JPH0321609A - Organic boron-containing polymer - Google Patents
Organic boron-containing polymerInfo
- Publication number
- JPH0321609A JPH0321609A JP1157518A JP15751889A JPH0321609A JP H0321609 A JPH0321609 A JP H0321609A JP 1157518 A JP1157518 A JP 1157518A JP 15751889 A JP15751889 A JP 15751889A JP H0321609 A JPH0321609 A JP H0321609A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- reacted
- straight chain
- polymer
- 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
- 229920000642 polymer Polymers 0.000 title abstract description 27
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title abstract description 15
- 229910052796 boron Inorganic materials 0.000 title abstract description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 6
- 230000005693 optoelectronics Effects 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 2
- 239000012279 sodium borohydride Substances 0.000 abstract description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 abstract description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003708 ampul Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000519695 Ilex integra Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は側鎖に棒状の２−（ｐ一置換フェニノレ）−
１． ３． ２−ジオキサポリナン骨格を有する有機ホ
ウ素含有ポリマーに関し，このボリマーはオプトエレク
トロニクス分野，特に光記録材料，偏光板，非線形光学
材料などへの応用が期待される０〔従来の技術〕
本発明の有機ホウ素含有ポリマーは文献未記載の化合物
である。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a rod-shaped 2-(p-monosubstituted phenyl)-
1. 3. Regarding organic boron-containing polymers having a 2-dioxaporinane skeleton, this polymer is expected to be applied in the field of optoelectronics, particularly in optical recording materials, polarizing plates, nonlinear optical materials, etc. [Prior Art] The organic boron-containing polymer of the present invention The polymer is a compound that has not been described in any literature.
本発明は新規な有機ホウ素含有ポリマーを提供すること
を目的とする。The object of the present invention is to provide a novel organic boron-containing polymer.
本発明は，一般式ＣＩ）
（式中Ｒは炭素数ｌ〜１３個の直鎖アルキル基，炭素数
１〜ｌ３個の直鎖アルコキシ基，２〜１４個の直鎖アル
コキシ力ルポニル基，ハロゲン原子又はシアノ基を，Ｘ
は水素原子又はメチル基を，ｎは２〜１５の整数をそれ
ぞれ示す）で表わされる繰返し単位を有する有機ホウ素
含有ボリマーである。The present invention is based on the general formula CI atom or cyano group,
is an organic boron-containing polymer having a repeating unit represented by a hydrogen atom or a methyl group, and n is an integer from 2 to 15.
上記一般式〔■〕の繰返し単位を有するポリマーの重量
平均分子量は約３，０００〜１，０００，０００ ，好
壕しくは５，０００ − １，０００，０００である。The weight average molecular weight of the polymer having the repeating unit of the general formula [■] is about 3,000 to 1,000,000, preferably 5,000 to 1,000,000.
オプトエレクトロニクス分野に適用する場合には，上記
一般式〔■〕におけるＲ基の種類やｎの値によって変化
するため特定できないが，特に好ましい重量平均分子量
の範囲は５，０００〜４００，０００である。分子量が
３．０００未満であると，物理的性質が一定せず実用上
好ましくない。When applied to the optoelectronics field, the weight average molecular weight is particularly preferably in the range of 5,000 to 400,000, although it cannot be specified because it varies depending on the type of R group and the value of n in the above general formula [■]. . If the molecular weight is less than 3.000, the physical properties will not be constant and this is not preferred in practice.
本発明の有機ホウ素含有ボリマーは，次の一般式〔■〕
（式中Ｒ．Ｘ及びｎは上記と同意義を有する）で表わさ
れる有機ホウ素含有七ノマーを重合して得られ．これら
七ノマーは例えば，次のようにして製造できる。The organic boron-containing polymer of the present invention is obtained by polymerizing an organic boron-containing heptanomer represented by the following general formula [■] (wherein R.X and n have the same meanings as above). These heptanomers can be produced, for example, as follows.
