JP2622151B2 - Trimethylolhexane derivative - Google Patents

Description

The present invention relates to a novel trimethylol alkane, and more particularly to a general formula: (Wherein ^one of R ¹ and R ² represents a methyl group and the other represents a hydrogen atom).

Since the trimethylolhexane derivative represented by the general formula (I) of the present invention has three highly reactive hydroxyl groups, it has an alkyd resin, a polyurethane resin, a plasticizer, a surfactant, a wetting agent, and a coating agent. It is useful as a raw material for agents, paints, adhesives, and fiber processing agents.

(Prior art) Trimethylolalkanes include 1,1,1-trimethylolethane and 1,1,1-trimethylolpropane.
1,1-Trimethylolalkanes are known, and these 1,1,1-trimethylolalkanes are used as raw materials for alkyd resins, polyurethane resins and the like.

(Problems to be Solved by the Invention) 1,1,1-Trimethylolalkanes such as 1,1,1-trimethylolethane and 1,1,1-trimethylolpropane are used as raw materials such as alkyd resins and polyurethane resins. When used as, the three hydroxyl groups of the 1,1,1-trimethylolalkane are used to form a bond such as an ester bond or a urethane bond with a functional group of another molecule. . However, in the 1,1,1-trimethylolalkane, the steric hindrance between the three hydroxyl groups is relatively large because the three methylol groups are bonded to the same carbon atom. Not all hydroxyl groups exhibit sufficiently high reactivity. In particular, in a state where two of the three hydroxyl groups of the 1,1,1-trimethylolalkane have reacted with another molecule to form a bond, the reaction of the remaining third hydroxyl group has occurred. Due to their rather low potency, the curing of resins obtained using 1,1,1-trimethylolalkanes takes a long time. Therefore, 1,1,1
-Trimethylolalkane is not necessarily said to have sufficiently satisfactory properties as a raw material for a resin.

Accordingly, an object of the present invention is to provide a novel trimethylolalkane having three highly reactive hydroxyl groups.

(Means for Solving the Problems) According to the present invention, the above object is achieved by providing a trimethylolhexane derivative represented by the general formula (I).

As the trimethylolhexane derivative represented by the general formula (I), specifically, 1,1,6-trimethylol heptane represented by the formula and And 1,6,6-trimethylolheptane represented by

The trimethylolhexane derivative represented by the general formula (I) can be obtained, for example, by reacting 2-methyl-1,8-octanedial with formaldehyde in the presence of a base and hydrogenating the resulting product. Manufactured.

As the base to be present in the reaction system in the reaction between 2-methyl-1,8-octanedial and formaldehyde, a base usually used when reacting an aldehyde with formaldehyde to form methylol can be used,
Representative examples thereof include hydroxides or carbonates of alkali metals or alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate; Trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, N-
Methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylcyclohexylamine, heterocyclic such as tetraethylammonium hydroxide,
Aliphatic or alicyclic tertiary amines or quaternary ammonium salts; and anion exchangers such as Amberlyst A-27 (manufactured by Rohm and Haas). As formaldehyde, an aqueous formaldehyde solution is usually used. As the aqueous formaldehyde solution, a commercially available 5 to 50% by weight aqueous formaldehyde solution can be used as it is. Formaldehyde is used in an amount of 0.05 to 4 moles per mole of 2-methyl-1,8-octanedial, so that the yield of the precursor of the trimethylolhexane derivative represented by the general formula (I) is reduced. It is preferable because it becomes high. The methylolation reaction can be carried out in the absence of an organic solvent, but can also be carried out homogeneously or heterogeneously in the presence of an organic solvent inert in the methylolation reaction system. As such a solvent, it is preferable to use an organic solvent which is at least partially soluble in water, and specific examples thereof include lower aliphatic alcohols such as methanol, ethanol, propanol and butanol; and aliphatic alcohols such as diethyl ether, tetrahydrofuran and dioxane. Or alicyclic ethers.
When the reaction is carried out in a state in which a base such as a hydroxide or carbonate of an alkali metal or an alkaline earth metal, a tertiary amine, or a quaternary ammonium salt is dissolved in an aqueous solution, the base is dissolved in the aqueous solution. It is desirable to use it in such an amount that the pH is in the range of 8 to 13. The reaction temperature is preferably in the range of 5 to 70 ° C. because the yield of the precursor of the trimethylolhexane derivative represented by the general formula (I) is high.

The separation of the product from the reaction mixture obtained by the methylolation reaction in this manner is performed, for example, by extracting the reaction mixture with an organic solvent such as diethyl ether. The precursor of the trimethylolhexane derivative represented by the general formula (I) contained in the product obtained by the methylolation reaction is 2- (hydroxymethyl) -7-methyl-1,8-octanedial or 2- (hydroxy Methyl) -2-methyl-1,8-octanedial, but the product obtained by the methylolation reaction is usually used as it is in the next hydrogenation reaction without being isolated to each component. Is done.

The hydrogenation reaction of the product obtained by the methylolation reaction is usually performed in the presence of a hydrogenation catalyst. As the hydrogenation catalyst, a hydrogenation catalyst generally used when hydrogenating an aldehyde to convert it to an alcohol can be used. In general, a ruthenium catalyst such as ruthenium-carbon; It is industrially advantageous to use it. The hydrogenation reaction is usually performed at a pressure of 1 to 200 atm (absolute pressure) at a partial pressure of hydrogen gas at a temperature of 20 to 200 ° C. The hydrogenation reaction can be performed in the absence of a solvent, but can also be performed in the presence of an inert solvent in the hydrogenation reaction system. Examples of such a solvent include alcohols such as ethanol, butanol, 3-methylbutanol, and 3-methylpentane-1,5-diol; pentane, hexane, heptane, octane,
Saturated aliphatic hydrocarbons such as nonane and decane;
Organic solvents such as aromatic hydrocarbons such as toluene and xylene; ethers such as tetrahydrofuran; and water are used alone or in admixture of two or more.

The resulting trimethylolhexane derivative is separated and obtained by subjecting the reaction mixture obtained by the hydrogenation reaction to a separation / purification operation such as distillation after removing the hydrogenation catalyst and solvent as necessary. Is done.

The 2-methyl-1,8-octanedial used as a raw material in the process for producing the trimethylolhexane derivative represented by the general formula (I) is described in, for example, JP-A-58-15773.
It can be easily produced by hydroformylating 7-octenal according to the method described in JP-A-9.

(Examples) Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 2-methyl-1,8- was placed in a three-necked flask of the content 1 equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel.
Octanedial 156 g (1 mol), 86 g of 35% by weight aqueous formaldehyde solution (1 mol as formaldehyde)
And 200 ml of diethyl ether. Internal temperature 30-35
The mixture was stirred vigorously while maintaining the temperature at 100 ° C., and 100 g of a 10% by weight aqueous sodium carbonate solution was gradually added dropwise over 2 hours. After completion of the dropwise addition, stirring was continued for another 12 hours. The resulting reaction mixture was extracted three times with 100 ml each of diethyl ether. Diethyl ether was distilled off from the extract using an evaporator.
5 g was obtained.

After charging 300 ml of n-butanol, 5 g of 5% by weight ruthenium-carbonic acid and 10 ml of water into an autoclave of contents 1 equipped with a stirrer, an inlet for hydrogen gas and a raw material, a temperature controller and a sampling port, the autoclave was filled with hydrogen gas. Substituted enough. While maintaining the inside of the autoclave at 9 atm (gauge pressure) with hydrogen gas, 11
The temperature was raised to 0 ° C. Next, the residual liquid obtained by the above evaporation operation was continuously supplied into the autoclave at 50 ml / hr. During this time, the pressure and temperature were kept constant. After completion of the supply, the reaction was further performed for 1 hour. Ruthenium-carbon was removed from the obtained hydrogenation reaction mixture with a filter, and n-butanol was distilled off from the liquid using a rotary evaporator. The obtained residual liquid (190 g) was distilled under reduced pressure, and distilled under a pressure of 1 mmHg (absolute pressure) as a distillate having a boiling point of 145 to 161 ° C.
38 g of a mixture consisting of 45% by weight of trimethylol heptane and 55% by weight of 1,1,6-trimethylol heptane were obtained.

A small amount of this mixture is subjected to preparative gas chromatography [column packing: Silicoe GE SE 33 5% chromosorb W
(Gascro Industry Co., Ltd.); Column length: 2m; Column temperature: 120
Temperature from 250 ° C. to 1,6,6-trimethylol heptane and 1,1,6-trimethylol heptane, respectively. The analysis results of these fractions are shown below.

I) 1,6,6- trimethylol heptane Elemental analysis: C62.5%, H12.0%, calculated for _{O24.8% (C 10 H 22 O} 3: C63.1%, H11.6%, Mass spectrum: FD / MS 191 (M + 1) ¹ H-NMR spectrum (CDCl ₃ / DMF-d ₆ ): δ ppm 3.5 (t, 2H, —CH ₂ C H ₂ OH), 1.5 (m, 2H, -C H 2 CH 2 OH), 1.15~1.37 (m, 8H, CH 2) 4 -), 0.9 (s, 3H, CH 3 -) II) 1,1,6- trimethylol heptane elemental analysis: C63.0%, H11.0%, O25.2 % ( calculated for _{C 10 H 22 O 3: C63.1} %, H11.6%, O25.2%) mass spectrum: FD / MS 191 (M + 1) ¹ H-NMR spectrum (CDCl ₃ / DMF-d ₆ ): δ ppm 1.6 (m, 1H, -C H (CH 2 OH) 2), 1.15~1.37 (m, 8H, - ( CH 2) 4 -), 0.83 (d, 3H, CH 3 -) solution for separating Reference Example 1 produced water - liquid separator, condenser, thermometer and stirrer A trimethylol hexane derivative mixture 7.06 containing 1,6,6-trimethylol heptane and 1,1,6-trimethylol heptane at a ratio of 45 wt% and 55 wt%, respectively, in a 100 ml three-necked flask equipped with an apparatus.
g (37 mmol), 17.2 g (0.15 mol) of caproic acid and 20 ml of benzene. While boiling this mixture under heating under a nitrogen atmosphere, 0.41 g of p-toluenesulfonic acid was added.
Was added. The generated water was azeotroped with benzene and removed out of the system by a liquid-liquid separator. During the esterification reaction, the reaction mixture was analyzed by gas chromatography. Three minutes after the start of the reaction, the residual ratio of the trimethylolhexane derivative mixture became 1% or less,
Almost all of the trimethylolhexane derivative mixture was esterified. One hour after the start of the reaction, the monoesterified trimethylolhexane derivative mixture becomes 1% or less of the initially used trimethylolhexane derivative mixture, and about 99% of the initially used trimethylolhexane derivative mixture is diesterified or triestered. Was Four hours after the start of the reaction, the diesterified trimethylolhexane derivative mixture was 1% of the initially used trimethylolhexane derivative mixture.
Approximately 99% of the trimethylolhexane derivative mixture initially used was triesterized.

Reference Example 2 An esselization reaction was performed in the same manner as in Reference Example 1, except that 5.0 g (37 mmol) of 1,1,1-trimethylolpropane was used instead of 7.06 g (37 mmol) of the trimethylolhexane derivative mixture. . Six minutes after the start of the reaction, the residual ratio of 1,1,1-trimethylolpropane became 1% or less, and almost all of 1,1,1-trimethylolpropane was esterified. Two hours after the start of the reaction, the monoesterified 1,1,1-trimethylolpropane is 1% of the 1,1,1-trimethylolpropane originally used.
Approximately 99% of the 1,1,1-trimethylolpropane initially used was diesterified or triesterized. Four hours after the start of the reaction, the diesterified or triesterified 1,1,1-trimethylolpropane accounted for 11% and 88% of the initially used 1,1,1-trimethylolpropane, respectively. Eight hours after the start of the reaction, the 1,1,1-trimethylolpropane diesterified becomes 1% or less of the 1,1,1-trimethylolpropane initially used, and 1,1,1-trimethylolpropane initially used is used. About 99% of methylolpropane was triesterized.

(Effects of the Invention) According to the present invention, as is clear from the above-described examples,
A novel trimethylolalkane having three highly reactive hydroxyl groups is provided.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09J 167/00 JFV C09J 167/00 JFV

Claims (1)

(57) [Claims] (1) General formula (Wherein ^one of R ¹ and R ² represents a methyl group and the other represents a hydrogen atom).