CA2191453A1 - Preparation of copolymers of carbon monoxide and an aliphatic alpha-olefin - Google Patents
Preparation of copolymers of carbon monoxide and an aliphatic alpha-olefinInfo
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Abstract
A catalyst composition suitable for the copolymerisation of carbon monoxide with an aliphatic .alpha.-olefin, which catalyst composition comprises: a) a palladium compound, and b) an asymmetric phosphorus bidentate ligand of the general formula R5R6P-Q-CHR9-PR7R8, wherein Q is a 1,2-ferrocenyl bridging group, R5, R6, R7 and R8 are identical or different optionally polar substituted hydrocarbyl groups and R9 is hydrogen or an optionally polar substituted hydrocarbyl group; a process for the preparation of linear alternating copolymers of carbon monoxide with an aliphatic .alpha.-olefin having at least 3 carbon atoms, which process comprises contacting a mixture of the monomers with said catalyst composition; isotactic linear alternating copolymers of carbon monoxide with an aliphatic .alpha.-olefin having at least 3 carbon atoms.
Description
WO 9~ 998 2 1 9 1 4 5 3 r~l,~, A?n75 PREPARATION OF COPOLYMERS OF CARBON MONOXIDE AND AN ALIPHATIC
ALPhA-OLEFIN
This invention relates to a catalyst composition for the preparation of linear alternating copolymers of carbon monoxide and an aliphatic -olefin having at least three carbon atoms. The invention further relates to said preparation and to the resulting copolymers ~nd their use. In thes~ copolymers the units originating in carbon monoxide and the units originating in the olefinically unsaturated compound(s~ used in the preparation occur in an alternating order. Furthermore, the copolymers are regioregular and stereoregular, in particular isotactic.
The term "regioregular" used herein refers to the way in which the units originating in a monomer CH2=CH-R, R ~eing an aliphatic alXyl group, are bound to units originating in carbon monoxide.
Three possibilities are distinguishable, which are termed "head/head", "tail/tail" and "head/tail". They may be represented schematically as follows:
head/head: - (CH2) - (CHR) - (CO) - (CHR) - (CH2) -tail/tail: - (CHR~ - (CH2) - (CO) - (CH2) - (CHR) -head/tail: - (CH2)--(CHR) - (CO) - (CH2) - (CHR) -Regioregular copolymers are understood to be copolymers in which the units originating in the monomer CH2=CH-R are bound to the units originating in carbon monoxide pr~rln-i n:~ntl y in a head/tail fashion. The degree of regioregularity of such copolymers is expressed as the average regioregularity, which is defined as the percentage of the number of units originating in the monomer _5 CH2=CH-R which i~re bound to the units originating in carbon monoxide in a head/tail fashion.
The terri "stereoregular" used herein refers to the con-figuration of the chiral carbon atoms present in the regioregular copolymer chains relative to the configuration of the chiral carbon atoms together with which they form part of a diad. A diad in this 2 1 9 1 4 5 3 F~~ 75 conn~ction is urderstood to be a segment of the polymer chain which contains two chiral carbon ~toms which are int~rconnected through a - (CH2) - (CO) - bridge. As regards the relation between the configurations of the two chiral carbon atoms of a diad, two possibilities _re distinguishahle, which are referred to as "isotactic" and "syndiotactic": when the two chiral c~rbon atoms in a diad have the same configuration this diad is called an isotactic diad, whereas the diad is called syndiotactic when the configurations are opposed. These options can be schematically represented as h isotactic: -C- lCE~2) - (CO) -C-R R
h R
syndiotactic: _ -C- ~Ch2) - (CO) -C-R ~}
The regioregular copolymers can be divided according to the structure of their chains into three classes:
1~ Polymer mixtures in which the numoer of isotactic diads is substantially equal to the number of syndiotactic diads are referred to ?5 atactic.
2) Polymer mixtures in which the number of isotactic diads is larger than the number of syndiotactic diads are referred to as ~ 50tAot; ~r 3) Polymer mixturea in which the num'oer of syn~iotzlrt;c di~ds is larger than the number of isotactic diads are referred to ~s syndiotactic.
The _tactic polymer mixtures mentioned under 1) are stereoirregular, whereas the other regioregular polymer mixtures ~ ' rr~ l above po.3sess a degree of stereoregularity. The degree of stereoregularity of the isotactic polymer mixtures is expressed as the ~ver~lge ~tereor~ Ari ty or isotacticity, which is understood to be the porr~.nt?rJe of isotactic diads, rAlr~lAto~ on the total number of di~ds present in the polymer chains. On the basis of this WO95/32998 2 l ~1 453 r~ 75 definition, the isotactic polymer mixtures have an average stereoregularity of more than S0~.
EP-A-384517 and EP-A-410543 disclose copolymers of carbon monoxide with an aliphatic a-olefin having at least three carbon atoms which are made up of linear chains in which the units originating in carbon monoxide alternate with the units originating in the -olefin. These copolymers have a certain degree of regio-and stereoregularity, more specifically they are isotactic in nature. For the sake of simplicity the polymer mixtures may be 0 ~I~c~-ri he~ as isotactic linear alternating copolymers .
EP-A-384517 discloses that the copolymers in question can be prepared by contacting a mixture of the monomers with a catalyst composition r; ci n~ a palladium compound and an asymmetric phosphorus bidentate ligand of the general formula RlR2P-R'-PR3R4, wherein R' is a bivalent bridging group rort:l;n;n~ at least two carbon atoms in the bridge, and Rl, R2, R3 and R4 ~re identical or different optionally polar substituted hydrocarbyl groups, such as the (+)-form and the ~-)-form of 4,5-bis(diph~ny1rh^srh;r hyl)-2,2-dimethyl-1,3-dioxolzne and (-)-4,5-bis(dibutylrht~srh;r thyl)-2, 2-dimethyl-1, 3-dioxolane.
In Macromolecules 25, 3604 - 3606 (1992) it is taught that by using as the asy~metric ligand (6,6'-dimethylbiphenyl-2,2'-diyl)bis-(diCyclohexy1rh~crh;n ) an isotactic linear alternating carbon monoxide/propene copolymer can be prepared which h~s an isotacticity 2~ of about 88~, AS calculated from the 13C-NMR data provided.
EP-A-4105~3 teaches that when isotactic copolymers are prepared which have a lower degree of isotacticity than required for a certain application, they can be treat~sd to increase their degree of isotacticity, e . g ., by extracting the copolymers with a suitable solvent. It is disadvantageous that in this treatment a polymer byproduct is obtained which in many cases has to be r~ rci~1 because it does not fulfil the requirements as regards tacticity.
A further disadvantage is that when the treatment is applied to polymers which ar~ made up of aliph~tic -olefins having, e.g., more than 10 carbon atoms, it becomes increasingly more difficult to 21q345~
WO95/32998 r~ ' 71175 carry out the treatment efficiently and with the effect of obtaining n polymer with d high degree of isotdcticity. It would therefore be desirable to dify th~ polymerisation such that copolymers with a high degree of isotacticity can be prepared Pff;ri~.ntly, i.e. such that the treatment can be avoided and also that the rate of polymerisation is improved.
It hds now surprisingly been found that the polymerisation rate can be improved rrnc;~r?hly by using in the catalyst composition an asymmetric phosphorus bidentate ligand of the general formula RSR6P-Q-ChR9-PR7R8, wherein Q i5 a 1,2-ferrocenyl bridging group, RS, R6, R7 and R8 are identical or different optiondlly polar substituted hydrocarbyl groups and R9 is hydrogen or an optionzlly polar substituted hydrocarbyl group. With a speciflc ~ubstitution pattern of the ferrocenyl containing asymmetric ligdnd, viz. such thdt RS
and R6 are identicdl or different optionally poldr substitut~d Qromatic hydrocarbyl groups, R7 dnd R8 dre identicdl or different cycloaliphatic hydrocarbyl groups, and R9 is an aliphatic hydrocarbyl group, d polymerisation rate can be dchieved which ~ven exceeds the rate achieved with 1, 3-bis (diethy~ rhrsrh; nr~ propdne when used under otherwise comparable conditions. The latter ligand ha~
been indicdted to be excellently suitdble for obtdining a high polymerisation rate in the copolymerisation of cdrbon monoxide and dn aliphatic -olefin, yielding a linear alternating regioregular atdctic polymer, cf. EP-A-516238.
It is even more a surprise that the isotacticity of the copolymers which dre obtdined by using the ferrocenyl r~nt~ininr asymmetric ligand can be higher than achieved previously, even higher than 959~, substantidlly without loss of the regioreguldrity, which typically amounts to more than 959~, more typically more thrm 99~.
Ligdnds of the g~nerdl formula RSR6P-Q-C~R9-PR7R8 AS defined hereinbefore dre known from EP-A-564406.
The present finding led to the ef ficient synthesis of isotdctic copolymers of carbon monoxide dnd aliphdtic c-olefins, in particular these hdving more thdn 10 carbon atoms . Iln~Yr rte~l y it WO 9S/32998 2 1 9 1 4 5 3 ~ A7n7!j was subsequently found that the latter copolymers have a better performance than comparable regioregular, atactic copolymers when they are used in p~r~ff;n;r hydrocarbon oils as additive for improving the low temperature properties of the oil, such as the cold filter plugging point. Such use of comparable atactic copolymers is known from EP-A-468594. The role of the tacticity of a polymeric additive on its effectiveness as paraffinic oil additive, which has now been found, is unprecedented.
hrrrr~lingly, the present invention relates to a catalyst composition suitable for the copolymerisation of carbon monoxide with an aliphatic a-olefin, which catalyst composition comprises a) a palladium compound, and b) an asymmetric phosphorus bidentat~ ligand of the general formula RSR6P-Q-CHR9-PR7R8, wherein Q is a 1,2-ferrocenyl bridging group, R5, R6, R7 and R8 are identical or different optionally polar substituted hydrocarbyl groups and R9 is hydrogen or an optionally polar substituted hydrocarbyl group.
The invention further relates to a process for the preparation of copolymers of carbon monoxide with an aliphatic c~-olefin having at least 3 carbon atoms, which process comprises contacting a mixture of the monomers with a catalyst composition of th~
invention .
In addition the invention relates to a copolymer of carbon monoxide with an aliphatic -olefin having at least 3 carbon atoms which copolymer comprises linear chains in which the units originating in the aliphatic a-olefin alternate with units originating in carbon monoxide, and which copolymer has an isotacticity of 959~ or more.
The invention further relates to a copolymer of carbon monoxide with an aliphatic a-olefin having more than 1~ carbon atoms which copolymer comprises linear chains in which the units originating in the aliphatic -olefin alternate with units originating in carbon monoxide, and which copolymer is isotactic. The copolymer has pr~ferably an isotacticity of 95~ or more.
~IVO 95~32998 ~ 21 91 453 r~ /a A further embodiment of thi6 invention relates to a paraffinic hydrocarbon oil composition containing a paraffinic hydrocarbon oil And as an additive a copolymer of carbon monoxide with an aliphatic a-olefin having more than 10 carbon atoms which copolymer comprises linear chains in which the units originating in the aliphatic a-olefin altern~te with units originating in carbon monoxide, and which copolymer is isotactic.
The c~talyst composition of this invention is based on a pdlladium compound. The catalyst composition may be based on a precursor compound ~-nnt~;n;ng palladium in its zero-valent state.
