MX336995B

Heterogeneous ethylene alpha0olefin interpolymer.

Abstract

An interpolymer of ethylene and at least one alpha-olefin is claimed, wherein the ethylene interpolymer is characterized as having an average Mv and a valley temperature between the interpolymer and high crystalline fraction, Thc, such that the average Mv for a fraction above Thc from ATREF divided by average Mv of the whole polymer from ATREF (Mhc/Mp) is less then about 1.95 and wherein the interpolymer has a CDBI of less than 60%. The interpolymer of ethylene and at least one alpha-olefin can also be characterized as having a high density (HD) fraction and an overall density such that % HD fraction < -2733.3 + 2988.7x + 144111.5 (x - 0.92325)2 where x is the density in grams/cubic centimeter. Fabricated articles comprising the novel interpolymers are also disclosed.

MX336995B, drawing sheet 1 — Sheet 1 of 80

Term

3.5 yearsleft in the term

Expires 30 March 2030.

16 claims: 1 independent, 15 dependent

1
CLAIMS «S = REIVINDICACIONES «S= 1. Un ¡nterpollmero de etileno y por lo menos una alfaolefina preparados en un reactor individual en presencia de un sistema de catalizador de constituyentes múltiples, en donde el interpolímero es interpolímero ramificado de manera heterogénea producido en el reactor individual y en donde el interpolímero exhibe dos máximos y un mínimo desde 30°C hasta 120°C en ATREF y tiene un Mv promedio y una temperatura mínima entre la del interpolímero y la de la fracción altamente cristalina, Thc, de modo tal que el Mv promedio para una fracción por encima de Thc determinada por ATREF dividida entre el Mv promedio de todo el polímero determinado por ATREF (Mhc/Mp) es menor de 1.7 y en donde el ¡nterpollmero tiene un CDBI menor de 48%. one. An ethylene polymer and at least one alpha olefin prepared in a single reactor in the presence of a multi-constituent catalyst system, where the interpolymer is heterogeneously branched interpolymer produced in the single reactor and where the interpolymer exhibits two maxima and a minimum from 30 ° C to 120 ° C in ATREF and has a Mv average and a minimum temperature between that of the interpolymer and that of the highly crystalline fraction, Thc, so that the Mv average for a fraction above Thc determined by ATREF divided by the Mv average of all the polymer determined by ATREF (Mhc/ Mp) is less than 1.7 and where the nterpollmer has a CDBI less than 48%.

401 paragraphs in 47 sections, as filed

(54) Title: ETHYLENE / ALPHA-OLEPHINE HETEROGENEOUS INTERPOLYMER.

(54) Title: HETEROGENEOUS ETHYLENE ALPHAOOLEFIN INTERPOLYMER.

(57) Summary

An ethylene interpolymer and at least one alphaolefin are claimed, characterized in that the ethylene interpolymer is characterized by having an average Mv and a minimum temperature between that of the interpolymer and that of the highly crystalline fraction, The, such that the average Mv for a fraction greater than The determined by ATREF divided by the average Mv of all the polymer determined by ATREF (Mhc / Mp) is less than about 1.95 and because the interpolymer has a CDBI less than 60%. The ethylene interpolymer and at least one alphaolefin can also be characterized as having a high density fraction (HD - high density) and a total density such that the% of the HD fraction <-2733.3 + 2988.7X + 144111.5 (x- 0.92325) 2 where x is the density in grams / cubic centimeter. Articles of manufacture comprising the novel interpolymers are also described.

(57) Abstract

An interpolymer of ethylene and at least one alpha-olefin is claimed, where the ethylene interpolymer is characterized as having an average Mv and a valley temperature between the interpolymer and high crystalline fraction, The, such that the average Mv for a fraction above The from ATREF divided by average Mv of the whole polymer from ATREF (Mhc / Mp) is less then about 1.95 and where the interpolymer has a CDBI of less than 60%. The interpolymer of ethylene and at least one alpha-olefin can also be characterized as having a high density (HD) fraction and an overall density such that% HD fraction <-2733.3 + 2988.7X + 144111.5 (x - 0.92325) 2 where x is the density in grams / cubic centimeter. Fabricated articles comprising the novel interpolymers are also disclosed.

PATENT TITLE NO. 336995 _SE_

SCBHMÍA ÍM BXSMOMÍA

Institute

Mexican Property

Industrial

Holder (s): DOW GLOBAL TECHNOLOGIES LLC.

Address: 2040 Dow Center, Midland, Michigan, 48674, USA

Denomination: ETHYLENE / ALPHA-OLEPHINE HETEROGENEOUS INTERPOLYMER. Classification: lnt.CI.8: C08F210 / 02; C08J5 / 18; C08L23 / 06; C08L23 / 08

YUS

INGE

MX / y / 2011 / 01í 78

Pafs:

US

Validity: Twenty years

Date of V «patent reference

T> e in accordance with the aia from the fei in grants c <

irt uto

d <de pr • re: intacli

Intemack filing date for March 2010

PRIORI

Date:

the property

Pro Law | solii ion twenty years impi to maintain dustrial.

Pray them, entities cough .ey of the iace based on Ιο 0Ιβρΰ3ΒΤφΒ ······ ΙβΓ6 “fractions lll and 7 ° bis 2 of I id Industrial (Official Diaif the Federation (DOF) 06/27/1991, amended on 02 / 08/1994, 10/25/1996, 12/26/1997, j | / 05/1999, raccón V in subscribe the presen title lo / 01/2006, subsection a), 4th and 12th sections I and III of the Regulations of the Mexican Institute of Industrial Property (DOF 12/14/1999, amended on 07/01/2002, 07/15/2004, 07/28/2004 and 09/07/2007); Articles 1, 3, 4, 5, section V, subsection a), 16 sections I and III and 30 of the Organic Statute of the Mexican Institute of Industrial Property (DOF) 12/27/1999, amended on 10/10/2002, 07/29/2004, 08/04/2004 and 09/13/2007); 1, 3 and 5 Clause a) of the Agreement that dele gates powers to the Deputy Directors General, Coordinator, Divisional Directors, Heads of Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).

Issue Date: February 9, 2016

THE DIVISIONAL DIRECTOR OF PATENTS

NAHANNY CANAL REYES

Arenai No. 550, Floor 1,

Coi. Pueblo Santa María Tepapsn,

Xochimfloo Delegation,

CP 16070. Mexico City

Tel í55) 53 34 07 0C www.impi eob.rox

MX / 2016/10262

MEXICAN INSTITUTE DS THE PROPERTY

INDUSTRIAL

Field of Invention '-—

Films of ethylene alpha-olefin copolymer resins that can make films with improved aesthetic (optical) and abuse (impact) resistance properties create value for end users. Heterogeneous alpha-olefin copolymers of ethylene have both highly crystalline (coarse crystals) and copolymer (thin crystals) fractions.

Background of the Invention

The optical properties of a film can be defined in terms of gloss, turbidity, and surface clarity. Turbidity can depend on internal turbidity (dispersion of materials by volume) and external turbidity (dispersion of materials on the surface). Both the external and internal turbidity can be a function of the highly crystalline fraction content and the molecular weight of the highly crystalline fraction of the resin used to make the film. The highly crystalline fraction can be made from thick crystals that scatter light and, therefore, an increase in the content of the highly crystalline fraction increases the turbidity of the film and damages its optical properties. Decreasing the molecular weight of the highly crystalline fraction can increase the thickness of the crystals in the highly crystalline fraction. The thicker the crystals of the highly crystalline fraction, the worse the optics

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MEXICAN INSTITUTE

OF THE PROPERTY

INDUSTRIAL film. Therefore, a reduced nnntpn¡Hn and a higher molecular weight of the crystalline fraction would be dasaabjes for better optics, although too high a molecular weight can cause fusion fracture problems due to high fusion elasticity. Also, increasing the molecular weight of the highly crystalline fraction, for better optics, could damage the impact resistance properties of the film. A higher molecular weight of the copolymer fraction is desirable for a higher impact resistance of the film. For a melt index (MI ol2) of the resin in particular, increasing the molecular weight of the highly crystalline fraction for better optics, has to be balanced by decreasing the molecular weight of the copolymer fraction so that the MI is kept constant. This decrease in the molecular weight of the copolymer will damage the impact resistance properties. Therefore, an optimal molecular weight of the highly crystalline fraction is desirable for balanced optical properties and impact resistance. The thick crystals derived from the highly crystalline fraction provide resistance to the film, improving its anti-tear properties. Decreasing the content of the highly crystalline fraction to improve the optics could therefore damage the anti-tear property of the film. In order to achieve a balance of the anti-tear and optical properties an optimum content of highly crystalline fraction is desirable.

The turbidity of the film surface may depend on the molecular weight distribution of the ethylene alpha-olefin copolymer.

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A very broad molecular weight distribution usually increases the resin melt elasticity that generates a surface fusion fracture while a very narrow molecular weight distribution can cause processing issues at the nozzle, causing surface fusion fracture. Since the presence of surface fusion fracture damages the optical properties of the film, an optimal molecular weight distribution is also required for improved optical properties.

The impact resistance properties of the films may depend on the molecular weight distribution and the content of the copolymer fraction. The narrower the molecular weight distribution and the higher the content of the copolymer fraction, the greater the impact resistance of the film. Too narrow a molecular weight distribution could damage the optical and process properties (film fabrication) and therefore an optimal molecular weight distribution is required for a balance of process, impact resistance and optical properties . Also, an increase in the content of the copolymer fraction could be achieved at a cost of reduction in the content of the highly crystalline fraction and this could damage the anti-tear property of the film. Therefore, in order to achieve a good balance of the properties of the process, impact resistance, anti-tear and optics, a particular combination of molecular weight distribution and a highly crystalline and copolymer fraction content is required.

The present invention is a family of resins, and a process for making them, with this particular combination of molecular weight distribution and highly crystalline fraction content and copolymer and molecular weight. For equivalent density and melt index, this combination of resin characteristics produces a film with balanced optics, impact resistance, anti-tear and process properties.

