JPH02142748A - Polyether compound - Google Patents

Abstract

NEW MATERIAL:The polyether compound of formula I [at least a part of X is oxycyclohexane skeleton containing vinyl group and expressed by formula II and the compound contains at least one skeleton of formula II in one molecule; Y is OH (or H when an initiator is an amine free from OH and COOH) or an organic carboxylic acid ester residue and the compound contains at least one residue of said ester in one molecule; R is organic compound residue having lactive hydrogen atoms; n1-nl are 0 or 1-100: the sum of n1-nl is 1-100; lis 1-1000]. EXAMPLE:The compound of formula III. USE:Useful as a raw material for epoxy resin, etc., having high heat-resistance, weather resistance and water resistance, low viscosity and excellent curability. PREPARATION:The compound of formula I can he produced by reacting a compound having l active hydrogen atoms with a compound having >=1 epoxy group in the presence of a catalyst.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is an alicyclic polyether compound having both an ether group and a vinylic double bond, and which has an organic carboxylic acid ester structure at the terminal. The present invention relates to a novel alicyclic polyether compound having the following properties.

More specifically, heat resistance, weather resistance, and water resistance have been improved.
The present invention also relates to a novel alicyclic polyether compound that is a raw material for alicyclic epoxy having low viscosity and improved water absorption.

[Prior Art] Conventionally, polyether compounds with terminal hydroxyl groups, allyl groups, vinyl groups, etc. have been widely used as raw materials for resins such as paints, adhesives, and molding materials.

For example, a polyether compound having both a hydroxyl group and a vinyl group is disclosed in JP-A-60-161940 (USP
4,565,859) and others.

This is a 4-
This is ring-opening polymerization of vinylcyclohexene-1-oxide.

Since the basic skeleton of this polyether compound is composed of an oxycyclohexane ring, when used as a resin raw material, a resin excellent in terms of 2 hardness, 9 strength, etc. can be obtained.

Also, since it does not have an aromatic ring, it has excellent weather resistance.

Furthermore, the double bond is a so-called terminal double bond, so it is highly reactive and can be used in a variety of reactions. Also.

For example, it can be used as a silane coupling agent M material by adding a silane compound.

Utilizing the radical polymerizability of the vinyl group, it can be used as a modifier for unsaturated polynisder. Furthermore, by epoxidizing this vinyl group using a suitable epoxidizing agent, an epoxy resin having excellent heat resistance, water resistance, weather resistance, and curability can be obtained.

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

[Problem to be solved by the invention] However, the above-mentioned Japanese Patent Application Laid-Open No. 60-161940 (U
SP 4,565,859) The polyether compound disclosed in the above (SP 4,565,859) is similar to the polyether compound of the present invention.
Since it contains the structure II) or has an OH group at the end, it has a high viscosity even if it has a relatively low molecular weight. .

Furthermore, when producing an epoxy resin using such a polyneedle compound as a raw material to create a cured product, some problems remain, such as a high water absorption rate of the cured product.

For this purpose, attempts have been made to modify polyether compounds depending on the purpose and method of use.

We're not getting enough.

In view of this situation, the present inventors investigated and found that the O at the molecular terminal of the alicyclic polyether compound disclosed in the above publication was
The discovery that low viscosity can be achieved by introducing ester bonds into some or all of the H groups, and as a result, the water resistance of the cured epoxy resin obtained from the polyether compound is improved. This led to the invention.

[Structure of the Invention] That is, the present invention is based on the following general formula (I) [However, in the general formula (I), X is oxydicyclohexane having a vinyl group, all or part of which is represented by the following general formula (11). It is essential that at least one skeleton (II) is contained in at least one molecule. H)t represents an organic carboxylic acid ester residue, and at least one molecule contains one or more of the residues.

R is an organic compound residue having active hydrogen.

nl, n2...nj are O or an integer from 1 to 100, and the sum thereof is from 1 to 100. J! represents an integer from 1 to 100] is a polyether compound J represented by:

Next, the present invention will be explained in detail.

