CN102399315A - Supported non-metallocene catalyst and its preparation method and use - Google Patents
Supported non-metallocene catalyst and its preparation method and use Download PDFInfo
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- CN102399315A CN102399315A CN2010102859581A CN201010285958A CN102399315A CN 102399315 A CN102399315 A CN 102399315A CN 2010102859581 A CN2010102859581 A CN 2010102859581A CN 201010285958 A CN201010285958 A CN 201010285958A CN 102399315 A CN102399315 A CN 102399315A
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- 0 CCCCC1C*CC1 Chemical compound CCCCC1C*CC1 0.000 description 11
- WDNSDJNLXKBBGV-UHFFFAOYSA-N CC(C)(C)C(C1)C(O)=C(CNc(cccc2)c2Sc2ccccc2)C=C1C(C)(C)C Chemical compound CC(C)(C)C(C1)C(O)=C(CNc(cccc2)c2Sc2ccccc2)C=C1C(C)(C)C WDNSDJNLXKBBGV-UHFFFAOYSA-N 0.000 description 1
- YDMNRNQBTLECJZ-PPFNPFNJSA-N CC(C)(C)c(cc1C(C)(C)C)cc(/C=N/C(CCC=C2)=C2P(c2ccccc2)c2ccccc2)c1O Chemical compound CC(C)(C)c(cc1C(C)(C)C)cc(/C=N/C(CCC=C2)=C2P(c2ccccc2)c2ccccc2)c1O YDMNRNQBTLECJZ-PPFNPFNJSA-N 0.000 description 1
- UWIUYFUKPYTLMJ-MTDXEUNCSA-N CC(C)(C)c(cc1C(C)(C)C)cc(/C=N/c(cccc2)c2Sc2ccccc2)c1O Chemical compound CC(C)(C)c(cc1C(C)(C)C)cc(/C=N/c(cccc2)c2Sc2ccccc2)c1O UWIUYFUKPYTLMJ-MTDXEUNCSA-N 0.000 description 1
- OFWDYQMSNKRMLQ-UHFFFAOYSA-N CC(C)(C)c(cc1C(C)(C)C)cc(C=C)c1O Chemical compound CC(C)(C)c(cc1C(C)(C)C)cc(C=C)c1O OFWDYQMSNKRMLQ-UHFFFAOYSA-N 0.000 description 1
- OAWNLHYHBAVUHJ-UHFFFAOYSA-N Cc1ccccc1P(c1ccccc1)(c1ccccc1)=O Chemical compound Cc1ccccc1P(c1ccccc1)(c1ccccc1)=O OAWNLHYHBAVUHJ-UHFFFAOYSA-N 0.000 description 1
- FZRBUKHIEIDICR-RIYZIHGNSA-N [O-][N+](c(cc1/C=N/c(cccc2)c2P)ccc1O)=O Chemical compound [O-][N+](c(cc1/C=N/c(cccc2)c2P)ccc1O)=O FZRBUKHIEIDICR-RIYZIHGNSA-N 0.000 description 1
Abstract
The invention relates to a supported non-metallocene catalyst and its preparation method. The preparation method of the supported non-metallocene catalyst is an in-situ preparation method, is simple, is easy for operation, realizes control on non-metallocene content and has an obvious copolymerization effect. The invention also relates to a use of the supported non-metallocene catalyst in alkene homopolymerization/copolymerization. Compared with the prior art, the use of supported non-metallocene catalyst has the characteristics of high alkene catalysis activity, high polymer bulk density and controllable molecular weight distribution.
Description
Technical field
The present invention relates to a kind of non-metallocene catalyst.Particularly, the present invention relates to a kind of load type non-metallocene catalyst, its preparation method and the application in alkene homopolymerization/copolymerization thereof.
Background technology
The non-metallocene catalyst that middle and later periods nineteen nineties occurs; Claim luxuriant rear catalyst again; The central atom of Primary Catalysts has comprised nearly all transition metal; Reach at some aspect of performance, even surpass metallocene catalyst, become after Ziegler, Ziegler-Natta and metallocene catalyst the 4th generation olefin polymerization catalysis.By the excellent property of the polyolefin products of such catalyzer manufacturing, and low cost of manufacture.The non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus; Do not contain cyclopentadienyl group or its deriveding group,, it is characterized in that central ion has stronger Electron Affinities like indenyl and fluorenyl etc.; And have cis alkyl or halogen metal division center; Carry out alkene insertion and σ-key easily and shift, the easy alkylation of central metal helps the generation at cation activity center; The title complex that forms has the geometric configuration of qualification, stereoselectivity, electronegativity and chirality controllability, and in addition, formed metal-carbon key polarizes easily, more helps the polymerization and the copolymerization of alkene.Therefore, even under higher polymeric reaction temperature, also can obtain the olefin polymer of higher molecular weight.
But homogeneous catalyst has been proved it in olefinic polyreaction has the active duration weak point, glue still easily, promotor MAO consumption is high; And obtain the too low or too high weak point of polymericular weight; Only might be applied to the solution polymerization process or the high-pressure polymerization process of alkene, seriously limit its industrial applicability.
Patent ZL 01126323.7, ZL 02151294.9ZL 02110844.7 and WO 03/010207 disclose a kind of alkene homopolymerization/catalyst for copolymerization or catalystsystem; Has alkene homopolymerization/copolymerization performance widely; But need higher promotor consumption during in olefinic polymerization at the disclosed catalyzer of this patent or catalystsystem; Could obtain suitable olefin polymerizating activity, and it is short to exist active duration in the polymerization process, phenomenons such as the sticking still of polymkeric substance.
Common way is that non-metallocene catalyst is technological through certain loadization, processes loaded catalyst, thereby improves the polymerization of alkene and the particle form of resulting polymers.It shows as the initial activity that has suitably reduced catalyzer to a certain extent; Prolong the polymerization activity life-span of catalyzer; Reduce even avoided the caking in the polymerization process or gathered phenomenon cruelly, improve the form of polymkeric substance, improve the apparent density of polymkeric substance; Can make it satisfy more polymerization technique process, like vapour phase polymerization or slurry polymerization etc.
To patent ZL 01126323.7, ZL 02151294.9ZL 02110844.7 and the disclosed non-metallocene catalyst of WO03/010207, patent CN200310106156.x, CN200310106157.4, CN200410066070.3, CN200410066069.0,200510119401.x etc. provide multiple mode to carry out load to obtain load type non-metallocene catalyst.But these patents all relate to the Nonmetallocene organic cpds that contains transition metal are carried on the carrier after the processing, and catalyst preparation process is comparatively complicated.
The catalyzer that with the Magnesium Chloride Anhydrous is carrier demonstrates advantages of high catalytic activity in olefin polymerization process, but this type of catalyst strength is poor, and is broken easily in polymerization reactor, thereby causes polymer morphology bad.Silicon dioxide carried catalyzer has good flowability, can be used for slurry polymerization and gas fluidised bed polymerisation, but simple silicon dioxide carried metallocene and non-metallocene catalyst then show lower catalytic activity.Therefore, just possibly prepare and have high catalytic activity, the catalyzer of the controlled and good abrasion strength resistance of globule size if magnesium chloride and silicon-dioxide are well organically combined.
Patent 200610026765.8 discloses one type of single active center's Z-N olefin polymerization catalysis.This catalyzer as electron donor, handles through pretreated carrier (like silica gel), metallic compound (like titanium tetrachloride) and electron donor through in magnesium compound (like magnesium chloride)/tetrahydrofuran solution, adding that the back obtains with the salicylic alidehyde imine that contains coordinating group or substituted salicylic alidehyde imine verivate.
Patent 200610026766.2 is similar with it, discloses one type and has contained heteroatomic organic cpds and the application in Ziegler-Natta catalyst thereof.
Patent 200910180601.4 discloses a kind of preparation method of load type non-metallocene catalyst; It is that magnesium compound and Nonmetallocene title complex are dissolved in the solvent; Add porous support after drying, obtain load type non-metallocene catalyst through thermal activation treatment.Patent 200910180606.7 discloses a kind of preparation method of load type non-metallocene catalyst; It is that magnesium compound and Nonmetallocene title complex are dissolved in the solvent; Add through behind the porous support of thermal activation treatment; It is dry to add the washing of precipitation agent after-filtration again, obtains load type non-metallocene catalyst.What these two kinds of methods were all used is the porous support that thermal activation treatment is crossed; Though porous support through thermal activation treatment, dewaters and dehydroxylation, still contains the free hydroxyl of more amount on the surface; Follow-up load non-metallocene metal complexes is had a negative impact, limited its active performance.
Chinese patent 200910180100.6,200910180607.1,200910210988.3,200910210984.5,200910210987.9,200910210991.5 disclosed load type non-metallocene catalyst preparing methods and above-mentioned patent are similar; What all use is thermal activation treatment porous support of crossing and the magnesium compound solution reaction that contains Nonmetallocene part or Nonmetallocene title complex; React with the chemical processing agent that contains IVB family metallic compound more at last, obtain load type non-metallocene catalyst.
Chinese patent 200910180602.9 discloses a kind of preparation method of load type non-metallocene catalyst, and it is that magnesium compound and Nonmetallocene title complex are dissolved in the solvent, obtains load type non-metallocene catalyst after the drying.Patent 200910180605.2 discloses a kind of preparation method of load type non-metallocene catalyst, and it is that magnesium compound and Nonmetallocene title complex are dissolved in the solvent, adds the precipitation agent deposition, obtains load type non-metallocene catalyst after the filtration washing drying.What these two kinds of methods adopted is the magnesium compound carrier, the particle form of catalyzer is difficult to control, has limited the polymer beads form that polymerization thus obtains.
Patent 200910180603.3,200910180604.8,200910210989.8,200910210986.4,200910210985.X, 200910210990.0 disclosed load type non-metallocene catalyst preparing methods and above-mentioned patent are similar; What all use is that magnesium compound is as carrier; Still exist the particle form of catalyzer to be difficult to control, limited the polymer beads form that polymerization thus obtains.
Above patent all relates to the Nonmetallocene organometallic compound that contains transition metal is carried on the carrier after the processing; And because the carrier reaction bonded at non-metallocene catalyst and place is limited; The Nonmetallocene organic cpds mainly is to exist with the physical adsorption attitude in the load type non-metallocene catalyst that obtains, and is unfavorable for the control of polymer beads form and the performance of non-metallocene catalyst performance.
Patent CN200710162667.1, CN200710162676.0 and PCT/CN2008/001739 disclose a kind of magnesium compound load type non-metallocene catalyst and preparation method thereof; It adopts magnesium compound (like magnesium halide, alkyl magnesium, alkoxyl magnesium, alkyl alkoxy magnesium); Or magnesium compound passes through the modification magnesium compound that chemical treatment (treatment agent is aluminum alkyls, aluminum alkoxide) obtains; Or the modification magnesium compound that adopts magnesium compound-THF-alcohol to obtain through post precipitation is a carrier; Successively contact by various combination with active metallic compound with the Nonmetallocene part, and the original position load of accomplishing.Because magnesium compound as single carrier, causes the catalyzer physical strength low, in polymerization process, form fine polymer powder easily, influenced the steady running of polymerization production equipment.
Even so, the ubiquitous problem of the load type non-metallocene catalyst that exists in the prior art is that the load process is complicated.For the carrier loaded non-metallocene catalyst of porous support list; Carrier needs after thermal activation treatment to handle with the chemical reagent of its reaction with aluminum alkyls etc. again; Need strict control preparation condition for the carrier loaded non-metallocene catalyst of magnesium compound list, these two kinds of methods all are difficult to obtain good form polymkeric substance through olefinic polymerization.And the Nonmetallocene title complex is carried on the carrier, and part Nonmetallocene title complex is to pile up on carrier with physical adsorption way, both bonding forces a little less than, the Nonmetallocene title complex takes place and comes off and produce fine powder in polymerization process easily.And the composite carrier load non-metallocene catalyst that forms for porous support and magnesium compound; Such as Chinese patent 200410066068.6; And based on load method and a kind of carry type non-metallocene calalyst for polymerization of olefine, its preparation method and the application thereof of the disclosed a kind of high reactivity non-metallocene catalyst of the patent PCT/CN2005/001737 of its application; Because the existence of alcohol in the system; Can have a negative impact to load Nonmetallocene title complex performance on it, limit giving full play to of Nonmetallocene title complex intrinsic performance.
Therefore, present present situation is, still needs a kind of load type non-metallocene catalyst, and its preparation method is simple, is fit to suitability for industrialized production, and can overcomes those problems that exist in the prior art load type non-metallocene catalyst.
Summary of the invention
The inventor through diligent discovering, makes said load type non-metallocene catalyst through using a kind of specific preparation method on the basis of existing technology, in order to the solution foregoing problems, and has accomplished the present invention thus.
According to the preparation method of this load type non-metallocene catalyst, need not add proton donor and electron donor (such as in this area for this reason and the conventional diether compounds that uses) etc., also need not harsh reaction requirement and reaction conditions.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.
Particularly, the present invention relates to the content of following aspect:
1. the preparation method of a load type non-metallocene catalyst may further comprise the steps:
Make the chemical processing agent and optional porous support reaction, the step that obtains to modify carrier that are selected from IV B family metallic compound through thermal activation treatment;
Magnesium compound is dissolved in the solvent, obtains the step of magnesium compound solution;
Said modification carrier, said magnesium compound solution are contacted with the Nonmetallocene part, obtain the step of mixed serum;
In said mixed serum, add precipitation agent, obtain the step of complex carrier; With
Make the chemical processing agent and the reaction of said complex carrier that are selected from said IV B family metallic compound, obtain the step of said load type non-metallocene catalyst.
