CN101560273A - Olefinic polymerization catalyst, preparation method and polymerization method - Google Patents
Olefinic polymerization catalyst, preparation method and polymerization method Download PDFInfo
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Abstract
The invention relates to an olefinic polymerization catalyst, a preparation method and a polymerization method. The olefinic polymerization catalyst comprises three components: A is solid catalyst component, B is organo-aluminum compound, and C is external electron donor and organic silicon compound; wherein, the A component contains titanium, magnesium and chlorine elements as well as internal electron donor which is the combination of 2, 4- diaryl acid pentanediol ester (PBA) and 1, 3-diether (BMF), the combination of the PBA and 1, 4- diaryl ether (BN), or the combination of PBA and aromatic acid ester. The olefinic polymerization catalyst has higher catalytic activity, the activity of the catalyst used for propylene polymerization can be regulated within the range of 40.0-120.0Kg pp/g Cat, and isotactic index and molecular weight distribution index of polypropylene are also can be adjusted within the wide range.
Description
Technical field
The present invention relates to olefinic polyreaction with the component of catalyzer and preparation method thereof and polymerization process.This catalyzer is applicable to the homopolymerization or the copolyreaction of alpha-olefins such as ethene, propylene, 1-butylene, iso-butylene.
Technical background
Ziegler-Natta catalyst is the main flow of industrial olefinic polyreaction with catalyzer.At present, industrial polyolefin catalyst is the metallocene carried catalyst more than 95%, its synthetic preparing carriers and two aspects of internal electron donor development of mainly comprising.The exploitation of internal electron donor is promoting the development of Ziegler-Natta catalyst, it is by monobasic acid ester, develop into the binary aryl esters as ethyl benzoate and ethyl p-ethoxybenzoate etc., as n-butyl phthalate, diisobutyl phthalate, dioctyl phthalate (DOP) etc.The catalyzer that these electron donors constitute is present industrial widely used catalyzer, and its price comparison is cheap, but its activity is lower, and catalyst levels is big, ash oontent height in the polymkeric substance, and polymericular weight is difficult for shortcomings such as conciliation, can not meet the need of market.More in recent years having the new electron donor of property constantly is developed, as succinate (CN1313869A), maleate (EP 1395617), glutarate (CN 1306544 A) and two aromatic acids-2,4-pentadiol ester (CN 1453298 A) etc., these esters are that the catalyst activity that electron donor constitutes increases, and the polymkeric substance over-all properties makes moderate progress.1,3-diether (EP 1395617), particularly fragrance 1,3-diether compounds such as (CN 1268957A, CN 1141285 A) is that the catalyzer of electron donor preparation has the highest current catalyst activity, even can save external electron donor, but polyolefinic molecular weight distribution is narrower, has limited polyolefinic application.1, compound internal electron donor (CN 1831017A, US-2008-0161513-A such as 4-virtue diether
1) appearance overcome the shortcoming of the catalyzer of above-mentioned all electron donors preparation, be the new direction of Ziegler-Natta catalyst electron donor exploitation.
Summary of the invention
Catalyst for olefines polymerizing contains A, B, C three components: A is an ingredient of solid catalyst, titaniferous, magnesium, chlorine element and internal electron donor, and B is a promotor, C is an external electron donor.The objective of the invention is shortcoming at the catalyzer of existing electron donor preparation, in exploitation 2,4-two aromatic acid pentadiol esters are on the basis of high activated catalyst component of internal electron donor, develop 2, the catalyst component of the combination internal electron donor of 4-two aromatic acid pentadiol esters, improve the performance of catalyzer, make olefinic polymerization or copolymerization not only have better comprehensive performance with catalyzer, but also can be as required to certain performance of catalyzer, regulate as the isotactic index of catalyst activity, poly-alpha olefins and molecular weight distributing index etc.
It is 2 that the present invention works out novel combination internal electron donor, and 4-two aromatic acid pentadiol esters (hereinafter to be referred as PBA) are respectively with 1,3-diether (hereinafter to be referred as BMF), 1,4-virtue diether (hereinafter to be referred as BN) or with organic aryl esters combination.
2,4-two aromatic acid pentadiol esters comprise that the mol ratio of 4-two aromatic acid pentadiol esters and two aromatic acids is 1: 1 mixing 2,4-two aromatic acid pentadiol esters with 2.Aromatic acid wherein comprises phenylformic acid, naphthoic acid and five yuan of fragrant heterocycle formic acid three major types.
The benzoic acids aromatic acid is phenylformic acid, 1～3 alkyl substituted benzoic acid.1～3 alkyl is the straight or branched alkyl that contains 1～6 carbon atom, and alkyl is identical, also can be different.As 3,4,5-trimethylbenzoic acid, 3, the 5-mesitylenic acid, 3,5-diethylbenzene formic acid, 3,5-dipropyl phenylformic acid, 3,5-di-isopropyl phenylformic acid, 3,5-dibutyl phenylformic acid, 3,5-diisobutyl phenylformic acid, 3, the 5-di-tert-butyl benzoic acid, 3,5-diamyl phenylformic acid, 3,5-diisoamyl phenylformic acid, 3,5-two tert.-amylbenzene formic acid, 3,5-dihexyl phenylformic acid, 4-tolyl acid, 4-ethyl benzoate, the 4-propylbenzoic acid, 4-isopropyl acid, 4-butylbenzoic acid, 4-isobutyl-benzene formic acid, 4-p t butylbenzoic acid, 4-amylbenzene formic acid, 4-isoamylbenzene formic acid, 4-tert.-amylbenzene formic acid, 4-hexyl benzene formic acid etc.
Naphthoic acid class aromatic acid is that 1-naphthoic acid, 1～5 alkyl replace the 1-naphthoic acid.1～5 alkyl is the straight or branched alkyl that contains 1～6 carbon atom, and alkyl is identical, also can be different.As 3,4,5,6,7-pentamethyl--1-naphthoic acid, 3,4,5,6-tetramethyl--1-naphthoic acid, 3,4,5-front three-1-naphthoic acid, 4,5-dimethyl-1-naphthoic acid, 4,5-diethyl-1-naphthoic acid, 4,5-dipropyl-1-naphthoic acid, 4,5-di-isopropyl-1-naphthoic acid, 4,5-dibutyl-1-naphthoic acid, 4,5-diisobutyl-1-naphthoic acid, 4,5-di-t-butyl-1-naphthoic acid, 4,5-diamyl-1-naphthoic acid, 4,5-diisoamyl-1-naphthoic acid, 4,5-two tert-pentyls-1-naphthoic acid, 4,5-dihexyl-1-naphthoic acid, 4-methyl isophthalic acid-naphthoic acid, 4-ethyl-1-naphthoic acid, 4-propyl group-1-naphthoic acid, 4-sec.-propyl-1-naphthoic acid, 4-butyl-1-naphthoic acid, 4-isobutyl--1-naphthoic acid, the 4-tertiary butyl-1-naphthoic acid, 4-amyl group-1-naphthoic acid, 4-isopentyl-1-naphthoic acid, 4-tert-pentyl-1-naphthoic acid, 4-hexyl-1-naphthoic acid etc.
Naphthoic acid class aromatic acid also comprises 2-naphthoic acid, 1～5 alkyl replacement-2-naphthoic acid.1～5 alkyl is the straight or branched alkyl that contains 1～6 carbon atom, and alkyl is identical, also can be different.As 4,5,6,7,8-pentamethyl--2-naphthoic acid, 4,5,6,8-tetramethyl--2-naphthoic acid, 4,5,8-trimethylammonium-2-naphthoic acid, 4,5-dimethyl-2-naphthoic acid, 4,5-diethyl-2-naphthoic acid, 4,5-dipropyl-2-naphthoic acid, 4,5-di-isopropyl-2-naphthoic acid, 4,5-dibutyl-2-naphthoic acid, 4,5-diisobutyl-2-naphthoic acid, 4,5-di-t-butyl-2-naphthoic acid, 4,5-diamyl-2-naphthoic acid, 4,5-diisoamyl-2-naphthoic acid, 4,5-two tert-pentyls-2-naphthoic acid, 4,5-dihexyl-2-naphthoic acid, 4-methyl-2-naphthoic acid, 4-ethyl-2-naphthoic acid, 4-propyl group-2-naphthoic acid, 4-sec.-propyl-2-naphthoic acid, 4-butyl-2-naphthoic acid, 4-isobutyl--2-naphthoic acid, 4 tertiary butyls-2-naphthoic acid, 4-amyl group-2-naphthoic acid, 4-isopentyl-2-naphthoic acid, 4-tert-pentyl-2-naphthoic acid, 4-hexyl-2-naphthoic acid etc.
Five yuan of fragrant heterocycle formic acid class aromatic acids comprise furancarboxylic acid, 1～3 alkyl substituted furan formic acid.1～3 alkyl is the straight or branched alkyl that contains 1～6 carbon atom, and alkyl is identical, also can be different.As 3,4,5-trimethylammonium furancarboxylic acid, 4,5-dimethyl furan formic acid, 4,5-diethyl furancarboxylic acid, 4,5-dipropyl furancarboxylic acid, 4,5-di-isopropyl furancarboxylic acid, 4,5-dibutyl furancarboxylic acid, 4,5-diisobutyl furancarboxylic acid, 4,5-di-t-butyl furancarboxylic acid, 4,5-diamyl furancarboxylic acid, 4,5-diisoamyl furancarboxylic acid, 4,5-two tert-pentyl furancarboxylic acids, 4,5-dihexyl furancarboxylic acid, 5-methyl furan formic acid, 5-ethyl furan formic acid, 5-propyl group furancarboxylic acid, 5-sec.-propyl furancarboxylic acid, 5-butyl furancarboxylic acid, 5-isobutyl-furancarboxylic acid, 5-tertiary butyl base furancarboxylic acid, 5-pentyl furan formic acid, 5-isopentyl furancarboxylic acid, 5-tert-pentyl furancarboxylic acid, 5-hexylfuran formic acid etc.;
Five yuan of fragrant heterocycle formic acid class aromatic acids also comprise thiophenic acid, 1～3 alkylated substituted thiazoline phenol formic acid.1～3 alkyl is the straight or branched alkyl that contains 1～6 carbon atom, and alkyl is identical, also can be different.As 3,4,5-trimethylthiophene formic acid, 4,5-thioxene formic acid, 4,5-diethyl thiophenic acid, 4,5-dipropyl thiophenic acid, 4,5-di-isopropyl thiophenic acid, 4,5-dibutyl thiophenic acid, 4,5-diisobutyl thiophenic acid, 4,5-di-t-butyl thiophenic acid, 4,5-diamyl thiophenic acid, 4,5-diisoamyl thiophenic acid, 4,5-two tert-pentyl furancarboxylic acids, 4,5-dihexyl furancarboxylic acid, 5-thiotolene formic acid, 5-ethylthiophene formic acid, 5-propyl group thiophenic acid, 5-sec.-propyl thiophenic acid, 5-butyl thiophene formic acid, 5-isobutyl-thiophenic acid, 5-tertiary butyl thiophenic acid, 5-amylic thiophene formic acid, 5-isopentyl thiophenic acid, 5-tert-pentyl thiophenic acid, 5-hexyl thiophene formic acid etc.
Above-mentioned each aromatic acid and 2, the reaction of 4-pentanediol is synthetic with 2,4-two aromatic acid pentadiol esters, any two aromatic acids and 2, the reaction of 4-pentanediol is synthetic to mix 2,4-two aromatic acid pentadiol esters.
Prepared the magnesium chloride alcohol adduct with synthesis type magnesium chloride and carrier model magnesium chloride preparation method, further prepared olefinic polymerization, copolymerization catalyst A component with multiple combination electron donor; The catalyzer that this A component makes has advantages of high catalytic activity and controllability, is used for alpha-olefin such as propylene polymerization, and activity of such catalysts can be regulated between 40.0～120.0KgPP/gCat; Polyacrylic isotactic index, molecular weight distribution also can be in regulated in wider range; Synthesize have good flowability, higher polymkeric substance apparent density and the good propene polymer of form.
Olefinic polymerization, copolymerization comprise A ingredient of solid catalyst, B cocatalyst component organo-aluminium compound and C external electron donor compound with catalyzer.The A ingredient of solid catalyst also contains three kinds of alternative combination internal electron donor: PBA and 1 except that containing Ti, Mg and Cl element, 3-diether (BMF) combination, and its preferred mol ratio is 0.1～30; PBA and 1,4-two aryl oxides (BN) combination, its preferred mol ratio is 0.1～30; PBA and the combination of organic aryl esters, its preferred mol ratio is 0.1～40.When internal electron donor is PBA and BMF combination, can be without the C component.
Described 1, the 3-diether is 9, and two (methoxyl methyl) fluorenes of 9-or general formula are CH
3OCH
2CR
4R
5CH
2OCH
32,2-dialkyl group-1,3-Propanal dimethyl acetal, wherein R
4And R
5Be respectively and contain C
3～C
16Straight or branched alkyl, C
3～C
10Cycloalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl, R
4And R
5Be identical or different.As 2,2-di-isopropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1, the 3-Propanal dimethyl acetal, 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal, 2,2-di-t-butyl-1,3-Propanal dimethyl acetal, 2,2-diisoamyl-1, the 3-Propanal dimethyl acetal, 2,2-two tert-pentyls-1,3-Propanal dimethyl acetal, 2,2-phenylbenzene-1, the 3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-the tertiary butyl-1, the 3-Propanal dimethyl acetal, 2-isobutyl--2-the tertiary butyl-1,3-Propanal dimethyl acetal etc.
Preparation, use 1, the 3-diether is 9, two (methoxyl methyl) fluorenes of 9-are easily.
1,4-virtue diether comprises 2,2 '-dialkoxy-1,1 '-dinaphthalene, 6,6 '-dialkyl-2,2 '-dialkoxy-1,1 '-dinaphthalene or 6,6 '-dihalo--2,2 '-dialkoxy-1,1 '-dinaphthalene.Wherein alkyl is to contain C
3-C
12Straight or branched alkyl, dialkyl are identical or different; Alkyl in the dialkoxy is C
1-C
4Straight or branched alkyl, dialkyl group are identical or different; Halogen is chlorine or bromine.As 2,2 '-dimethoxy-1,1 '-dinaphthalene, 2,2 '-diethoxy-1,1 '-dinaphthalene, 2,2 '-dipropoxy-1,1 '-dinaphthalene, 2,2 '-dibutoxy-1,1 '-dinaphthalene, 6,6 '-dimethyl-2,2 '-dimethoxy-1,1 '-dinaphthalene, 6,6 '-diethyl-2,2 '-dimethoxy-1,1 '-dinaphthalene, 6,6 '-dipropyl-2,2 '-dimethoxy-1,1 '-dinaphthalene, 6,6 '-dibutyl-2,2 '-dimethoxy-1,1 '-dinaphthalene, 6,6 '-diisobutyl-2,2 '-dimethoxy-1,1 '-dinaphthalene, 6,6 '-di-t-butyl-2,2 '-dimethoxy-1,1 '-dinaphthalene, 6,6 '-dihexyl-2,2 '-dimethoxy-1,1 '-dinaphthalene, 6,6 '-two bromo-2,2 '-dimethoxy-1,1 '-dinaphthalene etc.
Organic aryl esters is alkyl substituted benzoic acid alkyl ester, bialkyl ortho phthalate, and wherein alkyl is to contain C
1～C
8The straight or branched alkyl.As ethyl benzoate, butyl benzoate, methoxybenzoic acid ethyl ester, ethoxy benzonitrile acetoacetic ester, diethyl phthalate, dipropyl phthalate, n-butyl phthalate, diisobutyl phthalate, dioctyl phthalate (DOP) etc.
The titanium compound of preparation catalyst A component is that to be selected from chemical formula be Ti R
n(OR ')
mX
4-m-nCompound, R, R ' are respectively the alkyl with 1-8 carbon atom in the formula, X is a chlorine, 0≤m≤4,0≤n≤4 or TiCl
3, use titanium tetrachloride and four titan-alkoxides more convenient.
Preparation ingredient of solid catalyst A is reacted into the magnesium chloride alcohol adduct with Magnesium Chloride Anhydrous and alcohol under 110～150 ℃, react 1～2h with titanium compound and internal electron donor in 100～120 ℃ again, filter, solid adds titanium compound again in 100～120 ℃ of reaction 1～2h, so repeat 1～3 time, with the inert solvent washing, form through vacuum-drying.Must under-10～-30 ℃, carry out when alcohol adduct and titanium compound reaction.Through practice especially with following three kinds of methods for well:
Wherein method one (synthesis type magnesium chloride) is a Magnesium Chloride Anhydrous and alcohol reacts 2～5h in the solvent of unreactive hydrocarbons, in the presence of electron donor or the complex compound that formed by electron donor and titanium compound, in 110～140 ℃, generates stable synthesis type magnesium chloride alcohol adduct; The complex compound that electron donor and titanium compound form is in advance titanium compound and electron donor to be added in the unreactive hydrocarbons solvent, and 0.5～2h obtains complex solution in the stirring at room reaction.Alcohol adduct is added drop-wise in the Ti compound then, in the presence of internal electron donor, react 1～2h in 100～120 ℃, the solid that filters out is added the Ti compound again, again in 100～120 ℃ of reaction 1～2h, after the re-treatment like this 1～3 time, use inert solvent that products therefrom is washed, obtain ingredient of solid catalyst by vacuum-drying at last.
Method two (synthesis type magnesium chloride) is that Magnesium Chloride Anhydrous and excessive alcohol generate stable synthesis type magnesium chloride alcohol adducts 110～140 ℃ of reactions, reduces temperature then and adds the SiO that handles well
2, be warmed up to 110～140 ℃ again and continue reaction 1～3h, vacuumize and handle the carrier that obtains good fluidity.This carrier is added in the Ti compound, in the presence of internal electron donor, reacts 1～2h in 100～120 ℃.To filter out solid and add the Ti compound again, and, so after the re-treatment 1～3 time, use inert solvent that products therefrom is washed, obtain ingredient of solid catalyst by vacuum-drying at last again in 100～120 ℃ of reaction 1～2h.
Method three (carrier model magnesium chloride) be with magnesium chloride with alcohol in mineral oil in 110～150 ℃ of reactions, the alcohol adduct that generates is dispersed in the mineral oil, the alcohol adduct that will be dispersed in the mineral oil by high speed dispersion emulsification or other means is dispersed into drop then, be sprayed onto low temperature again and receive in the solvent, make the rapid quenching of emulsion droplet be solidified into microspheroidal.The method of narrating in Chinese patent ZL94103454.2 prepares stable spherical magnesium chloride alcohol adduct, with this spherical alcohol adduct after inert solvent washing and vacuum-drying, be added in the Ti compound, in the presence of internal electron donor, react 1～2h in 100～120 ℃, the solid that filters out is added the Ti compound again, again in 100～120 ℃ of reaction 1～2h, so after the re-treatment 1～3 time, use inert solvent to products therefrom wash, drying obtains ingredient of solid catalyst.
The specific surface area of Zhi Bei A ingredient of solid catalyst is 100～400m as stated above
2/ g, porosity is 0.4～1.5cm
3/ g.
It is R that B cocatalyst component organo-aluminium compound is selected from chemical formula
mAlX
3mCompound, R is C in the formula
1-C
8The straight or branched alkyl, X is a halogen, 1≤m≤3.Using triethyl aluminum, triisobutyl aluminium is easily.
External electron donor compound of the present invention is organosilicon, ether, ester, heterogeneous ring compound.The general formula of silicoorganic compound is R
1 aR
2 bSi (OR
3)
c, R in the formula
1, R
2Be C
1～C
10Straight or branched alkyl, C
3～C
10Cycloalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl, R
1, R
2Can be identical or different, R
3Be C
1-C
6The straight or branched alkyl, a, b, c are integer, 0≤a≤3,0≤b≤3,1≤c≤3, a+b+c=4.The object lesson of silicoorganic compound comprises: dimethylformamide dimethyl oxygen base silicon, diethyl dimethoxy silicon, dipropyl dimethoxy silicon, dibutyl dimethoxy silicon, diisobutyl dimethoxy silica, dicyclopentyl dimethoxyl silicon, dicyclohexyl dimethoxy silicon, phenylbenzene dimethoxy silicon, methyl tertbutyl dimethoxy silicon, methylcyclopentyl dimethoxy silicon, methylcyclohexyl dimethyl-silicon, aminomethyl phenyl dimethoxy silicon, methyl trimethoxy oxygen base silicon, ethyl trimethoxy silicon, propyl trimethoxy silicon, sec.-propyl trimethoxy silicon, butyl trimethoxy silicon, isobutyl-trimethoxy silicon, methyltriethoxy silane, ethyl triethoxy silicane, propyl-triethoxysilicane, sec.-propyl triethoxysilicane, butyl triethoxysilicane, cyclopentyl trimethoxy silicon, cyclohexyl trimethoxy silicon, cyclopentyl triethoxysilicane, cyclohexyl triethoxysilicane, phenyl trimethoxy silicon, phenyltriethoxy silane.Use 2 if be used for the internal electron donor of olefin polymerization catalysis, 4-two aromatic acid pentadiol esters and 1, the combination of 3-diether then also can obtain the poly-alpha olefins of higher isotactic index without external electron donor.
Olefine polymerizing process
Olefine polymerizing process of the present invention is known slurry polymerization, vapour phase polymerization and mass polymerization.Earlier alkene and promotor organo-aluminium compound and the 3rd component being added the electron donor compound during mass polymerization quantitatively is added in the autoclave, and then with the ingredient of solid catalyst for preparing, add in the autoclave by certain promotor organo-aluminium compound/ingredient of solid catalyst (in titanium) mol ratio, after feeding hydrogen, close charging valve and reacting by heating still, be warming up to temperature of reaction, keep isothermal reaction, finish until polyreaction.Reduce temperature of reaction kettle to room temperature, isolate polyolefine, the polyolefinic physicochemical property of dry back test.
Described alkene (CH
2In=CHR) the polyreaction, A ingredient of solid catalyst (calculating by Ti) is B/A=1～1000 with the mol ratio of B cocatalyst component and C external electron donor compound, C/B=0～1; R is hydrogen or C
1-C
8Alkyl.
Polyreaction of the present invention is carried out under 40～150 ℃ temperature usually.When polyreaction was carried out in gas phase, the working pressure scope was generally 1～4MPa.The working pressure scope of slurry polymerization is generally at 0.1～2MPa.When mass polymerization, the working pressure scope is generally at 1～5MPa.
The present invention is further illustrated with the following examples.
Embodiment 1
A) alcohol adduct preparation:
The there-necked flask that agitator and thermometer are housed adds anhydrous MgCl after nitrogen is fully replaced
25 grams, decane 30ml and 2-Ethylhexyl Alcohol 23.0ml.Warming while stirring to 130 ℃, and under this temperature, react 2h.In advance 1.5ml tetrabutyl titanate and 2ml diisobutyl phthalate (hereinafter to be referred as DIBP) are added in the 5ml toluene, 0.5h obtains complex solution in the stirring at room reaction.This toluene solution is added in the there-necked flask, and continues reaction 1h at 130 ℃.Reaction finishes, and is cooled to room temperature, forms stable alcohol adduct solution.
B) preparation of A ingredient of solid catalyst
In 30min, the alcohol adduct drips of solution of above-mentioned preparation is added to agitator and thermometer to be housed and fully to replace, fill through nitrogen adds the 200ml titanium tetrachloride in advance and remain in-20 ℃ the reactor.Dropwise, be warming up to 70 ℃, add 2-(2-thiophenic acid)-4-(to ethyl benzoate) pentadiol ester of 3.0mmol, add DIBP 1.0ml when continuing to be warming up to 110 ℃, under this temperature, react 2h.Reaction finishes, filter out liquid after, add the 200ml titanium tetrachloride again and at 110 ℃ of reaction 1.5h.Leach reaction solution after reaction finishes, wash 60min at 60 ℃ with trichloromethane, be washed till in the filtrate till the no free chlorion with hexane then, solid product gets the A ingredient of solid catalyst through vacuum-drying.
A ingredient of solid catalyst analytical results:
Titanium content: 2.6wt%; Specific surface area: 252.57m
2/ g; Median size: 21.45 μ m.
C) polyreaction
On 2 liters of stainless steel cauldrons, the agitator that changes 600 rev/mins of scooters is housed, after nitrogen is fully replaced, adding refining propylene of 1.5L and 4.0ml concentration is the hexane solution and the 0.1ml CHMMS (cyclohexyl methyl dimethoxy silicon) of the triethyl aluminum of 1mol/L, and adds by b) the A catalyst component 0.0049mmol (press titanium calculating) of step preparation.Then, be warming up to 70 ℃, adding dividing potential drop is the hydrogen of 0.2MPa.Polyreaction 1.5h under this temperature.After reaction finished, logical water coolant to room temperature, stopped the still temperature drop to stir, and gets rid of unreacting gas, obtains reaction product, gets the 574g white polymer through vacuum-drying.
Catalyst activity is 54.9KgPP/g.Cat; Polymkeric substance apparent density 0.44g/cm
3Polymkeric substance isotactic index 95.9% (boiling heptane extraction process).Polymer melt index 5.12.
Embodiment 2
B with embodiment 1) in the step, 70 ℃ of 2-(2-thiophenic acid)-4-(to ethyl benzoate) pentadiol esters that add 3.0mmol change adding 2 into, 2 '-dimethoxy-1,1 '-dinaphthalene, adding DIBP (diisobutyl phthalate) 1.0ml during with 110 ℃ changes into and adds 2-(cuminic acid)-4-(3, the 5-mesitylenic acid) pentadiol ester, other step is with embodiment 1.
Catalyst activity is 53.7KgPP/g.Cat; Polymkeric substance apparent density 0.44g/cm
3Polymkeric substance isotactic index 96.7%.
Embodiment 3
B with embodiment 1) in the step, 70 ℃ of 2-(2-thiophenic acid)-4-(to ethyl benzoate) pentadiol esters that add 3.0mmol change adding 2 into, 2 '-dimethoxy-1,1 '-dinaphthalene, adding DIBP (diisobutyl phthalate) 1.0ml during with 110 ℃ changes into and adds 2,-two (2-naphthoic acid) pentadiol ester, other step
Suddenly with embodiment 1.
Catalyst activity is 54.6KgPP/g.Cat; Polymkeric substance apparent density 0.44g/cm
3Polymkeric substance isotactic index 97.7%.
Embodiment 4
Method according to Chinese patent ZL94103454.2, in mineral oil, in 110-150 ℃, magnesium chloride and alcohol reaction, the alcohol adduct that generates is dispersed in the mineral oil, the alcohol adduct that will be dispersed in the mineral oil by Φ 1.5mm kapillary is dispersed into drop then, be sprayed onto low temperature and receive in the solvent, make the rapid quenching of emulsion droplet be solidified into microspheroidal, through inert solvent washing final vacuum do ball type carrier.The 5g ball type carrier of preparation is added to agitator and thermometer to be housed and fully to replace, fill through nitrogen and adds the 200ml titanium tetrachloride in advance and remain in-20 ℃ the reactor.Be warming up to 70 ℃ then, 2,2 of adding 3.0mmol '-dimethoxy-1,1 '-dinaphthalene, continue to be warming up to 110 ℃, add 2,4-two (p-methylbenzoic acid) pentadiol ester 1.0ml, under this temperature, react 2h, filter out liquid after, add again the 200ml titanium tetrachloride and 110 ℃ the reaction 1.5h.Leach reaction solution after reaction finishes, wash 60min at 60 ℃ with trichloromethane, be washed till in the filtrate till the no free chlorion with hexane then, solid product gets (A) ingredient of solid catalyst through vacuum-drying.It contains Ti is 3.2%.
Method by embodiment 1 is carried out propylene polymerization, and catalyst activity is 51.0KgPP/g.Cat, and the polymkeric substance apparent density is 0.45g/cm
3, the polymkeric substance isotactic index is 98.6%.
Embodiment 5
Add 2 with 70 ℃ among the embodiment 4,2 '-dimethoxy-1,1 '-dinaphthalene and 110 ℃ of adding two (p-methylbenzoic acid)-2, the 4-pentadiol ester changes 110 ℃ into and adds two (p-methylbenzoic acid)-2,4-pentadiol ester 1.0mmol and DIBP 1.0ml, other step is constant.Catalyst activity 60.0KgPP/g.cat, the polymkeric substance apparent density is 0.44g/cm
3Molecular weight distribution index M WD 5.313.
Embodiment 6
With 70 ℃ among the embodiment 4 add 2,2 '-dimethoxy-1,1 '-dinaphthalene changes into and adds 2.0mmol 9, two (methoxyl methyl) fluorenes of 9-, other step is constant.Catalyst activity 47.3KgPP/g.cat, the polymkeric substance apparent density is 0.41g/cm
3Molecular weight distribution index M WD 3.601.
Embodiment 7
With 110 ℃ among the embodiment 4 addings 2,4-two (p-methylbenzoic acid) pentadiol ester changes 110 ℃ into and adds 2,4-two (3,4, the 5-trimethylbenzoic acid) pentadiol ester, and other step is constant.Catalyst activity 58.0KgPP/g.cat, the polymkeric substance apparent density is 0.44g/cm
3
Embodiment 8
With 70 ℃ among the embodiment 4 add 2,2 '-dimethoxy-1,1 '-dinaphthalene and 110 ℃ add 2,4-two (p-methylbenzoic acid) pentadiol ester changes 110 ℃ into and adds 2,4-two (furancarboxylic acid) pentadiol ester 1.0mmol and 9, two (methoxyl methyl) fluorenes 3.0mmol of 9-, other step is constant.Catalyst activity 97.0KgPP/g.cat, the polymkeric substance apparent density is 0.44g/cm
3The polymkeric substance isotactic index is 97.6%.。
Embodiment 9:
Add 2 with 70 ℃ among the embodiment 4,2 '-dimethoxy-1,1 '-dinaphthalene changes into and adds 2.0mmol9, two (methoxyl methyl) fluorenes of 9-, 110 ℃ of addings 2,4-two (p-methylbenzoic acid) pentadiol ester 1.0ml changes into and adds 2-(2-thiophenic acid)-4-(cuminic acid) pentadiol ester 1mmol, and other step is constant.Catalyst activity 50.2KgPP/g.cat, the polymkeric substance apparent density is 0.42g/cm
3
Embodiment 10
With 70 ℃ among the embodiment 4 add 2,2 '-dimethoxy-1,1 '-dinaphthalene changes into and adds 2.0mmol9, two (methoxyl methyl) fluorenes of 9-and 110 ℃ add 2,4-two (p-methylbenzoic acid) pentadiol ester 1.0ml changes into and adds 2,4-two (1-naphthoic acid) pentadiol ester 1mmol, and other step is constant.Catalyst activity 59.8KgPP/g.cat, the polymkeric substance apparent density is 0.44g/cm
3
Embodiment 11
Add 2 with 70 ℃ among the embodiment 4,2 '-dimethoxy-1,1 '-dinaphthalene and 110 ℃ of addings 2,4-two (p-methylbenzoic acid) pentadiol ester 1.0ml changes 110 ℃ into and adds 2,4-two (4-methyl isophthalic acid-naphthoic acid) pentadiol ester 1mmol and DIBP 1ml, other step is constant.Catalyst activity 49.0KgPP/g.cat, the polymkeric substance apparent density is 0.43g/cm
3
Embodiment 12
Add 2 with 70 ℃ among the embodiment 4,2 '-dimethoxy-1,1 '-dinaphthalene and 110 ℃ of addings 2,4-two (p-methylbenzoic acid) pentadiol ester 1.0ml changes 70 ℃ into and adds 2.0mmol 9, two (methoxyl methyl) fluorenes of 9-and 110 ℃ add 2-(2-thiophenic acid)-4-(p-tert-butyl benzoic acid) pentadiol ester 1mmol, and other step is constant.Catalyst activity 51.6KgPP/g.cat, the polymkeric substance apparent density is 0.44g/cm
3
Embodiment 13
Add 2 with 70 ℃ among the embodiment 4,2 '-dimethoxy-1,1 '-dinaphthalene and 110 ℃ of addings 2,4-two (p-methylbenzoic acid) pentadiol ester 1.0ml changes 70 ℃ into and adds 2.0mmol 9, two (methoxyl methyl) fluorenes of 9-and 110 ℃ add 2,4-two (2-thiophenic acid) pentadiol ester 1mmol, other step is constant.Catalyst activity 42.4KgPP/g.cat, the polymkeric substance apparent density is 0.41g/cm
3
Embodiment 14
Add 2 with 70 ℃ among the embodiment 4,2 '-dimethoxy-1,1 '-dinaphthalene and 110 ℃ of addings 2,4-two (p-methylbenzoic acid) pentadiol ester 1.0ml changes 70 ℃ into and adds 2.0mmol 9, two (methoxyl methyl) fluorenes of 9-and 110 ℃ add 2-(2-thiophenic acid)-4-(3, the 5-mesitylenic acid) pentadiol ester 1mmol, other step is constant.Catalyst activity 43.6KgPP/g.cat, the polymkeric substance apparent density is 0.42g/cm
3
Claims (11)
1. catalyst for olefines polymerizing contains A, B, C three components: A is an ingredient of solid catalyst, titaniferous, magnesium, chlorine element and internal electron donor, and B is a promotor, C is an external electron donor.Catalyst activity can be regulated in 40.0～120.0Kg PP/g Cat when it is characterized in that being used for propylene polymerization, and polyacrylic isotactic index, molecular weight distributing index also can be regulated in wide region;
The specific surface area of wherein said A component solid catalyst is 100～400m
2/ g, porosity is 0.4～1.5cm
3/ g;
Describedly contain magnesium, the chlorine element is meant synthesis type magnesium chloride or carrier model magnesium chloride;
The described titanium elements that contains is meant compounds such as titanium tetrachloride, tetraalkyl titanium, four titan-alkoxides, titanous chloride or tri-alkoxy titanium;
Described internal electron donor is 2,4-two aromatic acid pentadiol esters and 1,3-diether combination, 2,4-two aromatic acid pentadiol esters and 1,4-virtue diether combination or 2, the combination of 4-two aromatic acid pentadiol esters and organic aryl esters;
Described 2,4-two aromatic acid pentadiol esters are with 2,4-two aromatic acid pentadiol esters or any two mol ratios be 1: 1 aromatic acid inequality mix 2,4-two aromatic acid pentadiol esters; Aromatic acid wherein is the carbocyclic ring aromatic acid, or the heterocycle aromatic acid;
Described carbocyclic ring aromatic acid is one of following kind: phenylformic acid, 1～3 alkyl substituted benzoic acid, 1-naphthoic acid, 1～5 alkyl replace 1-naphthoic acid, 2-naphthoic acid, 1～5 alkyl replacement 2-naphthoic acid; Alkyl wherein is to contain C
1～C
6Straight chained alkyl, or branched-chain alkyl; Alkyl is identical, or different;
Described heterocycle aromatic acid is one of following kind: furancarboxylic acid, 1～3 alkyl substituted furan formic acid, thiophenic acid, 1～3 alkylated substituted thiazoline phenol formic acid; Alkyl wherein is to contain C
1～C
6Straight chained alkyl, or branched-chain alkyl; Alkyl is identical, or different;
Wherein said B promotor is that chemical formula is R
mAlX
3-mOrgano-aluminium compound, wherein R is C
1～C
8The straight or branched alkyl, X is a halogen, 1≤m≤3;
It is R that wherein said C external electron donor is selected from chemical formula
1 aR
2 bSi (OR
3)
cSilicoorganic compound.R in the formula
1, R
2Be C
1～C
10Straight or branched alkyl, C
3～C
10Cycloalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl, R
1, R
2Be identical or different; R
3Be C
1～C
6The straight or branched alkyl; A, b, c are integer, 0≤a≤3,0≤b≤3,1≤c≤3, a+b+c=4.
2, according to the described catalyst for olefines polymerizing of claim 1, the internal electron donor that it is characterized in that A component in the described catalyzer is 2,4-two aromatic acid pentadiol esters and 1, and the combination of 3-diether, its mol ratio is 0.1～30;
Described 1, the 3-diether is 9, and two (methoxyl methyl) fluorenes of 9-or general formula are CH
3OCH
2CR
4R
5CH
2OCH
32,2-dialkyl group-1,3-Propanal dimethyl acetal, wherein R
4And R
5Be respectively and contain C
3～C
16Straight or branched alkyl, C
3～C
10Cycloalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl, R
4And R
5Be identical or different.
3, according to the described catalyst for olefines polymerizing of claim 1, the internal electron donor that it is characterized in that A component in the described catalyzer is 2,4-two aromatic acid pentadiol esters and 1, and the combination of 4-virtue diether, its mol ratio is 0.1～30;
Described 1,4-virtue diether comprises 2,2 '-dialkoxy-1,1 '-dinaphthalene, 6,6 '-dialkyl-2,2 '-dialkoxy-1,1 '-dinaphthalene or 6,6 '-dihalo--2,2 '-dialkoxy-1,1 '-dinaphthalene;
Wherein alkyl is to contain C
3-C
12Straight or branched alkyl, dialkyl are identical or different; Alkyl in the dialkoxy is C
1-C
4Straight or branched alkyl, dialkyl group are identical or different; Halogen is chlorine or bromine.
4, according to the described catalyst for olefines polymerizing of claim 1, the internal electron donor that it is characterized in that A component in the described catalyzer is 2,4-two aromatic acid pentadiol esters and the combination of organic aryl esters, and its mol ratio is 0.1～40;
Described organic aryl esters is: alkyl substituted benzoic acid alkyl ester or bialkyl ortho phthalate, wherein alkyl is to contain C
1～C
8The straight or branched alkyl.
5, according to the described catalyst for olefines polymerizing of claim 1, it is characterized in that the internal electron donor combination of A component in the described catalyzer is 2,4-two aromatic acid pentadiol esters and 1, during the combination of 3-diether, can be without the C component.
6,, it is characterized in that described catalyst B component is triethyl aluminum or triisobutyl aluminium according to the described catalyst for olefines polymerizing of claim 1.
7. catalyst for olefines polymerizing as claimed in claim 1, wherein the A component prepares with following method in the solid catalyst: be reacted into stable magnesium chloride alcohol adduct with Magnesium Chloride Anhydrous and alcohol under 110～150 ℃, react 1～2h with titanium compound and internal electron donor in 100～120 ℃ again, filter, solid adds titanium compound again in 100～120 ℃ of reaction 1～2h, so repeat 1～3 time,, form through vacuum-drying with the inert solvent washing; Must under-10～-30 ℃, carry out when alcohol adduct and titanium compound reaction.
8, according to the preparation method of A component in the solid catalyst in claim 7 catalyst for olefines polymerizing, it is characterized in that the steps include: that Magnesium Chloride Anhydrous and alcohol in the solvent of unreactive hydrocarbons, in the presence of electron donor, in 110～140 ℃ of reaction 2～5h, generate stable synthesis type magnesium chloride alcohol adduct; Alcohol adduct is added drop-wise in the Ti compound then, in the presence of internal electron donor, react 1～2h in 100～120 ℃, the solid that filters out is added the Ti compound again, again in 100～120 ℃ of reaction 1～2h, after the re-treatment like this 1～3 time, use inert solvent that products therefrom is washed, obtain ingredient of solid catalyst by vacuum-drying at last.
9, according to the preparation method of A component in the solid catalyst in claim 7 catalyst for olefines polymerizing, it is characterized in that the steps include: that Magnesium Chloride Anhydrous and alcohol in the solvent of unreactive hydrocarbons, in the presence of the complex compound of electron donor and titanium compound formation, in 110～140 ℃ of reaction 2～5h, generate stable synthesis type magnesium chloride alcohol adduct; Alcohol adduct is added drop-wise in the Ti compound then, in the presence of internal electron donor, react 1～2h in 100～120 ℃, the solid that filters out is added the Ti compound again, again in 100～120 ℃ of reaction 1～2h, after the re-treatment like this 1～3 time, use inert solvent that products therefrom is washed, obtain ingredient of solid catalyst by vacuum-drying at last;
The complex compound that described electron donor and titanium compound form is in advance titanium compound and electron donor to be added in the unreactive hydrocarbons solvent, and 0.5～2h obtains complex solution in the stirring at room reaction.
10, according to the preparation method of A component in the described catalyst for olefines polymerizing of claim 7, it is characterized in that the steps include: Magnesium Chloride Anhydrous with alcohol in mineral oil in 110～150 ℃ of reactions, the alcohol adduct that generates is dispersed in the mineral oil, the alcohol adduct that will be dispersed in the mineral oil by high speed dispersion emulsification means is dispersed into drop then, be sprayed onto low temperature again and receive in the solvent, make the rapid quenching of emulsion droplet be solidified into microspheroidal carrier model magnesium chloride alcohol adduct; With it after inert solvent washing and vacuum-drying obtain, be added in the cryogenic titanium compound, in the presence of internal electron donor, react 1～2h in 100～120 ℃, the solid that filters out is added titanium compound again, again in 100～120 ℃ of reaction 1～2h, so after the re-treatment 1～3 time, use inert solvent to products therefrom wash, drying obtains ingredient of solid catalyst.
11, the polymerization process in olefinic polymerization of catalyst for olefines polymerizing is characterized in that CH
2The polyreaction of=CHR is finished in the presence of catalyst A ingredient of solid catalyst, B cocatalyst component and C external electron donor compound;
Be B/A=1～1000 wherein by the A ingredient of solid catalyst of Ti calculating and the mol ratio of B cocatalyst component and C external electron donor compound, C/B=0～1; R is hydrogen or C
1-C
8Alkyl; Polyreaction is finished in liquid phase body, slurry or gas phase.
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