Discussion of the Background : In the last decade, great interest has emerged concerning the polymerization of (meth) acrylates, particularly methyl meth- acrylate (MMA), under ambient conditions. A number of new polymerization systems have been reported, and a recent review covers most of the literature on the polymerization of MMA at am- bient temperatures (T. P. Davis, D. M. T. Haddelton, S. N. Rich- ards, J. M. S.-Rev. Macromol. Chem Phys, 1994, C34,243).

For example, a process known as Group Transfer Polymerization (GTP), introduced in the early 1980's, produced poly (methyl meth- acrylate) (PMMA) and allowed control of molecular weight dis- tribution (MWD), molecular weight and molecular architecture at ambient temperatures (Webster et al. J. Am Chem. Soc. 1983,105, 5706).

Reetz et al (Angew. Chem. Int. Ed. Engl. 1988,27,1371; Polymer Preprints (Am. Chem. Soc., Div. Polym. Chem.) 1991,32,296) have postulated that, in the anionic polymerization of n-butyl acrylate at ambient temperatures using a tetrabutylammonium coun- tercation, the intramolecular Claisen type termination reaction is decreased because the electrostatic attraction between the alkoxide and the bulky n-Bu4N+ cation is weak, thereby thermody- namically and kinetically disfavoring the formation of the ter- mination by-product tetrabutylammonium alkoxide. However, anionic polymerizations with ammonium countercations also suffer from some drawbacks, such as low yield, which may be the result of a Hoffmann elimination of a-hydrogen from the ammonium cation at a rate competitive with polymerization.

A distinct improvement on the methods described is constituted by the anionic polymerization in the presence of phosphonium counterions (WO 96/28487, U. S. patent application Serial No.

08/609,732). According to WO 96/28487 the polymerization is car- ried out at temperatures of up to 40°C.

The polymerization of acrylic acid derivatives at temperatures of more than 20°C and particularly between 40 and 120°C in the pres- ence of an initiator corresponding to or containing the structure where E may be CRIVRv and where C together with Ri and Rv may form an unsaturated isocyclic ring was disclosed in DE-A 36 32 361 and DE-A 37 00 195. Since a phosphonium species is found to be cova- lently linked to the polymer chain formed a mechanism according to Klippert and Ringsdorf (Makromol. Chem. 1972,53,289-306) where the ylide carbon atom attacks the acrylic or methacrylic monomer can be postulated. The initiator (V) can also be used in its protonated form. As shown in the examples the best results are obtained when the initiator is employed as Lewis acid adduct.

Merely very poor yields, incomplete monomer conversion and polymers having a broad molecular weight distribution are ob- tained when the reaction is performed in the presence of the neu- tral catalyst. In the case of the protonated species the acidic proton may cause chain termination. Therefore, the scope of the polymerization using (V) is limited.

Another entry to metal-free anionic polymerization of acrylates and methacrylates disclosed by Seebach and Pietzonka (Angew.

Chem. Int. Ed. Engl. 1993,32,716) makes use of the P4-phospha- zene base introduced by Schwesinger and Schlemper (Angew. Chem.

1987,99,1212) which forms a very soft and bulky cation. The initiating system can for example be prepared by treating ethyl acetate with the P4-phosphazene base. Polymerization of for example methylmethacrylate is accomplished at 60°C furnishing pre- dominantly a syndiotatic polymer material. However, the P4-phos- phazene base is not readily available and therefore not favorable for large scale production. In addition, the formation of block copolymers has not yet been disclosed.

Thus, a need exists for a method for producing poly (meth) acrylate polymers and copolymers having a narrow molecular weight dis- tribution, which provides effective control of (co) polymer molec-

ular weight, of molecular weight distribution and of (co) polymer stereoregularity in good yields and at technically favorable tem- peratures, also allowing for large scale production.

OBJECTS OF THE INVENTION Accordingly, it is one object of the present invention to provide a novel method for anionically producing (co) polymers which pro- vides a (co) polymer having a narrow molecular weight distribu- tion.

It is a further object of the present invention to provide a novel method for producing (co) polymers by anionic polymerization which provides effective control of (co) polymer molecular weight.

It is a further object of the present invention to provide a novel method for producing (co) polymers by anionic polymerization which provides the (co) polymer in good yields.

It is a further object of the present invention to provide a novel method for producing (co) polymers which achieves the above objects in a controlled manner at temperatures higher than 40°C and in particular at temperatures higher than 60°C.

It is a further object of the present invention to provide a novel initiator for producing (co) polymers by anionic polymerization.

Furthermore, it is one object of the present invention to provide a novel method for anionically producing poly (meth) acrylate (co) polymers which provides a (co) polymer having a narrow molecu- lar weight distribution.

It is a further object of the present invention to provide a novel method for producing poly (meth) acrylate (co) polymers by anionic polymerization which provides effective control of (co) polymer molecular weight.

It is a further object of the present invention to provide a novel method for producing poly (meth) acrylate (co) polymers by anionic polymerization which can provide effective control of (co) polymer stereoregularity (e. g. syndiotacticity).

It is a further object of the present invention to provide a novel method for producing poly (meth) acrylate (co) polymers by anionic polymerization which provides the (co) polymer in good yields.

It is a further object of the present invention to provide a novel method for producing poly (meth) acrylate (co) polymers which achieves the above objects in a controlled manner at temperatures higher than 40°C and in particular at temperatures higher than 60°C.

It is a further object of the present invention to provide a novel initiator for producing poly (meth) acrylate (co) polymers by anionic polymerization.

These and other objects, which will become apparent in the fol- lowing detailed description of the preferred embodiments, have been provided by a method for producing a (co) polymer, particu- larly a (meth) acrylate (co) polymer, which comprises: mixing a monomer of the formula I, or a monomer of the formula II, or a mixture of both I and II: with an initiator corresponding to or containing [ (R6R7R8PR9) +] n Qn- (III) and/or (R6R7R8PR9) + (Q')- (IV) and conducting the reaction at a temperature of from more than 40°C, in the presence or the absence of a solvent, for a length of time sufficient to polymerize the monomer (s) and to form a (co) polymer; and isolating the formed (co) polymer, wherein: R1 is selected from the group consisting of H, CN, CF3, alkyl of from 1 to 6 carbon atoms and C6-to Cis-aryl, R2 is independently selected from the group consisting of CN, C (=Xl) R3, C (=X1) NR4R5 and heterocyclic rings capable of stabi- lizing an a-anion,

X1 is iminoalkyl of from 1 to 20 carbon atoms, iminoaryl of from 6 to 18 carbon atoms, 0 or S, R3 is alkyl of from 1 to 20 carbon atoms, substituted alkyl of from 1 to 20 carbon atoms having as sub- stituents one or more halides, -0-alkyl of from 1 to 20 carbon atoms, substituted-0-alkyl of from 1 to 20 carbon atoms having as substituents one or more halides, -0-alkyl of from 3 to 20 carbon atoms having one or more epoxy units, -0-cycloalkyl of from 3 to 15 carbon atoms, -0-cycloalkyl of from 3 to 15 carbon atoms having as substi- tuents one or more halides, -0-cycloalkyl of from 5 to 12 carbon atoms having one or more epoxy units, -0-alkenyl of from 2 to 12 carbon atoms, -0-R'-O-R''or-O-R'-NR''R''', wherein R'is an alkylene chain of from 2 to 10 carbon atoms, C6-to Cl8-arylene, an alkylene chain having one or more ether units in the chain, R''is C1-to Clo-alkyl, C6-to C1a-aryl, C3-to C1o-cyclo- alkyl, or C3-to C30-organosilyl and R'''is H, C1-to Cl0-alkyl, C6-to Cis-aryl, C3-to Clo-cycloalkyl, C3-to C30-organosilyl, or -S-alkyl of from 1 to 20 carbon atoms; R4 and R5 are independently alkyl of from 1 to 20 carbon atoms, alkyl of from 1 to 20 carbon atoms having as substituents one or more halides, or are joined together to form an alkylene ring of from 2 to 8 carbon atoms or an alkylene ring of from 2 to 8 carbon atoms containing one or more additional hetero- atoms, selected from the group consisting of the elements of group VA and VIA of the periodic table of the elements, thus forming a 3-to 10-membered ring, cycloalkyl of from 3 to 12 carbon atoms, or alkenyl of from 2 to 12 carbon atoms; X2 is aminoalkyl of from 1 to 20 carbon atoms, aminoaryl of from 6 to 18 carbon atoms, 0, S or-C (Ra) (Rb)-, wherein Ra and Rb are independently H, C1-to C20-alkyl, C3-to C12-cycloalkyl or C6-to C, B-aryl, L is an organic radical of value m, m is an integer of from 2 to 20;

R6, R7 and R8 are independently C6-to C22-aryl or substituted C6- to C22-aryl having one or more substituents selected from the group consisting of alkyl of from 1 to 20 carbon atoms, oxy- alkyl of from 1 to 20 carbon atoms, C6-to C22-aryl, substi- tuted C6-to C22-aryl, oxy-C6-to C22-aryl, substituted oxy-C6- to C22-aryl, alkylene-oxy-alkyl of from 2 to 20 carbon atoms, aminodialkyl of from 2 to 30 carbon atoms, amino (alkyl) (aryl) of from 7 to 30 carbon atoms, aminodiaryl of from 12 to 36 carbon atoms, halides, thio-alkyl of from 1 to 20 carbon atoms, thio-C6-to C22-aryl, and substituted thio-C6-to C22-aryl, R9 is C1o-to C22-aryl or substituted C1o-to C22-aryl having one or more substituents selected from the group consisting of alkyl of from 1 to 20 carbon atoms, oxyalkyl of from 1 to 20 carbon atoms, C6-to C22-aryl, substituted C6-to C22-aryl, oxy-aryl of from 6 to 22 carbon atoms, substituted oxy-aryl of from 6 to 22 carbon atoms, alkylene-oxy-alkyl of from 2 to 20 carbon atoms, aminodialkyl of from 2 to 30 carbon atoms, amino (alkyl) (aryl) of from 7 to 30 carbon atoms, aminodiaryl of from 12 to 36 carbon atoms, halides, thio-alkyl of from 1 to 20 carbon atoms, thio-C6-to C22-aryl, and substituted thio-C6-to C22-aryl, Q is CRORR, NR13Rl4, OR15, SR16 or Rl7 (CR1R11) p (NR13) q (O) r (S) 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'isRl8-CRlORllRl2,Rl8-NRl3Rl4R18-OR15,Rl8-gRl6Rl8-z; Rio and Rll are independently alkyl, each of from 1 to 20 carbon atoms, alkyl of from 1 to 20 carbon atoms having as substitu- ents one or more halides, C6-to C, B-aryl, substituted C6-to Cis-aryl, CN, C (=X1) R3 as defined above, C (=X1) NR4R5 as defined above, organosilyl having from 3 to 30 carbon atoms, or ei- ther RIO or Rll are H, or R10 and RII are joined together to form a ring, having from 3 to 10 carbon atoms, R12 is H, alkyl of from 1 to 20 carbon atoms, C6-to C, B-aryl, or a (co) polymer radical; R13 and R14 are independently alkyl of from 1 to 20 carbon atoms, C6-to Cis-aryl, C7-to C20 aralkyl, C3-to C30-organosilyl, C (=X1) R3 as defined above, or R13 and R14 are joined together to form a heterocycle,

R15 and R16 are independently alkyl of from 1 to 20 carbon atoms, cycloalkyl of from 3 to 10 carbon atoms or C6-to C18-aryl, R17 is an organic radical of value n, R18 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 compounds III or IV and n is an integer of from 1 to 30.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present process can be used to make polymers and copolymers (statistical copolymers as well as block copolymers) (hereinafter " (co) polymers") from a wide variety of monomers. Vinyl monomers suitable for the present process should preferably bear at least one electron-withdrawing and/or formal negative charge-stabiliz- ing group, such as an ester group, a keto group, a sulfone group, a phosphonate group, a heterocyclic ring, etc. In the context of the present invention both acrylates and methacrylates fall under the definition of the term (meth) acrylates. The initiator can comprise any stabilized carbanion, but preferably one in which the corresponding neutral carbon acid has a pKa of from 12 to 37, and more preferably, a pKa of from 18 to 35. Alternatively the initiator can comprise amide anions, oxide anions or sulfide anions. It is within the scope of the present invention that mix- tures of different anions may be used as well. The key to the present process involving the anionic, metal-free polymerization of a vinyl monomer lies in the use of a phosphonium countercation containing at least one annellated aromatic ring as substituent on the phosphorous atom. In the context of this invention the term initiator encompasses also mixtures of two or more different initiators.

