JPS58206579A - Polyepoxy compound - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R is H or CH3; Y is -O- or formula II). EXAMPLE:A compound of formula III. USE:Useful as a structural material or matrix resin in composite materials of carbon fibers, etc., and having the thermal anisotropy. PROCESS:Terephthalaldehyde is reacted with p-aminophenol or p-aminobenzoic acid in a solvent, e.g. tetrahydrofuran (THF), if necessary in the presence of an acidic catalyst, e.g. p-toluenesulfonic acid, at 20-60 deg.C for 1-10hr to give a precursor of formula III (Z is -OH or -COOH), which is then epoxidized with an epihalohydrin or beta-methylepihalohydrin to afford the aimed compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyepoxy compound having thermal anisotropy. The polyepoxy compound of the present invention is a structural material,
Matrix resins, adhesives, sealants for carbon fiber composites,
It is used as a powder coating resin for C4J.

In certain polymer compounds, the molten sacrificial material is anisotropic at a certain temperature! It is known that highly elastic products can be obtained by processing and molding wood with a high grade of 1-& using the property of 4: (the property of molecules arranging in one direction in the molten state). ing.

For example, Bernard et al.
When n=4, X represents C03 or Ctt, or n=
6 and X represents H, Cl-1a or Ct.
Molded products such as filaments and fiber films obtained by bath melting at 0°C and processing by extrusion molding etc. The molecular arrangement observed in polymers that exhibit anisotropy in the molten state can be seen, and this molded product has high tensile strength, bending strength,
It is described in JP-A-56-79123 that mechanical strength such as torsional elastic modulus and bending elastic modulus was high.

In addition, Jacksoro etc. are made of polyethylene terephthalate.
),! : A copolyester obtained by reacting with 40 to 80 mol of p-acetoxybenzoic acid μ thermal anisotropy (it is a net liquid crystal)? It has been reported that injection molded products of this material retain the alignment of liquid crystal molecules and have a high bending elastic modulus (J, of Polymer
8science: Vol, 14.2043-
2058 pages (19, 76)].

Additionally, Morgan has diamines and diketones.
The polyazomethi/compound or copolyazomethine compound obtained by reacting diacetone and/or aminoaldehyde with aminoketone exhibits thermal anisotropy, and the fiber obtained by spinning in a state where this compound exhibits thermal anisotropy is an excellent 11 Law r elastic modulus, tensile Ili! It has been reported that it exhibits degrees of li, etc. (USP No. 4°048.148).

In addition, there is a document that reports the production of molded products using a polymer compound that exhibits thermal anisotropy, such as "M" by Sirign.
ur, Polymer Journal, vol.
15.61 pages (1979).

The molded products described above are products with a two-dimensional structure, and are extruded,
Although it exhibits a high tensile strength and a high elastic modulus in a direction that coincides with the axis of the injection and discharge direction, it has the disadvantage that its mechanical strength is considerably inferior in a direction perpendicular to the axis.

One possible way to solve this poor strength problem is to use a compound that provides a three-dimensional crosslinked product. Acrylates having azomethine IIV (ll-) represented by the general formula, [in the formula,
, Vol, 9.123Q(176) and Bu l
1, Sac, CheaIl.

Fr., 1973. 579 pages or 605 pages]
.

It is difficult to obtain a cured product with a uniform composition by mixing additives such as materials. This can be seen from the fact that the mechanical properties of the cured product are not disclosed in the above report.

The present inventors have synthesized and studied various compounds with the aim of obtaining polymer-gold-giving compounds with a three-dimensional structure and a long pot life at temperatures where the compound exhibits thermal isotropy. , discovered that a polyepoxy compound represented by the following formula (I) exhibits thermal anisotropy and achieves this objective,
The present invention has been achieved [wherein 1 is 11 or C11a, and Y is 10-' or -QC-].

That is, the present invention provides a novel polyepoxy compound represented by the above formula (I).

The novel polyepoxy compound represented by the above general formula (I) is prepared in a ratio of 1 mole of terephthalaldehyde to 2 moles of p-aminophenol or p-aminobenzoic acid.
Tetrahydrofuran, N,N-methylpolamide,
20 to 60°C in a motivating medium such as l,4-dioxane, and optionally in the presence of an acidic catalyst such as p-toluenesulfonic acid.
The precursor represented by the following formula (U) is obtained by reacting for 1 to 10 hours at
? , b LeJ was obtained, and this precursor was
Alternatively, it is produced by epoxy/conversion using β-methylepihalohydrin.

There are two methods for epoxidizing this precursor: (1) a one-step method in which addition reaction and de-Rogge/hydrogenation reaction are carried out simultaneously using an alkali; The addition reaction is first carried out at a temperature of 50 to 150°C, and then the de-addition is carried out with an alkali at a temperature of 35 to 80°C.
There is a two-stage method in which the hydrogen halogenide reaction is carried out, but the latter two-stage method is preferred from the viewpoint of yield and quality of the product.

