JPH03229717A - Phenolic resin containing propenyl group - Google Patents

Abstract

PURPOSE:To prepare a phenolic resin improved in processability and heat resistance, and giving a cured article improved in strengths so as to be suitable for the use as a compounding ingredient for various resin compsn., curing agent and modifier for various resins, etc., by giving a specific structure to the phenolic resin. CONSTITUTION:One mol of a phenolic compd. (e.g. 2-allylphenol) is reacted with 0.05-1mol of an aldehyde compd. in the presence of an alkali or acid catalyst in an org. solvent at 100-150 deg.C for 4-8hr to give a polymer, which is isomerized with an alkali to give a propenyl phenol resin of the formula [wherein R<1> is H or a 1-11C (substd.) monovalent hydrocarbon group; X is H or halogen; l is 0 or higher; m is 1 or higher; and l+m is 1-50].

Description

[Detailed Description of the Invention] Product No. 1 The present invention relates to phenolic resins, and more specifically, the present invention relates to phenolic resins, and more particularly, the present invention relates to phenolic resins, and more specifically, the present invention relates to phenolic resins that are conjugated to aromatic groups and that provide cured products with excellent processability and heat resistance, high strength, and particularly high glass transition temperature. The invention relates to phenolic resins containing groups.

Phenolic resin, which has a long-spreading property, is used as a material for casting, impregnation, lamination, and molding, as well as in various electrical insulation materials and structural materials. In recent years, the conditions for using materials in each of these applications have tended to become stricter, and in particular, the heat resistance of materials has become an important characteristic.

Conventional phenolic resins include phenol noholac resin, orthocresol novolac resin, bisphenol A, and triphenolmethane, which all exhibit relatively high heat resistance, but their heat resistance is insufficient. It was not satisfactory, and had the disadvantage that it required heating at high temperature for a long time to develop practical strength, and furthermore, the workability was not sufficient.

The present invention was made in view of the above circumstances, and is a cured product that is suitable for use as a component of various resin compositions, a curing agent or a modifier for various resins, has good processability, excellent heat resistance, and has high strength. The purpose of the present invention is to provide a phenolic resin that provides the following properties.

In order to solve the problem, the present inventors conducted intensive studies to achieve the above object, and as a result, the following general formula (1) obtained by isomerizing and polymerizing a phenol compound (however, in the formula R'
is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 11 carbon atoms, X is a hydrogen atom or a haloken atom, and l
is an integer of 0 or more, m is an integer of 1 or more, and j2+m is an integer of 1 to 50. ) The phenolic resin containing a propenyl group conjugated with an aromatic group has good processability, excellent moldability, heat resistance, long-term heat deterioration resistance, and high strength cured product. It was found that this compound is excellent as a curing agent for epoxy resins for encapsulating semiconductor devices.

In this case, the propenyl group-containing phenol resin conjugated with the aromatic group is the =SiH group of the organosilicon compound,
It has been found that it is highly reactive with vinyl groups, epoxy groups, and phenolic hydroxyl groups of various organic compounds, and is useful for modifying organopolysiloxanes, maleimide resins, epoxy resins, and other phenolic resins that have these functional groups, for example. It is something. Therefore, the present invention provides a propenyl group-containing phenol resin represented by the above formula (1).

The present invention will be explained in more detail below.

The propenyl group-containing phenol resin according to the present invention is a propenyl group-containing phenol resin conjugated with an aromatic group represented by the following general formula (1).

Here, R' in the formula is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 11 carbon atoms, preferably 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, t-butyl group, propenyl group. group, phenyl group, etc., and X is hydrogen or a halogen atom.

In addition, l is an integer greater than or equal to 0, m is an integer greater than or equal to 1, and 1
+m is an integer from 1 to 50, preferably from 1 to 10.

