JPH0324049A - Novel aliphatic triisocyanate and production thereof - Google Patents

Abstract

NEW MATERIAL:4-Phenyl-4-isocyanatomethyl-1,7-diisocyanatoheptane of formula I. USE:Useful as a raw material for various polyurethane resins for paint, film, adhesive, fiber, etc., and especially as a curing agent for non-yellowing two-pack polyurethane paint. PREPARATION:The objective compound of formula I can be produced by phosgenating 4-phenyl-4-aminomethyl-1,7-diaminoheptane of formula II or its salt by two stage cold and hot process. The 1st stage reaction is carried out at 0-15 deg.C and the 2nd stage is performed at >=140 deg.C. The compound of formula II is a novel compound which can be produced by converting benzyl cyanide to di(cyanoethyl) compound, synthesizing 3-phenyl-3-cyano-1,5-dicyanopentane and hydrogenating the compound in the presence of a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to aliphatic triisocyanates and methods 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, especially as a curing agent for non-yellowing two-component polyurethane paints. [Prior Art] Several aliphatic triisocyanate compounds are already known. For example, tri(poly)isocyanates obtained by modifying 1,6-diisocyanatohexane (hereinafter abbreviated as MDI) are well known. Also,
Recently, 1,8-diisocyanato-4-isocyanatomethyl-octane (hereinafter abbreviated as TIN) is synthesized by phosgenating triene obtained by hydrogenating a tricyano compound obtained by trimerizing acrylonitrile. 1,6,11-undecane triisocyanate (hereinafter referred to as TIUD), which is synthesized by phosgenating 1,6,11-undecane triisocyanate obtained from raw materials such as ε-cabrolactam (abbreviated as) (Unexamined Japanese Patent Publication No. 1987-
61352), and JP-A-53-135931 discloses a lysine ester triisocyanate prepared by esterifying lysine and ethanolamine in the presence of an acid catalyst and phosgenating the resulting triamine hydrochloride. NART (hereinafter abbreviated as LTI) is introduced. [Problems to be Solved by the Invention] The object of the present invention is to provide a novel aliphatic triisocyanate compound whose structure is completely different from that of modified 1,6-diisocyanatohexane, TIN, TIUD, and LTI. (Means for solving !III) An object of the present invention is to provide a novel aliphatic triisocyanate compound represented by the following structural formula (I), 4-phenyl-4-isocyanatomethyl-1.7. - diisocyanatohebutane (hereinafter abbreviated as TIPO). Conventionally known aliphatic trifunctional isocyanates include the aforementioned water adduct of HDI, adduct obtained by reacting trimethylolpropane, and modified isocyanurate. There are various modified products such as TDI of the present invention, but when compared with the TDI of the present invention, the following disadvantages can be cited: modification increases the cost considerably, the modified product takes a form dissolved in a solvent, It is necessary to remove unreacted HDI, which has a high vapor pressure and is harmful to the human body.
Isocyanates contain high molecular weight substances and therefore have high viscosity. The TIPO of the present invention has the following excellent properties compared to conventionally known aliphatic triisocyanates. The TIPO of the present invention has low viscosity and low toxicity. NCOi
All bond to primary carbons and have high reactivity. Also, since aromatic rings and methylene chains coexist in the structure, TIP
Polyurethane resin using O can have both appropriate hardness and elasticity (flexibility). Furthermore, due to the coexistence of the aromatic ring and methylene oxide, it is expected to have excellent compatibility with various solvents. In particular, when used as a curing agent for polyurethane paints, it has excellent quick-drying properties, and the resulting coating film is non-yellowing, cross-linkable, water resistant, acid resistant, alkali resistant, impact resistant,
A polyurethane resin coating with excellent adhesion, stain resistance, light stability, high hardness, and exceptionally superior coating properties compared to conventional aliphatic triisocyanates used as curing agents. It is possible to obtain a membrane. TIPO 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 production of TIPO will be described below. 4-phenyl-4-aminomethyl-1,7-diaξnohebutane represented by the above formula (n) is a novel compound synthesized by the present inventors, and is a compound obtained by converting pendyl cyanide into di(
3-phenyl-3-cyano (cyanoethyl) 1.5
-It is obtained by combining dicyanobentane and then hydrogenating it using a catalyst. The method for phosgenating the above-mentioned 4-phenyl-4-aξnomethyl-1.7-diaminohbutane includes a method in which this triamine compound is directly reacted with phosgene (cold and hot two-step method), or a hydrochloride salt of this triamine compound. There is a method (hydrochloride method) in which salts such as the following are pre-prepared, suspended in an inert solvent, and reacted with phosgene. Generally, when a polyisocyanate is synthesized by reacting a fatty polyamine compound with phosgene, the carbamoyl compound and amine hydrochloride that are present in the intermediate stage of the reaction become solid lumps in an organic solvent in the two-step cold and hot process. The progress of the reaction is often significantly hindered. The inventors of the present invention
