Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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
- 2 -
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
-- 3 -
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 ~ ~ .
~ ~ . . .. .. . .
-6 -
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 ~ ~
--7 -
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
-- 8 --
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,
- 12 -
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
- 13 -
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
- 14 -
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
- 15-
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~ --
... .. ..
- 16-
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 .
- 17-
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
- 18-
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
- 19-
R~ CAT. R
Il I
POLY- C + > POLY - C+ (Ir)
5 R2 R2
(carbenium ion)
Rl Rl
10 POLY - C+ + CO > POLY -C-CO+ (III)
2 R2
(acylium ion)
15 Rl Rl O
l 11
POLY - C - C+O + R3YH ~ POLY - C - C - YR3 (I~
R2 R2
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 ~
.' , . ... ....
., . .. -
-20 -
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 , , , , ,, ~
.
-21 -
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
- 22 -
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
-23 -
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)
R2
o
Il
40 which expression contains the acyl group -C-YR3. It will be understood that while the
9 ~7 ~ . :
-24 -
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 . -. .
.. ..
-25 -
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
-26-
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~
-27 -
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
-28 -
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 ~
-29 -
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 - - -
-30-
~ .
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
