US20110003940A1 - Ethylene-based polymer compositions for use as a blend component in shrinkage film applications - Google Patents

Ethylene-based polymer compositions for use as a blend component in shrinkage film applications Download PDF

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US20110003940A1
US20110003940A1 US12/814,902 US81490210A US2011003940A1 US 20110003940 A1 US20110003940 A1 US 20110003940A1 US 81490210 A US81490210 A US 81490210A US 2011003940 A1 US2011003940 A1 US 2011003940A1
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Teresa P. Karjala
Rongjuan Cong
Colleen M. Tice
Sarah M. Hayne
Mehmet Demirors
Lori L. Kardos
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Priority to US12/814,902 priority Critical patent/US20110003940A1/en
Assigned to DOW GLOBAL TECHNOLOGIES INC. reassignment DOW GLOBAL TECHNOLOGIES INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HAYNE, SARAH M., CONG, RONGJUAN, DEMIRORS, MEHMET, HERMEL-DAVIDOCK, THERESA J.
Publication of US20110003940A1 publication Critical patent/US20110003940A1/en
Priority to MX2012014835A priority patent/MX355375B/es
Priority to CN201180039227.1A priority patent/CN103168072B/zh
Priority to RU2013101567/04A priority patent/RU2013101567A/ru
Priority to MYPI2012005363A priority patent/MY160184A/en
Priority to PCT/US2011/027912 priority patent/WO2011159376A1/en
Priority to JP2013515330A priority patent/JP5975987B2/ja
Priority to BR112012032006-8A priority patent/BR112012032006B1/pt
Priority to EP18206327.1A priority patent/EP3473673A1/en
Priority to KR1020137000801A priority patent/KR20130089230A/ko
Priority to EP11708669.4A priority patent/EP2580279B1/en
Priority to ES11708669T priority patent/ES2716549T3/es
Priority to US13/453,541 priority patent/US8629214B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/30—Control of physical parameters of the fluid carrier of temperature
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/50—Conditioning of the sorbent material or stationary liquid
    • G01N30/52—Physical parameters
    • G01N30/54—Temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/05—Bimodal or multimodal molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • the invention is an ethylene-based polymer composition characterized by a Comonomer Distribution Constant greater than about 45 and as high as 400, wherein the composition has less than 120 total unsaturation unit/1,000,000 C, wherein the composition is further characterized as comprising a MW Ratio at each temperature is less than or equal to 1.00 for each fraction comprising more than 1.0 wt % which represents the area of the fraction divided by the total area of all fractions, preferably where the MW Ratio increases with the temperature of each fraction and also preferably wherein the MW Ratio is less than 0.10 for each temperature that is equal to or lower than 50° C.
  • the cumulative weight fraction can be less than 0.10 for the fractions with a temperature up to 50° C. and preferably the cumulative weight fraction is not less than 0.03 for the fractions with a temperature up to 85° C.
  • compositions are also contemplated, especially at least one film layer, as are thermoplastic formulations comprising the compositions and at least one natural or synthetic polymer, especially wherein the synthetic polymer is LDPE and the % LDPE is greater than 30% in which in which a blown film comprising the formulation has a MD shrink tension is greater than 15 cN, puncture is greater than 60 ft-lb/in 3 , and haze is less than 20%.
  • the compositions can be at least partially cross-linked (at least 5 wt % gel).
  • the compositions can have a comonomer distribution profile comprising a mono or bimodal distribution from 35° C. to 120° C., excluding the purge and can also have a Mw from about 80,000 to about 200,000 g/mol.
  • the invention is a process comprising:
  • M 3 is Ti, Hf or Zr, preferably Zr;
  • Ar 4 independently each occurrence is a substituted C 9-20 aryl group, wherein the substituents, independently each occurrence, are selected from the group consisting of alkyl; cycloalkyl; and aryl groups; and halo-, trihydrocarbylsilyl- and halohydrocarbyl-substituted derivatives thereof, with the proviso that at least one substituent lacks co-planarity with the aryl group to which it is attached;
  • T 4 independently each occurrence is a C 2-20 alkylene, cycloalkylene or cycloalkenylene group, or an inertly substituted derivative thereof;
  • R 21 independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or di(hydrocarbyl)amino group of up to 50 atoms not counting hydrogen;
  • R 3 independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen, or two R 3 groups on the same arylene ring together or an R 3 and an R 21 group on the same or different arylene ring together form a divalent ligand group attached to the arylene group in two positions or join two different arylene rings together; and
  • R D independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R D groups together are a hydrocarbylene, hydrocarbadiyl, diene, or poly(hydrocarbyl)silylene group, especially where the reaction of step (B) occurs by graft polymerization.
  • FIG. 1 is comonomer distribution profile for Example 1
  • FIG. 2 is 1 H NMR integral regions for unsaturation
  • FIG. 6 is melt strength data at 190° C. of 0.5 MI type samples: Examples 1, 2, 3, and 7 and Comparative Example 2;
  • FIG. 7 is melt strength data at 190° C. of 0.85 MI type samples: Examples 4, 5, 6, and 8 and Comparative Example 1;
  • FIG. 8 is conventional GPC plot for Examples 1-5;
  • FIG. 9 is conventional GPC plot for Examples 6-8 and Comparative Examples 1-2;
  • FIG. 10 is CEF plot for Examples 1-4 and Comparative Example 1;
  • FIG. 11 is CEF plot for Examples 5-8 and Comparative Example 2;
  • FIG. 12 is MW Ratio plot for Examples 1-4 and Comparative Examples 1-2.
  • FIG. 13 is MW Ratio plot for Examples 5-8 and Comparative Examples 1-2.
  • processing aids such as plasticizers
  • plasticizers can also be included in the ethylenic polymer product.
  • these aids include, but are not limited to, the 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 feedstocks.
  • exemplary classes of 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.).
  • ethylenic polymers are treated with one or more stabilizers, for example, antioxidants, such as IRGANOX 1010 and IRGAFOS 168 (Ciba Specialty Chemicals; Glattbrugg, Switzerland).
  • stabilizers for example, antioxidants, such as IRGANOX 1010 and IRGAFOS 168 (Ciba Specialty Chemicals; Glattbrugg, Switzerland).
  • polymers are treated with one or more stabilizers before an extrusion or other melt processes.
  • other polymeric additives include, but are not limited to, ultraviolet light absorbers, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents, fire retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity control agents and anti-blocking agents.
  • the ethylenic polymer composition may, for example, comprise less than 10 percent by the combined weight of one or more additives, based on the weight of the embodiment ethylenic polymer.
  • a particular benefit of the claimed polymers is the absence of catalyst kill agents, other than water, thus eliminating the need for calcium stearate.
  • the ethylenic polymer may be employed in a variety of conventional thermoplastic fabrication processes to produce useful articles, including objects comprising at least one film layer, such as a monolayer film, or at least one layer in a multilayer film prepared by cast, blown, calendered, or extrusion coating processes; molded articles, such as blow molded, injection molded, or rotomolded articles; extrusions; fibers; and woven or non-woven fabrics.
  • Thermoplastic compositions comprising the ethylenic polymer include blends with other natural or synthetic materials, polymers, additives, reinforcing agents, ignition resistant additives, antioxidants, stabilizers, colorants, extenders, crosslinkers, blowing agents, and plasticizers.
  • the ethylenic polymer may be used in producing fibers for other applications.
  • Fibers that may be prepared from the ethylenic polymer or blends thereof include staple fibers, tow, multicomponent, sheath/core, twisted, and monofilament.
  • Suitable fiber forming processes include spunbonded and melt blown techniques, as disclosed in U.S. Pat. No. 4,340,563 (Appel, et al.), U.S. Pat. No. 4,663,220 (Wisneski, et al.), U.S. Pat. No. 4,668,566 (Nohr, et al.), and U.S. Pat. No. 4,322,027 (Reba), gel spun fibers as disclosed in U.S. Pat. No.
  • Additives and adjuvants may be added to the ethylenic polymer post-formation.
  • Suitable additives include fillers, such as organic or inorganic particles, including clays, talc, titanium dioxide, zeolites, powdered metals, organic or inorganic fibers, including carbon fibers, silicon nitride fibers, steel wire or mesh, and nylon or polyester cording, nano-sized particles, clays, and so forth; tackifiers, oil extenders, including paraffinic or napthelenic oils; and other natural and synthetic polymers, including other polymers that are or can be made according to the embodiment methods.
  • fillers such as organic or inorganic particles, including clays, talc, titanium dioxide, zeolites, powdered metals, organic or inorganic fibers, including carbon fibers, silicon nitride fibers, steel wire or mesh, and nylon or polyester cording, nano-sized particles, clays, and so forth; tackifiers, oil extenders, including paraffinic or nap
  • Blends and mixtures of the ethylenic polymer with other polyolefins may be performed.
  • Suitable polymers for blending with the embodiment ethylenic polymer include thermoplastic and non-thermoplastic polymers including natural and synthetic polymers.
  • Exemplary polymers for blending include polypropylene, (both impact modifying polypropylene, isotactic polypropylene, atactic polypropylene, and random ethylene/propylene copolymers), various types of polyethylene, including high pressure, free-radical low density polyethylene (LDPE), Ziegler-Natta linear low density polyethylene (LLDPE), metallocene PE, including multiple reactor PE (“in reactor” blends of Ziegler-Natta PE and metallocene PE, such as products disclosed in U.S.
  • LDPE free-radical low density polyethylene
  • LLDPE Ziegler-Natta linear low density polyethylene
  • metallocene PE including multiple reactor PE (“in reactor” blends of Ziegler-Natta PE and metal
  • 6,448,341 (Kolthammer, et al.)), ethylene-vinyl acetate (EVA), ethylene/vinyl alcohol copolymers, polystyrene, impact modified polystyrene, Acrylonitrile-Butadiene-Styrene (ABS), styrene/butadiene block copolymers and hydrogenated derivatives thereof (Styrene-Butadiene-Styrene (SBS) and Styrene-Ethylene-Butadiene-Styrene (SEBS), and thermoplastic polyurethanes.
  • EVA ethylene-vinyl acetate
  • ABS Acrylonitrile-Butadiene-Styrene
  • SBS Styrene-Ethylene-Butadiene-Styrene
  • SEBS Styrene-Ethylene-Butadiene-Styrene
  • Homogeneous polymers such as olefin plastomers and elastomers, ethylene and propylene-based copolymers (for example, polymers available under the trade designation VERSIFYTM Plastomers & Elastomers (The Dow Chemical Company), SURPASSTM (Nova Chemicals), and VISTAMAXXTM (ExxonMobil Chemical Co.)) can also be useful as components in blends comprising the ethylenic polymer.
  • VERSIFYTM Plastomers & Elastomers The Dow Chemical Company
  • SURPASSTM Nova Chemicals
  • VISTAMAXXTM ExxonMobil Chemical Co.
  • the ethylenic polymer maybe employed as sealant resins.
  • SCBD short chain branching distribution
  • CDC Comonomer Distribution Constant
  • MWD molecular weight distribution
  • LCB long chain branching
  • the ethylenic polymer may be employed as a pipe and tubing resin through an optimization of the SCBD and MWD, with low unsaturation levels for improved ESCR (environmental stress crack resistance) and higher PENT (Pennsylvania Edge-Notch Tensile Test).
  • the ethylenic polymer may be employed in applications where ultraviolet (UV) stability, and weatherability are desired through an optimization of the SCBD and MWD, in combination with low unsaturation levels, and low levels of low molecular weight, high comonomer incorporated oligomers.
  • the ethylenic polymer may be employed in applications where low levels of plate-out, blooming, die build-up, smoke formation, extractables, taste, and odor are desired through an optimization of the SCBD and MWD with low levels of low molecular weight, high comonomer incorporated oligomers.
  • the ethylenic polymer may be employed in stretch film applications. Surprisingly, certain SCBD, in combination with certain MWD, and a certain level of long chain branching (LCB) shows improved stretchability and dynamic puncture resistance.
  • LCB long chain branching
  • composition includes a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
  • blend or “polymer blend,” as used, mean an intimate physical mixture (that is, without reaction) of two or more polymers.
  • a blend may or may not be miscible (not phase separated at molecular level).
  • a blend may or may not be phase separated.
  • a blend 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.
  • the blend may be affected by physically mixing the two or more polymers on the macro level (for example, melt blending resins or compounding) or the micro level (for example, simultaneous forming within the same reactor).
