CN102453145B - Polymerization method for alkene - Google Patents

Polymerization method for alkene Download PDF

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CN102453145B
CN102453145B CN 201010519781 CN201010519781A CN102453145B CN 102453145 B CN102453145 B CN 102453145B CN 201010519781 CN201010519781 CN 201010519781 CN 201010519781 A CN201010519781 A CN 201010519781A CN 102453145 B CN102453145 B CN 102453145B
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cyclohexyl
alkylaluminoxane
sba
carrier
tertiary butyl
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CN102453145A (en
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邱波
谢伦嘉
亢宇
王洪涛
王彦强
郭顺
郑刚
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 polymerization method for alkene. According to the method, under polymerization conditions for alkene, one or more alkene contacts with a supported catalyst; the invention is characterized in that: the supported catalyst comprises a supporter, a compound having a structure as represented by formula 1 and alkylaluminoxane, and the compound and alkylaluminoxane are loaded on the supporter, wherein, the supporter is SBA-15, R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' are individually hydrogen, hydroxy groups or C1-C5 alkyl groups, at least one of R1, R2, R3, R4 and R5is a hydroxy group while at least another one of R1, R2, R3, R4 and R5 is a C1-C5alkyl group, at least one of R1', R2', R3', R4' and R5' is a hydroxy group while at least another one of R1', R2', R3', R4' and R5' is a C1-C5 alkyl group, M is one selected from the group consisting of titanium, zirconium and hafnium, and X is halogen. The polymerization method for alkene provided in the invention has the advantages of low cost and high efficiency. The formula 1 is described in the specification.

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 methylaluminoxane (MAO), makes the research of metallocene catalyst enter into a stage that develops rapidly.At present, relevant metallocene load research report is very many, wherein with SiO 2For the research of the report of carrier at most, for example: CN1174848A, CN1174849A, CN1356343A, US4,808,561, US5,026,797, US5,763,543, US5,661,098 all disclose with SiO 2Carried metallocene catalyst for carrier.
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 tangible 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, the inserted mode of monomer is different with freeboard with propagation process in the polymerization process, and 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 molecular sieve, has following advantage:
(1) molecular sieve of synthetic does not contain the impurity that easily makes polymer degradation, will improve the ageing resistance of polyolefine material;
(2) the molecular sieve nano pore has the dual-use function of carrier and reactor, catalyst cupport efficient height, and polymerization process is controlled easily, and can key in the active centre in the skeleton of polymerization reactor, 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 by with Cp 2ZrCl 2Loading on the SBA-15 that handles through MAO goes up and obtains.
CN1923862A discloses a kind of olefin polymerization catalysis of mesoporous molecular sieve carriedization, and this catalyzer is upward to obtain by the semi-sandwich alum metallic compound shown in the following formula being loaded on the SBA-15 that handles through MAO,
Figure BSA00000318642600021
Summary of the invention
The objective of the invention is to overcome the cost of carried metallocene catalyst of prior art than higher, provide a kind of cost low and olefine polymerizing process efficiently.
The invention provides a kind of olefine polymerizing process, this method is included under the olefinic polymerization condition, one or more alkene are contacted with loaded catalyst, it is characterized in that, described loaded catalyst comprises carrier and loads on the compound with the structure shown in the formula 1 and alkylaluminoxane on the described carrier, described carrier is SBA-15
Figure BSA00000318642600031
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, hydroxyl or C independently of one another 1-C 5Alkyl, R 1, R 2, R 3, R 4And R 5In at least one be hydroxyl, and another is C at least 1-C 5Alkyl, R 1', R 2', R 3', R 4' and R 5' at least one be hydroxyl, and another is C at least 1-C 5Alkyl, M is a kind of in titanium, zirconium and the hafnium, X is halogen.
According to the present invention, the compound of the structure shown in the described formula 1, have substituting group on the phenyl ring, and it is loaded on the mesoporous material SBA-15 of high mechanical strength and good catalysis absorption property, can make loaded catalyst of the present invention well bring into play its catalytic activity.Specifically, loaded catalyst according to the present invention is when being used for catalysis in olefine polymerization, and catalytic efficiency can reach 1300-1800gPE/ (gcath) (6 * 10 7-7 * 10 7GPE/ (molZrh).And under the same conditions, the catalytic efficiency behind the 955 silica gel load catalyzer of using always in the existing industry is generally 400-500gPE/ (gcath) (2 * 10 7-4 * 10 7GPE/ (mol Zrh).
Description of drawings
Fig. 1 is 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-FI-1.
A among Fig. 2 is the attached graphic representation of nitrogen adsorption-desorption of SBA-15-FI-1, and the b among Fig. 2 is the graph of pore diameter distribution of SBA-15-FI-1.
Fig. 3 is the scanning electron microscope analysis structure, and wherein, a1 and a2 are the stereoscan photograph of SBA-15, and b1 and b2 are the stereoscan photograph of SBA-15-FI-1.
Embodiment
The invention provides a kind of olefine polymerizing process, this method is included under the olefinic polymerization condition, one or more alkene are contacted with loaded catalyst, it is characterized in that, described loaded catalyst comprises carrier and loads on the compound with the structure shown in the formula 1 and alkylaluminoxane on the described carrier, described carrier is SBA-15
Figure BSA00000318642600041
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, hydroxyl or C independently of one another 1-C 5Alkyl, R 1, R 2, R 3, R 4And R 5In at least one be hydroxyl, and another is C at least 1-C 5Alkyl, R 1', R 2', R 3', R 4' and R 5' at least one be hydroxyl, and another is C at least 1-C 5Alkyl, M is a kind of in titanium, zirconium and the hafnium, X is 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 zirconium.
According to the present invention, the X in the formula 1 is 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 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 chlorine.
According to the present invention, wherein, the R on the phenyl in the above-mentioned formula 1 1, R 2, R 3, R 4, R 5, R 1', R 2', R 3', R 4' and R 5' be hydrogen, hydroxyl or C independently of one another 1-C 5Alkyl, R 1, R 2, R 3, R 4And R 5In at least one be hydroxyl, and another is C at least 1-C 5Alkyl, R 1', R 2', R 3', R 4' and R 5' at least one be hydroxyl, and another is C at least 1-C 5Alkyl.
Among the present invention, described 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.
Preferably, the R in the formula 1 1Or R 5Be hydroxyl, and R 2Or R 4Be C 1-C 5Alkyl, R 1' or R 5' be hydroxyl, and R 2' or R 4' be C 1-C 5Alkyl, R 1, R 2, R 3, R 4, R 5, R 1', R 2', R 3', R 4' and R 5' in all the other are hydrogen.
For the compound with the structure shown in the formula 1 among clearer description the present invention, the part-structure in the formula 1 (structure as shown in Equation 2) is decided to be Y, the part-structure in the formula 1 (structure as shown in Equation 3) is decided to be Y '.The structure of formula 2 and formula 3 is as follows:
Figure BSA00000318642600051
Formula 2
Figure BSA00000318642600052
Formula 3
Particularly, satisfying the Y of above-mentioned requirements or the specific examples of Y ' comprises: N-cyclohexyl-3-cresotinic acid aldimine groups, N-cyclohexyl-3-ethyl salicylic alidehyde imine base, N-cyclohexyl-3-n-propyl salicylic alidehyde imine base, N-cyclohexyl-3-sec.-propyl salicylic alidehyde imine base, N-cyclohexyl-3-normal-butyl salicylic alidehyde imine base, N-cyclohexyl-3-sec-butyl salicylic alidehyde imine base, N-cyclohexyl-3-isobutyl-salicylic alidehyde imine base, N-cyclohexyl-3-tertiary butyl salicylic alidehyde imine base, N-cyclohexyl-3-n-pentyl salicylic alidehyde imine base, N-cyclohexyl-3-isopentyl salicylic alidehyde imine base, N-cyclohexyl-3-tert-pentyl salicylic alidehyde imine base, N-cyclohexyl-3-neo-pentyl salicylic alidehyde imine base, N-cyclohexyl-5-cresotinic acid aldimine groups, N-cyclohexyl-5-ethyl salicylic alidehyde imine base, N-cyclohexyl-5-propyl group salicylic alidehyde imine base, N-cyclohexyl-5-sec.-propyl salicylic alidehyde imine base, N-cyclohexyl-5-butyl salicylic alidehyde imine base, N-cyclohexyl-5-sec-butyl salicylic alidehyde imine base, N-cyclohexyl-5-isobutyl-salicylic alidehyde imine base, N-cyclohexyl-5-tertiary butyl salicylic alidehyde imine base, N-cyclohexyl-5-amyl group salicylic alidehyde imine base, N-cyclohexyl-5-isopentyl salicylic alidehyde imine base, N-cyclohexyl-5-tert-pentyl salicylic alidehyde imine base, N-cyclohexyl-5-neo-pentyl salicylic alidehyde imine base.
