CN1137154C - Ethylene Polymerizing solid catalyst composition, its preparation process, application and solid catalyst - Google Patents
Ethylene Polymerizing solid catalyst composition, its preparation process, application and solid catalyst Download PDFInfo
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Abstract
The present invention provides an olefinic polymerization solid catalyst component which comprises 1.5 to 4.5 wt% of magnesium, 0.6 to 1.5 wt% of titanium, 6.0 to 18.0 wt% of chlorine, 0.7 to 8.0 wt% of alkoxy and 0.5 to 3.5 wt% of aluminium. The olefinic polymerization solid catalyst component is used for olefinic polymerization with higher catalytic activity without the need of pre-polymerization, is particularly suitable for homopolymerization (copolymerization) for an ethene fluidized bed, and has the advantages of stable polymerization reaction, no agglomeration, no phenomenon of sticking wall, good sensitivity of polymerization hydrogen adjustment, good particle form of the polymer and high stacking density.
Description
The present invention relates to a kind of ingredient of solid catalyst, preparation method and the application of this catalyst component in ethene gas-phase polymerization or copolymerization, and solid catalyst.
The polyethylene gas-phase polymerization process is short with its technological process of production, easy and simple to handle, without solvent, starting material and energy expenditure are low, and it is easy to switch the trade mark, the transition material is few, be fit to produce characteristics such as full density polythene and is better than high-pressure process, solution method and slurry process, and therefore vapor phase process is with the fastest developing speed in the world.
Because ethene gas-phase polymerization technology is under gas phase state, ethene and alpha-olefin comonomer directly contact with catalyzer carries out polyreaction, therefore in suitability for industrialized production, in order to make polymerization technique stablize and guarantee the quality of polyvinyl resin, employed catalyzer must possess following over-all properties:
(1) catalyzer should have higher activity, but its initial activity must be lower, and has kinetics of polymerization reaction behavior stably;
(2) catalyzer and polymkeric substance thereof should have good particle form and high tap density, narrow size-grade distribution, no minuteness particle, make it among polymerization reactor, form preferable fluidized state, help the raising of polymerization single polymerization monomer mass transfer effect and removing of heat of polymerization, avoid forming local " focus " and phenomenons such as generation is lumpd, sticking wall;
(3) catalyzer should have the copolymerization performance of good ethene and alpha-olefin and density and molecular weight that hydrogen response makes polymkeric substance are regulated easily, to produce the polyvinyl resin of different purposes.
As everyone knows, ethylene gas phase catalyst major part is to adopt the method for dipping the ziegler-natta type catalyst active ingredient to be fixed on the solid carrier of organic or inorganic, is known at the halogenide that adopts silica gel or divalent metal in the art.United States Patent (USP) 4,421,674 disclose a kind of support of the catalyst, be that microspheres with solid with silicon-dioxide is suspended in the ethanolic soln of magnesium chloride, obtain a kind of spheric support of the catalyst, this carrier has the nuclear of microspheres with solid formation and the shell of active magnesium chloride, but owing to adopted spray-dired method, makes comparatively difficulty and complicated of preparation technology.
Chinese patent CN105756A discloses a kind of ethene (being total to) polymerization solid catalyst component that partly is made of the catalytic activity of particulate silica support and titaniferous, magnesium, chlorine and alkoxyl group, and its preparation method is the ethanolic soln that a) prepares magnesium chloride; B) with described solution impregnation silicon-dioxide; C) from suspension, remove unabsorbed ethanol; D) from solid, remove the ethanol of absorption; E) muriate, alkoxide or the alkyl chloride oxide compound of gained solid and titanium are interacted; And according to circumstances also can interact with alkyl aluminum chloride.This method for preparing catalyst is comparatively convenient and simple, but the particle form and the tap density of the resulting polymers that (only provides gas phase agitated bed aggregated data) when being used for the vapour phase polymerization of ethene are all not ideal enough, can't satisfy the requirement of industrialization gas-phase polymerization process.
For excessive electron donor ethanol, in aforesaid method, only adopt the ethanolic soln evaporate to dryness of simple steam seasoning, and partly remove the ethanol of absorption by the method for drying under reduced pressure magnesium chloride.The inventor, is still contained too much absorbed ethanol, thereby has been reduced activity of such catalysts after adopting the aforesaid method dealcoholysis through discovering repeatedly in the catalyst solid.Simultaneously in the method, though that uses that relatively large magnesium chloride can improve catalyzer carries titanium amount and activity, magnesium chloride is excessive will to cause that fine powder increases in the polymkeric substance, cause caking even quick-fried bed when using in fluidized-bed easily, and blocking pipeline, cl content is big in the polymkeric substance.
