JP2008195855A - Polymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer having a new structure and to provide a method for producing the polymer. <P>SOLUTION: The polymer is prepared by carrying out ring opening addition reaction of (a) a compound having two or more oxetanyl groups in a molecule with (b) an arylene dihalide represented by formula (I): X<SP>1</SP>-CH<SB>2</SB>-Ar-CH<SB>2</SB>-X<SP>2</SP>(wherein Ar is a divalent aromatic group; X<SP>1</SP>and X<SP>2</SP>are each independently a halogen atom). The method for producing the polymer comprises a step of carrying out ring opening addition reaction of (a) a compound having two or more oxetanyl groups in the same molecule with (b) an arylene dihalide represented by formula (I). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymer obtained by a ring-opening polyaddition reaction between a compound having two or more oxetanyl groups in the same molecule and an arylene halide, and a method for producing the same.

The ultraviolet (UV) / electron beam (EB) curing reaction has been widely developed in fields such as printing, paints, coating materials, adhesives and photosensitive dry films. The UV / EB curing reaction is superior in terms of resource saving, energy saving, environmental conservation, space saving, productivity, etc., compared to conventional curing methods, ie, drying methods containing a large amount of solvent and curing methods by heating. Because.
In addition, UV curable materials have been improved in various ways along with the spread of photocuring applications. Among them, radical polymerization type UV curable materials based on acrylates have problems due to reaction mechanisms such as volume shrinkage. Considering the development of new industries in the future, the development of UV curing technology that can be applied to various uses is indispensable, and the development of a UV curing system based on a new concept is required.

On the other hand, epoxides, which are three-membered cyclic ether compounds, are very useful substances for organic synthesis and polymer synthesis because they exhibit a variety of reactivity not found in other cyclic ethers due to large strain energy. Furthermore, a polymer material using an epoxy compound is excellent in heat resistance, chemical resistance, electrical insulation, and the like. However, it is known that storage stability is poor due to its high reactivity.
In addition, oxetanes, which are four-membered cyclic ethers, have very low reactivity compared to epoxies, although their ring strain energy is comparable to that of epoxies. Known and good storage stability. In recent years, it has been found that the reaction of oxetanes has the same reactivity as epoxides by selecting reaction conditions and catalysts. This suggests that oxetanes can be used as an alternative to epoxies, which is also useful in terms of environment.

  As the synthesis of polymers using oxetanes, the addition reaction between a polymer having one oxetane ring in the side chain of a repeating structural unit and a polycarboxylic acid having two or more carboxyl groups in the molecule has been reported. (For example, refer to Patent Document 1). Moreover, the method by the polyaddition reaction of an oxetane compound and a polyfunctional carboxylic acid compound is known (for example, refer patent document 2).

Japanese Patent Laid-Open No. 11-236438 JP 2002-003585 A

  An object of the present invention is to provide a polymer having a novel structure and a method for producing the same.

As a result of intensive studies to overcome the problems in the prior art, the present inventors have found that the above problems can be achieved by the following <1> and <3>, and have completed the present invention. It is described below together with <2>, <4> and <5> which are preferred embodiments.
<1> Polymerization obtained by ring-opening polyaddition reaction of a compound (a) having two or more oxetanyl groups in the same molecule and an arylene halide (b) represented by the formula (I) object,

（式中、Ａｒは二価の芳香族基を表し、Ｘ¹及びＸ²はそれぞれ独立に、ハロゲン原子を表す。）
＜２＞ 前記（ａ）が下記式（II）で表される同一分子内に２つのオキセタニル基を有する化合物であり、式（III）で表される繰り返し構造を含む上記＜１＞に記載の重合物、

(In the formula, Ar represents a divalent aromatic group, and X ¹ and X ² each independently represent a halogen atom.)
<2> The compound according to <1>, wherein (a) is a compound having two oxetanyl groups in the same molecule represented by the following formula (II) and includes a repeating structure represented by the formula (III): Polymer,

