CN100343290C - Metallocene catalyst for production of polyolefine with broad peak or double peaks molecular weight distribution in monoreactor and its preparation - Google Patents
Metallocene catalyst for production of polyolefine with broad peak or double peaks molecular weight distribution in monoreactor and its preparation Download PDFInfo
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- CN100343290C CN100343290C CNB021472165A CN02147216A CN100343290C CN 100343290 C CN100343290 C CN 100343290C CN B021472165 A CNB021472165 A CN B021472165A CN 02147216 A CN02147216 A CN 02147216A CN 100343290 C CN100343290 C CN 100343290C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 238000009826 distribution Methods 0.000 title claims abstract description 32
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 8
- 239000012968 metallocene catalyst Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 73
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 125000000524 functional group Chemical group 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 71
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 150000002894 organic compounds Chemical class 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- 229910007926 ZrCl Inorganic materials 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 22
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 16
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- -1 Ursol D Chemical compound 0.000 claims description 11
- 230000002902 bimodal effect Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000013256 coordination polymer Substances 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 238000005243 fluidization Methods 0.000 claims description 7
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 150000002334 glycols Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000969 carrier Substances 0.000 abstract description 7
- 238000004458 analytical method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZNEMGFATAVGQSF-UHFFFAOYSA-N 1-(2-amino-6,7-dihydro-4H-[1,3]thiazolo[4,5-c]pyridin-5-yl)-2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound NC=1SC2=C(CN(CC2)C(CC=2OC(=NN=2)C=2C=NC(=NC=2)NC2CC3=CC=CC=C3C2)=O)N=1 ZNEMGFATAVGQSF-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940038032 nitrogen 20 % Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 1
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Abstract
The present invention provides a metallocene compound loaded catalyst for producing polyolefine with broad peak or double-peak molecular weight distribution in a mono-reactor, and a preparation method thereof. The catalyst can be realized by that after at least one organo-functional group compound is combined on an inorganic oxide carrier of which the surface contains a hydroxy group, a metallocene compound is loaded on the inorganic oxide carrier and can be realized by that after different metallocene compounds are respectively loaded on a plurality of nanometer grade small inorganic oxide carriers, the metallocene compounds are mixed with the nanometer grade small inorganic oxide carriers. Thus, a molar ratio of different functional groups on the carriers can be regulated, or the different combination of different metallocene compounds loaded on different carriers can be regulated so as to achieve the aim for producing the polyolefine with different molecule structures according to different application requirements.
Description
Invention field
The present invention relates to a kind of catalyzer and method for making thereof of in single reactor, producing polyolefinic load metallocene compound with broad peak or bimodal molecular weight distribution.
Background technology
As everyone knows, the catalyzer with the metallocene compound preparation has the characteristics at single-activity center.Very narrow with the molecular weight of polyethylene that it is produced, MWD is generally less than 3, has well-proportioned side chain to distribute on the co-polymer main chain.This just makes that the mechanical property of polymkeric substance is extremely strong, and optical property is splendid, thereby has wide application field.But because mechanical property is extremely strong, make processing output low, consumed energy is many, brings great technical difficulty to industrial application.
The solution of conventional art is by being blended directly in together in the micropore of a certain amount of silica-gel carrier that impregnated in the load metallocene compound or with two kinds of catalyzer with Ziegler-Natta catalyst.Patent US 6,051,525 as Exxon Neftegas Limited discloses a kind of catalyzer with a plurality of active centre.It is with Z-N component magnesium compound and TiCl
4Impregnated on the silica-gel carrier.In addition, as the disclosed a kind of catalyzer of Chinese patent CN 1250058A, by metallocene catalyst and two kinds of catalyzer mechanically mixing of Z-N and make.Because the mechanical property of the polymkeric substance that Ziegler-Natta catalyst is produced and optical property are had not as good as the metallocene polymers product, the molecular weight of polyethylene that two kinds of catalyzer are produced after dipping, mechanically mixing distributes, though also realized the purpose of broad peak or bimodal distribution, improved certain processing characteristics, but it and the polymer phase ratio that pure metallocene catalyst is produced, its mechanical property and optical property are all impaired greatly.Influenced the advantage of metallocene polymers.Characteristics of the present invention are the polyethylene that are combined into broad peak or bimodal distribution by the different molecular weight that a plurality of single active center metallocene catalyst is produced.Catalyzer of the present invention is earlier with several different organo-functional groups such as hydroxyl (OH), carboxyl (COOH), amido (NH
2), (CN) etc., organic assembling by a certain percentage, and be carried on the carrier with the method for chemical reaction or physics dipping makes metallocene compound and organo-functional group coordination load to itrile group then.Under the condition that the promotor aikyiaiurnirsoxan beta exists, metallocene contacts with ethene and polycoordination further takes place, and the polyethylene of generation has wider molecular weight distribution, and molecular weight distribution MWD is more than 4, and molecular weight distribution has the bimodal pattern feature.And the molar content ratio of different functional groups on the adjustment carrier, the distribution of molecular weight of polyethylene is changed, thereby realize adjusting the organic assembling of different molecular structures, to reach different application requiring.The mechanical property that had so both kept metallocene polymers is strong, the advantage of good in optical property, has solved the shortcoming of difficult processing again, has widened the Application Areas of metallocene polymers simultaneously.As make high-strength thin-film and high-density products such as pressure water pipe, gas pipe.
