CN103613690A - Olefin polymerization catalyst and preparation method and application thereof - Google Patents
Olefin polymerization catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN103613690A CN103613690A CN201310598556.0A CN201310598556A CN103613690A CN 103613690 A CN103613690 A CN 103613690A CN 201310598556 A CN201310598556 A CN 201310598556A CN 103613690 A CN103613690 A CN 103613690A
- Authority
- CN
- China
- Prior art keywords
- alcohol
- olefin polymerization
- compound
- magnesium halide
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to an efficient olefin polymerization catalyst and a preparation method and application thereof, belonging to the field of olefin polymerization. A main catalyst of the olefin polymerization catalyst is made from a magnesium halide support, a transition metal halide, monohydric alcohol with less than 5 carbon atoms, alcohol with more than 5 carbon atoms, an organosilicon compound, an organophosphorus compound and an organoboron compound, wherein the mole ratio of magnesium halide to the transition metal halide to monohydric alcohol with less than 5 carbon atoms to alcohol with more than 5 carbon atoms to the organosilicon compound to the organophosphorus compound to the organoboron compound is 1: (1-40): (0.01-5): (0.01-10): (0.01-10): (0.01-5): (0.01-5); a cocatalyst of the olefin polymerization catalyst is an organoaluminum compound. Particles of the catalyst disclosed by the invention are good in morphology, are spherical and are not adhered to the wall of a container; the catalyst is high in activity and good in hydrogen regulation performance, the melt index MFR (Melt Flow Rate) of polyethylene is adjustable in the range of 0.1g/10min to 600g/10min, and the bulk density of polyethylene particles is high, so that the catalyst is applicable to slurry-method polymerization, loop-tube polymerization, gas-phase method polymerization or combined polymerization processes.
Description
Technical field
The invention belongs to olefin polymerization catalysis and field of olefin polymerisation, be specifically related to for the equal polymerization of alkene or the catalyzer of copolymerization and the preparation method of catalyzer and application.
Background technology
Olefin polymerization catalysis is the core of polyolefin polymerization technology, development from olefin polymerization catalysis, sum up and mainly contain two aspects: (1) exploitation can be prepared 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, further improving on the basis of catalyst performance, simplify catalyst preparation process, reduce 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 the effort of nearly 30 years, the catalytic efficiency of polyethylene catalysts was the order of magnitude and improves, thereby has simplified polyolefinic production technique, has reduced energy consumption and material consumption.
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 promotor costliness, Primary Catalysts load also has difficulties etc.Therefore, just current industrial production and share of market, traditional Z-N catalyzer will be the 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 hydrogen response, control granules of catalyst regularity and size distribution.In producing at present, need to develop that preparation technology is simple, hydrogen response good, size distribution spherical or class spherical catalyst uniformly.
Patent 96106647.4X discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl
2be dissolved in the mixture of a kind of alcohol and alkane, form liquid MgCl
2alcohol adducts, this liquid MgCl
2alcohol adducts and TiCl
4contact, obtain olefin polymerization catalysis, but the hydrogen regulation performance of catalyzer is poor, and poly melting index MFR can only regulate in 0.1g/10min – 220g/10min.
Patent 200480008242.X discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl
2directly be dissolved in ethanol and prepared solid MgCl
2alcohol adducts, then by TiCl
4load on solid MgCl
2on alcohol adducts, obtained olefin polymerization catalysis.
Patent 201110382706.5 discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl
2be dissolved in the organic solvent of isooctyl alcohol and ethanol and prepared solid MgCl
2alcohol adduct, then by TiCl
4load on solid MgCl
2on alcohol adduct, obtained olefin polymerization catalysis, this catalyzer has good hydrogen to adjust effect.But catalyst activity is on the low side, Primary Catalysts particle easily sticks on wall of container.
Patent CN85100997A, CN200810227369.0, CN200810227371.8, CN200810223088.8 disclose a kind of olefin polymerization catalysis and preparation method thereof, by MgCl
2particle is dissolved in the system of organic epoxy compounds, organo phosphorous compounds and inert organic solvents, obtains MgCl
2solution, then with TiCl
4contact, prepared the Primary Catalysts of olefinic polymerization.The effect of described organo phosphorous compounds is to make MgCl
2a necessary component in the solvent system of grain dissolution.
This patent finds, in catalyst preparation process, adds inert organic solvents, carbonatoms to be less than the alcohol that 5 monohydroxy-alcohol, carbonatoms are greater than 5, MgCl
2after grain dissolution, then add organo phosphorous compounds, silicoorganic compound and organoboron compound, prepare liquid MgCl
2alcohol adduct, then by TiCl
4with this liquid MgCl
2alcohol adduct contact, adds poly-hydroxy solids afterwards again, obtains olefin polymerization catalysis, can improve the particle form of solid main catalyst, the hydrogen regulation performance of catalyst olefinic polymerization, polyolefinic tap density; This patent is found, after magnesium halide carrier dissolves, add again organo phosphorous compounds and organoboron compound, can obviously improve catalyzer catalytic activity and polyolefinic tap density, can eliminate the static of solid main catalyst particle, Primary Catalysts particle does not stick on wall of container.The particle form of olefin polymerization catalysis provided by the present invention is good, and size distribution is even; Catalyzer hydrogen regulation performance is excellent, and poly melting index MFR can regulate in 0.1g/10min – 600g/10min; Catalyst loadings is high, and catalyst activity is high, and solid main catalyst particle does not stick on wall of container; Morphology is good, and tap density is high, and fine powder is few; Be applicable to slurry polymerization processes, endless tube polymerization technique, gas-phase polymerization process or polymerization mix technique; The preparation technology of Primary Catalysts is simple, cost is low, low for equipment requirements, and energy consumption is little, and environmental pollution is little.
Summary of the invention
The object of the present invention is to provide a kind of for olefinic polymerization or ethene (or propylene) with the catalyzer of copolymerization monomer copolymerizable, the application of the preparation method of catalyzer and catalyzer.
