CN101798361B - Olefin polymerization catalysts - Google Patents
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- CN101798361B CN101798361B CN 201010108673 CN201010108673A CN101798361B CN 101798361 B CN101798361 B CN 101798361B CN 201010108673 CN201010108673 CN 201010108673 CN 201010108673 A CN201010108673 A CN 201010108673A CN 101798361 B CN101798361 B CN 101798361B
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Abstract
The invention relates to non-metallocene single active site olefin polymerization or copolymerization catalysts or a catalyst system, a synthesizing method for the catalysts and application in catalyzing olefin polymerization. The catalysts are polydentate ligand third or fourth group transition metal complexes and have the following structural formula that: the catalysts can be used in homopolymerization and copolymerization of olefin by a slurry packing method or a gas phase method of olefin under the condition of homogeneous phase or after the catalysts are loaded on a carrier.
Description
Technical field
The present invention relates to a class new olefine polymerization and copolymerization catalyst or catalyst system, synthetic method and the application aspect catalysis in olefine polymerization thereof.
Background technology
Since having found Ziegler-Natta catalyst from nineteen fifties, highly active MgCl
2The catalyzer of the titanium of load has shown good catalytic performance, (K.Ziegler, etc., Angew.Chem.1995,67,424; K.Ziegler etc., Angew.Chem.1995,67,541; N.Kashiwa etc., USP-3642746,1968) industrial at present, this catalyzer has been used for high density polyethylene(HDPE) (HDPE), linear low density polyethylene (LLDPE), the production of the polymkeric substance of syndiotactic polypropylene (i-pp).Yet the catalyzer in this many active centre can't well be controlled polymer architecture, performance by regulating catalyst structure at present.The discovery of the 4th family's metallocene catalyst has then solved this problem preferably, owing to have single active center, make people can obtain polymkeric substance (W.Kaminsky etc., the Adv.Organomet.Chem.1980 of expected structure as required by the structure that changes catalyzer, 18,99; W.Kaminsky etc., Angew.Chem., Int.Ed.Engl.1980,19,390; H.H.Brintzinger etc., Angew.Chem.Int.Ed.Engl.1995,34,1143).In recent ten years, also flourish as the research of olefin polymerization catalysis with the metal complexes that the part that contains ligating atoms such as N, O, P replaces cyclopentadiene and transition-metal coordination to obtain, this class catalyzer is collectively referred to as " luxuriant rear catalyst ", since nineteen ninety-five, have some new outstanding catalyzer to be synthesized out gradually, wherein representational early transition metal title complex has following several:
Summary of the invention
The invention provides a class new olefine polymerization and copolymerization catalyst or catalyst system, namely relate to a class for the catalyst system of the 3rd or 4 group 4 transition metal complexes of the polydentate ligand of olefinic polymerization.
The present invention also provides the synthetic method of above-mentioned catalyzer, comprises polydentate ligand and generates the synthetic method of metal complexes with the 3rd, 4 group 4 transition metals.
The present invention also provides the purposes of above-mentioned catalyzer, and this catalyst system is used for catalysis in olefine polymerization after can being directly used in catalysis in olefine polymerization or loadization, and alkene comprises ethene, alpha-olefin etc.
