JPS58142908A - Preparation of polyepoxy compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound, having improved heat resistance, electrical and tensile characteristics, and useful as molding materials, etc., by condensing glyoxal with a phenol, removing the unreacted substances, etc. to give a specific methylol content, and reacting the resultant condensation product with an epihalohydrin. CONSTITUTION:One mole glyoxal is condensed with 2.1-3.0mol phenol in the presence of an acid catalyst to give a polyphenol, and the unreacted phenol and water formed as a by-product are removed from the resultant product. The methylol groups remaining in the polyphenol are then condensed with the polyphenol and phenol through dehydration to give <=5% methyl group content. The resultant condensation product is then reacted with an epihalohydrin or beta- methylepihalohydrin to afford the aimed compound consisting of polyglycidyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an epoxy compound that provides a cured product with excellent heat resistance, electrical properties, and tensile properties. Useful as mold material, impregnation material, adhesive, and sealant.

Traditionally, epoxy resin has been used for its excellent electrical insulation, adhesive properties,
Due to its mechanical strength and heat resistance, it can be used as a sealant for electrical and electronic parts, CF
It is widely used in RP matrices, paints, adhesives, etc.

Various epoxy compounds such as glycidyl ether type and glycidyl ester type are known as polyfunctional epoxy compounds for epoxy resins. However, the types and physical properties of the publicly available polyfunctional epoxy compounds are not necessarily sufficient to satisfy all the various resin applications in terms of curing properties, curing speed, etc. .

For example, a bifunctional epoxy compound obtained by reacting bisphenol A, epichlorohydrin, and an aqueous solution of caustic soda has a low heat distortion temperature, and when kept at high temperature for a long time, the strength of the bend decreases and the weight decreases. It has major drawbacks.

In addition, the shell chemistry equation represented by the following formula α)
Although jO1,1 overcomes the drawbacks of the aforementioned difunctional epoxy compounds, it is not currently commercially available.

IJ This 01g-functional epoxy compound is obtained by condensing phenol, glyokyl, and t-acid catalyst in the presence of a t-acid catalyst.・(1) Enol, isolated from by-produced water, is produced by reacting this with Ebichlor and Dorino (U.S. Patent No. 1.111)
Is Lm @ No. 1, see specification No. 8.013.087), and production of the above polyphenol 0Ill
The molecular weight of the product and the content of the phenol skeleton (hereinafter referred to as ``nuclear body'') are determined by the mixing ratio of O phenol and G11 oxazole.
It is known that polyphenols with different high molecular weights have a life-long life. The amount of O1s molecular weight O polyphenol decreases as the molar amount of phenol used per 1 mol of Griot is smaller, that is, closer to 4 mol <S
When X<□, the proportion of □ in the produced polyenol of the tetranuclear polyphenol shown by the above formula is dangerously low.

The process of producing the polyepoxy compound represented by formula (1) by reacting the polyphenol represented by the above formula (seal) with epichlorohydrin is as follows: is obtained, followed by a step of dehydrochlorination with an alkali.

However, the polyepoxy compound obtained by the method described in this patent has the following drawbacks.
(1) Contains 1 to 6 gel body tubes by weight.

[No] The content of saponifiable chlorine is high at 1.0□ to 2% by weight.

The mechanical strength of the cured product obtained when the amount of gel body increases,
Heat resistance is impaired. A high content of movable chlorine impairs the electrical properties of the cured product, and also has the drawback of increasing acoustic corrosion of laminated and encapsulated metals.

The inventor's eyes are the manufacturing method described in the above-mentioned US Patent Specification, α
) and (11), it was found that the polyphenol before reacting with epichlorohydrin contains polyphenols with 1 active methylol group (＼＼｜ﾓ＼ﾓ) as shown by the following formula ゛ between 5” and 13/wt. It was concluded that this active methylol group undergoes a dehydration condensation reaction with the phenolic hydrogen group to produce a three-dimensional structure as a by-product. It has been found that the generation of such gel bodies can be reduced by allowing 111t- of such gel bodies to be produced, leading to the present invention.

