CN1958621B - Solid catalyst components in use for polymerizing olefin, catalyst, and application of catalyst - Google Patents
Solid catalyst components in use for polymerizing olefin, catalyst, and application of catalyst Download PDFInfo
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Abstract
This invention provides components and applications of a solid catalyst for olefin polymerization. The solid catalyst comprises: magnesium halide/silica gel composite carrier prepared by spray drying, at least one diester compound, at least one dibasic aliphatic carboxylate or aromatic carboxylate, and Ti compound. The cooperation of the two inner electron donors can ensure high catalytic activity, high steric regularity and high hydrogen sensitivity. The final polymer has high packing density and wide molecular weight distribution, thus is easy for industrial production and post-treatment.
Description
Technical field
The present invention relates to a kind of ingredient of solid catalyst and catalyzer and catalyzer application that is used for olefinic polymerization, relate to a kind of employing catalyzer, its application and application in olefinic polymerization of this catalyzer in the preparation olefin polymerization catalysis 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 stereotaxis ability, 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 EP036 1493, 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, at first magnesium halide is mixed with the silica gel of median size less than 30 μ m with the solution of electron donor compound formation, the spray-dried globular complex carrier particle that makes, load 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 compound.Adopt this catalyzer gained acrylic resin to have higher degree of isotacticity, but catalyst activity is also unsatisfactory.
Patent EP 0361494, and CN1141285A uses the Z-N catalyzer that contains two ethers internal electron donors to have active height, hydrogen is transferred outstanding characteristics such as responsive, high upright structure orientation property and resulting polymers narrow molecular weight distribution.We find in real work, the MgCl that uses spraying drying to make
2/ SiO
2Spherical complex carrier, when preparing the Z-N catalyzer as internal electron donor with diether, the gained catalyzer has shown higher catalyzing propone polymerization activity, responsive hydrogen regulation performance and high upright structure orientation property, but gained alfon narrow molecular weight distribution have brought inconvenience for the post-treatment treating processes; In addition, gained propene polymer bulk density is lower, also is not easy to be used for actual industrial production.Phthalate is lower as the resulting molecular weight distribution broad of the catalyzer of internal electron donor, resin bulk density, but catalyst activity is not very high, and hydrogen regulation performance neither be fine.
Pass through repetition test, when we find the compound use of internal electron donor compound of diether and routine, molecular weight distribution, the bulk density of gained activity of such catalysts, upright structure orientation property and hydrogen response and final polymkeric substance reach certain balance, the high reactivity of catalyzer, high hydrogen response and upright structure orientation property can be guaranteed, higher bulk density can be obtained having again and than the polymkeric substance of wide molecular weight distribution.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 diether compound that is selected from shown in general formula (I):
R in the formula
I, R
II, R
III, R
IV, R
VAnd R
VIMutually the same or inequality, be the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl, and R
VIIAnd R
VIIICan be identical or different, be the C of straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; R
I-R
VIGroup between can be keyed to ring;
(3) electron donor b: at least a monobasic or polyhydric aliphatic family carboxylicesters or aromatic carboxylic acid esters, the cyanate compound of being selected from;
(4) halogenated titanium: at least a being selected from as general formula Ti (OR)
N-yX
yContain the Ti compound, wherein, n is the valency of titanium, and y is the integer between 1 to n, and X is a halogen, Ti (OR)
4-mX
mShown titanium compound, R is C independently in the formula
1～C
14Aliphatic group;
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, the preferred R wherein of above-mentioned electron donor a
VIIAnd R
VIIIBe 1 of C1-C4 alkyl, the 3-diether.Relevant these 1,3 diether compounds patent disclosures are in ZL89108368, CN1141285A, CN1436766 and CN1436796A, and its associated viscera is introduced the present invention as a reference.
The example of operable ethers includes but not limited to: 2-(2-ethylhexyl)-1,3 Propanal dimethyl acetals, two-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-butyl-1, the 3-Propanal dimethyl acetal, 2-sec-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-1, the 3-Propanal dimethyl acetal, the 2-tertiary butyl-1, the 3-Propanal dimethyl acetal, 2-cumyl-1, the 3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1, the 3-Propanal dimethyl acetal, 2-(2-cyclohexyl ethyl)-1, the 3-Propanal dimethyl acetal, 2-(2-cyclohexyl ethyl)-1, the 3-Propanal dimethyl acetal, 2-(rubigan)-1, the 3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1, the 3-Propanal dimethyl acetal, 2-(1-naphthyl)-1, the 3-Propanal dimethyl acetal, 2 (to fluorophenyl)-1, the 3-Propanal dimethyl acetal, 2-(1-decahydro naphthyl)-1, the 3-Propanal dimethyl acetal, 2 (to tert-butyl-phenyl)-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1, the 3-Propanal dimethyl acetal, 2,2-dibutyl-1, the 3-Propanal dimethyl acetal, 2,2-diethyl-1, the 3-di ethyl propyl ether, 2,2-two cyclopentyl-1, the 3-di ethyl propyl ether, 2,2-dipropyl-1, the 3-di ethyl propyl ether, 2,2-dibutyl-1, the 3-di ethyl propyl ether, 2-methyl-2-ethyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1, the 3-Propanal dimethyl acetal, 2, two (rubigan)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the 2-phenylethyls)-1 of 2-, the 3-Propanal dimethyl acetal, 2, two (the 2-cyclohexyl ethyls)-1 of 2-, 3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1, the 3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal, 2, two (the 2-ethylhexyls)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (p-methylphenyl)-1 of 2-, the 3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal, 2,2-phenylbenzene-1, the 3-Propanal dimethyl acetal, 2,2-dibenzyl-1, the 3-Propanal dimethyl acetal, 2-isobutyl--2-cyclopentyl-1, the 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal, 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-dibutoxy propane, 2-isobutyl--2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2,2-two sec-butyls-1, the 3-Propanal dimethyl acetal, 2,2-di-t-butyl-1, the 3-Propanal dimethyl acetal, 2,2-di neo-pentyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-benzyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-cyclohexyl methyl-1, the 3-Propanal dimethyl acetal.And 9, two (methoxyl methyl) fluorenes of 9-, 9, two (methoxyl methyl)-2,3 of 9-, 6,7-tetramethyl-fluorenes, 9, two (methoxyl methyl)-2,3 of 9-, 4,5,6,7-hexafluoro fluorenes, 9, two (methoxyl methyl)-2 of 9-, the 3-benzofluorene, 9, two (methoxyl methyl)-2,3 of 9-, 6,7-dibenzo fluorenes, 9, two (methoxyl methyl)-2 of 9-, 7-di-isopropyl fluorenes, 9, two (methoxyl methyl)-1 of 9-, 8-difluoro fluorenes, 9, two (methoxyl methyl)-2 of 9-, 7-two cyclopentyl fluorenes, 9, two (methoxyl methyl)-1 of 9-, 8-dichloro fluorenes, 9, two (methoxyl methyl)-1,2 of 9-, 3,4-tetrahydrochysene fluorenes, 9, two (methoxyl methyl)-1,2 of 9-, 3,4,5,6,7,8-octahydro fluorenes, 9, two (the methoxyl methyl)-4-tertiary butyl fluorenes of 9-.Preferred 9, two (methoxyl methyl) fluorene compounds of 9-.
Other at least a electron donor compound b can be selected from ester, ether, ketone, amine and the silane compound etc. except that compound a in the catalyst component of the present invention.Preferred monobasic or polyhydric aliphatic family carboxylicesters or aromatic carboxylic acid esters, cyanate compound.
Wherein monobasic or polyhydric aliphatic family carboxylicesters or aromatic carboxylic acid esters are as benzoates, phthalate, the malonic ester compounds of structure shown in (IV) formula: 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; The glutarate compounds of structure shown in (V) formula: R in the formula
1And R
2Be alkyl, R
3-R
8For hydrogen or contain the alkyl R of 1～20 carbon atom
3-R
8Preferred those are linked into the alkyl of ring by halogen replacement and two substituting groups on same carbon atom; The succinate compounds of structure shown in (VI): 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; Cyano group ester compound shown in the structure (VII), R in the formula
1～R
5For hydrogen or contain alkyl, alkenyl, the aryl of 1～20 carbon atom, n is the integer between the 0-3; Pivalate or carbonates; The maleic acid diester compounds of structure shown in (VIII), R in the formula
1And R
2Be methyl or ethyl; And the alkoxide compound shown in (IX): R in the formula
1-R
6, R
1-R
2nGroup is hydrogen, halogen and the replacement identical or inequality or the C of unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene, C
10-C
20Fused ring aryl or C
2-C
10Ester group, but R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2nComprise one or several heteroatoms as carbon or hydrogen atom or both substituents on (n is 0～10 integer) group, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, and one or more in these groups can connect into ring.
The compound that can be used as electron donor b use includes but not limited to: 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.
Total consumption of internal electron donor, per 1 mole magnesium compound in the solid catalyst is about between 0.01～1, preferably at 0.05～0.5 relatively.
Except that above-mentioned electron donor, ingredient of solid catalyst of the present invention also comprises a kind of magnesium compound/mineral compound spherical complex carrier of spray drying forming and the Ti compound that contains a Ti-X key at least, and X is a halogen.
Being used for preferred Ti compound of the present invention is TiCl
4And TiCl
3Also can use general formula to be Ti (OR)
N-yX
yTitanium-containing compound, wherein n is the valency of titanium, preferred bromine of halogen and chlorine, y are the numerical value between 1 to n; Suitable magnesium compound comprises that magnesium dihalide, form are Mg (OR)
2Alkoxyl magnesium, or any can be after certain reaction and process, the magnesium-containing compound of generation magnesium dihalide and the mixture of these compounds.Object lesson such as magnesium dichloride, dibrominated magnesium, two magnesium iodides and Mg (OR)
2Deng, be preferably active magnesium dichloride.This active especially MgCl
2Be characterised in that, in X ray diffracting spectrum, appear at nonactive MgCl
2The strongest diffraction peak intensity in the diffraction spectrogram reduces and is expanded into one to swoon.Mineral compound commonly used is silicon oxide, aluminum oxide, diatomite, molecular sieve etc., preferred SiO
2, particularly preferably be the little silica gel particle of particle diameter less than 1um.The consumption of mineral compound and the amount ratio of magnesium compound should be in 0.05～10 scopes.The preparation of magnesium compound/mineral compound spherical complex carrier is preferably carried out with the method for spraying drying or spray congealing, can be with reference to disclosed concrete technological line among the Chinese patent CN1524886, and its associated viscera is introduced the present invention as a reference.
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.
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.
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.
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/g carrier), in 1～3 hour, slowly be warming up to 100～120 ℃, and in temperature-rise period, add electron donor compound a and electron donor compound b simultaneously, 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 hydrogen or the hydrocarbyl group with 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, alkylaluminium cpd is AlR
nX
3-nShown compound, R is that hydrogen or carbon atom number are alkyl, aralkyl and the alkyl of 1-20 in the formula; The alkoxy compound of aluminium; And the mixture of above-mentioned organo-aluminium compound.The preferred AlR that uses
nX
3-nCompound.Alkylaluminium cpd of the present invention comprises: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, three n-butylaluminum, aluminium diethyl monochloride and Al
2Et
3Cl
3Deng.
The consumption of organo-aluminium compound (2) 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 that is suitable for comprises silicon compound, amine, heterogeneous ring compound, ketone, succinate class, 1,3-diether compound and some other ester class and ether compound.Preferred external electron donor compound is form such as R
1 aR
2 bSi (OR
3 3)
cSilicon compound, wherein a and b are 0～2 integers, c is 1～3 integer, and a, b, c three number sums equal 4.R in the formula
1, R
2And R
3Be alkyl, cycloalkyl and aryl with 1～20 carbon atom.The preferred silicon compound of the present invention comprises: methylcyclohexyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base dimethoxy silane, cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane and tert-butyl trimethoxy silane 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 present invention also provides the catalyzer that is formed by above-mentioned ingredient of solid catalyst, organo-aluminium compound and the reaction of external electron donor compound at CH
2The polymerization of=CHR alkene and the application in the copolymerization process, wherein R is hydrogen or the hydrocarbyl group with 1～12 carbon atom.Being preferred for the polymeric alpha-olefin is ethene, propylene, butylene, 4-methyl-1-pentene, 1-hexene and 1-octene, particularly preferably is ethene and propylene.Polymerization can be carried out according to currently known methods: in liquid monomer or monomer in the solution in inert solvent, in the gas phase or by operating in the polymerization mix technology of gas-liquid in mutually.Polymerization temperature is usually between 0～150 ℃, preferably between 60～100 ℃.Pressure in the polymerization process is preferably 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, the unpolymerized propylene monomer of emptying 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 the acrylic resin that obtains sees Table 2.
Embodiment 1
The complex carrier preparation is with example 1.Unique situation that is different from example 1 is in the catalyst preparation process, adds 0.25mL 9, the n-butyl phthalate mixing electron donor of two (methoxyl methyl) fluorenes of 9-and 0.75mL.Propylene polymerization processes is with embodiment 1.
Solid catalyst is formed and some physical parameters tests see Table 1, and the performance data test result of catalyst activity and the acrylic resin that obtains sees Table 2.
Embodiment 2
The complex carrier preparation is with example 1.In catalyst preparation process, unique situation that is different from the example 1 is to add 0.50mL 9, the n-butyl phthalate mixing electron donor of two (methoxyl methyl) fluorenes of 9-and 0.50mL.Propylene polymerization processes is with embodiment 1.
Solid catalyst is formed and some physical parameters tests see Table 1, and the performance data test result of catalyst activity and the acrylic resin that obtains sees Table 2.
Embodiment 3
The complex carrier preparation is with example 1.In catalyst preparation process, unique situation that is different from the example 1 is to use 0.75mL 9, the n-butyl phthalate mixing electron donor of two (methoxyl methyl) fluorenes of 9-and 0.25mL.Propylene polymerization processes is with embodiment 1.
Solid catalyst is formed and some physical parameters tests see Table 1, and the performance data test result of catalyst activity and the acrylic resin that obtains sees Table 2.
Comparative Examples 2
The complex carrier preparation is with example 1.In catalyst preparation process, unique situation that is different from the example 1 is to add 1.0mL 9, two (methoxyl methyl) fluorene compounds of 9-.Propylene polymerization processes is with embodiment 1.
Solid catalyst is formed and some physical parameters tests see Table 1, and the performance data test result of catalyst activity and the acrylic resin that obtains 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.
aDiether:9, two (methoxyl methyl) fluorenes of 9-
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 bulk density is higher; Simple use 9, the catalyst activity that two (methoxyl methyl) fluorene compounds of 9-are done internal electron donor is higher, gained propene polymer degree of isotacticity height but bulk density is low, and molecular weight distribution is narrower.And two kinds of internal electron donor compounds are used, both guaranteed the greater activity of gained catalyzer, high upright structure orientation property and high hydrogen response, and can guarantee also that simultaneously final acrylic resin had higher bulk density and wider molecular weight distribution and helps industrial production and polymkeric substance post-treatment treating processes.
Claims (8)
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 dissolving 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 diether compound that is selected from shown in general formula (I):
R in the formula
I, R
II, R
III, R
IV, R
VAnd R
VIMutually the same or inequality, be the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl, and R
VIIAnd R
VIIIIdentical or different, be the C of straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; R
I-R
VIGroup between randomly be keyed to ring;
(3) electron donor b: at least a monobasic or polyhydric aliphatic family carboxylicesters or aromatic carboxylic acid esters, the cyanate compound of being selected from;
(4) halogenated titanium: at least a general formula Ti (OR) that is selected from
N-yX
yDescribed titanium compound, wherein, n is the valency of titanium, and y is the integer between 1 to n, and X is a halogen, and R is C independently
1～C
14Aliphatic group;
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
VIIAnd R
VIIIBe selected from C
1-C
4Alkyl.
3. the ingredient of solid catalyst that is used for olefinic polymerization according to claim 1, wherein electron donor b is selected from least a in benzoates, phthalate, malonic ester class, succinate class, glutarate class, cyano group ester class, maleic acid diester class, alkoxide and the pivalate compounds.
4. 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.
5. 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.
6. one kind is used for CH
2The catalyzer of=CHR olefinic polyreaction, wherein R is hydrogen or C
1-C
12Alkyl, comprise the reaction product of following component:
(1) the described catalyst component of one of claim 1-5;
(2) alkylaluminium cpd;
(3) external electron donor component.
7. catalyzer according to claim 6, wherein alkylaluminium cpd such as AlR
nX
3-nShown in, R is that hydrogen or carbon atom number are 1～20 alkyl or aralkyl in the formula, X is a halogen, n=1,2 or 3.
8. the application of the described catalyzer of one of claim 6～7 in olefinic polymerization.
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| CN2005101174389A CN1958621B (en) | 2005-10-31 | 2005-10-31 | Solid catalyst components in use for polymerizing olefin, catalyst, and application of catalyst |
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| CN1958621B true CN1958621B (en) | 2010-12-22 |
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Cited By (1)
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| CN111072807A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
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| CN111072814A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
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