CN102718898B - Olefin polymerization method - Google Patents
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- CN102718898B CN102718898B CN201110080314.3A CN201110080314A CN102718898B CN 102718898 B CN102718898 B CN 102718898B CN 201110080314 A CN201110080314 A CN 201110080314A CN 102718898 B CN102718898 B CN 102718898B
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Abstract
The invention provides an olefin polymerization method, characterized by contacting one or more olefins with a loaded metallocene catalyst under olefin polymerization conditions, wherein the loaded metallocene catalyst comprises a carrier and a metallocene compound loaded on the carrier, and the carrier is rodlike macroporous silica. According to the loaded metallocene catalyst of the invention, the metallocene compound has a sandwich structure and has substituents on cyclopentadienyl, wherein the rodlike macroporous silica has highly-ordered large aperture (11-12 nanometers) and pore volume, good mechanical strength and good macro-molecule catalytic and adsorption properties, thus high catalytic activity is achieved.
Description
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.Due to catalyzed by homogeneous metallocene catalyst, to reach the required methylaluminoxane of high reactivity (MAO) consumption large, and production cost is high, and the polymkeric substance obtaining is without particle shape, cannot in widely used slurry process or gas phase polymerization technique, use.And the activity of metallocene catalyst is very high, in polymerization process, is easy to occur local polymerization velocity very fast, and then causes implode.
The effective way addressing the above problem is carried out load processing solubility metallocene catalyst exactly.At present, relevant Methods for Immobilization of Metallocene Catalysts research report is very many, wherein with SiO
2for example, for the report most study of carrier: CN1095474C, CN1049439C, CN1157419C, US4808561, US5026797, US5763543 and US5661098 all disclose with SiO
2for the carried metallocene catalyst of carrier.But, for furtheing investigate new support/catalyst/co-catalyst system, be necessary to attempt different carriers, to promote further developing of carried catalyst and polyolefin industry.
Molecular sieve is to have evenly regular one dimension or the material of solid netted sieve aperture, and surfactivity is higher, absorption property good, have obvious molecule shape selectivity energy, and it allows the monomer of certain size and the polymkeric substance of formation thereof to insert in the duct of molecular sieve.And because molecular sieve has nano pore, in polymerization process, the inserted mode of monomer is different from freeboard with propagation process, the chance that double-basis stops has been reduced in limited space to a certain extent, makes polyreaction show the feature of " living polymerization ".
Olefin polymerization catalysis is carried on to molecular sieve, and tool has the following advantages:
(1) molecular sieve of synthetic does not contain the impurity that easily makes polymer degradation, will improve the ageing resistance of polyolefine material;
(2) molecular sieve nano pore has the dual-use function of carrier and reactor, and catalyst cupport efficiency is high, and polymerization process is easily controlled, and can in the skeleton of polymerization reactor, key in active centre, accelerates reaction process, improves productive rate;
(3) monomer is inserted with polyreaction and has three-dimensional selection effect, can improve polyolefinic molecular weight and fusing point.
As can be seen here, the olefin coordination polymerization that appears as of molecular sieve carried olefin polymerization catalysis has been opened up a new field.
Compared with industrial silica gel, ordered mesoporous molecular sieve has larger specific surface area, can process larger molecule or group, can make catalyzer bring into play well its due catalytic activity.The mesopore molecular sieve that at present conventional aperture is 5-7 nanometer is as support of the catalyst.Therefore, how to obtain the carried metallocene catalyst of high catalytic efficiency, and then carry out efficiently olefinic polymerization and remain a technical problem urgently to be resolved hurrily.
Summary of the invention
The catalytic efficiency that the object of the invention is to the carried metallocene catalyst that overcomes prior art is still lower, causes the not high problem of efficiency of the olefinic polyreaction that adopts carried metallocene catalyst, and a kind of olefine polymerizing process is efficiently provided.
The present inventor finds, the mesoporous material that suitably increases (if aperture is 11-20 nanometer) by employing aperture is as carrier, the activity of the catalyzer obtaining can obviously improve, trace it to its cause, may be that to adopt aperture be that the mesopore molecular sieve of 5-7 nanometer is during as carrier for existing catalyzer, in loading process, metallocene enters duct and is easy to stop up, and causes the catalytic activity of catalyzer not give full play of, thereby causes the efficiency of olefinic polymerization not high.In addition, in the time carrying out vinyl polymerization, because load metallocene is mainly that load enters abundant inside, duct, when polymerization inductive phase longer, there will not be the implode phenomenon that impairs polymerization reaction kettle.
The invention provides a kind of olefine polymerizing process, the method is included under olefinic polymerization condition, one or more alkene are contacted with carried metallocene catalyst, it is characterized in that, described carried metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on described carrier, and described carrier is bar-shaped macropore mesoporous silicon oxide, and the most probable aperture of described bar-shaped macropore mesoporous silicon oxide is 11-20 nanometer, described metallocene compound has the structure shown in 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 the one in titanium, zirconium and hafnium, X is halogen.
