CN1272349C - Polyolefine catalyst, its making method, using method, and polymer made from said catalyst - Google Patents
Polyolefine catalyst, its making method, using method, and polymer made from said catalyst Download PDFInfo
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- CN1272349C CN1272349C CN 01137457 CN01137457A CN1272349C CN 1272349 C CN1272349 C CN 1272349C CN 01137457 CN01137457 CN 01137457 CN 01137457 A CN01137457 A CN 01137457A CN 1272349 C CN1272349 C CN 1272349C
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Abstract
The present invention carries out heat treatment on preactivated Zieglar-Natta catalyst and can control the molecular weight distribution of polyolefin produced by the catalyst; at the same time, the catalyst can retain high activity and a good villus form still.
Description
Consult related application
The application is filed on January 28th, 1997, and sequence number is 08/789,862, and the continuation that is entitled as the U.S. Patent application of " Ziegler-Natta catalyst that is used for olefinic polyreaction " applies for that partly this paper introduces this application as a reference.
Background of invention
The present invention relates to the manufacture method of catalyzer, this catalyzer, using method, the polymerization process of this catalyzer and the polymkeric substance that makes by this catalyzer.On the other hand, the present invention relates to the manufacture method of polyolefin catalyst, this catalyzer, the using method of this catalyzer, polyolefinic polyreaction and polyolefine.Aspect also having one, the invention still further relates to the manufacture method of Ziegler-Natta catalyst, this catalyzer, the using method of this catalyzer, polyolefinic polyreaction and polyolefine.
Background technology
Since the twentieth century initial stage fifties, the polyolefin catalyst of Ziegler-type, their common manufacture method and using method afterwards have been widely known by the people in polymerization field approximately.
But, though Ziegler-type catalyst has been known many, people still constantly seek to improve they polymer yield, catalyst life, catalyst activity and their make the method for polyolefinic ability with some performance.
Be published on March 10th, 1981, the United States Patent (USP) 4 of Kimura etc., 255,544 have disclosed a kind of use comprises that the catalyzer of following ingredients carries out the method for ethylene polymerization: (A) reaction product of magnesium compound and titanium halide, (B) organo-aluminium compound, wherein composition A makes solid matter by dialkoxy magnesium and halogenous silicon compound and alcohol reaction, and solid matter and titanium halide make containing to react in the presence of the silicon compound of alkoxyl group then.
Be published in April 3 nineteen ninety, the United States Patent (USP) 4 of Job etc., 914,069 has disclosed and has had the improved activity and the preparation method of olefin polymer catalyst composition optionally, and this preparation method is: the magnesium compound that (a) will contain at least a aryloxy, alkyl or carbonate or alkoxyl group carries out halogenation with titanic first halogenide and first electron donor; (b) products therefrom is contacted with titanic second halogenide; (c) the treated halogenated products that makes with the unreactive hydrocarbons liquid scrubbing.In the method, second electron donor is used for step (a) or (b), and the product of step (b) contacts with titanic trihalid in 40-140 ℃ temperature in step (b2), subsequently the treated product of washing in step (c).
Be published on October 13rd, 1992, the United States Patent (USP) 5 of Shelly, 155,187 have disclosed the polymerization process that a kind of use is generally the catalyzer of following substance reaction product: the metallic compound of silicon-containing compound, dialkyl magnesium, alcohol, halide, aluminium alkoxide and contain the second halid metallic compound.
Be published on March 11st, 1997, the United States Patent (USP) 5,610,246 of Buehler etc. has disclosed a kind of method of carrying out propylene polymerization with silicon-dioxide as the catalyzer of carrier of using.This catalyzer comprises the product that is contacted gained by silicon-dioxide with any order and following material: (1) at least a magnesium-containing compound that dissolves in hydrocarbon; (2) be selected from the first following improvement compound: silicon halogenide, boron halogenide, aluminium halogenide and their mixture are second compound of special improvement then.
Be published on May 20th, 1997, the United States Patent (USP) 5,631,334 of Zandona has disclosed a kind of manufacture method that is used at least a alkene (being total to) polymeric catalyst solid, and this method comprises makes magnesium and at least a transition metal coprecipitation.
But although prior art makes progress, these prior arts do not have to disclose or proposed to activate in advance the thermal treatment of polyolefin catalyst.
In addition, the reference of these prior arts does not disclose yet or proposes, and the thermal treatment of preactivated polyolefin catalyst is for any influence of molecular weight distribution (" MWD ").
Therefore, this area needs polyolefin catalyst.
This area also needs to make the method for polyolefin catalyst.
This area also needs the polymerization process of alkene.
This area also needs the polyolefine of various molecular weight distribution.
This area also needs to be convenient to make the polyolefinic polyolefin catalyst of various molecular weight distribution, and this catalyzer also has high reactivity and good fine hair form.
This area also needs to use through heat treated pre-activation polyolefin catalyst makes polyolefine produce the method for molecular weight distribution.
According to this specification sheets, comprise its accompanying drawing and claims, these and other of this area need be conspicuous for those of skill in the art.
Summary of the invention
The purpose of this invention is to provide polyolefin catalyst.
Another object of the present invention provides the manufacture method of this polyolefin catalyst.
Another object of the present invention provides the polymerization process of alkene.
Another object of the present invention provides the polyolefine of various molecular weight distribution.
Another object of the present invention provides the polyolefinic polyolefin catalyst of being convenient to make various molecular weight distribution, and this catalyzer also has high reactivity and good fine hair form.
A further object of the invention provides use makes polyolefine produce the method for molecular weight distribution through heat treated pre-activation polyolefin catalyst.
