Process for producing a (meth)acrylate compound

Abstract

Provided is a method for producing a (meth)acrylate compound, which can perform esterification at a high introduction rate and can efficiently recover the obtained ester compound. A method for producing a (meth)acrylate compound, which includes: 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. In formula (1), R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from a hydrogen atom and an alkyl group, and at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is selected from a single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, and alkylene-*, X is a hydrogen atom, and at least a portion thereof reacts with the (meth)acrylic anhydride to become a (meth)acryloyl group.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for producing a (meth)acrylate compound. BACKGROUND

[0002] In the past, esterification of a phenol compound to produce an ester compound has been studied.

[0003] For example, Patent Literature 1 discloses a method for producing a phenyl ester, characterized by esterifying a phenol with a carboxylic acid represented by the following general formula (I) in a solvent that is azeotropic with water, using an acid catalyst,

[0004]

[0005] (In formula (I), R1 represents hydrogen or a methyl group)

[0006] A boronic acid in an amount of 2 to 50 mol% relative to the carboxylic acid represented by the aforementioned general formula (I) and a 2,2-dialkylmalonic acid represented by the following general formula (II) are added to the reaction system of the aforementioned esterification reaction, respectively.

[0007]

[0008] (In formula (II), R2 or R3 represents a linear or branched alkyl group having a carbon number of 2 to 10).

[0009] In addition, Patent Literature 2 discloses a curable composition containing a capped poly(arylene ether) produced by the reaction of an uncapped poly(arylene ether) with an acid anhydride capping agent and an olefinically unsaturated monomer, the water absorption amount of the aforementioned composition after curing being less than 1% by weight after 7 days at 85°C and a relative humidity of 85%. It is described therein that the reaction of the uncapped poly(arylene ether) with the acid anhydride capping agent is performed in the presence of a capping catalyst containing 4-dialkylaminopyridine.

[0010] Further, Patent Literature 3 describes that a prescribed polyphenylene ether oligomer is reacted with 2-methylacrylic anhydride (methacrylic anhydride) in the presence of sodium acetate to obtain a polyphenylene ether oligomer having a functional group at the terminal.

[0011] Prior Art Documents

[0012] Patent Literature

[0013] Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 2011-105667

[0014] Patent Literature 2: Japanese Patent Application Laid-Open (JP-A) No. 2007-507592

[0015] Patent Literature 3: Japanese Patent Application Laid-Open (JP-A) No. 2019-210451 SUMMARY

[0016] Problem to be solved by the invention

[0017] As described above, a method of esterifying a phenol compound is disclosed. However, the present inventors, in the course of their research, attempted esterification of an oligophenyl ether having a hydroxyl group at both terminals, in accordance with the description of the examples of Patent Literature 1, but the introduction rate of the ester was extremely low. In addition, in accordance with the description of the examples of Patent Literature 2, esterification of an oligophenyl ether having a hydroxyl group at both terminals was attempted using 4-dimethylaminopyridine (DMAP) as a catalyst, but it was difficult to separate the catalyst from the product, and in addition, a large amount of a by-product also remained. DMAP is originally expensive, and there are problems in terms of cost. On the other hand, it is known that when sodium acetate used in the examples of Patent Literature 3 is used as a catalyst, the introduction of a (meth)acryloyl group is difficult unless an excess amount is used, with respect to (meth)acrylic anhydride.

[0018] The present invention was made in order to solve these problems, and aims to provide a method for producing a (meth)acrylate compound, which is a method for esterifying a phenol compound and obtaining an ester compound produced thereby, can perform esterification with a high introduction rate, and can efficiently recover the obtained ester compound.

[0019] Solution to the problem

[0020] Based on the above problem, it was found that the above problem can be solved by performing esterification using (meth)acrylic anhydride in the presence of a prescribed basic catalyst. Specifically, the above problem was solved by the following means.

[0021] <1> A method for producing a (meth)acrylate compound, comprising:

[0022] 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,

[0023]

[0024] In formula (1), R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from a hydrogen atom and an alkyl group, and R 1 , R 2 , R 3 , R 4 , and R 5at least one of X and Y in the formula (1) is selected from a single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, and alkylene-*, * is a bonding position with other moieties, and X is a hydrogen atom, at least a part of which is reacted with (meth)acrylic anhydride to become a (meth)acryloyl group.

[0025] <2> The method for producing a (meth)acrylate compound according to <1>, wherein a proportion of X which is a hydrogen atom after the reaction with (meth)acrylic anhydride in the polymer having the structure represented by the formula (1) is 10 mol% or less.

[0026] <3> The method for producing a (meth)acrylate compound according to <1> or <2>, wherein the polymer having the structure represented by the formula (1) is further reacted with an acyl compound, and a part of X after the reaction is an acyl group.

[0027] <4> The method for producing a (meth)acrylate compound according to any one of <1> to <3>, wherein the polymer having the structure represented by the formula (1) has a number average molecular weight of 1,000 to 10,000.

[0028] <5> The method for producing a (meth)acrylate compound according to any one of <1> to <4>, wherein a hydroxyl value, which is a mass of 1 mol of a hydroxyl group of the polymer having the structure represented by the formula (1), is 100 to 5,000 g / mol.

[0029] <6> The method for producing a (meth)acrylate compound according to any one of <1> to <5>, wherein, per 1 mol of a hydroxyl group of the polymer having the structure represented by the formula (1), a total of 1.0 to 10.0 mol of at least one of potassium carbonate, rubidium carbonate, and cesium carbonate, and 1.0 to 10.0 mol of (meth)acrylic anhydride are used.

[0030] <7> The method for producing a (meth)acrylate compound according to any one of <1> to <6>, wherein the polymer having the structure represented by the formula (1) comprises a polymer represented by the formula (2) or the formula (3),

[0031]

[0032] In the formula (2), R 11 to R 18 are each independently selected from a hydrogen atom and an alkyl group, Y 1 is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, or -C(R 9 )(R 10 , R 9 , and R 10Each group is independently composed of a hydrogen atom, alkyl group, alkynyl group, hydroxyl group, amino group, aryl group, or heterocyclic group, R. 9 and R 10 The atoms can be arbitrarily bonded to form a ring structure, where X is a hydrogen atom, at least a portion of which reacts with (meth)acrylic anhydride to form (meth)acryloyl groups, n is an integer greater than or equal to 0, m is an integer greater than or equal to 0, and m+n is an integer greater than or equal to 1.

[0033]

[0034] In equation (3), R 21 Y is alkyl, hydroxyl, or aryl. 2 The atom is -CH2-, -CH2O-, or -CH2OCH2-, where X is a hydrogen atom, at least a portion of which reacts with (meth)acrylic anhydride to become (meth)acryloyl group, l is an integer greater than or equal to 1, k is an integer greater than or equal to 2, z is an integer from 0 to 3, and * is the bonding site with other constituent units or terminal groups.

[0035] <8> according to <1> ~ <7> The method for producing the (meth)acrylate compound according to any one of the above methods, wherein the aforementioned reaction is carried out in the presence of at least one of an aromatic hydrocarbon solvent and an ether solvent.

[0036] The effects of the invention

[0037] The present invention provides a method for manufacturing (meth)acrylate compounds, which is a method for esterifying phenol compounds to obtain ester compounds. The esterification can be carried out with a high induction rate and the obtained ester compounds can be effectively recovered. Attached Figure Description

[0038] Figure 1 The raw material resin (SA90) compound is shown. 1 H NMR spectrum.

[0039] Figure 2 The (meth)acrylate compound obtained in Example 5 is shown. 1 H NMR spectrum.

[0040] Figure 3 The (meth)acrylate compound obtained in Comparative Example 1 is shown. 1 H NMR spectrum. Detailed Implementation

[0041] The following is a detailed description of a method for implementing the present invention (hereinafter referred to simply as "this embodiment"). It should be noted that the following "this embodiment" is merely an example to illustrate the present invention, and the present invention is not limited to this embodiment.

