JPS63199228A - Thermosetting resin raw material composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin raw material composition, capable of providing cured articles having a high modulus of elasticity and excellent heat resistance, by blending tetracyanobenzene with a specific bisphthalonitrile and curing agent in a specific proportion. CONSTITUTION:A thermosetting resin raw material composition, obtained by blending (A) tetracyanobenzene with (B) bisphthalonitrile expressed by formula I (R is organic group consisting of conjugated double bond, e.g. a group expressed by formula II, etc.) and (C) a curing agent (preferably m- phenylenediamine, etc.). The component (A) is used in an amount of 1-50pts.wt., preferably 2-30pts.wt. based on 100pts.wt. component (B) and the component (C) is used in an amount of 1-10pts.wt. based on 100pts.wt. total amount of the components (A) and (B).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a bisphthalonitrile compound that forms a three-dimensional network structure. More specifically, the present invention relates to a thermosetting resin raw material composition that increases crosslinking density through the reactivity of a bisphthalonitrile compound, resulting in a cured product having a high modulus of elasticity and good heat resistance.

[Prior Art] It has been reported that a three-dimensional network structure is formed in certain bisphthalonitrile compounds by heating and melting them or by heating and melting them with a curing agent and causing condensation polymerization (Jou
rnal of Applied Polymer 5
science, Vol 29, 3339 (1984
)).

In addition, attempts have been made to develop polymeric materials with high elastic modulus through in-phase polymerization of diacetylene compounds (for example, J.
internal of Polymer 5science
, VolB9, 133 (1971), Jour
nal of Polymer 5science.

Polymer-Physics Edition V
ol 12, 1511 (1974)).

[Problems to be Solved by the Invention] Bisphthalonitrile and diacetylene compounds can form a three-dimensional network structure by utilizing the high reactivity of cyano groups and acetylene groups. However, in the results of previous studies, the crosslinking density of the cured product was not sufficiently increased, and the elastic modulus was insufficient at about 10 GPa at most.

[Means for Solving the Problems] Therefore, the present inventors have conducted intensive research into further increasing the modulus of elasticity and improving the heat resistance of a molded article using a condensate of bisphthalonitrile.

That is, the present invention includes the following components (A), (B), and (C), and (B)
Component (A>1 to 50 parts by weight per 100 parts by weight of component) and 1 to 10 parts by weight of component (C) per 100 parts by weight of component (A>±(B)). The present invention relates to a thermosetting resin raw material composition characterized by the following.

(A>Component amount Tetracyanobenzene (B) component: bisphthalonitrile represented by the following formula (in the formula,
(R represents an organic group consisting of a conjugated double bond in a broad sense) Component (C): Curing agent R in the component (B) in the present invention represents an organic group consisting of a conjugated double bond in a broad sense. Here, the conjugated double bond in a broad sense is:
The bond in the normal conjugate principal axis direction represented by -C=C- is characterized in that the bond strength is stronger than that of one σ bond due to the delocalization of at least π electrons. Specific examples of R include CHz, CI, etc. in the above compound.
For example, Ct-h C1 and the like are substituted. That is, the bonding direction of R consists of conjugated double viscosity in a broad sense, and the side chain bond may be one σ bond.

As the curing agent for component (C) in the present invention, amine compounds are usually suitable.

For example, m-phenylenediamine, P-phenylenediamine, 4,4°-methylenedianiline, 4-aminophenyl ether, 4.4'(P-phenylenedioxy)
Examples include dianiline and 4-aminophenylsulfone. These may be used alone or in combination of two or more.

In the composition of the present invention, the amount of component (A) to be blended with respect to 100 parts by weight of component (B) depends on the chemical structure of component (B), but is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight. Weight parts are good. If the amount of component (B) is less than 1 part by weight, the crosslinking density of the composition will be difficult to increase, and the strength and elastic modulus of the cured product after thermal crosslinking will be low, which is not preferable. On the other hand, if the blending amount of component (B) exceeds 50 parts by weight, the crosslink density increases to some extent, but on the other hand, flexibility is lost and the cured product becomes extremely brittle, which is not preferred in practice.

