Patent Grant
7041764
Selected iron and cobalt complexes of 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines) are catalysts for the copolymerization of ethylene and/or propylene and α-olefins. Novel polymers may be produced.
Copolymers of ethylene and/or propylene and α-olefins, such as linear low density polyethylene (LLDPE) are important items of commerce, millions of tons being produced annually. These polymers are used in a myriad of ways, such as for fiber, films, molding resins, etc. In most cases, ethylene and α-olefins are copolymerized using a catalyst, often a transition metal compound or complex. These catalysts may vary in cost per unit weight of polymer produced, the structure of the polymer produced, the possible need to remove the catalyst from the polymer, the toxicity of the catalyst, etc. Due to the commercial importance of copolymerizing ethylene, new polymerization catalysts are constantly being sought.
B. L. Small, et al., J. Am. Chem. Soc., vol. 120, p. 4049–4050 (1998), and G. J. P. Britovsek, et al., J. Chem. Soc., Chem. Commun., p. 849–850 (1998) report the polymerization of ethylene using catalysts containing Fe or Co complexes of 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines). Copolymerization of α-olefins and ethylene are not reported.
This invention concerns a first polymerization process, comprising, contacting, at a temperature of about −100° C. to about +200° C., a compound of the formula
with one or both of ethylene and propylene, and an olefin of the formula H2C═CHR21 and:
This invention also concerns a second polymerization process, comprising contacting, at a temperature of about −100° C. to about +200° C., a Co[II], Co[III], Fe[II] or Fe[III] complex of a tridentate ligand of the formula
with one or both of ethylene and propylene, and an olefin of the formula H2C═CHR21 wherein:
and provided that a Co[II], Co[III], Fe[II] or Fe[III] atom also has bonded to it an empty coordination site or a ligand that may be displaced by said ethylene, and a ligand that may add to said ethylene.
This invention also concerns a third polymerization process, comprising, contacting, at a temperature of about −100° C. to about +200° C., one or both of ethylene and propylene, an olefin of the formula H2C═CHR21, and a compound of the formula
wherein:
T2 is an end group.
Herein, certain terms are used. Some of them are:
Note the similarity of the structure on the left-hand side of this equation to compound (IX) (see below).
Compounds useful as ligands herein in iron and cobalt complexes are diimines of 2,6-pyridinedicarboxaldehyde or 2,6-diacylpyridines of the general formula
wherein R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group, R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl, and R6 and R7 are aryl or substituted aryl.
(IV) may be made by the reaction of a compound of the formula
with a compound of the formula H2NR6 or H2NR7, wherein R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group, R4 and R5 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, R4 and R5 are each hydrocarbyl or substituted hydrocarbyl, and R6 and R7 are aryl or substituted aryl. These reactions are often catalyzed by carboxylic acids, such as formic acid.
Preferred compounds of formula (IV) and compounds in which (IV) is a ligand are those of compound (III) [note
that (III) is a subset of (IV)], whether present in compounds such as (I), (II), (IV), (VII), (IX) and (XII). In (III), and hence in (I), (II), (IV) (VII), (IX) and (XII) that match the formula of (III), it is preferred that:
Also in (III), and hence in (I), (II), (IV) (VII), (IX) and (XII) that match the formula of (III), it is preferred that:
and provided that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are vicinal to one another, taken together may form a ring.
Specific preferred compounds (III) [and also in (I), (II), (IV), (VII), (IX) and (XII)] are:
In the polymerization processes described herein, it can be seen from the results that it is preferred that there be at least some steric crowding caused by the tridentate ligand about the Co or Fe atom. Therefore, it is preferred that groups close to the metal atom be relatively large. It is relatively simple to control steric crowding if (III) is the tridentate ligand, since control of steric crowding can be achieved simply by controlling the size of R8, R12, R13 and R16. These groups may also be part of fused ring systems, such as 9-anthracenyl.
In the first polymerization process it is preferred that X is chloride, bromide and tetrafluoroborate. It is also preferred that M is Fe[II] or Fe[III].
