JP6515230B2 - Allyl ether resin and epoxy resin - Google Patents

Description

  The present invention relates to allyl ether resins and epoxy resins useful in electrical and electronic materials applications.

Conventionally, allyl ether compounds have been used to produce cured products using the reactivity of the allyl ether. In general, it is cured by radical polymerization or the like to form a network polymer.
Specifically, conventionally, allyl ether compounds such as ethylene glycol monoallyl ether, resorcinol diallyl ether, catechol diallyl ether, 1,4-bis (allyloxymethyl) cyclohexane, etc. are reactive diluents, crosslinking agents, flame retardants, etc. It has been used as an additive, a raw material of a photocurable monomer, etc. (Patent Document 1).
Furthermore, allyl ether compounds can be used as raw materials for epoxy resins by oxidation reactions. The obtained epoxy resin can be used for various uses, such as a coating material, a structural material, an electric and electronic material (patent document 2).
On the other hand, allyl ether compounds are known to be phenolic compounds having an allyl group by Claisen rearrangement.

Japanese Patent Application Laid-Open No. 2005-170890 Japanese Patent Application Laid-Open No. 2012-067253 Japanese Patent Application Laid-Open No. 59-227918

In the synthesis of allyl ether compounds, a reaction of 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. Although it is possible to reduce the halogen content by using a compound such as allyl bromide which is easy to be eliminated, the amount of halogen to be eliminated is larger than that of allyl chloride, and allyl is easy to obtain in the general market. Halogenation with chloride is of industrial importance. In Patent Document 3, an attempt is made to use allyl chloride in order to avoid this problem, but it is only adapted to cresol novolac, which is relatively high in solvent solubility, and may 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 can not be removed during washing with water, and subsequent purification as allyl ether is difficult. The reaction is inhibited in the denaturation step such as conversion to cause a side reaction.
In addition, a reaction using allyl carbonate or allyl ester is disclosed as a method in which halogen is not mixed, but allyl carbonate or allyl ester as a raw material is expensive and is not suitable for general use in industrial applications. In addition, it is not preferable industrially because it is necessary to react an allylated carboxylic acid such as allyl acetate and use an expensive catalyst at the time of synthesis.
That is, an object of the present invention is to provide an allyl ether resin which is suitable for an electric and electronic material and a raw material thereof, and can be obtained at low cost with low halogen, and an epoxy resin using the same.

As a result of intensive investigations in view of the above-described situation, the present inventors have completed the present invention.
That is, the present invention
(1)
An allyl ether resin represented by the following formula (1)

(In the formula, a plurality of R's each independently represent a hydrogen atom or an alkyl group. A plurality of a's each independently represent a value of 1 to 3 and n represents 1 to 10)
(2)
In the chromatogram obtained by high performance liquid chromatography measurement, the impurity peak present between the peak of the compound of n = 1 and the peak of the compound of n = 2 in the formula (1) is 1.5 area% The allyl ether resin according to the above (1), which is the following:
(3)
An epoxy resin obtained by using the allyl ether resin according to (1) or (2) and at least one of hydrogen peroxide, peracetic acid and carboxylic acid peroxide,
About.

  Low halogen allyl ether resins suitable for electrical and electronic materials and their raw materials are obtained. In addition, the allyl ether resin of the present invention becomes a precursor of a cured product excellent in low dielectric properties, flame retardancy and toughness by the polymerization, epoxidation or Claisen transition of itself.

3 is a high performance liquid chromatogram of allyl ether resin in Example 1. 7 is a high performance liquid chromatogram of allyl ether resin in Example 2.

  The allyl ether resin of the present invention has a structure of the following formula (1).