Furthermore, in the composition of the present invention, (A>+(B) component 1
The curing agent <C) component is arranged in an amount of 1 to 10 parts by weight per 00 parts by weight. When the amount of component (C) is less than 1 part by weight, there are disadvantages such as a slow curing rate, which is not preferred in practice. On the other hand, if the amount of component (C) exceeds 10 parts by weight, the curing speed increases, but the substantial crosslinking density decreases, making it impossible to obtain desirable mechanical properties.

The following components can be added to the composition of the present invention as necessary.

(1) Powdered reinforcing agents and fillers, such as metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, basic Magnesium silicate, fired clay, finely powdered silica, fused silica, crystalline silica, carbon black, kaolin, finely powdered mica, quartz powder, metal hydroxides such as aluminum hydroxide, graphite, asbestos, molybdenum disulfide, trioxide such as antimony. Additionally, there are fibrous reinforcements and fillers, such as inorganic fibers such as glass fibers, rock wool, ceramic fibers, asbestos, and carbon fibers, and synthetic fibers such as paper, pulp, wood flour, linters, and polyamide fibers. The amount of these powder or fibrous reinforcing materials and fillers used varies depending on the purpose, but as a laminated material or molding material, up to 500 parts by weight can be used per 100 parts by weight of the resin composition.

(2) Colorants, pigments, flame retardants such as titanium dioxide, yellow lead carbon black, iron black, molybdenum red, navy blue,
These include inorganic phosphorus such as ultramarine, cadmium yellow, cadmium red, and red phosphorus, and organic phosphorus such as triphenyl phosphate.

(3) Furthermore, various synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded product, etc. For example, phenolic resin,
Examples include one or a combination of two or more of alkyd resins, melamine resins, fluororesins, vinyl chloride resins, acrylic resins, silicone resins, and polyester resins. The amount of these resins to be used is within a range that does not impair the original properties of the resin composition of the present invention, that is, 5% of the total resin amount.
Less than 0% by weight is preferred.

(A> component, (B) component, (C) component and various additives can be blended by heating and melt mixing, by roll, by kneader, etc.)
Examples of such methods include kneading using an organic solvent, mixing using an appropriate organic solvent, and the like.

1. Synthesis of Components - 1,2,4,5-tetracyanobenzene is usually synthesized by using pyrometic acid tetraamide as an intermediate.

To prepare this intermediate, the ammonium salt of pyromellitic acid is heated to obtain a pyromellitic acid di-stage reaction (He
tody Polucheniya Khim Rea
ktivovi Preparatov No. 12.
108 (19fS5)). To synthesize 1,2,4,5-tetracyanobenzene from the intermediate pyromellitic acid tetraamide thus obtained, dehydration with thionyl chloride using dimethylformamide as a solvent (Chem.
istry and Industry, 1964, 7
52) is taken.

-Synthesis of component B- The synthesis method for component B is the reaction of 4-nitrophthalonitrile and an alkali salt of biphenol ("Re5inS for Ae").
rospace”, Am, Chem, Soc, S
ymp, Ser., 132.25 (1980))
based on.

[Method for measuring properties and evaluating effectiveness (1) Flexural modulus The method for measuring the flexural modulus is based on the ASTM standard method.
-D790-66 can be used. However, the molded product of the present invention may not necessarily be large enough to be measured by the ASTH measurement method. Therefore, the following method was used to measure the flexural modulus of the small molded product.

That is, as a method for measuring the above-mentioned flexural modulus, the length of the test piece is 30 IrI! ri, width 5m, height 1#1lI2, distance between fulcrums 16#, fulcrum tip radius 2R1 pressure wedge tip radius 5R1, test speed 0.5 s/min. In this case, although the flexural modulus was measured slightly smaller than the ^STH method, almost similar values were obtained.

(2) Conductive paint (“Dotite to
(i1 Fujikura Kasei Silver Paste) was applied and dried, and the resistance value was measured using a digital multi-thermometer (manufactured by Takeda Riken Kogyo ■). The electrical conductivity was determined from this resistance value according to a conventional method.

(3) Impact resistance The impact resistance of the sample was measured by using a Charpy impact tester (■Toyo Seiki rupture) to calculate the energy required for rupture when struck with a hammer by the cross-sectional area of the sample. The value was evaluated as an impact value.

The test was performed using a cross-sectional area of 5ms” (Igx 5m>, length of 40
The plate-shaped object of M was struck perpendicularly to the length direction to break it.