The present invention provides (co) polymers, and particularly poly (meth) acrylates, having a relatively narrow molecular weight distribution, in quantitative or nearly quantitative yields at reaction temperatures higher than 40°C. Molecular weights of the (co) polymers produced by the present process, which may be weight average or number average molecular weights, may be controlled by controlling the molar ratio of initiator to monomer, and may range from 500 g/mol to 300,000 g/mol, preferably from 1,000 to 200,000 g/mol, and most preferably from 2,000 to 100,000 g/mol.

Even at 70°C the (co) polymers produced exhibit a narrow molecular

weight distribution (Mw/Mn < 1.2) (e. g., a Mw/Mn of about 1.18 for a PMMA produced using [(l-Naphthyl) P (Ph) 3 + (CPh3)- (Ph denoting phenyl), having a Mn of 19,000 g/mol). In the context of the pres- ent application, a narrow molecular weight distribution refers to a (co) polymer having number average molecular weight (Mn) of < 2. 0, preferably < 1.5, and most preferably < 1. 2.

The polymerization rate of the present method is relatively mod- erate over a very wide temperature range, allowing for a control of reaction conditions and product parameters. Monomer conver- sions typically are complete (e. g., at least 90%, preferably at least 95% and most preferably at least 98% of the monomer are consumed during the polymerization reaction).

Because the present reacting step is a"living"polymerization, the process can be applied to the preparation of block and multi- block copolymers. The bulky phosphonium cations are believed to prevent intramolecular cation coordination to the ante-penulti- mate ester carbonyl group.

Polymers produced using the present process have a variety of uses. For example, PMMA is the polymer used to make transparent molds such as glaslike sheets. Furthermore, the polymers produced by the present method have sufficiently narrow molecular weight distributions as to provide PMMA or other polymer standards for size exclusion chromatography.

Monomers suitable for polymerization in the present method in- clude those of the formula (I) : wherein RI is selected from the group consisting of H, CN, CF3, alkyl which can be linear, branched or cyclic of from 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, i-propyl or cyclohexyl and C6-to C, 8-aryl, in particular H, methyl or phenyl, R2 is independently selected from the group consisting of CN, C (=X1) R3, C (=Xl) NR4R5 and heterocyclic rings capable of stabi- lizing an a-anion, in particular C (=O) R3,

X1 is iminoalkyl which can be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl or cyclo- hexyl, iminoaryl of from 6 to 18 carbon atoms, in particular of from 6 to 10 carbon atoms, such as phenyl, O or S, in par- ticular O, R3 is alkyl which can be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl or cyclohexyl, sub- stituted alkyl of from 1 to 20 carbon atoms having as substi- tuents one or more halides, such as fluorine or chlorine, e. g. trifluoromethyl or pentafluoroethyl, -0-alkyl of from 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-do- decyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, 2-methylpropyl, 2-methylbutyl, 2-methylhexyl, 2-methyloctyl, 2-ethylbutyl, 2-ethylpentyl, 2-ethylhexyl, 2-ethyloctyl, 3-methylbutyl, 3-methylpentyl, 3-methylhexyl, 3-methyloctyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethyloctyl, wherein methyl, n-butyl, t-butyl, 2-ethylhexyl and n-dodecyl are particularly preferred, substituted-O-alkyl which can be linear or branched of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, having as substituents one or more C6-to Cis-aryl groups, such as 2-phenylethyl, 2-phenyl-n-propyl, 2-phenyl-n- butyl, 2-phenyl-n-pentyl, 2-phenyl-n-hexyl or 2-phenyl-n-oc- tyl, substituted-O-alkyl which can be linear or branched of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon chlorine atoms, having as substituents one or more halides, such as chlorine or fluorine, in particular those of from 1 to 6 carbon atoms, such as trifluoromethyl, pentafluoroethyl or 2,2,2-trifluoroethyl, -0-alkyl which can be linear or branched of from 3 to 20 carbon atoms having one or more epoxy units, in particular those having 1 to 10 carbon atoms, such as 0- (2, 3-epoxy-1-propyl), -0-cycloalkyl of from 3 to 15 carbon atoms, in particular of from 3 to 12 carbon atoms, such as cyclohexyl, 4-t-butylcy- clohexyl or i-bornyl, -0-cycloalkyl of from 3 to 15 carbon atoms having as substi- tuents one or more halides, such as chlorine or fluorine, in particular of from 5 to 12 carbon atoms, such as 2-chlorocy- clohexane, -0-cycloalkyl of from 3 to 12 carbon atoms having one or more

epoxy units, such as 2,3-epoxycyclohexane, -0-alkenyl of from 2 to 12 carbon atoms, in particular of from 3 to 10 carbon atoms, such as-O-allyl or-O-dihydrodi- cyclopentadienyl, -O-R'-O-R''or-0-R'-NR''R''', wherein R'is an alkylene chain which can be linear, branched or cyclic of from 1 to 10 carbon atoms, in particular of from 2 to 4 carbon atoms, such as ethylen, 1, 2-propylene, 1,3-propylene or 1,4-butylene, C6- to Gia-arylene, in particular o-, m-or p-phenylene, an alkylene chain having one or more ether units in the chain, such as-(CH2CH2O) 1 to 5 (CH2CH2)-, in particular 1 to 3 ether units, R''is C1-to Clo-alkyl, which can be linear or branched in particular C1-to C6-alkyl, such as methyl, ethyl, n-propyl, i-propyl or n-butyl, C6-to Cis-aryl, in particular C6-to Clo-aryl, such as phenyl, C3-to Cl0-cycloalkyl, in particular C3-to C6-cycloalkyl, such as cyclohexyl, or C3-to C30-organosilyl, in particular C3-to C18-organosilyl in which the tetravalent silicon atom is preferably substituted with radicals selected from the group consisting of alkyl which can be linear, branched or cyclic having from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, i-propyl, n-butyl, t-butyl or cyclohexyl, aryl having from 6 to 18 carbon atoms, in particular of from 6 to 10 carbon atoms, such as phenyl, and aralkyl, being formed from a C1-to C6-alkylene moiety, in particular a C1-to C3-alkylene moiety, and a C6-to C, B-aryl moiety, in particu- lar a C6-to Clo-aryl moiety, such as benzyl, examples are trimethylsilyl, triethylsilyl, triphenylsilyl, dimethyl- phenylsilyl or methyldiphenylsilyl, and R'''is H and other- wise as defined above for R'', -S-alkyl which can be linear or branched of from 1 to 20 carbon atoms, in particular of from 2 to 12 carbon atoms, such as ethyl, n-propyl, i-propyl, cyclohexyl, n-dodecyl or t-dodecyl ; R4 and R5 are independently alkyl which can be linear or branched of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl or cyclohexyl, alkyl which can be linear or branched of from 1 to 20 carbon atoms having as substituents one or more ha- lides, in particular those of from 1 to 10 carbon atoms, such as fluorine or chlorine, e. g. trifluoromethyl, or are joined together to form an alkylene ring, in particular an alkylene ring of from 2 to 8, preferably from 2 to 5 carbon atoms, such as tetrahydropyrolidin, or an alkylene ring containing one or more additional heteroatoms, selected from the group consisting of the elements of group VA and VIA of the peri-

odic table of the elements, in particular such a ring con- taining of from 2 to 8 carbon atoms and preferably having an oxygen or nitrogen atom in the ring, such as a morpholino ring, thus forming a 3-to 10-membered ring, cycloalkyl of from 3 to 12 carbon atoms, such as cyclohexyl, or alkenyl of from 2 to 12 carbon atoms, in particular of from 3 to 10 carbon atoms, such as allyl.

More specifically, preferred monomers include acrylate and meth- acrylate esters of alkanols of from 1 to 20 carbon atoms, in par- ticular of from 1 to 12 carbon atoms, such as methyl acrylate, n- butyl acrylate, t-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate or 2-ethylhexyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, allyl methacrylate, dicyclopentadienylmethacrylate or acrylonitrile. Preferred monomers are also vinyl heterocycles selected from the group consisting of vinyl pyridines, preferably 2-pyridine or 4-pyridine and vinyl pyrimidines. Also preferred are cyanoacrylate esters of C1-to C20-alcohols. The most pre- ferred monomers are methyl methacrylate, 2-ethylhexylacrylate, n- butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, allyl methacrylate, in particular methylmethacrylate (MMA) and t-butylmethacrylate.

Monomers suitable for polymerization in the present method in- clude also those of the formula II wherein: R1 and xl are as defined above; X2 is aminoalkyl which can be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl or cyclo- hexyl, aminoaryl of from 6 to 18 carbon atoms, preferably phenyl, O, S or-C (Ra) (Rb)-, wherein Ra and Rb are indepen- dently H, C1-to C20-alkyl which can be linear or branched, preferably C1-to Clo-alkyl such as methyl, ethyl, n-propyl or i-propyl, C3-to C12-cycloalkyl, preferably C3-to C6-cyclo-

alkyl such as cyclohexyl, or C6-to C, B-aryl, preferably phenyl; O being particularly preferred, L is an organic radical of value m, in particular an aliphatic moiety such as an alkylene of from 1 to 30 carbon atoms, pre- ferably of from 1 to 16 carbon atoms, or an aromatic moiety such as an arylene of from 6 to 18 carbon atoms, which may be substituted with m functional groups CH2=C (R1) C (=Xl) X2-, as defined above, such as 1,2-ethylene, 1,2-propylene, 1,3-propylene, bisphenylen, pentaerythryl, and m is an integer of from 2 to 20.

More specifically, preferred monomers (II) include di-and poly- acrylate esters and di-and polymethacrylate esters derived from di-and polyols having from 2 to 20 carbon atoms, in particular from 2 to 16 carbon atoms, such as ethylene glycol, 1,4-butane- diol, pentaerythrit, resorcinol, hydroquinone, brenzcatechinol, polyether units having 2 or more hydroxy groups or glycerol.

In the context of the present invention, with respect to for- mula (I) and (II),"C6-to C, 8-aryl" preferably refers to phenyl and naphthyl, which may be substituted from 1 to 5 times (in the case of phenyl) or from 1 to 7 times (in the case of naphthyl) and preferably from 1 to 3 times (in both cases) as defined above. Most preferably,"aryl"in (I) or (II) refers to phenyl.

