JPS62227925A - Production of thermosetting resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin excellent in moldability, curability, oxidation resistance and heat decomposition resistance, by polycondensing a fused polycyclic aromatic hydrocarbon and a specified aromatic compound in the presence of an acid catalyst and polycondensing the obtained mixture with a phenol. CONSTITUTION:A fused polycyclic aromatic hydrocarbon (A) selected from among naphthalene, phenanthrene, anthracene, pyrene, fluoranthene, pitch containing them, etc. is polycondensed with an aromatic compound (B) having at least two functional groups of the formula (wherein X is OH, Cl or Br), e.g., xylylene glycol, in the presence of an acid catalyst (e.g., toluenesulfonic acid). To this reaction mixture, a monohydric or polyhydric mononuclear phenol such as (alkyl)phenol or resorcinol or a polynuclear phenol (C) which has phenol nuclei having reactive hydrogen atoms and linked together through bridging groups and is obtained from a phenol and (para)formaldehyde is added din an amount which is 10wt% based on component A and provides a molar ratio of component B to components A and B of 0.8-5 and polycondensed.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a thermosetting resin that is mold-hardenable and has excellent oxidation resistance and thermal decomposition resistance.

Conventional thermosetting resins include phenolic resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin,
Polyimide resin etc. are known (June 15, 1985)
(Refer to pages 149-151 of "Engineering Plastics Handbook," published by New Technology Development Center, Japan).

Generally, these resins have superior heat resistance compared to thermoplastic resins, but with the exception of polyimide resins,
The maximum temperature that can be used for a long time is about 150 to 200°C.

On the other hand, polyimide resin has a long usable temperature of 25
Although it has excellent heat resistance of 0 to 300°C, it has the disadvantage of poor moldability.

Recently, fused polycyclic polynuclear aromatic resins have been attracting attention as new thermosetting resins.

The condensed polycyclic polynuclear aromatic resin uses pyrene, phenanthrene, naphthalene, anthracene, or a mixture thereof as a condensed polycyclic aromatic hydrocarbon, and p-xylylene glycol and an acid catalyst as a crosslinking agent. It is obtained by polycondensation in an inert gas atmosphere using a sulfonic acid containing p-) toluene (1932).
Collection of lecture abstracts of the 51st Autumn Annual Meeting of the Chemical Society of Japan held on March 3, 1980, pages 539-541, and December 1985.
(See p. 183 of the 12th Annual Meeting of the Carbon and Carbon Science Society, held from March 11th to 13th).

This condensed polycyclic polynuclear aromatic resin is made three-dimensional by heating the B-stage resin at 100 to 300°C.
The cured product exhibits excellent oxidation resistance and thermal decomposition resistance.

However, this condensed polycyclic polynuclear aromatic resin has a slow curing speed compared to general-purpose thermosetting resins such as phenol resins and epoxy resins, and its moldability is an important issue.

Problems to be Solved The present invention provides a method for producing a thermosetting resin having improved mold curability in the above condensed polycyclic polynuclear aromatic resin.

As a result of various tests and studies, the presenters detailed the invention, and found that by using phenols with high condensation reactivity with the crosslinking (priming agent) together with the condensed polycyclic aromatic hydrocarbon, the condensed polycyclic polynuclear aromatic resin The present invention was completed based on the discovery that curability can be greatly improved without impairing heat resistance.

In other words, the present invention provides a method for combining a condensed polycyclic aromatic hydrocarbon and an aromatic compound having two or more functional groups represented by the general formula CH2X (where x==(ll, C1, Br)) in the presence of an acid catalyst. This is a method for producing a thermosetting resin, which is characterized by polycondensing the resin, then adding a phenol, and subjecting it to rough polycondensation.

The resin obtained by this invention is a new thermosetting resin that has both easy moldability, hardness and high heat resistance.

In this invention, the condensed polycyclic aromatic hydrocarbons include naphthalene, phenanthrene, anthracene, pyrene, fluoranthene, acenaphthene, methylnaphthalene, derivatives thereof, or tar fractions containing them alone or in mixtures. You can use it. Examples of phenols include mononuclear or polyvalent mononuclear phenols such as phenol, alkylphenol, resorcinol, and naphthol, phenols represented by phenol and alkylphenol, formaldehyde, and paraformaldehyde, which is a substance with the same effect as formaldehyde. Polynuclear phenols bonded via bridging groups obtained by acid-catalyzed condensation with ketones such as acetone, which still have active reactive hydrogen in the phenol nucleus, can be used.