Olefinic polymerization provided by the present invention or ethene (or propylene) are comprised of Primary Catalysts and promotor with the catalyzer of copolymerization monomer copolymerizable; Described Primary Catalysts is comprised of magnesium halide carrier, transition metal halide, the monohydroxy-alcohol that is less than C5, the alcohol that is greater than C5, silicoorganic compound, organo phosphorous compounds and organoboron compound.The mol ratio of magnesium halide, transition metal halide, the monohydroxy-alcohol that is less than C5, the alcohol that is greater than C5, silicoorganic compound, organo phosphorous compounds and organoboron compound is: 1:(1-40): (0.01 – 5): (0.01 – 10): (0.01-10): (0.01-5): (0.01 – 5).Of the present invention, aspect one of them, the mass ratio of described poly-hydroxy solids and magnesium halide carrier is (0.05 – 20): 100.Primary Catalysts and promotor with magnitude relation, be: the transition metal halide in Primary Catalysts and the mol ratio of promotor are 1:(10-500).
Wherein, as carrier, to be selected from general formula (1) be Mg (R) to described magnesium halide
ax
bcompound at least one, 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.Specifically be selected from least one 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, 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 one, in formula, M is Ti, Zr, Hf, Fe, Co, Ni etc.; X is halogen atom, is selected from Cl, Br, F; 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 there is C
1～C
10aromatic base.R
1specifically can be selected from: at least one in methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl-, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, o-aminomethyl phenyl, m-aminomethyl phenyl, p-aminomethyl phenyl, o-sulfonic group phenyl, formyl radical, acetyl or benzoyl base etc.Described Ti, Zr, Hf, Fe, Co, the transition metal halides such as Ni, 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.Wherein, preferred titanium tetrachloride.The mol ratio of transition metal halide and magnesium halide is (8-40) preferably: 1.
Wherein, the described monohydroxy-alcohol that is less than C5 is that carbonatoms is less than or equal to 5 fatty alcohol, selects ethanol, methyl alcohol, propyl alcohol, butanols or amylalcohol, preferred alcohol.Be less than the monohydroxy-alcohol of C5 and the mol ratio of magnesium halide preferably (0.05 – 3.5): 1.Add be less than C5 monohydroxy-alcohol especially ethanol can obviously improve the hydrogen regulation performance of catalyzer.
Wherein, the described alcohol that is greater than C5 is that carbonatoms is fatty alcohol or alicyclic ring alcohol or the aromatic alcohol of C6 – C20, preferred fat alcohol, selects enanthol, isooctyl alcohol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alcohol, pentadecanol or hexadecanol in fatty alcohol, preferably isooctyl alcohol.Be greater than the alcohol of C5 and the mol ratio of magnesium halide preferably (1 – 8): 1.
Wherein, described silicoorganic compound meet general formula R
x 3r
y 4si (OR
5)
zand general formula (R
6o) (R
7o) (R
8o) (R
9o) Si, wherein R
3and R
4be respectively alkyl or halogen, R
5, R
6r
7r
8and R
9alkyl or the cyclic hydrocarbon radical of C1 to C20,0≤x <, 2,0≤y < 2, and 0 < z≤4, x+y+z=4.Silicoorganic compound are selected from tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2-ethyl hexyl oxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, n-propyl triethoxyl silane, n-propyl Trimethoxy silane, decyl Trimethoxy silane, decyl triethoxyl silane, cyclopentyl-trimethoxy-silane, cyclopentyl triethoxyl silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, isobutyl triethoxy silane, cyclohexyltriethyloxysilane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, one chlorine Trimethoxy silane, one chlorine triethoxyl silane, ethyl three isopropoxy silane, vinyl three butoxy silanes, trimethyl phenoxysilane, methyl three allyloxy silane, vinyl nitrilotriacetic base silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dibutyl dimethoxy silane, diisopropyl dimethoxy silane, di-isopropyl diethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl methyldiethoxysilane, tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, Cyclohexylmethyldimethoxysilane, methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, two o-tolyl dimethoxy silane, two o-tolyl diethoxy silanes, tolyl dimethoxy silane between two, tolyl diethoxy silane between two, biconjugate tolyl dimethoxy silane, biconjugate tolyl diethoxy silane, trimethylammonium methoxy silane, trimethylethoxysilane, three cyclopentyl methoxy silane, three cyclopentyl Ethoxysilanes, two cyclopentyl-methyl methoxy silane, cyclopentyl dimethyl methyl TMOS, diethoxy isopropoxy tert.-butoxy silane, three isopropoxy tert.-butoxy silane, diisopropoxy two tert.-butoxy silane, diethoxy cyclohexyloxy tert.-butoxy silane, diethoxy phenoxy group tert.-butoxy silane, one oxyethyl group diisopropoxy tert.-butoxy silane, oxyethyl group isopropoxy tert.-butoxy cyclohexyloxy silane, triethoxy methoxyl group silicon, triethoxy pentyloxy silicon, triethoxy hexyloxy silicon, one or more in trimethoxy pentyloxy silicon or triethoxy phenoxy group silicon etc.One or more in preferred tetramethoxy-silicane, tetraethoxysilane, triethoxy methoxyl group silicon, triethoxy pentyloxy silicon or triethoxy hexyloxy silicon.The mol ratio of silicoorganic compound and magnesium halide is (0.5-8): 1.
Described organo phosphorous compounds is selected from least one in the hydrocarbyl carbonate of ortho-phosphoric hydrocarbyl carbonate or phosphorous acid.Concrete as: at least one 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 phosphorous acid benzene methyl.Wherein, preferred ortho-phosphoric acid tri-n-butyl.The mol ratio of organo phosphorous compounds and magnesium halide is (0.01-5): 1.Add organo phosphorous compounds can obviously improve the catalytic activity of catalyzer.
Described organoboron compound is selected from least one in organic boric acid ester, wherein ester group carbonatoms is 1-50, is specifically selected from one or more in trimethyl borate, triethyl borate, tributyl borate, triamyl borate, the own ester of boric acid three, boric acid three heptyl esters, boric acid three monooctyl esters, boric acid ester in three ninth of the ten Heavenly Stems, the different monooctyl ester of boric acid three, boric acid ester in three last of the ten Heavenly stems, boric acid 30 diester etc.The mol ratio of organoboron compound and magnesium halide is (0.01-5): 1.Add organoboron compound can obviously improve catalytic activity, the hydrogen regulation performance of catalyzer, polyolefinic tap density, polyolefinic melting index etc.