Summary of the invention
The invention provides a kind of load metallocene catalyst that is used to produce broad peak or wide/bimodal molecular weight distribution polyolefin, its empirical formula is
PLMX
2
LMX in the formula
2Be one or more metallocene compounds, wherein L is the cyclopentadiene or derivatives thereof, and M is selected from group vib metal Ti, Zr or Hf, and X is a halogen,
P is the carrier of load metallocene, and it is the inorganic oxide S that hydroxyl is contained on a kind of surface, or contains on the inorganic oxide of hydroxyl the inorganic oxide in conjunction with one or more organo-functional group on the surface again,
Can be represented by the formula:
S (A-R-A)
nOr
S (A-R-A)
n(B-R '-B)
mOr
S (A-R-A)
n(C-R '-C)
mOr
S (A-R-A)
n(D-R '-D)
mOr the combination of other similar type be connected,
In the formula, A-R-A, B-R '-B, C-R '-C, D-R '-D represent to have an organic compound of binary functional group at least with the S surface hydroxyl reacts respectively; A, B, C or D represent respectively different organo-functional groups (or with other functional groups after residue),
N=1-20, R can be selected from alkyl, aryl or the cycloalkyl of 1-20 carbon atom;
M=1-20, R ' can be selected from the alkyl or aryl of alkyl, aryl, cycloalkyl or the heteroatoms replacement of 1-50 carbon atom;
The inorganic oxide P of hydroxyl is contained on the surface, for the class spheric of diameter 0.2-1000 micron has microporous inorganic oxides, or the inorganic oxide of any form of the tiny median size 0.1-200 nanometer of nano level;
When P is the tiny inorganic oxide of nano level, gets this inorganic oxide and be divided at least two groups, every group of different metallocene compound (L ' MX of difference load
2, L " MX
2Or L " ' MX
2Deng), the inorganic oxide of respectively organizing with the different metallocene compounds of load is mixed then, and forms (PL ' MX
2+ PL " MX
2) catalyzer of form.
The present invention also provides above-mentioned Preparation of catalysts method.Comprise:
A. when carrier S be diameter 0.2-1000 micron class spheric when having the surface of micropore to contain the inorganic oxide of hydroxyl:
(1) carrier S is placed an activation furnace, under nitrogen gas stream, be warming up to 350-650 ℃ (preferred temperature 420-500 ℃), add a certain amount of organic compound A-R-A of binary functional group at least that has, the lip-deep hydroxyl of monobasic functional group A and carrier S reacts, and forms as empirical formula S (A-R-A)
nShown structure, n=1-20 in the formula, R can be selected from alkyl, aryl or the cycloalkyl of 1-20 carbon atom, hydroxyl is 1 with (A-R-A) mol ratio of compound on the S surface: 10-10: 1, with this mixture constant temperature after 4-6 hour, reduce to envrionment temperature, be formed on the carrier carrier I, use for next step load metallocene compound in conjunction with a kind of organo-functional group A;
(2) the carrier I that also step (1) can be made, be warming up to 80-200 ℃ again, add a certain amount of have another kind of organic compound B-R '-B, the C-R '-C or the D-R '-D of binary functional group at least, former one of be combined among functional group A on the carrier S and the B of functional group, C or the D reacts, and forms as empirical formula S (A-R-A)
n(B-R '-B)
m, S (A-R-A)
n(C-R '-C)
m, S (A-R-A)
n(D-R '-D)
mOr the combination of other similar type and the structure that is connected, m=1-20 in the formula, R ' can be selected from the alkyl or aryl of alkyl, aryl, cycloalkyl or the heteroatoms replacement of 1-50 carbon atom, the mol ratio of functional group A and B or C or D is 10 on the S surface: 1-1: 10, with this mixture constant temperature after 8 hours, reduce to envrionment temperature, the carrier II that makes in conjunction with more than one organo-functional groups uses for next step load metallocene compound;
(3) carrier I that step (1) or (2) are made or II insert one and have in the preparation bottle of agitator, add a certain amount of toluene and make solvent, add LMX again
2Metallocene compound and a certain amount of methylaluminoxane (MA0) stirred 4 hours down at 40 ℃, took out toluene then under vacuum, to the product drying, became free-flowing;
B. when carrier S be any form surface of the tiny median size 0.1-200 nanometer of nano level when containing the inorganic oxide of hydroxyl:
(1) carrier S is placed a rotary funace, add a certain amount of organic compound A-R-A of binary functional group at least that has simultaneously, oxygen in coming out of the stove with nitrogen replacement, use the nitrogen fluidisation, be warming up to 420-480 ℃ then, the lip-deep hydroxyl of monobasic functional group A and carrier S reacts, and forms as empirical formula S (A-R-A)
nShown structure, n=1-20 in the formula, R can be selected from alkyl, aryl or the cycloalkyl of 1-20 carbon atom, this mixture constant temperature was cooled to envrionment temperature after 6 hours, nitrogen is preserved down, be formed on the carrier carrier III, use for next step load metallocene compound in conjunction with a kind of organo-functional group;
(2) the carrier III that also step (1) can be made, be warming up to 80-200 ℃ again, add a certain amount of another kind of organic compound B-R '-B of binary functional group at least that has, C-R '-C or D-R '-D, former one of be combined among functional group A on the carrier S and the B of functional group, C or the D reacts, and forms as empirical formula S (A-R-A)
n(B-R '-B)
m, S (A-R-A)
n(C-R '-C)
m, S (A-R-A)
n(D-R '-D)
mOr the combination of other similar type and the structure that is connected, m=1-20 in the formula, R ' can be selected from the alkyl or aryl of alkyl, aryl, cycloalkyl or the heteroatoms replacement of 1-50 carbon atom, under nitrogen atmosphere, this mixture constant temperature was cooled to envrionment temperature after 6 hours, nitrogen is preserved down, be formed on the carrier carrier IV, use for next step load metallocene compound in conjunction with more than one organo-functional groups;
(3) can also directly get carrier S, the organic compound that does not add any band binary functional group, insert in the rotary funace, under nitrogen gas stream, be warming up to 800 ℃, constant temperature 6 hours, reduce under the envrionment temperature nitrogen and preserve, make the carrier V that does not link the binary functional compounds, use for next step load metallocene compound;
(4) with the various different metallocene compound LMX of carriers difference load that make
2, L is the cyclopentadiene or derivatives thereof in the formula, and M is selected from group vib metal: Ti, Zr or Hf, and X is a halogen
Get among the preparation bottle A that a certain amount of carrier III or IV or V add belt stirrer, add after a certain amount of toluene stirs, add a certain amount of MAO, stirred 1 hour down, add a kind of metallocene compound L ' MX at 40 ℃
2, stirred 4 hours down at 45 ℃;
Get among the preparation bottle B of a certain amount of carrier III or IV or V adding belt stirrer, with above-mentioned reinforced and operation, difference only is to add another kind of metallocene compound L again " MX
2Replace L ' MX
2
Get among the preparation bottle C of a certain amount of carrier III or IV or V adding belt stirrer, with above-mentioned reinforced and operation, difference only is to add another kind of metallocene compound L again " ' MX
2Replace L ' MX
2
(5) the various products with the different metallocene compounds of load mix
Product among preparation bottle A, B and the C is taken out, together add in the preparation bottle of another belt stirrer, stirred at ambient temperature 1 hour, boil off toluene solvant with nitrogen purging then, the product in bottle becomes the catalyzer of solid state.
