JP2007091598A - Reaction product of polyfunctional carboxylic acid and bisoxazoline and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bisoxazoline compound useful as a raw material for a curable resin composition and composed of an oligomer soluble in organic solvents and to provide a method for producing the compound. <P>SOLUTION: The compound is represented by general formula (1) (wherein, R<SB>1</SB>is an organic group; and n represents a positive number of ≥1). The method for producing the compound is provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a reaction product of a polyvalent carboxylic acid and a bisoxazoline and a method for producing the same.

  A compound produced by reacting bisoxazoline with a polyvalent carboxylic acid is a raw material of a curable resin composition, and this resin composition has advantages such as curability, chemical resistance, solvent resistance, and water resistance. Therefore, it is widely used in the fields of paints, surface treatment agents, coating agents, adhesives, pressure-sensitive adhesives, sealing agents, molding materials and the like. Moreover, this compound is used also for uses, such as a crosslinking agent to the various resin which has a carboxyl group, and the modifier of polyester.

  Here, in the reaction of bisoxazoline with a bifunctional reactant such as dicarboxylic acid, dithiol compound, monomercapto-monocarboxylic acid, and monoamino-monocarboxylic acid, bisoxazoline is difficult to dissolve in an organic solvent. In general, the reaction is carried out in bulk.

More recently, a reaction in a solution system is also performed using a solvent such as ethyl acetate.
Japanese Patent Publication No. 5-117253

However, the prior art described in the above literature has room for improvement in the following points.
First, when reacting in a bulk, there is a problem that it is difficult to react at a high temperature (160 ° C. or higher).
Secondly, even when diluted with a solvent, a high molecular weight substance may also be produced when mixed and reacted in a reaction vessel at one time. Low molecular weight substances such as dimers or trimers There was a problem that it was difficult to generate only.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a bisoxazoline compound composed of a low molecular weight compound soluble in an organic solvent, and a reaction method for obtaining the compound. .

(式中、Ｒ_１は有機基、ｎは１以上の正数を表す。)
[２]Ｒ_１が下記式（２）で表されることを特徴とする[１]記載の化合物。

(式中、Ｒ_２は−CH₂−、−C(CH₃)₂−、−O−、−S−、−SO₂−、−CO−、−NHCO−、−C(CF₃)₂−のいずれかを表す。)
[３]得られた生成物の平均重合度ｎが１以上、８以下である[１]又は[２]記載の化合物。
[４]ビスオキサゾリンと下記式で表されるカルボン酸を反応させて得られる化合物。

(式中、Ｒ_２は−CH₂−、−C(CH₃)₂−、−O−、−S−、−SO₂−、−CO−、−NHCO−、−C(CF₃)₂−のいずれかを表す。)
[５]ビスオキサゾリンと多価カルボン酸を反応させる方法であって、
当該２つの成分の一方を溶剤で希釈して反応容器に準備する工程と、
当該２つの成分の他方を溶剤で希釈した溶液を、前記準備した反応容器に滴下する工程、及び、
前記滴下後の混合溶液を加熱処理する工程、
を含むことを特徴とするビスオキサゾリンと多価カルボン酸を反応させる方法。 The above problem is solved by the following means.
[1] A compound represented by the structure represented by the general formula (1).

(In the formula, R ₁ represents an organic group, and n represents a positive number of 1 or more.)
[2] The compound according to [1], wherein R ₁ is represented by the following formula (2).

Wherein R ₂ is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ — Represents one of these.)
[3] The compound according to [1] or [2], wherein the average degree of polymerization n of the obtained product is 1 or more and 8 or less.
[4] A compound obtained by reacting bisoxazoline with a carboxylic acid represented by the following formula.

Wherein R ₂ is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ — Represents one of these.)
[5] A method of reacting a bisoxazoline with a polyvalent carboxylic acid,
Preparing one of the two components in a reaction vessel by diluting with a solvent;
Dropping a solution obtained by diluting the other of the two components with a solvent into the prepared reaction vessel; and
Heat-treating the mixed solution after the dropping,
A method of reacting a bisoxazoline with a polyvalent carboxylic acid, comprising

  ADVANTAGE OF THE INVENTION According to this invention, the reaction method for obtaining the bisoxazoline compound which consists of a low molecular weight body soluble in an organic solvent, and its compound can be provided.

  The present invention relates to a compound represented by the general formula (1). This compound is produced by reacting a specific bisoxazoline with a polyvalent carboxylic acid. The following is an example, and the present invention is not limited to the following. The compounds of the present invention are described in detail below.

  In the compound represented by the general formula (1) of the present invention, the dicarboxylic acid or polyvalent carboxylic acid diluted solution is divided into two times at 2.0 to 9.0 g / min into the reaction solution in which bisoxazoline is dissolved. The reaction temperature is 100 to 160 ° C. and the reaction is performed for 1 to 8 hours.

The stirring speed in the reaction of the present invention is 120 to 180 rpm, the dropping speed of the diluting solution is 2.0 to 9.0 g / min, and the dropping temperature of the diluting liquid is 110 to 160 ° C.

  As the bisoxazoline compound, an aliphatic or aromatic bisoxazoline compound, and as the dicarboxylic acid compound, an aliphatic or aromatic dicarboxylic acid or polyvalent carboxylic acid is preferable.

