CN101845104A - Olefin polymerization catalyst and preparation method thereof - Google Patents
Olefin polymerization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to olefin polymerization catalyst and a preparation method thereof, which belong to the fields of the olefin polymerization catalyst and olefin polymerization. The olefin polymerization catalyst mainly consists of a main catalyst and a cocatalyst and is characterized in that the main catalyst consists of a carrier, a transition metal halide, an organic alcoholic compound, an organo-siloxane compound and an electron donor with the molar ratio of 1:0.01-20:0.1-6:0.01-5:0.01-5; the cocatalyst is an organo-aluminum compound; and the molar ratio of the transition metal halide to the cocatalyst in the main catalyst is 1:30-500. The catalyst has good particle shape, and the particles are ball-shaped; the catalyst has high activity, the polymer molecular weight is high, and the polymer molecular weight distribution is wide (MWD=3-65); the catalyst is suitable for a slurry packing method, a gas-phase polymerization process or a combination polymerization process; and the preparation method is simple, has low requirements to facility and has little environmental pollution.
Description
Technical field
The invention belongs to olefin polymerization catalysis and field of olefin polymerisation, be specifically related to be used for the catalyzer and the Preparation of catalysts method of vinyl polymerization or propylene polymerization or copolymerization.
Background technology
Olefin polymerization catalysis is the core of polyolefin polymerization technology, development from olefin polymerization catalysis, summarize and get up to mainly contain two aspects: (1) exploitation can prepare property or the more excellent polyolefin resin catalyzer of performance, as metallocene catalyst and non-luxuriant late transition metal catalyst etc.; (2) for the production of general purpose polyolefin resin, on the basis of further improving catalyst performance, simplify catalyst preparation process, reduce the catalyzer cost, develop environment amenable technology, to increase the benefit, enhance the competitiveness.Before the eighties in 20th century, the emphasis of polyethylene catalysts research is to pursue catalyst efficiency, and through nearly 30 years effort, the catalytic efficiency of polyethylene catalysts is the order of magnitude and improves, thereby has simplified polyolefinic production technique, has reduced energy consumption and material consumption.
Yet traditional Z-N catalyst ethene/senior Alpha-olefin-copolymerization is fashionable, and the insertion amount of senior Alpha-alkene is little.Bialek[Bialk M, et al.Polymer, 2000,41:7899], adopt vanadium series catalyst MgCl
2(THF)
2/ VCl
4/ Et
2AlCl catalyzed ethylene and 1-octene copolymer close, and the insertion amount of 1-octene is 0.47% in the multipolymer, under the same polymeric condition, and Titanium series catalyst MgCl
2(THF)
2/ TiCl
4/ Et
2The monomer insertion amount of AlCl is lower than vanadium system, is 0.39%.
But, the Ziegler-Natta catalyst of loading type is ripe in industrial application, therefore, improve traditional Z-N catalyzer, improve the copolymerization ability of 1-octene, the research of ethene/1-octene copolymer compound that preparation 1-octene molar content is high has certain theoretical significance and important application value.We (application number: 200910083230.8) find that traditional efficient Ziegler-Natta catalyst is with modifications such as alcohol after, catalyzer is catalyzed ethylene and senior Alpha-alpha-olefinic copolymerization effectively, but the olefin-copolymerization that the efficient Ziegler-Natta catalyst catalyzed ethylene/steric restriction that adopts this modification is big is fashionable, the copolymerized ability of comonomer is low, therefore, the present invention further improves the efficient Ziegler-Natta catalyst of tradition, improve the copolymerization ability of senior Alpha-alkene, the research for preparing the high ethene/senior Alpha-olefin copolymer of senior Alpha-alkene molar content has important significance for theories and important application value.
Summary of the invention
The object of the present invention is to provide high catalyst component that is used for vinyl polymerization or ethene and copolymerization monomer copolymerizable of a kind of catalytic activity and preparation method thereof.
Ethylene copolymerization catalyst provided by the present invention is made up of Primary Catalysts and promotor; Wherein, described Primary Catalysts is made up of carrier, transition metal halide, organic alcohol compound, organosilicone compounds and electron donor.Carrier, transition metal halide, organic alcohol compound, organosilicone compounds and electron donor with magnitude relation be: the mol ratio of carrier, transition metal halide, organic alcohol compound, organosilicone compounds and electron donor is 1: 0.01-20: 0.1-6: 0.01-5: 0.01-5; Described promotor is an 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.
Described carrier is meant inorganic oxide carrier, halide carrier or polymer support.Inorganic oxide carrier is SiO
2Or Al
2O
3Before load, spend activation treatment 4 hours through 100 degree-700;
Wherein, described halide carrier be in the complex compound, magnesium dihalide molecular formula of the water of magnesium dihalide, magnesium dihalide or alcohol one of them or two halogen atoms by hydroxyl or halogen hydroxyl oxygen base institute metathetical derivative.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, described polymer support is cyclodextrin, polystyrene.
One of feature of the present invention is to add electron donor in the Primary Catalysts preparation process, and described electron donor is organic silanol, organosilicon mercaptan compound or organosilicon amine compound.Electron donor can add one or both or two or more.
Wherein, described organosilicon alkylol cpd is selected from organic silanol that carbonatoms is 1-15, carbonatoms is the organic silanol of the branched-chain alkyl of 1-15, carbonatoms is the organic silanol of the cycloalkyl of 1-15, carbonatoms be organic silanol of the isomery of 1-15 or carbonatoms be the organic silanol of 6-30 aryl at least a, specifically comprise: trimethyl silanol, the trimethoxy silanol, triethyl silanol, the triethoxy silanol, the triphenyl silanol, the triple phenoxyl silanol, the thricyclohexyl silanol, the triisopropyl silanol, three different oxygen propyl group silanols, dimethyl phonyl silanol, diethoxy phenyl silanol, dimethyl oxyethyl group silanol, dimethoxy oxyethyl group silanol.In the process of preparation Primary Catalysts, add organic silanol and transition metal halide reaction, make the compound of all or part of generation of transition metal halide such as general formula (1).
MP
zCl
x(ASiR
3)
y
(general formula 1)
M represents Ti, Zr, Hf, Fe, Co, Ni, V, Nd, Y, Sc or Sm etc. in the general formula (1); R represents the alkyl of C1-C15, C1-C15 cycloalkyl, the aryl of C6-C30, the alkoxyl group of C1-C15, the cycloalkyloxy of C1-C15, the aryloxy of C6-C30 etc.; A represents oxygen element; P represents cyclopentadienyl, indenyl or the fluorenyl or derivatives thereof of C5-C30; When P is single cyclopentadienyl ligand, x=2, y=1, Z=1; When P is dicyclopentadiene or bridging cyclopentadienyl ligand, x=1, y=1, Z=2; When P does not exist, x=1,2 or 3, y=1,2, or 3, x+y=4, Z=0.
