JP2787080B2 - High carbon number aliphatic triol unsaturated aliphatic carboxylic acid ester composition containing high carbon number aliphatic diol unsaturated aliphatic carboxylic acid ester, method for producing the same, and high carbon number aliphatic diol / triol mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated aliphatic carboxylic acid ester composition of a high carbon number aliphatic triol containing an unsaturated aliphatic carboxylic acid ester of a high carbon number aliphatic diol, a method for producing the same, and a composition thereof. The present invention relates to a high carbon number aliphatic diol / triol mixture useful as an intermediate material for obtaining a product.

[0002]

2. Description of the Related Art Conventionally, high carbon number aliphatic diols having 20 or more carbon atoms have been known. This diol is produced by polymerizing a higher unsaturated fatty acid to form a dimer (dimer acid) and subjecting it to a reduction treatment. The high-carbon aliphatic diol thus obtained is reacted with acrylic acid or methacrylic acid to be used as a raw material for a vinyl polymerization reaction (JP-A-60-157106).
No. JP-A-3-236349). However, the polymer obtained by polymerizing the acrylic acid or methacrylic acid ester of this diol is still unsatisfactory in heat resistance, and also unsatisfactory in terms of impact resistance, flexibility and the like. .

[0003]

The objects of the present invention are as follows. (1) To provide a polymerization reaction composition containing an unsaturated carboxylic acid ester of a high-carbon aliphatic alcohol which gives a polymer having excellent heat resistance, impact resistance and flexibility. (2) To provide a method for producing a polymerization reaction composition containing an unsaturated carboxylic acid ester of a high-carbon aliphatic alcohol which gives a polymer having excellent heat resistance, impact resistance and flexibility. (3) To provide an intermediate material for obtaining the composition for polymerization reaction. Still other objects of the present invention will be clearly understood from the description herein below.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have obtained a trimer obtained by subjecting a higher unsaturated fatty acid or a lower alkyl ester thereof to a polymerization reaction treatment. High-carbon aliphatic triols formed by reduction, triols obtained by trimerizing higher unsaturated aliphatic alcohols, and trimers of lower fatty acid esters of higher unsaturated aliphatic alcohols are obtained by hydrolysis. The unsaturated carboxylic acid ester of a triol has been found to be suitable as a comonomer in the polymerization reaction of the unsaturated carboxylic acid ester of the high-carbon aliphatic diol, and the unsaturated carboxylic acid ester of the aliphatic triol and the aliphatic diol The polymer obtained by the polymerization reaction of the mixture with the unsaturated carboxylic acid ester of It found to have a specific effect which can not be achieved by ester polymer, and have completed the present invention.

That is, according to the present invention, 30 to 97% by weight of an unsaturated carboxylic acid ester (A) of an aliphatic diol having at least 22 carbon atoms, and a high carbon number fat having at least 33 carbon atoms. There is provided a composition for a polymerization reaction comprising 3 to 70% by weight of an unsaturated aliphatic carboxylic acid ester (B) of an aromatic triol.

According to the present invention, there is also provided a high carbon multiplier aliphatic diol having at least 22 carbon atoms.
% By weight and a mixture of 3 to 70% by weight of a high carbon number aliphatic triol having at least 33 carbon atoms with an unsaturated aliphatic carboxylic acid or a lower alkyl ester thereof. An article manufacturing method is provided.

Still further, according to the present invention, a high carbon number aliphatic diol having at least 22 carbon atoms is provided.
A mixture of ９７97% by weight and 3-70% by weight of a high carbon number aliphatic triol having at least 33 carbon atoms is provided.

[0008] The composition for polymerization reaction of the present invention contains an unsaturated aliphatic carboxylic acid ester of a high carbon number diol (A) and an unsaturated aliphatic carboxylic acid ester of a high carbon number triol (B). All of the diols and triols which are the bases of these esters can be produced using higher unsaturated fatty acids or lower alkyl esters thereof or esters with higher unsaturated aliphatic alcohols or lower fatty acids as the base course. As a raw material, it is preferable to use esters thereof, rather than using higher unsaturated fatty acids or higher unsaturated aliphatic alcohols themselves.In this case, the viscosity of the reaction mixture decreases during their polymerization reaction, When the catalyst is filtered from the reaction product after the reaction, there is an advantage that the filtration speed is improved.

A higher unsaturated fatty acid or lower alkyl ester thereof, or a higher unsaturated aliphatic alcohol or lower fatty acid thereof used for obtaining a dimer and a trimer as a raw material of the polymerization reaction composition of the present invention. As the ester, a raw material having an iodine value of 30 to 130 g (iodine) / 100 g, preferably 40 to 120 g (iodine) / 100 g, more preferably 50 to 100 g (iodine) / 100 g is used. Here, when the iodine value exceeds 130 g (iodine) / 100 g, the content of the ring-containing diol B increases. 30g (iodine) / 10
If it is 0 g or less, the number of double bonds in the molecule is too small, so that the dimerization reaction does not easily proceed, and it takes a long time to obtain dimers and trimers. The higher unsaturated fatty acid contains 1 to 4, preferably 1 or 2 unsaturated bonds (double bond), and has a total carbon number of 11 to 22, preferably 1 to 2.
Those having 4 to 20, more preferably 16 to 18 are used. Specific examples of such higher unsaturated fatty acids include, for example, oleic acid, elaidic acid, octadecenoic acid, linoleic acid, palmitoleic acid, myristoleic acid, linolenic acid, isooleic acid, eicosenoic acid, docosenoic acid, branched octadecenoic acid, Examples include branched hexadecenoic acid and undecylenic acid. These higher unsaturated fatty acids can be used alone or in the form of a mixture. In addition, the mixture may be a mixture having different numbers of carbon atoms, or a mixture having different numbers of unsaturated bonds. Furthermore, higher unsaturated fatty acids or a mixture thereof may contain higher saturated fatty acids, and the mixing ratio is preferably 40% by weight or less, more preferably 20% by weight or less. As the lower alkyl ester of the higher unsaturated fatty acid (hereinafter, also simply referred to as higher unsaturated fatty acid ester), a lower alkyl ester having 1 to 6, preferably 1 to 4 carbon atoms, for example, methyl ester, ethyl ester, propyl ester , Butyl ester and the like. These higher unsaturated fatty acid esters can be used alone or in the form of a mixture. In addition, the mixture may be a mixture having different numbers of carbon atoms, or a mixture having different numbers of unsaturated bonds. Further, the higher unsaturated fatty acid ester or a mixture thereof may be mixed with a higher saturated fatty acid ester, and the mixing ratio is preferably 40% by weight or less, and more preferably 20% by weight or less.

