JPS6289719A - Novel vinyl ester resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled resin having high heat resistance and flexibility, by reacting a dicyclopentadiene-modified epoxy resin with acrylic acid, etc. CONSTITUTION:(A) A dicyclopentadiene-modified epoxy resin expressed by formula I (R is methyl or H; n is an integer 0-15) is mixed with (B) preferably 0.7-1.1 equivalents, based on one equivalent epoxy group, acrylic acid or a reactive derivative thereof and reacted in the presence of an esterification catalyst, preferably tetraethylammonium bromide, preferably at 90-130 deg.C to give 1-16 acid value of the resultant resin. As a result, the aimed resin expressed by formula II is obtained.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel vinyl ester resin which is dissolved in vinyl monomer and whose cured product has high heat resistance and flexibility, and a method for producing the same. It is.

(Prior art and problems to be solved by the invention) In recent years, unsaturated epoxy ester resins (vinyl ester resins) are produced by dissolving a reaction product of an epoxy resin and an unsaturated basic acid in a polymerizable monomer such as styrene. However, it is steadily being used in the market as a product that combines the performance of epoxy resin with the workability and curing properties of unsaturated polyester resin.

Similar to unsaturated polyester resins, such vinyl ester resins are used in a wide range of fields, including corrosion-resistant reinforced plastic materials, lining materials, coating materials, impregnating materials, enclosing agents, and casting materials.

Furthermore, this vinyl ester resin can be made to have a wide variety of performances by selecting epoxy compounds with different types and degrees of polymerization as the ester groove component, or by blending these.

The above-mentioned vinyl ester resin is made by ring-opening the epoxy group of an epoxy compound with the carboxyl group of an unsaturated basic acid such as acrylic acid, methacrylic acid, etc., and esterifying it to produce epoxy ertel. . The most common epoxy resin used for vinyl ester resins is the diglycidyl ether type of bisphenol A.

However, although these vinyl ester resins made from diglycidyl ether type epoxy of hisphenol A have significantly higher acid resistance and alkali resistance than general unsaturated polyester resins, their heat distortion temperature The temperature is about 110'C at most, and its use at high temperatures is severely restricted.

In addition, conventionally commercially available epoxy acrylate resins having a novolac skeleton are produced by reacting a phenolic compound with a polymerine to form a solid novolac, and then reacting epichlorohydrin with a novolac type epoxy resin represented by the following formula (III) (in the formula R is H or CH3, n is O
Indicates an integer between ~10. ] This is reacted with acrylic acid and/or methacrylic acid in the presence of a vinyl monomer solvent such as styrene or methyl methacrylate to produce a resin vinyl monomer solution.

This epoxy acrylate resin (vinyl ester resin) having a novolac skeleton is represented by the following formula (1v).

(IV) [In the formula, R is H or CH3, and EXAC is CH3
, n represents an integer of 0 to 10. ] However, this epoxy acrylate resin having a novolak skeleton is also not fully satisfactory in terms of its heat distortion temperature.

[Means for solving problems]

The present invention has been made to solve these problems, and is represented by the following general formula (1) (wherein R is a methyl group or a hydrogen atom, and n is an integer from O to 15). The present invention provides a new vinyl ester resin and a method for producing the same.

The novel vinyl ester resin of the present invention represented by the above general formula CI) is characterized in that it is dissolved in a vinyl monomer and the cured product thereof has high heat resistance and flexibility.

The novel vinyl ester resin of the present invention represented by the general formula [Eng. It is obtained by reacting a dicyclopentadiene-modified epoxy resin with acrylic acid or a reactive derivative of acrylic acid.

In the present invention, the dicyclopentadiene-modified epoxy resin represented by the above general formula (II) is produced by polymerizing dicyclopentadiene and phenols (phenol, orthocresol, valaclesol, isopropylphenol, etc.) in a Lewis acid catalyst. It can be obtained by reacting the obtained dicyclopentadiene-modified phenol resin with epichlorohydrin.

In the esterification reaction between the dicyclopentadiene-modified epoxy resin represented by the above general formula (n) and acrylic acid, 0.5 to 1.8 equivalents of acrylic acid per equivalent of epoxy base,
Preferably, the mixture is mixed at a ratio of 0.7 to 1.1 degrees centigrade, and heated to 70 to 180'C, preferably 90 degrees centigrade, in the presence of an esterification catalyst.
At a temperature of ~130'C, the acid value of the resulting resin is 1-16.
It can be suitably produced by reacting until it becomes.

Such ester reaction is preferably carried out in an oxygen or air atmosphere.

Generally the reaction time is 2 to 16 hours, preferably 4 to 8 hours. As the reaction solvent, any solvent that does not inhibit the esterification reaction can be used as necessary. Further, in order to obtain a cured product without distilling off the solvent, it is convenient to use a vinyl monomer such as styrene or divinylbenzene which is copolymerizable with the vinyl ester resin to be produced.

It is not preferable to use an excessive amount of acrylic acid because it reduces the rate of esterification reaction with the epoxy resin and significantly deteriorates the alkali resistance of the cured product obtained. (Also, a portion of the acrylic acid may be replaced by a saturated-basic acid, a saturated dibasic acid, or an unsaturated dibasic acid. These acids may be added to the total acid component used (
On the other hand, it is preferable to use up to 80% by weight, preferably 10 to 60% by weight. Examples of acids that can be used in place of some of the above acrylic acids include propionic acid, benzoic acid, phthalic acid, terephthalic acid, tetrahydrophthalic anhydride, succinic acid, divicic acid, fumaric acid, maleic anhydride. Examples include acids.
(Esterification catalysts used in the present invention include, for example, (1) 3@amines such as N,N-dimedylaniline, pyridine, triethylamine, hexamethylene diamine, etc. and their non-IIM salts, such as salts of hydrochloric acid, or salts of organic acids, such as acetic acid. .

(2) 4-treated ammonium salts such as tetramethylammonium bromide and trimethylbenzylammonium chloride.

3) Sulfonic acids and sulfonium salts such as para-toluenesulfonic acid and trinoenylsulfonium chloride.

4) Sulfonium salts such as trimethylsulfonium chloride and dimethylphenylsulfonium chloride.

5) Phosphonium salts such as phosphonium iodide.

6) Metal halides such as lithium chloride, lithium bromide, stannous chloride, and zinc chloride.

7) Total hydroxides such as potassium hydroxide and lithium hydroxide.

Among these esterification catalysts, tetraethylammonium bromide has much better compatibility with the dicyclopentadiene-modified epoxy resin than other catalysts, provides a fast reaction rate, and achieves a high reaction rate. This is preferable because it allows

These esterification catalysts are used at a ratio of 0.005 to 3 ff/m parts per 100 parts by weight of the mixture of the ethylene oxide resin and the acid component.

Further, the ester reaction is preferably carried out in the presence of a hand reaction inhibitor, such as p-hydroquinone, naphthoquinone, henzoquinone, di-tert-butyl hydroxytoluene, hydroquinone monomethyl ether, tert-butyl catechol, etc. Examples include mono- or polyhydric phenols and quinones. The amount used is about 0.001 to 1.0 parts by weight, preferably 0.005 parts by weight, per 100 parts by weight of the reaction mixture.
~0.5 parts by weight.

According to the practice of the present invention, the vinyl ester resin produced by "A" can be cured alone in the presence of a polymerization initiator, but the vinyl ester resin can be bulked with a vinyl monomer that can be coproduced with the vinyl ester resin. It will be easier to handle if it is made into a low viscosity liquid.

At this time, the vinyl monomer is 30 to 120 parts by weight, preferably 40 to 8 parts by weight, based on 100 parts by weight of the vinyl ester resin.
It is used in a proportion of 0 parts by weight.

