JPS62292741A - Novel phenolic compound and epoxy curing agent - Google Patents

Abstract

NEW MATERIAL:A phenolic compound expressed by formula I [Y is CH2, SO, S, O or CO; A is formula II (R1-R5 are H or 1-10C alkyl). EXAMPLE:Mono alpha-methylallyl ether of 4,4'-dihydroxydiphenyl ether. USE:An epoxy curing agent, particularly useful as a latent one-pack type epoxy curing agent, having improved storage stability and rapidly curable at normal practical curing temperatures and usable as a raw material for various high polymers, medicines, raw material for agricultural chemicals or raw material for other useful compounds. PREPARATION:For example, a bisphenol expressed by formula III or alkali metal salt thereof is reacted with an olefinic compound expressed by formula IV {Z is halogen or R6SO3 [R6 is (substituted) phenyl or lower alkyl]} in a polar aprotic solvent and, as necessary, in the presence of an acid binder to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel phenolic compound and a novel latent-wavy epoxy curing agent containing the phenolic compound.

<Prior art> Epoxy resins are generally used as a mixed system containing a curing agent and a catalyst, and are cured at room temperature or by heating.
This epoxy resin composition has poor storage stability, undesirable gelling and hardening before use, and a short pot life.

Specifically, 9 For example, in the case of a two-component epoxy resin composition, when a curing agent is added to the epoxy resin, the bot life is short, ranging from several minutes to several days, so the two must be mixed each time they are used. Therefore, mistakes in formulation and mixing can lead to defective products and material loss, and even if a curing agent is mixed in advance, it will not harden as it is.
A so-called latent wave type is strongly desired.

Several latent epoxy curing agents have been proposed so far, and representative compounds include dicyandiamide, carboxylic acid anhydrides, acid hydrazide compounds, boron trifluoride-amine adducts, guanamines, and melamine. (High functionality and application development of epoxy resin J
CMC company.

(Published on February 8, 1983) <Problems to be solved by the invention> However, the curing temperature of dicyandiamide, carboxylic acid anhydride, melamine, and guanamine is too high.

Furthermore, since the curing time is too long, curing accelerators such as tertiary amines and aromatic oxy compounds are also used. Therefore, storage stability is naturally poor, and satisfactory stability is not obtained as a dispersed epoxy resin composition. In addition, boron trifluoride-amine adduct is not only highly hygroscopic, but also has skin irritation and metal corrosive properties, so it has a large wholesaler in practical terms. In addition, dicyandiamide and acid hydrazide compounds melt near their melting point and harden with epoxy resin, so when mixed with liquid epoxy resin at room temperature, they form a slurry system, and during the heat curing process, particles settle and become uniform. It is difficult to obtain a cured resin and is unsatisfactory as a latent curing agent. Further, the following general formula (wherein, X is a divalent hydrocarbon such as an alkylene group, a cycloalkylene group, a monocyclic or polycyclic arylene group, or -C(CH3)z, Co-

Indicates a divalent hydrocarbon group bonded by a divalent atomic group such as SOz or CH2. ) is known to be used together with an epoxy resin (Japanese Unexamined Patent Publication No. 56-4647).

However, this compound also. In particular, when used as a curing agent for amine-based epoxy resins, the pot life was short and storage stability was unsatisfactory. That is, virtually no latent W-type epoxy curing agents with excellent storage stability are known.

Means for Solving Problems〉 Under these circumstances, the present inventors conducted intensive research to develop a latent-molded epoxy curing agent with higher performance. The present invention has been achieved by discovering that a latent-corrugated epoxy resin composition can be formed which has excellent storage stability when used as a curing agent and which cures rapidly at normal curing temperatures.

That is.

An object of the present invention is to provide a new phenolic compound that can be used as a secondary epoxy curing agent.

Furthermore, another object is to provide a novel phenolic compound useful as a raw material for molecule molecules, pharmaceuticals, agricultural chemicals, or other useful compounds. The object of the present invention is to provide a novel phenolic compound represented by the general formula CI].

AOOH (wherein, Y is CH2, S, O, So or CO, R1
, RI R3, R4 and Rs each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

) and the novel phenolic compound represented by [I] above.

The configuration of the present invention will be explained in detail below.

The phenolic compound of the present invention is produced by one method, for example, as follows.

(A) A method of reacting bisphenols represented by the general formula [■] on the next page or their alkali metal salts with an olefinic compound represented by the general formula [V] on the next page.

