Method for preparing polyaryletherketone-based copolymer by using quaternary copolymerization technology

Patent metadata

Field	Value
Publication number	US-8981034-B2
Application number	US-201013318195-A
Country	US
Kind code	B2
Filing date	Jun 23, 2010
Priority date	Jun 26, 2009
Publication date	Mar 17, 2015
Grant date	Mar 17, 2015

Abstract

A method for preparing polyaryletherketone-based copolymer by using quaternary copolymerization technology comprises: (1) adding high-temperature organic solvent into a three-necked flask equipped with a thermometer, a nitrogen-feeding pipe, and a stirrer; then stirring and heating; orderly adding 4,4′-difluordiphenylketone, 4,4′-bifluorotriphenyldione, hydroquinone, and 4,4′-dihydroxydiphenylketone after the high-temperature organic solvent has been melted, and stirring to completely dissolve them; adding alkali carbonate of 1-5% excessive amount relative to total mole of hydroquinone and 4,4′-dihydroxydiphenylketone; heating to 220-230° C. while stirring, and maintaining the temperature for 20-40 minutes to complete the first salt-forming reaction, (2) heating to 250-260° C., and maintaining the temperature for 20-40 minutes to complete the second salt-forming reaction, (3) heating to 300-320° C. to start condensation polymerization, and maintaining the temperature for 3-4 hours to complete the polymerization, and (4) pouring the obtained polymer solution into distilled water at room temperature to cool to strip-shaped solid, pulverizing, extracting with ethanol to remove organic solvent, extracting with deionized water to remove byproduct salts, and vacuum-drying to obtain quaternary copolymer containing PEEK, PEEKK, PEK, and PEKEKK repeating units in molecule chains. When the mole ratio of hydroquinone to 4,4′-dihydroxydiphenylketone is above 99:1 and the mole ratio of 4,4′-difluorodiphenylketone to 4,4′-bifluorotriphenyldione is above 99:1, the obtained quaternary copolymer mainly contains PEEK chain segments, and has the same macrophysical properties as those of PEEK.

First claim

The invention claimed is:

1. A method for preparing poly(aryl ether ketone) copolymers using quaternary copolycondensation technology, including the following steps: sulfolane is first added into a three-necked bottle equipped with a thermometer, a nitrogen pipe and a stirrer, stirred and heated, after melted the mixture is added in turn with four monomers, 4,4′-difluorobenzophenone, 1,4-bis(4-fluorobenzyl)benzene, hydroquinone and 4,4′-dihydroxybenzophenone, and stirred well until completely dissolved, then added with alkali metal carbonate, which is 1% to 5% more than the sum of hydroquinone and 4,4′-dihydroxybenzophenone in mole number, to the system, and heated up to a temperature of 200 to 230° C. under stirring to complete the first salt-forming reaction by reacting 20 to 40 minutes under constant temperature of 220 to 230° C.; then the temperature is heated up to 250 to 260° C. and the second salt-forming reaction is completed in 20 to 40 minutes under constant temperature of 250 to 260° C., followed by heated up to 300 to 320° C. for starting the polycondensation reaction, and the polymerization reaction is completed in 3 to 4 hours during this phase under the constant temperature of 300 to 320° C.; finally, the above polymer solution is poured into the distilled water at room temperature and cooled into stripy solids, and the solids are crushed and extracted with ethanol to remove the solvent sulfobenzide or sulfolane in the polymer, and then added with deionized water to extract the by-product salts, followed by vacuum drying, wherein the charge ratio of the four monomers is controlled to obtain one of four quaternary copolymers, wherein each one of the four quaternary copolymers contains-structural repeat units PEEK, PEEKK, PEK and PEKEKK in the molecular chain, with one of the repeat units constituting major part of the copolymer obtained and the remaining three of the repeat units constituting minor part of the copolymer obtained, such that the copolymer obtained has equivalent macroscopic properties with a corresponding homopolymer that is constituted solely by the one of the repeat units constituting the major part of the copolymer obtained.

2. The method according to claim 1 , characterized in that the alkali metal carbonates are K 2 CO 3 , Na 2 CO 3 , or their mixture in different proportions.

3. The method according to claim 1 , characterized in that the mole ratio of hydroquinone and 4,4′-dihydroxybenzophenone is greater than 99:1 and the mole ratio of 4,4′-difluorobenzophenone and 1,4-bis(4-fluorobenzyl)benzene is greater than 99:1, the resulted quaternary copolymers contains the PEEK segment as the major component in its molecular chain and has equivalent macroscopic properties with PEEK, in which the mole number of hydroquinone is the same as that of 4,4′-difluorobenzophenone and the mole number of 4,4′-dihydroxybenzophenone is the same as that of 1,4-bis(4-fluorobenzyl)benzene.

4. The method according to claim 1 , characterized in that the mole ratio of hydroquinone and 4,4′-dihydroxybenzophenone is greater than 99:1 and the mole ratio of 1,4-bis(4-fluorobenzyl)benzene and 4,4′-difluorobenzophenone is greater than 99:1, the resulted quaternary copolymers contains the PEEKK segment as the major component in its molecular chain and has equivalent macroscopic properties with PEEKK, in which the mole number of hydroquinone is the same as that of 1,4-bis(4-fluorobenzyl)benzene and the mole number of 4,4′-dihydroxybenzophenone is the same as that of 4,4′-difluorobenzophenone.

5. The method according to claim 1 , characterized in that when the mole ratio of 4,4′-dihydroxybenzophenone and hydroquinone is greater than 99:1 and the mole ratio of 4,4′-difluorobenzophenone and 1,4-bis(4-fluorobenzyl)benzene is greater than 99:1, the resulted quaternary copolymers contains the PEK segment as the major component in its molecular chain and has equivalent macroscopic properties with PEK, in which the mole number of 4,4′-dihydroxybenzophenone is the same as that of 4,4′-difluorobenzophenone and the mole number of hydroquinone is the same as that of 1,4-bis(4-fluorobenzyl)benzene.

6. The method according to claim 1 , characterized in that when the mole ratio of 4,4′-dihydroxybenzophenone and hydroquinone is greater than 99:1 and the mole ratio of 1,4-bis(4-fluorobenzyl)benzene and 4,4′-difluorobenzophenone is greater than 99:1, the resulted quaternary copolymers contains the PEKEKK segment as the major component in its molecular chain and has equivalent macroscopic properties with PEKEKK, in which the mole number of 4,4′-dihydroxybenzophenone is the same as that of 1,4-bis(4-fluorobenzyl)benzene and the mole number of hydroquinone is the same as that of 4,4′-difluorobenzophenone.

Assignees

• Wu Zhongwen
• Ma Rongtang
• Kingfa Science & Technology Co

Inventors

• Wu Zhongwen
• Ma Rongtang

Classifications

• C08G65/4093

  characterised by the process or apparatus used · CPC title

• C08G2650/40

  containing ketone groups, e.g. polyarylethylketones, PEEK or PEK · CPC title

• C08G65/4012 Primary

  Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones · CPC title

• C08G65/00 Primary

  Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule · CPC title

• C08G65/02

  from cyclic ethers by opening of the heterocyclic ring · CPC title