The preferred 0.01-5 of mol ratio of described organic silanol and carrier: 1.
Wherein, described organosilicon amine compound is selected from the organosilicon amine that carbonatoms is 1-20, carbonatoms is the branched-chain alkyl organosilicon amine of 1-20, carbonatoms be the cycloalkyl organosilicon amine of 1-20 or carbonatoms be 6-30 aryl organosilicon amine at least a, specifically comprise: trimethyl silicon based methylamine, trimethyl silicon based tertiary butyl amine, trimethyl silicon based isobutylamine, trimethyl silicon based n-butylamine, the silica-based methylamine of trimethoxy, the silica-based methylamine of triethyl, the silica-based ethylamine of triethoxy, the basic amine of two (trimethyl silicanes), the silica-based methylamine of triphenyl, the silica-based methylamine of triple phenoxyl, the silica-based methylamine of thricyclohexyl, the triisopropylsilyl methylamine, the silica-based methoxyl group amine of three different oxygen propyl group, the silica-based methylamine of 3,5-dimethylphenyl, the silica-based methylamine of diethoxy phenyl, dimethyl ethyl-silicone methylamine, dimethoxy ethyl-silicone methylamine.In the process of preparation Primary Catalysts, add organosilicon amine and transition metal halide reaction, make the compound of all or part of generation of transition metal halide such as general formula (1).
M represents Ti, Zr, Hf, Fe, Co, Ni, V, Nd, Y, Sc or Sm etc. in the general formula (1); R represents the alkyl of C1-C15, C1-C15 cycloalkyl, the aryl of C6-C30, the alkoxyl group of C1-C15, the cycloalkyloxy of C1-C15, the aryloxy of C6-C30 etc.; A represents secondary amine; P represents cyclopentadienyl, indenyl or the fluorenyl or derivatives thereof of C5-C30; When P is single cyclopentadienyl ligand, x=2, y=1, Z=1; When P is dicyclopentadiene or bridging cyclopentadienyl ligand, x=1, y=1, Z=2.When P does not exist, x=1,2 or 3, y=1,2, or 3, x+y=4, Z=0.
The preferred 0.01-5 of mol ratio of described organosilicon amine and carrier: 1.
Wherein, described organosilicon mercaptan compound is selected from the organosilicon mercaptan that carbonatoms is 1-20, carbonatoms is the branched-chain alkyl organosilicon mercaptan of 1-20, carbonatoms be the cycloalkyl organosilicon mercaptan of 1-20 or carbonatoms be 6-30 aryl organosilicon organosilicon mercaptan at least a, specifically comprise: trimethyl silicane mercaptan, trimethoxy silicon mercaptan, triethyl silicon mercaptan, triethoxysilicane mercaptan, two (trimethyl silicane) mercaptan, triphenyl silicon mercaptan, triple phenoxyl silicon mercaptan, thricyclohexyl silicon mercaptan, triisopropyl silicon mercaptan, three different oxygen propyl group silicon mercaptan, 3,5-dimethylphenyl silicon mercaptan, diethoxy phenyl silicon mercaptan, dimethyl oxyethyl group silicon mercaptan, dimethoxy oxyethyl group silicon mercaptan.In the process of preparation catalyzer, add organosilicon mercaptan and transition metal halide reaction, make the compound of all or part of generation of transition metal halide such as general formula (1).
M represents Ti, Zr, Hf, Fe, Co, Ni, V, Nd, Y, Sc or Sm etc. in the general formula (1); R represents the alkyl of C1-C15, C1-C15 cycloalkyl, the aryl of C6-C30, the alkoxyl group of C1-C15, the cycloalkyloxy of C1-C15, the aryloxy of C6-C30 etc.; A represents element sulphur; P represents cyclopentadienyl, indenyl or the fluorenyl or derivatives thereof of C5-C30; When P is single cyclopentadienyl ligand, x=2, y=1, Z=1; When P is dicyclopentadiene or bridging cyclopentadienyl ligand, x=1, y=1, Z=2; When P does not exist, x=1,2 or 3, y=1,2, or 3, x+y=4, Z=0.
The preferred 0.01-5 of mol ratio of described organosilicon mercaptan compound and carrier: 1.
One of feature of the present invention is to add transition metal halide in the Primary Catalysts preparation process, and it is M (R that described transition metal halide is selected from general formula
1)
4-mX
mCompound at least a, in the formula, M is Ti, Zr, Hf, Fe, Co, Ni, V, Nd, Y, Sc or Sm etc.; X is a halogen atom, is selected from Cl, Br, F; M is 0 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.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 Ti, Zr, Hf, Fe, Co, Ni, V, Nd, Y, transition metal halides such as Sc or Sm specifically can select one or more the mixing in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, tetrabutyl titanate, isopropyl titanate, methoxyl group titanous chloride, dibutoxy titanium dichloride, three butoxy titanium chlorides, four phenoxide titaniums, a chlorine triple phenoxyl titanium, two chlorodiphenyl oxygen base titaniums, trichlorine one phenoxide titanium for use.Wherein, preferred titanium tetrachloride, cyclopentadiene titanous chloride, cyclopentadiene tri-chlorination zirconium, pentamethyl-cyclopentadiene titanous chloride, Dicyclopentadiene (DCPD) titanium dichloride, two pentadiene zirconium dichlorides, bridging two indenyl titanium dichloride, bridging two fluorenyl zirconium dichlorides, CGC catalyzer, salicylic alidehyde imine titanium (zirconium) catalyzer (F1).The preferred 0.01-20 of the mol ratio of transition metal halide and carrier: 1.
One of feature of the present invention is to add organosilicone compounds in the Primary Catalysts preparation process, and described organosilicone compounds is that general molecular formula is Si (OR
4)
4Organosilicone compounds in one or more, in the formula, R
4For carbonatoms is the alkyl of 1-15, four R
4Can be the same or different.Specifically can be selected from: the mixing of one or more in triethoxy isopropoxy silane, diethoxy isopropoxy tert.-butoxy silane, three isopropoxy tert.-butoxy silane, diisopropoxy two tert.-butoxy silane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2-ethyl hexyl oxy) silane.Preferred triethoxy isopropoxy silane, diethoxy isopropoxy tert.-butoxy silane, three isopropoxy tert.-butoxy silane, diisopropoxy two tert.-butoxy silane.
The preferred 0.01-5 of the mol ratio of described organosilicone compounds and carrier: 1.