(In the formula, a plurality of R's each independently represent a hydrogen atom or an alkyl group. A plurality of a's each independently represent a value of 1 to 3; n represents 1 to 10)

The allyl ether resin of the present invention is obtained by the reaction of a phenolic resin and an allyl halide. As a phenol resin used as a raw material, phenols (phenol, a C1-C4 alkyl substituted phenol), 4,4'-bis (chloromethyl) -1,1'- biphenyl, 4,4'-bis (methoxy) Reactants with methyl) -1,1′-biphenyl are preferred. Particularly preferred is a reaction product of phenol, cresol or naphthol with 4,4'-bis (chloromethyl) -1,1'-biphenyl or 4,4'-bis (methoxymethyl) -1,1'-biphenyl.
These materials are superior in flame retardance to general resins such as cresol novolak, and can be used to produce compositions that can exhibit flame retardance without the addition of halogen as a flame retardant, which is useful for environmental impact Because of the high hydrophobicity of the system, migration of ions such as chlorine contained can be kept, and not only it has high electrical reliability, but the combination of low halogen and these structures is an electrical and electronic component. It is important as a material.

The allyl ether resin of the present invention, when measured by high performance liquid chromatography (HPLC), in the obtained chromatogram, between the peak of the compound of n = 1 and the peak of the compound of n = 2 in the formula (1) The impurity peak can be confirmed in
If the amount of this impurity peak is less than 1.5 area% in area ratio, particularly less than 1.0 area%, the subsequent epoxidation reaction is likely to proceed, and if it exceeds 2.0 area%, the reaction proceeds. Give a big impact. Therefore, the allyl ether resin of the present invention preferably has the above-mentioned impurity peak amount of less than 1.5% by area.
Specifically, an example is shown below regarding what said R is a hydrogen atom in said Formula (1). Figures 1 and 2 provide HPLC data. In FIG. 1 and FIG. 2, three large peaks visible in about 31 minutes correspond to a compound of n = 1, and three large peaks visible in the vicinity of 35 minutes (a shoulder peak is visible but converted as one). ), Which corresponds to a compound of n = 2. In FIG. 2, an impurity peak is observed between 32 and 34 minutes in the meantime. The presence of this peak is undesirable because it adversely affects during the subsequent epoxidation step. An example of a high performance liquid chromatogram as preferred is that shown in FIG.

The allyl ether resin of the present invention preferably has a softening point of 120 ° C. or less.
When the softening point exceeds 120 ° C., compatibility with the solvent is very difficult, so it is difficult to remove the salt by washing or the like, and it is not preferable from the concern of corrosion in the field requiring electric reliability.

It is preferable to use an allyl halide (for example, allyl chloride) to be used in the present invention which has a small amount of the polymer. For example, allyl chloride tends to polymerize with each other to become polyallyl chloride.
The residue of polyallyl chloride not only increases the amount of total chlorine, but also contributes to the increase in molecular weight of allyl ether resin, and may leave a trace amount of gel during production. Further, in order to reduce the amount of chlorine, it is necessary to add a considerable amount of a basic substance, which not only is industrially unfavorable but also produces highly toxic allyl alcohol in the system.
These polyallyl chloride compounds can be easily confirmed by gas chromatography or the like, and a specific amount thereof is preferably a polymer of 1 area% or less with respect to the allyl chloride monomer in area ratio, more preferably It is preferably 0.5 area%, more preferably 0.2 area% or less, and particularly preferably 0.05 area% or less.
In addition, 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 moles, preferably 1.0 to 1.10 moles, per mole of the hydroxyl group of the raw material phenol resin (hereinafter, also simply referred to as raw material phenolic resin). More preferably, it is 1.0 to 1.05 mol.

As a base which can be used when etherifying allyl chloride in the present invention, an alkali metal hydroxide is preferable, and sodium hydroxide, potassium hydroxide and the like can be mentioned as specific examples thereof, and solid substances are used. The aqueous solution may be used, but in the present invention, it is particularly preferable to use a flake-shaped solid from the viewpoint of solubility and handling.
The amount of the alkali metal hydroxide used is usually 1.0 to 1.15 moles, preferably 1.0 to 1.10 moles, more preferably 1.0 to 1.10 moles per mole of the hydroxyl group of the starting phenolic resin. It is .05 mol.