H H [11 is o-so alignment] That is, the present invention uses a polyphenol extracted by a condensation reaction of glyoxypur and phenols, and shrimp...hydrin ta is an I-methyW lohydrin ν. In the method of reacting a polyepoxy compound tm, the polyepoxy compound O#! is characterized by passing through the next O step. Step 1, which provides a production method: 1 mol of griot and 2.1 to 307 phenols
A second step of condensing the polyphenol with the polyphenol in the presence of an acid catalyst to obtain a polyphenol: A third step of removing unreacted phenols and dead water from the polyphenol produced: The remaining methylol group of the above polyphenol is converted into a polyphenol and a polyphenol. The first decoy process S=' makes the content of the methylol group less than S- by dehydration condensation reaction with enols. - React to produce polydalicidyl ether.

Next, the content of the present invention will be explained in more detail. I will clarify.

The first step of polyphenol production is glyoxal 1
phenol 1lt-2, 1 to 30 mol, preferably 7 to 16 mol per mole, and 4O-1 in the presence of an acid catalyst F.
50C, preferably 7G-1$OC at normal pressure or 1'~
3 to 20 hours, preferably 3 to 8 hours under pressure of Sq/-
This is done by reacting for a period of time.

Phenols include monohydric phenols such as phenol, cresol, and alkylphenol; bisphenol F
, bisphenol A, catechol, resorcinol, and other polyhydric phenols. Among these, phenol
Monohydric phenols, such as cresol and para-butylphenol, which have an alkyl group having 1 to 5 carbon atoms, are more preferable than polyhydric phenols because of their ability to form gels and their ease of handling in reactions. .

Examples of the acid catalyst include sulfuric acid, hydrochloric acid, p-)luenesulfo/acid, and among these, gaseous hydrochloric acid or an aqueous solution of hydrochloric acid is preferred. These acid catalysts are glyoxal 1
It is used in a ratio of 0.1 to 10 moles to 0 moles.

The polyphenol thus produced contains a polyphenol having an active methylol group in a proportion of 5 to 10% by weight, depending on the mole tKt of the phenol used.

If phenols are used in excess of more than 4 moles in the reaction of this Kiichi step, it is difficult to reduce the content of polyphenols having methylol groups to less than S weight even if the reaction is continued further.

Therefore, in the present invention, the water produced in the second process and the water removed from the produced polymer enable the phenol@0 condensation reaction with the active methyl group of the polyphenol, thereby substantially converting the methylol group of the polyphenol. To &<
This prevents the formation of gel bodies.

Note that the second process S is a process for removing by-product water from the product, but since it is generally difficult to separate water and phenols, papermaking is carried out by distilling them together under reduced pressure. Depending on the acid catalyst Ota@, some O may be distilled off together with water.
In that case, the insufficient amount O acid catalyst tf in the third root
I & Add.

The reaction for reducing active methyl groups in polyphenols in the third step can be carried out under the same temperature and pressure conditions as in the first step. The amount of phenols charged Fio, s~3 times the weight of polyphenols. After the reaction is completed, unreacted phenols are distilled off under reduced pressure together with by-produced water.

If necessary, the obtained polyphenols are thoroughly washed with water and dried.

Polyphenols and shrimp halohydrin of the fourth type are friends!
-Methylevihalohydrin and 1-The methods for carrying out the epoxy compound as a raw material include a one-step method in which the addition reaction and dehydrohalogenation reaction are carried out at once using a (he)alkali, and There is a two-step method in which an addition reaction is first carried out using a catalyst, followed by a dehydrohalogenation reaction with an alkali, but the latter two-step method is preferred in terms of yield and product quality. preferable.

The above shrimp halohydrin and! -Methyl shrimp halohydrin (hereinafter referred to as "shrimp halohydrin")
As a company, such as epichlorohydrin, shrimp bromohydrin,! -Methyl Ebbromohi F'Jy and/-Methyl Ebbromohi)-17. The amount of "epihalohydrin" used is 8 to 10 mol, preferably 12 to 16 mol, per 1 mol of raw material polyphenol. Excessive use of shrimp halohydrin can be recovered by distillation and reused.

Examples of the alkali include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, potassium carbonate, and sodium carbonate, with sodium hydroxide and potassium hydroxide being preferred.

Furthermore, the catalysts used in the two-step process (above) include, for example, tetramethylammonium chloride, tetraethylammonium bromide, triethylmethylammonium chloride, tetraethylammonium iodide,
・11IN such as cetyltriethylammonium blonde
Examples include phosphonium salts such as tetramethylphosphonium talolide and methyltriphenylphosphonicumpronde.

