JPH0977843A - Production of vinyl ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily modify a vinyl ester with fumaric acid by subjecting the hydroxyl group of the vinyl ester to the ring-opening addition reaction of maleic anhydride and subsequently transferring the maleic acid residue in the product molecule into the fumaric acid residue at a low temperature. SOLUTION: A method for producing a vinyl ester comprises subjecting (A) the hydroxyl group of vinyl ester obtained by the reaction of an epoxy compound with an unsaturated monobasic acid to the ring-opening addition reaction of (B) maleic anhydride especially at 80-120 deg.C, preferably adding 0.1-1.0% of an acid chloride as a low temperature transition catalyst and subsequently transferring the maleic acid residue in the reaction product into the fumaric acid residue at a reaction temperature of 80-110 deg.C to modify the vinyl ester with the fumaric acid. Alternatively, the method comprises transferring (C) the maleic acid residue of an acid-terminated unsaturated polyester obtained by the ring-opening addition reaction of maleic anhydride and a glycol compound into the fumaric acid residue at a low temperature, and subsequently reacting the terminal acid residue of the component C with (D) an epoxy compound and (E) an unsaturated monobasic acid to modify the vinyl ester group of the unsaturated polyester.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the fumaric acid modification of a vinyl ester or the vinyl ester modification of an unsaturated polyester by easily carrying out the fumaric acid transfer of maleic acid at a low temperature, which normally has to be carried out at a high temperature. The present invention provides a method for producing a vinyl ester, characterized by:

[0002]

2. Description of the Related Art Vinyl ester is used in a state of being dissolved in a reactive diluent such as styrene monomer or methyl methacrylate, and originally has excellent corrosion resistance, chemical resistance, water resistance, and boiling resistance. Suitable for use under relatively severe conditions such as molded products such as fiber reinforced plastics (FRP) mixed with fibers and resin filled with inorganic fillers, tank lining materials, chemical tanks, ducts, pipes, large chimneys, etc. There is. Further, in recent years, it has been widely used as a molding resin for a semi-transparent artificial marble bathtub or the like since the technology for producing a light-colored vinyl ester was established.

Generally, a vinyl ester is an epoxy resin having at least one epoxy group in the molecule and an unsaturated monobasic acid such as (meth) acrylic acid having at least one unsaturated bond in the molecule as a tertiary amine or , A quaternary ammonium salt as an addition reaction catalyst, and optionally a polymerization inhibitor and a solvent in combination, at a reaction temperature of 90 ° C to 130 ° C.
Obtained by reacting in the presence of air.

Further, in an attempt to further improve the originally excellent performance, various modifications such as urethane modification utilizing hydroxyl groups present in vinyl ester, ring-opening addition modification with acid anhydride, and allyl modification have been made. There is. Further, modification of vinyl ester with unsaturated polyester or modification of unsaturated polyester with vinyl ester is also carried out in the same manner, and development of resins utilizing the characteristics of each resin is being studied.

The modification of the unsaturated polyester is carried out by using an unsaturated polyester having a lower molecular weight than that of the usual unsaturated polyester, but for the production of the low molecular unsaturated polyester, the reaction temperature is the same as in the usual unsaturated polyester production method. 1
The production was carried out at 80 to 220 ° C. for a reaction time of 4 to 8 hours, and the vinyl esterification reaction was carried out at 80 ° C. to 130 ° C. for 2 to 5 hours.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a maleic acid-modified vinyl ester obtained by a ring-opening addition reaction of maleic anhydride for the production of a vinyl ester, wherein maleic acid is converted to fumaric acid excellent in reactivity with styrene. It is an object of the present invention to provide a method for producing a vinyl ester which is transferred at a low temperature and a method for producing a modified vinyl ester by an unsaturated polyester which is obtained by transferring a fumaric acid in an unsaturated polyester at a low temperature.