（式中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子、又は、炭素数１〜６のアルキル基を表し、Ａは二価の連結基を表し、Ａｒは二価の芳香族基を表し、Ｘ¹及びＸ²はそれぞれ独立に、ハロゲン原子を表す。）
＜３＞ 同一分子内に２つ以上のオキセタニル基を有する化合物（ａ）と式（I）で表されるアリーレンジハライド（ｂ）との開環重付加反応を行う工程を含むことを特徴とする重合物の製造方法、

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A represents a divalent linking group, and Ar represents a divalent aromatic group. , X ¹ and X ² each independently represents a halogen atom.)
<3> including a step of performing a ring-opening polyaddition reaction between the compound (a) having two or more oxetanyl groups in the same molecule and the arylene halide (b) represented by the formula (I) A method for producing a polymer,

（式中、Ａｒは二価の芳香族基を表し、Ｘ¹及びＸ²はそれぞれ独立に、ハロゲン原子を表す。）
＜４＞ 前記（ａ）が下記式（II）で表される同一分子内に２つのオキセタニル基を有する化合物である上記＜３＞に記載の重合物の製造方法、
＜５＞ 前記開環重付加反応を第四級オニウム塩の存在下で行う上記＜３＞又は＜４＞に記載の重合物の製造方法。

(In the formula, Ar represents a divalent aromatic group, and X ¹ and X ² each independently represent a halogen atom.)
<4> The method for producing a polymer according to <3>, wherein (a) is a compound having two oxetanyl groups in the same molecule represented by the following formula (II):
<5> The method for producing a polymer according to <3> or <4>, wherein the ring-opening polyaddition reaction is performed in the presence of a quaternary onium salt.

  ADVANTAGE OF THE INVENTION According to this invention, the polymer which has a novel structure, and its manufacturing method can be provided.

  The polymer of the present invention is represented by the compound (a) having two or more oxetanyl groups in the same molecule (hereinafter also referred to as “compound (a)” or “(a)”) and the formula (I). It is obtained by ring-opening polyaddition reaction with arylene halide (b) (hereinafter also referred to as “compound (b)” or “(b)”).

（式中、Ａｒは二価の芳香族基を表し、Ｘ¹及びＸ²はそれぞれ独立に、ハロゲン原子を表す。）

(In the formula, Ar represents a divalent aromatic group, and X ¹ and X ² each independently represent a halogen atom.)

  Below, the polymer of this invention and its manufacturing method are explained in full detail.

(Polymer)
The polymer of the present invention is a polymer obtained by a ring-opening polyaddition reaction between a compound (a) having two or more oxetanyl groups in the same molecule and an arylene halide (b) represented by the formula (I) And a polymer having a partial structure as shown in the following formula (c) at least in part. The polymer of the present invention is a polymer having a halomethyl group as shown in the following formula (c). The “halomethyl group” in the present invention is a general term for a fluoromethyl group, a chloromethyl group, a bromomethyl group, and an iodomethyl group.

（式中、Ｒは一価の置換基を表し、Ａはｎ価の連結基を表し、ｎは２以上の整数を表し、Ａｒは二価の芳香族基を表し、Ｘ¹及びＸ²はそれぞれ独立に、ハロゲン原子を表し、ｎ個存在するＲは同一であっても異なっていてもよく、また、波線部はＡとの結合部分を表す。）

(In the formula, R represents a monovalent substituent, A represents an n-valent linking group, n represents an integer of 2 or more, Ar represents a divalent aromatic group, and X ¹ and X ² represent Each independently represents a halogen atom, and n existing Rs may be the same or different, and the wavy line part represents a bonding part to A.)

