JPH02145556A - Aliphatic triisocyanate compound and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an aliphatic triisocyanate and a method for producing the same.

The isocyanate of the present invention is an aliphatic triisocyanate with a novel structure, and can be used as a raw material for various polyurethane resins such as paints, films, adhesives, and fibers, particularly as a curing agent for non-yellowing two-component polyurethane paints.

[Conventional technology]

Some aliphatic triisocyanate compounds are already known6. For example, triisocyanate compounds obtained by modifying 1,6-dicyanatohexane (hereinafter abbreviated as HDI)
(Poly)isocyanates are well known. Recently, 1,8 diisocyanato-4-incyanatomethyl-octane (hereinafter abbreviated as TIN) (hereinafter abbreviated as TIN) (JP-A-Show 56-6
1341), L6,11-undecane triisocyanate (hereinafter abbreviated as TIUD) synthesized by phosgenating 1,,6,11-undecanetriamine obtained from raw materials such as e-caprolactam (Japanese Patent Publication No. 5761352), Furthermore, in JP-A-53-135931, lysine ester triisocyanate (hereinafter referred to as LT) is synthesized by esterifying lysine and ethanolamine in the presence of an acid catalyst and phosgenating triamine hydrochloride.
(abbreviated as I) is introduced.

(Problems to be Solved by the Invention) The purpose of the present invention is to provide a novel aliphatic triisocyanate compound whose structure is completely different from that of a modified product of 1,6-dicyanatohexane, TIN, TIUD, and LTI. There is.

[Means to solve the problem]

The object of the present invention is to use 1,7-dicyanato-4-(3-isocyanatopropyl)-hebutane (hereinafter abbreviated as TID), which is a novel aliphatic triisocyanate compound having the following structural formula. achieved.

Conventionally known aliphatic trifunctional isocyanates include various modified products such as the aforementioned water adduct of HDI, adduct obtained by reacting trimethylolpropane, and modified isocyanurate, but when compared with TID of the present invention, The following drawbacks can be mentioned.

Namely, denaturation incurs considerable costs, the denatured product is dissolved in a solvent, and unreacted HDI, which has a high vapor pressure after denaturation and is harmful to the human body, must be removed. Poly(tri) excluding unreacted HDI
Since isocyanate contains a high molecular weight substance, it has a high viscosity.

In addition, the recently developed TIN, TIUD, and LTI are
Although it is a low viscosity and low toxicity aliphatic triisocyanate that has improved the drawbacks of the DI modified product, it has the following drawbacks.

TIN has a minimum number of carbons of 5 between NCO groups, and NG
Since the distance between O groups is relatively short, polyurethane resins using this triisocyanate lack flexibility and elasticity, and may have unreacted NGO groups. T
TUD has an NGO group bonded to a secondary carbon and is considered to have low reactivity. In addition, since LTI has an ester group structure, the acid resistance, alkali resistance,
There are concerns about poor hot water resistance.

Compared to the conventionally known aliphatic triisocyanates mentioned above, the TTD of the present invention has the excellent properties described below.

TID of the present invention has low viscosity and low toxicity. All NGO groups are bonded to primary carbons and have high reactivity. The number of carbon atoms between NGO groups is 7, which is longer than TIN and TIUD. For this reason, polyurethane resin using TID has flexibility and
It has excellent elasticity (possible elasticity). It has excellent quick drying properties especially when used as a curing agent for polyurethane paints.
The resulting coating film is non-yellowing, has excellent cross-linking properties, water resistance, acid resistance, alkali resistance, impact resistance, adhesion, stain resistance, light stability, high hardness, and has conventional aliphatic It is possible to obtain a polyurethane resin coating film having exceptionally excellent coating properties compared to when triisocyanates are used as a curing agent.

The TID of the present invention is an aliphatic triisocyanate compound having a completely new structure that has not been previously known, and was synthesized as a result of intensive research by the present inventors. The manufacturing method of TID will be described below.

The triisocyanate of the present invention is produced by phosgenating 1,7-diamitu-4-aminopropyl-hebutane represented by the above formula (II).

The aliphatic triamine compound is a novel compound synthesized by the present inventors, and after cyanoethylating nitromethane to synthesize tris-(β-cyanoethyl)nitromethane, tri-n-butyltin hydride and azobisisobutyronitrile are synthesized. Tris-(β-cyanoethyl)methane is obtained by a denitration reaction using as a reducing agent, and then hydrogenated using Raney cobalt as a catalyst.

As a method for phosgenating the above-mentioned 1,7-diami2-4-aminopropyl-hebutane, there is a method in which this triamine compound is directly reacted with phosgene, or a salt such as a hydrochloride of this triamine compound is synthesized in advance, and this is There are methods such as suspending it in an active solvent and reacting it with phosgene. The former method is called "cold-thermal two-stage phosgenation," and although there are no particular restrictions on the reaction method, it is generally placed in an inert reactor equipped with a phosgene gas introduction tube and capable of sufficient stirring in the reaction system. A solvent is added, cooled to 0-5"C, and phosgene gas is introduced to dissolve a predetermined amount of phosgene in the inert solvent.

Thereafter, an aliphatic triamine solution dissolved in an inert solvent is added while introducing a predetermined amount of phosgene gas. During this time, the reaction solution is kept below 15°C, and the generated hydrogen chloride and excess phosgene are taken out of the system through a reduction cooler.The main reaction is the production of carbamyl chloride and amine hydrochloride, and the inside of the reactor is in the form of a slurry. Become. After addition of the amine solution, the reaction is continued for a predetermined period of time.

The above process is called cold phosgenation.

Next, the inside of the reaction system is heated and the temperature is raised to about 140°C in about 1 hour. When the temperature is raised, dissolved phosgene tends to vaporize and foam, so the phosgene flow rate is reduced compared to when cold phosgenation is performed. After raising the temperature, the reaction is continued for a predetermined period of time, and the reaction is terminated when the slurry of the reaction liquid is completely dissolved.

The above process is called thermal phosgenation.

The main reactions of thermal phosgenation are the decomposition of carbamyl chloride into incyanate and the phosgenation of amine hydrochloride into isocyanate. After the completion of thermal phosgenation, the inside of the reaction system is maintained at 140° C. and a predetermined amount of nitrogen gas is blown in to remove dissolved gas. After cooling, the inert solvent is distilled off under reduced pressure to obtain a crude aliphatic triisocyanate. The crude aliphatic triisocyanate is purified by vacuum distillation.

The latter method is called "amine hydrochloride phosgenation method," and the hydrochloride of the aliphatic triamine is synthesized in advance. The hydrochloride is easily synthesized by a well-known method by treating an aliphatic triamine with hydrogen chloride or concentrated hydrochloric acid. The above-mentioned aliphatic triamine hydrochloride, which has been sufficiently dried and pulverized, is dispersed in an inert solvent in a reactor similar to that used in the above-mentioned "cold-hot two-stage phosgenation method", and the reaction temperature is increased to 80°C. The temperature is maintained at ~140°C, and phosgene gas is introduced to synthesize isocyanate. The progress of the reaction can be estimated based on the amount of hydrogen chloride gas generated and the disappearance of the aliphatic triamine hydrochloride insoluble in the inert solvent of the raw material, and the reaction solution becoming transparent and homogeneous. 0 Hydrogen chloride generated and excess phosgene gas After the reaction is completed, nitrogen gas is introduced into the reaction solvent to remove the dissolved phosgene, and after cooling and filtration, the inert solvent is distilled off under reduced pressure to obtain the crude aliphatic trifluoride. Obtain isocyanate. It is sufficient to introduce 3 to 10 times the theoretical amount of phosgene in both the "cold and hot two-stage phosgenation method" and the "amine hydrochloride phosgenation method." Further, as the inert solvent, aromatic hydrocarbons and chlorinated aromatic hydrocarbons are used, and ortho-dichlorobenzene is preferable.

The TID obtained by the above procedure has a boiling point of 168 to 170"
C/ 0.1 mm 11 g (oil bath point of distillation flask 18
It is a colorless and transparent liquid substance with a temperature of 0 to 190'C), and the following spectral data and elemental analysis values (examples) are shown.

(1) Elemental analysis value (C+3H+JsOs) CI
N CI Calculated value (χ) 58.85 7.22 15.84 Analysis value (χ) 58.95 7.53 15.90 0
．． 10 (2) NGO content NCO% = 47.5% (calculated value NCO% = 47.51%) (3) GC-MS analysis CI (isobutane)-MS spectrum (?IH)” -266 (Note TID Molecular weight = 265.31) (4) IR spectrum (NaC1 crystal plate, liquid film method) 1st
The figure shows the IR spectrum.

Absorption wave number C1-1 2870, 2840, 2230-2240 (isocyanate group), 1460.1355 (5) 'II-NMR spectrum (100 Mllz,
(in CDCl+) Figure 2 shows the NMRR spectrum.

” 13H in total [Example] Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 Using 1,7-diamitu-4-aminopropyl-hebutane represented by formula (n) as a raw material, phosgenation was performed by a cold and hot two-step method.

