Manufacture of polyketones

Details Manufacture of polyketones Manufacture of polyketones

2001-08-08

2003-03-25

Truong, Duc (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From ketone or ketene reactant

C528S287000, C528S167000, C528S176000, C528S190000

Reexamination Certificate

active

06538098

ABSTRACT:

FIELD OF THE INVENTION
Polyketones are manufactured by the phosphoric acid/carboxylic acid anhydride catalyzed reaction of a dicarboxylic acid with an electron rich aromatic compound which behaves as a difunctional compound.
TECHNICAL BACKGROUND
Polyketones, especially aromatic polyketones, are important engineering polymers, often having the advantages of chemical resistance, good high temperature properties, good tensile properties, and others. Typical engineering polyketones are poly(etheretherketone) (PEEK) (I), and poly(etherketone) (PEK) ((II), having the repeat units
Most commonly these polymers have been made by the condensation of an aromatic hydroxy compound with an aromatic fluoride. For example, PEEK may be made by the reaction of 4,4′-difluorobenzophenone with the dianion of hydroquinone, while PEK may be made by the reaction of 4,4′-difluorobenzophenone with the dianion of 4,4′-dihydroxybenzophenone, or the base promoted self condensation of 4-fluoro-4′-hydroxybenzophenone. While these reactions suffice to make the desired polymers, they have serious disadvantages. The benzophenone monomers required are expensive, and the reactions produce byproducts such as inorganic fluorides which must be properly disposed of
Another method of making aromatic ketones is the Friedel-Crafts synthesis. While this may employ somewhat cheaper ingredients the reaction is often more difficult to run and unwanted byproducts are produced. For example at least stoichiometric quantities of a Lewis acid such as aluminum chloride must be used, which later must be separated from the polymer and discarded or otherwise used. Therefore improved methods of making polyketones are desired.
T. P. Smyth et al. J. Org. Chem, vol. 63, p. 8946-8951 (1998) describe a reaction for forming aromatic ketones reacting a carboxylic acid with an aromatic compound using as an activation system, a combination of phosphoric acid and trifluoroacetic anhydride. No mention is made of using such a reaction to form polymers.
U.S. Pat. No. 4,861,856 discloses a process for preparing polyketones and poly (ketone -sulfone) polymers, whereby reactive aromatic compounds are contacted with aromatic dicarboxylic acids in the presence of trifluoroacetic anhydride and phosphorous pentoxide. U.S. Pat. No. 4,839,459 discloses a pros for preparing poly(ether-ketone) polymers.
EP A 229 470 to co-poly ketones, process for making them and process for blending them with other polymers.
SUMMARY OF THE INVENTION
This invention concerns, a process for the production of polyketones, comprising contacting an aromatic compound which is bireactive, a dicarboxylic acid, phosphoric acid, and a carboxylic acid anhydride.
DETAILS OF THE INVENTION
By hydrocarbyl herein is meant a univalent radical containing carbon and hydrogen while substituted hydrocarbyl means hydrocarbyl substituted with one or more functional groups including complete replacement of the hydrogens). By hydrocarbylene is meant a divalent group containing only carbons and hydrogen containing two free valences to different carbon atoms by hydrocarbylene is meant a group containing carbon and hydrogen with to free valences to the same carbon atoms, each of these valences bound to a different atom. By substituted hydrocarbylene is meant a hydrocarbylene group substituted with one or more function groups, and in which all of the hydrogen may be replaced.
By a “bireactive” compound herein is meant a compound, such as an aromatic compound, in which substantially all molecules of that compound will each react twice in the ketone forming polymerization process. Since normally the “reactive group” in such a compound is a hydrogen bound to a carbon atom, which is not usually thought of as a functional group, this term is used.
