CN102453135A - Olefin polymerization method - Google Patents
Olefin polymerization method Download PDFInfo
- Publication number
- CN102453135A CN102453135A CN2010105193110A CN201010519311A CN102453135A CN 102453135 A CN102453135 A CN 102453135A CN 2010105193110 A CN2010105193110 A CN 2010105193110A CN 201010519311 A CN201010519311 A CN 201010519311A CN 102453135 A CN102453135 A CN 102453135A
- Authority
- CN
- China
- Prior art keywords
- carrier
- alkylaluminoxane
- sba
- alkyl
- metallocene catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a high-efficiency olefin polymerization method, which comprises a step of: contacting one or more olefins with a supported metallocene catalyst under the olefin polymerization conditions, wherein the supported metallocene catalyst comprises a carrier, and a metallocene compound and alkyl aluminoxane which are supported on the carrier, and is characterized in that: the carrier is SBA-15; the metallocene compound has a structure shown as a formula 1; and in the formula, R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' independently refer to hydrogen or alkyl with 1o 5 carbon atoms, at least one of R1, R2, R3, R4 and R5 refers to alkyl with 1 to 5 carbon atoms, at least one of R1', R2', R3', R4' and R5' refers to alkyl with 1 to 5 carbon atoms, M refers to one of titanium, zirconium and hafnium, and X is halogen. In the olefin polymerization method, the catalyst with high catalytic activity is used, and the catalytic efficiency is high, so a great amount of polymer can be obtained through a small amount of catalyst.
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.Because to reach the required MAO of high reactivity (MAO) consumption big for the homogeneous phase metallocene catalyst, production cost is high, and the polymkeric substance that obtains do not have particle shape, can't on widely used slurry process or gas phase polymerization technology, use.And the activity of metallocene catalyst is very high, and it is very fast in polymerization process, to be easy to take place local polymerization velocity, and then causes implode.
The effective way that addresses the above problem is carried out the load processing to the solubility metallocene catalyst exactly.At present, relevant metallocene catalyst load research report is very many, wherein with SiO
2Maximum for the report research of carrier, for example: CN1095474C, CN1049439C, CN1157419C, US4808561, US5026797, US5763543 and US5661098 all disclose with SiO
2Carried metallocene catalyst for carrier.Yet, 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 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.And 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 ".
Olefin polymerization catalysis is carried on molecular sieve, has following advantage:
(1) molecular sieve of synthetic does not contain the impurity that is prone to make polymer degradation, will improve polyolefine hydrocarbon aging resistance of materials;
(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.
Compare with zeolite molecular sieve, ordered mesoporous molecular sieve (aperture is the molecular sieve of 2-50nm) has bigger specific surface area and relatively large aperture, can handle bigger molecule or group, can make catalyzer bring into play its due catalytic activity well.
CN1718596A discloses a kind of carried metallocene catalyst, and this catalyzer is through with Cp
2ZrCl
2Loading on the SBA-15 that handles through MAO goes up and obtains.But the catalytic activity of the disclosed carried metallocene catalyst of CN1718596A awaits further to improve.
CN1923862A discloses a kind of olefin polymerization catalysis of mesoporous molecular sieve carriedization, and this catalyzer is upward to obtain through the semi-sandwich alum metallic compound shown in the following formula being loaded on the SBA-15 that handles through MAO,
But the catalytic activity of the disclosed catalyzer of CN1923862A is the highest also has only 10
6GPE/ (molZrh).
Therefore, the carried metallocene catalyst that how to obtain to have high catalytic activity remains a technical problem that needs to be resolved hurrily.
Summary of the invention
The catalytic efficiency (of carried metallocene catalyst that the objective of the invention is to overcome prior art is still lower, causes adopting the not high problem of efficient of the olefinic polyreaction of carried metallocene catalyst, and a kind of olefine polymerizing process efficiently is provided.
The invention provides a kind of olefine polymerizing process; This method is included under the olefinic polymerization condition, and one or more alkene are contacted with carried metallocene catalyst, and said carried metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on the said carrier; It is characterized in that; Said carrier is SBA-15, 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.
According to olefine polymerizing process of the present invention; Metallocene compound in the carried metallocene catalyst that adopts has sandwich structure; And have substituting group on the cyclopentadienyl moiety, it is loaded on the mesoporous material SBA-15 of high mechanical strength and good catalysis absorption property, can access a Stability Analysis of Structures; Therefore the carried metallocene catalyst that catalytic activity is high has high catalytic activity.Particularly, according to olefine polymerizing process of the present invention, carried metallocene catalyst is when being used for catalysis in olefine polymerization, and catalytic efficiency (can be 4000-7000gPE/ (gcath) (10
7And the catalyzer catalytic efficiency (under the same conditions that the disclosed semi-sandwich alum metallic compound of CN1923862A loads on the SBA-15 that MAO handles is 1000gPE/ (gcath) gPE/ (mol Zrh)); The open Cp of CN1718596A
2ZrCl
2The catalyzer catalytic efficiency (under the same conditions that loads on the SBA-15 that MAO handles is 10
6GPE/ (molZrh).
Description of drawings
Fig. 1 is an X-ray diffracting spectrum, and wherein, a is the x-ray diffraction pattern of SBA-15, and b is the x-ray diffraction pattern of SBA-15-BU-1.
A among Fig. 2 is that nitrogen adsorption-desorption of SBA-15-BU-1 attaches graphic representation, and the b among Fig. 2 is the graph of pore diameter distribution of SBA-15-BU-1.
Fig. 3 is a transmission electron microscope photo, and wherein, a is the transmission electron microscope photo of SBA-15, and b is the transmission electron microscope photo of SBA-15-BU-1.
Fig. 4 is a stereoscan photograph, and wherein, a1 and a2 are the stereoscan photograph of SBA-15, and b1 and b2 are the stereoscan photograph of SBA-15-BU-1.
Embodiment
The invention provides a kind of olefine polymerizing process; This method is included under the olefinic polymerization condition, and one or more alkene are contacted with carried metallocene catalyst, and said carried metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on the said carrier; It is characterized in that; Said carrier is SBA-15, 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.
According to 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 the present invention, the X in the formula 1 is a halogen.What particularly, the X in the formula 1 can be in fluorine, chlorine, bromine and the iodine is a kind of.Preferably, the X in the formula 1 is a chlorine or bromine.X in the different metallocene compound molecules can be identical or different, and 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 a kind of.
The specific examples that satisfies the cyclopentadienyl moiety of above-mentioned requirements comprises: methyl cyclopentadienyl, 1,2-dimethyl--cyclopentadienyl moiety, 1,3-dimethyl--cyclopentadienyl moiety, 1; 2,3-trimethylammonium-cyclopentadienyl moiety, 1,2; 4-trimethylammonium-cyclopentadienyl moiety, 1; 2,3,4-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, 1-methyl-2-ethyl-cyclopentadienyl moiety, 1-methyl-3-ethyl-cyclopentadienyl moiety, n-propyl cyclopentadienyl moiety, sec.-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, n-butyl cyclopentadienyl, sec.-butyl cyclopentadienyl moiety, isobutyl-cyclopentadienyl moiety, tertiary butyl cyclopentadienyl moiety, 1; 3-di-n-butyl-cyclopentadienyl moiety, 1-methyl-3-normal-butyl-cyclopentadienyl moiety, 1; 3-two sec.-butyls-cyclopentadienyl moiety, 1-methyl-3-sec.-butyl-cyclopentadienyl moiety, 1,3-diisobutyl-cyclopentadienyl moiety, 1-methyl 3-isobutyl--cyclopentadienyl moiety, 1,3-di-t-butyl-cyclopentadienyl moiety, the 1-methyl 3-tertiary butyl-cyclopentadienyl moiety, n-pentyl cyclopentadienyl moiety, isopentyl cyclopentadienyl moiety, tert-pentyl cyclopentadienyl moiety, neo-pentyl cyclopentadienyl moiety, 1; 3-two n-pentyls-cyclopentadienyl moiety, 1-methyl-3-n-pentyl-cyclopentadienyl moiety, 1; 3-diisoamyl-cyclopentadienyl moiety, 1-methyl-3-isopentyl-cyclopentadienyl moiety, 1,3-two tert-pentyls-cyclopentadienyl moiety, 1-methyl-3-tert-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, ethyl cyclopentadienyl moiety, n-propyl cyclopentadienyl moiety, sec.-propyl cyclopentadienyl moiety, n-butyl cyclopentadienyl, sec.-butyl cyclopentadienyl moiety, isobutyl-cyclopentadienyl moiety, tertiary butyl cyclopentadienyl moiety, n-pentyl cyclopentadienyl moiety, isopentyl cyclopentadienyl moiety, tert-pentyl cyclopentadienyl moiety, neo-pentyl cyclopentadienyl moiety.