When carrying out the reaction using the stage method, we observed the formation of fairly hard lumps at 100 to 110°C during the temperature raising stage from stage 1 to stage 2, but when the temperature was raised to 140°C or higher, the lumps disappeared. They found that it softens and eventually disperses in the form of a slurry. Furthermore, this slurry becomes a clear solution upon completion of the phosgenation reaction. Thus, in the cold-thermal two-stage process, the first stage reaction is carried out at 0 to 15°C, and the second stage reaction is carried out at 140'C or higher, preferably 150 to 160°C, resulting in a relatively short reaction time. The yield is <TIPO
can be obtained. In addition, in the hydrochloride method, 140°C or higher, preferably 150°C
Similar results can be obtained by performing the reaction in one stage at ~160°C. [Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the following Examples. (Example 1) Production of 4-phenyl-4-aminomethyl-1,7-diaξ-hebutane 3-phenyl-3-cyano-1,5-dicyanopenkune 33 synthesized by di(cyanoethyl)ation of penzyl cyanide .6g (0.15 mol) to 160g of ethanol
and charged into a 400cc tM1 autoclave equipped with an induction stirrer. As a catalyst, 10 g of Raney cobalt (expanded before use) ethanol paste and 0.8 g of acetic acid were added, and stirring was started. After purging the autoclave space with nitrogen, it was pressurized with hydrogen to 80 kg/d, and the internal temperature was reduced to 100 kg/d in the autoclave warming heater.
Raise the temperature to ℃. The internal pressure becomes approximately 90 kg/d due to temperature rise, but hydrogen is introduced to increase the pressure to 110 kg/cd.
Hydrogen absorption through the hydrogenation reaction has already begun, and after 90
~ 110kg/cd, 100 soil, 10℃, continue with anti-2. 2 hours and 30 minutes after the start of hydrogen charging, hydrogen absorption stops, so the reaction is considered complete. After filtering off the catalyst, the elemental analysis values of the triamine obtained by filtration were as follows. Elemental analysis value (C.l1tsNi-235.3)C
H N calculation (l [(%) ?1.44 10.71
17.85 Actual value (%) 71.14 1
0.91 17.52 (Example 2) Production of 4-phenyl-4-isocyanatomethyl-1.7-diisocyanatohebutane 4-phenyl-4-aminomethyl- produced in Example 1
Using 1,7-diaminohbutane as a raw material, phosgenation was carried out by a cold and hot two-step process. 450 g of orthodichlorobenzene was charged into a 21 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, and the phosgene gas was added. 100g/
It was introduced into the flask at a rate of 1 h for 1 hour. Then, 4 dissolved in 300 g of orthodichlorobenzene
25.0 g (0.106 mol) of -phenyl-4-aminomethyl-1,7-diaminohbutane was added dropwise over 60 minutes. When dropping amine, add 100 g of phosgene gas/
Cold phosgenation was carried out at 5-10°C while introducing at a rate of h. Furthermore, even after the amine dropwise addition was completed, phosgene gas was introduced at 100 g/h for 1 hour from 5 to'c to continue cold phosgenation. Next, the temperature of the reaction solution was raised to 150° C. over 30 minutes while introducing phosgene at a rate of 25 g/h. After raising the temperature, thermal phosgenation was carried out by introducing phosgene gas at a rate of 75 g/h for 2 hours and then at a rate of 50 g/h for 4 hours at a reaction temperature of 150"C. During the process of thermal phosgene, the reactants were converted into ortho-phosgene. Completely dissolved in dichlorobenzene. After completion of thermal phosgenation,
Nitrogen gas is supplied at 300ad/s at a reaction liquid temperature of 140”C±5℃.
The gas was introduced at a rate of in for 2 hours to perform degassing. After cooling and filtration, orthodichlorobenzene was distilled off at a reduced pressure of about 1 mHH to obtain 31.6 g of a brown reaction liquid. This reaction solution was detarred by vacuum simple distillation, and 21.1
g of distillate was obtained. This fraction 17. 87.5 g of zinc stearate was added to Og, and high vacuum distillation was performed while refluxing. Zinc stearate was added to remove trace amounts of hydrolyzable chlorine compounds as by-products. This results in a vacuum level of 1 to 1. ．． 2 mHg abs 200
Fraction 14 at ~210°C. Obtained Og. (Colorless transparent liquid NCO%39.8%, same theory {[40.2
%) The elemental analysis values of this product were as follows.

Elemental analysis value (C+, H+-NsOs) C H N Cl calculation {1 (%) 65.16 6.11 13.
41 0 Actual value (%) 64.77 6.0
m 13.16 0.01 In the GC-MS spectrum, (M")-313 was observed, which matched with the molecule i1 313.4 of the compound of formula (I). Also, the purity from the GC chart was 97.9%, Hydrolyzable chlorine content is 100
It was 0 ppm. From the above, this fraction was identified as the compound of formula (I).

Claims (1)

[Claims] 1) 4-phenyl-4-isocyanatomethyl-1 represented by formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)
,7-diisocyanatoheptane2) Formula (II) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(II) 4-phenyl-4-aminomethyl-1,7-
A method for producing 4-phenyl-4-isocyanatomethyl-1,7-diisocyanatoheptane, which comprises reacting diaminoheptane or a salt thereof with phosgene.