Patent ID: 6232417
Filing Date: 2001-05-15
Classification: C08G,G03F,Y10S

Abstract:
A method for preparing a polycyclic polymer comprising polymerizing a monomeric reaction composition comprising at least two types of polycyclic monomers one of which containing a pendant acid labile group and another of which containing a pendant polar functional group in the presence of a catalyst represented by the formula:E.sub.n M(Q).sub.f (R.sup.z).sub.gwherein M is a Group VIII transition metal, Q is an electron withdrawing ligand selected from the group consisting of linear and branched (C.sub.1 to C.sub.10) perhaloalkyl, (C.sub.7 to C.sub.24) perhaloalkaryl and perhaloaryl groups, n is an integer of 0, 1, 2 or 3; f is an integer of 1, 2 or 3; g is an integer of 0 or 1; when f is 1, R.sup.z must be present; and E when present is selected from a monodentate or bidentate ligand wherein said monodentate ligand is selected from the group consisting of p-arenes; ethers and thioethers of the formulae R.sup.i --O--R.sup.i and R.sup.i --S--R.sup.i wherein R.sup.i can be the same or different and represents a linear and branched (C.sub.1 to C.sub.10) alkyl group, the R.sup.i groups that are connected to the oxygen or sulfur heteroatom can be taken together to represent heterocyclic ring containing 4 to 8 carbon atoms; cyclic diethers containing 3 to 6 carbon atoms; ketones represented by the formula R.sup.i --C(O)--R.sup.i wherein R.sup.i is as defined above; substituted or unsubstituted cyclic ketones containing 5 to 8 carbon atoms wherein said substituents are selected from linear or branched (C.sub.1 to C.sub.10) alkyl and (C.sub.6 to C.sub.24) aryl groups; amines of the formula N(R.sup.d).sub.3 wherein R.sup.d independently represents linear or branched (C.sub.1 to C.sub.10) alkyl, (C.sub.7 to C.sub.10) aralyl, (C.sub.6 to C.sub.24) aryl and cycloaliphatic groups containing 5 to 8 carbon atoms, wherein said alkyl, aryl and cycloaliphatic substituents optionally contain halogen atoms selected from chlorine, bromine, fluorine and iodine; pyridine, and substituted pyridine containing linear and branched (C.sub.1 to C.sub.10) alkyl groups; phosphines of the formula P(R.sup.d).sub.3, phosphine oxides of the formula (R.sup.d).sub.3 PO; phosphites of the formula P(OR.sup.d).sub.3 wherein R.sup.d in each of the phosphine, phosphine oxide and phosphite formulae is as defined above; ester compounds of the formula R.sup.i C(O)OR.sup.i wherein R.sup.i is defined above; lactones and linear and branched (C.sub.1 to C.sub.6) alkyl and (C.sub.6 to C.sub.15) aryl substituted lactones wherein the lactone ring contains 3 to 8 carbon atoms; and said bidentate ligand is selected from a hemilabile chelating ligand containing phosphorus, oxygen, nitrogen and sulfur represented by the formula: ##STR59##wherein Y and Z independently represent phosphorus, oxygen, carbonyl, nitrogen and sulfur which are optionally substituted with linear and branched(C.sub.1 to C.sub.1) alkyl and (C.sub.6 to C.sub.24) aryl groups and K represents an unsubstituted and substituted hydrocarbon backbone moiety containing from 2 to 25 carbon atoms, or a divalent alkylene ether moiety wherein the alkylene radicals independently contain from 1 to 10 carbon atoms, said substituents if present are selected from linear and branched (C.sub.1 to C.sub.10) alkyl, (C.sub.5 to C.sub.15) alicyclic and (C.sub.6 to C.sub.24 aryl), halides, and amine; and R.sup.z is a substituted or unsubstituted allyl ligand represented by the formula: ##STR60##wherein