More preferably, R
1And R
1' for being the normal-butyl or the tertiary butyl.The specific examples that satisfies the cyclopentadienyl moiety of above-mentioned requirements is tertiary butyl cyclopentadienyl moiety, n-butyl cyclopentadienyl.
According to the present invention, said alkylaluminoxane can be metallocene catalyst field various alkylaluminoxanes commonly used.Usually, the alkyl in the said alkylaluminoxane is C
1-C
5Alkyl.Said C
1-C
5Alkyl be a kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec.-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and the neo-pentyl.Be preferably methyl, promptly 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 (normal-butyl-cyclopentadienyl moiety) zirconium dichlorides; And when alkylaluminoxane is MAO, when said carried metallocene catalyst is used for the polyreaction of catalyzed alkene, demonstrate excellent especially catalytic activity.
According to the present invention; The feasible total amount with said carried metallocene catalyst of said alkylaluminoxane and the metallocene compound charge capacity on said carrier is a benchmark; The total amount of said metallocene compound and alkylaluminoxane can be 10-60 weight %; Be preferably 45-55 weight %, more preferably 48-52 weight % most preferably is 50 weight %.The content of said carrier can be 40-90 weight %, is preferably 45-55 weight %, and more preferably 48-52 weight % most preferably is 50 weight %.
According to the present invention, the ratio between said alkylaluminoxane and the metallocene compound can be the known ratio of the technician of field of olefin polymerisation.Particularly, the mol ratio of the M in aluminium in the said alkylaluminoxane and the said metallocene compound can be 50-200: 1, be preferably 90-110: and 1,95-105 more preferably: 1, most preferably be 102: 1.
According to the present invention, said carrier is SBA-15, and said SBA-15 can be the known SBA-15 with various microscopic appearances of technician in the synthetic field of molecular sieve.Particularly, said SBA-15 is bar-shaped, and the length of rod can be the 30-100 micron; The most probable aperture of said SBA-15 can be the 6-10 nanometer, is preferably the 6-7 nanometer, more preferably 6.2 nanometers; Pore volume can be 0.5-1.5 milliliter/gram, is preferably 0.8-1.2 milliliter/gram, more preferably 1.0 milliliters/gram; Specific surface area can be the 600-700 meters squared per gram, is preferably the 630-660 meters squared per gram, more preferably 646 meters squared per gram.
The mesoporous material SBA-15 of above-mentioned specification has high mechanical strength that the wide aperture, pore volume of high-sequential, thicker hole wall keep and good catalysis absorption property; Have bigger specific surface area and relatively large aperture; Can handle bigger molecule or group; In load behind metallocene compound and the alkylaluminoxane; Can access a Stability Analysis of Structures, bar-shaped loaded metallocene catalytic, this stable structure makes the metallocene compound and the alkylaluminoxane that load on the mesoporous material SBA-15 can be good at bringing into play its catalytic activity.
Above-mentioned carried metallocene catalyst can be through under protection of inert gas, successively load alkylaluminoxane and metallocene compound and prepare on carrier.
According to the present invention, 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.
Said on carrier the method for load alkylaluminoxane and metallocene compound can be various carrying method well known in the art, for example: 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.
According to the present invention, in the above-mentioned carried metallocene catalyst of preparation, also be included in before the load alkylaluminoxane, under protection of inert gas, said carrier was heated 5-20 hour under 300-500 ℃ temperature.
According to the present invention, prepare the method for above-mentioned carried metallocene catalyst, for example: can may further comprise the steps:
(1) thermal activation step under nitrogen protection, in 300-500 ℃ of calcining 5-20 hour, obtains the carrier after the thermal activation with carrier such as bar-shaped SBA-15;
(2) carrier after the thermal activation is transferred in the reactor drum after nitrogen is fully replaced, adds toluene, alkylaluminoxane; Count in molar ratio, carrier (in silicon-dioxide): toluene: the amount ratio of alkylaluminoxane is 1: 3-10: 0.1-1, stirred 1-10 hour in 25-80 ℃ again; After finishing; Use hexane wash again 2 times, at last solid is dried up with nitrogen, obtain the carrier of load alkylaluminoxane;
(3) under nitrogen protection, the carrier of load alkylaluminoxane is joined in the reactor drum, add toluene, stir and process slurries; In the container of crossing with nitrogen replacement in advance, solution is processed in the metallocene compound dissolving, counted in molar ratio, carrier (in silicon-dioxide): toluene: the amount ratio of metallocene compound is 1: 3-15: 2 * 10
-3-5 * 10
-3, under 25-80 ℃ of agitation condition, slowly the metallocene compound drips of solution is added in the reactor drum; Stirring reaction 0.3-2 hour, reaction was left standstill after finishing; Leach liquid,, dry up with nitrogen with toluene and hexane wash 3 times; Obtain carried metallocene catalyst, described metallocene compound solution is preferably the toluene solution of metallocene compound.
According to olefine polymerizing process of the present invention, said one or more alkene carry out in the presence of the solution that contains aluminum alkyls and/or alkylaluminoxane with contacting preferably of said carried metallocene catalyst.That is,, preferably when carrying out polymerization, in reaction system, replenish and add the solution that contains aluminum alkyls and/or alkylaluminoxane according to olefine polymerizing process of the present invention.Be in the effect that aluminum alkyls and/or the alkylaluminoxane of alkylaluminoxane on loading on said carrier in the solution play the cleaning reaction poisonous substance, thereby make the metallocene compound that loads on the said carrier can bring into play katalysis better.
According to olefine polymerizing process of the present invention, when said one or more alkene carry out in the presence of the solution that is containing aluminum alkyls and/or alkylaluminoxane with contacting of said carried metallocene catalyst.Whole aluminium and the mol ratio of the M in the said metallocene compound can be various mol ratios known in the field in said aluminum alkyls and the said alkylaluminoxane (comprise the alkylaluminoxane that loads on the said carrier and be in the alkylaluminoxane in the solution).Alkyl in said aluminum alkyls and the said alkylaluminoxane C that respectively does for oneself
1-C
5Alkyl.Preferably, said aluminum alkyls is a triethyl aluminum, and said alkylaluminoxane is a MAO.
The alkylaluminoxane that is in the solution can be identical with the kind that loads on alkylaluminoxane on the said carrier (that is, replenishing the alkylaluminoxane that the alkylaluminoxane that adds and said carried metallocene catalyst contain), also can difference; Be preferably identical.
According to olefine polymerizing process of the present invention, said alkene 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.More preferably, said alkene is one or more in ethene, 1-butylene, 1-amylene and the 1-hexene.
According to olefine polymerizing process of the present invention, because the present invention is through using said loaded catalyst to improve the efficient of polyreaction, so the present invention does not limit for said olefinic polymerization condition is special.Can be the known polymerizing condition of the technician of field of olefin polymerisation.Preferably, said contact is carried out in the presence of solvent, and to have the compound of the structure shown in the formula 1, the concentration of said loaded catalyst in solvent is 1 * 10
-8-1 * 10
-3Mol is preferably 1 * 10
-8-1 * 10
-5Mol.The polymeric temperature can be-78 ℃ to 100 ℃, is preferably 0 ℃-90 ℃; Pressure can be 0.01-10MPa, is preferably 0.01-2MPa.Said solvent is selected from alkyl or aromatic hydrocarbon or halohydrocarbon.Be preferably a kind of in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform, the ethylene dichloride or their mixture, most preferably be a kind of in hexane, toluene, the heptane or their mixture.
The present invention is the structure of loaded catalyst through X-ray diffraction method, nitrogen adsorption desorption method and ESEM method alkylaluminoxane of having measured or characterized carrier S BA-15 and load and carrier with metallocene compound.Measure the content of aluminium and metal M in the loaded catalyst through ultimate analysis.
Through specific embodiment the present invention is further specified below, but embodiments of the invention have more than and are limited to following examples.
In following examples, X-ray diffraction analysis is to carry out on the X-ray diffractometer of D8 Advance in the model available from German Bruker AXS company; TEM analysis is to carry out on the transmission electron microscope of Tecnai 20 in the model available from Dutch FEI Co.; Scanning electron microscope analysis is to carry out on the sem of XL-30 in the model available from U.S. FEI Co..Ultimate analysis is to carry out on the 7500CX instrument in the model available from U.S. An Jielun company.
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.
Present embodiment is used for explanation according to carried metallocene catalyst of the present invention and preparation method thereof.
1) rod-like mesoporous material SBA-15 (is available commercially from high-tech share ltd of Changchun Jilin University; The length of rod is the 30-100 micron; Its pore structure parameter is as shown in table 1) 400 ℃ of calcinings 10 hours (thermal activation) under nitrogen protection; Remove hydroxyl and remaining moisture, obtain the rod-like mesoporous material after the thermal activation;
2) 0.4 gram of the rod-like mesoporous material after the thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced; Add 10 milliliters of purified toluene; MAO (MAO is purchased the Albemarle company from the U.S.) auxiliary agent 0.47 restrains in 50 ℃ and stirred 4 hours.After finishing, use 20 milliliters of hexane wash three times again, at last solid is dried up with nitrogen, obtain alkylaluminoxane/SBA-15 complex compound carrier (MAO/SBA-15).
3) under nitrogen protection; Alkylaluminoxane/SBA-15 complex compound carrier is joined in the reactor drum; Add 20 milliliters of purified toluene, stir and process slurries, under 30 ℃; Slowly dropping 10ml contains the toluene solution of two (n-butyl cyclopentadienyl) zirconium dichlorides (being purchased the Aesar from Alfa) of metallocene compound of 49 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid,, follow,, solid is dried up with nitrogen, obtain carried metallocene catalyst and the carried metallocene catalyst called after SBA-15-BU-1 of gained with 40 milliliters of hexane wash twice with 10 milliliters of toluene wash three times.Through X-ray diffraction method, nitrogen adsorption desorption method and ESEM carrier S BA-15 and SBA-15-BU-1 are characterized, its result such as Fig. 1, Fig. 2, Fig. 3 and shown in Figure 4, the pore structure parameter of SBA-15-BU-1 is as shown in table 1.Measure the content of aluminium and zirconium in the loaded catalyst through ultimate analysis.
A among Fig. 1 is the x-ray diffraction pattern of SBA-15, and the b among Fig. 1 is the x-ray diffraction pattern of SBA-15-BU-1.Can find out significantly that from x-ray diffraction pattern sample SBA-15 and SBA-15-BU-1 all diffraction peak occurs in little angular region.(100) diffraction peak intensity of face is high, peak shape is narrow, explains that rod-like mesoporous material SBA-15 and SBA-15-BU-1 have good six side's long-range order pore passage structures.
A among Fig. 2 is that (X-coordinate is relative pressure (p/p for nitrogen adsorption-desorption graphic representation of carried metallocene catalyst SBA-15-BU-1
0)), the b among Fig. 2 is a graph of pore diameter distribution, shows that by nitrogen adsorption-desorption thermo-isopleth among a carried metallocene catalyst SBA-15-BU-1 is the meso-hole structure of typical orderly hexagonal structure.Can find out that by b graph of pore diameter distribution (X-coordinate is the aperture, and unit is 0.1nm) SBA-15-BU-1 has narrow pore size distribution, and the duct is very even.
A among Fig. 3 is the transmission electron microscope picture of SBA-15, and the b among Fig. 3 is the transmission electron microscope picture of SBA-15-BU-1.From Fig. 3, can know and see that SBA-15 is the orderly pore passage structures of six sides, SBA-15-BU-1 duct shape remains unchanged basically behind the load metallocene.
Fig. 4 is the microscopic appearance figure of SBA-15 and SBA-15-BU-1.Wherein, a1 among Fig. 4 and a2 are the microscopic appearance figure of SBA-15, and b1 among Fig. 4 and b2 are the microscopic appearance figure of SBA-15-BU.Can know that by Fig. 4 the microscopic appearance figure of mesoporous material SBA-15 and SBA-15-BU-1 is bar-shaped.
