Method for producing (meth)acrylic acid ester compounds

Abstract

Provided is a method for producing a (meth)acrylic acid ester compound, the method making it possible to carry out esterification at a high introduction rate and to efficiently recover the resultant ester compound.　The present invention provides a method for producing a (meth)acrylic acid ester compound, the method including reacting a polymer having a structure represented by formula (1) with a (meth)acrylic acid anhydride in the presence of at least one of potassium carbonate, rubidium carbonate, and cesium carbonate. In formula (1), R1, R2, R3, R4, and R5 each independently are selected from hydrogen atoms and alkyl groups, at least one of R1, R2, R3, R4, and R5 is selected from a single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, and alkylene group-*, and X is a hydrogen atom. At least a portion thereof reacts with the (meth)acrylic acid anhydride to yield a (meth)acrylic group.

Description

[Technical Field]

[0001] The present invention relates to a method for producing (meth)acrylic acid ester compounds. [Background technology]

[0002] Conventionally, the production of ester compounds by esterifying phenol compounds has been considered. For example, Patent Document 1 describes a solvent that forms an azeotrope with water, and phenol and the following general formula (I) [ka] A method for producing a phenyl ester by esterifying a carboxylic acid represented by formula (I) (wherein R1 represents hydrogen or a methyl group) with an acid catalyst, wherein boric acid and the following general formula (II) are added to the reaction system of the esterification reaction. [ka] A method for producing a phenyl ester is disclosed, characterized by adding 2,2-dialkylmalonic acid represented by formula (II) (wherein R2 or R3 represents a linear or branched alkyl group having 2 to 10 carbon atoms) to a carboxylic acid represented by the general formula (I) in an amount of 2 to 50 mol%.

[0003] Furthermore, Patent Document 2 discloses a curable composition comprising a sealed poly(arylene ether) produced by the reaction of an unsealed poly(arylene ether) with an anhydride chelating agent and an olefinic unsaturated monomer, wherein the water absorption of the cured composition after 7 days at 85°C and 85% relative humidity is less than 1% by weight. Here, it is stated that the reaction between the unsealed poly(arylene ether) and the anhydride chelating agent is carried out in the presence of a sealing catalyst containing 4-dialkylaminopyridine.

[0004] Furthermore, Patent Document 3 describes a method of reacting a predetermined polyphenylene oxide oligomer with 2-methacrylic anhydride (methacrylic anhydride) in the presence of sodium acetate to obtain a polyphenylene oxide oligomer with functionalized terminal groups. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2011-105667 [Patent Document 2] Special Publication No. 2007-507592 [Patent Document 3] Japanese Patent Publication No. 2019-210451 [Overview of the project] [Problems that the invention aims to solve]

[0006] As described above, methods for esterifying phenol compounds have been disclosed. However, in the inventors' investigation, when they attempted to esterify an oligophenylene ether having hydroxyl groups at both ends according to the example in Patent Document 1, the ester introduction rate was extremely low. Furthermore, when they attempted to esterify an oligophenylene ether having hydroxyl groups at both ends using 4-dimethylaminopyridine (DMAP) as a catalyst, according to the example in Patent Document 2, it was difficult to separate the catalyst from the product, and a large amount of by-products remained. Moreover, DMAP is expensive, which poses a cost problem. On the other hand, when they used sodium acetate as a catalyst, as used in the example in Patent Document 3, they found that it was difficult to introduce the (meth)acrylic group unless an excessive amount of (meth)acrylic anhydride was used. The present invention aims to solve these problems and to provide a method for producing (meth)acrylic acid ester compounds by esterifying phenol compounds, which allows for esterification with a high introduction rate and efficient recovery of the obtained ester compounds.

Means for Solving the Problem

[0007] Under the above problems, it has been found that the above problems can be solved by esterification using (meth)acrylic anhydride in the presence of a predetermined basic catalyst. Specifically, the above problems have been solved by the following means. <1>A method for producing a (meth)acrylic acid ester compound, comprising reacting a polymer having a structure represented by formula (1) with (meth)acrylic anhydride in the presence of at least one of potassium carbonate, rubidium carbonate, and cesium carbonate.

Chemical formula

[0008] The present invention provides a method for producing (meth)acrylic acid ester compounds by esterifying a phenol compound, which allows for esterification with a high introduction rate and efficient recovery of the obtained ester compound. [Brief explanation of the drawing]

[0009] [Figure 1] The 1H NMR spectrum of the raw material resin (SA90) compound is shown. [Figure 2] The 1H NMR spectra of the (meth)acrylic acid ester compounds obtained in Example 5 are shown. [Figure 3] The 1H NMR spectrum of the (meth)acrylic acid ester compound obtained in Comparative Example 1 is shown. [Modes for carrying out the invention]

[0010] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). Note that the following embodiment is illustrative for explaining the present invention, and the present invention is not limited to this embodiment. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In this specification, all physical properties and characteristic values ​​shall be those at 23°C unless otherwise specified. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, when notation is not specified as substituted or unsubstituted, unsubstituted is preferred. In this specification, "(meth)acrylic" refers to both acrylic and methacrylic, or either of them. In the present invention, methacrylic is preferred. If the standards described herein differ in measurement methods, etc., from year to year, unless otherwise specified, the standards in effect at the time of filing shall apply.

[0011] The method for producing (meth)acrylic acid ester compounds of this embodiment (hereinafter sometimes simply referred to as "the method of this embodiment") is characterized by reacting a polymer having the structure represented by formula (1) with (meth)acrylic anhydride in the presence of at least one of potassium carbonate, rubidium carbonate, and cesium carbonate. With this configuration, esterification can be performed with a high introduction rate, and the obtained (meth)acrylic acid ester compound can be efficiently recovered. For example, in the method of this embodiment, most of the excess reaction reagents and by-products can be removed by a single filtration after the reaction, and the target (meth)acrylic acid ester compound can be recovered in high yield. In this embodiment, the esterification reaction is carried out in the presence of at least one of potassium carbonate, rubidium carbonate, and cesium carbonate. That is, potassium ions, rubidium ions, or cesium ions esterify the phenolic hydroxyl group (OX) moiety in formula (1). - It is presumed that the reaction proceeds in this manner. In particular, potassium ions, rubidium ions, and cesium ions have large cation sizes, so it is presumed that phenoxy anions are more likely to become free, and thus have high nucleophilic attack on the acylating agent. On the other hand, sodium ions and lithium ions ionize the OH group to form O - It has little ability to convert to O- It is presumed that the ionic bonding force with sodium ions or lithium ions is strong, resulting in low reactivity to acylating agents. Also, potassium bicarbonate, for example, has a lower ionic radius and basicity compared to potassium carbonate due to the influence of hydrogen (H), and O - It is presumed that the reactivity is low because its ability to convert is small. In this embodiment, a carbonate is also used. If a catalyst with stronger basicity than the carbonate is used, it is presumed that the catalyst will attack the methacrylic anhydride. For example, potassium hydroxide and cesium hydroxide decompose methacrylic anhydride into methacrylic acid. In this embodiment, a carbonate was selected to preferentially activate the phenolic hydroxyl group (OX) moiety of formula (1). Furthermore, carbonates are inexpensive and have high industrial value. Furthermore, the (meth)acrylic acid ester compound obtained by the manufacturing method of this embodiment can have performance equivalent to that of conventional low-dielectric resins. In addition, a resin with a high glass transition temperature can be obtained, resulting in a material with excellent heat resistance. The details of the manufacturing method of this embodiment will be described below.

