CN104974278B - It is a kind of for the catalytic component of ethylene polymerization, preparation method and catalyst - Google Patents
It is a kind of for the catalytic component of ethylene polymerization, preparation method and catalyst Download PDFInfo
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Abstract
The invention discloses a kind of for the catalytic component of ethylene polymerization, preparation method and catalyst.Catalytic component is to include the reaction product of following components：A. magnesium compound；B. gallium compound；C. a kind of formula is R1OH Organic Alcohol, wherein R1For C1~C12Aliphatic alkyl or C7~C12Aromatic hydrocarbyl；D. organic epoxy compound thing；E. organic phosphorus compound；F. a kind of formula is Ti (O R2)n X1 4-nTitanium compound, wherein X1For halogen, R2For C1~C14Aliphatic alkyl or aromatic hydrocarbyl, n is 0,1,2,3,4.The catalytic component of the present invention contains gallium element, with higher active and higher bulk density when the catalyst of preparation is for vinyl polymerization.
Description
Technical field
The present invention relates to catalyst for ethylene field, furtherly, it is related to a kind of catalyst for ethylene polymerization
Component, preparation method and catalyst.
Background technology
Ziegler-Natta catalyst traditional at present has been proceeded to by magnesium chloride by classical titanium-Al catalysts
The stage being modified Deng compound activating, other various organic compounds；And by merely improving catalytic activity, develop into and pass through
Catalyst is adjusted to improve the performance of polymeric articles.
It can be summarized simply as follows using titanium compound and magnesium compound as the reaction mechanism of the titanium-magnesium catalyst of solvent logical
Cross various methods and be combined titanium compound with magnesium compound and obtain major catalyst, various auxiliary agents can be added therebetween and are changed
Property, then combined again with the co-catalyst such as aluminium compound for ethylene polymerization.
One conventional method is to carry out the preparation of magnesium solution first, such as by making magnesium or magnesium compound and electron donor
（Electron donor can include alcohol, amine, cyclic ethers or organic carboxyl acid etc.）Magnesium solution is prepared in the presence of varsol, then by making
Magnesium solution and halogen contained compound such as titanium tetrachloride reaction, prepare the catalyst of magnesium carrying, various accelerator can be added therebetween
It is modified.
Chinese patent CN85100997.2 discloses a kind of catalyst system for alkene homopolymerization and combined polymerization, and this is urged
Agent system includes：（First）Ingredient of solid catalyst containing Ti,（Second）Alkyl aluminum compound,（Third）Organosilicon, wherein（First）Group
Point be organic epoxy compound thing to be dissolved in by magnesium halide and organic phosphorus compound forms homogeneous solution, the solution and titanium tetrahalide or its
Derivative is mixed, in the presence of precipitation additive such as organic acid anhydride, organic acid, ether, ketone compound, separates out solids；This solid
Thing is handled with multi-carboxylate, it is attached on solids, then is handled and obtained with titanium tetrahalide and inert diluent.This is urged
When agent system is used for propylene polymerization, catalyst activity is higher, and the isotacticity of resulting polymers is higher, and apparent density is also larger,
But during for vinyl polymerization, then there is the deficiency that catalyst activity is relatively low, hydrogen adjusts not enough sensitivity.
Chinese patent CN98101108.X propose it is a kind of be used for ethylene homo close or the catalyst of combined polymerization and this urge
The preparation method of agent, wherein catalyst are to be dissolved in organic epoxy compound thing, organic phosphorus compound by magnesium halide to add
Electron donor formation homogeneous solution, then acted on at least one precipitation additive and the halide of transition metals Ti or derivatives thereof
And obtain, combined during polymerization with organo-aluminum compound.During the catalyst preparation as necessary component precipitation additive be organic acid
One kind in acid anhydride, organic acid, ether, ketone, during in particular by phthalic anhydride as precipitation additive, in order to preferably be urged
Agent separates out effect, first phthalic anhydride must be completely dissolved in mixed solvent system, then cool again mixes with titanium compound, because
The use of this such precipitation additive accordingly extends the manufacturing cycle of catalyst.In addition, above-mentioned help precipitation system（Such as phthalic anhydride）Phase
It is larger to toxicity, higher is required to operating condition.
