CN100417669C - Solid catalyst composition used for olefine polymerization and catalyst thereof - Google Patents
Solid catalyst composition used for olefine polymerization and catalyst thereof Download PDFInfo
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- CN100417669C CN100417669C CNB2005101126934A CN200510112693A CN100417669C CN 100417669 C CN100417669 C CN 100417669C CN B2005101126934 A CNB2005101126934 A CN B2005101126934A CN 200510112693 A CN200510112693 A CN 200510112693A CN 100417669 C CN100417669 C CN 100417669C
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Abstract
This invention provides a solid catalyst composition used for alkenes polymerization and its catalyst, this catalyst composition contains following composition's reaction product: the Composite carrying agent is produced by spray drying halogenated magnesium and gel silica, at least one diatomic alcohol esters compound and at least one compound selected from bibasic aliphatic carboxylic acid esters or aromatic series carboxylic ester, and halogenated Titanium compound.When two Internal electronic compounds of stated catalyst is used by matching, it is not only ensured to be high activity of prepared catalyst, but also ensured that prepared polymer possess good tacticity.
Description
Technical field
The present invention relates to a kind of ingredient of solid catalyst and catalyzer thereof that is used for olefinic polymerization, relate to catalyzer and its application in preparation olefin polymerization catalysis of a kind of employing more specifically by magnesium halide and spray-dried complex carrier that makes of silica gel and the preparation of compound internal electron donor.
Technical background
As everyone knows, the Ziegler-Natta catalyst that be used for olefinic polyreaction, particularly has an alpha-olefin polymerization of three carbon or more carbon atoms generally includes Primary Catalysts and promotor two portions.Primary Catalysts is mostly by MgCl
2Carrier, titanium compound (are generally TiCl
4) and internal electron donor reaction form.The industry generally believes, MgCl
2Play skeleton function in carrier, the pattern of carrier has directly determined the pattern of its prepared catalyzer and the olefin polymer particle that obtains.TiCl
4Play the effect that forms the active centre.And internal electron donor plays the effect that improves catalytic activity and stereospecificity, and influences hydrogen response and other all many-sided performance of final catalyzer.
Up to now, multiple electron donor compound is disclosed, common as the aromatic esters compounds, comprise aromatic acid monoesters class and aromatic acid di-esters compound, as (seeing CN8510097, EP0045977 etc.) such as ethyl benzoate, n-butyl phthalate, phthalic acid isobutyl esters; Binary aliphatic carboxylic acid ester compound, common comprise malonic ester compounds, succinate compounds etc. (are seen CN1236732, CN1236733, CN1236734, CN1292800; PCT International Application No. WO 0063261 etc.); Two ethers electron donors (seeing EP0361493, EP0728724 etc.), and cyanate electron donor (seeing CN1242780), maleic acid ester class electron donor, two ketone electron donors (seeing CN1105671A) and two amine electron donor polytype compounds such as (seeing CN1087918).Adopt the different prepared catalyzer of internal electron donor compound to have different characteristics, some catalyzer has higher activity, some catalyzer has hydrogen regulation performance preferably, and the polyolefin resin of some Preparation of Catalyst then has wider molecular weight distribution.In order to obtain having the catalyzer of excellent comprehensive performance, people attempt to adopt two or more internal electron donor to prepare catalyzer again, and its associated viscera is disclosed in the patents such as WO9957160, WO0230998, WO03002617, JP2001139621, JP2002249507, CN1242780A and CN1268957.
Know again, Chinese patent CN1524886 disclose a kind of be used for olefinic polymerization particularly propylene polymerization or copolymerization catalyst complex carrier and adopt the catalyst component and the catalyzer of this complex carrier, it at first mixes with the solution of electron compound formation magnesium halide with the silica gel of median size less than 30 μ m, the spray-dried globular complex carrier particle that makes, load has titanium compound and conventional internal electron donor on this carrier then, as obtaining catalyzer behind the aliphatic carboxylic acid esters, of binary or the aromatic carboxylic acid esters of binary, particularly phthalate.Adopt this catalyzer gained acrylic resin to have higher degree of isotacticity, but catalyst activity is also unsatisfactory.
In addition, Chinese patent CN1436796, CN1453298, PCT/CN03/00110 and the PCT/CN03/00111 catalyzer that then discloses a class dibasic alcohol ester compound and adopted this compound to make.Pass through repetition test, we find by on the basis of the disclosed catalyst system of Chinese patent CN1524886, after above-mentioned dibasic alcohol ester compound and conventional internal electron donor compound are used, the stereoregular performance of gained activity of such catalysts and final acrylic resin reaches certain balance, promptly when obtaining high activated catalyst, also can guarantee the tacticity that acrylic resin is higher, this point is crucial for the industrial application of catalyzer.
Summary of the invention
The invention provides a kind of ingredient of solid catalyst that is used for olefinic polymerization, it contains the reaction product of following component:
(1) complex carrier: magnesium halide is contacted formation solution with the compound of one or more solubilized magnesium halides, then this solution is mixed the spray-dried carrier granule that makes with the earth silicon material of median size less than 10 μ m;
(2) electron donor a: at least a binary alcohol esters compounds that is selected from shown in general formula (I):
R in the formula
1-R
6Can be identical or inequality, be hydrogen or C
1-C
10The alkyl of straight or branched, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
7-C
10Alkaryl or aralkyl; R
1-R
6In two or more groups mutually bonding generate one or several condensed ring structure; R
7And R
8Can be identical or inequality, represent C
1-C
10Straight or branched alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aryl, the benzene ring hydrogen can randomly be replaced by halogen atom in described aryl or alkaryl or the aryl;
(3) electron donor b: at least a aliphatic carboxylic acid esters, of monobasic or binary and the aromatic carboxylic acid esters's compound of monobasic or binary of being selected from;
(4) halogenated titanium: at least a being selected from as general formula Ti (OR)
4-mX
mShown titanium compound, R is C independently in the formula
1～C
14Aliphatic group, preferred C
1～C
14Alkyl; X is selected from F, Cl, Br or its mixture; M is 1～4 integer,
Wherein in every mole of magnesium halide in the complex carrier, the total amount of electron donor a and electron donor b is the 0.01-1 mole, and the mol ratio of electron donor a and electron donor b is 0.1-10, and titanium compound is 1～100 mole.
Particularly, employed magnesium halide such as Mg (OR in the above-mentioned complex carrier
1)
2-mX
mShown in, R in the formula
1Be identical or different C
1～C
14Straight chain, side chain or cyclic alkyl, X are selected from F, Cl, Br or its mixture, m is 1 or 2.Concrete compound is including, but not limited to magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.Described halogenated magnesium compound can be used alone or as a mixture.
The suitable compound that is used to dissolve described magnesium halide comprises the alkyl ester of optional halogenated fat or aromatic alcohol, aliphatic ether, cyclic ethers, aliphatic ketone, fat or aromatic carboxylic acid.Particularly suitable be the saturated fatty alcohol of the optional halogenated 1-8 of a containing carbon atom; The lower alkyl esters that contains the aliphatic saturated monocarboxylic acid of 1-4 carbon atom; Contain the aromatics monobasic of 7-8 carbon atom or the lower alkyl esters of polycarboxylic acid; Contain 2-8 carbon atom, be preferably the aliphatic ether of 4-5 carbon atom; Contain the cyclic aliphatic ether of 4-5 carbon atom, preferably contain the monoether or the diether of 4 carbon atoms; With contain 3-6 carbon atom, be preferably the aliphatic ketone of 4-5 carbon atom." low alkyl group " refers to the alkyl of 1-6 carbon atom at this.
Preferably, described compound is to comprise at least a optional halogenated C
1-8Fatty Alcohol(C12-C14 and C12-C18) or C
7-10The system of aromatic alcohol.More preferably described compound is optional halogenated C
1-8Fatty Alcohol(C12-C14 and C12-C18) and C
7-10At least a in the aromatic alcohol, or described alcohol and C
1-6Aliphatic ether, C
3-5The C of cyclic ethers or fat or aromatic carboxylic acid
1-6The mixture of alkyl ester.