Olefinic polymerization provided by the invention and copolymerization catalyst are the described title complex of following structural formula (I):
The general further is elaborated to the structure of the represented transistion metal compound of above-mentioned general formula (I) below: in said structure:
(I) in the formula ...: be coordinate bond, covalent linkage or ionic linkage, also Cheng Jian not in the present invention;
(I) in the formula
Be singly-bound or two key;
(I) a in the formula and b are the integers of 1-30, the integer of 1-10 preferably, and the integer of 1-5 more preferably, wherein can equate also can be unequal for a and b;
Z: be 1,2 or 3;
N:2 or 3;
(I) M in the formula refers to the 3rd or 4 family's metals, and preferred the 4th group 4 transition metal is specifically as follows scandium, titanium, zirconium, hafnium, preferred titanium, zirconium, hafnium;
(I) D in the formula is oxygen, boron, aluminium, silicon, carbon, germanium or tin;
(I) R in the formula
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10Be hydrogen atom, C
1-C
30Alkyl, halogen atom, C
1-C
30Silica-based, the C of organic alkoxy
1-C
30The group that contains nitrogen, sulphur, oxygen, phosphorus, Siliciumatom and other safing function group, above-mentioned group is identical or different to each other, wherein adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
R
z: refer to z identical or different containing heteroatoms or do not contain heteroatomic R group, wherein adjacent group becomes ring or Cheng Jiancheng ring not each other in key, and R is C
1-C
30Alkyl, C
1-C
30Oxy radical, C
1-C
30Sulfur-containing group, C
1-C
30Nitrogen-containing group, C
1-C
30Boron-containing group, C
1-C
30Phosphorus-containing groups, C
1-C
30Contain aluminium base group, C
1-C
30Halogen group, C
1-C
30Silicon-containing group, C
1-C
30Germanic group, C
1-C
30Contain tin group or C
1-C
30Contain the heterogeneous ring compound residue;
Described C
1-C
30Alkyl refer to contain C
1-C
30Alkyl, C
3-C
30Cyclic group, C
2-C
30Group, the C of carbon-carbon double bonds
2-C
30Group, the C of carbon containing carbon triple bond
6-C
30Aryl radical or C
6-C
30Aryl radical, the C of replacement
8-C
30Condensed ring alkyl or C
4-C
30Heterogeneous ring compound;
Described C
6-C
30The substituted aroma alkyl refer to contain on the aryl radical one or more C
1-C
10Alkyl, halogen, C
1-C
10Alkoxyl group, C
1-C
10Amido, C
1-C
10Silica-based as substituted radical, contain in the process of compound of substituted hydrocarbon radical in use, these substituting groups are inertia, namely these substituting groups do not have substantial interference to related process; Described halogen refers to fluorine, chlorine, bromine or iodine.
(I) X in the formula is halogen, C
1-C
30Alkyl, C
1-C
30Oxy radical, C
1-C
30Nitrogen-containing group, C
1-C
30Boron-containing group, C
1-C
30Contain aluminium base group or C
1-C
30Silicon-containing group, several X are identical or different, become ring or Cheng Jiancheng ring not each other in key; (I) R in the formula
1-R
10Represented C
1-C
30Alkyl, can be exemplified below particularly:
C such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl
1-C
30, preferred C
1-C
20Straight chain or have the alkyl of side chain;
C such as vinyl, propenyl
1-C
30, preferred C
1-C
20Straight chain or have the thiazolinyl of side chain;
C such as ethynyl, proyl
1-C
30, preferred C
1-C
20Straight chain or have the alkynyl of side chain;
Cyclopropyl, cyclobutyl, cyclopentyl, C such as cyclohexyl, cyclobutadiene base, cyclopentadienyl
1-C
30, preferred C
1-C
20Contain substituting group or do not contain substituent cycloalkyl, cycloalkenyl group;
C such as phenyl, xenyl, naphthyl, phenanthryl, anthryl
6-C
30Group, preferably contain C
1-C
8The aryl radical that replaces of alkyl or do not contain substituent aromatic group, more preferably contain C
1-C
5The aryl radical that replaces of alkyl or do not contain substituent aromatic group;
The hydrogen atom of above-mentioned alkyl also can be replaced by halogen, for example C such as trifluoromethyl, trifluoroethyl, pentafluorophenyl group
1-C
30, preferred C
1-C
20Straight chain or have the halo alkyl of side chain;
In addition, above-mentioned alkyl can also be replaced by following groups: alkoxyl group, aryloxy, ester group, ether, carboxyl, carboxylic acid ester groups, hydroxyl, peroxy, acid anhydride, and heterogeneous ring compound residue etc. contains the oxygen base; Nitrogen-containing groups such as amino, imino-, amide group, diazanyl, hydrazono-, nitro, nitroso-group, cyano group, isocyano-, cyanate ester based, diazo, azido-, amidino groups, ammonium, ammonium salt; Boron-containing groups such as borane base, diborane base; Sulfur-containing groups such as sulfydryl, thioic acid sulfoacid ester group, dithio perester radical, alkylthio, arylthio; Phosphino-, phosphorus-containing groups such as phosphate-based; Silicon-containing group such as trimethyl silicon based, that triethyl is silica-based, triethoxy is silica-based; And the group of germanic or stanniferous.