According to U.S. Pat 4719193, to component before the titaniferous solid heat-treat can reduce before the amount of electron donor in the component, thereby reduced and be used for the consumption of the activator of component before the pre-activation before the polymerization.Significantly improved catalytic activity simultaneously.But this patent only reduces the amount of electron donor with physical method, the degree of minimizing is limited, and the lateral reactivity of catalyzer can not be brought into play fully.Have now found that, the amount of the electron donor in the carrier of catalyzer is further reduced, can improve the catalytic activity of catalyzer, improve other performances of catalyzer simultaneously.
One of purpose of the present invention is low or need shortcomings such as pre-polymerization in order to overcome in the above-mentioned prior art catalyst activity, a kind of olefins polymerizing solid catalyst component is proposed, this catalyst component has advantages of high catalytic activity when being used for olefinic polymerization and need not pre-polymerization, be specially adapted to all (being total to) polymerizations of ethene fluidized-bed, stable polymerization reaction, do not lump, do not glue wall, the polymerization hydrogen response is good, and the polymer beads form is good, tap density is high.
Two of purpose of the present invention has been to provide a kind of preparation method of above-mentioned catalyst component.
Three of purpose of the present invention has been to provide the application of a kind of above-mentioned catalyst component in ethene gas-phase polymerization or copolymerization.
Four of purpose of the present invention has been to provide a kind of catalyzer that comprises above-mentioned catalyst component.
The ingredient of solid catalyst of a kind of for olefines polymerization of the present invention, it is characterized in that: include following component: magnesium 1.5～4.5wt%, be preferably 2.0～3.8wt%, titanium 0.6～1.5wt%, be preferably 0.7～1.3wt%, chlorine 6.0～18.0wt%, be preferably 8.0～15.0wt%, alkoxyl group 1.0～8.0wt%, be preferably 2.0～4.5wt%, aluminium 0.5～3.5wt%, be preferably 1.5～3.0wt%, and preparation by the following method:
(1) preparation of carrier:
(a) ethanolic soln of preparation magnesium compound;
(b) the porous inorganic oxide carrier is dipped in the above-mentioned solution;
(c) heating removes excess ethanol from suspension, and the mol ratio that makes oxyethyl group and magnesium is 1.5～4;
(d) under 30～60 ℃, solids and at least a general formula that step (c) is obtained are SiCl
mR
4-mHalogen silicon compound or at least a general formula be AlR
nX
3-nAluminum compound reaction after, the mol ratio that makes oxyethyl group and magnesium is 0.3～1.4,0≤m≤4 wherein, R is an alkyl, X is a kind of among Cl, Br, the I, n is 0,1,2 or 3.
(2) load of active ingredient: reactant and at least a general formula that step (1) is obtained are Ti (OR)
xCl
4-xTitanium compound react, wherein x is the number of 0-4, R is C
1-C
14Fat or aryl radical, the mol ratio of titanium and magnesium is 0.5～15; Be R with at least a general formula again
n' Si (OR ")
4-nSilicon compound react wherein R ' and R " be C
1-C
14Aliphatic group, can be identical also can be inequality, n is the number of 0-4, the mol ratio of silicon compound and titanium compound is 0.01～1.0;
(3) reactant and the general formula that step (2) is obtained is AlR
pCl
3-pAlkyl aluminum chloride reaction, the mol ratio of aluminium and titanium is 1～4,0≤p≤3 wherein, R is an alkyl;
(4) reactant of washing, drying step (3) gained obtains ingredient of solid catalyst.
In the above-mentioned catalyst component, it is MgX that described magnesium compound is selected from general formula usually
2Compound, wherein X is bromine, iodine, especially chlorine, concrete compound has magnesium dichloride, dibrominated magnesium, two magnesium iodides, is preferably magnesium dichloride.During the preparation magnesium compound solution, the mol ratio of ethanol and magnesium compound is 35～60, is preferably 40～50.
