CN1769311A - Catalyst components for olefinic polyreaction and catalyst thereof - Google Patents
Catalyst components for olefinic polyreaction and catalyst thereof Download PDFInfo
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- CN1769311A CN1769311A CN 200410086376 CN200410086376A CN1769311A CN 1769311 A CN1769311 A CN 1769311A CN 200410086376 CN200410086376 CN 200410086376 CN 200410086376 A CN200410086376 A CN 200410086376A CN 1769311 A CN1769311 A CN 1769311A
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Abstract
The invention relates a catalyst component used for alkene aggregation and its catalyst. The catalyst component is prepared by special polyatomic alcohol esters compounds, titanium compounds, and the composite carrier of magnesium halide and silica sols. When the catalyst component is used in alkene aggregation, not only the polymerization activity is high, but also the hydrogen sensitivity is good, and the molecular weight distribution of the polyaromatics is wide, the packing density is higher.
Description
Technical field
The present invention relates to a kind of olefinic polymerization particularly propylene polymerization or copolymerization catalyst component and catalyzer thereof of being used for, more specifically, relate to a kind of complex carrier, a kind of special polyol ester compounds and titanium compound of adopting and react catalyst component and the catalyzer thereof that obtains.
Technical background
As everyone knows, efficient carrier model Ziegler-Natta catalyst has been widely used in the copolymerization of the polymerization of ethene, propylene and they and other alpha-olefin.In disclosed patented technology, efficient supported catalyst is single carrier with magnesium chloride usually, in order to improve catalytic activity, at first take different physics or chemical process to prepare magnesium chloride support, then transistion metal compound and electron donor compound formation catalyst active center in the load.In now disclosed many patents be with magnesium chloride load on porous inorganic oxide carriers such as silica gel, and then, finally obtain olefin polymerization catalysis with halogen titanium compound and electron donor compound treatment.For example, English Patent GB2028347 has provided the method that a kind of preparation is loaded in porous inorganic oxide supported catalyst component, promptly use magnesium chloride solution impregnation of silica carrier, make solvent evaporation afterwards, the solid product that obtains again with particularly titanium compound reaction of transistion metal compound.And for example Chinese patent CN1035186C discloses a kind of technology of utilizing silica supports to prepare efficient polypropylene catalyst.It is that the porous silica carrier that hydroxyl is contained on the surface is scattered in the tetrahydrofuran solution of magnesium chloride, and dry above-mentioned suspension obtains MgCl
2/ SiO
2Complex carrier is used titanium tetrachloride and this carrier of electron donor compound treatment again, finally obtains catalyst prod.But this activity of such catalysts is lower.When for example being internal electron donor with the diisobutyl phthalate, two hours polymerization activity was up to 20kgPP/gCat when catalyzer was used for propylene polymerization.Also have many patents to describe this technology, for example in patents such as US5559071, US5625015, WO94/14855, WO94/14856, WO95/11263, WO95/15216, WO95/12622, WO96/16093, WO96/05236, WO97/23518, WO98/01481, WO99/46306, WO00/22011, WO00/40623, WO00/05277 and EP0295312, all disclose this Preparation of catalysts technology by immersion process for preparing complex carrier type catalyzer.
But the prepared catalyzer of carrier that the method that adopts above-mentioned magnesium chloride solution dipping obtains, when being used for propylene polymerization, polymerization activity is all unsatisfactory.This may be because the method for this dipping is to utilize the particle form of silica-gel carrier itself to control the particle form of final catalyzer basically, the particle of the general porous silica gel that adopts is bigger, usually median size is～50 μ m, limited the charge capacity of active ingredient on silica gel, made final activity of such catalysts not high.
U.S. Pat 4376062 discloses a kind of catalyzer of complex carrier type, it is in the electron donor solvent, in tetrahydrofuran (THF), Magnesium Chloride Anhydrous and titanium tetrachloride contact reacts are obtained containing the slurries or the solution of active ingredient, be after the smoke-like silicon-dioxide of 0.007～0.05 μ m mixes then with itself and particle diameter, obtain median size after spray-dried and be the catalyst prod about 25 μ m.Be used for vinyl polymerization after this catalyzer and activator (aluminum alkyls) effect, show high polymerization activity.But for being used for propylene polymerization,, adding internal electron donor and be very important, use the aromatic carboxylates or the diether compound of binary in the prior art usually in order to obtain high normal propene polymer.And above-mentioned preparation method will be unfavorable for stably controlling the composition of each component on carrier.Owing in the slurries of spraying, contain a large amount of titanium tetrachlorides, easily spray drying device is caused corrosion simultaneously, be unfavorable for suitability for industrialized production.Therefore, be necessary very much to provide a kind of preparation method of new complex carrier to overcome above-mentioned defective.
In addition, in recent years, some disclosed patented technologies are pointed out, contain the internal electron donor of the special polyol ester compounds of two or more ester groups as catalyst component by use, can be so that the performance of conventional Ziegler-Natta catalyst improves greatly.As disclosed olefin polymerization catalyst components such as Chinese patent CN1436766A, CN1436796A and CN1453298A.The inventor finds by repetition test, adopt a kind of improved complex carrier and a kind of special prepared catalyst component of polyol ester compounds, when being used for propylene polymerization, not only polymerization activity is higher, hydrogen response is good, and the molecular weight distribution broad of resulting polymers, the bulk density of polymkeric substance is higher.
