CN1271094C - Loading type bifunctional calulyst system and its preparation method and application - Google Patents
Loading type bifunctional calulyst system and its preparation method and application Download PDFInfo
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- CN1271094C CN1271094C CN 03158194 CN03158194A CN1271094C CN 1271094 C CN1271094 C CN 1271094C CN 03158194 CN03158194 CN 03158194 CN 03158194 A CN03158194 A CN 03158194A CN 1271094 C CN1271094 C CN 1271094C
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Abstract
The present invention relates to a loading type bifunctional catalyst system. An inorganic material loading post transition metal complex with a layered structure is used as an oligomerisation catalyst, and a silicon dioxide loading metallocene coordination compound is used as a copolymerization catalyst. Aluminum alkyl is used as a unique cocatalyst, and ethene is used as a unique monomer. The preparation method of the present invention mainly comprises the preparation of the montmorillonite loading oligomerisation catalyst and the silicon dioxide loading copolymerization catalyst. Firstly, a montmorillonite carrier and a silicon dioxide carrier are prepared. Secondly, the carriers are respectively loaded with the oligomerisation catalyst and the copolymerization catalyst to form the loading type bifunctional catalyst system. The method has the advantages of simple preparation technology and easy synthesis of the catalyst system. The density, the branching degree and other physical mechanical properties of different linear low-density polyethylene can be controlled by regulating a proportion of the two catalysts. The catalyst obtained by the synthetic method of the present invention has high stability. A polymer obtained by catalyzing ethylene polymerization is not stuck to a kettle and has large apparent density, a good shape and good industrial application prospects.
Description
Technical field
The present invention relates to a kind of load bifunctional catalysis system.
The invention still further relates to the preparation method of above-mentioned catalyst system, relate in particular to the preparation method of montmorillonite load catalyst for oligomerization and silicon dioxide carried catalyst for copolymerization in the catalyst system.
The invention still further relates to the application of above-mentioned catalyst system in the preparation linear low density polyethylene.
Background technology
Realize that with metallocene catalyst the copolymerizing linear low-density polyethylene (LLDPE) of ethene and alpha-olefin is a research focus in the last few years, required alpha-olefin is generated by ethylene oligomerization usually, and rectifying separation obtains hexene, octene, decene etc. then.If can use a kind of bifunctional catalyst system, in reaction system, be alpha-olefin with ethylene oligomerization by catalyst for oligomerization, ethene and alpha-olefin in-situ copolymerization generate LLDPE under the effect of catalyst for copolymerization simultaneously, will simplify production technique, reduce production costs greatly.J.Polym.Sci, Polym.Chem.Ed.22,3027 (1984); 24,1069 (1986); Petrochemical complex, 23.491 (1994).
Traditional Ziegler-Natta catalyst is used for ethene and the fashionable LLDPE that can not get high insertion rate of alpha-olefin copolymer, and is poorer for its copolymerization performance of high carbon number alpha-olefin.And the methylaluminoxane (MAO) that the eighties Kaminsky finds can improve its catalytic activity and copolymerization performance (Angew.Chem.Int.Ed.Engl.19,396 (1980)) during as the promotor of metallocene greatly.At present, ethene and propylene, the high carbon number alpha-olefin copolymer by metallocene catalysts is the focus of polyolefine material research.In recent years, emerging constrained geometry catalyst is present optimal copolymerization catalyst for ethylene.Bazan[J.Am.Chem.Soc.120 (5), 1082-1083 (1998)] design synthetic (C6H5B-OEt) 2ZrCl2 can close under the effect of MAO in the catalyzed ethylene oligomerisation, obtain ethylene oligomer, and then utilize constrained geometry catalyst and in-situ copolymerization, successfully prepare LLDPE.But the weak point of this method is used ethylene oligomerization catalyst instability, and the alpha-olefin selectivity only is 40-90%, its oligomerization product is the 1-alkene, 2-alkyl-1-alkene and 2-alkene, wherein, 2-alkyl-1-alkene and 2-alkene can not form multipolymer with ethene.
Summary of the invention
The object of the present invention is to provide a kind of load bifunctional catalysis system, form by catalyst for oligomerization, catalyst for copolymerization and promotor.
In the catalyst system provided by the invention, catalyst for oligomerization is that the alpha-diimine pyridine iron of montmorillonite load is that (alpha-olefin selectivity＞99%, carbon number distribution are C to title complex
4～C
30, be mainly C
8～C
14), its molecular structural formula is as follows:
R
1＝-H，-CH
3 X＝Br，Cl
R
2＝-CH
3，-CH
2CH
3，-CH(CH
3)
2，-OCH
3
R
3＝-CH
3，-CH
2CH
3，-CH(CH
3)2，-OCH
3，-Br，-Cl，-F
X＝-Br，-Cl
Described montmorillonite carrier is generally porous laminated.The example of non-limiting scope is as Na-polynite, Mg-polynite, Ca-polynite, H-polynite or Li-polynite etc.
The weight ratio of described carrier and catalyst for oligomerization is 5: 1～100: 1, and the best is 20: 1～80: 1.
Catalyst for copolymerization is a silica supports load catalyst for copolymerization, and wherein catalyst for copolymerization is that Ti, Zr, Hf etc. are the cyclopentadienyl compound of central atom with metallocene.The cyclopentadienyl compound can be single bridging, and doube bridge connection or non-bridge crosslinking structure are that the metallocene of central atom is best with bridging Zr, and these compounds are:
Et (Ind)
2ZrCl
2, Me
2Si (Ind)
2ZrCl
2, Et (Ind)
2ZrMe
2, Me
2Si (Ind)
2ZrMe
2, Cp
*SiMe
2NButZrCl
2, Cp
*SiMe
2NBu
tTiCl
2Or IndSiMe
2NBu
tZrCl
2Deng.In the described compound: Et is an ethyl, and Ind is an indenyl, and Me is a methyl, and Cp is luxuriant ring, and But is a butyl.
Described silica supports is generally vesicular.The granular size of preferred vector is 0.1-1000 μ m, and specific surface area is 60-500m
2/ g, pore volume are 0.1-7.0cm
3/ g, the aperture is 3-70nm.
The weight ratio of described carrier and catalyst for copolymerization is 5: 1～100: 1, and the best is 10: 1～50: 1.
The mol ratio of described catalyst for oligomerization and catalyst for copolymerization is 1: 200～10: 1, and the best is 1: 50～4: 1.
Described promotor is an aluminum alkyls, as trimethyl aluminium (TMA), triethyl aluminum (TEA), triisobutyl aluminium (TIBA) etc., wherein be best with TEA, the mol ratio of Fe in Al in the described alkylaluminoxane and the described dual-function catalyst and the total amount of Zr or Ti or Hf etc. is 50: 1～5000: 1, the best is 100: 1～3000: 1, and catalyst for oligomerization, the concentration of load catalyst for copolymerization total amount in polymerization system are 2 * 10 in the described dual-function catalyst
-6Mol/L～2000 * 10
-6Mol/L, the best is 20 * 10
-6Mol/L～400 * 10
-6Mol/L.
The method of catalyst for copolymerization in the above-mentioned catalyst system of preparation provided by the invention, carry out in the following order:
1, the preparation of montmorillonite carrier
With polynite vacuum-drying, add the alkylalumoxane solution stir process, with the non-aqueous non-polar solvent washing, to filter, drying makes montmorillonite carrier.The preferred preparation scheme is as follows: with polynite vacuum-drying 1-15 hour 30-200 ℃ the time, add alkylalumoxane solution, the concentration of described alkylalumoxane solution is 0.1-10mol/L, be preferably in 1-3mol/L, aluminium and polynite weight ratio 1: 1-1: 20, at 20-80 ℃ of stir process 4-12 hour, unreacted alkylaluminoxane is washed with non-aqueous non-polar solvent, filter, drying obtains montmorillonite carrier.
2, the preparation of the ethylene oligomerization catalyst of montmorillonite load
Ethylene oligomerization catalyst and dry toluene will be added in the above gained montmorillonite carrier, the weight ratio of polynite and catalyst for oligomerization is 5: 1～100: 1, the weight ratio of toluene and polynite is 50: 1～5: 1,20～120 ℃ of reactions 2～24 hours, preferably 30～90 ℃ of reactions 4～16 hours, with the dry toluene flush away ethylene oligomerization catalyst of load not, 30～90 ℃ of vacuum-drying 3～9 hours obtains the montmorillonite load ethylene oligomerization catalyst.