Oxy radical refers to that substituting group contains alkoxyl group, as OMe, and OEt, O (CH)
5CH
3, CH
2OC
4H
9Deng;
Sulfur-containing group refers to contain sulfide based structural in the substituting group, as SMe, and SBu
i, CH
2SPr
i
C
1-C
30Boron-containing group refer to contain boron in the substituting group, and alkyl carbon number summation is no more than 30, as (C
6F
5)
4B
-
Contain aluminium base group and refer to contain in the substituting group aluminium element;
Phosphorus-containing groups refers to contain phosphine groups in the substituting group, as PPh
2, CH
2PPh
2
Nitrogen-containing group refers to contain in the substituting group nitrogen element;
Silicon-containing group refers to contain in the substituting group element silicon;
Contain element Ge in the germanic group substituting group;
Contain tin group and refer to contain in the substituting group tin element.
Described C
1-C
30The alkyl of replacement refer to contain on the alkyl one or more substituted radical, contain in the process of compound of substituted hydrocarbon radical in use, these substituting groups should not have substantial interference to related reaction process; Described halogen refers to fluorine, chlorine, bromine or iodine.
(I) in the formula all parts the absolute value of electronegative sum should be identical with the positively charged absolute value of metal M in the structural formula, all parts comprise X and polydentate ligand;
The synthetic method of catalyzer of the present invention is to arrive in the temperature range that refluxes at-78 ℃, catalyzer is to be respectively 1:0.1～6 an o'clock reaction by the negative ion metallizing thing of the part of following structural formula or part with mol ratio to obtain in 0.5-40 hour in organic solvent, prolongs the reaction times to not influence of reaction.Organic solvent can be tetrahydrofuran (THF), sherwood oil, toluene or methylene dichloride etc.
Wherein:
A and b are the integers of 1-30, the integer of 1-10 preferably, and the integer of 1-5 more preferably, wherein can equate also can be unequal for a and b;
Z: be 1,2 or 3;
R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10Be hydrogen atom, C
1-C
30Alkyl, halogen atom, C
1-C
30Silica-based, the C of organic alkoxy
1-C
30The group that contains nitrogen, sulphur, oxygen, phosphorus, Siliciumatom and other safing function group, above-mentioned group is identical or different to each other, wherein adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
D is oxygen, boron, aluminium, silicon, carbon, germanium or tin;
R
z: refer to z identical or different containing heteroatoms or do not contain heteroatomic R group, wherein adjacent group becomes ring or Cheng Jiancheng ring not each other in key, and R is C
1-C
30Alkyl, C
1-C
30Oxy radical, C
1-C
30Sulfur-containing group, C
1-C
30Nitrogen-containing group, C
1-C
30Boron-containing group, C
1-C
30Phosphorus-containing groups, C
1-C
30Contain aluminium base group, C
1-C
30Halogen group, C
1-C
30Silicon-containing group, C
1-C
30Germanic group, C
1-C
30Contain tin group or C
1-C
30Contain the heterogeneous ring compound residue;
Described C
1-C
30Alkyl refer to contain C
1-C
30Alkyl, C
3-C
30Cyclic group, C
2-C
30Group, the C of carbon-carbon double bonds
2-C
30Group, the C of carbon containing carbon triple bond
6-C
30Aryl radical or C
6-C
30Aryl radical, the C of replacement
8-C
30Condensed ring alkyl or C
4-C
30Heterogeneous ring compound;
Described C
6-C
30The substituted aroma alkyl refer to contain on the aryl radical one or more C
1-C
10Alkyl, halogen, C
1-C
10Alkoxyl group, C
1-C
10Amido, C
1-C
10Silica-based as substituted radical, contain in the process of compound of substituted hydrocarbon radical in use, these substituting groups are inertia, namely these substituting groups do not have substantial interference to related process; Described halogen refers to fluorine, chlorine, bromine or iodine.
Described compound can be under homogeneous phase condition, catalysis in olefine polymerization under the effect of promotor, also can load after promotor effect under catalysis in olefine polymerization.Concrete carrying method is as follows:
5%-50% with vehicle weight is dissolved in methylene dichloride or toluene with the represented transition metal complex of formula (I), join in the carrier then, stirred 1-3 hour in 30-80 ℃, methylene dichloride or toluene are removed with normal hexane the washing dry or direct decompression of final vacuum for several times in the filtration back, and with hexane wash for several times, the supported olefin polymerization catalyst that obtains good fluidity after the vacuum-drying is preserved standby.Described carrier refers to the complex carrier of silica gel, spherical magnesium chloride or silica gel and magnesium chloride, but the concrete preparation method of carrier also not only is confined to method that embodiment gives.
