアミノ基、ジエチルアミノ基、メチルアミノ基、
エチルアミノ基、ヒドロキシ基、メトキシ基、エトキシ
基などを挙げることができる。中でも好ましいのは、ジ
メチルアミノ基、ジエチルアミノ基であり、さらに好ま
しくはジメチルアミノ基である。Examples of such electron donating groups include amino group, dimethylamino group, diethylamino group, methylamino group,
Examples include ethylamino group, hydroxy group, methoxy group, and ethoxy group. Among them, dimethylamino group and diethylamino group are preferred, and dimethylamino group is more preferred.
本発明の共重合体は、例えば、次の反応工程１〜４を経
て製造することができる。The copolymer of the present invention can be produced, for example, through the following reaction steps 1 to 4.
（反応工程１）
（ＩＩＩ ）
［式（ＩＩＩ ）及び（ＩＶ）中、Ｄは前記と同義であ
る］
前記式（ＩＩＩ ）で示されるアニリン化合物とこれに
対してやや過剰のｐ−ヒドロキシベンズアルデヒドとを
エタノール等の溶媒中で酢酸を触媒とし、溶媒を留去し
ながら反応させて前記式（ＩＶ）で示されるアゾメチン
化合物を合成する。(Reaction step 1) (III) [In formulas (III) and (IV), D has the same meaning as above] An aniline compound represented by the above formula (III) and p-hydroxybenzaldehyde in a slight excess with respect to the aniline compound is reacted in a solvent such as ethanol using acetic acid as a catalyst while distilling off the solvent to synthesize an azomethine compound represented by the formula (IV).
（反応工程２）
ａｌｌ
（ＩＶ ） ＋ Ｃ４ｆｃＨ２ｈ ０１（（Ｖ）
［式（Ｖ）及び（Ｖｌ）中、Ｘ及びＤは前記と同義であ
る］
アゾメチン化合物（ＩＶ ）とクロロアルコール（Ｖ）
とを水素化ナトリウムの存在下に不活性溶媒中で反応さ
せて化合物（Ｖｌ）を合成する。(Reaction step 2) all (IV) + C4fcH2h 01 ((V) [In formulas (V) and (Vl), X and D have the same meanings as above] Azomethine compound (IV) and chloroalcohol (V)
Compound (Vl) is synthesized by reacting them in an inert solvent in the presence of sodium hydride.
不活性溶媒としては、反応成分に対して不活性であれば
特に制限はないが、Ｎ、Ｎ−ジメチルホルムアミド、ヘ
キサメチレンフオスホニルアミド等の極性溶媒が好まし
い。The inert solvent is not particularly limited as long as it is inert to the reaction components, but polar solvents such as N,N-dimethylformamide and hexamethylene phosphonylamide are preferred.
反応モル比は、アゾメチン化合物（ＩＶ）１モルに対し
てクロロアルコール（Ｖ）が１，０〜２０（＠モル量、
好ましくは、１．２〜１．５１合モル量である。The reaction molar ratio is 1.0 to 20 (@molar amount,
Preferably, the amount is 1.2 to 1.51 total moles.
水素化ナトリウムの使用量は、アゾメチン化合物（ＩＶ
）と等モル量が好ましい。The amount of sodium hydride used is based on the azomethine compound (IV
) is preferably used in an equimolar amount.
反応温度は、８０〜２００℃、好ましくは１００〜１５
０℃である。The reaction temperature is 80-200°C, preferably 100-15°C.
It is 0°C.
反応時間は、２〜３０時間である。Reaction time is 2 to 30 hours.
（反応工程３）
（■ロ ）
ＣＩ＋□ ＝（：Ｒ’
［式（Ｖｌｌ）及び（■）中、Ｒ’、Ｄ及びＸは、前記
と同義である］
化合物（Ｖｌ）と（メタ）アクリロイルクロリド（■旧
とをトリエチルアミンの存在下に不活性溶媒中て反応さ
せて重合活性モノマー（■）を合成する。(Reaction step 3) (■B) CI+□ = (:R' [In formulas (Vll) and (■), R', D and X have the same meanings as above] Compound (Vl) and (meth)acryloyl A polymerizable monomer (■) is synthesized by reacting chloride (■) with chloride in an inert solvent in the presence of triethylamine.