According to olefine polymerizing process of the present invention, because metallocene compound described in used catalyst has sandwich structure, and on cyclopentadienyl, have substituting group, carrier is that most probable aperture is the bar-shaped macropore mesoporous silicon oxide of 11-20 nanometer, and therefore the catalytic activity of catalyzer obviously improves.
Particularly, according to olefine polymerizing process of the present invention, ethylene homo catalytic efficiency can reach 1887gPE/gcat.h (, 3.4 × 10
7gPE/mol Zrh), and in the situation that other conditions are identical, ethylene homo catalytic efficiency when industrial 955 silica gel loads have the metallocene compound of the structure shown in formula 1 only for 1300gPE/gcath (, 2.9 × 10
7gPE/mol Zrh).
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern (a) of bar-shaped macropore meso-porous titanium dioxide silicon carrier KKSBA-15, X-coordinate unit be 2 θ (°), ordinate zou is intensity;
Fig. 2 is the x-ray diffraction pattern (b) of carried metallocene catalyst KKSBA-15-BU, X-coordinate unit be 2 θ (°), ordinate zou is intensity;
Fig. 3 and Fig. 4 are respectively the N of bar-shaped macropore meso-porous titanium dioxide silicon carrier KKSBA-15 (a) and carried metallocene catalyst KKSBA-15-BU (b)
2adsorption desorption graphic representation, wherein, X-coordinate is relative pressure, unit is p/p
0, ordinate zou is pore volume absorption, unit is cm
3/ gSTP;
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution (b) of bar-shaped macropore meso-porous titanium dioxide silicon carrier KKSBA-15 (a) and carried metallocene catalyst KKSBA-15-BU, wherein, X-coordinate is aperture, and unit is nm, ordinate zou is dv/dlog, and unit is cm
3/ g;
In Fig. 7, a is the stereoscan photograph of bar-shaped macropore meso-porous titanium dioxide silicon carrier KKSBA-15, the stereoscan photograph of b carried metallocene catalyst KKSBA-15-BU.
Embodiment
The invention provides a kind of olefine polymerizing process, the method is included under olefinic polymerization condition, one or more alkene are contacted with carried metallocene catalyst, wherein, described carried metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on described carrier, and described carrier is bar-shaped macropore Metaporous silicon dioxide material, and the most probable aperture of described bar-shaped macropore mesoporous silicon oxide is 11-20 nanometer, described metallocene compound has the structure shown in 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 the one in titanium, zirconium and hafnium, X is halogen.
According to the present invention, the M in formula 1 can be the one in titanium, zirconium and hafnium.M in different metallocene compounds can be identical or different, and preferably, M is zirconium.
According to the present invention, the X in formula 1 is halogen.Particularly, the X in formula 1 can be the one in fluorine, chlorine, bromine and iodine.Preferably, the X in formula 1 is chlorine or bromine.X in different metallocene compounds can be identical or different, and more preferably, the X in formula 1 is chlorine.
According to the present invention, in formula 1, cyclopentadienyl is to form η 5 keys and the derivative with the cyclopentadienyl of alkyl substituent with central metal M.Preferably, the R on the cyclopentadienyl in 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
4, 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.
In the present invention, described C
1-C
5alkyl can be one or more in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.
The specific examples that meets the cyclopentadienyl of above-mentioned requirements comprises: methyl-cyclopentadienyl, 1,2-dimethyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, 1,2,3-trimethylammonium-cyclopentadienyl, 1,2,5-trimethylammonium-cyclopentadienyl, 1,2,3,4-tetramethyl--cyclopentadienyl, 1,2,3,5-tetramethyl--cyclopentadienyl, pentamethyl-cyclopentadienyl, ethyl-cyclopentadienyl, 1,2-diethyl-cyclopentadienyl, 1,3-diethyl-cyclopentadienyl, 1,2,4-triethyl-cyclopentadienyl, 1,3,5-triethyl-cyclopentadienyl, methyl-2-ethyl-cyclopentadienyl, 1-methyl-3-ethyl-cyclopentadienyl, n-propyl-cyclopentadienyl, 1,3-diη-propyl-cyclopentadienyl, 1-methyl-3-n-propyl-cyclopentadienyl, 1,3-di-isopropyl-cyclopentadienyl, 1-methyl-3-sec.-propyl-cyclopentadienyl, normal-butyl-cyclopentadienyl, 1,3-di-n-butyl-cyclopentadienyl, 1-methyl-3-normal-butyl-cyclopentadienyl, sec-butyl-cyclopentadienyl, 1,3-di-sec-butyl-cyclopentadienyl, 1-methyl-3-sec-butyl-cyclopentadienyl, 1-isobutyl--cyclopentadienyl, 1,3-diisobutyl-cyclopentadienyl, 1-methyl 3-isobutyl--cyclopentadienyl, the tertiary butyl-cyclopentadienyl, 1,3-di-t-butyl-cyclopentadienyl, the 1-methyl 3-tertiary butyl-cyclopentadienyl, n-pentyl-cyclopentadienyl, 1,3-, bis-n-pentyls-cyclopentadienyl, 1-methyl-3-n-pentyl-cyclopentadienyl, 1-isopentyl-cyclopentadienyl, 1,3-diisoamyl-cyclopentadienyl, 1-methyl-3-isopentyl-cyclopentadienyl, 1-tert-pentyl-cyclopentadienyl, 1,3-, bis-tert-pentyls-cyclopentadienyl, 1-methyl-3-tert-pentyl-cyclopentadienyl, neo-pentyl-cyclopentadienyl, 1,3-di neo-pentyl-cyclopentadienyl, 1-methyl-3-neo-pentyl-cyclopentadienyl.
Preferably, the R in formula 1
1, R
1' and 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 meets the cyclopentadienyl of above-mentioned requirements comprises: methyl-cyclopentadienyl, ethyl-cyclopentadienyl, n-propyl-cyclopentadienyl, sec.-propyl-cyclopentadienyl, normal-butyl-cyclopentadienyl, sec-butyl-cyclopentadienyl, isobutyl--cyclopentadienyl, the tertiary butyl-cyclopentadienyl, n-pentyl-cyclopentadienyl, isopentyl-cyclopentadienyl, tert-pentyl-cyclopentadienyl, neo-pentyl-cyclopentadienyl.
More preferably, R
1and R
1' be C
4alkyl, R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.Particularly, described cyclopentadienyl is n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl, isobutyl-cyclopentadienyl, tertiary butyl cyclopentadienyl.
According to the present invention, described alkylaluminoxane can be the conventional various alkylaluminoxanes in metallocene catalyst field.Usually, the alkyl in described alkylaluminoxane is C as above
1-C
5alkyl.Preferably, described alkylaluminoxane is methylaluminoxane.
The present inventor finds in research process, the R in formula 1
1and R
1' be normal-butyl, M is zirconium, X is chlorine, be that described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, and when alkylaluminoxane is methylaluminoxane, when described carried metallocene catalyst is used for the polyreaction of catalyzed alkene, demonstrate excellent catalytic activity.
According to the present invention, loading on metallocene compound on described carrier and the amount of alkylaluminoxane can change within a large range.The present inventor finds, take the total amount of described carried metallocene catalyst as benchmark, the total amount of described metallocene compound and alkylaluminoxane is 20-50 % by weight, and the content of described carrier is 50-80 % by weight.Under preferable case, take the total amount of described carried metallocene catalyst as benchmark, the total amount of described metallocene compound and alkylaluminoxane is 30-40 % by weight, and the content of described carrier is 60-70 % by weight.Further under preferable case, take the total amount of described carried metallocene catalyst as benchmark, the total amount of described metallocene compound and alkylaluminoxane is 33-34 % by weight, and the content of described carrier is 66-67 % by weight.
According to the present invention, the ratio loading between described alkylaluminoxane and the metallocene compound on described carrier can be the known ratio of technician of field of olefin polymerisation.Preferably, the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound can be that the mol ratio of M can be 50-200: 1, be preferably 80-120: and 1, more preferably 90-110: 1, most preferably be 100: 1.
According to carried metallocene catalyst of the present invention, described metallocene compound has sandwich structure, and on cyclopentadienyl, there is substituting group, according to carried metallocene catalyst of the present invention, wherein, the length of bar-shaped carrier is 2-20 micron, length-to-diameter ratio is 2-8, specific surface area is 300-600 meters squared per gram, and pore volume is 0.3-1.5 ml/g, and most probable aperture is 11-20 nanometer;
Under preferable case, the length of bar-shaped carrier is 3-15 micron, and length-to-diameter ratio is 3-7, and specific surface area is 300-500 meters squared per gram, and pore volume is 0.5-1.2 ml/g, and most probable aperture is 11-15 nanometer;
Further, under preferable case, the length of bar-shaped carrier is 3-9 micron, and length-to-diameter ratio is 4-6 micron, and specific surface area is 300-400 meters squared per gram, and pore volume is 0.8-1.2 ml/g, and most probable aperture is 11-12 nanometer;
Under most preferred case, the length of bar-shaped carrier is 4 microns, and length-to-diameter ratio is 5, and specific surface area is 351 meters squared per gram, and pore volume is 1.0 mls/g, and most probable aperture is 12 nanometers.
Described bar-shaped macropore mesoporous silicon oxide can prepare by the method comprising the following steps:
(1) template, water and HCl are stirred to dissolving at 25-60 ℃ of temperature;
(2) step (1) gained solution and tetraethoxy are stirred more than 0.2 hour at 25-60 ℃ of temperature;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) alcoholic solvent that is 1-4 by step (3) gained crystallization product with carbonatoms contact, with removed template method;
Described template is polyoxyethylene-polyoxytrimethylene-polyoxyethylene triblock copolymer.
Described crystallization condition comprises that crystallization temperature is 90-180 ℃, and crystallization time is 10-40 hour.
The condition that described crystallization product contacts with the alcoholic solvent that carbonatoms is 1-4 comprises that temperature is 90-120 ℃, and the time is 10-40 hour.
Described crystallization product and carbonatoms are that the weight ratio of the alcoholic solvent of 1-4 is 1: 100-300.
Described carbonatoms is that the alcoholic solvent of 1-4 is ethanol.
Meter in molar ratio, polyoxyethylene-polyoxytrimethylene-polyoxyethylene: water: hydrogenchloride=1: 9000-15000: 100-500, preferably 1: 10000: 290.Wherein, the mole number of polyoxyethylene-polyoxytrimethylene-polyoxyethylene calculates according to the molecular-weight average of polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
According to the present invention, described carried metallocene catalyst can be by under protection of inert gas, successively load alkylaluminoxane and metallocene compound and obtain on carrier.In the carried metallocene catalyst that described alkylaluminoxane and the metallocene compound charge capacity on described carrier makes to obtain, the content of alkylaluminoxane and metallocene compound meets previously described requirement.
According to the present invention, the kind of described alkylaluminoxane and metallocene compound have been described in detail above, repeats no more herein.
Can adopt the method for well known to a person skilled in the art that alkylaluminoxane and metallocene compound are loaded on described carrier.Preferably, successively on carrier, the method for load alkylaluminoxane and metallocene compound comprises: under protection of inert gas, described carrier is contacted with the first solution, described the first solution contains described alkylaluminoxane and the first solvent; The carrier that has removed described the first solvent is contacted with the second solution, and described the second solution contains described metallocene compound and the second solvent, and removes the second solvent.Described the first solvent and the second solvent can be identical or different, are preferably toluene.
Under preferable case, meter in molar ratio, carrier: toluene: the amount ratio of alkylaluminoxane is 1: 10-100: 0.1-2.
Under preferable case, meter in molar ratio, carrier: toluene: the amount ratio of metallocene compound is 1: 20-150: 2 × 10
-3-19 × 10
-3.
Wherein, the mole number of alkylaluminoxane is in RAlO, and wherein R is alkyl, and the mole number of for example methylaluminoxane is with CH
3alO (58) meter, the mole number of carrier is in silicon-dioxide.
The present invention is for described carrier being contacted with the first solution and the carrier that has removed described the first solvent being not particularly limited with the method that the second solution contacts, the whole bag of tricks that can be known to the skilled person, for example: dipping, spraying.Adopt the method for dipping can make solution enter more fully in the duct on carrier, therefore, the present invention is preferably flooded.
Carrier is not particularly limited with the condition that the second solution contacts with the first solution, for example: carrier can comprise with the condition that described the first solution contacts: the time is 1-10 hour, and temperature is 25-80 ℃; The described carrier that has removed toluene can be comprised with the condition that described the second solution contacts: the time is 0.3-2 hour, and temperature is 25-80 ℃.
According to the present invention, toluene preferably adopts and well known to a person skilled in the art that method refines before use, for example: can within 24-48 hour, refine by toluene is refluxed on sodium, with except impurity such as water in desolventizing.
According to the present invention; also preferably before alkylaluminoxane described in load and described metallocene compound; under protection of inert gas; described carrier is heated to 7-10 hour at the temperature of 300-900 ℃, for example, to remove the volatile matter (: water) containing in the hydroxyl of carrier surface and carrier.Preferably; the method according to this invention is included in described in load before alkylaluminoxane and described metallocene compound, under protection of inert gas, described carrier is heated to 9-10 hour at the temperature of 350-450 ℃; more preferably, at the temperature of 400 ℃, heat 10 hours.
According to the present invention, can be for not there is not chemically interactive various gas with carrier, alkylaluminoxane, metallocene compound in described rare gas element.For example, described rare gas element can be nitrogen, argon gas.
According to the present invention, described alkylaluminoxane and the metallocene compound charge capacity on described carrier makes total amount take described carried metallocene catalyst as benchmark, the total amount of described metallocene compound and alkylaluminoxane can be 20-50 % by weight, more preferably 30-40 % by weight, is further preferably 33-34 % by weight; The content of described carrier can be 50-80 % by weight; More preferably 60-70 % by weight, is further preferably 66-67 % by weight; The mol ratio of M in aluminium in described alkylaluminoxane and described metallocene compound can be 50-200: 1 is preferably 80-120: 1, and more preferably 90-110: 1, most preferably be 100: 1.A preferred embodiment of the invention, the preparation method of described carried metallocene catalyst comprises:
The 1st step, using triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene as template, join in aqueous hydrochloric acid, press molar feed ratio, triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene: water: hydrogenchloride=1: 9000-15000: 100-500, preferably 1: 10000: 290, at 25 ℃ of-60 ℃ of temperature, be stirred to dissolving;
The 2nd step adds tetraethoxy in previous step gained solution, at 25 ℃ of-60 ℃ of temperature, stirs more than 25 minutes, preferably at 40 ℃, stirs 24 hours;
The 3rd step, is placed in closed reaction vessel by upper step gained solution, crystallization 10 hours-40 hours at 90 ℃ of-180 ℃ of temperature, preferably crystallization 24 hours at 150 ℃;
The 4th step, filters crystallization after product, wash, be dried, and obtains the former powder of bar-shaped macropore mesoporous silicon oxide;
The 5th step, washs the former powder of bar-shaped gained macropore mesoporous silicon oxide 10 hours-40 hours at 90 ℃ of-120 ℃ of temperature with ethanol, preferably at 100 ℃, washs 10 hours, and removed template method, obtains bar-shaped macropore mesoporous silicon oxide;
The 6th step, thermal activation step under nitrogen protection, in 300-900 ℃ of calcining 7-10 hour, is preferably calcined bar-shaped upper step gained macropore mesoporous silicon oxide 10 hours at 400 ℃, obtains the bar-shaped macropore mesoporous silicon oxide after thermal activation;
The 7th step, bar-shaped macropore mesoporous silicon oxide after thermal activation is transferred in the reactor after nitrogen is fully replaced, add toluene and alkylaluminoxane, meter in molar ratio, bar-shaped macropore mesoporous silicon oxide (take silicon-dioxide): toluene: the amount ratio of alkylaluminoxane is 1: 10-100: 0.1-2, preferably 1: 45: 1, stir 1-10 hour in 25-80 ℃ again, preferably at 50 ℃, stir 4 hours, after, with hexane washing 3 times, afterwards solid is dried up with nitrogen again, obtain the bar-shaped macropore mesoporous silicon oxide of load methylaluminoxane;
The 8th step, under nitrogen protection, joins the bar-shaped macropore mesoporous silicon oxide of load methylaluminoxane in reactor, adds stirring solvent to make slurries; In the container of crossing with nitrogen replacement in advance, metallocene compound is dissolved and makes solution, under 25-80 ℃ of agitation condition, preferably under 30 ℃ of stirrings, slowly metallocene compound solution is added drop-wise in reactor, meter in molar ratio, bar-shaped macropore mesoporous silicon oxide (take silicon-dioxide): toluene: the amount ratio of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of metallocene compound is 1: 20-150: 2 × 10
-3-19 × 10
-3, stirring reaction 0.3-2 hour, preferable amount ratio is 1: 45: 12.4 × 10
-3, stir 0.5 hour, after reaction finishes, leave standstill, leach liquid, with the washing of toluene and hexane, dry up with nitrogen, obtain described carried metallocene catalyst.
According to olefine polymerizing process of the present invention, described one or more alkene can carry out with contacting of described carried metallocene catalyst under the existence of solvent, and described solvent is preferably and replaces or unsubstituted alkane or replacement or unsubstituted aromatic hydrocarbons.In the time that described alkane and aromatic hydrocarbons have substituting group, described substituting group is preferably halogenic substituent.More preferably, described solvent is one or more in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform and methylene dichloride.
The consumption of described solvent can carry out appropriate selection according to concrete use occasion.Preferably, to make the concentration of described carried metallocene catalyst be 1 × 10 to the consumption of described solvent
-8-1 × 10
-3mol/L, is preferably 1 × 10
-8-1 × 10
-5mol/L.
According to olefine polymerizing process of the present invention, described one or more alkene carry out under the solution that contains aluminum alkyls and/or alkylaluminoxane exists with contacting preferably of described carried metallocene catalyst.,, according to olefine polymerizing process of the present invention, preferably, in the time carrying out polymerization, in reaction system, supplement the solution that interpolation contains aluminum alkyls and/or alkylaluminoxane.Play the effect of cleaning reaction poisonous substance in the aluminum alkyls in solution and/or alkylaluminoxane with together with alkylaluminoxane on loading on described carrier, thereby the metallocene compound that makes to load on described carrier can be brought into play katalysis better.
According to olefine polymerizing process of the present invention, when the solution that containing aluminum alkyls and/or alkylaluminoxane with contacting of described carried metallocene catalyst at described one or more alkene carries out under existing, the mol ratio of the M in described aluminum alkyls and described alkylaluminoxane (comprising the alkylaluminoxane that loads on described carrier and the alkylaluminoxane in solution) in whole aluminium and described metallocene compound can be 100-3000: 1.
Described aluminum alkyls can be the aluminum alkyls of the known various promotors as metallocene catalyst of the technician of field of olefin polymerisation.Preferably, the alkyl in described aluminum alkyls can be C
1-C
5alkyl.More preferably, described aluminum alkyls is triethyl aluminum.
Alkylaluminoxane in solution can be identical with the kind that loads on the alkylaluminoxane (, the alkylaluminoxane that the supplementary alkylaluminoxane adding contains with described carried metallocene catalyst) on described carrier, also can be different; Be preferably identical.
According to olefine polymerizing process of the present invention, described alkene can be one or more in ethene, alpha-olefin and diolefin.Preferably, described alkene is ethene, C
3-C
101-alkene, C
4-C
8diolefin in one or more.More preferably, described alkene is one or more in ethene, 1-butylene, 1-amylene and 1-hexene.
According to olefine polymerizing process of the present invention, because the present invention is efficiency by improve polyreaction with described carried metallocene catalyst, therefore the present invention is not particularly limited for described olefinic polymerization condition.It can be the known polymerizing condition of technician of field of olefin polymerisation.Preferably, in metallocene compound, the concentration of described carried metallocene catalyst can be 1 × 10
-8-1 × 10
-5mol/L.The temperature of polymerization can be-78 ℃ to 100 ℃, is preferably 0 ℃-90 ℃; Pressure can be 0.01-10MPa, is preferably 0.01-2MPa.
Below in conjunction with embodiment, the present invention is described in detail.
In following examples, X-ray diffraction analysis carries out on the X-ray diffractometer that purchased from the model of company of German Bruker AXS company is D8 Advance; TEM (transmission electron microscope) analysis is to carry out on the transmission electron microscope of Tecnai 20 in the model purchased from company of Dutch FEI Co.; In the scanning electronic microscope that scanning electron microscope analysis is XL-30 in the model purchased from FEI Co. of the U.S., carry out.Ultimate analysis is carried out on the instrument of the model 7500CX purchased from An Jielun company of the U.S..Nitrogen adsorption-desorption experiment condition comprises: the U.S. Autosorb-1 of Kang Ta company nitrogen adsorption desorption instrument, sample is degassed 4 hours at 200 ℃.
Preparation example 1
This preparation example is for the preparation of the carried metallocene catalyst using in olefine polymerizing process according to the present invention.
The 1st step, joins 4.0 grams of P123 (material that is 9003-11-6 in the registration number of U.S. chemical abstract, its average molecular mass Mn=5800) in the hydrochloric acid of 16.4ml 37% and the solution of 128ml water, is stirred to P123 dissolves completely at 40 ℃;
The 2nd step, then 8.86 grams of tetraethoxys are joined in above-mentioned solution and stirred 24 hours at 40 ℃;
The 3rd step, transferred to gained solution in teflon-lined reactor, 150 ℃ of crystallization 24 hours;
The 4th step obtains former powder mesoporous material after filtering, wash, being dried;
The 5th step, under reflux conditions washs former powder mesoporous material 24 hours with ethanol, and removed template method obtains bar-shaped macroporous/mesoporous material (called after KKSBA-15).
By bar-shaped macroporous/mesoporous material KKSBA-15 under nitrogen protection 400 ℃ calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the bar-shaped macroporous/mesoporous material through thermal activation.
0.25 gram of bar-shaped macroporous/mesoporous material through thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, adds 20 milliliters of refining toluene, 0.25 gram of methylaluminoxane (purchased from Albemarle Corporation of the U.S.) to stir 4 hours in 50 ℃.After, then with 20 milliliters of hexane washings three times, finally solid is dried up with nitrogen, obtaining load has the bar-shaped macroporous/mesoporous material of methylaluminoxane (called after MAO/KKSBA-15).
Under nitrogen protection; the MAO/KKSBA-15 obtaining is all joined in 250 milliliters of glass reactors; add 20 milliliters of refining toluene; at 30 ℃; slowly drip two (n-butyl cyclopentadienyl) zirconium dichlorides of 20.9 milligrams (purchased from AlfaAesar; article No. H27576), stirring reaction 0.5 hour.After reaction finishes, leave standstill, after layering, leach liquid, by 10 milliliters of toluene wash three times, follow, by 40 milliliters of hexane washed twice, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after KKSBA-15-BU).This carried metallocene catalyst is characterized with x-ray diffractometer (XRD), the experiment of nitrogen adsorption-desorption, scanning electron microscope, X-ray energy spectrometer and ICP ultimate analysis.
Fig. 1 is the little angle x-ray diffraction pattern of bar-shaped macropore mesoporous silicon oxide KKSBA-15, and Fig. 2 is the little angle x-ray diffraction pattern of carried metallocene catalyst KKSBA-15-BU.Can obviously be found out by XRD spectra, all there is Small angle spectrum peak in bar-shaped macropore mesoporous silicon oxide KKSBA-15 and carried metallocene catalyst KKSBA-15-BU, illustrates that the macropore KKSBA-15-BU of load metallocene has the peculiar two-dimentional hexagonal hole of mesoporous material road structure.
Fig. 3 and Fig. 4 are respectively the N of macropore meso-porous titanium dioxide silicon carrier KKSBA-15 and carried metallocene catalyst KKSBA-15-BU
2adsorption desorption graphic representation, wherein, X-coordinate is relative pressure, unit is p/p
0.Fig. 4 shows that KKSBA-15-BU has the IV type thermoisopleth of sharp-pointed capillary condensation speed, and this thermoisopleth has H1 hysteresis loop, and this shows that KKSBA-15-BU has the aperture size distribution of homogeneous.
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution of macropore meso-porous titanium dioxide silicon carrier KKSBA-15 and carried metallocene catalyst KKSBA-15-BU, and wherein, X-coordinate is aperture, and unit is nm.As seen from the figure, KKSBA-15 and KKSBA-15-BU have six sides' meso-hole structure, and duct is very even.
Fig. 7 is stereoscan photograph, and a is the stereoscan photograph of composite mesopore silica supports KKSBA-15, and b is the stereoscan photograph of carried metallocene catalyst KKSBA-15-BU.As seen from the figure, the microscopic appearance of KKSBA-15 and KKSBA-15-BU is bar-shaped, and in loading process, KKSBA-15-BU has good mechanical property.
Table 1 is the pore structure parameter of bar-shaped macropore mesoporous silicon oxide KKSBA-15 and carried metallocene catalyst KKSBA-15-BU.
Table 1 pore structure parameter
Data by upper table 1 can find out, bar-shaped macropore mesoporous silicon oxide KKSBA-15 after load metallocene, pore volume, specific surface area and aperture all reduce to some extent, this explanation metallocene in load-reaction process enters into the inside of bar-shaped macropore mesoporous silicon oxide.
Ultimate analysis ICP result shows, load the aluminium content of bar-shaped macropore mesoporous silicon oxide KKSBA-15-BU of two (n-butyl cyclopentadienyl) zirconium dichlorides (BUCP) of methylaluminoxane (MAO) and metallocene compound be 14.6 % by weight, the content of Zr is 0.5 % by weight, and the mol ratio of Al/Zr is 100: 1.Learn through converting, take the total amount of catalyzer as benchmark, the total content of methylaluminoxane (MAO) and metallocene compound is 33.6 % by weight, and the content of carrier is 66.4 % by weight.
The present embodiment is used for explanation according to olefine polymerizing process of the present invention.
In the stainless steel polymermaking autoclave of 2 liters, with the each displacement of nitrogen and ethene three times, then add 200 milliliters of hexanes, by still temperature rise to 80 ℃, then add 800 milliliters of hexanes, along with adding of hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol/L, then add 47.7 milligrams of KKSBA-15-BU, pass into ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 90 grams of polyethylene particle powders, the bulk density (BD) of this polyethylene particle powder is 0.222g/ml, melting index MI
2.16=0.025g/10min.Determine as calculated, the efficiency of catalyzer is 1887gPE/gcath (, 3.4 × 10
7gPE/mol Zrh).
The present embodiment is used for explanation according to olefine polymerizing process of the present invention.
In the stainless steel polymermaking autoclave of 2 liters, with the each displacement of nitrogen and ethene three times, then add 200 milliliters of hexanes, by still temperature rise to 70 ℃, then add 800 milliliters of hexanes, along with adding of hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution and 10 milliliters of hexenes of 1 mol/L, then add the KKSBA-15-BU of 44.6 milligrams, pass into ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 68 grams of polymkeric substance, the bulk density (BD) of this polymkeric substance is 0.205g/ml, melting index MI
2.16=0.058g/10min.Determine as calculated, the efficiency of catalyzer is 1525gPE/gcath (, 2.8 × 10
7gPE/mol Zrh).
Preparation comparative example 1
This prepares comparative example for illustrating that carrier is the preparation of the carried metallocene catalyst of ES955 silica gel.
By ES955 silica gel under nitrogen protection 400 ℃ calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the silica gel through the ES955 of thermal activation.
Under nitrogen protection; 0.9 gram of ES955 silica gel is joined in 250 milliliters of glass reactors; add again 1.0 grams of methylaluminoxane and 10mL toluene; under 50 ℃ of conditions; after stirring reaction 4 hours, by toluene wash 3 times, then wash three times with 20 milliliters of hexanes; finally solid is dried up with nitrogen, obtaining load has the ES955 of methylaluminoxane (called after MAO/ES955).
Under nitrogen protection; MAO/ES955 is joined in 250 milliliters of glass reactors; add 20 milliliters of refining toluene (with sodium backflow 24 hours); at 30 ℃; slowly drip two (normal-butyl-cyclopentadienyl) zirconium dichlorides of metallocene compound of 44 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid, by 10 milliliters of toluene wash three times, follow, by 40 milliliters of hexane washed twice, solid is dried up with nitrogen, obtain carried metallocene catalyst (called after MAO/ES955-BU).
Results of elemental analyses demonstration, the content of the aluminium in ES955-BU is 32.4 % by weight, and the content of Zr is 0.41 % by weight, and the mol ratio of Al/Zr is 270: 1.
Preparation comparative example 2
This prepares comparative example for illustrating that metallocene compound is bicyclic pentadiene zirconium dichloride CpZrCl
2the preparation of carried metallocene catalyst.
Adopt the method identical with preparation example 1 to prepare carried metallocene catalyst, different, adopt bicyclic pentadiene zirconium dichloride CpZrCl
2as metallocene compound, obtain carried metallocene catalyst (called after KKSBA-15-Cp).Results of elemental analyses demonstration, the aluminium content in KKSBA-15-Cp is 24 % by weight, and the content of Zr is 1 % by weight, and the mol ratio of Al/Zr is 81: 1.
Comparative example 1
Adopt the method identical with embodiment 1 to carry out the homopolymerization of ethene, different is, the catalyzer adopting is ES955-BU prepared by preparation comparative example 1, add 50 milligrams of ES955-BU, result obtains 65g polyethylene particle powder, the bulk density (BD) of this polyethylene particle powder is 0.331g/ml, melting index: MI
2.16=0.119g/10min.Determine as calculated, the efficiency of catalyzer is 1300gPE/gcath (, 2.9 × 10
7gPE/mol Zrh).
Comparative example 2
Adopt the method identical with embodiment 2 that ethene and hexene are carried out to copolymerization, different is, the catalyzer adopting is ES955-BU prepared by preparation comparative example 1, add 60 milligrams of ES955-BU, obtain 60 grams of polymkeric substance, the density (BD) of this polymer stacks is 0.299g/ml, and melting index is MI2.16=0.679g/10min.Determine as calculated, the efficiency of catalyzer is 1000gPE/gcath (, 2.2 × 10
7gPE/mol Zrh).
Comparative example 3
Adopt the method identical with embodiment 1 to carry out the homopolymerization of ethene, different, the catalyzer of employing is KKSBA-15-Cp prepared by preparation comparative example 2.Result obtains 36g polyethylene particle powder, adds 93 milligrams of KKSBA-15-Cp, and the bulk density (BD) of this polyethylene particle powder is 0.30g/ml, melting index: MI
2.16=0.011g/10min.Determine as calculated, the efficiency of catalyzer is 387gPE/gcath (, 3.5 × 10
6gPE/mol Zrh).
Comparative example 4
Adopt the method identical with embodiment 2 that ethene and hexene are carried out to copolymerization, different is, the catalyzer adopting is KKSBA-15-Cp prepared by preparation comparative example 2, add 98 milligrams of KKSBA-15-Cp, obtain the multipolymer of 43 grams of ethene and hexene, the density (BD) of the multipolymer heap of this ethene and hexene is 0.304g/ml, and melting index is MI
2.16=0.077g/10min.Determine as calculated, the efficiency of catalyzer is 439gPE/gcath (, 4.0 × 10
6gPE/mol Zrh).
Claims (15)
1. an olefine polymerizing process, the method is included under olefinic polymerization condition, one or more alkene are contacted with carried metallocene catalyst, it is characterized in that, described carried metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on described carrier, and described carrier is bar-shaped macropore mesoporous silicon oxide, and the most probable aperture of described bar-shaped macropore mesoporous silicon oxide is 11-20 nanometer, described metallocene compound has the structure shown in formula 1
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 the one in titanium, zirconium and hafnium, X is halogen.
The length of described carrier is 2-20 micron, and length-to-diameter ratio is 2-8, and specific surface area is 300-600 meters squared per gram, and pore volume is 0.3-1.5 ml/g; Described specific surface area adopts nitrogen adsorption-desorption method to measure.
2. olefine polymerizing process according to claim 1, wherein, take the total amount of described carried metallocene catalyst as benchmark, the total amount of described metallocene compound and alkylaluminoxane is 20-50 % by weight, the content of described carrier is 50-80 % by weight.
3. olefine polymerizing process according to claim 1 and 2, wherein, the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound is 50-200:1.
4. olefine polymerizing process according to claim 1, wherein, M is zirconium, X is chlorine.
5. olefine polymerizing process according to claim 1, wherein, the R in described metallocene compound
1, R
1' be C
1-C
5alkyl, and R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen; Alkyl in described alkylaluminoxane is C
1-C
5alkyl.
6. olefine polymerizing process according to claim 5, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides.
7. according to the olefine polymerizing process described in claim 5 or 6, wherein, described alkylaluminoxane is methylaluminoxane.
8. olefine polymerizing process according to claim 1, wherein, described carrier is made by the method comprising the following steps:
(1) template, water and HCl are stirred to dissolving at 25-60 ℃ of temperature;
(2) step (1) gained solution and tetraethoxy are stirred more than 0.2 hour at 25-60 ℃ of temperature;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) alcoholic solvent that is 1-4 by step (3) gained crystallization product with carbonatoms contacts, with removed template method;
Described template is polyoxyethylene-polyoxytrimethylene-polyoxyethylene triblock copolymer.
9. olefine polymerizing process according to claim 8, wherein, described crystallization condition comprises: crystallization temperature is 90-180 ℃, crystallization time is 10-40 hour.
10. olefine polymerizing process according to claim 8, wherein, the condition that described crystallization product contacts with the alcoholic solvent that carbonatoms is 1-4 comprises that temperature is 90-120 ℃, and the time is 10-40 hour, and the weight ratio of the alcoholic solvent that crystallization product and carbonatoms are 1-4 is 1:100-300.
Olefine polymerizing process described in 11. according to Claim 8 or 10, wherein, the alcoholic solvent that described carbonatoms is 1-4 is ethanol.
12. olefine polymerizing process according to claim 8, wherein, meter in molar ratio, polyoxyethylene-polyoxytrimethylene-polyoxyethylene: water: hydrogenchloride=1:9000-15000:100-500.
13. olefine polymerizing process according to claim 1, wherein, described alkene is one or more in ethene, alpha-olefin and diolefin.
14. olefine polymerizing process according to claim 13, wherein, described alkene is ethene, C
3-C
101-alkene, C
4-C
8diolefin in one or more.
15. methods according to claim 1, wherein, described contact is carried out in solvent, and described olefinic polymerization condition comprises: in metallocene compound, the concentration of described carried metallocene catalyst is 1 × 10
-8-1 × 10
-5mol/L, temperature is-78 ℃ to 100 ℃, pressure is 0.01-10MP
a.
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| Cristian Covarrubias,et al.(High catalytic activity of SBA-15-supported metallocene toward ethylene polymerization: The effect of the ordered porous structure of the support.《Catalysis Communications》.2008,第10卷995-1001. * |
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