CN1948351A - Polymer carrier Ziegler-Natta catalyst for olefin hydrocarbon polymerization and its preparation method - Google Patents
Polymer carrier Ziegler-Natta catalyst for olefin hydrocarbon polymerization and its preparation method Download PDFInfo
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Abstract
This invention relates to a Z-N catalyst that uses polymer as carrying agent is utilized for aethylenum homopolymerization/alpha- alkenes copolymerization and its preparation. The expression of this catalyst is P-S .Mgx MClY(nTHF),in the expression M is titanium or Vanadium; X=1-40,Y=5-96,n=5-10;P-S is benzene vinyl copolymer carrying agent containing Lewis base functional group-OH,-COOH,-COOR, -CONH2, ixo-equal molecular weight is 10000-40000.Its preparation: First stated copolymer carrying agent that contains Lewis base functional group is dissolved in polar solvent and agretopes with magnesic chloride, second generating emboliform catalyst by the method that it is resolved with chloride of metal titanium or Vanadium and THF by nonpolar solvent or drying spray. This catalyst has very high catalytic activity to aethylenum polymerization, Applied to gas and slurry polymerization process, its products don't have inorganic ash content contained in common inorganic carrying agent.
Description
Technical field
The invention belongs to the olefin polymerization catalysis field, be specifically related to polymer carrier Ziegler-Natta catalyst and preparation method that a kind of ethylene homo or ethylene/alpha-olefin copolymerization are used.
Background technology
Z-N (Zigeler-Natta) polyolefin catalyst is to form with the muriate of the muriate of certain metal (titanium, vanadium etc.) of IVB～VB family, magnesium and at least a electron donor, though originate from the fifties, but it remains the main catalyzer of olefinic polymerization so far, all occupies important position no matter be in industrial application or in the research and development field.People constantly improve its catalytic production rate and performance, but five during the last ten years, be still with traditional preparation method, be about to the catalyst activity component and be carried on and a kind ofly have appropriate specific surface area and pore volume in solvent on the insoluble carrier, these carriers comprise: inorganics such as magnesium dichloride, silica gel, aluminum oxide, diatomite and crosslinked polystyrene etc.
In the patent of having announced, most Zigeler-Natta (Z-N, as follows) catalyzer is all made carrier with silica gel.Because specific surface area, the pore volume of silica gel have certain restriction, active ingredient can not be disperseed effectively, thereby its catalytic production rate is generally all below 10000kgPE/kg-cat, though silica gel can be broken into superfine particulate in the polymer chain propagation process, it still can cause the mist degree of product and appearance ratings to descend; In addition, patent such as the US4568730 that has only only a few to announce adopted a kind of crosslinked polystyrene to make carrier.But crosslinked polystyrene can not dissolve in solvent, in the muriatic process with the muriate of the method load magnesium of chemical bonding or physics dipping and titanium, because of swelling action has the phenomenon of being clamminess, causes difficult treatment.And under the post-treatment temperature of polyolefin products, melt, form " flake " influence the film product visual appearance, " pit " etc., in injection moulding blowing series products, also cause molecule " defective " easily, influence its physicals than infusibility.
An effective means is the lower molecular weight simple linear polymer carrier that contains functional group.The simple linear polymer carrier is fusion fully in the post-treatment of polyolefin products, can further reduce the inorganic ash in the polyolefine, can not influence the quality of polyolefin products.The more important thing is may command polymer support functional group and skeleton structure, reach the purpose of improving catalyst performance and improving catalytic activity.US6413901, US6448348 have announced a kind of Z-N catalyzer of making carrier with polyvinyl chloride, though catalytic activity is greatly improved, but its specific surface area, pore volume are less, limited the raising of catalytic production rate, and polyvinyl chloride and poly intermiscibility extreme difference, the product appearance quality is caused certain detrimentally affect; US5290745 has announced the Z-N catalyzer that a kind of spraying drying is made, its catalytic production rate than traditional raising 2～3 times, the visual appearance that records film product with ASTM D-1922 standard from+10 bring up to+30, but in preparation of catalysts, added a kind of diameter at the silica gel CAB-O-SIL that does not have micropore of 0.06～0.2um (white carbon black TS-610), it does not dissolve in solvent, and is immiscible with polyolefine.
Summary of the invention
The object of the present invention is to provide a kind of high catalytic activity polymer support Z-N catalyzer and this Preparation of catalysts method that is used for ethylene homo or ethylene/alpha-olefin copolymerization.This method is different fully with traditional Z-N catalyzer and carrying method thereof.It adopts the line style styrol copolymer that contains Lewis base functional group as carrier, and it is dissolved in the polar solvent fully, adds MgCl then
2, metal M (titanium or vanadium) muriate, form the solution of homogeneous transparent, resolve or be prepared into insoluble polymer support Z-N catalyzer with non-polar solvent with spray-dired method.
