JP3072113B2 - Polyether compound, epoxy compound and composition comprising epoxy compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]

The present invention relates to a novel polyether compound, an epoxy compound and an epoxy resin composition comprising the epoxy compound. More specifically, the present invention relates to a novel epoxy resin composition comprising an alicyclic epoxy compound and an aliphatic epoxy compound having excellent heat resistance, water resistance and weather resistance, and a novel polyether compound and epoxy compound serving as a starting material thereof.

[Prior art]

The most widely used epoxy resin in the industry at present is the so-called epbis-type epoxy resin produced by the reaction of bisphenol with 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.

Embedded image However, (III) is used as a heat-resistant epoxy diluent because of its very low viscosity, but has a problem that it is highly toxic and causes the skin of workers to be extremely rash. (IV) contains few impurities, has a low hue, and has a high heat distortion temperature of its cured product, but has a problem of poor water resistance due to 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. Sho 60-166675 (= USP 4,56
5,859) proposed a novel epoxy resin having an oxycyclohexane skeleton. Japanese Patent Application Laid-Open No. 61-206542 has proposed a novel epoxy resin obtained by copolymerizing vinylcyclohexene oxide and alpha-olefin epoxide.

[Problems to be solved by the invention]

Furthermore, not only the purpose of solving the above-mentioned problems but also the uses of epoxy resins have been diversified, and those having a higher softening temperature depending on the method of use and the purpose of use, water resistance and flexibility. There is a demand for those having various performances, such as those having excellent properties. For example, the type disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 60-166675, which is characterized by being a solid alicyclic epoxy resin, is required to be liquid. A liquid alicyclic epoxy resin of the type disclosed in JP-A-60-166675 can be obtained if the molecular weight is less than 1,000. Also, disclosed in JP-A-61-206542, those obtained by copolymerizing vinylcyclohexene oxide and alpha-olefin epoxide can be obtained in a liquid state even if the molecular weight is set to 1,000 or more. In this case, the epoxy equivalent becomes large, which is not preferable. On the other hand, the epoxy resin disclosed in Japanese Patent Application Laid-Open No. 61-206542, which uses allyl glycidyl ether, is liquid and has an appropriate epoxy equivalent, but the water resistance is significantly deteriorated. In view of such circumstances, as a result of investigations by the present inventors, they have found an epoxy resin that is liquid, has a reasonable epoxy equivalent, and has excellent water resistance. In addition, the present inventors have found that a liquid to a solid state can be freely synthesized by appropriately adjusting and combining the mixing ratio of the two types of epoxy compounds and their respective molecular weights, thereby completing the present invention.

Configuration of the Invention

 That is, the present invention relates to the following general formula (1)

Embedded image [In the general formula (1), n is 0 to 20] A polyether compound obtained by subjecting a monoepoxy compound of an alkadiene represented by the following formula to ring-opening addition polymerization to a compound having one or more active hydrogens ” The following general formula (1)

Embedded image [In the general formula (1), n is 0 to 20] A polyether compound obtained by subjecting a monoepoxy compound of an alkadiene represented by the following formula to ring-opening addition polymerization to a compound having one or more active hydrogens is epoxidized. An epoxy compound characterized by being obtained. (A) and (b) (a) an epoxy obtained by epoxidizing a polyether compound obtained by ring-opening addition polymerization of 4-vinylcyclohexene-1-oxide to a compound having one or more active hydrogens; Compound [B], (b) the following general formula (1)

Embedded image [In the general formula (1), n is 0 to 20] A polyether compound obtained by subjecting a monoepoxy compound of an alkadiene represented by the following formula to ring-opening addition polymerization to a compound having one or more active hydrogens is epoxidized. A composition comprising the obtained epoxy compound [A]. It is. Next, the present invention will be described in detail. Examples of the compound having one or more active hydrogens used for producing the polyether compound and the epoxy compound of the present invention include alcohols, phenols, carboxylic acids, amines, and thiols. 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, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylol propane,
Examples include polyhydric alcohols such as trimethylolethane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S. 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, may also be used. 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 dimercaptopropionic acid ester, 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. Compounds having at least one epoxy group and at least one vinyl group, which are starting compounds forming the skeleton of the epoxy compound [A] in the epoxy resin composition of the first invention and the epoxy resin composition of the third invention, respectively, are ranked higher. The compound represented by the concept is represented by the following general formula.

Embedded image However, R ¹ , R ² , R ³ , and R ⁴ are hydrogen or an organic compound residue, and —CH ＝ CH ₂ may be bonded to any alkyl group of R ¹ , R ² , R ³ , and R ⁴ . Further, n and m are integers of 1 or more. The following compounds may be mentioned as specific examples thereof as well as those included in the general concept.

Embedded image n is 0-20.