The described example that is used to dissolve halogenated magnesium compound includes but not limited to: methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, n-Octanol, isooctyl alcohol, ethylene glycol, propylene glycol, chloroethanol, ethapon, ether, butyl ether, methyl-formiate, ethyl acetate, butylacetate, hexyl ether, tetrahydrofuran (THF) (THF), acetone, methyl iso-butyl ketone (MIBK), ethyl benzoate, diethyl phthalate, n-butyl phthalate, diisobutyl phthalate etc., preferred alcohol, Virahol, propyl carbinol, ethapon, tetrahydrofuran (THF), ethyl benzoate, diethyl phthalate.Electron donor can use separately or several being used.
Suitable be used to dissolve halogenated magnesium compound and also comprise the system that contains organic epoxy compounds and/or organo phosphorous compounds, described organic epoxy compounds is selected from least a in aliphatic epoxide, diepoxide or halogenated aliphatic epoxide with 2～8 carbon atoms or diepoxide, the glycidyl ether.For example: oxyethane, propylene oxide, butylene oxide ring, vinyl oxyethane, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether.Described organo phosphorous compounds is selected from the C of ortho-phosphoric acid or phosphorous acid
1-C
10Hydrocarbyl carbonate or halo hydrocarbyl carbonate.For example: 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, tricresyl phosphite benzene methyl.
In order to make magnesium halide and above-claimed cpd contact reacts form uniform solution, generally, every mole of magnesium halide needs 3～50 moles of described compounds, is preferably 6～30 moles.The preparation of this solution can be carried out in the presence of a kind of inert organic solvents, and this solvent does not form adducts with magnesium halide.The preferred C of described inert solvent
5-12Alkane, C
1-6Halohydrocarbon and C
6-12Aromatic hydrocarbons, for example hexane, heptane, ethylene dichloride, toluene, dimethylbenzene, ethylbenzene etc.
Obtain more short grained complex carrier for the ease of spray shaping, described earth silicon material is generally selected the silicon-dioxide of median size less than 10 μ m for use, be preferably less than 5 μ m, more preferably particle diameter also claims aerosil less than the pyrogenic silica of 1 μ m.The specific surface area of this silicon-dioxide is generally 200 ± 50m
2/ g.
With solution and the slurry that obtains after silicon-dioxide mixes being suitable for spraying, usually, the add-on of silicon-dioxide is 10～200g in every liter of solution.
Spraying drying can be carried out according to the following steps: the slurries that solution is obtained after earth silicon material mixes carry out spraying drying with the inertia dry gas by the spraying drying instrument, obtain the globular solid particulate.
In order to make complex carrier of the present invention be applicable to the catalyzer that the preparation propylene polymerization is used better, needing this complex carrier usually is that mean diameter is the spherical particle of 5-60 μ m, preferred 10-40 μ m, more preferably 12-30 μ m.。
Particularly, in the binary alcohol esters compounds shown in the above-mentioned electron donor a general formula (I), R preferably
1, R
2, R
5, R
6Be not hydrogen simultaneously; More preferably, R
1And R
2, R
5And R
6In a group is arranged respectively is hydrogen, and another group is selected from C
1-C
10The alkyl of straight or branched, C
3-C
10Cycloalkyl, C
6-C
10Aryl and C
7-C
10Alkaryl or aralkyl; Concrete as methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, phenyl or halogenated phenyl etc.
Particularly, in the diol ester compound of above-mentioned general formula (I), R preferably
7And R
8Group is selected from methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, amyl group, cyclopentyl, cyclohexyl, phenyl, halogenated phenyl, aminomethyl phenyl, halogenated aminomethyl phenyl, indenyl, benzyl or phenylethyl.More preferably, R
7And R
8Group is selected from phenyl, halogenated phenyl, aminomethyl phenyl or halogenated aminomethyl phenyl
The example of suitable binary alcohol esters compounds includes but not limited to:
Described electron donor compound a is disclosed among CN1436766A and CN1436796A, PCT/CN03/00110 and the PCT/CN03/00111, and all associated visceras are introduced the present invention as a reference in the described patent.
Particularly, above-mentioned electron donor b comprises benzoates, phthalate, malonic ester class, succinate class, glutarate class or pivalate class.
Wherein malonic ester compounds is shown in general formula (II), in the formula, and R
1And R
2Be methyl or ethyl, R
3And R
4Be alkyl or the-oxyl that contains 1～20 carbon atom;
Glutarate compounds wherein shown in general formula (III), R in the formula
1And R
2Be alkyl, R
3-R
8For hydrogen or contain the alkyl of 1～20 carbon atom, R
3-R
8Preferred those are linked into the alkyl of ring by halogen replacement and two substituting groups on same carbon atom;
Succinate compounds wherein shown in general formula (IV), R in the formula
1And R
2For containing the alkyl of 1～20 carbon atom, the optional heteroatoms that contains, preferred R
3～R
6Be not 1～20 alkyl simultaneously for the carbon atom quantity of hydrogen, the optional heteroatoms that contains.
Concrete compound is as ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate, dinoctyl phthalate; Diethyl malonate, butyl ethyl malonate, 2,3-di-isopropyl ethyl succinate, 2,3-di-isopropyl di-iso-octyl succinate, 2,3-di-isopropyl dibutyl succinate, 2,3-di-isopropyl succsinic acid dimethyl esters, 2,2-dimethyl succinate diisobutyl ester, 2-ethyl-2-methylsuccinic acid diisobutyl ester, 2-ethyl-2-methylsuccinic acid diethyl ester, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, 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 butyl esters etc.The preferred phthalate compound that uses.
Particularly, above-mentioned halogenated titanium is selected from as general formula Ti (OR)
4-mX
mAt least a in the shown titanium compound, R is C independently in the formula
1～C
14Aliphatic group, preferred C
1～C
14Alkyl, more preferably normal-butyl/isobutyl-, 2-ethylhexyl, n-octyl and phenyl; X is selected from F, Cl, Br or its mixture; M is 1～4 integer.Concrete compound can be selected titanium tetrahalide, particularly titanium tetrachloride for use; Three chlorocarbon oxygen machine base titanium, particularly trichlorine butoxy and Trichlorophenoxy titaniums; Four titan-alkoxides, particularly four titanium butoxide, purity titanium tetraethoxide etc.
Wherein in every mole of magnesium halide in the complex carrier, the total amount of electron donor a and electron donor b is the 0.01-1 mole, is preferably 0.05～0.5 mole; The mol ratio of electron donor a and electron donor b is 0.1-10, is preferably 0.2～5; Titanium compound is 1～100 mole, is preferably 1～10 mole.
The preparation of above-mentioned ingredient of solid catalyst of the present invention can be carried out according to various disclosed methods, can be with reference to disclosed concrete technological line among the Chinese patent CN1524886, and its associated viscera is introduced the present invention.Before complex carrier and titanium compound reaction or after the reaction, can also adopt electron donor compound a and b to handle.
Compound a and compound b can be used in many ways jointly, can add under identical or different step or condition, preferably add in identical step and condition.
Specifically, ingredient of solid catalyst of the present invention can prepare as follows:
(1) preparation magnesium chloride solution
Can prepare magnesium chloride solution according to disclosed certain methods, such as using US4784983 and the disclosed magnesium chloride dissolution system of US4861847 to prepare magnesium chloride solution.
Preferably, among the present invention, magnesium chloride solution prepares as follows:
In the reactor of stirring is housed, add the mixture of a kind of alcohol or two kinds and two or more alcohol, also can add a kind of ether or ester again, add Magnesium Chloride Anhydrous then, heating makes the magnesium chloride dissolving.Wherein alcohol is 3～50: 1 with the mol ratio of magnesium chloride, and the mol ratio of ether or ester and magnesium chloride is 0～20: 1.The dissolving of above-mentioned magnesium chloride also can be carried out in a kind of inert organic solvents, and the consumption of solvent is 0～20ml/gMgCl
2
(2) prepare spherical MgCl
2/ SiO
2Complex carrier
Add smoke-like silica gel in above-mentioned magnesium chloride solution, the add-on of silica gel is 0.1～2g/gMgCl
2, used silica gel is the aerosil of average particulate diameter less than 10 μ m.Stirred 0.5～3 hour down at 10～100 ℃ afterwards, make slurries.Then slurries are carried out spraying drying with the inertia dry gas by the spraying drying instrument, obtaining median size is the spherical MgCl of 5～60 μ m
2/ SiO
2Complex carrier.Inlet air temperature during spraying drying is controlled at 80～300 ℃, and air outlet temperature is controlled at 50～200 ℃.Usually, consisting of of complex carrier:
MgCl
2: 20%～60% (weight)
SiO
2: 10%～60% (weight)
Alcohol: 5%～40% (weight)
Ether: 0～20% (weight)
Solvent:＜5% (weight)
(3) preparation ingredient of solid catalyst
Above-mentioned complex carrier is suspended in TiCl
4Mixed solution (TiCl with hexane
4Amount is 5～10mlTiCl
4/ g carrier, hexane and TiCl
4Volume ratio be 0～2) in, slowly be warmed up to 80～100 ℃, after keeping for some time under this temperature, liquid is filtered; Add excessive TiCl
4(TiCl
4Amount is 12～16mlTiCl
4/ g carrier), in 1～3 hour, slowly be warming up to 100～120 ℃, and add electron donor compound a and electron donor compound b simultaneously in temperature-rise period, total amount is 0.01-1 mole/molMgCl
2React 1～2 hour after-filtration; Randomly, add a certain amount of TiCl
4, kept 1～2 hour at 120 ℃, filtrate is filtered; With the solids washing, then solids is vacuumized drying with inert solvent such as hexane etc. under 30 ℃～50 ℃, promptly get ingredient of solid catalyst of the present invention.
In particular, the present invention also provides a kind of alkene CH that is used for
2The catalyzer of=CHR polyreaction, wherein R is the alkyl of hydrogen or 1～12 carbon atom, this catalyzer comprises the reaction product between following material:
(1), a kind of above-mentioned ingredient of solid catalyst;
(2), a kind of alkylaluminium cpd, and randomly,
(3), one or more electron donor compounds (external electron donor).
Wherein, the alkylaluminium cpd preferred formula is AlR
nX
3-nCompound, R is the alkyl of hydrogen or carbonatoms 1～20, particularly alkyl, aralkyl, aryl etc. in the formula; X is halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Alkylaluminium cpd of the present invention comprises: trialkylaluminiums such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum; Alkyl aluminium hydrides such as one hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum; Aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, aluminum alkyls muriates such as ethyl aluminum dichloride wherein are preferably triethyl aluminum and triisobutyl aluminium.
The consumption of aluminum alkyls is: wherein the mol ratio of titanium is 5-5000 in aluminium and the solid constituent (1), is preferably 20-500.
The external electron donor compound is preferably silicoorganic compound.Its general formula is RnSi (OR ')
4-n, 0＜n in the formula≤3, R and R ' they are alkyl of the same race or not of the same race, cycloalkyl, aryl, haloalkyl etc. in the general formula, R also can be halogen or hydrogen atom.Silicoorganic compound of the present invention comprise the trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, two phenoxy group dimethoxy silane, the phenylbenzene diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, (1,1,1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1,1,1-three fluoro-2-propyl group)-methyl dimethoxysilane etc.
The consumption of external electron donor (3) is: the mol ratio of organo-aluminium compound and described external electron donor compound is 0.1～500, and is preferred 1～300, more preferably 3～100.
The polymerization of alkene is carried out according to currently known methods, in liquid monomer or monomer in the liquid phase of the solution in inert solvent, or in gas phase, or by operating in the polymerization mix technology of gas-liquid in mutually.Polymerization temperature is generally 0 ℃～150 ℃, preferably 60 ℃～100 ℃.Polymerization pressure is a normal pressure or higher
Embodiment
The invention is further illustrated by the following examples, to deepen the understanding of the present invention.Invention itself is not subjected to the restriction of these embodiment.
Below given embodiment be for better the explanation rather than the restriction the present invention.
Comparative Examples 1
Spherical MgCl
2/ SiO
2The preparation of complex carrier is carried out in two steps:
1) preparation of spraying drying mother liquor: at process N
2Fully add the ethanol of 200mL in the 350mL reactor that the metathetical band stirs through processed.Under room temperature, add the 20g Magnesium Chloride Anhydrous while stirring, the adding speed of control magnesium chloride remains on below 40 ℃ system temperature.Magnesium chloride add finish after, the mixed system temperature is risen to 70 ℃, and, obtains even MgCl this temperature constant temperature 4 hours
2Ethanolic soln.The TS-610 that adds the 12.5g particle diameter and the be 0.1um silica gel of being fuming continues to stir 1 hour, obtains the spraying drying mother liquor.
2) spraying drying prepares MgCl
2/ SiO
2Ball type carrier: use B-290 spraying drying instrument to prepare complex carrier.Utilize peristaltic pump that the mother liquor that obtains is incorporated into two-fluid spray nozzle by pipeline, atomizing enters kiln.Control feed liquid and spray gas N
2Flow is respectively 8mL/min and 1400L/h, and spraying temperature degree is a room temperature.Carrier gas N
2Flow control is at the 11000L/min place, and the instrument inlet port temperature is 190 ℃, and the instrument temperature out is stabilized near 105 ℃.Obtain spherical MgCl in the collection of the exit, below of cyclonic separator
2/ SiO
2The complex carrier particle.Chemical composition analysis is the result show: Mg 13.5wt%, Cl 35.6wt%, C in the carrier
2H
5OH41.2wt%, D
50Be 43.9um.
Synthesizing of solid catalyst:
Get above-mentioned carrier 9g, slowly adding is chilled to the TiCl of 0 ℃ 100mL in advance
4In, be warming up to 40 ℃ in 1 hour, add n-butyl phthalate (DNBP) 1.0mL, in 0.5 hour, be warming up to 100 ℃ then, kept two hours, filter out liquid phase.Add 100mL TiCl
4, be warming up to 120 ℃ in 0.5 hour, keep one hour after, filter out liquid phase.Remaining solid obtains solid catalyst component through 60 ℃ of hexane wash five times, after vacuumizing drying.Gained solid catalyst chemical constitution and some physical parameter test results see Table 1.
Propylene polymerization:
70 ℃ with propylene gas 2L stainless steel autoclave is purged 1 hour after, add the hexane solution and the above-mentioned ingredient of solid catalyst that makes of 9mg of hexane solution that 1mL concentration is the triethyl aluminum of 1M, cyclohexyl methyl dimethoxy silane that 0.5mL concentration is 0.1M under the room temperature, in the nitrogen atmosphere.Close autoclave, add hydrogen and the 1L liquid propene of 4NL.Under agitation condition, be warming up to 70 ℃ in 5 minutes.After one hour, stop stirring, emptying end polymeric propylene monomer in reaction under this temperature, temperature in the kettle is cooled to room temperature, open the still lower discharge port and discharge polypropylene GRANULES.The performance data test result of catalyst activity and gained acrylic resin sees Table 2.
Embodiment 1
The complex carrier preparation is with Comparative Examples 1.Unique situation that is different from Comparative Examples 1 is in the catalyst preparation process, adds 0.25mL 4-ethyl-3 simultaneously, the n-butyl phthalate mixing electron donor of 5-heptanediol dibenzoate and 0.75mL.Propylene polymerization processes is with embodiment 1.
See Table 1 with body catalyst composition and the test of some physical parameters, the performance data test result of olefine resin saw Table 2 in catalyst activity and gained were poly-.
Embodiment 2
The complex carrier preparation is with Comparative Examples 1.In catalyst preparation process, unique situation that is different from the Comparative Examples 1 is to add 0.50mL 4-ethyl-3, the n-butyl phthalate mixing electron donor of 5-heptanediol dibenzoate and 0.50mL.Propylene polymerization processes is with embodiment 1.
Solid catalyst is formed and some physical parameter tests see Table 1, and the performance data test result of catalyst activity and gained acrylic resin sees Table 2.
Embodiment 3
The complex carrier preparation is with Comparative Examples 1.In catalyst preparation process, unique situation that is different from the Comparative Examples 1 is to use 0.75mL 4-ethyl-3, the n-butyl phthalate mixing electron donor of 5-heptanediol dibenzoate and 0.25mL.Propylene polymerization processes is with embodiment 1.
See Table 1 with body catalyst composition and the test of some physical parameters, the performance data test result of olefine resin saw Table 2 in catalyst activity and gained were poly-.
Comparative Examples 2
The complex carrier preparation is with Comparative Examples 1.In catalyst preparation process, unique situation that is different from the Comparative Examples 1 is to add 1.0mL 4-ethyl-3,5-heptanediol dibenzoate electron donor.Propylene polymerization processes is with embodiment 1.
Solid catalyst is formed and some physical parameter tests see Table 1, and the performance data test result of catalyst activity and gained acrylic resin sees Table 2.
Table 1 catalyzer composition, specific surface area and testing graininess result
Annotate: "-" expression is not carried out corresponding test job to sample in the table.A:4-ethyl-3,5-heptanediol dibenzoate
Table 2 mass polymerization result
Known by above result: the catalyst activity that uses the n-butyl phthalate electron donor to obtain merely is lower, and gained propene polymer degree of isotacticity is higher; The simple 4-ethyl-3 that uses, the catalyst activity height of 5-heptanediol dibenzoate electron donor, but gained propene polymer degree of isotacticity is lower.
With 4-ethyl-3 in the catalyzer, the increase of 5-heptanediol dibenzoic acid ester content, catalyst activity increases, but polymers obtained degree of isotacticity reduces gradually; Increase with n-butyl phthalate content in the catalyzer, catalyst activity reduces, and the resulting polymers degree of isotacticity progressively increases.Shown in embodiment 2 and 3, two kinds of internal electron donor compounds are used in the catalyzer, have both guaranteed the high reactivity of gained catalyzer, have guaranteed that also final acrylic resin has higher degree of isotacticity.
Claims (11)
1. ingredient of solid catalyst that is used for olefinic polymerization, it contains the reaction product of following component:
(1) complex carrier: magnesium halide is contacted formation solution with the compound of one or more solubilized magnesium halides, then this solution is mixed the spray-dried carrier granule that makes with the earth silicon material of median size less than 10 μ m;
(2) electron donor a: at least a binary alcohol esters compounds that is selected from shown in general formula (I):
R in the formula
1-R
6Identical or inequality, be hydrogen or C
1-C
10The alkyl of straight or branched, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
7-C
10Alkaryl or aralkyl; R
1-R
6In two or more groups mutually bonding generate one or several condensed ring structure; R
7And R
8Identical or inequality, represent C
1-C
10Straight or branched alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aryl, the benzene ring hydrogen is randomly replaced by halogen atom in described aryl or alkaryl or the aryl;
(3) electron donor b: at least a aliphatic carboxylic acid esters, of monobasic or binary and the aromatic carboxylic acid esters's compound of monobasic or binary of being selected from;
(4) halogenated titanium: at least a being selected from as general formula Ti (OR)
4-mX
mShown titanium compound, R is C independently in the formula
1～C
14Aliphatic group, X is selected from F, C1 or Br, m is 1～4 integer,
Wherein in every mole of magnesium halide in the complex carrier, the total amount of electron donor a and electron donor b is the 0.01-1 mole, and the mol ratio of electron donor a and electron donor b is 0.1-10, and titanium compound is 1～100 mole.
2. the ingredient of solid catalyst that is used for olefinic polymerization according to claim 1, in the wherein said general formula (I), R
1, R
2, R
5, R
6Be not hydrogen simultaneously.
3. the ingredient of solid catalyst that is used for olefinic polymerization according to claim 1, in the wherein said general formula (I), R
1And R
2, R
5And R
6In a group is arranged respectively is hydrogen, and another group is selected from C
1-C
10The alkyl of straight or branched, C
3-C
10Cycloalkyl, C
6-C
10Aryl and C
7-C
10Alkaryl or aralkyl.
4. the ingredient of solid catalyst that is used for olefinic polymerization according to claim 1, wherein electron donor b is selected from phthalate, malonic ester class, succinate class, glutarate class and pivalate compounds.
5. the ingredient of solid catalyst that is used for olefinic polymerization according to claim 1, wherein in every mole of magnesium halide in the complex carrier, the total amount of electron donor a and electron donor b is 0.05～0.5 mole; The mol ratio of electron donor a and electron donor b is 0.2～5.
6. the ingredient of solid catalyst that is used for olefinic polymerization according to claim 1, the median size of earth silicon material is less than 1 μ m in the wherein said complex carrier.
7. the ingredient of solid catalyst that is used for olefinic polymerization according to claim 1, the mean diameter of wherein said complex carrier are 5-60 μ m.
8. one kind is used for CH
2The catalyzer of=CHR olefinic polyreaction, wherein R is hydrogen or C
1-C
6Alkyl or aryl, described catalyzer comprises the reaction product of following component:
(1) the described catalyst component of one of claim 1-7;
(2) alkylaluminium cpd;
(3) randomly, external electron donor component.
9. catalyzer according to claim 8, wherein alkylaluminium cpd such as AlR
nX
3-nShown in, R is identical or different straight chain in the formula, side chain or ring-type C
1～C
20Alkyl, X are halogen, n=1,2 or 3.
10. catalyzer according to claim 8, wherein the external electron donor component is a general formula R
4NSi (OR
5)
4-nSilicoorganic compound, 0≤n in the formula≤3, R
4Be alkyl, cycloalkyl, aryl or haloalkyl, R
4Randomly be halogen or hydrogen atom; R
5Be alkyl, cycloalkyl, aryl or haloalkyl.
11. catalyzer according to claim 10, the ratio between ingredient of solid catalyst (1), alkylaluminium cpd component (2) and the external electron donor component (3) wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1: 5～1000: 0～500.
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| CN101724105B (en) * | 2008-10-24 | 2011-10-12 | 中国石油化工股份有限公司 | Catalyzer component for olefin polymerization reaction and catalyzer thereof |
| CN102453149B (en) * | 2010-10-21 | 2013-06-05 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, olefin polymerization catalyst and olefin polymerization method |
| CN102453147B (en) * | 2010-10-21 | 2013-06-05 | 中国石油化工股份有限公司 | Catalyst component, catalyst and method for olefin polymerization |
| CN103087229B (en) * | 2011-11-01 | 2015-02-11 | 中国石油化工股份有限公司 | Catalyst component and catalyst used in ethylene polymerization |
| US9790291B2 (en) * | 2013-03-14 | 2017-10-17 | Formosa Plastics Corporation, Usa | Non-phthalate compounds as electron donors for polyolefin catalysts |
| CN104558285B (en) * | 2013-10-24 | 2017-02-15 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst |
| CN104558289B (en) * | 2013-10-25 | 2017-09-29 | 中国石油化工股份有限公司 | Olefin polymerization catalysis and its application and polypropylene and its polymerization |
| CN105199024B (en) * | 2014-06-24 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof |
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| CN1436796A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
| CN1453298A (en) * | 2003-04-21 | 2003-11-05 | 中国石油化工股份有限公司 | Catalyst for olefine polymerizing reaction and its components |
| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
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| CN1436796A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
| CN1524886A (en) * | 2003-02-24 | 2004-09-01 | 中国石油化工股份有限公司 | Compound carrier for olefin polymerization catalyst, catalyst components and the catalyst |
| CN1453298A (en) * | 2003-04-21 | 2003-11-05 | 中国石油化工股份有限公司 | Catalyst for olefine polymerizing reaction and its components |
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