(B) Bisphenols represented by the above general formula [TV] or their alkali metal salts and an acetylene compound represented by the following general formula [VI] Example R+ RI C:ECC-Z ・------ ------
[VI] For example, propargyl chloride, propargyl bromide.

α,α-Dimethylpropargyl chloride, etc. are reacted in the same manner as in (A) above, and then methanol, ethanol, isopropanol, benzene, toluene, etc. are used as a solvent to react with Lindlar catalyst or quinoline-poisoned P d
/ B a A method for obtaining the compound of the present invention by partial hydrogenation using a S○4 catalyst or the like under normal pressure or increased pressure.

(In the general formula [■, [V], [VI], Y represents CH2, So, S, O or CO. Also, + R
++ Rx+ R31R41Rs each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Further, 2 represents a halogen atom or an R6S Oi group.

RG represents a substituted or unsubstituted phenyl group or lower alkyl group. ) (C) halogen-substituted biphenyls and furyl alcohol,
A method of reacting furyl- or propargyl-type alcohol, typified by meta-allyl alcohol, ethyl-substituted furyl alcohol, or propargyl alcohol, with an alkali metal salt.

(D) A method in which bisphenols represented by the above general formula [IV] are selectively converted into monoacetate to protect the phenol hydroxyl group, and then reacted in the same manner as in (A) and then hydrolyzed with an acid or base. can be mentioned.

Preferred specific examples of bisphenols used as raw materials include bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) ether, and bis(4-hydroxyphenyl) ether.
Examples thereof include 4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)ketone, and bisphenol F.

Preferred specific examples of the olefinic compound used as the other raw material include furyl chloride, crotyl chloride, prenyl chloride, metaallyl chloride, 2,3-dimethylpropenyl chloride, 2-hexenyl chloride, 2-octenyl chloride, and 2-chloride. Decenyl, as well as bromides to replace their chlorides,
Examples include iodide, p-toluenesulfonic acid ester, benzenesulfonic acid ester, metasulfonic acid ester compounds, and the like.

As the reaction solvent, water, an organic solvent, a mixed solvent of water and an organic solvent, etc. can be used. Preferred solvents include alcohols such as methanol, ethanol, isopropanol, and methyl cellosolve; polar aprotic solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and hexamethylphosphorylamide; acetone; and methyl ethyl ketone. Ketones such as methyl isobutyl ketone, benzene, toluene.

xylene, chlorobenzene, dichlorobenzene.

Aromatic solvents such as trichlorobenzene, chloroform,
Alkyl halides such as dichloromethane and 1,2-dichloroethane or mixtures thereof are used.

In addition, in a water-organic solvent system, when a solvent incompatible with water is used as the organic solvent, it is preferable to use a phase transfer catalyst as the reaction accelerator. As the phase transfer catalyst, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, N-
Laurylpyridinium chloride, N-lauryl-4-
Examples include picolinium chloride and benzyltriethylammonium hydroxide. The reaction is carried out in the presence of an acid binder, if necessary. As acid binders, inorganic bases such as caustic soda, caustic potash, soda carbonate, potassium carbonate, calcium carbonate, calcium oxide, magnesium oxide, zinc oxide, magnesium hydroxide, zinc hydroxide, calcium hydroxide, and sodium acetate, potassium acetate, etc. Alkali metal salts or alkaline earth metal salts of organic acids are used.

The molar ratio of the olefinic compound to the bisphenols is usually in the range of 0.1 to 2.0 times the molar range, but
Preferably, 0.8 to 1.2 times the mole is used.

Further, when an acid binder is used, it is usually used in an amount of 0.1 to 2.0 times the mole of the bisphenol, preferably 0.8 to 1.2 times the mole of the bisphenol. The reaction temperature is usually 20 to 150°C and the reaction time is usually 1 to 20 hours.

The method for isolating the phenolic compound of the present invention thus obtained varies depending on the physical properties of the phenolic compound, but usually the inorganic salt obtained from the acid binder is removed by filtration or decantation, if necessary. The solvent used in the latter 9 reactions was distilled off to obtain a concentrated solution, and if necessary, chloroform and ethyl acetate were added using a column packed with silica gel.

A method can be adopted in which benzene, toluene, cyclohexane, etc. are separated using a single solvent or a mixture thereof as an eluent.

