JPS60104132A - Preparation of polymer - Google Patents

Abstract

PURPOSE:To prepare a polymer showing stringiness, having high polymerization degree, stable in atmosphere from safely handleable raw materials by a relatively easy method, by blending a zirconium alkoxide with an aliphatic dicarboxylic acid in a solvent, reacting them. CONSTITUTION:A zirconium alkoxide is blended with an aliphatic dicarboxylic acid in a solvent and reacted. A compound shown by the formula (R1O)(R2O) ZrR3R4 (R1 and R2 are preferably <=12C alkyl; R3 and R4 are alkyl, alkoxy, etc.) is used as the zirconium alkoxide. Oxalic acid, succinic acid, etc. are used the aliphatic acid. Both the components are reacted under reflux approximately at the boiling point of the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a zirconium-containing polymer having moldability for producing Zirphere fibers, coating agents, films, etc. and
More specifically, a zirconium-containing polymer with excellent molding performance was produced by reacting this 71t in a solvent and then removing the solvent and alcohol. It is a method of manufacturing.

In recent years, in a wide range of fields such as the aerospace industry, the information electronics industry, and the industry, the need for improved materials has rapidly increased with technological development. For example, in the aerospace industry, there is a strong desire for the development of silica that has properties superior to those of conventional materials, such as heat resistance at high temperatures and high mechanical properties. One way to improve the properties of such abrasive materials is to replace conventional materials such as plastics and metals with tungsten tri
Did you cover the surface of the IF with boron or silicon carbide? M synthetic fiber cord, tungsten, molybdenum, metal without steel 61 fibers (((, polycrystalline fiber with alumina, zirconia, silicon carbide, silicon nitride, etc.), metal whiskers with copper, alumina, silicon carbide, etc. Ceramic whiskers, or carbon f, 11i H (and possibly composite reinforcement).

Among these new composite use enhancement technologies, Zirconia TM
t (f stands for zirconia's high melting point (2700"C), which makes it excellent at high temperatures (it does not lose its shallow properties), and is also suitable for high-temperature oxidation that cannot be used with carbon fibers or fully flexed fibers. Can be used in a sexual atmosphere.

Generally, the following methods are known for producing precursor fibers for ceramic fibers.

(2) Inorganic salt method A metal hydroxide or a metal salt is dissolved and mixed together with an organic polymer in a medium, and the mixture is spun.

■) Sol method Spinning an aqueous sol with metal hydroxide.

■) Slurry method A slurry solution of metal salts containing metal oxides is spun.

(2) Pulling a single crystal from a melt - Inorganic gold II (2) Precursor polymer method An inorganic gold II polymer is synthesized using a metal alkoxide or an alkyl metal as a starting monomer, and then it is spun.

Among these methods, methods I) to ■) are also used by Isusha to give the spinning stock solution a thread-like appearance. The zirconia content in [is lower. For this reason, Luconia U & Fiber (S) lacks density and has extremely low strength, which is a fatal flaw. However, its application is severely restricted. On the other hand, the +]if-suspended polymer in (■) has spinnability due to the high molecular weight of the metal-containing polymer, so it can be spun without adding any 41 machine polymer as an auxiliary agent. Is possible. Therefore, the precursor fiber has a high metal content, and the zirconia fiber that has a dense convexity by firing
It is an extremely advantageous method that is suitable for industrial mass production, as it is possible to obtain long fibers with high yields. Synthesis is difficult, and even if it could be made, the raw materials would be treated as alkyl metals-11, it would be necessary to use dangerous materials, and it would not be possible to obtain a degree of polymerization high enough to exhibit sufficient spinnability. Furthermore, there is a major problem in that the produced polymer is hydrolyzed by moisture in the atmosphere and can only be used in unstable conditions such as depolymerization.

In view of the 41 circumstances mentioned in item 1, the present invention aims to produce a popular and stable zirconium-containing inorganic material that has a sufficiently high degree of polymerization to exhibit spinnability using a relatively easy method from raw material monomers that are safe to handle. An object of the present invention is to provide a method for producing a high molecular weight polymer.

The present invention has the following 11 components to achieve this object. Zunawaji The present invention involves mixing luconium-11 alkoxide and aliphatic 7-carboxylic acid in a solvent,
Features, that make you react! This is a method for producing 1,000 combinations.

Here, fluconium alkoxide has the general formula (I<10)
(R20) It is shown as T i R3R4, and this back R
I and R2 are alkyl groups, and the number of carbon atoms is preferably j2 or less. Furthermore, R3 and R4 are alkyl groups, alkyl metals, formyloxy, (, acetate groups, halogen groups, hydroxyl groups, phenoxy groups, etc.) having the same number of carbon atoms as each other. Furthermore, aliphatic dicarboxylic acids include nouric acid, malonic acid, succinic acid, geltaric acid, ampinoic acid, pimelic acid, superic acid, azelaic acid, ceranic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, and ntraconic acid. such as acids.