Summary of the invention
The present invention relates to a kind of catalyst component that is used for olefinic polymerization, it contains the reaction product of following component:
(1) a kind of complex carrier, it is magnesium halide to be contacted with one or more electron donor compounds form solution, this solution mixes with the silica-gel carrier of median size less than 30 μ m, the spray-dried spherical particle that makes;
(2) at least aly be selected from the polyol ester compounds shown in the general formula (I):
R in the formula
1-R
6, R
1-R
2nGroup is hydrogen, halogen or the replacement identical or inequality or the C of unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene, C
10-C
20Fused ring aryl or C
2-C
10Ester group; But R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2nComprise one or several heteroatoms on the group arbitrarily as carbon or hydrogen atom 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;
(3) general formula Ti (OR)
4-mX
mShown titanium compound, R is C in the formula
1～C
14Aliphatic group, X is identical or different, is selected from from F, Cl and Br, m is 1～4 integer.
In above-mentioned complex carrier, wherein said magnesium halide such as Mg (OR
1)
2-mX
mShown in, R in the formula
1Be C
1～C
14Alkyl, X is identical or different, is selected from from F, Cl and Br, and m is 1 or 2, R
1Be straight chain, side chain or cyclic alkyl.Concrete compound is as magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.Described halogenated magnesium compound can be used alone or as a mixture.
In above-mentioned complex carrier, suitable electron donor compound comprises the alkyl ester of fat or aromatic alcohol, aliphatic ether, cyclic ethers, aliphatic ketone, fat or aromatic carboxylic acid.Particularly suitable be the alkyl ester that contains the aliphatic saturated monocarboxylic acid of 1-4 carbon atom; The alkyl ester that contains the aromatics of 7-8 carbon atom; Contain 2-8 carbon atom, be preferably the aliphatic ether of 4-5 carbon atom; Contain the cyclic aliphatic ether of 4-5 carbon atom, preferably contain the monoether or the diether of 4 carbon atoms; With contain 3-6 carbon atom, be preferably the aliphatic ketone of 4-5 carbon atom.For example: methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol, n-Octanol, isooctyl alcohol, ethylene glycol, propylene glycol, chloroethanol, ethapon, ether, butyl ether, methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF) (THF), acetone, methyl iso-butyl ketone (MIBK) etc. are preferably ethanol, Virahol, propyl carbinol, tetrahydrofuran (THF).Electron donor can use separately or several being used.
In above-mentioned complex carrier, suitable electron donor compound also comprises and contains organic epoxy compounds and/or organo phosphorous compounds, and described organic epoxy compounds is selected from and comprises at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine of carbonatoms.For example: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether.Described organo phosphorous compounds is selected from the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.For example: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, phosphorous acid benzene methyl.
In above-mentioned complex carrier, form uniform solution in order to make magnesium halide and electron donor contact reacts, generally, every mole of magnesium halide needs 3～50 moles of electron donor compounds, is preferably 6～30 moles.The preparation of this solution can be carried out in the presence of a kind of inert organic solvents, and this solvent does not form adducts with magnesium halide.The aromatic hydrocarbons of the preferred alkane of solvent, halohydrocarbon and 6-12 carbon atom, for example hexane, heptane, ethylene dichloride, toluene, dimethylbenzene, ethylbenzene etc.
Obtain more short grained complex carrier for the ease of spray shaping, described silica supports material is generally selected the silica gel of median size less than 30 μ m for use, be preferably less than 10 μ m, more preferably particle diameter also claims aerosil less than the smoke-like silica gel of 1 μ m.The specific surface area of this silica gel is generally 200 ± 50m
2/ g.
With solution and the slurry that obtains after silica gel mixes being suitable for spraying, usually, the add-on of silica gel is 10～200g in every liter of solution.
Spraying drying can be carried out according to the following steps: the slurries that solution is obtained after silica-gel carrier mixes carry out spraying drying with the inertia dry gas by the spraying drying instrument, obtain the globular solid particulate.
In order to make complex carrier of the present invention be applicable to the catalyzer of preparation for olefines polymerization better, needing this complex carrier usually is the spherical particle of mean diameter 5-70 μ m, and preferred average diameter of particles is a 10-60 μ m spherical particle.
In the catalyst component of the present invention, the polyol ester compounds shown in the described general formula (I) is disclosed among Chinese patent CN1436766A, CN1436796A and the CN1453298A, and its associated viscera is introduced the present invention as a reference.
In above-mentioned polyol ester compounds, the compound shown in the preferred formula (II).
R wherein
1-R
6, R
1-R
2Definition in group such as the general formula (I).
The also compound shown in the preferred formula (III), wherein R
1-R
2Definition in group such as the general formula (I); R ' is the C of hydrogen identical or inequality, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl.
Above-mentioned general formula (I), (II) and (III) shown in the polyol ester compounds in, preferred R
1And R
2In have at least one to be selected from phenyl, halogenated phenyl, alkyl phenyl or halogenated alkyl phenyl.
