JP3185807B2 - Aliphatic polycyclic diisocyanate compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel aliphatic polycyclic diisocyanate compound and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, diisocyanate compounds are useful compounds used as raw materials for polyurethanes and the like. In general, polyurethanes obtained from aliphatic polycyclic diisocyanate compounds have better yellowing resistance than polyurethanes obtained from aromatic diisocyanate compounds.Furthermore, aliphatic polycyclic diisocyanate compounds have heat resistance. It is an excellent compound.

As such alicyclic diisocyanate compounds having a diisocyanate group and an aliphatic polycyclic structure, compounds described in JP-B-59-3991 are known. However, in the aliphatic polycyclic diisocyanate compound described in the publication, since isocyanate groups are randomly substituted in different alicyclic skeletons, when a polyurethane or the like is synthesized, the alicyclic structure is randomly incorporated into the main chain of the polyurethane. And the regularity of the three-dimensional structure is not seen at all,
It is not preferable because mechanical properties such as heat resistance, weather resistance, chemical resistance, water resistance, and abrasion resistance, or optical properties such as transparency are not sufficiently exhibited.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an aliphatic polyurethane which has a structure which is stereochemically substituted with two isocyanate groups adjacent to a specific alicyclic skeleton which has not been known before. It is an object of the present invention to provide a polycyclic diisocyanate compound and a method for producing the same.

The present invention relates to a compound represented by the general formula

[0006]

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(Wherein n represents 0 or 1), and an aliphatic polycyclic diisocyanate compound represented by the general formula:

[0008]

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[0009] The present invention relates to a process for producing an aliphatic polycyclic diisocyanate compound, wherein a phosgene is reacted with a diamine compound represented by the formula (wherein n is the same as described above).

The aliphatic polycyclic diisocyanate compound of the present invention can be obtained by reacting a diamine compound represented by the general formula (2) with phosgenes.

Known reaction conditions can be adopted as they are. That is, phosgenes having an equivalent or more, preferably about 1.5 to 15 mol, of the amino group of the diamine compound are allowed to act. As phosgenes, in addition to phosgene, trichloromethyl chloroformate (usually diphosgene) and bistrichloromethyl carbonate (usually triphosgene) can also be used. Further, the diamine compound may be used as a hydrochloride with hydrogen chloride. As the solvent, benzene,
Aromatic hydrocarbons such as toluene, xylene and cumene, chlorinated hydrocarbons such as monochlorobenzene, and saturated alkyl esters such as ethyl acetate and glycol acetate can be used.
The temperature is usually preferably from 0 to 250 ° C.

As a method for producing the above-mentioned diamine compound as a raw material, for example, fumaronitrile or maleonitrile is reacted with cyclopentadiene or dicyclopentadiene,

[0013]

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(Wherein n is the same as described above), and then a dinitrile compound is reduced to obtain a diamine compound.

More specifically, first, fumaronitrile or maleonitrile is reacted with cyclopentadiene or dicyclopentadiene, and a 1: 1 adduct of cyclopentadiene with fumaronitrile or maleonitrile (compound of general formula (3) where n = 0) To manufacture.

Next, the 1: 1 adduct is hydrogenated in the presence of a catalyst such as nickel to reduce the double bond and the cyano group to form an aliphatic polycyclic diamine compound (compound of general formula (2) wherein n = 0)
To manufacture.

The above 1: 1 adduct is further reacted with cyclopentadiene or dicyclopentadiene to give a 2: 1 adduct of cyclopentadiene with fumaronitrile or maleonitrile (compound of general formula (3) where n = 1) And hydrogenating the 2: 1 adduct in the presence of a catalyst such as nickel to reduce the double bond and cyano group in the same manner as described above to obtain an aliphatic polycyclic diamine compound (n = 1 in the general formula (2)). Is produced.

