JPS60135418A - Production of modified phenolic resin - Google Patents

Abstract

PURPOSE:To obtain a modified phenolic resin excellent in flexibility and heat resistance and useful for paints, adhesives and molding materials, by reacting a reaction product between a specified compound and a phenol with an aldehyde. CONSTITUTION:1mol of a phenol of formula I (wherein R1 is H, a 1-8C alkyl or alkenyl, OH, a group of formula II or the like, and R2 is H, 1-8C alkyl or alkenyl) is reacted with 0.05-3mol of a compound of formula III (wherein R3-4 are each a group of formula IV or V) at 0-180 deg.C in the presence of an acidic catalyst such as sulfuric acid, and the product is neutralized and then dehydrated to obtain a compound (A). Compound A is reacted with an aldehyde in an amount to provide a ratio of the total number of moles of the OH groups in component A and OH groups in the phenol of formula I to the number of moles of the aldehyde groups of 1:0.1-2 at 80 deg.C-refluxing temperature for 30min-4hr in the presence (or absence) of a phenol of formula I in the presence of an acidic or alkaline catalyst to obtain the titled resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing modified phenolic resins which are very useful as paints, adhesives, molding materials and the like.

As a conventional method for producing phenolic resins, a method is known in which phenols are reacted with an alkylating agent such as formaldehyde in the presence of an acidic catalyst F. As a result of intensive studies to improve the flexibility and heat resistance of the phenolic resin obtained in this way, the present inventors replaced conventional aldehydes such as formaldehyde with the following: is the same as R8, and may be the same or different. ) The flexibility and heat resistance of conventional phenol novolak resins can be improved by blending the phenolic resin obtained by reacting the compound represented by (-F) with the presence of an acidic catalyst into a phenol novolak resin, etc. He discovered that it could be improved and filed Japanese Patent Application No. 87978/1983.

Further, the present inventors have conducted intensive studies to modify phenol novolak resins based on Japanese Patent Application No. 58-87978, and as a result, they have discovered the present invention.

That is, the present invention is based on the general formula (A) R+ 2 (wherein, R1 is an alkyl group with H1 having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, a -on group, and R2 is an alkyl group having H1 having 1 to 8 carbon atoms; ~8 alkyl group or C1-8 alkenyl group) and general formulas)
show. The definition of hole 4 is the same as Rs, and may be the same or different. ) in the presence of an acidic catalyst to form a compound obtained by the general formula 41 (wherein H1 is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, - (JR group, 几2 is ■,
It represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 1 to 8 carbon atoms. ) is a method for producing a modified phenolic resin, which is characterized by reacting the modified phenolic resin with an aldehyde in the presence or substantially absence of the phenol represented by the following formula under an acidic catalyst or an alkaline catalyst.

The invention will be described in detail below.

Specific examples of the phenols represented by the general formula 4 of the present invention include phenol, cresol, ethylphenol, isopropylphenol, isopropenylphenol, tert-butylphenol, octylphenol, xylenol, resorcinol, catechol, hydroquinone,
These include phenylphenol, cumylphenol, 4°4'-dihydroxy-diphenyl-2,2-propane, and the like.

Specific examples of compounds of general formula) are 1,8-diisopropenylbenzene, 4-diisopropenylbenzene, 8-diisopropenylbenzene,
(2-hydroxy-2-propyl)-isopropenylbenzene, 4-(2-hydroxy-2-propyl)-isopropenylbenzene, 1,8-di(2-hydroxy-2
-brobyl)benzene, 1,4-di(2-hydroxy-
2-propyl)benzene, etc. These compounds are
They can be used alone or in combination of two or more.

The production of the compound of general formula 4 is not particularly limited, but
For example, the general formula +a+ can be obtained by dehydrogenation of diisopropylbenzene or by air oxidation of diisopropylbenzene. ) It can also be obtained by reducing the hydroperoxide represented by the formula with sodium sulfite, hydrogen, etc. Furthermore, carbinols represented by the general formula can be dehydrated to obtain olefins represented by the general formula. These compounds can be used alone or as a mixture of two or more in the reaction.

In the present invention, phenols of general formula (3) and general formula (
In the method for producing a compound obtained by reacting the compound B) in the presence of an acidic catalyst, the proportion of the phenols and the compound represented by the general formula) is not particularly limited,
It is determined according to the desired properties of the compound to be obtained. In other words, the higher the proportion of phenols added, the more phenols react in the resulting compound, and the higher the heat resistance can be obtained. Usually, the compound of the general formula (Bl) is used in an amount of 0.05 to 8 times the mole per mole of phenols.As a catalyst, mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, silica-alumina, acid clay, etc. Solid acids, organic acids such as formic acid, oxalic acid, P-toluenesulfonic acid, aluminum chloride,
Examples include free delta raft catalysts such as iron chloride and zinc chloride. The amount used is not particularly limited and is determined in consideration of the reaction temperature and the desired properties of the compound to be obtained, but it is usually 0.00% per 1 part by weight of the total of the phenols and the compound of the general formula (Bl). It is used in the range of .001 to aooxm parts.

