JPS6351422A - Production of thermosetting resin - Google Patents

Abstract

PURPOSE:To obtain at low cost the titled resin in an industrially advantageous manner without using any special crosslinking agent, by reaction on heating in the presence of acid catalyst, of a chloromethylated or hydroxymethylated product of the raw material consisting mainly of condensed polycyclic aromatic compound. CONSTITUTION:First, a raw material consisting mainly of condensed polycyclic aromatic compound (pref., naphthalene) is chloromethylated or hydroxymethylated to form a chloromethylated or hydroxymethylated product with the number of chloromethyl group or hydroxymethyl group >=1.1 on average, respectively. Thence, this product is allowed to react on heating to pref. 100-200 deg.C in the presence of an acid catalyst such as toluenesulfonic acid, thus obtaining the objective resin. For the chloromethylating agent, a combination of formaldehyde and hydrochloric acid is preferably used; and, said hydroxymethylated product can be prepared, in general, by hydrolysis of the chloromethylated product in its aqueous alkali solution.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a method for producing a thermosetting condensed polycyclic polynuclear aromatic hydrocarbon resin, and more specifically, to a method for producing a thermosetting condensed polycyclic aromatic hydrocarbon resin, and more specifically, a method for producing a thermosetting polycyclic aromatic hydrocarbon resin, and more specifically, The present invention relates to a method for producing a thermosetting hydrocarbon resin by subjecting a chloromethylated product or a hydroxymethylated product to a heating reaction in the presence of an acid catalyst.

[Prior art]

Previously, one of the inventors of the present invention has developed an acid-catalyzed method using a raw material mainly composed of a fused polycyclic aromatic compound and a crosslinking agent mainly composed of an aromatic compound having at least two hydroxymethyl groups or halomethyl groups. We discovered a condensed polycyclic polynuclear aromatic hydrocarbon resin with excellent heat resistance that can be easily and inexpensively produced by carrying out a heating reaction in the presence of C0PNA.
It was named resin (Japanese Patent Application No. 60-30055).

However, in the case of this method, it is necessary to use P-xylylene glycol or the like as a crosslinking agent in addition to the raw material, and a lower cost manufacturing method is desired.

〔the purpose〕

An object of the present invention is to provide a method for producing C0PNA resin without using a special crosslinking agent.

〔composition〕

According to the present invention, the average number of chloromethyl groups or hydroxymethyl groups per molecule obtained by chloromethylating or hydroxymethylating a raw material containing a fused polycyclic aromatic compound as a main component is at least 1.1. A method for producing a thermosetting resin is provided, which comprises subjecting a chloromethylated product or a hydroxymethylated product to a heating reaction in the presence of an acid catalyst.

The present invention will be explained in detail below.

[Raw material condensed polycyclic aromatic compound]

The raw material used in the present invention is a condensed polycyclic aromatic compound or a mixture containing this as a main component. The fused polycyclic aromatic compound used in the present invention preferably has 2-5 rings, and specific examples of such compounds include naphthalene, phenanthrene, anthracene, pyrene, chrysene, naphthacene, fluoranthene, perylene, It includes picene and its alkyl derivatives, various benzopyrenes, various benzoperylenes, etc., and also includes hydrocarbons with polycyclic and polynuclear structures in which their condensed benzene nuclei are connected with methylene groups, phenylene groups, xylylene groups, etc. 1. The fused polycyclic aromatic compound used as a raw material in the present invention does not necessarily need to be used alone; a mixture thereof can also be used, and a compound containing a mixture thereof as a main component can also be used.

Such a raw material containing a mixture of polycyclic aromatic compounds as a main component must be obtained from petroleum or coal and have an aromatic carbon fraction fa value of 0.6 or more and an aromatic ring hydrogen content Ha
Examples include heavy oils or pitches having a value of 20% or more. The fa value and lla value in this case are defined by the following equations.

However, this fa value is a value obtained by calculating by the Brown-Ladner method using elemental analysis values and iH-NMR, and the Ha value is a value obtained using 1H-NMR.

If heavy oils or pitches with an fa value of less than 0.6 are used, a thermosetting resin with excellent heat resistance cannot be obtained due to the low aromatic content, and if the Ha value is less than 20%. When small heavy oils or pitches are used, a resin with a poor degree of crosslinking is produced because the number of hydrogen atoms in the aromatic ring is small. In particular, it is preferable to use one having an fa value of 0.7 or more and a tla value of 3 parts or more.

