JPS62525A - Production of radical-curable unsaturated alkyd - Google Patents

Abstract

PURPOSE:To obtain an unsaturated alkyd excellent in workability, water resistance and chemical resistance, by reacting an epoxy resin with a phenolic resin at a specified ratio and esterifying the product with an alpha,beta-unsaturated polybasic acid. CONSTITUTION:An epoxy resin having 2-4 epoxy groups in the molecule is reacted with a phenol at an equivalent ratio of the phenol groups to the epoxy groups of 0.5-1/1 in the presence of a curing catalyst for epoxy resin. The obtained reaction product is esterified with an alpha,beta-unsaturated polybasic acid or its anhydride at 150-250 deg.C in an inert gas atmosphere. In this way, a radical- curable unsaturated alkyd having repeating units of a reaction product having an allyloxymethylene groups as side chains and having an ester bond between the epoxy resin and the alpha,beta-unsaturated polybasic acid and having the number of the repeating units of 2-20 is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a radically curable unsaturated alkyd having a novel structure useful for various uses such as paints, adhesives, molding materials, and FRP.

[Conventional technology]

Currently, unsaturated polyester resins and vinyl ester resins are widely used as radical-curable resins that can be cured at room temperature.

However, as the uses of resins have become more diverse, the performance required of resins has become more detailed and demanding, and it is often the case that existing Y resins are insufficient to meet these demands. For example, in the case of gel coat, which is commonly used as a coloring and surface protection layer for FRP, there is a movement to improve water resistance, alkali resistance, and corrosion resistance against specific chemicals without increasing costs.

Vinyl ester resins have extremely excellent water resistance and chemical resistance, so of course they can be used for this purpose, and in fact, their boiling resistance itself is extremely good, so they are generally used as dull coats. However, there is a need for further improvement in the workability required for gel coats, such as suitability for spraying, ability to provide chikuntrobi, and no color fading, and efforts to improve the gel coat continue in line with these expectations. However, the desired results have not been achieved at this stage.

On the other hand, as for unsaturated I-lyester resin, CH of bisphenol type polyester shown by the following formula.

Styrene solutions have become the mainstream gel coat for bathtubs due to their excellent workability. However, it has the disadvantage that its hot water resistance is inferior to that of vinyl ester resin, and it does not meet high requirements.

[Problem that the invention seeks to solve]

As a result of intensive research to improve the various drawbacks of these existing resins, the present inventors discovered that unsaturated alkyl and do having a new structure represented by the general formula below have better water resistance and chemical resistance than these existing resins. They found that they have at least the same or better properties and are superior in terms of workability, and have completed the manufacturing method of the present invention.

[Means for solving problems]

That is, in the present invention, an epoxy resin having 2 to 4 epoxy groups in one molecule and a phenol are cured for epoxy resin at a ratio of 0.5 to 1 equivalent of phenol group to 1 equivalent of epoxy group. It is characterized by reacting in the presence of a catalyst, then adding an α-β unsaturated polybasic acid or its acid anhydride to the resulting reaction product, and performing an esterification reaction at 150 to 250°C in an inert atmosphere. A radical curing method in which the repeating unit is a reaction product having an allyloxymethylene group in the side chain and an ester bond between an epoxy resin and an α-β unsaturated polyhydrochloric acid, and the number of repeating units is 2 to 20. The object of the present invention is to provide a method for producing unsaturated alkyds.

[Effect]

The radically curable unsaturated alkyd obtained by the method of the present invention has fewer allyloxymethylene double bonds in the side chain, and is therefore presumed to have a favorable effect on the boiling resistance and heat distortion temperature of the resin. Ru. In addition, the main chain of the unsaturated alkyd obtained by the method of the present invention is an epoxy resin and α-β.
Since it consists of repeating units in which an unsaturated polybasic acid is ester bonded, it is thought that it has excellent workability when used as a styrene solution.

The unsaturated alkyd obtained by the method of the present invention has 2 to 20 repeating units (approximately 1.000 to 10 in terms of molecular weight).
000). When the repeating unit is smaller than 2, the curing properties of the resin are poor, and when it is larger than 20, it becomes difficult to carry out the present invention, which is not preferable.

In order to aid understanding of the present invention, the reaction formula can be shown as a model as shown in the following formula.

CM.

Epoxy resin phenol addition reaction product CI) Addition reaction product 1:I) + uooc-ci=cu
-coon→unsaturated alkyl fumaric acid, etc. Epoxy resins used in the present invention include, for example, the following types.

(a) Various diglycidyl ethers of bisphenol A or bisphenol F represented by the following general formulas.

(b) Polyglycidyl ether type epoxy resin (n = 0 to 2, R1 is -H or -CH3)
eC) A so-called peracetic acid type epoxy resin having two or more than two groups obtained by oxidizing a double bond in the molecule.

A typical example is Union Carbide's Unox-4.
221 is mentioned.

b) Epoxy resins having a diphenyl structure, such as YX-4000 manufactured by Yuka Shell Co., Ltd. (e) Other epoxy resins such as triazine triglycidyl ether, resorcin diglycidyl ether, etc.

Further, examples of phenols to be reacted with the epoxy resin include the following types. Namely, phenol, ortho-cresol, meta-cresol, ortho-cresol, 2
, 3-xylenol, 2,4-xylenol, 2,5-
Xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, Nocraethylphenol, Nograine propylphenol, No<? -y Tasha IJ -f thylphenol, /" 7 ocflphenol, nogranonylphenol, no<?raphmylphenol, nographenylphenol, adduct of phenol and styrene, 2.5--/brome Phenol, 2.
5-nochlorophenol, nocrachlorophenol, α
-naphthol, β-naphthol.

Monoderivatives of dihydric phenols such as hydroquinone monomethyl ether are also available, but they are less advantageous in terms of cost.

Epoxy resin curing reaction catalysts are useful for the reaction between epoxy resins and phenols, and it is particularly effective to use aromatic tertiary amines, quaternary ammonium salts, and the like. Typical examples include benzyldimethylamine, tris(dimethylamino)phenol, trimethylbenzylammonium chloride, and the like.

The reaction product between epoxy resin and phenols has an additional α
- Maleic anhydride, maleic acid, fumaric acid, and itaconic acid are the types of α-β unsaturated polybasic acids to be added to β-unsaturated polybasic acids or their acid anhydrides and esterified to form unsaturated alkyds. Can be mentioned. The esterification is carried out in an inert gas stream at a temperature of 150 DEG to 250 DEG C., preferably 180 DEG to 230 DEG C.

Although the produced unsaturated alkyd can be used as it is, it is preferably used in the form of a resin dissolved in a desired monomer. At that time, it is necessary to add polymerization inhibitors such as polyhydric phenols, quinones, and copper salts to maintain the stability of the resin. Examples of the monomer include styrene, vinyltoluene, chlorostyrene, diallyl phthalate, sialyl terephthalate, diallyl isophthalate, methyl methacrylate, tert-butyl methacrylate, inbutyl methacrylate, and cyclohexyl methacrylate. The most representative monomers are aromatic monomers such as styrene and vinyltoluene. It goes without saying that the resin produced by the method of the present invention may contain fillers, reinforcing materials, colorants, stabilizers, and polymers, if necessary.

〔Example〕

Next, examples will be shown below to help understand the present invention.

Example 1 1t Seno J? equipped with a stirrer, fractional condenser, thermometer, gas inlet pipe. In a rubble flask, 232 g of 3509.3.5-xylenol (232 g of 3509.3.5-xylenol (0 hydroxyl group per equivalent of epoxy group) of Asahi Dow's DER-330 as an epoxy resin
．． When 1.8 g of benzyl methylamine (95 equivalents) is charged and heated, it rapidly starts to generate heat when the temperature exceeds 110°C, so it is cooled to prevent the temperature from exceeding 160°C.

After the reaction was then carried out at 150 to 160° C. for 5 hours, it was confirmed by infrared spectroscopy that the free epoxy groups had completely disappeared.

Next, 110 g of fumaric acid was added and esterified at 200 to 210° C. in a nitrogen gas stream, resulting in an acid value of 14.1, so 0.129 of hydroquinone was added, and the mixture was poured into a metal vat and solidified.

A dark brown unsaturated alkyd product was obtained with a melting point of about 110-115°C.

The average molecular weight was 4,600.

A system in which 100 parts of unsaturated alkyd (A) was pulverized and 2 parts of styrene ketone monooxide, 1 part of cobalt naphthenate, and 0.2 parts of dimethylaniline was added was oxidized at room temperature in 49 minutes, and slowly exothermed. The maximum temperature reached 133°C.

The heat distortion temperature of the cast product was 108°C.

Example 2 As a bisphenol A epoxy resin, Epicoat 807 manufactured by Yuka Shell Co., Ltd. was used as a bisphenol A epoxy resin of 350. ! 9. Phenol 179
g (ratio of epoxy groups to phenolic OH 1:0.
95) was weighed into the same apparatus as in Example 1, and mixed uniformly at 50°C, trimethylbenzylammonium chloride o, sg was added and the temperature was raised to 110°C to 13°C.
Since it rapidly generates heat at 0°C and reaches around 160°C, it is cooled during this time to keep it below 160°C.

After reacting at 155 to 160° C. for 3 hours, infrared spectroscopic analysis showed that the absorption of epoxy groups completely disappeared.

Then maleic anhydride 90. ! Add i+, 200~2
When esterified in an inert gas stream at 10° C., the acid value became 21.4 after 5 hours.

Hydroquinone sail 1. ! Add 9 and inject into a metal vat,
Cooling. An unsaturated alkyd (C) having a melting point of about 100° C. and an average molecular weight of about 2,600 was obtained.

Grind 100 parts of unsaturated alkyd (C), dissolve it in 100 parts of polymethylstyrene by heating at 60°C, cool it to room temperature, and add 100 parts of unsaturated alkyd (C) to 100 parts of unsaturated polyester resin, which has a donor color number of 2.
~3, with a viscosity of 3.9 poise.

100 parts of unsaturated polyester resin (D), methyl ethyl ketone A? -2 parts of oxide, 1 part of cobalt nanthenate
The system to which 0.1 part of dimethyl ayu 9f was added was kept at room temperature,
It turned into a keratinium in 33 minutes and slowly generated heat, reaching a maximum temperature of 14.
The temperature reached 4℃.

The heat distortion temperature of this casting resin was 98°C.

Example 3 In a four-bottle flask equipped with a stirrer, a fractional distillation condenser, a gas inlet tube, and a thermometer, 370 ji of Epicoat 827 from Yuka Shell Co., Ltd. as an epoxy resin was added. Lacresol 195g (ratio of epoxy group to phenolic hydroxyl group is 1:0.9), benzyldimethylamine 1.5g
When heated, it rapidly generates heat when the temperature exceeds 110°C, so it is necessary to cool it to prevent it from rising above 160°C.

After the reaction was then carried out at 150 to 160° C. for 5 hours, it was confirmed by infrared spectroscopy that the free epoxy groups had completely disappeared.

Next, add 110 g of fumaric acid and add 200 to 200 g of fumaric acid in an inert atmosphere.
When heated at 10° C. for 6 hours, the acid value became 19.6, so 0.139 of hydroquinone was added, and the mixture was poured into a metal vat and solidified.

An unsaturated alkyd [F]) having a yellowish brown color and a melting point of about 110°C to 115°C was obtained. The average molecular weight was 3200.

100 parts of styrene was added to 100 parts by weight (hereinafter referred to as "parts") of the unsaturated alkyd (■), heated to 60 to 70°C and stirred to form an unsaturated polyester resin (F') with a Gardner color number of 2 to 2. 3. Obtained with a viscosity of 9.6 voids.

A system in which 100 parts of unsaturated polyester resin (F), 2 parts of methyl ethyl ketone oxide, and 2 parts of cobalt naphthenate were added was fluorinated in 49 minutes, and the maximum temperature reached 139° C. while gently generating heat.

The heat distortion temperature of the cast product was 108°C.

Example 4 In a fourth flask equipped with a stirrer, a fractionating condenser, a gas inlet tube, and a thermometer, 360 g of Asahi Dow's DER-330 as an epoxy resin and 188 g of phenol were added.
! 9 (The ratio of epoxy group and 7-tri-nol hydroxyl group is 1:1
), benzyldimethylamine 1.51 and 150~
Heat to 160°C.

Initially, due to the ring-opening reaction of the epoxy, heat is generated rapidly, so the temperature is kept below 180° C. by cooling during this period.

When heated to 150-160°C for 3 hours, it was confirmed by infrared spectroscopy that the epoxy groups had completely disappeared.

Next, 110 g of fumaric acid was added and esterification was carried out at 200 to 210° C. in a nitrogen stream. The reaction was stopped at an acid value of 26.9. 1 g of hydroquinone was added, and the mixture was poured into a metal vat and cooled.

An unsaturated alkyd (G) having a yellowish brown color, a melting point of about 110° C., and a molecular weight of about 2,400 was obtained.

100 parts of unsaturated alkyd p) is pulverized and dissolved in 100 parts of styrene while stirring and heating to 50-60°C. An unsaturated polyester resin with a Gardner color number of 3 to 4 and a viscosity of 5.4 poise was obtained.

100 parts of unsaturated polyester resin (6), 2 parts of methyl ethyl ketone/9-oxide, and 2 parts of cobalt naphthenate were added and mixed uniformly. The resin turned into a keloid in about 55 minutes, and gradually generated heat, reaching a maximum temperature of 131. ℃ reached.

A continuous boiling test was conducted on a casting plate measuring 5 cm x 5 cm and 3 mm thick, and no abnormality in appearance was observed even after 2000 hours of boiling, indicating excellent water resistance.

In addition, there were no abnormalities in a continuous boiling test using a 10% caustic soda aqueous solution for up to 500 hours, and extremely good alkali resistance was similarly observed.

Example 5 In a 1 t portable flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas inlet tube, 380 g of YX-4000 from Yuka Shell Co., Ltd. as an epoxy resin and 1 phenol were added.
69 g (0.g equivalent of hydroxyl group per equivalent of epoxy group) and 1.5 g of pen-solz methylamine were charged, and 11
, If the temperature is raised to around 0℃, it will rapidly generate heat, so cool it down.
Prevented the temperature from rising above 160°C.

Subsequently, the reaction was carried out at 150 to 160°C for 5 hours, and as a result of infrared spectroscopic analysis, it was confirmed that the absorption of epoxy groups completely disappeared.

Next, 110.9% of fumaric acid was charged, and 19% of fumaric acid was added in an inert gas stream.
Esterification was proceeded at 0 to 210°C, stopped at an acid value of 11.4, and 0.19% of hydroquinone was added, and the mixture was poured into a metal vat and cooled.

The obtained unsaturated alkyd (1) has a melting point of about 120°C,
It was dark brown in color and had a molecular weight of about 5,000.

100 parts of unsaturated alkyd (I) was ground and dissolved in 100 parts of styrene by heating to 70 to 80°C.

The obtained unsaturated polyester resin (J) has a viscosity of 5.8
Poise and Gardner colors were 5 to 6.

To 100 parts of unsaturated polyester resin (J), 2 parts of methyl ethyl ketone oxide and 2 parts of naphthenic acid conolate were added, and the added material became dull in 20 minutes and gradually generated heat, reaching a maximum exothermic temperature of 157°C. did.

The heat distortion temperature of the cast product was 121°C.

Example 6 1t-2A equipped with a stirrer, a fractionating condenser, a thermometer, and a gas inlet tube. In a rubble flask, add 360 g of Asahi Dow's DEN-431 as an epoxy resin and 1 phenol.
7C1 (00g equivalent of hydroxyl group per equivalent of epoxy group)
, 1.59% of benzyldimethylamine was charged, and the temperature was heated to 110°C.
If you heat it up to a certain temperature, it will start to generate heat rapidly, so please cool it down.
Prevented the temperature from rising above 60°C.

The mixture was then heated at 150 to 160 DEG C. for 3 hours, and as a result of infrared spectroscopic analysis, it was confirmed that free epoxy groups had completely disappeared.

Adding 116 g of itefumaric acid (1 equivalent of carxyl group to 1 equivalent of epoxy group) and esterifying it at 200 to 210°C in a nitrogen gas stream resulted in an acid value of 9.4 in about 5 hours.
Therefore, 0.05 F of hydroquinone was added and poured into a metal vat.

The obtained unsaturated alkyd (A) is reddish brown and has a melting point of about 1
It was 00℃.

100 parts of styrene was added to 100 parts of unsaturated alkyd (6), heated to 60 to 70°C, and dissolved to produce an unsaturated polyester resin (6). The Gardner color number was 4 to 5 and the viscosity was about 15 poise.

A system in which 100 parts of unsaturated polyester resin, 2 parts of methyl ethyl ketone oxide, 1 part of cobalt naphthenate, and 0.2 parts of dimedone was added, turned into a slag and generated heat in 39 minutes at room temperature, reaching a maximum temperature of 158°C. .

The heat distortion temperature of the casting resin was 129°C.

Example 7 In a 1t Ceno 4 rubble flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas inlet tube, 260 g of Unox 4221, 188 g of phenol (1 equivalent of phenolic hydroxyl group per 1 equivalent of epoxy group), and 1 benzyldimethylamine were added. Charge .5g and raise the temperature to 160-170°C. Since the heat generation was weak and did not occur rapidly, there was no need for cooling.

After the reaction was then carried out at 160 to 170° C. for 10 hours, it was confirmed by infrared spectroscopic analysis that the free epoxy groups had completely disappeared.

Next, 98 g of maleic anhydride was added, and 2
When esterified for 6 hours at 10-220°C, the acid value was 19.
1, 0.03 g of hydroquinone was added and poured into a metal vat to solidify.

An unsaturated alkyd (b) was obtained which was dark yellowish brown in color and had a melting point of about 110°C.

Grind 100 parts of unsaturated alkyl, and add 100 parts of styrene.
The mixture was heated and dissolved at 60 to 70°C.

An unsaturated polyester resin (2) having a Gardner color number of 4 to 5 and a viscosity of 4.7 poise was obtained.

An unsaturated polyester resin (1100 parts, to which 2 parts of cobalt naphthenate and 2 parts of methyl ethyl ketone A-oxide were added) was dulled at 50°C for 15 minutes and then generated heat, reaching a maximum temperature of 144°C.

The heat distortion temperature of the cast product was 134°C.

Example 8 100 parts of unsaturated alkyd (b) was ground and dissolved in 100 parts of diallyl terephthalate by heating at 90 to 100°C. A viscous, slushy unsaturated polyester resin was obtained at room temperature.

Unsaturated polyester resin 1) In 100 parts, 5 parts of benzoyl peroxide, 1 part of NOF IE-HEXA 3M, and 1 part of Percumil D were heated and dissolved, and initially at 60°C for 24 hours.
Then at 80°C for 24 hours, at 100°C for 6 hours, at 130°C
Casting for measurement of heat distortion temperature was performed under curing conditions of 4 hours.

The heat distortion temperature of this cast product was 220°C or higher.

Claims (1)

[Claims] An epoxy resin having 2 to 4 epoxy groups in one molecule and a phenol are mixed in the presence of a curing catalyst for epoxy resin at a ratio of 0.5 to 1 equivalent of phenol group to 1 equivalent of epoxy group. reaction, then adding an α-β unsaturated polybasic acid or its acid anhydride to the obtained reaction product, and carrying out an esterification reaction at 150 to 250°C in an inert atmosphere. A radically curable unsaturated alkyd, which has an allyloxymethylene group in the molecule and has a repeating unit of a reaction product having an ester bond between an epoxy resin and an α-β unsaturated polyhydrochloric acid, and has 2 to 20 repeating units. manufacturing method.