CN1077577C - Ethylene dimerization catalyst and catalyst system composed of said dimerization catalyst and ethylene polymerization catalyst - Google Patents
Ethylene dimerization catalyst and catalyst system composed of said dimerization catalyst and ethylene polymerization catalyst Download PDFInfo
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Abstract
The present invention relates to an ethylene dimerization catalyst for and a catalytic system prepared from the ethylene dimerization catalyst and an ethylene polymerization catalyst, wherein the ethylene dimerization catalyst is prepared from components A and B; the components A are a chlorine-free inorganic porous solid carrier, alkoxy titanium with a general formula of Ti(OR)4 and an electron donor compound selected from ester, ether and estolide by contact; the component B is a liquid alkoxy silicon compound. One double-function catalytic system prepared from the ethylene dimerization catalyst and the ethylene polymerization catalyst by combination can prepare copolymers of ethene and butene-1 of different density from single ethene.
Description
The present invention relates to the olefin polymerization catalysis field, the bifunctional catalysis system that relates in particular to the ethylene dimerization catalyzer and form by this dimerization catalyst and ethylene rolymerization catalyst.
Report about the ethylene dimerization catalyzer in the prior art has a lot, mainly contains the catalyst based and aluminum alkyl catalyst of Ti-base catalyst, nickel-base catalyst, tantalum or niobium at present.Wherein the butylene of nickel-base catalyst-1 selectivity is not high, easily generates butylene-2; Though two kinds of catalyzer selectivity height then, catalyst activity is very low.Use Ti-base catalyst to prepare the selectivity height of butylene-1, by product is few, has lot of advantages.
The product butylene-1 of ethylene dimerization mainly is intended for a kind of comonomer and the ethylene copolymer preparation has better processability energy, intensity and flexible LLDPE and HDPE.And in recent years, adopt the catalyzed ethylene oligomerisation simultaneously in same polymeric kettle of a kind of catalyst system to become α-alkene, and make α-alkene " on the spot " copolymerization of ethene and generation and the double-function catalyzing route for preparing ethene and α-olefin copolymer has caused the very big interest of people.This technology adds α-olefinic monomer with traditional employing and compares with the preparation method of ethylene copolymer, can save independent preparation and the process of separating α-alkene, need not to add comonomer, be single raw material only with ethene, just can prepare ethylene copolymer, can simplify production technique, reduce production costs.
This double-function catalyzing route can be realized by two kinds of methods: a kind of is to handle to obtain two kinds of catalytic active centers on same support of the catalyst, is respectively applied for ethylene oligomerization and copolymerization.The patented technology US4988657 of such catalyzer such as Phillips and the patented technology US5137994 of UCC.The limitation of this method is that the oligomerisation/copolymerization active centre ratio of catalyzer is just definite in the preparation, and the output adjustability of α-alkene is restricted when polymerization, but can not become a kind of catalyzer of flexible density polymer.Therefore, more investigator is devoted to develop the bifunctional catalyst system that is combined by a kind of ethylene oligomerization catalyst and a kind of ethylene rolymerization catalyst.This catalyst system can be by regulating the density that two kinds of catalyst consumption are regulated polymerization product.
The patented technology EP230983 of Phillips, patent name are " ethylene dimerization and polymerization ", disclose a kind of method that ethene is transformed to dimer, oligopolymer and superpolymer.Used dimerization catalyst is a kind of insoluble solid that is loaded with the positive alkyl ester of Ti or V at least on the surface.Its preparation has two kinds of technology, and a kind of is that for example methyl alcohol treatment S i-Ti is cogelled, makes Ti and methoxyl group bonding with alcohol; Another kind method is the alkyl ester with Ti or V, as Ti (OC
2H
5)
4, Ti (OC
3H
7)
4, Ti (OC
4H
9)
4, Ti (OC
6H
4CH
3)
4, VO (OC
2H
5)
3Deng a kind of inorganic porous property solid carrier of processing.
