JPH0625194B2 - Novel epoxy resin manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a novel alicyclic epoxy resin having excellent heat resistance, weather resistance and water resistance.

<< Prior Art >> The most widely used epoxy resin in the industry today is a so-called EPB type epoxy resin produced by a reaction of bisphenol A and epichlorohydrin.

This resin has a wide range of products from liquid to immobilization, and has the advantage that epoxy group is highly reactive and can be cured at room temperature with polyamine.

However, although the cured product has excellent water resistance and toughness, it has disadvantages such as poor weather resistance, poor electrical properties such as tracking resistance, and low heat distortion temperature. .

In particular, recently, epoxy resins obtained by reacting phenol or novolac resins with epichlorohydrin have been used as encapsulating resins for VLSI and the like.
Since it is contained in ppm, it causes problems such as deterioration of electric characteristics of electric parts. An alicyclic epoxy resin is an epoxy resin that does not contain chlorine and has excellent electric characteristics and heat resistance.

These are produced by an epoxidation reaction of a compound having a 5- or 6-membered cycloalkenyl skeleton.

The epoxy group of these resins is a so-called internal epoxy group, which is usually heat-cured with an acid anhydride, but cannot be room-temperature cured with polyamine because of its low reactivity.

Therefore, the use range of the alicyclic epoxy resin is made extremely narrow. Aliphatic epoxy resin (III), (I
Those having the structure of V) are industrially manufactured and used.

<< Problems to be Solved by the Invention >> (III) is used as a heat-resistant epoxy diluent because of its very low viscosity, but it has a problem that it is highly toxic and the operator's skin is significantly rashed. (IV) has few impurities, has a low hue, and has a high heat distortion temperature of its cured product,
Poor water resistance is a problem due to the ester bond.

Furthermore, since (III) and (IV) are both low-viscosity epoxy resins, solid epoxy resin molding systems such as transfer molding cannot be applied.

In view of such problems, the present inventor has conducted earnest studies to develop a new epoxy resin, and as a result, a polyether compound having a vinylcyclohexane skeleton is reacted with an epoxidizing agent to form an alicyclic compound, which has a fast curing terminal. Having an epoxy group, any state from liquid to solid can be obtained, water resistance, heat resistance, excellent electrical characteristics, and found a method for producing an epoxy resin having excellent reactivity, the present invention Completed

<< Structure of Invention >> That is, the present invention relates to "the general formula (I) An unsaturated compound represented by the general formula (II) characterized by reacting with an organic peracid [However, in the general formula (I) and the general formula (II), R ¹
Is a residue obtained by removing a hydrogen atom from an organic compound having 1 hydroxyl group, n1, n2, ..., Nl are 0 or an integer of 1 to 100, and the sum thereof is 1 to 100, and l is 1 to 100. An integer, A is an oxycyclohexane skeleton having a vinyl group, It is represented by. B is an oxycyclohexane skeleton having a substituent and has the following formula It is represented by.

X is -CH = CH ₂ (R ² is any one of H, an alkyl group, an alkylcarbonyl group, and an arylcarbonyl group), At least one is contained in the resin of general formula (II)].

Next, the present invention will be described in detail.

In the novel epoxy resin represented by the formula (II) of the present invention, R ¹ is a residue obtained by removing a hydrogen atom from an organic compound having ¹ hydroxyl group, and has ¹ hydroxyl group as a precursor thereof. Examples of organic compounds include alcohols and phenols.

The alcohol may be a monohydric alcohol or a polyhydric alcohol.

For example, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol and other aliphatic alcohols, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
1.3 butanediol, 1.4 butanediol, pentanediol, 1.6 hexanediol, neopentyl glycol, oxypivalic acid, neopentyl glycol ester, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol , Dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, and other polyhydric alcohols. Examples of phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A,
Examples include bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, phenol novolac resin, and cresol novolac resin.

Further, as the compound having a hydroxyl group, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, polyester polyol resin, Examples thereof include polycaprolactone polyol resin, polypropylene polyol, polytetramethylene glycol, polycarbonate polyols and hydroxyl group-containing polybutadiene, and cellulose-based polymers such as hydroxyethyl cellulose and cellulose acetate.

In addition, a compound having a hydroxyl group is unsaturated 2 in its skeleton.
It may have a heavy bond, and specific examples thereof include allyl alcohol and 3-cyclohexenemethanol.

Any of these organic compounds can be used, and two or more of them may be mixed.

In the general formulas (I) and (II), n1, n2, ... Nl are 0 or integers of 1 to 100, respectively, and the sum thereof is 1 to 100. l represents an integer of 1 to 100. n1, n2, ...
-The sum of nl is 1 to 100, but if it is 100 or more, it becomes a resin having a high melting point, is difficult to handle, and cannot be practically used.