The amount of alkali used is at least 42 mol, usually 2.02 to 2.2 mol, per 1 mol of raw material polyphenol. The alkali is added to the reaction system in the form of solid particles and in the form of an aqueous solution. The amount of a catalyst such as a quaternary ammonium salt used is usually about 0.05 to 3.0 parts by weight per 100 parts by weight of polyphenol as a raw material.

The reaction temperature varies depending on the type of reaction, but is usually 5.
0" to 120"C, preferably -6 to 116"C
The reaction time is until the reaction is actually completed, and varies depending on the reaction temperature, etc., but is usually between O.S. and 10 W@, preferably between 111 L and 8 hours.

After completion of the reaction, excess "Herohydrin" and water were removed under reduced pressure, and the by-produced a2potassium 10-genide TF
Depending on p, a single polyepoxy compound can be obtained.
The polyepoxy resin produced through the first step and the fourth step is usually melted in an organic solvent such as methyl isobutyl ketone, toluene, or benzene, and washed repeatedly with water to remove the alkali halide salt. Possible dark circles 9 removed,
It is further purified by removing the organic solvent r*.

The polyepoxy compound thus produced has a low saponifiable hydrogen content of 0.1 weight or less and a low gel content, so it is useful as a resin for the electronic industry.

The tetrafunctional epoxy compound thus produced can be used alone or in combination with other epoxy compounds to produce epoxy iu.
It can be used as t. That is, if this tetrafunctional O epoxy compound alone or in combination with one or more other epoxy compounds is subjected to a curing (crosslinking) reaction with an appropriate curing agent, the thermal property The result is an extremely excellent cured product. There are no particular restrictions on the other epoxy compounds used in combination, and various epoxy compounds may be used in combination depending on the intended use. Other epoxy compounds to be used in combination include, for example, polyglycidyl ethers such as bisphenol A or bumo bisphenol, phthalic acid, polyglycidyl esters such as cyclohedonadicarboxylic acid, and organic acids such as tjL157ta acid. Anhydrides: urea derivatives such as diquandiand, melaon, and guanamine; l11g group boria f such as triethylenetetramine, diethylenetriane, xylylenethiadine, isophoronediamine, etc.
and adducts thereof with epoxy compounds such as ethylene oxide and propylene oxide, or acrylic compounds such as acrylonitrile and acrylic acid, etc. can be used.

Furthermore, in addition to a curing agent, the curable epoxy-fatty compound using the four-functional epoxy compound obtained by carrying out the present invention may optionally contain a lubricant, an organic solvent, a reactive diluent, etc. Various additives such as additives, extenders, fillers, reinforcing agents, pigments, flame retardants, thickeners, and flexibility agents can be blended.

The cured product obtained by blending this polyepoxy compound obtained by carrying out the present invention and curing it in a resin composition has a heat distortion temperature higher than that of conventional general-purpose bisphenol-based polyepoxy compounds. The thermal properties of the paper are extremely superior, and the mechanical properties are the same or better.

A more specific theory #4t is given below with examples,
These Examples are illustrative only, and the present invention is not limited to the Examples. Note that parts and numbers in the examples are based on weight.

Example 1 Glyoxal 58i1 (40-aqueous solution), 171 parts of phenol, and 12 parts of 36-hydrochloric acid aqueous solution were placed in a 1-liter flask equipped with a condenser, stirrer, and thermometer, and the temperature was raised to 100°C with vigorous stirring to approx. After the reaction was completed for 6 hours, the pressure inside the reaction system was reduced to about 1O-H1, and the is
Polyphenol α) by removing unreacted phenol at o~151OC! I got 10I11.

The active methylol group content of this polyphenol 011 was approximately 11).

Incidentally, the content of active methylol groups was calculated from the intensity ratio of the sample t-tortoise dichloroform K11 solution and the nuclear aerosol resonance spectrum [adjusted].

Example 2 35 parts of a polyphenol ring was prepared in the same manner as in Example 1, except that O-cresol was used instead of phenol.

The residual active methylol group content of this polyphenol O is approximately 1
%Met.

Example 1 0200 parts of the polyphenol obtained in Example 1, 150 parts of phenol, and 117 parts of 3-hydrochloric acid were charged into a flask and stirred at 190°C for 6 hours.

After the reaction is completed, reduce the pressure in the reaction system to f#10 ankle,
Unreacted phenol was removed at 160-180C to obtain polyphenol@1.

The remaining active methyl group-containing 1llF of this polyphenol
i was about i, o-.

Example 2 In the above Example 1, the polyphenol
The polyphenol (1) obtained in 20ON61- was used in the same way except that 11l of 0-cresol 17g was used instead of phenol to obtain 24gm1t of poly7 eryl fl).The content of residual active methylol groups in this polyphenol was about 1
．． It was i Is.

Production Examples of Polyepoxy Compounds Example 1 The polyphenol @1i0i1S obtained in Example 1, 97410 parts of eviqualhydride, and tetramethylammonium bromide, s@Vr, a three-lobe flask equipped with a temperature change needle, a cooler, and a pushing device. Pour into a container and let it react at 1℃ for 3 hours.

Then, the reaction solution was cooled to vr@OC, and the water separator r**
After attaching, sodium hydroxide, 99%, 48-
Water Sat, beaked for about 8 hours. At this time, the reaction source fl'! The reaction was carried out while maintaining the temperature at the azeotropic temperature of vitalolhydrin and water, and removing the water produced.

After the completion of dropping the aqueous solution of 13 rim, remove the remaining epichlorohydrin from the system under reduced pressure, and add 2 mfj parts of methyl isobutyl ketone and ts of pure water to the remaining product.
o@1 added. Thereafter, the organic layer was further washed two to three times with the same amount of water, and finally, methyl isobutyl ketone was distilled off from the organic layer under reduced pressure to obtain the desired polyepoxy compound in a yield of 9$.

The physical properties of this polyepoxy compound were as follows.

Epoxy equivalent zoo (theoretical value 18S) Saponifiable chlorine content 0.04 points ■t Gel content Approximately 04 Comparative Example 1 Same as above except that the polyphenol σ〉 obtained in Example I was used instead of JDK polyphenol σ〉 obtained in Example I. A polyepoxy compound having the following physical properties was obtained by VC at a yield of 5. 1k per epoxy 212 Saponifiable chlorine content 1.2 Melting point 17C !J!Example 2 In Example 1, 160 parts of polyphenol (v) obtained in Example 2 was used instead of 160 parts of polyphenol-). A polyepoxy compound having the following physical properties was obtained in the same manner as in Example 1.

Epoxy equivalent Snow 10 Saponifiable chlorine content o, os Melting point 92c Gel content Approx. A polyepoxy compound having the following physical properties was obtained in the same manner except that the polyphenol obtained in the above example was used as a substitute for polyphenol D.

Epoxy equivalent zs.

Saponifiable chlorine content 1.8 Chronic melting point 0c Gel content 5.8 Manufacturing example of cured product Polyepoxy compound 10 obtained in Example 1 or Comparative Example 1
0 parts, anhydrous methylnazic [I! 80 parts and N,N-dimethylbenzylamine 111 as a curing accelerator at 7 oc. After degassing for 10 minutes under reduced pressure of OmH9, it was injected into a casting sheet metal mold, precured with SO for 3 hours, heated at 150°C for 3 hours, and then heated at 200°C for 3 hours to completely cure. ,vertical! s・-
A cured product with a width of 1 s/-1 and a thickness of 3 cm was obtained.

The physical properties of this cured product are shown in the following table.

Claims (1)

[Claims] (1) In a method for producing a polyepoxy compound tm by reacting a polyphenol obtained by a combined reaction of Da9 oxypur and phenols with Ebihatte90 hydrin or I-methyl halohydrin, the following O step is carried out. s
A method for producing a polyepoxy compound according to the method No. S: Condensation of 1 mole of Grio-Yozuichiru and mol of phenols IILI to SO under an acid catalyst under a cloth to obtain a polyphenol.
. Second step: The third step S= removes unreacted phenols and by-produced water from the produced polyphenols. The remaining methylol group O content of the polyphenol is reduced to below ts by subjecting the polyphenol to a t-dehydration condensation reaction with phenols.
. Fourth step: producing polydalicidyl ether by reacting the polyphenol obtained in the above step with shrimp halohydrin or I-methyl shrimp halohydrin 7