The higher unsaturated aliphatic alcohol as a raw material contains 1 to 4, preferably 1 or 2, unsaturated bonds (double bond), and has a total carbon number of 11 to 2.
2, preferably 14 to 20, more preferably 16 to 1
8 is used. Specific examples of such higher unsaturated aliphatic alcohols include, for example, palmitoleyl alcohol, oleyl alcohol, elaidyl alcohol, octadecenyl alcohol, eicosenyl alcohol, and the like. These higher unsaturated aliphatic alcohols can be used alone or in a mixture. In addition, the mixture may be a mixture having different numbers of carbon atoms, or a mixture having different numbers of unsaturated bonds. Further, the higher unsaturated aliphatic alcohol or a mixture thereof may be mixed with a higher saturated aliphatic alcohol, and the mixing ratio is preferably 40% by weight or less, preferably 20% by weight or less. The lower fatty acid ester of the higher unsaturated aliphatic alcohol as a raw material (hereinafter, referred to as
Examples of the higher unsaturated aliphatic alcohol ester) include lower fatty acid esters having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as acetate, propionate, butyrate and valerate. These higher unsaturated aliphatic alcohol esters can be used alone or in the form of a mixture. In addition, the mixture may be a mixture having different numbers of carbon atoms, or a mixture having different numbers of unsaturated bonds. Further, the higher unsaturated aliphatic alcohol ester or a mixture thereof may be mixed with a higher saturated aliphatic alcohol ester, and the mixing ratio is preferably 40% by weight or less, preferably 20% by weight or less.

Next, the method for producing the composition of the present invention will be described in detail. The method for producing a composition containing an unsaturated aliphatic carboxylic acid ester of a high carbon number aliphatic diol according to the present invention comprises dimerizing and trimming a raw material of a higher unsaturated fatty acid or an ester thereof or a higher unsaturated aliphatic alcohol or an ester thereof. A polymerization step for quantification, a step of producing an alcohol comprising a diol and a triol from a product obtained from the polymerization step, and an esterification step of reacting the obtained alcohol with an unsaturated aliphatic carboxylic acid or an ester thereof. ing. Hereinafter, each of these steps will be described.

(Polymerization Step) In the polymerization step, the above-mentioned higher unsaturated fatty acids or their esters, higher unsaturated aliphatic alcohols or their esters (hereinafter, these are also simply referred to as higher unsaturated raw materials) are used as raw materials. This is a step of synthesizing a monomer and a trimer. As the polymerization catalyst, a liquid or solid Lewis acid and Bronsted acid are used,
Preferably, a solid acid catalyst which is a kind of Bronsted acid is used. Examples of such materials include various activated clays such as montmorillonite-based activated clay and bentonite-based activated clay, synthetic zeolites, silica / alumina, silica / magnesia, and the like. The amount of the catalyst is 1 to 20% by weight, preferably 2 to 8% by weight, based on the higher unsaturated raw material.
The reaction temperature is 200 to 270 ° C, preferably 230 to 25.
0 ° C. 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 air, but in order to obtain a polymer having a good color tone, it is preferable to employ an inert gas atmosphere such as nitrogen gas or argon gas.

The polymerization reaction product of the higher unsaturated raw material comprises a mixture containing a dimer and a trimer of a high carbon unsaturated raw material, and usually contains an unreacted unsaturated raw material. In this case, the dimer and the trimer can be separated and recovered in a state independent of each other, or can be separated and recovered in the form of a mixture of both. As a method for separating a dimer and a trimer, a molecular distillation method, a thin film distillation method, an extraction method, a chromatographic separation method, an adsorption separation method and the like can be adopted.

In this polymerization step, when a higher unsaturated fatty acid is used as a raw material having a high carbon number, a dimer (dimer acid) having two carboxyl groups (—COOH) and a trimer having three carboxyl groups (—COOH) are used. The product (trimer acid) is obtained. When a higher unsaturated fatty acid ester is used as a raw material, an ester group (—COOR, R: lower alkyl group)
(Dimer ester) having two and trimer (trimer ester) having three. When a higher unsaturated aliphatic alcohol is used as a raw material, a dimer having two hydroxyl groups (—OH) (dimer diol) and a trimer having three hydroxyl groups (trimer triol) are obtained. When a higher unsaturated aliphatic alcohol ester is used as a raw material, a dimer having two ester groups (—OCOR, R: lower alkyl group) (dimer diol ester) and a trimer having three ester groups (trimer triol ester) ) Is obtained.

The dimer and trimer obtained in the above polymerization step may be an isomer having a different unsaturated bond position,
Consists of a mixture of cis / trans isomers. The position of the unsaturated bond in the dimer and trimer and the 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 in any position, and the cis / trans ratio may be in any range. When a higher unsaturated aliphatic higher alcohol is used as a raw material, a small amount of a compound having an ether bond in the molecule is produced as a by-product during the polymerization reaction by a dehydration-condensation reaction of the alcohol. Such by-products do not need to be particularly removed, since no particular inconvenience occurs even if is mixed in the dimer or trimer.

The dimer and trimer obtained by using the higher unsaturated fatty acid or its ester in the polymerization step as a raw material are subjected to a reduction treatment step to convert them into diol and triol, respectively. The dimer and trimer obtained from the higher unsaturated aliphatic alcohol ester are subjected to a hydrolysis or saponification treatment step to convert them into a diol and a tolyl, respectively. On the other hand, dimers and trimers obtained using higher unsaturated aliphatic alcohols as raw materials can be used as raw materials for producing unsaturated carboxylic esters as they are diols and triols. it can. Hereinafter, these reduction treatment steps, hydrolysis and saponification steps will be described in detail.