Table 1
Can find out from the pore structure parameter of rod-like mesoporous material SBA-15 shown in the table 1 and SBA-15-BU-1; Mesoporous material SBA-15 pore structure parameter after the load of process metallocene all reduces to some extent, and this result shows that clearly MAO and metallocene enter into the mesoporous material duct really.
Results of elemental analyses shows; Load two (n-butyl cyclopentadienyl) zirconium dichlorides of promotor MAO (MAO) and metallocene compound) the content of aluminium of rod-like mesoporous material SBA-15 be 21.3 weight %; The content of Zr is 0.70 weight %, and the mol ratio of Al/Zr is 102.Weight according to SBA-15-BU-1 after the weight of carrier S BA-15 before the load and the load can be known: the total amount with carried metallocene catalyst is a benchmark; The total content of MAO (MAO) and metallocene compound is 50 weight %, and the content of carrier is 50 weight %.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for explaining the catalytic activity according to loaded catalyst of the present invention.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexane solvents then; With still temperature rise to 80 ℃, add 800 milliliters of hexane solvents again, along with the adding of hexane; Triethyl aluminum (TEA) hexane solution of 2 milliliter of 1 mol is added; Then add the SBA-15-BU65.5 milligram, feed ethene and pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, weigh 421 grams, the efficient of catalyzer is 6427gPE/ (gcath) (8.4 * 10
7GPE/ (mol Zrh)), poly bulk density (BD) is 0.326g/ml, melting index: MI
2.16=0.061g/10min.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for explaining the catalytic activity according to loaded catalyst of the present invention.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexane solvents then; With still temperature rise to 80 ℃, add 800 milliliters of hexane solvents again, along with the adding of hexane; Triethyl aluminum (TEA) hexane of 2 milliliter of 1 mol and the hexene solution of 10ml are added; Then add the SBA-15-BU37.4 milligram, feed ethene and pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, collected polymer particle powder, weigh 216 grams, the efficient of catalyzer is 5775gPE/ (gcath) (7.5 * 10
7GPE/ (mol Zrh)), the bulk density of polymkeric substance (BD) is 0.293g/ml, melting index: MI
2.16=0.401g/10min.
Comparative Examples 1
Two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of silica gel (ES955) load metallocene catalyst) preparation also is used for ethylene homo
1) with the 400 ℃ of calcinings 10 hours (thermal activation) under nitrogen protection of ES955 silica gel, removes hydroxyl and remaining moisture, obtain the ES955 silica gel after the thermal activation;
2) under nitrogen protection, 0.9 gram ES955 silica gel is joined in the reactor drum, add 1.0 gram MAO (MAO; Be purchased Albemarle company from the U.S.) and the 10ml toluene solution, under 50 ℃ of conditions, stirring reaction is after 4 hours; With toluene wash 3 times, after finishing, use 20 milliliters of hexane wash three times again; At last solid is dried up with nitrogen, obtain alkylaluminoxane/ES955 silica gel complex compound carrier (MAO/ES955).
3) under nitrogen protection; Alkylaluminoxane/ES955 silica gel complex compound carrier is joined in the reactor drum; Add 20 milliliters of purified toluene, stir and process slurries, under 30 ℃; Slowly dropping 10ml contains the toluene solution of two (n-butyl cyclopentadienyl) zirconium dichlorides (being purchased the Aesar from Alfa) of metallocene compound of 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.Supported catalyst called after ES955-BU with gained.
Results of elemental analyses shows; Load two (n-butyl cyclopentadienyl) zirconium dichlorides of promotor MAO (MAO) and cyclopentadienyl catalyst precursor) the content of aluminium of 955 silica gel be 32.4 weight %; The content of Zr is 0.41 weight %, and the mol ratio of Al/Zr is 270.
Experiment Comparative Examples 1
Adopt with enforcement embodiment 1 identical method and carry out the homopolymerization of ethene, different is that the catalyzer of employing is the ES955-BU of Comparative Examples 1 preparation.The result obtains 65g polyethylene particle powder, and catalyst efficiency is 1295gPE/ (gcath) (2.9 * 10
7GPE/ (mol Zrh)), the bulk density of this polyethylene particle powder (BD) 0.331 is g/ml, melting index: MI
2.16=0.119g/10min.
