JPS593991B2 - Shinkina Takanshikiji Isocyanate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel polycyclic diisocyanate which is liquid and has a low vapor pressure.

As is well known, diisocyanates that are liquid at room temperature have better processing properties than solid diisocyanates.

Moreover, diisocyanates with low vapor pressures are industrially desirable because they are easy to handle in terms of toxicity. Furthermore, while aromatic diisocyanates turn yellow during polyurethanization, aliphatic diisocyanates do not turn yellow. The present inventor has discovered the previously invented polycyclic diamine represented by the general formula (1) (Japanese Patent Application No. 50-61
11)・・・・・・・・・(1) (In the formula, R may be the same or different, each represents hydrogen or a methyl group, and A or B represents an amino acid group, one of which is an amino group. One is a methyl group, the other is hydrogen, and X and y are each o or 1
, where n means 1 or 2), was reacted with phosgene to convert the amino group into 30 ml of isocyanate, thereby obtaining an alicyclic diisocyanate that is liquid at room temperature and has a low vapor pressure. .

Furthermore, it has been found that the diisocyanate obtained by the present invention exhibits excellent reactivity and is a useful raw material for polyurethane resins. 35 The polycyclic diamine of formula (1) used in the present invention is acrylonitrile or acrolein or a methyl substituted product thereof, cyclopentadiene, 1
・3-butadiene, 1,3-pentadiene, isoprene,
It is obtained by adding two or three molecules of a conjugated diene such as 2,4-hexadiene to form a polycyclic unsaturated compound, hydroformylating the unsaturated group within the ring, and then reducing the compound with ammono.

In this way, the materials of the present invention can all be assembled from materials that are industrially produced in large quantities or are by-products. In formula (1), whether R is hydrogen or a methyl group, or whether x and y are O or 1, depends on whether the acrylic monomer and conjugated diene are methyl substituted,
For example, menocrylonitrile, isoprene, etc. can be freely selected depending on how they are used in combination, but in any case they have the essential characteristics of the diisocyanate obtained by the present invention. Also, n in formula (1)
Although the essential characteristics will not be lost through selection of the number, the one that provides preferable physical properties depending on the purpose of use should be selected. However, since the characteristics of liquid and low vapor pressure according to the present invention are probably derived from the polycyclic structure, it is an important condition of the present invention that n is 1 or 2 or a mixture thereof. In addition,
In formula (1), whether the aminomethyl group is present at A or B is automatically determined depending on the type of R and reaction conditions. In the present invention, the method for reacting the polycyclic diamine of formula (1) with phosgene is not particularly different from that for reacting other amino compounds, and known reaction conditions can be applied as is.

That is, isocyanate is easily produced by acting with phosgene in an amount equal to or more than the amino group, preferably 1.5 moles or more. At this time, if hydrogen chloride is present, the reaction is likely to start. The operation becomes easier when aromatic hydrocarbons such as benzene, toluene, xylene, and cumene, chlorinated hydrocarbons such as monochlorobenzene, and saturated lower alkyl esters such as ethyl acetate and glycol acetate are used as solvents. The reaction proceeds even at low temperatures below zero, but at the end of the reaction the temperature reaches up to 180°C, for example 120°C.
Completion can be accelerated by heating. The polycyclic diisocyanate obtained by the present invention has good handling properties and is useful not only for urethane elastomers and urethane foams but also for urethane paints.

For example, in the presence of pyridine, polyoxypropylene glycol is heated to 145°C to form an elastomer, and then heated to 160°C.
When press-molded, it becomes a transparent flexible film. In addition, a prepolymer is obtained by reacting with trimethylolpropane at 60°C, and by mixing polyester polyol (Daismophen 1100) and triethylene diamine and diluting it with a paint solvent, a polyurethane paint is obtained. Forms a highly hard coating film, similar to when used. Next, the manufacturing method of the present invention will be explained in more detail with reference to Examples.

Example 1 Put four pieces of toluene 2007 into a Lokolben, attach a stirrer, dropping funnel, thermometer, gas introduction pipe and cooler,
The outlet of the condenser was connected to a trap containing 30% caustic soda in water.

It is then cooled to 0°C with a cryogen, 10y of phosgene is bubbled into toluene, and then the mixture of diamines )±)l and . Enemy L pant-4▼▼? -20y (boiling point: 1544-157°C/1.5mmHg) was mixed with toluene 207, and the mixture was added from a dropping funnel over 5 hours.

Blow in phosgene at the same time as diamine addition, and in 5 hours,
Added another 70 yards. Then, after leaving it overnight at 0-5℃,
After gradually raising the temperature and keeping it at 90-100°C for 2 hours, the condenser was removed, a simple distillation apparatus was installed, and the exhaust port was connected to an alkali trap. Then the temperature is raised to 110-12
Toluene was gradually concentrated at 0° C. over 3 hours to reduce the reaction solution to 1/3 of the total volume. After that, it is cooled, the insoluble matter is removed by filtering, the toluene is distilled off, and the 180-19
A mixture 157 (75% yield) of liquid diisocyanate [)T)] was obtained in a fraction of 5° C./0.5 to 1 mlHg.

Example 2 200 tons of xylene was placed in four Locolbens, and a stirrer, dropping funnel, thermometer, gas introduction tube, and cooler were attached, and the outlet of the cooler was connected to a trap containing a 30% caustic soda aqueous solution.

Mixture with diamine TT ↓↓z▲▼▲Crystal ZVV↓↓z↓1琐▲Z 2O7 was added and hydrogen chloride was bubbled in to saturate the solution.

Thereafter, 50 y of phosgene was blown in for 3 hours while maintaining the temperature at 00 to 5°C. Thereafter, 307 phosgene was blown into the Kolben over 2 hours while gradually raising the temperature to 100°C.

It was then held at reflux temperature for 5 hours. The remaining phosgene was then expelled through nitrogen gas. The solution was cooled, filtered with F, xylene was distilled off at normal pressure, and then distilled under reduced pressure.
Liquid diisocyanate 0CNH2C with a fraction of 175-185℃/0.5-1mmHg
@ and one. ．． ,,． 〕Two〉〕,,,．． A mixture with (8)
6% yield) was obtained.

Example 3 H2NH2C'>C. ]MiΣYumiEko, -, -7 and ``
The mixture was dissolved in methanol 1007, and while cooling the solution, hydrogen chloride was blown into the solution at 15 to 20°C to obtain a dihydrochloride.

Thereafter, menonol was distilled off to obtain solid dihydrochloride 25y. Dichlorobenzene 1007 and the above-mentioned dihydrochloride 207 were placed in a four-piece Locolben, and a stirrer, a thermometer, a gas inlet tube, and a cooler were attached, and the mixture was heated to 160° C. and reacted while blowing in phosgene 507 for 5 hours.

Claims (1)

[Claims] ▲ Numerical formulas, chemical formulas, tables, etc. is hydrogen, X and Y each represent 0 or 1, and n represents 1 or 2) by reacting phosgene with a polycyclic diamine,
It is characterized in that the amino group of the polycyclic diamine is changed to an isocyanate. Either A or B in the above general formula is CH_2NC
A method for producing a new polycyclic diisocyanate.