The inorganic oxide that hydroxyl is contained on the employed surface of catalyzer of the present invention is selected from SiO
2Or Al
2O
3Can have at least that the organic compound of binary functional group comprises: di-carboxylic acid class, two amines, two nitriles and glycols with the inorganic oxide surface hydroxyl reacts.Wherein said surface in conjunction with a kind of organo-functional group A contains that the mol ratio of hydroxyl and A is 1 in the inorganic oxide of hydroxyl: 10-10: 1, be preferably 3: 1-1: 3.Wherein said surface in conjunction with two kinds of organo-functional group A and B or C or D contains that the mol ratio of A and B or C or D is 10 in the inorganic oxide of hydroxyl: 1-1: 10, be preferably 3: 1-1: 3.
Catalyzer of the present invention is employed to have at least that the organic compound of binary functional group comprises: terephthalic acid, Ursol D, quadrol, ethylene glycol, butyleneglycol, succinonitrile etc., preferred terephthalic acid.The metallocene compound LMX of catalyst cupport of the present invention
2Particularly, as CP
2ZrCl
2, CP
2ZrCl
2, (CH
3CP)
2ZrCl
2, (en) (Ind)
2ZrCl
2, (Me
2Si) (1,4,7-Me
3Ind)
2ZrCl
2Deng.
Also comprise methylaluminoxane (MAO) in the catalyzer of the present invention, wherein the mol ratio of Al/Zr is 30-500, preferred 80-150.
Catalyzer of the present invention is used in to produce in the single reactor to have in the olefin polymetiation process of broad peak or bimodal molecular weight distribution.Comprise: vinyl polymerization, propylene polymerization, ethylene-alpha-olefin polymerization and ethene and the copolymerization of alhpa olefin more than two kinds.The size distribution of wherein said production polymericular weight, can recently realize by regulating on a kind of carrier the mole of several functional groups of bonded, also can by respectively behind load metallocene compound not of the same race on the tiny carrier of several nano levels remix realize.Described polyreaction has different hydrogen and transfers responsive, can not add or add less the hydrogen molecular weight regulator.
In specific embodiment, the present invention relates to following content:
1. load metallocene catalyst that is used to produce broad peak or wide/bimodal molecular weight distribution polyolefin, its empirical formula is
PLMX
2
LMX in the formula
2Be one or more metallocene compounds, wherein L is the cyclopentadiene or derivatives thereof, and M is the group vib metal that is selected from Ti, Zr or Hf, and X is a halogen,
P is the carrier of the described metallocene compound of load, and it is the inorganic oxide that combines one or more organo-functional group on a kind of inorganic oxide S that contains hydroxyl on the surface,
Described carrier P represents with following formula:
S (A-R-A)
nOr S (A-R-A)
n(B-R '-B).
In the formula, A-R-A and B-R '-B represents respectively and can contain the organic compound of binary functional group at least that has that the hydroxyl on the inorganic oxide S surface of hydroxyl reacts with described surface;
Described A and B represent respectively different organo-functional groups or with other functional groups after residue,
N=1-20, R are alkyl, aryl or the cycloalkyl that is selected from 1-20 carbon atom;
M=1-20, the alkyl or aryl that R ' replaces for alkyl, aryl, cycloalkyl or the heteroatoms that is selected from 1-50 carbon atom;
Wherein, the inorganic oxide S that hydroxyl is contained on described surface is that the class spheric of diameter 0.2-1000 micron has microporous inorganic oxides, or the inorganic oxide of any form of the tiny median size 0.1-200 nanometer of nano level.
2. according to the catalyzer of aspect 1, the inorganic oxide S that hydroxyl is contained on wherein said surface is selected from SiO
2Or Al
2O
3
3. according to the catalyzer of aspect 1, wherein said have at least that the organic compound of binary functional group comprises: di-carboxylic acid class, two amines, two nitriles or glycols.
4. according to the catalyzer of aspect 1, wherein in the described carrier P that combines a kind of organo-functional group A, the mol ratio of hydroxyl and organo-functional group A is 1: 10-10: 1.
5. according to the catalyzer of aspect 4, the mol ratio of wherein said hydroxyl and described organo-functional group A is 3: 1-1: 3.
6. according to the catalyzer of aspect 1, wherein in the described carrier P that combines two kinds of organo-functional group A and B, the mol ratio of organo-functional group A and organo-functional group B is 10: 1-1: 10.