Purposes-the reaction of catalyzer, polymerization and polymerisate
The catalyzer of above-mentioned catalyzer of the present invention and loading type can be used for catalysis in olefine polymerization under the promotor effect, alkene comprises ethene, alpha-olefin etc., and alpha-olefin refers to C
3～C
18Terminal olefin, for example propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecylene, 1-vaccenic acid and its mixture etc.; Polymerization comprises the equal polymerization polymerization together of above-mentioned monomer.
Slurry polymerization, endless tube polymerization, vapour phase polymerization or other forms of polymerization technique are adopted in polymerization.
Polymerization is generally carried out in inert solvent, for example hydro carbons, cyclic hydrocar-bons or aromatic hydrocarbons.For being conducive to reactor operation and polymerisate, inert solvent can use the hydro carbons less than 12 carbon, is exemplified below but is not limited in this, hexane, toluene, chlorobenzene and composition thereof.
Polymerization temperature maintains 0 to 150 ℃, for reaching good catalytic activity and throughput, can maintain 20 to 120 ℃.
Polymerization pressure can change in 0.1 to 50MPa, and operation can obtain reactor operating parameters and polymkeric substance preferably in 0.1 to 10MPa.
Described promotor W is alkylaluminium cpd, alkylaluminoxane or weakly coordinating anion; Described alkylaluminium cpd is preferable over AlEt
3, AlMe
3Or Al (i-Bu)
3Alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta, MMAO (methylaluminoxane of modification) etc.; Weakly coordinating anion is preferable over [B (3,5-(CF
3)
2C
6H
3)
4]
-,-OSO
2CF
3Or ((3,5-(CF
3)
2) C
6H
3)
4B
-Catalyzer and promotor can any order adding system carry out polymerization.The variable-scale of the employed catalyzer of polymerization and promotor.Usually the mol ratio of catalyzer and promotor is 1: 1-5000, generally can be 1: 10-2000 be in order to make catalytic activity, polymer property and production cost all maintain other carbon containing functional groups that scope safing function group preferably refers to be different from alkyl and substituted hydrocarbon radical, this functional group is not to all there being substantive the interference in the reaction that may participate at the compound that contains this functional groups, here the indication functional groups comprises halogen, C
1-C
10Ester group, C
1-C
10Amido, C
1-C
10Alkoxyl group, C
1-C
10Oxy radicals such as nitro, C
1-C
10Nitrogen-containing group, C
1-C
10Silicon-containing group, C
1-C
10Germanic group, C
1-C
10Sulfur-containing group or C
1-C
10Contain tin group, when functional groups when the atoms metal, these functional groups should not replace desirable coordinating group;
In sum, the invention provides a kind of olefinic polymerization and copolymerization catalyst and catalyst system, preparation method and its usage, this catalyzer can under the effect of promotor in the equal polymerization polymerization together that is used for catalyzed ethylene, alpha-olefin etc. under the homogeneous phase condition or after the load.
Description of drawings
The ethene of Fig. 1 catalyst A 1 catalysis and the carbon of octene copolymer spectrum (deuterium is solvent for orthodichlorobenzene);
The SEM picture of the ethylene homo of (C2) catalysis behind Fig. 2 catalyst cupport;
The SEM picture of the ethene of (C2) catalysis and 1-hervene copolymer behind Fig. 3 catalyst cupport;
Specific implementation method
The following examples will better illustrate the present invention, but what need emphasize is that the present invention never only limits to content that this several embodiment explains.
Following examples have shown not ipsilateral of the present invention.Given embodiment comprises synthetic, metal complex synthetic of part, the load of catalyzer, converging operation, polymerizing condition and polymerisate.All operations comprises reaction, preparation and stores and all carry out that the Schlenk of employing standard operates under the inert atmosphere of drying.Titanium in the loaded catalyst (Ti) assay carries out on the OPTRMA-3000 inductive coupling plasma emission spectrograph at ICP-AES.Polymericular weight (M
w, M
n) and molecular weight distribution (PDI=M
w/ M
n) utilize Waters Alliance GPC2000 1,2, under 135 ℃, be that standard specimen is measured with the polystyrene in 4 trichlorobenzene (flow velocity 1.0mL/min).Polymkeric substance
13C-NMR composes on Varian XL-400MHz nuclear magnetic resonance analyser with D
4-o-dichlorobenzene is solvent, measures down at 110 ℃.Monomer insertion rate is according to document (J C Randall, JMS-Rev.Maromol.Chem.Phys.1989, C29 (2﹠amp altogether; 3), method 201-317) calculates.