Ｂｒ（ＣＨｚ）ｎＣＨ（ＣＯ２ＣｚＨｓ）， （
Ａ：１〔Ｃ〕
Ｘ
（上記式中ｎ，ｆｌ及びＸは上記と同意義を有し，ＤＢ
Ｕは１．８−ジアザビシクロ（５，４．０：） ウンデ
カ−７−エンを示す）。Br(CHz)nCH(CO2CzHs), (
A:1[C]X (in the above formula, n, fl and X have the same meanings as above, DB
U represents 1,8-diazabicyclo(5,4.0:)undec-7-ene).
このようにして得られた一種又は二棟以上の七ノマーを
重合して，本発明の有機ホウ素含有ボリマーとすること
ができる。One or more heptanomers thus obtained can be polymerized to form the organic boron-containing polymer of the present invention.
重合方法としては，例えば熱ラジカル重合，開始剤を用
いるラジカル重合，紫外線や放射線を用いるラジカル重
合，プチノレリチウムなどを開始剤とするアニオン重合
などの各方法を採用することができる。As the polymerization method, various methods can be employed, such as thermal radical polymerization, radical polymerization using an initiator, radical polymerization using ultraviolet rays or radiation, and anionic polymerization using petinorelithium or the like as an initiator.
ラジカル重合の開始剤として，過酸化物．ジアゾ化物な
ど各種のものが知られているが，過酸化ベンゾイル，ア
ゾビスイソブチロニトリノレなど比較的取扱いやすい化
合物が用いられる。Peroxide as an initiator for radical polymerization. Various types of diazotides are known, but relatively easy-to-handle compounds such as benzoyl peroxide and azobisisobutyronitriole are used.
また重合方法には，塊状重合，スラリー重合，溶液重合
などの種々の方法があるが，いずれの方法で重合しても
よい。Further, there are various polymerization methods such as bulk polymerization, slurry polymerization, and solution polymerization, and any of these methods may be used.
重合時間は重合温度や開始剤の極類により一定しないが
，例えば過酸化ペンゾイノレやアゾビスイソプチロニト
リノレを使用する場合には，重合温度３０〜９０℃で１
〜２０時間が適している。The polymerization time varies depending on the polymerization temperature and the polarity of the initiator, but for example, when using peroxide penzoinole or azobisisobutyronitrinole, the polymerization time is
~20 hours is suitable.
ポリマー分子量の調節は，公知の方法，例えば分子量調
節剤の添加やモノマーに対する重合開始剤の濃度の調節
によシ任意に行うことができる。The polymer molecular weight can be arbitrarily adjusted by known methods, such as adding a molecular weight regulator or adjusting the concentration of polymerization initiator relative to the monomer.
溶液重合法で行う場合の溶媒としては，公知の不活性溶
媒が用いられ，例えばジクロロメタン，テトラヒドロフ
ラン，ベンゼン，トノレエン，キシレンなどの溶媒が好
適である。As a solvent when carrying out the solution polymerization method, a known inert solvent is used, and suitable solvents include, for example, dichloromethane, tetrahydrofuran, benzene, tonoleene, and xylene.
このように重合して得た本発明の有機ホウ素含有ポリマ
ーは例えばオフ゜トエレクトロニクス分野への利用が考
えられるが，各用途の必要に応じて，他のホウ素を含有
しない重合性モノマーとの共重合，異種の本発明有機ホ
ウ素含有ポリマー同志の混合，他のボリマーとの混合，
安定剤，可塑剤などの添加による本発明有機ホウ素含有
ポリマーの改良を行い適用できる。The organic boron-containing polymer of the present invention obtained by polymerization as described above can be used, for example, in the field of off-board electronics, but it may be copolymerized with other boron-free polymerizable monomers, or Mixing different types of organic boron-containing polymers of the present invention, mixing with other polymers,
The organic boron-containing polymer of the present invention can be improved and applied by adding stabilizers, plasticizers, etc.
本発明の有機ホウ素含有ボリマーは新規な化合物であシ
，オフ゜トエレクトロニクス分野，特に光記録材料，偏
光板，非線形光学材料などへの応用が期待される。The organic boron-containing polymer of the present invention is a new compound and is expected to find application in the field of optical electronics, particularly in optical recording materials, polarizing plates, nonlinear optical materials, and the like.
以下に実施例を例示して，本発明を説明するが，実施例
中の％は重量％を示すものとする。The present invention will be explained below with reference to Examples, in which % indicates weight %.
