CN109438595A - A kind of ethene gas-phase polymerization slurry type catalyst and preparation method thereof - Google Patents
A kind of ethene gas-phase polymerization slurry type catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of ethene gas-phase polymerization slurry type catalyst and preparation method thereof, which includes the active component and activator component of titaniferous；The active component of the titaniferous is that load has at least one magnesium compound, a kind of titanium-containing compound, at least one electron donor compound and at least one copolymerization performance modifying agent containing boric acid ester compound on silica supports；The electron donor compound is selected from one kind or their mixture of alcohol or ether, and the additional amount control of electron donor compound is 5 moles to 300 moles in every mole of titanium；The general formula of the activator component is AlR 'nX3‑nOrgano-aluminum compound, the alkyl that R ' is hydrogen or carbon atom number is 1~20 in formula, X is halogen, and n is the number of 1 < n≤3.The catalyst has many advantages, such as that catalytic activity is high, copolymerization performance is good, Granularity Distribution is uniform, fine powder content is few, can be used for the higher linear alpha olefins combined polymerization such as ethylene and 1- hexene, 1- octene and produces high performance polyvinyl resin.
Description
Technical field
The invention belongs to catalyst fields, and in particular to a kind of slurry type high activity for ethene gas-phase polymerization technique,
The catalyst and preparation method thereof of high copolymerization performance, the catalyst are mainly applied in ethene gas-phase polymerization or combined polymerization, especially
It is the application of the gas-phase fluidized-bed frozen state of ethylene or super frozen state technique.
Background technique
Since the 1950s, Ziegler-Natta catalyst was successfully applied to the industrial production of polyolefin, polyene
Hydrocarbon industrial development is rapid.The polyethylene production capacity in China increases at a high speed always, China's polyethylene production capacity in 2005 less than 5,000,000 tons/
Year, cut-off to 2016 nearly 19,000,000 tons/year of China's polyethylene production capacity.From the point of view of domestic polyethylene (PE) production capacity is by the type of business,
Middle petroleum accounting is maximum, accounts for the 33% of aggregated capacity；Middle petrochemical industry is secondly, account for the 27% of aggregated capacity；Third is ranked in joint venture, accounts for
23%；4th is coal-to-olefin enterprise, and the enterprise for expanding energy in recent years is mostly coal-to-olefin enterprise, such as middle coal, extension, treasured
Rich, Pucheng, Shenhua Yulin；5th is local enterprise, proportion 3%.
Gas-phase polyethylene technique is short, easy to operate, low, suitable without solvent, investment and operating cost because of its process flow
Symphysis produces the features such as full density polythene, the favor by the major polyethylene production manufacturer in the whole world.Typical gas phase process has
The Uniopl technique of Univation company, the Innovene technique of BP Amoco company, the Spherilene work of Basell company
Evolue technique of skill, Lupotech G technique and Mitsui Chemicals, Inc. etc..Recently as condensation, super condensation operation technology
It promotes and applies, so that gas phase full density polythene device rapid development.By the driving of full density polythene demand, China is in recent years
Also gas-phase polythene technique process units is largely introduced, it is contemplated that the production capacity to the end of the year 2021, China's gas-phase polyethylene will
Reach 1133.4 ten thousand tons/year.
Core technology of the catalyst technology as polyethylene industrial development is researched and developed process in recent years and is also constantly being accelerated, be
Polyethylene industrial expansion provides powerful technical support.Currently, the catalyst for producing gas-phase polythene mainly has three
Kind: first is that chromium-based catalysts, dipping contains chromium compound, including chromium oxide catalyst and Organic Chromium on silica gel or Alusil carrier
Catalyst；Second is that titanium-based Ziegler-Natta catalyst, mainly Ti-base catalyst, with chemical bonds on magnesium-containing carrier
Transistion metal compound；Third is that the single site catalysts such as metallocene.Titanium-based Ziegler-Natta catalyst is because of its preparation
The advantages that simple process, production cost are low, catalytic activity is high is currently the mainstream catalyst of gas-phase polythene technique.