Wherein, described poly-hydroxy solids refers to and has polyhydric solid compounds or with the solid-state material of polyol or itself have polyhydric solid-state material.For example, poly-hydroxy solids can be carbonoxide pipe, carbonoxide ball, graphite oxide, silica gel, polymer alumina, poly-hydroxy POSS(polyhedral oligomeric silsesquioxanes), Mierocrystalline cellulose, polysaccharide, chitin etc.In one aspect of the invention, the mass ratio of poly-hydroxy solids and magnesium halide carrier described in described Catalysts for Olefin Polymerization is (0.05 – 20): 100.Wherein, described poly-hydroxy POSS can be dihydroxyl POSS, trihydroxy-POSS, tetrahydroxy POSS, hexahydroxy-POSS or eight hydroxyl POSS etc.; The mass ratio of described poly-hydroxy solids and magnesium halide carrier is (0.05 – 20): 100.
One of feature of the present invention is in the preparation process of solid main catalyst, to add the monohydroxy-alcohol that is less than C5 and the alcohol that is greater than C5, the described alcohol that is less than C5 is that carbonatoms is less than or equal to 5 fatty alcohol, be selected from ethanol, methyl alcohol, propyl alcohol, butanols or amylalcohol, preferred alcohol, is less than the alcohol of C5 and the mol ratio of magnesium halide preferably (0.01 – 5): 1; The described alcohol that is greater than C5 is that carbonatoms is fatty alcohol or alicyclic ring alcohol or the aromatic alcohol of C6 – C20, preferred fat alcohol, in fatty alcohol, select enanthol, isooctyl alcohol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alcohol, pentadecanol or hexadecanol, preferred isooctyl alcohol, described isooctyl alcohol is 2-ethyl-1-hexanol.Be greater than the alcohol of C5 and the mol ratio of magnesium halide preferably (0.01 – 10): 1.Add be less than C5 alcohol especially ethanol can obviously improve the hydrogen regulation performance of catalyzer.
One of feature of the present invention is to add organo phosphorous compounds in the preparation process of solid main catalyst, and described organo phosphorous compounds is selected from least one in the hydrocarbyl carbonate of ortho-phosphoric hydrocarbyl carbonate or phosphorous acid.Concrete as: at least one 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 phosphorous acid benzene methyl, preferably ortho-phosphoric acid tri-n-butyl.The mol ratio of organo phosphorous compounds and magnesium halide is (0.05-5) preferably: 1.Add organo phosphorous compounds can obviously improve the catalytic activity of catalyzer.
One of feature of the present invention is to add organoboron compound in the preparation process of solid main catalyst, in described organoboron compound, ester group carbonatoms is 1-50, is specifically selected from one or more in trimethyl borate, triethyl borate, tributyl borate, triamyl borate, the own ester of boric acid three, boric acid three heptyl esters, boric acid three monooctyl esters, boric acid ester in three ninth of the ten Heavenly Stems, the different monooctyl ester of boric acid three, boric acid ester in three last of the ten Heavenly stems, boric acid 30 diester etc.The mol ratio of organoboron compound and magnesium halide is (0.01-5): 1.Add organoboron compound can obviously improve catalytic activity, the hydrogen regulation performance of catalyzer, polyolefinic tap density, polyolefinic melting index etc.
Another advantage of the present invention is in the preparation process of solid main catalyst, to add poly-hydroxy solids.The present invention is not produced to any restriction, contriver thinks, add poly-hydroxy solids can improve the particle form of solid main catalyst.The present invention is not produced to any restriction, contriver thinks, adds poly-hydroxy solids can eliminate the static of solid main catalyst particle, and the particle non-stick container wall of solid main catalyst is easy to process.Described poly-hydroxy solids is carbonoxide pipe, carbonoxide ball, graphite oxide, silica gel, polymer alumina, poly-hydroxy POSS, Mierocrystalline cellulose, polysaccharide, chitin etc.
The preparation method of olefin polymerization catalysis provided by the present invention comprises the following steps:
1) magnesium halide carrier is scattered in inert organic solvents, adds the monohydroxy-alcohol that is less than C5 and the alcohol that is greater than C5, in 30 to 150 ℃ stirring and dissolving 1 to 5h, preferably 60 ℃ to 130 ℃.
2) by 1) solution is cooled to 10 ℃ to 80 ℃, adds organo phosphorous compounds, silicoorganic compound and organoboron compound, reacts 0.5 to 3h.
3) at-25 to 30 ℃, by step 2) system that obtains contacts with transition metal halide, then add poly-hydroxy solids, and react 0.5-5h at-25 to 30 ℃, again system is warming up to 20-150 ℃, preferably 50-120 ℃, reacts 0.5-5h, in temperature-rise period, solid particulate is separated out gradually, after reaction finishes, with toluene or normal hexane washed product 4-6 time, remove by filter unreacted reactant;
Washed product contacts with transition metal halide, and reacts 0.5-5h at-25 to 30 ℃, then system is warming up to 20-150 ℃, reaction 0.5-5h; Standing, layering, removes by filter unreacted reactant, adopts toluene or hexane washed product; This step repeats 0-4 time;
The mol ratio of transition metal halide and magnesium halide is: (1-40): 1;
Vacuum-drying obtains pulverulent solids Primary Catalysts.Vacuum-drying temperature is 40 ℃ to 130 ℃, preferably 50 ℃ to 100 ℃; The vacuum-drying time is 0.5 hour to 5 hours, preferably 1 hour to 4 hours.Preferably, the mol ratio of wherein said transition metal halide and described magnesium halide can be: (1-40): 1; The mass ratio of described poly-hydroxy solids and magnesium halide carrier is (0.1-10): 100.Preferred, described magnesium halide carrier, transition metal halide, C
1-5monohydroxy-alcohol, be greater than C
5the mol ratio of alcohol, silicoorganic compound, organo phosphorous compounds and organoboron compound be: 1:(1-40): (0.01 – 5): (0.01 – 10): (0.01-10): (0.01-5): (0.01-:5).