  • linear refers to polymers where the polymer backbone of the polymer lacks measurable or demonstrable long chain branches, for example, the polymer can be substituted with an average of less than 0.01 long branch per 1000 carbons.
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer, and the term “interpolymer” as defined.
  • the terms “ethylene/ ⁇ -olefin polymer” is indicative of interpolymers as described.
  • interpolymer refers to polymers prepared by the polymerization of at least two different types of monomers.
  • the generic term interpolymer includes copolymers, usually employed to refer to polymers prepared from two different monomers, and polymers prepared from more than two different types of monomers.
  • ethylene-based polymer refers to a polymer that contains more than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and, optionally, may contain at least one comonomer.
  • ethylene/ ⁇ -olefin interpolymer refers to an interpolymer that contains more than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and at least one ⁇ -olefin.
  • ethylenic polymer refers to a polymer resulting from the intermolecular bonding of a crystalline ethylene-based polymer and at least one highly long chain branched ethylene-based polymer.
  • Samples that are measured for density are prepared according to ASTM D 1928. Measurements are made within one hour of sample pressing using ASTM D792, Method B.
  • Melt index, MI or I 2 is measured in accordance with ASTM D 1238, Condition 190° C./2.16 kg, and is reported in grams eluted per 10 minutes.
  • I 10 is measured in accordance with ASTM D 1238, Condition 190° C./10 kg, and is reported in grams eluted per 10 minutes.
  • Differential Scanning Calorimetry can be used to measure the melting and crystallization behavior of a polymer over a wide range of temperature.
  • the TA Instruments Q1000 DSC equipped with an RCS (refrigerated cooling system) and an autosampler is used to perform this analysis.
  • RCS refrigerated cooling system
  • a nitrogen purge gas flow of 50 L/min is used.
  • Each sample is melt pressed into a thin film at about 175° C.; the melted sample is then air-cooled to room temperature ( ⁇ 25° C.).
  • a 3-10 mg, 6 mm diameter specimen is extracted from the cooled polymer, weighed, placed in a light aluminum pan (ca 50 mg), and crimped shut. Analysis is then performed to determine its thermal properties.
  • the thermal behavior of the sample is determined by ramping the sample temperature up and down to create a heat flow versus temperature profile. First, the sample is rapidly heated to 180° C. and held isothermal for 3 minutes in order to remove its thermal history. Next, the sample is cooled to ⁇ 40° C. at a 10° C./minute cooling rate and held isothermal at ⁇ 40° C. for 3 minutes. The sample is then heated to 150° C. (this is the “second heat” ramp) at a 10° C./minute heating rate. The cooling and second heating curves are recorded. The cool curve is analyzed by setting baseline endpoints from the beginning of crystallization to ⁇ 20° C. The heat curve is analyzed by setting baseline endpoints from ⁇ 20° C. to the end of melt. The values determined are peak melting temperature (T m ), peak crystallization temperature (T a ), heat of fusion (H f ) (in Joules per gram), and the calculated % Crystallinity for polyethylene samples using Equation (1):
  • Resins were compression-molded into 3 mm thick ⁇ 1 inch circular plaques at 350° F. for 5 minutes under 1500 psi pressure in air. The sample is then taken out of the press and placed on the counter to cool.
  • a constant temperature frequency sweep is performed using a TA Instruments “Advanced Rheometric Expansion System (ARES),” equipped with 25 mm parallel plates, under a nitrogen purge.
  • the sample is placed on the plate and allowed to melt for five minutes at 190° C.
  • the plates are then closed to 2 mm, the sample trimmed, and then the test is started.
  • the method has an additional five minute delay built in, to allow for temperature equilibrium.
  • the experiments are performed at 190° C. over a frequency range of 0.1 to 100 rad/s.
  • the strain amplitude is constant at 10%.
  • the stress response is analyzed in terms of amplitude and phase, from which the storage modulus (G′), loss modulus (G′′), complex modulus (G*), dynamic viscosity ⁇ *, and tan ( ⁇ ) or tan delta are calculated.
  • CEF Crystallization Elution Fractionation
  • PolymerChar in Spain B. Monrabal et al, Macromol. Symp. 257, 71-79 (2007).
  • Ortho-dichlorobenzene (ODCB) with 600 ppm antioxidant butylated hydroxytoluene (BHT) is used as the solvent.
  • Sample preparation is done with an autosampler at 160° C. for 2 hours under shaking at 4 mg/ml (unless otherwise specified).
  • the injection volume is 300 ⁇ l.
  • the top oven temperature where the detectors and injection loop are located at is at 150° C.
  • the temperature profile of CEF is: crystallization at 3° C./min from 110° C.
  • the flow rate during crystallization is at 0.052 ml/min.
  • the flow rate during elution is at 0.50 ml/min.
  • the data is collected at one data point/second.
  • the CEF column is packed by the Dow Chemical Company with glass beads at 125 micron ⁇ 6% (MO-SCI Specialty Products) with 1 ⁇ 8 inch stainless tubing. The glass beads are acid washed by MO-SCI Specialty.
  • the column volume is 2.06 ml.
  • the column temperature calibration is performed by using a mixture of NIST Standard Reference Material Linear polyethylene 1475a (1.0 mg/ml) and Eicosane (2 mg/ml) in ODCB. The temperature is calibrated by adjusting the elution heating rate so that the NIST linear polyethylene 1475a has a peak temperature at 101.0° C., and Eicosane has a peak temperature of 30.0° C.
  • the CEF column resolution is calculated with a mixture of NIST linear polyethylene 1475a (1.0 mg/ml) and hexacontane (Fluka, purum, ⁇ 97.0%) (1 mg/ml).
  • a baseline separation of hexacontane and NIST polyethylene 1475a is achieved.
  • the area of hexacontane (from 35.0 to 67.0° C.) to the area of NIST 1475a from 67.0 to 110.0° C. is 50 to 50
  • the amount of soluble fraction below 35.0° C. is ⁇ 1.8 wt %.
  • Equation 2 The CEF column resolution is defined by Equation 2:
  • the column resolution is 6.0
  • CDC comonomer distribution constant
  • the comonomer distribution index is the total weight fraction of polymer chains with the comonomer content ranging from 0.5 of the median comonomer content (C median ) and 1.5 of the C median from 35.0 to 119.0° C.
  • the Comonomer Distribution Shape Factor is defined as a ratio of the half width of the comonomer distribution profile divided by the standard deviation of the comonomer distribution profile from the peak temperature (T p ) further divided by 100.
  • the CDC is calculated according to the following steps:
  • the comonomer content calibration curve is constructed by using a series of reference materials with known amount of comonomer content. Eleven reference materials with narrow comonomer distribution (monomodal comonomer distribution in CEF from 35.0 to 119.0° C.) with weight average molecular weight M w of 35,000 to 115,000 g/mol (by conventional GPC) at a comonomer content ranging from 0.0 mole % to 7.0 mol % are analyzed with CEF at the same experimental conditions as specified in the CEF experimental sections.
  • the comonomer content calibration is calculated by using the peak temperature (T p ) of each reference material and its comonomer content.
  • R 2 is the correlation constant for the calibration.
  • the Comonomer Distribution Index is the total weight fraction with a comonomer content ranging from 0.5 mulitplied by C median to 1.5 multiplied by C median . If T median is higher than 98.0° C., the Comonomer Distribution Index is defined as 0.95.
  • the maximum peak height is obtained from the CEF comonomer distribution profile by searching each data point to determine the highest peak from 35.0° C. to 119.0° C. (if two peaks are identical then the lower temperature peak is selected).
  • the half width is defined as the temperature difference between the front temperature and the rear temperature at half of the maximum peak height.
  • the front temperature at half of the maximum peak height is searched forward from 35.0° C., while the rear temperature at half of the maximum peak is searched backward from 119.0° C.
  • the half-width of the polymer is calculated as the arithmetic average of the half width of each peak.
  • Example 1 An example of the comonomer distribution profile for Example 1 is shown in FIG. 1 .
  • the chromatographic system consist of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220.
  • the column and carousel compartments are operated at 140° C.
  • Three Polymer Laboratories 10- ⁇ m Mixed-B columns are used with a solvent of 1,2,4-trichlorobenzene.
  • the samples are prepared at a concentration of 0.1 g of polymer in 50 mL of solvent.
  • the solvent used to prepare the samples contains 200 ppm of the antioxidant butylated hydroxytoluene (BHT). Samples are prepared by agitating lightly for 4 hours at 160° C.
  • BHT antioxidant butylated hydroxytoluene
  • the injection volume used is 100 microliters and the flow rate is 1.0 mL/min
  • Calibration of the GPC column set is performed with twenty one narrow molecular weight distribution polystyrene standards purchased from Polymer Laboratories.
  • the polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 8:
  • M polyethylene A ( M polystyrene ) B (Eq. 8)
  • M is the molecular weight
  • A has a value of 0.4316 and B is equal to 1.0.
  • a third order polynomial is determined to build the logarithmic molecular weight calibration as a function of elution volume. Polyethylene equivalent molecular weight calculations are performed using Viscotek TriSEC software Version 3.0. The precision of the weight-average molecular weight ⁇ M w is excellent at ⁇ 2.6%.
  • Zero-shear viscosities are obtained via creep tests that are conducted on an AR-G2 stress controlled rheometer (TA Instruments; New Castle, Del.) using 25-mm-diameter parallel plates at 190° C.
  • the rheometer oven is set to test temperature for at least 30 minutes prior to zeroing the fixtures.
  • a compression molded sample disk is inserted between the plates and allowed to come to equilibrium for 5 minutes.
  • the upper plate is then lowered down to 50 ⁇ m above the desired testing gap (1.5 mm) Any superfluous material is trimmed off and the upper plate is lowered to the desired gap. Measurements are done under nitrogen purging at a flow rate of 5 L/min.
  • the default creep time is set for 2 hours.
  • a constant low shear stress of 20 Pa is applied for all of the samples to ensure that the steady state shear rate is low enough to be in the Newtonian region.
  • the resulting steady state shear rates are in the range of 10 ⁇ 3 to 10 ⁇ 4 s ⁇ 1 for the samples in this study.
  • Steady state is determined by taking a linear regression for all the data in the last 10% time window of the plot of log (J(t)) vs. log(t), where J(t) is creep compliance and t is creep time. If the slope of the linear regression is greater than 0.97, steady state is considered to be reached, then the creep test is stopped. In all cases in this study the slope meets the criterion within 2 hours.
  • the steady state shear rate is determined from the slope of the linear regression of all of the data points in the last 10% time window of the plot of strain vs. time.
  • the zero-shear viscosity is determined from the ratio of the applied stress to the steady state shear rate.
  • a small amplitude oscillatory shear test is conducted before and after the creep test on the same specimen from 0.1 to 100 rad/s.
  • the complex viscosity values of the two tests are compared. If the difference of the viscosity values at 0.1 rad/s is greater than 5%, the sample is considered to have degraded during the creep test, and the result is discarded.
  • ZSVR zero-shear viscosity ratio
  • the ZSV value is obtained from the creep test at 190° C. via the method described above.
  • the Mw-gpc value is determined by the conventional GPC method as described previously.
  • the correlation between the ZSV of linear polyethylene and its Mw-gpc value was established based on a series of linear polyethylene reference materials.
  • a description for the ZSV-Mw relationship can be found in: Karjala, Maria P.; Sammler, Robert L.; Mangnus, Marc A.; Hazlitt, Lonnie G.; Johnson, Mark S.; Hagen, Charles M., Jr.; Huang, Joe W. L.; Reichek, Kenneth N. “Detection of low levels of long-chain branching in polyolefins.” Annual Technical Conference, Society of Plastics Engineers (2008), 66 th , p. 887-891.
  • Melt strength is measured at 190° C. using a Göettfert Rheotens 71.97 (Göettfert Inc.; Rock Hill, S.C.), melt fed with a Göettfert Rheotester 2000 capillary rheometer equipped with a flat entrance angle (180 degrees) of length of 30 mm and diameter of 2 mm.
  • the extrudate passes through the wheels of the Rheotens located at 100 mm below the die exit and is pulled by the wheels downward at an acceleration rate of 2.4 mm/s 2 .
  • the force (in cN) exerted on the wheels is recorded as a function of the velocity of the wheels (in mm/s). Melt strength is reported as the plateau force (cN) before the strand broke.
  • the baseline is corrected from 7 to ⁇ 2 ppm.
  • the signal from the residual 1 H of TCE is set to 100.
  • the integral I total from ⁇ 0.5 to 3 ppm is used as the signal from the whole polymer in the control experiment.
  • the number of CH 2 groups, NCH 2 , in the polymer is calculated from Equation 10:
  • NCH 2 I total /2 (Eq. 10)
  • the baseline is corrected from 6.6 to 4.5 ppm.
  • the signal from the residual 1 H of TCE is set to 100, the corresponding integrals for unsaturations (I vinylene , I trisubstituted , I vinyl and I vinylidene ) are integrated based on the region shown in FIG. 2 .
  • the number of unsaturation units for vinylene, trisubstituted, vinyl and vinylidene are calculated as in Equations 11-14.
  • N vinylene I vinylene /2 (Eq. 11)
  • N vinyl I vinyl /2 (Eq. 13)
  • N vinylidene I vinylidene /2 (Eq. 14)
  • N trisubstitutedd /1,000,000 C ( N trisubstituted /NCH 2 )*1,000,000 (Eq. 16)
  • the experiment is performed with an instrument constructed according to Gillespie and Li Pi Shan et al. (Apparatus for Method for Polymer Characterization, WO2006081116).
  • the data acquisition rate is one data point/second.
  • the TREF columns are constructed from acetone-washed 1 ⁇ 8 inch ⁇ 0.085 inch 316 stainless steel tubing.
  • the tubing is cut to a length of 42 inches and packed with a dry mixture (60:40 volume:volume) of pacified 316 stainless steel cut wire of 0.028 inch diameter (Pellet Inc., North Tonawanda, N.Y.) and 30-40 mesh spherical technical grade glass beads.
  • This combination of column length and packing material results in an interstitial volume of approximately 1.75 mL.
  • the TREF column ends are capped with Valco microbore HPLC column end fittings equipped with a 10 ⁇ m stainless steel screen. These column ends provide the TREF columns with a direct connection to the plumbing of the cross fractionation instrument within the TREF oven.
  • the TREF columns are coiled, outfitted with an resistance temperature detector (RTD) temperature sensor, and wrapped with glass insulation tape before installation. During installation, extra care is given to level placement of the TREF column with the oven to ensure adequate thermal uniformity within the column Chilled air is provided at 40 L/min to the TREF ovens via a chiller whose bath temperature is 2° C.
  • RTD resistance temperature detector
  • sample solutions are prepared as 4 mg/mL solutions in 1,2,4-trichlorobenzene (TCB) containing 180 ppm butylated hydroxytoluene (BHT) and the solvent is sparged with nitrogen. A small amount of decane is added as a flow rate marker to the sample solution for GPC elution validation. Dissolution of the samples is completed by gentle stirring at 145° C. for four hours.
  • TCB 1,2,4-trichlorobenzene
  • BHT butylated hydroxytoluene
  • Samples are injected via a heated transfer line to a fixed loop injector (Injection loop of 500 mL) directly onto the TREF column at 145° C.
  • the column After the sample has been injected onto the TREF column, the column is taken “off-line” and allowed to cool.
  • the temperature profile of the TREF column is as follows: cooling down from 145° C. to 110° C. at 2.19° C./min, cooling down from 110° C. to 30° C. at 0.110° C./min, and thermal equilibrium at 30° C. for 16 minutes.
  • the column is placed back “on-line” to the flow path with a pump elution rate of 0.9 ml/min for 1.0 minute.
  • the heating rate of elution is 0.119° C./min from 30° C. to 110° C.
  • the 16 fractions are collected from 30° C. to 110° C. at 5° C. increments per fraction. Each fraction is injected for GPC analysis. Each of the 16 fractions are injected directly from the TREF column over a period of 1.0 minute onto the GPC column set. The eluent is equilibrated at the same temperature as the TREF column during elution by using a temperature pre-equilibration coil (Gillespie and Li Pi Shan et al., Apparatus for Method for Polymer Characterization, WO2006081116).
  • Elution of the TREF is performed by flushing the TREF column at 0.9 ml/min for 1.0 min
  • the first fraction, Fraction (30° C.) represents the amount of material remaining soluble in TCB at 30° C.
  • the cross fractionation instrument is equipped with one 20 ⁇ m guard column and four Mixed A-LS 20 ⁇ m columns (Varian Inc., previously PolymerLabs), and the IR-4 detector from PolymerChar (Spain) is the concentration detector.
  • the GPC column set is calibrated by running twenty one narrow molecular weight distribution polystyrene standards.
  • the molecular weight (MW) of the standards ranges from 580 to 8,400,000 g/mol, and the standards are contained in 6 “cocktail” mixtures. Each standard mixture (“cocktail”) has at least a decade of separation between individual molecular weights.
  • the standards are purchased from Polymer Laboratories (Shropshire, UK).
  • the polystyrene standards are prepared at 0.005 g in 20 mL of solvent for molecular weights equal to or greater than 1,000,000 g/mol and 0.001 g in 20 mL of solvent for molecular weights less than 1,000,000 g/mol.
  • the polystyrene standards are dissolved at 145° C. with gentle agitation for 30 minutes.
  • the narrow standards mixtures are run first and in the order of decreasing highest molecular weight component to minimize degradation.
  • a logarithmic molecular weight calibration is generated using a fourth-order polynomial fit as a function of elution volume.
  • the polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 19 as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968):
  • M polyethylene A ( M polystyrene ) B (Eq. 19)
  • M is the molecular weight
  • A has a value of 0.40 and B is equal to 1.0.
  • the plate count for the four Mixed A-LS 20 ⁇ m columns needs to be at least 19,000 by using a 200 ⁇ l injection volume of a 0.4 mg/ml solution of Eicosane in 1,2,4-Trichlorobenzene (TCB) bypassing the TREF column.
  • the plate count calculates from the peak retention volume (RV pk max ) and the retention volume (RV) width at 1 ⁇ 2 height (50% of the chromatographic peak) to obtain an effective measure of the number of theoretical plates in the column by using Equation 20 (Striegel and Yau et al., “Modern Size-Exclusion Liquid Chromatography”, Wiley, 2009, Page 86):
  • the molecular weight distribution (MWD) of each fraction is calculated from the integrated GPC chromatogram to obtain the weight average molecular weight for each fraction, MW (Temperature).
  • the establishment of the upper integration limit is based on the visible difference between the peak rise from the baseline.
  • the establishment of the lower integration limit is viewed as the return to the baseline or the point of the elution volume of the polystyrene narrow molecular weight standard of 3250 molecular weight (whichever is earlier).
  • the white noise level of the IR-4 detector is calculated from the IR-4 detector upon analyzing the GPC chromatogram before the upper integration limit (prior to polymer elution).
  • the detector response at each acquisition time contributed from the polymer chains is first corrected for the baseline correction to obtain the baseline subtracted signal (IR(RV), RV is the elution volume of the GPC chromatogram).
  • the baseline corrected IR-4 response is further corrected for white noise: IR(RV) is used in the GPC calculation only if IR(RV) is larger than the white noise value.
  • a typical white noise for the IR is determined to be 0.35 mV while the whole-polymer (direct 0.50 mg GPC-injection on the GPC column bypassing the TREF column) peak height in mV is typically around 240 for a polyolefin polymer (high density polyethylene, polydispersity M w /M n approximately 2.6). Care should be maintained to provide a signal to noise ratio (the peak height of whole polymer injection to the white noise) of at least 500 at 1.0 mg/ml 500 ⁇ L injection volume for a polyolefin polymer (high density polyethylene, polydispersity M w /M n approximately 2.6).
  • the area of each individual GPC chromatogram corresponds to the amount of polyolefinic material eluted from the TREF fraction.
  • the weight percentage of the TREF fraction at a specified temperature range of the Fraction, Wt % (Temperature), is calculated as the area of the individual GPC chromatogram divided by the sum of the areas of the 16 individual GPC chromatograms.
  • the GPC molecular weight distribution calculations (Mn, Mw, and Mz) are performed on each chromatogram and reported only if the weight percentage of the TREF fraction is larger than 1.0 wt %.
  • the GPC weight-average molecular weight, Mw is reported as MW (Temperature) of each chromatogram.
  • Wt % (30° C.) represents the amount of material eluting from the TREF column at 30° C. during the TREF elution process.
  • Wt % (35° C.), Wt % (40° C.), Wt % (45° C.), Wt % (50° C.), Wt % (55° C.), Wt % (60° C.), Wt % (65° C.), Wt % (70° C.), Wt % (75° C.), Wt % (80° C.), Wt % (85° C.), Wt % (90° C.), Wt % (95° C.), Wt % (100° C.), and Wt % (105° C.) represent the amount of material eluting from the TREF column with a temperature range of 30.01° C.
  • the cumulative weight fraction is defined as the sum of the Wt % of the fractions up to a specified temperature.
  • the cumulative weight fraction is 1.00 for the whole temperature range.
  • the highest temperature fraction molecular weight, MW (Highest Temperature Fraction), is defined as the molecular weight calculated at the highest temperature containing more than 1.0 wt % material.
  • the MW Ratio of each temperature is defined as the MW (Temperature) divided by MW (Highest Temperature Fraction).
  • Gel content is determined in accordance to ASTM D2765-01 Method A in xylene. The sample is cut to required size using a razor blade.
  • All raw materials ethylene, 1-octene
  • the process solvent a narrow boiling range high-purity isoparaffinic solvent trademarked Isopar E and commercially available from Exxon Mobil Corporation
  • Hydrogen is supplied in pressurized cylinders as a high purity grade and is not further purified.
  • the reactor monomer feed (ethylene) stream is pressurized via a mechanical compressor to above reaction pressure at 750 psig.
  • the solvent and comonomer (1-octene) feed is pressurized via a mechanical positive displacement pump to above reaction pressure at 750 psig.
  • the individual catalyst components are manually batch diluted to specified component concentrations with purified solvent (Isopar E) and pressured to above reaction pressure at 750 psig. All reaction feed flows are measured with mass flow meters and independently controlled with computer automated valve control systems.
  • the continuous solution polymerization reactors consist of two liquid full, non-adiabatic, isothermal, circulating, and independently controlled loops operating in a series configuration. Each reactor has independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds.
  • the combined solvent, monomer, comonomer and hydrogen feed to each reactor is independently temperature controlled to anywhere between 5° C. to 50° C. and typically 40° C. by passing the feed stream through a heat exchanger.
  • the fresh comonomer feed to the polymerization reactors can be manually aligned to add comonomer to one of three choices: the first reactor, the second reactor, or the common solvent and then split between both reactors proportionate to the solvent feed split.
  • the total fresh feed to each polymerization reactor is injected into the reactor at two locations per reactor roughly with equal reactor volumes between each injection location.
  • the fresh feed is controlled typically with each injector receiving half of the total fresh feed mass flow.
  • the catalyst components are injected into the polymerization reactor through specially designed injection stingers and are each separately injected into the same relative location in the reactor with no contact time prior to the reactor.
  • the primary catalyst component feed is computer controlled to maintain the reactor monomer concentration at a specified target.
  • the two cocatalyst components are fed based on calculated specified molar ratios to the primary catalyst component.
  • the feed streams are mixed with the circulating polymerization reactor contents with Kenics static mixing elements.
  • each reactor The contents of each reactor are continuously circulated through heat exchangers responsible for removing much of the heat of reaction and with the temperature of the coolant side responsible for maintaining an isothermal reaction environment at the specified temperature. Circulation around each reactor loop is provided by a screw pump.
  • the effluent from the first polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the first reactor loop and passes through a control valve (responsible for maintaining the pressure of the first reactor at a specified target) and is injected into the second polymerization reactor of similar design.
  • a control valve responsible for maintaining the pressure of the first reactor at a specified target
  • As the stream exits the reactor it is contacted with water to stop the reaction.
  • various additives such as anti-oxidants, can be added at this point.
  • the stream then goes through another set of Kenics static mixing elements to evenly disperse the catalyst kill and additives.
  • the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from the other lower boiling reaction components.
  • the stream then enters a two stage separation and devolatization system where the polymer is removed from the solvent, hydrogen, and unreacted monomer and comonomer.
  • the recycled stream is purified before entering the reactor again.
  • the separated and devolatized polymer melt is pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transferred into a hopper. After validation of initial polymer properties, the solid polymer pellets are manually dumped into a box for storage. Each box typically holds ⁇ 1200 pounds of polymer pellets.
  • the non-polymer portions removed in the devolatilization step pass through various pieces of equipment which separate most of the ethylene which is removed from the system to a vent destruction unit (it is recycled in manufacturing units). Most of the solvent is recycled back to the reactor after passing through purification beds. This solvent can still have unreacted co-monomer in it that is fortified with fresh co-monomer prior to re-entry to the reactor. This fortification of the co-monomer is an essential part of the product density control method. This recycle solvent can still have some hydrogen which is then fortified with fresh hydrogen to achieve the polymer molecular weight target.
  • Tables 2-4 summarize the conditions for polymerization for examples of this invention.
  • Table 5 summarizes catalysts and catalysts components referenced in Table 4.
  • All (co)monomer feeds ethylene, 1-octene
  • the process solvent a narrow boiling range high-purity isoparaffinic solvent trademarked Isopar E and commercially available from Exxon Mobil Corporation
  • High purity hydrogen is supplied by a shared pipeline; it is mechanically pressurized to above reaction pressure at 500 psig prior to delivery to the reactors; and it is not further purified on site other than to remove any potential residual moisture.
  • the reactor monomer feed (ethylene) streams are pressurized via mechanical compressor to above reaction pressure at 500 psig.
  • the solvent feeds are mechanically pressurized to above reaction pressure at 500 psig.
  • the comonomer (1-octene) feed is also mechanically pressurized to above reaction pressure at 500 psig and is injected directly into the feed stream for the first reactor.
  • Three catalyst components are injected into the first reactor (CAT-B, RIBS-2, and MMAO-3A).
  • the RIBS-2 catalyst component is diluted to a predefined concentration at the supplier.
  • the CAT-B and MMAO-3A catalyst components are further batch-wise diluted on site to the desired plant concentration with purified solvent (Isopar E) prior to injection into the reactor.
  • Two catalyst components are injected into the second reactor (Ziegler-Natta premix, and triethylaluminum (TEA)). All catalyst components are independently mechanically pressurized to above reaction pressure at 500 psig. All reactor catalyst feed flows are measured with mass flow meters and independently controlled with positive displacement metering pumps.
  • the continuous solution polymerization reactors consist of two liquid full, non-adiabatic, isothermal, circulating, and independently controlled loops operating in a series configuration. Each reactor has independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds.
  • the combined solvent, monomer, comonomer and hydrogen feed to each reactor is independently temperature controlled to anywhere between 10° C. to 50° C. and typically 15° C. by passing the feed stream through a series of heat exchangers.
  • the fresh comonomer feed to the polymerization reactors can be aligned to add comonomer to one of three choices: the first reactor, the second reactor, or the common solvent where it is then split between both reactors proportionate to the shared solvent feed split.
  • the comonomer is fed to the first reactor.
  • the total fresh feed to each polymerization reactor is injected into the reactor at two locations per reactor roughly with equal reactor volumes between each injection location.
  • the fresh feed to the first reactor is controlled typically with each injector receiving half of the total fresh feed mass flow.
  • the fresh feed to the second reactor in series is controlled typically to maintain half of the total ethylene mass flow near each injector, and since the non-reacted ethylene from the first reactor enters the second reactor adjacent to the fresh feed this injector usually has less than half of the total fresh feed mass flow to the second reactor.
  • the catalyst components for the first reactor are injected into the polymerization reactor through specially designed injection stingers and are each separately injected into the same relative location in the first reactor with no contact time prior to the reactor.
  • the catalyst components for the second reactor (Ziegler-Natta and TEA) are injected into the second polymerization reactor through specially designed injection stingers and are each injected into the same relative location in the second reactor.
  • the primary catalyst component feed for each reactor (CAT-B for the first reactor and a Ziegler-Natta premix for the second reactor) is computer controlled to maintain the individual reactor monomer concentration at a specified target.
  • the cocatalyst components (RIBS-2 and MMAO-3A for the first reactor and TEA for the second reactor) are fed based on calculated specified molar ratios to the primary catalyst component.
  • the feed streams are mixed with the circulating polymerization reactor contents with Kenics static mixing elements.
  • the contents of each reactor are continuously circulated through heat exchangers responsible for removing much of the heat of reaction and with the temperature of the coolant side responsible for maintaining an isothermal reaction environment at the specified reactor temperature.
  • Circulation around each reactor loop is provided by a screw pump.
  • the effluent from the first polymerization reactor exits the first reactor loop and passes through a control valve (responsible for controlling the pressure of the first reactor at a specified target) and is injected into the second polymerization reactor of similar design.
  • a control valve responsible for controlling the pressure of the first reactor at a specified target
  • the stream exits the second reactor it is contacted with water to stop the reaction (this water is delivered as water of hydration contained with calcium stearate).
  • various additives such as anti-oxidants (typically Irganox 1010), are also added at this point.
  • the stream then goes through another set of Kenics static mixing elements to evenly disperse the water catalyst kill and any additives.
  • the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and dissolved polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from the other lower boiling reaction components.
  • the stream then enters a two stage separation and devolatization system where the polymer is removed from the solvent, hydrogen, and non-reacted monomer and comonomer.
  • the recycled stream is purified before entering the reactor again.
  • the separated and devolatized polymer melt is then combined with a small side stream of additional additives contained within a polymer melt injected into the process by a single screw extruder.
  • additives typically Irganox 1076 and Irgafos 168 are mixed with the main process polymer melt by another series of Kenics static mixing element.
  • the fully additive loaded polymer stream then enters a die specially designed for underwater pelletization, is cut into uniform solid pellets, dried, and transferred into a hopper. During transfer to the hopper, a dry blend of fluoroelastomer processing aid is added to the polymer pellet stream.
  • the non-polymer portions removed in the devolatilization step pass through various pieces of equipment which separate most of the monomer which is removed from the system, cooled, mechanically compressed, and sent via pipeline back to a light hydrocarbons processing plant for reuse. Most of the solvent and comonomer are recycled back to the reactor after passing through purification beds. This solvent can still have non-reacted co-monomer in it that is fortified with fresh co-monomer prior to re-entry to the reactor as previously discussed. This fortification of the co-monomer is an essential part of the product density control method.
  • This recycle solvent can contain some dissolved hydrogen which is then fortified with fresh hydrogen to achieve the polymer molecular weight target. A very small amount of solvent temporarily leaves the system where it is purified and reused or purged from the system as a co-product.
  • Tables 6-8 summarize the conditions for polymerization for Comparative Example 2 of this invention.
  • Comparative Example 1 is a ethylene/octene polyethylene produced by a Ziegler-Natta catalyst.
  • the production of Comparative Example 2 was previously described with conditions given in Tables 6-8.
  • the examples are in the general I 2 melt index range of 0.3-0.9 with densities in the range of 0.918 to 0.936 g/cm 3 .
  • the comparative examples are also in this general melt index and density range.
  • the I 10 /I 2 range of the examples are from 7.8-14.3. These examples have higher I 10 /I 2 values or improved processability as compared to the comparative examples with lower I 10 /I 2 values of 7.4-8.3.
  • DMS viscosity, tan delta, and complex modulus versus phase angle data are given in Tables 11-14, respectively, and plotted in FIGS. 3-5 , respectively.
  • the viscosity data of Table 11 and FIG. 3 as well as the viscosity at 0.1 rad/s over that at 100 rad/s in Table 11 show that many of the Examples show high shear thinning behavior of viscosity decreasing rapidly with increasing frequency as compared to the Comparative Examples. From Table 12 and FIG. 4 , many of the Examples have low tan delta values or high elasticity as compared to the Comparative Examples.
  • Table 14 and FIG. 5 shows a form of the DMS data which is not influenced as greatly by the overall melt index (MI or I 2 ) or molecular weight. The more elastic material are lower on this plot (i.e., lower phase angle for a given complex modulus); the Examples are generally lower on this plot or more elastic than the Comparative Examples.
  • Tan Delta Freq Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 CE 1 CE 2 0.10 2.76 2.02 2.35 4.27 5.14 5.38 2.27 2.17 7.44 3.94 0.16 2.50 1.90 2.15 3.67 4.52 4.58 2.01 2.01 6.13 3.50 0.25 2.32 1.81 1.99 3.23 4.05 3.99 1.83 1.88 5.31 3.20 0.40 2.18 1.75 1.88 2.91 3.67 3.57 1.68 1.78 4.53 2.96 0.63 2.07 1.70 1.80 2.68 3.35 3.24 1.58 1.71 3.88 2.79 1.00 1.98 1.65 1.74 2.49 3.05 2.98 1.50 1.64 3.34 2.63 1.58 1.89 1.60 1.68 2.34 2.75 2.74 1.45 1.57 2.87 2.47 2.51 1.81 1.54 1.63 2.20 2.46 2.53 1.42 1.50 2.47 2.30 3.98 1.71 1.47 1.56 2.05 2.18 2.31 1.39 1.42 2.15 2.12 6.31 1.60 1.39 1.48
  • melt strength data are shown in Table 15 and plotted in FIGS. 6-7 .
  • the melt strengths are influenced by the melt index with the melt index in general being higher for lower melt index materials.
  • Examples 1 and 2 have high melt strength values, relatively, as compared to the Comparative Examples.
  • Zero shear viscosity (ZSV) data for the Examples and Comparative Examples are shown in Table 17. In general, the Examples have high ZSV ratios as compared to the Comparative Examples.
  • Unsaturation data for the Examples and Comparative Examples are shown in Table 18.
  • the Examples have very low total unsaturation values as compared to the Comparative Examples. All other unsaturation values (vinylene, trisubstituted, vinyl, and vinylidene) are also lower for the Examples as compared to the Comparative Examples.
  • Short chain branching distribution data are shown in Table 19 and FIGS. 10-11 .
  • the Examples have higher CDC and Comonomer Distribution Index than the Comparative Examples.
  • the Examples have a monomodal or bimodal distribution excluding the soluble fraction at temperature ⁇ 30° C.
  • the MW Ratio is measured by cross fractionation (TREF followed by GPC) for the Examples and Comparative Examples.
  • the MW Ratio is shown in Tables 20 and 21 and FIGS. 12-13 .
  • the Examples have MW Ratio values increasing from a low value (close to 0.10) with temperature, and reaching a maximum value of 1.00 at the highest temperature with these values monotonically increasing.
  • the Comparative Examples having MW Ratio values larger than 1.00 for some temperatures and some MW Ratios at higher temperatures being lower than MW Ratio values at lower temperatures.
  • the Examples have MW Ratios for the temperatures ⁇ 50° C. of less than 0.10, while the Comparative Examples have MW Ratios larger than 0.10 for some temperatures ⁇ 50° C.
  • the Examples have a cumulative weight fraction less than 0.10 for the temperature fractions up to 50° C.
  • Films are made on a 6 inch die with a linear low density (LLDPE) type screw. During film fabrication, no internal bubble cooling is used. Several different series of samples are made. Films are made of 100% of the Examples and Comparatives Examples. Films of blends of the Examples and Comparative Examples with a high pressure low density polyethylene, Dow high pressure low density polyethylene (LDPE) LDPE 132I (0.25 MI, 0.921 g/cm 3 ) are also made. Two different types of blends are made: a) LLDPE-rich with 65 wt % linear low density polyethylene or LLDPE (the Examples and Comparative Examples) and 35 wt % LDPE 132I and b)
  • LLDPE-rich with 65 wt % linear low density polyethylene or LLDPE the Examples and Comparative Examples
  • Table 22 General blown film parameters used to produce the blown films for the LLDPE-rich films are shown in Table 22.
  • the temperatures in Table 22 show the temperatures closest to the pellet hopper (Barrel 1) and in increasing order as the polymer is being extruded through the die (upper die).
  • LLDPE-rich film Set 1 made under film process conditions shown in Table 22 are shown in Tables 23-24.
  • Examples 3-8 show good MD and CD shrink tension and free shrink, which is advantageous for use in shrink film, good optics (haze, gloss, clarity), and generally good film properties (puncture, dart, and tear).
  • Table 25-26 show data for Examples 1 and 2 (LLDPE-Rich Film Set 2 in Table 22) as compared to Comparative Examples 1-2.
  • Examples 1-2 show good MD and CD shrink tension and free shrink, which is advantageous for use in shrink film, good optics (haze, gloss, clarity), and generally good film properties (puncture, dart, and tear).
  • the film properties of the LDPE-rich samples are shown in Tables 27-28.
  • the Examples show good MD and CD shrink tension and free shrink, which is advantageous for use in shrink film, good optics (haze, gloss, clarity), and generally good film properties (puncture, dart, and tear).
  • the Examples show higher shrink tension coupled with higher puncture and good haze, while maintaining a high secant modulus as compared to the Comparative Examples.

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