Synthesizing of embodiment one ligand L 1
In the reaction flask of 100ml, add 1.22g (10.0mmol) salicylic aldehyde, 3.21g (10.0mmol) 1-triethoxy silica base-2-naphthylamines, 0.5ml Glacial acetic acid, the 30mL dehydrated alcohol, after being heated to backflow 12h, stopped reaction makes to be chilled to room temperature,-30 ℃ freezing, namely obtain product, with cold washing with alcohol for several times, obtain yellow crystals L11.1g (26%) after the drying.
Ultimate analysis: actual measurement (calculated value): C:65.08 (64.92); H:6.73 (6.40); N:3.53 (3.29)
Synthesizing of embodiment two ligand L 2
Obtain ligand L 2 according to the synthetic method similar to ligand L 1 by 3,5-di-tert-butyl salicylaldehyde and neighbour-trimethylsiloxy group aniline reaction.
Ultimate analysis: actual measurement (calculated value): C:72.83 (72.49); H:8.89 (8.87); N:3.69 (3.52)
Synthesizing of embodiment three ligand L 3
Obtain ligand L 3 according to the synthetic method similar to ligand L 1 by 3,5-di-tert-butyl salicylaldehyde and the 4-tertiary butyl-2-benzene boryl aniline reaction.
Ultimate analysis: actual measurement (calculated value): C:82.23 (82.11); H:8.94 (8.89); N:3.32 (3.09)
Synthesizing of embodiment four ligand L 4
Obtain ligand L 4 according to the synthetic method similar to ligand L 1 by 3,5-di-tert-butyl salicylaldehyde and the trimethyl silicon based aniline reaction of 2-.
Ultimate analysis: actual measurement (calculated value): C:75.89 (75.53); H:9.81 (9.24); N:3.91 (3.67)
Embodiment five ligand L 5～L13's is synthetic
Ligand L 5, L6, L7, L8, L9, L10, L11, L12, L13. have been synthesized respectively according to the synthetic method similar to ligand L 1
L5
Ultimate analysis: actual measurement (calculated value): C:66.12 (66.04); H:5.39 (5.28); N:3.54 (3.67)
L6
Ultimate analysis: actual measurement (calculated value): C:63.20 (63.81); H:7.36 (7.01); N:3.49 (3.90)
L7
Ultimate analysis: actual measurement (calculated value): C:75.87 (75.62); H:8.87 (8.83); N:3.69 (3.83)
L8
Ultimate analysis: actual measurement (calculated value): C:72.62 (72.41); H:8.67 (8.45); N:3.54 (3.67)
L9
Ultimate analysis: actual measurement (calculated value): C:75.83 (75.58); H:8.96 (8.82); N:3.49 (3.83)
L10
Ultimate analysis: actual measurement (calculated value): C:71.87 (71.33); H:7.78 (7.11); N:5.69 (5.20)
L11
Ultimate analysis: actual measurement (calculated value): C:71.56 (71.40); H:8.10 (7.99); N:3.18 (3.96)
L12
Ultimate analysis: actual measurement (calculated value): C:72.87 (72.45); H:8.78 (8.46); N:3.69 (3.67)
L13
Ultimate analysis: actual measurement (calculated value): C:61.19 (60.77); H:6.96 (6.71); N:4.05 (3.73)
Six layers of 486mg of embodiment (42%)
10ml tetrahydrofuran solution with 850mg (2.0mmol) ligand L 1 under-78 ℃ is added dropwise in the 10ml tetrahydrofuran (THF) of 79mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Vacuum desolventizes, and adds 40ml toluene, under the room temperature this negative solution is dropped to TiCl
4In the 10ml toluene solution of 379mg (2.0mmol), dropwise, continue under the room temperature and stir 12h.Centrifugal, the supernatant liquid desolventizing namely obtains thick product, obtains title complex A1 532mg (46%) with the toluene recrystallization.
Ultimate analysis: actual measurement (calculating) C:47.79 (47.73); H:4.61 (4.53); N:2.48 (2.42)
Embodiment seven
Obtain other title complex A2 (69%) with the experimental technique similar to title complex A1; A3 (22%); A4 (59%); A5 (71%); A6 (35%); A7 (53%); A8 (35%); A9 (32%); A10 (48%); A11 (74%); A12 (73%); A13 (65%).