[0042] Note that "~" in the present specification is used in the sense of including the numerical value recited immediately before and after it as a lower limit value and an upper limit value.

[0043] In the present specification, unless otherwise specified, various physical property values and characteristic values are assumed to be those at 23°C.

[0044] In the present specification, in the description of a group (radical), the description of "not having a substituent" and "having no substituent" includes a group (radical) having no substituent, and also includes a group (radical) having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group), but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the description of "not having a substituent" and "having no substituent" is preferably "having no substituent".

[0045] In the present specification, "(meth)acryloyl group" means both acryloyl group and methacryloyl group, or either one of them. In the present application, methacryloyl group is preferred.

[0046] The specifications shown in the present specification are assumed to be those based on the specifications at the time of filing, unless otherwise specified, depending on the year, the method of measurement, and the like.

[0047] The production method of the (meth)acrylate compound of the present embodiment (hereinafter, sometimes referred to simply as "the production method of the present embodiment") is characterized by 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. By being configured as such, esterification can be performed at a high introduction rate, and the obtained (meth)acrylate compound can be efficiently recovered. For example, in the production method of the present embodiment, almost all of the remaining reaction reagents and by-products can be removed by filtration once after the reaction, and the target substance, i.e., the (meth)acrylate compound, can be recovered at a high yield.

[0048] In the present embodiment, the esterification reaction is performed in the presence of at least one of potassium carbonate, rubidium carbonate, and cesium carbonate. That is, it is presumed that the potassium ion, the rubidium ion, or the cesium ion changes the phenolic hydroxyl group (OX) site in formula (1) to O - , and the reaction is performed. In particular, it is presumed that the potassium ion, the rubidium ion, and the cesium ion are large in size as cations, and thus the phenoxy anion easily becomes free, and the nucleophilic attack property to the acylating agent can be improved. On the other hand, it is presumed that, with respect to the sodium ion and the lithium ion, the ability to ionize OH to O - is small, and even if ionization occurs, the ionic bonding force with the sodium ion or the lithium ion is strong, and the reactivity with the acylating agent is low. In addition, it is presumed that, with respect to potassium bicarbonate and the like, the ionic radius and the basicity are low compared to potassium carbonate due to the influence of hydrogen (H), and O - - ​The ability of the catalyst is small, and thus the reactivity is low. In addition, a carbonate is used in the present embodiment. If a catalyst stronger than a carbonate is used, it is presumed that the catalyst attacks the methacrylic anhydride. For example, potassium hydroxide and cesium hydroxide decompose the methacrylic anhydride into methacrylic acid. In the present embodiment, in order to activate the phenolic hydroxyl group (OX) site of the compound of formula (1) preferentially, a carbonate is selected. Furthermore, carbonates are inexpensive, and have high industrial value.

[0049] Furthermore, the (meth)acrylate compound obtained by the production method of the present embodiment can be one having the same performance as conventional low-dielectric resins. Furthermore, a resin having a high glass transition temperature can be obtained, and a material having excellent heat resistance can be obtained.

[0050] Hereinafter, the details of the production method of the present embodiment will be described.

[0051] In the production method of the present embodiment, a polymer having a structure represented by formula (1) is reacted with a (meth)acrylic anhydride, and an esterification reaction is performed. As a result, a (meth)acrylate compound in which a (meth)acryloyl group is introduced to the phenolic hydroxyl group possessed by the polymer having a structure represented by formula (1), i.e., the X site of formula (1), is obtained.

[0052] In the production method of the present embodiment, a polymer having a structure represented by formula (1) is used as a raw material. By using such a resin, a thermosetting resin having excellent low-dielectric properties and heat resistance can be produced.

[0053] Formula (1)

[0054]

[0055] (In formula (1), R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from a hydrogen atom and an alkyl group, and at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is selected from a single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, and an alkylene group-*, * being a bonding position to other sites. X is a hydrogen atom, at least a part of which is reacted with a (meth)acrylic anhydride to become a (meth)acryloyl group.)

[0056] R 1 , R 2 , R 3 , R 4 , and R 5each independently is selected from the group consisting of a hydrogen atom and an alkyl group. For the alkyl group, an alkyl group having 1 to 10 carbons is preferred, and an alkyl group having 1 to 5 carbons is more preferred. For the alkyl group, any of a linear, branched, or cyclic alkyl group can be used, but a linear or branched alkyl group is preferred, and a linear alkyl group is further preferred. The alkyl group can or can not have a substituent, but a substituent is preferred. When a substituent is present, as the substituent, a halogen atom, an alkenyl group, an alkynyl group, or an aryl group is exemplified. For the alkyl group, specifically, a methyl group, an ethyl group, or a propyl group is preferred, and a methyl group is further preferred.

[0057] For the aforementioned single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, or alkylene-*, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, or alkylene-* is preferred, and -O-* is more preferred.

[0058] In the present embodiment, for R 1 , R 2 , R 3 , R 4 , and R 5 , preferably, two or three are hydrogen atoms, two or three are alkyl groups (preferably methyl groups), and the remaining is a single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, or alkylene-* (preferably -O-*) is preferred, and more preferably, R 2 and R 4 are hydrogen atoms, R 1 and R 5 are alkyl groups (preferably methyl groups), and R 3 is a single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, or alkylene-*.

[0059] In formula (1), * indicates a bonding position to other moieties, but is generally bonded to the main chain of the polymer. However, for the structure shown in formula (1), it can also be bonded to the side chain of the polymer.

[0060] In the polymer (raw material) having the structure shown in formula (1), at least a part of X, which is a hydrogen atom, is reacted with (meth)acrylic anhydride to become a (meth)acryloyl group. In the present embodiment, the proportion of X that is a hydrogen atom after the reaction with (meth)acrylic anhydride is preferably 15 mol% or less, more preferably 10 mol% or less, further preferably 7 mol% or less, and even more preferably 3 mol% or less. The lower limit of the proportion of X that is a hydrogen atom is preferably 0 mol% or more. Note that, as described later in detail, a part of X can be reacted with an acyl compound or the like to become an acyl group or the like.

[0061] The polymer having the structure represented by formula (1) is not particularly limited as long as it has the structure represented by formula (1). The structure represented by formula (1) can be present at the terminal of the polymer or at a portion other than the terminal of the polymer. As one embodiment of the polymer having the structure represented by formula (1), a polyphenylene ether compound having the structure represented by formula (1) at least at the terminal (preferably both terminals) is exemplified. In addition, as one embodiment of the polymer having the structure represented by formula (1), a polyphenylene ether compound having the structure represented by formula (1) is exemplified.

[0062] The polymer having the structure represented by formula (1) is specifically preferably a polymer represented by formula (2) or formula (3).

[0063]

[0064] (in formula (2), R 11 ~R 18 are each independently selected from a hydrogen atom and an alkyl group, a Y 1 is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, or -C(R 9 )(R 10 )-, R 9 and R 10 are each independently a hydrogen atom, an alkyl group, an alkynyl group, a hydroxyl group, an amino group, an aryl group, or a heterocyclic group, R 9 and R 10 are optionally bonded to each other to form a ring structure, X is a hydrogen atom, at least a portion of which is reacted with (meth)acrylic anhydride to become a (meth)acryloyl group. n is an integer of 0 or more, m is an integer of 0 or more, and m+n is an integer of 1 or more.)

[0065] R 11 ~R 18 are each independently selected from a hydrogen atom and an alkyl group. The alkyl group is preferably an alkyl group having a carbon number of 1 to 10, and more preferably an alkyl group having a carbon number of 1 to 5. The alkyl group can be any of a straight chain, a branched chain, and a cyclic one, but is preferably a straight chain or a branched chain, and further preferably a straight chain. The alkyl group can have or not have a substituent, but is preferably not to have a substituent. When the alkyl group has a substituent, a halogen atom, an alkenyl group, an alkynyl group, and an aryl group are exemplified as the substituent. The alkyl group is specifically preferably a methyl group, an ethyl group, and a propyl group, and further preferably a methyl group.

