PROCESS TO FORM AN ETHYLENE-BASED POLYMER

专利摘要:
POLYMERIZATIONS VIA HIGH PRESSURE FREE RADICALS TO PRODUCE ETHYLENE-BASED POLYMERS A process for forming an ethylene-based polymer, said process comprising at least the following: polymerizing a mixture comprising ethylene, in the presence of at least one radical initiator free, 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 mol% to 80 mol% based on 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% by weight of polymer formed (APT40% by weight) (based on the total amount of polymer formed) is less than or equal to 200°C.
公开号:BR112018009036B1
申请号:R112018009036-0
申请日:2016-11-10
公开日:2022-01-04
发明作者:Otto J. Berbee；Cornelis J. F. Hosman；Joaquin Flores；Sergio E. Gonçalves；Sarat Munjal；Michael E. Bishop；Luiz Rodriguez
申请人:Dow Global Technologies Llc；Dow Brasil Sudeste Industrial Ltda；
IPC主号:

专利说明:

BACKGROUND OF THE INVENTION
[001] Low Density Polyethylene (LDPE) is produced in an autoclave and/or a tubular reactor at high pressure and temperature. High pressure free radical polymerizations are disclosed in the following references: US Patents 8,445,606, 4,135,044, 7,582,709 and JP050534422 (Abstract). The tubular process is preferred over the autoclave process for its ability to increase conversion by abstracting the heat of polymerization by cooling the tubular reaction sections and cooling sections. However, it would be desirable to combine the greater conversion potential of a tubular process with the product capability of an autoclave process. Another important parameter is the polymer production from a high pressure polymerization process, which can range from 40 to 450 KTA or greater. Polymer production from a high pressure tubular process is affected by the level of conversion and monomer yield. The conversion is governed by the properties of the desired products of the polymers to be produced. Monomer yield depends on the design and operating conditions of a secondary compressor system, which compresses the monomer feed stream to the required reactor inlet pressure.
[002] Another important parameter is the energy required to produce a polyethylene polymer unit at high pressure. This energy requirement is largely determined by the compression energy required by the secondary compressor system. Thus, there is a need to maximize polymer production by increasing the level of conversion for a given amount of compression energy and/or using less compression energy to compress the monomer reactor feed stream by reducing the inlet pressure of the reactor. reactor. The requirements to maximize polymer production, increase product capacity and/or reduce energy requirement have been met by the following invention. SUMMARY OF THE INVENTION
[003] A process for forming an ethylene-based polymer, in the presence of at least one free radical, said process comprises at least the following: polymerization of 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 mol% to 80 mol%, 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% by weight formed polymer (40% by weight APT) (based on the total amount of formed polymer) is less than or equal to 200°C.
[004] A process for forming an ethylene-based polymer, in the presence of at least one free radical, said process comprises at least the following: polymerization of a mixture comprising ethylene, in the presence of at least one free radical initiator, and in a reactor configuration comprising at least four reaction zones and at least three 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 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 polymerization; and wherein the average polymerization temperature of the first 40% by weight formed polymer (APT40% by weight) (based on the total amount of polymer formed) is less than or equal to 200°C. BRIEF DESCRIPTION OF THE DRAWINGS
[005] Figure 1 is a process flow diagram containing a tubular reactor used for comparative polymerizations CP1 to CP3, CP1.1 and CP1.2. Figure 2 is a process flow diagram containing a tubular reactor used for comparative polymerizations CP4 to CP6 and IP5.1. Figure 3 is a process flow diagram containing a tubular reactor used for comparative IP 5.2 and IP 5.3 polymerizations. Figure 4 is a process flow diagram containing a tubular reactor used for comparative polymerizations CP7 to CP9 and IP 8.1.
[006] Figure 5 is a process flow diagram containing a tubular reactor used for comparative IP 8.2 and IP 10.2 polymerizations. Figure 6 is a process flow diagram containing a tubular reactor used for comparative polymerizations CP10 to CP12, IP10.1, IP11.1 and IP12.1. Figure 7 represents “temp. versus reactor length” to determine the Tp,i values (used in the determination of APT40% and APT60%). Figure 8 represents the normalized molecular weight distribution as a function of gas front, at constant conversion level, and at varying front peak temperature(s), and in fresh CTA(s) and fresh ethylene (offset) variables. DETAILED DESCRIPTION
[007] New polymerization processes have been discovered that provide ethylene-based polymers with narrow and significant molecular weight distributions at reduced pressure levels with high polymer production. It has also been found that both wide and narrow MWD polymers can be produced at constant polymer production, providing better economics for polymerization processes. It has been found that the piston discharges of the second compression stage of a secondary compressor system can be arranged for equal or different distributions of ethylene feed streams over the reaction zones to increase the molecular weight distribution range of the polymeric products. . Furthermore, it was also found that by delivering fresh ethylene to the reactor side, and/or delivering fresh CTA to the reactor front, the narrow MWD products and process capabilities can be further improved.
[008] As discussed above, there is provided a process for forming an ethylene-based polymer, in the presence of at least one free radical, said process comprises at least the following: polymerization of a mixture comprising ethylene, in the presence of at least a 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 mol% to 80 mol%, based on the total moles of ethylene and, optionally, a or more comonomers and optionally one or more CTAs, fed to polymerization; and wherein the average polymerization temperature of the first 40% by weight formed polymer (APT40% by weight) (based on the total amount of polymer formed) is less than or equal to 200°C.
[009] In one embodiment, the reactor configuration comprises at least three ethylene feed streams.
[0010] In one embodiment, the reactor configuration comprises only two ethylene feed streams.
[0011] The invention provides a process for forming a polymer based on ethylene, in the presence of at least one free radical, said process comprises at least the following: polymerization of a mixture comprising ethylene, in the presence of at least one initiator of free radicals, and in a reactor configuration comprising at least four reaction zones and at least three 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 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 polymerization; and wherein the average polymerization temperature of the first 40% by weight formed polymer (APT40% by weight) (based on the total amount of polymer formed) is less than or equal to 200°C.
[0012] In one embodiment, the reactor configuration comprises at least four ethylene feed streams.
[0013] In one embodiment, the reactor configuration comprises only three ethylene feed streams.
[0014] An inventive process may comprise a combination of two or more embodiments described herein.
[0015] In one embodiment, the maximum temperature for each reaction zone except reaction zone 1 is > 271°C, or > 272°C, or > 274°C, or > 276°C, or > 278 °C, or > 280 °C. In one embodiment, the maximum temperature for each reaction zone, except for reaction zone 1 and reaction zone 2, is > 271°C, or > 272°C, or > 274°C, or > 276°C, or > 278°C or > 280°C. In one embodiment, the minimum temperature for each reaction zone, except for reaction zone 1, reaction zone 2, and reaction zone 3, is > 271, or > 272, or > 274, or > 276, or > 278 °C or > 280 °C. In one embodiment, the maximum temperature for each reaction zone is <340°C, or <330°C, or <320°C.
[0016] In one embodiment, the combined amount of monomers and CTA(s) fed to the first reaction zone is 20 to 40 mol% of the combined amount of monomers and CTA(s) fed to the polymerization . In one embodiment, the amount of ethylene, and optionally one or more comonomers, and optionally one or more CTAs, fed to the first reaction zone is from 45 mole% to 75 mole%, or from 40 to 70 mole%, with based on the total moles of ethylene and, optionally, one or more comonomers, and optionally one or more CTAs, fed to the polymerization. In one embodiment, the combined amount of monomers and CTA(s) fed to the first reaction zone is 20 to 60 mole%, or 20 to 50 mole%, or 20 to 45 mole%, of the combined amount of monomers and CTA. (s) fed to polymerization.
[0017] In one embodiment, the average polymerization temperature of the "first 40% by weight polymer (based on total amount of polymer formed) formed" is less than or equal to 200°C, or <199°C, or < 198°C, or <197°C, or <196°C, or <195°C.
[0018] In one embodiment, the first “40% by weight of the total polymer is formed at a polymer weighted average polymerization temperature, T1,” and the remaining “60% by weight of the total polymer is formed at a temperature weighted average polymerization of T2” polymer and wherein (T2 -T1) > 58°C or > 59°C or > 60°C, or > 61°C, or > 62°C, or > 63°C, or > 64°C, or > 65°C.
[0019] In one embodiment, the ethylene conversion is > 28%, or > 29%, or > 30%, or > 31%.
[0020] In one embodiment, ethylene is fed to a first reaction zone (1) and to two or more subsequent reaction zones, zone n and zone n+1 or zone n+2, where n > 1, and where ethylene comprises fresh ethylene and ethylene recycling, and wherein at least two of the following ratios are satisfied: a) for reaction zone n, the ratio, Rn, of “mol fraction of fresh ethylene fed to the first reaction zone (RZ1 )” for “mole fraction of fresh ethylene fed to reaction zone n (RZn)” is (Rn = RZ1/RZn) from 0 to 1; b) for reaction zone n+1, the ratio, Rn+1, of “mol fraction of fresh ethylene to first reaction zone (RZ1)” to “mol fraction of fresh ethylene fed to the reaction zone (RZn+1) )” is (Rn+1 = RZ1/RZn+1) from 0 to 1; c) for reaction zone n+2, the ratio, Rn+2, of “mol fraction of fresh ethylene fed into the first reaction zone (RZ1)” to “mol fraction of fresh ethylene fed to the reaction zone (RZn+ 2)” is (Rn+2 = RZ1/RZn+2) from 0 to 1; and wherein the "total amount of ethylene fed to the polymerization process" is derived from at least one fresh stream of ethylene and at least one stream of recycled ethylene.
[0021] In one embodiment, ethylene is fed to a first (1) and a subsequent reaction zone, and wherein the following conditions are satisfied: a) the first ethylene-based feed streams to the reactor do not contain ethylene fresh; b) the ethylene-based feed to a subsequent reactor zone contains fresh ethylene;
[0022] In one embodiment, ethylene is fed to a first reaction zone (1) and to two subsequent reaction zones, and in which the following conditions are met: a) the first reaction zone does not receive fresh ethylene; b) the first ethylene-based feed to a subsequent reaction zone does not contain fresh ethylene; c) the second ethylene-based feed to a subsequent reaction zone contains fresh ethylene;
[0023] In one embodiment, ethylene is fed to a first reaction zone (1) and to three subsequent reaction zones, and in which the following conditions are met: a) the first reaction zone does not receive fresh ethylene; b) the second non-ethylene reaction zone receives fresh ethylene. c) the third ethylene based feed stream contains optionally fresh ethylene d) the fourth ethylene based feed stream contains fresh ethylene.
[0024] In one embodiment, the first ethylene feed stream comprises from 0 to 100 mol% of the total fresh CTA added to the polymerization and wherein the activity of the CTA system in the first ethylene feed is greater than or equal to the activity of CTA system on each subsequent ethylene feed.
[0025] In one embodiment, the first ethylene feed stream comprises from 20 to 100 mole% or from 25 to 100 mole% or from 30 to 100 mole% or from 35 to 100 mole% or from 40 to 100 mole% or from 45 to 100% molar, or from 50 to 100% molar of the total amount of fresh CTA added to the polymerization. In another embodiment, the activity of the CTA system on the first ethylene feed is greater than or equal to the activity of the CTA system on each subsequent ethylene feed. In one embodiment, the first ethylene feed stream comprises from 20 to 100 mole% or from 25 to 100 mole% or from 30 to 100 mole% or from 40 to 100 mole% or from 45 to 100 mole% or from 50 to 50 to 100% molar of the total amount of CTA fed to the polymerization, and wherein the activity of the CTA system on the first ethylene feed is greater than or equal to the activity of the CTA system on each subsequent ethylene feed. In one embodiment, the first ethylene feed stream comprises from 20 to 100 mole% or from 25 to 100 mole% or from 30 to 100 mole% or from 40 to 100 mole% or from 45 to 100 mole% or from 50 to 50 to 100% molar of the total amount of fresh CTA added to the polymerization, and wherein the activity of the CTA system on the first ethylene feed is equal to the activity of the CTA system on the second ethylene feed.
[0026] In one embodiment, the first ethylene feed stream comprises from 20 to 100 mole%, or from 25 to 100 mole%, or from 30 to 100 mole%, or from 40 to 100 mole%, or from 45 to 45 to 100 moles. 100% molar, or 50 to 100% molar of the total amount of fresh CTA added to the polymerization and where the activity of the CTA system in the first ethylene feed is greater than the activity of the CTA system in the second ethylene feed.
[0027] In one embodiment, the first ethylene feed stream comprises from 20 to 100 mole% or from 25 to 100 mole% or from 30 to 100 mole% or from 40 to 100 mole% or from 45 to 100 mole% or from 50 to 100 mol% of the total amount of CTA added to the polymerization, and wherein the activity of the CTA system in the first ethylene feed is equal to the activity of the CTA system in the third ethylene feed. In one embodiment, the first ethylene feed stream comprises from 20 to 100 mole% or from 25 to 100 mole% or from 30 to 100 mole% or from 40 to 100 mole% or from 45 to 100 mole% or from 50 to 50 to 100% molar of the total amount of CTA added to the polymerization, and where the activity of the CTA system in the first ethylene feed is greater than the activity of the CTA system in the third ethylene feed.
[0028] In one embodiment, the first ethylene feed comprises at least one CTA and wherein the activity of the CTA system on the first ethylene feed is greater than or equal to the activity of the CTA system on each subsequent ethylene feed.
[0029] An inventive process may comprise a combination of two or more embodiments described herein.
[0030] In one embodiment, the secondary compressor system comprises 3, 6, 9, 12, 15 or 18 pistons operating in the second compression stage. In one embodiment, the secondary compressor system comprises 4, 8, 10, 14, 16 or 20 pistons operating in the second compression stage. In one embodiment, the two-piston discharges are combined for each feed stream. In one embodiment, discharges from two or a multiple of two plungers are combined for each feed stream.
[0031] In one embodiment, the piston discharges are i) arranged in a fixed distribution over the ethylene-based feed streams, and in which, optionally, two or more discharges are combined in this fixed distribution, or ii) controlled during a polymerization, and wherein, optionally, two or more discharges are combined and used as one or more ethylene-based feed streams. In another embodiment, for option ii), the discharges are controlled using one or more throttling valves and/or split valves.
[0032] In one embodiment, one or more throttling valves and/or split valves are used to direct the flow of one or more piston discharges to the reactor.
[0033] In one embodiment, the secondary compressor system discharge streams are divided into three ethylene feed streams, each stream having the same amount in moles of ethylene-based components.
[0034] In one embodiment, the total ethylene-based feed flow to the reactor is 40 to 350 tons per hour, or 50 to 300 tons per hour, or 60 to 250 tons per hour. In one embodiment, the total ethylene-based feed flows into the reactor at 30 to 400 tons per hour, or 50 to 400 tons per hour, or 75 to 400 tons per hour, or 10 to 400 tons per hour.
[0035] In one embodiment, the invention provides a process for controlling polymeric properties, particularly rheological properties such as melt elasticity, G' and melt strength through process conditions such as peak temperatures, reset temperatures, CTA and fresh ethylene distribution, ethylene-based feed stream to multiple reaction zones, maintaining reactor inlet pressure and conversion level. Melt elasticity, melt strength and/or other rheological properties are each an indicator of MWD or vice versa are influenced by MWD.
[0036] In one embodiment, the invention provides a high pressure polymerization process to form an ethylene-based polymer, the process comprising at least the following step:
[0037] polymerization of a reaction mixture comprising ethylene, with the use of a reactor configuration comprising (A) at least two reaction zones, a first reaction zone (reaction zone 1) and a reaction zone i (zone of reaction i where i > 2), (B) at least two ethylene feed streams, each feed stream comprising a percentage of the total make-up ethylene fed to the high pressure polymerization process, in which a first stream of ethylene is sent to reaction zone 1 and a second stream of ethylene is sent to reaction zone i, and (C) operating the first reaction zone(s) at very peak temperature(s) write-off(s).
[0038] An inventive process may comprise a combination of two or more embodiments, as described herein.
[0039] In one embodiment, when the polymerization temperature (the temperature in the reactor, excluding the preheat section) is less than or equal to 180°C, the temperature of the cooling medium is greater than or equal to 180°C, or preferably greater than or equal to 185°C, more preferably greater than or equal to 190°C, more preferably greater than or equal to 195°C. In one embodiment, when the polymerization temperature is less than or equal to 190°C, the temperature of the cooling medium is greater than or equal to 180°C, or preferably greater than or equal to 185°C, more preferably greater or equal to 190°C, more preferably, greater than or equal to 195°C. In one embodiment, when the polymerization temperature is less than or equal to 200°C, the temperature of the cooling medium is greater than or equal to 180°C, or preferably greater than or equal to 185°C, more preferably greater or equal to 190°C, more preferably, greater than or equal to 195°C.
[0040] In one embodiment, the reactor configuration comprises at least one tubular reactor. In one embodiment, the polymerization takes place in a reactor with multiple or at least three reaction zones. In one embodiment, the polymerization takes place in a reactor configuration comprising at least three reaction zones, reaction zone 1 and reaction zone i (i >2) and wherein reaction zone i is downstream of zone reaction 1. In one embodiment, i is 2-5, or 2-4. In one embodiment, i = 2.
[0041] In one embodiment, the only reactors in the reactor configuration are tubular reactors.
[0042] In one embodiment, the first reaction zone is a tubular reaction zone. In one embodiment, each reaction zone is a tubular reaction zone.
[0043] In one embodiment, the first reaction zone is an autoclave reaction zone.
[0044] In one embodiment, i is greater than or equal to 3, or 4, or 5, or 10, or 20, or more.
[0045] In one embodiment, the reactor configuration comprises at least one Primary compressor and at least one Boost (Secondary) compressor.
[0046] In one embodiment, the process comprises only one Primary compressor.
[0047] In one embodiment, the ethylene-based polymer is a polyethylene homopolymer.
[0048] In one embodiment, the ethylene-based polymer is LDPE.
[0049] In one embodiment, the ethylene-based polymer is an ethylene-based interpolymer that comprises at least one comonomer.
[0050] In one embodiment, the process comprises 2, or 3, or 4, or 5, or 6, or more ethylene feed streams. In one embodiment, the first and second ethylene feed streams each comprise from 1 to 100 mole percent (mol percent), or 5 to 95 mole percent, or 10 to 90 mole percent, or 20 to 80 % molar, or from 30 to 70% molar, or from 35 to 65%, or from 40 to 60%, or from 45 to 55%, of the total ethylene fed to the polymerization process.
[0051] In one embodiment, the ethylene fed to the first reaction zone is at least 10 mole percent of the total ethylene fed to the polymerization. In one embodiment, the ethylene fed to the first reaction zone is 10 to 90 mole percent, or 20 to 80 mole percent, or 25 to 75 mole percent, or 30 to 70 mole percent, or 40 to 60 mole percent. mole percent of the total ethylene fed to the polymerization. In one embodiment, the ethylene-based feed stream is fed to at least three reaction zones, wherein the ethylene-based feed stream fed to the first reaction zone is from 25 to 50 mole percent or from 30 to 45 % molar or from 30 to 40% molar or 32 to 38% molar of the total ethylene fed to the polymerization.
[0052] In one embodiment, the make-up ethylene does not contain a chain transfer agent other than one or more residual compounds originating from the ethylene production/fractionation process.
[0053] In one embodiment, the total amount of fresh ethylene (offset) is distributed over all reaction zones. In one embodiment, make-up ethylene is distributed only to reaction zone i (i > 1). In one embodiment, the total amount of fresh CTA (compensation) is only delivered to the first reaction zone. In one embodiment, the total amount of fresh CTA (compensation) is delivered to all reaction zones that receive an ethylene-based feed stream.
[0054] In one embodiment, each feed to each reaction zone contains the same CTA system. In another embodiment, the CTA system of each feed contains a single CTA.
[0055] In one embodiment, each of the polymerization conditions in the reaction zones, independently, comprises a peak temperature of <400°C, or <380°C, or <360°C, or <340°C, or < 320°C, and an inlet pressure less than 1000 MPa, or less than 500 MPa, or less than 400 MPa, or less than 350 MPa.
[0056] In one embodiment, the maximum polymerization temperature in reaction zone 1 is < 260°C, or < 255, or < 250°C, or < 248°C, or < 246°C, or < 244°C , or < 242°C, or < 240°C. In one embodiment, the maximum polymerization temperature in reaction zones 1 and 2 is < 260°C, or < 255, or < 250°C, or < 248°C, or < 246°C, or < 244°C, or < 242°C or < 240°C. In one embodiment, the maximum polymerization temperature in reaction zones 1, 2 and 3 is < 260°C, or < 255, or < 250°C, or < 248°C, or < 246°C, or < 244° C or < 242°C or < 240°C.
[0057] In one embodiment, no fresh CTA is delivered to the first reaction zone. In one embodiment, 0 to 100% of the total fresh CTA is delivered to the first reaction zone.
[0058] In one embodiment, the reactor configuration comprises at least one tubular reactor, and each tubular reactor has one or more cooling zones. In one embodiment, the average speed of the reaction process in zone i is 10 to 20 m/s, or 12 to 20 m/s, or 12 to 18 m/s. In one embodiment, the reactor configuration comprises at least one tubular reactor, and each tubular reactor has one or more heat transfer zones. In one embodiment, the reactor configuration comprises at least one tubular reactor, and each tubular reactor is equipped with multiple heat transfer zones, and where heat is exchanged between the process side and a heat transfer medium.
[0059] In one embodiment, the reactor configuration comprises at least one tubular reactor, and the cooling and/or heating to each reactor is provided by pressurized liquid water operating in a co-current mode and/or counter-current mode. current, in multiple cooling zones that surround the reactor. In one embodiment, the reactor configuration comprises at least one tubular reactor and heating to each reactor is provided by pressurized steam.
[0060] In one embodiment, the reactor configuration comprises at least one tubular reactor and the cooling and/or heating of each reactor is provided by a liquid heat transfer fluid (e.g., a silicone oil and/or a polyglycol (eg DOWTHERM fluids)), operating in co-current mode and/or counter-current mode, in multiple cooling zones around the reactor.
[0061] In one embodiment, the high pressure reactor tubes used for the reactor assembly are typically equipped with a jacket to allow heat transfer with the aid of the heat transfer medium flowing through this jacket. In one embodiment, the reactor configuration comprises at least one tubular reactor and each tubular reactor is equipped with multiple jackets, and wherein each jacket has an inlet and an outlet and wherein the respective inlets and outlets of the two or more jackets are connected. in series with each other to form a heat transfer zone. In another embodiment, the inlet temperatures of the heat transfer zones are uniform, and each inlet temperature is 20 to 240°C. In another embodiment, at least two inlet temperatures of the heat transfer zones are uniform and each inlet temperature is 20 to 240°C. In another embodiment, each inlet temperature of a heat transfer zone is different from the inlet temperatures of the other heat transfer zones, and each inlet temperature is 20 to 240°C.
[0062] In one embodiment, the reactor configuration comprises at least one tubular reactor and each tubular reactor is equipped with multiple jackets and wherein each jacket has an inlet and an outlet and wherein the inlets and outlets of multiple jackets are connected in series to each other to form one or more heat transfer zones. In another embodiment, the inlet temperatures of the heat transfer zones are uniform, and each inlet temperature is 20 and 240°C. In another embodiment, at least two inlet temperatures of the heat transfer zones are uniform and each inlet temperature is 20 and 240°C. In another embodiment, each inlet temperature of a heat transfer zone is different from the inlet temperatures of the other heat transfer zones, and each inlet temperature is 20 and 240°C.
[0063] In one embodiment, the maximum discharge pressure of the secondary compressor system is limited to < 3,100 bar or < 3,000 bar or < 2,900 bar, or < 2,800 bar, or < 2,700 bar, or < 2,600 bar, or < 2,500 bar, or < 2,500 bar, or < 2,400 bar, or < 2,300 bar.
[0064] In one embodiment, the efficiency of the secondary compressor system is maximized to satisfy the design load of the secondary compressor system when operating at maximum discharge pressure. In one embodiment, the performance of the secondary compressor system is maximized to satisfy the minimum load (mechanical or electrical) of the secondary compressor system drive when operating at minimum discharge pressure.
[0065] In one embodiment, the efficiency of the secondary compressor system is maximized by maximizing the piston and/or cylinder size to satisfy the secondary compressor design load and/or the maximum load (mechanical or electrical) of the system drive. secondary compressor when operating at maximum discharge pressure.
[0066] In one embodiment, two or more piston discharges are combined to form a reactor feed, and wherein these pistons are out of phase. Such an arrangement allows for the reduction of flow fluctuations and pressure pulsations in the compressor discharge lines and in the reactor feed lines. In one embodiment, the 2, 3, or 4-piston discharges are aligned with an ethylene-based reactor feed and wherein these discharges are out of phase with each other. In one embodiment, the discharges of the multiples of 2 or 3 or 4 pistons are aligned with a reactor feed and wherein the discharges in each multiple are out of phase. In one embodiment, the discharges of two or more pistons are aligned with an ethylene-based reactor feed and wherein these discharges are out of phase with each other. In one embodiment, the discharges of the multiples of 2 or more pistons are in line with a reactor feed and wherein the discharges in each multiple are out of phase.
[0067] In one embodiment, the mixture further comprises at least one CTA selected from an aldehyde, an alkane, an acetate, a ketone, an alcohol, an ester, a mercaptan, a phosphine, a phosgene, an alpha-olefin or a combination of them. In one embodiment, the mixture further comprises at least one CTA selected from an aldehyde, an alkane, a ketone, an alcohol, an ester, an alpha-olefin, or a combination thereof.
[0068] In one embodiment, the total ethylene-based feed flow to the reactor configuration is from 30 to 400 tons per hour, or from 50 to 400 tons per hour, or from 75 to 400 tons per hour, or from 100 to 400 tons per hour. In one embodiment, the total ethylene-based feed flow to the reactor configuration is 40 to 350 tons per hour, or 50 to 300 tons per hour.
[0069] In one embodiment, the ethylene-based polymer has a melt index (I2) of 0.10 to 20.0 g/10 min.
[0070] In one embodiment, the ethylene-based polymer comprises ethylene and one or more comonomers, and preferably a comonomer. Comonomers include, but are not limited to, α-olefins, acrylates, methacrylates, and anhydrides, each typically having no more than 20 carbon atoms. α-olefin comonomers, which have a combined monomer and CTA functionality, can have 3 to 10 carbon atoms, or alternatively, α-olefin comonomers can have 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1 -pentene and combinations thereof. Preferably, the α-olefin comonomers are selected from propylene, 1-butene and combinations thereof. In one embodiment, the ethylene-based polymer is an LDPE. initiators