(Reduction Treatment Step) The reduction treatment is a step of reducing the dimer acid and trimer acid or the dimer acid ester and trimer acid ester obtained in the polymerization step to convert them into diols and triols. Although dimer acid and trimer acid can be reduced alone, it is preferable to reduce the mixture of both. Also,
The dimer acid ester and the trimer acid ester can also be reduced alone, but it is preferable to reduce the mixture of both. When the reduction treatment is performed as a mixture, the mixing ratio between the dimer acid (or dimer acid ester) and the trimer acid (or trimer acid ester) is determined by adjusting the weight ratio between the diol and the triol in the product obtained by the reduction treatment. Should be selected within the range. Examples of the reduction method include a catalytic reduction method using a hydrogen gas and a catalyst, and a reduction method using a hydrogenating agent such as lithium aluminum hydride (LiAlH ₄ ), lithium borohydride (LiBH ₄ ), and metallic sodium / alcohol. A known method can be adopted. As the catalyst used in the catalytic reduction method, nickel, Raney-nickel, Raney-cobalt, platinum black, platinum oxide, copper-chromium, copper-zinc, palladium, palladium black, and a porous material such as alumina or silicamina were held. A catalyst made of a hydrogen activating 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 a hydrogen pressure of 100-250 kg / cm ² . The reaction time is usually 1 to 15 hours.

In the reduction method using a hydrogenating agent, the reaction temperature is equal to or higher than the hydrogen generation temperature of the hydrogenating agent,
Depends on the type of hydrogen additive. For example, when LiAlH ₄ is used as a hydrogenating agent, the reaction temperature is 0 ° C.
To 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 such that the carboxyl group (—COOH) or ester bond (—COOR, R: lower alkyl group) contained in dimer acid (or its ester) or trimer acid (or its ester) is a hydroxymethyl group. It may be an amount sufficient to be reduced to (-CH ₂ OH), usually 1 to 5 times the stoichiometric amount, preferably 1.5 to 3 times is used. Specifically, a method for reducing dimer acid (or its ester) or trimer acid (or its ester) using lithium aluminum hydride as a hydrogenating agent is as follows. Lithium aluminum chloride is dispersed in an ethereal solvent such as diethyl ether, and the raw material to be treated diluted with diethyl ether is gradually added to this dispersion under stirring at 0 ° C. to room temperature for 1 to 2 hours. To be dropped. 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, 1
About 0% by weight of dilute sulfuric acid is added to remove lithium aluminum from the ether group, and then washed with water until the waste liquid becomes neutral. By removing the ether from the ether layer, diols and triols can be obtained.

In the above-mentioned reduction treatment, as a by-product of the reaction, alcohol produced by a reduction reaction of dimer acid, trimer acid or ester thereof as a raw material is produced by a reaction between the alcohol and a raw material having a high carbon number. Ester and aldehydes and hydrocarbons produced by the reduction reaction of the raw materials are produced in small amounts, but these by-products are mixed into the diols and triols, and are not separated from these, in the next step of esterifying unsaturated fatty acids and These by-products do not need to be particularly removed since they do not cause any particular inconvenience even when introduced into the highest polymerization step. Further, a small amount of -COOH group or -COOR group which has not been reduced in the reduction treatment step may be present in the molecule. Further, diols and triols are composed of a mixture of a cis-form and a trans-form, and the cis / trans ratio changes depending on the reduction temperature. In the present invention, however, the cis / trans ratio falls within any range. You may.

(Hydrolysis or Saponification Step) Dimers and trimers of higher unsaturated aliphatic alcohol esters containing two or three ester groups as a raw material having a high carbon number contain two or three ester groups. The dimers and trimers are hydrolyzed under acidic conditions to obtain triols,
The saponification treatment is performed under alkaline conditions. The hydrolysis treatment under acidic conditions is performed using an acidic catalyst such as hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid. On the other hand, the saponification treatment under alkaline conditions is performed using an alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide or the like in an equivalent amount or more with respect to the ester bond. In the present invention, the hydrolysis treatment or the saponification treatment is applied to dimers and trimers of higher unsaturated aliphatic alcohol ester obtained from the polymerization step. In this case, diol and triol can be separated and recovered from the processed product, but this is not practical. The products of the hydrolysis or saponification process are:
Preferably, the mixture is led to an esterification treatment step with an unsaturated carboxylic acid or an ester thereof.

Each of the diols and triols obtained as described above is a slightly yellowish substance showing a coarse liquid at room temperature. These diols and triols each have a structure in which two or three hydroxyl groups are bonded to an aliphatic hydrocarbon chain. In this case, the aliphatic hydrocarbon chain includes not only a linear hydrocarbon chain but also a fatty acid. Ring-containing hydrocarbon chains are included, and in some cases, small amounts of aromatic ring-containing hydrocarbon chains. In the case of a diol, the content of the ring-containing diol obtained by adding the alicyclic diol and the aromatic ring-containing diol is 0 to 50% by weight, preferably 5 to 40% by weight.
% By weight. Further, the aliphatic hydrocarbon chain to which a hydroxyl group is bonded is saturated or unsaturated. The amount of unsaturated bonds contained in the diol having an unsaturated bond is represented by an iodine value of 0.01 to 130 g (iodine) / 10
0 g, usually 0.1 to 120 g (iodine) / 100 g. The amount of unsaturated bond contained in the triol having an unsaturated bond is represented by an iodine value of 0.01 to 1
30 g (iodine) / 100 g, usually 0.1 to 120 g
(Iodine) / 100 g. The mixture of the diol and the triol obtained as described above is subjected to an esterification reaction with an unsaturated carboxylic acid having an ethylenic bond or an ester thereof. The physical property values of the dimer diol and the trimer triol mixture vary depending on the composition ratio of both,
The values when the weight ratio of dimer diol to dimer triol is 7: 3 are as follows. Hydroxyl value 175
１９195 (KOHmg / g), viscosity 1500-2100
cp (25 ° C.), iodine value 15-50 (KOHmg /
g), specific gravity 0.89 to 0.91. Next, esterification in which a mixture of a diol and a triol is reacted with an unsaturated carboxylic acid or an ester thereof will be described in detail.