The method of catalyst for copolymerization in the above-mentioned catalyst system of preparation provided by the invention, carry out in the following order:
With silicon-dioxide vacuum-drying, add the alkylalumoxane solution stir process, protection of inert gas is standby; Copolymerization catalyst for ethylene and alkylalumoxane solution are mixed stirring, and protection of inert gas is standby; Under the protection of inert gas, carrier and catalyst solution are mixed stir process, remove behind the catalyzer of not load with the non-polar solvent washing, vacuum-drying obtains the load catalyst for copolymerization.The preferred preparation scheme is as follows: with silicon-dioxide vacuum-drying 1-15 hour 30-400 ℃ the time, add alkylalumoxane solution, the concentration of described alkylalumoxane solution is 0.1-10mol/L, be preferably in 1-3mol/L, the weight ratio 1 of aluminium and silicon-dioxide: 1-1: 20, at 20-120 ℃ of stir process 4-12 hour, protection of inert gas was standby; Copolymerization catalyst for ethylene is dissolved in the alkylaluminoxane, the concentration of described alkylalumoxane solution is 0.1-10mol/L, is preferably in 1-3mol/L, the weight ratio 1 of aluminium and catalyst for copolymerization: 1-1: 20, at 20-120 ℃ of stir process 4-12 hour, protection of inert gas was standby; Both are mixed, the weight ratio of described silicon-dioxide and catalyst for copolymerization is 5: 1-100: 1, the weight ratio of alkylaluminoxane and silicon-dioxide is 50: 1-5: 1, at 20-120 ℃ of stir process 4-12 hour, remove the catalyzer and the alkylaluminoxane of not load, with non-aqueous non-polar solvent washing, 30-90 ℃ obtained the load catalyst for copolymerization in vacuum-drying 3-9 hour.
The application of catalyst system provided by the invention in the preparation linear low density polyethylene:
Under nitrogen or argon gas atmosphere, earlier alkyl aluminum solutions is scattered in the non-polar organic solvent, after stirring 1～30 minute, add load ethylene oligomerization and load catalyst for copolymerization, the weight ratio of catalyst for oligomerization and catalyst for copolymerization (Fe/Zr) is 5: 1～100: 1, the best is 20: 1～80: 1, Al: (Fe+Zr or Ti or Hf etc.) mol ratio 100～5000, be preferably 200～2000, feed olefinic monomer, carried out polyreaction 0.5～5 hour at 20～90 ℃, be preferably 1～3 hour, add acidifying ethanol and stop polyreaction, washing, drying obtains linear low density polyethylene, and the apparent density of polymkeric substance is greater than 0.32g/cm
3
Polymerization system technology of the present invention is simple, has high catalytic activity, and the product form is good, and apparent density is big (greater than 0.32g/cm
3), having than low melting point, its melting range is 90～127 ℃, density range is at 0.900～0.950g/cm
3, the tensile strength scope is 3～30MPa.
In sum, the present invention is that title complex is a catalyst for oligomerization with the alpha-diimine pyridine iron of montmorillonite load, silicon dioxide carried metallocene complex is a catalyst for copolymerization, aluminum alkyls is unique promotor, ethene is only monomer, original position generates alpha-olefin, and the linear low density polyethylene that goes out to have simultaneously branch chain of different length with the in-situ copolymerization prepared in reaction.The present invention has simplified production technique, owing to do not need expensively to add common monomer, and need not MAO, only need an a small amount of aluminum alkyls can reach maximum catalytic activity, thereby can reduce production costs; By changing the loading condition and the polymerizing condition of catalyzer, can realize the molecule of polymkeric substance is cut out; Described load dual-function catalyst helps the form of controlling polymers, and the apparent density of the polymkeric substance that obtains is greater than 0.32g/cm
3, suppressing sticking still phenomenon, this will be adapted at carrying out in slurry polymerization and the gas phase polymerization apparatus suitability for industrialized production.
