JP2639833B2 - Polyether compound - Google Patents

Description

The present invention relates to an alicyclic polyether compound having both an ether group and a vinylic double bond, and having an organic carboxylic acid ester structure at a terminal. It relates to a novel alicyclic polyether compound.

More specifically, the present invention relates to a novel alicyclic polyether compound which is a raw material of an alicyclic epoxy having improved heat resistance, weather resistance, and water resistance and low viscosity and improved water absorption.

[Prior Art] Conventionally, polyether compounds having a hydroxyl group at the end, allyl group, vinyl group, etc. have been widely used as resin raw materials such as paints, adhesives and molding agents.
Examples of polyether compounds having both a hydroxyl group and a vinyl group include those disclosed in JP-A-60-161940 (US Pat. No. 4,565,859). It is based on 4-vinylcyclohexene-1 using an organic compound having active hydrogen as an initiator.
-Ring-opening polymerized oxide.

Since this polyether compound has a basic skeleton composed of an oxycyclohexane ring, when used as a resin raw material, a resin excellent in hardness, strength, and the like can be obtained. Moreover, since it does not have an aromatic ring, it is excellent in weather resistance.

Further, the double bond is rich in reactivity because of the so-called terminal double bond, and can be used for various reactions. Further, for example, it can be used as a raw material of a silane coupling agent by adding a silane compound, and can be used as a modifier such as an unsaturated polyester by utilizing the radical polymerizability of a vinyl group. Further epoxidation of this vinyl group using a suitable epoxidizing agent, heat resistance, water resistance, weather resistance,
An epoxy resin having excellent curability can be obtained.

As described above, polyether compounds are industrially very important substances.

[Problem to be Solved by the Invention] However, Japanese Patent Application Laid-Open No. 60-161940 (US Pat.
5,859) is the same as the polyether compound of the present invention, However, since the terminal is an OH group, the viscosity becomes high even with a relatively low molecular weight. In addition, when a cured product is prepared by producing an epoxy resin using such a polyether compound as a raw material, some problems remain, such as a high water absorption of the cured product.

For this purpose, attempts have been made to modify the polyether compound in accordance with the purpose of use and the method of use, but no satisfactory compound has been obtained.

In view of such circumstances, as a result of investigations by the present inventors, low viscosity was achieved by introducing an ester bond to part or all of the OH group at the molecular terminal of the alicyclic polyether compound disclosed in the above publication. As a result, it has been found that the cured product of the epoxy resin obtained from the polyether compound has improved water resistance, leading to the present invention.

[Means for Solving the Problems] That is, the present invention provides a compound represented by the following general formula (I): [However, in the general formula (I), X is constituted by an oxycyclohexane skeleton having a vinyl group represented by the following general formula (II), and it is essential that at least one skeleton (II) is contained in one molecule. Y represents H or an acyl group, and contains at least one acyl group in at least one molecule; R is a residue consisting of a part obtained by removing the active hydrogen from an organic compound having one active hydrogen, n1, n2... Nl are each an integer of 0 or 1 to 100, and the sum is 1 to 100; l
Represents an integer of 1 to 100, and the R is bonded to a bonding end other than -O- in the formula (II)]. It is.

 Next, the present invention will be described in detail.

In the novel polyether compound represented by the formula (I) of the present invention, R is a residue consisting of a portion obtained by removing active hydrogen from an organic compound having active hydrogen.

Organic substances having active hydrogen as its precursor include:
Examples 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, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, And polyhydric alcohols such as dipentaerythritol.

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, toluenediamine , Hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine and the like.

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;

Further, 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 compounds having active hydrogen can be used, and two or more of them may be used in combination.

In the novel polyether compound represented by the general formula (I) of the present invention, X represents an oxycyclohexane skeleton having a vinyl group. It is composed of

The oxycyclohexane skeleton (II) is 4-vinylcyclohexene obtained by dimerization of butadiene. Is partially epoxidized to 4-vinylcyclohexene-1-
Oxide Is ring-opened.

In the general formula (I), X is not limited to the case of (II) alone, and X may have a ring-opened skeleton of an epoxy compound having one or more epoxy groups other than 4-vinylcyclohexene-1-oxide. Absent. Two or more compounds having one or more epoxy groups may be used.

 Specific examples include the following compounds.