(Unsaturated aliphatic carboxylic acid esterification step) As the unsaturated aliphatic carboxylic acid or its ester used for esterification of the diol / triol mixture, those represented by the following general formula can be used. _{^{R 11 OCO (CH 2) nCR}} 1 = CR 2 R 3 (1) In the ^{formula, R 1, R 2, R} 3 and R ¹¹ represents a hydrogen or a lower alkyl group. The carbon number of the lower alkyl group is 1-6, preferably 1-4. n shows the number of 0 or 1. Examples of the unsaturated aliphatic carboxylic acids and esters thereof include acrylic acid, methacrylic acid, crotonic acid, and methyl, ethyl, propyl, and butyl esters thereof. By the esterification reaction of the diol / triol mixture with the unsaturated carboxylic acid or its ester, both the diol and the triol are converted to unsaturated carboxylic esters. In this case, the unsaturated carboxylic acid ester of diol and the unsaturated carboxylic acid ester of triol can be represented by the following general formula.

(Unsaturated aliphatic carboxylic acid of diol
Tell) In the above formula, R^FourHas at least 22 carbon atoms
1 shows an aliphatic hydrocarbon chain. R^FiveAnd R⁶Is hydrogen or a general formula -CO (CH_Two) NCR¹= CR^TwoR^Three (Where R¹, R^Two, R^ThreeAnd n have the same meaning as above
Represents an unsaturated aliphatic carboxylic acid residue represented by
Is at least one of them (ie 1 or 2
) Is an unsaturated aliphatic carboxylic acid residue. (Triau
Unsaturated aliphatic carboxylic acid ester)In the above formula, R⁷Has at least 33 carbon atoms
Represents an aliphatic hydrocarbon chain;⁸, R⁹And R^TenIs hydrogen or
Is the general formula -CO (CH_Two) NCR¹= CR^TwoR^Three (Where R¹, R^Two, R^ThreeAnd n have the same meaning as above
Represents an unsaturated aliphatic carboxylic acid residue represented by
Has at least one of these (ie, 1, 2 or
3) are unsaturated aliphatic carboxylic acid residues. Diol
And Triols in Triol / Triol Mixtures
Is diol: 30 to 97% by weight, preferably
40 to 95% by weight, more preferably 60 to 90% by weight
And triol: 3 to 70% by weight, preferably 5 to 60%
% By weight, more preferably 10 to 40% by weight.

The esterification reaction of the diol / triol mixture with the unsaturated aliphatic carboxylic acid or its ester is
According to a conventionally known method, the reaction is performed in the presence of a catalyst and a polymerization inhibitor. Examples of the catalyst include acid catalysts such as hydrogen fluoride, boron trifluoride, p-toluenesulfonic acid, and methanesulfonic acid, and bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, and sodium carbonate. Alkoxides of metals such as aluminum, sodium, potassium, lithium, titanium and the like, and alcohols such as methanol, ethanol, propanol and butanol. The catalyst is used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of the diol, the triol and the unsaturated aliphatic carboxylic acid or its ester.
% By weight. 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-nitrosodimethylamine,
Conventionally used materials such as p-nitrosodimethylaniline and phenokiazine can be used. The amount of the polymerization inhibitor used is 0.00% based on the total amount of the diol, the triol, and the unsaturated aliphatic carboxylic acid or its 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 1 to 10 hours.

The amount of the unsaturated aliphatic carboxylic acid or its ester to be reacted with the diol / triol mixture is
It is a ratio of 1 equivalent of a hydroxyl group in the diol / triol mixture, usually 0.33 to 5 equivalent. In order to esterify substantially all of the hydroxyl groups in the diol / triol, the unsaturated carboxylic acid or its ester is
1.0 to 5 per equivalent of hydroxyl group in the triol mixture.
0 equivalents, preferably 1.05 to 1.5 equivalents. When only a part of the hydroxyl groups contained in the diol / triol mixture is esterified to leave unreacted free hydroxyl groups, all of the hydroxyl groups to be esterified among the hydroxyl groups contained in the diol / triol mixture are used. The equivalent is 0.33 to 1.2 times equivalent, preferably 0.5 to 1.05 times equivalent.

The binding ratio of the unsaturated aliphatic carboxylic acid or its ester to the hydroxyl group contained in the diol / triol mixture (reaction rate of the hydroxyl group) should be controlled by the amount of the unsaturated carboxylic acid or its ester used and the reaction time. Can be. When a polymerization reaction is carried out using an unreacted unsaturated carboxylic acid ester mixture containing a free hydroxyl group as a raw material, the resulting polymer contains a free hydroxyl group. 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 has a reactivity with a hydroxyl group with respect to the hydroxyl group. There is also the advantage that the desired properties can be imparted to the polymer by reacting various reactants.

In the esterification reaction of the mixture of diol and triol with the unsaturated aliphatic carboxylic acid or its ester, the unreacted unsaturated aliphatic carboxylic acid or its ester is contained in the reaction product. These unreacted unsaturated aliphatic carboxylic acids or esters thereof are separated and removed from the reaction product by distilling the reaction product under reduced pressure or washing with an alkali aqueous solution as required. In the esterification reaction, as a reaction raw material,
When an unsaturated aliphatic carboxylic acid is used, water is by-produced,
When an unsaturated aliphatic carboxylic acid ester is used, alcohol is by-produced. Such by-products are preferably continuously separated and removed from the reaction system. For this purpose, the reaction temperature is maintained at a temperature equal to or higher than the boiling point of the by-product at the reaction pressure or equal to or higher than the azeotropic point of the by-product and the unsaturated carboxylic acid or its ester, and the by-product is separated by distillation; An inert gas is allowed to flow through the reaction system, and the by-products in the gas phase are separated and removed from the reaction system together with the inert gas. Further, water or alcohol as a by-product may be separated and removed by distillation under reduced pressure. In the esterification step using acrylic acid, methacrylic acid, or the like, a side reaction occurs due to the reaction with the residue due to not separating the untreated product in the alcoholization step by the catalytic reduction in the previous step. That is, the remaining OH group of the esterified product formed by the esterification reaction between the OH group of the alcohol generated during the catalytic reduction (alcoholization) and the carboxyl group remaining without being completely alcoholized is converted into acrylic acid or methacrylic acid. It has been esterified with an acid. These by-products are 0.1-
Generates 5%. Such by-products can be removed and used, but even if they are mixed in the product as by-products, they do not cause any particular inconvenience in the next polymerization treatment step, so they are used without particular removal. be able to.