[0066] R 11 , R 12 , R 13 , and R 14 are preferably those in which 1 to 3 are hydrogen atoms and the remaining portions are alkyl groups (preferably methyl groups), and more preferably R 13 and R 14 are hydrogen atoms, and R11 and R 12 is an alkyl group (preferably a methyl group).

[0067] For R 15 , R 16 , R 17 , and R 18 , it is preferred that 1 to 3 of them are hydrogen atoms and the rest are alkyl groups (preferably methyl groups), more preferably 1 or 2 of them are hydrogen atoms and the rest are alkyl groups.

[0068] Y 1 is a single bond, -0-, -S-, -S(=0)-, -S(=0)2-, -C(=0)-, or -C(R 9 )(R 10 )-, preferably a single bond, -0-, or -C(R 9 )(R 10 )-, more preferably a single bond or -C(R 9 )(R 10 )-.

[0069] R 9 and R 10 are each independently a hydrogen atom, an alkyl group, an alkynyl group, a hydroxyl group, an amino group, an aryl group, or a heterocyclic group, R 9 and R 10 may optionally be bonded to each other to form a ring structure. For the alkyl group, the alkynyl group, the aryl group, and the heterocyclic group, it can have or not have a substituent, but it is preferred that it does not have a substituent. As the substituent, a halogen atom, an alkenyl group, an alkynyl group, and an aryl group are exemplified.

[0070] R 9 and R 10 are each independently preferably a hydrogen atom, an alkyl group having a carbon number of 1 to 10, an alkynyl group having a carbon number of 2 to 10, a hydroxyl group, an amino group, an aryl group having a carbon number of 6 to 12, or a 5-membered ring or 6-membered ring heterocyclic group, more preferably a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or a hydroxyl group, further preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.

[0071] For X, the same meaning as that of formula (1) is applied.

[0072] n is an integer of 0 or more, preferably an integer of 1 or more, more preferably an integer of 5 or more, and in addition, preferably an integer of 50 or less, more preferably an integer of 20 or less.

[0073] m is an integer of 0 or more, preferably an integer of 1 or more, more preferably an integer of 5 or more, and in addition, preferably an integer of 50 or less, more preferably an integer of 20 or less.

[0074] 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 furthermore, preferably an integer of 100 or less, more preferably an integer of 30 or less.

[0075]

[0076] (In formula (3), R 21 is an alkyl group, a hydroxyl group, or an aryl group, and Y 2 is -CH2-, -CH2O-, or -CH2OCH2-, X is a hydrogen atom, at least a part of which is reacted with (meth)acrylic anhydride to become a (meth)acryloyl group. I is an integer of 1 or more, k is an integer of 2 or more, and z is an integer of 0 to 3.

[0077] R 21 is an alkyl group, a hydroxyl group, or an aryl group, and preferably an alkyl group.

[0078] The alkyl group is preferably an alkyl group having a carbon number of 1 to 15, more preferably an alkyl group having a carbon number of 2 to 10, and more preferably an alkyl group having a carbon number of 3 to 7. The alkyl group can be any of a straight chain, a branched chain, and a cyclic one, but is preferably a straight chain or a branched chain, and further preferably a branched chain. The alkyl group can have or not have a substituent, but preferably does not have a substituent. When the alkyl group has a substituent, as the substituent, a halogen atom, an alkenyl group, an alkynyl group, and an aryl group are exemplified. Specifically, as the alkyl group, a methyl group, an ethyl group, and a butyl group are preferred, and further a tert-butyl group is preferred.

[0079] As the aryl group, a phenyl group is preferred.

[0080] Y 2 is -CH2-, -CH2O-, or -CH2OCH2-, and preferably -CH2-.

[0081] X has the same meaning as in formula (1).

[0082] I is an integer of 1 or more, preferably an integer of 4 or more, more preferably an integer of 5 or more, and furthermore, preferably an integer of 50 or less, more preferably an integer of 20 or less.

[0083] k is an integer of 2 or more, preferably an integer of 3 or more, more preferably an integer of 6 or more, and furthermore, preferably an integer of 50 or less, more preferably an integer of 20 or less.

[0084] z is an integer of 0 to 3, preferably an integer of 0 or more, more preferably an integer of 1 or more, and furthermore, preferably an integer of 3 or less, more preferably an integer of 1 or less.

[0085] * is a bonding site to another constitutional unit or a terminal group. As the terminal group, a hydrogen atom and a hydroxyl group are exemplified, and preferably a hydrogen atom.

[0086] The polymer represented by formula (2) and the polymer represented by formula (3) can also include other constitutional units within the scope of the gist of the present application. The polymer represented by formula (2) and the polymer represented by formula (3) do not include other constitutional units, or the proportion of other constitutional units is preferably 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).

[0087] In the production method of the present embodiment, the polymer having the structure represented by formula (1) (further, the polymer represented by formula (2), the polymer represented by formula (3)) generally accounts for 90% by mass or more of the raw material, i.e., the polymer component, and preferably accounts for 95% by mass or more.

[0088] In the production method of the present embodiment, one kind of polymer having the structure represented by formula (1) (further, the polymer represented by formula (2), the polymer represented by formula (3)) can be used, or two or more kinds thereof can be used.

[0089] The polymer having the structure represented by formula (1) preferably has a mass per 1 mol of hydroxyl group, i.e., a hydroxyl value, of 100 to 5,000 g / mol. By being equal to or greater than the lower limit of the aforementioned range, the dielectric properties of the resulting (meth)acrylate compound can be reduced. In addition, by being equal to or less than the upper limit of the aforementioned range, a sufficient amount of (meth)acryloyl groups can be introduced into the resulting (meth)acrylate compound, and the (meth)acrylate compound can become more excellent in heat resistance. The aforementioned hydroxyl value is more preferably 2,000 g / mol or less, further preferably 1,200 g / mol or less, and still more preferably 200 g / mol or more, further preferably 300 g / mol or more.

[0090] The aforementioned hydroxyl value is measured as described in the Examples below.

[0091] The polymer having the structure represented by formula (1) preferably has a number average molecular weight of 1,000 to 10,000. By being within the aforementioned range, the resulting (meth)acrylate compound tends to have a balanced and excellent performance when cured. Specifically, the (meth)acrylate compound tends to be more excellent in low dielectric properties, heat resistance, easy curability, uniform film-forming properties, and the like. The aforementioned number average molecular weight is more preferably 1,200 or more, further preferably 1,500 or more, and still more preferably 6,000 or less, further preferably 5,000 or less, still more preferably less than 4,000, and yet more preferably 3,500 or less.

[0092] The aforementioned number average molecular weight (Mn) is measured as described in the Examples below.

[0093] For the polymer having the structure represented by Formula (1) used in the present embodiment, it is preferable that both the number average molecular weight and the hydroxyl value described above are satisfied. In this case, the effects of the present application are more effectively exerted.

[0094] Further, the molecular weight distribution (Mw / Mn) is more preferably 1.01 or greater, further preferably 1.10 or greater, and additionally, more preferably 10.0 or less, further preferably 5.00 or less, and even more preferably 3.00 or less. In particular, in the present embodiment, even if the molecular weight distribution (Mw / Mn) is 1.50 or greater, the hydroxyl groups can be appropriately esterified.

[0095] The weight average molecular weight (Mw) described above was measured as described in the Examples described below.

[0096] Next, the catalyst used in the production method of the present embodiment will be described. In the present embodiment, at least one of potassium carbonate, rubidium carbonate, and cesium carbonate is used as the catalyst. By using these catalysts, the reaction of the polymer having the structure represented by Formula (1) and (meth)acrylic anhydride can be effectively promoted. Furthermore, the (meth)acrylate compound obtained can be recovered at a high yield.

[0097] In the present embodiment, among potassium carbonate, rubidium carbonate, and cesium carbonate, potassium carbonate and cesium carbonate are preferable, and potassium carbonate is more preferable.