R.sup.20, R.sup.21, and R.sup.22 independently represent hydrogen, linear or branched (C.sub.1 to C.sub.5) alkyl, (C.sub.6 to C.sub.14) aryl, (C.sub.7 to C.sub.10) aralkyl such as benzyl, --COOR.sup.38, --(CH.sub.2).sub.n OR.sup.38, Cl and (C.sub.5 to C.sub.6) cycloaliphatic, wherein R.sup.38 is linear and branched (C.sub.1 to C.sub.5) alkyl, and n is 1 to 5, any two of R.sup.20, R.sup.21, and R.sup.22 may be linked together to form an alicyclic group and wherein said polycyclic monomers are represented by the formulae: ##STR61##wherein R.sup.1 to R.sup.4 independently represent a substituent selected from the group consisting of hydrogen, linear and branched (C.sub.1 to C.sub.10) alkyl, --(A).sub.n C(O)OR*, --(A).sub.n --C(O)OR, --(A).sub.n --OR, --(A).sub.n --OC(O)R, --(A).sub.n --C(O)R, --(A).sub.n --OC(O)OR, --(A).sub.n --OCH.sub.2 C(O)OR*, --(A).sub.n --C(O)O--A'--OCH.sub.2 C(O)OR*, --(A).sub.n --OC(O)--A'--C(O)OR*, --(A).sub.n C(R).sub.2 CH(R)(C(O)OR**), and --(A).sub.n C(R).sub.2 CH(C(O)OR**).sub.2 wherein n is 0 or 1, m is an integer from 0 to 5, --A-- and --A'-- independently represent a divalent radical selected from the group consisting of linear and branched (C.sub.1 to C.sub.10) alkylene, (C.sub.2 to C.sub.10) alkylene ethers, polyethers, or a divalent cyclic group of the formula: ##STR62##wherein a is an integer from 2 to 7, and the diagonal bond projecting from the center of the cyclic structure represents the divalent nature of the cyclic moiety and can be connected to anyone of the carbocyclic atoms (--CH.sub.2 --) in the ring with the proviso that the carbocyclic atom to which the bond is connected will have one less hydrogen atom to satisfy the valance of carbon, R represents hydrogen or linear and branched (C.sub.1 to C.sub.10) alkyl, and R* represents an acid labile group that is cleavable by a photoacid initiator and is selected from the group consisting of --C(CH.sub.3).sub.3, --Si(CH.sub.3).sub.3, --CH(R.sup.P)OCH.sub.2 CH.sub.3, --CH(R.sup.P)OC(CH.sub.3).sub.3, or the following cyclic groups: ##STR63##wherein R.sup.P represents hydrogen or a linear or branched (C.sub.1 to C.sub.5) alkyl group, R** independently represents R and R* and at least one of R.sup.1 to R.sup.4 must be selected from a substituent containing said acid labile group; and wherein R.sup.5 to R.sup.8 independently represent a substituent selected from the group consisting of hydrogen, linear and branched (C.sub.1 to C.sub.10) alkyl, and a polar substituent represented as follows: --(A).sub.n --C(O)OR"", --(A).sub.n --OR"", --(A).sub.n --OC(O)R"", --(A).sub.n --OC(O)OR"", --(A).sub.n --C(O)R"", --(A).sub.n --OC(O)C(O)OR"", --(A).sub.n --O--A'--C(O)OR"", --(A).sub.n --OC(O)--A'--C(O)OR"", --(A).sub.n --C(O)O--A'--C(O)OR"", --(A).sub.n --C(O)--A'--OR"", --(A).sub.n --C(O)O--A'--OC(O)OR"", --(A).sub.n --C(O)O--A'--O--A'--C(O)OR"", --(A).sub.n --C(O)O--A'--OC(O)C(O)OR"", --(A).sub.n --C(R"").sub.2 CH(R"")(C(O)OR""), and --(A).sub.n --C(R"").sub.2 CH(C(O)OR"").sub.2, wherein n is 0 or 1, p is an integer from 0 to 5, R"" represents a substituent selected from hydrogen, linear and branched (C.sub.1 to C.sub.10) alkyl, linear and branched (C.sub.1 to C.sub.10) alkoxyalkylene, polyethers, monocyclic and polycyclic (C.sub.4 to C.sub.20) cycloaliphatic moieties, cyclic ethers, cyclic diethers, cyclic ketones, and cyclic esters (lactones), with the proviso that when R"" is an alkyl, lactone, cycloaliphatic or cyclic ketone group --A-- must be present and can not represent an alkylene radical.