Elastic substantially linear olefin polymers

A copolymer of ethylene with a C.sub.3 -C.sub.20 alpha-olefin characterized as having long chain branches, a melt flow ratio, I.sub.10 /I.sub.2,.gtoreq.5.63, and a molecular weight distribution, M.sub.w /M.sub.n, defined by the equation:

• M.sub.w /M.sub.n .ltoreq.(I.sub.10 /I.sub.2)-4.63,
• produced by continuously contacting ethylene and a C.sub.3 -C.sub.20 alpha-olefin with a catalyst composition in a polymerization reactor under continuous steady state polymerization conditions in a solution process, wherein said catalyst composition is made from components comprising:
• (a) a metal coordination complex corresponding to the formula:
• ##STR9## wherein:
• M is titanium,
• R' each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms;
• Z is a moiety comprising boron, or a member of group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, said moiety having up to 20 nonhydrogen atoms;
• X independently each occurrence is an anionic ligand group or neutral Lewis base ligand group having up to 30 non-hydrogen atoms;
• n is 0, 1, 2, 3, or 4, and is 2 less than the valence of M;
• and
• Y is an anionic or nonanionic ligand group bonded to Z and M comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, optionally Y and Z together form a fused ring system, and
• (b) an activating cocatalyst, and
• wherein said continuous process conditions include recovering the copolymer by continuously removing said copolymer via a reactor exit stream.

A copolymer of ethylene with a C.sub.3 -C.sub.20 alpha-olefin characterized as having long chain branches, a melt flow ratio, I.sub.10 /I.sub.2, 25.63, and a molecular weight distribution, M.sub.w /M.sub.n, defined by the equation:

• M.sub.w /M.sub.n .ltoreq.(I.sub.10 /I.sub.2)-4.63,
• produced by continuously contacting ethylene and a C.sub.3 -C.sub.20 alpha-olefin with a catalyst composition in a polymerization reactor under continuous steady state polymerization conditions, wherein said catalyst composition is made from components comprising:
• (a) a metal coordination complex corresponding to the formula:
• ##STR10## wherein:
• M is a metal of group 3-10, or the Lanthanide series of the Periodic Table of Elements;
• R' each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms and two or more R' groups can form a fused ring system;
• X each occurrence independently is selected from the group consisting of hydride, halo, alkyl, aryl, silyl, germyl, aryloxy, amide, siloxy, neutral Lewis base ligands and combinations thereof having up to 20 non-hydrogen atoms;
• Y is --O--, --S--, --NR*--, --PR*--, or neutral two electron donor ligand selected from the group consisting of OR*, SR*, NR*.sub.2 and PR*.sub.2 ;
• and
• Z is SiR*.sub.2, CR*.sub.2, SiR*.sub.2 SiR.sub.2, CR*.sub.2 CR*.sub.2, CR*.dbd.CR*, CR*.sub.2 SiR*.sub.2, GeR*.sub.2, BR*, BR*.sub.2 ;
• wherein
• R* each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or more R* groups from Y, Z, or both Y and Z form a fused ring system;
• and
• n is 1 or 2;
• and
• (b) an activating cocatalyst, and
• wherein said continuous process conditions include recovering the copolymer by continuously removing said copolymer via a reactor exit stream.

A copolymer of ethylene with a C.sub.3 -C.sub.20 alpha-olefin characterized as having long chain branches, a melt flow ratio, I.sub.10 /I.sub.2, .ltoreq.5.63, and a molecular weight distribution, M.sub.w /M.sub.n, defined by the equation:

• M.sub.w /M.sub.n .ltoreq.(I.sub.10 /I.sub.2)-4.63,
• produced by continuously contacting ethylene and a C.sub.3 -C.sub.20 alpha-olefin with a catalyst composition in a polymerization reactor under continuous steady state polymerization conditions, wherein said catalyst composition is made from components comprising:
• (a) an amidosilane or amidoalkanediyl compound corresponding to the formula:
• ##STR11## wherein:
• M is titanium, zirconium or hafnium, bound in a .eta..sup.5 bonding mode to the cyclopentadienyl group;
• R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl and combinations thereof having up to 10 carbon or silicon atoms and two or more R' groups can form a fused ring system;
• E is silicon or carbon;
• X independently each occurrence is hydride, halo, alkyl, aryl, aryloxy or alkoxy of up to 10 carbons;
• m is 1 or 2;
• and
• n is 1 or 2;
• and
• (b) an activating cocatalyst, and
• wherein said continuous process conditions include recovering the copolymer by continuously removing said copolymer via a reactor exit stream.