The slurry type catalyst that Univation company develops is a kind of novel magnesium titanium system slurry catalyst, in frozen state
Under operating condition, catalyst activity is 20000~25000gPE/gcat, 0.32~0.36g/cm of bulk density of product3.Phase
For other types solid catalyst, active high, the charging accurate stable of slurry catalyst, prepare it is convenient, flexible, can be effective
The features such as reduction reactor static, properties of product are excellent, unit product catalyst is at low cost, development prospect is very considerable, at
For the leading catalyst of gas-phase method total density polyvinyl technique.The gas-phase polyethylene device of 95% or more foreign countries uses at present
Slurry type catalyst.
CN 108299577A discloses a kind of olefin polymerization catalysis and its preparation method and application, the Invention Announce
Catalyst is mainly to be made of catalyst body component and co-catalyst, and the host component of catalyst by metallic element or/and contains
There are compound, the organic compound containing lone pair electrons, the dispersing agent reaction of metallic element to be made, co-catalyst is organic calorize
Object is closed, solution-air, gas-solid, under gas-liquid-solid state ethylene homo or the ethylene and alpha-olefin copolymer of alkene are primarily adapted for use in.
CN 102260360B discloses a kind of ethylene rolymerization catalyst and its preparation and application；By titaniferous active component and
Activator component composition；Titaniferous active component is that load has at least one magnesium dihalide, at least one on silica supports
Halogenated titanium, at least one electron donor compound and a kind of component of modifying agent；Electron donor compound is selected from alcohol or ether, modified
Agent is thiocyanate groups propyl-triethoxysilicane；Activator component is organo-aluminum compound；For ethene gas-phase polymerization or altogether
Have many advantages, such as that catalytic activity is high, polyethylene powder bulk density is high, fine powder is few when polymerization.
CN 1986575A discloses a kind of preparation method of slurry catalyst for ethene gas-phase polymerization technique.This is urged
Magnesium chloride is modified first in agent preparation process to improve the homogeneity of active constituent, while high using emulsion reactor
The fast molding method of shear granulation, resulting catalyst include one kind active solid of titanium containing magnesium component, at least one electron donor
With at least one activator, it is carried on inertia nanoscale silica gel.Resulting catalyst granules size distribution is concentrated, and is had higher
Polymerization activity, fine powder content is lower, is suitable for the Unipol gas-phase polymerization process that catalyst is fed as a slurry.
CN 103772550A discloses a kind of catalyst for ethylene polymerization, including following component: the solid catalyst of titaniferous
Component, be organic epoxy compound object is dissolved in by magnesium halide, organic phosphorus compound adds electron donor compound and is formed
Then homogeneous solution is acted on silicon compound and precipitation additive, then mixed with the halide of titanium or derivatives thereof, consolidate
Body catalyst component；The catalyst activity is higher, and hydrogen regulation performance is excellent, is suitable for ethylene slurry polymerization or gas-phase polymerization, especially suitable
Gas-phase fluidized bed polymerization process for the ethylene that catalyst is fed as a slurry.
Making a general survey of ethene gas-phase polymerization catalyst patent can be seen that the preparation process complexity of catalyst, and operating condition is harsh,
It all needs for active constituent to be supported on silica-gel carrier, while electron donor compound and activating agent is added, and using spraying dry
Catalyst Precursors are made in dry mode, are re-dissolved in mineral oil and are made into slurry type catalyst.The catalyst tool that related patents are related to
There is the features such as catalytic activity is high, polyethylene powder bulk density is high, fine powder is few, size distribution is uniform, hydrogen regulation performance is excellent, but
It is not obviously improved in terms of copolymerization performance.In use, ethylene and 1- hexene or 1- octene copolymer are especially catalyzed
When symphysis produces high-performance polyethylene often in performance copolymerization performance it is bad, because 1- hexene in reactor, 1- octene concentration is high due to lead
The problems such as causing recycle gas compressor hydrops.Therefore, the copolymerization performance for improving catalyst is Ziegler-Natta catalyst exploitation neck
One of most important research hotspot in domain.
Summary of the invention
The first purpose of this invention is to provide a kind of ethene gas-phase polymerization slurry type catalyst, to solve existing catalysis
The bad technical problem of copolymerization performance in agent use process, the catalyst pass through the preparation process in catalyst activity component parent
Middle copolymerization performance modifying agent of the addition containing boric acid ester compound, gained catalytic component are reinstated with organo-aluminium activator promotor one
When ethylene copolymerization reaction, the copolymerization performance of catalyst system can be significantly improved, the application efficiency of comonomer is improved.
To achieve the above object, the present invention is achieved by the following technical scheme:
A kind of ethene gas-phase polymerization slurry type catalyst, active component and activator component including titaniferous；
The active component of the titaniferous is that load on silica supports has at least one magnesium compound, is a kind of containing titanizing
Close object, at least one electron donor compound and at least one copolymerization performance modifying agent containing boric acid ester compound, titaniferous
Active component in each component molar ratio control in 1 < Mg/Ti < 20,0 <borate/Ti < 0.1；The electron donor chemical combination
Object is selected from one kind or their mixture of alcohol or ether, and the additional amount control of electron donor compound is 5 in every mole of titanium
Mole to 300 moles；
The general formula of the activator component is AlR 'nX3-nOrgano-aluminum compound, R ' is hydrogen in formula or carbon atom number is 1
~20 alkyl, X are halogen, and n is the number of 1 < n≤3.
As a preference of the present invention, the magnesium compound is magnesium dihalide, preferably MgCl2、MgBr2、MgI2Or it is mixed
Close object.
As a preference of the present invention, the titanium-containing compound is Ti (OR)4-nXnOr TiX3, R is C in formula1~C4Rouge
Fat alkyl, X are one kind of F, Cl, Br, the integer that n is 1~4, preferably TiCl3Or TiCl4。
As a preference of the present invention, the electron donor compound is C1~C4Alcohol, C2~C6Aliphatic ether, C3~C4
One or more of cyclic ethers mixture, preferably methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, second
The mixture of one or more of ether, hexyl ether or tetrahydrofuran, most preferably tetrahydrofuran.
As a preference of the present invention, the boric acid ester compound contains the one kind of silicon (- Si) in molecular structure
Compound, preferably three (trimethyl silane) borates, three (triethylsilane) borates etc..
As present invention further optimization, the additional amount of the electron donor compound is preferably controlled in every mole of titanium
It is 10 moles to 100 moles.
As present invention further optimization, silica supports particle size range is 0.01~1 μm, preferably 0.01
~0.1 μm.
Second object of the present invention is to provide a kind of preparation method of ethene gas-phase polymerization slurry type catalyst, the party
Method have the following steps are included:
(1) preparation of parent: magnesium compound, titanium-containing compound, electron donor compound being added in reactor and reacted, it
Reactor is added in the boric acid ester compound being dissolved in electron donor compound afterwards, continues to react, prepares parent；?
During preparing parent, the molar ratio of each component is 1 < Mg/Ti < 20,0 <borate/Ti < 0.1, electron donor compound plus
Entering amount control in every mole of titanium is 5 moles to 300 moles；
(2) preparation of catalyst suspension: step (1) resulting parent is blended to obtain with smoke-like silica supports
Be suitable for the suspension of spray drying: the silica supports wherein selected are hydrophobic types, i.e. the water that does not adsorb of its surface,
Silica supports partial size be 0.01~1 μm, in suspension the content of silica supports be 10~60%, preferably 20~
40%；
(3) shaping of catalyst: the suspension that step (2) obtains is spray-dried, the active group of solid titaniferous is obtained
Point, average diameter of particles is at 10~50 μm；
(4) catalyst prereduction: in order to make the active component of the solid titaniferous obtained after spray drying be suitable for production second
Alkene polymer, must also be reduced into titanium atom in the active component of the titaniferous using organo-aluminum compound can make ethylene effective
The valence state of polymerization；Generally in hydrocarbon solvent, the active component and activator component for the solid titaniferous that step (3) is obtained are carried out
Reaction, obtains catalyst；The activator component is general formula AlR 'nX3-nOrgano-aluminum compound, R ' is that hydrogen or carbon are former in formula
The alkyl that subnumber is 1~20, X are halogen, and n is the number of 1 < n≤3.
