JPH0421647A - Polyether compound and epoxy resin - Google Patents

Abstract

NEW MATERIAL:A polyether compound of formula [R<1> is an organic compound residue having lx active hydrogens; n<1>-n<l> are integers of 0, 1-100, the sum of n<1>-n<l> being 1-100; (l) is an integer of 1-100; A is a group of formula II or III (X<1>-X<3> are (h), organic substituents; (m) is an integer of 0 or larger); but at least one skeleton of formula II is contained in one molecule]. USE:An intermediate for preparing epoxy resins having excellent heat resistance, weather resistance and transparency and having improved water absorbability. PREPARATION:A compound of formula IV is addition-polymerized to a compound of formula V (R<11>-R<14> are H, organic compound residues) to provide the compound of formula I. The further epoxidation of the double bonds in the compound of formula I with an epoxidizing agent gives a new epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polyether compound and alicyclic epoxy resin.

More specifically, the present invention relates to novel alicyclic epoxy resins with improved water resistance, weather resistance and heat resistance.

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

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 has excellent water resistance and is strong, it still has poor weather resistance.
It has drawbacks such as 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, but chlorine or several 110
0 pp, 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 manufactured by epoxidation reaction of compounds having a 5-membered or 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 alicyclic epoxy resins, the following (III) and (1■
) is manufactured and used industrially.

[Problems to be Solved by the Invention] However, although (III) is used in heat-resistant epoxy diluents because of its extremely low viscosity, it has the problem of being highly toxic and causing severe irritation to the skin of workers. .

(IV) has few impurities, a low hue, and a cured product having a high heat deformation temperature, but has a problem of poor water resistance due to ester bonds.

Furthermore, since both (III) and (1v) are low-viscosity epoxy resins, solid epoxy resin molding systems such as transfer molding cannot be applied.

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

However, although the exposi resin disclosed in JP-A No. 60-166675 has excellent heat resistance, weather resistance, and heat resistance, and is also excellent in transparency, it has a drawback that it has relatively high water absorption at high temperatures. It becomes.

As a result of studies conducted by the present inventors under these circumstances, it has been found that an epoxy resin can be obtained that has excellent heat resistance, weather resistance, and heat resistance, as well as excellent transparency, and is also improved in terms of water absorption. They discovered this and arrived at the present invention.

[Components of the invention That is, the present invention [The following general formula (I) Polie represented by Chill compound” and "The following general formula (I) epoxy resin expressed by It is.

Next, the present invention will be explained in detail.

In the polyether compound represented by the general formula (I) and the new epoxy resin represented by the general formula (II) of the present invention, the organic compound having one or more active hydrogens which is a precursor of R1 includes alcohols, Phenols,
Examples include 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, octatool, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol,
Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 13
Butanediol, 14-butanediol, pentanediol, 16-hexanediol, neopentyl glycol, ochinepivalic acid neopentyl glycol ester, cyclohexane dimetatool, glycerin, diglycerin,
Polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A1 hydrogenated bisphenol F
Examples include polyhydric alcohols such as monohydrogenated bisphenol S.

Examples of phenols include phenol, cresyl, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, A1 bisphenol F for bisphenol, 4,4°-dihydroxybenzophenone, bisphenol S1 phenolic 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, isoporonediamine, toluenediamine, hexamethylenediamine, quinlenamine, diethylenetriamine, triethylenetetramine, and ethanolamine.

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

Furthermore, other compounds having active hydrogen include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl 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, the compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, and tetrahydrophthalic acid. be.

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

Next, in the polyether compound represented by the general formula (I) of the present invention, A consists of the following skeleton (a) or (b), and at least one skeleton of (a) is contained in one molecule. This is essential.

In skeleton (a), X, X2, X3, and R3 represent hydrogen or an organic substituent, and m is an integer of 0 or more.

The compound that is a starting material for producing the polyether compound and epoxy resin of the present invention and provides the skeleton of (a) or (b) above is a compound having the following structure.

Specific compounds represented by m include the following various compounds, and these may be used alone or in combination of two or more. (Hereinafter in the margin) Specific compounds represented by U (Vl) include the following various compounds, and these may be used alone or in combination of two or more types.

α-olefin epoxide represented by 2 to 25, CH3CH2CH2 (in the above formula, Ph is a benzene nuclear residue) (the following is a blank space) 15 1B' 17 (R, R, R are C9 to C11 tert-carboxylic acid residues) Glycidyl ethers of polyalcohols and polyglycols such as alicyclic epoxy resins (hereinafter referred to as blanks) (where R is a hydrogen atom, an alkyl group, etc.),
Polyolefin-type epoxy resins such as epoxidized soybean oil and epoxidized linseed oil, heterocyclic epoxy resins such as diglycidylhydantoin and triglycidyl isocyanurate, glycidylamine-based resins such as tetraglycidyldiaminodiphenylmethane and triglycidyl P-aminophenol, Examples include glycidyl ester resins such as diglycidyl phthalate and diglycidyl tetrahydrophthalate, as well as bisphenol A epoxy resins, bisphenol F epoxy resins, and novolac epoxy resins.