One of feature of the present invention is to add organic alcohol compound in the Primary Catalysts preparation process, described organic alcohol compound be selected from isomery alcohol that straight chain alcohol that carbonatoms is 1-15, branched alkyl alcohol that carbonatoms is 1-15, cycloalkyl alcohol that carbonatoms is 1-15 or carbonatoms be 1-15 at least a.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 etc.; Cycloalkanol, as hexalin, methyl-cyclohexanol; Aromatic alcohol, as Bian alcohol, methyl Bian alcohol, sec.-propyl Bian alcohol etc.Wherein, preferred fat alcohol, especially at least a in preferred alcohol, butanols, 2-Ethylhexyl Alcohol or the glycerol.The adding of organic alcohol is transferred important to the hydrogen of polymkeric substance.The preferred 0.5-6 of the mol ratio of described organic alcohol compound and magnesium halide: 1.
When making carrier with halogenide, can add organic epoxy compounds and make solubility promoter in the preparation process of Primary Catalysts, described organic epoxy compounds is selected from least a in the inner ether that aliphatics alkene that carbonatoms is 2-8, diolefine that carbonatoms is 2-8, halogenated aliphatic alkene that carbonatoms is 2-8, oxide compound that carbonatoms is the diolefine of 2-8, glycidyl ether that carbonatoms is 2-8 or carbonatoms be 2-8.Concrete as: at least a in oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane or the methyl glycidyl ether.Wherein, at least a in preferred propylene oxide or the epoxy chloropropane.
The preferred 0-5 of mol ratio of described organic epoxy compounds and magnesium halide: 1.
When making carrier with halogenide, can add organophosphate and make solubility promoter in the preparation process of Primary Catalysts, described organophosphate is selected from least a in the hydrocarbyl carbonate of ortho-phosphoric hydrocarbyl carbonate or phosphorous acid.Concrete as: at least a in ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid three propyl ester, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or the phosphorous acid benzene methyl.Wherein, preferred ortho-phosphoric acid tri-n-butyl.
The preferred 0.5-5 of the mol ratio of described organophosphate and magnesium halide: 1.
When making carrier with halogenide, halogenide is dissolving earlier, separates out with the spheroidal particle state again, and one of feature of the present invention is to add saturated alkane or naphthenic hydrocarbon is done precipitation additive in the preparation process of Primary Catalysts.Add precipitation additives in halogenide dissolving back in 50 degree-120 degree, add precipitation additives in-10 degree-30 degree after splashing into titanium tetrachloride, be warming up to 50 degree-80 degree and add precipitation additives.Described precipitation additive is C5-C20 saturated alkane or naphthenic hydrocarbon, preferred normal hexane, normal heptane, octane, hexanaphthene.Helping catalyzer separates out with particle form.
One of feature of the present invention is when adopting halogenide to make carrier, halogenide is dissolving earlier, separate out with the spheroidal particle state again, add halide mixture pellet shaping promotor in the preparation process of Primary Catalysts, described promotor is vacuum grease, Vaseline, white oil, Chinese wax, organic silicone oil, low-molecular-weight polyolefine (Mn=500-10000) or low-molecular-weight polystyrene (Mn=500-30000) etc.
Precipitation additive of the present invention is saturated alkane or naphthenic hydrocarbon, preferred normal hexane, normal heptane or hexanaphthene.One of feature of the present invention effect that precipitation additive adds several times in the preparation process of Primary Catalysts is better than once adding, and preferred 3 times, dissolve the back fully at carrier halogenide respectively and add, drip TiCl
4The back adds, and drips TiCl
4After add again more than being warming up to 50 degree.The amount of the precipitation additive that adds can equate at every turn, also can be unequal.
In the Primary Catalysts preparation process, can add precipitation additive or halide mixture pellet shaping promotor, or the both adds.
It is AlR that described promotor organo-aluminium compound is selected from general formula
5 nX
3-nCompound 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, n is the integer of 0＜n≤3, specifically can be selected from: the mixing of one or both in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-tert aluminium, trioctylaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride, the sesquialter ethyl aluminum chloride etc.; Methylaluminoxane, ethyl aikyiaiurnirsoxan beta etc.Wherein, the mixing of one or both in preferred triethyl aluminum or triisobutyl aluminium or the methylaluminoxane.
As the preferred technical solution of the present invention, Primary Catalysts and promotor with magnitude relation be: the mol ratio of transition metal halide and promotor is 1: 30-500.
The preparation method of olefin polymerization catalysis provided by the present invention may further comprise the steps:
1) with carrier at 10-150 ℃, be scattered in the organic solvent, add organic alcohol compound again;
2) under-40-30 ℃, add transition metal halide in the solution that in step 1), obtains, dropwise the back and add organosilicone compounds and electron donor, and be warming up to 40-110 ℃, reacted 0.5-24 hour, in temperature-rise period, particle is separated out and formed to solids gradually, after reaction finishes, adopt toluene or normal hexane washing 4-6 time, filter, remove unreacted reactant, solubility promoter, precipitation additive, shaping particles promotor and solvent, vacuum is drained, and obtains main catalyst component.Solubility promoter, precipitation additive, shaping particles promotor and solvent do not participate in chemical reaction in catalyst preparation process.
3) be 1 with Primary Catalysts and promotor by the mol ratio of promotor and transition metal halide: 30-500 mixes, and obtains olefin polymerization catalysis.
Described organic solvent is selected from toluene, dimethylbenzene, hexane, heptane, octane or decane, or their mixed solvent, preferred toluene, hexane, heptane or decane.
The purposes of ethylene rolymerization catalyst provided by the present invention is: can be used as the copolymerization catalyst of vinyl polymerization or ethene and alpha-olefin, wherein, the preferred propylene of described alpha-olefin, 1-butylene, the 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, cyclopentenes, 4-methyl-1-pentene, 1,3-butadiene, isoprene, vinylbenzene, vinyl toluene, norbornylene, replace norbornylene, methyl methacrylate, methyl acrylate, butyl acrylate, vinyl cyanide is to vinyl benzene formonitrile HCN etc.
Olefin polymerization catalysis provided by the present invention has following beneficial effect:
The particle form of ethylene copolymerization catalyst provided by the present invention is good, and is spherical in shape; The catalyst activity height is used for the fashionable alpha-olefin insertion of ethene and alpha-olefin copolymer rate height; Through GPC test, polymericular weight height, molecular weight distribution broad (MWD=3-65); Be applicable to slurry process, gas-phase polymerization process or polymerization mix technology; The preparation method is simple, and is low for equipment requirements, and environmental pollution is little.
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is limited to following embodiment not to the utmost.