不活性溶媒としては、反応成分に対して不活性であれば
特に制限はないが、ジオキサン、テトラヒドロフラン等
の環状エーテル系溶媒が好ましい。The inert solvent is not particularly limited as long as it is inert to the reaction components, but cyclic ether solvents such as dioxane and tetrahydrofuran are preferred.
反応モル比は、化合物（Ｖｌ）１モルに対して、（メタ
）アクリロイルクロリド（Ｖｌｌ）が１．０〜２０倍モ
ル量、好ましくは、１２〜１５倍モル量である。The reaction molar ratio is 1.0 to 20 times, preferably 12 to 15 times, molar amount of (meth)acryloyl chloride (Vll) to 1 mole of compound (Vl).
トリエチルアミンの使用量は、（メタ）アクリロイルク
ロリドと等モル量が好ましい。The amount of triethylamine used is preferably equimolar to (meth)acryloyl chloride.
反応温度は、０〜８０℃、好ましくは０〜４０℃である
。The reaction temperature is 0 to 80°C, preferably 0 to 40°C.
反応時間は、２〜２０時間である。Reaction time is 2 to 20 hours.
（反応工程４）
重合活性モノマー（■）と（メタ）アクリル酸メチルモ
ノマー又は（メタ）アクリル酸エチルモノマーとを不活
性溶媒中で重合開始剤の存在下に重合させて本発明の共
重合体を得ることができる。(Reaction step 4) The copolymer of the present invention is obtained by polymerizing the polymerization active monomer (■) and the methyl (meth)acrylate monomer or the ethyl (meth)acrylate monomer in an inert solvent in the presence of a polymerization initiator. can be obtained.
共重合体の組成比は、各モノマーの仕込み量を調節する
ことにより、所定の組成比に制御することができる。The composition ratio of the copolymer can be controlled to a predetermined composition ratio by adjusting the amount of each monomer charged.
重合開始剤としては、ベンゾイルペルオキシド、アゾビ
スイソブチロニトリル、ラウロイルペルオキシド等のラ
ジカル開始剤やｎ−ブチルリチウム、ナトリウムナフタ
レン等のアニオン開始剤を挙げることができる。Examples of the polymerization initiator include radical initiators such as benzoyl peroxide, azobisisobutyronitrile, and lauroyl peroxide, and anionic initiators such as n-butyllithium and sodium naphthalene.
重合開始剤の使用量は、使用するモノマーの合計モル数
に対して、１１５０〜１１５００倍モル量、好ましくは
、１／１００〜ｌ／３００倍モル量、さらに好ましくは
、ｌ／１００〜１／２００倍モル量である。The amount of the polymerization initiator to be used is 1150 to 11500 times, preferably 1/100 to 1/300 times, more preferably 1/100 to 1/300 times the total number of moles of monomers used. It is 200 times the molar amount.
不活性溶媒としては、重合活性モノマー（■）に対して
不活性であれば特に制限はないが、トルエン、ベンゼン
、ヘキサン等の炭化水素系溶媒が好ましい。The inert solvent is not particularly limited as long as it is inert to the polymerization active monomer (■), but hydrocarbon solvents such as toluene, benzene, and hexane are preferred.
重合温度は、−１００〜８０℃である。The polymerization temperature is -100 to 80°C.
重合時間は、２〜３０時間である。Polymerization time is 2 to 30 hours.
得られた本発明の共重合体の精製には、再沈法を採用す
ることができる。A reprecipitation method can be employed to purify the obtained copolymer of the present invention.
このようにして得られた本発明の共重合体は、数平均分
子量が、１０００〜１００万であり、示差走査熱量計（
ＤＳＣ）による吸熱ピークは、重合体の分子量によって
多少異なるが、８０〜１４０°Ｃに観測することができ
る（昇温速度。The copolymer of the present invention thus obtained has a number average molecular weight of 1,000 to 1,000,000, and a differential scanning calorimeter (
The endothermic peak (DSC) can be observed at 80 to 140°C (temperature increase rate), although it varies somewhat depending on the molecular weight of the polymer.
１０℃／ｍ１ｎ）。10°C/m1n).