[0098] The form of potassium carbonate, rubidium carbonate, and cesium carbonate is not particularly limited, but it is preferable that it is in a powder form. Further, the form of potassium carbonate, rubidium carbonate, and cesium carbonate is preferably a fine powder (average particle diameter of about 10 to 200 μm). If a powder form is used, the specific surface area becomes large, and the reactivity can be improved.

[0099] In the production method of the present embodiment, 1.0 mole or more (mol / mol-OH) of at least one of potassium carbonate, rubidium carbonate, and cesium carbonate is used per 1 mole of the hydroxyl group of the polymer having the structure represented by Formula (1), more preferably 3.0 moles or more, and additionally, preferably 10.0 moles or less, and more preferably 7.0 moles or less. By being equal to or greater than the lower limit value described above, the reactivity of the hydroxyl group of the polymer having the structure represented by Formula (1) and (meth)acrylic anhydride has a tendency to be further improved. By being equal to or less than the upper limit value described above, the effect of reducing the production cost has a tendency to be further improved.

[0100] In the production method of the present embodiment, one of potassium carbonate, rubidium carbonate, and cesium carbonate can be used alone, or two or more of them can be used. When two or more are used, the total amount is preferably within the range described above.

[0101] In the production method of the present embodiment, the esterification reaction can be performed without using 4-dimethylaminopyridine (DMAP) that has conventionally been used. That is, in the production method of the present embodiment, the esterification reaction can be performed in a state where DMAP is substantially absent. By substantially absent is meant that the amount of DMAP present is preferably 0.1 mol or less, more preferably 0.05 mol or less, further preferably 0.03 mol or less, and even more preferably 0.01 mol or less, relative to the total amount of 1.0 mol of potassium carbonate, rubidium carbonate, and cesium carbonate. The lower limit is 0 mol.

[0102] In addition, in the production method of the present embodiment, the esterification reaction is preferably performed in a state where an esterification catalyst other than potassium carbonate, rubidium carbonate, and cesium carbonate is substantially absent. By substantially absent is meant that the amount of the esterification catalyst other than potassium carbonate, rubidium carbonate, and cesium carbonate present is preferably 0.1 mol or less, more preferably 0.05 mol or less, further preferably 0.03 mol or less, and even more preferably 0.01 mol or less, relative to the total amount of 1.0 mol of potassium carbonate, rubidium carbonate, and cesium carbonate. The lower limit is 0 mol. By setting to such a range, the (meth)acrylate compound can be isolated at a higher yield.

[0103] In the present embodiment, a polymer having a structure represented by formula (1) is reacted with (meth)acrylic anhydride. By (meth)acrylic anhydride is meant methacrylic anhydride and / or acrylic anhydride, and methacrylic anhydride is preferred. By using methacrylic anhydride, the effect of improving the heat resistance when producing a thermosetting resin is more effectively exerted.

[0104] In the production method of the present embodiment, the proportion of the (meth)acryloyl group among X in the polymer having a structure represented by formula (1) (the introduction rate of the (meth)acryloyl group in the phenolic hydroxyl group) is preferably 85 mol% or more, more preferably 90 mol% or more, further preferably 93 mol% or more, and even more preferably 97 mol% or more. As for the upper limit, 100 mol% is ideal, but 99.9 mol% or less is practical.

[0105] In addition, in the esterification reaction, 1.0 moles or more of (meth)acrylic anhydride is preferably used per 1 mole of the hydroxyl group of the polymer having the structure represented by formula (1), and 1.1 moles or more is more preferable. By being 1.0 moles or more, there is a tendency to convert the hydroxyl group of the polymer having the structure represented by formula (1) to the (meth)acryloyl group at a higher ratio. In addition, 10.0 moles or less of (meth)acrylic anhydride is preferably used per 1 mole of the hydroxyl group of the polymer having the structure represented by formula (1), 8.0 moles or less is more preferable, 5.0 moles or less is further preferable, 4.5 moles or less is more preferable, 3.0 moles or less is further more preferable, and 2.0 moles or less is further more preferable. By being 10.0 moles or less, purification becomes easier, and manufacturing costs can be reduced more effectively.

[0106] In the manufacturing method of the present embodiment, when both of methacrylic anhydride and acrylic anhydride are used, the total amount is within the above range.

[0107] The manufacturing method of the present embodiment can be configured so that the polymer having the structure represented by formula (1) is further reacted with an acyl compound, and a part of X after the reaction is an acyl group. When the polymer having the structure represented by formula (1) used in the manufacturing method of the present embodiment contains a large amount of phenolic hydroxyl groups, only reacting with (meth)acrylic anhydride can introduce a large amount of (meth)acryloyl groups. However, when the (meth)acrylate compound obtained by the manufacturing method of the present embodiment is used as a low dielectric material, if a large amount of (meth)acryloyl groups are introduced into the (meth)acrylate compound than necessary, the dielectric constant and the dielectric loss tangent sometimes become high. In addition, as the raw material oligomer (the polymer having the structure represented by formula (1)), it is sometimes difficult to select only those having a small amount of phenolic hydroxyl groups. In this case, by being configured so that the polymer having the structure represented by formula (1) is reacted not only with (meth)acrylic anhydride but also with an acyl compound, and a part of X after the reaction is a (meth)acryloyl group and the other part is an acyl group, a desired low dielectric material can be obtained.

[0108] In the production method of the present embodiment, when the (meth)acrylic anhydride is reacted with the acyl compound, the (meth)acrylic anhydride and the acyl compound can be reacted simultaneously, or either of them can be reacted in advance. In the production method of the present embodiment, it is preferable that the acyl compound be reacted after the (meth)acrylic anhydride is reacted. By reacting the acyl compound after the (meth)acrylic anhydride is reacted, a polymer having an amount of (meth)acryloyl group suitable for the production of a low dielectric material and a low residual hydroxyl group rate can be obtained. Further, it is preferable that the acylation reaction using the acyl compound be performed in the same reaction system, but it can be performed in a reaction system in which potassium carbonate, rubidium carbonate, and cesium carbonate are substantially absent. For example, the polymer having the structure represented by Formula (1) can be reacted with the (meth)acrylic anhydride, the reactants can be recovered, and the acyl compound can be reacted in another reaction system.

[0109] The acyl compound is not particularly limited in terms of its kind, and acetic anhydride is preferable from the viewpoint of production cost. In the present embodiment 9, acetic anhydride is reacted and replaced at a ratio of 1:1 in terms of the molar ratio of methacryloyl group to acetyl group, but the replacement can be performed at an arbitrary ratio in consideration of the hydroxyl equivalent of the raw resin for the reaction.

[0110] In the production method of the present embodiment, when the acyl compound is reacted, the proportion of the acyl group replacing X in the polymer having the structure represented by Formula (1) is preferably 5 mol% or more, and more preferably 10 mol% or more. By being equal to or more than the lower limit value described above, there is a tendency that a resin having more excellent dielectric properties can be obtained. Further, the proportion of the acyl group replacing X in the polymer having the structure represented by Formula (1) is preferably 90 mol% or less, and more preferably 80 mol% or less. By being equal to or less than the upper limit value described above, the thermosetting property of the polymer having the structure represented by Formula (1) can be more favorably maintained.

[0111] Further, in the esterification reaction, 0.1 mol or more of the acyl compound per 1 mol of the hydroxyl group of the polymer having the structure represented by Formula (1) is preferable, and 0.2 mol or more is more preferable. By being equal to or more than the lower limit value described above, the residual rate of the hydroxyl group of the polymer having the structure represented by Formula (1) can be effectively reduced. The acyl compound is preferably 10 mol or less, and more preferably 5 mol or less, per 1 mol of the hydroxyl group of the polymer having the structure represented by Formula (1). By being equal to or less than the upper limit value described above, there is a tendency that purification is more easily performed and production cost is reduced.

[0112] The acyl compound can be used in only one kind, or two or more kinds can be used. When two or more kinds are used, the total amount is preferably within the range described above.