X ¹ and X ^{2 in} the formula (I) each independently represent a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), preferably a chlorine atom, bromine atom or iodine atom, From the viewpoint of balance between stability and stability, a chlorine atom or a bromine atom is more preferable. When modifying the halomethyl group in the obtained polymer, it is particularly preferably a bromine atom having excellent reactivity.
Ar in the formula (I) represents a divalent aromatic group, and is preferably a phenylene group, a biphenylene group, a naphthalenediyl group, or an anthracenediyl group, more preferably a phenylene group, More preferred is a 4-phenylene group.
The phenylene group, naphthalenediyl group, or anthracenediyl group may have a substituent. The substituent is not particularly limited as long as it is a group that does not cause a problem in the ring-opening polyaddition reaction between the compound (a) and the compound (b), and the number of substituents is not particularly limited as much as possible.
Examples of substituents include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups, alkyl groups having 1 to 6 carbon atoms, and halogen-substituted alkyl groups having 1 to 6 carbon atoms. , An aryl group having 4 to 12 carbon atoms, a halogen-substituted aryl group having 4 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and 1 to 7 carbon atoms Preferred examples include an acyl group, an acyloxy group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, and an amide group having 2 to 7 carbon atoms. A halogen atom (fluorine atom, chlorine atom, bromine) Atom, iodine atom), nitro group, alkyl group having 1 to 6 carbon atoms, or alkoxy group having 1 to 6 carbon atoms can be exemplified more preferably.
Moreover, the arylene halide (b) represented by the formula (I) that can be used in the present invention may be used singly or in combination of two or more.

  Specific examples of the compound (b) include 1,2-bis (chloromethyl) benzene, 1,3-bis (chloromethyl) benzene, 1,4-bis (chloromethyl) benzene, 4,4-bis (chloro Methyl) biphenyl, 2,4-bis (chloromethyl) mesitylene, 2,3-bis (chloromethyl) naphthalene, 1,4-bis (chloromethyl) tetrafluorobenzene, 2,5-bis (chloromethyl) -p Xylene, 1,4-bis (chloromethyl) -2,5-dimethoxybenzene, 9,10-bis (chloromethyl) anthracene, 3,6-bis (chloromethyl) durene, 2,6-bis (chloromethyl) ) Pyridine, 1,2-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) benzene, 1,4-bis (bromomethyl) benzene, 4,4-bis ( Lomomethyl) biphenyl, 2,4-bis (bromomethyl) mesitylene, 2,3-bis (bromomethyl) naphthalene, 1,4-bis (bromomethyl) tetrafluorobenzene, 2,5-bis (bromomethyl) -p-xylene, , 4-bis (bromomethyl) -2,5-dimethoxybenzene, 9,10-bis (bromomethyl) anthracene, 3,6-bis (bromomethyl) durene, 2,6-bis (bromomethyl) pyridine, 1,2-bis (Iodomethyl) benzene, 1,3-bis (iodomethyl) benzene, 1,4-bis (iodomethyl) benzene, 4,4-bis (iodomethyl) biphenyl, 2,4-bis (iodomethyl) mesitylene, 2,3-bis (Iodomethyl) naphthalene, 1,4-bis (iodomethyl) tetrafluorobenzene, , 5-bis (iodomethyl) -p-xylene, 1,4-bis (iodomethyl) -2,5-dimethoxybenzene, 9,10-bis (iodomethyl) anthracene, 3,6-bis (iodomethyl) durene, 2, Examples include 6-bis (iodomethyl) pyridine.

As the compound (a) having two or more oxetanyl groups in the same molecule that can be used in the present invention, the compound (a) and the compound (b) can be opened as long as the compound has two or more oxetanyl groups. As long as there is no problem in the cycloaddition reaction, the structure other than the oxetanyl group is not particularly limited, and any compound can be selected.
The compound (a) that can be used in the present invention is preferably a compound having 2 or 3 oxetanyl groups, and when a linear polymer is obtained, it may be a compound having 2 oxetane rings. More preferred.
Further, as compound (a), a compound having two oxetane rings, a compound having three oxetane rings, a compound having four oxetane rings, and five or more oxetane rings as described later. Preferred examples are compounds.
Moreover, the compound (a) which can be used for this invention may be used individually by 1 type, or may be used in combination of 2 or more type.

<Compound having two oxetane rings>
Examples of the compound having two oxetane rings include a compound represented by the following formula (1).

R ^{1 in} formula (1) represents a hydrogen atom or an optionally branched alkyl group having 1 to 6 carbon atoms, and R ² represents an optionally branched alkylene group having 2 to 6 carbon atoms. , A phenylene group, a phenylene group having 1 to 2 alkyl groups having 1 to 6 carbon atoms which may be branched, a biphenylene group, and 2 alkyl groups having 1 to 6 carbon atoms which may be branched. Represents a group represented by the following formula (2), a group represented by the formula (3) or a group represented by the formula (4).

R ^{3 in the} formula (2) represents an optionally branched alkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 to 10.

R ^{4 in} formula (3) represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom. Examples of the bonding position of the group having an oxetane ring in the formula (3) include 1,2-position, 1,3-position, and 1,4-position, and preferably 1,4-position.

R ^{5 in the} formula (4) represents an oxygen atom, a sulfur atom, a methylene group, —NH—, —SO—, —SO ₂ —, —C (CF ₃ ) ₂ — or —C (CH ₃ ) ₂ —. . The bonding positions of the group having an oxetane ring in the formula (4) are 2, 2 ′ position, 2, 3 ′ position, 2, 4 ′ position, 3, 3 ′ position, 3, 4 ′ position, and 4, 4 ′ position. Preferably, the 4,4 ′ position is more preferable.

  Moreover, as a compound which has two oxetane rings, the compound etc. which are shown by following formula (5) are mentioned.

R ^{1 in} formula (5) is the same group as in formula (1), and R ⁶ and R ⁷ each independently represents an alkylene group which may have 1 to 8 carbon atoms. .
R ⁶ and R ⁷ are preferably the same group, preferably an alkylene group which may have 1 to 3 carbon atoms, and more preferably a methylene group.

  Examples of the compound having two oxetane rings that can be used in the present invention include carbonate bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and 3,7-bis (3-oxetanyl) -5-oxa. -Nonane, 3,3 '-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis (3-ethyloxetane), 1,2-bis [(3-ethyl-3-oxetanylmethoxy) Methyl] benzene, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [ (3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl 3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3 -Oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3 -Oxetanylmethoxy) hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 2,3-bis [(3-ethyloxetan-3-yl) methoxymethyl] norbornane, 4,4'-bis [( 3-ethyloxetane-3-yl) metoxy ] Biphenyl, 2,2'-bis [(3-ethyl-3-oxetanyl) methoxy] biphenyl, 2,7-bis [(3-ethyloxetan-3-yl) methoxy] naphthalene, 3,3 ', 5 5′-tetramethyl [4,4′-bis (3-ethyloxetane-3-yl) methoxy] biphenyl, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3 -Ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified Bisphenol F (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-{[(3- Preferable examples include til-3-oxetanyl) methoxy] methyl} oxetane.

  Among these, compounds having two oxetane rings include 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (1,3-BEOMB), 1,4-bis [(3 -Ethyl-3-oxetanylmethoxy) methyl] benzene (1,4-BEOMB), 4,4′-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl (4,4′-BEOBP), 2, 2′-bis [(3-ethyl-3-oxetanyl) methoxy] biphenyl, 3-ethyl-3-{[(3-ethyl-3-oxetanyl) methoxy] methyl} oxetane (OXT-221) and the like are more preferable examples. it can.

<Compound having 3 to 4 oxetane rings>
Examples of the compound having 3 to 4 oxetane rings that can be used in the present invention include compounds represented by the following formula (6).

R ^{1 in} formula (6) is the same group as in formula (1), and R ⁸ is a carbon number that may have a trivalent (j = 3) or tetravalent (j = 4) branch. 4 to 12 alkyl, more preferably j = 3 in the following formula (7), j = 4 in the following formula (8), and j = 4 in the following formula (9).

R ^{9 in} Formula (6) represents a C 1-6 alkyl group which may have a branch. R ^{7 in} formula (6) is preferably a methyl group, an ethyl group or a propyl group.

<Compound having 5 or more oxetane rings>
Examples of the oxetane compound having 5 or more oxetane rings in the molecule include those in which 5 or more oxetane rings are bonded to a phenol novolac polymer, and those in which 5 or more oxetane rings are bonded to an alkyl chain.

  In addition, as an oxetane compound having two or more oxetane rings in the molecule, a compound in which a group having an oxetanyl group is bonded to silicate or silsesquioxane can be exemplified, and one oxetanyl group is included in silicate or silsesquioxane. A compound in which two or more groups are bonded is preferable.

  Examples of compounds having an oxetane ring in the molecule that can be used in the present invention include 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (1,3-BEOMB), 1,4. -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (1,4-BEOMB), 4,4′-bis [(3-ethyloxetan-3-yl) methoxy] biphenyl (4,4′- BEOBP), 2,2′-bis [(3-ethyl-3-oxetanyl) methoxy] biphenyl, 3-ethyl-3-{[(3-ethyl-3-oxetanyl) methoxy] methyl} oxetane (OXT-221, Manufactured by Toagosei Co., Ltd.), oxetanylsilsesquioxane (OX-SQ series, manufactured by Toagosei Co., Ltd.), oxetanyl silicate (OXT-191, Toagoi) Phenol novolac oxetane is preferable, and 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (1,3-BEOMB), 1,4-bis [(3- Ethyl-3-oxetanylmethoxy) methyl] benzene (1,4-BEOMB), 4,4′-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl (4,4′-BEOBP), 2,2 More preferred examples include '-bis [(3-ethyl-3-oxetanyl) methoxy] biphenyl and 3-ethyl-3-{[(3-ethyl-3-oxetanyl) methoxy] methyl} oxetane.

  The polymer of the present invention comprises (a) a compound having two oxetanyl groups in the same molecule represented by the following formula (II) and an arylene halide (b) represented by the formula (I). More preferably, it contains a repeating structure obtained by a ring-opening polyaddition reaction and represented by the formula (III). Examples of the terminal of the repeating structure represented by the formula (III) include a halogen atom and a hydrogen atom.

（式中、Ｒ¹及びＲ²はそれぞれ独立に、水素原子、又は、炭素数１〜６のアルキル基を表し、Ａは二価の連結基を表し、Ａｒは二価の芳香族基を表し、Ｘ¹及びＸ²はそれぞれ独立に、ハロゲン原子を表す。）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A represents a divalent linking group, and Ar represents a divalent aromatic group. , X ¹ and X ² each independently represents a halogen atom.)

R ¹ and R ² in the above formulas (II) and (III) are each independently a hydrogen atom or an alkyl group which may have 1 to 6 carbon atoms, among which a hydrogen atom, methyl Group or ethyl group is preferred.
A in the formulas (II) and (III) represents a divalent linking group, and is preferably a divalent hydrocarbon group, and the group —CH ₂ —O—R constituting the formula (1) described above. ^2- O—CH ₂ — and the group —R ⁶ —O—R ⁷ — constituting the above-described formula (5) are more preferable. In the group —CH ₂ —O—R ² —O—CH ₂ —, R ² is more preferably a methylene group, a phenylene group or a biphenylene group.
Examples of the divalent hydrocarbon group for R ² include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and a group obtained by combining two or more thereof, which may be linear or branched. Although it can illustrate, it is preferable that it is a C1-C6 alkylene group.

The alkyl group and the divalent hydrocarbon group (an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and a combination thereof) may be linear or branched. It may have a structure and may have a substituent shown below. Further, if possible, the substituent may be further substituted.
Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, and a halogen-substituted alkyl having 1 to 6 carbon atoms. Group, an aryl group having 4 to 12 carbon atoms, a halogen-substituted aryl group having 4 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and 1 to 7 carbon atoms And an acyloxy group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, and an amide group having 2 to 7 carbon atoms, preferably a halogen atom (a fluorine atom, a chlorine atom, A bromine atom, an iodine atom), a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms can be exemplified more preferably.

When the polymer of the present invention is a polymer obtained by using a compound having two oxetanyl groups in the same molecule as the compound (a), the number average molecular weight Mn of the polymer of the present invention is 500 to 500,000. It is preferable that it is, and it is more preferable that it is 800-120,000.
When the polymer of the present invention is a polymer obtained by using a compound having two oxetanyl groups in the same molecule as the compound (a), the molecular weight distribution of the polymer of the present invention (weight average molecular weight Mw / The number average molecular weight Mn) is preferably 1.5 to 3.0, more preferably 1.7 to 2.8.

(Production method of polymer)
The method for producing a polymer of the present invention performs a ring-opening polyaddition reaction between a compound (a) having two or more oxetanyl groups in the same molecule and an arylene halide (b) represented by the formula (I). Including a step (hereinafter also referred to as “ring-opening polyaddition step”).

<Ring-opening polyaddition process>
The ring-opening polyaddition step in the method for producing a polymer of the present invention comprises the opening of a compound (a) having two or more oxetanyl groups in the same molecule and an arylene halide (b) represented by formula (I). This is a step of performing a cycloaddition reaction.
The reaction between the compound having an oxetane ring in the molecule and phosphoric acid in the ring-opening polyaddition step may be performed using a catalyst or non-catalyst, but is preferably performed using a catalyst.
In the ring-opening polyaddition step, it is preferable to use a compound having two oxetanyl groups in the same molecule as the compound (a).

<Catalyst>
The ring-opening polyaddition reaction preferably uses a catalyst in terms of reactivity, cost, and energy efficiency.
The catalyst is preferably a basic catalyst, more preferably a quaternary onium salt, a crown ether complex, or a tertiary amine. Among these basic catalysts, in terms of reactivity, it is more preferable to use a quaternary onium salt or a crown ether complex, and it is particularly preferable to use a quaternary onium salt.

  The quaternary onium salts include tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetraethylammonium bromide, tetraethyl chloride, tetraethyl iodide, n-dodecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, trimethylbenzylammonium Bromide, cetyldimethylbenzylammonium chloride, cetyldimethylbenzylammonium bromide, cetylpyridium sulfate, tetraethylammonium acetate, trimethylbenzylammonium benzoate, trimethylbenzylammonium borate, 5-benzyl-1,5-diazabicyclo [4.3.0]- 5-nonenium And quaternary ammonium salts such as 5-benzyl-1,5-diazabicyclo [4.3.0] -5-nonenium tetrafluoroborate, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetraphenyl Phosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, triphenylmethoxymethylphosphonium chloride, triphenylmethylcarbonylmethylphosphonium chloride, triphenylethoxycarbonylmethylphosphonium chloride, trio Cutylbenzylboronium chloride, trioctylmethylphosphonium chloride Trioctyl ethyl phosphonium acetate, and tetra-octyl phosphonium chloride, quaternary phosphonium salts such as trioctyl ethyl phosphonium dimethyl phosphate can be exemplified. Among these, quaternary phosphonium salts are preferably used, and tetraphenylphosphonium chloride is particularly preferable.

  Examples of the crown ether complex include 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, 21-crown-7, and 24-crown-8. These include inorganic salts or organic salts such as KF, KCl, KBr, CsF, CsCl, CsBr, potassium thiocyanate, sodium phenoxide, potassium phenoxide, sodium benzoate, potassium benzoate, sodium acetate, or potassium acetate. Used as a complex. Of these, dibenzo-18-crown-6 is preferred.

  Examples of the tertiary amine include diethylaminopropylamine, N-aminoethylpiperazine, benzyldimethylamine, and tris (dimethylaminomethyl) phenol.

  The reaction conditions in the ring-opening polyaddition reaction may be determined according to the type of compound used. Specifically, it is preferable to carry out under the following conditions. The reaction can be carried out either continuously or batchwise.

<Catalyst concentration>
The amount of the catalyst used is preferably 0.1 to 40 mol%, more preferably 1 to 20 mol%, and particularly preferably 5 to 20 mol% with respect to the number of moles of the oxetanyl group. Within the above range, the reaction rate is high, and this is preferable from the viewpoint of cost.

<Reaction temperature and reaction time>
60-240 degreeC is preferable and, as for the reaction temperature in the said ring-opening polyaddition reaction, 120-200 degreeC is more preferable.
On the other hand, the reaction time is not particularly limited and can be appropriately selected in consideration of other reaction conditions such as reaction temperature.

<Use ratio between (a) and (b)>
Although there is no restriction | limiting in particular in the usage-ratio of the compound (a) in the manufacturing method of the polymer of this invention, and a compound (b), For example, when producing the polymer which has an oxetanyl group at the terminal as a polymer of this invention Is preferably used in a small excess amount of compound (a) relative to compound (b). When a polymer having a halide group derived from compound (b) at the end is desired as the polymer of the present invention, compound (a It is preferable to use b) in a small excess with respect to compound (a).

