JPH04225012A - Tetra-nuclear phenolic novolak and its production - Google Patents

Abstract

PURPOSE:To obtain the subject novolak having low softening temperature and excellent handleability and workability, and giving a cured product having excellent heat-resistance in high yield by reacting an o-cresol binuclear dimethylol compound with an aromatic compound having allyl group, etc. CONSTITUTION:The objective tetra-nuclear phenolic novolak expressed by formula III (R1, R2, R6 and R7 are H or allyl; R3, R4, R5 and R8 to R10 are H, <=5C alkoxy or <=5C alkyl) can be produced by adding a compound of formula II (R11 and R12 are H or allyl; R13 and R15 are H, <=5C alkoxy or <=5C alkyl) (e.g. 2-allylphenol) to an o-cresol binuclear dimethylol compound of formula I, stirring the mixture in nitrogen atmosphere at room temperature, adding p-toluenesulfonic acid to the mixture, reacting at 50 deg.C for 2hr, adding an organic solvent such as methyl isobutyl ketone to dissolve the reaction product, washing the obtained solution with water, separating the organic layer and finally distilling out the solvent.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tetranuclear phenolic novolak and a method for producing the same.

0002

[Prior Art] Phenolic novolaks are widely used as phenolic resins in electrical, electronic, architectural, paint-related, etc., but conventional phenolic novolaks have a wide molecular weight distribution, and their differences are mainly due to differences in softening temperature. It has been used for various purposes.

0003

[Problems to be Solved by the Invention] However, demands for higher performance for resins using phenolic novolacs have been increasing in recent years, and conventional novolaks with a wide molecular weight distribution are no longer able to meet the demands.

[0004] For example, in electrical and electronic equipment, there has been a remarkable increase in integration, performance, and reliability.
At the same time, it is desired that the insulating materials, components, etc. used therefor be further improved in various performances such as heat resistance, moisture resistance, and dimensional stability.

Conventionally, phenolic novolacs used for these materials have low viscosity products (low softening temperature products) containing a large amount (for example, 25% by weight) of low-molecular compounds such as binuclear bodies, and have poor heat resistance in the cured product. Some bisphenol-based compounds are liquid at room temperature and are easy to use, but because they are difunctional, they have a drawback in heat resistance when cured.

[0006] Although phenolic novolacs with a high softening temperature improve the heat resistance of the cured product, the high softening temperature causes poor workability and has drawbacks such as limited use due to compatibility. have

[0007]

[Means for Solving the Problems] As a result of various studies on phenolic novolacs, the present inventors found that a specific tetranuclear phenolic novolak has a cured product with excellent heat resistance despite its low softening temperature. The present inventors discovered that the phenolic novolak is a phenolic novolak, and completed the present invention.

That is, the present invention provides (1) formula [1]

00
09]

[C4]

(In the formula, R1, R2, R6, R7 each independently represent a hydrogen atom or an allyl group, and R1, R2
, R6, and R7 are allyl groups, and R3
, R4, R5, R8, R9, and R10 each independently represent a hydrogen atom, an alkoxyl group having 5 or less carbon atoms, or an alkyl group having 5 or less carbon atoms. ) is a tetranuclear phenolic novolac.

(2) Formula [2]

0012

[C5]

The O-cresol dinuclear dimethylol compound represented by the formula [3]

[0014]

[C6]

(In the formula, R11 and R12 each independently represent a hydrogen atom or an allyl group, and R13, R14, R
15 each independently represents a hydrogen atom, an alkoxyl group having 5 or less carbon atoms, or an alkyl group having 5 or less carbon atoms. )
The above formula [ characterized by reacting a compound represented by
The present invention relates to a method for producing a tetranuclear phenol novolac represented by [1].

In the present invention, the tetranuclear phenol novolak [1] is obtained by reacting the O-cresol dinuclear dimethylol compound represented by the above formula [2] with the compound represented by the formula [3]. However, the reaction is preferably carried out in the presence of an acid catalyst, and the compound of formula [1] can be easily obtained by dehydration condensation.

Examples of catalysts used include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as p-toluenesulfonic acid and oxalic acid. Oxalic acid is preferred.

The amount of the catalyst used is preferably 0.1 to 0.1 to the O-cresol dinuclear dimethylol compound (formula [2]).
The range is 30% by weight, more preferably 0.2 to 1
It is 0% by weight.

