CN1344749A - Intercalated loaded metallocene catalyst and its catalysis in olefine polymerization - Google Patents
Intercalated loaded metallocene catalyst and its catalysis in olefine polymerization Download PDFInfo
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Abstract
The present invention relates to one new type catalysts. The intercalated loaded metallocene catalyst is prepared by using clay as main amterial and through first simple ion exchange process, alpha-amino acid ester and hydrochloric acid treatment and modification with methyl aluminium alkoxide. It has high loading rate, high activity and high stability. The catalyst of the present invention is used in olefine slurry polymerization and can prepare polyolefine resin with performance superior to that of product obtained with other loaded metallocene catalyst.
Description
Technical field: the present invention relates to intercalated loaded type metallocene catalyst and the application aspect olefinic polymerization thereof.
Background technology:, the some shortcomings part is arranged also although zirconocene catalyst is very high to polymerization in homogeneous phase catalytic efficiencies such as ethene, propylene.When MAO made promotor, aluminium/zirconium was than too high; Be not suitable for high temperature polymerization; Because the product that homogeneous system generates is unformed powder, tap density is minimum, easily attached on the reactor wall, forms firm rete, so be not suitable for slurry and vapour phase polymerization.After the carrierization, can obviously reduce aluminium/zirconium ratio, improve the product form.Carrierization also can change the coordination environment of central metal, influences the catalytic selectivity and the directional property in active centre.SiO particularly
2Do carrier and can also make product that better particle form is arranged,, reduce the energy consumption of producing so that exempt the granulation process of product.At present, all olefin production companies mostly adopt the catalyzer of inorganic carrierization to carry out actual production in the world.Mineral-type carrier commonly used mainly contains: silicon-dioxide, aluminum oxide, magnesium chloride, polynite etc.Because of the residual all kinds of hydroxyl hydrogens of carrier surface, make active effective constituent inactivation with the carried metallocene catalyst of above-mentioned preparing carriers, cause active the reduction, catalyst cupport instability simultaneously, the actual negative carrying capacity is low, and the effective active composition of load is low.
It also is a kind of method that direct inorganic materials supported catalyst with nano-scale is used for catalyzed polymerization.It is the load metallocene catalyst preparation method of carrier with the nano material that China applies for a patent that 00105161.X reported, wherein used nano material is for handling polynite, the hectorite that forms through amine salt, amino acid, saponite, mica and sepiolite etc., but the structure of above-mentioned supported catalyst and unclear.The shortcoming of this method shows that also nano-powder is difficult to obtain simultaneously, and costs an arm and a leg, and powder easily caking disperses inhomogeneous in material.
Summary of the invention: the method that the purpose of this invention is to provide a kind of intercalated loaded metallocene catalyst and catalysis in olefine polymerization thereof.Gained catalyzer master metal load rate height, to the olefin polymerizating activity height, and preparation cost is low, and the resulting polymers rerum natura has clear improvement.
The present invention prepares the intercalated loaded metallocene catalyst that the stratiform inorganic materials is a carrier with graft process, is made of carrier, Primary Catalysts, promotor and properties-correcting agent.Carrier mainly contains polynite, bentonite and halloysite etc., its unit cell is made up of two-layer silicon-oxy tetrahedron therebetween layer of aluminum oxygen octahedra, connect by public Sauerstoffatom between the two, the clay seam internal surface has negative charge, each negative charge footprint area 25-100
2, specific surface area 700-800m
2/ gram.Wherein the present invention preferably interlayer cation be the clay of sodium ion, the sodium ion exchange capacity is at 90-110meq/100g.The adjacent crystal layer of this class clay has negative charge, therefore, is generally adsorbing positively charged ion between the clay crystal layer, and this structure makes water and other polar molecule can enter between the clay crystal layer, and the exchange interaction between extraneous positively charged ion and inner positively charged ion can take place.Clay and water are mixed, just can form a stable clay water suspensoid, clay crystal layer wherein is under the hydration of interlayer cation, and is separated from one another.The present invention carries out ion exchange reaction by the clay of amino acid methyl ester hydrochloride and purifying, and the former is inserted in the latter's the interlayer, causes layered metal oxide or salt interlamellar spacing to increase greatly.Can make metallocene catalyst be easy to insert the interlayer of layered vector like this, increase the specific surface area of clay greatly, promote the raising of metallocene catalyst charge capacity.Simultaneously because above-mentioned layered metal oxide or salt have bigger interlamellar spacing and suitable passage, make monomer such as ethene can freely be diffused into interlayer and contact with the catalyst center metal ion, carry out polyreaction.
Intercalated loaded metallocene catalyst prepares by following steps among the present invention: clay was heat-treated 5-10 hour at 400-600 ℃; At room temperature heat treated clay is cleaned the solubility salt at 50% aqueous ethanolic solution, separate, purifying, repetitive operation three times; Being suitable for clay of the present invention is polynite and sodium bentonite; Clay with amino acid methyl ester hydrochloride and above-mentioned purifying at room temperature carried out ion exchange reaction 10-30 hour, was preferably 15-24 hour, adopted 50% aqueous ethanolic solution washing after drying; Suitable amino acid methyl ester hydrochloride is the a-amino acid ester hydrochloride, as α-glycine methyl ester hydrochloride and α-Phenylalanine methyl ester hydrochloride; In dry toluene with above-mentioned gained modified clay under 40-70 ℃, being preferably in 50-60 ℃ reacted 4-6 hour with promotor methylaluminoxane (MAO) down, the MAO add-on is that per 100 gram modified clays add 167-500ml MAO (1.5M), falls unreacted MAO with pure toluene wash; In dry toluene, be that the metallocene complex of 1: 1 cationization mixes with gained modified clay and metallocene compound or with mol ratio that boride forms, per 100 gram modified clays add metallocene catalyst 5-10 gram, carry out coordination reaction, metallocene compound is assembled in the laminated clay interplanar, form intercalated loaded metallocene catalyst, temperature of reaction is 40-60 ℃, and the reaction times is 10-20 hour; The ratio that the atoms metal content of Primary Catalysts accounts for the intercalated loaded metallocene catalyst total amount is that every gram catalyzer contains zirconium atom 26.7-62.5 milligram; Suitable metallocene compound is bis cyclopentadienyl zirconium dichloride and cyclopentadienyl titanium dichloride.
Promotor is to make Primary Catalysts form the compound in metallic cation active centre among the present invention, and as alkylaluminoxane and boride etc., suitable alkylaluminoxane is a methylaluminoxane, and suitable boride is trityl-tetrafluoro boron ((Ph
3C) BF
4).Wherein the mol ratio with boride formation is metallocene complex bis cyclopentadienyl zirconium dichloride (Cp in hexane solution of 1: 1 cationization
2ZrCl
2) and (Ph
3C) BF
4At 0 ℃ of reaction 6h down, after filtration, washing, drying, obtain chlorination (trityl-tetrafluoro boron)-chlorine zirconocene ([Cp with 1: 1 mol ratio
2ZrCl]
+[Cl (Ph
3C) BF
4]
-) title complex.
Above-mentioned catalyzer can be used for ethylene homo under the slurry polymerization processes and closes with ethene and alpha-olefin copolymer and close, ethylene pressure is 1.3 normal atmosphere, and polymerization temperature is 60 ℃, and polymerization time is 1 hour, add MAO and be 50-800 to aluminium/main metal molar ratio, its activity is 0.78-2.00 * 10
6G/ (mol.M.h).
Kept most of active ingredient owing to load factor is high, thereby the promotor consumption reducing, is example with the methylaluminoxane, and its aluminium/central metal atom rubs than being also to keep greater activity at 200 o'clock, also keeps active at 50 o'clock.Compare with other supported catalyst, the present invention has improved the stability of catalyzer greatly owing to adopt the preparing carriers intercal type metallocene supported catalyst of functionalization, the load factor height, and the catalytic activity height, the polymer morphology of its generation is good, the molecular weight height, bulk density is big.