[0113] In the production method of the present embodiment, the esterification reaction is preferably performed in the presence of a solvent. In the production method of the present embodiment, a solvent can not be used when the polymer having the structure represented by Formula (1) is in a liquid state, but a solvent is generally used when the polymer having the structure represented by Formula (1) is in a non-liquid state. By using a solvent, ionization of potassium carbonate, rubidium carbonate, and cesium carbonate, and ionization of the phenolic hydroxyl group of the polymer having the structure represented by Formula (1) can be effectively performed.

[0114] The solvent used in the production method of the present embodiment is not particularly limited as long as the polymer having the structure represented by Formula (1) is dissolved and does not significantly hinder the esterification reaction in the present embodiment, but a non-protic solvent is preferred, and at least one of an aromatic hydrocarbon solvent and an ether solvent is more preferred. By using a non-protic solvent, ionization of the phenolic hydroxyl group derived from the phenolic hydroxyl group has a tendency to be effectively performed. -

[0115] As the solvent, specifically, toluene, dimethylacetamide (DMAC), cyclopentyl methyl ether (CPME), 4-methyltetrahydropryran (MTHP), 1,4-dioxane are exemplified. As the solvent, from the viewpoint of being low polarity and being a good solvent for the polymer having the structure represented by Formula (1), and having a boiling point suitable for the esterification reaction, toluene is preferred. In addition, from the viewpoint of effectively recovering / reusing the solvent, cyclopentyl methyl ether (CPME) which is high in hydrophobicity and difficult to generate a peroxide is preferred.

[0116] As the solvent, a dehydrating solvent is preferred. By using a dehydrating solvent, the yield of the obtained (meth)acrylate compound can be improved.

[0117] In the production method of the present embodiment, when a solvent is used, the amount thereof is preferably 0.1 mL or more, more preferably 1.0 mL or more, and further preferably 2.0 mL or more, per 1 g of the polymer having the structure represented by Formula (1). By being 0.1 mL or more, the fluidity for smoothly performing the esterification reaction can be effectively ensured. In addition, the amount of the aforementioned solvent is preferably 200 mL or less, more preferably 100 mL or less, and further preferably 50 mL or less, per 1 g of the polymer having the structure represented by Formula (1). By being 200 mL or less, the concentration for smoothly performing the esterification reaction can be maintained, and there is a tendency for the effect of reducing the production cost to be further improved.

[0118] In the production method of the present embodiment, one kind of solvent can be used, or two or more kinds of solvents can be used. When two or more kinds of solvents are used, the total amount is preferably within the above range.

[0119] ​The (meth)acrylate compound obtained by the present embodiment can be a methacrylate compound or an acrylate compound, but a methacrylate compound is preferred.

[0120] In the present embodiment, the reaction temperature of the esterification reaction is preferably -20°C or higher, more preferably 0°C or higher, and further preferably 20°C or higher. By being equal to or higher than the aforementioned lower limit value, there is a tendency for the esterification reaction to proceed smoothly and for the hydroxyl group of the polymer having the structure represented by formula (1) to be converted to a (meth)acryloyl group at a high rate. In addition, the reaction temperature of the esterification reaction is preferably 200°C or lower, more preferably 180°C or lower, and further preferably 150°C or lower. By being equal to or lower than the aforementioned upper limit value, there is a tendency for side reactions such as polymerization to be prevented by the (meth)acryloyl group and for the safety of the manufacturing to be improved.

[0121] In the present embodiment, the reaction time of the esterification reaction is preferably 0.5 hours or more, more preferably 1.0 hours or more, and further preferably 2.0 hours or more. By being equal to or more than the aforementioned lower limit value, there is a tendency for the hydroxyl group of the polymer having the structure represented by formula (1) to be converted to a (meth)acryloyl group at a high rate. In addition, the reaction time of the esterification reaction is preferably 120 hours or less, more preferably 72 hours or less, and further preferably 48 hours or less. By being equal to or less than the aforementioned upper limit value, there is a tendency for the effect of reducing the manufacturing cost to be further improved.

[0122] In the present embodiment, the esterification can be performed in a normal atmosphere (in the presence of air) or in a non-reactive gas atmosphere. By performing the esterification in a normal atmosphere, the manufacturing cost can be reduced even more. If the esterification is performed in a non-reactive gas atmosphere, the esterification reaction can be performed in a non-aqueous or deoxygenated system, and the esterification can be made to proceed even more efficiently.

[0123] In the manufacturing method of the present embodiment, it is preferred that filtration be performed after the esterification reaction. In the manufacturing method of the present embodiment, the (meth)acrylate compound can be recovered at a high recovery rate by filtration in one step. The diameter of the filter used for the filtration in the present embodiment is preferably 0.2 to 7.0 μm. As for the filtration, it is preferred that the filtration be performed after the esterification reaction and after cooling to room temperature (for example, 20 to 40°C). The reaction solution after the filtration is preferably subjected to vacuum drying, and more preferably vacuum drying is performed after distilling off most of the reaction solvent.

[0124] As described above, in the manufacturing method of the present embodiment, the (meth)acrylate compound can be separated at a high recovery rate by only the filtration operation, but it is needless to say that other purification operations such as liquid separation operations and recrystallization can be performed in order to further increase the purity.

[0125] In the production method of the present embodiment, the amount of impurities, i.e., (meth)acrylic acid, with respect to 1 mole of the polymer having the structure represented by formula (1), is preferably less than 1 mole%, more preferably 0.8 mole% or less, further preferably 0.6 mole% or less, and even more preferably 0.4 mole% or less. As a lower limit value of the amount of the aforementioned impurities, i.e., (meth)acrylic acid, 0 mole% is ideal, but 0.01 mole% or more is practical.

[0126] In the production method of the present embodiment, when the polymer having the structure represented by formula (1) is allowed to react with an acyl compound in addition to the reaction with (meth)acrylic anhydride, the amount of impurities derived from the acyl compound with respect to 1 mole of the polymer having the structure represented by formula (1) is preferably less than 1 mole%, more preferably 0.8 mole% or less, further preferably 0.6 mole% or less, and even more preferably 0.4 mole% or less. As a lower limit value of the amount of the aforementioned impurities, i.e., impurities derived from the acyl compound, 0 mole% is ideal, but 0.01 mole% or more is practical. The impurities derived from the acyl compound refer to, for example, acetic acid when the acyl compound is acetic anhydride.

[0127] <Use>

[0128] The (meth)acrylate compound obtained by the production method of the present embodiment can be used as it is, or can be used in the form of a resin composition in which other curable compounds, additives are compounded. As the other curable compounds, compounds having a carbon-carbon unsaturated bond group and epoxy resins are exemplified. As the additives, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickening agents, flow adjusting agents, lubricants, antifoaming agents, dispersants, leveling agents, brightening agents, polymerization inhibitors, and the like can be mentioned.

[0129] It is preferable that the (meth)acrylate compound obtained by the production method of the present embodiment or the resin composition containing the aforementioned (meth)acrylate compound is cured and used as a cured product. For such a cured product, it is suitable to be used as an insulating layer of a printed circuit board, a material for semiconductor packaging, from the viewpoint that the heat resistance is excellent and the dielectric properties are excellent.

[0130] Example

[0131] The present application is further concretely described below by way of examples. The materials, amounts used, proportions, contents of treatment, order of treatment, and the like shown in the following examples can be appropriately changed without departing from the gist of the present application. Therefore, the scope of the present application is not limited to the specific examples shown below.

[0132] When the measuring apparatus and the like used in the examples are unavailable due to discontinuation of production or the like, other apparatuses having equivalent performance can be used for the measurement.

[0133] The number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the raw resin were calculated using gel permeation chromatography (GPC) with conversion to standard polystyrene. The apparatus used was an integrated LC (SHIMADZU LC-2010HT) and RI detector (SHIMADZU RID-20A). The chromatographic column consisted of four Shodex guard columns (KF-G 4A) and Shodex GPC standard columns (KF-801, KF-802, KF-803, KF-804) connected in series. The sample dissolved in THF (tetrahydrofuran) was determined by liquid chromatography at a flow rate of 1.0 mL and a temperature of 40°C.