Polyol ester compounds described in the catalyst component of the present invention specifically can adopt:
HDGNR10 deposited clone (SEQ ID NO: 22) encoded by the G-protein Chemokine Receptor
(CCR5) Other preferred non-conservative substitution include: M1 replaced with D, E, H, K, R, N, Q, F,
W, Y, P, or C; D2 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P,
Or C; Y3 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; Q4
Replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C; V5 replaced
D, E, H, K, R, N, Q, E, W, Y, P, or C; S6 replaced with D, E, H, K, R, N, Q, F, W,
Y, P, or C; S7 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; P8 substitution is D,
E, H, K, R, A, G, I, L, S, T, M, M, N, Q, F, W, Y, or C; I9 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; Y10 replaced with D, E, H, K, R, N, Q, A, G, I, L, S,
T, M, V, P, or C; D11 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y,
P, or C; I12 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; N13 substitution is D,
E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C; Y14 replaced with D, E, H, K,
R, N, Q, A, G, I, L, S, T, M, V, P, or C; Y15 replaced with D, E, H, K, R, N, Q, A,
G, I, L, S, T, M, V, P, or C; T16 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or
C; S17 replaced with D, E, H, K, R, N, Q, W, Y, P, or C; E18 replaced with H, K, R,
A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; P19 replaced with D, E, H, K, R, A,
G, I, L, S, T, M, V, N, Q, F, W, Y, or C; C20 replaced with D, E, H, K, R, A, G, I,
L, S, T, M, V, N, Q, F, W, Y, or P; Q21 replaced with D, E, H, K, R, A, G, I, L, S,
T, M, V, F, W, Y, P, or C; K22 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F,
W, Y, P, or C; I23 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; N24 for
On behalf of D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C; V25 substitution is D,
E, H, K, R, N, Q, F, W, Y, P, or C; K26 replaced with D, E, A, G, I, L, S, T, M, V,
N, Q, F, W, Y, P, or C; Q27 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F,
W, Y, P, or C; 128 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; A29 for
On behalf of D, E, H, K, R, N, Q, F, W, Y, P, or C; A30 replaced with D, E, H, K, R, N,
Q, F, W, Y, P, or C; R31 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y,
P, or C; L32 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; L33 replaced
D, E, H, K, R, N, Q, F, W, Y, P, or C; P34 replaced with D, E, H, K, R, A, G, I, L,
S, T, M, V, N, Q, F, W, Y, or C; P35 replaced with D, E, H, K, R, A, G, I, L, S, T,
M, V, N, Q, F, W, Y, or C; L36 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or
C; Y37 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; S38 for
On behalf of D, E, H, K, R, N, Q, F, W, Y, P, or C; L39 replaced with D, E, H, K, R, N,
Q, F, W, Y, P, or C; V40 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
F41 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; I42 alternative
Is D, E, H, K, R, N, Q, F, W, Y, P, or C; F43 replaced with D, E, H, K, R, N, Q,
A, G, I, L, S, T, M, V, P, or C; G44 replaced with D, E, H, K, R, N, Q, F, W, Y, P,
Or C; F45 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; V46
Replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; G47 replaced with D, E, H, K, R,
N, Q, F, W, Y, P, or C; N48 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F,
W, Y, P, or C; M49 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; L50 for
On behalf of D, E, H, K, R, N, Q, F, W, Y, P, or C; V51 replaced with D, E, H, K, R, N,
Q, F, W, Y, P, or C; I52 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; L53
Replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; I54 replaced with D, E, H, K, R, N,
Q, F, W, Y, P, or C; L55 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; 156
Replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; N57 replaced with D, E, H, K, R,
A, G, I, L, S, T, M, V, F, W, Y, P, or C; C58 replaced with D, E, H, K, R, A, G, I,
L, S, T, M, V, N, Q, F, W, Y, or P; K59 replaced with D, E, A, G, I, L, S, T, M, V,
N, Q, F, W, Y, P, or C; R60 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W,
Y, P, or C; L61 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; K62 replaced
Is D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; S63 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; M64 replaced with D, E, H, K, R, N, Q, F, W, Y, P,
Or C; T65 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; D66 substitution is H,
K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; I67 replaced with D, E, H, K,
R, N, Q, F, W, Y, P, or C; Y68 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T,
M, V, P, or C; L69 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; L70 for
On behalf of D, E, H, K, R, N, Q, F, W, Y, P, or C; N71 replaced with D, E, H, K, R, A,
G, I, L, S, T, M, V, F, W, Y, P, or C; L72 replaced with D, E, H, K, R, N, Q, F, W,
Y, P, or C; A73 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; I74 replaced
D, E, H, K, R, N, Q, F, W, Y, P, or C; S75 replaced with D, E, H, K, R, N, Q, F,
W, Y, P, or C; D76 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P,
Or C; L77 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; F78 replaced with D, E,
H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; F79 replaced with D, E, H, K, R, N,
Q, A, G, I, L, S, T, M, V, P, or C; L80 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; L81 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; T82 replaced
D, E, H, K, R, N, Q, F, W, Y, P, or C; V83 replaced with D, E, H, K, R, N, Q, F,
W, Y, P, or C; P84 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W,
Y, or C; F85 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C;
W86 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; A87 alternative
Is D, E, H, K, R, N, Q, F, W, Y, P, or C; H88 replaced with D, E, A, G, I, L, S, T,
M, V, N, Q, F, W, Y, P, or C; Y89 replaced with D, E, H, K, R, N, Q, A, G, I, L, S,
T, M, V, P, or C; A90 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; A91
Replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; A92 replaced with D, E, H, K, R,
N, Q, F, W, Y, P, or C; Q93 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F,
W, Y, P, or C; W94 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P,
Or C; D95 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C;
F96 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; G97 replaced
Is D, E, H, K, R, N, Q, F, W, Y, P, or C; N98 replaced with D, E, H, K, R, A, G,
I, L, S, T, M, V, F, W, Y, P, or C; T99 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; M100 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; C101 substitution
Is D, E, H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, or P; Q102 replaced
D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C; L103 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; L104 replaced with D, E, H, K, R, N, Q, F, W, V, P,
Or C; T105 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; G106 substitution is D,
E, H, K, R, N, Q, F, W, Y, P, or C; L107 replaced with D, E, H, K, R, N, Q, F, W,
Y, P, or C; Y108 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or
C; F109 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; I110
Replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; G111 replaced with D, E, H, K, R,
N, Q, F, W, Y, P, or C; F112 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T,
M, V, P, or C; F113 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P,
Or C; S114 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; G115 substitution is D,
E, H, K, R, N, Q, F, W, Y, P, or C; I116 replaced with D, E, H, K, R, N, Q, F, W,
Y, P, or C; F117 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or
C; F 118 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; I119
Replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; I120 replaced with D, E, H, K, R,
