JPS59179526A - Preparation of organo-aluminum polymer having high molecular weight - Google Patents

Abstract

PURPOSE:To prepare an organo-aluminum polymer having high molecular weight and suitable for the forming of fiber, etc., easily and efficiently, by reacting an organo-aluminum compound with a specific amount of water in the presence of a specific amount of an organic acid. CONSTITUTION:The objective polymer is prepared by reacting the organo- aluminum compound of formula [X and Y are H, alkyl or alkoxy); R is organic residue (e.g., CH3, cyclohexyl, vinyl, phenyl, etc.)] with water. The reaction is carried out in the presence of 0.2-10mol of an organic acid (e.g. lauric acid, hexanoic acid, butyric acid, valeric acid, etc.) using 1.0-3.5mol of water based on 1mol of the organo-aluminum compound, preferably at 0-60 deg.C.

Description

[Detailed description of the invention] This is related to the manufacture of.

In recent years, the emergence of high-strength, ultra-heat-resistant materials has been desired in various industrial fields, and alumina fibers, which are suitable for composite materials such as metals and ceramics, are also attracting attention as one such material.

As an excellent method for producing alumina fibers, a method based on firing precursor fibers made of organoaluminum polymers has been attracting attention. Although it is already known that an organoaluminum polymer can be obtained by the reaction of an organoaluminum compound and water, it is possible to obtain an organoaluminum polymer by the reaction of an organoaluminum compound with water. It has been difficult to obtain a high molecular weight polymer suitable for forming fibers etc. from an 00R organoaluminum compound having a molecular structure of 00R and water.

For this reason, the present inventors have conducted extensive research into methods for obtaining high-molecular-weight organoaluminum polymers suitable for molding fibers, etc., and have found that the reaction of organoaluminum compounds with water produces organoaluminum compounds. If an organic acid is added in a molar ratio of θ to /θ times, the amount of water added will be in the range of /θ to 35 times in molar ratio, and a high molecular weight organoaluminum compound suitable for forming fibers etc. It was discovered that this can be obtained easily and efficiently.

In the present invention, when producing an organoaluminum polymer by reacting an organoaluminum compound having a molecular structure of the general formula with water, water is added at a molar ratio of /θ
to 3. The present invention provides a method for producing a high molecular weight organoaluminium polymer suitable for forming fibers by adding an organic acid in an amount of 0.2 to 10 times in molar ratio.

Organoaluminium compounds used in water droplets, hydrogen,
As long as it is an alkyl group or an alkoxyl group and R is an organic residue, it is effective whether X and Y are the same residue or different residues.

In addition to hydrogen, the main alkyl groups regarding base,
Indicates a secondary butyl group and a tertiary butyl group. (Mr. Rishita),
There are various alkyl groups such as normal pentyl group and its isomer M, normal hexyl group and its isomers, and alkyl groups include: methoxyl group, ethoxyl group, normal propoxyl group, inopropoquinyl group normal butyl group, etc. Various alkoxyl groups such as a normal prokyl group and its isomers, a normal hekypnoxyl group and its isomers, and the like can be mentioned.

For group R, various organic residues such as saturated and unsaturated aliphatic substituents, Δ cycloaliphatic substituents, and aromatic substituents are effective.

The main organic residues include saturated aliphatic substituents: methyl group, ethyl group, normal procanyl group, inopropyl group, normal butyl group and its isomers, normal pentyl group and its There are various alkyl groups such as isomers, normal nonyl group and its isomers, and alicyclic substituents include 7-chlorohexyl group.

Examples of unsaturated aliphatic substituents include various aluminum groups such as vinyl, caryl, and crotyl groups;
Other examples include mono-, di-, and tri-unsaturated hydrocarbon groups such as butadienyl and octatrienyl groups, as well as common alkynyl groups such as ethynyl and probyl groups.

Examples of aromatic groups include various aryl groups such as phenyl, tolyl, anisyl, and naphthyl groups.

Furthermore, for saturated aliphatic substituents, unsaturated aliphatic substituents, alicyclic substituents, aromatic substituents, etc., chlorine, amino groups, hydroxyl groups, carboxyl groups, various alkokyl/yl groups, aryl groups, etc. It is also effective even if it contains one or more of various substituents such as.

