CN102453138A - Olefin polymerization method - Google Patents

Olefin polymerization method Download PDF

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CN102453138A
CN102453138A CN2010105193356A CN201010519335A CN102453138A CN 102453138 A CN102453138 A CN 102453138A CN 2010105193356 A CN2010105193356 A CN 2010105193356A CN 201010519335 A CN201010519335 A CN 201010519335A CN 102453138 A CN102453138 A CN 102453138A
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olefine polymerizing
polymerizing process
process according
metallocene
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CN102453138B (en
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邱波
郑刚
谢伦嘉
亢宇
王洪涛
郭顺
王彦强
刘长城
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention provides a high-efficiency olefin polymerization method, which comprises a step of: contacting one or more olefins with a supported metallocene composite catalyst under the olefin polymerization conditions, wherein the supported metallocene composite catalyst comprises a carrier, and specific metallocene compound and alkyl aluminoxane which are supported on the carrier; and the carrier is a complex of SBA-15 like a bread circle and silica gel. When the supported metallocene composite catalyst prepared by supporting the metallocene which has a sandwich structure and of which the cpcyclopentadienyl has substituent to a methyl aluminoxane (MAO) treated carrier, namely the complex of the SBA-15 like a bread circle and the silica gel is used for olefin polymerization, the olefin polymerization efficiency is greatly improved.

Description

A kind of olefine polymerizing process
Technical field
The present invention relates to a kind of olefine polymerizing process.
Background technology
The Application and Development of metallocene catalyst is after traditional Ziegler-Natta catalyst; The another important breakthrough in olefin polymerization catalysis field; Particularly in the eighties; People such as Kaminsky and Sinn develops efficient promotor MAO (MAO), makes the research of metallocene catalyst enter into a stage that develops rapidly.Because it is big that the homogeneous phase metallocene catalyst reaches the required MAO consumption of high reactivity, production cost is high, and can not obtain the granulous polymkeric substance, can't on widely used slurry process or gas phase polymerization technology, use.In order to address the above problem, to adopt usually and load to the method for carrying out the metallocene loadization on the carrier to the solubility metallocene catalyst.At present, in relevant metallocene load research report with SiO 2For the report of carrier is studied at most.Especially aspect support/catalyst/co-catalyst system research remarkable progress having been arranged, promoted further developing of carried catalyst and polyolefin industry.
Molecular sieve is to have the evenly regular one dimension or the material of solid netted sieve aperture, and surfactivity is higher, absorption property good, have tangible molecule shape selectivity ability, and its allows the monomer of certain size and the polymkeric substance of formation thereof to insert in the duct of molecular sieve.Because molecular sieve has nano pore, monomeric inserted mode is different with freeboard with propagation process in the polymerization process, and double-basis terminated chance has been reduced in limited space to a certain extent, makes polyreaction show the characteristic of " living polymerization ".Especially (aperture=2～50nm), it compares with zeolite molecular sieve ordered mesoporous molecular sieve, has bigger specific surface area and relatively large aperture, can handle bigger molecule or group, can make catalyzer well bring into play its due catalytic activity.
When after olefin polymerization catalysis is carried on molecular sieve, being applied to olefinic polymerization, have following advantage:
(1) molecular sieve of synthetic does not contain the impurity that is prone to make polymer degradation, can improve the ageing resistance of polyolefine material;
(2) the molecular sieve nano pore has the dual-use function of carrier and reactor drum, and catalyst cupport efficient is high, and polymerization process is controlled easily, and can in the skeleton of polymerization reactor, key in the active site, accelerates reaction process, improves productive rate;
(3) insertion has three-dimensional selection effect with polyreaction to monomer, can improve polyolefinic molecular weight and fusing point.
This shows that the olefin coordination polymerization that appears as of molecular sieve carried olefin polymerization catalysis has been opened up a new field.
The molecular sieve carried metallocene catalyst of reporting on the document at present is mainly catalyzer ((a) Weckhuysen B M, Rao R R, Pelgri J, et al.Chem.Eur.J., 2000, the 6:2960 that ordered mesoporous material MCM-41 goes up load metallocene; (b) Rao R R, Weckhuysen B M, Schoonheydt R A.Chem.Commun., 1999,445), but the activity of this catalyzer when catalyzed ethylene polymerization is merely 7.3 * 10 5GPE/ (mol Zr h) (Chen S T, Guo C Y, Lei L, et al.Polymer, 2005,46:11093.), also have only 1 * 10 and handle behind the MCM-41 again the catalytic activity that the resulting catalyzer of load metallocene carries out vinyl polymerization with MAO 6GPE/ (mol Zrh) is still lower.
Therefore, how to obtain the carried metallocene catalyst of high catalytic activity, and then carry out olefinic polymerization efficiently and remain a technical problem that needs to be resolved hurrily.