7. according to the catalyzer of aspect 6, the mol ratio of wherein said organo-functional group A and described organo-functional group B is 3: 1-1: 3.
8. according to the catalyzer of aspect 3, wherein said have at least that the organic compound of binary functional group comprises: terephthalic acid, Ursol D, quadrol, ethylene glycol, butyleneglycol or succinonitrile.
9. according to the catalyzer of aspect 8, wherein said have at least that the organic compound of binary functional group is a terephthalic acid.
10. according to the catalyzer of aspect 1, wherein said LMX
2Comprise: CP
2ZrCl
2, CP
2ZrCl
2, (CH
3CP)
2ZrCl
2, (en) (Ind)
2ZrCl
2Or (Me
2Si) (1,4,7-Me
3Ind)
2ZrCl
2
11., wherein also comprise methylaluminoxane according to the catalyzer of aspect 1 or 10.
12. according to the catalyzer of aspect 11, wherein the mol ratio of Al/Zr is 30-500.
13. according to the catalyzer of aspect 12, wherein the mol ratio of Al/Zr is 80-150.
14., comprise the steps: according to each described Preparation of catalysts method of aspect 1-13
A. the inorganic oxide S that contains hydroxyl when the surface is diameter 0.2-1000 micron class spheric when microporous inorganic oxides is arranged,
(1) the inorganic oxide S that described surface is contained hydroxyl places an activation furnace, under nitrogen gas stream, be warming up to 350-650 ℃, add a certain amount of organic compound A-R-A of binary functional group at least that has, monobasic functional group A and the lip-deep hydroxyl of described inorganic oxide S are reacted, form empirical formula S (A-R-A)
nShown structure, n=1-20 in the formula, R is alkyl, aryl or the cycloalkyl that is selected from 1-20 carbon atom, the mol ratio of lip-deep hydroxyl of described inorganic oxide S and A-R-A compound is 1: 10-10: 1, with this mixture constant temperature after 4-6 hour, reduce to envrionment temperature, be formed in described surface and contain the carrier I that combines a kind of organo-functional group A on the inorganic oxide S of hydroxyl, use for next step load metallocene compound;
(2) the carrier I that also step (1) can be made is warming up to 80-200 ℃ again, adds a certain amount of another kind of organic compound B-R '-B of binary functional group at least that has, and itself and organo-functional group B are reacted, and forms empirical formula S (A-R-A)
n(B-R '-B).Shown structure, n=1-20 in the formula, R is alkyl, aryl or the cycloalkyl that is selected from 1-20 carbon atom, m=1-20, the alkyl or aryl that R ' replaces for alkyl, aryl, cycloalkyl or the heteroatoms that is selected from 1-50 carbon atom, the mol ratio of lip-deep organo-functional group A of described inorganic oxide S and organo-functional group B is 10: 1-1: 10, with this mixture constant temperature after 8 hours, reduce to envrionment temperature, be formed in described surface and contain the carrier II that combines more than one organo-functional groups on the inorganic oxide S of hydroxyl, use for next step load metallocene compound;
(3) carrier I that step (1) or (2) are made or II insert one and have in the preparation bottle of agitator, add a certain amount of toluene and make solvent, add formula LMX again
2Metallocene compound and a certain amount of methylaluminoxane, at formula LMX
2In, L is the cyclopentadiene or derivatives thereof, and M is the group vib metal that is selected from Ti, Zr or Hf, and X is a halogen, stirs 4 hours down at 40 ℃, takes out toluene then under vacuum, to the product drying, becomes free-flowing, obtains load metallocene catalyst thus; Perhaps
When b. the inorganic oxide S that contains hydroxyl when the surface is the inorganic oxide of any form of the tiny median size 0.1-200 nanometer of nano level,
(1) described inorganic oxide S is placed a rotary funace, add a certain amount of organic compound A-R-A of binary functional group at least that has simultaneously, oxygen in coming out of the stove with nitrogen replacement, use the nitrogen fluidisation, be warming up to 420-480 ℃ then, monobasic functional group A and the lip-deep hydroxyl of described inorganic oxide S are reacted, form empirical formula S (A-R-A)
nShown structure, n=1-20 in the formula, R is alkyl, aryl or the cycloalkyl that is selected from 1-20 carbon atom, this mixture constant temperature was cooled to envrionment temperature after 6 hours, nitrogen is preserved down, be formed in described surface and contain the carrier III that combines a kind of organo-functional group A on the inorganic oxide S of hydroxyl, use for next step load metallocene compound;
(2) the carrier III that also step (1) can be made is warming up to 80-200 ℃ again, adds a certain amount of another kind of organic compound B-R '-B of binary functional group at least that has, and itself and organo-functional group B are reacted, and forms empirical formula S (A-R-A)
n(B-R '-B).Shown structure, in the formula, n=1-20, R is alkyl, aryl or the cycloalkyl that is selected from 1-20 carbon atom, m=1-20, the alkyl or aryl that R ' replaces for alkyl, aryl, cycloalkyl or the heteroatoms that is selected from 1-50 carbon atom, under nitrogen atmosphere, this mixture constant temperature was cooled to envrionment temperature after 6 hours, nitrogen is preserved down, and being formed in described surface contains the carrier IV that combines more than one organo-functional groups on the inorganic oxide S of hydroxyl, uses for next step load metallocene compound;
(3) carrier that step (1) or (2) the are made different metallocene compound LMX of load respectively
2, L is the cyclopentadiene or derivatives thereof in the formula, and M is the group vib metal that is selected from Ti, Zr or Hf, and X is a halogen, and its method is:
Get a certain amount of carrier III or IV, add among the preparation bottle A of belt stirrer, add after a certain amount of toluene stirs, add a certain amount of methylaluminoxane, stirred 1 hour down, add a kind of metallocene compound, stirred 4 hours down at 45 ℃ at 40 ℃;
Get a certain amount of carrier III or IV again, add among the preparation bottle B of belt stirrer, with above-mentioned reinforced and operation, difference only is to add another kind of metallocene compound;
Get a certain amount of carrier III or IV again, add among the preparation bottle C of belt stirrer, with above-mentioned reinforced and operation, difference only is to add another metallocene compound;
(4) product that will prepare among bottle A, B and the C takes out, together add in the preparation bottle of another belt stirrer, stirred at ambient temperature 1 hour, boil off toluene solvant with nitrogen purging then, product in bottle becomes solid state, obtains load metallocene catalyst.