For the production of general purpose polyolefin resin, on the basis of catalyst performance is further improved, simplify catalysis
Agent preparation technology, reduces catalyst cost, develops environmentally friendly technology, to increase the benefit, and it is a hair to enhance the competitiveness
Open up direction.It is therefore desirable to be improved for above-mentioned problem.
The content of the invention
To solve produced problem in the prior art, the invention provides a kind of catalyst group for ethylene polymerization
Point, preparation method and catalyst.The catalytic component of the present invention contains gallium element, and the catalyst of preparation is used to have during vinyl polymerization
There is higher active and higher bulk density.
An object of the present invention is to provide a kind of catalytic component for ethylene polymerization.
The catalytic component is to include the reaction product of following components：
A. magnesium compound；
B. gallium compound；
C. a kind of formula is R1OH Organic Alcohol, wherein R1For C1~C12Aliphatic alkyl or C7~C12Aromatic hydrocarbon
Base；
D. organic epoxy compound thing；
E. organic phosphorus compound；
F. a kind of formula is Ti (O R2)n X1 4-nTitanium compound, wherein X1For halogen, R2For C1~C14Aliphatic hydrocarbon
Base or aromatic hydrocarbyl, n are 0,1,2,3,4；
The consumption of each component is in terms of every mole of magnesium compound, and gallium compound is 0.0001~0.05 mole, and Organic Alcohol is 0.1
~10 moles, organic epoxy compound thing is 0~5 mole, and organic phosphorus compound is 0~5 mole, and titanium compound rubs for 0.2~100
You.
Described magnesium compound is selected from the alcohol adduct and dihalo- of magnesium dihalide, the hydrate of magnesium dihalide or magnesium dihalide
Change one kind in the derivative that one of halogen atom is replaced by alkyl or oxyl in magnesium molecular formula, or their mixing
Thing；It is preferred that magnesium dichloride, dibrominated magnesium, magnesium diiodide；More preferably magnesium dichloride；
Described magnesium halide is properly added inert diluent such as when dissolving：Benzene,toluene,xylene, normal heptane, n-decane,
1,2- dichloroethanes, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound.Here so-called inertia refers to that the diluent is not joined
Plus react and harmful effect will not be produced to the dissolving of magnesium halide.
The one kind or their compositions of described gallium compound in gallium halide, triethyl-gallium, preferably gallium trichloride；
Described formula is R1OH Organic Alcohol includes C1~C12Fatty alcohol or C7~C12Aromatic alcohol, for example：Methanol,
One kind in ethanol, propyl alcohol, isopropanol, butanol, isobutanol, 2-Ethylhexyl Alcohol, n-octyl alcohol, lauryl alcohol, phenmethylol, benzyl carbinol,
Or their mixture.Preferred alcohol, butanol, 2-Ethylhexyl Alcohol, phenmethylol, benzyl carbinol.
Described organic epoxy compound thing includes carbon number in 2~8 aliphatic olefin, alkadienes or halogenated aliphatic
The compounds such as oxide, glycidol ether and the inner ether of alkene or alkadienes.Such as：Oxirane, expoxy propane, epoxy butane,
In butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran
One or more.Wherein, preferably oxirane, expoxy propane, epoxychloropropane, tetrahydrofuran, with tetrahydrofuran, ring
Oxygen chloropropane is best.
Described organic phosphorus compound includes the hydrocarbyl carbonate or halogenation hydrocarbyl carbonate of orthophosphoric acid or phosphorous acid.Such as：Orthophosphoric acid three
Methyl esters, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triphenylmethyl methacrylate, Trimethyl phosphite, triethyl phosphite, phosphorous acid
One or more in tributyl, triphenyl phosphite, phosphorous acid benzene methyl.Wherein preferably orthophosphoric acid trimethyl, positive phosphorus
Triethylenetetraminehexaacetic acid ester and orthophosphoric acid tributyl, orthophosphoric acid tributyl are best.