Alternatively, the concentrated liquid may include caustic soda, carbonated soda,
It is also possible to isolate the desired product by adding caustic potassium or calcium carbonate to convert it into an alkali salt, followed by acid precipitation with an acid such as hydrochloric acid, sulfuric acid, oxalic acid, or acetic acid. Furthermore, again.

The reaction solution or concentrate can also be isolated by precise distillation.

The phenolic compound of the present invention thus obtained exhibits excellent effects when used as an epoxy curing agent.

When the phenolic compound of the present invention is used as an epoxy curing agent, a compound having two or more 1,2-epoxide groups per molecule is used as the epoxy resin that can be completely cured. Preferred epoxy resins include bisphenol A diglycidyl ether, tetraglycidyldiaminodiphenylmethane, and triglycidylmethaminophenol.

Triglycidyl para-aminophenol, tetrabromo bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, fluoroglycitur triglycidyl ether, tetrahydroxybenzophenone tetraglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetramethylbisphenol A diglycidyl ether, bisphenol C Diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, diglycidyl aniline, tetraglycidyl metaxylylene diamine, diglycidyl tribromoaniline, tetraglycidyl bisaminomethylcyclohexane, phenol novolac type epoxy, cresol novolac type epoxy, etc. .

Generally, an epoxy resin and an epoxy curing agent can be made into a cured epoxy resin by heating to a predetermined curing temperature. (used for meaning) is
It is determined as appropriate depending on the materials of the epoxy resin and epoxy curing agent and the intended use of the cured product.

When the phenolic compound of the present invention is used as an epoxy curing agent, the epoxy curing agent and the epoxy resin are usually mixed together at ￥ 300,000 yen temperature or, if necessary, by heating slightly below the curing temperature. A method is employed in which a liquid type epoxy resin composition is formed and, at the time of desired use, this composition is heated to a curing temperature to form a cured product.

The epoxy curing agent of the present invention mainly contains the phenolic compound of the present invention, and may contain other epoxy curing agents as long as the properties of the phenolic compound of the present invention are not impaired. do not have.

The epoxy curing agent of the present invention is usually 0.7 to 2.0 equivalents, preferably 1.0 to 1.5 equivalents, per equivalent of epoxy resin.
Equivalent weights are used (calculated assuming 2 hydroxy groups per molecule of the phenolic compound of the invention).

Furthermore, the epoxy curing agent of the present invention can be used together with a curing accelerator and a radical polymerization initiator.

As curing agent accelerators, boron trifluoride amine complexes such as boron trifluoride monoethylamine complex, boron trifluoride piperidine complex, triethylamine, dimethylaniline, 1
, 8-diazabicyclo(5,4,0)undecene-7, phosphine compounds such as triphenylpht-sphine, and imidazole compounds such as 2-ethyl-4-methylimidazole, N-methylimidazole, and N-phenylimidazole. , metal acetylacetonates such as aluminum acetylacetonate, iron acetylacetonate, cobalt acetylacetonate, borate compounds such as triphenylborate, and quaternary ammonium salts such as tetramethylammonium bromide. These curing accelerators are used in an amount of about 0.005 to 5 ohr, preferably about 0.005 to 1 phr, based on the total resin content.

In general, there are no particular restrictions on the radical initiator, and most can be used; examples include peroxides such as azobisisobutyronitrile, dicumyl peroxide, and methyl ethyl ketone peroxide. It will be done.

A mixed solution of the epoxy curing agent comprising the phenolic compound of the present invention, a glycidyl ether type epoxy resin such as bisphenol A diglycidyl ether, and a curing accelerator such as metal acetylacetonate can have a very long pot life. A mixture of a glycidylamine type epoxy resin such as ZaraNi tetraglycidyldiaminodiphenylmethane and the novel phenolic compound of the present invention has a much superior pot life compared to the case of using a conventional diol type curing agent such as bisphenol A. is obtained. Moreover, all of the above compositions have a normal concentration of 160 to 20
It can be cured quickly at a curing temperature of 0°C to obtain a cured epoxy resin.

Effects> The compound of the present invention is a new substance, and has the following properties: CH2, SO, S,
0, two aromatic rings are bonded via CO, one aromatic ring is substituted with an allyl ether group, and the other aromatic ring is substituted with OH
It has a structure substituted with a group.

The phenolic compound of the present invention has a very ideal specific action when used as an epoxy curing agent, especially a latent one-component epoxy curing agent. Usually, an OH type epoxy curing agent contains 2WII or more OH groups in the molecule.