Brief Description of the Invention

In one embodiment, an ethylene interpolymer and at least one alpha-olefin are made, characterized in that the interpolymer has an Mv average and a minimum temperature between that of the interpolymer and that of the highly crystalline fraction, Thc, such that the Mv average for a fraction greater than Thc determined by ATREF divided by the average Mv of all the polymer determined by ATREF (Mhc/ Mp) is less than about 1.95, preferably less than 1.7, and where the interpolymer has a CDBI less than 60%, preferably less than 55%.

In a second embodiment, an ethylene interpolymer and at least one alpha-olefin are made, where the interpolymer is characterized by having a high-density fraction (HD) and a total density such that% of the fraction HD <-2733.3 + 2988.7x + 144111.5 (x - 0.92325)2 where x is the density in grams / cubic centimeter.

In any embodiment, preferably the interpolymer s

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heterogeneously branched. The film can be made from interpolymers of any embodiment, especially films that comprise the Dart A impact test of at least 550 grams, or that comprise a turbidity of <10%, or that comprise 45 degree gloss units of > 75 units, or comprising a Normalized MD anti-tear property> 400 grams / thousandth of an inch. The film may comprise at least one layer comprising the interpolymer of either the first or second embodiment.

In either embodiment, the interpolymer may further comprise at least one natural or synthetic polymer, preferably low-density polyethylene. The interpolymer of any embodiment may comprise a melt index of from about 0.1 to about 10 g / 10 min., Or may comprise a total density of from about 0.9 to about 0.935 g / cm.3, or can comprise long chain branches less than 1 per 1000 C atoms, or can comprise a molecular weight distribution, Mw/ Mn, less than about 5.

A manufactured article may comprise the interpolymer of either the first or second embodiment. Furthermore, the interpolymer of either the first or second embodiment can be at least partially crosslinked to at least 5%, by weight, of gel.

A third embodiment is a process for making an interpolymer of ethylene and at least one aifa-olefin comprising the steps of contacting ethylene with at least one alpha-olefin under temperature and pressure polymerizations with a composition

ΪΒΖ & ίεΛΒΙΛΛ

catalyst in order to form an ethylene / alpha-olefin interpolymer having an Mv average and a minimum temperature between that of the interpolymer and that of the highly crystalline fraction, Thc. such that the Mv average for a fraction greater than Thc determined by ATREF divided by the Mv average of all the polymer determined by ATREF (Mhc/ Mp) is less than about 1.95 and has a CDBI of less than 60%, where the polymerization conditions comprise an aluminum to catalyst metal mole ratio of from about 1: 1 to about 5: 1, and recover the interpolymer from ethylene / alpha-olefin, preferably where the catalyst composition comprises the product that results from combining:

(A) a magnesium halide prepared by contacting:

(1) at least one hydrocarbon soluble magnesium component represented by the general formula R "R'Mg.xAIR'3 where each R" and R 'are alkyl groups (2) at least one source of low metal or non-metal halide conditions such that the reaction temperature does not exceed about 60 ° C, preferably does not exceed about 40 ° C, and most preferably does not exceed about 35 ° C;

(B) at least one transition metal compound represented by the formula Tm (OR) and Xy-x where Tm is a metal from Groups IVB, VB, VIB, VIIB or VIII of the Periodic Table; R is a hydrocarbyl group having from 1 to about 20, preferably from 1

up to about 10 carbon atoms, and (C) an additional halide source if insufficient amount of component (A-2) is present to provide the desired excess ratio X: Mg.

Brief Description of the Figures

The above summary as well as the following detailed description will be better understood when read in conjunction with the accompanying drawings. However, it should be understood that the invention is not limited to the arrangements and instrumentalities shown. The components in the drawings are not necessarily to scale, with emphasis instead of being true to the principles of the present invention. Furthermore, in the drawings, similar reference numbers designate the corresponding parts through the various views.

Figure 1 graphically depicts the Short Chain Branch Distribution and log Mv data determined by ATREF for Inventive Example 1 and Comparative Example 1.

Detailed description of the invention

The following description is presented to enable the person skilled in the art to make and use the described compositions and methods. The described general principles can be applied to the modalities and applications different from those detailed without isolating from the spirit and scope of the described compositions and methods. The compositions

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INDUSTRIAL

and methods described are not intended to be limited to the modalities shown, but should encompass the widest scope consistent with the principles and characteristics described.

The balance of the properties of the process, impact resistance, anti-tear and optics was reached by elaborating a unique combination of resin molecular weight distribution and a highly crystalline and copolymer fraction content. The resin characteristics and film property details are listed in Table 1, Figure 1, and Figure 2. The content of the high-density fraction dropped significantly and that of the copolymer fraction increased. The viscosity average molecular weight ratio of the highly crystalline fraction to that of the entire polymer decreased, indicating a lower molecular weight of the highly crystalline fraction. The viscosity average molecular weight ratio of the copolymer fraction to that of the entire polymer was increased, indicating a higher molecular weight of the copolymer fraction. These differences in resin characteristics were achieved by reducing the reactor temperature from approximately 160 ° C to approximately 180 ° C, in particular 175 ° C and reducing the Al / Ti molar ratio from approximately 1: 1 to approximately 5: 1, particularly 1: 1 to approximately

2.5:1.

The film made from the inventive resin, which has a unique combination of molecular characteristics, had significantly improved impact resistance and optics without any

INDUSTRIAL sacrifice in MD anti-tear property and process.

This resin can be used for applications where improvements in optical and impact resistance properties are required without sacrificing the film's anti-tear and process properties during film manufacture.

The low reactor temperature is useful for narrowing the molecular weight distribution. The reactor temperature of 175 ° C delivered a product with a narrow molecular weight distribution without significantly reducing the production output (Ib / hr). A further significant reduction in temperature could further narrow the molecular weight distribution but significantly better than the output and would also cause the product to harm the resin process (film making).

The low Al / Ti ratio is useful for narrowing the molecular weight distribution and also for reducing the highly crystalline fraction and increasing the copolymer fraction. For a HEC-3 catalyst with a 3.0 Ti / 40 Mg ratio, an Al / Ti ratio of 1.5 delivered a product with a narrow molecular weight distribution, a lower crystalline fraction and a more copolymer fraction without affecting stability. of the reactor.

Preferably, the reactor temperature ranges from about 160 ° C to about 180 ° C.

Preferably, the ratio of aluminum to metal atom, preferably Al / Ti, ranges from about 1: 1 to about 5: 1.

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MEXICAN INSTITUTE OF PROPERTY

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The melt index of the described ethylene polymer can vary from approximately 0.01 to approximately 1000 g / 10 minutes, measured according to ASTM 1238-04 (2.16 kg and 190 ° C).

Ethylene-based polymers

Suitable ethylene-based polymers can be prepared with Ziegler-Natta catalysts. Examples of linear ethylene-based polymers include high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE). Suitable polyolefins include, but are not limited to, ethylene / diene interpolymers, ethylene / α-olefin interpolymers, ethylene homopolymers, and mixtures thereof.

Suitable ethylene-based heterogeneous linear polymers include linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), and very low-density polyethylene (VLDPE). For example, some interpolymers produced using a ZieglerNatta catalyst have a density of about 0.89 to about 0.94 g / cm3 and they have a melt index (l2) from approximately 0.01 to approximately 1,000 g / 10 minutes, measured according to ASTM 1238-04 (2.16 kg and 190 ° C).

Preferably, the melt index (l2) can range from about 0.1 to about 50 g / 10 minutes. Heterogeneous linear ethylene-based polymers can have a molecular weight distribution, Mw/ Mn, from approximately 3.5

up to about 5.

The linear ethylene-based polymer may comprise units derived from one or more α-olefin copolymers as long as there is at least 50 mole percent polymerized ethylene monomer in the polymer.

High-density polyethylene (HDPE) can have a density in the range from about 0.94 to about 0.976 g / cm3. HDPE is typically an ethylene homopolymer or an ethylene interpolymer and low levels of one or more aolefin copolymers. HDPE contains relatively few branching chains relative to the various ethylene copolymers and one or more α-olefin copolymers. HDPE can be comprised of less than 5 mol% of units derived from one or more α-olefin comonomers.

Linear ethylene-based polymers such as linear low-density polyethylene and ultra-low-density polyethylene (ULDPE) are characterized by the absence of long-chain branching, as opposed to conventional low-crystallinity, highly branched polymers based on ethylene such as LDPE . Heterogeneous linear ethylene-based polymers such as LLDPE can be prepared by solution, aqueous paste, or gas phase polymerization of ethylene and one or more α-olefin comonomers in the presence of a Ziegler-Natta catalyst, by processes such as those described in US Patent No. 4,076,698 (Anderson, et al.). The relevant discussions of these two kinds of materials, and their

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preparation methods are found in the Pat

4,950,541 (Tabor, et al.). Other patents and publications for making LLDPE include WO 2008/0287634, US 4198315, US 5487938, EP 0891381, and US 5977251.

An α-olefin comonomer can have, for example, from 3 to 20 carbon atoms. Preferably, the aolefin comonomer can have 3 to 8 carbon atoms. Exemplary aolefin comonomers include, but are not limited to, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1- heptene, 4,4-dimethyl-1-pentene, 3-ethyl-1-pentene,

1-octene, 1-niene, 1-decene, 1-dodecene, 1-tetradecene, 1hexadecene, 1-octadecene and 1-eicosenne. Commercial examples of linear ethylene-based polymers that are interpolymers include ATTANE ™ Ultra Low Linear Density Polyethylene Copolymer, DOWLEX ™ Polyethylene Resins, and FLEXOMER ™ Very Low Density Polyethylene, all available from The Dow Chemical Company.

In a further aspect, when used in reference to an ethylene homopolymer (ie, a high-density ethylene homopolymer that contains no comonomers and, consequently, no short-chain branching), the terms "homogeneous ethylene polymer or "Homogeneous linear ethylene polymer" can be used to describe such a polymer.

The ethylene-based polymers described herein are relatively non-homogeneous (or heterogeneous) polymers of ethylene having short chain ramifications and characterized by a

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D £ IA PXOttÉDA »O *» *

INDUSTRIAL relatively low Composition Distribution Breadth Index (CDBI). That is, the ethylene polymer has a CDBI less than or equal to about 55 percent, preferably less than or equal to about 50 percent, more preferably less than or equal to about 45 percent, but they usually include a fraction of Measurable high density (crystalline) polymer.