In the above-mentioned catalyst component, described porous inorganic oxide carrier mainly is selected from following compounds: SiO
2, Al
2O
3, TiO
2, ZrO
2And contain SiO
2Take from ZrO with one or more
2, TiO
2, MgO and Al
2O
3The inorganic oxide mixture.Specially suitable carrier is unformed pelletized silica, is characterized in: volume of voids is 1.5-2ml/g, specific surface area 230-350m
2/ g, the hole mean diameter is 18-30nm.These SiO
2Can be polygonal granular form or also can be the globoid form, the preferred class spheroid.
As before the support of the catalyst, can earlier inorganic oxide be heat-treated, also may be as far as possible all to remove contained small amount of moisture with it activation.
Thermal treatment can comprise makes inorganic oxide under 100-800 ℃ temperature calcination 4-10 hour, 80-150 ℃ following vacuum-drying 1-20 hour.
In the above-mentioned catalyst component, can also add one or more of following electron donor ester or ether in the described magnesium compound ethanolic soln.Particular compound as: ethyl benzoate, diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, tetrahydrofuran (THF), be preferably: diethyl phthalate, tetrahydrofuran (THF).
Be dipped in the process of magnesium compound ethanolic soln at the porous inorganic oxide carrier, the weight ratio of magnesium compound and porous inorganic oxide carrier is crucial, generally should be controlled at 1: 3～1: 15, it more preferably is 1: 4～1: 12, most preferably be 1: 5～1: 10, if this ratio is too high, the load magnesium compound is more on inorganic oxide carrier, then can increase in the fine powder rate of polymkeric substance in the polymerization process, particularly vapour phase polymerization fluidized-bed process; If this ratio is low excessively, the carrier utilization ratio is lower, can increase the cost of catalyzer, and activity of such catalysts reduces simultaneously.
The contriver in the preparation of said catalyst carrier, removes the electron donor (ethanol) that partially absorb by simple exsiccant method through discovering repeatedly, make the mol ratio of oxyethyl group and magnesium be 1.5～4 after, adopting at least a general formula is SiCl
mR
4-mHalogen silicon compound or at least a general formula be AlR
nX
3-nAluminum compound handle and be very important, after this handles with before being untreated, compare the support of the catalyst that obtains, crystallite is loose, forms many holes, and specific surface is big, the exposure and the mass transfer that help the active centre active centre concentration is increased, thereby activity improve a lot.The particular compound of halogen silicon compound is as silicon tetrahalogen, METHYL TRICHLORO SILANE, ethyl trichlorosilane, propyltrichlorosilan, dimethyldichlorosilane(DMCS), diethyl dichlorosilane, and preferred halogen silicon compound is a silicon tetrachloride.General formula AlR
nX
3-nAluminum compound, wherein X is a kind of among Cl, Br, the I, n is 0,1,2 or 3, R is C
1～C
5Alkyl, concrete compound is as trimethyl aluminium, triethyl aluminum, aluminium diethyl monochloride, diethyl aluminum chloride, ethyl sesquialter aluminum chloride, diisobutyl aluminum chloride, preferred aluminum compound is an aluminium diethyl monochloride.The add-on of halogen silicon compound or aluminum compound, should make that the mol ratio of oxyethyl group and magnesium is 0.3～1.4 in the last reaction product, the add-on of general halogen silicon compound is 0.5～4 with the molar ratio computing of silicon and magnesium, and the add-on of aluminum compound is 0.3～3 with the molar ratio computing of aluminium and magnesium.
In the above-mentioned catalyst component, described general formula is Ti (OR)
xCl
4-xTitanium compound, wherein x is the number of 0-4, R is C
1-C
14Fat or aryl radical, the mol ratio of titanium and magnesium is 0.5～15, is preferably 2～8; Particular compound as: titanium tetrachloride, purity titanium tetraethoxide, four titanium n-butoxide, four isobutoxy titaniums, four titanium propanolates, a chlorine triethoxy titanium, a chlorine three titanium butoxide are preferably: titanium tetrachloride, four titanium butoxide or four isobutoxy titaniums.
In the above-mentioned catalyst component, described general formula is R
n' Si (OR ")
4-nSilicon compound, wherein R ' and R " be C
1-C
14Aliphatic group, can be identical also can be inequality, n is the number of 0-4, the mol ratio of silicon compound and titanium compound is 0.01～1.0, is preferably 0.05～0.5; Particular compound as: tetraethoxysilane, four butoxy silanes, tetrapropoxysilane, methyltrimethoxy silane, Union carbide A-162 are preferably tetraethoxysilane.
In the above-mentioned catalyst component, described general formula is AlR
pCl
3-pAlkyl aluminum chloride reaction, the mol ratio of aluminium and titanium is 1～6, is preferably: 1～4.0＜p≤3 wherein, R is an alkyl; Particular compound as: aluminium diethyl monochloride, ethyl aluminum dichloride, ethyl sesquialter aluminum chloride, diisobutyl aluminum chloride, isobutyl-al dichloride are preferably: aluminium diethyl monochloride.
The present invention relates to a kind of preparation method of above-mentioned ingredient of solid catalyst, its feature exists, and comprises following steps:
1) preparation of carrier:
(a) ethanolic soln of preparation magnesium compound, temperature of reaction is 30～70 ℃;
(b) the porous inorganic oxide carrier is dipped in the above-mentioned solution;
(c) heating removes excess ethanol from suspension, and the mol ratio that makes oxyethyl group and magnesium is 1.5～4;
(d) under 30～60 ℃, solids and at least a general formula that step (c) is obtained are SiCl
mR
4-mHalogen silicon compound or at least a general formula be AlR
nX
3-nAluminum compound reaction, the mol ratio that makes oxyethyl group and magnesium is 0.3～1.4,0≤m≤4 wherein, R is an alkyl, X is a kind of among Cl, Br, the I, n is 0,1,2 or 3.
(2) load of active ingredient: under 30～70 ℃, reactant and at least a general formula that step (1) is obtained are Ti (OR)
xCl
4-xTitanium compound react, wherein x is the number of 0-4, R is C
1-C
14Fat or aryl radical, the mol ratio of titanium and magnesium is 0.5～15; Be R with at least a general formula again
n' Si (OR ")
4-nSilicon compound react wherein R ' and R " be C
1-C
14Aliphatic group, can be identical also can be inequality, n is the number of 0-4, the mol ratio of silicon compound and titanium compound is 0.01～1.0;
(3) reactant and the general formula that step (2) is obtained is AlR
pCl
3-pAlkyl aluminum chloride reaction, the mol ratio of aluminium and titanium is 1～4,0≤p≤3 wherein, R is an alkyl;
(4) reactant of washing, drying step (3) gained obtains ingredient of solid catalyst.
The invention still further relates to a kind of catalyzer that is used for vinyl polymerization or copolymerization, this catalyzer is made of above-mentioned ingredient of solid catalyst and conventional ziegler-natta promotor aluminum alkyls, and aluminum alkyls can adopt triethyl aluminum, tri-butyl aluminum, triisobutyl aluminium.In catalyzer of the present invention, in the promotor in aluminium and the active solid catalyst component mol ratio of titanium be 20: 1～250: 1, be preferably 100: 1～200: 1.
Catalyzer of the present invention is applicable to the equal polymerization of ethene and the copolymerization of ethene and alpha-olefin, alpha-olefin is the alkene of 3～10 carbon atoms, for example: propylene, butene-1, hexene-1,4-methylpentene-1, octene-1, polymerization technique can adopt slurry polymerization or the vapour phase polymerization in inert solvent.Polymerization temperature is 50～100 ℃.Owing to adopted special method to prepare support of the catalyst in the catalyzer of the present invention, therefore resulting catalyzer more is applicable to the vapour phase polymerization of ethene, and has shown very good performance.
Compare with prior art, the present invention has following advantage: after 1, catalyzer of the present invention was used for ethene gas-phase polymerization, catalytic activity was higher, and does not need pre-polymerization.In embodiment of the present invention (embodiment), polymerizing condition is: stagnation pressure 1MPa, and hydrogen dividing potential drop 0.2MPa, 85 ℃ of temperature, agitated bed polymerization 2 hours, its activity is: 120～350kgPE/gTi.2, the polymer bulk density height that makes by catalyzer of the present invention.The gas phase agitated bed can reach 0.42g/ml, fluidized-bed can reach 0.36g/ml.The polymer beads form is good, narrow diameter distribution, fine powder is few, in the polymkeric substance less than the content of the fine powder of 140 μ m less than 0.5wt%.3, the catalyzer by the present invention's preparation is particularly suitable for ethene gas-phase polymerization, and the polymerization initial activity is low, and the polymerization curve is steady, there are not caking and wall sticking phenomenon, density and melting index adjustability are good, have good copolymerization performance, are particularly useful for making LLDPE (linear low density polyethylene).
Embodiment:
The following examples only are used for that the present invention will be described, rather than limitation of the present invention.
In the following embodiments, the dehydration activation condition of silicon-dioxide is: at N
2Flow down in 600 ℃ the heating 4 hours after in 110-120 ℃ of following vacuum-drying 10 hours, the pore structure of made silicon-dioxide: specific surface area 280m
2/ g, pore volume 1.55ml/g, mean pore size 20nm.
Testing method:
1, melt index (MI): with reference to 190 ℃ of ASTM D1238-57T, the 2.16kg load
2, polymer bulk density (B.D): with reference to ASTM D1895-69
3, density polymer (d): GB1033
4, the mensuration of the degree of branching: infrared spectroscopy, U.S. FT-IR Mattson Cgguus embodiment 1:
Preparation of catalysts: all processes is carrying out (down together) in 250ml glass reaction bottle under the high purity nitrogen.1, the preparation of carrier: with the anhydrous MgCl of 1.5g
2Join in 40 milliliters the dehydrated alcohol,, forms transparent uniform solution and add 9 and restrain SiO under agitation in 60 ℃ of reactions 1.5 hours
2, after stirring 1 hour under 60 ℃, be warming up to 79 ℃, steam free ethanol under the nitrogen gas stream, continue to be warming up to 140 ℃, flow down at N2 and steam the ethanol that partially absorbs, make about 12 gram white solid powder, wherein the mol ratio of oxyethyl group and magnesium is 3.58; Thereupon, add dry hexane 60ml, SiCl
41.35ml, reacted 1 hour down in normal temperature, make suspension I, the mol ratio of oxyethyl group and magnesium is 0.5 in the analysis solids.2, the load of active ingredient titanium: in suspension I, add 1.8mlTiCl
4With 60 ℃ of reactions after 1 hour, add 0.5mlSi (OEt)
4React half an hour; Mother liquor is extracted in sedimentation out, after hexane (each 60ml) filtering and washing 3 times, adds the 60ml hexane, makes suspension II.3, carry out reduction reaction with aluminum alkyls and handle, in suspension II, add 2.3mlAlEt
2The hexane solution of Cl (2.21mmolAl/ml hexane) is warming up to 70 ℃ in reaction under 30 ℃ after 1 hour, gradually at N
2Flow down, steam hexane, make the dark ginger-colored pressed powder of 12.5g, through compositional analysis (wt%): Mg3.65%, Al2.08%, Cl15.0%, TiO.90%, OEt3.50%.
Ethene gas-phase polymerization: all processes is in high-purity N
2Carry out under the protection.Raise to press in 2 and to add 0.149g in the stirring tanks and go up controlling catalyst component, 3mmol triethyl aluminum and the 30g polyethylene powder mixture of drying treatment.Under agitation, feed hydrogen to 0.2Mpa, feed ethene again, still is pressed and is kept 1.0Mpa, under 85 ℃, and polyreaction 2 hours.Make the 219g spherical polyethylene, apparent density 0.40g/cm3, MI0.43g/10min, poly productive rate are 163KgPE/gTi, 1.5KgPE/gcat.The polyethylene size distribution saw Table for 1 (down together).Embodiment 2: Preparation of catalysts:
Other Preparation of Catalyst conditions are with embodiment 1, only in the preparation with carrier, and AlEt
2The hexane solution 10.6ml of Cl (2.21mmol/ml hexane) replaces SiCl
41.35ml, reacted 1 hour down with 30 ℃, after dry 3 times of hexane filtering and washing, add dry hexane 60ml, make suspension I, the mol ratio of oxyethyl group and magnesium is 0.8 in the analysis solids.Catalyst component compositional analysis (wt%): Mg3.59%, Al2.38%, Cl14.2%, Ti0.86%, OEt4.38%.