Compounds of formula [3] include 2-allylphenol, allyl phenyl ether, 2-allyl-4-
Examples include methylphenol, 2-allyl-6-methylphenol, 4-allyl-2-methoxyphenol, and 2-allylphenol is preferred.

In the tetranuclear phenolic novolak of formula [1], when allyl groups are attached to both of the two terminal benzene nuclei, the above-mentioned allyl group-containing compounds are used as compounds of formula [3]. One or more types may be used, but if an allyl group is attached to only one of the two terminal benzene nuclei of the tetranuclear phenol novolak of formula [1], as a compound of formula [3], The allyl group-containing compound and other phenols are used in combination.

Examples of other phenols include phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol,
1 as a substituent for 2,3,6-trimethylphenol, etc.
Examples include phenols having ~3 lower alkyl groups (for example, methyl groups).

When the above allyl group-containing compound and other phenols are used in combination as the compound of formula [3], the proportion of the allyl group-containing compound used is 10 mol % of the total amount of the compound of formula [3]. It is preferable that it is more than 2, especially 2
It is preferably 0 mol% or more. However, when the reaction product obtained by the reaction is used as it is and it is desired to use a reaction product with a large alkenyl equivalent, the proportion of the allyl group-containing compound used can be 10 mol % or less. That is, the proportion of the allyl group-containing compound to be used can be freely selected as required.

The amount of the compound of formula [3] to be used is preferably in the range of 1 to 50 moles, particularly preferably in the range of 2 to 15 moles, per mole of the O-cresol dinuclear dimethylol compound (formula [2]). .

The reaction can be carried out without a solvent, but it can also be carried out in a solvent, and the solvent may be benzene, toluene, methyl isobutyl ketone, etc. as long as it does not react with the raw materials or products. , any of them can be used without particular limitation.

The reaction is usually carried out under normal pressure, but it can also be carried out under reduced pressure and temperature to such an extent that the water produced in the reaction is removed from the reaction system and the raw material compounds used in the reaction are not distilled off.

When a solvent is not used, the reaction temperature is higher than the melting point of the starting compound used, but when a solvent is used, the reaction can be carried out at a temperature independent of the melting point of the starting compound. The reaction temperature is usually in the range of 20°C to 150°C, preferably 40°C to 100°C.

The reaction time is not particularly limited, but is usually 10
minutes to 20 hours, preferably 30 minutes to 10 hours.

After the completion of the reaction, the used catalyst is removed by washing with water, etc., and then the used solvent and excess compound of formula [3] are distilled off under reduced pressure to obtain a high amount of the target tetranuclear phenol novolac. obtained in high yield.

The reaction product thus obtained (alkenyl group-containing phenol novolak) varies depending on the proportion of the allyl group-containing compound and other phenols used as the compound of formula [3], but usually contains 1% by weight or more of the tetranuclear phenolic novolac of formula [1], but by increasing the proportion of the allyl group-containing compound used, the formula [1] in the reaction product (alkenyl group-containing phenolic novolak) The content of the tetranuclear phenol novolak can be 30% by weight or more or 50% by weight or more.

The alkenyl group-containing phenolic novolak obtained by the above reaction usually contains 15% by weight or less, more preferably 10% by weight or less of dinuclear phenolic novolak.
It contains at most 5% by weight, particularly preferably at most 5% by weight.

Examples of these dinuclear phenol novolaks include compounds represented by formula [4].

[0032]

[C7]

The smaller the amount of the dinuclear phenol novolak contained in the alkenyl group-containing phenol novolak, the better. Therefore, it is preferable to select conditions such that the compound of formula [4] is not produced as a by-product as much as possible. . The alkenyl group-containing phenol novolak may also contain polynuclear phenolic novolaks such as pentanuclear, hexanuclear, and octnuclear.

[0034] Here, the term "X-nuclear" refers to a compound having X benzene nuclei in one molecule, such as tetranuclear,
Nuclear body means a compound having four or two benzene nuclei in one molecule, respectively.

The tetranuclear phenolic novolac of the present invention has a low softening temperature and is therefore easy to handle, and the cured product obtained using the modified product with silicone compounds has excellent heat resistance and low stress properties. . Therefore, the tetranuclear phenolic novolac of the present invention can be used as a curing agent for epoxy resin laminates and epoxy resin molding materials with excellent heat resistance for electronic and electrical equipment applications, and can also be used as a curing agent for epoxy resin raw materials and other derivatives. It can also be used as a raw material.