[0134] Example 1

[0135] Following the following procedure, toluene (8 mL) was used as the solvent to dissolve the oligophenyl ether (SABIC Corporation, SA-90, R group) with hydroxyl groups at both ends. a In the reaction, na+ma is approximately 12. 828 mg (1 mmol of hydroxyl group) 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, with an average particle size of less than 150 μm).

[0136] The reaction solution was cooled to 0.5 mL in air, filtered through a 0.45 μm filter, and vacuum dried for 1 hour (pressure less than 1 hPa, 40 °C). It was then dissolved in deuterated chloroform and analyzed by proton nuclear magnetic resonance spectroscopy. 1 ¹H NMR analysis was performed, and the methacrylamide conversion rate (OH modification rate) and the residual methacrylic acid rate (impurity) were calculated according to the following procedure. It was confirmed that the oligophenyl ether with hydroxyl groups at both ends was introduced with a high conversion rate of 94 mol% of methacryloyl groups onto the hydroxyl groups.

[0137]

[0138] For the methacrylylation rate (OH modification rate) and methacrylic acid residue rate (proportion of impurities) of the polymer, based on the proton nuclear magnetic resonance spectrum ( 1 The result was calculated from the H NMR analysis. The NMR apparatus used was a BRUKER AVANCE III 500 (500 MHz). Specifically, the reaction solution was cooled to 0.5 mL in air and filtered through a 0.45 μm filter. The filtrate was then vacuum dried for 1 hour (pressure less than 1 hPa, 40 °C). It was then dissolved in deuterated chloroform and subjected to [further processing] at 25 °C.1 HNMR analysis. Here, the SA-90 of the oligophenylene ether having two terminal hydroxyl groups was analyzed by H NMR. 1 The H NMR spectrum (range of 4 ppm to 7 ppm) is shown in Fig. 1. Figure 1 Figure 1 In the present example, the integral ratio of the proton (c) bonded to the aromatic ring of the nucleus in the vicinity of 6.8 to 7.0 ppm was 4.0, and the integral ratio of the proton (a) of the hydroxyl group in the vicinity of 4.1 to 4.6 ppm was 1.8. The theoretical value of the integral ratio of the proton (a) of the hydroxyl group should be 2.0, but actually 1.8 was observed. For this reason, one of the reasons is that the proton of the hydroxyl group is easily subjected to proton exchange in the solution, the peak is broadened, and observation becomes difficult. In the present example, the integral ratio of the proton (b) bonded to the aromatic ring of the repeating structural unit of the polymer was 24.1, and the methacryloylation rate and the methacrylic acid residual rate were calculated. 1 In the analysis method other than H NMR, the hydroxyl group is easily subjected to intermolecular hydrogen bonding and the like, and there are many cases where quantification is difficult. Therefore, the integral ratio of the proton (b) bonded to the aromatic ring of the repeating structural unit of the polymer (24.1) was compared, and the methacryloylation rate and the methacrylic acid residual rate were calculated.

[0139] In addition, the hydroxyl value of the raw material resin was also calculated by NMR analysis (integral ratio of the proton (b) to the proton (c)) in the same manner as described above. The calculated hydroxyl value was the same value as the standard value of the product of the raw material resin.

[0140] Example 2

[0141] In Example 1, the catalyst was changed from 5 mmol of potassium carbonate to 5 mmol of cesium carbonate (1.63 g), and the same was performed except for this. It was confirmed that the methacryloyl group was introduced at a high conversion rate of 96 mol% to the hydroxyl group of the oligophenylene ether having two terminal hydroxyl groups. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Example 1.

[0142] Example 3

[0143] In Example 1, the solvent was changed to dimethylacetamide (DMAC), and the same was performed except for this. It was confirmed that the methacryloyl group was introduced at a high conversion rate of 90 mol% to the hydroxyl group of the oligophenylene ether having two terminal hydroxyl groups. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Example 1.

[0144] Example 4

[0145] In Example 1, the solvent was changed to 1,4-dioxane (Dioxane), and the same was performed except for this. It was confirmed that the methacryloyl group was introduced at a high conversion rate of 99 mol% to the hydroxyl group of the oligophenylene ether having two terminal hydroxyl groups. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Example 1.

[0146] Example 5 ​

[0147] In Example 1, the solvent was changed to cyclopentyl methyl ether (CPME), and otherwise the same was performed. It was confirmed that the oligophenylene ether having a hydroxyl group at both terminals had a methacryloyl group introduced at a high conversion of more than 99 mol% on the hydroxyl group.

[0148] The obtained oligophenylene ether having a methacryloyl group at both terminals was 1 The H NMR spectrum (range of 4 ppm to 7 ppm) is shown in Figure 2 . Figure 2 The integral ratio of the protons (d 1 , d 2 ) of the double bonds of the methacryloyl groups in the vicinity of 5.7 to 5.8 ppm and 6.3 to 6.4 ppm was 2.0, respectively, and the methacryloylation rate was calculated to be 24.1 / (26.2-2.0) x 100 = more than 99%. The hydroxyl group residual rate was calculated from the integral ratio (0.012) of the protons (a) of the hydroxyl groups in the vicinity of 4.1 to 4.6 ppm to be 0.012 / (2.0+0.012) x 100 = 0.6%, and was almost consistent with the methacryloylation rate (more than 99%). In addition, the methacrylic acid residual rate per 1 molecule of the polymer was calculated from the integral ratio (0.002, 0.002) of the protons (e 1 , e 2 ) of the double bonds of the methacrylic acid in the vicinity of 5.5 to 5.6 ppm and 6.1 to 6.2 ppm to be 0.002 x 24.1 / (26.2-2.0) x 100 = 0.2%.

[0149] Example 6

[0150] In Example 1, the solvent was changed to 4-methyltetrahydro pyran (MTHP), and otherwise the same was performed. It was confirmed that the oligophenylene ether having a hydroxyl group at both terminals had a methacryloyl group introduced at a high conversion of 99 mol% on the hydroxyl group. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Example 1.

[0151] Example 7

[0152] In Example 1, the oligophenylene ether having a hydroxyl group at both terminals (SABIC Corporation, SA-90) was changed to OPE-2000 (Mitsubishi Gas Chemical Company, Inc., group R b in which nb+mb was about 12. 821 mg (1 mmol of the amount of the hydroxyl group), and otherwise the same was performed. It was confirmed that the oligophenylene ether had a methacryloyl group introduced at a high conversion of 95 mol% on the hydroxyl group. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Example 1.

[0153]

[0154] Example 8

[0155] In Example 7, the solvent was changed to cyclopentyl methyl ether (CPME), and otherwise the same was performed. It was confirmed that the methacryloyl group was introduced at a high conversion rate of 98 mol% on the hydroxyl group of the oligophenyl ether. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Example 1.

[0156] Example 9

[0157] According to the following scheme, as the solvent, cyclopentyl methyl ether (CPME) (8 mL) was used, and p-t-butyl-modified xylene resin (Xy-PTBP) (manufactured by Mitsubishi Gas Chemical Company, Inc., nc of about 6, mc of about 4) 3.46 g (hydroxyl group amount of 10 mmol) was reacted with 6 mmol (925 mg) of methacrylic anhydride (MAA) in the presence of 50 mmol (6.91 g) of potassium carbonate at 100°C for 6 hours, and further, with 32 mmol (3.27 g) of acetic anhydride (Ac2O) at 100°C for 6 hours.

[0158] After the reaction solution 0.5 mL was air-cooled, it was filtered through a 0.45 μm filter, and vacuum-dried (pressure of less than 1 hPa, 40°C) for 1 hour. This was dissolved in deuterated chloroform, and the methacryloylation rate and the methacrylic acid residual rate were calculated by proton nuclear magnetic resonance spectrum (1H NMR) analysis. 1 The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Example 1. On the hydroxyl group of Xy-PTBP, the methacryloyl group and the acetyl group were introduced at a ratio (molar ratio) of 1:1, in total, more than 99 mol. In Xy-PTBP-MA-Ac, nc was about 6, mc was about 2, and ld was about 2.