The formula of described titanium compound is Ti (OR2)n X1 4-n, wherein X1For halogen, R2For C1~C14Aliphatic hydrocarbon
Base or aromatic hydrocarbyl, n are 0,1,2,3,4.As titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide,
One chlorine triethoxy titanium, dichlorodiethyl epoxide titanium, one kind in the ethanolato-titanium of trichlorine one or their mixture, preferably four chlorinations
Titanium.
In the above-mentioned catalytic component for ethylene polymerization, other electron donors can also be added（Such as tetrem
TMOS）.
In the catalytic component of the present invention for ethylene polymerization, consumption between each reactant is often to rub
That magnesium compound meter, preferably 0.1~10 mole of Organic Alcohol, 0.2~5 mole；0~5 mole of organic epoxy compound thing, preferably 0~3
Mole；0~5 mole of organic phosphorus compound, preferably 0~2 mole；0.2~100 mole of titanium compound, preferably 1.0~50 moles；
0.0001~0.05 mole of gallium compound, preferably 0.0005~0.025 mole.
The second object of the present invention is to provide a kind of preparation method of the catalytic component for ethylene polymerization.
Including：
Magnesium halide is first reacted in the presence of inert diluent with organic epoxy compound thing, Organic Alcohol and organic phosphorus compound
Homogeneous solution is formed, then is reacted with titanium compound, gallium compound and the catalytic component is made.
The inert diluent be aliphatic hydrocarbon or aromatic hydrocarbon, such as hexane, hexamethylene, heptane, decane, toluene,
Dimethylbenzene etc..
Specifically include following steps：
（1）By magnesium compound and Organic Alcohol, organic epoxy compound thing, organic phosphatization in the presence of stirring and inert diluent
Compound is at moderate temperatures as 0~150 DEG C of reaction forms mixed liquor；
（2）At moderate temperatures such as -35~60 DEG C, mixed liquor is mixed with titanium compound, gallium compound, heated up, 10
At a temperature of~150 DEG C, stir 1 minute~10 hours；The catalytic component is made after settling, filtering, wash.
Wherein, preferably：
Step（1）In, reaction forms mixed liquor at a temperature of 40~130 DEG C；
Step（2）In, at a temperature of -30~50 DEG C, mixed liquor is mixed with titanium compound, gallium compound；Programming rate
To heat up per hour 4~200 DEG C；Reactant mixture at 20~130 DEG C, at a temperature of, stir 1 minute~10 hours.
It can specifically follow the steps below：
By magnesium compound and Organic Alcohol, organic epoxy compound thing, organophosphor chemical combination in the presence of stirring and inert diluent
Thing is at a temperature of 0~150 DEG C, and best 40~130 DEG C of reactions form mixed liquor；At a temperature of -35~60 DEG C, best -30~50
DEG C, titanium compound is instilled in the mixed liquor or instills the mixed liquor in titanium compound, gallium is added before combination or after mixing
Compound；A period of time can be first maintained after completion of dropwise addition and then is heated up, when gradually heating up, programming rate to heat up 4 per hour
~200 DEG C preferably；Again by reactant mixture at a temperature of 10~150 DEG C, best 20~130 DEG C, stir 1 minute~10 hours；
Stop stirring, sedimentation, filtering remove mother liquor, solids washed with varsols such as toluene and hexanes, the catalysis of the present invention is made
Agent component.The catalytic component can be used in the form of solids or suspension.
The third object of the present invention is to provide a kind of catalyst for ethylene polymerization.
The catalyst includes the reaction product of following components：
（1）Catalytic component described in one of claim 1-4；
（2）Formula is AlR4 nX2 3-nOrgano-aluminum compound, R in formula4The alkyl for being 1~20 for hydrogen or carbon number, X2For
Halogen, n is the integer of 0 ＜ n≤3.Above-claimed cpd includes but is not limited to：Triethyl aluminum, aluminium diethyl monochloride, the ethyl of dichloro one
Aluminium, sesquialter aluminium ethide, dichloro aluminium isobutyl, triisobutyl aluminium, a chlorine diisopropyl aluminium, chloromethyl n-propyl aluminium, a chlorine two
Phenyl aluminium etc..Wherein preferred triethyl aluminum.
Wherein, component（2）In aluminium and component（1）In titanium mol ratio be 5~1000, preferably 20~800.
Liquid phase polymerization can be used during polymerization, gas-phase polymerization can be also used.Carry out liquid phase polymerization when, can use propane,
Hexane, heptane, hexamethylene, iso-butane, isopentane, naphtha, raffinate oil, hydrogasoline, kerosene, benzene,toluene,xylene etc. it is full
Make reaction medium with the atent solvent such as aliphatic hydrocarbon or aromatic hydrocarbon, prepolymerization can be first carried out before polymerization.Polymerization methodses can be used
Batch (-type), semi continuous or continous way.
In order to adjust the molecular weight of final polymer, molecular weight regulator is made using hydrogen.
Catalyst prepared by the present invention is relative with higher catalytic activity and higher bulk density.
Embodiment
With reference to embodiment, the present invention is further illustrated.Raw materials used for the present invention below, the data are only for reference,
Raw materials used source structure of the invention is not limited.
Anhydrous magnesium chloride：It is commercially available, technical grade；
Gallium trichloride：It is commercially available, analyze pure；0.05g/ml solution is made into toluene；
Tributyl phosphate：Analyze pure, Beijing Yili Fine Chemicals Co., Ltd.；
Epoxychloropropane：Analysis is pure, Tianjin recovery fine chemistry industry research institute；
Absolute ethyl alcohol：Analyze pure, Beijing Chemical Plant；
Titanium tetrachloride：Analyze pure, Beijing Yili Fine Chemicals Co., Ltd.；
Silicon tetrachloride：99.8+%, 500mL bottles, ACROS；
N-decane：Chemical pure, Beijing Xing Jin chemical plant；
2-Ethylhexyl Alcohol；Analyze pure, Beijing Xing Jin chemical plant；
Toluene：Analyze pure, Beijing Chemical Plant；
Hexane：Technical grade, it is commercially available；
Tetrahydrofuran：It is commercially available, analyze pure；
Ethene：Polymer grade, Yanshan Petro-Chemical Industry Corporation purifies through molecular sieve, nickel accelerant；
Triethyl aluminum：ACROS companies of Sweden are produced, and 1mol/l solution is made into hexane.
Embodiment 1：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.56mol toluene, stir
Lower addition 0.026mol epoxychloropropane, 0.022mol tributyl phosphates are mixed, 0.062mol ethanol is warming up to 60 DEG C, maintains 1.5
Hour, 4ml gallium trichlorides toluene solution (containing gallium trichloride 0.00013mol) is added, the solution is cooled to -10 DEG C, then will
0.27mol titanium tetrachlorides are instilled in it, are maintained 40 minutes, then heat to 85 DEG C, maintain 1 hour, 4 are washed with hexane after filtering
It is secondary, it is dried to obtain ingredient of solid catalyst.
Embodiment 2：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.56mol toluene, stir
Lower addition 0.026mol epoxychloropropane, 0.022mol tributyl phosphates are mixed, 0.062mol ethanol is warming up to 60 DEG C, maintains 1.5
Hour, 4ml gallium trichlorides toluene solution (containing gallium trichloride 0.00013mol) is added, the solution is cooled to -10 DEG C, then will
0.27mol titanium tetrachlorides are instilled in it, are maintained 40 minutes, then heat to 85 DEG C, maintain 1 hour, 4 are washed with hexane after filtering
It is secondary, 4ml gallium trichlorides toluene solution (containing gallium trichloride 0.00013mol) is added, ingredient of solid catalyst is dried to obtain.
Embodiment 3：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.56mol toluene, stir
Lower addition 0.026mol epoxychloropropane, 0.022mol tributyl phosphates are mixed, 0.062mol ethanol is warming up to 60 DEG C, maintains 1.5
Hour, the solution is cooled to -10 DEG C, then 0.27mol titanium tetrachlorides are instilled in it, maintain 40 minutes, add 4ml tri-chlorinations
Gallium toluene solution (contains gallium trichloride 0.00013mol), maintains 30 minutes, then heats to 85 DEG C, maintains 1 hour, is used after filtering
Hexane is washed 4 times, is added 4ml gallium trichlorides toluene solution (containing gallium trichloride 0.00013mol), is dried to obtain solid catalyst
Component.
Embodiment 4：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.30mol n-decanes,
Stirring is lower to add 0.14mol isooctanol, is warming up to 130 DEG C, maintains 1 hour, the solution is cooled into -10 DEG C, adds 4ml trichlorines
Change gallium toluene solution (containing gallium trichloride 0.00013mol), maintain 30 minutes, then 0.27mol titanium tetrachlorides are instilled in it, tie up
Hold 40 minutes, then heat to 110 DEG C, maintain 1 hour, washed after filtering with hexane 4 times, be dried to obtain solid catalyst group
Point.
Embodiment 5：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.30mol n-decanes,
Stirring is lower to add 0.14mol isooctanol, is warming up to 130 DEG C, maintains 1 hour, the solution is cooled into 50 DEG C, adds 0.053mol
Ethanol, continues cool to 30 DEG C, adds 4ml gallium trichlorides toluene solution (containing gallium trichloride 0.00013mol), continue cool to-
10 DEG C, then 0.27mol titanium tetrachlorides are instilled in it, maintain 70 minutes, then heat to 110 DEG C, maintain 1 hour, after filtering
Washed with hexane 4 times, be dried to obtain ingredient of solid catalyst.
Embodiment 6:
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.56mol toluene, stir
Lower addition 0.026mol epoxychloropropane, 0.019mol phenmethylols are mixed, 0.11mol ethanol is warming up to 60 DEG C, maintained 1.5 hours,
Then the solution is cooled to 10 DEG C, adds 4ml gallium trichlorides toluene solution (containing gallium trichloride 0.00013mol), then should
Solution is cooled to -10 DEG C, then 0.27mol titanium tetrachlorides are instilled in it, maintains 70 minutes, then heats to 85 DEG C, maintenance 1 is small
When, washed after filtering with hexane 4 times, be dried to obtain ingredient of solid catalyst.
Embodiment 7:
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.56mol toluene, stir
Lower addition 0.026mol epoxychloropropane, 0.017mol benzyl carbinols are mixed, 0.11mol ethanol is warming up to 60 DEG C, maintained 1.5 hours,
Then the solution is cooled to 10 DEG C, adds 8ml gallium trichlorides toluene solution (containing gallium trichloride 0.00026mol), then should
Solution is cooled to -10 DEG C, then 0.27mol titanium tetrachlorides are instilled in it, maintains 40 minutes, then heats to 85 DEG C, maintenance 1 is small
When, washed after filtering with hexane 4 times, be dried to obtain ingredient of solid catalyst.
Embodiment 8：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.56mol toluene, stir
Lower addition 0.078mol epoxychloropropane, 0.066mol tributyl phosphates are mixed, 0.0062mol ethanol is warming up to 60 DEG C, maintenance
1.5 hours, 20ml gallium trichlorides toluene solution (containing gallium trichloride 0.00065mol) is added, the solution is cooled to -5 DEG C, then
1.08mol titanium tetrachlorides are instilled in it, maintained 40 minutes, 85 DEG C are then heated to, maintains 1 hour, is washed after filtering with hexane
Wash 4 times, be dried to obtain ingredient of solid catalyst.
Embodiment 9：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.84mol toluene, stir
Lower addition 0.026mol epoxychloropropane, 0.022mol tributyl phosphates are mixed, 0.062mol ethanol is warming up to 60 DEG C, maintains 1.5
Hour, 16ml gallium trichlorides toluene solution (containing gallium trichloride 0.00052mol) is added, the solution is cooled to -10 DEG C, then will
0.09mol titanium tetrachlorides are instilled in it, are maintained 40 minutes, then heat to 85 DEG C, maintain 1 hour, 4 are washed with hexane after filtering
It is secondary, it is dried to obtain ingredient of solid catalyst.
Embodiment 10：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.84mol toluene, stir
Lower addition 0.026mol epoxychloropropane, 0.022mol tributyl phosphates are mixed, 0.062mol ethanol is warming up to 60 DEG C, maintains 1.5
Hour, 12ml gallium trichlorides toluene solution (containing gallium trichloride 0.00039mol) is added, the solution is cooled to -10 DEG C, then will
0.54mol titanium tetrachlorides are instilled in it, are maintained 40 minutes, then heat to 85 DEG C, maintain 1 hour, 4 are washed with hexane after filtering
It is secondary, it is dried to obtain ingredient of solid catalyst.
Embodiment 11：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.30mol n-decanes,
Stirring is lower to add 0.14mol isooctanol, is warming up to 130 DEG C, maintains 1 hour, the solution is cooled into 50 DEG C, 0.037mol tetrahydrochysenes
Furans, continues cool to 30 DEG C, adds 1ml gallium trichlorides toluene solution (containing gallium trichloride 0.000033mol), continues to cool down
To -5 DEG C, then 1.35mol titanium tetrachlorides are instilled in it, maintained 70 minutes, then heat to 110 DEG C, maintained 1 hour, filtering
Washed afterwards with hexane 4 times, be dried to obtain ingredient of solid catalyst.
Comparative example 1：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.56mol toluene, stir
Lower addition 0.026mol epoxychloropropane, 0.022mol tributyl phosphates, 0.060mol ethanol are mixed, 60 DEG C are warming up to, maintenance 1 is small
When, plus 0.0074mol phthalic anhydrides maintenance half an hour, the solution is cooled to -15 DEG C, then 0.36mol titanium tetrachlorides are instilled in it,
Maintain 1 hour, then heat to 60 DEG C, maintain 1 hour, washed after filtering with hexane 4 times, be dried in vacuo, obtain solid catalysis
Agent component.
Comparative example 2:
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.56mol toluene, stir
Lower addition 0.026mol epoxychloropropane, 0.022mol tributyl phosphates, 0.060mol ethanol are mixed, 65 DEG C are warming up to, plus
0.0081mol phthalic anhydrides, maintain 2.5 hours, the solution are cooled into -10 DEG C, 0.54mol titanium tetrachlorides are instilled in it, maintain
70 minutes, 85 DEG C are then heated to, maintains 1 hour, is washed after filtering with hexane 4 times, is dried in vacuo, obtains solid catalyst group
Point.
Comparative example 3：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.56mol toluene, stir
Lower addition 0.026mol epoxychloropropane, 0.022mol tributyl phosphates, 0.060mol ethanol are mixed, 60 DEG C are warming up to, maintenance 1 is small
When, plus 0.0074mol phthalic anhydrides maintenance half an hour, the solution is cooled to -15 DEG C, then 0.36mol titanium tetrachlorides are instilled in it,
Maintain 1 hour, then heat to 60 DEG C, maintain 1 hour, washed after filtering with hexane 4 times, be dried to obtain solid catalyst group
Point.
Comparative example 4：
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.30mol n-decanes,
Stirring is lower to add 0.15mol2- ethyl hexanols, is warming up to 115 DEG C, maintains 1 hour, 50 DEG C are cooled to, by 0.026mol SiCl4
Instill in it, continue to cool to -10 DEG C, 0.45mol titanium tetrachlorides are instilled in it, maintain 1 hour, then heat to 120 DEG C,
Maintain 1 hour, 2 times, hexane washing 4 times washs with toluene after filtering, ingredient of solid catalyst is dried to obtain.
Comparative example 5:
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.75mol toluene, stir
Lower addition 0.089mol epoxychloropropane, 0.033mol tributyl phosphates are mixed, 50 DEG C are warming up to, maintained 3.0 hours, plus
0.0081mol phthalic anhydrides, maintain 2 hours, the solution are cooled into -10 DEG C, 0.36mol titanium tetrachlorides are instilled in it, maintain 70
Minute, 85 DEG C are then heated to, is maintained 1 hour, is washed after filtering with hexane 4 times, be dried to obtain ingredient of solid catalyst.
Comparative example 6:
Through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 0.042mol are sequentially added2, 0.56mol toluene, stir
Lower addition 0.051mol epoxychloropropane, 0.019mol phenmethylols are mixed, 0.071mol ethanol is warming up to 60 DEG C, maintenance 1.5 is small
When, the solution is then cooled to -10 DEG C, then 0.27mol titanium tetrachlorides are instilled in it, maintain 40 minutes, then heat to
85 DEG C, maintain 1 hour, washed after filtering with hexane 4 times, be dried to obtain ingredient of solid catalyst.
（Two）Vinyl polymerization：Volume is 2 liters of stainless steel kettle through H2After being sufficiently displaced from, hexane 1000ml is added wherein,
Concentration is 1mol/L triethyl aluminium solution 1.0ml, 10mg ingredient of solid catalyst, is warming up to 70 DEG C, hydrogenation arrives 0.26MPa
（Gauge pressure）, then being passed through ethene makes pressure in kettle reach 0.72MPa（Gauge pressure）, at 80 DEG C, it polymerize 2 hours.Result of the test is shown in Table 1.
The polymer performance of table 1
Added it can be seen from the data of table 1 in the catalyst of titanium magnesium system is used for ethene obtained by gallium compound
The catalyst of polymerization has higher active and preferable bulk density.
Claims (9)
1. a kind of catalytic component for ethylene polymerization, it is characterised in that the catalytic component is to include following components
Reaction product：
A. magnesium compound；
B. gallium compound；The one kind or their mixture of described gallium compound in gallium halide, triethyl-gallium；
C. a kind of formula is R1OH Organic Alcohol, wherein R1For C1~C12Aliphatic alkyl or C7~C12Aromatic hydrocarbyl；
D. organic epoxy compound thing；
E. organic phosphorus compound；
F. a kind of formula is Ti (O R2)n X1 4-nTitanium compound, wherein X1For halogen, R2For C1~C14Aliphatic alkyl or
Aromatic hydrocarbyl, n is 0,1,2,3,4；
The consumption of each component is in terms of every mole of magnesium compound, and gallium compound is 0.0001~0.05 mole, and Organic Alcohol is 0.1~10
Mole, organic epoxy compound thing is 0~5 mole, and organic phosphorus compound is 0~5 mole, and titanium compound is 0.2~100 mole.
2. it is used for the catalytic component of ethylene polymerization as claimed in claim 1, it is characterised in that：
Described magnesium compound is selected from the alcohol adduct and magnesium dihalide of magnesium dihalide, the hydrate of magnesium dihalide or magnesium dihalide
One kind in the derivative that one of halogen atom is replaced by alkyl or oxyl in molecular formula, or their mixture；
Described Organic Alcohol is selected from methanol, ethanol, propyl alcohol, butanol, 2-Ethylhexyl Alcohol, n-octyl alcohol, lauryl alcohol, phenmethylol, benzene second
One kind or their mixture in alcohol；
Described titanium compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine three
Ethanolato-titanium, dichlorodiethyl epoxide titanium, one kind in the ethanolato-titanium of trichlorine one or their mixture；
Described organic epoxy compound thing is selected from oxirane, expoxy propane, epoxy butane, butadiene oxide, and butadiene is double
One or more in oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran；
Described organic phosphorus compound is selected from orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triphen
Ester, Trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite, one kind in phosphorous acid benzene methyl or
It is several.
3. it is used for the catalytic component of ethylene polymerization as claimed in claim 2, it is characterised in that：
Described magnesium compound is magnesium dichloride；
Described gallium compound is gallium trichloride；
The Organic Alcohol is one kind in ethanol, butanol, 2-Ethylhexyl Alcohol, phenmethylol, benzyl carbinol or combination；
The organic epoxide is one kind in oxirane, expoxy propane, epoxychloropropane, tetrahydrofuran or combination；
The organic phosphorus compound is orthophosphoric acid trimethyl, orthophosphoric acid triethyl, one kind in orthophosphoric acid tributyl or combination；
The titanium compound is titanium tetrachloride.
4. it is used for the catalytic component of ethylene polymerization as claimed in claim 1, it is characterised in that：
The consumption of each component is in terms of every mole of magnesium compound, and gallium compound is 0.0005~0.025 mole, and Organic Alcohol is 0.2~5
Mole, organic epoxy compound thing is 0~3 mole, and organic phosphorus compound is 0~2 mole, and titanium compound is 1~50 mole.
5. a kind of preparation method of catalytic component for ethylene polymerization as described in one of Claims 1 to 4, it is special
Levy and be that methods described includes：
Magnesium compound is first reacted into shape in the presence of inert diluent with organic epoxy compound thing, Organic Alcohol and organic phosphorus compound
Into homogeneous solution, then reacted with titanium compound, gallium compound and the catalytic component is made.
6. preparation method as claimed in claim 5, it is characterised in that methods described includes：
(1) by magnesium compound and Organic Alcohol, organic epoxy compound thing, organic phosphorus compound in the presence of stirring and inert diluent
Reaction forms mixed liquor at a temperature of 0~150 DEG C；
(2) at a temperature of -35~60 DEG C, mixed liquor is mixed with titanium compound, gallium compound, heated up, in 10~150 DEG C of temperature
Under, stir 1 minute~10 hours；
(3) settle, filter, wash after be made the catalytic component.
7. a kind of catalyst for ethylene polymerization, it is characterised in that reaction of the catalyst comprising following components is produced
Thing：
(1) catalytic component described in one of claim 1-4；
(2) formula is AlR4 nX2 3-nOrgano-aluminum compound, R in formula4The alkyl for being 1~20 for hydrogen or carbon number, X2For halogen
Element, n is the integer of 0 ＜ n≤3.
8. it is used for the catalyst of ethylene polymerization as claimed in claim 7, it is characterised in that：
The mol ratio of aluminium in component (2) and the titanium in component (1) is 5~1000.
9. being used for the catalyst of ethylene polymerization as claimed in claim 7, its feature exists：
The mol ratio of aluminium in component (2) and the titanium in component (1) is 20~800.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079478A (en) * | 1992-05-29 | 1993-12-15 | 住友化学工业株式会社 | The catalyzer that ethene closes with alpha-olefin copolymer and make the method for its multipolymer with it |
| CN1523044A (en) * | 2003-02-17 | 2004-08-25 | 中国石油化工股份有限公司 | Catalyst component for polymerizing ethylene and catalyst thereof |
| CN103087224A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Catalyst ingredient used for ethylene polymerization, and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079478A (en) * | 1992-05-29 | 1993-12-15 | 住友化学工业株式会社 | The catalyzer that ethene closes with alpha-olefin copolymer and make the method for its multipolymer with it |
| CN1523044A (en) * | 2003-02-17 | 2004-08-25 | 中国石油化工股份有限公司 | Catalyst component for polymerizing ethylene and catalyst thereof |
| CN103087224A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Catalyst ingredient used for ethylene polymerization, and preparation method thereof |
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