Method for preparing (co) polymers by metal-free anionic polymerization in the presence of a phosphonium cation containing at least one annellated aromatic ring

A method for preparing a (co)polymer having an average M.sub.w /M.sub.n .ltoreq.1.2, comprising the steps of:

• mixing a monomer of the formula I, or a monomer of the formula II, or a mixture of both I and II:
• ##STR11## with an initiator corresponding to or containing
• ((R.sup.6 R.sup.7 R.sup.8 PR.sup.9).sup.+).sub.n Q.sup.n- (III) and/or (R.sup.6 R.sup.7 R.sup.8 PR.sup.9).sup.+ (Q').sup.- (IV)
• and conducting the reaction at temperature of from 50.degree. C. to 150.degree. C., in the presence or the absence of a solvent, for a length of time sufficient to polymerize the monomer(s) to form a (co)polymer;
• and isolating the formed (co)polymer, wherein
• R.sup.1 is selected from the group consisting of CN, methyl and phenyl,
• R.sup.2 is independently selected from the group consisting of CN and C(.dbd.O)R.sup.3,
• X.sup.1 is O,
• R.sup.3 is alkyl of from 1 to 20 carbon atoms, substituted alkyl of from 1 to 20 carbon atoms, having as substituents one or more halides, --O-alkyl of from 1 to 20 carbon atoms, substituted --O-alkyl of from 1 to 20 carbon atoms having as substituents one or more halides,
• --O-alkyl of from 3 to 20 carbon atoms having one or more epoxy units,
• --O-cycloalkyl of from 3 to 15 carbon atoms,
• --O-cycloalkyl of from 3 to 15 carbon atoms having as substituents one or more halides,
• --O-cycloalklyl of from 5 to 12 carbon atoms having one or more epoxy units,
• --O-alkenyl of from 2 to 12 carbon atoms,
• --O--R'--O--R" or --O--R'--NR"R'", wherein R' is an alkylene chain of from 2 to 10 carbon atoms, C.sub.6 - to C.sub.18 -arylene, an alkylene chain having one or more ether units in the chain, R" is C.sub.1 - to C.sub.10 -alkyl, C.sub.6 - to C.sub.18 -aryl, C.sub.3 - to C.sub.10 -cycloalkyl, or C.sub.3 - to C.sub.30 -organosilyl and R'" is H, C.sub.1 - to C.sub.10 -alkyl, C.sub.6 - to C.sub.18 -aryl, C.sub.3 - to C.sub.10 -cycloalkyl, C.sub.3 - to C.sub.30 -organosilyl, or --S-alkyl of from 1 to 20 carbon atoms;
• X.sup.2 is 0;
• L is an alkylene of from 1 to 16 carbon atoms, or an arylene of from 6 to 18 carbon atoms, which may be substituted with m functional groups CH.sub.2 .dbd.C(R.sup.1)C(.dbd.O)O--
• m is an integer of from 2 to 20;
• R.sup.6 R.sup.7 and R.sup.8 are independently C.sub.6 - to C.sub.14 -aryl or substituted C.sub.6 - to C.sub.14 -aryl having one or more substituents selected from the group consisting of alkyl of from 1 to 16 carbon atoms, oxyalkyl of from 1 to 16 carbon atoms, C.sub.6 - to C.sub.14 -aryl, oxy-C.sub.6 - to C.sub.14 -aryl, substituted oxy-6- to C.sub.14 -aryl, alkylene-oxy-alkyl of from 3 to 17 carbon atoms, aminodialkyl of from 2 to 14 carbon atoms, amino(alkyl) (aryl) (aryl) of from 7 to 15 carbon atoms, aminodiaryl of from 12 to 28 carbon atoms, halides, thio-alkyl of from 1 to 16 carbon atoms, and substitute thio-C.sub.6 - to C.sub.14 -aryl,
• R.sup.9 is 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl, said naphthyl, anthracenyl or phenanthryl having one or more substituents selected from the group consisting of halides, alkyl of from 1 to 20 carbon atoms, oxyalkyl of from 1 to 20 carbon atoms, C.sub.6 - to C.sub.22 -aryl, substituted C.sub.6 - to C.sub.22 -aryl, oxy-aryl of from 6 to 18 carbon atoms, substituted oxyalkyl of from 6 to 20 carbon atoms, aminodialkyl having from 2 to 30 carbon atoms, amino(alkyl)(aryl) having from 7 to 30 carbon atoms, aminodiaryl of from 12 to 36 carbon atoms, thio-alkyl of from 1 to 20 carbon atoms, thio-C.sub.6 - to C.sub.22 -aryl, and substituted thio-C.sub.6 - to C.sub.22 -aryl,
• Q is CR.sup.10 R.sup.11 R.sup.12, NR.sup.13 R.sup.14, OR.sup.15, SR.sup.16 or R.sup.17 (CR.sup.10 R.sup.11).sub.p (NR.sup.13).sub.q (O).sub.r (S).sub.s wherein p, q, r and s are independently an integer of from 0 to 30 and where the sum of p to s is at least 2;
• Q' is R.sup.18 --CR.sup.10 R.sup.11 R.sup.12, R.sup.18 --NR.sup.13 R.sup.14, R.sup.18 --OR.sup.15, R.sup.18 --SR.sup.16, R.sup.18 --Z;
• R.sup.10 and R.sup.11 are independently alkyl, each of from 1 to 10 carbon atoms, alkyl of from 1 to 10 carbon atoms having as substituents one or more halides, C.sub.6 - to C.sub.14 -aryl, substituted C.sub.6 - to C.sub.14 -aryl, CN, C(.dbd.O)R.sup.3 as defined above, organosilyl having from 3 to 18 carbon atoms, or either R.sup.10 or R.sup.11 are H, or R.sup.10 and R.sup.11 are joined together to form a ring, having from 3 to 10 carbon atoms,
• R.sup.12 is H, alkyl of from 1 to 10 carbon atoms, C.sub.6 - to C.sub.14 -aryl, or a (co)polymer radical;
• R.sup.13 and R.sup.14 are independently alkyl of from 1 to 10 carbon atoms, C.sub.6 - to C.sub.14 -aryl, C.sub.7 - to C.sub.15 aralkyl, C.sub.3 - to C.sub.18 -organosilyl, or R.sup.13 and R.sup.14 are joined together to form a heterocycle,
• R.sup.15 and R.sup.16 are independently alkyl of from 1 to 10 carbon atoms, cycloalkyl of from 3 to 10 carbon atoms or C.sub.6 - to C.sub.14 -aryl,
• R.sup.17 is an alkylene of from 2 to 10 carbon atoms, cycloalkylene of from 3 to 10 carbon atoms, or an C.sub.6 - to C.sub.10 -arylene,
• R.sup.18 is a (co)polymer radical;
• Z is a radical derived from an initiator for the anionic polymerization of anionic polymerizable monomers other than radicals derived from compound Ill or IV,
• n is an integer of from 1 to 30.