JP2916487B2 - Polyether compound and epoxy resin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel polyether compound and an alicyclic epoxy resin.

More specifically, the present invention relates to a novel cycloaliphatic epoxy resin having improved water resistance, weather resistance and heat resistance.

[Background Art] The epoxy resin most widely used in the industry at present is a so-called epi-bis type epoxy resin produced by a reaction between bisphenol A and epichlorohydrin. This resin has the advantage that a wide range of products from liquid to solid can be obtained, and the reactivity of the epoxy group is high, and it can be cured at room temperature with polyamine.

However, the cured product is excellent in water resistance and has poor weather resistance despite being characterized by toughness,
There are drawbacks such as poor electrical properties such as tracking resistance and low heat distortion temperature. Particularly recently, epoxy resin obtained by reacting phenol or novolak resin with epichlorohydrin is used for sealing resin such as VLSI, but the resin contains several hundred ppm of chlorine, which deteriorates the electrical characteristics of electrical components. And other problems have occurred. An alicyclic epoxy resin is an epoxy resin which does not contain chlorine and has excellent electric properties and heat resistance.

These are produced by an epoxidation reaction of a compound having a 5-membered or 6-membered cycloalkenyl skeleton.
The epoxy group of these resins is a so-called internal epoxy group, which is usually cured by heating with an acid anhydride, but cannot be cured at room temperature with a polyamine due to low reactivity.

Therefore, the use range of the alicyclic epoxy resin is remarkably narrow.

The following alicyclic epoxy resins (III) and (IV)
Is industrially manufactured and used.

[Problems to be Solved by the Invention] However, (III) is used as a heat-resistant epoxy diluent because its viscosity is very low, but it has a problem that it is highly toxic and the operator's skin is significantly rash. (IV) contains few impurities, has a low hue, and has a high heat deformation temperature of its cured product, but has a problem of poor water resistance based on ester bonds.

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

From such a background, Japanese Patent Application Laid-Open No. 60-166675 (= USP
4,565,859) proposed a novel epoxy resin having an oxycyclohexane skeleton. However, Japanese Patent Application Laid-Open
The epoxy resin disclosed in 166675 is excellent in heat resistance, weather resistance and heat resistance, and is excellent in transparency, but has a drawback that it has relatively high water absorption at high temperatures.
As a result of investigations by the present inventors from such a situation, it is found that an epoxy resin having excellent heat resistance, excellent weather resistance and heat resistance, excellent transparency, and improved water absorption can be obtained. And reached the present invention.

[Constitution of the Invention] That is, the present invention relates to the following “general formula (I) Wherein, in the general formula (I), R ¹ is a residue obtained by removing active hydrogen from an organic compound having ¹ active hydrogen, n 1, n 2.
... nl is 0 or an integer of 1 to 100, respectively, and the sum is 1
And l represents an integer of 1 to 100. A represents a skeleton of the following (a) and / or (b), and it is essential that at least one skeleton of (a) is contained in one molecule.

—R ³ —O— (b) In the skeletons (a) and (b), X ¹ and X ³ represent hydrogen or an alkyl group, and X ² represents an alkylene group, an alicyclic skeleton, an ether bond or an ester bond. R ³ represents a residue of an epoxy compound, m is an integer of 0 or more, and X ¹ and X ³
Is hydrogen and the skeleton when m is 0 is 50% or less of the entire skeleton represented by (a). > ”And“ The following general formula (II) Wherein, in the general formula (II), R ¹ is a residue obtained by removing active hydrogen from an organic compound having ¹ active hydrogen, n 1, n 2.
... nl is 0 or an integer of 1 to 100, respectively, and the sum is 1
L is an integer of 1 to 100, and is a general formula (I
In I), B is the following (c) and / or (b)
Represents the skeleton of In the skeleton (c), X ¹ represents hydrogen or an alkyl group, X ² represents an alkylene group, an alicyclic skeleton, or an alkylene group having an ether bond or an ester bond, and R ³ represents a residue of an epoxy compound. And m is an integer of 0 or more, and when X ¹ is hydrogen and m is 0, the skeleton is 50% or less of the entire skeleton represented by (a), and Y is However, X ³ represents hydrogen or an alkyl group, R ² is hydrogen, an alkyl group, an alkylcarbonyl group, any one of an arylcarbonyl group, Is essential in the resin, and when X ¹ and X ³ are hydrogen and m is 0, the skeleton is 50% or less of the entire skeleton represented by (a). 〉 ”.

 Next, the present invention will be described in detail.

In the novel epoxy resin represented by the polyether compound represented by the general formula (I) of the present invention and the general formula (II), an organic compound having one or more active hydrogen which is a precursor of R ¹ include alcohols Phenols, carboxylic acids, amines, thiols and the like.

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

For example, methanol, ethanol, propanol, butanol, pentanol, hexanol, aliphatic alcohols such as octanol, 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, neopentyl glycol oxypivalate, cyclohexane dimethanol, glycerin, glycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, diphenyl Examples include polyhydric alcohols such as pentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S. Examples of phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, phenol resin, cresol novolak resin, and the like.

Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane diacid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid, and terephthalic acid. Acids and the like.

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

As amines, monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, Examples include toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, and ethanolamine.

As thiols, methyl mercaptan, ethyl mercaptan, propyl mercaptan, mercapto such as phenyl mercaptan, polyhydric alcohol ester of mercaptopropionic acid or mercaptopropionic acid, for example, ethylene glycol dimercaptopropionate, trimethylolpropane trimercaptopropionic acid, Pentaerythritol pentamercaptopropionic acid;

Still other compounds having active hydrogen include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene-maleic Examples include acid copolymer resins, alkyd resins, polyester polyol resins, polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, and polytetramethylene glycol.

Further, 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. is there.

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 has the following skeleton (a) or (b), and at least one skeleton of (a) is contained in one molecule. It is essential.

In the skeleton (a), X ¹ and X ³ represent hydrogen or an alkyl group, X ² represents an alkylene group, an alicyclic skeleton, an alkylene group having an ether bond or an ester bond, and m represents 0 or more. It is an integer, and the skeleton when X ¹ and X ³ are hydrogen and m is 0 is 50% or less of the whole skeleton represented by (a).

Specific compounds represented by (V) include the following various compounds, which may be used alone or as a mixture of two or more.

Specific compounds represented by (VI) include the following various compounds, which may be used alone or in combination of two or more.

α-olefin epoxide represented by n = 2 to 25 (In the above formula, Ph is a benzene nucleus residue) (R ¹⁵ , R ¹⁶ and R ¹⁷ are alkyl groups of a C9 to C11 tert-carboxylic acid ester) Alicyclic epoxy resin [Where R is a hydrogen atom, an alkyl group, etc.] Polyalcohols such as glycidyl ether of polyglycol and polyglycol; polyolefin type epoxy resins such as epoxidized soybean oil and epoxidized linseed oil; Cyclic epoxy resins, glycidylamine resins such as tetraglycidyl diaminodiphenylmethane, triglycidyl P-aminophenol, glycidyl ester resins such as diglycidyl phthalate ester and diglycidyl tetrahydrophthalate ester, and other bisphenol A
Type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin and the like. These may be used in combination of two or more.

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

In the skeletons (a), (b) and (c), X ¹ and
X ³ represents hydrogen or an alkyl group; X ² represents any of an alkylene group, an alicyclic skeleton, and an alkylene group having an ether bond or an ester bond; R ³ represents a residue of an epoxy compound; Is an integer greater than or equal to
When X ¹ and X ³ are hydrogen and m is 0, the skeleton is 50% or less of the entire skeleton represented by (a).

Also, Y However, X ³ represents hydrogen or an alkyl group, R ² is hydrogen, an alkyl group, an alkylcarbonyl group, any one of an arylcarbonyl group, It is essential that at least one or more is contained in the resin.

When X ¹ and X ³ are hydrogen and m is 0, the skeleton is 50% or less of the entire skeleton represented by (a).

(C) includes the unreacted one described in (a) above, the epoxidized one, and the one without the epoxy group-opened structure.

That is, the compounds having active hydrogen described above in (V) and (V
The polyether compound (I) of the present invention can be obtained by addition polymerization of I), and the epoxy resin (II) of the present invention can be obtained by epoxidizing the double bond thereof with an epoxidizing agent.

First, a polyether compound (I) is obtained by addition polymerization reaction.
Is described. In this reaction, the molecular weight, that is, the value of n can be variously adjusted by changing the reaction ratio between the compound having active hydrogen and the compound having an epoxy group containing (V).

In addition, it is preferable to react the compound having an epoxy group containing (V) per molecule of the compound having active hydrogen at a rate of 2 to 100 in total. If the sum is more than 100, it becomes a solid having a high melting point, and is not practically usable.

(V) and (VI) are 1 to 99% of (V) and 99 to 1 of (VI).
%.

If (V) is 1% or less, the vinyl group content becomes too low and the characteristics of the cyclohexane skeleton are not obtained.

When (VI) is 1% or less, the desired reforming cannot be performed.

In the general formulas (I) and (II), n ₁ , n ₂ ... N _l are each 0 or an integer of 1 to 100. The sum is 1-100
However, if it is 100 or more, it becomes a resin having a high melting point and is difficult to handle, so that it is not practically usable.

l 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, 1 = 3. In the polyether compound (I) of the present invention, a compound having at least one epoxy group [Where R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are hydrogen or an organic compound residue] Are randomly or ether-bonded to blocks.

Therefore, B in the epoxy resin (II) is inevitably [However, Y is R ² is an alkyl group, an alkylcarbonyl group, or an arylcarbonyl group] and Are randomly or ether-bonded to blocks.

When (V) and (VI) are added to the compound having active hydrogen, a random polymer is formed by simultaneously reacting (V) and (VI).

Further, if either (V) or (VI) is reacted first and the other is reacted with the reaction adduct, a block copolymer can be formed.

 In the present invention, either reaction mode may be used.

The above polyether compound is used in the presence of a catalyst. (X ¹ , X ² , X ³ , R ² and _m are the same as above) and Is subjected to ring-opening polymerization using the organic compound having active hydrogen.

Examples of the catalyst used in the reaction include amines such as methylamine, ethylamine, propylamine, and piperazine;
Organic bases such as pyridines and imidazoles, and quaternary ammonium salts such as tetrabutylammonium bromide;
Organic acids such as formic acid, acetic acid and propionic acid, inorganic acids such as sulfuric acid and hydrochloric acid, alcoholates of alkali metals such as sodium methylate, alkalis such as KOH and NaOH, BF ₃ , ZNCl
₂ , Lewis acids such as AlCl ₃ and SnCl ₄ or complexes thereof, and organometallic compounds such as triethylaluminum and diethylzinc.

The amount of catalyst varies depending on the type, but
It can be used in the range of 0.01 to 10%, preferably 0.1 to 5%. Reaction temperature is -20 to 200 ° C, preferably 0 ° C
~ 120 ° C. The reaction can also be performed using a solvent.

As the solvent, those having active hydrogen cannot be used.

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

An epoxy resin (II) according to the second invention is synthesized by reacting the epoxidizing agent with the polyether compound (I) as the first explanation having the vinyl group side chain thus synthesized. However, usable epoxidizing agents include peracids and hydroperoxides.

The peracids include formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like.

Of these, peracetic acid is industrially produced in large quantities,
It is a preferable epoxidizing agent because it can be obtained at low cost and has high stability. Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like. At the time of epoxidation, a catalyst can be used if necessary.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. In the case of hydroperoxides, a mixture of tungstic acid and caustic soda is hydrogen peroxide, or an organic acid is hydrogen peroxide,
Alternatively, a catalytic effect can be obtained by using molybdenum hexacarbonyl in combination with tertiary butyl hydroperoxide.

The epoxidation reaction is performed by adjusting the presence or absence of a solvent and the reaction temperature in accordance with the apparatus and the physical properties of the raw materials. The reaction temperature range that can be used is determined by the reactivity of the epoxidizing agent used. Regarding peracetic acid, which is a preferred epoxidizing agent, 0-70
° C.

This is because the reaction is slow at 0 ° C or lower, and decomposition of peracetic acid occurs at 70 ° C.

In the case of a tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate system, which is an example of a hydroperoxide, the temperature is preferably from 20C to 150C for the same reason.

The solvent can be used for the purpose of lowering the viscosity of the raw material, stabilizing the epoxidizing agent by dilution, and the like. In the case of peracetic acid, aromatic compounds, ethers, aliphatic hydrocarbons, esters and the like can be used. For example, 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 charged molar ratio of the epoxidizing agent to the unsaturated bond can be changed depending on the purpose such as how much the 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 based on the unsaturated group. However, it is usually disadvantageous that the molar ratio exceeds 2 times from the viewpoint of economy and the side reaction described below. In the case of peracetic acid, the molar ratio is preferably 1 to 1.5 times.

In addition to the substituents in the starting material of -R ³ -O- depending on the conditions of the epoxidation reaction is a residue of a compound having the epoxidation at the same time at least one epoxy group of a vinyl group (b) And generate Reacts with the epoxidizing agent, (X ¹ , X ² , X ³ , R ² and _m are the same as described above). The target compound can be extracted from the crude reaction solution by ordinary chemical engineering means such as concentration.

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

Synthesis Example-1 Hexanol 4.5 g, α-limonene monoepoxide 100 g
, And 130 g of a 10% BF3 etherate / ethyl acetate solution was added dropwise while maintaining the reaction temperature at 50 ° C. After the completion of the dropwise addition, it was confirmed by gas chromatography analysis that α-limonene monoepoxide had completely disappeared. It was confirmed that 37% was produced and 11% of the by-product was produced.

Subsequently, ethyl acetate was added, and the resultant was washed with 100 g of pure water three times. Then, 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. Number average molecular weight by GPC is 5
24.

Next, 40 g of this compound was dissolved in 40 g of ethyl acetate, and while maintaining the internal temperature at 50 ° C., 54 g of a 30% peracetic acid solution was added dropwise over 4 hours.

After aging at 50 ° C. for 4 further 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.