In the esterification of the diol / triol mixture, 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. . 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 composition for polymerization reaction of the present invention comprises an unsaturated aliphatic carboxylic acid ester of diol (A) and an unsaturated aliphatic carboxylic acid ester of triol (B), and the proportion of the component (A) is as follows. 30-97% by weight, preferably 4
It is 0 to 95% by weight, more preferably 60 to 90% by weight, and the proportion of the component (B) is 3 to 70% by weight, preferably 10 to 60% by weight, and more preferably 10 to 40% by weight. If the proportion of the unsaturated carboxylic acid ester (B) of the triol is less than the above range, the effect of the addition becomes insufficient, while if it is too large, the color tone of the mixture is deteriorated and the obtained polymer is colored. Become like These mixtures have relatively high viscosities and are generally difficult to separate by separation means such as distillation. These physical property values are generally as follows. The free hydroxyl group in the composition for polymerization reaction is represented by a hydroxyl value of 5 KOHm
g / g, and when it is desired to esterify substantially the entire amount, it is adjusted to less than 2 KOH mg / g, preferably less than 1 KOH mg / g.
It is not necessarily limited to this range depending on the purpose. When the composition contains a free hydroxyl group, it is 2-134
KOHmg / g, preferably 2-37 KOHmg / g,
More preferably, it is 2 to 30 KOHmg / g, but it is not necessarily limited to this range depending on the purpose.
The hue of the polymerization reaction composition of the present invention is 250 or less, preferably 200 or less, expressed as APHA, and is usually 50 or less.
APHA of ~ 150 is shown. Also, its viscosity (25 ° C,
B-type viscometer) is 400 cp or less, preferably 350 c
p or less, and usually 70 to 330 cp. Specific physical property values when the weight ratio of dimer methacrylate to trimer methacrylate is 7: 3 are as follows. Saponification value 135-150 (KOHmg / g) Viscosity 100-200 cP (25 ° C) Esterification rate 95-100 Specific gravity 0.91-0.94

(Polymerization Step) The polymerization reaction of the composition for polymerization reaction of the present invention can be carried out in the presence of a polymerization initiator according to a conventionally known vinyl polymerization method. As the polymerization initiator, azo-based radical polymerization such as azobisisobutyronitrile (AlBN) or azobisvaleronitrile (AVN) or peroxide-based radical polymerization such as benzoyl peroxide (BPO) or lauryl peroxide (LPO) is used. Initiators can be used. 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. Further, this polymerization reaction system, if necessary, other vinyl monomers, for example, an unsaturated carboxylic acid ester of an alcohol having 10 or more carbon atoms,
Acrylic acid or its ester, methacrylic acid or its ester, hydroxyethyl methacrylate and the like can also be added. Regarding the polymer obtained by polymerization of the composition of the present invention, those obtained from the unsaturated carboxylic acid ester-containing composition containing no free hydroxyl group have remarkably improved physical properties such as heat resistance, impact resistance and mechanical strength. It shows the value obtained. In addition, those obtained from the unsaturated carboxylic acid ester-containing composition containing a free hydroxyl group have hydrophilicity, adhesiveness, paintability, and excellent dyeability, and are reactive with the hydroxyl group with respect to the hydroxyl group. The desired properties can be imparted to the polymer by reacting various reactants having The polymer obtained by polymerization of the composition of the present invention,
Since it is excellent in transparency, heat resistance, and low in specific gravity, it can be applied to various uses such as a field in which inorganic glass is used as a high-performance acrylic resin. Furthermore, the diol / triol mixture obtained in the present invention can also be used as a urethane raw material.

[0031]

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] 1000 g of the raw material high carbon unsaturated fatty acid ester having the composition shown in Table 1 and 70 g of montmorillonite-based activated clay as a catalyst were placed in a 2-liter autoclave, and a polymerization reaction was carried out at 230 ° C. for 5 hours under a nitrogen atmosphere. After the polymerization reaction product was filtered, thin-film distillation was performed to remove the monomer fraction (200 to 200 ° C / 0.3 to 0.5 mmHg), and then the dimer fraction was distilled (250 to 280 ° C / 0.3 ~
(0.5 mmHg) to separate a dimer fraction and a trimer fraction. The product obtained is about 45 dimethyl dimer
0 g and about 150 g of trimethyl trimerate. Next, 225 g of this dimethyl dimerate and 25 g of trimethyl trimer were mixed to obtain a dimer / trimer weight ratio = 9.
/ 1 mixture was obtained.

Next, stirrer, condenser, thermometer, dropping funnel, the reaction apparatus attach the N ₂ inlet was replaced with N _2, 32 g was charged lithium aluminum hydride (LiAlH _4), N ₂ At room temperature while stirring
1200 ml of diethyl ether is gradually added from the dropping funnel. 250 g of the above-obtained mixture was placed in the diethyl ether dispersion of LiAlH ₄ thus formed.
Was diluted with 350 ml of diethyl ether,
Drop slowly over a period of time. At this time, the liquid temperature rises due to the heat of the reaction. After dropping, aging for 30 minutes, 6 drops from dropping funnel
5 g of water are slowly added dropwise. This solution is slowly poured into a beaker containing 350 g of ice. Then 10%
250 g of a sulfuric acid aqueous solution is added, and then an appropriate amount of diethyl ether is added to extract an ether layer. The ether layer was further washed several times with water until the wastewater became neutral.The solvent of the obtained ether layer was distilled off under reduced pressure, and a mixture of diol and triol, which were transparent viscous liquids slightly yellowish, was obtained. Liquid 2
10 g are obtained. The iodine value of this mixture was 68 g (iodine) / 100 g.

Next, 210 g of the mixture of the diol and the triol obtained above, 74 g of methacrylic acid, p-ion were added to a reactor equipped with a stirrer, an N ₂ introduction pipe, a thermometer, a cooling pipe, and a test pipe. 0.15 g of methoxyphenol, 1.42 g of p-toluenesulfonic acid and cyclohexane 120
g, 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 produced water from the system by a water test tube, esterification was carried out for about 6 hours until the amount of produced water became 14.0 g, and after cooling, dissolved in 180 g of diethyl ether, 35g
And the aqueous layer was separated and removed. Further, after washing with water several times until the waste water becomes neutral, p-methoxyphenol was washed with 0.1 ml of water.
When 15 g is added and the solvent is distilled off under reduced pressure, 237 g of a methacrylic acid ester, which is a transparent liquid slightly yellowish, is obtained. This substance has the following properties.

