JPS6099134A - Production of organic aluminum polymer having high molecular weight - Google Patents

Abstract

PURPOSE:To obtain an organic aluminum polymer having high molecular weight and suitable for the forming of fiber, etc., by adding an organic acid in the condensation polymerization reaction of a specific organic aluminum compound with water. CONSTITUTION:1mol of an organic aluminum compound having the molecular structure of formula (X is H, alkyl or alkoxy; R1, R2 and R3 are alkyl) is subjected to the condensation polymerization reaction with 1-3.5mol. preferably 1-2mol of water. The polymerization is carried out in the presence of 0.1- 10mol, preferably 0.2-3.5mol of an organic acid (e.g. acetic acid, acrylic acid, succinic acid, etc.). The organic acid may be added to the system simultaneous or prior to the addition of water or after the polymerization. The solution viscosity of the resultant organic aluminum polymer is >=0.6.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to the production of high molecular weight organoaluminum polymers.

In recent years, materials with high strength and high heat resistance have emerged (desired by various industrial fields), and are suitable for composite materials such as metals and ceramics (Alumina fiber is also attracting attention as one such material). It's been 0.

As an excellent method for producing alumina fibers, a method by firing a precursor fiber C made of an organoaluminum polymer has been attracting attention; There was no way to easily and efficiently manufacture a ship. That is, it is already known that an organoaluminum polymer can be obtained by a condensation polymerization reaction between an organoaluminum compound and water, but depending on the method of Publication E-11, fibers etc. can be obtained by a condensation polymerization reaction between an organoaluminum compound and water. It has been difficult to obtain high molecular weight polymers suitable for molding.

For this reason, the present presenters have conducted various studies on methods for obtaining high-molecular-weight organoaluminum polymers suitable for forming fibers, etc., and have found that mononium compounds (Tazo and residues X, Y,
By adding an organic acid in addition to water to (all Z represents hydrogen, alkyl group, or alkoxyl group, and R represents an organic residue), a high molecular weight organoaluminum compound suitable for molding into fibers etc. can be easily produced. However, he discovered that it could be obtained efficiently and filed a patent application (58-067564, 58
-056266, 58-079887).

However, surprisingly, the general formula X-At-C0R
In the condensation polymerization reaction between an organoaluminum metal material having 2 and water, it is possible to form fibers etc. in the same manner as above by adding an organic acid in addition to water to the organic aluminum metal material. A high molecular weight organoaluminum polymer can be easily obtained, and in this case, the speed of the condensation polymerization reaction is moderately low, and the molecular weight of the resulting polymer is 1
Yasutaka Ichikawa (I found out that it is extremely easy to do).

The present invention has the general formula X-Al-0COR, and R,COO
COR2 A I OCORZ type organic aluminum 0
OR3 When producing an organoaluminium polymer from the reaction between an aluminum compound and water, it is possible to form fibers etc. by applying water and an organic acid to the aluminum compound. This paper presents a method for producing organoaluminum polymers for nails.

In nature, it is an organic alkyl group, an alkyl group, an alkoxyl group, and R1 and R2 are organic residues, and even if R1 and R2 are the same residue, they may be different residues. There is no problem.

In addition, R1, R2 in RICOOAl-0COR,2
, R3COR3 are all alkyl groups, and even if the three residues are completely different residues or the same residues, any two residues are the same residues and the remaining residues are different residues. It doesn't matter if there is.

In addition to hydrogen, the main alkyl groups include: methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, and their isomers (for example, for butyl groups, isobutyl group,
Indicates a secondary butyl group and a tertiary butyl group. , hereinafter the same)
, normal pentyl group and its isomers, normal hexyl group and its isomers, and various other alkyl groups.

Various organic residues such as saturated and unsaturated aliphatic substituents, alicyclic substituents, and aromatic substituents are effective for R2 and R3.

The main organic residues include saturated aliphatic substituents: methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group and its isomers, normal pentyl group and its isomers. There are various alkyl groups such as normal nonyl groups, normal nonyl groups, and isomers thereof, and alicyclic substituents include cyclohexyl groups and the like.