In the first polymerization process described herein an iron or cobalt complex (II) is contacted with ethylene, an α-olefin and a neutral Lewis acid W capable of abstracting X−, hydride or alkyl from (II) to form a weakly coordinating anion, and must alkylate or be capable of adding a hydride ion to the metal atom, or an additional alkylating agent or an agent capable of adding a hydride anion to the metal atom must be present. The neutral Lewis acid is originally uncharged (i.e., not ionic). Suitable neutral Lewis acids include SbF5, Ar3B (wherein Ar is aryl), and BF3. Suitable cationic Lewis acids or Bronsted acids include NaBAF, silver trifluoromethanesulfonate, HBF4, or [C6H5N(CH3)2]+[B(C6F5)4]−. In those instances in which (II) (and similar catalysts which require the presence of a neutral Lewis acid or a cationic Lewis or Bronsted acid), does not contain an alkyl or hydride group already bonded to the metal atom, the neutral Lewis acid or a cationic Lewis or Bronsted acid also alkylates or adds a hydride to the metal or a separate alkylating or hydriding agent is present, i.e., causes an alkyl group or hydride to become bonded to the metal atom.
It is preferred that R20 contains 1 to 4 carbon atoms, and more preferred that R20 is methyl or ethyl.
For instance, alkyl aluminum compounds (see next paragraph) may alkylate (II). However, not all alkyl aluminum compounds may be strong enough Lewis acids to abstract X31 or an alkyl group from the metal atom. In that case a separate Lewis acid strong enough to do the abstraction must be present.
A preferred neutral Lewis acid, which can alkylate the metal, is a selected alkyl aluminum compound, such as R193Al, R19AlCl2, R192AlCl, and “R19AlO” (alkylaluminoxanes), wherein R19 is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminum compounds include methylaluminoxane (which is an oligomer with the general formula [MeAlO]n), (C2H5)2AlCl, C2H5AlC2, and [(CH3)2CHCH2]3Al.
Metal hydrides such as NaBH4 may be used to bond hydride groups to the metal M.
In the second polymerization process described herein a cobalt or iron complex of (I) is either added to the polymerization process or formed in situ in the process. In fact, more than one such complex may be formed during the course of the process, for instance formation of an initial complex and then reaction of that complex to form a living ended polymer containing such a complex.
Examples of such complexes which may be formed initially in situ include
wherein R1 through R7, and M are as defined above, T1 is hydride or alkyl or any other anionic ligand into which ethylene or an α-olefin can insert, Y is a neutral ligand capable of being displaced by ethylene, propylene or an α-olefin, or a vacant coordination site, the “parallel lines” are an ethylene molecule coordinated to the metal, and Q is a relatively non-coordinating anion. Complexes may be added directly to the process or formed in situ. For instance, (VII) may be formed by the reaction of (II) with a neutral Lewis acid such as an alkyl aluminum compound. Another method of forming such a complex in situ is adding a suitable iron or cobalt compound such as iron [II] acetylacetonate, (I) and an alkyl aluminum compound. Other metal salts in which anions similar to acetylacetonate are present, and which may be removed by reaction with the Lewis or Bronsted acid. For instance metal halides and carboxylates (such as acetates) may be used, particularly if they are slightly soluble in the process medium. It is preferred that these precursor metal salts be at least somewhat soluble in the process medium.
After the polymerization has started, the complex may be in a form such as
wherein R1 through R7, M, and Q are as defined above, and P is a divalent polymeric groups containing repeat units derived from ethylene and/or propylene and/or an α-olefin, and T2 is an end group, for example the groups listed for T1 above. Those skilled in the art will note that (IX) is in essence a polymer containing a so-called living end. It is preferred that M be in +2 oxidation state in (VII), (VIII) and (IX). Compounds such as (VII), (IX) and (XII) may or may not be stable away from an environment similar to that of the polymerization process, but they may be detected by NMR spectroscopy, particularly one or both of 1H and 13C NMR, and particularly at lower temperatures. Such techniques, especially for polymerization “intermediates” of these types are known, see for instance World Patent Application 96/23010, especially Examples 197–203, which is hereby included by reference.
