JP6143332B2 - Allyl ether resin and method for producing the same - Google Patents

Description

  The present invention relates to an allyl ether resin useful for electrical and electronic materials, a high-purity allyl ether polymer useful as an epoxy resin raw material, and a method for producing the same.

Conventionally, an allyl ether compound has been used to produce a cured product using the reactivity of the allyl ether. Generally, it is cured by radical polymerization or the like to form a network polymer.
Specifically, allyl ether compounds such as ethylene glycol monoallyl ether, resorcinol diallyl ether, catechol diallyl ether, and 1,4-bis (allyloxymethyl) cyclohexane have been conventionally used as reactive diluents, crosslinking agents, flame retardants, and the like. Additive (It has been used as a raw material for photocurable monomers, etc. (Patent Document 1 JP 2005-170890).
Furthermore, the allyl ether compound can be used as a raw material for the epoxy resin by an oxidation reaction. The obtained epoxy resin can be used for various applications such as paints, structural materials, electric and electronic materials, etc. (Patent Document 2 JP 2012-067253 A).

JP 2005-170890 A JP 2012-067253 A JP 59-227918 A

In the synthesis of an allyl ether compound, a reaction between an allyl halide and a phenol compound is often used, but the obtained allyl ether compound contains a halogen, and the epoxy resin obtained therefrom also contains a halogen. By using a compound such as allyl bromide that is easy to desorb, it is possible to reduce the halogen content. However, allyl chloride has a large amount of desorbed halogen, and allyl bromide is easily available in the general market. Low halogenation with chloride is industrially important. In Patent Document 3, attempts have been made with allyl chloride to avoid this problem, but it is only suitable for cresol novolac, which has relatively high solvent solubility, and can be used for other resins. difficult. In particular, when a resin such as a phenol aralkyl resin is used as a raw material, the solubility in a solvent such as toluene is very poor, the salt does not escape when washed with water, and subsequent purification as an allyl ether is difficult. In the denaturation process such as chemical conversion, the reaction is inhibited and a side reaction is caused.
Although a reaction using allyl carbonate or allyl ester is disclosed as a method not containing halogen, allyl carbonate and allyl ester as raw materials are expensive and are not suitable for general use for industrial purposes. In addition, since allyl carboxylic acids such as allyl acetate must be reacted and an expensive catalyst must be used during the synthesis, it is not industrially preferable, and the allyl etherified phenols and aldehydes obtained are used as acid catalysts. Although there is a method of addition condensation in the presence, when the allyl ether resin is converted into an epoxy resin by oxidation of the phenolic hydroxyl group that appears due to the Claisen transition during the condensation, the residual phenolic hydroxyl group inhibits the reaction.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
An allyl ether resin obtained by a reaction between a phenol resin and allyl chloride, allyl ether resin obtained by allyl etherification using a metal hydroxide in the presence of allyl chloride, phenol resin and water,
(2)
An allyl ether resin obtained by using a production method characterized in that the allyl chloride polymer in the allyl chloride used in (1) is 2% or less.
(2)
An epoxy resin obtained by using the allyl ether resin according to item (1) and at least one of hydrogen peroxide and carboxylic acid peroxide,
(3)
An allyl ether resin having a phenol aralkyl structure, wherein the total chlorine content is 30 ppm or less and the hydroxyl group equivalent is 10,000 g / eq or more,
(4)
An allyl ether resin having a phenol-dicyclopentadiene structure, wherein the total chlorine content is 30 ppm or less, and the hydroxyl group equivalent is 10,000 g / eq or more,
(5)
The allyl ether resin according to claim 1, which is obtained by allyl etherification in the presence of an aprotic polar solvent during the allyl etherification.
About.

  A low halogen allyl ether resin suitable for electrical and electronic materials and raw materials thereof can be obtained.

The allyl ether resin of the present invention is a resin suitable for electrical and electronic material applications with a small amount of residual phenolic hydroxyl groups and a small amount of residual halogen.
The allyl ether resin of the present invention is synthesized using a phenol resin (including a phenol compound) and allyl chloride. At this time, it is preferable to use a phenol resin having a total chlorine content of 5 ppm (combustion method) or less and an allyl chloride containing the polymer (dimerized product or more) at 1% or less. In addition, water is essential for the solvent used in the present invention.

Examples of the phenol resin used as the raw material for the allyl ether resin of the present invention include phenol novolacs, bisphenols, biphenols, trisphenol methanes, and phenol aralkyls. Specifically, as bisphenols, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′- Tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ) Ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hy Loxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1 , 4-bis (chloromethyl) benzene, polycondensate with 1,4-bis (methoxymethyl) benzene, etc., and modified products thereof, but are not limited thereto.
In the present invention, biphenols, phenol aralkyls, and phenol-tricyclodecane resins are preferable, and tetramethylbiphenol, phenols (phenol, C1-C4 alkyl-substituted phenol, naphthol, dihydroxybenzene), Cyclopentadiene, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4-bis (chloromethyl) benzene or 1 , 4-bis (methoxymethyl) benzene and a reaction product with 1,4-benzenedimethanol are preferred. Particularly preferably, a reaction product of phenol or cresol, naphthol and 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, phenol or It is a reaction product of cresol, naphthol and 1,4-bis (chloromethyl) benzene or 1,4-bis (methoxymethyl) benzene, 1,4-benzenedimethanol. It is a reaction product of phenol, cresol, naphthol and dicyclopentadiene.
Compared to resins such as general cresol novolac, these materials are superior in flame retardancy, and can be used as a flame retardant to produce a composition that can exhibit flame retardancy without adding halogen, which is useful for environmental impact. In addition to the high hydrophobicity of the system, it can stop the movement of ions such as chlorine, which is contained somewhat, and not only has high electrical reliability, but also the combination of low halogen and these structures is an electric and electronic component It is important as a material.

