EP1178995A1 - Manufacture of olefin/carbon monoxide polymers - Google Patents
Manufacture of olefin/carbon monoxide polymersInfo
- Publication number
- EP1178995A1 EP1178995A1 EP00930743A EP00930743A EP1178995A1 EP 1178995 A1 EP1178995 A1 EP 1178995A1 EP 00930743 A EP00930743 A EP 00930743A EP 00930743 A EP00930743 A EP 00930743A EP 1178995 A1 EP1178995 A1 EP 1178995A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrocarbyl
- hydrogen
- carbon monoxide
- independently
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 17
- 229920000642 polymer Polymers 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000007848 Bronsted acid Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 5
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 4
- 150000002815 nickel Chemical class 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000011236 particulate material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960004132 diethyl ether Drugs 0.000 description 2
- 229940117927 ethylene oxide Drugs 0.000 description 2
- 229920005684 linear copolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UGNSMKDDFAUGFT-UHFFFAOYSA-N 4,4-dimethyl-2-phenyl-5h-1,3-oxazole Chemical compound CC1(C)COC(C=2C=CC=CC=2)=N1 UGNSMKDDFAUGFT-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000287181 Sturnus vulgaris Species 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- AKJFBIZAEPTXIL-UHFFFAOYSA-N chloro(dicyclohexyl)phosphane Chemical compound C1CCCCC1P(Cl)C1CCCCC1 AKJFBIZAEPTXIL-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- BNKYCUREFTUHLF-UHFFFAOYSA-N dichloro-(3-dichlorophosphanylphenyl)phosphane Chemical compound ClP(Cl)C1=CC=CC(P(Cl)Cl)=C1 BNKYCUREFTUHLF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- BXBLTKZWYAHPKM-UHFFFAOYSA-M magnesium;methanidyl(trimethyl)silane;chloride Chemical compound [Mg+2].[Cl-].C[Si](C)(C)[CH2-] BXBLTKZWYAHPKM-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
Definitions
- Olefin/carbon monoxide copolymers are items of commerce, being useful for injection molded parts for various industrial uses. Usually these copolymers are alternating (to a great extent) copolymers. The most common method of making these polymers is catalyzing the copolymerization with various complexes of palladium. While these complexes are satisfactory from a reaction viewpoint, economically they have the great disadvantage of using palladium, a very expensive metal . Thus cheaper catalysts that would make these polymers are being sought .
- each Ar is aryl or substituted aryl; each R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Cy is cyclohexyl; each R 4 is independently alkyl containing 1 to 20 carbon atoms ;
- Cy is cyclohexyl; each R is independently alkyl containing 1 to 20 carbon atoms; R is hydrogen or n-alkyl containing 1 to 20 carbon atoms ; and each R is hydrocarbyl or substituted hydrocarbyl .
- substituted hydrocarbyl herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted” are heteroaromatic rings. All of the hydrogen atoms in a substituted hydrocarbyl group may be substituted, as in perfluoroalkyl . Other groups may be "substituted" in an analogous manner.
- (inert) functional group herein is meant a group other than hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions to which the compound containing the group is subjected.
- the functional groups also do not substantially interfere with any process described herein that the compound in which they are present may take part in.
- Examples of functional groups include halo (fluoro, chloro, bromo and iodo) , ether such as -OR wherein R is hydrocarbyl or substituted hydrocarbyl.
- relatively noncoordinating anions or “weakly coordinating anions” are meant those anions as are generally referred to in the art in this manner, and the coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al . , Chem . Rev . , vol. 88 p. 1405-1421 (1988), and S. H. Stares, Chem. Rev. , vol. 93, p. 927-942 (1993), both of which are hereby included by reference.
- Such anions are those formed from the aluminum compounds in the immediately preceding paragraph and X " , including R 3 A1X , R 9 2 A1C1X “ , R 9 A1C1 2 X “ , and “R 9 A10X “ “ , wherein R 9 is alkyl.
- Included within the meaning of adding a specified complex of nickel is the addition of ingredients which are known in the art to form such a complex under the process conditions .
- each R is independently an alkyl containing 1 to 4 carbon atoms, more preferably each R 4 is independently methyl or ethyl, and especially every R is ethyl.
- each R is independently alkyl, more preferably each R is independently an alkyl containing 1 to 4 carbon atoms, and especially every R is methyl .
