BRANCHED POLYETHYLENES BY HYDROSILATION GRAFTING TO IMPROVE PROCESSABILITY OF POLYETHYLENE FIELD OF THE INVENTION

[0001] This invention relates to coupling of vinyl terminated polyolefins with a polysilane or a polysiloxane in the presence of a non-metallocene catalyst.

BACKGROUND OF THE INVENTION

[0002] Methods for the production of polyolefins with end-functionalized groups are typically multi-step processes that often create unwanted by-products and waste of reactants and energy. For reviews of methods to form end-functionalized polyolefins, see: S. B. Amin and T. J. Marks, Angew. Chem. Int. Ed. 2008, 47, pp. 2006-2025; T. C. Chung, Prog. Polym. Sci. 2002, 27, pp. 39-85; and R. G. Lopez, F. D'Agosto, C. Boisson, Prog. Polym. Sci. 2007, 32, pp. 419-454. A process with a reduced number of steps would be desirable.

[0003] U.S. Patent No. 4,1 10,377 discloses secondary aliphatic amines alkylated with alpha-olefins, such as ethylene, propylene, hexene, and undecene. Likewise, several literature references disclose hydroaminoalkylation of olefins using various catalysts (see J. Am. Chem. Soc. 2008, 130, pp. 14940-14941 ; J. Am. Chem. Soc. 2007, 129, pp. 6690-6691; Angew. Chem. Int. Ed. 2009, 48, pp. 8361-8365; Angew. Chem. Int. Ed. 2009, 48, pp. 4892- 4894; Yuki Gosei Kagaku Kyokaishi (2009), 67(8), pp. 843-844; Angewandte Chemie, International Edition (2009), 48(6), pp. 1153-1 156; Tetrahedron Letters (2003), 44(8), pp. 1679-1683; and Synthesis (1980), (4), pp. 305-306.

[0004] WO 98/33842 discloses the production of branched polyolefins comprising a silicon containing polymeric backbone with branches extending therefrom in which the branches are formed of polyolefins wherein the branched polymers are produced by a hydrosilation reaction between the polyolefin prearms with a hydrosilane containing group.

[0005] U.S. Patent No. 6,084,030 discloses branched polyolefin polymers in the form of a comb, star, nanogel, and structural combinations thereof comprising a plurality of polyolefin arms selected from the group consisting of (1) polymers of ethylene; (2) polymers of propylene; and (3) copolymers of ethylene with one or more 1-alkenes, said arms being linked to the polymeric backbone, wherein the reactive polymeric backbone is formed from a siloxane, and said backbone contains at least 4-300 polyolefin arms, and said branched polyolefin polymer is prepared by coupling the polyolefin prearms with said polymeric backbone.

[0006] U.S. Patent No. 8,399,725 discloses certain vinyl terminated oligomers and polymers that are functionalized for use in lubricant applications.

[0007] U.S. Patent No. 8,372,930 discloses certain vinyl terminated oligomers and polymers that are functionalized in U.S. Patent No. 8,399,725.

[0008] U.S. Patent No. 8,283,419 discloses a process to functionalize propylene homo- or co-oligomer comprising contacting an alkene metathesis catalyst with a heteroatom containing alkene and a propylene homo- or co-oligomer having terminal unsaturation.

[0009] U.S. Patent No. 8,501,894 discloses a process to functionalize polyolefins comprising contacting a metallocene catalyst with a hydrosilane, and one or more vinyl terminated polyolefins. This invention further relates to the hydrosilane-functionalized polyolefins produced thereby.

[0010] U.S. Publication No. 2012-0245293 discloses a process to functionalize polyolefins comprising contacting a metallocene catalyst with a difunctional diblock hydrosilane, and one or more vinyl terminated polyolefins. This invention further relates to the diblock hydrosilane-functionalized polyolefins produced thereby.

[0011] End-functionalized polyolefins that feature a chemically reactive or polar end group are of interest for use in a broad range of applications as compatibilizers, tie-layer modifiers, surfactants, and surface modifiers.

[0012] Thus, there is an ongoing need to develop a means to provide functionalized polyolefins with different polymeric architectures by efficient reactions, particularly reactions with good conversion, preferably under mild reaction conditions with a minimal number of steps, preferably one or two steps, preferably without solvent.

SUMMARY OF THE INVENTION

[0013] This invention relates to a modified polyolefin represented by the formula:

wherein:

Z is a group represented by the formula:

L ³ — Si PO ¹ wherein PO ¹ is a substituted or unsubstituted hydrocarbyl group having from 20 or 30 or 40 or 50 or 100 or 200 to 10,000 carbon atoms;

R ¹ is Z, hydrogen, a C _j to a C20 substituted or unsubstituted hydrocarbyl group, or PO ⁴ , wherein PO ⁴ is a substituted or unsubstituted hydrocarbyl group having from 20 to

10,000 carbon atoms;

each R ² , R ³ , R ⁴ , and R ⁵ , independently, is hydrogen, a to a Cj substituted or unsubstituted hydrocarbyl group, wherein R ² and R ³ and/or R ⁴ and R ⁵ may form a cyclic structure with Si, or, a PO ⁴ ;

each L ¹ , L ² , and L ³ , independently, is a bond or a linking group;

m is an integer from 1 to 1000;

0 is an integer from 0 to 1000; and

X ¹ and X ² , each independently, is hydrogen, a C _[ to a C20 substituted or unsubstituted hydrocarbyl group, or a PO ⁴ ;

wherein each PO ¹ and PO ⁴ may be the same or different.

[0014] This invention also relates to modified polyolefin represented by the formula:

wherein:

Z is a group represented by the formula:

L ³ — Si PO ¹

wherein PO ¹ is a substituted or unsubstituted hydrocarbyl group having from 20 or 30 or 50 or 100 to 10,000 carbon atoms derived from a vinyl terminated macromonomer;

each R ¹ , R ² , R ³ , R ⁴ , and R ⁵ , independently, is hydrogen, a C _j to a C20 substituted or unsubstituted hydrocarbyl group, where R ² and R ³ may form a cyclic structure with Si, or a PO ⁴ , wherein PO ⁴ is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms derived from a vinyl terminated macromonomer; each L, L ¹ , L ² , and L ³ , is a bond or a linking group;

m is an integer from 1 to 1000 (preferably m is from 100 to 500);

n is an integer 1 to 1000 (preferably n is from 100 to 500);

o is an integer from 0 to 1000 (preferably o is 0; preferably o is from 100 to 500); and

X ¹ and X ² , each independently, is hydrogen, a C _[ to a C20 substituted or unsubstituted hydrocarbyl group, or a PO ⁴ ;

wherein each PO ¹ and PO ⁴ may be the same or different.

BRIEF DESCRIPTION OF THE FIGURES

[0015] Figure 1 depicts an extensional rheology plot for Example 2 comparative modified polymers.

[0016] Figure 2 is a VanGurp-Palmen Plot for Example 2 comparative modified copolymers and their comparison with raw materials.

[0017] Figure 3 provides a complex viscosity vs. frequency plot for Example 2 comparative modified copolymers and their comparison with raw materials.

DETAILED DESCRIPTION

[0018] This invention is related to polyolefins modified by hydrosilylation. Methods of producing these modified polyolefins are also disclosed. Articles comprising these modified polyolefins are also within the scope of this invention.

[0019] The present invention relates to ethylene-based hydrosilylated polyolefins and blends thereof, especially for blown film applications. Films made using conventional high density polyethylene typically have low processability and often tend to have gels. The low processability of these HDPE polymers coupled with the undesirable gel formation affects bubble stability in blown film processes. Current attempts to improve this involve adding LDPE at low loadings, typically at around 5 wt%; however, this generally leads to an undesirable decrease in mechanical properties such as dart drop strength, bubble stability, and tear properties.

[0020] The inventors have surprisingly found that blends of the hydrosilylated polyolefins (and/or macromers) disclosed herein with HDPE, even at lower loadings than traditionally used for LDPE, demonstrated improved processability without the same sacrifice of desirable properties such as haze, internal haze, and desired mechanical properties. This provides a cost advantage as less of the modified polyolefin is needed. The inventive processes to produce these modified polyolefins, the modified polyolefins, and applications for their use are described, in turn, below. Note that any definitions not set forth herein are described in detail in "Branched Polyethylenes by Hydrosilation Grafting to

Improve Processability of Polyethylene", U.S. S.N. , filed concurrently herewith.

Processes to Produce Modified Polyolefins

[0021] This invention relate to processes to prepare a modified polyolefin comprising the steps of:

(i) contacting a non-metallocene catalyst, a hydrosilylation modifier, and one or more vinyl terminated polyolefin selected from a vinyl terminated polyolefin and a vinyl terminated macromonomer;

wherein when the vinyl terminated polyolefin is a vinyl terminated macromonomer, the hydrosilylation modifier is represented by one of more of the formulae:

wherein when the vinyl terminated polyolefin is a vinyl terminated polyolefin, the hydrosilylation modifier is represented by the formula:

wherein R ¹ is hydrogen, Z', or a Q to a C20 substituted or unsubstituted hydrocarbyl group; and wherein Z' is a group represented by the formula:

R ⁴ L ³ — Si H

R ⁵

each R ² , R ³ , R ⁴ , and R ⁵ , independently, is a H, or a Ci to a C20 substituted or unsubstituted hydrocarbyl group, where R ² and R ³ and/or R ⁴ and R ⁵ may form a cyclic structure with Si;

each L, L ¹ , L ² , and L ³ , independently, is a bond or a linking group;

m is an integer from 1 to 1000;

n is an integer from 1 to 1000;

0 is an integer from 0 to 1000;

each of X ¹ and X ² , independently, is hydrogen or a Q to a C20 substituted or unsubstituted hydrocarbyl group;

wherein the vinyl terminated polyolefin is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms and at least 5% allyl chain ends; and

(ii) obtaining a modified polyolefin.