However, since the compound of the present invention has only one OHM in the molecule, it does not function as an epoxy curing agent as it is.

That is, in a system in which the phenolic compound of the present invention coexists with an epoxy resin while being heated to a temperature below the curing temperature, the allyl ether group of the phenolic compound does not contribute to an increase in molecular weight, and therefore the pot life is long. Become. When the phenolic compound of the present invention is heated to a curing temperature, the allyl ether group becomes an allyl group and an OH group through the Claisen rearrangement reaction as shown below, thus forming a compound with two OH groups, which can be used as an epoxy curing agent. It becomes effective. That is, the generated OH groups react with the epoxy groups of the epoxy resin to obtain a cured epoxy resin having a desired high molecular weight.

That is, the phenolic compound of the present invention has an extremely effective effect, especially as a wave-type epoxy curing agent.

Utilizing the Claisen rearrangement reaction as in the present invention, reacting a curing agent at a desired time in a corrugated epoxy resin composition;
Up to now, no attempt has been made to improve the pot life of epoxy curing agents, and this was discovered for the first time in the present invention.

The phenolic compounds of the present invention are particularly useful as curing agents for latent-corrugated epoxy resins, such as adhesives, coatings, encapsulants for ICs, glass fibers, carbon fibers, polyamide fibers, etc. Matrix resin for FRP etc., or other laminated products, cast products, etc.
It is useful as epoxy products such as molded products.

Alternatively, raw materials for polyamide resin, polyurethane, polycarbonate resin, polyester phenol resin, polyether sulfone, ion exchange resin, etc., polymer additives, or raw materials for polymer additives, raw materials for synthetic tannins, raw materials for pharmaceuticals and agricultural chemicals, pigments, and photographs. It is also useful in applications such as medicines, binders for electrostatic toners, raw materials for waxes, varnishes, and lacquers, raw materials for ink preparation, and additives for plating.

<Examples> Next, the present invention will be specifically explained with reference to Examples, but these Examples are not intended to limit the present invention.

Example 1 Synthesis of monoallyl ether of 4.4-dihydroxydiphenyl ether (compound 1) 59 g (0.29 mol) of 4.4-dihydroxydiphenyl ether was dissolved in 100rd acetone, and aqueous KOH solution (KO816
, 4 g (0°29 mol)/water 15!111) were added to form a salt. 44.2 y (0.37 mol) of allyl bromide was added dropwise to the mixture over 40 minutes while stirring under heating under reflux, and the reaction was continued for an additional 8 hours. After the reaction, cool to air temperature, remove the precipitate by decantation, add 200 d of ethyl acetate to make a solution, and add 200 d of water to this solution.
Washed twice with Ovi. After distilling off the solvent from this solution using an evaporator, the concentrated liquid was mixed with silica gel (Mer
ck7734)/chloroform system.

After distilling off the solvent of this separated fraction, it was recrystallized from aqueous ethanol to yield 19.691! ! (purity 98.7%
).

The analysis results of Compound 1 were as follows.

mpnia 1-73℃ IR: ~3300cIR-1 (phenolic OH>, 1
640.995.920cm-1 (vinyl) 1H-NM
R (CDCffl 3 ): 4.5 ppm (double
et 2H, -CH2-), 5.1 to 5.6 ppm
(double doublet 2H1=CH2)
, 5.7-6.3 pDm (multiplet
1 H, vinyl-CH=), 5.4 ppm (singl
et 1H, -0H), 6.7-7.0ppm (mu
ltiplet 8H1aromatic H> All of the above analysis results support the structure of Compound 1.

Example 2 Synthesis of mono-methyl allyl ether (compound 2) of 4.4-dihydroxydiphenyl ether 4.4-dihydroxydiphenyl ether 50s (0
, 25 mol) was dissolved in 200 rrIl of acetone, and a KOH aqueous solution (KOH 14 g (0.25 mol V water 15
m) was added to form a salt.

To this was added crotyl chloride 45s (0.5 mol) at room temperature with stirring, and the mixture was further reacted under heating and reflux for 2 hours. After the reaction is completed, acetone is distilled off from the reaction mixture using an evaporator to obtain fJ? Add benzene to the f-product,
After being made into a solution, this solution was washed twice with water. After removing benzene from the solution, the concentrate was immersed in silica gel (Mer'ck 773).
4)/Chromatographic separation using a benzene-cyclohexane system. After collecting the monoallyl ether fraction and distilling off the solvent, it was recrystallized from benzene/cyclohexane solvent to give compound 2 as 1
2.8g was obtained (purity 100%).