There is no problem even if two or more of these are mixed and used.

In the epoxy resin represented by the general formula (I) of the present invention, B represents the following skeleton (C) or (b).

In skeletons (a), (b) and (c), X,
X2X3 and R3 represent hydrogen or an organic substituent, and m is an integer of 0 or more.

HOR2 However, R2 is any one of hydrogen, an alkyl group, an alkylcarbonyl group, and an arylcarbonyl group.

It is essential that one or more of both are included.

(C) includes unreacted products of the above-mentioned (a), epoxidized products, and also products with a structure in which the epoxy group is ring-opened.

That is, the above-mentioned (V) (vl) is added to the compound having active hydrogen.
The polyether compound (1) of the present invention is obtained by addition polymerizing the epoxy resin (I+) of the present invention, and the epoxy resin (I+
) can be obtained.

First, the part for producing polyether compound (1) by addition polymerization reaction will be described.

In this reaction, the molecular weight, that is, the value of n, can be variously adjusted by changing the reaction ratio of the compound having active hydrogen and the compound having an epoxy group containing (■).

Further, it is preferable to react a total of 2 to 100 compounds having epoxy groups containing (■) per molecule of the compound having active hydrogen.

If the sum is 100 or more, it becomes a solid with a high melting point and cannot be used in practice.

(■) and m) are (■) from 1 to 99%, (l from 99 to 1%)
React at the rate of

If (V) is 1% or more, the vinyl group content will be too low and the characteristics of the cyclohexane skeleton will not be apparent.

If (Vl) is less than 1%, the desired modification cannot be achieved.

nl, n2... in general formulas (1) and (11)
- nΩ is 0 or an integer from 1 to 100, respectively.

The sum is from 1 to 100, but if it is more than 100, the resin has a high melting point and is difficult to handle and cannot be used in practice.

g is an integer from 1 to 100 and is determined by the number of functional groups of the compound having active hydrogen.

For example, when trimethylolpropane is used as a compound having active hydrogen, it becomes D-3.

In the polyether compound (1) of the present invention, a compound having at least one epoxy group [However, R
.

Therefore, B in the epoxy resin (I+) is also necessarily HOR2 R2 is any one of hydrogen, an alkyl group, an alkylcarbonyl group, or an arylcarbonyl group] and 13R14 is ether bonded randomly or in blocks. Become.

When (v) and (1) are added to a compound having active hydrogen, a random polymer is formed when (v) and m) are reacted simultaneously.

Furthermore, a block copolymer can be formed by reacting either (■) or (Vl) first and reacting the other with the reaction adduct.

Either reaction format may be used in the present invention.

The above-mentioned polyether compound can be obtained by ring-opening polymerization of and using the above-mentioned organic compound having active hydrogen in the presence of a catalyst.

Catalysts used during the reaction include amines such as methylamine, ethylamine, propylamine, and piperazine, organic bases such as pyridines and imidazoles, quaternary ammonium salts such as tetrabutylammonium bromide, formic acid, acetic acid, propionic acid, etc. Organic acids, inorganic acids such as sulfuric acid and hydrochloric acid, alkali metal alcolades such as sodium methylate, alkalis such as KOH and NaOH, B
F 3Z n CD A J7 C to I S
Examples include Lewis 2'3' acids such as nC14 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 120°C.
It is ℃.

The reaction can also be carried out using a solvent.

A solvent 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 (11), which is the second invention, is synthesized by allowing an epoxidizing agent to act on the polyether compound (1), which is the first invention, having a vinyl group side chain synthesized in this way. However, examples of epoxidizing agents that can be used include peracids and hydroperoxides.

Examples of peracids include performic acid, peracetic acid, perbenzoic acid, and 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.

Examples of hydroperoxides include hydrogen peroxide, tert-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.

In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tert-butyl hydroperoxide. be able to.

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, aromatic compounds, ethers, aliphatic hydrocarbons, esters, etc. can be used.

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.

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.

Depending on the conditions of the epoxidation reaction, in addition to 1R3,-0-(b), which is the residue of a compound having at least one epoxy group, substituents in the raw materials or generated As a result of the reaction between the epoxidizing agent and the epoxidizing agent, a mixture of .

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

[Effects of the Invention] Next, the polyether compound and epoxy resin of the present invention will be explained with reference to Examples.

Synthesis example-1 Hexanol 4.5g, α-limonene monoepoxide 1
00g and 10g while maintaining the reaction temperature at 50°C.
%BF3 etherate/ethyl acetate solution was added dropwise.

