JPH03123775A - Epoxy compound - Google Patents

Abstract

NEW MATERIAL:An alicyclic epoxy compound. USE:Epoxy resins. These resins are highly resistant to heat, weathering and water, being high in softening temperature and having blocking resistance, thus being useful in wide applications such as sealers for ICs, LSIs and LEDs, matrix resins for composite materials and coatings. PREPARATION:4-Vinylcyclohexene-1-oxide and a compound having two epoxy groups are added to an active hydrogen-carrying organic compound (e.g. trimethylolpropane) in the presence of a catalyst (e.g. BF3 etherate) at -20-200 deg.C to effect copolymerization into a polyether compound. This compound is then epoxidized using a peracid and a hydroperoxide to obtain the objective epoxy compound.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a novel alicyclic compound obtained by epoxidizing a polyether compound having both an ether group and a vinyl double bond using an epoxidizing agent. Relating to the formula epoxy compound.

More specifically, the present invention relates to a novel alicyclic epoxy compound that has excellent heat resistance, weather resistance, and water resistance, and has improved blocking resistance due to an increased softening temperature.

[Prior Art] Epoxy resins, which are currently widely used in industry, are produced by the reaction of bisphenol and epichlorohydrin. It is a so-called epi-bis type epoxy resin.

This resin can be used in a wide range of products, from liquids to solids, and has the advantage that the epoxy group has high reactivity and can be cured at room temperature with polyamines.

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

In particular, recently, epoxy resins made by reacting phenol or novolak resin with epichlorohydrin have been used as sealing resins for VLSIs, etc., but t! There are 1 number of chlorine in 1 fat.
It contains 100pp, which causes problems such as deteriorating the electrical characteristics of electrical parts. Alicyclic epoxy resins are examples of epoxy resins that do not contain chlorine and have excellent electrical properties and heat resistance.

These are produced by epoxidation reaction of compounds having a 5R ring and a 6-membered cycloalkenyl skeleton.

The epoxy groups of these resins are so-called internal epoxy groups and are usually cured by heating with acid anhydrides, but cannot be cured at room temperature with polyamines due to their low reactivity.

Therefore, the scope of use of alicyclic epoxy resins is extremely narrow.

As the alicyclic epoxy resin, the following (111) is used.

(Those having the structure m are manufactured industrially.

It is used.

1 [Problem to be solved by the invention] However, (111) is used as a heat-resistant epoxy diluent because of its extremely low viscosity;
It is highly toxic and causes severe skin irritation to workers.

Although (IV) contains few impurities, has a low hue, and has a high heat deformation temperature of its cured product, it is susceptible to ester bonds and has poor water resistance.

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

Against this background, Japanese Patent Application Laid-Open No. 166675/1983 (
=USP 4,565,859), a new epoxy resin having an oxycyclohexane skeleton was proposed.

However, the expository resin disclosed in JP-A No. 60-166675 has only a relatively low softening temperature.

Therefore, the epoxy resin produced by the above method is prone to blocking especially when left under high temperature in summer.
It was used with the addition of anti-blocking agents such as calcium stearate.

However, the addition of antiblocking agents results in a loss of versatility.

Furthermore, in addition to the purpose of solving the above-mentioned problems, the uses of epoxy resin are becoming more diverse.
Depending on the method and purpose of use, products with various performances such as those with a higher softening temperature, those with excellent water resistance and flexibility, etc. are required.
It has become necessary to modify the epoxy resin disclosed in JP-A-60-166675.

This is the result of studies conducted by the inventors based on this situation.

An epoxy compound obtained by epoxidizing a polyether compound obtained by addition copolymerizing 4-vinylcyclohexene-1-oxide and a compound having two or more epoxy groups with a compound having one or more active hydrogen is an epoxy compound. It has a higher softening temperature than a case where a compound having two or more groups is not copolymerized. That is, the inventors have found that the blocking resistance is improved and that excellent properties in various respects such as heat resistance, water resistance, flexibility, and glass transition temperature are not lost, leading to the present invention.