Summary of the invention
The catalytic activity of olefin polymerization catalysis that the objective of the invention is to overcome prior art is still lower, causes adopting the not high problem of efficient of olefinic polyreaction, and a kind of olefine polymerizing process efficiently is provided.
In order to address the above problem; Contriver of the present invention finds through further investigation; Use when having substituent metallocene as olefin polymerization catalysis on the cyclopentadienyl moiety; Show different catalysis behaviors when not having substituent metallocene on the cyclopentadienyl moiety as olefin polymerization catalysis; On with cyclopentadienyl moiety, having substituent metallocene and load on catalyzer on the mesoporous material MCM-41 that MAO handled when carrying out vinyl polymerization, do not have substituent metallocene to load on catalyzer on the mesoporous material MCM-41 that MAO handled on its catalytic activity and the cyclopentadienyl moiety and compare and do not have considerable change, still is 1 * 10 6About gPE/ (mol Zrh); This might be that hole wall structure thermostability and the hydrothermal stability of mesoporous material MCM-41 is relatively poor; Just there is part to cave at the loading process hole wall, influenced load effect, to such an extent as to influenced catalytic activity; But have substituent metallocene on cyclopentadienyl moiety and load on catalyzer on the mixture of SBA-15 that MAO handled and silica gel when carrying out olefinic polymerization; With compare with the catalyzer that does not have substituent metallocene to load on the mixture of SBA-15 that MAO handled and silica gel on the cyclopentadienyl moiety, catalytic activity but obviously improves, and can reach 5.1 * 10 7G PE/ (molZr h), this might be that substituting group on the cyclopentadienyl moiety of metallocene has played certain effect when metallocene loads on the carrier, has improved load effect, thereby has made catalytic activity improve greatly.Accomplished the present invention based on above-mentioned cognition.
The invention provides a kind of olefine polymerizing process; This method is included under the olefinic polymerization condition, and a kind of alkene is contacted with the loaded metallocene composite catalyst, it is characterized in that; Said loaded metallocene composite catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on the carrier; Said carrier is the mixture of donut-like SBA-15 and silica gel, and said metallocene compound has the structure shown in the formula 1
Figure BSA00000318712200031
Wherein, R 1, R 2, R 3, R 4, R 5, R 1', R 2', R 3', R 4' and R 5' be hydrogen or C independently of one another 1-C 5Alkyl, and R 1, R 2, R 3, R 4And R 5In at least one be C 1-C 5Alkyl, R 1', R 2', R 3', R 4' and R 5' at least one be C 1-C 5Alkyl, M is a kind of in titanium, zirconium and the hafnium, X is a halogen.
According to olefine polymerizing process of the present invention; To have sandwich structure through using; And have substituent metallocene on the cyclopentadienyl moiety when loading to the loaded metallocene composite catalyst that obtains on the mixture of carrier donut-like SBA-15 that MAO handled and silica gel, improved olefinic polymerization efficient greatly as olefinic polymerization.
Description of drawings
Fig. 1 is an X-ray diffracting spectrum, and wherein, figure a is the x-ray diffraction pattern of donut-like SBA-15, and figure b is the x-ray diffraction pattern of loaded metallocene composite catalyst SBA-15-M-GJ-BU-1;
Fig. 2 is that (X-coordinate is relative pressure p/p for nitrogen adsorption-desorption graphic representation of donut-like SBA-15 (a1) and loaded metallocene composite catalyst SBA-15-M-GJ-BU-1 (a2) 0), and the pore size distribution curve figure of donut-like SBA-15 (b1) and loaded metallocene composite catalyst SBA-15-M-GJ-BU-1 (b2) (X-coordinate is nm);
Fig. 3 is an ESEM microscopic appearance photo, (a1) with (a2) be the microscopic appearance photo of donut-like SBA-15; (b1) and (b2) be the microscopic appearance photo of loaded metallocene composite catalyst SBA-15-M-GJ-BU-1;
Fig. 4 is a transmission electron microscope photo, (a1) with (a2) be the pore passage structure transmission electron microscope photo of donut-like SBA-15; (b1) and (b2) be the pore passage structure transmission electron microscope photo of loaded metallocene composite catalyst SBA-15-M-GJ-BU-1.
Embodiment
According to olefine polymerizing process provided by the invention; This method is included under the olefinic polymerization condition, and a kind of alkene is contacted with the loaded metallocene composite catalyst, it is characterized in that; Said loaded metallocene composite catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on the carrier; Said carrier is the mixture of donut-like SBA-15 and silica gel, and said metallocene compound has the structure shown in the formula 1
Figure BSA00000318712200051
Wherein, R 1, R 2, R 3, R 4, R 5, R 1', R 2', R 3', R 4' and R 5' be hydrogen or C independently of one another 1-C 5Alkyl, and R 1, R 2, R 3, R 4And R 5In at least one be C 1-C 5Alkyl, R 1', R 2', R 3', R 4' and R 5' at least one be C 1-C 5Alkyl, M is a kind of in titanium, zirconium and the hafnium, X is a halogen.
According to olefine polymerizing process of the present invention, what the M in the formula 1 can be in titanium, zirconium and the hafnium is a kind of.M in the different metallocene compound molecules can be identical or different, and preferably, M is a zirconium.
According to olefine polymerizing process of the present invention, the X in the formula 1 is a halogen.Particularly, the X in the formula 1 can be fluorine, chlorine, bromine and iodine.X in the different metallocene compound molecules can be identical or different, and preferably, the X in the formula 1 is chlorine and/or bromine.More preferably, the X in the formula 1 is a chlorine.
According to the present invention, in the formula 1, cyclopentadienyl moiety is for forming η with central metal 5Key and have the verivate of the cyclopentadienyl of alkyl substituent.Preferably, the R on the cyclopentadienyl moiety in the formula 1 1, R 2, R 3, R 4, R 5, R 1', R 2', R 3', R 4' and R 5' be hydrogen or C independently of one another 1-C 5Alkyl, and R 1, R 2, R 3, R 4And R 5In at least one be C 1-C 5Alkyl, R 1', R 2', R 3', R 4' and R 5' at least one be C 1-C 5Alkyl.
Among the present invention, said C 1-C 5Alkyl can be in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec.-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and the neo-pentyl one or more.
The specific examples that satisfies the cyclopentadienyl moiety of above-mentioned requirements comprises: methyl-cyclopentadienyl moiety, 1,2-dimethyl--cyclopentadienyl moiety, 1,3-dimethyl--cyclopentadienyl moiety, 1; 2,3-trimethylammonium-cyclopentadienyl moiety, 1,2; 5-trimethylammonium-cyclopentadienyl moiety, 1,2,3; 4-tetramethyl--cyclopentadienyl moiety, 1,2,3; 5-tetramethyl--cyclopentadienyl moiety, pentamethyl-cyclopentadienyl moiety, ethyl-cyclopentadienyl moiety, 1,2-diethylammonium-cyclopentadienyl moiety, 1,3-diethylammonium-cyclopentadienyl moiety, 1; 2; 4-triethyl-cyclopentadienyl moiety, 1,3,5-triethyl-cyclopentadienyl moiety, methyl-2-ethyl-cyclopentadienyl moiety, 1-methyl-3-ethyl-cyclopentadienyl moiety, n-propyl-cyclopentadienyl moiety, 1; 3-di-cyclopentadienyl moiety, 1-methyl-3-n-propyl-cyclopentadienyl moiety, 1; 3-di-isopropyl-cyclopentadienyl moiety, 1-methyl-3-sec.-propyl-cyclopentadienyl moiety, normal-butyl-cyclopentadienyl moiety, 1,3-di-n-butyl-cyclopentadienyl moiety, 1-methyl-3-normal-butyl-cyclopentadienyl moiety, sec.-butyl-cyclopentadienyl moiety, 1,3-two sec.-butyls-cyclopentadienyl moiety, 1-methyl-3-sec.-butyl-cyclopentadienyl moiety, 1-isobutyl--cyclopentadienyl moiety, 1; 3-diisobutyl-cyclopentadienyl moiety, 1-methyl 3-isobutyl--cyclopentadienyl moiety, the tertiary butyl-cyclopentadienyl moiety, 1; 3-di-t-butyl-cyclopentadienyl moiety, the 1-methyl 3-tertiary butyl-cyclopentadienyl moiety, n-pentyl-cyclopentadienyl moiety, 1,3-two n-pentyls-cyclopentadienyl moiety, 1-methyl-3-n-pentyl-cyclopentadienyl moiety, 1-isopentyl-cyclopentadienyl moiety, 1,3-diisoamyl-cyclopentadienyl moiety, 1-methyl-3-isopentyl-cyclopentadienyl moiety, 1-tert-pentyl-cyclopentadienyl moiety, 1; 3-two tert-pentyls-cyclopentadienyl moiety, 1-methyl-3-tert-pentyl-cyclopentadienyl moiety, neo-pentyl-cyclopentadienyl moiety, 1,3-di neo-pentyl-cyclopentadienyl moiety, 1-methyl-3-neo-pentyl-cyclopentadienyl moiety.
Preferably, the R in the formula 1 1And R 1' be C independently of one another 1-C 5Alkyl, R 2, R 3, R 4, R 5, R 2', R 3', R 4' and R 5' be hydrogen.The specific examples that satisfies the cyclopentadienyl moiety of above-mentioned requirements comprises: methyl-cyclopentadienyl moiety, ethyl-cyclopentadienyl moiety, n-propyl-cyclopentadienyl moiety, sec.-propyl-cyclopentadienyl moiety, normal-butyl-cyclopentadienyl moiety, sec.-butyl-cyclopentadienyl moiety, isobutyl--cyclopentadienyl moiety, the tertiary butyl-cyclopentadienyl moiety, n-pentyl-cyclopentadienyl moiety, isopentyl-cyclopentadienyl moiety, tert-pentyl-cyclopentadienyl moiety, neo-pentyl-cyclopentadienyl moiety.
According to olefine polymerizing process of the present invention, said alkylaluminoxane can be metallocene catalyst field various alkylaluminoxanes commonly used.Usually, the alkyl in the said alkylaluminoxane is aforesaid C 1-C 5Alkyl.Preferably, said alkylaluminoxane is a MAO.
Contriver of the present invention finds in research process, the R in formula 1 1And R 1' be normal-butyl, M is a zirconium, X is a chlorine; Be that said metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides; And when alkylaluminoxane is MAO, when said loaded metallocene composite catalyst is used for the polyreaction of catalyzed alkene, demonstrate excellent catalytic activity.
According to olefine polymerizing process of the present invention, the metallocene compound and the mol ratio of said carrier that load on the said carrier can change within a large range.Contriver of the present invention finds; Total amount with said carried metallocene catalyst is a benchmark; The total amount of said metallocene compound and alkylaluminoxane is weight %; When the content of said carrier is 90-40 weight %, not only can obtains gratifying catalytic effect, but also can reduce cost.More preferably, be benchmark with the total amount of said carried metallocene catalyst, the total amount of said metallocene compound and alkylaluminoxane is 45-55 weight %, 50 weight % more preferably, the content of said carrier is 55-45 weight %, more preferably 50 weight %.
According to olefine polymerizing process of the present invention, donut-like SBA-15 in said carrier and silica gel weight ratio can change within a large range.Contriver of the present invention finds that the weight ratio of donut-like SBA-15 and silica gel is 0.5-20 in the said carrier:, not only can obtain gratifying catalytic effect, but also can reduce cost at 1 o'clock.More preferably, the weight ratio of donut-like SBA-15 and silica gel is 1-10 in the said carrier: 1.
According to olefine polymerizing process of the present invention, the ratio between said alkylaluminoxane and the metallocene compound can be the known content of the technician of field of olefin polymerisation.Particularly, the mol ratio of aluminium in the said alkylaluminoxane and the M in the said metallocene compound can be 30-100: 1.
Among the present invention, said carrier is donut-like SBA-15 and silica gel, can be through under atmosphere of inert gases, donut-like SBA-15 and silica gel being mixed and roasting obtains.The temperature of said roasting can be 300-900 ℃, and the time of roasting can be 7-10 hour.The internal diameter of said donut-like SBA-15 and the ratio of external diameter can be 0.3-0.9, and median size can be 3-20 μ m, and mean thickness can be 0.1-2 μ m.The various donut-like that donut-like described in the present invention can it has been generally acknowledged that for this area; For example can be for having opening or not having the various circular of opening or type circular, said internal diameter and external diameter be meant respectively said bagel interior week the place radius and the periphery of circle belong to the radius of circle; The thickness of each donut-like SBA-15 is meant the mean thickness of each position of this donut-like SBA-15.The most probable aperture of said donut-like SBA-15 can be 7-10nm, is preferably 8-9nm, more preferably 8.4nm; Specific surface area is the 600-1000 meters squared per gram, is preferably the 650-800 meters squared per gram, more preferably 706 meters squared per gram; Pore volume is 0.5-3 milliliter/gram, is preferably 1-2 milliliter/gram, more preferably 1.5 milliliters/gram.Said donut-like SBA-15 can be commercially available, also can be synthetic according to the conventional compound method of donut-like SBA-15 in this area.Such as synthesizing donut-like SBA-15: with triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene (like P123) and N through following method; Dinethylformamide (DM F); Join in the aqueous hydrochloric acid; By the mole feed ratio; Triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene: N, dinethylformamide (DMF): water: hydrogenchloride=1: 300～700: 10000～20000: 100～500 are stirred to dissolving under 25 ℃～60 ℃ temperature; Add tetraethoxy in the gained solution, under 25 ℃～60 ℃ temperature, stir and carried out crystallization in 10 hours～40 hours; With the filtration of crystallization after product, washing, drying, obtain the donut-like mesoporous material raw powder; With gained donut-like mesoporous material raw powder in retort furnace 250 ℃～800 ℃ temperature lower calcinations 10 hours～40 hours, remove the masterplate agent, obtain the donut-like SBA-15 of removed template method.Said silica gel can directly be commercially available, and preferably, the median size of said silica gel is 10-30 μ m, and specific surface area is the 100-300 meters squared per gram, like 955 silica gel.
The preparation method of loaded metallocene composite catalyst according to the invention is included under the atmosphere of inert gases, successively alkylaluminoxane and metallocene compound is loaded on the carrier.
Said carrier, alkylaluminoxane and metallocene compound define hereinbefore, hereinafter repeat no more.
The method of the said loaded metallocene composite catalyst of preparation according to the present invention is included under the protection of inert gas, successively load alkylaluminoxane and metallocene compound on carrier.Can adopt the method for well known to a person skilled in the art that alkylaluminoxane and metallocene compound are loaded on the said carrier.Preferably, successively the method at load alkylaluminoxane and metallocene compound on the carrier comprises: under protection of inert gas, said carrier is contacted with first solution, said first solution contains the said alkylaluminoxane and first solvent; The carrier that has removed said first solvent is contacted with second solution, and said second solution contains the said metallocene compound and second solvent, and removes solvent, said first solvent and second solvent toluene of respectively doing for oneself.
The present invention does not have the special qualification can be for well known to a person skilled in the art the whole bag of tricks, for example for the method for said contact: dipping, spraying.The method of employing dipping can be so that solution gets in the duct on the carrier more fully, and therefore, the present invention is preferably flooded.
With not special qualification of condition that the carrier and first solution contact with second solution, for example: carrier can comprise with the condition that said first solution contacts: the time is 1-10 hour, and temperature is 25-80 ℃; The said carrier that has removed first solvent can be comprised with the condition that said second solution contacts: the time is 0.3-2 hour, and temperature is 25-80 ℃.
Preferably; The method for preparing said loaded metallocene composite catalyst also is included in before the load alkylaluminoxane; Under protection of inert gas; Said carrier was heated 7-10 hour under 300-900 ℃ temperature, (for example: water) with the volatile matter that contains in the hydroxyl of removing carrier surface and the carrier.
Prepare in the method for said loaded metallocene composite catalyst, chemically interactive all gases can not take place with carrier, alkylaluminoxane, metallocene compound for various in said rare gas element.For example, said rare gas element can be nitrogen, argon gas.
Method according to the said loaded metallocene composite catalyst of said preparation; With molar ratio computing, the charge capacity of said metallocene compound on said carrier (in silicon-dioxide) makes that the amount ratio mol ratio of said carrier and said metallocene compound is 1: 2 * 10 -3-9 * 10 -3, be preferably 1: 3 * 10 -3-8 * 10 -3Can realize that the total amount with said carried metallocene catalyst is a benchmark; The total amount of said metallocene compound and alkylaluminoxane can be 10-60 weight %; Be preferably 45-55 weight %, 50 weight % more preferably, the content of said carrier can be 90-40 weight %; Be preferably 55-45 weight %, more preferably 50 weight %; The weight ratio of donut-like SBA-15 and silica gel can be 0.5-20 in the said carrier: 1, be preferably 0.5-10: and 1, further be preferably 0.5: 1; The mol ratio of M in aluminium in the said alkylaluminoxane and the said metallocene compound can be 100-200: 1, be preferably 120-180: and 1,150-170 more preferably: 1, be preferably 164: 1 especially.
According to olefine polymerizing process of the present invention, said alkene can be various alkene with polymerizable double bond, for example, can be in ethene, terminal olefin and the diolefin one or more.Preferably, said alkene is ethene, C 3-C 101-alkene, C 4-C 8Diolefin in one or more.Said C 3-C 101-alkene be propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.Said C 4-C 8Diolefin be 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,3-heptadiene, 1,4-heptadiene, 1,3-octadiene and 1,4-octadiene etc.
According to olefine polymerizing process of the present invention, said olefinic polymerization condition can be carried out under the conventional condition of field of olefin polymerisation, and preferably, said olefinic polymerization condition comprises that temperature can be-78 ℃ to 100 ℃, and pressure can be 0.01-10MPa.Said olefinic polymerization is carried out in the presence of solvent, and said olefinic polymerization condition comprises: in metallocene compound, the concentration of said carried metallocene catalyst can be 1 * 10 -8-1 * 10 -5Mol, temperature can be-78 ℃ to 100 ℃, is preferably-20 ℃ to 90 ℃, more preferably 20 ℃ to 80 ℃, further be preferably 70 ℃, pressure can be 0.01-10MPa, is preferably 0.1-5MPa, more preferably 1MPa.Said solvent can be hexane.
Below in conjunction with embodiment the present invention is carried out detailed description.
In following examples, X-ray diffraction analysis is to carry out on the X-ray diffractometer of D8 Advance in the model available from company of German Bruker AXS company; TEM analysis is to carry out on the transmission electron microscope of Tecnai 20 in the model available from company of Dutch FEI Co.; Scanning electron microscope analysis is to carry out on the sem of XL-30 in the model available from company of U.S. FEI Co..The ultimate analysis of U.S. An Jielun company is carried out on available from model 7500CX instrument.