[0035]

Table 2 粘度 Viscosity (B-type viscometer at 25 ° C) 38 cp Acid value 0.2 KOHmg / g Hydroxyl value 0.3 KOHmg / g IR analysis (neat): νcm ~ ¹ 1720, 1638, 1160 NMR analysis (in CDCl ₃ ): δ value (ppm) 6.11┐ vinyl proton 4H 5.50┘ 4.15 ester adjacent proton 4H 1.92 methyl proton 6H 1.73-0.80 fat Group-based proton 64H か ら From the data shown in Table 2, almost all of -OH is methacrylic acid. It can be seen that a methacrylic acid ester of a diol / triol mixture which has been converted into an ester was obtained.

Example 2 In the same manner as in Example 1, a raw material higher unsaturated fatty acid ester having the composition shown in Table 1 was reacted, the reaction product was filtered, and thin film distillation was performed to obtain dimethyl dimerate and trimethyl trimerate. Were mixed at a ratio of 75 g and 175 g, respectively, and then this mixture was hydrogenated using lithium aluminum hydroxide in the same manner as in Example 1 to obtain a mixture of diol and triol. The iodine value of this mixture is 71 g (iodine)
/ 100 g. When this mixture was reacted with methacrylic acid, a methacrylic acid ester as a yellowish transparent liquid was obtained. This substance has the following properties.

[0037]

[Table 3] 粘度 Viscosity (B-type viscometer at 25 ° C) 148 cp Acid value 0.3 KOHmg / g Hydroxyl value 0.4 KOHmg / g IR analysis (neat): νcm ~ ¹ 1719, 1638, 1162 NMR analysis (in CDCl ₃ ): δ value (ppm) 6.12┐ vinyl proton 6H 5.55┘ 4.15 ester adjacent proton 6H 1.93 methyl proton 9H 1.75-0.80 fat Group proton 97H か ら From the data in Table 3, almost all of the -OH groups are converted to methacrylic acid esters. It can be seen that the resulting methacrylate of a diol / triol mixture was obtained.

Example 3 In the same manner as in Example 1, a polymerization reaction was carried out using 1000 g of the higher unsaturated fatty acid methyl ester having the composition shown in Table 1 as a catalyst and 70 g of montmorillonite-based activated clay as a catalyst. After filtering the obtained polymerization reaction product, to remove the monomer fraction,
Thin film distillation (200-220 ° C / 0.3-0.5mmH
g) to obtain 500 g of a compound Ω. GPC analysis of compound Ω with tetrahydrofuran solvent (column: TSK-G
EL G1000HXL (manufactured by Tosoh Corporation) showed that the dimer fraction was 71% and the trimmer fraction was 29%. Next, 500 g of the compound Ω and 15 g of a copper-chromium-based reduction catalyst were charged into an autoclave equipped with a stirrer, a thermometer, and a hydrogen gas inlet tube.
The reaction was performed for 10 hours while maintaining the pressure at 20 kg / cm ² . The catalyst was filtered from the obtained reaction product to obtain compound (410 g). Table 4 shows the analysis values of the physical properties and the result of the GPC analysis of the compound Ψ. From this result, it can be seen that Compound Ψ is an alcoholate composed of dimer diol (71%) and trimer triol (29%).

Table 4 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Hydroxyl value 192.5 KOHmg / g Ester value 2.3 KOHmg / g Iodine value 31.2 KOHmg / g IR analysis (neat): νcm ~ ¹ 3,050-3,700 NMR analysis (in CDCl _3): [delta] value (ppm) 3.63 Alcohol adjacent protons 2H 1.7 to .8 aliphatic protons 34H GPC analysis: dimer fraction: 71% trimer fraction: 29% ━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Next, using the device shown in Example 1, compound
g, 74 g of methacrylic acid, p-methoxyphenol 0.1 g.
15 g, 2.1 g of p-toluenesulfonic acid and 120 g of cyclohexane were charged, and the same operation as in Example 1 was carried out.
I got The analytical values of compound Φ are as shown in Table 5.
From this result, it was found that Compound Φ was a mixture of a methacrylic ester of dimer diol (71%) and a methacrylic ester of trimertriol (29%).

５ Viscosity (B-type viscometer at 25 ° C.) 78 cPs Acid value 5KOHmg / g Hydroxyl value 0.7KOHmg / g IR analysis (neat): νcm ~ ¹ 1720, 1638, 1160 NMR analysis (in CDCl ₃ ): δ value (ppm) 6.11 vinyl proton 1H 5.50 vinyl proton 1H 4.15 ester adjacent proton 2H 1.92 methyl proton 3H 1.7-0.8 Aliphatic proton 34H GPC analysis: Dimer fraction: 71% Trimer fraction: 29% ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━

Comparative Example 1 In the same manner as in Example 1, the raw material higher unsaturated fatty acid ester having the composition shown in Table 1 was subjected to a polymerization reaction, and the reaction product was filtered, followed by thin-film distillation to obtain a monomer fraction (200 to 220). ° C /
After removing 0.3 to 0.5 mmHg, a dimer fraction (250 to 280 ° C / 0.3 to 0.5 mmHg) was distilled to obtain about 450 g of dimethyl dimer. Next, dimethyl dimer was hydrogenated using lithium aluminum hydride in the same manner as in Example 1 to obtain a diol. It showed an iodine value of 65 g (iodine) / 100 g. When this diol was further reacted with methacrylic acid, a transparent liquid methacrylic ester slightly yellowish was obtained. This substance has the following properties.

[0040]

[Table 6] Viscosity (B-type viscometer at 25 ° C) 36 cp Acid value 0.2 KOHmg / g Hydroxyl value 0.3 KOHmg / g IR analysis (neat): νcm ~ ¹ 1720, 1638, 1160 NMR analysis (in CDCl ₃ ): δ value (ppm) 6.10 {vinyl proton 4H 5.54} 4.15 ester adjacent proton 4H 1.92 methyl proton 6H 1.73-0.80 fat Group proton 64H ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Comparative Example 2 In the same manner as in Example 1, the raw material higher unsaturated fatty acid ester having the composition shown in Table 1 was reacted, and the reaction product was filtered, and then subjected to thin-film distillation to remove the monomer fraction and the dimer fraction. (250
280 ° C / 0.3-0.5 mmHg) to obtain trimethyl trimerate. Next, as in Example 1, hydrogenation was performed using lithium aluminum hydroxide to obtain a triol. The iodine value of this product is 72 g (iodine) / 100
g. Further, when this triol was reacted with methacrylic acid, a methacrylic acid ester as a yellowish transparent liquid was obtained. This substance has the following properties.