The analysis results for Compound 2 were as follows.

mpnia 6-79℃ IR: ~3300cm-' (phenolic OH), 1
620.1000.950cm-1 (vinyl) I H-
NMR (CDC173>: 1.7 ppm (double
let 3 H, -CH3) , 4.40 I) m(
doublet 2 Hl-CH2-), 5. ap
pm(multiplet 2H1-C:H=CH-
), 6.1ppm (Sinlet IH, -0H),
6.8~7.01)l)m(multiplet 8
H.

aromatic H) All of the above analytical results support the structure of Compound 2.

Example 3 Mono β- of 4.4-dihydroxydiphenyl ether
Synthesis of Methyl Allyl Ether (Compound 3) CH3 The reaction was carried out in the same manner as in Example 2 except that methalyl chloride was used instead of crotyl chloride. Chromatographic separation and recrystallization were performed in the same manner to obtain 8.3 g (purity 100%).

The analysis results for Compound 3 were as follows.

mp Near 2-74°C IR: ~3300cm-1 (phenolic OH>,
1660.1000,900cm-” (vinyl) I
H-NMR (CDC13): 1.8 pI)m(si
nglet 3t-(,-CH3), 4.4 pp
m(singlet 2 Hl-CH2-), 5.
oppm(double 2H, -CH2=),
6.1 ppm (singlet 1 Hl-OH>
, 6.8~7°OpDm (multiple 8
H, aromatic H>All these results support the structure of compound 3.

Example 4 Mono α- of 4.4-dihydroxydiphenyl ether
Synthesis of methyl allyl ether (compound 4) CH3 4,4--dihydroxydiphenyl ether 6C1 (0
, 34 mol) in 400 d of acetone, and add KO to this.
H aqueous solution (KOH 20g (0.36 mol)/water 20!n
! > was added to produce salt. To this was added 45s (0.5 mol) of 3-chloro-1-butene under stirring at room temperature,
The mixture was further reacted under heating under reflux for 5 hours. After the reaction is complete, acetone is distilled off from the reaction mixture using an evaporator.
Benzene was added to 1q of the obtained concentrate to dissolve it, and this solution was washed twice with water. After distilling off benzene from the solution, the concentrate was subjected to chromatographic separation several times using silica gel (MerCk7734>/benzene-cyclohexane system), and after distilling off the solvent of the separated fractions, 19.8 g of compound 4 was obtained with a purity of 9.
5%).

IR: ~3400 cm-1 (phenolic OH),
1610.1000.930c! n-1 (vinyl) I
H-NMR (CDC!3): 1.4 ppm (double
let 3 Hl-CH3> 1.4.5-4.9p
pm(multiplet 1H,:;CH-0-)
, 5, Q ~ 5.4 ppm (double do
ublet 2H, vinyl;=CHz), 6.0
~6.4 pDm (multiplet 2 Hl-
OH and vinyl-〇H=), 6.7-6.9 ppm (mu
ltiplet 8H1aromatic H) All of the above analytical results support the structure of Compound 4.

Example 5 Mono α of 4.4-dihydroxydiphenyl ether,
Synthesis of α-dimethylallyl ether (compound 5) CH3 4,4-dihydroxydiphenyl ether 5Oy (0
-2475 mol) was dissolved in 300 d of acetone, and added to this was a KOH aqueous solution (14 s of KOH (0.25 mol)/1 mol of water).
(M) was added to form a salt. To this was added 1,1-dimethyl-2-propynyl chloride 389, and the mixture was heated under reflux for 3 hours. After the reaction was completed, acetone was distilled off from the reaction mixture, the residue was dissolved in benzene, and after washing twice with water, the benzene was distilled off. The residue was chromatographed on a silica gel (Merck Silcagel 7734)/benzene system, the monopropargyl ether fraction was collected, and the benzene was distilled off. Crystals precipitated from the residue were recrystallized from a benzene-cyclohexane solvent to obtain white crystals. Yield: 14.8 g (MA degree 100%) The analysis results of this white crystal compound were as follows.

mp: 99-100°C 1H-NMR (CDC13): 1.65 pI) m (si
nglet 6 H, dimethyl), 2. '531) p
m (singlet 1 H, HC ball), 5.86p
Dm (singlet 1H, -0H), 6.6-7
．． 3pprn(multiplet 8H, aroma
atic H> From the above results, it was confirmed to be an acetylene compound having the following formula structure.