2. according to the aforementioned described preparation method in arbitrary aspect; It is characterized in that; Said porous support is selected from the refractory oxide or in infusibility composite oxides, clay, molecular sieve, mica, polynite, wilkinite and the zeyssatite one or more of partial cross-linked form, period of element Table II A, IIIA, IV A or the IV B family metal of olefin homo or multipolymer, Z 150PH or its multipolymer, Schardinger dextrins, polyester or copolyesters, polymeric amide or copolyamide, ryuron or multipolymer, Voncoat R 3310 or multipolymer, methylacrylic acid ester homopolymer or multipolymer, styrene homopolymers or multipolymer, these homopolymer or multipolymer; Be preferably selected from partial cross-linked styrene polymer, silicon-dioxide, aluminum oxide, Natural manganese dioxide, oxidation sial, oxidation magnalium, titanium oxide, molecular sieve and the polynite one or more, more preferably be selected from silicon-dioxide.
3. according to the aforementioned described preparation method in arbitrary aspect; It is characterized in that; Said magnesium compound is selected from one or more in magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and the alkyl alkoxy magnesium; Be preferably selected from the magnesium halide one or more, more preferably magnesium chloride.
4. according to the aforementioned described preparation method in arbitrary aspect, it is characterized in that said solvent is selected from C
6-12Aromatic hydrocarbon, halo C
6-12In aromatic hydrocarbon, ester and the ether one or more are preferably selected from C
6-12In aromatic hydrocarbon and the THF one or more, most preferably THF.
5. according to the aforementioned described preparation method in arbitrary aspect, it is characterized in that said Nonmetallocene part is selected from one or more in the compound with following chemical structural formula:
Be preferably selected from compound (A) with following chemical structural formula and in the compound (B) one or more:
More preferably be selected from compound (A-1) to compound (A-4) with following chemical structural formula and in compound (B-1) to the compound (B-4) one or more:
In above all chemical structural formulas,
Q is 0 or 1;
D is 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
-NR
23R
24,-N (O) R
25R
26,
-PR
28R
29,-P (O) R
30OR
31, sulfuryl, sulfoxide group or-Se (O) R
39, wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C
1-C
30Alkyl;
D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C
1-C
30Alkyl, sulfuryl, sulfoxide group,
-N (O) R
25R
26,
Or-P (O) R
32(OR
33), wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyanic acid, and wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, and wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
G is selected from C
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group;
Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, and wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyanic acid, and wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R
1To R
4, R
6To R
36, R
38And R
39Be selected from hydrogen, C independently of one another
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, is preferably formed aromatic ring; And
R
5Be selected from lone-pair electron on the nitrogen, hydrogen, C
1-C
30Alkyl, substituted C
1-C
30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; When Rw be oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R
5In N, O, S, P and Se can be used as coordination and carry out coordination with atom and said center IV B family atoms metal,
Said Nonmetallocene part further is preferably selected from one or more in the compound with following chemical structural formula:
Said Nonmetallocene part most preferably is selected from one or more in the compound with following chemical structural formula:
6. according to the aforementioned described preparation method in arbitrary aspect, it is characterized in that,
Said halogen is selected from F, Cl, Br or I;
Said nitrogen-containing group is selected from
-NR
23R
24,-T-NR
23R
24Or-N (O) R
25R
26
Said phosphorus-containing groups is selected from
-PR
28R
29,-P (O) R
30R
31Or-P (O) R
32(OR
33);
Said oxy radical be selected from hydroxyl ,-OR
34With-T-OR
34
Said sulfur-containing group is selected from-SR
35,-T-SR
35,-S (O) R
36Or-T-SO
2R
37
The said seleno group that contains is selected from-SeR
38,-T-SeR
38,-Se (O) R
39Or-T-Se (O) R
39
Said group T is selected from C
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group;
Said R
37Be selected from hydrogen, C
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group;
Said C
1-C
30Alkyl is selected from C
1-C
30Alkyl, C
7-C
50Alkaryl, C
7-C
50Aralkyl, C
3-C
30Cyclic alkyl, C
2-C
30Thiazolinyl, C
2-C
30Alkynyl, C
6-C
30Aryl, C
8-C
30Condensed ring radical or C
4-C
30Heterocyclic radical, wherein said heterocyclic radical contain 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;
Said substituted C
1-C
30Alkyl is selected from and has one or more aforementioned halogens or aforementioned C
1-C
30Alkyl is as substituent aforementioned C
1-C
30Alkyl;
Said safing function property group is selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, contains tin group, C
1-C
10Ester group and nitro,
Wherein, said silicon-containing group is selected from-SiR
42R
43R
44Or-T-SiR
45Said germanic group is selected from-GeR
46R
47R
48Or-T-GeR
49Saidly contain tin group and be selected from-SnR
50R
51R
52,-T-SnR
53Or-T-Sn (O) R
54Said R
42To R
54Be selected from hydrogen, aforementioned C independently of one another
1-C
30Alkyl, aforementioned substituted C
1-C
30Alkyl or aforementioned safing function property group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and said group T ditto defines.
7. according to the aforementioned described preparation method in arbitrary aspect, it is characterized in that, is 1 in the said magnesium compound of Mg element and the mol ratio of said Nonmetallocene part: 0.0001-1; Preferred 1: 0.0002-0.4, more preferably 1: 0.0008-0.2, further preferred 1: 0.001-0.1; The ratio of said magnesium compound and said solvent is 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml; In the said magnesium compound of magnesium compound solid and the mass ratio of said porous support is 1: 0.1-20, preferred 1: 0.5-10, more preferably 1: 1-5; The volume ratio of said precipitation agent and said solvent is 1: 0.2～5; Preferred 1: 0.5～2, more preferably 1: 0.8～1.5, and be respectively 1 in the said magnesium compound of Mg element independently of one another with mol ratio in the said chemical processing agent of IV B family metallic element: 0.01-1; Preferred 1: 0.01-0.50, more preferably 1: 0.10-0.30.
8. according to the aforementioned described preparation method in arbitrary aspect; It is characterized in that; Said IV B family metallic compound is selected from one or more in IV B family metal halide, IV B family metal alkyl compound, IV B family metal alkoxide compound, IV B family metal alkyl halides and the IV B family metal alkoxide halogenide; Be preferably selected from the IV B family metal halide one or more, more preferably be selected from TiCl
4, TiBr
4, ZrCl
4, ZrBr
4, HfCl
4And HfBr
4In one or more, most preferably be selected from TiCl
4And ZrCl
4In one or more.
9. according to the aforementioned described preparation method in arbitrary aspect; It is characterized in that; Said precipitation agent is selected from one or more in alkane, naphthenic hydrocarbon, halogenated alkane and the halo naphthenic hydrocarbon; Be preferably selected from pentane, hexane, heptane, octane, nonane, decane, hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane, methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane, three NBBs, chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, bromo cyclononane and the bromo cyclodecane one or more; Further be preferably selected from hexane, heptane, decane and the hexanaphthene one or more, most preferably hexane.
10. load type non-metallocene catalyst, it is by making according to each described preparation method of aspect 1-9.
11. alkene homopolymerization/copolymerization process; It is characterized in that; Being Primary Catalysts according to aspect 10 described load type non-metallocene catalysts; To be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is promotor, makes alkene homopolymerization or copolymerization.
12. an alkene homopolymerization/copolymerization process is characterized in that, may further comprise the steps:
According to each described preparation method of aspect 1-9 make load type non-metallocene catalyst and
With said load type non-metallocene catalyst is Primary Catalysts, is promotor to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more, makes alkene homopolymerization or copolymerization.
Technique effect
Preparing method's technology simple possible of load type non-metallocene catalyst of the present invention; The charge capacity of Nonmetallocene component is adjustable; Can give full play to itself and chemical processing agent reaction in generates and has the active Nonmetallocene title complex of olefinic polymerization catalysis component; And obtain the performance of polyolefin product at catalysis in olefine polymerization, and the polymerization catalyst activity is higher, and polymer stacks density is also higher.
Adopt method for preparing catalyst provided by the invention, owing to complex carrier is obtaining after the abundant post precipitation filtration washing drying under the precipitation agent effect through mixed slurry, so the combination of key substance is comparatively tight in the catalyzer.
Method for preparing catalyst provided by the invention and resulting thus load type non-metallocene catalyst; Wherein the Nonmetallocene part is with after IVB family metallochemistry treatment agent original position combines; The effect of the molecular weight distribution of narrowing is arranged; And therefore MWD that chemical processing agent has a wide fluidized polymer and the effectiveness that improves polymer stacks density can come the telomerized polymer structure properties through regulating the relative proportioning with the complex carrier chemical processing agent of Nonmetallocene part, such as MWD etc.
And, when employing load type non-metallocene catalyst that the present invention obtained and promotor constitute catalystsystem, show significant comonomer effect during copolymerization, promptly under equal relatively condition, the copolymerization activity is higher than the homopolymerization activity.
Embodiment
Following specific embodiments of the invention is elaborated, but it is pointed out that protection scope of the present invention does not receive the restriction of these embodiments, but is confirmed by claims of appendix.
The present invention relates to a kind of preparation method of load type non-metallocene catalyst, may further comprise the steps: make the chemical processing agent and optional porous support reaction, the step that obtains to modify carrier that are selected from IV B family metallic compound through thermal activation treatment; Magnesium compound is dissolved in the solvent, obtains the step of magnesium compound solution; Said modification carrier, said magnesium compound solution are contacted with the Nonmetallocene part, obtain the step of mixed serum; In said mixed serum, add precipitation agent, obtain the step of complex carrier; With make chemical processing agent and the reaction of said complex carrier that is selected from said IV B family metallic compound, obtain the step of said load type non-metallocene catalyst.
Below said porous support is carried out bright specifically.
According to the present invention, as said porous support, such as can enumerate this area when making supported olefin polymerization catalyst as carrier and conventional those organic or inorganic porosu solids that use.
Particularly; As said organic porosu solid; Such as enumerating olefin homo or multipolymer, Z 150PH or its multipolymer, Schardinger dextrins, (being total to) polyester, (being total to) polymeric amide, ryuron or multipolymer, Voncoat R 3310 or multipolymer, methylacrylic acid ester homopolymer or multipolymer; And styrene homopolymers or multipolymer etc.; And the partial cross-linked form of these homopolymer or multipolymer, wherein preferably partial cross-linked (such as degree of crosslinking be at least 2% but less than 100%) styrene polymer.
Embodiment preferred according to the present invention; Preferably on the surface of said organic porosu solid, have such as any one or the multiple active function groups that are selected from hydroxyl, primary amino, secondary amino group, sulfonic group, carboxyl, carboxamido-group, the mono-substituted carboxamido-group of N-, sulfoamido, the mono-substituted sulfoamido of N-, sulfydryl, acylimino and the hydrazide group wherein preferred carboxyl and hydroxyl.
According to an embodiment of the invention, before use said organic porosu solid is carried out thermal activation treatment.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under the inert atmosphere said organic porosu solid being carried out heat treated.Here said inert atmosphere be meant only contain extremely trace in the gas or do not contain can with the component of said organic porosu solid reaction.As said inert atmosphere, such as enumerating nitrogen or rare gas atmosphere, nitrogen atmosphere.Because the poor heat resistance of organic porosu solid, so this thermal activation process is with the structure of not destroying said organic porosu solid itself with basic composition is prerequisite.Usually, the temperature of this thermal activation is 50～400 ℃, preferred 100～250 ℃, and the thermal activation time is 1～24h, preferred 2～12h.After the thermal activation treatment, said organic porosu solid need be preserved subsequent use in malleation under the inert atmosphere.
As said inorganic porous solid; Such as the refractory oxide that can enumerate period of element Table II A, IIIA, IV A or IV B family metal (such as silicon-dioxide (being called silicon oxide or silica gel again), aluminum oxide, Natural manganese dioxide, titanium oxide, zirconium white or Thorotrast etc.); Perhaps any infusibility composite oxides of these metals (such as oxidation sial, oxidation magnalium, titanium oxide silicon, titanium oxide magnesium and titanium oxide aluminium etc.), and clay, molecular sieve (such as ZSM-5 and MCM-41), mica, polynite, wilkinite and zeyssatite etc.As said inorganic porous solid, can also enumerate the oxide compound that generates through pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound, such as the silica gel that obtains by the silicon tetrachloride pyrohydrolysis, the aluminum oxide that perhaps obtains etc. by the aluminum chloride pyrohydrolysis.
As said inorganic porous solid, preferred silicon-dioxide, aluminum oxide, Natural manganese dioxide, oxidation sial, oxidation magnalium, titanium oxide silicon, titanium oxide, molecular sieve and polynite etc., preferred especially silicon-dioxide.
According to the present invention; Suitable silicon-dioxide can pass through the ordinary method manufacturing; It perhaps can be the commerical prod that to buy arbitrarily; Such as the Grace that can enumerate Grace company 955, Grace948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245 and Aerosil812, the ES70 of Ineos company, ES70X, ES70Y, ES70W, ES757, EP 10X and EP11, and CS-2133 of Pq Corp. and MS-3040.
Embodiment preferred according to the present invention preferably has hydroxyl isoreactivity functional group on said inorganic porous solid surface.
According to the present invention, in one embodiment, before use said inorganic porous solid is carried out thermal activation treatment.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under the inert atmosphere said inorganic porous solid being carried out heat treated.Here said inert atmosphere be meant only contain extremely trace in the gas or do not contain can with the component of said inorganic porous solid reaction.As said inert atmosphere, such as enumerating nitrogen or rare gas atmosphere, nitrogen atmosphere.Usually, the temperature of this thermal activation is 200-800 ℃, and preferred 400～700 ℃, most preferably 400～650 ℃, heat-up time is such as being 0.5～24h, preferred 2～12h, most preferably 4～8h.After the thermal activation treatment, said inorganic porous solid need be preserved subsequent use in malleation under the inert atmosphere.