[0042]

表 Viscosity (B-type viscometer at 25 ° C.) 325 cp Acid value 0.3 KOHmg / g Hydroxyl value 0.7 KOHmg / g IR analysis (neat): νcm ~ ¹ 1718, 1638, 1163 NMR analysis (in CDCl ₃ ): δ value (ppm) 6.12┐ vinyl proton 6H 5.55┘ 4.15 ester adjacent proton 6H 1.92 methyl proton 9H 1.75-0.80 fat Group proton 97H ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Example 4 1000 g of the raw material higher unsaturated aliphatic alcohol having the composition shown in Table 8 below and 50 g of bentonite-based activated clay were placed in an autoclave having an internal volume of 2 liters, and reacted at 230 ° C. for 5 hours in a nitrogen atmosphere. . After filtering the reaction product,
Thin film distillation (180-250 ° C / 0.3-0.5mmH
g) to obtain a mixture consisting of 400 g of dimer diol and 120 g of trimer triol.

[Table 8]

Example 5 1000 g of acetic acid ester of higher unsaturated fatty alcohol having the composition shown in Table 8 and montmorillonite-based 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. The obtained reaction product is filtered and then subjected to thin-film distillation (200 to 280 ° C / 0.3 to 0.5 m
mHg) to give dimer diol acetate 450
g of trimertriol acetate 150 g was obtained. Next, an aqueous solution of sodium hydroxide and ethanol were added to the mixture in excess of the saponification equivalent, and the mixture was saponified for 10 hours under reflux. Ether was added to the obtained product, and excess sodium hydroxide was neutralized with dilute sulfuric acid. Ether is Na ₂ SO ₄
After drying under reduced pressure, ether was distilled off under reduced pressure to obtain a mixture of dimer diol and trimer triol.

Example 6 100 g of a mixture of trimer triol / dimer diol = 1/9 obtained in Example 1 and methyl methacrylate 1
2 g, p-methoxyphenol 0.1 g, and tetraisopropoxytitanate 2.0 g were stirred using a stirrer, a N ₂ inlet tube,
A thermometer and cooling tube were added to the attached reactor. 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, and the mixture was thoroughly washed with water. 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:

[0046]

[Table 9] Acid value 0.1 KOHmg / g Hydroxyl value 103 KOHmg / g IR analysis (neat) ： Νcm ~ ¹ 3100-3650, 1719, 1639, 1164 NMR analysis (in CDCl ₃ ): δ value (ppm) 6.12┐ vinyl proton 2H 5.55┘ 4.15 ester adjacent proton 2H 3.63 alcohol ４ 4H 1.92 methyl Proton 3H 1.73-0.80 Aliphatic proton 97H ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ From the data in Table 9, diol It can be seen that an ester obtained by reacting one -OH group of the / triol mixture with methyl methacrylate was obtained.

Reference Example 1 (Production of polymer) 0.05 g of benzoyl peroxide was added as a polymerization initiator to 10 g of the methacrylic acid ester obtained in Examples 1, 2, and 3 and Comparative Examples 1 and 2 and dissolved. I let it. Next, these solutions were transferred to a 20 ml test tube and kept at 90 ° C. for 8 hours in an oil bath to obtain a transparent to slightly yellowish polymer. The melting point of the obtained polymer was determined by DS
C (Differential Scanning C
alorimeter) measurement (RIGAKU TAS-
Calculated from the endothermic onset temperature of Table 2 below. The diol MMA in Table 10 indicates a methacrylate of a diol, and the triol MMA
MA represents a methacrylate of triol.

[0048]

[Table 10]

Reference Example 2 When the methacrylic acid ester obtained in Example 6 was polymerized according to the method of Reference Example 1, a polymer insoluble in acetone, toluene, ethanol and the like was obtained. This polymer exhibited excellent values in both heat resistance and mechanical strength as compared with the methacrylate polymer obtained in Comparative Example 1 shown in Table 10.

Reference Example 3 0.1 g of perbutyl PV (manufactured by NOF CORPORATION) as a polymerization initiator was added to 10 g of the compound Φ obtained in Example 3 and dissolved. Next, this solution was polymerized by the method shown in Reference Example 1, and the endothermic onset temperature of the obtained polymer was measured by using DSC. The polymer is acetone, toluene,
It was insoluble in ethanol and the like. Next, compound Φ50 g,
To each of 50 g of the diol MMA shown in Comparative Example 1, 0.5 g of perbutyl PV was added and dissolved.
Injected into a glass plate of 0 cm x 10 cm x 4 mm, 30
The temperature was raised to 80 ° C. in minutes, and a polymerization reaction was carried out at this temperature for 6 hours to obtain a plate-shaped resin molded product. The following items were evaluated with respect to the obtained molded product. Table 11 shows the obtained results. Specific gravity: Measured according to ASTM D792. Refractive index: Measured according to ASTM D542. Parallel light transmittance: measured in accordance with JIS K7105.

[Table 11] From Table 9, it can be seen that compound Φ gives a resin molded product whose endothermic onset temperature in DSC, which is a measure of heat resistance, is higher than that of diol MMA (Comparative Example 1).