The reaction temperature is usually 0°C to 180°C, and generally, the lower the temperature, the more acidic catalyst is used to improve the efficiency of the reaction, and the higher the temperature, the less acidic catalyst is needed. Furthermore, when carbinols are used as the compound of general formula 03), water generated in the reaction can be removed from the reaction system in order to carry out the reaction efficiently, or the reaction can be carried out more smoothly. Suitable organic fd agents, such as benzene, toluene, hexane, heptane, etc., can also be used to increase the concentration. The reaction pressure is usually atmospheric pressure F, but if water is produced in the reaction, it can be carried out under reduced pressure to remove water from the reaction system, or under increased pressure if the acidic catalyst is a gas. You can also do it with

The compound obtained by the reaction of such phenols with the compound of the general formula Φ) ranges from liquid at room temperature to 200%
It is possible to obtain a solid material having a softening point of .degree. C., and it can be adjusted depending on the intended use of the modified phenolic resin for the purpose of the present invention.

The compound obtained by the reaction of phenols with the compound of the general formula () may be subjected to the next reaction with aldehydes after the reaction, neutralization treatment, dehydration, and operations such as organophilic solvent. After removing unreacted phenols by distillation, this bottom liquid may be subjected to the next reaction with aldehydes for dehydration and organic solvent operations, and further, after removing unreacted phenols by distillation. The distilled liquid may be subjected to operations such as recrystallization using an organic solvent, etc. to obtain a purified product, and the purified product may be subjected to the next reaction with aldehydes, and there is no particular restriction. Usually, this operation method is determined by arbitrarily adjusting the required molar ratio of the -UkL group of the phenol and the aldehyde group in the following reaction with the aldehyde, depending on the intended use of the modified phenolic resin.

The reaction of the compound obtained by the reaction of the phenol of general formula 4 with the compound of general formula ) and the aldehyde is carried out in the presence or substantially absence of the phenol of general formula , carried out in a similar manner to resol production. The mixing ratio of the compound obtained by the reaction of the phenol of the general formula 4 with the compound of the general formula () and the phenol of the general formula is not particularly limited and may be determined depending on the intended use of the modified phenol resin.

The aldehydes used in this reaction are not particularly limited, but depending on the purpose of use of the resulting modified phenol resin, the aldehydes used are usually the 101i group of the compound obtained by the reaction of the phenol with the compound of general formula 2 and the compound of general formula 4. The ratio of the total number of -OR groups of phenols to the number of moles of Go and the number of moles of aldehyde groups: t: o, t-t, o for acidic catalysts, l: range of 1.0 to 2.0 for alkaline catalysts It is used by adjusting it so that it becomes .

The aldehydes used in the production of the modified phenolic resin of the present invention include general formaldehyde, paraformaldehyde, and furfural acetaldehyde, and the acidic catalysts include sulfuric acid, hydrochloric acid, oxalic acid, formic acid, paratoluenesulfonic acid, etc. However, as the alkaline catalyst, sodium hydroxide, potassium hydroxide, barium hydroxide, slaked lime, aqueous ammonia, triethanolamine, triethylamine, etc. are used. Usually, this reaction is carried out at a temperature of 80°C to reflux for 80 minutes to 4 hours, and if necessary, after performing operations such as neutralization, washing with water, and dehydration under reduced pressure, the contents are cooled and solidified. Alternatively, it can be recovered as a liquid modified phenolic resin.

The modified phenolic resin obtained in the present invention is used for a wide variety of purposes, and its applicability to various uses is due to the -OH group of this resin, and a typical example is the improvement of conventional phenolic resins. be.

For example, by blending phenol novolac resin obtained by reacting phenol and formaldehyde with acidic solution,
Alternatively, when the resin obtained by the method of the present invention is used alone as a binder for shell molds, it can provide strength to sand molds,
It also serves as a low expansion agent. Furthermore, by blending the resin obtained by the method of the present invention with a phenol novolak resin, or
The heat resistance of the cured product can be improved by curing the resin obtained by the method of the present invention alone with hexamethylene lentithramine.

Furthermore, by blending it as a curing agent component in urethane resins and epoxy resins, the heat resistance of paints, molding materials, laminates, etc. can be improved.

In addition to application methods that take advantage of such reactivity, it is also used as a phenolic resin modified with formaldehyde, rosin, cashew, etc., and blended into hot melt adhesives and rubber adhesives to provide adhesive properties.

As described above, the modified phenolic resin obtained according to the present invention can be used in many applications such as paints, molding materials, laminates, adhesives, and foundry sand binders.

The present invention will be explained in more detail with reference to Examples below, but the scope of the present invention is not limited thereby.

Example 1 Phenol 141.2f (1.5 mol) was added to a reactor equipped with a thermometer, stirrer, dropping funnel and reflux condenser.
1. Charge 194.8 f (1.0 mol) of 8-di(2-hydroxy-2-propyl)benzene and raise the temperature to 100°C. Next, concentrated hydrochloric acid (8.85 F) was added dropwise from the dropping funnel, and the reaction was carried out under reflux for 4 hours.

After (7), 87% formalin water 40.6F (0.5
Gradually drop 0 mol) from the dropping funnel〇, after the dropping is completed,
The reaction was continued at reflux for 80 minutes. After the reaction was completed, the reaction product was neutralized with sodium chloride water, washed twice with 200-warm water, and the reaction product was dehydrated under reduced pressure to obtain a transparent solid resin 295f with a pale yellow color.

The softening point of this resin was 105°C.

Reference Example 1 In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 752.9 g (8.0 mol) of phenol and 194.8 f (1
, 0 mo#), toluene 1200- was charged as a solvent, and the reaction was carried out for 2 hours at a temperature range of 25 to 80"C while blowing hydrogen chloride. After the reaction was completed, it was neutralized with 10% NaOH water and further washed with water. , dehydration, solvent removal, and phenol removal were performed under heating and reduced pressure.The obtained contents were recrystallized from toluene to obtain 1.8-di(2-p-hydroxyphenyl-2-propyl)benzene (2-p-hydroxyphenyl-2-propyl)benzene (with a molecular weight of 846). The following compound -(
b). >2251 was obtained. (Melting point 187-140
℃). Furthermore, 69% by weight of 1,8-si(2-p-hydroxyphenyl-2-propyl)benzene was extracted from the recrystallized P solution.
125f of the containing compound -(b) was recovered and subjected to the reaction in the following examples of the present invention.

Example 2 27.7% of the compound (a) obtained in Reference Example 1 was placed in a reactor.
F (0.08 mol) and phenol 79.0f (0.8 mol)
4 mol) and heated to dissolve.

Next, 1.0 ml of oxalic acid was added as a catalyst, followed by 67.4 F (0.88 mol) of 87% formalin water, and the reaction was carried out under reflux for 1.5 hours.

After the reaction was completed, the reaction product was washed with decane silane twice with 200-g warm water, and the reaction product was heated and dehydrated under reduced pressure to obtain a transparent, pale yellow solid resin 105f. The softening point of this resin was 107°C.

Example 8 The compound -(b) obtained in Reference Example 1 was converted to 29.69(-o
n group equivalent to 0.16 mol) and phenol 79, Of
(0.84 mol) and oxalic acid 1.0f, 87
After adding 67.41% (0.88 mol) of formalin water, the same operation as in Example 2 was carried out to obtain a transparent, pale yellow solid resin 102f. The softening point of this resin is 102
It was ℃.

Example 4 84.6% of the compound-(a) obtained in Reference Example 1 was placed in a reactor.
F (0,10 mol), phenol 76.8F (0,80
mol), 87% formalin water 89.8F (1.10 mol), and aqueous ammonia (specific gravity 0.8814f) as a catalyst were charged and heated to the boiling point over 45 minutes, and the reaction was further carried out under reflux F for 80 minutes. 200TTt after the completion of the reaction
The reaction product was decanotated twice with warm water, and the reaction product was heated and dehydrated under reduced pressure to obtain a pale yellowish brown solid resin 180f. The softening point of this resin was 71°C.

Example 5 The same reaction and post-treatment as in Reference Example 1 were carried out using phenol and 1,4-di(2-hydroxy-2-propyl)benzene to produce 1°4-di(2-P-hydroxyphenyl- Compound containing 88% by weight of 2-propyl)benzene
I got an e field. (However, this refers to the concentrated distillate after dehydration, desolvation, and dephenolization under heating and reduced pressure after the reaction.) This compound equivalent) and phenol 82.8F (0,88
mol) and 1. mol of oxalic acid. Of, 67.4F (0.88 mol) of 87% formalin water was added and the same operation as in Example 2 was carried out to obtain a transparent, pale yellow solid resin 10.
I got 7f. The softening point of this resin was 113°C.

