JP7592528B2 - Vinyl ether/vinyl phosphorus copolymer and method for producing same - Google Patents

Description

The present invention relates to a copolymer of vinyl ether and vinyl phosphorus. The present invention also relates to a method for producing the copolymer of vinyl ether and vinyl phosphorus.

Organophosphorus compounds are chemical substances that are widely used in a variety of products, such as flame retardants, plasticizers, insecticides, pharmaceuticals, agricultural chemicals, and ligands for metal complexes. In recent years, organophosphorus compounds have been attracting particular attention industrially as functional materials, such as metal surface treatment agents, and as constituent materials for flame-retardant resins and in the field of electronic materials.

In recent years, various chemical products have been proposed as functional materials of organic phosphorus compounds. For example, Patent Document 1 proposes the use of a copolymer of hydroxyalkyl (meth)acrylate and vinylphosphonic acid as an adhesion enhancing additive.

JP 2018-168376 A

However, the copolymer of hydroxyalkyl (meth)acrylate and vinylphosphonic acid described in Patent Document 1 is not compatible with monomers for thermosetting resins such as diisocyanates at room temperature, and in order to use it as a polyol, which is a raw material for polyurethane, a solvent was required to make the copolymer compatible with the monomers. Therefore, a process such as removing the solvent was required, which was unsuitable from the viewpoint of the manufacturing process. Therefore, an object of the present invention is to provide a phosphorus atom-containing copolymer that is compatible with monomers for thermosetting resins at room temperature. Another object of the present invention is to provide a method for manufacturing a phosphorus atom-containing copolymer that is compatible with monomers for thermosetting resins at room temperature.

As a result of intensive research into solving the above problems, the inventors discovered that a copolymer of a specific vinyl ether and a specific vinyl phosphorus can solve the above problems, and thus completed the present invention.

（一般式（１）中、Ｒ^１は、直鎖状、分岐鎖状、もしくは環状の、炭素数１～１０の脂肪族炭化水素基または炭素数３～７のエーテルから２個の水素原子を除いた基を表し、ｎは１～５の整数を示す。）
で表され、
前記ビニルリンが、下記一般式（２）：

（一般式（２）中、Ｒ^２およびＲ^３は、それぞれ独立して、ヒドロキシ基、置換もしくは非置換のアルキル基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアラルキル基、置換もしくは非置換のアリール基、または置換もしくは非置換のアリールオキシ基を示す。また、Ｒ^２およびＲ^３は、互いに結合して環状構造を形成していてもよい。）
で表される、共重合体。
［２］ 前記共重合体の数平均分子量（Ｍｎ）が、５００～１００００の範囲内である、［１］に記載の共重合体。
［３］ 前記ビニルエーテルが、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、およびジエチレングリコールモノビニルエーテルからなる群から選択される少なくとも１種である、［１］または［２］に記載の共重合体。
［４］ 前記一般式（２）中、Ｒ^２およびＲ^３が、それぞれ独立して、ヒドロキシ基、炭素数１～８のアルキル基、炭素数１～８のアルコキシ基、炭素数１～８のアリールオキシ基、または炭素数５～１２のアリール基である、［１］～［３］のいずれかに記載の共重合体。
［５］ 前記ビニルリンが、ビニルホスホン酸ジメチル、ビニルホスホン酸ジエチル、ビニルホスホン酸ジフェニル、ジフェニルビニルホスフィンオキシド、および９，１０－ジヒドロ－９－オキサ－１０－ビニル－１０－ホスファフェナントレン－１０－オキシドからなる群から選択される少なくとも１種である、［１］～［４］のいずれかに記載の共重合体。
［６］ 前記共重合体が、熱硬化性樹脂用モノマーと１０～３０℃で相溶する、［１］～［５］のいずれかに記載の共重合体。
［７］ 前記熱硬化性樹脂用モノマーが、ジイソシアネートである、［６］に記載の共重合体。
［８］ 前記ジイソシアネートが、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、およびトルエンジイソシアネートからなる群から選択される少なくとも１種である、［７］に記載の共重合体。
［９］ ［１］～［８］のいずれかに記載の共重合体と、熱硬化性樹脂用モノマーとを含む、熱硬化性樹脂組成物。
［１０］ ビニルエーテルとビニルリンの共重合体の製造方法であって、
下記一般式（１）：

（一般式（１）中、Ｒ^１は、直鎖状、分岐鎖状、もしくは環状の、炭素数１～１０の脂肪族炭化水素基または炭素数３～７のエーテルから２個の水素原子を除いた基を表し、ｎは１～５の整数を示す。）
で表されるビニルエーテルと、
下記一般式（２）：