According to the present invention, the surface-area of said porous support is not had special qualification, but be generally 10～1000m
2/ g (BET method mensuration), preferred 100～600m
2/ g; The pore volume of this porous support (determination of nitrogen adsorption) is generally 0.1～4cm
3/ g, preferred 0.2～2cm
3/ g, and preferred 1～500 μ m of its median size (laser particle analyzer mensuration), more preferably 1～100 μ m.
According to the present invention, said porous support can be a form arbitrarily, such as micropowder, granular, spherical, aggregate or other form.
Below said chemical processing agent is carried out bright specifically.
According to the present invention, with IV B family metallic compound as said chemical processing agent.
As said IV B family metallic compound, such as enumerating IV B family metal halide, IV B family metal alkyl compound, IV B family metal alkoxide compound, IV B family metal alkyl halides and IV B family metal alkoxide halogenide.
As said IV B family metal halide, said IV B family metal alkyl compound, said IV B family metal alkoxide compound, said IV B family's metal alkyl halides and said IV B family metal alkoxide halogenide, such as the compound that can enumerate following general formula (IV) structure:
M(OR
1)
mX
nR
2 4-m-n (IV)
Wherein:
M is 0,1,2,3 or 4;
N is 0,1,2,3 or 4;
M is an IV B family metal in the periodic table of elements, such as titanium, zirconium and hafnium etc.;
X is a halogen, such as F, Cl, Br and I etc.; And
R
1And R
2Be selected from C independently of one another
1-10Alkyl is such as methyl, ethyl, propyl group, normal-butyl, isobutyl-etc., R
1And R
2Can be identical, also can be different.
Particularly, as said IV B family metal halide, such as enumerating titanium tetrafluoride (TiF
4), titanium tetrachloride (TiCl
4), titanium tetrabromide (TiBr
4), titanium tetra iodide (TiI
4);
Zirconium tetrafluoride (ZrF
4), zirconium tetrachloride (ZrCl
4), tetrabormated zirconium (ZrBr
4), zirconium tetraiodide (ZrI
4);
Tetrafluoride hafnium (HfF
4), hafnium tetrachloride (HfCl
4), hafnium (HfBr
4), tetraiodide hafnium (HfI
4).
As said IV B family metal alkyl compound, such as enumerating tetramethyl-titanium (Ti (CH
3)
4), tetraethyl-titanium (Ti (CH
3CH
2)
4), four isobutyl-titanium (Ti (i-C
4H
9)
4), tetra-n-butyl titanium (Ti (C
4H
9)
4), triethyl methyltitanium (Ti (CH
3) (CH
3CH
2)
3), diethyl-dimethyl titanium (Ti (CH
3)
2(CH
3CH
2)
2), trimethylammonium ethyl titanium (Ti (CH
3)
3(CH
3CH
2)), triisobutyl methyltitanium (Ti (CH
3) (i-C
4H
9)
3), diisobutyl dimethyl-titanium (Ti (CH
3)
2(i-C
4H
9)
2), trimethylammonium isobutyl-titanium (Ti (CH
3)
3(i-C
4H
9)), triisobutyl ethyl titanium (Ti (CH
3CH
2) (i-C
4H
9)
3), diisobutyl diethylammonium titanium (Ti (CH
3CH
2)
2(i-C
4H
9)
2), triethyl isobutyl-titanium (Ti (CH
3CH
2)
3(i-C
4H
9)), three normal-butyl methyltitanium (Ti (CH
3) (C
4H
9)
3), di-n-butyl dimethyl-titanium (Ti (CH
3)
2(C
4H
9)
2), trimethylammonium normal-butyl titanium (Ti (CH
3)
3(C
4H
9)), three normal-butyl methyltitanium (Ti (CH
3CH
2) (C
4H
9)
3), di-n-butyl diethylammonium titanium (Ti (CH
3CH
2)
2(C
4H
9)
2), triethyl normal-butyl titanium (Ti (CH
3CH
2)
3(C
4H
9)) etc.;
Tetramethyl-zirconium (Zr (CH
3)
4), tetraethyl-zirconium (Zr (CH
3CH
2)
4), four isobutyl-zirconium (Zr (i-C
4H
9)
4), tetra-n-butyl zirconium (Zr (C
4H
9)
4), triethyl methylcyclopentadienyl zirconium (Zr (CH
3) (CH
3CH
2)
3), diethyl-dimethyl zirconium (Zr (CH
3)
2(CH
3CH
2)
2), trimethylammonium ethyl zirconium (Zr (CH
3)
3(CH
3CH
2)), triisobutyl methylcyclopentadienyl zirconium (Zr (CH
3) (i-C
4H
9)
3), diisobutyl zirconium dimethyl (Zr (CH
3)
2(i-C
4H
9)
2), trimethylammonium isobutyl-zirconium (Zr (CH
3)
3(i-C
4H
9)), triisobutyl ethyl zirconium (Zr (CH
3CH
2) (i-C
4H
9)
3), diisobutyl diethylammonium zirconium (Zr (CH
3CH
2)
2(i-C
4H
9)
2), triethyl isobutyl-zirconium (Zr (CH
3CH
2)
3(i-C
4H
9)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH
3) (C
4H
9)
3), di-n-butyl zirconium dimethyl (Zr (CH
3)
2(C
4H
9)
2), trimethylammonium normal-butyl zirconium (Zr (CH
3)
3(C
4H
9)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH
3CH
2) (C
4H
9)
3), di-n-butyl diethylammonium zirconium (Zr (CH
3CH
2)
2(C
4H
9)
2), triethyl normal-butyl zirconium (Zr (CH
3CH
2)
3(C
4H
9)) etc.;
Tetramethyl-hafnium (Hf (CH
3)
4), tetraethyl-hafnium (Hf (CH
3CH
2)
4), four isobutyl-hafnium (Hf (i-C
4H
9)
4), tetra-n-butyl hafnium (Hf (C
4H
9)
4), triethyl methylcyclopentadienyl hafnium (Hf (CH
3) (CH
3CH
2)
3), diethyl-dimethyl hafnium (Hf (CH
3)
2(CH
3CH
2)
2), trimethylammonium ethyl hafnium (Hf (CH
3)
3(CH
3CH
2)), triisobutyl methylcyclopentadienyl hafnium (Hf (CH
3) (i-C
4H
9)
3), diisobutyl dimethyl-hafnium (Hf (CH
3)
2(i-C
4H
9)
2), trimethylammonium isobutyl-hafnium (Hf (CH
3)
3(i-C
4H
9)), triisobutyl ethyl hafnium (Hf (CH
3CH
2) (i-C
4H
9)
3), diisobutyl diethylammonium hafnium (Hf (CH
3CH
2)
2(i-C
4H
9)
2), triethyl isobutyl-hafnium (Hf (CH
3CH
2)
3(i-C
4H
9)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH
3) (C
4H
9)
3), di-n-butyl dimethyl-hafnium (Hf (CH
3)
2(C
4H
9)
2), trimethylammonium normal-butyl hafnium (Hf (CH
3)
3(C
4H
9)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH
3CH
2) (C
4H
9)
3), di-n-butyl diethylammonium hafnium (Hf (CH
3CH
2)
2(C
4H
9)
2), triethyl normal-butyl hafnium (Hf (CH
3CH
2)
3(C
4H
9)) etc.
As said IV B family metal alkoxide compound, such as enumerating tetramethoxy titanium (Ti (OCH
3)
4), purity titanium tetraethoxide (Ti (OCH
3CH
2)
4), four isobutoxy titanium (Ti (i-OC
4H
9)
4), four titanium n-butoxide (Ti (OC
4H
9)
4), triethoxy methoxyl group titanium (Ti (OCH
3) (OCH
3CH
2)
3), diethoxy dimethoxy titanium (Ti (OCH
3)
2(OCH
3CH
2)
2), trimethoxy ethanolato-titanium (Ti (OCH
3)
3(OCH
3CH
2)), three isobutoxy methoxyl group titanium (Ti (OCH
3) (i-OC
4H
9)
3), two isobutoxy dimethoxy titanium (Ti (OCH
3)
2(i-OC
4H
9)
2), trimethoxy isobutoxy titanium (Ti (OCH
3)
3(i-OC
4H
9)), three isobutoxy ethanolato-titanium (Ti (OCH
3CH
2) (i-OC
4H
9)
3), two isobutoxy diethoxy titanium (Ti (OCH
3CH
2)
2(i-OC
4H
9)
2), triethoxy isobutoxy titanium (Ti (OCH
3CH
2)
3(i-OC
4H
9)), three n-butoxy methoxyl group titanium (Ti (OCH
3) (OC
4H
9)
3), two n-butoxy dimethoxy titanium (Ti (OCH
3)
2(OC
4H
9)
2), trimethoxy titanium n-butoxide (Ti (OCH
3)
3(OC
4H
9)), three n-butoxy methoxyl group titanium (Ti (OCH
3CH
2) (OC
4H
9)
3), two n-butoxy diethoxy titanium (Ti (OCH
3CH
2)
2(OC
4H
9)
2), triethoxy titanium n-butoxide (Ti (OCH
3CH
2)
3(OC
4H
9)) etc.;
Tetramethoxy zirconium (Zr (OCH
3)
4), tetraethoxy zirconium (Zr (OCH
3CH
2)
4), four isobutoxy zirconium (Zr (i-OC
4H
9)
4), four n-butoxy zirconium (Zr (OC
4H
9)
4), triethoxy methoxyl group zirconium (Zr (OCH
3) (OCH
3CH
2)
3), diethoxy dimethoxy zirconium (Zr (OCH
3)
2(OCH
3CH
2)
2), trimethoxy oxyethyl group zirconium (Zr (OCH
3)
3(OCH
3CH
2)), three isobutoxy methoxyl group zirconium (Zr (OCH
3) (i-OC
4H
9)
3), two isobutoxy dimethoxy zirconium (Zr (OCH
3)
2(i-OC
4H
9)
2), trimethoxy isobutoxy zirconium (Zr (OCH
3)
3(i-C
4H
9)), three isobutoxy oxyethyl group zirconium (Zr (OCH
3CH
2) (i-OC
4H
9)
3), two isobutoxy diethoxy zirconium (Zr (OCH
3CH
2)
2(i-OC
4H
9)
2), triethoxy isobutoxy zirconium (Zr (OCH
3CH
2)
3(i-OC
4H
9)), three n-butoxy methoxyl group zirconium (Zr (OCH
3) (OC
4H
9)
3), two n-butoxy dimethoxy zirconium (Zr (OCH
3)
2(OC
4H
9)
2), trimethoxy n-butoxy zirconium (Zr (OCH
3)
3(OC
4H
9)), three n-butoxy methoxyl group zirconium (Zr (OCH
3CH
2) (OC
4H
9)
3), two n-butoxy diethoxy zirconium (Zr (OCH
3CH
2)
2(OC
4H
9)
2), triethoxy n-butoxy zirconium (Zr (OCH
3CH
2)
3(OC
4H
9)) etc.;
Tetramethoxy hafnium (Hf (OCH
3)
4), tetraethoxy hafnium (Hf (OCH
3CH
2)
4), four isobutoxy hafnium (Hf (i-OC
4H
9)
4), four n-butoxy hafnium (Hf (OC
4H
9)
4), triethoxy methoxyl group hafnium (Hf (OCH
3) (OCH
3CH
2)
3), diethoxy dimethoxy hafnium (Hf (OCH
3)
2(OCH
3CH
2)
2), trimethoxy oxyethyl group hafnium (Hf (OCH
3)
3(OCH
3CH
2)), three isobutoxy methoxyl group hafnium (Hf (OCH
3) (i-OC
4H
9)
3), two isobutoxy dimethoxy hafnium (Hf (OCH
3)
2(i-OC
4H
9)
2), trimethoxy isobutoxy hafnium (Hf (OCH
3)
3(i-OC
4H
9)), three isobutoxy oxyethyl group hafnium (Hf (OCH
3CH
2) (i-OC
4H
9)
3), two isobutoxy diethoxy hafnium (Hf (OCH
3CH
2)
2(i-OC
4H
9)
2), triethoxy isobutoxy hafnium (Hf (OCH
3CH
2)
3(i-C
4H
9)), three n-butoxy methoxyl group hafnium (Hf (OCH
3) (OC
4H
9)
3), two n-butoxy dimethoxy hafnium (Hf (OCH
3)
2(OC
4H
9)
2), trimethoxy n-butoxy hafnium (Hf (OCH
3)
3(OC
4H
9)), three n-butoxy methoxyl group hafnium (Hf (OCH
3CH
2) (OC
4H
9)
3), two n-butoxy diethoxy hafnium (Hf (OCH
3CH
2)
2(OC
4H
9)
2), triethoxy n-butoxy hafnium (Hf (OCH
3CH
2)
3(OC
4H
9)) etc.
As said IV B family metal alkyl halides, such as enumerating trimethylammonium titanium chloride (TiCl (CH
3)
3), triethyl titanium chloride (TiCl (CH
3CH
2)
3), triisobutyl titanium chloride (TiCl (i-C
4H
9)
3), three normal-butyl chlorination titanium (TiCl (C
4H
9)
3), dimethyl-titanium dichloride (TiCl
2(CH
3)
2), diethylammonium titanium dichloride (TiCl
2(CH
3CH
2)
2), diisobutyl titanium dichloride (TiCl
2(i-C
4H
9)
2), three normal-butyl chlorination titanium (TiCl (C
4H
9)
3), methyl titanous chloride (Ti (CH
3) Cl
3), ethyl titanous chloride (Ti (CH
3CH
2) Cl
3), isobutyl-titanous chloride (Ti (i-C
4H
9) Cl
3), normal-butyl titanous chloride (Ti (C
4H
9) Cl
3);
Trimethylammonium titanium bromide (TiBr (CH
3)
3), triethyl titanium bromide (TiBr (CH
3CH
2)
3), triisobutyl titanium bromide (TiBr (i-C
4H
9)
3), three normal-butyl bromination titanium (TiBr (C
4H
9)
3), dimethyl-dibrominated titanium (TiBr
2(CH
3)
2), diethylammonium dibrominated titanium (TiBr
2(CH
3CH
2)
2), diisobutyl dibrominated titanium (TiBr
2(i-C
4H
9)
2), three normal-butyl bromination titanium (TiBr (C
4H
9)
3), methyl titanium tribromide (Ti (CH
3) Br
3), ethyl titanium tribromide (Ti (CH
3CH
2) Br
3), isobutyl-titanium tribromide (Ti (i-C
4H
9) Br
3), normal-butyl titanium tribromide (Ti (C
4H
9) Br
3);
Trimethylammonium zirconium chloride (ZrCl (CH
3)
3), triethyl zirconium chloride (ZrCl (CH
3CH
2)
3), triisobutyl zirconium chloride (ZrCl (i-C
4H
9)
3), three normal-butyl chlorination zirconium (ZrCl (C
4H
9)
3), dimethyl-zirconium dichloride (ZrCl
2(CH
3)
2), diethylammonium zirconium dichloride (ZrCl
2(CH
3CH
2)
2), diisobutyl zirconium dichloride (ZrCl
2(i-C
4H
9)
2), three normal-butyl chlorination zirconium (ZrCl (C
4H
9)
3), methyl tri-chlorination zirconium (Zr (CH
3) Cl
3), ethyl tri-chlorination zirconium (Zr (CH
3CH
2) Cl
3), isobutyl-tri-chlorination zirconium (Zr (i-C
4H
9) Cl
3), normal-butyl tri-chlorination zirconium (Zr (C
4H
9) Cl
3);
Trimethylammonium zirconium bromide (ZrBr (CH
3)
3), triethyl zirconium bromide (ZrBr (CH
3CH
2)
3), triisobutyl zirconium bromide (ZrBr (i-C
4H
9)
3), three normal-butyl bromination zirconium (ZrBr (C
4H
9)
3), dimethyl-dibrominated zirconium (ZrBr
2(CH
3)
2), diethylammonium dibrominated zirconium (ZrBr
2(CH
3CH
2)
2), diisobutyl dibrominated zirconium (ZrBr
2(i-C
4H
9)
2), three normal-butyl bromination zirconium (ZrBr (C
4H
9)
3), methyl tribromide zirconium (Zr (CH
3) Br
3), ethyl tribromide zirconium (Zr (CH
3CH
2) Br
3), isobutyl-tribromide zirconium (Zr (i-C
4H
9) Br
3), normal-butyl tribromide zirconium (Zr (C
4H
9) Br
3);
Trimethylammonium hafnium chloride (HfCl (CH
3)
3), triethyl hafnium chloride (HfCl (CH
3CH
2)
3), triisobutyl hafnium chloride (HfCl (i-C
4H
9)
3), three normal-butyl chlorination hafnium (HfCl (C
4H
9)
3), dimethyl-hafnium dichloride (HfCl
2(CH
3)
2), diethylammonium hafnium dichloride (HfCl
2(CH
3CH
2)
2), diisobutyl hafnium dichloride (HfCl
2(i-C
4H
9)
2), three normal-butyl chlorination hafnium (HfCl (C
4H
9)
3), methyl tri-chlorination hafnium (Hf (CH
3) Cl
3), ethyl tri-chlorination hafnium (Hf (CH
3CH
2) Cl
3), isobutyl-tri-chlorination hafnium (Hf (i-C
4H
9) Cl
3), normal-butyl tri-chlorination hafnium (Hf (C
4H
9) Cl
3);
Trimethylammonium bromination hafnium (HfBr (CH
3)
3), triethyl bromination hafnium (HfBr (CH
3CH
2)
3), triisobutyl bromination hafnium (HfBr (i-C
4H
9)
3), three normal-butyl bromination hafnium (HfBr (C
4H
9)
3), dimethyl-dibrominated hafnium (HfBr
2(CH
3)
2), diethylammonium dibrominated hafnium (HfBr
2(CH
3CH
2)
2), diisobutyl dibrominated hafnium (HfBr
2(i-C
4H
9)
2), three normal-butyl bromination hafnium (HfBr (C
4H
9)
3), methyl tribromide hafnium (Hf (CH
3) Br
3), ethyl tribromide hafnium (Hf (CH
3CH
2) Br
3), isobutyl-tribromide hafnium (Hf (i-C
4H
9) Br
3), normal-butyl tribromide hafnium (Hf (C
4H
9) Br
3).
As said IV B family metal alkoxide halogenide, such as enumerating trimethoxy titanium chloride (TiCl (OCH
3)
3), triethoxy titanium chloride (TiCl (OCH
3CH
2)
3), three isobutoxy titanium chloride (TiCl (i-OC
4H
9)
3), three n-butoxy titanium chloride (TiCl (OC
4H
9)
3), dimethoxy titanium dichloride (TiCl
2(OCH
3)
2), diethoxy titanium dichloride (TiCl
2(OCH
3CH
2)
2), two isobutoxy titanium dichloride (TiCl
2(i-OC
4H
9)
2), three n-butoxy titanium chloride (TiCl (OC
4H
9)
3), methoxyl group titanous chloride (Ti (OCH
3) Cl
3), oxyethyl group titanous chloride (Ti (OCH
3CH
2) Cl
3), isobutoxy titanous chloride (Ti (i-C
4H
9) Cl
3), n-butoxy titanous chloride (Ti (OC
4H
9) Cl
3);
Trimethoxy titanium bromide (TiBr (OCH
3)
3), triethoxy titanium bromide (TiBr (OCH
3CH
2)
3), three isobutoxy titanium bromide (TiBr (i-OC
4H
9)
3), three n-butoxy titanium bromide (TiBr (OC
4H
9)
3), dimethoxy dibrominated titanium (TiBr
2(OCH
3)
2), diethoxy dibrominated titanium (TiBr
2(OCH
3CH
2)
2), two isobutoxy dibrominated titanium (TiBr
2(i-OC
4H
9)
2), three n-butoxy titanium bromide (TiBr (OC
4H
9)
3), methoxyl group titanium tribromide (Ti (OCH
3) Br
3), oxyethyl group titanium tribromide (Ti (OCH
3CH
2) Br
3), isobutoxy titanium tribromide (Ti (i-C
4H
9) Br
3), n-butoxy titanium tribromide (Ti (OC
4H
9) Br
3);
Trimethoxy zirconium chloride (ZrCl (OCH
3)
3), triethoxy zirconium chloride (ZrCl (OCH
3CH
2)
3), three isobutoxy zirconium chloride (ZrCl (i-OC
4H
9)
3), three n-butoxy zirconium chloride (ZrCl (OC
4H
9)
3), dimethoxy zirconium dichloride (ZrCl
2(OCH
3)
2), diethoxy zirconium dichloride (ZrCl
2(OCH
3CH
2)
2), two isobutoxy zirconium dichloride (ZrCl
2(i-OC
4H
9)
2), three n-butoxy zirconium chloride (ZrCl (OC
4H
9)
3), methoxyl group tri-chlorination zirconium (Zr (OCH
3) Cl
3), oxyethyl group tri-chlorination zirconium (Zr (OCH
3CH
2) Cl
3), isobutoxy tri-chlorination zirconium (Zr (i-C
4H
9) Cl
3), n-butoxy tri-chlorination zirconium (Zr (OC
4H
9) Cl
3);
Trimethoxy zirconium bromide (ZrBr (OCH
3)
3), triethoxy zirconium bromide (ZrBr (OCH
3CH
2)
3), three isobutoxy zirconium bromide (ZrBr (i-OC
4H
9)
3), three n-butoxy zirconium bromide (ZrBr (OC
4H
9)
3), dimethoxy dibrominated zirconium (ZrBr
2(OCH
3)
2), diethoxy dibrominated zirconium (ZrBr
2(OCH
3CH
2)
2), two isobutoxy dibrominated zirconium (ZrBr
2(i-OC
4H
9)
2), three n-butoxy zirconium bromide (ZrBr (OC
4H
9)
3), methoxyl group tribromide zirconium (Zr (OCH
3) Br
3), oxyethyl group tribromide zirconium (Zr (OCH
3CH
2) Br
3), isobutoxy tribromide zirconium (Zr (i-C
4H
9) Br
3), n-butoxy tribromide zirconium (Zr (OC
4H
9) Br
3);
Trimethoxy hafnium chloride (HfCl (OCH
3)
3), triethoxy hafnium chloride (HfCl (OCH
3CH
2)
3), three isobutoxy hafnium chloride (HfCl (i-OC
4H
9)
3), three n-butoxy hafnium chloride (HfCl (OC
4H
9)
3), dimethoxy hafnium dichloride (HfCl
2(OCH
3)
2), diethoxy hafnium dichloride (HfCl
2(OCH
3CH
2)
2), two isobutoxy hafnium dichloride (HfCl
2(i-OC
4H
9)
2), three n-butoxy hafnium chloride (HfCl (OC
4H
9)
3), methoxyl group tri-chlorination hafnium (Hf (OCH
3) Cl
3), oxyethyl group tri-chlorination hafnium (Hf (OCH
3CH
2) Cl
3), isobutoxy tri-chlorination hafnium (Hf (i-C
4H
9) Cl
3), n-butoxy tri-chlorination hafnium (Hf (OC
4H
9) Cl
3);
Trimethoxy bromination hafnium (HfBr (OCH
3)
3), triethoxy bromination hafnium (HfBr (OCH
3CH
2)
3), three isobutoxy bromination hafnium (HfBr (i-OC
4H
9)
3), three n-butoxy bromination hafnium (HfBr (OC
4H
9)
3), dimethoxy dibrominated hafnium (HfBr
2(OCH
3)
2), diethoxy dibrominated hafnium (HfBr
2(OCH
3CH
2)
2), two isobutoxy dibrominated hafnium (HfBr
2(i-OC
4H
9)
2), three n-butoxy bromination hafnium (HfBr (OC
4H
9)
3), methoxyl group tribromide hafnium (Hf (OCH
3) Br
3), oxyethyl group tribromide hafnium (Hf (OCH
3CH
2) Br
3), isobutoxy tribromide hafnium (Hf (i-C
4H
9) Br
3), n-butoxy tribromide hafnium (Hf (OC
4H
9) Br
3).
As said IV B family metallic compound, preferred said IV B family metal halide, more preferably TiCl
4, TiBr
4, ZrCl
4, ZrBr
4, HfCl
4And HfBr
4, TiCl most preferably
4And ZrCl
4
These IV B family metallic compound can use a kind of separately, perhaps uses multiple with ratio combination arbitrarily.
According to the present invention, make the chemical processing agent and the said optional porous support reaction that are selected from said IV B family metallic compound through thermal activation treatment, obtain to modify carrier (below be called chemical treatment reaction I); Perhaps, make chemical processing agent that is selected from said IV B family metallic compound and the complex carrier reaction that is described below, obtain load type non-metallocene catalyst of the present invention (below be called chemical treatment reaction II).
According to the present invention, in said chemical treatment reaction I and said chemical treatment reaction II, employed separately said chemical processing agent can be the same or different.
As the mode of carrying out said chemical treatment reaction I or chemical treatment reaction II (unless otherwise indicated, following content is with being applicable to said chemical treatment reaction I and II simultaneously), such as enumerating following content.
When said chemical processing agent is liquid state at normal temperatures; Can use said chemical processing agent through the mode that in the reaction object that remains to utilize this chemical processing agent to handle (such as said optional through the porous support of thermal activation treatment or the complex carrier that is described below, as follows), directly drips the said chemical processing agent of predetermined amount.
When said chemical processing agent when being solid-state at normal temperatures, for measure with easy to operate for the purpose of, preferably use said chemical processing agent with the form of solution.Certainly, when said chemical processing agent is liquid state at normal temperatures, also can use said chemical processing agent as required sometimes, not have special qualification with the form of solution.
When the solution of the said chemical processing agent of preparation, to this moment employed solvent do not have special qualification, as long as it can dissolve this chemical processing agent.
Particularly, can enumerate C
5-12Alkane, C
5-12Naphthenic hydrocarbon, halo C
5-12Alkane, halo C
5-12Naphthenic hydrocarbon, C
6-12Aromatic hydrocarbons or halo C
6-12Aromatic hydrocarbons etc.; Such as enumerating pentane, hexane, heptane, octane, nonane, decane, undecane, dodecyl, pentamethylene, hexanaphthene, suberane, cyclooctane, toluene, ethylbenzene, YLENE, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro undecane, chlorinated dodecane, chlorocyclohexane, chlorotoluene, chloro ethylbenzene and xylene monochloride etc.; Wherein preferred pentane, hexane, decane, hexanaphthene and toluene, most preferably hexane and toluene.
These solvents can use a kind of separately, perhaps are used in combination multiple with ratio arbitrarily.
It the concentration of said chemical processing agent in its solution is not had special qualification, can suitably select as required, as long as can realize implementing said chemical treatment with the said chemical processing agent of predetermined amount.As previously mentioned,, can directly use chemical processing agent to carry out said processing, but use after also can it being modulated into the chemical treatment agent solution if chemical processing agent is liquid.Be that the volumetric molar concentration of said chemical processing agent in its solution generally is set at 0.01～1.0mol/L, but is not limited to this easily.
As carrying out said chemically treated method; Such as enumerating; Under the situation that adopts solid chemical processing agent (such as zirconium tetrachloride); The solution that at first prepares said chemical processing agent, the said chemical processing agent of adding (the preferred dropping) predetermined amount in described pending reaction object (such as said optional through the porous support of thermal activation treatment or the complex carrier that is described below, as follows) then; Under the situation that adopts liquid chemical treatment agent (such as titanium tetrachloride); Can be directly (but also can after being prepared into solution) the said chemical processing agent of predetermined amount is added in (the preferred dropping) described pending reaction object; And chemical treatment reaction (in case of necessity by stirring) was carried out 0.5～24 hour; Preferred 1～8 hour, more preferably 2～6 hours, filter then, wash and dry getting final product.
