CA2078769A1 - Polybutene process - Google Patents
Polybutene processInfo
- Publication number
- CA2078769A1 CA2078769A1 CA 2078769 CA2078769A CA2078769A1 CA 2078769 A1 CA2078769 A1 CA 2078769A1 CA 2078769 CA2078769 CA 2078769 CA 2078769 A CA2078769 A CA 2078769A CA 2078769 A1 CA2078769 A1 CA 2078769A1
- Authority
- CA
- Canada
- Prior art keywords
- polybutene
- catalyst
- hcl
- organo
- mixture
- 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.)
- Abandoned
Links
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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Lubricants (AREA)
Abstract
Polybutene is prepared from a mixed C4 hydrocarbon feedstream using an organo-aluminum/HCl catalyst system wherein the HCl is introduced separately into the feedstream to form organochloride in the feedstream. Polybutene product having a very narrow molecular weight distribution is obtained over the Mn range of 700 to 3,000. Dispersants derived from this polybutene exhibit substantially improved performance in lubricating oil compositions.
Description
W0~1~14719 PCT/VS91/02012 IMPROVED POLYBUTENE PROCESS ~PT-805 BA~GRow D OF THE INVENTION
FIE~p OF THE INVEN~ON
This invcntion relates to the polymerization o isobutyl-n--containlng feedstrea~s and, more particularly,~, this lnv-ntion relates to the production of polybutenes ~rom a mixed C4 feedstream utilizing an organo-aluminum chloride-hydrogen chloride co-catalyst system.
~ESCRlPrION OF PRIQ~ART
The production of isobutylene polymers from mixed C4 hydrocarbon feedstreams is generally known in the ar,t. It is also known to uti:ize AlCl3 as ths polymerization catalyst in such processes and the prior art disclo~es a number of co-catalyst or catalyst promoters, including hydrogen chloride for use under various conditions in isobutylene polymerizatlon.
Repres-ntative disclosur-s includ~ U.S. Patent No.
FIE~p OF THE INVEN~ON
This invcntion relates to the polymerization o isobutyl-n--containlng feedstrea~s and, more particularly,~, this lnv-ntion relates to the production of polybutenes ~rom a mixed C4 feedstream utilizing an organo-aluminum chloride-hydrogen chloride co-catalyst system.
~ESCRlPrION OF PRIQ~ART
The production of isobutylene polymers from mixed C4 hydrocarbon feedstreams is generally known in the ar,t. It is also known to uti:ize AlCl3 as ths polymerization catalyst in such processes and the prior art disclo~es a number of co-catalyst or catalyst promoters, including hydrogen chloride for use under various conditions in isobutylene polymerizatlon.
Repres-ntative disclosur-s includ~ U.S. Patent No.
2,957,930 which shows the use of lO t~ 20% AlC13 catalyst in the production of polyisobutylene from a Cl to C5 potroleum gas feedstocX with 0.08 ~o 0.12 percent HCl, relative to AlC13, used as a catalyst promoter. This rQ~or~nce notes that correspondingly small quantities of water vapor or chloroform, which can react with AlCl3 to .
: - . . , . . , .. ,. . . . ... -- : , -.- . .
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20787~9 2 - -r-l-a-- NCl, may also b- us~d Brltish Patent No.
1,195,760 (1970) disclo-~s th- production of olefin polym-r~ by polym-rlzation in th- pres-nc- of the catalyst comprising a llquid compl-x Or AlC13, HCl and an alkyl b-nzan- Polym~rization products includ~ matcrials other than polyisobutyl-n- and product~ with a narrow ~olecular weight dlstribution ar- diaclosad in this raference U S Pat-nt No 3,349,06S r-lat-~ to a proces~ ~or formlng butyl rubber rrOm r~-d~tr-ams comprlsing isobutyl-n- and isopr~ne, employing a catalyst system or dlalkyl aluminu~ halida - hydrogen halld- catalyst system Th- pat-nt llluJtrat-- th- additlon ot HCI to th- monomer f--d b-fore addltlon o~ diethyl alumlnum chloridQ in s-v-ral example~ (Q . g., Exa~ple 8, run V) U S Patent No 3,119,884 dl-closas a series Or vertical column r-actors uso~ul for polymerizing isobutylen- and further disclosQs a catalyst comprising AlC13 and HCl or a substance whlch g-n-rat~s HCl The catalyst system is descrlb-d as an acld promoted AlC13 cataly~t In such a system, a reaction b-twaen HCl and AlC13 occurs to form H~AlC14_ which is the species that initiat-s polyn~rizatlon Accordlng to this process, one m-thod of introducing catalysts and reactants is to have the thre- mat-rials, i e , AlC13, HC1 and liquid feed, enter th~ r-actor through the sama duct This necessarily r~sults in polyo-rlzation beginning in th- duct line in an xoth-rmic r action and the raaction is not controlled by th- r-frig-ration ~ystem of the r-actor Any product for~-d under theJe conditions will have an undesirable low 201ecular weight and broad mol-cular w-ight distribution U S Patent Nos 3,200,169 and 3,200,170 deal with th~ rcaction mixture Qparation methods after polym-rization of propylen- or butyl-n- feeds utilizing an ammonia troatment proc-ss RCl is disclosed in the ræf-r-ncQs as a suitable catalyst promoter added to the roaction zonc which contains an AlC13 cataly~t U S Pat-nt No 3,501,551 i~ dir-cted to a proces~
ror produelng nornal buten- poly~-rs at ~olecular ~eights of from about 200-7So wher-in a C3_5 hydrocarbon mixture eontaining i~obutyl-n- and normal butylenes as sub-tantially th- only ol-rln~ pr---nt ar- reacted in liquid pha-- with an alu~inum ehlorid- eatalyst to ~or~ a r-aetion mixtur- eontaining only i~obutyl-n- poly~-r~ The i-obutyl-n- poly~-r~ ar- s-parat-d and ther-a~ter th-r sulting r-aetlon uixtur- is tr-at-d wlth a Fri-d-l-Crarts eataly-t to ~orm a s-eond r-aetion nlxtur- eontaining nornal butyl-n- polymers, Th- aluminum ehloride in th-first polym-rization section is indieat-d to be added alone or in eombination with promoter~, sueh as alkyl chlorid-, g , isopropyl chloride U S Patent No 3,639,661 relat-s to proc~sses for poly~-rization of isobutylen- employing as polynerization catalysts ith-r a reaetion produet of tltanium tetra~luoride with a ehlorino bearing Friedel-Crafts eatalyst which is solubla in isobutyl-n- or a reaction produet o~ titanium t-traehlorid- or boron trichlorid- with a tluorin- b-aring eompound whos- fluorin- atoms ar-eapabl- o~ partly r-plaeing chlorin- atoms in th- titanium t-traehlôrid- or boron tetraehloride ~t is indicat~d that th- eataly~t ean b- mad- in sltu by adding the eatalyst eo~ponents separately to the r-aetion medium U S Patent No 3,991,129 relates to the produetion o~ polybutene employing reeyeled reaction liquid, liqu-~ied buten-s -and FriQd-l-Crafts eatalyst, whieh is stated to be preferably aluminuo chloride pr~oted with hy~roehlorie aeid gas or its water equivalent The .. .~ . .
eatalyst is adnixed with th- r eyel--and ~resh feed lines upstr-am~o~ ;a -~tatie mixer prior to eharging to the polym-rization reaetion eolumn s, . _ .. ~ " , . ~ .. ' ' .. . .. .
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WO 91/14719 pcr/us91/o2ol2 2078769 - 4 ~ ' U S Pat-nt No 3,932,37l r-lat-s to a process for pr-paring low bulk visco~ity poly~er- compri~ing copoly~ers of i~ool-fln~ and con~ugated diol-fln~, g, isobutene isopr-ne mixtures, as in th- pr-paration of butyl rubber, employing an ethyl aluminum dichlorido catalyst optionally pro~ot-d with hydrog-n chlorlde or a C3 to C7 organic halid- conpound Hydrog-n chlorid- is di~closed as a pro~ot-r which can eomprlJ- frol~ O l to 50 wt % of the total cataly-t sy-t-m In Ex~pl- 2, b-nzoyl chloride proloot-r i~ add-d to an l~obutyl-n~ opr-n- monomer mlxtur- whlch is then contactad wlth ethyl aluminum dichlorid- (EADC)' in a contlnuou~ r-actor U S Patent No 3,985,822 relat-~ to the production of poly-n-butenes by u~- Or AlC13 promoted with HCl but th- objective is to reduce the isobutylene cont-nt of the polym-r product U S Patent No 3,997,129 disclos-~ polybutylenes froDI a Cl to C5 liquefi-d rerln-ry stream wherein the !' catalyst i~ solid partiCl~s o~ AlCl3 promoted with HCl gas or its equival~nt This proc-s~ employ~ a static mlxer for mixing catalysts and f--d - prlor to conducting polymerization U S Pat-nt NOJ 4,038,474 and 4,039,733 each relate to ethyl aluminum diehloride - HCl catalyzed proc~ses ~or pr-paring polymers from a C4 olefln-styrene Dlono~er mixture, whieh in '474 contains at least 20% ~-styran- and whieh in ~733 eontains divinyl benzene for p~rtial ero~-linXing -Example~ 4, S and 6 of '47~ describe proc-dur~s in whieh -the C4 olefin-~tyrQne Dlono~oers are fi~t bl~nded 'with ~Cl and a h~droearbon~-olvent, and then tr~ated with EADC to e~feet polym rization - - -U S Patent No 4,465,887~ relates to a proces~ for produclng butylene poly~er-~ havlng' ~iioI-eular weigh'ts of fro~ about 400-5,000 wherein tho reod~trea~ containing ~ixed butene~ i~ fraetionated to r~ove reeited amounts of -: ,"' WO9t/14719 PCT/US91!02012 ei--2-but-n- ~h- ov-rhead fraetion trom th- fractionating st-p eontaln- l~obutyl-n- and i- reaet-d in th- pr~sence of an alu~lnu~ ehlorld- eatalyst to polym-rlz~ th- isobutyl~ne and to form a r-aetion mixtur- eonsistlng of isobutylene poly~-rs and unr-aetion hydroearbons ineluding nor~al buten-- Thi- r-aetion' ~ixtur- i~ flash~d distilled or r-eo~-r th- lsobutyl-n- poly~-rs and th- unreact-d hydroearbon mlxtur- 1- th-n r-aet-d in a pr-~ene- of a eataly-t y-t-m eon-l~tlng o~ alumlnuD ehloride and a promot-r to polym-rlz- butyl-n-J in tho fraetion and form in a -eond r-aetlon product mixture eontaining butylen-poly~-rs having lower ~olecule w-ights, e g , of fro~
400-900 ~olecular weight ~he patent indicates that a ' pro~ot-r is ~ential of a ~-eond polymorization reaetion, and indieates that typieal promot~rs ar- isopropyl ehlorld-, t-butyl ehlorid-, wat-r and hydrogen chlorid-Th- pat-nt's promot-rs are added to the r-aetor separately from th- alu~inum chloride and the first hydrocarbon r-aetion mixtur- eontaining th- unr-acted normal buten-U S Pat-nt No 4,S58,170 i's direeted to a process for pr-paration Or polyisobutyl-n- from a mix-d C4 hydroearbon f--d~tream u~ing an AlC13 - HCl catalyst syst-m wh-r-in th- HCl i~ introdue-d s-parat~ly into th-f--dsti-am, prior to eontaeting th- fe~dstream with the AlC13, to for~ organoehlorid- in th- feedstream, e g , th- t-butylehloride i3 formed by r~action of the HCl with th- f- drtr-a~'s'isobutyl-n-B-lgiu~- Pat'-nt- No 73~,006 relates to the alkylatlon of aromatic hydrocarbons u~ing n-butene polymers, where$n the polym-rs are produced fzom a refiner Ytr-a~ eontaining n-butene basically fr-e fro~'isobutylene whie~ aro polyn-riz~d in th- pr-~nce of aiurminum chloride uropean Patent No ll5i63S r'èlat-s to a eontinuou~ proe~ for producing''polyisobutyiéne'from isobutylane 'feed~, wherein sol~ent~'and ~ono~ér ~aporized .
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2 0 7 ~y~ PCT/US91/02012 during th- polym-rization ar- r-cycl-d after liquefaction to th- polyn-rization zon-U K Pat-nt No 1,449,840 d-serib-s a process for alXylating b-nz-n-, wh-r-in b-nzene ~s contacted with a polybut-n- in tho pr~--nc- of aluminum ehloride The polybut-n- its-lf is pr-par-d by polyu rizlng a uix~d C4 f--d-tock eontaining rrou 2-20 wt % of isobutene The polybut-n-s ar- tated to b- pr-par-d by eon~-ntional polym-rization proe-~ w ing a Fri-d-l-Craft~ eatalyst sueh a~ aluninum ehlorid-U X Pat-nt Applieation 2,001,662A r-lat~- to the pr-paration of polybutene by polyu-rization o~ a C4 ol-fin str-am ov-r a ~ixed bed~ eatalyst eompri-ing a ~ewis aeid ehloride (AlC13 being illu~trated) int-realated with graphit-, with HCl being added optionally as a promoter The pat-nt diselo ~ that~the HCl nay b- added to the mononer f~-d b~fore it conta'ets th- eataly-t b-d SUMMARY OF TH~ PR~8~ v~NI~Q~
Th- pres-nt inv-ntion is eonsid-red distingui~hed fro~ th- for-going r-f-r-ne-- in that it produees a polybut-n- whieh ia sp-eially suitabl- aJ the oil solubl-hydroearbon eompon-nt o~ a lubrieatlng oil disp~rsant based upon th- r-aetion of poLyisobut-nyl suceinic anhydride with eompound~ ~uch a~ thyl-n- polyamin-s and polyol~
Polybut-n- produeed in this inv-ntion are eharacterized by a narrow ~ol-eular weight di~tribution in the di~persant ~ol-eul~r weight rang-, that i~, a nueb-r av-rag- moleeular w-ight (Rn) Or about 700 to 3,000 Mol-eular ,w-ight di~tribution is used h-r- in it~ normal sense as a ~-asure o~ th-'breadth of mol-eular weight,,distribution and i~, d-~in-d a~ ~th~ ratio of ,Rw ,(w-ight a~erage ~ol-eular w~ight? to ~n (nu~b-r av-ragQ mol-eular weight) This narrow,molecular weight di~tribution re~ults in a 'product having a relativ~ly lower viscosity than , . .
, , WO91~14719 PCT/~S91/02012 - 7 2~78769 polybutan-a produc~d in h-r~tofor- conventional processes in th- a~- mol-cular ~-ight rang- The process is esp-cially charactariz~d in th- techniqu- Or addition of HCl co-catalyst to the feed~tream prior to the feedstream entering th- r-actor Oth-r m thods Or providing HCl which th- prior art consider~ ~uitabl-, i - , such as adding HCl to th- r-actor its-lt, adding wat-r or othar HCl-generating r-ag-nt~ or adding HCl to thyl aluninun dichloride (EADC) prior to initlation o~ polym-rization ar- not sultable in thi~ inv-ntion and do not provlda th- d-gr-- o~ process control and product guality achi-ved har-in In particular, it has bean surprisingly found that th- us- Or organo-aluminum chloride catalyst, instead Or AlCl3 as described in U S Patent No 4,558,170, in co~bination with HCl pre-addition to the monomers, provid--a polybut-n- Or still further narrowed mol-cular weight distribution, high-r catalyst efticiency, higher monomer conv-rsion, and d-crQased light ends by-product ma~e, as compar-d to product obtainad in u~- or H2O/AlCl3 or H20/EADC a~ a promoter/catalyst ~ystem ~BI~F DEscRIE~ N OF THE ACcoMPANYrNG DRAWI~G
Figure l is a schQm~atic illu~tration of one embodiment Or th- process th- pr-sent invention DETA~ L~ESCR~pTION OF TH~ INVENTION
In accordance with the prQ~nt invention ther- has b-~n di~co~ered a process ror praparing low molecular w-ight polybutene having an ~n in the range o~
about 700 to about 3,000 (and pr-ferably from about 900 to 2,500?, and a molecular weight di~tribution les~- than about 2 0 fro~ a feedstrea~ ~ixtur- Or C4 hydrocarbons containing at least about 6% by-w-ight isobutylene in a stirrQd reaction zone maintained at a t-mperature of about , - - - ~ - -, .. , . . . _.. ..
, ~
207~769 8 --50 C to +30 C, whieh compris-- (a) in~-cting HCl into tho r--d-tr-ao uixtur- in an anount o~ ~ron about 25 to 200 parts by w-lght p-r one ~illion partJ by weîght of the feedstr-au nixtur-, in the substantlal absenee of the organo-aluoinuu eatalyst and und-r condltion~ sufficient to ub-tantially eonpl-tely r-aet th- ln~-et-d HCl with f--d~tr-au nonon-rs, ther-by produclng a tr-ated ~eedstrean nixtur- whlch eontaln~ not gr-at-r than about 1 0 ppm free HCl; (b) lntrodueing th- tr-at-d r--d~tr-au nixture and th- organo-aluninu~ ehlorid- eatalyst aa -parat- streams into th- r-aetion zone (e) eontaeting the introduced tr-at-d f--dstr-a~ ~ixture and th- lntroduc-d cataly~t in th- r-aetion zon- for a tlme and under eondltions suf~lel-nt to forn a poly~erizatlon r-action mixtur-contalning the polybut-ne; (d) wlthdrawing th-poly~-rization r-aetion mixtur- ~rou th- reaetion zon-and (-) reeovering the polybutene product from said withdrawn polymerization reaetion ~lxture The polybutenes can b- r-eover-d fro~ th- r-aetion mixtur- by quenching the withdrawn r-aetion ~ixtur- with aqu-ou- alXali and s-parating ther-rro~ polybutene~ produet, which ean then be stripp-d Or unr-aet-d C4 hydroearbons and polybuten-~b-low ~n or 300 ~u~lel-ntly to provid- l-gs than 25 wt ~ polybut-n- b-low ~n of 500 in the final product Th- f--dstoek ~or th- process o~ this invention co~pris-- a ~ixtur- of pre~sure lique~ied C4 hydrocarbons (~ueh a- eatalytie crack-d C4 or st-an craeked C4 rraetions) whieh eompriso at least about 6%, up to about 50% i~obutylene- together with butene-l, cis- and tran~-but-ne-2, n-butane, isobutane and less than about 1%
butadi-ne -- Th- pr~ferred C4 fe-dstr-an i~ derived fro~
r~rinery eatalytie~ or st-an eraeking and contains fro~
about 6-4S% by--w-ight isobutylén-, ~ro~ about 25-3S%
~aturat-d butanes and fro~ about 15-50% 1- and 2-butene~
. , , WO91/14719 PCT/US91!02012 .
Th- C~ product- oth-r than i-obutyl-n- ~unction as the r-action m~dlum and ar- a non-critical aspect of this inv-ntion Th- isobutyl-n- cont-nt of tho feedseock should not how-ver fall b-low about S wt % Or th- reedstrea~
Th- C4 f-ed~trQam pr-ferably is substantially fr-- o~ H2 and sulrur contaminant- (- g , n-rcaptans)~
g c20 wppm H2 and <5 wppm S Such low l~v-ls Or fre-H2 minimiz- th- d-gr-- o~ saturation in th- polybutene product~ Or thl- inv-ntion, and th- low S l-v-l~ ar-d-~ir-d to avoid und-Jir-d Jid--raaction- with th- monomer, poly~er and cataly-t componant~, and to a~oid th- n~Qd to r-~ort to add-d exp-nJ- and t-chnlcal difficulties in r-moving th- sulfur contaminants from the poly~ers thereby form-d Furthor, the C4 f--dstr-a~ is pr-f-rably substantially anhydrous, that it, contains l--- than about 0 05 wtt water, more preferably l-s- than about 300 wppn watQr, based on the C4 monom-rs in the fe-dstream It has b--n found that water, which can b- typically present in catalytically crack-d or ~t-am crack-d C4 streams, is not an eff-ctiv- co-cataly~t in the manufactur- of th-polybut-n- poly~-rs of th- pr-s-nt inv-ntion employing the organo-aluminum catalyst/HCl pr--reactod cocatalyst systems in th- pre~-nt inv-ntion Rath-r, such xc--~ amounts of water ar- unde~ir-d du- to ~id--r-actions of th- water with th- organo-alu~inum catalyst which decreas- th-~ e~fectiv~
catalyst conc-ntration in th- r-actor, and do not orfer any o~fs-tting onhancement in th- rate of polym-rization or in ~ny ob--rv-~ polymer perrornanc- prop-rty The drying of th- C4- feed~trea~ can bQ
acco~pli~hed by contacting-th- ~tream with a dessicant which is substantially nonr~activ- with any organic compon~nt of the stream, such as-CaCl2,- molecular sieves (- g ,~ ~ol ~i-v-s 3A and l3X fro~''Lind- Division, Union Carbide), and th~ lik- The-drying-of th- f~-dstream can bo ~fected in one or ~or~ veJs~ls containing a solid .
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WO 91/14719 PCT/US91!02012 2a7~769 - lo d---ieant through whieh C4 f--dstr-an is passed, and us-rully ean eomprl~- a s-ri-- Or s~parat- vessels arranged in parall-l to faseilitat- th- charging to any ~essel of fr~sh d-ssicant in tb- continuous praetic- of the process of this inv-ntlon Th- C4 f--dstream is maintain-d at a sui~icient pr ~-ur- to b- in liquid form both in th- reaetor inlet and in th- r-action mixture its-lr at the r-aetion tenperature, whieh i~ g-n-rally from about -50~C to +30 C, eon~-ntional eoollng m-ans (- g , providing eooling colls within th-r-aetor eoollng th- ext-rnal surfae-s or th- r-actor;
withdrawing a portion ot the r-aetion mixtur- from the r-aetion zon- to an external cooler and reeyeling it to th~
reaetion zon-; ete ) being useq to malntain th~ r-action at th-Je t~mperatures in view Or the -exothermie nature of th-r-aetion Pr-f-rred reaetion t-mperatur-s are rrom about -15 C to +lS C and most pr~f-ried fron about -S C to +lS C G-nerally, relativQly high-r t-mp-ratures tend to produe- r-lativ-ly low moleeular weight polym-r Reaction pr--sur~s ar- gen-rally fro~ about 100 to 600 kPa, and more typieally fro~ about 200 to 400 kPa Th~ proee~s of th- pr-s-nt invention employ~
eith-r a tubular r-aetor or a ~tirr-d r-aetor ~pr-~-rably a eontlnuouJ typ- ~tirr-d r-actor) having two separate inlet m-anJ for introduetion of C4 feedstream and the organo-aluoinuu ehlorid- catalyst, the latter b~ing added alon- or in adoixtur- with a dilu-nt or solv-nt which is substantl~lly in-rt -under th~ pr-mixing and polym~rization eonditions Us-ful dilu-nts ~nclud- liquid saturated hydroearbons, -such as n-butan-, isobutane or mixtures of saturated butan~s ... ... ~... . .
h-- f--dstrea~ inl~t means- (~ g , a eonduit) is fitt~d with a d-~iee for inj-etion -(pref-rably for continuous inj-ction) of HCl (preferably gas-ous HCl) co-eatalyst into the~ C4 feedstr~a~ ae a point-prior to :
r-actor ntry ~h- HCl in~-ction point ~hould b- placed in th- C~ f--dstrea~ suffici-ntly in advance of the reactor entry to p-r~it ~ub~tantially compl-t- r-action of the HCl in th- f--d~tr-an with 1- and 2-but-n-s prior to the polymerization r-action zone Th- HCl 1~ b-li-ved to react with th- i~obutylon- to form t-butyl chlorid~ in th~
r-~ulting tr-at-d f--d~tr-am mixtur- Other organo chlorid-~ can also b- forn-d principally a 2-chlorobutane from r-action wlth th- 1- and 2-but-n-~ Or th- monomer f--d~tr-am Th- conc-ntration o~ tr-- HCl in th- treat-d te-d~tr-am mixtur- at th- point or r-actor ntry should ther-ror- be not gr-ater than about 1 0 ppm (parts per milllon) or less in order to achieve th- advantage of th~
inv-ntion Th- concentration of th~ HCl can b- d~ter~in-d by conv-ntional means for exampl- by analyzing th-feed~tr-a~ for organic chloride~ and free HCl u~ing a ga~
chromatograph equipped with a Hall detector Th- rate of mixing (and hence reaction) o~ the monon-rs and the HCl can b- convenisntly enhanc-d by us- o~ an in-lin- static (kin-tic) mi in the feed~tr~an conduit down~tream of th~
HCl in~-ction point (Alt-rnativ-ly or in addition th~
HCl can b- add-d to the C4 f--dstream prior to an in-lin-indirect h-at xchang-r to ~id in nixing th- HCl and th~
monom-r~ prior to th- r-actor by m-~ns o~ the turbulence gen-ra~-d in pa~-ing th-r-though ) To further enhance the rat- of mixing of the HCl and monom-r~ th- mixture of the HCl and th- C4 feQdstream is pr-r-rably ~aintained at a t-mp~r~ture of from at least about S C - g fron about 5 to 70 C
Pr-f-rably the organo-aluminu~ chloride cataly~t i not admixed with th- C4 r--d~tream prior to or during the inj-ction o~ the HCl (and prererably is not ad~ixed with th- C4 monom-r containing ~trea~ prior to the charging Or the treat-d feedstrea~ m$xtur- -into the reactor); otherwise uncontroll-d exother3ic poly~-rization .
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... ~
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2~8769 12 - ' - will b- initlat-d unless extr-me mea~ures are taken (such a~ malnt~ining th- ad~ixtur- at a t-mperature below that which polymerizatlon proce-d~ ) Of course, the extent of such und-sired pr--polymerization will vary, dependinq on 'th- r-~id-nc- ti~e of th- admixtur- outsid- o'f the I -r-actor'~ r-action zon-' ~h-r-~or-, the tr-at-d f--dJtr-am mixture, containlng th- C4 ~onom-rs and th- pr--r-acted HCl, is pr-~-rably add-d (pr-~-rably contlnuou-ly) to the r-actor with organo-aluminum chloride cataly~t b-ing introduced into th- r-action mixture through a ~-parat- inl-t Th- proce~s Or this inv-ntion can b- practiced in a batchwi~e, semi-continuous or (as i~ pr-ferred) in a continuou~ manner Pre~-rably, th- tr-at-d fe-d~troam mixture, containing the C4 monomers and th- pr--teacted HCl, and the organo-aluminu~ chlorlde catalyst streams are add-d to the reaction zon- ~ubstantially simultaneously, at a rat- surrici-nt to maintain the sel~cted ratio o~ the monom-r~ and organo-aluminum cataly~t in th- liquid r-action mixtur- However, it is al~o po~sible to add th--- str-ams in a ~tag-wis- mann-r to a liquid reaction mixtur- .
Polym-rlzatlon occurs in an exothermic reaction by contacting- the two inco~ing streams in a cooled reactor with r-actor temp-ratur~, prefera~ly maintained at about -lS C to ~15 C For a continuou--typ- stirred reactor, ' av-rag r-actant residenc- tim- wilI generally be about lO
- to ~S ~inut-~ Th-re will generally b- employed o ool to 0 008 mol-~ ~preferably Srom about 0 002 to 0 006 moles) of organo-alu~inuc catalyst per mole of isobutylen- charged in th- fe-dstr-am and from about 25 to 300 ppm by weight (and ~pre~-rably from; about 'S0 to -150 ppm by weightj' of HCl ~~co-c~tal'y~t -pe-r''~part by w~ight of C4 ~r--dstream - - ~G~n-rally, the ~organo-aluminum chlorid- catalyst and HCl-cocataly'st~will bo employed in a ratio Or~ fro~ about l I
' _ 13 _ 2~787~9 to ~ part- by v-ight, pr-~orably ~rom about l 3 to 3 parts by w-ight, and mor- prer-rably ~ron about l 5 to 2 7 parts by w-ight, o~ th- organo-aluminum chlorid- catalyst per part by weight of the HCl-cocataly~t (calculated as HCl) Th- organo-aluminum chlorid- u~-ful in the process o~ thi~ inv~ntlon compris-~ at l-a~t on- co~pound o~ the fornula (I) (R)xAltclj3-x wh-r-ln R in Cl to C20 hydrocarbyl and x is an integ-r of ~rou l to 2 R can comprl~e branch-d or straight chain-d alkyl, cycloalkyl, aryl, alkaryl, ar~lkyl, alkenyl, and alkynyl, and hydrocarbyl (- g , Cl to ClO) sub~titut-d d-rivative~ thereo~ When R is alkyl, th-alkyl group can contain from l to 20, pref-rably'from l to lO, and most pre~rably ~rom l to 4, carbon atom~
Illu-trativ- Or such alkyl group- ar- m-thyl, ethyl, isopropyl, propyl, n-butyl, isobutyl, t-rtbutyl, p-ntyl, hexyl, heptyl, octyl, nonyl, d-cyl, dodecyl, tridecyl, t-tradecyl, octadecyl and th- like When R i~ alkenyl, th-alk-nyl group can contain rrom 2 to 20, pr-rQrably ~rom 2 to lO, and mo~t pr~erably rrom 2 to 4, carbon atoms Illu~trative of such alkenyl groups eth-nyl, isopropenyl, prop-nyl, n-but-nyl, i-obut-nyl, t-rtbut-nyl, pentonyl, h~x-nyl, h-pt-nyl, oct-nyl, nonenyl, d~cenyl, dodecenyl, trid-c-nyl, t-trad-cenyl, octad-c~nyl and the like When R
l~ ~lkynyl, th- alkynyl' group can contain ~rom 2 to 20, -pr r-rably fro~ 2 to lO,''and mo~t prQferably from 2 to 4, carbon ato~ Illustrativ- Or ~uch alkynyl groups ar-othynyl, isopropynyI,~propynyl, n-butynyl, isobutynyl, tertbutynyl, pentynyl, h-xynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, tridecynyl, t-tradecynyl,~ octad~cynyl and th~ like When R is~~'aryl, th- aryl group can contain `fro~ 6--to lO carbon ato~s'~Iliu trativ- ot such ary~ group~
ar~' ph-nyl, naphthyl and the like WhQn R i~ aikaryl, th~
alXaryl qroup can contain''from 7 to 20, preferably ;trom 7 .
..
.
2 0 ~ 719 PCr/US91/02012 to 15, and most pr-rerably from 7 to 10, carbon atoms ~llu-tratlv- Or such alkaryl group~ ar- tolyl, xylyl, di(-thyl)phenyl, di(hexyl)ph-nyl, and the llke When R i~
aralkyl, th- aralkyl group can contain ~roDI ~ to 20,`
pref-rably from 7 to ~5, and mo-t prer-rably fro~ 7 to 10, carbon atomJ Illu~trative of ~uoh aralkyl groups ar~
b-nzyl, thylb-nzyl, ph-nylh-xyl, naphthylh-xyl, and the 1 lk- Wh-n R i- cycloalXyl, th- cycloalkyl group can contain frol- ~ to 20, pr-~-rably ~ro- 3 to 10, and most pr-f-rably ~rom 3 to 4, carbon aton~ ~llu-trativ- Or such cycloalkyl groups ar- cylcopropyl, cyclobutyl, cyclopentyl, cycloh-xyl, cycloheptyl, cyclooctyl, cyclononyl, cyclod-cyl, cyclododecyl, cyclotridQcyl, cyclotQtradecyl, cyclooctad-cyl and the lik- Illustrativ- or hydrocarbyl-substituted der; vatives o~ th- ~or-going group-ar- 2--thylcyclohexyl, cyclopropylph-nyl, ph-nylcylohexyl, and th- lik-lllustrative of us-rul organo-aluminum chloride~
ar- ( CN3 ) AlC12, ( CN3 ) 2AlCl, C2H5AlC12, ( C2H5 ) 2AlCl, ( CH3 ) 2CNAlC12, ~ ( CH3 ) 2 CH ~ 2AlCl, (C3H7) A1C12 ~ (C3H7) 2A1C1, CH3CN(CH3 ) A1C12 t CH3 CB ( CH3 ) ~ 2AlCl, ~ CN3 ) 3 CAlCl, ~ ( CB3 ) 3 C ~ 2Al Cl, C6N13AlC12, CSHllAlcl2, C1OH21AlCl2, and mixtures th-r-o~ Esp-cially preferred are C2HSAlC12 ~ (C2H5j 2AlCl and mixtures th~reof Ps~-r-rr-d ar- organo-aluminum chloride catalysts which are liguid- und-r th- reaction conditions Th- polybutene pNpar-d in accordance with this invention generally contain an av-rage of about 1 double bond por polymer chain and up to about 10 percent or the polymer chain~ may be satur~t-d -ferring r~ow to Figure 1 wher-in on- ~bodi~ent of th- process of thi~ invention i9 illustrated, a C4 . ., . .;: , ~. - -- - .
fe~dstre~ 2 is pa ~ed through a drying zon- 10 for removal of water (~ g, u4ing CaC12) ~he dri~d C4 stream 11 .,. ... . .1 WO 91/14719 PCI/I~S91/02012 is th-n pa~--d through tubular heat xchanger 12 for cooling o~ th- f--dstr-an to th- d--ir-d reaction t-mp-ratur- HCl ga~ is introduced via conduit 4 into conduit 11 up-tr-aDI o~ exchanger 12 The treated f-edstrea~ is th-n introduc-d via conduit 14 into reactor 20, th- fr-- HCl ContQnt ot th- thus-introduced feed 14 b-ing as d-scrib-d abov- I$quld organo-aluminu~ cataly~t ~- g, thyl alul~inum dichloride) ia introduced into r-actor 20 vla a s-parat- condult 18 A portion o~ the liquld r-actlon m-dlum ls withdrawn vla conduit 22 and pas~-d to xt-rnal h-at exchang-r 30 via conduit 24 for coollng o~ th- r-action liquid, and the cooled liquid is r-introduced to reactor -20 via conduit 26, to aid in r-action t-mperaturo control Poly~er r-action liguid is withdrawn ~rom the reactor 20 via conduit 22 and passed to conduit 28 and introduced into a ~irst ~rat-r washing zon-40 (to which water is introduced via conduit 42) to quench th- catalyst Th- aqueous and organic layers ar- allowed to s-parat-, and the upp-r aqu-ous lay-r is withdrawn via conduit 44 The washed organic lay-r containing the polyDI-r is withdrawn via conduit 46 and passed to an aqu-oua caustic contactlng zon- 50 ~or furth-r n-utrallzatlon and r~oval o~ catalyst resldue- Agu-ou~
caustic i~ introducQd via conduit 52, tho separated aqueous lay-r is withdrawn via conduit 54, and th- treated organic lay-r is pa---d fro~ zono 50 to a s-cond water washing zon-60, - for contacting with additional WatQr, introduced via conduit 62 A s-cond aqueou~ straam 64 is removed and a ~cond washed organic strea~ 60 containing the poly~ner which is preferably substantially free o~ the catalyst (- q , a~ -determined by a substantially neutral pH, and by an alu~inu3l1 ~content of less than about 10 wppm Al) is wlthdraw ~ a- strea~ 66 , ~ .
' WO91/14719 PCT/US91!02012 Polyn-r str-am 66 can then b~ passed to distlllation zon- 70 for r-mo~al Or C4 s (butanes and unr-acted but-n-s) as an ov-rh~ad product 72 The bottoms 74 can b- p~-d to a s-cond distillation zone 80 for re~oval oS th- light polym~r fraction a~ an s-cond overhead product 82 Th- r-sulting ~-cond bottom~ str-am 84 can th-n b- pass~d to a third dlstillation zon- 90 for r-moval oS wat-r th-r-Srom a~ a third overh~ad produet 92 if steam stripping ls nploy-d ln à prlor dl~tlllation, to ~orm the poly~-r product Jtr-am 94 ~ t will be und~rstood that r-actor 20 and contacting zon-s 40 S0 and 60 can b~ provided with suitabl~ agitators for mixing ot the str-ams so contacted and that the distillations in zon-~ 70 80 and 90 can b-aceomplished by m-ans known to those skilled ln th- art employing eonv-ntional distillatlon -quipm~nt and tQehniqu-s Th- proe-ss oS this invention ean b- operated eontinuou~ly or on a batchwise or s~mi-continuou- basis Th- polybuten- prepar-d in aceordanee with thi~
inv-ntion offers a number oS advantag-s over polybu~ene prQpar-d by prior art t-ehniques with r-sp-et to those prop-rties whleh ar- lmportant ~or lts u~e in making lubricating oil disp-r~ant typleally in a form of the r-aetion produet oS polyisobutenyl succinic anhydride wi~h polyamin-s or polyols ~ h- signlSlcant aspect is that th~ proeess of this inv-ntion p-r~it-s a mor~ pr~cis- control Or polybutenQ
produetion than h~retoforQ possibl~ ~n lubricating oil disp-rsant technology it is known that a relatively higher '' , ~
~ol~eular weight polybut~ne group provides dispersant additiv~ exhibiting better engin- p-rfor~anee in terms Or sludg~ di~~p rsaney and varnish d-posit inhibition How-v~r conv-ntional techniqu~s for ~anufacturing polybut~no ha~- h-ratofore be~n so~ewhat unsati~factory sinc- thQ viscosities of such rslatively high~r molecular .
: - . . , . . , .. ,. . . . ... -- : , -.- . .
.
: ~ .
20787~9 2 - -r-l-a-- NCl, may also b- us~d Brltish Patent No.
1,195,760 (1970) disclo-~s th- production of olefin polym-r~ by polym-rlzation in th- pres-nc- of the catalyst comprising a llquid compl-x Or AlC13, HCl and an alkyl b-nzan- Polym~rization products includ~ matcrials other than polyisobutyl-n- and product~ with a narrow ~olecular weight dlstribution ar- diaclosad in this raference U S Pat-nt No 3,349,06S r-lat-~ to a proces~ ~or formlng butyl rubber rrOm r~-d~tr-ams comprlsing isobutyl-n- and isopr~ne, employing a catalyst system or dlalkyl aluminu~ halida - hydrogen halld- catalyst system Th- pat-nt llluJtrat-- th- additlon ot HCI to th- monomer f--d b-fore addltlon o~ diethyl alumlnum chloridQ in s-v-ral example~ (Q . g., Exa~ple 8, run V) U S Patent No 3,119,884 dl-closas a series Or vertical column r-actors uso~ul for polymerizing isobutylen- and further disclosQs a catalyst comprising AlC13 and HCl or a substance whlch g-n-rat~s HCl The catalyst system is descrlb-d as an acld promoted AlC13 cataly~t In such a system, a reaction b-twaen HCl and AlC13 occurs to form H~AlC14_ which is the species that initiat-s polyn~rizatlon Accordlng to this process, one m-thod of introducing catalysts and reactants is to have the thre- mat-rials, i e , AlC13, HC1 and liquid feed, enter th~ r-actor through the sama duct This necessarily r~sults in polyo-rlzation beginning in th- duct line in an xoth-rmic r action and the raaction is not controlled by th- r-frig-ration ~ystem of the r-actor Any product for~-d under theJe conditions will have an undesirable low 201ecular weight and broad mol-cular w-ight distribution U S Patent Nos 3,200,169 and 3,200,170 deal with th~ rcaction mixture Qparation methods after polym-rization of propylen- or butyl-n- feeds utilizing an ammonia troatment proc-ss RCl is disclosed in the ræf-r-ncQs as a suitable catalyst promoter added to the roaction zonc which contains an AlC13 cataly~t U S Pat-nt No 3,501,551 i~ dir-cted to a proces~
ror produelng nornal buten- poly~-rs at ~olecular ~eights of from about 200-7So wher-in a C3_5 hydrocarbon mixture eontaining i~obutyl-n- and normal butylenes as sub-tantially th- only ol-rln~ pr---nt ar- reacted in liquid pha-- with an alu~inum ehlorid- eatalyst to ~or~ a r-aetion mixtur- eontaining only i~obutyl-n- poly~-r~ The i-obutyl-n- poly~-r~ ar- s-parat-d and ther-a~ter th-r sulting r-aetlon uixtur- is tr-at-d wlth a Fri-d-l-Crarts eataly-t to ~orm a s-eond r-aetion nlxtur- eontaining nornal butyl-n- polymers, Th- aluminum ehloride in th-first polym-rization section is indieat-d to be added alone or in eombination with promoter~, sueh as alkyl chlorid-, g , isopropyl chloride U S Patent No 3,639,661 relat-s to proc~sses for poly~-rization of isobutylen- employing as polynerization catalysts ith-r a reaetion produet of tltanium tetra~luoride with a ehlorino bearing Friedel-Crafts eatalyst which is solubla in isobutyl-n- or a reaction produet o~ titanium t-traehlorid- or boron trichlorid- with a tluorin- b-aring eompound whos- fluorin- atoms ar-eapabl- o~ partly r-plaeing chlorin- atoms in th- titanium t-traehlôrid- or boron tetraehloride ~t is indicat~d that th- eataly~t ean b- mad- in sltu by adding the eatalyst eo~ponents separately to the r-aetion medium U S Patent No 3,991,129 relates to the produetion o~ polybutene employing reeyeled reaction liquid, liqu-~ied buten-s -and FriQd-l-Crafts eatalyst, whieh is stated to be preferably aluminuo chloride pr~oted with hy~roehlorie aeid gas or its water equivalent The .. .~ . .
eatalyst is adnixed with th- r eyel--and ~resh feed lines upstr-am~o~ ;a -~tatie mixer prior to eharging to the polym-rization reaetion eolumn s, . _ .. ~ " , . ~ .. ' ' .. . .. .
. .
: ' . . ...
.' : ''' ~'' . ,,' :' ', '` '' "' ' ~'' .
WO 91/14719 pcr/us91/o2ol2 2078769 - 4 ~ ' U S Pat-nt No 3,932,37l r-lat-s to a process for pr-paring low bulk visco~ity poly~er- compri~ing copoly~ers of i~ool-fln~ and con~ugated diol-fln~, g, isobutene isopr-ne mixtures, as in th- pr-paration of butyl rubber, employing an ethyl aluminum dichlorido catalyst optionally pro~ot-d with hydrog-n chlorlde or a C3 to C7 organic halid- conpound Hydrog-n chlorid- is di~closed as a pro~ot-r which can eomprlJ- frol~ O l to 50 wt % of the total cataly-t sy-t-m In Ex~pl- 2, b-nzoyl chloride proloot-r i~ add-d to an l~obutyl-n~ opr-n- monomer mlxtur- whlch is then contactad wlth ethyl aluminum dichlorid- (EADC)' in a contlnuou~ r-actor U S Patent No 3,985,822 relat-~ to the production of poly-n-butenes by u~- Or AlC13 promoted with HCl but th- objective is to reduce the isobutylene cont-nt of the polym-r product U S Patent No 3,997,129 disclos-~ polybutylenes froDI a Cl to C5 liquefi-d rerln-ry stream wherein the !' catalyst i~ solid partiCl~s o~ AlCl3 promoted with HCl gas or its equival~nt This proc-s~ employ~ a static mlxer for mixing catalysts and f--d - prlor to conducting polymerization U S Pat-nt NOJ 4,038,474 and 4,039,733 each relate to ethyl aluminum diehloride - HCl catalyzed proc~ses ~or pr-paring polymers from a C4 olefln-styrene Dlono~er mixture, whieh in '474 contains at least 20% ~-styran- and whieh in ~733 eontains divinyl benzene for p~rtial ero~-linXing -Example~ 4, S and 6 of '47~ describe proc-dur~s in whieh -the C4 olefin-~tyrQne Dlono~oers are fi~t bl~nded 'with ~Cl and a h~droearbon~-olvent, and then tr~ated with EADC to e~feet polym rization - - -U S Patent No 4,465,887~ relates to a proces~ for produclng butylene poly~er-~ havlng' ~iioI-eular weigh'ts of fro~ about 400-5,000 wherein tho reod~trea~ containing ~ixed butene~ i~ fraetionated to r~ove reeited amounts of -: ,"' WO9t/14719 PCT/US91!02012 ei--2-but-n- ~h- ov-rhead fraetion trom th- fractionating st-p eontaln- l~obutyl-n- and i- reaet-d in th- pr~sence of an alu~lnu~ ehlorld- eatalyst to polym-rlz~ th- isobutyl~ne and to form a r-aetion mixtur- eonsistlng of isobutylene poly~-rs and unr-aetion hydroearbons ineluding nor~al buten-- Thi- r-aetion' ~ixtur- i~ flash~d distilled or r-eo~-r th- lsobutyl-n- poly~-rs and th- unreact-d hydroearbon mlxtur- 1- th-n r-aet-d in a pr-~ene- of a eataly-t y-t-m eon-l~tlng o~ alumlnuD ehloride and a promot-r to polym-rlz- butyl-n-J in tho fraetion and form in a -eond r-aetlon product mixture eontaining butylen-poly~-rs having lower ~olecule w-ights, e g , of fro~
400-900 ~olecular weight ~he patent indicates that a ' pro~ot-r is ~ential of a ~-eond polymorization reaetion, and indieates that typieal promot~rs ar- isopropyl ehlorld-, t-butyl ehlorid-, wat-r and hydrogen chlorid-Th- pat-nt's promot-rs are added to the r-aetor separately from th- alu~inum chloride and the first hydrocarbon r-aetion mixtur- eontaining th- unr-acted normal buten-U S Pat-nt No 4,S58,170 i's direeted to a process for pr-paration Or polyisobutyl-n- from a mix-d C4 hydroearbon f--d~tream u~ing an AlC13 - HCl catalyst syst-m wh-r-in th- HCl i~ introdue-d s-parat~ly into th-f--dsti-am, prior to eontaeting th- fe~dstream with the AlC13, to for~ organoehlorid- in th- feedstream, e g , th- t-butylehloride i3 formed by r~action of the HCl with th- f- drtr-a~'s'isobutyl-n-B-lgiu~- Pat'-nt- No 73~,006 relates to the alkylatlon of aromatic hydrocarbons u~ing n-butene polymers, where$n the polym-rs are produced fzom a refiner Ytr-a~ eontaining n-butene basically fr-e fro~'isobutylene whie~ aro polyn-riz~d in th- pr-~nce of aiurminum chloride uropean Patent No ll5i63S r'èlat-s to a eontinuou~ proe~ for producing''polyisobutyiéne'from isobutylane 'feed~, wherein sol~ent~'and ~ono~ér ~aporized .
.
2 0 7 ~y~ PCT/US91/02012 during th- polym-rization ar- r-cycl-d after liquefaction to th- polyn-rization zon-U K Pat-nt No 1,449,840 d-serib-s a process for alXylating b-nz-n-, wh-r-in b-nzene ~s contacted with a polybut-n- in tho pr~--nc- of aluminum ehloride The polybut-n- its-lf is pr-par-d by polyu rizlng a uix~d C4 f--d-tock eontaining rrou 2-20 wt % of isobutene The polybut-n-s ar- tated to b- pr-par-d by eon~-ntional polym-rization proe-~ w ing a Fri-d-l-Craft~ eatalyst sueh a~ aluninum ehlorid-U X Pat-nt Applieation 2,001,662A r-lat~- to the pr-paration of polybutene by polyu-rization o~ a C4 ol-fin str-am ov-r a ~ixed bed~ eatalyst eompri-ing a ~ewis aeid ehloride (AlC13 being illu~trated) int-realated with graphit-, with HCl being added optionally as a promoter The pat-nt diselo ~ that~the HCl nay b- added to the mononer f~-d b~fore it conta'ets th- eataly-t b-d SUMMARY OF TH~ PR~8~ v~NI~Q~
Th- pres-nt inv-ntion is eonsid-red distingui~hed fro~ th- for-going r-f-r-ne-- in that it produees a polybut-n- whieh ia sp-eially suitabl- aJ the oil solubl-hydroearbon eompon-nt o~ a lubrieatlng oil disp~rsant based upon th- r-aetion of poLyisobut-nyl suceinic anhydride with eompound~ ~uch a~ thyl-n- polyamin-s and polyol~
Polybut-n- produeed in this inv-ntion are eharacterized by a narrow ~ol-eular weight di~tribution in the di~persant ~ol-eul~r weight rang-, that i~, a nueb-r av-rag- moleeular w-ight (Rn) Or about 700 to 3,000 Mol-eular ,w-ight di~tribution is used h-r- in it~ normal sense as a ~-asure o~ th-'breadth of mol-eular weight,,distribution and i~, d-~in-d a~ ~th~ ratio of ,Rw ,(w-ight a~erage ~ol-eular w~ight? to ~n (nu~b-r av-ragQ mol-eular weight) This narrow,molecular weight di~tribution re~ults in a 'product having a relativ~ly lower viscosity than , . .
, , WO91~14719 PCT/~S91/02012 - 7 2~78769 polybutan-a produc~d in h-r~tofor- conventional processes in th- a~- mol-cular ~-ight rang- The process is esp-cially charactariz~d in th- techniqu- Or addition of HCl co-catalyst to the feed~tream prior to the feedstream entering th- r-actor Oth-r m thods Or providing HCl which th- prior art consider~ ~uitabl-, i - , such as adding HCl to th- r-actor its-lt, adding wat-r or othar HCl-generating r-ag-nt~ or adding HCl to thyl aluninun dichloride (EADC) prior to initlation o~ polym-rization ar- not sultable in thi~ inv-ntion and do not provlda th- d-gr-- o~ process control and product guality achi-ved har-in In particular, it has bean surprisingly found that th- us- Or organo-aluminum chloride catalyst, instead Or AlCl3 as described in U S Patent No 4,558,170, in co~bination with HCl pre-addition to the monomers, provid--a polybut-n- Or still further narrowed mol-cular weight distribution, high-r catalyst efticiency, higher monomer conv-rsion, and d-crQased light ends by-product ma~e, as compar-d to product obtainad in u~- or H2O/AlCl3 or H20/EADC a~ a promoter/catalyst ~ystem ~BI~F DEscRIE~ N OF THE ACcoMPANYrNG DRAWI~G
Figure l is a schQm~atic illu~tration of one embodiment Or th- process th- pr-sent invention DETA~ L~ESCR~pTION OF TH~ INVENTION
In accordance with the prQ~nt invention ther- has b-~n di~co~ered a process ror praparing low molecular w-ight polybutene having an ~n in the range o~
about 700 to about 3,000 (and pr-ferably from about 900 to 2,500?, and a molecular weight di~tribution les~- than about 2 0 fro~ a feedstrea~ ~ixtur- Or C4 hydrocarbons containing at least about 6% by-w-ight isobutylene in a stirrQd reaction zone maintained at a t-mperature of about , - - - ~ - -, .. , . . . _.. ..
, ~
207~769 8 --50 C to +30 C, whieh compris-- (a) in~-cting HCl into tho r--d-tr-ao uixtur- in an anount o~ ~ron about 25 to 200 parts by w-lght p-r one ~illion partJ by weîght of the feedstr-au nixtur-, in the substantlal absenee of the organo-aluoinuu eatalyst and und-r condltion~ sufficient to ub-tantially eonpl-tely r-aet th- ln~-et-d HCl with f--d~tr-au nonon-rs, ther-by produclng a tr-ated ~eedstrean nixtur- whlch eontaln~ not gr-at-r than about 1 0 ppm free HCl; (b) lntrodueing th- tr-at-d r--d~tr-au nixture and th- organo-aluninu~ ehlorid- eatalyst aa -parat- streams into th- r-aetion zone (e) eontaeting the introduced tr-at-d f--dstr-a~ ~ixture and th- lntroduc-d cataly~t in th- r-aetion zon- for a tlme and under eondltions suf~lel-nt to forn a poly~erizatlon r-action mixtur-contalning the polybut-ne; (d) wlthdrawing th-poly~-rization r-aetion mixtur- ~rou th- reaetion zon-and (-) reeovering the polybutene product from said withdrawn polymerization reaetion ~lxture The polybutenes can b- r-eover-d fro~ th- r-aetion mixtur- by quenching the withdrawn r-aetion ~ixtur- with aqu-ou- alXali and s-parating ther-rro~ polybutene~ produet, which ean then be stripp-d Or unr-aet-d C4 hydroearbons and polybuten-~b-low ~n or 300 ~u~lel-ntly to provid- l-gs than 25 wt ~ polybut-n- b-low ~n of 500 in the final product Th- f--dstoek ~or th- process o~ this invention co~pris-- a ~ixtur- of pre~sure lique~ied C4 hydrocarbons (~ueh a- eatalytie crack-d C4 or st-an craeked C4 rraetions) whieh eompriso at least about 6%, up to about 50% i~obutylene- together with butene-l, cis- and tran~-but-ne-2, n-butane, isobutane and less than about 1%
butadi-ne -- Th- pr~ferred C4 fe-dstr-an i~ derived fro~
r~rinery eatalytie~ or st-an eraeking and contains fro~
about 6-4S% by--w-ight isobutylén-, ~ro~ about 25-3S%
~aturat-d butanes and fro~ about 15-50% 1- and 2-butene~
. , , WO91/14719 PCT/US91!02012 .
Th- C~ product- oth-r than i-obutyl-n- ~unction as the r-action m~dlum and ar- a non-critical aspect of this inv-ntion Th- isobutyl-n- cont-nt of tho feedseock should not how-ver fall b-low about S wt % Or th- reedstrea~
Th- C4 f-ed~trQam pr-ferably is substantially fr-- o~ H2 and sulrur contaminant- (- g , n-rcaptans)~
g c20 wppm H2 and <5 wppm S Such low l~v-ls Or fre-H2 minimiz- th- d-gr-- o~ saturation in th- polybutene product~ Or thl- inv-ntion, and th- low S l-v-l~ ar-d-~ir-d to avoid und-Jir-d Jid--raaction- with th- monomer, poly~er and cataly-t componant~, and to a~oid th- n~Qd to r-~ort to add-d exp-nJ- and t-chnlcal difficulties in r-moving th- sulfur contaminants from the poly~ers thereby form-d Furthor, the C4 f--dstr-a~ is pr-f-rably substantially anhydrous, that it, contains l--- than about 0 05 wtt water, more preferably l-s- than about 300 wppn watQr, based on the C4 monom-rs in the fe-dstream It has b--n found that water, which can b- typically present in catalytically crack-d or ~t-am crack-d C4 streams, is not an eff-ctiv- co-cataly~t in the manufactur- of th-polybut-n- poly~-rs of th- pr-s-nt inv-ntion employing the organo-aluminum catalyst/HCl pr--reactod cocatalyst systems in th- pre~-nt inv-ntion Rath-r, such xc--~ amounts of water ar- unde~ir-d du- to ~id--r-actions of th- water with th- organo-alu~inum catalyst which decreas- th-~ e~fectiv~
catalyst conc-ntration in th- r-actor, and do not orfer any o~fs-tting onhancement in th- rate of polym-rization or in ~ny ob--rv-~ polymer perrornanc- prop-rty The drying of th- C4- feed~trea~ can bQ
acco~pli~hed by contacting-th- ~tream with a dessicant which is substantially nonr~activ- with any organic compon~nt of the stream, such as-CaCl2,- molecular sieves (- g ,~ ~ol ~i-v-s 3A and l3X fro~''Lind- Division, Union Carbide), and th~ lik- The-drying-of th- f~-dstream can bo ~fected in one or ~or~ veJs~ls containing a solid .
: ' - ', ~
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WO 91/14719 PCT/US91!02012 2a7~769 - lo d---ieant through whieh C4 f--dstr-an is passed, and us-rully ean eomprl~- a s-ri-- Or s~parat- vessels arranged in parall-l to faseilitat- th- charging to any ~essel of fr~sh d-ssicant in tb- continuous praetic- of the process of this inv-ntlon Th- C4 f--dstream is maintain-d at a sui~icient pr ~-ur- to b- in liquid form both in th- reaetor inlet and in th- r-action mixture its-lr at the r-aetion tenperature, whieh i~ g-n-rally from about -50~C to +30 C, eon~-ntional eoollng m-ans (- g , providing eooling colls within th-r-aetor eoollng th- ext-rnal surfae-s or th- r-actor;
withdrawing a portion ot the r-aetion mixtur- from the r-aetion zon- to an external cooler and reeyeling it to th~
reaetion zon-; ete ) being useq to malntain th~ r-action at th-Je t~mperatures in view Or the -exothermie nature of th-r-aetion Pr-f-rred reaetion t-mperatur-s are rrom about -15 C to +lS C and most pr~f-ried fron about -S C to +lS C G-nerally, relativQly high-r t-mp-ratures tend to produe- r-lativ-ly low moleeular weight polym-r Reaction pr--sur~s ar- gen-rally fro~ about 100 to 600 kPa, and more typieally fro~ about 200 to 400 kPa Th~ proee~s of th- pr-s-nt invention employ~
eith-r a tubular r-aetor or a ~tirr-d r-aetor ~pr-~-rably a eontlnuouJ typ- ~tirr-d r-actor) having two separate inlet m-anJ for introduetion of C4 feedstream and the organo-aluoinuu ehlorid- catalyst, the latter b~ing added alon- or in adoixtur- with a dilu-nt or solv-nt which is substantl~lly in-rt -under th~ pr-mixing and polym~rization eonditions Us-ful dilu-nts ~nclud- liquid saturated hydroearbons, -such as n-butan-, isobutane or mixtures of saturated butan~s ... ... ~... . .
h-- f--dstrea~ inl~t means- (~ g , a eonduit) is fitt~d with a d-~iee for inj-etion -(pref-rably for continuous inj-ction) of HCl (preferably gas-ous HCl) co-eatalyst into the~ C4 feedstr~a~ ae a point-prior to :
r-actor ntry ~h- HCl in~-ction point ~hould b- placed in th- C~ f--dstrea~ suffici-ntly in advance of the reactor entry to p-r~it ~ub~tantially compl-t- r-action of the HCl in th- f--d~tr-an with 1- and 2-but-n-s prior to the polymerization r-action zone Th- HCl 1~ b-li-ved to react with th- i~obutylon- to form t-butyl chlorid~ in th~
r-~ulting tr-at-d f--d~tr-am mixtur- Other organo chlorid-~ can also b- forn-d principally a 2-chlorobutane from r-action wlth th- 1- and 2-but-n-~ Or th- monomer f--d~tr-am Th- conc-ntration o~ tr-- HCl in th- treat-d te-d~tr-am mixtur- at th- point or r-actor ntry should ther-ror- be not gr-ater than about 1 0 ppm (parts per milllon) or less in order to achieve th- advantage of th~
inv-ntion Th- concentration of th~ HCl can b- d~ter~in-d by conv-ntional means for exampl- by analyzing th-feed~tr-a~ for organic chloride~ and free HCl u~ing a ga~
chromatograph equipped with a Hall detector Th- rate of mixing (and hence reaction) o~ the monon-rs and the HCl can b- convenisntly enhanc-d by us- o~ an in-lin- static (kin-tic) mi in the feed~tr~an conduit down~tream of th~
HCl in~-ction point (Alt-rnativ-ly or in addition th~
HCl can b- add-d to the C4 f--dstream prior to an in-lin-indirect h-at xchang-r to ~id in nixing th- HCl and th~
monom-r~ prior to th- r-actor by m-~ns o~ the turbulence gen-ra~-d in pa~-ing th-r-though ) To further enhance the rat- of mixing of the HCl and monom-r~ th- mixture of the HCl and th- C4 feQdstream is pr-r-rably ~aintained at a t-mp~r~ture of from at least about S C - g fron about 5 to 70 C
Pr-f-rably the organo-aluminu~ chloride cataly~t i not admixed with th- C4 r--d~tream prior to or during the inj-ction o~ the HCl (and prererably is not ad~ixed with th- C4 monom-r containing ~trea~ prior to the charging Or the treat-d feedstrea~ m$xtur- -into the reactor); otherwise uncontroll-d exother3ic poly~-rization .
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2~8769 12 - ' - will b- initlat-d unless extr-me mea~ures are taken (such a~ malnt~ining th- ad~ixtur- at a t-mperature below that which polymerizatlon proce-d~ ) Of course, the extent of such und-sired pr--polymerization will vary, dependinq on 'th- r-~id-nc- ti~e of th- admixtur- outsid- o'f the I -r-actor'~ r-action zon-' ~h-r-~or-, the tr-at-d f--dJtr-am mixture, containlng th- C4 ~onom-rs and th- pr--r-acted HCl, is pr-~-rably add-d (pr-~-rably contlnuou-ly) to the r-actor with organo-aluminum chloride cataly~t b-ing introduced into th- r-action mixture through a ~-parat- inl-t Th- proce~s Or this inv-ntion can b- practiced in a batchwi~e, semi-continuous or (as i~ pr-ferred) in a continuou~ manner Pre~-rably, th- tr-at-d fe-d~troam mixture, containing the C4 monomers and th- pr--teacted HCl, and the organo-aluminu~ chlorlde catalyst streams are add-d to the reaction zon- ~ubstantially simultaneously, at a rat- surrici-nt to maintain the sel~cted ratio o~ the monom-r~ and organo-aluminum cataly~t in th- liquid r-action mixtur- However, it is al~o po~sible to add th--- str-ams in a ~tag-wis- mann-r to a liquid reaction mixtur- .
Polym-rlzatlon occurs in an exothermic reaction by contacting- the two inco~ing streams in a cooled reactor with r-actor temp-ratur~, prefera~ly maintained at about -lS C to ~15 C For a continuou--typ- stirred reactor, ' av-rag r-actant residenc- tim- wilI generally be about lO
- to ~S ~inut-~ Th-re will generally b- employed o ool to 0 008 mol-~ ~preferably Srom about 0 002 to 0 006 moles) of organo-alu~inuc catalyst per mole of isobutylen- charged in th- fe-dstr-am and from about 25 to 300 ppm by weight (and ~pre~-rably from; about 'S0 to -150 ppm by weightj' of HCl ~~co-c~tal'y~t -pe-r''~part by w~ight of C4 ~r--dstream - - ~G~n-rally, the ~organo-aluminum chlorid- catalyst and HCl-cocataly'st~will bo employed in a ratio Or~ fro~ about l I
' _ 13 _ 2~787~9 to ~ part- by v-ight, pr-~orably ~rom about l 3 to 3 parts by w-ight, and mor- prer-rably ~ron about l 5 to 2 7 parts by w-ight, o~ th- organo-aluminum chlorid- catalyst per part by weight of the HCl-cocataly~t (calculated as HCl) Th- organo-aluminum chlorid- u~-ful in the process o~ thi~ inv~ntlon compris-~ at l-a~t on- co~pound o~ the fornula (I) (R)xAltclj3-x wh-r-ln R in Cl to C20 hydrocarbyl and x is an integ-r of ~rou l to 2 R can comprl~e branch-d or straight chain-d alkyl, cycloalkyl, aryl, alkaryl, ar~lkyl, alkenyl, and alkynyl, and hydrocarbyl (- g , Cl to ClO) sub~titut-d d-rivative~ thereo~ When R is alkyl, th-alkyl group can contain from l to 20, pref-rably'from l to lO, and most pre~rably ~rom l to 4, carbon atom~
Illu-trativ- Or such alkyl group- ar- m-thyl, ethyl, isopropyl, propyl, n-butyl, isobutyl, t-rtbutyl, p-ntyl, hexyl, heptyl, octyl, nonyl, d-cyl, dodecyl, tridecyl, t-tradecyl, octadecyl and th- like When R i~ alkenyl, th-alk-nyl group can contain rrom 2 to 20, pr-rQrably ~rom 2 to lO, and mo~t pr~erably rrom 2 to 4, carbon atoms Illu~trative of such alkenyl groups eth-nyl, isopropenyl, prop-nyl, n-but-nyl, i-obut-nyl, t-rtbut-nyl, pentonyl, h~x-nyl, h-pt-nyl, oct-nyl, nonenyl, d~cenyl, dodecenyl, trid-c-nyl, t-trad-cenyl, octad-c~nyl and the like When R
l~ ~lkynyl, th- alkynyl' group can contain ~rom 2 to 20, -pr r-rably fro~ 2 to lO,''and mo~t prQferably from 2 to 4, carbon ato~ Illustrativ- Or ~uch alkynyl groups ar-othynyl, isopropynyI,~propynyl, n-butynyl, isobutynyl, tertbutynyl, pentynyl, h-xynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, tridecynyl, t-tradecynyl,~ octad~cynyl and th~ like When R is~~'aryl, th- aryl group can contain `fro~ 6--to lO carbon ato~s'~Iliu trativ- ot such ary~ group~
ar~' ph-nyl, naphthyl and the like WhQn R i~ aikaryl, th~
alXaryl qroup can contain''from 7 to 20, preferably ;trom 7 .
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2 0 ~ 719 PCr/US91/02012 to 15, and most pr-rerably from 7 to 10, carbon atoms ~llu-tratlv- Or such alkaryl group~ ar- tolyl, xylyl, di(-thyl)phenyl, di(hexyl)ph-nyl, and the llke When R i~
aralkyl, th- aralkyl group can contain ~roDI ~ to 20,`
pref-rably from 7 to ~5, and mo-t prer-rably fro~ 7 to 10, carbon atomJ Illu~trative of ~uoh aralkyl groups ar~
b-nzyl, thylb-nzyl, ph-nylh-xyl, naphthylh-xyl, and the 1 lk- Wh-n R i- cycloalXyl, th- cycloalkyl group can contain frol- ~ to 20, pr-~-rably ~ro- 3 to 10, and most pr-f-rably ~rom 3 to 4, carbon aton~ ~llu-trativ- Or such cycloalkyl groups ar- cylcopropyl, cyclobutyl, cyclopentyl, cycloh-xyl, cycloheptyl, cyclooctyl, cyclononyl, cyclod-cyl, cyclododecyl, cyclotridQcyl, cyclotQtradecyl, cyclooctad-cyl and the lik- Illustrativ- or hydrocarbyl-substituted der; vatives o~ th- ~or-going group-ar- 2--thylcyclohexyl, cyclopropylph-nyl, ph-nylcylohexyl, and th- lik-lllustrative of us-rul organo-aluminum chloride~
ar- ( CN3 ) AlC12, ( CN3 ) 2AlCl, C2H5AlC12, ( C2H5 ) 2AlCl, ( CH3 ) 2CNAlC12, ~ ( CH3 ) 2 CH ~ 2AlCl, (C3H7) A1C12 ~ (C3H7) 2A1C1, CH3CN(CH3 ) A1C12 t CH3 CB ( CH3 ) ~ 2AlCl, ~ CN3 ) 3 CAlCl, ~ ( CB3 ) 3 C ~ 2Al Cl, C6N13AlC12, CSHllAlcl2, C1OH21AlCl2, and mixtures th-r-o~ Esp-cially preferred are C2HSAlC12 ~ (C2H5j 2AlCl and mixtures th~reof Ps~-r-rr-d ar- organo-aluminum chloride catalysts which are liguid- und-r th- reaction conditions Th- polybutene pNpar-d in accordance with this invention generally contain an av-rage of about 1 double bond por polymer chain and up to about 10 percent or the polymer chain~ may be satur~t-d -ferring r~ow to Figure 1 wher-in on- ~bodi~ent of th- process of thi~ invention i9 illustrated, a C4 . ., . .;: , ~. - -- - .
fe~dstre~ 2 is pa ~ed through a drying zon- 10 for removal of water (~ g, u4ing CaC12) ~he dri~d C4 stream 11 .,. ... . .1 WO 91/14719 PCI/I~S91/02012 is th-n pa~--d through tubular heat xchanger 12 for cooling o~ th- f--dstr-an to th- d--ir-d reaction t-mp-ratur- HCl ga~ is introduced via conduit 4 into conduit 11 up-tr-aDI o~ exchanger 12 The treated f-edstrea~ is th-n introduc-d via conduit 14 into reactor 20, th- fr-- HCl ContQnt ot th- thus-introduced feed 14 b-ing as d-scrib-d abov- I$quld organo-aluminu~ cataly~t ~- g, thyl alul~inum dichloride) ia introduced into r-actor 20 vla a s-parat- condult 18 A portion o~ the liquld r-actlon m-dlum ls withdrawn vla conduit 22 and pas~-d to xt-rnal h-at exchang-r 30 via conduit 24 for coollng o~ th- r-action liquid, and the cooled liquid is r-introduced to reactor -20 via conduit 26, to aid in r-action t-mperaturo control Poly~er r-action liguid is withdrawn ~rom the reactor 20 via conduit 22 and passed to conduit 28 and introduced into a ~irst ~rat-r washing zon-40 (to which water is introduced via conduit 42) to quench th- catalyst Th- aqueous and organic layers ar- allowed to s-parat-, and the upp-r aqu-ous lay-r is withdrawn via conduit 44 The washed organic lay-r containing the polyDI-r is withdrawn via conduit 46 and passed to an aqu-oua caustic contactlng zon- 50 ~or furth-r n-utrallzatlon and r~oval o~ catalyst resldue- Agu-ou~
caustic i~ introducQd via conduit 52, tho separated aqueous lay-r is withdrawn via conduit 54, and th- treated organic lay-r is pa---d fro~ zono 50 to a s-cond water washing zon-60, - for contacting with additional WatQr, introduced via conduit 62 A s-cond aqueou~ straam 64 is removed and a ~cond washed organic strea~ 60 containing the poly~ner which is preferably substantially free o~ the catalyst (- q , a~ -determined by a substantially neutral pH, and by an alu~inu3l1 ~content of less than about 10 wppm Al) is wlthdraw ~ a- strea~ 66 , ~ .
' WO91/14719 PCT/US91!02012 Polyn-r str-am 66 can then b~ passed to distlllation zon- 70 for r-mo~al Or C4 s (butanes and unr-acted but-n-s) as an ov-rh~ad product 72 The bottoms 74 can b- p~-d to a s-cond distillation zone 80 for re~oval oS th- light polym~r fraction a~ an s-cond overhead product 82 Th- r-sulting ~-cond bottom~ str-am 84 can th-n b- pass~d to a third dlstillation zon- 90 for r-moval oS wat-r th-r-Srom a~ a third overh~ad produet 92 if steam stripping ls nploy-d ln à prlor dl~tlllation, to ~orm the poly~-r product Jtr-am 94 ~ t will be und~rstood that r-actor 20 and contacting zon-s 40 S0 and 60 can b~ provided with suitabl~ agitators for mixing ot the str-ams so contacted and that the distillations in zon-~ 70 80 and 90 can b-aceomplished by m-ans known to those skilled ln th- art employing eonv-ntional distillatlon -quipm~nt and tQehniqu-s Th- proe-ss oS this invention ean b- operated eontinuou~ly or on a batchwise or s~mi-continuou- basis Th- polybuten- prepar-d in aceordanee with thi~
inv-ntion offers a number oS advantag-s over polybu~ene prQpar-d by prior art t-ehniques with r-sp-et to those prop-rties whleh ar- lmportant ~or lts u~e in making lubricating oil disp-r~ant typleally in a form of the r-aetion produet oS polyisobutenyl succinic anhydride wi~h polyamin-s or polyols ~ h- signlSlcant aspect is that th~ proeess of this inv-ntion p-r~it-s a mor~ pr~cis- control Or polybutenQ
produetion than h~retoforQ possibl~ ~n lubricating oil disp-rsant technology it is known that a relatively higher '' , ~
~ol~eular weight polybut~ne group provides dispersant additiv~ exhibiting better engin- p-rfor~anee in terms Or sludg~ di~~p rsaney and varnish d-posit inhibition How-v~r conv-ntional techniqu~s for ~anufacturing polybut~no ha~- h-ratofore be~n so~ewhat unsati~factory sinc- thQ viscosities of such rslatively high~r molecular .
4~19 PCT/US91!02012 weight materials increased proportional to the molecular weight, thereby causing a number of problems in both handling and manufacture of the dispersant products. These problems were due to the inherently broader nolecular weight distribution of~ such products. Here, the present process offers the advantage of controlling molecular weight in that a narrow molecular weight distribution is obtained which, for a given molecular weight range, results in a material having a relatively lower viscosity.
Molecular weight distribution of the product is less than 2, generally from about 1.40 to l.95, e.g., fro~ about 1.50 to l.90, preferably from about 1.60 to l.90, and more preferably from about l.70 to l.90. Preferred polybutenes are those having an ~n of about 900 to 2,500.
In the process of the present invention, a high degree of reactor controllability is achieved and the target specification of ~olecular weight and molecular weight distribution which is desired can be met through monitoring and adjùstment of incoming catalyst addition rate, such as the HCl addition rate relative to isobutene content, reactor temperature, residence time, feedstream introduction rate and the like. These parameters and the quality of the Sinished product can be monitored at close time intervals in the practice o~ the present invention.
Thus, for a given polybutene molecular weight desired, process conditions can be defined which will direct the process toward the target product.
The process of this invention also provides a number of product quality improvements in the polybutene product which are carried over to the quality of the dispersant additive ultimately produced. It has been --observed in accordance with this invention that ultra `violet absorption values for the product are relatively -`- iowèr than prior ~art product. Thesé analyses have been considered a measure of instability in dispersant products, probably related to the presence of moieties other than WO 91/147t9 PCl'/USgl!02012 ^
207~769 18 -polybu~-n- Al-o, th~ produet~ prepar-d in accordance to th- in~-ntion xhlblt relatlv-ly low-r chlorine l-vel which i-- a distlnet advantage sine- it doe~ t~nd to ~in~ize or liminat- xp-nsiv- elay flltratlon techniques commonly u--d ln ord-r to m-et naxlmum chlorln- sp-clfication in polybut-n--eontainlng products Anoth-r ~dvantag- of th- lnv-ntlon is a signlSleant r-duetlon ln th- guantlty ot ~o eall-d ~light nds~ ln th- polybut-n- produet Th-s- ar- polybut-nes in th- und-slrabl- ~n rang- of about 200 to S00 Th-proe-~a of thlJ inv-ntion ~inimiz-- th- quantity o~ the~e mat-rial- and th- yi-ld of desired produet in the high nol-eulaz weight range incroas-s accordingly Products Or thls inv-ntlon will generally contain l--s than about 35%
by w-ight of such low molecular w~lght polybut-ne~ in th-r-action mixtur- prior to produet Slnlshing Art-r stripping of volatiles and llght nd- Or ~n oS
l--s 300 and b-low, th- finlshed produet polybutene will eontain l-~s than 25% by w-ight of polybut-n- havlng an ~n b-low 500 Th- exact amount Or acc-ptable low mol-eular w-ight polybut-n- wlll vary dep-ndlng on produet viseosity " Th- t-ehnlqu- o~ addltlon Or HCl to th- ~-edJtrea~
in th- ab--ne- of organo-alumlnum chlorid- to form a pr--r-aet-d f--d~tr-am oSf-rs the further advantage of sub-tantially r-ducing th- presenc- oS chlorinated polybut-n- in th- Sinish-d produet Wh-n dispersant pr-eur-or, 1 - , polybut-n- succinic anhydride, is mad~
Sro~ polybut-ne, any produets Sr,om the reaction o~
ehlorlnat-d polybutene are dlstlnctly disadvantageous Any polymerization proeess which p-r~it~ fr~- ~Cl to ~xist in th- r-aetor has this problem ,and th- pres-nt invention ' ''`~uee-~-fully avolds it through u of tho pr--react-d f d~tr-am , , - --- !
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WO91/14719 PCT/USs1/02012 ~ n th- pr-~ent inv-ntion, HCl in~-cted into the f--d-tr-an r-aet~ quickly with l~obutyl-ne to produce t-butyl chlorid- which, upon ont~ring the reactor, functions ai a co-eataly~t wlth organo-aluninuu chloride to initiat- th- polyn-rization, th- organo-alu~inun chloride r-aetlng wlth th- t-butyl ehlorld- to foro thyl alu~inu~
triehlorld- and a t-butyl eation and th-reby lnltiating polyD-rlzation In eontra~t to thi-, wh-n HCl l~ us-d to pronot- organo-aluulnu~ ehlorld-, th- p-el-~ H+~tAlCl3 whleh i~ forn-d by r-aetlon b-tw-en HCl and organo-aluminu~
ehlorld- initiate~ th- polymerization Polyo-rizatlon in aeeordane- with th- present inventlon i~ ~or- ef~icient and provide- a d-gre- of proe-ss control and product quality not obtain~bl- with prior art proeedure- based upon th- u--of organo-aluminu~ chloride and HCl Polybut-n-~ prepar-d in aeeordane- with thi~
inv-ntion are particularly u~eful as a f--d~tock ~or the produetlon of iuprov-d lubrieating oll additlv-s, ineluding disp-rsant~ On- clas~ of u--~ul addltive ar- th-polybut-ne-~ubstltuted nono- and dlearboxyllc aeid-, anhydrlde~ and -t-rs whleh ean b- mad- by r-aetion of th-polybut-n- wlth a uonounsaturat-d mono- or dicarboxylle aeld, anhydrld- or ~t-r Sueh ~at-rial~ ean b- ~ade by eonventional u-thod~ wh-r-in wlth a uonounsaturated earboxylie r-aetant eompri~lng at least on- ue~ber s-leeted frou th- group eon~isting of (l) monounsaturated C4 to ClO diearboxylie aeid ~preferably wh-r-in (a) the earboxyl groups-are vicinyl,~ loeat-d on ad~aeent e~rbon ato~) and (b) at l~ast one, pr-ferably both, of ~aid ad~ae-nt earbon ato~s are part of said mono un~aturation~ (il) derivativ-a of (i) such a- anhydrides or~Cl to C5 aleohol derived mono- or~-di-e~ter~ of (i) i) ~onoun~aturated- C3 to Cl0 ~onocarboxylie-acid wherain th~ earbon-earbon double bond is eon~ugated to th-earboxy group,-i -, of the structur2 WO 91J14719 PCr/US91!02012 20787~9 o "
--C--C--C-:
and (iv) dor$vatlves o~ (iil) such a~ C1 to C5 alcohol d-riv-d monoe-ters Or (iii) Upon r-action with the polybut-n- tha monounsaturation Or th- nonounsaturated earboxylie r-aetant bocome~ saturated Thus for example mal-ie anhydrid- b-eome~ a polybut-n- sub-titut-d suecinlc anhydrld-, and aerylle acld boco~-s a polybutene ~ub-titut-d propionic aeid Typleally, rro~ about 0 7 to about 4 0 (- g ~ 0 8 to 2 C) pr-f-rably fron about 1 0 to about 2 0, and most pr-r-rably rrO~ about 1 1 to about 1 7 moles o~ said ~onoun~aturated carboxylic reaetant are charged to the r-actor p-r nole Or polybutene charg-d Normally not all Or tho polybuten- reaet~ with th- ~onoun~aturated carboxylic r-aetant and th- reaetion mixtur- wlll eontain unfunctionalizQd polybutene The unfunetlonaliz-d polybutena is typieally not r-~oved from th~ r-aetion mixtur- (b-cause sueh removal 1- difrieult and would b- comoereially in~easible) and tho product mixture ~tripp-d Or any monoun~aturat-d earboxylic r-actant i~
employ-d for Surth-r r-action with the amine or alcohol as doscrib-d horeinafter to ~aX- the disp-rsant Char~et-rlzatlon Or th- av-rtge numb-r o~ moles o~
monoun-aturat-d earboxylle r-actant which have rQact~d per ~ol- o~ polybut-ne charg-d to th- r~action- (wheth~r it has undergon- r-aetion or not) is derined herein as functlon~lity Said functionality is basad upon (i) d-t-roln~tion of th- saponification number of the resulting produet mixtur- -using potassium hydroxide and (ii) th~
nu~ber av~rag- molecular woight of the polybutene charged u-ing t-ehniqu~s w-l} known in th~ art Fun^ctionality i~
d~fin-d ~olely vith referenee- to the resuiting produet ~mixturo - Although the amount of~ said unfunctionalized polybut~n- eontainod- in the resulting product mixture can wos1/l47l9 PCTtUS91!02012 ` - 21 - 2 0 78 769 b- ub-equently mod~fi-d, l - incr-a~-d or decreased ~y t-chniqu-- ~nown in the art, such modl~ieations do not alt-r runetionality a~ da~ined above Tho ter~s "polybuten~ ~ub-tituted monoearboxylic acid material" and ~poly~utena ~ub~tituted dicarboxyllc acid mat-rial~ as used h-r-in ar- int-nd-d to r-f-r to th- produet mixture whether it ha- und-rgon- such modification or not Accordingly, th- runctionallty Or th- polybut-ne ~ub~titut-d mono- and dlearboxylle aeld mat-rlal will b-typleally at l-a-t about O S, pra~rably at l-a~t about 0 7, and mo-t pr-f-rably at l-ast about 0 9 and wlll vary typieally from about 0 5 to about 2 8 (- g , 0 6 to 2), pr-f-rably from about 0 8 to about l 4, and most preferably fro~ about 0 9 to about l 3 Exemplary of such monounsaturatad carboxylic reactants ar- fumaric aeid, itaconie aeld, mal-ic acid, malaie anhydride, chloromaloic aeld, chloromaleic anhydrld-, acrylic aeid, methacrylic acid, crotonic acid, einnamic acid, and lower alkyl ~e g , Cl to C4 alkyl) aeid at~rs of th- for-going, e g , methyl maleate, ethyl fumarat-, methyl fumarat-, etc Th- polybuten- can be react-d with th-monoun~aturat-d carboxylic r-actant by a vari-ty of ~ethods For xample, th- polybutene can be first halog-natod, chlorinated or brominated to about l to 8 wt %, pr-f-rably 3 to 7 wt % chlorin-, or bromin-, bas-d on -th- w-ight of polybutene, by passing th- chlorino or bromin- through the polybut-n- at a te~p-rature of 60 to 250 C, pr-f-rably llO to 160 C, ~ g 120 to 140 C, for - about o 5 to lO, preferably l to 7 hour~ Th- halog-nated ~ -polybut-ne may then b- r~act~d with su~ficient .. . .. - , , ~onounsaturat-d carboxylic r-aetant ~at lOO to 250 C, -- -usualIy about 180 to 235 C, for about 0 5 to lO,-e g 3 to 8 hours, so th- product obtained ~ill contain the d~sired nu~b~r of mol~s of th~ monounsaturated carboxylic reactant WO 91/147l9 Pcr/us9l/o2ol2 .
p-r mol- Or th- halog-nat-d polybut-n- Proce-s-~ o~ this g-n-ral typ- ar- taught in U S Pat-nts 3, 087, 436;
3, 172, 892; 3, 2~2, 746 and oth-rs Alt-rnativQly, the polybut-n- and th- monounsaturated carboxyllc reactant are Dlix-d and h-at-d whil- adding chlorino to the hot' mat-rial Proc-~ses of thls typ- ar- disclosed in U s Pat-nt~ 3,21S,707; 3,231,587 3,912,764; 4,110,349 4,234,435; and in U X 1,440,219 Alt-rnat-ly, th- polybut-n- and the oonoun-aturat-d carboxyllc r-actant can b- contactod at l- at-d t-mp-r~tur- to caus- a ther~al "-n-" reaction to tak- plac- Th-noal "-n-" r-actlon~ ha r- b--n h-retofor-d--crib-d in U S Patonts 3,361,673 and 3,401,118, the d$Jclosur-~ of which are horQby incorporated by rof-rence in th-$r ntirety Pr-f-rably, tho polybut-nos used in thi~ invention contain l-s- than S wt%, more pref-rably 1-~ than 2 wt%, and mo~t pr-r-rably les~ than 1 wt% or a polybutene fraction comprising polybut-n- mol-cules having a mol-cular w-ight Or l-s- than about 300, ag d-t-rmin-d by high t-~p-ratur- g-l p-rDIeation chromatography mploying the corr-sponding polybuten- calibration cur~- Such pre~errod polybut-n-~ hav- b--n round to p-rmit th- pr-paration o~
reaction products, particularly when employing IDalQic anhydrid- a~ th- unsaturat-d acid r-actant, with d-creas-d J-dim-nt In th- vent th- polybutene produced as d--cr~-d abov- contains greater than about 5 wt% Or such a low l~ol-cular w~ight polybut-n- ~raction, th- polybutene can b- rlr~t tr-ated by con~entional m-ans to remov~ the low mol-cular w~ight fraction to th- desired lev-l prior to initia'cing the ene reaction, and preferably prior to cont~cing tho polybutene w$th th- sel-cted ur~aturated c~rboxylic r ctant(s) For exampl-, ;th- polybut-n- can b-h-at-d, pr-ferably with inert gas (- g, nitrogen) ''-tripplng, at l-vated temperatur- under a roduced pr-ssure wos1/147l9 pcT/uss1/o2ol2 ~ 23 - 2078769 to volatiliz- the low ~ol-cular w-ight polybutene compon-nt- whlch can then b- r-nov-d ~ron the heat tr-atm-nt v----l The preclse te~p-ratur-, pr~gure and ti~- ~or such heat treatmQnt ean vary wid-ly ~epending on ~ueh faetor~ a~ as th- polybuten- nu~ber av-rage molecular w ight, th- amount of th- low molecular w ight fraction to b- r-mov-d and oth-r factor~ C-n-rally, a t-mperatur- o~
from about 60 to 250 C and a pr---ur- o~ ~ron about 0 1 to 1 0 atmo~ph-r-~ and a tim- o~ ~rou about 0 5 to 20 hour~
(- g , 2 to 8 hour~) wlll b- su~lel-nt ln this proc-~s, the s-l~ct-d polybutene and monounaaturat-d carboxylic r-actant and halog-n (e g , elhorin- gas), where employed, are eontaeted for a tim- and und-r eondltions efrective to form the de~lred polybuten-sub-tituted mono- or dicarboxylie acid naterial G-n-rally, th- polybutene and monounsaturated carboxylic r-aetant will b- eontacted in a polybuten- to unsaturated carboxylie re~etant mole ratio usually rrom about 1 1 to 1 10, and pre~erably from about 1 1 to 1 5, at an l-vated t-mp-rature, generally fron about 120 to 260 C, preferably rrOm about 160 to 240 C The mole ratio o~ halogen to monoun~aturated earboxylie reaetant charged will aiso ~ary and will gen-rally rang- ~rom about 0 5 1 to 4 1, and nore typieally rron about 0 7 1 to 2 1 (e g , from about 0 9 to 1 4 1) Th- r-aetion wlll be g-nerally carried out, with ~tirring ~or a ti~- o~ from about 1 to 20 hour~, preferably from ~bout 2 to 6 hour~
8y th- use Or halogen, about 6S to 95 wt ~ Or tho polybutene will normally reaet with the monounsaturated earboxylie aeid reaetant Upon carrying out a th-rmal reaetion without the U5Q of halogen or ~a catalyst, then u~ually only about 50 to 7S wt %- of th- polybutene will r-aet ~ Chlorination helps incre~s~-th~ r-activity ., ., ~ . . , . . . . . , . , ................. -- - . , .. . .. , . ., .. ~ . . ... .
wosl/l47l9 PCT/US91/02012 . .
- - 24 ~
2078769 Ir d--ired, a cataly-t or pronot-r for reaction Or th- polybut-n- and nonounsaturat-d carboxylic reaetant (wh-th-r the polybutene and nonounsaturat-d carboxylic r-actant ar- contact-d in th- pr---nc- or ab~enco Or halog-n (- g , chlorin-)) can b- ~ploy-d in th- reaction zon- Such cataly-t of pronot-rs inelud- alkoxides o~ Ti, Zr, V and Al, and nick-l salts (- g , N1 ac-toac-tonat- and Ni lodid-) which cataly-ts or prouot-r- wlll b- g-neraliy nploy-d in an auount of tron ~bout 1 to 5,000 ppu by w-lght, ba~-d on th- na~ of th- r-actlon n-d~um Th- r-actlon is pr-f-rably conduct-d in th-sub~tantlal ab--nc- f 2 and wat-r ~to avoid competing sld- r-actions), and to this end can b~ conducted in an atnosph-r- Or dry N2 gas or oth-r gas in-rt under th-r-action conditions She reactants can b- charg-d ~-parat-ly or tog-th-r as a mixtur- to th- reaction zon-, and the r-actlon can b- carrled out continuously, ~-ni-continuously or batchwis- Although not generally nec-~sary, th- reaction can b- carried out in th- pr-senc-o~ a liquid dilu-nt or solvont, e g , a hydrocarbon diluent ~uch as mln-ral lubricating oil, tolu-n-, xyl-n-, dichlorobenz-ne and th- lik- ~h- polybut-n- substituted nono- or dlcarboxy~ie acid uaterlal thu- form-d can b-reeov-r-d fron th- liquid r~actlon mixture, e g , a~ter str~pping th- r-actlon mixtur-, if desirod, with an inert ga- sueh a- N2 to r-mov- unroacted un~aturated carboxylic r-actant ~`
Dlsp-r~ants gen-rally comprise tha r-action product o~ polybutenyl succinic anhydrid- or the acid for~
th-r-o~ with ~onoamine~ or polya~in-~ having up to about 30 carbon ato~, hav~ng at least on~ primary or s~condary a~ino group such as the alkylen- polya~ines, particularly th- ethyl-n- polyanines, th- polyoxyalkylen-; anines, aro~atic and cycloaliphatic a~ine-, hydroxyamines, ~ono-aliphatic and di-aliphatic ~ubstitutod aoin~s User ', ... .. . . .,. " . , ~ , -t -` 2~7~769 dlJp-r~ant- ar- al-o ~or~-d by reactlng ~onohydric and polyhydrle aleohols wlth th- polybutenyl succinic anhydride or diacld provld-d from th- polybut-nea mad- in accordance with thia inv-ntion and pr-f-rr-d mat-rials are thus d-rlv-d from polyols having 2 to 6 OH groups eontaining up to about 20 earbon atoms sueh as th- alkan- polyols and alkyl-n- glyeol~ Also sultabl- ar- th- polyoxyalkylene aleohois sueh a polyoxy-thyl-n- alcohola and polyoxypropyl-n- aleohol~, ~onohydrie and polyhydrle ph-nolJ and naphthols, oth-r aleohol~ and amlno aleohols and th- llk- ~orat~d darivatlvas of th- ~or~going dl~p-rsant~ ar- also use~ul, esp~elally borated nitrogan eontalning disp-rsants rQsulting ~rom boratlon with boron oxld-, boron halida, boron aeids and st-r- to provid- 0 2 to 2 0 wt 5 boron in the disp-rsant M-tals and m-tal-eontaining eompounds can also for~ us-ful disper~ants and th--- ar~ eompounds capabl- of forming salt- with th-polyisobut-nyl sueeinie anhydrldo or aeid o~ th- pr-sent inv~ntlon and thi~ ineludes m-tals sueh as th- alkali m-tals, alkalin- oarth matals, zlne, cadmiu~, l-ad, eobalt, nlek-l, eopp-r, lron, ehro~ium, magn-sium and d-rivativ-~th-r-or sueh a~ oxld-J, earboxylat--, hal~d-s, pho~phat--, sulfat-s, earbonat-s, hydroxld-s and the llk-Also u--~ul ar- Mannieh ~as- eondensate di~p-rsants whar-ln-tha polybut n-s of thls ln~ention ara r-aet-d with a hydroxy-substitut~d aromatie compound (e g ph-nol) in an alkylation r-action to form a polybut-n--Jubstitut-d hydroxyaromatic eompound This polybutan~-~ubstituted hydroxyaro~atie co~pound~ean then b-eond-nsed in a Mannich Bas- reaetion with an~ amin- (e g , any oS th- mono- or polyamln~ d-acribed abov~) and an ald-hyd- (- g , formaldehyd~ Sueh alkylation and Mannieh Bas- r-aetion- can;bo -aecomplish-d u-ing--any of th-eonvsntional alkylation and Mannich ~as~- eondensation ~-t~od~
WO91/1471s PCT/US91/020t2 20787~9 ~ ubrlcating oil conpo~lt$on- will usually contain dlsp rsants in anounts of rrOn about l to 15 wt % ba~ed on th- ov-rall w-ight of th- compositlon ~ubricating oil eompo-itions wlll typically contain oth-r additives in eu~to~ary a~ounts to provid- th-ir nor~al attendant funetion- sueh a- m-tal d-t-rg-nt- or bas~c n-tal d-t-rg-nt, antl-w-ar additlv-s, antl-oxldant-, visco~ity modl~l-rs and th- ll~- Dl~p-r-ant- ar- conv-niently' paekag-d and di-p-ns-d in th- for~ o~ olution concontrat~s eontalning about 20 to S0 wt % di~p-rsant in ~ln-ral oils Th- lnv-ntion is furthar lllustrat-d by th-following xanpl-s (wherein parts are by w-lght UnlQsS
oth-rwis- indlcatod) which are not to be considered a~
li~itativ- or its ~cop-' A liquid C4 feedstrea~ conpos-d o~ 3a wt %
i~obut-n-, 30 wt % butene-1,4 wt ~ i~obutano, lo wt n-butan-, 18 wt % but-n--l and 1eSJ than 0 2% butadl-n- wa~
dri-d with CaCl2 and then introdueed into a r-actor feed lin- Sh- moistur- content'ln the feed aft-r irying was 1-SJ than 40 ppm Anhydrous gas-ous ~Cl was introduc-d into th- f-ed lln- in advanea of th- r~aetor ntry point to for~ a tr-at-d ~-adstr-am Sh- a~ount of NCl introduc-d into tho ~--d lin- was in th- rang- of S0 to 190 ppm by w-ight w$th av-rag- of about 74 ppm HCl by'weight Analy-i- of th- tr-at-d ~feQdstr-a~ show-d it to contain than O l'ppm~fr--'~Cl'and show-d that t-butylchloride ;was th- ~a~or organo-chloride in the tr-at-d feedstream, ~ ~ whleh~ was ~ound to have an ov-rall organo-chlorid-- eonc~ntration of 80 ppm-to 280 ppm by w-ight She-tr-ated f-odstr-a~ wa~-add-d-'to a;-continuoun stirr-d r-aetor at a - rat- of-~about' 13 4 cub~ meters- p-r hour Sh- r-actor -r-~d-nc- ~ti~-"was maintained at about 30 ~inute-, the reactor prossur- was maintained at about 2 1 ~ar, and the .
. ' , `~ ' ~
' :
.
W091/14719 PCT/US9t/02012 - 27 _ 2 0787 ~9 r-actor t-mp-rature was maintain-d at about 5 C
Ethylalumlnum dlchloride (EADC) was simultaneously added as a 15 wt% solutlon ln ISOPAR- ~, an in-rt hydrocarbon solvent, to provld- an amount Or EADC qual to 0 023 wt %
of the C4 fe-d~tr-am R~actlon product was withdrawn at a rat- corr-~ponding to the total f--d introduction rate Th- polym-rization r-action mixtur- was withdrawn from the r-actor and th- cataly~t r-~ov-d by th- st-p~ of water' washlng and aqu-ous caustlc tr-atment Or the wa~hed organic lay-r A c~ustlc tr-a~ed organlc lay-r wa- then obtained whlch waa sub~-ct-d to a s-cond wat-r washlng step Th-wa~h-d organic product was then stripped o~ unr-acted C4 hydrocarbons and oligo~er les8 than ~n~300 ,,to foro a finish-d polybutene product containing less,than 25 wt % o~ polybutene of Rn~soo or 1QSS.
97% Or isobutsn- was found converted to polybut-n-, and less than O l ppm o~ tree HCl remained ~n th- reactor vapor phase Th~ finished product polybutene was found to have a number av-rag- mol-cular weight of about 1300, an average viscoslty o~ 580 to 640 cSt at lOO C
and a mol-cular weight distribution of about l 80 to l 90 The stripped light oligomer was about 8 wt % of the total ~inlshed polybut-n- product Th- re~idue chlorlne in tho, fini~hed polybut-n- product was ~ound to b- about 50 ppm ~ y~
Th- proc-dure of Exampl~ l wa~ r-peated except that amount o~ HCl introduced into the feed lin- was in th-range of lSO to 220 ppm by weight with a~eragQ of about l90 ppm NCl by w-ight Analysi~- o~ the troated f-edstream ,~howed it to contain less than O l ppm ~ree HCl and ~howed !~! that t-butylchloride~,was the major organo-chloridQ in the tr-at-d r--dstr-am which wa~ found to have an ov-rall organo-chlorid- concentration Or l90 ppm to 320 ppm The reactor t~mperature was maintained at about lO C, th~
WO91/14719 PCT/US91/020t2 ~0787~9 28 -r-actor pr---ur- wa~ ~aintain~d at about 2 l Bar, a~d the r-actor r--id-nc- tim- was maintain-d at about 30 minutes Th- EADC ~olution ~a~ added to-provid- an amount of EADC
oqual to 0 030 wt % Or th- C4 ~--d~tr-a~ 98% of i~obut-ne was round to b- convert-d to poly~utene, and less than O l ppu of rr-e HCl r-mained in th- r-actor vapor pha~- Th- ~ini~h-d product polybut-n- wa- found to have a nuob-r a~-rag- mol-cular w-ight of about 9S0, an average vi-co-lty of l90 to 240 cSt at lOO C, and a molecuiar w-ight dl~tribution Or about l 80 to l 90 Th- r-sidue chlorin- in th- rini~hed polybuteno w~ tound to b- about 70 ppl-.
CoM~AI~vE ExA~ i 3~5 The procodurQ of Example l was repeated except that the cataly~t compri~ed ~inely dividod AlCl3 rather than EA~C, using the run condition~ described in Table I
belo~
Table I
Comparative Comparativ~ Comparative Exa~ 3 ExamDle 4 Ex~ 5 R-actor t-mp C l to 3 5 0 to -2 Wt % AlC13 in f~-d 08- 67 08- 67 08- 67 ~Cl coc~t, ppm in feed 150 100-200 70 I~obut-n- conv-r , 99 - 98 Mol wt , ~ - 1300 900 _ 950 Hal wt di~tr (MW/Mnj 1 90-l 95 1 90-l 95 l 90-l 95 Residue chlorin-, pp~ - lO0 _~lO0 - lO0 Visco~ity, cSt at lOO C 590-640 210 l90-247 .. , ,~ . . ~ - . . . . -. ., . .. . - .
: . .
WO9l/14719 PCT/US91/02012 Not- F-eds for Comp Exa~ples 3, 4 and 5;
Co~ponent (wt %l Com~ Exs 3 and 4 Com~ Ex 5 isobuteno 23 15-22 but-n~ 22 15-22 - saturat-d butan-- 55 --i~obutan- -- 4S-55 n-butan- -- 6-8 butadien- < 0 2 0 2 Total 100 100 COMPA~A~VE EX~MP~S 6-7 Th- proc-dure of Example 1 i~ repeated except that wat-r, rather than HCl, was employed as co-catalyst ~he condition~ of the reaction are described in ~able II
Table II
Comparative Comparative E~ e 6 Examplç 7 reactor te~p C lO 10 wt % EADC in f--d 0 085 o 082 H2O cocat, ppm in d 135 100 isobuten- con~-r , % 93 6 86 6 ~ol wt distr (MW/Mn) _ 2 1 _ 2 3 r-sidu- chlorine, pp~ 56 56 Not~
Feed rat- 12 M3/hr R-~ctor pressure 2 0 Bar Residence ti~e about 30 ~inutes - Cataly~t added as a 15% EADC solution in ISOPAR -L
~olv~nt " .
.- : .
2~787~9 Th- abov- data lllustrate th- simultaneou~ improved low chlorin- r-sldual conc-ntrations and narrower molecular w-ight distribution- achi-ved by the proc-s~ of the present -invention ov-r tho~- achi-v~d by u~e of the AlC13/HCl catalyst/co-catalyst sy~tem wh-n compar-d at the same nu~b~r av-rag- mol-cular w-ight product, and theso data furth-r illu~trate th- inprov-d mol-cular weight distribution achiev-d by the pr-~-nt process conpared to an EADC/wat-r cataly~t/co-c~taly~t ~y~t-n G-n-rally th- polybuten- products produced by the proc-~ o~ thi~ inv-ntion will contain 1-~ than about 100 wpp~, pr-f-rably 1- than about 75 wppm, and most preferably lecis than about 60 wppm chlorin- (as Cl) Th- principle~, preferrQd e~bodiments, and modes of operation of the present invention have be-n described in th- foregoing ~p-ci~ication The inv-ntion which i5 int-nd-d to be protected herein, however, is not to be constru-d as li~it-d to the particular for~ disclo~ed, I
sinc- th-se ar- to be regarded as illu~trativ- rather than restrictiv- Variations and changes may b- made by those Ci~ill-d in the art without departing ~rom the spirit o~ the inv-ntion ` ;'~ ;. '~' ,,: ;" ' . ,' .
Molecular weight distribution of the product is less than 2, generally from about 1.40 to l.95, e.g., fro~ about 1.50 to l.90, preferably from about 1.60 to l.90, and more preferably from about l.70 to l.90. Preferred polybutenes are those having an ~n of about 900 to 2,500.
In the process of the present invention, a high degree of reactor controllability is achieved and the target specification of ~olecular weight and molecular weight distribution which is desired can be met through monitoring and adjùstment of incoming catalyst addition rate, such as the HCl addition rate relative to isobutene content, reactor temperature, residence time, feedstream introduction rate and the like. These parameters and the quality of the Sinished product can be monitored at close time intervals in the practice o~ the present invention.
Thus, for a given polybutene molecular weight desired, process conditions can be defined which will direct the process toward the target product.
The process of this invention also provides a number of product quality improvements in the polybutene product which are carried over to the quality of the dispersant additive ultimately produced. It has been --observed in accordance with this invention that ultra `violet absorption values for the product are relatively -`- iowèr than prior ~art product. Thesé analyses have been considered a measure of instability in dispersant products, probably related to the presence of moieties other than WO 91/147t9 PCl'/USgl!02012 ^
207~769 18 -polybu~-n- Al-o, th~ produet~ prepar-d in accordance to th- in~-ntion xhlblt relatlv-ly low-r chlorine l-vel which i-- a distlnet advantage sine- it doe~ t~nd to ~in~ize or liminat- xp-nsiv- elay flltratlon techniques commonly u--d ln ord-r to m-et naxlmum chlorln- sp-clfication in polybut-n--eontainlng products Anoth-r ~dvantag- of th- lnv-ntlon is a signlSleant r-duetlon ln th- guantlty ot ~o eall-d ~light nds~ ln th- polybut-n- produet Th-s- ar- polybut-nes in th- und-slrabl- ~n rang- of about 200 to S00 Th-proe-~a of thlJ inv-ntion ~inimiz-- th- quantity o~ the~e mat-rial- and th- yi-ld of desired produet in the high nol-eulaz weight range incroas-s accordingly Products Or thls inv-ntlon will generally contain l--s than about 35%
by w-ight of such low molecular w~lght polybut-ne~ in th-r-action mixtur- prior to produet Slnlshing Art-r stripping of volatiles and llght nd- Or ~n oS
l--s 300 and b-low, th- finlshed produet polybutene will eontain l-~s than 25% by w-ight of polybut-n- havlng an ~n b-low 500 Th- exact amount Or acc-ptable low mol-eular w-ight polybut-n- wlll vary dep-ndlng on produet viseosity " Th- t-ehnlqu- o~ addltlon Or HCl to th- ~-edJtrea~
in th- ab--ne- of organo-alumlnum chlorid- to form a pr--r-aet-d f--d~tr-am oSf-rs the further advantage of sub-tantially r-ducing th- presenc- oS chlorinated polybut-n- in th- Sinish-d produet Wh-n dispersant pr-eur-or, 1 - , polybut-n- succinic anhydride, is mad~
Sro~ polybut-ne, any produets Sr,om the reaction o~
ehlorlnat-d polybutene are dlstlnctly disadvantageous Any polymerization proeess which p-r~it~ fr~- ~Cl to ~xist in th- r-aetor has this problem ,and th- pres-nt invention ' ''`~uee-~-fully avolds it through u of tho pr--react-d f d~tr-am , , - --- !
. .. . . . . . . - .. .. .
WO91/14719 PCT/USs1/02012 ~ n th- pr-~ent inv-ntion, HCl in~-cted into the f--d-tr-an r-aet~ quickly with l~obutyl-ne to produce t-butyl chlorid- which, upon ont~ring the reactor, functions ai a co-eataly~t wlth organo-aluninuu chloride to initiat- th- polyn-rization, th- organo-alu~inun chloride r-aetlng wlth th- t-butyl ehlorld- to foro thyl alu~inu~
triehlorld- and a t-butyl eation and th-reby lnltiating polyD-rlzation In eontra~t to thi-, wh-n HCl l~ us-d to pronot- organo-aluulnu~ ehlorld-, th- p-el-~ H+~tAlCl3 whleh i~ forn-d by r-aetlon b-tw-en HCl and organo-aluminu~
ehlorld- initiate~ th- polymerization Polyo-rizatlon in aeeordane- with th- present inventlon i~ ~or- ef~icient and provide- a d-gre- of proe-ss control and product quality not obtain~bl- with prior art proeedure- based upon th- u--of organo-aluminu~ chloride and HCl Polybut-n-~ prepar-d in aeeordane- with thi~
inv-ntion are particularly u~eful as a f--d~tock ~or the produetlon of iuprov-d lubrieating oll additlv-s, ineluding disp-rsant~ On- clas~ of u--~ul addltive ar- th-polybut-ne-~ubstltuted nono- and dlearboxyllc aeid-, anhydrlde~ and -t-rs whleh ean b- mad- by r-aetion of th-polybut-n- wlth a uonounsaturat-d mono- or dicarboxylle aeld, anhydrld- or ~t-r Sueh ~at-rial~ ean b- ~ade by eonventional u-thod~ wh-r-in wlth a uonounsaturated earboxylie r-aetant eompri~lng at least on- ue~ber s-leeted frou th- group eon~isting of (l) monounsaturated C4 to ClO diearboxylie aeid ~preferably wh-r-in (a) the earboxyl groups-are vicinyl,~ loeat-d on ad~aeent e~rbon ato~) and (b) at l~ast one, pr-ferably both, of ~aid ad~ae-nt earbon ato~s are part of said mono un~aturation~ (il) derivativ-a of (i) such a- anhydrides or~Cl to C5 aleohol derived mono- or~-di-e~ter~ of (i) i) ~onoun~aturated- C3 to Cl0 ~onocarboxylie-acid wherain th~ earbon-earbon double bond is eon~ugated to th-earboxy group,-i -, of the structur2 WO 91J14719 PCr/US91!02012 20787~9 o "
--C--C--C-:
and (iv) dor$vatlves o~ (iil) such a~ C1 to C5 alcohol d-riv-d monoe-ters Or (iii) Upon r-action with the polybut-n- tha monounsaturation Or th- nonounsaturated earboxylie r-aetant bocome~ saturated Thus for example mal-ie anhydrid- b-eome~ a polybut-n- sub-titut-d suecinlc anhydrld-, and aerylle acld boco~-s a polybutene ~ub-titut-d propionic aeid Typleally, rro~ about 0 7 to about 4 0 (- g ~ 0 8 to 2 C) pr-f-rably fron about 1 0 to about 2 0, and most pr-r-rably rrO~ about 1 1 to about 1 7 moles o~ said ~onoun~aturated carboxylic reaetant are charged to the r-actor p-r nole Or polybutene charg-d Normally not all Or tho polybuten- reaet~ with th- ~onoun~aturated carboxylic r-aetant and th- reaetion mixtur- wlll eontain unfunctionalizQd polybutene The unfunetlonaliz-d polybutena is typieally not r-~oved from th~ r-aetion mixtur- (b-cause sueh removal 1- difrieult and would b- comoereially in~easible) and tho product mixture ~tripp-d Or any monoun~aturat-d earboxylic r-actant i~
employ-d for Surth-r r-action with the amine or alcohol as doscrib-d horeinafter to ~aX- the disp-rsant Char~et-rlzatlon Or th- av-rtge numb-r o~ moles o~
monoun-aturat-d earboxylle r-actant which have rQact~d per ~ol- o~ polybut-ne charg-d to th- r~action- (wheth~r it has undergon- r-aetion or not) is derined herein as functlon~lity Said functionality is basad upon (i) d-t-roln~tion of th- saponification number of the resulting produet mixtur- -using potassium hydroxide and (ii) th~
nu~ber av~rag- molecular woight of the polybutene charged u-ing t-ehniqu~s w-l} known in th~ art Fun^ctionality i~
d~fin-d ~olely vith referenee- to the resuiting produet ~mixturo - Although the amount of~ said unfunctionalized polybut~n- eontainod- in the resulting product mixture can wos1/l47l9 PCTtUS91!02012 ` - 21 - 2 0 78 769 b- ub-equently mod~fi-d, l - incr-a~-d or decreased ~y t-chniqu-- ~nown in the art, such modl~ieations do not alt-r runetionality a~ da~ined above Tho ter~s "polybuten~ ~ub-tituted monoearboxylic acid material" and ~poly~utena ~ub~tituted dicarboxyllc acid mat-rial~ as used h-r-in ar- int-nd-d to r-f-r to th- produet mixture whether it ha- und-rgon- such modification or not Accordingly, th- runctionallty Or th- polybut-ne ~ub~titut-d mono- and dlearboxylle aeld mat-rlal will b-typleally at l-a-t about O S, pra~rably at l-a~t about 0 7, and mo-t pr-f-rably at l-ast about 0 9 and wlll vary typieally from about 0 5 to about 2 8 (- g , 0 6 to 2), pr-f-rably from about 0 8 to about l 4, and most preferably fro~ about 0 9 to about l 3 Exemplary of such monounsaturatad carboxylic reactants ar- fumaric aeid, itaconie aeld, mal-ic acid, malaie anhydride, chloromaloic aeld, chloromaleic anhydrld-, acrylic aeid, methacrylic acid, crotonic acid, einnamic acid, and lower alkyl ~e g , Cl to C4 alkyl) aeid at~rs of th- for-going, e g , methyl maleate, ethyl fumarat-, methyl fumarat-, etc Th- polybuten- can be react-d with th-monoun~aturat-d carboxylic r-actant by a vari-ty of ~ethods For xample, th- polybutene can be first halog-natod, chlorinated or brominated to about l to 8 wt %, pr-f-rably 3 to 7 wt % chlorin-, or bromin-, bas-d on -th- w-ight of polybutene, by passing th- chlorino or bromin- through the polybut-n- at a te~p-rature of 60 to 250 C, pr-f-rably llO to 160 C, ~ g 120 to 140 C, for - about o 5 to lO, preferably l to 7 hour~ Th- halog-nated ~ -polybut-ne may then b- r~act~d with su~ficient .. . .. - , , ~onounsaturat-d carboxylic r-aetant ~at lOO to 250 C, -- -usualIy about 180 to 235 C, for about 0 5 to lO,-e g 3 to 8 hours, so th- product obtained ~ill contain the d~sired nu~b~r of mol~s of th~ monounsaturated carboxylic reactant WO 91/147l9 Pcr/us9l/o2ol2 .
p-r mol- Or th- halog-nat-d polybut-n- Proce-s-~ o~ this g-n-ral typ- ar- taught in U S Pat-nts 3, 087, 436;
3, 172, 892; 3, 2~2, 746 and oth-rs Alt-rnativQly, the polybut-n- and th- monounsaturated carboxyllc reactant are Dlix-d and h-at-d whil- adding chlorino to the hot' mat-rial Proc-~ses of thls typ- ar- disclosed in U s Pat-nt~ 3,21S,707; 3,231,587 3,912,764; 4,110,349 4,234,435; and in U X 1,440,219 Alt-rnat-ly, th- polybut-n- and the oonoun-aturat-d carboxyllc r-actant can b- contactod at l- at-d t-mp-r~tur- to caus- a ther~al "-n-" reaction to tak- plac- Th-noal "-n-" r-actlon~ ha r- b--n h-retofor-d--crib-d in U S Patonts 3,361,673 and 3,401,118, the d$Jclosur-~ of which are horQby incorporated by rof-rence in th-$r ntirety Pr-f-rably, tho polybut-nos used in thi~ invention contain l-s- than S wt%, more pref-rably 1-~ than 2 wt%, and mo~t pr-r-rably les~ than 1 wt% or a polybutene fraction comprising polybut-n- mol-cules having a mol-cular w-ight Or l-s- than about 300, ag d-t-rmin-d by high t-~p-ratur- g-l p-rDIeation chromatography mploying the corr-sponding polybuten- calibration cur~- Such pre~errod polybut-n-~ hav- b--n round to p-rmit th- pr-paration o~
reaction products, particularly when employing IDalQic anhydrid- a~ th- unsaturat-d acid r-actant, with d-creas-d J-dim-nt In th- vent th- polybutene produced as d--cr~-d abov- contains greater than about 5 wt% Or such a low l~ol-cular w~ight polybut-n- ~raction, th- polybutene can b- rlr~t tr-ated by con~entional m-ans to remov~ the low mol-cular w~ight fraction to th- desired lev-l prior to initia'cing the ene reaction, and preferably prior to cont~cing tho polybutene w$th th- sel-cted ur~aturated c~rboxylic r ctant(s) For exampl-, ;th- polybut-n- can b-h-at-d, pr-ferably with inert gas (- g, nitrogen) ''-tripplng, at l-vated temperatur- under a roduced pr-ssure wos1/147l9 pcT/uss1/o2ol2 ~ 23 - 2078769 to volatiliz- the low ~ol-cular w-ight polybutene compon-nt- whlch can then b- r-nov-d ~ron the heat tr-atm-nt v----l The preclse te~p-ratur-, pr~gure and ti~- ~or such heat treatmQnt ean vary wid-ly ~epending on ~ueh faetor~ a~ as th- polybuten- nu~ber av-rage molecular w ight, th- amount of th- low molecular w ight fraction to b- r-mov-d and oth-r factor~ C-n-rally, a t-mperatur- o~
from about 60 to 250 C and a pr---ur- o~ ~ron about 0 1 to 1 0 atmo~ph-r-~ and a tim- o~ ~rou about 0 5 to 20 hour~
(- g , 2 to 8 hour~) wlll b- su~lel-nt ln this proc-~s, the s-l~ct-d polybutene and monounaaturat-d carboxylic r-actant and halog-n (e g , elhorin- gas), where employed, are eontaeted for a tim- and und-r eondltions efrective to form the de~lred polybuten-sub-tituted mono- or dicarboxylie acid naterial G-n-rally, th- polybutene and monounsaturated carboxylic r-aetant will b- eontacted in a polybuten- to unsaturated carboxylie re~etant mole ratio usually rrom about 1 1 to 1 10, and pre~erably from about 1 1 to 1 5, at an l-vated t-mp-rature, generally fron about 120 to 260 C, preferably rrOm about 160 to 240 C The mole ratio o~ halogen to monoun~aturated earboxylie reaetant charged will aiso ~ary and will gen-rally rang- ~rom about 0 5 1 to 4 1, and nore typieally rron about 0 7 1 to 2 1 (e g , from about 0 9 to 1 4 1) Th- r-aetion wlll be g-nerally carried out, with ~tirring ~or a ti~- o~ from about 1 to 20 hour~, preferably from ~bout 2 to 6 hour~
8y th- use Or halogen, about 6S to 95 wt ~ Or tho polybutene will normally reaet with the monounsaturated earboxylie aeid reaetant Upon carrying out a th-rmal reaetion without the U5Q of halogen or ~a catalyst, then u~ually only about 50 to 7S wt %- of th- polybutene will r-aet ~ Chlorination helps incre~s~-th~ r-activity ., ., ~ . . , . . . . . , . , ................. -- - . , .. . .. , . ., .. ~ . . ... .
wosl/l47l9 PCT/US91/02012 . .
- - 24 ~
2078769 Ir d--ired, a cataly-t or pronot-r for reaction Or th- polybut-n- and nonounsaturat-d carboxylic reaetant (wh-th-r the polybutene and nonounsaturat-d carboxylic r-actant ar- contact-d in th- pr---nc- or ab~enco Or halog-n (- g , chlorin-)) can b- ~ploy-d in th- reaction zon- Such cataly-t of pronot-rs inelud- alkoxides o~ Ti, Zr, V and Al, and nick-l salts (- g , N1 ac-toac-tonat- and Ni lodid-) which cataly-ts or prouot-r- wlll b- g-neraliy nploy-d in an auount of tron ~bout 1 to 5,000 ppu by w-lght, ba~-d on th- na~ of th- r-actlon n-d~um Th- r-actlon is pr-f-rably conduct-d in th-sub~tantlal ab--nc- f 2 and wat-r ~to avoid competing sld- r-actions), and to this end can b~ conducted in an atnosph-r- Or dry N2 gas or oth-r gas in-rt under th-r-action conditions She reactants can b- charg-d ~-parat-ly or tog-th-r as a mixtur- to th- reaction zon-, and the r-actlon can b- carrled out continuously, ~-ni-continuously or batchwis- Although not generally nec-~sary, th- reaction can b- carried out in th- pr-senc-o~ a liquid dilu-nt or solvont, e g , a hydrocarbon diluent ~uch as mln-ral lubricating oil, tolu-n-, xyl-n-, dichlorobenz-ne and th- lik- ~h- polybut-n- substituted nono- or dlcarboxy~ie acid uaterlal thu- form-d can b-reeov-r-d fron th- liquid r~actlon mixture, e g , a~ter str~pping th- r-actlon mixtur-, if desirod, with an inert ga- sueh a- N2 to r-mov- unroacted un~aturated carboxylic r-actant ~`
Dlsp-r~ants gen-rally comprise tha r-action product o~ polybutenyl succinic anhydrid- or the acid for~
th-r-o~ with ~onoamine~ or polya~in-~ having up to about 30 carbon ato~, hav~ng at least on~ primary or s~condary a~ino group such as the alkylen- polya~ines, particularly th- ethyl-n- polyanines, th- polyoxyalkylen-; anines, aro~atic and cycloaliphatic a~ine-, hydroxyamines, ~ono-aliphatic and di-aliphatic ~ubstitutod aoin~s User ', ... .. . . .,. " . , ~ , -t -` 2~7~769 dlJp-r~ant- ar- al-o ~or~-d by reactlng ~onohydric and polyhydrle aleohols wlth th- polybutenyl succinic anhydride or diacld provld-d from th- polybut-nea mad- in accordance with thia inv-ntion and pr-f-rr-d mat-rials are thus d-rlv-d from polyols having 2 to 6 OH groups eontaining up to about 20 earbon atoms sueh as th- alkan- polyols and alkyl-n- glyeol~ Also sultabl- ar- th- polyoxyalkylene aleohois sueh a polyoxy-thyl-n- alcohola and polyoxypropyl-n- aleohol~, ~onohydrie and polyhydrle ph-nolJ and naphthols, oth-r aleohol~ and amlno aleohols and th- llk- ~orat~d darivatlvas of th- ~or~going dl~p-rsant~ ar- also use~ul, esp~elally borated nitrogan eontalning disp-rsants rQsulting ~rom boratlon with boron oxld-, boron halida, boron aeids and st-r- to provid- 0 2 to 2 0 wt 5 boron in the disp-rsant M-tals and m-tal-eontaining eompounds can also for~ us-ful disper~ants and th--- ar~ eompounds capabl- of forming salt- with th-polyisobut-nyl sueeinie anhydrldo or aeid o~ th- pr-sent inv~ntlon and thi~ ineludes m-tals sueh as th- alkali m-tals, alkalin- oarth matals, zlne, cadmiu~, l-ad, eobalt, nlek-l, eopp-r, lron, ehro~ium, magn-sium and d-rivativ-~th-r-or sueh a~ oxld-J, earboxylat--, hal~d-s, pho~phat--, sulfat-s, earbonat-s, hydroxld-s and the llk-Also u--~ul ar- Mannieh ~as- eondensate di~p-rsants whar-ln-tha polybut n-s of thls ln~ention ara r-aet-d with a hydroxy-substitut~d aromatie compound (e g ph-nol) in an alkylation r-action to form a polybut-n--Jubstitut-d hydroxyaromatic eompound This polybutan~-~ubstituted hydroxyaro~atie co~pound~ean then b-eond-nsed in a Mannich Bas- reaetion with an~ amin- (e g , any oS th- mono- or polyamln~ d-acribed abov~) and an ald-hyd- (- g , formaldehyd~ Sueh alkylation and Mannieh Bas- r-aetion- can;bo -aecomplish-d u-ing--any of th-eonvsntional alkylation and Mannich ~as~- eondensation ~-t~od~
WO91/1471s PCT/US91/020t2 20787~9 ~ ubrlcating oil conpo~lt$on- will usually contain dlsp rsants in anounts of rrOn about l to 15 wt % ba~ed on th- ov-rall w-ight of th- compositlon ~ubricating oil eompo-itions wlll typically contain oth-r additives in eu~to~ary a~ounts to provid- th-ir nor~al attendant funetion- sueh a- m-tal d-t-rg-nt- or bas~c n-tal d-t-rg-nt, antl-w-ar additlv-s, antl-oxldant-, visco~ity modl~l-rs and th- ll~- Dl~p-r-ant- ar- conv-niently' paekag-d and di-p-ns-d in th- for~ o~ olution concontrat~s eontalning about 20 to S0 wt % di~p-rsant in ~ln-ral oils Th- lnv-ntion is furthar lllustrat-d by th-following xanpl-s (wherein parts are by w-lght UnlQsS
oth-rwis- indlcatod) which are not to be considered a~
li~itativ- or its ~cop-' A liquid C4 feedstrea~ conpos-d o~ 3a wt %
i~obut-n-, 30 wt % butene-1,4 wt ~ i~obutano, lo wt n-butan-, 18 wt % but-n--l and 1eSJ than 0 2% butadl-n- wa~
dri-d with CaCl2 and then introdueed into a r-actor feed lin- Sh- moistur- content'ln the feed aft-r irying was 1-SJ than 40 ppm Anhydrous gas-ous ~Cl was introduc-d into th- f-ed lln- in advanea of th- r~aetor ntry point to for~ a tr-at-d ~-adstr-am Sh- a~ount of NCl introduc-d into tho ~--d lin- was in th- rang- of S0 to 190 ppm by w-ight w$th av-rag- of about 74 ppm HCl by'weight Analy-i- of th- tr-at-d ~feQdstr-a~ show-d it to contain than O l'ppm~fr--'~Cl'and show-d that t-butylchloride ;was th- ~a~or organo-chloride in the tr-at-d feedstream, ~ ~ whleh~ was ~ound to have an ov-rall organo-chlorid-- eonc~ntration of 80 ppm-to 280 ppm by w-ight She-tr-ated f-odstr-a~ wa~-add-d-'to a;-continuoun stirr-d r-aetor at a - rat- of-~about' 13 4 cub~ meters- p-r hour Sh- r-actor -r-~d-nc- ~ti~-"was maintained at about 30 ~inute-, the reactor prossur- was maintained at about 2 1 ~ar, and the .
. ' , `~ ' ~
' :
.
W091/14719 PCT/US9t/02012 - 27 _ 2 0787 ~9 r-actor t-mp-rature was maintain-d at about 5 C
Ethylalumlnum dlchloride (EADC) was simultaneously added as a 15 wt% solutlon ln ISOPAR- ~, an in-rt hydrocarbon solvent, to provld- an amount Or EADC qual to 0 023 wt %
of the C4 fe-d~tr-am R~actlon product was withdrawn at a rat- corr-~ponding to the total f--d introduction rate Th- polym-rization r-action mixtur- was withdrawn from the r-actor and th- cataly~t r-~ov-d by th- st-p~ of water' washlng and aqu-ous caustlc tr-atment Or the wa~hed organic lay-r A c~ustlc tr-a~ed organlc lay-r wa- then obtained whlch waa sub~-ct-d to a s-cond wat-r washlng step Th-wa~h-d organic product was then stripped o~ unr-acted C4 hydrocarbons and oligo~er les8 than ~n~300 ,,to foro a finish-d polybutene product containing less,than 25 wt % o~ polybutene of Rn~soo or 1QSS.
97% Or isobutsn- was found converted to polybut-n-, and less than O l ppm o~ tree HCl remained ~n th- reactor vapor phase Th~ finished product polybutene was found to have a number av-rag- mol-cular weight of about 1300, an average viscoslty o~ 580 to 640 cSt at lOO C
and a mol-cular weight distribution of about l 80 to l 90 The stripped light oligomer was about 8 wt % of the total ~inlshed polybut-n- product Th- re~idue chlorlne in tho, fini~hed polybut-n- product was ~ound to b- about 50 ppm ~ y~
Th- proc-dure of Exampl~ l wa~ r-peated except that amount o~ HCl introduced into the feed lin- was in th-range of lSO to 220 ppm by weight with a~eragQ of about l90 ppm NCl by w-ight Analysi~- o~ the troated f-edstream ,~howed it to contain less than O l ppm ~ree HCl and ~howed !~! that t-butylchloride~,was the major organo-chloridQ in the tr-at-d r--dstr-am which wa~ found to have an ov-rall organo-chlorid- concentration Or l90 ppm to 320 ppm The reactor t~mperature was maintained at about lO C, th~
WO91/14719 PCT/US91/020t2 ~0787~9 28 -r-actor pr---ur- wa~ ~aintain~d at about 2 l Bar, a~d the r-actor r--id-nc- tim- was maintain-d at about 30 minutes Th- EADC ~olution ~a~ added to-provid- an amount of EADC
oqual to 0 030 wt % Or th- C4 ~--d~tr-a~ 98% of i~obut-ne was round to b- convert-d to poly~utene, and less than O l ppu of rr-e HCl r-mained in th- r-actor vapor pha~- Th- ~ini~h-d product polybut-n- wa- found to have a nuob-r a~-rag- mol-cular w-ight of about 9S0, an average vi-co-lty of l90 to 240 cSt at lOO C, and a molecuiar w-ight dl~tribution Or about l 80 to l 90 Th- r-sidue chlorin- in th- rini~hed polybuteno w~ tound to b- about 70 ppl-.
CoM~AI~vE ExA~ i 3~5 The procodurQ of Example l was repeated except that the cataly~t compri~ed ~inely dividod AlCl3 rather than EA~C, using the run condition~ described in Table I
belo~
Table I
Comparative Comparativ~ Comparative Exa~ 3 ExamDle 4 Ex~ 5 R-actor t-mp C l to 3 5 0 to -2 Wt % AlC13 in f~-d 08- 67 08- 67 08- 67 ~Cl coc~t, ppm in feed 150 100-200 70 I~obut-n- conv-r , 99 - 98 Mol wt , ~ - 1300 900 _ 950 Hal wt di~tr (MW/Mnj 1 90-l 95 1 90-l 95 l 90-l 95 Residue chlorin-, pp~ - lO0 _~lO0 - lO0 Visco~ity, cSt at lOO C 590-640 210 l90-247 .. , ,~ . . ~ - . . . . -. ., . .. . - .
: . .
WO9l/14719 PCT/US91/02012 Not- F-eds for Comp Exa~ples 3, 4 and 5;
Co~ponent (wt %l Com~ Exs 3 and 4 Com~ Ex 5 isobuteno 23 15-22 but-n~ 22 15-22 - saturat-d butan-- 55 --i~obutan- -- 4S-55 n-butan- -- 6-8 butadien- < 0 2 0 2 Total 100 100 COMPA~A~VE EX~MP~S 6-7 Th- proc-dure of Example 1 i~ repeated except that wat-r, rather than HCl, was employed as co-catalyst ~he condition~ of the reaction are described in ~able II
Table II
Comparative Comparative E~ e 6 Examplç 7 reactor te~p C lO 10 wt % EADC in f--d 0 085 o 082 H2O cocat, ppm in d 135 100 isobuten- con~-r , % 93 6 86 6 ~ol wt distr (MW/Mn) _ 2 1 _ 2 3 r-sidu- chlorine, pp~ 56 56 Not~
Feed rat- 12 M3/hr R-~ctor pressure 2 0 Bar Residence ti~e about 30 ~inutes - Cataly~t added as a 15% EADC solution in ISOPAR -L
~olv~nt " .
.- : .
2~787~9 Th- abov- data lllustrate th- simultaneou~ improved low chlorin- r-sldual conc-ntrations and narrower molecular w-ight distribution- achi-ved by the proc-s~ of the present -invention ov-r tho~- achi-v~d by u~e of the AlC13/HCl catalyst/co-catalyst sy~tem wh-n compar-d at the same nu~b~r av-rag- mol-cular w-ight product, and theso data furth-r illu~trate th- inprov-d mol-cular weight distribution achiev-d by the pr-~-nt process conpared to an EADC/wat-r cataly~t/co-c~taly~t ~y~t-n G-n-rally th- polybuten- products produced by the proc-~ o~ thi~ inv-ntion will contain 1-~ than about 100 wpp~, pr-f-rably 1- than about 75 wppm, and most preferably lecis than about 60 wppm chlorin- (as Cl) Th- principle~, preferrQd e~bodiments, and modes of operation of the present invention have be-n described in th- foregoing ~p-ci~ication The inv-ntion which i5 int-nd-d to be protected herein, however, is not to be constru-d as li~it-d to the particular for~ disclo~ed, I
sinc- th-se ar- to be regarded as illu~trativ- rather than restrictiv- Variations and changes may b- made by those Ci~ill-d in the art without departing ~rom the spirit o~ the inv-ntion ` ;'~ ;. '~' ,,: ;" ' . ,' .
Claims
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing low molecular weight polybutene having an Mn in the range of 700 to 3,000 and a molecular weight distribution of about 1.40 to 1.90 from a feedstream mixture of C4 hydrocarbons containing at least 6% by weight isobutylene in a stirred reaction zone maintained at a temperature of -50°C to +30°C
in the presence of organo-aluminum chloride catalyst, which comprises:
(a) injecting HCl in an amount of from 25 to 300 parts by weight per one million parts by weight of said feedstream mixture into said feedstream mixture, in the absence of said organo-aluminum chloride catalyst and to completely react said injected HCl with isobutylene, thereby producing a treated feedstream mixture which contains less than 1.0 ppm free HCl;
(b) simultaneously introducing said treated feedstream mixture and said organo-aluminum chloride catalyst as separate streams into said reaction zone;
(c) contacting said introduced treated feedstream mixture and said introduced catalyst in the reaction zone for a time to form a polymerization reaction mixture containing said polybutene;
(d) withdrawing said polymerization reaction mixture from said reaction zone; and (e) recovering said polybutene product from said withdrawn polymerization reaction mixture.
2. The process of claim 1 wherein said catalyst comprises at least one member selected from the group consisting of compounds of the formula:
(R)xAl(Cl)3-x wherein R is C1 to C20 hydrocarbyl and x is an integer of from 1 to 2.
3. The process of claim 2 wherein said R group comprises branched or straight chained alkyl having from 1 to 10 carbon atoms.
4. The process of claim 3 wherein said R group comprises C1 to C4 alkyl.
5. The process of claim 4 wherein said alkyl group comprises at least one member selected from the group Consisting of methyl, ethyl, isopropyl, propyl, n-butyl, isobutyl, and tert-butyl.
6. The process of claim 1 wherein said catalyst comprises at least one member selected from the group c o n s i s t i n g o f (C H 3 )A l C l 2, (C H 3 )2 A l C l, C 2 H 5 A l C l 2 , (C 2 H 5 ) 2 A l C l , ( C H 3 ) 2 C H A l Cl 2 , [ ( C H 3 ) 2 C H ] 2 A l C l , ( C 3 H 7 ) A l C l 2 , ( C 3 H 7 ) 2 A l C l , C H 3 C H ( C H 3 ) A l C l 2 , [ C H 3 C H ( C H 3 ) ) 2 A l C l , ( C H 3 ) 3 C A l C l , [ ( C H 3 ) 3 C ] 2 A l C l , C 6 H 1 3 A l C l 2 , C 5 H 1 1 A l C l 2, and C 1 0 H 2 1 A l C l 2 .
7. The process of claim 1 wherein said catalyst comprises C 2 H 5 A l C l 2 , ( C 2 H 5 ) 2 A l C l and mixtures thereof.
8. The process of claim 1 wherein there is employed 0.001 to 0.008 moles of ethyl aluminum dichloride catalyst per mole of said isobutylene.
9. The process of claim 1 wherein the temperature range is about -15'°C to +15°C.
10. The process of claim 1 wherein the polybutene has an Mn of about 900 to about 2,500.
11. The process of claim 8 wherein the ethyl aluminum dichloride catalyst is added in an amount of from about 0.002 to 0.006 moles per mole of said isobutylene.
12. The process of claim 1 wherein the ethyl aluminum dichloride and HCl are added in a wt:wt ratio of from about 1 to 4.
13. The process of claim 1 wherein said reaction is effected in a stirred tank reactor.
14. The process of claim 1 wherein said reaction is effected in a tubular reactor.
15. A continuous process for preparing low molecular weight polybutene having an Mn in the range of about 700 to about 3,000 and a molecular weight distribution of about 1.50 to 1.90 from a feedstream mixture of C4 hydrocarbons containing at least about 6%
by weight isobutylene in a stirred reaction zone maintained at a temperature of about -15°C to +15°C in the presence of organo-aluminum chloride catalyst, which comprises:
(a) injecting HCl in an amount of from about 25 to 300 parts by weight per one million parts by weight of said feedstream mixture into said feedstream mixture, in the substantial absence of said organo-aluminum chloride catalyst and under conditions sufficient to substantially completely react said injected HCl with isobutylene, thereby producing a treated feedstream mixture which contains not greater than about 1.0 ppm free HCl:
(b) simultaneously continuously introducing said treated feedstream mixture and said organo-aluminum chloride catalyst as separate streams into said reaction zone;
(c) contacting said introduced treated feedstream mixture and said introduced catalyst in the reaction zone for a time and under conditions sufficient to form a polymerization reaction mixture containing said polybutene;
(d) continuously withdrawing said polymerization reaction mixture from said reaction zone; and (e) recovering said polybutene product from said withdrawn polymerization reaction mixture.
16. The process of claim 15 wherein said withdrawn polymerization reaction mixture is quenched with aqueous alkali and said polybutene product is recovered from said quenched polymerization reaction mixture.
17. The process of claim 15 wherein said catalyst comprises at least one member selected from the group consisting of compounds of the formula:
(R)xAl(Cl)3-x wherein R is C1 to C20 hydrocarbyl and x is an integer of from 1 to 2.
18. The process of claim 17 wherein said R group comprises branched or straight chained alkyl having from 1 to 10 carbon atoms.
19. The process of claim 18 wherein said R group comprises C1 to C4 alkyl.
20. The process of claim 19 wherein said alkyl group comprises at least one member selected from the group consisting of methyl, ethyl, isopropyl, propyl, n-butyl, isobutyl, and tert-butyl.
21. The process of claim 15 wherein said catalyst comprises at least one member . selected from the group consisting of ( C H 3 ) A l C 1 2 , ( C H l ) 2 A l C l, C 2 H 5 A l C l 2 , ( C 2 H 5 ) 2 A l C l , ( C H 3 ) 2 C H A l C l 2 , [ ( C H 3 ) 2 C H ] 2 A l C l , ( C 3 H 7 ) A l C l 2 , ( C 3 H 7 ) 2 A l C l , C H 3 C H ( C H 3 ) A l C 1 2 , ( C H 3 C H ( C H 3 ) ] 2 A l C l , ( C H 3 ) 3 C A l C l , [ ( C H 3 ) 3 C ] 2 A l C l , C 6 H 1 3 A l C l 2 , C 5 H 1 1 A l C l 2 , and C10H21AlCl2.
22. The process of claim 16 wherein said catalyst comprises C 2 H 5 A l C l 2 , ( C 2 H 5 ) 2 A l C l and mixtures thereof.
23. The process of claim 15 wherein the organo-aluminum catalyst is introduced into said recation zone in an amount of from about 0.001 to 0.008 moies per mole of said isobutylene.
24. The process of claim 15 wherein the polybutene product has a viscosity of 190 to 250 centistokes at 100°C.
25. The process of claim 15 wherein the polymerization temperature is from about -5°C to +15°C.
26. The process of claim 16 wherein the polybutene has an Mn of 900 to 2,500.
27. The process of claim 16 wherein the organo-aluminum chloride is added in admixture with C4 hydrocarbons.
28. The process of claim 19 wherein the organo-aluminum chloride catalyst comprises a member selected from the group consisting of (alkyl)x aluminum (chloride)3-x, wherein the alkyl group contains from 1 to 4 carbon atoms, and x is an integer of from 1 to 2.
29. The process of claim 16 wherein the organo-aluminum chloride catalyst comprises ethyl aluminum dichloride.
30. The process of claim 31 wherein said ethyl aluminum dichloride is added in admixture with C4 hydrocarbons.
31. The process of claim 32 wherein the polymerization temperature is from -5°C to +15°C.
32. The process of claim 33 wherein the polybutene has an Mn of 900 to 2,500.
33. The process of claim 34 wherein said ethyl aluminum dichloride catalyst is introduced into said reaction zone in an amount of from 0.002 to 0.006 moles per mole of said isobutylene.
34. The process of any of claims 1 to 33 wherein the polybutene product has a molecular weight distribution of about 1.40 to 1.70.
35. The process of claim 35 wherein said withdrawn polymerization reaction mixture is quenched with aqueous alkali and said polybutene product is recovered from said quenched polymerization reaction mixture.
36. The process of any of claims 1 to 33 wherein the polybutene product has a molecular weight distribution of about 1.80 to 1.90.
37. The product produced by the process of
claim 1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US49913490A | 1990-03-26 | 1990-03-26 | |
US499,134 | 1990-03-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2078769A1 true CA2078769A1 (en) | 1991-09-27 |
Family
ID=23983971
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2078769 Abandoned CA2078769A1 (en) | 1990-03-26 | 1991-03-25 | Polybutene process |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0522057A1 (en) |
JP (1) | JPH05506048A (en) |
BR (1) | BR9106284A (en) |
CA (1) | CA2078769A1 (en) |
MX (1) | MX25062A (en) |
WO (1) | WO1991014719A2 (en) |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5250076B2 (en) * | 1974-04-23 | 1977-12-21 | ||
US4146692A (en) * | 1977-08-25 | 1979-03-27 | Exxon Research & Engineering Co. | Process and product for manufacture of elastomeric co- or terpolymers |
DE3368936D1 (en) * | 1982-08-13 | 1987-02-12 | Exxon Research Engineering Co | Process for preparing polyisobutylene |
DE3300155A1 (en) * | 1983-01-05 | 1984-07-05 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE CONTINUOUS PRODUCTION OF ISOBUTYLENE POLYMERISATS |
US4952739A (en) * | 1988-10-26 | 1990-08-28 | Exxon Chemical Patents Inc. | Organo-Al-chloride catalyzed poly-n-butenes process |
US4935576A (en) * | 1988-11-25 | 1990-06-19 | Exxon Chemical Patents Inc. | Polybutene process |
-
1991
- 1991-03-25 EP EP19910907532 patent/EP0522057A1/en not_active Withdrawn
- 1991-03-25 CA CA 2078769 patent/CA2078769A1/en not_active Abandoned
- 1991-03-25 JP JP91507360A patent/JPH05506048A/en active Pending
- 1991-03-25 BR BR919106284A patent/BR9106284A/en not_active Application Discontinuation
- 1991-03-25 WO PCT/US1991/002012 patent/WO1991014719A2/en not_active Application Discontinuation
- 1991-03-26 MX MX2506291A patent/MX25062A/en unknown
Also Published As
Publication number | Publication date |
---|---|
MX25062A (en) | 1993-06-01 |
WO1991014719A3 (en) | 1991-11-14 |
EP0522057A1 (en) | 1993-01-13 |
WO1991014719A2 (en) | 1991-10-03 |
JPH05506048A (en) | 1993-09-02 |
BR9106284A (en) | 1993-04-13 |
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