JPH04103603A - Polyvinyl alcohol derivative and its production - Google Patents
Polyvinyl alcohol derivative and its productionInfo
- Publication number
- JPH04103603A JPH04103603A JP22288890A JP22288890A JPH04103603A JP H04103603 A JPH04103603 A JP H04103603A JP 22288890 A JP22288890 A JP 22288890A JP 22288890 A JP22288890 A JP 22288890A JP H04103603 A JPH04103603 A JP H04103603A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- polymer
- nitrophthalonitrile
- alcohol derivative
- 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 7
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 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 claims abstract description 17
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006467 substitution reaction Methods 0.000 claims abstract 3
- 239000000126 substance Substances 0.000 claims 4
- 239000012776 electronic material Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 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 20
- 238000010521 absorption reaction Methods 0.000 description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 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
- 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
- 229920005604 random copolymer Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 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
- -1 alkali metal salt Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000006519 CCH3 Chemical group 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
- 238000001816 cooling Methods 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
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 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
- 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
- 229920002554 vinyl polymer Polymers 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】
［産業上の利用分野コ
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、高分子錯
体触媒などに、好ましく適用できる。In particular, it can be preferably applied to electronic materials, polymer dyes, polymer semiconductors, polymer complex catalysts, 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［ＩＩ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 [II].
［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［ＩＩ］で示
される繰り返し単位を有する重合体と、
畷
（、Ｖ ＋ Ｈ［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。］、］３−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［ＩＩ］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［ＩＩ ］
［式中、−■−は、ポリビニルアルコールまたは暖
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。］、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３×１０２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 and 1.0 or less. ] (2) A polymer having a repeating unit represented by the following general formula [II], group, and X represents a natural number. ], ] 3-Nitrophthalonitri. A method for producing a polyvinyl alcohol derivative according to item (1) above." For the polyvinyl alcohol derivative, a polymer having a repeating unit represented by the following general formula [II] is used as a starting material, but (V + 7-H [II] [wherein -■- is polyvinyl alcohol or warm polyvinyl represents a vinyl alcohol unit residue of the 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.Polymerization of these starting materials The degree is preferably 3 x 102 or more.
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３−
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℃〜１５０℃程度に加熱し反応さ
せる。なお、アルカリ金属塩の量は３−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。３−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３−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。That is, it dissolves in dimethyl sulfoxide, dimethyl formamide, etc. Next, alkali metal carbonates such as potassium carbonate, sodium carbonate, lithium carbonate, etc.
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 3-nitrophthalonitrile. The amount of 3-nitrophthalonitrile is preferably from equivalent to 1/10 equivalent to the hydroxyl group of polyvinyl alcohol or polyvinyl alcohol derivative. Either of the alkali metal salt and 3-nitrophthalonitrile may be added first, they may be added at the same time, or they may be added sequentially while reacting.
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。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［
ＩＩ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かできる。The reaction time varies depending on the temperature, but is preferably about 30 minutes to 10 hours. 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. After washing the solid with water and drying it, the following general formula [
A polyvinyl alcohol derivative having a repeating unit represented by II can be obtained.
［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。］ここで、ビニルアルコール
単単位系とは、ＣＨ２−ＣＨ−
を意味する。すなわち、本発明の一般式［ＩＩで示され
るポリビニルアルコール誘導体は、−−ＣＨ２−ＣＨ←
−で示される単位と、ｙ ／ ｘが１．０に満たない場
合には、−←ＣＨ２ＣＨ＋−で示される単位等とを有す
る。[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
above, and below 1.0. ] Here, the vinyl alcohol single unit system means CH2-CH-. That is, the polyvinyl alcohol derivative represented by the general formula [II of the present invention is -CH2-CH←
It has a unit represented by -, and a unit represented by -←CH2CH+- when y/x is less than 1.0.
Ｈ
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。H Also, in the above polyvinyl alcohol derivative, y /
x needs to be 0.1 or more in order to substantially exhibit the effect of having a phthalonitrile group.
［実施例コ
実施例１
４．４１ｇ （０，１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１００ｍ１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
ながら２７．６４ｇ （０，２０ｍ０１）の炭酸カリウ
ムと１７．３１ｇ （０，１０ｍ０１）の３−ニトロフ
タロニトリルを添加した。８０℃に昇温しで４時間反応
させた。この反応液を室温に冷却した後、６５０ ｍｌ
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、細かくしてから水洗し、乾燥したところ１
５．６ｇの淡黄色ポリマーが得られた。Examples Example 1 4.41 g (0.1 hydroxyl equivalent) of polyvinyl alcohol ("Gohsenol" NH-26) was dissolved in 100 ml of dimethyl sulfoxide. While stirring the solution, 27.64 g (0.20 m01) of potassium carbonate and 17.31 g (0.10 m01) of 3-nitrophthalonitrile were added. The temperature was raised to 80°C and the mixture was reacted for 4 hours. After cooling this reaction solution to room temperature, 650 ml
The mixture was slowly poured into a 3N aqueous hydrochloric acid solution. The precipitated polymer was collected by filtration, pulverized, washed with water, and dried.