Embodiment
Embodiment 1
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 5g successively, epoxy chloropropane 3.5ml, tributyl phosphate 5.5ml through nitrogen, toluene 75ml, hexane 3ml, ethanol 3.2ml, be warming up to 70 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, Dropwise 5 8ml titanium tetrachloride dropwises the back and adds 0.5g trimethyl silanol, 3.5ml triethoxy isopropoxy silane, behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h, add hexane 3ml, be warming up to 60 ℃ of constant temperature, add hexane 3ml, reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of 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-octene 35mL, constant voltage isothermal reaction 2h.MWD＝45。
Embodiment 2
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 5g successively, epoxy chloropropane 7.5ml, tributyl phosphate 10.5ml, toluene 75ml, hexane 3ml, ethanol 6.2ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, drip the 40ml titanium tetrachloride, dropwise the back and add the 0.5g trimethyl silanol, behind the reaction 1h, be warming up to 60 ℃ of constant temperature, hexane 3ml, reaction 2h stops to stir, and leaves standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of 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 40mL, constant voltage isothermal reaction 2h.MWD＝15。
Embodiment 3
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 5g successively, epoxy chloropropane 5ml through nitrogen, tributyl phosphate 10.5ml, toluene 75ml, hexane 3ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride dropwises the back and adds the 1g trimethyl silanol, behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h are warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.17ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene to 0.73MPa, adds 4-methyl-1-pentene 30mL, constant voltage isothermal reaction 2h.MWD＝20.
Embodiment 4
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, Dropwise 5 5ml titanium tetrachloride, dropwise the back and add the 0.8g triethyl silanol, 2ml diethoxy isopropoxy tert.-butoxy silane is behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h, be warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.17ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene to 0.73MPa, adds 3-methyl-1-butene 40mL, constant voltage isothermal reaction 2h.MWD＝38.
Embodiment 5
1) preparation Primary Catalysts: in the reactor of fully replacing, add polystyrene support 5g successively, normal hexane 75ml through nitrogen, be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride dropwises the back and adds 0.5g trimethoxy silanol, behind the reaction 1h, be warming up to 80 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen to 0.20MPa after being warming up to 80 ℃, charges into ethene to 0.60MPa, adds isoprene 30mL, constant voltage isothermal reaction 2h.MWD＝35.
Embodiment 6
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, add 3g cyclopentadiene titanous chloride, add the 1.5g trimethyl silanol again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 25ml (10%wt/v), charge into ethene to 0.45MPa after being warming up to 70 ℃, add 1-amylene 30mL, constant voltage isothermal reaction 2h.MWD＝3.6.
Embodiment 7
1) preparation Primary Catalysts: in the reactor of fully replacing, add Cyclodextrin carrier 5g successively, toluene 75ml through nitrogen, be cooled to-25 ℃, add 3g cyclopentadiene titanous chloride, add the 0.5g trimethyl silanol again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 40ml (10%wt/v), charge into ethene to 0.45MPa after being warming up to 70 ℃, add vinylbenzene 30mL, constant voltage isothermal reaction 2h.MWD＝4.1.
Embodiment 8
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, add 3g cyclopentadiene titanous chloride, add the 1.5g trimethyl silanol again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: with 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, in still, add main catalyst component 20mg successively, dehydration hexane 200ml, MAO solution 35ml (10%wt/v), charge into ethene to 0.25MPa after being warming up to 70 ℃, add p-methylstyrene 30mL, constant voltage isothermal reaction 2h.MWD＝3.5.
Embodiment 9
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, add 3g Dicyclopentadiene (DCPD) zirconium dichloride, add 0.5g trimethylammonium tertiary butyl amine and 0.5g trimethyl silanol again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 25ml (10%wt/v), charge into ethene to 0.5MPa after being warming up to 70 ℃, add 1-hexene 40mL, constant voltage isothermal reaction 2h.
Embodiment 10
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 3g Dicyclopentadiene (DCPD) zirconium dichloride, add 1.5g trimethyl silicane tertiary butyl amine again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 30ml (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add cyclopentenes 50mL, constant voltage isothermal reaction 2h.MWD＝3.7.
Embodiment 11
1) preparation Primary Catalysts: in the reactor of fully replacing, add MgCl successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 3g ethyl bridging two indenyl titanium dichloride, add 0.5g triethoxy silanol again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 15mL (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add cyclopentenes 40mL, constant voltage isothermal reaction 2h.
Embodiment 12
1) preparation Primary Catalysts: in the reactor of fully replacing, add MgCl successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stir, add 3g pentamethyl-cyclopentadiene titanous chloride, add 0.5g triphenyl silanol again, 1.0g diethoxy isopropoxy tert.-butoxy silane, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains good fluidity, the main catalyst component of narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 35ml (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add cyclopentenes 30mL, constant voltage isothermal reaction 2h.MWD＝4.2.
Embodiment 13
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75mL again, stir, add 3g CGC titanium catalyst, add 0.5g triphenyl silanol again, 1.0g triethoxy isopropoxy silane, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 25ml (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add cyclopentenes 30mL, constant voltage isothermal reaction 2h.MWD＝3.6.
Embodiment 14
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 3g salicylic alidehyde imine titanium catalyst (F1), add the 0.5g trimethyl silanol again, behind the reaction 1.5h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 20ml (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add cyclopentenes 25mL, constant voltage isothermal reaction 2h.MWD＝4.0.
Embodiment 15
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 3g salicylic alidehyde imine nickel catalyzator, add 0.5g trimethyl silicane mercaptan again, behind the reaction 1.5h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 25ml (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add cyclopentenes 20mL, constant voltage isothermal reaction 2h.
Embodiment 16
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, drips the 40ml titanium tetrachloride, dropwise the back and add the 0.5g triethyl silanol, 0.3g trimethylammonium isobutylamine, 2ml triethoxy isopropoxy silane is behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h, be warming up to 80 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of 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 0.28MPa after being warming up to 80 ℃, charges into ethene 0.45MPa, adds 3-Methyl-1-pentene 35mL, constant voltage isothermal reaction 2h.MWD＝38.
Embodiment 17
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml, be cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds the 20ml titanium tetrachloride again, dropwises the back and adds the 0.5g trimethyl silanol, 2ml triethoxy isopropoxy silane, behind the reaction 4h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h, be warming up to 80 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains good fluidity, the main catalyst component of narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of 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 0.28MPa after being warming up to 80 ℃, charges into ethene 0.45MPa, adds 3-Methyl-1-pentene 35mL, constant voltage isothermal reaction 2h.
Embodiment 18
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml, be cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds the 10ml titanium tetrachloride again, dropwises the back and adds the 0.5g trimethyl silanol, 1.5ml the different third oxygen tert-butoxy silane of diethoxy, behind the reaction 2h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h, be warming up to 55 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains good fluidity, the main catalyst component of narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of 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 0.28MPa after being warming up to 80 ℃, charges into ethene 0.45MPa, adds 1-octene 25mL, constant voltage isothermal reaction 2h.MWD＝43.