攪拌器，滴下ロート及び還流冷却器を備えた２００ Ｃ
Ｃの三ツ口フラスコに，ジプロモアノレカン７６ｍ ｍ
ｏ ＋と無水エタノー／ｌ／ ５Ｑ ｍｌを仕込み，窒
素気流中テ，予めマロン酸ジエチノレ７５ ｍｍｏｌと
ナトリウムエトキシド７６ ｒｎｍｏｌを無水エタノー
／Ｌ／ ５０ ｍｌに混合溶解させた溶液をエタノール
が還流するように加熱しながら滴下した。滴下は１５分
間で終了し，エタノール還流下にｌ７時間攪拌反応させ
た。200 C with stirrer, addition funnel and reflux condenser
In a three-necked flask, add 76 mm of dipromoanolecane.
O + and anhydrous ethanol/l/5Q ml were prepared, and in a nitrogen stream, a solution prepared by previously mixing and dissolving 75 mmol of diethyl malonate and 76 rnmol of sodium ethoxide in 50 ml of anhydrous ethanol/l was heated so that the ethanol refluxed. was added dropwise while heating. The dropwise addition was completed in 15 minutes, and the mixture was stirred and reacted for 17 hours under ethanol reflux.
反応終了後は，エタノールを留去，残留物から工−テル
抽出した。エーテ／Ｖ溶液を１０％水酸化ナトリウム水
溶液，水の順で洗浄し，無水硫酸ナトリウムで乾燥した
。エーテル溶液から未反応のマロン酸シエチルとジプロ
モアルカンを減圧下留去し，次式〔Ａ〕の化合物を得た
。After the reaction was completed, the ethanol was distilled off, and the residue was extracted with alcohol. The ATE/V solution was washed with a 10% aqueous sodium hydroxide solution and then with water, and dried over anhydrous sodium sulfate. Unreacted ethyl malonate and dipromoalkane were distilled off from the ether solution under reduced pressure to obtain a compound of the following formula [A].
Ｂｒ（ＣＨ２）。ＣＨ （ＣＯ２Ｃ２Ｈ６）２［Ａ）例
．ｎ＝８の場合のプロトンＮＭＲピークは３０分間反応
させた。反応後は不溶物をガラスフィノレターで除き，
メタノール溶液を濃，縮した。濃縮物からエーテル抽出
し，エーテ／Ｖ溶峡を濃縮後，カラムクロマトグラフィ
ー（ ２００メンシュのシリカゲ／” １００ ？ ，
展開溶媒：ベンセンから酢酸エチルの傾斜）により単離
Ｍ製し，２−プロモアノレキル−１．３−プロパンジオ
ールＣＢ］ ヲ得た。Br(CH2). CH (CO2C2H6)2[A) Example. The proton NMR peak for n=8 was reacted for 30 minutes. After the reaction, remove insoluble matter with a glass fino letter,
The methanol solution was concentrated. After extracting ether from the concentrate and concentrating the ether/V lysate, column chromatography (200-mesh silica/100?,
Developing solvent: gradient from benzene to ethyl acetate) to obtain 2-promoanolekyl-1,3-propanediol CB.
得られた各化合物の性状と物性と共に結果を第１表に示
す。The results are shown in Table 1 along with the properties and physical properties of each compound obtained.
この化合物は，これ以上精製せずに次の反応に使用した
。This compound was used in the next reaction without further purification.
攪拌器，温度計及び還流冷却器を備えた２ｔの四ツ目フ
ラスコに，上記化合物［Ａ］ ４Ｑ ｍｍｏｌ ト）タ
ノー／Ｌ’ ５００ ｍｔを仕込み，溶解させた後，攪
拌しながらナトリウムボロハイドライド５９４ｍｍｏｌ
を３０分間かけて少しづつ投入した。投入開始直後
から発熱が始ｔｂ，やがてメタノールが還流し始めるが
．還流がゆるやかに続くように投入する。In a 2t four-eye flask equipped with a stirrer, a thermometer, and a reflux condenser, the above compound [A] 4Q mmol t)tanol/L' 500 mt was charged and dissolved, and then 594 mmol of sodium borohydride was added while stirring.
was added little by little over 30 minutes. Immediately after the start of charging, heat generation started, and soon methanol started to reflux. Pour in so that the reflux continues slowly.