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

Organic substances having active hydrogen that are precursors include alcohols, phenols, carboxylic acids, amines,
Examples include thiols.

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, 1.3
Butanediol, 1.4 butanediol, pentanediol, 1.6 hexanediol, neopentyl glycol,
Examples include polyhydric alcohols such as neopentyl glycol oxypivalate, cyclohexane dimetatool, glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol.

Examples of phenols include phenol, cresyl, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, A1 bisphenol F for bisphenol, 4,4°-dihydroxybenzophenone, bisphenol S, phenol resin, cresol novolak resin, and the like.

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.

Compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid, can also be used.

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, polyhydric alcohol esters of mercaptopropionic acid or mercap-1-propionic acid, such as nitride ethylene glycol dimercaptopropionate, and trimethylolpropane trimercaptopropion. acids, pentaerythritol pentamercaptopropionic acid, etc.

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.

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, tetra-dolphthalic acid, etc. There is.

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 is mainly composed of an oxycyclohexane skeleton having a vinyl group.

The oxycyclohexane skeleton (II) is a ring-opened 4-vinylcyclohexene obtained by trimerizing butadiene.

In general formula (1), X is not limited to the case of (11) alone, and even if an epoxy compound having one or more epoxy groups other than 4-vinylcyclohexene-1-oxide contains a ring-opened skeleton. There is no problem. 1 epoxy group
Two or more kinds of compounds having at least one of these compounds may be used.

Specifically, the following compounds may be mentioned.

Alicyclic polyether compounds such as partially epoxidized α-olefin epoxide represented by 4 1-oxide vinylcyclo to A 2-25 (R5, R6, R7 are esters of C9-C11 tert-carboxylic acids) (However, Ry is a hydrogen atom, an alkyl group, etc.) Polyolefin-type epoxy resins such as glycidyl ethers of any polyalcohols and polyglycols, epoxidized soybean oil, and epoxidized linseed oil.

Heterocyclic epoxy resins such as diglycidyl dantoin 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 tetrahydrophthalate, bisphenol A epoxy resins, bisphenol F epoxy resins, and novolac epoxy resins.

In the polyether compound represented by the general formula (I) of the present invention, nl, n2...n, I! is 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100. nl
, n2... If the sum of nl exceeds 100, the molecular weight of the epoxy resin produced will be too high to be practically usable.

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

All or part of Y in the polyether compound represented by the general formula (1) is composed of an organic carboxylic acid ester residue, and it is essential that at least one molecule contains one or more of the residues.

The organic carboxylic acid ester residue is formic acid.

Examples include ester residues such as acetic acid and propionic acid.

Further, a part of Y may remain OH.

Now, in order to obtain the polyether compound of the present invention represented by the general formula (I), first of all, a compound having one or more of the above-mentioned active hydrogen groups and a compound having one or more epoxy groups (4
-vinylcyclohexene 1-oxide) in the presence of a catalyst. The compound obtained by this reaction is a polyether compound represented by the general formula (I) in which all the Y portions are OH groups and all the side chains of the X portions are vinyl groups.

That is, it has the following structure.

"However, organic bases such as pyridines, imidazoles, 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, and alkali metals such as sodium methylate. Alcolades, alkalis such as KOH and NaOH, BF3
, ZnCJl , A,llC,Q , SnC,l1
Lewis acids such as No. 4 or their complexes, and organometallic compounds such as triethylaluminum and diethylzinc can be used.

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 -20~200℃, preferably O'C~12
It is 0°C.

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.

The molar ratio of raw materials to be used in the reaction is as follows.

4 per mole of a compound having active hydrogen as an initiator
- Mixing 1 to 100 moles of vinylcyclohexene-1-oxide and 99 to 0 moles of a compound having one or more epoxy groups other than 4-vinylcyclohexene 1-oxide, so that the total amount of epoxy compounds is 100 moles or less React as follows.

If the amount of 4-vinylcyclohexene-1-oxide is 1 mole or less in a total of 100 moles of the epoxy compound, the content of vinyl groups will be so small that the characteristics of the cyclohexane skeleton will not be apparent.