A copolymer of ethylene with a C.sub.3 -C.sub.20 alpha-olefin characterized as having long chain branches, a melt flow ratio, I.sub.10 /I.sub.2,.gtoreq.5.63, and a molecular weight distribution, M.sub.w /M.sub.n, defined by the equation:

• M.sub.w /M.sub.n .ltoreq.(I.sub.10 /I.sub.2)-4.63,
• produced by continuously contacting ethylene and a C.sub.3 -C.sub.20 alpha-olefin with a catalyst composition in a polymerization reactor under continuous steady state polymerization conditions, wherein said catalyst composition is made from components comprising:
• ##STR12## wherein:
• M is Ti X each occurrence independently is selected from the group consisting of hydride, halo, alkyl, aryl, silyl, germyl, aryloxy, amide, siloxy, neutral Lewis base ligands and combinations thereof having up to 20 non-hydrogen atoms;
• Y is --O--, --S--, --NR*--, --PR*--, or neutral two electron donor ligand selected from the group consisting of OR*, SR*, NR*.sub.2 and PR*.sub.2 ;
• Z is SiR*.sub.2, CR*.sub.2, Si,R*.sub.2 SiR.sub.2, CR*.sub.2 CR*.sub.2, CR*.dbd.CR*, CR*.sub.2 SiR*.sub.2, GeR*.sub.2, BR*, BR*.sub.2 ;
• wherein
• R* each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or more R* groups from Y, Z, or both Y and Z form a fused ring system;
• n is 1 or 2;
• R' each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms and two or more R' groups can form a fused ring system;
• A.sup.- is a non-coordinating, compatible anion;
• and
• (b) an activating cocatalyst, and
• wherein said continuous process conditions include recovering the copolymer by continuously removing said copolymer via a reactor exit stream.

A copolymer of ethylene with a C.sub.3 -C.sub.20 alpha-olefin characterized as having long chain branches, a melt flow ratio, I.sub.10 /I.sub.2,.gtoreq.5.63, and a molecular weight distribution, M.sub.w /M.sub.n, defined by the equation:

• M.sub.w /M.sub.n .ltoreq.(I.sub.10 /I.sub.2)-4.63,
• produced by contacting ethylene and a C.sub.3 -C.sub.20 alpha-olefin with a catalyst composition in a polymerization reactor under continuous steady state polymerization conditions, wherein said catalyst composition fed to the reactor is made from components consisting essentially of:
• (a) at least one supported or unsupported metal coordination complex corresponding to the formula:
• ##STR13## wherein:
• M is titanium;
• R' each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms and two or more R' groups can form a fused ring system;
• Z is a moiety comprising boron, or a member of group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, said moiety having up to 20 nonhydrogen atoms;
• X independently each occurrence is an artionic ligand group or neutral Lewis base ligand group having up to 30 non-hydrogen atoms;
• n is 0, 1, 2, 3, or 4, and is 2 less than the valence of M;
• and
• Y is an artionic or non-anionic ligand group bonded to Z and M comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, optionally Y and Z together form a fused ring system, and
• (b) at least one activating cocatalyst and,
• wherein said continuous process conditions includes recovering the copolymer by continuously removing said copolymer via a reactor exit stream.

A copolymer of ethylene with a C.sub.3 -C.sub.20 alpha-olefin characterized as having long chain branches, a melt flow ratio, I.sub.10 /I.sub.2, .gtoreq.5.63, and a molecular weight distribution, M.sub.w /M.sub.n , defined by the equation:

• M.sub.w /M.sub.n .ltoreq.(I.sub.10 I.sub.2)-4.63,
• produced by contacting ethylene and a C.sub.3 -C.sub.20 alpha-olefin with a catalyst composition in a polymerization reactor under continuous steady state polymerization conditions, wherein said catalyst composition fed to the reactor is made from components comprising:
• (a) a metal coordination complex comprising a metal atom of groups 3-10 or the Lanthanide series of the Periodic Table of the Elements and a delocalized .pi.-bonded moiety substituted with a constrain inducing moiety, said complex having a constrained geometry about the metal atom such that the angle at the metal atom between the centroid of the delocalized, substituted .pi.-bonded moiety and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar .pi.-bonded moiety lacking in such constrain-inducing substituent,
• and provided further that for such complexes comprising more than one delocalized, substituted .pi.-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted .pi.-bonded moiety, and
• (b) an activating cocatalyst, and
• wherein said continuous process conditions include recovering the copolymer by continuously removing said copolymer via a reactor exit stream.

A copolymer of ethylene with a C.sub.3 -C.sub.20 alpha-olefin characterized as having long chain branches, a melt flow ratio, I.sub.10 /I.sub.2,.gtoreq.5.63, and a molecular weight distribution, M.sub.w /M.sub.n, defined by the equation:

• M.sub.w /M.sub.n .ltoreq.(I.sub.10 I.sub.2)-4.63,
• produced by continuously contacting ethylene and a C.sub.3 -C.sub.20 alpha-olefin with a catalyst composition in a polymerization reactor under continuous steady state polymerization conditions, wherein said catalyst composition is made from components comprising:
• (a) a metal coordination complex comprising a metal atom of groups 3-10 or the Lanthanide series of the Periodic Table of the Elements and a delocalized .pi.-bonded moiety substituted with a constrain inducing moiety,
• said complex having a constrained geometry about the metal atom such that the angle at the metal atom between the centroid of the delocalized, substituted .pi.-bonded moiety and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar .pi.-bonded moiety lacking in such constrain-inducing substituent,
• and provided further that for such complexes comprising more than one delocalized, substituted .pi.-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted .pi.-bonded moiety, and
• (b) an activating cocatalyst, and
• wherein said continuous process conditions include recovering the copolymer by continuously removing said copolymer via a reactor exit stream and said copolymer is further characterized as having a critical shear stress at onset of gross melt fracture of greater than 4.times.10.sup.6 dynes/cm.sup.2.

A copolymer of ethylene with a C.sub.3 -C.sub.20 alpha-olefin produced by continuously contacting ethylene and a C.sub.3 -C.sub.20 alpha-olefin with a catalyst composition in a polymerization reactor under continuous steady state polymerization conditions such that the copolymer has a I.sub.10 /I.sub.2,.gtoreq.5.63, a molecular weight distribution, M.sub.w /M.sub.n, defined by the equation:

• M.sub.w M.sub.n .ltoreq.(I.sub.10 /I.sub.2)-4.63,
• and a critical shear stress at onset of gross melt fracture of greater than 4.3.times.10.sup.6 dynes/cm.sup.2, wherein said catalyst composition is made from components comprising:
• (a) a metal coordination complex comprising a metal atom of groups 3-10 or the Lanthanide series of the Periodic Table of the Elements and a delocalized .pi.-bonded moiety substituted with a constrain inducing moiety,
• said complex having a constrained geometry about the metal atom such that the angle at the metal atom between the centroid of the delocalized, substituted .pi.-bonded moiety and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar .pi.-bonded moiety lacking in such constrain-inducing substituent,
• and provided further that for such complexes comprising more than one delocalized, substituted .pi.-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted .pi.-bonded moiety, and
• (b) an activating cocatalyst, and
• wherein said continuous process conditions include recovering the copolymer by continuously removing said copolymer via a reactor exit stream and wherein the copolymer has 0.01 to 3 long chain branches per 1000 carbons.

A copolymer of ethylene with a C.sub.3 -C.sub.20 alpha-olefin characterized as having long chain branches, a melt flow ratio, I.sub.10 /I.sub.2,.gtoreq.5.63, and a molecular weight distribution, M.sub.w /M.sub.n, defined by the equation:

• M.sub.w /M.sub.n .ltoreq.(I.sub.10 /I.sub.2)-4.63,
• produced by continuously contacting ethylene and a C.sub.3 -C.sub.20 alpha-olefin with a catalyst composition under continuous steady state polymerization conditions, wherein said catalyst composition is made from components comprising:
• (a) a metal coordination complex corresponding to the formula:
• ##STR14## wherein:
• M is a metal of group 3-10, or the Lanthanide series of the Periodic Table of Elements;
• R' each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms and two or more R' groups can form a fused ring system;
• Z is a moiety comprising boron, or a member of group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, said moiety having up to 20 non-hydrogen atoms;
• X independently each occurrence is an artionic ligand group or neutral Lewis base ligand group having up to 30 non-hydrogen atoms;
• n is 0, 1, 2, 3, or 4, and is 2 less than the valence of M;
• and
• Y is an anionic or nonanionic ligand group bonded to Z and M comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, optionally Y and Z together form a fused ring system, and
• (b) an activating cocatalyst, and
• wherein said continuous process conditions include recovering the copolymer by continuously removing said copolymer via a reactor exit stream and said recovered copolymer is further characterized as having a critical shear stress at onset of gross melt fracture of greater than 4.times.10.sup.6 dynes/cm.sup.2.

A copolymer of ethylene with a C.sub.3 -C.sub.20 alpha-olefin characterized as having long chain branches, a melt flow ratio, I.sub.10 /I.sub.2,.gtoreq.5.63, and a molecular weight distribution, M.sub.w /M.sub.n, defined by the equation:

• M.sub.w /M.sub.n .ltoreq.(I.sub.10 /I.sub.2)-4.63,
• produced by contacting ethylene and a C.sub.3 -C.sub.20 alpha-olefin with a catalyst composition in a polymerization reactor under continuous steady state polymerization conditions, wherein said catalyst composition fed to the reactor is made from components comprising:
• a.
• a metal coordination complex comprising a metal atom of groups 3-10 or the Lanthanide series of the Periodic Table of the Elements and a delocalized .pi.-bonded moiety substituted with a constrain inducing moiety,
• said complex having a constrained geometry about the metal atom such that the angle at the metal atom between the centroid of the delocalized, substituted n bonded moiety and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar .pi.-bonded moiety lacking in such constrain-inducing substituent,
• and provided further that for such complexes comprising more than one delocalized, substituted .pi.-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted .pi.-bonded moiety, and
• (b) an activating cocatalyst, and
• wherein said continuous process conditions include recovering the copolymer by continuously removing said copolymer via a reactor exit stream and said copolymer is further characterized as having a critical shear stress at onset of gross melt fracture of greater than 4.times.10.sup.6 dynes/cm.sup.2.

An olefin copolymer of ethylene and 1-octene having a melt flow ratio, I.sub.10 /I.sub.2,.gtoreq.5.63, a molecular weight distribution M.sub.w /M.sub.n, defined by the equation:

• M.sub.w /M.sub.n .ltoreq.(I.sub.10 /I.sub.2)-4.63,
• and a molecular weight distribution from 1.5 to 2.5, and a critical shear stress at onset of gross melt fracture of greater than 4.times.10.sup.6 dyne/cm.sup.2, obtained by a continuous solution polymerization process comprising the steps of:
• (a) introducing ethylene and hydrogen into a solvent comprising a mixture of C.sub.8 -C.sub.10 saturated hydrocarbons and 1-octene to provide a reactor feed mixture;
• (b) continuously injecting said reactor feed mixture into a continuously stirred reactor;
• (c) combining a metal-coordination complex of the formula:
• ##STR15## wherein:
• M is titanium bound in an .eta..sup.5 bonding mode to the cyclopentadienyl group;
• R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl and combinations thereof having up to 10 carbon or silicon atoms and two or more R' groups can form a fused ring system;
• E is silicon or carbon;
• X independently each occurrence is hydride, halo, alkyl, aryl, aryloxy or alkoxy of up to 10 carbons;
• m is 1;
• and
• n is 2, and
• an activating cocatalyst, to form a polymerization catalyst;
• (d) continuously injecting said polymerization catalyst into the reactor;
• (e) continuously recovering the copolymer by continuously removing said copolymer via a reactor exit stream;
• wherein the reactor pressure is 490 psig, the ethylene content of the reactor, after reaching steady state, is maintained below 4 percent by weight of the reactor contents and the polymerization reactor temperature is in the range from 114 C to 200 C.