投入完了後もゆるやかに還流するように加熱し，第
１ 表
Ｂ ’ （ ＣＨｚ ）ｎ Ｃ Ｈ （ Ｃ Ｈ２ ０
Ｈ ）２攪拌器，温度計及び還流冷却器付共沸脱水器を
備えた２００ ＣＣの三ツ口フラスコに製造例ｌで得た
２−グロモアルキル−１．３−プロパンシオー／Ｌ／１
０ｍｍｏ＋ ４−置換フェニルホロン酸１０ｍｍｏ
ｌ及びトノレエン５Ｑ ｍｌを仕込み，還流温度で共沸
脱水反応を行なった。ＦＪ１〜２時間で反応を終了し，
トルエンヲ減圧下留去，カラムクロマトクラフィー（
２００メッシュのシリカゲ／’６０？，展開溶媒：シク
ロルエタン）により単離精製し２−（４一置換フェニ／
ｌ’ ） − ４−プロモアルキ／ｌ’−１．３．２−
ンオキサポリナン〔Ｃ〕を得た。After the addition is complete, heat it so that it gently refluxes.
1 Table B' (CHz)n C H (C H2 0
H) 2-Glomoalkyl-1,3-propanesio obtained in Production Example 1/L/1 in a 200 CC three-necked flask equipped with a stirrer, a thermometer and an azeotropic dehydrator with a reflux condenser.
0mmo+ 4-substituted phenylphoronic acid 10mmo
1 and 5Q ml of tonoleene were charged, and an azeotropic dehydration reaction was carried out at reflux temperature. The reaction was completed in 1 to 2 hours,
Distillation of toluene under reduced pressure, column chromatography (
200 mesh silikage/'60? , developing solvent: cycloethane) to isolate and purify the 2-(4-monosubstituted phenyl/
l') - 4-promoalkyl/l'-1.3.2-
Oxapolinan [C] was obtained.
得られた各化合物の性状と物性と共に結果を第２表に示
す。The results are shown in Table 2 along with the properties and physical properties of each compound obtained.
（４） マロン酸ジエチルからの収率。(4) Yield from diethyl malonate.
（４）第２表中の記号は次のことを示す。(4) The symbols in Table 2 indicate the following.
Ｃ：結晶相，Ｓ＾：液晶相のスメクチックＡ相，■．等
方性液体相。C: Crystal phase, S^: Smectic A phase of liquid crystal phase, ■. Isotropic liquid phase.
攪拌器，温度計及び還流冷却器を備えた５Ｑ ｃｃ置換
フェニ／Ｌ’ ） −４−プロモアルキル−１． ３．
２ −ジオキサポリナン［：Ｃ：］ ２ ｍｍｏ＋
及びアクリノレ酸３ｍｍｏ＋の無水ベンゼン溶液ＩＱｍ
ｌと１，８−ジアザジシクロ（５，４，０〕ウンデカ−
７−エン（ＤＢＵ）３ｍ ｍｏ ＋の無水ベンゼン溶液
５ ｍｌを窒素気流下に仕込み，攪拌溶解した。反応温
度６０℃で２時間攪拌し，反応終了後は室温に戻し，ベ
ンゼンを留去，カラムクロマトグラフィー（２００メッ
シュのシリカゲ／Ｌ’２０ｙｌ展開溶媒；ジクロルメタ
ン）とヘキサンからの再結晶によシ単離精製し，２−（
４−置換フェニ／Ｌ／ ） − ４−アクリルオキシア
ルキル−１． ３． ２−ジオキサボリナン〔■〕を得
た。5Q cc substituted phenyl/L')-4-promoalkyl-1. equipped with stirrer, thermometer and reflux condenser. 3.