Suitable initiators include those of the formula III : [ (R6R7R8pR9) +] n Qn- (III) wherein R6, R7 and R8 are independently C6-to C22-aryl, in particular C6- to C14-aryl, such as phenyl, naphthyl, fluorenyl, anthracenyl or phenanthryl, or substituted C6-to C22-aryl, in particular C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-hexadecyl, cyclopropyl, cyclopentyl or cyclohexyl; oxyalkyl of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, in which alkyl may be linear, branched or cyclic, such as-0- <BR> <BR> methyl,-0-ethyl,-0-n-propyl,-0-i-propyl,-0-n-butyl,<BR> ; -O-i-butyl,-O-t-butyl,-O-n-pentyl,-O-n-hexyl,-O-n-heptyl,

-0-n-octyl,-0-n-nonyl,-0-n-decyl,-0-n-dodecyl,-0-n-hexa- decyl,-O-cyclopropyl,-0-cyclopentyl,-0-cyclohexyl, -O- (CH2CH20) 1 to 5-CH3 ; C6-to C22-aryl, in particular C6-to C14-aryl, such as phenyl; substituted C6-to C22-aryl, in par- ticular C6-to C14-aryl, having one or more substituents se- lected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-dodecyl or cyclohexyl; oxy-C6-to C22-aryl, in particular oxy-C6-to C14-aryl, such as -0-phenyl ; substituted oxy-C6-to C22-aryl, in particular oxy-C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particu- lar of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-dodecyl or cyclohexyl; alky- lene-oxy-alkyl of from 2 to 20 carbon atoms, in particular of from 3 to 17 carbon atoms, such as- (CH2) 1 to s-°-(CH2cH2°) o to 5-CH3; aminodialkyl of from 2 to 30 carbon atoms, in particu- lar of from 2 to 14 carbon atoms, such as dimethylamino, die- thylamino, di (n-propyl) amino, di (i-propyl) amino, di (n-bu- tyl) amino, di (i-butyl) amino, (methyl) (ethyl) amino; aminoalky- laryl of from 7 to 30 carbon atoms, in particular of from 7 to 15 carbon atoms, such as (methyl) (phenyl) amino, (ethyl) (phenyl) amino; aminodiaryl of from 12 to 36 carbon atoms, in particular of from 12 to 28 carbon atoms, such as diphenylamino, dinaphthylamino or (naphthyl) (phenyl) amino; halides, in particular fluoride, chloride, bromide or iodide, preferably fluoride, chloride or bromide; thio-alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, in which alkyl may be linear, branched or cyclic, such as-S-methyl,-S-ethyl,-S-n-propyl,-S-i-propyl,-S-n-butyl, -S-i-butyl,-S-t-butyl,-S-n-pentyl,-S-n-hexyl,-S-n-heptyl, -S-n-octyl,-S-n-nonyl,-S-n-decyl,-S-n-dodecyl,-S-n-hexa- decyl,-S-cyclopropyl,-S-cyclopentyl,-S-cyclohexyl ; thio- Ce-to C22-aryl, in particular thio-C6-to C14-aryl, such as phenyl or naphthyl; substituted thio-C6-to C22-aryl, in par- ticular thio-C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-dodecyl or cyclohexyl.

The C6-to C22-aryl in R6, R7 and R8 may be mono-, di-, poly-or persubstituted with substituents as defined above. Thus, if the aryl moiety is phenyl or naphthyl, phenyl may have from 1 to 5 substituents, naphthyl may have from 1 to 7 substituents, most preferably phenyl or naphthyl may have from 1 to 3 substituents.

Longer chain substituents, e. g. C10-to C20-alkyl, such as dode- cyl, hexadecyl or eicosyl, or-0-C1o-to C20-alkyl, such as-O-do- decyl,-0-hexadecyl or-O-eicosyl, on, for example, the phenyl or the nathphyl may be preferred if it is desired to increase the solubility of the initiator in solvents like for example tetrahy- drofurane (THF) or ethylbenzene. Most preferably, each of R6, R7 and R8 is phenyl.

R9 is C1o-to C22-aryl, in particular C1o-to ¬14-aryl, such as 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-an- thracenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl, or substituted C1o-to C22-aryl, in particular C1o-to C14-aryl, such as 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-hexadecyl, cyclopropyl, cyclopentyl or cyclohexyl; oxyalkyl of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, in which the alkyl radical may be linear, branched or cyclic, such as-0-methyl,-0-ethyl,-0-n-propyl,-0-i-propyl, -O-n-butyl,-O-i-butyl,-O-t-butyl,-O-n-pentyl,-O-n-hexyl,< BR> -O-n-heptyl,-O-n-octyl,-O-n-nonyl,-O-n-decyl,-O-n-dode-<B R> cyl,-0-n-hexadecyl,-0-cyclopropyl,-0-cyclopentyl,-0-cy- clohexyl,-0- (CH2CH20) 1 to s-CH3 ; C6-to C22-aryl, in particular C6-to C14-aryl, such as phenyl; substituted C6-to C22-aryl, in particular C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-dodecyl or cyclohexyl; oxy- aryl of from 6 to 22 carbon atoms, in particular of from 6 to 14 carbon atoms, such as-O-phenyl or-O-naphthyl ; substi- tuted oxy-aryl of from 6 to 22 carbon atoms, in particular of from 6 to 14 carbon atoms, having one or more substituents selected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl,

n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-dodecyl or cyclohexyl; alkylene-oxy-alkyl of from 2 to 20 carbon atoms, in particular of from 3 to 17 carbon atoms, such as-(CH2) 1 to 5-O- (CH2CH2O) o to 5-CH3; aminodialkyl of from 2 to 30 carbon atoms, in particular of from 2 to 14 carbon atoms, such as dimethylamino, diethylamino, di (n-propyl) amino, di (i-pro- pyl) amino, di (n-butyl) amino, di (i-butyl) amino, (methyl) (ethyl) amino; amino (alkyl) (aryl) of from 7 to 30 car- bon atoms, in particular of from 7 to 15 carbon atoms, such as (methyl) (phenyl) amino, (ethyl) (phenyl) amino; aminodiaryl of from 12 to 36 carbon atoms, in particular of from 12 to 28 carbon atoms, such as diphenylamino, dinaphthylamino or (naphthyl) (phenyl) amino; halides, in particular fluoride, chloride, bromide or iodide, preferably fluoride, chloride or bromide; thio-alkyl of from 1 to 20 carbon atoms, in particu- lar of from 1 to 16 carbon atoms, in which alkyl may be lin- ear, branched or cyclic, such as-S-methyl,-S-ethyl, -S-n-propyl,-S-i-propyl,-S-n-butyl,-S-i-butyl,-S-t-butyl, -S-n-pentyl,-S-n-hexyl,-S-n-heptyl,-S-n-octyl,-S-n-nonyl, -S-n-decyl,-S-n-dodecyl,-S-n-hexadecyl,-S-cyclopropyl, -S-cyclopentyl,-S-cyclohexyl; thio-C6-to C22-aryl, in par- ticular thio-C6-to C14-aryl, such as thiophenyl; substituted thio-C6-to C22-aryl, in particular thio-C6-to C14-aryl, hav- ing one or more substituents selected from the group consist- ing of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-dodecyl or cyclohexyl.

The C6-to C22-aryl in R9 may be mono-, di-, poly-or persubsti- tuted with substituents as defined above. Thus, naphthyl may be substituted or from 1 to 7 times, anthracenyl and phenanthryl of from 1 to 9 times. Preferably naphthyl, anthracenyl or phenan- thryl may be substituted of from 1 to 5 times.

Longer chain substituents, e. g. C10-to C20-alkyl, such as dode- cyl, hexadecyl or eicosyl, or-O-Clo-to-O-C2o-alkyl, such as- O-dodecyl,-O-dodecyl or-0-eicosyl, on the annellated rings may be preferred if it is desired to increase the solubility of the initiator in solvents like for example tetrahydrofurane (THF), toluene, cyclohexane, dimethoxyethane, ethylbenzene or mixtures thereof. Most preferably, R9 is naphthyl.

Q is CRIOR11RI2, NR13Rl4, OR15, SR16 or R17 (CRlOR11) p (NR13) q (O) r (S) 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;

Rio and Rll are independently alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclopentyl or cyclo- hexyl; alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, having as substituents one or more halides, such as fluorine or chlorine, e. g. trifluoromethyl or 2,2,2-trifluoroethyl; C6-to C18-aryl, in particular C6-to C14-aryl, such as phenyl or naphthyl; substituted C6-to C1a-aryl, in particular C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 10 car- bon atoms, in particular of from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl or cyclohexyl, C6-to Cl0-aryl, such as phenyl, and halides, such as fluoride, chloride or bromide; CN; C (=X1) R3 as defined above, in particular C (O) R3, R3 being preferably selected from the group consisting of alkyl which may be linear, branched or cyclic having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl or cyclohexyl, alkyl of from 1 to 10 carbon atoms having as substituents one or more halides, such as fluorine or chlorine, e. g. trifluoromethyl or 2,2,2-trifluoroethyl, aryl having from 6 to 14 carbon atoms, such as phenyl or naphthyl, and alkoxy having from 1 to 10 carbon atoms, such as 0-methyl, O-ethyl, 0-n-propyl, O-i-propyl, 0-t-butyl or 0-cyclohexyl ; C (=X1) NR4R5 as defined above, in particular C (O) NR4R5, R4, R5 being preferably se- lected from the group consisting of alkyl which may be lin- ear, branched or cyclic having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl or cyclohexyl, al- kyl of from 1 to 10 carbon atoms having as substituents one or more halides, such as fluorine or chlorine, e. g. trifluo- romethyl or 2,2,2-trifluoroethyl, aryl having from 6 to 14 carbon atoms, such as phenyl or naphthyl; and aralkyl having from 7 to 15 carbon atoms, such as benzyl; organosilyl having from 3 to 30 carbon atoms, in particular of from 3 to 18 car- bon atoms, in which the tetravalent silicon atom is prefer- ably substituted with radicals selected from the group con- sisting of alkyl which can be linear, branched or cyclic hav- ing from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, i-propyl, n-butyl, t-bu- tyl or cyclohexyl, aryl having from 6 to 18 carbon atoms, in particular of from 6 to 10 carbon atoms, such as phenyl, and aralkyl, being formed from a C1-to C6-alkylene moiety, in particular a C1-to C3-alkylene moiety, and a C6-to Cis'aryl moiety, in particular a C6-to Gio-aryl moiety, such as

benzyl, examples are trimethylsilyl, tri-i-propylsilyl, tri- phenylsilyl, t-butyldimethylsilyl or t-butyldiphenylsilyl; either R10 or Rll alone can be H, and R10 and Rll may be joined together to form a ring, having from 3 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl or said rings being unsaturated or having one or more annellated aromatic systems.

R12 is H, alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, which may be linear, branched or cyclic such as methyl, ethyl, n-propyl, i-propyl or cyclo- hexyl, C6-to C, 8-aryl, in particular C6-to Clo-aryl, such as phenyl or naphthyl, preferably phenyl, or a (co) polymer radi- cal; R13 and R14 are independently alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, which may be lin- ear, branched or cyclic, such as methyl, ethyl, i-propyl or cyclohexyl, C6-to C, B-aryl, in particular C6-to Clo-aryl, such as phenyl or naphthyl, preferably phenyl, C7-to C20 aralkyl, in particular C7-to C15-aralkyl, such as benzyl, C3- to C30-organosilyl, in particular C3-to C18-organosilyl, in which the tetravalent silicon atom is preferably substituted with radicals selected from the group consisting of alkyl which can be linear, branched or cyclic having from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, i-propyl, n-butyl, t-butyl or cyclo- hexyl, aryl having from 6 to 18 carbon atoms, in particular of from 6 to 10 carbon atoms, such as phenyl, and aralkyl, being formed from a C1-to C6-alkylene moiety, in particular a C1-to C3-alkylene moiety, and a C6-to C18-aryl moiety, in particular a C6-to Clo-aryl moiety, such as benzyl, examples are trimethylsilyl, triethylsilyl or triphenylsilyl ; C (=X1) R3 as defined above, in particular C (O) R3, R3 being preferably selected from the group consisting of alkyl which may be lin- ear, branched or cyclic having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl or cyclo- hexyl; alkyl of from 1 to 10 carbon atoms having as substitu- ents one or more halides, such as fluorine or chlorine, e. g. trifluoromethyl or 2,2,2-trifluoroethyl, aryl having from 6 to 14 carbon atoms, such as phenyl or naphthyl, and alkoxy having from 1 to 10 carbon atoms, such as 0-methyl, O-ethyl, 0-n-propyl, O-i-propyl, 0-t-butyl or 0-cyclohexyl ; or R13 and R14 may be joined together to form a heterocycle, such as 2-pyrrolidone, 3,4-dihydropyrrol-2,5-dione or phthalimide.

