JP2007091650A - Method for producing polymerizable compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a side chain-type radically polymerizable compound. <P>SOLUTION: The method for producing the compound represented by general formula (5) by using a compound represented by general formula (1) as a starting material, and introducing substituents to hydroxy groups of the compound in order is provided. (In the formulas, R<SP>1</SP>is an alkyl group; R<SP>2</SP>is an alkyl group which may be substituted; R<SP>3</SP>is H or a methyl group; R<SP>4</SP>and R<SP>5</SP>are each an alkylene group; Y<SP>1</SP>, Y<SP>3</SP>and Y<SP>4</SP>are each a carbonyl group or a single bond; and Y<SP>2</SP>is a single bond or oxygen). The side chain-type radically polymerizable compound can be efficiently produced by the production method. The light scattering type liquid crystal device containing the polymerizable compound as a constituent member is useful as a constituent member of a light-scattering type liquid crystal device because of being driven at a low voltage even in a wide temperature range. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a novel polymerizable compound, and more specifically, a polymerizable compound that can be suitably used as a light control layer forming material for a light-scattering liquid crystal device that can be driven at a low voltage in a wide temperature range and has excellent electro-optical characteristics. It relates to the manufacturing method.

  With the development of the information society, the demand for information and communication materials is increasing. In particular, light-scattering liquid crystal devices do not require polarizing plates and have little viewing angle dependency, so advertising boards, decorative display boards, watches, computers, projections, digital paper, portable information terminals, optical shutters, It is highly expected as a liquid crystal display element or an optical element used for the above.

A liquid crystal device having a light control layer comprising a polymer matrix and a liquid crystal composition, which is obtained by irradiating or heating a light control layer forming material comprising a radical polymerizable composition and a liquid crystal composition as a light scattering liquid crystal device. It has been known.
The device does not depend on the type of liquid crystal compound used, and the change in drive voltage is small in a wide temperature range of about -20 ° C to 70 ° C, and the absolute value of the drive voltage is 20 V or less. Is required. In particular, when the liquid crystal driving method is TFT driving, it is indispensable to lower the voltage to 10 V or less and to remove impurities, and the development of a polymerizable compound that satisfies these characteristics is in progress, and the following general formula (E Side-chain type radically polymerizable compounds as schematically represented by) have been developed.

（式中、Mcは主鎖を表し、Sc¹は側鎖1を表し、Sc²は側鎖2を表すが、Sc¹＞Sc²であり、Mc及びScは主に炭素原子により構成される。）
当該側鎖型ラジカル重合性化合物の製造は、従来次に示すようなグリシジルエーテルを用いて行われていた（特許文献１及び２参照。）。

(In the formula, Mc represents a main chain, Sc ¹ represents a side chain 1, Sc ² represents a side chain 2, Sc ¹ > Sc ² , and Mc and Sc are mainly composed of carbon atoms. .)
The production of the side chain radically polymerizable compound has heretofore been performed using glycidyl ether as shown below (see Patent Documents 1 and 2).

（式中、Ｒ^１は一般式（１）と同じ意味を表し、Ｒ^２及びＹ^１は一般式（２）と同じ意味を表し、Ｒ^５及びＹ^４は一般式（４）と同じ意味を表す。）しかしながら、当該製造方法では、原料として用いられたグリシジルエーテルの開環反応時に２級水酸基の他に、１級水酸基を生成する反応由来の不純物を取り除くことが困難であり、液晶表示素子の構成部材として用いることが可能な高純度の側鎖型ラジカル重合性化合物を製造することは困難であった。

(Wherein R ¹ represents the same meaning as in general formula (1), R ² and Y ¹ represent the same meaning as in general formula (2), and R ⁵ and Y ⁴ represent the same meaning as in general formula (4). However, in this production method, it is difficult to remove impurities derived from the reaction that generates primary hydroxyl groups in addition to secondary hydroxyl groups during the ring-opening reaction of glycidyl ether used as a raw material. It was difficult to produce a high-purity side-chain type radical polymerizable compound that can be used as a constituent member.

Moreover, as a manufacturing method of a side chain type radically polymerizable compound, the manufacturing method by mixing a polyhydric hydroxyl compound, a fatty acid, and acrylic acid simultaneously, and performing esterification is disclosed (refer patent document 3). ). However, in the production method described in the cited document, a structure other than the target product is produced in a large amount, and impurities required to be mixed into the final product cannot obtain the characteristics required as a polymerizable liquid crystal composition. There has been a problem that the quality of the liquid crystal device varies greatly. In particular, in a light-scattering liquid crystal device for driving a TFT, it is necessary to minimize the mixing of impurities, and it is necessary to remove similar structures other than the target compound, polar impurities, and the like in the manufacturing process. However, it is difficult to efficiently extract only the target compound from the mixture obtained by the production method described in the cited document, and there is a problem that production efficiency is greatly reduced.
Under such circumstances, a method using an oxetane derivative as shown below has been developed as a method for efficiently producing a side chain type radically polymerizable compound (see Patent Document 4).

（式中、Ｒ^１は一般式（１）と同じ意味を表す。）しかしながら、当該方法を用いても目的物の純度は必ずしも十分ではなく、側鎖型ラジカル重合性化合物を効率的に製造する方法としてより効率的な方法の開発が求められていた。

(In the formula, R ¹ has the same meaning as in the general formula (1).) However, even if this method is used, the purity of the target product is not always sufficient, and a side chain type radical polymerizable compound is efficiently produced. The development of more efficient methods has been demanded.

JP-A-11-29527 JP 2002-293828 A JP 2004-352851 A JP 2005-225831 A

  The problem to be solved by the present invention is to provide an efficient production method of a side chain type radical polymerizable compound.

As a result of various studies on the production method of the side chain type radical polymerizable compound, the present inventors have found that the above-mentioned problems can be solved by producing an alcohol derivative having a specific structure. It came to complete.
The present invention provides a general formula (1)

（式中、Ｒ^１は、炭素原子数１〜１５のアルキル基を表す。）で表される化合物に、一般式（２）

(Wherein R ¹ represents an alkyl group having 1 to 15 carbon atoms), and the compound represented by the general formula (2)

（式中、Ｒ^２は炭素原子数１〜２０の直鎖又は分岐アルキル基を表し、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、基中に存在する水素原子はハロゲンによって置換されていても良く、Ｙ^１はカルボニル基又は単結合を表し、Ｘ^１は水酸基、置換スルホニルオキシ基又はハロゲンを表すが、Ｙ^１がカルボニル基を表し、Ｘ^１が水酸基を表す場合、当該化合物の酸無水物であっても良い。）で表される化合物、一般式（３）

(In the formula, R ² represents a linear or branched alkyl group having 1 to 20 carbon atoms, and one or two or more carbon atoms present in the group are such that oxygen atoms are not directly bonded to each other. A single bond between one or more carbons which may be replaced by an oxygen atom and which is present in the group may be replaced by a double bond or a triple bond, and a hydrogen atom present in the group May be substituted by halogen, Y ¹ represents a carbonyl group or a single bond, X ¹ represents a hydroxyl group, a substituted sulfonyloxy group or a halogen, Y ¹ represents a carbonyl group, and X ¹ represents a hydroxyl group. In this case, it may be an acid anhydride of the compound.), A compound represented by the general formula (3)