Embodiment 19
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml,, be cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds the 15ml titanium tetrachloride again, dropwise the back and add the 0.5g trimethyl silanol, 1.5ml the different third oxygen tert-butoxy silane of diethoxy behind the reaction 3h, is warming up to 65 ℃ of isothermal reaction 5h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of 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 0.28MPa after being warming up to 80 ℃, charges into ethene 0.45MPa, adds 1-hexene 20mL, constant voltage isothermal reaction 2h.MWD＝51.
Embodiment 20
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, add the 30ml titanium tetrachloride, dropwise the back and add 0.5g triethyl silanol, the different third oxygen tert-butoxy silane of 1.5ml diethoxy, 0.5g trimethyl silicane 2, the 6-diisopropylamine is behind the reaction 3h, be warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of 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 0.28MPa after being warming up to 80 ℃, charges into ethene 0.45MPa, adds 1-hexene 25mL, constant voltage isothermal reaction 2h.MWD＝56.
Embodiment 21
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 5g successively, epoxy chloropropane 7.5ml through nitrogen, toluene 75ml, hexane 3ml, ethanol 4ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, drip the 40ml titanium tetrachloride, dropwise the back and add the 0.5g trimethyl silanol, 3.5ml tetraethoxysilane behind the reaction 2h, is warming up to 60 ℃ of constant temperature, add hexane 3ml, reaction 2h stops to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.17ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 80 ℃, charges into ethene 0.45MPa, adds 1-butylene 35g, constant voltage isothermal reaction 2h.MWD＝26。
Embodiment 22
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 5g successively, epoxy chloropropane 7.5ml through nitrogen, tributyl phosphate 7.5mL, toluene 75ml, hexane 5ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, Dropwise 35 ml titanium tetrachloride, hexane 5ml, dropwise the back and add the 0.5g trimethyl silanol, the different third oxygen tert-butoxy silane of 1.5ml diethoxy is behind the reaction 2h, be warming up to 60 ℃, add hexane 5ml, isothermal reaction 2h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 80 ℃, charges into ethene 0.45MPa, adds 1-octene 20mL, constant voltage isothermal reaction 2h.
Embodiment 23
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 5g successively through nitrogen, phenol 7.5ml, toluene 75ml, hexane 10ml, ethanol 6.2ml is warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, drip the 30ml titanium tetrachloride, dropwise the back and add the 0.5g trimethyl silanol, the different third oxygen tert-butoxy silane of diethoxy, 0.5ml, hexane 10ml, behind the reaction 2h, be warming up to 60 ℃, add hexane 10ml, isothermal reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) vinyl polymerization: 0.5 liter of 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 0.28MPa after being warming up to 85 ℃, charges into ethene 0.45MPa, constant voltage isothermal reaction 2h.
Embodiment 24
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 5g successively, epoxy chloropropane 3.5ml, tributyl phosphate 5.5ml, vacuum grease 0.3g, toluene 75ml, hexane 3ml, ethanol 3.2ml is warming up to 70 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, drip the 40ml titanium tetrachloride, dropwise the back and add 0.5g dimethoxy oxyethyl group silanol, triethoxy isopropoxy silane 1ml, hexane 5ml is behind the reaction 2h, be warming up to 60 ℃, add hexane 8ml, isothermal reaction 2h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 85 ℃, charges into ethene 0.45MPa, adds 1-octene 20mL, constant voltage isothermal reaction 2h.MWD＝23.
Embodiment 25
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 5g successively, epoxy chloropropane 5.5ml, tributyl phosphate 5.5ml through nitrogen,, toluene 75ml, hexane 8ml, ethanol 3ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, drip the 25ml titanium tetrachloride, dropwise the back and add the 0.5g trimethyl silanol, 2ml three isopropoxy tert.-butoxy silane, hexane 8ml is behind the reaction 2h, be warming up to 60 ℃ of constant temperature, add hexane 8ml, reaction 2h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 85 ℃, charges into ethene 0.45MPa, adds 1-hexene 25mL, 1-octene 10mL, constant voltage isothermal reaction 2h.
Embodiment 26
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 5g successively, epoxy chloropropane 3.5ml, tributyl phosphate 5.5ml, white oil 0.5g, toluene 75ml, ethanol 3.2ml, be warming up to 70 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, drip the 25ml titanium tetrachloride, dropwise the back and add the 0.5g trimethyl silanol, triethoxy tert.-butoxy silane behind the reaction 2h, is warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 85 ℃, charges into propylene, ethylene pressure to 0.55MPa, adds 1-hexene 10mL, 1-octene 10mL, pentadiene 3mL, constant voltage isothermal reaction 2h.MWD＝60.
Embodiment 27
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, be cooled to-10 ℃, add the 15ml titanium tetrachloride, dropwise the back and add 0.5g triethyl silanol, the different third oxygen tert-butoxy silane of 1.5ml diethoxy, 0.5g 2, the 6-diisopropyl phenol behind the reaction 3h, is warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains good fluidity, the main catalyst component of narrow diameter distribution;
2) vinyl polymerization: 0.5 liter of 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 0.28MPa after being warming up to 80 ℃, charges into ethene 0.45MPa, constant voltage isothermal reaction 2h.MWD＝46.
Embodiment 28
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, is cooled to-10 ℃, add the 15ml titanium tetrachloride, dropwise the back and add the 1.5g triethyl silanol, 0.5g 2, the 6-diisopropyl phenol, behind the reaction 3h, be warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) vinyl polymerization: 0.5 liter of 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 0.28MPa after being warming up to 80 ℃, charges into ethene 0.45MPa, divinyl 30g, constant voltage isothermal reaction 2h.MWD＝55.
Embodiment 29
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, adds 2M n-Butyl Lithium (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 3g cyclopentadiene titanous chloride, add 1.0g triphenyl silanol again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 35ml (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add norbornylene 20mL, constant voltage isothermal reaction 2h.MWD＝4.5.
Embodiment 30
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, adds the 0.5g sodium tert-butoxide, be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 3g salicylic alidehyde imine titanium (F1) catalyzer, add the 1.0g trimethyl silanol again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: with 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, in still, add main catalyst component 20mg successively, dehydration hexane 200ml, MAO solution 35ml (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add hydroxyl norbornylene 20mL, constant voltage isothermal reaction 2h.
Embodiment 31
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stir, add 5g salicylic alidehyde imine titanium (F1) catalyzer, add the 1.0g trimethyl silanol again, triethoxy isopropoxy silane, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: with 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, in still, add main catalyst component 20mg successively, dehydration hexane 200ml, MAO solution 35ml (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add methyl methacrylate 20mL, constant voltage isothermal reaction 2h.