(VII), (IX) and (XII) may also be used, in the absence of any “co-catalysts” or “activators” to polymerize ethylene in a third polymerization process. Except for the ingredients in the process, the process conditions for the third process, such as temperature, pressure, polymerization medium, etc., may be the same as for the first and second polymerization processes, and preferred conditions for those processes are also preferred for the third polymerization process.
In all the polymerization processes herein, the temperature at which the ethylene copolymerization is carried out is about −100° C. to about +200° C., preferably about −60° C. to about 150° C., more preferably about −50° C. to about 100° C.
For copolymerization one or more α-olefins of the formula H2C═CHR21 may be used. It is preferred that R21 have 1 to 18 carbon atoms, more preferably 2 to 8 carbon atoms, and/or that R21 be n-alkyl. Since ethylene is polymerized considerably faster than propylene and most α-olefins by these catalysts, in order to obtain substantial incorporation of the α-olefin(s), the concentration of ethylene in the polymerization should preferably be relatively low compared to the concentration of the propylene and α-olefin(s). This will most often entail using ethylene at a low partial pressure, preferably less than 1.0 MPa, more preferably less than 500 kPa, and especially preferably less than 300 kPa (all these ethylene partial pressures are absolute partial pressures). If the α-olefin is a gas its partial pressure should preferably be relatively high. If the α-olefin is used in the liquid phase, its liquid concentration should preferably be relatively high.
NMR analysis of the product copolymers shows that the end groups are both saturated and unsaturated (olefinic), although saturated end groups usually outnumber unsaturated end groups. It is suspected that saturated end groups may arise through initiation and chain transfer involving alkyl aluminum compounds present in the polymerization. Unsaturated end groups are believed to arise though a β-hydride elimination-type mechanism. A small proportion of the olefinic ends appear to be internal olefins, but the majority of the olefinic ends are usually α-olefins (terminal olefins).
It is preferred that the product copolymer have at least 0.5 mole percent (total), more preferably 0.75 mole percent (total), especially preferably 1 mole percent (total), and highly preferably at least about 2 mole percent (total) of α-olefin(s) incorporated into the product copolymer. When 1-hexene is a comonomer the percent incorporated versus short chain branches, assuming all such branches are butyl, is shown in the following Table.
In copolymers of ethylene and H2C═CHR21 produced herein the polymer will contain —R21 branches and methyl branches. The total amount of H2C═CHR21 is taken as the total of the —R21 branches in the polymer, calculated according to a suitable formula, for example branches per 1000 carbon atoms or mole percent of H2C═CHR21 incorporated. It is believed that the methyl branches in the copolymer are associated with the end groups (but are not the end groups themselves). for example, end groups associated with methyl branches are
˜˜˜˜˜CH2CH(CH3)CH2CH2CH3 and
˜˜˜˜˜CH2CH(CH3)CH2CH2CH2CH3
are the methyl branch associated groups for 1-pentene and 1-hexene respectively (and similar structures for higher and lower homologs), wherein “˜˜˜˜” is the remainder of the polymer chain. Such groups are detectable by 13C-NMR because methyl branches near the chain ends are somewhat different than methyl branches further in the interior of the polymer chain, see for instance the Examples herein. Note that the group beyond the methine carbon atom (towards the chain end) is actually —R21 In other words the methyl branch is attached to the same carbon atom as an —R21 group. Not all polymer chains have such chain ends, but usually at least some of them are present in these copolymers.
A preferred monomer combination is ethylene and one or more olefins of the formula H2C═CHR21.
During the polymerization process often some or most of the olefin comonomer H2C═CHR21 will be unused in the polymerization. Testing of this unused comonomer at the end of the polymerization process shows that it is usually essentially unaltered (not isomerized), so it may be recovered and recycled into the polymerization, if desired. This recycling may take place without purification, or the comonomer may be purified being recycled to the polymerization, as by distillation.
The polymerization processes herein may be run in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, ethylene, propylene, α-olefin, and polyolefin may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Specific useful solvents include hexane, toluene and benzene.
The copolymerizations herein may also initially be carried out in the solid state [assuming (II), (III) (IV) or (VII) is a solid] by, for instance, supporting (II), (III) (IV) or (VII) on a substrate such as silica or alumina or an organic substrate such as a polymer, activating it with the Lewis (such as W, for instance an alkylaluminum compound) or Bronsted acid and exposing it to an olefin. The support may also be able to take the place of the Lewis or Bronsted acid, for instance an acidic clay such as montmorillonite. Another method of making a supported catalyst is to start a polymerization or at least make an iron or cobalt complex of another olefin or oligomer of an olefin such as 1-hexene on a support such as silica or alumina. These “heterogeneous” catalysts may be used to catalyze polymerization in the gas phase or the liquid phase. By gas phase is meant that the monomers are transported to contact with the catalyst particle while they are in the gas phase.
Hydrogen may be used as a chain transfer agent in all of the polymerization processes described herein.
In all of the polymerization processes described herein oligomers and copolymers of ethylene and/or propylene are made. They may range in molecular weight from oligomers, to lower molecular weight oils and waxes, to higher molecular weight polyolefins. One preferred product is a polymer with a degree of polymerization (DP) of about 10 or more, preferably about 40 or more. By “DP” is meant the average number of repeat (monomer) units in a polymer molecule.
In the Examples, the pressures given are gauge pressures. Methods of NMR analysis for polymer branching, and the notation used herein to describe the branching as determined by 13C NMR, are found in U.S. Pat. No. 5,880,241 (equivalent of World Patent Application 96/23010), which is hereby included by reference. Syntheses of the diimine ligands and their Co and Fe complexes are found in B. L. Small, et al., J. Am. Chem. Soc., vol. 120, p. 4049–4050 (1998), and G. J. P. Britovsek, et al., J. Chem. Soc., Chem. Commun., p. 849–850 (1998), which are both hereby included by reference. The following abbreviations and terms are used:
Tm—melting point
In a drybox under a nitrogen atmosphere, (XIII) (8 mg, 0.015 mmol) was weighed into a Schlenk flask and slurried in 20 ml anhydrous toluene. 1-Octene (3 ml, dried by distillation from sodium) was added and the Schlenk flask sealed and removed from the drybox. The flask was flushed well with ethylene and pressurized to 35 kPa. PMAO-IP (0.8 ml) was added and the solution turned orange and warmed. After 30 min the reaction was quenched by addition of MeOH. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=2.7 g white polymer. DSC (10° C./min, N2); Tm=123.2° C., shoulder on peak at 100° C. GPC (120° C., TCB); Mn=1500, PDI=5.6. The lowered (from pure polyethylene) melting point shows incorporation of comonomer.
In a drybox under a nitrogen atmosphere, (XIII) (7.5 mg, 0.014 mmol) was weighed into a Schlenk flask and slurried in 10 ml anhydrous toluene. 1-Hexene (3 ml, dried by distillation from sodium) was added and the Schlenk flask sealed and removed from the drybox. The flask was flushed well with ethylene and pressurized to 35 kPa. PMAO-IP (0.8 ml) was added and the solution turned green and warmed. After 30 min the reaction was quenched by addition of MeOH. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=6.0 g white polymer. DSC (10° C./min, N2); Tm=126.3° C., shoulder on low temperature side of peak. GPC (120° C., TCB); Mn=2420, PDI=8.0. 13C-NMR analysis indicated a total of 2.5 mol % 1-hexene incorporation. The branching was >75% butyl branches (1,2 or 2,1 incorporation). Amyl and methyl branches were also observed at low levels. No ethyl or propyl branches were observed.
In a drybox under a nitrogen atmosphere, (XIII) (2.0 mg) was weighed into a flask and slurried in 35 ml 1-hexene (Aldrich, 99+%, filtered through Al2O3 and stored over activated molecular sieves). The flask was stoppered and removed from the drybox. PMAO-IP (1.0 ml) was added to 5 ml anhydrous toluene and placed in a vial and removed from the drybox. The 1-hexene slurry was placed in a 100 ml Parr® stirred autoclave under an atmosphere of nitrogen. Stirring was started and the reactor heated to 50° C. The PMAO solution was then added to the reactor with 140 kPa ethylene. After 10 min the reaction was quenched by addition of MeOH. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=7.8 g white polymer. DSC (10° C./min., N2); Tm=102.0° C. with a minor peak at 112.0° C. GPC (120° C., trichlorobenzene); Mn=2534, PDI=2.3. 13C-NMR analysis (5 weight percent in TCB, 120° C.) indicated a total of 3.9 mol % 1-hexene incorporation. Of this most resulted in butyl branches (1,2 or 2,1 incorporation). Trace amounts of amyl and methyl branches were also observed. No ethyl or propyl branches were observed. The observed NMR is given below together with the assignments. The assignments of D, E and F are shown in the structure below, with “P” representing the rest of the polymer chain.
In a drybox under a nitrogen atmosphere, (XIII) (6.1 mg, 0.011 mmol) was weighed into a Schlenk flask and slurried in 10 ml anhydrous toluene. 1-Hexene (5 ml, dried by distillation from sodium) and anhydrous toluene (15 ml) were added and the Schlenk flask sealed and removed from the drybox. The flask was cooled to 0° C. and then flushed well with ethylene and pressurized to 35 kPa. PMAO-IP (0.9 ml) was added and the solution turned green and warmed. After 30 min the reaction was quenched by addition of MeOH. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=2.7 g white polymer. DSC (10° C./min, N2); Tm=127.6° C., shoulder on low temperature side of peak. GPC (120° C., trichlorobenzene); Mn=2120, PDI=19.1. 13C-NMR analysis indicated a total of 1.2 mol % 1-hexene incorporation. Only methyl and butyl branches were observed (1,2 or 2,1 incorporation).
In a drybox under a nitrogen atmosphere, (XIII) (7.5 mg, 0.014 mmol) was weighed into a Schlenk flask and slurried in 10 ml anhydrous toluene. Anhydrous toluene (30 ml) was added and the Schlenk sealed and removed from the drybox. The flask was cooled to 0° C. and then flushed well with ethylene and pressurized to 35 kPa. PMAO-IP (0.9 ml) was added and the solution turned orange and warmed. After 30 min the reaction was quenched by addition of MeOH. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=1.9 g white polymer. DSC (10° C./min, N2); Tm=132.7° C. GPC (120° C., trichlorobenzene); Mn=2900, PDI=19.1.
In a drybox under nitrogen, (XIII) (1.8 mg) was placed in 1-hexene (25 ml, Aldrich 99+%, filtered through activated Al2O3 and stored over activated molecular sieves) in a Hoke cylinder and sealed. PMAO-IP (0.9 ml) was placed in 2 ml anhydrous toluene in a vial and sealed. The containers were removed from the drybox. The 1-hexene slurry was placed in a Parr® stirred autoclave. Ethylene (70 kPa) was added, stirring started and the mixture heated to 75° C. The PMAO-IP solution was added to the reactor with an additional 160 kPa ethylene. After 81 min the reaction was quenched by addition of MeOH. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=1.61 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=115.5° C. GPC (135° C., TCB); Mn=1090, PDI=1.8. 13C-NMR analysis indicated a total of 1.4 mol % 1-hexene incorporation. The observed number of short chain branches per 1000 CH2 groups were methyl 1.9, butyl 7.1 and amyl 1.4.
In a drybox under nitrogen, (XIV) (6.0 mg) was placed in a Schlenk flask and anhydrous toluene (5 ml) and 1-hexene (10 ml, Aldrich 99+%, filtered through activated Al2O3 and stored over activated molecular sieves) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and PMAO-IP (0.9 ml) added. After 30 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=2.43 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=123.1° C., 109.2° C. (broad). GPC (135° C., TCB); Mn=1620, PDI=8.4. 13C-NMR analysis indicated a total of 2.1 mol % 1-hexene incorporation. The observed number of short chain branches per 1000 CH2 groups were methyl 0.8, butyl 10.5 and amyl 1.5.
In a drybox under nitrogen, (XIII) (3.0 mg) was placed in a Schlenk flask and anhydrous toluene (5 ml) and 1-hexene (10 ml, Aldrich 99+%, filtered through activated Al2O3 and stored over activated molecular sieves) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and MMAO-3A (0.45 ml, Akzo, 6.42 wt % Al in heptane) added. After 30 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=1.1 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=121.0° C., ˜80° C. (broad). GPC (135° C., TCB); Mn=1507, PDI=6.6. 13C-NMR analysis indicated a total of 6.4 mol % 1-hexene incorporation. The observed number of short chain branches per 1000 CH2 groups was methyl 1.9 butyl 30.5 and amyl 0.5. In addition, isobutyl ends are observed on the polymer (from the MMAO activator), and in this instance the isobutyl ends are not included in the methyl branch total.
In a drybox under nitrogen, (XIII) (6.3 mg) was placed in a Schlenk flask and anhydrous toluene (5 ml) and 1-heptene (10 ml, distilled from Na) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and PMAO-IP (0.9 ml) added. After 30 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=0.87 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=122.3° C. GPC (135° C., TCB); Mn=2680, PDI=5.9. 13C-NMR analysis (10 weight percent in TCB, 120° C.) indicated a total of 5.3 mol % 1-heptene incorporation. The observed number of short chain branches per 1000 CH2 groups were methyl 2.3, and amyl 24.6. The observed NMR is given below together with the assignments. The assignments of D, E and F are shown in the structure below, with “P” representing the rest of the polymer chain.
In a drybox under nitrogen, (XIII) (6.3 mg) was placed in a Schlenk flask and anhydrous toluene (15 ml added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and PMAO-IP (0.9 ml) added. After 30 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=1.1 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=127.2° C. GPC (135° C., TCB); Mn=1220, PDI=9.0. No branching was observed in the 13C-NMR analysis.
In a drybox under nitrogen, (XIV) (6.0 mg) was placed in a Schlenk flask and anhydrous toluene (5 ml) and 1-heptene (10 ml, distilled from Na) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and PMAO-IP (0.9 ml) added. After 30 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=0.95 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=123.4° C., 110.6° C. GPC (135° C., trichlorobenzene); Mn=2540, PDI=5.3. 13C-NMR analysis indicated a total of 3.0 mol % 1-heptene incorporation. The observed number of short chain branches per 1000 CH2 groups were methyl 0.7, and amyl 14.4.
In a drybox under nitrogen, (XIV) (6.0 mg) was placed in a Schlenk flask and anhydrous toluene (15 ml) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and PMAO-IP (0.9 ml) added. After 30 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. DSC (10° C./min., N2); Tm(2nd heat)=131.20° C. GPC (135° C., TCB); Mn=1410, PDI=20.0. No branching was observed in the 13C-NMR analysis.
In a drybox under nitrogen, (XIII) (6.1 mg) was placed in a Schlenk flask and anhydrous toluene (5 ml) and 1-pentene (10 ml, filtered through activated Al2O3 and stored over activated molecular sieves) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and PMAO-IP (0.9 ml) added. After 30 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=0.82 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=117.8° C., ˜90° C. (broad). GPC (135° C., TCB); Mn=1028, PDI=3.8. 13C-NMR analysis indicated a total of 10.0 mol % 1-pentene incorporation. The observed number of short chain branches per 1000 CH2 groups were methyl 6.3, and propyl 50.9. GC analysis of the supernatant indicated negligible isomerization of the unreacted 1-pentene.
In a drybox under nitrogen, (XIII) (1.4 mg) was placed in ˜6 ml anhydrous toluene in a vial. 1-Pentene (30 ml, filtered through activated Al2O3 and stored over activated molecular sieves), anhydrous toluene (5 ml) and PMAO (0.5 ml, Akzo, 10.9 wt % Al in toluene) was placed in a Hoke cylinder and sealed. The containers were removed from the drybox. The 1-pentene slurry was placed in a 100 ml Parr® stirred autoclave. Ethylene (41 kPa) was added and stirring started. The catalyst solution was added to the reactor with an additional 10 psi ethylene. After 12 min the reaction was quenched by addition of MeOH. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=1.6 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=123.6° C. 13C-NMR analysis indicated a total of 0.8 mol % 1-pentene incorporation.
In a drybox under nitrogen, (XIII) (3.0 mg) was placed in a Schlenk flask and anhydrous toluene (5 ml) and 1-pentene (10 ml, filtered through activated Al2O3 and stored over activated molecular sieves) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and MMAO-3A (0.45 ml, Akzo, 6.42 wt % Al in heptane) added. After 30 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=1.9 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=128.0° C. GPC (135° C., TCB); Mn=1716, PDI=7.0. 13C-NMR analysis (10 weight percent in TCB, 120° C.) indicated a total of 4.5 mol % 1-pentene incorporation. The observed number of short chain branches per 1000 CH2 groups were methyl 2.4, propyl 21.7, and amyl 0.4. Any isopropyl or isobutyl end groups present due to initiator are not counted in the methyl group total. The observed NMR is given below together with the assignments. The assignments of A, B, C, D, E and F are shown in the structure below, with “P” representing the rest of the polymer chain.
In a drybox under nitrogen, (XIII) (3.0 mg) was placed in a Schlenk flask and anhydrous toluene (5 ml) and 1-pentene (10 ml, filtered through activated Al2O3 and stored over activated molecular sieves) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and AlEt3 (0.3 ml, 0.1M solution in toluene/hexane) and B(C6F5)3 (0.0146 g in 0.5 ml toluene) were added. After 30 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=0.21 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=127.6° C. 13C-NMR analysis indicated a total of 0.64 mol % 1-pentene incorporation.
In a drybox under nitrogen, (XIII) (3.0 mg) was placed in a Schlenk flask and anhydrous toluene (5 ml) and 1-pentene (10 ml, filtered through activated Al2O3 and stored over activated molecular sieves) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and IBAO-0.65 (0.45 ml, Akzo, 3.5 wt % Al in toluene) added. After 90 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. DSC (10° C./min., N2); Tm(2nd heat)=115.5° C. (bimodal). GPC (135° C., TCB); Mn=1957, PDI=8.9. 13C-NMR analysis (10 weight percent in TCB, 140° C.) indicated a total of 8.2 mol % 1-pentene incorporation. The observed number of short chain branches per 1000 CH2 groups were methyl 3.4, and propyl 39.0. (amyl not integrated due to overlap). Any isopropyl or isobutyl end groups present due to initiator are not counted in the methyl group total. The assignments of A, B, C, D, E and F are shown in the structure below, with “P” representing the rest of the polymer chain.
Note: Existence of Me branches implies that these do not arise from the activator.
In a drybox under nitrogen, (XIII) (4.5 mg) was placed in a Schlenk flask and anhydrous toluene (5 ml) and 4-methyl-1-pentene (10 ml, filtered through activated Al2O3 and stored over activated molecular sieves) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and PMAO-IP (0.9 ml) added. After 30 min the reaction was quenched by addition of MeOH/10% HCl. The solid polymer was filtered, washed well with MeOH/10% HCl, MeOH and finally acetone and dried under vacuum. Yield=4.65 g white polymer. DSC (10° C./min., N2); Tm(2nd heat)=121.4° C., 100.6° C. (broad). GPC (135° C., TCB); Mn=1740, PDI=5.0. 13C-NMR analysis indicated a total of 4.1 mol % 4-methyl-1-pentene incorporation.
In a dry box under nitrogen atmosphere, the iron complex 2,6-diacetylpyridinebis(2,4,6-trimethylphenylimine)iron dichloride (1.5 mg, 2.86 □mol) was weighed into a vial and diluted to 10 ml with toluene (Aldrich, Anhydrous 99.8%). An aliquot of 3 ml containing 0.45 mg (0.86 □mol) of catalyst was transferred to the injector vessel with 50 ml of toluene. To a second vessel, 100 ml of CaH2 purified 1-octene (Aldrich, 98%) was mixed with 2 ml of MMAO-3A (Akzo Nobel). These solutions were transferred by pressure to a 600 ml Parr® autoclave reactor. The polymerization temperature was 120° C. and the ethylene pressure was 860 kPa, adjusted by a pressure regulator. The polymerization was run for 30 min. The reaction was quenched with methanol. The solid polymer was filtered and washed with acetone. Yield=2.68 g, DSC (10° C./min): Tm=126.2° C., HOF=212 J/g.
In a dry box under nitrogen atmosphere, an aliquot of 3 ml from the same stock solution of Example 16 was diluted with 50 ml of toluene and transferred to the injector vessel. To the second vessel, 80 ml of CaH2 purified 1-octene (Aldrich, 98%) was mixed with 2 ml of MMAO-3A (Akzo Nobel). These solutions were transferred by pressure to a 600 Parr® autoclave reactor. The polymerization temperature was 60° C. and the ethylene pressure was 860 kPa, adjusted by a pressure regulator. The polymerization was run for 30 min. The reaction was quenched with methanol. The solid polymer was filtered, washed with acetone, and dried under vacuum. Yield=38.9 g, DSC (10° C./min): Tm=132.7° C., HOF=226 J/g.
In a dry box under nitrogen atmosphere, the iron complex [2,6-diacetylpyridinebis{(3,5-trifluoromethyl)phenylimine}] iron dichloride was weighed (6 mg, 9.7 □mol) and diluted to 100 ml of toluene (Aldrich, anhydrous, 99.8%) and spiked with 20 drops of methylene chloride (Aldrich). To this solution, 5.6 ml of MMAO-3A (Akzo Nobel) was added. This catalyst solution was transferred via cannula to a feed vessel of a catalyst pump. The pumping rate was constant for 15 min, resulting in 3.8 mg of catalyst used. For the comonomer, 85 ml of CaH2 purified 1-hexene (Aldrich, 99%) was transferred to the reactor through a feed vessel. A 500 ml Zipperclave® reactor was charged with 165 ml of hexane (Aldrich, anhydrous, 95%+). The polymerization was run at 50° C. and 1.01 MPa of ethylene pressure. After 30 min, the reaction was quenched with methanol. The solid polymer was filtered, washed with acetone and dried under vacuum. Yield=1.4 g, DSC (10° C./min): Tm=126.6° C., with a shoulder at about 118° C. HOF=194 J/g. GPC Mw=11345, PDI=7.44.
Example 18 above was repeated with the same iron complex solution available in the catalyst pump feed vessel. No comonomer was added to this example. The catalyst pumping rate was constant for the first 15 min of the run, resulting in 2.3 mg of catalyst used. A 500 ml Zipperclave® reactor was charged with 250 ml of hexane (Aldrich, anhydrous, 95%). The polymerization was run at 50° C. and 1.01 MPa of ethylene pressure. After 30 min, the reaction was quenched with methanol. The solid polymer was filtered, washed with acetone and dried under vacuum. Yield=3.4 g, DSC (10° C./min): Tm=130.3° C., HOF=278 J/g. Mw=14434, PDI=6.03
This application is a divisional of application Ser. No. 10/251,041, filed Sep. 20, 2002, now U.S. Pat. No. 6,803,432, which is a continuation of application Ser. No. 09/946,170, filed Sep. 4, 2001, now abandoned, which is a continuation of application Ser. No. 09/317,563, filed May 24, 1999, now abandoned, which claims benefit of Provisional Application No. 60/087,152, filed May 29, 1998.
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| Number | Date | Country |
|---|---|---|
| 0 824 111 | Feb 1998 | EP |
| WO 9827124 | Jun 1998 | WO |
| WO 9830612 | Jul 1998 | WO |
| WO 9838228 | Sep 1998 | WO |
| WO 9912981 | Mar 1999 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20050020789 A1 | Jan 2005 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60087152 | May 1998 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10251041 | Sep 2002 | US |
| Child | 10919181 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 09946170 | Sep 2001 | US |
| Child | 10251041 | US | |
| Parent | 09317563 | May 1999 | US |
| Child | 09946170 | US |
