JPH03231902A - Polyvinyl alcohol derivative and production thereof - Google Patents
Polyvinyl alcohol derivative and production thereofInfo
- Publication number
- JPH03231902A JPH03231902A JP2783990A JP2783990A JPH03231902A JP H03231902 A JPH03231902 A JP H03231902A JP 2783990 A JP2783990 A JP 2783990A JP 2783990 A JP2783990 A JP 2783990A JP H03231902 A JPH03231902 A JP H03231902A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- polymer
- alcohol derivative
- nitrophthalonitrile
- derivative
- 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
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims description 42
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims description 37
- 150000001298 alcohols Chemical class 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 claims abstract description 15
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000012776 electronic material Substances 0.000 abstract description 3
- UZJZIZFCQFZDHP-UHFFFAOYSA-N 3-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=CC(C#N)=C1C#N UZJZIZFCQFZDHP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical group N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000002560 nitrile group Chemical group 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- -1 lithium carbonate Nitrophthalonitrile Chemical compound 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QJGQUHMNIGDVPM-BJUDXGSMSA-N Nitrogen-13 Chemical compound [13N] QJGQUHMNIGDVPM-BJUDXGSMSA-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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 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、フタロニトリル基を側鎖に有する新規なポリ
ビニルアルコール誘導体およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polyvinyl alcohol derivative having a phthalonitrile group in its side chain and a method for producing the same.
特に、電子材料、高分子色素、高分子半導体などに、好
ましく適用できる。In particular, it is preferably applicable to electronic materials, polymer dyes, polymer semiconductors, and the like.
［従来の技術］
従来、フタロニトリル基を側鎖に有するポリマーを得る
ための実用的な方法は無く、従って、側鎖にフタロニト
リル基を有するポリマーは従来知られていない。[Prior Art] Conventionally, there is no practical method for obtaining a polymer having a phthalonitrile group in a side chain, and therefore, a polymer having a phthalonitrile group in a side chain is not known.
［発明が解決しようとする課題］
本発明は、上記に鑑みなされたもので側鎖にフタロニト
リル基を有する新規なポリビニルアルコ−ル誘導体とそ
の製造方法を提供することを目的とする。[Problems to be Solved by the Invention] The present invention has been made in view of the above and aims to provide a novel polyvinyl alcohol derivative having a phthalonitrile group in the side chain and a method for producing the same.
［課題を解決するための手段］
本発明は、上記目的を達成するために下記の構成を有す
る。[Means for Solving the Problems] The present invention has the following configuration to achieve the above object.
「（１）繰返し単位が、下記一般式［Ｉ］で示されるこ
とを特徴とするポリビニルアルコール誘導体。"(1) A polyvinyl alcohol derivative characterized in that the repeating unit is represented by the following general formula [I].
［式中、−■−は、ポリビニルアルコールまたはポリビ
ニルアルコール誘導体のビニルアルコール単位残基を示
す。Ｘおよびｙは、自然数を示し、ｙ／ｘが０．１以上
、１． ０以下である。］（２）下記一般式［］Ｉ］で
示される繰り返し単位を有する重合体と、
（ｖ＋−１−Ｈ［■コ
［式中、−Ｖ−は、ポリビニルアルコールまたはポリビ
ニルアルコール誘導体のビニルアルコール単位残基を示
し、Ｘは自然数を示す。］、］４−ニトロフタロニトリ
とを置換反応させることにより製造することを特徴とす
る上記（１）項記載のポリビニルアルコール誘導体の製
造方法。」本発明のポリビニルアルコール誘導体は、始
発物質として、下記一般式［■］で示される繰り返し単
位を有する重合体を用いるが、
（Ｖ＋−７−Ｈ
［■コ
［式中、＝■−は、ポリビニルアルコールまたはポリビ
ニルアルコール誘導体のビニルアルコール単位残基を示
し、Ｘは自然数を示す。コ、かかるポリビニルアルコー
ルまたはポリビニルアルコール誘導体としては市販の完
全けん化ポリビニルアルコールまたは部分けん化ポリビ
ニルアルコールを用いることが出来る。これら始発物質
の重合度は３ Ｘ ］、 ０２以上が好ましい。[In the formula, -■- represents a vinyl alcohol unit residue of polyvinyl alcohol or a polyvinyl alcohol derivative. X and y represent natural numbers, and y/x is 0.1 or more, 1. It is less than or equal to 0. ](2) A polymer having a repeating unit represented by the following general formula []I], A method for producing a polyvinyl alcohol derivative as described in item (1) above, characterized in that the polyvinyl alcohol derivative is produced by a substitution reaction with 4-nitrophthalonitrile, wherein X is a natural number.'' The present invention For the polyvinyl alcohol derivative, a polymer having a repeating unit represented by the following general formula [■] is used as a starting material. This represents the vinyl alcohol unit residue of the polyvinyl alcohol derivative, and X represents a natural number. Commercially available fully saponified polyvinyl alcohol or partially saponified polyvinyl alcohol can be used as such polyvinyl alcohol or polyvinyl alcohol derivative. The degree of polymerization is preferably 3.times.02 or higher.
