EP1530599A2 - Procede de polymerisation de monomeres a polymerisation cationique - Google Patents

Procede de polymerisation de monomeres a polymerisation cationique

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Publication number
EP1530599A2
EP1530599A2 EP03784815A EP03784815A EP1530599A2 EP 1530599 A2 EP1530599 A2 EP 1530599A2 EP 03784815 A EP03784815 A EP 03784815A EP 03784815 A EP03784815 A EP 03784815A EP 1530599 A2 EP1530599 A2 EP 1530599A2
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EP
European Patent Office
Prior art keywords
less
reactor
contact time
group
initiator
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP03784815A
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German (de)
English (en)
Inventor
David Y. Chung
Robert N. Webb
Michael F. Mcdonald
Yuan-Ju Chen
Richard D. Hembree
John P. Soisson
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Publication of EP1530599A2 publication Critical patent/EP1530599A2/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene
    • C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons

Definitions

  • the present invention relates to an improved method for production of isobutylene-based polymers useful in rubber compounds.
  • the copolymers are made by a cationic slurry polymerization process at approximately -95 °C using a catalyst comprising a Lewis Acid and an initiator.
  • Initiators such as water and anhydrous HC1 are used extensively.
  • Related patents are EP 0 279 456; WO 00/40624; U.S. 4,385,560, 5,169,914, and 5,506,316, herein incorporated by reference.
  • the commercial reactors used to make these rubbers are well mixed vessels of greater than 10 to 30 liters in volume with a high circulation rate provided by a pump impeller.
  • the polymerization and the pump both generate heat and, in order to keep the slurry cold, the reactor contains a heat exchanger.
  • CFSTR continuous flow stirred tank reactor
  • slurry (reacted monomers) is circulated through tubes of a heat exchanger by a pump, while boiling ethylene on the shell side provides cooling, the slurry temperature being determined by the boiling ethylene temperature, the required heat flux and the overall resistance to heat transfer.
  • the heat exchanger surfaces progressively foul, often referred to as film fouling, which causes the slurry temperature to rise. This often limits the practical slurry concentration that can be used in most reactors from 21 to 28 wt% relative to the total weight of the slurry, diluent, and unreacted monomers.
  • the slurry side heat transfer coefficient can be related to the viscosity of the slurry by the Sieder-Tate equation for turbulent fluid flow as shown below in equation (2):
  • h s ⁇ U rry is the slurry side heat transfer coefficient
  • D is the diameter of the reactor heat transfer tube
  • k is the thermal conductivity of the reactor polymerizing slurry
  • v is the average velocity of the slurry inside the tube
  • p is the average density of the slurry
  • ⁇ b is the average bulk viscosity of the polymerizing slurry
  • c p is the specific heat of the polymerizing slurry
  • ⁇ w is the average wall viscosity of the polymerizing slurry. Therefore, h s ⁇ urry is proportional to (1/ ⁇ b ) 0' in equation
  • TMPCI 2-chloro-2,4,4-trimethyl-pentane
  • tertiary alkyl halide initiators such as tert-butylchloride (a C 4 tertiary halide) have been shown by Kennedy et al. in U.S. Patent No. 3,560,458 to improve isobutylene polymerization in small scale, batch experiments when compared to HCl. Yet, there is little to no improvement when comparing tert-butylchloride and TMPCI in small scale batch experiments. Further, the lack of steady state conditions in the small batch process means that heat transfer and viscosity changes would not be apparent when going to a continuous, slurry process, nor would the associated problem of reactor fouling.
  • the inventors have unexpectedly found that certain alkyl halide compounds greater than C 4 significantly reduces reactor fouling associated with using HCl as an initiator for butyl rubber polymerization in continuous slurry reactors.
  • the present invention enables a higher slurry concentration and/or longer run lengths than would otherwise be practical in most commercial reactors.
  • an object of the present invention is to provide a method of improving heat transfer within a butyl reactor by employing an improved catalyst system for the polymerization of an isoolefin with a conjugated diene to form butyl rubber.
  • the improved catalyst system comprises a Lewis Acid and an initiator that improves heat transfer from the polymerizing slurry to the heat exchanging system built into the reactor by lowering the heat transfer coefficient of the slurry. This will ultimately lower the fouling rate, and allow higher concentrations of monomer to be injected into the reactor and higher slurry concentrations to be maintained, and/or allow the reactor to run for a longer period of time before washing, thus improving the commercial value of the product and process.
  • An embodiment of the present invention is a method of improving the heat transfer capability within a continuous slurry polymerization reactor in preparing random copolymers of one or more isoolefin monomers and one or more conjugated diene monomers, the reacted monomers forming a slurry within the reactor.
  • the method comprises reacting in a polar diluent the isoolefin and diene monomers, a Lewis acid, and an initiator, wherein the initiator has the formula:
  • X is a halogen
  • R ⁇ is selected from the group consisting of to C 8 alkyl, and C 2 to C 8 alkenyl
  • R is selected from the group consisting of C] to C 8 alkyl, C 2 to C 8 alkenyl and phenylalkyl
  • R 2 is selected from the group consisting of C 4 to C oo alkyl, C to Cg alkenyl, phenyl phenylalkyl, alkylphenyl, C 3 to C 10 cycloalkyl, and
  • R 6 wherein X is a halogen; R 5 is selected from the group consisting of to C 8 alkyl, and C 2 to C 8 alkenyl; R 6 is selected from the group consisting of C ⁇ to C 8 alkyl, C 2 to C 8 alkenyl and phenylalkyl; and R is selected from the group consisting of phenylene, biphenyl, ⁇ , ⁇ -diphenylalkane and ⁇ (CH 2 ) admir ⁇ , wherein n is an integer from 1 to 10; and wherein R l9 R , and R 3 can also form adamantyl or bornyl ring systems, the X group being in a tertiary carbon position; wherein the Lewis acid and the initiator are contacted with a contact time of from less than 60s prior to contacting with the isoolefin and the diene monomers. Further, the slurry within the reactor is in a concentration of 50 wt% or less in one embodiment.
  • the invention provides for a catalyst system and process for production of isoolefin copolymers containing a para-alkylstyrene comonomers.
  • An improved catalyst system and process has been discovered which affords many unexpected advantages for commercial slurry polymerization of these copolymers generally, and in particular isobutylene /r ⁇ r ⁇ -methylsytrene (IPMS) copolymers.
  • IPMS isobutylene /r ⁇ r ⁇ -methylsytrene copolymers.
  • the invention is particularly useful in production of isoolefin-para-alkylstyrene (IP AS) copolymers having a higher PAS content, particularly isobutylene-para-methylstyrene (IPMS) copolymers having a higher PMS content (e.g. 10-20 weight percent PMS).
  • the copolymers produced contain isobutylene as the isoolefin and para-methylstyrene as the para-alkylstyrene comonomer. Discussion of these preferred embodiments should not be construed so as to limit the broad invention, which is applicable generally to copolymers of one or more isoolefin and one or more para-alkylstyrene (PAS) monomers.
  • PAS para-alkylstyrene
  • an improved polymerization system for copolymerizing an iso-mono-olefin having from 4 to 7 carbon atoms and para-alkylstyrene monomers.
  • the process produces copolymers containing between about 80 and 99.5 wt% of the isoolefin such as isobutylene and between about 0.5 and 20 wt% of the para-alkylstyrene such as para- methylstyrene.
  • the copolymers comprise between about 10 and 99.5 wt% of the isoolefin, or isobutylene, and about 0.5 and 90 wt% of the para-alkylstyrene, or para-methylstyrene.
  • the invention provides for a continuous slurry polymerization process for preparing random copolymers of one or more isoolefin monomers and one or more para-alkylstyrene monomers comprising reacting in an anhydrous polymerization system of said monomers, a polar solvent, a Lewis acid, and an initiator, said polymerization system being capable of forming an in-situ electron pair donor initiator having the formula:
  • R ⁇ is an alkyl, alkenyl, aryl, aralkyl, or aralkenyl group containing up to 30 carbon atoms but not less than 3 carbon atoms unless R ! contains at least one olefmic unsaturation,
  • R 2 and R 3 are alkyl, aryl, or aralkyl groups containing up to 30 carbon atoms and can be the same or different, x is a halogen or a carboxy, hydroxyl, or alkoxyl group, and n is a positive whole number; and wherein the Lewis acid and the initiator are contacted with a contact time of from less than 60s prior to contacting with the isoolefin and the para-alkylstyrene monomers.
  • the invention provides for the production of a polyisoolefm rubber. It is produced by the polymerization reaction between isoolefin monomers.
  • the olefin polymerization feeds employed in the present invention are those olefinic compounds conventionally used in the preparation of isobutylene-type rubber polymers.
  • the polyisoolefm rubber are prepared by reacting monomers of a C 4 to C 6 isoolefin monomer component such as isobutene.
  • the isoolefin is a C 4 to C 6 compound such as isobutylene, isobutene, 2-methyl-l-butene, 3 -methyl- 1-butene, 2-methyl-2-butene, and 4-methyl-l-pentene.
  • the isoolefin is isobutylene.
  • the invention provides for a polymerization method for use in a continuous slurry polymerization reactor in preparing a homopolymer of an isoolefin, the reacted monomers forming the slurry within the reactor, a Lewis acid, and an initiator, wherein the initiator has the formula:
  • X is a halogen
  • R ⁇ is selected from the group consisting of C ⁇ to Cg alkyl, and C 2 to C 8 alkenyl
  • R 3 is selected from the group consisting of, C 1 to C 8 alkyl, C 2 to C 8 alkenyl and phenylalkyl
  • R 2 is selected from the group consisting of C 4 to C 200 alkyl, C 2 to C 8 alkenyl, phenyl, phenylalkyl, alkylphenyl, C 3 to C 10 cycloalkyl, and
  • R « wherein X is a halogen;
  • R 5 is selected from the group consisting of, Ci to C 8 alkyl, and C 2 to C 8 alkenyl;
  • R is selected from the group consisting of, to C 8 alkyl, C 2 to C 8 alkenyl and phenylalkyl; and
  • R is selected from the group consisting of phenylene, biphenyl, ⁇ , ⁇ -diphenylalkane and ⁇ (CH 2 ) n ⁇ , wherein n is an integer from 1 to 10; and wherein R ls R 2 , and R 3 can also form adamantyl or bornyl ring systems, the X group being in a tertiary carbon position; and wherein the Lewis acid and the initiator are contacted with a contact time of from less than 60s and prior to contacting with the isoolefin.
  • alternative contact times may be from less than 60s, less than 30s, less than 25s, less than 20s, less than 15s, less than 10s, or less than 5s.
  • Figure 1 is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the reactor slurry side heat transfer coefficient as a function of reactor turnover;
  • Figure 2 is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the reactor slurry side heat transfer coefficient as a function of reactor turnover;
  • Figure 3 is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the percentage isobutylene conversion within the reactor as a function of the reactor residence time;
  • Figure 4A is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the reactor pressure as a function of reactor residence time with TMPCI initiator present
  • Figure 4B is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as reactor pressure as a function of reactor residence time with HCl as the initiator;
  • Figure 5 is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the amperage drawn to power the reactor pump impeller as a function of reactor residence time, wherein TMPCI is present during the first part of the reaction, and HCl is present in the second part of the reaction; and
  • Figure 6 is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the slurry temperature as a function of reactor residence time, wherein TMPCI is present during the first part of the reaction, and HCl is present in the second part of the reaction.
  • Figure 7 is a graphical representation of data showing catalyst efficiency plotted as a function of TMPC1/EADC contact times.
  • the invention concerns a catalyst system and process for production of isoolefin copolymers containing a conjugated diene comonomer.
  • An improved catalyst system and process has been discovered which affords many unexpected advantages for commercial slurry polymerization processes.
  • the discussion and examples below are focused on embodiments of the broad invention. To the extent that the description is specific, this is done solely for the purpose of illustrating exemplifying embodiments and should not be taken as restricting the invention to these embodiments.
  • the polymerization system of the invention contains a mixture of at least two monomers, a Lewis acid catalyst, an initiator, and a polar diluent.
  • the copolymerization reactor is maintained substantially free of impurities which can complex with the catalyst, the initiator, or the monomers, and the polymerization reaction is conducted under conditions to limit or avoid chain transfer and termination of the growing polymer chains.
  • Anhydrous conditions are highly preferred and reactive impurities, such as components containing active hydrogen atoms (water, alcohol and the like) must be removed from both the monomer and diluents by techniques well-known in the art.
  • the "polymerization system” is the catalyst system and the monomers and reacted monomers within the butyl-type reactor.
  • slurry refers to reacted monomers that have polymerized to a stage that they have precipitated from the diluent.
  • concentration is the weight percent of these reacted monomers—the weight percent of the reacted monomers by total weight of the slurry, diluent, unreacted monomers, and catalyst system.
  • butyl rubber is defined to mean a polymer predominately comprised of repeat units derived from isobutylene but including repeat units derived from a conjugated diene.
  • Butyl rubber is produced by the polymerization reaction between isoolefin and a conjugated diene comonomers, thus containing isoolefin-derived units and conjugated diene-derived units.
  • the olefin polymerization feeds employed in connection with the catalyst and initiator system are those olefinic compounds, the polymerization of which are known to be cationically initiated, and are free of aromatic monomers such as para-alkylstyrene monomers.
  • the olefin polymerization feeds employed in the present invention are those olefinic compounds conventionally used in the preparation of butyl-type rubber polymers.
  • the butyl polymers are prepared by reacting a comonomer mixture, the mixture having at least (1) a C 4 to C 6 isoolefin monomer component such as isobutene with (2) a multiolefin, or conjugated diene, monomer component.
  • the isoolefin is in a range from 70 to 99.5 wt% by weight of the total comonomer mixture in one embodiment, and 85 to 99.5 wt% in another embodiment.
  • the conjugated diene component in one embodiment is present in the comonomer mixture from 30 to 0.5 wt% in one embodiment, and from 15 to 0.5 wt% in another embodiment. In yet another embodiment, from 8 to 0.5 wt% of the comonomer mixture is conjugated diene.
  • the isoolefin is a C to C 6 compound such as isobutene or 2-methyl-l- butene, 3-methyl-l-butene, 2-methyl-2-butene, and 4-methyl-l-pentene.
  • the multiolefin is a C 4 to C 14 conjugated diene such as isoprene, butadiene, 2,3- dimethyl-l,3-butadiene, myrcene, 6,6-dimefhyl-fulvene, hexadiene and piperylene.
  • butyl rubber polymer of the invention is obtained by reacting 95 to 99.5 wt% of isobutylene with 0.5 to 8 wt% isoprene, or from 0.5 wt% to 5.0 wt% isoprene in yet another embodiment.
  • the invention provides for a catalyst system and process for production of isoolefin copolymers containing a para-alkylstyrene comonomers.
  • An improved catalyst system and process has been discovered which affords many unexpected advantages for commercial slurry polymerization of these copolymers generally, and in particular isobutylene ? ⁇ r -methylsytrene (IPMS) copolymers.
  • IPMS isobutylene ? ⁇ r -methylsytrene copolymers.
  • the invention is particularly useful in production of isoolefin-para-alkylstyrene (IPAS) copolymers having a higher PAS content, particularly isobutylene-para-methylstyrene (IPMS) copolymers having a higher PMS content (e.g. 10-20 weight percent PMS).
  • the copolymers produced contain isobutylene as the isoolefin and para-methylstyrene as the para-alkylstyrene comonomer. Discussion of these preferred embodiments should not be construed so as to limit the broad invention, which is applicable generally to copolymers of one or more isoolefin and one or more para-alkylstyrene (PAS) monomers.
  • PAS para-alkylstyrene
  • an improved polymerization system for copolymerizing an iso-mono-olefin having from 4 to 7 carbon atoms and para-alkylstyrene monomers.
  • the process produces copolymers containing between about 80 and 99.5 wt% of the isoolefin such as isobutylene and between about 0.5 and 20 wt% of the para-alkylstyrene such as para- methylstyrene.
  • the copolymers comprise between about 10 and 99.5 wt% of the isoolefin, or isobutylene, and about 0.5 and 90 wt% of the para-alkylstyrene, or para-methylstyrene.
  • the invention provides for the production of a polyisoolefin rubber. It is produced by the polymerization reaction between isoolefin monomers.
  • the olefin polymerization feeds employed in the present invention are those olefinic compounds conventionally used in the preparation of isobutylene-type rubber polymers.
  • the polyisoolefin rubber are prepared by reacting monomers of a C 4 to C 6 isoolefin monomer component such as isobutene.
  • the isoolefin is a C 4 to C 6 compound such as isobutylene, isobutene, 2-methyl-l-butene, 3 -methyl- 1-butene, 2-methyl-2-butene, and 4-methyl-l-pentene.
  • the isoolefin is isobutylene.
  • Isomonoolefin and conjugated diene, particularly isobutylene and isoprene, can be copolymerized under cationic conditions.
  • the copolymerization is carried out by means of a Lewis Acid catalyst.
  • Lewis Acid catalysts including Friedel-Crafts catalysts
  • Desirable catalysts are Lewis Acids based on metals from Group 4, 13 and 15 of the Periodic Table of the Elements, including boron, aluminum, gallium, indium, titanium, zirconium, tin, vanadium, arsenic, antimony, and bismuth.
  • the metals are aluminum, boron and titanium, with aluminum being desirable.
  • weaker acids are preferred as they lead to less alkylation and branching and higher monomer conversion rates.
  • the Group 13 Lewis Acids have the general formula R perpetratMX 3 .
  • M is a Group 13 metal
  • R is a monovalent hydrocarbon radical selected from the group consisting of to C 12 alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals
  • n is an integer from 0 to 3
  • X is a halogen independently selected from the group consisting of fluorine, chlorine, bromine, and iodine, preferably chlorine.
  • arylalkyl refers to a radical containing both aliphatic and aromatic structures, the radical being at an alkyl position.
  • alkylaryl refers to a radical containing both aliphatic and aromatic structures, the radical being at an aryl position.
  • Lewis acids include aluminum chloride, aluminum bromide, boron trifluoride, boron trichloride, ethyl aluminum dichloride (EtAlCl 2 or EADC), diethyl aluminum chloride (Et 2 AlCl or DEAC), ethyl aluminum sesquichloride (Et ⁇ AlC ⁇ s or EASC), trimethyl aluminum, and triethyl aluminum.
  • the Group 4 Lewis Acids have the general formula MX ⁇ , wherein M is a Group 4 metal and X is a ligand, preferably a halogen.
  • Nonlimiting examples include titanium tetrachloride, zirconium tetrachloride, or tin tetrachloride.
  • the Group 15 Lewis Acids have the general formula MX y , wherein M is a
  • X is a ligand, preferably a halogen, and y is an integer from 3 to 5.
  • Nonlimiting examples include vanadium tetrachloride and antimony pentafluoride.
  • Lewis acids may be any of those useful in cationic polymerization of isobutylene copolymers including: A1C1 3 , EADC, EASC, DEAC, BF 3 , TiCU, etc. with EASC and EADC being especially preferred.
  • Catalyst efficiency (based on Lewis Acid) in the reactor is maintained between 10000 lb. of polymer/lb. of catalyst and 300 lb. of polymer/lb. of catalyst and desirably in the range of 4000 lb. of polymer/lb. of catalyst to 1000 lb. of polymer/lb. of catalyst by controlling the molar ratio of Lewis Acid to initiator.
  • the Lewis Acid catalyst is used in combination with an initiator.
  • the initiators are those initiators which are capable of being precomplexed in a suitable diluent with the chosen Lewis Acid to yield a complex which is in equilibrium with a carbenium ion pair which rapidly forms a propagating polymer chain in the reactor. These initiators yield a fast, simple initiation of polymerization in the reactor as opposed to the slow stepwise initiations involving several polar complexes in equilibrium characteristic of the catalyst systems such as water or HCl initiators conventionally used in commercial cationic slurry polymerization of isobutylene copolymers.
  • the initiator is a tertiary halide greater than C 4 , wherein the initiator has the formula (A):
  • X is a halogen
  • Rj is selected from the group consisting of to C 8 alkyl, and C 2 to C 8 alkenyl
  • R 3 is selected from the group consisting of d to C 8 alkyl, C 2 to C 8 alkenyl and phenylalkyl
  • R 2 is selected from the group consisting of C 4 to C 200 alkyl, C 2 to C 8 alkenyl, phenyl, phenylalkyl, alkylphenyl, C to C 10 cycloalkyl, and
  • X is a halogen
  • R 5 is selected from the group consisting of to C 8 alkyl, and C 2 to C 8 alkenyl
  • Re is selected from the group consisting of to Cg alkyl, C 2 to C 8 alkenyl and phenylalkyl
  • Rj is selected from the group consisting of phenylene, biphenyl, ⁇ , ⁇ -diphenylalkane and ⁇ (CH 2 ) n ⁇ , wherein n is an integer from 1 to 10; and wherein R l5 R 2 , and R 3 can also form adamantyl or bornyl ring systems, the X group being in a tertiary carbon position.
  • Multifunctional initiators are employed where the production of branched copolymers is desired, while mono- and di-functional initiators are preferred for the production of substantially linear copolymers.
  • the initiator is an oligomer of isobutylene as in structure (D):
  • X is a halogen
  • m is from 1 to 60, and mixtures thereof.
  • m is from 2 to 40.
  • This structure is also described as a tertiary alkyl chloride-terminated polyisobutylene having a Mn up to 2500 in one embodiment, and up to 1200 in another embodiment.
  • Non-limiting examples of suitable initiators are cumyl esters of hydrocarbon acids, and alkyl cumyl ethers.
  • Representative initiators comprise compounds such as 2-acetyl-2-phenylpropane, i.e., cumyl acetate; 2- methoxy-2-phenyl propane, i.e., cumylmethyl-ether; l,4-di(2-mefhoxy-2- propyl)benzene, i.e., di(cumylmethyl ether); the cumyl halides, particularly the chlorides, i.e., 2-chloro-2-phenylpropane, i.e., cumyl chloride (1-chloro-l- methylethyl)benzene; l,4-di(2-chloro-2-propyl)benzene, i.e., di(cumylchloride); l,3,5-tri(2-chloro-2-propyl)benzene, i.e
  • initiators may be found in U.S. Patent No. 4,946,899, herein incorporated by reference for purposes of U.S. patent practice. These initiators are generally C 5 or greater tertiary or allylic alkyl or benzylic halides and may include poly functional initiators. Desirable examples of these initiators include: TMPCI, TMPBr, 2,6-dichloro-2,4,4,6-tetramethylheptane, cumyl chloride as well as 'di-' and 'tri-' cumyl chloride or bromide. In another embodiment, the initiator is a tertiary alkyl chloride-terminated polyisobutylene with a Mn (number average molecular weight) up to 2500.
  • Mn number average molecular weight
  • the TMPCI is made by dissolving isobutylene dimer in methylchloride and then adding anhydrous HCl to form the alkyl chloride.
  • TMPCI is then purged by nitrogen and the resulting solution of TMPCI in methylchloride is used as the initiator stream in a continuous plant to make butyl polymers.
  • the TMPCI stream is mixed with a cold methylchloride (chloromethane) stream and an aluminum alkyl stream to form the catalyst system.
  • This stream is then injected into the continuous flow stirred tank reactor ("CFSTR") used to produce butyl polymers under much more controllable and economic conditions than has previously been possible.