The objective of the invention is to realize by the following technical solutions:
It is a kind of that what be used for ethylene homo or ethylene/alpha-olefin copolymerization is carrier Z-N catalyzer with the polymkeric substance, it is characterized in that: 1) this catalyzer is to be carrier with the styrol copolymer P-S that contains Lewis base functional group, this multipolymer viscosity-average molecular weight 10000～40000; 2) the Lewis base functional group coordination in the muriate of magnesium and the described multipolymer forms mixture P-SMgCl
23) this mixture P-SMgCl
2Form the copolymerization carrier catalyzer with the muriate and the tetrahydrofuran (THF) (THF, as follows) of metal M, its expression formula is: P-SMg
XMcl
YNTHF, in the formula, M is titanium or vanadium; X=1～40; Y=5～96; N=5～10; P-S is the styrol copolymer carrier that contains Lewis base functional group;-S is meant Lewis base functional group, and this Preparation of catalysts method is as follows:
Under anaerobic, anhydrous and nitrogen protection, the styrol copolymer carrier that will contain Lewis base functional group is dissolved among the polar solvent THF, adds the muriate of muriate, titanium or the vanadium of magnesium again, and makes its dissolving; The muriate of the muriate of copolymerization carrier and magnesium, metal titanium or vanadium forms mixture, and the weight ratio of the muriate add-on of wherein said copolymerization carrier, magnesium dichloride, titanium or vanadium is 70～90: 30～20: 10.
Above-mentioned system is the solution of homogeneous transparent, more described solution is prepared into the copolymerization carrier catalyzer of particle state with non-polar solvent parsing or spray-dired method.
Above-mentioned polymer support Z-N catalyzer is a benchmark with the catalyzer, and in weight percentage, it consists of: TiCl
3Or VCl
33.1～9.3%; MgCl
211.4～23.8%; THF 15～25%, and all the other are copolymerization carrier.
Above-mentioned polymer support Z-N catalyzer, X=3～6 in its described expression formula; Y=9～15.
Above-mentioned polymer support Z-N catalyzer, its described Lewis base functional group-S be meant-OH ,-COOH ,-COOR or-CONH
2
Above-mentioned polymer support Z-N catalyzer, the muriate of its described metal M is a titanous chloride.
Above-described polymer support Z-N Preparation of catalysts method is characterized in that: under anhydrous, anaerobic and nitrogen protection,
1) the styrol copolymer carrier that will contain Lewis base functional group is dissolved among the polar solvent THF;
2) muriate with magnesium adds above-mentioned steps 1) dissolve among the polar solvent THF of copolymerization carrier, stirring is dissolved the muriate of magnesium fully under 60～80 ℃ temperature, the muriate of its part magnesium and the described Lewis base functional group co-polymer carrier coordination formation mixture P-SMgCI that contains
2
3) muriate with metal M joins step 2) contain P-SMgCI
2Polar solvent THF in, under 60～80 ℃ of stirring condition, the muriate of metal M is dissolved fully, form uniform clear solution; The weight ratio of the muriate consumption of described copolymerization carrier, magnesium dichloride, metal M is 70～90: 30～20: 10;
4) with above-mentioned steps 3) in the mass transport that forms in non-polar solvent, resolve rapidly or be prepared into insoluble polymer supported catalyst with spray-dired method; Its expression formula is: P-SMg
XMcl
YNTHF; In the formula, M is titanium or vanadium; X=1～40; Y=5～96; N=5～10, P-S is the styrol copolymer carrier that contains Lewis base functional group, its viscosity-average molecular weight 10000～40000.
Above-mentioned polymer support Z-N Preparation of catalysts method is a benchmark with the catalyzer, and in weight percentage, it consists of: TiCl
3Or VCl
33.1～9.3%; MgCl
211.4～23.8%; THF 15～25%, and all the other are copolymerization carrier.
Above-mentioned polymer support Z-N Preparation of catalysts method, X=3 in the described expression formula～6; Y=9～15.
Above-mentioned polymer support Z-N Preparation of catalysts method, described Lewis base functional group-S is meant-OH ,-COOH ,-COOR or-CONH
2
Above-mentioned polymer support Z-N Preparation of catalysts method, the muriate of described metal M is a titanous chloride.
Above-described polymer support Z-N catalyzer is used for ethylene homo or ethylene/alpha-olefin copolymerization process, and its described catalyzer is suitable for slurry polymerization and gas-phase polymerization process.
Above-mentioned polymer support Z-N catalyzer is used for the method for ethylene homo or ethylene/alpha-olefin copolymerization, and its described alpha-olefin is butylene, hexene or octene.