15. preparation method according to aspect 14, wherein the inorganic oxide S that contains hydroxyl when the surface is that diameter 0.2-1000 micron class spheric is when having microporous inorganic oxides, in step (1), when the inorganic oxide S that described surface is contained hydroxyl places activation furnace, under nitrogen gas stream, be warming up to 420-500 ℃.
16. according to the preparation method of aspect 14, the inorganic oxide S that hydroxyl is contained on wherein said surface is selected from Si0
2Or Al
20
3
17. according to the preparation method of aspect 14, wherein said have at least that the organic compound of binary functional group comprises: di-carboxylic acid class, two amines, two nitriles or glycols.
18. according to the preparation method of aspect 17, wherein said have at least that the organic compound of binary functional group comprises: terephthalic acid, Ursol D, quadrol, ethylene glycol, butyleneglycol or succinonitrile.
19. according to the preparation method of aspect 18, wherein said have at least that the organic compound of binary functional group is a terephthalic acid.
20. according to the preparation method of aspect 14, wherein said LMX
2Comprise: CP
2ZrCl
2, (CH
3CP)
2ZrCl
2, (en) (Ind)
2ZrCl
2Or (Me
2Si) (1,4,7-Me
3Ind)
2ZrCl
2
21. have application in the olefin polymer of broad peak or bimodal molecular weight distribution in production according to each catalyzer of aspect 1-13.
22. according to the application of aspect 21, wherein said olefinic polymerization comprises: vinyl polymerization, propylene polymerization, ethylene-alpha-olefin polymerization or ethene and the copolymerization of alhpa olefin more than two kinds.
23. application according to aspect 21, the size distribution of wherein said polymericular weight, recently realize by the mole of regulating several functional groups of bonded on a kind of carrier, perhaps by respectively behind the metallocene compound not of the same race of load on the tiny carrier of a few part nano levels remix realize.
24., wherein in described polyreaction, do not add or add less the hydrogen molecular weight regulator according to the application of aspect 21.
Description of drawings
Fig. 1 is the graph of molecular weight distribution of the gpc analysis of example 4 polymerisate samples.
Fig. 2 is the graph of molecular weight distribution of the gpc analysis of example 5 polymerisate samples.
Fig. 3 is the graph of molecular weight distribution of the gpc analysis of example 6 polymerisate samples.
Fig. 4 is the graph of molecular weight distribution of the gpc analysis of example 7 polymerisate samples.
Fig. 5 is the graph of molecular weight distribution of the gpc analysis of example 8 polymerisate samples.
Fig. 6 is the graph of molecular weight distribution of the gpc analysis of example 9 polymerisate samples.
Fig. 7 is the graph of molecular weight distribution of the gpc analysis of example 10 polymerisate samples.
Fig. 8 is the graph of molecular weight distribution of the gpc analysis of example 11 polymerisate samples.
Fig. 9 is the graph of molecular weight distribution of the gpc analysis of example 12 polymerisate samples.
Embodiment
The preparation of example 1 carrier I
The model of getting the production of GRACE company is 955 silica gel 110g, adds in the fluidized-bed electrical heater of a φ 67 * 200, adds 5.5g terephthalic acid (PTA) simultaneously.After about 1 hour, be warmed up to 426～500 ℃ with the nitrogen fluidisation, constant temperature 8 hours, 200～300mmH keep-ups pressure
2O.Cool to envrionment temperature then, and nitrogen protection down, make carrier I and use for load metallocene.
The preparation of example 2 carrier II
In the electrical heater in example 1, keep 70g carrier I, and temperature is raised to 160～210 ℃, keep the nitrogen fluidisation.Get the diethylamine of 2ml, be injected in the fluidisation process furnace, move 4 hours, pressure keeps 200～300mmH
2O cools to envrionment temperature then, and nitrogen protection, makes carrier II and uses for load metallocene.
Example 3 load metallocene compounds
Get the carrier I 1.48g of example 1 preparation, add in the preparation bottle that has a magnetic agitation, add methylaluminoxane (MAO) and toluene solution 6.5ml (10%wt), 40 ℃ down stirring move 1 hour.Add bis cyclopentadienyl zirconium dichloride (CP then
2ZrCl
2) solution 15ml, zirconium content 7.44 * 10
-6Mol/ml stirs operation 4 hours down at 45 ℃.Under vacuum, remove toluene solvant at last, become free-pouring solid, use for polymerization up to catalyzer.Wherein the Al/Zr ratio of Ji Suaning is 81.5.
Example 4 polyreactions
With gas-phase fluidized-bed reactive system nitrogen replacement 3 times of φ 76 * 600, the catalyzer 0.22g that gets preparation in the example 3 adds in the Gas-phase reactor, boosts to 2.0Mpa to reactor, therein ethylene 80% (vol), nitrogen 20% (vol).Temperature of reaction is controlled between 108-110 ℃, and polymerization time 30 minutes is reduced to 0.01Mpa with pressure in the reactor, blows out unreacted reactant with nitrogen.Take out polymkeric substance and carry out sample analysis mensuration, the assay determination result is as follows:
Melting index M1:0.168g/10min
Density D: 0.958g/cm
3
Molecular weight distributing index MWD:4.15
Graph of molecular weight distribution is seen Fig. 1.