  In order to accelerate the reaction, quaternary ammonium salts such as tetramethyl ammonium chloride, tetramethyl ammonium bromide and trimethylbenzyl ammonium chloride may be added as a catalyst. The amount of quaternary ammonium salt to be used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per mole of the hydroxyl group of the starting phenol mixture.

In this reaction, non-protonic polar solvents such as dimethylsulfoxide (DMSO), dimethylformamide, dimethylacetamide, dimethylimidazolidinone, N-methylpyrrolidone and the like are preferable, and it is particularly preferable to use dimethylsulfoxide as a solvent.
The amount of the aprotic polar solvent used is preferably 20% by weight to 300% by weight, more preferably 25% by weight to 250% by weight, particularly preferably 25% by weight to 200% by weight, based on the total weight of the phenolic resin. . Aprotic polar solvents are not useful for purification such as water washing 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, which is not preferable.
In addition, it is also possible to use another solvent in this reaction. When using, it is preferable to use together C1-C5 alcohol. The alcohol having 1 to 5 carbon atoms is an alcohol such as methanol, ethanol or isopropyl alcohol. In addition, non-aqueous solvents such as methyl ethyl ketone, methyl isobutyl ketone and toluene may be used in combination, but the use of 100% by weight or less based on dimethyl sulfoxide is preferable. Particularly preferably, it is 0.5 to 50% by weight. When non-aqueous solvents such as methyl ethyl ketone, methyl isobutyl ketone and toluene are used in excessive excess, Claisen's transition occurs at the time of reaction, residual phenolic hydroxyl groups increase, and the amount of allyl chloride in the system runs short, Other than the intended structure may be produced, or all of the phenolic hydroxyl groups may not be allyletherified.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In the present invention, in particular, it is preferable to increase 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, by-products are formed, which is not preferable.
After completion of the reaction, the solvents are removed by heating under reduced pressure. The salt deposited during the reaction may be left as it is. The recovered allyl ether resin is dissolved in a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone and the like) as a solvent, and 40 ° C to 90 ° C, more preferably 50 In the state heated at -80 degreeC, it water-washes until a water layer becomes pH 5-8. At this time, when the pH is stopped at pH 8 or more, if the reaction such as epoxidation is performed later, the reaction may not proceed properly because the system of the catalyst is broken.
In the allyl etherification reaction, it is preferable to blow in an inert gas such as nitrogen (in air or liquid). When there is no blowing of an inert gas, coloring may occur in the obtained resin. Although the blowing amount of the inert gas varies depending on the volume of the kettle, the blowing of the inert gas in an amount capable of replacing the volume of the kettle in 0.5 to 20 hours is preferable.

The allyl ether resin of the present invention can be used in various applications.
Specifically, as a crosslinker for a curable resin as the allyl ether resin itself, further, as a raw material of an epoxy resin, a raw material of a phenolic resin by Claisen transition, and a curable resin composition containing those epoxy resin and phenolic resin in the composition It 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 and hydrogen peroxide, and the hydroxyl equivalent above becomes important, and furthermore, these are halogens The small amount is useful for various known materials, in particular, electric and electronic material applications requiring electric 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 a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with hydrogen peroxide water, a method of oxidizing with air (oxygen), a method of oxidizing with carboxylic acid peroxide, etc. Absent.
Specific examples of the method of epoxidation with peracid include the method described in JP-A-2006-52187.
Although various methods can be applied to the method of epoxidation with hydrogen peroxide water, specifically, JP-A-59-108793, JP-A-62-234550, and JP-A-H09-03059. 5-213919, JP-A-11-349579, JP-B-1-33471, JP-A-2001-17864, JP-B-3-57102, JP-A As described in JP 2011-225654, JP-A 2011-079794, JP-A 2011-084558, JP-A 2010-088363, JP-A 2010-09521, etc. Methods can be adapted.

Hereinafter, particularly preferable methods for obtaining the epoxy resin of the present invention will be exemplified.
First, the allyl ether resin, polyacids and quaternary ammonium salt of the present invention are reacted in the state of an organic substance, an aqueous solution of hydrogen peroxide.