R15 and R16 are independently alkyl which can be linear or branched of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, t-butyl or cycloalkyl of from 3 to 10 carbon atoms, such as cyclohexyl; C6-to C, B-aryl, in particular C6-to C14-aryl, such as phenyl or naphthyl; R17 is an organic radical of value p+q+r+s, in particular an al- kylene of from 1 to 20 carbon atoms, preferably of from 2 to 10 carbon atoms, such as ethylene, 1,2-propylene, 1,3-propy- lene, 1,4-butylene or 1,6-hexylene, cycloalkylene of from 3 to 10 carbon atoms, such as 1,4-cyclohexylene, or C6-to Cl8-arylene, in particular C6-to Clo-arylene, such as o-, m-, p-phenylene; n is an integer of from 1 to 30.

In the context of the present invention,"heterocyclic rings capable of stabilizing an a-anion"refer to those heterocyclic rings which can stabilize a formal negative charge at a carbon atom covalently bound to the heterocyclic ring, such as is postu- lated for"living"anionic polymers. Thus, the vinyl group under- going polymerization should be attached to the heterocyclic ring such that one or more of the heteroatoms in the heterocyclic ring stabilizes the negative charge on the"living"polymer inter- mediate. Accordingly, suitable vinyl heterocycles include 2-vinyl pyridine, 4-vinyl pyridine, 2-vinyl pyrrole, 5-vinyl pyrrole, 2-vinyl oxazole, 5-vinyl oxazole, 2-vinyl thiazole, 5-vinyl thiazole, 2-vinyl imidazole, 5-vinyl imidazole, 3-vinyl pyrazole, 5-vinyl pyrazole, 3-vinyl pyridazine, 6-vinyl pyridazine, 3-vinyl isoxazole, 3-vinyl isothiazoles, 2-vinyl pyrimidine, 4-vinyl pyrimidine, 6-vinyl pyrimidine, and any vinyl pyrazine, wherein 2-vinyl pyridine and 4-vinyl pyridine are preferred. The vinyl heterocycles mentioned above may bear one or more (preferably 1 or 2) C1-to C6-alkyl such as methyl, ethyl, n-propyl, i-propyl or cyclohexyl or C1-to C6-alkoxy groups such as methoxy, ethoxy, n-propoxy or i-propoxy, cyano groups, ester groups or halides such as chlorides. Further, those vinyl heterocycles which, when unsubstituted, contain an N-H group are protected at that posi- tion with a conventional blocking or protecting group, such as a C1-to C6-alkyl group, a C3-to C30-organo silyl group, an acyl group, etc.

If R12 is a (co) polymer radical it may be derived from a homopoly- mer, a statistical copolymer or a block copolymer, irrespective of the method of making such (co) polymers. The (co) polymer radi- cal R12 can thus be obtained via anionic, radical or polycondensa-

tion methods. In this respect R12 may represent for example a polymethylmethacrylate, a polystyrene, a polyether or a poly- phenylene ether radical. The molecular weight Mw of (co) polymer radical R12 usually is in the range of 500 to 200 000 g/mol.

A preferred initiator component Q is CRlORlIR12. Preferably, R10 and Rll are independently phenyl or phenyl having from 1 to 3 sub- stituents selected from the group consisting of alkyl of from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, alkoxy of from 1 to 4 carbon atoms, such as methoxy, ethoxy, n- propoxy or i-propoxy, phenyl and halogen such as fluorine, chlo- rine or bromine; and R12 is preferably H, alkyl of from 1 to 6 carbon atoms, phenyl, such as methyl, ethyl, n-propyl, i-propyl, or phenyl having from 1 to 3 substituents selected from the group consisting of alkyl of from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, alkoxy of from 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy or i-propoxy, phenyl and halo- gen. Preferably, each of R10, Rll and R12 is phenyl.

Examples of R10 and Rll being joined together to form a ring to- gether with C include fluorenyl and indenyl ring systems as well as substituted derivatives thereof, such as benzindenyl.

Preferred initiator components Q are also ester enolates of esters formed from straight-chain or branched carboxylic acids and alcohols having from 1 to 6 carbon atoms, such as methyl iso- butyrate or t-butylisobutyrate.

Another preferred initiator component Q is [Rl7 (CRl0Rll) p (NR13) q (O) r (S) s] n~ wherein p, q, r and s are indepen- dently an integer of from 0 to 30 and where the sum of p to s is at least 2. R17 may be an organic radical of value n. R17 is pre- ferably an alkylene moiety of from 2 to 15 carbon atoms, cycloal- kylene of from 3 to 10 carbon atoms or C6-to C14-arylene capable of bearing n functional groups, (CRl°Rll), (NR13), (O) and/or (S), as described above. Suitable as initiator components Q2-of type R17 (CRl°Rll) 2 are for example 1,3-bis (1-methyl-alkan-1-yl) benzene, 1, 3-bis (l-phenyl-alkan-1-yl) benzene or 1,1,4,4-tetraphenylbu- tan (1, 4) diyl.

The present invention is also concerned with a method for prepar- ing a compound corresponding to or containing [(R6R7R8R9) +] n Qn~ (III), comprising the steps of:

reacting a phosphonium salt (R6R7R8pR9) + T- with a metal salt selected from the group consisting of G+ (CRl0RllRl2)-, G+ (NR13Rl4)-, G+ (OR15)-, G+ (SR16)-and [ (p+q+r+s) x G+l (R17 [ (CRlOR11) I p [ (NR13)-1 q [0-1 r [S-I) at a temperature of from more than 15°C, in the presence of an in- ert solvent, for a length of time sufficient to form a compound according to formula III, wherein R6, R7 and R8 are independently C6-to C22-aryl, in particular C6- to C14-aryl, such as phenyl, naphthyl, fluorenyl, anthracenyl or phenanthryl, or substituted C6-to C22-aryl, in particular C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-hexadecyl, cyclopropyl, cyclopentyl or cyclohexyl; oxyalkyl of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, in which alkyl may be linear, branched or cyclic, such as-O- <BR> <BR> methyl,-O-ethyl,-O-n-propyl,-O-i-propyl,-O-n-butyl,<BR> ; -O-i-butyl,-O-t-butyl,-O-n-pentyl,-O-n-hexyl,-O-n-heptyl,< ;BR> -0-n-octyl,-0-n-nonyl,-0-n-decyl,-0-n-dodecyl,-0-n-hexa-< BR> decyl,-O-cyclopropyl,-O-cyclopentyl,-O-cyclohexyl, -O- (CH2CH20) 1 to 5-CH3 ; cato C22-aryl, in particular C6-to C14-aryl, such as phenyl; substituted C6-to C22-aryl, in par- ticular C6-to C14-aryl, having one or more substituents se- lected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-dodecyl or cyclohexyl, oxy-Ce-to C22-aryl, in particular oxy-C6-to C14-aryl, such as -0-phenyl ; substituted oxy-C6-to C22-aryl, in particular oxy-C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particu- lar of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-dodecyl or cyclohexyl; alky- lene-oxy-alkyl of from 2 to 20 carbon atoms, in particular of from 3 to 17 carbon atoms, such as- (CH2) 1 to 5-0- (CH2CH20) o to 5-CH3 ; aminodialkyl of from 2 to 30 carbon atoms, in particu- lar of from 2 to 14 carbon atoms, such as dimethylamino, die- thylamino, di (n-propyl) amino, di (i-propyl) amino, di (n-bu- tyl) amino, di (i-butyl) amino, (methyl) (ethyl) amino ; aminoalky-

laryl of from 7 to 30 carbon atoms, in particular of from 7 to 15 carbon atoms, such as (methyl) (phenyl) amino, (ethyl) (phenyl) amino; aminodiaryl of from 12 to 36 carbon atoms, in particular of from 12 to 28 carbon atoms, such as diphenylamino, dinaphthylamino or (naphthyl) (phenyl) amino; halides, in particular fluoride, chloride, bromide or iodide, preferably fluoride, chloride or bromide; thio-alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, in which alkyl may be linear, branched or cyclic, such as-S-methyl,-S-ethyl,-S-n-propyl,-S-i-propyl,-S-n-butyl, -S-i-butyl,-S-t-butyl,-S-n-pentyl,-S-n-hexyl,-S-n-heptyl, -S-n-octyl,-S-n-nonyl,-S-n-decyl,-S-n-dodecyl,-S-n-hexa- decyl,-S-cyclopropyl,-S-cyclopentyl,-S-cyclohexyl ; thio- Ce-to C22-aryl, in particular thio-C6-to C14-aryl, such as phenyl or naphthyl; substituted thio-C6-to C22-aryl, in par- ticular thio-C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-dodecyl or cyclohexyl; R9 is C10-to C22-aryl, in particular Clo-to C14-aryl, such as 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-an- thracenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl, or substituted C1o-to C22-aryl, in particular C1o-to C14-aryl, such as 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-hexadecyl, cyclopropyl, cyclopentyl or cyclohexyl; oxyalkyl of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, in which the alkyl radical may be linear, branched or cyclic, such as-0-methyl,-0-ethyl,-0-n-propyl,-0-i-propyl, -0-n-butyl,-0-i-butyl,-0-t-butyl,-0-n-pentyl,-0-n-hexyl,< BR> -0-n-heptyl,-0-n-octyl,-0-n-nonyl,-0-n-decyl,-0-n-dode-<B R> cyl,-O-n-hexadecyl,-O-cyclopropyl,-O-cyclopentyl,-O-cy- clohexyl,-O- (CH2CH20) 1 to 5-CH3 ; cato C22-aryl, in particular C6-to C14-aryl, such as phenyl; substituted C6-to C22-aryl, in particular C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par-

ticular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-dodecyl or cyclohexyl; oxy- aryl of from 6 to 22 carbon atoms, in particular of from 6 to 14 carbon atoms, such as-O-phenyl or-O-naphthyl ; substi- tuted oxy-aryl of from 6 to 22 carbon atoms, in particular of from 6 to 14 carbon atoms, having one or more substituents selected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-dodecyl or cyclohexyl; alkylene-oxy-alkyl of from 2 to 20 carbon atoms, in particular of from 3 to 17 carbon atoms, such as-(CH2) 1 to 5-O-(CH2CH2O) o to s-CH3i aminodialkyl of from 2 to 30 carbon atoms, in particular of from 2 to 14 carbon atoms, such as dimethylamino, diethylamino, di (n-propyl) amino, di (i-pro- pyl) amino, di (n-butyl) amino, di (i-butyl) amino, (methyl) (ethyl) amino; amino (alkyl) (aryl) of from 7 to 30 car- bon atoms, in particular of from 7 to 15 carbon atoms, such as (methyl) (phenyl) amino, (ethyl) (phenyl) amino; aminodiaryl of from 12 to 36 carbon atoms, in particular of from 12 to 28 carbon atoms, such as diphenylamino, dinaphthylamino or (naphthyl) (phenyl) amino; halides, in particular fluoride, chloride, bromide or iodide, preferably fluoride, chloride or bromide; thio-alkyl of from 1 to 20 carbon atoms, in particu- lar of from 1 to 16 carbon atoms, in which alkyl may be lin- ear, branched or cyclic, such as-S-methyl,-S-ethyl, -S-n-propyl,-S-i-propyl,-S-n-butyl,-S-i-butyl,-S-t-butyl, -S-n-pentyl,-S-n-hexyl,-S-n-heptyl,-S-n-octyl,-S-n-nonyl, -S-n-decyl,-S-n-dodecyl,-S-n-hexadecyl,-S-cyclopropyl, -S-cyclopentyl,-S-cyclohexyl; thio-C6-to C22-aryl, in par- ticular thio-C6-to C14-aryl, such as thiophenyl; substituted thio-C6-to C22-aryl, in particular thio-C6-to C14-aryl, hav- ing one or more substituents selected from the group consist- ing of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-dodecyl or cyclohexyl, Q is CRlORllRl2, NR13Rl4, OR15, SR16 or R17 (CRlOR11) p (NR) q (o) (S) 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; R10 and Rll are independently alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclopentyl or cyclo-

