CN104059181A - Supported non-metallocene catalyst used for ethylene polymerization - Google Patents
Supported non-metallocene catalyst used for ethylene polymerization Download PDFInfo
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- CN104059181A CN104059181A CN201310091192.7A CN201310091192A CN104059181A CN 104059181 A CN104059181 A CN 104059181A CN 201310091192 A CN201310091192 A CN 201310091192A CN 104059181 A CN104059181 A CN 104059181A
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Abstract
The invention relates to a supported non-metallocene catalyst used for ethylene polymerization and a preparation method thereof. The catalyst comprises a non-metallocene compound, chlorinated alkyl silicon, alkyl aluminoxane and a silica gel carrier reaction product; the preparation method comprises the following steps: 1) preparation of a chlorinated alkyl silicon modified silica gel carrier, 2)preparation of an alkyl aluminoxane modified silica gel carrier, and 3)preparation of the modified silica gel supported non-metallocene catalyst; and the obtained non-metallocene catalyst has high polymerization activity for catalyzing vinyl polymerization or copolymerization. The preparation method of the silica gel carrier is simple, and the obtained supported catalyst particles have good particle morphology and have adjustable size.
Description
Technical field
The present invention relates to a kind of preparation method of the supported non-metallocene metal catalyst for vinyl polymerization, and the application of gained catalyzer aspect olefinic polymerization.
Technical background
In the evolution of olefin polymerization catalysis, the non-metallocene catalyst that nineteen nineties develops has obtained great development and concern.Particularly, containing the 4th group 4 transition metal complexes (EP0874005, WO0155231) of phenoxy group-imine ligand, there is very high catalysis in olefine polymerization activity, and can obtain the polyolefin resin of the features such as functionalization, have a good application prospect.But being proved in olefinic polyreaction, homogeneous catalyst has that active duration is short, easily glutinous still, promotor methylaluminoxane consumption are high, and obtain the too low or too high weak point of polymericular weight, the solution polymerization process or the high-pressure polymerization process that are only likely applied to alkene, seriously limited its industrial applicability.
At present, report is very many in recent years in relevant non-metallocene catalyst loadization research, as patent CN1539855A, CN1539856A, CN1789291, CN1789292, CN1962702A, CN1769309A, CN1769310A, CN101423573A, CN101798361A, CN102399313A etc. provide various ways to carry out load to obtain load type non-metallocene catalyst, wherein adopt the catalyzer of Magnesium Chloride Anhydrous load non-metallocene metal to there is good particle form, as CN102039186A, CN102039189A, CN102039187A, CN102039185A, CN101942048A, but this type of catalyst strength is poor, easily broken in polymerization reactor, thereby cause polymer morphology bad, and in carrier, contain alcohol, water, the components such as alkoxyl group, carrier preparation is complicated.And the research of catalyzer taking Si02 as carrier report is also a lot, as CN102399331A, CN1539855A, CN1769309A, CN1727062A, CN1962702A, but carrier preparation is complicated, in polymerization process, still to introduce a large amount of methylaluminoxane, above drawbacks limit the industrial application of silica gel load non-metallocene catalyst.
Also there is document to use and contain the composite carrier load such as magnesium chloride, silica gel Nonmetallocene (CN1539856A, CN102399317A, CN102039185A, CN102399331A, CN101423574A, CN1539855A), but supported catalyst preparation method complexity, and need to add a large amount of MAO in the time of polymerization.
Summary of the invention
One of the object of the invention is to provide a kind of non-metallocene catalyst with alkylaluminoxane/chlorination silicon alkyl/silica gel load and preparation method thereof.
Two of the object of the invention is by above-mentioned load non-metallocene metal catalyst, for vinyl polymerization or copolymerization, to have high polymerization activity.