N, Q, F, W, Y, P, or C; L121 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
L122 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; T123 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; 1124 replaced with D, E, H, K, R, N, Q, F, W, Y, P,
Or C; D125 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C;
R126 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; Y127 for
On behalf of D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; L128 substitution is D,
E, H, K, R, N, Q, F, W, Y, P, or C; A129 replaced with D, E, H, K, R, N, Q, F, W,
Y, P, or C; V130 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; V131 for
On behalf of D, E, H, K, R, N, Q, F, W, Y, P, or C; H132 replaced with D, E, A, G, I, L,
S, T, M, V, N, Q, F, W, Y, P, or C; A133 replaced with D, E, H, K, R, N, Q, F, W,
Y, P, or C; V134 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; F135 replaced
Is D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; A136 replaced with D, E,
H, K, R, N, Q, F, W, Y, P, or C; L137 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; K138 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C;
A139 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; R140 replaced with D, E, A,
G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; T141 replaced with D, E, H, K, R, N,
Q, F, W, Y, P, or C; V142 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
T143 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; F144 replaced with D, E, H,
K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; G145 replaced with D, E, H, K, R, N,
Q, F, W, Y, P, or C; V146 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
V147 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; T148 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; S149 replaced with D, E, H, K, R, N, Q, F, W, Y, P,
Or C; V150 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; I151 substitution is D,
E, H, K, R, N, Q, F, W, Y, P, or C; T152 replaced with D, E, H, K, R, N, Q, F, W,
Y, P, or C; W153 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or
C; V154 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; V155 replaced with D, E,
H, K, R, N, Q, F, W, Y, P, or C; A156 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; V157 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; F158 replaced
D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; A159 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; S160 replaced with D, E, H, K, R, N, Q, F, W, Y, P,
Or C; L161 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; P162 substitution is D,
E, H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, or C; G163 replaced with D, E,
H, K, R, N, Q, F, W, Y, P, or C; I164 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; I165 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; F166 replaced
D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; T167 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; R168 replaced with D, E, A, G, I, L, S, T, M, V, N,
Q, F, W, Y, P, or C; S169 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
Q170 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C; K171
Replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; E172 substitution is H,
K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; G173 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; L174 replaced with D, E, H, K, R, N, Q, F, W, Y, P,
Or C; H175 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C;
Y176 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; T177 for
On behalf of D, E, H, K, R, N, Q, F, W, Y, P, or C; C178 replaced with D, E, H, K, R, A,
G, I, L, S, T, M, V, N, Q, F, W, Y, or P; S179 replaced with D, E, H, K, R, N, Q, F,
W, Y, P, or C; S180 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; H181
Replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; F182 substitution is D,
E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; P183 replaced with D, E, H, K,
R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, or C; Y184 replaced with D, E, H, K, R,
N, Q, A, G, I, L, S, T, M, V, P, or C; S185 replaced with D, E, H, K, R, N, Q, F,
W, Y, P, or C; Q186 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P,
Or C; Y187 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C;
Q188 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C; F189
Replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; W190 replaced
D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; K191 replaced with D, E, A,
G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; N192 replaced with D, E, H, K, R, A,
G, I, L, S, T, M, V, F, W, Y, P, or C; F193 replaced with D, E, H, K, R, N, Q, A,
G, I, L, S, T, M, V, P, or C; Q194 replaced with D, E, H, K, R, A, G, I, L, S, T, M,
V, F, W, Y, P, or C; T195 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
L196 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; K197 replaced with D, E, A,
G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; I198 replaced with D, E, H, K, R, N, Q,
F, W, Y, P, or C; V199 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; I200
Replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; L201 replaced with D, E, H, K, R,
N, Q, F, W, Y, P, or C; G202 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
L203 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; V204 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; L205 replaced with D, E, H, K, R, N, Q, F, W, Y, P,
Or C; P206 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, or
C; L207 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; L208 replaced with D, E,
H, K, R, N, Q, F, W, Y, P, or C; V209 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; M210 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; V211 replaced
Is D, E, H, K, R, N, Q, F, W, Y, P, or C; I212 replaced with D, E, H, K, R, N, Q,
F, W, Y, P, or C; C213 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, N, Q, F,
W, Y, or P; Y214 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or
C; S215 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; G216 replaced with D, E,
H, K, R, N, Q, F, W, Y, P, or C; I217 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; L218 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; K219 replaced
D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; T220 replaced with D, E, H, K,
R, N, Q, F, W, Y, P, or C; L221 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or
C; L222 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; R223 replaced with D, E,
A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; C224 replaced with D, E, H, K, R,
A, G, I, L, S, T, M, V, N, Q, F, W, Y, or P; R225 replaced with D, E, A, G, I, L, S,
T, M, V, N, Q, F, W, Y, P, or C; N226 replaced with D, E, H, K, R, A, G, I, L, S, T,
M, V, F, W, Y, P, or C; E227 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F,
W, Y, P, or C; K228 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P,
Or C; K229 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C;
R230 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; H231 for
On behalf of D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; R232 replaced with D, E,
A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; A233 replaced with D, E, H, K, R,
N, Q, F, W, Y, P, or C; V234 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
R235 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; L236 for
On behalf of D, E, H, K, R, N, Q, F, W, Y, P, or C; I237 replaced with D, E, H, K, R, N,
Q, F, W, Y, P, or C; F238 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M,
V, P, or C; T239 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; I240 replaced
Is D, E, H, K, R, N, Q, F, W, Y, P, or C; M241 replaced with D, E, H, K, R, N,
Q, F, W, Y, P, or C; I242 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