hexyl; alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, having as substituents one or more halides, such as fluorine or chlorine, e. g. trifluoromethyl or 2,2,2-trifluoroethyl; C6-to C18-aryl, in particular C6-to C14-aryl, such as phenyl or naphthyl; substituted C6-to Cis-aryl, in particular C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 10 car- bon atoms, in particular of from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl or cyclohexyl, C6-to Clo-aryl, such as phenyl, and halides, such as fluoride, chloride or bromide; CN; C (=X1) R3 as defined above, in particular C (0) R3, R3 being preferably selected from the group consisting of alkyl which may be linear, branched or cyclic having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl or cyclohexyl, alkyl of from 1 to 10 carbon atoms having as substituents one or more halides, such as fluorine or chlorine, e. g. trifluoromethyl or 2,2,2-trifluoroethyl, aryl having from 6 to 14 carbon atoms, such as phenyl or naphthyl, and alkoxy having from 1 to 10 carbon atoms, such as 0-methyl, O-ethyl, 0-n-propyl, 0-i-propyl, 0-t-butyl or 0-cyclohexyl ; C (=X1) NR4R5 as defined above, in particular C (0) NR4R5, R4, R5 being preferably se- lected from the group consisting of alkyl which may be lin- ear, branched or cyclic having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl or cyclohexyl, al- kyl of from 1 to 10 carbon atoms having as substituents one or more halides, such as fluorine or chlorine, e. g. trifluo- romethyl or 2,2,2-trifluoroethyl, aryl having from 6 to 14 carbon atoms, such as phenyl or naphthyl; and aralkyl having from 7 to 15 carbon atoms, such as benzyl; organosilyl having from 3 to 30 carbon atoms, in particular of from 3 to 18 car- bon atoms, in which the tetravalent silicon atom is prefer- ably substituted with radicals selected from the group con- sisting of alkyl which can be linear, branched or cyclic hav- ing from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, i-propyl, n-butyl, t-bu- tyl or cyclohexyl, aryl having from 6 to 18 carbon atoms, in particular of from 6 to 10 carbon atoms, such as phenyl, and aralkyl, being formed from a C1-to C6-alkylene moiety, in particular a C1-to C3-alkylene moiety, and a C6-to C, B-aryl moiety, in particular a C6-to Clo-aryl moiety, such as benzyl, examples are trimethylsilyl, tri-i-propylsilyl, tri- phenylsilyl, t-butyldimethylsilyl or t-butyldiphenylsilyl; either R10 or Rll alone can be H, and R10 and R11 may be joined together to form a ring, having from 3 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl or said rings

being unsaturated or having one or more annellated aromatic systems.

R12 is H, alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, which may be linear, branched or cyclic such as methyl, ethyl, n-propyl, i-propyl or cyclo- hexyl, C6-to C, 8-aryl, in particular C6-to Clo-aryl, such as phenyl or naphthyl, preferably phenyl, or a (co) polymer radi- cal; R13 and R14 are independently alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, which may be lin- ear, branched or cyclic, such as methyl, ethyl, i-propyl or cyclohexyl, C6-to C, 8-aryl, in particular C6-to Clo-aryl, such as phenyl or naphthyl, preferably phenyl, C7-to C20 aralkyl, in particular C7-to C15-aralkyl, such as benzyl, C3- to C30-organosilyl, in particular C3-to C, 8-organosilyl, in which the tetravalent silicon atom is preferably substituted with radicals selected from the group consisting of alkyl which can be linear, branched or cyclic having from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, i-propyl, n-butyl, t-butyl or cyclo- hexyl, aryl having from 6 to 18 carbon atoms, in particular of from 6 to 10 carbon atoms, such as phenyl, and aralkyl, being formed from a C1-to C6-alkylene moiety, in particular a C1-to C3-alkylene moiety, and a C6-to C, 8-aryl moiety, in particular a C6-to Clo-aryl moiety, such as benzyl, examples are trimethylsilyl, triethylsilyl or triphenylsilyl; C (=X1) R3 as defined above, in particular C (0) R3, R3 being preferably selected from the group consisting of alkyl which may be lin- ear, branched or cyclic having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl or cyclo- hexyl; alkyl of from 1 to 10 carbon atoms having as substitu- ents one or more halides, such as fluorine or chlorine, e. g. trifluoromethyl or 2,2,2-trifluoroethyl, aryl having from 6 to 14 carbon atoms, such as phenyl or naphthyl, and alkoxy having from 1 to 10 carbon atoms, such as 0-methyl, O-ethyl, 0-n-propyl, O-i-propyl, 0-t-butyl or 0-cyclohexyl ; or R13 and R14 may be joined together to form a heterocycle, such as 2-pyrrolidone, 3,4-dihydropyrrol-2,5-dione or phthalimide.

R15 and R16 are independently alkyl which can be linear or branched of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, t-butyl or cycloalkyl of from 3 to 10 carbon atoms, such

as cyclohexyl; C6-to Cis-aryl, in particular C6-to C14-aryl, such as phenyl or naphthyl; R17 is an organic radical of value p+q+r+s, in particular an al- kylene of from 1 to 20 carbon atoms, preferably of from 2 to 10 carbon atoms, such as ethylene, 1,2-propylene, 1,3-propy- lene, 1,4-butylene or 1,6-hexylene, cycloalkylene of from 3 to 10 carbon atoms, such as 1,4-cyclohexylene, or C6-to Gia-arylene, in particular C6-to Clo-arylene, such as o-, m-, p-phenylene; n is an integer of from 1 to 30.

G+ is an inorganic cation and T-is an inorganic anion.

The C6-to C22-aryl in R9 may be mono-, di-, poly-or persubsti- tuted with substituents as defined above. Thus, naphthyl may be substituted or from 1 to 7 times, anthracenyl and phenanthryl of from 1 to 9 times. Preferably naphthyl, anthracenyl or phenan- thryl may be substituted of from 1 to 5 times.

Thus, among other methods the initiators according to the present invention in which Q is (CRl0RllRl2) can be conveniently prepared by cation exchange (metathesis) from the corresponding alkali or earth alkali metal carbanions and phosphonium salts, e. g. phosphonium halides. The metathesis reaction can be conducted at a temperature of from-78 to 120°C, preferably of from-30 to 80°C and more preferably of from more than 15°C. Usually the initiators of the present invention are prepared by cation exchange at room temperature from the corresponding alkali or earth alkali metal carbanion and phosphonium halide salts. The alkali and earth alkali metal carbanion salts can be prepared in accordance with known procedures as for example described in Ch. Elschenbroich, A. Salzer, Organometallchemie, Teubner Verlag, Stuttgart, 1986 and references cited therein (e. g., treatment of a compound of the formula Rl0RllRl2CH with an alkali metal hydride reagent; direct treatment of the compound of the formula Rl0RllRl2CH with an alkali metal; by a metal-halide exchange between an alkali metal and the halide atom of a compound of the formula Rl0RllRl2C (Hal), where (Hal) is chloride, bromide or iodide; or by carbometalla- tion of alkenes or alkynes. Alkali metals include lithium, so- dium, potassium, rubidium and cesium, preferably lithium and po- tassium, and most preferably potassium. Earth alkali metals in-

clude magnesium, calcium, strontium, barium, preferably magnesium.

The initiators according to the present invention in which Q is NR13Rl4, OR15 or SR16 can also be conveniently prepared by cation exchange at temperatures of from-78 to 120°C, preferably of from -30 to 80°C and more preferably of from more than 15°C from the corresponding alkali or earth alkali metal salts of nitrogen (amide), oxygen (alcoholate) or sulfur (thiolate) anions and phosphonium salts, e. g. phosphonium halides. The alkali and earth alkali metal amide, oxide (alcoholate) or sulfide (thiolate) salts can be prepared in accordance with known prodedures (e. g. treatment of a compound of the formula RlOR11NH, R15OH or R16SH with an alkali metal hydride reagent; direct treatment of the compound of the formula R13Rl4NH, R150H or R16SH with an alkali metal; etc.). Alkali metals include lithium, sodium, potassium, rubidium and cesium, preferably lithium and potassium, and most preferably potassium. Earth alkali metals include magnesium, calcium, strontium, barium, preferably magnesium.

Polyanions of polyamines, polyols, polythiols or of compounds having a variety of the abovementioned functional groups, such as compounds according to the formula Rl7 (CHRl0Rll) p (NHRl3) q (OH) r (SH) s are also suitable for the preparation of initiators in which Q is Ri7 (CRl°R11) p (NR13) q (0) r (S) s. These can also be prepared as de- scribed above by cation exchange at temperatures of from-78 to 120°C, preferably of from-30 to 80°C and more preferably of from more than 15°C from the corresponding alkali or earth alkali metal salts, e. g. by treatment of a compound Rl7 (cHRl0Rll) p (NHR13) q (OH) r (SH) s with an alkali or earth alkali metal or with an alkali or earth alkali metal hydride reagent.

Such initiators can be prepared from, for example, dianions like for example [Rl7 (CRl°R11) 2] 2- wherein R10 and Rll are as defined above and R17 is- (CH2CH2)- by treating vinyl compounds with naphthyl sodium (NaCloH8-) (cf. M. Morton, Anionic Polymerization: Principles and Practice, Academic Press, New York, 1983), or from, for example, a diamide, a dialcoholate or a dithiolate, which is then metathesized with a tetrasubstituted phosphonium salt [(R6R7R8PR9) +] [T-], e. g. a phosphonium halide, to provide a multifunctional initiator of the formula [ (R6R7R8PR9) +] [Rl7 (QRlORll) p (NRl3) q (0) r (S) g] - where p+q+r+s22, and wherein R6, R7, R8, R9, R10, Rll, R13 and R17 are as defined above.

The alkali or earth alkali metal salts, e. g. halide salts, formed as a result of cation exchange can be filtered off prior to use of the initiator in polymerization, but filtration is not neces- sary for polymerization to be successful.

The cation metathesis reaction occurs very rapidly (e. g., within seconds) and quantitatively, even at-78°C, in concurrence with previous reports. A bathochromic shift in the maximum absorbance wavelength (&m=) is observed during cation metathesis.

Many phosphonium reagents (R6R7R8PR9) + T-, e. g. phosphonium halide, nitrate or borate salts, are commercially available. Others can be made by reacting a phosphine (i. e., a compound of the formula PR6R7R8) with an alkyl or aryl halide of the formula R9 (Hal) in accordance with known methods and procedures (cf. Horner et al., Chem. Ber. 1966,99,2782). Among others tris-triphenyl-2-naph- thyl-phosphonium bromide or tris-triphenyl-l-naphthyl-phosphonium perchlorate can be prepared by these methods.

Also mixtures of initiators according to the present invention as disclosed above and below can be employed. Initiator mixtures can either be derived from species with differences in the phosphonium substituents or with differences in Q, or from dif- ferences in both. For example mixtures of carbanionic, amide, ox- ide or sulfide based initiators as well as mixtures of any com- bination of these species can be employed.

Initiators according to the present invention having as initiator compounds Q'CRRR,'NRR,'ORl5or'SR can be employed in anionic polymerization methodology to form homo-or copolymers of, for example, acrylates or methacrylates.