[0036]

[Examples] The present invention will be specifically explained below with reference to Examples.

Example 1 O-cresol 2 was placed in a gas container equipped with a thermometer and a stirrer.
Nuclear dimethylol compound (formula [2]) 200g (0.6
9 mol) and 924.6 g of 2-allylphenol (6.
9 mol) was charged and stirred at room temperature under a nitrogen atmosphere. P-
Add 2 g of toluenesulfonic acid (1.0% by weight based on the O-cresol dinuclear dimethylol compound), being careful not to generate heat.
The mixture was added gradually so that the liquid temperature did not exceed 50°C.

After the addition, the mixture was heated to 50° C. on an oil bath and reacted for 2 hours. After that, 500 ml of methyl isobutyl ketone was added and the mixture was transferred to a 2 liter separating funnel and washed with water. After washing with water until the washing water shows neutrality, the solvent in the organic layer and excess 2-
Allylphenol was removed under reduced pressure to obtain 340 g of a pale yellow viscous substance [product (A)].

The softening temperature of the product (A) is 40.1°C, and the hydroxyl group equivalent (g/eq) is 131 alkenyl equivalent (g/eq).
q) was 265.

Tetrahydrofuran (THF) as a solvent
When the product (A) was analyzed using the following GPC apparatus, the molecular weight distribution curve shown in FIG. 1 was obtained.

[0041] GPC device: Shimadzu Co., Ltd. Column: TSK-G-3000HXL (1 piece)
+TSK-G-2000HXL (2 pieces)
Medium: Tetrahydrofuran 1ml/min Detection: UV (254nm)

004
2] The retention time at which bisphenol F appears under these analysis conditions is 29.5 minutes, so the retention time of the main peak corresponds to the retention time of a tetranuclear substance having four benzene nuclei. The content of the compound in the product (A) was 90% by weight.

When the main peak compound was separated and analyzed by mass spectrometry (FAB-MS), it was found that M+
520 was obtained. Therefore, it was found that the compound of the main peak was a compound having the chemical structure of the following formula [5].

[0044]

[Chemical formula 8]

Further, from FIG. 1, it was found that the product (A) contained 0.3% by weight of the dinuclear phenol novolak.

Example 2 In Example 1, the amount of 2-allylphenol was changed to 370 g.
Reaction was carried out in the same manner as in Example 1 except that (2.76 mol) was used.
After treatment, 337 g of a pale yellow solid [product (B)] was obtained. The softening temperature of the product (B) was 57.4° C. and 275 in terms of alkenyl equivalent (g/eq).

The results of analysis of product (B) using a GPC device are shown in FIG. Note that the analysis conditions are the same as in Example 1. The retention time of the main peak is 4 as in Figure 1.
The content of the main peak compound in the product (B), which corresponds to the retention time of the nuclear body, is 60% by weight as shown in FIG. It was found that it contained 7% by weight.

[0048] Similarly to Example 1, the main peak compound was fractionated and analyzed by mass spectroscopy.
M+520 was obtained, and the main peak compound was of formula [5]
It was found that it has the chemical structure of

Example 3 In Example 1, 924.6 g of 2-allylphenol
184.9g (1.38g) of 2-allylphenol instead of
mol) and O-cresol 149.0g (1.38 mol)
The reaction and treatment were carried out in the same manner as in Example 1 except that 326 g of a pale yellow solid [product (C)] was obtained. Product (C) had a softening temperature of 84.0°C and an alkenyl equivalent (g/eq) of 735.

GPC analysis of product (C) is shown in FIG.
The analysis conditions are the same as in Example 1). The retention time of the main peak corresponds to the retention time of the tetranuclear body as in Figure 1, and from Figure 3, the main peak compound product (C
) was found to be 58% by weight, and the product (C) was found to contain 0.6% by weight of dinuclear phenol novolak.

[0051] In addition, in the same manner as in Example 1, the main peak compound was fractionated and analyzed by mass spectroscopy.
M+520, M+494 and M+468 were obtained, and the main peak compounds were the following (C-1), (C-2), (
It was found to be a mixture of three compounds C-3).

[0052]

[Chemical formula 9]

[0053]

Example 4 In Example 1, 924.6 g of 2-allylphenol
The reaction and treatment were carried out in the same manner as in Example 1, except that 92.5 g (0.69 mol) of 2-allylphenol and 223.6 g (2.07 mol) of O-cresol were used instead of 2-allylphenol. Product (D)] 320 g was obtained. The softening temperature of the product (D) is 84.5°C and the alkenyl equivalent (g/eq) is 1
It was 450.

GPC analysis of product (D) is shown in FIG.
The analysis conditions are the same as in Example 1). The retention time of the main peak corresponds to the retention time of the tetranuclear body as in Figure 1, and from Figure 4, the main peak compound product (D)
The content of the product (D) is 59% by weight, and the product (D) is 2% by weight.
It was found that it contained 0.7% by weight of the nuclear phenolic novolak.

[0056] Similarly to Example 1, the main peak compound was fractionated and analyzed by mass spectroscopy.
M+520, M+494 and M+468 were obtained, and the main peak compounds were the above (C-1), (C-2), (C
-3) was found to be a mixture of three compounds.

Example 5 In Example 1, 924.6 g of 2-allylphenol
184.9g (1.38g) of 2-allylphenol instead of
mol) and 168.4 g (1.38 mol) of 2,6-xylenol
The reaction and treatment were carried out in the same manner as in Example 1 except that mol) was used to obtain 337 g of a pale yellow solid [product (E)]. product (
The softening temperature of E) is 80.6°C and the alkenyl equivalent (g/e
q) was 790.

The GPC analysis of product E is shown in FIG. 5 (analytical conditions are the same as in Example 1). The retention time of the main peak corresponds to the retention time of the tetranuclear body as in Figure 1, and from Figure 5, the content of the compound of the main peak in the product (E) is 61% by weight, and ) was found to contain 0.6% by weight of the dinuclear phenolic novolak.

[0058] Similarly to Example 1, the main peak compound was fractionated and analyzed by mass spectroscopy.
M+520, M+508 and M+496 were obtained, and the main peak compounds were the following (E-1), (E-2), (
It was found to be a mixture of three compounds E-3).

[0059]

[Chemical formula 10]

Example 6 In Example 1, 924.6 g of 2-allylphenol
184.9g (1.38g) of 2-allylphenol instead of
mol) and 2,3,6-trimethylphenol 188.0
The reaction and treatment were carried out in the same manner as in Example 1, except that 334 g of a pale yellow solid [product (F)] was obtained, except that 1.38 mol of the product was used. The product (F) had a softening temperature of 80.2°C and an alkenyl equivalent (g/eq) of 820.

GPC analysis of product (F) is shown in FIG.
The analysis conditions are the same as in Example 1). The retention time of the main peak corresponds to that of the tetranuclear body as in Figure 1, and from Figure 6, the main peak compound product (F
) was found to be 60% by weight, and the product (F) was found to contain 0.5% by weight of dinuclear phenolic novolac.

[0063] Similarly to Example 1, the main peak compound was fractionated and analyzed by mass spectroscopy.
M+524, M+522 and M+520 were obtained, and the main peak compounds were the following (F-1), (F-2), (
It was found to be a mixture of three compounds of F-3).

[0064]

[Chemical formula 11]

Compound (F-1): In formula [8]
R22=allyl group, R23=H, R24=H,
R25=allyl group, R26=H,
R27=H, Compound (F-2): In formula [8], R22=allyl group, R23=H,
R24=H, R25=methyl group,
R26=methyl group, R27=methyl group Compound (F-
3): In formula [8], R22~
All R27 are methyl groups

Application Example 1 The alkenyl group-containing phenolic novolak [Product (A
)] 50g and methyl isobutyl ketone 500ml, 2
After charging 0.05 g of a 2-ethylhexanol-modified chloroplatinic acid solution with a platinum concentration of % by weight and performing azeotropic dehydration for 1 hour,
Silicone oil (G) under reflux {Chisso Co., Ltd., FM
-1121, H equivalent: 2334}440.4 g was added dropwise over 30 minutes. After further reacting at the same temperature for 3 hours, the solvent was washed with water and concentrated under reduced pressure to obtain 487.6 g of pale yellow viscous material (
Product A1) was obtained.

Application Example 2 In Application Example 1, 50 g of the product (B) obtained in Example 2: 424.4 g of silicone oil (G) was used instead of the product (A) obtained in Example 1. The reaction and treatment were carried out in the same manner as in Example 1, and 472.7 g of pale yellow viscous material (product B1
) was obtained.

