JPS60258224A - 2-)2 -aminoethoxy-2-ethylamino)alkanol as epoxy curing agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to curable epoxy resins. For more details,
2-[2-7minoethoxy 2-ethylaminocoalkanol as a curing agent.

Epoxy resins constitute a wide class of polymeric materials with a wide range of physical properties. This resin is characterized by epoxy groups that are cured by reaction with certain catalysts or curing agents to provide a cured epoxy resin composition with certain desired properties. Conventional curing agents include compounds such as polyamines, polycarboxylic acids, anhydrides and Lewis acids.

U.S. Patent Nos. 3,420,828 and 4,338,4
No. 08 describes the synthesis of bis(aminoethyl and ether derivatives, such as 2-[2-aminoethoxy-2-ethylaminocoethanol).

The present invention relates to an epoxy resin composition comprising a polyepoxide and a curing agent represented by the formula % (wherein A represents an alkylene group having 2 to 4 carbon atoms).

The cured resin is useful in applications such as decorative coatings, personnel, adhesives, laminates, and potting materials.

Component A of the two-component composition of the invention consists of an epoxy-based resin, usually a polyepoxide. Generally, epoxy-based resins have an average of at least 1.8
is a vicinal polyepoxide containing a compound having a reactive 1,2-epoxy group.

These polyepoxide materials may be monomeric, polymeric, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and may optionally contain other substituents other than the epoxy group, such as hydroxy It may be substituted with a group, an ether group, an aromatic halogen atom, etc.

Preferred polyepoxides are prepared by epoxidizing the corresponding alkyl ether or by combining an excess molar amount of epichlorohydrin with an aromatic hydroxy compound, i.e., impropylidene bisphenol, novolac, resorcinol, aromatic amine derivatives, etc., in a known manner. It is a glycidyl ether produced by reaction. Epoxy derivatives of methylene or impropylidene bisphenol are particularly preferred.

Commonly used types of polyepoxides useful in the present invention include resinous epoxy polyethers obtained by the reaction of epihalohydrins, such as shrimp chlorohydrin, with polyhydric phenols or polyhydric alcohols. The epoxy resin typically has an average of at least 1.
It has 8 reactive 1,2-epoxy groups. An exemplary, but by no means exhaustive list of suitable dihydric phenols includes: 4,4'-isopropylidene bisphenol, 2,4'-dihydroxydiphenylmethane, 3,3'-dihydroxy Diphenol diethylmethane, 3,4°-dihydroxydiphenylmethylpropylmethane, 2,3″-dihydroxydiphenylethylphenylmethane, 4,4″-dihydroxydiphenylprobylphenylmethane, 4.4″-dihydroxydiphenylbutylphenyl methane, 2
, 2°-dihydroxydiphenylditolylmethane, 4
．． Examples include 4'-dihydroxydiphenyltolylmethylmethane. Other polyhydric phenols that can co-react with epichlorohydrin to give these epoxy polyethers include compounds such as resorcinol, hydroquinone, substituted hydroquinones such as methylhydroquinone, and the like.

Polyhydric alcohols that can co-react with epihalohydrin to give resinous epoxy polyethers include:
Ethylene glycol, propylene glycol, butylene gellicol, bentanediol, bis-(4-hydroxycyclohexyl)dimethylmethane, 1,4-dimethylolbenzene, glycerin, 1,2,6-hexanetriol, trimethylolpropane, mannitol, sorbitol , erythritol, pentaerythritol, dimers, trimers and higher polymers thereof, such as polyethylene glycol, polypropylene glycol, triglycerin, dipentaerythritol, etc., polyallyl alcohol, 2.2', 3.3' - polyhydric hydroxythioethers such as tetrahydroxydipropyl sulfide,
Partial esterification products of mercapto alcohols such as monothioglycerin and dithioglycerin, polyhydric alcohols such as monostearin and pentaerythritol monoacetate,
There are halogenated polyhydric alcohols such as monochlorohydrin such as glycerin, sorbitol, and pentaerythritol.

Other polymerizable polyepoxides according to the invention that can be amine-cured are preferably treated with basic catalysts, e.g.
In the presence of sodium hydroxide or potassium hydroxide, an epihalohydrin such as epichlorohydrin, an aldehyde such as formaldehyde, and a resinous condensate of a -valent phenol, such as phenol itself or a polyhydric phenol, are combined. There is an epoxy novolank resin obtained by reaction. For further details regarding the properties and production of these epoxy resins, please refer to the Handbook of Epoxy Resins written by Riichi H9 and Nebille.
Re5ins), Manufacture Hill Book Co., New York, 1967.

