CN103183754A - Olefin polymerization catalyst and preparation method thereof - Google Patents
Olefin polymerization catalyst and preparation method thereof Download PDFInfo
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- CN103183754A CN103183754A CN2013100790975A CN201310079097A CN103183754A CN 103183754 A CN103183754 A CN 103183754A CN 2013100790975 A CN2013100790975 A CN 2013100790975A CN 201310079097 A CN201310079097 A CN 201310079097A CN 103183754 A CN103183754 A CN 103183754A
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Abstract
The invention relates to an olefin polymerization catalyst and a preparation method thereof; the main catalyst consists of a magnesium compound, a transition metal halide, a halogenated silicon compound, an organic alcohol compound, a metal acid ester and an organic alcohol ether compound; the molar ratio of the magnesium compound, the transition metal halide, the silicon halide compound, the organic alcohol compound and the metal acid ester is 1: (0.1-30): (0.1-20): (0.5-10): (0.01-10); the mass ratio of the magnesium halide to the organic alcohol ether compound is as follows: 100: 0.1 to 20; the cocatalyst is an organic aluminum compound; the molar ratio of transition metal halide to co-catalyst is 1: 30-500; the olefin polymerization catalyst provided by the invention has good particle shape and high bulk density; the catalyst has high activity, and the insertion rate of alpha-olefin is high when the catalyst is used for copolymerization of ethylene and alpha-olefin; is suitable for slurry method, gas phase polymerization process or combined polymerization process.
Description
Technical field
The invention belongs to olefin polymerization catalysis and field of olefin polymerisation, be specifically related to the catalyzer and the method for preparing catalyst that close for vinyl polymerization or ethene and alpha-olefin copolymer.
Background technology
Olefin polymerization catalysis is the core of polyolefin polymerization technology.The Ziegler-Natta catalyst existing nearly 60 years history so far of coming out, although during occurred as polyolefin catalysts such as metallocene and Nonmetallocenes, its industrial problems is more, as the promotor costliness, the load problem is difficult for solution etc.Therefore, just present industrial production and share of market, traditional Z-N catalyzer will be the absolute leader of following for some time internal olefin polymerization field.In recent years, Z-N catalyst prod both domestic and external emerges in an endless stream, and catalyst stability and polymerization catalyzed activity also improve constantly.But still having deficiency aspect granules of catalyst regularity and the size distribution, this will directly cause, and gained polyolefin products tap density is low, fine powder content is high, even sticking still in producing, hang still, block the generation of problems such as pipeline, greatly influenced the industrial production benefit.What be badly in need of in producing at present is to develop the uniform spherical catalyst product of the simple size distribution of a kind of preparation technology.
Patent CN101857650 discloses a kind of preparation method of easy spherical polyolefin catalyst carrier, be specially anhydrous magnesium halide is dissolved in tetrahydrofuran (THF) formation solution, be precipitation agent with the glycol ether, slowly splash into glycol ether in the magnesium halide solution, keep high-speed stirring, gained system standing demix is isolated bottom precipitation and washing, after isolate precipitation again after gained precipitation soaked with muriate or alkyl aluminum solutions, and with alkane its washing is obtained spherical carrier of catalyst.But the titanium amount of carrying of this class carrier is lower.
Patent CN1097426A discloses a kind of method for preparing catalyst, and this catalyzer at first adopts chlorination reagent and alkyl magnesium prepared in reaction carrier, carries titanium then and generates catalyzer.The catalyzer form of this method preparation is the class sphere, and fine polymer powder content is low, and macrobead content is low, but catalyst activity is low.
Patent CN101096389A has reported a kind of ethylene rolymerization catalyst, and this catalyzer adopts silicon halide as the precipitation agent of magnesium chloride, though solved bulk density and the fine powder content problem of polymkeric substance, year titanium amount and the activity of catalyzer are very low.
Patent CN102558403A has reported a kind of ethylene rolymerization catalyst, this catalyzer has added alkoxyl silicone as electron donor, adds organic alcohol ether and has improved the catalyzer form as the form renovation agent, and catalyst particle size is evenly distributed, active higher, the fine polymer powder content that obtains is low.
This patent finds that in catalyst preparation process, transition metal active centres and electron donor can be separated out simultaneously at carrier and be generated, and original position is carried on the carrier.Alcohol in the dissolution system and reactive organic silicon compound original position generate electron donor, and metal acid ester cpds and silicoorganic compound original position generate transition metal active centres.The Primary Catalysts particle form of the present invention's preparation is good, and granules of catalyst is spherical in shape, charge capacity height, active high, and catalyzer does not split away off from carrier.The polyethylene bulk density height of preparation, fine powder content is low.Be applicable to slurry polymerization processes, gas-phase polymerization process or polymerization mix technology.