In addition, unsaturated aliphatic substituents include various alkenyl groups such as vinyl, allyl, and crotyl groups, as well as mono-, di-, and tri-unsaturated hydrocarbons such as butadienyl and octatrienyl MNj. and also alkynyl groups such as ethynyl, propynyl, etc.

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

Furthermore, regarding saturated aliphatic substituents, unsaturated aliphatic substituents, alicyclic substituents, aromatic substituents, etc., chlorine, amino groups, hydroxyl groups, carboxyl groups, various alkoxyl groups, aryl groups, etc. It may contain one or more of various substituents.

In addition to the various organoaluminum compounds mentioned above, the organoaluminum compound may be a mixture of two or more organoaluminum compounds containing organic residues with different R's.

The preferred amount of water used for the reaction with the organoaluminum compound is 1.0 to 3.5 times the molar ratio of the organoaluminum compound, but 10 to 2.
．． A range of 0 times the amount is a particularly preferred range.

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, propionic acid, butyric acid, i-nobutyric acid, pivalic acid, octanoic acid, wau-monoic acid, and stearic acid. Examples of unsaturated aliphatic monocarboxylic acids include various unsaturated aliphatic monocarboxylic acids such as diacrylic acid, methacrylic acid, crotonic acid, and oleic acid, and examples of alicyclic carboxylic acids include cyclohexanecarboxylic acid.

The main aromatic monocarboxylic acids include succinic acid, glutaric acid, phthalic acids, cyclohexanedicarphonic acids, etc., and the main hydroxycarboxylic acids include 1-nocholic acid, lactic acid, Examples include mandelic acid.

Furthermore, mf containing substituents in the main chain of the molecule. etc.

However, the type of organic acid added in the reaction between the organoaluminum compound and water is preferably selected based on the following criteria. That is, organic residues (&, R2 or R1) contained in the organoaluminum compound used in the condensation polymerization reaction
, R2, R3) corresponding to two or three types of organic acids (R2C0OH or Rz C0OH on RICOO1,
R2C0OH, RsC0OH), the organic residue remaining in the polymer produced by condensation polymerization is considered to be the residue corresponding to the organic acid with the lowest acidity; It is preferable to use an acid or an organic acid with higher acidity than this organic acid.

-For example, when the organic residues of the organic aluminium compound used in the reaction are propionyl and undecyl groups, the corresponding organic acids are propionic acid and lauric acid, so the preferred organic acids for addition are propionyl and undecyl groups. In addition to lauric acid, which is less acidic, typical organic acids that are more acidic than lauric acid include hexanoic acid, butyric acid, valeric acid,
Examples include acetic acid, methacrylic acid, acrylic acid, etc. (representative organic acids are listed from among saturated and unsaturated aliphatic monocarboxylic acids, but are not limited to these organic acids). I can do it.

Further, in the present invention, the various organic acids described above may be used alone or in a mixture of two or more types.

Organoaluminum compounds, water, and organic acids can be used without a solvent, but it is generally more convenient to handle them if they are diluted with an organic solvent, and they are also effective against condensation polymerization reactions. It is true.゛In particular, when using a solid acid as the organic acid, it is better to use it after diluting it with an organic solvent.

Any organic solvent that dissolves organoaluminum compounds, water, and organic acids and does not react with these substances is effective, but in particular benzene, toluene, xylene, tetralin, decalin, and pentane. , hydrocarbon solvents such as hexane and heptane, ether solvents such as dioxane, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and anisole, and tertiary amine solvents such as pyridine, picoline, and triethylamine. Examples include polar solvents such as dimethyl sulfoxide and dimethyl formamide.・In the condensation polymerization reaction between an organoaluminum compound and water, there is no problem in adding water all at once, but it is preferable to drop it gradually, and it is more convenient to use the water that is added dropwise after being diluted with a solvent. It is.

Regarding the order of addition of the organoaluminum compound, water, and organic acid, it is acceptable if the organic aluminum compound is added later, but the order of addition of water and organic acid to the organoaluminum compound is determined. is convenient.

