JPS6242950A - Curable unsaturated alkyd and production thereof - Google Patents

Abstract

NEW MATERIAL:A curable unsaturated alkyd shown by the formula I (R1 and R2 are H or methyl, repectively; n is 0 or 2; m is 2-20). USE:Useful for various uses such as coating compound, adhesive, molding material, FRP, etc., by dissolving the curable unsaturated alkyd in a monomer copolymerizable with the unsaturated bond in the molecule and curing it in the presence of a radical catalyst. Having improved properties in water resistance and chemical resistance and improved workability. PREPARATION:An epoxy resin shown by the formula II of bisphenol diglycidyl ether type is reacted with p-cumyl phenol in an amount to eliminate the epoxy group in the epoxy resin to give a compound shown by the formula III and the hydroxyl group in the compound is esterified with an alpha,beta-unsaturated polybasic acid or its anhydride, to give a compound shown by the formula I.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a radically curable unsaturated alkyd having a novel structure useful for various uses such as paints, adhesives, molding materials, and FRP, and a method for producing the same. .

[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 become more diverse, the performance required of the resins becomes more detailed and sophisticated, and it is often felt that existing resins are insufficient to meet these demands. For example, in the case of coloring FRP and coatings that are commonly used as surface protective layers, 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 naturally they can be used in this way, and in fact, their boiling resistance itself is extremely good, so they are generally used as r-coat. However, there is a need for further improvements in the workability required for r-coat, such as sprayability, thixotropy, and no color fading, and efforts to improve it continue in line with these expectations. However, the desired results have not been achieved at this stage.

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

Styrene solutions are popular for their good workability and have become the mainstream for bathtub coatings. However, its hot water resistance is inferior to that of vinyl ester resins, and it has the drawback that it does not meet all 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 found that an unsaturated alkyd with a new structure represented by the general formula below has lower water resistance and drug resistance than these existing resins. It has been discovered that the present invention has properties equivalent to or superior to those of other materials, and is superior in terms of workability.

[Failure to solve the problem]

That is, the present invention provides a curable material represented by the general formula % (wherein R1 and R2 each represent a methyl group spanning hydrogen, n is 0 to 2, and m is an integer of 2 to 20). All unsaturated alkyds are available.

Furthermore, in the present invention, an epoxy resin represented by the general formula %) is reacted with a certain amount of roughmylphenol in an amount that eliminates the epoxy groups in the epoxy resin to form a reaction product [I] (hereinafter referred to as a blank). After generating, the hydroxyl group in the reaction product [j) is converted to α
-Providing a method for producing a curable unsaturated alkyd represented by the general formula %, characterized by esterification with a β-unsaturated polybasic acid or its anhydride, wherein R, , R2, n and m are the same as above].

[Effect]

The unsaturated alkyd of the present invention has a novel structure represented by the above general formula, and has a pasic ξ runoenooxymethylene group in the side chain, so it is bulky and has fewer double bonds per molecular weight. However, it is estimated that this has a favorable effect on the boiling resistance and heat distortion temperature of the resin. The main chain of the unsaturated alkyd of the present invention is composed of repeating units in which bisphenol noglyzodyle ether and α-β unsaturated polybasic acid are ester-bonded, so like bisphenol-type polynister, it can be used as a styrene solution. It is thought that it will have excellent workability when used. The number of repeating units is 2 to 20 (equivalent to about 1 to 10,000 when converted to molecular weight), and if the number of repeating units is smaller than 2, the resin will have poor curability and if it is larger than 20, it will be difficult to carry out the present invention. .

The unsaturated alkyd according to the present invention is dissolved in a polymerizable monomer (hereinafter abbreviated as mono=7-) capable of bonding with unsaturated bonds in the molecule, and then cured in the presence of a radical catalyst. It can be used for various purposes such as paint, adhesive, molding, FRP, etc.

The method for synthesizing the unsaturated alkyd of the present invention is to react bisphenol nogly/norneedle type Epoquin resin with gramafylphenol, and then convert the hydroxyl group in the reaction product [1] into an α-β unsaturated polybasic acid. Another method is esterification using the anhydride. The flow is shown below using a typical example.

(Hereinafter, blank spaces) The epoxy resin used in the present invention is of the phenylglycyl ether type, commonly referred to as the so-called bisphenol type.

For example, the type shown by the following general formula synthesized from bisphenol A and epichlorohydrin (see the margin below) φ Mouth-mouth n is preferably in the range of 0 to 2, and it is necessary to increase the number of repeating units. There isn't.

Furthermore, a methylene-bisphenylglyceride sol ether type epoxy resin commonly known as bisphenol F-type epoxy resin can also be used.

The reaction ratio of the epoxy resin and glafumylphenol is suitably 1 equivalent or less of phenolic hydroxyl group or more than 0.5 equivalents per 1 equivalent of epoxy group.

If the amount is less than 0.5 equivalent, it is not preferred because it tends to gel when esterified with an unsaturated polybasic acid or its acid anhydride.

During the reaction, tertiary amines that are generally used as curing accelerators for epoxy resins, such as benzyldimethylamine, tris(dimethylamino)phenol, or quaternary amines, are used.
The use of grade ammonium salts and the like is highly effective in terms of promoting the reaction.