Example 6 p-cresol 648.81 (6.0 mol), 1.8-
Di(2-hydroxy-2-propyl)benzene 194.
Using 8F (1.0 mol) and toluene 1000 as a solvent, the same reaction and post-treatment operations as in Reference Example 1 were carried out to obtain 1,3-di[2-(2-hydroxy-5-methylphenyl)2 A compound containing 87M1L% of -propyl]benozene) was obtained. (However, dehydration under heating and reduced pressure after the reaction,
Concentrated can liquid after solvent removal and p-cresol removal). ) to 28.41 (-0fi group).
12 mole equivalent) and p-cresol 95.1F (0,88
After adding 1.5 f of oxalic acid and 67.49 (0.88 mol) of 87% formalin water, the same procedure as in Example 2 was carried out to obtain a transparent, pale yellow solid resin. I got 96f.

The softening point of this resin was 109°C.

Example 7 Resorcinol 880.1 F (8 mol), 1,8-di(
2-Hydroxy-2-propyl)-benzene 194.8
F (1.0 mol), Benmono 10100O as a solvent,
1,000 ml of concentrated hydrochloric acid was charged and the reaction was carried out at 5°C for 15 hours. After the reaction was completed, the ocher oil layer was separated and neutralized with hot soda water. After neutralization, unreacted resorcin contained in the oil layer was removed by hot water purification, and the oil layer was cooled in an ice water bath. Upon cooling, a pale yellowish solid was precipitated, and by oral separation, a pale yellowish compound (e) was obtained.

This compound (e) contains 1,3-di[2-(2゜4-dihydroxyphenyl)-2-propyl]benzene at 95%
He was breathing heavily.

This compound -(e) is 29.8 II (-OR group Te0
．． 8 mol equivalent) and resorcinol 77, LfCo, 7 mol)
and 1. oxalic acid. of, 37% formalin water 6
7.4F (0.88 mol) was added and the same operation as in Example 2 was carried out to obtain a pale yellowish brown solid resin 110f.

The softening point of this resin was 101°C.

Example 8 Compound -(b) obtained in Reference Example 1 was heated to 44.4F(-0
H group equivalent to 0.24 mol) and phenol □71.5F (
0.76 mol) of oxalic acid, 1 of oxalic acid, 67.410.88 mol of 87% formalin water) were added, and the same operation as in Example 2 was carried out to obtain a transparent, pale yellow solid resin. 118f was obtained. The softening point of this resin was 104''C.

Examples of evaluations for nonyl molding, phenol molding, and materials using the obtained resin are shown below.

Evaluation for nonyl mold> 50M parts of this solid resin and 50 parts of commercially available phenol novolac resin were mixed with No. 7 silica sand 800 preheated to 150°C.
After mixing to 0 parts by weight, 2 parts of hexamethylenetetramine
60 parts by weight of 0% water bath solution was added and further mixed, and when the sand particles became loose, 8 parts by weight of calcium stearate was added.

The resulting resin-coated sand was used to perform as a shell mold in a mold at 250'C. Opening during heat treatment and Part 25
It was investigated by hot strength at 0 ”G!.Similarly, compared to the case of using only phenol novolac resin and hexamethylenetetramine, when the solid resin of the present invention is used, strength is developed with less hexamine. It has been found.

Experimental values are shown below.

When this solid resin was used to modify a phenolic resin molding material, the results shown in F were obtained, and the heat resistance,
It was found that the bending strength was improved.

Experimental values are shown below.

(1) Preparation of molding material and molding The formulation shown in Table 2 was kneaded for 5 minutes with two rolls (110 to 120°C), then cooled and pulverized to obtain a molding material.

This was compression molded at 170°C for 2 minutes at 180 Kg/mG.

Table 2 Molding material formulation (N'kk part) (2) Physical properties of the molded product Table 8 shows the physical properties of the molded product obtained in (1).

Claims (1)

[Scope of Claims] General formula (4) (wherein R+l is H1 an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, -OH group, and R2 is H1
It represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 1 to 8 carbon atoms. ) and the general formula direction are shown. The definition of R4 is the same as R8, and may be the same as or different from Re. ) in the presence of an acidic catalyst. (In the formula, R1 is H1 an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an -OH group, and Rz is H1
Indicates an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 1 to 8 carbon atoms. ) A method for producing a modified phenolic resin, which comprises reacting the modified phenolic resin with an aldehyde under an acidic catalyst or an alkaline catalyst in the presence or substantially absence of the phenol represented by the following formula.