Based on the present invention, said filtration, washing and drying can adopt conventional method to carry out, and wherein washer solvent can adopt used identical solvent when dissolving said chemical treatments.This washing is generally carried out 1～8 time, and preferred 2～6 times, most preferably 2～4 times.
So far, through aforesaid chemical treatment reaction I, obtained the modification carrier.
According to the present invention, magnesium compound is dissolved in the solvent (not comprising alcoholic solvent), obtain magnesium compound solution.
Below said magnesium compound is carried out bright specifically.
According to the present invention, term " magnesium compound " uses the common notion in this area, refers to as the conventional organic or inorganic solid water-free magnesium-containing compound that uses of the carrier of supported olefin polymerization catalyst.
According to the present invention, as said magnesium compound, such as enumerating magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium.
Particularly, as said magnesium halide, such as enumerating magnesium chloride (MgCl
2), magnesium bromide (MgBr
2), magnesium iodide (MgI
2) and Sellaite (MgF
2) etc., wherein preferred magnesium chloride.
As said alkoxyl group magnesium halide, such as enumerating methoxyl group chlorination magnesium (Mg (OCH
3) Cl), oxyethyl group magnesium chloride (Mg (OC
2H
5) Cl), propoxy-magnesium chloride (Mg (OC
3H
7) Cl), n-butoxy magnesium chloride (Mg (OC
4H
9) Cl), isobutoxy magnesium chloride (Mg (i-OC
4H
9) Cl), methoxyl group magnesium bromide (Mg (OCH
3) Br), oxyethyl group magnesium bromide (Mg (OC
2H
5) Br), propoxy-magnesium bromide (Mg (OC
3H
7) Br), n-butoxy magnesium bromide (Mg (OC
4H
9) Br), isobutoxy magnesium bromide (Mg (i-OC
4H
9) Br), methoxyl group magnesium iodide (Mg (OCH
3) I), oxyethyl group magnesium iodide (Mg (OC
2H
5) I), propoxy-magnesium iodide (Mg (OC
3H
7) I), n-butoxy magnesium iodide (Mg (OC
4H
9) I) and isobutoxy magnesium iodide (Mg (i-OC
4H
9) I) etc., wherein preferred methoxyl group chlorination magnesium, oxyethyl group magnesium chloride and isobutoxy magnesium chloride.
As said alkoxyl magnesium, such as enumerating magnesium methylate (Mg (OCH
3)
2), magnesium ethylate (Mg (OC
2H
5)
2), propoxy-magnesium (Mg (OC
3H
7)
2), butoxy magnesium (Mg (OC
4H
9)
2), isobutoxy magnesium (Mg (i-OC
4H
9)
2) and 2-ethyl hexyl oxy magnesium (Mg (OCH
2CH (C
2H
5) C
4H
-)
2) etc., wherein preferred magnesium ethylate and isobutoxy magnesium.
As said alkyl magnesium, such as enumerating methyl magnesium (Mg (CH
3)
2), magnesium ethide (Mg (C
2H
5)
2), propyl group magnesium (Mg (C
3H
7)
2), normal-butyl magnesium (Mg (C
4H
9)
2) and isobutyl-magnesium (Mg (i-C
4H
9)
2) etc., wherein preferred magnesium ethide and normal-butyl magnesium.
As said alkyl halide magnesium, such as enumerating methylmagnesium-chloride (Mg (CH
3) Cl), ethylmagnesium chloride (Mg (C
2H
5) Cl), propyl group magnesium chloride (Mg (C
3H
7) Cl), normal-butyl chlorination magnesium (Mg (C
4H
9) Cl), isobutyl-chlorination magnesium (Mg (i-C
4H
9) Cl), methyl-magnesium-bromide (Mg (CH
3) Br), ethylmagnesium bromide (Mg (C
2H
5) Br), propyl group magnesium bromide (Mg (C
3H
7) Br), normal-butyl bromination magnesium (Mg (C
4H
9) Br), isobutyl-bromination magnesium (Mg (i-C
4H
9) Br), methyl magnesium iodide (Mg (CH
3) I), ethyl magnesium iodide (Mg (C
2H
5) I), propyl group magnesium iodide (Mg (C
3H
7) I), normal-butyl iodate magnesium (Mg (C
4H
9) I) and isobutyl-iodate magnesium (Mg (i-C
4H
9) I) etc., wherein preferable methyl magnesium chloride, ethylmagnesium chloride and isobutyl-chlorination magnesium.
As said alkyl alkoxy magnesium, such as enumerating methyl methoxy base magnesium (Mg (OCH
3) (CH
3)), methyl ethoxy magnesium (Mg (OC
2H
5) (CH
3)), methyl propoxy-magnesium (Mg (OC
3H
7) (CH
3)), methyl n-butoxy magnesium (Mg (OC
4H
9) (CH
3)), methyl isobutoxy magnesium (Mg (i-OC
4H
9) (CH
3)), ethyl magnesium methylate (Mg (OCH
3) (C
2H
5)), ethyl magnesium ethylate (Mg (OC
2H
5) (C
2H
5)), ethyl propoxy-magnesium (Mg (OC
3H
7) (C
2H
5)), ethyl n-butoxy magnesium (Mg (OC
4H
9) (C
2H
5)), ethyl isobutoxy magnesium (Mg (i-OC
4H
9) (C
2H
5)), propyl group magnesium methylate (Mg (OCH
3) (C
3H
7)), propyl group magnesium ethylate (Mg (OC
2H
5) (C
3H
7)), propyl group propoxy-magnesium (Mg (OC
3H
7) (C
3H
7)), propyl group n-butoxy magnesium (Mg (OC
4H
9) (C
3H
7)), propyl group isobutoxy magnesium (Mg (i-OC
4H
9) (C
3H
7)), normal-butyl magnesium methylate (Mg (OCH
3) (C
4H
9)), normal-butyl magnesium ethylate (Mg (OC
2H
5) (C
4H
9)), normal-butyl propoxy-magnesium (Mg (OC
3H
7) (C
4H
9)), normal-butyl n-butoxy magnesium (Mg (OC
4H
9) (C
4H
9)), normal-butyl isobutoxy magnesium (Mg (i-OC
4H
9) (C
4H
9)), isobutyl-magnesium methylate (Mg (OCH
3) (i-C
4H
9)), isobutyl-magnesium ethylate (Mg (OC
2H
5) (i-C
4H
9)), isobutyl-propoxy-magnesium (Mg (OC
3H
7) (i-C
4H
9)), isobutyl-n-butoxy magnesium (Mg (OC
4H
9) (i-C
4H
9)) and isobutyl-isobutoxy magnesium (Mg (i-OC
4H
9) (i-C
4H
9)) etc., wherein preferred butyl magnesium ethylate.
These magnesium compounds can use a kind of separately, also can multiple mixing use, and do not have special restriction.
When using with multiple blended form, the mol ratio between any two kinds of magnesium compounds in the said magnesium compound mixture is such as being 0.25～4: 1, preferred 0.5～3: 1, more preferably 1～2: 1.
Below carry out bright specifically to the step that obtains said magnesium compound solution.
Particularly, make said magnesium compound (solid) be dissolved in appropriate solvent (promptly being used for dissolving the solvent of said magnesium compound), thereby obtain said magnesium compound solution.
As said solvent, such as enumerating C
6-12Aromatic hydrocarbon, halo C
6-12Aromatic hydrocarbon, ester and ether equal solvent.Specifically such as enumerating toluene, YLENE, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, ETHYLE ACETATE and THF etc.Wherein, preferred C
6-12Aromatic hydrocarbon and THF, most preferably THF.
According to the present invention one preferred embodiment, said solvent preferably can dissolve said magnesium compound (solid) and Nonmetallocene part hereinafter described simultaneously.At this moment, as said solvent, such as enumerating said C
6-12Aromatic hydrocarbon, said halo C
6-12Aromatic hydrocarbon and THF etc.
It is pointed out that the present invention in preparation during said load type non-metallocene catalyst, in any step, all do not use alcoholic solvent (such as aromatic alcohols such as fatty alcohols such as ethanol, phenylcarbinols etc.) as solvent.
These solvents can use a kind of separately, also can use with the multiple mixing of ratio arbitrarily.
In order to prepare said magnesium compound solution, said magnesium compound (perhaps according to circumstances, with said magnesium compound and said Nonmetallocene part) metering added to dissolve in the said solvent to getting final product.When the said magnesium compound solution of preparation; Ratio in the said magnesium compound (solid) of magnesium elements and the said solvent that is used to dissolve said magnesium compound is generally 1mol: 75～400ml; Preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml.
Preparation time (being the dissolution time of said magnesium compound etc.) to said magnesium compound solution does not have special qualification, but is generally 0.5～24h, preferred 4～24h.In this preparation process, can utilize and stir the dissolving promote said magnesium compound etc.This stirring can be adopted any form, such as stirring rake (rotating speed is generally 10～1000 rev/mins) etc.As required, can promote dissolving through suitable heating (but top temperature must be lower than the boiling point of said solvent) sometimes.
According to the present invention; Term " Nonmetallocene title complex " refers to a kind of active organometallics of olefinic polymerization catalysis (therefore said Nonmetallocene title complex also is called as non-metallocene olefin polymerization property title complex sometimes) that when making up with aikyiaiurnirsoxan beta, can demonstrate; This compound comprises central metal atom and at least one and said central metal atom with co-ordination bond bonded polydentate ligand (preferably tridentate ligand or more polydentate ligand), and term " Nonmetallocene part " is aforesaid polydentate ligand.
According to the present invention, said Nonmetallocene part is selected from the compound with following chemical structural formula:
According to the present invention; Group A, D and E (group is used in coordination) in this compound forms co-ordination bond through its contained coordination with the contained IV B family atoms metal generation coordination reaction of using as chemical processing agent among atom (such as heteroatomss such as N, O, S, Se and P) and the present invention of IV B family metallic compound, and forming thus with this IV B family atoms metal is the title complex (being Nonmetallocene title complex of the present invention) of central atom.
In a more concrete embodiment, said Nonmetallocene part is selected from compound (A) and the compound (B) with following chemical structural formula:
In a more concrete embodiment, said Nonmetallocene part is selected from compound (A-1) to compound (A-4) with following chemical structural formula and compound (B-1) to compound (B-4):
In above all chemical structural formulas,
Q is 0 or 1;
D is 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
-NR
23R
24,-N (O) R
25R
26,
-PR
28R
29,-P (O) R
30OR
31, sulfuryl, sulfoxide group or-Se (O) R
39, wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C
1-C
30Alkyl;
D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C
1-C
30Alkyl, sulfuryl, sulfoxide group,
-N (O) R
25R
26,
Or-P (O) R
32(OR
33), wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyanic acid that (CN), wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, and wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
G is selected from C
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group;
Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, and wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyanic acid (CN), such as enumerating-NR
23R
24,-N (O) R
25R
26,-PR
28R
29,-P (O) R
30R
31,-OR
34,-SR
35,-S (O) R
36,-SeR
38Or-Se (O) R
39, wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R
1To R
4, R
6To R
36, R
38And R
39Be selected from hydrogen, C independently of one another
1-C
30Alkyl, substituted C
1-C
30Alkyl (wherein preferred halo alkyl, such as-CH
2Cl and-CH
2CH
2Cl) or safing function property group, above-mentioned group can be the same or different to each other, and wherein adjacent group is such as R
1With R
2, R
6With R
7, R
7With R
8, R
8With R
9, R
13With R
14, R
14With R
15, R
15With R
16, R
18With R
19, R
19With R
20, R
20With R
21, R
23With R
24, perhaps R
25With R
26Deng combining togather into key or Cheng Huan, be preferably formed aromatic ring, such as unsubstituted phenyl ring or by 1-4 C
1-C
30Alkyl, substituted C
1-C
30Alkyl (wherein preferred halo alkyl, such as-CH
2Cl and-CH
2CH
2Cl) or the substituted phenyl ring of safing function property group; And
R
5Be selected from lone-pair electron on the nitrogen, hydrogen, C
1-C
30Alkyl, substituted C
1-C
30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R
5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R
5In N, O, S, P and Se can be used as coordination and carry out coordination with atom and said center IV B family atoms metal.
According to the present invention, in aforementioned all chemical structural formulas, as the case may be, any adjacent two or more groups are such as R
21With group Z, perhaps R
13With group Y, can combine togather into ring, be preferably formed and comprise the heteroatomic C that comes from said group Z or Y
6-C
30Heteroaromatic, such as pyridine ring etc., wherein said heteroaromatic is optional to be selected from C by one or more
1-C
30Alkyl, substituted C
1-C
30The substituting group of alkyl and safing function property group replaces.
In context of the present invention,
Said halogen is selected from F, Cl, Br or I;
Said nitrogen-containing group is selected from
-NR
23R
24,-T-NR
23R
24Or-N (O) R
25R
26
Said phosphorus-containing groups is selected from
-PR
28R
29,-P (O) R
30R
31Or-P (O) R
32(OR
33);
Said oxy radical be selected from hydroxyl ,-OR
34With-T-OR
34
Said sulfur-containing group is selected from-SR
35,-T-SR
35,-S (O) R
36Or-T-SO
2R
37
The said seleno group that contains is selected from-SeR
38,-T-SeR
38,-Se (O) R
39Or-T-Se (O) R
39
Said group T is selected from C
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group; With
Said R
37Be selected from hydrogen, C
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group.
In context of the present invention, said C
1-C
30Alkyl is selected from C
1-C
30Alkyl (preferred C
1-C
6Alkyl is such as isobutyl-), C
7-C
50Alkaryl (such as tolyl, xylyl, diisobutyl phenyl etc.), C
7-C
50Aralkyl (such as benzyl), C
3-C
30Cyclic alkyl, C
2-C
30Thiazolinyl, C
2-C
30Alkynyl, C
6-C
30Aryl (such as phenyl, naphthyl, anthryl etc.), C
8-C
30Condensed ring radical or C
4-C
30Heterocyclic radical, wherein said heterocyclic radical contain 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom, such as pyridyl, pyrryl, furyl or thienyl etc.