Embodiment 32
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 5g salicylic alidehyde imine iron catalyst, add the 1.0g trimethyl silanol again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: with 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, in still, add main catalyst component 20mg successively, dehydration hexane 200ml, MAO solution 35ml (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add butyl acrylate 20mL, constant voltage isothermal reaction 2h.
Embodiment 33
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 5g salicylic alidehyde imine titanium (F1) catalyzer, add the 1.0g triethyl silanol again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, MAO solution 35ml (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, add vinyl cyanide 10mL, constant voltage isothermal reaction 2h.
Embodiment 34
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 5g salicylic alidehyde imine zirconium (F1) catalyzer, add the 1.0g trimethyl silanol again, behind the reaction 1h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: with 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, in still, add main catalyst component 20mg successively, dehydration hexane 200mL, MAO solution 35mL (10%wt/v), charge into ethene 0.45MPa after being warming up to 70 ℃, adding is to vinyl benzene formonitrile HCN 10g, constant voltage isothermal reaction 2h.
Embodiment 35
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 5g successively, epoxy chloropropane 3.5ml, tributyl phosphate 5.5ml, Chinese wax 0.2g, toluene 75ml, ethanol 3.2ml, be warming up to 70 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, drip the 25ml titanium tetrachloride, dropwise the back and add 0.5g octyl mercaptan, 1.0g diethoxy isopropoxy tert.-butoxy silane behind the reaction 2h, is warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) copolymerization of propylene: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 85 ℃, charges into propylene pressure to 0.55MPa, adds 1-octene 20mL, constant voltage isothermal reaction 2h.MWD＝24.
Embodiment 36
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 5g successively, epoxy chloropropane 3.5ml, tributyl phosphate 5.5ml, polyolefine 0.1g, toluene 75ml, hexane 3ml, ethanol 3.2ml is warming up to 70 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, drip the 25ml titanium tetrachloride, white oil 1 gram, add 1,8-naphthalene two dibutyl phthalate 3g are behind the reaction 2h, be warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) propylene polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml), triethoxy isopropoxy silane 1.0g charges into hydrogen 0.28MPa after being warming up to 85 ℃, charges into propylene pressure to 0.55MPa, constant voltage isothermal reaction 2h.MWD＝24.
Embodiment 37
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 5g successively, epoxy chloropropane 3.5ml, tributyl phosphate 5.5ml, polystyrene 0.1g, toluene 75ml, hexane 8ml, ethanol 3.2ml is warming up to 70 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, add the 2.5g vanadium tetrachloride, dropwise the back and add the 0.5g trimethyl silanol, 1.0g triethoxy isopropoxy silane, hexane 8ml is behind the reaction 2h, be warming up to 60 ℃ and add hexane 3ml, isothermal reaction 2h stops to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 85 ℃, charges into ethylene pressure to 0.55MPa, adds 3-methyl-1-butene 30mL, constant voltage isothermal reaction 2h.
Embodiment 38
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 5g successively, epoxy chloropropane 3.5ml, tributyl phosphate 5.5ml, polyethylene wax 0.3g, toluene 75ml, ethanol 3.2ml, be warming up to 70 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, add 2.5g four Neodymium trichlorides, dropwise the back and add the 0.5g trimethyl silanol, 1.0g diethoxy isopropoxy tert.-butoxy silane behind the reaction 2h, is warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 85 ℃, charges into ethylene pressure to 0.55MPa, adds cyclopentenes 30mL, constant voltage isothermal reaction 2h.
Embodiment 39
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, add toluene 75ml again, stir, add 2.5g four Neodymium trichlorides, dropwise the back and add 0.5g 2,4-dimethyl sulphide substituting phenol, 0.5g trimethyl silanol behind the reaction 2h, is warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into ethylene pressure to 0.55MPa after being warming up to 85 ℃, adds isoprene 30mL, constant voltage isothermal reaction 2h.
Embodiment 40
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 2.5g four Neodymium trichlorides, dropwise the back and add the 1.5g trimethyl silanol, behind the reaction 2h, be warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into ethylene pressure to 0.55MPa after being warming up to 85 ℃, adds isoprene 30mL, constant voltage isothermal reaction 2h.
Embodiment 41
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add the 2.5g vanadium tetrachloride, dropwise the back and add the 1.5g trimethyl silanol, behind the reaction 2h, be warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into ethylene pressure to 0.55MPa after being warming up to 85 ℃, adds isoprene 30mL, constant voltage isothermal reaction 2h.
Embodiment 42
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stir, add 5g salicylic alidehyde imine titanium (F1) catalyzer, add 1.0g again to methoxybenzenethiol, the 0.5g triethyl silanol, behind the reaction 2h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200mL, MAO solution 35mL (10%wt/v), charge into ethene to 0.45MPa after being warming up to 70 ℃, add vinyl cyanide 10g, constant voltage isothermal reaction 2h.
Embodiment 43
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
2Carrier 5g, toluene 75ml is cooled to-25 ℃, add 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stir, add 5g cyclopentadiene titanous chloride, add 1.0g 2 again, the 6-thiophenol dimethyl benzene, behind the reaction 3h, be warming up to 60 ℃ of isothermal reaction 4h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200mL, MAO solution 35mL (10%wt/v), charge into ethene to 0.45MPa after being warming up to 70 ℃, add cyclopentenes 15g, constant voltage isothermal reaction 2h.
Embodiment 44
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 2.5g four Ytterbium trichlorides, dropwise the back and add the 1.5g trimethyl silanol, behind the reaction 2h, be warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into ethylene pressure to 0.55MPa after being warming up to 85 ℃, adds isoprene 30mL, constant voltage isothermal reaction 2h.
Embodiment 45
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 2.5g four Scium trichlorides, dropwise the back and add the 1.5g trimethyl silanol, behind the reaction 2h, be warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into ethylene pressure to 0.55MPa after being warming up to 85 ℃, adds cyclopentenes 30mL, constant voltage isothermal reaction 2h.
Embodiment 46
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml is cooled to-25 ℃, adds 2M benzylmagnesium chloride (5mL), be warming up to 50 ℃ of reaction 3h, room temperature is washed till no chlorion with toluene and normal hexane, adds toluene 75ml again, stirs, add 2.5g four samarium trichlorides, dropwise the back and add the 1.5g trimethyl silanol, behind the reaction 2h, be warming up to 60 ℃ of isothermal reaction 2h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into ethylene pressure to 0.55MPa after being warming up to 85 ℃, adds vinyl cyanide 20mL, constant voltage isothermal reaction 2h.
