CN104144936B - P N P part - Google Patents

Abstract

New P N P part is used for ethylene oligomerization.Described part is characterized by that at least one is bonded to the aromatic fluorocarbon group alkoxide groups of P atom, itself and i) chromium source；And ii) combination of activator such as MAO, the part of the present invention may be used for the preparation oligomerization product containing high-purity alpha alkene mixture.In a preferred embodiment, the part of the present invention can selective oligomerization, wherein most product liquid is the mixture of hexene and octene.The amount of the by-product polymer produced in preferred oligomerization is the most relatively low.

Description

P-N-P part

Technical field

The invention provides the P-N-P part of new class.Described part is in ethylene oligomerization reaction.Described ligand features exists In the aromatic fluorocarbon group alkoxide (fluorocarbyl alkoxide) with at least one and P atomic linkage.

Background technology

Alhpa olefin by the presence of simple aluminum alkyl catalyst (in so-called " chain growth " method) or, organic In the presence of metalNicatalyst, (in so-called Shell higher alkene method or " SHOP " method), ethylene oligomerization comes commercially prepared.This Two kinds of methods the most all produce thick oligomerization product, its have wide distribution there is even-numbered carbon atom alhpa olefin (that is: butylene- 1, hexene-1, octene-1 etc.).Then typically in series distillation column, the various alhpa olefins in thick oligomerization product are separated.Butene-1 It is typically the most shotten, because it also produces as by-product in various cracking and refinery practice in a large number in these alkene. Hexene-1 and octene-1 usually need the price that comparison is high, because these alkene are as linear low density polyethylene (LLDPE) comonomer demand is higher.

Technology according to the demand of hexene-1 is combined into hexene-1 for ethylene selectivity trimerization has been put into business recently Application.Patent documentation disclose can be used for the method comprise chromium source and the catalyst of pyrrolidine (pyrrolide) part, ginseng See, such as United States Patent (USP) (" USP ") 5,198,563 (Reagen etc. transfer Phillips Petroleum).

Another kind of high activity trimerization catalyst by Wass etc. be disclosed in WO 02/04119 (present United States Patent (USP) 7, 143,633 and 6,800,702).The disclosed catalyst such as Wass is formed by chromium source and chelating diphosphine ligand and Carter etc. enters One step has been described in detail (Chem. Comm. 2002, the 858-9 page).As described in Chem. Comm. article, These catalyst preferably comprise diphosphine ligand, and two of which phosphine atom and two are each bonded by the phenyl of o-methoxy substitution. Hexene-1 is prepared by these high activity of catalyst and highly selective.

Similar diphosphine/tetraphenyl part is disclosed in WO04/056478 and WO 04/056479 by Blann etc. and (is now US 2006/0229480 and US 2006/0173226).But, compared with the part of Wass etc., the disclosed diphosphine such as Blann/ Tetraphenyl part is typically free of polar substituent in ortho position." tetraphenyl " diphosphine ligand required in ' 480 applications is all (any kind of) ortho-substituent and ' " tetraphenyl " diphosphine ligand feature required in 226 must not all be had on four phenyl It is, in meta or para position, there is polar substituent.Both approaches all shows that (compared with the part of Wass etc.) reduces preparation The amount of hexene and add the amount of octene.But, hexene fraction usually contains a large amount of interior hexene (internal hexenes), This is undesirable.Therefore, the chromium-based catalysts of the part containing Blann etc. typically produces more octene (if to octene If demand height, this is favourable) but these parts have the drawback that the hexene stream of generation is by a considerable amount of internal olefin institute Pollute.

Internal olefin is undesirable pollutant in linear low density polyethylene (LLDPE) process units, because internal olefin It is not easy to introduce in LLDPE with most of transition-metal catalysts.Thus, if in described alhpa olefin LLDPE to be used in technique, From alhpa olefin, preferably remove/separate internal olefin.As the skilled person will appreciate, due to these hexene isomers Close boiling point, thus relatively difficult by separating hexene-1 from interior hexene in distillation.

Optionally, therefore produce the height in co-product (co-product) hexene with very low loadings of internal olefin The method of the octene-1 of content represents preferably supplements prior art.Additionally, the present invention can be with the polymerization of relatively small amount Thing by-product selective oligomerization reacts.

Summary of the invention

In a preferred embodiment, the invention provides the P-N-P-part of new class, be defined by the formula:

Wherein Ar₁Selected from the miscellaneous alkyl of aromatic hydrocarbyl and aromatics；Ar^FIt is aromatics fluorohydrocarbon epoxide (fluorocarbyl Oxide)；Ar₃And Ar₄Independently selected from aromatic hydrocarbyl；The miscellaneous alkyl of aromatics and aromatics fluorohydrocarbon epoxide；And R₁Selected from alkyl and miscellaneous hydrocarbon Base.

These molecules are particularly suitable for being used as part in the method make ethylene oligomerization.Possible optional purposes includes for hydrogen Change and/or the part of hydroformylation reaction.

One preferred example of the part according to the present invention is defined by the formula:

In another embodiment, the invention provides a kind of method for ethylene oligomerization, wherein said method bag Include and make ethylene and comprise i) chromium source；Ii) part of following formula definition and iii) catalyst system of activator contacts:

Wherein Ar₁、Ar^F、R₁、Ar₃And Ar₄As defined above.

[preferred embodiment of the present invention]

As used in this article term " substituted ", " alkyl ", " aromatics " and " miscellaneous alkyl " refer to the meaning of they routines Think.It is briefly described below.

Term " substituted " (as in " substituted the phenyl ") meaning is the hydrogen of at least one and the carbon atom bonding of phenyl Atom is replaced base or substituted radical is replaced.Such as, the phenyl that wherein hydrogen is replaced by fluorine atom (especially at ortho position) provides " fluorine is substituted " group, it is preferred in the part of the present invention.