Summary of the invention
The object of the present invention is to provide a kind of catalytic activity high be used for catalyst component that vinyl polymerization or ethene and alpha-olefin copolymer close and preparation method thereof.
Ethylene rolymerization catalyst provided by the present invention is made up of Primary Catalysts and promotor; Wherein, described Primary Catalysts is made up of magnesium compound, transition metal halide, halogenated silicon compound, organic alcohol compound, metal acid esters and organic pure ether compound.Described Primary Catalysts mainly is made up of carrier and transition metal halide, and carrier generates by the muriate liberation method, and transition metal halide is to be generated by titanic acid ester and silicon halide reaction.The mol ratio of magnesium compound, transition metal halide, halogenated silicon compound, organic alcohol compound, metal acid esters is 1:(0.1-30): (0.1-20): (0.5-10): (0.01-10); The mass ratio of magnesium halide and organic pure ether compound is: 100:0.1 – 20; Described promotor is organo-aluminium compound; Primary Catalysts and promotor with magnitude relation be: the transition metal halide in the Primary Catalysts and the mol ratio of promotor are 1:30-500.
Wherein, to be selected from general formula (1) be Mg (R) to described magnesium compound carrier
aX
bCompound at least a.R is selected from C
1～C
20Aliphatic group, C
1～C
20Fatty alkoxyl group, C
3～C
20Alicyclic radical or C
6～C
20Aryl radical; X is selected from halogen; A=0,1 or 2, b=0,1 or 2, a+b=2.Concrete compound is as at least a in magnesium dichloride, dibrominated magnesium, two magnesium iodides, chlorination magnesium methylate, chlorination magnesium ethylate, chlorination propoxy-magnesium, chlorination butoxy magnesium, chlorination phenoxy group magnesium, magnesium ethylate, isopropoxy magnesium, butoxy magnesium, chlorination isopropoxy magnesium, dibutylmagnesium, the butyl magnesium chloride etc.Wherein, preferred magnesium dichloride.
Wherein, to be selected from general formula (2) be M (R to described transition metal halide
1)
4-mX
mCompound at least a, in the formula, M is transition metal, is selected from Ti, Zr, Hf; X is halogen atom; M is 1 to 4 integer; R
1Be selected from C
1～C
20Aliphatic group, C
1～C
20Fatty alkoxyl group, C
1～C
20Cyclopentadienyl and derivative, C
1～C
20Aryl radical, C
1～C
20Fragrant alkoxyl group, COR` or COOR`, R` has C
1～C
10Fatty group or have C
1～C
10Aromatic base.R
1Specifically can be selected from: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl-, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, neighbour-aminomethyl phenyl ,-at least a in aminomethyl phenyl, right-aminomethyl phenyl, neighbour-sulfonic group phenyl, formyl radical, acetyl or benzoyl base etc.Described transition metal halide specifically can be selected one or more the mixing in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, zirconium tetrachloride, tetrabormated zirconium, hafnium tetrachloride, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, methoxyl group titanous chloride, dibutoxy titanium dichloride, three butoxy titanium chlorides, a chlorine triple phenoxyl titanium, two chlorodiphenyl oxygen base titaniums, trichlorine one phenoxide titanium for use.Wherein, preferred titanium tetrachloride.The mol ratio of transition metal halide and magnesium halide preferred (1 – 30): 1.
One of feature of the present invention is to add a kind of halogenation silicoorganic compound as the precipitation agent of magnesium halide in the Primary Catalysts preparation process.