The solid main catalyst obtaining is mainly by Mg, Ti, and Cl, C, Si, O, P, B etc. are elementary composition.
Described inert organic solvents is selected from C
5～C
15stable hydrocarbon, C
5～C
10alicyclic hydrocarbon or C
6～C
15aromatic hydrocarbon, preferably decane, octane, dodecane, toluene, dimethylbenzene, hexane, heptane or hexanaphthene, or their mixed solvent.
Olefin polymerization catalysis provided by the present invention also need be comprised of promotor.Described promotor is for common are machine aluminium compound, preferred triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride, methylaluminoxane MAO etc.; The mol ratio of solid main catalyst and promotor is 1:(10-500).
The purposes of olefin polymerization catalysis provided by the present invention is: can be used as that ethylene homo closes, the copolymerization catalyst of the equal polymerization of propylene or ethene (or propylene) and alpha-olefin, comonomer can be one or more, and wherein, described alpha-olefin is selected from C
3～C
20alkene, preferred propylene, 1-butylene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, cyclopentenes, 4-methyl-1-pentene, 1,3-butadiene, isoprene, vinylbenzene, vinyl toluene etc.
Olefin polymerization catalysis provided by the present invention has following beneficial effect:
The particle form of the alpha-olefinic copolymerization catalyzer the object of this invention is to provide is good, spherical in shape, and granules of catalyst does not stick on wall of container; The hydrogen regulation performance of catalyzer is excellent, and poly melting index MFR can regulate in 0.1g/10min – 600g/10min; Catalyst activity is high; Polyolefinic tap density is high; Be applicable to slurry process, gas-phase polymerization process or polymerization mix technique; Preparation method is simple, cost is low, low for equipment requirements, and environmental pollution is little.
The quality percentage composition of ethanol and other alcohol in employing GC mensuration Primary Catalysts.The quality percentage composition of Mg and Ti in employing ICP mensuration Primary Catalysts.Adopt XPS to measure Si in Primary Catalysts, Cl, the quality percentage composition of P and B.The results are shown in Table 1.
The condition determination of the melting index of polyethylene and polyethylene and ethylene copolymers is that testing load is that 5kg, temperature are 190 ℃.Standard sieve is measured fine powder and the macrobead content of polyolefin particles, and it is fine powder that polyolefin particles diameter is less than 200 orders, and being greater than 20 orders is macrobead.The results are shown in Table 3.
The condition determination of the melting index of isotatic polypropylene is that testing load is that 2.16kg, temperature are 230 ℃.
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited only to following embodiment.
Embodiment
Embodiment 1
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 20ml, ethanol 0.2ml, isooctyl alcohol 6.5ml, stirs and is warming up to 120 ℃, reaction 2h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add successively ortho-phosphoric acid tri-n-butyl 2.1ml, tetraethoxysilane 0.15ml and tributyl borate 2.1ml, keeping temperature is 50 ℃ of reaction 2h.System is down at-15 ℃, drips 30ml titanium tetrachloride, then add 0.01 gram, fructose, reaction 1h, is warming up to 110 ℃ and reacts 2h again.Stop stirring, standing, layering, filters, and four times (each 30 milliliters) of hexane washing, in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, non-stick container wall, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 2
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 30ml, ethanol 0.25ml, isooctyl alcohol 7ml, stirs and is warming up to 120 ℃, reaction 2h, solid dissolves the solution that forms homogeneous completely.Be cooled at 60 ℃, add successively ortho-phosphoric acid tri-n-butyl 1.1ml, tetraethoxysilane 0.5ml and tributyl borate 1.0ml, keeping temperature is 60 ℃ of reaction 2h.System is down at-10 ℃, drips 40ml titanium tetrachloride, then add 0.2 gram of tetrahydroxy eight siloxanes, reaction 1h, is warming up to 100 ℃ and reacts 3h again.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 3
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 20ml, ethanol 0.2ml, isooctyl alcohol 8ml, stirs and is warming up to 100 ℃, reaction 2h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add successively the own ester 0.5ml of ortho-phosphoric acid tri-n-butyl 13ml, tetraethoxysilane 2ml and boric acid three, be warming up to 80 ℃ of reaction 2h.System is down at-15 ℃, drips 35ml titanium tetrachloride, then add tetrahydroxy POSS0.2 gram, reaction 1h, is warming up to 65 ℃ and reacts 2h again.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 4
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 20ml, ethanol 2ml, isooctyl alcohol 7ml, stirs and is warming up to 90 ℃, reaction 4h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add successively ortho-phosphoric acid tri-n-butyl 0.5ml, triethoxy methoxy silane 0.5ml and tributyl borate 0.1ml, be warming up to 100 ℃ of reaction 2h.System is down at-15 ℃, drips 15ml titanium tetrachloride, then add eight hydroxyl POSS0.1 gram, reaction 1h, is warming up to 120 ℃ and reacts 2h again.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 80 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 5
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 20ml, ethanol 0.1ml, isooctyl alcohol 4ml, stirs and is warming up to 80 ℃, reaction 5h, solid dissolves the solution that forms homogeneous completely.Be cooled at 40 ℃, add successively ortho-phosphoric acid triethyl 5ml, tetraethoxysilane 4ml and tributyl borate 0.05ml, keeping temperature is 40 ℃ of reaction 2h.System is down at-15 ℃, drips 25ml titanium tetrachloride, then add 0.05 gram of carbonoxide pipe, reaction 3h, is warming up to 110 ℃ and reacts 2h again.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 90 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 6
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 20ml, ethanol 2.5ml, isooctyl alcohol 3ml, stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add successively tributyl phosphate 3ml, tetraethoxysilane 8ml and tributyl borate 10ml, keeping temperature is 50 ℃ of reaction 3h.System is down at-15 ℃, drips 40ml titanium tetrachloride, then add 0.05 gram, carbonoxide ball, reaction 1h, is warming up to 70 ℃ and reacts 2h again.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 100 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 7
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 20ml, isooctyl alcohol 6.5ml and ethanol 0.1ml, stir and be warming up to 60 ℃, reaction 4h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add successively ortho-phosphoric acid triphenylmethyl methacrylate 6ml, triethoxy cyclopentyloxy silane 3ml, ethanol 0.2ml and tributyl borate 3ml, keeping temperature is 50 ℃ of reaction 4h.System is down at-15 ℃, drips 35ml titanium tetrachloride, then add 0.5 gram of graphite oxide, reaction 1h, is warming up to 95 ℃ and reacts 4h again.Stop stirring, standing, layering, filter twice of toluene wash (each 30 milliliters), four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 8
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, dodecane 20ml, ethanol 0.3ml, decyl alcohol 6ml, stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add successively ortho-phosphoric acid tri-n-butyl 6ml, diethoxy isopropoxy tert.-butoxy silane 5ml and tributyl borate 0.5ml, keeping temperature is 50 ℃ of reaction 3h.System is down at-10 ℃, drips 30ml titanium tetrachloride, then add 0.03 gram, silica gel, reaction 1h, is warming up to 80 ℃ and reacts 3h again.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 9
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, toluene 30ml, propyl alcohol 3ml, isooctyl alcohol 6.5ml, stirs and is warming up to 50 ℃, reaction 5h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add ortho-phosphoric acid tri-n-butyl 6ml, tetraethoxysilane 6ml and tributyl borate 0.1ml, keeping temperature is 50 ℃ of reaction 2h.System is down at 0 ℃, drips 15ml titanium tetrachloride, then add 0.05 gram, aluminum oxide, reaction 1h, is warming up to 90 ℃ and reacts 2h again.Stop stirring, standing, layering, filters hexane washed twice (each 30 milliliters).At 0 ℃, in reactor, add n-decane 20ml, be added dropwise to 25ml titanium tetrachloride, reaction 1h, is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 110 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 10
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, octane 30ml, butanols 4ml, isooctyl alcohol 6.5ml, stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add ortho-phosphoric acid tri-n-butyl 2ml, tetraethoxysilane 2ml and tributyl borate 2ml, keeping temperature is 50 ℃ of reaction 2h.System is down at-5 ℃, drips 45ml titanium tetrachloride, then add 0.03 gram of chitin, reaction 1h, is warming up to 90 ℃ and reacts 2h again.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 120 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 11
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 15ml, methyl alcohol 1.5ml, lauryl alcohol 5ml, stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add ortho-phosphoric acid tri-n-butyl 4ml, tetraethoxysilane 6ml and tributyl borate 4ml, keeping temperature is 50 ℃ of reaction 2h.System is cooled to 25 ℃, then is added dropwise in the 25ml titanium tetrachloride of-10 ℃, then add 0.07 gram of modified-cellulose, at 0 ℃ of reaction 1h, in 4 hours, be warming up to 110 ℃ and react again 2h.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 50 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 12
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 40ml, ethanol 0.5ml, isooctyl alcohol 6.5ml, stirs and is warming up to 120 ℃, reaction 2h, solid dissolves the solution that forms homogeneous completely.Be cooled at 60 ℃, add ortho-phosphoric acid tri-n-butyl 3ml, tetraethoxysilane 6ml and tributyl borate 1ml, keeping temperature is 60 ℃ of reaction 2h.System is cooled to 25 ℃, then is added dropwise in the 25ml titanium tetrachloride of-15 ℃, then add 0.2 gram, magnesium chloride, at-5 ℃ of reaction 1h, in 4 hours, be warming up to 100 ℃ and react again 2h.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 50 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 13
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 20ml, ethanol 0.1ml, isooctyl alcohol 6.5ml, stirs and is warming up to 110 ℃, reaction 3h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add ortho-phosphoric acid tri-n-butyl 1ml, tetraethoxysilane 2ml and tributyl borate 0.25ml, at 50 ℃ of temperature, react 2h.System is down at 0 ℃, drips 15ml titanium tetrachloride, reaction 1h, is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, layering, filters hexane washed twice (each 30 milliliters).At 0 ℃, in reactor, add n-decane 20ml, be added dropwise to 25ml titanium tetrachloride, then add 0.1 gram, silica gel, reaction 1h, is warming up to 80 ℃ and reacts 3h again.Stop stirring, standing, layering, filters hexane washed twice (each 30 milliliters).At 0 ℃, in reactor, add n-decane 20ml again, be added dropwise to 25ml titanium tetrachloride, reaction 2h, is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 14
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 20ml, toluene 10ml, ethanol 1ml, isooctyl alcohol 6.5ml, stirs and is warming up to 100 ℃, reaction 4h, solid dissolves the solution that forms homogeneous completely.Be cooled at 40 ℃, add ortho-phosphoric acid tri-n-butyl 0.5ml, tetraethoxysilane 2ml and tributyl borate 0.5ml, be warming up to 70 ℃ of reaction 2h.System is down at-15 ℃, drips 15ml titanium tetrachloride, then add 0.05 gram of trihydroxy-six siloxanes, reaction 1h, is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, layering, filters hexane washed twice (each 30 milliliters).At 0 ℃, in reactor, add n-decane 20ml, be added dropwise to 25ml titanium tetrachloride, reaction 1h, is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 15
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 20ml, ethanol 0.4ml, isooctyl alcohol 6.5ml, stirs and is warming up to 120 ℃, reaction 0.5h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add ortho-phosphoric acid tri-n-butyl 1ml, succinate 15ml tetraethoxysilane 5ml and the different monooctyl ester 0.5ml of boric acid three, keeping temperature is 50 ℃ of reaction 3h.System is down at-15 ℃, drips 15ml titanium tetrachloride, then add 0.15 gram, silica gel, reaction 1h, is warming up to 90 ℃ and reacts 2h again.Stop stirring, standing, layering, filter, hexane washed twice (each 30 milliliters) adds n-decane 20ml at 0 ℃ in 60 ℃ of vacuum-dryings after 2 hours in reactor, be added dropwise to 25ml titanium tetrachloride, reaction 1h, is warming up to 80 ℃ and reacts 2h again and stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 16
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, n-decane 18ml, isooctyl alcohol 8.5ml, stirs and is warming up to 110 ℃, reaction 4h, solid dissolves the solution that forms homogeneous completely.Be cooled at 40 ℃, add ortho-phosphoric acid tri-n-butyl 0.5ml, ethanol 0.25mL, tetraethoxysilane 2ml, tributyl borate 0.35ml, then add 0.05 gram of silicon-dioxide, be warming up to 70 ℃ of reaction 2h.System is down at-15 ℃, drips 15ml titanium tetrachloride, reaction 1h, is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, layering, filters, five times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 17
In the reactor of fully replacing through nitrogen, add 1g mono-chlorobutyl magnesium, n-decane 16ml, isooctyl alcohol 12.5ml, stirs and is warming up to 100 ℃, reaction 3h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add ortho-phosphoric acid tri-n-butyl 0.25ml, ethanol 0.5mL, tetraethoxysilane 5ml, boric acid ester 0.15ml in three ninth of the ten Heavenly Stems, then add 0.03 gram of silicon-dioxide, be warming up to 100 ℃ of reaction 2h.System is down at-15 ℃, drips 25ml dichloro two octyloxy titaniums, reaction 1h, is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 18
In the reactor of fully replacing through nitrogen, add 1g mono-chlorobenzyl base magnesium, n-decane 16ml, isooctyl alcohol 12.5ml, stirs and is warming up to 100 ℃, reaction 3h, solid dissolves the solution that forms homogeneous completely.Be cooled at 60 ℃, add ortho-phosphoric acid tri-n-butyl 0.25ml, ethanol 0.5mL, tetraethoxysilane 5ml, boric acid ester 0.15ml in three last of the ten Heavenly stems, then add 0.03 gram of silicon-dioxide, be warming up to 100 ℃ of reaction 2h.System is down at-15 ℃, drips 35ml trichlorine benzyloxy titanium, reaction 1h, is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, layering, filters, four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Comparative example 1
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, decane 20ml, isooctyl alcohol 16ml, ethanol 0.4ml, stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add ortho-phosphoric acid tri-n-butyl 2ml and tetraethoxysilane 5ml, keeping temperature is 50 ℃ of reaction 2h.System is down at-15 ℃, drips 35ml titanium tetrachloride, reaction 1h, is warming up to 100 ℃ of reaction 2h.Stop stirring, standing, layering, filters, and four times (each 30 milliliters) of hexane washing, in 80 ℃ of vacuum-dryings 2 hours, obtain pulverulent solids Primary Catalysts, and Primary Catalysts particle easily adheres on wall of container.Standing, layering is slow.
Comparative example 2
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, decane 20ml, isooctyl alcohol 16ml, stirs and is warming up to 120 ℃, reaction 3h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add tetraethoxysilane 2ml, ethanol 0.4ml and tributyl borate 0.5ml, keeping temperature is 50 ℃ of reaction 2h.System is down at-15 ℃, drips 15ml titanium tetrachloride, reaction 1h, is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, layering, filters hexane washed twice (each 30 milliliters).At 0 ℃, be added dropwise to 25ml titanium tetrachloride, reaction 1h, is warming up to 80 ℃ of reaction 2h again.Stop stirring, standing, layering, filters, and four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain pulverulent solids Primary Catalysts, and Primary Catalysts particle is fluffy, and tap density is low.
Comparative example 3
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, decane 20ml, isooctyl alcohol 16ml, stirs and is warming up to 120 ℃, reaction 3h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add tetraethoxysilane 2ml and ethanol 0.4ml, keeping temperature is 50 ℃ of reaction 2h.System is down at-15 ℃, drips 15ml titanium tetrachloride, then add 0.05 gram of silicon-dioxide, reaction 1h, is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, layering, filters, and four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain pulverulent solids Primary Catalysts.
Comparative example 4
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, decane 20ml, isooctyl alcohol 16ml, ethanol 0.4ml, stir and be warming up to 120 ℃, reaction 3h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add tetraethoxysilane 2ml, keeping temperature is 50 ℃ of reaction 2h.System is down at-15 ℃, drips 15ml titanium tetrachloride, then add 0.05 gram of silicon-dioxide, reaction 1h, is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, layering, filters, and four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain pulverulent solids Primary Catalysts.
Comparative example 5
In the reactor of fully replacing through nitrogen, add 1g magnesium dichloride, decane 20ml, isooctyl alcohol 16ml, stirs and is warming up to 120 ℃, reaction 3h, solid dissolves the solution that forms homogeneous completely.Be cooled at 50 ℃, add tetraethoxysilane 2ml, keeping temperature is 50 ℃ of reaction 2h.System is down at-15 ℃, drips 15ml titanium tetrachloride, reaction 1h, is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, layering, filters, and four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain pulverulent solids Primary Catalysts.
Application mode one
Vinyl polymerization: 2 liters of stainless steel autoclaves, after nitrogen is fully replaced, are added to main catalyst component component 10mg successively in still, dehydration hexane 1000ml, promotor AlEt
3solution 1.17ml (2mmol/ml), is filled with hydrogen 0.28MPa after being warming up to 75 ℃, then is filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Application mode two
Ethylene copolymerization: 2 liters of stainless steel autoclaves, after nitrogen is fully replaced, are added to main catalyst component 10mg successively in still, dehydration hexane 1000ml, AlEt
3solution 1.17ml (2mmol/ml), adds 20ml1-hexene.Be warming up to after 75 ℃, be filled with hydrogen 0.28MPa, then be filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Application mode three
Propylene polymerization: 2 liters of stainless steel autoclaves, after nitrogen is fully replaced, are added to main catalyst component 10mg successively in still, dehydration hexane 1000ml, AlEt
3solution 1.17ml (2mmol/ml), adds external electron donor triethoxy cyclopentyloxy silicon 10ml (0.18M hexane solution), is warming up to after 80 ℃, is filled with hydrogen 0.1MPa, then is filled with propylene to 3MPa, constant voltage isothermal reaction 2h.Polyacrylic melting index MFR=40.5g/10min, tap density is 0.45g/cm
3.
Olefinic polymerization the results are shown in Table 2.
Mg, Si, phosphorus, boron in table 1 Primary Catalysts, be less than the monohydroxy-alcohol of C5 and be greater than the quality percentage composition of the alcohol of C5
Table 2 olefinic polymerization result
Table 3 polyethylene fine powder and macrobead content and melting index
Note
*: vinyl polymerization condition is hydrogen pressure: ethylene pressure=0.73MPa:0.27MPa, and the condition determination of melting index is that temperature is 190 ℃, loads as 2.16kg.
Claims (10)
1. olefin polymerization catalysis is comprised of Primary Catalysts and promotor, it is characterized in that: described Primary Catalysts is comprised of magnesium halide, transition metal halide, the monohydroxy-alcohol that is less than or equal to C5, the alcohol that is greater than C5, silicoorganic compound, organo phosphorous compounds, organoboron compound and poly-hydroxy solids; Magnesium halide, transition metal halide, the mol ratio that is less than C5 or equals the monohydroxy-alcohol of C5, the alcohol that is greater than C5, silicoorganic compound, organo phosphorous compounds and organoboron compound are: 1:(1-40): (0.01 – 5): (0.01 – 10): (0.01-10): (0.01-5): (0.01-5); The mass ratio of poly-hydroxy solids and magnesium halide carrier is (0.05 – 20): 100; Described promotor is organo-aluminium compound; Transition metal halide in Primary Catalysts and the mol ratio of promotor are 1:(10-500).
2. olefin polymerization catalysis according to claim 1, is characterized in that: it is Mg (R) that described magnesium halide carrier is selected from general formula (1)
ax
bcompound at least one, 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 or 1; B=1 or 2, and a+b=2.
3. olefin polymerization catalysis according to claim 1, is characterized in that: it is M (R that transition metal halide is selected from general formula (2)
1)
4-mx
mcompound at least one, in formula, M is Ti, Zr, Hf, Fe, Co or Ni; X is halogen atom, is selected from Cl, Br, F; 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` is C
1～C
10fatty group or C
1～C
10aromatic base; The mol ratio of transition metal halide and magnesium halide (5-40): 1.
4. olefin polymerization catalysis according to claim 1, it is characterized in that: the described monohydroxy-alcohol that is less than or equal to C5 is that carbonatoms is less than or equal to 5 fatty alcohol or alicyclic ring alcohol, be less than or equal to the monohydroxy-alcohol alcohol of C5 and the mol ratio of magnesium halide for (0.01 – 5): 1.
5. olefin polymerization catalysis according to claim 1, is characterized in that: the described alcohol that is greater than C5 is that carbonatoms is fatty alcohol, alicyclic ring alcohol or the aromatic alcohol of C6 – C20, is greater than the alcohol of C5 and the mol ratio of magnesium halide for (0.01 – 10): 1.
6. olefin polymerization catalysis according to claim 1, is characterized in that: described silicoorganic compound meet general formula R
x 3r
y 4si (OR
5)
zand general formula (R
6o) (R
7o) (R
8o) (R
9o) Si, wherein R
3and R
4be respectively alkyl or halogen, R
5, R
6r
7r
8and R
9alkyl or the cyclic hydrocarbon radical of C1 to C20,0≤x≤2,0≤y≤2, and 0 < z≤4, x+y+z=4; The mol ratio of silicoorganic compound and magnesium halide is (0.01-10): 1.
7. olefin polymerization catalysis according to claim 1, is characterized in that described organo phosphorous compounds is selected from least one in the hydrocarbyl carbonate of ortho-phosphoric hydrocarbyl carbonate or phosphorous acid; The mol ratio of organo phosphorous compounds and magnesium halide (0.01-5): 1.
8. olefin polymerization catalysis according to claim 1, is characterized in that described organoboron compound is selected from least one in organic boric acid ester, and wherein ester group carbonatoms is 1-50, and the mol ratio of organoboron compound and magnesium halide is (0.01-5): 1.
9. the preparation method of olefin polymerization catalysis according to claim 1, is characterized in that: comprise the following steps:
1) magnesium halide carrier is scattered in inert organic solvents, adds the monohydroxy-alcohol that is less than or equal to C5 and the alcohol that is greater than C5, at 50 ℃ to 150 ℃, stirring and dissolving 1 is to 5h;
2) by 1) solution is cooled to 10 ℃ to 80 ℃, adds organo phosphorous compounds, silicoorganic compound and organoboron compound, reacts 0.5 to 3h;
3) at-25 to 30 ℃, by step 2) system that obtains contacts with transition metal halide, and add poly-hydroxy solids, at-25 to 30 ℃, react 0.5-5h, then system is warming up to 20-150 ℃, reaction 0.5-5h; Standing, layering, removes by filter unreacted reactant, adopts toluene or hexane washed product;
Washed product contacts with transition metal halide, and reacts 0.5-5h at-25 to 30 ℃, then system is warming up to 20-150 ℃, reaction 0.5-5h; Standing, layering, removes by filter unreacted reactant, adopts toluene or hexane washed product, and this step repeats 0-4 time;
The mol ratio of transition metal halide and magnesium halide is: (1-40): 1;
Vacuum-drying obtains pulverulent solids Primary Catalysts;
Wherein, described inert organic solvents is selected from C
5～C
15stable hydrocarbon, C
5～C
10alicyclic hydrocarbon or C
6～C
15aromatic hydrocarbon or their mixed solvent;
Wherein, described poly-hydroxy solids is carbonoxide pipe, carbonoxide ball, graphite oxide, silica gel, polymer alumina, poly-hydroxy POSS, Mierocrystalline cellulose, polysaccharide, chitin; The mass ratio of described poly-hydroxy solids and magnesium halide carrier is (0.05 – 20): 100.
10. the application of olefin polymerization catalysis according to claim 1, it is characterized in that: described olefin polymerization catalysis is the catalyzer of the copolymerization of vinyl polymerization, propylene polymerization, ethene and alpha-olefin or the copolymerization of propylene and alpha-olefin, wherein, described alpha-olefin is selected from C
3～C
20alkene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310598556.0A CN103613690A (en) | 2013-11-25 | 2013-11-25 | Olefin polymerization catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310598556.0A CN103613690A (en) | 2013-11-25 | 2013-11-25 | Olefin polymerization catalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103613690A true CN103613690A (en) | 2014-03-05 |
Family
ID=50164417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310598556.0A Pending CN103613690A (en) | 2013-11-25 | 2013-11-25 | Olefin polymerization catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103613690A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829761A (en) * | 2015-04-30 | 2015-08-12 | 北京化工大学 | Olefin efficient polymerization catalyst, and preparation method and application thereof |
| CN104829758A (en) * | 2015-05-17 | 2015-08-12 | 北京化工大学 | Alkene polymerization catalyst as well as preparation method and application thereof |
| CN104829760A (en) * | 2015-04-30 | 2015-08-12 | 北京化工大学 | Olefin polymerization catalyst, and preparation method and application thereof |
| CN108690153A (en) * | 2018-04-13 | 2018-10-23 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst, preparation method and application thereof |
| CN110483247A (en) * | 2019-07-16 | 2019-11-22 | 北京国达恒泰科贸有限责任公司 | Metal alkoxides powder and preparation method and application |
| US10927195B2 (en) | 2018-02-11 | 2021-02-23 | Petrochina Company Limited | Olefin coordination polymerization catalyst and use thereof |
| US11014994B2 (en) | 2016-05-04 | 2021-05-25 | Petrochina Company Limited | Olefin coordination polymerization catalyst, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845104A (en) * | 2010-05-21 | 2010-09-29 | 北京化工大学 | Olefin polymerization catalyst and preparation method thereof |
| CN102464733A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, preparation method thereof and olefin polymerization method |
| CN102492061A (en) * | 2011-11-26 | 2012-06-13 | 北京化工大学 | Alkene polymerization catalyst, preparation method thereof, and application thereof |
| CN102993344A (en) * | 2011-09-13 | 2013-03-27 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, and catalyst thereof |
| CN103073662A (en) * | 2013-01-29 | 2013-05-01 | 北京化工大学 | Olefin polymerization catalyst, and preparation method and application of catalyst |
-
2013
- 2013-11-25 CN CN201310598556.0A patent/CN103613690A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845104A (en) * | 2010-05-21 | 2010-09-29 | 北京化工大学 | Olefin polymerization catalyst and preparation method thereof |
| CN102464733A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, preparation method thereof and olefin polymerization method |
| CN102993344A (en) * | 2011-09-13 | 2013-03-27 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, and catalyst thereof |
| CN102492061A (en) * | 2011-11-26 | 2012-06-13 | 北京化工大学 | Alkene polymerization catalyst, preparation method thereof, and application thereof |
| CN103073662A (en) * | 2013-01-29 | 2013-05-01 | 北京化工大学 | Olefin polymerization catalyst, and preparation method and application of catalyst |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829761A (en) * | 2015-04-30 | 2015-08-12 | 北京化工大学 | Olefin efficient polymerization catalyst, and preparation method and application thereof |
| CN104829760A (en) * | 2015-04-30 | 2015-08-12 | 北京化工大学 | Olefin polymerization catalyst, and preparation method and application thereof |
| CN104829760B (en) * | 2015-04-30 | 2017-06-27 | 北京化工大学 | A kind of olefin polymerization catalysis and preparation method and application |
| CN104829761B (en) * | 2015-04-30 | 2017-06-27 | 北京化工大学 | Alkene catalyst structure and preparation method and application |
| CN104829758A (en) * | 2015-05-17 | 2015-08-12 | 北京化工大学 | Alkene polymerization catalyst as well as preparation method and application thereof |
| US11014994B2 (en) | 2016-05-04 | 2021-05-25 | Petrochina Company Limited | Olefin coordination polymerization catalyst, and preparation method and application thereof |
| US10927195B2 (en) | 2018-02-11 | 2021-02-23 | Petrochina Company Limited | Olefin coordination polymerization catalyst and use thereof |
| CN108690153A (en) * | 2018-04-13 | 2018-10-23 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst, preparation method and application thereof |
| CN108690153B (en) * | 2018-04-13 | 2021-03-30 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst, preparation method and application thereof |
| CN110483247A (en) * | 2019-07-16 | 2019-11-22 | 北京国达恒泰科贸有限责任公司 | Metal alkoxides powder and preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073662B (en) | Olefin polymerization catalyst, and preparation method and application of catalyst | |
| CN102911299B (en) | High-activity olefin polymerization catalyst, preparation method and application | |
| CN103613690A (en) | Olefin polymerization catalyst and preparation method and application thereof | |
| CN102492061B (en) | Alkene polymerization catalyst, preparation method thereof, and application thereof | |
| CN102112431B (en) | Internal donor for olefin polymerization catalysts | |
| CN102875704B (en) | Olefin polymerization catalyst, preparation method and application thereof | |
| CN102762602B (en) | New internal and external donor compounds for olefin polymerization catalysts | |
| CN104829760A (en) | Olefin polymerization catalyst, and preparation method and application thereof | |
| CN102834420B (en) | Internal and external donor compounds for olefin polymerization catalysts ii | |
| CN104829758B (en) | Olefin polymerization catalysis and preparation method and application | |
| CN104356257A (en) | Preparation method and applications of alkoxyl magnesium carrier | |
| CN104583244B (en) | Catalyst for olefines polymerizing and preparation method thereof | |
| CN102558404B (en) | Polyol ether polyolefin catalyst and preparation and application thereof | |
| CN104080824A (en) | Internal electron donor for olefin polymerization catalysts, method of making and using the same | |
| CN104903359A (en) | Process of polymerization catalyst production with controlled catalyst properties and use of same in olefin polymerizations | |
| CN101880342B (en) | Olefin polymerization catalyst, preparation and application thereof | |
| CN103183754A (en) | Olefin polymerization catalyst and preparation method thereof | |
| CN103113500B (en) | Alkene coordination polymerization catalyst as well as preparation method and application thereof | |
| CN104053682B (en) | For the high activity catalyst component and its application method of olefinic polymerization | |
| CN101891849B (en) | Polyolefin catalyst and preparation and application thereof | |
| CN102558403B (en) | Glycol ether polyolefin catalyst and preparation and application thereof | |
| CN101565478A (en) | Ethylene copolymerization catalyst | |
| CN101885793B (en) | Ethylene polymerization catalyst, preparation and application thereof | |
| CN101845104B (en) | Olefin polymerization catalyst and preparation method thereof | |
| CN101885795B (en) | Electron donor catalyst, preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140305 |