- the amount of compound (I), (II), (III), and/or (IV) supplied to the polymerization process may vary, but is conveniently selected in the range of from about 0.1 to about 2 moles of compound per gram atom of nickel . Preferably, the amount is in the range of from about 0.5 to about 1.5 moles of compound per mole nickel compound.
- Preferred Bronsted acids are strong acids, i.e. those which have a pKa of less than about 6, in particular less than about 4, more in particular less than about 2, when measured in aqueous solution at 18°C.
- suitable Bronstead acids are protic acids that may also participate in the nickel salts, e.g. trifluoroacetic acid.
- protic acids which may be used are sulfonic acids and hydrohalogenic acids, in particular hydrogen fluoride, tetrafluoroboric acid and hexafluoroboric acid (HBF 4 and HBF 5 ) .
- the activity of the catalyst composition may be such that amounts in the range from 10 ' to 10 " gram atom of nickel per mole of olefinically unsaturated compound to be copolymerized are adequate. Preferably, the amount will be from 10 " to 10 " , on the same basis.
- R is hydrogen or an alkyl containing 1 to 4 carbon atoms, more preferably R is hydrogen (ethylene) or methyl (propylene) , and especially preferably R is hydrogen.
- the molar ratio of on the one hand carbon monoxide to on the other hand the olefinically unsaturated compound (s) may be selected within a wide range, for example in the range of from about 1:50 to about 20:1. However, it is preferred to employ a molar ratio in the range of from about 1:20 to about 2:1.
- the process of the invention is conveniently carried out in the presence of a diluent .
- a diluent is used in which the copolymers are insoluble or virtually insoluble so that they form a suspension upon their formation.
- Recommended diluents are polar organic liquids, such as ketones, ethers, esters or amides.
- protic liquids are used, such as monohydric and dihydric alcohols, in particular the lower alcohols having at most 4 carbon atoms per molecule, such as methanol and ethanol .
- the process of this invention may also be carried out as a gas phase process, in which case the catalyst is typically deposited on a solid particulate material or chemically bound thereto .
- a solid particulate material suspended in the diluent before the monomers are contacted with the catalyst composition.
- Suitable solid particulate materials are silica, polyethylene and a copolymer of carbon monoxide and an olefinically unsaturated compound, preferably a copolymer which is based on the same monomers as the copolymer to be prepared.
- the quantity of the solid particulate material is preferably in the range of from about 0.1 to about 20 g, particularly from about 0.5 to about 10 g, per 100 g diluent .
- the copolymers can be recovered from the polymerization mixture by using conventional techniques. When a diluent is used the copolymers may be recovered by filtration or by evaporation of the diluent. The copolymer may be purified to some extent by washing.
- Copolymers are suitably prepared in which the units originating from carbon monoxide on the one hand and the units originating from the olefinically unsaturated compound (s) on the other hand occur in an alternating or substantially alternating arrangement.
- the term "substantially alternating” will generally be understood by one skilled in the art as meaning that the molar ratio of the units originating from carbon monoxide to the units originating from the olefinically unsaturated compound is above about 35:65, in particular above about 40:60. When polymers are completely alternating this ratio equals 50:50.
- the copolymers produced have a number average molecular weight (Mn) of at least about 10,000, more preferably more than about 20,000, and especially preferably more than about 30,000.
- Mn number average molecular weight
- the Mn may be measured by Gel Permeation Chromatography using hexafluoroisopropanol as a solvent .
- the nickel content of the copolymers will typically be above about 0.01 ppm by weight, relative to the weight of the copolymer. It is preferred to prepare copolymers which have a nickel content in the range of from about 0.05 to about 300 ppm, in particular from about 0.1 to about 200 ppm, relative to the weight of the copolymer.
- the copolymers are substantially free, preferably free of palladium. "Substantially free of palladium" means to the skilled person that the palladium content is lower than the value normally achieved when a palladium based catalyst is employed in the copolymerization, for example less than 1 ppm by weight, in particular less than 0.1 ppm, relative to the weight of the copolymer.
- the weight ratio of palladium to nickel is less than about 1:50, in particular less than about 1:100 or most in particular even less than about 1:200.
- This procedure is general for cationic nickel-catalyzed ethylene/carbon monoxide (E/CO) copolymerization.
- a reactor was charged with nickel [II] acetate tetrahydrate (0.05 mmol) and the diphosphine (0.06 mmol) .
- a methanol solution of trifluoroacetic acid (0.2 mmol/5mL) was added, and the reactor was brought out of the drybox.
- the reactor was evacuated, charged with ethylene (350 kPa; all pressures are gauge pressures) and E/CO (1:1, 3.90 MPa) and the reaction was run for 16 h at 90 °C. Under these conditions, the final pressure was 5.17 MPa. Polymer was recovered from the shaker vials, washed with methanol and dried under high vacuum overnight .
- the samples were submitted for Differential Scanning Calorimetry (melting point Tm, determined at a heating rate of 10°C/min on the first heat, and taken as the peak of the endotherm) .
- Example 3 determination of the molecular weight of the polymer by Differential Scanning Calorimetry in hexafluoroisopropanol gave a number average molecular weight of 81,800, and a weight average molecular weight of 129,000.
- Comparative Example A the "Compound" used was
- Example 5 In a drybox, 1.20 g R-(+)-l, 1' -bi-2-naphthol (Aldrich Chemical Co., Milwaukee, WI, U.S.A.), 2.00 g dicyclohexylphosphorus chloride (Strem Chemical) and 1.70 g triethylamine were dissolved in 25 mL THF . The mixture was allowed to stir at room temperature for 35 h. The mixture was filtered through Celite ® , followed by 3X10mL tetrahydrofuran wash. The combined filtrate was evaporated under reduced pressure. The product was dried in vacuo overnight. White solid was obtained. The conversion was quantitative.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
Abstract
Olefin/carbon monoxide copolymers are prepared by contacting these monomers with nickel complexes of selected diphosphine ligands. The copolymers are useful as molding resins.
Description
TITLE MANUFACTURE OF OLEFIN/CARBON MONOXIDE POLYMERS
FIELD OF THE INVENTION Olefin/carbon monoxide copolymers are prepared by contacting these monomers with nickel complexes of selected diphosphine ligands. Also disclosed is a novel phosphorous containing ligand.
TECHNICAL BACKGROUND
Olefin/carbon monoxide copolymers are items of commerce, being useful for injection molded parts for various industrial uses. Usually these copolymers are alternating (to a great extent) copolymers. The most common method of making these polymers is catalyzing the copolymerization with various complexes of palladium. While these complexes are satisfactory from a reaction viewpoint, economically they have the great disadvantage of using palladium, a very expensive metal . Thus cheaper catalysts that would make these polymers are being sought .
One method of reducing the catalyst cost is to find a catalyst which uses a cheaper transition metal. WO97/00127 and W097/23492 describe nickel complexes of specified ligands which copolymerize ethylene and carbon monoxide. Neither of these references describes the diphosphine ligands discussed herein.
SUMMARY OF THE INVENTION
This invention concerns a first process for producing olefin/carbon monoxide copolymers, comprising the step of contacting one or more olefins of the formula H2C=CHR , carbon monoxide, a Bronsted acid and a nickel complex of a ligand of the formula
. PAr1 2
Ar1 9P'
( i i :
R6 3SiCH2 P P CH2SiR6 3 (V) wherein: each Ar is aryl or substituted aryl; each R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Cy is cyclohexyl; each R4 is independently alkyl containing 1 to 20 carbon atoms ;
R is hydrogen or n-alkyl containing 1 to 20 carbon atoms; and each R6 is independently hydrocarbyl or substituted hydrocarbyl .
This invention also concerns a second process for producing olefin/carbon monoxide copolymers, comprising the step of contacting one or more olefins of the formula H2C=CHR5, carbon monoxide, a Bronsted acid, a nickel [II] compound, and a ligand of the formula
R6 3SiCH2 P Λ P CH2SiR6 3 (V)
wherein: each Ar is independently aryl or substituted aryl; each R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
Cy is cyclohexyl; each R is independently alkyl containing 1 to 20 carbon atoms; R is hydrogen or n-alkyl containing 1 to 20 carbon atoms ; and each R is hydrocarbyl or substituted hydrocarbyl .
Also disclosed herein is a compound of the formula
CH2SiR 3
wherein R , Cy and R are as defined above.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Herein, certain terms are used. Some of them are: A "hydrocarbyl group" is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
By "substituted hydrocarbyl" herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted" are heteroaromatic rings. All of the hydrogen atoms in a substituted hydrocarbyl group may be substituted, as in perfluoroalkyl . Other groups may be "substituted" in an analogous manner. By "(inert) functional group" herein is meant a group other than hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions to which the compound containing the group is subjected. The functional groups also do not substantially interfere with any process
described herein that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo) , ether such as -OR wherein R is hydrocarbyl or substituted hydrocarbyl. By "relatively noncoordinating anions" (or "weakly coordinating anions") are meant those anions as are generally referred to in the art in this manner, and the coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al . , Chem . Rev . , vol. 88 p. 1405-1421 (1988), and S. H. Stares, Chem. Rev. , vol. 93, p. 927-942 (1993), both of which are hereby included by reference. Among such anions are those formed from the aluminum compounds in the immediately preceding paragraph and X", including R 3A1X , R9 2A1C1X", R9A1C12X", and "R9A10X"" , wherein R9 is alkyl. Other useful noncoordinating anions include BAF" {BAF = tetrakis [3 , 5-bis (trifluoromethyl) phenyl] borate} , SbF6 ~, PF6 and BF4 ", trifluoromethanesulfonate, p-toluenesulfonate, (RfS02)2N~, and (CSF5)4B\ Included within the meaning of adding a specified complex of nickel is the addition of ingredients which are known in the art to form such a complex under the process conditions .
In (II) it is preferred that every Ar is phenyl or substituted phenyl, more preferably phenyl.
In (III) it is preferred that every R is hydrogen. In (IV) it is preferred that each R4 is independently an alkyl containing 1 to 4 carbon atoms, more preferably each R4 is independently methyl or ethyl, and especially every R is ethyl.
In (V) it is preferred that each R is independently alkyl, more preferably each R is independently an alkyl containing 1 to 4 carbon atoms, and especially every R is methyl . The amount of compound (I), (II), (III), and/or (IV) supplied to the polymerization process may vary, but is conveniently selected in the range of from about 0.1 to
about 2 moles of compound per gram atom of nickel . Preferably, the amount is in the range of from about 0.5 to about 1.5 moles of compound per mole nickel compound.
Preferred Bronsted acids are strong acids, i.e. those which have a pKa of less than about 6, in particular less than about 4, more in particular less than about 2, when measured in aqueous solution at 18°C. Examples of suitable Bronstead acids are protic acids that may also participate in the nickel salts, e.g. trifluoroacetic acid. Examples of protic acids which may be used are sulfonic acids and hydrohalogenic acids, in particular hydrogen fluoride, tetrafluoroboric acid and hexafluoroboric acid (HBF4 and HBF5) .
The activity of the catalyst composition may be such that amounts in the range from 10' to 10" gram atom of nickel per mole of olefinically unsaturated compound to be copolymerized are adequate. Preferably, the amount will be from 10" to 10" , on the same basis.
In preferred olefins, R is hydrogen or an alkyl containing 1 to 4 carbon atoms, more preferably R is hydrogen (ethylene) or methyl (propylene) , and especially preferably R is hydrogen. In one preferred polymer ethylene and another olefin, preferably propylene or 1-butene, more preferably propylene, are used. Generally, the molar ratio of on the one hand carbon monoxide to on the other hand the olefinically unsaturated compound (s) may be selected within a wide range, for example in the range of from about 1:50 to about 20:1. However, it is preferred to employ a molar ratio in the range of from about 1:20 to about 2:1.
The process of the invention is conveniently carried out in the presence of a diluent . Preferably a diluent is used in which the copolymers are insoluble or virtually insoluble so that they form a suspension upon their formation. Recommended diluents are polar organic liquids, such as ketones, ethers, esters or amides. Preferably, protic liquids are used, such as monohydric and dihydric
alcohols, in particular the lower alcohols having at most 4 carbon atoms per molecule, such as methanol and ethanol . The process of this invention may also be carried out as a gas phase process, in which case the catalyst is typically deposited on a solid particulate material or chemically bound thereto .
When a diluent is used in which the formed copolymer forms a suspension it is preferred to have a solid particulate material suspended in the diluent before the monomers are contacted with the catalyst composition. Suitable solid particulate materials are silica, polyethylene and a copolymer of carbon monoxide and an olefinically unsaturated compound, preferably a copolymer which is based on the same monomers as the copolymer to be prepared. The quantity of the solid particulate material is preferably in the range of from about 0.1 to about 20 g, particularly from about 0.5 to about 10 g, per 100 g diluent .
The conditions under which the process of the invention is performed, include the use of elevated temperatures and pressures, such as between about 0°C and about 200°C, in preferably between about 30°C and about 130°C, and pressures (of ethylene and CO combined) between about 0.1 MPa and about 200 MPa, in particular between about 0.5 MPa and about 10 MPa. The pressure of carbon monoxide is typically at least about 0.1 MPa. Preferably the partial pressure of the CO is approximately equal to the pressure of ethylene.
The copolymers can be recovered from the polymerization mixture by using conventional techniques. When a diluent is used the copolymers may be recovered by filtration or by evaporation of the diluent. The copolymer may be purified to some extent by washing.
Copolymers are suitably prepared in which the units originating from carbon monoxide on the one hand and the units originating from the olefinically unsaturated compound (s) on the other hand occur in an alternating or substantially alternating arrangement. The term
"substantially alternating" will generally be understood by one skilled in the art as meaning that the molar ratio of the units originating from carbon monoxide to the units originating from the olefinically unsaturated compound is above about 35:65, in particular above about 40:60. When polymers are completely alternating this ratio equals 50:50.
It is preferred to prepare copolymers which have a melting point above 150 °C, as determined by Differential Scanning Calorimetry (DSC) . For example, linear copolymers of carbon monoxide and ethylene and linear copolymers of carbon monoxide, ethylene and an α-olefin which are alternating or substantially alternating fall into this category. It is particularly preferred to prepare linear alternating copolymers of carbon monoxide and ethylene or linear alternating copolymers of carbon monoxide, ethylene and an α-olefin in which the molar ratio of the other α-olefin (R is n-alkyl) to ethylene is typically above about 1:100, preferably in the range of from about 1:100 to about 1:3, more preferably in the range of about 1:50 to about 1:5.
It is preferred that the copolymers produced have a number average molecular weight (Mn) of at least about 10,000, more preferably more than about 20,000, and especially preferably more than about 30,000. The Mn may be measured by Gel Permeation Chromatography using hexafluoroisopropanol as a solvent .
Furthermore, for practical reasons the nickel content of the copolymers will typically be above about 0.01 ppm by weight, relative to the weight of the copolymer. It is preferred to prepare copolymers which have a nickel content in the range of from about 0.05 to about 300 ppm, in particular from about 0.1 to about 200 ppm, relative to the weight of the copolymer. The copolymers are substantially free, preferably free of palladium. "Substantially free of palladium" means to the skilled person that the palladium content is lower than the value normally achieved when a palladium based catalyst is employed in the
copolymerization, for example less than 1 ppm by weight, in particular less than 0.1 ppm, relative to the weight of the copolymer. Alternatively it is preferred that, if palladium is present, the weight ratio of palladium to nickel is less than about 1:50, in particular less than about 1:100 or most in particular even less than about 1:200.
Methods for making compound (I) are found in WO97/00127, for making (III) in Example 4 [other compounds (III) can be made by analogous methods] , and for making (IV) in WO00/21970. Both of these references are incorporated by reference herein for all purposes as if fully set forth. Compound (II) is available commercially.
Examples 1-4 and Comparative Example A Ethylene/CO Copolymerization
This procedure is general for cationic nickel-catalyzed ethylene/carbon monoxide (E/CO) copolymerization.
A reactor was charged with nickel [II] acetate tetrahydrate (0.05 mmol) and the diphosphine (0.06 mmol) . A methanol solution of trifluoroacetic acid (0.2 mmol/5mL) was added, and the reactor was brought out of the drybox. The reactor was evacuated, charged with ethylene (350 kPa; all pressures are gauge pressures) and E/CO (1:1, 3.90 MPa) and the reaction was run for 16 h at 90 °C. Under these conditions, the final pressure was 5.17 MPa. Polymer was recovered from the shaker vials, washed with methanol and dried under high vacuum overnight . The samples were submitted for Differential Scanning Calorimetry (melting point Tm, determined at a heating rate of 10°C/min on the first heat, and taken as the peak of the endotherm) .
Results of the polymerizations and the structure of the diphosphines ("Compound") are given in Table 1. In Example 3, determination of the molecular weight of the polymer by Differential Scanning Calorimetry in hexafluoroisopropanol gave a number average molecular weight of 81,800, and a weight average molecular weight of 129,000. In Comparative Example A the "Compound" used was
( I )
Table 1
Example 5 In a drybox, 1.20 g R-(+)-l, 1' -bi-2-naphthol (Aldrich Chemical Co., Milwaukee, WI, U.S.A.), 2.00 g dicyclohexylphosphorus chloride (Strem Chemical) and 1.70 g triethylamine were dissolved in 25 mL THF . The mixture was allowed to stir at room temperature for 35 h. The mixture was filtered through Celite®, followed by 3X10mL tetrahydrofuran wash. The combined filtrate was evaporated under reduced pressure. The product was dried in vacuo overnight. White solid was obtained. The conversion was quantitative. H-NMR (CD2C12, δ): 0.25-1.85 (44H) , 7.10- 8.10 (12H, Ar-H) . 31P-NMR (CD2Cl2 , δ): 114.33 (s) .
Example 6
A round bottom flask was charged with 1 , 3-bis (dichlorophosphino) benzene (1.0 g, 3.57 mmol). Diethyl ether (20 mL) was added and the solution was cooled to -30°C. Trimethylsilylmethylmagnesium chloride (1.0 M in
diethylether , 17.9 mL, 17.9 mmol) was added slowly and the reaction was slowly warmed to room temperature. The next day, water (2.0 mL) was added and the reaction was stirred 30 min. The solvent was removed in vacuo . Toluene (35 mL) was added and the reaction was stirred an additional 30 min. The reaction mixture was filtered and the product was washed with toluene (2x5 mL) and dried in vacuo . A pale yellow oil (0.52 g, 30%), (Me3SiCH2)2P(C2H-4)P(CH2SiMe3)2, was recovered. 31P NMR (121.5 MHz, 20°C, C6D6) δ-44.8.
Claims
1. A process for producing olefin/carbon monoxide copolymers, comprising the step of contacting one or more olefins of the formula H2C=CHR , carbon monoxide, a Bronsted acid and a nickel complex of a phosphorous-containing ligand, characterized in that said ligand is of the formula
wherein : each Ar is aryl or substituted aryl; each R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Cy is cyclohexyl; each R is independently alkyl containing 1 to 20 carbon atoms; R is hydrogen or n-alkyl containing 1 to 20 carbon atoms ; and eeaacchh R is independently hydrocarbyl or substituted hydrocarbyl
2. A process for producing olefin/carbon monoxide copolymers, comprising the step of contacting one or more olefins of the formula H2C=CHR , carbon monoxide, a Bronsted acid, a nickel [II] compound, and a phosphorous-containing ligand, characterized in that said ligand is of the formula
wherein : each Ar is independently aryl or substituted aryl; each R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Cy is cyclohexyl; each R is independently alkyl containing 1 to 20 carbon atoms ;
R is hydrogen or n-alkyl containing 1 to 20 carbon atoms ; and each R is hydrocarbyl or substituted hydrocarbyl
3. The process as recited in claim 1 or 2 , characterized in that said contacting is carried out at a temperature of about 30°C to about 130°C.
4. The process as recited in claim 1 or 2, characterized in that: every Ar is phenyl or substituted phenyl; every R is hydrogen; each R4 is independently alkyl containing 1 to 4 carbon atoms; and each R is independently alkyl .
5. The process as recited in claim 4 characterized in that : every Ar is phenyl; and every R is methyl or ethyl; and every R is methyl.
6. The process as recited in claim 1 or 2 , cchhaarraacctteerriizzed in that R5 is hydrogen, or R is both hydrogen and methyl .
7. The process as recited in claim 1 or 2 , characterized in that an alternating polymer is produced.
8. The process as recited in claim 1 or 2 , characterized in that said Bronsted acid has a pKa of about 2 or less.
9. A compound of the formula
(III) (V) wherein: each R ,3 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
Cy is cyclohexyl ; and each R is hydrocarbyl or substituted hydrocarbyl.
10. The compound as recited in claim 9, characterized in that every R is hydrogen, and every R is methyl.
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US133924P | 1999-05-13 | ||
PCT/US2000/013318 WO2000069867A1 (en) | 1999-05-13 | 2000-05-12 | Manufacture of olefin/carbon monoxide polymers |
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DE19548146C1 (en) * | 1995-12-21 | 1997-11-20 | Basf Ag | Tris (pyrazolyl) borate metal complex catalysts and their use |
DE19649072A1 (en) * | 1996-11-28 | 1998-06-04 | Basf Ag | Thermoplastic, elastomeric carbon monoxide / olefin copolymers |
US6137012A (en) * | 1998-10-13 | 2000-10-24 | E. I. Du Pont De Nemours And Company | Phosphole and diphosphole ligands for catalysis |
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