Regarding organoaluminum compounds, in addition to the above-mentioned various organoaluminum compounds, it is also possible to use a mixture of two types of organoaluminum compounds containing different tangential residues. If the amount of water used in the reaction is in the molar ratio range of 10 to 3 times the amount of the organoaluminum compound, it is effective for producing a high molecular weight organoaluminum polymer, but it is effective for producing a high molecular weight organoaluminum polymer. A range of amounts is preferred.

Most organic acids are effective, but the main ones include saturated and unsaturated aliphatic monocarboxylic acids excluding formic acid, alicyclic carboxylic acids, aromatic monocarboxylic acids, dicarboxylic acids, Examples include hydroxylcarboxylic acids and the various organic acids mentioned above containing substituents in the main chain of the molecule.

The main saturated aliphatic monocarboxylic acids include various saturated aliphatic monocarboxylic acids such as acetic acid, globio-acid, butyric acid, imbutyric acid, pivalic acid, octanoic acid, lauric acid, and stearic acid; Aliphatic monocarboxylic acids include niacrylic acid, methacrylic acid, crotonic acid,
There are various unsaturated aliphatic-nocarboxylic acids such as oleic acid, and examples of alicyclic carboxylic acids include cyclohexanecarboxylic acid.

The main aromatic monocarboxylic acids include succinic acid, lucuric acid, 7 tars, cyclohexane dicarboxylic acids, etc. The main hydroquinocarboxylic acids include glycolic acid, lactic acid, mandelic acid, etc. can be given.

Furthermore, the main substituents in the above organic acids containing substituents in the main chain of the molecule include chlorine, amino groups, hydroxyl groups, carboxyl groups, various alkoosyl groups, phenyl groups, aryl groups, etc. .

In addition, the type of organic acid added in the reaction between the organoaluminum compound and water is the same as the organic acid (R000H) corresponding to the organic residue (■) in the aluminum compound used. It is preferable to use an organic acid having higher acidity than this organic acid.

For example, when the organic residue of the organoaluminum compound used in the reaction is a decyl group, the corresponding organic acid is lauric acid. Typical highly acidic organic acids include hexanoic acid, butyric acid, valeric acid, acetic acid, methacrylic acid, and acrylic acid (saturated and unsaturated).
Although representative organic acids are listed among aliphatic monocarboxylic acids, the present invention is not limited to only these organic acids. ) Organoaluminum compounds, water, and organic acids can be used without a solvent, but it is generally easier to handle them if they are diluted with an organic solvent. It is also effective for reactions.0 Especially when using a solid acid as the organic acid, it is better to use it after diluting it with an organic solvent.

As an organic solvent, any organic solvent that dissolves organoaluminum compounds, water, and organic acids, and that does not easily react with these substances, is effective, but in particular benzene, toluene, kiln, tetralin, and decalin. ,
Hydrocarbon solvents such as pentane, hexane and heptane, ether solvents such as dioxane, diethyl ether, 1.2-:)methoxyethane, tetrahydrofuran and anisole, and tertiary amines such as pyridine, picoline and triethylamine. Solvents include polar solvents such as dimethylsulfokind and dimethylpho/IL amide.

Water can be added all at once in the reaction between organoaluminum and compounds and water, but since the reaction is quite rapid, it is preferable to add it dropwise gradually, and the water added dropwise should also be used diluted with a solvent. It is preferable to do so.

Regarding the addition of the organic acid, it may be added all at once as in the case of water, but it is preferable to add it gradually.

Regarding the reaction temperature for producing organoaluminum polymers, see 2.
Although it is not particularly limited as long as it is 0,000 or less, it is desirable to select it depending on the type of organoaluminum compound, organic acid, and organic solvent used. Also, industrially Ooc
It is economical to do this between 0 and θ0c.

The solution viscosity of the organoaluminum polymer obtained by the method of the present invention is expressed as the relative viscosity representing the amount of polymer (2
t-s:, + (tetrachloroethano.

Mixed solution of equal amounts of phenol, 30°c1 concentration oJg/6.
1), but according to the results obtained by the present presenters using a known method when the amount of water added was θ/ to 72 times the amount of water added to the same organoaluminum compound, the obtained polymer The relative viscosity was below about 02υ.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example: Shiinobutylaluminum 3-ethoxyprobionate obtained by the reaction of triimbutylaluminum and ethoxynolopionic acid/! Add g (tJ'rnmel) and 30rn1 of tetrahydro7ran into a dropping flask, and stir at room temperature in a nitrogen atmosphere at room temperature with distilled water/θg (1 mm incl. 1). Trahi de ro franc 10+n! solution and ethoxypropionic acid j, &4tg (,29m
m*1) was gradually added dropwise to react. - By standing overnight at room temperature, a homogeneous, transparent, viscous solution was obtained.

This solution exhibited good spinnability at room temperature, which is a guideline for fiber forming. Next, this solution was poured into 3'OQml of hexane and reprecipitated to obtain 6 g of a white powdery organoaluminum polymer. A mixed solution of this polymer in equal weight of phenol and tetrachloroethane (concentration OJg/d1,
The relative viscosity at a temperature of 300C was 10/.

Example λ Diethylaluminum laurylate obtained by reaction of triethylaluminum and lauric acid using the same atmosphere and → apparatus as in the same example//, Jg (J-/mBz1)
, nato 2 human o 757 J'θml ic water 7.2
4g (70mrn gold 1) and lauric acid 2g,
(/, 2mm 宕1) was added and reacted with TOOC. After several hours, the system became a homogeneous and viscous solution. Then, the solvent tetrahydrofuran was removed under reduced pressure, and the residue was washed with hexane and dried. The result was a white resin-like organic aluminium.This polymer was dissolved in tetrahydrofuran (concentration 20,
The relative viscosity of +g/a1.13 g :tooc) is
It was 2ri/.

Example 3 In the reaction system of Example 3, the organic acid added to lauric acid was mixed with 6.03 g of ρ methoxypropionic acid (tJ
' mnr y 1) was used and left overnight in ooc. A homogeneous viscous solution was obtained in the same manner as in Example 1, and this was poured into a large amount of hexane to obtain 3 Jg of a white powdery organoaluminum polymer.

The relative viscosity of an equal weight mixed solution of phenol and tetrachloroethane (concentration: otg/dl, temperature 3θOa) of this polymer was /.

Example Using the same atmosphere and the same apparatus as in Example, a benzene solution of isopboquine secondary butoxyaluminum propiohenate (Lltmmol) and jθml of water θgtg □1 mmol) and propionic acid 90. g (/2 jmmol) was added at the same time and reacted at room temperature.

- After standing overnight, the system was poured into hexane and re-precipitated to form polymer 31? I got IQ. Equal weight mixed solution of phenol and tetrachloroethane (m degrees θtg/dl, temperature 3
The relative viscosity of 00(J) was □72.

Example! Diimpropoquine Aluminum Secondary Ptoki/Dota 4
tjg (J4mmol) and benzoic acid 303g (+2.
JOml containing a mixed product of diimpropoxyaluminum rambenzoate and impropoxy 2-butoxy7aluminum benzoate obtained by reaction with tmmol)
In the example/in the same atmosphere and atmosphere as in the same apparatus as in the example, a solution of benzoic acid (gOJ'mmol/gOJ' mmol) of benzoic acid 3θ! g
(2 tmmol) was added, reacted with a jooc, and left overnight at the same temperature. After that, use the same method as in Example 3 to prepare organic aluminum! - 3 g of polymer t was obtained. Its dimethylformamide solution (concentration (Ig/d1, temperature 3o'a)
The relative viscosity of was 3/.

Patent applicant: Isoji Taniguchi

Claims (1)

[Claims] When producing an organoaluminum polymer by reacting a luminium compound with water, the molar ratio of water to the organoaluminum compound is /θ to O+2 35 times, and the molar ratio of an organic acid is ← A method for producing a high molecular weight organoaluminum polymer characterized by adding . may also be present in different residues. Further, R represents one or two kinds of organic residues υ.