The partial analysis data are as follows:
A9
Ultimate analysis: actual measurement (calculated value): C:53.72 (53.26); H:6.86 (6.02); N:2.89 (2.70)
A11
Ultimate analysis: actual measurement (calculated value): C:49.87 (49.80); H:5.56 (5.37); N:3.09 (2.77)
A12
Ultimate analysis: actual measurement (calculated value): C:51.91 (51.68); H:6.11 (5.85); N:2.61 (2.62)
A13
Ultimate analysis: actual measurement (calculated value): C:45.62 (45.47); H:4.40 (4.29); N:3.18 (3.31)
Embodiment eight
40ml tetrahydrofuran solution with 850mg (2.0mmol) ligand L 1 under-78 ℃ is added dropwise in the 15ml tetrahydrofuran (THF) of 80mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Under 50 ℃ this negative solution is dropped to ZrCl
4Among the 15ml THF of 2THF 755mg (2.0mmol), dropwise, continue to reflux to stir and spend the night.Vacuum desolventizes, and adds methylene dichloride 20ml and makes dissolving fully, and centrifugal, supernatant concentration adds a small amount of hexane, freezingly obtains thick product, obtains complex B 1423mg (34%) with the dichloromethane/hexane recrystallization.
Ultimate analysis: actual measurement (calculating) C:44.79 (44.40); H:4.61 (4.21); N:2.48 (2.25)
Embodiment nine
Obtain other complex B 2 (93%) with the experimental technique similar to complex B 1; B3 (26%); B4 (61%); B8 (21%); B9 (27%); B10 (75%);
The partial analysis data are as follows:
B2
Ultimate analysis: actual measurement (calculating) C:48.93 (48.51); H:5.84 (5.77); N:2.24 (2.36)
B3
Ultimate analysis: actual measurement (calculating) C:57.36 (57.28); H:6.48 (6.05); N:2.12 (2.15)
B4
Ultimate analysis: actual measurement (calculating) C:50.12 (49.85); H:5.95 (5.93); N:2.39 (2.42)
Embodiment ten
Under the ethene atmosphere of 0.1Mpa, successively toluene 30ml, MMAO (mol ratio of MMAO and catalyzer is 1000) are added in the polymerization bottle through taking out roasting 100ml, vigorous stirring places 50 ℃ of oil baths then, the constant temperature certain hour is with catalyst A 1, A2, A4, A6, A9, A11, A13, B1, B2, B4, B7, B11, (4 μ mol) toluene solution adds, and reacts after 15 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance gets polyethylene in 50 ℃ of vacuum-drying to constant weights after precipitation, filtration, washing.Ethylene homo result such as following table.
| Cat | W(g) | Activity (10 5g/mol·h) | M w | M w/M n | T m(℃) |
| A1 | 1.260 | 1.26 | 64606 | 2.02 | 129.3 |
| A2 | 1.099 | 1.10 | 135900 | 2.04 | 132.1 |
| A4 | 0.025 | 0.025 | 149563 | 1.93 | 132.4 |
| A6 | 1.393 | 1.39 | 90058 | 1.88 | 130.7 |
| A9 | 1.419 | 1.42 | 107386 | 2.14 | 129.9 |
| A11 | 1.361 | 1.36 | 117230 | 2.06 | 130.1 |
| A13 | 0.562 | 0.56 | 85982 | 2.05 | - |
| B1 | 0.846 | 0.85 | 16497 | 2.18 | - |
| B2 | 1.541 | 1.54 | 13652 | 2.19 | - |
| B4 | 1.037 | 1.04 | 20103 | 2.06 | - |
| B7 | 0.964 | 0.96 | 35648 | 2.14 | - |
| B11 | 0.698 | 0.70 | 76982 | 2.30 | - |
Annotate: Cat: catalyzer; W: polyethylene weight; Activity: activity; M
w: weight-average molecular weight; M
w/ M
n: molecular weight distribution; T
m: fusing point.