本発明の共重合体を主成分とする高分子材料は、キャス
トあるいはスピンコード等の方法によりフィルムあるい
は薄膜に成形して、光情報処理や光通信などのオプトエ
レクトロニクス分野で用いられる電気光学−デバイス、
第二高調波発生デバイス、導波路等のデバイスの材料と
して、好適に用いることができる。The polymeric material containing the copolymer of the present invention as a main component can be formed into a film or thin film by a method such as casting or spin cording, and can be used in electro-optic devices used in optoelectronic fields such as optical information processing and optical communications. ,
It can be suitably used as a material for devices such as second harmonic generation devices and waveguides.
（実施例）
以下、実施例を示し本発明の高分子化合物をさらに具体
的に説明する。なお本発明はこの実施例によってなんら
限定されるものではない。(Example) Hereinafter, the polymer compound of the present invention will be explained in more detail with reference to Examples. Note that the present invention is not limited in any way by this example.
［実施例１］
メタクリル酸６−４−ジメチルアミノフエニ■４−ジメ
チルアミノ−Ｎ−（４−ヒドロキシベンジリデン）アニ
リンの合成
ｐ−ジメチルアミノアニリン（２７，２ｇ０．２ｍｏ／
）とｐ−ヒドロキシベンズアルデヒド（２６，８ｇ、０
．２２ｍｏｆ ）をエタノール］ｐに溶解し、触媒とし
て酢酸２−を加えた。次に、この滴液を常圧で加熱しな
がらエタノールを留去した６留去エタノール量が０．８
ｇ程度になったときに加熱をやめ、反応混合物を氷水で
冷却し、４−ジメチルアミノ−Ｎ−（４−ヒドロキシベ
ンジリデン）アニリンの結晶を析出させた。結晶は？戸
別し、エタノールで充分洗浄した後、乾燥した。[Example 1] 6-4-dimethylaminophene methacrylate ■ Synthesis of 4-dimethylamino-N-(4-hydroxybenzylidene)aniline p-dimethylaminoaniline (27.2g0.2mo/
) and p-hydroxybenzaldehyde (26.8 g, 0
．． 22mof) was dissolved in ethanol]p, and acetic acid 2- was added as a catalyst. Next, the ethanol was distilled off while heating this droplet at normal pressure.The amount of ethanol distilled off was 0.8
When the temperature reached about 1.5 g, heating was stopped, and the reaction mixture was cooled with ice water to precipitate crystals of 4-dimethylamino-N-(4-hydroxybenzylidene)aniline. What about crystals? They were taken from house to house, thoroughly washed with ethanol, and then dried.
収量４３．２ｇ （９０％） 、 ｍ、ｐ、２６４〜２
６５°Ｃ
■４−ジメチルアミノーＮ−［４−（６−ヒドロキシへ
キサメチレンオキシ）ベンジリデン１アニリンの合成
得られた４−ジメチルアミノ−Ｎ−（４−ヒドロキシベ
ンジリデン）アニリン（１６，８ｇ、０．０７ｍｏｆ）
をＮ、Ｎ−ジメチルホルムアミド３００ｉに溶解し、０
°Ｃまて冷却した。次に、この滴液に水素化ナトリウム
（１，７６ｇ、０．０７３５ｍｏｆ）を撹拌しながら加
えた。Yield 43.2g (90%), m, p, 264~2
65°C ■ Synthesis of 4-dimethylamino-N-[4-(6-hydroxyhexamethyleneoxy)benzylidene 1 aniline The obtained 4-dimethylamino-N-(4-hydroxybenzylidene)aniline (16.8 g, 0.07mof)
was dissolved in 300 i of N,N-dimethylformamide and 0
Cooled to °C. Next, sodium hydride (1.76 g, 0.0735 mof) was added to this droplet with stirring.
Ｈ２の発生が終了した後、この溶液に１−クロロヘキサ
ノール（１４，３ｇ、０．１０５ｍｏＪ）を添加し、１
２０°Ｃで５〜８時間撹拌！−た。反応終了後、反応混
合物を１５℃の水に注いだ。After the evolution of H2 was completed, 1-chlorohexanol (14.3 g, 0.105 moJ) was added to the solution and 1
Stir at 20°C for 5-8 hours! -ta. After the reaction was completed, the reaction mixture was poured into 15°C water.
析出した結晶を７戸別して４−ジメチルアミン−Ｎ−［
４−（６−ヒドロキシへキサメチレンオキシ）ベンジリ
デン１アニリンの粗結晶を得た。粗結晶はエタノールで
再結晶させて精製した。The precipitated crystals were separated into 7 units and 4-dimethylamine-N-[
Crude crystals of 4-(6-hydroxyhexamethyleneoxy)benzylidene-1-aniline were obtained. The crude crystals were purified by recrystallization with ethanol.
収量１９．５ｇ （８２％） 、 ｍ、ｐ、８６〜８７
°Ｃ■メタクリル酸６−（４−ジメチルアミノフェニル
イミノメチルフェノキシ）ヘキシルの合成得られた４−
ジメチルアミノ−Ｎ−［４−（６−ヒドロキシへキサメ
チレンオキシ）ベンジリデン１アニリン（１２，９ｇ、
０．０３８ｍｏｌ ）を溶媒ジオキサン２００ｄに溶解
させた。Yield 19.5g (82%), m, p, 86-87
°C ■ Synthesis of 6-(4-dimethylaminophenyliminomethylphenoxy)hexyl methacrylate The obtained 4-
Dimethylamino-N-[4-(6-hydroxyhexamethyleneoxy)benzylidene 1 aniline (12.9g,
0.038 mol) was dissolved in the solvent dioxane 200d.
次に、このン容液にトリエチルアミン（５９１−１０，
０４２ｍｏｆ）と、メタクリロイルクロリド（４，１０
ｄ、０．０４２ｍｏｐ）とを加え、２５°Ｃで５時間撹
拌した。この反応混合物を酢酸エチルで抽出し、有機層
を水で充分に洗浄した後に、硫酸マグネシウムで乾燥し
、次いで酢酸エチルを留去してメタクリル酸６−（４−
ジメチルアミノフェニルイミノメチルフェノキシ）ヘキ
シルの粗結晶を得た。粗結晶は、ヘキサン／酢酸エチル
（１１）の混合溶媒で再結晶させて精製した。Next, add triethylamine (591-10,
042mof) and methacryloyl chloride (4,10mof)
d, 0.042mop) and stirred at 25°C for 5 hours. This reaction mixture was extracted with ethyl acetate, and the organic layer was thoroughly washed with water, dried over magnesium sulfate, and then ethyl acetate was distilled off to remove methacrylic acid 6-(4-
Crude crystals of dimethylaminophenyliminomethylphenoxy)hexyl were obtained. The crude crystals were purified by recrystallization with a mixed solvent of hexane/ethyl acetate (11).
収量７．０ｇ （４５％） 、 ｍ、ｐ、８５〜８６°
Ｃ■メタクリル酸６−（４−ジメチルアミノフェニルイ
ミノメチルフェノキシ）ヘキシルとメタクリル酸メチル
との共重合
得られたメタクリル酸６−（４−ジメチルアミノフェニ
ルイミノメチルフェノキシ）ヘキシル（２，４６ｇ、６
． ＯＸ ｌ Ｏ−”ｍｏｌ）とメタクリル酸メチル
（０，６ｇ、６． Ｏｘ １０−３ｍｏｌ ）とをトル
エン（１，０ｍｆ）中で、ラウロイルペルオキシド（１
２ｍｇ、３． Ｑｘ １０−５ｍｏｐ）の存在下に７０
°Ｃで５時間重合させ、次いでその反応混合物をメタノ
ール中に注いで表題の目的物を得た。Yield 7.0g (45%), m, p, 85-86°
C■ Copolymerization of 6-(4-dimethylaminophenyliminomethylphenoxy)hexyl methacrylate and methyl methacrylate The resulting 6-(4-dimethylaminophenyliminomethylphenoxy)hexyl methacrylate (2.46 g, 6
．． In toluene (1.0 mf), lauroyl peroxide (1
2mg, 3. 70 in the presence of Qx 10-5mop)
Polymerization was carried out at °C for 5 hours, and then the reaction mixture was poured into methanol to obtain the title product.
これをクロロホルムに溶解し、次いでメタノール中で再
沈させて精製した。This was purified by dissolving it in chloroform and then reprecipitating it in methanol.
この精製物は、ゲル濾過クロマトグラフィー（ＧＰＣ）
により、数平均分子量が７〜８万の共重合体であること
を確認した。This purified product was subjected to gel filtration chromatography (GPC).
It was confirmed that the copolymer had a number average molecular weight of 70,000 to 80,000.
同定は、’Ｈ−ＮＭＲ（４００ＭＨｚ、ＣＤＣｆｆ、）
により行い、得られた共重合体が側鎖にアゾメチン基を
有する表題の目的物であることを確認した。Identification was by 'H-NMR (400MHz, CDCff,)
It was confirmed that the obtained copolymer was the title target product having an azomethine group in the side chain.
その’Ｈ−ＮＭＲスペクトルを第１図に示し、’Ｈ−Ｎ
ＭＲの測定結果を以下に示す。The 'H-NMR spectrum is shown in Figure 1.
The MR measurement results are shown below.
Ｃ１１３
Ｃ１１゜
値（ｐｐｍ １ 帰属 積分比０８〜
２、Ｏａ １７．７
３．５〜３．６ ｂ ２．９３９〜
４． Ｏｃ ３・８６６〜７．８
ｄ ８．０８．３〜８．４ ｅ
１．０２．８〜２、ｇ ｆ５．９
［但し、前記帰属ａの積分比（１７，７）の内、４．８
は、ポリメタクリル酸メチルに帰因する〕また、共重合
体のメタクリル酸６−（４−ジメチルアミノフェニルイ
ミノメチルフェノキシ）ヘキシルとメタクリル酸メチル
との組成比（ｍ＝ｎ）は、アゾメチンプロトン（ｅ）に
対するメチルエステルプロトン（ｂ）の比から算出した
。C113 C11° value (ppm 1 Attribution Integral ratio 08~
2, Oa 17.7 3.5~3.6 b 2.939~
4. Oc 3・866～7.8
d 8.08.3~8.4 e
1.02.8~2, g f5.9 [However, of the integral ratio (17,7) of the above assignment a, 4.8
is attributed to polymethyl methacrylate] In addition, the composition ratio (m=n) of 6-(4-dimethylaminophenyliminomethylphenoxy)hexyl methacrylate and methyl methacrylate in the copolymer is determined by the azomethine proton ( It was calculated from the ratio of methyl ester proton (b) to e).
ｍ：ｎ＝１：１、 （ｂ ／ ｅ ＝ ２ 、 ９
）得られた目的物の第二高調波発生（ＳＨＧ）について
評価した。m:n=1:1, (b/e=2,9
) Second harmonic generation (SHG) of the obtained target product was evaluated.
ガラスセルに充填した粉末サンプルに、ＮｄＹＡＧレー
ザ−（Ｓｐｅｃｔｒａ Ｐｈｙｓｉｃｓ社製ＹＡＧレー
ザーＤＣＲ−３、ピーク出力１１０ＭＷ）の１．０６４
１７１１１線を照射したところ、緑色の発光が認められ
た。The powder sample filled in the glass cell was heated with 1.064 mL of NdYAG laser (YAG laser DCR-3 manufactured by Spectra Physics, peak output 110 MW).
When irradiated with 17111 rays, green light emission was observed.
［実施例２］
実施例１の■の工程で用いた１−クロロヘキサノールに
代えて、１−クロロプロパツール（９，９ｇ、Ｏ，１０
５ｍｏｎ’）を用いたほかは実施例１と同様にしてメタ
クリル酸３−（４−ジメチルアミノフェニルイミノメチ
ルフェノキシ）プロピルを合成し、これとメタクリル酸
メチルとを実施例１と同様にして共重合させた。[Example 2] 1-chloropropatol (9.9 g, O, 10
3-(4-dimethylaminophenyliminomethylphenoxy)propyl methacrylate was synthesized in the same manner as in Example 1, except that 5mon') was used, and this and methyl methacrylate were copolymerized in the same manner as in Example 1. I let it happen.
得られた表題の共重合体は、ゲル濾過クロマトグラフィ
ー（ＧＰＣ）により、数平均分子量が６〜７万の共重合
体であることを確認した。The title copolymer thus obtained was confirmed by gel filtration chromatography (GPC) to have a number average molecular weight of 60,000 to 70,000.
同定は、実施例１と同様にして行ない、得られた重合体
が側鎖にアゾメチン基を有する表題の目的物であること
を確認した。Identification was carried out in the same manner as in Example 1, and it was confirmed that the obtained polymer was the title target product having an azomethine group in the side chain.
’Ｈ−ＮＭＲの測定結果を以下に示す。'H-NMR measurement results are shown below.
Ｃ１ｌ 、 ＣＩ＋。C1l, CI+.