In addition, heavy oils and pitches have a molecular weight of approximately 20
Examples of such heavy oils and pitches for which it is preferable to use 0 or more include coal tar, coal tar pitch, petroleum-based heavy aromatic components, petroleum-based pitch, or fractionated components thereof. It will be done.

Coal tar pitch is a complex mixture consisting mainly of fused polycyclic aromatic compounds with 3 to 5 rings, and has an average molecular weight of 30
It is around 0, which is generally larger than that of a pure 3-4Q condensed polycyclic aromatic compound.

As petroleum-based heavy oils and pitches, for example, catalytic cracking residue oil of vacuum gas oil, thermal cracking residue oil of naphtha, pitch prepared from these, and heavy oil fractions generated in the pitch manufacturing process are preferable. It is used in

[Chloromethylation of raw materials]

Chloromethylation of the raw material in the present invention.

This is carried out according to a conventionally known method, and in this case, a conventionally known chloromethylating agent is preferably used, for example, a combination of formaldehyde or a formaldehyde-forming substance and hydrochloric acid or hydrogen chloride. Formaldehyde-forming substances are those that generate formaldehyde under reaction conditions, and include, for example, formalin, trioxane, paraformaldehyde, and the like. Moreover, this chloromethylation reaction is advantageously carried out in the presence of a catalyst. In this case, the catalyst is
Inorganic acids such as phosphoric acid and sulfuric acid, metal chlorides such as aluminum chloride, zinc chloride, and iron chloride, and chlorides or oxychlorides of sulfur and phosphorus are used. The chloromethylation reaction is carried out in either an open system or a closed system, and the reaction temperature is room temperature to 200°C, preferably 100 to 150°C.

The reaction is preferably carried out in a closed system, and in this case autogenous pressure is usually used as the reaction pressure.

In the present invention, the chloromethylation rate of the raw material is at least 1.1, preferably in the range of 1.5 to 4, expressed as the average number of chloromethyl groups per molecule of the raw material. When the chloromethylation rate is less than 1.1,
Heating under an acid catalyst does not give the desired cured product. Further, even if the chloromethylation rate is set to 4 or more, no particular advantage is obtained. The chloromethylation rate can be adjusted by adjusting the addition ratio of the chloromethylating agent to the raw material and the reaction time. Generally, for 1 mole of raw material, 2 to 5 moles of formaldehyde and 2 to 5 moles of chlorinating agent (as hydrogen chloride).
~10 moles, and the catalyst is in a proportion of 0 to 5 moles. The reaction time is about 1 to 20 hours.

After the chloromethylation reaction, the resulting reaction solution is cooled to precipitate the chloromethylated product as crystals, which are filtered off and washed with water to recover the chloromethylated product.

[Hydroxymethylation of raw material]

The hydroxymethylated product can be obtained by subjecting the chloromethylated product to hydrolysis in an alkaline aqueous solution.

The alkali includes hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as sodium carbonate and potassium carbonate, with carbonates being preferred. The addition ratio of alkali is 1.1 to 3 m01 in terms of sodium or potassium to 1 mol of chlorine in the raw chloromethylated product. The amount of water used is 10 to 50% by weight based on the raw material chloromethylated product.
It's double. The hydrolysis reaction is carried out either in an open system or in a closed system, and the reaction temperature is 80-150°C. Reaction time is 0.5-3 hours.

After the hydrolysis reaction, the resulting reaction solution is cooled to precipitate the product as crystals, which are filtered and washed with water to obtain the desired hydroxymethylated product.

[Manufacture of thermosetting resin]

A desired thermosetting resin (B-stage resin) can be obtained by heat-reacting the chloromethylated or hydroxymethylated raw material in the presence of an acid catalyst. In this case, as the acid catalyst, either a Lewis acid or a Brønsted acid can be used, but a Brønsted acid such as toluenesulfonic acid, xylene sulfonic acid, or sulfuric acid is usually used. The amount of acid catalyst used is 0.2 to 2% of the chloromethylated or hydroxymethylated material of the raw material.
It is adjusted within the range of 0% by weight, taking into account the reaction conditions and the reactivity of the chloromethylated product or hydroxymethylated product. The reaction is carried out in the presence or absence of a solvent, and the reaction temperature is about 70 to about 300°C, preferably 100 to 200°C.