5.6 g of pale yellow polymer was obtained.
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−’の吸収は実質的に認められｆ、３−ニトロ
フタロニトリルに存在した１５４Ｑａｎ−’、１３６０
ｃｍ−１のニトロ基の吸収もなくなり、２２５０ａｎ−
’にニトリル基の吸収、１２６０Ｃ１１１−’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３．４％、窒素１５．８％であり、
一咲ＣＨ２−ＣＨ÷１−
■
（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 the infrared absorption spectrum of this polymer was taken, it was found that the hydroxyl groups present in polyvinyl alcohol had 3200 to 36
Absorption at 00 cm-' was substantially observed f, 154Qan-', 1360 present in 3-nitrophthalonitrile.
There is no absorption of nitro group at cm-1, and 2250 an-
Absorption of a nitrile group was observed in ', and absorption of an ether bond was observed in 1260C111-'. Also, the elemental analysis value is carbon 69
．． 9%, hydrogen 3.4%, nitrogen 15.8%, calculated value as a polyvinyl alcohol derivative expressed as Issaki CH2-CH÷1- (n is a natural number), carbon 70.6% , hydrogen at 3.6% and nitrogen at 16.5%, showing almost the same values, indicating the production of a polymer with this structure.
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、１４０℃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 140°C to obtain a light 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”ＮＬ−０５）を５０ｍ１
のジメチルスルフオキシドに溶解した。Example 2 50ml of 1.47g (0,0334 hydroxyl equivalent) of polyvinyl alcohol (“Gohsenol” NL-05)
of dimethyl sulfoxide.
この溶液を撹拌しながら９． ２３ｇ （０，０６６８
ｎ＋ｏｌ ）の炭酸カリウムと４．６３ｇ （０，０２
６７ｍｏｌ）の３−ニトロフタロニトリルを加えた。9. While stirring this solution. 23g (0,0668
n + ol ) of potassium carbonate and 4.63 g (0,02
67 mol) of 3-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、４．５０ｇ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３−ニトロフタロニトリルに存在した１５
４０ｃｍ−’、１３６０ａｎ利のニトロ基の吸収が認め
られず、２２５０ｃｍ−’にニトリル基の吸収、１２６
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６８゜９％、水素３．６％、窒素１５，９％
であり、−−ＣＨ２ＣＨ←単位を１として、
Ｈ
−←ＣＨ２ＣＨ←−
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 4.50 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, decreased and the 15 which existed in 3-nitrophthalonitrile
No absorption of nitro group was observed at 40cm-', 1360an, and absorption of nitrile group at 2250cm-', 126
Absorption of ether bonds was observed at 0 cm-'. Elemental analysis values: carbon 68.9%, hydrogen 3.6%, nitrogen 15.9%
and --CH2CH← unit is 1, H -←CH2CH←- Calculated value of 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
４．４１ｇ （０，１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１００ｍ１のジ
メチルスルフオキシドに溶解した。この溶液を撹拌しな
がら２０．７３ｇ （０，１５ｍｏｌ ）の炭酸カリウ
ムと８．６６ｇ （０，０５ｍｏｌ）の３−ニトロフタ
ロニトリルを加えた。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、９．９５ｇ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３−ニトロフタロニトリルに存在した１５４０
Ｃｍ −’、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、１２６
０ａＯ−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４．３％、窒素１３゜４％
であり、−ＣＣＨ２−ＣＨ＋単位を１として、Ｈ
−←ＣＨ２−ＣＨ＋−
単位が１であるランダムコポリマーの計算値、炭素６７
６３％、水素４．７％、窒素１３．１％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。Example 3 4.41 g (0.1 hydroxyl equivalent) of polyvinyl alcohol ("Gohsenol" NH-26) was dissolved in 100 ml of dimethyl sulfoxide. While stirring this solution, 20.73 g (0.15 mol) of potassium carbonate and 8.66 g (0.05 mol) of 3-nitrophthalonitrile were added. The temperature was raised to 90°C and the mixture was reacted for 4 hours. The reaction solution was treated in the same manner as in Example 1 to obtain 9.95 g of a pale yellowish brown polymer. In the infrared absorption spectrum of this polymer, 1540, which was present in 3-nitrophthalonitrile,
Cm-', no absorption of nitro group was observed at 1360 cm-', absorption of nitrile group at 2250 cm-', 126
Absorption of ether bond was observed at 0aO-1. Elemental analysis values are 66.7% carbon, 4.3% hydrogen, and 13.4% nitrogen.
Calculated value for a random copolymer in which -CCH2-CH+ unit is 1, H -←CH2-CH+- unit is 1, carbon 67
63%, hydrogen 4.7%, and nitrogen 13.1%, which are almost the same values, and the production of a polymer with this structure is recognized.