For those containing aromatic benzene rings as acids, it is difficult to decarburize the precursor fibers into zirconia fibers by firing, and the resulting zirconia fibers have poor mechanical properties, heat resistance, and other properties. Performance will be reduced by 1. The solvent to be used may be selected from a wide range of alcohols, hydrocarbons, chlorinated hydrocarbons, ethers, ketones, and furans, taking into consideration the solubility and boiling point of alkoxides and dicarboxylic acids. These fluconium alkokids and aliphatic dicarboxylic acids are dissolved in a solvent and reacted. Usually, it is preferable to stir the reaction with stirring near the boiling point of the solvent. Thereafter, by removing the solvent and the produced alcohol by a method of depressurization, a polymer having a zirconium content j can be obtained. 1lij using this? rK resting body lc
In this process, n′f
It is also possible to use the solution by leaving an appropriate amount of solvent and alcohol and adjusting the solution viscosity to 10 to 50,000 v·r, which is necessary for spinning. At this time, the spinning l+k contains several components such as polyethylene glycol, polyvinyl alcohol, and polyvinyl acetate, aliphatic carboxylic acids such as vinylic acid, lauric acid, and stearic acid, and other components. The addition of additives is desirable for improving spinnability.

The method of the present invention is characterized in that a stable inorganic polymer can be easily obtained by using an easily handled metal alkoxide as a starting material. Since a chain-like product with a high degree of polymerization can be obtained, the high yarn + lI is combed with λ'' to produce the precursor yarn.
It is possible to convert l to 7Hj. Furthermore, the obtained no-fil
, ;'+,' molecules have high water resistance and are hydrolyzed by water 1
(It also has the characteristic that it accepts 'l' and is 115' and 11. Also, in terms of quality, a precursor fiber with high m content is obtained, and it has high strength and can obtain 1( Can be done.

The zirconium gold platinum jHB (('
J-polymer can be coated on glass, plastic films, etc., made of Norconia woven fabric 1F, and used as an electrode. It is also possible to use it as a dielectric film by multi-layer coating with a film.Furthermore, after impregnating a porous heat-resistant base thin film or a sheet with an inorganic polymer solution,
It is also possible to make a ceramic film by firing.

The present invention will be specifically explained below using examples.

The reduced viscosity of the polymer (7 sp/c) was measured using tetrahydrofuran solvent, and the polymer concentration C = (1, Ig
/di at 30°C.

Example 1 1 mole of tetraisopropoxysilconium and 1 mole of succinic acid were dissolved and mixed in 300 ml of ethanol E, and the mixture was reacted under reflux for 111.7 minutes in a nitrogen atmosphere, and then heated to 150°C under pressure and obedience. The solvent was removed in 3 hours to obtain a solid polymer.This sample had reduced viscosity.After degassing this solution, it was spun using a nozzle with a diameter of 200μ.
It was wound at a speed of 20 m/min to obtain a precursor Mt of 10 μm.

Example 2 1 mole of tetrabutoxyzirconium and 1 mole of fumaric acid were dissolved and mixed in 500 ml of benzene, and the mixture was reacted under reflux for 1 hour in a nitrogen stream.
Polymerization was carried out while removing the n' medium at 0''C between 511. 8 to benzene
The viscosity of the solution dissolved at 0% market was 270 voids. After defoaming this solution, spinning was performed using a nozzle with a diameter of 300 II, and the spinning speed was 8.0 m/min.
A 7 μm precursor fiber was obtained.

Example 3゜ Tetrabutquin zirconium I mol and H γ di 1-.

Dissolve 1 mole of phosphoric acid in butanol (300 ml)
1J and reacted under reflux for 1 hour in a nitrogen stream. Thereafter, polymerization was carried out at 140'C for 2.5 hours without removing the solvent to obtain a solid polymer of 7-1. this test)
The reduced viscosity 'Fl sp/c of :;l was 0.52. When this was dissolved in benzene at 20% by weight, the solution viscosity was 110 points. After degassing this solution, it was spun using a nozzle with a diameter of 200 μm and wound at a speed of 100 m/min. The diameter of the precursor leave i+ (was 6μ.

Patent applicant: Toyobo Co., Ltd. Procedural correction divination (method) L Incident display 1981 Patent Application No. 212787 2 Name of the invention Polymer manufacturing method & person making corrections Relationship to the case: Patent applicant Dojimahama 2-chome, Kita-ku, Osaka 2t68-υ Date of amendment order February 8, 1982 (Shipping date: February 26, 1982)

Claims (1)

[Claims] A method for producing a polymer, the method comprising mixing zirconium alkoxide and aliphatic dicarboxylic acid in a solvent and reacting the mixture.