[0022] Accordingly, this invention relates to a process to modify polyolefins, for example, high density polyethylene (HDPE), comprising contacting a non-metallocene catalyst with a hydrosilylation modifier (typically a polyhydrosilane), and one or more vinyl terminated polyolefins. "Modified polyolefin," "hydrosilylated polyolefin," and "polyhydrosilane-modified polyolefin" may be used interchangeably throughout this disclosure.

[0023] Each of the non-metallocene catalyst, the hydrosilylation modifier, and the vinyl terminated polyolefins will be discussed in turn, below. The reactants are typically combined in a reaction zone, such as a BRABENDER™ extruder, mill equipment, a reaction vessel or a stirred tank reactor. Preferably, the process is carried out without the use of a solvent (except the solvent that may be present in the catalyst, if the catalyst used is in a solution formulation). Preferably, the process of this invention occurs in the melt phase. Preferably, the process of this invention occurs in an extruder such as a BRABENDER™ extruder. Preferably, the process occurs at a temperature in the range of from 60°C to 300°C, and more preferably from 100°C to 250°C.

[0024] The process may be batch, semi-batch, or continuous. As used herein, the term "continuous" means a system that operates without interruption or cessation. For example, a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.

[0025] Preferably, the productivity of the process is at least 200 g of a hydrosilane- modified polyolefin per mmol of catalyst per hour, preferably at least 5000 g/mmol/hour, preferably at least 10,000 g/mmol/hr, preferably at least 300,000 g/mmol/hr.

[0026] This invention further relates to a process, preferably an in-line process, preferably a continuous process, to produce a modified polyolefin, comprising introducing polymer and non-metallocene catalyst into a reactor, obtaining a reactor effluent containing vinyl terminated polyolefin, optionally removing (such as flashing off) any solvent, unused monomer, and/or other volatiles, obtaining vinyl terminated polyolefin (such as those described herein), introducing vinyl terminated polyolefin, non-metallocene catalyst, and hydrosilylation modifier, as described herein, into a reaction zone (such as a reactor, an extruder, a pipe, and/or a pump), and obtaining the modified polyolefin described herein.

[0027] Typically, the modified polyolefin is added in small amounts to a base polymer, in order to improve the properties of the blend as compared to the base polymer alone. The base polymer may be comprised of one or more other polymers, including but not limited to, thermoplastic polymer(s) and/or elastomer(s). Accordingly, the process may further comprise: (iii) adding a polymer; and, (iv) obtaining a blend comprising the modified polyolefin. Preferably, the polymer from step (iii) is added during step (i). Alternately, the polymer from step (iii) is added after step (i).

[0028] Preferably, the amount of modified polyolefin in the blend is from 0.5 wt% to 10.0 wt%, based on the total weight of the blend. Preferably, the amount of modified polyolefin is from 0.5 wt% to 5.0 wt%, based on the total weight of the blend. Most preferably, the amount of modified polyolefin is from 0.5 wt% to 3.0 wt%, based on the total weight of the blend.

[0029] Typically, the amount of base polymer in the blend is from 90.0 wt% to 99.5 wt%, based on the total weight of the blend. Preferably, the amount of base polymer is from 95.0 wt% to 99.5 wt%, based on the total weight of the blend. Most preferably, the amount of modified polyolefin is from 97.0 wt% to 99.5 wt%, based on the total weight of the blend. Non-Metallocene Catalyst

[0030] Suitable non-metallocene catalysts include, for example, chloroplatinic acid, platinum complexes such as platinum cyclovinylmethylsiloxane from Gelest Inc. (Morrisville, PA), rhodium complexes, peroxides, for example TRIGONOX-101 from Akzo Nobel (Baton Rouge, LA) and di-cumyl peroxide, Ziegler Natta catalysts, and iridium, cobalt, ruthenium, osmium, nickel and palladium complexes.

[0031] Preferably, the non-metallocene catalyst is one or more of:

platinum-divinyltetramethyldisiloxane complex (desirably, in a solvent such as xylene); platinum-carbonyl-cyclovinylmethylsiloxane complex; platinum- cyclovinylmethylsiloxane complex; platinum-octanal/octanol complex; hexachloroplatinic acid; and dimethylplatinum cyclooctadiene complex; all available from Gelest Inc. (Morrisville, PA).

[0032] Preferably, the non-metallocene catalyst is a platinum-cyclovinylmethylsiloxane complex, having the following structure:

[0033] The amount of non-metallocene catalyst used may range from 5 ppm of metal to 1000 ppm. Preferably, the amount of non-metallocene catalyst used ranges from 5 ppm to 25 ppm of metal. For example, 18 ppm platinum of a platinum catalyst may be used.

Hydrosilylation Modifier

[0034] The polyolefins are modified in this invention with a hydrosilylation modifier, preferably a polyhydrosilane. Preferably, the hydrosilylation modifier is represented by one or more of the following formulae:

wherein R ¹ is hydrogen, Z', or a Q to a C20 substituted or unsubstituted hydrocarbyl group; and wherein Z' is a group represented by the formula:

R ⁴

-L ³ — Si H

R ⁵

each R ² , R ³ , R ⁴ , and R ⁵ , independently, is hydrogen, or a C _j to a C20 substituted or unsubstituted hydrocarbyl group, where R ² and R ³ and/or R ⁴ and R ⁵ may form a cyclic structure with Si;

each L, L ¹ , L ² , and L ³ , independently, is a bond or a linking group;

m is an integer from 1 to 1000;

n is an integer from 1 to 1000; and

0 is an integer from 0 to 1000.

[0035] Preferably, the hydrosilylation modifier is represented by the following formula: H

R ⁴ Si R ⁵

L ³ R ²

I m I ^ϋ

R ¹ R ³

wherein R ¹ is hydrogen, Z', or a to a C20 substituted or unsubstituted hydrocarbyl group; and wherein Z' is a group represented by the formula:

R ⁴ L ³ — Si H

R ⁵

each R ² , R ³ , R ⁴ , and R ⁵ , independently, is hydrogen, or a C _j to a C20 substituted or unsubstituted hydrocarbyl group, where R ² and R ³ and/or R ⁴ and R ⁵ may form a cyclic structure with Si (preferably R ¹ is an aromatic group; preferably phenyl);

each L ¹ , L ² , and L ³ , independently, is a bond or a linking group (preferably, L ¹ is O);

m is an integer from 1 to 1000 (preferably m is 100 to 500); and

0 is zero.

[0036] Preferably of this invention, one or more of the terminal groups of the hydrosilylation modifier is a hydrogen atom, or a to a C20 substituted or unsubstituted hydrocarbyl group. Each hydrosilylation modifier has at least one hydrogen atom attached to a silicon group. This hydrogen atom reacts during the hydrosilylation reaction with the vinyl group of the polyolefin to be modified. Where one of the terminal groups is hydrogen, this provides an additional site for reaction during the hydrosilation process. Accordingly, more than one mole of vinyl terminated polyolefin may react with such a hydrosilylation agent having more than one hydrogen atoms available for reaction.

[0037] Preferably, the hydrosilylation modifier may be poly-(phenyl dimethylhydrosiloxy)siloxane, hydride terminated or polymethylhydrosiloxane, trimethylsilyl terminated, both of which are commercially available from Gelest Inc. (Morrisville, PA).

[0038] Preferably of this invention, the molar ratio of the hydride groups of the hydrosilylation modifier to the vinyl group of the vinyl terminated polyolefin may be 20: 1, preferably 10: 1, more preferably 5: 1, more preferably 3: 1, and more preferably 2: 1. One of skill in the art will appreciate that this ratio may be tailored for desired modified polyolefin structure or for economics.

Vinyl Terminated Polyolefins

[0039] The vinyl terminated polyolefin that is reacted with the hydrosilylation modifier is a substituted or unsubstituted hydrocarbyl group having from 20 or 30 or 40 or 50 or 100 to 10,000 carbon atoms and at least 5% vinyl chain ends (relative to total unsaturations). The vinyl terminated polyolefin may be selected from a vinyl terminated polyolefin and a vinyl terminated macromonomer.

[0040] Preferably, the vinyl terminated polyolefins have greater than 50% allyl chain ends (relative to total unsaturation), preferably greater than 60% allyl chain ends, preferably greater than 70% allyl chain ends, preferably greater than 80% allyl chain ends, preferably greater than 90% allyl chain ends, and most preferably greater than 95% allyl chain ends.

[0041] Preferred vinyl terminated polyolefins include high density polyethylene (HDPE), for example those commercially available from ExxonMobil Chemical Company (Baytown, Texas) under the tradename PAXON™ polyethylene.

[0042] Preferably herein, the vinyl terminated polyolefin comprises vinyl terminated macromonomers (also referred to as "vinyl terminated oligomers" or "macromers"), and most preferably, the vinyl terminated polyolefin is a vinyl terminated macromonomer (VTM). Macromonomers having allyl chain ends (as defined below) are referred to as "vinyl terminated macromonomers". Preferably, the vinyl terminated polyolefin comprises macromonomers having at least 5% (at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%; at least 80%, at least 90%, or at least 95%) allyl chain ends (relative to total unsaturation).