（式中、Ｒ^３は水素原子又はメチル基を表し、Ｒ^４は炭素原子数１〜６の直鎖又は分岐アルキレン基又は単結合を表すが、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、基中に存在する水素原子はハロゲンによって置換されていても良く、Ｙ^２は単結合又は酸素原子を表し、Ｙ^３はカルボニル基又は単結合を表し、を表し、Ｘ^２は水酸基、置換スルホニルオキシ基又はハロゲンを表すが、Ｙ^３がカルボニル基を表し、Ｘ^２が水酸基を表す場合、当該化合物の酸無水物であっても良い。）で表される化合物及び一般式（４）

(In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a single bond, but one or two or more present in the group. Carbon atoms may be replaced by oxygen atoms as if the oxygen atoms are not directly bonded to each other, and single bonds between one or more carbons present in the group may be double bonds or triple bonds The hydrogen atom present in the group may be substituted by a halogen, Y ² represents a single bond or an oxygen atom, Y ³ represents a carbonyl group or a single bond, and X ² represents a hydroxyl group, a substituted sulfonyloxy group or a halogen, and when Y ³ represents a carbonyl group and X ² represents a hydroxyl group, the compound may be an acid anhydride of the compound. General formula (4)

（式中、Ｒ^５は直鎖であっても分岐していていても良い炭素原子数５〜２５のアルキレン基又はアルカントリイル基を表し、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、ｎは２又は３を表し、Ｙ^４はカルボニル基又は単結合を表し、を表し、Ｘ^３は水酸基、置換スルホニルオキシ基又はハロゲンを表す。）で表される化合物をそれぞれ反応させることによる一般式（５）

(In the formula, R ⁵ represents a linear or branched alkylene group having 5 to 25 carbon atoms or alkanetriyl group, and one or more carbon atoms present in the group. An atom may be replaced by an oxygen atom as if the oxygen atoms are not directly bonded to each other, and a single bond between one or more carbons present in the group may be a double bond or a triple bond. And n ⁴ represents 2 or 3, Y ⁴ represents a carbonyl group or a single bond, and X ³ represents a hydroxyl group, a substituted sulfonyloxy group or a halogen. General formula (5) by reacting each

（式中、Ｒ^５及びｎは一般式（４）と同じ意味を表し、Ｒ^１は一般式（１）と同じ意味を表し、Ｒ^２及びＹ^１は一般式（２）と同じ意味を表し、Ｒ^３、Ｒ^４、Ｙ^２及びＹ^３は一般式（３）と同じ意味を表す。）で表される重合性化合物の製造方法である。

(Wherein R ⁵ and n represent the same meaning as in general formula (4), R ¹ represents the same meaning as in general formula (1), and R ² and Y ¹ represent the same meaning as in general formula (2). , R ³ , R ⁴ , Y ² and Y ³ represent the same meaning as in the general formula (3).).

  The production method of the present invention makes it possible to efficiently produce a side chain type radically polymerizable compound. A light-scattering liquid crystal device including the polymerizable compound as a constituent member is useful as a display element because it can be driven at a low voltage even in a wide temperature range.

  The production method of the present invention is characterized in that the compound represented by the general formula (1) is reacted with the compound represented by the general formula (2), the general formula (3) and the general formula (3). It is. The order of reaction of the compounds represented by the general formula (2), the general formula (3) and the general formula (3) can be started from any compound. However, from the viewpoint of ease of purification of the intermediate, the compound represented by the general formula (1) is generally reacted with the halogen compound represented by the general formula (2), a carboxylic acid or a derivative thereof. Formula (6)

（式中、Ｒ^１は一般式（１）と同じ意味を表し、Ｒ^２及びＹ^１は一般式（２）と同じ意味を表す。）で表される化合物とした後、一般式（３）で表されるアルコール、カルボン酸又はこれらの誘導体を反応させることにより、一般式（７）

(Wherein R ¹ represents the same meaning as in general formula (1), and R ² and Y ¹ represent the same meaning as in general formula (2)), and then the general formula (3) Is reacted with an alcohol, carboxylic acid or a derivative thereof represented by the general formula (7)

（式中、Ｒ^１は一般式（１）と同じ意味を表し、Ｒ^２及びＹ^１は一般式（２）と同じ意味を表し、Ｒ^３、Ｒ^４、Ｙ^２及びＹ^３は一般式（３）と同じ意味を表す。）で表される化合物とした後、一般式（４）で表される化合物を反応させることが好ましい。

(In the formula, R ¹ represents the same meaning as in general formula (1), R ² and Y ¹ represent the same meaning as in general formula (2), and R ³ , R ⁴ , Y ² and Y ³ represent the general formula ( It is preferable to react the compound represented by the general formula (4) after the compound represented by the same meaning as 3).

The reaction for producing the compound represented by the general formula (6) from the trimethylolpropane derivative represented by the general formula (1) and the compound represented by the general formula (2) is a basic compound such as triethylamine or pyridine. It is preferable to perform the following. A solvent having high solubility with the raw material alcohol is selected as the reaction solvent. It is not preferable to carry out the reaction in a state in which the raw material alcohol is dispersed using a solvent having low solubility because a large amount of dialkyl and trialkyl forms are generated. The reaction temperature is preferably about room temperature, and it is preferable to suppress the dropping rate of the compound represented by the general formula (2).
Dialkyl and trialkyl compounds by-produced in the reaction are polar solvents such as hexane, heptane and other hydrocarbon solvents, dimethyl sulfoxide (hereinafter abbreviated as DMSO), N, N-dimethylformamide (hereinafter abbreviated as DMF), methanol, and the like. Since it moves to the hydrocarbon solvent side by two-liquid separation with a solvent, the target product can be easily removed (transfer to a polar solvent). Thereafter, the target product is extracted from the polar solvent. Furthermore, a dialcohol derivative represented by the general formula (6) having a high purity can be obtained by recrystallization or distillation.
In particular, a combination of hexane or heptane and methanol or a methanol / water mixed solvent is preferable because it not only has a high resolution, but also facilitates removal of the solvent after the separation.

Further, after protecting the two hydroxyl groups of the compound represented by the general formula (1) as a cyclic acetal derivative, the compound represented by the general formula (2) is reacted, and then the cyclic acetal is removed to remove the general formula (6). It is also preferable to go through a step of obtaining a compound represented by:
In this case, the ketone derivative used for protection is not particularly limited, but a ketone derivative having 10 or less carbon atoms is preferable from the viewpoint of availability and cost, and acetone, methyl ethyl ketone, and the like are preferable.
When the protection step is added, the intermediate cyclic acetal derivative is specifically represented by the general formula (8)

（式中、Ｒ^１は一般式（１）と同じ意味を表し、Ｒ^５及びＲ^６はそれぞれ独立して水素原子又はアルキル基を表す。）で表される化合物が好ましい。
特に、Ｙ^１が単結合を表す場合、保護工程を経由する方法が好ましい。

(Wherein R ¹ represents the same meaning as in general formula (1), and R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group).
In particular, when Y ¹ represents a single bond, a method through a protection step is preferable.