According to the present invention, in context of the present invention, according to the particular case of the relevant group of its bonded, said C
1-C
30Alkyl refers to C sometimes
1-C
30(divalent group perhaps is called C to hydrocarbon two bases
1-C
30Alkylene) or C
1-C
30Hydrocarbon three bases (trivalent group), this is obvious to those skilled in the art.
In context of the present invention, said substituted C
1-C
30Alkyl refers to the aforementioned C that has one or more inert substituents
1-C
30Alkyl.So-called inert substituent refers to these substituting groups aforementioned coordination (is referred to aforementioned group A, D, E, F, Y and Z, the perhaps also optional R that comprises with group
5) there is not substantial interference with the coordination process of central metal atom (aforementioned IV B family atoms metal); In other words, limit by the chemical structure of part of the present invention, these substituting groups do not have ability or have no chance (such as the influence that receives steric hindrance etc.) forms co-ordination bond with said IV B family's atoms metal generation coordination reaction.Generally speaking, said inert substituent refers to aforementioned halogen or C
1-C
30Alkyl (preferred C
1-C
6Alkyl is such as isobutyl-).
In context of the present invention, said safing function property group does not comprise aforesaid C
1-C
30Alkyl and aforesaid substituted C
1-C
30Alkyl.As said safing function property group, such as enumerating aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, containing tin group, C
1-C
10Ester group and nitro (NO
2) etc.
In context of the present invention, limit by the chemical structure of part of the present invention, said safing function property group has following characteristics:
(1) do not disturb said group A, D, E, F, Y or Z and said IV B family atoms metal the coordination process and
(2) coordination ability with said IV B family atoms metal is lower than said A, D, E, F, Y and Z group, and does not replace the existing coordination of these groups and said IV B family atoms metal.
In context of the present invention, said silicon-containing group is selected from-SiR
42R
43R
44Or-T-SiR
45Said germanic group is selected from-GeR
46R
47R
48Or-T-GeR
49Saidly contain tin group and be selected from-SnR
50R
51R
52,-T-SnR
53Or-T-Sn (O) R
54And said R
42To R
54Be selected from hydrogen, aforesaid C independently of one another
1-C
30Alkyl, aforesaid substituted C
1-C
30Alkyl or aforesaid safing function property group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and the definition of said group T is the same.
As said Nonmetallocene part, such as enumerating following compound:
Said Nonmetallocene part is preferably selected from following compound:
Said Nonmetallocene part further is preferably selected from following compound:
Said Nonmetallocene part more preferably is selected from following compound:
These Nonmetallocene parts can use a kind of separately, perhaps are used in combination multiple with ratio arbitrarily.
According to the present invention, said Nonmetallocene part is not as the normally used diether compounds of electronic donor compound capable in this area.
Said Nonmetallocene part can be made according to any method well known by persons skilled in the art.About the particular content of its method of manufacture, such as can be referring to WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 etc., the full text that this specification sheets is introduced these documents at this point as a reference.
According to the present invention, said modification carrier, said magnesium compound solution are contacted with said Nonmetallocene part, obtain mixed serum.
When making said mixed serum; The way of contact of said modification carrier, said magnesium compound solution and said Nonmetallocene part and engagement sequence etc. there is not special qualification; Such as enumerating said modification carrier is mixed earlier with said magnesium compound solution, and then to the scheme that wherein adds said Nonmetallocene part; Make said modification carrier, said magnesium compound solution and said Nonmetallocene part blended scheme simultaneously; Said Nonmetallocene part and said magnesium compound are dissolved in the foregoing solvent simultaneously; Make the mixing solutions (being also referred to as magnesium compound solution hereinafter sometimes) of magnesium compound and Nonmetallocene part thus, and then make said modification carrier and said mixing solutions blended scheme or the like.
In addition; In order to make said mixed serum; Such as can be to the temperature of the boiling point that is lower than employed any solvent at normal temperature; Make the contact reacts of said modification carrier, said magnesium compound solution and said Nonmetallocene part carry out 0.1～8h, preferred 0.5～4h, optimum 1～2h (in case of necessity by stirring) gets final product.
At this moment, the mixed serum that is obtained is a kind of system of pulpous state.Though unessential, in order to ensure the homogeneity of system, this mixed serum preferably carries out certain hour (2～48h, preferred 4～24h, most preferably 6～18h) airtight leaving standstill after preparation.
Through in said mixed serum, being metered into precipitation agent, solid matter is precipitated out from this mixed serum, obtain complex carrier thus.
Below said precipitation agent is carried out bright specifically.
According to the present invention, term " precipitation agent " uses the common notion in this area, refers to reduce the solubleness of solute (such as said magnesium compound) in its solution and and then unreactiveness liquid that it is separated out with solid form from said solution.
According to the present invention; As said precipitation agent; For said magnesium compound, be poor solvent such as enumerating, and for the said solvent that is used to dissolve said magnesium compound, be the solvent of good solvent, such as enumerating alkane, naphthenic hydrocarbon, halogenated alkane and halo naphthenic hydrocarbon.
As said alkane, such as enumerating pentane, hexane, heptane, octane, nonane and decane etc., wherein preferred hexane, heptane and decane, most preferably hexane.
As said naphthenic hydrocarbon, such as enumerating hexanaphthene, pentamethylene, suberane, cyclodecane and cyclononane etc., most preferably hexanaphthene.
As said halogenated alkane, such as enumerating methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane and three NBBs etc.
As said halo naphthenic hydrocarbon, such as enumerating chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, bromo cyclononane and bromo cyclodecane etc.
These precipitation agents can use a kind of separately, also can use with the multiple mixing of ratio arbitrarily.
The adding mode of precipitation agent can or drip preferred disposable adding for disposable adding.In this precipitation process, can utilize to stir to promote the dispersion of precipitation agent, and help the final deposition of solid product.This stirring can be adopted any form, such as stirring rake (rotating speed is generally 10～1000 rev/mins) etc.
Temperature to said precipitation agent does not have special qualification yet, but general preferred normal temperature.And this precipitation process is generally also preferably carried out at normal temperatures.
Post precipitation filters, washs and drying the solid product that is obtained fully, obtains complex carrier thus.Do not have special qualification for said filtration, washing and exsiccant method, can use conventional those that use in this area as required.
As required, said washing is generally carried out 1～6 time, preferred 2～3 times.Wherein, washer solvent preferably uses the solvent identical with precipitation agent, but also can be different.
Said drying can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or the vacuum, and heat drying method, most preferably heat drying method under the vacuum under preferred rare gas element desiccating method or the vacuum.
Said exsiccant TR is generally normal temperature to 100 ℃, exceeds and no longer reduce up to quality of material with drying time of drying.Such as; When adopting the THF conduct to be used to dissolve the solvent of said magnesium compound; Drying temperature is generally about 80 ℃, under vacuum, got final product in dry 2～12 hours, and when adopting the toluene conduct to be used to dissolve the solvent of said magnesium compound; Drying temperature is generally about 100 ℃, under vacuum, gets final product in dry 4～24 hours.
Then; Through aforesaid chemical treatment reaction II; Make said chemical processing agent and said complex carrier carry out chemical reaction; Cause Nonmetallocene part generation coordination reaction contained in said chemical processing agent and this complex carrier, thereby original position generates Nonmetallocene title complex (original position load reaction) on this complex carrier, obtains load type non-metallocene catalyst of the present invention thus.
In said chemical treatment reaction II; Owing to contain said magnesium compound and said Nonmetallocene part in the said complex carrier; So obviously, just can not select for use this moment has the solvent of stripping capacity to dissolve said chemical processing agent to said magnesium compound or said Nonmetallocene part, to avoid the inappropriate stripping of these materials in treating processes.
According to the present invention; As the consumption of said Nonmetallocene part, make to reach 1: 0.0001-1, preferred 1: 0.0002-0.4 in the said magnesium compound (solid) of Mg element and the mol ratio of said Nonmetallocene part; More preferably 1: 0.0008-0.2, further preferred 1: 0.001-0.1.
According to the present invention, as the consumption of the said solvent that is used to dissolve said magnesium compound, make the said magnesium compound (solid) and the ratio of said solvent reach 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml.
According to the present invention,, make to reach 1: 0.1-20, preferred 1: 0.5-10, more preferably 1: 1-5 in the said magnesium compound of magnesium compound solid and the mass ratio of said porous support as the consumption of said porous support.
According to the present invention; In said chemical treatment reaction I and said chemical treatment reaction II; The consumption of said chemical processing agent can be the same or different, and selects independently of one another, thereby makes and in each chemical treatment reaction, to reach 1 in the said magnesium compound (solid) of Mg element and mol ratio in the said chemical processing agent of IV B family metal (such as Ti) element independently of one another: 0.01-1; Preferred 1: 0.01-0.50, more preferably 1: 0.10-0.30.
According to the present invention,, make that the said precipitation agent and the volume ratio of the said solvent that is used to dissolve said magnesium compound are 1: 0.2～5, preferred 1: 0.5～2, more preferably 1: 0.8～1.5 as the consumption of said precipitation agent.
Known to those skilled in the artly be that aforementioned all method steps all preferably carries out under the condition of anhydrous anaerobic basically.Here the content that said anhydrous basically anaerobic refers to water and oxygen in the system continues less than 10ppm.And load type non-metallocene catalyst of the present invention needs pressure-fired preservation in confined conditions subsequent use after preparation usually.
In one embodiment, the invention still further relates to the load type non-metallocene catalyst of making by the preparation method of aforesaid load type non-metallocene catalyst (being also referred to as carry type non-metallocene calalyst for polymerization of olefine sometimes).
In a further embodiment, the present invention relates to a kind of alkene homopolymerization/copolymerization process, wherein with load type non-metallocene catalyst of the present invention as catalyst for olefines polymerizing, make alkene homopolymerization or copolymerization.
With regard to this alkene homopolymerization/copolymerization process involved in the present invention; Except the following content that particularly points out; Other contents of not explaining (such as polymerization with addition manner of reactor drum, alkene consumption, catalyzer and alkene etc.); Can directly be suitable for this area conventional known those, do not have special restriction, omit its explanation at this.
According to homopolymerization/copolymerization process of the present invention; With load type non-metallocene catalyst of the present invention is Primary Catalysts; To be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is promotor, makes alkene homopolymerization or copolymerization.
Primary Catalysts and the promotor adding mode in polymerization reaction system can be to add Primary Catalysts earlier; And then the adding promotor, perhaps add promotor earlier, and then add Primary Catalysts; Or add together after both contact mixing earlier, perhaps add simultaneously respectively.Primary Catalysts and promotor added respectively fashionablely both can in same reinforced pipeline, add successively, also can in the reinforced pipeline of multichannel, add successively, and both add simultaneously respectively and fashionablely should select the multichannel pipeline that feeds in raw material.For the continous way polyreaction; The adding continuously simultaneously of the reinforced pipeline of preferred multichannel, and for the intermittence type polymerization reaction, preferably both mix back adding together in same reinforced pipeline earlier; Perhaps in same reinforced pipeline, add promotor earlier, and then add Primary Catalysts.
According to the present invention; Reactive mode to said alkene homopolymerization/copolymerization process does not have special qualification; Can adopt well known in the art those, such as enumerating slurry process, emulsion method, solution method, substance law and vapor phase process etc., wherein preferred slurries method and vapor phase process.
According to the present invention, as said alkene, such as enumerating C
2～C
10Monoolefine, diolefin, cyclic olefin and other ethylenically unsaturated compounds.
Particularly, as said C
2～C
10Monoolefine is such as enumerating ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene and vinylbenzene etc.; As said cyclic olefin, such as enumerating 1-cyclopentenes and norbornylene etc.; As said diolefin, such as enumerating 1,4-divinyl, 2,5-pentadiene, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc.; And as said other ethylenically unsaturated compounds, such as enumerating vinyl acetate and (methyl) propenoate etc.Wherein, the homopolymerization of optimal ethylene, the perhaps copolymerization of ethene and propylene, 1-butylene or 1-hexene.
According to the present invention, homopolymerization refers to only a kind of polymerization of said alkene, and copolymerization refers to the polymerization between the two or more said alkene.
According to the present invention, said promotor is selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, wherein preferred aikyiaiurnirsoxan beta and aluminum alkyls.
As said aikyiaiurnirsoxan beta, such as enumerating the line style aikyiaiurnirsoxan beta shown in the formula (I-1): (R) (R) Al-(Al (R)-O)
n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in the formula (II-1) :-(Al (R)-O-)
N+2-.
In aforementioned formula, radicals R is same to each other or different to each other (preferably identical), is selected from C independently of one another
1-C
8Alkyl, preferable methyl, ethyl and isobutyl-, most preferable; N is the arbitrary integer in the 1-50 scope, the arbitrary integer in preferred 10～30 scopes.
As said aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide and normal-butyl alumina alkane, further preferable methyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide, and most preferable aikyiaiurnirsoxan beta.
These aikyiaiurnirsoxan beta can be used a kind of separately, perhaps are used in combination multiple with ratio arbitrarily.
As said aluminum alkyls, such as enumerating the compound shown in the following general formula (III-1):
Al(R)
3(III-1)
Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from C independently of one another
1-C
8Alkyl, preferable methyl, ethyl and isobutyl-, most preferable.
