JP2847210B2 - High carbon number aliphatic triol, method for producing the same, and unsaturated aliphatic carboxylic acid ester of high carbon number aliphatic triol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high carbon number aliphatic triol, a method for producing the same, and an unsaturated aliphatic carboxylic acid ester of the high carbon number aliphatic triol.

[0002]

2. Description of the Related Art Conventionally, high carbon number aliphatic diols having 20 or more carbon atoms have been known. Such a diol having a high carbon number is produced by polymerizing a higher unsaturated fatty acid to form a dimer (dimer acid) and reducing it.
The diol thus obtained is used as a raw material for a vinyl polymerization reaction by reacting acrylic acid or methacrylic acid with the diol (JP-A-60-157106,
JP-A-3-236349). On the other hand, the trimer (trimer acid) obtained by the polymerization of higher unsaturated fatty acids, unlike the case of the dimer acid, has not been developed for any particular use at present.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel high-carbon aliphatic compound which can be produced from a higher unsaturated fatty acid or a lower alkyl ester thereof, and a method for producing the same. Another object of the present invention is to provide a novel high carbon number aliphatic compound which can be produced using a higher unsaturated aliphatic alcohol or a lower fatty acid ester thereof as a raw material, and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that triols obtained by reducing trimers of higher unsaturated fatty acids or lower alkyl esters thereof, Triols obtained by trimerizing higher unsaturated aliphatic alcohols and triols obtained by hydrolyzing trimers of lower fatty acid esters of higher unsaturated aliphatic alcohols have hydroxyl groups such as polyester and polyurethane by themselves. In addition to being able to be used advantageously as a polymerization raw material or a flexible cross-linking agent in the polymerization reaction involved, those obtained by reacting an unsaturated aliphatic carboxylic acid such as acrylic acid or methacrylic acid with this triol are used as a raw material for a vinyl polymerization reaction or The present inventors have found that they can be advantageously used as a flexible crosslinking agent in a vinyl polymerization reaction, and have completed the present invention.

That is, according to the present invention, after a higher-unsaturated fatty acid having at least 14 carbon atoms or a lower alkyl ester thereof is subjected to a polymerization reaction treatment, a trimer is separated and recovered from the resulting polymerization reaction product. , the trimer and reduction treatment, the method for producing a high carbon number aliphatic triol and converting a carboxyl group or a lower alkyl ester groups contained in the trimer to -CH 2 _OH group provides Is done.

Further, according to the present invention, after a polymerization reaction of a higher unsaturated aliphatic alcohol having at least 14 carbon atoms, a trimer is separated and recovered from the polymerization reaction product obtained. And a method for producing a high carbon number aliphatic triol.

Further, according to the present invention, at least 14
After the lower fatty acid ester of a higher unsaturated aliphatic alcohol having three carbon atoms is subjected to a polymerization reaction treatment, a trimer is separated and recovered from the resulting polymerization reaction product, and the trimer is subjected to a hydrolysis treatment. There is provided a method for producing a high carbon number aliphatic triol, which comprises separating and recovering the triol.

Furthermore, an aliphatic hydrocarbon chain R having at least 42 carbon atoms, which is obtained by the above-mentioned production method.
And a high carbon number aliphatic triol having a structure in which three hydroxyl groups are bonded to each other.

Furthermore, according to the present invention, the general formula [Wherein, R represents the aliphatic hydrocarbon chain, and R ⁴ ,
R ⁵ and R ⁶ are hydrogen or a general formula —CO (CH ₂ ) n CR ¹ ＣＲCR ² R ³ (2) (wherein R ¹ , R ² and R ³ represent hydrogen or a lower alkyl group, and n is The aliphatic aliphatic carboxylic acid residue represented by the formula (1), wherein at least one of them is an unsaturated aliphatic carboxylic acid residue: Is provided.

The high carbon number aliphatic triol of the present invention can be produced using, as a starting material, a higher unsaturated fatty acid having at least 14 carbon atoms or a lower alkyl ester thereof alone or as a mixture. As the higher unsaturated fatty acid, those containing 1 to 4, preferably 1 to 2, unsaturated bonds can be used. The total carbon number of the higher unsaturated fatty acid used in the present invention is 14 to 22, preferably 16 to 22.
Eighteen. Illustrating specific examples of the higher unsaturated fatty acids,
For example, oleic acid, elaidic acid, octadecenoic acid,
Linoleic acid, palmitoleic acid, myristoleic acid, linolenic acid, isooleic acid, eicosenoic acid, docosenoic acid,
Examples include branched octadeyanic acid and branched hexadecenoic acid.