In the general formula (I), A is a oxycyclohexane skeleton having a vinyl group, It is represented by. In the general formula (II), B is an oxycyclohexane skeleton having a substituent, It is represented by.

X is -CH = CH ₂ In Although, At least one in the resin of general formula (II).

R ² is any one of H, an alkyl group, an alkylcarbonyl group, and an arylcarbonyl group.

Among the substituents X of B in the general formula (II), It is essential that at least one is included, The larger the amount, the more preferable.

In particular The less, the more preferable.

That is, in the present invention, the substituent X is Is the main one.

The production of the novel epoxy resin represented by the general formula (II) is a polyether resin obtained by ring-opening polymerization of 4-vinylcycloxene-1-oxide with an organic compound having a hydroxyl group as an initiator, that is, It can be produced by epoxidizing a polyether compound having a vinyl group side chain with an organic peracid.

4-Vinylcyclohexene-1-oxide is obtained by partially epoxidizing 4-vinylcyclohexene obtained by the dimerization reaction of butadiene with peracetic acid or the like.

It is preferable to use a catalyst when polymerizing 4-vinylcycloxene-1-oxide in the presence of active hydrogen.

As the catalyst, amines such as methylamine, ethylamine, propylamine and piperazine, organic basic acids such as pyridine and imidazole, organic acids such as formic acid, acetic acid and propionic acid, inorganic acids such as sulfuric acid and hydrochloric acid, sodium methylate Alkalates of alkali metals such as KOH, Na
Alkali such as OH, BF ₃ , ZnCl ₂ , AlC
l _3, SnCl Lewis acid or its complexes such as _4, triethylaluminum can be mentioned an organic metal compound such as diethyl zinc.

These catalysts can be used in the range of 0.01 to 10%, preferably 0.1 to 5%, based on the starting material.

The reaction temperature is -70 to 200 ° C, preferably -30 ° C to 1
It is 00 ° C.

The reaction can also be carried out using a solvent.

A solvent having active hydrogen cannot be used as the solvent.

That is, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, benzene, toluene,
Aromatic solvents such as xylene, ethers, aliphatic hydrocarbons, esters and the like can be used.

The 4-vinylcycloxene-1-oxide having a vinyl group side chain thus synthesized can be epoxidized with an epoxidizing agent to produce a novel epoxy resin represented by the general formula (II). It is essential to use organic peracids as the epoxidizing agent.

As organic peracids, formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like can be used. Of these, peracetic acid is a preferable epoxidizing agent because it is industrially available at low cost and has high stability. A catalyst may be used in the epoxidation, if necessary.

For example, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the physical properties of the equipment and raw materials.

The reaction temperature range that can be used depends on the reactivity of the epoxidizing agent used.

Peracetic acid, which is a preferred epoxidizing agent, is 0-
70 ° C is preferred. At 0 ° C or lower, the reaction is slow, and at 70 ° C, decomposition of peracetic acid occurs.

The solvent can be used for the purpose of reducing the viscosity of the raw material and stabilizing it by diluting the epoxidizing agent.

In the case of peracetic acid, aromatic compounds, ether compounds,
An ester compound, a ketone compound, etc. can be used as a solvent.

The charged molar ratio of the epoxidizing agent to the unsaturated bond can be changed according to the purpose such as how much unsaturated bond is desired to remain.

When a compound having a large number of epoxy groups is intended, the epoxidizing agent is preferably added in an equimolar amount or more with respect to the unsaturated group.

However, it is usually disadvantageous to exceed 2 times the molar amount in view of economical efficiency and side reaction problems described below.
A 1.5-fold molar amount is preferred.

Depending on the conditions of the epoxidation reaction, the epoxy value of the olefin bond and the substituents in the raw material And comes to As a result of reacting with the epoxidizing agent, a modified substituent is generated and contained in the target compound.

The ratio of the three groups of the substituent and the modified substituent in the target compound is determined by the kind of the epoxidizing agent, the molar ratio of the epoxidizing agent-olefin bond and the reaction conditions. When the epoxidizing agent is peracetic acid, the modified substituent mainly has a structure as shown below and is generated from the generated epoxy group and by-product acetic acid.

The target compound can be taken out from the reaction crude liquid by ordinary chemical engineering means such as concentration.

[Effects of the Invention] The present invention will be described below with reference to examples.

Example-1 116 g (2 mol) of allyl alcohol, 496 g (4 mol) of 4-vinylcyclohexene-1-oxide and B
3.1 g of F ₃ etherate was mixed at 60 ° C. and reacted until the conversion of 4-vinylcyclohexene-1-oxide was 98% or more by gas chromatography analysis.