On the other hand, if the total amount of epoxy compounds exceeds 100 moles, the active hydrogen-containing compound loses its function as an initiator, and its molecular weight becomes too high to be of practical use.

In addition, when using a compound having two or more epoxy groups, 5
Mix so that the content is within 0 mol%. If the amount exceeds 50 mol %, the molecular weight becomes too high to be practically usable.

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

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

Alternatively, a transesterification reaction with esters such as ethyl acetate and butyl acetate may be performed.

During esterification and transesterification reactions.

Although it is not necessary to use a catalyst, commonly used catalysts such as protic acids such as sulfuric acid and toluenesulfonic acid, Lewis acids such as BF3.5nCj3 and their complex salts, and bases such as pyridine and NaOH can also be used. .

The amount of catalyst used varies depending on the type, but is 10% or less, preferably 5% or less based on the starting material.

Type and amount of esterifying agent1 The ratio of terminal OH groups and carboxylic acid ester groups can be adjusted by selecting the reaction conditions, but it is necessary to esterify one or more OH groups in one molecule. .

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

Solvents can also be used to control the reaction.

The polyether compound thus synthesized can be taken out from the crude reaction solution by conventional chemical engineering means such as concentration.

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

[Example J Synthesis Example-1> 38 g (0.28 mol) of trimethylolpropane and 4
-vinylcyclohexene-1-oxide 527g (4
, 25 mol) followed by BF3 ethylate 10%
126 g of ethyl acetate solution was added dropwise over 4 hours to cause a reaction.

At this time, the temperature inside the system was maintained at 50°C.

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

Subsequently, 97 g (0.95 mol) of acetic anhydride was added to
Heated at 0°C for 3 hours.

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

Furthermore, the results of analysis using gas chromatography and NMR were as follows.

[However, nl+n2+n3-average 15. 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.

A corresponding polyether compound was obtained in the same manner as Synthesis Example 1 except that 153 g (1.5 mol) of acetic anhydride was used.

Synthesis Example-3> Synthesis Example-1 except that 62 g (1 mol) of ethylene glycol, 248 g (2 mol) of 4-vinylcyclohexene-1-oxide, and 204 g (2 mol) of acetic anhydride were used.
Obtain the corresponding polyether compound in the same manner.

<Synthesis Example-4> 134 g (1 mol) of trimethylolpropane and 327 g (3 mol) of 4-vinylcyclohexene-1-oxide
A corresponding polyether compound was obtained in the same manner as in Synthesis Example 1, except that 367 g (3.6 mol) of acetic anhydride was used.

Comparative Synthesis Examples 1 to 4> A polyether compound having an OH group at the terminal was obtained in the same manner as Synthesis Example 1 except that the acetylation reaction using acetic anhydride in Synthesis Examples 1 to 4 was omitted.

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

"Application Example" The various polyether compounds obtained in Synthesis Example 1 and Comparative Synthesis Example 1 were epoxidized using peracetic acid to obtain corresponding epoxy compounds.

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

After pulverizing these epoxy resin compositions, they were heated at 150°C for 3
It was press-molded for 0 minutes and then cured at 200° C. for 2 hours.

Next was the pressure test (121℃).

When the water absorption rate was measured, it was 3.3% for the epoxy compound of Comparative Example-1, while it was 2.6% for the epoxy compound of Example-1. .

[Effects of the Invention] The polyether compound of the present invention synthesized in this manner can be produced in a low viscosity grade,
It has excellent water resistance and can be used for various purposes.

Table-1

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [However, in the general formula (I), X may be expressed in whole or in part by the following general formula (II). It is essential that at least one skeleton (II) is contained in one molecule, and Y is OH (provided that the initiator has OH or COOH). (H) or an organic carboxylic acid ester residue in the case of an amine that does not have a formula, and includes at least one such residue in one molecule. organic compound residues having active hydrogen, n1, n
2... nl is 0 or an integer of 1 to 100, the sum of which is 1 to 100, l represents an integer of 1 to 100] A polyether compound represented by the following.