（一般式（２）中、Ｒ^２およびＲ^３は、それぞれ独立して、ヒドロキシ基、置換もしくは非置換のアルキル基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアラルキル基、置換もしくは非置換のアリール基、または置換もしくは非置換のアリールオキシ基を示す。また、Ｒ^２およびＲ^３は、互いに結合して環状構造を形成していてもよい。）
で表されるビニルリンとを、溶媒存在下または無溶媒で、ラジカル重合開始剤を用いて重合させる工程を含む、製造方法。
［１１］ 前記ラジカル重合開始剤が、アゾ系重合開始剤および過酸化物系重合開始剤からなる群から選択される少なくとも１種である、［１０］に記載の製造方法。
［１２］ 前記ラジカル重合開始剤が、エステル型アゾ化合物およびニトリル型アゾ化合物からなる群より選択される少なくとも１種である、［１０］または［１１］に記載の製造方法。
［１３］ 前記溶媒が、有機溶媒である、［１０］～［１２］のいずれかに記載の製造方法。
［１４］ 前記有機溶媒が、アルコール、エステル、ケトン、エーテル、塩素系溶媒、炭化水素溶媒、および芳香族炭化水素からなる群から選択される少なくとも１種である、［１３］に記載の製造方法。
［１５］ 前記有機溶媒が、エタノール、ブタノール、酢酸ブチル、およびトルエンからなる群から選択される少なくとも１種である、［１３］または［１４］に記載の製造方法。 That is, according to the present invention, the following inventions are provided.
[1] A copolymer of vinyl ether and vinyl phosphorus,
The vinyl ether is represented by the following general formula (1):

(In general formula (1), R ¹ represents a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group in which two hydrogen atoms have been removed from an ether group having 3 to 7 carbon atoms, and n represents an integer of 1 to 5.)
It is expressed as
The vinyl phosphorus is represented by the following general formula (2):

(In general formula (2), ^R2 and ^R3 each independently represent a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group. ^R2 and ^R3 may be bonded to each other to form a cyclic structure.)
A copolymer represented by the formula:
[2] The copolymer according to [1], wherein the number average molecular weight (Mn) of the copolymer is within the range of 500 to 10,000.
[3] The copolymer according to [1] or [2], wherein the vinyl ether is at least one selected from the group consisting of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether.
[4] The copolymer according to any one of [1] to [3], wherein in the general formula (2), R ² and R ³ are each independently a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 1 to 8 carbon atoms, or an aryl group having 5 to 12 carbon atoms.
[5] The copolymer according to any one of [1] to [4], wherein the vinyl phosphorus is at least one selected from the group consisting of dimethyl vinylphosphonate, diethyl vinylphosphonate, diphenyl vinylphosphonate, diphenylvinylphosphine oxide, and 9,10-dihydro-9-oxa-10-vinyl-10-phosphaphenanthrene-10-oxide.
[6] The copolymer according to any one of [1] to [5], which is compatible with a monomer for a thermosetting resin at 10 to 30° C.
[7] The copolymer according to [6], wherein the monomer for a thermosetting resin is a diisocyanate.
[8] The copolymer according to [7], wherein the diisocyanate is at least one selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate.
[9] A thermosetting resin composition comprising the copolymer according to any one of [1] to [8] and a monomer for a thermosetting resin.
[10] A method for producing a vinyl ether and vinyl phosphorus copolymer, comprising the steps of:
The following general formula (1):

(In general formula (1), R ¹ represents a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group in which two hydrogen atoms have been removed from an ether group having 3 to 7 carbon atoms, and n represents an integer of 1 to 5.)
and a vinyl ether represented by the formula:
The following general formula (2):

(In general formula (2), ^R2 and ^R3 each independently represent a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group. ^R2 and ^R3 may be bonded to each other to form a cyclic structure.)
and a vinyl phosphorus represented by the formula (I) in the presence or absence of a solvent, using a radical polymerization initiator.
[11] The method according to [10], wherein the radical polymerization initiator is at least one selected from the group consisting of azo-based polymerization initiators and peroxide-based polymerization initiators.
[12] The method according to [10] or [11], wherein the radical polymerization initiator is at least one selected from the group consisting of ester-type azo compounds and nitrile-type azo compounds.
[13] The method according to any one of [10] to [12], wherein the solvent is an organic solvent.
[14] The method according to [13], wherein the organic solvent is at least one selected from the group consisting of alcohols, esters, ketones, ethers, chlorinated solvents, hydrocarbon solvents, and aromatic hydrocarbons.
[15] The method according to [13] or [14], wherein the organic solvent is at least one selected from the group consisting of ethanol, butanol, butyl acetate, and toluene.

According to the present invention, it is possible to provide a phosphorus atom-containing copolymer that is compatible with a monomer for a thermosetting resin, such as a diisocyanate, at room temperature. Furthermore, according to the present invention, it is possible to provide a method for producing such a copolymer.

FIG. 1 shows the MALDI-MS spectrum of the copolymer of Example 9.

[Copolymer of vinyl ether and vinyl phosphorus]
The copolymer according to the present invention is a copolymer of the specific vinyl ether described below and the specific vinyl phosphorus described below. Moreover, such a copolymer is a liquid to glassy substance at room temperature (e.g., 10 to 30°C) and is easily compatible with a monomer for a thermosetting resin at room temperature. For example, such a copolymer is compatible with a monomer for a thermosetting resin such as a diisocyanate at room temperature, and is therefore useful as a polyol, which is a raw material for polyurethane. The copolymer according to the present invention may be any of a random copolymer, a block copolymer, and an alternating copolymer, but is preferably a random copolymer.