Wherein, to be selected from general formula be Si (R to described halogenation silicoorganic compound
2)
4-nX
nCompound at least a.In the formula, X is halogen atom; N is 1 to 4 integer; R
2Be selected from C
1～C
20Aliphatic group, C
1～C
20Fatty alkoxyl group, C
3～C
20Cycloalkyl, C
6～C
20Aryl radical, C
6～C
20Fragrant alkoxyl group.R
2Specifically can be selected from: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl-, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, methoxyl group, oxyethyl group, propoxy-, butoxy, phenyl, naphthyl, neighbour-aminomethyl phenyl ,-aminomethyl phenyl, right-aminomethyl phenyl, etc. at least a.Spendable compound is as silicon tetrachloride, Silicon bromide, silicon tetraiodide, monomethyl trichlorosilicane, an ethyl trichlorosilicane, phenylbenzene silicon dichloride, aminomethyl phenyl silicon dichloride, dimethyl one methoxyl group chlorination silicon, dimethyl one oxyethyl group silicon chlorides, diethyl one oxyethyl group silicon chlorides, phenylbenzene one methoxyl group chlorination silicon etc., the preferred silicon tetrachloride of the present invention or phenylbenzene silicon dichloride.The mol ratio of halogenation silicoorganic compound and magnesium halide preferred (1-20): 1
One of feature of the present invention is to add a kind of organic alcohol compound or its mixture in the Primary Catalysts preparation process.
Organic alcohol compound of the present invention is selected from C
2-C
15Fatty Alcohol(C12-C14 and C12-C18), C
3-C
15Alicyclic ring alcohol or C
6-C
15Aromatic alcohol in a kind of or their mixture.Specifically comprise: ethanol, ethylene glycol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 1, ammediol, glycerol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol, sorbyl alcohol, hexalin, methyl-cyclohexanol, Bian alcohol, methyl Bian alcohol, sec.-propyl Bian alcohol etc.Wherein, preferred fat alcohol, especially a kind of in preferred alcohol, butanols, 2-Ethylhexyl Alcohol or the glycerol or their mixture.The mol ratio of described organic alcohol compound and magnesium halide preferred (1-10): 1.
One of feature of the present invention is to add a kind of metal acid ester cpds in the Primary Catalysts preparation process.
Wherein to be selected from general formula be M (R to the metal acid ester cpds
3)
4Compound at least a.In the formula, M is transition metal, is selected from Ti, Zr, Hf, R
3Be selected from C
1～C
20Fatty alkoxyl group, C
1～C
20Fragrant phenoxy group.Particular compound can be selected from: purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide, four hexyloxy titaniums, tetrabutyl zirconate, tetraethoxy zirconium etc.Preferred four titanium butoxide.The mol ratio of described metal acid esters and magnesium halide preferred (0.1-10): 1.
Wherein, described organic pure ether compound is characterized by terminal group and contains hydroxyl, shown in general formula (3), and general formula (3): HO (CH
2CH
2O)
f(CH
2)
gR
4, wherein, f is 2 to 20 integer, g is 1 to 10 integer; R
4Be selected from C
1～C
30Aliphatic group, C
3～C
30Cycloalkyl, C
6～C
30Aryl radical, C
2～C
30Heterocyclylalkyl, specifically be selected from diethylene glycol ether, Diethylene Glycol butyl ether, diethylene glycol monobutyl ether, triglycol list ether, diglycol monotertiary allyl ethers, triglycol monoisopropyl ether, triethylene glycol butyl ether, 2-(2-(2-cyclopentyl oxyethyl group) oxyethyl group) ethanol, glycol ether ethyl cyclopentadienyl ether, triglycol propyl group hexamethylene ether, glycol ether phenyl ethyl ether, triglycol furyl ether, triglycol pyridyl isopropyl ether.The mass ratio of magnesium halide and organic pure ether compound is: 100:0.1-20.
One of feature of the present invention has provided the preparation method of vinyl polymerization Primary Catalysts, may further comprise the steps:
1) magnesium compound is scattered in the organic solvent, the back adds organic alcohol compound, 30-150 ℃ of following stirring and dissolving 1-5h.
2) with 1) solution is cooled to 10-80 ℃, adds metal acid ester cpds and organic pure ether compound, reacts 0.5-3h under this temperature.
3) under-40-30 ℃, make step 2) in the solution that obtains contact with halogenated silicon compound, reacted 0.5-5 hour, and be warming up to 40-110 ℃, reacted 0.5-5 hour.
4) under-40-30 ℃, the system that obtains in the step 3) is contacted with transition metal halide, reaction 0.5-5h.System is warming up to 20-150 ℃, reaction 0.5-5h, in temperature-rise period, particle is separated out and formed to solids gradually, and reaction is left standstill after finishing, and filters, and adopts toluene or normal hexane washing 4-6 time, and vacuum is drained, and obtains Primary Catalysts.
Described organic solvent is selected from toluene, dimethylbenzene, hexane, heptane, octane or decane, or their mixed solvent, preferred toluene, hexane, heptane or decane.