[0051]

The composition for polymerization reaction of the present invention comprises a mixture of an unsaturated carboxylic acid ester of a high carbon number aliphatic diol and an unsaturated carboxylic acid ester of high carbon number aliphatic triol, The polymerization reaction can be carried out by using a radical polymerization initiator and / or a photopolymerization initiator. This polymerization reaction composition can be used as a raw material for the polymerization reaction itself, and various polymerization reaction systems involving unsaturated bonds, for example, unsaturated polyester, epoxy acrylate resin, urethane acrylate resin, acrylate It can be used as a copolymerization reaction component when synthesizing a resin or the like. Further, the composition of the present invention can be used as a reactive diluent for the photocurable resin composition. Such compositions are flexible,
Since it gives a cured film with excellent flexibility, water resistance and electrical insulation, it can be used for overcoating agents, inks, paints,
It can be used as a surface treatment agent and the like. In the polymer comprising the polymerization reaction composition of the present invention, those obtained from the unsaturated carboxylic acid ester-containing composition containing no free hydroxyl group have remarkably improved physical properties such as heat resistance, impact resistance and mechanical strength. It was done. In addition, those obtained from the unsaturated carboxylic acid ester-containing composition containing a free hydroxyl group have hydrophilicity, adhesiveness, paintability, and other advantages such as excellent dyeability. There is also an advantage in that desired properties can be imparted to the polymer by reacting various reactive agents having reactivity with hydroxyl groups. The high carbon aliphatic diol / high carbon number aliphatic triol mixture of the present invention is derived from a higher unsaturated fatty acid or a lower alkyl ester thereof or a higher unsaturated fatty alcohol or a lower fatty acid ester thereof. It is suitable as a raw material for producing a polymerization reaction composition. The method for producing the composition for polymerization reaction of the present invention uses the above-mentioned mixture of high carbon number aliphatic diol / high carbon number aliphatic triol as a raw material, and is industrially advantageously carried out. When the high-carbon aliphatic diol / high-carbon aliphatic triol mixture of the present invention and its unsaturated carboxylic acid ester are produced, side reactions such as formation of a small amount of aldehyde groups and ether bonds may occur. The present invention is not limited by the present invention.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 69/58 C07C 69/58 C08F 220/20 C08F 220/20 (72) Inventor Yuichi Asao 1-chome, Honjo, Sumida-ku, Tokyo No. 3-7 Inside Lion Corporation (56) References JP-A-3-236349 (JP, A) JP-A-7-304700 (JP, A) JP-A-7-292044 (JP, A) JP-A Sho 51-66303 (JP, A) JP-A-53-69290 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 69/54, 69/58, 67/08 C07C 31 / 20,31 / 22,29 / 44 C08F 20 / 20,220 / 20 (54) [Title of the Invention] Unsaturated aliphatic of high carbon number aliphatic triol including unsaturated aliphatic carboxylic acid ester of high carbon number aliphatic diol Carboxylic acid ester composition, method for producing the same, and high carbon number aliphatic diol / triol Real mixture

Claims (8)

(57) [Claims] 1. An unsaturated aliphatic carboxylic acid ester (A) of a high carbon number aliphatic diol having at least 22 carbon atoms, and 30 to 97% by weight of a high carbon number aliphatic diol having at least 33 carbon atoms. A composition comprising 3 to 70% by weight of an unsaturated aliphatic carboxylic acid ester of triol (B). 2. An unsaturated aliphatic carboxylic acid of an aliphatic diol.
The acid ester has the general formula [In the above formula, R^FourHas at least 22 carbon atoms
An aliphatic hydrocarbon chain;^FiveAnd R⁶Is hydrogen or general
Formula -CO (CH_Two) NCR¹= CR^TwoR^Three (Where R¹, R^TwoAnd R^ThreeRepresents hydrogen or a lower alkyl group
And n is a number of 0 or 1).
Indicates rubonic acid residues, at least one of which
Is an unsaturated carboxylic acid residue].
2. The composition of claim 1, wherein 3. An unsaturated aliphatic carboxy group of an aliphatic triol.
The acid ester has the general formula  [In the above formula, R⁷Has at least 33 carbon atoms
An aliphatic hydrocarbon chain;⁸, R⁹And R^TenIs hydrogen or
General formula -CO (CH_Two) NCR¹= CR^TwoR^Three (Where R¹, R^TwoAnd R^ThreeRepresents hydrogen or a lower alkyl group
And n is a number of 0 or 1).
Indicates rubonic acid residues, at least one of which
Is an unsaturated carboxylic acid residue].
3. The composition of claim 1 or claim 2. 4. High carbon number aliphatic diol having at least 33 carbon atoms and 30 to 97% by weight of high carbon number aliphatic diol having at least 22 carbon atoms.
A method for producing a composition for polymerization reaction, characterized by reacting a mixture of about 70% by weight with an unsaturated aliphatic carboxylic acid or a lower alkyl ester thereof. 5. Higher unsaturated fatty acids having 11 to 22 carbon atoms or esters thereof are polymerized to produce dimer and trimer high carbon unsaturated fatty acids or esters thereof. To a mixture of the corresponding diols and triols, followed by esterification with an unsaturated aliphatic carboxylic acid or lower alkyl ester thereof to form a high carbon aliphatic diol having at least 22 carbon atoms. Unsaturated aliphatic carboxylic acid ester and at least 3
A process for producing a mixture of unsaturated aliphatic carboxylic acid esters of a high carbon number aliphatic triol having 3 carbon atoms. 6. An ester of a higher unsaturated aliphatic alcohol having 11 to 22 carbon atoms is polymerized to produce dimer and trimer esters of a higher carbon unsaturated fatty alcohol,
Next, the obtained product is hydrolyzed or saponified to produce a mixture of aliphatic diols having a high carbon number and aliphatics having a high carbon number, and subsequently an unsaturated aliphatic carboxylic acid or a lower alkyl ester thereof. With at least 2
Process for producing unsaturated aliphatic carboxylic acid esters of high carbon number aliphatic diols having two carbon atoms and unsaturated aliphatic carboxylic acid esters of high carbon number aliphatic triols having at least 33 carbon atoms . 7. A higher unsaturated fatty alcohol having 11 to 22 carbon atoms is polymerized to produce dimer and trimer unsaturated fatty alcohols having a higher carbon number, and the resulting mixture is subjected to extraction. It is subsequently esterified with an unsaturated aliphatic carboxylic acid or a lower alkyl ester thereof to form an unsaturated aliphatic carboxylic acid ester of a high carbon number aliphatic diol having at least 22 carbon atoms and a high aliphatic acid diol having at least 33 carbon atoms. A method for producing an unsaturated aliphatic carboxylic acid ester of an aliphatic triol having a carbon number. 8. High carbon number aliphatic diols having at least 22 carbon atoms and 30 to 97% by weight of high carbon number aliphatic diols having at least 33 carbon atoms.
A mixture with ~ 70% by weight.