Polyketone and process for producing the same

Inactive Publication Date: 2005-04-07
ASAHI KASEI FIBERS CORPORATION
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

In order to attain the above objects, the inventors have conducted an intensive research to improve the heat resistance of polyketones by controlling the conditions for the production of polyketones with high molecular weight and high melting point and controlling the structure of polyketones, and, as a result, it has been found that the above objects can be attained by reducing the content of Pd in polyketones and render the proportion of the terminal structures of polyketones within a specific range. Thus, the present invention has been accomplished.

Problems solved by technology

Polyketones mainly composed of repeating units comprising ethylene and carbon monoxide have a high melting point of 200° C. or higher, nevertheless, they suffer from the problems that thermal modifications such as three-dimensional crosslinking occur under heating for a long period of time to cause deterioration of molding processability due to loss of flowability, and furthermore mechanical performance and heat resistance performance of the molded products are lowered owing to decrease of the melting point.
However, in this method, there are problems that long-term heating of a dope in which polyketone is dissolved causes thermal modification of the polyketone which results in the deterioration of flowability and spinnability of the dope and that mechanical properties of the resulting fibers or films are thus deteriorated.
If a polyketone is heated, it undergoes chemical reactions, such as Paal-Knorr reaction to produce a furan ring and the formation of intramolecular or intermolecular crosslinking due to aldol condensation, resulting in the progress of heat deterioration of the polyketones.
Therefore, these methods cannot be put to industrially practical use, taking into consideration the costs for washing facilities, and washing and extracting solvents.
Furthermore, since heat deterioration of polyketones also occurs due to the lengthy heat treatment, the heat resistance of the resulting polyketones is not sufficient, although the Pd content is small.
Moreover, since the complicated Pd extraction treatment must be carried out after the polymerization, the method cannot be industrially employed from the viewpoints of productivity and cost.
The method thus has problems that the polymerization rate is very low and that lengthy heat treatment is required during the solvent extraction.
The techniques are thus insufficient to be used for fibers or films with high strength.
Such a polyketone has not been obtained by known techniques.

Method used

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  • Polyketone and process for producing the same
  • Polyketone and process for producing the same
  • Polyketone and process for producing the same

Examples

Experimental program
Comparison scheme
Effect test

example 1

25 micromoles of palladium acetate, 30 micromoles of 1,3-bis{di(2-methoxyphenyl)phosphino}propane, 1 millimole of sulfuric acid and 2.5 millimoles of 1,4-benzoquinone were dissolved in 40 ml of acetone to prepare a catalyst solution. This catalyst solution was introduced into a stainless steel autoclave of 2000 ml in capacity which contained 1000 ml of methanol-water mixed solvent (containing 12 vol % of water). Before the introduction of the catalyst, the methanol-water mixed solvent in the autoclave was previously subjected to nitrogen replacement three times at 30° C. and 3 MPa.

After the autoclave was closed, the content was heated while stirring, and when the internal temperature reached 85° C., ethylene was added until the internal pressure reached 4.5 MPa and subsequently carbon monoxide was added until the internal pressure reached 9.0 MPa. Thereafter, a mixed gas comprising 1:1 of ethylene and carbon monoxide was continuously fed and stirring was continued for 4 hours whi...

example 2

In 4 ml of acetone were dissolved 1.25 micromole of palladium acetate, 1.5 micromole of 1,3-bis(diphenylphosphino)propane and 50 micromoles of sulfuric acid, to obtain a catalyst solution. This was dissolved in 50 ml of a methanol / water mixed solvent containing 2000 ppm of water, and this solution was introduced into a stainless steel autoclave of 100 ml in capacity which was subjected to nitrogen replacement.

Thereafter, the temperature was raised to 80° C., and ethylene was introduced until the internal pressure reached 4.5 MPa and subsequently carbon monoxide was introduced until the internal pressure reached 9.0 MPa. Thereafter, a mixed gas comprising 1:1 of ethylene and carbon monoxide was continuously fed, and polymerization was carried out for 4 hours in the same formulation as in Example 1 while keeping the internal pressure at 9.0 MPa and the internal temperature at 85° C., thereby obtaining 1.33 g of a polyketone. The polymerization activity was 20.0 kg / g-Pd·hr, and the ...

example 3

The polymerization was carried out in the same manner as in Example 1, except that the composition of the catalyst solution comprised 10 micromoles of palladium acetate, 12 micromoles of 1,3-bis{di(2-methoxyphenyl)phosphino}propane, 1 millimole of sulfuric acid and 5.0 millimoles of 1,4-benzoquinone, and that the polymerization time was 10 hours, whereby 274 g of polyketone was obtained. The polymerization activity was 25.7 kg / g-Pd·hr, and the [η] was 6.3 dl / g. The content of Pd in this polyketone was 2 ppm, and the ratio of terminal group A / terminal group B was 2.0. This polyketone had good heat resistance.

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Abstract

There is provided a polyketone comprising repeating units, 95-100 mole % of which are 1-oxotrimethylene and having an intrinsic viscosity of 2.5-20 dl / g, wherein the content of Pd element is 0-20 ppm, terminal structures include an alkyl ester group (terminal group A) and an alkyl ketone group (terminal group B), and the equivalent ratio of terminal group A / terminal group B is 0.1-8.0. The polyketone of the present invention can be used in any forms, such as fibers and films, and can be applied to a wide variety of the uses such as clothing, reinforcing materials for rubbers, resins, cements, and optical fibers, electronic materials, battery materials, civil engineering materials, medical materials, daily commodities, fishery materials, and packaging materials.

Description

TECHNICAL FIELD The present invention relates to a polyketone which is high in molecular weight, can exhibit ultra-high strength when made into fibers, has excellent heat stability and chemical resistance, and is excellent in stability of quality during long-term storage, processability at high temperatures and in wet heat, and stability as a dope in inorganic salt solvents, as well as a method for producing the polyketone. BACKGROUND ART Polyketones having a structure in which repeating units derived from carbon monoxide and repeating units derived from ethylenically unsaturated compounds are substantially alternately connected with each other are excellent in mechanical properties and thermal properties and high in wear resistance, chemical resistance and gas barrier properties, and thus are expected to be used in various fields. For example, polyketones are useful material as resins, fibers and films having high strength and high heat resistance. Particularly, when a high molec...

Claims

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Application Information

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IPC IPC(8): B60C9/00C08G67/02D01F6/30D01F6/76
CPCB60C9/0042D01F6/76D01F6/30C08G67/02C08G85/00
Inventor TANIGUCHI, RYUKATO, JINICHIROKOMATSU, TAKASHI
Owner ASAHI KASEI FIBERS CORPORATION
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