The distance between the fulcrums was chosen as 20111111. Hammer weight (1LF) speed, cutting edge radius, and support trapezoid shape were in accordance with JIS standards. , impact resistance is poor if the impact value is less than AKI・cm/ctit, 4KJ・ram/crA
The above items were judged to be good.

[Effects of the Invention] Furthermore, since this crosslinked body is constituted by π-electron conjugated bonds, it exhibits excellent electrical conductivity.

Therefore, the composition of the present invention can be used in a wide range of fields such as electronic materials, aerospace, precision machinery, and structural materials.
Available.

[Examples] A more specific explanation will be given below with reference to Examples, but these Examples are merely illustrative, and the present invention is not limited by the Examples.

Example 1 109 parts by weight of pyromellitic anhydride, 100 parts by weight of urea, and about 700 parts by weight of monochlorobenzene were mixed with a stirring blade,
The mixture was placed in a reaction vessel equipped with a condenser and a thermometer.

The reaction was carried out under distant current (118-125° C.) for 7.5 hours with stirring. After cooling, the mixture was passed through a glass filter and the resulting slightly yellow powder was air-dried.

Add 350 parts by weight of concentrated ammonia water to the air-dried powder.
．． The mixture was stirred for 5 hours and then passed through the mouth. The obtained powder was further extracted twice with 350 parts by weight of concentrated aqueous ammonia to remove unreacted substances. After the extraction with aqueous ammonia is completed, wash with water until the 0 solution becomes neutral. Rough vacuum drying yielded 107 parts ffi of pale pink pyromellitic acid tetraamide.

37.5 parts by weight of the romellitic acid tetraamide obtained here was placed in a container, and 25 parts by weight of dehydrated dimethylformamide was added.
0 parts by weight were added. Using a water bath, dilute the reaction solution in the container from -1 to
While maintaining the temperature at -2°C, 178 parts by weight of thionyl chloride was added dropwise over 2.5 hours while stirring.

After completion of the dropwise addition, the reaction was allowed to proceed at room temperature for 2 days. After the reaction was completed, the resulting orange transparent solution was passed through a glass filter and poured into a mixture of 200 parts by weight of ice and 100 parts by weight of concentrated hydrochloric acid. The precipitated crystals were separated using a glass filter, washed with water until the liquid became neutral, and then dried. 18 parts by weight of 1,2,4,5-tetracyanobenzene was obtained as a pale yellow powder.

24 parts by weight of the 1,2,4.5-tetracyanobenzene thus obtained was recrystallized using 390 parts by weight of acetic acid. Needle-shaped crystals with 19 folds were obtained. 11 in this crystal
It was recrystallized using 0 weight part of Medil cellosolve.

13 parts by weight of almost white plate-like crystals were obtained.

The melting point was 272-273°C.

Next, 4,4°-bis(4-phenyleneoxyphthalo-
Nitrile) was synthesized by the following method.

I passed my mouth in Sfilter. Place the obtained Laguis-colored powder in a container, and add 1 part of concentrated ammonia water while stirring the liquid with a black stirring blade.
10 parts by weight were added. After stirring the suspension for 1 hour, the crystals were separated using a glass filter. The obtained crystals were washed with water until the liquid became neutral, and then dried under vacuum.

23 parts by weight of 4-nitrophthalamide were obtained.

Next, 21 parts by weight of 4-nitrophthalamide and 88 parts by weight of dimethylformamide were charged into a reaction vessel, the liquid temperature was maintained at -29 to -34°C while stirring, and 62 parts by weight of thionyl chloride was added over 1 hour. dripped. After dropping, the temperature of the solution was slowly returned to room temperature over 4 hours. The resulting green-brown clear solution was allowed to stand overnight and then poured into a mixture of 50 parts by weight of concentrated hydrochloric acid and 100 parts by weight of crushed ice. Since the crystals will precipitate slowly, the temperature should be kept at 10°C or below with occasional stirring.
I've changed the date since I started using the clock. The resulting cake was washed until the 0 liquid became neutral and dried under vacuum, resulting in about 11 parts by weight of 4-
The nitrile was obtained as a gray-green powder.

The melting point was 140-144°C.