[0159]

[0160] Comparative Example 1

[0161] In Example 1, the potassium carbonate was changed to 0.2 mmol of 4-dimethylaminopyridine (DMAP), and otherwise the same was performed. The introduction rate of the methacryloyl group in the hydroxyl group of the hydroxyl oligophenyl ether was 92 mol%.

[0162] Unlike in the case of the examples, even after the reaction, a large part of the DMAP (37% with respect to the polymer 1 molecule) and the by-produced methacrylic acid (137% with respect to the polymer 1 molecule) remained.

[0163] In addition, DMAP is high in price, and thus is also disadvantageous in cost compared to the potassium carbonate method.

[0164] The two end methyl methacrylato-oligo-phenyl ether obtained in Comparative Example 1 was subjected to GPC measurement. 1 The H NMR spectrum (range of 4 ppm to 7 ppm) is shown in Fig. 1. Figure 3 . Figure 3 The integral ratio of the protons (d 1 , d 2 ) of the double bonds of the methyl methacryloyl groups in the vicinity of 5.7 to 5.8 ppm and 6.3 to 6.4 ppm was 2.0, respectively, and the methacryloylation rate was calculated to be 24.1 / (28.2-2.0) x 100 = 92%. As to the protons (a) of the hydroxyl groups in the vicinity of 4.1 to 4.6 ppm, they were not observed because of exchange with the protons of the methyl methacrylate present in a large amount in the solution. Instead, several peaks of uncertain structure were observed. Further, from the integral ratio (1.49, 1.49) of the protons (e 1 , e 2 ) of the double bonds of the methyl methacrylate in the vicinity of 5.5 to 5.6 ppm and 6.1 to 6.2 ppm, the residual rate of the methyl methacrylate per 1 molecule of the polymer was calculated to be 1.49 x 24.1 / (28.2-2.0) x 100 = 137%. From the integral ratio (0.6) of the protons (g 1 ) bound to the hetero ring of DMAP in the vicinity of 6.6 ppm, the residual rate of DMAP per 1 molecule of the polymer was calculated to be (0.6 / 2) x 24.1 / (28.2-2.0) x 100 = 28%. From the integral ratio (0.2) of the protons (g 2 ) bound to the hetero ring of DMAP / methyl methacrylate salt in the vicinity of 6.7 ppm, the residual rate of the additional DMAP per 1 molecule of the polymer was calculated to be (0.2 / 2) x 24.1 / (28.2-2.0) x 100 = 9%. Further, from the integral ratio (0.09, 0.09) of the protons (f 1 , f 2 ) of the double bonds of the methacrylic anhydride in the vicinity of 5.8 ppm and 6.2 ppm, the residual rate of the methacrylic anhydride per 1 molecule of the polymer was calculated to be (0.09 / 2) x 24.1 / (28.2-2.0) x 100 = 4%.

[0165] Comparative Example 2

[0166] In Example 1, the potassium carbonate was changed to 5 mmol of sodium carbonate, and the same was conducted except for this. The introduction rate of the methyl methacryloyl groups to the hydroxyl groups of the hydroxyl-oligo-phenyl ether was 21 mole%. As to the methacryloylation rate and the residual rate of the methyl methacrylate, the same was measured as in Comparative Example 1.

[0167] Comparative Example 3

[0168] Example 1 was conducted in the same manner except that potassium carbonate was changed to 5 mmol of lithium carbonate. The methacryloyl group introduction rate in the hydroxyl group of the hydroxyl-oligo-phenyl ether was 5 mol%. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Comparative Example 1.

[0169] Comparative Example 4

[0170] Example 1 was conducted in the same manner except that potassium carbonate was changed to 5 mmol of calcium carbonate. The methacryloyl group introduction rate in the hydroxyl group of the hydroxyl-oligo-phenyl ether was 3 mol%. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Comparative Example 1.

[0171] Comparative Example 5

[0172] Example 1 was conducted in the same manner except that potassium carbonate was changed to 5 mmol of potassium bicarbonate. The methacryloyl group introduction rate in the hydroxyl group of the hydroxyl-oligo-phenyl ether was 7 mol%. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Comparative Example 1.

[0173] Comparative Example 6

[0174] Example 1 was conducted in the same manner except that potassium carbonate was changed to 5 mmol of potassium hydroxide. The methacryloyl group introduction in the hydroxyl group of the hydroxyl-oligo-phenyl ether could not be confirmed. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Comparative Example 1.

[0175] From Examples and Comparative Examples 2 and 3, it was found that the ionic radius of the alkali metal carbonate is related to the reactivity of methacryloylation, and it was considered that if sodium carbonate having a smaller ionic radius than potassium carbonate is used, the conversion rate is greatly reduced. It was presumed that the larger the ionic radius of the metal cation, the higher the nucleophilic attack of the phenoxy anion to MAA when the phenolic hydroxyl group is activated.

[0176] Also with the carbonate of the alkaline earth metal, if calcium carbonate having the same ionic radius as lithium carbonate is used, the conversion rate of methacryloylation is as low as 3 mol% (Comparative Example 4). In addition, even if a bicarbonate, i.e., potassium bicarbonate, is used, the conversion rate of methacryloylation is as low as 5 mol% (Comparative Example 5). Potassium hydroxide is highly basic, but MAA is decomposed under the influence of the hydroxide ion thereof, and the reaction does not proceed at all (Comparative Example 6).

[0177] Comparative Example 7

[0178] In Example 1, methacrylic anhydride (MAA) was changed to methacryloyl chloride (MAC) 1.2 mmol (125 mg), and the same was performed except for this. The introduction rate of methacryloyl group to the hydroxyl group of the oligophenylene ether having a hydroxyl group at both terminals was 46 mol%. MAC is more reactive than MAA, but is also more decomposable due to trace moisture or the like in the reaction system, and thus all of the MAC was consumed at a conversion rate of about half. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Comparative Example 1.

[0179] Comparative Example 8

[0180] In accordance with the following scheme, using a reactor additionally provided with a Dean-Stark apparatus, p-xylene (20 mL) was used as a solvent, and the oligophenylene ether having a hydroxyl group at both terminals (SABIC Corp., SA-90) 2.07 g (hydroxyl group amount 2.5 mmol) was subjected to a reaction for 24 hours at 130°C while being distilled together with 5 mmol of methacrylic acid (MA) in the presence of 0.5 mmol of B(OH)3 / H2SO4.

[0181] After the reaction solution 0.5 mL was air-cooled, it was filtered through a 0.45 μm filter, and vacuum-dried (pressure less than 1 hPa, 40°C) for 1 hour. This was dissolved in deuterated chloroform, and the methacryloylation rate and the methacrylic acid residual rate were calculated by1H NMR analysis. 1 The introduction rate of methacryloyl group to the hydroxyl group of the oligophenylene ether having a hydroxyl group at both terminals was 4 mol%. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Comparative Example 1.

[0182]

[0183] Comparative Example 9

[0184] In Comparative Example 8, instead of B(OH)3 / H2SO4, p-Me-C6H4SO3H-H2O (p-toluenesulfonic acid monohydrate, PTSA-H2O) 0.25 mmol was used, the amount of methacrylic acid (MA) was changed from 5 mmol to 12.5 mmol, and the same was performed except for this. The introduction rate of methacryloyl group to the hydroxyl group of the oligophenylene ether having a hydroxyl group at both terminals was 6 mol%. The methacryloylation rate and the methacrylic acid residual rate were measured in the same manner as in Comparative Example 1.

[0185] Comparative Example 10

[0186] In Comparative Example 8, instead of B(OH)3 / H2SO4, AMBERLYST (registered trademark) 15 (manufactured by Sigma-Aldrich Corporation) was used in an amount of 10% by mass relative to the mass of the oligophenyl ether having a hydroxyl group at both terminals (manufactured by SABIC, SA-90), the amount of methacrylic acid (MA) was changed from 5 mmol to 12.5 mmol, and otherwise the same was performed. The introduction rate of the methacryloyl group to the hydroxyl group of the oligophenyl ether having a hydroxyl group at both terminals was 6 mol%.