[0012] In the manufacturing method of this embodiment, a polymer having the structure represented by formula (1) is reacted with (meth)acrylic anhydride to carry out an esterification reaction. As a result, a (meth)acrylic acid ester compound is obtained in which a (meth)acrylic group is introduced to the phenolic hydroxyl group of the polymer having the structure represented by formula (1), i.e., the X position of formula (1). In the manufacturing method of this embodiment, a polymer having the structure represented by formula (1) is used as a raw material. By using such a resin, it becomes possible to manufacture a thermosetting resin with excellent low dielectric properties and heat resistance. Formula (1) [ka] (In formula (1), R 1 , R 2 , R 3 , R 4 and R 5Each is independently selected from a hydrogen atom and an alkyl group, and R 1 , R 2 , R 3 , R 4 and R 5 At least one of these is selected from a single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, and an alkylene group -*, where * indicates the bonding position with other sites. X is a hydrogen atom, at least some of which reacts with (meth)acrylic anhydride to form a (meth)acrylic group. R 1 , R 2 , R 3 , R 4 and R 5 Each of these is independently selected from a hydrogen atom and an alkyl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may or may not have substituents, but is preferably without substituents. If substituents are present, examples of substituents include halogen atoms, alkenyl groups, alkynyl groups, and aryl groups. Specifically, the alkyl group is preferably a methyl group, an ethyl group, or a propyl group, and is more preferably a methyl group. The single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, or alkylene group-* is preferably -O-*, -S-*, -S(=O)-*, -S(=O)2-*, or alkylene group-*, with -O-* being more preferred.

[0013] In this embodiment, R 1 , R 2 , R 3 , R 4 and R 5 It is preferable that two or three of them are hydrogen atoms, two or three are alkyl groups (preferably methyl groups), and the rest are single bonds, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, or alkylene groups -* (preferably -O-*), R2 and R 4 is a hydrogen atom, and R 1 and R 5 is an alkyl group (preferably a methyl group), and R 3 It is more preferable that the bond is a single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, or an alkylene group-*.

[0014] In formula (1), * indicates the bonding site with other sites, but it is usually bonded to the main chain of the polymer. However, the structure represented by formula (1) may also be bonded to the side chains of the polymer. In a polymer (raw material) having the structure represented by formula (1), X is a hydrogen atom, and at least a portion of it reacts with (meth)acrylic anhydride to form a (meth)acrylic group. In this embodiment, the proportion of hydrogen atoms in X after reaction with (meth)acrylic anhydride is preferably 15 mol% or less, more preferably 10 mol% or less, even more preferably 7 mol% or less, and even more preferably 3 mol% or less. The lower limit of the proportion of hydrogen atoms in X is preferably 0 mol% or more. As will be described in detail later, a portion of X may react with acyl compounds, etc., to form acyl groups, etc.

[0015] A polymer having the structure represented by formula (1) is not particularly defined as long as it has the structure represented by formula (1). The structure represented by formula (1) may be present at the ends of the polymer or in parts other than the ends of the polymer. One embodiment of a polymer having the structure represented by formula (1) is that it has the structure represented by formula (1) at least at the ends (preferably both ends). Another example of a polymer having the structure represented by formula (1) is a polyphenylene ether compound having the structure represented by formula (1).

[0016] The polymer having the structure represented by formula (1) is preferably a polymer of the following formula (2) or formula (3). [ka] (In formula (2), R 11 ~R 18 Each is independently selected from a hydrogen atom and an alkyl group, Y 1 These are single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, or -C(R 9 )(R 10 )- and R 9 and R 10 Each of these is independently a hydrogen atom, an alkyl group, an alkynyl group, a hydroxyl group, an amino group, an aryl group, or a heterocyclic group, and R 9 and R 10 The atoms may be bonded to each other to form a ring structure, and X is a hydrogen atom, at least a portion of which reacts with (meth)acrylic anhydride to form a (meth)acrylic group. n is a non-negative integer, m is a non-negative integer, and m+n is a non-negative integer. R 11 ~R 18 Each of these is independently selected from a hydrogen atom and an alkyl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may or may not have substituents, but is preferably without substituents. If substituents are present, examples of substituents include halogen atoms, alkenyl groups, alkynyl groups, and aryl groups. Specifically, the alkyl group is preferably a methyl group, an ethyl group, or a propyl group, and is more preferably a methyl group. R 11 , R 12 , R 13 and R 14 It is preferable that 1 to 3 of them are hydrogen atoms and the rest are alkyl groups (preferably methyl groups), R 13 and R 14 is a hydrogen atom, and R 11 and R 12 It is more preferable that the alkyl group (preferably a methyl group) is an alkyl group. R 15 , R16 , R 17 and R 18 Preferably, one to three of these are hydrogen atoms and the rest are alkyl groups (preferably methyl groups), and more preferably, one or two of these are hydrogen atoms and the rest are alkyl groups.

[0017] Y 1 These are single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, or -C(R 9 )(R 10 )- and single bond, -O- or -C(R 9 )(R 10 )- is preferred, and a single bond or -C(R 9 )(R 10 )- is preferable. R 9 and R 10 Each of these is independently a hydrogen atom, an alkyl group, an alkynyl group, a hydroxyl group, an amino group, an aryl group, or a heterocyclic group, and R 9 and R 10 These groups may be bonded to each other to form a ring structure. Alkyl groups, alkynyl groups, aryl groups, and heterocyclic groups may or may not have substituents, but it is preferable that they are not substituted. Examples of substituents include halogen atoms, alkenyl groups, alkynyl groups, and aryl groups. R 9 and R 10 Each of these is preferably independently a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkynyl group, a hydroxyl group, an amino group, a C6-C12 aryl group, or a 5-membered or 6-membered heterocyclic group; more preferably a hydrogen atom, a C1-C5 alkyl group, or a hydroxyl group; even more preferably a hydrogen atom or a methyl group; and even more preferably a methyl group. X is equivalent to equation (1).

[0018] n is an integer greater than or equal to 0, preferably an integer greater than or equal to 1, more preferably an integer greater than or equal to 5, preferably an integer less than or equal to 50, and more preferably an integer less than or equal to 20. m is an integer of 0 or more, preferably an integer of 1 or more, more preferably an integer of 5 or more, and preferably an integer of 50 or less, more preferably an integer of 20 or less. m + n is an integer of 1 or more, preferably an integer of 10 or more, more preferably an integer of 11 or more, and preferably an integer of 100 or less, more preferably an integer of 30 or less.