A kind of supported non-metallocene metal catalyst for vinyl polymerization of the present invention, this catalyzer comprises the reaction product of following component:
(1) Nonmetallocene compound;
(2) chlorination silicon alkyl;
(3) alkylaluminoxane;
(4) silica-gel carrier;
The described Nonmetallocene compound of component (1), refers to the metal complexes shown in general formula 1 and 2,
In general formula 1, R
1be selected from and replace or unsubstituted C
1-C
20aliphatic group or C
6-C
30aryl radical, R
2-R
6identical or different, be hydrogen atom, halogen atom, C
1-C
20aliphatic group, C
3-C
20cyclic hydrocarbon radical or C
6-C
20aryl radical, on described alkyl, arbitrary hydrogen or carbon atom are optionally replaced by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin heteroatoms;
M is the transition metal of the 4th family in the periodic table of elements, and X is the one being selected from halogen, alkyl,-oxyl, acid group and amido, when n is 2 or when larger, multiple X groups are identical or different; M and n are the integers of 1-3, and m+n=4;
In general formula 2: M is the transition metal of the 4th family in the periodic table of elements; N is the integer of >2, when m is 2 or when larger, multiple X groups are identical or different; M is the integer that meets M valence state;
X is selected from the one in halogen, alkyl,-oxyl, acid group, amido;
R
1-R
8identical or different, be hydrogen atom, halogen atom, C
1-C
20aliphatic group, C
3-C
20cyclic hydrocarbon radical or C
6-C
20aryl radical, the arbitrary hydrogen described in it on alkyl or carbon atom are optionally replaced by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin heteroatoms;
R
9-R
10identical or different, be selected from and replace or unsubstituted C
1-C
20aliphatic group or C
6-C
30aryl radical;
R
1-R
10in two or more groups be optionally mutually keyed to ring;
Y is a bridge joint group, is C
1-C
20aliphatic group or C
6-C
20aryl radical, arbitrary hydrogen or the carbon atom described in it on alkyl optionally replaced by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin heteroatoms;
The described chlorination alkyl of component (2) silica modifier refers to compound: Cl described in following general formula
nsi (R
1)
4-n
R in formula
1represent C
1-C
20alkyl, n represents the integer of 1-4,
The described alkylaluminoxane general formula of component (3) is:
In formula, R represents C
1-C
12alkyl, a represents the integer of 4-30.
In Nonmetallocene compound general formula (1), R
1be selected from n-hexyl, cyclohexyl and phenyl; R
2-R
6be selected from hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and the tertiary butyl;
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, preferably title complex is substituting group M, X and the R in structural formula
1-R
6title complex 1-75 for as described below:
1, M=Ti, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=Cl;
2、M=Ti，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=Cl；
3, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=Cl;
4, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=Cl;
5, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=Et, R
6=t-Bu, X=Cl;
6, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=i-Pr, R
6=t-Bu, X=Cl;
7、M=Ti，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=Ph，X=Cl；
8, M=Ti, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=Br;
9、M=Ti，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=Br；
10, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=Br;
11, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=Br;
12, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=Et, R
6=t-Bu, X=Br;
13、M=Ti，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=I；
14, M=Ti, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=CH
3;
15、M=Ti，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=CH
3；
16, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=CH
3;
17, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=CH
3;
18, M=Ti, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=Bz;
19、M=Ti，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=Bz；
20, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=Bz;
21, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=Bz;
22, M=Ti, R
1=cyclohexyl, R
2=R
3=R
4=R
5=CH
3, R
6=t-Bu, X=Bz;
23, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=Et, R
6=t-Bu, X=Bz;
24, M=Ti, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=i-Pr, R
6=t-Bu, X=Bz;
25, M=Zr, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=Cl;
26、M=Zr，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=Cl；
27, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=Cl;
28, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=Cl;
29, M=Zr, R
1=cyclohexyl, R
2=R
3=R
4=R
5=CH
3, R
6=t-Bu, X=Cl;
30, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=Et, R
6=t-Bu, X=Cl;
31, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=i-Pr, R
6=t-Bu, X=Cl;
32, M=Zr, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=Br;
33、M=Zr，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=Br；
34, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=Br;
35, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=Br;
36, M=Zr, R
1=cyclohexyl, R
2=R
3=R
4=R
5=CH
3, R
6=t-Bu, X=Br;
37, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=Et, R
6=t-Bu, X=Br;
38, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=i-Pr, R
6=t-Bu, X=Br;
39, M=Zr, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=I;
40、M=Zr，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=I；
41, M=Zr, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=CH
3;
42、M=Zr，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=CH
3；
43, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=CH
3;
44, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=CH
3;
45, M=Zr, R
1=cyclohexyl, R
2=R
3=R
4=R
5=CH
3, R
6=t-Bu, X=CH
3;
46, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=Et, R
6=t-Bu, X=CH
3;
47, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=i-Pr, R
6=t-Bu, X=Et;
48, M=Zr, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=Bz;
49、M=Zr，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=Bz；
50, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=Bz;
51, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=Bz;
52, M=Zr, R
1=cyclohexyl, R
2=R
3=R
4=R
5=CH
3, R
6=t-Bu, X=Bz;
53, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=Et, R
6=t-Bu, X=Bz;
54, M=Zr, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=i-Pr, R
6=t-Bu, X=Bz;
55, M=Hf, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=Cl;
56、M=Hf，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=Cl；
57, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=Cl;
58, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=Cl;
59, M=Hf, R
1=cyclohexyl, R
2=R
3=R
4=R
5=CH
3, R
6=t-Bu, X=Cl;
60, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=Et, R
6=t-Bu, X=Cl;
61, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=i-Pr, R
6=t-Bu, X=Cl;
62, M=Hf, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=CH
3;
63、M=Hf，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=CH
3；
64, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=CH
3;
65, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=CH
3;
66, M=Hf, R
1=cyclohexyl, R
2=R
3=R
4=R
5=CH
3, R
6=t-Bu, X=CH
3;
67, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=Et, R
6=t-Bu, X=CH
3;
68, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=i-Pr, R
6=t-Bu, X=CH
3;
69, M=Hf, R
1=cyclohexyl, R
2=R
3=R
4=R
5=H, R
6=t-Bu, X=Bz;
70、M=Hf，R
1=Ph，R
2=R
3=R
4=R
5=H，R
6=t-Bu，X=Bz；
71, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=CH
3, R
6=t-Bu, X=Bz;
72, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=R
6=t-Bu, X=Bz;
73, M=Hf, R
1=cyclohexyl, R
2=R
3=R
4=R
5=CH
3, R
6=t-Bu, X=Bz;
74, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=Et, R
6=t-Bu, X=Bz;
75, M=Hf, R
1=cyclohexyl, R
2=R
3=R
5=H, R
4=i-Pr, R
6=t-Bu, X=Bz;
In general formula 2:
M is the transition metal of the 4th family in the periodic table of elements, is selected from early transition metal titanium, zirconium and hafnium; N is the integer of 1-10, and m is the integer that meets M valence state;
X is selected from halogen and alkyl, preferably from chlorine, bromine, methyl, ethyl and benzyl;
R
1-R
8identical or different, be selected from hydrogen atom, halogen atom, C
1-C
20aliphatic group, C
3-C
20cyclic hydrocarbon radical and C
6-C
20aryl radical; Preferably hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, cyclohexyl and phenyl;
R
9-R
10identical or different, be selected from and replace or unsubstituted C
1-C
20aliphatic group and C
6-C
30aryl radical, be selected from methyl, ethyl, propyl group, sec.-propyl, cyclohexyl, phenyl, 2,6-di-tert-butyl-phenyl, 2,4,6-trimethylphenyl;
Y is a bridge joint group, is selected from C
1-C
20aliphatic group and C
6-C
20aryl radical, arbitrary hydrogen or carbon atom described in it on alkyl are optionally replaced by heteroatomss such as oxygen, nitrogen, boron, sulphur and silicon; Preferably methylene radical, ethylidene, propylidene, butylidene, isopropylidene, isobutylidene, phenyl, substituted-phenyl;
For the present invention, preferably title complex is substituting group M, X, Y and the R in structural formula
1-R
10title complex 1-40 for as described below:
1, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=methyl, X=Cl, Y=C (CH
3)
2;
2, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=ethyl, X=Cl, Y=C (CH
3)
2;
3, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=propyl group, X=Cl, Y=C (CH
3)
2;
4, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=sec.-propyl, X=Cl, Y=C (CH
3)
2;
5、M=Ti，R
1=R
5=R
9=R
10=t-Bu，R
2=R
3=R
4=R
6=R
7=R
8=H，X=Cl，Y=C(CH
3)
2；
6, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=cyclohexyl, X=Cl, Y=C (CH
3)
2;
7, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=phenyl, X=Cl, Y=C (CH
3)
2;
8, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=2,4,6-trimethylphenyl, X=Cl, Y=C (CH
3)
2;
9, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=2,6-di-tert-butyl-phenyl, X=Cl, Y=C (CH
3)
2;
10, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=phenyl, R
10=2,6-di-tert-butyl-phenyl, X=Cl, Y=C (CH
