JPH0516422B2 - - Google Patents
Info
- Publication number
- JPH0516422B2 JPH0516422B2 JP3459085A JP3459085A JPH0516422B2 JP H0516422 B2 JPH0516422 B2 JP H0516422B2 JP 3459085 A JP3459085 A JP 3459085A JP 3459085 A JP3459085 A JP 3459085A JP H0516422 B2 JPH0516422 B2 JP H0516422B2
- Authority
- JP
- Japan
- Prior art keywords
- triisocyanate
- phosgene
- present
- reaction
- dimethoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 8
- -1 isocyanate compound Chemical class 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LOZJNNNVLREXGU-UHFFFAOYSA-N 3-amino-4,5,6,7-tetrachloroisoindol-1-one Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(N)=NC2=O LOZJNNNVLREXGU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000001058 brown pigment Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012262 resinous product Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規な芳香族トリイソシアナートお
よびその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel aromatic triisocyanate and a method for producing the same.
本発明は、その蒸気圧が常温においてほとんど
ないために、毒性が少なく、安定な芳香族イソシ
アナートを提供するものである。 The present invention provides a stable aromatic isocyanate with little toxicity since its vapor pressure is almost nonexistent at room temperature.
本発明のイソシアナートは、新規な構造のポリ
イソシアナートであり、化学工業における各種の
原料として有用である。例えば、着色顔料として
オキサミドアゾメチン顔料（特開昭55ー152749）
の原料となり、３−イミノ−４，５，６，７−テ
トラクロロイソインドリン−１−オンと不活性溶
媒中で反応させると、赤褐色の鮮明な顔料が得ら
れる。その他に、ポリウレタン樹脂やポリ尿素樹
脂として、発泡体、弾性体、合成皮革、塗料、接
着剤、シーラント、フイルム等に用いられる。 The isocyanate of the present invention is a polyisocyanate with a novel structure and is useful as a variety of raw materials in the chemical industry. For example, as a coloring pigment, oxamide azomethine pigment (Japanese Patent Application Laid-Open No. 152749-1982)
When reacted with 3-imino-4,5,6,7-tetrachloroisoindolin-1-one in an inert solvent, a bright reddish-brown pigment is obtained. In addition, it is used as a polyurethane resin or polyurea resin in foams, elastic bodies, synthetic leather, paints, adhesives, sealants, films, etc.
（発明の構成）
本発明は、３個のイソシアネート基を有する式
（）で示される２，５−ジメトキシ−４，4′，
4″−トリイソシアナト−トリフエニルアミン（以
下、トリイソシアナートと略記する）を提供する
ものである。(Structure of the Invention) The present invention provides 2,5-dimethoxy-4,4', represented by the formula () having three isocyanate groups,
The present invention provides 4″-triisocyanato-triphenylamine (hereinafter abbreviated as triisocyanate).
そして、前記トリイソシアナートは、次の式
（）で示される２，５−ジメトキシ−４，4′，
4″−トリアミノトリフエニルアミン（以下、トリ
アミンと略記する）またはその塩をホスゲンと反
応させることによつて製造することができる。 The triisocyanate is 2,5-dimethoxy-4,4', represented by the following formula ().
It can be produced by reacting 4''-triaminotriphenylamine (hereinafter abbreviated as triamine) or a salt thereof with phosgene.
本発明に係るトリイソシアナートは、式（）
のトリアミンを直接ホスゲンと反応させる方法、
または式（）のトリアミンの塩酸塩、炭酸塩、
硫酸塩、リン酸塩、酢酸塩等を不活性反応溶媒中
に懸濁あるいは溶解させてホスゲンと反応させる
方法によつて製造される。 The triisocyanate according to the present invention has the formula ()
A method of directly reacting triamine with phosgene,
or hydrochloride, carbonate of triamine of formula (),
It is produced by suspending or dissolving sulfate, phosphate, acetate, etc. in an inert reaction solvent and reacting it with phosgene.
たとえば、不活性反応溶媒中にトリアミンを溶
解させ、低温でホスゲンと反応させて、一旦カル
バミルクロライド化合物を得、次いで、80〜230
℃で熱分解させてトリイソシアナートとする。出
発物質のトリアミンを塩として反応させる場合
は、十分に微粉化して不活性溶媒中に懸濁させる
ことが重要である。該ホスゲン化においては、反
応温度は約60〜230℃が好適である。230℃を超え
ると、樹脂状の生成物が多量に生成して、目的の
トリイソシアナートの収量が低下し、一方、60℃
より低いと、反応が遅くなり、反応の完結に長時
間を要する。 For example, once a carbamyl chloride compound is obtained by dissolving triamine in an inert reaction solvent and reacting with phosgene at low temperature, then
It is thermally decomposed at ℃ to produce triisocyanate. When the starting triamine is reacted as a salt, it is important to sufficiently pulverize it and suspend it in an inert solvent. In the phosgenation, the reaction temperature is preferably about 60 to 230°C. If the temperature exceeds 230°C, a large amount of resinous products will be formed and the yield of the desired triisocyanate will decrease;
If it is lower, the reaction will be slower and it will take a longer time to complete the reaction.