<Reaction solvent>
The ring-opening polyaddition reaction may be performed without solvent or using a reaction solvent. Examples of the reaction solvent include, but are not limited to, N, N-dimethylacetamide, N-methylpyrrolidone, chlorobenzene and dimethyl sulfoxide.

  EXAMPLES The present invention will be specifically described below using examples, but the present invention is not limited to these examples. Mn is the number average molecular weight, and Mw / Mn is the molecular weight distribution.

The measurement equipment used in the examples is shown below.
・ Infrared spectrophotometer (IR): FT-IR 420 type manufactured by JASCO Corporation ・¹ H nuclear magnetic resonance apparatus:
500 MHz-NMR; JNM-ECA-500 manufactured by JEOL Ltd.
Gel permeation chromatography (GPC, used for size exclusion chromatography measurement (SEC)): HLC-8220 manufactured by Tosoh Corporation
(Column: TSKgelSuperAW3000 + 2500 × 3 standard; polystyrene, solvent; tetrahydrofuran (THF), detector; RI with built-in HLC-8220, UV-8220)

(Example 1: Polymer obtained by polyaddition reaction of 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene (1,4-BEOMB) with α, α'-dichloro-p-xylene Synthesis)

In a glove box, 0.15 g (0.4 mmol) of tetraphenylphosphonium chloride (TPPC) was weighed as a catalyst in an ampule tube, a two-way cock was attached, taken out from the glove box, and dried under reduced pressure at 150 ° C. for 3 hours. . Then, again in the glove box 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene (1,4-BEOMB) 0.612 g (2 mmol) and α, α′-dichloro-p-xylene 0.350 g (2 mmol) is weighed, 1 ml of N-methylpyrrolidone (NMP) is added as a solvent, a two-way cock is attached, the glove box is taken out, the mixture is repeatedly frozen and degassed with liquid nitrogen, and sealed tube Went. This was thawed at room temperature and then reacted at a reaction temperature of 160 ° C. for 48 hours. After completion of the reaction, the reaction solution was diluted with a small amount of tetrahydrofuran (THF), washed once with water, and decanted to recover the precipitate. Thereafter, the precipitate was diluted with a small amount of chloroform and reprecipitated and purified once with methanol to obtain a yellow viscous liquid (polymer 1). The structure was confirmed by IR and ¹ H-NMR.
In addition, the yield was calculated | required by measuring the quantity of the insoluble part in methanol among the obtained reaction materials. Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were calculated by size exclusion chromatography (SEC) using THF as an eluent. This is also the case with the following examples.

The yield of polymer 1 obtained as a yellow viscous liquid is 0.850 g (yield: 88%), the conversion of compound (a) is 99% or more, and Mn is 5,140. , Mw / Mn was 2.1. Further, IR and ¹ HNMR data of the polymer 1 are shown below.
IR (film, cm ⁻¹ ) 1508 and 1463 (ν C = C aromatic), 1228 and 1099 (ν COC ether), 987 (ν COC cyclic ether), 752 (ν C-Cl chloromethyl).
¹ H-NMR (500 MHz, CDCl ₃ , tetramethylsilane (TMS)): δ (ppm) = 0.87-0.93 (m, 3.0H, H ^c ), 1.51-1.62 (m, 2.0H, H ^d ), 3.43 -3.47 (m, 2.0H, H ^f ), 2.64-3.73 (m, 2.0H, H ^h ), 3.81-3.9 (m, 2.0H, H ^g ), 4.47-4.56 (m, 2.0H, H ^j ) , 6.77-6.86 (m, 2.0H, H ^b ), 7.19-7.31 (m, 2.0H, H ^a ).

(Examples 2 and 3: Examination of reaction temperature in polyaddition reaction of 1,4-BEOMB and α, α'-dichloro-p-xylene)

  Polymers were synthesized at various reaction temperatures by polyaddition reaction of 1,4-BEOMB and α, α'-dichloro-p-xylene. The experimental operation was performed in the same manner as in Example 1. The results are shown in Table 1.

  At a reaction temperature of 140 ° C. (Example 2), the conversion rate of 1,4-BEOMB was low and the yield and molecular weight were low, but Polymer 1 was obtained. By increasing the reaction temperature to 160 ° C. (Example 1), the conversion rate increased, and the yield and molecular weight also increased. Further, it was confirmed that both the yield and the molecular weight were almost constant at a temperature higher than that (Example 3).

(Example 4: Synthesis of polymer by polyaddition reaction of 1,4-BEOMB and α, α'-dibromo-p-xylene)

  Example 1 except that polyaddition reaction of 1,4-BEOMB and α, α′-dibromo-p-xylene was carried out at 130 ° C. for 24 hours in 1 ml of NMP using 20 mol% of TPPC as a catalyst. The reaction was performed under the same conditions. As a result, Polymer 2 was obtained with a yield of 79% and a number average molecular weight of 6,300 and a molecular weight distribution of 2.09. Compared with the case of using α, α′-dichloro-p-xylene, when α, α′-dibromo-p-xylene was used, a corresponding polymer with a high molecular weight was obtained at a low temperature in a short time. .

(Examples 5 to 12: Examination of reaction conditions in polyaddition reaction of 1,4-BEOMB and α, α′-dibromo-p-xylene)
The polyaddition reaction of 1,4-BEOMB and α, α′-dibromo-p-xylene was carried out at various reaction temperatures in 24 ml for 48 hours in 1 ml NMP using 20 mol% TPPC as a catalyst. The reaction was carried out under the same conditions as in Example 1 except that (120, 130, 140, 150, 160 ° C.). The results are shown in Table 2.

(Example 13: Polyaddition reaction of 1,4-BEOMB and α, α′-dibromo-p-xylene)
Example 1 except that polyaddition reaction of 1,4-BEOMB and α′-dibromo-p-xylene was carried out in 1 ml of NMP at 130 ° C. for 72 hours using 20 mol% of TPPC as a catalyst. The reaction was performed under the same conditions. The results are shown in Table 3.

(Examples 14 and 15: Synthesis of polymers by reaction of various bisoxetane compounds with α, α'-dibromo-p-xylene)

  Examples 14 and 15 include various bisoxetanes (1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene (1,3-BEOMB), 4,4′-bis [(3- The reaction was carried out using ethyl-3-oxetanyl) methoxy] biphenyl (4,4′-BPOX)). The same as in Example 1 except that 20 mol% of TPPC was used as a catalyst for the reaction of various bisoxetanes with α, α′-dibromo-p-xylene in 130 ml at 48 ° C. in 1 ml NMP. The reaction was conducted under conditions. The results are shown in Table 4.

The ¹ H-NMR of polymer 3 obtained by using 1,3-BEOMB and α, α′-dibromo-p-xylene is shown below.

The ¹ H-NMR of polymer 4 obtained by using 4,4′-BPDOX and α, α′-dibromo-p-xylene is shown below.

Claims (5)

A polymer obtained by ring-opening polyaddition reaction of a compound (a) having two or more oxetanyl groups in the same molecule and an arylene halide (b) represented by the formula (I).

(In the formula, Ar represents a divalent aromatic group, and X ¹ and X ² each independently represent a halogen atom.) (A) is a compound having two oxetanyl groups in the same molecule represented by the following formula (II):
The polymer of Claim 1 containing the repeating structure represented by Formula (III).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A represents a divalent linking group, and Ar represents a divalent aromatic group. , X ¹ and X ² each independently represents a halogen atom.) A polymer comprising a step of performing a ring-opening polyaddition reaction between a compound (a) having two or more oxetanyl groups in the same molecule and an arylene halide (b) represented by the formula (I) Manufacturing method.

(In the formula, Ar represents a divalent aromatic group, and X ¹ and X ² each independently represent a halogen atom.)   The method for producing a polymer according to claim 3, wherein (a) is a compound having two oxetanyl groups in the same molecule represented by the following formula (II).   The method for producing a polymer according to claim 3 or 4, wherein the ring-opening polyaddition reaction is performed in the presence of a quaternary onium salt.