Below Preparation of catalysts method of the present invention is further specified:
1. the preparation of styrol copolymer carrier
The method preparation of styrol copolymer usefulness radical polymerization (З а к, А. Г., К у э н e ч о б, Н. and А., Л ц щ а н с к ц ǔ, И. and С.,
З. А., С м о л я н с к ц ǔ, А. and Л., В ы с о-к о м о л e к. and с о e о), 1974, A16,886.; Zheng Wenzhi, Li Yuliang, Yu Guangqian etc.Journal of Molecular Catalysis, 1996,10 (3): 178), described styrol copolymer comprises poly-(styrene-propene acid), gather (styrene-propene acid amides), gather (styrene-propene alcohol), gather (styrene-propene acid methyl esters).
Have stirring at one, chuck heating/refrigerative prepares in the container, add a kind of polar solvent (solvent with dioxane, glacial acetic acid, tetrahydrofuran (THF) etc.), vinylbenzene and contain the another kind of monomer of functional group, monomeric concentration 20～35%.Vinylbenzene is 90: 10～50: 50 with the another kind of monomeric mol ratio that contains functional group, add Diisopropyl azodicarboxylate (ABIN) and benzoyl peroxide (BPO) mixed initiator of reactant weight 0.5～3.0% (Wt) again, described two kinds of initiator weight ratios are 1: 1.After reaction vessel was used the rare gas element pump drainage, under agitation the speed with 1 ℃/min heated up, and temperature rises to 90～100 ℃ and stops heating, feeds the recirculated cooling water cooling, and polymerization time is 2～4 hours.Styrol copolymer is introduced in another container that precipitation agent is housed, and under brute force stirred, multipolymer parsed in a large amount of precipitation agents, and in 40～80 ℃ of following vacuum-dryings 48 hours.
It is the intrinsic viscosity ([η]) that solvent is measured solution with the naphthane that the molecular weight of styrol copolymer ties up to 25 ℃, calculates by following formula then: [η]=7.7 * 10
-4M
0.93
2. the preparation of polymer supported catalyst
The Preparation of catalysts all operations all carries out under anhydrous, anaerobic and nitrogen protection.
Under 70 ℃, have in stirring, the chuck heating/refrigerative catalyst preparation container at one, polymer support, tetrahydrofuran (THF) are joined in the catalyst preparation container with the method for gravity blanking, stirring makes its dissolving, the muriate that adds magnesium then, react and add the muriate of titanium or vanadium again after 4 hours, and make its dissolving.The muriate of above-mentioned copolymerization carrier, magnesium dichloride, titanium or vanadium is by 70～90: 30～20: 10 weight ratio adds in the described container, and continuing to be stirred to the mixture that copolymerization carrier in the container, magnesium dichloride, titanous chloride form is a transparent solution.Its method 1: with above-mentioned solution under nitrogen gas pressure, being 1000mm and the set that has jacket hot tracing tube bank by several diameters less than 0.5mm, length is introduced in the container that hexane (heptane) be housed with the speed of 7～10m/s, and this container has stirring, chuck heating unit.Polymer supported catalyst resolves to the solids state rapidly in this container.The filtering solvent boils off tetrahydrofuran (THF), obtains the solids catalyzer.Its method 2: under nitrogen pressure, it is in the spray-dryer of 3000mm for 450mm length that above-mentioned solution is introduced a diameter by pipeline, feed hot nitrogen from its underpart, THF evaporates away rapidly, granules of catalyst is deposited to its temperature of linking to each other with moisture eliminator bottom less than in 10 ℃ the container, and in 50～80 ℃ of dryings.THF content is between 15～25% (wt) in the solid catalyst, and Mg/Ti (mol ratio) is 3～10: between 1 (its analytical procedure is method commonly used in the art).The size distribution of solid catalyst represents with logarithmic percentage ratio D10, D50, D90, the corresponding D50 of 40um for example, the diameter that shows particle be 40um account for 50%; The corresponding D90 of 60um, show particle have 90% less than 60um; The corresponding D10 of 20um, show particle have 10% less than 20um.
Catalyzer of the present invention is applicable to the slurry polymerization and the gas-phase polymerization process of olefinic polymerization, preferably gas-phase polymerization process.The catalyzer injection mode can be with the method for nitrogen purging, also can be mixed and made into to pump up behind the slurries with a kind of organic solvent to be injected in the reactor.
The used promotor of polyreaction comprises triethyl aluminum, aluminium diethyl monochloride or triisobutyl aluminium, and triethyl aluminum preferably, AI/Ti (mol ratio) is 10～100: 1, preferably 40～60: 1.The melting index of characterize polymers characteristic is regulated with hydrogen, and the mol ratio that makes hydrogen and ethene is 0.12～0.4.The density of characterize polymers characteristic is regulated by alpha-olefin, and during the ethylene/alpha-olefin copolymerization, the mol ratio of alpha-olefin and ethene is 0.1～0.5.Described alpha-olefin comprises butene-1, hexene-1, octene-1.
Under these conditions, gas phase polymerization 2 hours, the catalytic production rate of catalyzer of the present invention is all more than 10000kgPE/kg-cat.
With the density of the polyvinyl resin of Catalyst Production of the present invention at 0.900g/cm
3More than (according to ASTM D-1503 canonical measure); The tap density of polyvinyl resin is at 0.35g/cm
3More than (according to ASTM D-1895 canonical measure); The outward appearance of polyethylene film is in (according to ASTM D-1922 canonical measure) more than+30.
The present invention is different fully with traditional Z-N catalyzer and carrying method thereof.It adopts the line style styrol copolymer that contains Lewis base functional group as carrier, and it is dissolved in the polar solvent fully, adds MgCl then
2, metal M muriate (muriate of titanium or vanadium, as follows), form the solution of homogeneous transparent.MgCl
2Form mixture P-SMgCl with the functional pendant groups coordination on the polymer chain
2, make part MgCl
2Be fixed on the polymer chain.When the muriate of free magnesium, the muriate of metal M (muriate of titanium or vanadium) molecular crystal being become in the process of particle, be fixed on the MgCl on the polymer chain with non-polar solvent parsing or spray-dired method
2Played the effect of " nucleus ", this effect has increased the crystalline randomness, makes MgCI
2High dispersing (showing that macroscopic view goes up the volumetric expansion of mixture), and with the muriate eutectic of metal M, interact by the chlorine bridged bond, make the muriate of Primary Catalysts metal titanium or vanadium disperse its surface well, even reach unit molecule dispersive degree, the number in active centre is increased greatly, thereby improved the catalytic activity of catalyzer.This catalyzer is used for ethene gas-phase polymerization, and its catalytic production rate is all more than 10000kgPE/kg-cat.Because the employing molecular weight is 10000～40000 polymer support, fusion fully under the general processing temperature of polyolefine, and do not contain inorganic ash content, can not influence quality product.
Embodiment
Now the present invention is further described as follows in conjunction with embodiment:
Embodiment 1
Preparation of catalysts
The preparation of poly-(styrene-propene acid) copolymerization carrier: 60Kg dioxane, 20Kg styrene/acrylic are added in the reactor; the styrene/acrylic mol ratio is 80: 20, adds reactant weight (20Kg) 1.5% (Wt) Diisopropyl azodicarboxylate/benzoyl peroxide mixed initiator again.Reaction vessel is with behind the nitrogen pump drainage, is warming up to 95 ℃ with the speed of 1 ℃/min, stops to heat up and feeds the recirculated cooling water cooling, and polymerization time is 4 hours, and polymkeric substance is introduced in another container that a large amount of hexane/water are housed, and the volume ratio of hexane and water is 1: 2.Under brute force stirs, multipolymer is parsed.Multipolymer in 60 ℃ of following vacuum-dryings 48 hours, must be gathered (styrene-propene acid) multipolymer.Record the viscosity-average molecular weight W of multipolymer
ηBe 38430.
Poly-(styrene-propene acid) copolymerization carrier Preparation of catalysts: under 70 ℃ condition, with nitrogen to one have stirring, chuck heating/refrigerative catalyst preparation container (10L) carries out drying, pump drainage, with nitrogen pressure is risen to 0.3Mpa.Get poly-(styrene-propene acid) carrier 500g of above-mentioned preparation, join in the catalyst preparation container, add 5L THF and stir to move and makes its dissolving with the method for gravity blanking.Add the 140g magnesium dichloride then, react and add the 56g titanous chloride after 4 hours, restir operation 4 hours, pressure in the preparation container is risen to 0.7Mpa, are 0.5mm with above-mentioned mixed solution by several diameters, to be 1000mm and the set that has jacket hot tracing tube bank guide in the high-speed stirring container (500L) that solvent hexane is housed with the speed of 7～10m/s length, and mixture resolves to solid catalyst particle rapidly in this container.Sedimentation leached solvent after 12 hours, and starting is stirred in and is heated to 70 ℃ under the vacuum state and boils off THF, obtains polymer supported catalyst.Catalyzer is formed: Ti 1.69% (wt); Mg 4.20% (wt); THF17.8% (wt), all the other are polymer support.
Embodiment 2
Preparation of catalysts
The preparation of poly-(styrene-propene acid) copolymerization carrier: 80Kg dioxane, 20Kg styrene/acrylic are added in the reactor; the styrene/acrylic mol ratio is 70: 30; add reactant weight (20Kg) 3.0% (Wt) Diisopropyl azodicarboxylate/benzoyl peroxide mixed initiator again, be warming up to 95 ℃ of polymerizations 2 hours.Other step is identical with the preparation of embodiment 1 copolymerization carrier with processing condition.Record multipolymer viscosity-average molecular weight W
ηBe 18300.
The preparation of poly-(styrene-propene acid) polymer supported catalyst: get the styrol copolymer 500g of above-mentioned preparation, THF 5L, magnesium dichloride 180g, titanous chloride 68g.Other step is identical with the preparation process of example 1 polymer supported catalyst.The composition Ti 1.97% (wt) of polymer supported catalyst; Mg 4.02% (wt); THF 18.2% (wt), all the other are polymer support.
Embodiment 3
Preparation of catalysts
The preparation of poly-(styrene-propene alcohol) copolymerization carrier: 60Kg dioxane, 20Kg vinylbenzene/vinylcarbinol are added in the reactor; vinylbenzene/vinylcarbinol mol ratio is 80: 20, adds reactant weight (20Kg) 2.5% (Wt) Diisopropyl azodicarboxylate/benzoyl peroxide mixed initiator again.Other step is identical with the preparation of embodiment 1 copolymerization carrier with processing condition.Record multipolymer viscosity-average molecular weight W with viscosimetry
ηBe 31000.
Poly-(styrene-propene alcohol) copolymerization carrier Preparation of catalysts: poly-(styrene-propene alcohol) the copolymerization carrier 500g that gets above-mentioned preparation, join among the 5L THF, add 170g magnesium dichloride, titanous chloride 60g, other step is identical with the preparation process of example 1 polymer supported catalyst with processing condition.The composition Ti1.58% (wt) of polymer supported catalyst; Mg 3.80% (wt); THF 18.7% (wt), all the other are polymer support.
Embodiment 4
Preparation of catalysts
The preparation of poly-(styrene-propene acid amides) copolymerization carrier: 80Kg glacial acetic acid, 20Kg vinylbenzene/acrylamide adding are had in the reactor of glass lining; the mol ratio of vinylbenzene/acrylamide is 85: 15, adds reactant weight (20Kg) 2.0% (Wt) Diisopropyl azodicarboxylate/benzoyl peroxide mixed initiator again.Reactor is with behind the nitrogen pump drainage, is warming up to 95 ℃ with the speed of 1 ℃/min, stops to heat up and feeds the recirculated cooling water cooling, and polyase 13 hour is introduced polymkeric substance in another container that a large amount of hexane/water are housed, and the volume ratio of hexane and water is 1: 2.Under brute force stirs, multipolymer is parsed.Multipolymer was in 60 ℃ of following vacuum-dryings 48 hours.Gathered (styrene-propene acid amides) multipolymer.Record multipolymer relative molecular weight W with viscosimetry
ηBe 23000.
The preparation of poly-(styrene-propene acid amides) copolymerization carried catalyst: get the copolymerization carrier 500g of above-mentioned preparation, join among the 5LTHF, add the 180g magnesium dichloride, it is identical that 68g titanous chloride, other step and processing condition and example 1 multipolymer carry preparation not.The composition Ti 1.69% (wt) of catalyzer, Mg 4.20% (wt), THF 17.8% (wt), all the other are polymer support.
Embodiment 5 Preparation of catalysts
Poly-(styrene-propene acid) copolymerization carrier Preparation of catalysts: under 70 ℃ condition, with nitrogen to one have stirring, chuck heating/refrigerative catalyst preparation container (10L) carries out drying, pump drainage, with nitrogen pressure is risen to 0.3Mpa.Get poly-(styrene-propene acid) 310g of embodiment 2 preparation, join in the catalyst preparation container, add 3L THF and stir to move and makes its dissolving with the method for gravity blanking.Add the 110g magnesium dichloride then, react and add the 40g titanous chloride after 4 hours, restir operation 4 hours, pressure in the preparation container is risen to 0.7Mpa, it is in the spray-dryer of 3000mm for 450mm length that above-mentioned mixed solution is introduced a diameter by pipeline, the bottom feeding temperature of this moisture eliminator is 150 ℃ a hot nitrogen, and THF evaporates away rapidly from the droplet that spraying forms, and is discharged to cooling recovery system from the top of moisture eliminator; The solid polymer support catalyst sedimentation that spraying forms to the internal temperature that links to each other with the moisture eliminator bottom less than in 10 ℃ the container.Catalyzer is formed: Ti 1.70% (wt); Mg 4.80% (wt); THF 18.5% (wt), all the other are polymer support.