  The total chlorine content of the phenol resin used in the present invention is preferably 5 ppm or less. This is because by using a material having a concentration of 5 ppm or less, a resin having excellent flame retardancy and high electrical reliability can be obtained.

As the allyl halide (for example, allyl chloride) used in the present invention, it is preferable to use one having a small amount of the polypolymer (dimer or higher). Allyl chlorides tend to polymerize to form polyallyl chloride, which is the multipolymer.
This residual polyallyl chloride not only increases the total chlorine content, but also contributes to an increase in the molecular weight of the allyl ether compound, leaving a small amount of gel in the product and reducing this chlorine content. Requires the addition of a considerable amount of a basic substance, which is not preferable in the industry and produces highly allylic alcohol in the system.
These polyallyl chloride compounds can be easily confirmed by gas chromatography (GC) or the like, and the specific amount is a polymer of 1 area% or less with respect to the allyl chloride monomer in the area ratio. More preferably, it is 0.5 area%, More preferably, it is 0.2 area% or less, Most preferably, it is 0.05 area% or less.
The purity of allyl chloride is preferably 90 area% or more, more preferably 97 area% or more, and particularly preferably 99 area% or more.
The amount of allyl chloride used is usually 1.0 to 1.15 mol, preferably 1.0 to 1.10 mol, more preferably 1.0 to 1.05 mol, based on 1 mol of the hydroxyl group of the raw material phenol resin. It is.

In the present invention, an alkali metal hydroxide is preferable as a base that can be used when etherifying allyl chloride. Specific examples thereof include sodium hydroxide and potassium hydroxide. The aqueous solution may be used, but in the present invention, it is particularly preferable to use a solid material formed into a flake shape from the viewpoint of solubility and handling.
The usage-amount of an alkali metal hydroxide is 1.0-1.15 mol normally with respect to 1 mol of hydroxyl groups of a raw material phenol resin, Preferably it is 1.0-1.10 mol, More preferably, it is 1.0-1. 0.05 mole.

  In order to accelerate the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of hydroxyl group in the raw material phenol mixture.

In this reaction, water is used as a reaction solvent. The amount of water used is 2% to 50%, more preferably 5% to 40%, and particularly preferably 5% to 30% by weight based on the total weight of the phenolic resin.
The use of water is important in this reaction. By promoting the polarization during the reaction, there is an effect of facilitating the progress of the reaction.

In this reaction, an aprotic polar solvent such as alcohol having 1 to 5 carbon atoms and dimethyl sulfoxide having good compatibility with water may be used in combination as another solvent. A solvent having good compatibility with water is not particularly limited as long as it is compatible with water at a concentration of 50% or more. In this reaction, an aprotic polar solvent such as dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetamide, dimethylimidazolidinone, N-methylpyrrolidone and the like are preferable, and dimethyl sulfoxide is particularly preferably used as the solvent.
This solvent is useful for reacting the resin and water uniformly (or more nearly uniformly). When the reaction system is so separated, the progress of the reaction tends to be inhibited.
Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. The amount of the solvent used in combination is 0.2 to 20 times, more preferably 0.5 to 15 times, and particularly preferably 0.7 to 12 times the total weight of water. In particular, aprotic polar solvents such as dimethyl sulfoxide are not useful for purification such as washing with water, and it is not preferable to use them in large quantities. Moreover, since the boiling point is high and removal of the solvent is difficult, a large amount of energy is consumed, so that it is not preferable that the amount is too large.
Further, non-aqueous solvents such as methyl ethyl ketone, methyl isobutyl ketone, and toluene can be used in combination, but it is preferable to use 100% by weight or less based on the total amount of water and the above-mentioned solvents used in combination. Particularly preferred is 0.5 to 50% by weight. If a non-aqueous solvent such as methyl ethyl ketone, methyl isobutyl ketone, and toluene is used in an excessive amount, the Claisen transition occurs during the reaction, the residual phenolic hydroxyl group increases, and the amount of allyl chloride in the system is insufficient. Problems such as the production of a structure other than the target structure, and the fact that all phenolic hydroxyl groups are not allyl etherified occur.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, it is preferable to raise the reaction temperature in two or more stages for higher purity epoxidation. The first stage is particularly preferably 35 to 50 ° C, and the second stage is particularly preferably 45 to 70 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 5 hours. If the reaction time is short, the reaction does not proceed, and if the reaction time is long, a by-product is formed, which is not preferable.
After completion of the reaction, the solvents are distilled off under heating and reduced pressure. The salt precipitated during the reaction may be used as it is. The recovered allyl ether resin is dissolved by using aromatic hydrocarbons such as toluene and xylene and ketone compounds having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) as a solvent. In the state heated to 40 to 90 ° C., more preferably 50 to 80 ° C., the water layer is washed with water until it becomes pH 5 to 10, more preferably pH to 9, particularly preferably. At this time, if the pH is stopped at 8 or more, if the reaction such as epoxidation is performed later, the catalyst system is destroyed, and the reaction does not proceed well.
The allyl etherification reaction is preferably carried out by blowing an inert gas such as nitrogen (in the air or in the liquid). If no inert gas is blown, the resulting resin may be colored. The amount of inert gas blown in varies depending on the volume of the kettle, but it is preferable to blow in an amount of inert gas that can replace the volume of the kettle in 0.5 to 20 hours.

