JPS63227616A - Epoxy resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin useful as electrical or electronic casting materials, coating compound and adhesive, having both excellent heat resistance and mechanical characteristics, by adding an epihalohydrin to a specific polyamine and successively reacting with an aqueous solution of a caustic alkali. CONSTITUTION:An epihalohydrin (preferably epichlorohydrin) is added to a polyamine {e.g. 2,2-bis[4-(4-aminophenoxy)phenyl]propane} shown by formula I (Ar1 and Ar2 are aromatic hydrocarbon derived from 6-20C bihydric phenol residue; R1 and R2 are H, halogen or 1-3C alkyl) and successively reacted with an aqueous solution of a caustic alkali to give the aimed epoxy resin shown by formula II (G is glycidyl). The amount of the epihalohydrin used is preferably 2-5 equivalents based on sum of active hydrogen of the polyamine.

Description

Detailed Description of the Invention "Industrial Field of Application" The present invention relates to a glycidylamine-based epoxy resin that provides a cured product with excellent thermal and mechanical properties, especially a glycidylamine-based epoxy resin containing 06-
The present invention relates to an epoxy resin having a structure in which an aromatic hydrocarbon group derived from a C211 dihydric phenol residue and an N,N-diglycidylaminoaryl group are connected by an ether bond.

"Conventional technology and problems" Epoxy resin is used in paints, electricity/electronics, adhesives, civil engineering/architecture, etc.
It is used in many fields such as matrix resin for FRP. Among them, glycidylamine resins (hereinafter referred to as general glycidylamine resins), such as tetraglycidyldiaminodiphenylmethane and triglycidyl (m-9p->aminophenol), have a higher crosslinking density than general-purpose epi-bis type resins. Because it has a is extremely brittle and cannot be said to have sufficient mechanical properties.

In order to improve this, (I) polyalkylene glycol diglycidyl ether (Asahi Denka Co., Ltd. ED-50) was added to the curing system.
6 etc.), urethane modified epoxy resin (Asahi Denka Co., Ltd. EP)
(2) a compound having a soft segment such as an alkylene ether amine (Mitsui Texaco Co., Ltd. Diefermine series, etc.) in part or all of the curing agent; , or CTBN.

A method using a rubber component such as ATBN is known.

However, although these improvement methods increase mechanical strength, they have the drawback of decreasing heat resistance, and there is a desire to develop epoxy resins with excellent mechanical properties and heat resistance.

"Means for Solving the Problems" In view of the above circumstances, the inventors of the present invention have conducted extensive research into improving mechanical properties without sacrificing the excellent heat resistance that is characteristic of general glycidylamine-based epoxy resins. As a result, we have arrived at the present invention.

That is, the first aspect of the present invention is the following general formula N) (wherein, Arl
, A r 2 each represent an aromatic hydrocarbon group derived from a dihydric phenol residue of 06 to C2°, R + , R
z each independently represents a hydrogen atom, a halogen atom, or an 01-C3 alkyl group, and G represents a glycidyl group. ) The second aspect of the present invention is an epoxy resin represented by the following general formula (ff> (where Ar, , Ar2 each represent an aromatic hydrocarbon group derived from Cb to C20 dihydric phenol residues). and R+ and Rz each independently represent a hydrogen atom, a halogen atom, a C
It represents an 8-C3 alkyl group, and C represents a glycidyl group. General formula (I) characterized by adding shrimp halohydrin to polyamines represented by ) and then reacting with an aqueous caustic solution (wherein, Art , Art , R + , Rz , and G each represent the above-mentioned patent claims) Scope Same as the content described in paragraph 1.

Each content is a method for producing an epoxy resin represented by the following.

As is clear from the above structural formula, the epoxy resin of the present invention has an aromatic hydrocarbon group derived from a dihydric phenol residue of 06 to C2° as a skeleton and an N,N-diglycidylaminoaryl group connected through an ether bond. It has a structure. Compared to general glycidyldiamine-based epoxy resins, the epoxy resin of the present invention has a main chain extended by the arylene ether, which contributes to a reduction in the density of epoxy groups, that is, the crosslink density. Furthermore, since the ether bond has a large flexibility, it imparts flexibility to the cured product, and the alignment of the aromatic rings suppresses the decrease in heat resistance to a small degree that has almost no practical effect.

The polyamines used in the present invention (hereinafter referred to as polyamines) have a structure in which an aromatic hydrocarbon group derived from a 06 to C20 dihydric phenol residue and an aminoaryl group are connected by an ether bond as a skeleton. be. Such polyamines can be used regardless of the production method, but taking bis(4-(4-aminophenoxy)phenyl)sulfone as an example, (I) 4.4'-
A method of reacting an alkali metal salt of a dihydric phenol such as dihydroxyphenylsulfone disodium salt with a nitro compound such as dinitrobenzene, and then reducing the reaction;
(2) It can be produced by a method of reacting a civalide such as 4.4'-dichlorodiphenylsulfone with an aminophenol over a basic catalyst.