In order to preferably produce the triol of the present invention using the above-mentioned higher unsaturated fatty acid or its lower alkyl ester, the above-mentioned higher unsaturated fatty acid or its C1-C3 fatty acid is preferably used.
6, preferably 1 to 4 lower alkyl esters, for example, methyl ester, ethyl ester, propyl ester, butyl ester, etc. are subjected to a polymerization reaction treatment. in this case,
The higher unsaturated fatty acids or lower alkyl esters thereof are used alone or in a mixture. When these raw materials are used as a mixture, the mixture may be a mixture having different numbers of carbon atoms, or a mixture having different numbers of unsaturated bonds. The higher unsaturated fatty acid or lower alkyl ester thereof may be mixed with a higher saturated fatty acid or lower alkyl ester, and the mixing ratio is specified to be 40% by weight or less, preferably 20% by weight or less. Good.

As the polymerization catalyst, a liquid or solid Lewis acid and Bronsted acid are used, and a solid acid catalyst which is a kind of Bronsted acid is preferably used. As such a material, activated clay (preferably montmorillonite activated clay, bentonite activated clay), synthetic zeolite, silica / alumina, silica / magnesia and the like are used. The amount of the catalyst is 1 to 20% by weight, preferably 2 to 8% by weight, based on the amount of the polymerization raw material. The reaction temperature is 200 to 270 ° C, preferably 230 to 250 ° C
It is. The reaction pressure may be any of reduced pressure, normal pressure, and increased pressure, but is usually 1 to 10 atm (absolute pressure), preferably 2 to 10 atm. The reaction time depends on the amount of the catalyst and the reaction temperature and is not fixed, but usually 5 to 10 hours is sufficient. The reaction atmosphere may be in the air,
In order to obtain a good color tone, it is preferable to use an inert gas atmosphere such as a nitrogen gas or an argon gas.

The polymerization reaction product thus obtained comprises a mixture of trimer acid (or lower alkyl ester thereof) which is a trimer and dimer acid (or lower alkyl ester thereof) which is a dimer. , Usually containing unreacted higher unsaturated fatty acids (or lower alkyl esters thereof).
In the present invention, trimer acid (or a lower alkyl ester thereof) is separated and recovered from the polymerization reaction product. Methods for separating trimer acid (or its lower alkyl ester) from the polymerization reaction product include molecular distillation, thin film distillation, extraction,
A chromatographic separation method, an adsorption separation method, or the like can be employed. The trimer obtained in the polymerization step comprises isomers having different unsaturated bond positions, or a mixture of cis / trans isomers. The position of the unsaturated bond in the trimer and its cis / trans ratio vary depending on the polymerization temperature and the catalyst used. In the case of the present invention, the unsaturated bond may be located at any position, The cis / trans ratio may be in any range. In addition, when a higher unsaturated aliphatic alcohol is used as a raw material, a small amount of a compound having an ether bond in a molecule is by-produced by a dehydration condensation reaction of the alcohol during the polymerization reaction, and such a by-product is converted into a trimer. Such by-products do not need to be particularly removed, since contamination does not cause any particular inconvenience.

Next, the trimer acid (or lower alkyl ester thereof) thus obtained is subjected to a reduction treatment. As a reduction method, a catalytic reduction method using hydrogen gas and a catalyst, lithium aluminum hydride (LiAl
A conventionally known method such as a reduction method using a hydrogenating agent such as H ₄ ), lithium borohydride (LiBH ₄ ), or metallic sodium / alcohol can be employed. Examples of the catalyst used in the catalytic reduction method include nickel, Raney nickel, Raney cobalt, platinum black, platinum oxide, copper-chromium, copper-zinc, palladium, palladium black, hydrogen activation supported on a porous material such as alumina and silica mina. A catalyst made of a metal (a transition metal such as nickel, cobalt, molybdenum, platinum, and palladium) is exemplified. In the case of the catalytic reduction method, the reaction temperature is 50 to 300 ° C, preferably 150 to 280 ° C, and the reaction pressure is 1 to 300 kg / cm ² , preferably 100 to 25.
A hydrogen pressure of 0 kg / cm ² is employed. The reaction time is usually 1 to 15 hours.