Embodiment 47
1) preparation Primary Catalysts: in the reactor of fully replacing, add MgCl successively through nitrogen
25g, toluene 75ml, trimethyl silicon based methylamine 1g, tributyl phosphate 4ml, hexane 8ml, ethanol 3ml is warming up to 80 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Be cooled to-25 ℃, add the 30ml titanium tetrachloride, dropwise the back and add the 1.5g trimethyl silanol, diethoxy propoxy-tert.-butoxy silane 1.5mL, hexane 8ml is behind the reaction 2h, be warming up to 60 ℃, add hexane 8ml, isothermal reaction 2h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 85 ℃, charges into ethylene pressure to 0.55MPa, adds 1-hexene 20mL, constant voltage isothermal reaction 2h.
Embodiment 48
1) preparation Primary Catalysts: in the reactor of fully replacing, add MgCl successively through nitrogen
25g, toluene 75ml, the silica-based amine ethoxylate 1g of triphenyl, tributyl phosphate 4ml, octanol 3ml, white oil 0.2g is warming up to 110 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Be cooled to-25 ℃, add the 30ml titanium tetrachloride, dropwise the back and add the 1.5g trimethyl silanol, diethoxy isopropoxy tert.-butoxy silicon 1.1g behind the reaction 4h, is warming up to 60 ℃ of isothermal reaction 3h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 85 ℃, charges into ethylene pressure to 0.68MPa, adds 1-decene 20mL, constant voltage isothermal reaction 2h.
Embodiment 49
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
25g, toluene 75ml, the silica-based methylamine 1g of triethyl is warming up to 70 ℃, isothermal reaction 1h under stirring; Be cooled to 25 ℃, add 3g cyclopentadienyl titanous chloride, behind the reaction 4h, be warming up to 60 ℃ of isothermal reaction 3h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, toluene wash twice, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: with 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, in still, add main catalyst component 20mg successively, dehydration hexane 200ml, MAO solution 15ml (10wt/v), add 1-hexene 20mL, charge into ethylene pressure to 0.3MPa after being warming up to 65 ℃, constant voltage isothermal reaction 1h.
Embodiment 50
1) preparation Primary Catalysts: in the reactor of fully replacing, add SiO successively through nitrogen
23g, toluene 75ml, the silica-based phenoxy group amine of thricyclohexyl 1g is warming up to 70 ℃, isothermal reaction 1h under stirring; Be cooled to 25 ℃, add 3g double salicylaldehyde imines titanium, the 0.5g trimethyl silanol, behind the reaction 4h, be warming up to 60 ℃ of isothermal reaction 3h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: with 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, in still, add main catalyst component 20mg successively, dehydration hexane 200ml, MAO solution 20ml (10wt/v), add 3-Methyl-1-pentene 20mL, charge into ethylene pressure to 0.3MPa after being warming up to 65 ℃, constant voltage isothermal reaction 1h.
Embodiment 51
1) preparation Primary Catalysts: in the reactor of fully replacing, add MgCl successively through nitrogen
25g, toluene 75ml, epoxy chloropropane 3.5ml, tributyl phosphate 5.5ml, vacuum grease 0.3g, toluene 75ml, ethanol 3.2ml, two (trimethyl silicane) amine 0.5g, dimethyl phonyl silanol 0.5g, octanol 3ml is warming up to 90 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, and constant temperature 1h; Be cooled to-25 ℃, add the 30ml titanium tetrachloride, dropwise the back and add the 0.5g trimethyl silanol, diethoxy isopropoxy tert.-butoxy silicon 2mL behind the reaction 4h, is warming up to 60 ℃ of isothermal reaction 3h, stop to stir, leave standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt
3Solution 1.5ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 85 ℃, charges into ethylene pressure to 0.68MPa, adds 1-hexene 20mL, constant voltage isothermal reaction 2h.MWD＝38。
The results are shown in Table 1.
Table 1
| Embodiment | Transition metal atoms and content thereof (wt%) in the Primary Catalysts | Catalytic efficiency (KgPE/g cat) | Tap density (g/cm 3) | Comonomer | The molar content mol% of comonomer in the polymkeric substance |
| ??1 | ??Ti，5.2 | ??53.4 | ??0.30 | The 1-octene | ??16.4 |
| ??2 | ??Ti.5.1 | ??51.3 | ??0.30 | The 1-hexene | ??18.8 |
| ??3 | ??Ti，5.0 | ??57.9 | ??0.31 | 4-methyl-1-pentene | ??14.6 |
| ??4 | ??Ti，2.1 | ??7.9 | ??0.38 | 3-methyl-1-butene | ??17.8 |
| ??5 | ??Ti，0.8 | ??2.8 | ??0.30 | Isoprene | ??4.1 |
| ??6 | ??Ti，1.8 | ??6.7 | ??0.36 | The 1-amylene | ??19.8 |
| ??7 | ??Ti，1.8 | ??6.0 | ??0.36 | Vinylbenzene | ??18.6 |
| ??8 | ??Ti，1.8 | ??6.6 | ??0.37 | P-methylstyrene | ??20.1 |
| ??9 | ??Zr，1.9 | ??6.5 | ??0.37 | The 1-hexene | ??20.7 |
| ??10 | ??Zr，4.1 | ??45.2 | ??0.38 | Cyclopentenes | ??21.6 |
| ??11 | ??Ti，3.6 | ??45.0 | ??0.32 | Cyclopentenes | ??12.8 |
| ??12 | ??Ti，4.2 | ??44.4 | ??0.33 | Cyclopentenes | ??15.2 |
| Embodiment | Transition metal atoms and content thereof (wt%) in the Primary Catalysts | Catalytic efficiency (KgPE/g cat) | Tap density (g/cm 3) | Comonomer | The molar content mol% of comonomer in the polymkeric substance |
| ??13 | ??Ti.3.4 | ??45.1 | ??0.30 | Cyclopentenes | ??24.6 |
| ??14 | ??Ti，3.5 | ??46.6 | ??0.31 | Cyclopentenes | ??23.4 |
| ??15 | ??Ni，3.4 | ??45.3 | ??0.30 | Cyclopentenes | ??22.3 |
| ??16 | ??Ti，2.1 | ??6.80 | ??0.38 | The 3-Methyl-1-pentene | ??15.8 |
