Titanium, zirconium- and hafnium containing initiators in the polymerization of acrylic monomers to "living" polymers
AssigneeE. I. Du Pont de Nemours and Company
InventorsWilliam B. Farnham, Walter R. Hertler
Life of this patent
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Abstract
Process for preparing "living" polymer, the process comprising contacting one or more acrylic monomers under polymerizing conditions with a polymerization-initiating amount of a tetra-coordinate organotitanium, organozirconium or organo-hafnium polymerization initiatior, and "living" polymers produced thereby.
Claims24
Process for preparing "living" polymer, the process comprising contacting one ore more acrylic monomers under polymerizing conditions with a polymerization-initiating amount of a tetracoordinate organotitanium, organozirconium or organohafnium polymerization initiator of the formula (R.sup.4).sub.3-a MZ.sub.a+1 or O[M(R.sup.4).sub.2 Z.sup.1 ].sub.2 wherein:
- each R.sup.4, independently, is --CH.sub.3, --F, --Cl, --Br, --I, --OR.sup.5, --NHR.sup.5, --NR.sub.2.sup.5, cyclopentadienyl, C.sub.6-20 aryl or C.sub.7-21 arylmethyl, or any of the last three groups containing substituents that are inert under polymerizing conditions;
- two R.sup.4 groups taken together are ##STR7## wherein each Z', independently, is O or NR', R', is C.sub.1-4 alkyl, and each of m and n is 2 to 4;
- each R.sup.5, independently, is hydrocarbyl which is aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic containing up to 20 carbon atoms, or said hydrocarbyl radical containing one or more functional substituents that are unreactive under polymerizing conditions;
- Z is an activating substituent selected from the group consisting of ##STR8## and mixtures thereof;
- X" is --OS(R.sup.1).sub.3, --OR.sup.6 or --NR'R";
- Z' is O or NR';
- m is 2, 3 or 4;
- n is 3, 4 or 5;
- Z.sup.1 is ##STR9## R.sup.6 is (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms;
- (b) a polymeric radical containing at least 20 carbon atoms;
- (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof;
- (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions;
- or
- (e) a radical of (a), (b), (c) or (d) containing one or more initiating sites;
- and
- each R.sup.1, independently, is a hydrocarbyl radical which is aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms or --H, provided that at least one R.sup.1 groups is not --H;
- each of R.sup.2 and R.sup.3 is independently selected from --H and hydrocarbyl, defined as for R.sup.6 above, subparagraphs (a) to (e);
- each of R' and R" is independently selected from C.sub.1-4 alkyl;
- M is Ti, Zr or Hf;
- and
- a is 0, 1 or 2, provided, however, when Z is --OC(X").dbd.C(R.sup.2)(R.sup.3), one R.sup.4 group and X", taken together, can be
- --Z'(CH.sub.2).sub.2 Z'--
- wherein Z' is defined as above.
"Living" polymer consisting essentially of at least four repeat units of at least one acrylic monomer and having at least one initiating site that comprises Ti, Zr or Hf and that is capable of polymerizing further in the presence of acrylic monomer(s), said polymer being of the formula R.sub.p [Z.sup.3 PQM(R.sup.4).sub.3 ].sub.p, O[M(R.sup.4).sub.2 QPZ"].sub.2 or (R.sup.4).sub.3-a M[QPZ"].sub.a+1 wherein:
- Rp is a hydrocarbyl radical which is aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic containing up to 20 carbon atoms, or a polymeric radical containing at least 20 carbon atoms, of valence p, optionally containing one or more ether oxygen atoms, keto groups and/or functional substitutents that are unreactive under polymerizing conditions;
- p is an integer and is at least 1;
- z.sup.3 is a diradical selected from the group consisting of ##STR10## and mixtures thereof;
- Z" is selected from the group consisting of ##STR11## P is a divalent polymeric radical consisting essentially of at least four repeat units of at least one acrylic monomer;
- Q is a divalent radical consisting essentially of one or both tautomeric forms of an acrylic repeat unit;
- each R.sup.4, independently, is --CH.sub.3, --F, --Cl, --Br, --I, --OR.sup.5, --NHR.sup.5, --NR.sub.2.sup.5, cyclopentadienyl, C.sub.6-20 aryl or C.sub.7-21 arylmethyl, or any of the last threee groups containing substituents that are inert under polymerizing conditons, and/or two R.sup.4 groups taken together are ##STR12## wherein each Z', independently, is O or NR', R' is C.sub.1-4 alkyl, and each of m and n is 2 to 4;
- M is Ti, Zr or Hf;
- a is 0, 1 or 2;
- X" is --OSi(R.sup.1).sub.3, --OR.sup.6 or --NR'R";
- R.sup.6 is
- (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms;
- (b) a polymeric radical containing at least 20 carbon atoms;
- (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof;
- (d) a radical of (a), (b) or (c) containing one or more functional substitutents that are unreactive under polymerizing conditions;
- or
- (e) a radical of (a), (b), (c) or (d) containing one or more initiating sites;
- each R.sup.5, independently, is hydrocarbyl which is aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic containing up to 20 carbon atoms, or said hydrocarbyl radical containing one or more functional substitutents that are unreative under polymerizing conditions;
- each of R.sup.2 and R.sup.3 is independently selected from --H and hydrocarbyl, defined as for R.sup.6 above, subparagraphs (a) to (e);
- each R.sup.1, independently, is a hydrocarbyl radical which is aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms or --H, provided that at least one R.sup.1 group is not --H;
- and
- each of R' and R" is independently selected from C.sub.1-4 alkyl.
Dependencies are inferred from the claim text.