CN101928359B - Catalyst for olefin polymerization - Google Patents
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Abstract
The invention provides a catalyst for olefin polymerization, which comprises reaction products of the following components: (1) a catalyst component which is formed by loading a titanium compound shown as a general formula (II) of Ti(ORw)4-kXk and at least two electron donor compounds a and b on alcohol adduct particles shown as a general formula (I) of MgC12.nRqOH; (2) an alkylaluminium compound; and (3) an external electron donor compound which is tetraalkoxide silane shown as a general formula (IV) of Si(ORx)4, wherein Rx represents C1 to C20 alkyl or naphthenic base or C6 to C10 aryl or aralkyl. The catalyst has high activity and high orientation capability. A polymer has wide molecular weight distribution. Meanwhile, the hydrogen regulation sensitivity of the catalyst is greatly improved.
Description
Technical field
The present invention relates to a kind of catalyzer that is used for olefinic polyreaction, more particularly, relate to a kind of olefin polymerization catalysis that comprises spherical catalyst component, promotor and external electron donor compound four-oxyl silane.
Technical background
As everyone knows; The catalyst system that is used for the polyreaction of terminal olefin and composition thereof generally is made up of three parts, and they are: the external electron donor compound that adds when (1) Primary Catalysts (solid catalyst), (2) promotor (being generally the aluminum alkyls compounds), (3) polymerization.
In polymerization process, using one or more external electronic donor compounds to come the taxis of controlling polymers and form is that those skilled in the art are total to knowledge.External electron donor is except the taxis of impact polymer; Have influence on the performance of others such as activity of such catalysts and hydrogen response to some extent toward the contact meeting; But its influence in the effect of playing in a certain respect, then can be played spinoff often in other respects.Though known have many kinds of compounds to can be used as external electron donor, specific catalyst uses different external electron donor compounds may produce the different polymer performance.Choosing suitable external electron donor can be compatible especially with specific catalyst.That is to say; Find a kind of suitable external electron donor can improve the performance (like MWD and hydrogen response etc.) of polymeric articles significantly; And influence or influence are very not little to other performance simultaneously, find that therefore one group is used for the external electron donor that special catalyst can make polymkeric substance have fine over-all properties and is necessary.
European patent EP 385765A provides a kind of catalyst system, and this catalyst system is made up of dicyclopentyl dimethoxyl silane, two kinds of external electron donors of propyl-triethoxysilicane and Ziegler-Natta catalyst.U.S. Pat 5,100,981 disclose a kind of catalyst system, and it is made up of the mixture of Primary Catalysts and two kinds of external electron donors, and said two kinds of external electron donors are methylcyclohexyl dimethoxy silane (CHMMS) and phenyl triethoxysilane.Japanese Patent JP19820199728 also provides a kind of catalyst system; This system also is made up of Ziegler-Natta catalyst and two kinds of silane external electron donor mixtures; Described external electron donor is oil of Niobe and tetraethoxysilane, but polymer active that obtains and degree of isotacticity are all lower; Japanese Patent JP19820174495, JP19920331459 use tetraethoxysilane as external electron donor separately, but polymer active, degree of isotacticity are all very low.
Chinese patent ZL95191937.7 mentions dicyclopentyl dimethoxyl silane (DCPMS) and tetraethoxysilane (TEOS) is united the polymerization method of use as external electron donor; It can improve the melt flow index of polymkeric substance, but uses tetraethoxysilane (TEOS) all very low as polymer active and the isotactic index that external electron donor obtains separately.
In sum; As far as present electron donor compound; The industry it has been generally acknowledged that; In olefinic polyreaction, use four-oxyl silicon compounds as the polymkeric substance over-all properties that external electron donor obtains bad (very low like activity, degree of isotacticity is very low etc.) separately, almost do not use the catalyst system that be used for olefinic polymerization of four-oxyl silicon compounds separately as the external electron donor compound.
Chinese patent CN02100896.5, CN02100900.7, CN03109781.2, CN03140565.7, CN200410073623.8, CN200410073621.9 etc. have described and have used polyol ester compounds and the composite catalyst component as internal electron donor of adjacent benzene dicarboxylic acid ester compound; When this catalyst component is used for propylene polymerization; External electron donor commonly used is alkyl two-oxyl silane, such as methylcyclohexyl dimethoxy silane (CHMMS) etc.Chinese patent CN03109781.2 has also used different external electron donors; For example except using methylcyclohexyl dimethoxy silane; Also used second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane (DCPMS), two (cyclobutylmethyl) dimethoxy silane etc., this catalyst system shows high reactivity, high orientation property and the prepared wide characteristics of molecular weight distribution.But find that from disclosed patent the hydrogen response of this type catalyst system is poor, especially more outstanding during polymerization under the low-hydrogen density condition.The hydrogen response of catalyst system is poor, when being used for industrial production, will produce a series of adverse influences, and in producing, the consumption of hydrogen will increase; Directly perhaps can't produce or the like through the polymkeric substance of the higher melt index of polymerization reactor production is very difficult.
How keeping composite with polyol ester compounds and adjacent benzene dicarboxylic acid ester compound is the characteristics of the catalyst system of internal electron donor; Improve the hydrogen response of this catalyst system simultaneously; Thereby improving the over-all properties of catalyst system, is the important technological problems that needs solution.
The inventor is surprised to find that in research work; Add four-oxyl silicon compounds as the external electron donor compound at the spherical solid catalyst component that is internal electron donor with polyol ester compounds and adjacent benzene dicarboxylic acid ester compound during in olefinic polymerization; Can not only keep this high activity of catalyst, high orientation property and the prepared wide characteristics of molecular weight distribution; The hydrogen response of this catalyzer improves greatly simultaneously; And polymerization method is simple, only needs to use separately to get final product, and need not add other external electron donor and carry out compound use.
Summary of the invention
The object of the present invention is to provide a kind of catalyzer that is used for olefinic polyreaction, this catalyzer has very high polymerization activity, the higher degree of isotacticity of polymkeric substance tool that obtains, and the hydrogen response of catalyzer improves greatly simultaneously.
The catalyzer that is used for olefinic polyreaction of the present invention comprises the reaction product of following component:
(1) a kind of catalyst component, this catalyst component are like general formula (I) MgCl
2.nR
qLoad is just like general formula (II) Ti (OR on the alcohol adduct particle shown in the OH
w)
4-kX
kShown titanium compound and at least two kinds of electron donor compound as, b;
R in its formula of (I)
qFor carbon number is 1～18 alkyl, n is 0.1～6, and preferred n is 2～3.5;
R in its formula of (II)
wBe 1～20 alkyl, X is F, C1 or Br, and k is 1～4 integer;
Be selected from the diol-lipid compound shown in the general formula (III) wherein for electric body compound a:
R in the formula (III)
1-R
6, R
1-R
2nGroup is the C of hydrogen, halogen, replacement or unsubstituted straight or branched identical or inequality
1-C
20Alkyl, C
3-C
20Naphthenic base, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene, C
10-C
20Fused ring aryl or ester group, R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2nComprise one or several heteroatoms on the group arbitrarily as carbon or Wasserstoffatoms or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6And R
1-R
2nOne or more in the group can link up into ring; N is the integer of 0-10;
Be selected from monobasic or polyhydric aliphatic family carboxylicesters or aromatic carboxylic acid esters or diether compound wherein for electric body compound b;
(2) a kind of alkylaluminium cpd;
(3) a kind of external electron donor compound is like general formula (IV) Si (OR
x)
4Four shown-oxyl silane, wherein R
xIt for carbonatoms 1～20 alkyl or cycloalkyl, carbonatoms 6～10 aryl or aralkyl.
Give electric body compound a preferred formula (V) in the wherein said component (1).
R wherein
1-R
6, R
1-R
2Definition in group such as the general formula (III).
Give the also compound shown in the preferred formula (VI) of electric body compound a in the described component (1).
R wherein
1-R
6, R
1-R
2Definition in group such as the general formula (III), R ' is the C of hydrogen identical or inequality, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Naphthenic base, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl.
Particular compound is like 2-ethyl-1, ammediol dibenzoate, 2-propyl group-1, ammediol dibenzoate, 2-sec.-propyl-2-isopentyl-1,3 Ucar 35 dibenzoate, 1; 3-butyleneglycol mesitylenic acid ester, 2-methyl isophthalic acid, 3-butyleneglycol two m-chlorobenzoic acid esters, 2,3-dimethyl--1; 3-butyleneglycol dibenzoate, 1,3-pentanediol pivalate, 2,4-pentanediol dibenzoate, 2-methyl isophthalic acid; 3-pentanediol phenylformic acid laurate, 2,2-dimethyl--1,3-pentanediol dibenzoate, 2; 4-heptanediol dibenzoate, 2-methyl-3,5-heptanediol dibenzoate, 9, two (benzoyloxy methyl) fluorenes of 9-etc.Be preferably 2,4-pentanediol dibenzoate, 4-ethyl-3,5 heptanediol dibenzoate.
Other a kind of electron donor compound b is monobasic or polyhydric aliphatic family carboxylicesters or aromatic carboxylic acid esters and diether compound in the component of the present invention (1).For example: benzoic ether, phthalic ester, malonic ester, succinate, glutarate etc.Concrete as: ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate, dinoctyl phthalate, ethyl malonate, TERT-BUTYL 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, naphthalene dicarboxylic acids diethyl ester, naphthalene dicarboxylic acids dibutylester, triethyl trimellitate, tributyl trimellitate, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tri-n-butyl, PMA tetra-ethyl ester, PMA four butyl esters etc.
Wherein give 1 shown in the diether compound preferred formula (VII) described in the electric body compound b, 3-two ethers,
R wherein
I, R
II, R
III, R
IV, R
VAnd R
VIMutually the same or inequality, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Naphthenic base, 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 selected from the C of straight or branched
1-C
20Alkyl, C
3-C
20Naphthenic base, 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.Preferred R
VIIAnd R
VIIIBe selected from C
1-C
41 of alkyl, the 3-diether.
Above-mentioned 1 among the present invention, the 3-diether compound is disclosed among Chinese patent CN1020448C, CN100348624C and the CN1141285A.Its disclosed associated viscera is all introduced the present invention as a reference.
In component (1), the general formula of described titanium compound is: Ti (OR
w)
4-kX
k, R wherein
wBe 1～20 alkyl, X is F, Cl, Br or its mixture, and k is 1～4 integer.Specifically can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, the titanous chloride or their mixture for use, preferred titanium tetrachloride.
Component of the present invention (1) catalyst component can prepare according to the preparation method of disclosed solid catalyst among the Chinese patent CN1036011C, MgCl of the present invention
2.nR
qThe OH alcohol adduct is disclosed among Chinese patent CN1036011C, CN1330086A and the CN100491410C, and its disclosed associated viscera is all introduced the present invention as a reference.
The concrete preparation method of magnesium halide alcohol adduct carrier: anhydrous magnesium halide and low-carbon alcohol are mixed; Temperature reaction generates the magnesium halide alcohol adduct melt; Temperature of reaction is 90～140 ℃; In dispersion medium, after high shear forces, put into the refrigerative inert media, form spherical magnesium halide alcohol adduct particle, after washing, drying, obtain ball type carrier.High shear forces can adopt conventional method to obtain, like high-speed mixing method (like CN1330086), spray method (like US6020279) and high-gravity rotating bed (like CN1580136A) and mulser method (CN1463990A) etc.Dispersant system adopts the hydro carbons inert solvent, like kerosene, white oil, silicone oil, Yellow Protopet 2A, Vaseline wet goods.Heat-eliminating medium is selected from pentane, hexane, heptane, sherwood oil, raffinates oil etc.
The compound method of component of the present invention (1) catalyst component: the above-mentioned magnesium halide alcohol adduct that obtains is suspended in the titanium compound of precooling or the mixture of titanium compound and inert solvent (like hexane, heptane, octane, decane, toluene etc.), and (temperature is-30 ℃～0 ℃; Preferably-20 ℃～-10 ℃) in; Then said mixture is heated to 80 ℃～130 ℃, in temperature-rise period, adds electron donor compound a and electron donor compound b.Add titanium compound then and handle one or many.At last, repeatedly wash with inert solvent and obtain ingredient of solid catalyst.
Prepare in the process at component of the present invention (1) catalyst component, electron donor compound a and electron donor compound b can be used in many ways jointly, and the two can use in different step He under the different condition, also can add simultaneously.Wherein in every mole of magnesium, the electron donor compound a is 0.001～0.5 mole, preferred 0.001～0.1 mole; The electron donor compound b is 0.01～5 mole, preferred 0.05～1 mole.
Component of the present invention (2) alkylaluminium cpd, its general formula is AlR ' "
3, R ' " is C identical or inequality
1-8Alkyl, one of them or two alkyl can be replaced by chlorine, can select for use one or more aluminum alkyls mix to use, preferred triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, chlorination aluminum alkyls, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2Cl etc. are 1～1000 use abovementioned alkyl aluminum compound with the Al/Ti mol ratio generally.
Component of the present invention (3) external electron donor compound is like general formula (IV) Si (OR
x)
4Four shown-oxyl silane, wherein R
xIt for carbonatoms 1～20 alkyl or cycloalkyl, carbonatoms 6～10 aryl or aralkyl.Specifically can select tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes, four pentyloxy silane, four hexyloxy silane, tetraisopropoxysilan, tetraisobutoxy-silicane alkane, Fourth Ring pentyloxy silane, Fourth Ring hexyloxy silane, tetraphenoxy-silicane alkane, tetrem alkene TMOS, tetrapropylene TMOS, four iso-butylene TMOSs etc. for use, preferred tetraethoxysilane (TEOS).General formula is Si (OR
x)
4The consumption of four-oxyl silane for to count 0.005～0.5 mole with every mole of aluminum alkyl compound, preferably count 0.01～0.25 mole with every mole of aluminum alkyl compound.
General formula (IV) Si (OR
x)
4Four shown-oxyl silane can adopt compound method commonly used to prepare in the laboratory, also can buy on the market by general chemical product purchasing way.
Component (2) alkylaluminium cpd and component (3) external electron donor compound can be separately or as two kinds of mixture of ingredients and component (1) catalyst component contact reacts.
Above-mentioned catalyst system is suitable for alkene CH
2=CHR
y(R wherein
yBe the alkyl or aryl of hydrogen or 1～6 carbon) and the polyreaction that contains the mixture of (if necessary) a small amount of diolefine, be specially adapted to the polyreaction of propylene.
The polymerization of alkene is carried out according to currently known methods, in the liquid phase of liquid monomer or the solution of monomer in inert solvent, or in gas phase, or through operating in the polymerization mix technology of gas-liquid in mutually.Polymerization temperature is generally 0 ℃～150 ℃, preferably 60 ℃～100 ℃.Polymerization pressure is a normal pressure or higher.
Embodiment
Provide following examples so that the present invention is described better, be not used for limiting scope of the present invention.
Testing method:
1, melt index: measure according to ASTM D1238-99.
2, polymkeric substance degree of isotacticity: adopt the heptane extraction process to measure (heptane boiling extracting 6 hours); Promptly get 2g exsiccant polymer samples, place extractor with boiling heptane extracting 6 hours, afterwards; Residuum is dried to constant weight, and resulting polymers weight (g) is degree of isotacticity with 2 ratio.
3, molecular weight and distribution tests: it is the mensuration (standard specimen: PS of solvent under 150 ℃ with the trichlorobenzene that polymericular weight and MWD MWD (MWD=Mw/Mn) adopt PL-GPC220; Flow velocity: 1.0ml/min, pillar: 3xPlgel 10um M1xED-B 300x7.5nm).
4, xylene soluble part is measured: the content of measuring xylene soluble part in the multipolymer according to the method for ISO10350-1.
Embodiment 1
Diol ester compound 2, the preparation of 4-pentanediol dibenzoate
The preparation of (1) 2,4-pentanediol
10g2,4-diacetylmethane and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g Peng Qinghuana, 0.1g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ETHYLE ACETATE continuous extraction 15h.Remove and desolvate, column chromatography gets colourless liquid 2,4-pentanediol, yield 90%.
The preparation of (2) 2,4-pentanediol dibenzoates
0.03mol 2, add 30ml THF and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol Benzoyl chloride 99min., reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na
2SO
4Drying is removed and is desolvated.Column chromatography or underpressure distillation get colourless liquid 2,4-pentanediol dibenzoate, yield 95%.
1H NMR (δ, ppm, TMS): 1.3～1.4 (8H, m, methyl H); 2.0～2.1 (2H, m, methylene radical H); 5.2～5.3 (2H, m, the methyne H of ester group); 7.3～8.0 (10H, m, phenyl ring H).
Embodiment 2
The preparation of 2A, solid catalyst A (Primary Catalysts)
In the glass reaction bottle that abundant metathetical 300ml band stirs through high pure nitrogen, add the titanium tetrachloride of 100ml, be cooled to-20 ℃; Add spherical magnesium chloride alcohol adduct (preparation method is referring to Chinese patent CN1330086A), slowly be warming up to 110 ℃ stage by stage, in temperature-rise period, add 2 of preparation among the embodiment 1; 4-pentanediol dibenzoate 2.5mmol and Witcizer 300 3.9mmol; Behind 110 ℃ of constant temperature 0.5h, elimination liquid adds titanium tetrachloride and handles secondary; Use hexane wash then five times, obtain solid catalyst A (Primary Catalysts) after the vacuum-drying.