In the reduction method using a hydrogen additive, the reaction temperature is equal to or higher than the hydrogen generation temperature of the hydrogen additive, and differs depending on the type of water cable additive. For example, when LiAlH ₄ is used as a hydrogenating agent, the reaction temperature is 0 ° C.
35 ° C. are employed, the case of using LiBH _4, the reaction temperature is 20 to 50 ° C.. The reaction time is usually 1 to 10 hours. The proportion of the hydrogenating agent used is determined by the ester bond (-) in the trimer acid or its lower alkyl ester.
COOR, R: may be an amount sufficient to be reduced to a lower alkyl group) a hydroxymethyl group _(-CH 2 OH), usually 1 to 5 times the stoichiometric amount, preferably 1.5 to 3 times Used.

Specifically, a method for reducing trimer acid (or lower alkyl ester thereof) using lithium aluminum hydride as a hydrogenating agent is as follows. Lithium aluminum hydride is dispersed in an ethereal solvent such as diethyl ether, and the trimer acid (or lower alkyl ester thereof) diluted with diethyl ether is added to the dispersion under stirring at 0 ° C. to room temperature. 1 to
Add dropwise slowly over 2 hours. After the completion of the dropping, stirring is continued for about 30 minutes, and then about 4 times mol of water is gradually added dropwise to the lithium aluminum hydride to terminate the reaction. Subsequently, about 10% by weight of dilute sulfuric acid is added to the reaction mixture to remove lithium aluminum from the ether layer, and then washed with water until the waste liquid becomes neutral. The triol can be obtained by removing the ether from the ether layer. In the above, an example in which the trimer separated and recovered from the polymerization product is subjected to a reduction treatment has been described, but the reduction treatment may be applied to the polymerization product in some cases. In this case, a trimer triol is separated and recovered from the obtained reduction treatment product.

In the above-mentioned reduction treatment, as reaction by-products, an ester formed by the reaction between the alcohol formed by the reduction reaction of trimer acid or its ester and its raw material, an aldehyde formed by the reduction reaction of the raw material, Although a small amount of hydrogen is produced, these by-products do not need to be particularly removed since their incorporation into triols does not cause any particular inconvenience. Furthermore, -COOH groups or -COOR not reduced in the reduction treatment step
A small amount of the group may remain in the molecule. Triol is composed of a mixture of a cis-form and a trans-form, and the cis-to-trans ratio changes depending on the reduction temperature. In the present invention, the cis-to-trans ratio may be in any range.

The triol of the present invention is, as described above,
In addition to being able to be produced using a higher unsaturated fatty acid or a lower alkyl ester thereof as a raw material, it can also be produced using a higher unsaturated fatty alcohol or a lower fatty acid ester thereof as a raw material. As the higher unsaturated aliphatic alcohol, those containing 1 to 4, preferably 1 to 2, unsaturated bonds are used. The total carbon number of the higher unsaturated aliphatic alcohol used in the present invention is 14 to 22, preferably 16 to 18. Examples of higher unsaturated aliphatic alcohols include palmitoleyl alcohol, oleyl alcohol, elaidyl alcohol, octadecenyl alcohol, and eicosenyl alcohol. In the lower fatty acid ester of the higher unsaturated aliphatic alcohol, examples of the lower fatty acid component include those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as acetic acid, propionic acid, butyric acid, and valeric acid.

When a triol is produced using these higher unsaturated aliphatic alcohols or lower fatty acid esters thereof, when a higher unsaturated aliphatic alcohol is used as a raw material,
This is polymerized, and a trimer triol (trimer triol) is separated and recovered from the obtained polymerization reaction product. Also,
When a lower fatty acid ester of a higher unsaturated aliphatic alcohol is used as a raw material, the lower fatty acid ester is polymerized, and a trimer (a lower fatty acid ester of trimer triol) is separated and recovered from the resulting polymerization reaction product. Decompose or saponify to separate and recover the trimer triol. The polymerization reaction in these cases can be performed in the same manner as in the case of the polymerization reaction of the higher unsaturated fatty acid or lower alkyl ester thereof described above, and the separation and recovery of trimer from the polymerization reaction product can also be performed. The same can be done. The lower fatty acid esterification of trimertriol or the hydrolysis treatment of the polymerization reaction product can be performed in the presence of an acidic catalyst such as hydrochloric acid, sulfuric acid, and P-toluenesulfonic acid. On the other hand, the saponification process
It can be carried out in the presence of an alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. The higher unsaturated fatty alcohol or its lower fatty acid ester is used alone or in a mixture. When used as a mixture, the mixture may be a mixture having different numbers of carbon atoms or a mixture having different numbers of unsaturated bonds.