  • CFSTR continuous flow stirred tank reactor
  • isobutylene dimers are reacted with HCl inline and then fed directly into the reactor. Polymerization Reaction Conditions
  • the selected diluent or diluent mixture should provide a diluent medium having some degree of polarity in order for the polymerization to proceed at a reasonable rate.
  • a mixture of nonpolar and polar diluents can be used.
  • a mixture of, or a single polar diluent is more desirable.
  • Suitable nonpolar diluent components includes hydrocarbons and preferably aromatic or cyclic hydrocarbons or mixtures thereof. Such compounds include, for instance, methylcyclohexane, cyclohexane, toluene, carbon disulfide and others.
  • polar diluents include halogenated hydrocarbons, normal, branched chain or cyclic hydrocarbons.
  • Specific compounds include the preferred liquid diluents such as ethyl chloride, methylene chloride (dichloromethane, CH 2 C1 2 ), methylchloride (chloromethane, CH 3 C1), CO 2 , CHC1 3 , CC1 4 , n-butyl chloride, chlorobenzene, and other chlorinated hydrocarbons.
  • Methylchloride is desirably used in an embodiment of the invention.
  • the mixture is preferably at least 70 % polar diluent, on a volume basis.
  • product molecular weights are determined by reaction time, temperature, concentration, the nature of the reactants, and similar factors. Consequently, different reaction conditions will produce products of different molecular weights. Synthesis of the desired reaction product will be achieved, therefore, through monitoring the course of the reaction by the examination of samples taken periodically during the reaction, a technique widely employed in the art and shown in the examples or by sampling the effluent of a continuous reactor.
  • the reactors that may be utilized in the practice of the present invention include any conventional reactors and equivalents thereof capable of performing a continuous slurry process, such as disclosed in U.S. 5,417,930, herein incorporated by reference.
  • the reactor pump impeller can be of the up-pumping variety or the down-pumping variety.
  • the reactor will contain sufficient amounts of the catalyst system of the present invention effective to catalyze the polymerization of the monomer containing feed-stream such that a sufficient amount of polymer having desired characteristics is produced.
  • the feed-stream in one embodiment contains a total monomer concentration greater than 30 wt% (based on the total weight of the monomers, diluent, and catalyst system), greater than 35 wt% in another embodiment. In yet another embodiment, the feed-stream will contain from 35 wt% to 50 wt% monomer concentration based on the total weight of monomer, diluent, and catalyst system.
  • the feed-stream is substantially free from silica cation producing species.
  • substantially free of silica cation producing species it is meant that there is no more than 0.0005 wt% based on the total weight of the monomers of these silica species in the feed stream.
  • Typical examples of silica cation producing species are halo-alkyl silica compounds having the formula RiR ⁇ SiX or R 1 R 2 SiX 2 , etc., wherein "R” is an alkyl and "X" is a halogen.
  • the feed stream should be free of aromatic-containing monomers such as para-alkylstyrene.
  • the reaction conditions will be such that desirable temperature, pressure and residence time are effective to maintain the reaction medium in the liquid state and to produce the desired polymers having the desired characteristics.
  • the monomer feed-stream is typically substantially free of any impurity which is adversely reactive with the catalyst under the polymerization conditions.
  • the monomer feed preferably should be substantially free of bases (such as caustic), sulfur-containing compounds (such as H 2 S, COS, and organo- mercaptans, e.g., methyl mercaptan, ethyl mercaptan), N-containing compounds, oxygen containing bases such as alcohols and the like.
  • the polymerization reaction temperature is conveniently selected based on the target polymer molecular weight and the monomer to be polymerized as well as standard process variable and economic considerations, e.g., rate, temperature control, etc.
  • the temperature for the polymerization is between -10°C and the freezing point of the polymerization system in one embodiment, and from -25 °C to -120°C in another embodiment.
  • the polymerization temperature is from -40°C to -100°C, and from -70°C to -100°C in yet another embodiment.
  • the temperature range is from -80°C to -100°C.
  • the temperature is chosen such that the desired polymer molecular weight is achieved.
  • the reaction pressure will be from 200 kPa to 1600 kPa in one embodiment, from 300 kPa to 1200 kPa in another embodiment, and from 400 kPa to 1000 kPa in yet another embodiment.
  • the catalyst (Lewis Acid) to monomer ratio utilized will be those conventional in this art for carbocationic polymerization processes.
  • the catalyst to monomer mole ratios will be from 0.10 to 20, and in the range of 0.5 to 10 in another embodiment.
  • the ratio of Lewis Acid to initiator is from 0.75 to 2.5, or from 1.25 to 1.5 in yet another desirable embodiment.
  • the overall concentration of the initiator is from 50 to 300 ppm within the reactor in one embodiment, and from 100 to 250 ppm in another embodiment.
  • the concentration of the initiator in the catalyst feed stream is from 500 to 3000 ppm in one embodiment, and from 1000 to 2500 in another embodiment.
  • Another way to describe the amount of initiator in the reactor is by its amount relative to the polymer. In one embodiment, there is from 0.25 to 5.0 moles polymer/mole initiator, and from 0.5 to 3.0 mole polymer/mole initiator in another embodiment.
  • the reacted monomers within the reactor form a slurry.
  • the term "slurry” refers to reacted monomers that have polymerized to a stage that they have precipitated from the diluent.
  • the slurry "concentration” is the weight percent of these reacted monomers— the weight percent of the reacted monomers by total weight of the slurry, diluent, unreacted monomers, and catalyst system.
  • the concentration of the slurry is equal to or greater than 10 wt%.
  • the slurry is present in the reactor in a concentration equal to or greater than 25 wt%.
  • the slurry concentration in the reactor is less than or equal to 50 wt%.
  • the slurry is present in the reactor from 20 to 50 wt%. And in yet another embodiment, the slurry concentration is present in the reactor from 30 to 40 wt%.
  • the slurry is characterized by having a heat transfer coefficient (h s ⁇ urr y) as defined above in equation (2). In one embodiment of the invention, the heat transfer coefficient of the slurry is from 200 to 500 Btu/hr-ft 2o F. In another embodiment of the invention, the heat transfer coefficient of the slurry is from 300 to 450 Btu/hr-ft 2o F.
  • the order of contacting the monomer feed-stream, catalyst, initiator, and diluent is not critical to this invention.
  • the initiator and Lewis Acid are pre-complexed by mixing together in cold methylchloride or other suitable cold polar diluent, immediately before injection into the continuous reactor through a catalyst nozzle in the standard way. Other methods may also be employed that will inject the initiator into the reactor.
  • the monomer is not contacted with the Lewis Acid and initiator at before entering the reactor.
  • Lewis Acid and the initiator are added to the reactor separately.
  • the stabilizing initiator and Lewis Acid are allowed to precomplex by mixing together with varying contact times.
  • contact times may vary from 0.001s, 0.002s, 0.003s, 0.004s, 0.005s, 0.006s, 0.007s, 0.008s, 0.009s, 0.010s, 0.020s, 0.030s, 0.040s, 0.050s, 0.060s, 0.070s, 0.080s, 0.090s, 0.100s, 0.200s, 0.300s, 0.400s, 0.500s, 0.600s, 0.700s, 0.800s, 0.900s, Is, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, to 10s.
  • Preferable ranges include 20s or less, 30s or less, 40s or less, 50s or less, 60s or less, 70s or less, 80s or less, 90s or less, 100s or less, 110s or less, and 120s or less.
  • Other preferable ranges include from l ⁇ s to 120s, lOO ⁇ s to 60s, l ⁇ s to 30s, 0.45s to 25s, 0.01s to 20s, 0.05s to 10s, and 0.10s to 5s.
  • the stabilizing initiator and Lewis Acid are precomplexed and injected into the reactor through a single reactor nozzle.
  • the stabilizing initiator and Lewis Acid are precomplexed and injected into the reactor through a single reactor nozzle.
  • Lewis Acid when fed into the reactor separately, are precomplexed in a mixing zone within the reactor. While not wishing to be bound to theory, it is believed that the Lewis Acid and the stabilizing initiator combine to yield a stable complex which is in equilibrium with a carbenium ion pair that directly forms a propagating polymer chain in the reactor. It has been discovered that shorter contact times have an unexpected beneficial effect on catalyst efficiency.
  • TMPCI and EADC are combined at contact times in the ranges from l ⁇ s to 120s, lOO ⁇ s to 60s, l ⁇ s to 30s, 0.45s to 25s, 0.01s to 20s, 0.05s to 10s, or 0.10s to 5s prior to combining with isobutylene as the isoolefin and isoprene as the conjugated diene comonomer.
  • TMPCI and EASC are combined at contact times in the ranges from l ⁇ s to 120s, lOO ⁇ s to 60s, l ⁇ s to 30s, 0.45s to 25s, 0.01s to 20s, 0.05s to 10s, or 0.10s to 5s prior to combining with isobutylene as the isoolefin and isoprene as the conjugated diene comonomer.
  • the polymerization of isobutylene and isoprene to form butyl rubber comprises several steps.
  • a reactor having a pump impeller capable of up-pumping or down-pumping is provided.
  • the pump impeller is typically driven by an electric motor with a measurable amperage.
  • the reactor typically is equipped with parallel vertical reaction tubes within a jacket containing liquid ethylene.
  • the total internal volume, including the tubes, is greater than 30 to 50 liters, thus capable of large scale volume polymerization reactions.
  • the reactor typically uses liquid ethylene to draw the heat of the polymerization reaction away from the forming slurry.
  • the pump impeller keeps a constant flow of slurry, diluent, catalyst system and unreacted monomers through the reaction tubes.
  • a feed-stream of the isoprene and isobutylene in a polar diluent is charged into the reactor, the feed-stream containing less than 0.0005 wt% of cation producing silica compounds, and typically free of aromatic monomers.
  • the catalyst system is then charged into the feed-stream, the catalyst system having a Lewis acid and an initiator present in a molar ratio of from 0.50 to 10.0.
  • the feed-stream of monomers and catalyst system are allowed to contact one another, the reaction thus forming a slurry of butyl rubber, wherein the slurry has a concentration of from 25 wt% to 50 wt%.
  • the thus formed butyl rubber is allowed to exit the reactor through an outlet or outflow line while simultaneously allowing the feed-stream charging to continue, thus constituting the continuous slurry polymerization.
  • the present invention improves this process in a number of ways, ultimately reducing the amount of clogging that occurs in the exit port which is measured by pressure inconsistencies or "jumps".
  • the overall residence time in the reactor can vary, depending upon, e.g., catalyst activity and concentration, monomer concentration, feed injection rate, production rate, reaction temperature, and desired molecular weight, and generally will be between about one minute and five hours, and preferably between about 10 and 60 minutes.
  • the principle variable controlling residence time is the monomer feed injection rate.
  • the resultant polymer from one embodiment of the invention is a polyisobutylene/isoprene polymer (butyl rubber) that has a molecular weight distribution of from about 2 to 5, and an unsaturation of from 0.5 to 2.5 mole per 100 mole of monomer. This product may be subjected to subsequent halogenation to afford a halogenated butyl rubber.
  • the new catalyst system and process affords many unexpected advantages for commercial slurry polymerization of isoolefins and conjugated dienes.
  • the improvements obtained with this new initiator are demonstrated in commercial plant scale tests.
  • the following examples reflect embodiments of the invention and are by no means intended to be limiting of the scope of the invention.
  • the molecular weights (Mw) were determined by Gel Permeation Chromatography using a Waters Chromatograph operating at ambient temperature (30°C).
  • the HCl (Matheson) was used as a 260 ppm solution, and the tert-butylchloride (t-BuCl, Aldrich Chemical Company) was used as a 710 ppm solution.
  • the TMPCI was made by ExxonMobil Chemical Company from isobutylene dimers and HCl by methods common in the art. The monomers are manufactured by ExxonMobil Chemical Company (Houston, Texas).
  • the molecular weights in Table 1 are an average of three runs for each experiment.
  • the conditions in Table 2 correspond to TMPCI initiated reactions as well as the HCl and tert-butylchloride initiated reactions except for the following: in the case of the TMPCI initiated reaction, the feed blends were increased from 30.7 wt% to 39 wt%. In the comparative examples, the feed blend was constant at 30.7 wt%.
  • the monomers are manufactured by ExxonMobil Chemical Company (Houston, Texas). The methylchloride (Dow Chemical Company), EADC (Albemarle), and HCl (Matheson) were used as received, and the TMPCI was made by ExxonMobil Chemical Company by reacting isobutylene dimers and HCl from methods common in the art.
  • Figure 1 The monomers are manufactured by ExxonMobil Chemical Company (Houston, Texas). The methylchloride (Dow Chemical Company), EADC (Albemarle), and HCl (Matheson) were used as received, and the TMPCI was made by Exx
  • Figure 1 is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the reactor slurry side heat transfer coefficient as a function of reactor turnover.
  • the slurry side heat transfer coefficient (h s ⁇ ur r ) is the heat transfer coefficient (h) of the slurry within the butyl reactor tubes, as opposed to the heat transfer resistance of the reactor tube walls and/or the heat transfer coefficient of the boiling ethylene used to remove heat from the reactor.
  • the value of "h” (Btu/hr-ft 2 -°F) is a function of the viscosity of the slurry ( ⁇ b ), and is related as such by the well known Sieder-Tate equation (2) discussed above.
  • the reactor was operated with a frozen methylchloride (the diluent) film coating the tubes.
  • the difference between the bulk slurry temperature and the frozen ice film was then measured.
  • the temperature of the frozen ice film can be calculated from the monomer concentration in the reactor and the correlation with its freezing point. Using the equation (3) below, the value for the slurry side heat transfer coefficient h s ⁇ U ⁇ y was obtained:
  • T s ⁇ Urr y is the average bulk temperature of the reactor slurry
  • T eciice (MeCl is methylchloride) is the average temperature of the frozen ice film, as defined in equation (4) below:
  • FIG. 1 shows comparative data between HCl initiated butyl polymerization and TMPCI initiated butyl polymerization at various slurry concentrations.
  • a best fit line is drawn through the linear portion of the data, which takes into account the time for the slurry concentration in the reactor to build up to its steady state value of three turnovers, and hence the initially large h s i urr values.
  • the slurry concentration is 25.3 wt% by total weight of slurry, diluent, monomers, and other reactor components.
  • the TMPCI initiated reaction has a higher h s ⁇ urry value, thus translating by equation (1) to a lower viscosity.
  • the slurry concentration for the TMPCI initiated reaction is increased to 29 wt%, the h s ⁇ urry value, and hence the viscosity, does not change appreciably.
  • the slurry concentration is increased to 32.5 wt% for the TMPCI initiated reaction, the value of h s i un y is above that of the HCl initiated reaction.
  • Figure 2 is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the reactor slurry side heat transfer coefficient as a function of reactor turnover. A best fit line (linear regression) is drawn through the linear portion of the data, which takes into account the time for the slurry concentration in the reactor to build up to its steady state value of three turnovers, and hence the initially large hsiuny values.
  • HCl, tert-butylchloride (Aldrich Chemical Company), and TMPCI are used as initiators in separate butyl reactions and compared.
  • the values for h s ⁇ Urr y for the HCl initiated reaction are around 300 Btu/hrft 2o F (1.7 kW/m 2 K) after about 4 to 6 reaction turnovers at a slurry level of 25.6 wt% and production rate of 6.0 Klb/hr (2.72 T/hr).
  • tert-butylchloride is the initiator at a slurry level of 25.4 wt% and production rate of 6.3 Klb/hr (2.86 T/hr)
  • the s ⁇ urry values decrease, thus indicated that the slurry viscosity increases slightly.
  • Figure 3 The present example shows how the conversion of monomers within the reactor increases when an embodiment of the invention is used.
  • Figure 3 is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the percentage isobutylene conversion within the reactor as a function of the reactor residence time.
  • the isobutylene conversion increases from about 86.5 to about 87.5% over a residence time of 0.85 hours.
  • the conversion for tert-butylchloride initiated polymerization is about 87.5%.
  • the conversion is from about 88.5% to about 89.5% isobutylene over a time period of from 0.55 hours to about 0.7 hours.
  • This embodiment of the invention shows a 15% decrease of the amount of unreacted monomer remaining, i.e., a significant improvement in monomer conversion.
  • Figure 4 The present example in Figure 4 highlights the lowered agglomeration tendency due to the lowered viscosity of the butyl slurry when using embodiments of the invention.
  • Figure 4A is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the reactor pressure as a function of reactor residence time with TMPCI initiator present.
  • Figure 4B is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as reactor pressure as a function of reactor residence time with HCl as the imtiator.
  • the pressure is measured at the feed inlet to the reactor, and is representative of the internal pressure within the reactor itself. When the internal reactor pressure rises, this is indicative of agglomeration of the slurry in the outlet or overflow line, and is detected as a clogging and, hence, pressure increase, at that point in the reactor.
  • the data in Figure 4 A is with a slurry concentration of 32.5 wt%, while the slurry concentration for the HCl initiated reaction in Figure 4B is 30 wt%. Note the differences in the y-axis scale between the two graphs.
  • the data show that the baseline pressure level at about 41 psia is relatively constant until the reactor is turned off after about a 20 hour run. However, when HCl is used as the initiator, even at the lower slurry level, there are significant pressure buildups after 8 hours of reaction time, the pressure buildups or "kickings" are indications of agglomeration and clogging of the butyl reactor.
  • Figure 5 is a graphical representation of data showing butyl polymerization conditions in an embodiment of the invention, the data plotted as the amperage drawn to power the reactor pump impeller as a function of reactor residence time, wherein TMPCI is present during the first part of the reaction, and HCl is present in the second part of the reaction.
  • the butyl polymerization reaction is run for about 22 hours at a slurry concentration of 25 wt% using TMPCI as the initiator in a concentration of 2000 ppm in the catalyst stream entering the reactor, and 200 ppm in the reactor.
  • HCl is added to the reactor, while the TMPCl-laden slurry is allowed to exit the reactor.
  • the concentration of HCl in the catalyst stream entering the reactor is normally in the range of from 100 to 200 ppm, and the concentration in the reactor is between from 10 to 20 ppm.
  • the transition period from HCl to TMPCI initiator is about 2 hours.
  • the motor that drives the reactor pump impeller must work harder to stir the slurry, as indicated by the increased power draw. This is consistent with the lower viscosity with TMPCI as the initiator. While not wishing to be bound by an equation, the results in Figure 5 are consistent with what equation (2) would predict. Specifically, the h s ⁇ ur ry values when HCl is the initiator range from about 411 to 592 Btu/hrft 2 -°F (2.33 to 3.36 kW/m 2 K), while that of the TMPCI initiated reaction varies from 241 to 261 Btu/hrft 2 -°F (1.37 to 1.48 kW/m 2 K).
  • the diluent, methyl chloride was passed through a drying column before reaction.
  • the feed blend (10 wt% of monomer solution) was prepared from the mixture of monomer(s) and diluent before reaction and stored at ⁇ -95°C in the cold bath.
  • the initiator and coinitiator stock solutions were prepared by mixing methyl chloride with distilled TMPCI and methyl chloride with 25 wt% EADC.
  • the glassware used for the polymerizations was cleaned with 150ml methyl chloride and 15 ⁇ l of 25.3 wt% EADC and prechilled to ⁇ -95°C in the cold bath right before reaction. 300ml of feed blend was transferred into the clean glass reactor and chilled to — 95°C in cold bath before reaction.
  • the initiator was mixed with the feed blend at — 95 °C in cold bath and then the coinitiator was added.
  • the initiator and coinitiator were mixed in a glass vial with different contact times (2 sec, 5 sec, 60 sec, 180 sec, and 360 sec) before being added to the reactor.
  • 25ml Isopropanol with BHT as a stabilizer was added to quench the reaction.
  • the polymer was dried in a vacuum oven at 45 °C overnight. The polymer was then removed and weighed to calculate the catalyst efficiency.
  • the present invention has several advantages. Because of the rapid reactor mass fouling rate that typically occurs, reactors had to be operated at very low slurry concentrations and heat loads to achieve the run lengths required to allow washing and turnaround to be accomplished in the time available before the fouled reactor had to be put back into production to replace another fouled reactor.
  • the present invention will allow the butyl reactors to be run at higher slurry concentrations and/or run at a lower concentration for a longer period of time before fouling. In one embodiment of the invention, the run length is increased from 30% to 200% relative to the run length when HCl or C 4 or smaller initiators are used in the catalyst system.
  • Embodiments of the invention improve the heat transfer within the reactor.
  • the improved heat transfer can allow either higher slurry concentrations, or longer run length.
  • the heat transfer coefficient is thus higher due to the lower viscosity of the slurry as would be predicted using the Sieder-Tate equation for turbulent flow. Not only are higher slurry concentrations possible due to the improved heat transfer, but a higher monomer conversion rate is also achieved. Further, there is a lower overflow line plugging rate with embodiments of the present invention and steadier reactor operation due to the lower pump power consumption.

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  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne un nouveau système catalyseur qui améliore le potentiel de transfert thermique d'un système de traitement de suspension de réaction butylique dans la production de polymères à base d'isobutylène en processus de polymérisation continue de suspension. On conduit le procédé de polymérisation dans un système de polymérisation anhydre qui renferme un mélange de monomères dans un diluant polaire, avec un acide de Lewis et un C5 ou initiateur supérieur à halogénure tertiaire.
EP03784815A 2002-08-13 2003-07-25 Procede de polymerisation de monomeres a polymerisation cationique Withdrawn EP1530599A2 (fr)

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GB2425537B (en) * 2005-04-25 2009-03-25 Peter William Herbert Bennett Manufacture of coke from a blend of coal and polymers
CN101130585B (zh) * 2006-08-25 2010-11-10 北京化工大学 一种丁基橡胶的制备方法
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US9079990B2 (en) * 2010-06-01 2015-07-14 Exxonmobil Chemical Patents Inc. Methods of production of alkylstyrene/isoolefin polymers
US9034998B2 (en) * 2011-12-16 2015-05-19 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9631038B2 (en) 2013-10-11 2017-04-25 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US9771442B2 (en) 2015-05-13 2017-09-26 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
JP6827919B2 (ja) * 2015-05-26 2021-02-10 株式会社カネカ 熱可塑性エラストマーの製造方法及び熱可塑性エラストマー
US10167352B1 (en) 2017-06-28 2019-01-01 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10047174B1 (en) 2017-06-28 2018-08-14 Infineum International Limited Polymerization initiating system and method to produce highly reactive olefin functional polymers
SG11202000232RA (en) * 2017-07-12 2020-02-27 Arlanxeo Deutschland Gmbh Process for the production of isoolefin polymers with improved initiator system preparation
US10174138B1 (en) 2018-01-25 2019-01-08 University Of Massachusetts Method for forming highly reactive olefin functional polymers
US10829573B1 (en) 2019-05-21 2020-11-10 Infineum International Limited Method for forming highly reactive olefin functional polymers

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WO2002050129A1 (fr) * 2000-12-20 2002-06-27 Exxonmobil Chemical Patents Inc. Processus de polymerisation de monomeres a polymerisation cationique
EP1358230B1 (fr) * 2000-12-20 2006-06-07 ExxonMobil Chemical Patents Inc. Procede permettant de polymeriser des monomeres polymerisables par voie cationique

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