2-dioxaporinane [:C:] 2 mmo+
and anhydrous benzene solution IQm of acrinoleic acid 3mmo+
l and 1,8-diazadicyclo(5,4,0]undec-
5 ml of an anhydrous benzene solution of 3 m mo + of 7-ene (DBU) was charged under a nitrogen stream and dissolved with stirring. The reaction temperature was stirred for 2 hours at 60°C, and after the reaction was completed, the temperature was returned to room temperature, the benzene was distilled off, and the mixture was purified by column chromatography (200 mesh silicage/L'20yl developing solvent; dichloromethane) and recrystallization from hexane. Isolated and purified, 2-(
4-substituted phenyl/L/)-4-acryloxyalkyl-1. 3. 2-dioxaborinane [■] was obtained.
製造例４ ２−（４一置換フェニ）ＩＩ／） −
４−メタアクリノレアクリル酸の代シにメタアクリノレ
酸を使／ｆｉする以外は製造例３と向一の条件で合成し
．２−（４一置換フェニＡ／ ） − ４一メタアクリ
ルオキシアルキｙＬｙ−１．３．２−ジオキサボリナン
〔■〕を得た。Production Example 4 2-(4-monosubstituted phenyl)II/) −
Synthesis was carried out under the conditions of Production Example 3 and Koichi, except that methacrylinoleic acid was used in place of 4-methacrylinoleacrylic acid. 2-(4-monosubstituted phenylA/)-4-methacryloxyalkyl-yLy-1.3.2-dioxaborinane [■] was obtained.
製造例３及び４で得られた各化合物の性状と物性と共に
結果を第３表に示す。The results are shown in Table 3 along with the properties and physical properties of each compound obtained in Production Examples 3 and 4.
（ニ） 第３表中の記号は次のことを示す。(d) The symbols in Table 3 indicate the following.
Ｃ：結ｄ％相，Ｓ＾：液晶相のスメクチックＡ相，■：
等方性液体相，※，塩素（ｃｇの元素分析値。C: Crystalline d% phase, S^: Smectic A phase of liquid crystal phase, ■:
Isotropic liquid phase, *, chlorine (elemental analysis value of cg).
の合戊
ＩＱ ｍｌのガラヌアンフ゜ルに製造例３及び４で得ら
れた各化合物〔■〕，アゾビヌイソブチロニトリル及び
乾燥トノレエンの所定量を入れ，凍結脱気した後，アン
プルの口を封じ，第４表における重合条件で反応させた
。反応後，アンプルの口を切り，メタノー）Ｖ １００
ｍｌ中へ注ぎ込み，析出した不溶物を遠心分離，固形
物をペンセンに溶解，凍結乾燥，精製して有機ホウ素含
有ポリマーを得た。A predetermined amount of each compound [■] obtained in Production Examples 3 and 4, azobinisobutyronitrile, and dry tonoleene were added to a combined IQ ml of garanu ampoule, and after freezing and degassing, the opening of the ampoule was sealed. The reaction was carried out under the polymerization conditions shown in Table 4. After the reaction, cut the ampoule and add methanol) V 100
The precipitated insoluble matter was centrifuged, and the solid matter was dissolved in pentene, freeze-dried, and purified to obtain an organic boron-containing polymer.
重合条件及ひボリマーの収量は第４表に，ボリマーの分
析結果及び性質は第５表にそれぞれ示す。The polymerization conditions and polymer yield are shown in Table 4, and the analysis results and properties of the polymer are shown in Table 5.
実施例２ 有機ホウ素含有ボリマー（相互のＩＲ
ス ペ ク ト ノレ
１０ ｍｌのガラスアンプルに製造例３で得られた七ノ
マーｍ５を０．３５９及び七ノマーＮ＋１７を０．３！
Ｍ．アゾビヌインプチロニトリル５．３η及び乾燥トノ
レエン８ｍｌを入れ，凍結脱気した後，アンプルの口を
封じ． ６０℃で１０時間反応させた。アンプルの口を
切り，メタノー／” １００ ｒｎｔ中へ注ぎ込み，析
出した不溶物を遠心分離した後，ベンセンに溶解，凍結
乾燥させて精製し，有機ホウ素含有ボリマーを得た。こ
のポリマーを窒素（Ｎ）分析した結果，０６５９％の窒
素を含有していた。 計算した結果，ボリマーはモノマ
ー醜５とモノマーＮａ７がモｐ比で８３．３対１６．７
の割合で共重合していることが判明した。Example 2 Organoboron-containing polymer (mutual IR
In a 10 ml glass ampoule, 0.359 of the heptanomer m5 obtained in Production Example 3 and 0.3 of the heptanomer N+17!