Application Example 3 In Application Example 1, 50 g of the product (C) obtained in Example 3 and 158.8 g of silicone oil (G) were used instead of the product (A) obtained in Example 1. The reaction and treatment were carried out in the same manner as in Example 1, and 206.2 g of pale yellow viscous material (product C1
) was obtained.

Application Example 4 Application Example 1 except that 50 g of the product (D) obtained in Example 4 and 80.5 g of silicone oil (G) were used instead of the product (A) obtained in Example 1. Reacted and treated in the same manner as in Example 1, yielding 128.5 g of pale yellow viscous material (product D1).
I got it.

Application Example 5 In Application Example 1, 50 g of the product (E) obtained in Example 5 and 147.7 g of silicone oil (G) were used instead of the product (A) obtained in Example 1. The reaction and treatment were carried out in the same manner as in Example 1, yielding 195.8 g of a pale yellow viscous substance (product E1).
) was obtained.

Application Example 6 Application Example 1 except that 50 g of the product (F) obtained in Example 6 and 142.3 g of silicone oil (G) were used instead of the product (A) obtained in Example 1. The reaction and treatment were carried out in the same manner as in Example 1, and 189.6 g of pale yellow viscous material (product F1
) was obtained.

Reference Examples 1 to 6, Comparative Example 1 O-cresol novolak type epoxy resin (EOCN-1020: manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent (g/eq): 200, softened in the proportions shown in Table 1) temperature 66.4℃)
Silicone-modified phenolic novolak resins A1, B1, C1, obtained in Application Examples 1, 2, 3, 4, 5 and 6,
D1, E1, F1 and commercially available phenol novolak resin (
Nippon Kayaku Co., Ltd. (softening temperature: 83.0° C.) was used as a curing agent, and triphenylphosphine was used as a catalyst to heat cure the material and measure each physical property using the apparatus and method shown in the footnotes of Table 1. As a comparative example, only the phenol novolak resin shown in Table 1 was used as a curing agent, and the physical properties were measured in the same manner as above, and the results are shown in Table 1.

As is clear from Table 1, the glass transition temperature of the cured product when the alkenyl group-containing phenolic novolac of the present invention, which is mainly composed of the tetranuclear phenolic novolak, is modified with silicone and used as a curing agent. shows almost the same level as the comparative example, and while maintaining heat resistance, the elastic modulus is significantly reduced and stress is reduced.

1) Thermomechanical measuring device: Shinku Riko Co., Ltd.
TM-7000 2) JIS K 6911

[0075]

Effects of the Invention The tetranuclear phenol novolak of the present invention has a low softening temperature, so it is easy to handle and has excellent workability. According to the production method of the present invention, a tetranuclear phenolic novolak can be easily obtained in high yield.

[Brief explanation of the drawing]

FIG. 1: Molecular weight distribution curve of product (A) obtained in Example 1

FIG. 2: Molecular weight distribution curve of product (B) obtained in Example 2

FIG. 3: Molecular weight distribution curve of product (C) obtained in Example 3

FIG. 4: Molecular weight distribution curve of product (D) obtained in Example 4

FIG. 5: Molecular weight distribution curve of product (E) obtained in Example 5

FIG. 6: Molecular weight distribution curve of product (F) obtained in Example 6

[Figure 7] Molecular weight distribution curve of commercially available O-cresol novolak

Claims (2)

[Claims] Claim 1: Formula [1] [Formula 1] (wherein R1, R2, R6, R7 each independently represent a hydrogen atom or an allyl group, R1, R2, R6, R7
At least one of R3, R4, R5 is an allyl group, and R3, R4, R5
, R8, R9, and R10 each independently represent a hydrogen atom, an alkoxyl group having 5 or less carbon atoms, or an alkyl group having 5 or less carbon atoms. ) is a tetranuclear phenolic novolac. Claim 2: An O-cresol dinuclear dimethylol compound represented by the formula [2] [Chemical formula 2] is combined with a formula [3] [Chemical formula 3] (wherein R11 and R12 are each independently a hydrogen atom or an allyl R13, R14, and R15 each independently represent a hydrogen atom, an alkoxyl group having 5 or less carbon atoms, or an alkyl group having 5 or less carbon atoms. A method for producing a tetranuclear phenol novolak represented by the formula [1] in Item 1.