The multifunctional initiators corresponding to or containing [ (R6R7R8pR9) +] n [R (CRl°Ril) p (NRl3) q (O) r (S) s] n-as mentioned above can be used in the process of the present invention to produce block copolymers such as branched, diblock, triblock or multi- block copolymers. Blockcopolymers can, for example, have a first, central poly (meth) acrylate or polyacrylonitrile block, and a second, distinct poly (meth) acrylate or polyacrylonitrile block at both ends of the first, central block.

Appropriate dianions as initiators for block copolymer synthesis according to the present invention are for example

[ (PR6R7R8R9) +] 2 (RllRlOC (R) CRR) 2- [ (PR6R7R8R9) + 2 (RlON (Rl7) NR10) 2- [ (PR6R7R8R9) +] 2 (ORO) - [(PR6R7R8R9)+]2 (SR17S)2- where R6, R7, R8, R9, Rio and R17 are as defined above. Such initi- ators can be used in the process of the present invention to make a triblock copolymer having, for example, a first, central poly (meth) acrylate or polyacrylonitrile block, and second, dis- tinct poly (meth) acrylate or polyacrylonitrile blocks at the ends of the first, central block.

The present invention is thus also concerned with methods of mak- ing block copolymers of the formula A-(R11R10C(R17)CR10R11-A A-(Rl3N (Rl7) NRl3)-A<BR> A- (OR170)-A<BR> A- (SR17S)-A B-A-(R11R10C(R17)CR10R11)-A-B <BR> <BR> B-A- (Rl3N (Rl7) NR13)-A-B<BR> B-A- (OR170)-A-B<BR> B-A-(SR17S)-A-B C-B-A-(R11R10C(R17)CR10R11)-A-B-C C-B-A-(Rl3N(Rl7)NR13)-A-B-c <BR> <BR> C-B-A-(oRl70)-A-B-C<BR> C-B-A- (SR17S)-A-B-C etc. (i. e., with successive blocks attached to each end), where A, B and C are distinct (co) polymer blocks produced by anionic polymerization of one or more monomers of the formula: wherein R1, R2 X1, X2 and L are as defined above, using at least one of the present phosphonium salts of carbon, nitrogen-, oxy- gen-and sulfurbased anions.

Branched (co) polymers having three or more chains can be prepared from, for example, appropriate phosphonium salts of compounds having three or more carbonions, or nitrogen, oxygen and sulfur anions (so-called"multi-anionic"initiators), such as tris-, te- tra-, penta-or hexa (hydroxymethyl) benzene, glycerol, erythritol,

diethylene triamine, triethylene tetramine, dithioerythritol, di- thiothreitol or trihydroxycyclohexane.

Generally initiator components of the formula [Rl7(CR10R11)p(NR13R14)p(0)r(S)s]n- can be used for the production of branched or multiblock (co) polymers, where n can be at least 2, preferably from 2 to 6.

Thus, a preferred initiator is one in which n is 2, and R17 is - (CH2CH2)-- Triblock copolymers can be prepared from dianionic initiators de- scribed above by reacting the dianionic initiator with a first monomer to prepare a"living"anionic first block, followed by reacting the"living"anionic first block with a second monomer to provide terminal blocks on each end of the"living"first block. Thus, the present invention also concerns a method for preparing a triblock copolymer comprising: mixing a first monomer of the formula I, with an initiator of the formula [ (PR6R7R8R9) +] [Rl7 (CRlORll) p (NRl3) q (o) (S) s] - and conducting the reaction at a temperature of from more than 40°C, in particular more than 45°C, in the presence or the absence of a solvent, for a length of time sufficient to polymerize the first monomer I, wherein the substituents and indices are as de- fined above, adding a second monomer of the formula I:

where R1 and R2 are as defined above, the second monomer being distinct from the first monomer, at a temperature of from more than 40°C, in particular more than 45°C and reacting for a length of time sufficient to form a triblock (co) polymer intermediate, quenching the triblock (co) polymer intermediate with an acyl ha- lide, an acid anhydride or a substance containing an active hy- drogen atom to form a triblock (co) polymer; and isolating the formed triblock (co) polymer.

Successive blocks can be added to each end of the"living" anionic chain by successively adding different monomers or by changing reaction conditions appropriately (e. g., lowering the reaction temperature to increase or otherwise alter stereoregu- larity) after the first"adding"step above, but prior to quench- ing.

The present invention also encompasses an initiator corresponding to or containing a compound according to formula IV: (R6R7R8pR9) + (Q')- (IV), wherein R6, R7 and R8 are independently C6-to C22-aryl, in particular C6- to C14-aryl, such as phenyl, naphthyl, fluorenyl, anthracenyl or phenanthryl, or substituted C6-to C22-aryl, in particular C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-hexadecyl, cyclopropyl, cyclopentyl or cyclohexyl; oxyalkyl of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, in which alkyl may be linear, branched or cyclic, such as-O- methyl,-O-ethyl,-O-n-propyl,-O-i-propyl,-O-n-butyl,<BR> ; -O-i-butyl,-O-t-butyl,-O-n-pentyl,-O-n-hexyl,-O-n-heptyl,< ;BR> -O-n-octyl,-O-n-nonyl,-O-n-decyl,-O-n-dodecyl,-O-n-hexa- decyl,-O-cyclopropyl,-O-cyclopentyl,-0-cyclohexyl, -0- (CH2CH20) 1 to 5-CH3 ; Ce-to C22-aryl, in particular C6-to C14-aryl, such as phenyl; substituted Ce-to C22-aryl, in par- ticular C6-to C14-aryl, having one or more substituents se- lected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl,

n-propyl, i-propyl, t-butyl, n-dodecyl or cyclohexyl, oxy-C6-to C22-aryl, in particular oxy-C6-to C14-aryl, such as -0-phenyl ; substituted oxy-C6-to C22-aryl, in particular oxy-C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particu- lar of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-dodecyl or cyclohexyl; alky- lene-oxy-alkyl of from 2 to 20 carbon atoms, in particular of from 3 to 17 carbon atoms, such as-(CH2) 1 to 5-o-(CH2CH2o) 0 to 5-CH3; aminodialkyl of from 2 to 30 carbon atoms, in particu- lar of from 2 to 14 carbon atoms, such as dimethylamino, die- thylamino, di (n-propyl) amino, di (i-propyl) amino, di (n-bu- tyl) amino, di (i-butyl) amino, (methyl) (ethyl) amino; aminoalky- laryl of from 7 to 30 carbon atoms, in particular of from 7 to 15 carbon atoms, such as (methyl) (phenyl) amino, (ethyl) (phenyl) amino; aminodiaryl of from 12 to 36 carbon atoms, in particular of from 12 to 28 carbon atoms, such as diphenylamino, dinaphthylamino or (naphthyl) (phenyl) amino; halides, in particular fluoride, chloride, bromide or iodide, preferably fluoride, chloride or bromide; thio-alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, in which alkyl may be linear, branched or cyclic, such as-S-methyl,-S-ethyl,-S-n-propyl,-S-i-propyl,-S-n-butyl, -S-i-butyl,-S-t-butyl,-S-n-pentyl,-S-n-hexyl,-S-n-heptyl, -S-n-octyl,-S-n-nonyl,-S-n-decyl,-S-n-dodecyl,-S-n-hexa- decyl,-S-cyclopropyl,-S-cyclopentyl,-S-cyclohexyl ; thio- Ce-to C22-aryl, in particular thio-C6-to C14-aryl, such as phenyl or naphthyl; substituted thio-C6-to C22-aryl, in par- ticular thio-C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-dodecyl or cyclohexyl; R9 is Clo-to C22-aryl, in particular C1o-to C14-aryl, such as 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-an- thracenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl, or substituted C1o-to C22-aryl, in particular Clo-to C14-aryl, such as 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-pro-

pyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-hexadecyl, cyclopropyl, cyclopentyl or cyclohexyl; oxyalkyl of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, in which the alkyl radical may be linear, branched or cyclic, such as-O-methyl,-O-ethyl,-O-n-propyl,-O-i-propyl, -O-n-butyl,-O-i-butyl,-O-t-butyl,-O-n-pentyl,-O-n-hexyl,< BR> -0-n-heptyl,-0-n-octyl,-0-n-nonyl,-0-n-decyl,-0-n-dode-<B R> cyl,-0-n-hexadecyl,-0-cyclopropyl,-0-cyclopentyl,-0-cy- clohexyl,-0- (CH2CH20) 1 to 5-CH3 Cs-to C22-aryl, in particular C6-to C14-aryl, such as phenyl; substituted C6-to C22-aryl, in particular C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-dodecyl or cyclohexyl; oxy- aryl of from 6 to 22 carbon atoms, in particular of from 6 to 14 carbon atoms, such as-0-phenyl or-O-naphthyl ; substi- tuted oxy-aryl of from 6 to 22 carbon atoms, in particular of from 6 to 14 carbon atoms, having one or more substituents selected from the group consisting of alkyl which may be lin- ear, branched or cyclic of from 1 to 20 carbon atoms, in par- ticular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-dodecyl or cyclohexyl; alkylene-oxy-alkyl of from 2 to 20 carbon atoms, in particular of from 3 to 17 carbon atoms, such as-(CH2) 1 to 5-0- (CH2CH20) o to 5-CH3 ; aminodialkyl of from 2 to 30 carbon atoms, in particular of from 2 to 14 carbon atoms, such as dimethylamino, diethylamino, di (n-propyl) amino, di (i-pro- pyl) amino, di (n-butyl) amino, di (i-butyl) amino, (methyl) (ethyl) amino; aminoalkylaryl of from 7 to 30 carbon atoms, in particular of from 7 to 15 carbon atoms, such as (methyl) (phenyl) amino, (ethyl) (phenyl) amino; aminodiaryl of from 12 to 36 carbon atoms, in particular of from 12 to 28 carbon atoms, such as diphenylamino, dinaphthylamino or (naphthyl) (phenyl) amino; halides, in particular fluoride, chloride, bromide or iodide, preferably fluoride, chloride or bromide; thio-alkyl of from 1 to 20 carbon atoms, in particu- lar of from 1 to 16 carbon atoms, in which alkyl may be lin- ear, branched or cyclic, such as-S-methyl,-S-ethyl, -S-n-propyl,-S-i-propyl,-S-n-butyl,-S-i-butyl,-S-t-butyl, -S-n-pentyl,-S-n-hexyl,-S-n-heptyl,-S-n-octyl,-S-n-nonyl, -S-n-decyl,-S-n-dodecyl,-S-n-hexadecyl,-S-cyclopropyl, -S-cyclopentyl,-S-cyclohexyl; thio-C6-to C22-aryl, in par- ticular thio-C6-to C14-aryl, such as thiophenyl; substituted thio-C6-to C22-aryl, in particular thio-C6-to C14-aryl, hav- ing one or more substituents selected from the group consist-