Embodiment 6
Present embodiment is vinyl polymerization (slurry polymerization)
Still formula slurry polymerization reactor to a 10L is qualified with the nitrogen pump drainage under the condition more than 80 ℃.Whipped state adds the 1.0mol.L of 5L heptane solvent, 50mL down
-1The promotor triethyl aluminum, the catalyzer 233mg that gets embodiment 1 preparation adds reactor, continuously stirring.Reconcile the dividing potential drop 0.28Mpa of hydrogen, ethylene partial pressure 0.75Mpa was in 85 ℃ of polymerizations 2 hours.Get polyethylene product 1631g, catalytic production rate 7000kgPE/kg-cat.
Embodiment 7
Present embodiment is ethylene/vinyl-1 copolymerization (slurry polymerization)
Still formula slurry polymerization reactor to a 10L is qualified with the nitrogen pump drainage in 80 ℃.Under whipped state, add 5L heptane solvent and 50mL 1.0mol.L
-1Promotor triethyl aluminum, 0.5L hexene-1, the catalyzer 265mg that gets embodiment 4 preparation adds reactor, continuously stirring.Reconcile hydrogen partial pressure 0.28Mpa, ethylene partial pressure 0.75Mpa was in 85 ℃ of reactions 2 hours.Get polyethylene product 1640g, catalytic production rate 6188kgPE/kg-cat.Poly density 0.918g/cm
3
Embodiment 8
Present embodiment is ethylene/butylene-1 copolymerization (vapour phase polymerization)
Adding median size to the gas-phase fluidized-bed reactor of 400 * 1200mm is that the polyvinyl resin 2000g of 1.2mm makes seed bed, charges into nitrogen and makes and boost to 0.6Mpa in the reactor, and starting fluidizing agent compressor is qualified with the nitrogen purging displacement below 50 ℃.The temperature of seed bed is raised to 88～90 ℃, continues to use nitrogen purging, the water-content in seed bed is less than 5ppm.Keep the fluidizing agent compressor to move continuously, in seed bed, add the 1.0mol.L of 50mL
-1Triethyl aluminum (TEAL) solution falls the water completely consumed.Slowly introduce hydrogen, ethene, butene-1, reactor pressure is raised to 2.0～2.1Mpa, the gas composition of control fluidizing gas velocity 0.6～0.8m/s. conditioned reaction is:
Ethene: 38.2% (v/v)
Butene-1: 6.90% (v/v)
Butane: 0.70% (v/v)
Methane: 0.30% (v/v)
Hydrogen: 5.70% (v/v)
Nitrogen: 48.2% (v/v)
TEAL concentration 300PPm
Controlling reactor pressure is at 2.0～2.1Mpa, and temperature of reactor is at 88～90 ℃.Get embodiment 3 catalyzer 148mg and add in the reactor, control pressure is constant.When polyreaction begins, regulate the cooling water inflow control reaction temperature of water cooler, ongoing operation polymerization reactor operation 2 hours.Inject the CO termination reaction.Take out polymkeric substance 5084g, remove seed bed, get product 3084g.Catalytic production rate 20837kgPE/kg-cat, poly density is 0.920g/cm
3
Embodiment 9
This example is ethylene/butylene-1 copolymerization (vapour phase polymerization)
Get the catalyzer 145.7mg of embodiment 2 preparation, carry out vapour phase polymerization at the gas-phase fluidized-bed reactor of 400 * 1200mm.Its operation steps is identical with embodiment 8 with other condition.Get product 3022g.Catalytic production rate 20741kgPE/kg-cat, poly density is 0.921g/cm
3
Embodiment 10
Present embodiment is ethylene/butylene-1 copolymerization (vapour phase polymerization)
Get the catalyzer 108mg of embodiment 5 preparation, carry out vapour phase polymerization at the gas-phase fluidized-bed reactor of 400 * 1200mm.Its operation steps and other condition are identical with example 8.Get product 3318g.Catalytic production rate 30722kgPE/kg-cat, poly density is 0.918g/cm
3
Above embodiment (1～5) selects the catalyzer of different styrol copolymer preparing carriers, is used for vinyl polymerization (embodiment 6～10), and the composition of each routine polymer supported catalyst and polyethylene product Physical Property Analysis result list following each table respectively in.
Table 1 polymer support Z-N of the present invention catalyzer is formed
| Example | Carrier | Ti％(w) | Mg％(w) | THF％(w) | Ti/mmol/g | Mg/mmol/g | Mg/Ti (mol ratio) |
| 1 2 3 4 5 | P-COOH P-COOH P-OH P-CONH2 P-COOH | 1.69 1.97 1.58 1.69 1.70 | 4.20 4.02 3.80 4.20 4.80 | 17.8 18.2 18.7 17.8 18.5 | 0.35 0.41 0.33 0.35 0.36 | 1.73 1.65 1.56 1.73 1.98 | 4.94 4.02 4.73 4.94 5.50 |
Table 2 polymer support Z-N of the present invention catalyzer is used for ethene slurry polymerization result
| Embodiment | Carrier | The Al/Ti mol ratio | Catalytic production rate KgPE/Kg-Cat | Catalytic activity KgPE/molTi.h | Melting index g/10min | Tap density g/cm 3 | The film appearance grade |
| 6 7 | P-COOH P-CONH2 | 49 48 | 7000 6188 | 10000 8840 | 0.90 1.00 | 0.350 0.340 | +30 +30 |
Table 3 polymer support Z-N of the present invention catalyzer is used for the ethene gas-phase polymerization result
| Embodiment | Carrier | TEAL concentration/ppm | Catalytic production rate KgPE/Kg-Cat | Catalytic activity KgPE/molTi.h | Melting index g/10min | Tap density g/cm 3 | The film appearance grade |
| 89 10 reference examples reference examples reference examples | The white carbon black silica gel-955 of P-OH P-COOH P-COOH polyvinyl chloride | 300 300 300 300 300 300 | 20837 20741 30722 10555 3890 3640 | 31570 25310 42670 25330 18700 43590 | 0.98 1.01 1.09 0.98 0.78 0.99 | 0.360 0.330 0.360 0.367 0.356 0.360 | +30 +30 +30 +30 +10 ＜+10 |
Note:
White carbon black-usefulness patent US5290745 announces the result of catalyst test;
Silica gel 955-makes the result that carried catalyst is tested with traditional with silica gel;
Polyvinyl chloride-usefulness patent US6413901 announces the result of catalyst test.
From the data of table 3 as can be seen: by catalyzer of the present invention polymerization gas-phase fluidized-bed reactor, its catalytic activity is all more than 25000kg PE/molTih; More than the catalytic production rate 20000kgPE/kg-cat; The appearance of films quality grade is more than+30, and the catalytic of silica gel (955) is active and productivity is all lower.The catalytic production rate of white carbon black (US5290745 announces the result of catalyst test) is higher, but its catalytic activity is more general.The catalytic activity of polyvinyl chloride (US6413901 announces the result of catalyst test) is higher, but its catalytic production rate is very low, needs the catalyzer of adding reactor more, and the carrier polyvinyl chloride can cause the visual appearance grade of polyethylene film to descend.
The invention is not restricted to above-mentioned described content; every a kind of linear polymer is dissolved in a kind of solvent with resolving and the polymer support Z-N catalyzer of spray-dired method preparation as the muriate of carrier and IVB or VB group 4 transition metal titanium or vanadium, and enlightened by this patent and the improvement of drawing all belongs within the protection domain of the present invention.
Use a kind of aluminum alkyls before catalyzer of the present invention uses catalyzer is carried out prereduction.Used aluminum alkyls is trimethyl aluminium, triethyl aluminum, tri-n-hexyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, a chlorobutyl aluminium etc., preferably aluminium diethyl monochloride, tri-n-hexyl aluminum, or the mixture of the two.
The invention is not restricted to above-mentioned described content; every a kind of polymkeric substance that contains functional group is dissolved in polar solvent as the titanium of carrier and IVB or VB group 4 transition metal or the muriate of vanadium, resolves or the polymer support Z-N catalyzer of the method preparation of spraying and be subjected to this patent enlightenment and the improvement of drawing all belongs to the protection domain of this patent with non-polar solvent.
Claims (12)
- It is 1, a kind of that what be used for ethylene homo or ethylene/alpha-olefin copolymerization is carrier Ziegler-Natta catalyst with the polymers, it is characterized in that: 1) this catalyzer is a carrier with the styrol copolymer that contains Lewis base functional group, this multipolymer viscosity-average molecular weight 10000～40000; 2) the Lewis base functional group coordination in the muriate of magnesium and the described copolymerization carrier forms mixture P-SMgCl 23) this mixture P-SMgCl 2Form the copolymerization carrier catalyzer with the muriate and the tetrahydrofuran THF of metal M, its expression formula is: P-SMg XMcl YNTHF, in the formula, M is titanium or vanadium; X=1～40; Y=5～96; N=5～10, P-S is that the styrol copolymer that contains Lewis base functional group carries not;-S is a Lewis base functional group; This Preparation of catalysts method is as follows:Under anhydrous, anaerobic and nitrogen protection, the styrol copolymer carrier that will contain Lewis base functional group is dissolved among the polar solvent THF, adds the muriate of muriate, titanium or the vanadium of magnesium again, and makes its dissolving; The muriate of the muriate of copolymerization carrier and magnesium, metal titanium or vanadium forms mixture, and the weight ratio of the muriate add-on of the muriate of wherein said copolymerization carrier, magnesium, titanium or vanadium is 70～90: 30～20: 10;Above-mentioned system is the solution of homogeneous transparent, more described solution is prepared into the above-mentioned copolymerization carrier catalyzer of particle state with non-polar solvent parsing or spray-dired method.