In this piece patent application of Phillips, the polymerizing condition of ethylene dimerization is: in 2 liter polymeric kettles, be solvent with the Trimethylmethane, in 80 ℃, carry out endless tube method slurry polymerization, polymerization time 30 minutes under ethylene pressure 550psig (38.67 normal atmosphere) condition.
Solid ethylene dimerization catalyzer that obtains as mentioned above and the copolymerization catalyst for ethylene that contains trialkylaluminium are as TiCl
3.0.33AlCl
3Or, can directly prepare ethylene copolymer by ethene as disclosed Ti in the patents such as US 4198718, US 4069169, US 4327158, US 4325837, US 4312784-Mg series catalysts contact, shared.
Dimerization is to carry out under the condition identical with above-mentioned dimerization reaction with the coupling of copolymerization.
The shortcoming of this prior art is, the ethylene dimerization activity of such catalysts is very low, under above-mentioned polymerizing condition, the dimerization activity be 12350～24700g/gTi.h. (gram/gram titanium. hour); If consider pressure factor, activity have only 319～639g/gTi.h.atm (gram/gram titanium. hour .1 normal atmosphere ethene).Simultaneously, the matching problem of still unresolved dimerization catalyst of this patent and polymerizing catalyst does not have to form good bifunctional catalysis system, does not provide the good embodiment that makes vinyl polymerization with this dimerization catalyst and catalyst for copolymerization coupling.Have only a unsteady example of technological process, polyreaction because of uncontrollable, stopped reaction after 10 minutes.
The patent application CN86101889A of UCC, exercise question is " carrying out the method for the copolyreaction of ethylene dimerization reaction and ethene and dimers simultaneously ", discloses a kind of continuous process that dimerisation products copolymerization in ethylene dimerization reaction generation butene-1 and ethene and the fluidized-bed is carried out simultaneously.Used catalyst system comprises following component:
A. structural formula is Ti (OR)
4Four titan-alkoxides, each R is the alkyl that contains outside the unsaturated aliphatic hydrocarbon base of 1～12 carbon atom in the formula;
B. empirical formula is magnesium-titanium based composition and use thereof in packaging of MgmTi (OR) nXp (ED) g, and R is aliphatics or the aromatic hydrocarbyl that contains 1～14 carbon atom in the formula, and X is a halogen, and ED is a kind of organic electronic donor compound.M is 0.5～56, and n is 0,1,2, and p is 2～116, and g is 2～80.This magnesium-titanium based composition and use thereof in packaging adopts a kind of inert support material to dilute.
C. a structural formula is AlR
3Trialkyl aluminium compound, R is the saturated hydrocarbyl that contains 1～14 carbon atom in the formula.
Adopt above-mentioned catalyst system, in fluidized-bed reactor, under 30～115 ℃, ethylene partial pressure is 5.6-19MPa, and ethene is contacted with the catalyst system of effective catalytic amount continuously, can prepare the multipolymer of ethene and butene-1.It is pointed out that some butene-1 adds reactor from external source in polymerization process in order to obtain the many polymkeric substance of butene-1 content.Having prepared density thus is 0.86～0.96g/cm
3Ethylene copolymer.
This ethylene dimerization catalyzer of the prior art is the alkoxy titanium compound that well-known non-modified is handled, and catalyst activity is very low.And as one of composition of vinyl polymerization bifunctional catalysis system, the ethylene dimerization catalyst component of this liquid state makes solid-state ethylene rolymerization catalyst part inactivation.Therefore, the consumption of dimerization catalyst can not be too much, the density polymer adjustability is restricted, when the butene-1 of " on the spot " generation can not be satisfied the demand, also to replenish the butene-1 of external source, and the loss of activity of dimerization catalyst is very fast in polymerization process, does not match on reaction kinetics with polymerizing catalyst.
The objective of the invention is to overcome the low shortcoming of ethylene dimerization catalyst activity in the above-mentioned patented technology, prepare a kind of highly active ethylene dimerization catalyzer.
Another object of the present invention provides a kind of stable bifunctional catalysis system that is combined to form by ethylene dimerization catalyzer and ethylene rolymerization catalyst, in this catalyst system, dimerization catalyst does not destroy the activity of polymerizing catalyst, two kinds of catalyzer can be coordinated to use, on catalytic activity, mutually promote, can prepare a series of adjustable density by single ethene, have the ethylene copolymer of excellent physical and mechanical property.
Ethylene dimerization catalyzer of the present invention is made up of the Ti series catalysts component A of not halogen-containing carrierization and liquid alkoxy-silicon compound B component, and component A is to be Ti (OR) by a kind of not chloride inorganic porous property solid carrier and a kind of general formula
4Titan-alkoxide and a kind of electron donor compound contact that is selected from ester class, ethers and anhydrides make.Among the ingredient of solid catalyst A of gained, titanium content is 1.6～8.4%, and the mol ratio of titan-alkoxide and electron donor is 1/1～10/1.B component is liquid alkoxy-silicon compound, and the consumption of B component makes among the component A among the Ti and B component the mol of Si than in 1/10～10/1 scope usually.
A kind of bifunctional catalysis system is formed in above-mentioned ethylene dimerization catalyzer and ethylene rolymerization catalyst coupling, is raw material with single ethene, can make the ethene of different densities and the multipolymer of butene-1.Used ethylene rolymerization catalyst is the supported catalysts of titanium-magnesium system; Promotor is an alkylaluminium cpd.
Carrier among the dimerization catalyst component A of the present invention is the porous inorganic oxide, and for example silica gel, aluminum oxide, alumino silica gel etc. are preferably silica gel, and this carrier has high specific surface area and big pore volume.Usually specific surface area is 250～300m
2/ g.
Carrier is handled through high-temperature activation under the atmosphere of anaerobic usually, and activation temperature is at 100～600 ℃.
Carrier through high-temperature activation contacts in inert solvent with alkoxy titanium compound and a kind of electron donor compound.Remove solvent then, obtain titaniferous supported catalysts component A.
The alkoxy titanium compound Ti (OR) that the present invention adopts
4In, R is C
1-C
10Alkyl or aralkyl, be preferably: Ti (OC
4H
9)
4, Ti (OiC
3H
7)
4Or Ti (OC
6H
4CH
3)
4
The amount of the used titan-alkoxide of catalyst component A can change in the scope of broad among preparation the present invention, needs as much as possiblely at bonding on the carrier or adhere to Ti usually, and Ti content is 1.6%～8.4% in the catalyzer that makes.
Electron donor compound used among the component A comprises ester class, ethers, acid anhydrides etc., for example ethyl benzoate, methyl methacrylate, dibutyl phthalate, THF, Tetra hydro Phthalic anhydride, triphenylphosphine, tetraethoxy-silicane etc.
The amount of used electron donor also can change in relative broad range.Usually the mol ratio that requires titan-alkoxide and electron donor compound is 1/1～10/1, and best is 2/1～5/1.
Used solvent can be the representative examples of saturated aliphatic hydro carbons of straight or branched during preparation component A, as hexane, heptane, iso-pentane; Or naphthenic hydrocarbon, as pentamethylene, hexanaphthene and aromatic hydrocarbons,, preferably use the aliphatic hydrocarbon kind solvent of removing by distillation easily as benzene, toluene.
The temperature of reaction for preparing catalyst component A of the present invention is preferably 40～150 ℃, more preferably 50～80 ℃.Reaction pressure is preferably normal pressure, and the reaction times is preferably 0.5～4 hour.After reaction finishes, by evaporation or filtering method with solvent and solids constituent from, obtain solid powdery catalyst component A.
Catalyst component B is liquid alkoxy-silicon compound, for example Si (OEt) among the present invention
4, SiCH
3(OCH
3)
3, SiPh
2(OCH
3)
2, be preferably Si (OEt)
4
The consumption of B component makes usually among the component A that the mol ratio of Si is preferably 1/3～3/1 among the Ti and B component in 1/10～10/1 scope.
Component A is used in combination with B component and constitutes ethylene dimerization catalyzer of the present invention.It is to have added the electron donor compound among the catalyst component A in prior art that this catalyzer is distinguished, this has not only improved the dimerization activity of catalyzer, and improved the selectivity that dimerization produces butene-1 greatly, make the superpolymer that produces sticking wall in the polymerization process hardly.And the effect of B component is that the dimerization activity of catalyzer is improved significantly.
The used promotor of the present invention is that general formula is AlR
3Alkylaluminium cpd.
In the bifunctional catalysis system of being made up of aforesaid ethylene dimerization catalyzer of the present invention and ethylene rolymerization catalyst, it is supported catalysts that ethylene rolymerization catalyst is preferably titanium.The general method for making of described catalyzer prepares for halogenated titanium and at least a electron donor compound are contacted with a kind of solid carrier in inert solvent.Wherein the electron donor compound comprises alcohol, acid anhydrides, ester etc., and solid carrier can be selected from magnesium chloride, alkoxyl magnesium or silica gel.
Ethylene dimerization catalyzer among the present invention can also be combined to form bifunctional catalysis system with other some ethylene rolymerization catalysts well-known in the art.
This vinyl polymerization bifunctional catalysis system of the present invention can be applied to ethylene thick liquid polymerizing and vapour phase polymerization, density and other performance that the proportioning by regulating dimerization catalyst and polymerizing catalyst can the controlled polymerization product.
Compare with prior art, the present invention has following advantage:
1. by changing the composition of dimerization catalyst, improved the activity of dimerization catalyst greatly.For example in aforementioned prior art EP230983, the ethylene dimerization activity of such catalysts is 319～639g/gTi.h.atm. only, and the activity of dimerization catalyst can reach 5158g/gTi.h.atm among the present invention.
2. dimerization catalyst does not destroy the activity of polymerizing catalyst in the vinyl polymerization bifunctional catalysis system of the present invention, the ethylene dimerization catalyzer has dimerization kinetic curve stably, can coordinate to use with ethylene rolymerization catalyst, can prepare the adjustable ethylene copolymers of performance such as density, the degree of branching by single ethene.The catalyst activity height of bifunctional catalysis system, in every gram catalyzer, polymerization activity reaches 1900-6800g polyethylene/g catalyzer, and polymerization process is steady.The density range that makes multipolymer is 0.89～0.96g/cm
3, and the density range that can regulate multipolymer as required.Multipolymer has good physical and mechanical property, and the resisting environmental stress and cracking value of institute's test sample product was greater than 600 hours.
The present invention is further described by the following embodiment, but the invention is not restricted to following embodiment.Embodiment 1: the ethylene dimerization Preparation of catalysts
The preparation of component A: in having the 100ml there-necked flask of electronic stirring, add 4mlTi (OBu)
4, 40ml the normal hexane solvent, 0.6ml dibutyl phthalate and the 3g that cross through molecular sieve drying be at 500 ℃ of SiO that activated
2Stir, the slurries that form after 2 hours, are removed normal hexane at 65 ℃ of constant temperature, obtain mobile well white powder, Ti content is 7.95% (weight) in the dry powder.
The preparation of B component: get 2ml Si (OEt)
4, be diluted to the solution for standby of 50ml with normal hexane.
Above-mentioned catalyzer is used for ethylene dimerization:
In 2 liters of polymeric kettles, the normal hexane of adding 1000ml and catalyst component A 0.0389g (3.093mgTi), B component 1ml, promotor AiEt
32.0mmol.Add hydrogen and ethylene gas subsequently.Polymerization stagnation pressure 8.3 normal atmosphere, hydrogen partial pressure 2.8 normal atmosphere.In 80 ℃ of reactions 2 hours.In reaction process, detect the content of butene-1 in the gas phase.Polymerization after 1 hour in the gas phase butene-1 content be 21.12% (volume); Polymerization butene-1 content 44.16% (volume) in the gas phase after 2 hours.Strong butylene flavor is arranged during discharging, and it is brown that solution is, no pressed powder.Coabsorption ethene 328g, catalyst activity 56741g/gTi, the consideration ethylene pressure is 5158g/gTi.h.atm.
Polymeric reaction temperature changes 70 ℃ into, and other condition is the same, and catalyst activity is 53720g/gTi; When polymerization temperature is 60 ℃, catalyst activity 24950g/gTi.Comparative example 1: the ethylene dimerization catalyzer that does not add electron donor among the component A.
The preparation of component A: in having the 100ml there-necked flask of electronic stirring, add the normal hexane solvent that 40ml crosses through molecular sieve drying, 8mlTi (OBu)
4, 6gSiO
2, the slurries that form after 2 hours, are removed normal hexane at 65 ℃ of constant temperature, obtain mobile well white powder, Ti content is 8.4% (weight) in the dry powder.
The preparation of B component is with embodiment 1.
Above-mentioned catalyzer is used for ethylene dimerization:
In 2 liters of polymeric kettles, add 1000ml normal hexane and catalyst component A 0.0747g (6.2748mgTi), B component 1ml, promotor AlEt
32.0mmol.Polymerization stagnation pressure 8.3 normal atmosphere, hydrogen partial pressure 2.8 normal atmosphere.In 80 ℃ of reactions 2 hours.React after 1 hour, butene-1 accounts for 13.46% (volume) in the gas phase; React after 2 hours, butene-1 accounts for 47.52% (volume) in the gas phase.Strong butene-1 flavor is arranged during discharging, the small amount of solid powder is arranged, it is brown that solution is.Coabsorption ethene 144g, catalyst activity 22948g/gTi.Comparative example 2: the ethylene dimerization catalyzer that does not add B component.
The preparation of component A is with comparative example 1 in the dimerization catalyst.
In 2 liters polymeric kettle, add the 1000ml normal hexane, add catalyst component A0.2065g (17.34mgTi) and 2.0mmol AlEt in the comparative example 1
3Polymerization stagnation pressure 8.3 normal atmosphere, hydrogen partial pressure 2.8 normal atmosphere.In 80 ℃ of reactions 2 hours.After the polymerization 1 hour, butene-1 content is 0.96% (volume) in the gas phase, polymerization after 2 hours gas phase butene-1 content be 13.66% (volume).Coabsorption ethene 76.5g, catalyst activity 4411g/gTi.Embodiment 2: the ethylene dimerization Preparation of catalysts
The preparation of component A: in the 100ml there-necked flask that has electronic stirring, add the 0.356g Tetra hydro Phthalic anhydride, 40ml normal hexane, 4mlTi (OBu)
4, stir, heat up, phthalic anhydride is dissolved fully after, add 3gSiO
2, reaction mixture, steams and removes normal hexane after 4 hours at 65 ℃ of constant temperature, obtains the mobile well powder of white, dry powder Ti content 7.62% (weight).
The preparation of B component is with embodiment 1.
Above-mentioned catalyzer is used for ethylene dimerization:
Polymeric temperature, pressure condition be with example 1, catalyst levels: component A 0.0424g (3.23mgTi), B component 1ml, promotor AlEt
32.0mmol.Polymerization after 1 hour in the gas phase butene-1 content be 20.2% (volume), polymerization after 2 hours gas phase butene-1 content be 33.26% (volume).Catalyst activity 32043g/gTi.Embodiment 3: ethylene dimerization catalyzer and ethylene rolymerization catalyst are formed bifunctional catalysis system.
The ethylene dimerization Preparation of catalysts is with embodiment 1.
The preparation of ethylene rolymerization catalyst:
With 10g Mg (OEt)
2With 19.4ml TiCl
4In the 70ml heptane,, make ingredient of solid catalyst A in 85 ℃ of reactions down; With 7.5g ZrCl
4, 14.79ml concentration is the AlEt of 2.21mmol/ml
2Cl and 11.25mlEtOH reacted 2 hours down in 30 ℃, made ingredient of solid catalyst B; Under 60 ℃, 5.0g component A is mixed with the 0.5g B component again, drip the TiCl of 9.6ml
4Si (OEt) with 1.5ml
4, continue reaction 2 hours, obtain the light yellow solid fine catalyst.
The polymerization of ethene under the dual-function catalyst effect:
In 2 liters of polymeric kettles, add the promotor AlEt of 1000ml normal hexane and 2mmol
3, dropping into dimerization catalyst component A is 0.0430g (3.1347mgTi), and B component is 0.5ml and the above-mentioned polymerizing catalyst that contains 0.1992mgTi, adds hydrogen and ethene subsequently, and hydrogen partial pressure 2.0 normal atmosphere keep polymerization stagnation pressure 11.0 normal atmosphere.In 85 ℃ of polymerizations 4 hours.Polymerization process is steady, obtains polymer powder 376g, and total catalyst activity is 113000gPE/gTi, and in catalyzer, activity is 6800gPE/gcat..Density polymer 0.9372g/cm
3, bulk density (BD) is 0.34, melting index (MI
2.16) be 0.096, the degree of branching is 4.9CH
3/ 1000C.Embodiment 4: ethylene dimerization catalyzer and ethylene rolymerization catalyst are formed bifunctional catalysis system.
The ethylene dimerization Preparation of catalysts is with embodiment 1.
The preparation of ethylene rolymerization catalyst is with embodiment 3.
In 2 liters of polymeric kettles, add the promotor AlEt of 1000ml normal hexane and 2mmol
3, dropping into dimerization catalyst component A0.0156g (1.1372mgTi), B component 1ml and contain the above-mentioned polymerizing catalyst of 0.1976mgTi adds hydrogen and ethene subsequently, and hydrogen partial pressure 2.8 normal atmosphere keep polymerization stagnation pressure 8.3 normal atmosphere.In 80 ℃ of polymerizations 2 hours.Polymerization process is steady.Obtain polymer powder 68g, total catalyst activity is 52000gPE/gTi, and density polymer is 0.9518g/cm
3, MI
2.16Be 0.36, the degree of branching is 2.2CH
3/ 1000C.Embodiment 5: ethylene dimerization catalyzer and ethylene rolymerization catalyst are formed bifunctional catalysis system.
The ethylene dimerization Preparation of catalysts is with embodiment 1.
The preparation of ethylene rolymerization catalyst is with embodiment 3.
In 2 liters of polymeric kettles, add the promotor AlEt of 1000ml normal hexane and 2mmol
3, dropping into dimerization catalyst component A is 0.088g (7.03mgTi), B component 1ml, after the stirring at room 5 minutes, add the above-mentioned polymerizing catalyst that contains 0.2211mgTi, add hydrogen and ethene subsequently, hydrogen partial pressure 2.0 normal atmosphere keep polymerization stagnation pressure 8.3 normal atmosphere.In 80 ℃ of polymerizations 2 hours.Polymerization process is steady, obtains polymer powder 130g, and total catalyst activity is 17928gPE/gTi.Density polymer 0.9275g/Gm
3, melting index (MI
2.16) be 0.75, the degree of branching is 11.6CH
3/ 1000C.Embodiment 6: ethylene dimerization catalyzer and ethylene rolymerization catalyst are formed bifunctional catalysis system.
The ethylene dimerization Preparation of catalysts is with embodiment 1.
Ethylene rolymerization catalyst is the vinyl polymerization PZ catalyzer of commercially available Mitsui.
In 2 liters of polymeric kettles, add the promotor AlEt of 1000ml normal hexane and 2mmol
3, dropping into dimerization catalyst component A is 0.0787g (6.257mgTi), and B component 1ml and contain the above-mentioned polymerizing catalyst of 0.205mgTi adds hydrogen and ethene subsequently, and hydrogen partial pressure 2.8 normal atmosphere keep polymerization stagnation pressure 8.3 normal atmosphere.In 80 ℃ of polymerizations 2 hours.Polymerization process is steady.Polymerization butene-1 content 3.89% in the gas phase after 1 hour, polymerization is gas phase butene-1 content 4.16% after 2 hours.Obtain polymer powder 116g, total catalyst activity is 17950gPE/gTi.Density polymer 0.9389g/cm
3Degree of branching 4.4CH
3/ 1000C.
Claims (12)
1. ethylene dimerization catalyzer is made up of the Ti series catalysts component A and the liquid alkoxy-silicon compound B component of not halogen-containing carrierization, and wherein component A is to be Ti (OR) by a kind of not chloride inorganic porous property solid carrier and a kind of general formula
4Titan-alkoxide and a kind of electron donor compound that is selected from ethers, ester class or anhydrides in a kind of inert organic solvents, contact and make; Among the ingredient of solid catalyst A of gained, titanium content is 1.6～8.4%, and the mol ratio of titan-alkoxide and electron donor is 1/1～10/1; B component is liquid alkoxy-silicon compound, and the consumption of B component makes among the component A among the Ti and B component the mol ratio of Si usually in 1/10～10/1 scope; The promotor of this dimerization catalyst is that general formula is AlR
3Alkylaluminium cpd.
2. ethylene dimerization catalyzer as claimed in claim 1, wherein the carrier among the component A is the porous inorganic oxide, can be selected from silica gel, aluminum oxide, alumino silica gel.
3. ethylene dimerization catalyzer as claimed in claim 2, wherein the carrier among the component A is a silica gel.
4. an ethylene dimerization catalyzer as claimed in claim 1, wherein the alkoxy titanium compound Ti (OR) among the component A
4Be selected from: Ti (OC
4H
9)
4, Ti (OiC
3H
7)
4, Ti (OC
6H
4CH
3)
4In at least a.
5. an ethylene dimerization catalyzer as claimed in claim 4, wherein the alkoxy titanium compound Ti (OR) among the component A
4Be Ti (OC
4H
9)
4
6. ethylene dimerization catalyzer as claimed in claim 1, wherein used electron donor compound is selected from ethyl benzoate, methyl methacrylate, dibutyl phthalate, tetrahydrofuran (THF), Tetra hydro Phthalic anhydride, triphenylphosphine and four alkoxyl silicones among the component A.
7. ethylene dimerization catalyzer as claimed in claim 1, wherein the scope of the mol ratio of titan-alkoxide among the component A and electron donor compound is 2/1～5/1.
8. ethylene dimerization catalyzer as claimed in claim 1, wherein alkoxy-silicon compound is selected from Si (OEt) in the B component
4, SiCH
3(OCH
3)
3And SiPh
2(OCH
3)
2
9. ethylene dimerization catalyzer as claimed in claim 1, wherein the consumption of B component makes among the component A that the mol ratio of Si is 1/5～5/1 among the Ti and B component.
10. one kind is the bifunctional catalysis system that ethylene rolymerization catalyst is formed by each described ethylene dimerization catalyzer and titanium among the claim 1-9, and promotor is that general formula is AlR
3Alkylaluminium cpd.
11. a bifunctional catalysis system as claimed in claim 10, wherein titanium is that ethylene rolymerization catalyst is that titanium is a supported catalysts.
12. a bifunctional catalysis system as claimed in claim 10, wherein the titanium electron donor compound that to be ethylene rolymerization catalyst be selected from alcohol, acid anhydrides or ester class by halogenated titanium and one or both contacts with a kind of solid carrier in inert solvent and makes.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0135441A1 (en) * | 1983-09-20 | 1985-03-27 | Institut Français du Pétrole | Process for the synthesis of butene-1 by dimerisation of ethylene |
| FR2565591A1 (en) * | 1984-06-08 | 1985-12-13 | Inst Francais Du Petrole | PROCESS FOR PRODUCING ETHYLENE-BUTENE-1 COPOLYMER FROM ETHYLENE |
| CN87103082A (en) * | 1986-04-28 | 1988-03-30 | 住友化学工业株式会社 | Process for producing alpha-olefin polymers |
| GB2223501A (en) * | 1988-10-07 | 1990-04-11 | Ghizela Davidovici | Process for the dimerization of ethylene and copolymerization to polyethylene |
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