M. Add 5.3 η of azobinuinputilonitrile and 8 ml of dry tonoleene, freeze and degas, and then seal the ampoule. The reaction was carried out at 60°C for 10 hours. The ampoule was cut open and poured into methanol/100rnt, and the precipitated insoluble matter was centrifuged, dissolved in benzene, and purified by freeze-drying to obtain an organic boron-containing polymer. ) As a result of analysis, it contained 0659% nitrogen.As a result of calculation, the polymer had a mop ratio of monomer Ugly 5 and monomer Na7 of 83.3 to 16.7.
It was found that they were copolymerized at a ratio of .
得られたボリマーの分析結果及び性質を次に示す。The analysis results and properties of the obtained polymer are shown below.
元素分析
ν＝′：杢ｏ１（田一’） ： ２２１０（Ｃ＝Ｎ）．
１７４５（Ｃ＝０）． １３２０（Ｃ−０）。Elemental analysis ν=': Mochi o1 (Taichi'): 2210 (C=N).
1745 (C=0). 1320 (C-0).
ＮＭＲ ヌ ベ ク ト ノレ
δ’ｉ＆’ｆ３（ｐｐｍ） ： ７．８３〜７．８１（
Ｉｎ）， ７．６６（ｄ．Ｊ＝８Ｈｚ） ，７、５９〜
７．５７（ｍ）， ７．１５〜７．１３（Ｉｎ）． ４
．１２〜３．７１（Ｉｎ）．２．５７（ｂ）． ２．０
１〜１．１２（ｍ）， ０．８７（ｔ， Ｊ＝７Ｈｚ）
。NMR value δ'i&'f3 (ppm): 7.83~7.81 (
In), 7.66 (d.J=8Hz), 7, 59~
7.57 (m), 7.15-7.13 (In). 4
．． 12-3.71 (In). 2.57(b). 2.0
1 to 1.12 (m), 0.87 (t, J=7Hz)
.
材１ ＝ ２５０ ０００ （ポリスチレン標準 （注二Ｇ， Ｓ＾及び■は第５表の記号と同意義を示す）。Material 1 = 250 000 (Polystyrene standard (Note 2G, S^ and ■ indicate the same meanings as the symbols in Table 5).
第１図は実施例１で得られたホリマーｍｌの赤外吸収ス
ベク｝／レであり．第２図は同じボリマ−（７）７’ｌ
ｆｆｌ−ンＮＭＲスペクトルである。Figure 1 shows the infrared absorption of ml of polymer obtained in Example 1. Figure 2 shows the same bolimer (7) 7'l
ffl-n NMR spectrum.
Claims (1)
１〜１３個の直鎖アルコキシ基、２〜１４個の直鎖アル
コキシカルボニル基、ハロゲン原子又はシアノ基を、Ｘ
は水素原子又はメチル基を、ｎは２〜１５の整数をそれ
ぞれ示す）で表わされる繰返し単位を有する有機ホウ素
含有ポリマー。[Claims] 1. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, R is a linear alkyl group having 1 to 13 carbon atoms, a straight chain alkyl group having 1 to 13 carbon atoms, A straight chain alkoxy group, 2 to 14 straight chain alkoxycarbonyl groups, a halogen atom or a cyano group,
is a hydrogen atom or a methyl group, and n is an integer of 2 to 15, respectively).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1157518A JP2691300B2 (en) | 1989-06-20 | 1989-06-20 | Organic boron-containing polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1157518A JP2691300B2 (en) | 1989-06-20 | 1989-06-20 | Organic boron-containing polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0321609A true JPH0321609A (en) | 1991-01-30 |
| JP2691300B2 JP2691300B2 (en) | 1997-12-17 |
Family
ID=15651427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1157518A Expired - Fee Related JP2691300B2 (en) | 1989-06-20 | 1989-06-20 | Organic boron-containing polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2691300B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07261209A (en) * | 1994-03-25 | 1995-10-13 | Hitachi Ltd | Nonlinear optical device |
| JP2008518054A (en) * | 2004-10-22 | 2008-05-29 | ザ リージェンツ オブ ザ ユニバーシティ オブ ミシガン | Covalent organic skeletons and polyhedra |
| JP2018525498A (en) * | 2015-08-20 | 2018-09-06 | エコール・シュペリュール・ドゥ・フィシック・エ・シミー・アンデュストリエル・ドゥ・ラ・ヴィル・ドゥ・パリ | Patent application title: POLYMER COMPOSITION CONTAINING CROSSLINKED POLYMER CONTAINING BORONATE ESTER FUNCTIONAL CAPABLE OF EXCHANGE REACTION |
-
1989
- 1989-06-20 JP JP1157518A patent/JP2691300B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07261209A (en) * | 1994-03-25 | 1995-10-13 | Hitachi Ltd | Nonlinear optical device |
| JP2704111B2 (en) * | 1994-03-25 | 1998-01-26 | 株式会社日立製作所 | Nonlinear optical element |
| JP2008518054A (en) * | 2004-10-22 | 2008-05-29 | ザ リージェンツ オブ ザ ユニバーシティ オブ ミシガン | Covalent organic skeletons and polyhedra |
| JP2018525498A (en) * | 2015-08-20 | 2018-09-06 | エコール・シュペリュール・ドゥ・フィシック・エ・シミー・アンデュストリエル・ドゥ・ラ・ヴィル・ドゥ・パリ | Patent application title: POLYMER COMPOSITION CONTAINING CROSSLINKED POLYMER CONTAINING BORONATE ESTER FUNCTIONAL CAPABLE OF EXCHANGE REACTION |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2691300B2 (en) | 1997-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5493088B2 (en) | Method for increasing refractive index imparting effect in a compound having a dibenzothiophene skeleton | |
| CN109553568B (en) | Conjugated alkynyl anthracene derivative and method for regulating atom transfer radical polymerization by using same as visible light photosensitizer | |
| Ueda et al. | Synthesis and homopolymerization kinetics of α-methylene-δ-valerolactone, an exo-methylene cyclic monomer with a nonplanar ring system spanning the radical center | |
| JPH0321609A (en) | Organic boron-containing polymer | |
| Shiohara et al. | Asymmetric anionic polymerization of alkyl-substituted N, N-diphenylacrylamide derivatives | |
| CN115536668A (en) | Fat iodonium salt and preparation method and application thereof | |
| JPS62215608A (en) | Production of alkenylsilyl group-containing high polymer compound | |
| JPH04173812A (en) | New methacrylic acid derivative and its polymer | |
| US4163014A (en) | 3,4,5,6-Tetrahydropyromellitdiimides | |
| JPS61171463A (en) | Acrylic acid ester compound containing azo bond | |
| SU869290A1 (en) | Bis-aryl-o-carborane as intermediate product in synthesis of polymers of polyphenylene type | |
| JPS6124588A (en) | Polymerizable crown ether compound | |
| JPS63150324A (en) | Novel sulfur-containing polymer and its production | |
| JPH0149717B2 (en) | ||
| Matsumoto et al. | Synthesis and Characterization of Poly (N-trialkylsilylmaleimide) s through Radical and Anionic Polymerizations. | |
| US4125536A (en) | Pyrolysis product of N-substituted-1-cyclohexene-1,2-dicarboximides | |
| Liu et al. | Synthesis of chiral polymers containing the acetoxybornyl group and their applications on the asymmetric induction | |
| JPH0317085A (en) | Dioxaborinane compound | |
| JPH04332705A (en) | Novel maleimide derivative and polymer comprising repeating unit thereof | |
| JP2022106267A (en) | Novel precision polymerization catalyst for use in production of substituted polyacetylenes | |
| JPH01233252A (en) | Polycyclic phenoxyllene compound and production thereof | |
| US4225505A (en) | Pyrolysis of N-substituted-1-cyclohexene-1,2-dicarboximides and hydrolysis of product to pyromellitic anhydride | |
| JPS63115832A (en) | 4-(9-triptycenyl)styrene | |
| CN115894399A (en) | Fluorene derivative photoinitiator and preparation method and application thereof | |
| JP2021147518A (en) | Olefin polymerization catalyst, transition metal complex, and olefin copolymer production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |