JPS6026775B2 - Lysine ester triisocyanate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel aliphatic triisocyanates.

Conventional aliphatic polyisocyanates provide improved photostability to the urethanes derived therefrom, but because they are made from low molecular weight diisocyanates, they have a molecular weight distribution and contain diisocyanates with high vapor pressure.

This diisocyanate with a high vapor pressure is harmful to the human body and must be removed, but the polyisocyanate other than this diisocyanate contains high molecular weight substances and therefore has a significantly high viscosity. The object of the present invention is to provide new polyisocyanates having aliphatic isocyanate groups, with functional groups greater than 2 and with a significantly lower viscosity.

Still another object of the present invention is to obtain a polyisocyanate which has a low vapor pressure and is substantially odorless at room temperature. The objects of the present invention are achieved by the novel triisocyanates described below.

That is, the present invention is a lysine ester triisocyanate represented by the following general formula: (wherein R is an alkylene group having 2 to 5 carbon atoms).

The chemical structure of IJ digestel triisocyanate of the above general formula is confirmed by infrared absorption, nuclear magnetic resonance and mass analysis. In other words, in the infrared absorption spectrum, it is 2225
Ka-1 shows absorption by isocyanate group and ester carbonyl around 1740-1, and the nuclear magnetic resonance spectrum shows a peak centered around 1.7-4 (proton of methylene group) and around 3.5-legged. (a proton bonded to a carbon atom having an isocyanate group) and a peak centered around 4.4 skin or 4. ■
Tsuyoshi and 5. It shows two peaks centered near the Q skin (protons bonded to carbon atoms with isocyanate groups and carbonyl groups, and protons bonded to carbon atoms with oxygen atoms in esters), and the integral values of each peak are equivalent. Proportional to the number of protons. In the mass vector, in addition to the peak corresponding to the molecular weight, m/e153 (this is OCN-CH2
A peak is shown at CQC Day 2 (a characteristic peak corresponding to a fragment of CQC Day-NCC). Therefore, compounds of the above general formula can be immobilized by these physical means. The novel triisocyanates can be prepared, for example, by phosgenation of the corresponding lysine aminoalkyl esters.

Since this lysine aminoalkyl ester is also a previously unknown compound, the method for producing it and then the method for producing the triisocyanate of the present invention will be explained. Lysine aminoalkyl esters are prepared by reacting lysine with an alkanolamine in an inert liquid reaction soot in the presence of hydrogen chloride or an acid such as p-toluenesulfonic acid, and the resulting water entrains with the reaction medium. It can be produced by separating. Lysine aminoalkyl esters are obtained as hydrochloride or p-toluenesulfonate. p-Toluenesulfonate can be easily converted to hydrochloride by passing it through a CI-type strongly basic ion exchange column as a methanol solution. The lysine can be either optically active or racemic, and the alkanolamine contains 2 to 5 carbon atoms, one primary or secondary hydroxyl group and one primary amine/group.

Particularly preferred alkanolamines are ethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol, 5-amino-1-pentanol, 2,2-dimethyl-3-amino -1-propanol. Examples of the reactive substance include aromatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated Abizuka hydrocarbons, and tetramethylene sulfone. The lysine ester triisocyanate of the present invention is produced, for example, by phosgenating a lysine aminoalkyl ester obtained by the method described above. Lysine aminoalkyl esters are usually used in the form of hydrochloride for phosgenation. dispersing the hydrochloride salt in an inert liquid reaction medium and maintaining the temperature of the reaction soot between about 80 and 15 degrees centigrade;
Introduce phosgene. The triisocyanate of the present invention can be obtained by distilling off the reaction soot under hydraulic pressure and then performing high vacuum distillation. Suitable liquid reactive soot substances include aromatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated alicyclic hydrocarbons, and the like. The triisocyanates of the present invention have several advantages over previously known polyisocyanates.

In other words, it is a transparent liquid with very low viscosity at room temperature, almost colorless, and because it is not manufactured from low molecular weight diisocyanates, it does not contain diisocyanates with high vapor pressure, and is completely odorless and does not irritate the mucous membranes of the eyes at room temperature. do not. Therefore, the triisocyanate of the present invention is a compound useful as a raw material for producing polyurethane, and is particularly suitable for use as an isocyanate component in two-component polyurethane paints.

This paint has no pungent odor and forms a long-lasting coating with excellent surface hardness, good solvent resistance, light stability and film resistance. Example 1 After the loss, the thermometer, gas inlet pipe and Dean-S are connected to the rk
122. in a four-loaf flask fitted with a reflux condenser and fitted with a reflux condenser. (2.0 mol) of ethanolamine, 100
1' of o-dichlorobenzene and 420' of toluene were added, and hydrogen chloride gas was introduced under water cooling to convert ethanolamine into hydrochloride.

Next 182. IJ dine-hydrochloride (1.0 mol) was added, the reaction mixture was heated to 8000 ℃ to melt the ethanolamine hydrochloride, and hydrogen chloride gas was introduced to give lysine dihydrochloride. Further hydrogen chloride gas was passed through at a rate of 20 to 30° per minute, and the reaction mixture was heated to reflux temperature (116 °C
) and maintained at this temperature until no more water came out. This took about 8 hours. Decant the cooling solvent and
A strained solution of methanol and ethanol was added to the oil, heated, and allowed to stand at room temperature to precipitate crystals. This was taken in a furnace and recrystallized from a mixed solution of methanol and ethanol to obtain IJ gin 3-aminoethyl ester trihydrochloride 1.6 acid having a melting point of 175°C. Next, the elemental analysis values and the main peaks in the infrared absorption and nuclear magnetic resonance spectra are shown.

C8th. Calculated value for 9N302/9HCI: C32
．． 18%, day 7.43%, N14.07%, actual value: C
32.38%, day 7.43%, N14.22%, infrared absorption spectrum (KBr): 2100-1850 (ammonium salt), 1740 (ester carbonyl), 122
0ga-1 (Ester A Reishi; Gunsho Noodles Kyumasu Koken J4
．． 48 (2 days, -COOCH2-), 7.0-9. &Blood (Team, N day).

Example 2 After rinsing, 12. he(
0.2 mol) of ethanolamine, 87. Spot (0.46
moles) of p-toluenesulfonic acid hydrate, 18.3 g
Add (0.1 mol) of IJ gin hydrochloride and 180' of benzene, and while praying,
) was heated.

The resulting water was removed by azeotropic distillation with benzene and the reaction was completed after 9 hours. After cooling, the benzene layer was removed, and the oily substance in the lower layer was washed several times with acetone to precipitate crystals. This was taken in a furnace and recrystallized from a mixture of ethanol and isopropanol to obtain 4 keys of lysine 3-aminoethyl ester nitrilethosulfonate having a melting point of 200-204°C. Next, the elemental analysis values and the main peaks in the infrared absorption and nuclear magnetic resonance spectra are shown.

Calculated value for C8 days, 9N302, length 7 days but 03: C
49.35%, day 6.14%, N5.95%.

Actual values: C49.22%, day 6.08%, N6.06%
. Infrared absorption spectrum (KBr): 2100-1850
(Ammonium salt), 1750-1 (ester carbonyl), nuclear magnetic resonance spectrum (DMSO-d.): 1
．． 0 to 2.1 (thin), 2.26 (spots, Toru Tsubafune and others; Ze 3 day visitor 1 Sanzu Toru also Mo Hiroko jH; 4,35 (ga, -
COOCH2-), 7.42 (1 is, quare etJ,
=29.3HZ, J2=9.8HZ, aromatic nucleus proton)
7.5-9・Chest (ban, old-H). The above p-toluenesulfonate salt was dissolved in 50' methanol and the solution was mixed with Type CI Dowexl-X2 resin (DowChem).
Lysine 3-aminoethyl ester trihydrochloride was obtained by passing it through a 250-mesh (50-100 mesh) column manufactured by ical.

Example 3 In the apparatus of Example 1, 3 females (0.4 mol) of 3-family/-1
-Propanol and 100% of toluene were added, and hydrogen chloride gas was introduced to convert it to hydrochloride.

Next, 36.6 g (0.2 mol) of lysine hydrochloride was added, and hydrogen chloride was introduced again to form lysine dihydrochloride. The reaction mixture was heated to reflux temperature (110q○) while hydrogen chloride was passed through. After 11 hours the azeotrope of water stopped.

Remove the toluene, add ethanol to the oil and warm it.
When left at room temperature, crystals precipitated. It is filtered and recrystallized from methanol and ethanol solution to give a melting point of 1 to 14.
5oo of lysine y-aminopropyl ester trihydrochloride-
47 g of hydrate was obtained. Next, the elemental analysis values and the main peaks in the infrared absorption and nuclear magnetic resonance spectra are shown. C9
Calculated value for HaN302/3HC1/day 20: C3
2.69%, day 7.93%, N12.71%, actual value:
C33.04%, day 7.82%, N12.89%, infrared absorption spectrum (KBr): 2200-1850 (ammonium salt), 1740 (ester carbonyl), 12
15 Skin-1 (Ester Ether).