Since the compound of the formula (3) is usually obtained as a mixture of a 1: 1 adduct and a 2: 1 adduct, each may be separated by distillation under reduced pressure or the like and then derived into a diamine compound. Alternatively, the mixture may be separated into a diamine compound after being induced. Further, the mixture may be separated into the diisocyanate compound after being induced.

The compound of the formula (3) may be converted to a diamine compound after hydrogenation of only the double bond and separation of each compound by distillation under reduced pressure or the like.

When fumaronitrile is used as a raw material, a trans diamine compound is obtained, and when maleonitrile is used, mainly a cis diamine compound is obtained.

That is, in the production of the above diamine compound, diamine compounds of isomers having different steric structures can be obtained, and both can be used in the production method of the present invention. The diamine compound is derived into a diisocyanate compound while maintaining its steric structure. Therefore, the aliphatic polycyclic diisocyanate compound of the general formula (1) of the present invention includes compounds having various steric structures, and each compound can be synthesized.

[0022]

According to the present invention, a novel aliphatic polycyclic diisocyanate compound is provided. The alicyclic diisocyanate compound is useful as a raw material for polyurethane and the like.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0024]

Example 1 (i) trans-2,3-dicyano-1α, 2,3,4
α, 4aα, 5β, 8β, 8aα-octahydro-1,
Synthesis of 4: 5,8-Dimethanonaphthalene (compound of general formula (3) wherein n is 1) In a four-necked flask equipped with a stirrer, a cooler, a thermometer, and a dropping funnel, 117 g of fumaronitrile (1.50 Mol), 99 g (0.75 mol) of dicyclopentadiene (hereinafter abbreviated as DCPD), o-dichlorobenzene 3
15 g was charged and dissolved by heating to a liquid temperature of 170 ° C. to 180 °
° C. After confirming the temperature rise by the reaction heat, about 1 hour 1
The mixture was kept at 80 ° C. to obtain a reaction mixture mainly composed of a 1: 1 adduct of cyclopentadiene and fumaronitrile (trans-2,3-dicyanonorbornene-5). Further, 99 g (0.75 mol) of DCPD was supplied to the reaction mixture via a dropping funnel over 3 hours, and the temperature was maintained at the same temperature for 1 hour, and a 2: 1 adduct of cyclopentadiene and fumaronitrile (trans-2,3-dicyanonorbornene) was added. -5 to which cyclopentadiene is added), ie, trans-
2,3-dicyano-1α, 2,3,4α, 4aα, 5
A reaction mixture containing β, 8β, 8aα-octahydro-1,4: 5,8-dimethanonaphthalene as a main component was obtained.

Next, the obtained reaction mixture was distilled under reduced pressure to remove o-dichlorobenzene first,
36 g of a fraction of 6 to 139 ° C / 6 mmHg (a fraction having a 1: 1 adduct as a main component) and a boiling point of 136 to 139 ° C /
203 g of a 0.35 mmHg fraction (a fraction containing a 2: 1 adduct as a main component) was obtained. The fraction of the 2: 1 adduct was recrystallized from ethanol to obtain 174 g of white crystals having a melting point of 108 to 110 ° C.

(Ii) trans-2,3-bisaminomethyl-1α, 2,3,4α, 4aα, 5β, 6,7,8
Synthesis of β, 8aα-decahydro-1,4: 5,8-dimethanonaphthalene (compound of general formula (2) where n is 1) 148 g of the dicyano compound synthesized in (i) above in a 1-liter stirred autoclave ( 0.70 mol), methanol 300 ml and Raney nickel 62 g were charged and sealed, and then 200 ml of liquid ammonia was injected. Then 1
Keep the temperature at 00 ° C, inject hydrogen gas, and pressure 100kg
/ Cm ² while stirring. After absorbing a predetermined amount of hydrogen gas in 4 hours, the same temperature and the same pressure were maintained for another 1 hour. Thereafter, the mixture was cooled to room temperature, and after removing ammonia, the catalyst was separated by filtration and the solvent was distilled off under reduced pressure to obtain 124 g of white crystals.