Embodiment:
Embodiment 1
Earlier polynite was handled 5 hours in 400 ℃ retort furnace, take by weighing 6 grams after cooling and place centrifuge tube, add the 50ml50% aqueous ethanolic solution and clean the solubility salt, the normal temperature lower magnetic force stirred 10 minutes, centrifugation is 10 minutes then, discard clear liquid, add the 50ml50% aqueous ethanolic solution again, repeat aforesaid operations three times; Add 50ml50% aqueous ethanolic solution and 1 gram α-glycine methyl ester hydrochloride then, the normal temperature lower magnetic force stirred 24 hours, added the washing of 50ml50% aqueous ethanolic solution again and separated repetitive operation three times.The thorough drying under infrared lamp of the polynite that will handle at last places in the vacuum drying oven then 80 ℃ of following vacuum-dryings 24 hours.
Get the carrier that 3 grams were handled through glycine methyl ester salt; add 50ml toluene (following used toluene is and uses sodium Metal 99.5-potassium-sodium alloy to handle); the toluene solution that adds 15ml1.5M aluminium trimethide oxidation alkane; stirred 4 hours down at 50 ℃; take solvent then away; wash 3 times with the each 20ml of toluene; add 0.2 gram bis cyclopentadienyl zirconium dichloride then; 50ml toluene; stirred 10 hours down at 40 ℃, drain solvent, toluene wash; make load metallocene catalyst (being called for short catalyzer 1); whole process must be under nitrogen protection, and the anhydrous and oxygen-free operation is by the content of inductive coupling plasma body-atomic emission spectrum mensuration atoms metal zirconium; every gram supported catalyst contains 48 milligrams of zirconium atoms, and promptly zirconium accounts for load metallocene catalyst gross weight ratio (be called for short carry a zirconium amount) and is 6.25wt%.With being catalyzer (being called for short catalyzer 2) the do contrast experiment of carrier with the quadrat method preparation with the polynite of only handling in 400 ℃ retort furnace, recording and carrying the zirconium amount is 1.48wt%.
Carry out ethene slurry polymerization (ethylene pressure is 1.3 normal atmosphere, and polymerization temperature is 60 ℃, and polymerization time is 1 hour, adds MAO to always aluminium/the zirconium mol ratio is 800, and the aluminium zirconium that occurs below is than being total mol ratio) with catalyzer 1, its activity is 1.28 * 10
6G/ (mol.Zr.h)
With 2 pairs of ethene slurry polymerizations of catalyzer, its activity is 1.04 * 10 under similarity condition
6G/ (mol.Zr.h).Adopt the basic molecular structure parameter of high temperature GPC test polymer, the result is as follows: the weight-average molecular weight M of catalyzer 1 resulting polymers
w=18.95 * 10
4, number average
Molecular weight M
n=9.11 * 10
4, molecular weight distributing index is 2.08, the product bulk density is 0.44g/cm
3The weight-average molecular weight M of catalyzer 2 resulting polymers
w=12.34 * 10
4, number-average molecular weight M
n=5.32 * 10
4, molecular weight distributing index is 2.32, the product bulk density is 0.37g/cm
3
Embodiment 2
With embodiment 1 catalyzer ethene slurry polymerization, aluminium zirconium ratio is 400, and all the other are with embodiment 1.The activity of catalyzer cat1 is 1.31 * 10
6G/ (mol.Zr.h), the activity of cat2 is 0.98 * 10
6G/ (mol.Zr.h).Adopt the basic molecular structure parameter of high temperature GPC test polymer, the result is as follows: the weight-average molecular weight M of catalyzer 1 resulting polymers
w=15.88 * 10
4, number-average molecular weight M
n=7.49 * 10
4, molecular weight distributing index is 2.12, the product bulk density is 0.42g/cm
3The weight-average molecular weight M of catalyzer 2 resulting polymers
w=9.87 * 10
4, number-average molecular weight M
n=4.35 * 10
4, molecular weight distributing index is 2.27, the product bulk density is 0.32g/cm
3
Embodiment 3
With embodiment 1 catalyzer ethene slurry polymerization, aluminium zirconium ratio is 200, and all the other are with embodiment 1, and catalyzer 1 activity is 1.27 * 10
6/ (mol.Zr.h).Catalyzer 2 activity are 0.91 * 10
6G/ (mol.Zr.h).Adopt the basic molecular structure parameter of high temperature GPC test polymer, the result is as follows: the weight-average molecular weight M of catalyzer 1 resulting polymers
w=12.74 * 10
4, number-average molecular weight M
n=6.06 * 10
4, molecular weight distributing index is 2.10, the product bulk density is 0.40g/cm
3The weight-average molecular weight M of catalyzer 2 resulting polymers
w=10.27 * 10
4, number-average molecular weight M
n=4.80 * 10
4, molecular weight distributing index is 2.14, the product bulk density is 0.32g/cm
3
Embodiment 4
With embodiment 1 catalyzer ethene slurry polymerization, aluminium zirconium ratio is 50, and all the other are with embodiment 1, and catalyzer 1 activity is 0.85 * 10
6/ (mol.Zr.h).Catalyzer 2 activity are 0.78 * 10
6G/ (mol.Zr.h).Adopt the basic molecular structure parameter of high temperature GPC test polymer, the result is as follows: the weight-average molecular weight M of catalyzer 1 resulting polymers
w=9.87 * 10
4, number-average molecular weight M
n=4.61 * 10
4, molecular weight distributing index is 2.14, the product bulk density is 0.37g/cm
3The weight-average molecular weight M of catalyzer 2 resulting polymers
w=7.24 * 10
4, number-average molecular weight M
n=3.38 * 10
4, molecular weight distributing index is 2.14, the product bulk density is 0.28g/cm
3
Embodiment 5
Do the slurry copolymerization of ethene and octene-1 with embodiment 1 catalysis 1, octene-1 is 3 milliliters, and all the other are with embodiment 1.The catalytic activity of catalyzer 1 is 1.98 * 10
6G/ (mol.Zr.h), catalyzer 2 activity of such catalysts are 0.41 * 10
6G/ (mol.Zr.h).Adopt the basic molecular structure parameter of high temperature GPC test polymer, the result is as follows: the weight-average molecular weight M of catalyzer 1 resulting polymers
w=23.06 * 10
4, number-average molecular weight M
n=10.52 * 10
4, molecular weight distributing index is 2.14, the product bulk density is 0.44g/cm
3The weight-average molecular weight M of catalyzer 2 resulting polymers
w=14.97 * 10
4, number-average molecular weight M
n=6.60 * 10
4, molecular weight distributing index is 2.27, the product bulk density is 0.44g/cm
3
Embodiment 6
Earlier sodium bentonite was handled 5 hours in 600 ℃ retort furnace, take by weighing 6 grams after cooling and place centrifuge tube, add the 50ml50% aqueous ethanolic solution and clean the solubility salt, the normal temperature lower magnetic force stirred 10 minutes, centrifugation is 10 minutes then, discard clear liquid, add the 50ml50% aqueous ethanolic solution again, repeat aforesaid operations three times; Add 50ml50% aqueous ethanolic solution and 1 gram α-phenylalanine methyl ester hydrochloride then, the normal temperature lower magnetic force stirred 15 hours, added the washing of 50ml50% aqueous ethanolic solution again and separated repetitive operation three times.The sodium bentonite that to handle at last thorough drying under infrared lamp places in the vacuum drying oven then 80 ℃ of following vacuum-dryings 24 hours.