V243 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; Y244 replaced with D, E, H,
K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; F245 replaced with D, E, H, K, R, N,
Q, A, G, I, L, S, T, M, V, P, or C; L246 replaced with D, E, H, K, R, N, Q, F, W,
Y, P, or C; F247 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or
C; W248 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; A249
Replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; P250 replaced with D, E, H, K, R,
A, G, I, L, S, T, M, V, N, Q, F, W, Y, or C; Y251 replaced with D, E, H, K, R, N,
Q, A, G, I, L, S, T, M, V, P, or C; N252 replaced with D, E, H, K, R, A, G, I, L, S,
T, M, V, F, W, Y, P, or C; I253 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or
C; V254 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; L255 replaced with D, E,
H, K, R, N, Q, F, W, Y, P, or C; L256 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; L257 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; N258 replaced
D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C; T259 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; F260 replaced with D, E, H, K, R, N, Q, A, G, I, L,
S, T, M, V, P, or C; Q261 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F, W,
Y, P, or C; E262 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P,
Or C; F263 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C;
F264 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; G265 for
On behalf of D, E, H, K, R, N, Q, F, W, Y, P, or C; L266 replaced with D, E, H, K, R, N,
Q, F, W, Y, P, or C; N267 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F,
W, Y, P, or C; N268 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P,
Or C; C269 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, or
P; S270 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; S271 replaced with D, E,
H, K, R, N, Q, F, W, Y, P, or C; S272 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; N273 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or
C; R274 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; L275
Replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; D276 replaced with H, K, R, A, G,
I, L, S, T, M, V, N, Q, F, W, Y, P, or C; Q277 replaced with D, E, H, K, R, A, G, I,
L, S, T, M, V, F, W, Y, P, or C; A278 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; M279 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; Q280 replaced
Is D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C; V281 replaced with D,
E, H, K, R, N, Q, F, W, Y, P, or C; T282 replaced with D, E, H, K, R, N, Q, F, W,
Y, P, or C; E283 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P,
Or C; T284 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; L285 substitution is D,
E, H, K, R, N, Q, F, W, Y, P, or C; G286 replaced with D, E, H, K, R, N, Q, F, W,
Y, P, or C; M287 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; T288 for
On behalf of D, E, H, K, R, N, Q, F, W, Y, P, or C; H289 replaced with D, E, A, G, I, L,
S, T, M, V, N, Q, F, W, Y, P, or C; C290 replaced with D, E, H, K, R, A, G, I, L, S,
T, M, V, N, Q, F, W, Y, or P; C291 replaced with D, E, H, K, R, A, G, I, L, S, T,
M, V, N, Q, F, W, Y, or P; I292 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or
C; N293 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C;
P294 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, or C;
I295 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; I296 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; Y297 replaced with D, E, H, K, R, N, Q, A, G, I, L,
S, T, M, V, P, or C; A298 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
F299 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; V300 for
On behalf of D, E, H, K, R, N, Q, F, W, Y, P, or C; G301 replaced with D, E, H, K, R, N,
Q, F, W, Y, P, or C; E302 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F,
W, Y, P, or C; K303 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P,
Or C; F304 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C;
R305 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; N306 for
On behalf of D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C; Y307 replaced
D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; L308 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; L309 replaced with D, E, H, K, R, N, Q, F, W, Y, P,
Or C; V310 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; F311 substitution is D,
E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P, or C; F312 replaced with D, E, H, K,
R, N, Q, A, G, I, L, S, T, M, V, P, or C; Q313 replaced with D, E, H, K, R, A, G, I,
L, S, T, M, V, F, W, Y, P, or C; K314 replaced with D, E, A, G, I, L, S, T, M, V, N,
Q, F, W, Y, P, or C; H315 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y,
P, or C; I316 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; A317 replaced
D, E, H, K, R, N, Q, F, W, Y, P, or C; K318 replaced with D, E, A, G, I, L, S, T,
M, V, N, Q, F, W, Y, P, or C; R319 replaced with D, E, A, G, I, L, S, T, M, V, N,
Q, F, W, Y, P, or C; F320 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M,
V, P, or C; C321 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y,
Or P; K322 replaced with D, E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C;
C323 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, or P;
C324 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, or P;
S325 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; I326 replaced with D, E, H,
K, R, N, Q, F, W, Y, P, or C; F327 replaced with D, E, H, K, R, N, Q, A, G, I, L,
S, T, M, V, P, or C; Q328 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F, W,
Y, P, or C; Q329 replaced with D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P,
Or C; E330 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C;
A331 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; P332 replaced with D, E, H,
K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, or C; E333 replaced with H, K, R, A,
G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; R334 replaced with D, E, A, G, I, L, S,
T, M, V, N, Q, F, W, Y, P, or C; A335 replaced with D, E, H, K, R, N, Q, F, W, Y,
P, or C; S336 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; S337 replaced
D, E, H, K, R, N, Q, F, W, Y, P, or C; V338 replaced with D, E, H, K, R, N, Q, F,
W, Y, P, or C; Y339 replaced with D, E, H, K, R, N, Q, A, G, I, L, S, T, M, V, P,
Or C; T340 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; R341 substitution is D,
E, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; S342 replaced with D, E, H, K, R,
N, Q, F, W, Y, P, or C; T343 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C;
E344 replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; E345
Replaced with H, K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; Q346 replaced
Is D, E, H, K, R, A, G, I, L, S, T, M, V, F, W, Y, P, or C; E347 substitution is H,
K, R, A, G, I, L, S, T, M, V, N, Q, F, W, Y, P, or C; I348 replaced with D, E, H, K,
R, N, Q, F, W, Y, P, or C; S349 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or
C; V350 replaced with D, E, H, K, R, N, Q, F, W, Y, P, or C; G351 replaced with D, E,
H, K, R, N, Q, F, W, Y, P, or C;, and / or L352 replaced with D, E, H, K, R, N, Q, F,
W, Y, P, or C
...
In the catalyst component of the present invention, general formula Ti (OR)
4-mX
mShown titanium compound, R is C in the formula
1～C
14Aliphatic group, X is Cl or Br, m 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.Titanium compound should be a completely soluble liquefied compound under application of temperature, in the non-polar solvent.
Ratio between reactant complex carrier, polyol ester compounds and the titanium compound is: polyol ester compounds/0.5～2 mole titanium compound of 5～20 gram complex carrier/2～10 mmoles.