CH3 Methanol 507! The above acetylene compound 149! Add 0.07 g of Lindlar catalyst to the 'IK
A hydrogenation reaction was carried out at the lowest temperature for 7 hours at a hydrogen pressure of Ej/cti+. After the reaction is completed, the catalyst is separated from the furnace, methanol is distilled off, and 1
39 crude crystals (compound 5) were obtained (purity 97.5%).

The analysis results of Compound 5 were as follows.

mp: 57-59°C IR: ~3400cm-' (phenolic OH), 1
640.960rm-' (vinyl), 1385.136
8cm-' (Zeminal, dimethyl) 1H-NMR (CD
Cf3): 1.4Dpm (singlet 6
H, dimethyl), 4.9-5.3 p pm (double
e doublet 2 H, CH2= ), 5.8
~6.2 ppm (multiplet 1 H1=
CH-), 6. I Di)m(singlet 1
Hl-OH>, 6.7~7.0ppm (multi
plet8HSaromatic H> The above analysis results all support the structure of Compound 5.

Example 6 Monoallyl ether of bisphenol F (compound 6.7
) Synthesis (Compound 6) (Compound 7) Bisphenol F (Honshu Chemical Co., Ltd., 0.〇-integral, 0.p
- monolithic, p, p'' monolithic mixture >90 g (0.45 mol)
was dissolved in 200ml of acetone, and a KOH aqueous solution (
When 7 JO of KOH289 (0.5 mol)/water 20 ml) was added and stirred, salt was formed and precipitated. While heating and refluxing this suspension, 2 y of allyl bromide 60y (0.52 mol) was added.
The mixture was added dropwise over a period of time, and after the addition, the mixture was heated under reflux for 4 hours while stirring. After the reaction was completed, acetone was distilled off from the reaction mixture using an evaporator, and the residue was dissolved in benzene and washed with water. Benzene was distilled off and the residue was immersed in silica gel (Me
Chromatography was performed using rCk silica gel 7734)/cyclohexane-benzene system. After the diallyl compound was eluted with cyclohexane, the monoallyl ether of bisphenol F was eluted and separated into the following four fractions by elution with benzene.

1st fraction 6.19 2nd fraction 13.29 3rd fraction 7.1g 4th fraction 19.09 Yield needle 45.4S? The first fraction (compound 6) and the third fraction (compound 7) showed almost single peaks in liquid chromatography analysis.

The analysis results of Compound 6 and Compound 7 were as follows.

Compound 6 (1st fraction) IR: 3400 cm” (phenolic OH), 164
5.985.920cm-1 (vinyl terminal) I H-N
MR (CDCJ3): 3.9ppm (single
t2H1φ-CH2-φ), 4.4ppm (do
ublet 2H, allyl CH2), 5, 1-5.5
pp m (double doublet 2 H
1-terminal vinyl=CH2), 5.7-6.3 pI) m(
mu1 plet 1H, vinyl -〇H=), 6.
6-7.5ppm (multiplet 9H1ar
omatic l-1 and -OH>13C-NMR:
112.01116.4.120.5.121.9.1
26.8.127.7.128. ○, 128.7.13
0.4.130.7.154.2.154.6ppm (
aromatic (:, >30.7 (-C
H2-), 69.6 (allyl CH2), 119.
0.132.3 (C of vinyl group) MS: M 240 Comparison of calculated and measured 13C shift, measurement of proton NOE difference spectrum, and measurement of proton spin decoupling all support the structure of compound 6 .

Compound 7 (3rd fraction) IR: ~3500cm''1 (phenolic OH), 16
50.1000.930cm-1 (vinyl) I H-N
MR (CDCf 3 ):, 3.9 ppm (singl
et 2 @, φ-CH2-φ), 4.4 ppm
(double 2 H, allyl-CH2-), 5
．． 1 to 5.5 ppm (double doublet
2H1 terminal vinyl = CH2), 5.6 ppm (si
nglet 1 Hl-OH>, 5.7-6.3
p p m (multiplet 1 H, allyl -CH=), 6.6-7.3 ppm (multiple
et 8H.

aromatic H) 13CNMR: 114.9.115.7.120.8.
127.4.127.7.129.6.130.8.1
32.1.153.7.157.1ppm (more than aro
matic C) 35.4 ppm (-CH2-), 68.9 pl) m (allyl CH2) 117.6.133.31) l) m (vinyl group C) M
Comparison of calculated and measured S:M 240 13c shift, measurement of proton NOE difference spectrum, and measurement of proton spin decoupling all support the structure of compound 7.