Embedded image [However, Ph represents a phenyl group bonded at the para position]

Embedded image The polyether compound in the present invention is obtained by reacting the compound having one or more active hydrogens with the compound having one or more epoxy groups and one or more vinyl groups (hereinafter abbreviated as compound [C]) in the presence of a catalyst. Obtainable. In this reaction, the molecular weight can be variously adjusted by changing the reaction ratio of [C] to the compound having one or more active hydrogens. In addition, it is desirable to carry out the reaction at a ratio of [C] of 2 to 100 molecules per molecule of the compound having one or more active hydrogens. When [C] is reacted at a ratio exceeding 100 molecules, it becomes a solid having a high melting point, and is not practically usable. The polyether compound according to the first invention is a precursor of the epoxy compound [A] according to the second invention. The epoxy compound [A] and the epoxy compound [B]
[A] is mixed at a ratio of 1 to 100% and [B] at a ratio of 99 to 0%. When [A] is 1% or less, the mixture does not become liquid and has almost the same physical properties as [B]. Further, an epoxy compound [A] and an epoxy compound [B]
The epoxy resin composition, which is a mixture of the above, may be prepared by synthesizing the epoxy compounds [A] and [B] and then mixing them, or may be epoxidized after mixing the polyether compounds of the precursors of the respective epoxy compounds. . The polyether compound of the present invention represents [C] in the form of a superordinate compound.

Embedded image Then

Embedded image It becomes the thing which carried out the ether bond like this. In the present invention, either reaction mode may be used. 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 the catalyst varies depending on the type, but it is preferably 0.01 to 10%, preferably
It can be used in the range of 0.1 to 5%. The reaction temperature is from -20 to 200C, preferably from 0C to 120C. 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. Now, the epoxy resin of the second invention is synthesized by applying an epoxidizing agent to the polyether compound of the first invention having a vinyl group side chain synthesized in this way, Epoxidizing agents that can be used include peracids and hydroperoxides. The peracids include formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like. Of these, peracetic acid is a preferred epoxidizing agent because it is industrially produced in large quantities, is available 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 is preferred. At 0 ° C or lower, the reaction is slow, and at 70 ° C, peracetic acid is decomposed. In the case of tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate, 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 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, due to economical problems and the side reactions described below,
Exceeding the molar amount is usually disadvantageous, and 1
1.51.5-fold molar is preferred. Depending on the conditions of the epoxidation reaction, the compound having an unreacted vinyl group in the raw material and the epoxy group generated by epoxidation at the same time as the epoxidation of the vinyl group in the compound having at least one epoxy group and one vinyl group A mixture of polyether structures and polyether structures with modified substituents is formed. When the epoxidizing agent is peracetic acid, the modified substituent has the following structure.

Embedded image The modified substituent is derived from the formed epoxy group and acetic acid by-produced. Vinyl group -CH = CH ₂ unreacted epoxy groups generated by the epoxidation reaction

Embedded image And modified substituents

Embedded image The formation ratio of the mixture of the three is determined by the type of the epoxidizing agent, the molar ratio of the epoxidizing agent, the olefin bond, the reaction conditions, and the like. Epoxy group in epoxy resin of the present invention

Embedded image It is essential that at least one or more is contained in the resin,

Embedded image The more, the more preferable.

Embedded image [R ³ is any one of H, an alkyl group, an alkylcarbonyl group and an arylcarbonyl group] is preferably as small as possible. The target compound can be extracted from the crude reaction solution by ordinary chemical industrial means such as concentration. Next, the present invention will be described with reference to examples. Synthesis Example 1 9.3 g of butanol and 100 g of 4-vinylcyclohexene-1-oxide were mixed, and 130 g of a 10% BF ₃ etherate / ethyl acetate solution was added dropwise while maintaining the reaction temperature at 50 ° C. After the reaction, low-boiling components were removed by distillation to obtain 103 g of a transparent liquid polyether compound (hereinafter, referred to as compound [A1]). The number average molecular weight by GPC of the compound [A1] was 818. Next, 50 g of the compound [A1] and 50 g of ethyl acetate were mixed, and 30 g of peracetic acid was added dropwise while maintaining the reaction temperature at 30 ° C. to perform epoxidation. After the reaction, low boiling components are removed by distillation, and a transparent solid epoxy compound (hereinafter, epoxy compound [A2]) 55
g was obtained. The oxirane oxygen concentration of this epoxy compound (A2) is 9.
53%, softening point was 65 ° C. Example 1 9.3 g of butanol and 115 g of 1,2-epoxy-9-decene were obtained in the same manner as in Synthesis Example 1 to obtain 118 g of a transparent liquid polyether compound (hereinafter, referred to as compound [B1]). The number average molecular weight by GPC of the compound [B1] was 1043. Next, 50 g of compound [B1] and 50 g of ethyl acetate were mixed, and epoxidation was carried out by dropwise addition of 25 g of peracetic acid while maintaining the reaction temperature at 60 ° C. After the reaction, 53.5 g of a transparent liquid epoxy compound (hereinafter referred to as epoxy compound [B2]) is removed by distillation to remove low boiling components.
I got The oxirane oxygen concentration of this epoxy compound (B2) is 8.
12%, viscosity was 4000 cps at 25 ° C. Example 2 10.8 g of benzyl alcohol and 63 g of 1.2-epoxy-7-octene were polyetherified in the same manner as in Synthesis Example 1,
Epoxidation was further performed with 38 g of peracetic acid to obtain 81 g of a transparent liquid epoxy compound (hereinafter, epoxy compound [C2]). The oxirane oxygen concentration was 9.31% and the viscosity was 3,200 cps. Comparative Example 1 13.4 g of trimethylolpropane and 87 g of 4-vinylcyclohexene-1-oxide were polyetherified and epoxidized in the same manner as in Example 1 to obtain 108 g of a transparent solid epoxy compound (hereinafter referred to as epoxy compound [D2]). Obtained. The oxirane oxygen concentration was 8.65% and the softening point was 75 ° C. Comparative Example 2 7.4 g of butanol, 62 g of 4-vinylcyclohexene-1-oxide, α-olefin epoxide 4 having 12 to 14 carbon atoms
In the same manner as in Example 1, 110 g of a transparent liquid epoxy compound (hereinafter referred to as epoxy compound [E2]) was obtained. Oxirane oxygen concentration is 5.48% and viscosity is 15000cps (25 ℃)
Met. In each of the above examples, the softening point was measured according to JIS K6911, and the viscosity was measured using a rotary E-type viscometer. Methylhexahydrophthalic anhydride (blending ratio: ethylhexahydrophthalic anhydride / epoxy compound = 1.0) and triphenylphosphine (blending amount 1%) were added to the epoxy compound and epicode 828 (oiled shell) produced in the above example. After casting, 120 ° C x 2 hours, then 240
The composition was cured at 1 ° C. × 1 hour. <Measurement of water absorption of cured product> A test piece of 4 cm square was prepared from the cured resin, and the temperature was 80 ° C and the relative humidity was 8
The change in weight after 7 days under 5% was measured to be the water absorption. The results obtained above are shown in Table 1.

[Table 1]

【The invention's effect】

As is evident from Table 1, the epoxy resin composition of the present invention has a lower epoxy equivalent weight than a conventional epoxy compound produced by copolymerizing α-olefin epoxide or allyl glycidyl ether even when a liquid one is produced. Does not increase, and the water absorption does not deteriorate. Utilizing such features, it can be expected to exhibit excellent performance in a wide range of fields such as sealants for ICs and LSIs, sealants for LEDs, matrix resins for composites, and paints.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 65/00-65/48 C08G 59/00-59/72 C08L 63/00

Claims (12)

(57) [Claims] (1) The following general formula (1): [In the general formula (1), n is 0 to 20] A polyether compound obtained by subjecting a monoepoxy compound of an alkadiene represented by the following formula to ring-opening addition polymerization to a compound having one or more active hydrogens. 2. The polyether compound according to claim 1, wherein n in the general formula (1) is 4. 3. The polyether compound according to claim 1, wherein n in the general formula (1) is 6. 4. The polyether compound according to claim 1, wherein n in the general formula (1) is 12 to 14. 5. A compound represented by the following general formula (1): [In the general formula (1), n is 0 to 20] A polyether compound obtained by subjecting a monoepoxy compound of an alkadiene represented by the following formula to ring-opening addition polymerization to a compound having one or more active hydrogens is epoxidized. An epoxy compound characterized by being obtained. 6. The epoxy compound according to claim 5, wherein n in the general formula (1) is 4. 7. The epoxy compound according to claim 5, wherein n in the general formula (1) is 6. 8. The epoxy compound according to claim 5, wherein n in the general formula (1) is 12 to 14. 9. The following (a) and (b) (a) a polyether compound obtained by ring-opening addition polymerization of 4-vinylcyclohexene-1-oxide to a compound having one or more active hydrogens by epoxidation. (B) the following general formula (1): [In the general formula (1), n is 0 to 20] A polyether compound obtained by subjecting a monoepoxy compound of an alkadiene represented by the following formula to ring-opening addition polymerization to a compound having one or more active hydrogens is epoxidized. A composition comprising the obtained epoxy compound. 10. The composition according to claim 9, wherein n in the formula (1) is 4. 11. The composition according to claim 9, wherein n in the general formula (1) is 6. 12. The composition according to claim 9, wherein n in the general formula (1) is 12 to 14.