Ethylene rolymerization catalyst provided by the present invention also needs to be made up of the promotor organo-aluminium compound.It is Al (R that described promotor organo-aluminium compound is selected from general formula
5)
yX
3-yCompound in one or both mixing, in the formula, R
5For hydrogen or carbonatoms are that the alkyl of 1-20 or alkoxyl group, X are halogen, y is the integer of 0＜y≤3.
The purposes of catalyst for ethylene provided by the present invention is: the catalyzer that can make vinyl polymerization or ethene and copolymerization monomer copolymerizable, wherein, the preferred propylene of described comonomer, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 1,3-dibutene, isoprene, vinylbenzene, vinyl toluene, norbornylene etc.
Olefin polymerization catalysis provided by the present invention has following beneficial effect:
The particle form of ethylene rolymerization catalyst provided by the present invention is good, the bulk density height; The catalyst activity height is used for ethene and the fashionable a-alkene of a-olefin-copolymerization insertion rate height; Be applicable to slurry process, gas-phase polymerization process or polymerization mix technology.
Embodiment
Embodiment 1
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 8ml is warming up to 120 ℃, constant temperature 2h under stirring; Add 1.7ml four titanium butoxide then, diethylene glycol ether 0.02ml, 60 ℃ of reaction 1h.Be cooled to-20 ℃, drip the 11ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-25 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 60 ℃ of reaction 2h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: the 0.5L stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.2ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene to 0.73MPa, constant voltage isothermal reaction 2h.Polymerization result sees Table 1.
3) ethylene copolymerization: the 0.5L stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.2ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene to 0.73MPa, adds 1-hexene 35mL, constant voltage isothermal reaction 2h.Polymerization result sees Table 1.
Embodiment 2
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 8ml is warming up to 100 ℃, constant temperature 3h under stirring; Add 1.7ml four titanium butoxide then, diethylene glycol ether 0.02ml, 20 ℃ of reaction 1h.Be cooled to-20 ℃, drip the 20ml silicon tetrachloride, be warming up to 60 ℃ of reaction 1h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-25 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 120 ℃ of reaction 2h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 3
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 8ml is warming up to 150 ℃, constant temperature 1h under stirring; Add 13.6ml four titanium butoxide then, Diethylene Glycol butyl ether 0.02ml, 80 ℃ of reaction 1h.Be cooled to-20 ℃, drip 11ml dimethyl silicon dichloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-35 ℃, drip the 20ml titanium tetrachloride, reaction 3h is warming up to 80 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 4
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml is warming up to 80 ℃, constant temperature 2h under stirring; Add 1.7ml four titanium butoxide then, Diethylene Glycol butyl ether 0.02ml, 30 ℃ of reaction 1h.Be cooled to 10 ℃, drip the 11ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-25 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 150 ℃ of reaction 1h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 5
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 8ml is warming up to 120 ℃, constant temperature 2h under stirring; Add 1.7ml four titanium butoxide then, Diethylene Glycol butyl ether 0.02ml, 20 ℃ of reaction 3h.Be cooled to-5 ℃, drip 11ml phenylbenzene silicon dichloride, be warming up to 100 ℃ of reaction 1h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-20 ℃, drip the 20ml titanium tetrachloride, reaction 4h is warming up to 60 ℃ of reaction 5h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 6
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, ethanol 5ml is warming up to 80 ℃, constant temperature 4h under stirring; Add 1.7ml four titanium butoxide then, diethylene glycol monobutyl ether 0.02ml, 60 ℃ of reaction 3h.Be cooled to-20 ℃, drip 11ml one ethyl trichlorosilicane, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-25 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 120 ℃ of reaction 2h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 7
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, heptane 20ml, 2-Ethylhexyl Alcohol 8ml is warming up to 100 ℃, constant temperature 3h under stirring; Add 1.7ml four titanium butoxide then, diethylene glycol monobutyl ether 0.02ml, 70 ℃ of reaction 1h.Be cooled to-10 ℃, drip the 11ml silicon tetrachloride, be warming up to 100 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-25 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 60 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 8
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml, ethanol 0.5ml is warming up to 120 ℃, constant temperature 2h under stirring; Add 1.7ml four titanium butoxide then, triglycol list ether 0.04ml, 60 ℃ of reaction 1h.Be cooled to-20 ℃, drip 6ml one phenyl trichlorosilicane, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-25 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 120 ℃ of reaction 2h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 9
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml, ethanol 0.5ml is warming up to 100 ℃, constant temperature 3h under stirring; Add 1.7ml four titanium butoxide then, triglycol list ether 0.04ml, 60 ℃ of reaction 2h.Be cooled to-20 ℃, drip 11ml phenylbenzene silicon dichloride, be warming up to 60 ℃ of reaction 3h after dropwising, obtain the turbid liquid of oyster white.Be cooled to 5 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 120 ℃ of reaction 2h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 10
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml, ethanol 0.5ml is warming up to 80 ℃, constant temperature 4h under stirring; Add 6.8ml four titanium butoxide then, triglycol list ether 0.04ml, 60 ℃ of reaction 1h.Be cooled to-20 ℃, drip the 11ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-25 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 140 ℃ of reaction 1h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 11
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml, butanols 0.5ml is warming up to 100 ℃, constant temperature 2h under stirring; Add 6.8ml four titanium butoxide then, diglycol monotertiary allyl ethers 0.06ml, 60 ℃ of reaction 1h.Be cooled to-20 ℃, drip the 11ml silicon tetrachloride, be warming up to 100 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-25 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 60 ℃ of reaction 5h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 12
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml, ethanol 0.5ml is warming up to 120 ℃, constant temperature 3h under stirring; Add 6.8ml four titanium butoxide then, triethylene glycol butyl ether 0.5ml, 60 ℃ of reaction 3h.Be cooled to-30 ℃, drip the 20ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to 10 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 13
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml, ethanol 0.5ml is warming up to 120 ℃, constant temperature 2h under stirring; Add the 6.8ml tetraisopropoxy titanium then, glycol ether phenyl ethyl ether 0.02ml, 60 ℃ of reaction 1h.Be cooled to-20 ℃, drip the 11ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-25 ℃, drip the 20ml titanium tetrachloride, reaction 2h is warming up to 50 ℃ of reaction 5h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 14
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml, propyl alcohol 0.5ml is warming up to 120 ℃, constant temperature 3h under stirring; Add 6.8ml four titanium butoxide then, Diethylene Glycol propyl ether 0.5ml, 60 ℃ of reaction 3h.Be cooled to-30 ℃, drip 20ml dimethyl one oxyethyl group silicon chlorides, be warming up to 80 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to 10 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 15
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml, ethanol 0.5ml is warming up to 100 ℃, constant temperature 3h under stirring; Add 3.4ml four titanium butoxide then, triethylene glycol butyl ether 0.5ml, 60 ℃ of reaction 3h.Be cooled to-10 ℃, drip the 15ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to 10 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 100 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 16
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, n-Octanol 6ml, butanols 0.5ml is warming up to 120 ℃, constant temperature 3h under stirring; Add 6.8ml four titanium butoxide then, triethylene glycol butyl ether 0.5ml, 60 ℃ of reaction 3h.Be cooled to-30 ℃, drip 10ml aminomethyl phenyl silicon dichloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to 10 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 17
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, hexalin 10ml, ethanol 0.5ml is warming up to 80 ℃, constant temperature 3h under stirring; Add 6.8ml four titanium butoxide then, triethylene glycol butyl ether 0.5ml, 80 ℃ of reaction 3h.Be cooled to-30 ℃, drip the 20ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to 10 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 100 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 18
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, n-Heptyl alcohol 8ml,, ethanol 0.5ml is warming up to 120 ℃, constant temperature 3h under stirring; Add 6.8ml four titanium butoxide then, triethylene glycol butyl ether 0.5ml, 60 ℃ of reaction 3h.Be cooled to-30 ℃, drip the 20ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-15 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 120 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 19
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml, ethanol 0.5ml is warming up to 110 ℃, constant temperature 3h under stirring; Add 6.8ml four titanium butoxide then, triglycol monoisopropyl ether 0.02ml, 60 ℃ of reaction 3h.Be cooled to-30 ℃, drip the 20ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-10 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 100 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 20