Nuclear magnetic resonance spectrum (DMSO-&): 1-3~2-
4 (mother H), 2-5 to 3-2 (4 days, one CH2 -N-
COOCH2-), 7.0-9.5 (plaques, N-H). Example 4 To the apparatus of Example 2, 1 spot (0.2 mol) of 3-amino/-1-propanol, 91. 18.3 g (0.43 mol) of p-toluenesulfonic acid hydroxide of bamboo (0.43 mol)
1 mol) Norizin (d) hydrochloride and 180 g of benzene were added and heated in an oil tank (110 to 120°C) while stirring.

This temperature was maintained until no water azeotropically distilled off with benzene. This took approximately 8 hours. The benzene layer was decanted and the lower oil was washed with acetone to precipitate crystals. This was taken in a furnace and recrystallized several times from a mixture of ethanol and isopropanol to achieve a melting point of 193-200o.
51 g of IJ gin y-aminopropyl ester tripe-toluenesulfonate monohydrate of O was obtained. Next, the elemental analysis values and the main peaks in the infrared absorption and nuclear magnetic coherence vectors are shown.

Calculated values for C9 day 2, N302, length 7 & S03, H Nu: C48.83%, day 6.42%, N5.70%.

Actual values: C48.52%, day 6.34%, N5.78%
. Infrared absorption spectrum (KBr): 2100-1870
(ammonium salt), 1743 arc-1 (ester carbonyl), nuclear magnetic resonance spectrum (DMSO-also): 1.
1~2,2 (thin), 2,25? A>) 3i Kenzo Sa・(Niomisaki-goro Sagi Tomiai-suzu Qrute ta Z~.q female r to tJ,=
26HZ J2=8 days 2, aromatic nucleus proton)・7.3～
9. Skin (general; -H). The above p-toluenesulfonate 1
The methanol solution containing the female was transferred to CI type Dbwexl-X2.
The mixture was passed through a column of resin (manufactured by Dow Chemical, 50-100 mesh) to obtain lysine y-aminopropylester trihydrochloride.

Example 5 6. The apparatus of Example 1 was added. Female (0.8 mol) 1-amino-
Add 2-propanol, 180 g of toluene and 40 g of ○-dichlorobenzene, and introduce hydrogen chloride gas under ice cooling to convert to 1-amino-2-propanol hydrochloride.
Next 73. Nori sine hydrochloride (0.4 mol) was added and hydrogen chloride was introduced to give lysine dihydrochloride.

Pass hydrogen chloride gas at a rate of 20 to 30 per minute,
The reaction mixture was heated at reflux temperature (116-1170) for 7 hours. Then, a small amount of 0-dichlorobenzene was added, the reflux temperature was raised to 12,500°C, and the mixture was further heated for 7 hours. After cooling, the solvent was removed, the oil was poured into ethanol, and isopropanol was added to this solution to precipitate an oil.
When the top solution was decanted, aqueous ethanol was added to the oil, and the mixture was allowed to stand at room temperature, crystals gradually precipitated. This was taken in a furnace and recrystallized from methanol to give Trizine P-aminoisopropylester trihydrochloride hydrate (melting point 137oo).
) 21 numbers; obtained. Next, the elemental analysis values and the main peaks in the infrared absorption and nuclear magnetic resonance spectra are shown.

C9HaN302・Rough CI・Calculated value for day 20: C3
2.69%, day 7.93%, N12.71%.

Actual value: C32.81%, day 8.05%, N12.69
%. Infrared absorption spectrum (HBr): 2200-185
0 (ammonium salt), 1745 (ester carbonyl), 1220ka-1 (ester ether). Nuclear magnetic resonance spectrum (DMSO-also): 1.33 (crime.doub)
let J=7HZ2 >CH-CH3), room: you; this cloud head 2 winter sun window nimi J da #, - auspicious day 3), Example 6 the ocean crossing machine, thermometer, gas inlet pipe and reflux condenser. Finely crush 25g of gin 8 into a four-necked flask
- Add aminoethyl ester trihydrochloride and 300 ml of o-dichlorobenzene, and pass 120 ml of phosgene through the suspension at a rate of 0.4 mol/hour.
The food was heated for one hour.