Examples of crosslinking agents include xylylene glycol, naphthalene dimetatool, biphenyl dimetatool, xylylene dichloride, xylylene dichloride, etc. in which two or more hydrogen atoms of the aromatic nucleus are -CH2X groups (X=CH, (l, Br)
A variety of aromatic compounds substituted with can be used.

As the acid catalyst, various organic acids, inorganic acids, and Lewis acids such as toluenesulfonic acid, phenolsulfonic acid, xylenesulfonic acid, sulfuric acid, tin chloride, aluminum chloride, and zinc chloride can be used.

In this invention, the polycyclic aromatic hydrocarbon and the crosslinking agent are subjected to a secondary reaction in the presence of an acid catalyst, and then the phenols are added for a secondary reaction.If the phenols are added from the beginning, the crosslinking agent is Because it selectively reacts with phenols in a three-dimensional manner, the reaction with condensed polycyclic aromatic hydrocarbons is inhibited, and many unreacted condensed polycyclic aromatic hydrocarbons remain in the cured product. This is because sufficient properties such as heat resistance cannot be obtained.

In the present invention, the phenol can be blended in any proportion to the condensed polycyclic aromatic hydrocarbon, but in order to obtain an industrially useful molded and cured product, the proportion is preferably 10% by weight or more.

Crosslinker and target tIl! When the blending ratio of the bridge raw material (total amount of phenols and condensed polycyclic aromatic hydrocarbons) is 0.8 or less in terms of molar ratio of the crosslinking agent to the raw material to be crosslinked, the produced lubricant does not exhibit thermosetting properties, and on the other hand, when it is 5 or more,
The number of ether bonds increases due to the reaction between crosslinking agents, resulting in a decrease in thermal decomposition resistance and mechanical properties (particularly impact resistance). Therefore, the molar ratio of the crosslinking agent to the raw material to be crosslinked is preferably 0.8 to 5, more preferably 1 to 3.

The resin obtained by which invention has both 5 molding hardenability and high heat resistance, is suitable for structural materials and electronic materials that require heat resistance, and is judged to have an extremely high valence of 11σ.

Examples will be shown below, but the present invention is not limited to these Examples in any way.

Examples Example 1 44.6 parts by weight of phenanthrene (hereinafter parts are simply referred to as parts) [0.25mall, l)-xylylene glycol 69.1 parts [0-5mol], p-
) 6.9 parts of luenesulfonic acid (monohydrate) was charged into a glass reactor and reacted for 15 minutes at 120°C in a nitrogen stream, and then 23.5 parts of phenol [0.25 mol
] was added and the condensation reaction was continued for an additional 13 minutes.

The temperature of the generated resin was raised at a rate of 6°C/m, and the apparent viscosity was 1.
The pour point, which is defined as the temperature at which 0' poise is reached, was measured and found to be 118°C. In addition, we measured the curing characteristics of the produced resin using a flow tester (nozzle diameter 1 m, length 11, pressure 10 kgf/cd), and found that curing was defined as no outflow from the nozzle. Hardened.

Example 2 44.6 parts of phenanthrene [0.25 mol, rn-
Xylylene glycol 103.5 parts [0.75mall
, I) -Toluenesulfone* (monohydrate) 8.8 parts was charged into a glass reactor, and 1
After reacting for 5 minutes, m-Kutsol 27.0 parts [0
, 25 mol] and the condensation reaction was further carried out for 13 minutes.

When the pour point and curing properties of the resin produced in the same manner as in Example 1 were measured, the pour point was 110°C and the curing property was 140°C.
It was cured by heat treatment for 1.5 minutes.

Example 3 42 parts of naphthalene [0.25mall] was poured into a 4.4-biphenylene vessel and reacted for 15 minutes at 120°C in a nitrogen stream, and then 36.0 parts of 1-naphthol [0.25m
All were added and the condensation reaction was further carried out for 13 minutes. The pour point of the resulting resin was 121'C, and the curing properties were cured by heat treatment at 140C for 2 minutes.