本発明に用いられる不活性溶媒としては、通常
のホスゲン化に用いられる脂肪族系炭化水素、芳
香族系炭化水素、塩素化脂肪族炭化水素、塩素化
芳香族炭化水素、塩素化脂環族炭化水素等が挙げ
られる。特にモノクロルベンゼン、ｏ−ジクロル
ベンゼン、１，２，４−トリクロルベンゼン等が
好ましい。反応終了後、不活性溶媒を留去し、残
留生成物を減圧昇華または再結晶することによ
り、本発明の２，５−ジメトキシ−４，4′，4″−
トリイソシアナト−トリフエニルアミンを単離す
ることができる。 Examples of inert solvents used in the present invention include aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, and chlorinated alicyclic hydrocarbons used in normal phosgenation. Examples include hydrogen. Particularly preferred are monochlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, and the like. After the reaction is completed, the inert solvent is distilled off, and the remaining product is sublimated under reduced pressure or recrystallized to obtain the 2,5-dimethoxy-4,4′,4″-
Triisocyanato-triphenylamine can be isolated.
（発明の効果）
本発明のトソシアナートは、従来公知のポリイ
ソシアナートに比べ、水分に対する安定性に優れ
たイソシアナートである。例えば、４，4′，4″−
トリイソシアナト−トリフエニルアミンは、水中
での安定性に欠けるが、本発明のポリイソシアナ
ートは、水中に分散しておいても驚くほど安定
で、その後に各種用途に用いることができる。(Effects of the Invention) The tosocyanate of the present invention is an isocyanate that has excellent stability against moisture compared to conventionally known polyisocyanates. For example, 4,4′,4″−
Although triisocyanato-triphenylamine lacks stability in water, the polyisocyanate of the present invention is surprisingly stable even when dispersed in water, and can be subsequently used in various applications.
（実施例）
２，５−ジメトキシ−４，4′，4″−トリアミノ
−トリフエニルアミン40ｇに水200ｇおよび35％
濃塩酸50ｇを加え溶解させる。これに活性炭を10
ｇ加え、過し、液を減圧下で濃縮する。濃縮
液を大量のアセトニトリル中に投入すると、白色
の沈殿が生成するので、これを過し、結晶を減
圧下に乾燥すると、白色固体の２，５−ジメトキ
シ−４，4′，4″−トリアミノトリフエニルアミン
塩酸塩が49ｇ得られた。(Example) 40 g of 2,5-dimethoxy-4,4',4''-triamino-triphenylamine, 200 g of water and 35%
Add 50g of concentrated hydrochloric acid and dissolve. Add 10 activated charcoal to this
g, filter, and concentrate the liquid under reduced pressure. When the concentrated solution is poured into a large amount of acetonitrile, a white precipitate is formed, which is filtered and the crystals are dried under reduced pressure to form a white solid of 2,5-dimethoxy-4,4',4''-tritrilineate. 49 g of aminotriphenylamine hydrochloride was obtained.
かくして得られたトリアミン塩酸塩を微粉末と
し、さらに減圧下で乾燥を行う。この乾燥粉末45
ｇおよび反応溶媒としてモノクロルベンゼン900
ｇを１四ツ口フラスコに入れ、攪拌器、ガス導
入管、還流冷却器および温度計をとりつけた。懸
濁液を攪拌しながら昇温させ、60℃からホスゲン
を吹き込み始めた。ホスゲンの吹き込みを続けな
がら120℃にまで昇温し、そのまま120℃で３時間
反応を続けたところ、懸濁物はほぼなくなり、褐
色の透明液となつた。反応液を冷却後、ホスゲン
および溶媒を留去すると、粗トリイソシアナート
41ｇが得られた。 The triamine hydrochloride thus obtained is made into a fine powder and further dried under reduced pressure. This dry powder 45
g and monochlorobenzene 900 as reaction solvent
g was placed in a four-necked flask, which was equipped with a stirrer, a gas inlet tube, a reflux condenser, and a thermometer. The temperature of the suspension was raised while stirring, and phosgene was started to be blown in from 60°C. The temperature was raised to 120° C. while continuing to blow phosgene, and the reaction was continued at 120° C. for 3 hours, resulting in almost no suspended matter and a brown transparent liquid. After cooling the reaction solution, phosgene and the solvent are distilled off to form crude triisocyanate.
41g was obtained.