Ethyl acetate was added to the obtained reaction crude liquid and washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous liquid.

As a result of infrared absorption spectrum analysis of the structure of the obtained polyether compound, 810 and 850 cm ⁻¹ found in the raw material were obtained.
Absorption by the epoxy group of
Absorption due to ether bond exists at ⁰ , 1150 cm ^-1, and allyl alcohol in the product is trace amount by gas chromatography analysis, but absorption of OH group remains at 3450 cm ^-1 in infrared absorption spectrum. From this, it was confirmed that this compound has a structure represented by the following formula.

_{CH 2 = CHCH 2 -O [A} ] n -H (n = average 2) A is Represents

434 g of this compound was dissolved in ethyl acetate and charged into a reactor, to which 388 g of peracetic acid was added as an ethyl acetate solution.
Dropped over time. During this period, the reaction temperature was kept at 40 ° C. After the addition of peracetic acid was completed, the mixture was aged at 40 ° C. for 6 hours.

Ethyl acetate was added to the reaction crude liquid, and the mixture was washed with alkaline water containing 416 g of sodium carbonate and then well with distilled water.

The ethyl acetate layer was concentrated to give a viscous transparent liquid. This compound had an oxirane oxygen content of 9.97%, and absorption by an epoxy group was observed at 1260 cm ^-1 in an infrared absorption spectrum.

Furthermore, the absorption by the vinyl group is seen in 1640 cm ^-1, absorption by the OH group in 3450 cm ^-1, 1730 cm ^-1
To Since the absorption by the compound is observed, the compound is represented by the structure (R ¹ ,: glycidyl ether group or allyl group of the general formula (I),
It was confirmed that n = average 2, including a part of a group obtained by adding acetic acid to an epoxy group).

Example-2 In the same manner as in Example-1, 158 g of allyl alcohol,
868 g of 4-vinylcyclohexene-1-oxide and 4.7 g of BF ₃ etherate were reacted to obtain a viscous liquid product.

In the infrared absorption spectrum of the product, the absorption due to the epoxy groups at 810 and 850 cm ^-1 found in the raw material has disappeared, the absorption due to the ether bond at 1080 and 1150 cm ^-1 exists, and it was generated by gas chromatography analysis. Although the amount of allyl alcohol in the product was a trace amount, it was confirmed from the infrared absorption spectrum that an OH group was absorbed at 3450 cm ^-1 , and thus this compound was confirmed to have a structure represented by the following formula.

_{CH 2 = CHCH 2 -O [A} ] n -H (n = average 7) A is Represents

Further, 492 g of this compound and 395 g of peracetic acid were reacted in the same manner as in Example 1 to obtain a viscous transparent liquid. This compound has an oxirane oxygen content of 9.27%, and the absorption by an epoxy group at 1260 cm ^-1 in the infrared absorption spectrum,
The absorption by the residual vinyl group was observed in 1640 cm ^-1, absorption by the OH group in 3450 cm ^-1, the 1730 cm ^-1 Since the absorption by the compound is observed, the compound is represented by the structure (R ¹ ,: glycidyl ether group or allyl group of the general formula (I),
It was confirmed that n = 7 on average, including a part of a group obtained by adding acetic acid to an epoxy group).

Methanol 64g in the same manner as in Example -3 Example -1, 4-vinylcyclohexene-1-oxide 744g and BF ₃
4.1 g of etherate was reacted to obtain a viscous liquid product.

In the infrared absorption spectrum of the product, the absorption due to the epoxy groups at 810 and 850 cm ^-1 found in the raw material has disappeared, the absorption due to the ether bond at 1080 and 1150 cm ^-1 exists, and it was generated by gas chromatography analysis. Although the amount of allyl alcohol in the product was a trace amount, it was confirmed that the present compound has a structure represented by the following formula, since it has an OH group absorption at 3450 cm ⁻¹ in the infrared absorption 0 spectrum.

CH ₃ —O [A] _n —H (n = average 3) A is Represents

Further, as in Example-1, 573 g of this compound was reacted with 387 g of peracetic acid to obtain a viscous transparent liquid. This compound has an oxirane oxygen content of 9.03% and has an infrared absorption spectrum at 1260 cm ^-1, which is absorbed by an epoxy group.
The absorption by the residual vinyl group was observed in 1640 cm ^-1, absorption by the OH group in 3450 cm ^-1, the 1730 cm ^-1 It was confirmed that the present compound has the structure of the general formula (I) (R ¹ ,: methyl group, n = average 3, partly including a group in which acetic acid is added to an epoxy group).

