Dow Global Technolgoies LLC

Stefan Hinrichs

Otto J Berbee

Teresa Plumley Karjala

Cornelis F J Den Doelder

John O Osby

Sarat Munjal

Christopher R Eddy

Jian Jim Wang

Sean W Ewart

Karl Zuercher

Mehmet Demirors

Bharat Indu Chaudhary

Lonnie G Hazlitt

Wallace W Yau

Cornelis J Hosman

Werner Zschoch

James L Cooper

Jose Ortega

Hayley A Brown

Cornelis J F Hosman

Eva-Maria Kupsch

Rajesh P Paradkar

Carmelo Declet Perez

Nhi T Y Dang

Jeffery S Bradley

Nhi Dang

Bernard A Fehr

Sergio E Goncalves

Jian Wang

Juergen Siebdrat

Cornelis F Den Doelder

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

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 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

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

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

Ethylene-based polymers comprising the following properties: (A) a density from 0.9190 g/cc to 0.9240 g/cc; (B) a hexane extractable level that is less than or equal to the lower of: (1) (A+(B*density (g/cc))+(C*log(MI) dg/min)) based on total weight of the ethylene-based polymer; where A=250.5 wt %, B=&#x2212;270 wt %/(g/cc), C=0.25 wt %/[log(dg/min)], or (2) 2.0 wt %; (C) a G' (at G&#x2033;=500 Pa, 170&#xb0; C.) that meets the following equation: G&#x2032;&#x2265;D+E[log (12)], where D=150 Pa and E=&#x2212;60 Pa/[log(dg/min)]; and (D) a melt index () from 1.0 to 20 dg/min; are made in process comprising the step of contacting in a reaction configuration, comprising a first tubular reaction zoneand a last tubular reaction zone i, in which i is greater than or equal to (&#x2265;) 3, under high pressure polymerization conditions, and in which the first reaction zonehas a peak polymerization temperature greater than the peak temperature of the ith reaction zone, and wherein the difference in these two peak temperatures is &#x2265;30&#xb0; C.

Process for producing ethylene-based polymers with low hexane extractables

A process to form an ethylene-based polymer comprises polymerizing a reaction mixture comprising ethylene, at least one monomeric chain transfer agent, 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 the 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 melt strength

Ethylene-based polymer is made by a process comprising polymerizing a reaction mixture comprising ethylene and at least one chain transfer agent system; wherein the polymerization takes place in the presence of at least one free-radical initiator; and wherein the polymerization takes place in a reactor configuration comprising at least one tubular reactor with at least three reaction zones; and wherein at least two reaction zones receive an ethylene feed; and wherein the degree of polymerization in the first reaction zone is less than, or equal to, (5/LCBf)*3150; and wherein the ethylene-based polymer formed by the process comprises the following properties: (A) LCBf&#x2265;(4.7+0.5*log(I2)); and (B) I2 from 0.2 to 25 dg/min.

Process for producing ethylene-based polymers with reduced gel counts and low reactor fouling

The invention provides an ethylene homopolymer formed from a free-radical, high pressure polymerization process in a tubular reactor system, said homopolymer comprising the following properties: (A) a density from 0.9190 to 0.9250 g/cc; (B) a hexane extractable level that is less than, or equal to, 2.6 wt %, based on the total weight of the polymer; (C) a G (at G&#x2033;=500 Pa, 170C) that meets the following equation: G&#x3e;D+E[log(12)], where D=150 Pa and E=&#x2212;60 Pa/[log(dg/min)]; and (D) a melt index (12) from 1.0 to 20 dg/min.

Ethylene-based polymers with low hexane extractables

The invention provides an ethylene-based polymer comprising the following properties: The invention also provides an ethylene-based polymer comprising the following properties:

Low density ethylene-based polymers with broad molecular weight distributions and low extractables

A process to form an ethylene-based polymer including polymerizing ethylene and at least one asymmetrical polyene comprising an 'alpha, beta unsaturated-carbonyl end' ('&#x3b1;,&#x3b2; unsaturated-carbonyl end') and a &#x201c;C&#x2014;C double bond end,&#x201d; wherein the polymerization takes place in the presence of at least one free-radical initiator; and wherein the polymerization takes place 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.

Processes to form ethylene-based polymers using asymmetrical polyenes

The invention provides an ethylene-based polymer comprising the following properties:

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Wondelgem, Belgium

Stefan Hinrichs