The allyl ether resin thus obtained has a total chlorine content of 30 ppm or less, more preferably 20 ppm or less, and a hydroxyl group equivalent of 10,000 g / eq or more, particularly preferably 20000 g / eq or more.
When it exceeds 20000 g / eq , the amount of hydroxyl groups that can be substantially measured is exceeded, indicating that it is almost 100% allyl etherified. Furthermore, there is no allyl alcohol residue.

The allyl ether resin can be used for various applications.
Specifically, as an allyl ether resin itself, as a curable resin crosslinking agent, further as an epoxy resin raw material, a phenol resin raw material by Claisen transition, and a curable resin composition containing these epoxy resin and phenol resin in the composition Can be used.
In particular, when used as an epoxy resin raw material, the phenolic hydroxyl group inhibits the reaction during the reaction with an oxidizing agent such as peracid or hydrogen peroxide. Since the amount is small, it is useful for various known materials, particularly for electrical and electronic materials that require electrical reliability.

The allyl ether resin of the present invention can be oxidized to form the epoxy resin of the present invention. Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
Specific examples of the epoxidation method using peracid include the method described in JP-A-2006-52187.
Various methods can be applied to the method of epoxidation with hydrogen peroxide solution. Specifically, JP-A-59-108793, JP-A-62-234550, JP-A-5-213919, JP 11-349579 A, JP 1-33471 A, JP 2001-17864 A, JP 3-57102 A, JP 2011-225654 A, JP 2011-079794 A, JP Techniques such as those described in JP2011-084558A, JP2010-08383A, JP2010-095521A, and the like can be applied.

A specific example is described about the method of obtaining an epoxy resin from the phenol resin of this invention.
The phenol resin of the present invention can be converted to an epoxy resin by oxidation. Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
Specific examples of the epoxidation method using peracid include the method described in JP-A-2006-52187.
Various methods can be applied to the method of epoxidation with hydrogen peroxide solution. Specifically, JP-A-59-108793, JP-A-62-234550, JP-A-5-213919, Techniques such as those disclosed in JP-A-11-349579, JP-B-1-33471, JP-A-2001-17864, JP-B-3-57102 and the like can be applied.

Hereinafter, a particularly preferable method for obtaining the epoxy resin of the present invention will be exemplified.
First, the diolefin compound, polyacids and quaternary ammonium salt of the present invention are reacted in an emulsion of an organic substance and hydrogen peroxide water.

The polyacid used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, but a polyacid containing tungsten or molybdenum is preferred, a polyacid containing tungsten is more preferred, and tungstates are particularly preferred.
Specific polyacids include tungsten acids such as tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid and 12-tungstosilicic acid, and molybdenum systems such as molybdic acid and phosphomolybdic acid. And the acid salts of these.
Examples of counter cations of these salts include ammonium ions, alkaline earth metal ions, and alkali metal ions.
Specific examples include alkaline earth metal ions such as calcium ions and magnesium ions, and alkali metal ions such as sodium, potassium, and cesium, but are not limited thereto. Particularly preferred counter cations are sodium ion, potassium ion, calcium ion and ammonium ion.

The amount of polyacid used is 0.5 to 20 mmol, preferably 1 in terms of metal elements (tungstenic acid is tungsten atom, molybdic acid is molybdenum atom) with respect to 1 mol of allyl group of the phenolic resin of the present invention. 0.0 to 20 mmol, more preferably 2.5 to 15 mmol.

As the quaternary ammonium salt, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be used, and particularly preferably, the alkyl chain is all an aliphatic chain. Can be used.
Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt, trihexa Examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to. Particularly preferred are those having 25 to 100 carbon atoms.
Specific examples of the anionic species of these salts include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions, and the like, but are not particularly limited thereto.
When the number of carbon atoms exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer may deteriorate. When the number of carbon atoms is 10 or less, the hydrophilicity is increased, and the compatibility of the quaternary ammonium salt with the organic layer is similarly deteriorated.
The amount of quaternary ammonium salt used is preferably 0.01 to 10 times the valence of the tungstic acid used. More preferably, it is 0.05-6.0 times equivalent, More preferably, it is 0.05-4.5 times equivalent.
For example, since tungstic acid is divalent with H ₂ WO ₄ , the quaternary ammonium carboxylate is preferably in the range of 0.02 to 20 mol with respect to 1 mol of tungstic acid. Moreover, since it is trivalent in the case of tungstophosphoric acid, it is 0.03 to 20 mol similarly, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 40 mol is preferable.
When the amount of the quaternary ammonium carboxylate is more than 10 times equivalent to the valence of tungstic acids, the post-treatment is not only difficult, but it also serves to suppress the reaction, which is not preferable.