[0187] In Comparative Example 8, methacryloyl modification of SA-90 based on MA was performed in a B(OH)3 / H2SO4 co-catalyst system. As a result, in a xylene solvent, it was considered that the reaction proceeded when the reaction temperature was set to 130°C, but the conversion rate was very low at 4% even when 1.7 times MA and 3 times or more B(OH)3 / H2SO4 were used compared to the example described in Japanese Patent Application Publication No. 2011-105667. As a reason for the low efficiency of the methacrylation reaction compared to the example described in Japanese Patent Application Publication No. 2011-105667, it was presumed that the reactivity was reduced due to steric hindrance of the 2,6-dimethyl group adjacent to the phenolic hydroxyl group at the terminal of SA-90, and the catalytic activity was hindered due to the interaction of B(OH)3 / H2SO4 and the oligophenylene group of the main chain of SA-90. In addition, when p-toluenesulfonic acid, which is commonly used as an acid catalyst for esterification, or AMBERLYST 15, a solid acid, was used, the conversion rate was low at around 6% even when a large amount (12.5 mmol) of MA was used (Comparative Examples 9 and 10).

[0188] Example 10

[0189] As shown in the scheme below, the same was performed on a 25-fold scale in Example 8. It was confirmed that the methacryloyl group was introduced at a high conversion rate of 95 mol% to the methacryloyl group on the hydroxyl group of the oligophenyl ether.

[0190] The obtained compound was a beige powder, and the amount of residual hydroxyl group was 5 mol%.

[0191]

[0192] Comparative Examples 11 to 13

[0193] In Example 1, the type of catalyst was changed to sodium acetate (AcONa), the amount of catalyst and the type of solvent were changed as shown in Table 5, and otherwise the same was performed. The results are shown in Table 5.

[0194] The results of Examples 1 to 9 and Comparative Examples 1 to 13 are summarized below. In the following table, if an impurity is not specifically shown, it means methacrylic acid (MA). AcOH means acetic acid. The amount of impurity sometimes exceeds 100 mol% because, for example, when 1.2 mmol of methacrylic anhydride is used with respect to 1 mmol of hydroxyl group, 240 mol% of methacrylic anhydride is added with respect to 1 molecule of polymer. If the amount of impurity with respect to hydroxyl group, methacryloyl group is to be calculated, since the values of residual hydroxyl group, introduced methacryloyl group are different in each example / comparative example, comparison becomes difficult, and thus it is set to the value with respect to 1 molecule of polymer.

[0195] [Table 1]

[0196]

[0197] [Table 2]

[0198]

[0199] [Table 3]

[0200]

[0201] [Table 4]

[0202]

[0203] [Table 5]

[0204]

[0205] In Tables 1 to 5, "100-OH modification rate" corresponds to "the proportion (mol%) of X of formula (1) being a hydrogen atom".

[0206] N.D. means not detected.

[0207] The unit of hydroxyl value (g / mol) indicates the mass of hydroxyl group per 1 mole of polymer (raw material resin).

[0208] mol / mol-OH indicates the amount of addition (mol) per 1 mole of hydroxyl group of raw material resin (polymer having the structure shown in formula (1)).

[0209] Example 11

[0210] The (meth)acrylate compound (OPE-2MA) obtained in Example 10 was heat-cured and a resin was produced.

[0211] Specifically, 1 part by mass of Purbityl (registered trademark) P was added to the OPE-2MA obtained in Example 10, and vacuum heat pressing was performed at 200°C for 2 hours at a pressure of 1.92 MPa at a temperature increase rate of 3°C / min to obtain a cured product having a thickness of 1.2 mm.

[0212] For the obtained resin, the dielectric constant, the dielectric loss tangent, and the glass transition temperature were measured.

[0213] <Measurement of Glass Transition Temperature>

[0214] For the glass transition temperature of the cured product, dynamic viscoelasticity measurement was performed on the obtained cured product cut into 5 mm in width, 40 mm in length, and the peak temperature of the obtained dynamic elastic modulus was set as the glass transition temperature. The unit was represented in °C.

[0215] Apparatus used: DMS6100, EXSTAR6000, manufactured by Seiko Instruments Inc.

[0216] Temperature increase rate: 5°C / min

[0217] Frequency: sinusoidal wave, 10 Hz

[0218] <Measurement of Dielectric Properties>

[0219] For the dielectric constant and the dielectric loss tangent of the cured product, the obtained cured product was cut into 1.2 mm in thickness, 0.8 mm in width, and 100 mm in length, and the values at 10 GHz were measured by the cavity perturbation method.

[0220] Apparatus used: 8722ES Network Analyzer, manufactured by Agilent Technologies, Inc.

[0221] For the obtained cured product, the dielectric constant (D k ) was 2.461 (10 GHz), the dielectric loss tangent (D f ) was 0.00423 (10 GHz), and the glass transition temperature (T g ) was 155°C (10 Hz). For the physical properties (D k , D f , T g ) of the thermoset resin of OPE-2MA, the same performance values as those of the cured product of a general two-terminal methacryl group-containing polyphenylene ether were obtained.

[0222]

Claims

1. A method for producing a (meth)acrylate 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, In formula (1), R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from a hydrogen atom and an alkyl group, and at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is selected from a single bond, -O-*, -S-*, -S(=O)-*, -S(=O)2-*, and an alkylene group-*, * is a bonding position with other moieties, X is a hydrogen atom, at least a part of which is reacted with (meth)acrylic anhydride to become a (meth)acryloyl group, wherein the polymer having a structure represented by formula (1) comprises a polymer represented by formula (2) or formula (3), 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, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, or -C(R 9 )(R 10 )-, R 9 and R 10 are each independently a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or a hydroxyl group, X is a hydrogen atom, at least a part of which is reacted with (meth)acrylic anhydride to become a (meth)acryloyl group, n is an integer of 0 or more, m is an integer of 0 or more, and m+n is an integer of 1 or more, In formula (3), R 21 is an alkyl group having 1 to 15 carbon atoms or a hydroxyl group, Y 2 is -CH2-, -CH2O-, or -CH2OCH2-, X is a hydrogen atom, at least a part of which is reacted with (meth)acryloyl anhydride to become a (meth)acryloyl group, 1 is an integer of 1 or more, k is an integer of 2 or more, z is an integer of 0 to 3, and * is a bonding site with other constitutional units or a terminal group.

2. The method for producing a (meth) acrylate compound according to claim 1, wherein, a proportion of X being hydrogen atoms in the polymer having a structure represented by formula (1) after the reaction with (meth)acrylic anhydride is 10 mol% or less.

3. The method for producing a (meth) acrylate compound according to claim 1 or 2, wherein, further reacting the polymer having a structure represented by formula (1) with an acyl compound, a part of X after the reaction being acyl groups.

4. The method for producing a (meth) acrylate compound according to claim 1 or 2, wherein, a number average molecular weight of the polymer having a structure represented by formula (1) is 1,000 to 10,000.

5. The method for producing a (meth)acrylate compound according to claim 1 or 2, wherein, a hydroxyl value, which is a mass of hydroxyl groups per 1 mol of the polymer having a structure represented by formula (1), is 100 to 5,000 g / mol.

6. The method for producing a (meth) acrylate compound according to claim 1 or 2, wherein, per 1 mol of hydroxyl groups of the polymer having a structure represented by formula (1), a total of 1.0 to 10.0 mol of at least one of potassium carbonate, rubidium carbonate, and cesium carbonate, and 1.0 to 10.0 mol of (meth)acrylic anhydride are used.

7. The method for producing a (meth)acrylate compound according to claim 1 or 2, wherein, the reaction is performed in the presence of at least one of an aromatic hydrocarbon solvent and an ether solvent.

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