Chemical formula

[0019] R 21 is an alkyl group, a hydroxyl group, or an aryl group, and an alkyl group is preferred. The alkyl group is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 2 to 10 carbon atoms, and even more preferably an alkyl group having 3 to 7 carbon atoms. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably branched. The alkyl group may or may not have a substituent, but preferably does not have a substituent. When having a substituent, examples of the substituent include a halogen atom, an alkenyl group, an alkynyl group, and an aryl group. Specifically, the alkyl group is preferably a methyl group, an ethyl group, or a butyl group, and more preferably a t-butyl group. The aryl group is preferably a phenyl group. Y 2 is -CH2-, -CH2O-, or -CH2OCH2-, and -CH2- is preferred. X is synonymous with formula (1). l is an integer greater than or equal to 1, preferably an integer greater than or equal to 4, more preferably an integer greater than or equal to 5, preferably an integer less than or equal to 50, and more preferably an integer less than or equal to 20. k is an integer greater than or equal to 2, preferably 3 or greater, more preferably 6 or greater, preferably 50 or less, and more preferably 20 or less. z is an integer between 0 and 3, preferably an integer greater than or equal to 0, more preferably an integer greater than or equal to 1, preferably an integer less than or equal to 3, and more preferably an integer less than or equal to 1. * indicates a bonding site with another constituent unit or terminal group. Examples of terminal groups include hydrogen atoms and hydroxyl groups, with hydrogen atoms being preferred.

[0020] The polymer represented by formula (2) and the polymer represented by formula (3) may contain other constituent units without departing from the spirit of the present invention. Preferably, the polymer represented by formula (2) and the polymer represented by formula (3) do not contain other constituent units, or the proportion of other constituent units is 3% by mass or less (preferably 1% by mass or less) of the polymer represented by formula (2) and the polymer represented by formula (3). In the manufacturing method of this embodiment, the polymer having the structure represented by formula (1) (and moreover, the polymers represented by formulas (2) and (3)) usually accounts for 90% by mass or more, and preferably 95% by mass or more, of the polymer components that are the raw materials. In the manufacturing method of this embodiment, one polymer having the structure represented by formula (1) (and furthermore, polymers represented by formulas (2) and (3)) may be used, or two or more may be used.

[0021] The polymer having the structure represented by formula (1) preferably has a hydroxyl value of 100 to 5,000 g / mol, which is the mass of the polymer per mole of hydroxyl groups. Setting it above the lower limit can lower the dielectric properties of the resulting (meth)acrylic acid ester compound. Setting it below the upper limit allows a sufficient amount of (meth)acrylic groups to be introduced into the resulting (meth)acrylic acid ester compound, resulting in a (meth)acrylic acid ester compound with superior heat resistance. The hydroxyl value is more preferably 2,000 g / mol or less, even more preferably 1,200 g / mol or less, even more preferably 200 g / mol or more, and even more preferably 300 g / mol or more. The hydroxyl value is measured according to the example described below.

[0022] The number-average molecular weight of the polymer having the structure represented by formula (1) is preferably 1,000 to 10,000. By setting it within this range, the performance of the resulting (meth)acrylic acid ester compound after curing tends to be well-balanced and excellent. Specifically, it tends to be better in terms of low dielectric properties, heat resistance, ease of curing, and uniform film formation. The number-average molecular weight is more preferably 1,200 or more, even more preferably 1,500 or more, even more preferably 6,000 or less, even more preferably 5,000 or less, even more preferably less than 4,000, and even more preferably 3,500 or less. The aforementioned number-average molecular weight (Mn) is measured according to the example described below. In this embodiment, it is preferable that the polymer having the structure represented by formula (1) satisfies both the number-average molecular weight and the hydroxyl value. In such cases, the effects of the present invention are more effectively exhibited. Furthermore, the molecular weight distribution (Mw / Mn) is more preferably 1.01 or higher, even more preferably 1.10 or higher, even more preferably 10.0 or lower, even more preferably 5.00 or lower, and even more preferably 3.00 or lower. In particular, in this embodiment, even if the molecular weight distribution (Mw / Mn) is 1.50 or higher, the hydroxyl groups can be appropriately esterified. The weight-average molecular weight (Mw) is measured according to the example described below.

[0023] Next, the catalyst used in the manufacturing method of this embodiment will be described. In this embodiment, at least one catalyst from potassium carbonate, rubidium carbonate, and cesium carbonate is used. By using these catalysts, the reaction between the polymer having the structure represented by formula (1) and the (meth)acrylic anhydride can be effectively promoted. Furthermore, the obtained (meth)acrylic ester compound can be recovered in high yield. In this embodiment, among potassium carbonate, rubidium carbonate, and cesium carbonate, potassium carbonate and cesium carbonate are preferred, and potassium carbonate is more preferred. While there are no specific requirements regarding the form of potassium carbonate, rubidium carbonate, and cesium carbonate, they are preferably in powder form. Furthermore, the form of potassium carbonate, rubidium carbonate, and cesium carbonate is preferably in the form of fine powder (average particle size of about 10 to 200 μm). Using powdered materials increases the specific surface area and thus enhances reactivity.

[0024] In the manufacturing method of this embodiment, it is preferable to use at least 1.0 mole (mol / mol-OH) or more of potassium carbonate, rubidium carbonate, and cesium carbonate in total per mole of hydroxyl groups of the polymer having the structure represented by formula (1), more preferably 3.0 moles or more, preferably 10.0 moles or less, and more preferably 7.0 moles or less. Setting the amount above the lower limit tends to further improve the reactivity between the hydroxyl groups of the polymer having the structure represented by formula (1) and (meth)acrylic anhydride. Setting the amount below the upper limit tends to further improve the effect of reducing manufacturing costs. In the manufacturing method of this embodiment, only one of potassium carbonate, rubidium carbonate, and cesium carbonate may be used, or two or more may be used. When two or more are used, it is preferable that the total amount is within the above range.

[0025] In the manufacturing method of this embodiment, the esterification reaction can be carried out without using 4-dimethylaminopyridine (DMAP), which has been commonly used in the past. That is, in the manufacturing method of this embodiment, the esterification reaction can proceed in a state where DMAP is substantially absent. Substantially absent means that the amount of DMAP present is preferably 0.1 moles or less, more preferably 0.05 moles or less, even more preferably 0.03 moles or less, and even more preferably 0.01 moles or less, per 1.0 mole of the total amount of potassium carbonate, rubidium carbonate, and cesium carbonate. The lower limit is 0 moles. In the production method of this embodiment, it is also preferable to carry out the esterification reaction in a state in which esterification catalysts other than potassium carbonate, rubidium carbonate, and cesium carbonate are substantially absent. "Substantially absent" means that the amount of esterification catalysts other than potassium carbonate, rubidium carbonate, and cesium carbonate is preferably 0.1 moles or less, more preferably 0.05 moles or less, even more preferably 0.03 moles or less, and even more preferably 0.01 moles or less, per 1.0 mole of the total amount of potassium carbonate, rubidium carbonate, and cesium carbonate. The lower limit is 0 moles. By keeping the amount within this range, (meth)acrylic acid ester compounds can be isolated in a higher yield.

[0026] In this embodiment, a polymer having the structure represented by formula (1) is reacted with (meth)acrylic anhydride. (Meth)acrylic anhydride refers to methacrylic anhydride and / or acrylic anhydride, with methacrylic anhydride being preferred. By using methacrylic anhydride, the effect of improving the heat resistance when producing a thermosetting resin is more effectively exhibited.