The molecular weight and molecular weight distribution of the copolymer according to the present invention can be appropriately set according to the application, and are not particularly limited. For example, from the viewpoint of low viscosity, the number average molecular weight (Mn) is preferably in the range of 500 to 10,000, more preferably in the range of 600 to 10,000, more preferably in the range of 800 to 8,000, and particularly preferably in the range of 1,000 to 6,000. The weight average molecular weight (Mw) is preferably in the range of 1,000 to 30,000, preferably in the range of 1,200 to 25,000, and even more preferably in the range of 1,500 to 15,000. Furthermore, the molecular weight distribution (Mw/Mn) is preferably less than 4.0, more preferably 3.5 or less, even more preferably less than 3.0, and even more preferably less than 2.0. Furthermore, from the viewpoint of low viscosity, the molecular weight distribution (Mw/Mn) is preferably 1.1 or more, and more preferably 1.2 or more.
In this specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by GPC (gel permeation chromatography) under the measurement conditions described below.

（一般式（１）中、Ｒ^１は、直鎖状、分岐鎖状、もしくは環状の、炭素数１～１０の脂肪族炭化水素基または炭素数３～７のエーテルから２個の水素原子を除いた基を表し、ｎは１～５の整数を示す。） (Vinyl ether)
The vinyl ether, which is a raw material monomer for the copolymer according to the present invention, is represented by the following general formula (1).

(In general formula (1), R ¹ represents a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group in which two hydrogen atoms have been removed from an ether group having 3 to 7 carbon atoms, and n represents an integer of 1 to 5.)

In general formula (1), examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ include an alkylene group having 1 to 10 carbon atoms or a group in which two hydrogen atoms have been removed from an alicyclic hydrocarbon having 5 to 10 carbon atoms. Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples of the alicyclic hydrocarbon having 5 to 10 carbon atoms include cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 ^2,6 ]decane, and decahydronaphthalene.

In general formula (1), examples of the ether having 3 to 7 carbon atoms represented by R ¹ include methyl ethyl ether, diethyl ether, methyl propyl ether, methyl isopropyl ether, ethyl propyl ether, ethyl isopropyl ether, methyl butyl ether, ethyl butyl ether, methyl sec-butyl ether, ethyl sec-butyl ether, methyl tert-butyl ether, and ethyl tert-butyl ether.

In general formula (1), the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 7, and more preferably 1 to 5, and the number of carbon atoms in the group obtained by removing two hydrogen atoms from the ether is preferably 3 to 6, and more preferably 3 to 5.
In formula (1), n is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

Examples of vinyl ethers represented by the general formula (1) include alkyl vinyl ethers such as hydroxymethyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-pentyl vinyl ether, 3-hydroxy-2-methyl-propyl vinyl ether, 2-hydroxy-1-methylethyl vinyl ether, 2-hydroxy-1-methylpropyl vinyl ether, 1-hydroxy-2-methylpropyl vinyl ether, and 3-hydroxy-3-methylpropyl vinyl ether; 2-hydroxycyclopentyl vinyl ether, 3-hydroxycyclopentyl vinyl ether, 2-hydroxycyclohexyl vinyl ether, 3-hydroxycyclohexyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 4-(hydroxymethyl)cyclohexyl vinyl ether, and 4-(2-hydroxypropyl)cyclohexyl vinyl ether. cycloalkyl vinyl ethers such as 2-hydroxycycloheptyl vinyl ether, 2-hydroxycyclooctyl vinyl ether, 4-hydroxycyclooctyl vinyl ether, and 2-hydroxycyclodecanyl vinyl ether; and alkoxy vinyl ethers such as diethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, 2-hydroxy-1-methoxyethyl vinyl ether, 1-hydroxy-2-methoxyethyl vinyl ether, 2-(hydroxymethoxy)ethyl vinyl ether, 1-(hydroxymethoxy)ethyl vinyl ether, 3-hydroxy-1-methoxypropyl vinyl ether, 3-hydroxy-1-ethoxypropyl vinyl ether, 4-hydroxy-1-ethoxybutyl vinyl ether, and 2-(2-hydroxyethyl)-1-methylethyl vinyl ether. Among these, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether are preferred in terms of radical polymerizability.

（一般式（２）中、Ｒ^２およびＲ^３は、それぞれ独立して、ヒドロキシ基、置換もしくは非置換のアルキル基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアラルキル基、置換もしくは非置換のアリール基、または置換もしくは非置換のアリールオキシ基を示す。また、Ｒ^２およびＲ^３は、互いに結合して環状構造を形成していてもよい。） (Vinyl phosphorus)
Vinyl phosphorus, which is a raw material monomer for the copolymer of the present invention, is represented by the following general formula (2).

(In general formula (2), ^R2 and ^R3 each independently represent a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group. ^R2 and ^R3 may be bonded to each other to form a cyclic structure.)

In the general formula (2), the number of carbon atoms of the alkyl groups of R ² and R ³ is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. The number of carbon atoms of the alkoxy group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. The number of carbon atoms of the cycloalkyl group is preferably 4 to 12, more preferably 5 to 10, and even more preferably 6 to 10. The number of carbon atoms of the aralkyl group is preferably 6 to 12, and more preferably 6 to 10. The number of carbon atoms of the aryl group is preferably 6 to 12, and more preferably 6 to 10. The number of carbon atoms of the aryloxy group is preferably 6 to 12, and more preferably 6 to 10. The number of carbon atoms of the substituents is not included in the above carbon numbers.