Examples of the shrimp halohydrin or β-methyl shrimp halohydrin used include epichlorohydrin, shrimp bromohydrin, l-methylepichlorohydrin, and human shrimp bromohydrin 7. The amount of shrimp helohydrin or β-methyl shrimp halohydrin used is 2 to 100 mol per 1 mol of the raw material precursor.
Preferably it is 6 to 60 mol, and Ebino Lohydrin used in excess or! -Methyl shrimp...Rohydrin can be recovered by distillation and reused.

Examples of the alkali to be used include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, potassium carbonate, and sodium carbonate, with sodium hydroxide or potassium hydroxide being preferred.

The amount of alkali used is, per 1 mole of raw material precursor,
Usually it is 1.8 to 2.2 moles. Alkali is usually
It is added to the reaction system in the form of solid particles or as an aqueous solution.

Catalysts that can be further used include, for example, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonicum promide, triethylmethylammonium chloride, tetraethylammonium iodide, cetyltriethylammonium bromide, benzyldimethylamine, triethylamine, N, N, N'
, tertiary amines such as N'-tetramethylethylenediamine, triphenylethylphosphonium diethyl phosphate, and the like.

Particularly preferred is tetramethylammonium chloride or tetraethelammonium chloride.

The amount of catalyst used is usually about 0.1 to 3.0 parts per 100 parts of the raw material precursor.

Reaction 1, in the one-step method, for example, excess shrimp... lohydrin or! - 100% of the precursor dissolved in methyl shrimp halohydrin (hereinafter referred to as shrimp halohydrin)
At a temperature of ~150℃, gradually add an aqueous solution of alkaline to 0.5~
The process was carried out for 2 hours while the water in the reaction system was azeotroped with shrimp lohydrin and removed from the system.
This is done by In the two-step process, the precursor and excess tk
The addition reaction was carried out by flowing epichlorohydrin for 1 to 4 hours in the presence of a catalyst such as a quaternary ammonium salt.
The water produced is azeotropically distilled with epichlorohydrin.
E''F (150aaHf-400aaHf), aqueous alkali solution was added dropwise to perform a ring-closing reaction.

IJ of the general formula (I) obtained by this reaction
Because epoxy compounds have poor solubility in solvents, it is not possible to use conventional purification methods, that is, dissolve them in an M agent such as toluene or methyl isobutyl ketone, wash with water to remove salts, and then distill off the solvent. Undesirable. A preferred purification method includes, after the completion of the reaction, cooling the reaction solution to completely precipitate the product, separating it with salt to remove salt, and then repeatedly washing the product with water using a mixer to remove the salt. Examples include a method of drying under reduced pressure. vl as necessary
The produced polyepoxy compound is recrystallized using dioxane.

The thus obtained polyepoxy compound represented by the general formula (I) becomes saturated with liquid crystal when heated. Also,
When cured using a curing agent at a temperature that indicates liquid crystal, a cured product with a three-dimensional structure with high mechanical strength can be obtained.As a 3° curing agent, there are various curing agents similar to those used in known epoxy resins. Can be used. Tomoe is aliphatic amines,
Aromatic amines, complex amines, Lewis acids such as boron trifluoride and their salts, organic! ! Type 1, organic acid anhydrides, urea or derivatives thereof, polymercaptans, etc. Specific examples include aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfone, 2,4-diamino-m-xylene, and benzyldimethylamine; 2-methylimidazole, 2,4.5-)riphenylimidazole, 1 - Imidazole or imidazole substitutes such as cyanoethyl-2-methylimidazole, or salts of these with organic acids: organic carboxylic acids such as fumaric acid, trimellit, hexahydrophthalic acid; phthalic anhydride, endo anhydride Organic acid anhydrides such as methylenetetrahydrophthalic acid and hexahydroduic anhydride; urea derivatives such as dicyandiamide, melamine, and guanamine; aliphatic polyamines such as triethylenetetramine, diethylenetriamine, xy7lylene diamine, and isophorone di-H7, and their ethylene oxides , epoxy compounds such as propylene oxide or acrylonitrile, Acrylic II! ! Examples include adducts with specialized acrylic compounds; chlorinated triphenylphosphonium salts; chlorinated benzyltrimethylammonium salts.

Among these, imidazoles such as imidazole, 2-methylimidal-A/, 2-xf imitasol, 2-ethyl-4-methylimidazole, 2.4.5-triphenylimidazole, and 1-cyanoethyl-2-methylimidazole; Or those QI conductors, such as C+tZ-CNS (product name) manufactured by Shikoku Kasei Kogyo ■, C*1”
1-AZINE (m product name) t: for iterii
When curing the precursor while it exhibits thermal properties,
A cured proboscis with a three-dimensional structure that maintains the orientation of the precursor well and exhibits an excellent elastic modulus is obtained.

□ Furthermore, in addition to the curing agent, the polyepoxidized product of the present invention may also contain additives such as shavings, organic solvents, reactive diluents, thickening agents, fillers, reinforcing agents, pigments, and hardening agents. Various additives such as combustion agents, thickeners, and captivating agents may be included.