Next, 52 parts by weight of dimethyl sulfoxide, 59 parts by weight of P, P-biphenol, 16 parts by weight of potassium carbonate,
and 11 parts by weight of 4-nitrophtanitrile were placed in a reaction vessel purged with nitrogen. The temperature of the mixed solution was raised from room temperature while stirring, and the temperature was kept at 56-59°C for 4 hours to react. After the reaction was completed, the obtained reddish-brown dispersion was returned to room temperature and poured little by little into 125 parts by weight of cooled 3N HCl. Foaming occurred, but when this stopped and the mixture cooled to rift °C, the precipitated crystals were separated.

Wash it with water until it becomes neutral and vacuum dry it.
．． 3 parts by weight of 4,4°-bis(4-phenyleneoxyphthalonitrile) were obtained as a pale yellow powder.

The melting point was 235-238°C.

A polyphthalonitrile molded article was produced by condensation polymerization from 1,2,4.5-tetracyanobenzene and 4,4-bis(4-phenyleneoxyphthalonitrile) synthesized as described above in the following manner.

4.97 parts by weight of 4°-bis(4-phenyleneoxyphthalonitrile), 3 parts by weight of 1,2,4.5-tetracyanobenzene, and 3 parts by weight of P-phenylenediamine were placed in a reaction vessel and thoroughly blended. l Heat and melt at 250°C. After stirring for about 5 minutes after melting, the melt becomes slightly sticky, so heating is stopped and the mixture is cooled. Crush this into powder.

The powdered prepolymer is placed in a mold and molded into a plate (thickness: 11111L, width: 50m, length: 80m) using a compression press at 200°C and a pressure of 15 K'j/-. .

The obtained molded product was heat treated in a nitrogen atmosphere from 250 to 900°C in 50°C steps for 30 minutes at each temperature.

If the sample is suddenly treated at a high temperature, foaming or the like may occur, so it is preferable to gradually increase the treatment temperature in this way.

The flexural modulus of the obtained molded body was 25 GPa, and the electrical conductivity was 2.
, ix 10257 cm, and the impact resistance was good.

Example 2 and Comparative Example 1.2 Polyphthalonitrile molded products were made under the conditions of Example 1 by changing the blending ratio of tetracyanobenzene and bisphthalonitrile and the amount of curing agent added. Table 1 shows the properties of these molded products.

These results show that molded bodies obtained from compositions within the scope of the present invention are excellent in elastic modulus, electrical conductivity, and impact resistance.

Comparative Example 3 After replacing the reaction vessel with stirring blades with nitrogen, 38.4 parts by weight of dimethyl sulfoxide and 5.3 parts by weight of bisphenol^
, 11.7 parts by weight of potassium carbonate, and 8.1 parts by weight of purified 4-nidotophthalonitrile were added in this order, and the temperature was raised while stirring while gradually introducing nitrogen.

Fever is observed at around 45℃. The reddish-brown dispersion obtained by reacting at 56-62° C. for 4 hours was poured into 95 parts by weight of cooled 3N HCl. After cooling to 10° C., the precipitated crystals were separated daily, washed with water until they became neutral, and then dried in vacuum. 10.7 parts by weight of 4,4°-isopropylidene-bis(4-phenyleneoxyphthalonitrile) was obtained as a pale yellow powder.

To 90 parts by weight of the 4,4-isopropylidene-bis(4-phenyleneoxyphthalonitrile) thus obtained, 10 parts by weight of tetracyanobenzene and 3 parts by weight of P-phenylenediamine were placed in a reaction vessel. Heat and melt at 250°C. After stirring for 5 minutes, the mixture was placed in a mold, and a molded article was obtained by the method of Example 1 below.

This molded article had a low flexural modulus of 3 GPa, poor impact resistance, and did not exhibit desirable properties.

Claims (1)

[Claims] Contains the following components (A), (B) and (C), and (B)
Component (A) is blended in proportions of 1 to 50 parts by weight per 100 parts by weight of components, and component (C) is blended in proportions of 1 to 10 parts by weight relative to 100 parts by weight of components (A) + (B). A thermosetting resin raw material composition characterized by the following. (A) Component: Tetracyanobenzene (B) Component: Bisphthalonitrile shown by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R represents an organic group consisting of a conjugated double bond in a broad sense) (C) Component: Hardening agent