As a preference of the present invention, the hydrocarbon solvent can be isopentane, hexane, heptane, toluene, dimethylbenzene, stone
One or more of mixture in cerebrol or mineral oil.
As a preference of the present invention, the molar ratio of aluminium and titanium is 10~500.
The catalyst that the present invention obtains after carrying out reduction is added in polymer reactor after can drying, can also be by the work of this titaniferous
The suspension of property component and activator component is added directly into reactor, has been carried out again with additional activator in the reactor
Full activation, activator can select AlEt3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2The mixing of one or more of Cl
Object.
The advantages and positive effects of the present invention:
(1) catalyst provided by the invention can be mentioned obviously since boric acid ester compound, boric acid ester compound is added
High ethylene and 1- hexene or 1- octene copolymer symphysis produce copolymerizable when high-performance polyethylene, and it is bad to solve previous copolymerization performance
Problem, the homopolymerization or combined polymerization with long-chain alpha-olefin which is suitable for ethylene, wherein when copolymerization alpha-olefin using propylene,
One of 1- butylene, 1- amylene, 1- hexene, 1- octene, 4-methyl-1-pentene.
(2) polyethylene catalysts provided by the invention are able to produce being total to for full density polythene product, especially catalyst
Poly- performance significantly improves, to improve the comprehensive performance of polyethylene product.
(3) catalyst provided by the invention is in use, polymerization technique is more suitable for using vapor phase method, slurry process or solwution method
In gas fluidised bed polymerisation, especially gas-phase fluidized-bed frozen state or super condensation mode.Simultaneously as catalyst of the present invention
Partial size is thinner, therefore inert diluent can be used by catalyst dilution, such as mineral oil etc. is realized by delivery pump feeding manner
Catalyst uniform feeding, stable operation.
(4) improvement of copolymerization performance depends on the selectivity in coordination polymerization activated centre, by electron donor to work
Property the electronic action of the metal center and regulation of three-dimensional effect, the coordination to large volume comonomer may be implemented, insertion, chain increase
The efficiency of long reaction, to improve the copolymerization ability in activated centre.Boric acid ester compound proposed by the present invention passes through modulation
Substituent group volume size and electron are strong and weak, effectively improve activated centre titanium to the coordination polymerization performance of comonomer.
Specific embodiment
It is detailed below by embodiment and comparative example to make those skilled in the art understand technical solution of the present invention and advantage
Describe bright technical solution of the present invention in detail, but and for limiting the scope of the invention.
Embodiment 1
1. catalyst preparation
To by N23.0g TiCl is added in the 250mL there-necked flask being sufficiently displaced from4, 6.9 grams of MgCl2With 155mL tetrahydro furan
It mutters, 60 DEG C is warming up under stirring, isothermal reaction 2 hours, 0.044g tri- (trimethyl silane) borate is added and (is dissolved in 10mL tetra-
In hydrogen furans, borate/Ti=0.01), isothermal reaction 2 hours, it is cooled to 30 DEG C.
Pass through N to one210.5 grams of silica gel (Cabot are added in the 250mL there-necked flask being sufficiently displaced from
CorporationTS-610, partial size are 0.02~0.1 μm) after, the mother liquor after cooling is added, is kept for 30 DEG C of temperature, stirring 2
Hour, the mother liquor after stirring is spray-dried mother liquor with spray drying device, spray condition: 160 DEG C of inlet temperature, out
80 DEG C of temperature of mouth, obtains ingredient of solid catalyst, wherein Ti content is 2.21%, Mg content is 6.19%, THF content is
26.7%.Mineral oil is added into obtained ingredient of solid catalyst, is made into the mineral oil solution containing solids 30%, according to
The content of THF presses THF:AlEt2Cl:Al(C6H13)3AlEt is added in the molar ratio of=1:0.45:0.22After Cl reacts 30 minutes,
Add Al (C6H13)3。
2. the slurry polymerization of ethylene
2L reaction kettle is heated to 100 DEG C, 1h is vacuumized, is replaced with drying nitrogen, then blows row with hydrogen.To polymeric kettle
Middle addition 1L hexane, 20mL 1- hexene, while the triethyl aluminum and above-mentioned catalyst 30mg of 1mmol is added, then raise temperature to 75
DEG C, hydrogen 0.18MPa is added, ethylene, which is added, after adding hydrogen makes pressure in kettle reach 1.03MPa, after being warming up to 85 DEG C, reaction 2
After hour, cooling discharge, slurry polymerization the results are shown in Table 1.
Embodiment 2
1. catalyst preparation
To by N23.0g TiCl is added in the 250mL there-necked flask being sufficiently displaced from4, 6.9 grams of MgCl2With 160mL tetrahydro furan
It mutters, 60 DEG C is warming up under stirring, isothermal reaction 2 hours, 0.048g tri- (triethylsilane) borate is added and (is dissolved in 10mL tetra-
In hydrogen furans, borate/Ti=0.01), isothermal reaction 2 hours, it is cooled to 30 DEG C.
Pass through N to one210.5 grams of silica gel (Cabot are added in the 250mL there-necked flask being sufficiently displaced from
CorporationTS-610, partial size are 0.02~0.1 μm) after, the mother liquor after cooling is added, is kept for 30 DEG C of temperature, stirring 2
Hour, the mother liquor after stirring is spray-dried mother liquor with spray-dried instrument, spray condition: 160 DEG C of inlet temperature, outlet
80 DEG C of temperature, ingredient of solid catalyst is obtained, wherein Ti content is 2.16%, Mg content is 6.33%, THF content is
28.6%.Mineral oil is added into obtained ingredient of solid catalyst, is made into the mineral oil solution containing solids 30%, according to
The content of THF presses THF:AlEt2Cl:Al(C6H13)3AlEt is added in the molar ratio of=1:0.45:0.22After Cl reacts 30 minutes,
Add Al (C6H13)3。
2. the slurry polymerization of ethylene
2L reaction kettle is heated to 80 DEG C or so, 1h is vacuumized, is replaced with drying nitrogen, then blows row with hydrogen.Xiang Ju
It closes and 1L hexane, 20mL 1- hexene is added in kettle, while the triethyl aluminum and above-mentioned catalyst 30mg of 1mmol is added, then heat up
To 75 DEG C, hydrogen 0.18MPa is added, ethylene, which is added, after adding hydrogen makes pressure in kettle reach 1.03MPa, after being warming up to 85 DEG C,
After reaction 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
Embodiment 3
1. catalyst preparation
To by N23.0g TiCl is added in the 250mL there-necked flask being sufficiently displaced from4, 6.9 grams of MgCl2With 170mL tetrahydro furan
It mutters, 60 DEG C is warming up under stirring, isothermal reaction 2 hours, 0.088g tri- (trimethyl silane) borate is added and (is dissolved in 10mL tetra-
In hydrogen furans, borate/Ti=0.02), isothermal reaction 2 hours, it is cooled to 30 DEG C.
Pass through N to one210.5 grams of silica gel (Cabot are added in the 250mL there-necked flask being sufficiently displaced from
CorporationTS-610, partial size are 0.02~0.1 μm) after, the mother liquor after cooling is added, is kept for 30 DEG C of temperature, stirring 2
Hour, the mother liquor after stirring is spray-dried mother liquor with spray-dried instrument, spray condition: 160 DEG C of inlet temperature, outlet
80 DEG C of temperature, ingredient of solid catalyst is obtained, wherein Ti content is 2.17%, Mg content is 6.41%, THF content is
27.8%.Mineral oil is added into obtained ingredient of solid catalyst, is made into the mineral oil solution containing solids 30%, according to
The content of THF presses THF:AlEt2Cl:Al(C6H13)3AlEt is added in the molar ratio of=1:0.45:0.22After Cl reacts 30 minutes,
Add Al (C6H13)3。
2. the slurry polymerization of ethylene
2L reaction kettle is heated to 80 DEG C or so, 1h is vacuumized, is replaced with drying nitrogen, then blows row with hydrogen.Xiang Ju
It closes and 1L hexane, 20mL 1- hexene is added in kettle, while the triethyl aluminum and above-mentioned catalyst 50mg of 1mmol is added, then heat up
To 75 DEG C, hydrogen 0.18MPa is added, ethylene, which is added, after adding hydrogen makes pressure in kettle reach 1.03MPa, after being warming up to 85 DEG C,
After reaction 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
Embodiment 4
1. catalyst preparation
To by N23.0g TiCl is added in the 250mL there-necked flask being sufficiently displaced from4, 6.9 grams of MgCl2With 170mL tetrahydro furan
It mutters, 60 DEG C is warming up under stirring, isothermal reaction 2 hours, 0.132g tri- (trimethyl silane) borate is added and (is dissolved in 10mL tetra-
In hydrogen furans, borate/Ti=0.03), isothermal reaction 2 hours, it is cooled to 30 DEG C.
Pass through N to one210.5 grams of silica gel (Cabot are added in the 250mL there-necked flask being sufficiently displaced from
CorporationTS-610, partial size are 0.02~0.1 μm) after, the mother liquor after cooling is added, is kept for 30 DEG C of temperature, stirring 2
Hour, the mother liquor after stirring is spray-dried mother liquor with spray-dried instrument, spray condition: 160 DEG C of inlet temperature, outlet
80 DEG C of temperature, ingredient of solid catalyst is obtained, wherein Ti content is 2.09%, Mg content is 6.41%, THF content is
27.5%.Mineral oil is added into obtained ingredient of solid catalyst, is made into the mineral oil solution containing solids 30%, according to
The content of THF presses THF:AlEt2Cl:Al(C6H13)3AlEt is added in the molar ratio of=1:0.45:0.22After Cl reacts 30 minutes,
Add Al (C6H13)3。
2. the slurry polymerization of ethylene
2L reaction kettle is heated to 80 DEG C or so, 1h is vacuumized, is replaced with drying nitrogen, then blows row with hydrogen.Xiang Ju
It closes and 1L hexane, 20mL 1- hexene is added in kettle, while the triethyl aluminum and above-mentioned catalyst 50mg of 1mmol is added, then heat up
To 75 DEG C, hydrogen 0.18MPa is added, ethylene, which is added, after adding hydrogen makes pressure in kettle reach 1.03MPa, after being warming up to 85 DEG C,
After reaction 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
Embodiment 5
1. catalyst preparation
To by N23.0g TiCl is added in the 250mL there-necked flask being sufficiently displaced from4, 6.9 grams of MgCl2With 170mL tetrahydro furan
It mutters, 60 DEG C is warming up under stirring, isothermal reaction 2 hours, 0.176g tri- (trimethyl silane) borate is added and (is dissolved in 10mL tetra-
In hydrogen furans, borate/Ti=0.04), isothermal reaction 2 hours, it is cooled to 30 DEG C.
Pass through N to one210.5 grams of silica gel (Cabot are added in the 250mL there-necked flask being sufficiently displaced from
CorporationTS-610, partial size are 0.02~0.1 μm) after, the mother liquor after cooling is added, is kept for 30 DEG C of temperature, stirring 2
Hour, the mother liquor after stirring is spray-dried mother liquor with spray-dried instrument, spray condition: 160 DEG C of inlet temperature, outlet
80 DEG C of temperature, ingredient of solid catalyst is obtained, wherein Ti content is 2.03%, Mg content is 6.35%, THF content is
27.06%.Mineral oil is added into obtained ingredient of solid catalyst, is made into the mineral oil solution containing solids 30%, according to
The content of THF presses THF:AlEt2Cl:Al(C6H13)3AlEt is added in the molar ratio of=1:0.45:0.22After Cl reacts 30 minutes,
Add Al (C6H13)3。
2. the slurry polymerization of ethylene
2L reaction kettle is heated to 80 DEG C or so, 1h is vacuumized, is replaced with drying nitrogen, then blows row with hydrogen.Xiang Ju
It closes and 1L hexane, 20mL 1- hexene is added in kettle, while the triethyl aluminum and above-mentioned catalyst 50mg of 1mmol is added, then heat up
To 75 DEG C, hydrogen 0.18MPa is added, ethylene, which is added, after adding hydrogen makes pressure in kettle reach 1.03MPa, after being warming up to 85 DEG C,
After reaction 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
Embodiment 6
With embodiment 3, the difference is that addition is 20mL 1- octene in ethylene sluny polymerization process.Slurry polymerization
It the results are shown in Table 1.
Embodiment 7
With embodiment 3, the difference is that addition is 30mL 1- octene in ethylene sluny polymerization process.Slurry polymerization
It the results are shown in Table 1.
Comparative example 1
1. catalyst preparation
To by N23.0g TiCl is added in the 250mL there-necked flask being sufficiently displaced from4, 6.9 grams of MgCl2With 170mL tetrahydro furan
It mutters, 60 DEG C is warming up under stirring, isothermal reaction 2 hours, is cooled to 30 DEG C.
Pass through N to one210.5 grams of silica gel (Cabot CorporationTS- are added in displaced 250mL there-necked flask
610, partial size is 0.02~0.1 μm) after, the mother liquor after cooling is added, is kept for 30 DEG C of temperature, is stirred 2 hours, after stirring
Mother liquor is spray-dried mother liquor with spray-dried instrument, spray condition: 160 DEG C of inlet temperature, 80 DEG C of outlet temperature, consolidate
Body catalyst component, wherein Ti content is 2.44%, Mg content is 6.22%, THF content is 31.3%.It is urged to obtained solid
Mineral oil is added in agent component, is made into the mineral oil solution containing solids 30%, THF:AlEt is pressed according to the content of THF2Cl:
Al(C6H13)3AlEt is added in the molar ratio of=1:0.45:0.22After Cl reacts 30 minutes, Al (C is added6H13)3。
2. the slurry polymerization of ethylene
2L reaction kettle is heated to 80 DEG C or so, 1h is vacuumized, is replaced with drying nitrogen, then blows row with hydrogen.Xiang Ju
It closes and 1L hexane, 20mL 1- hexene is added in kettle, while the triethyl aluminum and above-mentioned catalyst 30mg of 1mmol is added, then heat up
To 75 DEG C, hydrogen 0.18MPa is added, ethylene, which is added, after adding hydrogen makes pressure in kettle reach 1.03MPa, after being warming up to 85 DEG C,
After reaction 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
Comparative example 2
Catalyst preparation is carried out according to embodiment 3 in publication CN 102260360B, the slurry polymerization evaluation of ethylene is same
Embodiment 3, the results are shown in Table 1.
1 vinyl polymerization lab scale evaluation result of table
Ethene gas-phase polymerization Ziegler-Natta catalyst of the invention, is added suitable boric acid in its preparation process
Ester type compound, under the premise of high activity, the high heap density of polyethylene product, the low fine content of guarantee catalyst are low, significantly
The copolymerization performance of catalyst is improved, i.e., under same concentration of comonomers, the relative density of polyethylene product reduces significantly.
Claims (10)
1. a kind of ethene gas-phase polymerization slurry type catalyst, active component and activator component including titaniferous；It is characterized in that,
The active component of the titaniferous is that load has at least one magnesium compound, a kind of titanium-containing compound, extremely on silica supports
A kind of few electron donor compound and at least one copolymerization performance modifying agent containing boric acid ester compound, the active group of titaniferous
The molar ratio of each component is controlled in 1 < Mg/Ti < 20,0 <borate/Ti < 0.1 in point；The electron donor compound is selected from alcohol
Or one kind or their mixture of ether, electron donor compound additional amount control every mole of titanium be 5 moles extremely
300 moles；
The general formula of the activator component is AlR 'nX3-nOrgano-aluminum compound, R ' is hydrogen in formula or carbon atom number is 1~20
Alkyl, X are halogen, and n is the number of 1 < n≤3.
2. a kind of ethene gas-phase polymerization slurry type catalyst according to claim 1, which is characterized in that the magnesium chemical combination
Object is magnesium dihalide, and the magnesium dihalide includes MgCl2、MgBr2、MgI2Or mixtures thereof.
3. a kind of ethene gas-phase polymerization slurry type catalyst according to claim 1, which is characterized in that described contains titanizing
Conjunction object is Ti (OR)4-nXnOr TiX3, R is C in formula1~C4Aliphatic group, X is one kind of F, Cl, Br, the integer that n is 1~4.
4. a kind of ethene gas-phase polymerization slurry type catalyst according to claim 1, which is characterized in that the electron
Body compound is C1~C4Alcohol, C2~C6Aliphatic ether, C3~C4One or more of cyclic ethers mixture.
5. a kind of ethene gas-phase polymerization slurry type catalyst according to claim 1, which is characterized in that the borate
Class compound contains a kind of compound of silicon (- Si), including three (trimethyl silane) borates, three (three in molecular structure
Ethylsilane) borate.
6. a kind of ethene gas-phase polymerization slurry type catalyst according to claim 1, which is characterized in that the electron
The additional amount control of body compound is 10 moles to 100 moles in every mole of titanium.
7. a kind of ethene gas-phase polymerization slurry type catalyst according to claim 1, which is characterized in that silica supports
Particle size range is 0.01~1 μm.
8. a kind of preparation method of ethene gas-phase polymerization slurry type catalyst, which is characterized in that this method has including following step
It is rapid:
(1) preparation of parent: magnesium compound, titanium-containing compound, electron donor compound being added in reactor and reacted, and later will
Reactor is added in the boric acid ester compound being dissolved in electron donor compound, continues to react, prepares parent；It is preparing
During parent, the molar ratio of each component is 1 < Mg/Ti < 20,0 <borate/Ti < 0.1, the additional amount of electron donor compound
Control is 5 moles to 300 moles in every mole of titanium；
(2) preparation of catalyst suspension: step (1) resulting parent is blended with smoke-like silica supports and is suitble to
In the suspension of spray drying: the silica supports wherein selected are hydrophobic types, i.e. the water that does not adsorb of its surface, dioxy
SiClx diameter of carrier is 0.01~1 μm, and the content of silica supports is 10~60% in suspension；
(3) shaping of catalyst: the suspension that step (2) obtains being spray-dried, the active component of solid titaniferous is obtained,
Average diameter of particles is at 10~50 μm；
(4) catalyst prereduction: in hydrocarbon solvent, the active component and activator group of the solid titaniferous that step (3) is obtained
Divide and reacted, obtains catalyst；The activator component is general formula AlR 'nX3-nOrgano-aluminum compound, R ' is hydrogen in formula
Or the alkyl that carbon atom number is 1~20, X are halogen, n is the number of 1 < n≤3.
9. a kind of preparation method of ethene gas-phase polymerization slurry type catalyst according to claim 8, which is characterized in that institute
The hydrocarbon solvent stated is mixing one or more of in isopentane, hexane, heptane, toluene, dimethylbenzene, naphtha or mineral oil
Object.
10. according to a kind of preparation method of ethene gas-phase polymerization slurry type catalyst, which is characterized in that catalyst is in aluminium and titanium
Molar ratio is 10~500.
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