Specifically, ingredient of solid catalyst of the present invention can prepare as follows:
(1) preparation magnesium chloride solution
Can prepare magnesium chloride solution according to disclosed certain methods, such as using US4784983 and the disclosed magnesium chloride dissolution system of US4861847 to prepare magnesium chloride solution.
Preferably, among the present invention, magnesium chloride solution prepares as follows:
In the reactor of stirring is housed, add one or more above-mentioned suitable electron donor compounds, for example alcohol, ether or ester add Magnesium Chloride Anhydrous then, and heating makes the magnesium chloride dissolving.Wherein alcohol is 3～50: 1 with the mol ratio of magnesium chloride, and the mol ratio of ether or ester and magnesium chloride is 0～20: 1.The dissolving of above-mentioned magnesium chloride also can be carried out in a kind of inert organic solvents, and the consumption of solvent is 0～20ml/gMgCl
2
(2) prepare spherical MgCl
2/ SiO
2Complex carrier
Add smoke-like silica gel in above-mentioned magnesium chloride solution, the add-on of silica gel is 0.1～2g/gMgCl
2, used silica gel is the aerosil of average particulate diameter less than 10 μ m.Stirred 0.5～3 hour down at 10～100 ℃ afterwards, make slurries.Then slurries are carried out spraying drying with the inertia dry gas by the spraying drying instrument, obtaining median size is the spherical MgCl of 5～60 μ m
2/ SiO
2Complex carrier.Inlet air temperature during spraying drying is controlled at 80～300 ℃, and air outlet temperature is controlled at 50～200 ℃.Usually, consisting of of complex carrier:
MgCl
2: 20%～60% (weight)
SiO
2: 10%～60% (weight)
Alcohol: 5%～40% (weight)
Ether: 0～20% (weight)
Solvent:＜5% (weight)
(3) preparation ingredient of solid catalyst
Above-mentioned ball type carrier is suspended in TiCl
4Mixed solution (TiCl with hexane
4Amount is 5～10mlTiCl
4/ g carrier, hexane and TiCl
4Volume ratio be 0～2) in, slowly be warmed up to 80～100 ℃, after keeping for some time under this temperature, liquid is filtered; Add excessive TiCl
4(TiCl
4Amount is 12～16mlTiCl
4/ g carrier), in 1～3 hour, slowly be warming up to 100～120 ℃, and add the polyol ester compounds in temperature-rise period, its add-on is 0.05～0.25mol/molMgCl
2React 1～2 hour after-filtration; Randomly, add a certain amount of TiCl
4, kept 1～2 hour at 120 ℃, filtrate is filtered; With the solids washing, then solids is vacuumized drying with inert solvent such as hexane etc. under 30 ℃～50 ℃, promptly get ingredient of solid catalyst of the present invention.
In addition, the invention still further relates to a kind of catalyzer that is used for olefinic polyreaction, it comprises the reaction product of following component:
(1) above-mentioned catalyst component of the present invention (active ingredient),
(2) alkylaluminium cpd component, its general formula such as AlR
1 nX
3-nShown in, R in the formula
1Be identical or different C
1～C
20Alkyl can be a straight chain, and side chain or cyclic alkyl, X are halogen, n=1,2 or 3.Preferred triethyl aluminum, triisopropylaluminiuand, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium or aluminium diethyl monochloride etc.Can select for use one or more aluminum alkyls to mix use.
(3) randomly, a kind of external electron donor compound, for example list or polyfunctional carboxylic acids, carboxylic acid anhydride and carboxylicesters, ketone, ether, alcohol, lactone, and organophosphorus and silicoorganic compound.Preferably have organic silicon compound, as general formula R
nSi (OR)
4-nSilicoorganic compound, 0≤n in the formula≤3, R and R
*Be of the same race or different alkyl, cycloalkyl, aryl, haloalkyl, R also can be halogen or hydrogen atom.
In many cases, particularly when this catalyzer was used for propylene polymerization, the use of external electron donor compound was very necessary.
The ratio between ingredient of solid catalyst (1), alkylaluminium cpd component (2) and the external electron donor component (3) wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1: 5～1000: 0～500.
Wherein component (2) and optional component (3) can be separately or as two kinds of mixture of ingredients and active ingredient contact reacts.
Above-mentioned catalyzer is suitable for alkene, particularly CH
2=CHR alkene (wherein R is 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.
The polymerization of alkene is carried out according to currently known methods, is dissolved in the liquid phase of inert solvent in liquid monomer or monomer, or in gas phase, or by operating in the polymerization mix technology of gas-liquid in mutually.Polymerization temperature is generally 0 ℃～150 ℃, preferably 60 ℃～100 ℃.Polymerization pressure is a normal pressure or higher.
Embodiment
Following Example is used for illustrating the present invention, is not to be used for limiting the scope of the invention.
Embodiment 1
1, the preparation of magnesium chloride solution:
Using N
2Fully add 34.5ml ethanol successively, 18.5ml propyl carbinol, 32.4ml tetrahydrofuran (THF) in the 350ml glass reactor that the metathetical band stirs.Under the situation that the feed glass reactor temperature does not sharply rise, slowly add Magnesium Chloride Anhydrous 9.5g while stirring, slowly heat up then, temperature makes Magnesium Chloride Anhydrous fully dissolving in this solution in the controlling reactor under stirring about 60 ℃.After the system for the treatment of is dissolved substantially, kept again 2.5 hours, obtain magnesium chloride solution.
2, the preparation of complex carrier:
In above-mentioned magnesium chloride solution, add pyrogenic silica 6g (Cabot Corporation, TS-610, particle diameter is 0.02～0.1 μ m), fully stirred 1 hour, form uniform suspension, carry out spraying drying then in the spraying drying instrument, the control inlet air temperature is that 200 ℃, air outlet temperature are 130 ℃, obtains median size and be the spherical complex carrier about 20 μ m.That analyzes the gained carrier consists of (weight percentage): MgCl
2: 43.3%; SO
2: 26.5%; Ethanol: 11.2%; Propyl carbinol: 14.7%; Tetrahydrofuran (THF): 4.3%.
3, Preparation of catalysts:
Get above-mentioned complex carrier 7.0g, slowly add in the titanium tetrachloride of the 100ml that is pre-chilled to-20 ℃, be warmed up to 40 ℃ in 1 hour, add 9 at 40 ℃, 9-two (benzoyloxy methyl) fluorenes 1.0ml rose to 100 ℃ in 0.5 hour then, kept 2 hours, and mother liquor is filtered.Add titanium tetrachloride 100ml again, be warmed up to 120 ℃ in 0.5 hour, kept 1 hour, mother liquor is filtered.Wash these solidss 5 times with hexane at 60 ℃, each hexane consumption is 60ml, and washing time is 5 minutes.With the solids drying, obtain ingredient of solid catalyst at last.
Propylene polymerization:
2 liters of autoclaves are at room temperature introduced the hexane solution (concentration of triethyl aluminum is 1.0mmol/ml) of 2ml triethyl aluminum, hexane solution (concentration of CHMDMS is 0.1mmol/ml), 10ml anhydrous hexane and 10.6mg such as the above-mentioned prepared solid spherical catalyst component of 2.0ml cyclohexyl methyl dimethoxy silane (CHMDMS) in the stream of nitrogen gas after vacuumizing and replacing successively with nitrogen and propylene.Close autoclave, introduce the hydrogen of 4.0NL and the liquid propene of 1.0L; In under agitation 5 minutes temperature is risen to 70 ℃., stop stirring after 1 hour 70 ℃ of following polyreactions, remove unreacted propylene monomer, polymeric kettle is cooled to room temperature, obtains the 328.5g polypropylene, measure polyacrylic degree of isotacticity (I.I.)=95.91%, melting index (M.I)=28.17g/10min, Mw/Mn=10.25.Activity of such catalysts is 31.0Kg polypropylene/g ingredient of solid catalyst, and polymer stacks density is 0.46g/ml.
Embodiment 2
1, the preparation of magnesium chloride solution:
With embodiment 1.
2, the preparation of complex carrier:
With embodiment 1.
3, catalyzer is synthetic:
Get above-mentioned complex carrier 7.0g, slowly add in the titanium tetrachloride of the 100ml that is pre-chilled to-20 ℃, be warmed up to 40 ℃ in 1 hour, add 2-sec.-propyl-2-isopentyl-1 at 40 ℃, ammediol dibenzoate 1.0ml rose to 100 ℃ in 0.5 hour then, kept 2 hours, mother liquor is filtered.Add titanium tetrachloride 100ml again, be warmed up to 120 ℃ in 0.5 hour, kept 1 hour, mother liquor is filtered.Wash these solidss 5 times with hexane at 60 ℃, each hexane consumption is 60ml, and washing time is 5 minutes.With the solids drying, obtain ingredient of solid catalyst at last.
Propylene polymerization:
Polymerization process is with embodiment 1.Activity of such catalysts is 32.0Kg polypropylene/g ingredient of solid catalyst, the polyacrylic degree of isotacticity (I.I.)=97.6% that obtains, and melting index (M.I)=25.20g/10min, Mw/Mn=7.78, polymer stacks density is 0.45g/ml.
Embodiment 3
1, the preparation of magnesium chloride solution:
Using N
2Fully be added in successively through in the abundant metathetical reactor of high pure nitrogen in the 350ml glass reactor that the metathetical band stirs, add anhydrous MgCl successively
20.05mol, toluene 95ml, epoxy chloropropane (ECP) 0.05mol and tributyl phosphate (TBP) 0.046mol are warming up to 50 ℃ under stirring, and dissolve fully until solid.
2, the preparation of complex carrier:
In above-mentioned solution, add pyrogenic silica 3g (Cabot Corporation, TS-610, particle diameter are 0.02～0.1 μ m), fully stirred 1 hour, form slurries.Carry out spraying drying then in the spraying drying instrument, the control inlet air temperature is that 220 ℃, air outlet temperature are 160 ℃, obtains median size and be the spherical complex carrier about 20 μ m.
3, Preparation of catalysts:
Preparation of catalysts is with embodiment 2.
Propylene polymerization:
Polymerization process is with embodiment 2.Activity of such catalysts is 25.4Kg polypropylene/g ingredient of solid catalyst, polyacrylic degree of isotacticity (I.I.)=97.32%, melting index (M.I)=25.97g/10min, Mw/Mn=8.52.Polymer stacks density is 0.46g/ml.
The comparative example 1
Preparation of catalysts: (do not adopt complex carrier of the present invention, and adopt polyol ester compound of the present invention)
In through the abundant metathetical reactor of high pure nitrogen, add anhydrous MgCl successively
20.05mol, toluene 95ml, epoxy chloropropane (ECP) 0.05mol and tributyl phosphate (TBP) 0.046mol, be warming up to 50 ℃ under stirring, and kept 2.5 hours, solid dissolves fully, add Tetra hydro Phthalic anhydride 0.0095mol then, kept again 1 hour, and solution was cooled to-25 ℃, in one hour, drip TiCl
456ml slowly is warming up to 80 ℃, in temperature-rise period, progressively separates out solids.Add 9,9-two (benzoyloxy methyl) fluorenes 1ml kept under 80 ℃ 1 hour.Filter the back and wash twice, obtain pale brown look solid sediment with toluene 100ml.Add toluene 60ml then, TiCl
440ml handled 2 hours down at 90 ℃, and re-treatment is once again after the venting filtrate.Add under 110 ℃ of the toluene 100ml and wash 5 minutes three times, hexane 100ml washes four times, obtains ingredient of solid catalyst.
Propylene polymerization:
Polymerization process is with embodiment 1.Activity of such catalysts is 42.5Kg polypropylene/g ingredient of solid catalyst, the polyacrylic degree of isotacticity (I.I.)=98.5% that obtains, and melting index (M.I)=4.5g/10min, molecular weight distribution mw/mn=5.9, polymer stacks density is 0.44g/ml.
The comparative example 2
Preparation of catalysts: (adopt complex carrier of the present invention, and do not adopt polyol ester compounds of the present invention, adopting conventional aromatic carboxylates's class is internal electron donor)
1, the preparation of magnesium chloride solution:
With embodiment 1.
2, the preparation of complex carrier:
With embodiment 1.
3, catalyzer is synthetic:
Get above-mentioned complex carrier 7.0g, slowly add in the titanium tetrachloride of the 100ml that is pre-chilled to-20 ℃, be warmed up to 40 ℃ in 1 hour, add n-butyl phthalate 1.0ml, rose to 100 ℃ in 0.5 hour then, kept 2 hours, mother liquor is filtered at 40 ℃.Add titanium tetrachloride 100ml again, be warmed up to 120 ℃ in 0.5 hour, kept 1 hour, mother liquor is filtered.Wash these solidss 5 times with hexane at 60 ℃, each hexane consumption is 60ml, and washing time is 5 minutes.With the solids drying, obtain ingredient of solid catalyst at last.
Propylene polymerization:
Polymerization process is with embodiment 1.Activity of such catalysts is 24.4Kg polypropylene/g ingredient of solid catalyst, the polyacrylic degree of isotacticity (I.I.)=97.15% that obtains, and melting index (M.I)=29.53g/10min, Mw/Mn=5.56, polymer stacks density is 0.45g/ml.
Table 1
| Embodiment | Catalytic activity KgPP/gcat | Degree of isotacticity wt% | Melting index g/10min | Molecular weight distribution mw/mn | Apparent density g/cm 3 |
| Example 1 | 31.0 | 95.9 | 28.2 | 10.25 | 0.46 |
| Example 2 | 32.0 | 97.6 | 25.2 | 7.78 | 0.45 |
| Example 3 | 25.4 | 97.3 | 26.0 | 8.52 | 0.46 |
| Contrast 1 | 42.5 | 98.5 | 4.5 | 5.90 | 0.44 |
| Contrast 2 | 24.4 | 97.2 | 29.5 | 5.56 | 0.45 |
From table 1 embodiment and Comparative Examples related data more as can be seen, the complex carrier that the present invention adopts combines the catalyzer that obtains with novel internal electron donor and is used for propylene polymerization, has advantages of high catalytic activity.The polymkeric substance that obtains has higher tacticity, the molecular weight distribution broad, and it is big that polymer stacks density becomes, and the over-all properties of catalyzer is better.
Claims (10)
1, a kind of catalyst component that is used for olefinic polymerization, it contains the reaction product of following component:
(1) a kind of complex carrier, it is magnesium halide to be contacted with one or more electron donor compounds form solution, this solution mixes with the silica-gel carrier of median size less than 30 μ m, the spray-dried spherical particle that makes;
(2) at least aly be selected from the polyol ester compounds shown in the general formula (I):
R in the formula
1-R
6, R
1-R
2nGroup is hydrogen, halogen or the replacement identical or inequality or the C of unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene, C
10-C
20Fused ring aryl or C
2-C
10Ester group; But R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2nComprise one or several heteroatoms on the group arbitrarily as carbon or hydrogen atom 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;
(3) general formula Ti (OR)
4-mX
mShown titanium compound, R is C in the formula
1～C
14Aliphatic group, X is identical or different, is selected from from F, Cl and Br, m is 1～4 integer.
2, the catalyst component that is used for olefinic polymerization according to claim 1, it is characterized in that, preparation during complex carrier used electron donor compound be selected from the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of alkyl ester, phosphoric acid or phosphorous acid of oxide compound, aliphatic ketone, fat or the aromatic carboxylic acid of fat or aromatic alcohol, aliphatic ether, cyclic ethers, aliphatics alkene or halogenated aliphatic alkene.
3, the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that, the average particle diameter of used silica gel is less than 1 μ m during the preparation complex carrier.
4, the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that, the mol ratio of described electron donor compound and magnesium halide is 3～50: 1 during the preparation complex carrier.
5, the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that, the polyol ester compounds shown in the described general formula (I) comprises the compound shown in general formula (II):
R wherein
1-R
6, R
1-R
2Definition in group such as the general formula (I).。
6, the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that, the polyol ester compounds shown in the described general formula (I) comprises the compound shown in general formula (III):
R wherein
1-R
2Definition in group such as the general formula (I); R ' is the C of hydrogen identical or inequality, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl.
7, a kind of CH that is used for
2The catalyzer of=CHR olefinic polyreaction, wherein R is hydrogen or C
1-C
6Alkyl or aryl, comprise the reaction product of following component:
(1) the described catalyst component of one of claim 1-6;
(2) alkylaluminium cpd,
(3) randomly, external electron donor component.
8, catalyzer according to claim 7, wherein alkylaluminium cpd such as AlR
1 nX
3-nShown in, R in the formula
1Be identical or different C
1～C
20Alkyl can be a straight chain, and side chain or cyclic alkyl, X are halogen, n=1,2 or 3.
9, catalyzer according to claim 7, wherein the external electron donor component is a general formula R
nSi (OR`)
4-nSilicoorganic compound, 0≤n in the formula≤3, R is of the same race or different alkyl, cycloalkyl, aryl, haloalkyls with R., R also can be halogen or hydrogen atom.
10, catalyzer according to claim 7, the ratio between catalyst component (1), alkylaluminium cpd component (2) and the external electron donor component (3) wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1: 5～1000: 0～500.
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