(Structure of the Invention) That is, 1 the present invention is a polyether compound obtained by addition copolymerizing 4-vinylcyclohexene-1-oxide and a compound having two or more epoxy groups with a compound having one or more active hydrogen. "Epoxy compound obtained by epoxidizing" Next, the present invention will be described in detail.

In the novel epoxy compound of the present invention and its raw material polyether compound, organic compounds having active hydrogen include alcohols, phenols, carboxylic acids, amines, thiols, and the like.

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

For example, aliphatic alcohols such as methanol, ethanol, propatool, butanol, pentanol, hexanol, octanol, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol1. triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
1.3 butanediol, 1.4 butanediol, betanediol, 1.6 hexanediol, neopentyl glycol, oxypivalic acid neopentyl glycol ester, cyclohexane dimetatool, glycerin, diglycerin, polyglycerin, trimethylolpropane, Examples include polyhydric alcohols such as trimethylolethane, pentaerythritol, and dipentaerythritol.

Examples of phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4°-dihydroxybenzophenone, bisphenol S, phenol resin, and cresol novolac resin.

Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecanoic acid, trimellitic acid, pyromellitic acid,
Examples include polyacrylic acid, phthalic acid, isophthalic acid, and terephthalic acid.

Also included are compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid.

Amines include monomethylamine, dimethylamine,
monoethylamine, diethylamine, propylamine,
Monobutylamine, dibutylamine, pentylamine,
Examples include hexylamine, cyclohexylamine, octylamine, dodecylamine, 4.4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, and ethanolamine.

Examples of thiols include mercapto compounds such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol esters of mercaptopropionic acid, such as ethylene glycol dimercaptopropionic acid ester, trimethylolpropane trimercaptopropionic acid, Examples include pentaerythritol pentamercaptopropionic acid.

In addition, examples of compounds having active hydrogen include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, droxyethyl cellulose,
Examples include acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin, polypropylene polyol, polytetramethylene glycol, and the like.

In addition, compounds with active hydrogen have unsaturated 2:! I! It may have a bond, and specific examples include:
Examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, and tetradolphthalic acid.

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

4-vinylcyclohexene-1-oxide in the present invention is a compound represented by the following formula, and is industrially produced by partially epoxidizing 4-vinylcyclohexene obtained by duplexing butadiene with peracetic acid, hydrogen peroxide, etc. has been done.

The compound having two or more epoxy groups in the present invention may be any compound having two or more epoxy groups in the molecule.

These can be used alone or in combination of two or more.

For example, alicyclic epoxy resins such as epoxy resins, glycidyl ethers of polyalcohols and polyglycols such as [where R is a hydrogen atom or an alkyl group], polyolefin epoxy resins such as epoxidized soybean oil and epoxidized linseed oil.

Heterocyclic epoxy resins such as diglycidyl hydantoin and triglycidyl isocyanurate, glycidylamine resins such as tetraglycidyl diaminodiphenylmethane and triglycidyl P-aminophenol, and diglycidyl phthalate esters.

Examples include glycidyl ester resins such as diglycidyl esteryl tetradolphthalate, glycidyl ester resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and novolac type epoxy resins.

The polyether compound, which is a precursor of the novel epoxy compound of the present invention, is prepared by combining the aforementioned compound having one or more active hydrogens, 4-vinylcyclohexene-1-oxide, and a compound having two or more epoxy groups in the presence of a catalyst. It can be obtained by reaction.

In this case, in the polyether compound obtained, 4-
Vinylcyclohexene-1-oxide and compounds having two or more epoxy groups include linear structures in which they are randomly bonded to each other through ether bonds formed by ring opening of their epoxy groups, and some also include crosslinked structures. Change in structure.

The key point of the present invention is that this partially crosslinked structure is introduced into the molecule, and is thought to contribute to increasing the softening temperature of the resulting epoxy compound, that is, improving blocking resistance.