Examples of ^R2 and ^R3 include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, and a hexyl group; alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; cycloalkyl groups such as a cyclohexyl group; aralkyl groups such as a benzyl group and a phenethyl group; aryl groups such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group; and aryloxy groups such as a phenoxy group.

In general formula (2), examples of the substituent that ^R2 and ^R3 may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a heterocyclic group, an alkylidene group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group. The number of carbon atoms contained in the substituent is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 to 3.

Examples of vinyl ethers represented by general formula (2) include dimethyl vinylphosphonate, diethyl vinylphosphonate, diphenyl vinylphosphonate, diphenylvinylphosphine oxide, and 9,10-dihydro-9-oxa-10-vinyl-10-phosphaphenanthrene-10-oxide.

（一般式（３）中、Ｒ^２およびＲ^３は、一般式（２）中のＲ^２およびＲ^３と同義である。）
また、Ｒ^２およびＲ^３の好ましい態様については、上述の通りである。 (Method of synthesizing vinyl phosphorus)
The vinyl phosphorus represented by the above general formula (2) can be obtained, for example, by a hydrophosphorylation reaction of a phosphorus compound represented by the following general formula (3). Specifically, vinyl phosphorus can be synthesized by subjecting the raw material phosphorus compound represented by the following general formula (3) and acetylene to a hydrophosphorylation reaction in the presence of a catalyst.

(In formula (3), ^R2 and ^R3 have the same meanings as ^R2 and ^R3 in formula (2).)
The preferred embodiments of ^R2 and ^R3 are as described above.

The molar ratio of the phosphorus compound represented by general formula (3) and acetylene, which are raw materials for the hydrophosphorylation reaction, is preferably 0.01 to 1000, more preferably 0.1 to 100, and even more preferably 1 to 15, when the molar ratio of the phosphorus compound is taken as 1.

The reaction temperature for the hydrophosphorylation reaction is not particularly limited, but taking into consideration the reaction efficiency, reaction rate, and by-products, it is preferably -20 to 60°C, more preferably -15 to 40°C, and even more preferably -10 to 10°C. If the reaction temperature is within the above range, the reaction rate of the hydrophosphorylation reaction can be improved, and the conversion rate of the raw material phosphorus compound to vinyl phosphorus can be improved.

The reaction time for the hydrophosphorylation reaction is not particularly limited, but taking into consideration the reaction efficiency, reaction rate, and by-products, it is preferably 30 to 1000 minutes, more preferably 60 to 900 minutes, and even more preferably 120 to 800 minutes. If the reaction time is within the above range, the hydrophosphorylation reaction can be sufficiently advanced, and the conversion rate of the raw material phosphorus compound to vinyl phosphorus can be improved.

The hydrophosphorylation reaction may be carried out in the presence or absence of an organic solvent, but is preferably carried out in the absence of a solvent. The hydrophosphorylation reaction can be carried out by using a solvent-free method and gentle heating. The absence of a solvent makes it possible to omit the step of removing the solvent after the reaction is completed, thereby reducing production costs. The organic solvent is not particularly limited, but examples thereof include aromatic hydrocarbons, other hydrocarbons, alcohols, ethers, ketones, esters, etc.

The hydrophosphorylation reaction is preferably carried out under an inert gas atmosphere, taking into consideration the reaction efficiency, reaction rate, and by-products. As the inert gas, it is preferable to use nitrogen, argon, etc.

（一般式（１）中、Ｒ^１は、直鎖状、分岐鎖状、もしくは環状の、炭素数１～１０の脂肪族炭化水素基または炭素数３～７のエーテルから２個の水素原子を除いた基を表し、ｎは１～５の整数を示す。）
で表されるビニルエーテルと、
下記一般式（２）：

（一般式（２）中、Ｒ^２およびＲ^３は、それぞれ独立して、ヒドロキシ基、置換もしくは非置換のアルキル基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアラルキル基、置換もしくは非置換のアリール基、または置換もしくは非置換のアリールオキシ基を示す。また、Ｒ^２およびＲ^３は、互いに結合して環状構造を形成していてもよい。）
で表されるビニルリンとを、溶媒存在下または無溶媒で、ラジカル重合開始剤を用いて重合させる工程を含むものである。なお、一般式（１）中のＲ^１ならびに一般式（２）中のＲ^２およびＲ^３の好ましい態様については、上述の通りである。 [Method for producing a copolymer of vinyl ether and vinyl phosphorus]
The method for producing the copolymer according to the present invention comprises reacting a compound represented by the following general formula (1):

(In general formula (1), R ¹ represents a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group in which two hydrogen atoms have been removed from an ether group having 3 to 7 carbon atoms, and n represents an integer of 1 to 5.)
and a vinyl ether represented by the formula:
The following general formula (2):

(In general formula (2), ^R2 and ^R3 each independently represent a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group. ^R2 and ^R3 may be bonded to each other to form a cyclic structure.)
The method includes a step of polymerizing a vinyl phosphorus represented by the formula (1) with a radical polymerization initiator in the presence or absence of a solvent. The preferred embodiments of R ¹ in the formula (1) and R ² and R ³ in the formula (2) are as described above.