具体的な好ましい反応例を以下に示す。Specific preferred reaction examples are shown below.
まずポリビニルアルコールまたはポリビニルアルコール
誘導体を、活性水素を持たない極性溶剤。First, polyvinyl alcohol or a polyvinyl alcohol derivative is a polar solvent that does not have active hydrogen.
すなわち、ジメチルスルフオキシド、ジメチルホルムア
ミドなどに溶解する。次いで、炭酸カリウム、炭酸ナト
リウム、炭酸リチウムなどのアルカリ金属炭酸塩と４−
ニトロフタロニトリルを上記溶液に加えて、撹拌しなが
ら加熱し、例えば４０°Ｃ〜１５０程度に加熱し反応さ
せる。なお、アルカリ金属塩の量は４−ニトロフタロニ
トリルの等モル量ないし４倍モル量が好ましい。４−ニ
トロフタロニトリルの量はポリビニルアルコールまたは
ポリビニルアルコール誘導体の水酸基と等量から１０分
の１−当量が好ましい。アルカリ金属塩と４−ニトロフ
タロニトリルはどちらを先に加えても良いし、また−時
に加えてもよいし、反応させつつ逐次的に加えてもよい
。反応時間は温度により異なるが３０分から１０時間程
度であることが好ましい。That is, it dissolves in dimethyl sulfoxide, dimethyl formamide, etc. Next, alkali metal carbonate such as potassium carbonate, sodium carbonate, lithium carbonate
Nitrophthalonitrile is added to the above solution and heated while stirring to, for example, about 40° C. to 150° C. to react. The amount of the alkali metal salt is preferably an equimolar amount to 4 times the molar amount of 4-nitrophthalonitrile. The amount of 4-nitrophthalonitrile is preferably from equivalent to 1/10 of the hydroxyl group of polyvinyl alcohol or polyvinyl alcohol derivative. Either of the alkali metal salt and 4-nitrophthalonitrile may be added first, they may be added at the same time, or they may be added sequentially while reacting. The reaction time varies depending on the temperature, but is preferably about 30 minutes to 10 hours.
反応終了後、反応物を大量の水もしくは希塩酸中に注ぎ
、生じた固体を濾別する。その固体を水洗した後、乾燥
することにより、下記一般式［Ｉ］で示される繰り返し
単位を有する、ポリビニルアルコール誘導体を得ること
ができる。After the reaction is complete, the reaction product is poured into a large amount of water or diluted hydrochloric acid, and the resulting solid is filtered off. By washing the solid with water and drying it, a polyvinyl alcohol derivative having a repeating unit represented by the following general formula [I] can be obtained.
［式中、−Ｖ−は、ポリビニルアルコールまたはポリビ
ニルアルコール誘導体のビニルアルコール単位残基を示
す。Ｘおよびｙは、自然数を示し、ｙ／ｘが０．１以上
、１． ０以下である。コここで、ビニルアルコール単
位残基とは、ＣＨ２−ＣＨ−
を示し、また、上記ポリビニルアルコール誘導体におい
てｙ／ｘは、フタロニトリル基を有することによる効果
を実質的に発現させるために０． １以上であることが
必要である。[In the formula, -V- represents a vinyl alcohol unit residue of polyvinyl alcohol or a polyvinyl alcohol derivative. X and y represent natural numbers, and y/x is 0.1 or more, 1. It is less than or equal to 0. Here, the vinyl alcohol unit residue represents CH2-CH-, and in the polyvinyl alcohol derivative, y/x is 0.0 to substantially exhibit the effect of having a phthalonitrile group. It needs to be 1 or more.