値（ｐｐｍ） 帰属 積分比０．８〜
２．Ｏａ １１．９３５〜３．６ ｂ
２．９３９〜４． Ｏｃ
３．９６．５〜７．７ ｄ ８．０
Ｂ、 ３〜８．４ ｅ １．、０２
８〜２．９ ｆ ５．９［但し、前
記帰属ａの積分比（１ｔ、９）の内、４．８は、ポリメ
タクリル酸メチルに帰因する］また、共重合体の組成比
を実施例１と同様にして算出した。Value (ppm) Attribution Integral ratio 0.8~
2. Oa 11.935~3.6b
2.939~4. Oc
3.96.5~7.7d 8.0
B, 3-8.4 e 1. ,02
8 to 2.9 f 5.9 [However, of the integral ratio (1t, 9) of the above assignment a, 4.8 is attributable to polymethyl methacrylate] In addition, the composition ratio of the copolymer was determined. Calculated in the same manner as in Example 1.
ｍ：ｎ＝１：１、 （ｂ／ｅ＝２．９）得られた目的
物に実施例１と同様にしてＮｄ：ＹＡＧレーザーの１．
０６４Ｐ線を照射したところ、緑色の発光が認められた
。m:n=1:1, (b/e=2.9) The obtained target object was treated with the Nd:YAG laser in the same manner as in Example 1.
When irradiated with 064P radiation, green light emission was observed.
［発明の効果］
本発明によると、光情報処理や光通信等のオプトエレク
トロニクス分野で用いる種々のデバイス、例えば、電気
光学−デバイス、第二高調波発生デバイス、圧電デバイ
ス、導波路１、特にフィルム状デバイス、積層体又は集
合体デバイスとして有用な高分子材料を提供することが
できる。[Effects of the Invention] According to the present invention, various devices used in the field of optoelectronics such as optical information processing and optical communication, such as electro-optical devices, second harmonic generation devices, piezoelectric devices, waveguides 1, especially films. A polymer material useful as a shaped device, a laminate, or an aggregate device can be provided.
第１図は、実施例１で得られたメタクリル酸６−（４−
ジメチルアミンフェニルイミノメチルフェノキシ）ヘキ
シルとメタクリル酸メチルとの共重合体の’ Ｈ−ＮＭ
Ｒスペクトル図である。Figure 1 shows the methacrylic acid 6-(4-
'H-NM of a copolymer of dimethylaminephenyliminomethylphenoxy)hexyl and methyl methacrylate
It is an R spectrum diagram.
Claims (1)
し、Ｒ＾２はメチル基又はエチル基を表わす］で示され
る繰り返し単位５〜７０モル％及び 次式（II）： ▲数式、化学式、表等があります▼（II） （式中、Ｒ＾２は水素原子又はメチル基を表わし、Ｘは
１〜２０の整数を表わし、Ｄは電子供与基を表わす）で
示される繰り返し単位９５〜３０モル％からなり、数平
均分子量が１０００〜１００万であることを特徴とする
共重合体。[Claims] Following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In formula (I), R^1 represents a hydrogen atom or a methyl group, and R^2 represents a methyl group. or ethyl group] and the following formula (II): ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^2 represents a hydrogen atom or a methyl group. , X represents an integer of 1 to 20, and D represents an electron donating group), and has a number average molecular weight of 1,000 to 1,000,000. Combined.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17455890A JPH0463811A (en) | 1990-07-03 | 1990-07-03 | Copolymer having azomethine group in side chain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17455890A JPH0463811A (en) | 1990-07-03 | 1990-07-03 | Copolymer having azomethine group in side chain |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0463811A true JPH0463811A (en) | 1992-02-28 |
Family
ID=15980659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17455890A Pending JPH0463811A (en) | 1990-07-03 | 1990-07-03 | Copolymer having azomethine group in side chain |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0463811A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105518036A (en) * | 2013-07-04 | 2016-04-20 | 日产化学工业株式会社 | Polarized ultraviolet-anisotropic material |
-
1990
- 1990-07-03 JP JP17455890A patent/JPH0463811A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105518036A (en) * | 2013-07-04 | 2016-04-20 | 日产化学工业株式会社 | Polarized ultraviolet-anisotropic material |
| CN105518036B (en) * | 2013-07-04 | 2018-01-02 | 日产化学工业株式会社 | Polarized UV rays anisotropisation material |
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