Any buffer can be used, but it is preferable to use an aqueous phosphate solution in this reaction. The pH is preferably adjusted between pH 4 and 10, more preferably pH 5-9. When the pH is 4 or less, the hydrolysis reaction and polymerization reaction of the epoxy group easily proceed. On the other hand, when the pH is 10 or more, the reaction becomes extremely slow and the reaction time is too long.
In particular, in the present invention, when the tungstic acid as a catalyst is dissolved, the pH is preferably adjusted to be between 5 and 9.
For example, in the case of a phosphoric acid-phosphate aqueous solution which is a preferable buffer solution, a buffer solution is used in an amount of 0.1 to 10 mol% of phosphoric acid (or phosphorous such as sodium dihydrogen phosphate) with respect to hydrogen peroxide. Acid salt) and adjusting the pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.). Here, it is preferable that the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added. It is also possible to adjust using sodium dihydrogen phosphate, disodium hydrogen phosphate, or the like. A preferable phosphate concentration is 0.1 to 60% by weight, and more preferably 1 to 45% by weight.
In this reaction, a buffer solution is not used, but disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium tripolyphosphate, etc. (or hydrates thereof) can be converted to phosphate without adjusting pH. May be added directly. In the sense of simplifying the process, there is no troublesome pH adjustment, and direct addition is particularly preferable. The amount of phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol%, based on hydrogen peroxide. Is equivalent. At this time, if the amount exceeds 5 mol% equivalent to hydrogen peroxide, pH adjustment is required. If the amount is less than 0.1 mol% equivalent, the hydrolyzate of the produced epoxy compound tends to proceed or the reaction is slow. The harmful effect of becoming.

  This reaction is epoxidized using hydrogen peroxide. As the hydrogen peroxide used in this reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by weight is preferable because of easy handling. When the concentration exceeds 40% by weight, handling becomes difficult and the decomposition reaction of the produced epoxy resin also tends to proceed.

  This reaction preferably uses an organic solvent. The amount of the organic solvent to be used is 0.3 to 10, preferably 0.3 to 5, more preferably 0.5 to 2.5 by weight with respect to the diolefin compound 1 as the reaction substrate. is there. When the weight ratio exceeds 10, the progress of the reaction is extremely slow, which is not preferable. Specific examples of organic solvents that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. It is done. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, ethers such as diethyl ether, tetrahydrofuran and dioxane, ester compounds such as ethyl acetate, butyl acetate and methyl formate, and nitriles such as acetonitrile Compounds and the like can also be used. Particularly preferred solvents are alkanes such as hexane, cyclohexane and heptane, and aromatic hydrocarbon compounds such as toluene and xylene.

As a specific reaction operation method, for example, when the reaction is performed in a batch-type reaction kettle, a diolefin compound, hydrogen peroxide (aqueous solution), heteropolyacid (catalyst), buffer solution, quaternary ammonium salt and organic solvent are added. In addition, stir in two layers. There is no specific designation for the stirring speed. Since heat is often generated when hydrogen peroxide is added, a method of gradually adding hydrogen peroxide after each component may be added.
At this time, after adjusting the pH by adding a buffer solution (or water and phosphate) and tungstic acid, add a quaternary ammonium salt, an organic solvent, and a compound having a carbon-carbon double bond, and stir in two layers. Then, a technique of dropping hydrogen peroxide is used.
Alternatively, while stirring water, an organic solvent, and a compound having a carbon-carbon double bond, tungstic acid and phosphoric acid (or phosphates) are added, pH is adjusted, and then a quaternary ammonium salt is added. However, it is possible to use a method of dropping hydrogen peroxide when stirring in two layers.

  Although reaction temperature is not specifically limited, 0-90 degreeC is preferable, More preferably, it is 0-75 degreeC, Most preferably, it is 15-60 degreeC. When the reaction temperature is too high, the hydrolysis reaction tends to proceed, and when the reaction temperature is low, the reaction rate becomes extremely slow.

  Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long-time reaction is not preferable because it consumes a large amount of energy. The preferred range is 1 to 48 hours, more preferably 3 to 36 hours, and still more preferably 4 to 24 hours.

  After completion of the reaction, quenching of excess hydrogen peroxide is performed. The quenching treatment is preferably performed using a basic compound. It is also preferable to use a reducing agent and a basic compound in combination. As a preferable treatment method, there is a method of quenching the remaining hydrogen peroxide using a reducing agent after adjusting neutralization to pH 6 to 10 with a basic compound. When the pH is 6 or less, heat generated when reducing excess hydrogen peroxide is large, and decomposition products may be generated.

Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C and the like. As the amount of the reducing agent used, excess hydrogen peroxide is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, still more preferably 0.05 to 3 times mol, based on the number of moles. is there.
These are preferably added as an aqueous solution, and the concentration is 0.5 to 30% by weight.

Basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphorus such as sodium phosphate and sodium hydrogen phosphate. Examples thereof include basic solids such as acid salts, ion exchange resins, and alumina.
The amount used is water or organic solvents (for example, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, hydrocarbons such as cyclohexane, heptane and octane, methanol, ethanol, isopropyl alcohol, etc. The amount used is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times the number of moles of excess hydrogen peroxide. Mol, more preferably 0.05 to 3 times mol. These may be added as water or a solution of the aforementioned organic solvent, or may be added alone.
When a solid base that does not dissolve in water or an organic solvent is used, it is preferable to use an amount of 1 to 1000 times by weight with respect to the amount of hydrogen peroxide remaining in the system. More preferably, it is 10-500 times, More preferably, it is 10-300 times. In the case of using a solid base that does not dissolve in water or an organic solvent, the treatment may be carried out after separation of an aqueous layer and an organic layer described later.

