JPH0198613A - Epoxy resin and its production - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin which can be easily handled and can give a cured product excellent in a toughness such as bending strength and bending modulus, by reacting a specified oligocarbonate with an epihalohydrin and conducting the ring closure of the product through dehydrohalogenation by the addition of an alkali. CONSTITUTION:A bisphenol such as bisphenol A or bisphenol F is reacted with phosgene or diphenyl carbonate to obtain an oligocarbonate (A) of formula I (wherein R2-3 are each H, a lower alkyl or a phenyl, or they may be combined together to form a ring, X is a lower alkyl or a halogen, m is the number of substituents other than H and is 0-4, and n is 0-5). Component A is reacted with 2-20mol., per OH group of component A, of an epihalohydrin (B) of formula II (wherein R1 is H or an alkyl, and Y is a halogen) at 50-120 deg.C in an anhydrous state in the presence of a catalyst (C) such as quat. ammonium salt, and the product is subjected to ring closure through dehydrohalogenation by slowly adding thereto an alkali such as NaOH to obtain an epoxy resin of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin and a method for producing the same, and more particularly to an epoxy resin that provides a cured product with excellent toughness and a method for producing the same.

In general, epoxy resins and their cured products are widely used in applications such as electrical equipment materials, paints, adhesives, civil engineering and construction materials, and composite materials. ,
Properties such as toughness, flexibility, and chemical resistance are required.

Conventional commercially available epoxy resins such as bisphenol A diglycidyl ether and bisphenol F diglycidyl ether are liquid at room temperature, and such liquid epoxy resins are mixed with a curing agent and, if necessary, a filler. Many cured products have been produced for various uses. However, the cured products of epoxy resins such as bisphenol A diglycidyl ether and bisphenol F diglycidyl ether produced in this way have low bending strength or bending modulus, and do not have the toughness required in many applications. The problem is that it does not have a satisfactory level.

For this reason, in many applications where toughness is required, cured products of epoxy resins with high epoxy equivalents, such as phenoxy resins, are usually used. However, in general, epoxy resins with high epoxy equivalents, such as phenoxy resins, are solid at room temperature, and cured products are produced by curing epoxy resins with high epoxy equivalents, such as phenoxy resins. In this case, the epoxy resin with a high epoxy equivalent weight must be dissolved in a suitable solvent. Compared to liquid epoxy resins such as diglycidyl ether of 1 and diglycidyl ether of bisphenol F, there is a problem in that it is difficult to handle when producing a cured epoxy resin product.

The inventors of the present invention conducted intensive studies to solve these problems, and found that an epoxy resin derived from carbonate having a specific structure can be cured with excellent toughness such as bending strength and bending elasticity. The present invention has been completed based on this discovery.

The present invention is intended to solve the problems associated with the prior art as described above, and can provide a cured product with excellent toughness such as bending strength and bending elasticity, and can be cured at room temperature. An object of the present invention is to provide an epoxy resin which is in a liquid state and is therefore easy to handle when producing a cured product, and a method for producing the same.

1. The epoxy resin according to the present invention has -mona [I] (in the formula, R
4 is hydrogen or an alkyl group.

R2 and R3 may be the same or different, and each may be hydrogen, a lower alkyl group, or a phenyl group, or R2 and R3 may be mutual. X is a lower alkyl group or a halogen group. m is the number of substituents other than hydrogen, and is O-4. n is O-5. ).

The method for producing an epoxy resin according to the present invention includes the following steps:
] (In the formula, R2 and R3 may be the same or different, and each is hydrogen, a lower alkyl group, or a phenyl group, or R2 and R3 are bonded to the bean,
The common bond between R2 and R3 is a halogen group. m is the number of substituents other than hydrogen, and must be O-4. n is O~
It is 5. ) is reacted with shrimp helohydrin represented by -Momonena [111] (in the formula, R1 is hydrogen or an alkyl group, and Y is a halogen group), and an alkali is added to the colander. It is characterized by dehydrohalogenation and ring-closing reaction.

The epoxy resin according to the present invention can provide a cured product having excellent toughness, and since it is liquid at room temperature, it is easy to handle when producing the cured product.

Hereinafter, the epoxy resin according to the present invention will be specifically explained. The epoxy resin according to the present invention has the following structure: -Momonena [I] (wherein R1 is hydrogen or an alkyl group).

R2 and R3 may be the same or different, and each is hydrogen, a lower alkyl group, or a phenyl group, or R2 and R3 are tautogenic groups. m is the number of substituents other than hydrogen, and is O-4. n is O~5
It is. ).

In the formula, R1 is hydrogen or an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an i-butyl group, and among these, hydrogen and a methyl group are preferable.

In the formula, R2 and R3 may be the same or different, and each is hydrogen, a lower furkyl group, a phenyl group, or R2 and R3 together with the carbon atom to which R2 and R3 are commonly bonded, For example, the following groups are formed.

In the formula, X is a lower alkyl group or a halogen group,
Specifically, they include methyl group, ethyl group, propyl group, ropetyl group, 5ec-butyl group, t-butyl group, chlorine, bromine, and iodine. Moreover, in the formula, m is the number of substituents other than hydrogen, and ranges from 0 to 4.

This m may be the same for each aromatic group.
may be different.

In the formula, n is the number of repetitions and is 0 to 5.

In a preferred epoxy resin according to the present invention, R1 is hydrogen, R2 and R3 are both methyl groups, and m
is 0, (in the formula, n is O-5).

Such epoxy resins are made by using aliphatic polyamines, aromatic polyamines, dicyandiamide, polybasic carboxylic acids or their acid anhydrides, etc. as curing agents, which are used as curing agents for ordinary bisphenol A-based epoxy resins. Can be hardened. The cured product obtained in this way (9) has a higher bending strength and bending strength compared to cured products obtained from conventionally commercially available liquid epoxy resins such as diglycidyl ether of bisphenol A and diglycidyl ether of bisphenol F. It has excellent toughness such as elasticity. Furthermore, the epoxy resin according to the present invention is liquid at room temperature and is easy to handle when producing a cured product.

One method for producing epoxy resin Next, six IB methods for producing epoxy resin according to the present invention will be explained.

The epoxy resin according to the present invention is characterized by -mona [nl (in the formula, R
2 and R3 may be the same or different, and each is hydrogen, a lower alkyl group, or a phenyl group, or R2 and R3 are a halogen group. m is the number of substituents other than hydrogen, and is O-4. n is O-5. ) to the oligocarbonate represented by -monana [
I11] (wherein R1 is hydrogen or an alkyl group,
Y is a halogen group. ) It can be produced by reacting an epihalohydrin represented by the following formula, adding an alkali to a colander, dehydrohalogenating it, and carrying out a ring-closing reaction.

4R 凰■ t! of the epoxy resin according to the present invention! In method A,
- Monka [II] ... [■] (In the formula, R2 and R3 may be the same or different, and each is hydrogen, a lower alkyl group, a phenyl group, or R2 and R3 It is a halogen group.

m is the number of substituents other than hydrogen, and is O-4. n is O-5. ) is used as a starting material.

R2, R3, and X1m1n in the oligocarbonate represented by the general formula [II] are each represented by the general formula [I
] R2, R3, X in the epoxy resin represented by
Teal like m and n.

The above oligocarbonates that serve as starting materials are A, F, and H.
egoty in ”Con+prehensive
Organic Chemistry”, ed, 1
．． 0.5uthertand, pergamon P
ress.

1979, Part 9, 10. (1979, Bergamon Press.

1.0. As shown in Chapters 9 and 10 of "Comprehensive Organic Chemistry" edited by Sutherland (A, F. Hegarty), the reaction of bisphenols such as bisphenol A1 bisphenol F1 bisphenol AD with phosgene or the above It can be easily synthesized by transesterification reaction between bisphenols and diphenyl carbonate.

In this way, the oligocarbonate represented by -Momonena [I[] is synthesized by the reaction between bisphenols and phosgene or by the transesterification reaction between bisphenols and diphenyl carbonate. After the reaction is complete,
Usually, unreacted bisphenols remain, but it is not necessary to specifically remove these unreacted bisphenols, and oligocarbonate containing unreacted bisphenols can be used as a starting material.

Epihalohydrin The oligocarbonate as described above is reacted with an epihalohydrin represented by -Momonena[1[1] (wherein R1 is hydrogen or an alkyl group and Y is a halogen group).

In the formula, R1 is the same as R1 in the epoxy resin represented by -mona [I]. Moreover, in the above formula, Y is a halogen group. Specifically, chlorine, bromine or iodine is used, with chlorine being particularly preferred.

However, in the method for producing an epoxy resin according to the present invention, first, an amount of oligocarbonate represented by -Momonena [II] and an excess molar amount, preferably 2 to 20 times the molar amount per one hydroxyl group of the oligocarbonate, are added. Preferably, the epihalohydrin represented by the general formula [111] in 3 to 15 times the molar amount is mixed with a catalyst such as a quaternary ammonium salt such as tetramethylammonium chloride or a quaternary phosphonium salt such as triphenylphosphonium bromide. The reaction is carried out while the system is preferably maintained in an anhydrous state.

The reaction temperature is 50-120°C, preferably 60-100°C.
The reaction is usually carried out under normal pressure.

Next, the reaction product obtained by the above reaction is added with a
When a 2.0-fold molar amount of alkali metal hydroxide, preferably sodium hydroxide, is gradually added, the reaction product is dehydrohalogenated to cause a ring-closing reaction, yielding 1q of the epoxy resin according to the present invention. At this time, the temperature is 50-90℃, preferably 60-80℃, and the pressure is 60-500Jll.
IllH() is preferably 90 to 300!IIIRHg. Water generated during the reaction is continuously removed from the system by azeotropic distillation with epichlorohydrin.

The epoxy resin thus obtained is similar to ordinary bisphenol A-based epoxy resins, and contains aliphatic polyamines, aromatic polyamines, dicyandiamide, polybasic carboxylic acids, or their anhydrides. It can be heated and cured according to a conventional method using a curing agent such as.

Heat curing of such epoxy resins is usually performed at room temperature or at
Preferably, the reaction is carried out at 200°C for 1 to 20 hours.

■ Rigoshiri The epoxy resin according to the present invention has a structure represented by -monka [I], and includes an aliphatic polyamine used as a curing agent for ordinary bisphenol A-based epoxy resins, By using aromatic polyamines, etc., it is possible to provide a cured product with excellent toughness such as bending strength and bending elasticity, and since it is liquid at room temperature, the cured product can be
! This has the effect of being easy to handle during construction.
-The present invention will be explained below using Examples and Reference Examples, but the present invention is not limited to these Examples and Reference Examples.

In a 2-g capacity three-tube flask equipped with a cross-screen stirrer, a thermometer, and a condenser, the formula [nl.

Oligocarbonate (number average molecule m570
n = 2.0, bisphenol Δ content 22% by weight) 2529 (0.885 equivalent as OH group), epichlorohydrin 1154SF (12,48 mol), tetramethylammonium chloride 0.9119 (0,0
083 mol) and reacted at 95°C for 5 hours.

Subsequently, after a water removal device was attached to the Mitsuro flask, solid sodium hydroxide 509 (1.33 mol) was roughly added into the Mitsuro flask over a period of 2 hours. The reaction temperature at this time was 70°C, and the pressure was 150a*
I set it to HO.

Water as a by-product was continuously removed from the Mitsuro flask together with epichlorohydrin by azeotropic distillation.

Excess unreacted epichlorohydrin was recovered by reducing the pressure in the flask, and then 300 g of xylene was added to the flask, and insoluble inorganic salts and the like were filtered off.

The above-mentioned filtrate thus obtained was gradually dropped into a strongly stirred 20% by weight aqueous monosodium phosphate solution at a temperature in the range of 0 to 5°C.

The solution thus obtained was then added to the aqueous layer for 11 m
The organic layer was collected, and the water remaining in the organic layer was azeotroped with xylene and removed from the system.

The liquid obtained by azeotropically removing water from the organic layer with xylene was filtered through a 04 type glass filter, and the xylene was distilled off under reduced pressure from the filtrate. A viscous liquid was obtained.

Next, we investigated the physical properties of this viscous liquid. The results are shown below.