The order of addition of organic acids to water is as follows:
It may be added after the condensation polymerization reaction, or condensate containing an organic acid added to the organoaluminum compound may be added. There is no harm in adding it.

The amount of the organic acid used in the present invention is preferably in the range of 0.1 to 10 parts by molar ratio to 1 part of the organoaluminum compound (in the range of 0.2 to 3.5 parts). is a particularly preferred range.

The reaction temperature during the production of the organoaluminum polymer is not particularly limited as long as it is 200°C or less, but it is preferably selected depending on the types of organoaluminum compound, organic acid, and organic solvent used. Also industrially (
It is economical to carry out the heating between 0°C and around 60°C.

The solution viscosity of the organoaluminum polymer obtained by the method of the present invention is approximately 0 as the relative viscosity indicating the molecular weight of the polymer.
．． 6 or more (tetrachloroethane and phenol mixed solution in equal amounts, 30°C, concentration 0.5 g/d1), and was a high molecular weight polymer suitable for molding fibers, etc., whereas for the same organoaluminum compound The amount of water added is 1.0
According to the results conducted by the present inventors using a known method in an amount ranging from 1.2 to 1.2, the molecular weight was as low as 0.2 or less.

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

Example 1 Di(β-ethquinpropionic acid)ethylaluminum (5Qmmo I) obtained by the reaction of 1 equivalent of triethylaluminum and 2 equivalents of β-ethoxypropionic acid and 50 ml of toluene were added to a dropping funnel, a reflux condenser, and a three-way cock. A 10 ml solution of 1,4-dioxane containing 0.9 g (5 Q mmol) of distilled water and 1.18 g of β-ethoxypropionic acid ( 10 mmol I) was added dropwise to react. After several hours, a clear viscous solution formed. This solution showed good stringability, which is a measure of fiber-forming properties. Next, this solution was poured into 500 ml of hexane, and by reprecipitation, a white powdery organoaluminum polymer 12.7
I got g. A mixed solution of this polymer in equal weight of phenol and tetrachloroethane (concentration 0.5 g/formerly, temperature 30°C)
The relative viscosity of was 0.76.

Example 2 2.95 g (25 mmol) of β-ethoxypropionic acid was further added to the viscous solution obtained in the reaction of Example 1, and the mixture was left at room temperature overnight. The system became more viscous than before the addition of acid. Thereafter, reprecipitation was performed in the same manner as in Example 1 to obtain 13.1 g of an organoaluminum polymer. The relative viscosity of this polymer (same solvent, same conditions as Example 1) was 098
Met.

Example 3 In the same apparatus as in Example 1, 11.5 g (5
Qmmol) and 50ml of tetrahydrofuran were placed in the same apparatus as in Example 1, and while stirring at 50°C, 0.9ml of water was added.
g (5Qmmol) and propionic acid 3.7g
(5Qmmol) of tetrahydrofuran 20ml
The solution was reacted dropwise. When kept at 50'C for several hours, the system became a homogeneous viscous solution, which was poured into a large amount of hexane and reprecipitated, yielding 11.4 g of an organoaluminum polymer in the form of a white powder. The relative viscosity of this polymer (same solvent, same conditions as Example 1) was 1.8.

Example 4 Aluminum isopropoxide 1 was added to the same equipment as in Example 1.
24.2 g (5
Pour 100 ml of bender and 1.1 g (60 mmol) of water at 80°C in a nitrogen atmosphere.
was reacted dropwise. Then add 5 g of lauric acid (25 m
mol) and continued stirring at 80°C for several hours, and then -
It was left at room temperature day and night. The system became a homogeneous viscous solution. Then, the solvent benzene was removed under reduced pressure, and the residue was washed with hexane and dried. As a result, 21 g of a white resin-like organic aluminum polymer was obtained. The relative viscosity of a benzene solution (concentration 0.5 g/old, temperature 30°C) of this polymer is 5
．． It was 05.

Example 5 In the same apparatus as in Example 1, monopropionic acid mono(β
-ethoxypropionic acid)isobutylaluminum 13
．． 7 g' (50 mmol) and tetrahydrofuran 3
Add 1.8 g (1.8 g) of water while stirring at room temperature.
0Q mmol and 7.4 g of propionic acid (10Q
50 ml of a tetrahydrofuran solution containing 50 mmol) was added dropwise. Thereafter, the mixture was stirred at room temperature for 10 hours to obtain a viscous solution. Then, it was poured into a large amount of hexane and reprecipitated to obtain 10.5 g of an organoaluminum polymer. The relative viscosity of this polymer (same solvent, same conditions as Example 1) was 1.3
Met.

Example 6 In the same apparatus as in Example 1, aluminum tricaprylate was prepared by reacting 1 equivalent of ethylaluminum diisopropoxide with 3 equivalents of caprylic acid. '8 g (50 mm
1) and 100 ml of toluene, and while stirring at 100°C in a nitrogen atmosphere, add 28.8 g of caprylic acid.
(100 mmol) was added dropwise. 1 hour later, 0 more water
．． 9 (50 mmol) in a dioxane solution containing 10 m
1 was added dropwise, and stirring was continued at the same temperature for 3 hours. The resulting homogeneous and viscous solution was removed from the toluene under reduced pressure, and the residue was washed with ethanol and dried.

As a result, a white rubbery organoaluminum polymer of 20.5
I got g.

A toluene solution of this polymer (concentration 0.5 g/old, temperature 3
The relative viscosity at 0° C.) was 0.69.

Patent applicant: Tani I” 52

Claims (1)

[Scope of Claims] A polymerization process characterized by adding water and an organic acid to an organoaluminide metal compound when producing an organoaluminum polymer by reacting an organoaluminum compound having a 0COR2 type molecular structure with water. Method for producing molecular weight organoaluminum polymers. X represents hydrogen, an alkyl group, or an alkoxyl group. In addition, R1, R2, and R3 all represent an alkyl group, and in the X-Al-0COR type organic aluminum C0R2 compound, R1 and R2 may be the same residue or different residues. Well done, KI Coo-AI
-C0R in OCOR2 type organoaluminum compounds
5, R1, R2, and R3 may be completely different residues or the same residue, or any two residues may be the same residue and the remaining residues may be different residues. . 2. The manufacturing method according to claim 1, wherein the molar ratio of water to 1 part of the organoaluminum compound is 1.0 to 3.5 parts and the organic acid is 0.2 to 10 parts. 3. The manufacturing method according to claim 1, characterized in that when adding water and an organic acid to the organoaluminum compound, the organic acid is added at the time of the reaction between the organoaluminum compound and water. 4. The manufacturing method according to claim 1, wherein when adding water and an organic acid to the organoaluminum compound, the organic acid is added after the reaction between the organoaluminum compound and water. 5. The manufacturing method according to claim 1, characterized in that when adding water and an organic acid to the organoaluminum compound, water is added after adding the organic acid to the organoaluminum compound. 6. When adding water and an organic acid to an organoaluminum compound, a part of the organic acid is first added during the reaction between the organoaluminum compound and water, and the remainder of the organic acid is added after the reaction. The manufacturing method described in Scope 1. 7. When adding 1.0 to 3.5 parts of water and 0.2 to 10 parts of organic acid in molar ratio to 1 part of organoaluminum compound, the organic acid is added at the time of reaction between the organoaluminum compound and water. The manufacturing method according to claim 2, characterized in that: 8 When adding 1.0 to 3.5 parts of water and 0.2 to 10 parts of organic acid in molar ratio to 1 part of organoaluminum compound, add the organic acid after the reaction between the organoaluminum compound and water. Characteristic Claim 2
Manufacturing method described in section. 9 When adding 1.0 to 3.5 parts of water and 0.2 to 10 parts of organic acid in molar ratio to 1 part of organoaluminum compound, add water after adding the organic acid to the organoaluminum compound. Characteristic Claim 2
Manufacturing method described in section. 10 When adding 1.0 to 3.5 parts of water and 0.2 to 10 parts of organic acid in molar ratio to 1 part of organoaluminum compound, a part of the organic acid is first reacted with the organoaluminum compound and water. Claim 2, characterized in that the remainder of the organic acid is added after the reaction.
Manufacturing method described in section.