After completion of the dropwise addition, gas chromatography analysis confirmed that α-limonene monoepoxide had completely disappeared, while 37% of the following compound and 11% of its by-products were produced.

Subsequently, after adding ethyl acetate and washing with 100 g of pure water three times, ethyl acetate and the above-mentioned by-products were removed by distillation to obtain a transparent liquid compound.

NMR analysis and IR analysis confirmed that the compound had the following structure.

The number average molecular weight by GPC was 524.

Next, 40 g of this compound was dissolved in 40 g of ethyl acetate, and while maintaining the system temperature at 50°C, 50% of a 30% peracetic acid solution was added.
4 g was added dropwise over 4 hours.

After aging at 50° C. for 4 and 3 hours, washing with 130 g of pure water was performed three times.

Acetic acid and ethyl acetate were removed by distillation to obtain a viscous liquid.

It was confirmed by NMR analysis and IR analysis that an epoxy compound having the following structure was produced.

Synthesis Example-2 134 g of trimethylolpropane and 456 g of α-limonene monoepoxide were mixed, and while maintaining the reaction temperature at 50°C, 10% BF3 etherate/ethyl acetate solution 12
0 g was added dropwise.

After the dropwise addition was completed, it was confirmed by gas chromatography analysis that 99.7% of α-limonene monoepoxide had been converted.

By-product formation was 6%.

The number average molecular weight by GPC was 490.

(Margin below) In addition, In the above formula, A represents the following structure vinegar.

moreover, Synthesis example Perform epoxidation in the same way as A compound having the following structural formula was obtained.

In addition, In the above formula, B represents the following structure vinegar.

(Margin below) The oxirane oxygen concentration was 6.2%.

Synthesis example-3 13.4 g of trimethylolpropane, 2.3 epoxy
Mix 267 g of 6-vinylbicyclo[4,4,0]octane and add 10% BF3 while maintaining the reaction temperature at 50°C.
37 g of etherate/ethyl acetate solution was added dropwise.

After completion of the dropwise addition, it was confirmed by gas chromatography analysis that 99.7% of α-limonene monoepoxide had been converted.

By-product formation was 6%.

The number average molecular weight by GPC was 1400.

In addition, In the above formula, A represents the following structure vinegar.

moreover, Synthesis example- Perform epoxidation in the same way as A compound having the following structural formula was obtained.

In addition, In the above formula, B represents the following structure vinegar.

(Leaving space below) Comparative Synthesis Example 4 g of trimethylolpropane 1B and 186 g of 4-vinylcyclohexenoquine were mixed, and 32 g of a 10% BF3 etherate/ethyl acetate solution was added dropwise while maintaining the reaction temperature at 50°C.

Furthermore, epoxidation was performed in the same manner as in Synthesis Example 1 to obtain a compound having the following structural formula.

In addition, in the above formula, B represents the following structure.

The oxirane oxygen concentration was 8.80%.

Application Example Synthesis Example 3, the epoxy resin obtained in Comparative Synthesis Example, commercially available Epicote 828, methylhexahydrophthalic anhydride (MHHPA) as a curing agent, and benzyldimethylamine (BDMA) as an accelerator were blended as shown in Table 1. then 12
It was cured at 0°C for 2 hours and then at 200°C for 2 hours.

Next, a TMA test was performed using a 3 mm square test piece,
The Tg value was determined.

Further, the water absorption rate was determined after 196 hours at 75° C. and 85% RH using a test piece of 60 mm x 40 mm x 3 mm. (Leaving space below) EPI: Epoxy resin obtained in Synthesis Example 3 EP2: Epoxy resin obtained in Comparative Synthesis Example Table 1 shows that the epoxy resin of the present invention has excellent moisture resistance without impairing heat resistance. Obviously, polyether compounds are useful compounds as precursors thereof.

Claims (2)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) A polyether compound represented by; (2) Epoxy resin represented by the following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II); <However, in general formulas (I) and (II), R^1
is an organic compound residue having l active hydrogens, n1, n2
... nl is 0 or an integer from 1 to 100, the sum of which is 1 to 100, and l represents an integer from 1 to 100. In the general formula (I), A represents the following skeleton (a) or (b), and it is essential that at least one skeleton of (a) is contained in one molecule. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) -R_3-O-...(b) In general formula (II), B is the following (c) or the above (b)
represents the skeleton of ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(c) In skeletons (a), (b) and (c), X_1,
^2, X_3, R_3 represent hydrogen or an organic substituent, and m is an integer of 0 or more. In addition, Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R^2 is hydrogen, an alkyl group, an alkylcarbonyl group , an arylcarbonyl group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼It is essential that the resin contains at least one ▼.