Examples of such polyamines include 2゜2-bis(I(4-aminophenoxy)phenyl)propane (BAPP manufactured by Wakayama Seika Kogyo Co., Ltd.), bis(4-(4-aminophenoxy)phenyl)sulfone, (same BAPS)
, I, 4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(4-aminophenoxy)
Benzene (TPE-R), I, 3-bis(3-aminophenoxy)benzene (TPE-M), 2゜2-
Bis(4-(3-aminophenoxy)phenyl)propane, bis(4-(4-aminophenoxy)phenylcomethane, bis(4-(3-aminophenoxy)phenylcomethane, bis(4-(5-amino) naphthoxy)phenyl]sulfone, 2゜2-bis[3,5-dibromo-4-(
4-aminophenoxy)phenyl]propane, bis[3
, 5-dimethyl-4-(4-aminophenoxy)phenylcomethane, 2,2-bisC4-C3-chloro-5-aminophenoxy)phenyl]propane, and the like.

Moreover, any plurality of these polyamines can be used in combination as necessary.

Among these compounds, 2,2-bis[4-(4-
aminophenoxy)phenyl]propane, bis(4-(
It is preferable to use 4-aminophenoxy)phenyl]sulfone etc. from the viewpoint of ease of raw material availability, balance of performance, etc., and in each general formula (I), an epoxy resin in which Ar2 is as shown below can be obtained; A method for producing epoxy resin will be explained. For glycidylation of polyamines, conventionally known methods for glycidylation of aromatic amines can be applied. For example, it is also possible to adopt a manufacturing method in which polyamines are heated and dissolved in epihalohydrin, and an aqueous caustic alkali solution is continuously added dropwise to this solution to react. However, in order to improve the purity of the obtained resin, a two-step method is preferred, in which active hydrogen is first added to polyamines to eliminate active hydrogen, and then an aqueous caustic solution is reacted. It has been found that the two-step method suppresses the ring-opening reaction of the epoxy group, resulting in a highly pure resin.

In addition, for the addition reaction of polyamines and epihalohydrin,
Particular preference is given to using water as addition catalyst. The amount of water used is 0.05 to 5.0 mol% based on polyamines,
Any amount can be selected preferably within the range of 0.5 to 2.0 mol%.

As the epihalohydrin, epichlorohydrin, β-methylepichlorohydrin, shrimp bromohydrin, shrimp iodohydrin, etc. can be used, but epichlorohydrin is preferably used because of its industrial ease of availability. The amount of epihalohydrin used may be at least equivalent to the total active hydrogen of the polyamines, but it is preferably used in an amount of 2 to 5 equivalents to help dissolve the polyamine.

The addition reaction temperature and time are 005 to 1 at 20 to 110°C.
2 hours, preferably 1.0 to 6.0 hours at 70 to 80°C.

In the second step, a dehydrohalogenation reaction is performed using caustic alkali. Caustic alkalis include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide,
Although barium hydroxide and the like can be used, sodium hydroxide is preferably used because of its industrial availability. Although caustic alkali can be used as a solid or as an aqueous solution, an aqueous solution is preferred for ease of handling. The amount of caustic alkali to be used is 1.0 to 2.
0 equivalent, preferably 1.1 to 1.5 equivalent. The temperature and time of the dehydrohalogenation reaction are 20 to 70 °C and 10
minutes to 3 hours, preferably 0.5 to 2.0 at 40 to 60°C
It's time.

As a catalyst for the dehydrohalogenation reaction, it is particularly suitable to use a phase transfer catalyst selected from quaternary ammonium salts, quaternary phosphonium salts, and quaternary arsonium salts. Generally well-known phase transfer catalysts include quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium bromide, and triethylmethylammonium chloride; class phosphonium salt;
Quaternary arsonium salts and the like can be used.

The amount of phase transfer catalyst used is from 0.01 to polyamines.
Any amount can be selected within the range of 100 mol%, preferably 0.05 to 5 mol%.

The dehydrohalogenation reaction is usually carried out in epihalohydrin, but excess epihalohydrin can also be distilled off before the reaction. In this case, inert solvents such as ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as chloroform and methylene chloride may be used as diluents. desirable.

After the reaction is completed, the salt produced is removed by filtration or washing with water, and unreacted shrimp halohydrin or inert solvent is distilled off to obtain the epoxy resin (I) of the present invention.