Examples of such vinyl monomers include styrene, methacrylate, methyl methacrylate, vinyltoluene, poly[]]rosdylene vinylpenvin, acrylonitrile, methacrylonitrile, cyclopentadiene, cyhynylbenzene, vinylpyridine. , vinyl acetate, diacrylphthalate, glycidyl methacrylate, etc., and one or more of these can also be used in combination.

After the reaction is completed, polyacrylate is precipitated by adding a poor solvent for polyacrylate, such as water, and separated from the solvent.

In addition, polyacrylate is a poor solvent for organic acids.)
8 medium, such as methyl isobutyl ketone, toluene, xylene, chloroform, methyl ethyl ketone, etc.
After the polyacrylate is transferred from the organic acid layer to these solvent layers and the organic acid layer is separated, these solvents are distilled off to separate the polyacrylate.

The polyacrylate thus obtained is mixed with a polymerization initiator in a solvent such as acetone, toluene, chloroform, methyl acetate, or a vinyl monolayer such as methyl methacrylate or styrene, and used for paints and prepregs. .

The vinyl toluene liquid diluted with the vinyl monomer is then cured at room temperature in the presence of an initiator such as a combination of methyl ethyl ketone peroxide and cobalt salt, similar to the liquid unsaturated polyester resin composition. It is also possible to cure at a high temperature by adding a high temperature decomposition initiator such as benzoyl peroxide.

(Example) The present invention will be further explained with reference to Examples below.

In the examples, parts and percentages are by weight unless otherwise specified.

Example 1 Dicyclopentadiene modified epoxy resin (DCE-40
0, 500 parts of epoxy (ff1280g/eQ), 150 parts of acrylic acid, 3.0 parts of tetramethylammonium bromide, 20.3 parts of hydrogin, and 15 parts of toluene.
00 parts was placed in a flask equipped with a stirring blade and a condenser, and the reaction was carried out by heating to 100'C over an oil solution, and the acid value became almost zero after 3 hours.

Add 200 d of 10% sodium hydrogen carbonate aqueous solution to this reaction solution.
, add distilled zi1oooy to remove excess acrylic acid, and distilled water 10100O! After extraction and washing three times, the organic layer was separated and the organic solvent was distilled off to obtain 593 g of the desired new vinyl ester resin. The analysis results are shown in Table 1.

To 100 parts of this reaction product, 54 parts of styrene were added and mixed to obtain a viscous solution with a Gardner hue of 3.5 sq. viscosity at 7 to 8.25°C.

Example 2 A target resin was obtained under the same conditions as in Example 1, except that the esterification catalyst used in Example 1 was changed to 1 to 2.5 parts of ethylbenzylammonium bromide.

The analysis results are shown in Table 1.

Table-1 1>Solvent CHC,? , λmax.

2>KBr method 3) 13C-NMR1 tJjA CDC, e3

[Brief explanation of drawings]

Figure 1 is a chart showing the infrared absorption spectrum of the vinyl ester resin of Example 1 of the present invention, and Figure 2 is a chart showing the GP of the same resin.
FIG. 3 is a chart showing GPC of the vinyl ester resin of Example 2 of the present invention, and FIG. 4 is a chart showing the nuclear magnetic resonance spectrum of the present invention.

Claims (1)

[Claims] 1) The following general formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [I] [In the formula, R represents a methyl group or a hydrogen atom, and n represents an integer from 0 to 15. ] A new vinyl ester resin. 2) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] [In the formula, R represents a methyl group or a hydrogen atom, and n represents an integer from 0 to 15. ] A method for producing a novel vinyl ester resin represented by the following general formula [I], which comprises reacting a dicyclopentadiene-modified epoxy resin represented by the following with acrylic acid or a reactive derivative of acrylic acid. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R represents a methyl group or a hydrogen atom, and n represents an integer from 0 to 15. ]