Epoxy equivalent ω 292 Viscosity (55° C.) 76.000 C, P, S Further, the results of examining the infrared absorption spectrum of the above viscous liquid are shown in FIG.

From the above results, the pale yellow viscous material of 384S obtained by distilling xylene from the filtrate under reduced pressure has the formula [■]°”
.

It was identified as an epoxy resin containing the structure represented by (100=2).

Reference Example 1 309 epoxy resins obtained in the above Example 1 were collected,
It contains triethylenetetramine (TT) as a curing agent.
A mixture containing 2.5 g of A> and a composition ratio of 8.4 parts by weight of curing agent to 100 parts by weight of epoxy resin was heated at room temperature for 16 hours, then heated at 100°C for 2 hours to cure the epoxy resin. I got something.

The physical properties of the cured epoxy resin thus obtained were measured according to JIS K 6911. The measured results are shown in Table 1.

Irrigation-1 309 samples of Yuepomitsu R-140P (epoxy equivalent: 188, bisphenol A type epoxy resin, trade name of Mitsui Petrochemical Industries, Ltd.) were collected, and 3.9 g of triethylenetetramine (TTA>) was added as a curing agent. In addition, the composition ratio was set to 12 parts of the curing agent to the most heavy part of Epomic R-140P100.
．． The mixture made into a 9-fold part was cured, and the physical properties of the obtained cured product were determined according to JIS K 69 in the same manner as in Reference Example 1.
Measurement was carried out according to 11.

The results are shown in Table 1.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum of the epoxy resin obtained in Example 1. Agent Patent Attorney Shunichi Suzuki October 14, 1988 Commissioner of the Japan Patent Office Yoshi1) Bunki Tono1, Indication of the case 1988 Patent Application No. 257,9452, Name of the invention Epoxy resin and its production Method 3: Relationship with the case of the person making the amendment Patent applicant name: Mitsui Petrochemical Industries, Ltd. 4, agent (zip code: 141): 6, 3rd floor, Araku Building, 2-19-2 Nishi Gotanda, Parts Ward, Tokyo. Column 7 of “Detailed Description of the Invention” of the specification to be amended, content of amendment (1) In the specification, page 12, line 8 to w410, “(formula) %formula%” (formula) and (2) In the third to last line from the bottom of page 22 of the specification, the following is corrected: [Formula [■] °.

Claims (4)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R_1 is hydrogen or an alkyl group. R_2 and R_3 are different even if they are the same. each may be hydrogen, a lower alkyl group, a phenyl group, or R_2 and R_3 may be bonded to each other,
R_2 and R_3 may form a ring together with the carbon atom to which they are commonly bonded. X is a lower alkyl group or a halogen group. m is the number of substituents other than hydrogen, and is 0 to 4. n is 0-5. ) Epoxy resin represented by. (2) The epoxy resin according to claim 1, wherein R_1 is hydrogen, R_2 and R_3 are both methyl groups, and m is 0. (3) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [II] (In the formula, R_2 and R_3 may be the same or different, and each represents hydrogen and lower It may be an alkyl group, a phenyl group, or R_2 and R_3 may be bonded to each other to form a ring with the carbon atom to which R_2 and R_3 are commonly bonded. X is a lower alkyl group or a halogen group. group. m is the number of substituents other than hydrogen and is 0 to 4. n is 0 to 5.) to the oligocarbonate represented by the general formula [III] ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼... [III] (In the formula, R_1 is hydrogen or an alkyl group, and Y is a halogen group.) React the epihalohydrin represented by the formula, add an alkali, General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼... [I] (In the formula, R_1 is hydrogen or an alkyl group. R_2 , R_3 may be the same or different, and each is hydrogen, a lower alkyl group, a phenyl group, or R_2 and R_3 are bonded to each other,
R_2 and R_3 may form a ring together with the carbon atom to which they are commonly bonded. X is a lower alkyl group or a halogen group. m is the number of substituents other than hydrogen, and is 0 to 4. n is 0-5. ) A method for producing an epoxy resin represented by (4) The method for producing an epoxy resin according to claim 3, wherein R_1 is hydrogen, R_2 and R_3 are methyl groups, m is 0, and Y is chlorine.