According to an embodiment of the invention, provide a kind of polyolefin catalyst.This catalyzer is made by the method that comprises the following steps: being that dialkyl magnesium and the general formula of MgRR ' is R by general formula a), " the alcohol reaction of OH, synthetic general formula is Mg (OR ")
2Solubility dialkoxy magnesium, two or more among wherein R, R ' and the R " each contains the alkyl of 1-20 carbon atom or the alkyl of replacement naturally, and, R, R ', R " can be identical, also can difference; B) contact with the dialkoxy magnesium compound with weak halogenating agent, this weak halogenating agent can form reaction product " A " with alkoxyl group of a halogen displacement; C) contact with reaction product " A " with first halogenation/titanizing agent, form reaction product " B "; D) contact with reaction product " B " with stronger second halogenation/titanizing agent, form reaction product " C "; E) contact with reaction product " C " with the pre-activator of organoaluminum, form preactivated catalyzer; F) heat preactivated catalyzer.In step f), the preactivated catalyzer of temperature range internal heating about 90-150 ℃ was about 30 minutes heat-up time-24 hours.
Another embodiment of the invention provides polyolefin polymer.The manufacture method of this polymkeric substance comprises, one or more 'alpha '-olefin monomers are in contact with one another in the presence of catalyzer of the present invention.Usually monomer is a vinyl monomer, and polymkeric substance is a polyethylene polymer.
Another embodiment of the invention has provided the catalyst system that comprises polyolefin catalyst of the present invention and inert support.Usually inert support is a magnesium compound.
Another embodiment of the invention has provided the manufacture method of this catalyzer.This method generally includes the following step: being that dialkyl magnesium and the general formula of MgRR ' is R by general formula a), " the alcohol reaction of OH, synthetic general formula is Mg (OR ")
2Solubility dialkoxy reactive magnesium product, two or more among wherein R, R ' and the R " each contains the alkyl of 1-20 carbon atom or the alkyl of replacement naturally, and, R, R ', R " can be identical, also can difference; B) contact with the dialkoxy magnesium compound with weak halogenating agent, this weak halogenating agent can form reaction product " A " with alkoxyl group of a halogen displacement; C) contact with reaction product " A " with first halogenation/titanizing agent, form reaction product " B "; D) contact with reaction product " B " with stronger second halogenation/titanizing agent, form reaction product " C "; E) contact with reaction product " C " with the pre-activator of organoaluminum, form preactivated catalyzer; F) heat preactivated catalyzer.In step f), the preactivated catalyzer of temperature range internal heating about 90-150 ℃ was about 30 minutes heat-up time-24 hours.
The present invention also has an embodiment that the polymerization process of alpha-olefin is provided.This polymerization process generally includes the following step: one or more alpha-olefins are in contact with one another in the presence of catalyzer; B) discharge polyolefin polymer.Monomer is vinyl monomer preferably, and polymkeric substance polyethylene preferably.The catalyzer that is used for this method is made by the following step: be that the dialkyl magnesium of MgRR ' and general formula are that " alcohol of OH synthesizes the solubility dialkoxy magnesium that general formula is Mg (OR ") 2 to R by general formula i), wherein R, R ' and R " each contains the alkyl of 1-20 carbon atom or the alkyl of replacement naturally; and; R, R ', R " in two or more can be identical, also can difference; Ii) contact with dialkyl magnesium compound with weak halogenating agent, this weak halogenating agent can form reaction product " A " with alkoxyl group of a halogen displacement; Iii) use first halogenation/titanizing agent to contact, form reaction product " B " with reaction product " A "; Iv) use the second stronger halogenation/titanizing agent to contact, form reaction product " C " with reaction product " B "; V) contact with reaction product " C ", form preactivated catalyzer with the pre-activator of organoaluminum; Vi) heat preactivated catalyzer.
According to this specification sheets, comprise its accompanying drawing and claims, the these and other objects of this area are conspicuous for those of skill in the art.
Description of drawings
Fig. 1 is a bar graph, and it has shown the influence of thermal treatment to the intrinsic molecular weight distribution of catalyzer.
Embodiment
The manufacture method of catalyst component of the present invention generally includes the following step: the dialkanyl oxide that is formed metal by metal diaikyl and alcohol, the metal halide dialkanyl oxide, in one or more step, use halogenation/titanizing agent to form catalyst component, handle catalyst component forming preactivated catalyzer with pre-activator such as organoaluminum, and preactivated catalyzer is heat-treated.
The mechanism that method of the present invention proposed is as follows usually:
1.
；
2.
；
3.
；
4.
；
5.
；
6. the thermal treatment of pre-activated catalyst
In following formula, M can be any suitable metal, and preferably IIA family most preferably is Mg.In following formula, " each is alkyl naturally, or the hydrocarbyl portion that replaces, and R and R ' contain 1-20 carbon atom, preferably contain 1-10 carbon atom, more preferably contain 2-6 carbon atom, also will preferably contain 2-4 carbon atom for R, R ', R ", R and R "." contain 3-20 carbon atom usually, R contains 2-6 carbon atom to R usually, and R " " contains 2-6 carbon atom usually, and is generally butyl.R, R ', R ", R , R " " in two or more any combination can be identical, perhaps the R group can be different.
At the ClAR of following formula
xIn, A is irreducibility oxyphie compound preferably, and it can be with alkoxyl group of a chloride ions displace, and R is alkyl preferably, and x is that the valency of A subtracts 1.The example of A comprises titanium, silicon, aluminium, carbon, tin and germanium, titanium most preferably wherein, and x most preferably is 3.The example of R is the hydrocarbyl portion that contains 2-6 carbon atom, comprises methyl, ethyl, propyl group, sec.-propyl and contains the resemblance of 2-6 carbon atom.
When the accurate composition of product " A " is unknown, think that it contains part chlorating metallic compound, an one example is ClMg (OR ").First halogenation/titanation step is made product " B ", the title complex of its chances are chlorination and part chlorination metal and titanium compound, for example, may be by (MCl
2)
y(TiCl
x(OR)
4-x)
Z 'Expression.Second chlorination/titanizing makes product " C ", and it also may be the title complex of chlorination and part chlorination metal and titanium compound, but is different from product " B ", may be by (MCl
2)
y(TiCl
X '(OR)
4-x ')
Z 'Expression.The chlorination degree of estimating " product C " is greater than " product B ".The Different Complex that big chlorination degree can be made different compounds.Though these descriptions to reaction product now provide most possible chemistry to explain that the present invention described in claims is not subjected to the restriction of these theoretical mechanisms.
It is any at the metal diaikyl and the metal dialkanyl oxide that are used for making when of the present invention the suitable polyolefins catalyzer to be applicable to that metal diaikyl of the present invention and the metal dialkanyl oxide of making comprise.Preferred metal dialkanyl oxide and metal diaikyl comprise the metal dialkanyl oxide and the metal diaikyl of IIA family metal.Preferred metal dialkanyl oxide or metal diaikyl are dialkoxy magnesium or dialkyl magnesium.
In embodiments of the present invention, dialkyl magnesium [MgRR '] can be wherein R and the aforesaid any dialkyl magnesium of R '.Certainly, R and R ' can be identical, also can be different.The non-limitative example of the dialkyl magnesium that is suitable for comprises magnesium ethide, dipropyl magnesium, dibutylmagnesium, butyl ethyl magnesium etc.Butyl ethyl magnesium (BEM) is preferred dialkyl magnesium.
In embodiments of the present invention, the metal dialkanyl oxide preferably general formula be Mg (OR ")
2Magnesium compound, wherein R " is to contain the alkyl of 1-20 carbon atom or the alkyl of replacement.The dialkoxy magnesium compound is that general formula is that magnesium compound and the general formula of MgRR ' is R " reaction product of the alcohol of OH; wherein R and R ' they are the alkyl that contains 1-10 carbon atom; and can be identical; also can be different; and alcohol is straight or branched alcohol, and R wherein " is the alkyl that contains 4-20 carbon atom.
The metal dialkanyl oxide most preferably is solvable and irreducibility.The advantage of irreducibility compound is that it forms MgCl
2, rather than the Ti of the solubility that forms by compound (as MgRR ') reduction
+ 3Class, the latter often forms the catalyzer with wide size-grade distribution.In addition, Mg (OR ")
2Reactivity littler than MgRR ', with weak chlorizating agent chlorination, to carry out chlorination/titanizing and carry out second chlorination/titanizing with strong reagent with weak reagent simultaneously then be progressively and reaction more by force successively, it can produce the more product of homogeneous, promptly produces bigger granules of catalyst and the more catalyst grain size distribution of homogeneous.
The non-limitative example of the preferred type metal dialkanyl oxide that is suitable for comprises dibutoxy magnesium, two pentyloxy magnesium, two hexyloxy magnesium, two (2-ethyl hexyl oxy) magnesium and anyly is suitable for making the soluble alkoxide of system.Most preferred metal alkoxide type is two (2-ethyl hexyl oxy) magnesium.
As nonrestrictive example, dialkoxy magnesium is as two (2-ethyl hexyl oxy) magnesium, can reaction make as 2-Ethylhexyl Alcohol as butyl ethyl magnesium (BEM) and alcohol (R " OH) by alkyl magnesium compound (MgRR '), be expressed from the next:
Under the BEM situation, RH and R ' H are to be respectively butane and ethane.Reaction is at room temperature carried out, and reactant forms solution.Any two or more R groups can be identical, and the R group also can be different mutually.
In embodiments of the present invention, can use any alcohol that can produce required metal dialkanyl oxide.As non-limitative example, alcohol can be that general formula is R " any alcohol of OH, wherein R " are the alkyl that contains 4-20 carbon atom.Alcohol can be straight chain alcohol or branched-chain alcoho.The non-limitative example of alcohol comprises ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 2-Ethylhexyl Alcohol etc.Preferred alcohol is 2-Ethylhexyl Alcohol.
The add-on of alcohol is usually about 0.5-4 equivalent (with respect to the equivalent of magnesium or metallic compound total amount), preferably about 1-3 equivalent.Though think that almost any alcohol can both use, preferably use higher branched-chain alcoho, for example 2-ethyl-1-hexanol.Employed alcohol contains 3 carbon atoms usually at least, preferably contains 4 at least, and more preferably at least 5, and at least 6 carbon atoms most preferably.
Alkyl metal cpd is owing to electron-deficient bonding, so be highly associating, this causes producing the very high high molecular form of viscosity in solution.Can reduce this high viscosity as triethyl aluminum by adding aluminum alkyls.Aluminum alkyls can destroy the association between each metal alkylide molecule.Aluminum alkyls is preferably 0.001 with the ratio of metal: 1-1: 1, and 0.01-0.1 more preferably: 1, most preferably be 0.03: 1-0.05: 1.In addition, the electron donor as ether, for example isoamyl ether (DIAE) can be used to further reduce the viscosity of metal alkylide.Electron donor is about 0 with the preferable range of the ratio of metal: 1-10: 1, and preferred scope is about 0.1: 1-1: 1.
The reagent that is used for the metal halide alkoxide in halogenation step comprises any at the halogenating agent that is used for producing when of the present invention the suitable polyolefins catalyzer.Halogenation step is chlorinating step preferably, and preferred halogenating agent is a muriate.
Preferred muriate halogenation agent (agent chlorizating agent ") is monochloride preferably, and it only carries out the part chlorination to dialkoxy magnesium.Preferred chlorizating agent general formula is ClAR
xOr ClAOR
x, wherein A is an irreducibility oxyphie compound, and it can be with alkoxyl group of a chloride ions displace, and R is an alkyl, subtracts 1 and x is the valency of A.The example of A is titanium, silicon, aluminium, carbon, tin and germanium, most preferably titanium and silicon, and wherein x is 3.R is the hydrocarbyl portion that contains 2-6 carbon atom, and its example is methyl, ethyl, propyl group, sec.-propyl and the resemblance that contains 2-6 carbon atom.To the effective chlorizating agent example of the present invention is ClTi (O
iPr)
3And ClSi (Me)
3, the ratio of preferred titanium and magnesium is 0.5-5.0.
The halogenation of metal alkoxide is carried out in hydrocarbon solvent under inert atmosphere usually.The non-limitative example of suitable solvents comprises toluene, heptane, hexane, octane etc.Preferred solvent is a hexane.
In this halogenation step, the common scope of the mol ratio of metal alkoxide and halogenating agent is about 6: 1-1: 3, and preferable range is about 3: 1-1: 2.Preferred scope is about 2: 1-1: 2, and most preferred scope is about 1: 1.
Halogenation step is carried out in 0-100 ℃ temperature range usually, and the scope in reaction times is about 0.5-24 hour.Halogenation step is preferably carried out in about 20-90 ℃ temperature range, and the preferable range in reaction times is about 1-4 hour.
In case carry out halogenation step, and the metal dialkanyl oxide is by halogenation, product " A " is subjected to a step or multistep halogenation/titanizing is handled.
In a step or multistep halogenation/titanation step, the preferably quaternary titanium compound of halogenation/titanizing agent, all four substituting groups all are identical, and substituting group is halogen ion or alkoxyl group or the phenoxy group that contains 2-10 carbon atom, for example TiCl
4, or Ti (OR)
4Preferably chlorination of halogenation/titanizing agent/titanizing agent.
It is preferred that chlorination/the titanizing agent can be the simplification compound, also can be the mixture of compound.Method of the present invention provides the activatory catalyzer later in first chlorination/titanation step; But chlorination/titanizing preferably carries out twice at least, all uses the different compounds or the mixture of compound at every turn, comprises along with each chlorination/titanation step is successively used stronger chlorination/titanizing agent.
The preferably weak titanizing agent of first chlorination/titanizing agent, for example, the blend of halogenated titanium and organic titanate.First chlorination/titanizing agent is more preferably TiCl
4With Ti (OBu)
4Blend, TiCl
4/ Ti (OBu)
4Be about 0.5: 1-6: 1, most preferably be 2: 1-3: 1.Think that the blend of halogenated titanium and organic titanate reacts, and forms halogenated alkoxy titanium (titanium alkoxyhalide), Ti (OR)
aX
b, wherein OR and X are respectively alkoxyl group and halogen ion, a+b is the valency of titanium, is generally 4, and a and b can be mark, a=2.5 for example, b=1.5.
Perhaps, first chlorination/titanizing agent can be the simplification compound.Example as the first chlorination/titanizing agent of simplification compound is Ti (OC
2H
5)
3Cl, Ti (OC
2H
5)
3Cl, Ti (OC
3H
7)
2Cl
2, Ti (OC
3H
7)
3Cl, Ti (OC
4H
9) Cl
3, Ti (OC
6H
13)
2Cl
2, Ti (OC
2H
5)
2Br
2And Ti (OC
12H
5) C
3
First halogenation/titanation step is carried out in hydrocarbon solvent usually.The non-limitative example of the hydrocarbon solvent that is suitable for comprises heptane, hexane, toluene, octane etc.Preferred solvent is a hexane.
In soluble product " A ", add after first halogenation/titanizing agent under the room temperature, be settled out solid product " B ".
The consumption of halogenation/titanizing agent must be enough to be settled out solid product from solution.Usually, the consumption of halogenation/titanizing agent is in the ratio of titanium with metal, and scope is about 0.5-5 usually, and preferable range is about 1-4, the about 1.5-2.5 of most preferred scope.
With any suitable recovery technology the solid product " B " that is settled out in first titanation step is reclaimed then, and wash with hydrocarbon solvent.
The compound that is suitable for use as second halogenation/titanizing agent comprises that those are suitable for use as the compound of first halogenation/titanizing agent, and different is the second halogenation/preferably stronger reagent of titanizing agent.The second stronger halogenation/titanizing agent is halogenated titanium preferably, is more preferably titanium tetrachloride [TiCl
4], wherein titanium is preferably 0 with the ratio of magnesium: 1-2: 1.
Usually the mode of carrying out of second halogenation/titanation step is to make solid product " B " form slurries in hydrocarbon solvent, generation reaction product, i.e. catalyst component " C ".The cited hydrocarbon solvent that is applicable to first halogenation/titanation step all is an available.Usually, the common scope of titanium tetrachloride consumption is about the 0.1-5 equivalent, and preferable range is about the 0.15-4 equivalent, and most preferred range is about the 0.175-2.5 equivalent.
Catalyst component " C " can mix with organoaluminum co-catalyst component (" pre-activator "), forms the pre-activated catalyst that is suitable for olefinic polymerization.Generally, the promotor that uses with the transition metal that contains catalyst component " C " is the organometallic compound of Ia, IIa, IIIa family metal, as aluminum alkyls, alkyl aluminium hydride (aluminumalkyl hydrides), lithium alkylide aluminium, zinc alkyl(s), alkyl magnesium etc.
Pre-activator is organo-aluminium compound preferably.The pre-activator of organoaluminum preferably structural formula is AlR^
3Aluminum alkyls, wherein R^ is alkyl or the halogen ion that contains 1-8 carbon atom, R^ can be identical, also can be different, and to have a R^ at least be alkyl.The pre-activator of organoaluminum is more preferably trialkylaluminium, for example trimethyl aluminium (TMA), triethyl aluminum (TEAl) and triisobutyl aluminium (TiBAl).Most preferred pre-activator is TEAl.Al is 0.01 with the ratio of titanium: 1-2: 1, preferably 0.25: 1-1.2: 1.
Then, in about 90-150 ℃ temperature range, preactivated catalyzer is heat-treated the about 100-125 of preferred temperature range ℃.Slurries leave standstill certain retention time under this high temperature, and this time range is about 0.5-24 hour, the about 1-4 of the preferable range of retention time hour.Subsequently, final solid catalyst is recovered, and washs with hydrocarbon solvent.
Perhaps, electron donor can add with halogenating agent, weak first halogenation/titanizing agent, stronger second halogenation/titanizing agent.Most preferably, in second halogenation/titanation step, use electron donor.
It is well-known being used to prepare polyolefinic electron donor, and any suitable electron donor of suitable catalyst that can provide may be used to the present invention.
Electron donor is also referred to as Lewis base, is the organic compound of oxygen, nitrogen, phosphorus or sulphur, and it can provide an electron pair for catalyzer.
Electron donor can be simple function group or multi-functional compound; preferably be selected from aliphatic carboxylic acid or aromatic carboxylic acid and their alkane ester, fatty ether or cyclic ethers, ketone, vinyl acetate, acryl derivative, particularly alkyl acrylate or alkyl methacrylate and silane.The preferred example of the electron donor that is suitable for is a n-butyl phthalate.The more preferably example of the electron donor that is suitable for is that general formula is RSi (OR ')
3Alkyl silyl alkoxide, methyl (triethoxy) silicomethane [MeSi (OEt for example
3)], wherein R and R ' they are the alkyl that contains 1-5 carbon atom, can be identical, and also can be different.
The carrier of catalyst system of the present invention should be chemically with all nonreactive inert solid of any traditional Ziegler-Natta catalyst composition.This carrier is magnesium compound preferably.Being used to catalyst component that the magnesium compound example of carrier is provided is magnesium halide, dialkoxy magnesium, halogenated alkoxy magnesium and magnesium carboxylates.Preferred magnesium compound is magnesium chloride (MgCl
2).
Perhaps, Ziegler-Natta catalyst can pass through prepolymerization.Prepolymerized method generally is,, contacts with catalyzer with small amounts of monomer with after promotor contacts at catalyzer.The explanation of prepolymerization method can be referring to United States Patent (USP) 5,106,804; 5,135,158; With 5,594,071, this paper is incorporated herein by reference.
Catalyzer can be used in the homopolymerization or copolyreaction method of any known any kind alpha-olefin.For example, catalyzer of the present invention is used for catalyzed ethylene, propylene, butylene, amylene, hexene, 4-methylpentene and other contains the alpha-olefin of 2 carbon atoms and their mixture at least.Catalyzer of the present invention is preferred for vinyl polymerization, produces polyethylene.
The catalyzer that the present invention makes has the high activity that depends in part on the olefinic polymerization condition at least.Usually, catalyst activity is at least 6,000 gram polyethylene/gram catalyzer (gPE/g), but also may be greater than 100,000 gram polyethylene/gram catalyzer.
In addition, the catalyzer that makes of the present invention provides the polymkeric substance with good fine hair form.Therefore, catalyzer of the present invention provides the macrobead of the polymkeric substance with homogeneous size-grade distribution, and its medium and small, superfine particle (approximately less than 125 microns) only exists with lower concentration.Catalyzer of the present invention comprises the big powder of the easy conversion with high powder accumulation density, and it is applicable to the production method of polyreaction.
Polymerization process can be body, slurry or vapor phase process.Preferably in slurry polymerization, use catalyzer of the present invention.Polymeric reaction condition (as temperature and pressure) depends on used type of device and used polymerization process type, and is as known in the art.For example, temperature range can be about 50-200 ℃, and pressure range can be about 10-800 pound/inch
2
Olefinic monomer can be added in the polymerization zone of thinner, thinner is to be the non-reaction heat-carrying agent of liquid under reaction conditions.The example of this thinner is hexane and Trimethylmethane.For the copolyreaction of ethene and another alpha-olefin (for example butylene or hexene),, the content of second alpha-olefin can be 0.01-20 mole %, preferred 0.02-10 mole %.
For polymerization process, preferably be contained in in-line power daughter and externally fed daughter or the stereoregular selective control agent (SCA) of catalyzer in synthetic, deactivated catalyst when polyreaction.The in-line power daughter can be used for the formation reaction of catalyzer in chlorination or chlorination/titanation step.Be suitable for the compound that as in-line power daughter prepares conventional carriers type Ziegler-Natta catalyst composition and comprise ethers, two ethers, ketone, lactone, the electron donor that contains N, P and/or S atom and the ester of special category.Particularly suitable be phthalic ester, for example diisobutyl phthalate, dioctyl phthalate (DOP), diphenyl phthalate and Unimoll BB; Malonic ester, for example propanedioic acid diisobutyl ester and diethyl malonate; PIVALIC ACID CRUDE (25) alkane ester and aromatic ester; Toxilic acid alkane ester, cycloalkanes ester and aromatic ester; Carbonic acid alkane ester and aromatic ester, for example carbonic acid diisobutyl ester, ethylene phenyl ester and diphenyl carbonate; Succinate, for example diethyl succinate and ethyl succinate.
The externally fed daughter that can be used for preparing catalyzer of the present invention includes organic silane compound.For example general formula is SiR
m(OR ')
4-mOrganoalkoxysilane, wherein R is selected from alkyl, cycloalkyl, aryl and vinyl; R ' is an alkyl; M is 0-3, and R can be identical with R '; When m was 0,1 or 2, R ' base can be identical, also can be different; When m was 2 or 3, the R base can be identical, also can be different.
Externally fed daughter of the present invention is preferably selected from the silane compound that is expressed from the next:
Wherein R1 and R4 contain primary carbon, secondary carbon or tertiary carbon atom to link alkyl or cycloalkyl on the silicon, and R1 and R4 can be identical, also can be different; R2 and R3 are alkyl or aryls.R1 can be methyl, sec.-propyl, cyclopentyl, cyclohexyl or the tertiary butyl; R2 and R3 can be methyl, ethyl, propyl group or butyl, and need not identical; R4 also can be methyl, sec.-propyl, cyclopentyl, cyclohexyl or the tertiary butyl.Concrete externally fed daughter is cyclohexyl methyl dimethoxy silane (CMDS), diisopropyl dimethoxy silane (DIDS), cyclohexyl sec.-propyl dimethoxy silane (CIDS), dicyclopentyl dimethoxyl silane (CPDS) or di-t-butyl dimethoxy silane (DTDS).
The poly molecular weight distribution (Mw/Mn) that makes with above-mentioned catalyzer is at least 4.0, preferably is at least 5.0, more preferably is at least 6.0, most preferably is at least 7.0.
Embodiment
The present invention roughly as mentioned above, following embodiment just describes some embodiment of the present invention.Should be appreciated that these embodiment provide in illustrational mode, never is to be used for limiting specification sheets or appending claims.
Preparation of catalysts
The controlled polyethylene catalysts of present embodiment explanation form, it is convenient to the intrinsic molecular weight distribution (MWD) of the polymkeric substance that is made by this catalyzer is finely tuned.Molecular weight distribution is regulated, make the various grade polymer that are applied to from injection molding (narrow MWD) to blown film (wide MWD) with regard to available single catalyst system.
The manufacture method of catalyzer is as follows:
Step 1
Make the solubility intermediate A with BuEtMg/DIAE/TEAl (1: 0.6: 0.03)+2-Ethylhexyl Alcohol (2.09).
With intermediate A+1.0 ClTi (OPr)
3Make the solubility intermediate B.
Step 3
With intermediate B+Ti (OBu)
4/ TiCl
4(2.0: 1.0) make the solid pre-catalyst.
Pre-catalyst+TiCl
4(0.25)+TEAl makes final catalyzer.
Step 5
Then final catalyzer is heat-treated in 90 ℃, heat treatment time is as shown in table 1 below.
Polyreaction
The reactor (autoclave of design) that is used for polymerising ethylene has 4 liters capacity, and the mixing auger oar of four mixing baffles and two reverse pitch is housed.By Teledyne-Hastings raydist (Raydist) mass flow controller ethene and hydrogen are fed in the reaction vessel, keep the reaction pressure of inside constant with the dome that back pressure regulator is housed simultaneously.Kammer valve regulation (in the reactor jacket) steam and the cold water of Barber-Coleman controller is linked in use, keeps temperature of reaction.
Hexane uses as thinner.
The test variable:
80 ℃ of temperature
60 minutes reaction times
125 pounds/inch of pressure
2
0.2 milliliter of slurries of catalyzer (about 10 milligrams of catalyzer)
Promotor TEAl@0.25 mmole/liter
Flow velocity H
2/ C
2@0.25
Table 1
| Time (hour, 90 ℃) | Promotor | SR5 | M w/M n |
| 0 (contrast) | TEAl | 10.4 | 5.4 |
| 2 | TEAl | 11.1 | 6.7 |
| 4 | TEAl | 11.7 | 6.8 |
| 6 | TEAl | 12.5 | 6.4 |
| 24 | TEAl | 12.8 | 6.8 |
Catalyst solution was taken a sample in the time of 2,4,6 and 24 hours.Shown in SR5 and GPC data that table 1 and Fig. 1 (TEAl promotor) illustrate, significantly widened intrinsic molecular weight distribution in the thermal treatment in this stage.Can find out also that thus molecular weight distribution increases all the time steadily in 6 hours heat-processedes at first.After this, widen degree and become flat.In addition, data presentation might be according to the purposes of polymkeric substance, and the fine setting catalyzer makes molecular weight distribution reach required numerical value.At last, find that catalyzer do not lose high reactivity or good fine hair form during thermal treatment.
Though specifically described illustrated embodiment of the present invention, should be appreciated that, it is evident that the present invention can carry out various other improvement, and can under the situation of spirit and scope of the invention, easily carry out by those skilled in the art.Therefore, do not wish that appended claim scope is subjected to the restriction of this paper previous embodiment and description, but but regard claims as comprise feature all granted patent of the present invention, that have novelty scope, comprise that those can be considered as being equal to all features of content under the present invention by the technician in the field relevant with the present invention.
Claims (54)
1. polyolefin catalyst is characterized in that it makes with the method that comprises the following steps
A) be Mg (OR ") with halogenating agent contact general formula
2Solubility dialkoxy magnesium compound, this halogenating agent can form reaction product A with alkoxyl group of halogen displacement, wherein " be to contain the alkyl of 1-20 carbon atom or the alkyl of replacement, described halogenating agent general formula is ClAR to R
x, wherein A is an irreducibility oxyphie compound, and R is the hydrocarbyl portion that contains 2-6 carbon atom, and x is that the valency of A subtracts 1;
B) blend of using halogenated titanium and organic titanate forms reaction product B as first halogenation/titanizing agent contact reacts product A;
C) with the stronger second halogenation/titanizing agent contact reacts product B of halogenated titanium conduct, form reaction product C;
D) with the pre-activator contact reacts of organoaluminum product C, form preactivated catalyzer;
E) at 90-150 ℃ the preactivated catalyzer of temperature range internal heating, be 30 minutes-24 hours heat-up time.
2. catalyzer as claimed in claim 1, " the reaction product that the alcohol reaction of OH obtains; wherein the R of alkyl magnesium, R ' are the alkyl that contains 1-10 carbon atom; can be identical; also can difference; described alcohol is straight chain alcohol or branched-chain alcoho, R " is the alkyl that contains 4-20 carbon atom that it is characterized in that described solubility dialkoxy magnesium compound is is that alkyl magnesium and the general formula of MgRR ' is R by general formula.
3. catalyzer as claimed in claim 2 is characterized in that described solubility dialkoxy magnesium compound is two (2-ethyl hexyl oxy) magnesium.
4. catalyzer as claimed in claim 2 is characterized in that described alkyl magnesium compound is magnesium ethide, dipropyl magnesium, dibutylmagnesium or butyl ethyl magnesium.
5. catalyzer as claimed in claim 2 is characterized in that described alcohol is ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol or 2-Ethylhexyl Alcohol.
6. catalyzer as claimed in claim 2 is characterized in that the reaction of described alkyl magnesium and alcohol also comprises aluminum alkyls.
7. catalyzer as claimed in claim 6 is characterized in that described aluminum alkyls is a triethyl aluminum.
8. catalyzer as claimed in claim 7 is characterized in that the described aluminum alkyls and the ratio of magnesium are 0.001: 1-1: 1.
9. catalyzer as claimed in claim 1 is characterized in that described catalyzer has the fine hair form that is suitable for the polymerization production method, and can provide the size-grade distribution of homogeneous and a spot of granularity less than 125 microns particle.
10. catalyzer as claimed in claim 2 is characterized in that the reaction of described alkyl magnesium and alcohol also comprises electron donor.
11. catalyzer as claimed in claim 10 is characterized in that the described electron donor and the ratio of magnesium are 0: 1-10: 1.
12. catalyzer as claimed in claim 11 is characterized in that described electron donor is an ether.
13. catalyzer as claimed in claim 1 is characterized in that described weak first halogenation/titanizing agent is TiCl
4And Ti (OBu)
4Blend, TiCl
4/ Ti (OBu)
4Be 0.5: 1-6: 1.
14. catalyzer as claimed in claim 1 is characterized in that it is RSi (OR ') that described step b) also comprises general formula
3Electron donor, wherein R and R ' are the alkyl that contains 1-5 carbon atom, can be identical, also can be different.
15. catalyzer as claimed in claim 14 is characterized in that described electron donor is a methyl-triethoxysilane.
16. catalyzer as claimed in claim 1 is characterized in that the described second stronger halogenation/titanizing agent is a titanium tetrachloride, wherein titanium is 0 with the ratio of magnesium: 1-2: 1.
17. catalyzer as claimed in claim 1 is characterized in that the pre-activator of described organoaluminum is that general formula is AlR^
3Aluminum alkyls, wherein R^ is alkyl or the halogen ion that contains 1-8 carbon atom, R^ can be identical, also can be different, and to have a R^ at least be alkyl.
18. catalyzer as claimed in claim 17 is characterized in that the pre-activator of described organoaluminum is a trialkylaluminium.
19. catalyzer as claimed in claim 18 is characterized in that the described aluminium and the scope of the ratio of titanium are 0.1: 1-2: 1.
20. the manufacture method of catalyzer is characterized in that it comprises:
A) be Mg (OR ") with halogenating agent contact general formula
2Solubility dialkoxy magnesium compound, this halogenating agent can form reaction product A with alkoxyl group of halogen displacement, wherein " be to contain the alkyl of 1-20 carbon atom or the alkyl of replacement, described halogenating agent general formula is ClAR to R
x, wherein A is an irreducibility oxyphie compound, and R is the hydrocarbyl portion that contains 2-6 carbon atom, and x is that the valency of A subtracts 1;
B) blend of using halogenated titanium and organic titanate forms reaction product B as first halogenation/titanizing agent contact reacts product A;
C) with the stronger second halogenation/titanizing agent contact reacts product B of halogenated titanium conduct, form reaction product C;
D) with the pre-activator contact reacts of organoaluminum product C, form preactivated catalyzer;
E) at 90-150 ℃ the preactivated catalyzer of temperature range internal heating, be 30 minutes-24 hours heat-up time.
21. method as claimed in claim 20, it is characterized in that described solubility dialkoxy magnesium compound is the " reaction product that the alcohol reaction of OH obtains; wherein the R of alkyl magnesium, R ' are the alkyl that contains 1-10 carbon atom; can be identical; also can be different; described alcohol is straight chain alcohol or branched-chain alcoho, and pure R " is the alkyl that contains 4-20 carbon atom that is that alkyl magnesium and the general formula of MgRR ' is R by general formula.
22. method as claimed in claim 20 is characterized in that described solubility dialkoxy magnesium compound is two (2-ethyl hexyl oxy) magnesium.
23. method as claimed in claim 21 is characterized in that described alkyl magnesium compound is magnesium ethide, dipropyl magnesium, dibutylmagnesium or butyl ethyl magnesium.
24. method as claimed in claim 21 is characterized in that described alcohol is ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol or 2-Ethylhexyl Alcohol.
25. method as claimed in claim 21 is characterized in that the reaction of described alkyl magnesium and alcohol also comprises aluminum alkyls.
26. method as claimed in claim 25 is characterized in that described aluminum alkyls is a triethyl aluminum.
27. method as claimed in claim 26 is characterized in that the described aluminum alkyls and the ratio of magnesium are 0.001: 1-1: 1.
28. method as claimed in claim 20 is characterized in that described catalyzer has the fine hair form that is suitable for the polymerization production method, and can provide the size-grade distribution of homogeneous and a spot of granularity less than 125 microns particle.
29. method as claimed in claim 21 is characterized in that the reaction of described alkyl magnesium and alcohol also comprises electron donor.
30. method as claimed in claim 29 is characterized in that the described electron donor and the scope of the ratio of magnesium are 0: 1-10: 1.
31. method as claimed in claim 20 is characterized in that described halogenating agent is ClTi (O
iPr)
3
32. method as claimed in claim 31, it is characterized in that wherein titanium and the ratio of magnesium be 0.5-5.0.
33. method as claimed in claim 20 is characterized in that described weak first halogenation/titanizing agent is TiCl
4And Ti (OBu)
4Blend, TiCl
4/ Ti (OBu)
4Be 0.5: 1-6: 1.
34. method as claimed in claim 21 is characterized in that the reaction of described alkyl magnesium and alcohol also comprises electron donor.
35. method as claimed in claim 20 is characterized in that the described second stronger halogenation/titanizing agent is a titanium tetrachloride, wherein titanium is 0 with the ratio of magnesium: 1-2: 1.
36. method as claimed in claim 35, the consumption that it is characterized in that described titanium tetrachloride is the 0.1-5.0 equivalent.
37. method as claimed in claim 20 is characterized in that the pre-activator of described organoaluminum is that general formula is AlR^
3Aluminum alkyls, wherein R^ is alkyl or the halogen ion that contains 1-8 carbon atom, R^ can be identical, also can be different, and to have a R^ at least be alkyl.
38. method as claimed in claim 37 is characterized in that the pre-activator of described organoaluminum is a trialkylaluminium.
39. method as claimed in claim 38 is characterized in that the scope of wherein aluminium and the ratio of titanium is 0.1: 1-2: 1.
40. method as claimed in claim 39 is characterized in that the pre-activator of described organoaluminum is TEAl.
41. method as claimed in claim 20 is characterized in that described electron donor is present in step a), b), c) or d) in any one the step, electron donor wherein is 0 with the ratio of metal: 1-10: 1.
42. method as claimed in claim 20 is characterized in that described catalyzer is used to make molecular weight distribution and is at least 4.0 polyethylene.
43. the polymerization process of alpha-olefin is characterized in that it comprises:
A) one or more 'alpha '-olefin monomers are in contact with one another in the presence of catalyzer;
Wherein catalyzer is made by the following step:
I) be Mg (OR ") with halogenating agent and general formula
2Solubility dialkoxy magnesium compound contact, this halogenating agent can be replaced an alkoxyl group with a halogen, formation reaction product A, wherein " be alkyl or the substituted alkyl that contains 1-20 carbon atom, described halogenating agent general formula is ClAR to R
x, wherein A is an irreducibility oxyphie compound, and R is the hydrocarbyl portion that contains 2-6 carbon atom, and x is that the valency of A subtracts 1;
The blend of ii) using organic titanate forms reaction product B as first halogenation/titanizing agent contact reacts product A;
Iii) use halogenated titanium as stronger second halogenation/titanizing agent contact reacts product B, form reaction product C;
Iv), form preactivated catalyzer with the pre-activator contact reacts of organoaluminum product C;
V) at 90-150 ℃ the preactivated catalyzer of temperature range internal heating, be 30 minutes-24 hours heat-up time.
44. method as claimed in claim 43 is characterized in that it also comprises:
B) discharge polyolefin polymer.
45. method as claimed in claim 43 is characterized in that described monomer is a vinyl monomer, described polymkeric substance is a polyethylene.
46. method as claimed in claim 45 is characterized in that described poly molecular weight distribution is at least 4.0.
47. method as claimed in claim 43 is characterized in that described polyreaction carries out in body, slurry or gas phase.
48. method as claimed in claim 43 is characterized in that described halogenating agent is ClTi (OiPr)
3
49. method as claimed in claim 43 is characterized in that described first halogenation/titanizing agent is TiCl
4And Ti (OBu)
4Blend, TiCl
4/ Ti (OBu)
4Ratio be 0.5: 1-6: 1.
50. method as claimed in claim 49 is characterized in that described step I i) in the ratio of the titanium that exists and magnesium be 0.5-5.0.
51. method as claimed in claim 43 is characterized in that the described second stronger halogenation/titanizing agent is TiCl
4
52. method as claimed in claim 51 is characterized in that described TiCl
4Consumption be the 0.1-5.0 equivalent.
53. method as claimed in claim 43 is characterized in that the pre-activator of described organoaluminum is TEAl.
54. method as claimed in claim 43 is characterized in that described electron donor is present in any step among step I-iv, and the ratio of electron donor and metal is 0: 1-10: 1.
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|---|---|---|---|
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