- 2, polymer carrier Ziegler-Natta catalyst according to claim 1 is characterized in that: be benchmark with the catalyzer, in weight percentage, it consists of: TiCl 3Or VCl 33.1～9.3%; MgCl 211.4～23.8%; THF 15～25%, and all the other are copolymerization carrier.
- 3, polymer carrier Ziegler-Natta catalyst according to claim 1 is characterized in that: X=3 in the described expression formula～6; Y=9～15.
- 4, polymer carrier Ziegler-Natta catalyst according to claim 1 is characterized in that: described Lewis base functional group-S is meant-OH ,-COOH ,-COOR or-CONH 2
- 5, polymer carrier Ziegler-Natta catalyst according to claim 1 is characterized in that: the muriate of described metal M is a titanous chloride.
- 6, the preparation method of polymer carrier Ziegler-Natta catalyst as claimed in claim 1 is characterized in that: under anhydrous, anaerobic and nitrogen protection,1) the styrol copolymer carrier that will contain Lewis base functional group is dissolved among the polar solvent THF;2) muriate with magnesium adds above-mentioned steps 1) dissolve among the polar solvent THF of copolymerization carrier, stirring is dissolved the muriate of magnesium fully under 60～80 ℃ temperature, the muriate of its part magnesium and the described Lewis base functional group polymer support coordination formation mixture P-SMgCI that contains 23) muriate with metal M joins step 2) contain P-SMgCI 2Polar solvent THF in, wherein the weight ratio of the muriatic add-on of copolymerization carrier, magnesium dichloride and metal M is 70～90: 30～20: 10; Under 60～80 ℃ of stirring condition, the metal M muriate is dissolved fully, form uniform clear solution;4) with above-mentioned steps 3) in the mass transport that forms in non-polar solvent, resolve rapidly or be prepared into insoluble polymer supported catalyst with spray-dired method; Its expression formula is: P-SMg XMCl YNTHF; M is titanium or vanadium in the formula; X=1～40; Y=5～96; N=5～10, P-S is the styrol copolymer carrier that contains Lewis base functional group, its viscosity-average molecular weight 10000～40000 ,-S is a Lewis base functional group.
- 7, the preparation method of polymer carrier Ziegler-Natta catalyst according to claim 6 is a benchmark with the catalyzer, and in weight percentage, it consists of: TiCl 3Or VCl 33.1～9.3%; MgCl 211.4～23.8%; THF 15～25%, and all the other are copolymerization carrier.
- 8, the preparation method of polymer carrier Ziegler-Natta catalyst according to claim 6, X=3 in the described expression formula～6; Y=9～15.
- 9, the preparation method of polymer carrier Ziegler-Natta catalyst according to claim 6, described Lewis base functional group-S be meant-OH ,-COOH ,-COOR or-CONH 2
- 10, the preparation method of polymer carrier Ziegler-Natta catalyst according to claim 6, the muriate of described metal M is a titanous chloride.
- 11, polymer carrier Ziegler-Natta catalyst as claimed in claim 1 is used for ethylene homo or ethylene/alpha-olefin copolymerization process, it is characterized in that: this catalyzer is suitable for slurry polymerization and gas-phase polymerization process.
- 12, polymer carrier Ziegler-Natta catalyst according to claim 11 is used for ethylene homo or ethylene/alpha-olefin copolymerization process, it is characterized in that: described alpha-olefin is butylene, hexene or octene.
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| WO2012022127A1 (en) * | 2010-08-19 | 2012-02-23 | 中国石油化工股份有限公司 | Catalytic composition for polymerization of olefin and preparation method thereof |
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| CN1030771C (en) * | 1987-03-17 | 1996-01-24 | 住友化学工业株式会社 | Process for producing olefin polymers and catalyst used therein |
| IT1217744B (en) * | 1988-05-31 | 1990-03-30 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| US5409875A (en) * | 1993-03-08 | 1995-04-25 | Queen's University | Polymer-supported catalyst for polymerization and copolymerization of olefins |
| US6448348B1 (en) * | 1998-10-16 | 2002-09-10 | Saudi Basic Industries Corporation | Process for polymerizing olefins with supported Ziegler-Natta catalyst systems |
| EP1233029B1 (en) * | 2001-02-15 | 2003-11-12 | Saudi Basic Industries Corporation | Supported catalyst composition for polymerization of olefins; method for preparing the same and process for polymerization using the same |
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