Since the propenyl group-containing phenol resin conjugated with the aromatic group of the present invention represented by formula (1) has a propenyl group as a functional group in the molecule, it is capable of radical reactions with vinyl group-containing compounds. Yes, also ';ESiH
It is also possible to carry out an addition reaction with an orcappolysiloxane compound containing , a compound having an epoxy group or a phenolic hydroxyl group, and it is effective as a modifier for epoxy resins, other phenolic resins, maleimide resins, etc.

The propenyl group-containing phenol resin of the present invention can be easily synthesized by isomerizing and polymerizing a phenol compound.

In this case, the raw material phenol compound can be selected depending on the intended propenyl group-containing phenol resin, and for example, 2-allyl substituted phenol is preferred.

Furthermore, the isomerization of phenolic compounds is described in the Journal of the American Chemical Society.
rnal of American Chem
ical 5ociety) J No. 1709-
It is preferable to use the alkali isomerization method described on page 1713 (1956).

Further, polymerization to obtain a novolak compound can be carried out by using a known alkali or acid catalyst and reacting it with an aldehyde compound.

Here, specific examples of the aldehyde compound include formaldehyde and salicylaldehyde. Also,
Although the amount of the aldehyde compound to be used is not particularly limited, it is preferable that the molar ratio of the raw material aldehyde compound/phenol compound is 0.05 to 1, particularly 0.011 to 0.7. Molar ratio of aldehyde compound/phenol compound is 0
．． If the molar ratio is less than 0.05, the molecular weight of the obtained polymer may become small, and if this molar ratio exceeds 1, it may result in kelization.

Furthermore, among alkali and acid catalysts, examples of alkali catalysts include KOH and NaOH, and examples of acid catalysts include hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, acetic acid, butyric acid, and propionic acid. The amount of the alkali or acid catalyst used can be a catalytic amount, and is usually used in an amount of 0.5 to 2% by weight based on the phenol compound.

This polymerization reaction is preferably carried out in an organic solvent such as toluene, and the reaction conditions are not particularly limited, but
It is preferable to carry out the reaction at 100-150°C for 4-8 hours.

Note that the phenol compound may be polymerized after being alkali isomerized, or may be polymerized and then alkali isomerized.

Specifically, among the ferno resins according to the present invention, a propenyl group-containing phenol novolac resin conjugated with an aromatic group represented by the following formula (2) can be synthesized, for example, according to the following reaction formula I or (2).

In other words, in the above reaction, the raw material 2-allyl-substituted phenol is alkali isomerized to propenyl-substituted phenol, and then it is reacted with formaldehyde in the presence of an alkali-acid catalyst to form noholak (reaction formula I). ), or alkaline isomerization (
Reaction formula ■).

In this case, in the noholak reaction of reaction formula (1), the following side reactions occur.

(n, p, and q are uniform) The above side reactions are likely to occur when strong acids such as hydrochloric acid, sulfuric acid, nitric acid, and para-toluenesulfonic acid are used as acid catalysts. Therefore, in order to prevent the above side reactions, it is necessary to As a catalyst, a weak acid such as acetic acid, butyric acid, propionic acid (p k a 4.
It is preferable to use 0~5.0).

In the above reaction formula (2), the reaction catalyst for converting 2-allyl-substituted phenol into resol by the novolac conversion method is particularly KOH, NaOH, etc. as an alkali catalyst, and hydrochloric acid, nitric acid, oxalic acid, etc. as a methylation catalyst. , para-toluenesulfonic acid and the like are preferably used.

Further, in the novolac formation in the above reaction formula I, (2), the molar ratio of phenol and formaldehyde is preferably formaldehyde/phenol -0.4 to 1, particularly 0.5 to 0.7. If the formaldehyde/phenol molar ratio is less than 0.4, the molecular weight may become small;
If it exceeds ■, it may gel.

Among the phenol resins according to the present invention, a double bond-containing polyfunctional phenol resin conjugated with an aromatic group represented by the following formula (3) can be synthesized according to the following reaction formula.