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

  The amount of the polyacid used is 0.5 to 20 millimoles, preferably 0.5 to 20 millimoles, in terms of metal element (tungsten atoms for tungenic acid, molybdenum atoms for molybdic acid) per 1 mole of allyl group of the allyl ether resin of the present invention 1.0 to 20 millimoles, more preferably 2.5 to 15 millimoles.

As the quaternary ammonium salt, quaternary ammonium salts having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be used, and those having all aliphatic alkyl chains are particularly preferable. It can be used.
Specifically, tridecanylmethyl ammonium salt, dilauryl dimethyl ammonium salt, trioctyl methyl ammonium salt, trialkylmethyl (mixed type of compound wherein the alkyl group is an octyl group and a compound having a decanyl group) ammonium salt, trihexamethyl These include decyl methyl ammonium salt, trimethyl stearyl ammonium salt, tetrapentyl ammonium salt, cetyl trimethyl ammonium salt, benzyl tributyl ammonium salt, dicetyl dimethyl ammonium salt, tricetyl methyl ammonium salt, di-cured tallow alkyl dimethyl ammonium salt, etc. It is not limited to. In particular, those having 25 to 100 carbon atoms are preferable.
Specific examples of the anion species of these salts include, but are not particularly limited to, halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions and the like.
When the carbon number exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer may be deteriorated. When the number of carbon atoms is 10 or less, the hydrophilicity is increased, and the compatibility of the quaternary ammonium salt to the organic layer is also deteriorated, which is not preferable.
The amount of use of the quaternary ammonium salt is preferably 0.01 to 10 times equivalent to 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 in H ₂ WO ₄ , the carboxylate of quaternary ammonium is preferably in the range of 0.02 to 20 moles with respect to 1 mole of tungstic acid. Further, since tungstophosphoric acid is trivalent, it is preferably 0.03 to 20 moles, and silicotungstic acid is tetravalent, so 0.04 to 40 moles are preferable.
When the amount of quaternary ammonium carboxylate is more than 10 times equivalent of the valence of tungstic acid, not only the number of post-treatment steps may increase but also the reaction may be inhibited.

The above reaction may be carried out using a buffer. Although any buffer can be used, it is preferable to use a phosphate aqueous solution in this reaction. The pH is preferably adjusted to pH 4 to 10, more preferably pH 5 to 9. When the pH is 4 or less, the hydrolysis reaction of the epoxy group and the polymerization reaction tend to proceed. When the pH is 10 or more, the reaction becomes extremely slow and the reaction time is too long.
In the present invention, it is particularly preferable to adjust the pH to be between 5 and 9 when the catalyst tungstic acid is dissolved.
The method of using the buffer solution is, for example, 0.1 to 10 mol% equivalent of phosphoric acid (or phosphorus such as sodium dihydrogen phosphate) with respect to hydrogen peroxide in the case of phosphoric acid-phosphate aqueous solution which is a preferable buffer solution. Acid salts are used, and pH adjustment is carried out with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, etc.). It is preferable to add pH so that it may become the above-mentioned pH when adding hydrogen peroxide here. Moreover, it is also possible to adjust using sodium dihydrogen phosphate, disodium hydrogen phosphate or the like. The preferred phosphate concentration is 0.1 to 60% by weight, more preferably 1 to 45% by weight.
Also, in this reaction, no buffer solution is used, and disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium tripolyphosphate, etc. (or their hydrates) are phosphated without pH adjustment. It may be used by adding it directly. In the sense of simplification of the process, there is no need to worry about pH adjustment, and direct addition is particularly preferable. The amount of phosphate used in this case is usually 0.1 to 5 mole%, preferably 0.2 to 4 mole%, more preferably 0.3 to 3 mole%, based on hydrogen peroxide. It is an equivalent. At this time, if it exceeds 5 mol% equivalent to hydrogen peroxide, pH adjustment is required, and if it is 0.1 mol% equivalent or less, the hydrolyzate of the produced epoxy compound tends to progress, or the reaction is slow And other harmful effects occur.