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 10ml, ethanol 0.5ml is warming up to 120 ℃, constant temperature 3h under stirring; Add 6.8ml four titanium butoxide then, 2-(2-(2-cyclopentyl oxyethyl group) oxyethyl group) ethanol 0.5ml, 60 ℃ of reaction 3h.Be cooled to-30 ℃, drip 10ml dimethyl oxyethyl group silicon chlorides, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-10 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 100 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 21
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, decyl alcohol 6ml, ethanol 0.5ml is warming up to 120 ℃, constant temperature 3h under stirring; Add 6.8ml four titanium butoxide then, triethylene glycol butyl ether 0.5ml, 80 ℃ of reaction 3h.Be cooled to-30 ℃, drip the 20ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-10 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Embodiment 22
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, decane 20ml, 2-Ethylhexyl Alcohol 6ml, ethanol 0.5ml is warming up to 120 ℃, constant temperature 3h under stirring; Add 8.4ml four titanium butoxide then, triethylene glycol butyl ether 0.5ml, 60 ℃ of reaction 3h.Be cooled to-30 ℃, drip the 20ml silicon tetrachloride, be warming up to 60 ℃ of reaction 2h after dropwising, obtain the turbid liquid of oyster white.Be cooled to-10 ℃, drip the 20ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 3h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Comparative Examples 1
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, heptane 20ml, 2-Ethylhexyl Alcohol 6.7ml is warming up to 100 ℃, constant temperature 2h under stirring; Be cooled to room temperature, drip the 10ml silicon tetrachloride, dropwise afterreaction 0.5h, obtain the turbid liquid of oyster white.Drip the 2ml titanium tetrachloride, be warming up to 70 ℃ of reaction 1h.Stop to stir, leave standstill suspension, layering, the elimination supernatant liquid, normal hexane washing four times, vacuum is drained, and obtains the main catalyst component of good fluidity, narrow diameter distribution.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
Comparative Examples 2
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 1g successively, 15ml toluene, epoxy chloropropane, tributyl phosphate, ethanol, be warming up to 80 ℃ under stirring, and keep 15 minutes to dissolving fully, add Tetra hydro Phthalic anhydride then, keep 1h, be cooled to-25 ℃ and drip the 14ml titanium tetrachloride, be warming up to 80 ℃, reaction 3h, filter back toluene and hexane wash, the dry catalyzer that gets.
2) vinyl polymerization: ethylene polymerisation process is identical with embodiment 1.Polymerization result sees Table 1.
3) ethylene copolymerization: the ethylene copolymerization process is identical with embodiment 1.Polymerization result sees Table 1.
Table 1
Claims (8)
1. an olefin polymerization catalysis is made up of Primary Catalysts and promotor, it is characterized in that: described Primary Catalysts is made up of magnesium compound, transition metal halide, halogenated silicon compound, organic alcohol compound, metal acid esters and organic pure ether compound; The mol ratio of magnesium compound, transition metal halide, halogenated silicon compound, organic alcohol compound and metal acid esters is 1:(0.1-30): (0.1-20): (0.5-10): (0.01-10); The mass ratio of magnesium halide and organic pure ether compound is: 100:0.1 – 20; Described promotor is organo-aluminium compound; Transition metal halide in the Primary Catalysts and the mol ratio of promotor are 1:30-500.
2. olefin polymerization catalysis according to claim 1, it is characterized in that: it is Mg (R) that described magnesium compound is selected from general formula (1)
aX
bCompound at least a, R is selected from C
1～C
20Aliphatic group, C
1～C
20Fatty alkoxyl group, C
3～C
20Alicyclic radical or C
6～C
20Aryl radical; X is selected from halogen; A=0,1 or 2, b=0,1 or 2, a+b=2.
3. olefin polymerization catalysis according to claim 1, it is characterized in that: it is M (R that described transition metal halide is selected from general formula (2)
1)
4-mX
mCompound at least a, in the formula, M is Ti, Zr, Hf; X is halogen atom, and m is 1 to 4 integer; R
1Be selected from C
1～C
20Aliphatic group, C
1～C
20Fatty alkoxyl group, C
1～C
20Cyclopentadienyl and derivative, C
1～C
20Aryl radical, COR` or COOR`, R` has C
1～C
10Fatty group or have C
1～C
10Aromatic base, the mol ratio of transition metal halide and magnesium compound (1-30): 1.
4. olefin polymerization catalysis according to claim 1, it is characterized in that: described organic alcohol compound is selected from C
2-C
15Fatty Alcohol(C12-C14 and C12-C18), C
3-C
15Alicyclic ring alcohol or C
6-C
15Aromatic alcohol, the mol ratio of organic alcohol compound and magnesium compound preferred (1-10): 1.
5. olefin polymerization catalysis according to claim 1, it is characterized in that: it is Si (R that described halogenated silicon compound is selected from general formula
2)
4-nX
nCompound at least a.In the formula, X is halogen atom, and n is 1 to 4 integer; R
2Be H, C
1～C
20Aliphatic group, C
1～C
20Fatty alkoxyl group, C
3～C
20Alicyclic radical or C
6～C
20Aryl radical, the mol ratio of halogenated silicon compound and magnesium compound (1-20): 1.