In the above reaction, salicylaldehyde is used as an aldehyde compound to polymerize allyl-substituted phenol, and the amount of salicylaldehyde used is such that the molar ratio of allyl-substituted phenol to salicylaldehyde is salicylaldehyde/allyl-substituted phenol = 0.1. ~0.5,
In particular, it is preferable to set it to 0.11 to 0.3. If the molar ratio of salicylaldehyde/allyl-substituted phenol is less than 0.1, the yield may be low;
If it exceeds 5, the molecular weight may become high.

Among the phenolic resins of the present invention, a polyfunctional phenolic resin containing a double bond conjugated with an aromatic group represented by the following formula (4) can be synthesized according to the following reaction formula.

Br ■ CH2CH=CH2 That is, in the above reaction, the polyphenol compound is allyl etherified, further subjected to Claisen rearrangement, and then alkali isomerized to synthesize the desired phenol resin. According to this method, the desired phenol resin is synthesized by the above formula (4). Propenyl group-containing phenol resins can be synthesized in high yields with few side reactions.

Furthermore, among the phenol resins of the present invention, a propenyl group-containing polyfunctional phenol resin represented by the following formula (5) can be synthesized according to the following reaction formula.

In the above reaction, polymerization is performed by reacting allyl-substituted phenol with salicylaldehyde and formaldehyde in the presence of an alkali-acid catalyst, and the ratio (mole ratio) of the phenol compound, salicylaldehyde, and formaldehyde is as follows: Salicylaldehyde: formaldehyde = l: 0.05-0.25:
It is preferable to use each component so that it becomes 0.2-0.5. In this case, the higher the ratio of salicylaldehyde and formaldehyde, the easier it will be to gel.
If the amount is too small, the molecular weight may become small and the yield may also become worse.

In addition, since the reactivity of salicylaldehyde is slower than that of formaldehyde, it is preferable that salicylaldehyde is first reacted to form a resol, and then reacted with formaldehyde.

λj Stirring υ Result The propenyl group-containing phenolic resin of the present invention has excellent processability, is highly reactive with epoxy resins, other phenolic resins, and maleimide resins, and has good heat resistance. Maleimide resin modified with phenolic resin has excellent mechanical properties at high temperatures, long-term heat deterioration resistance, and provides a cured product with high strength. Therefore, the propenyl group-containing phenolic resin of the present invention is extremely useful as a component of various resin compositions, and as a curing agent or modifier for various resins.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

[Example 1] 134% of 2-allylphenol was added to a four-liter flask equipped with a condenser, a thermometer, and a stirrer under an N2 atmosphere.
g (1.0 mol), 37% formaldehyde aqueous solution 45
g (0,05 mol), salicylaldehyde 1.2 g (0
, 01 mol) was added. NaOH1,0g while stirring
was added thereto, and the reaction was then carried out under reflux for 6 hours. 6 hours later,
2.4 g of oxalic acid and 100 g of toluene were added, and the mixture was heated and dehydrated under refluxing toluene for 2 hours. After 2 hours, toluene was removed under reduced pressure, and the mixture was reacted at 150°C for 1 hour. After that, it was cooled and the reaction product was converted into MIBK (methyl isobutyl ketone).
By diluting with water and removing the solvent after washing with water, 112 g of the following compound A having an OH equivalent of 153 was obtained.

(n”=5.m=1) Compound 8 The identity of Compound A was confirmed by NMR and IR.

Phenolic resin (compound A) 9 was added to a four-bottle flask equipped with a condenser, a thermometer, and a stirrer under an atmosphere of N2.
(OH equivalent weight 153).

While stirring, add 100 g of methanol and 50 g of n-butavine.
After that, 61 g of KOH was added, and after heating and dissolving, the metal was removed and the reaction was carried out at 110 to 120'C for 6 hours. After 6 hours, MIBK200d was added, neutralized with hydrochloric acid, and the solvent was removed to reduce the softening point to 95°C1OH equivalent 1
880 g of the following compound No. 54 was obtained (yield: 89%).

(n'=5.m=1) compound The infrared absorption spectrum of Compound B is shown in FIG.