  The reaction is epoxidized with hydrogen peroxide. As hydrogen peroxide used for this reaction, the aqueous solution which is a density | concentration of 10 to 40 weight% of hydrogen peroxide is preferable from the easiness of the handling. When the concentration is more than 40% by weight, handling becomes difficult, and decomposition reaction of the produced epoxy resin also easily progresses.

  It is preferable to use an organic solvent in this reaction. 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 in weight ratio to the allyl ether resin 1 of the present invention which is a reaction substrate. .5. If the weight ratio is more than 10, the progress of the reaction may be extremely slow. Specific examples of the organic solvent which 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. Be 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, nitriles such as acetonitrile Compounds and the like can also be used. Particularly preferable 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 carried out in a batch type reaction kettle, the allyl ether resin of the present invention, hydrogen peroxide (aqueous solution), heteropoly acid (catalyst), buffer, quaternary ammonium salt, Add the organic solvent and stir in two layers. There is no particular specification for the stirring speed. Since heat is generated in many cases at the time of addition of hydrogen peroxide, hydrogen peroxide may be gradually added after each component is added.
At this time, after adding a buffer solution (or water and phosphate) and tungstic acids to adjust the pH, a quaternary ammonium salt, an organic solvent and the allyl ether resin of the present invention are added and stirred in two layers. The method of dropping hydrogen peroxide is used.
Alternatively, while stirring a mixture of water, an organic solvent and the allyl ether resin of the present invention, tungstic acids and phosphoric acid (or phosphates) are added, pH adjustment is performed, and then a quaternary ammonium salt is added, and two layers are formed. A method may be used in which hydrogen peroxide is dropped to the place where stirring is performed.

  The reaction temperature is not particularly limited, but is preferably 0 to 90 ° C, more preferably 0 to 75 ° C, and particularly preferably 15 to 60 ° C. When the reaction temperature is too high, the hydrolysis reaction is likely 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., it is not preferable from the viewpoint of industrial production because a long-time reaction 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, excess hydrogen peroxide is quenched. 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. A preferable treatment method is a method of adjusting the neutralization so that the pH value of the basic compound is higher than 6 and then quenching the remaining hydrogen peroxide using a reducing agent. If the pH is 6 or less, the exotherm upon reduction of the excess hydrogen peroxide is large, which may result in decomposition products.

As the reducing agent, sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C and the like can be mentioned. The amount of use of the reducing agent 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 molar number of excess hydrogen peroxide is there.
These are preferably added as an aqueous solution, the concentration of which is 0.5 to 30% by weight.

Examples of 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, and phosphorus such as sodium phosphate and sodium hydrogen phosphate. And basic solids such as acid salts, ion exchange resins, and alumina.
The amount thereof used is water or an organic solvent (eg, 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 and the like The amount used is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times the molar amount of the excess hydrogen peroxide, if it is soluble in various solvents such as The molar amount is more preferably 0.05 to 3 times the molar amount. These may be added as water or a solution of the above-mentioned organic solvent, or may be added alone.
When using a solid base which does not dissolve in water or an organic solvent, it is preferable to use an amount of 1 to 1000 times by weight the amount of hydrogen peroxide remaining in the system. More preferably, it is 10 to 500 times, more preferably 10 to 300 times. When using a solid base which does not dissolve in water or an organic solvent, treatment may be performed after separation of the aqueous layer and the organic layer described later.