From the above results and the results of IR, NMR, and MS measurements, it can be concluded that the compounds in the front and rear peaks in liquid chromatography are isomers of compound 6 and compound 7, and the first fraction ~
The fourth fraction was identified as the following compound.

Example 7 Synthesis of monoallyl ether of 4.4-dihydroxybenzophenone (compound 8) 4.4-Monodihydroxybenzophenone 60y (0,2
Dissolve 8 mol) in 200 ml of acetone and add KOH to this.
Aqueous solution (KO815,79 (0.28 mol)/water 15d
) was added to form salt.

Allyl bromide 42°33(
0.35 mol) was added dropwise over 55 minutes, and the reaction was continued for an additional 5 hours. After the reaction was completed, the precipitate was removed by decantation after cooling to room temperature, 600 d of ethyl acetate was added to form a solution, and the solution was washed twice with water. From this solution, vinegar and ethyl acetate were removed using an evaporator, and the concentrate was chromatographed using a silica gel (Merck 7734)/chloroform-ethyl acetate system. The solvent of this separated fraction was distilled off to obtain 29.2 g of slightly yellow compound 8 (purity 100%).
.

The analysis results of Compound 8 were as follows.

mp: 122-124℃ IR: 3150cm-1 (phenolic OH), 161
0 cm-1 (carbonyl), 1640.1000.93
0 cm-'(vinyl)' H-NMR (CDCi' 3/da-DMSO):
4.6ppm (double 2H, -CH2-)
, 5.1~5.6DDm (double doublet
2H.

= CH2), 5.8-6.4 D pm (mult
ipletlH, vinyl-〇H=), 6.8-7.9p
pm(multiolet 8H, aromatic
H>, 9.0~10Dpm (singlet, br
oad 1H.

-0H) All of the above analytical results support the structure of compound 8.

Example 8 Synthesis of monoallyl ether of 4.4-thiodiphenol (compound 9) 4.4-thiodiphenol 100 g (0.45 mol)
was dissolved in 400 d of acetone, and KO day aqueous solution (K
33 OH (0.59 mol)/20 ml of water was added and stirred. Further, 65 g (0.53 mol) of allyl bromide was added dropwise thereto at room temperature over 1 hour, and after the dropwise addition, the mixture was heated under reflux for 2 hours.

After the reaction was completed, acetone was distilled off from the reaction mixture using an evaporator, and benzene was added to the residue to dissolve it, washed twice with saturated brine, and finally washed with water.

After distilling off the benzene, the residue was chromatographed using a silica gel (M, Erck silica gel 7734)/benzene system.

A fraction of the target compound 9 was separated as a fraction in which the diallyl compound was eluted and sent. Compound 9 was obtained by distilling off the solvent of this separated fraction.

The results of instrumental measurement and analysis of Compound 9 (yield: 153.1 g (purity: 98.9%)) were as follows.

IR knee 3300cm-' (phenolic OH>, 1
640.980,910 (vinyl) MS: M 2
58'H-NMR (CDCI!3): 4.5 ppm (d
oublet 2 Hl-CH2-), 5.3 pp
m(double doublet 2 H, vinyl=
CH2), 5.7-6.4 ppm (multip
let2H, -CH= and -OH (broad) overlap), 6.5 to 7.4 pl) m (mLlltiplet
8H1 aromatic H) Elemental analysis: CHS Measured value 69.5 5.4 12.5 Theoretical value
69.7 5.5 12.4 All of the above analytical results support the structure of Compound 9.

Comparative Example 1 Synthesis of Orthoallyl Bisphenol A (Comparative Compound 1) CH3 Bisphenol A 90.6y was dissolved in 400ml of acetone, and a KOH aqueous solution (KO 122°43/water 2
0 mf was added to form salt.

60 g of allyl bromide was added dropwise to this at 70° C. while stirring, and the mixture was reacted for 7 hours. After the reaction was completed, acetone was distilled off from the reaction mixture, benzene was added thereto, the mixture was washed with water, and then benzene was distilled off.

