Molecular weight reduction of unsaturated polymers

The process of modifying the properties of a polymer by effecting a decrease in molecular weight or inherent viscosity wherein said polymer is characterized by a carbon backbone with internal unsaturation in the polymer carbon backbone and an initial weight average molecular weight of at least about 1000 as determined by light scattering, wherein said process comprises contacting said polymer with an olefin disproportionation catalyst comprising a homogeneous catalyst under contacting conditions of temperature and pressure at which said olefin disproportionation catalyst is active for the olefin reaction, for a time sufficient to effectuate said modification,

• wherein said homogeneous catalyst comprises (a) a transition metal compound, and (b) an organometallic compound, wherein said (a) is represented by the formula [(L).sub.a M.sub.c Z.sub.d ].sub.x wherein each (L) represents an inorganic ligand;
• M is molybdenum, tungsten, rhenium, ruthenium, or rhodium;
• Z is a halide, CN, SCN, OCN, or SnCl.sub.3 radical;
• a and d each represent a number 1 to 5;
• c represents a number 1 to 4;
• and x represents a number indicative of the polymeric state of the compound;
• wherein said (b) component of said homogeneous catalyst is an organometallic adjuvant comprising (1) R.sub.e AlX.sub.f, (2) a mixture of compounds of (1), (3) a mixture of one or more of AlX.sub.3 or R.sub.e AlX.sub.f compounds with one or more compounds represented by the formula R.sub.g.sup.1 M.sup.1 X.sub.h, (4) R.sub.g M.sup.1 Y.sub.h compound, (5) AlX.sub.3 compound, or (6) M.sup.1 M.sup.2 H.sub.j, wherein each R is an aromatic or saturated aliphatic hydrocarbon radical having up to 20 carbon atoms including alkoxy and halo derivatives thereof, wherein each X is halogen, Y is halogen or hydrogen, each M.sup.1 is a metal of Group IA, IIA, IIB, or IIIA, except Al, each M.sup.2 is a metal of Group IA, IIA, IIB, or IIIA;
• e represents a number 1 to 3, f represents a number 0 to 2, such that the sum of e and f equals 3;
• g represents a number 1 to 3, h represents a number 0 to 2, such that the sum of g and h is equal to the valence of M.sup.1, j is an integer equal to the sum of the valences of M.sup.1 and M.sup.2 .

The process of modifying the properties of a polymer of a cyclic monoolefin by effecting a reduction in the molecular weight of said polymer, wherein said polymer is characterized by a carbon backbone with internal unsaturation in the polymer carbon backbone and an initial weight average molecular weight of at least about 1000 as determined by light scattering, wherein said process comprises contacting said polymer with an olefin disproportionation catalyst comprising a homogeneous catalyst under contacting conditions of temperature and pressure at which said olefin disproportionation catalyst is active for the olefin reaction, for a time sufficient to effectuate said modification,

• wherein said homogeneous olefin disproportionation catalyst comprises an effective ratio of (a) a transition metal compound represented by the formula (L.sub.a M.sub.c Z.sub.d).sub.x wherein each L represents a ligand;
• M is a metal of Group IB, IIIB, IVB, VB, VIB, VIIB, or the iron and cobalt subgroups of Group VIII;
• Z is a halide, CN, SCN, OCN, or SnCl.sub.3, a and b are numbers 0 to 6, c is 1 to 4, and x is a number indicative of the polymeric state of the compound;
• such that at least one of L or Z is present;
• and
• wherein said organometallic adjuvant (b) component of said homogeneous catalyst comprises (1) R.sub.e AlX.sub.f, (2) a mixture of compounds of (1), (3) a mixture of one or more of AlX.sub.3 or R.sub.e AlX.sub.f compounds with one or more compounds represented by the formula R.sub.g.sup.1 M.sup.1 X.sub.h, (4) R.sub.g M.sup.1 Y.sub.h compound, (5) AlX.sub.3 compound, or (6) M.sup.1 M.sup.2 H.sub.j, wherein each R is an aromatic or saturated aliphatic hydrocarbon radical having up to 20 carbon atoms including alkoxy and halo derivatives thereof, wherein each X is halogen, Y is halogen or hydrogen, each M.sup.1 is a metal of Group IA, IIA, IIB, or IIIA, except Al, each M.sup.2 is a metal of Group IA, IIA, IIB, or IIIA;
• e represents a number 1 to 3, f represents a number 0 to 2, such that the sum of e and f equals 3;
• g represents a number 1 to 3, h represents a number 0 to 2, such that the sum of g and h is equal to the valence of M.sup.1, j is an integer equal to the sum of the valences of M.sup.1 and M.sup.2.

A process for treating polymers of cyclomonoolefins characterized by having internal unsaturation in the polymer backbone and having an initial weight average molecular weight of about 1,000 to about 10,000,000 as determined by light scattering, said process comprising contacting said polymer of cyclomonoolefin with a homogeneous olefin disproportionation catalyst, under contacting conditions of temperature and pressure at which said olefin disproportionation catalyst is active for the olefin reaction, wherein said contacting of said polymer with said catalyst results in the generation of cyclomonoolefin monomer,

• wherein said homogeneous olefin disproportionation catalyst comprises (a) a transition metal compound and (b) an organometallic compound wherein the molar ratio of (b) to (a) is about 0.1:1 to about 10:1, and
• wherein said (a) transition metal compound is represented by the formula (L.sub.a M.sub.c Z.sub.d).sub.x wherein each L is an organic or inorganic ligand;
• M is a transition metal of Group IB, IIIB, IVB, VB, VIB, VIIB, or the iron and cobalt subgroups of Group VIII;
• Z is halide, CN, SCN, OCN, or SnCl.sub.3 ;
• a and b are numbers 0 to 6, c is 1 to 4, and x is a number indicative of the polymeric state of the compound;
• such that at least one L or Z is present;
• and
• said (b) component is (1) R.sub.e AlX.sub.f, (2) a mixture of compounds of (1), (3) a mixture of one or more of AlX.sub.3 or R.sub.e AlX.sub.f compounds with one or more compounds having the formula R.sub.g.sup.1 M.sup.1 X.sub.h, (4) an R.sub.g M.sup.1 Y.sub.h compounds, (5) an AlX.sub.3 compound, or (6) M.sup.1 M.sup.2 H.sub.j wherein each R is an aromatic or saturated aliphatic hydrocarbon radical having up to 20 carbon atoms including alkoxy and halo derivatives thereof, preferably an alkyl radical having up to 10 carbon atoms;
• each R.sup.1 is hydrogen or R;
• each X is a halogen;
• Y is halogen or hydrogen;
• each M.sup.1 is a metal of Group IA, IIA, IIB or IIIA, except Al, and each M.sup.2 is a metal of Group IA, IIA, IIB or IIIA;
• e is 1, 2, or 3, f is 0, 1 or 2, the sum of e and f being 3;
• g is 1, 2 or 3, h is 0, 1 or 2, the sum of g and h being equal to the valence of M.sup.1, j is an integer such that it is equal to the sum of the valences of M.sup.1 and M.sup.2.

The process of increasing the molecular weight of a polymer, wherein said polymer is characterized by a carbon backbone with internal unsaturation in the polymer carbon backbone and an initial weight average molecular weight of at least about 1000 as determined by light scattering, wherein said process comprises contacting said polymer with an effective amount of a homogeneous olefin disproportionation catalyst under contacting conditions of temperature and pressure at which said disproportionation catalyst is active for the olefin reaction, whereby the molecular weight of said polymer is increased,

• wherein said homogeneous catalyst comprises (a) a transition metal compound and (b) an organometallic compound in a ratio of said (b):(a) effective to increase said molecular weight,
• wherein said (a) transition metal compound is represented by the formula [(L).sub.a M.sub.c Z.sub.d ].sub.x wherein (L) represents a ligand;
• M is molybdenum, tungsten, rhenium, ruthenium or rhodium;
• Z is a halide, --CN, --SCN, --OCN, or --SnCl.sub.3 radical;
• a and d each represent a number 1 to 5;
• c represents a number 1 to 4;
• x represents a number indicative of the polymeric state of the compound;
• and wherein at least one of (L) and Z is present in said [(L).sub.a M.sub.c Z.sub.d ].sub.x,
• and wherein said (b) organometallic component comprises (1) R.sub.e AlX.sub.f, (2) a mixture of compounds of (1), (3) a mixture of one or more of AlX.sub.3 or R.sub.e AlX.sub.f compounds with one or more compounds represented by the formula R.sub.g.sup.1 M.sup.1 X.sub.h, (4) R.sub.g M.sup.1 Y.sub.h compound, (5) AlX.sub.3 compound, or (6) M.sup.1 M.sup.2 H.sub.j ;
• wherein R is an aromatic or saturated aliphatic hydrocarbon radical having up to 20 carbon atoms including alkoxy and halo derivatives thereof;
• X is halogen;
• Y is halogen or hydrogen;
• M.sup.1 is a metal of Group IA, IIA, IIB, or IIIA, except Al;
• M.sup.2 is a metal of Group IA, IIA, IIB, or IIIA;
• e represents a number 1 to 3, and f represents a number 0 to 2, such that the sum of e and f equals 3;
• g represents a number 1 to 3, and h represents a number 0 to 2, such that the sum of g and h is equal to the valence of M.sup.1 ;
• and j is an integer equal to the sum of the valences of M.sup.1 and M.sup.2.