［実施例コ
実施例１
１．４７ｇ （０，０３３４水酸基当量）のポリビニル
アルコール（“ゴーセノール”ＮＨ−２６）を３０ｍ１
のジメチルスルフオキシドに溶解した。[Example Example 1 1.47 g (0,0334 hydroxyl equivalent) of polyvinyl alcohol (“Gohsenol” NH-26) was added to 30 ml
of dimethyl sulfoxide.
この溶液を撹拌しながら９． ２３ｇ （０，０６６８
ｍｏｌ）の炭酸カリウムと５．７８ｇ （０，０３３４
ｍｏｌ）の４−ニトロフタロニトリルを加えた。9. While stirring this solution. 23g (0,0668
mol) of potassium carbonate and 5.78 g (0,0334
mol) of 4-nitrophthalonitrile was added.
８０℃に昇温しで５時間反応させた。この反応液を室温
に冷却した後、８０ｍ１の３規定塩酸水溶液にゆっくり
注いだ。析出したポリマーを濾取し、細か（してから水
洗し、乾燥したところ５．１５ｇの淡黄色ポリマーが得
られた。The temperature was raised to 80°C and the mixture was reacted for 5 hours. After the reaction solution was cooled to room temperature, it was slowly poured into 80 ml of 3N aqueous hydrochloric acid solution. The precipitated polymer was collected by filtration, washed with water, and dried to obtain 5.15 g of pale yellow polymer.
このポリマーの赤外吸収スペクトルをとったところ、ポ
リビニルアルコールに存在した水酸基の３２００−３６
００ｃｍ−’の吸収と４−ニトロフタロニトリルに存在
した１５４０ｃｍ ’ １３６０ｃｍ−’のニトロ基
の吸収が認められず、２２５０ｃｍ−１にニトリル基の
吸収、１２６０ｃｍ−’にエーテル結合の吸収が認めら
れた。また元素分析値は炭素６９゜９％、水素３．３％
、窒素１５．９％であり、（ｎは、自然数を示す）
で示されるポリビニルアルコール誘導体としての計算値
、炭素７０．６％、水素３．６％、窒素１６．５％とほ
ぼ同じ値を示し、この構造のポリマーの生成が認められ
る。When we took an infrared absorption spectrum of this polymer, we found that the hydroxyl groups present in polyvinyl alcohol were 3200-36
Absorption at 00 cm-' and absorption of the nitro group at 1540 cm' and 1360 cm-' present in 4-nitrophthalonitrile were not observed, and absorption of the nitrile group at 2250 cm-1 and absorption of the ether bond at 1260 cm-' were observed. . Elemental analysis values are 69.9% carbon and 3.3% hydrogen.
, nitrogen is 15.9%, which is almost the same value as the calculated value for a polyvinyl alcohol derivative, where carbon is 70.6%, hydrogen is 3.6%, and nitrogen is 16.5%. The formation of a polymer with this structure is observed.
このポリマーのジメチルホルムアミド溶液をガラス板に
薄く塗り、１−４０℃で乾燥すると淡褐色透明なフィル
ムが得られた。A dimethylformamide solution of this polymer was applied thinly to a glass plate and dried at 1-40°C to obtain a pale brown transparent film.
実施例２
１．４７ｇ （０，０３３４水酸基当量）のポリビニル
アルコール（“ゴーセノール”Ｎ Ｌ−０５＞を３０ｍ
１のジメチルスルフオキシドに溶解した。Example 2 1.47 g (0,0334 hydroxyl equivalent) of polyvinyl alcohol (“Gohsenol” N L-05) was added to 30 m
1 in dimethyl sulfoxide.
この溶液を撹拌しながら９．２３ｇ （０，０６６８ｍ
ｏｌ ）の炭酸カリウムと４．６３ｇ （０，０２６７
ｍｏｌ）の４−ニトロフタロニトリルを加えた。While stirring this solution, 9.23g (0,0668m
ol ) of potassium carbonate and 4.63 g (0,0267
mol) of 4-nitrophthalonitrile was added.
