JPH01268655A - 1,1,7-trimethylolheptane - Google Patents

Abstract

NEW MATERIAL:1,1,7-Trimethylolheptane of formula. USE:Raw material for alkyd resin, polyurethane resin, plasticizer, surfactant, humectant, coating agent, paint, adhesive, textile processing agent, etc. PREPARATION:The compound of formula can be produced e.g. by reacting (A) octa-2,7-dien-1-ol which is easily available by the dimerization and hydration of butadiene with (B) H2 and CO at a molar ratio (H2/CO) of preferably 3/1-1/3 and total partial pressure of H2 and CO of 5-300atm (abs) at 80-150 deg.C in the presence of (C) a hydroformylation catalyst e.g. a compound produced by modifying dicarbonyl acetylacetonatorhodium with a ligand of tris(o-t- butylphenyl)phosphite.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel trimethylolalkane, and more particularly to 1,1,7-trimethylolhebutane represented by the formula %.

1.1.7-) Limethylolhebutane of the present invention has three highly reactive hydroxyl groups, so it can be used for alkyd resins, polyurethane resins, plasticizers, surfactants, wetting agents, coating agents. It is useful as a raw material for paints, adhesives, fiber processing agents, etc.

(Prior art) Trimethylolalkanes include 1.1.1-)limethylolethane s 1,1.1-) Limelow,
II/7'C! 1.1.1-1) Limethylolalkanes such as bread are known, and these 1.1.1-)limethylolalkanes are used as raw materials for alkyd resins, polyurethane resins, and the like.

(Problem to be solved by the invention) The above 1.1.1-trimethylolethane, 1,1.1
- When using 1.1.1-)limethylolalkane such as trimethylolpropane as a raw material for alkyd resins, poly9 urethane resins, etc., three hydroxyl groups possessed by the 1.1゜1-)limethylolalkane is used to form bonds such as ester bonds and urethane bonds with functional groups of other molecules. However, 1
, 1.1-) In limethylolalkane, the three methylol groups are bonded to the same carbon atom, so the steric hindrance between the three hydroxyl groups is relatively large, and these three hydroxyl groups However, not all of them exhibit sufficiently high anti-rusting properties. In particular, in a state where two of the three hydroxyl groups of 1,1.1-)limethylolalkane react with other molecules to form a bond, the remaining third hydroxyl group Since the reactivity is rather low, the curing of the resins obtained using 1,1.1-)limethylolalkane takes a long time. Therefore, it cannot be said that 1,1.1-)limethylolalkane has sufficiently satisfactory properties as a raw material for resins.

Therefore, an object of the present invention is to provide a novel trimethylolalkane having three hydroxyl groups and having high reactivity.

According to the invention, the above object is achieved by providing butane to 'LL7-)limethylol.

The OL of the present invention, 1.7-)limethylolhebutane, can be produced by, for example, hydroformylating octa-2,7-renin-1-ol and hydrogenating the resulting product (hereinafter, this method is referred to as production method A). ), 1,9-nonanedial is reacted with formaldehyde in the presence of a base, and the resulting product is hydrogenated (hereinafter, this method is referred to as Production Method B). Manufacturing method A and Chi method BK
” will be explained in detail below.

Process A The hydroformylation reaction of octa-2,7-dien-1-ol is carried out by reacting octa-2,7-renin-1-ol with hydrogen and carbon monoxide in the presence of a hydroformylation catalyst. be exposed. As the hydroformylation catalyst, hydroformylation catalysts commonly used in the hydroformylation of olefinic compounds can be used, and rhodium catalysts, cobalt catalysts, ruthenium catalysts, etc. are used, but from the viewpoint of high reaction yield, Preference is given to using rhodium catalysts. As the rhodium catalyst, rhodium complex compounds such as rhodium carboel and dicarbonylacetylacetonatrodicum; rhodium compounds such as rhodium acetate, rhodium chloride, and rhodium oxide can be used. These rhodium complex compounds, rhodium compounds, etc. are modified with ligands such as phosphines such as triphenylphosphine and tricyclohequinylphosphine; phosphites such as triphenylphosphite and tris(o-t-butylphenyl)phosphite. can also be used as a rhodium catalyst. As the rhodium catalyst, it is preferred to use a rhodium catalyst modified with phosphites such as high enyl) phosphites at low catalyst concentrations. The rhodium catalyst is usually used at a concentration of 0.005 to 5 milligram atoms of rhodium/1C reaction mixture). In the hydroformylation reaction, the total partial pressure of hydrogen gas and carbon monoxide is 5 to 30
It is preferable to carry out the reaction under a pressure of 0 atmosphere (absolute pressure) and at a temperature of 80 to 150°C. The ratio of hydrogen gas to carbon monoxide gas is preferably within the range of about 3/1 to 1/3 as hydrogen/carbon monoxide molar ratio of the gas entering the reactor. In addition, a gas inert to the hydroformylation reaction, such as methane, ethane, propane, nitrogen,
There is no problem even if small amounts of helium, argon, carbon dioxide, dimethyl ether, etc. coexist in the reaction system. The hydroformylation reaction is preferably carried out in the absence of a solvent, but it can also be carried out in the presence of an inert solvent in the hydroformylation reaction system. Such solvents include alcohols such as ethanol, butanol, 3-methylbutanol, 3-methylpentane-1,s-diol; pentane, he-+? Examples include saturated aliphatic hydrocarbons such as heftane, octane, nonane, and decane. The precursor of 1,1,7-)limethylolhebutane obtained by the hydroformylation reaction is 2-hydroxymethyl-1,
This precursor is believed to be 9-nonane dial.
-Hydroxy-7-nonenal.

C City-CH (CHz), C) bcHcHzOH-C City-
C1(z(CHz)3G(=CHCH20H-HO) Therefore, in order to increase the yield of the 1,1.7-trimethylolhebutane precursor, it is desirable to allow a sufficient reaction time for the hydroformylation reaction.

The product obtained by the hydroformylation reaction can be separated from the reaction mixture by, for example, removing the hydroformylation catalyst and optionally the solvent from the reaction mixture by filtration, distillation, or the like. will be carried out. The product obtained in this way is usually not isolated into its individual components. It is then subjected to the next hydrogenation reaction.

The hydrogenation reaction of the product obtained by the hydroformylation reaction is usually carried out in the presence of a hydrogenation catalyst. As the hydrogenation catalyst, hydrogenation catalysts that are commonly used when hydrogenating aldehydes to convert them into alcohols can be used, and generally include ruthenium catalysts such as ruthenium-carbonate; nickel catalysts such as Raney nickel and nickel-Cainku earth. It is industrially advantageous to use The hydrogenation reaction is usually carried out at a partial pressure of hydrogen gas of 1 to 200 atmospheres (absolute pressure) and a temperature of 20 to 200°C. The hydrogenation reaction can be carried out in the absence of a solvent, but it can also be carried out in the presence of an inert solvent in the hydrogenation reaction system. Such solvents include alcohols such as ethanol, butanol% 3-methylbutanol, 3-methylpentane-1,5-diol; pentane, hexane, heptane,
Saturated aliphatic hydrocarbons such as octane, nonane, decane;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Organic solvents such as ethers such as tetrahydrofuran and water are used alone or in combination of two or more.

The produced 1,1.7-)limethylolhebutane is
The reaction mixture obtained by the hydrogenation reaction is separated and obtained by removing the hydrogenation catalyst and solvent as necessary and then subjecting it to separation and purification operations such as distillation and crystallization.

In addition, in this method for producing 1.1.7-trimethylolhebutane, it is easily produced by hydration of off/-2,7-meritol used as a raw material.

Production method B As the base to be present in the reaction system in the reaction of 1.9-nonanedial and formaldehyde, bases that are commonly used when reacting aldehyde with formaldehyde to form methylol can be used, and representative examples thereof as lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, lithium carbonate,
Alkali metal hydroxides or carbonates of alkaline earth metals such as sodium carbonate and potassium carbonate; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, N-methylpyrrolidine,
N-methylpiperidine, N-methylmorpholine, N,N
- Heterocyclic, aliphatic or alicyclic tertiary amine or quaternary ammonium salt such as dimethylcyclohexylamine, tetraethylammonium hydroyaside; Amberlyst A-27 (manufactured by Rohm and Haas) Examples include anion exchangers. As formaldehyde, an aqueous formaldehyde solution is usually used. As the formaldehyde aqueous solution, an industrially available 5 to 50 weight formaldehyde aqueous solution can be used as it is.

Formaldehyde is used in a ratio of 0.05 to 4 mol per 1 mol of 1,9-nonanedial.
．． 7-) Limethylolhebutane is preferred because the yield of the butane precursor is increased. The methylolation reaction can be carried out in the absence of an organic solvent, but it can also be carried out homogeneously or heterogeneously in the presence of an inert organic solvent in the methylolation reaction system.

As such a solvent, it is preferable to use an organic solvent that is at least partially soluble in water, specific examples of which include lower aliphatic alcohols such as methanol, ethanol, propatool, and butanol; fatty acids such as diethyl ether, tetrahydrofuran, and dioxane. Examples include group or alicyclic ethers. When the reaction is carried out in an aqueous solution with a base such as an alkali gold or alkaline earth metal hydroxide or carbonate, tertiary amine, or quaternary ammonium salt, the base is It is desirable to use the aqueous solution in an amount such that the aqueous solution φ is within the range of 1 (8 to 13).Also, the reaction temperature is 1.1.7-. Therefore, 5 to 70℃
It is preferably within the range of .

Separation of the product from the reaction mixture thus obtained by the methylolation reaction is carried out, for example, by extracting the reaction mixture with an organic solvent such as diethyl ether. The precursor of 1,1,7-)limethylolhebutane contained in the product obtained by the methylolation reaction is 2
-Hydroxymethyl-1,9-nonanedial, but the product obtained by the methylolation reaction is usually directly subjected to the next hydrogenation reaction without being isolated into each component.

The hydrogenation reaction of the product obtained by the methylolation reaction and the separation and purification of 1.1.7-)limethylolhebutane from the reaction mixture are carried out at the aforementioned manufacturing company. Color 1.1.7 - Trimethylol He is carried out in a similar manner to the operation employed in the production of butane.

Incidentally, it can be easily produced by hydroformylating 7-octenal according to the method described for 1.1.7-) Listyrol to Butane.

(Examples) Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples.

Example 1 Octa-2,7-renin-1-ol 500 t1 dicarbonylacetylacetonatrodium 3.7 F, ) lithium (o- t
-butylphenyl) phosphite (1.38F) and triethanolamine (0.17F) were charged, and the inside of the autoclave was sufficiently purged with a mixed gas of hydrogen and carbon monoxide (molar ratio: 2:1). Using the same gas mixture, the inside of the autoclave was kept at 90 atmospheres (gauge pressure) and heated at 100℃ for 10 minutes.
The reaction was allowed to take place under stirring for an hour. The catalyst was separated from the resulting hydroformylation reaction mixture by treating it with a thin film evaporator under a pressure of 1 HP (absolute pressure) and an external heating temperature of 150°C. Evaporation fraction is 665
2 was obtained.

After charging 5QQm of n-butanol, 232% of nickel clay, and 50R1 of water into a 2-ton autoclave equipped with a stirring device, an inlet for hydrogen gas and raw materials, a temperature controller, and a sampling port, the inside of the autoclave was thoroughly filled with hydrogen gas. Replaced. While maintaining the inside of the autoclave at 9 atm (gauge pressure) with hydrogen gas, the temperature was raised to 160° C. with stirring. Next, the evaporated fraction obtained above was continuously supplied into the autoclave at a rate of 170 ml/hr. During this time, pressure and temperature were kept constant. After the supply was completed, the reaction was further continued for 1 hour.

Nickel quartz was removed from the resulting hydrogenation reaction mixture using a filter, and n-butanol was distilled off from the r solution using a rotary evaporator.

Analysis of the resulting residual liquid 7309 by gas chromatography revealed that 27% of the residual liquid was 1.1.7-trimethylolhebutane.

The resulting residual liquid was distilled under reduced pressure to obtain 3802 fractions with a boiling point of 168 to 170°C under a pressure of 1 Cod Hy (absolute pressure).

If this fraction is left at room temperature, crystals will gradually precipitate. By separating the precipitated crystals and washing them with a mixed solution of tetrahydro7 run and diethyl ether (volume ratio: 50:50), a product having the following physical properties was obtained.
．． 7-) 1182 crystals of butane to listyrol were obtained.

Elemental analysis, C63.5, Hll, 5%, 025.
0% (calculated value as Cl0H2203: C63,1
%.

Mass spectrum: FD/MS 191 (M+1) hydroxyl value = 878 ~ KOH/7'' H-NMR spectrum (CDCl5: /DMF
-da): δp voice 3.5~3°64 (dd, 2H
, CHCH2-0H).

3.52~3.66 (a a, 2H,>cHcdan2
-0H).

1.47 (m, 2H, -CIhCHz-OH).

1.15-1.37 Cm, 1014. -(Cdanz)
50Hg) Example 2 In a 1-ton three-meter flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, 1,9-nonanedial 156F (1 mol) and a 35% by weight aqueous formaldehyde solution 862 (as formaldehyde) were added. 1 mol) and 200 d of diethyl ether were added. Internal temperature 30-35
While stirring vigorously while maintaining the temperature at 0.degree. C., 10% by weight aqueous sodium carbonate solution 1002 was gradually added dropwise over 2 hours. After the dropwise addition was completed, stirring was continued for an additional 12 hours. The resulting reaction mixture was extracted three times with 1QQd each of diethyl ether.

Diethyl ether was distilled off from the extract using an evaporator to obtain 181f of residual liquid.

In a 1 ton autoclave equipped with a stirring device, hydrogen gas and raw material inlet, temperature controller and sampling port, 300 d of n-butanol and 5% by weight of luteum carbon 5? After charging 10 - of water, the inside of the autoclave was sufficiently replaced with hydrogen gas. While maintaining the inside of the autoclave at 9 atmospheres (gauge pressure) with hydrogen gas, the temperature was raised to 110° C. with stirring. Next, the residual liquid obtained in the above evaporation operation was continuously fed into the autoclave at a rate of 5 ON Ll/hr. During this time, pressure and temperature were kept constant. After the supply was completed, the reaction was further continued for 1 hour. Ruthenium carbon was removed from the obtained hydrogenation reaction mixture using a filter, and n-butanol was distilled off from the r liquid using a rotary evaporator. The resulting residual liquid 195f was distilled under reduced pressure to a boiling point of 167-1 under a pressure of 1 cod Hf (absolute pressure).
1, 1.7, which has the following physical properties as a fraction at 71°C.
-) 572 of rimethylolhebutane was obtained. The purity of the obtained 1,1.7-)rimethylolhebutane was 98% as a result of analysis by gas chromatography.

Elemental analysis: C63.3%, 811.8%, 024
．． Calculated value as 9% (Cl0) 12203: C63,
1%, H11.6qb, 025.2%)゛Mass spectrum: FD7MS 191 (M+1) Hydroxyl value
:880 Cape KOH/f"H-NMR spectrum (CD(J, ,/DMF-d
s): δppm3.5-3.64 (d d, 2
H,>CHCdanz-OH).

3.52-3.66 (dd, 2H, nCHCH2-O
H).

3.5 (t, 2H, -CH2CH2-0H).

1.5 (m, 2H, - (Aim 2 CH2-OH) +
1゜15~1.37 (m+100, - (CH2
) 5-CH'-) Reference Example 1 1.1.7-) Limethylol was placed in a 100 x 100× Mitsulo flask equipped with a liquid-liquid separator for separating produced water, a condenser, a thermometer and a stirring device. Heptane 7.06F
(37 mmol), 17.2 f (0.15 mol) of caproic acid and 20 j of benzene and 0.41 f of %p-)luenesulfonic acid were added while the mixture was boiling under heating under nitrogen atmosphere.

The produced water is azeotroped with benzene and removed from the system using a liquid-liquid separator. During the esterification reaction, the reaction mixture was analyzed by gas chromatography. 1.1.7-) The residual rate of butane to limethylol is 1% or less 3 minutes after the start of the reaction.5.1.1.
7-) Almost all of the butane to limethylol was esterified. One hour after the start of the reaction, about 99% of the 1,1.7-)limethylolhebutane used was converted into a diester or triester. Also, 94 hours after the start of the reaction, the diesterified 1, 1,7-trimethylol hebutane was less than 1- of the initially used 1, 1,7-)limethylol hebutane, and the initially used 1, 1- .7
-) Approximately 99q6 of rimethylolhebutane is tri-esterified.

Reference Example 2 Same as Reference Example 1 except that 1.1.1-trimethylolpronone 5°0 (37 mmol) was used instead of 1.1.7-trimethylolhebutane (7.06 PC37 mmol) The esterification reaction was carried out. 1.1.1-) The residual rate of limethylolpropane should be 1% or less after the start of the reaction.

1.1.1-) Almost all of the limethylolpropane was esterified. Two hours after the start of the reaction, the monoesterified 1,1.1-)limethylolpropane was 1% or less of the 1,1.1-)limethylolpropane initially used. Approximately 99% of the 1°1-trimethylolpropane was diesterized or triesterified. 4 hours after the start of the reaction, the diesterified or triesterified 1,1.1-)limethylolpropane was converted to the initially used 1,1.1-)limethylolpropane, respectively.
-11% of trimethylolpropane and 88%. Also, after 8 hours from the start of the reaction, the diesterified 1゜1,1-) tyrolpropane is less than 1% of the initially used 1゜1.1-trimethylolpropane. , 1.1-) Approximately 99% of the limethylolpropane was triesterified.

(Effects of the Invention) According to the present invention, as is clear from the above examples, a novel trimethylolalkane having three hydroxyl groups and having high reactivity is provided.

Patent applicant RiRashi Co., Ltd.

Claims (1)

[Claims] 1,1,7-trimethylolheptane.