More preferably, the R in the formula 1 1And R 1' be hydroxyl, R 2And R 2' be the tertiary butyl, R 3, R 4, R 5, R 1', R 2', R 3', R 4' and R 5' be hydrogen.Satisfying the Y of above-mentioned requirements or the specific examples of Y ' is N-cyclohexyl-3-tertiary butyl salicylic alidehyde imine base.
According to the present invention, described alkylaluminoxane can be metallocene catalyst field various alkylaluminoxanes commonly used.Usually, the alkyl in the described alkylaluminoxane is C 1-C 5Alkyl.Described 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, namely described alkylaluminoxane is methylaluminoxane.
The present inventor finds in research process, the R in formula 1 1And R 1' be hydroxyl, R 2And R 2' be the tertiary butyl, M is zirconium, X is chlorine, be that described compound with the structure shown in the formula 1 is two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichlorides, when described alkylaluminoxane is methylaluminoxane, adopt the described loaded catalyst of method preparation of the present invention in the polyreaction of catalyzed alkene, to demonstrate excellent especially catalytic activity.
According to the present invention, described alkylaluminoxane is benchmark with the feasible total amount with described loaded catalyst of the charge capacity of compound on described carrier with the structure shown in the formula 1, described have the compound of the structure shown in the formula 1 and the total amount of alkylaluminoxane can be 10-60 weight %, be preferably 45-55 weight %, more preferably 48-52 weight % most preferably is 50 weight %.The content of described 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, described alkylaluminoxane and the ratio that has between the compound of the structure shown in the formula 1 can be the known ratio of the technician of field of olefin polymerisation.Particularly, the mol ratio of the M in the aluminium in the described alkylaluminoxane and the described compound with the structure shown in the formula 1 can be 200-500: 1, be preferably 250-350: and 1, more preferably 312: 1.
According to loaded catalyst of the present invention, described carrier is SBA-15, and described SBA-15 can be the known SBA-15 with various microscopic appearances of technician in the synthetic field of molecular sieve.Particularly, described SBA-15 is bar-shaped, and the length of rod can be the 30-100 micron; The most probable aperture of described 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 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 after having the compound and alkylaluminoxane of the structure shown in the formula 1, obtain a Stability Analysis of Structures, bar-shaped supported catalyst, this stable structure makes the compound with the structure shown in the formula 1 and the alkylaluminoxane that load on the mesoporous material SBA-15 can be good at bringing into play its catalytic activity.
Above-mentioned loaded catalyst can be by under protection of inert gas, and successively the load alkylaluminoxane prepares with having the compound of the structure shown in the formula 1 on carrier.
According to the present invention, chemically interactive all gases can not take place with carrier, alkylaluminoxane, compound with the structure shown in the formula 1 for various in described rare gas element.For example, described rare gas element can be nitrogen, argon gas.
Described on carrier load alkylaluminoxane and method with compound of the structure shown in the formula 1 can be various carrying method well known in the art, for example: dipping, spraying.Adopt the method for dipping can be so that solution enters in the duct on the carrier more fully, therefore, the present invention be preferably flooded.
The method of above-mentioned loaded catalyst preferably also is included in before the load alkylaluminoxane, under protection of inert gas, described carrier is heated 5-20 hour under 300-500 ℃ temperature.
Above-mentioned loaded catalyst,, for example, can prepare by following 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 after nitrogen is fully replaced, add toluene, alkylaluminoxane, count in molar ratio, carrier (in silicon-dioxide): toluene: the amount ratio of alkylaluminoxane is 1: 3-10: 0.1-2, 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, add toluene, stir and make slurries; The compound dissolution that will have the structure shown in the formula 1 in the container of crossing with nitrogen replacement is in advance made solution, counts in molar ratio, and carrier (in silicon-dioxide): toluene: the amount ratio with compound of the structure shown in the formula 1 is 1: 3-15: 2 * 10 -3-5 * 10 -3Under 25-80 ℃ of agitation condition, the compound solution that slowly will have the structure shown in the formula 1 is added drop-wise in the reactor, and stirring reaction 0.3-2 hour, after reaction finishes, leave standstill, leach liquid, use toluene and hexane wash 3 times, dry up with nitrogen, obtain loaded catalyst, described compound solution with the structure shown in the formula 1 is preferably the toluene solution of the compound with the structure shown in the formula 1.
According to olefine polymerizing process of the present invention, described one or more alkene carry out in the presence of the solution that contains aluminum alkyls and/or alkylaluminoxane with contacting preferably of described loaded catalyst.That is, according to olefine polymerizing process of the present invention, preferably when carrying out polymerization, in reaction system, replenish the solution that interpolation contains aluminum alkyls and/or alkylaluminoxane.Be in the effect that aluminum alkyls in the solution and/or the alkylaluminoxane of alkylaluminoxane on loading on described carrier play the cleaning reaction poisonous substance, thereby make the compound with the structure shown in the formula 1 that loads on the described carrier can bring into play katalysis better.
According to olefine polymerizing process of the present invention, when described one or more alkene carried out in the presence of the solution that is containing aluminum alkyls and/or alkylaluminoxane with contacting of described loaded catalyst, the mol ratio of the M in described aluminum alkyls and the described alkylaluminoxane (comprise the alkylaluminoxane that loads on the described carrier and be in alkylaluminoxane in the solution) in whole aluminium and the described compound with the structure shown in the formula 1 can be various mol ratios known in the field.Alkyl in described aluminum alkyls and the described alkylaluminoxane C that can respectively do for oneself 1-C 5Alkyl.Preferably, described aluminum alkyls is triethyl aluminum, and described alkylaluminoxane is methylaluminoxane.
The alkylaluminoxane that is in the solution can be identical with the kind that loads on alkylaluminoxane on the described carrier (that is, replenishing the alkylaluminoxane that the alkylaluminoxane that adds and described loaded catalyst contain), also can difference; Be preferably identical.
According to olefine polymerizing process of the present invention, described alkene can be in ethene, alpha-olefin and the diolefin one or more.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 the 1-hexene.
According to olefine polymerizing process of the present invention, because the present invention is by using described loaded catalyst to improve the efficient of polyreaction, so the present invention is not particularly limited for described olefinic polymerization condition.Can be the known polymerizing condition of the technician of field of olefin polymerisation.Preferably, described 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 described loaded catalyst in solvent is 1 * 10 -8-1 * 10 -3Mol is preferably 1 * 10 -8-1 * 10 -5Mol.The temperature of polymerization can be-78 ℃ to 100 ℃, is preferably 0 ℃-90 ℃; Pressure can be 0.01-10MPa, is preferably 0.01-2MPa.Described 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 by X-ray diffraction method, nitrogen adsorption desorption method and the scanning electron microscope method alkylaluminoxane of having measured or characterized carrier S BA-15 and load and carrier with compound of the structure shown in the formula 1.Measure the content of aluminium and metal M in the loaded catalyst by ultimate analysis.
Below by specific embodiment the present invention is further specified, but embodiments of the invention have more than and are limited to following examples.
In following examples, X-ray diffraction analysis is that the X-ray diffractometer of D8 Advance carries out in the model available from German Bruker AXS company; Scanning electron microscope analysis is that the scanning electronic microscope of XL-30 is carried out in the model available from U.S. FEI Co..Ultimate analysis is carried out at the model 7500CX instrument 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 instrument, sample was 200 ℃ of degassings 4 hours.
Two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichlorides among the following embodiment are synthetic according to the method for embodiment among the CN1850871A 1, and concrete steps are as follows:
(1) preparation ligand compound 3-tertiary butyl salicylidene hexahydroaniline:
Get 17.8g (0.1mol) 3-tertiary butyl salicylic aldehyde and 0.2mol hexahydroaniline and join in the 100ml ethanol medium, stir reflux down, reacted 2 hours, be cooled to room temperature, namely have a large amount of crystal to produce.Filtration, solid finally obtain part 3-tertiary butyl salicyl hexahydroaniline, productive rate 92% with 30ml alcohol solvent recrystallization.
(2) lithium salts of preparation 3-tertiary butyl salicyl hexahydroaniline:
In 100ml Schlenk bottle, add 2.910g (11.5mmol) 3-tertiary butyl salicyl hexahydroaniline and 30ml tetrahydrofuran (THF), solvent is cooled to-70 ℃, Dropwise 5 .72ml (2.0113molL-1 under agitation, 11.5mmol) butyllithium, dropwise, naturally rise to room temperature, stirred 3 hours, obtain the tetrahydrofuran solution of 3-tertiary butyl salicylidene hexahydroaniline lithium salts.
(3) preparation of two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichloride:
Tetrahydrofuran solution with above-mentioned 3-tertiary butyl salicylidene hexahydroaniline lithium salts is cooled to-70 ℃, and slowly drips 0.79g (3.4mmol) ZrCl under this temperature 4The 30ml tetrahydrofuran solution in, rise to room temperature then naturally, stirring is spent the night.Decompression is drained reaction solution down, adds 30ml toluene, filters, and filtrate was placed 18 hours at-20 ℃, separates out two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichlorides of 0.40g.
Embodiment 1
Present embodiment is used for explanation according to loaded catalyst of the present invention and preparation method thereof.
1) under protection of nitrogen gas, rod-like mesoporous material SBA-15 (is available commercially from (high-tech share company limited of Changchun Jilin University), the length of rod is the 30-100 micron, its pore structure parameter is as shown in table 1) be under 400 ℃ in temperature, calcine 10 hours (thermal activation), remove hydroxyl and remaining moisture, obtain the rod-like mesoporous material SBA-15 after the thermal activation;
2) the 0.96 rod-like mesoporous material SBA-15 of gram after the thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, add 10 milliliters of refining toluene, methylaluminoxane (MAO is purchased the Albemarle company from the U.S.) auxiliary agent 0.95 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 carrier (MAO/SBA-15).
3) under nitrogen protection; alkylaluminoxane/SBA-15 complex compound carrier is joined in the reactor; add 20 milliliters of refining toluene; slurries are made in stirring; under 30 ℃; slowly dropping 10ml contains the toluene solution of two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichlorides of 44 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid, with 10 milliliters of toluene wash three times, then, with twice of 40 milliliters of hexane wash, solid is dried up with nitrogen, obtain loaded catalyst and with the supported catalyst called after SBA-15-FI-1 of gained, by X-ray diffraction method, nitrogen adsorption desorption method and scanning electron microscope carrier S BA-15 and SBA-15-FI-1 are characterized, its result such as Fig. 1, Fig. 2 and shown in Figure 3, the pore structure parameter of SBA-15-FI-1 is as shown in table 1.Measure the content of aluminium and zirconium in the loaded catalyst by ultimate analysis.
A among Fig. 1 is the x-ray diffraction pattern of rod-like mesoporous material SBA-15, and b is the x-ray diffraction pattern of SBA-15-FI-1 among Fig. 1.Can find out significantly that from x-ray diffraction pattern sample SBA-15 and SBA-15-FI-1 all diffraction peak occurs in little angular region.(100) diffraction peak intensity height, the peak shape of face are narrow, illustrate that rod-like mesoporous material SBA-15 and SBA-15-FI-1 have six good side's long-range order pore passage structures.
A among Fig. 2 is that (X-coordinate is relative pressure (p/p0) for nitrogen adsorption-desorption graphic representation of loaded catalyst SBA-15-F1-1, b among Fig. 2 is the graph of pore diameter distribution of SBA-15-FI-1, shows that by the nitrogen adsorption-desorption thermoisopleth among a loaded catalyst SBA-15-FI-1 is the meso-hole structure of typical orderly hexagonal structure.By b graph of pore diameter distribution (X-coordinate is the aperture, and unit is 0.1nm) as can be seen SBA-15-FI-1 have narrow pore size distribution, but two pore size distribution curves appear, it is comparatively even to illustrate that the duct distributes.
Fig. 3 is the microscopic appearance figure of rod-like mesoporous material SBA-15 and SBA-15-FI-1.Wherein, the a1 among Fig. 3 and a2 are the microscopic appearance figure of rod-like mesoporous material SBA-15, and the b1 among Fig. 3 and b2 are the microscopic appearance figure of SBA-15-FI.As shown in Figure 3, the microscopic appearance figure of mesoporous material SBA-15 and SBA-15-FI-1 is bar-shaped.
Table 1
Figure BSA00000318642600121
From the pore structure parameter of the rod-like mesoporous material SBA-15 shown in the table 1 and SBA-15-FI-1 as can be seen, mesoporous material SBA-15 is through methylaluminoxane (MAO) and all minimizings to some extent of compound loaded back pore structure parameter with the structure shown in the formula 1, and the compound that this result shows methylaluminoxane (MAO) and has a structure shown in the formula 1 enters into the mesoporous material duct.
Results of elemental analyses shows, load the content of aluminium of rod-like mesoporous material SBA-15 of promotor methylaluminoxane (MAO) and two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichlorides be 19.7 weight %, the content of Zr is 0.21 weight %, and the mol ratio of Al/Zr is 312.According to the weight of SBA-15-FI-1 after the weight of carrier S BA-15 before the load and the load as can be known: the total amount with loaded catalyst is benchmark, methylaluminoxane (MAO) and the total content with compound of the structure shown in the formula 1 are 50 weight %, and the content of carrier is 50 weight %.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for illustrating 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, the SBA-15-FI-1 that then adds 1 preparation of 44.6 milligrams of above-described embodiments fed ethene and pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, weigh 227 grams, the efficient of catalyzer is 1600gPE/ (gcath) (6.7 * 10 7GPE/ (molZrh)), poly bulk density (BD) is 0.307g/ml, melting index: MI 2.16=88g/10min.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating 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 and the hexene solution of 10ml are added, then add the SBA-15-FI-1 of above-described embodiment 1 preparation of 59.5 milligrams, feed ethene and pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, collected polymer particle powder, weigh 232 grams, the efficient of catalyzer is 1455gPE/ (gcath) (6.3 * 10 7GPE/ (mol Zrh)), the bulk density of polymkeric substance (BD) is 0.333g/ml, melting index: MI 2.16=130.9g/10min.
Comparative Examples 1
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; 1.05 gram ES955 silica gel are joined in the reactor; add 1.04 gram methylaluminoxane (MAO is purchased the Albemarle company from the U.S.) and 10ml toluene solutions, under 50 ℃ of conditions; behind the stirring reaction 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; add 20 milliliters of refining toluene; slurries are made in stirring; under 30 ℃; slowly dropping 10ml contains the toluene solution of two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichlorides of 50 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid, with 10 milliliters of toluene wash three times, follow, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen.Supported catalyst called after ES955-FI with gained.
Results of elemental analyses shows, load in 955 silica gel of promotor methylaluminoxane (MAO) and two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichlorides the content of aluminium be 0.94 weight %, the content of Zr is 0.14 weight %, and the mol ratio of Al/Zr is 20.
Experiment Comparative Examples 1
Adopt the method identical with implementing embodiment 1 to carry out the homopolymerization of ethene, different is that the catalyzer of employing is the ES955-FI that Comparative Examples 1 prepares.The result obtains 65g polyethylene particle powder, and catalyst efficiency is 458gPE/ (gcath) (2.8 * 10 7GPE/ (mol Zrh)), the bulk density of this polyethylene particle powder (BD) 0.323 is g/ml, melting index: MI 2.16=34.3g/10min.
Experiment Comparative Examples 2
Adopt the method identical with implementing embodiment 2 to carry out the copolymerization of ethene, different is that the catalyzer of employing is the ES955-FI that Comparative Examples 1 prepares.The result obtains 76g polymer beads powder, and catalyst efficiency is 489gPE/ (gcath) (3.0 * 10 7GPE/ (mol Zrh)), the bulk density of this polymer beads powder (BD) is 0.332g/ml, melting index: MI 2.16=38.8g/10min.
Comparative Examples 2
This preparation example is for the preparation of the carried metallocene catalyst that uses in the olefine polymerizing process according to the present invention.
With SBA-15 (being purchased the high-tech share company limited from Changchun Jilin University) 400 ℃ of calcinings 10 hours under nitrogen protection, removing hydroxyl and remaining moisture, thereby obtain the SBA-15 through thermal activation;
Activated SBA-15 is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced with 0.56 gram, add 10 milliliters of refining toluene (refluxing 24 hours with sodium) and 1 gram methylaluminoxane (being purchased the Albemarle company from the U.S.), and stirred 4 hours at 50 ℃.After reaction is finished, 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 methylaluminoxane (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 refining toluene (refluxing 24 hours with sodium); stirred 30 minutes; under 30 ℃; 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, with 10 milliliters of toluene wash three times, follow, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after SBA-15-Cp).
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 the method identical with embodiment 1 to carry out the homopolymerization of ethene, different is the SBA-15-Cp that the catalyzer of employing prepares for preparation Comparative Examples 2.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.Determine that as calculated the efficient of catalyzer is 384gPE/ (gcath) (3.5 * 10 6G PE/ (mol Zrh)).
Experiment Comparative Examples 4
Adopt the method identical with embodiment 2 that ethene and hexene are carried out copolymerization, different is that the catalyzer of employing is for preparing the SBA-15-Cp that Comparative Examples 1 prepares.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.Determine that as calculated the efficient of catalyzer is 438gPE/ (gcath) (2.7 * 10 7G PE/ (mol Zrh)).

Claims (10)

1. olefine polymerizing process, this method is included under the olefinic polymerization condition, one or more alkene are contacted with loaded catalyst, it is characterized in that, described loaded catalyst comprises carrier and loads on two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichloride and alkylaluminoxanes on the described carrier, described carrier is SBA-15, and described carrier is bar-shaped, and the length of rod is the 30-100 micron.
2. method according to claim 1, wherein, total amount with described loaded catalyst is benchmark, and the total amount of described two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichlorides and alkylaluminoxane is 10-60 weight %, and the content of described carrier is 40-90 weight %; The mol ratio of the zirconium in the aluminium in the described alkylaluminoxane and described two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichloride is 200-500:1.
3. method according to claim 2, wherein, the mol ratio of the zirconium in the aluminium in the described alkylaluminoxane and described two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichloride is 250-350:1.
4. according to any described method among the claim 1-3, wherein, described alkylaluminoxane is methylaluminoxane.
5. method according to claim 1, wherein, the most probable aperture of described 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.
6. method according to claim 1, wherein, described alkene is one or more in ethene, alpha-olefin and the diolefin.
7. method according to claim 6, wherein, described alkene is ethene, C 3-C 101-alkene, C 4-C 8Diolefin in one or more.
8. method according to claim 1, wherein, described olefinic polymerization condition comprises: temperature is-78 ℃ to 100 ℃, pressure is 0.01-10MPa.
9. method according to claim 1, wherein, described contact is carried out in the presence of solvent, and in two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichloride, the concentration of described loaded catalyst in solvent is 1 * 10 -8-1 * 10 -3Mol, described olefinic polymerization condition comprises: temperature is-78 ℃ to 100 ℃, pressure is 0.01-10MPa.
10. method according to claim 9, wherein, in two [N-cyclohexyl-(3-tertiary butyl salicylic alidehyde imine base)] zirconium dichloride, the concentration of described loaded catalyst in solvent is 1 * 10 -8-1 * 10 -5Mol.
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