JPS63234028A - Polyether compound - Google Patents

Abstract

PURPOSE:To obtain the titled novel compound useful as a resin raw material to give a resin having improved hardness, strength, flexibility, water-resistance, etc., by reacting a compound having active hydrogen with a specific oxide having vinyl group and an epoxy compound. CONSTITUTION:The objective polyether compound of formula I [R1 is residue having l active hydrogen groups; n1-nl are 0-100; A is mixture of group of formula II and group of formula III (R2 is residue of a compound having epoxy group)] can be produced by mixing (A) 1mol. of a compound having active hydrogen (e.g. methanol and acetic acid), (B) preferably 2-100mol. of 4-vinylcyclohexene-1-oxide or 4-vinylbicyclo[2,2,1]heptene-1-oxide and (C) preferably 99-1mol.% (based on 1-99mol.% of the component B) of a compound having epoxy group and reacting the components e.g. at -20-+200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel polyether compound characterized by containing a vinylic double bond.

More specifically, the present invention relates to a novel polyether compound having both an ether group and a vinylic double bond.

(Prior art) Polyether compounds have traditionally been used in polyurethanes such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and paints.

It is widely used as a resin raw material for adhesives, molding materials, etc.

Many of these polyether compounds have a hydroxyl group at the end, and when used as resin raw materials, they have the disadvantage that their range of application is limited.

In order to overcome these drawbacks, polyether compounds in which the terminal end is an allyl group obtained by polymerizing the glycidyl group of allyl glycidyl ether, and polyether compounds in which the terminal end is a vinyl group by thermal decomposition of polypropylene glycol are used.

However, since these compounds have a linear molecular structure,
Resins obtained using these resins have excellent flexibility, but many are unsatisfactory in terms of hardness and strength.

Based on this foreground, the inventors of the present invention
No. 40 describes a new polyether compound that has a vinyl double viscosity in the molecule obtained by polymerizing 4-vinylcyclohexene 1-oxide and has a skeleton that can impart hardness as a resin/raw material. Also, patent application 1985-1985
No. 03 (=Application filed on August 18, 1986 under the provisions of Article 42-2, Paragraph 1 of the Patent Law, title of invention: polyether compound), 4-vinylbicyclo[2,2,11hebutene-1-oxide (vinylnorbornene oxide) has a vinyl double viscosity in the molecule obtained by polymerizing S
We have disclosed novel polyether compounds with skeletons that can impart hardness as raw materials for fats. These compounds are useful for modifying silane coupling agent raw materials, polyester resins, etc. by utilizing highly reactive double viscosity. be.

Further, the epoxy resin obtained by epoxidizing the vinyl double viscosity of the above-mentioned polyether compound with an epoxidizing agent is excellent as an epoxy resin having excellent heat resistance.

(Problems to be Solved by the Invention) However, as the methods and purposes of their use have diversified, the performance requirements for polyether compounds have also diversified.
1ten-1-oxy to vinylbicyclo[2,2゜1]
There has been a demand for modification of compounds obtained by polymerizing only vinylnorbornene oxide.

This is the result of studies conducted by the inventors based on this situation.

A mixture of 4-vinylbicyclo[2,2,11butene-1-oxide (vinylnorbornene oxide) or 4-vinylhexene-1-oxide and a compound having one epoxy group has one or more active hydrogen groups. A polyether compound obtained by addition polymerization to a compound containing
Polyether compounds disclosed in Japanese Patent Application No. 0-161940 and Japanese Patent Application No. 1985-1983 (filed on August 18, 1988 pursuant to Article 42-2, Paragraph 1 of the Patent Law) The present inventors have completed the present invention by discovering that they exhibit excellent properties in various respects such as heat resistance, water resistance, flexibility, and glass transition temperature without impairing their characteristics.

(Structure of the Invention) That is, the present invention provides the following formula (I
) where R1 is an organic compound residue having one active hydrogen.

nl, R2, ----nj are O or an integer from 1 to 100, and the sum thereof is from 1 to 100.

1 represents an integer from 1 to 100.

A is a mixture of (a) an oxydinorbornene skeleton having a vinyl group or an oxycyclohexane skeleton having a vinyl group, and (b) an alkyl ether skeleton.

However, R2 is an aliphatic or alicyclic organic compound residue having one epoxy group.

Next, the present invention will be explained in detail.

Examples of the active hydrogen-containing compound used to produce the polyether compound represented by the general formula (1) of the present invention include alcohols, phenols, carboxylic acids, amines, and thiols.

The alcohols may be monoalcohols or polyhydric alcohols.

For example, aliphatic alcohols such as methanol, ethanol, 10-panol, 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, betanediol, 1.6-hexanediol, neopentyl glycol, oxypivalic acid neopentyl glycol ester, cyclohexane dimetatool, glycerin, diglycerin, polyglycerin, trimethylolpropane,
Examples include polyhydric alcohols such as trimethylolethane, pentaerythritol, and dipentaerythritol.

Examples of phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A1 bisphenol F, 4,4°-dihydroxybenzophenone, bisphenol S, phenol resin, and cresol novolak 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, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, and ethanolamine.