Example 5 polyreactions
With gas-phase fluidized-bed reactive system nitrogen replacement 3 times of φ 76 * 600, the catalyzer 0.16g that gets preparation in the example 3 adds in the Gas-phase reactor, boosts to 3.0Mpa to reactor, therein ethylene concentration 60% (vol), butene-1 concentration 8% (vol); Nitrogen gas concn 32% (vol).Temperature of reaction between 80-89 ℃, polymerization time 30 minutes, the pressure release stopped reaction takes out polymkeric substance and carries out sample analysis and measure, the assay determination result is as follows:
Melting index M1:3.875g/10min
Density D: 0.924g/cm
3
Molecular weight distributing index MWD:4.14
Graph of molecular weight distribution is seen Fig. 2.
Example 6-11 inorganic oxide carries out polyreaction in conjunction with the mol ratio of hydroxyl and bonded organo-functional group on the catalyzer adjusting inorganic oxide surface of one or both different organo-functional groups
Carry out by the catalyzer of the carrier I of the method for above-mentioned example 1,2 and 3 preparation or II type with by above-mentioned example 4 or 5 described polyreactions.The results list is as follows.
| Instance number | Different functional groups compound mol ratio | Melting index MI g/10min | Molecular weight distribution MWD | Accompanying drawing |
| 6 | OH∶A 1∶1 | 0.17 | 4.60 | Fig. 3 |
| 7 | OH∶A 1∶2.5 | 0.463 | 4.18 | Fig. 4 |
| 8 | OH∶A∶B 1∶2∶1 | 1.769 | 6.11 | Fig. 5 |
| 9 | OH∶A∶B 1∶1∶1 | 2.065 | 7.00 | Fig. 6 |
| 10 | OH∶A 1∶0.5 | 0.133 | 4.57 | Fig. 7 |
| 11 | OH∶A 1∶0.2 | 0.087 | 5.16 | Fig. 8 |
Above-mentioned vapour phase polymerization test all is to carry out under the condition that no hydrogen exists.
OH represents the hydroxyl on the inorganic oxide surface; A represents that terephthalic acid and B represent quadrol.
The tiny inorganic oxide of example more than 12 part nano levels is the Preparation of catalysts and the polyreaction that form of the different metallocene compound remix of load respectively
1.A preparing carriers
Choose the undressed gas phase silica gel 20g that CABOT company produces.Its particle dia is 5～35 nanometers, and the mean sizes of assembling particle is 0.2 micron, and specific surface area is 50～380m
2/ g.Put into a rotary funace, add terephthalic acid (PTA) 0.6g simultaneously, the oxygen in coming out of the stove with nitrogen replacement is used the nitrogen fluidisation, is warmed up to 420-480 ℃ then.Behind the constant temperature 6 hours, cool to envrionment temperature, and as fluidizing medium.Nitrogen protection is stored down, uses for load metallocene catalyst.
2.B preparing carriers
Choose the undressed gas phase silica gel 30g that CABOT company produces.Its particle dia is 5～35 nanometers, and the mean sizes of assembling particle is 0.2 micron, and specific surface area is 50～380m
2/ g.Put into a rotary funace, do fluidizing medium, temperature in the stove is raised to 800 ℃ of constant temperature 6 hours, cool to envrionment temperature, use nitrogen protection, use for load metallocene catalyst with nitrogen.
3. load metallocene compound
Get A carrier 1.02g, add among the preparation bottle A who has a magnetic agitation, and add the 5ml toluene solvant, the MAO solution (10%wt) that the back that stirs adds 0.8ml stirred 1 hour down at 40 ℃, added (the Me of 1.86ml then
2Si) (1,4,7-Me
3Ind)
2ZrCl
2Solution (7.56 * 10
-6Mol-Zr/ml), stir operation 4 hours down at 45 ℃, the Al/Zr ratio of calculating is 86.6.Other gets A carrier 1.06g and adds among 1 preparation bottle B that has a magnetic stirring apparatus, and adds the 5ml toluene solvant, and the back that stirs adds the MAO solution (10%wt) of 0.8ml.Stirred 1 hour down at 40 ℃.Add 2.0ml (en) then (Ind)
2ZrCl
2Solution (7.0 * 10
-6Mol-Zr/ml), stir operation 4 hours down at 45 ℃.Get B carrier 1.01g and add among the preparation bottle C who has a magnetic stirring apparatus, and add the 5ml toluene solvant.Add the MAO solution (10%wt) of 1.0ml after stirring, stirred 1 hour down at 40 ℃.(the CH that adds 1.9ml then
3CP)
2ZrCl
2Solution (7.0 * 10
-6Mol-Zr/ml), stir operation 1 hour down at 45 ℃, the Al/Zr ratio of calculating is 105.1.
Product among preparation bottle A, the B is added among the preparation bottle C, and stir operation 1 hour at ambient temperature, evaporate with nitrogen purging then and desolvate, the product body in bottle becomes the catalyzer of solid state.
4. aggregation test:
With gas-phase fluidized-bed reactive system nitrogen replacement 3 times of φ 76 * 600mm, get the catalyzer 0.22g for preparing in aforementioned the example, add in the Gas-phase reactor.Boost to 2.01Mpa with reaction mass then, wherein: ethylene concentration 60% (vol), nitrogen 35.2% (vol), butene-1 4.8% (vol), temperature of reaction is controlled between 80-85 ℃, polymerization time 1 hour.Reactor pressure is reduced to 0.001Mpa, blow out the unreacted material with nitrogen.Take out polymkeric substance and carry out assay determination, the assay determination result is as follows:
Melting index M1:0.521g/10min
Density D: 0.929g/cm
3
Molecular weight distributing index MWD:16.80
Graph of molecular weight distribution is seen Fig. 9.