6. olefin polymerization catalysis according to claim 1, it is characterized in that: it is M (R that described metal acid ester cpds is selected from general formula
3)
4Compound at least a, in the formula, M is transition metal, is selected from Ti, Zr, Hf, R
3Be selected from C
1～C
20Fatty alkoxyl group, C
1～C
20Fragrant phenoxy group.The mol ratio (0.1-10) that belongs to ester compound and magnesium compound: 1.
7. olefin polymerization catalysis according to claim 1, it is characterized in that: described organic pure ether compound is that terminal group contains hydroxyl, shown in general formula (3), general formula (3): HO (CH
2CH
2O)
f(CH
2)
gR
4, wherein, f is 2 to 20 integer, g is 1 to 10 integer; R
4Be selected from C
1～C
30Aliphatic group, C
3～C
30Cycloalkyl, C
6～C
30Aryl radical, C
2～C
30Heterocyclylalkyl.
8. the preparation method of the described olefin polymerization catalysis of claim 1 is characterized in that: may further comprise the steps:
1) magnesium compound is scattered in the organic solvent, adds organic alcohol compound, 30-150 ℃ of following stirring and dissolving 1-5h;
2) with 1) solution is cooled to 10-80 ℃, adds metal acid ester cpds and organic pure ether compound, reacts 0.5-3h under this temperature;
3) under-40-30 ℃, make step 2) in the solution that obtains contact with halogenated silicon compound, reacted 0.5-5 hour, and be warming up to 40-110 ℃, reacted 0.5-5 hour;
4) under-40-30 ℃, the system that obtains in the step 3) is contacted with transition metal halide, reaction 0.5-5h, system is warming up to 20-150 ℃, reaction 0.5-5h, in temperature-rise period, particle is separated out and formed to solids gradually, after reaction finishes, leave standstill, filter, adopt toluene or normal hexane washing 4-6 time, vacuum is drained, and obtains Primary Catalysts;
5) be that 1:30-500 mixes with Primary Catalysts and promotor by transition metal halide and the mol ratio of promotor, obtain olefin polymerization catalysis.
Described organic solvent is selected from toluene, dimethylbenzene, hexane, heptane, octane or decane, or their mixed solvent;
It is Al (R that described promotor organo-aluminium compound is selected from general formula
5)
yX
3-yCompound in one or both mixing, in the formula, R
5For hydrogen or carbonatoms are that the alkyl of 1-20 or alkoxyl group, X are halogen, y is the integer of 0＜y≤3.
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| PCT/CN2013/000838 WO2014139062A1 (en) | 2013-03-13 | 2013-07-11 | Olefin polymerization catalyst and preparation method therefor |
| JP2015560506A JP6089123B2 (en) | 2013-03-13 | 2013-07-11 | Olefin polymerization catalyst and production method |
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| WO2014139062A1 (en) * | 2013-03-13 | 2014-09-18 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst and preparation method therefor |
| CN105440178A (en) * | 2014-09-28 | 2016-03-30 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, preparation method of olefin polymerization catalyst and olefin polymerization method |
| CN106519084A (en) * | 2015-09-15 | 2017-03-22 | 中国石油天然气股份有限公司 | Main catalyst for olefin polymerization catalyst, preparation method thereof and olefin polymerization catalyst |
| CN106905452A (en) * | 2017-01-07 | 2017-06-30 | 北京化工大学 | Alpha-olefin polymerization catalyst and preparation method and application |
| CN115246904A (en) * | 2021-04-26 | 2022-10-28 | 中国石油天然气股份有限公司 | Main catalyst component for solution-process ethylene polymerization, preparation method thereof, catalyst system and application thereof |
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| SG10202013131WA (en) * | 2016-06-30 | 2021-02-25 | Dow Global Technologies Llc | Procatalyst compositions useful for low comonomer incorporation and process for preparing the same |
| KR102467586B1 (en) * | 2017-11-17 | 2022-11-15 | 롯데케미칼 주식회사 | Method for producing a catalyst for ethylene polymerization and method for producing polyethylene using the same |
| KR102467604B1 (en) * | 2017-11-22 | 2022-11-15 | 롯데케미칼 주식회사 | Method for producing supporting particle |
| CN116554371A (en) * | 2023-03-27 | 2023-08-08 | 浙江大学 | Spherical catalyst for olefin polymerization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358761A (en) * | 2011-08-04 | 2012-02-22 | 北京化工大学 | Olefin polymerization catalyst and preparation method thereof |