NMR analysis and IR analysis confirmed that an epoxy compound having the following structure was formed. Oxirane oxygen concentration was 7.03%.

Synthesis Example-2 134 g of trimethylolpropane and 456 g of α-limonene monoepoxide were mixed, and 10
120 g of a% BF ₃ etherate / ethyl acetate solution was added dropwise.
After the completion of the dropwise addition, it was confirmed by gas chromatography analysis that 99.7% of α-limonene monoepoxide was converted. By-product formation was 6%. The number average molecular weight by GPC was 490.

In the above formula, A represents the following structure.

Further, epoxidation was carried out in the same manner as in Synthesis Example-1 to obtain a compound having the following structural formula.

In the above formula, B represents the following structure.

Oxirane oxygen concentration was 6.2%.

Synthesis Example-3 13.4 g of trimethylolpropane, 2,3-epoxy-6
267 g of vinylbicyclo [4.4.0] decane were mixed, and 37 g of a 10% BF ₃ etherate / ethyl acetate solution was added dropwise while maintaining the reaction temperature at 50 ° C.

After completion of the dropwise addition, 2,3-
99.7 epoxy-6-vinylbicyclo [4,4,0] decane
% Conversion was confirmed. By-product formation was 6%. The number average molecular weight by GPC was 1,400.

In the above formula, A represents the following structure.

Further, epoxidation was carried out in the same manner as in Synthesis Example-1 to obtain a compound having the following structural formula.

In the above formula, B represents the following structure.

The oxirane oxygen concentration was 6.30%.

Comparative Synthesis Example 13.4 g of trimethylolpropane and 186 g of 4-vinylcyclohexenoxide were mixed, and 32 g of a 10% BF ₃ etherate / ethyl acetate solution was added dropwise while maintaining the reaction temperature at 50 ° C. Further, epoxidation was carried out in the same manner as in Synthesis Example-1 to obtain a compound having the following structural formula.

In the above formula, B represents the following structure.

Oxirane oxygen concentration was 8.80%.

Application Examples Epoxy resin obtained in Synthesis Example 3 and Comparative Synthesis Example, commercially available Epicoat 828, methylhexahydrophthalic anhydride (MHHPA) as a curing agent, and benzyldimethylamine (BDMA) as an accelerator as shown in Table 1. It was blended and cured at 120 ° C. for 2 hours and further at 200 ° C. for 2 hours.

Next, a TMA test was performed using a 3 mm square test piece to determine a Tg value.

Also, using a test piece of 60 mm × 40 mm × 3 mm, 75
C., 85% RH, water absorption after 196 hours.

From Table 1, it can be seen that the epoxy resin represented by the general formula (II) of the present invention can be obtained without impairing the heat resistance.
It is clear that the epoxy resin has better moisture resistance (lower moisture absorption) than the epoxy resin described in JP-A-6675.

The polyether compound represented by the general formula (I) is a compound useful as a precursor thereof.

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula (I) Wherein, in the general formula (I), R ¹ is a residue obtained by removing active hydrogen from an organic compound having ¹ active hydrogen, n 1, n 2.
... nl is 0 or an integer of 1 to 100, respectively, and the sum is 1
L is an integer of 1 to 100, A is a skeleton of the following (a) and / or (b), and at least one skeleton of (a) is contained in one molecule. Required, —R ³ —O— (b) In the skeletons (a) and (b), X ¹ and X ³ represent hydrogen or an alkyl group, and X ² represents an alkylene group, an alicyclic skeleton, an ether bond or an ester bond. Wherein R ³ represents a residue of an epoxy compound; m is an integer of 0 or more; and when X ¹ and X ³ are hydrogen and m is 0, the skeleton is ( Not more than 50% of the entire skeleton represented by a). 〉. 2. The following general formula (II) Wherein, in the general formula (II), R ¹ is a residue obtained by removing active hydrogen from an organic compound having ¹ active hydrogen, n 1, n 2.
... nl is 0 or an integer of 1 to 100, respectively, and the sum is 1
L is an integer of 1 to 100, and is a general formula (I
In I), B is the following (c) and / or (b)
Represents the skeleton of In the skeleton (c), X ¹ represents hydrogen or an alkyl group, X ² represents an alkylene group, an alicyclic skeleton, or an alkylene group having an ether bond or an ester bond, and R ³ represents a residue of an epoxy compound. And m is an integer of 0 or more, and when X ¹ is hydrogen and m is 0, the skeleton is 50% or less of the entire skeleton represented by (a), and Y is Wherein X ³ represents hydrogen or an alkyl group, R ² is hydrogen,
An alkyl group, an alkylcarbonyl group, any one of an arylcarbonyl group, Is essential in the resin, and when X ¹ and X ³ are hydrogen and m is 0, the skeleton is 50% or less of the entire skeleton represented by (a). 〉.