９０℃に昇温しで４時間反応させた。反応液は実施例１
と同様に処理し、４．５２ｇの淡黄褐色ポリマーを得た
。このポリマーの赤外吸収スペクトルではポリビニルア
ルコールに存在した３２００〜３６００ｃｍ”の吸収が
小さくなり４−ニトロフタロニトリルに存在した１５４
０ｃｍ−’、１３６０ｃｍ１のニトロ基の吸収が認めら
れず、２２５０ｃｍ−１にニトリル基の吸収、１２６０
ｃ［ｎ−１にエーテル結合の吸収が認められた。元素分
析値は炭素６８゜８％、水素３．７％、窒素１５．２％
であり、−←ＣＨ２−ＣＨ＋−単位を１として、Ｈ
−〇〇Ｈ２−ＣＨう−
単位が４であるランダムコポリマーの計算値、炭素６９
．６％、水素３．９％、窒素１５．５％とほぼ同じ値を
示し、この構造のポリマーの生成が認められる。The temperature was raised to 90°C and the mixture was reacted for 4 hours. The reaction solution was Example 1.
It was treated in the same manner as above to obtain 4.52 g of a pale yellowish brown polymer. In the infrared absorption spectrum of this polymer, the absorption at 3200 to 3600 cm'', which existed in polyvinyl alcohol, became smaller, and the 154 which existed in 4-nitrophthalonitrile became smaller.
No absorption of nitro group was observed at 0 cm-', 1360 cm-1, absorption of nitrile group at 2250 cm-1, 1260
Absorption of ether bond was observed at c[n-1. Elemental analysis values: carbon 68.8%, hydrogen 3.7%, nitrogen 15.2%
and -←CH2-CH+- unit is 1, H -〇〇H2-CHu- Calculated value for a random copolymer with 4 units, carbon 69
．． 6%, hydrogen 3.9%, and nitrogen 15.5%, indicating the formation of a polymer with this structure.
このポリマーから実施例１と同様にして淡褐色透明なフ
ィルムが得られた。A pale brown transparent film was obtained from this polymer in the same manner as in Example 1.
実施例３
１．４７ｇ （０，０３３４水酸基当量）のポリビニル
アルコール（″ゴーセノール”ＮＨ−２６）を３０１１
１１のジメチルスルフオキシドに溶解した。Example 3 1.47 g (0,0334 hydroxyl equivalent) of polyvinyl alcohol ("Gohsenol" NH-26) was added to 3011
11 in dimethyl sulfoxide.
この溶液を撹拌しながら９．２３ｇ （０，０６６３ｍ
ｏｌ）の炭酸カリウムと２．８９ｇ （０，０１５７ｍ
ｏｌ）の４−ニトロフタロニトリルを加えた。While stirring this solution, 9.23g (0,0663m
ol) potassium carbonate and 2.89g (0,0157m
ol) of 4-nitrophthalonitrile was added.
８５℃に昇温しで４時間反応させた。反応液は実施例１
−と同様に処理し、３．３１ｇの淡黄褐色ポリマーを得
た。このポリマーの赤外吸収スペクトルでは４−ニトロ
フタロニトリルに存在した１５４Ｑｃｍ−１，１３６０
ｃｍ−１のニトロ基の吸収が認められず、２２５０ａｎ
−’にニトリル基の吸収、１．２６０ｃｍ−１にエーテ
ル結合の吸収が認められた。元素分析値は炭素６６．７
％、水素４．４％、窒素１３゜
３％であり、−←ＣＨ２ＣＨ９−単位を１としＨ
て、
一〇〇Ｈ２ＣＨ←−
＾
１．０
単位が１であるランダムコポリマーの計算値、炭素６７
．３％、水素４．７％、窒素１３．１％吉はぼ同じ値を
示し、この構造のポリマーの生成が認められる。The temperature was raised to 85°C and the reaction was carried out for 4 hours. The reaction solution was Example 1.
- 3.31 g of light yellowish brown polymer was obtained. The infrared absorption spectrum of this polymer shows 154Qcm-1,1360, which was present in 4-nitrophthalonitrile.
