JPS62207241A - Production of acryloyl group-and/or methyacryloyl group-containing compound - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as a curing agent capable of giving cured articles having very low water absorption, by subjecting an acrylic acid ester and/or methacrylic acid ester and epoxy resin to addition reaction. CONSTITUTION:A compound expressed by formula I [R1 is H or methyl; Y is O is S; Z is formula II (X is H, alkyl, halogen, nitro or methoxy; n is 1-5), formula III, IV, V, VI, VII or VIII], e.g. p-nitrophenyl methacrylate, etc., and an epoxy resin, e.g. Epikote, i.e. bisphenol type epoxy resin, etc., to afford the aimed acryloyl group and/or methacryloyl group-containing compound expressed by formula IX (R2 is epoxy residue). A quaternary onium salt, etc., is preferably used as a catalyst in the reaction and hydroquinone monomethyl ether, etc., is preferably used as a polymerization inhibitor.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing an acrylic ester group-containing compound.

[Prior art] Japanese Patent Publication No. 44-31472, Japanese Patent Publication No. 45-4069
As described in Japanese Patent Publication No. 45-15988, etc., unsaturated epoxy ester resins are unsaturated epoxy ester resins.
Basic acid and optionally unsaturated - partially saturated basic acid -
An acid component substituted with one or more selected from basic acids, saturated polybasic acids, anhydrous saturated polybasic acids, unsaturated polybasic acids, and anhydrous unsaturated polybasic acids and an epoxy resin are esterified. The compound is synthesized by carrying out a heating reaction in the presence of a reaction catalyst, a polymerization inhibitor, a solvent, or a polymerizable monomer (hereinafter referred to as a monomer) if necessary, and then adding a solvent or monomer if necessary. This resin can be cured at room temperature or by heating by using an organic peroxide as a curing catalyst and, if necessary, a metal salt or the like as an accelerator.

When using this resin with a solvent, it can be used as paint, prepreg, etc., and when using a monomer, it can be used as a reinforced plastic (F).
RP), casting, adhesion, paint, etc.

Although the above resin is a type of modified epoxy resin, it is an unsaturated polyester obtained by polycondensing acids such as maleic anhydride and phthalic acid with polyhydric alcohols such as ethylene glycol, and is dissolved in monomers such as styrene. It has the characteristic that it can be cured with organic peroxides, etc., just like the unsaturated polynisder resin made of polynisder. Furthermore, this unsaturated epoxy ester resin has performance equivalent to or superior to epoxy resins cured by amine or acid curing, especially in terms of chemical resistance, weather resistance, curing properties, workability, etc. For example, in terms of chemical resistance, epoxy resins are superior to epoxy resins.
When cured at room temperature or heat curing is possible, it is classified as alkali-resistant, and when cured with acid (heat-cured), it is classified as acid-resistant. Therefore, it is difficult to obtain a material that has both of these characteristics by curing at room temperature.

However, unsaturated epoxy ester resins have excellent acid resistance and alkali resistance no matter which curing catalyst system is used.

In addition, regarding curability, in epoxy resins, the amount of curing agent used is limited, so it is not very flexible to adjust the curability at a certain temperature, and most of the time it is adjusted by the curing temperature. This is the current situation. Therefore, when curing at room temperature,
In summer or winter, there are many problems because gelation is fast or it does not harden. It has the characteristic that by changing the amount used, it is possible to achieve roughly the same curing properties in both summer and winter.

[Problems to be Solved by the Invention] Conventional vinyl ester resins synthesized from epoxy resins and (meth)acrylic acid have secondary hydroxyl groups due to ring opening of epoxy groups. This results in higher viscosity and
It has a high water absorption rate and is not necessarily suitable for fields where high electrical performance is required.

Polymer, J., Vol. 16, p. 371 (1)
(984), Nishikubo et al. revealed that epoxy groups in polymer side chains and various esters react quantitatively under relatively mild conditions when a specific quaternary ammonium salt is used as a catalyst. Ta. In order to solve the above-mentioned problems, the acrylic ester group-containing compound synthesized by applying this reaction has curability and can be applied to the production of curable compositions, thereby solving the storage problems mentioned above. The inventors discovered that the problems could be solved and completed the present invention.

Therefore, the present invention provides the general formula % where R1 is a hydrogen atom or a methyl group, Y is an oxygen atom or a sulfur atom, and Z is a group selected from the group Q (x>n, , where X is a hydrogen atom, an alkyl group, a halogen atom, a nitro group, or a methoxy group, and n is 1
is an integer of ~5] with an epoxy resin, represented by the formula -a (wherein R,, Y and Z have the same meanings as above, and R2 is an epoxy residue). An object of the present invention is to provide a method for producing a compound containing an acryloyl group and/or a methacryloyl group.

[Function] The acryloyl group- and/or methacryloyl group-containing compound of the present invention can be produced according to the addition reaction shown in the following formula: R3 (In the above formula, R1, R2, Y and Z are as defined above. have the same meaning).

In the above-mentioned addition reaction, the reaction ratio of the epoxy resin and the acrylic acid phenyl esters and/or the methacrylic acid phenyl esters is 0.0.
It is necessary that the total ester group of acrylic acid phenyl esters and/or methacrylic acid phenyl esters be 1 mol per 5.0 to 2.0 mol, and acrylic ester groups synthesized at a reaction ratio outside this range. Containing compounds are not preferred because they are inferior in curability, hardness of cured film, solvent resistance, and water resistance.

Epoxy resins that can be used in the above C1 addition reaction include Epicote 828 (manufactured by Shell), higher molecular weight Ebibis type epoxy resin, epoxy novolac type epoxy resin, N,N-diglycidylaniline, and alicyclic type epoxy resin. Various epoxy compounds such as epoxy resins and ethylene glycol diglycidyl ether can be mentioned.

In addition, examples of acrylic esters and/or methacrylic esters that can be used in the above addition reaction include p-nitrophenyl methacrylate, 2,4-dichlorophenyl methacrylate, and phenyl methacrylate used in the examples described below. In addition to p-methoxyphenyl methacrylate and p-methoxyphenyl methacrylate, the following compounds may be mentioned:
R5 In the format, R1 and 2 have the same meanings as above.

1゛ CIl□=C o-o-z In the formula, R1 and 2 have the same meanings as above.

In addition, R1 (wherein Ro and R6 have the same meanings as above, and A is -c
Self-sensitizing oligomers such as o-Q*taher coc++5cisys) can also be synthesized.

Furthermore, some of the acrylic esters and/or methacrylic esters having aromatic or other active ester groups can be converted into di(ρ-nitrophenyl)adipic acid, diphenylthioadipate, cy(11-nitrophenyl) ) Isophthalic acid ester, tri(4-chlorophenyl)
It is also possible to change to polyfunctional esters such as trimellitic acid ester, and in this case, a high molecular weight telegelic oligomer can be obtained.

In addition, various tertiary amines, quaternary onium salts (phosphonium salts, ammonium salts), and crown ethers-KBr can be used as catalysts for the above-mentioned addition reaction; In order to advance the process, it is preferable to use quaternary onium salts rather than tertiary amines.Furthermore, for quaternary, the total number of carbon atoms in the alkyl groups represented by R1-R1 is 8 or more. It is preferable. Further, a part of the alkyl group may be substituted with a phenyl group or a benzyl group, and Br-1CI-2■- or F- is preferable as a counter ion of the quaternary onium salt.

Furthermore, in order to prevent gelation during the above-mentioned addition reaction, phenols, quinones, and other compounds having an anti-association effect can be used as polymerization inhibitors, if necessary. These polymerization inhibitors can also be added after the reaction.

Examples of these polymerization inhibitors include hydroquinone,
Examples include hydroquinone monomethyl ether, benzoquinone, phenothiazine, thiosemicarbasite, acetone thiocarbazone, copper salt, and the like.

In the examples described below, the addition reaction was carried out without a solvent from the viewpoint of confirming the structure and reactivity of the product, but a reaction solvent can normally be used in the addition reaction. Furthermore, from the viewpoint of controlling heat generation during reaction, adjusting the viscosity of the product, and application as a photocurable material,
It is preferable to use polyfunctional acrylates such as ethylene glycol cyacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylol-10-pantrimethacrylate, etc. as the reaction solvent.

EXAMPLES] The present invention will be further explained with reference to Examples (hereinafter simply referred to as "examples" unless otherwise specified) below.

-L p-nitrophenyl methacrylate 20.739 (0,
1 mol) and Epicote 828 (bisphenol type epoxy resin 17.83 g (0.1 mol as epoxy group) were placed in a 100 ml separable flask, and tetrabutylammonium bromide (TBAB) was added as a catalyst to this.
1.64# (0,005 mol) was added, and hydroquinone monomethyl ether (MQ) with a low Ji (0,01y) was added as a polymerization inhibitor, and the reaction was carried out at 120°C for 5 hours.The 0 reaction rate was determined as the epoxy equivalent. 99.5 mol% determined from
Met. The molecular weight (according to GPC) of the product obtained was approximately 600.

Further, when the same reaction was carried out at 110° C. for 5 hours, the reaction rate was 94.7 mol%.

When the obtained product was subjected to IR analysis, it was found that 3300
Almost no absorption based on 10H in cm-' is observed,
Esteric c = o at 1720 cm-' (1730 cm-' for p-nitrophenyl methacrylate), 1
640cm-' to C=C11240cm-■ and 116
Characteristic absorption of C-0-C (ester and ether) was shown at 0 cm'''1, and absorption of epoxy groups around 910 eel'''1 completely disappeared.

Further, the viscosity of the product was about 200 voids.