Example 4 Coal tar fraction boiling point 280-450°C) 44
．． 6 parts [0.25 mall as molecule flil18 (same as anthracene), p-xylylene glycol 6
9.1 parts [0.5mall] and 6.7 parts of p-toluenesulfonic acid (monohydrate) were charged into a glass reactor, and after reacting for 15 minutes at 140°C in a nitrogen stream, 23.5 parts of phenol was added. part [0.25 mol], and then add 1 part [0.25 mol]
The condensation reaction was carried out at 20°C for 13 minutes. The pour point of the resin produced was 103°C. In addition, the curing property is 150
It was cured by heat treatment at ℃ for 5 minutes.

Example 5 44.6 parts of phenanthrene [0.25mall, l)
-xylylene dichloride 87.52 parts [0.5 mol
After 7.8 parts of tin chloride was charged into a glass reactor and reacted for 15 minutes at 120°C in a nitrogen stream, 23.5 parts of phenol (0.25 mol) was added, and the condensation reaction continued for 13 minutes. I let it happen. The pour point of the resin produced is 110
'C. Further, the curing properties were determined by heat treatment at 140° C. for 2 minutes.

Comparative Example 1 Phenanthrene 89.3 parts [0.5 mol], ]p
- xylylene glycol 69.1 parts 0.5 mol,
When 7.9 parts of p-toluenesulfonic acid (monohydrate) was charged into a glass reactor and reacted with stirring in a nitrogen stream, a B-stage resin having a pour point similar to that of Example I was obtained. A heat treatment at 120'C for 120 minutes was required to obtain. The pour point of the resin produced was 108°C. Also, the curing properties are 150"C:.

It was cured by heat treatment for 30 minutes.

Comparative Example 2 44.6 parts of phenanthrene [0.25 mol, p-xylylene glycol 69.1 parts [0.5 mol, 23.5 parts of phenol [0.25 mall, l] -) luenesulfonic acid (monohydrate) 6.9 parts of the product was charged into a glass reactor, and a condensation reaction was carried out at 120° C. for 28 minutes in a nitrogen stream. The pour point of the resin produced was 132°C.

Further, when the raw material conversion rate was measured during the reaction (after 15 minutes at 120°C), it was found that phenol was 100%, p-xylylene glycol was 100%, and phenanthrene was 14%. This indicates that phenol is selectively reacting with the crosslinking agent.

The curing properties were determined by heat treatment at 140°C for 15 minutes.

Example 6 The cured resins obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were further post-cured at 200°C for 3 hours, and then heated in air at a rate of 5°C/sin under normal pressure to give a temperature of 10 %'If f
! The temperature at t i was measured. The results are shown in Table 1.

Furthermore, for comparison, a cured product of a commercially available phenol-novolac-hexamine-based resin has an average molecular weight of 600, hexamine of 8 wt%, a high carbonization yield grade, and a hardening condition of 150°C.
(Post-curing at 200'C for 2 minutes and post-curing at 200'C for 180 minutes) The temperature at the time of 10% traumatic reduction in air under the same conditions as above was measured and is also listed in Table 1.

Table 1 As shown in Table 1, the resin of the present invention has excellent oxidation resistance and thermal decomposition resistance compared to phenolic resin, and is almost equivalent to the condensed polycyclic polynuclear aromatic resin of Comparative Example 1. It is clear that it has a heat resistance of .

Moreover, the heat treatment time required for curing is about 176 times compared to the comparative example.
It is as short as ~l/15, and the molding processability is dramatically improved.

Claims (1)

[Claims] 1) A condensed polycyclic aromatic hydrocarbon and an aromatic compound having two or more functional groups represented by the general formula CH_2X (where X=OH, Cl, Br) in the presence of an acid catalyst Lower polycondensation,
A method for producing a thermosetting resin, which comprises then adding phenols and further polycondensing the resin. 2) The method for producing a thermosetting resin according to claim 1, wherein the aromatic compound having two or more functional groups represented by the general formula CH_2X is xylylene glycol. 3) Thermosetting according to claim 1, wherein the condensed polycyclic aromatic hydrocarbon is naphthalene, phenanthrene, anthracene, pyrene, fluoranthene, acenaphthene, methylnaphthalene, or a mixture thereof, such as pitch containing them. Method of manufacturing resin.