In the production of the above-mentioned triols, it is preferable to use esters thereof as starting materials, rather than to use higher unsaturated fatty acids or higher unsaturated aliphatic alcohols themselves. Advantageously, the viscosity of the reaction mixture decreases during the reaction, and when the catalyst is filtered from the reaction product after the reaction, the filtration rate is improved.

The triol obtained as described above is
It is a yellowish, viscous liquid substance at room temperature. The triol may contain an unsaturated bond. When the triol contains an unsaturated bond, its unsaturated bond content is represented by an iodine value of 0.01 to 130 g (iodine) / 100 g, usually 0.1 to 120 g (iodine) / 1.
The range is 00 g. The triol of the present invention is used as a crosslinking agent in a polycondensation reaction involving a hydroxyl group such as a polyesterification reaction with a polyvalent carboxylic acid, a polyurethane formation reaction with a polyvalent isocyanate, and a ring-opening polymerization reaction with a polyvalent epoxy compound. be able to. The polycondensate using the triol of the present invention as a cross-linking agent has improved properties such as heat resistance, impact resistance, and mechanical strength because a cross-linked structure is formed by the cross-linking agent. However, since the crosslinking agent has a long chain, the polycondensate has flexibility, and has excellent properties such as elongation and bending under tension and bending. In this case, the content of the triol used as a crosslinking agent in the polycondensate is 30 to
It is 80% by weight, preferably 40-70% by weight.

The triol of the present invention can have a polymerizable reactive group bonded through its hydroxyl group. As the compound providing such a polymerizable reactive group, an unsaturated aliphatic carboxylic acid having an ethylenic bond and a lower alkyl ester thereof can be used. By reacting an unsaturated aliphatic carboxylic acid or a lower alkyl ester thereof with triol, an unsaturated aliphatic carboxylic acid ester of triol represented by the general formula (1) can be obtained. Specific examples of the unsaturated aliphatic carboxylic acid and its lower alkyl ester include acrylic acid, methacrylic acid, crotonic acid and their methyl, ethyl, propyl and butyl esters.

The esterification reaction between the triol and the unsaturated aliphatic carboxylic acid or its lower alkyl ester is carried out according to a conventionally known method in the presence of a catalyst and a polymerization inhibitor. As the catalyst, hydrogen fluoride, boron trifluoride, p
-In addition to acid catalysts such as toluenesulfonic acid and methanesulfonic acid, basic catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate and sodium carbonate, aluminum, sodium, potassium, lithium,
Alkoxides of alcohols such as methanol, ethanol, propanol and butanol of metals such as titanium are used. The amount of the catalyst used is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of the triol and the unsaturated aliphatic carboxylic acid or its lower alkyl ester. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 6-tert-butyl-
2,4-xylenol, chloranil, 2,5-dichloro-p-benzoquinone, 2,6-dichloro-p-benzoquinone, 1,1-diphenyl-2-picrylhydrazyl,
p-benzoquinone, p-nitrosodiphenylamine, p
-Conventionally used ones such as nitrosodimethylaniline and phenothiazine can be used. The amount of the polymerization inhibitor used is 0.00% based on the total amount of the triol and the unsaturated aliphatic carboxylic acid or its lower alkyl ester.
It is a ratio of 01 to 1% by weight. The reaction temperature and the reaction time are determined based on a balance between the reaction rate and the amount of the polymer by-product, and are usually in the range of 50 to 130 ° C. and 5 to 10 hours. The resulting unsaturated aliphatic carboxylic acid ester of triol is purified, if necessary, by distilling off the unreacted unsaturated aliphatic carboxylic acid or its lower alkyl ester under reduced pressure or washing with an alkaline aqueous solution. You can also.

