Dow Global Technolgoies LLC

The Dow Chemical Company

Dow Brasil Sudeste Industrial Ltda

Otto J Berbee

Stefan Hinrichs

Teresa Plumley Karjala

Cornelis F J Den Doelder

John O Osby

Sarat Munjal

Cornelis J F Hosman

Jian Jim Wang

Christopher R Eddy

Mehmet Demirors

Sean W Ewart

Joaquin Flores

Karl Zuercher

Werner Zschoch

Cornelis J Hosman

Nhi T Y Dang

Nhi Dang

Lori L Kardos

Jeffery S Bradley

Sergio E Goncalves

Bryan Gutermuth

Bharat Indu Chaudhary

Lonnie G Hazlitt

Wallace W Yau

James L Cooper

Sjoerd A De Vries

Cornelis Den Doelder

Egbert Nijhof

Jose Ortega

Hayley A Brown

Eva-Maria Kupsch

Rajesh P Paradkar

Carmelo Declet Perez

Laura Nunez

Bernard A Fehr

Gerd Lohse

Juan Manuel Mezquita

Jian Wang

Roger G Gagnon

Mark Jasek

John T Keating

Gerrit Hommersom

Michael E Bishop

Larry A Morse

Luiz Rodriguez

Harald Beer

Cornelis F Den Doelder

Juergen Siebdrat

Cornelis FJ Den Doelder

Larry Morse

John Keating

Cornelis Jf Hosman

A high pressure, free radical polymerization process to form an ethylene-based polymer, the process comprising at least the following step: polymerizing a reaction mixture comprising ethylene, using a polymerization system comprising the following: (A) a reactor configuration comprising at least one reactor that comprises at least two reaction zones, a first reaction zone (reaction zone 1) and an ith reaction zone (where i&#x2265;2); wherein the ith reaction zone is the last reaction zone, and wherein i is the total number of reaction zones; (B) at least two ethylene-based feed streams, a first ethylene-based feed stream and an nth ethylene-based feed stream, wherein the first ethylene-based feed stream is sent to the first reaction zone, and the nth ethylene-based feed stream is the last ethylene based feed stream sent to the reactor configuration; wherein n&#x2264;i; and RZn/RZ1 does not equal 1.0, where RZ1=mole fraction of make-up ethylene in the first ethylene-based feed stream to the first reaction zone; where RZn=mole fraction of make-up ethylene in the last ethylene-based feed stream sent to the reactor configuration; (C) a control system to control the percentage of the make-up ethylene in the first ethylene-based feed stream, and the percentage of the make-up ethylene in the nth ethylene-based feed stream; and wherein at least one reaction zone receives a CTA make-up feed stream comprising an alpha-olefin, and wherein the alpha-olefin has a chain transfer activity constant (Cs) value &#x2264;0.10, and wherein the chain transfer activity constant (Cs) is measured at 1360 atm, 130&#xb0; C.

Ethylene-based polymers with new distributions of terminal and internal unsaturations

A high pressure polymerization, as described herein, to form an ethylene-based polymer, comprising the following steps: polymerizing a reaction mixture comprising ethylene, using a reactor system comprising at least three ethylene-based feed streams and a reactor configuration that comprises at least four reaction zones, and at least one of the following a) through c), is met: (a) up to 100 wt % of the ethylene stream to the first zone comes from a high pressure recycle, and/or up to 100 wt % of the last ethylene stream to a zone comes from the output from a Primary compressor system; and/or (b) up to 100 wt % of the ethylene stream to first zone comes from the output from a Primary compressor system, and/or up to 100 wt % of the last ethylene stream to a zone comes from a high pressure recycle; and/or (c) the ethylene stream to the first zone, and/or the last ethylene stream to a zone, each comprises a controlled composition; and wherein each ethylene stream to a zone receives an output from two or more cylinders of the last compressor stage of a Hyper compressor system.

High pressure, free radical polymerizations to produce ethylene-based polymers

The invention provides a composition comprising a first ethylene-based polymer, formed by a high pressure, free-radical polymerization process, and comprising the following properties:

Low density ethylene-based polymers with high melt strength

A high pressure polymerization process to form an ethylene-based polymer, the process comprising at least the following step: polymerizing a reaction mixture comprising ethylene and at least one comonomer, using a reactor system comprising a reactor configuration, and the following: (A) at least two reaction zones, a zone (reaction zone 1) and an ith zone (reaction zone i where i&#x2265;2), (B) at least two ethylene-based feed streams, each comprising a percentage of the total make-up ethylene fed to the polymerization process, and wherein a first stream is sent to reaction zone 1 and a second stream is sent to reaction zone i; (C) a control system to control the percentage of the total make-up ethylene in the stream sent to reaction zone 1, and the percentage of the total make-up ethylene in the stream sent to reaction zone i, and wherein the ratio (Q) of the molar concentration of the at least one comonomer fed to the first reaction zone, to the molar concentration of comonomer in the sum of all ethylene-based feeds to the reactor configuration, meets the following Equation 1: 0.23 ln(r1)&#x2212;2.16&#x2264;Q&#x2264;&#x2212;0.25 ln(r1)+2.15 (Equation 1); and wherein the comonomer has a reactivity ratio (r1) as follow: 0.3&#x2264;r1&#x2264;5.0, and a boiling point (1 atm)&#x2264;150&#xb0; C.

Process for making high pressure free radical ethylene copolymers

A process to form an ethylene-based polymer, as described herein, in a tubular reactor system comprising at least three ethylene-based feeds, and at least four reaction zones, and where the weight ratio of 'the ethylene-based feed to the second zone (EBF2)' to 'the ethylene-based feed to the first zone (EBF1),' is from 0.50 to 1.10; and the weight ratio of &#x201c;the ethylene-based feed to the third zone (EBF3)&#x201d; to &#x201c;the ethylene-based feed to the first zone (EBF1),&#x201d; is from 0.40 to 2.50; in each zone, the polymerization takes place at a start temperature&#x2265;135&#xb0; C.; and (a) for three or more ethylene based feeds, the peak temperatures in the first and the second zones, are each from 200&#xb0; C. to 250&#xb0; C.; and/or (b) for four or more ethylene based feeds, the peak temperatures in the first, the second and the third zones, are each from 200&#xb0; C. to 250&#xb0; C.; and the differential in peak temperatures of the first three zones (TP1, TP2, TP3) meets at least one relationship described herein.

Ethylene-based polymers formed by high pressure free radical polymerizations

A process for producing an ethylene-based polymer comprises polymerizing, by the presence of at least one free-radical initiator and using a high pressure tubular polymerization process, a reaction mixture containing ethylene and at least one CTA system comprising one or more CTA components to produce the ethylene-based polymer. The free-radical initiator is dissolved in a solvent comprising a saturated hydrocarbon to form an initiator solution which is added to the polymerization using an initiator feed line to an initiator injection pump. At least 50 wt % of the solvent has i) a dry point of less than or equal to 160&#xb0; C. and ii) an initial boiling point of greater than or equal to 100&#xb0; C. The polymerization process has a ratio of inlet pressure to first peak temperature of less than or equal to 9 Bar/&#xb0; C. At least one CTA make-up stream is fed into the polymerization process, wherein less than or equal to 30 wt % of the at least one CTA make-up stream comprises one or more saturated hydrocarbon CTA(s) with a maximum carbon atom number of 6 per molecule.

Methods for producing low volatile tubular low density ethylene-based polymers for clean extrusion coating processing

A process to form an ethylene-based polymer comprising polymerizing a mixture comprising ethylene, in the presence of a free-radical initiator, and in a tubular reactor system comprising at least two ethylene-based feed streams, and a reactor configuration that comprises at least three reaction zones; and the inlet pressure of the first zone is &#x3c;3200 Bar; and the ethylene conversion &#x3e;28%, and an m value from 20 mole % to 70 mole %, where m=mol % of ethylene-based feed stream to the first zone, based on total moles of ethylene-based feed streams fed to the reactor configuration; and the ratio (Q) of a 'MWDB of a broad polymer polymerized, to a 'MWDN of a narrow polymer polymerized, is as follows: {(T)*(&#x2212;2.3&#xd7;log(m)+7)}&#x2264;Q&#x2264;{(T)*(&#x2212;13.0&#xd7;log(m)+29.8)}; at the same melt index; and &#x201c;T' is the &#x201c;chain transfer activity ratio' as described herein.

Ethylene-based polymers comprising the following properties: (A) a density less than 0.9190 g/cc; (B) a hexane extractable level that meets the following equation: hexane extractable level &#x2264;A+B [log(12)], where A=2.65 wt %, and B&#x2014;0.25 wt %[log (dg/min)]; based on total weight of the ethylene-based polymer; (C) a G' (at G&#x2033;=500 Pa, 1 70&#xb0; C.) that meets the following equation: G&#x2032;&#x2265;C+D [log(12)], where C=150 Pa, and D=&#x2212;60 Pa/[log(dg/min)]; and (D) a melt index (12) from 0.7 to 20 dg/min; are made in high pressure tubular process that comprises at least three reaction zones with the peak polymerization temperature of the first reaction zone &#x2265;320&#xb0; C. and the peak polymerization temperature of the last reaction zone &#x2264;290&#xb0; C.

Ethylene-based polymers with low hexane extractables and low densities

A process to form an ethylene-based polymer comprises polymerizing a reaction mixture comprising ethylene, at least one symmetrical polyene and at least one chain transfer agent system comprising at least one chain transfer agent (CTA) in the presence of at least one free-radical initiator and in a reactor configuration comprising at least two reaction zones, reaction zone 1 and reaction zone i (i&#x2265;2), wherein reaction zone i is downstream from reaction zone 1. The ratio of 'the activity of the CTA system of the feed to the first reaction zone' to the 'activity of the CTA system of the cumulative feed to the reaction zone i,' (Z/Z), is less than or equal to (0.8&#x2212;0.2*log(Cs)), wherein Cs is from 0.0001 to 10.

Process to make tubular ethylene based polymers with high G' and broad MWD

A process is provided to form an ethylene-based polymer, in the presence of at least one free-radical, said process comprises at least the following: polymerizing a mixture comprising ethylene, in a reactor configuration comprising at least three reaction zones, and comprising two ethylene feed streams, and wherein the ratio (R), in percent, of the 'LCB content of the first 40 wt % of the total polymer formed' to 'the total LCB content in the final polymer' is &#x2264;22.5%; and wherein the amount of ethylene, and optionally one or more comonomers, and optionally one or more CTAs, fed to the first reaction zone, is from 40 mole % to 80 mole %, based on the total moles of ethylene, and optionally one or more comonomers, and optionally one or more CTAs, fed to the polymerization.

High pressure free radical polymerizations

The invention provides a composition comprising an ethylene-based polymer, comprising at least the following: A) a unit derived from Carbon Monoxide (CO); and B) a unit derived from at least one Rheology Modifying Agent (RMA) selected from the following RMA1, RMA2, RMA3, RMA4, RMA5, each as described herein, or a combination thereof.

Ethylene-based polymers comprising units derived from carbon monoxide and a rheology modifying agent

The invention provides a composition comprising a first ethylene-based polymer, formed by a high pressure, free-radical polymerization process, and a second ethylene-based polymer, formed by a high pressure, free-radical polymerization process, such composition comprising the following properties:

Low density ethylene-based polymer compositions with high melt strength and mid-high density control

Ethylene-based polymer, LDPE, is made in a high pressure polymerization process to comprising at least the step of polymerizing a reaction mixture comprising ethylene, using a reactor configuration comprising (A) at least two reaction zones, a first reaction zone (reaction zone 1) and an i reaction zone (reaction zone i where i&#x3e;2), (B) at least two ethylene feed streams, each feed stream comprising a percentage of the total make-up ethylene fed to the polymerization process, in which a first ethylene feed stream is sent to reaction zone 1 and a second ethylene feed stream is sent to reaction zone i, and (C) a control system to control the percentage of the total make-up ethylene in the ethylene feed stream sent to reaction zone 1 and the percentage of the total make-up ethylene in the ethylene feed stream sent to reaction zone i.

High pressure free radical polymerization process with flexible control of molecular weight distribution

A process to form an ethylene-based polymer, in the presence of at least one free-radical, said process comprises at least the following: polymerizing a mixture comprising ethylene in a reactor configuration comprising at least four reaction zones, and comprising at least three ethylene feed streams; and wherein the ratio of (R), in percent, of the LCB content of the 'first 40 wt % of the total polymer formed' to the 'total LCB content in the final polymer' is &#x2264;29%; and wherein the amount of ethylene, and optionally one or more comonomers, and optionally one or more CTAs, fed to the first reaction zone, is from 20 mole % to 70 mole %, based on the total moles of ethylene, and optionally one or more comonomers, and optionally one or more CTAs, fed to the polymerization.

A process to form an ethylene-based polymer, said process comprising at least the following: polymerizing a mixture comprising ethylene, in the presence of at least one free-radical initiator, and in a reactor configuration comprising at least three reaction zones and at least two ethylene feed streams; and wherein the inlet pressure of the first reaction zone is less than, or equal to, 3200 Bar; and wherein the amount of ethylene, and optionally one or more comonomers, and optionally one or more CTAs, fed to the first reaction zone is from 40 mole % to 80 mole %, based on the total moles of ethylene, and optionally one or more comonomers, and optionally one or more CTAs, fed to the polymerization; and wherein the average polymerization temperature of the first 40 wt % polymer formed (APT) (based on the total amount of polymer formed) is less than, or equal to, 200&#xb0; C.

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Hulst, Netherlands

Otto J Berbee