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
２．２０ｇ （０，０５水酸基当量）のポリビニルアル
コール（“ゴーセノール”ＮＭ−１１）を５０ｍ１のジ
メチルスルフオキシドに溶解した。この溶液を撹拌しな
がら６．９１ｇ （０，０５ｍｏｌ ）の炭酸カリウム
と１．７３ｇ （０，Ｏｌｍｏｌ ）の３−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、３．２４ｇの淡
黄褐色ポリマーを得た。Example 4 2.20 g (0.05 hydroxyl equivalents) of polyvinyl alcohol ("Gohsenol" NM-11) were dissolved in 50 ml of dimethyl sulfoxide. While stirring this solution, 6.91 g (0.05 mol) of potassium carbonate and 1.73 g (0.0 mol) of 3-nitrophthalonitrile were 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 3.24 g of a pale yellowish brown polymer.
このポリマーの赤外吸収スペクトルでは１５４００ｎ
−１，１３６０ａｎ−’のニトロ基の吸収が認められず
、２２５０ａｎ−’にニトリル基の吸収、１２６０ａｎ
−’にエーテル結合の吸収が認められた。元素分析値
は炭素６１．８％、水素６．２％、窒素７゜９％であり
、
一←ＣＨ２−ＣＨ←単位を４として、
？
Ｈ
−Ａ＝ＣＨ２ＣＨｅ−
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 infrared absorption spectrum of this polymer is 15400n.
-1,1360an-' absorption of nitro group was not observed, absorption of nitrile group at 2250an-', 1260an-'
-' absorption of ether bond was observed. The elemental analysis values are 61.8% carbon, 6.2% hydrogen, and 7°9% nitrogen, and the unit is 4. H -A=CH2CHe- Calculated value for a random copolymer with 1 unit, 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か得られた。A strong film was also obtained from this polymer.
実施例５
１．３１ｇ （０，０２水酸基当量）の部分けん化ポリ
酢酸ビニル（“ゴーセノール”ＫＨ−２０：けん化率８
０％）を４０ｍＩ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２．７６ｇ （０，０２ｍｏｌ
）の炭酸カリウムと１．７３ｇ（０，Ｏｌｍｏｌ ）
の３−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
、２．３５ｇの淡黄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、３−ニトロフタロニトリルに存在した１
５４０ｃｍ−’、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
２６０ｃｍ−’にエーテル結合の吸収が認められた。Example 5 1.31 g (0.02 hydroxyl equivalent) of partially saponified polyvinyl acetate ("Gohsenol" KH-20: saponification rate 8
0%) was dissolved in 40 mI dimethyl sulfoxide. While stirring this solution, 2.76g (0.02mol
) of potassium carbonate and 1.73 g (0, Olmol)
of 3-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 2.35 g of a pale yellow-green polymer. In the infrared absorption spectrum of this polymer, the absorption of the hydroxyl group at 3200 to 3600 cm-' present in the partially saponified polyvinyl acetate has decreased, and the absorption of the hydroxyl group present in the 3-nitrophthalonitrile has decreased.
No absorption of nitro group was observed at 540 cm-' and 1360 cm-', and no absorption of nitrile group at 2250 cm-'.
Absorption of ether bond was observed at 260 cm-'.
元素分析値は炭素６４．７％、水素５．１％、窒素１０
．８％であり、
一←ＣＨ２ＣＨ←−単位を２として、
Ｈ
−＋ＣＨ２−ＣＨ→−単位が２、
ＣＣＨ３
一←ＣＨ２ＣＨ→−
単位が２であるランダムコポリマーの計算値、炭素６５
．４％、水素５，１％、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 are 64.7% carbon, 5.1% hydrogen, and 10% nitrogen.
．． Calculated value for a random copolymer with 1←CH2CH←- units as 2, H − + CH2-CH→- units as 2, and CCH3 ←CH2CH→- units as 2, carbon 65.
．． 4%, hydrogen 5.1%, and nitrogen 10.9%, indicating the formation of a polymer with this structure.
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、▲数式、化学式、表等があります▼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、▲数式、化学式、表等があります▼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。］
、 ３−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, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ indicates the vinyl alcohol unit residue of polyvinyl alcohol or polyvinyl alcohol derivatives. 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, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is polyvinyl alcohol Alternatively, it represents a vinyl alcohol unit residue of a polyvinyl alcohol derivative, and x represents a natural number. ]
, 3-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 3-nitrophthalonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22288890A JPH04103603A (en) | 1990-08-23 | 1990-08-23 | Polyvinyl alcohol derivative and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22288890A JPH04103603A (en) | 1990-08-23 | 1990-08-23 | Polyvinyl alcohol derivative and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04103603A true JPH04103603A (en) | 1992-04-06 |
Family
ID=16789447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22288890A Pending JPH04103603A (en) | 1990-08-23 | 1990-08-23 | Polyvinyl alcohol derivative and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04103603A (en) |
-
1990
- 1990-08-23 JP JP22288890A patent/JPH04103603A/en active Pending
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