ing of alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-dodecyl or cyclohexyl; Q'isR-CRlORR,Rl8-NRl3Rl4,pIS-ORlS,Rl8.gRl6Rl8-z ; R10 and Rll are independently alkyl which may be linear, branched or cyclic of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclopentyl or cyclo- hexyl; alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, having as substituents one or more halides, such as fluorine or chlorine, e. g. trifluoromethyl or 2,2,2-trifluoroethyl; C6-to Cle-aryl, in particular C6-to C14-aryl, such as phenyl or naphthyl; substituted C6-to C, 8-aryl, in particular C6-to C14-aryl, having one or more substituents selected from the group consisting of alkyl which may be linear, branched or cyclic of from 1 to 10 car- bon atoms, in particular of from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl or cyclohexyl, C6-to Clo-aryl, such as phenyl, and halides, such as fluoride, chloride or bromide; CN; C (=X1) R3 as defined above, in particular C (0) R3, R3 being preferably selected from the group consisting of alkyl which may be linear, branched or cyclic having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl or cyclohexyl, alkyl of from 1 to 10 carbon atoms having as substituents one or more halides, such as fluorine or chlorine, e. g. trifluoromethyl or 2,2,2-trifluoroethyl, aryl having from 6 to 14 carbon atoms, such as phenyl or naphthyl, and alkoxy having from 1 to 10 carbon atoms, such as 0-methyl, O-ethyl, 0-n-propyl, 0-i-propyl, 0-t-butyl or 0-cyclohexyl ; C (=X1) NR4R5 as defined above, in particular C (0) NR4R5, R4, R5 being preferably se- lected from the group consisting of alkyl which may be lin- ear, branched or cyclic having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl or cyclohexyl, al- kyl of from 1 to 10 carbon atoms having as substituents one or more halides, such as fluorine or chlorine, e. g. trifluo- romethyl or 2,2,2-trifluoroethyl, aryl having from 6 to 14 carbon atoms, such as phenyl or naphthyl and aralkyl having from 7 to 15 carbon atoms, such as benzyl; organosilyl having from 3 to 30 carbon atoms, in particular of from 3 to 18 car- bon atoms, in which the tetravalent silicon atom is prefer- ably substituted with radicals selected from the group con- sisting of alkyl which can be linear, branched or cyclic hav-

ing from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, i-propyl, n-butyl, t-bu- tyl or cyclohexyl, aryl having from 6 to 18 carbon atoms, in particular of from 6 to 10 carbon atoms, such as phenyl, and aralkyl, being formed from a C1-to C6-alkylene moiety, in particular a C1-to C3-alkylene moiety, and a C6-to C, 8-aryl moiety, in particular a C6-to Gio-aryl moiety, such as benzyl, examples are trimethylsilyl, tri-i-propylsilyl, tri- phenylsilyl, t-butyldimethylsilyl or t-butyldiphenylsilyl; either R10 or Rll alone can be H, or R10 and Rll may be joined together to form a ring having from 3 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, and or said rings being unsaturated or having one or more annellated aro- matic systems.

R12 is H, alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, which may be linear, branched or cyclic such as methyl, ethyl, n-propyl, i-propyl or cyclo- hexyl, C6-to C, 8-aryl, in particular C6-to Clo-aryl, such as phenyl or naphthyl, preferably phenyl, or a (co) polymer radi- cal; R13 and R14 are independently alkyl of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, which may be lin- ear, branched or cyclic, such as methyl, ethyl, i-propyl or cyclohexyl; C6-to Gig-aryl, in particular C6-to Clo-aryl, such as phenyl or naphthyl, preferably phenyl; C7-to Czo aralkyl, in particular C7-to Cls-aralkylS such as benzyl; C3- to C30-organosilyl, in particular C3-to C, 8-organosilyl, in which the tetravalent silicon atom is preferably substituted with radicals selected from the group consisting of alkyl which can be linear, branched or cyclic having from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, i-propyl, n-butyl, t-butyl or cyclo- hexyl, aryl having from 6 to 18 carbon atoms, in particular of from 6 to 10 carbon atoms, such as phenyl, and aralkyl, being formed from a C1-to C6-alkylene moiety, in particular a C1-to C3-alkylene moiety, and a C6-to Cis-aryl moiety, in particular a C6-to Clo-aryl moiety, such as benzyl, examples are trimethylsilyl, triethylsilyl or triphenylsilyl; C (=X1) R3 as defined above, in particular C (0) R3, R3 being preferably selected from the group consisting of alkyl which may be lin- ear, branched or cyclic having from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl or cyclo- hexyl, alkyl of from 1 to 10 carbon atoms having as substitu- ents one or more halides, such as fluorine or chlorine, e. g. trifluoromethyl or 2,2,2-trifluoroethyl, aryl having from 6

to 14 carbon atoms, such as phenyl or naphthyl, and alkoxy having from 1 to 10 carbon atoms, such as 0-methyl, O-ethyl, 0-n-propyl, 0-i-propyl, 0-t-butyl or 0-cyclohexyl ; or R13 and R14 may be joined together to form a heterocycle, such as 2-pyrrolidone, 3,4-dihydropyrrol-2,5-dione or phthalimide; R15 and R16 are independently alkyl which can be linear or branched of from 1 to 20 carbon atoms, in particular of from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-pro- pyl, t-butyl or cycloalkyl of from 3 to 10 carbon atoms, such as cyclohexyl; C6-to C, 8-aryl, in particular C6-to C14-aryl, such as phenyl or naphthyl; R18 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 compounds III or IV.

The C6-to C22-aryl in R9 may be mono-, di-, poly-or persubsti- tuted with substituents as defined above. Thus, naphthyl may be substituted or from 1 to 7 times, anthracenyl and phenanthryl of from 1 to 9 times. Preferably naphthyl, anthracenyl or phenan- thryl may be substituted of from 1 to 5 times.

The (co) polymer group R18 can for example be derived from an anionic polymerization of one or more anionically polymerizable monomers by which a living polymer species is obtained or by a polymerization process according to the present invention.

Thus, the present invention is also concerned with a method for preparing an initiator corresponding to or containing (R6R7R8PR9) + (Ql)- (IV), comprising the steps of mixing a monomer of the for- mula I or of the monomer II or a mixture of monomers of formula I and II with an initiator corresponding to or containing (R6R7R8PR9) + (Q)- (III), wherein R6 to R9 are as defined above and Q is CR1R11Ri2 NR13R14 pRlS r SR16 wherein R10 to R16 are as de- fined above, and conducting the reaction at a temperature of from more than 40°C, in the presence or the absence of a solvent, for a length of time sufficient to polymerize the monomer (s) and to form a reaction mixture, and thus to form compound IV, in which R18 represents the living polymer chain according to the inven- tion; and isolating the formed compound IV without a quenching step, wherein RI, R2, X1, X2, R3, R4, R5 and R18 are as defined above.

Such an initiator can also be obtained by anionically polymeriz- ing one or more anionically polymerizable monomers and to form a living (co) polymer anion salt G+ (Rl8_z)- wherein G+ is an inorganic cation, in particular a cation selected from the group consisting of elements of group IA, IIA and IIIA of the periodic table of the elements, such as lithium, sodium, potassium, magnesium, calcium, bor or aluminum. R18 is a (co) poly- mer radical, having for instance molecular weight of from 500 to 300 000 g/mol, in particular of from 1 000 to 100 000 g/mol. Z may be a radical derived from an initiator for the anionic polymerization of anionic polymerizable monomers other than radi- cals derived from compounds III or IV. Radicals Z may either stem from alkali organyl or earth alkali organyl compounds, e. g. n-bu- tyl lithium or s-butyl lithium, or from metal-free systems like the ester enolate/protonated P4-phosphazene base system by Seebach and Pietzonka (vide infra) or the alkoxide/n-Bu4N+ system by Reetz et al (vide infra). Thus Z may be for example a butyl, a C-C-linked ester or an 0-linked alkoxy moiety.

Said (co) polymer anion salt is metathesized with a phosphonium salt of the formula (R6R7R8PR9) + T-, wherein T-is an inorganic anion, and R6, R7, R8 and R9 are as defined above, at a temperature in the range of-78 to 120°C to provide compound IV.

T-is preferably selected from the group consisting of a halide, nitrate, nitrite, borate, tetraphenyl borate [Ph4B-], tosylate [p-H3CC6H4SO3-], one-half equivalent of sulfite [or" (S03) o. 5"]. trifluoromethanesulfonate, on-half equivalent of sulfate [or "(SO4) 0. 5"].

Living (co) polymer anion salts can be prepared in accordance with known methods, for example, by an organometal reagent initiated (e. g., a Cl-C4-alkyllithium-initiated) polymerization of an anion- ically polymerizable monomer (e. g. styrene). These compounds can be used to initiate the polymerization of the next comonomer.

Suitable monomers for preparation of such a"living" (co) poly- meric anion include styrene, a-methylstyrene, styrene or a-methylstyrene having 1 to 5 (preferably 1 to 3, most preferably 1) Cl-C4-alkyl and/or Cl-C4-alkoxy substituents on the phenyl ring, butadiene, isoprene, dimethylbutadiene, or mixtures thereof. Preferably the (co) polymer anion is endcapped. Thus, the (co) polymeric anion salt can, for example, be reacted with a 1, 1-diarylethylene (for example, 1, 1-diphenylethylene) to form a (co) polymer diarylmethyl anion, which is then metathesized with a

tetrasubstituted phosphonium halide to provide an initiator of the formula: (co) polymer-(CH2CAr2)- (PR6R7RsR9) + where Ar is an aryl group as defined above.

Living (co) polymer anions as described above can also be reacted with, for example, aziridine, an epoxide or a thiirane to form (co) polymer initiators of the following formulas: (co) polymer-(cRl0Rll (Rl7) NRl3)- (PR6R7R8R9) + (co) polymer-(cRl0Rll (Rl7) o)- (PR6R7R8R9) + (co) polymer-(cRl0Rll (Rl7) s)- (PR6R7R8R9) + where RIO, Rll, R13 and Rl7 are as defined above.

Initiators according to formula IV which are obtained according to the method of the present invention may also be directly employed, i. e. without an isolating step, in the polymerization of monomers of the formula I or II which are distinct from the first monomers used. Monomer (s) of the formula I or II can then either be added to the initiator IV, neat or in solution, at a temperature of above or below 40°C.

The isolating step for compound IV is conducted in accordance with known procedures and methods, such as precipitating the polymeric initiator and filtering the precipitated initiator.

Precipitation can be conducted using a suitable inert non-sol- vent, such as a CS-C8-alkane or-cycloalkane, e. g. hexan, heptane, cyclohexane, pentane or mineral spirits. Preferably, the non-sol- vent for precipitating is hexane or mixtures of hexanes.

The (co) polymeric initiators corresponding to or containing a compound according to formula IV are then used to initiate the polymerization of the next anionically polymerizable comonomer (preferably of the formulas (I) or (II) as described above).

These initiators can for instance be used in the process of the present invention to make a block copolymer having, for example, a first polystyrene block and a second poly (meth) acrylate or polyacrylonitrile block.

Thus, the present invention also encompasses a method for prepar- ing a block (co) polymer, 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: with an initiator corresponding to or containing (R6R7R8PR9) + (Q')- (IV) and conducting the reaction at a temperature of from more than 40°C, in the presence or the absence of a solvent, for a length of time sufficient to polymerize the monomer (s) and form a reaction mixture, and quenching the reaction mixture with an acyl halide, an acid anhydride or a substance containing an active hyrogen atom to form a (co) polymer; and isolating the formed (co) polymer, wherein the substituents R1 to R16, R18, Xl, X2, L, Q'and Z as well as the index m are as defined above.

The present invention is thus also concerned with a method of making block copolymers of the formula: (co) polymer- (CH2CAr2)-A (co) polymer- (CRlORll (Rl7) NR13)-A (co) polymer-(CRl0Rll (Rl7) O)-A (co) polymer- (CR1R11 (R1) S)-A where (co) polymer is one produced by anionic polymerization (pre- ferably of styrene, a-methylstyrene, styrene or a-methylstyrene having 1 to 5 Cl-C4-alkyl and/or Cl-C4-alkoxy substituents on the phenyl ring, butadiene, isoprene, dimethylbutadiene, or mixtures thereof), R10, Rll, R13, pi and Ar are as defined above, and A is one or more distinct (co) polymer blocks of one or more monomers of the formula: where R1, R2, X1, X2, L and m are as defined above and (co) polymer refers to Q'as defined above.

Generally the method of making block copolymers also encompasses the synthesis of compounds like, for example, (co) polymer-A, where (co) polymer is one produced by anionic polymerization as described above, in particular a homo-or copolymer of acrylates or methacrylates, and A is one or more distinct (co) polymer blocks of one or more monomers of formula I or II.