2B, propylene polymerization
In 5 liters of autoclaves; Adopt stream of nitrogen gas to purge 1 hour down at 70 ℃; With gas-phase propene polymeric kettle is replaced 3 times then, under nitrogen protection, introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of external electron donor is 0.1mmol/ml), 10ml anhydrous hexane and 8～12mg solid catalyst (Primary Catalysts) of 1ml external electron donor.Close autoclave, introduce an amount of hydrogen and the liquid propene of 1.0～1.2Kg; Under agitation fast
interior temperature is risen to 70 ℃., stop stirring after 1 hour 70 ℃ of following polyreactions, remove unpolymerized propylene monomer, collected polymer is in 70 ℃ of following vacuum-dryings 2 hours, the calculated activity of weighing (AC).
Embodiment 3～7
The solid catalyst for preparing among the 2A with embodiment 2 is according to the method for propylene polymerization among the 2B of embodiment 2, and the amount that adds hydrogen respectively is 1NL, 2NL, 4NL, 6NL, 8NL.The external electron donor that adds during polymerization is the hexane solution of tetraethoxysilane (TEOS), and polymerization and test result are seen table one, table two.
Embodiment 8～12
According to the method for embodiment 3～7, during polymerization the external electron donor that adds is replaced by the hexane solution of tetramethoxy-silicane (TMOS), polymerization and test result are seen table one, table two.
Embodiment 13～17
According to the method for embodiment 3～7, during polymerization the external electron donor that adds is replaced by the hexane solution of tetrapropoxysilane (TPOS), polymerization and test result are seen table one, table two.
Embodiment 18～22
According to the method for embodiment 3～7, during polymerization the external electron donor that adds is replaced by the hexane solution of four butoxy silanes (TBOS), polymerization and test result are seen table one, table two.
The comparative example 1～5
Polymerization method just changes the external electron donor that adds into the hexane solution (concentration of CHMMS is 0.1mmol/ml) of 1ml cyclohexyl methyl dimethoxy silane (CHMMS) with embodiment 3～7, and polymerization result is seen table one, table two.
Table 1
| Numbering | External electron donor | Hydrogenation amount (NL) | Active (KgPP/gCat) | The degree of isotacticity of polymkeric substance (wt%) | Xylene soluble part in the polymkeric substance (Wt%) | Polymer melt index (g/10min) |
| Embodiment 3 | TEOS | 1 | 44.3 | 98.7 | 1.84 | 1.1 |
| Embodiment 4 | TEOS | 2 | 43.7 | 98.0 | 1.87 | 4.0 |
| Embodiment 5 | TEOS | 4 | 56.4 | 97.6 | 1.88 | 6.2 |
| Embodiment 6 | TEOS | 6 | 49.7 | 97.0 | 2.08 | 18.5 |
| Embodiment 7 | TEOS | 8 | 47.6 | 95.2 | 2.4 | 72.4 |
| Embodiment 8 | TMOS | 1 | 42.8 | 98.9 | 1.57 | 1.2 |
| Embodiment 9 | TMOS | 2 | 40.7 | 98.5 | 1.45 | 3.2 |
| Embodiment 10 | TMOS | 4 | 44.7 | 97.7 | 1.62 | 12.9 |
| Embodiment 11 | TMOS | 6 | 36.0 | 96.9 | 1.63 | 20.0 |
| Embodiment 12 | TMOS | 8 | 37.1 | 96.3 | 1.92 | 39.7 |
| Embodiment 13 | TPOS | 1 | 53.4 | 96.7 | 2.94 | 2.1 |
| Embodiment 14 | TPOS | 2 | 45.2 | 95.8 | 2.84 | 6.9 |
| Embodiment 15 | TPOS | 4 | 59.4 | 94.8 | 3.36 | 20.9 |
| Embodiment 16 | TPOS | 6 | 52.5 | 94.5 | 3.01 | 43.6 |
| Embodiment 17 | TPOS | 8 | 66.3 | 92.9 | 3.47 | 75.3 |
| Embodiment 18 | TBOS | 1 | 48.2 | 97.1 | 2.66 | 4.1 |
| Embodiment 19 | TBOS | 2 | 71.7 | 96.3 | 3.09 | 5.2 |
| Embodiment 20 | TBOS | 4 | 63.9 | 94.2 | 3.90 | 17.0 |
| Embodiment 21 | TBOS | 6 | 74.1 | 92.9 | 3.77 | 40.7 |
| Embodiment 22 | TBOS | 8 | 66.4 | 94.1 | 3.31 | 49.7 |
| Comparative Examples 1 | CHMMS | 1 | 49.0 | 99.0 | 1.84 | 0.4 |
| Comparative Examples 2 | CHMMS | 2 | 52.6 | 98.4 | 1.57 | 1.4 |
| Comparative Examples 3 | CHMMS | 4 | 63.3 | 98.3 | 1.63 | 1.7 |
| Comparative Examples 4 | CHMMS | 6 | 66.0 | 97.5 | 1.91 | 7.2 |
| Comparative Examples 5 | CHMMS | 8 | 65.5 | 97.08 | 2.02 | 16.48 |
Annotate: TEOS---tetraethoxysilane
TMOS---tetramethoxy-silicane
TPOS---tetrapropoxysilane
TBOS---four butoxy silanes
CHMMS---methylcyclohexyl dimethoxy silane
Can find out by table 1; Use the catalyst system of four-oxyl silane as external electron donor; After being used for propylene polymerization; Under identical hydrogen concentration condition, resulting polymer melt index (embodiment 3～7), the obviously melt index (Comparative Examples 1～5) of the polymkeric substance when using methylcyclohexyl dimethoxy silane (CHMMS) as external electron donor.
Can find out from resulting polymkeric substance over-all properties; Use the catalyst system of tetraethoxysilane (TEOS) as external electron donor; Under the situation that hydrogen response improves greatly; Polymerization catalyst degree of isotacticity active and resulting polymkeric substance reduces hardly, still remains on very high level.
Table 2
Annotate: TEOS---tetraethoxysilane
TMOS---tetramethoxy-silicane
TPOS---tetrapropoxysilane
TBOS---four butoxy silanes
CHMMS---methylcyclohexyl dimethoxy silane
Can find out by table 2; After using four-oxyl silane to be used for propylene polymerization as the catalyst system of external electron donor; Under identical condition; The polymkeric substance of the molecular weight distributing index of resulting polymkeric substance when using methylcyclohexyl dimethoxy silane (CHMMS) as external electron donor quite, be the polymkeric substance of MWD broad.
Claims (10)
1. catalyzer that is used for olefinic polyreaction comprises the reaction product of following component:
(1) a kind of catalyst component, this catalyst component are like general formula (I) MgCl
2.nR
qLoad is just like general formula (II) Ti (OR on the alcohol adduct particle shown in the OH
w)
4-kX
kShown titanium compound and at least two kinds of electron donor compound as, b;
R in its formula of (I)
qFor carbon number is 1～18 alkyl, n is 0.1～6;
R in its formula of (II)
wBe 1～20 alkyl, X is F, Cl, Br or its mixture, and k is 1～4 integer;
Be selected from the diol-lipid compound shown in the general formula (III) wherein for electric body compound a:
R in the formula (III)
1-R
6, R
1-R
2nGroup is the C of hydrogen, halogen, replacement or unsubstituted straight or branched identical or inequality
1-C
20Alkyl, C
3-C
20Naphthenic base, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene, C
10-C
20Fused ring aryl or ester group, R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2nComprise one or several heteroatoms on the group arbitrarily as carbon or Wasserstoffatoms or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6And R
1-R
2nOne or more in the group can link up into ring; N is the integer of 0-10;
Be selected from monobasic or polyhydric aliphatic family carboxylicesters or aromatic carboxylic acid esters or diether compound wherein for electric body compound b;
(2) a kind of alkylaluminium cpd;
(3) a kind of external electron donor compound is like general formula (IV) Si (OR
x)
4Four shown-oxyl silane, wherein R
xIt for carbonatoms 1～20 alkyl or cycloalkyl, carbonatoms 6～10 aryl or aralkyl.
2. the catalyzer that is used for olefinic polyreaction according to claim 1, wherein the electron donor compound a is selected from the diol-lipid compound shown in logical formula V in the component (1):
R wherein
1-R
6, R
1-R
2Definition in group such as the general formula (III).
3. the catalyzer that is used for olefinic polyreaction according to claim 1, wherein the electron donor compound a is selected from the diol-lipid compound shown in general formula (VI) in the component (1):
In its formula of (VI), R
1-R
6Definition in group such as the general formula (III), R ' is the C of hydrogen identical or inequality, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Naphthenic base, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl.
4. the catalyzer that is used for olefinic polyreaction according to claim 1, wherein the diether compound described in component (1) the electron donor compound b is 1 shown in the general formula (VII), 3-two ethers:
R in the general formula (VII)
I, R
II, R
III, R
IV, R
VAnd R
VIIdentical or inequality, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Naphthenic base, C
6-C
20Aryl, C
7-C
20A kind of in the aralkyl, R
VIIAnd R
VIIIIdentical or different, be selected from the C of straight or branched
1-C
20Alkyl, C
3-C
20Naphthenic base, 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.
5. the catalyzer that is used for olefinic polyreaction according to claim 4,1 shown in its formula of (VII), R in 3-two ethers
VIIAnd R
VIIIBe C
1-C
4Alkyl.
6. the catalyzer that is used for olefinic polyreaction according to claim 1, wherein giving electric body compound b in the component (1) is benzoic ether, phthalic ester, malonic ester, succinate or glutarate.
7. the catalyzer that is used for olefinic polyreaction according to claim 1, wherein in component (1) in every mole of magnesium chloride, be respectively 0.001～0.5 mole, 0.01～5 mole for electric body compound a and b.
8. the catalyzer that is used for olefinic polyreaction according to claim 7, wherein in component (1) in every mole of magnesium chloride, be respectively 0.001～0.1 mole, 0.05～1 mole for electric body compound a and b.
9. the catalyzer that is used for olefinic polyreaction according to claim 1, wherein the ratio between component (3) and the component (2) is 0.005～0.5 with the Si/Al mol ratio; Wherein the ratio between component (1) and the component (2) is 1～1000 with the Al/Ti mol ratio.
10. the catalyzer that is used for olefinic polyreaction according to claim 1, wherein four-oxyl silane described in the component (3) are tetraethoxysilane.
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| CN102898550B (en) * | 2011-07-26 | 2015-03-11 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and preparation method and catalyst thereof |
| CN102898552B (en) * | 2011-07-26 | 2015-04-15 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and preparation method and catalyst thereof |
| CN102898551B (en) * | 2011-07-26 | 2015-03-11 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and preparation method and catalyst thereof |
| CN102558405B (en) * | 2011-12-30 | 2014-11-05 | 北京化工大学 | Alpha-olefin polymerization catalyst and preparation method and application thereof |
| CN103304691B (en) * | 2012-03-08 | 2015-09-16 | 中国石油化工股份有限公司 | A kind of catalyst system for olefinic polyreaction |
| CN103819586B (en) * | 2012-11-16 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of catalyst system for olefinic polyreaction |
| CN104250321B (en) * | 2013-06-28 | 2016-08-17 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and olefin polymerization catalysis and olefine polymerizing process |
| CN104558293B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst |
| CN103923238B (en) * | 2013-10-31 | 2018-03-02 | 北京利和知信科技有限公司 | Catalytic component and catalyst for olefinic polymerization |
| CN104109213B (en) * | 2014-06-13 | 2017-11-07 | 北京利和知信科技有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN104017113B (en) * | 2014-06-13 | 2018-04-03 | 北京利和知信科技有限公司 | Catalytic component for olefinic polymerization and the catalyst containing the catalytic component and its application |
| CN104109212B (en) * | 2014-06-13 | 2017-11-07 | 北京利和知信科技有限公司 | Solid catalyst component for olefine polymerization and catalyst |
| CN104045748B (en) * | 2014-06-13 | 2017-12-26 | 北京利和知信科技有限公司 | Ingredient of solid catalyst and catalyst for olefinic polymerization |
| CN106608942B (en) * | 2015-10-27 | 2019-09-27 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and its preparation method and application and catalyst and its application for olefinic polymerization |
| CN107129547A (en) * | 2016-02-29 | 2017-09-05 | 中国石油化工股份有限公司 | Ingredient of solid catalyst, catalyst and application for olefinic polymerization |
| CN107129549A (en) * | 2016-02-29 | 2017-09-05 | 中国石油化工股份有限公司 | Ingredient of solid catalyst, catalyst and application for olefinic polymerization |
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