In the esterification reaction, when an unsaturated aliphatic carboxylic acid is used as a reaction raw material, water is produced as a by-product, and when an unsaturated aliphatic carboxylic acid lower alkyl ester is used, a lower alcohol is produced as a by-product. I do. Such by-products are preferably continuously separated and removed from the reaction system. To this end, the reaction temperature is maintained at a temperature not lower than the boiling point of the by-product at the reaction pressure or not lower than the azeotropic point of the by-product and the unsaturated aliphatic carboxylic acid or its ester, and the by-product is separated by distillation. Alternatively, an inert gas is allowed to flow through the reaction system to separate and remove by-products in a gaseous state together with the inert gas from the reaction system. Further, water or alcohol as a by-product can be removed under reduced pressure.

The amount of the unsaturated aliphatic carboxylic acid or lower alkyl ester thereof to be reacted with the triol is usually from 0.33 to 5.0 equivalents per equivalent of the hydroxyl group of the triol. In order to esterify substantially all of the hydroxyl groups in the triol, the unsaturated aliphatic carboxylic acid or lower alkyl ester thereof must have a hydroxyl group 1 in the triol.
1.0 to 5.0 equivalents per equivalent, preferably 1.05 to
It is preferred to use 2.0 equivalents. When only a part of the hydroxyl group contained in the triol is esterified and the hydroxyl group remaining in the final reaction remains, 0.32 to 1.0 equivalent of the total equivalent of the hydroxyl group to be esterified contained in the triol is used.
It is good to make 2 equivalents, preferably 0.5 to 1.05 equivalents. An acid chloride such as acrylic acid chloride (acryloyl chloride) or methacrylic acid chloride (methacryloyl chloride) can be used in place of the unsaturated aliphatic carboxylic acid or its ester to be reacted with triol. When an acid chloride is used, the reaction can be carried out at room temperature without a catalyst while removing hydrochloric acid gas generated as the reaction proceeds. A method of adding pyridine or the like to remove hydrochloric acid can also be adopted.

The binding ratio of the unsaturated aliphatic carboxylic acid or the lower alkyl ester thereof to the hydroxyl group contained in the triol (reaction rate of the hydroxyl group) is controlled by the amount of the unsaturated aliphatic carboxylic acid or the lower alkyl ester thereof and the reaction time. can do. When the unreacted unsaturated aliphatic carboxylic acid ester of a triol containing a hydroxyl group is subjected to homopolymerization or copolymerization reaction, a polymer containing a free hydroxyl group can be obtained. Since such a polymer contains a free hydroxyl group, it has a hydrophilic property and has an advantage of being excellent in adhesiveness, paintability, dyeability, and the like, and also has a reactivity with a hydroxyl group through the hydroxyl group. There is also the advantage that the desired properties can be imparted to the polymer by reacting various reactants.

The viscosity of the unsaturated aliphatic carboxylic acid ester of the triol of the present invention obtained as described above (25
C, B-type viscometer) is usually 600 cp or less. The free hydroxyl group in the unsaturated aliphatic carboxylic acid ester of triol is represented by a hydroxyl value of 5 KOHmg / g.
When it is desired to esterify substantially the entire amount, the amount is adjusted to less than 2 KOH mg / g, preferably to less than 1 KOH mg / g, but it is not necessarily limited to this range depending on the purpose. Absent. In the case of an unsaturated aliphatic carboxylic acid ester containing a free hydroxyl group,
2 to 134 KOH mg / g, preferably 2 to 37 KOH
mg / g, more preferably 2 to 30 KOH mg / g, but is not necessarily limited to this range depending on the purpose. The unsaturated aliphatic carboxylic acid ester of triol can be homopolymerized or copolymerized with another vinyl monomer to obtain a polymer. Examples of the comonomer in the case of copolymerization include unsaturated aliphatic carboxylic acid esters of alcohols having 10 or more carbon atoms and 20 carbon atoms.
Examples thereof include unsaturated aliphatic carboxylic acid esters of the above diols, and acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, hydroxyethyl methacrylate, and the like. The polymerization reaction of the unsaturated aliphatic carboxylic acid ester of triol or a vinyl monomer mixture containing the same is carried out by using an azo-based compound such as azobisisobutyronitrile (AlBN) or azobisvaleronitrile (AVN) as a polymerization initiator. It can be performed using a peroxide-based radical polymerization initiator such as oxide (BPO) and lauryl peroxide (LPO). In this case, since the molecular weight (degree of polymerization) needs to be adjusted, the polymerization is usually performed by adding a chain transfer agent such as mercaptan. The polymerization method includes bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and the like, and an appropriate method is used depending on the use of the polymer.

