CN104059181B - A kind of supported non-metallocene metallic catalyst for vinyl polymerization - Google Patents

A kind of supported non-metallocene metallic catalyst for vinyl polymerization Download PDF

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CN104059181B
CN104059181B CN201310091192.7A CN201310091192A CN104059181B CN 104059181 B CN104059181 B CN 104059181B CN 201310091192 A CN201310091192 A CN 201310091192A CN 104059181 B CN104059181 B CN 104059181B
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metallocene
alkyl
metallic catalyst
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formula
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CN104059181A (en
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李岩
高榕
廖浩瀚
刘东兵
周俊领
黄廷杰
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention discloses a kind of load non-metallocene metallic catalyst for vinyl polymerization and preparation method, this catalyst includes (a) non-metallocene compound；(b) chlorination silicon alkyl；The product of (c) alkylaluminoxane (d) silica-gel carrier；Its preparation method includes: the preparation of preparation (3) the modified silica-gel load non-metallocene metallic catalyst of preparation (2) the alkylaluminoxane modified silica gel carrier of (1) chlorination alkyl Si modification silica-gel carrier, obtained non-metallocene catalyst catalyzed ethylene polymerization or combined polymerization have the highest polymerization activity.Used silica gel support preparation method is simple, and the carried catalyst particle shape of gained is good, and size is adjustable.

Description

A kind of supported non-metallocene metallic catalyst for vinyl polymerization
Technical field
The present invention relates to the preparation method of a kind of supported non-metallocene metallic catalyst for vinyl polymerization, and institute Obtain catalyst application in terms of olefinic polymerization.
Technical background
In the evolution of olefin polymerization catalysis, it is non-metallocene catalyzed that nineteen nineties develops Agent has obtained great development and concern.Particularly the 4th group 4 transition metal containing phenoxy-imine ligands coordinates Thing (EP 0874005, WO 0155231), has the highest catalysis in olefine polymerization activity, and can obtain The vistanex of the features such as functionalization, has a good application prospect.But homogeneous catalyst gathers at alkene Close and reaction has been shown to have active duration is short, easily stick still, promoter MAO consumption Height, and obtain that polymer molecular weight is the lowest or the most high weak point, it is only the possibility to be applied to the molten of alkene Liquid polymerization technique or high-pressure polymerization process, seriously limit its industrial applicability.
At present, the relevant supported research of non-metallocene catalyst is reported the most, such as patent in recent years CN1539855A、CN1539856A、CN 1789291、CN 1789292、CN 1962702A、CN 1769309A、CN 1769310A、CN101423573A、CN 101798361A、CN 102399313A Carry out loading to obtain load type non-metallocene catalyst etc. providing various ways, wherein use anhydrous chlorination The catalyst of magnesium-supported Nonmetallocene has good particle shape, such as CN 102039186A, CN 102039189A, CN 102039187A, CN 102039185A, CN 101942048A, but this type of catalyst Intensity difference, is easily broken in polymer reactor, thus causes polymer morphology bad, and contains in carrier The components such as alcohol, water, alkoxyl, carrier preparation complexity.And with Si02Catalyst for carrier reports research also A lot, such as CN 102399331A, CN 1539855A, CN 1769309A, CN 1727062A, CN 1962702A, But carrier preparation complexity, is still to introduce substantial amounts of MAO in the course of the polymerization process, and disadvantage mentioned above limits The commercial Application of silica gel load non-metallocene catalyst.
Also have document use containing the composite carrier load Nonmetallocene such as magnesium chloride, silica gel (CN 1539856A, CN 102399317A, CN 102039185A, CN 102399331A, CN 101423574A, CN 1539855A), But supported catalyst preparation method is complicated, and need to add substantial amounts of MAO when polymerization.
Summary of the invention
One of the object of the invention is to provide the non-cyclopentadienyl of a kind of alkylaluminoxane/chlorination silicon alkyl/silica gel load Metallic catalyst and preparation method thereof.
The two of the object of the invention are above-mentioned load non-metallocene metallic catalyst is used for vinyl polymerization or combined polymerization, There is high polymerization activity.
A kind of supported non-metallocene metallic catalyst for vinyl polymerization of the present invention, this catalyst includes following group The product divided:
(1) non-metallocene compound；
(2) chlorination silicon alkyl；
(3) alkylaluminoxane；
(4) silica-gel carrier；
Component (1) described non-metallocene compound, refers to the metal complex shown in formula 1 and 2,
In formula 1, R1Selected from substituted or unsubstituted C1-C20Aliphatic group or C6-C30Aryl radical, R2-R6Identical or different, for hydrogen atom, halogen atom, C1-C20Aliphatic group, C3-C20Cyclic hydrocarbon radical or C6-C20 Aryl radical, on described alkyl arbitrary hydrogen or carbon atom optionally by halogen atom, oxygen, nitrogen, boron, sulfur, Phosphorus, silicon, germanium or stanna atom replace；
M is the transition metal of the 4th race in the periodic table of elements, and X is selected from halogen, alkyl, oxyl, acid One in root and amido, when n is two or more, multiple X group are identical or different；M and n is 1-3 Integer, and m+n=4；
In formula 2: M is the transition metal of the 4th race in the periodic table of elements；N is > integer of 2, when m is During two or more, multiple X group are identical or different；M is the integer meeting M valence state；
X one in halogen, alkyl, oxyl, acid group, amido；
R1-R8Identical or different, for hydrogen atom, halogen atom, C1-C20Aliphatic group, C3-C20Cyclic hydrocarbon Base or C6-C20Aryl radical, arbitrary hydrogen on its described alkyl or carbon atom optionally by halogen atom, oxygen, Nitrogen, boron, sulfur, phosphorus, silicon, germanium or stanna atom replace；
R9-R10Identical or different, selected from substituted or unsubstituted C1-C20Aliphatic group or C6-C30Virtue Fragrant alkyl；
R1-R10In two or more groups optionally mutual keyed jointing cyclization；
Y is a bridge joint group, for C1-C20Aliphatic group or C6-C20Aryl radical, its described hydrocarbon Arbitrary hydrogen on base or carbon atom are optionally by halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium or stanna Atom replaces；
Component (2) described chlorination alkyl silica modifier refers to compound described in below general formula: ClnSi(R1)4-n R in formula1Represent C1-C20Alkyl, n represents the integer of 1-4,
Component (3) described alkylaluminoxane formula is:
In formula, R represents C1-C12Alkyl, a represents the integer of 4-30.
In non-metallocene compound formula (1), R1Selected from n-hexyl, cyclohexyl and phenyl；R2-R6It is selected from Hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl and the tert-butyl group；
M is selected from titanium, zirconium and hafnium, m=n=2；
X is selected from chlorine, bromine, iodine, methyl, ethyl and benzyl；
For the present invention, preferred coordination compound is substituent group M in structural formula, X and R1-R6For as follows Described coordination compound 1-75:
1, M=Ti, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=Cl；
2, M=Ti, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=Cl；
3, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=Cl；
4, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=Cl；
5, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=Et, R6=t-Bu, X=Cl；
6, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=i-Pr, R6=t-Bu, X=Cl；
7, M=Ti, R1=Ph, R2=R3=R4=R5=H, R6=Ph, X=Cl；
8, M=Ti, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=Br；
9, M=Ti, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=Br；
10, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=Br；
11, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=Br；
12, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=Et, R6=t-Bu, X=Br；
13, M=Ti, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=I；
14, M=Ti, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=CH3；
15, M=Ti, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=CH3；
16, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=CH3；
17, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=CH3；
18, M=Ti, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=Bz；
19, M=Ti, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=Bz；
20, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=Bz；
21, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=Bz；
22, M=Ti, R1=cyclohexyl, R2=R3=R4=R5=CH3, R6=t-Bu, X=Bz；
23, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=Et, R6=t-Bu, X=Bz；
24, M=Ti, R1=cyclohexyl, R2=R3=R5=H, R4=i-Pr, R6=t-Bu, X=Bz；
25, M=Zr, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=Cl；
26, M=Zr, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=Cl；
27, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=Cl；
28, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=Cl；
29, M=Zr, R1=cyclohexyl, R2=R3=R4=R5=CH3, R6=t-Bu, X=Cl；
30, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=Et, R6=t-Bu, X=Cl；
31, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=i-Pr, R6=t-Bu, X=Cl；
32, M=Zr, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=Br；
33, M=Zr, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=Br；
34, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=Br；
35, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=Br；
36, M=Zr, R1=cyclohexyl, R2=R3=R4=R5=CH3, R6=t-Bu, X=Br；
37, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=Et, R6=t-Bu, X=Br；
38, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=i-Pr, R6=t-Bu, X=Br；
39, M=Zr, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=I；
40, M=Zr, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=I；
41, M=Zr, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=CH3；
42, M=Zr, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=CH3；
43, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=CH3；
44, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=CH3；
45, M=Zr, R1=cyclohexyl, R2=R3=R4=R5=CH3, R6=t-Bu, X=CH3；
46, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=Et, R6=t-Bu, X=CH3；
47, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=i-Pr, R6=t-Bu, X=Et；
48, M=Zr, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=Bz；
49, M=Zr, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=Bz；
50, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=Bz；
51, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=Bz；
52, M=Zr, R1=cyclohexyl, R2=R3=R4=R5=CH3, R6=t-Bu, X=Bz；
53, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=Et, R6=t-Bu, X=Bz；
54, M=Zr, R1=cyclohexyl, R2=R3=R5=H, R4=i-Pr, R6=t-Bu, X=Bz；
55, M=Hf, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=Cl；
56, M=Hf, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=Cl；
57, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=Cl；
58, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=Cl；
59, M=Hf, R1=cyclohexyl, R2=R3=R4=R5=CH3, R6=t-Bu, X=Cl；
60, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=Et, R6=t-Bu, X=Cl；
61, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=i-Pr, R6=t-Bu, X=Cl；
62, M=Hf, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=CH3；
63, M=Hf, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=CH3；
64, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=CH3；
65, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=CH3；
66, M=Hf, R1=cyclohexyl, R2=R3=R4=R5=CH3, R6=t-Bu, X=CH3；
67, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=Et, R6=t-Bu, X=CH3；
68, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=i-Pr, R6=t-Bu, X=CH3；
69, M=Hf, R1=cyclohexyl, R2=R3=R4=R5=H, R6=t-Bu, X=Bz；
70, M=Hf, R1=Ph, R2=R3=R4=R5=H, R6=t-Bu, X=Bz；
71, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=CH3, R6=t-Bu, X=Bz；
72, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=R6=t-Bu, X=Bz；
73, M=Hf, R1=cyclohexyl, R2=R3=R4=R5=CH3, R6=t-Bu, X=Bz；
74, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=Et, R6=t-Bu, X=Bz；
75, M=Hf, R1=cyclohexyl, R2=R3=R5=H, R4=i-Pr, R6=t-Bu, X=Bz；
In formula 2:
M is the transition metal of the 4th race in the periodic table of elements, selected from early transition metal titanium, zirconium and hafnium；N is The integer of 1-10, m is the integer meeting M valence state；
X is selected from halogen and alkyl, preferably is selected from chlorine, bromine, methyl, ethyl and benzyl；
R1-R8Identical or different, selected from hydrogen atom, halogen atom, C1-C20Aliphatic group, C3-C20's Cyclic hydrocarbon radical and C6-C20Aryl radical；Preferably hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, just Butyl, isobutyl group, the tert-butyl group, cyclohexyl and phenyl；
R9-R10Identical or different, selected from substituted or unsubstituted C1-C20Aliphatic group and C6-C30's Aryl radical, selected from methyl, ethyl, propyl group, isopropyl, cyclohexyl, phenyl, 2,6-di-t-butyl Phenyl, 2,4,6-trimethylphenyls；
Y is a bridge joint group, selected from C1-C20Aliphatic group and C6-C20Aryl radical, its institute State the arbitrary hydrogen on alkyl or carbon atom is optionally replaced by hetero atoms such as oxygen, nitrogen, boron, sulfur and silicon；Excellent Select methylene, ethylidene, propylidene, butylidene, isopropylidene, isobutylidene, phenyl, substituted-phenyl；
For the present invention, preferred coordination compound is substituent group M in structural formula, X, Y and R1-R10 Coordination compound 1-40 for as described below:
1, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=methyl, X=Cl, Y=C (CH3)2；
2, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=ethyl, X=Cl, Y=C (CH3)2；
3, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=propyl group, X=Cl, Y=C (CH3)2；
4, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=isopropyl Base, X=Cl, Y=C (CH3)2；
5, M=Ti, R1=R5=R9=R10=t-Bu, R2=R3=R4=R6=R7=R8=H, X=Cl, Y=C (CH3)2；
6, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=hexamethylene Base, X=Cl, Y=C (CH3)2；
7, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=phenyl, X=Cl, Y=C (CH3)2；
8, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=2,4,6- Trimethylphenyl, X=Cl, Y=C (CH3)2；
9, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=2,6- Di-tert-butyl-phenyl, X=Cl, Y=C (CH3)2；
10, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=phenyl, R10=2,6- Di-tert-butyl-phenyl, X=Cl, Y=C (CH3)2；
11, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=phenyl, R10= Cyclohexyl, X=Cl, Y=C (CH3)2；
12, M=Ti, R1=R5=t-Bu, R2=R3=R6=R7=H, R4=R8=CH3, R9=R10= Phenyl, X=Cl, Y=C (CH3)2；
13, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=hexamethylene Base, X=Cl, Y=O；
14, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=phenyl, X=Cl, Y=O；
15, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=hexamethylene Base, X=Cl, Y=S；
16, M=Ti, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=phenyl, X=Cl, Y=CH2CH2；
17, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=methyl, X=Cl, Y=C (CH3)2；
18, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=ethyl, X=Cl, Y=C (CH3)2；
19, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=the third Base, X=Cl, Y=C (CH3)2；
20, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=different Propyl group, X=Cl, Y=C (CH3)2；
21, M=Zr, R1=R5=R9=R10=t-Bu, R2=R3=R4=R6=R7=R8=H, X=Cl, Y=C (CH3)2；
22, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=ring Hexyl, X=Cl, Y=C (CH3)2；
23, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=benzene Base, X=Cl, Y=C (CH3)2；
24, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=2,4,6- Trimethylphenyl, X=Cl, Y=C (CH3)2；
25, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=2,6- Di-tert-butyl-phenyl, X=Cl, Y=C (CH3)2；
26, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=phenyl, R10 =2,6-di-tert-butyl-phenyl, X=Cl, Y=C (CH3)2；
27, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=phenyl, R10 =cyclohexyl, X=Cl, Y=C (CH3)2；
28, M=Zr, R1=R5=t-Bu, R2=R3=R6=R7=H, R4=R8=CH3, R9=R10= Phenyl, X=Cl, Y=C (CH3)2；
29, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=ring Hexyl, X=Cl, Y=O；
30, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=benzene Base, X=Cl, Y=O；
31, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=ring Hexyl, X=Cl, Y=S；
32, M=Zr, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=benzene Base, X=Cl, Y=CH2CH2；
33, M=Hf, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=first Base, X=Cl, Y=C (CH3)2；
34, M=Hf, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=different Propyl group, X=Cl, Y=C (CH3)2；
35, M=Hf, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=ring Hexyl, X=Cl, Y=C (CH3)2；
36, M=Hf, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=phenyl, X=Cl, Y=C (CH3)2；
37, M=Hf, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=phenyl, R10 =cyclohexyl, X=Cl, Y=C (CH3)2；
38, M=Hf, R1=R5=t-Bu, R2=R3=R6=R7=H, R4=R8=CH3, R9=R10= Phenyl, X=Cl, Y=C (CH3)2；
39, M=Hf, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=hexamethylene Base, X=Cl, Y=O；
40, M=Hf, R1=R5=t-Bu, R2=R3=R4=R6=R7=R8=H, R9=R10=hexamethylene Base, X=Cl, Y=S；
Component (2) described chlorination silicon alkyl refers to compound described in below general formula: ClnSi(R1)4-n
Wherein R1Represent C1-C20Alkyl, n represents the integer of 1-4；Described chlorination silicon alkyl is selected from trimethyl Chlorosilane, chlorotriethyl silane, tri isopropyl chlorosilane, dimethyl ethyl chlorosilane, diethylpropyl chlorine Silane, dipropyl methylchlorosilane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichlorophenyl silicon, two Chloromethyl n-pro-pyl silane, dichloromethyl phenyl silane, trichloromethyl silane, trichloroethyl silane, phenyl Trichlorosilane and Silicon chloride., preferably trim,ethylchlorosilane, chlorotriethyl silane, dichloro-dimethyl silicon, two Chlorine diethyl silicon, dichlorophenyl silicon, trichloromethyl silane, trichloroethyl silane and Silicon chloride..
Component (3) described alkylaluminoxane formula is:
The wherein preferred methyl of R, a represents the integer of 10-30.Preferably MAO (MAO) and improve MAO (MMAO).
Supported non-metallocene metallic catalyst for vinyl polymerization, it is characterised in that the ratio between each reactant Example is in terms of every gram of silica-gel carrier, and chloric ether SiClx addition is 0.01-3mmol, the addition of alkylaluminoxane For 0.01-30mmol, the addition of non-metallocene compound is 1-1000 μm ol.
The described supported non-metallocene metallic catalyst for vinyl polymerization, it is characterised in that supported non- In metallocene catalyst, aluminum weight content is 1-15%, and the weight content of central metal M is 0.05-2%.
The method of a kind of catalyst for ethylene polymerization of the present invention, comprises the steps:
(1) preparation of the silica-gel carrier of chlorination alkyl Si modification: under noble gas such as nitrogen is protected, by silicon Glue carrier adds in reactor, adds solvent, is dispersed into suspension, adds chlorination alkyl silicon, is warming up to 0 -90 DEG C, stirring reaction 3-24 hour, preferably 30-60 DEG C, stirring reaction 3-6 hour；Then with molten Agent is washed for several times, vacuum drying, obtains the silica-gel carrier containing chlorination alkyl Si modification of good fluidity, Described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；Preferably toluene or saturated alkane.
(2) preparation of the silica-gel carrier of alkylaluminoxane: under noble gas such as nitrogen is protected, by (1st) The silica-gel carrier obtained in step adds in reactor, adds solvent, is dispersed into suspension, adds alkyl alumina Alkane, is warming up to 0-90 DEG C, stirring reaction 3-24 hour, preferably 40-90 DEG C, and reaction 3-8 is little in stirring Time, then wash for several times with solvent, vacuum drying, obtain the silicon containing alkylaluminoxane of good fluidity Glue carrier, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；Preferably toluene.
(3) preparation of modified silica-gel load non-metallocene metallic catalyst: under noble gas such as nitrogen is protected, will At the silica-gel carrier containing alkylaluminoxane that (2nd) step prepares, join in solvent and make serosity, will The solution of non-metallocene compound is slowly dropped in this serosity, at 0-90 DEG C, reacts 3-24 hour, Preferably at 0-80 DEG C, react 1-120 minute, obtain supported non-metallocene single site catalysts, can Serosity is directly used in polyreaction, or gained reactant removing solvent, washing are obtained mobility after drying Good solid supported non-metallocene single active site catalyst, described solvent selected from toluene, benzene, dimethylbenzene, Hexane, heptane, hexamethylene, preferably toluene, hexane and both mixture.
In load non-metallocene metal catalytic agent method of the present invention, the catalyst of preparation can be used in different gathering In conjunction method, such as gas-phase polymerization and slurry polymerization etc..Can be used for all polymerizations or the copolymerization of alkene, special Be not applicable to ethylene homo close or the copolymerization of ethylene and other alpha-olefin, wherein alpha-olefin selected from propylene, Butylene, amylene, hexene, octene, 4-methylpentene-1 etc..
In the load non-metallocene metallic catalyst of ethylene polymerization, non-metallocene compound is loaded on chlorine Change on alkyl silicon/alkylaluminoxane/silica-gel carrier.
In supported non-metallocene metal catalytic agent method of the present invention, the catalyst of preparation is used directly for alkene Polymerized hydrocarbon, as in gas-phase polymerization process；Olefinic polymerization can also be used for by additional aluminum alkyl catalyst, Particularly add in slurry process alkyl aluminum can impurity in removing system, improve poly-to a certain extent Close activity, and expensive MAO need not be added and make promoter.
The solvent that wherein polymerization is used is selected from alkane, aromatic hydrocarbon or halogenated hydrocarbons, preferably hexane, pentane, heptan A kind of in alkane, benzene, toluene, dichloromethane, chloroform, dichloroethanes or their mixture, most preferably For a kind of in hexane, toluene, heptane or their mixture.
The supported non-metallocene metallic catalyst concentration when polymerization is 1 × 10-8Mol/L～1 × 10-3Mole/ Rising, preferred concentration range is 1 × 10-8Mol/L～1 × 10-5Mol/L.
Polymerization temperature is-78 DEG C-100 DEG C, preferably 0 DEG C-90 DEG C.
Polymerization pressure is 0.01-10.0MPa, preferably 0.01-2.0MPa.
The present invention compared with prior art has the following advantages:
1, modified silica gel carrier preparation method of the present invention is simple, and the catalyst granules form obtained is good, Catalyst particle size is adjustable.
2, in load non-metallocene metal catalytic agent method of the present invention, the catalyst of preparation has the highest ethylene Polymerization catalytic activity.
3, in load non-metallocene metal catalytic agent method of the present invention, the catalyst of preparation has good catalysis Ethylene and the combined polymerization performance of alpha-olefin, Copolymerization activity is high.
4, load non-metallocene metallic catalyst of the present invention obtains resin powder have well for olefinic polymerization Particle shape, bulk density is high, goes for slurry process and vapor phase method polymerization technique.
Analysis and characterization instrument used in the present invention is as follows:
1, ICP (plasma emission spectrum) characterizes: the weight percent of metal in quantitative determination carried catalyst Ratio.The P1000 type ICP-AES plasma emission spectrometer that PE company of the instrument selection U.S. produces.
2, polymer molecular weight and the sign of molecular weight distribution: molecular weight and distribution thereof are by gel permeation chromatography (GPC) measuring, instrument uses Waters Alliance GPCV 2000, and solvent is 1,2,4-trichloro-benzenes, Sample concentration is lmg/ml, and solvent flow rate is 1.0ml/min；Measuring temperature is 150 DEG C.Each sample is measured Secondary.