It will be understood by those skilled in the art that the polyepoxide compositions useful in accordance with the present invention are not limited to those containing the polyepoxides described above, but are merely representative of the group of polyepoxides as a whole.

Component B of the two-component composition of the invention consists of a novel curing agent and, optionally, an accelerator. The epoxy resin curing agent of the present invention has the following formula.

HOAN)ICH2CH2QG)[2fJ2NH2, where A is an alkylene group having 2.3 or 4 carbon atoms.

) In the examples, the synthesis of a fullkylene group in which A is 2 carbon atoms is shown.

The synthesis of these curing agents is described in US Pat. No. 3,420,882 and US Pat. No. 4,338,408, which are incorporated herein by reference in their entirety.

Generally, the reaction proceeds as follows. Bis(aminoethyl)ether of the formula % is disclosed in U.S. Pat.
According to No. 20,828, it reacts with an alkylene oxide of formula 0 (wherein R is hydrogen or lower alkyl or a mixture thereof), group).

The reactions of the invention should be carried out at elevated temperatures. Alkoxylation is preferably carried out at a temperature range of 50°C to 150°C. The curing agent can be separated from other products by distillation.

The starting materials are bis(aminoethyl)ether, alkylene oxide and alkylene group Fcoi. Yu, Yuo, wow, yeah. . , K, 1.1 □ The preparation of the compound is further illustrated in Examples.

The present invention also provides a method for producing an epoxy resin by bringing polyepoxide and a curing agent into contact with each other, the curing agent having the formula % (wherein A is an alkylene group having 2 to 4 carbon atoms) The present invention relates to a method for producing an epoxy resin characterized by contacting the resin.

A is an ethylene, propylene, or butylene group, and mixtures thereof can also be used. According to this method, a series of high-grade epoxy resins are produced, which can be used as coating agents and encapsulants.

Useful for adhesives, laminates, potting materials, etc. The cured epoxy resin is notable for rapid curing and outstanding flexibility, impact strength and adhesion, as demonstrated in the examples.

In the method of the invention, the curing agent and optional accelerator are mixed to form a compatible solution. Then the epoxy base resin is added and the ingredients are mixed thoroughly until a homogeneous mixture is obtained.

The curing agent is usually added to the composition in an amount such that for each epoxy group in the epoxy resin component, there is one reactive hydrogen atom in the curing component. They are known as stoichiometric amounts. Stoichiometry can be calculated from the chemical structure and analytical data of the components. Unfortunately, stoichiometry cannot always be calculated.

In the present invention, the appropriate amount of curing agent is that amount necessary to obtain the most desirable properties. The amount must be determined experimentally, and this can be done by conventional methods known in the art. in general,
The number of equivalents of reactive, curable groups ranges from 0.8 to 1.2 times the number of epoxy equivalents present in the curable epoxy resin composition, preferably from 0.9 to the stoichiometric amount. The exact amounts of the components according to the general requirements will depend, as stated above, first of all on the intended use of the cured resin.

For many applications, curing can be performed under atmospheric conditions. However, curing at high temperatures is necessary to achieve the highest properties. The permissible curing temperature range in the present invention is 120° C. with a curing time of 1 to 3 hours.
℃~180℃. Preferred curing is a curing time of 1 to
It is carried out at 125° C. for 2 hours.

If desired, the epoxy resin composition of the present invention can contain an accelerator to speed up the amine curing of the epoxy resin. In some applications, hardeners are beneficial and
This is especially the case when the epoxy resin is used as an adhesive in a flammable environment and therefore prolonged high temperature curing is inconvenient or even dangerous. Ho
Riichi and Nebile have published the "Epoxy Resin Handbook"
, pages 7-14, describe the use of certain amine-containing compounds as epoxy hardener-accelerators.

Many accelerators known in the art can be utilized in the present invention. Examples include salts of phenol,
Salicylic acid, US patent i2. Amine salts of fatty acids as described in H1,901, and U.S. Pat. No. 2,83
Preferred accelerators in the present invention include tertiary amines such as those described in U.S. Pat.
, No. 875,072. These accelerators contain piperazine and flukanolamine in a weight ratio of 8
It consists of a 1:l combination. The amount of the above accelerator is 10 parts by weight of the accelerator per 100 parts by weight of the curing agent.
It can be mixed with the polyoxyalkylene diamine curing agent in an amount of ˜50 parts by weight.

The following Examples illustrate the features of the present invention, and the present invention should not be limited thereto.