Examples of radical polymerization initiators include azo-based polymerization initiators and peroxide-based polymerization initiators. Azo-based polymerization initiators include ester-type azo compounds such as dimethyl 2,2'-azobis(2-methylpropionate) (MAIB), dimethyl 2,2'-azobis(2-methylbutyrate), and dimethyl 2,2'-azobis(2-methylpentanoate); 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2-azobis(2,4-dimethylvaleronitrile). Examples of such compounds include nitrile-type azo compounds such as bis(4-methoxy-2,4-dimethylvaleronitrile) and 1,1'-azobis(cyclohexane-1-carbonitrile); and acid amide-type azo compounds such as 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide.

Examples of peroxide-based polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, and cyclohexanone peroxide; diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, and lauroyl peroxide; dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide; peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-di-t-butylperoxycyclohexane, and 2,2-di(t-butylperoxy)butane; t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisobutylene. peroxyesters such as di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxylaurate, and t-hexylperoxybenzoate; and peroxycarbonates such as diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, and t-butylperoxyisopropylcarbonate.

Among the above radical polymerization initiators, azo-based polymerization initiators are preferred in terms of molecular weight reproducibility, azoester compounds and nitrile-type azo compounds are more preferred, azoester compounds are even more preferred, and dimethyl 2,2'-azobis(2-methylpropionate) (MAIB) is even more preferred.

The radical polymerization initiator may be used alone or in combination of two or more kinds. The amount of radical polymerization initiator used can be appropriately adjusted depending on the reaction temperature, the type of radical polymerization initiator, the type and composition of the vinyl ether and vinyl phosphorus raw materials, the molecular weight of the resulting copolymer, etc. For example, it is preferably 0.1 to 10 mol %, more preferably 0.5 to 5 mol %, based on the total amount of raw material monomers.

As the polymerization solvent, an organic solvent can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, and butanol; esters such as methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, methyl propionate, methyl lactate, and ethyl lactate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, 1,4-dioxane, and ethylene glycol dimethyl ether; chlorine-based solvents such as dichloromethane and trichloromethane, hydrocarbons such as hexane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene, and styrene. These organic solvents may be used alone or in combination of two or more. Among these, it is preferable to use at least one selected from the group consisting of ethanol, butanol, butyl acetate, and toluene.

(Polymerization method)
The polymerization method is not particularly limited, but for example, the raw material monomers, the radical polymerization initiator, and optionally a polymerization solvent are charged in advance into a reactor, and the polymerization can be initiated by raising the temperature. The molar ratio of the mixed amounts of the vinyl ether represented by general formula (1) and the vinyl phosphorus represented by general formula (2), which are raw material monomers, is preferably 95:5 to 5:95, more preferably 80:20 to 20:80.

Polymerization may also be initiated by adding a radical polymerization initiator to the heated raw material monomer or raw material monomer solution. The radical polymerization initiator may be added gradually or all at once. Alternatively, these methods may be combined, with a portion of the radical polymerization initiator being charged in advance in the reactor, and the remainder then being added gradually to the reaction system. In the case of gradually adding the initiator, the operation becomes more complicated, but the polymerization reaction is easier to control.

Furthermore, if there is concern about a temperature rise due to heat generation or if the reaction rates of multiple raw material monomers differ greatly, the raw material monomer or raw material monomer solution may be added in portions or continuously. In this case, the temperature may be raised to the reaction temperature when a portion of the raw material monomer or raw material monomer solution is added to the reactor, and the remainder may then be added in portions or continuously, or a solvent may be charged in the reactor in advance, and the raw material monomer or raw material monomer solution may be added in portions or continuously to the heated solvent. In addition, the radical polymerization initiator may be charged in the reactor in advance, or may be added to the system together with the monomer or separately, or a portion of the radical polymerization initiator may be charged in the reactor in advance, and the remainder may then be added successively to the reaction system. Such a method makes it easier to control the polymerization reaction, since it is possible to suppress a temperature rise due to heat generation.

After the reaction is completed, the vinyl ether and vinyl phosphorus copolymer produced is isolated by post-treatment using known operations and processing methods (e.g., neutralization, solvent extraction, water washing, separation, solvent distillation, reprecipitation, etc.).

The polymerization temperature may be appropriately selected depending on the type of radical polymerization initiator, and the reaction may be carried out by changing the temperature in stages. In general, it is preferable that the temperature is within the range of 50 to 180°C, and it is particularly preferable that the temperature is within the range of 60 to 170°C. If the reaction temperature is 50°C or higher, the reaction rate can be maintained, and if the reaction temperature is 180°C or lower, decomposition of the radical polymerization initiator can be suppressed and polymerization can be carried out efficiently.

The polymerization time varies depending on the type and amount of reagents and the reaction temperature, but is preferably 2 to 90 hours, more preferably 2 to 50 hours, and even more preferably 3 to 30 hours.

[Flame-retardant thermosetting resin composition]
The flame-retardant thermosetting resin composition according to the present invention contains the above-mentioned copolymer and a monomer for a thermosetting resin, and may further contain other components. The flame retardant component is phosphorus. By using a compound capable of undergoing a polymerization addition reaction with the copolymer (polyol) as a monomer for thermosetting resin, the copolymer and the monomer for thermosetting resin can be The flame-retardant component (phosphorus atom) is chemically bonded and incorporated into the resin obtained by the reaction. Therefore, the flame-retardant component does not bleed out from the resin, and a high flame-retardant effect is achieved by adding a small amount of copolymer. Furthermore, in the flame-retardant thermosetting resin composition according to the present invention, since the copolymer is compatible with the monomer for thermosetting resin at room temperature (e.g., 10 to 30° C.), It is easy to handle.

As the monomer for the thermosetting resin, one capable of undergoing a polymerization addition reaction with the above-mentioned copolymer (polyol) is preferred, and a diisocyanate is more preferred. Examples of diisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and naphthalene diisocyanate. These diisocyanates may be used alone or in combination of two or more. Among these, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate are preferred.

Other components include, for example, epoxy compounds. Examples of epoxy compounds include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, and bisphenol Z type epoxy resin; novolac type epoxy resins such as bisphenol A novolac type epoxy resin, phenol novolac type epoxy resin, and cresol novolac epoxy resin; biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, aryl alkylene type epoxy resin, tetraphenylol ethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, glycidyl methacrylate copolymer epoxy resin, and copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate. These epoxy compounds may be used alone or in combination of two or more.

Other components include, in addition to the epoxy compound, conventionally known additives used in thermosetting resin compositions, such as antioxidants, leveling agents, defoamers, chain transfer agents, heat stabilizers, matting agents, diluents, plasticizers, and thickeners.

The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these examples.

In the following Examples and Comparative Examples, the conversion rate of the raw material monomers was analyzed and the physical properties of the resulting copolymers were evaluated by the following methods.
(1) The analysis of the monomer conversion rate was carried out by gas chromatography (GC). The "monomer conversion rate" refers to the consumption rate of the monomer after polymerization relative to the monomer before the start of polymerization, calculated from the peak area of the monomer measured by gas chromatography (GC) under the measurement conditions described below (GC conditions).
Column: DB-1 (Agilent Technologies, Inc.)
Heating program: Hold at 50°C for 5 minutes → Heat at 10°C/min → Hold at 250°C for 5 minutes Carrier gas: Nitrogen Column flow rate: 0.95 ml/min Detector: Flame ionization detector (FID)
(2) Analysis of number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) was carried out by gel permeation chromatography (GPC) under the measurement conditions described below.
(GPC conditions)
Column: Shodex GPC LF804 x 3 (Showa Denko K.K.)
Solvent: Tetrahydrofuran Measurement temperature: 40°C
Flow rate: 1.0 ml/min. Calibration curve: standard polystyrene. Standard (3) Analysis of the chemical structure of the copolymer was carried out using MALDI-MS under the measurement conditions described below.
(MALDI-MS conditions)
Analytical equipment: Bruker Rapiflex TOF/TOF type Matrix-assisted laser deionization Reflector/Positive mode Mass measurement range: 100 to 6000
Matrix: Dithranol Cationizing agent: Sodium trifluoroacetate

<Synthesis Example 1 of Vinyl Phosphorus>
3.71 g of nickel chloride, 2.18 g of zinc, and 30.3 g of triphenylphosphine were weighed out in a 1 L three-neck flask, and the inside of the vessel was replaced with nitrogen. 42.0 g of toluene was added thereto, and the mixture was heated and stirred at 95° C. for 6 hours to obtain a mixture of a nickel complex and a low-polarity additive.

Next, 21.0 g of zinc chloride and the entire mixture of the nickel complex and low-polarity additive obtained above as a catalyst were added to 420 g of dimethyl phosphite, and acetylene gas was blown in. The reaction temperature changed between 25 and 28°C, and 3.19 mol of gas was absorbed over 660 minutes, yielding crude dimethyl vinylphosphonate. This crude was distilled under reduced pressure at a reduced pressure of 1.0 kPa, and 285 g of a fraction with a boiling point of 60 to 63°C was collected, yielding dimethyl vinylphosphonate.

<Synthesis Example 2 of Vinyl Phosphorus>
In a 170 L reactor, 50.6 kg of methanol was added to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA manufactured by Sanko Co., Ltd.) and dissolved. After replacing the atmosphere inside the reactor with nitrogen, 0.3 kg of tetrakis(trimethylphosphine)nickel(0) was added and stirred at 0°C for 10 minutes. Acetylene was blown into the reactor at a flow rate of 0.28 kg/h for 3.2 hours. Methanol was distilled off from the reaction liquid, and the fraction obtained by heating at 175°C under a vacuum of 0.3 mmHg was collected to obtain 9,10-dihydro-9-oxa-10-vinyl-10-phosphaphenanthrene-10-oxide.