Embodiment
Embodiment 1
(1) preparation of chlorination silicon alkyl/silica-gel carrier
Under nitrogen protection, take dry silica-gel carrier 2.5 grams and add in glass reactor, add 100 millis Rise dried hexane, be dispersed into suspension, add 1 milliliter of SiCl2(n-Bu)2, start stirring, be warming up to 30 DEG C, react 4 hours, vacuum drying, obtain the pressed powder of good fluidity.
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
Under nitrogen protection, take modified silica gel carrier obtained above 5.0 grams and add in glass reactor, add Enter 60 milliliters of dried toluene, be dispersed into suspension, add MAO (the methyl alumina of 18 milliliters of 10wt% Alkane) toluene solution, it is warming up to 50 DEG C, stirring reaction 4 hours, then with 50 milliliters × 3 toluene washings three Secondary, then wash with hexane, vacuum drying, obtain the pressed powder of good fluidity, i.e. contain aluminium methyl The silica-gel carrier of oxygen alkane.
(3) preparation of supported non-metallocene metallic catalyst A
Under nitrogen protection, the silica-gel carrier 2.50 grams containing MAO that will be previously obtained, join In glass reactor, add 35 milliliters of dried toluene and make serosity, be dissolved in 20 milliliters of toluene 0.168 gram of double-[N-(the 3-tert-butyl group-salicylidene) cyclohexylamine] zirconium dichloride [(L1)2ZrCl2, it closes Prejudice Chinese patent CN101173011, embodiment 6, its structure sees below formula] solution be added drop-wise in reactor, React 30 minutes at 30 DEG C, then with 35 milliliters of toluene washings, vacuum drying, obtain load non-metallocene metal Catalyst A.Characterizing through ICP, in catalyst A, Zr weight content is 0.46%, and Al weight content is 10.10%.
Comparing embodiment 1
(1) preparation of alkylaluminoxane/silica-gel carrier
Under nitrogen protection, take 7.01 grams of silica gel and add in glass reactor, add 90 milliliters of dried first Benzene, is dispersed into suspension, adds MAO (MAO) toluene solution of 40 milliliters of 10wt%, rises Temperature is to 50 DEG C, and stirring is reacted 4 hours, then washs three times with 50 milliliters × 3 toluene, then washes with hexane Wash, vacuum drying, obtain the pressed powder of good fluidity, i.e. alkylaluminoxane/silica-gel carrier.
(3) preparation of supported non-metallocene metallic catalyst A*
Under nitrogen protection, the above-mentioned alkylaluminoxane/silica-gel carrier prepared 2.50 grams is joined glass anti- Answer in device, add 30 milliliters of dried toluene and make serosity, be dissolved in 20 milliliters of toluene 0.168 gram Double-[N-(the 3-tert-butyl group-salicylidene) cyclohexylamine] zirconium dichloride [(L1)2ZrCl2, its synthesis is with embodiment 1 The synthesis of middle coordination compound] solution be added drop-wise in reactor, react 30 minutes at 30 DEG C, then with 30 in the least Rise toluene washing, vacuum drying, obtain supported non-metallocene metallic catalyst A*.Characterize through ICP, catalyst In A*, Zr weight content is 0.52%, and Al weight content is 14.11%.
Embodiment 2
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (1), only by SiCl in embodiment 12(n-Bu)2It is changed to SiCl4。
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2).
(3) preparation of supported non-metallocene metallic catalyst B
With embodiment 1 step (4), only by embodiment 1 0.168 gram double-[N-(the 3-tert-butyl group-neighbour's oxybenzene Methylene) cyclohexylamine] zirconium dichloride replaces with 0.152 gram of [double-[N-(the 3-tert-butyl group-salicylidene) benzene Amine] titanium chloride] (L2)2TiCl2(its structure sees below, and it synthesizes sees document Chemistry Letters, and 1999, 1065) load non-metallocene metallic catalyst B, is obtained.Characterizing through ICP, in catalyst B, Ti weight content is 0.31%, Al weight content is 11.12%.
Embodiment 3
(1), (2) are with (1), (2) preparation method in embodiment 2.
(3) preparation of supported non-metallocene metallic catalyst C
With embodiment 1 step (3), only by embodiment 1 0.168 gram double-[N-(the 3-tert-butyl group-neighbour's oxybenzene Methylene) cyclohexylamine] zirconium dichloride replaces with 0.198 gram of [double-[N-(3-phenyl-salicylidene) aniline] Titanium chloride] ((L3)2TiCl2(its structure sees below), it synthesizes sees document Chemistry Letters, 1999, 1065) load non-metallocene metallic catalyst C, is obtained.Characterizing through ICP, in catalyst C, Ti weight content is 0.36%, Al weight content is 11.19%.
Embodiment 4
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (1), only by SiCl in embodiment 12(n-Bu)2It is changed to CH3SiCl3。
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2).
(3) preparation of supported non-metallocene metallic catalyst D
With embodiment 1 step (3), only by embodiment 1 0.168 gram [double-[N-(the 3-tert-butyl group-neighbour's hydroxyl Benzylidene) cyclohexylamine] zirconium dichloride] replace with 0.165 gram of double-[N-(the 3-tert-butyl group-salicylidene) Aniline] zirconium dichloride (Chinese patent CN101173011, embodiment 11 are shown in its synthesis, and its structure sees below), Obtain load non-metallocene metallic catalyst D.Characterizing through ICP, in catalyst D, Zr weight content is 0.41%, Al weight content is 11.02%.
Embodiment 5
(1) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With (1), (2) in embodiment 1
(2) preparation of supported non-metallocene metallic catalyst E
With embodiment 1 step (3), only by embodiment 1 0.168 gram double-[N-(the 3-tert-butyl group-neighbour's oxybenzene Asia Methyl) cyclohexylamine] zirconium dichloride replaces with 0.225 gram of (L2)3Zr2Cl4[its structure is as follows, and synthesis is shown in that China is specially Profit CN1769310, embodiment 2] solution be added drop-wise in reactor, 30 DEG C react 30 minutes, then With 50 milliliters of toluene washings, vacuum drying, obtain supported non-metallocene metallic catalyst E.Characterize through ICP, In catalyst E, Zr weight content is 0.42%, and Al weight content is 10.07%.
Embodiment 6
(1) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With (1), (2) in embodiment 1
(2) preparation of supported non-metallocene metallic catalyst F
With embodiment 1 step (3), only by embodiment 1 0.168 gram [double-[N-(the 3-tert-butyl group-neighbour's hydroxyl Benzylidene) cyclohexylamine] zirconium dichloride] replace with 0.221 gram of (L5)3Zr2Cl4(its structure is as follows, and synthesis is shown in Chinese patent CN1769310, embodiment 1), obtain supported non-metallocene metallic catalyst F.Characterize through ICP, In catalyst F, Zr weight content is 0.43%, and Al weight content is 10.08%.
Embodiment 7
(1) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With (1), (2) in embodiment 1
(2) preparation of supported non-metallocene metallic catalyst G
With embodiment 1 step (3), only by embodiment 1 0.168 gram [double-[N-(the 3-tert-butyl group-neighbour's oxybenzene Asia Methyl) cyclohexylamine] zirconium dichloride] replace with 0.221 gram of (L5)3Ti2Cl4(its structure is as follows, and China is shown in synthesis Patent CN1769310, embodiment 4), obtain supported non-metallocene metallic catalyst G.Characterize through ICP, urge In agent G, Ti weight content is 0.32%, and Al weight content is 12.30%.
Embodiment 8
(1) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With (1), (2) in embodiment 1
(2) preparation of supported non-metallocene metallic catalyst H
With embodiment 1 step (3), only by embodiment 1 0.168 gram [double-[N-(the 3-tert-butyl group-neighbour's oxybenzene Asia Methyl) cyclohexylamine] zirconium dichloride] replace with 0.221 gram of (L5)9Zr8Cl16(its structure is as follows, and China is shown in synthesis Patent CN1769310, embodiment 3), obtain supported non-metallocene metallic catalyst H.Characterize through ICP, urge In agent H, Zr weight content is 0.38%, and Al weight content is 11.80%.
High pressure ethylene polymerization is tested
High pressure ethylene polymerization experimentation is as follows:
In the rustless steel polymerization autoclave of 2 liters, respectively replace three times with nitrogen and ethylene, be subsequently adding 1000 Milliliter hexane solvent, along with the addition of hexane, by triethyl aluminum (TEA) hexane of 2 milliliter of 1 mol/L Solution adds, and (when investigating ethylene copolymerization, being added with hexane by 10ml1-hexene), is subsequently added into above-mentioned reality Execute example prepare load metallocene catalyst 50～100 milligrams, be warming up to 80 DEG C, pressure risen to and maintains 1.0MPa, reacts 1 hour.After polyreaction terminates, cooling, collect polyethylene particle powder, weigh.
Concrete polymerization result is shown in Table 1.
Table 1, supported non-metallocene metallic catalyst polymerization result

Claims (8)

1. the supported non-metallocene metallic catalyst for vinyl polymerization, it is characterised in that under this catalyst includes The product of row component:
(1) non-metallocene compound；
(2) chlorination silicon alkyl or Silicon chloride. modifying agent；
(3) alkylaluminoxane；
(4) silica-gel carrier；
Component (1) described non-metallocene compound, refers to the metal complex shown in formula 1 or 2,
In formula 1, R1Selected from substituted or unsubstituted C1-C20Aliphatic group or C6-C30Aryl radical, R2-R6Identical or different, for hydrogen atom, C1-C20Aliphatic group, C3-C20Cyclic hydrocarbon radical or C6-C20Fragrance Alkyl；
M is the transition metal of the 4th race in the periodic table of elements, and X is selected from halogen, when n is two or more, Multiple X group are identical or different；M and n is the integer of 1-3, and m+n=4；
In formula 2: M is the transition metal of the 4th race in the periodic table of elements；N is the integer of 1-30, works as m During for two or more, multiple X group are identical or different；M is the integer meeting M valence state；
X is selected from halogen；
R1-R8Identical or different, for hydrogen atom or C1-C20Aliphatic group；
R9-R10Identical or different, selected from substituted or unsubstituted C1-C20Aliphatic group or C6-C30Fragrance Alkyl；
R1-R10In two or more groups optionally mutual keyed jointing cyclization；
Y is a bridge joint group, for C1-C20Aliphatic group；
Component (2) described chlorination silicon alkyl or Silicon chloride. modifying agent refer to compound described in below general formula: ClnSi(R1)4-n
R in formula1Represent C1-C20Alkyl, n represents the integer of 1-4；
Component (3) described alkylaluminoxane formula is:
In formula, R represents C1-C12Alkyl, a represents the integer of 4-30.
Supported non-metallocene metallic catalyst for vinyl polymerization the most according to claim 1, it is characterised in that In formula 1, R1Selected from C1-C20Aliphatic group or C6-C30Aryl radical, R2-R6Selected from hydrogen atom or C1-C20 Aliphatic group；M is selected from titanium, zirconium or hafnium；
In formula 2, M is selected from titanium, zirconium or hafnium；N is the integer of 1-10；R9-R10Selected from C1-C20Aliphatic group And C6-C30Aryl radical.
Supported non-metallocene metallic catalyst for vinyl polymerization the most according to claim 1, it is characterised in that Ratio between each reactant in terms of every gram of silica-gel carrier, chlorination silicon alkyl or Silicon chloride. modifying agent addition For 0.01-3mmol, the addition of alkylaluminoxane is 0.01-30mmol, the addition of non-metallocene compound Amount is 1-1000 μm ol.
Supported non-metallocene metallic catalyst for vinyl polymerization the most according to claim 1, it is characterised in that In supported non-metallocene metallic catalyst, the weight content of aluminum is 1-15%, and the weight content of central metal M is 0.05-2%.
Supported non-metallocene metallic catalyst for vinyl polymerization the most according to claim 1, it is characterised in that Described chlorination silicon alkyl, wherein R1Selected from methyl, ethyl or propyl group or phenyl；Described alkylaluminoxane, Wherein R is methyl, and a represents the integer of 10-30.
6. the preparation method of the supported non-metallocene metallic catalyst for vinyl polymerization that one of claim 1-5 is described, It is characterized in that, comprise the following steps:
The first step: under inert gas shielding, silica-gel carrier exists with chlorination silicon alkyl or Silicon chloride. modifying agent 0-90 DEG C is reacted 3-24 hour；
Second step: under inert gas shielding, by first step gained chlorination silicon alkyl or Silicon chloride. modified silicon Glue reacts 3-24 hour at 0-90 DEG C with alkylaluminoxane；
3rd step: under inert gas shielding, by second step gained alkylaluminoxane modified silica-gel with non-cyclopentadienyl gold Belong to compound to react 0.5-24 hour at 0-90 DEG C；
The dispersant more than reacted is selected from toluene, benzene, dimethylbenzene, hexane, heptane or hexamethylene.
The preparation method of catalyst the most according to claim 6, it is characterised in that in the first step is reacted, Reaction temperature is 30-60 DEG C；Dispersant used is selected from toluene, hexane, heptane or hexamethylene；At second step In reaction, reaction temperature is 20-90 DEG C；Dispersant used is toluene；In three-step reaction, used point Powder is selected from toluene or hexane.
8. the supported non-metallocene metallic catalyst for vinyl polymerization described in claim 1-5 any one is in second Application in alkene polymerization.
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