[0043] Preferably of the invention, the macromonomers have a Mn in the range of from 300 g/mol to 30,000 g/mol.

[0044] Preferably of the invention, the macromonomers are a recycle stream from another process, such as a polyolefin process, and may comprise a mixture of different macromonomers .

[0045] Preferably of the invention, the vinyl terminated polyolefin comprises a vinyl terminated macromonomer. Preferably, a vinyl terminated macromonomer, includes, one or more of:

(i) a vinyl terminated polymer having a Mn of at least 200 g/mol (measured by NMR) comprising of one or more C ₄ to C ₄ Q higher olefin derived units, where the higher olefin polymer comprises substantially no propylene derived units; and wherein the higher olefin polymer has at least 5% allyl chain ends;

(ii) a copolymer having a Mn of 200 g/mol or more (measured by NMR) comprising (a) from 20 mol% to 99.9 mol% of at least one C5 to C40 higher olefin, and (b) from 0.1 mol% to 80 mol% of propylene, wherein the higher olefin copolymer has at least 40% allyl chain ends;

(iii) a copolymer having a Mn of 200 g/mol or more (measured by !fi NMR), and comprises (a) from 80 mol% to 99.9 mol% of at least one C ₄ olefin, and (b) from 0.1 mol% to 20 mol% of propylene; wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;

(iv) a co-oligomer having a Mn of 200 g/mol to 30,000 g/mol (measured by !fi NMR) comprising 10 mol% to 90 mol% propylene and 10 mol% to 90 mol% of ethylene, wherein the oligomer has at least X% allyl chain ends (relative to total unsaturations), where: 1) X = (-0.94*(mol% ethylene incorporated) + 100), when 10 mol% to 60 mol% ethylene is present in the co-oligomer, 2) X = 45, when greater than 60 mol% and less than 70 mol% ethylene is present in the co-oligomer, and 3) X = (1.83* (mol% ethylene incorporated) -83), when 70 mol% to 90 mol% ethylene is present in the co-oligomer;

(v) a propylene oligomer, comprising more than 90 mol% propylene and less than 10 mol% ethylene wherein the oligomer has: at least 93% allyl chain ends, a number average molecular weight (Mn) of 500 g/mol to 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0, and less than 100 ppm aluminum;

(vi) a propylene oligomer, comprising: at least 50 mol% propylene and from 10 mol% to 50 mol% ethylene, wherein the oligomer has: at least 90% allyl chain ends, a Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, wherein monomers having four or more carbon atoms are present at from 0 mol% to 3 mol%;

(vii) a propylene oligomer, comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 mol% to 5 mol% C ₄ to olefin, wherein the oligomer has: at least 90% allyl chain ends, a Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0;

(viii) a propylene oligomer, comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 mol% to 5 mol% diene (preferably such as C ₄ to alpha- omega dienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene), wherein the oligomer has: at least 90% allyl chain ends, a Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7: 1 to 1.35: 1.0;

(ix) a homo-oligomer, comprising propylene, wherein the oligomer has: at least 93% allyl chain ends, a Mn of 500 g/mol to 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, and less than 1400 ppm aluminum;

(x) a co-oligomer having a Mn (^H NMR) of 7,500 to 60,000 g/mol comprising one or more alpha olefin derived units comprising ethylene and/or propylene, having 50% or greater allyl chain ends, relative to total number of unsaturated chain ends, and a g'vis of 0.90 or less (g'vis is determined using GPC-DRI, as described below);

(xi) a branched polyolefin having a Mn (GPC) greater than 60,000 g/mol comprising one or more alpha olefins comprising ethylene and/or propylene, having: (i) 50% or greater allyl chain ends, relative to total unsaturated chain ends; (ii) a g'vis of 0.90 or less; and optionally, (iii) a bromine number which, upon complete hydrogenation, decreases by at least 50% (bromine number is determined by ASTM D 1 159); and

(xii) a branched polyolefin having a Mn (!H NMR) of less than 7,500 g/mol comprising one or more alpha olefin derived units comprising ethylene and/or propylene, having: a ratio of percentage of saturated chain ends to percentage of allyl chain ends of 1.2 to 2.0 and 50% or greater allyl chain ends, relative to total unsaturated chain ends.

[0046] Any of the vinyl terminated macromonomers described herein may be homopolymers, copolymers, terpolymers, and so on.

[0047] Preferably, the vinyl terminated macromonomers may have a Tg of less than 0°C or less (as determined by differential scanning calorimetry as described below), preferably -10°C or less, more preferably -20°C or less, more preferably -30°C or less, more preferably - 50°C or less.

[0048] Preferably, the vinyl terminated macromonomers described herein may have a melting point (DSC first melt, as described below) of from 60°C to 130°C, alternately 50°C to 100°C. More preferably, the vinyl terminated macromonomers described herein have no detectable melting point by DSC following storage at ambient temperature (23°C) for at least 48 hours.

[0049] Preferably, the vinyl terminated macromonomers may be a liquid at 25°C. Also preferably, the vinyl terminated macromonomers may have an isobutyl chain end to allylic vinyl group ratio of 0.7: 1 to 1.35: 1.0, preferably 0.8: 1 to 1.35: 1.0, and more preferably 0.8: 1 to 1.2: 1.0.

[0050] Preferably, the vinyl terminated macromonomers may have less than 3 wt% of functional groups selected from hydroxide, aryls and substituted aryls, halogens, alkoxys, carboxylates, esters, acrylates, oxygen, nitrogen, and carboxyl, preferably less than 2 wt%, more preferably less than 1 wt%, more preferably less than 0.5 wt%, more preferably less than 0.1 wt%, more preferably 0 wt%, based upon the weight of the oligomer.

[0051] Vinyl terminated macromonomers generally have a saturated chain end (or terminus) and/or an unsaturated chain end or terminus. The unsaturated chain end of the vinyl terminated macromonomer comprises an "allyl chain end" or a "3-alkyl" chain end. An allyl chain end is represented by CH^CH-CH^., as shown in the formula: x" M

where M represents the polymer chain. "Allylic vinyl group," "allyl chain end," "vinyl chain end," "vinyl termination," "allylic vinyl group," and "vinyl terminated" are used interchangeably in the following description. The number of allyl chain ends, vinylidene chain ends, vinylene chain ends, and other unsaturated chain ends is determined using ^l R NMR at 120°C using deuterated tetrachloroethane as the solvent on an at least 250 MHz NMR spectrometer, and in selected cases, confirmed by ¹³ C NMR. Resconi has reported proton and carbon assignments (neat perdeuterated tetrachloroethane used for proton spectra, while a 50:50 mixture of normal and perdeuterated tetrachloroethane was used for carbon spectra; all spectra were recorded at 100°C on a BRUKER spectrometer operating at 500 MHz for proton and 125 MHz for carbon) for vinyl terminated oligomers in J. American Chemical Soc, 1 14, 1992, pp. 1025-1032 that are useful herein. Allyl chain ends are reported as a molar percentage of the total number of moles of unsaturated groups (that is, the sum of allyl chain ends, vinylidene chain ends, vinylene chain ends, and the like). Note that any description of the VTM not set forth herein are described in detail in "Branched Polyethylenes by Hydrosilation Grafting to Improve Processability of Polyethylene",

U.S. S.N. , filed concurrently herewith

Modified Polyolefins

[0052] This invention also relates to a modified polyolefin represented by the formula:

wherein:

Z is a group represented by the formula:

L ³ — Si PO ¹

wherein PO ¹ is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms;

Pv ¹ is Z, hydrogen, a Q to a C20 substituted or unsubstituted hydrocarbyl group, or PO ⁴ , wherein PO ⁴ is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms;

each R ² , R ³ , R ⁴ , and R ⁵ , independently, is hydrogen, a Q to a C20 substituted or unsubstituted hydrocarbyl group, wherein R ² and R ³ and/or R ⁴ and R ⁵ may form a cyclic structure with Si, or, a PO ⁴ ;

each L ¹ , L ² , and L ³ , independently, is a bond or a linking group;

m is an integer from 1 to 1000;

0 is an integer from 0 to 1000; and

X ¹ and X ² , each independently, is hydrogen, a C[ to a C20 substituted or unsubstituted hydrocarbyl group, or a PO ⁴ ;

wherein each PO ¹ and PO ⁴ may be the same or different.

[0053] This invention also relates to a modified polyolefin represented by the formula:

wherein:

Z is a group represented by the formula: R ⁴ L ³ — Si PO ¹

R ⁵

wherein PO ¹ is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms derived from a vinyl terminated macromonomer;

each R ¹ , R ² , R ³ , R ⁴ , and R ⁵ , independently, is a H, a Q to a C20 substituted or unsubstituted hydrocarbyl group, where R ² and R ³ may form a cyclic structure with Si, or a PO ⁴ , wherein PO ⁴ is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms derived from a vinyl terminated macromonomer;

each L, L ¹ , L ² , and L ³ , if present, is a bond or a linking group;

m is an integer from 1 to 1000;

n is an integer from 1 to 1000;

0 is an integer from 0 to 1000; and

X ¹ and X ² , each independently, is hydrogen, a C[ to a C20 substituted or unsubstituted hydrocarbyl group, or a PO ⁴ ;

wherein each PO ¹ and PO ⁴ may be the same or different.

[0054] Each PO ¹ and PO ⁴ , independently, is derived from a vinyl terminated polyolefin or a vinyl terminated macromonomer. Preferably, the PO ¹ and/or PO ⁴ in the formulae above is a hydrocarbyl or substituted hydrocarbyl having 100 to 10,000 carbon atoms, preferably 500 to 10,000, preferably 1000 to 10,000, preferably 5000 to 10,000 carbon atoms, preferably PO ¹ and/or PO ⁴ is derived from substituted or unsubstituted eicosene, polyethylene or polypropylene.

[0055] Preferably of the invention, R ¹ is an aromatic group; L ¹ is an oxygen atom; L ³ is an oxygen atom; each R ⁴ and R ⁵ , independently, is a to a C20 substituted or unsubstituted hydrocarbyl group; m is 100 to 500; and 0 is 0.

[0056] Preferably, the modified polyolefin has a Mn of from 500 to 50,000 g/mol, preferably from 1000 to 30,000 g/mol, preferably from 1500 to 10,000 g/mol. Preferably the "polyolefin" portion of the hydrosilane-modified polyolefin is derived from a homopolymer, homo-oligomer, copolymer or co-oligomer comprising one or more C2 to C40 olefins, preferably C2 to C40 alpha-olefins, preferably ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.

[0057] Preferably, the hydrosilane-modified polyolefin is an oligomer having a Mn of from 500 to 21,000 g/mol (preferably 700 to 21,000, preferably 800 to 20,000 g/mol) comprising one or more alpha-olefins selected from the group consisting of C2 to C40 alpha- olefins, preferably ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene. Preferably, the oligomer portion of the polyhydrosilane-modified polyolefin is an ethylene oligomer, e.g., a homo-oligomer of ethylene or co-oligomer of ethylene and up to 50 mol% (preferably from 0.5 mol% to 25 mol%, preferably from 1 mol% to 20 mol%) of one or more C2 to C40 alpha-olefin comonomers, preferably selected from the group consisting of propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene. Alternately, the oligomer portion of the polyhydrosilane-modified polyolefin is a propylene oligomer, e.g., a homo-oligomer of propylene or co-oligomer of propylene and up to 50 mol% (preferably from 0.5 mol% to 25 mol%, preferably from 1 mol% to 20 mol%) of one or more C2 to C40 alpha-olefin comonomers, preferably selected from the group consisting of ethylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.

[0058] Preferably, the polyhydrosilane-modified polyolefin is a polymer having a Mn of greater than 21,000 g/mol (preferably from 25,000 to 100,000, preferably 25,000 to 50,000 g/mol) comprising one or more alpha-olefins selected from the group consisting of C2 to C40 alpha-olefins, preferably ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene. Preferably, the polymer portion of the polyhydrosilane- modified polyolefin is an ethylene polymer, e.g., a homopolymer of ethylene or co-polymer of ethylene and up to 50 mol% (preferably from 0.5 mol% to 25 mol%, preferably from 1 mol% to 20 mol%) of one or more C3 to C40 alpha-olefin comonomers, preferably selected from the group consisting of propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene. Alternately, the polymer portion of the polyhydrosilane-modified polyolefin is propylene polymer, e.g., a homopolymer of propylene or a co-polymer of propylene and up to 50 mol% (preferably from 0.5 mol% to 25 mol%, preferably from 1 mol% to 20 mol%) of one or more C2 to C40 alpha-olefins comonomers, preferably selected from the group consisting of ethylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene.

[0059] More preferably, the polyhydrosilane-modified polyolefins consist essentially of propylene, functional group and, optionally, ethylene. Alternately, C4 olefins (such as isobutylene, butadiene, n-butene) are substantially absent from the polyhydrosilane-modified polyolefins. Alternately, C4.20 olefins are substantially absent from the polyhydrosilane- modified polyolefins. Alternately, isobutylene is substantially absent from the polyhydrosilane-modified polyolefins. By substantially absent is meant that the monomer is present in the polyolefin at 1 wt% or less, preferably at 0.5 wt% or less, preferably at 0 wt%.

[0060] Preferably, the polyhydrosilane-modified polyolefins produced herein have a melting point (DSC, second melt) of 100°C or more, preferably 120°C or more, preferably 130°C or more. More preferably, the polyhydrosilane-modified polyolefin produced herein is a polyhydrosilane-modified propylene polymer having a melting point (DSC, second melt) of 145°C or more, preferably 150°C or more, preferably 155°C or more. Preferably, the polyhydrosilane-modified polyolefin produced herein is a polyhydrosilane-modified ethylene polymer having a melting point (DSC, second melt) of 100°C or more, preferably 110°C or more, preferably 125°C or more.

[0061] The polyhydrosilane-modified polyolefins may be characterized by any degree of tacticity, including isotacticity or syndiotacticity, and/or may be atactic. Preferably, the polyhydrosilane-modified polyolefin has more than 50% meso dyads as measured by ¹³ C NMR, preferably more than 60%. Alternatively, the polyhydro-silane modified polyolefin has more than 50% racemic dyads as measured by ¹³ C NMR, preferably more than 60%.

[0062] Particularly useful polyhydrosilane-modified polyolefins may be isotactic, highly isotactic, syndiotactic, or highly syndiotactic propylene polymer, particularly isotactic polypropylene. As used herein, "isotactic" is defined as having at least 10% isotactic pentads, preferably having at least 40% isotactic pentads of methyl groups derived from propylene according to analysis by ¹³ C NMR. As used herein, "highly isotactic" is defined as having at least 60% isotactic pentads according to analysis by ¹³ C NMR. Most preferably, the polyhydrosilane-modified polyolefin (preferably polypropylene) has at least 85% isotacticity. As used herein, "syndiotactic" is defined as having at least 10% syndiotactic pentads, preferably at least 40%, according to analysis by ¹³ C NMR. As used herein, "highly syndiotactic" is defined as having at least 60% syndiotactic pentads according to analysis by ¹³ C NMR. More preferably, the polyhydrosilane modified polyolefin (preferably polypropylene) has at least 85% syndiotacticity.

[0063] Preferably, the polyhydrosilane-modified polyolefins described herein have less than 10% allyl chain ends, preferably less than 8%, preferably less than 6%, preferably less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%, preferably less than 1% (relative to total unsaturations as measured by NMR, using the protocol described in USSN 12/143,663, filed on June 20, 2008). No hydrogen or chain transfer/termination agent should be used during functionalization, derivatization, or stripping (of unreacted monomer) for measurement of unsaturations.

[0064] More preferably, the modified polyolefin may have a branching index, g' _vjs (as determined by GPC) greater than that of the unmodified polyolefin. The modified polyolefin produced herein has a branching index, g' _vjs (as determined by GPC), of 0.98 or less, alternately 0.96 or less, alternately 0.95 or less, alternately 0.93 or less, alternately 0.90 or less, alternately 0.85 or less, alternately 0.80 or less, alternately 0.75 or less, alternately 0.70 or less, alternately 0.65 or less, alternately 0.60 or less, alternately 0.55 or less.

Blends with Ethylene Polymers

[0065] The materials described herein may be combined with at least one ethylene polymer to prepare modified polyethylene blends.

[0066] In one aspect of the invention, the ethylene polymer is selected from ethylene homopolymer, ethylene copolymers, and blends thereof. Useful copolymers may comprise one or more comonomers in addition to ethylene and can be a random copolymer, a statistical copolymer, a block copolymer, and/or blends thereof. In particular, the ethylene polymer blends described herein may be physical blends or in situ blends of more than one type of ethylene polymer or blends of ethylene polymers with polymers other than ethylene polymers where the ethylene polymer component is the majority component (e.g., greater than 50 wt%). The method of making the polyethylene is not critical, as it can be made by slurry, solution, gas phase, high pressure, or other suitable processes, and by using catalyst systems appropriate for the polymerization of polyethylenes, such as Ziegler-Natta-type catalysts, chromium catalysts, metallocene-type catalysts, other appropriate catalyst systems, or combinations thereof, or by free-radical polymerization. Preferably, the ethylene polymers are made by the catalysts, activators and processes described in U.S. Patent Nos. 6,342,566; 6,384, 142; 5,741,563; PCT publications WO 03/040201 ; and WO 97/19991. Such catalysts are well known in the art, and are described in, for example, ZIEGLER CATALYSTS (Gerhard Fink, Rolf Mulhaupt and Hans H. Brintzinger, eds., Springer-Verlag 1995); Resconi et al; and I, II METALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000).

[0067] Preferred ethylene polymers and copolymers that are useful in this invention include those sold by ExxonMobil Chemical Company in Houston Texas, including those sold as ExxonMobil HDPE, ExxonMobil LLDPE, and ExxonMobil LDPE; and those sold under the ENABLE™, EXACT™, EXCEED™, ESCORENE™, EXXCO™, ESCOR™, PAXON™, and OPTEMA™ tradenames. [0068] Preferably of the invention, the ethylene copolymers preferably have a composition distribution breadth index (CDBI) of 60% or more, preferably 60% to 80%, preferably 65% to 80%. Preferably, the ethylene copolymer has a density of 0.910 to 0.950 g/cm ³ (preferably 0.915 to 0.940 g/cm ³ , preferably 0.918 to 0.925 g/cm ³ ) and a CDBI of 60% to 80%, preferably between 65% and 80%. Preferably these polymers are metallocene polyethylenes (mPEs).

[0069] More preferably, the ethylene copolymer comprises one or more mPEs described in US 2007/0260016 and U.S. Patent No. 6,476,171, e.g., copolymers of an ethylene and at least one alpha olefin having at least 5 carbon atoms obtainable by a continuous gas phase polymerization using supported catalyst of an activated molecularly discrete catalyst in the substantial absence of an aluminum alkyl based scavenger (e.g., triethylaluminum, trimethylaluminum, tri-isobutyl aluminum, tri-n-hexylaluminum, and the like), which polymer has a Melt Index of from 0.1 to 15 (ASTM D 1238, condition E); a CDBI of at least 70%, a density of from 0.910 to 0.930 g/cc; a Haze (ASTM D1003) value of less than 20; a Melt Index ratio (I21 I2, ASTMD 1238) of from 35 to 80; an averaged Modulus (M) (as defined in U.S. Patent No. 6,255,426) of from 20,000 to 60,000 psi (13790 to 41369 N/cm ² ); and a relation between M and the Dart Impact Strength (26 inch, ASTM D 1709) in g/mil (DIS) complying with the formula:

DIS>0.8 x [100+ε( ^{1 1} ·71-0·000268χΜ+2.183χ10-9χΜ2)] _;

where "e" represents 2.1783, the base Napierian logarithm, M is the averaged Modulus in psi and DIS is the 26 inch (66cm) dart impact strength. (See U.S. Patent No. 6,255,426 for further description of such ethylene polymers.)

[0070] More preferably, the ethylene polymer comprises a Ziegler-Natta polyethylene, e.g., CDBI less than 50, preferably having a density of 0.910 to 0.950 g/cm ³ (preferably 0.915 to 0.940 g/cm ³ , preferably 0.918 to 0.925 g/cm ³ ).

[0071] More preferably, the ethylene polymer comprises olefin block copolymers as described in EP 1 716 190.

[0072] More preferably, the ethylene polymer is produced using chrome based catalysts, such as, for example, in U.S. Patent No. 7,491,776 including that fluorocarbon does not have to be used in the production. Commercial examples of polymers produced by chromium include the Paxon™ grades of polyethylene produced by ExxonMobil Chemical Company, Houston Texas. [0073] More preferably, the ethylene polymer comprises ethylene and an optional comonomer of propylene, butene, pentene, hexene, octene nonene or decene, and said polymer has a density of more than 0.86 to less than 0.910 g/cm ³ , an Mw of 20,000 g/mol or more (preferably 50,000 g/mol or more) and a CDBI of 90% or more.

[0074] More preferably, the ethylene polymer comprises a substantially linear and linear ethylene polymers (SLEPs). Substantially linear ethylene polymers and linear ethylene polymers and their method of preparation are fully described in U.S. Patent Nos. 5,272,236; 5,278,272; 3,645,992; 4,937,299; 4,701,432; 4,937,301 ; 4,935,397; 5,055,438; EP 129,368; EP 260,999; and WO 90/07526. As used herein, "a linear or substantially linear ethylene polymer" means a homopolymer of ethylene or a copolymer of ethylene and one or more alpha-olefin comonomers having a linear backbone (i.e., no cross linking), a specific and limited amount of long-chain branching or no long-chain branching, a narrow molecular weight distribution, a narrow composition distribution (e.g., for alpha-olefin copolymers), or a combination thereof. More explanation of such polymers is discussed in U.S. Patent No. 6,403,692.

[0075] Ethylene homopolymers and copolymers useful in this invention typically have:

1. an M _w of 20,000 g/mol or more, 20,000 to 2,000,000 g/mol preferably 30,000 to 1,000,000, preferably 40,000 to 200,000, preferably 50,000 to 750,000, as measured by size exclusion chromatography according to the procedure described in the Test Methods section ofUSSN 13/584, 137, filed August 13, 2012; and/or

2. an M _w /M _n of 1 to 40, preferably 1.6 to 20, more preferably 1.8 to 10, more preferably 1.8 to 4, preferably 8 to 25 as measured by size exclusion chromatography as described in the Test Methods section of USSN 13/584, 137, filed August 13, 2012; and/or

3. a T _m of 30°C to 150°C, preferably 30°C to 140°C, preferably 50°C to 140°C, more preferably 60°C to 135°C as determined by the DSC method described in the Test Methods section of USSN 13/584, 137, filed August 13, 2012; and/or

4. a crystallinity of 5% to 80%, preferably 10% to 70%, more preferably 20% to 60% (alternatively, the polyethylene may have a crystallinity of at least 30%, preferably at least 40%, alternatively at least 50%), where crystallinity is determined by the DSC method described in the Test Methods section of USSN 13/584, 137, filed August 13, 2012; and/or

5. a heat of fusion of 300 J/g or less, preferably 1 to 260 J/g, preferably 5 to 240 J/g, preferably 10 to 200 J/g as measured by the DSC method described in the Test Methods section of USSN 13/584, 137, filed August 13, 2012; and/or 6. a crystallization temperature (Tc) of 15°C to 130°C, preferably 20°C to 120°C, preferably 25°C to 110°C, preferably 60°C to 125°C, as measured by the method described in the Test Methods section of USSN 13/584, 137, filed August 13, 2012; and/or

7. a heat deflection temperature of 30°C to 120°C, preferably 40°C to 100°C, more preferably 50°C to 80°C as measured according to ASTM D648 on injection molded flexure bars, at 66 psi load (455kPa); and/or

8. a Shore hardness (D scale) of 10 or more, preferably 20 or more, preferably 30 or more, preferably 40 or more, preferably 100 or less, preferably from 25 to 75 (as measured by ASTM D 2240); and/or

9. a percent amorphous content of at least 50%, alternatively at least 60%, alternatively at least 70%, even alternatively between 50% and 95%, or 70% or less, preferably 60% or less, preferably 50% or less, as determined by subtracting the percent crystallinity from 100 as described in the Test Methods section of U.S. Publication No. 2013-021 1008; and/or

10. a branching index (g' _v i _s ) °f 0.97 or more, preferably 0.98 or more, preferably 0.99 or more, preferably 1, as measured using the method described in the Test Methods section of USSN 13/584, 137, filed August 13, 2012; and/or

11. a density of 0.860 to 0.980 g/cm ³ (preferably from 0.880 to 0.940 g/cm ³ , preferably from 0.900 to 0.935 g/cm ³ , preferably from 0.910 to 0.930 g/cm ³ ) (alternately from 0.85 to 0.97 g/cm ³ , preferably 0.86 to 0.965 g/cm ³ , preferably 0.88 to 0.96 g/cm ³ , alternatively between 0.860 and 0.910 g/cm ³ , alternatively between 0.910 and 0.940 g/cm ³ , or alternatively between 0.94 to 0.965 g/cm ³ ) (determined according to ASTM D 1505 using a density-gradient column on a compression-molded specimen that has been slowly cooled to 25°C (i.e., over a period of 10 minutes or more) and allowed to age for a sufficient time that the density is constant within +/- 0.001 g/cm ³ ).

[0076] Preferably, the polyethylene comprises less than 20 mol% propylene units (preferably less than 15 mol%, preferably less than 10 mol%, preferably less than 5 mol%, preferably 0 mol% propylene units).

[0077] More preferably of the invention, the ethylene polymer is an ethylene copolymer, either random, or block, of ethylene and one or more comonomers selected from C3 to C20 a- olefins, typically from C3 to C Q a-olefins More preferably. Preferably, the comonomers are present from 0.1 wt% to 50 wt% of the copolymer, from 0.5 wt% to 30 wt% more preferably, from 1 wt% to 15 wt% even more preferably, and from 0.1 wt% to 5 wt% even more preferably, wherein a desirable copolymer comprises ethylene and C3 to C20 a-olefin derived units in any combination of any upper wt% limit with any lower wt% limit described herein. Preferably, the ethylene copolymer will have a weight average molecular weight of from greater than 8,000 g/mol, greater than 10,000 g/mol more preferably, greater than 12,000 g/mol even more preferably, greater than 20,000 g/mol even more preferably, less than 1,000,000 g/mol even more preferably, and less than 800,000 g/mol even more preferably, wherein a desirable copolymer may comprise any upper molecular weight limit with any lower molecular weight limit described herein.

[0078] More preferably, the ethylene copolymer comprises ethylene and one or more other monomers selected from the group consisting of C3 to C20 linear, branched or cyclic monomers, and Preferably is a C3 to linear or branched alpha-olefin, preferably butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-l, 3 -methyl pentene-1, 3,5,5-trimethyl-hexene-l, and the like. The monomers may be present at up to 50 wt%, preferably from 0 wt% to 40 wt%, more preferably from 0.5 wt% to 30 wt%, more preferably from 2 wt% to 30 wt%, more preferably from 5 wt% to 20 wt%.

[0079] Preferred linear alpha-olefins useful as comonomers for the ethylene copolymers useful in this invention include C3 to Cg alpha-olefins, more preferably 1 -butene, 1 -hexene, and 1 -octene, even more preferably 1 -hexene. Preferred branched alpha-olefins include 4- methyl-1 -pentene, 3 -methyl- 1 -pentene, and 3,5,5-trimethyl-l-hexene, 5-ethyl-l -nonene. Preferred aromatic-group-containing monomers contain up to 30 carbon atoms. Suitable aromatic-group-containing monomers comprise at least one aromatic structure, preferably from one to three, more preferably a phenyl, indenyl, fluorenyl, or naphthyl moiety. The aromatic-group-containing monomer further comprises at least one polymerizable double bond such that after polymerization, the aromatic structure will be pendant from the polymer backbone. The aromatic-group containing monomer may further be substituted with one or more hydrocarbyl groups including but not limited to to alkyl groups. Additionally, two adjacent substitutions may be joined to form a ring structure. Preferred aromatic-group- containing monomers contain at least one aromatic structure appended to a polymerizable olefinic moiety. Particularly preferred aromatic monomers include styrene, alpha- methylstyrene, para-alkylstyrenes, vinyltoluenes, vinylnaphthalene, allyl benzene, and indene, especially styrene, paramethyl styrene, 4-phenyl-l -butene, and allyl benzene.

[0080] Preferred diolefin monomers useful in the ethylene polymer or copolymer include any hydrocarbon structure, preferably C ₄ to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). It is further preferred that the diolefin monomers be selected from alpha, omega-diene monomers (i.e., di-vinyl monomers). More preferably, the diolefin monomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms. Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7- octadiene, 1,8 -nonadiene, 1,9-decadiene, 1, 10-undecadiene, 1, 1 1 -dodecadiene, 1, 12- tridecadiene, 1,13 -tetradecadiene, and low molecular weight polybutadienes (M _w less than 1000 g/mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene, or higher ring containing diolefins with or without substituents at various ring positions.

Applications

[0081] The modified polyolefins of this invention (and blends thereof as described above) may be used in any known thermoplastic or elastomer application. Examples include uses in molded parts, films, tapes, sheets, tubing, hose, sheeting, wire and cable coating, adhesives, shoe soles, bumpers, gaskets, bellows, films, fibers, elastic fibers, nonwovens, spun bonds, corrosion protection coatings and sealants. Preferred uses include additives for lubricants and/or fuels and in blown film applications.

[0082] This invention further relates to:

1. A modified polyolefin represented by the formula:

wherein:

Z is a group represented by the formula:

L ³ — Si PO ¹

Pv ⁵ wherein PO ¹ is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms;

R ¹ is Z, hydrogen, a Q to a C20 substituted or unsubstituted hydrocarbyl group, or PO ⁴ , wherein PO ⁴ is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms (preferably R ¹ is a methyl group or PO ⁴ ; alternately R ¹ is an aromatic group, preferably phenyl; preferably R ¹ is a phenyl group and R ⁴ and R ⁵ are methyl groups);

each R ² , R ³ , R ⁴ , and R ⁵ , independently, is hydrogen, a C _[ to a C20 substituted or unsubstituted hydrocarbyl group, wherein R ² and R ³ and/or R ⁴ and R ⁵ may form a cyclic structure with Si, or, a PO ⁴ ;

each L ¹ , L ² , and L ³ , independently, is a bond or a linking group (preferably each L ¹ , L ² , and L ³ , independently, is O, S, NR ^A , PR ^B , SiR ^c ₂ , or a Q to a C ₂ o substituted or unsubstituted hydrocarbyl group; wherein each R ^A , R ^B , and R ^c , independently, is hydrogen, or a to a C20 substituted or unsubstituted hydrocarbyl group; preferably each L ¹ , L ² , and L ³ , independently, is O);

m is an integer from 1 to 1000 (preferably m is from 100 to 500);

0 is an integer from 0 to 1000 (preferably 0 is 0; preferably 0 is from 100 to 500); and

X ¹ and X ² , each independently, is hydrogen; a C _[ to a C20 substituted or unsubstituted hydrocarbyl group, or PO ⁴ ;

wherein PO ¹ and PO ⁴ can be the same or different (preferably each of PO ¹ and PO ⁴ , independently, is derived from a vinyl terminated polyolefin selected from a vinyl terminated polyalphaolefin or a vinyl terminated macromonomer; preferably the vinyl terminated polyolefin is ethylene-based; preferably the polyalphaolefin is polyethylene).

2. The modified polyolefin of paragraph 1, wherein R ¹ is an aromatic group (group (preferably phenyl); L ¹ is an oxygen atom; L ³ is an oxygen atom; each R ⁴ and R ⁵ , independently, is a to a C20 substituted or unsubstituted hydrocarbyl group; m is 100 to 500; and 0 is 0.

3. A modified polyolefin represented by the formula:

; or

wherein:

Z is a group represented by the formula:

R ⁴ L ³ — Si PO ¹

R ⁵

wherein PO ¹ is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms derived from a vinyl terminated macromonomer;

each R ¹ , R ² , R ³ , R ⁴ , and R ⁵ , independently, is hydrogen, a to a C20 substituted or unsubstituted hydrocarbyl group, where R ² and R ³ may form a cyclic structure with

Si, or a PO ⁴ ;

wherein PO ⁴ is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms derived from a vinyl terminated macromonomer (preferably the vinyl terminated macromonomer is ethylene-based);

each L, L ¹ , L ² , and L ³ , is a bond or a linking group (preferably each L, L ¹ , L ² , and L ³ , independently, is O, S, NR ^A , PR ^B , SiR ^C 2, or a to a C20 substituted or unsubstituted hydrocarbyl group; wherein each R ^A , R ^B , and R ^c , independently, is hydrogen, or a to a C20 substituted or unsubstituted hydrocarbyl group; preferably each L, L ¹ , L ² , and L ³ , independently, is O;

m is an integer from 1 to 1000 (preferably m is from 100 to 500);

n is an integer 1 to 1000 (preferably n is from 100 to 500);

0 is an integer from 0 to 1000 (preferably 0 is 0; preferably 0 is from 100 to 500); and

X ¹ and X ² , each independently, is hydrogen, a C _[ to a C20 substituted or unsubstituted hydrocarbyl group, or a PO ⁴ .

4. The modified polyolefin of paragraphs 1 to 3, wherein the vinyl terminated macromonomer is one or more of:

(i) a vinyl terminated polymer having a Mn of at least 200 g/mol (measured by NMR) comprising of one or more C ₄ to C ₄ Q higher olefin derived units, where the higher olefin polymer comprises substantially no propylene derived units; and wherein the higher olefin polymer has at least 5% allyl chain ends;

(ii) a copolymer having a Mn of 200 g/mol or more (measured by !fi NMR) comprising (a) from 20 mol% to 99.9 mol% of at least one C5 to C40 higher olefin, and (b) from 0.1 mol% to 80 mol% of propylene, wherein the higher olefin copolymer has at least 40% allyl chain ends;

(iii) a copolymer having a Mn of 200 g/mol or more (measured by NMR), and comprises (a) from 80 mol% to 99.9 mol% of at least one C ₄ olefin, and (b) from 0.1 mol% to 20 mol% of propylene; wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;

(iv) a co-oligomer having a Mn of 200 g/mol to 30,000 g/mol (measured by !fi NMR) comprising 10 mol% to 90 mol% propylene and 10 mol% to 90 mol% of ethylene, wherein the oligomer has at least X% allyl chain ends (relative to total unsaturations), where: 1) X = (-0.94*(mol% ethylene incorporated) + 100), when 10 mol% to 60 mol% ethylene is present in the co-oligomer, 2) X = 45, when greater than 60 mol% and less than 70 mol% ethylene is present in the co-oligomer, and 3) X = (1.83* (mol% ethylene incorporated) -83), when 70 mol% to 90 mol% ethylene is present in the co-oligomer;

(v) a propylene oligomer, comprising more than 90 mol% propylene and less than 10 mol% ethylene wherein the oligomer has: at least 93% allyl chain ends, a number average molecular weight (Mn) of 500 g/mol to 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0, and less than 100 ppm aluminum;

(vi) a propylene oligomer, comprising: at least 50 mol% propylene and from 10 mol% to 50 mol% ethylene, wherein the oligomer has: at least 90% allyl chain ends, a Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, wherein monomers having four or more carbon atoms are present at from 0 mol% to 3 mol%;

(vii) a propylene oligomer, comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 mol% to 5 mol% C ₄ to olefin, wherein the oligomer has: at least 90% allyl chain ends, a Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0;

(viii) a propylene oligomer, comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 mol% to 5 mol% diene (preferably such as C ₄ to alpha- omega dienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene), wherein the oligomer has: at least 90% allyl chain ends, a Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7: 1 to 1.35: 1.0;

(ix) a homo-oligomer, comprising propylene, wherein the oligomer has: at least 93% allyl chain ends, a Mn of 500 g/mol to 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, and less than 1400 ppm aluminum;

(x) a co-oligomer having a Mn (^H NMR) of 7,500 to 60,000 g/mol comprising one or more alpha olefin derived units comprising ethylene and/or propylene, and having 50% or greater allyl chain ends, relative to total number of unsaturated chain ends and a g'vis of 0.90 or less (g'vis is determined using GPC-DRI, as described below);

(xi) a branched polyolefin having a Mn (GPC) greater than 60,000 g/mol comprising one or more alpha olefins comprising ethylene and/or propylene, and having: (i) 50% or greater allyl chain ends, relative to total unsaturated chain ends; (ii) a g'vis of 0.90 or less; and optionally; (iii) a bromine number which, upon complete hydrogenation, decreases by at least 50% (bromine number is determined by ASTM D 1 159); and

(xii) a branched polyolefin having a Mn (^H NMR) of less than 7,500 g/mol comprising one or more alpha olefin derived units comprising ethylene and/or propylene, and having: a ratio of percentage of saturated chain ends to percentage of allyl chain ends of 1.2 to 2.0; and 50% or greater allyl chain ends, relative to total unsaturated chain ends.

5. The modified polyolefin of claim 12, wherein R ¹ is a Cj to a C20 substituted or unsubstituted hydrocarbyl group; L ¹ is an oxygen atom, m is from 100 to 500; each R ² and R ³ , independently, are a to a C20 substituted or unsubstituted hydrocarbyl group; L ² is an oxygen atom; and 0 is from 100 to 500.

6. A blend comprising the modified polyolefin of paragraphs 1 or 3.

7. The blend of paragraph 6, further comprising polyethylene.

8. An article comprising the modified polyolefin of paragraphs 1 to 7 (preferably, the article is a blown film).

9. A process to prepare the modified polyolefin of paragraphs 1 to 5 (carried out in the melt phase), comprising the steps of:

(i) contacting a non-metallocene catalyst (non-metallocene catalyst is one or more of: chloroplatinic acid, platinum complexes such as platinum cyclovinylmethylsiloxane, rhodium complexes, peroxides, such as di-cumyl peroxide, Ziegler Natta catalysts, and iridium, cobalt, ruthenium, osmium, nickel and palladium complexes; more preferably platinum- divinyltetramethyldisiloxane complex (desirably, in a solvent such as xylene); platinum- carbonyl-cyclovinylmethylsiloxane complex; platinum-cyclovinylmethylsiloxane complex; platinum-octanal/octanol complex; hexachloroplatinic acid; and dimethylplatinum cyclooctadiene complex), a hydrosilylation modifier, and one or more vinyl terminated polyolefin selected from a vinyl terminated polyalphaolefin and a vinyl terminated macromonomer;

wherein when the vinyl terminated polyolefin is a vinyl terminated macromonomer, the hydrosilylation modifier is represented by one of more of the formulae:

r

wherein the vinyl terminated polyolefin is a polyalphaolefin, the hydrosilylation modifier is represented by the formula:

H

R ⁴ Si R ⁵

L ³ R ² X ^l 4-L X ii L ² )-X ²

R ¹ R ³

wherein R ¹ is hydrogen, Z', or a Ci to a C20 substituted or unsubstituted hydrocarbyl group; and wherein Z' is a group represented by the formula: R ⁴ L ³ — Si H

R ⁵

each R ² , R ³ , R ⁴ , and R ⁵ , independently, is a H, or a to a C20 substituted or unsubstituted hydrocarbyl group, where R ² and R ³ and/or R ⁴ and R ⁵ may form a cyclic structure with Si; each L, L ¹ , L ² , and L ³ , independently, is a bond or a linking group (each L ¹ , L ² , and L ³ , independently, is O, S, NR ^A , PR ^B , SiR ^C 2, or a to a C20 substituted or unsubstituted hydrocarbyl group; wherein each R ^A , R ^B , and R ^c , independently, is hydrogen, or a Ci to a C20 substituted or unsubstituted hydrocarbyl group);

m is an integer from 1 to 1000;

n is an integer from 1 to 1000;

0 is an integer from 0 to 1000;

each of X ¹ and X ² , independently, is hydrogen or a Q to a C20 substituted or unsubstituted hydrocarbyl group;

the vinyl terminated polyolefm is a substituted or unsubstituted hydrocarbyl group having from 20 to 10,000 carbon atoms (preferably the vinyl terminated polyolefm is one or more of a polyalphaolefin and a vinyl terminated macromonomer; preferably, the vinyl terminated polyolefm of step (i) is ethylene-based) and at least 5% allyl chain ends;

(ii) obtaining a modified polyolefm;

(iii) optionally, adding a polyalphaolefin (preferably, the polyalphaolefin from step (iii) is added during step (i), alternately, the polyalphaolefin from step (iii) is added after step (i); preferably, the polyalphaolefin of step (iii) is polyethylene); and

(iv) obtaining a blend comprising the modified polyolefm.

EXAMPLES

Tests and Materials

[0083] Products were characterized by Ή NMR as follows:

lR NMR data was collected at either 25°C or 120°C (for purposes of the claims, 120°C shall be used) in a 5 mm probe using a Varian spectrometer with a proton frequency of at least 400 MHz or a Bruker 500 MHz. Data was recorded using a maximum pulse width of 45°, 8 seconds between pulses and signal averaging 120 transients. Spectral signals were integrated and the number of unsaturation types per 1000 carbons was calculated by multiplying the different groups by 1000 and dividing the result by the total number of carbons. M _n of the macromer is determined by !fi NMR spectroscopy by comparison of integrals of the aliphatic region to the olefin region as determined using the protocol described in the Experimental section of USSN 12/143,663, filed on June 20, 2008.

[0084] GPC conditions are those described above.

[0085] 1% Secant Modulus (M), reported in pounds per square inch (psi), was measured as specified by ASTM D-882.

[0086] Yield strength and tensile strength, report as pounds per square inch (psi), were measured as specified by ASTM D-882 except that the gauge thickness, reported in mils, was measured using a HEIDENHAIN micrometer. For each film sample, twenty random film thickness data points were measured around the circumference of the bubble. From these measurements, an average gauge measurement was determined and reported.

[0087] Elongation at Yield and Elongation at Break, reported as a percentage (%), were measured as specified by ASTM D-882.

[0088] Elmendorf Tear, reported in grams (g) or grams per mil (g/mil), was measured as specified by ASTM D-1922. Verification of scale was done using the check weight method.

[0089] Haze, reported as a percentage (%), was measured as specified by ASTM D-1003, using procedure A. Internal haze refers to the inherent haze level of the film or molded article, excluding any surface-related contribution. The surface(s) is coated with an ASTM- approved inert liquid (Immersion Oil Type B, typically used for microscopy) to eliminate any contribution to haze from surface topology effects. The resulting haze value is termed internal haze, and is reported as a percentage (%). Haze measurements that include surface topology effects are referred to as total haze. Unless particularly specified, the haze levels reported here are total haze values.

[0090] Dart Drop Impact or Dart Drop Impact Strength (DIS), reported in grams (g) and/or grams per mil (g/mil), was measured as specified by ASTM D-1709, method A, unless otherwise specified.

Polyolefins

[0091] The commercially available polyolefins used in the Examples are as described below in Table 1.

TABLE 1: COMMERCIAL POLYOLEFINS

Polyolefins Source Description

> 95% vinyl chain ends

Ethylene-based polymer;

ExxonMobil Chemicals hexene comonomer;

EXCEED™ 1018CA

(Houston, Texas) MI = l .O g/lO min;

density = 0.918 g/cm ³

Ethylene-hexene copolymer;

ExxonMobil Chemicals metallocene-produced;

EXCEED™ 2018CA

(Houston, Texas) MI = 2.0 g/lOmin;

density = 0.918 g/cm ³

[0092] The commercially available polysiloxanes used in the Examples are as described below in Table 2.

General Procedure for Hydrosilylation

[0093] Vinyl terminated polymers, inclusive of polyolefins and vinyl terminated macromonomers, were modified with various polysiloxane backbones. Reactions were carried out in the melt in a BRABENDER™ extruder. The BRABENDER™ extruder was connected to a nitrogen gas inlet through which a continuous stream of nitrogen gas flowed. The catalyst was added by syringe once the torque stabilized. The silane was added, 1 minute later. The torque dropped initially and then rose to a point where it leveled, generally after 1 to 30 minutes. The modified polyolefin was then removed from the BRABENDER™ extruder and used without further modification.

General Procedure for Modified Polyolefins Blends

[0094] Viscosity matching when blending these hydrosilylated polymers with lower density LLDPE materials was of interest. Blends were prepared (between 10% to 50% vinyl terminated HDPE was blended with a base resin). Additives were used in all samples, except where the base resin already comprises an additive package. Where additional additives were used, the additive package was composed of 500 ppm IRGANOX™ 1076 and 1000 ppm IRGAFOS™ 168.

Films

[0095] The modified polyolefin may be blended with base resin materials, and the blend made into films (both compression molded and blown films).

[0096] The modified polyolefin material was formed into sheets via conventional compression molding techniques. 100mm x 100mm x 2mm pads were formed using the following conditions: 5 minutes preheat at ambient pressure at 190°C, followed by a 20 minute press cycle at 5 tons (4,535 kg) pressure and finally a 180 second press cycle at 10 tons (9,072 kg) pressure. The pressure was removed and the sample was cooled to 25°C over 5 minutes.

[0097] Blown films were prepared using a laboratory Haake blown film line. The line contained a 1" single screw extruder and a 1" mono-layer blown film die. The films produced had a 1.5 mil gauge and a 2.8 bubble blow-up ratio (BUR). "MD" refers to machine direction and "TD" refers to transverse direction.

[0098] Chromium catalyzed high density polyethylene (PAXON™ AL55-003), which has over 95% vinyl terminated chains, was modified with various polysiloxane modifiers. Example 1 (Inventive): Hydrosilylation of PAXON™ AL55-003 Polyethylene with PPDMHS

[0099] PAXON™ AL55-003 polyethylene (50g) was fed into the BRABENDER™ extruder set at 150°C. After 9 minutes, once the torque stabilized, a platinum cyclovinylmethylsiloxane complex catalyst (Gelest Inc., Morrisville, PA, 2.0 - 2.3% platinum concentration in cyclic methylvinylsiloxanes, 0.04 mL) was added by syringe. Hydride terminated polyphenyl-(dimethylhydrosiloxy)siloxane (PPDMHS, 0.9 mL) was then added 1 minute later. The resulting mixture was melt mixed at 40 rpm for an additional 10 minutes. The modified polyolefin was blended for 5 minutes further before removal to produce Example 1 modified polyolefin. FTIR showed suppression of the Si-H peak at 2170 cm ^-1 once the reaction was completed as this Si-H bond is converted to Si-C bonds during reaction. Example 1 modified polyolefin was made into a compression molded film.

[00100] Upon inspection, the compression molded films made from Example 1 modified polyolefin showed no gel particles. A polyolefin film having gels present can have reduced physical properties and be visually unacceptable for the product application. Therefore, it is highly desirable to reduce or eliminate gel formation during processing. The hydros ilylated (PPDMHS) PAXON™ polyethylene (Example 1) advantageously did not exhibit any gels. Example 2 (Comparative): Modified (PHMS) Polyethylene Blends

[00101] PAXON™ AL55-003 polyethylene (5g) was dry blended with EXCEED™ 1018 CA polyethylene pellets (45g). The blend was fed into a BRABENDER™ extruder set to a temperature of 150°C. After 9 minutes, once the torque stabilized, the platinum cyclovinylmethylsiloxane complex catalyst was added by syringe (0.04 mL). Polyhydromethylsiloxane (PHMS, 0.06 mL) was then added 1 minute later. The resulting mixture was melt mixed at 40 rpm for 15 minutes further to provide a 10% blend in EXCEED™ 1018 CA polyethylene.

[00102] The Example 2 10% blend in EXCEED™ 1018 CA polyethylene demonstrated extensional strain hardening (Figure 1) which provided improved bubble stability during blown film operations.

[00103] The rheological data were analyzed using the Van Gurp-Palmen treatment (reference: M. Van Gurp and J. Palmen, Rheology Bulletin, 67, 5, 1998), whereby the phase angle 6 (=tan 1 (G"IG')) is plotted against the absolute value of the complex modulus IG*I = (G'2 + G"2)"2. This representation of linear viscoelastic data is a powerful means of characterizing molecular and structural features of polymers. For example, low levels of long chain branching in polyolefins can be detected and quantified on a relative basis, using this methodology. For Example 2, rheological changes were observed in the Van Gurp-Palmen plot (Figure 2) and there was an increase in zero-shear viscosity on addition of the reactive PHMS with catalyst (Figure 3).

Examples 3-6 (Inventive): Modified Polyethylene Blends

[00104] The modified polyolefin blends for Examples 3 through 6 were prepared as follows. PAXON™ AL55-003 polyethylene was treated with PPDMHS as described above in Example 1 to produce the modified PAXON™ polyethylene. The amount of PPDMHS was varied from a mole to mole ratio of 8: 1, 4: 1, 2: 1, and 1 : 1 for Examples 3, 4, 5, and 6, respectively, based on the calculated moles of reactive end groups of the PAXON™ AL55- 003. The modified PAXON™ AL55-003 polyethylene (3 wt%) was then dry blended with EXCEED™ 2018 polyethylene to provide Example 3 through 6 blends. Blown films were prepared, as described above, using a laboratory HAAKE blown film line.

Example C (Comparative): No Modified Polyethylene [00105] Control Example C was EXCEED™ 2018 without the addition of the modified PAXON™ AL55-003 polyethylene. A blown film was prepared, as described above, for comparison to the inventive films.

TABLE 3: BLOWN FILMS MADE FROM EXAMPLES 3-6

Sample C

Example 3 Example 4 Example 5 Example 6

( CONTROL)

Ratio of PPDMHS:PAXON™

- 8: 1 4:1 2: 1 1 : 1 in Modified PAXON™ PE

Fihi i Properties

i 0 //o secant

MD (psi) 23,332 26,558 29,061 28,915 29,186

MD (MPa) 160.8 183.1 200.3 199.3 201.2 Tensile

Yield Strength

MD (psi) 1,293 1,401 1,294 1,355 1,395

TD (psi) 1,349 1,325 1,414 1,334 1,412

MD (MPa) 8.9 9.7 8.9 9.3 9.6

TD (MPa) 9.3 9.1 9.7 9.2 9.7 jLiongation {w, i ieiu /o)

MD 7.5 6.8 5.9 5.8 6.4

TD 6.1 6.4 5.7 5.5 6.5

Tensile Strength

MD (psi) 7,070 7,436 6,876 6,929 7,306

TD (psi) 7,339 6,667 7,433 6,210 7,113

MD (kPa) 48.7 51.2 47.4 47.7 50.4

TD (kPa) 50.6 45.9 51.2 42.8 49.0

Elongation @ Break (%)

MD 632 651 655 642

TD 624 652 668 593 651

Elmendorf Tear

MD (g) 350 344 318 316 344

TD (g) 432 481 561 519 322

MD (g/mil) 343 331 307 326 489

TD (g/mil) 415 428 449 453 450

MD (g/μηι) 13.5 13.0 12.0 12.8 19.2

TD (g/μηι) 16.3 16.8 17.6 17.8 17.6

Haze (%) 61.7* 13.1 13.7 12.9 10.7

Internal Haze (%) 4.3 2.1 2.2 2.1 1.5

Dart Drop, " i1%vie„tnou A

( ) 371 236 227 212 222

(g/mil) 294 207 185 178 183

Gauge Mic

Average (mils) 1.26 1.14 1.23 1.19 1.21

Low (mils) 0.87 0.86 1.00 0.92 0.91 TABLE 3: BLOWN FILMS MADE FROM EXAMPLES 3-6

Sample C

Example 3 Example 4 Example 5 Example 6 (CONTROL)

Ratio of PPDMHS:PAXON™

- 8: 1 4:1 2: 1 1 : 1 in Modified PAXON™ PE

High (mils) 1.60 1.37 1.41 1.55 1.53

Average (mils) 32.0 29.0 31.2 30.2 30.7

Low (μιη) 22.0 21.8 25.4 23.4 24.6

High (μπι) 40.6 34.7 35.8 39.4 38.9

Die Melt Temperature (°C) 165 164 164 164 165

Torque (m.g) 45.6 38.9 41.9 38.6 43.9

Extruder Speed (rpm) 33.0 33.0 33.0 34.0 34.0

Head Pressure (psi) 2963.8 2946.4 2920.3 2937.7 2982.6

Head Pressure (kPa) 20,435 20,315 20,135 20,255 20,564

Frost Line Height (inches) 2.5 2.5 2.5 2.5 2.5

Frost Line Height (m) 0.064 0.064 0.064 0.064 0.064

Output (g/min) 15.5 15.2 15.2 15.5 15.5

*Due in part to gels.

[00106] It was noted that blended Examples 3 through 6 exhibited a decrease in torque as compared to control Sample C. The decrease in torque reduces motor load and allows for the material to be processed using lower energy, or can also give higher throughputs for the same motor loads.

[00107] An increase in tensile strength was observed for Examples 3 through 6, compared with the control Sample C. The increase in tensile strength advantageously increases stiffness and load carrying ability for the polymers.

[00108] Also, dart drop was reduced in Examples 3 through 6 when compared to control sample C. The decrease in dart drop may be due to the increased orientation in the film. This generally is the consequence of adding high density material to LLDPE. Not to be limited by theory, it is believed that this can be mitigated by adding in a lower density PE.

Example 7 (Inventive): Vinyl Terminated Macromonomers

[00109] The vinyl-terminated macromonomers were prepared according to procedures described in U.S. Application Serial No. 61/704,606, filed on September 24, 2012; and U.S. Application Serial No. 61/704,604, filed on September 24, 2012.

[00110] Metallocene A, represented by the following structure was used herein:

Dimethylaniliniumtetrakis(perfluoronaphthyl)borate was used as the activator.

[00111] To a clean and dry standard 2 liter autoclave, hexene and TIBAL (triisobutylalumoxane) in toluene was added using a cannula. Hexanes were added from a storage tank. The autoclave was then sealed. The reactor was then heated to the set temperature and the agitator started. Once the temperature and pressure were stable, the metallocene A/ dimethylaniliniumtetrakis(perfluoronaphthyl)borate (previously prepared in a dry box) was flushed into the system using 200 ml hexanes.

[00112] At this point, ethylene gas was introduced and the inlet was left open so that a constant pressure of ethylene was maintained. The approximate polymer yield was followed by monitoring the flow rate of ethylene to the reactor (to replenish the used ethylene). After 20 minutes, the reactor was cooled to 25°C, depressurized, and the reactor opened to retrieve the polymer. The polymer was dried in a hood for 12 hours to remove residual hexanes and weighed to determine the overall yield. By this procedure, 4 different batches were prepared. The run conditions are shown below, in Table 4.

[00113] Because the molecular weights and thermal characteristics of polymer obtained from Runs 1 to 4 were similar, the polymer from these four runs were dry blended together to obtain a single polymer batch (VTM polymer), which was blended in at 3% by weight in EXCEED™ 2018 polyethylene to produce Example 7 polymer.

[00114] VTM polymer (50 g, 60% vinyl chain ends, 1.67 mmol) was fed into a BRABENDER™ extruder set to a temperature of 190°C. After 9 minutes, once the torque stabilized, PPDMHS (0.50 mL, 3.37 mmol, 2.02: 1 Si-H:vinyl ratio) was added by syringe. The platinum cyclovinylmethylsiloxane complex catalyst (40 mg) was then added 5 minutes later. The resulting mixture was melt mixed at 40 rpm for 10 minutes further and then the additive package was added and mixed for an additional 5 minutes. This PPDMHS-modified VTM polymer was blended at 3% by weight in EXCEED™ 2018 polyethylene to produce Example 8.

[00115] Blown films were prepared, as described above, for Examples 7 and 8 polymers using a laboratory HAAKE blown film line. Control Example C2 was EXCEED™ 2018 without the addition of the VTM polymer (either modified or unmodified). A blown film was prepared, as described above, for comparison to the inventive films.

[00116] The film properties are shown in Table 5, below.

[00117] Example 7 and 8 films had greater bubble stability than the control (C2) film. They also had no gels, in contrast to the control. Advantageously, the film properties remained the same, and the rheology of the blends showed greater zero-shear viscosity than the control (C2) resin.