No absorption of nitro group at cm-1 was observed, and 2250 an
Absorption of nitrile group was observed at -' and absorption of ether bond was observed at 1.260 cm-1. Elemental analysis value is carbon 66.7
%, hydrogen 4.4%, nitrogen 13°3%, -←CH2CH9- unit is 1 H, 100H2CH←- ^ 1.0 Calculated value for a random copolymer with 1 unit, carbon 67
．． 3% hydrogen, 4.7% hydrogen, and 13.1% nitrogen showed almost the same values, indicating the formation of a polymer with this structure.
このポリマから実施例１と同様にして淡褐色透明なフィ
ルムが得られた。A light brown transparent film was obtained from this polymer in the same manner as in Example 1.
実施例４
１．４７ｇ （０，０３３４水酸基当量）のポリビニル
アルコール（″ゴーセノール″Ｎ Ｈ−２６）を３０ｍ
１のジメチルスルフオキシドに溶解した。Example 4 1.47 g (0,0334 hydroxyl equivalent) of polyvinyl alcohol ("Gohsenol" NH-26) was added to 30 m
1 in dimethyl sulfoxide.
この溶液を撹拌しながら４．６２ｇ （０，０３３４ｍ
ｏｌ）の炭酸カリウムと１．１６ｇ （０，００６６８
ｍｏｌ）の４−ニトロフタロニトリルを加えた。While stirring this solution, 4.62 g (0,0334 m
ol) potassium carbonate and 1.16 g (0,00668
mol) of 4-nitrophthalonitrile was added.
８０℃に昇温しで５時間反応させた。反応液は実施例１
と同様に処理し、２．１．５ｇの淡黄褐色ポリマーを得
た。このポリマーの赤外吸収スペクトルでは１５４０ｃ
ｍ−” １３６０ｃｍ−’のニトロ基の吸収が認めら
れず、２２５０ｃｍ−’にニトリル基の吸収、１．２６
０ｃｍ−’にエーテル結合の吸収が認められた。元素分
析値は炭素６１．９％、水素６゜１
３％、窒素８，０％であり、
一＋ＣＨ２−ＣＨ←単位を４として、
ＯＴ−（
−（ＣＨ２−ＣＨ→−
〇
単位が１であるランダムコポリマーの計算値、炭素６２
．４％、水素６．４％、窒素８，１％とほぼ同じ値を示
し、この構造のポリマーの生成が認められる。The temperature was raised to 80°C and the mixture was reacted for 5 hours. The reaction solution was Example 1.
It was treated in the same manner as above to obtain 2.1.5 g of a pale yellowish brown polymer. The infrared absorption spectrum of this polymer is 1540c.
m-” Absorption of nitro group at 1360 cm-' was not observed, absorption of nitrile group at 2250 cm-', 1.26
Absorption of ether bonds was observed at 0 cm-'. The elemental analysis values are 61.9% carbon, 6.13% hydrogen, and 8.0% nitrogen. Calculated value for a random copolymer, carbon 62
．． 4%, hydrogen 6.4%, and nitrogen 8.1%, indicating the formation of a polymer with this structure.
このポリマーからも強靭なフィルムが得られた。A strong film was also obtained from this polymer.
実施例５
２．６２ｇ （０，０４水酸基当量）の部分けん化ポリ
酢酸ビニル（“ゴーセノール”Ｋｌ（−２０：けん化率
８０％）を６０ｍ１のジメチルスルフオキシドに溶解し
た。この溶液を撹拌しつつ５．５３ｇ （０，０４ｍｏ
ｌ ）の炭酸カリウムと３．４６ｇ（０，０２ｍｏｌ
）の４−ニトロフタロニトリルを加えた。８０℃に昇温
しで５時間反応させた。反応液は実施例１と同様に処理
し、４．８１ｇの淡黄２
緑色ポリマーを得た。このポリマーの赤外吸収スペクト
ルでは部分ケン化ポリ酢酸ビニルに存在した３２００〜
３６００ｃｍ−”の水酸基の吸収が減少しており、４−
ニトロフタロニトリルに存在した１５４０ｃｍ−１，１
３６０ｃｍ−”のニトロ基の吸収が認められず、２２５
０ｃｍ−”にニトリル基の吸収、１２６０ｃｍ−”にエ
ーテル結合の吸収が認められた。Example 5 2.62 g (0.04 hydroxyl equivalent) of partially saponified polyvinyl acetate ("Gohsenol" Kl (-20: saponification rate 80%) was dissolved in 60 ml of dimethyl sulfoxide. While stirring this solution, 5.53g (0.04mo
l ) of potassium carbonate and 3.46 g (0.02 mol
) of 4-nitrophthalonitrile was added. The temperature was raised to 80°C and the mixture was reacted for 5 hours. The reaction solution was treated in the same manner as in Example 1 to obtain 4.81 g of pale yellow 2 green polymer. The infrared absorption spectrum of this polymer shows the 3200-
The absorption of hydroxyl group at 3600 cm-” has decreased, and 4-
1540 cm-1,1 present in nitrophthalonitrile
No absorption of nitro group at 360 cm-” was observed, and 225
Absorption of a nitrile group was observed at 0 cm-'', and absorption of an ether bond was observed at 1260 cm-''.