3)
2;
11, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=phenyl, R
10=cyclohexyl, X=Cl, Y=C (CH
3)
2;
12, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
6=R
7=H, R
4=R
8=CH
3, R
9=R
10=phenyl, X=Cl, Y=C (CH
3)
2;
13, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=cyclohexyl, X=Cl, Y=O;
14, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=phenyl, X=Cl, Y=O;
15, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=cyclohexyl, X=Cl, Y=S;
16, M=Ti, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=phenyl, X=Cl, Y=CH
2cH
2;
17, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=methyl, X=Cl, Y=C (CH
3)
2;
18, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=ethyl, X=Cl, Y=C (CH
3)
2;
19, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=propyl group, X=Cl, Y=C (CH
3)
2;
20, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=sec.-propyl, X=Cl, Y=C (CH
3)
2;
21、M=Zr，R
1=R
5=R
9=R
10=t-Bu，R
2=R
3=R
4=R
6=R
7=R
8=H，X=Cl，Y=C(CH
3)
2；
22, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=cyclohexyl, X=Cl, Y=C (CH
3)
2;
23, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=phenyl, X=Cl, Y=C (CH
3)
2;
24, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=2,4,6-trimethylphenyl, X=Cl, Y=C (CH
3)
2;
25, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=2,6-di-tert-butyl-phenyl, X=Cl, Y=C (CH
3)
2;
26, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=phenyl, R
10=2,6-di-tert-butyl-phenyl, X=Cl, Y=C (CH
3)
2;
27, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=phenyl, R
10=cyclohexyl, X=Cl, Y=C (CH
3)
2;
28, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
6=R
7=H, R
4=R
8=CH
3, R
9=R
10=phenyl, X=Cl, Y=C (CH
3)
2;
29, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=cyclohexyl, X=Cl, Y=O;
30, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=phenyl, X=Cl, Y=O;
31, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=cyclohexyl, X=Cl, Y=S;
32, M=Zr, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=phenyl, X=Cl, Y=CH
2cH
2;
33, M=Hf, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=methyl, X=Cl, Y=C (CH
3)
2;
34, M=Hf, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=sec.-propyl, X=Cl, Y=C (CH
3)
2;
35, M=Hf, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=cyclohexyl, X=Cl, Y=C (CH
3)
2;
36, M=Hf, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=phenyl, X=Cl, Y=C (CH
3)
2;
37, M=Hf, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=phenyl, R
10=cyclohexyl, X=Cl, Y=C (CH
3)
2;
38, M=Hf, R
1=R
5=t-Bu, R
2=R
3=R
6=R
7=H, R
4=R
8=CH
3, R
9=R
10=phenyl, X=Cl, Y=C (CH
3)
2;
39, M=Hf, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=cyclohexyl, X=Cl, Y=O;
40, M=Hf, R
1=R
5=t-Bu, R
2=R
3=R
4=R
6=R
7=R
8=H, R
9=R
10=cyclohexyl, X=Cl, Y=S;
The described chlorination silicon alkyl of component (2) refers to compound: Cl described in following general formula
nsi (R
1)
4-n
Wherein R
1represent C
1-C
20alkyl, n represents the integer of 1-4, described chlorination silicon alkyl is selected from trimethylchlorosilane, chlorotriethyl silane, tri isopropyl chlorosilane, dimethyl ethyl chlorosilane, diethyl propyl chloride silane, dipropyl methyl chlorosilane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichloro phenylbenzene silicon, dichloromethyl n-propyl silane, dichloromethyl phenyl silane, trichloromethyl silane, trichloroethyl silane, phenyl-trichloro-silicane and silicon tetrachloride, preferably trimethylchlorosilane, chlorotriethyl silane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichloro phenylbenzene silicon, trichloromethyl silane, trichloroethyl silane and silicon tetrachloride.
The described alkylaluminoxane general formula of component (3) is:
Wherein R preferable methyl, a represents the integer of 10-30.Preferable methyl aikyiaiurnirsoxan beta (MAO) and improved methylaluminoxane (MMAO).
For the supported non-metallocene metal catalyst of vinyl polymerization, it is characterized in that, the ratio between each reactant is in every gram of silica-gel carrier, and chloric ether SiClx add-on is 0.01-3mmol, the add-on of alkylaluminoxane is 0.01-30mmol, and the add-on of Nonmetallocene compound is 1-1000 μ mol.
The described supported non-metallocene metal catalyst for vinyl polymerization, is characterized in that, aluminium weight content is 1-15% in supported non-metallocene metal catalyst, and the weight content of central metal M is 0.05-2%.
The method of a kind of catalyzer for ethylene polymerization of the present invention, comprises the steps:
(1) preparation of the silica-gel carrier of chlorination silicon alkyl modification: at rare gas element as under nitrogen protection, silica-gel carrier is added in reactor, add solvent, be dispersed into suspension, add chlorination alkyl silicon, be warming up to 0-90 DEG C, stirring reaction 3-24 hour, preferably 30-60 DEG C, stirring reaction 3-6 hour; Then with solvent wash for several times, vacuum-drying, obtains the silica-gel carrier that contains the modification of chlorination silicon alkyl of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene; Preferably toluene or saturated alkane.
(2) preparation of the silica-gel carrier of alkylaluminoxane: at rare gas element as under nitrogen protection, the silica-gel carrier obtaining in (1) step is added in reactor, add solvent, be dispersed into suspension, add alkylaluminoxane, be warming up to 0-90 DEG C, stirring reaction 3-24 hour, preferably 40-90 DEG C, stirring reaction 3-8 hour, then with solvent wash several, vacuum-drying, obtain the silica-gel carrier that contains alkylaluminoxane of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene; Preferably toluene.
(3) preparation of modified silica-gel load non-metallocene metal catalyst: at rare gas element as under nitrogen protection, the silica-gel carrier that contains alkylaluminoxane that will prepare in (2) step, join and in solvent, make slurries, the solution of Nonmetallocene compound is slowly added drop-wise in these slurries, at 0-90 DEG C, reaction 3-24 hour, preferably at 0-80 DEG C, reaction 1-120 minute, obtain supported non-metallocene single site catalysts, slurries can be directly used in to polyreaction, or gained reactant is removed to desolventizing, after washing is dry, obtain the solid supported non-cyclopentadienyl single site catalyst of good fluidity, described solvent is selected from toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene, preferably toluene, hexane and both mixtures.
The catalyzer of preparing in load non-metallocene metal catalytic agent method of the present invention can be used on different polymerization processs, as vapour phase polymerization and slurry polymerization etc.Can be used for equal polymerization or the copolymerization of alkene, be specially adapted to that ethylene homo closes or the copolymerization of ethene and other alpha-olefin, wherein alpha-olefin is selected from propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.
For the load non-metallocene metal catalyst of ethylene polymerization, Nonmetallocene compound is loaded on chlorination alkyl silicon/alkylaluminoxane/silica-gel carrier.
The catalyzer of preparing in supported non-metallocene metal catalytic agent method of the present invention can be directly used in olefinic polymerization, as in gas-phase polymerization process; Also can be used for olefinic polymerization by additional aluminum alkyl catalyst, particularly in slurry process, add aluminum alkyls can remove the impurity in system, improve to a certain extent polymerization activity, and need not add expensive MAO to make promotor.
The solvent that wherein polymerization is used is selected from alkane, aromatic hydrocarbon or halohydrocarbon, preferably a kind of in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform, ethylene dichloride or their mixture, most preferably is a kind of in hexane, toluene, heptane or their mixture.
The concentration of supported non-metallocene metal catalyst in the time of polymerization is 1 × 10
-8mol/L～1 × 10
-3mol/L, preferred concentration range is 1 × 10
-8mol/L～1 × 10
-5mol/L.
Polymerization temperature is-78 DEG C-100 DEG C, is 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 granules of catalyst form obtaining is good, and catalyst particle size is adjustable.
2, the catalyzer of preparing in load non-metallocene metal catalytic agent method of the present invention has very high vinyl polymerization catalytic activity.
3, the catalyzer of preparing in load non-metallocene metal catalytic agent method of the present invention has the copolymerization performance of good catalyzed ethylene and alpha-olefin, and Copolymerization activity is high.
4, load non-metallocene metal catalyst of the present invention obtains resin powder and has good particle form for olefinic polymerization, and tap density is high, goes for slurry process and vapor phase process polymerization technique.
The analysis and characterization instrument using in the present invention is as follows:
1, ICP (plasma emission spectrum) characterizes: the weight percent of metal in quantitative assay carried catalyst.The P1000 type ICP-AES plasma emission spectrometer that PE company of the instrument selection U.S. produces.
2, the sign of polymericular weight and molecular weight distribution: molecular weight and distribution thereof are measured by gel permeation chromatography (GPC), instrument adopts Waters Alliance GPCV2000, and solvent is 1; 2; 4-trichlorobenzene, sample concentration is lmg/ml, solvent flow rate is 1.0ml/min; Measuring temperature is 150 DEG C.Each sample measurement secondary.
Embodiment
Embodiment 1
(1) preparation of chlorination silicon alkyl/silica-gel carrier
Under nitrogen protection, get 2.5 grams of dry silica-gel carriers and add in glass reactor, add 100 milliliters of dried hexanes, be dispersed into suspension, add 1 milliliter of SiCl
2(n-Bu)
2, start stirring, be warming up to 30 DEG C, to react 4 hours, vacuum-drying, obtains the pressed powder of good fluidity.
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
Under nitrogen protection; get 5.0 grams of modified silica gel carriers obtained above and add in glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; add MAO (methylaluminoxane) toluene solution of 18 milliliters of 10wt%; be warming up to 50 DEG C, stirring reaction 4 hours, then uses 50 milliliters × 3 toluene wash three times; then wash with hexane; vacuum-drying, obtains the pressed powder of good fluidity, contains the silica-gel carrier of methylaluminoxane.
(3) preparation of supported non-metallocene metal catalyst A
Under nitrogen protection; by 2.50 grams of the silica-gel carriers that contains methylaluminoxane obtaining above; join in glass reactor; add 35 milliliters of dried toluene to make slurries, will be dissolved in 20 milliliters of toluene 0.168 gram two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride [(L1)
2zrCl
2, it is synthetic sees Chinese patent CN101173011, embodiment 6, its structure is shown in following formula] solution be added drop-wise in reactor, 30 DEG C of reactions 30 minutes, then use 35 milliliters of toluene wash, vacuum-drying, obtains load non-metallocene metal catalyst A.Characterize through ICP, in catalyst A, Zr weight content is that 0.46%, Al weight content is 10.10%.
Comparing embodiment 1
(1) preparation of alkylaluminoxane/silica-gel carrier
Under nitrogen protection; get 7.01 grams of silica gel and add in glass reactor, add 90 milliliters of dried toluene, be dispersed into suspension; add the MAO(methylaluminoxane of 40 milliliters of 10wt%) toluene solution; be warming up to 50 DEG C, stirring reaction 4 hours, then uses 50 milliliters × 3 toluene wash three times; then wash with hexane; vacuum-drying, obtains the pressed powder of good fluidity, i.e. alkylaluminoxane/silica-gel carrier.
(3) preparation of supported non-metallocene metal catalyst A*
Under nitrogen protection; 2.50 grams of the above-mentioned alkylaluminoxane/silica-gel carriers preparing are joined in glass reactor; add 30 milliliters of dried toluene to make slurries, will be dissolved in 0.168 gram of two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride [(L in 20 milliliters of toluene
1)
2zrCl
2, its synthetic synthetic with title complex in embodiment 1] solution be added drop-wise in reactor, 30 DEG C of reactions 30 minutes, then use 30 milliliters of toluene wash, vacuum-drying, obtains supported non-metallocene metal catalyst A*.Characterize through ICP, in catalyst A *, Zr weight content is that 0.52%, 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 1
2(n-Bu)
2be changed to SiCl
4.
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2).
(3) preparation of supported non-metallocene metal catalyst B
With embodiment 1 step (4), only 0.168 gram of two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride in embodiment 1 is replaced with to 0.152 gram of [two-[N-(the 3-tertiary butyl-salicylidene) aniline] titanium dichloride] (L
2)
2tiCl
2(under its structure is shown in, it is synthetic sees document Chemistry Letters, 1999,1065), obtain load non-metallocene metal catalyst B.Characterize through ICP, in catalyst B, Ti weight content is that 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 metal catalyst C
With embodiment 1 step (3), only 0.168 gram of two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride in embodiment 1 is replaced with to 0.198 gram of [two-[N-(3-phenyl-salicylidene) aniline] titanium dichloride] ((L
3)
2tiCl
2(its structure see under), it is synthetic sees document Chemistry Letters, 1999,1065), obtain load non-metallocene metal catalyst C.Characterize through ICP, in catalyzer C, Ti weight content is that 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 1
2(n-Bu)
2be changed to CH
3siCl
3.
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2).
(3) preparation of supported non-metallocene metal catalyst D
With embodiment 1 step (3), (it is synthetic sees Chinese patent CN101173011 only 0.168 gram [two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride] in embodiment 1 to be replaced with to 0.165 gram of two-[N-(the 3-tertiary butyl-salicylidene) aniline] zirconium dichloride, embodiment 11, under its structure is shown in), obtain load non-metallocene metal catalyst D.Characterize through ICP, in catalyzer D, Zr weight content is that 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 metal catalyst E
With embodiment 1 step (3), only 0.168 gram of two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride in embodiment 1 is replaced with to 0.225 gram of (L
2)
3zr
2cl
4the solution of [its structure is as follows, synthesizes and sees Chinese patent CN1769310, embodiment 2] is added drop-wise in reactor, 30 DEG C of reactions 30 minutes, then uses 50 milliliters of toluene wash, and vacuum-drying, obtains supported non-metallocene metal catalyst E.Characterize through ICP, in catalyzer E, Zr weight content is that 0.42%, 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 metal catalyst F
With embodiment 1 step (3), only 0.168 gram [two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride] in embodiment 1 replaced with to 0.221 gram of (L
5)
3zr
2cl
4(its structure is as follows, synthesizes and sees Chinese patent CN1769310, embodiment 1), obtains supported non-metallocene metal catalyst F.Characterize through ICP, in catalyzer F, Zr weight content is that 0.43%, 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 metal catalyst G
With embodiment 1 step (3), only 0.168 gram [two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride] in embodiment 1 replaced with to 0.221 gram of (L
5)
3ti
2cl
4(its structure is as follows, synthesizes and sees Chinese patent CN1769310, embodiment 4), obtains supported non-metallocene metal catalyst G.Characterize through ICP, in catalyzer G, Ti weight content is that 0.32%, 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 metal catalyst H
With embodiment 1 step (3), only 0.168 gram [two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride] in embodiment 1 replaced with to 0.221 gram of (L
5)
9zr
8cl
16(its structure is as follows, synthesizes and sees Chinese patent CN1769310, embodiment 3), obtains supported non-metallocene metal catalyst H.Characterize through ICP, in catalyzer H, Zr weight content is that 0.38%, Al weight content is
.
High-pressure ethylene polymerization experiment
High-pressure ethylene polymerization experiment process is as follows:
In the stainless steel polymermaking autoclave of 2 liters, with the each displacement of nitrogen and ethene three times, then add 1000 milliliters of hexane solvents, along with adding of hexane, the triethyl aluminum of 2 milliliter of 1 mol/L (TEA) hexane solution is added, (while investigating ethylene copolymerization, 10ml1-hexene is added with hexane), then add 50～100 milligrams of the load metallocene catalysts that above-described embodiment makes, be warming up to 80 DEG C, pressure is risen to and maintained 1.0MPa, react 1 hour.After polyreaction finishes, cooling, collects polyethylene particle powder, weighs.
Concrete polymerization result is listed in table 1.
Table 1, supported non-metallocene metal catalyst polymerization result
Claims (8)
1. for a supported non-metallocene metal catalyst for vinyl polymerization, it is characterized in that, this catalyzer comprises the reaction product of following component:
(1) Nonmetallocene compound;
(2) chlorination silicon alkyl;
(3) alkylaluminoxane;
(4) silica-gel carrier;
The described Nonmetallocene compound of component (1), refers to the metal complexes shown in general formula 1 and 2,
In general formula 1, R
1be selected from and replace or unsubstituted C
1-C
20aliphatic group or C
6-C
30aryl radical, R
2-R
6identical or different, be hydrogen atom, halogen atom, C
1-C
20aliphatic group, C
3-C
20cyclic hydrocarbon radical or C
6-C
20aryl radical, on described alkyl, arbitrary hydrogen or carbon atom are optionally replaced by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin heteroatoms;
M is the transition metal of the 4th family in the periodic table of elements, and X is the one being selected from halogen, alkyl,-oxyl, acid group and amido, when n is 2 or when larger, multiple X groups are identical or different; M and n are the integers of 1-3, and m+n=4;
In general formula 2: M is the transition metal of the 4th family in the periodic table of elements; N is the integer of 1-30, when m is 2 or when larger, multiple X groups are identical or different; M is the integer that meets M valence state;
X is selected from the one in halogen, alkyl,-oxyl, acid group and amido;
R
1-R
8identical or different, be hydrogen atom, halogen atom, C
1-C
20aliphatic group, C
3-C
20cyclic hydrocarbon radical or C
6-C
20aryl radical, the arbitrary hydrogen described in it on alkyl or carbon atom are optionally replaced by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin heteroatoms;
R
9-R
10identical or different, be selected from and replace or unsubstituted C
1-C
20aliphatic group or C
6-C
30aryl radical;
R
1-R
10in two or more groups be optionally mutually keyed to ring;
Y is a bridge joint group, is C
1-C
20aliphatic group or C
6-C
20aryl radical, arbitrary hydrogen or the carbon atom described in it on alkyl optionally replaced by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin heteroatoms;
The described chlorination alkyl of component (2) silica modifier refers to compound: Cl described in following general formula
nsi (R
1)
4-n
R in formula
1represent C
1-C
20alkyl, n represents the integer of 1-4;
The described alkylaluminoxane general formula of component (3) is:
In formula, R represents C
1-C
12alkyl, a represents the integer of 4-30.
2. the supported non-metallocene metal catalyst for vinyl polymerization according to claim 1, is characterized in that, in general formula 1, and R
1be selected from C
1-C
20aliphatic group or C
6-C
30aryl radical, R
2-R
6be selected from hydrogen atom, halogen atom or C
1-C
20aliphatic group; M is selected from titanium, zirconium or hafnium; X is selected from halogen or alkyl;
In general formula 2, M is selected from titanium, zirconium or hafnium; N is the integer of 1-10; R
1-R
8be selected from hydrogen atom, halogen atom or C
1-C
20aliphatic group; R
9-R
10be selected from C
1-C
20fat and aryl radical; X is selected from halogen or alkyl; Y is a bridge joint group, is selected from C
1-C
20aliphatic group or C
6-C
20aryl radical.
3. the supported non-metallocene metal catalyst for vinyl polymerization according to claim 1, it is characterized in that, ratio between each reactant is in every gram of silica-gel carrier, chloric ether SiClx add-on 0.01-3mmol, the add-on of alkylaluminoxane is 0.01-30mmol, and the add-on of Nonmetallocene compound is 1-1000 μ mol.
4. the supported non-metallocene metal catalyst for vinyl polymerization according to claim 1, is characterized in that, in supported non-metallocene metal catalyst, the weight content of aluminium is 1-15%, and the weight content of central metal M is 0.05-2%.
5. the supported non-metallocene metal catalyst for vinyl polymerization according to claim 1, is characterized in that, described chlorination silicon alkyl, wherein R
1be selected from methyl, ethyl or propyl group or phenyl; Described alkylaluminoxane, wherein R is methyl, a represents the integer of 10-30.
6. the preparation method of the supported non-metallocene metal catalyst for vinyl polymerization described in one of claim 1-5, is characterized in that, comprises the following steps:
The first step: under protection of inert gas, silica-gel carrier reacts 3-24 hour with chlorination silicon alkyl at 0-90 DEG C;
Second step: under protection of inert gas, the first step gained chlorination silicon alkyl modified silica-gel is reacted to 3-24 hour with alkylaluminoxane at 0-90 DEG C;
The 3rd step: under protection of inert gas, second step gained alkylaluminoxane modified silica-gel is reacted to 0.5-24 hour with Nonmetallocene compound at 0-90 DEG C;
More than the dispersion agent of reaction is selected from toluene, benzene, dimethylbenzene, hexane, heptane or hexanaphthene.
7. the preparation method of catalyzer according to claim 6, is characterized in that, in the first step reaction, temperature of reaction is 30-60 DEG C; Dispersion agent used is selected from toluene or saturated alkane; In second step reaction, temperature of reaction is 20-90 DEG C; Dispersion agent used is toluene; In three-step reaction, dispersion agent used is selected from toluene, hexane or both mixtures.
8. the supported non-metallocene metal catalyst for vinyl polymerization described in claim 1-5 any one is in the application of vinyl polymerization.
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| WO2000040622A1 (en) * | 1998-12-30 | 2000-07-13 | Univation Technologies, Llc | Germanium bridged metallocenes producing polymers with increased melt strength |
| JP2002179722A (en) * | 2000-12-18 | 2002-06-26 | Idemitsu Petrochem Co Ltd | Catalyst for producing stereoblock olefin polymer |
| CN1539855A (en) * | 2003-10-29 | 2004-10-27 | 扬子石油化工股份有限公司 | Loaded method of load type Non-metallocene catalyst-and polymerizing application |
| CN101423574A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Supported non-metallocene single site catalyst component and preparation method thereof and use |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000040622A1 (en) * | 1998-12-30 | 2000-07-13 | Univation Technologies, Llc | Germanium bridged metallocenes producing polymers with increased melt strength |
| JP2002179722A (en) * | 2000-12-18 | 2002-06-26 | Idemitsu Petrochem Co Ltd | Catalyst for producing stereoblock olefin polymer |
| CN1539855A (en) * | 2003-10-29 | 2004-10-27 | 扬子石油化工股份有限公司 | Loaded method of load type Non-metallocene catalyst-and polymerizing application |
| CN101423574A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Supported non-metallocene single site catalyst component and preparation method thereof and use |
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