<Production of Copolymer>
[Example 1]
Into a 50 mL glass Schlenk flask, 1.75 g (12.9 mmol) of vinyl phosphorus (hereinafter referred to as "P1M") obtained in Synthesis Example 1 above, 4.21 g (4.8 mmol) of 2-hydroxyethyl vinyl ether (hereinafter referred to as "HEVE"), and 0.046 g (1 mol % relative to the total amount of monomers) of methyl 2,2'-azobisisobutyrate ("V-601" manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as "MAIB") were added, and the mixture was polymerized at 70°C for 18 hours to obtain a copolymer. The yield of the obtained copolymer was 5.02 g.

[Example 2]
A copolymer was obtained by polymerization reaction in the same manner as in Example 1, except that 5.04 g (3.8 mmol) of diethylene glycol vinyl ether (hereinafter referred to as "DEGV") was added instead of HEVE. The yield of the obtained copolymer was 6.12 g.

[Comparative Example 1]
A copolymer was obtained by carrying out a polymerization reaction in the same manner as in Example 1, except that 5.00 g (3.8 mmol) of 2-hydroxyethyl methacrylate (hereinafter referred to as "HEMA") was added instead of HEVE. The yield of the obtained copolymer was 6.70 g.

<Evaluation of copolymer>
(Compatibility)
Each of the copolymers obtained in the above Examples 1 and 2 and Comparative Example 1 was mixed with hexamethylene diisocyanate at 20° C., and the compatibility was visually confirmed.

(GPC Analysis)
For the copolymer obtained in Example 1, the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were measured by the above-mentioned GPC analysis.

The results of Examples 1 and 2 and Comparative Example 1 above are listed in Table 1.

<Preparation of Flame-Retardant Thermosetting Resin Composition>
[Example 2]
1.0 g of the copolymer (P1M-DEGV) obtained above and 0.47 g of hexamethylene diisocyanate were added to a flask at 20° C. to obtain a flame-retardant thermosetting resin composition. The appearance of this flame-retardant thermosetting resin composition was a uniform viscous liquid. This flame-retardant thermosetting resin composition was subjected to a polymerization addition reaction at 110° C. for 2 hours to produce polyurethane. The flame-retardant thermosetting resin composition according to the present invention was suitable as a polyol for producing polyurethane.

[Comparative Example 1]
1.0 g of the copolymer (P1M-HEMA) obtained above and 0.48 g of hexamethylene diisocyanate were added to a flask at 20° C., but they were not mixed uniformly and were a mixture of solid resin and liquid. Therefore, the copolymer obtained in Comparative Example 1 was not suitable as a polyol for producing polyurethane.

<Production of Copolymer>
[Example 3]
In a flask, 1.36 g (10 mmol) of P1M and 0.88 g (10 mmol) of HEVE were added as raw material monomers, 46.1 mg (1 mol % relative to the total amount of monomers) of MAIB as a polymerization initiator, and butyl acetate as a solvent, and the mixture was polymerized at 70° C. for 18 hours to obtain a copolymer. The conversion rate of P1M was 100%, and the conversion rate of HEVE was 54.7%. The conversion rate of the monomers was measured by identifying each component by GC-FID under the above conditions.

[Example 4]
A copolymer was obtained by polymerization reaction in the same manner as in Example 3, except that 1.32 g (10 mmol) of DEGV was added instead of HEVE and no solvent was added. The conversion of P1M was 87.9%, and the conversion of DEGV was 79.7%.

[Example 5]
A copolymer was obtained by carrying out a polymerization reaction in the same manner as in Example 3, except that 1.16 g (10 mmol) of 4-hydroxybutyl vinyl ether (hereinafter referred to as "HBVE") was added instead of HEVE and no solvent was added. The conversion of P1M was 100%, and the conversion of HBVE was 35.6%.

[Example 6]
A copolymer was obtained by polymerization reaction in the same manner as in Example 3, except that 0.457 g (2 mmol) of diphenylvinylphosphine oxide (manufactured by Fujifilm Wako Chemicals Co., Ltd., hereinafter referred to as "P4M") was added instead of P1M, the amount of HEVE used was 1.94 g (22 mmol), and ethanol was added instead of butyl acetate. The conversion of P4M was 56.0%, and the conversion of HEVE was 58.7%.

[Example 7]
A copolymer was obtained by polymerization reaction in the same manner as in Example 3, except that 2.16 g (10 mmol) of the vinyl phosphorus obtained in Synthesis Example 2 (hereinafter referred to as "P5M") was added instead of P1M and no solvent was added. The conversion of P5M was 100%, and the conversion of HEVE was 68.3%.

[Example 8]
A copolymer was obtained by polymerization reaction in the same manner as in Example 3, except that 0.033 g (1 mol % based on the total amount of monomers) of 2,2'-azobisisobutyronitrile (hereinafter referred to as "AIBN") was added instead of MAIB. The conversion of P1M was 87.3%, and the conversion of HEVE was 77.3%.

[Example 9]
A copolymer was obtained by polymerization reaction in the same manner as in Example 3, except that 2.72 g (20 mmol) of P1M, 1.76 g (20 mmol) of HEVE, and 4.58 g of 2-butanol were added instead of butyl acetate. The conversion of P1M was 100%, and the conversion of HEVE was 66.7%.

[Example 10]
A copolymer was obtained by polymerization reaction in the same manner as in Example 3, except that 13.6 g (100 mmol) of P1M, 8.8 g (100 mmol) of HEVE, and 11.2 g of 2-butanol were added instead of butyl acetate. The conversion of P1M was 100%, and the conversion of HEVE was 56.9%.

[Example 11]
A copolymer was obtained by carrying out a polymerization reaction in the same manner as in Example 3, except that toluene was used instead of butyl acetate. The conversion of P1M was 100%, and the conversion of HEVE was 75.4%.

[Example 12]
A copolymer was obtained by polymerization reaction in the same manner as in Example 8, except that methyl ethyl ketone peroxide was used instead of AIBN. The conversion of P1M was 100%, and the conversion of HEVE was 45.3%.

<Evaluation of copolymer>
(Compatibility)
Each of the copolymers obtained in Examples 3 to 12 above was mixed with hexamethylene diisocyanate at 20° C., and the compatibility was visually confirmed.

(GPC Measurement)
The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were measured by the above GPC analysis for the copolymers obtained in the above Examples 3 to 5 and 8 to 12. The copolymers obtained in Examples 6 and 7 were not measured because they were not dissolved in the analysis solvent.

(MALDI-MS measurement)
The copolymer obtained in Example 9 was subjected to the above-mentioned MALDI-MS measurement. The obtained MALDI-MS spectrum is shown in FIG. 1. The monomers were randomly introduced from the positions of the peaks marked with circles. Based on these results, as well as the results of GPC analysis, the nature of the monomer, the change in the monomer over time during the reaction, and the absence of vinyl phosphorus elimination from the thermoset product, it was estimated that the copolymer was It was found to be a random copolymer. It was presumed that the copolymers obtained in the other Examples 1 to 8 and 10 to 12 were also random copolymers.

The results of Examples 3 to 12 above are listed in Table 2.

Claims (15)

A copolymer of vinyl ether and vinyl phosphorus (excluding copolymers using a fluorine-containing monomer as a raw material monomer) ,
The vinyl ether is represented by the following general formula (1):
(In general formula (1), R ¹ represents a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group in which two hydrogen atoms have been removed from an ether group having 3 to 7 carbon atoms, and n represents an integer of 1 to 5.)
It is expressed as
The vinyl phosphorus is represented by the following general formula (2):
(In general formula (2), ^R2 and ^R3 each independently represent a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group. ^R2 and ^R3 may be bonded to each other to form a cyclic structure.)
A copolymer represented by the formula: The copolymer according to claim 1, wherein the number average molecular weight (Mn) of the copolymer is in the range of 500 to 10,000. The copolymer according to claim 1 or 2, wherein the vinyl ether is at least one selected from the group consisting of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. The copolymer according to any one of claims 1 to 3, wherein in the general formula (2), R ² and R ³ are each independently a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The copolymer according to any one of claims 1 to 4, wherein the vinyl phosphorus is at least one selected from the group consisting of dimethyl vinylphosphonate, diethyl vinylphosphonate, diphenyl vinylphosphonate, diphenylvinylphosphine oxide, and 9,10-dihydro-9-oxa-10-vinyl-10-phosphaphenanthrene-10-oxide. The copolymer according to any one of claims 1 to 5, wherein the copolymer is compatible with a monomer for a thermosetting resin at 10 to 30°C. The copolymer according to claim 6, wherein the monomer for the thermosetting resin is a diisocyanate. The copolymer according to claim 7, wherein the diisocyanate is at least one selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate. A flame-retardant thermosetting resin composition comprising the copolymer according to any one of claims 1 to 8 and a monomer for a thermosetting resin. A method for producing a copolymer of vinyl ether and vinyl phosphorus (excluding copolymers using a fluorine-containing monomer as a raw material monomer) , comprising the steps of:
The following general formula (1):
(In general formula (1), R ¹ represents a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group in which two hydrogen atoms have been removed from an ether group having 3 to 7 carbon atoms, and n represents an integer of 1 to 5.)
and a vinyl ether represented by the formula:
The following general formula (2):
(In general formula (2), ^R2 and ^R3 each independently represent a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group. ^R2 and ^R3 may be bonded to each other to form a cyclic structure.)
and a vinyl phosphorus represented by the formula (I) in the presence or absence of a solvent, using a radical polymerization initiator. The method according to claim 10, wherein the radical polymerization initiator is at least one selected from the group consisting of azo-based polymerization initiators and peroxide-based polymerization initiators. The method according to claim 10 or 11, wherein the radical polymerization initiator is at least one selected from the group consisting of ester-type azo compounds and nitrile-type azo compounds. The method according to any one of claims 10 to 12, wherein the solvent is an organic solvent. The method according to claim 13, wherein the organic solvent is at least one selected from the group consisting of alcohols, esters, ketones, ethers, chlorinated solvents, hydrocarbon solvents, and aromatic hydrocarbons. The method according to claim 13 or 14, wherein the organic solvent is at least one selected from the group consisting of ethanol, butanol, butyl acetate, and toluene.