CN1251056A - Prepn. of catalyst - Google Patents

Prepn. of catalyst Download PDF

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Publication number
CN1251056A
CN1251056A CN98803699A CN98803699A CN1251056A CN 1251056 A CN1251056 A CN 1251056A CN 98803699 A CN98803699 A CN 98803699A CN 98803699 A CN98803699 A CN 98803699A CN 1251056 A CN1251056 A CN 1251056A
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catalyzer
ring
alkene
aromatic group
substituted
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E·范登布肯
E·德勒特
B·L·菲林加
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1895—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing arsenic or antimony

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  • Organic Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Catalysts (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A catalyst suitable for the polymerization of ethylenically unsaturated compounds. A bidentate ligand with the general formula (I), in which X=P, As, Sb, n=0 or 1, R1, R2=alkyl, alkoxy, aryloxy, cycloalkyl or a substituted or non-substituted (cyclo)aliphatic, (cyclo)olefinic or aromatic group with 1-24 C-atoms, or R1 and R2 may form together a substituted or non-substituted cycloaliphatic, cyclo-olefinic or aromatic group, R3, R4, R7, R8=H, alkyl, alkoxy, aryloxy, cycloalkyl or a substituted or non-substituted (cyclo)aliphatic, (cyclo)olefinic or aromatic group with 1-24 C-atoms, if n=1; R5 and/or R6=H, alkyl, alkoxy, aryloxy, cycloalkyl or a substituted or non-substituted (cyclo)aliphatic, (cyclo)olefinic or aromatic group with 1-24 C-atoms, and C' and C'' together with R3 and R6 may form a substituted or non-substituted (cyclo)aliphatic, (cyclo)olefinic or aromatic group, R4 and R5 being absent in the case, or C' and C'' may form an olefinic bond, R4 and R5 being absent in this case, with a source of cations of a metal of group 8, 9 or 10 of the periodic table of elements and an acid having a pKa of less than 4.

Description

Preparation of catalysts
A kind of catalyzer that relates to of the present invention, this catalyzer can be made by bidentate ligand, cationic source and a kind of acidifying are closed.
The invention still further relates to the method that makes alefinically unsaturated compounds polymerization and copolymerization with this catalyzer.
In the WO96/23010 of U.S. north Carlow Lehner state Du Pont company, the polymerization process of alkene has been discussed.This method uses the diimine palladium (II) in methylene dichloride or toluene and the title complex of nickel (II) to make catalyzer.
Because it is stable that this diimine title complex only is only under quite low temperature, so this olefine polymerizing process must be operated at low temperatures, therefore, the transformation efficiency of this method (mole number of the product of every mol catalyst) is quite low.
The inventor has now found that a kind of catalyzer highly stable under comparatively high temps.Therefore, use this catalyzer, alefinically unsaturated compounds can carry out under higher temperature.Thus, the transformation efficiency of polymerization process is high more a lot of than the method for WO96/23010 when with catalyzer of the present invention.
And without excluding air, and the diimine catalyzer of the method for WO96/23010 was by to air highstrung (diimine) PdMe when catalyzer of the present invention was synthetic 2Title complex is made.
Therefore, the present invention relates to be applicable to alefinically unsaturated compounds polymeric catalyzer, this catalyzer can be lower than 4 acid-respons with the cationic source of the periodic table of elements 8,9 or 10 family's metals and a kind of pKa by the bidentate ligand with following general formula and make:
Figure A9880369900041
In the formula, X=P, As, Sb, n=0 or 1, R 1, R 2=have 1-24 carbon atom alkyl, alkoxyl group, aryloxy, cycloalkyl or replacement or unsubstituted (ring) aliphatic series, (ring) alkene or aromatic group, or R 1And R 2That constitute to replace together or unsubstituted cyclic aliphatic, cyclenes or aromatic group.R 3, R 4, R 7, R 8If (ring)=H, the alkyl with 1-24 carbon atom, alkoxyl group, aryloxy, cycloalkyl or replacement or unsubstituted aliphatic series, (ring) alkene or aromatic group are n=1:R 5And/or R 6(ring)=H, alkyl, alkoxyl group, aryloxy, cycloalkyl or replacement or unsubstituted aliphatic series, (ring) alkene or aromatic group, and C ' and C " same R with 1-24 carbon atom 3And R 6Can form together replacement or unsubstituted cyclic aliphatic, cyclenes or aromatic group, R in this case 4And R 5Do not exist, or C ' and C " can form ethylene linkage, in this case R 4And R 5Do not exist.
In above-mentioned ligand, the X part can be phosphorus, arsenic or antimony, and phosphorus is the preferred elements that is added to the ligand that constitutes a catalyzer part of the present invention.
Catalyzer of the present invention comprises the periodic table of elements 8,9 or 10 family's metals, and is that edit as C.Morris with shown in 2406 pages of (1992) Science and Technology academic publishing dictionaries (Academic Press Dictionary of Science and Technology) San Diego Academic Press Inc. publication.
The metal that these families comprise has: Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt.Palladium is the preferable alloy of polymerizing catalyst of the present invention.
Generally use palladium salt as the palladium cationic source.
Suitable palladium salt is inorganic salt, as palladous sulfate, Palladous nitrate and phosphoric acid palladium.
Other suitable palladium salt is sulfonate, as methylsulfonic acid, trifluoromethane-sulfonic acid and right-toluenesulphonic acids and carboxylate salt, as acetic acid and propionic acid, halogenated acetic acid, for example three fluoro-and Tricholroacetic Acid, oxalic acid and citric acid.
Also can be as the cationic source of palladium of using by element form or with the metal manufacturing of zero-valent state, for example with complex form such as palladium-dibenzyl acetone or palladium-four-triphenylphosphine, these palladium sources generally are used in protonic acid mixes, and generates the palladium positively charged ion on the spot.
The palladium salt of carboxylic acid is preferred palladium cationic source, especially palladium.
Suitable palladium organometallic complex also can use, for example, and cyclooctadiene-chloro methyl palladium.
Catalyzer of the present invention can obtain by the sour deutero-negative ion source chemical combination that makes above-mentioned ligand and the above-mentioned same pKa of cationic source＜4 in solvent.These acid as negative ion source comprise H 2AsC 5, HF, HJO 3, H 3PO 3, H 3PO 4, H 3PO 7, HNO 3, H 2SeO 3, H 2TeO 3, H 2SO 4, CH 2CLCOOH, CHCl 2COOH, CCl 3COOH, CH 2BrCOOH, CH 2.COHCH 2(COOH) 3, COOH.CH:CH.COOH (trans), CH 2OH.COOH, COOH.CH:CH.COOH (cis), COOH.CHOH.CH 2.COOH, COOH.CH 2.COOH, CH 3.CHOH.COOH, H.COOH, COOH.COOH, COOH.CHOH.CHOH.COOH, CH 6H 5.CO.NH.CH 2.COOH, C 6H 4. (COOH) 2, C 6H 2(OH). (NO 2) 3, C 6H 4.OH.COOH, C 6H 4.NH 2.SO 3H, C 5H 4N 4O 3,
Figure A9880369900061
Tosic acid and CF 3SO 3H, both are preferred for the backs.These sour salt also can use in addition.
An example as catalyzer can prepare by the reaction between cyclooctadiene palladium chloro methyl and the silver triflate.
Method for preparing catalyst The suitable solvent of the present invention is hydrocarbon, alcohol, ether and ketone or their mixture.The example of The suitable solvent is toluene, pentane, CH 2Cl 2, ChCl 3Dme of, diox, water, 2-Ethylhexyl Alcohol, ethylene glycol, glycerine, ethylene glycol (diglyme) and diethyl ether.Preferred solvent is toluene, methyl alcohol or CH 2Cl 2
R in the bidentate ligand part of catalyzer of the present invention 1And R 2Can be mutually identical or different.They are preferably identical, and the both is the O-p-methoxy-phenyl.R 1And R 2It is favourable forming the ring octyl group together.
R in bidentate ligand 8Can be H or any organic group with 1-24 carbon atom.R 8Selection make the part (R 8-N=) to become the diisopropyl benzene amine groups be favourable.
The invention still further relates to the method that makes polymerization of ethylenically unsaturated hydrocarbons with above-mentioned catalyzer.In this manual, unless otherwise indicated, " polymerization " speech comprises " oligomeric " and " dimerization ".
The alefinically unsaturated compounds that uses as raw material in polymerization process of the present invention comprises unsaturated hydrocarbons and unsaturated compound, also comprises at least one other atom in its molecule, as oxygen or nitrogen-atoms except hydrogen and carbon atom.
Alkene, especially monoolefine is preferred raw material, for example, ethene, propylene, butylene, amylene, hexene, heptene, octene, Dicyclopentadiene (DCPD), 4-methylpentene, 4-pentenoic acid or its ester, norbornylene, may contain heteroatomic functionalized alkene and their mixture.They can be with other unsaturated hydrocarbons, for example cycloolefin such as cyclopentenes and tetrahydrobenzene, diolefine such as divinyl, 1,4-pentadiene and 1, the 5-hexadiene, the alkene that is replaced by aromatic group such as vinylbenzene, allyl benzene, p-methylstyrene and alpha-methyl styrene and acetylenically unsaturated compound such as acetylene, phenylacetylene and pseudoallyl acetylene use together.
The present invention is a light alkene for preparation one of monomer, and particularly to contain the multipolymer of functional group such as hydroxyl, cyano group, acid anhydride or ester group be particularly important for ethene and propylene and at least a other monomer.
Alkyl ester such as methyl acrylate, methyl methacrylate and ethyl propenoate that the example of this class suitable monomer is 3-butene-1-alcohol, 5-hexen-1-ol, 10-undecene-1-alcohol, acrylic or methacrylic is sour, vinyl acetate such as vinyl acetate and propionate and acid anhydride such as 5-norbornylene-2, the acid anhydride of 3-dicarboxylic acid.
CO as suitable comonomer can use.
If desired, polymerization process of the present invention can carry out in the presence of The suitable solvent.All kinds of SOLVENTS such as hydrocarbon, alcohol, ether, ester and ketone can use, and comprise excessive a kind of monomer, and condition is that this kind monomer is a liquid phase under the reaction conditions of this method.
Find that unexpectedly the polymerization product that uses different reaction solvents to obtain has different molecular weight.In general, the use non-polar solvent obtains the polymkeric substance of quite high molecular weight, and the existence of polar solvent will obtain oligopolymer, promptly contain the reaction product of 2-20 monomeric unit.For example basically by polar solvent such as water or two-or trivalent alcohol for example in the solvent formed of ethylene glycol and glycerine main product be oligopolymer.
On the contrary, if reaction solvent is made up of the dme (diglyme) or the diethyl ether of quite nonpolar compound such as ethylene glycol basically, then obtain the product of higher molecular weight.
The catalysis system that only needs catalytic amount in the method for the invention.Consumption is generally every mole and wants the polymeric alefinically unsaturated compounds to need 10 -1-10 -7The catalyzer of mole.Preferable amount is every mole and wants the polymeric alefinically unsaturated compounds to need 10 -2-10 -6Mol catalyst most preferably is every mole and wants the polymeric alefinically unsaturated compounds to need 10 -3-10 -5Mol catalyst.
Will be understood that the purposes of the product that obtains will especially depend on the molecular weight of product.
The purposes of oligomerization product is as the raw material of producing softening agent, lubricant and tensio-active agent.The product of higher molecular weight can be used as thermoplastics and is used to make film, thin plate and wrapping material etc.
Method of the present invention can be carried out under moderate reaction conditions, has both comprised that preparation mainly is that the nonpolar reaction medium of higher molecular weight products also comprises the polar reaction medium of making oligopolymer.
Temperature of reaction is generally 10-200 ℃, and 25-130 ℃ is preferred.
General reaction pressure is a superatmospheric pressure, and for example the 1-100 crust is not got rid of at this extraneous pressure.The preferred pressure scope is the 2-60 crust.
Catalysis system of the present invention can suitably prepare respectively, add want the polymeric monomer before by metallic cation source or its precursor and other above-mentioned composition are carried out chemical combination in the presence of The suitable solvent.Also can prepare on the spot and be added in the monomer that exists in the reaction medium and any other compound in the catalyzer by in reactor, introducing catalyst component.
Be the preparation catalyst system, the molar weight of above-mentioned metallic compound, ligand and acid equates basically.Generally speaking, excessive acid preferably, for example every grammeatom metal reaches 10, preferably reaches 5 normal acid.
The present invention illustrates with following non-limiting examples.
Embodiment 1
By corresponding amine and aldehyde as being shown in the synthesizing imine phosphine ligand " L " of reaction formula 1:
Reaction formula 1
The radicals R of the ligand L of different catalyzer 1, R 2And R 3Be shown in table 1:
Table 1
???L ????R 1 ????R 2 ???R 3
???a ???b ???c ???d ???e ???f ???g ???h ????Ph ????Ph ????Ph ??m-CH 3Oph ??o-CH 3Oph ??o-CH 3OPh ??o-CH 3Oph ??o-CH 3OPh ????H ????Me ????iPr ????iPr ????H ????H ????H ????iPr ???H ???H ???H ???H ???Cl ???H ???OMe ???H
Ph=phenyl Me=methyl iPr=sec.-propyl is by bidentate ligand L, Pd (OOC.CH 3) 2With weak acid promptly right-toluenesulphonic acids (p-TosOH) or CF 3SO 3H, non-coordinate negatively charged ion, generate catalyzer by anion exchange reaction.Embodiment 2
The method of synthetic ligand Lh
With 0.51 gram (2.86 mmole) 2, the right-toluenesulphonic acids of 6-diisopropyl aniline and catalytic amount joins two (2-the p-methoxy-phenyl)-phosphino-s of 1.0 gram (2.86 mmole) 2-[] phenyl aldehyde is dissolved in 50 milliliters the toluene.Under the Dean-Stark condition, this solution was refluxed 4 hours.To obtain yellow oily liquid after the solvent evaporation, this liquid is by CH 3Crystallization among the OH.Output: 1.27 gram (87%) analytical calculation: C 33H 36NO 2P:C 77.78
H?7.12
N?2.75
P 6.08 measured values: C 77.61
H?7.22
N?2.91
P?5.93
Carry out the synthetic of ligand La-Lg (comprising) with identical route.
Embodiment 3
By means of the catalyzer of discussing at embodiment 1 and table 1, at 20 crust ethene, 100 ℃ of temperature and in 50 milliliters solvent methanol, carry out oligomerization.Catalyzer comprises 0.1 mmole Pd (OOC.CH 3) 2, 0.11 mmole ligand and 0.21 mmole TosOH.Measure the ratio of product with gas chromatography.
Obtain higher alkene, as shown in table 2, C in table 2 6-C 5The summation of molar percentage almost is 100%.(％)
Table 2
Ligand in the ethylene oligomerization
Experiment Ligand Time (hour) T.O. * C 6(％) C 8(％) C 10(％) C 12(％) C 14(％) C 16(％)
1 2 3 4 5 6 7 8 La Lb Lc Ld Le Lf Lg Lh 9 9 9 5 5 5 5 5 250 250 250 150 150 500 800 1100 85 74 53 62 44 34 36 22 12 15 29 26 23 26 27 25 3 11 13 10 16 19 18 22 4 2 10 12 12 16 1 5 6 6 9 2 3 1 6
*Transformation efficiency (the ethene mole that every mol catalyst transforms) table 2 shows the proportion of products of various phosphine imide ligands.Along with nitrogen is given the sterically hindered increase of position, the molecular weight of product increases (experiment 1 with 6 with 8 compare with 3 with 2).And (in the situation of neighbour-methoxyl group homologue Lh) molecular weight increases (experiment 3,4 compare with 8) once more when introducing the more space hyte on phosphorus.
It should be noted that owing to two phenyl that replace with phosphorus-methoxyphenyl on the phosphorus active significantly increase (T.O. is by 250 to 1100) (table 2, experiment 8).In addition, catalytic activity also is subjected to the influence of imines to the electronics on the body, and particularly electronics discharges group has increased ratio.R for example 3Become methoxyl group (Le-Lg) by chlorine, make T.O. be increased to 800 by 150.
In addition, high temperature has increased the amount (table 4) of isomerization reaction (table 3) and branched product.Sterically hindered reduction in space also obtains more branched product (relatively Lc and Lh) on the ligand.
Table 3 temperature is to the influence of proportion of products
Ligand T(℃) Time (hour) ??T.O. ?C 6(％) ?C 8(％) ?C 10(％) C 12(％) ?C 14(％) C 16(％)
??Lh ??Lh ??Lh ?70 ?100 ?120 ????16 ????5 ????5 ??650 ??1100 ??1650 ??17 ??22 ??32 ??24 ??25 ??28 ???22 ???22 ???20 ??17???? ??16???? ??11??? ??12 ??9 ??6 ??8 ??6 ??3??
Table 4
C 6-C 12Straight chain
Ligand ??T(℃) Straight chain C 6(％) Straight chain C 8(％) Straight chain C 10(％) Straight chain C 12(％)
????Lc ????Lh ????Lh ??100 ??100 ??120 ???92 ???94 ???94 ????88 ????92 ????89 ?????83 ?????89 ?????77 ?????77 ?????83 ?????76
Can reach the fine tuning reaction by changing solvent and negatively charged ion.Typical consequence is summarized in the table 5.By MeOH to CH 2Cl 2Activity reduces slightly.Yet, work as CF 3SO 3 -As solvent C H 2Cl 2In gegenion the time (embodiment 3) transformation efficiency numeral significantly increase.
Table 5
Embodiment Ligand Solvent Negative ion source Time (hour) TO C 6(％) C 8(％) C 10(％) C 12(％) C 14(％) C 16(％)
1 2 3 4 5 6 7 8 Lc Lc Lc Lh Lh Lh Lh Lh MeOH CH 2Cl 2CH 2Cl 2MeOH MeOH MeOH CH 2Cl 2Diglyme p-TosOH p-TosOH CF 3SO 3H CF 3CO 2H p-TosOH CF 3SO 2H p-TosOH CF 3SO 3H 9 12 9 5 5 5 5 5 250 250 1000 800 1100 1100 750 1250 53 82 72 30 22 26 57 63 29 15 22 28 25 27 42 27 13 3 5 21 22 22 0.5 8 4 13 16 14 0.5 2 1 7 9 8 1 6 3
Embodiment 4 uses and condition identical in embodiment 3, comprise ligand N-{2-[pair-(2-p-methoxy-phenyl) phosphino-] benzylidene }-2, the Pd-catalyzer of 5-(di-isopropyl) aniline transformation efficiency numeral in 1.5 hours in ethylene glycol is about 1100 moles/mole palladiums.The ratio of product is: C 6: 25%, C 8: 27%, C 10: 23%, C 12: 17%, C 14: 5%, C 16: 3%.Straight chain is C 6: 95%, C 8: 92%, C 10: 86%, the experiment with 40 ethene that cling in methyl alcohol obtains following result: C 6: 26%, C 8: 26%, C 10: 20%, C 12: 14%, C 14: 9%, C 16: 5%.
Transformation efficiency is about 1350 moles/mole palladiums.The numeral of 1-alkene also is identical: C 6: 39%, C 8: 30%, C 10: 21%.
In a word, develop a kind of new metal that is used for ethylene oligomerization and be basic catalyst system.Noticeable feature is the stability of the brilliance in solvent at high temperature, generates C under these temperature 6-C 16Oligopolymer, and the selectivity that can regulate oligopolymer by the phosphine imide ligand.

Claims (11)

1. close and can obtain a kind of catalyzer by making bidentate ligand be lower than 4 acidifying with the cationic source of the periodic table of elements 8,9 or 10 family's metals and pKa with following general formula: In the formula, X=P, As, Sb, n=0 or 1, R 1, R 2=have 1-24 carbon atom alkyl, alkoxyl group, aryloxy, cycloalkyl or replacement or unsubstituted (ring) aliphatic series, (ring) alkene or aromatic group, or R 1And R 2That constitute to replace together or unsubstituted alicyclic ring, cyclenes or aromatic group, R 3, R 4, R 7, R 8If unsubstituted (ring) aliphatic series, (ring) alkene or the aromatic group of=H, the alkyl with 1-24 carbon atom, alkoxyl group, aryloxy, cycloalkyl or replacement are n=1:R 5And/or R 6(ring)=H, alkyl, alkoxyl group, aryloxy, cycloalkyl or replacement or unsubstituted aliphatic series, (ring) alkene or aromatic group with 1-24 carbon atom, C ' and C " same R 3And R 6Can form together replacement or unsubstituted (ring) aliphatic series, (ring) alkene or aromatic group, R in this case 4And R 5Do not exist, or C ' and C " can form the alkene key, in this case R 4And R 5Do not exist.
2. the catalyzer of claim 1 is characterized in that, X=P.
3. claim 1 or 2 catalyzer is characterized in that the metal of the periodic table of elements 8,9 or 10 families is Pd.
4. the arbitrary catalyzer of claim 1-3 is characterized in that it is right-toluenesulphonic acids or CF that pKa is lower than 4 acid 3SO 3H.
5. arbitrary catalyzer among the claim 1-4 is characterized in that bidentate ligand R 1And R 2It is neighbour-p-methoxy-phenyl group.
6. arbitrary catalyzer among the claim 1-5 is characterized in that (=N-R in the bidentate ligand 8) be the diisopropyl benzene amine groups.
7. arbitrary catalyzer among the claim 1-6 is characterized in that solvent is toluene, methyl alcohol or CH 2Cl 2
8. the method for the polymerization of ethylenically unsaturated organic compounds or copolymerization, it is characterized in that arbitrary catalyzer is as catalyzer among the claim 1-7.
9. the method for claim 8 is characterized in that alefinically unsaturated compounds is the mixture of the mixture of alpha-olefin or two or more alpha-olefins or at least a alpha-olefin and at least a functionalized alkene.
10. claim 8 or 9 method is characterized in that the proportional range between alefinically unsaturated compounds molar weight and the catalyzer molar weight is 10: 1-10 7: 1.
11. arbitrary method among the claim 8-10 is characterized in that polyreaction is to carry out under temperature range 10-200 ℃ and pressure 1-100 crust in solvent.
CN98803699A 1997-03-25 1998-03-24 Prepn. of catalyst Pending CN1251056A (en)

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EP97200901 1997-03-25
EP97200901.3 1997-03-25
EP97201295.9 1997-04-29
EP97201295 1997-04-29

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US6200925B1 (en) 1997-03-13 2001-03-13 Eastman Chemical Company Catalyst compositions for the polymerization of olefins
US6245871B1 (en) 1997-04-18 2001-06-12 Eastman Chemical Company Group 8-10 transition metal olefin polymerization catalysts
US6620896B1 (en) 1999-02-23 2003-09-16 Eastman Chemical Company Mixed olefin polymerization catalysts, processes employing such catalysts, and polymers obtained therefrom
US6355735B1 (en) 1999-08-17 2002-03-12 3M Innovative Properties Company Semi-interpenetrating polymer network from epoxy monomer and olefin
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WO1998042440A1 (en) 1998-10-01
CA2285080A1 (en) 1998-10-01

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