Examples of the α-β unsaturated polybasic acid or its acid anhydride used in the present invention include maleic anhydride, maleic acid, and fumaric acid. At that time, it can also be modified with a small amount of saturated polybasic acid.

Esterification is carried out in the usual manner, i.e. in an inert gas stream from 180 to
It is carried out at a temperature of about 220°C.

The unsaturated alkyds obtained by esterification are styrene, vinyltoluene, and sialyl phthalate.

It can be dissolved in copolymerizable monomers such as noaryl terephthalate and methacrylic acid ester, and can be provided for various uses.

At this time, in order to prevent gelation, it is necessary to add a small amount (0.01 to 0.5 phr) of commonly used polymerization suppressants such as polyhydric phenols and quinones.

It goes without saying that fillers, reinforcing materials, colorants, mold release agents, polymers, etc. can be used in combination, depending on the needs of the application.

〔Example〕

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

Note that the parts used are parts by weight.

Example 1 A stirrer, a temperature, a gas inlet pipe, a distillation condenser, and a separable flask were installed. 360 g of Asahi Dow's DER-332 as the xylene resin, P roughmylphenol, i24. ? (The ratio of epoxy groups to phenolic hydroxyl groups is l: 0.97), 2 g of 1-IJ methylbenzylammonium chloride was added, and the temperature was 120°C.
If the temperature exceeds 1, it will rapidly generate heat, so please cool it if necessary.
The temperature was maintained below 60°C.

After about 3 hours, as a result of infrared analysis (see Figure 1), free epoxy groups were no longer observed, so 116 g of fumaric acid was added and esterification was carried out at 200-210°C in a nitrogen gas stream. Ta.

The process was stopped at an acid value of 192 (estimated average molecular weight of about 5500), and 01 g of hydroquinone was added and poured into a metal vat to solidify. Unsaturated alkyd (A), yellowish brown, melting point approximately 110°C
was obtained (see Figure 2).

100 parts of unsaturated alkyd (A) was ground and dissolved in styrene 100 while heating at 60 to 70°C.

The obtained polyester resin (B) has a Gardner color number of 2.
-3, viscosity was 17 poise.

A yarn prepared by adding 2 parts of methyl di-derketone i''-oxide, 1 part of leafthenic acid, and 0.1 part of trimethylaniline to 100 seconds of unsaturated polycoastyl (B) was keeled in 136 minutes and slowly generated heat. Maximum temperature +31℃
It reached 7. The heat distortion temperature is 98℃/ζ0100
11 after testing a casting plate of rrm
The 0-zero strength retention rate was 93 (relative), which was excellent with no change in appearance.

Example 2 Into the same apparatus as in Example 1, 350 g of Dingpiquat 807 manufactured by Jieki Shell Co., Ltd. as bisphenol F type ehoquine resin was added.
, ・Mother cumylphenol 382.9 (ratio of epoxy group to hydroxyl group it-1: 0.9), 2 g of benyl dimethylamine was added for 10 minutes, and the temperature was raised (a) and rapidly from around 110℃. When the temperature was cooled to below 160°C and then kept at 150 to 160°C for 3 hours, it was determined that free epoxy groups disappeared as a result of infrared analysis.

Next, maleic anhydride 98! ! was added, esterification was carried out at 200 to 210°C in a nitrogen gas stream, and the mixture was stopped at an acid value of 20.9. Hydroquinone of 0.19 was added, and the mixture was poured into a metal vat and solidified.

An unsaturated alkyd C) having a yellowish brown color and a melting point of about 110° C. was obtained.

100 parts of unsaturated alkyd (C) was ground and dissolved in 100 parts of vinyltoluene at 60-70°C.

Gardner color number 2-3. An unsaturated polyester resin (D) having a viscosity of 39 poise was obtained.

100 parts of unsaturated polyester resin (D), 2 parts of methyl ethyl ketone peroxide, cobal naphthenate l-
Adding 1 part of zomethylaniline and 01 part of zomethylaniline turns into a gel in 23 minutes, generates heat slowly, and reaches a maximum exothermic temperature of 133.
℃ reached.

The heat distortion temperature was 96°C.

[Brief explanation of the drawing]

FIG. 1 shows the infrared spectrum of the reaction product of the epoxy/resin obtained in Example 1 and gramafylphenol. FIG. 2 shows the infrared spectrum of the unsaturated alkyd of the present invention obtained by the reaction of the above reaction product with fumaric acid.

Claims (2)

[Claims] (1) Curable unsaturated alkyd substantially represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R_1 and R_2 each represent hydrogen or a methyl group, and n is 0 to 2. , m is an integer from 2 to 20]. (2) An epoxy resin represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is reacted with paracumylphenol in an amount that eliminates the epoxy groups in the epoxy resin, and the reaction product [I] ▲ Formula ,
Chemical formulas, tables, etc. are available ▼ After producing a reaction product [I], the hydroxyl group in the reaction product [I] is esterified with an α-β unsaturated polybasic acid or its anhydride. A method for producing a curable unsaturated alkyd represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, R_1, R_2, n and m are the same as above].