この粗トリイソシアナートを真空昇華器へ入
れ、高真空下に加熱すると、冷却部に白色結晶の
２，５−ジメトキシ−４，4′，4″−トリイソシア
ナト−トリフエニルアミンが得られた。この物質
の物性値および分析値は以下のとおりである。 When this crude triisocyanate was placed in a vacuum sublimator and heated under high vacuum, white crystals of 2,5-dimethoxy-4,4',4''-triisocyanato-triphenylamine were obtained in the cooling section. The physical properties and analytical values of this substance are as follows.
融点：114〜115℃。該磁気共鳴スペクトルデー
タ（装置は日本電子株式会社製 PMX−60型、
溶媒はCDCl3）：３，46ppm（Ｓ，3H）、3.69ppm
（Ｓ，3H）、6.56ppm（Ｓ，2H）、6.83ppm（Ｓ，
8H）。元素分析：実測値C64.71％、H3.62％、
N12.96％、計算値C64.49％、H3.74％、N13.08
％。赤外吸収スペクトルでは2250cm-1に強い
NCO基の吸収が見られた。この赤外吸収スペク
トルを第１図に示す。測定に用いた装置は島津製
作所1R−400型赤外分光光度計で、測定法はKBr
法である。 Melting point: 114-115℃. The magnetic resonance spectrum data (the device is PMX-60 type manufactured by JEOL Ltd.,
Solvent is CDCl 3 ): 3,46ppm (S, 3H), 3.69ppm
(S, 3H), 6.56ppm (S, 2H), 6.83ppm (S,
8H). Elemental analysis: Actual value C64.71%, H3.62%,
N12.96%, calculated value C64.49%, H3.74%, N13.08
%. Strong infrared absorption spectrum at 2250 cm -1
Absorption of NCO groups was observed. This infrared absorption spectrum is shown in FIG. The equipment used for the measurement was a Shimadzu 1R-400 infrared spectrophotometer, and the measurement method was KBr.
It is the law.
図面は本発明の実施例で得られた２，５−ジメ
トキシ−４，4′，4″−トリイソシアナト−トリフ
エニルアミンの赤外吸収スペクトルを示す。
The drawing shows an infrared absorption spectrum of 2,5-dimethoxy-4,4',4''-triisocyanato-triphenylamine obtained in an example of the present invention.
Claims (1)
を反応させることを特徴とする式（） で示されるイソシアナート化合物の製造法。[Claims] 1 Formula () An isocyanate compound represented by 2 formula () A formula () characterized by reacting an amine compound or a salt thereof with phosgene represented by A method for producing an isocyanate compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3459085A JPS61194057A (en) | 1985-02-25 | 1985-02-25 | Aromatic triisocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3459085A JPS61194057A (en) | 1985-02-25 | 1985-02-25 | Aromatic triisocyanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61194057A JPS61194057A (en) | 1986-08-28 |
| JPH0516422B2 true JPH0516422B2 (en) | 1993-03-04 |
Family
ID=12418541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3459085A Granted JPS61194057A (en) | 1985-02-25 | 1985-02-25 | Aromatic triisocyanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61194057A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102408416B1 (en) * | 2018-06-07 | 2022-06-14 | 우리화인켐 주식회사 | Method of preparing diisocyanate and optical lens |
| KR102456419B1 (en) * | 2019-12-06 | 2022-10-19 | 에스케이씨 주식회사 | Method of preparing diisocyanate composition and optical lens |
| KR102217752B1 (en) * | 2019-12-05 | 2021-02-19 | 에스케이씨 주식회사 | Method of preparing diisocyanate composition and optical lens |
| US11964931B2 (en) | 2019-12-05 | 2024-04-23 | Sk Pucore Co., Ltd. | Method of preparing diisocyanate composition and optical lens |
| KR102217747B1 (en) * | 2019-12-05 | 2021-02-19 | 에스케이씨 주식회사 | Method of preparing diisocyanate composition and optical lens |
| KR102456416B1 (en) * | 2019-12-06 | 2022-10-19 | 에스케이씨 주식회사 | Diamine composition, and method of preparing diisocyanate composition and optical material using same |
| JP7126217B2 (en) | 2019-12-06 | 2022-08-26 | エスケイシー・カンパニー・リミテッド | Method for preparing diamine composition and diisocyanate composition |
| US11932591B2 (en) | 2019-12-06 | 2024-03-19 | Skc Co., Ltd. | Method of preparing diisocyanate composition and optical lens |
| US12049437B2 (en) | 2019-12-06 | 2024-07-30 | Sk Pucore Co., Ltd. | Diisocyanate composition, preparation method thereof and optical material using same |
| KR102457569B1 (en) * | 2019-12-06 | 2022-10-21 | 에스케이씨 주식회사 | Diisocyanate composition, preparation method thereof and optical material using same |
| KR102456421B1 (en) * | 2019-12-06 | 2022-10-19 | 에스케이씨 주식회사 | Method of preparing diisocyanate composition and optical lens |
-
1985
- 1985-02-25 JP JP3459085A patent/JPS61194057A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61194057A (en) | 1986-08-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |