CN103214602B - A kind of dialkoxy-magnesium support type solid catalyst and its preparation method and application - Google Patents
A kind of dialkoxy-magnesium support type solid catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of dialkoxy-magnesium support type solid catalyst, it adopts magnesium diaikoxide compound to be carrier, 1,3-diether compound or 1,3-diether compound and ester class is composite is prepared from for internal electron donor.The present invention also provides the preparation method of this solid catalyst, and the catalyst for olefines polymerizing containing this solid catalyst.When the present invention is by adopting 1,3-different diether compounds and its catalyzer with the composite gained of ester compound for propylene polymerization, demonstrate high reactivity.
Description
Technical field
The present invention relates to a kind of solid catalyst system for olefinic polymerization and preparation method thereof and the application in catalysis in olefine polymerization.Specifically, relate to a kind of adopt ether compound or itself and diester composite as internal electron donor to prepare dialkoxy-magnesium support type solid catalyst, and obtain high performance polyolefin catalyst thus.
Background technology
The development of High performance polyolefin resin depends on improving constantly of olefin polymerization catalysis performance.USP4,298,718 and USP4,495,338 propose the carrier adopting magnesium halide in active as Ziegler-Natta catalyst first, and the catalyzer that this carrier and titanium tetrachloride effect are formed shows high reactivity in propylene polymerization, but the poor property of stereotaxis.Researchist constantly makes great efforts the performance being devoted to improvement catalyzer subsequently.
GB2,111,066 discloses and is contacted with liquid titanium compound by magnesium chloride alcohol adduct, add simultaneously a kind of electronics give with body (as phthalic ester), form solid titanium catalyst, and add again when olefinic polymerization another kind of electronics give with body (oxygen radical silicide), obtain the polypropylene of high isotactic.
EP0361, solid catalyst component disclosed in 494 comprises the titanium compound of activated state magnesium halide and load at least one Ti-halogen compound key thereon and organic diether or polyether, as the catalyzer using 1,3-diether to prepare as electron donor compound.When this catalyst body ties up to polymerization, the polypropylene of high isotactic can be obtained without the need to adding external electron donor, and have higher activity.
CN1,143,651A further improves internal electron donor and/or the external electron donor of this kind of catalyzer, 1 of this system use, carbon atom on 3-diether its 2 forms special monocycle or polynuclear plane with the organic group containing two or three unsaturated link(age)s, i.e. ring polyenoid-1,3-diether, activity and the stereospecificity of catalyzer are improved to some extent.
Be that the polyolefin catalyst of carrier has a lot of outstanding advantage (EP1,209,172A1, EP1,270 with magnesium ethylate, 604A1, EP1,260,524A1, EP1,061,088A1), as high in activity, degree of isotacticity is high, hydrogen regulation performance good, polymer particle regularity is good.
The present invention finds in research process, adopt 1,3-diether compound or prepare dialkoxy-magnesium support type solid catalyst as internal electron donor with two ester compounds are composite, the catalyzer prepared thus, when catalysis in olefine polymerization, shows very high activity.
Summary of the invention
The object of the present invention is to provide a kind of employing 1,3-diether compound or prepare dialkoxy-magnesium support type solid catalyst with two ester compounds are composite as internal electron donor.
Another object of the present invention is the preparation method providing this dialkoxy-magnesium support type solid catalyst.
An also object of the present invention is that providing package contains the catalyst for olefines polymerizing of this dialkoxy-magnesium support type solid catalyst.
In order to realize the object of the invention, dialkoxy-magnesium support type solid catalyst provided by the invention, it adopts magnesium diaikoxide compound to be carrier, 1,3-diether compound or 1,3-diether compound and ester class is composite is prepared from for internal electron donor.
Wherein, described 1,3-diether compound is 1, the 3-diether compound with logical formula I, logical formula I:
Wherein: R, R
1, R
2, R
3, R
4and R
5may be the same or different, represent H or have straight chain or branched-alkyl, cycloalkyl, aryl, alkaryl or the aralkyl of 1-18 carbon atom; R
6and R
7may be the same or different, representative has the straight chain of 1-20 carbon atom or branched-alkyl, the cycloalkyl of a 3-20 carbon atom, the aryl of a 5-20 carbon atom, the alkaryl of a 7-20 carbon atom and aralkyl; R to R
7in one or more groups can link formation ring texture, the one or more heteroatomss being selected from halogen, N, O, S, P and Si can be comprised.
In the electron donor of logical formula I, preferred R
6and R
7alkyl and the more especially methyl of 1-6 carbon atom, and R
2, R
3, R
4and R
5group is preferably hydrogen.In addition, when R is methyl, ethyl, propyl group or sec.-propyl, R
2can be ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, isopentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl or benzyl; When r is hydrogen, R
2can be ethyl, butyl, sec-butyl, the tertiary butyl, 2-ethylhexyl, cyclohexyl-ethyl, diphenyl methyl, rubigan, 1-naphthyl, 1-decahydro naphthyl; R and R
2also can be identical, and can be ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, neo-pentyl, phenyl, benzyl, cyclohexyl, cyclopentyl.
The concrete example of the ethers that can advantageously use comprises: 2-(2-ethylhexyl) 1, 3-Propanal dimethyl acetal, 2-sec.-propyl-1, 3-Propanal dimethyl acetal, 2-butyl-1, 3-Propanal dimethyl acetal, 2-sec-butyl-1, 3-Propanal dimethyl acetal, 2-cyclohexyl-1, 3-Propanal dimethyl acetal, 2-phenyl-1, 3-Propanal dimethyl acetal, the 2-tertiary butyl-1, 3-Propanal dimethyl acetal, 2-cumyl-1, 3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1, 3-Propanal dimethyl acetal, 2-(2-cyclohexyl-ethyl)-1, 3-Propanal dimethyl acetal, 2-(rubigan)-1, 3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1, 3-Propanal dimethyl acetal, 2 (1-naphthyls)-1, 3-Propanal dimethyl acetal, 2 (to fluorophenyls)-1, 3-Propanal dimethyl acetal, 2 (1-decahydro naphthyls)-1, 3-Propanal dimethyl acetal, 2 (to tert-butyl-phenyls)-1, 3-Propanal dimethyl acetal, 2, 2-dicyclohexyl-1, 3-Propanal dimethyl acetal, 2, 2-diethyl-1, 3-Propanal dimethyl acetal, 2, 2-dipropyl-1, 3-Propanal dimethyl acetal, 2, 2-dibutyl-1, 3-Propanal dimethyl acetal, 2, 2-diethyl-1, 3-di ethyl propyl ether, 2, 2-bicyclopentyl-1, 3-Propanal dimethyl acetal, 2, 2-dipropyl-1, 3-di ethyl propyl ether, 2, 2-dibutyl-1, 3-di ethyl propyl ether, 2-methyl-2-ethyl-1, 3-Propanal dimethyl acetal, 2-methyl-2-propyl-1, 3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1, 3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1, 3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1, 3-Propanal dimethyl acetal, 2-methyl-2-methylcyclohexyl-1, 3-Propanal dimethyl acetal, 2, two (rubigan)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the 2-phenylethyl)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the 2-cyclohexyl-ethyl)-1 of 2-, 3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1, 3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1, 3-Propanal dimethyl acetal, 2, two (the 2-ethylhexyl)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (p-methylphenyl)-1 of 2-, 3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1, 3-Propanal dimethyl acetal, 2, 2-diisobutyl-1, 3-Propanal dimethyl acetal, 2, 2-phenylbenzene-1, 3-Propanal dimethyl acetal, 2, 2-dibenzyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclopentyl-1, 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal, 2, 2-diisobutyl-1, 3-di ethyl propyl ether, 2, 2-diisobutyl-1, 3-dibutoxy propane, 2-isobutyl--2-sec.-propyl-1, 3-Propanal dimethyl acetal, 2, 2-bis--sec-butyl-1, 3-Propanal dimethyl acetal, 2, 2-bis--tertiary butyl-1, 3-Propanal dimethyl acetal, 2, 2-di neo-pentyl-1, 3-Propanal dimethyl acetal, the iso-propyl group of 2--2-isopentyl-1, 3-Propanal dimethyl acetal, 2-phenyl-2-benzyl-1, 3-dimethoxy _ base propane, 2-cyclohexyl-2-cyclohexyl methyl-1, 3-Propanal dimethyl acetal.
In addition, 1,3-diether compounds of logical formula II particularly preferably is, logical formula II:
Wherein radicals R
6and R
7there is implication same as described above, and radicals R
2, R
3, R
4, R
5and R
9mutually the same or different, be selected from hydrogen, halogen; 1-20 carbon atom alkyl of straight chain or side chain; 3-20 carbon atom cycloalkyl, 6-20 carbon atom aryl, 7-20 carbon atom alkyl aryl and 7-20 carbon atom arylalkyl, and two or more of R
9group can bond together the ring texture forming condensation, and it is saturated or undersaturated, optionally with being selected from following R
8group replaces: halogen; 1-20 carbon atom alkyl of straight chain or side chain; 3-20 carbon atom cycloalkyl, 6-20 carbon atom aryl, 7-20 carbon atom alkyl aryl and 7-20 carbon atom arylalkyl; Described radicals R
9and R
8optionally containing one or more heteroatoms, as carbon atom or hydrogen atom or the substituting group of the two.
Preferably in 1,3-diether of logical formula I and logical formula II, whole R
2, R
3, R
4, R
5group is hydrogen, and whole R
6and R
7group is methyl.In addition 1,3-diether of logical formula II particularly preferably is, wherein two or more of R
9group bonds together to form one or more condensation ring texture, and preferred benzene ring structure, optionally uses R
8group replaces.Particularly preferably be the compound of logical formula III, logical formula III:
Wherein R
8group is identical or be differently hydrogen; Halogen; 1-20 carbon atom alkyl of straight chain or side chain; 3-20 carbon atom cycloalkyl, 6-20 carbon atom aryl, 7-20 carbon atom alkyl aryl and 7-20 carbon atom arylalkyl, optionally containing being selected from N, O, S, P, Si and halogen, one or more heteroatomss, as carbon atom or hydrogen atom or the substituting group of the two; Radicals R
2, R
3, R
4, R
5, R
6and R
7definition with logical formula II.
The object lesson of the compound that logical formula I and logical formula II comprise is:
Two (the methoxymethyl)-cyclopentadiene of 1,1-;
1,1-two (methoxymethyl)-2,3,4,5-tetramethyl-ring pentadiene;
1,1-two (methoxymethyl)-2,3,4,5-tetraphenyl cyclopentadiene;
1,1-two (methoxymethyl)-2,3,4,5-ptfe ring pentadiene;
1,1-two (methoxymethyl)-3,4-bicyclopentyl cyclopentadiene;
Two (methoxymethyl) indenes of 1,1-;
1,1-two (methoxymethyl)-2,3-dimethyl indenes;
1,1-two (methoxymethyl)-4,5,6,7-tetrahydroindene;
1,1-two (methoxymethyl)-2,3,6,7-tetrafluoro indenes;
1,1-two (methoxymethyl)-4,7-dimethyl indenes;
1,1-two (methoxymethyl)-3,6-dimethyl indenes;
Two (the methoxymethyl)-4-phenylindan of 1,1-;
Two (the methoxymethyl)-4-phenyl-2-methyl indenes of 1,1-;
Two (the methoxymethyl)-4-cyclohexyl indenes of 1,1-;
Two (methoxymethyl)-7-(3,3, the 3-trifluoro propyl) indenes of 1,1-;
Two (the methoxymethyl)-7-trimethyl silyl indenes of 1,1-;
Two (the methoxymethyl)-7-trifluoromethyl indenes of 1,1-;
1,1-two (methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene;
Two (the methoxymethyl)-7-methyl indenes of 1,1-;
Two (the methoxymethyl)-7-cyclopentyl indenes of 1,1-;
Two (the methoxymethyl)-7-sec.-propyl indenes of 1,1-;
Two (the methoxymethyl)-7-cyclohexyl indenes of 1,1-;
Two (the methoxymethyl)-7-tertiary butyl indenes of 1,1-;
Two (the methoxymethyl)-7-tertiary butyl-2-methyl indenes of 1,1-;
Two (the methoxymethyl)-7-phenylindan of 1,1-;
Two (the methoxymethyl)-2-phenylindan of 1,1-;
Two (methoxymethyl)-1H-benzo [e] indenes of 1,1-;
Two (methoxymethyl)-1H-2-methyl benzo [e] indenes of 1,1-;
Two (methoxymethyl) fluorenes of 9,9-;
9,9-two (methoxymethyl)-2,3,6,7-tetramethyl-fluorenes;
9,9-two (methoxymethyl)-2,3,4,5,6,7-hexafluoro fluorenes;
9,9-two (methoxymethyl)-2,3-benzofluorene;
9,9-two (methoxymethyl)-2,3,6,7-dibenzo fluorenes;
9,9-two (methoxymethyl)-2,7-di-isopropyl fluorenes;
9,9-two (methoxymethyl)-1,8-dichloro fluorenes;
9,9-two (methoxymethyl)-2,7-bicyclopentyl fluorenes;
9,9-two (methoxymethyl)-1,8-difluoro fluorenes;
9,9-two (methoxymethyl)-1,2,3,4-tetrahydrochysene fluorenes;
9,9-two (methoxymethyl)-1,2,3,4,5,6,7,8-octahydro fluorenes;
Two (the methoxymethyl)-4-tertiary butyl fluorenes of 9,9-.
These ethers can be independent or multiple used in combination.
Two (methoxyl methyl) fluorenes of recommendation 9,9-in these 1,3-diether, or general formula is CH
3oCH
2cRR
1cH
2oCH
3(wherein R, R
1definition with logical formula I) 2,2-dialkyl group-1,3-Propanal dimethyl acetals, as one or more the mixing in 2,2-phenylbenzene-1,3-methoxy propane, 2,2-diisobutyl-1,3-methoxy propanes.
Composite ester compound is selected to be the diester of aromatic binary carboxylic acid, as Bisphthalate or bis--terephthalate.
Bisphthalate comprises: dimethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, Methyl Benzene-o-dicarboxylate ethyl ester, Methyl Benzene-o-dicarboxylate isopropyl ester, Methyl Benzene-o-dicarboxylate n-propyl, the positive butyl ester of ethyl phthalate(DEP), ethyl phthalate(DEP) isobutyl ester, amyl phthalate, di-iso-amyl phthalate, dihexyl phthalate, heptyl phthalate ester, dinoctyl phthalate, dimixo-octyl phthalate, phthalic acid (2,2-dimethylhexanyl) diester, phthalic acid (2-ethylhexyl) diester, 2-nonyl-phthalate ester, Di Iso Decyl Phthalate, phthalic acid (2,2-dimethyl heptyl) diester, n-butyl phthalate isohexyl ester, n-butyl phthalate (2-ethylhexyl) ester, the just own ester of phthalic acid n-pentyl ester, phthalic acid n-pentyl ester ester in the different ninth of the ten Heavenly Stems, isoamyl phthalate ester in the positive last of the ten Heavenly stems, phthalic acid n-pentyl ester undecane ester, phthalic acid isopentyl isohexyl ester, the just own ester of phthalic acid (2-methylhexyl ester), phthalic acid n-hexyl (2-(ethyl hexyl) ester), the just own ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), phthalic acid n-hexyl (positive the last of the ten Heavenly stems ester), the positive heptyl ester of phthalic acid (2-(ethyl hexyl) ester), the positive heptyl ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), the positive heptyl ester of phthalic acid ester in the new ninth of the ten Heavenly Stems and phthalic acid 2-ethylhexyl (different the ninth of the ten Heavenly Stems ester).These esters can be independent or multiple used in combination.
Bis--terephthalate comprises: dimethyl terephthalate (DMT), diethyl terephthalate, terephthalic acid di-n-propyl ester, terephthalic acid diisopropyl ester, di-n-butyl terephthalate, di-n-butyl terephthalate, isobutyl terephthalate, terephthalic acid ethyl ester methyl ester, terephthalic acid methyl esters isopropyl ester, terephthaldehyde's acetoacetic ester (n-propyl), terephthaldehyde's acetoacetic ester (positive butyl ester), terephthaldehyde's acetoacetic ester (isobutyl ester), terephthalic acid two n-pentyl ester, terephthalic acid diisoamyl ester, terephthalic acid dihexyl, the positive heptyl ester of terephthalic acid two, terephthalic acid di-n-octyl, the different n-octyl of terephthalic acid two, terephthalic acid two (2,2-dimethylhexanyl) ester, terephthalic acid two (2-ethylhexyl) ester, terephthalic acid two ester in the positive ninth of the ten Heavenly Stems, terephthalic acid dinonyl, terephthalic acid two isodecyl ester, terephthalic acid two (2,2-dimethyl ethyl heptyl) ester, terephthalic acid positive butyl ester dissident ester, the positive butyl ester of terephthalic acid (2 ethylhexyl) ester, the just own ester of terephthalic acid n-pentyl ester, terephthalic acid n-pentyl ester dissident ester, terephthaldehyde's isoamyl valerate (heptyl ester), terephthalic acid, terephthalic acid n-pentyl ester (2-ethylhexyl) ester, terephthalic acid n-pentyl ester (different the ninth of the ten Heavenly Stems ester), terephthaldehyde's isoamyl valerate (positive the last of the ten Heavenly stems ester), terephthalic acid n-pentyl ester undecane ester, terephthaldehyde's isoamyl valerate dissident ester, terephthalic acid n-hexyl (2-(ethyl hexyl) ester), terephthalic acid n-hexyl (different nonyl ester), the just own ester of terephthalic acid (positive the last of the ten Heavenly stems ester), terephthalic acid n-heptyl (2-(ethyl hexyl) ester), terephthalic acid n-heptyl (different nonyl ester), terephthalic acid n-heptyl (new the last of the ten Heavenly stems ester), with terephthalic acid 2-ethylhexyl (different nonyl ester).These esters can be independent or multiple used in combination.
Recommendation diethyl phthalate in these diester, dipropyl phthalic butyl ester, terephthalic acid diisopropyl ester, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate, di-n-butyl terephthalate, isobutyl terephthalate, terephthalic acid di-n-octyl, Di-2-ethylhexyl terephthalate, one or more mixing in terephthalic acid two (2-ethylhexyl) ester or Di Iso Decyl Phthalate.
Described magnesium diaikoxide compound can adopt magnesium methylate, magnesium ethylate, propoxy-magnesium, butoxy magnesium, oxyethyl group magnesium methylate, oxyethyl group propoxy-magnesium or Butoxyethoxy magnesium etc. to prepare.It is magnesium ethylate or propoxy-magnesium preferably.It can be used alone or as a mixture.
Described magnesium diaikoxide compound can be prepared by the method that this area is conventional, and such as under halogen or metal halide exist, alcohol and reactive magnesium are made.
Described magnesium diaikoxide compound can be granular or pulverous.Also can be unformed or ball-type.If application ball-type, polymkeric substance has good grain type and narrower size distribution.Wherein round particle need not be strict ball-type can be oval or pebble-type.
The sphericity of particle is often no more than 3, and good situation is 1 to 2, is preferably 1 to 1.5, and sphericity method of calculation are the most minor axis of most major axis divided by particle of particle.
In addition, the conventional particle diameter of described magnesium diaikoxide compound is 1 μm-200 μm, and 5 to 150 μm better, is preferably 10-100 μm.These particles preferably have narrower size distribution in addition, and the coarse particle wherein contained is more few better.The particle being less than 5 μm in particle does not exceed 20%, and preferably not more than 10%, the particle being greater than 100 μm does not exceed 10%, preferably not more than 5%.The size-grade distribution S value of particle does not exceed 3, preferably not more than 2, S value calculating method is: ((D (90)-D (10))/D (50), D is diameter).
Wherein, the composite mol ratio of ester compound (diester of optimization aromatic di-carboxylic acid) and 1,3-diether is 0-1:5, is preferably 0.25-1:4, is more preferably 0.3-1:3, most preferably is 0.4-1:2.
Internal electron donor of the present invention adopts 1,3-diether compound or 1,3-diether compound and ester class composite time, consumption is add 0.001-10mol internal electron donor in every mol carrier magnesium diaikoxide compound, be preferably 0.01-1mol, be more preferably 0.02-0.6mol.
Specifically, the raw materials used component of dialkoxy-magnesium support type solid catalyst of the present invention comprises: (1) magnesium diaikoxide compound (being called for short component (1));
(2) there is the titanium compound of following formula: Ti(OR
1)
nx
4-n(R
1refer to C
1-4alkyl; X refers to chlorine, bromine, atomic iodine; N is between 0-3) (being called for short component (2));
(3) 1,3-diether compounds or 1,3-diether compound and ester class composite be internal electron donor (being called for short component (3));
(4) aromatic hydrocarbons or alkane (being called for short component (4)).
The preparation process of described dialkoxy-magnesium support type solid catalyst is as follows: the mixture of component (2) or component (4) or component (2) and (4) to mix with component (1) with random order or arbitrary combination or is repeatedly mixed and made into suspension within the scope of-20 DEG C-110 DEG C, component (3) is contacted one or many at-20 DEG C-110 DEG C with said mixture (if component (3) is made up of two kinds and above compound, can random order within the scope of-20 DEG C-110 DEG C respectively or mixing add), a certain temperature is kept 30 minutes to 4 hours at 0 DEG C-130 DEG C, can select with component (4) washing 3-6 time after filtration, can select again at 0 DEG C-130 DEG C, to contact one or many with the mixture of (4) with component (2) or component (4) or component (2), keep a certain temperature 30 minutes to 4 hours at every turn, finally by component (4) washing 3-6 time, drying forms.
Described method for preparing catalyst preferred method first component (1) and component (4) is mixed and made into suspension, then component (2) is added at-20 DEG C-30 DEG C, be warming up to 30 DEG C-80 DEG C, add component (3), be warming up to 90-110 DEG C and keep 1-3 hour, refilter, filtrate component (4) is carried out washing at least 2 times, mix at 80 DEG C-100 DEG C with the solution of component (4) and component (2) again and keep 1-3 hour, filter, finally by component (4) washing 3-6 time, drying forms.
The component (2) prepared in solid catalyst is one or more titanium tetrachloride or alkoxy titanium, and formula is as follows: Ti(OR
1)
nx
4-n.
Described component (2) comprises titanium tetrachloride, titanium tetrabromide, titanium tetra iodide or alkyl halide titanium, and alkyl halide titanium is as methoxytitanium trichloride, oxyethyl group titanous chloride, propoxy-titanous chloride, nbutoxytitanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, two n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride or three n-Butoxyl titanium-chlorides.Can be applied one or more used in combination in these halogenated titaniums.Wherein adopt titanium tetrachloride best results.
Component (4) for the preparation of solid catalyst of the present invention is a kind of room temperature is liquid aromatic hydrocarbons or alkane.Described aromatic hydrocarbons is: benzene,toluene,xylene, ethylbenzene, propyl benzene or trimethylbenzene etc., preferably uses toluene or dimethylbenzene.In addition, also can use other solvents of inertia, these organic solvents are saturated hydro carbons-alkane, comprising: hexane, heptane or hexanaphthene, and aromatic hydrocarbons and alkane can be used alone also can be used in combination.
The present invention is in the process preparing solid catalyst, and each component is preferably: component (1) is diethoxy magnesium or dipropoxy magnesium; Component (2) is titanium tetrachloride; Component (3) is that fragrance replaces 1,3-diether, (methoxyl methyl) fluorenes as two in 9,9-, or general formula is CH
3oCH
2cRR
1cH
2oCH
32,2-dialkyl group-1,3-Propanal dimethyl acetals, as 2,2-phenylbenzene-1,3-methoxy propane, 2,2-diisobutyl-1,3-methoxy propanes; Or component (3) is above-mentioned 1,3-diether and the composite use of Bisphthalate, diester is Bisphthalate, specifically with one or more diethyl phthalates, n-propyl phthalate, n-butyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate, phthalic acid (ethylhexyl) diester and didecyl phthalate; Component (4) is toluene or dimethylbenzene.
Solid catalyst of the present invention preferably adopts following methods to prepare:
Be 0.29-0.40g/cm by tap density
31mol component (1) and 4-7mol component (4) prepare suspension, then maintain-10-30 DEG C and drip 4-6mol component (2), after dropwising, system is slowly warming up to 30-80 DEG C, add 0.02-0.6mol component (3) (wherein diester and 1, the preferred 0.3-1:3 of ratio of 3-diether), then continue to be warming up to 90-110 DEG C of constant temperature 1-3 hour, elimination liquid, the solid of gained washs 2-6 time at 80-110 DEG C by 6-12mol component (4); Then the mixed solution adding component (2) and component (4) (volume ratio 1:4-3:2) is warming up to 70-110 DEG C of stir process 1-3 hour, elimination liquid, the solid of gained is by 6-15mol component (4) 40-60 DEG C of washing 2-9 time, and elimination liquid is also dry, obtains solid catalyst.
Titanium content through the solid catalyst of gained of the present invention is 1.8-4.0 (wt) %, and the tap density of solid catalyst is 0.40-0.70 gram/cm
3.(method is with the testing method of the carrier described by subsequent embodiment part)
Adopt the solid catalyst of gained of the present invention to can be used for preparing olefin polymerization catalysis, described olefin polymerization catalysis comprises following component:
(A) ingredient of solid catalyst of the present invention (being called for short component A)
(B) a kind of organo-aluminium compound (abbreviation B component), formula is as follows: R
2 palQ
3-P(R
2refer to the alkyl of C1-4; Q refers to that hydrogen atom or halogen atom are as chlorine, bromine, iodine, and the value of P is 0-3)
(C) optionally containing a kind of silicoorganic compound (being called for short component C), formula is as follows: R
3 qsi(OR
4)
4-q(R
3and R
4refer to C
1-12alkyl, cycloalkyl, phenyl, allyl group, aralkyl, vinyl, these groups can be the same or different, and the value of q is: 1-3).
Wherein: B component is preferably triethyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, diethyl aluminum bromide or ADEH.The organism of these aluminium can be used alone or two or morely to use simultaneously.What effect was best is triethyl aluminum and triisobutyl aluminium.
Component C specifically can be: trimethylmethoxysilane, trimethylethoxysilane, three n-propyl methoxy silane, three n-propyl Ethoxysilanes, three normal-butyl methoxy silane, triisobutyl Ethoxysilane, thricyclohexyl methyl-monosilane, thricyclohexyl Ethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diη-propyl dimethoxysilane, diisopropyl dimethoxy silane, diη-propyl diethoxy silane, diisopropyldiethoxysilane, di-n-butyl diethoxy silane, diisobutyl diethoxy silane, di-t-butyl dimethoxysilane, di-t-butyl dimethoxysilane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, di-t-butyl diethoxy silane, di-n-butyl diethoxy silane, n-butylmethyldimethoxyforane, two (2-ethylhexyl) dimethoxysilane, two (2-ethylhexyl) diethoxy silane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, dicyclopentyl dimethoxyl silane, bicyclopentyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl methyl diethoxy silane, cyclohexyl-ethyl dimethoxysilane, cyclohexyl sec.-propyl dimethoxysilane, cyclohexyl-ethyl diethoxy silane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl diethoxy silane, cyclopentyl sec.-propyl diethoxy silane, cyclopentyl isobutyl-dimethoxysilane, cyclohexyl n-propyl dimethoxysilane, cyclohexyl n-propyl diethoxy silane, cyclohexyl normal-butyl diethoxy silane, phenyl-methyl dimethoxysilane, phenyl-methyl diethoxy silane, amyl group ethyldimethoxysilane, amyl group ethyl diethoxy silane, cyclohexyldimethyl methoxy silane, cyclohexyl diethylmethoxysilane, cyclohexyl diethylmethoxysilane, cyclohexyl diethylethoxysilane, 2-ethylhexyl Trimethoxy silane, cyclohexyl dimethoxysilane, cyclohexyl diethoxy silane, 2-ethylhexyl triethoxyl silane, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, n-butyltrimethoxysilane, trimethoxysilane, tert-butyl trimethoxy silane, ne-butyltriethoxysilaneand, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, cyclopentyl-trimethoxy-silane, cyclopentyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, 2-ethylhexyl Trimethoxy silane, 2-ethylhexyl triethoxyl silane, amyltrimethoxysilane, amyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, cyclohexyl ring dicyclopentyldimetoxy silane, cyclohexyl ring amyl group diethoxy silane, cyclohexyl ring amyl group dipropoxy silane, 3-methyl cyclohexane cyclopentyl dimethoxysilane, 4-methyl cyclohexane cyclopentyl dimethoxysilane, 3,5-dimethyleyelohexane cyclopentyl dimethoxysilane, 3-methyl cyclohexane butylcyclohexyl dimethoxysilane, two (3-methylcyclohexyl) dimethoxysilane, 4-methyl cyclohexane butylcyclohexyl dimethoxysilane, two (4-methylcyclohexyl) dimethoxysilane, 3,5-dimethyleyelohexane butylcyclohexyl dimethoxysilane, two (3,5-Dimethylcyclohexyl) dimethoxysilane, tetrapropoxysilane, four butoxy silanes.First-selected in these silicoorganic compound: diη-propyl dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxysilane, di-n-butyl diethoxy silane, tert-butyl trimethoxy silane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl-ethyl diethoxy silane, cyclohexyl-ethyl dimethoxysilane, cyclohexyl-ethyl diethoxy silane, cyclopentyl-methyl dimethoxysilane, cyclopentyl-methyl diethoxy silane, cyclopentyl ethyl dimethoxysilane, cyclohexyl ring dicyclopentyldimetoxy silane, cyclohexyl ring amyl group diethoxy silane, 3-methyl cyclohexane cyclopentyl dimethoxysilane, 4-methyl cyclohexane cyclopentyl dimethoxysilane and 3, 5-dimethylcyclopentyl dimethoxysilane etc.These Compound C can be used alone or used in combination.
In order to the catalyzer applied in the present invention carries out olefinic polymerization, homopolymerization and copolymerization can be applied above by the catalyzer prepared by component A, B, C.The mol ratio of usual B component and component A is the titanium atom that the every mol of 1-1000mol is contained in component A, and preferably the every mol of 50-800mol is contained in the titanium atom in component A; The mol ratio of component C and B component is 0.002-10, is preferably 0.01-2, is preferably 0.01-0.5.
The order of addition(of ingredients) of each component is arbitrary, joins at first in paradigmatic system, then add component C with B component, and it is good for finally adding component A.
Polymerization technique in the present invention can carry out when having solvent or do not have solvent.Olefinic monomer can be gas phase or liquid phase.Add hydrogen further and can be used as molecular weight regulator.Certain polymerization also can be carried out when not having molecular weight regulator.Polymerization temperature is not higher than 200 DEG C, preferably not more than 100 DEG C.Polymerization pressure does not exceed 10MPa, preferably not more than 5MPa.Successive polymerization or batch polymerization process can be applied.And polyreaction can divide a step, two steps or multistep to carry out.
Apply the alkene that catalyzer of the present invention carries out homopolymerization or copolymerization to comprise, normal olefine: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-nonene, 1-decene; Branched-chain alkene is as 3-methyl-1-butene and 4-methyl-1-pentene; Diolefine is as divinyl, vinylcyclopentene and vinyl cyclohexene.Catalyzer of the present invention is preferably applied in polyethylene and polypropylene.These alkene can be independent or multiple used in combination.
Apply the polymerization (referring to mass polymerization here) of the alkene that catalyst component A, B, C of the present invention carry out, recommend the degree of isotacticity, particle properties etc. that carry out the reactive polymer of the incompatible increase catalyzer of pre-polymerization.This prepolymerization technology may be used for vinylbenzene homopolymerization equally.
In prepolymerization technology, the order of addition(of ingredients) of each component and monomer is arbitrary.Preferably first B component is joined and maybe will carry out, in the alkene gas be polymerized, after adding component A, then adding one or more alkene that will be polymerized containing inertia.In the prepolymerized process of alkene of application organosilane, advise that B component being joined rare gas element maybe will carry out in the prepolymerization system of the olefin gas be polymerized, and then adds component C, then adds component A, finally add alkene again.
Solid catalyst in olefin polymerization catalyst of the present invention is by employing 1,3-diether compound or to select and two ester compounds are composite is prepared from for internal electron donor, while maintaining with magnesium diaikoxide compound and being the olefin polymerization catalysis high isotactic of carrier, high hydrogen regulation performance, high-bulk-density, the activity of polymkeric substance has had and has significantly improved.By the catalyzer using different diether compounds can obtain different activities.In addition, the catalyzer of diether or two ester compound gained is used separately to have significant activity difference respectively, ratio difference both during composite use can cause the activity of catalyzer different, therefore by diether and two ester compounds in varing proportions composite, while meeting degree of isotacticity, form, polymerization, the adjustment of the activity of catalyzer can be realized, to meet different need of productions.
Embodiment
Further describe the present invention by embodiment below, be conducive to the understanding to the present invention and advantage thereof, better effects if, but described embodiment is only for illustration of the present invention instead of restriction the present invention.
In embodiment, the operation of Kaolinite Preparation of Catalyst is all carried out under high pure nitrogen protection.Specific embodiment is as follows.
Comparative example 1
The preparation of solid catalyst:
500ml through nitrogen fully replace with stir 5 mouthfuls of flasks in, add 10g diethoxy magnesium (tap density 0.33g/cm
3) and the prepare suspension of 80mL toluene, then maintain 30 DEG C and drip titanium tetrachloride 20mL.After dropwising, system is slowly warming up to 80 DEG C, add 3.6mLDNBP (dibutyl phthalate), then continue to be warming up to 110 DEG C of constant temperature 2 hours, then by clean for liquid press filtration, elimination liquid, the solid of gained washs 3 times at 90 DEG C with 100mL toluene.Then the mixed solution adding 40mL titanium tetrachloride and 80mL toluene is warming up to 110 DEG C of stir process 1 hour, elimination liquid, the solid of gained washs 5 times at 60 DEG C with 100mL hexane, elimination liquid is also dry, obtain 9.5g pressed powder and be ingredient of solid catalyst, analyzing titanium content is 2.57 (wt) %.
Note: in the present invention, the testing method of magnesium ethylate tap density is the laboratory simple method that the present invention sets up voluntarily, namely in nitrogen drying case, in 10mL graduated cylinder, magnesium ethylate pressed powder is flowed into glass funnel, when magnesium ethylate material level reaches 10mL, magnesium ethylate is added in stop vector cylinder, the quality m of magnesium ethylate in precise graduated cylinder, and the quality calculating every mL magnesium ethylate is the bulk density of magnesium ethylate, unit g/cm
3.
Polymerization evaluation is carried out using solid catalyst as the component of olefin polymerization catalysis:
At 5L stainless steel cauldron after nitrogen is fully replaced, add Cyclohexylmethyldimethoxysilane (CHMDMS) hexane solution that triethyl aluminum hexane solution that 5mL concentration is 0.5mol/L and 1mL concentration are 0.1mol/L and catalyzer 10mg prepared by comparative example 1, then add 10mL hexane and rinse charge line, add 2L (under standard state) hydrogen again, propylene is refined with 2.5L, control reaction 20 DEG C of pre-polymerizations 5 minutes, be warming up to 70 DEG C, at this temperature polyreaction 1 hour.After reaction terminates, lowered the temperature by reactor and stop stirring and discharge reaction product, drying obtains 403.27g polymkeric substance.Catalyst activity is 4.0 ten thousand g polypropylene/g catalyzer, and polymer bulk density is 0.45g/cm
3.(tap density of polymkeric substance adopts JISK6721 method)
Embodiment 1
Method for preparing catalyst is substantially with comparative example 1, and replace dibutyl phthalate unlike with two (methoxyl methyl) fluorenes of 3.5g9,9-, obtain 9.5g pressed powder and be ingredient of solid catalyst, analyzing titanium content is 3.02 (wt) %.
Solid catalyst adopts with the substantially identical polymerization evaluation of comparative example 1, unlike not adding Cyclohexylmethyldimethoxysilane (CHMDMS) hexane solution, catalyst activity is 6.2 ten thousand g polypropylene/g catalyzer, and polymer bulk density is 0.42g/cm
3.
Embodiment 2
The solid catalyst adopting embodiment 1 to prepare gained carries out polymerization evaluation, and polymerizing condition is identical with comparative example 1, and catalyst activity is 6.0 ten thousand g polypropylene/g catalyzer, and polymer bulk density is 0.43g/cm
3.
Embodiment 3
The solid catalyst adopting embodiment 1 to prepare gained carries out polymerization evaluation, polymerizing condition is substantially identical with comparative example 1, Cyclohexylmethyldimethoxysilane (CHMDMS) hexane solution is replaced unlike with diisopropyl dimethoxy silane (DIPDMS), catalyst activity is 7.1 ten thousand g polypropylene/g catalyzer, and polymer bulk density is 0.42g/cm
3.
Embodiment 4
The solid catalyst adopting embodiment 1 to prepare gained carries out polymerization evaluation, polymerizing condition is substantially identical with comparative example 1, Cyclohexylmethyldimethoxysilane (CHMDMS) hexane solution is replaced unlike with second, isobutyl dimethoxy silane (DIBDMS), catalyst activity is 8.0 ten thousand g polypropylene/g catalyzer, and polymer bulk density is 0.42g/cm
3.
Embodiment 5
Method for preparing catalyst, substantially with comparative example 1, replaces dibutyl phthalate unlike with 3.5g2,2-phenylbenzene-1,3-methoxy propane, obtains 9.5g pressed powder and be ingredient of solid catalyst.
Solid catalyst adopts with the substantially identical polymerization evaluation of comparative example 1, unlike not adding Cyclohexylmethyldimethoxysilane (CHMDMS) hexane solution, catalyst activity is 5.2 ten thousand g polypropylene/g catalyzer, and polymer bulk density is 0.43g/cm
3.
Embodiment 6
Method for preparing catalyst, substantially with comparative example 1, replaces dibutyl phthalate unlike with 2.9g2,2-diisobutyl-1,3-methoxy propane, obtains 9.2g pressed powder and be ingredient of solid catalyst.
Solid catalyst adopts with the substantially identical polymerization evaluation of comparative example 1, unlike not adding Cyclohexylmethyldimethoxysilane (CHMDMS) hexane solution, catalyst activity is 4.7 ten thousand g polypropylene/g catalyzer, and polymer bulk density is 0.42g/cm
3.
Embodiment 7
Method for preparing catalyst, substantially with comparative example 1, unlike adding 1.2mL n-butyl phthalate and two (methoxyl methyl) fluorenes of 2.3g9,9-, obtaining 9.1g pressed powder and being ingredient of solid catalyst.
Solid catalyst adopts with the substantially identical polymerization evaluation of comparative example 1, unlike not adding Cyclohexylmethyldimethoxysilane (CHMDMS) hexane solution, catalyst activity is 6.1 ten thousand g polypropylene/g catalyzer, and polymer bulk density is 0.43g/cm
3.
Embodiment 8
Method for preparing catalyst, substantially with comparative example 1, unlike adding 1.8mL n-butyl phthalate and two (methoxyl methyl) fluorenes of 1.7g9,9-, obtaining 8.9g pressed powder and being ingredient of solid catalyst.
Solid catalyst adopts with the substantially identical polymerization evaluation of comparative example 1, unlike not adding Cyclohexylmethyldimethoxysilane (CHMDMS) hexane solution, catalyst activity is 5.7 ten thousand g polypropylene/g catalyzer, and polymer bulk density is 0.43g/cm
3.
Embodiment 9
Method for preparing catalyst, substantially with comparative example 1, unlike adding 1.2mL n-butyl phthalate and 2.5g2,2-phenylbenzene-1,3-methoxy propane, obtaining 9.5g pressed powder and being ingredient of solid catalyst.
Solid catalyst adopts with the substantially identical polymerization evaluation of comparative example 1, unlike not adding Cyclohexylmethyldimethoxysilane (CHMDMS) hexane solution, catalyst activity is 4.8 ten thousand g polypropylene/g catalyzer, and polymer bulk density is 0.42g/cm
3.
Table 1: embodiment gathers
Note: DIPDMS is diisopropyl dimethoxy silane, and CHMDMS is Cyclohexylmethyldimethoxysilane, and DIBDMS is second, isobutyl dimethoxy silane
Can be found out by table 1, under same preparation method, adopting 1,3-diether compound or being significantly higher than with n-butyl phthalate with the activity of the composite catalyzer as internal electron donor gained of n-butyl phthalate is the catalyzer that internal electron donor obtains.The catalyst activity prepared by diether of different structure is adopted to have marked difference.By adopting the diether of different structure or by adopting diether and two ester compounds in varing proportions composite, all can realizing the adjustment of the activity of catalyzer.In addition, the activity by coordinating different external electron donors can regulate catalyzer further.
Although be above described in detail the present invention and quoted some specific exampless as proof; but for a person skilled in the art; only otherwise leave the spirit and scope of the present invention; the amendment not departing from spirit of the present invention that basis of the present invention is made or improvement, all belong to the scope of protection of present invention.
Claims (8)
1. a dialkoxy-magnesium support type solid catalyst, is characterized in that, its raw materials used component comprises: (1) magnesium diaikoxide compound, and described magnesium diaikoxide compound is magnesium ethylate or propoxy-magnesium, is called for short component (1);
(2) there is the titanium compound of following formula: Ti (OR
1)
nx
4-n, wherein R
1refer to C
1-4alkyl; X refers to chlorine, bromine, atomic iodine; N, between 0-3, is called for short component (2);
(3) 1,3-diether compounds or 1,3-diether compound and ester compound composite be internal electron donor, be called for short component (3); The two composite mol ratio is 0.4-1:2; 0.02-0.6mol internal electron donor is added in every mol carrier magnesium diaikoxide compound; Described ester compound is Bisphthalate or bis--terephthalate;
(4) aromatic hydrocarbons or alkane, is called for short component (4);
The preparation process of described dialkoxy-magnesium support type solid catalyst is as follows: the mixture of component (2) or component (4) or component (2) and (4) to mix with component (1) with random order or arbitrary combination or is repeatedly mixed and made into suspension within the scope of-20 DEG C-110 DEG C, at-20 DEG C-110 DEG C, component (3) is contacted one or many with said mixture, keep 30 minutes-4 hours at 0 DEG C-130 DEG C, selectivity component (4) washing 3-6 time after filtering; Selectivity contacts one or many with the mixture of (4) with component (2) or component (4) or component (2) again at 0 DEG C-130 DEG C, keeps 30 minutes to 4 hours at every turn; Finally by component (4) washing 3-6 time, drying forms.