The epoxy resin thus obtained is yellow to tan and liquid to solid at room temperature. In addition, the introduction of glycidyl groups into the resin is indicated by the infrared absorption spectrum of 905 to 905.
This can be confirmed from the absorption of the epoxy group at 920 cm-', the characteristic absorption at 2.5-4° Oppm in the proton nuclear magnetic resonance spectrum, and the measurement of the epoxy equivalent by the hydrochloric acid-pyridine method.

The epoxy resin obtained by the above manufacturing method can be cured by combining it with a curing agent in the same way as normal epoxy resins. The curing agents used are of any type, including tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, trimellitic anhydride, Acid anhydrides such as hensifhenonetetracarboxylic anhydride; chain aliphatic polyamines such as diethylenetriamine and triethylenetetramine; cycloaliphatic amine necks such as menthene diamine and isophorone diamine; (m-, p-) Alicyclic polyamines such as xylylene diamine; (m-, p-)
Aromatic polyamines such as phenylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone;Polyamides; Imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole; trifluoride Lewis acid-amine complexes represented by boron-amine complexes; dicyandiamide and its derivatives;
Examples include polyphenols such as cresol novolak, phenol novolac, and polyvinylphenol.

Furthermore, the epoxy resin of the present invention can also be used by optionally mixing it with other epoxy compounds.The epoxy compounds used in the mixture can be of any type and the blending ratio can be selected arbitrarily.

Furthermore, in addition to the curing agent, the epoxy resin of the present invention may optionally contain a curing accelerator such as a tertiary amine or imidazole; a filler such as silica or talc; a reinforcing agent such as glass fiber or carbon fiber; Various additives such as additives, pigments, flame retardants, etc. can be blended.

"Action/Effect" The epoxy resin of the present invention has a skeleton of 06 to C2°.
Aromatic hydrocarbon groups derived from phenol residues and N,N
- Because it has a structure in which diglycidylaminoaryl groups are connected by ether bonds, the mechanical properties of the cured product, including flexibility, are improved compared to general glycidylamine-based epoxy resins. On the other hand, in terms of thermal properties, the epoxy resin of the present invention inherits the characteristics of glycidylamine type resins, and the decrease in heat resistance of the resulting cured product is suppressed to a slight degree that has almost no practical effect.

As described above, since the epoxy resin of the present invention has both excellent heat resistance and mechanical properties, it is useful as, for example, casting materials for electrical and electronic applications, paints, adhesives, laminated materials, and matrix materials for FRP. be.

"Examples" A more specific explanation will be given below with reference to Examples, but the present invention is not limited in any way by the Examples. In addition, hereinafter, "parts" means "parts by weight."

Example 1 2.2-bisC4-(4-aminophenoxy)phenyl]propane (BAPP manufactured by Wakayama Seika Kogyo Co., Ltd.) 4
1.05 g (I00mM), -[: Pichlorohydrin 1.11 g (I, 20M), pure water 0.10
g was placed in a fourth flask, and the temperature was gradually raised to 70°C. After the initial fever subsides, keep the internal temperature at 75-80℃,
Stirring was continued for an additional 5 hours.

Next, the inner height was lowered to 50℃, and with strong stirring, 39.5 g of a 48.6% caustic soda aqueous solution (as caustic soda was added to 4.
The hep ′ -concave reaction continued.

The precipitated common salt was removed by filtration, and the aqueous layer containing salts was removed by decantation. 150m7 organic layer
! After washing 4 times with pure water and dehydrating with sulfur salt, unreacted epichlorohydrin was distilled off to obtain tetraglycidyl [2,
2-bis(4-(4-7minophenoxy)phenol)
I got a pro. Epoxy resin A was pale yellow in color and exhibited a viscous liquid state at room temperature. Figure 1 shows the infrared absorption spectrum of the epoxy resin.

The epoxy equivalent measured by the hydrochloric acid-pyridine method specified in JIS K-7231 was 172.

Example 2 2. Bis(4-(4-aminophenoxy)phenyl)sulfone (BAPS manufactured by Wakayama Seikagaku Kogyo Co., Ltd.) instead of 41.05 g of 2-bis(4-(4-aminophenoxy)phenyl)propane T-1 pipe x L-!-(
4-′? 65.2 g of L″q・Jxy)phenyl)sulfone (hereinafter referred to as epoxy resin B) was obtained.Epoxy resin B was solid at room temperature, and its melting point measured by microscopy was 48 to 55°C. The infrared absorption spectrum of epoxy resin B is shown in Figure 2.It was measured by the hydrochloric acid-pyridine method specified in JIS K-7231.Application Example 1 100 parts of epoxy resin A obtained in Example 1, methylnadic anhydride Mix 88.00 parts of Hitachi Chemical Co., Ltd. and 0.70 parts of benzyldimethylamine to make a festival, pour it into two glass plates fitted with 3111 spacers, and place it in the oven as it is. 100℃/
It was thermally cured under the conditions of 2Hr+150°C/IHr+180°C for 15Hr.

The obtained cured product was cut into a required size using a diamond cutter to make a sample, and the JIS K-69
Heating deformation temperature specified in 11 (hereinafter referred to as HDT)
, bending test, and room temperature water absorption were measured. Also, 120℃,
The water absorption rate after an accelerated test (hereinafter referred to as PCT) using heated steam at 2 atm was also measured. The sample pretreatment conditions and physical property measurements were conducted in accordance with the method specified in JIS K-6911.

Application Example 2 100 parts of the epoxy resin B obtained in Example 2, 83.59 parts of methylnadic anhydride (manufactured by Hitachi Chemical Co., Ltd.), and 0.70 parts of hensyl dimethylamine were mixed and heated to form a face. A sample was prepared by casting and thermosetting in the same manner as in Example 1, and its physical properties were measured.

Comparative Example 1 100 parts of tetraglycidyldiaminodiphenylmethane (epoxy equivalent of 120), 126.1 parts of methylnadic anhydride (Hitachi Chemical Co., Ltd.), 0 benzyldimethylamine
．． A cured product was prepared by casting and heat curing in the same manner as in Application Example 1, except that 70 parts were mixed to form a face, and the physical properties were measured.

Comparative Example 2 Triglycidyl p-aminophenol (epoxy equivalent: 1
23) 100 parts, Hitachi Chemical Co., Ltd. methylnadic anhydride 123.0 parts, benzyldimethylamine 0.70
A cured product was prepared by casting and heat curing in the same manner as in Application Example 1, except that the parts were mixed to form a face, and the physical properties were measured.

The blending ratio, curing conditions, and physical properties of the obtained cured product of Application Example 1.2 are summarized in Table 1. Similarly, Comparative Example 1
．． 2 is shown in Table 2.

Table 1 1); Methylnadic anhydride manufactured by Hitachi Chemical Co., Ltd. 2); N
, N-benzyldimethylamine Table 2); Methylnadic anhydride manufactured by Hitachi Chemical Co., Ltd. 2)-;
N,N-benzyldimethylamine 3); Tetraglycidyldiaminodiphenylmethane 4); Triglycidyl p-
aminophenol

[Brief explanation of the drawing]

FIGS. 1 and 2 show infrared absorption spectra of epoxy resins A and B obtained in Example 1.2, respectively.

Claims (1)

[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Ar_1Ar_2 are C_6 to C_2_, respectively)
R_1 and R_2 each independently represent a hydrogen atom, a halogen atom, and an alkyl group of C_1 to C_3, and G represents a glycidyl group. ) Epoxy resin represented by. 2. In the general formula (I), Ar_2 is an aromatic hydrocarbon group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Claim 1
Epoxy resin as described in section. 3. In the general formula (I), Ar_2 is an aromatic hydrocarbon group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Claim 1
Epoxy resin as described in section. 4. General formula (II) below ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, Ar_1 and Ar_2 are C_6 to C_2, respectively.
_0 represents an aromatic hydrocarbon group derived from a dihydric phenol residue, R_1 and R_2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group of C_1 to C_3, and G represents a glycidyl group. ) The general formula (I) is characterized by adding epihalohydrin to polyamines represented by the formula and then reacting it with an aqueous caustic solution. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Ar_1 , Ar_2, R_1, R_2, and G are each the same as described in claim 1 above. 5. A method for producing an epoxy resin represented by: 5. The amount of epihalohydrin used is represented by general formula (II). The production method according to claim 4, wherein the amount of epihalohydrin used is equal to or more than the equivalent amount to the total active hydrogen of the polyamines represented by general formula (II). 7. The manufacturing method according to claim 4 or 5, wherein the epihalohydrin is epichlorohydrin. 8. General 0 to polyamines as a catalyst for the addition reaction between polyamines represented by formula (II) and epihalohydrin.
．． Claim 4 using 05 to 5.0 mol% water
5. The manufacturing method according to item 5 or 7. 9. 0 to polyamines as a catalyst for the addition reaction between polyamines represented by general formula (II) and epihalohydrin.
．． 9. The manufacturing method according to claim 8, wherein 5 to 2.0 mol% of water is used. 10. The production method according to claim 4, 5, 7, or 8, wherein the addition reaction product of the polyamine represented by the general formula (II) and epihalohydrin is reacted with caustic alkali.