When the reaction proceeds as described above, the chloromethylated product or hydroxymethylated product undergoes a polycondensation reaction and becomes a polymer, and becomes an infusible cured product via the thermosetting resin.

In the present invention, the reaction is stopped before the resin becomes an infusible thermosetting material to obtain a thermosetting resin. This material still has heat-melting properties.

It is an uncured intermediate condensation reaction product. This thermosetting resin exhibits heat-melting properties and solubility in organic solvents such as N-methyl-2-pyrrolidone, and can be used as a binder or adhesive for various composite materials, as well as as a molding material. It can also be used as a raw material for carbon materials.

When used as an adhesive, the thermosetting resin can be dissolved in an appropriate organic solvent. In addition, when obtaining a molded product, the thermosetting resin alone or after mixing other components is heated to about 150 to about 300°C to substantially complete the polycondensation reaction to obtain a thermoset product. This curing treatment is preferably carried out under pressure in order to obtain a good molded product. Further, post-curing can also be performed to improve the physical properties of the molded product. This post cure is generally about 200 ~
It is carried out at a temperature of about 400°C.

According to another method of the present invention, a heat-infusible molded product is obtained by blending an acid catalyst with the chloromethylated product or hydroxymethylated product, using this blend as a molding material, and performing pressure and heat molding. You can also do that.

〔effect〕

According to the present invention, C0PNA resin can be obtained without using a special crosslinking agent such as P-xylylene glycol, so the manufacturing cost is low and it is very advantageous industrially.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Anthracene was chloromethylated using a conventional method.

9. Add toluene to the reaction product and recrystallize twice.
10-di(chloromethyl)-anthracene was obtained. This 9,10-di(chloromethyl)-anthracene 3.03
17.7 g (0.1 mol) of 1-chloromethylnaphthalene was mixed with g([), 0.1 mol). The average number of chloromethyl groups in this mixture is calculated according to the following formula: 1.
It is 1.

a: mol number of 1-chloromethylnaphthalene b: 9,1
Number of moles of 0-di(chloromethyl)-anthracene Add 0.21 g (]w of P-toluenesulfonic acid to the above mixture)
t%) and mixed in a mortar, the mixture was placed in a test tube and heated in an oil bath at 120°C for 40 minutes. When the softening point of the produced resin was measured using the Koka flow tester method, it was found to be 1.
The temperature was 06°C. After adding 4 weight 2 of P-toluenesulfonic acid to this resin and mixing in a mortar, 200 kg/cfflG
A cured product was obtained by holding at 200° C. for 1 hour under pressure. This cured product was heated at 30℃ in nitrogen using a thermobalance.
Thermogravimetric analysis was conducted at a heating rate of /min, and the results shown in curve 1 in the drawing were obtained.

Example 2 A stream of vacuum gas oil as a raw material! A catalytic cracking (FCC
) obtained by distilling the bottom oil obtained in 420-538
Distillate oil (average molecular m 270
, fa value 0.84) (hereinafter simply referred to as cracked oil) was used.

The cracked oil, paraformaldehyde (purity 80% by weight as C11□0), concentrated hydrochloric acid (purity 36% by weight as llcfl), and carbon tetrachloride were mixed in the proportions shown in Table 1, and a pressure-resistant glass autoclave was used. The reaction was carried out at 120°C for 5 hours.

Table 1 (raw material composition) Decomposed oil 26.8g (0.1moi) Paraformaldehyde 18.8g (0.5111ol)
Concentrated hydrochloric acid 101.4g (1.0mol)
Carbon tetrachloride 270 mρ After cooling the reaction product to room temperature, the total amount of the reaction product was reduced to 16
00 mA of n-hexane, and the precipitate was separated by filtration.The separated solid content was sufficiently washed with water and dried to obtain 13.8 g of chloromethylated product. When the molecular weight of this chloromethylated product was measured by vapor pressure equilibrium method, it was 663, and the amount of chlorine contained was 11.2% by weight (analytical method: JIS K
2264).

When the average number of chloromethyl groups per molecule of this chloromethylated product was calculated according to the following formula, it was 2.1.