2. dialkoxy-magnesium support type solid catalyst according to claim 1, is characterized in that,
Described 1,3-diether compound is 1, the 3-diether compound with logical formula I, logical formula I:
Wherein: R, R
1, R
2, R
3, R
4and R
5may be the same or different, represent H or have straight chain or branched-alkyl, cycloalkyl, aryl, alkaryl or the aralkyl of 1-18 carbon atom; R
6and R
7may be the same or different, representative has the straight chain of 1-20 carbon atom or branched-alkyl, the cycloalkyl of a 3-20 carbon atom, the aryl of a 5-20 carbon atom, the alkaryl of a 7-20 carbon atom and aralkyl; R to R
7in one or more groups can link formation ring texture, all can comprise the one or more heteroatomss being selected from halogen, N, O, S, P and Si.
3. dialkoxy-magnesium support type solid catalyst according to claim 2, is characterized in that, described 1,3-diether compound is 1,3-diether compounds of logical formula II, logical formula II:
Wherein radicals R
6and R
7there is the implication identical with logical formula I, and radicals R
2, R
3, R
4, R
5and R
9mutually the same or different, be selected from hydrogen, halogen; 1-20 carbon atom alkyl of straight chain or side chain; 3-20 carbon atom cycloalkyl, 6-20 carbon atom aryl, 7-20 carbon atom alkyl aryl and 7-20 carbon atom arylalkyl, and two or more of R
9group can bond together the ring texture forming condensation, and it is saturated or undersaturated, optionally with being selected from following R
8group replaces: halogen; 1-20 carbon atom alkyl of straight chain or side chain; 3-20 carbon atom cycloalkyl, 6-20 carbon atom aryl, 7-20 carbon atom alkyl aryl and 7-20 carbon atom arylalkyl; Described radicals R
9and R
8optionally containing one or more heteroatoms, as carbon atom or hydrogen atom or the substituting group of the two.
4. dialkoxy-magnesium support type solid catalyst according to claim 3, is characterized in that, described 1,3-diether compound is the compound of logical formula III, logical formula III:
Wherein R
8group is identical or be differently hydrogen; Halogen; 1-20 carbon atom alkyl of straight chain or side chain; 3-20 carbon atom cycloalkyl, 6-20 carbon atom aryl, 7-20 carbon atom alkyl aryl and 7-20 carbon atom arylalkyl, optionally containing the one or more heteroatomss being selected from N, O, S, P, Si and halogen, as carbon atom or hydrogen atom or the substituting group of the two; Radicals R
2, R
3, R
4, R
5, R
6and R
7definition with logical formula II.
5. dialkoxy-magnesium support type solid catalyst according to claim 1, is characterized in that, described 1,3-diether compound is two (methoxyl methyl) fluorenes of 9,9-, or general formula is CH
3oCH
2cRR
1cH
2oCH
3(wherein R, R
1definition with logical formula I) 2,2-dialkyl group-1,3-Propanal dimethyl acetals in one or more mixing.
6. dialkoxy-magnesium support type solid catalyst according to claim 5, is characterized in that, described 2,2-dialkyl group-1,3-Propanal dimethyl acetals are 2,2-phenylbenzene-1,3-Propanal dimethyl acetals or 2,2-diisobutyl-1,3-Propanal dimethyl acetal.
7. prepare the method for the dialkoxy-magnesium support type solid catalyst described in claim 1-6 any one, it is characterized in that, raw materials used component comprises: (1) magnesium diaikoxide compound, is called for short component (1);
(2) there is the titanium compound of following formula: Ti (OR
1)
nx
4-n, wherein R
1refer to C
1-4alkyl; X refers to chlorine, bromine, atomic iodine; N, between 0-3, is called for short component (2);
(3) 1,3-diether compounds or 1,3-diether compound and ester class composite be internal electron donor, be called for short component (3);
(4) aromatic hydrocarbons or alkane, is called for short component (4);
The preparation process of described dialkoxy-magnesium support type solid catalyst is as follows: the mixture of component (2) or component (4) or component (2) and (4) to mix with component (1) with random order or arbitrary combination or is repeatedly mixed and made into suspension within the scope of-20 DEG C-110 DEG C, at-20 DEG C-110 DEG C, component (3) is contacted one or many with said mixture, keep 30 minutes-4 hours at 0 DEG C-130 DEG C, selectivity component (4) washing 3-6 time after filtering; Selectivity contacts one or many with the mixture of (4) with component (2) or component (4) or component (2) again at 0 DEG C-130 DEG C, keeps 30 minutes to 4 hours at every turn; Finally by component (4) washing 3-6 time, drying forms.
8. the catalyst for olefines polymerizing containing dialkoxy-magnesium support type solid catalyst described in claim 1-6 any one.
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| CN105622410A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Fluorenyl group and carboxylic acid ester combined compound and application thereof |
| CN105622804A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Solid catalyst component used for olefin polymerization and catalyst used for olefin polymerization and application |
| CN105541623A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Fluorenyl group and carboxylate combination compound and application thereof |
| CN105622416B (en) * | 2014-11-03 | 2018-05-11 | 中国石油化工股份有限公司 | The preparation method for the compound that a kind of fluorene group and carboxylate combine |
| CN106565871B (en) * | 2015-10-13 | 2019-07-30 | 中国石油化工股份有限公司 | The preparation method of catalyst component for olefin and preparation method thereof and polyethylene |
| CN108239191B (en) * | 2016-12-23 | 2019-10-01 | 北京利和知信科技有限公司 | A kind of alkoxyl magnesium carrier model catalyst component for olefin polymerization, catalyst and its application |
| CN108341899A (en) * | 2017-01-22 | 2018-07-31 | 任丘市利和科技发展有限公司 | A kind of catalytic component, preparation method and applications being used for vinyl polymerization or combined polymerization based on alkoxyl magnesium carrier |
| CN107602736B (en) * | 2017-09-29 | 2020-02-07 | 营口市向阳催化剂有限责任公司 | Universal α -olefin polymerization industrial catalyst and application thereof |
| CN112574341B (en) * | 2020-12-17 | 2022-11-01 | 沧州利和科技发展有限责任公司 | Catalyst component for synthesizing high-rigidity polypropylene, catalyst and preparation method thereof |
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