In addition, depending on the reaction conditions described below, the epoxy group may be
There may be cases where some epoxy groups in a compound having more than 1 epoxy groups remain.

In the compound having one or more active hydrogen atoms used as an initiator in the present invention, the residue of the alkyl moiety, the ether group, and the terminal hydrogen atom remain in the epoxy compound.

For example, when trimethylolpropane CH3CH2C(CH20H) 3 is used as a compound having one or more active hydrogens, residues and terminal hydrogen atoms remain in the following structure in the resulting polyether compound.

CH3CH2C(CH2O)3(Y)nH3(I) [However, in formula (I), n is a natural number from 3 to 100, and a compound having one or more active hydrogens used in the reaction and 4-vinylcyclohexene-1 - Determined by the usage ratio of oxide and a compound having two or more epoxy groups, Y is 4-vinylcyclohexene-1-oxide and a compound having two or more epoxy groups. An ether bond formed by ring opening of the epoxy group moiety A random bond structure bonded with , a partially cross-linked structural part, and a structure in which more than 22 molecules of CHCHC(CH20) 3 (Y) nH3 are cross-linked at the Y part depending on the reaction conditions are also possible). A compound having one epoxy group other than 4-vinylcyclohexene-1-oxide can be copolymerized.

However, 4-vinylcyclohexene-1-oxide and 4-
What is the ratio to compounds having one epoxy group other than vinylcyclohexene-1-oxide?

The former must be in the range of 1-100%, and the latter must be in the range of 99-0%.

If the former is less than 1%, the content of vinyl groups will decrease and the characteristics of the cyclohexane skeleton will not appear. 0.01 to 1 mole of a compound having one or more active hydrogen, and 0.0.001 to 0.5 mole of a compound having two or more epoxy groups per 1 mole of the total
The reaction is carried out in a molar ratio, preferably 0.01 to 0.2 molar.

If the amount of the compound having one or more active hydrogen atoms is less than 0.01 mol, it will not function as an initiator.

In addition, compounds having two or more epoxy groups have 0°001
It is not possible to modify the epoxy compound at less than mol.
If the amount is 0.5 mol or more, the molecular weight becomes too high to be practically usable.

When addition-polymerizing a mixture of 4-vinylcyclohexene-1-oxide and a compound having two or more epoxy groups to a compound having one or more active hydrogens, 4-vinylcyclohexene-1-oxide and two epoxy groups The above compounds can be reacted simultaneously.

Alternatively, either 4-vinylcyclohexene-1-oxide or a compound having two or more epoxy groups can be reacted first, and the reaction adduct can be reacted with the other.

Furthermore, 4-vinylcyclohexene-1-oxide and a compound having two or more epoxy groups are reacted simultaneously, and either one of them is reacted, or 4-vinylcyclohexene-1-oxide is reacted with either one of them first. Catalysts used in the reaction, in which an oxide and a compound having two or more epoxy groups can be reacted simultaneously, include amines such as methylamine, ethylamine, propylamine, and piperazine, organic bases such as pyridines and imidazoles, and tetrahydrocarbons. Quaternary ammonium salts such as butylammonium bromide; organic acids such as formic acid, acetic acid, and propionic acid; inert acids such as sulfuric acid and hydrochloric acid; alkali metal alcoholades such as sodium methylate; alkalis such as KOH and NaOH; BF ZnCj AN Cj
Examples include 3'2'3' Lewis acids such as 5nCJ4 or complexes thereof, and organometallic compounds such as triethylaluminum and diethylzinc.

The amount of catalyst varies depending on the type, but it is 0% based on the starting material.
．． It can be used in a range of 0.01 to 10%, preferably 0.1 to 5%.

The reaction temperature is -20 to 200°C, preferably 0°C to 12°C.
It is 0°C.

The reaction can also be carried out using a solvent.