400 g of orthodichlorobenzene was charged into a 22 reaction flask equipped with a stirrer, a thermometer, a phosgene gas introduction tube, a cooling tube, and a dropping funnel, and while stirring, the reaction flask was placed in an ice water bath to maintain the internal temperature at approximately 5°C. , 75 g of phosgene gas
/h into the flask for 1 hour.

Next, 1 of the above 1,7-diami2-4-aminopropyl-hebutane dissolved in 250 g of orthodichlorobenzene.
2.5 g (0,0667 sol) was added dropwise over 30 minutes.

Cold phosgenation was carried out at 8 to 12'C while introducing phosgene gas at a rate of 50 g/h during the amine dropwise addition.

Due to the formation of carbamyl chloride, a colorless and transparent gel-like substance was formed in the flask due to the cold phosgenation.

The reaction solution was then heated to 140'C over 30 minutes. After raising the temperature, thermal phosgenation was carried out for 2 hours while introducing phosgene gas at a rate of 50 g/h at a reaction temperature of 140°C. During the thermal phosgenation process, the colorless and transparent gel was completely dissolved in orthodichlorobenzene. Total of 22 in cold and hot two-stage phosgenation
5 g of phosgene gas was introduced.

This was about 10 times the theoretical amount. After the completion of thermal phosgenation, degassing was carried out by introducing nitrogen gas at a rate of 300 m/in for 2 hours at a reaction temperature of 140"C. After cooling and filtration, the solvent orthodichlor was removed at a reduced pressure of about 1 mmHg. Benzene was distilled off to obtain 18 g of a brown reaction mixture.The brown reaction liquid was purified by vacuum distillation to give a boiling point of 168-17.
0'C10, 1mm) Ig (oil bath part 18 of distillation flask
Approximately 118 colorless and transparent liquid fractions (0-190°C) were obtained. Elemental analysis value, NGO content, GC-MS spectrum,
When we investigated the analytical values of the IR-spectrum and 'H-NMR spectrum, we found that they were the same as above, so TID (1
, 7-diisocyanato-4isocyanatopropyl-hebutane-a compound of formula (1)).

Example 2 Phosgenation was performed using 1,7-diamitu-4-aminopropyl-hebutane as a raw material by the hydrochloride method.

25 g (0,133 WAol) of the above triamine was dissolved in 25 mQ of methanol, and 50 g of 35% concentrated hydrochloric acid was gradually added dropwise under stirring at 25° C. or lower to produce a hydrochloride. Methanol and water were distilled off and concentrated under reduced pressure, and 100 m of methanol was added again for concentration to obtain viscous triamine hydrochloride. This is 2 at 70'C10,5nu++Hg
After drying for 4 hours, a pale red solid triamine hydrochloride was obtained. This hydrochloride was pulverized.

Triamine hydrochloride powder obtained by the above operation 19.8
g (0,0667+mol) was suspended in 400 g of orthodichlorobenzene and charged into a 12 reaction flask equipped with a stirrer, a thermometer, a phosgene gas introduction tube, and a cooling tube. 50g of phosgene while keeping the reaction temperature at 140°C.
/h for 3 hours and at a rate of 25g/h for 6 hours. At the end of the reaction, triamine hydrochloride almost disappeared. A total of 300 g of phosgene was used in the phosgenation by the hydrochloride method. This was about 15 times the theoretical amount. After completion of phosgenation, nitrogen gas was added to the reaction solution at 140"C for 300if.
/a+ip for 2 hours. After cooling, a small amount of undissolved matter was removed by filtration. Then, the solvent, orthodichlorobenzene, was distilled off under reduced pressure of about 1 mmHg to obtain about 17 g of a brown reaction product. The brown reaction liquid was purified by vacuum distillation to a boiling point of 175-180°C/0.15 anHg.
The analysis values of the 0 element analysis value, NGO content, IR-spectrum, and 'HNMR spectrum obtained from about 10 g of the fraction (185-195°C in the oil bath of the distillation flask) are the same as in Example 1. It was identified as TID (compound of 1,7-diisocyanato-4isocyanatopropyl-hebutane-formula (1)).

4,

[Brief explanation of the drawing]

Figure 1 is the IR spectrum of TID, Figure 2 is the N of TID.
It is a figure showing an MR spectrum.

Claims (1)

[Claims] 1) Formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 1,7-diisocyanato-4-isocyanatopropyl-heptane represented by (I) 2) Formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc.▼(II) 1,7-diisocyanate-4-, which is characterized by reacting 1,7-dimino-4-aminopropyl-heptane or its salt with phosgene. A method for producing isocyanate propyl-heptane.