3 gram sodium bentonites after α-phenylalanine methyl ester hydrochloride handles as carrier; add 50ml toluene (following used toluene is and uses sodium Metal 99.5-potassium-sodium alloy to handle); the toluene solution that adds the 5ml1.5M methylaluminoxane; stirred 6 hours down at 60 ℃; take solvent then away; wash 3 times with the each 20ml of toluene; add 0.4 gram bis cyclopentadienyl zirconium dichloride then; 50ml toluene; stirred 20 hours down at 60 ℃; drain solvent, toluene wash makes load metallocene catalyst (being called for short catalyzer 3); whole process must be under nitrogen protection; anhydrous and oxygen-free operation, every gram supported catalyst contains 62.5 milligrams of zirconium atoms, and promptly zirconium accounts for load metallocene catalyst gross weight ratio (being called for short the zirconium amount of carrying) and is 6.25wt%.The preparation that uses the same method is catalyzer (being called for short catalyzer 4) the do contrast experiment of carrier with silicon-dioxide-(vinylbenzene-co-4-vinylpyridine copolymer) matrix material, and carrying the zirconium amount is 3.78wt%.
Make the ethene slurry polymerization with catalyzer 3, aluminium zirconium ratio is 600, and all the other are with embodiment 1, and its activity is 1.64 * 10
6G/ (mol.Zr.h), the activity of catalyzer 4 is 0.97 * 10
6G/ (mol.Zr.h).Adopt the basic molecular structure parameter of high temperature GPC test polymer, the result is as follows: the weight-average molecular weight M of catalyzer 3 resulting polymers
w=17.29 * 10
4, number-average molecular weight M
n=8.19 * 10
4, molecular weight distributing index is 2.11, the product bulk density is 0.41g/cm
3The weight-average molecular weight M of catalyzer 4 resulting polymers
w=13.88 * 10
4, number-average molecular weight M
n=6.22 * 10
4, molecular weight distributing index is 2.23, the product bulk density is 0.37g/cm
3
Embodiment 7
3 gram sodium bentonites after α-Phenylalanine methyl ester hydrochloride handles as the preparing carriers load metallocene catalyst, wherein add 0.3 gram bis cyclopentadienyl zirconium dichloride, 50ml toluene, stirred 15 hours at 50 times, drain solvent, toluene wash, other is with embodiment 6, obtain load metallocene catalyst 5 (being called for short catalyzer 5), carrying the zirconium amount is 5.24wt%.With silicon-dioxide is the carried catalyst do contrast experiment (being called for short catalyzer 6) of carrier, and carrying a zirconium amount is 2.70wt%.
Do the slurry copolymerization of ethene and hexene-1 with this catalyzer, hexene-1 is 3 milliliters, and all the other polymerizing conditions are with embodiment 1, and its activity is 1.62 * 10
6G/ (mol.Zr.h).The activity of catalyzer 6 is 0.84 * 10
6G/ (mol.Zr.h).Adopt the basic molecular structure parameter of high temperature GPC test polymer, the result is as follows: the weight-average molecular weight M of catalyzer 5 resulting polymers
w=20.72 * 10
4, number-average molecular weight M
n=10.01 * 10
4, molecular weight distributing index is 2.07, the product bulk density is 0.47g/cm
3The weight-average molecular weight M of catalyzer 6 resulting polymers
w=15.91 * 10
4, number-average molecular weight M
n=7.20 * 10
4, molecular weight distributing index is 2.21, the product bulk density is 0.30g/cm
3
Embodiment 8
With the carrier loaded dichloro two luxuriantization titaniums of embodiment 1, the preparation method gets load metallocene catalyst 7 (being called for short catalyzer 7) with embodiment 1, and carrying a titanium amount is 4.53wt%.With silicon-dioxide is the catalyzer do contrast experiment (being called for short catalyzer 8) of carrier, and carrying a titanium amount is 1.77wt%.Make the ethene slurry polymerization with this catalyzer, all the other are with embodiment 6, and its activity is 1.43 * 10
6G/ (mol.Ti.h), the activity of catalyzer 8 is 0.80 * 10
6G/ (mol.Ti.h).Adopt the basic molecular structure parameter of high temperature GPC test polymer, the result is as follows: the weight-average molecular weight M of catalyzer 7 resulting polymers
w=14.41 * 10
4, number-average molecular weight M
n=6.61 * 10
4, molecular weight distributing index is 2.18, the product bulk density is 0.39g/cm
3The weight-average molecular weight M of catalyzer 8 resulting polymers
w=12.31 * 10
4, number-average molecular weight M
n=5.35 * 10
4, molecular weight distributing index is 2.26, the product bulk density is 0.31g/cm
3
Embodiment 9
Cp in hexane solution
2ZrCl
2With (Ph
3C) BF
4At 0 ℃ of reaction 6h down, after filtration, washing, drying, obtain [Cp with 1: 1 mol ratio
2ZrCl]
+[Cl (Ph
3C) BF
4]
-Title complex.Metallocene complex [Cp with the carrier loaded cationization of embodiment 1
2ZrCl]
+[Cl (Ph
3C) BF
4]
-, the preparation method gets load metallocene catalyst 9 (being called for short catalyzer 9) with embodiment 1, carries the pick amount and is 2.67wt%.Make the ethene slurry polymerization with this catalyzer, all the other are with embodiment 2, and its activity is 1.00 * 10
6G/ (mol.Zr.h).Adopt the basic molecular structure parameter of high temperature GPC test polymer, the result is as follows: the weight-average molecular weight M of resulting polymers
w=19.97 * 10
4, number-average molecular weight M
n=8.76 * 10
4, molecular weight distributing index is 2.28, the product bulk density is 0.35g/cm
3
Claims (7)
1. an intercalated loaded metallocene catalyst is made of clay, laminated clay crystal face properties-correcting agent and metallocene compound, it is characterized in that described catalyzer prepares by following steps: clay was heat-treated 5-10 hour at 400-600 ℃; At room temperature heat treated clay is cleaned the solubility salt at 50% aqueous ethanolic solution, separate, purifying, repetitive operation three times; With the amino acid methyl ester hydrochloride is laminated clay crystal face properties-correcting agent, at room temperature carries out ion exchange reaction 15-25 hour with the polynite of above-mentioned purifying, adopts 50% aqueous ethanolic solution washing after drying; In dry toluene with above-mentioned gained modified clay 50-60 ℃ down with promotor methylaluminoxane (MAO) reaction 4-6 hour, the MAO add-on is per 100 gram modified clays adding 167-500ml MAO (1.5M), washes away unreacted MAO with dry toluene; In dry toluene with gained modified clay and metallocene compound or to form mol ratio with boride be that the metallocene complex of 1: 1 cationization mixes, per 100 gram modified clays add metallocene catalyst 5-10 gram, temperature of reaction is 40-60 ℃, reaction times is 10-20 hour, contains zirconium atom 26.7-62.5 milligram in every gram intercalated loaded metallocene catalyst.
2. intercalated loaded metallocene catalyst according to claim 1 is characterized in that described clay is polynite and sodium bentonite.
3. intercalated loaded metallocene catalyst according to claim 1 is characterized in that described properties-correcting agent amino acid methyl ester hydrochloride is α-glycine methyl ester hydrochloride and α-Phenylalanine methyl ester hydrochloride.
4. intercalated loaded metallocene catalyst according to claim 1 is characterized in that described metallocene compound is bis cyclopentadienyl zirconium dichloride and cyclopentadienyl titanium dichloride.
5. intercalated loaded metallocene catalyst according to claim 1 is characterized in that described promoter aluminium alkyl oxygen alkane is a methylaluminoxane.
6. intercalated loaded metallocene catalyst according to claim 1 is characterized in that described boride is trityl-tetrafluoro boron (Ph
3C) BF
4
7. equal polymerization of intercalated loaded metallocene catalyst catalyzed ethylene according to claim 1 and ethene and alpha-olefin copolymer close, adopt slurry polymerization processes, ethylene pressure is 1.3 normal atmosphere, polymerization temperature is 60 ℃, polymerization time is 1 hour, add methylaluminoxane and be 50-800 to aluminium/main metal molar ratio, its activity is 0.78-2.00 * 10
6G/ (mol.M.h).
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|---|---|---|---|
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