Nitrogen adsorption-desorption experiment condition comprises: the U.S. Autosorb-1 of Kang Ta company nitrogen adsorption desorption appearance, sample was 200 ℃ of degassings 4 hours.
Preparation example 1
The preparation of donut-like SBA-15: with 2.0 gram triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene (P123; The registration number of U.S. chemical abstract is 9003-11-6; Average molecular mass Mn=5800 are available from lark prestige Science and Technology Ltd., goods number 1546106) and 15 gram N; Dinethylformamide (DMF) is (available from lark prestige Science and Technology Ltd.; Goods number 287533) joins in the solution of 11.2 grams, 37% hydrochloric acid and 64ml water, be stirred to P123 at 40 ℃ and dissolve fully, again 4.45 gram tetraethoxys are joined in the gained solution 40 ℃ of stirrings 24 hours.Obtain former powder mesoporous material after filtration, washing, the drying.With the former powder mesoporous material of gained in retort furnace 600 ℃ the calcining 24 hours, remove the masterplate agent, obtain donut-like SBA-15 (wherein, the internal diameter of bagel and the ratio of external diameter are 0.5, and median size is 5 μ m, and mean thickness is 2 μ m).
Is to mix at 1: 2 donut-like SBA-15 and 955 silica gel with weight ratio, and with the 400 ℃ of calcinings 10 hours under nitrogen protection of their mixture, removing hydroxyl and remaining moisture, thereby obtains the carrier complexes (called after SBA-15-M) through thermal activation;
The activated carrier complexes of 0.51 gram is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, adds 20 milliliters purified toluene and 0.52 gram MAO (MAO) (available from U.S. Albemarle company), and stirred 4 hours at 50 ℃.After reaction is accomplished, leave standstill, leach liquid after the layering, and with 20 milliliters of hexane wash three times, at last solid is dried up with nitrogen, obtaining load has the carrier complexes of MAO (called after MAO/SBA-15-M-GJ).
Under nitrogen protection; MAO/SBA-15-M-GJ is joined in 250 milliliters of glass reactors; Add 20 milliliters of purified toluene, under 30 ℃, two (n-butyl cyclopentadienyl) zirconium dichlorides that slowly drip 25 milligrams are (available from Alfa Aesar company; Goods number is H27576), stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid after the layering,, follow,, solid is dried up with nitrogen, obtain according to loaded metallocene composite catalyst of the present invention (called after SBA-15-M-GJ-BU-1) with 40 milliliters of hexane wash twice with 10 milliliters of toluene wash three times.Come this loaded metallocene composite catalyst is characterized with XRD, nitrogen adsorption-desorption experiment, transmission electron microscope and ESEM.
Fig. 1 is an X-ray diffracting spectrum, and wherein, figure a is the x-ray diffraction pattern of donut-like SBA-15, and figure b is the x-ray diffraction pattern of loaded metallocene composite catalyst SBA-15-M-GJ-BU-1.Can find out significantly that from XRD spectra SBA-15 1 diffraction peak occurs in little angular region; Explain that donut-like macroporous/mesoporous material SBA-15-M has good mesoporous phase structure; And have two-dimentional hexagonal structure, this is consistent with the mesoporous material XRD spectra of bibliographical information, and behind the load metallocene; Can find out an obvious diffraction spectrum peak in the XRD spectra of sample SBA-15-M-GJ-BU-1 in little angular region, this explanation mesoporous material structure in loading process remains unchanged basically.
Fig. 2 is that (X-coordinate is relative pressure p/p for nitrogen adsorption-desorption graphic representation of donut-like SBA-15 (a1) and loaded metallocene composite catalyst SBA-15-M-GJ-BU-1 (a2) 0); And the pore size distribution curve figure of donut-like SBA-15 (b1) and loaded metallocene composite catalyst SBA-15-M-GJ-BU-1 (b2) (X-coordinate is nm); Nitrogen adsorption-desorption isotherm shows that the donut-like mesoporous material of donut-like macroporous/mesoporous material SBA-15 and load metallocene is the IV class adsorption-desorption thermo-isopleth of typical IUPAC definition among Fig. 2; Proved that donut-like macroporous/mesoporous material SBA-15 has the mesoporous material of the distinctive one dimension column pore passage structure of bibliographical information; And the nitrogen adsorption-desorption thermo-isopleth of the donut-like SBA-15-M-GJ-BU-1 of load metallocene slightly changes, and this is that metallocene entering mesoporous material duct causes in the loading process.Can find out that by graph of pore diameter distribution donut-like macroporous/mesoporous material SBA-15 has narrow pore size distribution; And the duct is very even; Sample after the load keeps narrow pore size distribution and even duct basically, shows that the metallocene loading process does not destroy the meso-hole structure of donut-like mesoporous material to some extent.
Fig. 3 is an ESEM microscopic appearance photo, (a1) with (a2) be the microscopic appearance photo of donut-like SBA-15; (b1) and (b2) be the microscopic appearance photo of loaded metallocene composite catalyst SBA-15-M-GJ-BU-1.Can know that by figure the microscopic appearance figure of the donut-like mesoporous material of donut-like macroporous/mesoporous material SBA-15 and load metallocene is donut-like, and the ratio of the internal diameter of said SBA-15 and external diameter is 0.5, median size is 5 μ m, and mean thickness is 2 μ m.Microscopic appearance through behind the load-reaction remains unchanged basically, still keeps donut-like preferably, the often phenomenon of caving in of appearance of MCM-41 carrier institute do not occur.The spheroidal particle of 955 silica gel behind the load metallocene is high-visible.
Fig. 4 is a transmission electron microscope photo, (a1) with (a2) be the pore passage structure transmission electron microscope photo of donut-like SBA-15; (b1) and (b2) be the pore passage structure transmission electron microscope photo of loaded metallocene composite catalyst SBA-15-M-GJ-BU-1.Can know that from Fig. 4 the donut-like macroporous/mesoporous material of seeing sample donut-like macroporous/mesoporous material SBA-15 and load metallocene has the pore distribution figure of rule.
Table 1 is the pore structure parameter of donut-like SBA-15 and loaded metallocene composite catalyst SBA-15-M-GJ-BU-1.
Table 1
Figure BSA00000318712200131
Data from table 1 can find out that the pore structure parameter of SBA-15-M-GJ-BU-1 all reduces than SBA-15 to some extent, shows that MAO and metallocene compound enter into the duct of SBA-15 really.
Results of elemental analyses shows; Load among the loaded metallocene composite catalyst SBA-15-M-GJ-BU-1 of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of MAO (MAO) and metallocene compound aluminium content be 18.73 weight %; The content of Zr is 0.39 weight %, and the mol ratio of Al/Zr is 164.Total amount with said carried metallocene catalyst is a benchmark, and the total amount of said metallocene compound and alkylaluminoxane is 50 weight %, and the content of said carrier is 50 weight %.
Embodiment 1
This EXPERIMENTAL EXAMPLE is used for explaining olefine polymerizing process of the present invention.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then; With still temperature rise to 80 ℃, add 800 milliliters of hexanes again, along with the adding of hexane; Triethyl aluminum (TEA) (available from the auspicious Dehua of the Zhejiang good fortune worker ltd) hexane solution of 2 milliliter of 1 mol is added; Then add 85.2 milligrams of SBA-15-M-GJ-BU-1, feed ethene and pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 184 gram polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.29g/ml, and melting index is MI 2.16=0.026g/10min.Through calculating, the efficient of catalyzer is 2160g PE/gcat.h (5.1 * 107g PE/ (mol Zr h)).
Embodiment 2
This EXPERIMENTAL EXAMPLE is used for explaining olefine polymerizing process of the present invention.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then; With still temperature rise to 80 ℃, add 800 milliliters of hexanes again, along with the adding of hexane; Triethyl aluminum (TEA) (available from the auspicious Dehua of Zhejiang good fortune worker ltd) hexane solution and 10 milliliters of hexenes of 2 milliliter of 1 mol are added; Then add 79.3 milligrams of SBA-15-M-GJ-BU-1, feed ethene and pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 101 gram multipolymers, the bulk density of this multipolymer (BD) is 0.28g/ml, melting index: MI2.16=0.34g/10min, and the efficient of catalyzer is 1274g PE/gcat.h (3 * 107g PE/ (mol Zrh)).
Comparative Examples 1
With the 400 ℃ of calcinings 10 hours under nitrogen protection of ES955 silica gel, removing hydroxyl and remaining moisture, thereby obtain the ES955 silica gel after the thermal activation.
Under nitrogen protection, 0.9 gram ES955 silica gel is joined in 250 milliliters of glass reactors, add 1.0 gram MAO (MAO) (available from U.S. Albemarle company) and 10ml toluene solutions; Under 50 ℃ of conditions, stirring reaction is after 4 hours, with 30 milliliters of toluene wash 3 times; After finishing; Use 20 milliliters of hexane wash 3 times again, at last solid is dried up with nitrogen, obtaining load has the ES955 of alkylaluminoxane (called after MAO/ES955).
Under nitrogen protection; MAO/ES955 is joined in 250 milliliters of glass reactors, add 20 milliliters of purified toluene (refluxing 24 hours), stir with sodium; Under 30 ℃; Slowly drip the solution of two (n-butyl cyclopentadienyl) zirconium dichlorides (available from Alfa Aesar company, goods number is H27576) of metallocene compound that contain 49 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid,, follow,, solid is dried up with nitrogen with 40 milliliters of hexane wash twice with 10 milliliters of toluene wash three times.Carried metallocene catalyst (called after ES955-BU) with gained.
Results of elemental analyses shows that the aluminium content among the ES955-BU is weight 32.4%, and the content of Zr is weight 0.41%, and the mol ratio of Al/Zr is 270.
Comparative Examples 2
Adopt and carry out the homopolymerization of ethene with embodiment 1 identical method, different is that the catalyzer of employing is the ES955-BU of Comparative Examples 1 preparation.The result obtains 65g polyethylene particle powder, and the bulk density of this polyethylene particle powder (BD) is 0.33g/ml, melting index: MI 2.16=0.12g/10min.Confirm that through calculating the efficient of catalyzer is 1295gPE/gcath (that is, 2.9 * 10 7GPE/ (mol Zr h)).
Comparative Examples 3
Two (n-butyl cyclopentadienyl) zirconium dichlorides of silica gel (ES955-BU) load metallocene catalyst) preparation also is used for ethylene copolymer
Polymerization process is with embodiment 2, and polymerization result: the result obtains 76g polyethylene particle powder, and catalyst efficiency is 2260g PE/gcath (5.1 * 10 7GPE/ (mol Zr h)), bulk density (BD) is 0.299g/ml, melting index: MI 2.16=0.679g/10min.

Claims (17)

1. olefine polymerizing process; This method is included under the olefinic polymerization condition, and one or more alkene are contacted with the loaded metallocene composite catalyst, it is characterized in that; Said loaded metallocene composite catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on the carrier; Said carrier is the mixture of donut-like SBA-15 and silica gel, and said metallocene compound has the structure shown in the formula 1
Wherein, R 1, R 2, R 3, R 4, R 5, R 1', R 2', R 3', R 4' and R 5' be hydrogen or C independently of one another 1-C 5Alkyl, and R 1, R 2, R 3, R 4And R 5In at least one be C 1-C 5Alkyl, R 1', R 2', R 3', R 4' and R 5' at least one be C 1-C 5Alkyl, M is a kind of in titanium, zirconium and the hafnium, X is a halogen.
2. olefine polymerizing process according to claim 1 wherein, is a benchmark with the total amount of composite catalyst, and the total content of said metallocene compound and alkylaluminoxane is 10-60 weight %, and the content of said carrier is 90-40 weight %.
3. olefine polymerizing process according to claim 1, wherein, the weight ratio of donut-like SBA-15 and silica gel is 0.5-20 in the said carrier: 1.
4. according to claim 1,2 or 3 described olefine polymerizing process; Wherein, Said contact is carried out in the presence of the solution that contains aluminum alkyls and/or alkylaluminoxane, and whole aluminium and the mol ratio of the M in the said metallocene compound are 100-200 in said aluminum alkyls and the said alkylaluminoxane: 1.
5. olefine polymerizing process according to claim 4, wherein, the C that respectively does for oneself of the alkyl in said aluminum alkyls and the said alkylaluminoxane 1-C 5Alkyl.
6. olefine polymerizing process according to claim 5, wherein, said aluminum alkyls is a triethyl aluminum.
7. olefine polymerizing process according to claim 5, wherein, said alkylaluminoxane is a MAO.
8. olefine polymerizing process according to claim 1 and 2, wherein, M is a zirconium.
9. olefine polymerizing process according to claim 1 and 2, wherein, X is a chlorine.
10. olefine polymerizing process according to claim 1 and 2, wherein, R 1, R 2, R 3, R 4And R 5In any one be the normal-butyl or the tertiary butyl, R 1', R 2', R 3', R 4' and R 5' in any one be the normal-butyl or the tertiary butyl.
11. olefine polymerizing process according to claim 10, wherein, said metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides.
12. olefine polymerizing process according to claim 1, wherein, the internal diameter of said donut-like SBA-15 and the ratio of external diameter are 0.3-0.9, and median size is 3-20 μ m, and mean thickness is 0.1-2 μ m.
13. olefine polymerizing process according to claim 12, wherein, the most probable aperture of said donut-like SBA-15 is that 7-10nm, specific surface area are that 600-1000 meters squared per gram, pore volume are 0.5-3 milliliter/gram.
14. olefine polymerizing process according to claim 1, wherein, said alkene is one or more in ethene, terminal olefin and the diolefin.
15. olefine polymerizing process according to claim 14, wherein, said alkene is ethene, C 3-C 101-alkene, C 4-C 8Diolefin in one or more.
16. method according to claim 1, wherein, said olefinic polymerization condition comprises that temperature is-78 ℃ to 100 ℃, and pressure is 0.01-10MPa.
17. method according to claim 1, wherein, said olefinic polymerization is carried out in the presence of solvent, and said olefinic polymerization condition comprises: in metallocene compound, the concentration of said carried metallocene catalyst is 1 * 10 -8-1 * 10 -5Mol, temperature are-78 ℃ to 100 ℃, and pressure is 0.01-10MPa.
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