α-olefin epoxide represented by n = 2 to 25 _{(R 5, R 6, R} 7 is an ester of tert- carboxylic acid C9-C11) Alicyclic polyether compounds such as (Where R ^y is a hydrogen atom, an alkyl group, etc.) any glycidyl ether of polyalcohol and polyglycol,
Epoxidized soybean oil, polyolefin type epoxy resin such as epoxidized linseed oil, diglycidyl hydantoin, heterocyclic epoxy resin such as triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, glycidylamine resin such as triglycidyl P-aminophenol, Examples thereof include glycidyl ester resins such as diglycidyl phthalate and diglycidyl ester tetrahydrophthalate, and bisphenol A epoxy resins, bisphenol F epoxy resins, and novolak epoxy resins.

In the polyether compound represented by the general formula (I) of the present invention, n1, n2.
An integer of 0, the sum of which is 1 to 100.

If the sum of n1, n2,... nl exceeds 100, when an epoxy resin is produced, the molecular weight becomes too high and cannot be practically used.

1 is the number of active hydrogens of a compound having an active hydrogen of an initiator which is a precursor of R in the polyether compound represented by the general formula (I), and is an integer of 1 to 100.

All or a part of Y in the polyether compound represented by the general formula (I) is constituted by an acyl group, and it is essential that at least one or more acyl groups are contained in one molecule.

Examples of the acyl group include those derived from formic acid, acetic acid, propionic acid, and the like.

 Further, a part of Y may remain H.

In order to obtain the polyether compound of the present invention represented by the general formula (I), first, the above-mentioned various active hydrogens are
Are reacted with a compound having one or more epoxy groups (including 4-vinylcyclohexene-1-oxide) in the presence of a catalyst. In the compound obtained by this reaction, all of the Y moieties of the polyether compound represented by the general formula (I) are OH groups (however, when the initiator is an amine having no OH or COOH, H) A polyether compound in which all side chains are vinyl groups.

 That is, it has the following structure.

"However, X is R, l and n1, n2... Nl are the same as those in the general formula (I). 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 acid salts 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%.

The reaction temperature is from -20 to 200C, preferably from 0C to 120C.

The reaction can be carried out using a catalyst. 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.

The molar ratios of the raw materials used for the reaction are as follows.

1 to 100 mol of 4-vinylcyclohexene-1-oxide and 99 to 0 of a compound having at least one epoxy group other than 4-vinylcyclohexene-1-oxide per 1 mol of the compound having active hydrogen as an initiator. The reaction is carried out in such a manner that the total amount of the epoxy compounds is 100 mol or less by mixing in a molar range.

When the amount of 4-vinylcyclohexene-1-oxide is 1 mol or less per 100 mol of the total amount of the epoxy compound, the content of the vinyl group is small, so that the feature of the cyclohexane skeleton does not appear.

Conversely, if the total amount of the epoxy compounds exceeds 100 mol, the compound having active hydrogen does not function as an initiator, and the molecular weight becomes too high to be practically usable.

When a compound having two or more epoxy groups is used, 4-vinylcyclohexene-1-oxide is used.
Mix to within 50 mol%. If the content is more than 50 mol%, the molecular weight becomes too high and cannot be practically used.

Next, the part of the esterification reaction of the terminal OH group of the polyether compound represented by the general formula (IV) will be described.

Examples of the esterifying agent include organic carboxylic acids and salts thereof such as formic acid, acetic acid and propionic acid, halogenated amines such as acetyl chloride and benzoyl chloride, and organic carboxylic anhydrides such as acetic anhydride and propionic anhydride. it can.

Further, a transesterification reaction with an ester such as ethyl acetate or butyl acetate may be performed.

In the esterification reaction and transesterification reaction, a catalyst may not be used, but protonic acids such as sulfuric acid and toluenesulfonic acid, Lewis acids such as BF ₃ and SnCl ₃ and their complex salts, and bases such as pyridine and NaOH For example, a commonly used catalyst can be used.

The amount of the catalyst used varies depending on the type, but is 10% or less, preferably 5% or less, based on the starting materials. By selecting the type and amount of the esterifying agent and the reaction conditions, the terminal OH
The ratio of carboxylic acid groups and carboxylic acid ester groups can be adjusted, but it is necessary to esterify one or more OH groups in one molecule.

The temperature of esterification and transesterification is -20 ~
The temperature is 200 ° C, preferably 0 to 200 ° C.

Solvents can also be used to control the reaction.

The polyether compound synthesized in this manner can be taken out of the reaction crude liquid by ordinary chemical engineering means such as concentration.

 Next, the present invention will be described with reference to examples.

"Examples"<SynthesisExample-1> 38 g (0.28 mol) of trimethylolpropane and 527 g (4.25 mol) of 4-vinylcyclohexene-1-oxide were mixed, followed by 126 g of a 10% BF ₃ etherate solution in ethyl acetate.
Was added dropwise over 4 hours to cause a reaction.

 At this time, the inside of the system was kept at 50 ° C. during the dropwise addition.

After the completion of the dropwise addition, analysis by gas chromatography confirmed that trimethylolpropane and 4-vinylcyclohexene-1-oxide had almost disappeared.

Subsequently, 97 g (0.95 mol) of acetic anhydride was added and the mixture was added at 80 ° C for 3 hours.
Heated for hours.

Subsequently, washing was performed three times with pure water to remove the solvent.
It was confirmed by infrared absorption spectrum analysis that the terminal OH group had disappeared.

The results of analysis by gas chromatography and NMR were as follows.

[However, n1 + n2 + n3 = 15 on average, X is an oxycyclohexane skeleton having the following vinyl group <Synthesis Example 2> 32 g (1 mol) of methanol, 327 g (3 mol) of 4-vinylcyclohexene-1-oxide, 153 g (1.5 mol) of acetic anhydride
Mol) was used, and the corresponding polyether compound was obtained in the same manner as in Synthesis Example-1.

<Synthesis Example 3> 62 g (1 mol) of ethylene glycol, 248 g (2 mol) of 4-vinylcyclohexene-1-oxide, 20 acetic anhydride
A corresponding polyether compound was obtained in the same manner as in Synthesis Example 1 except that 4 g (2 mol) was used.

<Synthesis Example-4> Corresponding to Synthesis Example-1 except that 134 g (1 mol) of trimethylolpropane, 327 g (3 mol) of 4-vinylcyclohexene-1-oxide, and 367 g (3.6 mol) of acetic anhydride were used. A polyether compound was obtained.

<Comparative Synthesis Examples 1-4> A polyether compound having a terminal OH group was obtained in the same manner as in Synthesis Example 1 except that the oxidation reaction using acetic anhydride in Synthesis Examples 1-4 was omitted.

Table 1 shows the results of measuring the softening point and viscosity of the polyether compounds obtained in Synthesis Examples 1-4 and Comparative Synthesis Examples 1-4.
Shown in

"Application Examples" Epoxidation of various polyether compounds obtained in <Synthesis Example-1> and <Comparative Synthesis Example-1> using peracetic acid gave corresponding epoxy compounds.

1.0 equivalent of this epoxy compound was added to 1.0 equivalent of phenol novolak resin and triphenylphosphine, respectively.
An epoxy resin composition was obtained using 0.5% in the amounts shown in Table 1.

After pulverizing these epoxy resin compositions, they were press-molded at 150 ° C. for 30 minutes and further cured at 200 ° C. for 2 hours.

Subsequently, a pressure cooker test (121 ° C, 95% R
H, 144 hours), and the water absorption was measured. As a result, the epoxy compound of Comparative Example-1 was 3.3%, whereas the epoxy compound of Example-1 was 2.6%.

[Effect of the Invention] The polyether compound of the present invention synthesized as described above can produce a low-viscosity grade, is excellent in water resistance and the like, and can be used in various applications.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C07C69 / 22 C07C69 / 22 C08F 299/02 MRS C08F 299/02 MRS C08G 65/32 NQP C08G 65 / 32 NQP

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula (I) [However, in the general formula (I), X is constituted by an oxycyclohexane skeleton having a vinyl group represented by the following general formula (II), and it is essential that at least one skeleton (II) is contained in one molecule. Y represents H or an acyl group, and contains at least one acyl group in at least one molecule; R is a residue consisting of a part obtained by removing the active hydrogen from an organic compound having one active hydrogen, and n1, n2,.
Or an integer of 1 to 100, the sum of which is 1 to 100, 1 represents an integer of 1 to 100, and R is bonded to a non-O-bonding end in the formula (II)]. Compound.