By-products from the production of morpholine and 2-(2-amine ethoxy)ethanol (mostly methoxyethylmorpholine, bis(aminoethyl)ether and aminoethylmorpholine) are reacted with ethylene oxide as described below, The produced 11 hydroxyethyl bis(aminoethyl)ether was separated.

A +6 Jlj reactor was charged with 7.9 kg of the aforementioned by-product, heated to 80°C, and 0.95 kg of ethylene oxide was added. The reaction components were then reacted for 1 hour at 80° C. and subsequently stripped at 400 Pa and a temperature of 125° C. to remove 5.98 kg of unreacted material. Then,
The mixture was passed through a wiped thin film distiller at 13.3 Pa and a temperature of 180°C to separate 2-[2-aminoethoxy-2-ethylaminoco-ethanol. The results of gas chromatography analysis of the by-products are as follows.

Area (X) Water 6.0 Morpholine 1,4 Methoxytylmorpholine 18.0 Bis(aminoethyl)ether 66.8 Aminotylmorpholine 4.7 Piperazine/monoethanolamine 1.6 Nor
Set of heated epoxy "L epoxy resin (EEW 188)" 1002-[2-
Aminoethoxy-2-ethyl 24 amino]ethanol gelation time (min) (200g, mass) 23.3
Maximum exothermic temperature ("C) 184.8 Time to maximum exothermic temperature (win) 31.5
3 ■ D Izot impact strength (J
/Otori) 74.7 Tensile strength (MPa) 84.8 Tensile modulus (MPa) 3000 Elongation at break (%) 4.1 Bending strength (MPa) +09 Bending modulus (MPa) 315B Heat deformation temperature ('C )1.8MPa10.45MPa 8
0/85 Shore D hardness (0-10sec) H-899
Liquid glycidyl ether of bisphenol A cured at 80°C for 2 hours and 125°C for 3 hours. 100% by weight epoxy resin (EEW 188) cracked during thermal cycling. Several thermal cycles of the sample: 30 min in 140°C oven, 15 min in -20°C bath, 15 min at room temperature.

I checked for cracks and if there was no change, I put it back in the oven.

The sample was a Whatman 19X 19
6 mm cut from thimble filter paper for cellulose extraction
Ordinary steel washer supported by a ring of filter paper (outside size 25+
am, inner diameter 9.5+*m, thickness 1.8+sm) 50
g inclusions, which were made in an aluminum evaporating dish (milk test: diameter 5c+*×depth IC1).

"Liquid diglycidyl ether of bisphenol A. Epoxy equivalent: 188°"11,'
-3 Ether-heated epoxy -1 EPON 828 100 Hydroxypropyl BAEED34 -D bending strength (MPa) of ether-heated 3II11 epoxy 110 Bending modulus (MPa) 3100 Heat distortion temperature (C, 1,8 MPa 10.45 MPa )
[i0/82 Shore D hardness 78-75''Analysis: Total amine 11.4 meq/g Tertiary 7 Mi7 1.04 meq/g Primary amine 4.73+eeq/g Total 7-t=Tylated product 17 ．． Hmeq/g Gas Chromatograph Surface am Bis(aminoethyl)ether 2.8 Unknown (8 peaks) 17.5 2+2 hours at 80°C, 3 hours at 12'5°C Curing Test Method Summary Tensile Shear Strength (MPa) (ASTM Standard Test Method D-1002) T-Peel Strength (N/m) (ASTM Standard Test Method D-1878) Izod Impact Strength (J/layer) (ASTM Test D-258) Tensile Strength (MPa) (ASTM Test D-238) Tensile modulus (MPa) (ASTM test [1-838) Elongation at break (X) (ASTM test D-238) Bending strength (MPa) (ASTM test D-250) Bending modulus (MPa) (ASTM test D-2flO) Heat distortion temperature ("C) 1.8 MPa 10.45 MPa (A
STM test D-248) Shore D hardness (0-10 seconds) (ASTM test D-2240) Gel time (Cardco gel timer (Ball N, manufactured by Gardner))

Claims (1)

[Scope of Claims] An epoxy resin curing agent represented by the following formula (%) (in the formula, A represents an alkylene group having 2 to 4 carbon atoms). 2. An epoxy resin composition comprising (A) a polyepoxide and (B) a curing agent represented by the formula % (wherein A represents an alkylene group having 2 to 4 carbon atoms). 3. A method for producing an epoxy resin, which comprises bringing polyepoxide into contact with a curing agent represented by the formula % (wherein A represents a fullkylene group having 2 to 4 carbon atoms).