Particularly, as said aluminum alkyls, such as enumerating trimethylaluminium (Al (CH
3)
3), triethyl aluminum (Al (CH
3CH
2)
3), tri-propyl aluminum (Al (C
3H
7)
3), triisobutyl aluminium (Al (i-C
4H
9)
3), three n-butylaluminum (Al (C
4H
9)
3), triisopentyl aluminium (Al (i-C
5H
11)
3), three n-pentyl aluminium (Al (C
5H
11)
3), three hexyl aluminium (Al (C
6H
13)
3), three isohexyl aluminium (Al (i-C
6H
13)
3), diethylmethyl aluminium (Al (CH
3) (CH
3CH
2)
2) and dimethyl ethyl aluminium (Al (CH
3CH
2) (CH
3)
2) etc., wherein preferred trimethylaluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, further preferred triethyl aluminum and triisobutyl aluminium, and triethyl aluminum most preferably.
These alkyl aluminums can use a kind of separately, perhaps are used in combination multiple with ratio arbitrarily.
As said haloalkyl aluminium, said boron fluothane, said boron alkyl and said boron alkyl ammonium salt, can directly use conventional those that use in this area, do not have special restriction.
In addition, according to the present invention, said co-catalyst can use a kind of separately, also can be as required be used in combination multiple aforesaid co-catalyst with ratio arbitrarily, does not have special restriction.
According to the present invention,, need use polymerization to use solvent sometimes according to the difference of the reactive mode of said alkene homopolymerization/copolymerization process.
Use solvent as said polymerization, can use this area conventional those that use when carrying out alkene homopolymerization/copolymerization, do not have special restriction.
Use solvent as said polymerization, such as enumerating C
4-10Alkane (such as butane, pentane, hexane, heptane, octane, nonane or decane etc.), halo C
1-10Alkane (such as methylene dichloride), aromatic hydrocarbon solvent (such as toluene and YLENE) etc.Wherein, preferably use hexane to use solvent as said polymerization.
These polymerizations can be used a kind of separately with solvent, perhaps be used in combination multiple with ratio arbitrarily.
According to the present invention, the polymerization pressure of said alkene homopolymerization/copolymerization process is generally 0.1～10MPa, preferred 0.1～4MPa, and more preferably 1～3MPa, but be not limited to this sometimes.According to the present invention, polymeric reaction temperature is generally-40 ℃～200 ℃, and preferred 10 ℃～100 ℃, more preferably 40 ℃～90 ℃, but be not limited to this sometimes.
In addition, according to the present invention, said alkene homopolymerization/copolymerization process can carry out under the condition that has hydrogen to exist, and also can under the condition that does not have hydrogen to exist, carry out.Under situation about existing, the dividing potential drop of hydrogen can be 0.01%～99% of a said polymerization pressure, and is preferred 0.01%～50%, but is not limited to this sometimes.
According to the present invention; When carrying out said alkene homopolymerization/copolymerization process; Be generally 1～1000 in the said promotor of aluminium or boron and mol ratio: 1 in the said load type non-metallocene catalyst of central metal atom M; Preferred 10～500: 1, more preferably 15～300: 1, but be not limited to this sometimes.
Embodiment
Below adopt embodiment that the present invention is described in further detail, but the present invention is not limited to these embodiment.
(unit is g/cm to polymer stacks density
3) mensuration carry out with reference to CNS GB 1636-79.
The content of IV B family metal (such as Ti) and Mg element adopts the ICP-AES method to measure in the load type non-metallocene catalyst, and the content of Nonmetallocene part adopts analyses.
The polymerization activity of catalyzer calculates according to following method: after polyreaction finishes; Polymerisate in the reaction kettle is filtered and drying; The quality of this polymerisate of weighing then representes that divided by the ratio of the quality of used load type non-metallocene catalyst (unit is kg polymkeric substance/g catalyzer or kg polymkeric substance/gCat) for the polymerization activity of this catalyzer with this polymerisate quality.
Molecular weight Mw, Mn and the MWD (Mw/Mn) of polymkeric substance adopts the GPC V2000 type gel chromatography analyser of U.S. WATERS company to measure, and with 1,2, the 4-trichlorobenzene is a solvent, and surveying periodic temperature is 150 ℃.
Embodiment 1
Porous support adopts silicon-dioxide, i.e. silica gel, and model is the ES757 of Ineos company, at first with silica gel lasting roasting 4h and thermal activation under 600 ℃, nitrogen atmosphere.
Chemical processing agent adopts titanium tetrachloride (TiCl
4).Take by weighing the silica gel after the 5g thermal activation, add the 60ml hexane, under the stirring at normal temperature condition, add titanium tetrachloride,, filter at 60 ℃ down behind the reaction 2h, hexane wash 3 times, each 60ml, last vacuum is drained and is obtained modifying carrier.
Magnesium compound adopts Magnesium Chloride Anhydrous, and the solvent of dissolved magnesium compound and Nonmetallocene part adopts THF.It is the compound of
that the Nonmetallocene part adopts structure.
Take by weighing Magnesium Chloride Anhydrous and Nonmetallocene part, add behind the tetrahydrofuran solvent under the normal temperature fully that dissolving obtains magnesium compound solution, add then and modify carrier; Stir after 2 hours, add the precipitation agent hexane then and make it deposition, filter; Wash 2 times; Each washing composition consumption with it before add-on identical, vacuumize drying under the even heating to 60 ℃, obtain complex carrier.
Then in this complex carrier, add the 60ml hexane, under agitation condition with 30 minutes dropping titanium tetrachlorides, 60 ℃ of following stirring reactions 4 hours; Filter; Hexane wash 2 times, each hexane consumption 60ml, vacuum-drying obtains load type non-metallocene catalyst under the normal temperature.
Wherein proportioning does, magnesium compound and porous support mass ratio are 1: 2; In the Mg element, magnesium compound and Nonmetallocene part mol ratio are 1: 0.08, with the solvents tetrahydrofurane proportioning be 1mol: 240ml, be 1: 0.20 with twice chemical processing agent mol ratio, the volume ratio of precipitation agent and tetrahydrofuran solvent is 1: 1.
Said load type non-metallocene catalyst is designated as CAT-1.
Embodiment 2
Basic identical with embodiment 1, but following change is arranged:
Porous support is changed into 955 of Grace company, lasting roasting 8h under 400 ℃, nitrogen atmosphere and thermal activation.Chemical processing agent changes zirconium tetrachloride (ZrCl into
4), hexane changes toluene into.The Nonmetallocene part adopts the solvent of
dissolved magnesium compound and Nonmetallocene part to change into toluene, and precipitation agent is changed into hexanaphthene.
Then in this complex carrier, add 60ml toluene, under agitation condition with 30 minutes dropping zirconium tetrachlorides, 80 ℃ of following stirring reactions 4 hours; Filter; Toluene wash 2 times, each toluene consumption 60ml, 60 ℃ of following vacuum-dryings obtain load type non-metallocene catalyst.
Wherein proportioning does, magnesium compound and porous support mass ratio are 1: 1; In the Mg element, magnesium compound and Nonmetallocene part mol ratio are 1: 0.14, with the solvent toluene proportioning be 1mol: 160ml, be 1: 0.30 twice with the mol ratio of chemical processing agent, the volume ratio of precipitation agent and solvent is 1: 1.5.
Load type non-metallocene catalyst is designated as CAT-2.
Embodiment 3
Basic identical with embodiment 1, but following change is arranged:
Porous support adopts aluminium sesquioxide.With aluminium sesquioxide lasting roasting 6h under 700 ℃, nitrogen atmosphere.Chemical processing agent changes titanium tetrabromide (TiBr into
4)
Magnesium compound is changed into anhydrous magnesium bromide (MgBr
2), the Nonmetallocene part adopts
The solvent of dissolved magnesium compound and Nonmetallocene part is changed into ethylbenzene, and precipitation agent is changed into suberane.
Wherein proportioning does, magnesium compound and porous support mass ratio are 1: 4; In the Mg element; Magnesium compound and Nonmetallocene part mol ratio are 1: 0.20, with solvent ethylbenzene proportioning be 1mol: 300ml, successively (obvious is with the mol ratio of chemical processing agent; I is an elder generation with the chemical treatment reaction; After with chemical treatment reaction II being, as follows) be respectively 1: 0.10 and 1: 0.20, the volume ratio of precipitation agent and solvent is 1: 0.6.
Load type non-metallocene catalyst is designated as CAT-3.
Embodiment 4
Basic identical with embodiment 1, but following change is arranged:
Porous support adopts silica-magnesia mixed oxide (mass ratio 1: 1).The silica-magnesia mixed oxide is continued roasting 4h under 600 ℃, argon gas atmosphere.
Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC
2H
5)), the Nonmetallocene part adopts
The solvent of dissolved magnesium compound and Nonmetallocene part is changed into YLENE, and precipitation agent is changed into decane, and chemical processing agent adopts tetraethyl-titanium (Ti (CH
3CH
2)
4).
Wherein proportioning does, magnesium compound and porous support mass ratio are 1: 0.5; In the Mg element, magnesium compound and Nonmetallocene part mol ratio are 1: 0.05, with the solvent xylene proportioning be 1mol: 160ml, successively be respectively 1: 0.70 and 1: 0.10 with the chemical processing agent mol ratio, the volume ratio of precipitation agent and solvent is 1: 0.5.
Load type non-metallocene catalyst is designated as CAT-4.
Embodiment 5
Basic identical with embodiment 1, but following change is arranged:
The porous support adopting montmorillonite.With polynite lasting roasting 8h under 400 ℃, nitrogen atmosphere.Magnesium compound is changed into butoxy magnesium bromide (MgBr (OC
4H
9)), the Nonmetallocene part adopts
The solvent of dissolved magnesium compound and Nonmetallocene part is changed into diethylbenzene, and precipitation agent is changed into octane-iso, and complex carrier is handled with chemical processing agent and adopted tetra-n-butyl titanium (Ti (C
4H
9)
4).
Wherein proportioning does; Magnesium compound and porous support mass ratio are 1: 10; In the Mg element, magnesium compound and Nonmetallocene part mol ratio are 1: 0.4, with solvent diethylbenzene proportioning be 1mol: 120ml; Successively be respectively 1: 0.50 and 1: 0.20 with the chemical processing agent mol ratio, the volume ratio of precipitation agent and solvent is 1: 1.3.
Load type non-metallocene catalyst is designated as CAT-5.
Embodiment 6
Basic identical with embodiment 1, but following change is arranged:
Porous support adopts the PS of partial cross-linked (degree of crosslinking is 30%).This PS is continued oven dry 12h under 85 ℃, nitrogen atmosphere.
Magnesium compound is changed into methylmagnesium-chloride (Mg (CH
3) Cl), the Nonmetallocene part adopts
The solvent of dissolved magnesium compound and Nonmetallocene part is changed into chlorotoluene.
Zirconium tetrachloride is adopted in the porous support chemical treatment, and complex carrier is handled and adopted titanium tetrachloride, and in the Mg element, magnesium compound and zirconium tetrachloride mol ratio are 1: 0.30, with the titanium tetrachloride mol ratio be 1: 0.25.
Load type non-metallocene catalyst is designated as CAT-6.
Embodiment 7
Basic identical with embodiment 1, but following change is arranged:
Porous support adopts zeyssatite.With zeyssatite lasting roasting 8h under 500 ℃, nitrogen atmosphere.
Magnesium compound is changed into ethylmagnesium chloride (Mg (C
2H
5) Cl), the Nonmetallocene part adopts
Load type non-metallocene catalyst is designated as CAT-7.
Reference example 1-A
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound and Nonmetallocene part mol ratio are changed into 1: 0.16;
Load type non-metallocene catalyst is designated as CAT-1-A.
Reference example 1-B
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound and Nonmetallocene part mol ratio are changed into 1: 0.04;
Load type non-metallocene catalyst is designated as CAT-1-B.
Reference example 1-C
Basic identical with embodiment 1, but following change is arranged:
Porous support is handled without chemical processing agent;
Load type non-metallocene catalyst is designated as CAT-1-C.
Reference example 1-D
Basic identical with embodiment 1, but following change is arranged:
Complex carrier is handled without chemical processing agent;
Load type non-metallocene catalyst is designated as CAT-1-D.
Reference example 1-E
Basic identical with embodiment 1, but following change is arranged:
Complex carrier obtains by directly mixed serum being vacuumized drying at normal temperatures;
Load type non-metallocene catalyst is designated as CAT-1-E.
The application implementation example
Load type non-metallocene catalyst CAT-1～7 that make in the embodiment of the invention, CAT-1-A～E are carried out the homopolymerization and the copolymerization of ethene respectively according to following method under following condition:
Homopolymerization is: 5 liters of polymerization autoclaves; Slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa; Hydrogen partial pressure 0.2MPa; 85 ℃ of polymerization temperatures are 100: 1 in the promotor of aluminium with mol ratio in the load type non-metallocene catalyst of central metal atom, 2 hours reaction times.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, add 50mg load type non-metallocene catalyst and catalyst mixture then, continue to feed ethene and make the polymerization stagnation pressure constant at 0.8MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry back weighing quality.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.
Copolymerization is: 5 liters of polymerization autoclaves; Slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa; Hydrogen partial pressure 0.2MPa; 85 ℃ of polymerization temperatures are 100: 1 in the promotor of aluminium with mol ratio in the load type non-metallocene catalyst of central metal atom, 2 hours reaction times.At first 2.5 liters of hexanes are joined in the polymerization autoclave; Open and stir; Add 50mg load type non-metallocene catalyst and catalyst mixture then, disposable adding 1-hexene co-monomer 50g and hydrogen continue to feed ethene and make the polymerization stagnation pressure constant in 0.8MPa to 0.2MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry back weighing quality.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.
Table 1. load type non-metallocene catalyst is used for olefinic polyreaction effect table look-up
Visible by table 1, higher with the load type non-metallocene catalyst polymerization activity of method preparation provided by the invention, and polymer stacks density is higher.
Test-results data through sequence number in the contrast table 11 and sequence number 10,11 can be known; Though the Nonmetallocene part does not have the catalysis in olefine polymerization activity; But in catalyst preparation process provided by the invention, increase or reduce Nonmetallocene part add-on; Its activity increases thereupon or reduces, and the MWD of polymkeric substance also narrows down thereupon and broadens.After thereby the Nonmetallocene part being described in load type non-metallocene catalyst provided by the present invention and the chemical processing agent reaction in being combined; Formed and had the active Nonmetallocene title complex of catalysis in olefine polymerization component; It has the effect of the molecular weight distribution of narrowing, therefore can be through regulating the MWD that the relative proportioning with the complex carrier chemical processing agent of Nonmetallocene part is come telomerized polymer.
Sequence number 1 and 2 test-results data can be known in the contrast table 1, adopt load type non-metallocene catalyst provided by the invention, show significant comonomer effect, and promptly under equal relatively condition, the copolymerization activity is higher than the homopolymerization activity.
Test-results data through sequence number in the contrast table 11 and sequence number 12 can be known, adopt porous support provided by the present invention to handle the catalyst activity and the polymer stacks density that obtain through chemical processing agent and are higher than porous support without the resulting catalyzer of chemical processing agent.And the former resulting molecular weight distribution is wider than the latter, illustrates further thus, and method for preparing catalyst provided by the invention, chemical processing agent have the MWD and the effectiveness that improves polymer stacks density of wide fluidized polymer.
Test-results data through sequence number in the contrast table 11 and sequence number 14 can be known; The catalyst preparation process route that adopts complex carrier provided by the present invention to obtain by precipitation agent deposition, and thus the polymer stacks density that obtains of polymerization to be higher than complex carrier be directly to vacuumize dry and resulting catalyzer by mixed serum.And the former resulting molecular weight distribution is suitable with the latter, explanation thus, method for preparing catalyst provided by the invention, the particle form of telomerized polymer effectively.
Though more than combined the embodiment specific embodiments of the invention to carry out detailed explanation, it is pointed out that protection scope of the present invention does not receive the restriction of these embodiments, but confirm by claims of appendix.Those skilled in the art can carry out suitable change to these embodiments in the scope that does not break away from technological thought of the present invention and purport, and these embodiments after changing obviously are also included within protection scope of the present invention.
Claims (11)
1. the preparation method of a load type non-metallocene catalyst may further comprise the steps:
Make the chemical processing agent and optional porous support reaction, the step that obtains to modify carrier that are selected from IV B family metallic compound through thermal activation treatment;
Magnesium compound is dissolved in the solvent, obtains the step of magnesium compound solution;
Said modification carrier, said magnesium compound solution are contacted with the Nonmetallocene part, obtain the step of mixed serum;
In said mixed serum, add precipitation agent, obtain the step of complex carrier; With
Make the chemical processing agent and the reaction of said complex carrier that are selected from said IV B family metallic compound, obtain the step of said load type non-metallocene catalyst.
2. according to the described preparation method of claim 1; It is characterized in that; Said porous support is selected from the refractory oxide or in infusibility composite oxides, clay, molecular sieve, mica, polynite, wilkinite and the zeyssatite one or more of partial cross-linked form, period of element Table II A, IIIA, IV A or the IV B family metal of olefin homo or multipolymer, Z 150PH or its multipolymer, Schardinger dextrins, polyester or copolyesters, polymeric amide or copolyamide, ryuron or multipolymer, Voncoat R 3310 or multipolymer, methylacrylic acid ester homopolymer or multipolymer, styrene homopolymers or multipolymer, these homopolymer or multipolymer; Be preferably selected from partial cross-linked styrene polymer, silicon-dioxide, aluminum oxide, Natural manganese dioxide, oxidation sial, oxidation magnalium, titanium oxide, molecular sieve and the polynite one or more, more preferably be selected from silicon-dioxide.
3. according to the described preparation method of claim 1; It is characterized in that; Said magnesium compound is selected from one or more in magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and the alkyl alkoxy magnesium, is preferably selected from the magnesium halide one or more, more preferably magnesium chloride.
4. according to the described preparation method of claim 1, it is characterized in that said solvent is selected from C
6-12Aromatic hydrocarbon, halo C
6-12In aromatic hydrocarbon, ester and the ether one or more are preferably selected from C
6-12In aromatic hydrocarbon and the THF one or more, most preferably THF.
5. according to the described preparation method of claim 1, it is characterized in that said Nonmetallocene part is selected from one or more in the compound with following chemical structural formula:
Be preferably selected from compound (A) with following chemical structural formula and in the compound (B) one or more:
More preferably be selected from compound (A-1) to compound (A-4) with following chemical structural formula and in compound (B-1) to the compound (B-4) one or more:
In above all chemical structural formulas,
Q is 0 or 1;
D is 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
-NR
23R
24,-N (O) R
25R
26,
-PR
28R
29,-P (O) R
30OR
31, sulfuryl, sulfoxide group or-Se (O) R
39, wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C
1-C
30Alkyl;
D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C
1-C
30Alkyl, sulfuryl, sulfoxide group,
-N (O) R
25R
26,
Or-P (O) R
32(OR
33), wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyanic acid, and wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, and wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
G is selected from C
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group;
Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, and wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyanic acid, and wherein atom is used in N, O, S, Se and the P coordination of respectively doing for oneself;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R
1To R
4, R
6To R
36, R
38And R
39Be selected from hydrogen, C independently of one another
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, is preferably formed aromatic ring; And
R
5Be selected from lone-pair electron on the nitrogen, hydrogen, C
1-C
30Alkyl, substituted C
1-C
30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R
5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R
5In N, O, S, P and Se can be used as coordination and carry out coordination with atom and said center IV B family atoms metal,
Said Nonmetallocene part further is preferably selected from one or more in the compound with following chemical structural formula:
Said Nonmetallocene part most preferably is selected from one or more in the compound with following chemical structural formula:
6. according to the described preparation method of claim 5, it is characterized in that,
Said halogen is selected from F, Cl, Br or I;
Said nitrogen-containing group is selected from
-NR
23R
24,-T-NR
23R
24Or-N (O) R
25R
26
Said phosphorus-containing groups is selected from
-PR
28R
29,-P (O) R
30R
31Or-P (O) R
32(OR
33);
Said oxy radical be selected from hydroxyl ,-OR
34With-T-OR
34
Said sulfur-containing group is selected from-SR
35,-T-SR
35,-S (O) R
36Or-T-SO
2R
37
The said seleno group that contains is selected from-SeR
38,-T-SeR
38,-Se (O) R
39Or-T-Se (O) R
39
Said group T is selected from C
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group;
Said R
37Be selected from hydrogen, C
1-C
30Alkyl, substituted C
1-C
30Alkyl or safing function property group;
Said C
1-C
30Alkyl is selected from C
1-C
30Alkyl, C
7-C
50Alkaryl, C
7-C
50Aralkyl, C
3-C
30Cyclic alkyl, C
2-C
30Thiazolinyl, C
2-C
30Alkynyl, C
6-C
30Aryl, C
8-C
30Condensed ring radical or C
4-C
30Heterocyclic radical, wherein said heterocyclic radical contain 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;
Said substituted C
1-C
30Alkyl is selected from and has one or more aforementioned halogens or aforementioned C
1-C
30Alkyl is as substituent aforementioned C
1-C
30Alkyl;
Said safing function property group is selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, contains tin group, C
1-C
10Ester group and nitro,
Wherein, said silicon-containing group is selected from-SiR
42R
43R
44Or-T-SiR
45Said germanic group is selected from-GeR
46R
47R
48Or-T-GeR
49Saidly contain tin group and be selected from-SnR
50R
51R
52,-T-SnR
53Or-T-Sn (O) R
54Said R
42To R
54Be selected from hydrogen, aforementioned C independently of one another
1-C
30Alkyl, aforementioned substituted C
1-C
30Alkyl or aforementioned safing function property group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and said group T ditto defines.
7. according to the described preparation method of claim 1, it is characterized in that, is 1 in the said magnesium compound of Mg element and the mol ratio of said Nonmetallocene part: 0.0001-1; Preferred 1: 0.0002-0.4, more preferably 1: 0.0008-0.2, further preferred 1: 0.001-0.1; The ratio of said magnesium compound and said solvent is 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml; In the said magnesium compound of magnesium compound solid and the mass ratio of said porous support is 1: 0.1-20, preferred 1: 0.5-10, more preferably 1: 1-5; The volume ratio of said precipitation agent and said solvent is 1: 0.2～5; Preferred 1: 0.5～2, more preferably 1: 0.8～1.5, and be respectively 1 in the said magnesium compound of Mg element independently of one another with mol ratio in the said chemical processing agent of IV B family metallic element: 0.01-1; Preferred 1: 0.01-0.50, more preferably 1: 010-030.
8. according to the described preparation method of claim 1; It is characterized in that; Said IV B family metallic compound is selected from one or more in IV B family metal halide, IV B family metal alkyl compound, IV B family metal alkoxide compound, IV B family metal alkyl halides and the IV B family metal alkoxide halogenide; Be preferably selected from the IV B family metal halide one or more, more preferably be selected from TiCl
4, TiBr
4, ZrCl
4, ZrBr
4, HfCl
4And HfBr
4In one or more, most preferably be selected from TiCl
4And ZrCl
4In one or more.
9. according to the described preparation method of claim 1; It is characterized in that; Said precipitation agent is selected from one or more in alkane, naphthenic hydrocarbon, halogenated alkane and the halo naphthenic hydrocarbon; Be preferably selected from pentane, hexane, heptane, octane, nonane, decane, hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane, methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane, three NBBs, chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, bromo cyclononane and the bromo cyclodecane one or more; Further be preferably selected from hexane, heptane, decane and the hexanaphthene one or more, most preferably hexane.
10. load type non-metallocene catalyst, it is by making according to each described preparation method of claim 1-9.
11. alkene homopolymerization/copolymerization process; It is characterized in that; Being Primary Catalysts according to the described load type non-metallocene catalyst of claim 10; To be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is promotor, makes alkene homopolymerization or copolymerization.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108570120A (en) * | 2017-03-10 | 2018-09-25 | 北京利和知信科技有限公司 | Ingredient of solid catalyst and catalyst containing o-phenylenediamine class compound and its application |
| CN111077259A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Solid-phase extraction, derivatization, separation and determination method of aniline compounds in gasoline |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364818A (en) * | 2002-02-09 | 2002-08-21 | 中国科学院上海有机化学研究所 | New olefine polymerization catalyst |
| CN1789292A (en) * | 2004-12-17 | 2006-06-21 | 扬子石油化工股份有限公司 | Application of supported non-metallocene catalyst in ethene polymerization process by slurry method |
| US20080227936A1 (en) * | 2004-12-17 | 2008-09-18 | Yangzi Petrochemical Company Co., Ltd. | Supported Nonmetallocene Olefin Polymerization Catalyst, Preparation Method and Use Thereof |
| CN101357958A (en) * | 2007-07-31 | 2009-02-04 | 中国石油化工股份有限公司 | Supported vanadium oxide non-metallocene catalyst for polyethylene and preparation method |
| CN101412766A (en) * | 2007-10-16 | 2009-04-22 | 中国石化扬子石油化工有限公司 | Magnesium compound load type non-metallocene catalyst and preparation thereof |
| CN101654492A (en) * | 2008-08-21 | 2010-02-24 | 中国石化扬子石油化工有限公司 | Super-high molecular polyethylene and preparation method and application thereof |
| CN101654494A (en) * | 2008-08-21 | 2010-02-24 | 中国石化扬子石油化工有限公司 | Ethane copolymer and preparation method and application thereof |
| CN101798361A (en) * | 2010-02-10 | 2010-08-11 | 中国科学院上海有机化学研究所 | Olefin polymerization catalysts |
-
2010
- 2010-09-16 CN CN 201010285958 patent/CN102399315B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364818A (en) * | 2002-02-09 | 2002-08-21 | 中国科学院上海有机化学研究所 | New olefine polymerization catalyst |
| CN1789292A (en) * | 2004-12-17 | 2006-06-21 | 扬子石油化工股份有限公司 | Application of supported non-metallocene catalyst in ethene polymerization process by slurry method |
| US20080227936A1 (en) * | 2004-12-17 | 2008-09-18 | Yangzi Petrochemical Company Co., Ltd. | Supported Nonmetallocene Olefin Polymerization Catalyst, Preparation Method and Use Thereof |
| CN101357958A (en) * | 2007-07-31 | 2009-02-04 | 中国石油化工股份有限公司 | Supported vanadium oxide non-metallocene catalyst for polyethylene and preparation method |
| CN101412766A (en) * | 2007-10-16 | 2009-04-22 | 中国石化扬子石油化工有限公司 | Magnesium compound load type non-metallocene catalyst and preparation thereof |
| CN101654492A (en) * | 2008-08-21 | 2010-02-24 | 中国石化扬子石油化工有限公司 | Super-high molecular polyethylene and preparation method and application thereof |
| CN101654494A (en) * | 2008-08-21 | 2010-02-24 | 中国石化扬子石油化工有限公司 | Ethane copolymer and preparation method and application thereof |
| CN101798361A (en) * | 2010-02-10 | 2010-08-11 | 中国科学院上海有机化学研究所 | Olefin polymerization catalysts |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108570120A (en) * | 2017-03-10 | 2018-09-25 | 北京利和知信科技有限公司 | Ingredient of solid catalyst and catalyst containing o-phenylenediamine class compound and its application |
| CN108570120B (en) * | 2017-03-10 | 2019-12-31 | 北京利和知信科技有限公司 | Solid catalyst component containing o-phenylenediamine compounds, catalyst and application thereof |
| CN111077259A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Solid-phase extraction, derivatization, separation and determination method of aniline compounds in gasoline |
| CN111077259B (en) * | 2018-10-19 | 2022-12-09 | 中国石油化工股份有限公司 | Solid-phase extraction, derivatization, separation and determination method of aniline compounds in gasoline |
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