Claims (24)
1. load metallocene catalyst that is used to produce broad peak or wide/bimodal molecular weight distribution polyolefin, its empirical formula is PLMX
2
LMX in the formula
2Be one or more metallocene compounds, wherein L is the cyclopentadiene or derivatives thereof, and M is the group vib metal that is selected from Ti, Zr or Hf, and X is a halogen,
P is the carrier of the described metallocene compound of load, and it is the inorganic oxide that combines one or more organo-functional group on a kind of inorganic oxide S that contains hydroxyl on the surface,
Described carrier P represents with following formula:
S (A-R-A)
nOr S (A-R-A)
n(B-R '-B).
In the formula, A-R-A and B-R '-B represents respectively and can contain the organic compound of binary functional group at least that has that the hydroxyl on the inorganic oxide S surface of hydroxyl reacts with described surface;
Described A and B represent respectively different organo-functional groups or with other functional groups after residue,
N=1-20, R are alkyl, aryl or the cycloalkyl that is selected from 1-20 carbon atom;
M=1-20, the alkyl or aryl that R ' replaces for alkyl, aryl, cycloalkyl or the heteroatoms that is selected from 1-50 carbon atom;
Wherein, the inorganic oxide S that hydroxyl is contained on described surface is that the class spheric of diameter 0.2-1000 micron has microporous inorganic oxides, or the inorganic oxide of any form of the tiny median size 0.1-200 nanometer of nano level.
2. according to the catalyzer of claim 1, the inorganic oxide S that hydroxyl is contained on wherein said surface is selected from SiO
2Or Al
2O
3
3. according to the catalyzer of claim 1, wherein said have at least that the organic compound of binary functional group comprises: di-carboxylic acid class, two amines, two nitriles or glycols.
4. according to the catalyzer of claim 1, wherein in the described carrier P that combines a kind of organo-functional group A, the mol ratio of hydroxyl and organo-functional group A is 1: 10-10: 1.
5. according to the catalyzer of claim 4, the mol ratio of wherein said hydroxyl and described organo-functional group A is 3: 1-1: 3.
6. according to the catalyzer of claim 1, wherein in the described carrier P that combines two kinds of organo-functional group A and B, the mol ratio of organo-functional group A and organo-functional group B is 10: 1-1: 10.
7. according to the catalyzer of claim 6, the mol ratio of wherein said organo-functional group A and described organo-functional group B is 3: 1-1: 3.
8. according to the catalyzer of claim 3, wherein said have at least that the organic compound of binary functional group comprises: terephthalic acid, Ursol D, quadrol, ethylene glycol, butyleneglycol or succinonitrile.
9. catalyzer according to Claim 8, wherein said have at least that the organic compound of binary functional group is a terephthalic acid.
10. according to the catalyzer of claim 1, wherein said LMX
2Comprise: CP
2ZrCl
2, CP
2ZrCl
2, (CH
3CP)
2ZrCl
2, (en) (Ind)
2ZrCl
2Or (Me
2Si) (1,4,7-Me
3Ind)
2ZrCl
2
11., wherein also comprise methylaluminoxane according to the catalyzer of claim 1 or 10.
12. according to the catalyzer of claim 11, wherein the mol ratio of Al/Zr is 30-500.
13. according to the catalyzer of claim 12, wherein the mol ratio of Al/Zr is 80-150.
14., comprise the steps: according to each described Preparation of catalysts method of claim 1-13
A. the inorganic oxide S that contains hydroxyl when the surface is diameter 0.2-1000 micron class spheric when microporous inorganic oxides is arranged,
(1) the inorganic oxide S that described surface is contained hydroxyl places an activation furnace, under nitrogen gas stream, be warming up to 350-650 ℃, add a certain amount of organic compound A-R-A of binary functional group at least that has, monobasic functional group A and the lip-deep hydroxyl of described inorganic oxide S are reacted, form empirical formula S (A-R-A)
nShown structure, n=1-20 in the formula, R is alkyl, aryl or the cycloalkyl that is selected from 1-20 carbon atom, the mol ratio of lip-deep hydroxyl of described inorganic oxide S and A-R-A compound is 1: 10-10: 1, with this mixture constant temperature after 4-6 hour, reduce to envrionment temperature, be formed in described surface and contain the carrier I that combines a kind of organo-functional group A on the inorganic oxide S of hydroxyl, use for next step load metallocene compound;
(2) the carrier I that also step (1) can be made is warming up to 80-200 ℃ again, adds a certain amount of another kind of organic compound B-R '-B of binary functional group at least that has, and itself and organo-functional group B are reacted, and forms empirical formula S (A-R-A)
n(B-R '-B).Shown structure, n=1-20 in the formula, R is alkyl, aryl or the cycloalkyl that is selected from 1-20 carbon atom, m=1-20, the alkyl or aryl that R ' replaces for alkyl, aryl, cycloalkyl or the heteroatoms that is selected from 1-50 carbon atom, the mol ratio of lip-deep organo-functional group A of described inorganic oxide S and organo-functional group B is 10: 1-1: 10, with this mixture constant temperature after 8 hours, reduce to envrionment temperature, be formed in described surface and contain the carrier II that combines more than one organo-functional groups on the inorganic oxide S of hydroxyl, use for next step load metallocene compound;
(3) carrier I that step (1) or (2) are made or II insert one and have in the preparation bottle of agitator, add a certain amount of toluene and make solvent, add formula LMX again
2Metallocene compound and a certain amount of methylaluminoxane, at formula LMX
2In, L is the cyclopentadiene or derivatives thereof, and M is the group vib metal that is selected from Ti, Zr or Hf, and X is a halogen, stirs 4 hours down at 40 ℃, takes out toluene then under vacuum, to the product drying, becomes free-flowing, obtains load metallocene catalyst thus; Perhaps