Ethene gas-phase polymerization: polymerizing condition and operation are used above-mentioned catalyst component 0.15 gram with embodiment 1, make 165 gram polyethylene, apparent density 0.41g/cm3, and MI0.86g/10min, the poly productive rate of gained is 121.3kgPE/gTi, 1.1KgPE/gcat.The polyethylene size distribution sees Table 1.Embodiment 3:
Ethene-1-butylene copolymerization: converging operation is with embodiment 1.The solid catalyst 0.062g of embodiment 1, AlEt33mmol, 30g polyethylene powder (as dispersion agent).Polymerizing condition is: stagnation pressure 1.0Mpa, and hydrogen 0.1Mpa, 1-butylene content is 5.2V% in the ethylene raw material gas, 85 ℃ of temperature, polymerization time 2 hours makes the 233g multipolymer, the productive rate of gained multipolymer is 345kg/gTi, 3.76kgPE/gcat, and the density of multipolymer is 0.9226g/cm
3, degree of branching 20.4CH
3/ 1000C, MI2.0g/10min, apparent density 0.40g/cm
3The polyethylene size distribution sees Table 1.Embodiment 4:
Ethene-1-butylene copolymerization: converging operation is with embodiment 1.With the solid catalyst 0.121g of embodiment 2, AlEt33mmol, 30g polyethylene powder (as dispersion agent).Polymerizing condition is: stagnation pressure 1.0Mpa, and hydrogen 0.22Mpa, 1-butylene content is 6.3V% in the ethylene raw material gas, 85 ℃ of temperature, polymerization time 2 hours makes the 163g multipolymer, its productive rate is 162kgPE/gTi, 1.35kgPE/gcat, and the density of multipolymer is 0.9225g/cm
3, degree of branching 22CH
3/ 1000C, MI14g/10min, apparent density 0.42g/cm
3
Embodiment 5:
Ethene gas-phase polymerization: be aggregated on the Φ 100 fluidized-bed ethene gas-phase polymerization devices and carry out, with embodiment 1 catalyzer, its amount is 0.195g, AlEt35mmol, the 100g polyethylene powder is as dispersion agent, and polymerizing condition is: stagnation pressure 1.0Mpa, hydrogen concentration 20%, 90 ℃ of temperature, polymerization 4 hours gets the 660g polyethylene, and its productive rate is: 3.4kgPE/gcat, MI0.39g/10min, apparent density 0.36g/cm
3
Embodiment 6:
In Preparation of Catalyst, the SiO of used embodiment 1
2With 1.4wt%Al (with SiO
2Be benchmark) ratio add AlEt
3In 30 ℃ of activation treatment 1 hour.Other conditions and operation are with embodiment 1, and polymerizing condition and operation are with embodiment 1, and the poly productive rate of gained is 198gPE/gTi, 1.72kgPE/gcat, MI0.39g/10min, apparent density 0.40g/cm
3
Embodiment 7:
Preparation of Catalyst:
1, with the anhydrous MgCl of 1g
2, the 0.5ml dibutyl phthalate joins in 40 milliliters the dehydrated alcohol, and 60 ℃ of reactions of son 1.5 hours form transparent uniform solution.Add 6 gram SiO
2, after stirring 1 hour under 60 ℃, be warming up to 79 ℃, flow down at N2 and steam free ethanol, continue to be warming up to 140 ℃, steam the ethanol that partially absorbs, make about 8.6 gram white solid powder, thereupon, add dry hexane 60ml, 7.1ml AlEt
2The hexane solution of Cl (2.21mmolAl/ml hexane), reaction is after 1 hour down in 30 ℃, and the employing method of pumping filtration is used hexane wash 3 times, makes suspension I.
2, in suspension I, add 2.4mlTiCl
4After 1 hour, add 0.65mlSi (0Et) in 60 ℃ of reactions
4, react half an hour, use the suction filtration method, after hexane (each 60ml) filtering and washing 4 times, add the 60ml hexane, make suspension II.