λ-1 2,4-dichlorophenyl methacrylate 23.139
(0.1 mol) and Epicote 82817.83y (0.1 mol as epoxy group),
Add f (0,005 mol) and add a small amount of flk (0,01 g>
The reaction was carried out at 120° C. for 8 hours in the presence of MQ, and the zero reaction rate was determined from the epoxy equivalent and was 99.4 mol%. The molecular Jl (according to GPC) of the product obtained was approximately 600.

When the obtained product was subjected to IR analysis, it was found that 3300
Almost no absorption based on 10H is seen in c++-',
1720cm-'Number ester C=O11640cm
-' to C=C11240cm-' and 1160cm-'
showed a characteristic absorption of C-Q-c (ester and ether), and the absorption of epoxy groups around 910ef' completely disappeared.

16.18y (0.1 mol) of phenyl methacrylate and 17.83g of Epicote 828 (0 as epoxy group)
．． 1 mol) of TBABl, 64y (0,005
mole) and a small amount (0,011F) + 7)M Q and add 1
The reaction rate after 8 hours of reaction at 20°C was determined from the epoxy equivalent and was 94.8 mol%.

The average molecular weight (GPC) of the obtained product was about 560.

When the obtained product was subjected to IR analysis, it was found that 3300
There is almost no absorption based on 10H in cm-', and 1
720e+s-' with ester c=o, 1640c+@
-' c=c, 1240cm-' and 1160cm-'
Gel: C-0-C (1 sprue property and ether property)
It showed a characteristic absorption of 910 cm-', and the absorption of epoxy groups around 910 cm-' completely disappeared.

L p-methoxyphenyl methacrylate 19.12 g (0
, 1 mol) and 17.83 g (0.1 mol as epoxy group) of Epicote 828 were mixed with TBABl, 64
#(0,005-11-l), MQo, and 01y were added and reacted at 120° C. for 10 hours. The zero reaction rate was determined from the epoxy equivalent and was 91.9 mol %.

Molecule 11 of the product obtained (GPC) is approximately 600
Met.

When the obtained product was subjected to IR analysis, it was found that 3300
Weak absorption based on -OH is seen in the c-fine, and 1720e
Ester c=o for 164'Oc+*-', C for 164'Oc+*-'
=C51230cm-' and 1180cm-'co
-c characteristic absorption was exhibited, and the absorption of epoxy groups near 910e@-' almost disappeared.

From the above, it is presumed that in the reaction between p-methoxyphenyl methacrylate and Epicote 828, in addition to the reaction between the epoxy group and the ester group, a slight reaction between the epoxy group and water in the air occurs as a side reaction. Ru.

0.32 as a photo-enhancing agent to the product toy obtained in Example 1.
of benzoin ethyl ether and 0.1
Coat with a thickness of 1 and 20 cm with a 500 watt ultra-high pressure mercury lamp.
When light was irradiated for 1 minute from a distance of cm, a cured product was produced that was insoluble in solvents such as THF. The pencil hardness of the cured film is 2
It was H to 3H.

In addition, the water absorption rate (weight %) of the coating film is 0 when immersed for 24 hours at room temperature.
．． It was 07ffi amount%.

7.4 g of acrylic acid (
0.1 mol), tetrabutylammonium bromide and hydroquinone monomethyl ether of the same ff1ffi were added, and the mixture was reacted at 120"C for 3 hours.

The resulting resin was sloppy and unpaintable, so
Add 51F ethyl acetate to make a solution, add 0.33F benzoin ethyl ether, and place on a glass plate with 0.1F ethyl acetate.
It was applied to a thickness of 5 mm, left at room temperature for 1 hour and at 80° C. for 30 minutes to evaporate the solvent, and then photocured under the same conditions as in Example 5 (Reference Example).

The pencil hardness of the paint film is not much different from 2H, but the water absorption rate is 0.6
The weight was 1%.

9-L"I"u 16g of styrene was added to the resin obtained in Example 3, and after uniformly dissolving, 0.3# of benzoyl peroxide powder was added,
Dissolved.

The resulting mixture was transferred to a test tube with an inner diameter of 18 sn, and initially
It was cured by heating at 0°C for 2 hours and then at 120°C for 2 hours.

The hardness of the obtained cured resin is 1 on the Rockwell scale.
10 and 1, the glass transition temperature is 139°C, and 80
No change in appearance was observed even after 1000 hours of immersion in a 10% caustic soda solution at a temperature of It can also be hardened when using exacerbants, and
A cured product with very low water absorption can be obtained.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 is a hydrogen atom or a methyl group, Y is an oxygen atom or sulfur atom, Z is ▲ Numerical formula, chemical formula, table, etc. There are ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
a group selected from the group consisting of, where X is a hydrogen atom, an alkyl group, a halogen atom, a nitro group, a methoxy group, and n is 1
There are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼ (where R_1, Y and Z have the same meanings as above, and R_
2 is an epoxy residue).