CA2189073A1 - Prestripped polymer used to improve koch reaction dispersant additives - Google Patents

Abstract

The invention pertains to the prestripping of polymer prior to use in the Koch reaction for making dispersant additives. It was djscovered that by prestripping or removal of light hydrocarbon andunreacted monomer from the polymer before the carbonylation step of the Koch reaction, the amount of light ester impurities generated was minimized. Light ester is an undesirable byproduct that adversely affects the recycle of the catalyst from the functionalization step of the Koch reaction.

Description

2 1 Pj 9 ~J 7 3 r p~FcTRlppEn POLY~FR. usFn TO ~IPROVE E~Ol~T RF~CTION
DICPFR.c~NT ADDITIVES
The present invention is directed to an improvéd polyrner ~ ' process for the Koch reaction. The Koch reaction relates to reacting at least one carbon-carbon double bond with carbon monoxide in the presence of an acidic catalyst and a nucleophilic trapping agent to form a carbonyl or Illio~albvllJ functional group, 10 and derivatives thereo The term "polymer" is used herein to refer to materials comprising large molecules built up by the repetition of small, simple chemical units. In a ~JIIu~,rlbull polymer those units are ~ du~ ly formed of hydrogen amd carbon. Polymers are defned by average properties, and in the context of the invention polymers have a 15 number average molecular weight (Mn) of at least 500. Light polymer used herein refers to polymer having less than 300 molecular weight (e.g., 48 to 288).
The term "hJdlu~,r~Lu.." is used herein to refer to non polymeric compounds comprising hydrogen and carbon having uniform properties such as molecular weight.
However, the term 'I~JdIU~bUIII~ is not intended to exclude mixtures of such 20 compounds which ;..li~ are ~ ,; d by such uniforrn properties. Light '~, '.u~ ù,~ as used herein refers to compounds having a carbon number between C4 and C24, inclusive.
WO-A-9535330, Amidation of Ester r ~ ~ Polymers;
WO-A-9535324, Batch Koch C~bU~J Process; WO-A-9535329, Derivatives of 25 Polyamines With One Primary Amine and Secondary or Tertiary- Amines;
WO-A-9535325, Continuous Process for Production of F~lnrtir~n~l;7~i Olefins and;WO-A-9535328, Tllhrir~ting Oil Dispersants Derived from Heavy r~lr all contain related subject maKer as indicated by their titles.
WO-A-9413709, discloses reactions of a polymer having at least 30 one ethylenic double bond reacted via a Koch mechanism to form carbonyl or thio carbonyl group-containing compounds which may ~ ly be derivatized. The polyrners react with carbon monoxide in the presence of arl acid catalyst or a catalyst preferably complexed with the ' ,'"
trapping agent. A preferred catalyst is BF3 and preferred catalyst complexes include 35 BF3.H2O and BF3 complexed with 2,4- " ' ' ~r ~ The starting polymerreacts AMENDED SHEET

2 ~ ~9~73 Woss/3s326 P~ s ~o/4 with carbon monoxide at point of l ~liu~ to form either iso- or neo- acyl groupswith the ""~ l~ o~ trapping agent, e.g., with water, alcohol (preferably a substituted phenol) or thiol to form respectively a carboxylic acid, carboxylic ester group, or thio ester.
The '' ' ' polymer can be ~ ly derivatized with inter alia an amine, aicohol, amino alcohol, etc. to form a dispersant additive for lubricant The present invention relates to stripping (e.g., removal) of light polymer (e.g., lower molecular weight fiactions) on alternatively light hrllul~albull from the polymer 10 prior to the reaction described above. The removal ûf the light polymer results in a surprising reduction in the amount of heretofor unwanted by-products, such as light polymer esters formed during the Koch reaction.
The presence of light polymer ester may possibly adversely affect the ~,~. r.~, I.IAI.. ~ of the final dispersant product. Hence, it is desirable to eliminate or 15 minimize the content of light polymer present in the Koch reaction.
The presence of light polymer ester has a second deleterious effect on the process described above. In one ~ iJ~ ' of the process, the r polymer must be treated prior to the derivatization step. The crude ester produced in the carbonylation contains inter alia the r ' ~' ~ polymer, impurities, and in the 20 case of the use of the preferred IIL_~ 'i 1 '~ trapping agent, unreacted 2,4-d;~,l iu~u~ ol (DCP). Using, for example, CV~IlJuldL;ull~ the fi.- .~ ,. d polymer is treated to remove the unreacted DCP. The distillate is coliected and fractionally distilled to recover and recycle the unreacted DCP. However, some of the impurities, especially the light polymer esters that boil close to DCP as well as light chlorinated 25 çl-mrolmllc are also inadvertently recycled. In a continuous process, such as in a commercial facility, the recycle stream of desired unreacted DCP will be quicklysaturated with the undesirable cu..l~Jo~ such as the light esters.
Since the CVa~Ju~dLiOI~ is a single stage operation, an equilibrium level of undesirable c.c, l..J ~ (e.g., light esters) will build up in the process stream. In order 30 tû maintain low impurity levels the distillate may have to be purged (e.g., discarded).
This is very costly from the standpoint of the loss of valuable chemicals but also firom an ~ ' standpoint. Thus, it is very desirable to minimize the amount of light ester present in the crude ester fed to the evaporators. This is r ~ ~' ' I by minimizing the introduction of light ester precursors such as C4 to C24 olefins in the 35 polymer feed to the r, l;l I;~AI;OI~ process.
Both llYdlU~ Ull comro~n~1C. as well as polymeric rr~mrol~n~lC, have been reacted to form carboxyl group-containing compounds and their derivatives.

~ l ~9D73 wo95135326 r~ J.... lol4 Carboxyl groups have the general formula -CO-OR, where R can be H, a h~J~u~ llJJ group, or a substituted hydroearbyl group.
The synthesis of carboxyl group-containing ~ r ~ from olefinic l~ydlu~ l enmro~-n~lc, carbon monoxide, and water in the presence of metal 5 carboxyls is disclosed in references such as N. Bahrmann, Chapter 5, Koch Reactions, "New Synthesis with Carbon Monoxide" J. Falbe; Springer-Verlag, New York, 1980.
Hydl~ having olefinic double bonds react in two steps to form carboxylic acid-containing çn~ro~ e In the first step an olefin compound reacts with an acid catalyst and carbon monoxide in the absence of water. This is followed by a second 10 step in which the i..tc. ' formed during the first step undergoes hydrolysis or alcoholysis to form a carboxylic acid or ester. An advantage of the Koch reaction is that it can occur at moderate ICllI~,.dLUlC~ of-20C to +80C, and pressures up to 100 bar.
The Koch reaction can occur at double bonds where at least one carbon of the 15 double bond is di-substituted to form a "neo" acid or ester R' -C-COOR

(where R' and R" are not hydrogen).
The Koch reaction can also occur when both carbons are mono-substituted or one is ' ' and one is llncl~hctjtllt~rl to form an "iso" acid (i.e. -R'HC-25 COOR). Bahrmann et al.. discloses isobutylene converted to isobutyric acid via aKochtype reaction.
US-A-2831877 discloses a multi-phase, acid catalyzed, two-step process for the carboxylation of olefins with carbon monoxide.
Complexes of mineral acids in water with BF3 have been studied to carboxylate 30. olefins. US-A-3349107 discloses processes which use less than a ~ ;..,. l.icamount of acid as a catalyst. Examples of such complexes are H2O.BF3.H2O, H3PO4.BF3.H2O and HF BF3 H2 EP-A-0148592 relates to the production of carboxylic acid esters and/or carboxylic acids by catalyzed reaction of a polyrner having carbon-carbon double35 bonds, carbon monoxide and either water or an alcohol, optionally in the presence of oxygen. The catalysts are metals such as palladium, rhodium, ruthenium, iridium, and cobalt in ~..~...l.;., -~;o ~ with a copper compound, in the presence of a protonic acid such as llydl~ ' ' ;c acid. A preferred polymer is polyisobutene, which may have at least 80% ol its carbon-carbon double bonds in the form of terminal double bonds. Liquid ~ J 9 0 7 ~
,UL~ having a number average molocular weight in the range of from 200 to 2,500, preferably up to 1,000 are described US-A~927892 relates to reacting a poiymer or copolymer of a conjugated diene, at least part of which is formed by 1,2 pGI,~ , with carbon monoxide 5 and water and/or aicohol in the presence of a catalyst prepared by combining apaiiadium compound, certain ligands and/or acid except ll~d.l ' ' ,, acids having a pKa of less than 2. Useful Lewis acids include BF3.
Aithough there are disclosures in the a~t of olefinic h, ~uc~ubul~
at the carbon-carbon double bond to form a carboxyiic acid or derivative thereof via 10 Kochtype chemistry, there is no disclosuro that polymers containing carbon-carbon double bonds, including terminai olefinie bonds, either secondary or tertiary type olefinie bonds, could be ~u~,~,c~ruily reacted via the Koch mechanism. The Koch process is particularly useful to maice neo acid and neo ester r ~ ~ polymer.
The present invention is useful to improve the Koch process. Known cataiysts used to 15 ~ u~l~L~: low molecular weight olefinie l~ ilU~UbUII~ by the Koch mechanism were found to be unsuitable for use with polymerie materiai. Specific cataiysts have been found which can result in the formation of a carboxylic acid or ester at a carbon-carbon double bond of a polymer. Koch chemistry affords the advantage of the use of moderate ~...I.. .A~I... - and pressures, by using highly acidic catalysts and/or eareful 20 control of SUMMARY OF THE rNVENTIO~
The present invention is a process for improving the polyrner used in the Koch process for maicing dispersant additives comprising: removing light l~y ilUC~uiJull 25 fractions from said polymer prior to the ~ vllyh~liull step. The present invention is aiso a r ~- ~ h~ u~ ~ubu~ polymer wherein the polymer baekbone has Mn 2 500, 1~ .. ,. I l.... ~;, -1;.." is by groups of the formula -Co-Y-R3 wherein Y is O or S, and R3 is X l~ u~ub~ :, substituted l~ u~ yl, aryl, or substituted aryl, and wherem at least 50 mole % of the funetionai groups are attached to a tertiary carbon atom of the 30 polymer backbone, prepared by a process comprising: removing light IIY~iIUI~AIiJUII
from said polymer prior to r ~ The present invention is aiso a - ~ ~ }l~ u~luboll polymer wherein the polymer backbone has Mn 2 500, the polymer backbone prior to r - ~ containing less than 1 weight percent ilU~ ~UiJUII of carbon number C24 and below, r ~ is by groups of the 35 formula -Co-Y-R3 wherein Y is O or S, and R3 is lI, l~y~ilu~,~iJyl, substituted }I~ilU~,~Ui~, aryl, or substituted aryl, and wherein at least 50 mole % of the functionai groups are attached to a tertiary carbon atom of the polymer backbone.
AMENDED SHE~T

wo ss/3~326 2 1 ~ 9 Q 7 3 P~ o ~
The present invention relates to an improved process for ~ ~ ' of ilJ~ilu~.ali~ull polymer wherein the polymer backbone has IVin > 500 and light polymer (e.g., less than 300 molecular weight) has been removed prior to ~ ' and the '` ' is by groups of the formula:
-Co-Y-R3 wherein Y is O or S, and either R3 is H, hydrocarbyl and at least 50 mole % of the functionai groups are attached to a tertiary carbon atom of the polymer backbone or R3 is aryl, substituted aryl or substituted hydrocarbyl.
Thus the ~i ' ' polymer may be depicted by the formula:
POLY (CRlR2 Co-Y-R3)n (I) wherein POLY is a lly ilU1~11iJU.. pûlymer backbone having a number average molecular weight of at least 500, n is a number greater than 0, Rl, R2 and R3 may be the same or different and are each H, hydrocarbyl with the proviso that either Rl and R2 are selected such that at ieast 50 mole percent of the -CRIR2 groups wherein 15 bothRlandR2arenûtH,orR3isarylsubstitutedarylorsubstitutedll~i,u~.~..i,yl.
As used herein the term "Il~J~u~ yl" denotes a group having a carbon atom directly attached to the remainder of the molecule and having ~,., ' ly h,i.u~.~..l,un character within the context of this invention and includes polymeric Iy ilu~liJyl radicals. Such radicals include the following.
(l) Hydrocarbon groups; that is, aliphatic, (e.g., alkyl or alkenyl), alicyclic(e.g., cycloalkyl or o ~,10~ ,.yl), aromatic, aliphatic- and aiicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic radicais, and the like, as well as cyclic radicals wherein the ring is completed through another portion of the molecule (that is, the two indicated ~ may together form a cyclic radical). Such radicals are known to thûse skilled in the art; examples include methyl, ethyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, eicosyl, cyclûhexyl, phenyl and naphthyl (all isomers being included).
(2) Substituted 1. 1 ~i. u~, i,u.~ groups; that is, radicals containing non^
lly ilu~liJull cllhstitllPntc which, in the context of this invention, do not alter ~vl~iulll;llallLly hydrocarbon character ofthe radical Those skilled in the art will be aware of suitable ~ (e.g., halo, hydroxy, aikoxy, carbalkoxy, nitro, alkylsulfoxy).

(3) Hetero groups; that is, radicals which, while ~
lly ilu~ ull in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms will be apparent to those .. . . ..

~ I ~ q Q 7 ~ ~ .
~ ~ . . .. .. . .

skilled in the art and include, for example, nitrogen particularly non-basic nitrogen which would deactivate the Koch catalyst, oxygen and Sulfur.
In general, no more than three ~ or hetero atoms, and preferably no 5 more than one, will be present for each l0 carbon atoms in the llyllu~,Ou~v~-based radical. Polymeric hydrocarbyl radicals are those derived from l~J~u~ o~ polymers, which may be substituted and/or contain hetero atoms provided that they remain v~ ull in character. The 1~ J polymer may be dertved from a IIJJ~u~,albu~ polymer comprising non-aromatic carbon-carbon double bond, 10 also referred to as an olefinicaDy, ' bond, or an ethylenic double bond. The polymer is 5 ' ' at that double via a Koch reaction to form the carboxylic acid, carboxylic ester or thio acid or thio ester. It is the object of this invention to remove light polymer or light hJIlu~,~bu~l from the polymer prior to the 5 - .- -Koch reactions have not heretofore been applied to polymers having number average molecular weights greater than 50û. The l~Jlu~,~bvn polymer preferably has Mn greater than l,000. In the Koch process a polymer having at least one ethylenic double bond is contacted with an acid catalyst and carbon monoxide in the presence of a ' .' ' trapping agent such as water or alcohol. The catalyst is preferably a classical Broensted acid or Lewis acid catalyst. These catalysts are ~
from the transition metal catalysts of the type described in the prior art. The Koch reaction, as applied in the process of the present invention, may result in good yields of 5 ' ' polymer, even 90 mole % or greater.
POLY, in general formula I, represents a h~J~u~l~vll polymer backbone having Mn of at least 500 with the polymer less than 300 molecular weight removel, and/or Gght IIJIIU~bOn of carbon number C4 to C24. Mn may be deternnined by available techniques such as gel permeation ~L~VIII~I~U~ (GPC). POLY is derived from u .~ , lrd polymer.
Polvmers The polymers which are useful in the Koch reaction are polymers containing at least one carbon-carbon double bond (olef~nic or ethylenic) ~ Thus, the maxi~num number of functional groups per polymer chain is limited by the number of double bonds per chain. Such polymers have been found to be receptive to Koch - ' to form carboxylic acids or derivatives thereof, using the catalysts and trapping agents of the present invention. It is known that polymers useful AMEIIDED SHEET

~ 3 9 ~73 ~ ~ ~ ~ r ~ r ~ ~

in the Koch process include polymers containing a flictrihl~tinn of molecular weights ~WD).
Useful polyrners ~ in the ICoch reaction include polyalkenes including l~ull.u~,vl.~ ., copolymer (used .,1.5..,~bl,~ with ill~ )ol~..l.,.) and mixtures.
5 IIulllu~vl~ ,.D and il~ JVI,~ll~.D include those derived from pVI,~ ,.1'5bl~, olefin monomers of 2 to 16 carbon atoms; usually 2 to 6 carbon atoms.
Particular reference is made to the alpha olefin polymers made using organo metailic cvu~ A particularly preferred class of polymers are ethylene alpha olefin copolymers such as those disclosed in US-A-5017299. The 10 polymer ~ ;n~ can be terminal, internal or both. Preferred poly~ners haYe terminal ~ , preferahly a high degree of terminal Il ~ Terminal is the UllD5LUldL;UIl provided by the last monomer unit located in the pûlymer. The ll ~rll..Al;.~ can be located anywhere in this terminal monomer unit.
Terminal olefinic groups include vinylidene l...~ . RaRbC=CH2;
15 olefin . , RaRbC=CRCH; vinyl ~ , RaHC=CH2; 1,2~
terminal, 5L;Vn, RaHC=CHRb; 5nd tetra-substituted terminal ., --I"~AI~
RaRbC=CRCRd. At least one of Ra and Rb is a polyrneric group of the present invention, and the remaining Rb, Rc and Rd are h,~ u~,5~bv~ groups as defined vith respect to R, Rl, R2, and R3 above.
Low molecular weight polymers, also referred to herein as dispersant range molecular weight polymers, are polymers having Mn less than 20,000, preferably 500 to 20,000 (e.g. 1,000 to 20,000), more preferably 1,500 to 10,000 (e.g. 2,000 to8,000) and most preferably from 1,500 to 5,000. The number average molecular weights are measured by vapor phase osmometry. Low molecular weig~ht polymers are useful in forming dispersants for lubricant additives.
Medium molecuiar weight polymers Mn's ranging from 20,000 to 200,000, preferably 25,000 to 100,000; and more preferably, from 25,000 to 80,000 are usefui for viscosity index improvers for lubricating oil ~ , adhesive coatings, tacicifiers and seaiants. The medium Mn can be determined by membrane osmometry.The higher molecular weight materiais have Mn of greater than 200,000 and can range to 15,000,000 with specific -,.,l.~.l:, '~ of 300,000 to 10,000,000 and more specificaily 500,000 to 2,000,000. These polymers are useful in polymeric and blends including elastomeric, ~" "l.~.- l ;. ,. .~ Higher molecular weight materiais having Mnls of from 20,000 to 15,000,000 can be measured by gel permeation ~,L.l O , ' y with uniYersal caiibration, or by light scattering. Thevaiues of the ratio Mw/Mn, referred to as molecular weight flictrihlltifln (MWD) are AMENDED SHEET
,t not critical. HoweYer, a typical rninimum Mw/Mn value of 1.1-2.0 is preferred with typical ranges of I . I up to 4.
The olefin monomers are preferably poly ' '- terminal olefins; that is, olefins . ~ - ;I by the presence in their structure of the group -R-C=CH2, where5 R is H or a llyd~u~,~lJull group. However, pUIy~ internal olefin monomers (sometimes referred to in the patent literature as medial olefins) ~ I by the presence within their structure of the group:
C-C=C-C

can also be used to forln the ~GI~.'' When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are il~ V4.1...1~. For this invention, a pa~ticular ~ulyl~ .,l olefin monomer which can be classified as both a terminat olefin and an internal olefin, will be deemed a 15 terminal olefin. Thus, pentadiene-1,3 (ie., piperylene) is deemed to be a terminal olefin.
While the ~GI~1.dkc~ generally are h~l.u.,~ul,u.. ~u~ ,s, they can contain substituted l~.~d~u~bu~ groups such as lower allcoxy, lower alkyl mercapto, hydroxy, mercapto, and carbonyl, provided the non ~ u~.~bu~ moieties do not ~
20 irlterfere with the r '- ~- '- or d~ ~i~l;u.. reactions of this invention. When present, such substituted l~dlu~ bu~ groups normally will not contribute more than lû% by weight of the total weight of the ~ ." Since the polyalkene can contain such non-llyd~ . ~ substituent, it is apparent that the olefin monomers from which the pVI,r.liktll~s are made can also contain such ~ As used herein, the 25 term "lower" when used with a chemical group such as in "lower alk,YI" or "lower alkoxy" is intended to describe groups having up to seven carbon atoms.
The ~vl~ " may include aromatic groups and ~y~ .l.-l;.. groups such as would be obtained from ~ ' ' cyclic olefins or ~y I~r ';~ ; substituted-~u',~ .i~h, acrylic olefins. There is a general preference for pul~. " free from 30 aromatic and .,.~ ' groups (other than the diene styrene i..~ v4 .....
exception already noted). There is a further preference for pvl~t..~s derived from ho...v~vl~. and i~t~,uvl~ of terminal h~dlu~bv.. olefins of 2 to 16 carbon atoms. This fiurther preference is qualified by the proviso that, while illltl~)VI,~ of terminal olefins are usually preferred, ;llil:.yul~ optionally containing up to 4û% of 35 polymer units derived from internal olefins of up to 16 carbon atoms are also within a preferred group. A more preferred class of polyalkenes are those selected from the group consisting of l~u~u,uul,l and },vl~ of terminal olefins of 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. However, another preferred AMENDED SHEET

~ ~ 8 ~ 1~ 7 ~
class of polysLkenes are the latter, more preferred P~IJ 'I~.,.IL~ OPtIOnaIIY
containing up to 25% of polyrner units derived from intemai oleflns of up to 6 carbon atoms.
Specific exarnples of terminai and internai olefin monomers which can be used 5 to prepare the polyaikenes according to ~UI~ ;U114i, well-known pol~ 4~i techniques include ethylene; propylene; butene-l; butene-2; isobutene; pentene-l; etc.;
propylene-tetramer; u.~oi~u~;k,~lc, isobutylene trimer; butadiene-1,2; butadiene-1,3;
t4u;~1S-1,2; pentadiene-1,3; etc.
Useful polymers include aipha-olefin llolllo~ and ild~llJulyll~ and 10 ethylene aipha-olefin copolymers and ~ ul~ Specific examples of pGl~clktih~
irlclude PUIY~IU~JIC~ pul~vLlt~ ,." ethylene-propylene copolymers, ethylene-butene copolymers, propylene-butene .,upul~ ." ~y~ iJutc..., .,u~uI~...e." isobutene-butadiene-1,3 copolymers, etc., and ~c.~ ...., of isobutene, styrene and piperylene and copolymer of 80% of ethylene and 20% of propylene. A useful source of 15 ~ul~4ikeL/ are the poly(isobutene)s obtained by ~ul~ of C4 refinery stream having a butene content of 35 to 75% by wt., and an isobutene content of 3û to 60%
by wt., in the presence of a Lewis acid cataiyst such as aiuminum trichioride or boron trifiuoride.
Aisousefularethehighmolecularweightpoly-n-butenesofWO-A-9413714.
A preferred source of monomer for mai~ing poly-n-butenes is petroleum f;,.,J~c such as Raffinate II. These feedstocks are disclosed in the art such as in US-A-4952739.
FtllylPnP ~h~-OlPfin Co~)ûlyrnP
Preferred polyrners are polymers of ethylene and at least one aipha-olefin having the formula H2C=CEIR4 wherein R4 is straight chain or branched chain aikyl radicai comprising I to 18 carbon atoms and wherein the polymer contains a high degree of terminai ~Lh.,l.,~;;iLI.e - ~ Preferably R4 in the above formula is aikyl of from I to 8 carbon atoms and more preferably is aikyl of from I to 2 carbon 30 atoms. Therefore, usefui .. ~ .. ~ with ethylene in this invention include propylene, I-butene, hexene-l, octene-l, etc., and mixtures thereof (e.g. mixtures of propylene and l-butene, and the like). Preferred polymers are copolymers of ethylene and propylene and ethylene and butene-l.
The molar ethylene content of the polymers employed is preferably in the range of between 20 and 8û%, and more preferably between 30 and ~0%.
When butene-l is employed as, with ethylene, the ethylene content AMENDED SHEET

1 8 9 Q l 3 - 10- , of such copolymer is most preferably between 20 and 45 wt %, although higher or lower ethylene contents may be present. The most preferred ethylene-butene-l ~,v~vl~ are disclosed.in WO-A-9419436. The preferred method for making low molecular weight ethylene/v-olefin copolymer is described in WO-A-9413715.
Preferred ranges of number average molecular weights of polymer for use as precursors for dispersants are from 500 to 10,000, preferably from 1,000 to 8,000, most preferably from 2,500 to 6,000. A conYenient method for such ,'~ is by size exclusion .,1.., ~ (also known as gel permeation ~,LI.." '''K'~
(GPC)) which - ' " ".~, provides molecular weight distribution " Such 10 polymers generally possess an intrinsic viscosity (as measured in tetralin at 135C) of between 0.025 and 0.6 dl/g, preferably between 0.05 and 0.5 Wg, most preferably between 0.075 and 0.4 dl/g. These polymers preferably exhibit a degree of crystallinity such that, when grafted, they are essentially amorphous.
The preferred ethylene alpha-olefin polymers are fiurther ~ . ;1 in that5 up to 95% and more of the polymer chains possess terminal vinylidene-type - Thus, one end of such polymers will be of the formula POLY-C(Rl 1) =
CH2 wherein Rll is Cl to Clg alkyl, preferably Cl to C8 alkyl, and more preferably methyl or ethyl and wherein POLY represents the polymer chain. A minor amount oftbe polymer chains can contain terrninal ethenyl, , i.e. POLY-CH=CH2, 20 and a portion of the polymers can contain internal , e.g. POLY-CEI=CH(Rl 1), wherein Rl I is as defined above.
The preferred ethylene alpha-olefin polymer comprises polyrner chains, at least 30% of which possess terminal vinylidene, .. .- -~ ,n ~ ~ Preferably at least 50%, more preferably at least 60%, and most preferably at least 75% (e.g. 75 to 98%), of such 25 polymer chains exhibit terminal vinylidene, The percentage of polymer chains exhibiting terminal vinylidene ,. --~ ;.... may be determined by FTIR
v~vy;v analysis, titration, HNMR, or C 1 3NMR
The polymers can be prepared by l,vl.~ ~ monomer n~ixtures comprising ethylene with other monomers such as alpha-olefins, preferably from 3 to 4 carbon 30 atoms in the presence of a " - catalyst system comprising at least one "- (e.g., a ~ .r I 'IJ - '~ 1: .~: transition metal compound) and an activator, e.g.
alumoxane compound. The . content can be controlled through selection of the ,.. ~ -- catalyst component and by controlling partial pressure of the monomers.
The catalyst is preferably a bulky ligand transition metal compound. The bulky ligand may contain a multiplicity of bonded atoms, preferably carbon atoms, forming a AMENDED SHEET

~1~9Q73 ~ WO 95/35326 . ~ 14 _ 11 group which may be cyclic with one or more optional l.flCIU~ VIII:~. The bulky ligand may be a ~.1.~ fli .Iyl derivative which can be mono- or pvlyl~u~,h,~l. One or more bulk-y ligands may be bonded to the transition metal atom. The transition metal atom may be a Group IV, V or Vl transition metal ("Group" refers to an identified 5 group of the Periodic Table of Elements, ~ ;J.,Iy presented in "~dvanced Inorganic Chemistry," F.A. Cotton, G. Wilkinson, Fifth Edition, 1988, John Wiley .5:
Sons). Other ligands may be bonded to the transition metal, preferably detachable by a cocatalyst such as a llydlvcf~lbr~ or halogen leaving group. The catalyst is derivable from a compound of the formula 1 0 [L]mM[X]n wherein L is the bulk-y ligand, X is the leaving group, M is the transition metal and m and n are such that the total ligand valency uùllt~v~ids to the transition metal valency.
Preferably the cataiyst is four coordinate such that the compound is ionizable to a l+
valency state.
The ligands L and X may be bridged to each other and if two ligands L and/or X are present, they may be bridged. The Il~ÇPnPC may be full-sandwich compounds having two ligands L which are cyrlflppnr~ pnyl groups or half-sandwich cnmrf.~n~l~ having one ligand L only which is a cy~,lu~;..L..~ik,.lyl group.
For the purposes of this patent ~ the term '' "- " is defined 20 to contain one or more u~,lu~ ih,..yl moiety in .... ~ i.." with a transition metal of the Periodic Table of Elements. In one ~ û~ the .,.. l "-,f. catalyst component is ,c,u.~ ,..t~,d by the general formula (Cp)mMRnR'p wherein Cp is a substituted or llncllhctitll~Pfl ~ .lvi, fliPnyl ring; M is a Group IV, V or Vl transition metal; R and R' are; ~ lly selected halogen, hydrocarbyl group, or h~lluu~buAyl groups having 1-20 carbon atoms; m = 1-3, n = 0-3, p = 0-3, and thesum of m + n + p equals the oxidation state of M. In another Pmhf~flimPI.~ the "- - catalyst is represented by the formulas:
(C5R'm)pR"s(C5R m)MeQ3-p-x and R"s(CsR'm)2MeQ' wherein Me is a Group IV, V, or VI transition metal CsR'm is a substituted ~,y~.ll~J. ,,.1:. ..yl each R', which can be the same or different is hydrogen, alkenyl aryl alkaryl or arylalkyl radical having from i to 20 carbon atoms or two carbon atoms joined together to form a part of a C4 to C6 ring, R" is one or more of or a rf~mhin-~tif)n of a carbon, a germanium, a silicon, a ~ o~ u~uu~ or a nitrogen atom containing radical ~ on a bridging two CsR'm rings or bridging one CsR'm ring back to Me, when p = 0 and x = ~ otherwise x is always equal to 0, each Q which can be the same or different is an aryl alkyl, alkenyl, alkaryl, or arylalkyl radical having .. . ..

~ 1 ~qQ73 W095/35326 r_l, from I to 20 carbon atoms or halogen, Q' is an alkylidene radical having from I to 20 carbon atoms, s is 0 or I and when s is 0, m is 5 and p is 0. ] or 2 and when s is 1, m is 4andpis 1.
Various forms of the catalyst system of the l " ~ type may be used in the p~ process of this invention. Exemplary of the d~,lu~ of "- cataiysts in the art for the p~lJ...~.,i~io.~ of ethylene is the disclosure of US-A-4871705 to Hoel, US-A-4937299 to Ewen, et ai. and EP-A-0129368 published July 26, 1989, and US-A-5017714 and US-A-5120867 to Welborn, Jr. These ~ ' ' teach the structure of the "~r~n~ catalysts and include alumoxane as 10 the cocatalyst. There are a variety of methods for preparing alumoxane, one of which is described in US-A-4665208. ~ ~ ~
For the purposes of this patent ~ the terms "cocatalysts or activators" are used ;..~ ~1y and are defined to be any compound or component which can activate a bulky ligand transition metal compound. In one 15 I;llliJ~ " ' the activators generally contain a metal of Group Il and III of the Periodic Table of Elements. In the preferred rl l l .c~ , the bulky transition metal compound are iltlçl~nrc which are activated by trialkylaluminum f~r~mrollnric . l....,..~ ... ~
both linear and cyclic, or ionizing ionic activators or çr\mrçllnric such as tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, which ionize the neutral "
20 compound. Such ionizing compounds may contain an active proton, or some othercation associated with but not uuuld;~ d, or only loosely cc,o,l;,l~l~t;d to theremaining ion of the ionizing ionic compound. Such compounds are described in EP-A-0520 732, EP-A-0 277 003 and EP-A-0 277 004 published August 3, 1988, and US-A-5153157; 5198401 and 5241025. Further~ the l "~ catalyst component 25 can be a mono~iyl~p -~h-i .Iyl heteroatom containing compound. This heteroatom is activated by either an alumoxane or an ionic activator to form an active ~OI~ G~;UII
catalyst system to produce polymers useful in this invention. These types of catalyst systems are described in, for example, PCT lI~ ;UI~aI Publication WO 92/00333 published January 9, ~992, US-A-5057475; 5096867; 5055438 and 5227440 and EP-A-0 420 436, WO 91/04257. In addition, the "- catalysts useful in this invention can include non-c~lu~ yl catalyst ~ or ancillary ligands such as boroles or carbollides in c. .. "l l -' ;. .,. with a transition metal. Additionally, it is not beyond the scope of this invention that the catalysts and catalyst systems may be those described in US-A-5064802 and PCT p~bli~ationc WO 93/08221 and WO
93/08199 published April 29, ~993. Ail the catalyst systems ofthe invention may be, optionally, prepolymerized or used in çonjlln~ti~n with an additive or scavenging component to enhance catalytic productivity.

~1 ~sa~
W095/35326 ; I_I~L . /0/4 The polymer for use in the Koch reaction can include block and tapered Cu~,~lJ ~ derived from monomers comprising at least one conjugated diene with atleast monovinyl aromatic monomer, preferably styrene. Such polymers should not be completely hy~ O ' ' so that the polymeric ~ contains oiefinic double 5 bonds, preferably at least one bond per molecule. The Koch reaction can also include star polymers as disclosed in patents such as U.S. Patent Nos. 5,070,131; 4,10~,945;
3,711,406; and 5,049,294.
Po~vmer Stripping Polymers useful for dispersants in lubricant rr~' ~ can comprise a mhsture or distribution of molecular weights. This distribution is a result of the processes used to make the polymers. Number average molecular weight is a useful way to represent the molecular weight distribution.
It has been found desirable to minimi~e or reduce, or eliminate completely, the 15 amount of lower molecular weight polymers (e.g., light polymers) or monomers such as unreacted higher olefins from a given polymer molecular weight distribution to improve the ~,. r..l of the final product.
In the Koch process as described herein, it has been found useful to minimize the amount of low molecular weight (light) ester formed during the carbonylation step.
20 Light ester can be formed by two routes. Route one involves the introduction of light ester precursors such as C4 to C24 olefins which are impurities in the polymer feed.
Route two may involve the generation of breakdown products during the .,~ll,u..y.~lliu.
reaction.
This invention relates to "route one". It has been found that by stripping (e.g., 25 removing light polymer and unreacted monomers such as olefins) from the polymer feed prior to the u~ n~ step the amount of undesirable light polymer esters thatis generated is reduced. The stripping of the polymer feed can be a...,.. ,l.l;- ~ .1 by any suitable means. The stripping can take place in a batch or continuous process. The process equipment utilized is not critical providing that the necessary conditions of 30 t~ Ul ~ and negative pressure (e.g., vacuum) can be met. A short path evaporator is a useful means for stripping the polymers and is known in the art. A typical short path evaporator comprises a vessel with product feed, and residue discharge means, a heating means and a distillate overhead with a condenser, a collector and vacuumpump. The evaporator should be equipped with a condenser and collector means for35 recovery and disposal of the light polymer stripped from the polymer feed.
The evaporator should have sufficient volume to handle usefiul quantities of polymer feed (e.g., 50 kilograms per hour for a pilot unit and more for a commercial ~ 8q~73 faciGty) The evaporator should be capable of heating the polymer feed to L~ Lul~high enough for efficient eYaporation of the light polymer. Suitable t~ dLul~ are in the range of 180 to 300'C, preferrbly 200 to 240C, most preferably 220 to 230C.
The evaporator may operate at .' pressure but it is preferable to operate 5 under negative pressure (e.g., vacuum) for more efficient stripping. Suitable vacuum is irl the range of 0.067 to 6.67 kPA (0.5 to 50 mm Hg), preferably 0.133 to 4.0 kPA
(1.0 to 30 mm Hg), more preferably 0.2 to 2.667 kPA (1.5 to 20 mm Hg). The efiiciency of the Gght polymer stripping may be improved by optional agitation of the polymer feed in the eYaporator or the use of inert gases (e.g., nitrogen) to assisting in 10 separating the Gght polymer from the polymer residue. Techniques such as these are known in the art.
C~ubull~lt.L;ù.l is the part of the t; ~ "", process wherein the ' polymer is reacted with carbon monoxide in the presence of an acid catalyst, preferably BF3, and a ._ '~ ,' " trapping agent, Cu~ LIy 2,4-15 ' '' uph_...)l. The resultant product is an ester with an attendant leaving group.This ~ ' ' product can be ~u~u_.dly derivatized with an amine to form the useful dispersant for lubricant additive ~ ' '- An excess over the ' amount of 2,4-dh,l~lu~r' ' (DCP) is used in the reaction and it is necessaly to remove the unreacted DCP from the crude ester produced in the reaction and recover 20 it for reuse. The crude ester produced in the ~,cubu~yl~;ull reaction consists essentially of unreacted DCP, impurities and the r - ~- ~ poly~ner. The ' " ' polymer includes lower molecular weight polymer and unreacted olefin monomers which range in carbon number from C4 to C24 which have been esterified.
llle unreacted DCP can be removed from the crude polymer ester in a process 25 of c~JùlaL;u~l, stripping, or distillation. Processes of this type are known in the art and can be run in equipment such as fash drums, falling film L~ Julalula, forced film ûr wiped film c. tyulalul~, or short path c ~ulaLul~ or the like. In general, this equipment comprises a vessel ûr pipe wherein a liquid mass is heated to a tt..l~J~ .alul~
at which volatile material evaporates from the liquid mass. The process can be run at al.. ~"l--; pressure or under negative pressure (e.g., vacuum). Negative pressure is preferable. Agitation can be beneficial to assist in l;uu;d/~ o~ _ Use of an inert gas (e.g., nitrogen) passing through the liquid mass can also assist in Lu~u;~ Jo~
For removal of volatiles from viscous liquids, forced film or short path 35 _~r.~ulaLul~ are preferred. Short path c ~uùla~ul~ are particularly useful. Once the unreacted DCP is removed from the crude polymer ester it is desired to condense and collect it for subsequent reuse. This can be achieved by use of a condenser and collector either external or internal to the short path evaporator. During the . .
AMENDEO SHEET
~ . . . _ . ... . ..

~ Qaq~7~
W09S/35326 ~;111 5._1014 C~ Juld~ that boil lower than the 5 ' ' polymer, such as the DCP, light esters and chlorinated mixtures are removed overhead to the distillate stream. The bottom product of 5 ' ' polymer is ! ' , 'y derivatized in an amination reactor.
The distillate is collected and then fractionally distilled to recover and recycle the unreacted DCP. However, some of the impurities, especially light esters that boil close to DCP as well as light chlorinated ~ r ~ are also 1~ ly recycled.
Ultimately the recycle stream will become saturated with undesirable ~ r Since the evaporation is a single stage operation, an equilibrium level of ul.u.,~ lc..
10 will build up in the process streams. The levels of light ester will increase in the residue product, possibly adversely affecting the p~,.r.,...,~."~,t of the final dispersant.
In order to maintain low impurity levels, the distillate might have to be frequently purged. This is very costly. Thus, it is very desirable to minimize the amount of light ester present in the crude ester fed to the evaporators.
Hence, removal of the light ester precursors (C4 to C24 olefinic monomers or polymers) firom the polymer prior to the carbonylation step is desirable.
Koch Reaction In the Formula I, the letter n is generally greater than 0 and represents the 20 ~ ' y (F) or average number of functional groups per polymer chain. Thus, ~ y can be expressed as the average number of moles of functional groups per "mole of polymer". It is to be understood that the term "mole of polymer" includes both r ~ ~ and ~ ' ' polymer, so that F cOll~,a~u~lJa to n of Formula (I). The r - ~ ~ polymer will include molecules having no functional 25 groups. Specific preferred ~lllbOJ;~ la of n include 1 > n > 0; 2 > n > I; and n >2. n can be determined by C13 NMR. The optimum number of functional groups needed for desired p.,. r..l will typically increase with Mn of the polymer. The maximum value of n will be determined by the number of double bonds per polymer chain in the 1 polymer.
In specific and preferred embodiments the "leaving group" (-YR3) has a pKa of less than or equal to 12, preferably less than lO. and more preferably less than 8. The pKa is determined from the ul)lu::a~uO~ g acidic species HY-R3 in water at room Where the leaving group is a simple acid or alkyl ester, the r ~ ~
35 polymer is very stable especially as the % neo cl ~titllti~n increases. The Koch reaction is especially useful to make ''neo" filn~ti~n~ Pd polymer which are generally more stable and labile than iso structures. In preferred embodiments the polymer can . .

~ 1 8 ~ ~ 7~ --... .. ..

be at least 60, more preferably at least 80 mole percent r ' ~ I The polymer can be greater than 90, or 99 and even 100 mole percent neo.
In one preferred c~ -,-- the polymer defined by formula (I), Y is O
(oxygen), Rl and R2 can be the same or different and are selected from H, a 5 hydrocarbyl group, and a polymeric group.
In another preferred c..l~o.l;ll,.,.A Y is O or S, Rl and R2 can be the same or different and are selected from X a hydrocarbyl group a substituted hydrocarbyl group and a polymeric group, and R3 is selected from a substituted lyd~uL,al~yl group, an aromatic group and a substituted aromatic group. This . L ' is generally more 10 reactive towards d~,~iv~ Liu~l with amines and alcohol . ' especially where the R3 substituent contains electron ~;LIldl~ species. ~t has been found that in this . ..,l v l - ~, a preferred leaving group, IIYR3, has a pKa of less tharl 12, preferably less than 10 and more preferably 8 or less. pKa values can range typically from 5 to 12, preferably from 6 to 10, and most preferably from 6 to 8. The pKa of the leaving 15 group determines how readily the system will react with d.,.;~lLiLill~; compounds to produce derivatized product.
In a particularly preferred .",...l.~ .., R3 is ~oylG,.,,.~,d by the formula:
Xm Tp wherein X, which may be the same or different, is an electron wi~ substituent, T, which may be the same or different, represents a .~on e~ lUII WiLIldlll~.' ,,substituent (e.g. electron donating), and m and p are from 0 to 5 with the sum of m and p being from 0 to 5. More preferably, m is from I to 5 and preferably I to 3. In a 25 particularly preferred ~ .,,I,.,.!i -1 X is sdected from a halogen, preferably F or Cl, CF3, cyano groups and nitro groups and p = 0. A preferred R3 is derived from 2,4-~ ,llul~
The ~.,....~.~,~ l,.~.\ derived from the present invention includes derivatizedpolymer which is the reaction product of the Koch r '- ~- ~ polymer and a 30 derivatizing compound. Preferred derivatizing ~ . ' include nucleophilic reactant compounds including amines, alcohols, L . ' ' ', metal reactant compounds and mixtures thereo Derivatized polymer will typically contain at least one of the following groups: amide, imide, oxazoline, and ester, and metal salt. The suitability for a particular end use may be improved by ~ ~,uluulh~le selection of the 35 polymer Mn and r '- ~-~5/ used in the derivatized polymer as discussed hereinaf'er.
AMENDED SHEET
, , . . ,,, .. , . , .. , .. ,, .. ,,,, ... ,, . , .,,, . , . ,, . ., . ,, ., . , ., ., . ,,,,,, .,, .. , ., , . , ., . , . ,,, .,,,,, .. , ,, , , .. _ , 7 1! ~3 q ~ 7;~ r ~ r ~ r .

The Koch reaction permits controlled ' " of unsaturated polymers. When a carbon of the carbon-carbon double bond is substituted with hydrogen, it wiil result in an "iso" functionai group, i.e. one of Rl or R2 Of Formula I
is H; or when a carbon of the doubie bond is fuily substituted with lly ilu~ groups 5 it wiii result in an "neo" functionai group, i.e. both Rl or R2 of Forrnula I are non-hydrogen groups.
Polymers produced by processes which result in a terrninPlly l~nr~ rAt~d polymer chain can be r ~ ~ to a relatively high yield in accordance with the process of the present invention. It has been found that the neo acid r,.... ~
10 polymer can be derivatized to a relatively high yield. The Koch process aiso maices use of relatiYely inexpensive materiais i.e., carbon monoxide at relatively low L~ u~
and pressures. Aiso the leaving group -YR3 can be removed and recycled upon d~;v ~ the Koch r ~ ~ polymer with amines or aicohols. The or derivatized polymers of the present invention are useful as lubricant 15 additives such as dispersants, viscosity improvers and ,-- ~l~il~.... ll.... ~ viscosity improvers. The ~ .. derived from the present invention includes oleaginous c... ~ comprising the above r ~ 1, and/or derivatized polymer. Such ~l;.- ~- include lubricating oii ~ . and The Koch reaction aiso provides a process wilich comprises the step of ~ reacting in 20 admixture: (a) at least one h~u~,~bo~l polymer having a number average molecular weight of at least 500, and an average of at least one ethylenic double bond perpolymer chain; (b) carbon monoxide~ (c) at least one acid cataiyst~ and (d) a _ !. r' " trapping agent selected from the group consisting of water, hydroxy-containing compounds and thiol-containing . . ', the reaction being conducted 25 a) in the absence of reliance on transition metai as a cataiyst; or b) with at least one acid catalyst having a Hammett acidity of less than -7; or c) wherein functionai groups are formed at least 40 mole % of the ethylenic double bonds; or d) wherein the _ ' . ' ' trapping agent has a pKa of less than 12.
The process of the present invention relates to a polymer having at least one 30 ethylenic double bond reacted via a Koch mecha;Aism to form carbonyl or thio carbonyl group-containing . . ' which may ' . ~.~, be derivatized. The polymers react with carbon monoxide in the presence of an acid cataiyst or a cataiyst preferably complexed with the ' r~ ~ trapping agent. A preferred cataiyst is BF3 and preferred cataiyst complexes include BF3.H2O and BF3 complexed with 2,4-35 d;~,liu~.' ' The starting polymer reacts with carbon monoxide at points of --AI;--- to form either iso- or neo- acyl groups with the l ' ,' " trapping AMEN~ED SHEET

7~
wo ssl3s326 . ~l/~ 14 agent, e.g. with water, alcohol (preferably a substituted phenol) or thiol to form respectively a carboxylic acid, carboxylic ester group, or thio ester.
In a preferred process, at least one polymer having at least one carbon-carbon double bond is contacted with an acid catalyst or catalyst complex having a Hammett Scale acidity value of less than -7, preferably from -8.0 to -11.5 and most preferably firom -10 to -11.5. Without wishing to be bound by any particular theory, it is believed that a carbenium ion may form at the site of one of carbon-carbon double bonds. The carbenium ion may then react with carbon monoxide to form an acylium cation. Theacylium cation may react with at least one 1~ ,' ' trapping agent as defined 1 0 herein.
At least 40 mole %, preferably at least 50 mole %, more preferably at least 80 mole %, and most preferably 90 mole % of the polymer double bonds will react to form acyl groups wherein the non-carboxyl portion of the acyl group is determined by the identity of the llucl~,~Jr ' ' trapping agent, i.e. water forms acid, alcohol forms acid ester and thiol forms thio ester. The polymer fi~nrti~ 7Pd by the recited process of the present invention can be isolated using fluoride salts. The fluoride salt can be selected from the group consisting of ammonium fluoride, and sodium fluoride.
Preferred l ~ ' ' trapping agents are selected from the group consisting of water, monohydric alcohols, polyhydric alcohols hydroxyl-containing aromatic compounds and hetero substituted phenolic çomr~ ' The catalyst and . 5~, ' ''~
trapping agent can be added separately or combined to form a catalytic complex.
Following is an example of a terminally unsaturated polymer reacted via the Koch mechanism to form an acid or an ester. The polymer is contacted with carbonmonoxide or a suitable carbon monoxide source such as formic acid in the presence of an acidic catalyst. The catalyst contributes a proton to the carbon-carbon double bond to form a carbenium ion. This is followed by addition of CO to form an acylium ion which reacts with the ,. ' -rl ~ trapping agent. POLY, Y, Rl, R2 and R3 are defined as above.

~1 89~73 wo9sl35326 P~ ,or4 R~ CAT. R
Il I
POLY- C + > POLY - C+ (Ir) (carbenium ion) Rl Rl 10 POLY - C+ + CO > POLY -C-CO+ (III) (acylium ion) 15 Rl Rl O
l 11 POLY - C - C+O + R3YH ~ POLY - C - C - YR3 (I~

The Koch reaction is particularly useful to filnrtion~li7~ poly(alpha olefins) and ethylene alpha olefin copolymers formed using m~ loc~no-type catalysts. These polymers contain terminal vinylidene groups. There is a tendency for such terminal groups to ~ .lo...;..~ and result in neo-type (tertiary) carbenium ions. In order for the carbenium ion to form, the acid catalyst is preferably relatively strong. However, the strength of the acid catalyst is preferably balanced against detrimental side reactions which can occur when the acid is too strong The Koch catalyst can be employed by preforming a catalyst complex with the proposed ~ trapping agent or by adding the catalyst and trapping agent separately to the reaction mixture. This later ~Illbod;lll.,.l~ has been found to be a particular advantage since it eliminates the step of making the catalyst complex.
The following are examples of suitable acidic catalyst and catalyst complex materials with their respective Hammett Scale Value acidity: 60% H2SO4, -4.32;
BF3.3H2O, -4.5; BF3.2H2O, -7.0; WO3/A12O3, less than -8.2; SiO2/A12O3, less than-8.2; HF, -10.2; BF3.H2O, -11.4; -11.94; ZrO2 less than -12.7; SiO2/A12O3, -12.7 to -13.6; AIC13, -13.16 to -13.75; AlC13/CuSO4, -13.75 to -14.52.
It has been found that BF3.2HzO is ineffective at 1`.,... I;u -~ ;"k polymer through a Koch mechanism ion with polymers. In contrast, BF3.H2O resulted in high yields of carboxylic acid for the same reaction. The use of H2SO4 as a catalyst 40 involves control of the acid ~ CC~ iOll to achieve the desired Hammett Scale Value range. Preferred catalysts are H2SO4 and BF3 catalyst systems.
. , . _ _ , , . . , . _ 2 ~
.' , . ... ....
., . .. -Suitable BF3 catalyst complexes for use in the present inventlon can be c~ ,J by the for~nula:
BF3 xHOR
wherein R can represent hydrogen, II~Jlu.,a~iJyl (as defined below in connection with 5 R') -CO-R', -S2 - R', -PO-(OH)2, and mjxtures thereof wherein R' is llyd~v~,~uvyl, typicaiiy aikyl, e.g., Cl to C20 alkyl, and, e.g., C6 to C14 aryl, aralkyl, and allcaryl, and x is less than 2.
Foiiowing reaction with CO, the reaction mixture is further reacted with water or another .. I. ~,~,h''i. trapping agent such as an aicohol or phenolic, or thiol 10 compûund. The use of water releases the catalyst to forrn an acid. The use of hydroxy trapping agents releases the catalyst to form an ester, the use of a thiol releases the catalyst to form a thio ester.
Koch product, also referred to herein as r '' ~' ~ polymer, typicaUy will be derivatized as described hereinafter. Du.iY~Li~;v~ reactions involving ester 15 r ~' " 1 polymer will typicaiiy have to displace the alcohol derived moiety therefrom. Cl~nC~Tll~nfly~ the alcohol derived portion of the Koch 1~,....l,.~". l; .1 polymer is sometimes referred to herein as a leaving group. The ease with which a leaving group is displaced during ~ ,.L~Livr~ wiii depend on its acidity, i.e. the higher the acidity the more easily it wiii be displaced. The acidity in turn of the alcohol 20 is expressed in terms of its pKa Preferred nucleophilic trapping agents include water and hydroxy group containing ~ . ' Useful hydroxy trapping agents include aliphatic .,u ~l..,,. l~such as 'q~i~iG and polyhydric alcohols or aromatic compounds such as phenols and naphthols. The aromatic hydroxy cl~mrolln~lc from which the esters of this 25 invention may be derived are illustrated by the following specific example: phenol, -naphthol, cresol, resorcinol, catechol, 2-~ iulupl~ ol. Particularly preferred is 2,4-lu~UltJII~--;)I ' The aicohols preferably can contain up to 40 aliphatic carbon atoms. They may be ' ,~i., aicohols such as methanols, ethanol, benzyl aicohol, 2-30 1"~,.1"1~.' ' I, beta-~,llu~ lu~u~-i.,LIyl ether of ethylene giycol, etc.
The polyhydric aicohols preferably contain from 2 to 5 hydroxy radicals; e.g., ethylene giycol, diethylene giycol. Other useful polyhydric aicohols include glycerol, ' jl ether of giycerol, and iJ~ Y LLfiLul. Useful unsaturated aicohols include aiiyl aicohol, and propargyl alcohol. Particularly preferred aicohols include those 35 having the formula R~2CHOH where an R~ is, I~ ly hydrogen, an alkyl, aryl, ilu~y ii~yl, or cycloaikyl. Specific aicohols include aikanols such as methanol,ethanol, etc. Aiso preferred useful aicohols include aromatic alcohols, phenolic AMENDED SHEE~

~ 1 8 9 a ~ ~ f , , , , ,, ~
.

compounds and polyhydric alcohols as well as ' ,d.i., alcohols such as 1,4-butanediol.
It has been found that neo-acid ester r '' ~- ~ polymer is extremely stable due, it is believed, to stearic hindrance. t~ ly, the yield of derivatized polymer 5 obtainable therefrom will vary depending on the ease with which a derivatizingcompound can displace the leaving group of the r, . .. l l,,. ~,.l. . ~ polymer.The most preferred alcohol trapping agents may be obtained by substituting a phenol with at least one electron wi~ substituent such that the substituted phenol possesses a pKa within the above dcribed preferred pKa ranges. In addition, 10 phenol may also be substituted with at least one r~nn elc~,~lu~ dlr~ o substituent (e.g., electron donating), preferably at positions meta to the electron ..:;lld.,l.. _ substituent to block undesired alkylation of the phenol by the polymer during the Koch reaction. This further improves yield to dired ester r -, '.... ~;...I poly~ner.
Accordingly, and in view of the above, the most preferred trapping agents are 15 phenolic and substituted phenolic compounds .~.u..~,..t~,~ by the formula:
~ ,.
wherein X which may be the same or different, is an electron ..:~lld~ .:..o substituent, 20 and T which may be the same or different is a l.u.. el-,.,L.u.. ~. .lldld~. ..o group; m and p are from 0 to 5 with the sum of m and p being from 0 to 5, and m is preferably from I to 5, and more preferably, m is I or 2. X is preferably a group selected from halogen, cyano, and nitro, preferably located at the 2- andlor 4- position, and T is a group selected from hydrocarbyl, and hydroxy groups and p is I or 2 with T preferably 25 being located at the 4 and/or 6 position. More preferably X is selected from Cl, F, Br, cyano or nitro groups and m is preferably from I to 5, more preferably from I to 3, yet more preferably I to 2, and most preferably 2 located at the 2 and 4 locations relative to -OH.
The relative amounts of reactants and catalyst, and the conditions controlled in30 a manner sufficient to r. 1;.... 1;.. typically at least 40, preferably at least 80, more preferably at least 90 and most preferably at least 95 mole % of the carbon-carbon double bonds initially present in the, ~ ' ' polymer.
The amount of H2O, alcohol, or thiol used is preferably at least the , ... l.;. .. - l . ;.. amount required to react with the acylium cations. It is preferred to use AMENDED SHEET

W095/35326 ~t 89a7~ P IS95/07674 an excess of alcohol over the ~ I J ~ ~ i., amount. The alcohol performs the dual role of reactant and diluent for the reaction. However, the amount of the alcohol or water used should be sufficient to provide the desired yield yet at the same time not dilute the acid catalyst so as to adversely affect the Hammett Scale Value acidity.
The polymer added to the reactant system can be in a liquid phase. Optionally, the polymer can be dissolved in an inert solvent. The yield can be determined upon completion of the reaction by separating polymer molecules which contain acyl groups which are polar and hence can easily be separated from unreacted non-polar Separation can be performed using absorption techniques which are known in the art. The amount of initial carbon-carbon double bonds and carbon-carbon double bonds remaining after the reaction can be determined by C13 NMR
techniques.
In accordance with the process, the polymer is heated to a desired ~ 1ulc;
range which is typically between -20C to 200C~ preferably from 0C to 80C andmore preferably from 40C to 65C. Temperature can be controlled by heating and cooling means applied to the reactor. Since the reaction is exothermic usually cooling means are required. Mixin~ is conducted throughout the reaction to assure a uniform reaction medium.
The catalyst (and ml-l~ ), ' " trapping agent) can be prereacted to form a catalyst complex or are charged separately in one step to the reactor to form the catalyst complex in situ at a desired t~ lul~ and pressure, preferably under nitrogen. In a preferred system the ,. ~ ' " trapping agent is a substituted phenol used in ~".. I, .. lj,.. with BF3. The reactor contents are . (. 1;.. "~l~ mixed and then rapidly brought to a desired operating pressure using a high pressure carbon monoxide source. Useful pressures can be up to 138.000 kPa (20,000 psig). and typically will be at least 2070 kPa (300 psig), preferably at least ~,520 kPa (800 psig), and mostpreferably at least 6,900 kPa (1,000 psig), and typically will range from 3450 to 347500 kPa (500 to 5,000 psig) preferably from 4485 to 20~700 kPa (650 to 3,000 psig) and most preferably from 4485 to 13,800 kPa (650 to 2000 psig). The carbon monoxide pressure may be reduced by adding a catalyst such as a copper compound. The catalyst to polymer volume ratio can range from 0.25 to 4, preferably 0.5 to 2 and most preferably .75 to 1.3.
Preferably, the polymer, catalyst, i ~'~, ' " ~ trapping agent and CO are fed tothe reactor in a single step. The reactor contents are then held for a desired amount of time under the pressure of the carbon monoxide. The reaction time can range up to 5 hours and typically 0.5 to 4 and more typically from I to 2 hours. The reactor contents can then be discharged and the product which is a Koch r . ~ I

w09513926 ~ 1 89~7~ s. lO-~4 polymer comprising either a carboxylic acid or carboxylic ester or thiol ester functional groups separated. Upon discharge, any unreacted C0 can be vented off. Nitrogen can be used to flush the reactor and the vessel to receive the polymer.
Depending on the particular reactants employed, the r ' ~- ' polymer 5 containing reaction mixture may be a single phase, a cr. l. -:;...~ of a ~LiLiu~d~
polymer and acid phase or an emulsion with either the polymer phase or acld phase being the continuous phase. Upon completion of the reaction, the polymer is recovered by suitable means.
When the mixture is an emulsion, a suitable means can be used to separate the 10 polymer. A preferred means is the use ûf fluoride salts, such as sodium or ammonium fluoride in r~ ;..,. with an alcohol such as butanol or methanol to neutralize the catalyst and phase separate the reaction complex. The fluoride ion helps trap the BF3 complexed to the r ' 1 ~ polymer and helps break emulsions generated when the crude product is washed with water. Alcohols such as methanol and butanol and 15 commercial d~,."ul~;G~ also help tû break emulsions especially in ~.u ~ with fluoride ions. Preferably, . .. ~ ' trapping agent is combined with the fluoride salt and alcohols when used to separate polymers. The presence of the '~, ' "
trapping agent as a solvent minimizes L, irlcation ofthe r ' ~' ~ polymer.
Where the ml-' , ' ' trapping agent has a pKa of less than 12 the 20 ~ ' ' polymer can be separated from the r~l~rlPoFhilir trapping agent and catalyst by d~. ~ Ul ;~;o.l and distillation. It has becn found that where the ,,,,,1, ,,~1.1. trapping agent has lower pKa's, the catalyst, i.e. BF3 releases more easily from the reaction mixture.
As indicated above, polymer which has undergone the Koch reaction is also 25 referred to herein as r ' ~' ~ polymer. Thus, a fi~nrtinnqli7r-d polymer comprises molecules which have been chemically modified by at least one functional group so that the r".,..~ polymer is (a) capable of undergoing further chemical reaction . (e.g. derivatization) or (b) has desirable properties, not otherwise possessed by the polymer alone, absent such chemical ~,ln.l;~ ;nl~
It will be observed from the discussion of formula I that the functional group is ,L~ J as being l~ l,L~d by the parenthetical expression Rl 0 -(--C--C.--YR3) o Il 40 which expression contains the acyl group -C-YR3. It will be understood that while the 9 ~7 ~ . :

Rl I _ R2 moiety is not sdded to the polymer in the sense of being derived from a separate reactant it is still referred to as being part of the functional group for ease of discussion and description. Strictly speaking, it is the acyl 10 group which constitutes the functional group, since it is this group which is added during chemical, .1:1~ loreover, Rl and R2 represent groups originaUy present on, or, ,, part of, the 2 carbons bridging the double bond before r - ~- '- However, Rl and R2 were included within the ~,~CIILl..,;;.,~ so that neo acyl groups could be .I;~t;l, J from iso acyl groups in the formula depending ontheidentityofRl andR2.
Typically, where the end use of the polymer is for making dispersant, e.g. aS
derivatized polymer, the polymer will possess dispersant range molecular weights (Mn) as defined hereinafter and the r ~ will typically be :,;~I;Lh,~ Iower than for polymer intended for making derivatized -r - ~I V.I. improvers, where the polymer will posss viscosity modifier range molecular weights ~n) as defined hereinafter.
1~CCUI~ while any effective r - ~-7)I can be imparted to r ~ ~
polymer intended for subsequent '~ c.;i~L;ul., it is C~ yl ~~ 7 that such '-'- , expressed as F, for dispersant end uses, are typically not greater than 3, preferably riot greater than 2, and typically can range firom 0.5 to 3, preferably from û.8 to 2.0 (e.g. 0.8 to 1).
Similarly, effective r - ~-'- F for viscosity modifier end uses of derivatized polymer are . ' ' to be typically greater than 3, preferably greater tban 5, and typicaUy will range from S to lO. End uses involving very high molecular weight polymers . . r - ' ~- - which can range typically greater than 20, preferably greater than 30, and most preferably greater than 40, and typically can range from 20 to 60, preferably from 25 to 55 and most preferably from 30 to 50.
r~eriv~ti~l Polym~
The r - ~- ~ polymer can be used as a d~ lL/~
viscosity modifier if the functional group contains the requisite polar group. The fimctional group can also enable the polymer to participate in a variety of chemical reactions. Derivativ of ~ ' ' polymers can be formed through reaction of the functional group. These derivatized polymers may have the requisite properties for AMENDE~ SHEET

~ ~ ~ 89a13 . -. .
.. ..

a variety of uses including use as dispersants and viscosity modifiers A derivatized polymer is one which has been chemically modified to perform one or more functions in a ~ / improved way relative to the ~ ~ ' ' polymer and/or the , 1 polymer. R~~ iv~: of such functions, are d;..~ a~ ,y andlor 5 viscosity ,.~ ., in lubricating oil ~
The derivatizing compound typically contains at least one reactive derivatizing group selected to react ~vith the functional groups of the 1~ polymers by various reactions. ~ iV~ of such reactions are ~ - 51~hQtjhltjnn ^ , salt formation, and the like. The d~,liV '- _ compound preferably 10 also contains at least one additional group suitable for imparting the desired properties to the derivatized polymer, e.g., polar groups. 'rhus, such d~livrLi~..~ compounds typicaUy will contain one or more groups including arnine, hydroxy, ester, amide, imide, thio, thioamido, oxazoline, or carboxylate groups or form such groups at the completion of the d~,liv~lii~liu~l reaction.
The derivatized polymers include the reaction product of the above recited ' polymer with a ~ reactant which include amines, alcohols, ~ 1 ~ I and mixtures thereof to form oil soluble salts, amides, oxazoline, and esters. Alternatively, the ~ " ' polymer can be reacted v~ith basic metal salts to form metal salts of the polymer. Preferred metals are Ca, M6 Cu, Zn, Mo, and the 20 like.
Suitable properties sought to be imparted to the derivatized polymer include one or more of di*/.,la~l.,y, ~ viscosity .............. I.~ r ~' ' y~
friction -r '-, antiwear, antirust, seal swell, and the like. The preferred properties sought to be imparted to the derivatized polymer include dia~.,laQ~I~,y (both 25 mono- and ' ~ I) and viscosity . ~ l;"" primarily with attendant secondary dispersant properties. A " ~ I dispersant typically will function primarily as a dispersant viith attendant secondary viscosity ' ~
While the Koch r '- ~ ' and d~,~iv...i~iiu.. techniques for preparing ' ~ ' viscosity modi'ders (also referred to herein as ..... '~ viscosity index improvers or MFVI) are the same as for ashless di~r~rs~ntc the r ~ / of a ~ ' ' polymer intended for d~,.iv~ iu,. and eventual use as an MFVI will be controlled to be higher than r ' ~- ~ polymer intended for eventual use as a dispersant. This stems from the difference in Mn of the MFVI polymer backbone vs.
the Mn of the dispersant polymer backbone.
Accordingly, it is ~ .' ' that an M~VI will be derived from polymer having typically up to one and at least û.5 functional groups, (i.e. "n" of formula (I)) for each 20,000, preferably for each lO,000, AMENDED SHEET
, 21 ~9Q73 ~wo~s/3s326 r~l,u~.. . lo14 most preferably for each 5,000 Mn molecular weight segment in the backbone polymer.
Djspersants Dispersants maintain oil insolubles, resulting from oil use, in suspension in the _uid thus preventing sludge fl~rc~ on and ~nt~ al;u~l. Suitable dispersants include, for example, dispersants of the ash-producing (also known as detergents) and ashless type, the iatter type being preferred. The derivatized polymer ..~,..,I,..- ~;.,..~ of the present invention7 can be used as ashless dispersants and ' ~ ' viscosity 10 index improvers in lubricant and fuel r~ ,...I)n~:l;....
At least one fi.- tinnqli7qd polymer is mixed with at least one of amine, alcohol, including polyol, _ --" '-~1, etc., to form the dispersant additives. One class of particularly preferred dispersants are those derived from the fi~ ' ' polymer of the present invention reacted with (i) hydroxy compound, e.g., a polyhydric 15 alcohol or polyhydroxy-substituted aliphatic primary amine such as p~ ,.yll~l;lol or trismethyl. ~ ' - (ii) polyoxyalkylene polyamine, e.g. pol~u,.y~,.u~
diamine, and/or (iii) polyalkylene polyamine, e.g., polyethylene polyamine such as tetraethylene pentamine referred to herein as TEPA.
20 Derivqti7qtinn by Amine Compounds Useful amine compounds for derivatizing fi~n~tinnq'i7rqd polymers comprise at least one amine and can comprise one or more additional amine or other reactive or polar groups. Where the functional group is a carboxylic acid, carboxylic ester or thiol ester, it reacts with the amine to form an amide. Preferred amines are aliphatic25 saturated amines. Non-limiting examples of suitable amine compounds include: 1,2-pul~.,lh,l~ amines such as diethylene triamine; triethylene tetramirle; LeLIa~,lh~pentamine; etc.
Other useful amine compounds include: alicyclic diamines such as 1,4-30 di(~l~u~u~.,.llyl) e~,lullt.~ e, and heterocyclic nitrogen cu,.,~uul.J~ such as Mixtures of amine compounds may ad~a~l~ag~uu~ly be used. Usefulamines also include polyoxyalkylene polyamines. A particularly useful class of amines are the polyamido and relâted amines.
35 Derivatization by Alcohols The ~ ' ' polymers of the present invention can be reacted with alcohols, e.g. to form esters. The alcohols may be aliphatic cu.."luu,.J~ such as , ~ ¦ 8 ~? Q 73~

u-lullJdli~. and polyhydric alcohols or aromatic compounds such as phenols and naphthols. The aromatic hydroxy .~ .I u ~ l~ from which the esters may be derived are i,lustrated by the following specific eAamples: phenol, b~- . ' ' I, alpha-naphthol, cresoll resorcinol7 catechol, etc. Phenol and a?kylated phenols having up to 5 three alkyl ~ are preferred. The alcohols from which the esters may be derived preferably contain up to 40 aGphatic carbon atoms. They may be ~u~ul~rJl;~
alcohols such as methanols, ethanol, isooctanol, etc. A useful class of polyhydric alcohols are those having at least three hydroAy radicals, some of which have been esterified with a ' Jl;_ acid having from 8 to 30 carbon atoms7 such as 10 octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid, or tall oil acid.
The esters may also be derived from I ' alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol. Still another class of the alcohols capable of yielding the esters of this invention comprise the ether-alcohols and ' ' '-including, for example, the UA~." jh,.~-, UAy~J~,...,-, amino-alkylene-, and amino-15 arylene-substituted alcohols having one or more oxyalAylene, - . " yl~,..e oramino-arylene oxyarylene radicals. They are eAemplified by Cellosolve, carbitol,,JII.,.IUA~. ' 1, etc.
The r " ~' ~ polymer of this invention i5 reacted with the alcohols according to ~,u~ l? iulla~ n, or i ' techniques. This normaly involva heating the r '' ~' ~ polymer with the alcohol, optionally in the presence of a norma?ly Gquid, ' "~ inert, organic liquid ~Ul~.?~/ ''' ' and/or irl the presence of ~ cata?yst.
D-,~iv4~;~4~iù~l by Reactive M t. ~ I Corm~?oqnds Useful reactive metais or reactive meta?~ compounds are those which v~ill form metal salts of the 5 " ' polymer or meta?l-containing complexes with the ~ polymer. Metal complexes are typica?ly achieved by reacting the 'i ' ' polymers with amines and/or alcohols as discussed above and also with complex forming reactants either during or subsequent to amination. Complex-forming meta?~ reactants include the nitrates, nitrites, ha?~ida, ~ ?~uA~ ., etc.
The appropriate r '' ~' ~ polymer of this invention can be reacted with any individua?l derivatizing compound such as amine, a?cohol, reactive meta?, reactive metal compound or any ~ ;.. of t vo or more of any of these; that is, for example, one or more amines, one or more alcohols, one or more reactive meta,s or 35 reactive meta?~ , ' or a mixture of any of these. S ' ",~, inert organic AMENDED SHEi~

2 1 ~ 9 (~3 73 r iiquid diiuents may be used to faciiitate mixing, l~ U-~ control, and handiing of the reaction mixture.
The reaction products produced by reacting r ~ ~ polymer of this invention with d~,.iva~ compounds such as aicohols, nitrogen-containing reactants, 5 metai reactants, and the like wiii, in fact, be mixtures of various reaction products.
The r 1- ' polymers themselves can be mixtures of materiais. While the '` ' ' polymers themselves possess some dispersant ~ and can be used as dispersant additives in lubricants and fuels, best resuks are achieved when at least 30, preferably, at least S0, most preferably 100% of the functional groups are 1 0 derivatized.
Post Treatment The 'i ' ' and/or derivatized polymers from the present invention may be post-treated. WO-A-9413709 discloses processes for post treatment.

Lllbri~ tin~ C4~ v~;~;vl,, The Koch '` ' ' polymer, in addition to acting as ' for dispersant and MFVI Illal.ura~.Lul~;, can be used as molding release agents, molding agents, metai working lubricants, point thickeners and the i;ke. The primaly utiiity for 20 the products of the invention, from r - 1- I polymer ail the way through post-treated derivatized polymer, is as additives for oleaginous ~ ;t", The additives of the invention may be used by ,uv. aL;vll into an oleaginous materiai such as fuels and lubricating oiis. WO-A-9413709 discloses the use of the additive derived from the present invention in fuels and lubricating oils.

amvles Ill the examples below, a significant reduction in the amount of iight ester impurity generated was achieved by l,..,iLl;~.~.u.g the polymer prior to feeding the polymer to the l,albu~' reactor.
In Example I a polymer feed was prestripped in a short path evaporator to eiiminate light polymer (iight ester precursors). The distillate was discarded. This prestripped polymer was fed into the ~ a bu..J' reaction (Example A) and reactedurlder conditions ~ similar to polymer which was not prestripped (Example B). In Examples A and B a short path evaporator was used to strip unreacted 35 ~ih,l iu..r' ' (DCP) and other impurities from crude ester produced in a AMENDED SHEEr ~ 1 8 ~? P ~?3 r r ~

bul~rla~;vll reaction. The distillate from the ~ Jvlaliu.. ~ of Examples A and B was compared.
The data in Table I show that ' "~, less distillate was collected ~om the stripped polymer, 15.3 wt. % (Example A) than the unstripped polymer, 21.2 wt. %5 (Example B).
Table I
~'~Vl~;Ub~ Conditions Vacuum Feed rate Temp. kPA Distillate Residue FeedKelHr_ C (m~ Wt. o/o Ke/~r Polymer Feed 50 23û 0.2 (1.5) 0.4 49.7 (Example 1) StrippedPolymer 62 230 1.267(9.5) 15.3 47.1 (Example A) Unstripped Polymer 56 230 1.24 (9.3) 21.2 41.4 (Example B) From mass balances, the amount of light ester was calculated for each batch of crude ester. Then the mass of light ester was determined per kilogram of residueproduct ('` ' ' polymer). The C4-C24 light esters of Example A amounted to only 0.03 kg (mostly C4 and Cs esters) in 8.1 kg total distillate whereas the C4-C24 light esters of Example B amounted to 0.1 kg (mostly C4-C6 esters) of 11. I kg total 15 distillate, as determined by mass balance data. This near order of magnitude difference would have a dramatic economical effect on a ..;~1 scale operation, requiring disposal and expensive handling of a much higher amount of light ester. The light ester otherwise rapidly builds up in and deteriorates the production process unless removed by more expensive means.
There is a threefold lesser level of light ester present in the product producedfrom the stripped polymer feed. Example A had only 0.79 grams light ester per kg ~ polymer whereas Example B had 2.91 grarns.

~MENDED SHE~T

~ 2 1 ~9~3 - - -~ .
Molecular Weight Data by Gel Perrneation Ch~ J (GPC) for r.
Polymer Made From Stripped and Unstripped Polymer Feed (E~camples A & B) .
W~ioht P~ nt E' -T~IL h~ 500(1~ 2Q~Q~
UnstrippedPolymer(Examplel3] 235-240C 3530 227 1.32 4.12 6.33 CarbonylatedProductAfterShort 235-240C 3415 2.35 1.5 4.81 6.63 Path Strip at 1.33 I~PA (10 r~n Hg) Carbonylated Product After Short 235-240C 3467 2.32 1.38 4.68 6.64 Path Strip at 0.13 IIPA (I rr~m HO
Stripped Polymer (Example A) 235-240C 3647 2.19 1.03 3.86 6.26 CarbonylatedProdnctAfterShort 235-240C 3643 2.26 1.04 4.23 Path Strip at 1.33 kPA (10 rnm Hg) CarbonylatedProductAfterShort 235-240~C 3597 2.28 1.15 4.36 7.09 Path Strip at 0.13 kPA (I rnm Hg) 5 (1) weight percent of rnaterial less thart stated molecular weight (2) weight percent of material greater than stated molecular weight The data in Table 2 show that the ~.cll,u.. ,'i ' product after short path ..
.~C~ shows an improved quality when made from stripped polymer (Example 10 A) when compared to product made from unstripped polymer (Example B). Productfrom Example A shows a dllc "~, higher molecular weight (Mn), a narrower molecular weight distribution (Mw/~) and a lower amount of polymer less than 500and 1,000 molecular w~ight.

AMENOED SHEET

Claims (8)

CLAIMS:

1. A Koch process functionalized hydrocarbon polymer wherein the polymer backbone has Mn500, functionalization is by attachment of groups of theformula -CO-Y-R3 wherein Y is O or S, and R3 is H, hydrocarbyl, substituted hydrocarbyl, aryl, or substituted aryl, and wherein at least 50 mole % of the functional groups are attached to a tertiary carbon atom of the polymer backbone, prepared by a process comprising: removing light hydrocarbon from said polymer prior to functionalization, wherein said light hydrocarbon comprises C4 to C24 hydrocarbon.

2. The polymer of claim 1 wherein said light hydrocarbon comprises light hydrocarbon less than 300 number average molecular weight.

3. The process of claim 1 wherein said removing comprises heating of the polymer.

4. The process of claim 1 wherein said removing comprises stripping said polymer at a temperature of 180 - 300°C and under vacuum of 0.13 to 4.0 kPA (1.0 to 30 mm Hg.)

5. The process of claim 4 further comprising using an inert gas to remove said light hydrocarbon.

6. The process of claim 1 wherein said polymer is agitated.

7. The process of claim 1 wherein said process takes place in a short path evaporator.

8. A Koch process functionalized hydrocarbon polymer wherein the polymer backbone has Mn500, the polymer backbone prior to functionalization contains less than 1 weight percent hydrocarbon of carbon number C24 and below, functionalization is by attachment of groups of the formula -CO-Y-R3 wherein Y is O

or S, and R3 is H, hydrocarbyl, substituted hydrocarbyl, aryl, or substituted aryl, and wherein at least 50 mole % of the functional groups are attached to a tertiary carbon atom of the polymer backbone.