JP3819089B2 - Method for producing novolac type compound - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a novolac type compound.
[0002]
[Prior art]
JP-A-4-110317 describes that the desired novolak can be produced by the reaction of a halogenated methyl aromatic compound and an aromatic hydroxy compound. However, it is also described that there are problems such as generation of hydrogen halide gas. In addition, this reaction has a problem that, in principle, hydrogen halide which is an acid catalyst is generated, and the reaction rate increases at an accelerated speed, so that it is difficult to control the reaction.
[0003]
[Problems to be solved by the invention]
The present invention relates to the production of a novolak type resin using an industrially inexpensive halogenomethyl aromatic compound, in which the product does not cause gelation due to the corrosion of the apparatus or the severity of the reaction. It aims to be realized with.
[0004]
[Means for Solving the Problems]
That is, the present invention provides (1) a method for producing a novolak type compound by reacting a halogenated methyl aromatic compound represented by the following formula (1) with an aromatic hydroxyl compound in the presence of an alkaline substance,
R (—CH ₂ X) _n (1)
(In the formula, n represents an integer of 2 to 3. R represents a divalent or trivalent aromatic group, and X represents Cl or Br.)
(2) The production method according to the above (1), wherein a methyl halide aromatic compound in which R is a group derived from phenyl, naphthyl, or biphenyl,
(3) The production method according to the above (1) or (2), wherein the aromatic hydroxyl compound is selected from phenol, naphthols or biphenols.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Specific compounds represented by the above formula (1) include 1,4-bis (chloromethyl) benzene, 1,2-bis (chloromethyl) benzene, 1,3-bis (chloromethyl) benzene, 1,4 -Bis (bromomethyl) benzene, 4,4'-bis (chloromethyl) biphenyl, 2,4'-bis (chloromethyl) biphenyl, 2,2'-bis (chloromethyl) biphenyl, 4,4'-bis ( Bromomethyl) biphenyl, 2,4′-bis (bromomethyl) biphenyl, 2,2′-bis (bromomethyl) biphenyl, 2,6-bis (chloromethyl) naphthalene, 1,4-bis (chloromethyl) naphthalene, etc. Bischloromethylnaphthalene and bis (bromophenyl) naphthalene are exemplified, but are not limited to these as long as represented by the above formula (1).
[0006]
Aromatic hydroxyl compounds include phenol, o-cresol, m-cresol, p-cresol, 2,6-xylenol, 2,4-xylenol, catechol, resorcinol Hydroquinone, α-naphthol, β-naphthol, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, biphenol, bisphenol A, bisphenol F, and the like.
These aromatic hydroxyl compounds can be used singly or in combination of two or more, and the amount used is usually 0.1 with respect to 1 mol of the methyl halide group in the compound of formula (1). 8 to 20 mol, preferably 1 to 10 mol.
[0007]
Alkaline substances used include caustic soda, caustic potash, lithium hydroxide, soda, potassium carbonate, lithium carbonate, soda bicarbonate, potassium bicarbonate, calcium carbonate, magnesium carbonate, calcium oxide, magnesium oxide And soda acetate, potassium acetate, soda oxalate or ammonium carbonate, and organic amines such as triethylamine or dimethylaniline. The amount used is equimolar or slightly excessive with respect to 1 mole of the methyl halide group in the compound of formula (1).
[0008]
The reaction is usually carried out in a solvent. Solvents include hydrocarbons such as hexane, heptane, toluene, xylene, pseudocumene and cyclohexane, halogenated hydrocarbons such as dichloroethane, ethylene chloride and chlorobenzene, ethers such as dibutyl ether, dioxane and methoxyethanol. Aprotic polar solvents such as dimethylformamide, dimethylsulfoxide or dimethylimidazolidinone, alcohols such as methanol, ethanol, propanol or butanol, acetone, methyl ethyl ketone or methyl Although ketones such as isobutyl ketone, water, and the like can be used, it is not necessary to use a solvent. When using a solvent, it is preferable to use about 10 to 20 weight times of the compound of Formula (1). Also, when using aprotic polar solvents such as dimethyl sulfoxide, the reaction rate is slightly slow because they dissolve alkaline substances well, so the amount used is preferably 50% by weight or less in the total reaction mixture, preferably Is preferably limited to about 20% by weight or less. Further, a phase transfer catalyst such as tetrabutylammonium chloride and Triton B can be used in an amount of about 0.1 to 1% by weight based on the total reaction mixture.
[0009]
The reaction temperature is usually 40 ° C to 200 ° C, preferably 60 ° C to 150 ° C. Further, the reaction can be carried out while extracting generated water by azeotropic distillation or the like.
In order to control the reaction, the compound of the formula (1) or the alkaline substance can be added little by little, but it is preferable that the alkaline substance is present in a little excess than the compound of the formula (1). The reaction time is usually 1 hour to 25 hours, preferably 3 to 15 hours. For example, when the reaction slows down as in the case of using an aprotic polar solvent, it can be solved by adding some acids. Examples of acids that can be used here include Lewis acids such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, toluenesulfonic acids, BF3, aluminum chloride, and ferric chloride.
[0010]
The reaction system is preferably kept weakly acidic to neutral. Use of a solvent that does not completely dissolve the alkaline substance as the solvent system is suitable for maintaining this condition. For example, when the raw material aromatic hydroxy compound is used as a solvent, and hydrocarbons or halogenated hydrocarbons such as toluene, xylene, pseudocumene, chlorobenzene, hexane, cyclohexane, heptane, dichloroethane, ethylene chloride, dibutyl ether, dioxane When ethers such as acetone, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone are used, the reaction proceeds smoothly even if an alkaline substance is added at one time. The alkaline substance is preferably used as a solid. Further, it is preferable to complete the novolak reaction by adding the above acid catalyst when the generation of hydrogen halide by the reaction is almost completed. In this case, the concentration of the acid catalyst is suitably about 0.01 to 5% by weight.
[0011]
Salts are produced by the reaction. After completion of the reaction, salts are removed by filtration, washing with water, etc., and then the solvent and / or unreacted aromatic hydroxy compound is removed by distillation or dissolution in a solvent to obtain a novolak compound.
[0012]
【Example】
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[0013]
Example 1
A 300 ml, 4-necked flask was charged with 55 g of toluene, 20.7 g of phenol, and 23.3 g of soda carbonate, and the temperature was raised to 70 ° C. Here, 25.1 g of 4,4′-bis (chloromethyl) biphenyl was charged little by little. The addition was completed in 1 hour. Then, it was made to react at 80 degreeC for 8 hours, and 95 degreeC for 5 hours. Little generation of hydrogen chloride gas was observed. After completion of the reaction, the precipitated salt was removed, 0.1 g of methanesulfonic acid was added to the filtrate just in case, and the mixture was reacted at 90 ° C. for 1 hour. After excess methanesulfonic acid was neutralized with caustic soda, toluene was distilled off, and after cooling, 34 g of a novolak type compound was obtained. The resulting novolak compound had a softening point of 75 ° C. and a melt viscosity at 150 ° C. of 2.4 poise.
[0014]
Example 2
The reaction was conducted in the same manner as in Example 1 except that 17.5 g of 1,4-bis (chloromethyl) benzene was used as the compound of formula (1) to obtain 26.8 g of a novolak type compound. The resulting novolak compound had a softening point of 73 ° C. and a melt viscosity at 150 ° C. of 3.1 poise.
[0015]
Example 3
In Example 1, except that toluene was used, 50 g of phenol was used, and 19 g of potassium carbonate was used instead of soda carbonate, the reaction was carried out in the same manner as in Example 1, and 34.8 g of novolak type compound was obtained. Obtained. The resulting novolac compound had a softening point of 108 ° C. and a melt viscosity at 150 ° C. of 0.9 poise.
[0016]
【The invention's effect】
According to the present invention, a novolak type compound can be obtained more efficiently than a methyl halide aromatic compound. The obtained novolac-type compound is useful as an epoxy resin curing agent for semiconductor encapsulation or a raw material for epoxy resin synthesis.

Claims (3)

A method for producing a novolak type compound by reacting a halogenated methyl aromatic compound represented by the following formula (1) with an aromatic hydroxyl compound in the presence of an alkaline substance.
R (—CH ₂ X) _n (1)
(In the formula, n represents an integer of 2 to 3. R represents a divalent or trivalent aromatic group, and X represents Cl or Br.) The production method according to claim 1, wherein a halogenated methyl aromatic compound in which R is a group derived from phenyl, naphthyl or biphenyl is used. The method according to claim 1 or 2, wherein the aromatic hydroxyl compound is at least one selected from phenol, naphthols and biphenols.