Experiment Comparative Examples 2
Adopt with enforcement embodiment 2 identical methods and carry out the copolymerization of ethene, different is that the catalyzer of employing is the ES955-BU of Comparative Examples 1 preparation.The result obtains 76g polymer beads powder, and catalyst efficiency is 2260gPE/ (gcath) (5.1 * 10
7GPE/ (mol Zrh)), the bulk density of this polymer beads powder (BD) 0.299 is g/ml, melting index: MI
2.16=0.679g/10min.
Comparative Examples 2
With SBA-15 (being purchased high-tech share ltd) 400 ℃ of calcinings 10 hours under nitrogen protection, removing hydroxyl and remaining moisture, thereby obtain SBA-15 through thermal activation from Changchun Jilin University;
Activated SBA-15 is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced with 0.56 gram; Add 10 milliliters of purified toluene (refluxing 24 hours) and 1 gram MAO (being purchased Albemarle company), and stirred 4 hours at 50 ℃ from the U.S. with sodium.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 SBA-15-1 of MAO (called after MAO/SBA-15-2).
Under nitrogen protection; MAO/SBA-15-2 is joined in 250 milliliters of glass reactors; Add 20 milliliters of purified toluene (refluxing 24 hours), stirred 30 minutes, under 30 ℃ with sodium; Slowly drip the toluene solution that 10ml contains 60 milligrams bicyclic pentadiene zirconium dichloride (being purchased the company from Aldrich), 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 carried metallocene catalyst of the present invention (called after SBA-15-Cp) with 40 milliliters of hexane wash twice with 10 milliliters of toluene wash three times.
Results of elemental analyses shows that the aluminium content among the SBA-15-Cp is 24 weight %, and the content of Zr is 1 weight %, and the mol ratio of Al/Zr is 81.
Experiment Comparative Examples 3
Adopt and carry out the homopolymerization of ethene with embodiment 1 identical method, different is that the catalyzer of employing is the SBA-15-Cp of preparation Comparative Examples 2 preparations.The result obtains 36g polyethylene particle powder, and the bulk density of this polyethylene particle powder (BD) is 0.30g/ml, melting index: MI
2.16=0.011g/10min.Confirm that through calculating the efficient of catalyzer is 384gPE/ (gcath) (3.5 * 10
6GPE/ (mol Zrh)).
Experiment Comparative Examples 4
Adopt and with embodiment 2 identical methods ethene and hexene are carried out copolymerization, different is that the catalyzer of employing is the SBA-15-Cp of preparation Comparative Examples 1 preparation.Obtain 43 gram polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.304g/ml, and melting index is MI
2.16=0.077g/10min.Confirm that through calculating the efficient of catalyzer is 438gPE/ (gcath) (4.0 * 10
6G PE/ (mol Zrh)).
Claims (16)
1. olefine polymerizing process; This method is included under the olefinic polymerization condition, and one or more alkene are contacted with carried metallocene catalyst, and said carried metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on the said carrier; It is characterized in that; Said carrier is SBA-15, 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. method according to claim 1; Wherein, Total amount with said carried metallocene catalyst is a benchmark; The total amount of said metallocene compound and alkylaluminoxane is 10-60 weight %, and the content of said carrier is 40-90 weight %, and the mol ratio of the M in aluminium in the said alkylaluminoxane and the said metallocene compound is 50-200: 1.
3. method according to claim 2, wherein, the mol ratio of the M in aluminium in the said alkylaluminoxane and the said metallocene compound is 90-110: 1.
4. according to any described method among the claim 1-3, wherein, said alkylaluminoxane is a MAO.
5. according to any described method among the claim 1-3, wherein, M is a zirconium.
6. method according to claim 1, wherein, X is a chlorine.
7. method according to claim 1, wherein, R
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.
8. method according to claim 10, wherein, R
1And R
1' respectively the do for oneself normal-butyl or the tertiary butyl.
9. method according to claim 1, wherein, said metallocene compound is two (normal-butyl-cyclopentadienyl moiety) zirconium dichlorides, said alkylaluminoxane is a MAO.
10. method according to claim 1, wherein, said carrier is bar-shaped, the length of rod is the 30-100 micron.
11. method according to claim 10, wherein, the most probable aperture of said carrier is the 6-10 nanometer, and pore volume is 0.5-1.5 milliliter/gram, and specific surface area is the 600-700 meters squared per gram.
12. method according to claim 1, wherein, said alkene is one or more in ethene, terminal olefin and the diolefin.
13. method according to claim 12, wherein, said alkene is ethene, C
3-C
101-alkene, C
4-C
8Diolefin in one or more.
14. method according to claim 1, wherein, said olefinic polymerization condition comprises: temperature is-78 ℃ to 100 ℃, and pressure is 0.01-10MPa.
15. method according to claim 1, wherein, said contact is carried out in the presence of solvent, and to have the compound of the structure shown in the formula 1, the concentration of said carried metallocene catalyst in solvent is 1 * 10
-8-1 * 10
-3Mol, said olefinic polymerization condition comprises: temperature is-78 ℃ to 100 ℃, pressure is 0.01-10MPa.
16. method according to claim 15, wherein, to have the compound of the structure shown in the formula 1, the concentration of said carried metallocene catalyst in solvent is 1 * 10
-8-1 * 10
-5Mol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010519311 CN102453135B (en) | 2010-10-19 | 2010-10-19 | Olefin polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010519311 CN102453135B (en) | 2010-10-19 | 2010-10-19 | Olefin polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102453135A true CN102453135A (en) | 2012-05-16 |
| CN102453135B CN102453135B (en) | 2013-11-06 |
Family
ID=46036854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010519311 Active CN102453135B (en) | 2010-10-19 | 2010-10-19 | Olefin polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102453135B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456273A (en) * | 2017-02-17 | 2018-08-28 | 旭化成株式会社 | Polyethylene based polymers and its manufacturing method |
-
2010
- 2010-10-19 CN CN 201010519311 patent/CN102453135B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| 《POLYMER ENGINEERING AND SCIENCE》 20080331 A. Carrero et al Ethylene Polymerization Over (nBuCp)2ZrCl2/MAO Catalytic System Supported on Aluminosilicate SBA-15 Mesostructured Materials , * |
| A. CARRERO ET AL: "Ethylene Polymerization Over (nBuCp)2ZrCl2/MAO Catalytic System Supported on Aluminosilicate SBA-15 Mesostructured Materials", 《POLYMER ENGINEERING AND SCIENCE》 * |
| 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》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456273A (en) * | 2017-02-17 | 2018-08-28 | 旭化成株式会社 | Polyethylene based polymers and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102453135B (en) | 2013-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102453123B (en) | Supported metallocene catalyst and preparation method thereof | |
| CN102453144B (en) | Olefin polymerization method | |
| CN102453122B (en) | Loaded metallocene catalyst and preparation method thereof | |
| CN102453142B (en) | Olefin polymerization method | |
| CN102952209B (en) | Supported metallocene catalyst and preparation method and application thereof | |
| CN102453146B (en) | Olefin polymerization method | |
| CN102718898B (en) | Olefin polymerization method | |
| CN102453135B (en) | Olefin polymerization method | |
| CN102453141B (en) | Loaded metallocene catalyst and preparation method thereof | |
| CN102453139B (en) | Olefin polymerization method | |
| CN102952213B (en) | Load-type metallocene catalyst, preparation method thereof and application thereof | |
| CN102952217B (en) | Alkene polymerization method | |
| CN102952218A (en) | Alkene polymerization method | |
| CN102453158B (en) | Loaded metallocene catalyst and preparation method thereof | |
| CN102453136B (en) | Olefin polymerization method | |
| CN102453145B (en) | Polymerization method for alkene | |
| CN102453119A (en) | Loaded non-metallocene catalyst and preparation method thereof | |
| CN102453134B (en) | Olefin polymerization method | |
| CN102453120B (en) | Load type metallocene catalyst and preparation method thereof | |
| CN102952216B (en) | Olefin polymerization method | |
| CN102952210B (en) | Supported metallocene catalyst and preparation method and application thereof | |
| CN102952214B (en) | Olefin polymerization method | |
| CN102453138A (en) | Olefin polymerization method | |
| CN102952215B (en) | Olefin polymerization method | |
| CN102453137A (en) | Olefin polymerization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |