US 4,791,189 AGranted

Terminally unsaturated macromolecular monomers of polylactones and copolymers thereof

AssigneeThe B. F. Goodrich Company

InventorSimon H. Yu

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Abstract

Preparation of a macromolecular monomer of a lactone allows the preparation of copolymers of lactones with commonly available olefinically unsaturated monomers. There is no known method for the preparation of such copolymers. A cationic ring-opening polymerization of a lactone in conjunction with an unsaturated alcohol (propagator) having an acryloyl, allyl or styryl double bond, produces a polylactone macromer having an ethylenic double bond at one end and a hydroxyl group at the other. The polymerization proceeds by polyaddition of the lactone to the OH group which is the propagating species. The polylactone may include a polymeric or non-polymeric spacer. The propagator is a primary or secondary alcohol which, if cyclic may have a single internal double bond in one ring. The catalyst is an oxonium salt, or etherate of boron trifluoride. The macromer may be copolymerized with a wide variety of olefinically unsaturated monomers to form a macromer copolymer with pendant polylactone chains. In particular, block copolymers of terminally unsaturated macromers of ether-ester, or ester-ether structure may be tailored for specific applications.

A process for the manufacture of a polylactone macromer having an ethylenically unsaturated functional group near one end and a hydroxyl group at the other, comprising, polymerizing

(A) a cationically ring-openable lactone having the structure:
##STR25## wherein, n is an integer in the range from 4 to about 7;
R.sup.1 is a group selected from hydrogen, C.sub.1 -C.sub.20 alkyl, cycloalkyl, alkoxy and phenyl, and the number of R.sup.1 groups which are H is at least (n+2);
and,
(B) an ethylenically unsaturated primary or secondary alcohol selected from the group consisting of
(i) an acryloyl alcohol wherein the ethylenic unsaturation is adjacent a carbonyl group as in the structure ##STR26## wherein R.sup.2 is H or alkyl having from 1 to about 20 carbon atoms (C.sub.1 -C.sub.20);
R.sup.3, if present, is selected from the group consisting of branched or linear alkylene, haloalkylene, alkoxyl, haloalkoxyl, each C.sub.1 -C.sub.20, aralkylene, haloaralkylene, aralkoxyl, and haloaralkoxyl, each C.sub.7 -C.sub.20 ;
G is a polymeric polyether spacer containing no active hydrogen, and having a number average molecular weight Mn up to about 30,000;
(ii) a styrylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent an aromatic ring, said alcohol represented by the structure ##STR27## wherein, R.sup.3 and G, if either is present, is in an ortho-, meta-, or para-position of the phenyl ring which may be substituted, said position being relative to that of the olefinically unsaturated group;
and,
R.sup.4 and R.sup.5 are selected from the group consisting of hydrogen, C.sub.1 -C.sub.10 alkyl and haloalkyl, and, at least one of R.sup.4 and R.sup.5 is always H;
(iii) an allylically unsaturated primary or secondary alcohol represented by the structure ##STR28## wherein only G is optionally present;
or ##STR29## wherein, both R.sup.3 and G are each optionally present;
R.sup.6, R.sup.7 and R.sup.8 are independently selected from the group consisting of hydrogen, C.sub.1 -C.sub.20 alkyl and haloalkyl, and, C.sub.6 -C.sub.20 aryl and aralkyl;
in the presence of an effective amount of
(C) a cationic initiator selected from the group consisting of an oxonium salt and etherate of boron trifluoride at a temperature in the range from 0.degree. C. to 90.degree. C.;
so as to produce a macromer having substantially uniform molecular weight distribution such that its ratio of Mw/Mn is not above 5.0, with conversion in the range from about 81% to about 95%, said macromer having the structure
R--(M).sub.m --OH (LM)
wherein R represents the residue of said alcohol having a vinyl group,
M represents the polyester repeating unit of at least one said lactone which is ring-opened, and,
m represents an integer in the range from 2 to about 500.

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Abstract

Claims7