| CN102492061A (en) * | 2011-11-26 | 2012-06-13 | 北京化工大学 | Alkene polymerization catalyst, preparation method thereof, and application thereof |
| CN102558404A (en) * | 2011-12-15 | 2012-07-11 | 中国石油天然气股份有限公司 | Polyol ether polyolefin catalyst and preparation and application thereof |
| CN102875704A (en) * | 2012-09-05 | 2013-01-16 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst, preparation method and application thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6081208A (en) * | 1983-10-08 | 1985-05-09 | Chisso Corp | Manufacture of alpha-olefin polymer |
| JPH04218507A (en) * | 1990-04-13 | 1992-08-10 | Mitsui Petrochem Ind Ltd | Solid titanium catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for polymerizing olefins |
| ES2120534T3 (en) | 1993-04-29 | 1998-11-01 | Ticona Gmbh | PROCEDURE FOR THE MANUFACTURE OF A CATALYST SYSTEM FOR THE POLYMERIZATION AND COPOLYMERIZATION OF ETHYLENE IN HOMOPOLYMERS AND COPOLYMERS OF ULTRA-RELATED MOLECULA ETHYLENE. |
| JP3734061B2 (en) * | 1997-04-02 | 2006-01-11 | チッソ株式会社 | Modified olefin (co) polymer composition, method for producing the same, and modified olefin (co) polymer composition molded article |
| WO1998044042A1 (en) * | 1997-04-02 | 1998-10-08 | Chisso Corporation | Modified olefin (co)polymer composition, process for preparing the same, and modified olefin (co)polymer composition molding |
| EP1242472B1 (en) | 1999-10-23 | 2004-09-15 | Samsung General Chemicals Co., Ltd. | An improved catalyst for homo- and co-polymerization of olefin |
| CN101096389B (en) | 2007-06-22 | 2010-05-19 | 上海化工研究院 | A kind of ultrahigh molecular weight polyethylene catalyst and preparation method thereof |
| CN101857650B (en) | 2010-06-02 | 2013-05-22 | 金发科技股份有限公司 | Preparation method of polyolefin catalyst spherical carrier |
| CN102558403B (en) | 2011-12-15 | 2014-08-06 | 中国石油天然气股份有限公司 | Glycol ether polyolefin catalyst and preparation and application thereof |
| CN103183754A (en) * | 2013-03-13 | 2013-07-03 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst and preparation method thereof |
-
2013
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- 2013-07-11 DE DE112013006813.3T patent/DE112013006813B4/en active Active
- 2013-07-11 JP JP2015560506A patent/JP6089123B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358761A (en) * | 2011-08-04 | 2012-02-22 | 北京化工大学 | Olefin polymerization catalyst and preparation method thereof |
| CN102492061A (en) * | 2011-11-26 | 2012-06-13 | 北京化工大学 | Alkene polymerization catalyst, preparation method thereof, and application thereof |
| CN102558404A (en) * | 2011-12-15 | 2012-07-11 | 中国石油天然气股份有限公司 | Polyol ether polyolefin catalyst and preparation and application thereof |
| CN102875704A (en) * | 2012-09-05 | 2013-01-16 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst, preparation method and application thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014139062A1 (en) * | 2013-03-13 | 2014-09-18 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst and preparation method therefor |
| CN105440178A (en) * | 2014-09-28 | 2016-03-30 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, preparation method of olefin polymerization catalyst and olefin polymerization method |
| CN105440178B (en) * | 2014-09-28 | 2018-03-02 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalysis and preparation method thereof and the method for olefinic polymerization |
| CN106519084A (en) * | 2015-09-15 | 2017-03-22 | 中国石油天然气股份有限公司 | Main catalyst for olefin polymerization catalyst, preparation method thereof and olefin polymerization catalyst |
| CN106519084B (en) * | 2015-09-15 | 2019-02-15 | 中国石油天然气股份有限公司 | Main catalyst for olefin polymerization catalyst, preparation method thereof and olefin polymerization catalyst |
| CN106905452A (en) * | 2017-01-07 | 2017-06-30 | 北京化工大学 | Alpha-olefin polymerization catalyst and preparation method and application |
| CN115246904A (en) * | 2021-04-26 | 2022-10-28 | 中国石油天然气股份有限公司 | Main catalyst component for solution-process ethylene polymerization, preparation method thereof, catalyst system and application thereof |
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| WO2014139062A1 (en) | 2014-09-18 |
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