The unsaturated aliphatic carboxylic acid ester of triol of the present invention can be used as a comonomer in a vinyl polymerization reaction. In this case, the content of the unsaturated aliphatic carboxylic acid ester of the triol in the vinyl polymer is 5 to 95% by weight, preferably 30 to 90% by weight, and more preferably 60 to 90% by weight. Such a vinyl polymer obtained by using the unsaturated aliphatic carboxylic acid ester of triol of the present invention as a comonomer has improved heat resistance due to formation of a crosslinked structure. It has advantages such as excellent physical properties such as flexibility and impact resistance.

[0029]

Next, the present invention will be described in more detail with reference to examples. All the percentages shown below are percentages by weight.

Embodiment 1

[Table 1] Using a higher unsaturated fatty acid methyl ester having a composition shown in Table 1 as a raw material, 1000 g of the same and 70 g of montmorillonite-based activated clay as a catalyst are placed in an autoclave having an inner volume of 2 liters, and reacted at 230 ° C. for 5 hours in a nitrogen atmosphere. Was. After filtration of the reaction product, thin-film distillation (250-2
(80 ° C./0.3-0.5 mmHg) to remove the monomer-dimer fraction to obtain about 150 g of trimethyl trimerate. Next, a reactor equipped with a stirrer, a cooling pipe, a thermometer, a dropping funnel, and an N ₂ introduction pipe was replaced with N ₂ ,
20 g of lithium aluminum hydride (LiAlH ₄ )
Were charged, while flowing N ₂ portionwise, under stirring, at room temperature, it is slowly added diethyl ether 800ml from the dropping funnel. Into the thus formed LiAlH ₄ diethyl ether dispersion, a solution obtained by diluting 150 g of trimethyl trimerate obtained above with 200 ml of diethyl ether is slowly dropped over about 2 hours.
At this time, the temperature of the solution rises due to the heat of the reaction.
Keep the liquid temperature below about 30 ° C. After the dropwise addition, the mixture is heated for 30 minutes, and 38 g of water is slowly added dropwise from the dropping funnel. This solution is slowly poured into a beaker containing 200 g of ice. Thereto, 150 g of a 10% aqueous sulfuric acid solution is added, and then an appropriate amount of diethyl ether is added to extract an ether layer. Further, the ether layer was washed with water several times until the wastewater became neutral, and the solvent of the obtained ether layer was distilled off under reduced pressure to obtain a yellow viscous transparent viscous liquid, triol 12.
5 g are obtained. This is 72 g (iodine) / 10
It showed an iodine value of 0 g.

Next, stirrer, _{N 2} inlet, thermometer, condenser and reactor fitted with a water measuring tube, triols 125g obtained in, methacrylic acid 44 g, p-methoxyphenol 0.1 g, p- 8.5 g of toluenesulfonic acid and 80 g of cyclohexane were charged, and the mixture was heated to about 90 ° C. while stirring while flowing air little by little. Next, at the same temperature, while removing the generated water from the system by a water test tube, esterification was performed for about 6 hours until the amount of generated water became 8.3 g, and after cooling, dissolved in 100 g of diethyl ether and dissolved in 20 g of 10% sodium hydroxide. After neutralization, the aqueous layer was separated and removed. Further, after washing with water several times until the waste water becomes neutral, 0.1 g of p-methoxyphenol is added and the solvent is distilled off under reduced pressure.
142.6 g of methacrylic acid ester of triol, which is a yellowish transparent liquid, are obtained. This substance has the following properties.

[0032]

[Table 2] From the data shown in Table 2, it can be seen that a triester in which almost all of the —OH groups of the triol were methacrylic esters was obtained.

Example 2 200 g of trimethyl trimerate separated by the method shown in Example 1 was added to an autoclave equipped with a stirrer, a thermometer, and an H ₂ inlet tube, and 1.0% by weight of a copper chromium oxide catalyst was added. Hydrogen pressure 200 kg / cm ² , reaction temperature 23
It was kept at 0 ° C. for 6 hours. After cooling the reaction product, the catalyst was filtered to obtain 185 g of a yellowish transparent viscous liquid, triol. The iodine value of this product is 34 g
(Iodine) / 100 g. Next, esterification with methacrylic acid according to the method according to Example 1 yields a yellowish transparent liquid, methacrylic acid ester.
This substance has the following properties.