元素分析値は炭素６４．９％、水素５．１１％、窒素１
０．６％であり、
→ＣＨ２−ＣＨ←−単位が２、
ＯＣＣＨ３
１
単位が２であるランダムコポリマーの計算値、炭３
素６５．４％、水素５．］１１％窒素１０．９％とほぼ
同じ値を示し、この構造のポリマーの生成が認められる
。Elemental analysis values: carbon 64.9%, hydrogen 5.11%, nitrogen 1
Calculated values for a random copolymer with 2 →CH2-CH←- units and 2 OCCH3 1 units, carbon 65.4%, hydrogen 5. ]11%Nitrogen shows almost the same value as 10.9%, and the formation of a polymer with this structure is recognized.
このポリマーも強靭なフィルムを与える。This polymer also provides a tough film.
［発明の効果］
本発明のポリビニルアルコール誘導体は、フタロニトリ
ル基を有するために、種々の反応により、電子材料、色
素などに活用できる有用な誘導体に導くことができ、ま
た、フィルムなどにも容易に成形可能である。[Effects of the Invention] Since the polyvinyl alcohol derivative of the present invention has a phthalonitrile group, it can be converted into useful derivatives that can be used in electronic materials, pigments, etc. through various reactions, and can also be easily used in films, etc. It can be molded into
Claims (1)
とを特徴とするポリビニルアルコール誘導体。 ▲数式、化学式、表等があります▼［ I ］ ［式中、−Ｖ−は、ポリビニルアルコールまたはポリビ
ニルアルコール誘導体のビニルアルコール単位残基を示
す。ｘおよびｙは、自然数を示し、ｙ／ｘが０．１以上
、１．０以下である。］（２）下記一般式［II］で示さ
れる繰り返し単位を有する重合体と、 ▲数式、化学式、表等があります▼［II］ ［式中、−Ｖ−は、ポリビニルアルコールまたはポリビ
ニルアルコール誘導体のビニルアルコール単位残基を示
し、ｘは自然数を示す。］、 ４−ニトロフタロニトリルとを置換反応させることによ
り製造することを特徴とする請求項（１）記載のポリビ
ニルアルコール誘導体の製造方法。(1) A polyvinyl alcohol derivative characterized in that the repeating unit is represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, -V- represents a vinyl alcohol unit residue of polyvinyl alcohol or a polyvinyl alcohol derivative. x and y represent natural numbers, and y/x is 0.1 or more and 1.0 or less. ] (2) A polymer having a repeating unit represented by the general formula [II] below, and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, -V- is polyvinyl alcohol or polyvinyl alcohol derivative It represents a vinyl alcohol unit residue, and x represents a natural number. ], 4-nitrophthalonitrile. The method for producing a polyvinyl alcohol derivative according to claim 1, wherein the polyvinyl alcohol derivative is produced by a substitution reaction with 4-nitrophthalonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2783990A JPH03231902A (en) | 1990-02-07 | 1990-02-07 | Polyvinyl alcohol derivative and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2783990A JPH03231902A (en) | 1990-02-07 | 1990-02-07 | Polyvinyl alcohol derivative and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03231902A true JPH03231902A (en) | 1991-10-15 |
Family
ID=12232096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2783990A Pending JPH03231902A (en) | 1990-02-07 | 1990-02-07 | Polyvinyl alcohol derivative and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03231902A (en) |
-
1990
- 1990-02-07 JP JP2783990A patent/JPH03231902A/en active Pending
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