  Examples of the bisoxazoline compound containing an aliphatic group or an aromatic group include 2,2′-bis (2-oxazoline), 1,2-bis (2-oxazolin-2-yl) ethane, and 1,4-bis (2- Oxazolin-2-yl) butane, 1,8-bis (2-oxazolin-2-yl) butane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazoline- 2-yl) benzene and 1,3-bis (2-oxazolin-2-yl) benzene are selected, and two or more of these may be used. Of these, 1,3-bis (2-oxazolin-2-yl) benzene is particularly preferred.

  Examples of the aliphatic or aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, diphenyl ether-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, and benzophenone-4,4′-. Dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 2,2′-bis (4-carboxyphenyl) hexafluoropropane, 1,3-bis (carboxyphenyl) -1,1,3,3-tetramethyldisiloxane , Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and maleic acid, and two or more of these may be used. Of these, diphenyl ether-4,4'-dicarboxylic acid is preferred.

  Examples of the aliphatic or aromatic polyvalent carboxylic acid include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and 1,2,4. -Butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, etc. Two or more of these may be used.

  The reaction molar ratio of bisoxazoline and polyvalent carboxylic acid is 2.0 to 8.0 mol of polyvalent carboxylic acid with respect to 1.0 mol of bisoxazoline.

  Examples of the solvent used in the present invention include γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, and ethyl lactate.

  The diluted solution used in the present invention is prepared by diluting 100 parts by weight of dicarboxylic acid with 300 to 700 parts by weight of a solvent.

<Example>
4 equipped with 50.40 g (0.232 mol) of 2,2- (1,3-phenylene) bis-2-oxazoline and 260 g of γ-butyrolactone, equipped with thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube Placed in a separable flask at the mouth. When the flask containing the reaction solution is immersed in an oil bath and the temperature is raised while stirring, 2,2- (1,3-phenylene) bis-2-oxazoline is dissolved in the solvent at around 50 ° C. After confirming this, a diluted solution prepared by adding 14.80 g (0.058 mol) of diphenyl ether-4,4′-dicarboxylic acid to 30 g of γ-butyrolactone was added to the flask at a dropping rate of 4.48 g / min. throw into. Thereafter, a diluted solution prepared by adding 14.80 g (0.058 mol) of diphenyl ether-4,4′-dicarboxylic acid to 30 g of γ-butyrolactone again at around 120 ° C. was added at the same dropping rate. The reaction was carried out at 130 ° C. for an hour. From this, the result of GPC analysis of the obtained reaction solution is shown in FIG. A peak observed at an analysis time of 18 to 24 min is a product peak, and a high molecular weight compound is not generated. The average degree of polymerization of the obtained product is 6.

<Comparative example>
2,2- (1,3-phenylene) bis-2-oxazoline 50.40 g (0.232 mol), diphenyl ether-4,4′-dicarboxylic acid 29.60 g (0.116 mol) and γ − 320 g of butyrolactone was charged all at once into a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. The flask containing the reaction solution was immersed in an oil bath and the temperature was raised to 130 ° C. while stirring, and the reaction was performed for 3 hours. From this, the result of GPC analysis of the obtained reaction solution is shown in FIG. The molecular weight distribution of the peak of the product is broadened, and a high molecular weight compound is formed in the vicinity of 19 min. The average degree of polymerization of the product obtained is 18.

The measurement conditions of GPC in the present invention are a flow rate of 1.0 ml / min, and an eluent used is a solution mixed in a ratio of THF / DMF / phosphoric acid = 100: 100: 1.
The column is a gel pack column GL-S300MDT-5 manufactured by Hitachi Chemical Co., Ltd., and a UV detector manufactured by JASCO Corporation is set at a wavelength of 270 nm.

  The GPC charts of Example 1 and Comparative Example 1 are shown in FIGS. In FIG. 1, three peaks of product, bisoxazoline, and solvent are observed, whereas in FIG. 2, in addition to the three peaks observed in FIG. 1, a peak that is higher in molecular weight than the product is observed. Is done.

The compound of the present invention can be used as a crosslinking agent for resins containing functional groups that react with oxazolines such as carboxylic acids and hydroxyl groups.

FIG. 1 shows a GPC chart of Example 1. FIG. 2 shows a GPC chart of Comparative Example 1.

Explanation of symbols

1 Product peak 2 Relatively high molecular weight peak 3 Bisoxazoline peak 4 Solvent (γ-butyrolactone) peak

Claims (5)

The compound represented by the structure represented by General formula (1).

(In the formula, R ₁ represents an organic group, and n represents a positive number of 1 or more.) The compound according to claim 1, wherein R ₁ is represented by the following formula (2).

Wherein R ₂ is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ — Represents one of these.)   The compound according to claim 1 or 2, wherein the average degree of polymerization n of the obtained product is 1 or more and 8 or less. A compound obtained by reacting bisoxazoline with a carboxylic acid represented by the following formula.

Wherein R ₂ is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ — Represents one of these.) A method of reacting a bisoxazoline with a polyvalent carboxylic acid,
Preparing one of the two components in a reaction vessel by diluting with a solvent;
Dropping a solution obtained by diluting the other of the two components with a solvent into the prepared reaction vessel; and
Heat-treating the mixed solution after the dropping,
A method of reacting a bisoxazoline with a polyvalent carboxylic acid, comprising

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