(Iii) trans-2,3-bisisocyanatomethyl-1α, 2,3,4α, 4aα, 5β,
6,7,8β, 8aα-decahydro-1,4: 5,8-
Dimethanonaphthalene (compound of general formula (1) wherein n is 1)
In a four-necked flask equipped with a stirrer, a cooler, a thermometer, and a hydrogen chloride gas introducing tube, 22 g (0.10 mol) of the diamine compound synthesized in (ii) was mixed with o-dichlorobenzene 1
After dissolving in 00 ml, while stirring vigorously, dry hydrogen chloride gas was introduced to produce hydrochloride of diamine. The solution of this hydrochloride was brought to 130 ° C., and phosgene was introduced at a rate of about 20 g / hour for 5 hours. Then, the reaction temperature was increased to 180 ° C., and phosgene was introduced at a rate of about 10 g / hour for 5 hours. Then, the mixture was kept at the same temperature for 1 hour to complete the reaction. After o-dichlorobenzene was distilled off from the obtained mixture under reduced pressure, the boiling point was 169-173 ° C /
14 g of a transparent liquid fraction of 0.4 mmHg was obtained. This substance was identified by ¹ H-NMR, ¹³ C-NMR, IR-spectral analysis and mass spectrometry to confirm that it was the desired diisocyanate compound. The following shows the spectrum data.

¹ H-NMR (CDCl ₃ ): 3.2
(M, 4H), 2.28 (bs, 2H), 2.25
(D, 1H), 2.03 (s, 1H), 1.86 (d.
d. , 1H), 1.77 (dd, 1H), 1.6
(M, 2H), 1.5 (m, 2H), 1.35 (m, 2
H), 1.32 (d, 1H), 1.24 (dt, 1
H), 1.11 (d, 1H), 0.99 (m, 1H)
(Ppm).

¹³ C-NMR (CDCl ₃ ): 122.2
4, 121.83, 50.46, 49.90, 48.6
2, 46.32, 43.47, 42.21, 41.2
1, 41.15, 40.75, 39.97, 38.3
5, 32.66, 24.43 (ppm).

IR (neat): 2946, 2887,
2290 (sh), 2258 (cm ^-1 ).

MS (m / e): 272 (M ⁺ ).

[0032]

Example 2 trans-2,3-bisisocyanatomethyl-1α,
2,3,4α, 4aα, 5β, 6,7,8β, 8aα-
Synthesis of decahydro-1,4: 5,8-dimethanonaphthalene (compound of general formula (1) wherein n is 1) In a four-necked flask equipped with a stirrer, a cooler, a thermometer and a hydrogen chloride gas inlet tube. After dissolving 6.61 g (30 mmol) of the diamine compound synthesized in (ii) of Example 1 in 50 ml of o-dichlorobenzene, the mixture was vigorously stirred.
Dry hydrogen chloride gas was introduced to produce a diamine hydrochloride. Next, a dropping funnel was attached in place of the hydrogen chloride gas introduction pipe. The solution of the hydrochloride was heated to 170 to 180 ° C., and a solution in which 14.84 g (50 mmol) of bistrichloromethyl carbonate (commonly called triphosgene) was dissolved in 50 ml of o-dichlorobenzene was dropped from the dropping funnel over 5 hours. The reaction was carried out and further kept at the same temperature for 1 hour to complete the reaction. Thereafter, in the same manner as in (iii) of Example 1, 3.32 g of the objective diisocyanate compound was obtained. The substance was identified by ¹ H-NMR, ¹³ C-NMR, IR-spectral analysis and mass spectrometry, and was found to be the same as (iii) in Example 1.

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Claims (2)

(57) [Claims] 1. A compound of the general formula (In the formula, n represents 0 or 1.) An aliphatic polycyclic diisocyanate compound represented by the formula: 2. A compound of the general formula The method for producing an aliphatic polycyclic diisocyanate compound according to claim 1, wherein a phosgene is reacted with the diamine compound represented by the formula (where n represents 0 or 1).