Solvents and binders containing active hydrogen cannot be used.

i.e., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene,
Aromatic solvents such as xylene, ethers, aliphatic hydrocarbons, esters, etc. can be used.

Now, the epoxy resin of the present invention is synthesized by allowing an epoxidizing agent to act on the polyether compound having a vinyl group side chain synthesized in this way, and peracids can be used as the epoxidizing agent.

and hydroperoxides.

Peracids include performic acid, peracetic acid, and perbenzoic acid.

Examples include trifluoroperacetic acid.

Among these, peracetic acid is a preferred epoxidizing agent because it is produced industrially in large quantities, is available at low cost, and has high stability.

Hydrogen peroxide is a hydroperoxide.

Examples include tertiary butyl hydroperoxide and cumene peroxide.

A catalyst can be used during epoxidation if necessary.

For example, in the case of a peracid, an alkali such as soda carbonate or an acid such as sulfuric acid may be used as a catalyst.

Also, in the case of hydroperoxides, a mixture of tungstic acid and caustic soda with hydrogen peroxide.

Alternatively, the catalytic effect can be obtained by using an organic acid in combination with hydrogen peroxide and mono or molybdenum hexacarbonyl with tert-butyl hydroperoxide.

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

The usable reaction temperature range is determined by the reactivity of the epoxidizing agent used.

Regarding peracetic acid, which is a preferred epoxidizing agent, 0 to
70°C is preferred.

At temperatures below 0°C, the reaction is slow, and at 70°C, peracetic acid decomposes.

Also, for the tertiary butyl hydroperoxide/molybdenum dioxide diacetylacetonate system, which is an example of hydroperoxide, the temperature is 20°C to 150°C for the same reason.
is preferred.

The solvent can be used for purposes such as lowering the viscosity of the raw material and stabilizing the epoxidizing agent by diluting it.

In the case of peracetic acid, an aromatic compound, ether, and in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.

The molar ratio of the epoxidizing agent to the unsaturated bonds can be changed depending on the purpose, such as how much unsaturated bonds are desired to remain.

When the objective is to obtain a compound with a large number of epoxy groups, it is preferable to add the epoxidizing agent in an amount equivalent to or more than the amount of the unsaturated group.

However, it is usually disadvantageous to exceed 2 times the molar amount due to economic efficiency and the problem of side reactions described below, and in the case of peracetic acid, 1 to
1.5 times the molar amount is preferable.

The epoxy compound of the present invention obtained as a result of the above reaction is 1
When trimethylolpropane is used as a compound having more than one active hydrogen, it has the following structure.

CHCHC(CH20)3(Z)nH32 (II) However, n is necessarily the same as in the case of the polyether compound of formula <1) above. Z is a mixture in which the vinyl group contained in Y in the case of the polyether compound of formula (1) has been changed to the three groups described below] Depending on the conditions of the epoxidation reaction, 4-vinylcyclohexene-1 - Simultaneously with the epoxidation of the vinyl groups in the oxide, a mixture of cyclohexane polyether structures having unreacted vinyl groups in the raw material and cyclohexane polyether structures having modified substituents is produced.

In addition, when the epoxidizing agent is peracetic acid, -4-vinylcyclohexene-1-oxide is a cyclohexane polyether such as the following cyclohexane polynye containing a modified substituent or a cyclohexane polyether having an epoxy group produced by epoxidation. The above-mentioned modified substituent is generated from the generated epoxy group and the by-produced acetic acid.

Unreacted vinyl group -CH=CH2, epoxidized C-CH
2 HO0CCH3 1 The production ratio of the mixture of the three is determined by the type of epoxidizing agent, the molar ratio of the olefin bond between the epoxidizing agent and the reaction conditions.

Epoxy group in epoxy I fat of the present invention The smaller the amount of -CH-CH2 is, the more preferable it is.

OHOR [R3 is H, an alkyl group, an alkylcarbonyl group.

Any one arylcarbonyl group] The compound having two or more epoxy groups used in the present invention does not have a vinyl group like 4-vinylcyclohexene-1-oxide, so it does not participate in the epoxidation reaction. Therefore, the above-mentioned substituents do not occur.

It is essential that one or more compounds having two or more epoxy groups are also used simultaneously with 4-vinylcyclohexene-1-oxide.

When using , the part having a polyether structure generated from the above compound becomes a mixture of the following structures.

) 1 A linear structure may be formed only with these polyether structural parts produced from compounds having 2@ or more of epoxy groups, and in some cases, these polyether structural parts and 4-
The cyclohexane polyether structure produced from vinylcyclohexene-1-oxide may form a partially linear random structure and a partially crosslinked structure.

The target compound can be removed from the reaction crude solution by conventional chemical engineering means such as concentration.

(Effect of the invention) As mentioned above, the two epoxy compounds of the present invention are:

It exhibits a higher softening point than conventional epoxy compounds made from polymers of only 4-vinylcyclohexene-1-oxide.

Therefore, it can be applied to a wide range of applications depending on the purpose of use.

On the other hand, the conventional cured product of epoxide made from a polymer of 4-vinylcyclohexene-1-oxide alone has excellent characteristics such as heat resistance, mechanical properties, electrical properties, transparency, flexibility, and water resistance. has it as is.

Furthermore, it is possible to obtain a product with improved anti-blocking properties.

Utilizing these characteristics, we can develop encapsulants for ICs and LSIs, and
It is expected to demonstrate excellent performance in a wide range of fields, including ED sealants, matrix resins for composite materials, and paints.

It can also be used as an alternative to conventional epoxy resin applications.

Next, the present invention will be explained with reference to Examples.

“Example IJ 7.1 g (0.05 mol) of trimethylolpropane was mixed with 124 g (0.05 mol) of 4-vinylcyclohexene-1-oxide (
1.0 mol) and further dissolve 5.0 g of 4-vinylcyclohexene dieboxide (<0.03 mol).

Subsequently, 2.7 g of BF3 etherate was added dropwise as an ethyl acetate solution over 4 hours to cause a reaction.

The inside of the dropping medium thread was kept at 50°C.

After the dropwise addition was completed, analysis using gas chromatography revealed that most of trimethylolpropane, 4-vinylcyclohexene-1-oxide, and 4-vinylcyclohexene dieboxide had disappeared.

Subsequently, 200 g of ethyl acetate was added to the crude solution of the second reaction, and the mixture was washed three times with 300 g of pure water.

91% peracetic acid was added to the obtained ethyl acetate solution of the polyether.
2 g (1.2 mol) was added dropwise as an ethyl acetate solution over 4 hours.

The temperature inside the dripping medium thread is 50℃ (blank below) I kept it.

After further aging at 50° C. for 2 hours, it was washed three times with 300 g of pure water.

Next, low-boiling components were removed using a rotary evaporator.
The desired epoxy compound was obtained.

"Examples 2-3" Trimethylolgloban, 4-vinylcyclohexene-
A reaction was carried out in the same manner as in the example except that the reaction ratio of 1-oxide and 4-vinylcyclohexene dieboxide was changed to obtain an epoxy compound.

"Examples 4-5" Instead of 4-vinylcyclohexene diekiboside, 3
．． 4-Epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate [7oxide 2021
: manufactured by Daicel Chemical Co., Ltd.] to obtain an epoxy compound in the same manner.

"Comparative Examples 1-2" Trimethylolpropane and 4-vinylcyclohexene
An epoxy compound was similarly obtained using only 1-oxide.

Above are “Examples 1 to 5” “Comparative Examples 1-2J conclusion hand Continued Supplementary Positive spontaneous writing) The results are summarized in Table 1.

Showa 6 April 6, 3rd year

Claims (1)

[Claims] An epoxy compound obtained by epoxidizing a polyether compound obtained by addition copolymerizing 4-vinylcyclohexene-1-oxide and a compound having two or more epoxy groups with a compound having one or more active hydrogen.