Embodiment 11
Under the ethene atmosphere of 0.1Mpa, successively toluene 30ml, hexene (10mmol), MMAO (mol ratio of MMAO and catalyzer is 1000) are added in the polymerization bottle through taking out roasting 100ml vigorous stirring, place 25 ℃ of oil baths then, the constant temperature certain hour is with catalyst A 1, A2, A3, A5, B3, B7 (4 μ mol) toluene solution adds, react after 15 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance gets the multipolymer of ethene and hexene in 50 ℃ of vacuum-drying to constant weights after precipitation, filtration, washing.Copolymerization result such as the following table of ethene and hexene.
| Cat | W(g) | Activity (10 4g/mol·h) | H％ b | M w | M w/M n | T m(℃) |
| A1 | 1.996 | 2.00 | 12.1 | 53660 | 2.27 | 104.4 |
| A2 | 0.600 | 0.60 | 3.6 | 189461 | 2.48 | 105.5 |
| A3 | 1.469 | 1.47 | 7.8 | 72862 | 2.22 | 108.7 |
| A5 | 1.276 | 1.28 | 9.2 | 64743 | 2.34 | 102.2 |
| B3 | 0.569 | 0.57 | 8.2 | 56298 | 2.06 | - |
| B7 | 0.502 | 0.50 | 10.5 | 35687 | 2.16 | - |
Annotate: Cat: catalyzer; W: multipolymer weight; Activity: activity; M
w: weight-average molecular weight; M
w/ M
n: molecular weight distribution; T
m: fusing point.
Embodiment 12
The activation of A, silica gel
Silica gel adopts slow heating schedule with the ES-70 type that Pq Corp. produces, and activates under stream of nitrogen gas.Temperature rise rate is 5 ℃/min, and 200 ℃ of following constant temperature 1 hour continues to be warming up to 400 ℃, and constant temperature 1h 600 ℃ of following constant temperature 6 hours, slowly cools to room temperature, the ES-70 type silica gel that obtains activating then at last under nitrogen gas stream.
The evenly preparation of complex compound carrier of B, magnesium chloride and alcohol.
(content of water and oxygen is lower than 5ppm) gets the 2.0g Magnesium Chloride Anhydrous under the anhydrous and oxygen-free nitrogen atmosphere, adds the absolute dehydrated alcohol of 20ml, stir and form suspension liquid, be warming up to 70 ℃, reacted 2 hours, magnesium chloride dissolves fully, forms the solution of homogeneous transparent, and keeping stirring velocity is 2000 rev/mins, slowly drip hexane, magnesium chloride and the complex compound of alcohol are slowly separated out, and with solid 50ml hexane wash 3 times of separating out, vacuum is drained solvent, obtain the carrier of good fluidity, be designated as Zt-1.
Get 0.5gZt-1, add the 5ml hexane, under agitation, add the 1.0ml titanium tetrachloride, be warming up to 60 ℃, stirring reaction 2h, desolventizing is used 20ml hexane wash three times, the Zt-1. that obtains activating
The preparation of the complex carrier that C, magnesium chloride and pure and mild silica gel form.
Under the anhydrous and oxygen-free nitrogen atmosphere (content of water and oxygen is lower than 5ppm), get the 2.0g Magnesium Chloride Anhydrous, add the absolute dehydrated alcohol of 20ml, stir and form suspension liquid, be warming up to 70 ℃, reacted 2 hours, magnesium chloride dissolves fully, form the solution of homogeneous transparent, add 4.0g silica gel, continue reaction 2 hours, keeping stirring velocity is 2000 rev/mins, slowly drip hexane, solid is slowly separated out, and with solid 50ml hexane wash 3 times of separating out, vacuum is drained solvent, obtain the carrier of good fluidity, be designated as Zt-2.
Get 0.5gZt-2, add the 5ml hexane, under agitation, add the 1.0ml titanium tetrachloride, be warming up to 60 ℃, stirring reaction 2h, desolventizing is used 20ml hexane wash three times, the Zt-2. that obtains activating
The load of D, catalyzer.
Take by weighing 0.05g metal complex A1, join in the 10ml toluene, stirring and dissolving under room temperature, and then join among the carrier Zt-1 of 5g activation, reaction is 2 hours under room temperature, and solvent removed in vacuo obtains the catalyzer of good fluidity, is designated as C-1.
Adopt similar method, take by weighing 0.05g metal complex A1, join in the 10ml toluene, stirring and dissolving under room temperature, and then join among the carrier Zt-2 of 5g activation, reaction is 2 hours under room temperature, solvent removed in vacuo obtains the catalyzer C-2 of good fluidity respectively.
Embodiment ten triethylene slurry polymerizations
The 2L stainless steel is stirred polymeric kettle N
2Replace three times, ethene displacement twice just contains AlEt
3700mL hexane solution (0.015M) add in the still, start stirring (rotating speed=150rpm), and temperature in the kettle is preheating to about 60 ℃ with water bath with thermostatic control.At N
2Protection down; successively a certain amount of monomer (not having other common monomers during ethylene homo) altogether and 20mg catalyzer (with the above-mentioned hexane solution flushing of 20mL) are joined in the polymeric kettle; shed the still internal pressure then; treat that temperature in the kettle rises to about 80 ℃; feed ethylene gas; make the still internal pressure reach 0.8MPa, after five minutes, mixing speed is risen to 250rpm.Bath temperature transfers to 85 ℃.Stop to feed ethene behind the polymerization 1h, with recirculated cooling water temperature in the kettle is down to below 50 ℃, the gas in the emptying system and discharging obtain granulated polymer after the drying.
Concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M
w(g/mol), molecular weight distribution polymerization result data such as (PDI) are listed in the table below.
| Catalyzer | Comonomer | Comonomer consumption (g) | Catalytic activity (g polymkeric substance/g catalyzer) | M w (10 4 g/mol) | PDI | Comonomer insertion rate (mol-%) | Polymer stacks density (g/cm 3) |
| C-1 | - | 0 | 12550 | 235 | - | - | 0.31 |
| C-2 | - | 0 | 11300 | 211 | - | - | 0.29 |
| C-1 | The 1-hexene | 50 | 11000 | 105 | 2.2 | 0.8 | 0.28 |
| C-2 | The 1-hexene | 50 | 9800 | 97 | 2.5 | 0.5 | 0.31 |
Claims (5)
1. a class olefin polymerization catalysis, the structure of described catalyzer is as follows:
2. an olefin polymerization catalysis as claimed in claim 1 is characterized in that in organic solvent ,-78 ℃ under the temperature that refluxes, synthetic with mol ratio 1: 0.1～6 reactions 0.5-40 hour by the negative ion metallizing thing of part or these parts;
Described metallic compound TiCl
4Or ZrCl
42THF;
The concrete structure of described part is as follows:
Wherein, the part negative ion refers to the compound after hydrogen on the phenolic hydroxyl group of above-mentioned part and KH reaction back is left away;
THF refers to tetrahydrofuran (THF).
3. the application of an olefin polymerization catalysis as claimed in claim 1, it is characterized in that under homogeneous phase condition or after the load under the promotor effect catalysis in olefine polymerization.
4. the application of olefin polymerization catalysis as claimed in claim 3 is characterized in that described promotor refers to alkylaluminium cpd or weakly coordinating anion.
5. the application of an olefin polymerization catalysis, it is characterized in that the catalyst dissolution described in the claim 1 in methylene dichloride or toluene, join again in the carrier, in 0-100 ℃ of stirring 1-3 hour, finish load after the desolventizing vacuum-drying and the catalyzer after the load is used for olefinic polymerization.
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| CN101942048B (en) * | 2010-09-21 | 2013-03-13 | 中国科学院上海有机化学研究所 | Supported non-metallocene polyolefin catalyst, preparation method and application |
| CN102443082B (en) * | 2010-10-15 | 2014-11-05 | 中国科学院上海有机化学研究所 | Novel chromium catalyst and application thereof in catalysis of olefin oligomerization and polymerization |
| CN103183624B (en) * | 2011-12-30 | 2017-04-19 | 中国科学院上海有机化学研究所 | Catalyst used for olefine polymerization or copolymerization and preparation method thereof |
| CN106317264B (en) * | 2015-07-01 | 2018-11-30 | 中国石化扬子石油化工有限公司 | A kind of support type MgCl2/TiCl4 catalyst and its preparation method and application with salicylic alidehyde imine type modifier modification |
| CN110327975B (en) * | 2019-06-06 | 2020-05-19 | 浙江新和成股份有限公司 | Hydroformylation catalyst, preparation method and application thereof |
| CN112724291B (en) * | 2019-10-28 | 2021-12-31 | 中国石油化工股份有限公司 | Ethylene homopolymerization method and ethylene homopolymer |
| CN112724163B (en) * | 2019-10-28 | 2021-12-31 | 中国石油化工股份有限公司 | Bisphenol metal complex and preparation method and application thereof |
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