US 4,841,011 AGranted

Preparation of arylene oligomers

AssigneeRaychem Corporation

InventorIan D. H. Towle

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Abstract

Friedel Crafts preparation of arylene ether (especially arylene ether ketone) oligomers with an exceptionally high degree of isomeric purity and freedom from by-products can be achieved by adding to the Lewis acid reaction system a protic controlling agent selected from ROX, water, RCOOX, RSO.sub.3 X, and ROY, wherein R is organic, X is hydrogen or metal, and Y is metal. Contrary to conventional expectation, the protic agent does not significantly acylate or alkylate the Friedel Crafts reaction product, and controlling agents of relatively low molecular weight, e.g., benzoic acid, can surprisingly be selected to produce dispersions of the resulting oligomers.

Claims22

Dependent claims

A method of preparing an arylene oligomer having the repeat unit:

ti -Ar-O-Ar-B-
where
each B independently is a carbonyl (--CO--) or sulphonyl (--SO.sub.2 --) group, and each Ar is independently a substituted or unsubstituted phenylene moiety or a substituted or unsubstituted polynuclear moiety, aromatic carbon atoms of which are bonded directly to the --O-- or --CO-- or SO.sub.2 groups,
which comprises oligomerising a monomer system comprising (I) phosgene or an aromatic or aliphatic carboxylic or sulphonic diacid dihalide monomer and a polynuclear aromatic comonomer having two activated hydrogens or (II) a self-oligomerising polynuclear aromatic monomer containing both a carboxylic or sulphonic acid halide group and an active hydrogen atom, in a reaction medium comprising:
(A) a Lewis acid;
(B) a controlling agent comprising:
(i) R(OX).sub.a or added water which must be present in the reaction medium together with the Lewis acid before any monomer containing acid halide groups is added,
(ii) R(COOX).sub.a,
(iii) R(SO.sub.3 X).sub.a, or
(iv) (RO).sub.b Y, which, if the Y-O linkage(s) are reactive to acid halide groups, must be present in the reaction medium together with the Lewis acid before any monomer containing acid halide groups is added,
where R is a monovalent or polyvalent organic group compatible with the monomer(s) and the other components of the reaction medium,
each X independently is a hydrogen atom or a monovalent metal atom,
each a independently is 1 or 2,
Y is a multivalent metal atom, and
b is an integer equal to the valency of Y;
and
(C) optionally a non-protic diluent;
the various components being present in such proportions and the oligomerisation being conducted under such reaction conditions that a substantially linear arylene oligomer substantially free of pendant groups resulting from ortho substitution of para-linked aromatic rings in the oligomer back-bone is obtained either in a dispersed state, in which case the group R of the controlling agent (B) preferably has fewer than 8 aliphatic carbon atoms directly bonded to one another, or in a solution or gel state.

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A method of producing an arylene oligomer which comprises oligomerising a monomer system comprising:

(I)
(i) phosgene or an aromatic or aliphatic carboxylic or sulphonic diacid dihalide monomer and:
(ii) a polynuclear aromatic comonomer comprising:
(a) H-Ar-O-Ar-H
(b) H-(Ar-O).sub.n -Ar-H wherein n is 2 or 3
(c) H-Ar-O-Ar-(B-Ar-O.sup.-Ar).sub.m -H wherein m is 1, 2 or 3 or
(d) H-(Ar-O).sub.n -Ar-B-Ar-(O-Ar).sub.m -H wherein m is 1, 2, or 3, and
n is 2 or 3 or
(II)
a self-oligomerising carboxylic or sulphonic acid halide monomer of the formula
H-Ar-O-[(Ar-B).sub.p -(O-Ar).sub.q -(Ar-B).sub.r ].sub.k -Ar-B-Z
wherein Z is halogen, k is 0, 1 or 2, p is 1 or 2, q is 0, 1 or 2 and r is 0, 1 or 2;
or
(III)
a self-oligomerising carboxylic or sulphonic acid halide monomer the formula:
H-(Ar-O).sub.n -Ar-Y wherein n is 2 or 3 and Y is B-Z or B-Ar-B-Z;
where Z is halogen;
wherein each B independently is a carbonyl (-CO-) or sulphonyl (--SO.sub.2) group, and each Ar is independently selected from substituted or unsubstituted phenylene, and substituted and unsubstituted polynuclear aromatic moieties;
in a reaction medium comprising
(A) a Lewis acid in an amount of about one equivalent per equivalent of carbonyl or sulphonyl groups present in the monomer system plus about one equivalent per equivalent of controlling agent, plus an amount effective to act as a catalyst for the oligomerisation;
(B) a controlling agent, in an amount from 0.25 to 4 equivalents per equivalent of acid halide groups present in the monomer system, comprising:
(i) R(OX).sub.a or added water which must be present in the reaction medium together with the Lewis acid before any monomer containing acid halide group is added,
(ii) R(COOX).sub.a,
(iii) R(SO.sub.3 X).sub.a, or
(iv) (RO).sub.b Y, which, if the Y-O linkage(s) are reactive to acid halide groups, must be present in the reaction medium together with the Lewis acid before any monomer containing acid halide groups is added,
where R is an organic group compatible with with the monomer(s) and the other components of the reaction medium and, when the oligomer is produced in a dispersed state, preferably has fewer then 8 aliphatic carbon atoms directly bonded to one another,
each X independently is a hydrogen atom or atom or a monovalent metal atom,
each a independently is 1 or 2,
Y is a multivalent metal atom;
and
b is an integer equal to the valency
of Y;
and
(C) a non-protic diluent in an amount from 0 to about 93% by weight, based on the
weight of the total reaction mixture.

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Dependencies are inferred from the claim text.

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Abstract

A method of preparing an arylene oligomer having the repeat unit:

ti -Ar-O-Ar-B-
where
each B independently is a carbonyl (--CO--) or sulphonyl (--SO.sub.2 --) group, and each Ar is independently a substituted or unsubstituted phenylene moiety or a substituted or unsubstituted polynuclear moiety, aromatic carbon atoms of which are bonded directly to the --O-- or --CO-- or SO.sub.2 groups,
which comprises oligomerising a monomer system comprising (I) phosgene or an aromatic or aliphatic carboxylic or sulphonic diacid dihalide monomer and a polynuclear aromatic comonomer having two activated hydrogens or (II) a self-oligomerising polynuclear aromatic monomer containing both a carboxylic or sulphonic acid halide group and an active hydrogen atom, in a reaction medium comprising:
(A) a Lewis acid;
(B) a controlling agent comprising:
(i) R(OX).sub.a or added water which must be present in the reaction medium together with the Lewis acid before any monomer containing acid halide groups is added,
(ii) R(COOX).sub.a,
(iii) R(SO.sub.3 X).sub.a, or
(iv) (RO).sub.b Y, which, if the Y-O linkage(s) are reactive to acid halide groups, must be present in the reaction medium together with the Lewis acid before any monomer containing acid halide groups is added,
where R is a monovalent or polyvalent organic group compatible with the monomer(s) and the other components of the reaction medium,
each X independently is a hydrogen atom or a monovalent metal atom,
each a independently is 1 or 2,
Y is a multivalent metal atom, and
b is an integer equal to the valency of Y;
and
(C) optionally a non-protic diluent;
the various components being present in such proportions and the oligomerisation being conducted under such reaction conditions that a substantially linear arylene oligomer substantially free of pendant groups resulting from ortho substitution of para-linked aromatic rings in the oligomer back-bone is obtained either in a dispersed state, in which case the group R of the controlling agent (B) preferably has fewer than 8 aliphatic carbon atoms directly bonded to one another, or in a solution or gel state.

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