Examples of thiols include mercapto such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan, polyhydric alcohol esters of mercaptopropionic acid or mercapto-10 pionic acid, such as ethylene glycol dimercapto-10 pionic ester, trimethylolpropane trimercapto-10 Examples include pionic acid, pentaerythritol pentamercaptopropionic acid, and the like.

In addition, as compounds having active hydrogen, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose 7 acetate butylate, hydroxyethyl cellulose,
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,
Examples include polypropylene polyol and polytetramethylene glycol.

In addition, the compound having active hydrogen may have unsaturated type 2 packing in its skeleton, and specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, and tetrahydrophthalic acid. There is.

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

(a) The oxydinorbornene skeleton having a vinyl group or the oxycyclohexane skeleton having a vinyl group in the polyether compound represented by the general formula (I) of the present invention is 4-vinylbicyclo[2°2.1] to 1 ten -1-oxide (vinylnorbornene oxide) or 4-vinylcyclohexene 1-oxide is an organic compound residue in which the oxide moiety is ring-opened.

1-ten-1-oxide (vinylnorbornene oxide) to 4-vinylbicyclo[2,2,1] is a compound represented by the following formula, and is obtained by the Diels-Alder reaction between butadiene and citalopentadiene. It is manufactured industrially by evaporating heptene (vinylnorbornene) with peracetic acid, hydrogen peroxide, etc.

In addition, 4-vinylcyclohexene 1-oxide is a compound represented by the following formula, and is industrially produced by epoxidizing 4-vinylcyclohexene obtained by the dimerization reaction of butadiene with peracetic acid, hydrogen peroxide, etc. ing.

In the polyether compound represented by general formula (I) in the present invention, (b) alkyl ether skeleton -R2-
0- is an organic compound residue in which the epoxy group portion of a compound having one epoxy group represented by the following general formula (1113) is ring-opened, and specifically, compounds shown by the following formula fall under this. .

However, R1, R2, R3, R4 are hydrogen or n=2~
α-olefin epoxide represented by 25 (R5, R6, R, are esters of C9 to C11 tert-carboxylic acid) In other words, in the polyether compound represented by the general formula (I) of the present invention, -A- may be a mixture of only an oxydinorbornene skeleton having a vinyl group or an oxycyclohexane skeleton having a two-step group.

In addition, any compound represented by (III) may be used alone or in combination of two or more.

The polyether compound in the present invention is a compound having active hydrogen and 4-vinylbicyclo[2°2.1].
Thene-1-oxide (vinylnorbornene oxide)
or by reacting 4-vinylcyclohexene l-oxide and the compound having one epoxy group represented by the general formula (III) that produces the alkyl ether skeleton -R2-0- in the presence of a catalyst. Obtainable.

In this reaction, a compound having active hydrogen and 4-vinylbicyclo[2,2,1] are converted into 1-ten-1-oxide (vinylnorbornene oxide) or 4-vinylcyclohexene-1-oxide and a compound having one epoxy group. The molecular weight can be controlled in various ways by changing the reaction ratio.

In addition, a compound having one 1-ten-1-oxide (vinylnorbornene oxide) or 4-vinylcyclohexene 1-oxide and one epoxy group is added to 4-vinylbicyclo[2,2,1] per molecule of the compound having active hydrogen. It is desirable to react at a ratio of 2 to 10 O in total.

When the sum is 100 or more, it becomes a solid with a high melting point.

In reality, it cannot be used.

4-vinylbicyclo[2,2,1]hebutene-1-oxide (vinylnorbornene oxide) or 4-vinylcyclohexene 1-oxide and a compound having one epoxy group is 4-vinylcyclohexene 1-oxide or 4-vinyl Bicyclo[2,2,1]hebutene-1-oxide is reacted at a ratio of 1 to 99% and a compound having one epoxy group is reacted at a ratio of 99 to 1%.

If 4-vinylbicyclo[2,2,1]hebutene-1-oxide (vinylnorbornene oxide) or 4-vinylcyclohexene 1-oxide is less than 1%, the vinyl group content becomes too low and the norbornene skeleton or cyclohexane skeleton There are no characteristics.

(b) If the amount of the compound having one epoxy group represented by the above general formula (III) that forms the alkyl ether skeleton -R2-0- is less than 1%, the desired modification cannot be carried out.6 The polyether of the present invention Assuming that the compound (b) is a compound having one epoxy group represented by the above general formula (III) that forms an alkyl ether skeleton -R2-0-, the following is obtained when the compound is ether bonded randomly or in blocks.

4-vinylbicyclo[2,2
, 11 when adding 1-ten-1-oxide or 4-vinylcyclohexene 1-oxide (vinylnorbornene oxide) and a compound having one epoxy group,
When 1-ten-1-oxide (vinylnorbornene oxide) or 4-vinylcyclohexene 1-oxide and a compound having one epoxy group are simultaneously reacted with 4-vinylbicyclo[2,2,1], a random polymer is formed. .

Also, 1 ten-1 to 4-vinylbicycloC2,2,11
-oxide (vinylnorbornene oxide) or 4
A block copolymer can be formed by reacting either -vinylcyclohexene 1-oxide or a compound having one epoxy group first, and then reacting the reaction adduct with the other.