[0007]

Means for Solving the Problems That is, the present invention is directed to the fumaric acid modification of a vinyl ester obtained by the reaction of an epoxy compound and an unsaturated monobasic acid, after ring-opening addition of maleic anhydride to the hydroxyl group of the vinyl ester. Ring-opening addition reaction of maleic anhydride to glycol in the production method of vinyl ester by facilitating fumaric acid modification of vinyl ester by low-temperature transfer of maleic acid in fumaric acid, and vinyl ester modification of unsaturated polyester The maleic acid terminal of the acid-terminated unsaturated polyester oligomer obtained in 1. is transferred to fumaric acid at low temperature, and then the vinyl ester of the unsaturated polyester is easily modified by reacting the epoxy compound with the unsaturated monobasic acid. And a method for producing vinyl ester.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The epoxy compound used in the present invention is an epoxy resin having at least one epoxy group in the molecule, and is known, for example, as epi, bis type epoxy resin, novolac type epoxy resin, glycidyl ester type or glycidyl ether type epoxy resin. It is a compound. Further, examples of the unsaturated monobasic acid include methacrylic acid, acrylic acid, and crotonic acid, but some fumaric acid,
Maleic acid and itaconic acid may be used in combination.

The production of vinyl ester is a publicly known method, but in general, the reaction of an epoxy resin with an unsaturated monobasic acid is usually a reaction catalyst of secondary amine, tertiary amine, quaternary ammonium salt, lithium chloride or the like. Hydroquinone, methyl hydroquinone, tertiary butyl hydroquinone, 2,6-ditertiary butyl-4-methylphenol, etc. are added as a polymerization inhibitor as necessary,
It is carried out at a reaction temperature of 80 to 120 ° C. in the presence of oxygen.

In the method for producing a fumaric acid-modified vinyl ester of the present invention, the addition reaction of maleic anhydride to the secondary hydroxyl group present in the vinyl ester is 80 to 120.
Perform at ℃. Next, the transfer reaction of maleic acid to fumaric acid is
0.1 to 1.0% of acid chloride is added as a low temperature transfer catalyst, and the reaction temperature is 80 to 110 ° C.

Examples of the acid chloride used here include fumaric acid chloride, isophthalic acid chloride, succinic acid chloride, and fumaric acid monoalkyl ester chloride. When the transfer catalyst is added, the inside of the system becomes a strongly acidic state, so it may be necessary to prevent corrosion of the production equipment. Examples of the metal corrosion prevention method include a method for preventing corrosion by treating the manufacturing apparatus itself with phytic acid, a method for preventing reaction, and a method for deactivating the catalyst.
The present invention is no exception. This reaction may be a solventless method, but it is preferable to use a solvent method in order to effectively utilize the transfer catalyst. The transfer reaction time is 1 to 3 hours, and the transfer rate of 85% to 100% can be obtained.

Next, the vinyl ester modification method of unsaturated polyester will be explained. As the glycol component used in the unsaturated polyester synthesis, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,
4-butanediol, 2,3-butanediol, polypropylene glycol, polyethylene glycol, neopentyl glycol, hydrogenated bisphenol A, 1,4-
Examples include cyclohexanedimethanol, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, and the like which are generally used in the production of unsaturated polyesters.

The acid component includes maleic anhydride as an unsaturated dibasic acid anhydride, phthalic acid as an unsaturated dibasic acid, and phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, and others. Hexahydrophthalic anhydride, acid anhydride such as succinic anhydride, and adipic acid, isophthalic acid, terephthalic acid, dimethyl terephthalic acid ester and the like can be mentioned.

Maleic anhydride is desirable as the acid component used in the production of the unsaturated polyester in the present invention, but the glycol component is not particularly limited. The reaction method is
Maleic anhydride is charged at a ratio of 2 mol per 1 mol of the glycol component, and the reaction temperature is 80 ° C. to 130 ° C. The acid anhydride component is added to both ends of the glycol. The acid-terminated unsaturated polyester thus obtained is subjected to a rearrangement reaction by adding an acid chloride in a production vessel which is optionally subjected to a corrosion treatment as described above. The reaction temperature is 80 ° C. to 120 ° C., and the mixture is stirred for 2 hours under a nitrogen atmosphere, and then 2 to 2.2 mol of the epoxy resin and 2 to 2.2 mol of the unsaturated monobasic acid relative to 1 mol of the obtained unsaturated polyester. Mol, addition catalyst 0.1-0.5%, polymerization inhibitor 0.01-0.05%, reaction temperature 80 ° C-
The addition reaction of the epoxy resin and the addition reaction of the unsaturated monobasic acid are carried out at 130 ° C.

The epoxy resin may be added simultaneously with the unsaturated monobasic acid and the reaction catalyst, but preferably the epoxy resin is first reacted with the acid terminal unsaturated polyester in the presence of an addition reaction catalyst to give an acid value of 5 or less. After confirming the above, it is desirable to react by adding an unsaturated monobasic acid at the same time as the reaction catalyst.

Examples of the addition reaction catalyst used at this time include tertiary amines such as trimethylbenzylamine, triethylamine and triethanolamine, trimethylammonium chloride, trimethylammonium bromide,
Trimethylammonium iodide, triethylammonium chloride, quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylphosphonium chloride, diethylphosphonium chloride, phosphonium salts such as triethylphenylphosphonium chloride, lithium chloride, lithium chloride, Examples thereof include ethylene thiourea, tetrabutyl thiourea, and triphenylphosphine, but are not particularly limited thereto.

As the polymerization inhibitor during the reaction, known publicly known agents such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 2,6 ditertiarybutyl-4-methylphenol, t-butylhydroquinone and copper pieces are used. Further, in order to adjust the viscosity of the reaction liquid during the reaction, a reactive diluent may be used in combination, if necessary. Examples of reactive diluents include styrene monomers, allyl monomers, acrylic acid esters, and polyfunctional acrylates.

[0018]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. [Example 1] In a four-necked flask equipped with a cooling pipe, a gas introduction pipe, a thermometer, and a stirrer, 380 g of epoxy resin having an epoxy equivalent of 190 (Epicoat 828: manufactured by Yuka Shell Epoxy Co., Ltd.) and hydroquinone 0 Introducing 0.05 g, while blowing air 25 ml / min at an internal temperature of 115 ° C,
Trimethylbenzyl ammonium chloride 1.65g
Methacrylic acid containing 172g was added dropwise over about 0.5 hours, and after reacting at a reaction temperature of 120 ° C for about 3 hours, an acid value of 15 mg KO
H / g vinyl ester was obtained. To this, 180 g of maleic anhydride was added and after addition reaction at 120 ° C. for 1.5 hours, 3 g of fumaric acid chloride was added and reacted at 110 ° C. for 2 hours to perform fumaric acid transfer. 290 g of styrene monomer was added to the obtained vinyl ester to obtain a fumaric acid-modified vinyl ester resin.

Example 2 900 g of an epoxy resin having an epoxy equivalent of 480 (Epicoat 1001: manufactured by Yuka Shell Epoxy Co., Ltd.) was placed in a four-necked flask equipped with a cooling pipe, a gas introduction pipe, a thermometer and a stirrer. , Hydroquinone 0.1
g of methacrylic acid, 172 g of methacrylic acid containing 1.65 g of trimethylbenzylammonium chloride was added dropwise over a period of about 0.5 hours while blowing air of 25 ml / min at an internal temperature of 115 ° C., and after reacting at a reaction temperature of 120 ° C. for about 3 hours. A vinyl ester having an acid value of 12 mgKOH / g was obtained. To this, 270 g of maleic anhydride was added and after addition reaction at 120 ° C. for 1.5 hours, 5 g of isophthalic acid chloride was added to 110 ° C.
And reacted for 2 hours to transfer fumaric acid. To the obtained vinyl ester, 760 g of styrene monomer was added to obtain a fumaric acid-modified vinyl ester resin.

Example 3 In a four-necked flask equipped with a cooling pipe, N ₂ gas introduction pipe, thermometer and stirring device, 383 g of bisphenol A3PO adduct (KB280: manufactured by Mitsui Toatsu Chemicals, Inc.), anhydrous Charge 196 g of maleic acid and carry out addition reaction at 110-120 ° C. for 2 hours in a nitrogen stream.
An acid-terminated unsaturated polyester with an acid value of 201 mg KOH / g is obtained.

To this, 3.5 g of fumaric acid chloride was added and reacted at 120 ° C. for 2 hours to carry out a transfer reaction, and then 760 g of an epoxy resin having an epoxy equivalent of 190 (Epicoat 828: manufactured by Yuka Shell Epoxy Co., Ltd.), 172 g of methacrylic acid containing 1.65 g of trimethylbenzylammonium chloride was added at the same time, and styrene monomer 20 was added.
0 g was added and the mixture was reacted for 3 hours to obtain an unsaturated polyester-modified vinyl ester.

Example 4 A four-necked flask equipped with a cooling tube, a N ₂ gas introducing tube, a thermometer and a stirrer was charged with 62 g of ethylene glycol and 196 g of maleic anhydride.
Addition reaction is carried out at 110 to 120 ° C. for 2 hours in a nitrogen stream to obtain an acid-terminated unsaturated polyester having an acid value of 430 mgKOH / g.

To this, 5.5 parts of isophthalic acid chloride were added.
g, 120 ° C. for 1 hour to carry out a rearrangement reaction, to which 380 g and 400 g of epoxy resin having an epoxy equivalent of 190 and 200 (produced by Yuka Shell Epoxy Co., Ltd.) and 0.55 g of trimethylbenzylammonium chloride are added for 1 hour. By reaction, an epoxy-modified unsaturated polyester having an acid value of 2 mgKOH / g is obtained. Further, 172 g of methacrylic acid containing 1.1 g of trimethylbenzylammonium chloride was added in 0.5 hours, 200 g of styrene monomer was further added, and the mixture was reacted for 3 hours to obtain an unsaturated polyester-modified vinyl ester.

[Comparative Example 1] In a four-necked flask equipped with a cooling pipe, a gas introduction pipe, a thermometer, and a stirrer, 380 g of an epoxy equivalent 190 epoxy resin (Epicoat 828: manufactured by Yuka Shell Epoxy Co., Ltd.) , Hydroquinone 0.05
g of methacrylic acid, 172 g of methacrylic acid containing 1.65 g of trimethylbenzylammonium chloride was added dropwise over a period of about 0.5 hours while blowing air of 25 ml / min at an internal temperature of 115 ° C., and after reacting at a reaction temperature of 120 ° C. for about 3 hours. A vinyl ester having an acid value of 15 mgKOH / g was obtained. To this, 180 g of maleic anhydride was added and reacted at 120 ° C. for 1.5 hours to obtain a maleic acid-modified vinyl ester. To this, 290 g of styrene monomer was added to obtain a maleic acid-modified vinyl ester resin.

[Comparative Example 2] In a four-necked flask equipped with a cooling pipe, an N ₂ gas introduction pipe, a thermometer and a stirrer, 383 g of bisphenol A3PO adduct (KB280: manufactured by Mitsui Toatsu Chemicals, Inc.), anhydrous Charge 196 g of maleic acid and carry out addition reaction at 110-120 ° C. for 2 hours in a nitrogen stream.
An acid-terminated unsaturated polyester with an acid value of 201 mg KOH / g is obtained. To this, 760 g of epoxy resin having an epoxy equivalent of 190 (Epicoat 828: manufactured by Yuka Shell Epoxy Co., Ltd.),
Trimethylbenzyl ammonium chloride 0.55g
Is added and reacted for 1 hour to obtain an epoxy-modified unsaturated polyester having an acid value of 2 mgKOH / g. Furthermore, methacrylic acid 17 containing 1.1 g of trimethylbenzyl ammonium chloride
2g was added in 0.5 hours, and styrene monomer 20
0 g was added and the mixture was reacted for 3 hours to obtain an unsaturated polyester-modified vinyl ester.

[Test Results] Examples 1 to 4 and Comparative Examples 1 to 1
The conversion rate of maleic acid to fumaric acid of the vinyl ester resin obtained in 2 is shown in Table 1, and the properties of the cured product are shown in Table 2. Test piece preparation conditions were resin / 8% cobalt octylate / 55
% Methyl ethyl ketone peroxide 100 / each
After curing at room temperature with a compounding ratio of 0.5 / 1.0, after-curing at 80 ° C. for 1 hour was used.

[0027]

【table 1】

[Table 2]

[0028]

EFFECTS OF THE INVENTION The production method according to the present invention is particularly useful as a method for improving the performance of vinyl esters because it is easy to modify fumaric acid and unsaturated polyester, which has been difficult in the past.

Claims (2)

[Claims] 1. In a fumaric acid modification method of a vinyl ester obtained by a reaction of an epoxy compound and an unsaturated monobasic acid, maleic anhydride is ring-opened and added to a hydroxyl group of the vinyl ester, and then maleic acid is transferred to fumaric acid at a low temperature. A method for producing vinyl ester characterized by the above. 2. A maleic acid of an acid-terminated unsaturated polyester obtained by a ring-opening addition reaction of maleic anhydride and a glycol is subjected to low-temperature transfer to fumaric acid, and then the terminal acid of the unsaturated polyester is unsaturated with an epoxy compound. A method for producing a vinyl ester, which comprises reacting a basic acid.