By an “aromatic compound which is bireactive” is meant a compound which contains at least one aromatic ring which is bireactive. This compound may contain more than one aromatic ring. If more than one aromatic ring is present it may be fused ring system such as found in naphthalene or anthracene a ring system connected directly by a covalent bond, such as is found in biphenyl, or a ring system connected through another group, such as is found in diphenyl ether, diphenylmethane, and 2,2-diphenylpropane. Other groups may be present
on the aromatic rings so long as do not interfere with the ketone forming polymerization reaction. It is preferred that the aromatic rings are carbocyclic rings. It is also preferred that the aromatic ring or rings of this compound are naphthyl ring systems or phenyl ring(s), more preferably phenyl rings. More than one aromatic compound which is bireactive may be present to form a copolymer.
T. P. Smyth, et al. postulate that the ketone forming reaction is an electrophilic attack on an aromatic ring of the bireactive compound. It is well known in the art that in such electrophilic reactions a substrate, such as the bireactive compound, is more reactive the more “electron-rich” it is. Aromatic rings can be made more electron rich by having electron donating substituents attached to these rings. Such substituents include groups such as ether, alkyl, and tertiary amino, and are well known in the art. The presence of such groups will tend to make the bireactive compounds more reactive and ensure that it is in fact bireactive instead of monoreactive. Useful compounds for the bireactive compound include naphthalene, methylnaphthalene, methoxynaphthalene, benzyl ether, stilbene, diphenyl carbonate, benzyl phenyl ether, biphenyl, terphenyl, fluorene, and a compound of the formula
wherein R
1
is —O— (diphenyl ether), alkylidene (for example —CH
2
—, —CH
2
CH
2
—, or (CH
3
)
2
C<), and R
3
is hydrocarbylene, substituted hydrocarbylene or hydrocarbylidene, more preferably alkylene or alkylidene. Preferred bifunctional compounds are (III), especially when (III) is diphenyl ether. Useful groups for R
3
include 1,2-ethylene, 1,3-phenylene and 1,4-phenylene. More than one bireactive aromatic compound may be present to give a copolyketone.
Any carboxylic acid anhydride may be used. Carboxylic acid anhydride here has the usual meaning, a compound of the formula R
2
C(O)O(O)CR
2
wherein each R
2
is independently hydrocarbyl or substituted hydrocarbyl. It is preferred that both of R
2
are the same. It is preferred that Hammett &sgr;
m
for each of R
2
is about 0.2 or more, more preferably 0.4 or more. Hammett &sgr;
m
constants are well known in the art, see for instance C. Hansch, et al., Chem. Rev., vol. 91, p. 185ff (1991). Preferred groups for R
2
are perfluoroalkyl, and perfluoromethyl is especially preferred.
The dicarboxylic acid may be any organic dicarboxylic acid, and may contain other groups which do not interfere with the ketone forming reaction. Useful dicarboxylic acids include terephthalic acid, isophthalic acid, 4,4′-bibenzoic acid, 2-methylterephthalic acid, 2,6-naphthalene dicarboxylic acid, 2-chloroterephthalic acid, bis(4,4′-dicarboxyphenyl)ether, cyclohexane-dicarboxylic acid, norbornanedicarboxylic acid, 2,5-pyridinedicarboxylic acid, and 2,6-pyridinedicarboxylic acid. Preferred carboxylic acids are aromatic dicarboxylic acids, that is compounds in which the carboxyl groups are bound directly to aromatic rings. Preferred aromatic dicarboxylic acid are terephthalic acid, isophthalic acid, 4,4-bibenzoic acid and 2,6-napththalene dicarboxylic acid, and terephthalic acid and isophthalic acid are especially preferred. More than one dicarboxylic acid may be present in the process to give a copolyketone.
The molar ratio of the aromatic compound which is bireactive to dicarboxylic acid should preferably be about 1:1, especially preferably about 1.0:1.0, and more preferably 1.00:1.00, to achieve higher molecular weight polymer. This is normal for most condensation polymerizations to achieve higher molecular weight polymer. The molar ratio of carboxylic acid anhydride to dicarboxylic acid is preferably about 0.1 to about 20, more preferably about 2 to about 4. The molar ratio of phosphoric acid

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