3, in suspension, add AlEt
2The hexane solution of the hexane solution 2.6ml of Cl (2.21mmolAl/ml hexane), reaction is after 1 hour down in 30 ℃, and intensification gradually is at N
2Flow down, steam hexane, the gained catalyzer consists of:
Mg3.60wt％、Al2.52wt％、Cl13.68wt％、Ti0.85wt％、OEt3.98％。
Ethene-1-butylene copolymerization: 1-butylene content is 4.0% in the ethylene raw material gas, catalyzer add-on 0.115g, other converging operations and polymerizing condition be with embodiment 1, the productive rate of gained multipolymer: 109kgPE/gTi, 0.93kgPE/gcat, the density 0.9316g/cm of multipolymer
3, degree of branching 15.5CH
3/ 1000C, MI7.12, apparent density 0.42g/cm
3Embodiment 8:
Ethylene thick liquid polymerizing:
2 liters of withstand voltage stirring tanks of stainless steel.1 liter of solvent hexane, AlEt
32mmol, embodiment 2 catalyzer 0.143g, polymerizing condition is: H
20.28Mpa, stagnation pressure 1.0Mpa, 85 ℃, polymerization 2 hours, the poly productive rate of gained is: 352kgPE/gTi, 3.4kgPE/gcat, poly MI2.03g/10min, apparent density 0.36g/cm
3Comparative example 1:
1 does not add SiCl in the catalyst preparation step of embodiment 1
41.35ml (0.0143mol), other conditions are with embodiment 1.
Polymerizing condition is with embodiment 1.Catalyst levels is 0.165 gram, makes 103 gram polyethylene, and the polyethylene productive rate is 36kgPE/gTi, 0.62kgPE/gcat, MI0.53g/10min, apparent density 0.32g/cm
3, the polyethylene size distribution sees Table 1.Comparative example 2;
2 do not add Si (OEt) in the catalyst preparation step of embodiment 2
4, other conditions are with embodiment 2.
Polymerizing condition and operation are with embodiment 2, and the polyethylene productive rate is 96kgPE/gTi, 0.92kgPE/gcat, MI0.72g/10min, apparent density 0.37g/cm
3, the polyethylene size distribution sees Table 1.
Table 1:
| Embodiment | Catalyst activity kgPE/gTi | Apparent density g/cm 3 | Polymkeric substance particle diameter distribution wt% | ||
| ＞1250μm | 1250～140μm | ＜140μm | |||
| 1 | 163.0 | 0.40 | 1.8 | 97.7 | 0.5 |
| 2 | 121.3 | 0.42 | 1.7 | 97.9 | 0.4 |
| 3 | 345.0 | 0.40 | 1.0 | 98.5 | 0.5 |
| Comparative example 1 | 36.0 | 0.34 | 2.0 | 96.5 | 1.0 |
| Comparative example 2 | 96.0 | 0.37 | 3.0 | 96 | 1.0 |
Claims (10)
1, a kind of ingredient of solid catalyst of for olefines polymerization, it is characterized in that: include following component: magnesium 1.5～4.5wt%, titanium 0.6～1.5wt%, chlorine 6.0～18.0wt%, alkoxyl group 0.7～8.0wt%, aluminium 0.5～3.5wt%, and preparation by the following method:
(1) preparation of carrier:
(a) ethanolic soln of preparation magnesium compound, it is MgX that described magnesium compound is selected from general formula
2Compound, wherein X is bromine, iodine or chlorine;
(b) the porous inorganic oxide carrier is dipped in the above-mentioned solution;
(c) heating removes excess ethanol from suspension, and the mol ratio that makes oxyethyl group and magnesium is 1.5～4;
(d) under 30～60 ℃, solids and at least a general formula that step (c) is obtained are SiCl
mR
4-mHalogen silicon compound or at least a general formula be AlR
nX
3-nAluminum compound reaction, the mol ratio that makes oxyethyl group and magnesium is 0.3～1.4,0≤m≤4 wherein, R is an alkyl, X is a kind of among Cl, Br, the I, n is 0,1,2 or 3;
(2) load of active ingredient: reactant and at least a general formula that step (1) is obtained are Ti (OR)
xCl
4-xTitanium compound react, wherein x is the number of 0-4, R is C
1-C
14Fat or aryl radical, the mol ratio of titanium and magnesium is 0.5～15; Be R with at least a general formula again
n' Si (OR ")
4-nSilicon compound react wherein R ' and R " be C
1-C
14Aliphatic group, can be identical also can be inequality, n is the number of 0-4, the mol ratio of silicon compound and titanium compound is 0.01～1.0;
(3) reactant and the general formula that step (2) is obtained is AlR
pCl
3-pAlkyl aluminum chloride reaction, the mol ratio of aluminium and titanium is 1～4,0≤p≤3 wherein, R is an alkyl;
(4) reactant of washing, drying step (3) gained obtains ingredient of solid catalyst.
2, ingredient of solid catalyst according to claim 1, it is characterized in that, can also add one or more of following electron donor in the described magnesium compound ethanolic soln: ethyl benzoate, diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, tetrahydrofuran (THF).