Examples 1+1+ will be described below and a more detailed explanation will be given, but these examples are for water use, and the present invention is not limited by the examples.

Precursor production example Example 1 and the reaction was carried out at 50°C for 5 hours.

After the reaction, the system was cooled to 20° C. to precipitate a compound represented by the following formula, 4&.

Separate the 9 precipitated crystals into 1 and vacuum dry to obtain 2 Seiseki crystals.
6.6 f'i was obtained (yield 71.5 g). The melting point of this crystal exceeded 300°C.

Column 2 26.21 yellow crystals of the compound represented by the following formula were obtained in the same manner as in Example 1 above, except that 24.6 f of p-aminophenol was used in place 9 of 21.4 t of p-aminobenzoic acid (yield rate 76.2ch).

Example 1 The precursor obtained in the above Example 1 was charged at 37.29 m in a 500 m4 four-bottle flask equipped with a temperature g1, a condenser, and a stirring device.
0.1 mol), epichlorohydrin 37ON (47 mol)
, tetraenal ammonium chloride 0.371! (IMl for the precursor) and epichlorohydrin in an oil bath. Reflux for 2 hours to carry out the addition reaction.

In that section, the temperature of the reaction system was lowered to 60° C., and it was attached to a water separator and a tIIIF funnel, and 16.8 II of a 50% thorium hydroxide aqueous solution was added dropwise from the dropping funnel over a period of 1 hour.

During this time, the generated water and the added water were azeotropically removed together with the epichlorohydrin while adjusting the degree of vacuum so that the temperature of the reaction system was maintained at 50° to 70°C. I put it back inside.

After completion of the dropwise addition, the reaction was subcultured for another 2 hours, water in the system was completely removed, and Closing Reaction 1 was produced. After cooling the system to room temperature, the product is separated from the furnace together with the by-product salt.
Wash thoroughly with a mixer and J! ll: salt is completely removed,
After drying under reduced pressure, yellow crystals of 43.7 F (yield 90.3) of a polyepoxy compound represented by the following formula were obtained.

The EBOKI 7 equivalent of this product is 245 (theoretical value 242), and the elemental analysis values are C69,2, l-15,3, N.
5.8 excellent (theoretical value C69.4%,) 15.0chi, N5.8chi).

◆ As a result of polarizing microscope observation, this polyepoxy compound
It was confirmed that it melted at 82°C and showed anisotropy (nematic liquid crystal i), and that it showed isotropy at 265C.

The infrared absorption spectrum of this crystal is not shown in FIG.

Example 2 Several color crystals of the compound represented by the following formula were prepared in the same manner as in Example 1, except that the precursor 34.4 f fc obtained in Example 2 was used instead of the precursor 37.2 F obtained in Example 2. 4F (yield 93
, Person O) was obtained.

The equivalent weight of this chemical and compound is 216 (theoretical value 214), elemental analysis tri, C72.8%.

Hs, 9%, N6.3% (theoretical value C72,i, H5,6
%, N6.5%).

Polarized light g - As a result of observation, this polyepoxy compound has 2
It was confirmed that it melted at 11c and showed anisotropy, and showed isotropy at 271°C.

The infrared-edge absorption spectrum of this crystal is shown in FIG.

Production Example of Cured Product Example 1 To 100 u parts of the polyepoxy compound obtained in Example 1, 2,4-diamino-6-(2'-undecylimidazolyl(1) ethyl-8-triazine manufactured by Shikoku Kasei Kogyo Co., Ltd.) was added.゛C
A composition was prepared by mixing 5 parts by weight of *tZ-AZINE, which was placed on a hot stage attached to a polarized light microscope and heated to 220°C to observe the arrangement of molecules.

This composition exhibited anisotropy as soon as it melted in the bath, and became completely static and unmeltable after 15 minutes.

From the polarized light photograph (Figure 3) of this unfusible infusible material, it is clear that this infusible material has anisotropy of the ))-E arrangement that the precursor had.
It was confirmed that it has.

Example 2 Insoluble #11 in the same manner as in Example 5 above except that the polyepoxy compound obtained in Example 2 was used! I got a lot of money.

to field H1C1*Z-AZINE1c combination L7tm
The product exhibited anisotropy at the same time as it melted, and became an insoluble substance after 15 minutes.

FIG. 4 shows the polarized light micrograph Wk and Jlc of this infusible material.

[Brief explanation of drawings]

Figures 1 and 2 show Example 1 and Example 2, respectively. lJ
Figures 3 and 4 show the infrared absorption spectra of polyepoxy compounds obtained by curing them with a curing agent in a state where they exhibit thermal anisotropy. FIG. 3 is a diagram showing the arrangement of molecules of a bath infusible substance. Patent applicant: Director of the Agency of Industrial Science and Technology

Claims (1)

[Claims] l) A polyepoxy compound represented by the general formula [wherein I7 is l (or CHs, and Y is 10- or 100-] 1