Term " alkyl " refers to contain only the group of carbon and hydrogen.Preferably contain 1-50 carbon atom, especially 1- 24 carbon atoms, are especially those of 1-16 carbon atom.

Term " miscellaneous alkyl " refers to the group containing at least one atom in addition to carbon and hydrogen.Preferably hetero atom Including nitrogen, oxygen, sulfur, phosphorus, boron, chlorine, fluorine and silicon.Term fluorohydrocarbon base (fluorocarbyl) refers to contain only the base of fluorine and carbon Group.Term fluorohydrocarbon epoxide (fluorocarbyl oxide) refers to the group containing fluorine, carbon and oxygen.Preferably fluorohydrocarbon epoxide contains There are 6-20 carbon atom, especially 6-12 carbon atom and an oxygen atom.

Term " aromatics " refers to be included in the cyclic rings group of the unsaturated part of delocalization on annular atoms.

The part of the present invention contains at least one aromatics fluorohydrocarbon epoxide with P atomic linkage and with P atomic linkage at least One alkyl or miscellaneous alkyl.

Particularly preferred fluorohydrocarbon oxygen groups is

Particularly preferred alkyl is phenyl and substituted phenyl (the substituted phenyl of the most o-fluorine).

Part A: catalyst system

The catalyst system used in the method for the present invention must contain three kinds of necessary components, it may be assumed that

(i) chromium source；

(ii) the P-N-P part limited；With

(iii) activator.

These components respective preferred form is discussed below.

Chromium source (" component (i) ")

All chromium sources that the oligomerization process allowing the present invention is carried out can be used.Conventional example includes Chlorizate chromium；Acetyl Acetone chromium, chromium carbonyl and carboxylic acid chromium.Preferably chromium source includes chromium trichloride；2 ethyl hexanoic acid chromium (III)；Chromium acetylacetonate And carboxyl chromic compound (chromium carboxyl complexes) is such as six carboxyl chromium (III).

The part (" component (ii) ") used in oligomerization process

In general, the part used in the oligomerization process of the present invention is defined by the formula:

Wherein Ar₁Selected from the miscellaneous alkyl of aromatic hydrocarbyl and aromatics；Ar^FIt it is aromatics fluorohydrocarbon oxide-base；Ar₃And Ar₄Select independently From aromatic hydrocarbyl；The miscellaneous alkyl of aromatics and aromatics fluorohydrocarbon epoxide；And R₁Selected from alkyl and miscellaneous alkyl.For the sake of clarity, it is however emphasized that Be Ar₁、Ar^F、Ar₃And Ar₄It is respectively aromatic group.

Preferably each aromatic group contains only a ring structure.

It is especially preferred for using unsubstituted phenyl and o-substituted phenyl.Other preferred substituent group is selected from: C_1-8 Alkyl and C_1-4 Alkoxyl.

Ar^FGroup is preferably C₆F₅O (for the sake of clarity, if hydrogen atom is bonded with oxygen, then this preferred Ar^FGroup Pentafluorophenol will be become).

New highly preferred part contains phenyl, o-substituted phenyl and C₆F₅O, as in the embodiment shown.

Group that the nitrogen-atoms of the P-N-P part of the present invention contains the price meeting nitrogen (upper facial in refer to R₁).Excellent Selecting this group is C_1-20Alkyl, wherein isopropyl is particularly preferred.The miscellaneous alkyl with 3-50 atom can also be used.

Activator (" component (iii) ")

Described activator (component (iii)) can be to generate the active catalytic for ethylene oligomerization with component (i) and (ii) Any compound of agent.It is also possible to use the mixture of these activators.Suitably compound includes machine aluminium compound, organic boron Compound and mineral acid and salt, such as Tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate etc..Suitably organo-aluminium chemical combination Thing includes formula AlR₃Compound, wherein R is each independently C₁–C₁₂Alkyl, oxygen or halogen ion, and compound such as LiAlH₄Deng. Example include trimethyl aluminium (TMA), triethyl aluminum (TEA), triisobutyl aluminium (TIBA), tri-n-octylaluminium, methylaluminium dichloride, Ethylaluminium dichloride, chlorodimethylalumiu, diethylaluminum chloride, ethylaluminum sesquichloride, sesquialter methyl chloride aluminum and aikyiaiurnirsoxan beta. Aikyiaiurnirsoxan beta is in the art as typical oligomeric compound it is well known that it can add to alkyl by water is controlled Prepare on aluminium compound such as trimethyl aluminium.This compounds can be straight chain, ring-type, caged or its mixture. Generally it is believed that commercial available aikyiaiurnirsoxan beta is the mixture of straight chain and cyclic compound.Cyclic aluminoxane can be by formula [R⁶AlO] _S Represent and linear alumoxanes I is by formula R⁷(R⁸AlO) _S Representing, wherein s is the number of about 2-50, and wherein R⁶、R⁷And R⁸ Represent alkyl, preferably C₁-C₆Alkyl, such as methyl, ethyl or butyl.Alkylaluminoxane especially MAO (MAO) is excellent Choosing.(in document, MAO is also referred to as MAO and MAO).

It would be recognized by those skilled in the art that commercial available alkylaluminoxane can contain a certain proportion of trialkylaluminium. Such as, commodity MAO usually contains about 10 weight % trimethyl aluminiums (TMA), and commodity " modified MAO " (or " MMAO ") are containing TMA With TIBA.The amount of alkylaluminoxane is generally drawn at this on the mole foundation of aluminum (with including this trialkylaluminium that " dissociates ") State.Alkylaluminoxane and/or alkyl aluminum before the addition of the catalyst or can be added simultaneously to reaction medium adding catalyst In (that is: ethylene and/or diluent and/or solvent).Such technology is known to oligomeric field and to be disclosed in more detail in such as U.S.P. 5,491,272；5,750,817；5,856,257；In 5,910,619 and 5,919,996.

Suitably the example of organoboron compound is boroxin (boroxine), NaBH₄, trimethyl borine, boron triethyl, Four (phenyl) borate base ammonium, four (phenyl) borate, triphenyl borine, four (pentafluorophenyl group) boric acid diformazan Base phenyl ammonium, four [(double-3,5-trifluoromethyl) phenyl] sodium borate, four (pentafluorophenyl group) borate and three (five fluorine Phenyl) boron.

Activator compound (iii) can also be or contain the compound serving as reducing agent or oxidant, such as sodium or zinc gold Belong to, or oxygen etc..

In the preparation of the catalyst system used in the present invention, the amount of activating compounds to be used is surveyed by simple Examination can be easily determined by, and such as, can be used for making a small amount of ethylene oligomerization by preparation and thus measures the activity of catalyst of preparation Small sample.The amount being generally found use be enough to provide aluminum (or boron)/mol chromium of 0.5-1500 mol.MAO is currently preferred Activator.Preferably Al/Cr mol ratio is 1/1-1500/1.The part of the present invention has good response for the MAO of high-load, As in the embodiment shown.

Part B: process conditions

Chromium (component (i)) and part (component (ii)) can to produce the arbitrary mol ratio of oligomer, preferably 100: 1-1:100, and most preferably 10:1-1:10, particularly 3:1-1:3 exists.The generally amount of (i) and (ii) is roughly equal, it may be assumed that ratio Rate is 1.5:1-1:1.5.

In the present invention use catalyst system component (i)-(iii) can in any suitable solvent exist or Do not add simultaneously all together in the case of there is not ethylene or be sequentially added in any order, in order to obtaining active catalyst.Such as, Component (i), (ii) and (iii) and ethylene can together with contact simultaneously, or component (i), (ii) and (iii) can be simultaneously introduced Or be sequentially added in any order and then with contact ethylene, or component (i) and (ii) can together with add to be formed separable Metal ligand complex and be subsequently added into component (iii) and neutralize and contact ethylene, or component (i), (ii) and (iii) are permissible Add together to be formed separable metal ligand complex and then with contact ethylene.For contacting catalyst or caltalyst The suitable solvent of the component of system includes but not limited to: hydrocarbon solvent such as heptane, hexamethylene, toluene, 1-hexene etc., and polar solvent Such as diethyl ether, oxolane, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone etc..Described method can also be such as " body Method " carry out (that is: the method carried out in the presence of reactant) (substantially without extra solvent or diluent).

The catalytic component (i), (ii) and (iii) that use in the present invention can be unsupported or be supported on carrier material Such as silicon dioxide, aluminium oxide, MgCl₂Or on zirconium oxide, or it is supported on polymer such as polyethylene, polypropylene, polystyrene Or on poly-(aminostyryl).If necessary, described catalyst can be formed in situ in the presence of carrier material, or described Carrier material can simultaneously or sequentially with one or more catalytic component pre-preg or with one or more catalytic components Premixing.The amount of the carrier material used can be extensively varied, such as, by 100, deposit in 000 to 1g/g transistion metal compound Metal.In some cases, described carrier material can also serve as activator compound (iii) or as activator chemical combination The component of thing (iii).Example includes the carrier containing aikyiaiurnirsoxan beta structure division.

Oligomerization can be carried out under the conditions of solution phase, slurry phase, gas phase or body phase.Suitably temperature be 10 DEG C to+ 300 DEG C, preferably 10 DEG C to 100 DEG C, especially 30 DEG C to 60 DEG C.Suitably pressure is that air is depressed into 800 atmospheric pressure (gauge pressure), It is preferably 5 air and is depressed into 150 atmospheric pressure, especially 10-50 atmospheric pressure.

Not considering the process conditions used, described oligomerization is typically substantially eliminating oxygen gas and water and other plays and urges Carry out under conditions of the material of agent poisonous substance effect.And, oligomerization can control selectivity, improving activity and reduce oligomeric Carry out in the presence of the additive of the amount of the polymer formed in method.Optionally suitably additive include but not limited to hydrogen or Halide source.It is especially preferred for using hydrogen, since it is observed that hydrogen slow down the formation of by-product polymer.

Many is existed for oligomerization reactor select, including intermittently operated, semi-batch operation and continuous operation.The present invention's Reaction can be carried out under the process condition range that will be apparent to those skilled in the art: dilute at presence or absence unreactive hydrocarbons Release in the case of agent such as toluene or heptane as uniform liquid phase reactor；React as biphase liquid liquid；As slurry process, wherein Catalyst is for showing little or no deliquescent form；As substance law, the purest reactant and/or product Alkene is used as main medium；As vapor phase method, a part of reactant of at least a part of which or Product olefins are transported to via gaseous state Or its load form from catalyst.Evaporated cooling by one or more monomers or inert volatile liquid to can be used for from instead A kind of method of heat is removed in should.Described reaction can be in the Gas-phase reactor of known type, such as circulation fluidized bed, vertical or horizontal Agitated bed, fixed bed or fluidized-bed reactor, Liquid-phase reactor such as piston flow, continuous stirred tank or loop reactor or they Combination in carry out.Separate with catalyst and/or the broad range of method of purification is this area for carrying out product, reactant Known to the skilled person and can use: distill, filter, the sedimentation of liquid-liquid separation, slurry, extraction etc..In these methods one Kind or multiple can be carried out by oligomerization individually or its can the most several with described react merge；Its non-limit The example of property processed is the method using catalysis (or reactive) to distill.Favourable can also is that it includes more than one reaction Device, catalyst between reactor or after last reactor kill system (catalyst kill system) or collection The method becoming reactor/separator/purifier.Although the most all of catalytic component, reactant, inert substance and Product can disposably use (on a once-through basis), but usually make these materials economical advantages In one or more recirculatioies；For catalyst system, so may require the one in described catalytic component of recombinating Or it is multiple to reach active catalyst system.Oligomerization product is possibly also as solvent or diluent within the scope of the present invention.Also may be used Use inert diluent or the mixture of solvent.Preferably diluent or solvent is aliphatic series or aromatic hydrocarbon and halogenated hydrocarbon such as isobutyl Alkane, pentane, toluene, dimethylbenzene, ethylbenzene, cumene, mesitylene, heptane, hexamethylene, hexahydrotoluene, 1-hexene, 1-are pungent Alkene, chlorobenzene, dichloro-benzenes etc. and mixture such as Isopar^TM。

Change from the technology of the products distribution of oligomerization include controlling process conditions (such as component (i)-(iii's) Concentration, reaction temperature, pressure, the time of staying) and properly select the design of technique and this is that those skilled in the art institute is ripe Know.

Can be substantially pure maybe can to contain other olefin impurity and/or ethane for oligomeric ethylene raw.This One embodiment of inventive method comprise from other chemical process containing ethylene waste streams or from the thick second of cracker Alkene/ethane mixtures oligomeric.

In the presence of two or more oligomerisation catalysts, the most also carry out oligomerization.An enforcement In scheme, all of oligomerisation catalyst can be prepared by the modification of the novel P-N-P part of the present invention.Real at another Executing in scheme, the oligomerisation catalyst of multi-form can be applied in combination with being prepared standby catalyst by the P-N-P of the present invention.

In greatly preferred embodiment of the present invention, the present invention oligomerization product prepared is joined from being used for It is separated in the product stream of another kind of alhpa olefin production method of different alhpa olefins.As previously discussed, " conventional alpha olefin device " (wherein said term includes i) uses aluminum alkyl catalyst to produce those methods of alhpa olefin, ii by chain growth method) aforementioned " SHOP " method and iii) use so-called Lurgi method to be prepared alkene by forming gas) there is a series of distillation column with by described " thick α product " (that is: the mixture of alhpa olefin) be separated into alhpa olefin (such as butene-1, hexene-1 and octene-1).Prepared in accordance with the present invention Hexene-the octene product of mixing is highly suitable for the thick alhpa olefin product from existing alhpa olefin device (or from described dress " fraction " of the product put or fraction) addition/mixing, because the hexene-octene product of described mixing prepared in accordance with the present invention Can have low-down internal olefin content.So, the hexene-octene product of the present invention can be in the existing steaming of alhpa olefin device Evaporate in tower and be easily separated (without causing big burden in the operation of these distillation column, if the hexene of the present invention-octene produces Logistics contains a large amount of internal olefin, then such situation will occur on the contrary).As used herein, term " product liquid " meaning is Referring to the oligomer prepared by the method for the present invention, it has 20 carbon atoms of 4-(about).

From the product liquid of oligomerization process of the present invention preferably by 25-70 weight %, especially 50-70 weight % pungent Alkene-1 forms, and wherein weight % represents based on the gross weight of product liquid.

The preferred oligomerization process of the present invention be characterised by producing low-down internal olefin content (that is: the hexene of low content- 2, hexene-3, octene-2, octene-3 etc.), the hexene of the most preferably smaller than 10 weight % (especially less than 5 weight %) content and pungent Alkene is internal olefin.The internal olefin (such as hexene-2 or octene-2) of low content is the most desired, because:

A) internal olefin is generally of the boiling point closely of the boiling point with corresponding alhpa olefin (and therefore, it is difficult to by distillation Separate alkene)；With

B) internal olefin uses conventional catalyst (compared with alhpa olefin) to be difficult to and ethylene copolymer therefore in big portion Divide and copolyreaction is all not intended to use.

Although being unwilling to be bound by any theory, but it is believed that the o-fluoro substituents of preferred part is along with low Internal olefin content.Especially, in document, report produces similar oligomeric of other of the mixed octene/hexene product rich in octene Part (that is: the P-N-P part without o-fluoro substituents) generally produces the interior hexene of high-load.

It is usually preferable that make oligomerisation catalyst inactivate at the end of polyreaction.Generally, many polar compounds (as Water, alcohol and carboxylic acid) catalysqt deactivation will be made.Using alcohol and/or carboxylic acid is preferred and it is contemplated that combination.

Further preferably remove from liquid product stream catalyst (and by-product polymer, if any).For with other Known catalysqt deactivation/product recovery technology that oligomerisation catalyst is used together the most also should be suitable for the catalysis with the present invention Agent is used together (see for example U.S. 5,689,208 and 5,340,785).

One embodiment of the invention includes that component (i), (ii) and (iii) gather with the alkene of one or more types Close catalyst system (iv) and be used together so that ethylene oligomerization subsequently a part of oligomerization product being incorporated in high polymer.

Component (iv) can be one or more suitable polymerisation catalyst systems, and the example includes but not limited to routine Ziegler-Natta catalyst, metallocene catalyst, monocyclopentadienyl or " restriction geometry " catalyst, phosphinimine (phosphinimine) catalyst, the supported chromium oxide catalyst of thermal activation (such as " Phillips "-type catalyst), rear mistake Cross metal polymerization catalyst (such as diimine, diphosphine and salicylic alidehyde imine (salicylaldimine) nickel/palladium catalyst, ferrum and Cobalt pyridine radicals diimine catalysts etc.) and other so-called " single site catalysts " (SSC).

Ziegler-Natta catalyst is generally made up of two kinds of key components.A kind of component is alkyl I-III race's metal or I- III metal halide, is most commonly that Al (Et)₃Or Al (iBu)₃Or Al (Et)₂Cl and include Grignard reagent (Grignard reagents), n-BuLi or dialkyl zinc compounds.The second component is IV-VIII group 4 transition metal Salt, is most commonly that the halogenide such as TiCl of titanium or vanadium₄、TiCl₃、VCl₄Or VOCl₃.When generally mixing time institute in hydrocarbon solvent State catalytic component and can form uniform or uneven product.Such catalyst can pass through this area if necessary Mode known to the skilled person impregnated on carrier, and so for any main method becoming known for polyolefin coordination catalysis Such as solution, slurry and vapor phase method.In addition to two kinds of key components described above, it is also possible to add other chemical combination a certain amount of Thing (usually electron donor) is to improve polymerization behavior or the activity of catalyst further.

Metallocene catalyst, generally by transient metal complex, is most often and joins based on cyclopentadienyl group (Cp) type group The IV race metal composition of position.The broad range of structure of this type catalyst is known, including with substituted, connection And/or those of the Cp group etc. condensed with other member ring systems containing heteroatomic Cp group.It is frequently used other activator such as Borine or aikyiaiurnirsoxan beta, and if necessary, described catalyst can be load.

Monocyclopentadienyl or " restriction geometry " catalyst generally by transient metal complex, be most often based on One cyclopentadienyl group (Cp) type group being usually connected with other donor groups is connected the IV race metal group of (ligated) Become.The broad range of structure of this type catalyst is known, including with substituted, connect and/or containing heteroatomic Cp group that Cp group condenses with other member ring systems and a range of be connected and disconnected extra donor groups such as acyl Those of amine, amine and alkoxide.Be frequently used other activator such as borine or aikyiaiurnirsoxan beta, and if necessary, described in urge Agent can be load.

Typical thermal activation chromium oxide (Phillips) type catalyst uses the combination of carrier material, and described carrier material is Through being firstly added at least a part of which part chromium by being heated as the material containing chromium of sexavalence state in the presence of molecular oxygen.Carrier Generally being made up of the silicon dioxide of about 80-100 weight %, remainder (if any) is selected from refractory metal oxide such as Aluminum, boron oxide (boria), magnesium oxide, thorium oxide, zirconium oxide, titanium oxide or two or more these refractory metal oxides Mixture.Carrier can also comprise aluminium oxide, aluminum phosphate, boron phosphate and mutual mixture thereof or the mixing with silicon dioxide Thing.Chromium compound joins on carrier generally as chromium (III) compound such as acetate or acetylacetonate to avoid chromium (VI) toxicity.Then former (raw) catalyst is calcined several seconds to some hours in atmosphere at a temperature of 250-1000 DEG C Time.At least part of chromium is so made to be converted into sexavalence state.Cr (VI) is reduced to its activated form the most in the polymerization Occur, but can carry out at about 350 DEG C with CO at the end of burnout cycle.Such as fluorine, aluminum and/or titanium can for other compound To join in former Phillips catalyst so that it is modified.

Late transition metal (Late transition metal) and single site catalysts cover broad range of based on across The catalyst structure of the metal of the most whole transition system.

Component (iv) can also comprise one or more polymerization catalysts or catalyst system and one or more additionally Oligomerisation catalyst or catalyst system.Suitably oligomerisation catalyst includes but not limited to make dimerizing olefins (such as, nickel phosphine dimerization Catalyst) or trimerization or make olefin oligomerization to the most broader 1-alkene be distributed (such as ferrum and cobalt pyridine diimine is oligomeric urges Agent) those.

Component (iv) can independently be load or unsupported.Such as fruit component (i) and (ii) and optional (iii) quilt Load, then (iv) the most sequentially or simultaneously can load to maybe can load on identical carrier load respectively altogether On body.For some combines, component (i) (iii) can be part or all of component (iv).Such as, such as fruit component (iv) it is that then it can be (i), chromium source and if fruit component (iv) is containing alumoxane activator for the chromium oxide catalyst of thermal activation Then it can also be optional activator (iii).

Component (i), (ii), (iii) and (iv) can be the substantially any mol ratio producing polymer product.Required Precision ratio depend on the relative reactivity of component and product or the required performance of catalyst system.

Method of " connecting " can be by being first to carry out oligomerization, then make oligomerization product be entered by polyreaction OK.In the case of " series connection " method, various purification, analysis and rate-determining steps for oligomerization product can be optionally at trimerizations Close and introduce between the stage of reaction subsequently.Recirculation between the reactor of arranged in series is also possible.Such method Example is that ethylene uses the catalyst the most described oligomeric oligomerization product comprising component (i)-(iii) and ethylene in single reactor Copolymerization in single coupled reaction device, obtains branched polyethylene.Another example be from polyethylene process containing ethylene Waste streams oligomeric, then described oligomerization product is backed into as comonomer polyethylene process is used for prepare branched poly- Ethylene.

" in situ " example of method is to prepare the branched polyethylene being catalyzed by component (i)-(iv), described component (i)-(iv) With random order add make the active catalytic species derived from component (i)-(iii) some point (at some point) with Component (iv) is present in reactor together.

" connect " and " in situ " method can use current polymerization technique to be used for including the operation stage of component (iv).Institute Include that multiple reactor method it is believed that with the presence of the polymerization of major olefinic and can be used in the method.A kind of change is to urge oligomeric Agent bed introduce gaseous polymerization recirculation circuit in, this can as in mainstreaming recirculation circuit and or deaerating back Receive and the effluent in recirculation system or recirculation flow.

When there is component (iv), polymerizing condition can e.g. solution phase, slurry phase, gas phase or body phase, Qi Zhongwen Degree is-100 DEG C to+300 DEG C and under atmospheric pressure and higher pressure, particularly 1.5-50 atmospheric pressure.Reaction condition is general By polymer performance (such as density, melt index (MI), yield) to be prepared is had appreciable impact and similarly polymer want Ask many for domination response variables.The most wherein it is important that below the sintering temperature of polymer operation method in, Reaction temperature is general and preferably will tentatively be chosen such that polymeric reaction condition is optimal.And, polymerization or copolymerization can be Carry out in the presence of the additive of the molecular weight controlling polymer or copolymer.Use hydrogen as controlling polymer or copolymer The mode of mean molecule quantity is commonly available to the polymerization of the present invention.

Slurry phase polymerisation condition or gas phase polymerisation conditions are particularly useful for preparing the polyethylene of high or low density level and poly-third Alkene.Polymerizing condition can be interval, continuous print or semi-continuous in these methods.Further, it is possible to use it is one or more Reactor, the reactor of such as 2-5 series connection.Different reaction conditions can be used, as different in different reactors Temperature or density of hydrogen.

Once polymer product emits from reactor, then by such as reducing pressure or with fresh or recirculation flow, nitrogen Gas or light hydrocarbon (such as ethylene) purge of gas, substantially remove hydrocarbon that is any adjoint and that absorb from polymer or take off Gas.The gaseous state or the liquid hydrocarbon that reclaim can be recycled in purification system or polymeric area.

In slurry phase polymerization process, polymerization diluent is compatible with polymer and catalyst, and can be that alkane is as own Alkane, heptane, iso-butane or hydrocarbon or the mixture of alkane.Polymeric area is it may be that such as autoclave or similar reaction hold Device, or continuous print liquid full loop reactor, such as, make type known in polyethylene by Phillips legal system.When becoming silted up When implementing the polymerization of the present invention under the conditions of slurry, polymerization preferably higher than at 0 DEG C, most preferably at higher than 15 DEG C at a temperature of enter OK.Under slurry conditions polymerization temperature be preferably maintained below polymer start in the presence of polymerization diluent soften or sintering At a temperature of.If described temperature allows to be raised to more than described latter temperature, then react device fouling.In these temperature specified In the range of regulation polymerization can by provide control produce polymer mean molecule quantity useful in the way of.Control the another of molecular weight Outer useful mode is to be polymerized in the presence of serving as the hydrogen of chain-transferring agent.Generally, the density of hydrogen of use is the highest, preparation The mean molecule quantity of polymer the lowest.

In mass polymerization, use liquid monomer such as propylene as polymerisation medium.

It is well-known in the art for operating the method for gaseous polymerization.Such method is usually directed to agitation (such as By stirring, vibrate or fluidize) catalyst bed or containing catalyst subject polymer (that is: have in described polymerization wish Hope the polymer with same or similar physical property of preparation) bed and be added thereto to monomer stream and (making at least partly When monomer contacts with catalyst in bed under conditions of polymerization).Described bed generally by add cooling gas (such as recirculation Gaseous monomer) and/or volatile liquid (such as volatile inert hydrocarbon, or condensed formed liquid gaseous monomer) carry out cold But.In vapor phase method preparation and in polymeric area, directly formed solid by the polymer wherein separated and do not contain or the most not Containing liquid.If as it is well known to the skilled in the art, allow any liquid to enter the polymeric area of gaseous polymerization, be then polymerized In district, the amount of liquid is less relative to the amount of the polymer existed.This is formed with wherein polymer and dissolves in a solvent " slurry phase " method that " solution phase " method and wherein polymer are formed as the suspended substance in liquid diluent is contrary.

Vapor phase method can operation under the conditions of interval, semi-batch or so-called " continuously ".Grasp the most in such a situa-tion Make so that monomer is recycled to containing in the polymeric area of the stirring of polymerization catalyst continuously, it is provided that make-up monomers is poly-to replace The monomer closed, and with the speed suitable with polymer synthesis speed given either continuously or intermittently by polymeric area extracts being polymerized of generation Thing, add in polymeric area fresh catalyst with together with the polymer that replaces and generate by polymeric area in the catalysis that extracts Agent.

Operation is that this area institute is ripe for preparing the method for polyethylene, ethylene copolymer and polyacrylic gas fluidized bed method Know.Described method can such as carry out supporting described bed and dividing in the vertical cylindrical reactor equipped with perforation distribution plate Join the fluidizing gas stream entered by described bed.Cycle through the fluidizing gas of described bed in order to remove the polymerization from described bed Heat and be that monomer is supplied in polymerization in bed.Thus fluidizing gas generally comprise generally with some noble gases (such as nitrogen or lazy Property hydrocarbon such as methane, ethane, propane, butane, pentane or hexane) and optionally with the list together with the hydrogen of molecular weight regulator Body.Make by the top of bed out heat fluidizing gas optionally by deceleration area, (described district can have wider diameter The cylindrical part of reactor) and if necessary, by cyclone separator and or filter to separate essence from gas stream Fine solid particles.Then the gas making heat enters heat exchanger to remove at least part of heat of polymerization.Catalyst preferably continuously adds Enter or join at regular intervals in described bed.When described method starts, described bed comprises and is preferably similar to target polymerization The polymer fluidized of thing.Polymer is polymerized by monomer in described bed and prepares continuously.Preferably provide continuously or The mode of polymer is given off at regular intervals fluid bed to be maintained the height of needs from described bed.Described method is led to Often under relatively low pressure, such as 10-50 atmospheric pressure and operation at temperature such as 50-135 DEG C.The temperature of described bed is maintained at Less than the sintering temperature of described fluidized polymer to avoid agglomeration problem.

In the gas fluidized bed method of olefinic polymerization, generally described above by fluidizing gas stream by polymeric area (i.e.: Fluid bed) remove the heat released by exothermic polymerization reaction.The gas reactor making the heat out of the top by described bed passes through The heat exchanger that one or more wherein gases are cooled.Cooling gas reactor together with any supplementary gas the most again It is recycled to the bottom of described bed.In the gas fluidised bed polymerisation method of the present invention, it is desirable to by making liquid in described bed Add volatile liquid to described bed under conditions of evaporation and absorb extra from described bed from there through " evaporation latent heat " effect Heat of polymerization the extra cooling (and thus improving the space-time yield of the method) of described bed is provided.When the heat from described bed Recirculation gas enter heat exchanger time, volatile liquid can condense.In one embodiment of the invention, wave The property sent out liquid is separated from recirculation gas and is individually re-introduced in described bed.Thus, such as, volatile liquid is permissible Separate and be sprayed in described bed.In another embodiment of the present invention, volatile liquid and recirculation gas one Get up be recycled to described in.Thus volatile liquid can be by condensation in fluidizing gas stream out from reactor permissible It is recycled in described bed together with recirculation gas, or can separate from recirculation gas and then return to institute State in bed.

When the catalyst in Integration Method (integrated process) the middle use present invention is to prepare high polymer, That is: when there is component (iv), it may be considered that many method choice.These select include the most oligomeric and subsequently be aggregated in list " series connection " method solely but carried out in the reactor being connected is " former with what two of which reactions steps was all carried out in identical reactor Position " method.

In the case of gas phase " in situ " polymerization, component (iv) is permissible, the most in liquid form, such as substantially Solution in upper inert liquid diluent is incorporated in polymerization zone.Component (i)-(iv) can the most simultaneously or sequentially Ground together or any part being added separately to polymer reactor.In these cases it is preferred to the liquid containing component is made For in fine droplet spray to polymeric area.Diameter of droplets is preferably in 1-1000 micrometer range.

Although usually not requirement, when polymerization or combined polymerization complete, or terminate polymerization or combined polymerization or extremely when needing When few catalyst temporarily making the present invention or catalytic component inactivation, described catalyst can be with known to those skilled in the art Mode contact with water, alcohol, acetone or other suitable catalysqt deactivation agent.

Consider that the scope of acceptable polyethylene polymer includes high density polyethylene (HDPE), medium density polyethylene, low-density Polyethylene, ultra-low density polyethylene and elastomeric material.Particularly importantly there is 0.91-0.93 gram/cc (g/cc) The polymer of density, commonly known in the art as linear low density polyethylene.This base polymer and copolymer are widely used in flexibility During blown film or curtain coating mould (cast film) manufacture.

Depend on the purposes of polymeric articles, polymer formulations is typically led to a small amount of additive, such as acid scavenger, resist Oxidant, stabilizer etc..Generally, the introducing level of these additives is of about 25-2 based on described polymer weight, and 000 part/hundred Ten thousand weight portions (ppm), generally about 50-about 1000 ppm and be more typically 400-1,000 ppm.During use, according to The polymer of powder type prepared by the present invention or copolymer are compounded into pill routinely.Polymer group prepared in accordance with the present invention The example of the purposes of compound includes for forming fiber, extruded film, band, spunbond net, molding or thermoformed article etc..Described polymerization Thing can with Blown Film or casting film-forming, or may be used for preparing various molding or extruded product such as pipe and container such as bottle or Cylinder.Concrete additive bag for every kind of application can select as known in the art.The example of the additive supplemented Including slipping agent, anti-blocking agent, antistatic additive, releasing agent, primary oxidant and secondary oxidant, clarifier, nucleator, uv stabilizer Deng.The classification of additive is known in the art and includes phosphite antioxidant, azanol (such as N, N-dialkylhydroxyamines) With amine oxide (such as dialkyl methyl amine oxide) antioxidant, bulky amine light (uv) stabilizer, phenol stabilizer, benzofuranone (benzofuranone) stabilizer etc..

As it is known in the art, filler such as silicon dioxide, glass fibre, Talcum etc., nucleator also can be added in polymer And coloring agent.

The present invention is illustrated in more detail by following non-limiting embodiment.

Embodiment

Embodiment uses following abbreviation.

Angstrom unit

NMR=nuclear magnetic resonance, NMR

Et=ethyl

Bu=butyl

IPr=isopropyl

H₂=hydrogen

Psi=pound/square inch

Rpm=rev/min

GC=gas chromatography

FID=flame ionization detector

R_x=reaction

Wt=weight

C₆' s=hexene

C₈' s=octene

MAO=MAO

THF=oxolane.

Part synthesizes

Ordinary test condition for part synthesis

Relate to all of reaction of air and/or moisture sensitive compound use the most under a nitrogen standard Schlenk and Glove box techniques is carried out.Reaction dissolvent is purified (such as by distillation) and is stored in activation 13x molecule before the use On sieve.Diethylamine, triethylamine and 2-aminopropane. purchased from Aldrich and are dried before the use on 13x molecular sieve.The bromo-2-of 1-is fluoro- Benzene, Phosphorous chloride. (PCl₃), hydrogen chloride gas and n-BuLi are purchased from Aldrich and are used as.MAO (MAO) is purchased From Akzo and be used as.Buy deuterated solvent (CD₂Cl₂, toluene-d₈、THF-d₈) and store on 13x molecular sieve.? H NMR spectroscopy is recorded on Bruker 400 MHz spectrogrph. Et₂NPCl₂, (o-F-C₆H₄)₂P-NEt₂, (o-F-C₆H₄)₂PCl and (o-F-C₆H₄)₂The preparation of PNH (i-Pr) is known in the literature (such as U.S. 7,994,363).

Preparation (o-F-C₆H₄)₂PN(i-Pr)PCl(Ph)

By (the o-F-C in 40ml pentane₆H₄)₂PNH (i-Pr) (2.001g, 7.16mmol) is cooled to-70 DEG C.Drip Add n-BuLi (4.48mL, in hexane 1.6M, 7.16mmol) and produce cream-coloured slurry, it is stirred 1 hour at-78 DEG C And the most slowly it is heated up to 10 DEG C.Then described solution is cooled back to-10 DEG C and was added drop-wise in 30 minutes at-70 DEG C In dichlorophenyl phosphine (1.279g, 7.15mmol) in 30mL pentane, produce cream-coloured slurry, it is stirred at-70 DEG C 1 little Time be then heated up to room temperature.Through volatiles removed in vacuo.Described beige solid is made in 40mL pentane again slurry.Filter Go out solid and wash twice with 10mL pentane.Described filtrate pumping is down to 20 volume % and by solution recrystallization whole night, produces white Color solid, filters it with cold pentane and washs and be dried to 300m Torr.The yield of this reaction is substantially quantitative.¹H NMR (δ, DCM-d₂):7.85-7.18 (m, 13H), 3.86 (m, 1H), 1.32 (d, 4H), 1.04 (d, 3H)。³¹P NMR (δ, DCM-d₂):134.59 (s), 21.01 (s).¹⁹F NMR (δ, DCM-d₂):-105.49 (d), -106.44 (d).Single Crystal X-ray structure determination confirms the structure of this compound.

Preparation (o-F-C₆H₄)₂PN(i-Pr)P(Ph)(OC₆F₅)

At-70 DEG C, the Pentafluorophenol (0.191g, 1.04mmol) in 5mL diethyl ether is added drop-wise at 15mL diethyl ether In (o-F-C₆H₄)₂In PN (i-Pr) PCl (Ph) (0.424g, 1.01mmol) and triethylamine (0.17mL, 1.22mmol). The white solution of described muddiness is heated up to room temperature overnight, produces white slurry, its pumping is down to 300mTorr.Product is penta Alkane extracts and passes through to filter and separate from precipitate.The volume making pentane solution is down to several (a couple of) microlitre and product Thing recrystallization is whole night.By draining mother solution separation white solid and being dried under 300mTorr vacuum.¹H NMR (δ, DCM- d₂):7.62-6.90 (m, 13H), 3.94, (m, 1H), 1.45 (d, 3H), 1.05 (d, 3H)。³¹P NMR (δ, DCM-d₂):149.78 (s), 15.00 (s)。¹⁹F NMR (δ, DCM-d₂):-105.23 (d), -106.02 (d), - 158.39 (dd), -166.87 (t), -168.31 (t).Below the oligomeric embodiment of part B use this product (to claim For ligand 1).

Part B

Ethylene oligomerization

The continuous stirred tank reactor with 1000cc volume is used to test for these.Test operation condition and range.

Test at the temperature of reactor of about 60 DEG C-80 DEG C with under 8 MPa pressure.

Reactor cools down equipped with external jacket.Feedstock preparation unit (feed preparation unit) is installed to allow Ethylene dissolved in a solvent before joining reactor.

MAO is purchased from Akzo Nobel as the solution (7 weight % Al in isopentane) of modified MAO.

Reactor operates in a continuous manner, it may be assumed that removes product from reactor in course of reaction and adds supplementary raw material. Typical flow rate and reactor concentration are as follows:

Chromium is (as Cr (acetylacetone,2,4-pentanedione)₃): 0.00125-0.0025 mmol/ liter

Part/Cr mol ratio=1.8/1

Al/Cr mol ratio=900/1 (Akzo MMAO-3A)

G/ minute, ethylene feed speed=8

MAO solution+ml/ minute, hexamethylene ~ 33

The liquid fraction produced in these experiments is generally higher than 95% alhpa olefin.Described reactor is also equipped with hydrogen charging dress Put.

Table 1

Round #	Temperature of reactor (DEG C)	The reactor retention time (hour)	Conversion of ethylene (%)	Activity (g product/g Cr. hour)	C6, weight %	C8, weight %	C10+ weight %
								1	60	0.5	78.8	2,871,255	49.3	31.3	16.2
2	70	0.5	81.3	2,962,348	52.7	26.3	17.8
								3	80	0.5	78.5	2,860,324	55.6	25.2	16.0
4	80	1.0	81.2	2,958,704	51.5	28.4	16.7

Ethylene flow velocity=8g/ minute.

Hydrogen flow rate=0.018g/ minute.

Reactor pressure=8MPa

[Cr]=0.00253 mmol/ liter

Al/Cr (mol) = 900/1

Part/Cr (mol)=1.8/1

The most all use the ligand 1 of part A.

The level that polymer produces is the 1%(less than 1% of the reacted of the ethylene less than reaction Ethylene).Hexene-1 purity of 97% is observed in all hexenes.

Industrial applicibility

Provide new phosphorus-nitrogen-phosphorus (" P-N-P ") part.This part and catalytic chromium source metal and activator are (such as methyl Aikyiaiurnirsoxan beta) combination can be used for the selective oligomerization of ethylene.Gained oligomer is mainly linear alpha-olefin, and (especially octene is with own Alkene), its comonomer that can be used as preparing ethylene-alpha-olefin copolymer.

Claims (11)

1. part, is defined by the formula:

Wherein Ar₁It it is aromatic hydrocarbyl；Ar^FIt it is aromatic perfluorocarbon epoxide；Ar₃And Ar₄Independently selected from aromatic hydrocarbyl and aromatics perfluor Oxyl；And R₁It is C_1-20Alkyl.

2. the part of claim 1, wherein Ar^FIt is

3. the part of claim 2, wherein Ar₃And Ar₄It is individually aromatic hydrocarbyl.

4. the part of claim 3, wherein Ar₁It is phenyl and Ar₃With Ar₄It it is the substituted phenyl of o-fluorine.

5. the part of claim 1, wherein R₁It it is isopropyl.

6. for the method for ethylene oligomerization, wherein said method include making ethylene under the oligomerization conditions with comprise urging of following component Agent system contacts:

I) chromium source；

Ii) part being defined by the formula

Wherein Ar₁Selected from aromatic hydrocarbyl；Ar^FIt it is aromatic perfluorocarbon epoxide；Ar₃And Ar₄Complete independently selected from aromatic hydrocarbyl and aromatics Fluorohydrocarbon epoxide；And R₁It is C_1-20Alkyl, and

Iii) activator.

Method the most according to claim 6, described method is entered at the temperature of 10 DEG C-300 DEG C and the pressure of 5-150 atmospheric pressure OK.

Method the most according to claim 6, wherein said Cr source is selected from lower group: Chlorizate chromium；Chromium carbonyl；Carboxylic acid chromium and acetylacetone,2,4-pentanedione Chromium.

Method the most according to claim 6, wherein said activator comprises MAO.

Method the most according to claim 6, described method be further characterized by produce containing more than 25 weight % octene- The liquid product stream of 1.

11. molecules: