CN1258680A - Catalyst to make the isotactic degree of polypropylene easy to regulate, the preparation of its active component and its application - Google Patents
Catalyst to make the isotactic degree of polypropylene easy to regulate, the preparation of its active component and its application Download PDFInfo
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- CN1258680A CN1258680A CN 98126383 CN98126383A CN1258680A CN 1258680 A CN1258680 A CN 1258680A CN 98126383 CN98126383 CN 98126383 CN 98126383 A CN98126383 A CN 98126383A CN 1258680 A CN1258680 A CN 1258680A
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Abstract
The active component of the catalyst is prepared by forming homogeneous solution through dissolving magnesium halide in organic epoxide and organic phosphide, mixing the solution with titanium tetrahalide to separate solid matter in the presence of separation assistant, and treating the solid matter first with polyhydric carboxylic ester as inner electron donor and then with titanium tetrahalide and inert diluent. During polymerization, through the synergistic effect of different outer electron donor and the said inner electron donor, can be produced polypropylene with isotactic degree capable of being regulated in 91-99%.
Description
The present invention relates to a kind of catalyzer and method for making and this Application of Catalyst that the olefin polymer degree of isotacticity is easily transferred, more particularly, relate to a kind of method for making and this Application of Catalyst that makes easy catalyzer of transferring of polypropylene degree of isotacticity and active constituent thereof.
Early eighties, Mitsui oiling and U.S. Xi Mengte (Himont) company have developed preparation polyacrylic liquid-phase bulk polymerization caldron process technology (Hypol) and liquid-phase bulk polymerization endless tube Technology (Spheripol) in succession, the former adopts TK type high-effective carrier catalyst, and the latter then adopts GF-2A or FT4S catalyzer respectively according to the resin trade mark of producing different products.The polypropylene production technology of Chinese large-sized is mainly introduced the technology of above two companies, and the catalyzer that is adopted is also introduced thereupon.Mid-1980s, the research of the N-of Beijing Chemical Research Institute catalyzer successfully makes the polypropylene plant of China go on the road of catalyzer production domesticization.
Chinese patent 85100997 (N-catalyzer) discloses a kind of catalyst system that is used for olefinic polymerization and copolymerization, this catalyst system comprises: (first) contains the ingredient of solid catalyst of Ti, (second) alkylaluminium cpd, (the third) three kinds of components of silicoorganic compound, wherein (first) component is to be dissolved in organic epoxy compounds and organo phosphorous compounds forms homogeneous solution by magnesium halide, this solution mixes with the titanium tetrahalide or derivatives thereof, in the presence of compounds such as precipitation additive such as organic acid anhydrides, organic acid, ether, ketone, separate out solids; This solids is handled with the multi-carboxylate, and it is attached on the solids, handles with titanium tetrahalide and inert diluent and obtains.When this catalyst system is used for propylene polymerization, has very high activity, and active decline is little when prolonging polymerization time, the polymkeric substance apparent density is big, tacticity is very high, and when melting index increases, tacticity descends very little, exploitation for the spinning series products has unique advantages, but the shortcoming of this catalyst system is higher with the degree of isotacticity of the acrylic resin of this Catalyst Production, reach 99.5%, and be not easy to regulate, acrylic resin for different purposes, desired polyacrylic degree of isotacticity difference then requires degree of isotacticity height (should greater than 98%) for fiber-grade pp resin, and the film series products resin trade mark then requires relatively low degree of isotacticity (being generally about 94%), therefore this catalyzer is not suitable for developing the acrylic resin of more trades mark, especially is unsuitable for developing resins such as film grade resins or flat filament.Though and several catalyzer above-mentioned such as TK type catalyzer degree of isotacticity are lower, be difficult for regulating, and the particle shape of GF-2A catalyzer to be very not regular yet, FT4S Preparation of catalysts technology is comparatively complicated.
As everyone knows, the kind of internal electron donor and external electron donor, consumption and the mutual coupling between the two have very big influence for the degree of isotacticity of polymkeric substance.In disclosed all embodiments of Chinese patent 85100997 specification sheetss, the synthetic internal electron donor that all adopts of catalyzer is diisobutyl phthalate (DIBP) or n-butyl phthalate (DNBP), its consumption is ester/Mg (mol)=0.2, external electron donor all adopts dimethoxydiphenylsilane and above-mentioned internal electron donor to be complementary during polymerization, make the polypropylene degree of isotacticity of gained higher, and be difficult for regulating, simultaneously because the existence of phenyl, make the phenyl that can contain trace in the polymkeric substance of gained, cause certain pollution, therefore limited the application of this polymkeric substance.
Having selected not contain the external electron donor of phenyl and internal electron donor diisobutyl phthalate and n-butyl phthalate in the present invention is complementary, produce synergistic effect, and the ratio of in a big way, regulating Al/Si in aluminum alkyls and the external electron donor, therefore solved the problem of above-mentioned existence, made polyacrylic degree of isotacticity adjustable within the specific limits.
The objective of the invention is in order to overcome in the above-mentioned prior art, the shortcoming of the higher and difficult adjusting of polymkeric substance degree of isotacticity, a kind of catalyzer that the propene polymer degree of isotacticity is easily transferred is provided, wherein catalyst activity component is to be dissolved in organic epoxy compounds and organo phosphorous compounds forms homogeneous solution by magnesium halide, this solution mixes with the titanium tetrahalide or derivatives thereof, in the presence of precipitation additive, separate out solids, this solids is handled with the internal electron donor multi-carboxylate, it is attached on the solids, handle with titanium tetrahalide and inert diluent again and obtain, in polymerization process, adopt different external electron donors and the internal electron donor multi-carboxylate in the above-mentioned active constituent to be complementary, produce synergistic effect, the polyacrylic degree of isotacticity of being produced can be regulated between 99%～91%, especially can develop the lower product of degree of isotacticity being suitable for the needs of various different purposes trade mark resins, and the efficient of catalyzer and polyacrylic bulk density are remained unchanged.
Second purpose of the present invention provides a kind of preparation method of catalyst activity component of the present invention.
The 3rd purpose of the present invention provides the application of catalyzer of the present invention in propylene polymerization or copolymerization.
The present invention is used for the catalyzer of propylene polymerization or copolymerization, it is characterized in that, comprises following component:
A, titaniferous solid catalytic ingredient, its be by magnesium halide be dissolved in by organic epoxy compounds and
In the solvent system that organo phosphorous compounds and inert diluent are formed, form behind the homogeneous solution with four
The halogenated titanium or derivatives thereof mixes, and in the presence of precipitation additive, separates out solids; This solids
Handle with the multi-carboxylate, it is attached on the solids, again with titanium tetrahalide and inertia dilution
Agent is handled and is obtained, and wherein precipitation additive is a kind of in organic acid anhydride, organic acid, ether, the ketone,
The mol ratio of multi-carboxylate and magnesium halide is 0.03～0.25;
B, general formula are AlR
nX
3-nAlkylaluminium cpd, R is that hydrogen or carbonatoms are 1～20 in the formula
Alkyl;
C, R
nSi (OR)
4-n, 0≤n in the formula≤3, R and R ' they are alkyl or cycloalkyl of the same race or not of the same race;
Ratio between component B and the component A is 5～1000 with the molar ratio computing of aluminium and titanium,
Ratio between component B and the component C is 1～400 with the molar ratio computing of aluminium and silicon.
The described magnesium halide of catalyst component A of the present invention comprises that one of them halogen atom is by alkyl or halogen-oxyl institute metathetical derivative in complex compound, the magnesium dihalide molecular formula such as the water, alcohol of magnesium dihalide, magnesium dihalide, above-mentioned magnesium dihalide is specially magnesium dichloride, dibrominated magnesium, two magnesium iodides, is preferably magnesium dichloride.
The described organic epoxy compounds of catalyst component A of the present invention comprises that carbonatoms is at compounds such as the oxide compound of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine, glycidyl ether, inner ethers.Particular compound as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF) are preferably epoxy chloropropane.
The described organo phosphorous compounds of catalyst component A of the present invention comprises the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, phosphorous acid benzene methyl are preferably the ortho-phosphoric acid tri-n-butyl.
The described inert diluent of catalyst component A of the present invention can adopt hexane, heptane, octane, benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound.
The halogenide or derivatives thereof of the described transition metal Ti of catalyst component A of the present invention is meant that general formula is TiXn (OR)
4-n,=1～4, concrete as: titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium.In every mole of magnesium halide, the add-on of the halogenide or derivatives thereof of transition metal Ti is 0.5～150 mole, with 1～20 mole for well, be preferably titanium tetrachloride.
The described precipitation additive of catalyst component A of the present invention is selected from a kind of in organic acid, organic acid anhydride, organic ether, the organic ketone or their mixture.Concrete as: diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether.In every mole of magnesium halide, the add-on of precipitation additive is 0.03～1.0 mole, with 0.05～0.4 mole for well.
The described internal electron donor multi-carboxylate of catalyst component A of the present invention is selected from a kind of among aliphatics multi-carboxylate and the aromatic series multi-carboxylate.Concrete as: diethyl malonate, butyl ethyl malonate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, the phthalic ester diisobutyl ester, the phthalic ester di-n-butyl, the phthalic ester di-isooctyl, diethyl maleate, maleic acid n-butyl, the naphthalene dicarboxylic acids diethyl ester, the naphthalene dicarboxylic acids dibutylester, triethyl trimellitate, tributyl trimellitate, the benzene-1,2,3-tricarboxylic acid triethyl, the benzene-1,2,3-tricarboxylic acid tri-n-butyl, the pyromellitic acid tetra-ethyl ester, pyromellitic acid four fourths etc. are preferably the phthalic ester diisobutyl ester, the phthalic ester di-n-butyl.In every mole of magnesium halide, multi-carboxylate's add-on is 0.03～0.25 mole, is preferably 0.05～0.2 mole, is preferably 0.07～0.12 mole.
The described organo-aluminium compound of catalyst component B of the present invention, its general formula is AlR
nX
3-n, R is a hydrogen in the formula, carbonatoms is 1～20 alkyl, particularly alkyl, aralkyl, aryl; X is halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Particular compound is as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichloride, wherein with triethyl aluminum, triisobutyl aluminium for well.
The described R of catalyst component C of the present invention
nSi (OR)
4-n0≤n in the formula≤3, R and R ' are alkyl or cycloalkyl of the same race or not of the same race, concrete as: trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methylcyclohexyl dimethoxy silane, dibutyl dimethoxy silane are preferably methylcyclohexyl dimethoxy silane, dibutyl dimethoxy silane.
In catalyst system of the present invention, among the component B among aluminium and the component A mol ratio of titanium be 5～1000, with 100～800 for well; Ratio between component B and the component C is 1～400 with the molar ratio computing of aluminium and silicon, with 25～250 for well.
The preparation method of catalyst activity component A of the present invention is: under agitation magnesium halide is dissolved in the solvent system of being made up of organic epoxy compounds, organo phosphorous compounds and inert diluent, form homogeneous transparent solution, solvent temperature is 0～100 ℃, is preferably 30～70 ℃; In the presence of precipitation additive, under-35～60 ℃ of temperature, be preferably-30～5 ℃; Titanium compound is splashed into the magnesium halide homogeneous solution or magnesium halide solution is splashed in the titanium compound, and after separating out preceding or separate out, solids to add the multi-carboxylate, so that will be handled, the multi-carboxylate can partly be attached on the solids to the solids of separating out; Reaction mixture is warming up to 60～110 ℃ then, suspension was stirred under this temperature 10 minutes～10 hours, stop to stir the back solids and from mixture solution, separate out, filter, remove mother liquor, wash solids with inert diluent, make titaniferous solid catalytic ingredient A.
Catalyst A of the present invention, B, C component can directly apply to polymerization system, also can be applied to polymerization system after the pre-earlier complexing.
Catalyzer of the present invention can be used for the equal polymerization of propylene or the copolymerization of propylene and alpha-olefin, and alpha-olefin can adopt ethene, butylene, amylene, hexene, octene, 4-methylpentene-1.Liquid polymerization can be adopted during polymerization, also vapour phase polymerization can be adopted.
Having selected not contain the external electron donor of phenyl and internal electron donor diisobutyl phthalate and n-butyl phthalate in the present invention is complementary, produce synergistic effect, and in a big way, regulate aluminum alkyls and, make the polypropylene degree of isotacticity adjustable within the specific limits outward to the ratio of Al/Si in the electronics.For example: select different internal electron donor multi-carboxylates' dosage in the catalyzer of the present invention, with multi-carboxylate/MgCl
2Mol ratio change 0.2,0.11,0.074 into, in polymerization process, adopt external electron donor CHMMS, and regulate its dosage, Al/Si (mol) is regulated in 25,50,100,150,200,250, reduction along with lactone content, the reduction of silicone content, polyacrylic degree of isotacticity descend obviously, promptly when ester/Mg=0.2, Al/Si is than rising at 250 o'clock from 25, and degree of isotacticity reduces to 94% from 99%; When ester/Mg=0.11, Al/Si rises at 200 o'clock from 25, and degree of isotacticity reduces to 94% from 98%; And when ester/Mg=0074, Al/Si rises at 200 o'clock from 25, and degree of isotacticity drops to 87% from 97.5%.
When selecting for use internal electron donor and external electron donor DBMS (dibutyl dimethoxy silane) when being complementary, to work as DIBP/Mg=0.11, Al/Si rises at 200 o'clock from 25, and degree of isotacticity reduces to 92% from 98.5%; And when DNBP/Mg=0.11, Al/Si rises at 200 o'clock, degree of isotacticity from 97.5% to 90% from 25.
In Comparative Examples, adopt internal electron donor diisobutyl phthalate and external electron donor dimethoxydiphenylsilane to be complementary, when ester/Mg=0.2, Al/Si rises at 130 o'clock than from 25, degree of isotacticity reduces to 81% from 99%, even it is lower, polymer performance is relatively poor, and big like this fall is difficult to be used for the degree of isotacticity of telomerized polymer in actual applications.
In sum, the inside and outside electron donor that catalyzer of the present invention matches each other by use, and the ratio of regulating aluminum alkyls and giving Al/Si in the electronics outward, thereby reach the purpose of telomerized polymer degree of isotacticity, polyacrylic degree of isotacticity can be regulated between 94-99%, and kept other premium properties, and the efficient height of catalyzer for example, the tap density of polymkeric substance is big.Owing to adopted the external electron donor that does not contain phenyl, make polymkeric substance not have pollution problem simultaneously, widened the Application Areas of polymkeric substance.
Embodiment
Embodiment 1.
1, the preparation of (A) component in the catalyst system
In through the abundant metathetical reactor of high pure nitrogen, add magnesium chloride 4.8g (0.05mol) successively, toluene 85ml, epoxy chloropropane ECP 7.8ml (0.1mol), tributyl phosphate TBP8.2ml (0.03mol), rise to 50 ℃ under stirring, and kept 2.5 hours, treat that solid dissolves fully after, add Tetra hydro Phthalic anhydride 1.2g, continued to keep 1 hour, and solution was cooled to below-25 ℃, drip TiCl in 1 hour
456ml slowly is warming up to 80 ℃, gradually solids is separated out, and add internal electron donor n-butyl phthalate (DNBP) 2.7ml, and keep 80 ℃, 1 hour, behind the heat filtering, add toluene 100ml, the washing secondary obtains pale brown look solid.Add toluene 60ml, TiCl
440ml handled 2 hours for 90 ℃, removed filtrate, and re-treatment once.Add toluene 100ml, be warmed up to 110 ℃, carry out three washings, the time respectively is 10 minutes, adds hexane 100ml again, and the washing secondary gets solids 6.3g (A component).The A component contains Ti1.57wt%, Mg17.5wt%, chlorine 58.9wt%, DNBP10.3wt%.
2. polymerization
Volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt
30.0025mol methylcyclohexyl dimethoxy silane (CHMMS) 0.0001mol makes Al/S[(mol)=25, add above-mentioned solid A component 10mg and 0.4NL hydrogen again, feed liquid propene 2.5L, be warming up to 70 ℃, kept this temperature 2 hours.Pressure is put in cooling, and discharging gets the PP resin.The results are shown in Table 1:
Embodiment 2
Adopt the catalyst A component among the embodiment 1 to carry out propylene polymerization, external electron donor methylcyclohexyl dimethoxy silane (CHMMS) amount reduces, and makes Al/Si (mol)=50, and all the other the results are shown in Table 1 with embodiment 1:
Embodiment 3
External electron donor methylcyclohexyl dimethoxy silane (CHMMS) among the embodiment 1 amount is reduced, make Al/Si (mol)=100, all the other are with embodiment 1.The results are shown in Table 1:
Embodiment 4
External electron donor methylcyclohexyl dimethoxy silane (CHMMS) among the embodiment 1 amount is reduced, make Al/Si (mol)=150, all the other are with embodiment 1.The results are shown in Table 1:
Embodiment 5
External electron donor methylcyclohexyl dimethoxy silane (CHMS) among the embodiment 1 amount is reduced, make Al/Si (mol)=200, all the other are with embodiment 1.The results are shown in Table 1:
Embodiment 6
External electron donor methylcyclohexyl dimethoxy silane (CHMMS) among the embodiment 1 amount is reduced, make Al/Si (mol)=250, all the other are with embodiment 1.The results are shown in Table 1:
Table 1, the normal influence of external electron donor CHMMS consumption equity.
DNBP/Mg(mol)＝0.2
| Embodiment | ???Al/Si ???(mol) | Cat efficient Kgpp/gCat | ???TII％ | MI g/10 minute | ????BD ????g/ml |
| Example 1 | ????25 | ?????42.0 | ???98.8 | ????3.2 | ????0.45 |
| Example 2 | ????50 | ?????45.0 | ???98.1 | ????4.0 | ????0.44 |
| Example 3 | ????100 | ?????42.0 | ???97.5 | ????4.1 | ????0.44 |
| Example 4 | ????150 | ?????47.0 | ???96.5 | ????4.9 | ????0.44 |
| Example 5 | ????200 | ?????47.0 | ???96.0 | ????6.8 | ????0.44 |
| Example 6 | ????250 | ?????42.0 | ???93.5 | ????12.0 | ????0.42 |
Comparative Examples 1
Adopt the catalyst component A of example 1 to carry out propylene polymerization, external electron donor adopts dimethoxydiphenylsilane (DPMS), makes Al/Si (mol)=25, and other condition the results are shown in contrast table 1 with example 1.
Comparative Examples 2～7
Only Al/Si (mol) is changed into 50,70,100,110,120,130, other condition the results are shown in contrast table 1 with example 1.
Contrast table 1: the normal influence of external electron donor DPMS consumption equity
DNBP/Mg(mol)＝0.2
| Comparative Examples | ???Al/Si ???(mol) | Cat efficient Kgpp/gCat | ????TII％ | ????BD ????g/ml |
| Comparative Examples 1 | ????25 | ??????57.6 | ????98.2 | ????0.46 |
| Comparative Examples 2 | ????50 | ??????60.6 | ????98.1 | ????0.45 |
| Comparative Examples 3 | ????70 | ??????55.2 | ????97.8 | ????0.46 |
| Comparative Examples 4 | ????100 | ??????48.1 | ????97.3 | ????0.45 |
| Comparative Examples 5 | ????110 | ??????42.3 | ????81.6 | Can't survey |
| Comparative Examples 6 | ????120 | ??????48.0 | ????81.6 | Can't survey |
| Comparative Examples 7 | ????130 | ??????44.0 | Sticking, do not survey | Can't survey |
Embodiment 7
In the preparation with A component among the embodiment 1, add internal electron donor n-butyl phthalate (DNBP) 1.5ml, make ester/Mg=0.11, all the other are all with embodiment 1.The A component contains Ti1.51%, Mg17.5%, chlorine 58.2%, DNBP12.3%.
2. polymerization
With embodiment 1.The results are shown in Table 2:
Embodiment 8
Adopt the catalyst A component among the embodiment 7 to carry out propylene polymerization, external electron donor methylcyclohexyl dimethoxy silane (CHMMS) amount reduces, and makes Al/Si (mol)=50, and all the other the results are shown in Table 2 with embodiment 7:
Embodiment 9
Adopt the catalyst A component among the embodiment 7 to carry out propylene polymerization, external electron donor methylcyclohexyl dimethoxy silane (CHMMS) amount reduces, and makes Al/Si (mol)=100, and all the other the results are shown in Table 2 with embodiment 7:
Embodiment 10
Adopt the catalyst A component among the embodiment 7 to carry out propylene polymerization, external electron donor methylcyclohexyl dimethoxy silane (CHMMS) amount reduces, and makes Al/Si (mol)=150, and all the other the results are shown in Table 2 with embodiment 7:
Embodiment 11
Adopt the catalyst A component among the embodiment 7 to carry out propylene polymerization, external electron donor methylcyclohexyl dimethoxy silane (CHMMS) amount reduces, and makes Al/Si (mol)=200, and all the other the results are shown in Table 2 with embodiment 7:
Table 2, the normal influence of external electron donor CHMMS consumption equity.
DNBP/Mg(mol)＝0.11
| Embodiment | ??Al/Si ??(mol) | Cat efficient Kgpp/gCat | ???TII％ | MI g/10 minute | ????BD ????g/ml |
| Example 7 | ???25 | ?????42.0 | ???97.9 | ????1.5 | ????0.44 |
| Example 8 | ???50 | ?????43.0 | ???97.4 | ????6.1 | ????0.44 |
| Example 9 | ???100 | ?????45.0 | ???97.0 | ????7.5 | ????0.44 |
| Example 10 | ???150 | ?????44.0 | ???96.2 | ????8.1 | ????0.44 |
| Example 11 | ???200 | ?????41.0 | ???93.5 | ????13.9 | ????0.42 |
Embodiment 12
1, in the preparation with A component among the embodiment 1, add internal electron donor n-butyl phthalate (DNBP) 1.0ml, make ester/Mg=0.074, all the other are all with embodiment 1.The A component contains Ti1.35%, Mg18.2%, chlorine 59.5%, DNBP9.1%.
2. polymerization
With embodiment 1.The results are shown in Table 3:
Embodiment 13
Adopt the catalyst A component among the embodiment 12 to carry out propylene polymerization, external electron donor methylcyclohexyl dimethoxy silane (CHMMS) amount reduces, and makes Al/S[(mol)=50, all the other the results are shown in Table 3 with embodiment 12:
Embodiment 14
Adopt the catalyst A component among the embodiment 12 to carry out propylene polymerization, external electron donor methylcyclohexyl dimethoxy silane (CHMMS) amount reduces, and makes Al/Si (mol)=100, and all the other the results are shown in Table 3 with embodiment 12:
Embodiment 15
Adopt the catalyst A component among the embodiment 12 to carry out propylene polymerization, external electron donor methylcyclohexyl dimethoxy silane (CHMMS) amount reduces, and makes Al/Si (mol)=150, and all the other the results are shown in Table 3 with embodiment 12:
Embodiment 16
Adopt the catalyst A component among the embodiment 16 to carry out propylene polymerization, external electron donor methylcyclohexyl dimethoxy silane (CHMMS) amount reduces, and makes Al/Si (mol)=200, and all the other the results are shown in Table 3 with embodiment 16:
The normal influence of table 3 external electron donor CHMMS consumption equity.
DNBP/Mg(mol)＝0.074
| Embodiment | ??Al/Si ??(mol) | Cat efficient Kgpp/gCat | ???TII％ | MI g/10 minute | ????BD ????g/ml |
| Example 12 | ???25 | ????42.0 | ???97.5 | ????2.9 | ????0.44 |
| Example 13 | ???50 | ????44.0 | ???96.9 | ????4.8 | ????0.45 |
| Example 14 | ???100 | ????47.0 | ???96.2 | ????5.1 | ????0.44 |
| Example 15 | ???150 | ????34.0 | ???91.9 | ????7.1 | ????0.40 |
| Example 16 | ???200 | ????32.0 | ???87.4 | ????10.5 | ????0.34 |
Embodiment 17
1. the preparation of catalyst A component is with embodiment 1.The A component of gained contains Ti2.41%, Mg16.3%, chlorine 56.1%, DIBP18.9%.
2. polymerization
Change the external electron donor in the propylene polymerization of embodiment 1 into dibutyl dimethoxy silane (DBMS), all the other are with embodiment 1.The results are shown in Table 4:
Embodiment 18
Adopt the catalyst A component among the embodiment 17 to carry out propylene polymerization, external electron donor dibutyl dimethoxy silane (DBMS) amount reduces, and makes Al/Si (mol)=100, and all the other the results are shown in Table 4 with embodiment 17:
Embodiment 19
Adopt the catalyst A component among the embodiment 17 to carry out propylene polymerization, external electron donor dibutyl dimethoxy silane (DBMS) amount reduces, and makes Al/Si (mol)=150, and all the other the results are shown in Table 4 with embodiment 17:
Embodiment 20
Adopt the catalyst A component among the embodiment 17 to carry out propylene polymerization, external electron donor dibutyl dimethoxy silane (DBMS) amount reduces, and makes Al/Si (mol)=200, and all the other the results are shown in Table 4 with embodiment 17:
The normal influence of table 4 external electron donor DBMS consumption equity.
DIBP/Mg(mol)＝0.2
| Embodiment | ???Al/Si ???(mol) | Cat efficient Kgpp/gCat | ???TII％ | MI g/10 minute | ???BD ???g/ml |
| Example 17 | ???25 | ????39.0 | ???98.8 | ????4.6 | ???0.44 |
| Example 18 | ???100 | ????43.0 | ???97.2 | ????6.4 | ???0.45 |
| Example 19 | ???150 | ????42.0 | ???96.4 | ????7.2 | ???0.46 |
| Example 20 | ???200 | ????36.0 | ???92.3 | ????10.2 | ???0.42 |
Embodiment 21
1, in the preparation with A component among the embodiment 1, add internal electron donor n-butyl phthalate (DNBP) 1.0ml, make ester/Mg=0.074, all the other are all with embodiment 1.The A component contains Ti1.7%, Mg16.8%, chlorine 58.5%, DNBP11.93%.
2, polymerization
Change the external electron donor in the propylene polymerization of embodiment 1 into dibutyl dimethoxy silane (DBMS), all the other are with embodiment 1.The results are shown in Table 5:
Embodiment 22
Adopt the catalyst A component among the embodiment 21 to carry out propylene polymerization, external electron donor dibutyl dimethoxy silane (DBMS) amount reduces, and makes Al/Si (mol)=50, and all the other the results are shown in Table 5 with embodiment 21:
Embodiment 23
Adopt the catalyst A component among the embodiment 21 to carry out propylene polymerization, external electron donor dibutyl dimethoxy silane (DBMS) amount reduces, and makes Al/Si (mol)=100, and all the other the results are shown in Table 5 with embodiment 21:
Embodiment 24
Adopt the catalyst A component among the embodiment 21 to carry out propylene polymerization, external electron donor dibutyl dimethoxy silane (DBMS) amount reduces, and makes Al/Si (mol)=150, and all the other the results are shown in Table 5 with embodiment 21:
Embodiment 25
Adopt the catalyst A component among the embodiment 21 to carry out propylene polymerization, external electron donor dibutyl dimethoxy silane (DBMS) amount reduces, and makes Al/Si (mol)=200, and all the other the results are shown in Table 5 with embodiment 21:
Table 5, the normal influence of external electron donor DBMS consumption equity.
DNBP/Mg(mol)＝0.074
| Embodiment | ??Al/Si ??(mol) | Cat efficient Kgpp/gCat | ???TII％ | MI g/10 minute | ????BD ????g/ml |
| Example 21 | ??25 | ?????54.0 | ???97.8 | ????3.2 | ????0.45 |
| Example 22 | ??50 | ?????53.0 | ???97.0 | ????3.8 | ????0.45 |
| Example 23 | ??100 | ?????52.0 | ???95.6 | ????4.2 | ????0.45 |
| Example 24 | ??150 | ?????52.0 | ???93.8 | ????6.4 | ????0.42 |
| Example 25 | ??200 | ?????46.0 | ???90.2 | ????8.7 | ????0.41 |
Claims (13)
1. be used for the catalyzer of propylene polymerization or copolymerization, it is characterized in that, comprise following component:
A, titaniferous solid catalytic ingredient, its be by magnesium halide be dissolved in by organic epoxy compounds and
In the solvent system that organo phosphorous compounds and inert diluent are formed, form behind the homogeneous solution with four
The halogenated titanium or derivatives thereof mixes, and in the presence of precipitation additive, separates out solids; This solids
Handle with the multi-carboxylate, it is attached on the solids, again with titanium tetrahalide and inertia dilution
Agent is handled and is obtained, and wherein precipitation additive is a kind of in organic acid anhydride, organic acid, ether, the ketone,
The mol ratio of multi-carboxylate and magnesium halide is 0.03～0.25;
B, general formula are AlR
nX
3-nAlkylaluminium cpd, be hydrogen in the formula, carbonatoms is 1～20 hydrocarbon
Base;
C, general formula are R
nSi (OR ')
4-nSilicoorganic compound, 0≤n in the formula≤3, R is of the same race or different with R '
The alkyl or cycloalkyl of planting;
Ratio between component B and the component A is 5～1000 with the molar ratio computing of aluminium and titanium,
Ratio between component B and the component C is 1～400 with the molar ratio computing of aluminium and silicon.
2. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, it is characterized in that, the described magnesium halide of catalyst component A is selected from a kind of by in alkyl or the halogen-oxyl institute metathetical derivative of one of them halogen atom in the complex compound, magnesium dihalide molecular formula of the water of magnesium dihalide, magnesium dihalide or alcohol, or their mixture.
3. the catalyzer that is used for propylene polymerization or copolymerization according to claim 1, it is characterized in that, the described organic epoxy compounds of catalyst component A is oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, a kind of in butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, the tetrahydrofuran (THF), or their mixture.
4. the catalyzer that is used for propylene polymerization or copolymerization according to claim 1, it is characterized in that, the described organo phosphorous compounds of catalyst component A is a kind of in ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, the phosphorous acid benzene methyl, or their mixture.
5. the catalyzer that is used for propylene polymerization or copolymerization according to claim 1, it is characterized in that, the described multi-carboxylate of catalyst component A is selected from diethyl malonate, butyl ethyl malonate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, the phthalic ester diisobutyl ester, the phthalic ester di-n-butyl, the phthalic ester di-isooctyl, diethyl maleate, maleic acid n-butyl, the naphthalene dicarboxylic acids diethyl ester, the naphthalene dicarboxylic acids dibutylester, triethyl trimellitate, tributyl trimellitate, the benzene-1,2,3-tricarboxylic acid triethyl, the benzene-1,2,3-tricarboxylic acid tri-n-butyl, the pyromellitic acid tetra-ethyl ester, a kind of in pyromellitic acid four butyl esters, or their mixture.
6. the catalyzer that is used for propylene polymerization or copolymerization according to claim 1, it is characterized in that, the described precipitation additive of catalyst component A is a kind of in diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, the amyl ether, or their mixture.
7. the catalyzer that is used for propylene polymerization or copolymerization according to claim 1, it is characterized in that, the halogenide or derivatives thereof of the described transition metal of catalyst component A is a kind of 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, or their mixture.
8. the catalyzer that is used for propylene polymerization or copolymerization according to claim 1, it is characterized in that, catalyst component C is selected from trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methylcyclohexyl dimethoxy silane, dicyclohexyl diethoxy silane, dibutyl dimethoxy silane, a kind of in the second, isobutyl dimethoxy silane or their mixture.
9. the catalyzer that is used for propylene polymerization or copolymerization according to claim 1 is characterized in that, among the catalyst component A, in every mole of magnesium halide, multi-carboxylate's add-on is 0.05～0.2 mole.
10. the catalyzer that is used for propylene polymerization or copolymerization according to claim 1 is characterized in that, among the catalyst component A, in every mole of magnesium halide, multi-carboxylate's add-on is 0.07～0.12 mole.
11. the catalyzer that is used for propylene polymerization or copolymerization according to claim 1 is characterized in that, the ratio between catalyst component B and the component C is 25～250 with the molar ratio computing of aluminium and silicon.
12. the preparation method of component A is in the described catalyzer of one of claim 1～11: under agitation magnesium halide is dissolved in organic epoxy compounds, organo phosphorous compounds and adds again to the electronics activator, also can add metal halide, form homogeneous transparent solution, in the presence of precipitation additive, under-35～60 ℃ of temperature, be preferably-30～5 ℃; Titanium compound is splashed into the magnesium halide homogeneous solution or magnesium halide solution is splashed in the titanium compound, reaction mixture is warming up to 60～110 ℃ again, suspension was stirred under this temperature 10 minutes～10 hours, stopping to stir the back solids separates out from mixture solution, filter, remove mother liquor, with toluene and hexane wash solids, make titaniferous solid catalytic ingredient.
13. the described catalyzer of one of claim 1～11 is used for the equal polymerization of propylene or the copolymerization of propylene and other alkene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98126383A CN1097596C (en) | 1998-12-30 | 1998-12-30 | Catalyst to make the isotactic degree of polypropylene easy to regulate, the preparation of its active component and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98126383A CN1097596C (en) | 1998-12-30 | 1998-12-30 | Catalyst to make the isotactic degree of polypropylene easy to regulate, the preparation of its active component and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1258680A true CN1258680A (en) | 2000-07-05 |
| CN1097596C CN1097596C (en) | 2003-01-01 |
Family
ID=5229635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98126383A Expired - Lifetime CN1097596C (en) | 1998-12-30 | 1998-12-30 | Catalyst to make the isotactic degree of polypropylene easy to regulate, the preparation of its active component and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1097596C (en) |
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| WO2007124680A2 (en) | 2006-04-20 | 2007-11-08 | China Petroleum & Chemical Corporation | A process for the preparation of high performance polypropylene |
| CN1955195B (en) * | 2005-10-26 | 2010-06-16 | 中国石油化工股份有限公司 | Catalyst, preparation method and application for olefin polymerization or copolymerization |
| CN102190748A (en) * | 2010-03-19 | 2011-09-21 | 中国石油天然气股份有限公司 | Preparation method of propylene/1-butene random copolymer resin |
| EP2586801A1 (en) | 2011-10-29 | 2013-05-01 | China Petroleum&Chemical Corporation | Propylene random copolymer, method for its preparation, and compositions and articles containing the same |
| CN103772562A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | High isotacticity polypropylene production method |
| CN104558292A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of catalyst for olefin polymerization |
| US9068030B2 (en) | 2010-01-22 | 2015-06-30 | China Petroleum & Chemical Corporation | Propylene homopolymer having high melt strength and preparation method thereof |
| CN106608940A (en) * | 2015-10-27 | 2017-05-03 | 中国石油化工股份有限公司 | Preparation method for catalyst components used for olefin polymerization |
| EP3241863A1 (en) | 2016-04-28 | 2017-11-08 | China Petroleum&Chemical Corporation | Flame-retardant thermoplastic material and expanded beads thereof |
| EP3938097A4 (en) * | 2019-03-15 | 2022-11-30 | W. R. Grace & Co.-Conn | Catalyst system for producing olefin polymers with no fines |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1006071B (en) * | 1985-04-01 | 1989-12-13 | 中国石油化工总公司 | Catalyst system for olefin polymerization and copolymerization |
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1998
- 1998-12-30 CN CN98126383A patent/CN1097596C/en not_active Expired - Lifetime
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| CN1955195B (en) * | 2005-10-26 | 2010-06-16 | 中国石油化工股份有限公司 | Catalyst, preparation method and application for olefin polymerization or copolymerization |
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| WO2007124680A2 (en) | 2006-04-20 | 2007-11-08 | China Petroleum & Chemical Corporation | A process for the preparation of high performance polypropylene |
| US9068030B2 (en) | 2010-01-22 | 2015-06-30 | China Petroleum & Chemical Corporation | Propylene homopolymer having high melt strength and preparation method thereof |
| CN102190748A (en) * | 2010-03-19 | 2011-09-21 | 中国石油天然气股份有限公司 | Preparation method of propylene/1-butene random copolymer resin |
| CN102190748B (en) * | 2010-03-19 | 2013-03-27 | 中国石油天然气股份有限公司 | Preparation method of propylene/1-butene random copolymer resin |
| EP2586801A1 (en) | 2011-10-29 | 2013-05-01 | China Petroleum&Chemical Corporation | Propylene random copolymer, method for its preparation, and compositions and articles containing the same |
| CN103772562A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | High isotacticity polypropylene production method |
| CN104558292A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of catalyst for olefin polymerization |
| CN104558292B (en) * | 2013-10-28 | 2017-05-31 | 中国石油化工股份有限公司 | One kind is used for olefin polymerization catalysis preparation method |
| CN106608940B (en) * | 2015-10-27 | 2019-06-28 | 中国石油化工股份有限公司 | The preparation method of catalytic component for olefinic polymerization |
| CN106608940A (en) * | 2015-10-27 | 2017-05-03 | 中国石油化工股份有限公司 | Preparation method for catalyst components used for olefin polymerization |
| EP3241863A1 (en) | 2016-04-28 | 2017-11-08 | China Petroleum&Chemical Corporation | Flame-retardant thermoplastic material and expanded beads thereof |
| EP3241864A1 (en) | 2016-04-28 | 2017-11-08 | China Petroleum&Chemical Corporation | Flame retardant, composite flame retardant, flame retardant antistatic composition and flame resistant method |
| EP3938097A4 (en) * | 2019-03-15 | 2022-11-30 | W. R. Grace & Co.-Conn | Catalyst system for producing olefin polymers with no fines |
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| CN1097596C (en) | 2003-01-01 |
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