JPS58187421A - Reactive diluent - Google Patents

Abstract

PURPOSE:A novel reactive diluent for epoxy resins that contains 1,7-octadienediepoxide as a major component, thus effecting good dilution without any adverse effect on erosion and water resistance as well as mechanical properties. CONSTITUTION:The objective reactive diluent contains 1,7-octadienediepoxide of the formula as a major component. The compound is obtained by allowing an organic peracid such as peracetic acid to act on, e.g., 1,7-octadiene for epoxidization of its olefin linkages.

Description

[Detailed description of the invention] The present invention relates to new and useful reactive diluents.

Traditionally, n-butyl glycidyl ether (n
-BGIl! ) or phenyl glycidyl ether, cresol glycidyl ether or p-t-butylphenyl glycidyl ether (p-t-BPGE
), difunctional diluents such as neopentyl glycol diglycidyl ether or polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether;
．． Alicyclic epoxide diluents such as 2-cyclohexene oxide or 3-methoxycyclohexene oxide are known as typical diluents, but first, monofunctional diluents such as the aliphatic or (alkyl)phenyl diluents mentioned above are used. Although it has good dilutability, it has the disadvantage of reducing various physical properties such as corrosion resistance, water resistance, and mechanical properties, and the above-mentioned bifunctional diluent can increase the flexibility of the epoxy resin. However, although the above-mentioned 111111 group single-functional diluents have good diluting ability and can be expected to improve physical properties, they suffer from curing by acid anhydrides and are difficult to use with amines. It has the disadvantage that it cannot be cured.

However, as a result of intensive research in order to obtain a new type of diluent that overcomes all of the drawbacks of the various conventional reactive diluents as described above, the present inventors found that 1,7-octacyene diepoxide can be used as a diluent of this type. When applied to epoxy resin as n-BG [! The present inventors have completed the present invention by discovering that it has a diluent comparable to that of epoxy resins, is capable of amine curing, and has good compatibility with various epoxy resins. .

That is, the present invention provides a reactive diluent containing 1,7-octashiene diepoxide as a main component represented by the structural formula.

Here, in order to obtain the 1,7-octadiene diepoxide (hereinafter also referred to as 1.7-ODD), the structural formula CH
2-CB-Ct12CH2-CB2-Ct12-CB-
The 1,7-octadiene represented by CH2[11] is preferably treated with an organic peracid, such as performic acid or peracetic acid, and this 1,7-octadiene is
6 and US Pat. No. 3,622,646, it can be obtained by thermal decomposition of cyclooctene, or Tetrahedron LetLers
(2) p, 163 (1972), British Patent Nos. 1278806 and 1341324,
and JP-A-54-130504, 54 1305
As described in No. 05, No. 54-132507, No. 55-19274, and No. 55-19275, palladium compounds and/or trialkylphosphines, tricyclo It can be obtained by reductive linear doubling with formic acid or a salt thereof and water in the presence of a catalyst such as alkylphosphine or triphenylphosphine.

Next, when the 1,7-octadiene thus obtained is treated with an organic peracid, each of the olefin bonds is epoxidized to produce the desired diepoxide compound.

Here, typical organic peracids include peracid, peracetic acid, perbenzoic acid, etc., but in particular, acetaldehyde in air is prepared according to the method described in British Patent No. 737,974. It is industrially advantageous to use peracetic acid obtained by oxidation p.

Apart from the above, epoxidation known as an in 5-itu method can also be used, but in this method, for example, a formic acid solution is generally heated in advance and hydrogen peroxide is gradually added thereto.

The molar ratio of 1.1-octadiene and organic peracid such as peracetic acid is 1:2 to 1.
: The reaction temperature is preferably within the range of 3, and the reaction temperature is 0 to 100.
°C, preferably 50 to 70 °C is suitable,
The reaction time is usually 3 to 10 hours, preferably 4 to 6 hours.

Also, the progress rate of the reaction at this time is, for example, ^nal
ytic-al Chemistry VOL, 19,
p, 414 (194 cr), or Ind, Fng, Chem, VOL, 43, p.
72B (1951) by measuring the oxirane content of the product.

Typical solvents used in such epoxidation reactions include aliphatic ketones such as acetone or methyl ethyl ketone; esters such as ethyl acetate or n-butyl acetate; halogenated hydrocarbons such as chloroform or dichloroethane. ; or aromatic hydrocarbons such as benzene or toluene.

The above-mentioned 1.7 which is the main component of the diluent of the present invention thus obtained
-〇〇〇 is a material with good heat resistance and electrical insulation properties, adhesive, or It provides a resin for molding, but since the 1°7-ODD itself has a low viscosity, it is useful as a reactive diluent for well-known and commonly used bisphenol-type epoxy resins. 1.7-ODD and (meta)
The addition reaction product with acrylic acid can also be used as a diluent for UV-curable acrylic urethane resins.