After the hydrogen peroxide quench (or before quenching), if the organic layer and the aqueous layer are not separated, or if no organic solvent is used, the above-mentioned organic solvent is added and the operation is performed. The reaction product is extracted from the layer. The organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times in weight ratio to the raw material diolefin compound. This operation is repeated several times as necessary, and the separated organic layer is purified by washing with water as necessary.
From the obtained organic layer, if necessary, ion exchange resins and metal oxides (especially silica gel, alumina etc. are preferred), activated carbon (especially chemical activated carbon is particularly preferred), complex metal salts (especially basic complex metal salts). Are preferably removed), clay minerals (especially, lamellar clay minerals such as montmorillonite are preferred), impurities are removed, water washing and filtration are performed, and then the solvent is distilled off to obtain the desired epoxy compound.
In some cases, it may be further purified by column chromatography or distillation.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.
Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001)
ICI melt viscosity: compliant with JIS K 7117-2 (ISO 3219) Softening point: compliant with JIS K 7234 Total chlorine: compliant with JIS K 7243-3 (ISO 21672-3) Gel permeation chromatography (GPC):
Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)
The coupled eluent is tetrahydrofuran. The flow rate is 0.5 ml / min.
Column temperature is 40 ° C
Detection: RI (differential refraction detector)
Gas chromatography (GC):
Column HP-5 30mx0.32mmx0.25μm
Carrier gas Helium 1.0mL / min Split1 / 50
Injector temperature 300 ℃
Detector temperature 300 ℃
Oven temperature program After holding at 50 ° C. for 5 minutes, increase the temperature from 50 ° C. to 300 ° C. at 10 ° C./min. Hold at 300 ° C. for 5 minutes. High performance liquid chromatography (HPLC): Column ODS2 Eluent is acetonitrile-water gradient, Column temperature 40 ° C. Detection UV 274 nm, flow rate 1.0 ml / min.

Example 1
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 40 parts of water, 400 parts of dimethyl sulfoxide, and 210 parts of phenol biphenylene resin (hydroxyl equivalent 210 g / eq. Softening point 74 ° C.) were added while purging with nitrogen. After heating to ℃ and dissolving, cooled to 38-40 ℃, as it is, 44.4 parts of flaky sodium hydroxide (purity 99% manufactured by Tosoh) (1.1 mole equivalent to 1 mole equivalent of hydroxyl group of phenol biphenylene resin) ) Was added over 60 minutes, and then allyl chloride (purity 98.7 area% commercially available allyl chloride was separated by distillation. Allyl chloride polymer amount <0.2 area% confirmed by gas chromatography) 101.5 Parts (1.3 molar equivalents relative to 1 molar equivalent of hydroxyl group of phenol biphenylene resin, 1 mole of sodium hydroxide) Was added dropwise over 60 minutes, and the reaction was carried out at 38-40 ° C. for 5 hours and at 60-65 ° C. for 1 hour. After completion of the reaction, after distilling off water, dimethyl sulfoxide, etc. under reduced pressure by heating at 135 ° C. or less with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Then, 240 parts of allyl etherified phenol biphenylene resin (AEP1) of the present invention was obtained by distilling off the solvents from the oil layer using a rotary evaporator under nitrogen bubbling under reduced pressure. The obtained resin has a hydroxyl equivalent weight of 10,000 g / eq or more (it was confirmed by titration to be between 56000 and 113500 g / eq . Since the number of residual hydroxyl groups is small and accurate measurement is difficult, the following is more than 10000 The total chlorine content was 15 ppm. The obtained resin was semi-solid. The structural formula of the allyl etherified phenol biphenylene resin obtained as the main component is represented by the following formula (1).

(Example 2)
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 40 parts of water, 300 parts of dimethyl sulfoxide, and 207 parts of phenol biphenylene resin (hydroxyl equivalent 207 g / eq. Softening point 74 ° C.) were added while purging with nitrogen. After heating to ℃ and dissolving, cooled to 38-40 ℃, as it is, 44.4 parts of flaky sodium hydroxide (purity 99% made by Tosoh) (1.1 molar equivalent to 1 molar equivalent of hydroxyl group of phenol biphenylene resin) ) Was added over 60 minutes, and then allyl chloride (purity 99.5 area%, manufactured by Kashima Chemical. Allyl chloride polymer amount <0.2 area% confirmed by gas chromatography) 101.5 parts (of phenol biphenylene resin) 1.25 molar equivalents relative to 1 molar equivalent of hydroxyl group, 1.14 times moles relative to 1 mole of sodium hydroxide) Was added dropwise over 60 minutes, and the reaction was carried out at 38-40 ° C for 5 hours and at 60-65 ° C for 1 hour.
After completion of the reaction, after distilling off water, dimethyl sulfoxide, etc. under reduced pressure by heating at 135 ° C. or less with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Then, 237 parts of the allyl etherified phenol biphenylene resin (AEP2) of the present invention were obtained by distilling off the solvents from the oil layer using a rotary evaporator under nitrogen bubbling under reduced pressure. The hydroxyl group equivalent of the obtained resin was 10,000 g / eq or more, and the total chlorine was 2 ppm. The obtained resin was semi-solid.

(Comparative Example 1)
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 400 parts of dimethyl sulfoxide and 210 parts of phenol biphenylene resin (hydroxyl equivalent: 210 g / eq. Softening point: 74 ° C.) are added while purging with nitrogen, and the temperature is raised to 45 ° C. After dissolution, the mixture was cooled to 38-40 ° C., and 44.4 parts of flaky sodium hydroxide (purity: 99%, manufactured by Tosoh Corp.) (1.1 mol equivalent to 1 mol equivalent of hydroxyl group of phenol biphenylene resin) was added for 60 minutes After that, further allyl chloride (purity 98.7 area% commercial allyl chloride was separated by distillation. Allyl chloride polymer amount <0.2 area% confirmed by gas chromatography) 80.3 parts (phenol biphenylene) 1.05 molar equivalents relative to 1 molar equivalent of hydroxyl group of resin, and 1 mole of sodium hydroxide 1.0 mol) was added dropwise over 60 minutes, and the reaction was carried out at 38-40 ° C. for 5 hours and at 60-65 ° C. for 1 hour, but the reaction was monitored by HPLC (high performance liquid chromatography). The progress of could not be confirmed.

(Example 3)
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 40 parts of water, 300 parts of dimethyl sulfoxide, and 207 parts of phenol biphenylene resin (hydroxyl equivalent 207 g / eq. Softening point 74 ° C.) were added while purging with nitrogen. After heating to ℃ and dissolving, cooled to 38-40 ℃, as it is, 44.4 parts of flaky sodium hydroxide (purity 99% manufactured by Tosoh) (1.1 mole equivalent to 1 mole equivalent of hydroxyl group of phenol biphenylene resin) ) Was added over 60 minutes, and then allyl chloride (purity 98.1 area% commercially available allyl chloride was separated by distillation. Allyl chloride polymer amount <0.2 area% confirmed by gas chromatography) 101.5 Parts (1.1 molar equivalents relative to 1 molar equivalent of 1 hydroxyl group of phenol biphenylene resin, sodium hydroxide 1 The reaction was carried out at 38-40 ° C. for 5 hours and at 60-65 ° C. for 1 hour.
After completion of the reaction, after distilling off water, dimethyl sulfoxide, etc. under reduced pressure by heating at 135 ° C. or less with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Then, 237 parts of the allyl etherified phenol biphenylene resin (AEP3) of the present invention were obtained by distilling off the solvents from the oil layer while bubbling nitrogen under reduced pressure using a rotary evaporator. The hydroxyl group equivalent of the obtained resin was 10000 g / eq or more, and the total chlorine was 53 ppm. The obtained resin was semi-solid.

Example 4
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 40 parts of water, 400 parts of dimethyl sulfoxide, and 210 parts of phenol biphenylene resin (hydroxyl equivalent 210 g / eq. Softening point 74 ° C.) were added while purging with nitrogen. After heating to ℃ and dissolving, cooled to 38-40 ℃, as it is, 44.4 parts of flaky sodium hydroxide (purity 99% made by Tosoh) (1.1 molar equivalent to 1 molar equivalent of hydroxyl group of phenol biphenylene resin) ) Was added over 60 minutes, and then allyl chloride (purity 97.1 area% allyl chloride polymer produced by Tokyo Chemical Industry <0.21 area% confirmed by gas chromatography) 101.5 parts (hydroxyl group of phenol biphenylene resin) 60 equivalents of 1.3 mole equivalents per mole equivalent and 1.18 moles per mole of sodium hydroxide) The reaction was carried out dropwise over a period of 5 minutes at 38-40 ° C. and then at 60-65 ° C. for 1 hour.
After completion of the reaction, after distilling off water, dimethyl sulfoxide, etc. under reduced pressure by heating at 135 ° C. or less with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. After that, 232 parts of the allyl etherified phenol biphenylene resin (AEP4) of the present invention was obtained by distilling off the solvents from the oil layer using a rotary evaporator under nitrogen bubbling under reduced pressure. The hydroxyl group equivalent of the obtained resin was 10000 g / eq or more, and the total chlorine was 1065 ppm. The obtained resin was semi-solid.

(Example 5)
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 40 parts of water, 400 parts of dimethyl sulfoxide, and 210 parts of phenol biphenylene resin (hydroxyl equivalent 210 g / eq. Softening point 74 ° C.) were added while purging with nitrogen. After heating to ℃ and dissolving, cooled to 38-40 ℃, 42.4 parts of flaky sodium hydroxide (purity 99% made by Tosoh) as it is (1.05 molar equivalents relative to 1 molar equivalent of hydroxyl group of phenol biphenylene resin) ) Was added over 60 minutes, and then further allyl chloride (purity 97.1 area% allyl chloride polymer manufactured by Tokyo Chemical Industry <0.21 area% confirmed by gas chromatography) 82.0 parts (hydroxyl group of phenol biphenylene resin) 1.05 mole equivalent per 1 mole equivalent, 1.18 moles per mole of sodium hydroxide) 0 min over dropwise, as 5 hours at 38-40 ° C., was subjected to 1 hour of reaction at 60 to 65 ° C..
After completion of the reaction, after distilling off water, dimethyl sulfoxide, etc. under reduced pressure by heating at 135 ° C. or less with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Then, 231 parts of the allyl etherified phenol biphenylene resin (AEP5) of the present invention were obtained by distilling off the solvents from the oil layer while bubbling nitrogen under reduced pressure using a rotary evaporator. The obtained resin had a hydroxyl equivalent of 9300 g / eq and total chlorine of 950 ppm. The obtained resin was semi-solid.

(Example 6)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 40 parts of water, 400 parts of dimethyl sulfoxide, phenol-dicyclopentadiene type novolak (DCPD phenol resin, softening point 87 ° C., hydroxyl equivalent 168 g / eq. ) 168 parts, heated to 45 ° C., dissolved, cooled to 38-40 ° C., and left as it is, 44.4 parts of flaky sodium hydroxide (purity 99% manufactured by Tosoh Corporation) (1 mol equivalent of hydroxyl group of DCPD phenol resin) 1.1 mole equivalent) was added over 60 minutes, and then allyl chloride (purity 98.7 area%, commercially available allyl chloride was separated by distillation. Allyl chloride polymer amount <0.2 area% gas chromatograph (Confirmed by chromatography) 101.5 parts (1.3 parts per mole equivalent of hydroxyl group of DCPD resin) Le equiv, dropwise over 1.18 moles) 60 minutes against 1 mole of sodium hydroxide, as 5 hours at 38-40 ° C., was subjected to 1 hour of reaction at 60 to 65 ° C..
After completion of the reaction, after distilling off water, dimethyl sulfoxide, etc. under reduced pressure by heating at 135 ° C. or less with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Then, 172 parts of the allyl etherified DCPD phenol resin (AEP6) of the present invention were obtained by distilling off the solvents from the oil layer using a rotary evaporator under nitrogen bubbling under reduced pressure. The obtained resin had a hydroxyl group equivalent of 10,000 g / eq , a softening point of 52 ° C., and a total chlorine content of 10 ppm. The structural formula of the allyl etherified DCPD phenol resin obtained as the main component is represented by the following formula (2).

(Example 7)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while 40 parts of water, 200 parts of dimethyl sulfoxide, 3,3 ′, 5,5′-tetramethylbiphenol (hydroxyl equivalent 121 g / eq.) 128 parts were added, heated to 45 ° C. and dissolved, then cooled to 38-40 ° C., and 44.4 parts (3,3 ′, 5,5′-) of flaky sodium hydroxide (purity 99%, manufactured by Tosoh Corporation) Add 1.1 mole equivalent of 1 mole equivalent of hydroxyl group of tetramethylbiphenol over 60 minutes, and then further separate allyl chloride (purity 98.7 area% commercial allyl chloride by distillation. Allyl chloride polymer) Amount <0.2 area% (confirmed by gas chromatography) 101.5 parts (based on 1 molar equivalent of the hydroxyl group of 3,3 ′, 5,5′-tetramethylbiphenol) .3 molar equivalents, dropwise over 1.18 moles) 60 minutes against 1 mole of sodium hydroxide, as 5 hours at 38-40 ° C., was subjected to 1 hour of reaction at 60 to 65 ° C..
After completion of the reaction, after distilling off water, dimethyl sulfoxide, etc. under reduced pressure by heating at 135 ° C. or less with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Then, 157 parts of allyl etherified tetramethylbiphenol (AEP7) of the present invention were obtained by distilling off the solvents from the oil layer using a rotary evaporator under nitrogen bubbling under reduced pressure. The obtained resin had a hydroxyl group equivalent of 10,000 g / eq and a total chlorine content of 10 ppm. The structural formula of the allyl etherified tetramethylbiphenol resin obtained as the main component is represented by the following formula (3).

(Example 8)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while 40 parts of water, 200 parts of dimethyl sulfoxide, 3,3 ′, 5,5′-tetramethylbiphenol (hydroxyl equivalent 121 g / eq.) 128 parts were added, heated to 45 ° C. and dissolved, then cooled to 38-40 ° C., and 44.4 parts (3,3 ′, 5,5′-) of flaky sodium hydroxide (purity 99% manufactured by Tosoh Corporation) Then, 1.1 mole equivalent of 1 mole equivalent of hydroxyl group of tetramethylbiphenol was added over 60 minutes, and then allyl chloride (purity 97.1 area%, manufactured by Kanto Chemical Co., Ltd.) was separated by distillation. Aryl chloride polymer amount <0.21 area% confirmed by gas chromatography) 84.2 parts (3 moles of hydroxyl group of 3,3 ′, 5,5′-tetramethylbiphenol) 1.1 molar equivalents relative, dropwise over 1 molar) 60 minutes against 1 mole of sodium hydroxide, as 5 hours at 38-40 ° C., was subjected to 1 hour of reaction at 60 to 65 ° C..
After completion of the reaction, after distilling off water, dimethyl sulfoxide, etc. under reduced pressure by heating at 135 ° C. or less with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Then, 152 parts of allyl etherified tetramethylbiphenol (AEP8) of the present invention was obtained by distilling off the solvents from the oil layer using a rotary evaporator under nitrogen bubbling under reduced pressure. The obtained resin had a hydroxyl equivalent weight of 7020 g / eq and total chlorine of 320 ppm.

Example 9
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 20 parts of water, 1.9 parts of 12-tungstophosphoric acid / n hydrate, 1.0% of sodium tungstate / dihydrate 1.0 with nitrogen purge. After adjusting the pH to 6.0 with sodium dihydrogen phosphate dihydrate, 80 parts of allyl etherified tetramethylbiphenol (AEP7) obtained in Example 7 was added, and further 100 parts of toluene was added and dissolved. Then, 2.9 parts of trioctylmethylammonium acetate (TOMAA-50 Lion) was added to the agitation at room temperature, the temperature was raised to 60 ° C., and then 70 parts of 35% hydrogen peroxide (made by Junsei Kagaku) were added. It was dripped over 60 minutes.
After completion of dropping, after stirring at 60 ° C. for 40 hours, gas chromatography (measured with the above measurement conditions assuming that the holding time at 300 ° C. is 60 minutes) confirms that 90% by area or more of the raw material has been consumed. did. Then, 1% sodium hydroxide aqueous solution is added until the aqueous layer becomes pH 11 or more, and the aqueous layer is separated and drained. Furthermore, after adding 100 parts of 5% sodium thiosulfate aqueous solution and stirring for 30 minutes, it stood still and the organic layer isolate | separated into two layers was taken out.
To the obtained organic layer, 20 parts of activated carbon (Ajinomoto Fine Techno CP1) and 20 parts of montmorillonite (Kunimine Industries Kunipia F) were added and stirred at room temperature for 4 hours. After the treatment, the activated carbon and montmorillonite were removed by filtration under reduced pressure, and after washing with water, the solvent was distilled off with a rotary evaporator. The resulting epoxy resin had a softening point of 90 ° C. and an epoxy equivalent of 220 g / eq. The gel permeation chromatography (GPC) chart was confirmed. As a result, the bifunctional compound was 84 area%.

(Example 10)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 20 parts of water, 1.9 parts of 12-tungstophosphoric acid / n hydrate, 1.0% of sodium tungstate / dihydrate 1.0 with nitrogen purge. After adjusting the pH to 6.0 with sodium dihydrogen phosphate dihydrate, 80 parts of allyl etherified tetramethylbiphenol (AEP8) obtained in Example 8 was added, and further 100 parts of toluene was added and dissolved. Then, 2.9 parts of trioctylmethylammonium acetate (TOMAA-50 Lion) was added to the agitation at room temperature, the temperature was raised to 60 ° C., and then 70 parts of 35% hydrogen peroxide (made by Junsei Kagaku) were added. It was dripped over 60 minutes.
After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 40 hours and then gas chromatography was measured. As a result, the reaction rate (change rate from the raw material) was 64 area%, and it was confirmed that the reaction was remarkably slow compared to Example 9. did it.

(Example 11)
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 40 parts of water, 400 parts of dimethyl sulfoxide, and 199 parts of phenol biphenylene resin (hydroxyl equivalent 199 g / eq. Softening point 65 ° C.) were added while purging with nitrogen. After heating to ℃ and dissolving, cooled to 38-40 ℃, 44.4 parts of flaky caustic soda (purity 99% manufactured by Tosoh) as it is (1.1 molar equivalent to 1 molar equivalent of hydroxyl group of phenol biphenylene resin) The mixture was added over 60 minutes, and then further allyl chloride (purity 99.0 area% commercially available allyl chloride was separated by distillation. Allyl chloride polymer amount <0.02 area% confirmed by gas chromatography) 101.5 parts (phenol biphenylene) 1.3 molar equivalents relative to 1 molar equivalent of hydroxyl group of resin, and 1 molar equivalent of sodium hydroxide 1.18 moles) was added dropwise over 60 minutes, and the reaction was allowed to proceed at 38-40 ° C for 5 hours and at 60-65 ° C for 1 hour.
After completion of the reaction, after distilling off water, dimethyl sulfoxide, etc. under reduced pressure by heating at 135 ° C. or less with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Then, 202 parts of allyl etherified phenol biphenylene resin (AEP1) of the present invention was obtained by distilling off the solvents from the oil layer using a rotary evaporator under nitrogen bubbling under reduced pressure. The hydroxyl group equivalent of the obtained resin was 10000 g / eq or more, and the total chlorine was 24 ppm. The obtained resin was semi-solid.

From the above results, it was found that by using allyl chloride having a low degree of polymerization and using water as a solvent, the reaction efficiently proceeds and a low chlorine allyl ether resin can be obtained.

Claims (5)

An allyl ether resin obtained by reaction of a phenol resin and allyl chloride, which is obtained by allyl etherification using a metal hydroxide in the presence of allyl chloride, a phenol resin, water, and further an aprotic polar solvent. Method for producing allyl ether resin. The amount of water used is 2 to 50% by weight based on the total weight of the phenol resin, and the amount of metal hydroxide used is 1.0 to 1. The method for producing an allyl ether resin according to claim 1, wherein the amount is 15 mol. The method for producing an allyl ether resin according to claim 1 or 2, wherein the allyl chloride polymer in the allyl chloride is 2% or less. An allyl ether resin represented by the following formula (1) having a phenol aralkyl structure, wherein a hydroxyl group equivalent is 9300 g / eq or more.

An allyl ether resin represented by the following formula (2) having a phenol-dicyclopentadiene structure, wherein the total chlorine amount is 20 ppm or less and the hydroxyl group equivalent is 10,000 g / eq or more.