Further cooling was required at 6 o'clock, and the temperature was raised to 150 qo. Most of the suspension dissolved. After filtering, the solvent was distilled under reduced pressure, and the residue was distilled using an oil diffusion pump under a nitrogen atmosphere to obtain lysine diisocyanate 8-isocyanate ethyl ester 20 with a boiling point of 155 to 157 o/0.022 Hg.
．． 1 g (yield 90.1%) was obtained. Viscosity 2$ps/20
00. NCO content: 47.1% (calculated value 47.2%).
Infrared absorption spectrum: 2225 (isocyanate group),
1745 (ester carbonyl), 1460, 1355
, 1200 (ester ether), 1108, 1030
,805 skin-1. Nuclear magnetic resonance spectrum: 1, 2-2.
3 (fine), 3.2-3.95 (4 days, -CH2 -NC
O), 4.0-4. Yuryanagi, (9th, mass vector: m
/e153・ (○CNCH2CH2CH2CH2CHNC.

), 267 (molecular weight). Example 7 In the apparatus of Example 6, 25 g of zinc y-aminopropylester trihydrochloride was suspended in 300 o-dichlorobenzene by thoroughly drying under reduced pressure at 10,000 °C and finely crushed, and the liquid temperature was adjusted to 105 °C. Phosgene was passed through at a rate of 0.4 mol/hour for 1q hours while maintaining the temperature at .

Next, the temperature was gradually raised, and the reaction was finally carried out at 150° C. for 4 hours. Boiling point 153-1 treated in the same manner as Example 6 after cooling
55q0/0.036 side Hg lysine diisocyanate y-isocyanate propyl ester7. He (yield 34
%) was obtained as a pale yellow liquid. Viscosity 2 EU ps/20℃
. NCO content: 44.6% (calculated value 44.8%). Infrared absorption spectrum: 2225 (isocyanate group), 17
40 (ester carbonyl), 1458,1350,1
200 (Ester Ether), 1030 Ka-1. Nuclear magnetic resonance spectrum: 1.2-2.4 (fine), 3.2-3.
8 (Nagi, -CH2-NCO), 3.9-4. Tough blood (milk day, mass vector: m/e153 (OCNCH2CH2
CH2CH2CHNC○), 281 (molecular weight).

Example 8 Gin 8-aminoisopropylester trihydrochloride was added to the apparatus of Example 6 by thoroughly drying under reduced pressure in a vacuum oven and then pulverizing it into fine pieces. You are suspended in 250 ml of o-diku oo benzene, and while maintaining the temperature of the liquid at 10,000 ml, phosgene is added to 2.
I spent time in the fields.

The temperature was gradually raised to 15,000 over a further 1 hour. After wrapping, process in the same manner as in Example 6 to obtain a boiling point of 145-15.
Lysine diisocyanate 8 with 0qo/0.085 Hg
-Isocyanate isopropylester 2.1 g (yield 30%) was obtained as a pale yellow liquid. Viscosity 2*ps/2
0℃. NCO content: 44.6% (calculated value 44.8%).
Infrared absorption spectrum: 2225 (isocyanate group),
1740 (ester carbonyl), 1455, 1350
, 1200 (ester ether), 1100, 1060
, 860 arc-1. Nuclear magnetic resonance spectrum: 1.3 (but,
doyuletJ=7,3HZ,>CH-CH3), 1.
0-2.2 (fine), 3.0-3.8 (4 days, -CH2-
NCO), 4.42 (IH, triplet J=4.
9HZ, 5.0 string wind mass vector: m/e153 (OCNCH2CH2CH2CH2CHNCO), 28
1 (molecular weight).

Reference Example A two-component urethane paint with a high non-volatile content suitable for automobile repair was produced using the triisocyanate of the present invention.

Component A: Polyhydroxy acrylic resin (“Kotakus LH610'' manufactured by Toray Industries, Inc., non-volatile content: 5
0%) 112 parts titanium oxide pigment 65 parts Component B: Lysine ester triisocyanate components A and B of Example 6 were combined with N
Mixed at a CO/OH molar ratio of 1.

The non-volatile content of this mixture was approximately 7% by weight, and its viscosity was determined by food cup no. When measured using 4, it was 2 seconds. Therefore, it was spray painted on steel plates without further dilution. After forced drying under the conditions of 80oo x 30 minutes, it was left to stand for 2 days for evaluation.

The important characteristics of the coating were as follows. layer thickness
40. Pencil hardness: 6. Specular reflection (600 cross) 90. Gasoline resistance: No dissolution or swelling. After 10 months of outdoor exposure test, there was no change in appearance and no decrease in gloss was observed.

Claims (1)

[Scope of Claims] 1. A lysine ester triisocyanate represented by the following general formula: ▲There are numerical formulas, chemical formulas, tables, etc.▼ (wherein R is an alkyleryl group having 2 to 5 carbon atoms).