[0027] In the manufacturing method of this embodiment, the proportion of X in the polymer having the structure represented by formula (1) that is substituted with (meth)acrylic groups (the rate of introduction of (meth)acrylic groups to phenolic hydroxyl groups) is preferably 85 mol% or more, more preferably 90 mol% or more, even more preferably 93 mol% or more, and even more preferably 97 mol% or more. The upper limit is ideally 100 mol%, but 99.9 mol% or less is practical. Furthermore, in the esterification reaction, it is preferable to use 1.0 mole or more of (meth)acrylic anhydride per mole of hydroxyl groups of the polymer having the structure represented by formula (1), and more preferably 1.1 moles or more. By setting it above the lower limit, a higher proportion of hydroxyl groups of the polymer having the structure represented by formula (1) tend to be converted to (meth)acrylic groups. Also, it is preferable that the amount of (meth)acrylic anhydride per mole of hydroxyl groups of the polymer having the structure represented by formula (1) be 10.0 moles or less, more preferably 8.0 moles or less, even more preferably 5.0 moles or less, even more preferably 4.5 moles or less, even more preferably 3.0 moles or less, and even more preferably 2.0 moles or less. By setting it below the upper limit, purification becomes easier and manufacturing costs can be reduced more effectively. In the manufacturing method of this embodiment, when both methacrylic anhydride and acrylic anhydride are used, the total amount will be within the above range.

[0028] In the manufacturing method of this embodiment, the polymer having the structure represented by formula (1) may be further reacted with an acyl compound, so that a portion of X after the reaction is an acyl group. If the polymer having the structure represented by formula (1) used in the manufacturing method of this embodiment contains a large number of phenolic hydroxyl groups, reacting it with only (meth)acrylic anhydride will introduce a large number of (meth)acrylic groups. However, when the (meth)acrylic ester compound obtained by the manufacturing method of this embodiment is used as a low dielectric material, if an excessive number of (meth)acrylic groups are introduced into the (meth)acrylic ester compound, the dielectric constant and dielectric loss tangent may become high. In addition, it may be difficult to select only raw material oligomers (polymers having the structure represented by formula (1)) that have a small amount of phenolic hydroxyl groups. In such cases, the polymer having the structure represented by formula (1) can be reacted with an acyl compound in addition to (meth)acrylic anhydride, so that a portion of X after the reaction is an (meth)acrylic group and the other portion is an acyl group, thereby obtaining the desired low dielectric material. In the manufacturing method of this embodiment, when reacting an acyl compound with (meth)acrylic anhydride, the (meth)acrylic anhydride and the acyl compound may be reacted simultaneously, or one may be reacted first. In the manufacturing method of this embodiment, it is preferable to react the (meth)acrylic anhydride first, and then the acyl compound. By reacting the (meth)acrylic anhydride first, and then the acyl compound, a polymer can be obtained that has a suitable amount of (meth)acrylic groups for the production of low dielectric materials, while having a low residual hydroxyl group ratio. Furthermore, it is preferable to carry out the acylation reaction using the acyl compound in the same reaction system, but it may also be carried out in a reaction system where potassium carbonate, rubidium carbonate, and cesium carbonate are substantially absent. For example, after reacting a polymer having the structure represented by formula (1) with (meth)acrylic anhydride, the reactants may be recovered and the acyl compound may be reacted in a separate reaction system.

[0029] The acyl compound is not specifically defined in terms of type, but acetic anhydride is preferred from the viewpoint of manufacturing cost. In this Example 9, acetic anhydride was reacted to substitute the methacrylic group and acetyl group in a molar ratio of 1:1, but the substitution can be carried out in any ratio, taking into consideration the amount of hydroxyl group equivalents in the raw material resin being reacted.

[0030] In the manufacturing method of this embodiment, when reacting with an acyl compound, the proportion of X in the polymer having the structure represented by formula (1) that is substituted with an acyl group is preferably 5 mol% or more, and more preferably 10 mol% or more. Setting it above the lower limit tends to yield a resin with better dielectric properties. Furthermore, the proportion of X in the polymer having the structure represented by formula (1) that is substituted with an acyl group is preferably 90 mol% or less, and more preferably 80 mol% or less. Setting it below the upper limit helps to maintain better thermosetting properties of the polymer having the structure represented by formula (1). Furthermore, in the esterification reaction, it is preferable to use 0.1 moles or more of the acyl compound per mole of hydroxyl groups of the polymer having the structure represented by formula (1), and more preferably 0.2 moles or more. By setting the amount above the lower limit, the residual hydroxyl group rate of the polymer having the structure represented by formula (1) can be effectively reduced. It is preferable that the amount of the acyl compound be 10 moles or less per mole of hydroxyl groups of the polymer having the structure represented by formula (1), and more preferably 5 moles or less. By setting the amount below the upper limit, purification becomes easier, and manufacturing costs tend to decrease. One acyl compound may be used, or two or more may be used. When two or more are used, it is preferable that the total amount be within the above range.

[0031] In the manufacturing method of this embodiment, it is preferable to carry out the esterification reaction in the presence of a solvent. In the manufacturing method of this embodiment, if the polymer having the structure represented by formula (1) is in liquid form, a solvent may not be used, but if the polymer having the structure represented by formula (1) is in non-liquid form, a solvent is usually used. By using a solvent, the ionization of potassium carbonate, rubidium carbonate, and cesium carbonate, and the ionization of the phenolic hydroxyl groups of the polymer having the structure represented by formula (1) can be effectively carried out. The solvent used in the manufacturing method of this embodiment can be used without particular restriction as long as it dissolves the polymer having the structure represented by formula (1) and does not significantly inhibit the esterification reaction in this embodiment, but an aprotic solvent is preferred, and at least one of an aromatic hydrocarbon solvent and an ether solvent is more preferred. By using an aprotic solvent, the phenolic hydroxyl group-derived O - The effects on it tend to proceed effectively. Examples of suitable solvents include toluene, dimethylacetamide (DMAC), cyclopentyl methyl ether (CPME), 4-methyltetrahydropyran (MTHP), and 1,4-dioxane. From the viewpoint of being a low-polarity solvent, a good solvent for polymers having the structure represented by formula (1), and having a boiling point suitable for esterification reactions, toluene is preferred. Furthermore, from the viewpoint of efficiently recovering and reusing the solvent, cyclopentyl methyl ether (CPME), which is highly hydrophobic and less likely to generate peroxides, is preferred. A dehydrated solvent is preferred. Using a dehydrated solvent can increase the yield of the resulting (meth)acrylic acid ester compound.

[0032] In the manufacturing method of this embodiment, when a solvent is used, the amount is preferably 0.1 mL or more, more preferably 1.0 mL or more, and even more preferably 2.0 mL or more, per 1 g of polymer having the structure represented by formula (1). Setting the amount above the lower limit effectively ensures fluidity necessary for the esterification reaction to proceed smoothly. Furthermore, the amount of solvent is preferably 200 mL or less, more preferably 100 mL or less, and even more preferably 50 mL or less, per 1 g of polymer having the structure represented by formula (1). Setting the amount below the upper limit maintains a concentration necessary for the esterification reaction to proceed smoothly, and tends to further improve the effect of reducing manufacturing costs. In the manufacturing method of this embodiment, only one solvent may be used, or two or more solvents may be used. When two or more solvents are used, it is preferable that the total amount is within the above range.