When the trimethylolpropane derivative represented by the general formula (1) is directly etherified with an alkyl halide, a dialkyl or trialkyl form may be produced, and the yield of the target product may not be sufficiently improved. In this case, the trimethylolpropane derivative represented by the general formula (1) is preferably protected with ether after using acetone, dimethoxypropane or the like to protect the two hydroxyl groups.
In the case of acetone (R ⁵ = R ⁶ = hydrogen atom) or 2,2-dimethoxypropane (R ⁵ = R ⁶ = methyl group), the protective group is introduced in the presence of an acid catalyst such as p-toluenesulfonic acid. It is preferable to do. Various organic solvents can be used as the reaction solvent in this case, and typical solvents include toluene, DMF, THF, acetonitrile, and the like. Acetonitrile is preferred in terms of reaction time and yield.
When protecting the hydroxyl group with acetone, if the acetone is not removed by washing with water after the reaction, the deprotection reaction will occur during the distillation of the solvent and the yield will be reduced. In the case where the property is high and only acetone cannot be efficiently removed by washing with water, protection with 2,2-dimethoxypropane is preferred.

  Compound represented by general formula (8) by reaction of compound represented by general formula (8) and alkyl halide

（式中、Ｒ^１は一般式（１）と同じ意味を表し、Ｒ^５及びＲ^６はそれぞれ独立して水素原子又はアルキル基を表し、Ｒ^２及びＹ^１は一般式（２）と同じ意味を表す。）の製造は、塩基性条件による一般的な方法で実施することができる。その際、テトラブチルアンモニウムブロミド等の相間移動触媒存在下に行うことが好ましい。反応溶媒としては、無溶媒でも反応を行うことはできるがＤＭＳＯ、ＤＭＦ、Ｎ−メチルピロリジノン等の非水系極性溶媒を用いることが好ましく、反応収率の点でＤＭＳＯを用いることが特に好ましい。
保護基の除去は、酸性条件下溶媒中で行う一般的な方法を用いることができるが、エタノール等のアルコール中で希塩酸等を用い、加熱条件下行う方法が好ましい。保護基を除去することにより、一般式（６）で表される化合物を得ることができ前述の２液分離により、同様に純度の高い中間体を得ることができる。

(Wherein R ¹ represents the same meaning as in general formula (1), R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group, and R ² and Y ¹ have the same meaning as in general formula (2). Can be produced by a general method under basic conditions. In that case, it is preferable to carry out in the presence of a phase transfer catalyst such as tetrabutylammonium bromide. As the reaction solvent, the reaction can be carried out without a solvent, but a nonaqueous polar solvent such as DMSO, DMF, N-methylpyrrolidinone is preferably used, and DMSO is particularly preferably used in view of the reaction yield.
The removal of the protecting group can be performed by a general method performed in a solvent under acidic conditions, but a method performed under heating conditions using dilute hydrochloric acid or the like in an alcohol such as ethanol is preferable. By removing the protecting group, the compound represented by the general formula (6) can be obtained, and an intermediate having a high purity can be obtained by the above-described two-liquid separation.

The compound represented by the general formula (6) is sequentially reacted with the compound represented by the general formula (3) and the compound represented by the general formula (4). In consideration of the efficiency of the reaction, the general formula (3) It is preferable to react the compound represented by General Formula (4) after reacting the compound represented by General Formula (7).
The compound represented by the general formula (7) is produced by esterifying the compound represented by the general formula (6) and the general formula (3) with an acid catalyst or 1,3-dicyclohexylcarbodiimide (DCC), N-ethyl. Although it can be performed by esterification with a dehydrating condensing agent such as —N ′-(3-dimethylaminopropyl) carbodiimide (WSC), it is preferable to use a dehydrating condensing agent in terms of reaction yield.
An acrylic acid chloride (when X ² represents halogen in the general formula (3)) can be reacted in the presence of an amine catalyst instead of the acrylic acid derivative, but the acrylic acid derivative is more often used. It is preferable because the production of diacrylic body can be suppressed.
When an acrylate is used, the reactivity of the acrylate is higher in the general formula (7) generated from the general formula (6) as a starting material. In this case, when a phase transfer catalyst such as tetrabutylammonium bromide or cetyldimethylethylammonium bromide is used in the reaction system, the production of diacrylic body can be suppressed.
It is also possible to acrylate by dehydrochlorination using acrylic acid and chloropropionic acid or chloropropionic acid chloride instead of acrylic acid chloride.
The reaction product thus synthesized can be easily purified by the same polar-nonpolar two-liquid separation as described above, or a silica gel column.

By reacting the compound represented by the general formula (7) with the compound represented by the general formula (4), the general formula (5) as the final product is produced. In this case, the inner carboxylic acid derivative of the compound represented by the general formula (4) is esterified in the presence of the aforementioned dehydration condensing agent, or the inner carboxylic acid halide of the compound represented by the general formula (4) is used for the purpose. A compound represented by the general formula (5) can be produced. Even in this case, it is more preferable to use a dehydrating condensing agent.
Furthermore, by two-liquid separation using a hydrocarbon solvent such as hexane and heptane and a polar solvent such as DMSO, DMF, and methanol, the target product is transferred to the hydrocarbon solvent side, and raw materials, carbodiimide, and by-product urea compounds are easily obtained. Can be removed. In particular, a combination of hexane or heptane and methanol or a methanol / water mixed solvent is preferable because it not only has a high resolution, but also facilitates removal of the solvent after the separation.

In the general formula (1), R ¹ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a linear alkyl group having 1 to 4 carbon atoms. The trihydroxymethylalkane compound represented by the general formula (1) can be obtained by a condensation reaction with a corresponding aldehyde compound and paraform.
In the general formula (2), R ² is preferably a linear or branched alkyl group having 5 to 20 carbon atoms, more preferably a linear alkyl group having 5 to 14 carbon atoms, or a branched alkyl group having 8 to 18 carbon atoms. preferable. Specifically, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-octadecyl group, 2-n-heptylnonyl group, isomyristyl group 2-ethylhexyl group, butoxyethyl group, hexyloxyethyl group, n-butoxyethoxymethyl group, cyclohexyl group, polyethylene glycol monoether group, 4-octylcyclohexyl group and the like.
In General Formula (2), Y ¹ represents a carbonyl group or a single bond, X ¹ represents a hydroxyl group, a substituted sulfonyloxy group, or a halogen, Y ¹ is a carbonyl group, and X ¹ is a halogen, or A production method using a compound in which Y ¹ is a single bond and X ¹ is halogen is preferable from the viewpoint of cost reduction.

In the general formula (3), R ³ represents hydrogen or a methyl group, and hydrogen is more preferable because of high reactivity.
In the general formula (3), R ⁴ is preferably a single bond or preferably having 1 to 2 carbon atoms, Y ² is an oxygen atom, Y ³ is a single bond or a carbonyl group, and X ³ is preferably a hydroxyl group. . Specific compounds include acrylic acid, acrylic acid dimer, or hydroxyethyl acrylate.
In the general formula (4), R ⁵ is preferably an alkylene group having ^{5 to} 26 carbon atoms or an alkanetriyl group, and more preferably an alkylene group having 5 to 22 carbon atoms. Y ⁴ is preferably a carbonyl group, and X ³ is preferably a hydroxyl group or a halogen. Specific examples of the compound include adipic acid, suberic acid, sebacic acid, long-chain dibasic acid, and acid chlorides thereof.

In the general formula (8), R ⁵ and R ⁶ are each independently preferably an alkyl group having 1 to 5 carbon atoms, and more preferably 1 to 2 carbon atoms.

The composition of the polymerizable compound represented by the general formula (5) and the liquid crystal composition thus obtained is particularly useful as a light control layer forming material for a light scattering liquid crystal device.

Examples of the present invention will be shown below, and the present invention will be described more specifically. However, the present invention is not limited to these examples. In the following examples, “%” represents “% by mass” unless otherwise specified.
Example 1 Production of Compound Represented by Formula (M-1) (Example 1-1)
A reaction vessel equipped with a stirrer and a thermometer was charged with 100 g (750 mmol) of trimethylolpropane, 1.9 g (7.45 mmol) of P-toluenesulfonic acid pyridinium salt, and 500 ml of acetonitrile and stirred at room temperature. Next, 116.4 g (1.12 mol) of 2,2-dimethoxypropane was slowly added dropwise. After completion of the dropwise addition, the mixture is stirred at room temperature for 2 hours, and the reaction is terminated after confirming that the raw materials have disappeared. The reaction solution was concentrated to synthesize 135 g of the compound represented by the formula (10) in which trimethylolpropane was protected.

（実施例１−２）
次いで、撹拌装置、及び温度計を備えた反応容器に、上記で合成した式（１０）で表される化合物 130g（０．７５モル）、1-ブロモヘキサン １８４．８ｇ（１．１２モル）とセチルヂメチルアンモニウムブロミド１４．１ｇ、ＤＭＳＯ １Ｌを仕込む。反応容器を室温で攪拌しながら５０％水酸化カリウム水溶液 １３０ｇをゆっくり滴下した。滴下終了後、室温で１時間撹拌後、更に６０℃で２時間攪拌して反応を完結させた。原料が消失したのを確認して反応を終了させ、反応液に酢酸エチル １Ｌ、ｎ−ヘキサン ５００ｍｌを加えて、純水、食塩水で洗浄し、有機層を濃縮して式（１１）で表される化合物の粗生物を１８０ｇ得た。

(Example 1-2)
Next, in a reaction vessel equipped with a stirrer and a thermometer, 130 g (0.75 mol) of the compound represented by the formula (10) synthesized above, 184.8 g (1.12 mol) of 1-bromohexane, Charge 14.1 g of cetyldimethylammonium bromide and 1 L of DMSO. While stirring the reaction vessel at room temperature, 130 g of 50% aqueous potassium hydroxide solution was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour and further stirred at 60 ° C. for 2 hours to complete the reaction. After confirming the disappearance of the raw materials, the reaction was terminated, and 1 L of ethyl acetate and 500 ml of n-hexane were added to the reaction solution, washed with pure water and brine, and the organic layer was concentrated and represented by formula (11). 180 g of a crude product of the resulting compound was obtained.

（実施例１−３）
更に、撹拌装置、及び温度計を備えた反応容器に、上記で合成した式（１１）で表される化合物 １８０ｇ 、テトラヒドロフラン（以下ＴＨＦと略す）４００ｍｌ、１０％塩酸水溶液 ４００ｍｌ、を加え、６５℃で２時間攪拌する。反応終了後、ＴＨＦを留去して、酢酸エチル１Ｌを加え、純水 飽和食塩水で洗浄した。有機層の溶媒を留去した後にｎ−ヘキサン６００ｍｌに溶解させ、メタノール／水の４／１（体積比）混合溶液７００ｍｌで２回抽出した。メタノール／水層からメタノールを留去した後、酢酸エチル １Ｌを加え、純水、飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥、溶媒を留去、更に蒸留により精製を行い式（１２）で表される化合物を８０ｇ得た。

(Example 1-3)
Furthermore, 180 g of the compound represented by the formula (11) synthesized above, 400 ml of tetrahydrofuran (hereinafter abbreviated as THF), 400 ml of 10% hydrochloric acid aqueous solution were added to a reaction vessel equipped with a stirrer and a thermometer at 65 ° C. For 2 hours. After completion of the reaction, THF was distilled off, 1 L of ethyl acetate was added, and the mixture was washed with pure water and saturated brine. After the solvent of the organic layer was distilled off, it was dissolved in 600 ml of n-hexane and extracted twice with 700 ml of a methanol / water 4/1 (volume ratio) mixed solution. After distilling off methanol from the methanol / water layer, 1 L of ethyl acetate was added, washed with pure water and saturated brine, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was further purified by distillation. 80 g of the compound represented by 12) was obtained.

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：３．７０（ｍ，２Ｈ），３．５９（ｍ，２Ｈ），３．４２（ｍ，４Ｈ），２．９３（ｓ，２Ｈ），１．５９（ｍ，２Ｈ），１．３８−１．２６（ｍ，８Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：７５．０，７１．９，６５．８，４２．７，３１．５，２９．４，２９．１，２５．７，２３．０，２２．５，２２．５，１３．９，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ^−１
（実施例１−４）
次いで、撹拌装置、及び温度計を備えた反応容器に、上記で合成した式（１２）で表される化合物を５０ｇ（０．２３モル）、アクリル酸 ２４．７ｇ、ジメチルアミノピリジン ４．１５ｇ、塩化メチレン ５００ｍｌを仕込んだ。窒素ガスの雰囲気下でジイソプロピルカルボジイミド４３．２ｇ（０．３４モル）を室温でゆっくり滴下した。滴下終了後、更に２時間撹拌した後、４０℃で２時間反応させた。反応液をろ過した後、ろ液に塩化メチレン２００ｍｌ、１０％塩酸水溶液 ７００ｍｌを加え洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（１３）で表される化合物３５ｇを得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 3.70 (m, 2H), 3.59 (m, 2H), 3.42 (m, 4H), 2.93 (s, 2H), 1 .59 (m, 2H), 1.38-1.26 (m, 8H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 75.0, 71.9, 65.8, 42.7, 31.5, 29.4, 29.1, 25.7, 23.0, 22 .5, 22.5, 13.9, 7.4
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm ⁻¹
(Example 1-4)
Next, in a reaction vessel equipped with a stirrer and a thermometer, 50 g (0.23 mol) of the compound represented by the formula (12) synthesized above, 24.7 g of acrylic acid, 4.15 g of dimethylaminopyridine, 500 ml of methylene chloride was charged. Under an atmosphere of nitrogen gas, 43.2 g (0.34 mol) of diisopropylcarbodiimide was slowly added dropwise at room temperature. After completion of dropping, the mixture was further stirred for 2 hours, and then reacted at 40 ° C. for 2 hours. After filtering the reaction solution, the filtrate was washed with 200 ml of methylene chloride and 700 ml of 10% hydrochloric acid aqueous solution and further washed with saturated brine, and the organic layer was distilled off with anhydrous sodium sulfate. Purification was performed with a silica gel column (weight ratio) to obtain 35 g of a compound represented by the formula (13).

（物性値）
^１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４３（ｄ，１Ｈ），６．１２（ｑ，１Ｈ），５．８５（ｄ，１Ｈ），４．２０（ｓ，２Ｈ），３．５７（ｄ，２Ｈ），３．４４（ｍ，４Ｈ），２．８９（ｍ，１Ｈ），１．５５（ｍ，２Ｈ），１．３８−１．２６（ｍ，８Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１６６．３，１３０．８，１２８．２，１２７．９，７４．２，７１．９，６６．１，６４．５，４２．２，３１．７，２９．７，２５．７，２２．９，２２．５，１３．９，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ^−１
（実施例１−５）
更に、撹拌装置、及び温度計を備えた反応容器に、上記で合成した式（１３）で表される化合物 ３５ｇ（０．１２モル）セバシン酸 １２．９ｇ（０．０６モル）、ピロリジノピリジン ２．２７ｇ、塩化メチレン ３００ｍｌを仕込んだ。窒素ガスの雰囲気下で反応容器を０〜５℃に冷却してジイソプロピルカルボジイミド１９．３ｇ（０．１５モル）をゆっくり滴下した。滴下終了後、室温で４時間反応させた。反応液に塩化メチレン２００ｍｌ、１０％塩酸水溶液 ７００ｍｌを加え洗浄し、更に飽和食塩水で洗浄し有機層の溶媒を留去した後に、ｎ−ヘキサン５００ｍｌを加え、メタノール／水の４／１（体積比）混合溶液５００ｍｌで洗浄した。更に有機層を純水、飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥、溶媒を留去、更に５倍量（重量比）のシリカゲルカラムにより精製を行い目的の化合物（Ｍ−１）を３８．７ｇを得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.43 (d, 1H), 6.12 (q, 1H), 5.85 (d, 1H), 4.20 (s, 2H), 3 .57 (d, 2H), 3.44 (m, 4H), 2.89 (m, 1H), 1.55 (m, 2H), 1.38-1.26 (m, 8H),. 92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 166.3, 130.8, 128.2, 127.9, 74.2, 71.9, 66.1, 64.5, 42.2, 31 .7, 29.7, 25.7, 22.9, 22.5, 13.9, 7.4
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm ⁻¹
(Example 1-5)
Furthermore, in a reaction vessel equipped with a stirrer and a thermometer, 35 g (0.12 mol) of the compound represented by the formula (13) synthesized above, 12.9 g (0.06 mol) of sebacic acid, pyrrolidinopyridine 2.27 g and 300 ml of methylene chloride were charged. Under a nitrogen gas atmosphere, the reaction vessel was cooled to 0 to 5 ° C., and 19.3 g (0.15 mol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction was allowed to proceed at room temperature for 4 hours. The reaction solution was washed by adding 200 ml of methylene chloride and 700 ml of 10% aqueous hydrochloric acid, and further washed with saturated saline, and the solvent of the organic layer was distilled off. Then, 500 ml of n-hexane was added, and 4/1 (volume by volume of methanol / water). Ratio) Washed with 500 ml of the mixed solution. Further, the organic layer was washed with pure water and saturated brine, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and further purified with a 5-fold amount (weight ratio) silica gel column to obtain the target compound (M-1 ) Was obtained 38.7 g.

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４１（ｄ，２Ｈ），６．１２（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１１（ｓ，４Ｈ），４．０５（ｓ，４Ｈ），３．３５（ｔ，４Ｈ），３．２９（ｓ，４Ｈ），２．３１（ｔ，４Ｈ），１．６２（ｍ，４Ｈ），１．６−１．４７（ｍ，８Ｈ），１．２５（ｍ，２０Ｈ），０．９２−０．８（ｍ，１２Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．６，１６５．９，１３０．６，１２８．３，７１．６，７０．３，６４．７，６４．４，４１．５，３４．３，３１．９，２９．６−２９．０，２５．７，２５．０，２３．０，２２．６，１４．０，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９
（実施例２） 式（Ｍ−２）で表される化合物の製造
（実施例２−１）
トリメチロールプロパン（１モル）と２，２−ジメトキシプロパン（１．５モル）、ｐ−トルエンスルホン酸（０．０１モル）を用い、実施例１−１と同様にして式（１４）で表される化合物を得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.11 (s, 4H), 4 .05 (s, 4H), 3.35 (t, 4H), 3.29 (s, 4H), 2.31 (t, 4H), 1.62 (m, 4H), 1.6-1. 47 (m, 8H), 1.25 (m, 20H), 0.92-0.8 (m, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.6, 165.9, 130.6, 128.3, 71.6, 70.3, 64.7, 64.4, 41.5, 34 3, 31.9, 29.6-29.0, 25.7, 25.0, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
(Example 2) Production of a compound represented by the formula (M-2) (Example 2-1)
Using trimethylolpropane (1 mol), 2,2-dimethoxypropane (1.5 mol), and p-toluenesulfonic acid (0.01 mol), it is represented by the formula (14) in the same manner as in Example 1-1. The compound obtained was obtained.

（実施例２−２）
式（１４）で表される化合物（１モル）と１−ブロモデカン（１．５モル）、テトラブチルアンモニウムブロミド（０．０３モル）を用い、実施例１−２及び１−３と同様にして式（１５）で表される化合物を得た。

(Example 2-2)
Using the compound represented by the formula (14) (1 mol), 1-bromodecane (1.5 mol), and tetrabutylammonium bromide (0.03 mol), in the same manner as in Examples 1-2 and 1-3. A compound represented by the formula (15) was obtained.

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：３．７０（ｍ，２Ｈ），３．５９（ｍ，２Ｈ），３．４２（ｍ，４Ｈ），２．９３（ｓ，２Ｈ），１．５９（ｍ，２Ｈ），１．３８−１．２６（ｍ，１６Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：７５．０，７１．９，６５．８，４２．７，３１．５，２９．４，２９．１，２５．７，２３．０，２２．５，２２．５，１３．９，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ^−１
（実施例２−３）
得られた式（１５）で表される化合物（１モル）とアクリル酸（１．２モル）を用い、実施例１−４と同様にして式（１６）で表される化合物を得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 3.70 (m, 2H), 3.59 (m, 2H), 3.42 (m, 4H), 2.93 (s, 2H), 1 .59 (m, 2H), 1.38-1.26 (m, 16H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 75.0, 71.9, 65.8, 42.7, 31.5, 29.4, 29.1, 25.7, 23.0, 22 .5, 22.5, 13.9, 7.4
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm ⁻¹
(Example 2-3)
The compound represented by the formula (16) was obtained in the same manner as in Example 1-4, using the compound represented by the formula (15) (1 mol) and acrylic acid (1.2 mol).

（物性値）
^１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４３（ｄ，１Ｈ），６．１２（ｑ，１Ｈ），５．８５（ｄ，１Ｈ），４．２０（ｓ，２Ｈ），３．５７（ｄ，２Ｈ），３．４４（ｍ，４Ｈ），２．８９（ｍ，１Ｈ），１．５５（ｍ，２Ｈ），１．３８−１．２６（ｍ，１６Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１６６．３，１３０．８，１２８．２，１２７．９，７４．２，７１．９，６６．１，６４．５，４２．２，３１．７，２９．７，２５．７，２２．９，２２．５，１３．９，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ^−１
（実施例２−４）
得られた式（１６）で表される化合物とアジピン酸を用い、実施例１−５と同様にして式（Ｍ−２）で表される重合性化合物を得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.43 (d, 1H), 6.12 (q, 1H), 5.85 (d, 1H), 4.20 (s, 2H), 3 .57 (d, 2H), 3.44 (m, 4H), 2.89 (m, 1H), 1.55 (m, 2H), 1.38-1.26 (m, 16H),. 92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 166.3, 130.8, 128.2, 127.9, 74.2, 71.9, 66.1, 64.5, 42.2, 31 .7, 29.7, 25.7, 22.9, 22.5, 13.9, 7.4
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm ⁻¹
(Example 2-4)
Using the obtained compound represented by the formula (16) and adipic acid, a polymerizable compound represented by the formula (M-2) was obtained in the same manner as in Example 1-5.

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４１（ｄ，２Ｈ），６．１２（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１１（ｓ，４Ｈ），４．０５（ｓ，４Ｈ），３．３５（ｔ，４Ｈ），３．２９（ｓ，４Ｈ），２．３１（ｔ，４Ｈ），１．６２（ｍ，４Ｈ），１．６−１．４７（ｍ，８Ｈ），１．２５（ｍ，２８Ｈ），０．９２−０．８（ｍ，１２Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．６，１６５．９，１３０．６，１２８．３，７１．６，７０．３，６４．７，６４．４，４１．５，３４．３，３１．９，２９．６−２９．０，２５．７，２５．０，２３．０，２２．６，１４．０，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９
（実施例３） 式（Ｍ−３）で表される化合物の製造
（実施例３−１）
撹拌装置、及び温度計を備えた反応容器にトリメチロールプロパン２２０ｇ （１．６４モル）とトリエチルアミン７２．７ｇ（０．７２モル）、ＴＨＦ １．２Ｌを仕込んだ。反応容器を５℃以下に保ち、ｎ−デカノイルクロリド１２５ｇ（０．６６モル）を滴下ロートでゆっくり滴下した。滴下終了後、室温で3時間攪拌後、４０℃で１時間撹拌して反応を完結させた。反応液に酢酸エチル８００ｍｌ、ｎ−ヘキサン２００ｍｌ、加えて１０％塩酸水溶液１Ｌで洗浄後、水洗、飽和食塩水で洗浄した。有機層を濃縮した後、ｎ−ヘプタン１．２Ｌに溶解させ、メタノール／水の４／１（体積比）混合溶液１．２Ｌで抽出した。メタノール／水層からメタノールを留去して、酢酸エチル１Ｌ、ｎ-ヘキサン ２００ｍｌ、純水１Ｌ加えて水洗する。有機層を無水硫酸ナトリウムで乾燥、溶媒を留去して粗生成物を１４５ｇ得た。ｎ−ヘプタン ３００ｍｌで再結晶を2回行い、式（１７）で表される化合物を１３５ｇ得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.11 (s, 4H), 4 .05 (s, 4H), 3.35 (t, 4H), 3.29 (s, 4H), 2.31 (t, 4H), 1.62 (m, 4H), 1.6-1. 47 (m, 8H), 1.25 (m, 28H), 0.92-0.8 (m, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.6, 165.9, 130.6, 128.3, 71.6, 70.3, 64.7, 64.4, 41.5, 34 3, 31.9, 29.6-29.0, 25.7, 25.0, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
Example 3 Production of Compound Represented by Formula (M-3) (Example 3-1)
A reaction vessel equipped with a stirrer and a thermometer was charged with 220 g (1.64 mol) of trimethylolpropane, 72.7 g (0.72 mol) of triethylamine, and 1.2 L of THF. The reaction vessel was kept at 5 ° C. or lower, and 125 g (0.66 mol) of n-decanoyl chloride was slowly dropped with a dropping funnel. After completion of dropping, the mixture was stirred at room temperature for 3 hours and then stirred at 40 ° C. for 1 hour to complete the reaction. The reaction solution was washed with 800 ml of ethyl acetate, 200 ml of n-hexane, and 1 L of a 10% aqueous hydrochloric acid solution, followed by washing with water and saturated brine. The organic layer was concentrated, dissolved in 1.2 L of n-heptane, and extracted with 1.2 L of a methanol / water 4/1 (volume ratio) mixed solution. Methanol is distilled off from the methanol / water layer, and 1 L of ethyl acetate, 200 ml of n-hexane and 1 L of pure water are added and washed. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain 145 g of a crude product. Recrystallization was performed twice with 300 ml of n-heptane to obtain 135 g of a compound represented by the formula (17).

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：４．２２（ｓ，２Ｈ），３．５８（ｍ，４Ｈ），２．７４（ｍ，２Ｈ），２．３７（ｔ，２H），１．６２（ｍ，２Ｈ），１．３８−１．２６（ｍ，１４Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：６５．９，６４．１，４２．９，３４．３，３１．８，２９．４，２９．１，２５．０，２２．６，２２．５，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ^−１
（実施例３−２）
次いで、撹拌装置、及び温度計を備えた反応容器に上記で合成した式（１７）で表される化合物１１０ｇ（０．３８モル）、アクリル酸 ４１．２ｇ（０．５７モル）、ジメチルアミノピリジン ７ｇ、塩化メチレン８００ｍｌを仕込んだ。窒素ガスの雰囲気下でジイソプロピルカルボジイミド７２ｇ（０．５７モル）を室温でゆっくり滴下した。滴下終了後、更に２時間撹拌した後、４０℃で２時間反応させた。反応液をろ過した後、ろ液に塩化メチレン５００ｍｌ、１０％塩酸水溶液 １Ｌを加えて洗浄、更に飽和食塩水で洗浄した。有機層を無水硫酸ナトリウムで乾燥溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（１８）で表される化合物７８ｇを得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 4.22 (s, 2H), 3.58 (m, 4H), 2.74 (m, 2H), 2.37 (t, 2H), 1 .62 (m, 2H), 1.38-1.26 (m, 14H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 65.9, 64.1, 42.9, 34.3, 31.8, 29.4, 29.1, 25.0, 22.6, 22 .5, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm ⁻¹
(Example 3-2)
Next, 110 g (0.38 mol) of the compound represented by the formula (17) synthesized above in a reaction vessel equipped with a stirrer and a thermometer, 41.2 g (0.57 mol) of acrylic acid, dimethylaminopyridine 7 g and 800 ml of methylene chloride were charged. Under an atmosphere of nitrogen gas, 72 g (0.57 mol) of diisopropylcarbodiimide was slowly added dropwise at room temperature. After completion of dropping, the mixture was further stirred for 2 hours, and then reacted at 40 ° C. for 2 hours. After the reaction solution was filtered, 500 ml of methylene chloride and 1 L of a 10% hydrochloric acid aqueous solution were added to the filtrate for washing, and further washed with a saturated saline solution. The organic layer was purified by a 5-fold amount (weight ratio) silica gel column after distilling off the dry solvent with anhydrous sodium sulfate to obtain 78 g of a compound represented by the formula (18).

（物性値）
^１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４４（ｄ，１Ｈ），６．１２（ｑ，１Ｈ），５．８４（ｄ，１Ｈ），４．１６（ｓ，２Ｈ），４．０５（ｓ，２Ｈ），３．４４（ｄ，２Ｈ），２．４９（ｓ，１Ｈ），２．３２（ｔ，２Ｈ），１．６２（ｍ，２Ｈ），１．４３（ｑ，２Ｈ），１．３８−１．２６（ｍ，１２Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７４．１，１６６．３，１３１．１，１２８．２，１２７．９，６３．９，６３．７，６２．２，４２．６，３４．２，３１．７，３１．５，２９．７−２９．０，２４．９，２２．６，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ^−１
（実施例３−３）
更に撹拌装置、及び温度計を備えた反応容器に上記で合成した式（１８）で表される化合物７８ｇ（０．２７７モル）、長鎖二塩基酸ＩＰＳ−２２（岡村製油社製）５１．３ｇ（０．１３８モル）、ピロリジノピリジン２ｇ、塩化メチレン１Ｌを仕込んだ。窒素ガスの雰囲気下で反応容器を０〜５℃に冷却してジイソプロピルカルボジイミド４２ｇ（０．３３モル）をゆっくり滴下した。滴下終了後、室温で４時間反応させた。反応液に塩化メチレン２００ｍｌ、１０％塩酸水溶液 ７００ｍｌを加え洗浄し、更に飽和食塩水で洗浄し有機層の溶媒を留去した後に、ｎ−ヘキサン１Ｌを加え、メタノール／水の４／１（体積比）混合溶液６００ｍｌで２回洗浄した。更に有機層を純水、飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥、溶媒を留去、更に５倍量（重量比）のシリカゲルカラムにより精製を行い目的の化合物（Ｍ−３）を９８．５ｇを得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.44 (d, 1H), 6.12 (q, 1H), 5.84 (d, 1H), 4.16 (s, 2H), 4 .05 (s, 2H), 3.44 (d, 2H), 2.49 (s, 1H), 2.32 (t, 2H), 1.62 (m, 2H), 1.43 (q, 2H), 1.38-1.26 (m, 12H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 174.1, 166.3, 131.1, 128.2, 127.9, 63.9, 63.7, 62.2, 42.6, 34 2, 31.7, 31.5, 29.7-29.0, 24.9, 22.6, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm ⁻¹
(Example 3-3)
Furthermore, 78 g (0.277 mol) of the compound represented by the formula (18) synthesized above in a reaction vessel equipped with a stirrer and a thermometer, long-chain dibasic acid IPS-22 (manufactured by Okamura Oil Co., Ltd.) 3 g (0.138 mol), 2 g of pyrrolidinopyridine, and 1 L of methylene chloride were charged. Under a nitrogen gas atmosphere, the reaction vessel was cooled to 0 to 5 ° C., and 42 g (0.33 mol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction was allowed to proceed at room temperature for 4 hours. The reaction solution was washed with 200 ml of methylene chloride and 700 ml of a 10% aqueous hydrochloric acid solution, further washed with saturated saline, and the solvent of the organic layer was distilled off. Then, 1 L of n-hexane was added, and 4/1 (volume by volume of methanol / water). Ratio) Washed twice with 600 ml of the mixed solution. Further, the organic layer was washed with pure water and saturated brine, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and further purified with a 5 times amount (weight ratio) silica gel column to obtain the target compound (M-3 ) Was obtained.

（物性値）
^１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４２（ｄ，２Ｈ），６．１２（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１２（ｓ，４Ｈ），４．０４（ｓ，８Ｈ），２．３２（ｔ，８Ｈ），１．６２（ｍ，８Ｈ），１．５８（ｍ，４Ｈ），１．３８−１．２５（ｍ，４８Ｈ），０．９１−８０（ｍ，１８Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．５，１６５．７，１３１．１，１２７．９，６４．０，６３．７，４０．６，３４．２，３１．８，２９．７−２９．０，２６．８，２４．９，２３．０，２２．６，１４．０，１０．７，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９
（実施例４） 式（Ｍ−４）で表される化合物の製造
（実施例４−１）
トリメチロールプロパン（２．５モル）及びウンデシルクロリド（１モル）を用い実施例３−１と同様にして式（１９）で表される化合物を得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.42 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H), 4 .04 (s, 8H), 2.32 (t, 8H), 1.62 (m, 8H), 1.58 (m, 4H), 1.38-1.25 (m, 48H),. 91-80 (m, 18H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 165.7, 131.1, 127.9, 64.0, 63.7, 40.6, 34.2, 31.8, 29 .7-29.0, 26.8, 24.9, 23.0, 22.6, 14.0, 10.7, 7.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
(Example 4) Production of compound represented by formula (M-4) (Example 4-1)
A compound represented by the formula (19) was obtained in the same manner as in Example 3-1, using trimethylolpropane (2.5 mol) and undecyl chloride (1 mol).

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：４．２２（ｓ，２Ｈ），３．５８（ｍ，４Ｈ），２．７４（ｍ，２Ｈ），２．３７（ｔ，２H），１．６２（ｍ，２Ｈ），１．３８−１．２６（ｍ，１６Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：６５．９，６４．１，４２．９，３４．３，３１．８，２９．４，２９．１，２５．０，２２．６，２２．５，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ^−１
（実施例４−２）
化合物（１９）（１モル）及びアクリル酸（１．２モル）を用い実施例３−２と同様にして式（２０）で表される化合物を得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 4.22 (s, 2H), 3.58 (m, 4H), 2.74 (m, 2H), 2.37 (t, 2H), 1 .62 (m, 2H), 1.38-1.26 (m, 16H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 65.9, 64.1, 42.9, 34.3, 31.8, 29.4, 29.1, 25.0, 22.6, 22 .5, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm ⁻¹
(Example 4-2)
A compound represented by the formula (20) was obtained in the same manner as in Example 3-2 using the compound (19) (1 mol) and acrylic acid (1.2 mol).

（物性値）
^１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４４（ｄ，１Ｈ），６．１２（ｑ，１Ｈ），５．８４（ｄ，１Ｈ），４．１６（ｓ，２Ｈ），４．０５（ｓ，２Ｈ），３．４４（ｄ，２Ｈ），２．４９（ｓ，１Ｈ），２．３２（ｔ，２Ｈ），１．６２（ｍ，２Ｈ），１．４３（ｑ，２Ｈ），１．３８−１．２６（ｍ，１４Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７４．１，１６６．３，１３１．１，１２８．２，１２７．９，６３．９，６３．７，６２．２，４２．６，３４．２，３１．７，３１．５，２９．７−２９．０，２４．９，２２．６，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：３１００−３６００ｃｍ^−１
（実施例４−２）
化合物（２０）及びスベリン酸を用い実施例３−３と同様にして式（Ｍ−４）で表される化合物を得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.44 (d, 1H), 6.12 (q, 1H), 5.84 (d, 1H), 4.16 (s, 2H), 4 .05 (s, 2H), 3.44 (d, 2H), 2.49 (s, 1H), 2.32 (t, 2H), 1.62 (m, 2H), 1.43 (q, 2H), 1.38-1.26 (m, 14H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 174.1, 166.3, 131.1, 128.2, 127.9, 63.9, 63.7, 62.2, 42.6, 34 2, 31.7, 31.5, 29.7-29.0, 24.9, 22.6, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 3100-3600 cm ⁻¹
(Example 4-2)
A compound represented by the formula (M-4) was obtained in the same manner as in Example 3-3 using the compound (20) and suberic acid.

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４１（ｄ，２Ｈ），６．１２（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１２（ｓ，４Ｈ），４．０４（ｓ，８Ｈ），２．３２（ｔ，８Ｈ），１．６２（ｍ，８Ｈ），１．５８（ｍ，４Ｈ），１．２５（ｍ，３２Ｈ），０．９２−０．８（ｍ，１２Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．６，１６５．９，１３０．６，１２８．３，７１．６，７０．３，６４．７，６４．４，４１．５，３４．３，３１．９，２９．６−２９．０，２５．７，２５．０，２３．０，２２．６，１４．０，７．４
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９
（比較例）
本願発明に係る化合物に類似する化合物に関して、従来の方法で製造を行った。
撹拌装置、冷却管及び温度計を備えた四つ口フラスコに、ラウリン酸グリシジルエステル２５７ｇ（１．０モル）、アクリル酸１０８ｇ（１．５モル）、ｐ−メトキシフェノール１５０mg及び触媒としてＮ，Ｎ−ジメチルベンジルアミン１．３１ｇを入れ、８０℃で撹拌した。次に、反応液を１１０℃にゆっくり昇温し、同温度に保ちながら、１０時間撹拌して反応を完結させた。次に、５％水酸化ナトリウム溶液３００mlで洗浄し、更に、純水及び飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた後、有機溶媒を留去して、酸価０．８の淡褐色透明液状生成物を得た。
次に、撹拌装置、窒素導入管、冷却管及び温度計を備えた四つ口フラスコに、上記液状生成物３３．０ｇ、ｐ−メトキシフェノール２０mg、４−ジメチルアミノピリジン３．１ｇ、セバシン酸１０．１ｇ（０．０５モル）及びテトラヒドロフラン５００mlを加え、窒素気流下で、水氷バスを用いて５℃に保った。次に、ジシクロヘキシルカルボジイミド２０．６ｇ（０．１モル）のテトラヒドロフラン１００ml溶液を１時間かけてゆっくり滴下した。滴下終了後、水氷バスを外し、室温で２４時間撹拌して反応を完結させた。反応終了後、析出したジシクロヘキシル尿素を濾別し、濃縮した。濃縮液をトルエン２００mlに溶解させ、純水及び飽和食塩水で洗浄した後、有機層を無水硫酸ナトリウムで乾燥させた。有機層の溶媒を減圧留去し、濃縮液をシリカゲルクロマトグラフィー（濃縮液に対して４０倍量のシリカゲルを使用）を用いて精製して、次式

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.41 (d, 2H), 6.12 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H), 4 .04 (s, 8H), 2.32 (t, 8H), 1.62 (m, 8H), 1.58 (m, 4H), 1.25 (m, 32H), 0.92-0. 8 (m, 12H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.6, 165.9, 130.6, 128.3, 71.6, 70.3, 64.7, 64.4, 41.5, 34 3, 31.9, 29.6-29.0, 25.7, 25.0, 23.0, 22.6, 14.0, 7.4
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
(Comparative example)
A compound similar to the compound according to the present invention was produced by a conventional method.
In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 257 g (1.0 mol) of glycidyl laurate, 108 g (1.5 mol) of acrylic acid, 150 mg of p-methoxyphenol and N, N as a catalyst -1.31 g of dimethylbenzylamine was added and stirred at 80 ° C. Next, the reaction solution was slowly heated to 110 ° C. and stirred for 10 hours to complete the reaction while maintaining the same temperature. Next, it was washed with 300 ml of 5% sodium hydroxide solution, and further washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. 8 light brown transparent liquid product was obtained.
Next, in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a condenser tube and a thermometer, 33.0 g of the above liquid product, 20 mg of p-methoxyphenol, 3.1 g of 4-dimethylaminopyridine, 10 sebacic acid 10 0.1 g (0.05 mol) and 500 ml of tetrahydrofuran were added, and the mixture was kept at 5 ° C. using a water ice bath under a nitrogen stream. Next, a solution of 20.6 g (0.1 mol) of dicyclohexylcarbodiimide in 100 ml of tetrahydrofuran was slowly added dropwise over 1 hour. After completion of the dropwise addition, the water ice bath was removed and the reaction was completed by stirring at room temperature for 24 hours. After completion of the reaction, the precipitated dicyclohexylurea was filtered off and concentrated. The concentrated solution was dissolved in 200 ml of toluene, washed with pure water and saturated brine, and then the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrated solution was purified using silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrated solution).

で表わされる透明液状の側鎖型ラジカル重合性化合物２８ｇを得た。
比較例の方法では、最終工程におけるカラム精製において、４０倍量ものシリカゲルを使用しなければならないのに対して、本願発明の方法では５倍量と大幅に少ない量で精製が可能であった。更に、生成物の純度も本願発明の方法で製造された物が優れていた。

As a result, 28 g of a transparent liquid side chain type radical polymerizable compound represented by the formula:
In the method of the comparative example, 40 times the amount of silica gel must be used in the column purification in the final step, whereas in the method of the present invention, purification was possible in a significantly small amount of 5 times. Further, the product produced by the method of the present invention was excellent in the purity of the product.

Claims (6)

General formula (1)

(Wherein R ¹ represents an alkyl group having 1 to 15 carbon atoms), and the compound represented by the general formula (2)

(In the formula, R ² represents a linear or branched alkyl group having 1 to 20 carbon atoms, and one or two or more carbon atoms present in the group are such that oxygen atoms are not directly bonded to each other. A single bond between one or more carbons which may be replaced by an oxygen atom and which is present in the group may be replaced by a double bond or a triple bond, and a hydrogen atom present in the group May be substituted by halogen, Y ¹ represents a carbonyl group or a single bond, X ¹ represents a hydroxyl group, a substituted sulfonyloxy group or a halogen, Y ¹ represents a carbonyl group, and X ¹ represents a hydroxyl group. In this case, it may be an acid anhydride of the compound.), A compound represented by the general formula (3)

(In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a single bond, but one or two or more present in the group. Carbon atoms may be replaced by oxygen atoms as if the oxygen atoms are not directly bonded to each other, and single bonds between one or more carbons present in the group may be double bonds or triple bonds The hydrogen atom present in the group may be substituted by a halogen, Y ² represents a single bond or an oxygen atom, Y ³ represents a carbonyl group or a single bond, and X ² represents a hydroxyl group, a substituted sulfonyloxy group or a halogen, and when Y ³ represents a carbonyl group and X ² represents a hydroxyl group, the compound may be an acid anhydride of the compound. General formula (4)

(In the formula, R ⁵ represents a linear or branched alkylene group having 5 to 25 carbon atoms or alkanetriyl group, and one or more carbon atoms present in the group. An atom may be replaced by an oxygen atom as if the oxygen atoms are not directly bonded to each other, and a single bond between one or more carbons present in the group may be a double bond or a triple bond. And n represents 2 or 3, Y ⁴ represents a carbonyl group or a single bond, and X ³ represents a hydroxyl group, a substituted sulfonyloxy group or a halogen). General formula (5)

(Wherein R ⁵ , Y ⁴ and n represent the same meaning as in general formula (4), R ¹ represents the same meaning as in general formula (1), and R ² and Y ¹ represent the same as in general formula (2). The meaning is shown, R < ³ >, R < ⁴ >, Y < ² > and Y < ³ > represent the same meaning as General formula (3).) The manufacturing method of the polymeric compound represented by this. By reacting the compound represented by the general formula (1) with the compound represented by the general formula (2), the general formula (6)

(Wherein R ¹ represents the same meaning as in general formula (1), and R ² and Y ¹ represent the same meaning as in general formula (2)), and then the general formula (3) By reacting the compound represented by general formula (7)

(In the formula, R ¹ represents the same meaning as in general formula (1), R ² and Y ¹ represent the same meaning as in general formula (2), and R ³ , R ⁴ , Y ² and Y ³ represent the general formula ( The same meaning as 3). After the compound represented by) is reacted with the compound represented by the general formula (4), the polymerizability represented by the general formula (5) according to claim 1 Compound production method. After protecting the two hydroxyl groups of the compound represented by the general formula (1) as a cyclic acetal derivative, the compound represented by the general formula (2) is reacted, and then the cyclic acetal is removed. The manufacturing method of Claim 2 which obtains the compound to be obtained. The cyclic acetal derivative has the general formula (8)

(Wherein R ¹ represents the same meaning as in general formula (1), and R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group). Method. In the general formula (2) The method according to claim 3, wherein Y ¹ represents a single bond. The production method according to any one of claims 1 to 5, wherein in the general formula (2), R ² represents a linear or branched alkyl group having 5 to 20 carbon atoms.