When the molecular weight was measured using G, P, C, the number average molecular weight (M n ) was 7964, and the weight average molecular weight (
MW) is 10193, and the polydispersity (MW/M n
) was 1.28. The NMR spectrum was assigned to Fukishita.

Solvent: CD3COCD3 ppIll [σ] 1.67, 1.77: -CHFCH-CHi2.8
1 Knee f: C, H2-C tanto 3.60-3.77
：Number C6H2C 5.6~6.2 : -CH=
CH-CH.

6.7-7.2 EC6H, published [Example 2] Compounding (■ Synthesis 134 g of 2-alliphenol was added to a four-bottle flask equipped with a condenser, a thermometer, and a stirrer under an N2 atmosphere.
(1,0 mol), salicylaldehyde 15.2 g (0,
125 mol) was added. While stirring, add NaOH (30%
80 g of aqueous solution was added thereto, and the mixture was reacted under reflux for 6 hours. After 6 hours, 110 g of hydrochloric acid and 100 g of toluene were added, and the mixture was heated and dehydrated under refluxing toluene for 2 hours. 2 hours later,
Toluene was removed under reduced pressure, and the mixture was reacted at 150°C for 1 hour. After cooling, the reactants were diluted with MIBK and the solvent was removed after washing with water, resulting in an OH equivalent of 133 (theoretical amount 1
39 g of the following compound C of 30) was obtained (yield: 81% vs. salicylaldehyde).

Compound C was identified by NMR, I Synthesis 40 g of Compound C was placed in a four-bottle flask equipped with a condenser, a thermometer, and a stirrer under an N2 atmosphere (OH
equivalent weight 130). While stirring, add 100 g of methanol, n-
Add 50g of butanol, then add 18g of KOH, heat and melt, remove metal, and heat to 110-120°C.
The mixture was allowed to react for 6 hours. 6 hours later, MI BK200rr
ll, neutralize with hydrochloric acid and remove the solvent.
36 g of the following compound D with an OH equivalent of 34 (theoretical amount 130)
was obtained (yield 90%).

Confirmed by R.

Compound cucumber The infrared absorption spectrum of the compound is shown in Figure 2.

When the molecular weight was measured using G, P, and C, the number average molecular weight (M n ) was 391, the weight average molecular weight (MW) was 410, and the polydispersity (MW/Mn) was 1.05. The NMR spectrum was assigned to Fukishita.

Solvent: CD3COCD3 ppm [σ] 1.67, 1.77: -CH=CH-C Month 52.8
1: +C6H2-Cdan-to5.6~6.2:
-CH=CH-CH36,7 to 7.2 kN (-C6x+ [Example 3] A 21-meter four-lobe flask equipped with a heiwei condenser, a thermometer, and a stirrer was heated under an N2 atmosphere. 292g of phenolmethane
(1.0 mol), 363 g (3.0 mol) of allyl bromide, 414 g (3.0 mol) of potassium carbonate, and 600 g of acetone were added. After reacting under reflux for 8 hours, the solvent was removed by stripping. After that, MI BK6007
7Z7! The solution was dissolved in water, washed with water, and the solvent was removed to obtain 350 g of the allyl ether compound shown below (yield: 85%).

The identity of compound E was confirmed by IR and NMR.

350 g (0.88 mol) of Compound E was placed in an 11 flask equipped with a 41-pronged jig, a condenser, a thermometer, and a stirrer under an N2 atmosphere. The mixture was heated with stirring and reacted at 200° C. for 4 hours.

After the reaction was completed, the reaction mixture was cooled to obtain 333 g of Compound F produced by Claisen rearrangement with an OH equivalent of 139 (theoretical amount: 137). (Yield 95%) The identity of compound F was confirmed by NMR and IR.

Compound F and A (1) 300 g of Compound F was placed in a 21-meter four-eye flask equipped with a L in-flame condenser, a thermometer, and a stirrer under an atmosphere of N2. While stirring, 200 g of methanol was added.

Add 100g of n-butanol, then 123g of KOH.
After heating and melting, remove the metal and give 110 to 12
The reaction was carried out at 0°C for 6 hours. 6 hours later, MI BK500
By adding m/, neutralizing with hydrochloric acid and removing the solvent,
The following compound G261 with an OH equivalent of 141 (theoretical amount 137)
g (yield 87%).

Compound Ω The infrared absorption spectrum of Compound G is shown in FIG.

When the molecular weight was measured by G, P, C, the number average molecular weight (M n ) was 417, the weight average molecular weight (MW) was 431, and the polydispersity (M W / M n ) was 1.
．． It was 04. The NMR spectrum was assigned to Fukishita.

Solvent: CD3COCD3 ppm Cσ] 1.67.1.77: -CH=CH-C Month 12.81
Knee+C6H2-CH-)5.6~6.2:
-CH=CH-CH36, 7~7.2 Ni + C June neat [Example 4] O-talesol under N2 atmosphere in a 200-4-hole flask equipped with a condenser, a thermometer, and a stirrer. 10.8g
(0.2 mol), 38% formaldehyde aqueous solution M16.
2 g (0.2 mol) was added. NaO without stirring
0.1 g of H was added, and the reaction was then carried out under reflux for 6 hours. After 6 hours, 29.2 g of triphenolmethane (0,1
mole), 2.4 g of oxalic acid.

100 g of toluene was added, and the mixture was heated and dehydrated under refluxing toluene for 2 hours. After 2 hours, the toluene was removed under reduced pressure, the reaction was diluted with MIBK, and the O
42 g of phenolic resin with H equivalent of 109 (theoretical amount 1o7)
I got it. Thereafter, allyl etherification, Claisen rearrangement, and isomerization were performed in the same manner as in Example 3 to obtain the following compound H having an OH equivalent of 150 (theoretical amount: 147).

Compound H was identified by IR and NMR spectra.

[Experiment example]

In the same method as in Example 1, except that salicylaldehyde was not added, an OH equivalent of 148
(Theoretical amount: 146) of the following Compound I was obtained.

Next, compound CB obtained in Example 1 and compound CI] were used in the amounts shown in Table 1 for 50 parts of N,N'-4,4'-diphenylmethane bismaleimide, and The components shown in Table 1 were added thereto, and the resulting mixtures were uniformly melted and mixed using two heated rolls to produce two types of thermosetting resin compositions I and (2).

The following tests (a) to (c) were conducted on these two types of resin compositions.

(a) Using a mold that complies with spiral flow EMMI standards, 175℃, 70℃
It was measured under the condition of kg/cd.

(b) ζ and number JIS-6
175℃, 70kg/Ci, molding time 2 according to 911
A bending rod of 10×4×100 was formed under the conditions of 1 minute.
25 for those post-cured at 80°C for 4 hours
℃, measured at 250℃.

(c) Reciprocal test (using a test piece with a diagonal diameter of 4 mmφ x 15 mm,
The value was measured when the temperature was raised at a rate of 5°C per minute.

The results of the above tests are also listed in Table 1.

Table *(EoCN1020(65)) ・−・−'Japan I [
From the results in Table 1, compared to the composition using the propenyl group-containing phenolic resin CI which does not have a trinuclide, the propenyl group-containing phenol resin [B] having a trinuclide of the present invention is blended. The resulting composition was found to have excellent bending strength, especially at high temperatures, and a high glass transition temperature.

[Brief explanation of drawings]

Figures 1 to 3 show compounds B and D of the present invention, respectively. It is a graph showing the infrared absorption spectrum of G.

Claims (1)

[Claims] 1) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1) (However, in the formula, R^1 is a hydrogen atom or a carbon number of 1 to 11. unsubstituted or substituted monovalent hydrocarbon group, X is a hydrogen atom or a halogen atom, l is an integer of 0 or more, m is an integer of 1 or more, l + m is an integer of 1 to 50) A propenyl group-containing phenolic resin.