[0034]

[Table 3] From the data shown in Table 3, it can be seen that a triester in which almost all of the —OH of the triol was converted to a methacrylate ester was obtained.

Comparative Example 1 In the same manner as in Example 1, a higher unsaturated fatty acid methyl ester having the composition shown in Table 1 was subjected to a polymerization reaction, and the reaction product was filtered, and then subjected to thin film distillation to obtain a monomer fraction (200 to 220). ° C /
After removing 0.3 to 0.5 mmHg, the dimer acid fraction (250 to 280 ° C./0.3 to 0.5 mmHg) was distilled off to obtain about 450 g of dimethyl dimerate. Next, this was hydrogenated using lithium aluminum hydride in the same manner as in Example 1 to form a diol, and this diol was reacted with methacrylic acid to give a slightly yellowish transparent liquid methacrylate. was gotten.
This substance has the following properties.

[0036]

[Table 4]

Reference Example 1 To 10 g of each of the methacrylates obtained in Example 1 and Comparative Example 1, 0.05 g of benzoyl peroxide was added and dissolved as a polymerization initiator. These solutions were then transferred to 20 ml test tubes and placed in an oil bath at 90 ° C. for 5 minutes.
The polymerization was maintained for a certain time. The melting point of the obtained polymer was determined by DS
C (Differential Scanning C
alorimeter) measurement (RIGA manufactured by Rigaku Corporation)
Table 5 when calculated from the endothermic onset temperature of KUTAS-200). The polymer A shown in Table 5 is a polymer obtained from the triol methacrylate obtained in Example 1, and the polymer B is obtained from the diol methacrylate obtained in Comparative Example 1. Polymer.

[0038]

[Table 5] As described above, it was found that the polymer of the methacrylate ester of triol of the present invention had a higher melting point than that of the diol.

Reference Example 2 1.0 g of azobisisobutyronitrile as a polymerization initiator was added and dissolved in 200 g of the methacrylic acid ester obtained in Examples 1 and 2, respectively. Next, these solutions were transferred to a 10 cm × 10 cm × 1 cm container and kept at 90 ° C. for 8 hours in a thermostat. The obtained polymer was insoluble in organic solvents such as acetone, toluene, and ethanol, and was found to be a three-dimensionally crosslinked polymer.
These polymers exhibited excellent values in all of heat resistance, impact resistance, and mechanical strength.

Example 3 1000 g of a higher unsaturated aliphatic alcohol having the composition shown in Table 6 below and 50 g of bentonite-based activated clay were placed in an autoclave having an inner volume of 2 liters, and were placed in a nitrogen atmosphere under a nitrogen atmosphere.
The reaction was performed at 0 ° C. for 5 hours. After filtering the reaction product, thin-film distillation (220-250 ° C./0.3-0.5 mmHg) was performed to remove the monomer-dimer fraction to obtain about 120 g of trimer triol.

[Table 6]

Example 4 1000 g of acetic acid ester of a higher unsaturated aliphatic alcohol having the composition shown in Table 6 and montmorillonite activated clay 7
0 g was placed in an autoclave having an internal volume of 2 liters, and a polymerization reaction was carried out in the same manner as in Example 1. After filtering the obtained reaction product, thin-film distillation (250 to 280 ° C / 0.3 to 0.5
mmHg) to remove the monomer-dimer fraction, thereby obtaining about 150 g of an acetate of trimertriol.
Next, an aqueous solution of sodium hydroxide and ethanol were added to the triestertriol acetate in excess of the saponification equivalent, and the mixture was refluxed for 10 hours. Ether was added to the obtained product, and excess sodium hydroxide was neutralized with dilute sulfuric acid, and then thoroughly washed with water. Ether layer is N
After drying over a ₂ SO ₄ and distilling off the ether under reduced pressure, trimertriol was obtained.