When b. the inorganic oxide S that contains hydroxyl when the surface is the inorganic oxide of any form of the tiny median size 0.1-200 nanometer of nano level,
(1) described inorganic oxide S is placed a rotary funace, add a certain amount of organic compound A-R-A of binary functional group at least that has simultaneously, oxygen in coming out of the stove with nitrogen replacement, use the nitrogen fluidisation, be warming up to 420-480 ℃ then, monobasic functional group A and the lip-deep hydroxyl of described inorganic oxide S are reacted, form empirical formula S (A-R-A)
nShown structure, n=1-20 in the formula, R is alkyl, aryl or the cycloalkyl that is selected from 1-20 carbon atom, this mixture constant temperature was cooled to envrionment temperature after 6 hours, nitrogen is preserved down, be formed in described surface and contain the carrier III that combines a kind of organo-functional group A on the inorganic oxide S of hydroxyl, use for next step load metallocene compound;
(2) the carrier III that also step (1) can be made is warming up to 80-200 ℃ again, adds a certain amount of another kind of organic compound B-R '-B of binary functional group at least that has, and itself and organo-functional group B are reacted, and forms empirical formula S (A-R-A)
n(B-R '-B).Shown structure, in the formula, n=1-20, R is alkyl, aryl or the cycloalkyl that is selected from 1-20 carbon atom, m=1-20, the alkyl or aryl that R ' replaces for alkyl, aryl, cycloalkyl or the heteroatoms that is selected from 1-50 carbon atom, under nitrogen atmosphere, this mixture constant temperature was cooled to envrionment temperature after 6 hours, nitrogen is preserved down, and being formed in described surface contains the carrier IV that combines more than one organo-functional groups on the inorganic oxide S of hydroxyl, uses for next step load metallocene compound;
(3) carrier that step (1) or (2) the are made different metallocene compound LMX of load respectively
2, L is the cyclopentadiene or derivatives thereof in the formula, and M is the group vib metal that is selected from Ti, Zr or Hf, and X is a halogen, and its method is:
Get a certain amount of carrier III or IV, add among the preparation bottle A of belt stirrer, add after a certain amount of toluene stirs, add a certain amount of methylaluminoxane, stirred 1 hour down, add a kind of metallocene compound, stirred 4 hours down at 45 ℃ at 40 ℃;
Get a certain amount of carrier III or IV again, add among the preparation bottle B of belt stirrer, with above-mentioned reinforced and operation, difference only is to add another kind of metallocene compound;
Get a certain amount of carrier III or IV again, add among the preparation bottle C of belt stirrer, with above-mentioned reinforced and operation, difference only is to add another metallocene compound;
(4) product that will prepare among bottle A, B and the C takes out, together add in the preparation bottle of another belt stirrer, stirred at ambient temperature 1 hour, boil off toluene solvant with nitrogen purging then, product in bottle becomes solid state, obtains load metallocene catalyst.
15. preparation method according to claim 14, wherein the inorganic oxide S that contains hydroxyl when the surface is that diameter 0.2-1000 micron class spheric is when having microporous inorganic oxides, in step (1), when the inorganic oxide S that described surface is contained hydroxyl places activation furnace, under nitrogen gas stream, be warming up to 420-500 ℃.
16. according to the preparation method of claim 14, the inorganic oxide S that hydroxyl is contained on wherein said surface is selected from SiO
2Or Al
2O
3
17. according to the preparation method of claim 14, wherein said have at least that the organic compound of binary functional group comprises: di-carboxylic acid class, two amines, two nitriles or glycols.
18. according to the preparation method of claim 17, wherein said have at least that the organic compound of binary functional group comprises: terephthalic acid, Ursol D, quadrol, ethylene glycol, butyleneglycol or succinonitrile.
19. according to the preparation method of claim 18, wherein said have at least that the organic compound of binary functional group is a terephthalic acid.
20. according to the preparation method of claim 14, wherein said LMX
2Comprise: CP
2ZrCl
2, (CH
3CP)
2ZrCl
2, (en) (Ind)
2ZrCl
2Or (Me
2Si) (1,4,7-Me
3Ind)
2ZrCl
2
21. have application in the olefin polymer of broad peak or bimodal molecular weight distribution in production according to each catalyzer of claim 1-13.
22. according to the application of claim 21, wherein said olefinic polymerization comprises: vinyl polymerization, propylene polymerization, ethylene-alpha-olefin polymerization or ethene and the copolymerization of alhpa olefin more than two kinds.
23. application according to claim 21, the size distribution of wherein said polymericular weight, recently realize by the mole of regulating several functional groups of bonded on a kind of carrier, perhaps by respectively behind the metallocene compound not of the same race of load on the tiny carrier of a few part nano levels remix realize.
24., wherein in described polyreaction, do not add or add less the hydrogen molecular weight regulator according to the application of claim 21.
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| CN1345887A (en) * | 2000-09-28 | 2002-04-24 | 中国石油化工股份有限公司 | Semi-metallocene supported polyvinyl catalyst and preparation method thereof |
| CN1353120A (en) * | 2000-11-03 | 2002-06-12 | 中国石油化工股份有限公司 | Metallocene catalyst for polymerizing or copolymerizing ethylene and its preparing process and application |
| CN1300786A (en) * | 2000-11-08 | 2001-06-27 | 中国石油天然气股份有限公司兰州石化分公司 | Metallocene catalyst for polymerizing olefine |
| CN1356343A (en) * | 2000-12-05 | 2002-07-03 | 中国石油化工股份有限公司 | Carried metallocene catalyst and its preparing process |
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| CN1490341A (en) | 2004-04-21 |
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