Preferably the palladium compound is a palladium aalt, such as a salt of a carboxylic ncid. Particularly suitable i5 palladium acetA te .
The phosphorus bidentate ligand of the general formula RSR6P-Q-CHR9-PR7R8 as defined hereinbefore is asymmetric. I~epending of whether R9 is hydrogen or ~n optionally polar substituted hydrocarbyl group the ligand's structur~ provid~s for at l~ast one or at l~ast two el~m~nts of chirality. The ligdnd may b~ pr~sent as an optically inactiv~ mixtur~ of possibl~ st~re~;~ ~c or diastereoisom~rs, or it may b~ pres~nt as an optically activ~
mixture in which there is ah excess of a ster~oisomer or diast~r~o-isom~r, or th~ ligznd consists of on~ substantially pure st~reoisom~r or diaster~oisom~r. The skilled r~ad~r will appr~ciat~
that it will hav~ no bearing on th~ isotacticity of the copolymer wh~th~r th~ lig~nd us~d consists of on~ st~reoisomer or diaster~oisom~r or it consists of said st~reoisomer or dia~t~re~,; r and its optical antipode.
The group Q of the bidentate ligand is a bivalent 1, 2-f~rroc~nyl group which may contain furth~r substitu~nts attach~d to the pentadienyl groups, 1.~. oth~r than th~ RSR6P-- ~nd R7R8P-ChR9 groups in a 1,2-position, but this is not pr~ferred.
The hydrocArbyl groups R5 and R6 are prefer~bly optiondlly polar substitut~d aromatic hydrocarbyl groups which typic~Llly have 6 to 12 cdrbon atoms. Wh~n they are polar substituted, eligible substituents ar~ for exampl~ dialkylamino groups, whereas pr~ferred W0 95/32998 2 1 9 1 4 5 3 1 ~
polar substituents are alkoxy groups, such as methoxy groups. Polar substituents are typically positioned ortho with respect to the phosphorus atom. The groups RS and R6 are preferably identical.
They are in particular phenyl groups.
The hydrocarbyl groups R7 and R8 are preferably aliph~tic groups or more preferably cycloaliphatic groups, such groups typically contain no more than 10 c~rbon atoms. Optionally they may be connected to one another through a c4rbon-carbon bond, so that together with the phosphorus atom to which they are attached they form a heterocyclic phosphorus containing group. The groups R7 and R6 ~re preferably identical. They may in particular be selected for example from ethyl, 1-propyl, 2-propyl, I-butyl and 2-butyl groups, more in particular they are cyclohexyl groups.
The group R9 is hydrogen or an optionally polar substituted hydrocarbyl group, typically having no more than 10 carbon atoms.
The group R9 is prefera~hly other th~n hydrogen since this may further increase the isotacticity of the polymer obtained. The group R9 is in particular an alkyl group, more in particular a n-~lkyl group, such as an ethyl, 1-propyl or 1-butyl group, most in pzlrticular a methyl group.
Very good results can be achieved when as the phosphorus bidentate ligand one of the following is used:
(R~ [ (s)-2-~diphenylrh^srhino) ferrocenyl] }ethyldiphenylrhoerh;n,-, I(R)-1-[(5)-2-(dicyclohexylrhns~h;n^)ferrocenyl])ethyldiphenyl-rh~ph; n~.
{ (R) -1- [ (S ) -2- (dicyclohexylphosphino) ferrocenyl] ) ethyldicyclohexyl-phosphine, [2-(dipheny~rh^srh;n~ )ferrocenyl~methyldicyclohexylrh^srhine or {1-[2-(diphenylrho~rhino)ferrocenyl] )ethyldiethylrh^srh;n .
Even further improved results can be obtained by using ~ (R)-1-[ (S)-2- (diphenylrhosrh;n^) ferrocenyl] )ethyldicyclohexylrh^~rh;n~ as the phosphorus bidentate ligand.
The quantity of the phosphorus bidentate ligand present in the c~talyst composition of this invention may vary between wide limits.
Suitably the quantity is in the range of from O . 5-2 mol, in pdrticular from 0.~5-1.5 mol per mol of pA~
The catalyst composition of this invention may compr~se as an ~dditional component a component which i5 generally thought to act as a source of anions which are weakly or non-coordinating with palladium. The anion is preferably an anion of an acld having a pKa of less than 6 (~ rmi n~ in an aqueous solution at 18 C), suitably less than 4 and in particular less than 2. Examples of suitable acids having a pKa of less than 2 are mineral acids, such as perchloric acid, sulphonic acids, such as p-toluenesulphonic acid and trifluorome~hAnGc~lrh~nic acid, and halogen carboxylic acids, such a~ trifluoroacetic acid. ~he source oi arions may be incorporated in the catalyst composition in the form of an acid or in the form of a salt. Nickel perchlorate is a very suitable sourc~
of anlons. The catalyst composition may alternatively comprise as an additional compound an adduct of boric acid with a 1, 2-glycol, a catechol or a salicylic acid, a borate cuch as lithium tetrakis(perfluorophenyl)borate or sodium tetrakis~bis-3,5-(trifluoromethyl)ph~nyllborate or a borane such as tris (perfluorophenyl)borane, triphenylborane or tris [bis-3, 5-ttrifluoromethyl)ph~nyllborane It is also conc~ivable to use an alumoxane, such as methyl aluminoxane or t-butyl Al n~ Y n~ as an additional component. The quantity of these additional components when present in the c~talyst composition of this invention may vary between wide limits. Suitably the quantity is in the range of from 0.5-50 equivalents, ~n p~rticular from 1-25 equivalents per mol of p~llA~ owever, Alllrn;nnYAn~-c may be used in such a quantity that the molar ratio of aluminium to palladium is in the range of 4000:1-10:1, preferably 2000:1-100:1.
In order to increase the rate of polymerisation it is preferred to include in the catalyst composition a quinone, in particular a 1,4-quinone, such as a l,g-h~n7~q~in~ and a 1,4-naphthoquinone.
The quantity of quinone suitably lies lr the range of from 1-5000 mol, in particular from 5-1000 mol per mol of palladium.
The aliphatic ~-olefin used as one of the monomers of the process may be a branched or a straight chain olefilm The aliphatic WO95/32998 2~ ~ 1 453 r~l~L~ 7S
a-olefin may contain hetero atoms, such as oxyg~n and nitrogen, which are present when the aliphatic a-olefin is o.g. an olefinically unsaturated ester, alcohol or amide. The aliphatic a-olefin may also contain an aromatic substituent in such a manner that there is no conjugation of the aromatic substituent with the olefinic double bond, such as in 4-phenyl-1-butene. The aliphatic a-olefin is typically a hydrocarbon. The aliphatic a-olefin may be a single olefin but also a mixture of a-olefins may be used, or, if desired, a mixture of an a-olefin with ethene. In the latter case the units in the polymer chains originating in ethene do not contribute to the regio- and stereoregularity of the polymer. In such a case the regularity of the polymer is exclusively related to the parts of the polymer chains which contain units originating in the a-olefin.
When the polymer of this invention is to be used as an additive for a paraffinic hydrocarbon oil, the aliphatic a-olefin contains suitably more than 10 carbon atoms and typically not more than 40 carbon atoms, in particular not more than 30 carbon atoms.
Preferably it is a straight chain olefin. It is also possible that in addition to aliphatlc a-olefins having more than 10 carbon atoms one or more aliphatic a-olefins having not more than 10 carbon atoms are incorporated. Very suitable is a mixture of aliphatic a-olefins of carbon numbers in the range of from 12 to no more than 24. Very good results have been achieved with a polymer based on 1-hr _ _,lr _.. r .
When the polymer of this invention is to be used for other purposcs than as a paraffinic oil additive, e.g. in an rn ~ne~rjn application or as a packaging material, it is eligible to use an aliphatic a-olefin having at most 10 carbon atoms. It is particularly suitable to use a lower olein as the aliphatic a-olefin, i.e. an olefin ~ nntAin;n~ no more than 6 carbon atoms, as a single olefin or as a mixture rnr~inln~ aliphatic a-oleins, if desired in conjunction with ethene. Very good r~sults have been achieved with propene, 1-butene and 4-methyl-1-pentene as the aliphatic a-olefin.
WO 95/32998 1 ~
2t9t453 The preparation of the polymers is preferably carried out by contacting the monomers with the catalyst composition of this lnvention in a diluent in which the polymers are insoluble or virtually insoluble. Lower aliphatic alcohols and in particular methanol are suitable as diluents. Very suitable diluents contain for at least 80 9~v an :aprotic liquid and ~or at most 20 ~v a protic liquid such ns a lower aliphatic alcohol. The aprotic liquid may be A polar liquid, such as acetone, methyl acetate, tetrahydrofuran, dioxane, diethyleneglycol dimethyl ether,, bu-yL~,lactone, N-methylpyrroLidone or 5ll1rholAn~-, or an apolar liquid, such as n-hexane, cyclohexane or toluene. ~avourable resuLts can be obtained by using a mixture o~ tetrahyc~ro~uran and methanol. I~ desired, the polymerisation can also be carried out in the gas phase. The polymer preparation can take place batchwise or ~nt;nll~llrly.
When the polymerisation is carried out in a diluent which contains a lower 31iph2tic alcohol the rate of polymerisation may be ;nr-r~c~.~l by adding to the polymerisation mixture an ortho ester, such as a trialkyl orthoformate, in particular trimethyl orthoformate. The quantity of the ortho ester may vary between wide limits. Preferably it is used in a quantity of between 100 and 5000 mol, in particular 500 and 3000 mol per mol oi r~
The quantity of catalyst composition used in the preparation of the polymers may vary within wide limits. Per mol of olefinically unsaturated compound to be polymerised a quantity of catalyst composition is preferably used which contains 10-7 to 10-3 and in particular 10-6 to 10-4 mol o~ r~
The preparation of the polymers is preferably carried out at a t~ -rilt~-rr. of 20-150 C and a pressure o~ 2-150 bar ~nd in particular at a temperature of 30-130 ~C and a pressure of 5-100 bar. Suitably a temperature below 80 C, in particular below 60 C is selected as this leads to a higher isotacticity of the copolymer. The molar ratio of the olefinically unsaturated compounds relative to carbon monoxide i5 preferably 10:1 to 1:10 and in particular 5:1 to 1:5. The polymerisation may be carried out in the presence of hydrogen, in which case the hydrogen is suitably present WO 95/32998 P~ ^7~75 219~453 in a quantity of from 0.1-0.5 mol per mol of carbon monoxide.
The copolymers according to this invention may be recovered from the polymerisation mixture by any suitable method. Such methods are well known in the art.
According to the present invention the low-temperature t properties of paraffinic hydrocarbon oils, such as the cold filter plugging point and the pour point, can be improved by using as an additive an isotactic linear alternating copolymer of carbon monoxide and an aliphatic a-olefin having more than 10 carbon atoms.
The copolymer has preferably an isotacticity of 9S~ or more. The copolymer may also be used as an aid in extractive dewaxing processes. An example of such a dewaxing process is disclosed in EP-A-482636. Examples of paraffinic hydrocarbon oils include gas oils, diesel oils, lubricating olls and crude oils. Very favourable results can be achieved with paraffinic gas oils.