Example-4 134 g (1 mol) of trimethylolpropane and 1863 g (15 mol) of 4-vinylcyclohexene-1-oxide were reacted in the same manner as in Example-1 to obtain a viscous liquid product.

The obtained product was analyzed by elemental analysis, IR and NMR, and it was confirmed that this compound had a structure represented by the following formula.

A is Represents

In the IR absorption spectrum, the absorption due to the epoxy groups at 810, 850 and 1850 cm ⁻¹ found in the raw material as in Example 1 disappeared, and the absorption due to the ether bond was newly generated at 1080 cm ⁻¹ . Furthermore, absorption by vinyl groups remains at 910 and 1640 cm ^-1 .

The same peak as in Example-1 was confirmed by NMR. The elemental analysis values are shown below.

From the above results, it was confirmed that this compound has a structure represented by the formula (I).

Further, as in Example-1, 573 g of this compound was reacted with 387 g of peracetic acid to obtain a viscous transparent liquid.

This compound had an oxirane oxygen content of 9.03% and showed characteristic absorption due to an epoxy group at 1260 cm ^-1 in an infrared absorption spectrum.

Furthermore, the observed absorption by residual vinyl group 1640 cm ^-1, absorption by the OH group in 3450 cm ^-1, 1730
cm ^-1 Since the absorption by the compound is observed, the compound is represented by the structure (R ¹ ,: trimethylolpropane residue, l = 3,
It was confirmed that n1, n2, and n3 = 5 on average, including some groups in which acetic acid was added to the epoxy group).

Reference Example The total chlorine content in the epoxy resins synthesized in Examples-1, 2 and 3 was measured.

For the measurement, about 2 g of the sample material was weighed, decomposed and burned with oxygen, and the results shown in Table 1 were obtained. In a general epoxy resin starting from epichlorohydrin, total chlorine is several hundred pp
It can be seen that the total chlorine of the resin of the present invention is very small considering that it contains m.

Application Example 1 A curing agent was added to the products obtained in Examples 1, 2, and 3 to measure gel time, and the curability of the epoxy resin was examined. A novolac type phenol resin [PSF-4300, Gunei Chemical Industry Co., Ltd.] was used as a curing agent, and 2-undecylimidazole [Curezol C ₁₁ Z, Shikoku Chemical Industry Co., Ltd.] was used as a curing catalyst.

As a comparative resin, 3,4-epoxycyclohexylmethyl-3,4, which is a typical alicyclic epoxy resin, is used.
-Epoxycyclohexanecarboxylate [Celoxide 2021, Daicel Chemical Industries, Ltd.] was blended according to the following formulation, melt-mixed at 120 ° C for about 1 minute, and then cooled to obtain a formulation. JIS-
The gel time was measured at 120 ° C. by C2104-7 (hot plate method), and the results in Table 2 were obtained. It can be seen that the resin of the present invention has higher curability than conventional alicyclic epoxy resins.

Compounding formulation Epoxy resin 1.0 equivalent PSF-4300 1.1 equivalents Curezol C11Z 0.7% by weight (relative to the composition) Application Example 2 Using the compounds obtained in Examples 1, 2, and 3, the physical properties of cured products were measured.

The same cured product and curing catalyst as in Application Example 1 were used, and the following formulation was mixed in the same manner as in Application Example 1 to obtain a formulation. The obtained compound was crushed and press-molded to obtain a test piece. Molding is under pressure of 90-100 kgf / cm ² ,
The temperature was raised from 60 ° C to 170 ° C in about 30 minutes, and post-curing was performed for 2 hours in an oven set to 180 ° C. The obtained cured product was cut into a test piece city, JIS-K-6.
The physical properties were measured according to 911, and the results shown in Table 3 were obtained.

Compounding formulation Epoxy resin 1.0 equivalent PSF-4300 1.1 equivalents Curezol C ₁₁ Z 0.7% by weight (based on the formulation)

Claims (1)

[Claims] 1. A general formula (I) An unsaturated compound represented by the general formula (II) characterized by reacting with an organic peracid [However, in the general formula (I) and the general formula (II), R ¹
Is a residue obtained by removing a hydrogen atom from an organic compound having 1 hydroxyl group, n1, n2, ..., Nl are 0 or an integer of 1 to 100, and the sum thereof is 1 to 100, and l is 1 to 100. An integer, A is an oxycyclohexane skeleton having a vinyl group, It is represented by. B is an oxycyclohexane skeleton having a substituent and has the following formula It is represented by. X is -CH = CH ₂ (R ² is any one of H, an alkyl group, an alkylcarbonyl group, and an arylcarbonyl group), At least one is included in the resin of the general formula (II). ] The manufacturing method of the novel epoxy resin represented by these.