[0033] The (meth)acrylic acid ester compound obtained in this embodiment may be a methacrylic acid ester compound or an acrylic acid ester compound, but it is preferably a methacrylic acid ester compound.

[0034] In this embodiment, the reaction temperature for the esterification reaction is preferably -20°C or higher, more preferably 0°C or higher, and even more preferably 20°C or higher. Setting the temperature above the lower limit allows the esterification reaction to proceed smoothly, and a high proportion of the hydroxyl groups of the polymer having the structure represented by formula (1) tend to be converted to (meth)acrylic groups. Furthermore, the reaction temperature for the esterification reaction is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 150°C or lower. Setting the temperature below the upper limit prevents the (meth)acrylic groups from undergoing side reactions such as polymerization, and also tends to improve manufacturing safety. In this embodiment, the reaction time for the esterification reaction is preferably 0.5 hours or more, more preferably 1.0 hour or more, and even more preferably 2.0 hours or more. By setting the reaction time above the lower limit, a high proportion of hydroxyl groups in polymers having the structure represented by formula (1) tend to be converted to (meth)acrylic groups. Furthermore, the reaction time for the esterification reaction is preferably 120 hours or less, more preferably 72 hours or less, and even more preferably 48 hours or less. By setting the reaction time below the upper limit, the effect of reducing manufacturing costs tends to be further improved. In this embodiment, esterification may be carried out under a normal atmosphere (in the presence of air) or under an inert gas atmosphere. Carrying it out under a normal atmosphere can further reduce manufacturing costs. Carrying it out under an inert gas atmosphere allows the esterification reaction to proceed in a non-aqueous, deoxygenated system, and the esterification can be carried out more effectively.

[0035] In the manufacturing method of this embodiment, filtration is preferable after the esterification reaction. In the manufacturing method of this embodiment, the (meth)acrylic acid ester compound can be recovered with a high recovery rate in a single filtration. The diameter of the filter for filtration in this embodiment is preferably 0.2 to 7.0 μm. Filtration is preferably performed after the esterification reaction has cooled to room temperature (for example, 20 to 40°C). The reaction solution after filtration is preferably vacuum dried, and more preferably vacuum dried after most of the reaction solvent has been removed by distillation. As described above, in the manufacturing method of this embodiment, (meth)acrylic acid ester compounds can be isolated with a high recovery rate by filtration alone, but it goes without saying that liquid-liquid extraction, recrystallization, and other purification operations may be performed to further increase purity.

[0036] In the manufacturing method of this embodiment, the amount of (meth)acrylic acid, which is an impurity, is preferably less than 1 mol%, more preferably 0.8 mol% or less, even more preferably 0.6 mol% or less, and even more preferably 0.4 mol% or less, per mole of polymer having the structure represented by formula (1). The lower limit of the amount of (meth)acrylic acid, which is an impurity, is ideally 0 mol%, but 0.01 mol% or more is practical. In the manufacturing method of this embodiment, when a polymer having the structure represented by formula (1) is added to (meth)acrylic anhydride and reacted with an acyl compound, the amount of impurities derived from the acyl compound is preferably less than 1 mol%, more preferably 0.8 mol% or less, even more preferably 0.6 mol% or less, and most preferably 0.4 mol% or less, per mole of the polymer having the structure represented by formula (1). The lower limit of the amount of impurities derived from the acyl compound is ideally 0 mol%, but 0.01 mol% or more is practical. For example, if the acyl compound is acetic acid anhydride, the impurities derived from the acyl compound are acetic acid.

[0037] <Application> The (meth)acrylic acid ester compound obtained by the manufacturing method of this embodiment may be used as is, or it may be used as a resin composition in which other curable compounds or additives are added. Examples of other curable compounds include compounds having carbon-carbon unsaturated bond groups and epoxy resins. Examples of additives include flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, defoamers, dispersants, leveling agents, glossing agents, polymerization inhibitors, and the like. The (meth)acrylic acid ester compound obtained by the manufacturing method of this embodiment, or the resin composition containing the (meth)acrylic acid ester compound, is preferably cured and used as a cured product. Such cured products have excellent heat resistance and dielectric properties, and can therefore be suitably used as insulating layers for printed circuit boards and materials for semiconductor packages. [Examples]

[0038] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or other reasons, measurements can be taken using other instruments with equivalent performance.

[0039] The number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the raw resin were calculated using gel permeation chromatography (GPC) and converted to standard polystyrene. The apparatus used was an integrated LC (Shimadzu LC-2010). HT The equipment consisted of a radioisotope detector (SHIMADZU RID-20A) and four Shodex guard columns (KF-G 4A) and Shodex GPC standard columns (KF-801, KF-802, KF-803, KF-804) connected in series. Samples dissolved in THF (tetrahydrofuran) were measured by passing them through the detector under the conditions of THF as the eluent, a flow rate of 1.0 mL, and a temperature of 40°C.

[0040] Example 1 According to the following scheme, using toluene (8 mL) as a solvent, 828 mg (1 mmol of hydroxyl group amount) of oligophenylene ether having hydroxyl groups at both ends (manufactured by SABIC, SA-90, group R a in which na + ma is about 12.) was reacted with 185 mg (1.2 mmol) of methacrylic anhydride (MAA) at 100 °C for 6 hours in the presence of 691 mg (5 mmol) of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Corporation, average particle size 150 μm or less). After air-cooling 0.5 mL of the reaction solution, it was filtered through a 0.45 μm filter and vacuum dried (pressure less than 1 hPa, 40 °C) over 1 hour. This was dissolved in deuterated chloroform and the methacrylation rate (OH modification rate) and methacrylic acid residual rate (impurity) were calculated by proton nuclear magnetic resonance spectrum ( 1 1H NMR) analysis in the manner described below. It was confirmed that the methacryloyl group was introduced into the hydroxyl group of the oligophenylene ether having hydroxyl groups at both ends at a high conversion rate of 94 mol% of the methacryloyl group.