After quenching of hydrogen peroxide (or before quenching), at this time, the organic layer and the aqueous layer are not separated, or when the organic solvent is not used, the operation is performed by adding the above-mentioned organic solvent, water Extract the reaction product from the bed. In this case, the organic solvent used is 0.5 to 10 times, preferably 0.5 to 5 times by weight ratio to the allyl ether resin of the present invention which is the raw material. After repeating this operation several times as necessary, the separated organic layer is purified by washing with water if necessary.
Ion exchange resin and metal oxide (especially, silica gel, alumina and the like are preferable), activated carbon (especially, chemical activated carbon is particularly preferable), complex metal salt (among all, basic complex metal salt in particular) from the obtained organic layer. The impurities are preferably removed by a clay mineral (particularly, preferably a layered clay mineral such as montmorillonite) and the like, followed by washing with water, filtration and the like, 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 The present invention will next be described in more detail by way of examples, in which parts are 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: According to JIS K 7236 (ISO 3001).
Softening point: According to JIS K 7234.
Total chlorine: Weigh accurately about 0.1 g of the sample, burn the sample with the burner and absorb with the absorbent.
Absorbent solution: 20 mL of 0.1% hydrogen peroxide water
The obtained water absorption liquid was measured by ion chromatography.
Hydroxyl equivalent: in accordance with JIS K 0070.
Gel permeation chromatography (GPC): Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2), the connected eluent is tetrahydrofuran, the flow rate is 0.5 ml / min. Column temperature is 40 ° C, detection: RI (differential refraction detector)
High performance liquid chromatography (HPLC): column ODS2 eluent: acetonitrile-water gradient, column temperature 40 ° C. detection UV 274 nm, flow rate 1.0 ml / min.
Gas Chromatography (GC):
Column HP-5 30mx 0.32mm x 0.25μm
Carrier gas Helium 1.0mL / min Split1 / 50
Injector temperature 300 ° C
Detector temperature 300 ° C
Oven temperature program After holding for 5 minutes at 50 ° C., increase temperature from 50 ° C. to 300 ° C. at 10 ° C./min Hold for 5 minutes at 300 ° C. as it is.

Example 1
To a flask equipped with a stirrer, reflux condenser, and stirrer, add 40 parts of water, 400 parts of dimethyl sulfoxide, and 210 parts of phenol biphenylene resin (hydroxy group equivalent 210 g / eq. Softening point 74 ° C) while applying nitrogen purge, 45 The temperature is raised to ° C and dissolved, and then cooled to 38-40 ° C. 44.4 parts of sodium hydroxide in flake form (purity 99% made by Tosoh) (1.1 molar equivalent to 1 molar equivalent of hydroxyl group of phenol biphenylene resin) ) Over 60 minutes and then further allyl chloride (purity 98.7 area% commercial allyl chloride separated by distillation. Amount of allyl chloride polymer <0.2 area% confirmed by gas chromatography (GC)) 101.5 parts (1.3 molar equivalents relative to 1 molar equivalent of hydroxyl groups of phenol biphenylene resin, Potassium 1 mole dropwise 1.18 moles) over a period of 60 minutes for, as 5 hours at 38-40 ° C., was subjected to 1 hour of reaction at 60 to 65 ° C..
After completion of the reaction, remove water, dimethyl sulfoxide, etc. by distilling off heat and pressure at 135 ° C. or less with a rotary evaporator under reduced pressure, add 740 parts of methyl isobutyl ketone, repeat water washing and check that the aqueous layer has become neutral After that, the solvent was distilled off from the oil layer while bubbling nitrogen under reduced pressure using a rotary evaporator to obtain 240 parts of allyletherified phenol biphenylene resin (AEP1) of the present invention. The total chlorine of the obtained resin was 15 ppm. Moreover, the obtained resin was semisolid. And the chromatogram obtained by the measurement of the high performance liquid chromatography was as showing in FIG. The structural formula of the allyletherified phenol biphenylene resin obtained as the main component is represented by the following formula (2).

(Example 2)
To a flask equipped with a stirrer, reflux condenser, and stirrer, add 40 parts of water, 300 parts of dimethyl sulfoxide, and 207 parts of phenol biphenylene resin (hydroxy group equivalent of 207 g / eq. Softening point 74 ° C) while applying nitrogen purge, 45 The temperature is raised to ° C and dissolved, and then cooled to 38-40 ° C. 44.4 parts of sodium hydroxide in flake form (purity 99% made by Tosoh) (1.1 molar equivalent to 1 molar equivalent of hydroxyl group of phenol biphenylene resin) ) Over 60 minutes and then further allyl chloride (purity 98.1 area% commercially available allyl chloride is separated by distillation. Amount of allyl chloride polymer <0.2 area% confirmed by gas chromatography) 101.5 Sodium hydroxide (1.05 mole equivalent to one mole equivalent of hydroxyl group of phenol biphenylene resin Dropwise 1.0 mol) over 60 minutes relative to 1 mol, as 5 hours at 38-40 ° C., was subjected to 1 hour of reaction at 60 to 65 ° C..
After completion of the reaction, remove water, dimethyl sulfoxide, etc. by distilling off heat and pressure at 135 ° C. or less with a rotary evaporator under reduced pressure, add 740 parts of methyl isobutyl ketone, repeat water washing and check that the aqueous layer has become neutral After that, the solvents were distilled from the oil layer while bubbling nitrogen under reduced pressure using a rotary evaporator to obtain 237 parts of allyletherified phenol biphenylene resin (AEP2) of the present invention. Total chlorine was 53 ppm. And the chromatogram obtained by the measurement of the high performance liquid chromatography was as showing in FIG. Moreover, the obtained resin was semisolid. The representative structural formula is the same as that of the above formula (2).

(Example 3)
In a flask equipped with a stirrer, reflux condenser and stirrer, add 40 parts of water, 400 parts of dimethyl sulfoxide, and 223 parts of o-cresol biphenylene resin (hydroxy group equivalent 223 g / eq. Softening point 68 ° C) while nitrogen purge is performed. Then, the temperature is raised to 45 ° C. and dissolved, followed by cooling to 38-40 ° C., 44.4 parts of sodium hydroxide in flake form (purity 99% manufactured by Tosoh Corporation) 41.1 parts (one mole equivalent of hydroxyl group of cresol biphenylene resin) Molar equivalent) was added over 60 minutes, and then 101.5 parts of allyl chloride (purity 98.7 area% amount of allyl chloride polymer manufactured by Tokyo Chemical Industry Co., Ltd. <0.2 area% confirmed by gas chromatography) (cresol biphenylene resin) Per mole of hydroxyl group, 1.3 molar equivalent, 1.18 moles per mole of sodium hydroxide) The reaction mixture was added dropwise over 60 minutes, and the reaction was allowed to proceed at 38-40.degree. C. for 5 hours, and at 60-65.degree.
After completion of the reaction, remove water, dimethyl sulfoxide, etc. by distilling off heat and pressure at 135 ° C. or less with a rotary evaporator under reduced pressure, add 740 parts of methyl isobutyl ketone, repeat water washing and check that the aqueous layer has become neutral After that, the solvents were distilled from the oil layer while bubbling nitrogen under reduced pressure using a rotary evaporator to obtain 242 parts of an allyletherified cresol biphenylene resin (AEP3) of the present invention. The total chlorine of the obtained resin was 7 ppm. Moreover, the obtained resin was semisolid. The structural formula of the allyletherified o-cresol biphenylene resin obtained as the main component is represented by the following formula (3).

(Example 4)
20 parts of water, 3.8 parts of 12-tungstophosphoric acid n-hydrate, sodium tungstate dihydrate 2.0 with nitrogen purge applied to a flask equipped with a stirrer, a reflux condenser and a stirrer After adjustment to pH 5.0 with 1 part, sodium dihydrogen phosphate dihydrate, 88 parts of allyletherified phenol resin (AEP1) obtained in Example 1 is added, and 100 parts of toluene is further added and dissolved. After adding 5.8 parts of trioctyl methyl ammonium acetate (TOMAA-50 made by Lion) while stirring at room temperature and raising the temperature to 60.degree. C., add 70 parts of 35% hydrogen peroxide water (genuine chemical nature) Dropped over a minute.
After completion of dropping, the solution is stirred at 60 ° C. for 48 hours, 1% aqueous sodium hydroxide solution is added until the aqueous layer reaches pH 11 or more, the aqueous layer is separated, drained, and 100 parts of 5% aqueous sodium thiosulfate solution After stirring for 30 minutes, the mixture was allowed to settle and the organic layer separated into two layers was taken out.
To the obtained organic layer, 20 parts of activated carbon (Ajinomoto Fine Techno CP1) and 40 parts of montmorillonite (Kunimine Kogyo Kunipia F) were added, and stirred at room temperature for 4 hours. After treatment, activated carbon and montmorillonite were removed by vacuum filtration, and after washing with water, the solvent was distilled off with a rotary evaporator. The obtained epoxy resin is semisolid, and the epoxy equivalent is 3020 g / eq. Met.

(Example 5)
The synthesis was carried out in the same manner as in Example 4 except that AEP3 was used. The obtained epoxy resin is semisolid and has an epoxy equivalent of 10310 g / eq. Met.

The higher the epoxy equivalent, the lower the epoxy density of the produced epoxy. That is, it turns out that it is not epoxidized. The present results indicate that the allyl ether resin of the present invention is useful in the conversion to epoxy resin.

(Example 6)
To a flask equipped with a stirrer, reflux condenser, and stirrer, add 40 parts of water, 400 parts of dimethyl sulfoxide, and 199 parts of phenol biphenylene resin (hydroxyl equivalent of 199 g / eq. Softening point 65 ° C) while applying nitrogen purge, 45 The temperature is raised to ° C and dissolved, and then cooled to 38-40 ° C, and as it is flake shaped caustic soda (purity 99%, made by Tosoh) 44.4 parts (1.1 molar equivalent relative to hydroxyl equivalent of phenol biphenylene resin) for 60 minutes Add, and then further add allyl chloride (purity 99.0 area% commercially available allyl chloride separated by distillation. Amount of allyl chloride polymer <0.02 area% confirmed by gas chromatography) 101.5 parts (phenol biphenylene resin 1.3 molar equivalents to hydroxyl equivalent, 1.18 to 1 molar of sodium hydroxide ) 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, remove water, dimethyl sulfoxide, etc. by distilling off heat and pressure at 135 ° C. or less with a rotary evaporator under reduced pressure, add 740 parts of methyl isobutyl ketone, repeat water washing and check that the aqueous layer has become neutral After that, the solvent was distilled from the oil layer while bubbling nitrogen under reduced pressure using a rotary evaporator to obtain 202 parts of allyletherified phenol biphenylene resin (AEP 4) of the present invention. The hydroxyl equivalent of the obtained resin is 10000 g / eq. It is above and total chlorine was 24 ppm. Moreover, the obtained resin was semisolid.

Although the present invention has been described in detail with reference to particular embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.
The present application relates to the Japanese patent application filed on February 5, 2013 (Japanese Patent Application No. 2013-20240) and the Japanese patent application filed on March 7, 2013 (Japanese Patent Application No. 2013-45116). It is based and is incorporated by reference in its entirety. Also, all references cited herein are taken as a whole.

Claims (7)

The hydroxyl equivalent represented by the following formula (1) is 10000 g / eq. Allyl ether resin having a softening point of 120 ° C. or less.

(In the formula, a plurality of R's each independently represent a hydrogen atom or an alkyl group. A plurality of a's each independently represent a numerical value of 1 to 3 and n represents 1 to 10 ) The allyl ether resin according to claim 1 for a raw material of phenolic resin by Claisen transfer. A phenolic resin having an allyl group by Claisen transition of the allyl ether resin according to claim 1 . An epoxy resin obtained by using the allyl ether resin according to claim 1 or 2 and at least one of hydrogen peroxide and carboxylic acid peroxide, and having a total chlorine content of 53 ppm or less . The epoxy resin according to claim 4 , wherein the carboxylic acid peroxide is peracetic acid. A curable resin composition comprising the allyl ether resin according to claim 1 or claim 2 or the phenol resin according to claim 3 . A cured product obtained by curing the curable resin composition according to claim 6 .

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