The trimer triol 100g obtained in Example 5 Example 1, methyl methacrylate 11.5 g, p-methoxyphenol 0.1 g, stirrer tetraisopropoxytitanate 2.0 g, _{N 2} inlet, thermometer And a reactor fitted with a cooling tube. As the reactor began to heat, methanol began to distill and was held at this temperature for 6 hours when the reaction temperature rose to 90 ° C. After cooling the reaction product, a small amount of water was added, and the precipitated TiO ₂ was removed by filtration. Next, ether and water were added to the filtrate, washed well, the ether layer was dried over Na ₂ SO ₄ , and the ether was removed under reduced pressure to obtain a yellowish liquid. This material has the following properties:

[0043]

[Table 7] From the data in Table 7, it can be seen that one -OH of the trimer triol
It can be seen that a monoester having a methacrylic acid residue introduced into the group was obtained.

Reference Example 3 When the methacrylic acid ester obtained in Example 5 was polymerized according to the method of Reference Example 1, a polymer insoluble in acetone, toluene, ethanol and the like was obtained.

[0045]

The high carbon number triol of the present invention has a very large carbon number of 42 or more, and is added as a crosslinking agent to a polymerization reaction system involving a hydroxyl group such as a polyester reaction or a polyurethane reaction. Thereby, physical properties such as heat resistance, impact resistance, and mechanical strength are improved, and a polymer having a crosslinked structure excellent in flexibility can be obtained. Moreover, the triol of the present invention can introduce various reactive groups through its hydroxyl group. The triol of the present invention obtained by subjecting the unsaturated aliphatic carboxylic acid or its lower alkyl ester to an esterification reaction can be used as a vinyl polymerizable monomer. The polymer obtained by homopolymerization or copolymerization with another vinyl monomer has a crosslinked structure, and has improved properties such as heat resistance, impact resistance, and mechanical strength, and has excellent flexibility. Things. Further, the vinyl polymer obtained from the unsaturated aliphatic carboxylic acid ester mixture containing a free hydroxyl group of the present invention,
Since the polymer contains a free hydroxyl group, it has hydrophilicity, and has the advantage of being excellent in adhesiveness, coating property, dyeing property, etc., and has various reactivity with the hydroxyl group with respect to the hydroxyl group. Has the advantage that the desired properties can be imparted to the polymer. When the triol of the present invention and the unsaturated aliphatic carboxylic acid ester of the triol are produced, a small amount of an aldehyde group or a side reaction such as formation of an ether bond may occur, but the present invention is limited thereby. is not.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // B01J29 / 04 B01J29 / 04 X C07B 61/00 300 C07B 61/00 300 (72) Inventor Yuichi Asao Sumida, Tokyo 1-3-7, Ward Honjo Rion Co., Ltd. (58) Field surveyed (Int. Cl. ⁶ , DB name) C07C 31/22 C07C 29/44-29/46 C07C 67/08 C07C 69/54

Claims (5)

(57) [Claims] 1. A method of reducing a trimer of a higher unsaturated fatty acid having at least 14 carbon atoms or a lower alkyl ester thereof, and converting a carboxyl group or a lower alkyl ester group contained in the trimer into a —CH ₂ OH group. A process for producing a high carbon number aliphatic triol, which comprises converting 2. A high carbon number fatty acid, comprising subjecting a higher unsaturated aliphatic alcohol having at least 14 carbon atoms to a polymerization reaction treatment, and then separating and recovering a trimer from the obtained polymerization reaction product. For the production of triols. 3. A polymerization reaction of a lower fatty acid ester of a higher unsaturated aliphatic alcohol having at least 14 carbon atoms, followed by separation and recovery of a trimer from the polymerization reaction product, and hydrolysis of the trimer. A method for producing an aliphatic triol having a high carbon number, comprising treating and separating and recovering a trimer triol. 4. A high carbon number aliphatic having a structure in which three hydroxyl groups are bonded to an aliphatic hydrocarbon chain R having at least 42 carbon atoms, which is obtained by the production method according to claim 1, 2 or 3. Triol. 5. General formula[Wherein R represents the aliphatic hydrocarbon chain according to claim 4]
Then R⁴, R⁵And R⁶Is hydrogen or a general formula -CO (CH₂) NCR¹= CR²R³  (Where R¹, R²And R³Is hydrogen or lower alkyl group
And n represents a number of 0 or 1.)
Shows aliphatic carboxylic acid residues, but of these
One is an unsaturated aliphatic carboxylic acid residue]. In table
Unsaturated aliphatic cals of high carbon number aliphatic triols
Bonic esters.