Either reaction format may be used in the present invention.

Catalysts used during the reaction include amines such as methylamine, ethylamine, propylamine, and piperazine; organic salts such as pyridine and imidazoles; quaternary ammonium salts such as tetrabutylammonium bromide;
Organic acids such as formic acid, acetic acid, and 10-pionic acid; inorganic acids such as sulfuric acid and hydrochloric acid; alcoholades of alkali metals such as sodium methylate; alkali bases such as KOH and NaOH;
Examples include Lewis acids such as F3, ZnCj, AjCj%5nCj4, 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.

(Effect of the invention) Now, the polyether compound synthesized in this way is
The basic skeleton is composed of a norbornene ring or a cyclohexane ring, and a substituent with a side chain is introduced into the 8 groups, so when used as a resin raw material, it not only has excellent hardness of 9 and strength, but also has moderate flexibility. It is possible to obtain a resin that has properties and water resistance.

Additionally, those without aromatic rings have excellent weather resistance.

Also, double viscosity is the so-called terminal 2f! Due to the bond, it has high reactivity and can be used for various reactions.

For example, by adding a silane compound, it can be used as a raw material for a silane coupling agent, and by utilizing the radical polymerizability of vinyl groups, it can be used as a modifier for unsaturated polyesters and the like.

Furthermore, this double viscosity can be improved using a suitable epoxidizing agent.

For example, heat resistance and weather resistance can be achieved by epoxidizing using peracids and hydroperoxides.

Epoxy resins with excellent water resistance and curability can also be obtained.

As described above, the polyether compound of the present invention is industrially very important as a raw material for various resins.

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

Example-1 [Synthesis of 4-vinylbicyclo[2,2,11 to 1-ten-1-oxide (vinylnorbornene oxide)] 4-vinylbicyclo[2,2,1]hebutan-1-ene (vinylnorbornene >1697.4g (14.15 mol) was charged into the reactor, and to this was added 1075.8g of peracid.
(14.15 mol) was added dropwise as an ethyl acetate solution over 5.5 hours while maintaining the reaction temperature at 40°C.

After the completion of charging peracetic acid, the mixture was further aged at 40°C for 1 hour.

The obtained reaction crude liquid was thoroughly washed with distilled water.

A transparent liquid was obtained by rectifying the organic layer using a distillation column.

The boiling point of this liquid was 25 TOr and 91°C.

According to infrared absorption spectrum analysis of the product, 810 cm,
It was confirmed that an epoxy group absorption exists at 1270 cm, and that a vinyl group absorption exists at 1640 cm and 1820 cm. NMR analysis confirmed that this compound has a structure shown by the following formula. .

[Synthesis of polyether having the structure represented by general formula (I) from mixed oxide] 16 g (0.5 mol) of methanol, 4-vinylbicyclo[2,
476 g (3.5 mol) of 2,1]hebutene-1-oxide (vinylnorbornene oxide'), 434 g (3.5 mol) of 4-vinylcyclohexitin-1-oxide as a compound forming the alkyl ether skeleton, An ethyl acetate solution of 71 g (0.5 mol) of B F teratorate was mixed at 50°C, and the oxirane oxygen content was 1.
%.

The obtained reaction crude liquid was thoroughly washed with distilled water.

A viscous liquid was obtained by concentrating the organic layer.

Infrared absorption spectrum analysis of the product revealed that there was no absorption of epoxy groups at 810 cm and 1270 cm seen in the raw material, that there was absorption due to ether bonds at 1080 cm, and that there was absorption due to hydroxyl groups at 3440 cm.

It was confirmed that vinyl group absorption remained at 1640 cm and 1820 cm, and that the present compound had a skeleton represented by the following formula by NMR analysis.

It was confirmed that it is a polyether compound having the structure shown below.

Example-2 4- as a compound forming an oxycyclohexane skeleton
446.4 g of vinyl cyclohexene 1-oxide, α-olefin oxide (Cis"ia" molecular weight 205.1) as a compound forming the alkyl ether skeleton 18
4.6 g,) 40.2 g of trimethylolpropane were mixed, and a solution of 5% ethyl acetate of B F
8 g was added dropwise at 50° C. over 4 hours.

After confirming that the epoxide has disappeared, ethyl acetate 4
00g was added and washed four times using 400g of pure water.

300 g of the upper layer was concentrated to obtain a polyether compound.

The product was analyzed by infrared absorption spectrum and NMR in the same manner as in Example 1, and the two compounds were found to have the general formula (1
) was confirmed to have the structure shown in

Claims (1)

[Claims] The following formula (
Polyether compound represented by I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [However, R_1 is an organic compound residue having l active hydrogens. n1, n2,...nl are 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100. l represents an integer from 1 to 100. A is (a) an oxynorbornene skeleton with a vinyl group or an oxycyclohexane skeleton with a vinyl group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and (b) an alkyl ether skeleton - R_2 -O-. However, R_2 is an aliphatic or alicyclic organic compound residue having one epoxy group. ]