3, ingredient of solid catalyst according to claim 1 is characterized in that, the weight ratio of described magnesium compound and porous inorganic oxide carrier was controlled at 1: 3～1: 15.
4, ingredient of solid catalyst according to claim 1 is characterized in that, described general formula is SiCl
mR
4-mHalogen silicon compound add-on with the molar ratio computing of silicon and magnesium be 0.5～4 or general formula be AlR
nX
3-nThe add-on of aluminum compound be 0.3～3 with the molar ratio computing of aluminium and magnesium.
5, ingredient of solid catalyst according to claim 1 is characterized in that, general formula is SiCl
mR
4-mThe halogen silicon compound be selected from silicon tetrahalogen, METHYL TRICHLORO SILANE, ethyl trichlorosilane, propyltrichlorosilan, dimethyldichlorosilane(DMCS), the diethyl dichlorosilane one or more.
6, ingredient of solid catalyst according to claim 1 is characterized in that general formula is AlR
nX
3-nAluminum compound be selected from one or more of trimethyl aluminium, triethyl aluminum, aluminium diethyl monochloride, diethyl aluminum chloride, ethyl sesquialter aluminum chloride, diisobutyl aluminum chloride.
7, ingredient of solid catalyst according to claim 1 is characterized in that, general formula is R
n' Si (OR ")
4-nSilicon compound be selected from tetraethoxysilane, four butoxy silanes, tetrapropoxysilane, methyltrimethoxy silane, the Union carbide A-162 one or more.
8, the preparation method of the described ingredient of solid catalyst of a kind of claim 1 is characterized in that, may further comprise the steps:
1) preparation of carrier:
(a) ethanolic soln of preparation magnesium compound, temperature of reaction is 30～70 ℃, described magnesium compound
Being selected from general formula is MgX
2Compound, wherein X is bromine, iodine or chlorine;
(b) the porous inorganic oxide carrier is dipped in the above-mentioned solution;
(c) heating removes excess ethanol from suspension, and the mol ratio that makes oxyethyl group and magnesium is 1.5～4;
(d) under 30～60 ℃, solids and at least a general formula that step (c) is obtained are SiCl
mR
4-mHalogen silicon compound or at least a general formula be AlR
nX
3-nAluminum compound reaction, the mol ratio that makes oxyethyl group and magnesium is 0.3～1.4,
(2) load of active ingredient: under 30～70 ℃, reactant and at least a general formula that step (1) is obtained are Ti (OR)
xCl
4-xTitanium compound react, the mol ratio of titanium and magnesium is 0.5～15; Be R with at least a general formula again
n' Si (OR ")
4-nSilicon compound react, the mol ratio of silicon compound and titanium compound is 0.01～1.0;
(3) reactant and the general formula that step (2) is obtained is AlR
pCl
3-pAlkyl aluminum chloride reaction, the mol ratio of aluminium and titanium is 1～4;
(4) reactant of washing, drying step (3) gained obtains ingredient of solid catalyst.
9, a kind of vinyl polymerization or copolymerization catalysts is characterized in that, it is made up of described ingredient of solid catalyst of one of claim 1～7 and promotor aluminum alkyls.
10, the application of the described ingredient of solid catalyst of one of a kind of claim 1～7 in ethene gas-phase polymerization or copolymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991077628A CN1137154C (en) | 1999-05-27 | 1999-05-27 | Ethylene Polymerizing solid catalyst composition, its preparation process, application and solid catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991077628A CN1137154C (en) | 1999-05-27 | 1999-05-27 | Ethylene Polymerizing solid catalyst composition, its preparation process, application and solid catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1275579A CN1275579A (en) | 2000-12-06 |
| CN1137154C true CN1137154C (en) | 2004-02-04 |
Family
ID=5272915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991077628A Expired - Lifetime CN1137154C (en) | 1999-05-27 | 1999-05-27 | Ethylene Polymerizing solid catalyst composition, its preparation process, application and solid catalyst |
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| Country | Link |
|---|---|
| CN (1) | CN1137154C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148484B (en) * | 2007-08-06 | 2010-06-23 | 北京凯华创新科技有限公司 | Linear polyethylene catalyst, preparation method and application thereof |
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1999
- 1999-05-27 CN CNB991077628A patent/CN1137154C/en not_active Expired - Lifetime
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