Chemical formula

[0041] The methacrylation rate (OH modification rate) and methacrylic acid residual rate (proportion of impurities) of the polymer were calculated based on the results of proton nuclear magnetic resonance spectrum ( 1 1H NMR) analysis. A BRUKER AVANCEIII 500 (500 MHz) was used as the nuclear magnetic resonance apparatus. Specifically, after air-cooling 0.5 mL of the reaction solution, it was filtered through a 0.45 μm filter, and the filtrate was vacuum dried (pressure less than 1 hPa, 40 °C) over 1 hour. This was dissolved in deuterated chloroform and analyzed by 1H NMR at 25 °C 1 Here, for SA-90 which is an oligophenylene ether with hydroxyl groups at both ends 1Figure 1 shows the 1H NMR spectrum (in the range of 4 ppm to 7 ppm). In Figure 1, the theoretical value of the integral ratio of the proton (a) of the hydroxyl group around 4.1 to 4.6 ppm should be 2.0 compared to the integral ratio (4.0) of the proton (c) bonded to the aromatic ring of the core around 6.8 to 7.0 ppm, but it was actually observed to be 1.8. One reason for this is that the proton of the hydroxyl group undergoes proton exchange easily in solution, causing the peak to broaden and making it difficult to observe. 1 Even with analytical methods other than 1H NMR, hydroxyl groups readily form intermolecular hydrogen bonds, making quantitative determination often difficult. Therefore, the methacrylate rate and methacrylic acid retention rate were calculated by comparing them with the integral ratio (24.1) of protons (b) bonded to the aromatic ring of the repeating structural unit of the polymer. Furthermore, the hydroxyl value of the raw resin was determined by NMR analysis (integral ratio of proton(b) to proton(c)) following the method described above. The calculated hydroxyl value was equivalent to the standard value of the raw resin product.

[0042] Example 2 In Example 1, the catalyst was changed from 5 mmol of potassium carbonate to 5 mmol of cesium carbonate (1.63 g), and the rest of the procedure was carried out as before. It was confirmed that 96 mol% of methacrylic groups were introduced to the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends, with a high conversion rate. The methacrylate conversion rate and the residual methacrylic acid rate were measured in accordance with Example 1.

[0043] Example 3 In Example 1, the solvent was changed to dimethylacetamide (DMAC), and the rest of the procedure was carried out similarly. It was confirmed that 90 mol% of methacrylic groups were introduced to the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends, with a high conversion rate. The methacrylate conversion rate and the residual methacrylic acid rate were measured in accordance with Example 1.

[0044] Example 4 In Example 1, the solvent was changed to 1,4-dioxane, and the rest of the procedure was carried out similarly. It was confirmed that methacrylic groups were introduced with a high conversion rate of 99 mol% to the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends. The methacrylate conversion rate and the residual methacrylic acid rate were measured in accordance with Example 1.

[0045] Example 5 In Example 1, the solvent was changed to cyclopentyl methyl ether (CPME), and the rest of the procedure was carried out similarly. It was confirmed that methacrylic groups were introduced to the hydroxyl groups of the oligophenylene ether, which has hydroxyl groups at both ends, with a conversion rate of over 99 mol%. The obtained oligophenylene ether with both terminal methacrylate groups 1 Figure 2 shows the 1H NMR spectrum (in the range of 4 ppm to 7 ppm). The protons (d) of the double bond of the methacrylate group are visible around 5.7–5.8 ppm and 6.3–6.4 ppm in Figure 2. 1 d 2 Assuming the integral ratios of the protons (a) of the hydroxyl group around 4.1-4.6 ppm are both 2.0, the methacrylate rate was calculated to be 24.1 / (26.2-2.0)×100 = over 99%. When the hydroxyl group retention rate was calculated from the integral ratio (0.012) of the proton (a) of the hydroxyl group around 4.1-4.6 ppm, it was 0.012 / (2.0+0.012)×100 = 0.6%, which is almost consistent with the methacrylate rate (over 99%). In addition, the proton (e) of the double bond of methacrylic acid around 5.5-5.6 ppm and around 6.1-6.2 ppm 1 ,e 2 From the integral ratio (0.002, 0.002) of ), the residual methacrylic acid per polymer molecule was calculated to be 0.002 × 24.1 / (26.2 - 2.0) × 100 = 0.2%.

[0046] Example 6 In Example 1, the solvent was changed to 4-methyltetrahydropyran (MTHP), and the rest of the procedure was carried out similarly. It was confirmed that methacrylic groups were introduced with a high conversion rate of 99 mol% to the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends. The methacrylate conversion rate and the residual methacrylic acid rate were measured in accordance with Example 1.

[0047] Example 7 In Example 1, an oligophenylene ether having hydroxyl groups at both ends (SABIC, SA-90) was used with OPE-2000 (Mitsubishi Gas Chemical Company, R b In the middle, nb+mb was approximately 12. The amount was changed to 821 mg (hydroxyl group content 1 mmol), and the rest of the procedure was carried out similarly. It was confirmed that 95 mol% of methacrylic groups were introduced to the hydroxyl groups of oligophenylene ether with a high conversion rate. The methacrylate conversion rate and the residual methacrylic acid rate were measured according to Example 1. [ka]

[0048] Example 8 In Example 7, the solvent was changed to cyclopentyl methyl ether (CPME), and the rest of the procedure was carried out similarly. It was confirmed that 98 mol% of methacrylic groups were introduced to the hydroxyl groups of oligophenylene ether with a high conversion rate. The methacrylate conversion rate and the residual methacrylic acid rate were measured in accordance with Example 1.

[0049] Example 9 According to the scheme below, using cyclopentyl methyl ether (CPME) (8 mL) as the solvent, 3.46 g (10 mmol of hydroxyl groups) of p-tert-butyl modified xylene resin (Xy-PTBP) (manufactured by Mitsubishi Gas Chemical Co., Ltd., nc is approximately 6 and mc is approximately 4) was reacted with 6 mmol (925 mg) of methacrylic anhydride (MAA) at 100°C for 6 hours in the presence of 50 mmol (6.91 g) of potassium carbonate, and then reacted with 32 mmol (3.27 g) of acetic anhydride (Ac2O) at 100°C for 6 hours. After cooling 0.5 mL of the reaction mixture with air, it was filtered through a 0.45 μm filter and vacuum-dried for 1 hour (pressure less than 1 hPa, 40°C). This was dissolved in deuterated chloroform and the proton nuclear magnetic resonance spectrum was analyzed. 1The methacrylate conversion rate and methacrylic acid retention rate were calculated by 1H NMR analysis. Methacrylic and acetyl groups were introduced into the hydroxyl groups of Xy-PTBP in a 1:1 ratio (molar ratio), totaling over 99 mol%. The nd of Xy-PTBP-MA-Ac was approximately 6, the md was approximately 2, and the ld was approximately 2. The methacrylate conversion rate and methacrylic acid retention rate were measured according to Example 1. [ka]

[0050] Comparative Example 1 In Example 1, potassium carbonate was replaced with 0.2 mmol of 4-dimethylaminopyridine (DMAP), and the rest of the procedure was carried out as before. The rate of methacrylic group introduction to the hydroxyl groups of the hydroxyl oligophenylene ether was 92 mol%. Unlike in the examples, even after filtration following the reaction, most of the DMAP (37% per polymer molecule) and the by-product methacrylic acid (137% per polymer molecule) remained. Furthermore, DMAP is expensive, making it less cost-effective compared to the potassium carbonate method. The oligophenylene ether with both terminal methacrylate groups obtained in Comparative Example 1 1 Figure 3 shows the 1H NMR spectrum (in the range of 4 ppm to 7 ppm). The protons (d) of the double bond of the methacrylate group are visible around 5.7–5.8 ppm and 6.3–6.4 ppm in Figure 3. 1 d 2 Assuming the integral ratios of ) are 2.0, the methacrylate rate was calculated to be 24.1 / (28.2-2.0)×100 = 92%. The proton (a) of the hydroxyl group around 4.1-4.6 ppm was not observed due to proton exchange with methacrylic acid, which is abundant in the solution. Instead, several peaks of unknown structure were observed. In addition, the proton (e) of the double bond of methacrylic acid around 5.5-5.6 ppm and 6.1-6.2 ppm was observed. 1 ,e 2From the integral ratio (1.49, 1.49) of ), the residual methacrylic acid per polymer molecule was calculated to be 1.49 × 24.1 / (28.2 - 2.0) × 100 = 137%. Protons (g) bonded to the heterocycle of DMAP around 6.6 ppm 1 From the integral ratio (0.6) of ), the remaining DMAP per polymer molecule was calculated to be (0.6 / 2) × 24.1 / (28.2 - 2.0) × 100 = 28%. Protons (g) bonded to the heterocycle of DMAP methacrylate around 6.7 ppm 2 From the integral ratio (0.2) of ), the residual DMAP with methacrylic acid attached per polymer molecule was calculated to be (0.2 / 2) × 24.1 / (28.2 - 2.0) × 100 = 9%. Also, the proton (f) of the double bond of methacrylic anhydride around 5.8 ppm and 6.2 ppm 1 ,f 2 From the integral ratio (0.09, 0.09) of ), the residual rate of methacrylic anhydride per polymer molecule was calculated to be (0.09 / 2) × 24.1 / (28.2 - 2.0) × 100 = 4%.

[0051] Comparative Example 2 In Example 1, potassium carbonate was replaced with 5 mmol of sodium carbonate, and the rest of the procedure was carried out similarly. The rate of methacrylic group introduction to the hydroxyl groups of the hydroxyl oligophenylene ether was 21 mol%. The methacrylic conversion rate and the residual methacrylic acid rate were measured in accordance with Comparative Example 1.

[0052] Comparative Example 3 In Example 1, potassium carbonate was replaced with 5 mmol of lithium carbonate, and the rest of the procedure was carried out similarly. The rate of methacrylic group introduction to the hydroxyl groups of the hydroxyl oligophenylene ether was 5 mol%. The methacrylic conversion rate and the residual methacrylic acid rate were measured in accordance with Comparative Example 1.

[0053] Comparative Example 4 In Example 1, potassium carbonate was replaced with 5 mmol of calcium carbonate, and the rest of the procedure was carried out similarly. The rate of methacrylic group introduction to the hydroxyl groups of the hydroxyl oligophenylene ether was 3 mol%. The methacrylate rate and the residual methacrylic acid rate were measured in accordance with Comparative Example 1.

[0054] Comparative Example 5 In Example 1, potassium carbonate was replaced with 5 mmol of potassium bicarbonate, and the rest of the procedure was carried out similarly. The rate of methacrylic group introduction to the hydroxyl groups of the hydroxyl oligophenylene ether was 7 mol%. The methacrylic conversion rate and the residual methacrylic acid rate were measured in accordance with Comparative Example 1.

[0055] Comparative Example 6 In Example 1, potassium carbonate was replaced with 5 mmol of potassium hydroxide, and the rest of the procedure was carried out similarly. No introduction of methacrylic groups to the hydroxyl groups of the hydroxyl oligophenylene ether was observed. The methacrylate rate and the remaining methacrylic acid rate were measured in accordance with Comparative Example 1.

[0056] Examples and Comparative Examples 2 and 3 showed a correlation between the ionic radius of alkali metal carbonates and the reactivity of methacrylate. It was observed that using sodium carbonate, which has a smaller ionic radius than potassium carbonate, significantly reduced the conversion rate. It was inferred that the larger the ionic radius of the metal cation, the more exposed the phenoxyanion becomes when the phenolic hydroxyl group is activated, resulting in higher nucleophilic attack on MAA. Similarly, when using alkaline earth metal carbonates, calcium carbonate, which has an ionic radius equivalent to lithium carbonate, was used, the conversion rate to methacrylate was very low at 3 mol% (Comparative Example 4). Furthermore, even when using potassium bicarbonate, a bicarbonate, the conversion rate to methacrylate was very low at 5 mol% (Comparative Example 5). Although potassium hydroxide is strongly basic, the hydroxide ions in potassium hydroxide decomposed MAA, and the reaction did not proceed at all (Comparative Example 6).

[0057] Comparative Example 7 In Example 1, methacrylic anhydride (MAA) was replaced with 1.2 mmol (125 mg) of methacrylate chloride (MAC), and the rest of the procedure was carried out similarly. The rate of methacrylate group introduction to the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends was 46 mol%. Although methacrylate chloride (MAC) is more reactive than MAA, it is also more easily decomposed by trace amounts of water in the reaction system, so all of the MAC was consumed at about half the conversion rate. The methacrylate conversion rate and the remaining methacrylate rate were measured in accordance with Comparative Example 1.

[0058] Comparative Example 8 According to the scheme below, using a reactor equipped with a Dean-Stark apparatus, and with paraxylene (20 mL) as the solvent, 2.07 g of oligophenylene ether (SA-90, manufactured by SABIC, with hydroxyl groups at both ends) (hydroxyl group content 2.5 mmol) was reacted with 5 mmol of methacrylic acid (MA) in the presence of 0.5 mmol of B(OH)3 / H2SO4 at 130°C for 24 hours by azeotropic distillation. After cooling 0.5 mL of the reaction mixture with air, it was filtered through a 0.45 μm filter and vacuum-dried for 1 hour (pressure less than 1 hPa, 40°C). This was dissolved in deuterated chloroform and the proton nuclear magnetic resonance spectrum was analyzed. 1 The methacrylate conversion rate and methacrylic acid retention rate were calculated by 1H NMR analysis. The rate of methacrylate group introduction to the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends was 4 mol%. The methacrylate conversion rate and methacrylic acid retention rate were measured in accordance with Comparative Example 1. [ka]

[0059] Comparative Example 9 In Comparative Example 8, 0.25 mmol of p-Me-C6H4SO3H·H2O (p-toluenesulfonic acid monohydrate, PTSA-H2O) was used instead of B(OH)3 / H2SO4, and the amount of methacrylic acid (MA) was changed from 5 mmol to 12.5 mmol. The rest of the procedure was carried out in the same manner. The rate of introduction of methacrylic groups to the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends was 6 mol%. The methacrylate rate and the remaining methacrylic acid rate were measured in accordance with Comparative Example 1.

[0060] Comparative Example 10 In Comparative Example 8, instead of B(OH)3 / H2SO4, AMBERLYST® 15 (manufactured by Sigma-Aldrich) was used in an amount equal to 10% by mass relative to the mass of the oligophenylene ether having hydroxyl groups at both ends (SABIC, SA-90), and the amount of methacrylic acid (MA) was changed from 5 mmol to 12.5 mmol, with the rest of the procedure being the same. The rate of introduction of methacrylic groups to the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends was 6 mol%.

[0061] In Comparative Example 8, methacrylic modification of SA-90 was carried out using MA in a B(OH)3 / H2SO4 cocatalyst system. As a result, the reaction proceeded when the reaction temperature was 130°C in xylene solvent, but even when using 1.7 times the amount of MA and more than 3 times the amount of B(OH)3 / H2SO4 compared to the example described in Japanese Patent Application Publication No. 2011-105667, the conversion rate was very low at 4%. The reason for the low efficiency of the methacrylic reaction compared to the example described in Japanese Patent Application Publication No. 2011-105667 is presumed to be a decrease in reactivity due to steric hindrance by the 2,6-dimethyl group adjacent to the phenolic hydroxyl group at the end of SA-90, and inhibition of catalytic activity due to the interaction between B(OH)3 / H2SO4 and the oligophenylene ether group of the SA-90 main chain. In addition, when using p-toluenesulfonic acid or the solid acid AMBERLYST15, which are commonly used as acid catalysts for esterification, the conversion rate was low, around 6%, even when a large amount of MA (12.5 mmol) was used (Comparative Examples 9 and 10).

[0062] Example 10 As shown in the scheme below, the same procedure was carried out in Example 8 on a 25-fold scale. It was confirmed that 95 mol% of methacrylic groups were introduced to the hydroxyl groups of the oligophenylene ether with a high conversion rate. The resulting compound was a beige powder with a residual hydroxyl group content of 5 mol%. [ka]

[0063] Comparative Examples 11-13 In Example 1, the catalyst type was changed to sodium acetate (AcONa), and the amount of catalyst and the type of solvent were changed as shown in Table 5. All other procedures were carried out as before. The results are shown in Table 5.

[0064] The results of Examples 1-9 and Comparative Examples 1-13 are summarized below. In the table below, impurities refer to methacrylic acid (MA) unless otherwise specified. AcOH refers to acetic acid. The reason why the amount of impurities may exceed 100 mol% is that, for example, if 1.2 mmol of methacrylic anhydride is used for every 1 mmol of hydroxyl groups, then 240 mol% of methacrylic anhydride is added to one molecule of polymer. Calculating the amount of impurities relative to hydroxyl groups or methacrylic groups is difficult because the values ​​of residual hydroxyl groups and introduced methacrylic groups differ for each example and comparative example; therefore, the values ​​are given per molecule of polymer.

[0065] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5]

[0066] In Tables 1 to 5, the "100-OH denaturation rate" corresponds to "the proportion of hydrogen atoms (mol%) where X in equation (1) is..." ND indicates that it was not detected. The unit of hydroxyl value (g / mol) indicates the mass of the polymer (raw resin) per mole of hydroxyl groups. mol / mol-OH indicates the amount (in moles) added per mole of hydroxyl groups in the raw material resin (polymer having the structure represented by formula (1)).

[0067] Example 11 The (meth)acrylic acid ester compound (OPE-2MA) obtained in Example 10 was thermocured to produce a resin. Specifically, 1 part by mass of perbutyl® P was added to OPE-2MA obtained in Example 10, the temperature was increased at a rate of 3°C / min, and the material was vacuum hot-pressed at 200°C for 2 hours under a pressure of 1.92 MPa to obtain a cured product with a thickness of 1.2 mm. The dielectric constant, dielectric loss tangent, and glass transition temperature of the obtained resin were measured.

[0068] <Measurement of glass transition temperature> The glass transition temperature of the cured material was determined by performing dynamic viscoelasticity measurements on pieces of the cured material cut to 5 mm horizontally and 40 mm vertically, and the peak temperature of the obtained dynamic modulus was used as the unit. The unit is °C. Equipment used: Seiko Instruments Inc. DMS6100, EXSTAR6000 Heating rate: 5°C / min Frequency: Sine wave, 10Hz

[0069] <Measurement of dielectric properties> The dielectric constant and dielectric loss tangent of the cured material were measured at 10 GHz using the cavity resonance perturbation method for pieces of the cured material cut to a thickness of 1.2 mm, width of 0.8 mm, and length of 100 mm. Equipment used: Agilent 8722ES Network Analyzer

[0070] The resulting cured material has a dielectric constant (Dk ) is 2.461 (10 GHz), dielectric loss tangent (D f ) is 0.00423 (10 GHz), glass transition temperature (T g The temperature was 155°C (10Hz). Physical properties of the thermosetting resin of OPE-2MA (D k , D f , T g The performance values ​​were equivalent to those of cured polyphenylene ethers with methacrylate groups at both ends. [ka]

Claims

1. A method for producing a (meth)acrylic acid ester compound in which a (meth)acrylic group is introduced into at least a portion of X of a polymer represented by formula (2) or formula (3), comprising reacting a polymer represented by formula (2) or formula (3) with a (meth)acrylic anhydride in the presence of at least one of potassium carbonate, rubidium carbonate, and cesium carbonate. 【Chemistry 1】 (In formula (2), R １１ ~R １８ are each independently selected from a hydrogen atom and an alkyl group, Y １ is a single bond or -C(R ９ )(R １０ )-, R ９ and R １０ are each independently a hydrogen atom or a methyl group, R ９ and R １０ may be bonded to each other to form a ring structure, and X is a hydrogen atom. n is an integer of 0 or more, m is an integer of 0 or more, and m + n is an integer of 10 to 30.) 【Chemistry 2】 (In formula (3), R ２１ R is an alkyl group, a hydroxyl group, or an aryl group, and R in one structural unit ２１ One of them is the t-butyl group, Y ２ is, -CH ２ -ien-CH ２ O-, or -CH ２ OCH ２ -, where X is a hydrogen atom. l is an integer between 1 and 20, k is an integer between 2 and 20, and z is an integer between 1 and 3. * represents the left-hand component of formula (3), the right-hand component of formula (3), or a bonding site with a terminal group.

2. A method for producing a (meth)acrylic acid ester compound according to claim 1, wherein the proportion of the polymer represented by formula (2) or formula (3) in which X after reaction with (meth)acrylic anhydride is a hydrogen atom is 10 mol% or less.

3. A method for producing a (meth)acrylic acid ester compound according to claim 1 or 2, wherein a polymer represented by formula (2) or formula (3) is added to the (meth)acrylic anhydride, and further reacted with an acyl compound, wherein a portion of X after the reaction is an acyl group.

4. A method for producing a (meth)acrylic acid ester compound according to any one of claims 1 to 3, wherein the number average molecular weight of the polymer represented by formula (2) or formula (3) is 1,000 to 10,000.

5. A method for producing a (meth)acrylic acid ester compound according to any one of claims 1 to 4, wherein the hydroxyl value, which is the mass per mole of hydroxyl groups of the polymer represented by formula (2) or formula (3), is 100 to 5,000 g / mol.

6. A method for producing a (meth)acrylic acid ester compound according to any one of claims 1 to 5, wherein for every mole of hydroxyl groups of the polymer represented by formula (2) or formula (3), a total of 1.0 to 10.0 moles of at least one of potassium carbonate, rubidium carbonate, and cesium carbonate, and 1.0 to 10.0 moles of (meth)acrylic anhydride are used.

7. A method for producing a (meth)acrylic acid ester compound according to any one of claims 1 to 6, wherein the reaction is carried out in the presence of at least one of an aromatic hydrocarbon solvent and an ether solvent.

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