US 7,745,550 B2Granted

Tubular polymerization reactors and polymers made therein

AssigneeExxonMobil Chemical Patents Inc.

InventorsJan C Donck, Henri A Lammens

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Abstract

Tubular reactor apparatus and processes are provided for improved polymerization including using chain transfer agents and multiple monomer feeds spaced lengthwise along the tubular reactor providing high conversions of monomer into polymer. The invention also relates to polymers made from such a tubular reactor apparatus and processes including those polymers having a low haze value, a density over 0.92 g/cm3 and/or having terminal carbonyl groups. The apparatus and methods uncouple or reduce the dependency between the monomer concentration and transfer agent concentration. The uncoupling in other embodiments may also be varied leading to multiple desirable effects.

Claims20

Dependent claims

A polymerization process in a tubular reactor comprising:

a. compressing a monomer feed having a chain transfer agent concentration of less than 0.1 mol %;
b. polymerizing the compressed monomer feed of step (a) in a reactor tube to form a polymer-monomer mixture, wherein the reactor tube has at least a first, second, and third reaction zones spaced lengthwise along the reactor tube and wherein the reactor tube comprises:
i. multiple monomer feed injection positions spaced lengthwise along the reactor tube;
ii. multiple chain transfer agent stream injection positions spaced lengthwise along the reactor tube;
and
iii. multiple free-radical initiator injection positions spaced lengthwise along the reactor tube;
c. compressing a chain transfer agent to form at least one compressed chain transfer agent stream, wherein the chain transfer agent is compressed separately from the monomer feed;
d. blending the compressed chain transfer agent stream of step (c) with varying amounts of compressed monomer feed having a chain transfer agent concentration of less than 0.1 mol % to form a first, second, and third chain transfer agent-rich stream having different chain transfer agent concentrations, wherein
i. the first chain transfer agent-rich stream has a chain transfer agent concentration that is at least 60% higher than the chain transfer agent concentration of the second chain transfer agent-rich stream;
and
ii. the second chain transfer agent-rich stream has a chain transfer agent concentration that is at least 100% higher than the chain transfer agent concentration of the third chain transfer agent-rich stream;
e. introducing at least one compressed chain transfer agent-rich stream of step (d) into each of the first, second, and third reaction zones to modify the molecular weight of the polymer, wherein
i. the first chain transfer agent-rich stream is introduced to the first reaction zone upstream of the second reaction zone which receives the second chain transfer agent-rich stream;
and
ii. the second chain transfer agent-rich stream is introduced to the second reaction zone upstream of the third reaction zone receiving the third chain transfer agent-rich stream;
and
f. separating the polymer-monomer mixture received from the reactor tube into a volatile monomer-rich phase and a molten polymer phase.

14 more elements

A high pressure polymerization process in a tubular reactor comprising:

a. providing a reactor tube having at least three reaction zones spaced lengthwise along the reactor tube, wherein each reaction zone has a monomer feed injection point, a chain transfer agent stream injection point, and a free-radical initiator injection point;
b. providing to the first reaction zone:
i. a first chain transfer agent stream;
ii. a monomer feed having a chain transfer agent concentration of less than 0.1 mol;
and
iii. free-radical initiator;
wherein the monomer feed is polymerized to form a first polymer-monomer mixture;
c. providing to the second reaction zone:
i. the first polymer-monomer mixture from the first reaction zone;
ii. a second chain transfer agent stream;
iii. optionally, monomer feed having a chain transfer agent concentration of less than 0.1 mol %;
and
iv. optionally, free-radical initiator;
wherein the monomer from the first polymer-monomer mixture and any additional monomer feed is polymerized to form a second polymer-monomer mixture;
d. providing to the third reaction zone:
i. the second polymer-monomer mixture from the second reaction zone;
ii. a third chain transfer agent stream;
iii. optionally, monomer feed having a chain transfer agent concentration of less than 0.1 mol %;
and
iv. optionally, free-radical initiator;
wherein the monomer from the second polymer-monomer mixture and any additional monomer feed is polymerized to form a third polymer-monomer mixture;
wherein the first chain transfer agent stream has a chain transfer agent concentration that is at least 60% higher than chain transfer agent concentration of the second chain transfer agent stream;
and
wherein the second chain transfer agent stream has a chain transfer agent concentration that is
at least 100% higher than chain transfer agent concentration of the third chain transfer agent stream.

22 more elements

Dependencies are inferred from the claim text.

Facts

Application: 11/024,523Filed 29 Dec 2004 · continuation in part
Priority: 19 Dec 2001
Published: US 2005/0192414 A11 Sep 2005
Granted: 29 Jun 2010
Term ends: Not estimatedThe source records don’t support an estimate.

Classification10 codes

B01J 19/2415
Stationary reactors without moving elements inside: tubular reactors
C08F 2/00
Processes of polymerisation
C08F 10/00
Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double
C08F 10/02
Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond: ethene

Family

Application10/028,552Parent of this continuation-in-part · filed 19 Dec 2001
Application10/454,545Parent of this division · filed 4 Jun 2003
Application10/712,750Parent of this continuation-in-part · filed 12 Nov 2003
US 2005/0192414 A1Pre-grant publication · published 1 Sep 2005
US 6,899,852 B2Parent of this continuation-in-part
US 6,673,878 B2Parent of this division
Application10/712,750Parent of this division
US 6,596,241 B2Parent of this continuation-in-part
Application10/454,545Parent of this continuation-in-part
US 2003/0114607 A1Published application
US 2003/0206835 A1Published application
US 2004/0247493 A1Published application
US 7,745,550 B2This patent

From the US filing history. Foreign family members aren’t listed.

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