The obtained concentrate was purified by silica gel (Merck 7734)/
Chromatography was performed using a cyclohexane-benzene-ethyl acetate system, and the solvent of the separated fractions was distilled off to obtain 52.1 g of bisphenol A monoallyl ether H3 (purity 100%).

The above monoallyl ether 10y was heated at 180° C. for 4.5 hours to perform Claisen rearrangement.

(Silica gel (Merck 7734)
/Chloroform-ethyl acetate system chromatographic separation to obtain the target comparative compound 1.

The yield was 17.3y, and the analysis results of Comparative Compound 1 were as follows.

mpnia 5-77°C' H-NMR (CDCI!3): 1.6ppm (
singlet 6 Hl-CH3), 3. apl
)m(double 2 Hl-CH2-), 4
．． 9~5゜3ppm (double double
2H, CH2= ), 5.5ppm (sinc+le
t broad 2H, -QH>, 5.6 to 6.31
)l)m(mtJItiplet IHl-〇H-)
, 6.5-7.2ppm (mo1℃1plet7H
, aromatic H) Example 9 The compounds obtained in Examples 1 to 8 and Comparative Example 1 and tetraglycidyldiaminodiphenylmethane (Sumitomo Chemical Co., Ltd.
Mutual solubility, pot life, and glass transition temperature of the cured resin (1ELM434)
Physical properties such as Tg) were measured. The results are shown in Table 1.

Note that the equivalents of the phenolic compounds (compounds 1 to 9) of the present invention were calculated assuming that each molecule has two hydroxyl groups, assuming the formation of a molecular groove after completion of rearrangement. The pot life was defined as the time until fluidity (drapeability) and adhesiveness (tackiness) disappeared at 40'C. TQ
For the measurement, a sample of 15,711 g was taken from the cured resin plate.
40°C/mi using Daini Seikodai DSC (580 type)
Measured at a heating rate of n. Here, the cured resin plate was obtained by heating in an oven at 180°C for 2 hours and then at 200°C for 2 hours.

From the results in Table 1, the phenolic compound of the present invention (compound 1
-9) are diol compounds used for comparison (comparative compound 1)
It has a better pot life than . Moreover, it can be seen that a sufficiently cured resin plate can be obtained at a normal curing temperature. That is,
It is clear that it is useful as a curing agent for latent-corrugated epoxy resins.

Example 10 Regarding compound 4, bisphenol A diglycidyl ether (Yuka Shell Co., Ltd. E128) was used as the epoxy resin.
and O-cresol novolac epoxy (Sumitomo Chemical Co., Ltd.)
The physical properties were measured in the same manner as in Example 9, except that ESCN195XL> was used. The results are shown in Table 2.

In addition, 1 phr of aluminum acetylacetonate was added as a curing accelerator together with the curing agent.

From the results in Table 2, it can be seen that the phenolic compound of the present invention is a one-component glycidyl ether type epoxy and has a sufficient pot life, and a cured resin plate can be obtained at a normal curing temperature. That is, it is clear that it is useful as a curing agent for latent wave-type epoxy resins.

<Effects of the Invention> According to the present invention, a novel phenolic compound is provided. This phenolic compound has excellent storage stability when used as an epoxy curing agent, especially as a latent wave type epoxy curing agent, and can quickly cure epoxy resins at normal practical curing temperatures. . That is, it is possible to form an excellent latent wave-type epoxy resin composition.

According to the present invention, an excellent epoxy curing agent is provided.

Claims (4)

[Claims] (1) A novel phenolic compound represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...[I] (In the formula, Y represents CH_2, SO, S, O or CO. Also, A represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_1, R_2, R_3, R_4, R_5 are each (Independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) (2) A novel phenolic compound according to claim 1, which is represented by the following general formula [II]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
・[II] (In the formula, Y represents SO, S, O or CO. Also,
A stands for ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_
1, R_2, R_3, R_4, and R_5 each independently represent a hydrogen atom or a CH_3 group. ) (3) A novel phenolic compound according to claim 1, which is represented by the following general formula [III]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
・[III] (In the formula, A represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_1, R_2, R_3, R_4, and R_5 each independently represent a hydrogen atom or a CH_3 group.) (4) An epoxy curing agent containing a novel phenolic compound represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
・[I] (In the formula, Y represents CH_2, SO, S, O or CO. Also, A represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_1, R_2, R_3, R_4, R_5 are each (Independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)