| ??17 | ??Ti，4.0 | ??42.9 | ??0.39 | The 3-Methyl-1-pentene | ??16.2 |
| ??18 | ??Ti，3.9 | ??40.2 | ??0.39 | The 1-octene | ??11.2 |
| ??19 | ??Ti，4.1 | ??43.2 | ??0.38 | The 1-hexene | ??21.5 |
| ??20 | ??Ti，2.0 | ??6.7 | ??0.38 | The 1-hexene | ??16.6 |
| ??21 | ??Ti，4.8 | ??48.3 | ??0.31 | 1-butylene | ??30.6 |
| ??22 | ??Ti，4.9 | ??50.1 | ??0.31 | The 1-octene | ??13.8 |
| ??23 | ??Ti，4.6 | ??48.2 | ??0.32 | ??- | ??- |
| ??24 | ??Ti，4.8 | ??49.3 | ??0.31 | The 1-octene | ??12.1 |
Continuous table 1
| ??25 | ??Ti，4.7 | ??50.1 | ??0.31 | The 1-hexene | ??19.8 |
| ??26 | ??Ti，4.9 | ??50.7 | ??0.32 | 1-hexene 1-octene pentadiene | ??18.8 |
| ??27 | ??Ti，4.0 | ??44.7 | ??0.32 | ??- | ??- |
| ??28 | ??Ti，4.3 | ??41.8 | ??0.32 | Divinyl | ??8.2 |
| ??29 | ??Ti，3.9 | ??46.2 | ??0.29 | Norbornylene | ??5.1 |
| ??30 | ??Ti，3.6 | ??44.3 | ??0.29 | The hydroxyl norbornylene | ??4.2 |
| ??31 | ??Ti，3.7 | ??39.4 | ??0.30 | Methyl methacrylate | ??3.1 |
| ??32 | ??Fe，3.7 | ??38.7 | ??0.30 | Butyl acrylate | ??3.6 |
| ??33 | ??Ti，3.8 | ??32.7 | ??0.30 | Vinyl cyanide | ??5.8 |
| ??34 | ??Ti，3.8 | ??36.5 | ??0.30 | To the vinyl benzene formonitrile HCN | ??5.9 |
| ??35 | ??Ti，4.9 | ??50.8 | ??0.32 | The 1-octene | ??17.8 |
| ??36 | ??Ti，4.8 | ??43.2 | ??0.32 | ??- | ??- |
| ??37 | ??V，3.7 | ??37.2 | ??0.30 | 3-methyl-1-butene | ??8.6 |
| ??38 | ??Nd，3.8 | ??36.4 | ??0.31 | Cyclopentenes | ??9.2 |
| ??39 | ??Nd，3.9 | ??36.8 | ??0.31 | Isoprene | ??4.8 |
| ??40 | ??Nd，3.8 | ??36.7 | ??0.30 | Isoprene | ??6.1 |
| ??41 | ??V，3.8 | ??36.9 | ??0.30 | Isoprene | ??7.2 |
| ??42 | ??Ti，3.7 | ??36.8 | ??0.30 | Vinyl cyanide | ??6.3 |
| ??25 | ??Ti，4.7 | ??50.1 | ??0.31 | The 1-hexene | ??19.8 |
| ??43 | ??Ti，4.0 | ??42.6 | ??0.31 | Cyclopentenes | ??10.2 |
| ??44 | ??Y，3.9 | ??38.5 | ??0.29 | Isoprene | ??16.2 |
| ??45 | ??Sc，4.0 | ??40.2 | ??0.28 | Cyclopentenes | ??15.8 |
| ??46 | ??Sm，4.0 | ??36.8 | ??0.29 | Vinyl cyanide | ??10.2 |
| ??47 | ??Ti，5.2 | ??45.3 | ??0.38 | The 1-hexene | ??14.3 |
| ??48 | ??Ti，5.1 | ??43.8 | ??0.38 | 1-decene | ??7.6 |
| ??49 | ??Ti，2.1 | ??31.2 | ??0.30 | The 1-hexene | ??20.4 |
| ??50 | ??Ti，1.9 | ??28.6 | ??0.30 | The 3-Methyl-1-pentene | ??18.6 |
| ??51 | ??Ti，5.2 | ??50.1 | ??0.31 | The 1-hexene | ??16.1 |
Claims (6)
1. olefin polymerization catalysis is made up of Primary Catalysts and promotor, it is characterized in that: described Primary Catalysts is made up of carrier, transition metal halide, organic alcohol compound, organosilicone compounds and electron donor; The mol ratio of carrier, transition metal halide, organic alcohol compound, organosilicone compounds and electron donor is 1: 0.01-20: 0.1-6: 0.01-5: 0.01-5; Described promotor is an organo-aluminium compound; The transition metal halide in the Primary Catalysts and the mol ratio of promotor are 1: 30-500;
Described electron donor be carbonatoms be 1-20 organic silanol, organosilicon mercaptan compound or organosilicon amine compound one or both or two or more; It is AlR that described promotor organo-aluminium compound is selected from general formula
5 nX
3-nCompound 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, n is the integer of 0＜n≤3.
2. olefin polymerization catalysis according to claim 1 is characterized in that: carrier is meant inorganic oxide carrier, halide carrier or polymer support.
3. olefin polymerization catalysis according to claim 1 is characterized in that: it is M (R that described transition metal halide is selected from general formula
1)
4-mX
mCompound at least a, in the formula, M is Ti, Zr, Hf, Fe, Co, Ni, V, Nd, Y, Sc or Sm; X is a halogen atom, is selected from Cl, Br, F; M is 0 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.
4. olefin polymerization catalysis according to claim 1 is characterized in that: described organosilicone compounds is that general molecular formula is Si (OR
4)
4Organosilicone compounds in one or more, in the formula, R
4For carbonatoms is the alkyl of 1-15, four R
4Identical or different.
5. the preparation method of olefin polymerization catalysis according to claim 1 is characterized in that may further comprise the steps:
1) with carrier at 10-150 ℃, be scattered in the organic solvent, add organic alcohol compound again;
2) under-40-30 ℃, add transition metal halide in the solution that in step 1), obtains, dropwise the back and add organosilicone compounds and electron donor, and be warming up to 40-110 ℃, reacted 0.5-24 hour, in temperature-rise period, particle is separated out and formed to solids gradually, after reaction finishes, adopt toluene or normal hexane washing 4-6 time, filter, vacuum is drained, and obtains main catalyst component;
3) be 1 with Primary Catalysts and promotor by the mol ratio of transition metal halide and promotor: 30-500 mixes, and obtains olefin polymerization catalysis.
6. preparation method according to claim 4 is characterized in that: described organic solvent is selected from toluene, dimethylbenzene, hexane, heptane, octane or decane, or their mixed solvent.
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| CN103613690A (en) * | 2013-11-25 | 2014-03-05 | 北京化工大学 | Olefin polymerization catalyst and preparation method and application thereof |
| JP2016505085A (en) * | 2013-01-30 | 2016-02-18 | 中国石油天然気股▲ふん▼有限公司 | Widely distributed polyolefin catalyst and its production and application |
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