Embodiment
Embodiment 1
1, all operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
2, catalyst system
(a) preparation of the catalyst for oligomerization of montmorillonite load
With polynite vacuum-drying 8 hours 60 ℃ the time, the methylaluminoxane solution (weight ratio of methylaluminoxane solution and polynite was pressed 6: 1) that adds 1.8mol/L stir process 8 hours in the time of 60 ℃ obtains montmorillonite carrier with unreacted methylaluminoxane with toluene wash 3 times, filtration, drying.Take by weighing the above-mentioned polynite of 4 grams, add 30 milliliters of toluene and 0.1g{[(2-ArN=C (Me))
2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(Me)
2) solution 50 ℃ of down reactions 12 hours; With toluene flush away { [(2-ArN=C (Me)) of load not
2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(Me)
2); Wherein toluene solvant vacuumized remove, vacuumized dry 8 hours, obtain the ethylene oligomerization catalyst of the montmorillonite load of Fe content 40 μ mol/g, under noble gas, preserve standby at 60 ℃.
(b) preparation of silicon dioxide carried catalyst for copolymerization
With the vacuum-drying 8 hours 60 ℃ time of 1g silicon-dioxide, the methylaluminoxane solution (weight ratio of methylaluminoxane solution and silicon-dioxide was pressed 8: 1) that adds 1.8mol/L stir process 3 hours in the time of 120 ℃, nitrogen protection is standby.With 0.2gEt (Ind)
2ZrCl
2Be dissolved in wiring solution-forming in the methylaluminoxane of 8mL 1.8mol/L, stirred 3 hours down at 60 ℃, nitrogen protection is standby.After both were mixed, 50 ℃ were stirred 3 hours; With the toluene flush away Et of load (Ind) not
2ZrCl
2Wherein toluene solvant vacuumized remove, vacuumized dry 8 hours, obtain the silicon dioxide carried copolymerization catalyst for ethylene of zirconium content 50 μ mol/g, under noble gas, preserve standby at 60 ℃.
(c) promotor is TEA
3, a reactor that the 2L of agitator is housed is replaced three times with nitrogen and ethene respectively, feed ethene then, add the 1L hexane, add 3mL TEA, stir after 3 minutes, add the catalyst for oligomerization and silicon dioxide carriedization of the 200mg catalyst for copolymerization of 25mg montmorillonite load, be warming up to 70 ℃ and boost to 0.7MPa and carried out copolyreaction 2 hours rapidly, add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 2
1, all operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
2, catalyst system
(a) preparation of the catalyst for oligomerization of montmorillonite load
With polynite vacuum-drying 8 hours 60 ℃ the time, the methylaluminoxane solution (weight ratio of methylaluminoxane solution and polynite was pressed 6: 1) that adds 1.8mol/L stir process 8 hours in the time of 60 ℃ obtains montmorillonite carrier with unreacted methylaluminoxane with toluene wash 3 times, filtration, drying.Take by weighing the above-mentioned polynite of 4 grams, add 30 milliliters of toluene and 0.08g{[(2-ArN=C (Me))
2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(OMe)
2) solution 50 ℃ of down reactions 12 hours; With toluene flush away { [(2-ArN=C (Me)) of load not
2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(OMe)
2); Wherein toluene solvant vacuumized remove, vacuumized dry 8 hours, obtain the ethylene oligomerization catalyst of the montmorillonite load of Fe content 30 μ mol/g, under noble gas, preserve standby at 60 ℃.
(b) preparation of silicon dioxide carried catalyst for copolymerization, identical with embodiment 1.
(c) promotor is TEA
3, a reactor that the 2L of agitator is housed is replaced three times with nitrogen and ethene respectively, feed ethene then, add the 1L hexane, add 3mL TEA, stir after 3 minutes, add the catalyst for oligomerization and the silicon dioxide carried catalyst for copolymerization of 200mg of 60mg montmorillonite load, be warming up to 70 ℃ and boost to 0.7MPa and carried out copolyreaction 2 hours rapidly, add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 3
1, all operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
2, catalyst system
(a) preparation of the catalyst for oligomerization of montmorillonite load
With polynite vacuum-drying 8 hours 60 ℃ the time, the methylaluminoxane solution (weight ratio of methylaluminoxane solution and polynite was pressed 6: 1) that adds 1.8mol/L stir process 8 hours in the time of 60 ℃ obtains montmorillonite carrier with unreacted methylaluminoxane with toluene wash 3 times, filtration, drying.Take by weighing the above-mentioned polynite of 4 grams, add 30 milliliters of toluene and 0.4g{[(2-ArN=C (Me)) 2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(Me)
2) solution 50 ℃ of down reactions 12 hours; With toluene flush away { [(2-ArN=C (Me)) 2C of load not
5H
3N] FeCl
2(Ar=2,4-C
6H
4(OMe)
2); Wherein toluene solvant vacuumized remove, vacuumized dry 8 hours, obtain the ethylene oligomerization catalyst of the montmorillonite load of Fe content 160 μ mol/g, under noble gas, preserve standby at 60 ℃.
(b) preparation of silicon dioxide carried catalyst for copolymerization
With the vacuum-drying 8 hours 60 ℃ time of 1g silicon-dioxide, the methylaluminoxane solution (weight ratio of methylaluminoxane solution and silicon-dioxide was pressed 8: 1) that adds 1.8mol/L stir process 3 hours in the time of 120 ℃, nitrogen protection is standby.With 0.2g Me
2Si (Ind)
2ZrCl
2Be dissolved in wiring solution-forming in the methylaluminoxane of 8mL1.8mol/L, stirred 3 hours down at 60 ℃, nitrogen protection is standby.After both were mixed, 50 ℃ were stirred 3 hours; With the toluene flush away Et of load (Ind) not
2ZrCl
2Wherein toluene solvant vacuumized remove, vacuumized dry 8 hours, obtain the silicon dioxide carried copolymerization catalyst for ethylene of zirconium content 45 μ mol/g, under noble gas, preserve standby at 60 ℃.
(c) promotor is TEA
3, a reactor that the 2L of agitator is housed is replaced three times with nitrogen and ethene respectively, feed ethene then, add the 1L hexane, add 3mL TEA, stir after 3 minutes, add the catalyst for oligomerization and the silicon dioxide carried catalyst for copolymerization of 200mg of 50mg montmorillonite load, be warming up to 70 ℃ and boost to 0.7MPa and carried out copolyreaction 2 hours rapidly, add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 4
1, all operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
2, catalyst system
(a) preparation of the catalyst for oligomerization of montmorillonite load
With polynite vacuum-drying 8 hours 60 ℃ the time, the methylaluminoxane solution (weight ratio of methylaluminoxane solution and polynite was pressed 6: 1) that adds 1.8mol/L stir process 8 hours in the time of 60 ℃ obtains montmorillonite carrier with unreacted methylaluminoxane with toluene wash 3 times, filtration, drying.Take by weighing the above-mentioned polynite of 4 grams, add 30 milliliters of toluene and 0.17g{[(2-ArN=C (Me))
2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(OMe)
2) solution 50 ℃ of down reactions 12 hours; With toluene flush away { [(2-ArN=C (Me)) of load not
2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(OMe)
2); Wherein toluene solvant vacuumized remove, vacuumized dry 8 hours, obtain the ethylene oligomerization catalyst of the montmorillonite load of Fe content 60 μ mol/g, under noble gas, preserve standby at 60 ℃.
(b) preparation of silicon dioxide carried catalyst for copolymerization, identical with embodiment 3.
(c) promotor is TEA
3, a reactor that the 2L of agitator is housed is replaced three times with nitrogen and ethene respectively, feed ethene then, add the 1L hexane, add 3mL TEA, stir after 3 minutes, add the catalyst for oligomerization and the silicon dioxide carried catalyst for copolymerization of 200mg of 50mg montmorillonite load, be warming up to 70 ℃ and boost to 1.4MPa and carried out copolyreaction 2 hours rapidly, add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 5
1, all operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
2, catalyst system
(a) preparation of the catalyst for oligomerization of montmorillonite load
With polynite vacuum-drying 8 hours 60 ℃ the time, the methylaluminoxane solution (weight ratio of methylaluminoxane solution and polynite was pressed 6: 1) that adds 1.8mol/L stir process 8 hours in the time of 60 ℃ obtains montmorillonite carrier with unreacted methylaluminoxane with toluene wash 3 times, filtration, drying.Take by weighing the above-mentioned polynite of 4 grams, add 30 milliliters of toluene and 0.1g{[(2-ArN=C (Me))
2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(Me)
2) solution 50 ℃ of down reactions 12 hours; With toluene flush away { [(2-ArN=C (Me)) of load not
2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(OMe)
2); Wherein toluene solvant vacuumized remove, vacuumized dry 8 hours, obtain the ethylene oligomerization catalyst of the montmorillonite load of Fe content 40 μ mol/g, under noble gas, preserve standby at 60 ℃.
(b) preparation of silicon dioxide carried catalyst for copolymerization, identical with embodiment 1.
(c) promotor is TEA
3, a reactor that the 2L of agitator is housed is replaced three times with nitrogen and ethene respectively, feed ethene then, add the 1L hexane, add 6mL TEA, stir after 3 minutes, add the catalyst for oligomerization and the silicon dioxide carried catalyst for copolymerization of 200mg of 50mg montmorillonite load, be warming up to 70 ℃ and boost to 1.4MPa and carried out copolyreaction 2 hours rapidly, add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 6
1, all operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
2, catalyst system
(a) preparation of the catalyst for oligomerization of montmorillonite load
With polynite vacuum-drying 8 hours 60 ℃ the time, the methylaluminoxane solution (weight ratio of methylaluminoxane solution and polynite was pressed 6: 1) that adds 1.8mol/L stir process 8 hours in the time of 60 ℃ obtains montmorillonite carrier with unreacted methylaluminoxane with toluene wash 3 times, filtration, drying.Take by weighing the above-mentioned polynite of 4 grams, add 30 milliliters of toluene and 0.1g{[(2-ArN=C (Me))
2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(Me)
2) solution 50 ℃ of down reactions 12 hours; With toluene flush away { [(2-ArN=C (Me)) of load not
2C
5H
3N] FeCl
2(Ar=2,4-C
6H
4(OMe)
2); Wherein toluene solvant vacuumized remove, vacuumized dry 8 hours, obtain the ethylene oligomerization catalyst of the montmorillonite load of Fe content 40 μ mol/g, under noble gas, preserve standby at 60 ℃.
(b) preparation of silicon dioxide carried catalyst for copolymerization
With the vacuum-drying 8 hours 60 ℃ time of 1g silicon-dioxide, the methylaluminoxane solution (weight ratio of methylaluminoxane solution and silicon-dioxide was pressed 8: 1) that adds 1.8mol/L stir process 3 hours in the time of 120 ℃, nitrogen protection is standby.With 0.2g Cp
*SiMe
2NBu
tTiCl
2Be dissolved in wiring solution-forming in the methylaluminoxane of 8mL1.8mol/L, stirred 3 hours down at 60 ℃, nitrogen protection is standby.After both were mixed, 50 ℃ were stirred 3 hours; With the toluene flush away Cp of load not
*SiMe
2NBu
tTiCl
2Wherein toluene solvant vacuumized remove, vacuumized dry 8 hours, obtain the silicon dioxide carried copolymerization catalyst for ethylene of zirconium content 40 μ mol/g, under noble gas, preserve standby at 60 ℃.
(c) promotor is TEA
3, a reactor that the 2L of agitator is housed is replaced three times with nitrogen and ethene respectively, feed ethene then, add the 1L hexane, add 3mL TEA, stir after 3 minutes, add the catalyst for oligomerization and the silicon dioxide carried catalyst for copolymerization of 200mg of 50mg montmorillonite load, be warming up to 70 ℃ and boost to 1.4MPa and carried out copolyreaction 2 hours rapidly, add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 7
1, all operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
2, catalyst system
(a) preparation of the catalyst for oligomerization of montmorillonite load
With polynite vacuum-drying 8 hours 60 ℃ the time, the methylaluminoxane solution (weight ratio of methylaluminoxane solution and polynite was pressed 6: 1) that adds 1.8mol/L stir process 8 hours in the time of 60 ℃ obtains montmorillonite carrier with unreacted methylaluminoxane with toluene wash 3 times, filtration, drying.Take by weighing the above-mentioned polynite of 4 grams, the solution that adds 30 milliliters of toluene and 0.1g catalyst for oligomerization (structural formula is seen following formula) reacted 12 hours down at 50 ℃; With the toluene flush away catalyst for oligomerization of load not; Wherein toluene solvant vacuumized remove, vacuumized dry 8 hours, obtain the ethylene oligomerization catalyst of the montmorillonite load of Fe content 30 μ mol/g, under noble gas, preserve standby at 60 ℃.
(b) preparation of silicon dioxide carried catalyst for copolymerization, identical with embodiment 1.
(c) promotor is TEA
3, a reactor that the 2L of agitator is housed is replaced three times with nitrogen and ethene respectively, feed ethene then, add the 1L hexane, add 3mL TEA, stir after 3 minutes, add the catalyst for oligomerization and the silicon dioxide carried catalyst for copolymerization of 200mg of 25mg montmorillonite load, be warming up to 70 ℃ and boost to 0.7MPa and carried out copolyreaction 2 hours rapidly, add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Polymerizing condition among table 1. embodiment and aggregated data
| Embodiment | Catalyst for copolymerization (μ mol) | Catalyst for oligomerization (μ mol) | Polymerization pressure (Mpa) | Promotor/catalyzer (mol/mol) | Catalyst activity a | Fusing point (℃) | Apparent density (g/cm 3) |
| 1 | 1 | 10 | 0.7 | 400 | 5.4 | 123.8 | 0.34 |
| 2 | 1.8 | 10 | 0.7 | 400 | 7.8 | 120.6 | 0.38 |
| 3 | 8 | 9 | 0.7 | 250 | 11.3 | 103.6 | 0.38 |
| 4 | 3 | 9 | 1.4 | 350 | 37.2 | 110.2 | 0.40 |
| 5 | 2 | 10 | 1.4 | 700 | 24.5 | 116.3 | 0.39 |
| 6 | 2 | 8 | 1.4 | 420 | 30.3 | 113.5 | 0.37 |
| 7 | 0.75 | 10 | 0.7 | 400 | 6.53 | 124.6 | 0.36 |
aCatalyst activity: 10
6G PEmol
-1(Zr or Ti) h
-1Atm
-1
Claims (12)
1, a kind of load bifunctional catalysis system, wherein:
Catalyst for oligomerization is that montmorillonite load alpha-diimine pyridine iron is a title complex, and the molecular structural formula of catalyst for oligomerization is as follows; The particle of carrier is 0.1-1000 μ m, and specific surface area is 60-500m
2/ g, pore volume are 0.1-7.0cm
3/ g, the aperture is 3-70nm, the weight ratio of the neat catalyst for copolymerization of carrier is 5: 1～100: 1;
Described polynite is porous laminated structure;
R
1＝-H，-CH
3 X＝Br，Cl
R
2＝-CH
3，-CH
2CH
3，-CH(CH
3)
2，-OCH
3
R
3＝-CH
3，-CH
2CH
3，-CH(CH
3)
2，-OCH
3，-Br，-Cl，-F
X＝-Br，-Cl
Catalyst for copolymerization is silicon dioxide carried catalyst for copolymerization, and wherein catalyst for copolymerization is to be the cyclopentadienyl compound of central atom with Ti, Zr or Hf; The particle of carrier is 0.1-1000 μ m, and specific surface area is 60-500m
2/ g, pore volume are 0.1-7.0cm
3/ g, the aperture is 3-70nm, the weight ratio of carrier and catalyst for copolymerization is 5: 1～100: 1;
Promotor is an aluminum alkyls, and wherein the mol ratio of the total amount of the Fe in aluminium and the above-mentioned catalyzer and Zr or Ti or Hf is 50: 1～5000: 1;
Described silica supports is a vesicular;
The mol ratio of described catalyst for oligomerization and catalyst for copolymerization is 1: 200～10: 1;
Catalyst for oligomerization, the concentration of catalyst for copolymerization total amount in polymerization system are 2 * 10 in the described catalyst system
-6Mol/L～2000 * 10
-6Mol/L.
2, catalyst system as claimed in claim 1 is characterized in that, alpha-olefin selectivity＞99% in the described catalyst for oligomerization, and carbon number distribution is C
4～C
30
3, catalyst system as claimed in claim 1 or 2 is characterized in that, the carbon number distribution in the described catalyst for oligomerization is C
8～C
14
4, catalyst system as claimed in claim 1 is characterized in that, described cyclopentadienyl compound is single bridging, doube bridge connection or non-bridge crosslinking structure, and these compounds are Et (Ind)
2ZrCl
2, Me
2Si (Ind)
2ZrCl
2, Et (Ind)
2ZrMe
2, Me
2Si (Ind)
2ZrMe
2, Cp
*SiMe
2NBu
tZrCl
2, Cp
*SiMe
2NBu
tTiCl
2Or IndSiMe
2NBu
tZrCl
2
In the described compound: Et is an ethyl, and Ind is an indenyl, and Me is a methyl, and Cp is luxuriant ring, and But is a butyl.
5, catalyst system as claimed in claim 1 is characterized in that, described montmorillonite carrier is Na-polynite, Mg-polynite, Ca-polynite, H-polynite or Li-polynite;
Wherein the weight ratio of carrier and catalyst for oligomerization is 20: 1～80: 1.
6, catalyst system as claimed in claim 1 is characterized in that, described carrier is a silicon-dioxide;
Wherein the weight ratio of carrier and catalyst for copolymerization is 10: 1～50: 1.
7, catalyst system as claimed in claim 1 is characterized in that, the weight ratio of described catalyst for oligomerization and catalyst for copolymerization is 1: 50～4: 1.
8, catalyst system as claimed in claim 1 is characterized in that, described promotor trimethyl aluminium, triethyl aluminum or triisobutyl aluminium;
The mol ratio of the total amount of aluminium in the promotor and the Fe in the catalyzer and Zr or Ti or Hf is 100: 1～3000: 1;
Catalyst for oligomerization, the concentration of catalyst for copolymerization total amount in polymerization system are 20 * 10 in the catalyst system
-6Mol/L～400 * 10
-6Mol/L.
9, a kind of method for preparing montmorillonite load rear transition metal catalyst for oligomerization in the above-mentioned catalyst system, its key step is:
A) preparation of montmorillonite carrier: with polynite vacuum-drying 1-15 hour 30-200 ℃ the time, adding concentration is the 0.1-10mol/L alkylalumoxane solution, aluminium and polynite weight ratio 1: 1-1: 20, stirred 4-12 hour at 20-80 ℃, washing is filtered, and drying obtains montmorillonite carrier;
B) preparation of montmorillonite carrier load catalyst for oligomerization: will add catalyst for oligomerization and dry toluene in the step a gained montmorillonite carrier, reaction conditions is 20-120 ℃, 2-24 hour; The weight ratio of polynite and catalyst for oligomerization is 5: 1-100: 1, the weight ratio of toluene and polynite is 50: 1-5: 1, dry toluene washing, 30-90 ℃ vacuum-drying 3-9 hour, the montmorillonite load catalyst for oligomerization.
10, preparation method as claimed in claim 9 is characterized in that, the reaction conditions described in the step b is 30-90 ℃, 4-16 hour.
11, a kind of method for preparing silicon dioxide carried metallocene catalyst for copolymerization in the above-mentioned catalyst system, its key step is:
With silicon-dioxide vacuum-drying 1-15 hour 30-400 ℃ the time, adding concentration is the 0.1-10mol/L alkylalumoxane solution, and aluminium and silica weight are than 1: 1-1: 20, and 20-120 ℃ of stirring 4-12 hour, protection of inert gas was standby; Catalyst for copolymerization and alkylalumoxane solution are mixed stirring, and reaction conditions is 20-120 ℃, and 2-24 hour, the weight ratio of alkylaluminoxane and silicon-dioxide was 50: 1-5: 1; Both are mixed, and the weight ratio of silicon-dioxide and catalyst for copolymerization is 5: 1-100: 1, at 20-120 ℃ of stir process 4-12 hour, anhydrous hexane, 30-90 ℃ vacuum-drying 3-9 hour, must silicon dioxide carriedization catalyst for copolymerization.
12, as the application of the described load bifunctional catalysis system of above-mentioned each claim in the preparation linear low density polyethylene.
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| CN101947449A (en) * | 2010-09-13 | 2011-01-19 | 大连理工大学 | Method for preparing nano Ti-based montmorillonite Cu catalyst and application of catalyst to HC-SCR |
| CN105985476B (en) * | 2015-02-04 | 2019-05-03 | 中国石油天然气股份有限公司 | The preparation method of branched polyethylene copolymer |
| CN106317266B (en) * | 2016-08-19 | 2018-11-16 | 常爱荣 | A kind of complex carrier catalyst for olefinic polymerization and preparation method thereof |
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