The molecular weight of the copolymers which are eligible to be used as additive in the paraffinic hydrocarbon oils may vary between wide limits. By preference, copolymers are used having a weight average molecular weight (Mw) between 103 and 106, in particular between 2x103 and 105. The preference for a given molecular weight and also for a given number of carbon atoms of the aliphatic a-olefin~s) from which the copolymer is prepared is substantially determined by the nature and the quantity of the paraffins present in the paraffinic hydrocarbon oil. The quantity of copolymer which according to the invention is taken up into the paraffinic hydrocarbon oil may vary between wide limits. It is preferred to employ 1-10, 000 and in particular 10-1000 mg of copolymer per kg of p~r:~lff;nir hydrocarbon oil.
In addition to the present copolymers further additives may be added to the paraffinic hydrocarbon oil, such as other polymeric additives than copolymers according to this invention, antioxidants, corrosion inhibitors, metal deactivators and so called wax anti settling agents ("WASA"). Other polymeric additives are, for example, commercially available poly(ethene/vinyl carboxylate)s 35 ~nnt~;nln~ 20-35 9GW of the vinyl carboxylate, wherein the vinyl W095/32998 21 ~1 453 r~
carboxylate is typically vinyl acetate or vinyl propionate. This invention also relates to an additive composition per se comprising a copolymer of carbon monoxide with an aliphatic a-olefin having more than 10 carbon atoms which copolymer compris~s linear chains in which the units originating in the aliphatic a-olefin alternate with units originating in carbon monoxide, and which copolymer is i~otactic, and a poly(ethene/vinyl carboxylate) r~ntAinin~ 20-35 9~w of the vinyl carboxylate, wherein the vinyl carboxylate is typically vinyl acetate or vinyl propionate. With respect to their ability to improve the low-temperature properties o~ the paraffinic hydrocarbon oil the copolymers according to this invention may have a synergistic effect with the further additives mentioned, in particular with polytethene/vinyl carboxylate).
The polymer constituents of the other polymeric additives have typically a weight average molecular weight between 103 and 106, in particular between 104 and 105. ~hen other polymeric additives are present in the paraffinic hydrocarbon oil, the copolymer according to this invention constitutes preferably 1-90 ~w of the total of polymeric additives.
The invention will now be illustrated with reference to the following cxamples. The regio- and stereoregularity of the copolymers prepared according to Examples 1-15 was derived from 13C-NMR spectra (deutero-hexafluoroisopropanol solvent), by anzly~ing the signals in the carbonyl region.
E:xample A carbon monoxide/propene copolymer was prepared as follows. A
stirred autoclave was charged with 150 ml tetrahydrofuran, 39 g (65 ml) propene and a catalyst solution consisting of 1.5 ml tetrahydrofuran, 8 . 5 ml methanol 0. 06 mmol palladium acetate, 0.3 mmol nickel perchlorate, 0. 07 mmol I (R) -1- [ (S) -2- (diphenylphosphino) ferrocenyll )ethyldicyclo-hexyl rhr~rh~ n~ and 3 . 0 mmol 1, 4--n~rhthAqll; nrn~, W095/32998 21 91 453 r~l,~l h 1~
Air present in the autoclave was replaced by carbon monoxide, which was forced in to achieve a pressure of 80 bar. The contents of the autoclave were brought to a temperature of g2 C. After 41 hours the polymerisation was terminated by cooling to room temperature and releasing the pressure. The su~p~'n~i nn obtained was diluted with methanol. The solids were collected by filtration, washed with methanol and dried.
The yield of copolymer was q7 g. The polymerisation rate calculated from the copolymer yield was 180 g copolymer/ (g p~ .. i; hour). The isotacticity of the copolymer obtained was more than 959~. The product showed an optical rotation [c~] D of 28 . 4, as measured in hexafluoroisopropanol at a concentration in the range of 5-10 g/100 ml. The optical rotation is a molar value calculated on the basis of the molecular weight of the copolymer's repeating unit ~i.e. 70).
Example 2 A carbon monoxide/propene copolymer was prepared in substantially the same way as in Example 1, but with the following differences:
a) 0 07 mmol of ( (R) -l- [ (S) -2- (dicyclohexylphosphino) ferrocenyl] )-ethyldiphenylrh^sphin~ was used instead of ( (R) -1- [ (S) -2- (di-phenylrh~rhin~) ferrocenyl] )ethyldicyclohexylrhnsph;n~, and b) the reaction time was 114 hours instead of 41 hours.
The yield of copolymer was 20 . 3 g . The polymerisation rate was 28 g copolymer/ (g palladium.hour) . The isotacticity of the copolymer obtained was 88~.
Example 3 A carbon monoxide/propene copolymer was prep~red in substantially the s2me way as in Example 1, but with the following differences:
a) 0 07 mmol of ((R)-1-[(5)-2-(dicyclohexylrh^sphin^)ferrocenyl]}-ethyldicyclohexylrhosrh;n~ was used instead of ( (R) -1-[ (S)-2-(diphenylphosphino)ferrocenyl]~ethyldicyclohexylrh^~rh;n~, andb) the reaction time was 138 hours instead of ql hours.
The yield of copolymer was 30. 8 g. The polymerisation rate was 35 g copolymer/ ~g palladium.hour) . The isotacticity of the copolymer obtained was 90~.
Example 4 A carbon monoxide/propene copolymer was prepared in substantially the same way as in Example 1, but with the iollowing differences:
a~ 0.07 mmol of ((R)-l-[(S)-2-(diphenylrh~srh;nn)ferrocenyl3}-ethyldiphenylrh^srh;n~- was used instead of ~(R~-1-1(5)-2-(di-phenylrh~srh;no) ferrocenyll )ethyldicyclohexylEh^srhin~-, and b) the reaction time was 116 hours instead of 41 hours.
The yield o copolymer was 27 . 8 g. The polymerisation rate was 38 g copolymer/ (g palladium.hour) . The isotacticity of the copolymer obtained was 829~.
Ex~mple S (for ~ . - r; ~on, not according to the invention) -- ~ - . .......
A carbon noxide/propene copolymer was prepared in substantially the same way as in Example 1, but with the following differences:
~) 110 ml instead of lS0 ml tetrahydrofuran and 87 ml instead of 65 ml propene were used, b) the catalyst solution consisted of 3 . 9 ml tetrahydrofuran, 1. 4 ml methanol 0.091 mmol palla=dium acetate, 0. 65 mmol nickel perchlorate, 25 O.lOS mmol (-)-4,5-bis(dibutyl~nh~sph;n thyl)-2,2-dimethyl-1, 3-dioxolane and 6.3 m~ol 1,4--n~rh~h~ l;n~nf., c) the pressure of carbon monoxide was 45 bar instead of 80 b~r, d) the reaction time was 65.1 hours instead of 41 hours, and 30 e) the reaction mixture was diluted with water instead of methanol .
The yield of copolymer was 6. 83 g. The polymerisation r~te was 10.8 g copolymer/(g rAll~ hour). The product showed an optical rotation [CL3 2~ of +10 . 4, as measured in hexafluoroisoprop~nol .
WO 95/32998 1 ~
~lql453 Example 6 A c4rbon monoxide/propene copolymer was prepared as follows. A
stirred autoclave was charged with 75 ml tetrahydrofuran, 20 ml propene, 1 ml trimethyl orthoformate and a catalyst solution cons i s ting o f 4 . 0 ml methanol 0. 06 mmol palladium acetate, 0 . 3 mmol nickel perchlorate, 0. 07 mmol t (R) -1- [ (S) -2- (diphenylphosphino) ferrocenyl] )ethyldicyclo-hexylphosphine, and 3. 0 mmol 1, 4-naphthoquinone.
Air present in the autoclave was replaced by carbon monoxide, which was forced in to achieve a pressure of 80 bar. The contents of the autoclave were brought to a temperature of 46 C. The pressure was kept constant by supplying carbon monoxide. From the r~te of consumption of carbon monoxide it was calculated that the average polymeris~tion rate during the first hour of the polymerisation amounted to 490 g copolymer/ (g palladium.hour) .
After 10 hours the polymerisation was terminated by cooling to room temperature and releasing the pressure. The suspenJion obtained was diluted with methanol. The solids were collected by filtration, washed with methanol and dried.
The yield of copolymer was 16 g. The isotacticity of the copolymer obtained was more than 9S~. It had a melting point of 185 C.
Example 7 A carbon monoxide/propene copolymer was prepared in substantially the same way as in Example 6, but with the following differences:
a) 0.07 mmol of racemic (1-[2-(diphenylrho~Fh;n~)ferrocenyl])-ethyldiethylrh~sFh;n~ was used instead of I (R)-1-[ (S)-2-~di-phenylrh~eph;n~)ferrocenyl])ethyldicyclohexylphosphine, and b) the polymerisation temperature was 49 C instead of 46 C.
The average polymerisation r~te during the first hour of the polymerisation amounted to 195 g copolymer/ (g pAl 1 A~'l; hour) . The WO 95/32998 2 1 9 1 4 5 3 P~ l/~ . /a '-yield of copolymer was 10 g. The isotacticity of the copolymer obtained was estimated at about 70~.
Example 8 A caroon monoxide/propene copolymer was prep~red in substantially the same way as in Example 6, but with the following di f f erences:
a) 0 07 mmol of racemic [2-(diphenylrhn~ph;nn)ferrocenyl]methyldi cyclohexylrhn~rh;n~ was used instead of I (R)-l-l (S)-2-(di-phenylrhnsrh;n~n)ferrocenyl]~ethyldicyclohexylrhnsphinf~, and b) the polymerisation temperature was 49 C instead of 46 C.
The average polymerisation rate during the first hour of the polymerisation amounted to 270 g copolymer/ (g p=l 1~; hour) . The yield of copolymer was 12 g. The isotacticity of the copolymer obtained was estimated at about 80~.
Example 9 (for I "J~r~nn, not accordlng to the invention) A carbon monoxide/propene copolymer was prepared in substantially the same way as in Example 6, but with the difference that 0 . 07 mmol of 1, 3-bis (diethylphosphino~ propane was used instead of ( (R) -1- [ (S) -2- (diphenyl E~hnerh; nn) ferrocenyl] ) ethyldicyclohexyl-phosphine.
The average polymerisation rate during the first hour of the polymerisation amounted to 220 g copolymer/ (g palladium.hour) . The yield of copolymer was 11 g. The copolymer obtained was regioregular ~md atactic. It had a melting point of 131 C.
Example 10 ~.. . .
A carbon monoxide/4-methyl-1-pentene copolymer was prepared as follows. A stirred autoclave was charged with 8 . 4 g 4-methyl-1-pentene and a catalyst solution consisting of 14 ml t-butanol, 1.3 ml methanol, 2.1 ml toluene, 0.1 mmol palladium ~cetate, O . 3 mmol nic~cel perchlorate, 0.11 mmol 1 (R)-l-[ (5)-2-(diphenylrhnsrh;nn) ferrocenyl] )ethyldicyclo-hexylrhn~rhin--, and WO g5/32998 r~ 7s 1. 5 mmol 1, 4-naphthoquinone .
Air present in the autoclave was replaced by carbon monoxide, which was forced in to achieve a pressure of 40 bar. The contents of the autoclave were brought to a temperature of 40 C. After 168 hours the polymerisation was terminated by coollng to room temperature and releasing the pressure. The mixture obtained was stirred in methanol. The solids were collected by filtration, washed with methanol and dried.
The yield of copolymer was 10 g. The isotacticity of the copolymer obtained was more than 959~.
Example 11 A carbon monoxide/l-butene copolymer was prepared ufiing the procedure of Example 10, but with the following differences:
a) 10 g l-butene was used instead of 4-methyl-1-pentene, b) carbon monoxide was forced in to achieve a pressure of 43 bar instead of 40 bar, and c) the time of polymerisation was 21 hours instead of 168 hours.
The yield of copolymer was 9.1 g. The isotacticity of the copolymer obtained was more than 95~.
The 13C-NMR analyses further revealed that the copolymers prepared in the Examples 1 - 11 had a linear alternating structure.
By comparing the results of Examples 1 - 5 it becomes apparent that by using a ferrocenyl ~ntA~nin7 bidentate ligand according to this invention a polymerisation rate can be achieved which exceeds by far the polymerisation rate achieved in the known polymerisation using (-) -4, 5-bis ~dibutyl rhnsrh; - thyl) -2, 2-dimethyl-1, 3-dioxolane the ligand. Particularly good result~ are obtzined by selecting fcrrocenyl ront:~in;ng ligand of the general formula R5R6P-Q-CHR9-PR7R8, wherein Q is a 1,2-ferrocenyl bridging group, R5 and R6 are aromatic hydrocarbyl groups, R7 and R8 are cycloaliphatic hydrocarbyl groups, and R9 is an aliphatic hydrocarbyl group.
Copolymers obtained when using a ligand of the latter class can have an isotacticity of more than 95~ (cf. also Examples 10 and 11). The optical rotations measured in Examples 1 and 5 are indicative for a substantially higher isotacticity of the copolymer obtained in the former Example.
The results of Examples 6-9 confirm the results obtained in the Examples 1-5 and show that by using a ferrocenyl containing bidentate ligand ~ccording to this invention a polymerisation rate can be achieved which exceeds the rate achievable with 1, 3-bis~diethylphosphino)propane, which is a ligand according to the prior 2rt which hds been indicated to be very suitable for obtaining a high pol~ r; e~; nn rate in the copolymerisation of carbon monoxide with an aliphatic cc-olefin.
Comparison of Examples 6 and 8 shows that a higher isotacticity of the copolymer product can be obtained by introducing into the ferrocenyl containing bidentate lig~nd a chiral centre as the second element of chirality.
Example 12 A carbon monoxide/l-hl-Y~ n- copolymer was prepared as follows. A stirred zlutoclave was charged with 300 ml tetrahydrofuran, 300 ml l-h~y7~ n~ and a catalyst solution cons i 5 tlng o f 10 ml tetrahydrofuran, 17 ml methanol, 0 . 09 mmol palladium acetate, 0 . 45 mmol nickel perchlorate, 0.106 mmol { (P~) -1-[ ~5) -2- (diphenylrhnsrhinn) f~rrocenyl] )ethyldi-cyclohexylrhn~rh;n~, and 4.7 mmol 1,4--naphthn~-l;nnn~-.
Air pre~ent in the autoclave was replaced by carbon monoxide, which was forced in to achieve a pressure of 50 bar. The contents of the autoclave were brought to 21 temperature of q2 C. After 20 hours the polymerisation was terminated by cooling to room t ,-ri~t~-re and releasing the pressure. After the addition of methanol to the reaction mixture the copolymer was filt~red off, washed with methanol and dried.
The yield oi copolymer was 145 g. The pol~ r;~-t;nn rate c~lculated from the copolymer yield was ?60 g copolymer/ (g r,.ll;.,li hour~. The isotacticity of the copolymer obtained was WO 9a/32998 ~ 1 91 ~ 5 3 P~ a more than 95~.
Example 13 A carbon monoxide/l-h~Y~ r~n~ copolymer was prepared in substantially the same way as ln Example 12, but with the following dif ferences:
a) 90 ml xylene was used instead of 300 ml tetrahydrofuran, b) 90 ml l-h~-Y~ r~no was used instead of 300 ml, and c) the carbon monoxide partial pressure was 35 bar and in addition hydrogen was used at a partial pressure of 5 Dar.
The yield of copolymer was 14 g. The polymerisation rate calculated from the copolymer yield was 73 g copolymer/ (g palladium.hour). The isotacticity of the copolymer obtained was more than 95~. The weight average molecular weight of the copolymer was 32, S00.
Example 14 A carbon monoxide/l-hexadecene cDpolym~r was prepared in substantially the same way as in Example 12, but with the following differences:
a) 90 ml xylene was used instead of tetrahydrofuran, b) 90 ml l-h~ or~n~- was used instead of 300 ml, c) no 1,4-n:.rh~h~TI~n~n-- was present in the catAlyst solution, d) the temperature was 60 C instead of 42 C, and e) the carbon monoxide partial pressure was 40 bar and in addition hydrogen was used at a partial pressure of 1 bar.
The yield of copolymer was 29 g. The polymerisation rate calculated from the copolymer yield was 150 9 copolymer/ (g palladium.hour). The isotacticity of the copolymer obtained was about 809~i. The weight average molecular weight of the copolymer was 10,200.
Example 15 A carbon monoxide/l-h~Y~der~n~ copolymer was prepared in substantially the same way as in Example 12, but with the following differences:
a) 0.10 mmol of 1,3-bis(diethy1rh^srhinr)propane was used instead Of I IR) -1- [ (S) -2- (diphenylphosphino) ferrocenyl~ ) ethyldicyclo-WO 95/32998 2 1 9 1 4 5 3 PClll~P95102075 hexyl rh.~5rhi nF.~ and b) the reaction time was 19 hours instead of 21 hours.
The yield of copolymer was 47 . 4 g . The polymerisation rate czllculated from the copolymer yield was 262 g copolymer/ (g rAll;~,i; hour). The copolymer obtained was atactic.
Example 16 The following polymers, as such or in mixtures, were tested as additives in two gas oils (A and B~ in order to lower the cold filter plugging point (CFPP~ of the oils, as d~ rm;n~ in accordance with Standard Test Method IP 309/83:
Additive 1: the isotactic CO~l-h~ c~n~ copolymer of Example 13;
Additive 2: the isotactic CO/l-h~ r~n~ copolymer of Example 14;
Additive 3: an atactic CO/1-h~ n~ copolymer, having Mw 45,700;
Additive 4: an atactic cO/l-h~ n~ copolymer, having Mw 24, 600;
Additive 5: an atactic CO/l-h~Y7~l~o~n-- copolymer, having Mw 18,400;
Additive 6: an atactic CO/l-h~-X7~ nl~ copolymer, having Mw 15,000;
Additive 7: a commercially available poly (ethene/vinyl acetate) containing 25 ~w vinyl acetate, having Mw 75, 600, melt index according to A3TM-rl238 350 g/10 rlin, Additives 3, 4, 5 and 6 were prepared according to methods disclo~d ln EP-A-468594; these additives are not according to the invention;
th~y were tested for, 7r; ~n, The additives were introduced into the gas oils in the form of 50 ~w solution in toluene. The results of the testa are ~mbodied in Table I, where for esch of the gas oils the CFPP is reported aft~r addition of the indicated ~uantity of polymer solution (containing 50 ~w of active material), stated as mg of polymer solution per kg gas oil.
WO 9S/32998 2 1 9 1 4 ~ 3 1~11~1 gr . n7S
Table I
Additive ¦ Mw of CO/olefin ~ Added quantity ¦ CFPP
copolymer mg/kg gas oil C
Gas oil A
32,500 300 -16 2 10,200 300 -13 3 ) 45,700 300 -14 4 ) 24,600 300 -16 6 ) lS, 000 300 -16 1 + 7 32,500 100 + S0 -18 2 + 7 10,200 100 + S0 -20 3 + 7 ) 45,700 100 + S0 -13 4 t 7 ) 24,600 100 + S0 -16 7 ) - lS0 -17 Gas oil B
1 + 7 32,500 25 + 25 -27 2 + 7 10,200 25 + 25 -23 S + 7 ) 18,400 25 + 25 -17 7 ) - S0 -14 ) denotes: for: ,~r;cnn~ not according to the invention The 13C-NMR analyses reve~led that the copolymers prepared in the Examples 12-15 had a linear alternating structure.
The results of Examples 12 and 15 show again that by using a ferroc~nyl rnntA;n;ng bidentate ligand according to this invention a polymerisation rate can be achieved which exceeds the rate achievable with 1,3-bis(diethylphosphino)propane.
The results in Table I show that when copolymers according to this invention are used as additive for paraf~inic hydrocarbon oils the cold filter plugging points of the oils are decreased. The W0 95/32998 r~ 7n7S
performance of the copolymers according to the invention is better than the performance of comparable atactic copolymers, which can be deduced from the Table by taking the differences in the weight ~ver~ge molecular wei~ts into account: atactic copolymera with weight ~verage molecular weights of 32,500 and 10,200 would give cold filter plugging points of -lS C and -17 C, respectively, where the isotactic copolymers gave -16 C and -18 C. In pArticular by using the isotactic copolymers in con~unction with a poly-(ethene/vinyl acetate) very favourable results can be obtained.
ALPhA-OLEFIN
This invention relates to a catalyst composition for the preparation of linear alternating copolymers of carbon monoxide and an aliphatic -olefin having at least three carbon atoms. The invention further relates to said preparation and to the resulting copolymers ~nd their use. In thes~ copolymers the units originating in carbon monoxide and the units originating in the olefinically unsaturated compound(s~ used in the preparation occur in an alternating order. Furthermore, the copolymers are regioregular and stereoregular, in particular isotactic.
The term "regioregular" used herein refers to the way in which the units originating in a monomer CH2=CH-R, R ~eing an aliphatic alXyl group, are bound to units originating in carbon monoxide.
Three possibilities are distinguishable, which are termed "head/head", "tail/tail" and "head/tail". They may be represented schematically as follows:
head/head: - (CH2) - (CHR) - (CO) - (CHR) - (CH2) -tail/tail: - (CHR~ - (CH2) - (CO) - (CH2) - (CHR) -head/tail: - (CH2)--(CHR) - (CO) - (CH2) - (CHR) -Regioregular copolymers are understood to be copolymers in which the units originating in the monomer CH2=CH-R are bound to the units originating in carbon monoxide pr~rln-i n:~ntl y in a head/tail fashion. The degree of regioregularity of such copolymers is expressed as the average regioregularity, which is defined as the percentage of the number of units originating in the monomer _5 CH2=CH-R which i~re bound to the units originating in carbon monoxide in a head/tail fashion.
The terri "stereoregular" used herein refers to the con-figuration of the chiral carbon atoms present in the regioregular copolymer chains relative to the configuration of the chiral carbon atoms together with which they form part of a diad. A diad in this 2 1 9 1 4 5 3 F~~ 75 conn~ction is urderstood to be a segment of the polymer chain which contains two chiral carbon ~toms which are int~rconnected through a - (CH2) - (CO) - bridge. As regards the relation between the configurations of the two chiral carbon atoms of a diad, two possibilities _re distinguishahle, which are referred to as "isotactic" and "syndiotactic": when the two chiral c~rbon atoms in a diad have the same configuration this diad is called an isotactic diad, whereas the diad is called syndiotactic when the configurations are opposed. These options can be schematically represented as h isotactic: -C- lCE~2) - (CO) -C-R R
h R
syndiotactic: _ -C- ~Ch2) - (CO) -C-R ~}
The regioregular copolymers can be divided according to the structure of their chains into three classes:
1~ Polymer mixtures in which the numoer of isotactic diads is substantially equal to the number of syndiotactic diads are referred to ?5 atactic.
2) Polymer mixtures in which the number of isotactic diads is larger than the number of syndiotactic diads are referred to as ~ 50tAot; ~r 3) Polymer mixturea in which the num'oer of syn~iotzlrt;c di~ds is larger than the number of isotactic diads are referred to ~s syndiotactic.
The _tactic polymer mixtures mentioned under 1) are stereoirregular, whereas the other regioregular polymer mixtures ~ ' rr~ l above po.3sess a degree of stereoregularity. The degree of stereoregularity of the isotactic polymer mixtures is expressed as the ~ver~lge ~tereor~ Ari ty or isotacticity, which is understood to be the porr~.nt?rJe of isotactic diads, rAlr~lAto~ on the total number of di~ds present in the polymer chains. On the basis of this WO95/32998 2 l ~1 453 r~ 75 definition, the isotactic polymer mixtures have an average stereoregularity of more than S0~.
EP-A-384517 and EP-A-410543 disclose copolymers of carbon monoxide with an aliphatic a-olefin having at least three carbon atoms which are made up of linear chains in which the units originating in carbon monoxide alternate with the units originating in the -olefin. These copolymers have a certain degree of regio-and stereoregularity, more specifically they are isotactic in nature. For the sake of simplicity the polymer mixtures may be 0 ~I~c~-ri he~ as isotactic linear alternating copolymers .
EP-A-384517 discloses that the copolymers in question can be prepared by contacting a mixture of the monomers with a catalyst composition r; ci n~ a palladium compound and an asymmetric phosphorus bidentate ligand of the general formula RlR2P-R'-PR3R4, wherein R' is a bivalent bridging group rort:l;n;n~ at least two carbon atoms in the bridge, and Rl, R2, R3 and R4 ~re identical or different optionally polar substituted hydrocarbyl groups, such as the (+)-form and the ~-)-form of 4,5-bis(diph~ny1rh^srh;r hyl)-2,2-dimethyl-1,3-dioxolzne and (-)-4,5-bis(dibutylrht~srh;r thyl)-2, 2-dimethyl-1, 3-dioxolane.
In Macromolecules 25, 3604 - 3606 (1992) it is taught that by using as the asy~metric ligand (6,6'-dimethylbiphenyl-2,2'-diyl)bis-(diCyclohexy1rh~crh;n ) an isotactic linear alternating carbon monoxide/propene copolymer can be prepared which h~s an isotacticity 2~ of about 88~, AS calculated from the 13C-NMR data provided.
EP-A-4105~3 teaches that when isotactic copolymers are prepared which have a lower degree of isotacticity than required for a certain application, they can be treat~sd to increase their degree of isotacticity, e . g ., by extracting the copolymers with a suitable solvent. It is disadvantageous that in this treatment a polymer byproduct is obtained which in many cases has to be r~ rci~1 because it does not fulfil the requirements as regards tacticity.
A further disadvantage is that when the treatment is applied to polymers which ar~ made up of aliph~tic -olefins having, e.g., more than 10 carbon atoms, it becomes increasingly more difficult to 21q345~
WO95/32998 r~ ' 71175 carry out the treatment efficiently and with the effect of obtaining n polymer with d high degree of isotdcticity. It would therefore be desirable to dify th~ polymerisation such that copolymers with a high degree of isotacticity can be prepared Pff;ri~.ntly, i.e. such that the treatment can be avoided and also that the rate of polymerisation is improved.
It hds now surprisingly been found that the polymerisation rate can be improved rrnc;~r?hly by using in the catalyst composition an asymmetric phosphorus bidentate ligand of the general formula RSR6P-Q-ChR9-PR7R8, wherein Q i5 a 1,2-ferrocenyl bridging group, RS, R6, R7 and R8 are identical or different optiondlly polar substituted hydrocarbyl groups and R9 is hydrogen or an optionzlly polar substituted hydrocarbyl group. With a speciflc ~ubstitution pattern of the ferrocenyl containing asymmetric ligdnd, viz. such thdt RS
and R6 are identicdl or different optionally poldr substitut~d Qromatic hydrocarbyl groups, R7 dnd R8 dre identicdl or different cycloaliphatic hydrocarbyl groups, and R9 is an aliphatic hydrocarbyl group, d polymerisation rate can be dchieved which ~ven exceeds the rate achieved with 1, 3-bis (diethy~ rhrsrh; nr~ propdne when used under otherwise comparable conditions. The latter ligand ha~
been indicdted to be excellently suitdble for obtdining a high polymerisation rate in the copolymerisation of cdrbon monoxide and dn aliphatic -olefin, yielding a linear alternating regioregular atdctic polymer, cf. EP-A-516238.
It is even more a surprise that the isotacticity of the copolymers which dre obtdined by using the ferrocenyl r~nt~ininr asymmetric ligand can be higher than achieved previously, even higher than 959~, substantidlly without loss of the regioreguldrity, which typically amounts to more than 959~, more typically more thrm 99~.
Ligdnds of the g~nerdl formula RSR6P-Q-C~R9-PR7R8 AS defined hereinbefore dre known from EP-A-564406.
The present finding led to the ef ficient synthesis of isotdctic copolymers of carbon monoxide dnd aliphdtic c-olefins, in particular these hdving more thdn 10 carbon atoms . Iln~Yr rte~l y it WO 9S/32998 2 1 9 1 4 5 3 ~ A7n7!j was subsequently found that the latter copolymers have a better performance than comparable regioregular, atactic copolymers when they are used in p~r~ff;n;r hydrocarbon oils as additive for improving the low temperature properties of the oil, such as the cold filter plugging point. Such use of comparable atactic copolymers is known from EP-A-468594. The role of the tacticity of a polymeric additive on its effectiveness as paraffinic oil additive, which has now been found, is unprecedented.
hrrrr~lingly, the present invention relates to a catalyst composition suitable for the copolymerisation of carbon monoxide with an aliphatic a-olefin, which catalyst composition comprises a) a palladium compound, and b) an asymmetric phosphorus bidentat~ ligand of the general formula RSR6P-Q-CHR9-PR7R8, wherein Q is a 1,2-ferrocenyl bridging group, R5, R6, R7 and R8 are identical or different optionally polar substituted hydrocarbyl groups and R9 is hydrogen or an optionally polar substituted hydrocarbyl group.
The invention further relates to a process for the preparation of copolymers of carbon monoxide with an aliphatic c~-olefin having at least 3 carbon atoms, which process comprises contacting a mixture of the monomers with a catalyst composition of th~
invention .
In addition the invention relates to a copolymer of carbon monoxide with an aliphatic -olefin having at least 3 carbon atoms which copolymer comprises linear chains in which the units originating in the aliphatic a-olefin alternate with units originating in carbon monoxide, and which copolymer has an isotacticity of 959~ or more.
The invention further relates to a copolymer of carbon monoxide with an aliphatic a-olefin having more than 1~ carbon atoms which copolymer comprises linear chains in which the units originating in the aliphatic -olefin alternate with units originating in carbon monoxide, and which copolymer is isotactic. The copolymer has pr~ferably an isotacticity of 95~ or more.
~IVO 95~32998 ~ 21 91 453 r~ /a A further embodiment of thi6 invention relates to a paraffinic hydrocarbon oil composition containing a paraffinic hydrocarbon oil And as an additive a copolymer of carbon monoxide with an aliphatic a-olefin having more than 10 carbon atoms which copolymer comprises linear chains in which the units originating in the aliphatic a-olefin altern~te with units originating in carbon monoxide, and which copolymer is isotactic.
The c~talyst composition of this invention is based on a pdlladium compound. The catalyst composition may be based on a precursor compound ~-nnt~;n;ng palladium in its zero-valent state.
Preferably the palladium compound is a palladium aalt, such as a salt of a carboxylic ncid. Particularly suitable i5 palladium acetA te .
The phosphorus bidentate ligand of the general formula RSR6P-Q-CHR9-PR7R8 as defined hereinbefore is asymmetric. I~epending of whether R9 is hydrogen or ~n optionally polar substituted hydrocarbyl group the ligand's structur~ provid~s for at l~ast one or at l~ast two el~m~nts of chirality. The ligdnd may b~ pr~sent as an optically inactiv~ mixtur~ of possibl~ st~re~;~ ~c or diastereoisom~rs, or it may b~ pres~nt as an optically activ~
mixture in which there is ah excess of a ster~oisomer or diast~r~o-isom~r, or th~ ligznd consists of on~ substantially pure st~reoisom~r or diaster~oisom~r. The skilled r~ad~r will appr~ciat~
that it will hav~ no bearing on th~ isotacticity of the copolymer wh~th~r th~ lig~nd us~d consists of on~ st~reoisomer or diaster~oisom~r or it consists of said st~reoisomer or dia~t~re~,; r and its optical antipode.
The group Q of the bidentate ligand is a bivalent 1, 2-f~rroc~nyl group which may contain furth~r substitu~nts attach~d to the pentadienyl groups, 1.~. oth~r than th~ RSR6P-- ~nd R7R8P-ChR9 groups in a 1,2-position, but this is not pr~ferred.
The hydrocArbyl groups R5 and R6 are prefer~bly optiondlly polar substitut~d aromatic hydrocarbyl groups which typic~Llly have 6 to 12 cdrbon atoms. Wh~n they are polar substituted, eligible substituents ar~ for exampl~ dialkylamino groups, whereas pr~ferred W0 95/32998 2 1 9 1 4 5 3 1 ~
polar substituents are alkoxy groups, such as methoxy groups. Polar substituents are typically positioned ortho with respect to the phosphorus atom. The groups RS and R6 are preferably identical.
They are in particular phenyl groups.
The hydrocarbyl groups R7 and R8 are preferably aliph~tic groups or more preferably cycloaliphatic groups, such groups typically contain no more than 10 c~rbon atoms. Optionally they may be connected to one another through a c4rbon-carbon bond, so that together with the phosphorus atom to which they are attached they form a heterocyclic phosphorus containing group. The groups R7 and R6 ~re preferably identical. They may in particular be selected for example from ethyl, 1-propyl, 2-propyl, I-butyl and 2-butyl groups, more in particular they are cyclohexyl groups.
The group R9 is hydrogen or an optionally polar substituted hydrocarbyl group, typically having no more than 10 carbon atoms.
The group R9 is prefera~hly other th~n hydrogen since this may further increase the isotacticity of the polymer obtained. The group R9 is in particular an alkyl group, more in particular a n-~lkyl group, such as an ethyl, 1-propyl or 1-butyl group, most in pzlrticular a methyl group.
Very good results can be achieved when as the phosphorus bidentate ligand one of the following is used:
(R~ [ (s)-2-~diphenylrh^srhino) ferrocenyl] }ethyldiphenylrhoerh;n,-, I(R)-1-[(5)-2-(dicyclohexylrhns~h;n^)ferrocenyl])ethyldiphenyl-rh~ph; n~.
{ (R) -1- [ (S ) -2- (dicyclohexylphosphino) ferrocenyl] ) ethyldicyclohexyl-phosphine, [2-(dipheny~rh^srh;n~ )ferrocenyl~methyldicyclohexylrh^srhine or {1-[2-(diphenylrho~rhino)ferrocenyl] )ethyldiethylrh^srh;n .
Even further improved results can be obtained by using ~ (R)-1-[ (S)-2- (diphenylrhosrh;n^) ferrocenyl] )ethyldicyclohexylrh^~rh;n~ as the phosphorus bidentate ligand.
The quantity of the phosphorus bidentate ligand present in the c~talyst composition of this invention may vary between wide limits.
Suitably the quantity is in the range of from O . 5-2 mol, in pdrticular from 0.~5-1.5 mol per mol of pA~
The catalyst composition of this invention may compr~se as an ~dditional component a component which i5 generally thought to act as a source of anions which are weakly or non-coordinating with palladium. The anion is preferably an anion of an acld having a pKa of less than 6 (~ rmi n~ in an aqueous solution at 18 C), suitably less than 4 and in particular less than 2. Examples of suitable acids having a pKa of less than 2 are mineral acids, such as perchloric acid, sulphonic acids, such as p-toluenesulphonic acid and trifluorome~hAnGc~lrh~nic acid, and halogen carboxylic acids, such a~ trifluoroacetic acid. ~he source oi arions may be incorporated in the catalyst composition in the form of an acid or in the form of a salt. Nickel perchlorate is a very suitable sourc~
of anlons. The catalyst composition may alternatively comprise as an additional compound an adduct of boric acid with a 1, 2-glycol, a catechol or a salicylic acid, a borate cuch as lithium tetrakis(perfluorophenyl)borate or sodium tetrakis~bis-3,5-(trifluoromethyl)ph~nyllborate or a borane such as tris (perfluorophenyl)borane, triphenylborane or tris [bis-3, 5-ttrifluoromethyl)ph~nyllborane It is also conc~ivable to use an alumoxane, such as methyl aluminoxane or t-butyl Al n~ Y n~ as an additional component. The quantity of these additional components when present in the c~talyst composition of this invention may vary between wide limits. Suitably the quantity is in the range of from 0.5-50 equivalents, ~n p~rticular from 1-25 equivalents per mol of p~llA~ owever, Alllrn;nnYAn~-c may be used in such a quantity that the molar ratio of aluminium to palladium is in the range of 4000:1-10:1, preferably 2000:1-100:1.
In order to increase the rate of polymerisation it is preferred to include in the catalyst composition a quinone, in particular a 1,4-quinone, such as a l,g-h~n7~q~in~ and a 1,4-naphthoquinone.
The quantity of quinone suitably lies lr the range of from 1-5000 mol, in particular from 5-1000 mol per mol of palladium.
The aliphatic ~-olefin used as one of the monomers of the process may be a branched or a straight chain olefilm The aliphatic WO95/32998 2~ ~ 1 453 r~l~L~ 7S
a-olefin may contain hetero atoms, such as oxyg~n and nitrogen, which are present when the aliphatic a-olefin is o.g. an olefinically unsaturated ester, alcohol or amide. The aliphatic a-olefin may also contain an aromatic substituent in such a manner that there is no conjugation of the aromatic substituent with the olefinic double bond, such as in 4-phenyl-1-butene. The aliphatic a-olefin is typically a hydrocarbon. The aliphatic a-olefin may be a single olefin but also a mixture of a-olefins may be used, or, if desired, a mixture of an a-olefin with ethene. In the latter case the units in the polymer chains originating in ethene do not contribute to the regio- and stereoregularity of the polymer. In such a case the regularity of the polymer is exclusively related to the parts of the polymer chains which contain units originating in the a-olefin.
When the polymer of this invention is to be used as an additive for a paraffinic hydrocarbon oil, the aliphatic a-olefin contains suitably more than 10 carbon atoms and typically not more than 40 carbon atoms, in particular not more than 30 carbon atoms.
Preferably it is a straight chain olefin. It is also possible that in addition to aliphatlc a-olefins having more than 10 carbon atoms one or more aliphatic a-olefins having not more than 10 carbon atoms are incorporated. Very suitable is a mixture of aliphatic a-olefins of carbon numbers in the range of from 12 to no more than 24. Very good results have been achieved with a polymer based on 1-hr _ _,lr _.. r .
When the polymer of this invention is to be used for other purposcs than as a paraffinic oil additive, e.g. in an rn ~ne~rjn application or as a packaging material, it is eligible to use an aliphatic a-olefin having at most 10 carbon atoms. It is particularly suitable to use a lower olein as the aliphatic a-olefin, i.e. an olefin ~ nntAin;n~ no more than 6 carbon atoms, as a single olefin or as a mixture rnr~inln~ aliphatic a-oleins, if desired in conjunction with ethene. Very good r~sults have been achieved with propene, 1-butene and 4-methyl-1-pentene as the aliphatic a-olefin.
WO 95/32998 1 ~
2t9t453 The preparation of the polymers is preferably carried out by contacting the monomers with the catalyst composition of this lnvention in a diluent in which the polymers are insoluble or virtually insoluble. Lower aliphatic alcohols and in particular methanol are suitable as diluents. Very suitable diluents contain for at least 80 9~v an :aprotic liquid and ~or at most 20 ~v a protic liquid such ns a lower aliphatic alcohol. The aprotic liquid may be A polar liquid, such as acetone, methyl acetate, tetrahydrofuran, dioxane, diethyleneglycol dimethyl ether,, bu-yL~,lactone, N-methylpyrroLidone or 5ll1rholAn~-, or an apolar liquid, such as n-hexane, cyclohexane or toluene. ~avourable resuLts can be obtained by using a mixture o~ tetrahyc~ro~uran and methanol. I~ desired, the polymerisation can also be carried out in the gas phase. The polymer preparation can take place batchwise or ~nt;nll~llrly.
When the polymerisation is carried out in a diluent which contains a lower 31iph2tic alcohol the rate of polymerisation may be ;nr-r~c~.~l by adding to the polymerisation mixture an ortho ester, such as a trialkyl orthoformate, in particular trimethyl orthoformate. The quantity of the ortho ester may vary between wide limits. Preferably it is used in a quantity of between 100 and 5000 mol, in particular 500 and 3000 mol per mol oi r~
The quantity of catalyst composition used in the preparation of the polymers may vary within wide limits. Per mol of olefinically unsaturated compound to be polymerised a quantity of catalyst composition is preferably used which contains 10-7 to 10-3 and in particular 10-6 to 10-4 mol o~ r~
The preparation of the polymers is preferably carried out at a t~ -rilt~-rr. of 20-150 C and a pressure o~ 2-150 bar ~nd in particular at a temperature of 30-130 ~C and a pressure of 5-100 bar. Suitably a temperature below 80 C, in particular below 60 C is selected as this leads to a higher isotacticity of the copolymer. The molar ratio of the olefinically unsaturated compounds relative to carbon monoxide i5 preferably 10:1 to 1:10 and in particular 5:1 to 1:5. The polymerisation may be carried out in the presence of hydrogen, in which case the hydrogen is suitably present WO 95/32998 P~ ^7~75 219~453 in a quantity of from 0.1-0.5 mol per mol of carbon monoxide.
The copolymers according to this invention may be recovered from the polymerisation mixture by any suitable method. Such methods are well known in the art.
According to the present invention the low-temperature t properties of paraffinic hydrocarbon oils, such as the cold filter plugging point and the pour point, can be improved by using as an additive an isotactic linear alternating copolymer of carbon monoxide and an aliphatic a-olefin having more than 10 carbon atoms.
The copolymer has preferably an isotacticity of 9S~ or more. The copolymer may also be used as an aid in extractive dewaxing processes. An example of such a dewaxing process is disclosed in EP-A-482636. Examples of paraffinic hydrocarbon oils include gas oils, diesel oils, lubricating olls and crude oils. Very favourable results can be achieved with paraffinic gas oils.
The molecular weight of the copolymers which are eligible to be used as additive in the paraffinic hydrocarbon oils may vary between wide limits. By preference, copolymers are used having a weight average molecular weight (Mw) between 103 and 106, in particular between 2x103 and 105. The preference for a given molecular weight and also for a given number of carbon atoms of the aliphatic a-olefin~s) from which the copolymer is prepared is substantially determined by the nature and the quantity of the paraffins present in the paraffinic hydrocarbon oil. The quantity of copolymer which according to the invention is taken up into the paraffinic hydrocarbon oil may vary between wide limits. It is preferred to employ 1-10, 000 and in particular 10-1000 mg of copolymer per kg of p~r:~lff;nir hydrocarbon oil.
In addition to the present copolymers further additives may be added to the paraffinic hydrocarbon oil, such as other polymeric additives than copolymers according to this invention, antioxidants, corrosion inhibitors, metal deactivators and so called wax anti settling agents ("WASA"). Other polymeric additives are, for example, commercially available poly(ethene/vinyl carboxylate)s 35 ~nnt~;nln~ 20-35 9GW of the vinyl carboxylate, wherein the vinyl W095/32998 21 ~1 453 r~
carboxylate is typically vinyl acetate or vinyl propionate. This invention also relates to an additive composition per se comprising a copolymer of carbon monoxide with an aliphatic a-olefin having more than 10 carbon atoms which copolymer compris~s linear chains in which the units originating in the aliphatic a-olefin alternate with units originating in carbon monoxide, and which copolymer is i~otactic, and a poly(ethene/vinyl carboxylate) r~ntAinin~ 20-35 9~w of the vinyl carboxylate, wherein the vinyl carboxylate is typically vinyl acetate or vinyl propionate. With respect to their ability to improve the low-temperature properties o~ the paraffinic hydrocarbon oil the copolymers according to this invention may have a synergistic effect with the further additives mentioned, in particular with polytethene/vinyl carboxylate).
The polymer constituents of the other polymeric additives have typically a weight average molecular weight between 103 and 106, in particular between 104 and 105. ~hen other polymeric additives are present in the paraffinic hydrocarbon oil, the copolymer according to this invention constitutes preferably 1-90 ~w of the total of polymeric additives.
The invention will now be illustrated with reference to the following cxamples. The regio- and stereoregularity of the copolymers prepared according to Examples 1-15 was derived from 13C-NMR spectra (deutero-hexafluoroisopropanol solvent), by anzly~ing the signals in the carbonyl region.
E:xample A carbon monoxide/propene copolymer was prepared as follows. A
stirred autoclave was charged with 150 ml tetrahydrofuran, 39 g (65 ml) propene and a catalyst solution consisting of 1.5 ml tetrahydrofuran, 8 . 5 ml methanol 0. 06 mmol palladium acetate, 0.3 mmol nickel perchlorate, 0. 07 mmol I (R) -1- [ (S) -2- (diphenylphosphino) ferrocenyll )ethyldicyclo-hexyl rhr~rh~ n~ and 3 . 0 mmol 1, 4--n~rhthAqll; nrn~, W095/32998 21 91 453 r~l,~l h 1~
Air present in the autoclave was replaced by carbon monoxide, which was forced in to achieve a pressure of 80 bar. The contents of the autoclave were brought to a temperature of g2 C. After 41 hours the polymerisation was terminated by cooling to room temperature and releasing the pressure. The su~p~'n~i nn obtained was diluted with methanol. The solids were collected by filtration, washed with methanol and dried.
The yield of copolymer was q7 g. The polymerisation rate calculated from the copolymer yield was 180 g copolymer/ (g p~ .. i; hour). The isotacticity of the copolymer obtained was more than 959~. The product showed an optical rotation [c~] D of 28 . 4, as measured in hexafluoroisopropanol at a concentration in the range of 5-10 g/100 ml. The optical rotation is a molar value calculated on the basis of the molecular weight of the copolymer's repeating unit ~i.e. 70).
Example 2 A carbon monoxide/propene copolymer was prepared in substantially the same way as in Example 1, but with the following differences:
a) 0 07 mmol of ( (R) -l- [ (S) -2- (dicyclohexylphosphino) ferrocenyl] )-ethyldiphenylrh^sphin~ was used instead of ( (R) -1- [ (S) -2- (di-phenylrh~rhin~) ferrocenyl] )ethyldicyclohexylrhnsph;n~, and b) the reaction time was 114 hours instead of 41 hours.
The yield of copolymer was 20 . 3 g . The polymerisation rate was 28 g copolymer/ (g palladium.hour) . The isotacticity of the copolymer obtained was 88~.
Example 3 A carbon monoxide/propene copolymer was prep~red in substantially the s2me way as in Example 1, but with the following differences:
a) 0 07 mmol of ((R)-1-[(5)-2-(dicyclohexylrh^sphin^)ferrocenyl]}-ethyldicyclohexylrhosrh;n~ was used instead of ( (R) -1-[ (S)-2-(diphenylphosphino)ferrocenyl]~ethyldicyclohexylrh^~rh;n~, andb) the reaction time was 138 hours instead of ql hours.
The yield of copolymer was 30. 8 g. The polymerisation rate was 35 g copolymer/ ~g palladium.hour) . The isotacticity of the copolymer obtained was 90~.
Example 4 A carbon monoxide/propene copolymer was prepared in substantially the same way as in Example 1, but with the iollowing differences:
a~ 0.07 mmol of ((R)-l-[(S)-2-(diphenylrh~srh;nn)ferrocenyl3}-ethyldiphenylrh^srh;n~- was used instead of ~(R~-1-1(5)-2-(di-phenylrh~srh;no) ferrocenyll )ethyldicyclohexylEh^srhin~-, and b) the reaction time was 116 hours instead of 41 hours.
The yield o copolymer was 27 . 8 g. The polymerisation rate was 38 g copolymer/ (g palladium.hour) . The isotacticity of the copolymer obtained was 829~.
Ex~mple S (for ~ . - r; ~on, not according to the invention) -- ~ - . .......
A carbon noxide/propene copolymer was prepared in substantially the same way as in Example 1, but with the following differences:
~) 110 ml instead of lS0 ml tetrahydrofuran and 87 ml instead of 65 ml propene were used, b) the catalyst solution consisted of 3 . 9 ml tetrahydrofuran, 1. 4 ml methanol 0.091 mmol palla=dium acetate, 0. 65 mmol nickel perchlorate, 25 O.lOS mmol (-)-4,5-bis(dibutyl~nh~sph;n thyl)-2,2-dimethyl-1, 3-dioxolane and 6.3 m~ol 1,4--n~rh~h~ l;n~nf., c) the pressure of carbon monoxide was 45 bar instead of 80 b~r, d) the reaction time was 65.1 hours instead of 41 hours, and 30 e) the reaction mixture was diluted with water instead of methanol .
The yield of copolymer was 6. 83 g. The polymerisation r~te was 10.8 g copolymer/(g rAll~ hour). The product showed an optical rotation [CL3 2~ of +10 . 4, as measured in hexafluoroisoprop~nol .
WO 95/32998 1 ~
~lql453 Example 6 A c4rbon monoxide/propene copolymer was prepared as follows. A
stirred autoclave was charged with 75 ml tetrahydrofuran, 20 ml propene, 1 ml trimethyl orthoformate and a catalyst solution cons i s ting o f 4 . 0 ml methanol 0. 06 mmol palladium acetate, 0 . 3 mmol nickel perchlorate, 0. 07 mmol t (R) -1- [ (S) -2- (diphenylphosphino) ferrocenyl] )ethyldicyclo-hexylphosphine, and 3. 0 mmol 1, 4-naphthoquinone.
Air present in the autoclave was replaced by carbon monoxide, which was forced in to achieve a pressure of 80 bar. The contents of the autoclave were brought to a temperature of 46 C. The pressure was kept constant by supplying carbon monoxide. From the r~te of consumption of carbon monoxide it was calculated that the average polymeris~tion rate during the first hour of the polymerisation amounted to 490 g copolymer/ (g palladium.hour) .
After 10 hours the polymerisation was terminated by cooling to room temperature and releasing the pressure. The suspenJion obtained was diluted with methanol. The solids were collected by filtration, washed with methanol and dried.
The yield of copolymer was 16 g. The isotacticity of the copolymer obtained was more than 9S~. It had a melting point of 185 C.
Example 7 A carbon monoxide/propene copolymer was prepared in substantially the same way as in Example 6, but with the following differences:
a) 0.07 mmol of racemic (1-[2-(diphenylrho~Fh;n~)ferrocenyl])-ethyldiethylrh~sFh;n~ was used instead of I (R)-1-[ (S)-2-~di-phenylrh~eph;n~)ferrocenyl])ethyldicyclohexylphosphine, and b) the polymerisation temperature was 49 C instead of 46 C.
The average polymerisation r~te during the first hour of the polymerisation amounted to 195 g copolymer/ (g pAl 1 A~'l; hour) . The WO 95/32998 2 1 9 1 4 5 3 P~ l/~ . /a '-yield of copolymer was 10 g. The isotacticity of the copolymer obtained was estimated at about 70~.
Example 8 A caroon monoxide/propene copolymer was prep~red in substantially the same way as in Example 6, but with the following di f f erences:
a) 0 07 mmol of racemic [2-(diphenylrhn~ph;nn)ferrocenyl]methyldi cyclohexylrhn~rh;n~ was used instead of I (R)-l-l (S)-2-(di-phenylrhnsrh;n~n)ferrocenyl]~ethyldicyclohexylrhnsphinf~, and b) the polymerisation temperature was 49 C instead of 46 C.
The average polymerisation rate during the first hour of the polymerisation amounted to 270 g copolymer/ (g p=l 1~; hour) . The yield of copolymer was 12 g. The isotacticity of the copolymer obtained was estimated at about 80~.
Example 9 (for I "J~r~nn, not accordlng to the invention) A carbon monoxide/propene copolymer was prepared in substantially the same way as in Example 6, but with the difference that 0 . 07 mmol of 1, 3-bis (diethylphosphino~ propane was used instead of ( (R) -1- [ (S) -2- (diphenyl E~hnerh; nn) ferrocenyl] ) ethyldicyclohexyl-phosphine.
The average polymerisation rate during the first hour of the polymerisation amounted to 220 g copolymer/ (g palladium.hour) . The yield of copolymer was 11 g. The copolymer obtained was regioregular ~md atactic. It had a melting point of 131 C.
Example 10 ~.. . .
A carbon monoxide/4-methyl-1-pentene copolymer was prepared as follows. A stirred autoclave was charged with 8 . 4 g 4-methyl-1-pentene and a catalyst solution consisting of 14 ml t-butanol, 1.3 ml methanol, 2.1 ml toluene, 0.1 mmol palladium ~cetate, O . 3 mmol nic~cel perchlorate, 0.11 mmol 1 (R)-l-[ (5)-2-(diphenylrhnsrh;nn) ferrocenyl] )ethyldicyclo-hexylrhn~rhin--, and WO g5/32998 r~ 7s 1. 5 mmol 1, 4-naphthoquinone .
Air present in the autoclave was replaced by carbon monoxide, which was forced in to achieve a pressure of 40 bar. The contents of the autoclave were brought to a temperature of 40 C. After 168 hours the polymerisation was terminated by coollng to room temperature and releasing the pressure. The mixture obtained was stirred in methanol. The solids were collected by filtration, washed with methanol and dried.
The yield of copolymer was 10 g. The isotacticity of the copolymer obtained was more than 959~.
Example 11 A carbon monoxide/l-butene copolymer was prepared ufiing the procedure of Example 10, but with the following differences:
a) 10 g l-butene was used instead of 4-methyl-1-pentene, b) carbon monoxide was forced in to achieve a pressure of 43 bar instead of 40 bar, and c) the time of polymerisation was 21 hours instead of 168 hours.
The yield of copolymer was 9.1 g. The isotacticity of the copolymer obtained was more than 95~.
The 13C-NMR analyses further revealed that the copolymers prepared in the Examples 1 - 11 had a linear alternating structure.
By comparing the results of Examples 1 - 5 it becomes apparent that by using a ferrocenyl ~ntA~nin7 bidentate ligand according to this invention a polymerisation rate can be achieved which exceeds by far the polymerisation rate achieved in the known polymerisation using (-) -4, 5-bis ~dibutyl rhnsrh; - thyl) -2, 2-dimethyl-1, 3-dioxolane the ligand. Particularly good result~ are obtzined by selecting fcrrocenyl ront:~in;ng ligand of the general formula R5R6P-Q-CHR9-PR7R8, wherein Q is a 1,2-ferrocenyl bridging group, R5 and R6 are aromatic hydrocarbyl groups, R7 and R8 are cycloaliphatic hydrocarbyl groups, and R9 is an aliphatic hydrocarbyl group.
Copolymers obtained when using a ligand of the latter class can have an isotacticity of more than 95~ (cf. also Examples 10 and 11). The optical rotations measured in Examples 1 and 5 are indicative for a substantially higher isotacticity of the copolymer obtained in the former Example.
The results of Examples 6-9 confirm the results obtained in the Examples 1-5 and show that by using a ferrocenyl containing bidentate ligand ~ccording to this invention a polymerisation rate can be achieved which exceeds the rate achievable with 1, 3-bis~diethylphosphino)propane, which is a ligand according to the prior 2rt which hds been indicated to be very suitable for obtaining a high pol~ r; e~; nn rate in the copolymerisation of carbon monoxide with an aliphatic cc-olefin.
Comparison of Examples 6 and 8 shows that a higher isotacticity of the copolymer product can be obtained by introducing into the ferrocenyl containing bidentate lig~nd a chiral centre as the second element of chirality.
Example 12 A carbon monoxide/l-hl-Y~ n- copolymer was prepared as follows. A stirred zlutoclave was charged with 300 ml tetrahydrofuran, 300 ml l-h~y7~ n~ and a catalyst solution cons i 5 tlng o f 10 ml tetrahydrofuran, 17 ml methanol, 0 . 09 mmol palladium acetate, 0 . 45 mmol nickel perchlorate, 0.106 mmol { (P~) -1-[ ~5) -2- (diphenylrhnsrhinn) f~rrocenyl] )ethyldi-cyclohexylrhn~rh;n~, and 4.7 mmol 1,4--naphthn~-l;nnn~-.
Air pre~ent in the autoclave was replaced by carbon monoxide, which was forced in to achieve a pressure of 50 bar. The contents of the autoclave were brought to 21 temperature of q2 C. After 20 hours the polymerisation was terminated by cooling to room t ,-ri~t~-re and releasing the pressure. After the addition of methanol to the reaction mixture the copolymer was filt~red off, washed with methanol and dried.
The yield oi copolymer was 145 g. The pol~ r;~-t;nn rate c~lculated from the copolymer yield was ?60 g copolymer/ (g r,.ll;.,li hour~. The isotacticity of the copolymer obtained was WO 9a/32998 ~ 1 91 ~ 5 3 P~ a more than 95~.
Example 13 A carbon monoxide/l-h~Y~ r~n~ copolymer was prepared in substantially the same way as ln Example 12, but with the following dif ferences:
a) 90 ml xylene was used instead of 300 ml tetrahydrofuran, b) 90 ml l-h~-Y~ r~no was used instead of 300 ml, and c) the carbon monoxide partial pressure was 35 bar and in addition hydrogen was used at a partial pressure of 5 Dar.
The yield of copolymer was 14 g. The polymerisation rate calculated from the copolymer yield was 73 g copolymer/ (g palladium.hour). The isotacticity of the copolymer obtained was more than 95~. The weight average molecular weight of the copolymer was 32, S00.
Example 14 A carbon monoxide/l-hexadecene cDpolym~r was prepared in substantially the same way as in Example 12, but with the following differences:
a) 90 ml xylene was used instead of tetrahydrofuran, b) 90 ml l-h~ or~n~- was used instead of 300 ml, c) no 1,4-n:.rh~h~TI~n~n-- was present in the catAlyst solution, d) the temperature was 60 C instead of 42 C, and e) the carbon monoxide partial pressure was 40 bar and in addition hydrogen was used at a partial pressure of 1 bar.
The yield of copolymer was 29 g. The polymerisation rate calculated from the copolymer yield was 150 9 copolymer/ (g palladium.hour). The isotacticity of the copolymer obtained was about 809~i. The weight average molecular weight of the copolymer was 10,200.
Example 15 A carbon monoxide/l-h~Y~der~n~ copolymer was prepared in substantially the same way as in Example 12, but with the following differences:
a) 0.10 mmol of 1,3-bis(diethy1rh^srhinr)propane was used instead Of I IR) -1- [ (S) -2- (diphenylphosphino) ferrocenyl~ ) ethyldicyclo-WO 95/32998 2 1 9 1 4 5 3 PClll~P95102075 hexyl rh.~5rhi nF.~ and b) the reaction time was 19 hours instead of 21 hours.
The yield of copolymer was 47 . 4 g . The polymerisation rate czllculated from the copolymer yield was 262 g copolymer/ (g rAll;~,i; hour). The copolymer obtained was atactic.
Example 16 The following polymers, as such or in mixtures, were tested as additives in two gas oils (A and B~ in order to lower the cold filter plugging point (CFPP~ of the oils, as d~ rm;n~ in accordance with Standard Test Method IP 309/83:
Additive 1: the isotactic CO~l-h~ c~n~ copolymer of Example 13;
Additive 2: the isotactic CO/l-h~ r~n~ copolymer of Example 14;
Additive 3: an atactic CO/1-h~ n~ copolymer, having Mw 45,700;
Additive 4: an atactic cO/l-h~ n~ copolymer, having Mw 24, 600;
Additive 5: an atactic CO/l-h~Y7~l~o~n-- copolymer, having Mw 18,400;
Additive 6: an atactic CO/l-h~-X7~ nl~ copolymer, having Mw 15,000;
Additive 7: a commercially available poly (ethene/vinyl acetate) containing 25 ~w vinyl acetate, having Mw 75, 600, melt index according to A3TM-rl238 350 g/10 rlin, Additives 3, 4, 5 and 6 were prepared according to methods disclo~d ln EP-A-468594; these additives are not according to the invention;
th~y were tested for, 7r; ~n, The additives were introduced into the gas oils in the form of 50 ~w solution in toluene. The results of the testa are ~mbodied in Table I, where for esch of the gas oils the CFPP is reported aft~r addition of the indicated ~uantity of polymer solution (containing 50 ~w of active material), stated as mg of polymer solution per kg gas oil.
WO 9S/32998 2 1 9 1 4 ~ 3 1~11~1 gr . n7S
Table I
Additive ¦ Mw of CO/olefin ~ Added quantity ¦ CFPP
copolymer mg/kg gas oil C
Gas oil A
32,500 300 -16 2 10,200 300 -13 3 ) 45,700 300 -14 4 ) 24,600 300 -16 6 ) lS, 000 300 -16 1 + 7 32,500 100 + S0 -18 2 + 7 10,200 100 + S0 -20 3 + 7 ) 45,700 100 + S0 -13 4 t 7 ) 24,600 100 + S0 -16 7 ) - lS0 -17 Gas oil B
1 + 7 32,500 25 + 25 -27 2 + 7 10,200 25 + 25 -23 S + 7 ) 18,400 25 + 25 -17 7 ) - S0 -14 ) denotes: for: ,~r;cnn~ not according to the invention The 13C-NMR analyses reve~led that the copolymers prepared in the Examples 12-15 had a linear alternating structure.
The results of Examples 12 and 15 show again that by using a ferroc~nyl rnntA;n;ng bidentate ligand according to this invention a polymerisation rate can be achieved which exceeds the rate achievable with 1,3-bis(diethylphosphino)propane.
The results in Table I show that when copolymers according to this invention are used as additive for paraf~inic hydrocarbon oils the cold filter plugging points of the oils are decreased. The W0 95/32998 r~ 7n7S
performance of the copolymers according to the invention is better than the performance of comparable atactic copolymers, which can be deduced from the Table by taking the differences in the weight ~ver~ge molecular wei~ts into account: atactic copolymera with weight ~verage molecular weights of 32,500 and 10,200 would give cold filter plugging points of -lS C and -17 C, respectively, where the isotactic copolymers gave -16 C and -18 C. In pArticular by using the isotactic copolymers in con~unction with a poly-(ethene/vinyl acetate) very favourable results can be obtained.
Claims (20)
1. A catalyst composition suitable for the copolymerisation of carbon monoxide with an aliphatic .alpha.-olefin, which catalyst composition comprises a) a palladium compound, and b) an asymmetric phosphorus bidentate ligand of the general formula R5R6P-Q-CHR9-PR7R8, wherein Q is a 1,2-ferrocenyl bridging group, R5, R6, R7 and R8 are identical or different optionally polar substituted hydrocarbyl groups and R9 is hydrogen or an optionally polar substituted hydrocarbyl group.
2. A catalyst composition as claimed in claim 1, characterised in that in the general formula of the phosphorus bidentate ligand R5 and R6 are identical or different optionally polar substituted aromatic hydrocarbyl groups, R7 and R8 are identical or different cycloaliphatic hydrocarbyl groups, and R9 is an aliphatic hydrocarbyl group.
3. A catalyst composition as claimed in claim 2, characterised in that in the general formula of the phosphorus bidentate ligand R5 and R6 are phenyl groups, R7 and R8 are cyclohexyl groups, and R9 is a methyl group.
4. A catalyst composition as claimed in claim 3, characterised in that the phosphorus bidentate ligand is ((R) -1-[(S)-2-(diphenyl-phosphino) ferrocenyl]} ethyldicyclohexylphosphine.
5. A catalyst composition as claimed in any of claims 1-9, characterised in that it comprises as the palladium compound a palladium carboxylate, such as palladium acetate.
6. A catalyst composition as claimed in any of claims 1-5, characterised in that it comprises as an additional component an anion of an acid having a pKa of less than 2, in particular a mineral acid, such as perchloric acid, a sulphonic acid, such as p-toluenesulphonic acid or trifluoromethanesulphonic acid, or a halogen carboxylic acid, such as trifluoroacetic acid, typically in a quantity of 1-25 equivalents per mol palladium.
7. A catalyst composition as claimed in any of claims 1-6, characterised in that it comprises the phosphorus bidentate ligand in a quantity in the range of from 0.75-1.5 mol per mol of palladium.
8. A process for the preparation of copolymers of carbon monoxide with an aliphatic .alpha.-olefin having at least 3 carbon atoms, which process comprises contacting a mixture of the monomers with a catalyst composition as claimed in any of claims 1-7.
9. A process as claimed in claim 8, characterised in that the polymerisation is carried out by contacting the monomers with the catalyst composition in a diluent containing for at least 80 %v an aprotic liquid and for at most 20 %v a protic liquid such as a lower aliphatic alcohol, and in that it is carried out at a temperature of 30-130 °C, a pressure of 5-100 bar and a molar ratio of the olefinically unsaturated compounds relative to carbon monoxide of 5:1 to 1:5 and using a quantity of catalyst composition which per mol olefinically unsaturated compound to be polymerised contains 10-6-10-4 mol of palladium.
10. A copolymer of carbon monoxide with an aliphatic .alpha.-olefin having at least 3 carbon atoms which copolymer comprises linear chains in which the units originating in the aliphatic .alpha.-olefin alternate with units originating in carbon monoxide, and which copolymer has an isotacticity of 95% or more.
11. A copolymer of carbon monoxide with an aliphatic .alpha.-olefin having more than 10 carbon atoms which copolymer comprises linear chains in which the units originating in the aliphatic .alpha.-olefin alternate with units originating in carbon monoxide, and which copolymer is isotactic.
12. A copolymer as claimed in claim 11, characterised by an isotacticity of 95% or more.
- 24a -
- 24a -
13.-A copolymer as claimed in claim 11 or 12, characterised in that the .alpha.-olefin is a straight chain olefin having no more than 30 carbon atoms.
14. A copolymer as claimed in any of claims 11-13, characterised in that the copolymers have a weight average molecular weight (?w) between 103 and 106, in particular between 2x103 and 105.
15. A paraffinic hydrocarbon oil composition containing a paraffinic hydrocarbon oil and as an additive a copolymer as claimed in any of claims 11-14.
16. A paraffinic hydrocarbon oil composition as claimed in claim 15, characterised in that it contains the copolymer as claimed in any of claims 11-14 in a quantity of 1-10,000, in particular in a quantity of 10-1,000 mg of copolymer per kg of paraffinic hydrocarbon oil.
17. A paraffinic hydrocarbon oil composition as claimed in claim 15 or 16, characterised in that it contains as a further polymeric additive a poly(ethene/vinyl carboxylate) containing 20-35 %w of the vinyl carboxylate, wherein the vinyl carboxylate is vinyl acetate or vinyl propionate.
18. A paraffinic hydrocarbon oil composition as claimed in claim 17, characterised in that the copolymer as claimed in any of claims 11-14 constitutes 1-90 %w of the total of polymeric additives.
19. An additive composition comprising a copolymer as claimed in any of claims 11-14 and a poly (ethene/vinyl carboxylate) containing
20-35 %w of the vinyl carboxylate, wherein the vinyl carboxylate is typically vinyl acetate or vinyl propionate.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9410844A GB2289895A (en) | 1994-05-31 | 1994-05-31 | Preparation of copolymers of carbon monoxide and an alpha-olefin having more than 10 carbon atoms |
| GB9410884A GB2289855A (en) | 1994-05-31 | 1994-05-31 | Preparation of copolymers of carbon monoxide and an alpha-olefin |
| GB9410884.2 | 1994-05-31 | ||
| GB9410844.6 | 1994-05-31 | ||
| PCT/EP1995/002075 WO1995032998A1 (en) | 1994-05-31 | 1995-05-30 | Preparation of copolymers of carbon monoxide and an aliphatic alpha-olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2191453A1 true CA2191453A1 (en) | 1995-12-07 |
Family
ID=26304966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002191453A Abandoned CA2191453A1 (en) | 1994-05-31 | 1995-05-30 | Preparation of copolymers of carbon monoxide and an aliphatic alpha-olefin |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH10501013A (en) |
| CA (1) | CA2191453A1 (en) |
| DE (1) | DE69506104T2 (en) |
-
1995
- 1995-05-30 DE DE69506104T patent/DE69506104T2/en not_active Expired - Fee Related
- 1995-05-30 JP JP8500331A patent/JPH10501013A/en active Pending
- 1995-05-30 CA CA002191453A patent/CA2191453A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DE69506104T2 (en) | 1999-05-06 |
| JPH10501013A (en) | 1998-01-27 |
| DE69506104D1 (en) | 1998-12-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |