Embodiment
The present invention discloses a kind of load method of non-metallocene olefin polymerization catalyst, and this method mainly comprises the following steps:
The carrier thermal activation and or chemical activation: carrier is under 100-1000 ℃, inert atmosphere or reduced pressure, and drying or roasting 1~24h carry out thermal activation; Carrier contacts with in metal halide, chlorosilane, aluminum alkyls, the aikyiaiurnirsoxan beta one or more and carries out chemical activation;
In solvent, carrier is contacted with non-metallocene olefin polymerization catalyst, wash then, filter, dry with drain into flowable pressed powder.
Resulting thus loaded catalyst, it mainly forms the middle layer that comprises that carrier, chemical activating agent and chemical processing agent are formed, and non-metallocene olefin polymerization catalyst.Non-metallocene olefin polymerization catalyst shape copying carrier form is a pulverulent solids that do, flowable.
The used carrier of the present invention can be arbitrarily, the surface has the porosu solid of functional group.It can be:
1, contain the organic materials of organo-functional group such as polyethylene, polypropylene, polybutene, polyvinyl alcohol, cyclodextrin and above-mentioned polymkeric substance based on monomeric multipolymer, polyester, polymeric amide, polyvinyl chloride, polyacrylic ester, polymethacrylate, polystyrene or partial cross-linked polymkeric substance, organo-functional group are selected from hydroxyl, primary amino, secondary amino group, sulfonic group, carboxyl, amide group, the mono-substituted amide group of N-, sulfonic acid amido, the mono-substituted sulfonic acid amido of N-, sulfydryl, acylimino and hydrazide group.Preferred partial cross-linked styrene polymer with surface hydroxyl functional group;
2, A, IIIA, IVA family and IVB family metal oxide are at interior solid inorganic oxide or halogenide, as silicon oxide (silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium white, Thorotrast, magnesium chloride, and the mixture formed of inorganic oxide, functional group is selected from surface hydroxyl or carboxyl.Relatively suitable have oh group for the surface, comprise silicon oxide and with one or more IIA, mA family mixed oxide, as silicon oxide-magnesia mixed oxide, silica-alumina mixed oxide, the mixed oxide of the metal oxide of preferred silicon oxide, aluminum oxide and silicon oxide and one or more IIA, IIIA family is as solid support material.
3, the oxidation material for preparing by the pyrohydrolysis process of gaseous metal oxide compound or silicon compound.
Clay or molecular sieve are as mica, polynite, wilkinite, diatomite, ZSM-5, MCM-41.
The surface-area (BET method mensuration) that is fit to the carrier of wanting required for the present invention preferably from 10 to about 1000m
2/ g, more preferably from 100 to 600m
2/ g.Pore volume (determination of nitrogen adsorption) preferred 0.1 to 4cm
3Between/the g, more preferably 0.2 to 2cm
3/ g.The median size of carrier (laser particle analyzer mensuration) is from 1 to 500 μ m, more preferably from 1 to 100 μ m preferably.In above-mentioned solid support material, preferred IIA, IIIA, IVA family and IVB family metal oxide are at interior solid inorganic oxide or halide carrier with surface hydroxyl, most preferably silica gel.It can be any form, as granular, spherical, aggregate or other form.The content of hydroxyl can be measured with known technology, as infrared spectroscopy, nuclear magnetic resonance method, titanium tetrachloride method, metal alkylide or metal hydride titration technique.Suitable silica-gel carrier is arbitrarily can be by the commerical prod of buying, and as Grace955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid245, ES70, ES70X, ES757, Aerosil812, or CS-2133 and MS-3040.
Metal oxide surface generally all is by the tart surface hydroxyl, can makes it inactivation with catalyst reaction.Before using, carrier will experience the dehydroxylation process, and it can be under vacuum or inert atmosphere, calcination activation.Silica-gel carrier roasting 1~24h under 100-1000 ℃, inert atmosphere or reduced pressure finishes.Here said inert atmosphere be meant only contain in the gas and trace or do not contain can with the component of carrier reaction.Roasting condition is preferably at 500~800 ℃, N
2Or continuing 2~12h under the Ar atmosphere, optimum is 4~8h.Dehydroxylation silica gel through thermal activation need be preserved under inert atmosphere.
The purpose of the thermal activation of silica-gel carrier is to make carrier surface have highly active group, report (J AmChem Soc is arranged, 1996,118:401) point out, when drying temperature is 200 ℃~500 ℃, the oh group that is easy to remove is reversibly removed, produce the siloxane groups of low reaction activity, but surpass under 600 ℃ the situation at drying temperature, oh group forcibly is removed, change into water, produce and to have the high ring stress and the siloxane groups of high reaction activity very.Also can adopt chemical activating agent that the functional group of carrier surface is changed into other nonreactive siloxane groups.
Carrier also can be without the high-temperature roasting step, thus but the realization dehydroxylation process that directly contacts with chemical activating agent.Here said chemical activating agent, it can be the chemical reagent of any and carrier surface hydroxyl reaction, as chlorosilane, the halogenide of IIIA, IVB or VB metal, alkylate or halogenated alkyl compounds, dimethylchlorosilane, trimethylchlorosilane, aluminum alkyls are such as aluminium trimethide, aluminium triethyl, butyl aluminium; Aikyiaiurnirsoxan beta is such as methylaluminoxane and aikyiaiurnirsoxan beta, butyl aikyiaiurnirsoxan beta.For the temperature and time in this process, the present invention does not do strict the qualification, as at normal temperatures can be longer slightly, can lack under the high-temperature slightly, and generally between 0.5h~48h, preferred 1~10h.
Involved in the present invention to solvent can be mineral oil and different liquid hydrocarbons, the most basic requirement is that catalyzer can be dissolved in wherein, and both do not react.Typical solvent is the varsol of from 5 to 12 carbon atoms, or the varsol that is replaced by the chlorine atom, and as methylene dichloride or ether solvent such as ether or tetrahydrofuran (THF), acetone, ethyl acetate etc. also can use.Optimization aromatic solvent such as toluene and dimethylbenzene; Or the aliphatic solvent of 6 to 10 carbon atoms, as hexane, heptane, octane, nonane, decane and their isomer, the cycloaliphatic solvent of 6 to 12 carbon atoms is as hexane; Or their mixture.Most preferably toluene, hexane or methylene dichloride.
Carrier through thermal activation or chemical activation can directly contact with non-metallocene olefin polymerization catalyst solution, thereby load obtains carry type non-metallocene calalyst for polymerization of olefine.But discover that originally if obtain active more excellent carry type non-metallocene calalyst for polymerization of olefine, it is very crucial further handling.Compare with the extra activity that loaded catalyst is obtained, the cost of this treatment step is inappreciable.This process is that the carrier through thermal activation or chemical activation is contacted with chemical processing agent, incipient impregnation such as chemical processing agent solution spraying are on carrier, or solution impregnation, as carrier impregnation is stirred 0.5~72h in the chemical treatment agent solution, preferred 2~24h, most preferably 2~6h.Chemical processing agent is selected from one or more the polynary treatment agents formed in halogenide, alkylate, alkoxy compound or the halogenated alkyl compounds that chemical activating agent is selected from aikyiaiurnirsoxan beta, aluminum alkyls, borine, IVA, IVB or VB family metal.
Aikyiaiurnirsoxan beta adopts lienar for (I) particularly
R-(A1 (R)-O) just
n-AlR
2
And/or the aikyiaiurnirsoxan beta of ring-type type aikyiaiurnirsoxan beta (II).
Just-(Al (R)-O-)
N+2
In structure (I) with (II), the R group can be identical or different, and be the C1-C8 alkyl, comprises methylaluminoxane, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, butyl aikyiaiurnirsoxan beta etc.Preferred R group is identical and is methyl, isobutyl-, phenyl or benzyl, most preferable, and n is the integer of 1-50, preferred 10~30.
Aluminum alkyls or boron alkyl are for having the compound of following general formula (III):
N(R)
3
Wherein: N is aluminium or boron, R and structure (I) and (II) in definition identical, each in three R groups can be identical, also can be different.Comprise alkyl metal cpd comprise trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-propyl aluminum, tri-butyl aluminum, dimethylaluminum chloride, triisopropylaluminiuand, three sec-butyl aluminium, three cyclopentyl aluminium, three amyl group aluminium, triisopentyl aluminium, three hexyl aluminium, ethyl dimethyl aluminium, methyl diethyl aluminum, three amyl group aluminium, three pairs-tolyl aluminium, dimethyl aluminium methylate, dimethyl aluminium ethylate, trimethyl-boron, triethyl-boron, tri-isobutyl-boron, tripropyl boron, tri butyl boron,
Halogenide, alkylate, alkoxy compound or the halogenated alkyl compounds of IVA, IVB or VB family metal are as SiCl
4, SiBr
4, Si (OC
2H
5)
3Cl, Si (OC
2H
5) Cl
3, S (OC
4H
9) Cl
3, Si (OC
4H
9)
3Cl, Si (OC
3H
7)
2Cl
2Deng; TiCl
4, TiBr
4, Ti (OC
2H
5)
3Cl, Ti (OC
2H
5) Cl
3, Ti (OC
4H
9) Cl
3, Ti (OC
4H
9)
3Cl, Ti (OC
3H
7)
2Cl
2, Ti (OC
6H
13)
2Cl
2, Ti (OC
8H
17)
2Br, Ti (OC
12H
25) Cl
3VCl
4, VBr
4, V (OC
2H
5)
3Cl, V (OC
2H
5) Cl
3, V (OC
4H
9) Cl
3, V (OC
4H
9)
3Cl, ZrCl
4, ZrBr
4, Zr (OC
2H
5)
3Cl, Zr (OC
2H
5) Cl
3, Zr (OC
4H
9) Cl
3, Zr (OC
4H
9)
3Cl, Zr (OC
3H
7)
2Cl
2, Zr (OC
6H
13)
2Cl
2, Zr (OC
8H
17)
2Br, Zr (OC
12H
25) Cl
3
Mentioned reagent can be used alone, but also also mix together.The halogen compounds of preferred aikyiaiurnirsoxan beta, titanium or zirconium, or contain the mixture of aikyiaiurnirsoxan beta, more preferably the binary chemical processing agent formed of methylaluminoxane and titanium tetrachloride.
The present invention is surprised to find that, directly adopts the halogenide of titanium, as TiCl
4As chemical processing agent, with independent employing methylaluminoxane or methylaluminoxane and TiCl
4The binary system of being formed is compared, and still can obtain very high polymerization activity and active lifetime, and is that the particle of polymkeric substance is a size uniform spherical particle more unexpectedly.
The adding of chemical processing agent can soon can be slow, preferably slowly adds, and helps dispersion process as dropping.
Washing, filtration, drying and the process of draining are to adopt method well known in the art, as drip washing, promptly under airtight or reactive atmosphere, can not be by the drip washing solid but can be at one by on the sand core funnel of solvent, by washing repeatedly of solvent to reach the purpose of washing and filtering; Or adopt Xian to wash, and promptly leave standstill and remove supernatant liquid, and then add solvent, so repeat these processes to reach the purpose of washing and filtering; Or the most usual method be will need washing and filtering system to going in the sand core funnel, take out by the suction filtration effect and desolvate, and then add solvent, suction filtration again, thereby reach the purpose of washing and filtering.The drip washing washing effect is best, but uneconomical, needs the time longer, and Xian washes simple, but effect is not thorough, the preferred suction filtration method of the present invention.The minimum triplicate that needs of washing and filtering process.The nature washing times is many more, and washing effect is just good more, but also can increase the consumption of solvent simultaneously.Preferred 3~5 times.Treatment temp and wash temperature are not subjected to strict restriction at this patent, can be 0 ℃~100 ℃.Preferred 20~80 ℃, between optimum 40 ℃~60 ℃.
Solid is about in temperature carries out drying under reduced pressure under 0~120 ℃, till obtaining mobile catalyst support powder.The length of this drying process time depends on used temperature, and the airtight situation of the ability of vacuum system and system is relevant.
Non-metallocene olefin polymerization catalyst involved in the present invention is the title complex (IV) with following structure
It mainly comprises the catalyst I VA and the IVB of following structure.
In order more to be expressly understood catalyst I VA, we can use IVA-1, and IVA-2, IVA-3 and IVA-4 come refinement to describe.
In order more to be expressly understood catalyst I VB, we can use IVB-1, and IVB-2, IVB-3 and IVB-4 come refinement to describe.
In all above-mentioned structures:
M:1,2 or 3;
Q:0 or 1;
D:0 or 1;
M: transition metal atoms, especially titanium, zirconium, hafnium, chromium, iron, cobalt, nickel, palladium;
N:1,2,3 or 4;
X: be the alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, the boron-containing group that comprise the replacement of the alkyl of halogen atom, hydrogen atom, Cl-C30 and Cl-C30, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain the group of tin group, several X can be identical in the structural formula, also can be different, can also be each other in key Cheng Huan;
The halogen atom here comprises fluorine, chlorine, bromine or iodine;
In the structural formula all parts electronegative sum absolute value should with metal M in the structural formula positively charged absolute value identical, all parts comprise X and polydentate ligand;
A: Sauerstoffatom, sulphur atom, selenium atom,
-NR
23R
24,-N (O) R
25R
26,
-PR
28R
29,-P (O) R
30R
31, sulfuryl, sulfoxide group ,-Se (O) R
39
B: refer to nitrogen-containing group, phosphorus-containing groups or C
1-C
30Hydro carbons;
D: refer to Sauerstoffatom, sulphur atom, selenium atom, contain C
1-C
30The nitrogen-containing group of alkyl, contain C
1-C
30The phosphorus-containing groups of alkyl, sulfuryl, sulfoxide group,
-N (O) R
25R
26,
-P (O) R
30R
31,-P (O) R
32(OR
33), wherein N, O, S, Se, P are ligating atom;
E: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
F: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
G: be inertia group, comprise or the safing function group, comprise C
1-C
30Alkyl, C
1-C
30The alkyl or the safing function group of replacement;
Y, Z: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
→: refer to singly-bound or two key;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R
1, R
2, R
3, R
4, R
5, R
10, R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
18, R
19, R
20, R
21, R
22, R
23, R
24, R
27, R
28, R
29, R
30, R
31, R
32, R
33, R
34, R
35, R
36, R
38, R
39: hydrogen, C
1-C
30Alkyl, halogen atom, C
1-C
30Substituted hydrocarbon radical be meant halogenated alkyl especially, as-CH
2Cl ,-CH
2CH
2Cl or safing function group, above-mentioned group can be the same or different to each other, wherein adjacent group such as R
1With R
2, R
3, R
3With R
4, R
6, R
7, R
8, R
9And R
23With R
24Or R
25With R
26Deng can be each other in key Cheng Huan.
R5 refers to lone-pair electron on the nitrogen, hydrogen, C
1-C
30Alkyl, C
1-C
30Alkyl, the oxy radical of replacement comprise hydroxyl, alkoxyl group-OR
34, the alkyl that has ether comprises-T-OR
34, sulfur-containing group comprises-SR
35,-T-SR
35, nitrogen-containing group comprises-NR
23R
24,-T-NR
23R
24, phosphorus-containing groups comprises-PR
28R
29,-T-PR
28R
29,-T-P (O) R
30R
31Work as R
5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group, phosphorus-containing groups, R
5In N, O, S, P, Se also can participate in coordination with metal.
T: be C
1-C
30Alkyl or C
1-C
30Substituted hydrocarbon radical or safing function group; Such as following Nonmetallocene alkene olefin polymerization catalysis:
Preferred structure is to be the non-metallocene olefin polymerization catalyst shown in 1,3,6,16,23.Most preferred configuration is the non-metallocene olefin polymerization catalyst shown in 1 or 6.
Non-metallocene olefin polymerization catalyst is dissolved in the solvent, then the carrier with process step noted earlier contacts, here said contact both was meant and the carrier of flowable state can be joined in the solution of non-metallocene olefin polymerization catalyst, also the solution of non-metallocene olefin polymerization catalyst can be joined on the carrier of flowable state.Under agitation condition, react then.Temperature of reaction is not also done strict qualification in this patent, optionally temperature is as between 0 ℃~100 ℃, preferably between 20 ℃~60 ℃.
The chemical treating process of above-described carrier and the loading process of non-metallocene olefin polymerization catalysts all need carry out under the anhydrous and oxygen-free condition of strictness, here said anhydrous and oxygen-free condition is meant that the content of water and oxygen in the system continues less than 10ppm, and the anhydrous and oxygen-free condition is one of key factor that obtains highly active supported catalyst.
Carry type non-metallocene calalyst for polymerization of olefine having thus described the invention is a Primary Catalysts, aluminum alkyls, aikyiaiurnirsoxan beta or Lewis acid, boron fluothane, boron alkyl, boron alkyl ammonium salt are promotor, under the condition that is enough to react, carry out C2~C10 slurry olefin polymerization, vapour phase polymerization, letex polymerization, solution polymerization or copolymerization.
At the used C2 of polymkeric substance~C10 alkene with method preparation of the present invention, be selected from ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene, 1-cyclopentenes, norbornylene, norbornadiene or vinylbenzene, 1,4 divinyl, 2,5-pentadiene, 1, the 6-hexadiene, or contain the functional groups organic monomer, as the homopolymerization and the copolymerization process of vinyl acetate between to for plastic, methyl acrylate, ethyl propenoate, butyl acrylate.
Polyreaction can adopt technology well known in the art to carry out, preferred slurries polymerization and gaseous polymerization, polymerization single polymerization monomer with or comonomer and carry type non-metallocene calalyst for polymerization of olefine can under-40 ℃~120 ℃, normal pressure~10MPa, contact continuously or carry out off and on.Slurry polymerization process most preferably, especially for ethene, perhaps ethene and other alkene, the polymerization that contains the functional groups organic monomer and copolymerization process.
Polymer solvent can be to be selected from the solvent described in the front load process in the slurry polymerization process, preferred hexane solvent.
The promotor that can be used as this polymerization system has aluminum alkyls, aikyiaiurnirsoxan beta or Lewis acid, boron fluothane, boron alkyl, boron alkyl ammonium salt.Aluminum alkyls, aikyiaiurnirsoxan beta have been done detailed narration in front, and Lewis acid, boron fluothane, boron alkyl, boron alkyl ammonium salt then are meant the compound with following logical formula V:
[L-H]
+[NE
4]
-Or [L]
+[NE
4]
-
Wherein L is neutrality or male ionic Lewis acid, and H is a hydrogen atom, and N is aluminium or boron, and each E can be identical or different, for having the aryl of 6~12 carbon atoms, wherein has more than one hydrogen to be replaced by halogen atom, alkoxyl group or phenoxy group.Comprise trimethyl ammonium tetraphenyl boron, trimethyl ammonium four (right-tolyl) boron, the basic boron of tributyl ammonium four (five fluorine boron), trimethyl-phosphine tetraphenyl boron, trimethyl ammonium tetraphenyl aluminium, tripropyl ammonium tetraphenyl aluminium, trimethyl ammonium four (right-tolyl) aluminium, triethyl ammonium four (neighbours, right-3,5-dimethylphenyl) aluminium, tributyl ammonium four (right-trifluoromethyl) aluminium, trimethyl ammonium four (right-trifluoromethyl) aluminium, tributyl ammonium four (pentafluorophenyl group) aluminium, N, N-Diethyl Aniline tetraphenyl aluminium, N, N-ethylaniline four (pentafluorophenyl group) aluminium, diethyl ammonium four (pentafluorophenyl group) aluminium etc.
The preferred aikyiaiurnirsoxan beta of promotor, the most preferable aikyiaiurnirsoxan beta.
Here the said condition that is enough to carry out polyreaction for slurry polymerization, then is meant temperature condition, pressure condition, mixing speed situation.
If desired, hydrogen can be used as the polymericular weight conditioning agent to be added, and its branch covers 0.01~5% of polymer monomer pressure, and preferred 0.1%~2%.
Polymerization pressure is at 0.1~10MPa, preferred 0.5~4MPa, optimum 1~3MPa.The raising of polymerization pressure can increase The Thermal Capacity of Gaseous, thereby helps heat passage in the reaction process.
The present invention finds that too high polymerization pressure can cause sticking still, can not obtain the good polymkeric substance of form.
Embodiment 1
1.1 the preparation of loaded catalyst
1.1.1 the activation of carrier
Get ES-70 type silica gel (Crosfield company product) roasting under nitrogen atmosphere.Its roasting condition is: 5 ℃/Min of temperature rise rate, and 200 ℃ of following constant temperature 0.5h, 400 ℃ of following constant temperature 0.5h are then at 600 ℃ of following constant temperature 4h, naturally cooling under nitrogen atmosphere at last.Be designated as the ES-70-600 carrier.
1.1.2 the chemical treatment of carrier
Under the nitrogen atmosphere of anhydrous and oxygen-free (content of water and oxygen all is lower than 5ppm), get 2.0413g ES-70-600 carrier, add the 20ml toluene solvant and stir formation suspension.Get the toluene solution (brief note for former MAO, MAO accounts for 15wt%, Witco company product) of 2ml methylaluminoxane (MAO), under 25 ℃ and agitation condition, slowly be added drop-wise in the above-mentioned suspension.Continue to stir 2h.Get titanium tetrachloride (TiCl again
4) hexane solution (titanium content is 0.41mol/L) 10ml, under 25 ℃ and agitation condition, slowly drip in above-mentioned mixed system, continue to stir 2h at last again.
1.1.3 washing, filter, dry and drain
With the suspension suction filtration, with the washing of 4 * 30ml toluene solvant, at last with gained solid decompressing and extracting Cheng Gan, flowable powder under vacuum condition.
1.1.4 the load of catalyzer
Take by weighing the non-metallocene olefin polymerization catalyst of 96.5mg structural formula shown in (6), join in the 20ml toluene,, and then join among the support powder, stir 12h 25 ℃ of following stirring and dissolving.
Adopt the washing of 1.1.3 method, filter, dry and drain, obtain doing, can flow, the loaded catalyst of orange.
1.2 polymerization
In the 0.5L autoclave of crossing with the exsiccant nitrogen purging, add 98.2mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent simultaneously, at ethylene pressure is that 1.04MPa, mixing speed are to carry out vinyl polymerization under 50 ℃ of 560rpm and the constant temperature, and the reaction times is 1h.Take out polymkeric substance, dry removing desolvated.
Output: 12.4g, DSC scanning curve show that polyethylene has 134.96 ℃ and 141.13 ℃ of two melting peaks.
Embodiment 2
2.1 Preparation of catalysts
Preparation of catalysts process similar embodiment 1.1 is got 2.048g ES-70-600 carrier, adds the 20ml toluene solvant.Slowly drip the toluene solution (former MAO and toluene solvant carry out dilution in 1: 9, note by abridging to be rare MAO) of 2ml MAO, slowly drip 10ml TiCl again
4Hexane solution (titanium content is 0.41mol/L), wash then, filter, dry and drain.
The non-metallocene olefin polymerization catalyst that takes by weighing 224mg is dissolved in the 40ml toluene solvant, so joins among the support powder, stirs 12h.Wash at last, filter, dry and drain.
The titanium content of carry type non-metallocene calalyst for polymerization of olefine is 2.4%.
2.2 polymerization
Adding 48.7mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 1.04MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 150rpm, temperature of reaction is 30 ℃, behind the 30min, increases mixing speed to 570rpm with improve temperature of reaction to 60 ℃, continues to react 1.5h.
Output: 21.72g, 140.56 ℃ of polyethylene fusing points.
Adding 40.9mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 2MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 200rpm, temperature of reaction is 30 ℃, behind the 30min, increases mixing speed to 600rpm with improve temperature of reaction to 50 ℃, continues to react 4.5h.
Output: 60.35g, 140.31 ℃ of polyethylene fusing points.
Adding 163.8mg loaded catalyst, the former MAO of 6ml and 260ml hexane solvent in the 2L autoclave simultaneously, is that 1.1MPa carries out vinyl polymerization at ethylene pressure.Mixing speed 300rpm, initial reaction temperature is 30 ℃, behind the 3.5h, improves temperature of reaction to 50 ℃, continues reaction 1.5h.
Output: 48.80g, 140.31 ℃ of polyethylene fusing points.
2.3 copolymerization
Add 48.3mg loaded catalyst, the former MAO of 6ml and 500ml hexane solvent in the 2L autoclave simultaneously, opening mixing speed simultaneously is 300rpm.
Under 60 ℃, ethene and butylene are mixed according to mass ratio at 5: 1, in autoclave, provide interpolymer then, keep pressure 1.3MPa in the autoclave.Initial reaction temperature is 30 ℃, improves temperature of reaction to 50 ℃ behind the 30min, continues reaction 1.5h.
Output 23.74g, 127.81 ℃ of polyethylene fusing points.
Embodiment 3
Preparation of catalysts similar embodiment 1.1 is got 2.008g ES-70-600 carrier, adds the 20ml toluene solvant.Slowly drip 10ml TiCl
4Hexane solution (titanium content is 0.41mol/L), wash then, filter, dry and drain.Take by weighing the 191.4mg non-metallocene olefin polymerization catalyst and be dissolved in the 35ml toluene, join among the support powder, stir 12h.Wash at last, filter, dry and drain.
The titanium content of carry type non-metallocene calalyst for polymerization of olefine is 2.57%.
Polymerization process similar embodiment 1.2 is carried out.Adding 54.1mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 1.04MPa, mixing speed are to carry out vinyl polymerization under 50 ℃ of 560rpm and the constant temperature at ethylene pressure.Reaction times is 2h.
Output: 13.45g, 136.88 ℃ of polyethylene fusing points.
Adding 44mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 2.0MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 150rpm, temperature of reaction is 25 ℃, behind the 30min, increases mixing speed to 590rpm with improve temperature of reaction to 50 ℃, continues to react 1.5h.
Output: 24.65g.
Embodiment 4
Preparation of catalysts similar embodiment 1.1 is got 1.6884g ES-70-600 carrier, adds the 20ml toluene solvant.Slowly drip 10ml SiCl
4Toluene solution (0.435mol/L), wash then, filter, dry and drain.Take by weighing the 137.5mg non-metallocene olefin polymerization catalyst and be dissolved in the 15ml toluene, join among the support powder, stir 12h.Wash at last, filter, dry and drain.
The titanium content of carry type non-metallocene calalyst for polymerization of olefine is 0.605%.
Polymerization similar embodiment 1.5 is carried out.In the 0.5L autoclave, add 92.1mg loaded catalyst, the former MAO of 4ml simultaneously) and the 250ml hexane solvent.Reaction times is 1h.
Output: 4.817g, DSC scanning curve show that polyethylene has 137.39 ℃ and 141.66 ℃ of two melting peaks.
Embodiment 5
The reactivation process of carrier is similar to the 1.1.1 among the embodiment.Get ES-70 type silica gel at 650 ℃ of following constant temperature 4h, be designated as the ES-70-650 carrier.
Preparation of catalysts process similar embodiment 3 is got 2.155g ES-70-650 carrier, adds the 20ml toluene solvant.Slowly drip 10ml TiCl
4Toluene solution (titanium content is 0.41mol/L), washing, filter, dry and take out.Take by weighing the non-metallocene olefin polymerization catalyst of 51.6mg structural formula shown in (16) and be dissolved in the 25ml toluene, join among the support powder, stir 24h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 137.1mg loaded catalyst, the former MAO of 6ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 1.0MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 150rpm, temperature of reaction is 25 ℃, behind the 30min, increases mixing speed to 590rpm with improve temperature of reaction to 50 ℃, continues to react 1.5h.
Output: 24.83g, 134.55 ℃ of polyethylene fusing points.
Embodiment 6
Preparation of catalysts process similar embodiment 1.1.Get 1.03g ES-70-650 carrier, add the 20ml toluene solvant, slowly drip the rare MAO of 2ml.Wash then, filter, dry and drain.Take by weighing the non-metallocene olefin polymerization catalyst of 106mg structural formula shown in (6), be dissolved in the 20ml toluene solvant, add 5ml TiCl
4Hexane solution (titanium content is 0.41mol/L), stir 2h after, join again among the support powder, stir 12h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 56.4mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 2.0MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 200rpm, temperature of reaction is 25 ℃, behind the 30min, increases mixing speed to 600rpm and raising
Temperature of reaction to 50 ℃ continues reaction 1.5h.
Output: 12.30g, 137.97 ℃ of polyethylene fusing points.
Embodiment 7
Get ES-70 type silica gel at 300 ℃ of following constant temperature 6h, be designated as the ES-70-300 carrier.
Preparation of catalysts process similar embodiment 2.Get the 1gES-70-300 carrier, add the 20ml toluene solvant.Slowly drip the rare MAO of 4ml, slowly drip 10ml TiCl again
4Hexane solution (titanium content is 0.41mol/L), continue to stir 2h, wash then, filter, dry and drain.The non-metallocene olefin polymerization catalyst that takes by weighing 119mg is dissolved in the 20ml toluene, joins among the support powder, stirs 12h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 30.6mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is 2.0MPa at ethylene pressure, and mixing speed is to carry out vinyl polymerization under the 600rpm condition.Initial reaction temperature is 25 ℃, behind the 30min, improves temperature of reaction to 50 ℃, continues reaction 1.5h.
Output: 9.141g, 142.04 ℃ of polyethylene fusing points.
Embodiment 8
Preparation of catalysts process similar embodiment 3 takes by weighing 1.01g ES-70-300 carrier, adds the 20ml toluene solvant.Slowly drip 10mlTiCl
4Hexane solution (titanium content is 0.41mol/L), continue to stir 2h, wash then, filter, dry and drain.The non-metallocene olefin polymerization catalyst that takes by weighing 130mg is dissolved in the 20ml toluene, joins among the support powder, stirs 12h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 36mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is 2.0MPa at ethylene pressure, and mixing speed is to carry out vinyl polymerization under the 600rpm condition.Initial reaction temperature is 25 ℃, behind the 30min, improves temperature of reaction to 50 ℃, continues reaction 1.5h.
Output: 32.766g, 135.47 ℃ of polyethylene fusing points.
Embodiment 9
Preparation of catalysts similar embodiment 2 takes by weighing 1.071g ES-70-300 carrier, adds the 20ml toluene solvant.Slowly drip the toluene solution (1.01mol/L) of 1ml trimethyl aluminium (TMA), continue to stir 2h, slow again Dropwise 5 mlTiCl
4Hexane solution (titanium content is 0.41mol/L), continue to stir 2h.Through washing, filter, dry and drain into dried, flowable powder.The non-metallocene olefin polymerization catalyst that takes by weighing 104mg is dissolved in the 20ml toluene, and then joins among the support powder, stirs 12h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 36.4mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is 2.0MPa at ethylene pressure, and mixing speed is to carry out vinyl polymerization under the 600rpm condition.Initial reaction temperature is 30 ℃, behind the 30min, improves temperature of reaction to 50 ℃, continues reaction 1.5h.
Output: 18.27g, 138.36 ℃ of polyethylene fusing points.
Embodiment 10
Preparation of catalysts similar embodiment 3 takes by weighing 1.077g ES-70-300 carrier, adds the 20ml toluene solvant.Slow Dropwise 5 ml TiCl
4Hexane solution (titanium content is 0.41mol/L), continue to stir 2h, wash then, filter, dry and drain.The non-metallocene olefin polymerization catalyst that takes by weighing 101mg is dissolved in the 20ml toluene, joins among the support powder, stirs 12h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 36.3mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is 2.0MPa at ethylene pressure, and mixing speed is to carry out vinyl polymerization under the 600rpm condition.Initial reaction temperature is 30 ℃, behind the 30min, improves temperature of reaction to 40 ℃, continues reaction 1.5h.
Output: 34g, 137.32 ℃ of polyethylene fusing points.
Embodiment 11
The reactivation process of carrier is similar to the 1.1.1 among the embodiment.Get PQ-2133 type silica gel (Pq Corp.'s product) at 650 ℃ of following constant temperature 4h, be designated as the CS-2133-650 carrier.
Preparation of catalysts similar embodiment 3.Get 1.01g CS-2133-650 carrier, add the 20ml toluene solvant and stir formation suspension.Slow Dropwise 5 ml TiCl
4Hexane solution (titanium content is 0.41mol/L), wash then, filter, dry and drain.Take by weighing the non-metallocene olefin polymerization catalyst of 104mg structural formula shown in (16), join in the 25ml toluene,, and then join among the support powder, stir 24h 25 ℃ of following stirring and dissolving.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 46.6mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 2.0MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 150rpm, temperature of reaction is 30 ℃, behind the 30min, increases mixing speed to 600rpm with improve temperature of reaction to 50 ℃, continues to react 3h.
Output: 36g.
Embodiment 12
Take by weighing ES-70-300 silica-gel carrier 0.510g, add the 20ml toluene solvant, stir and form suspension, add 2.5ml dimethyldichlorosilane(DMCS) ((CH again
3)
2SiCl
2) toluene solution (contain (CH
3)
2SiCl
210%V/V).React 2h after scouring, filtration, drying, drain.And then the TiCl of adding 2.5ml
4Hexane solution (titanium content is 0.41mol/L), wash again, filter, dry, drain.Take by weighing the non-metallocene olefin polymerization catalyst of 70mg structural formula shown in (16), be dissolved in the 20ml toluene, join among the support powder, stir 48h.Wash at last, filter, dry and drain.
Output: 24.2g.
Embodiment 13
Preparation of catalysts similar embodiment 1.1.Take by weighing 0.9858g crosslinked polystyrene carrier, add toluene 60ml, drip the former MAO of 8ml again, constant temperature stirs 1h down for 50 ℃, washing, filter, dry and drain.Take by weighing the 251.5g non-metallocene olefin polymerization catalyst, be dissolved in the 60ml toluene, above-mentioned solid is joined in the catalyst solution, stir 3h, and then washing, filter, dry and drain.
The titanium content of carry type non-metallocene calalyst for polymerization of olefine is 0.538%.
Polymerization similar embodiment 1.2 is carried out.Adding 114.7mg loaded catalyst, the former MAO of 6ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 1.04MPa carries out vinyl polymerization at ethylene pressure.Mixing speed 600rpm, temperature of reaction is 45 ℃, reaction 3h.
Output: 13.25g, 139.21 ℃ of polyethylene fusing points.