Mata, this El 1, 7-0011 Niha r (INO
X 206J or r UNOX207J (or more,
It is also possible to use a mixture of known and commonly used reactive diluents such as those manufactured by Union Carbide (USA).

Next, the present invention will be specifically explained with reference to Examples and Application Examples, in which all parts and percentages are based on weight.

Reference Example (Preparation Example of 1,7-ODD) 110 parts of 1,7-octanoene was dissolved in acetone, and 762.9 parts of 24% 4% peracetic acid in acetone was added to the solution over 3 hours while stirring at 60°C. It was dripped gradually.

After the dropwise addition was completed, the mixture was stirred at the same temperature for 3 hours, then cooled to 25°C, and 130 parts of anhydrous sodium carbonate was gradually added to neutralize the acetic acid.

Next, insoluble sulfur and lithium acetate was suction filtered, the filtrate was concentrated under reduced pressure to remove acetone, and the remaining oil was distilled under reduced pressure, resulting in a colorless and transparent product with a boiling point of 91°C/8■I1.
136.3 parts (yield: 96%) of 1.7-octazidine diepocytosite were obtained.

The oxirane oxygen content of this product was 21.32%4, which was almost the same as the theoretical oxirane oxygen content of 22'', 50%.

Example 1 1.7-Octazidine diepoxide was used as a reactive diluent, and this was prepared as [Evicron 830J (Dainippon Ink Chemical *miw, diglycidyl ether of bisphenol F; hereinafter abbreviated as Epoxy Tree 111(1)). ) and “Ebiclone 850J (manufactured by the same company, bisphenol A
diglycidyl ether; hereinafter abbreviated as epoxy resin (2). ) were mixed respectively.

At this time, the addition ratio of 1,7-octazidine diepoxide was varied, and this addition ratio (mixing ratio) and viscosity (2
Gardner-Holt) relationship at 5°C was determined.

The results are shown in Figure 1. ? - The dilution capacity of octadiene dieboxide is n -B
Although it is slightly inferior to GB, it is about the same level. Considering the molecular weight, this is natural and reasonable since it has a higher molecular weight than n-BGB.

Example 2 Using 1.7-octazidine diepoxide as a reactive diluent, a curable composition of benzyldimethylamine was added to each mixed yarn of 1.7-octazidine diepoxide and epoxy resin R (1) and epoxy resin (2). A product was prepared and its reactivity (curing suitability) with amines was investigated.

That is, a total of 50 g of this mixture of dieboxide and various epoxy resins was collected in a 100 mff1 polypropylene cup, and triethylenetetramine corresponding to 80% of the epoxy equivalent was added thereto, mixed with stirring for 30 seconds, and then left to stand. Then, the dark fight until the whole gelatinized was measured, and the results were shown as the gel time in Figure Ii+2.

Application Examples 1 and 2 A curable composition was prepared by adding triethylenetetramine in an amount equivalent to the epoxy equivalent to the epoxy resin-reaction diluent mixture obtained according to the formulation shown in Table 11.

Next, the results of a performance test conducted on each molded article obtained by a conventional method using each of these compositions are shown in the same table.

Application Examples 3 and 4 The epoxy resin-reaction diluent mixture obtained according to the formulation shown in Table 2 was further added with liquid tetrahydrochloride (manufactured by Ebicuron B-570J (Dainippon Ink & Chemicals)) in an amount equivalent to the epoxy equivalent of the epoxy resin-reaction diluent mixture. A curable composition was prepared by adding a phthalic anhydride curing agent) and benzyldimethylamine.

Next, molded products were obtained using each of these compositions in a conventional manner.

The results of the performance tests conducted on each of the obtained molded products are summarized in the same table.

Chapter 1 Table / Table 2

[Brief explanation of the drawing]

Figure 141 is implemented! 1.7-OD of the mixture shown in P1]
2 is a graph showing the U relationship between the mixing ratio of D and the viscosity of the mixture, and FIG. 2 is a graph showing the 1.7-
It is a graph showing the relationship between the addition rate (%) of 0% and the gel time (minutes) of the composition. In Figure 1 and IFI Figure 2, the curve or straight line marked 1 represents the epoxy resin (1) -1,7,-ODD mixed system, and the curve or straight line marked 2 represents the epoxy resin (2) -1,7-ODD.
Represents the Dfi combined system. Patent ratio - Person Nippon Ink Chemical Industry Co., Ltd. Oxirane Chemical Co., Ltd. No. 1 m

Claims (1)

[Claims] A reactive diluent whose main component is 1,7-octazidine dieboxide represented by the following structural formula.