[0071] Free radical initiators are generally used to produce the ethylene-based polymers of the invention. A free radical initiator, as used herein, refers to a free radical generated by chemical and/or radiation means. Examples of free radical initiators include organic peroxides, including, but not limited to, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, and peroxyketals. Preferred initiators are t-butyl peroxy-pirate, di-t-butyl peroxide, t-butyl peroxyacetate and t-butyl peroxy-2-hexanoate, or mixtures thereof. In addition, oxygen can be used as an initiator. In one embodiment, these organic peroxide initiators are used in an amount of 0.001 to 0.2% by weight, based on the weight of polymerizable monomers. The peroxide initiator can be characterized and classified with its half-life temperature at certain time intervals. For example, the half-life temperature at 0.1 h indicates the temperature at which an initiator is radically dissociated to 50% in 0.1 h (or 6 minutes).
[0072] AkzoNobel shows in their brochure “Reactor Initiators and Additives for Half-Life Temperatures of Thermoplastics” at 0.1, 1.0 and 10 h for their commercial organic peroxide initiators. Due to typical residence times of less than five minutes in the high pressure reactor system and less than two minutes in individual reactor zones, the half-life temperature of 0.1 h is relevant for the classification and selection of peroxide initiators. organic. Organic peroxides can be classified into the following classes: Class 1: Low temperature initiator, with a half-life of 0.1 hour, ranging from 70 to 120°C. These peroxides are typically used to start; Class 2: Medium temperature initiator, with a half-life temperature of 0.1 hour, ranging from 120 to 150°C; Class 3: High temperature initiator, with a half-life temperature of 0.1 hour, above 150°C. Oxygen is believed to work by forming intermediate organic hydroperoxides, which typically decompose at temperatures above 180°C, so oxygen can be considered a high temperature initiator (Class 3).
[0073] Organic peroxides are often applied in mixtures of low and high temperature initiators, to initiate and/or accelerate the temperature development by the lowest temperature class of initiators, while the control temperature, respectively the maximum temperature of the zone of autoclave reaction and the maximum peak temperature for tubular reactor zone, is controlled and determined by the highest temperature class of initiators.
[0074] The temperature control of a reaction zone is therefore a function of the molar sum of initiators of the highest temperature class, fed into each zone, and may be further affected by the efficiency at which high temperature peroxides applied will dissociate or generate polymerization radicals. The mixture of single or multiple initiators, potentially diluted with a solvent, injected into reaction zone i is called the initiating system for reaction zone i. In one embodiment, oxygen is used alone, or in combination with other initiators, as a high temperature initiator. In one embodiment, the use and efficiency of the initiator is affected by the so-called cage effect or potential to form effective polymerization radicals.
[0075] In one embodiment, an initiator is added to at least one reaction zone and the initiator has a half-life temperature, in one second, greater than 255°C, preferably greater than 260°C. In another embodiment, such initiators are used at a maximum polymerization temperature between 320°C and 350°C. In another embodiment, the initiator comprises at least one peroxide group incorporated into a ring structure. Examples of such primers include, but are not limited to, TRIGONOX 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonean) and TRIGONOX 311 (3,3,5,7 ,7-pentamethyl-1,2,4-trioxepane), both available from Akzo Nobel, and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5- tetroxone) available from United Initiators. See also International Publications nos. WO 02/14379 and WO 01/68723.
[0076] In one embodiment, the polymerization pressure, measured at the first inlet of the reactor, is from 1000 bar to 4000 bar, or from 1400 to 3600 bar, or from 1800 to 3200 bar.
[0077] Depending on the final article processing step and end use, different product quality targets are defined for each product grade. Melt index, density and elasticity of the molten material are the main parameters to describe and measure the quality of the product and the consistency of the product produced. The melt index reflects the average molecular weight and can be adjusted and/or controlled by varying the level and contribution of the CTA systems. The level of short chain branching (SCB) is an indicator of the density of the product, which is typically allowed to vary within certain ranges, eg 0.924 ± 0.010 g/cm3. The level of long-chain branching (LCBf) strongly affects molecular weight distribution and hence viscoelastic properties, e.g. melt strength, and are important in applications such as blow and cast film, foam, extrusion coating. , etc. Properties such as SCB and LCB level are strongly affected by the applied polymerization temperature and pressure levels. In addition, the LCB level is also affected by the polymer level profile in the reactor system. Additions
[0078] An inventive composition may comprise one or more additives. Additives include, but are not limited to, stabilizers, plasticizers, antistatic agents, pigments, dyes, nucleating agents, fillers, glidants, fire retardants, processing aids, smoke inhibitors, viscosity control agents, and anti-blocking agents. . The polymeric composition may, for example, comprise less than 10% of the combined weight of one or more additives, based on the weight of the inventive polymer. In one embodiment, the polymers of this invention are treated with one or more stabilizers, for example, antioxidants, such as IRGANOX 1010, IRGANOX 1076 and IRGAFOS 168. In general, the polymers are treated with one or more stabilizers prior to extrusion or other processes. of fusion.
[0079] An inventive composition may further comprise at least one other polymer in addition to an inventive ethylene-based polymer. Blends and blends of the inventive polymer with other polymers can be prepared. Polymers suitable for blending with the inventive polymers include natural and synthetic polymers. Exemplary polymers for blending include propylene-based polymers (both impact polypropylene modification, isotactic polypropylene, atactic polypropylene, and random propylene/ethylene copolymers), various types of ethylene-based polymers, including high pressure free radical LDPE , heterogeneously branched LLDPE (typically via Ziegler-Natta catalysis), substantially linear or linear homogeneously branched PE (typically via a single site, including metallocene catalysis), including multi-reactor PE ("in-reactor" compositions of heterogeneously branched PE and homogeneously branched PE, such as the products disclosed in USP 6,545,088 (Kolthammer et al.), 6,538,070 (Cardwell et al.), 6,566,446 (Parikh et al.), 5,844,045 (Kolthammer et al. ), 5,869,575 (Kolthammer et al.) and 6,448,341 (Kolthammer et al.), ethylene vinyl acetate (EVA), ethylene/vinyl alcohol copolymers, polystyrene, modified polystyrene impact, ABS, styrene/butadiene block copolymers and hydrogenated derivatives thereof (SBS and SEBS) and thermoplastic polyurethanes. Other ethylene-based polymers include homogeneous polymers such as plastomers and olefinic elastomers (eg, polymers available under the tradenames AFFINITY Plastomers and ENGAGE Elastomers (The Dow Chemical Company) and EXACT (ExxonMobil Chemical Co.). propylene (for example, polymers available under the tradename VERSIFY Plastomers & Elastomers (The Dow Chemical Company) and VISTAMAXX (ExxonMobil Chemical Co.) may also be useful as components in blends comprising an inventive polymer. applications
[0080] The polymers, polymer blends and compositions of this invention can be employed in a variety of conventional thermoplastic manufacturing processes to produce useful articles, including extrusion coating onto various substrates; monolayer and multilayer films; molded articles, such as blow molded, injection molded or rotational molded articles; coatings; fibers; and woven or non-woven fabrics. An inventive polymer can be used in a variety of films, including, but not limited to, transparency and/or shrink films, glue shrink films, melt stretch films, silage films, stretch caps, sealants and foils. diaper backs. Other suitable applications include, but are not limited to, wires and cables, gaskets and profiles, adhesives; footwear components and car interior parts.
[0081] The invention also provides an ethylene-based polymer made by an inventive process. In one embodiment, the ethylene-based polymer is a polyethylene homopolymer. In one embodiment, the ethylene-based polymer is an ethylene-based interpolymer. In one embodiment, the ethylene-based polymer is LDPE. In one embodiment, the ethylene-based polymer has a density of 0.910-0.940 g/cm 3 . In one embodiment, the ethylene-based polymer has a melt index of 0.1 to 1000 g/10 min. In one embodiment, the ethylene-based polymer has a density of 0.910-0.940 g/cm 3 , and a melt index between 0.1 and 1000 g/10 min. In one embodiment, the ethylene-based polymer has a density of 0.910-0.940 g/cm 3 , and a melt index of 0.1 to 100 g/10 min. In one embodiment, the ethylene-based polymer has a density of 0.910-0.940 g/cm 3 , and a melt index of 0.1 to 50 g/10 min. In one embodiment, the ethylene-based polymer has a density of 0.9100.940 g/cm 3 , and a melt index of 0.1 to 20 g/10 min. In one embodiment, the ethylene-based polymer has a density of 0.910-0.940 g/cm 3 and a melt index of 0.2 to 20 g/10 min. An inventive polymer may comprise a combination of two or more embodiments as described herein.
[0082] The invention also provides a composition comprising an ethylene-based polymer of the invention. In one embodiment, the composition further comprises another ethylene-based polymer. The invention also provides an article comprising at least one component formed from an inventive composition. In one embodiment, the article is an extrusion coating resin. In another embodiment, the article is a film. In another embodiment, the article is an insulating material and/or a protective layer around a metal wire. In another embodiment, the article is foam. An inventive article may comprise a combination of two or more embodiments as described herein.
[0083] In one embodiment, Z1/Zi is controlled to be greater than 1. In one embodiment, Z1/Zi is controlled to be less than 1. In one embodiment, Z1/Zi is controlled to be from 0.2 to 2 .0, or 0.3 to 1.8, or 0.4 to 1.6, or 0.5 to 1.5.
[0084] In one embodiment, the efficiency of the secondary compressor system is maximized to satisfy the design load of the secondary compressor system when operating at maximum discharge pressure. In one embodiment, the performance of the secondary compressor system is maximized to satisfy the minimum load (mechanical or electrical) of the secondary compressor system drive when operating at minimum discharge pressure. In one embodiment, the throughput of the secondary compressor system is maximized by the maximization plunger and/or cylinder size, in order to meet the secondary compressor design load and/or the maximum load (mechanical or electrical) of the secondary compressor drive. secondary compressor system when operating at maximum discharge pressure. DEFINITIONS
[0085] Unless otherwise stated, implied by context, or customary in the art, all parts and percentages are based on weight, and all test methods are current as of the filing date of this application.
[0086] The terms "ethylene feed stream" or "ethylene based feed" or "ethylene based feed stream" or "ethylene feed" as used herein refer to a feed stream for a reaction zone, and which contains a greater amount of ethylene, based on the molar amount of all components in the feed stream. Optionally, one or more chain transfer agents, comonomers, other process components (such as lubricating oil, solvent, etc.) and/or impurities (such as initiator degradation products) may be present in the feed current.
[0087] The term “total ethylene feed stream”, as used herein, refers to the sum of all ethylene feed streams fed to the reactor configuration.
[0088] The term “ethylene-based feed components”, as used herein, refers to ethylene (fresh and/or recycled), and optionally CTA (fresh and/or recycled), solvent (fresh and/or recycled) , comonomer(s) (fresh and/or recycled) and/or other components (e.g. including but not limited to fresh and/or recycled lubricating oil(s), antioxidant(s), ethane, methane and/or dissociation initiator products), added to a reaction zone at an inlet to the reaction zone. In one embodiment, the ethylene-based feed components comprise the following: ethylene (fresh and/or recycled), and optionally CTA (fresh and/or recycled), solvent (fresh and/or recycled), comonomer(s) ( or recycled) and/or other components selected from the following: fresh and/or recycled lubricating oil(s), antioxidant(s), ethane, methane and/or dissociation initiating products. In another embodiment, the ethylene-based feed components comprise the following: ethylene (fresh and/or recycled) and, optionally, CTA (fresh and/or recycled), solvent (fresh and/or recycled), comonomer(s) (fresh and/or recycled) and/or other components selected from the following: fresh and/or recycled lubricating oils, antioxidant(s), ethane, methane, initiators (eg oxygen) and/or dissociation initiating products.
[0089] The term “LCB content” refers to a level of long chain branches per 1000 carbons (total carbons) incorporated in the polymer. The LCB content is calculated with the help of kinetics in “Transfer to Polymer” and “Propagation” of ethylene and optionally present comonomers. Comonomers containing a C=C double bond are represented in calculating the level of LCB per 1000C by its two carbons in its double bond group. The LCB content can be given as a level in the final polymer (final product LCBf), in the formation of the polymer in progression along the reactor (cumulative LCBf) or in the polymer formed locally as a function of the local polymerization conditions in the reactor (local LCBf ).
[0090] The term “ethylene conversion” or “ethylene conversion level”, as used herein, refers to the weight fraction of ethylene fed to the reactor, which is incorporated into the final polymer produced.
[0091] The term "composition", as used herein, includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.
[0092] The term "polymer" refers to a compound prepared by polymerization of monomers, of the same type or of a different type. The term generic polymer thus encompasses the term homopolymer (which refers to polymers prepared from only one type of monomer with the understanding that trace amounts of impurities can be incorporated into the polymeric structure) and the term "interpolymer" as defined below. Trace amounts of impurities may be incorporated on and/or into the polymer. The trace amount of impurities may include residues of initiators and other components, such as lubricating oil, solvent, etc., showing chain transfer activity.
[0093] The term "interpolymer" refers to polymers prepared by polymerizing at least two different types of monomers. The generic term interpolymer includes copolymers (which refer to polymers made from two different monomers) and polymers made from more than two different types of monomers.
[0094] The term "ethylene-based polymer" refers to a polymer comprising a major amount of polymerized ethylene, based on the weight of the polymer, and optionally at least one comonomer.
[0095] The term "ethylene-based interpolymer" refers to an interpolymer that comprises a major amount of polymerized ethylene, based on the weight of the interpolymer, and at least one comonomer.
[0096] The term "ethylene-based copolymer" refers to a copolymer comprising a major amount of polymerized ethylene, based on the weight of the copolymer, and a comonomer as the only types of monomer.
[0097] The term “Long-Chain Branching Frequency (LCBf)” used here refers to the ratio, described below, relative to the transfer to polymer steps, leading to long-chain branching per 1000 carbon atoms (or 500 carbon units). of ethylene) converted to polyethylene. Typically LCBf is the average number of the entire polymer. This relationship can be determined via NMR or calculated through simulations. The numbers used here are derived by simulations. The LCBf derived through simulations is the transfer ratio to polymer reaction rate RLCB and the propagation rate Rp, and the ratio multiplied by 500 for the conversion of an incorporated ethylene unit to 1000 incorporated carbon atoms. RLCB = kLCB*[Rad]*[Pol] and Rp = kp*[Rad]*[Ethylene]. The RLCB/Rp ratio would only indicate the frequency of LCB formation by one unit of converted ethylene. To derive the total LCBf of the entire polymer, the ratio must be integrated into the temperature, pressure and conversion profile of the reactor used. This is typically done in simulation software such as Predici by CiT or similar programs, which are capable of solving differential equations.
[0098] The term "high pressure polymerization process", as used herein, refers to a free radical polymerization process carried out at an elevated pressure (inlet pressure) of at least 1000 bar (100 MPa).
[0099] The terms “inlet flow” or “reaction zone inlet current”, as used here, refer to the total mass flow or total molar flow at the inlet of a reaction zone, and consists of the mass flow or molar stream transferred from the previous reaction zone and optional ethylene based feed streams, more optionally, CTA feed stream, more optionally initiator feed stream optionally fed alone or in conjunction with another feed stream. The terms "side stream" or "side feed stream", as used herein, refer to ethylene based feed stream, CTA system feed stream and/or initiator system, for sequential reaction zones.
[00100] The term "reactor system", as used herein, refers to devices used to polymerize and isolate a polymer. Such devices include, but are not limited to, one or more reactors, reactor preheater(s), monomeric reactor cooling device(s), secondary compressor(s), or hyperbaric compressor(s). ), primary compressor(s) and/or booster compressor(s). The term "reactor configuration", as used herein, refers to one or more reactors, and optionally one or more reactor preheaters, used to polymerize a polymer. Such reactors include, but are not limited to, autoclave reactor(s), tube reactor(s), and combinations of autoclave and tube reactors.
[00101] The term “inlet pressure” or “reactor inlet pressure”, as used here, refers to the pressure level at the first inlet of the first reaction zone.
[00102] The term "reaction zone", as used herein, refers to a reactor zone where the polymerization reaction is initiated or restarted by the addition of free radicals or components that dissociate and/or generate free radicals. Typically, the reaction medium is heated and/or cooled by a heat transfer medium flowing through a jacket around the reactor. A reaction zone may also start with the addition of fresh and/or recycled ethylene, and/or free radicals or components that dissociate and/or generate free radicals. The term "first reaction zone", as used herein, refers to the first reactor zone where polymerization is initiated by the addition of radicals and/or components that dissociate and/or generate radicals. The first reaction zone ends at the point where there is a fresh feed of radicals and/or components that dissociate and/or generate radicals and, optionally, recycled and/or fresh ethylene and/or comonomer(s).
[00103] The phrase “maximum temperature for a reaction zone” or “peak temperature” used here refers to the highest temperature measured in a reaction zone, for example, in an autoclave reaction zone (typically, recorded as a maximum zone temperature), in a tubular reaction zone (typically recorded as a peak temperature).
[00104] The phrase “average polymerization temperature of reaction zone i”, as used here, refers to the mean restart and peak temperature of reaction zone i. The phrase "average polymerization temperature of the first 40% by weight of polymer formed", as used herein, refers to the average temperature of polymerization in the reactor section at which the initial 40% by weight of the final amount of polymer is produced. The phrase "average polymerization temperature of the last 60% by weight of polymer formed", as used herein, refers to the average temperature of polymerization in the section of the reactor where the last 60% by weight of the total polymer is produced. This section starts at the end of the reactor section, where the first 40% of the final polymer is produced.
[00105] The term “hypercompressor inlet pressure”, as used here, refers to the pressure on the suction side of the hypercompressor system.
[00106] The term “secondary compressor system”, as used here, refers to one or more compressors and optional coolers, which are used to compress a gaseous feed in two compression stages, i.e. a first compression stage and a second compression stage; Typically, an ethylene-based feed stream is compressed from the suction pressure of the secondary compressor system, to the discharge pressure of the first compression stage, and is further compressed in the second compression stage, to the final discharge pressure of the compressor. secondary compressor system. The output of the first compression stage in combination with the input of the second compression stage plus the optional cooler(s) is also called the “interstage” of the secondary compressor system. Typically, the first stage compression compresses from a suction pressure in the range of 100 to 350 bar to an interstage pressure in the range of 800 to 1600 bar. Typically, the second stage compression compresses from an interstage pressure as described above to a final discharge pressure in the range of 2000 to 3600 bar.
[00107] The term "plunger", as used herein, refers to an alternative pressurizing device, within a set of cylinders, compressing a gaseous feed (e.g., an ethylene-based feed) from the suction pressure to the interstage pressure of the secondary compressor system, or from interstage pressure to the final discharge pressure of the secondary compressor system. Typically, the sizing of a piston and cylinder package is uniform within a compression stage (first or second) of a secondary compressor system, but differs between the first and second compression stages of a secondary compressor system. . Each plunger is housed within a set of cylinders.
[00108] The term “pulsation” refers to non-uniform flow conditions at the piston discharge caused by a reciprocating operation, including a loading and dispensing stage of the piston assembly during each rotation of the compressor drive shaft. . The non-uniform flow pattern causes variable pressure drop in the discharge system and therefore fluctuating pressure conditions in the compressor discharge and ethylene-based flow rates. When two or more piston discharges are combined, care must be taken to ensure that the flow patterns caused by the discharges of different pistons used to form an ethylene-based reactor feed stream do not overlap, minimizing differences. minimum and maximum flow and pressure fluctuations in the feed line to the reactor. Preferably, the flow patterns are complementary (or out of phase) with each other. Preferably, the pistons which are aligned with an ethylene-based reactor feed stream should be offset and/or multiples of 3 or 4 piston combinations aligned with the ethylene-based reactor feed stream.
[00109] The term “maximum allowable load” of a secondary compressor system refers to the maximum mechanical force (load) that can be applied to the compressor frame and/or associated components to cylinders, pistons, and connecting shaft assemblies. and drive. The “maximum allowable load” is determined by the weakest component. Maximum load is determined by the component manufacturer's design pressure as well as inertia forces during operation.
[00110] The term “maximum electrical load” of a secondary compressor system refers to the maximum power that an electric motor, driving the compressor, can deliver in continuous operation, based on the design of the motor manufacturer.
[00111] The term “split valve” refers to a device that controls the distribution of a feed stream (e.g., an ethylene-based feed stream) from the secondary compressor system and to two or more reactor zones. . The term “throttling valve” refers to a control valve that can be used to increase or decrease a flow through a line.
[00112] Secondary compressor or hypercompressor, is a device that compresses a feed stream; for example, at least one of the following: a) ethylene-based components from the HPR (High Pressure Recycle) and/or b) ethylene-based components, each from the Primary, each for a level of pressure required to feed the reactor at its inlet pressure. This compression can occur in one or several stages of compression and can be combined with intercooling. The Hiper comprises a reciprocating piston compressor, and may consist of single or multiple compressor structure(s).
[00113] The term “secondary compressor throughput”, as used herein, refers to the net amount of feed components, eg ethylene-based feed components, compressed and fed to the reactor configuration. Secondary yield is a function of compression volume and density of feed components, eg ethylene-based components, on the suction side. The pressure and temperature conditions on the suction side of the secondary compressor will define the density of the feed components, eg ethylene-based components, to be compressed. The term “discharge current”, as used here, refers to the current that comes from the discharge of a compressor (eg, a secondary compressor).
[00114] The term “fresh”, when used herein, in reference to an ethylene-based feed component (i.e., “fresh ethylene”, “fresh CTA”), refers to reagent supplied from a source(s) external(s) and not supplied internally from a recycled source(s). For example, in one embodiment, fresh ethylene is used as "make-up ethylene" necessary to make up for ethylene consumed by polymerization and/or lost through, for example, purging process ethylene and residual ethylene in the polymer. The term "recycled", when used herein, in reference to a reagent (i.e., "recycled ethylene", "recycled CTA"), refers to the unreacted reagent separated from the polymer in the high-speed separator(s). pressure and/or pressure separator(s), and returned/compressed to the reactor.
[00115] The terms “feed”, “feed stream” or “feed stream” as used herein refer to fresh and/or recycled components (e.g. ethylene, initiator, CTA and/or solvent) added to a reaction zone at an inlet.
[00116] The term “molar fraction”, as used here, refers to the molar ratio of a component in a mixture to the total moles of the components in the mixture. The molar fraction can be determined by calculating the ratios of molar quantities or molar flows. The phrase "mol fraction of fresh ethylene fed to the first reaction zone (RZ1)", as used here, refers to the molar amount of fresh ethylene fed (via the forward stream) to the first reaction zone, divided by the molar amount of ethylene and of the optional comonomer(s) and optional CTA(s) fed (via a forward current) to the first reaction zone. The phrase "mol fraction of fresh ethylene fed to the nth reaction zone (RZn)", as used here, refers to the molar amount of fresh ethylene fed (via a side stream) to the nth reaction zone divided by the molar amount of ethylene and optional comonomer(s) plus optional CTA(s) fed (via a side stream) to the nth reaction zone.
[00117] The term "CTA system" includes a single CTA, or a mixture of CTAs, added to the polymerization process, typically to control the melt index. A CTA system includes a component capable of transferring a hydrogen atom to a growing polymer molecule containing a radical, through which a radical is formed in the CTA molecule, which can then start a new polymer chain. CTA is also known as telogen or telomere. The terms “CTA activity” or “chain transfer activity coefficient” (Cs value), as used here, refer to the ratio of “chain transfer rate” to “ethylene propagation rate”. See the Mortimer references provided in the experimental section below.
[00118] The terms “Z1/Zi” as used herein are determined as follows. The “molar concentration of the reactor zone of a CTAj in a reactor zone i ([CTA]ji)” is defined as the “total molar amount of CTA fed (excluding a transfer from a previous reaction zone) into the reactor zones k = 1 ak = i” divided by “the total molar amount of ethylene fed (excluding transfers from a previous reaction zone) to reactor zones 1 ai”. Note that i > 1. This relationship is shown below in Equation AC.
In Equation AC, j > 1
, is the “number of moles of the ith CTA recently injected into the kth zone df reactor (where k = 1 ai)” and
is the “amount of moles of ethylene recently injected into the k-th reactor zone (where k = 1 ai)”.
[00119] The “transfer activity of a CTA (system) in a reactor zone I (Zi)” is defined as the “sum of the molar concentration of the reactor zone of each CTA in the reactor zone” multiplied by its constant of chain transfer activity (Cs) - see Equation BC. The chain transfer activity constant (Cs) is the ratio of the reaction rates Ks/Kp, at a reference pressure (1360 atm) and a reference temperature (130°C). This relationship is shown below in Equation BC, where ncompi is the total number of CTAs in the reactor zone i. Note that i > 1 and ncompi > 1.

[00120] The term “Rn = RZ1/RZn”, as used here, refers, for reaction zone n, to the ratio of the “mole fraction of fresh ethylene fed to the first reaction zone (RZ1)” to the “fraction molar fresh ethylene fed to reaction zone n (RZn)”.
[00121] For the polymerization of ethylene homopolymers, the values of RZ1 and RZn are determined as follows - see Equations AE and BE below.
n fresh,eth,n + neth,n (na 2) (E^BE)' where n fresh,eth,1 is the molar flow of fresh ethylene (from Primary) fed to reaction zone 1 [mol/h] , nfresh,eth,n is the molar flow of fresh ethylene (from Primary) fed to reaction zone n [mol/h], neth,1 is the molar flow of ethylene from HPR recycle to reaction zone 1 [ mol/h], neth, is the molar flux of ethylene from HPR fed to the reaction n [mol/h].
[00122] Equation AE and Equation BE, as used here, to calculate RZ1 and RZn, assume that 60 mol% of the total ethylene-based feed stream to the reactor is from the high pressure recycle (HPR) stream. The remaining 40 mol% of the ethylene-based feed stream is from the Primary, which includes the fresh ethylene stream and low pressure recycling (LPR). Fresh ethylene is 33.3 mol%, which includes ethylene converted and lost by the purge stream. Thus, the Low Pressure Recycle (LPR) flow is 6.7 mole %, which includes ethylene from LPR and secondary compressor leaks.
[00123] The term "initiator system" includes a single initiator, or a mixture of initiators, each typically dissolved in a solvent (eg, a hydrocarbon solvent) added to the polymerization process. The term “injection point”, as used here, refers to the inlet location of a device (used in a polymerization process) where a feed stream is added to the device. The term "feed conditions", as used herein, refers to the flows in moles of the components fed to the reactor, for example, ethylene, CTA, initiators and/or comonomer(s). The term “maximum outlet temperature” or “before temperature drops”, as used here, refers to the maximum temperature at the end of the last reaction zone.
[00124] The term “process velocity in reaction i”, as used here, is the flow of the process volume or ethylene-based component divided by the cross-sectional area of the reactor tube, used in a reaction zone. , and is calculated as follows:
where Φi [m3/s] is the volumetric flow of the total components (including monomer, comonomer, CTA, impurities, etc.) fed to reaction zone i, calculated by dividing the total mass flow fed to reaction i by the density of the flow; and di [m] is the inner diameter of the tube of the reactor zone i. The term “average process speed in reaction zone i” refers to the average process speed along the length of reaction zone i. TEST METHODS
[00125] Melt Index - Melt Index, or I2, is measured in accordance with ASTM D 1238, Condition 190°C/2.16 kg, and is reported in grams per 10 minutes. The I10 is measured in accordance with ASTM D 1238, Condition 190°C/10 kg, and is reported in grams eluted over 10 minutes. 13C NMR for Branching
[00126] Sample Preparation: Each polymer sample is prepared for 13C NMR by adding approximately 2.7 g of a 50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene containing 0.025 M Cr(AcAc)3 as a relaxing agent, to 0.25 g of sample in a 10 mm Norell 1001-7 NMR tube. The sample is dissolved and homogenized by heating the tube and its contents to 150°C using a heating block and heat gun.
[00127] Data Acquisition Parameters: Data are collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high temperature cryoprobe. Data is acquired using 1280 to 2560 transients per data file, a 6 second pulse repetition delay, 90 degree inversion angles, and inversion decoupling with a sample temperature of 120°C. All measurements are made on non-spinning samples in locked mode. Samples are thermally equilibrated for seven minutes prior to data acquisition. 13C NMR chemical shifts are internally referenced to the EEE triad, at 30.0 ppm.
[00128] LDPE contains many types of branches; e.g. 1,3-diethyl, ethyl branches to quaternary carbon (gem-diethyls), C4, C5 and more, and if butene or propylene is used, isolated C2 branches (from butene) or C1 branches (methyl , of propylene) are observed. All branch levels are determined by integrating the spectrum from about 40 ppm to 5 ppm and setting the integral value to 1000, then integrating the peaks associated with each branch type, as shown in Table A below. The peak integrals then represent the number of each branch type per 1000C in the polymer. The last column of Table A describes the carbon associated with each integral band. A direct measurement of the C6+ branches in the LDPE is given, where the long branches are not differentiated from the “chain ends”. This value represents a branching level that is defined differently in LLDPE, HDPE and other linear polymers. The peak of 32.2 ppm, representing the 3rd carbon from the end of all chains or branches of 6 or more carbons is used. To derive the number of C6+ branches by the long-chain branching mechanism, the measured C6+ number must be corrected for the presence of both main-chain end groups in LDPE molecules and the potential use of alpha-olefins with numbers carbon >8. Table A: Branch Type and 13C NMR Ranges Used for Quantitation
EXPERIMENTAL Flowchart used for CP1 to CP3, CP1.1 and CP1.2
[00129] Figure 1 shows a generalized flowchart of a simulated high pressure polymerization plant configuration containing a tubular reactor, where all components of a hypercompressor are sent to the first (front) reaction zone of the reactor, representing the configuration of the reactor “Todo de Gas Frontal”. Stream (1) is the new ethylene compensation, which is compressed together with the output of the Booster by the Primary to stream (2). The stream (2) is combined with the high pressure recycle stream (18) to the stream (3) and sent to the inlet of the secondary compressor system (Hiper). The secondary compressor system pressurizes the ethylene feed stream to a sufficient level of high pressure tubular reactor (Reactor) feeds. Current (4) represents make-up (fresh) feed from the CTA system in this reactor configuration it can be fed into the inlet(s), interstages or outside the Hyper. The CTA system can consist of a single component or multiple components and can include varying compositions. Current (6) has a potential comonomer supply. Comonomer streams (6) can be fed into the inlet(s), interstage(s), outlet(s) of the secondary compressor system and/or directly into the reaction zones. The discharge temperature of the secondary compressor system is typically in the range of 60 to 100°C. The ethylene feed to the first reaction zone is typically preheated to a temperature of 130 to 180°C, while the side feed ethylene is fed to the reactor at the discharge temperature of the secondary compressor system or cooled before being fed to the reactor. .
[00130] In the Reactor, polymerization is initiated with the help of an initiating system(s) via free radicals injected and/or activated at the entrance of each reaction zone. The maximum temperature in each reaction zone is controlled at a set point by regulating the concentration and/or amount fed into the initiating system at the start of each reaction zone. After finishing the reaction, and having applied several cooling steps, the reaction mixture is depressurized and/or cooled in (10), and separated in the high pressure separator (HPS). The HPS separates the reaction mixture into an ethylene-rich stream (15), containing small amounts of waxes and/or entrained polymer, and a polymer-rich stream (11), which is sent to the LPS for further separation. The ethylene stream (15) is cooled and cleaned in the stream (17). Stream (16) is a purge stream to remove impurities and/or inerts. The polymer separated into LPS is further processed in (12). The ethylene removed in the LPS is fed to the Booster where, during compression, condensables such as solvent, lubricating oil and other components are collected and removed by the chain (14). The output of the Booster is combined with the ethylene make-up stream (1), and further compressed by the Primer. Flowchart from CP4 to CP6 and IP5.1
[00131] Figure 2 shows a generalized flow gram of a simulated high pressure polymerization plant configuration containing a tubular reactor. Stream (1) is the fresh ethylene make-up, which is compressed together with the output of the Booster by the Primary to stream (2). The stream from the primary compressor (2) is combined with the high pressure recycle stream (17) to form the stream (18). The stream (18) is divided into stream (4) and stream (19). Chain (19) becomes chain (5). Currents (4) and (5) are sent to the secondary compressor system. The comonomer (current 6 and 7) and compensating CTA (current 4 and 5) are injected into current (4) and (5). Discharge current (9) from the secondary compressor is sent to the first (front) reaction zone, while current (8) is sent through line (20) as side current to the inlet of the second reaction zone. Current (6) and/or current (7) represent the compensation (fresh) feed of the AHU system. Optionally, the comonomer(s) can be fed via current (6) and/or (7). The CTA compensation currents (6) and/or (7) can be fed into the input(s), interstage(s), output(s) of the secondary compressor system and/or input(s) of the zones of reaction. The remaining parts of the scheme are described in the description of Figure 1. Flowchart used for IP5.2 and IP5.3
[00132] Figure 3 represents the high pressure polymerization in which ethylene is sent to the front (stream 9) and to the side (stream 20) of the reactor. In Figure 3, fresh ethylene in stream (2) from the primary compressor is sent to stream (4). All other remaining streams are discussed in the description of Figure 2 above. Flowchart from CP7 to CP9 and IP8.1
[00133] Figure 4 represents the high pressure polymerization in which ethylene is sent to the front (stream 9) and two side inlets (stream (20) and stream (21)) of the reactor. All other remaining streams are discussed in the description of Figure 2 above. Flowchart of IP8.2 and IP10.2.
[00134] Figure 5 shows a generalized flowchart of a simulated high pressure polymerization reactor system containing a tubular reactor, where all components of a hypercompressor are divided into three ethylene-based feed streams to the reactor. Stream (1) is the fresh ethylene make-up, which is compressed together with the output of the Boost compressor by the Primary compressor to stream (2). Current (2) is sent to (19). Stream 19 is sent to stream (19a) and the remaining ethylene from (19) is sent through line (3a) to (19b). High pressure recycle stream (18) is aligned with stream (19c) and the remaining ethylene from (18) is sent through line (3b) to line (19b). Streams (19c), (19b) and (19a) are compressed by the secondary compressor system to the reactor inlet pressure and are sent through 9, 20 and 21 respectively to the inlet of the first, second and third cooling zones. reaction. The stream (4), which represents the make-up (fresh) feed of the AHU system in this reactor configuration, can also be fed into the input(s), interstage or output of the compression stream of the secondary compressor system ( 19c). The CTA system can consist of a single component or multiple components, and can include varying compositions.
[00135] Current (6) and current (7) represent an optional comonomer supply that can also be fed into the input(s), interstage(s), output(s) of the secondary compressor system. Optionally, chains (4) and (6) can be aligned to (19b) and/or (19a) as well. The discharge temperature of the secondary compressor system is typically between 60 and 100°C. The ethylene feed to the first reaction zone is typically preheated to a temperature of 130 to 180°C, while the ethylene, fed to a side feed to the reactor, is fed at the discharge temperature of the secondary compressor system or cooled before from feeding the reactor. All other remaining parts of the reactor system are described above for Figure 1. Flowchart from CP10 to CP12, IP10.1, IP11.1 and IP12.1
[00136] The Process Flow Diagram used for CP10, CP11, CP12, IP10.1, IP11.1 and IP12.1 is shown in Figure 6. It is a generalized flowchart of a simulated high pressure polymerization reactor system containing a tubular reactor, where all three ethylene-based feed streams are split and kept separate along the secondary compressor system. Stream (1) is fresh ethylene (compensation), which is compressed along with the output of the Booster compressor by the Primary compressor to stream (2). The stream (2) is combined with the stream (17) of the high pressure recycle to form the stream (18). The fresh CTA system (stream 4) and the optional comonomer (stream 5) can be added to the stream (18) to make the stream (19). Stream (19) is then divided into stream (19a), stream (19b) and stream (19c) in which stream (19a) is sent after compression to the front of the reactor while stream (19b) and stream (19c) ) are sent to the reactor side via line (20) and line (21). All other remaining parts of the reactor system are described above for Figure 2. Polymerization Simulations
[00137] A polymerization simulation model with the applied reaction scheme and kinetics is described by Goto et al. (Goto et al; Journal of Applied Polymer Science: Applied Polymer Symposium, 36, 21-40, 1981 (Title: Computer model for commercial high pressure poly-ethylene reactor based on elementary reaction rates obtained experimentally). commercial high pressure based on experimentally obtained elemental reaction rates)) Other reactor and product modeling frameworks are available from ASPEN PLUS of Aspen Technology, Inc., Burlington, Massachusetts, USA; and PREDICI of Dr Wulkow, Computing in Technology GmbH (CiT), Rastede, Germany The process and product responses predicted by these modeling frameworks are determined by the reactor parameters, the reaction scheme, and the applied kinetic parameters. Applied kinetic parameters are described below.
[00138] The polymerization simulations were performed with the LDPE simulation model, Goto, as discussed above. The kinetic data used by Goto et al. were derived from high pressure free radical polymerization experiments of polyethylene carried out at varying temperatures, pressures and polymer concentrations, as described in the following references: K. Yamamoto, M. Sugimoto; Rate constant for long chain-chain branch formation in free-radical polymerization of ethylene; J. Macromol. Science-Chem., A13 (8), pp. 1067-1080 (1979). The elementary reaction steps are described by Goto et al. as follows: i) ethylene propagation, ii) radical termination, iii) backbiting or SCB formation, iv) polymer transfer or LCB formation, v) beta scavenging of secondary radicals leading to vinyl formation, and vi) beta scavenging of tertiary radicals leading to the formation of vinylidene.
[00139] The kinetic data for the main reactions are shown in Table 1, where ko is the pre-exponential or frequency factor; Ea is the activation energy, reflecting the temperature dependence; and ΔV is the activation volume, reflecting the pressure dependence. All kinetic constants are from Goto et al., except the ko, Ea, and ΔV values for backbiting, which were optimized to better reflect the level of methyl ramifications (as analyzed by the C13 NMR technique) in high-pressure polyethylene, in depending on pressure and temperature conditions. Table 1: Kinetic Constants for Main Reactions

[00140] In high pressure free radical polymerization (inlet pressure >100 MPa), branching can be formed by the following predominant reactions: a) backbiting reactions, which are intramolecular reactions, leading to ethyl and butyl branches, b ) reactions that incorporate alpha-olefins into the polymer molecule, and such alpha-olefins being used as chain transfer agents (eg propylene, 1-butene, etc.); c) reactions involving transfer to the polymer resulting in a polymeric branch with a carbon length that depends on the number of ethylene insertions before this branch is terminated. For example, intermolecular hydrogen transfer leads to the termination of a growing polymer molecule and the reactivation of a “dead” or inactive polymer molecule. For reactions involving transfer to polymer (“c” above), theoretically, this reaction can lead to branch length variation of ethyl and butyl branches up to 1,000 carbons and more. The formation of ethyl and butyl branches by this reaction occurs only at a very low and insignificant level, typically less than 0.1 per 1000 carbons. A long chain branch is formed from intermolecular hydrogen transfer ("c" above), and leads to a broadening of the molecular weight distribution of the final polymer. For the reactions in “b” above, the incorporation of an alpha-olefin does not result in a broadening of the molecular weight distribution of the final polymer. 13C NMR can be used to measure the level of long chain branching (LCB), defined as C6 or higher; however, corrections to the NMR spectrum can be made for the presence of any alpha-olefin (CTA) with a carbon number of eight or more by comparing the spectra of polymer samples taken with and without the presence of the alpha-olefin. higher. The kinetics developed by Goto et al. and Yamamoto et al. focuses on the relationship of process conditions such as temperature, pressure, and polymer concentration (expressed as incorporated ethylene units), the kinetic parameters of intermolecular hydrogen transfer (“transfer to polymer”), and the impact of the level of intermolecular hydrogen transfer in the molecular weight distribution of the final polymer. The long-chain branching rate is a function of temperature, pressure, and polymer concentration (expressed as the number of ethylene incorporated). The frequency of long-chain branching is a function of the ratio of long-chain branching rate versus propagation of ethylene and/or comonomers. Table 1 shows that long-chain branching has a higher activation energy than the propagation rate, and therefore the frequency of long-chain branching will be promoted by higher polymerization temperatures.
[00141] The kinetic data for the selected CTAs are given in Table 2. The kinetic constants were calculated with the help of the kinetic constants in the value of Cs (ks/kp) as determined by Mortimer (see References below), and the kinetics of ethylene propagation as given by Goto et al. (see Table 1). Table 2: Kinetic Constants for Selected CTAs

[00142] Propylene in addition to its CTA functionality will also act as a comonomer, resulting in additional methyl branches. These additional methyl branches generally reduce the density of the polymer by 0.001 to 0.004 g/cc. Furthermore, comonomer activity will increase the overall level of consumption per reactor pass, through which more propylene must be added to compensate for consumption as CTA and comonomer. References:
[00143] General: G. Luft, Chem.-Ing.-Tech., Hochdruck-Polyaethylen, Vol. 51 (1979) No. 10, pages 960-969. Peroxide efficiency: T. van der Molen et al., Ing. Chim. Ital, “Light-off” temperature and consumption of 16 initiators in LDPE production, Vol. 18, N. 1-2, Feb 1982, pages 7-15. Chain transfer activity and comonomer reactivity scheme data are described in the following: P.Ehrlich, G.A. Mortimer, Fundamentals of the free radical polymerization of ethylene, Adv. Polymer Sci., Vol. 7, 386-448 (1970); G. Mortimer, Journal of Polymer Science: Part A-1; Chain transfer in ethylene polymerization; Vol 4, p 881-900 (1966); G. Mortimer, Journal of Polymer Science: Part A-1, Chain transfer in ethylene polymerization. Part IV. Additional study at 1360 atm and 130°C; Vol. 8, p15131523 (1970); G. Mortimer, Journal of Polymer Science: Part A-1, Chain transfer in ethylene polymerization. Part V. The effect of temperature; Vol. 8, p1535-1542 (1970); G. Mortimer, Journal of Polymer Science: Part A-1, Chain transfer in ethylene polymerization Part V. The effect of pressure, Vol. 8, p. 1543-1548 (1970); and G. Mortimer, Journal of Polymer Science: Part A-1, Chain transfer in ethylene polymerization VII. Very reactive and depleteable transfer agents, Vol. 10, pp 163-168 (1972). See LDPE simulation model in S. Goto et al., Journal of Applied Polymer Science: Applied Polymer Symposium, 36, 21-40, 1981 (Computer model for commercial high pressure polyethylene reactor based on elementary reaction rates obtained experimentally). Initiator System
[00144] Table 3 shows that temperature and pressure exert a significant influence, via activation energy (Ea) and activation volume (ΔV), on propagation rates and free radical termination rates. Peroxide efficiency is affected by the Kp / Kt1/2 ratio and therefore will increase with higher temperature and/or higher pressure levels, and will decrease with lower temperature and/or lower pressure levels. For example, Theo van der Molen et al. (see References above), show in their article “Light-off temperature and consumption of 16 initiators in LDPE production”, that the consumption of initiators to reach a certain temperature level in a high pressure LDPE reactor is strongly affected. by operating pressure. Thus, decreasing the operating pressure, without increasing the amount of initiator system, will lead to lower peak or maximum zone temperatures and lower monomer conversion level for a given reactor system and vice versa. Table 3: Half Life Temperature at Different Times of each Organic Peroxide (*)
Note: (*): Akzo Nobel leaflet; (**): TRIGONOX is a trade name of AKZONOBEL. Tubular Reactor Simulations Detail
[00145] Table 4 and Table 5 present the reactor configurations and process conditions for inventive and comparative polymerizations. The type of CTAs used for simulations to control the melting index are propionaldehyde (PA), propylene and iso-butane. PA has the activity (Cs) of 0.33 with 10% conversion, propylene has Cs of 0.0122, and an assumed conversion of 20%, as it has both CTA and comonomer functionality, as measured by Mortimer at 1360 atm and 130°C. The melt index of the polymers used in the simulations is 1 g/10 min and 10 g/10 min, and can be easily extended to a wider MI range. The polymerizations are simulated for a high pressure tubular reactor, operating at a reactor inlet pressure less than or equal to 320 MPa (3,200 bar), using an ethylene-based yield of 60 tons/h (except for 35 Mt/h for CP2 and CP3)., data taken from document JP 05034422). The ethylene-based flow from the hypercompressor is divided by 100/0/0/0 (CP1 to CP3, CP1.1 and CP1.2) or 50/50/0/0 (CP4 to CP6, IP 5.1, IP 5.2 and IP 5.3) or 25/25/50/0 (CP7 to CP9, IP8.1 and IP8.2) and 33/33/33/0 (CP10, CP11, CP12, IP10.1, IP10.2, IP11.1 and IP12.1), which indicates that the ethylene-based current could be completely forwarded, or partially distributed both at the front and side of the reactor. A tubular reactor configuration comprises up to several thousand meters in total length, for four or more reaction zones. In this invention, the reactor length varies from 1300 to 1500 meters, depending on the reactor configuration. The inside diameters of the reactor tubes range from 27 mm to 54 mm for the first reaction zone and from 38 mm to 54 mm for the remaining part of the reactor. Reactor dimensions are selected to maintain a good process speed of about 12 to 14 m/s. The pressure drop in the reactor is around 500 bar for all simulations. In all simulations, the lateral stream was cooled to 40°C before feeding into the reactor.
[00146] Initiator systems comprising a mixture of multiple single initiators are injected into the reactor at different locations, to create multiple reaction zones, and thereby create a four-peak temperature profile, and raising the overall conversion. The half-life of each peroxide was listed in Table 3. Typically mixtures of tert-butyl peroxy-2-ethylhexanoate (TBPO) and di-tert-butyl peroxide (DTBP) were used; however, with low start and/or reset temperatures. Tert-butyl peroxy-pivalate (TBPIV) was added or in case of peak temperature reduction, 270°C or lower, DTBP was replaced by Tert-butyl peracetate (TBPA).
[00147] Water temperatures, to cool or heat the reaction zones, are operated with an inlet temperature of 155°C in a counter-current mode. Alternatively, water temperatures can be operated at other uniform or non-uniform settings. Cooling zones can be operated in co- and/or counter-current mode. The simulations were performed with an inlet temperature of the first reaction zone of 150°C. Derivation of Average Polymerization Temperature (APT) of the first 40% by weight (APT40%) of polymers formed and of the last 60% by weight (APT60%) of the final polymers formed
[00148] Assume that 40% by weight of polymer formation is achieved within reaction zone 3 at reactor length L3,a, one denoted by “Tp,Z3,a” (see Figure 7). The amount of polymer belonging to the first 40% by weight of the final polymer is calculated in (Eq. 1).

[00149] This amount of polymer formation can be achieved in either the first or second or third reaction zones. In the calculation example below, the first 40% by weight of the final polymer is formed in the third reaction zone.
[00150] Reaction zone 3 is considered to be two separate reaction zones, called Z3,a and Z3,b. Note that Z3,a has restart and peak temperatures of respectively Tre-int,Z3 and TP,Z3,a. Subsequently, Tp,Z3,a becomes the reset temperature of the reaction zone Z3,b.
[00151] The process simulation output may not reveal the exact temperature that pertains to the 40 wt% polymer formation point, but temperatures at both the upstream and downstream locations are available. The temperature belonging to the 40% polymer formation point is calculated from the above and after data points following the calculation below.
[00152] Calculation of Tp,Z3, a (polymerization temperature at 40% by weight of polymer formed)
see Figure 7 for a demonstration of Supporting Equation 1, Where and
are the % by weight of polymer form below (earlier) and above (later) 40% by weight of polymer formation (only at the left and right positions of "Tp,3,a" or L3,a in Figure 7). Data points are taken directly from the process simulation results.
are the temperatures to the left and right of Tp,Z3,a, corresponding to
The cumulative production over the length of the reactor (L) is indicated by “MP, L”. “L” is defined as the reactor length from the first inlet of the first reaction zone to the location of interest in the reactor. Production in the reaction zone (Zi) is indicated by “MP,Zi”, where “i” indicates the reaction zone number. The cumulative production at the end of reaction zone i is indicated by “MP, L,Zi”. The amount of polymer produced in the reaction zone Z3,a and Z3,b is calculated by the following equations.
Similar to the next reaction zone (e.g. reaction zone (i+1)), the following equations apply- [kg/h] (Eq- 5), w here HP, Z1, MP, Z2, MP, Z3 , MP, Z3, um, MP, Z3, b, MP, Z4 are the amount of polymer formed in reaction zone 1, 2, 3, 3a, 3b and 4 [kg/h], respectively- The average temperature of polymerization of each reaction zone (or reaction zone i) is an average restart temperature and peak temperature.
where i can be the first, second, third or fourth reaction zone-
are calculated in (Eq. 7) and (Eq. 8) as follows.
where Mp zi a is the amount of polymer produced in the reaction zone Zi,a.
Example of APT40%, APT60% and ΔAPT(60-40)% for IP8.1.
[00153] The process simulation result shows that 40% by weight of the final polymer is formed in reaction zone 3. At 38.8% by weight of the final polymer was formed at a temperature of 206°C. At 41.8% by weight of the final the polymer was formed at a temperature of 217°C. The temperature in the first 40% of polymer formed is
The amount of polymer formed in the reaction zone Z1 is 1494 [kg/h]. The amount of polymer formed in reaction zones (1+2) or MP,L, Z2 (amount of accumulative polymer formed at the end of reaction zone 2 in Figure 7) is 4399 [kg/h]. The amount of polymer formed in the reaction zones (1+2+3) or cumulative polymer at reactor position L3 (MP,L,Z3) is 14388 [kg/h]. The amount of polymer at the end of reaction zone 4 (or at the end of the reactor, in this case) is 19128 [kg/h]
[00154] Thus, the calculated amount of polymer formed in each relevant reaction subzone is as follows:

The average polymerization temperatures of each reaction zone, APT40% by weight, APT60% by weight and ΔA PT60-40)% are as follows:
. Normalized Molecular Weight Distribution (MWD)
[00155] The molecular weight distribution (representing the relationship between (dw/dlogM) and logM) is an important parameter used in polymerization projects, process development, improvement and operation. It is necessary to determine the types of polymer produced (narrow or wide MWD) that provide the desired properties of the product. Normalized MWD data can be obtained using commercial software package PREDICI (licensed by Dr. M. Wulkow, Computing in Technology, GmbH, Pater-Klbe-Straβe 7, D-26180 Rastede, Germany), for the construction of MWD kinetics of polymerization (Goto kinetics in this study), by solving polymeric population balance equations. The inputs required for the PREDICI are the Goto kinetics used, and the monomer and/or comonomer, initiator and CTA flows, temperature and pressure profiles, as well as elapsed time, all of which can be obtained from the simulation. of the process. The PREDICI software package can be used to generate the normalized MWD data.
[00156] In this study, the MWD of each polymer was calculated and subsequently normalized with the MWD of CP1 (100/0/0/0), following (Eq. 11). The simulated MWD value for CP1 is 5.71.
Comparative Polymerizations for Tubular Reactor: CP1. CP1.1, CP1.2, CP2 and CP3
[00157] Simulations of comparative polymers CP1. CP1.1, CP1.2, CP2 and CP3 were made for the 100/0/0/0 reactor configuration (where the ethylene-based feed stream is entirely sent to the first reaction zone). The diameter of the reactor's inner tube is 54 mm, giving an average process speed of 13.6 m/s over the entire length of the reactor. In the CP1 simulations. CP1.1, CP1.2, reactor inlet pressure and overall conversion level are maintained at 2,800 bar and 31.9%, respectively. The conversion level is kept at the target level by adjusting the latest maximum temperatures as shown in CP1.1 and CP1.2. While almost all simulations were performed for products with a melt rate of 1 g/10 min, the simulations and trends can easily be extended to different melt rates and CTA types. In the simulations for the 100/0/0/0 reactor configuration, all CTA, compensation and recycle, are fed to the first reaction zone. More details can be found in Table 4 and Table 5.
[00158] In CP1. ethylene is polymerized with high peak temperatures of 290, 290, 290 and 290°C in the four reaction zones resulting in an LCB content of 3.13/1000C in the final product. The temperature of the first 40% polymer produced (APT40%) and the last 60% polymer (APT60%) are 231°C and 272°C, corresponding to an ΔAPT (60-40)% of 42°C.
[00159] The normalized molecular weight distribution (MWD) is 100%, namely
The MWD of CP1 is used to calculate the normalized MWD values reported in Table 6. The APT 40% in % for CP1.1 is much smaller than for CP1. namely 204°C vs 231°C and therefore ΔAPT (60-40)% is increased from 42°C to 77°C. The overall LCB level is increased, resulting in a slightly wider MWD (103% vs. 100%). Decreasing APT 40% by weight does not result in a narrowing of MWD. Similar results were observed for CP1.2 where peak temperatures of 240°C/240°C/318°C/318°C are applied, giving similar APT at 40% by weight as in example CP1.1.
[00160] Additional simulations using reactor configuration and process conditions, described in document JP05034422, were performed and are shown in CP2 and CP3 (see Table 4 and 5). These two simulations are used to narrow the MWD of the polymers at a low reactor inlet pressure of 2400 bar. Operation at a lower first peak temperature (230°C at CP2) is shown to produce 40% higher APT, 60% higher APT, higher final LCBf as well as higher conversion level than equal temperature operation in the zones. reaction (see case CP3). Note that the conversion levels of these simulations are 23.0 and 22.6%, respectively. Comparative polymerizations for tubular reactor: CP4, CP5 and CP6
[00161] CP4 to CP6 represent the high pressure reactor configuration with a 50/50/0/0 ethylene feed distribution over the reaction zones. Simulations were performed for a product with 1MI and using a CTA with Cs = 0.33. In CP4, CP5 and CP6, fresh ethylene from the primary compressor and recycled ethylene from the HPR are equally distributed in both reactor feed streams, resulting in a CTA feed concentration (Z1/Zi=1) along the reactor.
[00162] In CP4, peak temperatures of 290, 290, 290 and 290°C and a reactor inlet pressure of 3,200 bar are applied, resulting in a normalized MWD of 104% and a conversion level of 31.9% . By lowering the reactor inlet pressure to the level of 2,800 bar, the normalized MWD is increased to 119%, keeping the conversion level at 31.9% (see CP5). CP6 shows how much peak temperatures have to be reduced, namely to 282, 282, 282 and 282°C, in order to reach a normalized MWD level similar to CP4. Also other properties, in terms of LCBf and APT, remain at the same level as for CP4, except for the lower overall conversion (30.7% vs. 31.9%). Comparative polymerizations for tubular reactor: CP7 to CP12.
[00163] The process conditions and product properties of comparative CP7 to CP9 are very similar to the comparative examples of CP4 to CP6; with the exception of the 25/25/50/0 ethylene feed distribution vs. 50/50/0/0. At CP7 to CP9, fresh ethylene from the primary compressor and recycled ethylene from the HPR and CTA (compensation and recycling) are distributed proportionally to the reactor feed streams, resulting in an equal CTA feed concentration throughout the reactor. . In addition, Examples CP10 to CP12 show the process conditions and properties of the simulated polymers using the equal ethylene-based feed current distribution in a 33/33/33/0 reactor configuration. This distribution of current flow equal to the reaction zone is suitable for secondary compression systems, comprising 3, 6, 9, 12, 15, etc., pistons in the second compression stage of the secondary compressor. The properties of the simulated polymer are shown in Table 6. Detailed information on the process conditions can be found in Table 4 and Table 5.



Inventive polymerization IP5.1, IP5.2, IP5.3, IP8.1, IP8.2, IP10.1, IP10.2, IP11.1 and IP12.1.
[00164] The polymers of the invention were simulated using different reactor configurations and operating conditions and as well as other important process parameters such as fresh ethylene and/or fresh CTA distribution (see Table 4 and Table 5 for more details ). IP5.1, IP5.2 and PI5.3 were prepared at the pressure level of 2,800 bar, with the first peak temperature decreasing to 240°C, while the remaining peak temperatures are increased to maintain the conversion level at 31 .9%. At IP5.1, the normalized MWD is decreased from 119% to 102% (IP5.1 vs. CP5) by decreasing the first peak temperature. In CP6, a similar normalized MWD decrease, as achieved in IP5.1, is obtained by reducing peak temperatures to 282, 282, 282 and 282°C, where the conversion level is reduced to 30.7 %. It is important to note that the IP5.1 example provides the same normalized MWD as CP6, but with a significantly higher conversion level (31.9% vs. 30.7%). Furthermore, applying fresh ethylene delivery to the reactor side, and/or delivering fresh CTA to the first reaction zone, further lowers the normalized MWD to 83% (IP5.2) and 80% (IP5. .3), respectively, compared to 102% for IP5.1; however, the conversion is unexpectedly held at 31.9%. The properties of the simulated polymers are shown in Table 6. Surprisingly, IP 5.1, IP5.2 and IP5.3 each show a lower normalized MWD relative to CP5, despite similar final LCB levels in each final polymer. Furthermore, the levels of APT40% by weight and ΔAPT(60-40)% are, respectively, significantly lower and higher than the corresponding levels for CP5.
[00165] Similar effects were obtained for IP8.1, IP8.2, IP10.1 and IP10.2 with two different ethylene feed streams to the reactor side. For example, IP 8.1 and IP 8.2 use the 25/25/50/0 ethylene based feed current configuration, while IP10.1 and IP10.2 use the 33/ 33/33/0. Simulations are done using 240°C as the first two peak temperatures, and keeping the conversion at 31.9%, increasing the last two peak times. The impact of the 25/25/50/0 and 33/33/33/0 reactor configurations on the possible MWD range is much more pronounced (a wider range of possible MWD values) than the impact for the 50/ 50/0/0 (IP5.1 to IP5.3) as shown in Figure 8. The influence of CTA type with CTA and comonomer activity was studied in CP11 and IP11.1. For example, propylene used as a CTA can also act as a comonomer, thus creating methyl groups in addition to the normal SCB level in the polymer produced, and this, in turn, lowers the final density of the polymer. Table 7 shows the influence of using propylene as a CTA on SCB and methyl levels. Table 7: Influence on the Methyl group and SCB level with propylene as CTA in CP11 and IP11.1

[00166] Additional simulations of CP12 and IP12.1 were performed to study the influence of higher MI(I2) on polymer properties, such as LCBf, MWD and APT 40% by weight. As shown in Table 6, despite both polymers having the same melt index (10 MI), and similar LCBf values, the inventive polymerization IP12.1 has a much lower normalized MWD of 89%, compared to a normalized MWD of 116% for CP12. These results indicate that the inventive processes can be used to produce polymers of varying melt index values and low, normalized MWD values. It can be concluded that: a) sending less ethylene to the first reaction zone, b) increasing the flow and/or the number of feed streams on the reactor side, and/or c) varying the operating conditions; each, in combination with the desired average polymerization temperature of the first 40% by weight of polymer formed (APT40% by weight), can be used to expand the MWD capacity of a tubular reactor configuration.
[00167] The impact of ethylene-based separation ratio (percentage of ethylene sent to the front of the reactor) and process conditions (pressure, temperature, CTA system selection and distribution of fresh ethylene and/or fresh CTA) on the properties of the product (represented by normalized MWD, LCBf, APT 40% by weight, ΔAPT (60-40)%) were investigated. The following was found: (i) decreasing APT 40% by weight and increasing ΔAPT (60-40)% improves the narrow MWD capacity of reactor configurations, where the overall ethylene based feed stream divided over the front reaction zone and the side reaction zone(s)(i); (ii) the inventive polymerization allows the production of narrow MWD products at the constant conversion level, in reactor configurations using a global ethylene-based feed stream distribution through the front reaction zone and the zone(s) ) of side reaction(s); (iii) at a constant conversion level, reducing the first and/or second peak temperature, and maintaining the pressure input level, will narrow the normalized MWD; (iv) applying different reactor conditions, for example (a) inventive application of APT 40% by weight and increasing APT conditions (60-40) for the production of narrow MWD products, (b) high pressure and low first and/or second peak temperatures, (c) fresh differentiated ethylene and fresh CTA distributions; the combination of (a) with (b) and/or (c) will increase the narrow MWD capacity of the process.
[00168] It was found that the production of LDPE with multiple (>2) ethylene feed streams, and the application of different operating conditions, namely a low peak temperature(s) in the first, second or third reaction zones, allows the production of narrow MWD polymers, at constant and/or high conversion levels. Furthermore, it has been surprisingly found that narrow MWD polymers can be produced at a high level of conversion, and low operating pressure, by applying low peak temperature(s) in the first, second or third reaction zones, and distributing the ethylene mainly to the reactor side, and/or distributing the fresh CTA mainly to the first and/or second reaction zones and selecting the Cs value of the CTA system. Surprisingly, it has been found that narrower MWD polymers can be made with a reactor configuration, where 30 to 40 mol% of the overall ethylene-based feed is sent to the front reaction zone, while the ethylene-based feed Remaining ethylene is split along two or more reaction zones. The ability to produce narrow MWD polymers at a lower reactor inlet pressure allows for optimization of the secondary compressor system with respect to energy consumption, or increased efficiency for the same energy consumption by expanding the piston sizes, and/or maintenance of outer cylinder sizes. Favorable ethylene-based feed distribution can be achieved by combining one or more piston discharge(s) from the secondary compression stage of the secondary compressor system, and sending the combined stream to the reactor feed streams. required. The use of throttling and/or split valves is another way to obtain the required flow distributions.

权利要求:
Claims (10)
[0001]
1. Process for forming an ethylene-based polymer, said process characterized in that it comprises 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 3,200 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 mol% to 80 mol%, 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% by weight formed polymer (APT40% by weight) (based on the total amount of polymer formed) is less than or equal to 200°C.
[0002]
2. Process for forming an ethylene-based polymer, said process characterized in that it comprises 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 four reaction zones and at least three 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 20 mol% to 70 mol%, 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% by weight formed polymer (APT40% by weight) (based on the total amount of polymer formed) is less than or equal to 200°C.
[0003]
3. Process according to claim 1, characterized in that the difference in polymerization temperature (T2-T1) between the last 60% by weight of the final polymer formed (T2) and the first 40% by weight of the final polymer formed (T1) is greater than or equal to 58°C.
[0004]
4. Process according to claim 1, characterized in that the ethylene is fed to a first reaction zone (1) and to two or more subsequent reaction zones, zone n and zone n+1 or zone n+2, in where n > 1, and where the ethylene comprises fresh ethylene and recycled ethylene, and where at least two of the following ratios are satisfied: a) for reaction zone n, the ratio, Rn, of "mole fraction of fresh ethylene fed to first reaction zone (RZ1)” for “mole fraction of fresh ethylene fed to reaction zone n (RZn)” is (Rn = RZ1/RZn) is less than or equal to 1; b) for reaction zone n+1, the ratio, Rn+1, of the “mol fraction of fresh ethylene fed to the first reaction zone (RZ1)” to “mol fraction of fresh ethylene fed to the reaction zone n+1 (RZn+1)” is (Rn+1 = RZ1/RZn+1) less than or equal to 1; c) for reaction zone n+2, the ratio, Rn+2, of “mol fraction of fresh ethylene fed to the first reaction zone (RZ1)” to “mol fraction of fresh ethylene fed to reaction zone n+2 (RZn+2)” is (Rn+2 = RZ1/RZn+2) is less than or equal to 1; and wherein the "total amount of ethylene fed to the polymerization process" is derived from at least one fresh stream of ethylene and at least one stream of recycled ethylene.
[0005]
5. Process according to claim 1, characterized in that the first ethylene feed comprises at least one CTA, and wherein the activity of the CTA system in the first ethylene feed is greater than or equal to the activity of the CTA system in each subsequent feed of ethylene.
[0006]
6. Process according to claim 1, characterized in that the polymerization occurs in at least one tubular reactor, and in which each ethylene fed to the reactor is generated from one or more discharge streams from a second stage of compression of a secondary compressor system.
[0007]
7. Process according to claim 6, characterized in that the discharge streams from the second compression stage of the secondary compressor system are combined into at least two feed streams from the reactor zone.
[0008]
8. Process according to claim 6, characterized in that each ethylene feed receives a discharge current generated from one or more pistons of the second compression stage of the secondary compressor system and in which each ethylene feed contains the same molar amount of ethylene-based feed components.
[0009]
9. Process according to claim 2, characterized in that the ethylene-based feed stream fed to the first reaction zone is 30 to 40% molar of the total ethylene supplied to the polymerization.
[0010]
10. Process according to claim 1, characterized in that the ethylene-based polymer is an LDPE.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

GB1370101A|1971-10-11|1974-10-09|Exxon Research Engineering Co|Production of polyethylene|

---

JPS5415904B2|1976-06-29|1979-06-18|

---

US4135044A|1977-08-08|1979-01-16|Exxon Research & Engineering Co.|Process for achieving high conversions in the production of polyethylene|

---

DE69211569T2|1991-12-30|1997-01-23|Dow Chemical Co|ETHYLENE INTERPOLYMER POLYMERIZATION|

---

US6545088B1|1991-12-30|2003-04-08|Dow Global Technologies Inc.|Metallocene-catalyzed process for the manufacture of EP and EPDM polymers|

---

US6448341B1|1993-01-29|2002-09-10|The Dow Chemical Company|Ethylene interpolymer blend compositions|

---

BR9405715A|1993-01-29|1995-11-28|Dow Chemical Co|Process for preparing an ethylene / a-olefin interpolymer composition and ethylene / a-olefin interpolymer composition|

---

US5869575A|1995-08-02|1999-02-09|The Dow Chemical Company|Ethylene interpolymerizations|

---

EP0928797B3|1998-01-12|2012-01-11|Dow Global Technologies LLC|Medium density ethylene polymers, a process to prepare these polymers and use of carbonyl group containing chain transfer agents in this process|

---

AT271075T|2000-03-16|2004-07-15|Basell Polyolefine Gmbh|METHOD FOR PRODUCING POLYETHYLENE|

---

CN1178958C|2000-08-15|2004-12-08|阿克佐诺贝尔股份有限公司|Use of trioxepans in process to make high-solid acrylic, styrenic and LDPE-type resins|

---

KR100419864B1|2001-11-15|2004-03-04|한국화학연구원|New Cross-linker, and Cross-linkable Solid polymer Electrolytes using the same|

---

US7745550B2|2001-12-19|2010-06-29|Exxonmobil Chemical Patents Inc.|Tubular polymerization reactors and polymers made therein|

---

CN1271102C|2003-06-12|2006-08-23|中国科学院化学研究所|Method for preparation of functional polyolefin block copolymer|

---

ES2421584T3|2005-03-09|2013-09-04|Saudi Basic Ind Corp|A process for the preparation of an ethylene copolymer in a tubular reactor|

---

RU2008108093A|2005-08-05|2009-09-10|Эксонмобил Кемикэл Пейтентс Инк. |METHOD AND INSTALLATION FOR OBTAINING POLYMERS AND CO-POLYMERS BASED ON ETHYLENE|

---

BRPI0614390A2|2005-08-05|2011-03-22|Exxonmobil Chem Patents Inc|high pressure polymerization compressor|

---

JP5034422B2|2005-11-28|2012-09-26|住友化学株式会社|Method for producing polyethylene|

---

US7989573B2|2005-12-16|2011-08-02|3M Innovative Properties Company|Method of free radically polymerizing vinyl monomers|

---

US7968661B2|2005-12-28|2011-06-28|3M Innovative Properties Company|Method of free radically polymerizing vinyl monomers|

---

KR20110084905A|2008-10-07|2011-07-26|다우 글로벌 테크놀로지스 엘엘씨|High pressure low density polyethylene resins with improved optical properties produced through the use of highly active chain transfer agents|

---

WO2010071653A1|2008-12-18|2010-06-24|Exxonmobil Chemical Patents Inc.|High pressure polymerization process|

---

BRPI1006804B1|2009-01-16|2019-10-22|Basell Polyolefine Gmbh|METHOD FOR REDUCING THE PRODUCTION OF A HIGH PRESSURE TUBULAR REACTOR AND PROCESS FOR PREPARATION OF ETHYLENE HOMOPOLYMERS OR COPOLYMERS|

---

ES2646270T3|2010-09-30|2017-12-13|Dow Global Technologies Llc|Interpolymers based on ethylene and their preparation processes|

---

EP2621963B1|2010-09-30|2016-07-06|Dow Global Technologies LLC|Polymerization process to make low density polyethylene|

---

CN103347907B|2010-12-17|2016-10-26|陶氏环球技术有限责任公司|Polymer based on ethylene and preparation method thereof|

---

CN103403040B|2011-03-03|2015-11-25|巴塞尔聚烯烃股份有限公司|There is the method preparing Alathon or multipolymer in the tubular reactor of the reaction zone of different chain transfer agent concentration having at least two|

---

IN2014CN02739A|2011-10-19|2015-07-03|Dow Global Technologies Llc|

---

BR112014009141A8|2011-10-21|2017-06-20|Novartis Ag|Dosage regimen for an s1p receptor modulator or agonist|

---

US9228036B2|2011-11-23|2016-01-05|Dow Global Technologies Llc|Low density ethylene-based polymers with broad molecular weight distributions and low extractables|

---

ES2587787T3|2012-03-09|2016-10-26|Basf Se|Continuous procedure for synthesis of graft polymers based on polyethers|

---

EP2999742A1|2013-05-22|2016-03-30|Dow Global Technologies LLC|Compositions containing low density ethylene-based polymers with high melt strength and films formed from the same|

---

JP6377141B2|2013-05-22|2018-08-22|ダウ グローバル テクノロジーズ エルエルシー|Low density ethylene-based compositions with improved melt strength, yield, and mechanical properties|

---

ES2637970T3|2013-05-22|2017-10-18|Dow Global Technologies Llc|Low density ethylene based polymer compositions with high melt strength and medium-high density control|

---

WO2015166297A1|2014-04-30|2015-11-05|Exxonmobil Chemical Patents Inc.|Process for manufacturing ethylene polymers and copolymers|

---

SG11201705241QA|2014-12-30|2017-07-28|Dow Global Technologies Llc|Process to control output and quality of ethylene-based polymer formed by high pressure free radical polymerization|

---

US10400046B2|2015-06-25|2019-09-03|Joseph J. Matsko|Portable powered paint system|

---

WO2017058570A1|2015-09-28|2017-04-06|Dow Global Technologies Llc|Process for producing ethylene-based polymers with reduced gel counts and low reactor fouling|

---

EP3168239A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|High pressure free radical polymerizations|

---

EP3168238A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|Ethylene-based polymers formed by high pressure free radical polymerizations|

---

EP3168237A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|High pressure, free radical polymerizations to produce ethylene-based polymers|

---

KR20180114081A|2016-02-23|2018-10-17|다우 글로벌 테크놀로지스 엘엘씨|Ethylene-based polymer and method for producing the same|

---

WO2017201110A1|2016-05-18|2017-11-23|Dow Global Technologies Llc|Ethylene-based polymers and processes to make the same|SG11201705241QA|2014-12-30|2017-07-28|Dow Global Technologies Llc|Process to control output and quality of ethylene-based polymer formed by high pressure free radical polymerization|

---

US10400046B2|2015-06-25|2019-09-03|Joseph J. Matsko|Portable powered paint system|

---

CN112321757A|2015-08-31|2021-02-05|埃克森美孚化学专利公司|Regulator control in high pressure polyethylene production|

---

EP3168238A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|Ethylene-based polymers formed by high pressure free radical polymerizations|

---

EP3168237A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|High pressure, free radical polymerizations to produce ethylene-based polymers|

---

EP3168239A1|2015-11-10|2017-05-17|Dow Global Technologies LLC|High pressure free radical polymerizations|

---

WO2019022974A1|2017-07-28|2019-01-31|Dow Global Technologies Llc|Low density ethylene-based polymers for low speed extrusion coating operations|

---

EP3661973A1|2017-07-31|2020-06-10|Dow Global Technologies LLC|Ethylene-based polymers with new distributions of terminal and internal unsaturations|

---

KR102133030B1|2017-12-18|2020-07-10|주식회사 엘지화학|Olefin polymer, method for preparing olefin polymer, and film using the same|

---

WO2020094449A1|2018-11-08|2020-05-14|Sabic Global Technologies B.V.|A process for the preparation of ethylene homo- or copolymers in a tubular reactor|

---

US20210095060A1|2019-09-30|2021-04-01|Exxonmobil Chemical Patents Inc.|High Pressure Polyethylene Tubular Reactor Processes For Improved Wire Coating Product|

法律状态:
2020-03-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-11-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-01-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/11/2016, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EPEP15382554.2|2015-11-10|

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EP15382554.2A|EP3168237A1|2015-11-10|2015-11-10|High pressure, free radical polymerizations to produce ethylene-based polymers|

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PCT/US2016/061390|WO2017083559A1|2015-11-10|2016-11-10|High pressure, free radical polymerizations to produce ethylene-based polymers|

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