CDBI is defined as the percentage by weight of polymeric molecules that have a comonomer content within 50 percent of the average total molar comonomer content and represents a comparison of the comonomer distribution in the polymer to the expected comonomer distribution for a Bernoulli distribution. The CDBI of polyolefins can be conveniently calculated from data obtained from techniques known in the art, such as, for example, temperature rising elution fractionation ("TREF") as described, for example, by Wild, et al., Journal of Polymer Science, Poly. Phys. Ed. Vol. 20, 441 (1982); LD Cady, “The Role of Comonomer Type and Distribution in LLDPE Product Performance, SPE Regional Technical Conference, Quaker Square Hilton, Akron , OH, 107-119 (October 1-2, 1985); or in US Patent Nos. 4; 798,081 (Hazlitt, et al.) and US Patent No. 5,008,204 (Stehling). However, the TREF technique does not include purge amounts in CDBI calculations. Plus

preferably, the comonomer distribution of the polymRrn sr __ determined using analysis of 13C NMR according to the techniques described, for example, in US Patent No. 5,292,845 (Kawasaki, et al.) And JC Randall in Rev. Macromol. Chem. Phys., C29,

201-317.

The presence of long chain branching can be determined in ethylene homopolymers using nuclear magnetic resonance spectroscopy of 13C and quantified using the method described by Randall (Rev. Macromol. Chem. Phys., C29, V, 2 & 3, 285-297).

There are other known techniques useful in determining the presence of long chain branches in ethylene polymers, including ethylene / 1-octene interpolymers. Two such exemplary methods are gel permeation chromatography coupled with a low angle laser light scattering detector (GPC-LALLS) and gel permeation chromatography coupled with a viscometer detector. differential (GPCDV). The use of these techniques for detection of long chain branches and the underlying theories have been well documented in the literature. See, for example, Zimm, GH and Stockmayer, WH, J.

Chem. Phys., 17, 1301 (1949), and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) 103-112.

The terms "heterogeneous" and "heterogeneously branched" mean that the ethylene polymer can be characterized as a mixture of interpolymer molecules having various mole ratios of ethylene to comonomer. Linear Ethylene Polymers

Heterogeneously branched are available from The Dow Chemical Company as DOWLEX ™ linear low-density polyethylene and as ATTANE ™ ultra-low-density polyethylene resins. Heterogeneously branched linear ethylene polymers can be prepared by solution, water paste, or gas phase polymerization of ethylene and one or more optional α-olefin comonomers in the presence of a Ziegler-Natta catalyst, by processes such as those described in US Patent No. 4,076,698 (Anderson, et al.). Heterogeneously branched ethylene polymers are typically characterized by having molecular weight distributions, Mw / Mn, of from about 3 to about 5, and, as such, are distinct from substantially linear ethylene polymers and heterogeneously branched linear ethylene polymers. with respect to both the compositional short chain branching distribution and the molecular weight distribution.

Very long chain branched ethylene based polymers

Very long chain branched ethylene-based polymers, such as low-density polyethylene (LDPE), which can be blended with novel heterogeneous ethylene polymers herein, can be made using a high-process pressure that uses free radical chemistry to polymerize the ethylene monomer. The typical density of the LDPE polymer ranges from about 0.91 to about 0.94

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g / cm3. Low-density polyethylene can have a melt index (l2) from about 0.01 to about 150 g / 10 minutes. Very long chain branched ethylene based polymers such as LDPE may also be referred to as "high pressure ethylene polymers", meaning that the polymer is partially or fully homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 13,000 psig with the use of free radical initiators, such as wastes (see, for example, US Patent No. 4,599,392 (McKinney, et al.)). The process creates a polymer with significant branches, including long chain branches.

Very long chain branched ethylene-based polymers are typically ethylene homopolymers; however, the polymer may comprise units derived from one or more aolefin copolymers as long as there is at least 50 mole percent of ethylene monomer used in the polymer.

Comonomers that can be used to form highly branched ethylene-based polymer include, but are not limited to, α-olefin comonomers, typically having no more than 20 carbon atoms. For example, α-olefin comonomers, for example, can have from 3 to 10 carbon atoms; or alternatively, the α-olefin comonomers, for example, can have from 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-niene, 1-decene, and 4 -methyl-1-pentene.

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Alternatively, exemplary comonomers include, but are not limited to, carboxylic acids C3-C8 α, β-unsaturated, in particular maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid and crotonic acid derived from carboxylic acids C3-C8 α, β-unsaturated, for example, carboxylic acid esters C3-C15 unsaturated, in particular alca, -C-alkanesters or anhydrides, in particular methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethihexyl, tertiary butyl acrylate, methacrylic anhydride, maleic anhydride, and itaconic anhydride. In another alternative, exemplary comonomers include, but are not limited to, vinyl carboxylates, eg, vinyl acetate. In another alternative, exemplary comonomers include, but are not limited to, n-butyl acrylate, acrylic acid, and methacrylic acid.

Process

To produce the ethylene-based polymer of the invention, a solution phase polymerization process can be used. Typically, such a process occurs in a well stirred reactor such as a loop reactor or a reactor from temperatures ranging from about 150 to about 300 ° C, preferably from about 160 to about 180 ° C, and at pressures from about 30 to approximately 1000 psi, preferably from approximately 30 to approximately 750 i

psi. The residence time in such a process varies from

about 2 to about 20 minutes, preferably from about 10 to about 20 minutes. Ethylene, solvent, catalyst, and optionally one or more comonomers are continuously fed into the reactor. Exemplary catalysts in these embodiments include, but are not limited to, Ziegler-Natta catalysts. Exemplary solvents include, but are not limited to, soparaffins. For example, such solvents are commercially available under the trademark ISOPAR E (ExxonMoblI Chemical Co., Houston, Texas). The resulting mixture of ethylene-based polymer and solvent is removed after the reactor and isolated to the polymer. Typically, the solvent is recovered by a solvent recovery unit, i.e. heat exchangers and vapor-liquid separator drums, and recycled back to the polymerization system.

To produce the very long chain branched ethylene-based polymer, a high pressure free radical initiated polymerization process is typically used. Two different types of high pressure free radical initiated polymerization process are known. In the first type, a stirred autoclave container having one or more reaction zones is used. Typically, the autoclave reactor has multiple injection points for either monomer or initiator feeds, or both. In the second type, a lined tube is used as the reactor, which has one, reactor zones. Suitable but not limiting reactor lengths can range from about 100 to about 3000 meters, preferably from 1000

MEXICAN INSTITUTE up to 2000 meters. The initiation of a reaction zone for any type of reaction is defined by the lateral injection of any initiator of the reaction, ethylene, telomere, comonomer (s) as well as any combination thereof. A high pressure process can be carried out in autoclave or tubular reactors or in a combination of autoclave and tubular reactors, each comprising one or more reaction zones.

The catalyst or initiator is injected in advance into the reaction zone where free radical polymerization is to be induced. In other processes of the embodiment, the ethylene-based polymer can be fed into the reaction system in the front reactor system and without being formed within the system itself. Termination of the catalyst activity can be accomplished by a combination of high reactor temperatures for the free radical polymerization portion of the reaction or by feeding the initiator into the reactor dissolved in a mixture of polar solvent such as isopropanol, water, or solvent from conventional initiators such as branched or unbranched alkanes.

The modality processes may include a process recycle loop to improve conversion efficiency. In some processes of the embodiment, the recycling loop may be treated to neutralize residues or derivatives of the above reaction cycle which may inhibit polymerization of either the ethylene-based polymer or the very long-chain branched ethylene-based polymer or inhibit that the reaction forms the described ethylenic polymer. In some

modality processes, fresoo-sheoto monomer flow is added ^^ - ^ ..

The ethylene used for the production of ethylene-based polymers or very long-chain branched ethylene-based polymer may be purified ethylene, which is obtained by removing polar components from a loop recycling stream or by using a system configuration reaction so that only fresh ethylene is used to make the ethylene-based polymers. It is not typical that purified ethylene is required to make very long chain branched ethylene based polymer. In such cases, ethylene from the recycling circuit can be used.

Chain transfer agents (CTAs) or telogens are typically used to control the melt index in a free radical polymerization process. Chain transfer involves termination of growing polymer chains, thus limiting the final molecular weight of the polymeric material. Typically, chain transfer agents are donors of hydrogen atoms that will react with an increasing polymer chain and stop the chain polymerization reaction. For high pressure free radical polymerization, these agents can be of many different types, such as saturated hydrocarbons, unsaturated hydrocarbons, aldehydes, ketones, or alcohols. Typically, CTAs that can be used include, but are not limited to, propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, propionaldehyde, ISOPAR (ExxonMobil Chemical Co.), and isopropanol. The number of CTAs to use in the process is

about 0.03 to about 10 weight percent of the total reaction mixture.

The melt index (MI ol2) of a polymer, which is inversely related to molecular weight, is controlled by manipulating the concentration of the chain transfer agent. For free radical polymerization, after the donation of a hydrogen atom, the CTA forms a radical that can react with the monomers, or with already formed oligomers or polymers, in order to start a new polymer chain. This means that any functional group present in the chain transfer agents will be introduced into the polymer chain. A large number of CTAs, eg, propylene and 1-butene having an olefinically unsaturated bond, can also be incorporated into the polymer chains themselves, by a copolymerization reaction. Polymers produced in the presence of chain transfer agents are modified in various physical properties such as process, optical properties such as turbidity and clarity, density, stiffness, yield strength, film removal, and tear resistance.

Hydrogen has been shown to be a chain transfer agent for high pressure free radical polymerization and in the production of high crystallinity ethylene based polymer. The control of the molecular weight carried out in the reaction zones for the described processes can be carried out by feeding hydrogen to the reaction zones where catalyst or initiator is injected. The control

of the final product melt index would be made by feeding the

-1ΓΈΠΙ chain transfer agents to reaction zones where free radical polymerization takes place. The free radical chain transfer agents could be fed by direct injection into the reaction zones or by feeding them to the front of the reactor. In some modality processes, it may be necessary to remove excess CTA from the recycle stream or limit injection to avoid formation of excess CTA early in the process.

The free radical initiators that are generally used to produce ethylene-based polymers are oxygen, which is usable in tubular reactors in conventional amounts from

0.0001 and 0.005% by weight extracted by weight of the polymerizable monomer, and peroxides. Preferred initiators are t-butyl peroxy pivalate, di-t-butyl peroxide, t-butyl peroxy acetate, and t-butyl peroxy 2hexanoate or mixtures thereof. These organic peroxy initiators are used in conventional amounts of between 0.005 and 0.2% by weight extracted from the weight of the polymerizable comonomers.

The peroxide initiator can be, for example, an organic peroxide. Exemplary organic peroxides include, but are not limited to, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, and peroxyketals.

Exemplary cyclic peroxides include, but are not

-23i IMPI 1 INDUSTRIAL limited to 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan. Such cyclic peroxides, for example, are commercially available under the trademark TRIGONOX 301 (Akzo Nobel; Arnhem, The Netherlands). Exemplary diacyl peroxides include, but are not limited to, di (3,5,5-trimethylhexanoyl) peroxide. Such diacyl peroxides, for example, are commercially available under the trademark TRIGONOX 36 (Akzo Nobel). Exemplary dialkyl peroxides include, but are not limited to, 2,5-dimethyl-2,5di (tert-butylperoxy) hexane; 2-5, dimethyl-2,5-di (tert-butylperoxy) hexino-3; tertiary di-amyl peroxide; tertiary di-butyl peroxide; and tertiary butyl cumyl peroxide. Such dialkyl peroxides, for example, are commercially available under the trademarks TRIGONOX 101, TRIGONOX 145, TRIGONOX 201, TRIGONOX B and TRIGONOX T (Akzo Nobel). Exemplary hydroperoxides include, but are not limited to, tertiary amyl hydroperoxide; and 1,1,3,3-tetramethylbutyl hydroperoxide. Such hydroperoxides, for example, are commercially available under the trademarks TRIGONOX TAHP and TRIGONOX TMBH (Akzo Nobel). Exemplary peroxycarbonates include, but are not limited to, tert-butylperoxy 2-ethylhexyl carbonate; carbonate

Tertiary amylperoxy 2-ethylhexyl; and tertiary butyl peroxy isopropyl carbonate. Such peroxycarbonates, for example, are commercially available under the trademarks TRIGONOX 117, TRIGONOX 131 and TRIGONOX BPIC (Akzo Nobel). Exemplary peroxydicarbonates include, but are not limited to,

di (2-ethylhexyl) peroxydicarbonates; and secondary di-butyl peroxydicarbonates. Such peroxydicarbonates, for example, are commercially available under the trademark TRIGONOX EHP and TRIGONOX SBP (Akzo Nobel). Exemplary peroxyesters include, but are not limited to, tertiary amyl peroxy-2-ethylhexanoate; tertiary amyl peroxyneodecanoate; tertiary amyl peroxypivalate; tertiary amyl peroxybenzoate; tertiary amyl peroxyacetate; 2,5dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane; tertiary butyl peroxy-2-ethylhexanoate; tertiary butyl peroxyneodecanoate; tertiary butyl peroxyneoheptanoate; tertiary butyl peroxypivalate; tertiary butyl peroxydiethyl acetate; tertiary butyl peroxyisobutyrate; 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate; 1,1,3,3-tetramethylbutyl peroxyneodecanoate; 1,1,3,3-tetramethylbutyl peroxypivalate; tertiary butyl peroxy-3,5,5-trimethylhexanoate; cumyl peroxyneodecanoate; tertiary butyl peroxybenzoate; and tertiary butyl peroxyacetate. Such peroxy ester solvents, for example, are commercially available under the trademarks TRIGONOX 121; TRIGONOX 123; TRIGONOX 125; TRIGONOX 127; TRIGONOX 133, TRIGONOX 141; TRIGONOX 21; TRIGONOX 23; TRIGONOX 257; TRIGONOX 25, TRIGONOX 27;

TRIGONOX 41; TRIGONOX 421; TRIGONOX 423; TRIGONOX 425; TRIGONOX 42; TRIGONOX 99; TRIGONOX C; and TRIGONOX F (Akzo Nobel). Exemplary peroxyketals include, but are not limited to, 1,1-di (tert-amylperoxy) cyclohexane; 1,1-di (tert-butylperoxy) cyclohexane; 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane;

-25y 2,2-di (tert-butylperoxy) butane. Such peroxyketals, for example, are commercially available under trademarks.

MEXICAN IHSTITUTE OF PROPERTY

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TRIGONOX 122, TRIGONOX 22, TRIGONOX 29, and TRIGONOX D (Akzo Nobel). The free radical initiator system may, for example, include a mixture or combination of any of the aforementioned peroxide initiators. The peroxide initiator may comprise less than 60 weight percent of the free radical initiator system.

The free radical initiator system further includes at least one hydrocarbon solvent. The hydrocarbon solvent can, for example, be a hydrocarbon solvent C5 a C30. Exemplary hydrocarbon solvents include, but are not limited to, mineral solvents, normal paraffinic solvents, isoparaffinic solvents, cyclic solvents, and the like. Hydrocarbon solvents can, for example, be selected from the group consisting of n-octane, iso-octane (2,2,4-trimethylpentane), n-dodecane, iso-dodecane (2,2,4,6, 6-pentamethylheptane), and other isoparaffinic solvents. Exemplary hydrocarbon solvents such as isoparaffinic solvents, for example, are commercially available under the trademarks ISOPAR C, ISOPAR E, and ISOPAR H (ExxonMobil Chemical Co.). The hydrocarbon solvent can comprise at least 99 weight percent of the free radical initiator system.

Catalysts suitable for use in the modality processes include any compound or combination of compounds.

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which is adapted to prepare polymers of the desired composition or type, either ethylene-based polymers or very long-chain branched ethylene-based polymers. Heterogeneous catalysts can be used. In some processes of the embodiment, heterogeneous catalysts may be used, including known Ziegler-Natta compositions, especially Group 4 metal halides supported on Group 2 metal halides or mixed halides and alkoxides, and known chromium or vanadium catalysts. In some processes of the embodiment, the catalysts for use may be homogeneous catalysts comprising a relatively pure organometallic compound or metal complex, especially metal-based compounds or complexes selected from Groups 3-10 or the lanthanide series . If more than one catalyst is used in a system, it is preferred that any catalyst employed does not significantly detrimentally affect the performance of another catalyst under the polymerization conditions. Desirably, no catalyst has its activity reduced by more than 25 percent, more preferably more than 10 percent under the polymerization conditions.

In processes of the embodiment employing a complex metal catalyst, such a catalyst can be activated to form an active catalyst composition by combination with a cocatalyst, preferably a single cation-forming catalyst, a strong Lewis acid, or a combination of the themselves. Suitable cocatalysts for use include aluminoxanes

polymeric or oligomeric, especially dimethyl aluminoxane, as well as compatible, inert, non-coordinating, ion-forming compounds. The so-called modified methyl aluminoxane (MMAO) or triethyl aluminum (TEA triethyl aluminum) is also suitable for use as a cocatalyst. A technique for preparing such modified aluminoxane is described in US Patent No. 5,041,584 (Crapo, et al.). Aluminoxanes can also be made as described in US Patent Nos. 5,542,199 (Lai, et al.); 4,544,762 (Kaminsky, et al.); 5,015,749 (Schmidt, et al.); and 5,041,585 (Deavenport, et al.).

In some processes of the embodiment, processing aids, such as plasticizers, may also be included in the ethylenic polymer product of the embodiment. These auxiliaries include, but are not limited to, phthalates, such as dioctyl phthalate and diisobutyl phthalate, natural oils such as lanolin, and paraffin, naphthenic and aromatic oils obtained from petroleum refining, and liquid resins from rosin or petroleum feed loads. Classes of exemplary oils useful as processing aids include white mineral oil such as KAYDOL oil (Chemtura Corp .; Middlebury, Conn.) And SHELLFLEX 371 naphthenic oil (Shell Lubricants; Houston, Tex.). Another suitable oil is TUFFLO oil (Lyondell Lubricants; Houston, Tex.).

In some processes of the embodiment, the ethylenic polymers of the embodiment are treated with one or more stabilizers, for example, antioxidants, such as IRGANOX 1010 and IRGAFOS 168 (Ciba

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Specialty Chemicals; Glattbrugg, Switzerland). In general, the polymers are treated with one or more stabilizers before extrusion or other metallic processes. In other processes of the embodiment, other polymeric additives include, but are not limited to, UV absorbers, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents, flame retardants, plasticizers, processing aids, lubricants. , stabilizers, smoke inhibitors, viscosity control agents and antiblocking agents. The ethylenic polymer composition of the embodiment may, for example, comprise less than 10 percent by the combined weight of one or more additives, based on the weight of the epidemic polymer of the embodiment.

The ethylenic polymer of the embodiment can be further compounded. In some ethylenic polymer compositions of the embodiment, one or more antioxidants can be further compounded in the polymer and the compressed composite polymer. The ethylenic compound polymer can contain any amount of one or more antioxidants. For example, the ethylenic compound polymer may comprise from about 200 to about 600 parts of one or more phenolic antioxidants per 1 million parts of the polymer. Furthermore, the ethylenic compound polymer can comprise from about 800 to about 1200 parts of a phosphite-based antioxidant per one million parts of the polymer. The compound described ethylenic polymer may further comprise about 300 to about 1250 parts stearate

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of calcium per million parts of polymer.

Crosslinking agents

Some suitable crosslinking agents have been described in Zweifel Hans et al., "Plastics Additives Handbook", Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 14, pages 725-812 (2001) ; Encyclopedia of Chemical Technology, Vol. 17, 2nd edition, Interscience Publishers (1968); and Daniel Seern, "Organic Peroxides (" Organic Peroxides "), Vol. 1, WileyInterscience, (1970), all of which are incorporated herein by reference.

Non-limiting examples of suitable crosslinking agents include peroxides, phenols, azides, aldehydeamine reaction products, substituted ureas, substituted guanidines; substituted xanthates; substituted dithiocarbamates; sulfur-containing compounds, such as thiazoias, suifenamides, thiuramidisulfides, paraquinoneadioxime, dibenzoparaquinoneadioxime, sulfur; imidazoles; silanes and combinations thereof.

Non-limiting examples of suitable organic peroxide crosslinking agents include alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacyl peroxides, peroxyketals, cyclic peroxides, and combinations thereof. In some embodiments, the organic peroxide is dicumyl peroxide, t-butylisopropylidene peroxybenzene, 1,1-di-t-butyl peroxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-hexane. di (t-butylperoxy), peroxide

t-butyl-cumyl, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-butyl-peroxy) hexin or a combination thereof. In one embodiment, the organic peroxide is dicumyl peroxide. Additional teachings regarding organic peroxide crosslinking agents are described in CP Park, "Polyolefin Foam", Chapter 9 of Handbook of Polymer Foams and Technology, edited by D. Klempner and KC Frisch, Hanser Publishers, pgs. 198-204, Munich (1991), which are incorporated herein by reference.

Non-limiting examples of suitable azide crosslinking agents include azidoformates, such as tetramethylenebis (azidoformate); aromatic polyazides, such as 4,4'-diphenylmethane diazide; and sulfonazides, such as p, p'oxibis (benzene sulfonylazide). The description of azide crosslinking agents can be found in US Patent Nos. 3,284,421 and 3,297,674, both of which are incorporated herein by reference.

Poly (sulfonylazide) is any compound that has at least two sulfonylazide groups (i.e., -SO2N3) which are reactive towards the ethylene / α-olefin interpolymer described herein. In some embodiments, the poly (sulfonylazide) s have an XRX structure where each X is -SO2NOT3 and R represents an unsubstituted or inertly substituted hydrocarbyl group, hydrocarbyl ether or containing silicon. In some embodiments, the R group has enough carbon, oxygen, or silicon, preferably carbon, atoms to separate

-31 CXSTnvro Mexican CELA PROPERTY INDUSTKLAL

Sulfonylazide groups sufficiently to allow a surface reaction between the ethylene / α-olefin interpolymer and the sulfonylazide groups. In other embodiments, the R group has at least 1, at least 2, or at least 3 carbon, oxygen, or silicon atoms, preferably carbon, among the sulfonylazide groups. The term "inertly substituted" refers to substitution with atoms or groups that do not undesirably interfere with the desired reaction (s) or desired properties of the resulting particulate polymers. Such groups include fluorine, aliphatic or aromatic ethers, siloxanes, and the like. Non-limiting examples of suitable R structures include aryl, alkyl, alkaryl, arylalkyl, silanyl, heterocyclyl, and other inert groups. In some embodiments, the R group includes at least one aryl group among the sulfonyl groups. In other embodiments, the R group includes at least two aryl groups (such as when R is 4,4'-diphenyl ether or 4,4'-biphenyl). When R is an aryl group, it is preferred that the group have more than one ring, as in the case of In some embodiments, the 1,5-pentanobis (sulfonylazide), naphthylenebis (sulfonylazides). poly (sulfonyl) azides include

1,8octanobis (sulfonylazide), 1,10-decanobis (sulfonylazide), 1,10octadecanobis (sulfoniiazide), 1 -octyl-2l4,6-benzene-tris (sulfoniiazide), 4,4'-d ifen i leterbis (su Ifon i I azide), 1,6-bis (4'-sulfonazidophenyl) hexane, 2,7naphthalene bis (sulfonylazide), and mixed chlorinated aliphatic hydrocarbons containing an average of from 1 to 8 chlorine atoms and from about 2 to 5 sulfonylazide groups per molecule, and combinations thereof. In others

Modalities, the poly (sulfonyllazides) include oxy-bis (4sulfonylazidobenzene), 2,7-naphthalenebis (sulfonylazido), 4,4'bs (sulfoniiazido) biphenyl, 4,4'-diphenyl etherbis (sulfonylazide) and bis- ( 4sulfonyl azidophenyl) methanol, and combinations thereof.

Non-limiting examples of suitable aldehydeamine reaction products include formaldehyde-ammonia, formaldehyde-ethylchloride-ammonia, acetaldehyde-ammonia, formaldehyde-aniline, butylraidehyde-aniline, heptaldehyde-aniline, and combinations thereof.

Non-limiting examples of suitable substituted ureas include trimethylthiourea, diethylthiourea, dibutylthiourea, tripentylthiourea, 1,3bis (2-benzothiazolylmercaptomethyl) urea, Ν, Ν-diphenylthiourea, and combinations thereof.

Non-limiting examples of suitable substituted guanidines include diphenylguanidine, di-o-tolylguanidine, diphenylguanidine phthalate, the di-o-tolylguanidine salt of dicatecol borate, and combinations thereof.

Non-limiting examples of suitable substituted xanthates include zinc ethylxantate, sodium isopropyloxantate, butylxanthan bisulfide, potassium isopropylxantate, zinc butylxantate, and combinations thereof.

Non-limiting examples of suitable dithiocarbamates include copper dimethyl dithiocarbamate, zinc dimethyl dithiocarbamate, tellurium diethyldithiocarbamate, cadmium dicyclohexyl dithiocarbamate, lead dimethyldithiocarbamate, lead dimethyl dithiocarbamate, dibutyl-

selenium dithiocarbamate, zinc pentamethylene dithiocarbamate, zinc didecyldithiocarbamate, isopropyloctyl-zinc dithiocarbamate, and combinations thereof.

Non-limiting examples of suitable thiazoles include 2-mercaptobenzothiazole, zinc mercaptothiazolyl mercaptide, 2-benzothiazolyl-N, N-diethylthiocarbamyl sulfide, 2,2'-dithiobis (benzothiazola), and combinations thereof.

Non-limiting examples of suitable imidazoles include 2-mercaptoimidazoline 2-mercapto-4,4,6-trimethyldihydropyrimidine, and combinations thereof.

Non-limiting examples of suitable sulfenamides include Nt-butyl-2-benzothiazola-, N-cyclohexylbenzothiazola-, N, Ndiisopropylbenzothiazola-, N- (2,6-dimethylmorpholine) -2-benzothiazola-, N, Ndiethylbenzothiazola-sulfenamide, and combinations from the same.

Nonlimiting examples of suitable thiuramidisulfides include N, N'-diethyl-, tetrabutyl-, N, N'-diisopropyldioctyl-, tetramethyl-, N, N'dicylohexyI-, N.N'-tetralaurylthiuramidisulfide, and combinations thereof.

In some embodiments, the crosslinking agents are silanes. Any silane can be used that can effectively graft to and / or crosslink the ethylene / α-olefin interpolymer of the polymer blend described herein. Non-limiting examples of suitable silane crosslinking agents include unsaturated silanes comprising an ethylenically unsaturated hydrocarbyl group, such as a vinyl, allyl, isopropenyl, butenyl group,

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cyclohexenyl or allyl gamma- (meth) acryloxy, and a hydrolyzable group such as a hydrocarbyloxy, hydrocarbonyloxy and hydrocarbylamino group. Non-limiting examples of suitable hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, proprionyloxy, alkyl and arylamino groups. In other embodiments, silanes are unsaturated alkoxysilanes that can be grafted onto the interpolymer. Some of these silanes and their methods of preparation are described in more detail in US Patent No. 5,266,627, which is incorporated herein by reference. In additional embodiments, the silane crosslinking agents are vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2methoxyethoxy) silane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, 3methacryloyloxypropyltrimethoxysilane, and combinations thereof.

The amount of the silane crosslinking agent can vary greatly, depending on the nature of the ethylene / α-olefin interpolymer or polymer blend, the silane used, the processing conditions, the amount of grafted initiator, the final application, and other factors. When vinyltrimethoxysilane (VTMOS - vinyltrimethoxysilane) is used, the amount of VTMOS is generally at least about 0.1 weight percent, at least about 0.5 weight percent, or at least 1 weight percent, based on the combined weight of the silane crosslinking agent and the interpolymer or polymer blend.

Applications

The ethylene polymer of the embodiment can be used in a variety of conventional thermoplastic manufacturing processes to

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producing useful articles, including objects comprising at least one layer of film, such as a monolayer film, or at least one layer on a multilayer film prepared by casting, melting, calendering, or extrusion coating processes; molded articles, such as blow molding, injection molding, or rotational molding; extrusions; fibers; and woven or non-woven fabrics. Thermoplastic compositions comprising the ethylenic polymer of the embodiment include blends with other natural or synthetic materials, polymers, additives, reinforcing agent, ignition resistant additives, antioxidants, stabilizers, colorants, extenders, crosslinkers, blowing agents and plasticizers.

The ethylenic polymer of the embodiment can be used in fiber production for other applications. Fibers that can be prepared from the ethylenic polymer of the embodiment or mixture thereof include artificial fibers, tow, multi-component, sheath / core, twist and monofilament. Suitable fiber-forming processes include filament weaving and extrusion blown techniques, as described in US Patent Nos. 4,340,563 (Appel, et al.), 4,663,220 (Wisneski, et al.), 4,668,566 (Nohr, et al.), And 4,322,027 (Reba), gel-spun fibers as described in US Patent No. 4,413,110 (Kavesh , et al.), woven and non-woven fabrics, as described in US Patent No. 3,458,706 (May), or structures made from such fibers, including blends with other fibers, such as polyester, nylon, or cotton, thermoformed articles, extruded shapes, including

profile extrusions and coextrusions, calendered articles, and extracted, twisted or pleated yarns or fibers.

The ethylenic polymer of the embodiment can be used in a variety of films, including, but not limited to, clarity shrink films, intercalation shrink films, cast stretch films, silage films, heat shrink films, sealants, upright bag films , cover films, and patterned diaper covers.

The ethylenic polymer of the embodiment is also useful in other direct end-use applications. The ethylenic polymer of the embodiment is useful for wire and cable coating operations, in blasting foils for vacuum forming operations, and formation molded articles, including the use of injection molding, blow molding process, or rotational molding processes. Compositions comprising the ethylenic polymer of the embodiment can also be formed into articles manufactured using conventional polyolefin processing techniques.

Other suitable applications for the ethylenic polymer of the embodiment include films and fibers; soft-touch goods, such as toothbrush holders and device holders; sealing gaskets and profiles; adhesives (including thermo printing adhesives and pressure sensitive adhesives); footwear (including soles and insoles for shoes); parts and profiles for the interior of the car; foam goods (both open and closed cells); impact modifiers for other thermoplastic polymers such

such as high-density polyethylene, isotactic polypropylene, or other olefin polymers; coated fabrics; hoses; pipeline; weatherstripping; sealing coatings; floor covering; and viscosity index modifiers, also known as pour point modifiers, for lubricants.

Further treatment of the ethylenic polymer of the embodiment may be performed to apply the ethylenic polymer of the embodiment for other end uses. For example, dispersions (both aqueous and nonaqueous) can also be formed using the present polymers or formulations comprising the same. The foams produced comprising the ethylenic polymer of the embodiment can also be formed, as described in PCT Publication No. 2005/021622 (Strandburg et al.). The ethylenic polymer of the embodiment can also be crosslinked by any known means, such as the use of peroxide, electron beam, silane, azide, or other crosslinking technique. The ethylenic polymer of the embodiment can also be chemically modified, such as by grafting (eg, by the use of maleic anhydride (MAH), silanes, or other grafting agent), halogenation, amination, sulfonation, or other chemical modification.

Additives and helpers may be added to the post-formation of the ethylenic polymer of the embodiment. Suitable additives include fillers, such as organic or inorganic particles, including clays, talc, titanium dioxide, zeolites, powdered metals, organic as well as inorganic fibers, including carbon fiber, fibers

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silicon nitride, steel wire or mesh, and nylon or polyester ties, nanoparticles, clays, etc .; glues, oil extenders, including paraffinic or naphthelene oils; and other natural or synthetic polymers, including other polymers that are manufactured or can be manufactured according to the methods of the embodiment.

Combinations and blends of the ethylenic polymer of the embodiment can be made with other polyolefins. Suitable polymers for blending with the ethylenic polymer of the embodiment include thermoplastic and non-thermoplastic polymers including natural and synthetic polymers. Exemplary blending polymers include polypropylene, (both impact modifying polypropylene, isotactic polypropylene, atactic polypropylene, and random ethylene / propylene copolymers), various types of polyethylene, including high pressure free radical LDPE, Ziegler's LLDPE -Natta, metallocene PE, including multiple reactor PE (in-reactor blends of Ziegler-Natta PE and metallocene PE, such as the products described in US Patents Nos. 6,545,088 (Kolthammer, et al.); 6,538,070 (Caldwell, et al.); 6,566,446 (Parikh, et al.); 5,844,045 (Kolthammer, et al.); 5,869,575 (Kolthammer, et al.); and 6,448,341 (Kolthammer, et al.)), ethylene vinyl acetate (EVA), ethylene / vinyl alcohol copolymers, polystyrene, impact modified polystyrene, ABS, styrene / butadiene block copolymers and derivatives hydrogenated thereof (SBS and SEBS), and thermoplastic polyurethanes. Homogeneous polymers such as elastomers and

olefin elastomers, ethylene-propylene-based copolymers (for example, polymers available under the trade designation Plastomers and Elastomers VERSIFY ™ (VERSIFY ™ Plastomers & Elastomers) (The Dow Chemical Company) and VISTAMAXX ™ (ExxonMobil Chemical Co.)) also they may be useful as blending components comprising the ethylenic polymer of the embodiment.

Combinations and blends of the ethylenic polymer of the embodiment may include blends of thermoplastic polyolefin (TPE), blends of thermoplastic elastomer (TPE), thermoplastic vulcanizates (TPV), and ethylenic polymer blends. The mixtures of TPE and TPV can be prepared by combining the ethylenic polymers of the embodiment, including the functionalized or unsaturated derivatives thereof, with an optional rubber, including conventional block copolymers, in particular an SBS block copolymer, and optionally an agent crosslinking or vulcanizing. TPO blends are generally prepared by blending the modality polymers with a polyolefin, and optionally a crosslinking or vulcanizing agent. The above blends can be used to form a molded object, and optionally crosslink the resulting molded article. A similar procedure using different components has been previously described in US Patent No. 6,797,779 (Ajbani, et al.).

D ending

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The term "composition", as used, includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

The terms "blend" or "polymer blend", as used, refers to an intimate (ie, no reaction) physical blend of two or more polymers. A mixture may or may not be miscible (no phase separation at the molecular level). A mixture may or may not be phased. A mixture may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art. Mixing can be accomplished by physically mixing the two or more polymers at the macro level (eg, melt blending resins or combining) or at the micro level (eg, simultaneous formation within the same reactor).

The term "linear" refers to polymers in which the main polymer structure lacks measurable or demonstrable long chain branches, for example, the polymer is replaced on average less than 0.01 long branches by 1000 carbons.

The term "polymer" refers to a polymeric compound prepared by polymerizing monomers, either of the same type or different. Consequently, the generic term polymer encompasses the term "homopolymer", generally used to refer to polymers prepared from only one type of monomer, and the term "interpolymer" as defined. The term "ethylene / a-41 polymer -

olefin ”is indicative of interpolymers as described.

The term "interpolymer" refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes copolymers, generally used to refer to polymers prepared from two different monomers, and polymers prepared from more than two different types of monomers.

The term "ethylene-based polymer" refers to a polymer that contains more than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomer) and, optionally, may contain at least one comonomer.

The term "ethylene / α-olefin interpolymer" refers to an interpolymer containing more than 50 mole percent copolymerized ethylene monomer (based on the total amount of polymerizable monomers) and at least one α-olefin.

The term "ethylenic polymer" refers to a polymer resulting from the bonding of an ethylene-based polymer and at least one very long-chain branched ethylene-based polymer.

Test methods

Density

Density (g / cm3) is measured in accordance with ASTM-D standard

-42'NSTgy? yA <Ex; cANOR

792-03, Method B, in isopropanol. Specimens are measured less than 1 hour from casting after isopropanol conditioning at 23 ° C for 8 minutes to achieve thermal equilibrium prior to measurement. Specimens are compression molded in accordance with ASTM-D-4703-00 Annex A with an initial warm-up period of approximately 5 minutes at 190 ° C and an increase rate of 15'C / minute by Procedure C. The specimen is cooled to 45 ° C in the press with continuous cooling until “cool to the touch”.

melt index

The melt index, ol2, is measured in accordance with ASTM D 1238, Condition 190 ° C / 2.16 kg, and is reported in grams evaded for 10 minutes. The l10 It is measured in accordance with ASTM D 1238, Condition 190 ° C / 2.16 kg, and is reported in grams evaded for 10 minutes.

DSC Crystallinity

DSC Differential Scanning Calorimetry can be used to measure the melting and crystallization behavior of a polymer over a wide temperature range. For example, the TA Instruments Q1000 DSC, equipped with an RCS (Registered Cooling System) and an Autosampler, is used to perform this analysis. During the test, a nitrogen purge gas flow of 50 ml / min is used. Every

· .- · ΛΧ * ι

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OF PROPERTY v \ ¡

INDUSTRIAL sample is melt-pressed into a thin film at approximately 175 ° C; the molten sample is then air cooled to room temperature (~ 25 ° C). A 3-10 mg specimen, 6 mm in diameter, is removed from the studied polymer, weighed, placed in a light aluminum mold (ca. 50 mg), and sealed by compression. Then, the analysis is performed to determine its thermal properties.

The thermal behavior of the sample is determined by increasing and decreasing the sample temperature in order to create a thermal flow against the temperature profile. Firstly, the sample is rapidly heated to 180 ° C and isothermal for 3 minutes in order to extract its thermal history. The sample is then cooled to -40 ° C at a cooling rate of 10 'C / minute and isothermal at -40 ° C for 3 minutes. The sample is then heated to 150 ° C (ie, the "second heating ramp") at a heating rate of 10'C / minute. The cooling and second heating curves are recorded. The cooling curve is analyzed by configuring the initial endpoints at the start of crystallization at -20 ° C. The heating curve is analyzed by configuring the initial endpoints from -20 ° C to the end of the melt. The determined values are the peak melting temperature (Tm), peak crystallization temperature (Tc), heat of fusion (HF) (in Joules per gram), and the% crystallinity calculated for the polyethylene samples using:

% of crystallinity = ((H,) / (292 J / g)) * 100.

Heat of fusion (HF) and the peak melting temperature are reported from the second heating curve. The peak crystallization temperature is determined from the cooling curve.

Gel Permeation Chromatography (GPC)

The GPC system consists of a Waters (Milford, MA) 150C high temperature chromatograph (other suitable high temperature GPC instruments include Polymer Laboratories (Shropshire, UK) Model 210 and Model 220) equipped with an integrated differential refractometer (Rl ). Additional detectors may include a Polymer ChAR IR4 infrared detector (Valencia, Spain), the Model 2040 Precision Detectors 2-angle laser light scattering detector (Amherst, MA), and a Viscotek 150R Capillary Solution 4 Viscometer. (Houston, TX). A GPC with the last two independent detectors and at least one of the first detectors is sometimes referred to as "3D-GPC", while the term "GPC" only generally refers to conventional GPC. Depending on the sample, the 15 degree angle or 90 degree angle of the light scattering detector is used for calculation purposes. Data collection is done using Viscotek TriSEC software, Version 3, and a data manager

Viscotek 4-channel DM400. The system is also equipped with an in-line solvent degassing device from Polymer Laboratories (Shropshire, UK). Suitable high temperature GPC columns such as four columns of

30 cm long Shodex HT803 microns or four 30 cm columns of Polymer Labs from the mixed 20 micron pore size package (MixA LS, Polymer Labs). The sample carousel compartment is operated at 140 ° C and the column compartment is operated at 150 ° C. The samples are prepared at a concentration of 0.1 g of polymer in 50 ml of solvent. The chromatographic solvent and the sample preparation solvent contain 200 ppm of butylated hydroxytoluene (BHT butylated hydroxytoluene). Both solvents are sprayed with nitrogen. The polyethylene samples are gently shaken at 160 ° C for four hours. The injection volume is 200 microliters. The flow rate through the GPC is adjusted to 1 ml / minute.

The adjusted GPC column is calibrated prior to performing the Examples by implementing twenty-one narrow molecular weight distribution polystyrene standards. The molecular weight (MW molecular weight) of the standards ranges from 580 to 8,400,000 grams per mole, and the standards are contained in 6 "cocktail" mixes. Each standard mixture has at least a decade of separation between the individual molecular weights. Standard mixtures are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared at 0.025 g in 50 mL of solvent for molecular weights equal to or greater than 1,000,000 grams per mole and 0.05 g in 50 mL of solvent for molecular weights less than 1,000,000 grams per mole. Polystyrene standards were resolved at 80 ° C with gentle agitation for 30 minutes. Narrow norm mixtures are implemented first and in decreasing order of weight component

higher molecular to minimize degradation. The peak molecular weights of the polyethylene norm are converted to Mw of polyethylene using the aforementioned Mark-Houwink K values (sometimes called a) for polystyrene and polyethylene. See the Examples section for a demonstration of this procedure.

With the 3D-GPC absolute weight average molecular weight ("Mw, Abs ”) and the intrinsic viscosity independently from suitable narrow polyethylene standards using the same conditions mentioned above. These narrow linear polyethylene standards can be obtained from Polymer Laboratories (Shropshire, UK; Parts Nos. PL2650-0101 and PL2650-0102).

The systematic approach for the determination of multi-detector compensation is carried out in a manner consistent with that published by Balke, Mourey, et al. (Mourey and Balke, Chromatography Polym., Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., Chapter 13, (1992)), optimizing the logarithmic results of the triple detector (Mw and viscosity intrinsic) of Dow 1683 wide polystyrene (American Polymer Standards Corp .; Mentor, OH) or its equivalent to the narrow standard column calibration results derived from the narrow polystyrene standard calibration curve. Molecular weight data, representing the volume compensation determination of the detector, are obtained in a manner consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil , P., Classical Light

Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injected concentration used in determining the molecular weight is obtained from the mass detector area and the mass detector constant derived from a suitable linear polyethylene homopolymer, or one of the polyethylene standards. The calculated molecular weights are obtained using a light scattering constant derived from one or more of the mentioned polyethylene standards and a refractive index concentration coefficient, dn / dc, of 0.014. Generally speaking, the response of the mass detector and the light scattering constant must be determined from a linear standard with a molecular weight greater than 50,000 daltons. Viscometer calibration can be performed using the methods described by the manufacturer or alternatively using published values of suitable linear standards such as the Standard Reference Materials (SRM) 1475a, 1482a, 1483, or 1484a. Chromatographic concentrations are assumed to be low enough to eliminate targeting of the 2two viral coefficient effects (effects of concentration on molecular weight).

Elution fractionation by analytical temperature rise (ATREF - Analytical Temperature Rising Elution Fractionation)

The high density fraction (percentage) is measured by

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temperature rise elution fractionation analysis (ATREF). ATREF analysis is performed according to the method described in US Patent No. 4,798,081 and Wilde, L; Ryle, TR; Knobeloch, DC; Peat, IR; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, Journal of Polymer Science, 20, 441-455 (1982). The composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column with inert support content (stainless steel shot) by slowly reducing the temperature to 20 ° C at a cooling rate of 0.1 ° C / min. The column is equipped with an infrared detector. Then, an ATREF chromatogram curve is generated by eluting the crystallized polymeric sample from the column, slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 to 120 ° C at a rate of 1.5 ° C / min. The viscosity average molecular weight (Mv) of the eluent polymer is measured and reported. An ATREF graph has the short chain branching distribution graph (SCBD) and a molecular weight graph. The SCBD plot has 3 peaks, one for the highly crystalline fraction (typically above 90 ° C), one for the copolymer fraction (typically between 30-90 ° C), and one for the purge fraction (typically below 30 ° C). The curve also has a valley between the copolymer fraction and the highly crystalline one. The is the lowest temperature in this valley. The% High Density Fraction (HD) is the area under the The previous curve. Mv is the weight

molecular average viscosity determined by ATREF. Mhc is the

Average mv for the previous fraction The. Me is the average Mv of the copolymer between 60-90 ° C. Mp is the average Mv of the entire polymer.

Fast Temperature Rising Elution Fractionation (FTREF)

Rapid TREF can be performed with a Polymer ChAR (Valencia, Spain) Crystex instrument in orthodichlorobenzene (ODCB) with a composition mode IR-4 infrared detector (Polymer ChAR, Spain) and dispersion detector Light (LS) (Precision Detector Inc., Amherst, MA).

When the F-TREF is tested, 120 mg of the sample is added in a Crystex reactor vessel with 40 ml of ODCB maintained at 160 ° C for 60 minutes with mechanical stirring to achieve sample dissolution. The sample is loaded onto the TREF column. The sample solution is then cooled in two stages: (1) from 160 ° C to 100 ° C at 40 ° C / minute, and (2) the polymer crystallization process started from 100 ° C to 30 ° C at 0.4'C / minute. Then, the sample solution is kept isothermally at 30 ° C for 30 minutes. The elution process increases in temperature from 30 ° C to 160 ° C at 1.5 ° C / minute with a flow rate of 0.6 ml / minute. The sample loading volume is 0.8 ml. The molecular weight of the sample (Mw) is calculated as the ratio of 15 ° or 90 °. The LS signal over the signal from the IR-4 detector's measurement sensor. The LS-MW calibration constant is obtained using polyethylene

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National Standards Office SRM 1484a. The elution temperature is reported as the current oven temperature. The pipe lag volume between the TREF and the detector is represented by the reported TREF elution temperature.

Preparative Temperature Rise Elution Fractionation (P-TREF - PreparativeTemperature Rising Elution Fractionation)

The temperature rise elution fractionation method (TREF) can be used to preparatively fractionate the polymers (P-TREF) and is derived from Wilde, L .; Ryle, TR; Knobeloch,

DC; Peat, IR; "Determination of Branching Distributions in Polyethylene and Ethylene Copolymers",

J. Polym. Se /., 20, 441-455 (1982), including dimensions of column, solvent, flow and temperature program. An infrared absorbance (IR) detector is used to monitor the elution of the polymer from the column. Separate programmable temperature liquid baths are also used - one per column load and one per column elution.

Samples are prepared by dissolving in trichlorobenzene (TCB) containing approximately 0.5% ditert-butyl-4-methylphenol at 160 ° C with a magnetic stir bar that provides stirring. Sample load is approximately one hundred milligrams per column found. After loading at 125 ° C, the column in the sample is cooled to 25 ° C for

approximately 72 hours. The sample and the cooled column are then transferred to the second programmable temperature bath and equilibrated at 25 ° C with a constant flow at 4ml / minute of TCB. A linear temperature program starts to increase the temperature by approximately 0.33 ° C / minute, reaching a maximum temperature of 102 ° C in approximately 4 hours.

Fractions are collected manually by placing a collection bottle at the exit of the IR rector. Based on previous ATREF analyzes, the first fraction is collected from 56 to 60 ° C. Subsequent small fractions, called subfractions, are collected every 4 ° C to 92 ° C, and then every 2 ° C to 102 ° C. Subfractions are referenced by the midpoint elution temperature at which the subfraction is collected.

Subfractions are frequently added to the larger regions by mid-point temperature ranges for testing. Fractions can be further combined into larger fractions for testing purposes.

A weighted average elution temperature is determined for each fraction based on the average of the elution temperature range for each subfraction and the weight of the subfraction versus the total weight of the sample. The weighted average temperature is defined as:

where T (f) is the temperature of the midpoint of a fraction or

INDUSTRIAL PROPERTY narrow segment and A (f) is the area of the segment, proportional to the amount of polymer, in the segment.

Data is stored digitally and processed using an EXCEL spreadsheet (Microsoft Corp .; Redmond, WA). The TREF plot, maximum peak temperatures, fraction weight percentages, and fraction weighted average temperatures were calculated using the spreadsheet program.

Turbidity is determined in accordance with ASTM-D-1003.

Gloss at 45 ° is determined according to ASTM-2457.

Elmendorf tear strength is measured in accordance with ASTM-D 1922.

Dart impact resistance is measured according to ASTM-D 1709-04, Method A.

C13 NMR Comonomer Content

It is known to use NMR spectroscopic methods to determine the composition of the polymer. ASTM D 5017-96, JC Randall et al., In "NMR and Macromolecules", ACS Series 247 Symposium, JC Randall, Ed., Am. Chem. Soc., Washington DC, 1984, chap. 9, and JC Randall in "Polymer Sequence Determination", Academic Press, New York (1977) provide general methods of polymer analysis by NMR spectroscopy.

Measurement of gei content

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When the ethylene interpolymer, either alone or included in a composition is at least partially articulated, the degree of crosslinking can be measured by dissolving the composition in a solvent for a specified duration, and calculating the percentage of gel or non-extractable component. The gel percentage usually increases with increasing levels of crosslinking. For cured articles according to the invention, the percentage of gel content is desirably in the range of at least about 5 to 100% measured in accordance with the ASTM standard.

D-2765.

Examples

Preparation of ethylene-based polymers

Multi-component catalyst

An exemplary multi-component catalyst system includes a Ziegler-Natta catalyst composition including a magnesium and titanium containing procatalyst and a cocatalyst. The procatalyst is a titanium-supported Ziegler-Natta catalyst characterized by a Mg: Ti molar ratio of 40: 1.0. The cocatalyst is a triethylaluminum. The procatalyst can have a Ti: Mg ratio between 1.0: 40 to 5.0: 40, preferably 3.0: 40. The procatalyst and cocatalyst components can be contacted either before entering the reactor or in the reactor. The procatalyst may, for example, be any other titanium-based Ziegler-Natta catalyst. The AI: Ti molar ratio of the

-54cocatalyst to the procatalyst component can range from about 1: 1 to about 5: 1.

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Multi-Component Catalyst System Overview

The multi-component catalyst system, as used herein, refers to a Ziegler-Natta catalyst composition that includes a magnesium and titanium containing procatalyst and a cocatalyst. The procatalyst may, for example, comprise the reaction product of magnesium dichloride, an alkylaluminum dihalide, and a titanium alkoxide.

The olefin polymerization procatalyst precursors comprise the product that results from combining:

(A) A magnesium halide prepared by contacting:

(1) at least one hydrocarbon soluble magnesium component represented by the general formula R "R'Mg.xAIR'3 where each R" and R 'are alkyl groups (2) at least one source of low metal or non-metal halide conditions such that the reaction temperature does not exceed about 60 ° C, preferably does not exceed about 40'C, and most preferably does not exceed about 35 ° C;

(B) at least one transition metal compound represented by the formula Tm (OR) and Xy-x where Tm is a metal from Groups IVB, VB, VIB, VIIB or VIII of the Periodic Table; R is a hydrocarbon group having from 1 to about 20, preferably from 1 to about 10 carbon atoms.

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MEXICAN INSTITUTE • f THE INDUSTIUAL ROWTY (C) an additional halide source if insufficient quantity of component (A-2) is present to provide the desired excess ratio X: Mg.

Particularly suitable transition metal compounds include, for example, titanium tetrachloride, titanium trichloride, vanadium tetrachloride, zirconium tetrachloride, tetra (isopropoxy) titanium, diethoxy tititanium dibromide, dibutoxy tititanium dichloride, tetraphenoxy titanium oxide, tri-isopropoxy, zirconium tetrapropoxide, mixtures thereof and the like.

Other suitable titanium compounds that can be employed as the transition metal component herein include those titanium complexes and / or compounds resulting from reacting:

(A) at least one titanium compound represented by the formula Ti (OR) x X4-x where each R is independently a hydrocarbyl group having from 1 to about 20, preferably from about 1 to about 10, most preferably from about 2 to about 4 carbon atoms; X is halogen and x has a value from zero to 4;

with (B) at least one compound containing at least one aromatic hydroxyl group.

The above procatalyst components are combined in proportions sufficient to provide atomic relationships as mentioned above.

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The above pro-catalytic reaction product is preferably prepared in the presence of an inert diluent. The concentrations of catalyst components are preferably such that when the essential components of the catalytic reaction product are combined, the resulting slurry ranges from about 0.005 to about 1.0 molar (moles / liter) with respect to magnesium. As an example of soluble inert organic diluents there may be mentioned liquefied ethane, propane, isobutane, n-butane, n-hexane, the various isomeric hexanes, isooctane, paraffinic mixtures of alkanes having from 8 to 12 carbon atoms, cyclohexane, methylcyclopentane , dimethylcyclohexane, dodecane, industrial solvents composed of saturated or aromatic hydrocarbons such as kerosene, naphtha, etc., especially when they are free of any olefin compounds and other impurities, and especially those that have boiling points in the range from about -50 ° C to about 200 ° C. The mixture of the procatalyst components to provide the desired catalytic reaction product is advantageously prepared under an inert atmosphere such as nitrogen, argon or other inert gas at temperatures in the range from about -100 ° C to about 200 ° C, preferably from about -20 ° C to about 100 ° C, since the magnesium halide support is prepared in such a way that the reaction temperature does not exceed about 60 ° C. In the preparation of the catalytic reaction product, it is not necessary to separate the soluble components

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in hydrocarbon of the hydrocarbon-insoluble components of the reaction product.

The procatalyst composition serves as a component of a Ziegler-Natta catalyst composition, in combination with a cocatalyst. The cocatalyst is preferably used in a titanium-based molar ratio in the procatalyst from 1: 1 to 100: 1, but more preferably in a molar ratio of from 1: 1 to 5: 1.

Inventive Example 1

Inventive Example 1 is made according to the following procedures: A heterogeneously branched ethylene / α-olefin copolymer is prepared using a multi-component catalyst system, as described hereinabove, suitable for (co) polymerizing ethylene and one or more aolefin comonomers, for example 1-octene, in two adiabatic spherical reactors, connected together in series, operating under a solution condition. Ethylene monomer, 1-octene comonomer, and hydrogen were combined with a solvent, eg, Isopar®, commercially available from ExxonMobii. Feed streams are purified from polar impurities such as water, carbon monoxide, sulfur compounds, and unsaturated compounds such as acetylene and shipped at 13 ° C before entering the reactor. The majority (85-90%) of the reaction occurs in the first standby reactor that is 10 feet (3 m) in diameter. Mixing is accomplished by

circulation of the solution, M Polymer / Catalyst / Cocatalyst / Solvent / Ethylene / Comonomer / Hydrogen not with stirrer equipped with mixing paddles. The feed (ethylene / comonomer / solvent / hydrogen) enter the reactor from the bottom and the catalyst / cocatalyst enter the reactor separately from the feed and also from the bottom. The temperature of the first reactor is approximately 175 ° C, and the pressure of the reactor is approximately 500 psi. The temperature of the second reactor, in series with the first, is increased to 202 ° C with approximately 10/15% of the remaining reaction occurring and without adding additional flows. The Al / Ti molar feed ratio of catalyst / cocatalyst is set to 1.5. The average residence time of the reactor is approximately 8 minutes per sphere reactor prior to termination post-reactor for a fluid specially designed for that purpose. After the polymer solution leaves the reactor, the solvent with unconverted ethylene monomer and 1-octene is removed from the polymer solution by a two-stage devolatilizer system, and then recycled. The recycled stream is purified before entering the reactor again. The polymer melt is pumped through a nozzle specially designed for underwater pelletizing. The tablets are transferred through sieves to remove particles of above and below average dimensions. The finished tablets are then transferred to wagons. The properties of the heterogeneously branched ethylene / α-olefin copolymer are listed in the Table

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one. Figure 1 is an ATREF of Inventive Example 1.

The heterogeneously branched ethylene / α-olefin copolymer is further processed by a Gloucester line blown film extrusion process with a 6 inch (15 cm) diameter Sano nozzle. The nozzle has a 70-thousandth-inch (0.17 cm) hole. The film is blown with a blowing ratio of approximately 2.5 and a frost line height of approximately 30 inches (76 cm). The width of the flat film is approximately 23.5 inches (60 cm), while the thickness of the films is approximately 2 thousandths of an inch (0.05 mm). The heterogeneously branched ethylene / α-olefin copolymer is melt extruded through an annular circular die. The thermal impression emerges from the nozzle thus forming a tube. The tube is expanded by air, and at the same time, cold air cools the framework to a solid state. The film tube is then collapsed into a V-shaped roller frame and clamped at the end of the frame to trap air within the bubble. The rear stretch cylinders also remove the film from the nozzle. The tube is cut and wrapped as a single film layer on a roll. The properties of the inventive film 1 are listed in Table 2.

Comparative Example 1

Comparative Example 1, a linear low density polyethylene, is made at a reactor temperature of 190 ° C and a ratio of

-60Al / Ti 3.5: 1. The other conditions remain i

Inventive Example 1. The properties of Comparative Example 1 are listed in Table 1. Figure 1 is an ATREF Comparative Example

one. Comparative Example 1 is processed by blown film extrusion processes, as described above. Comparative Example 1 is melt extruded through an annular circular die. The thermal impression emerges from the nozzle, thus forming a tube. The tube is expanded by air, and at the same time, cold air cools the framework to a solid state. The film tube is then collapsed into a V-shaped roller frame and clamped at the end of the frame to trap air within the bubble. The rear stretch cylinders also remove the film from the nozzle. The tube is cut and wrapped as a single film layer on a roll. The properties of the inventive film 1 are listed in Table 2.

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Table 1: Resin production and characterization data inventive and comparative example 1,

<td>Description</td><td>Example inventive 1</td><td>Comparative Example 1</td>

<td>MI resin (g / 10 minutes)</td><td> 0.80</td><td> 0.80</td>

<td>Resin density (g / cc)</td><td> 0.917</td><td> 0.917</td>

<td>Catalyst</td><td>HEC-3</td><td>HEC-3</td>

<td>Rx temperature. ('C)</td><td> 1.75</td><td> 190</td>

<td>% of HD fraction - ATREF</td><td> 10.6</td><td> 15.4</td>

The lowest temperature in the valley between the copolymer and highly crystalline fraction

Mv, average molecular weight of viscosity determined by ATREF

Mhc, Mv average for the fraction over The determined by ATREF

Me, Mv average copolymer between 60-90 ° C determined by ATREF

Mp, Mv average of all the polymer determined by ATREF% of HD fraction, area under the curve on The

Table 2; Properties of the films made from Inventive Example 1 and Comparative Example 1.

<td>Description</td><td></td><td>Inventive Example 1</td><td>Comparative Example 1</td>

<td>Target thickness</td><td>thousandth of an inch</td><td> 2</td><td> 2</td>

<td>Brightness at 45 °</td><td></td><td> 91</td><td> 70</td>

<td>Turbidity</td><td> %</td><td> 5.6</td><td> 10.6</td>

<td>normalized</td><td>g / thousandth of an inch</td><td> 477</td><td> 469</td>

Although the embodiments have been described in particular, it will be appreciated that various other modifications will be apparent and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims be limited to the examples and descriptions set forth, but rather that the claims encompass all of the patentable novelty features of the present invention, including all features that would be treated as equivalents by those skilled in the art to which the invention belongs.

The description of preferred or desired substitutes, ranges, end uses, processes, or combinations, more preferred or more desired, highly preferred or highly desired, or more preferred or more desired with respect to any of the disclosed compositions and methods, is intended to be also applicable to any other preceding or successive modality of the compositions and methods described, regardless of the identity of any other substitute, range, use, specific process or combination.

Unless stated otherwise, implicit from context or conventional in the art, all parts and percentages are based on weight.

All cited applications, publications, patents, testing procedures, and other documents, including priority documents, are fully incorporated for reference to such an extent that the description is not inconsistent with the compositions and methods.

owm.n> t described and for all jurisdictions where such a # B "WM" aBPieBW "e * e" WMW incorporation is allowed.

Depending on the context in which such values are described, and unless specifically stated otherwise, such values may vary by 1 percent, 2 percent, 5 percent, or sometimes 10 to 20 percent. When describing a numerical range with a lower limit, RL, and an upper limit, RU, several within the range are specifically described, including the limits themselves. In particular, the following numbers within the range are specifically described: R = RL + k * (RU-RL), where k is a variable that varies from 0.01 to 1.00 with an increase of 0.01, that is, k is 0.01 or 0.02 to 0.99 or 1.00. In addition, any numerical range defined by two R numbers as defined is also specifically described.

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