The weight or number average molecular weight of a block in the present block (co) polymers may range from 300 to 500,000 g/mol, more preferably 500 to 300,00 g/mol, and most preferably from 1,000 to 100,000 g/mol. Similar to the monodisperse (co) polymer described above, the weight or number average molecular weight of block B in the present triblock copolymer may range from 500 g/ mol to 300,000 g/mol, preferably from 1,000 to 200,000 g/mol, and more preferably from 2,000 to 60,000 g/mol. The present block copolymers are also preferably narrow in molecular weight in that they may have a MW/Mn value of < 2.0, preferably < 1.5, and most preferably < 1.2. Successive blocks may also be of the same mono- mer, but have a different tacticity.

The polymerization methods described can be conducted with or without a solvent. In the context of the present invention when a small quantity of liquid is required to solubilize or partially solubilize the initiator the polymerization is still run without a solvent.

Suitable solvents for the reacting or polymerizing step of the present method (in any of its various embodiments) include ethers, cyclic ethers, aliphatic and aromatic hydrocarbon sol- vents, and mixtures thereof. Suitable ethers include compounds of the formula R19OR20, in which each of R19 and R20 is independently an alkyl group of from 1 to 6 carbon atoms which may be further substituted with a Cl-C4-alkoxy group.

Preferably, when one of R19 and R20 is methyl, the other of R19 and R20 is alkyl of from 4 to 6 carbon atoms or Cl-C4-alkoxyethyl. Ex- amples include diethyl ether, ethyl propyl ether, dipropyl ether, methyl t-butyl ether, di-t-butyl ether, glyme (dimethoxyethane), diglyme (diethylene glycol dimethyl ether), etc.

Suitable cyclic ethers include THF and dioxane. Suitable aromatic hydrocarbon solvents include benzene, toluene, o-xylene, m-xy- lene, p-xylene and any isomer or mixture of isomers of cumene.

Suitable aliphatic hydrocarbon solvents include linear and cyclic compounds, such as hexane, cyclohexane or mineral spirits.

The initiator should be at least partially soluble in the sol- vent. Thus, when using an aromatic solvent, the reaction may be advantageously promoted by increasing the lipophilicity of the initiator (e. g., having a C6-C20-alkyl substituent in one or both of the ionic components [preferably at least in the phosphonium cation]). For example, if the initiator has the formula (R6R7RePR9) + (CRlOR11Rl2)-or (R6R7R8PR9) + (NRl3Rl4)-, where R6 to R14 are independently an aryl group, one or more of these aryl groups should include one or more alkyl substituents having from 1 to 20 carbon atoms, preferably having from 4 to 20 carbon atoms and more preferably having form 6 to 20 carbon atoms. To avoid molecular weight distribution broadening, the polymer should also be soluble in the solvent selected.

The polymerization may be conducted by addition of a solution of monomer into a solution of initiator. The monomer may also be added as such, i. e. without any solvent, to a solution of the initiator. It is also within the context of the present invention to add the initiator to the monomer (s) or to the monomer solu- tion, respectively. The initiator may be added neat, partially dissolved or completely dissolved.

The polymerization reaction can also be conducted in the absence of a solvent. According to the invention absence of a solvent does not exclude the addition of an initiator which is dissolved or partially dissolved in an inert solvent, which does not quench the reaction, to the reaction mixture.

According to the present invention the monomer (s) and the initia- tor are mixed at a temperature of at or below 40°C. However, mix- ing may also take place at temperatures of above 40°C. For reasons of convenience mixing of monomer (s) and initiator is usually con- ducted at room temperature. The reaction mixture can then immedi- ately be heated to a temperature of above 40°C or can be kept be- low 40°C for several minutes to hours prior to heating to a temperature of above 40°C. Polymerizations according to the pres- ent invention can also be conducted under adiabatic or nearly adiabatic conditions.

When the polymerization reaction is very exothermic a preferred temperature can be achieved by cooling the reaction in a controlled manner.

Although the present invention may be conducted at a temperature of from 40°C to 150°C, the preferred range is from 45°C to 140°C, more preferably from 50°C to 130°C, even more preferably from 60°C to 130°C, and most preferably from 65°C to 120°C.

It is believed that there exists an equilibrium between a dormant species [phosphorous ylid, probably present in an amount of more than 95% of all species) and a polymerization active species (phosphonium enolate, probably present in an amount of less than 5% of all species) such as is indicated in the scheme below: Phosphorous ylid (>95%) Phosphonium enolate (>5%) Thus, the initiators according to the invention as described above correspond to or contain for example compounds according to formula (III): [(R6R7R3PR9) +] nQn-or formula (IV) : [(R6R7R8PR9) +] (Q') The present isolating step is conducted in accordance with known procedures and methods, such as quenching the reaction mixture, precipitating the (co) polymer and filtering off the precipitated (co) polymer. Precipitation can be conducted using a suitable C5-C8-alkane or cycloalkane non-solvent, such as hexane, heptane, cyclohexane, pentane, mineral spirits, or a Cl-C6-alcohol, such as methanol, ethanol or isopropanol, or any mixture of suitable non- solvents. Preferably, the non-solvent for precipitating is hex- ane, mixtures of hexanes, or methanol.

Suitable quenching reagents for the termination of the polymerization in the present process include acyl halides, acid anhydrides and substances containing an active hydrogen atom.

Suitable acyl halides include halides, preferably chlorides, of organic acids, including carboxylic acids, sulfonic acids, phos- phonic acids, etc. Such acids are suitably of the formula R21CO (Hal), R21SO2 (Hal) and R21p (=O) (OR22) (Hal), in which R21 is alkyl of from 1 to 20 carbon atoms in which each of the hyrogen atoms may be independently replaced by a halide (preferably a fluoride or a chloride), alkenyl of from 2 to 20 carbon atoms, alkynyl of from 1 to 10 carbon atoms, phenyl which may be substi- tuted with from 1 to 5 halogen atoms or alkyl groups of from 1 to 4 carbon atoms, or aralkyl in which the aryl group is phenyl of substituted phenyl and the alkyl group is from 1 to 6 carbon atoms; (Hal) is a fluorine, chlorine, bromine or iodine atom; and R22 is alkyl of from 1 to 4 carbon atoms. Preferred acyl halides include benzenesulfonyl chloride, toluenesulfonyl chloride and those of the formule R23CO (Hal), in which R23 is alkyl of from 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl or i-propyl, vinyl, 2-propenyl or phenyl, and (Hal) is chlorine (e. g., acetyl chloride, propionyl chloride, (meth) acryloyl chloride and benzoyl chloride). The most preferred acyl halide is methacryloyl chlo- ride.

Suitable acid anhydrides include those of the formula (R23CO) 20, where R23 is as defined above. Preferred acid anhydrides include acetic anhydride, propionic anhydride, and (meth) acrylic anhydride.

Active hydrogen atom-containing substances include those substances in which a hydrogen atom is attached to a heteroatom, and which have a pKa less than the protonated nitrogen, oxygen or sulfur anion of the initiator. Such compounds include water, al- cohols of from 1 to 6 carbon atoms, aqueous solutions of ammonium salts (e. g., ammonium halide or ammonium carbonates), carboxylic and mineral acids (e. g., acetic acid, hydrochloric acid, etc.) or an aqueous solution thereof, etc., with acetic acid being the most preferred quenching agent.

However, if it is desired to isolate the living polymer by omit- ting the quenching step, only inert and anhydrous aprotic sol- vents, such as C5-C8-alkane or cycloalkane solvents, can be used for precipitation and washing. The precipitated (co) polymer can be filtered off by gravity or by vacuum filtration, in accordance with known methods (e. g., using a Buchner funnel and an aspira- tor). The polymer can then be washed with the liquid used to pre-

cipitate the polymer, if desired. The steps of precipitating, filtering and washing may be repeated, as desired. Care has to be taken in the isolation of the living polymer in that moisture should be excluded from the precipitation, washing and drying steps.

Once isolated, the (co) polymer may be dried by drawing air or an inert gas, e. g. nitrogen, through the (co) monomer, by vacuum, etc., in accordance with known methods (preferably by vacuum).

The present (co) polymer may be analyzed and/or characterized by size exclusion chromatography, in accordance with known proce- dures.

The syndiotactic content of PMMA prepared by the present process at 70°C is moderately high.

The reaction can be carried out in any suitable reactor, e. g. in a batch system or in a continuous flow system. Homo-and statis- tical copolymers can be prepared in a continuous stirring tank reactor.

The polymers produced by the present method have a narrow molecu- lar weight distribution. The ratio of weight average molecular weight to number average molecular weight (MW/Mn) is usually below 2.0, more preferably of 1.5 or less, and most preferably of 1.2 or less.

The number average molecular weight of polymer produced by the present method depends linearly on the conversion.

Having generally described this invention, a further under- standing can be obtained by reference to certain specific exam- ples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.

EXAMPLE Reagents and solvents The work was carried out under nitrogen. Tetrahydrofurane (THF) was titrated with tritylpotassium/THF solution to a persistent red color and then recondensed under reduced pressure.

Triphenylmethane was dried for 8h under reduced pressure and then admixed in THF with Na-K alloy. After 4h stirring, the remaining metal was filtered off and the concentration of Ph3CK/THF solution was determined by titration of acetanilide as 0.146 mol/l.

The methyl methacrylate was purified by introduction of nitrogen and storage over alumina, followed by stirring over CaH2 and sub- sequent recondensation under reduced pressure.

The (1-naphthyl) Ph3PBr was first dried for about 8h at about 100°C in a high vacuum. The (1-naphthyl) Ph3PBr thus predried was then slurried up in the THF and tritrated with tritylpotassium/THF solution at room temperature to a red color. The white (1-nap- thyl) Ph3PBr was then filtered off and subsequently dried under re- duced pressure.

I. Initiator preparation The initiator was prepared by adding a stoichiometric amount of (1-naphthyl) (phenyl) 3P+Br- (=NTPBr) to tritylpotassium in THF (50 ml) at room temperature to afford a 0.004 mol/1, red initia- tor solution.

II. Polymerization 1) 0.8 g methylmethacrylate (MMA) in THF (7 ml) were added drop- wise at room temperature to a 0.004 mol/1 initiator solution in THF (50 ml), prepared as described above. After stirring for 0.5h at room temperature and 21.7h at 70°C the polymerization was quenched by addition of methanol/acetic acid (10/1) and the polymer isolated by precipitation in methanol followed by filtration and drying to constant weight in a vacuum oven at 50°C. The weight of the isolated white polymethylmethacrylate powder corresponded to a yield of 100%.

2) 0.8 g MMA in THF (7 ml) were added dropwise at 70°C to a 0.004 mol/1 initiator solution in THF (50 ml), prepared as described above. After 21. 5h at 70°C the polymerization was quenched by addition of methanol/acetic acid (10/1) and the polymer isolated by precipitation in methanol followed by filtration and drying to constant weight in a vacuum oven at 50°C. The weight of the isolated white polymethylmethacrylate powder corresponded to a yield of 98%.

After specified intervalls small aliquots were taken from the polymerization mixture and quenched by addition of methanol/ace- tic acid (10/1). The number average molecular weight Mn and the ratio of weight average molecular weight to number average molec- ular weight Mw/Mn of the samples obtained were determined by size exclusion chromatography (SEC) relative to polymethylmeth- acrylate standards.

The results of the examples 1) and 2) are documented in the fol- lowing table.

Table: Example 1) Example 2) t/mina) Mn (g/mol) Mw/Mn Mn (g/mol) MW/Mn 6 1700 1. 05 1600 1. 05 19 2500 1. 03 49 3800 1. 11 130 14500 1. 07 180 9300 1. 17 1290 17300 1. 09 1300 19000 1. 18 a) reaction time at a temperature of 70°C.