(However, in formula 1, a represents the molecular weight of the chloromethylated product, and b represents the amount of chlorine it contains (st'1).) Next, 1% by weight of p-toluenesulfonic acid was added to the chloromethylated product, and the mixture was placed in a mortar. After mixing, the mixture was placed in a test tube and heated in a 170°C oil bath for 40 minutes. The softening point of the produced resin was measured using a Koka type flow tester and found to be 120°C. This resin has P-
After adding 1 mm% of toluenesulfonic acid and mixing in a mortar, a cured product was obtained by holding at 200° C. for 1 hour under a pressure of 200 kg/dG. This cured product was subjected to thermogravimetric analysis using a thermobalance in nitrogen at a heating rate of 30° C. for 7 minutes, and the results shown in curve 2 in the drawing were obtained.

Example 3 The cracked oil shown in Example 2, paraformaldehyde (purity 80 wt. The reaction was then carried out at 120°C for 200 hours.

Table 2 (Raw material composition) Decomposed oil 26.8g (0.1mol) Paraformaldehyde 28.2g (0.75mol) Concentrated hydrochloric acid 152.1g (1.50mol)
Carbon tetrachloride 270m Q After cooling the reaction product to room temperature, the total amount of the reaction product was reduced to 16
00 mn of n-hexane, and the precipitate was separated by filtration. The separated solid content was thoroughly washed with water, and after confirming that the washing water was neutral, it was dried. The solid content after drying is 19
．． It was 3g. When the molecular weight of this solid content (chloromethylated product) was measured by vapor pressure equilibrium method, it was 890,
Moreover, the amount of chlorine contained was 16.0% by weight. Therefore, the average number of chloromethyl groups per molecule is 4
．． It was 0. Moreover, its softening point was 148° C. when measured using a Koka type flow tester.

Add p-toluenesulfonic acid 5 times to the above solid content, fjt
% and mixed in a mortar, under pressure of 200 kg/aJG, 2
A cured product was obtained by holding at 00°C for 1 hour.

This cured product was subjected to thermogravimetric analysis using a thermobalance in nitrogen at a heating rate of 30° C./min, and the results shown in curve 3 in the drawing were obtained.

Example 4 The chloromethylated product obtained in Example 2, sodium carbonate (anhydrous), and distilled water were mixed in the proportions shown in Table 3, and a reaction was carried out at 110°C for 2 hours using a pressure-resistant glass autogelape. Table 3 Water 210g After cooling the reaction product to room temperature, the precipitate was separated by filtration.

The separated solid content was thoroughly washed with water, and after drying, 5.9 g of hydroxymethylated product was obtained. The amount of chlorine contained in this hydroxymethylated product was 0.1 weight ff1% or less.

To this hydroxymethylated product, p-toluenesulfonic acid 5
A hardened product was obtained by adding % of the weight and mixing in a mortar and holding at 250°C for 1 hour under a pressure of 200 kg/a (G). Thermogravimetric analysis was conducted at a heating rate of , and the results shown in curve 4 in the drawing were obtained.

Comparative Example 1 - 17.7 g (0.1 mol) of chloromethylnaphthalene (number of chloromethyl groups per molecule: 1) and 0.18 g (1.0% by weight) of p-toluenesulfonic acid were mixed in a mortar and placed in a test tube. and heated in a 120°C oil bath for 2 hours.

The softening point of the produced resin was measured with a Koka type flow tester and found to be 80°C. 4% by weight of p-toluenesulfonic acid was added to this heated reaction product, mixed in a mortar, and heated to 200°C.
Attempts were made to heat mold the product using a hot press, but the melt flowed out of the mold and no molded product could be obtained.

[Brief explanation of drawings]

The drawing is a graph showing the results of thermogravimetric analysis of the cured product, where curve-1 shows the results of Example 1, curve-2 shows the results of Example 2, curve-3 shows the results of Example 3, and curve-4 shows the results of Example 4. . Applicant's agent Patent attorney Toshiaki Ikeura (and 1 other person) Tsukuminato, L ('(-)

Claims (1)

[Claims] (1) 1 obtained by chloromethylating or hydroxymethylating a raw material whose main component is a condensed polycyclic aromatic compound
A method for producing a thermosetting resin, which comprises subjecting a chloromethylated product or a hydroxymethylated product having an average number of chloromethyl groups or hydroxymethyl groups of at least 1.1 per molecule to a heating reaction in the presence of an acid catalyst.