CN107501444A - Support type benzene oxygen imines polyolefin catalyst and preparation method and application - Google Patents
Support type benzene oxygen imines polyolefin catalyst and preparation method and application Download PDFInfo
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- CN107501444A CN107501444A CN201710897805.4A CN201710897805A CN107501444A CN 107501444 A CN107501444 A CN 107501444A CN 201710897805 A CN201710897805 A CN 201710897805A CN 107501444 A CN107501444 A CN 107501444A
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- AZXAJUZMRICQJC-UHFFFAOYSA-N CC(C1)C=C(C=O)C(O)=C1C(C)(C)c1ccccc1 Chemical compound CC(C1)C=C(C=O)C(O)=C1C(C)(C)c1ccccc1 AZXAJUZMRICQJC-UHFFFAOYSA-N 0.000 description 1
- OQACDTOVKOJFPW-STKMKYKTSA-N CC(CCCC1)C1/N=C/c(cc(C(C)(C)c1ccccc1)cc1C(C)(C)c2ccccc2)c1O Chemical compound CC(CCCC1)C1/N=C/c(cc(C(C)(C)c1ccccc1)cc1C(C)(C)c2ccccc2)c1O OQACDTOVKOJFPW-STKMKYKTSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/28—Titanium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Abstract
The present invention relates to a kind of support type benzene oxygen imines polyolefin catalyst and preparation method and application, first by the derivative of phenol, paraformaldehyde, organic catalyst and triethylamine mixing, using acetonitrile as solvent, salicylaldehyde derivatives are prepared, salicylaldehyde derivatives and primary amine or imines are reacted in ethanol, obtain schiff bases, then catalyst precarsor is prepared again, catalyst precarsor is supported on carrier, obtain catalyst, the catalyst can be used for catalyzed ethylene polymerization, it can also be used to be catalyzed propylene homo or ethene and linear alkene copolymerization of the carbon number 3~8, it can also be used for being catalyzed the copolymerization of ethene and ENB.Compared with prior art, when the present invention is used to be catalyzed ethylene homo, High molecular weight polyethylene of the molecular weight 200,000 1,000 ten thousand can be obtained, its average grain diameter can<180 μm, 40 mesh sieving rates can reach 99%, and catalytic activity is up to 30000g polyethylene/g catalyst.
Description
Technical field
The present invention relates to olefin coordination polymerization field, more particularly, to support type benzene oxygen imines polyolefin catalyst and system
Preparation Method and application.
Background technology
Find that Ziegler-Natta catalyst effectively can obtain high density polymerization by catalysis in olefine polymerization from the 1950s
Since thing, by the technological innovation of nearly 70 years, polyolefin catalyst obtained significant progress.On the one hand, it is different by adding
Electron donor, to MgCl2Carrier carries out the method that different processing greatly improves Z-N catalyst performances, in polyolefin industry
In obtained very extensive application；On the other hand, scientific research personnel assigns polymer by the new catalyst system of developmental research
New functional characteristic, solves the insoluble application demand of a part of traditional Z-N catalyst.In these new catalyst system and catalyzings,
One kind is containing the metallocene catalyst that luxuriant ring is representative in the part that Kaminsky in 1980 and Sinn are synthesized, by nearly 40 years
Research, the problem that activity declines to a great extent after it is loaded just progressively solves, and progressively popularization and application in the industry；It is another kind of be with
The benzene oxygen imine catalyst (FI catalyst) of Fujita of Mitsui Chemicals, Inc. in 1998 et al. research and development is the Nonmetallocene of representative
Catalyst, industrial applications report are still seldom.Hinder that Catalyst is applied clinically and popularized it is critically important the reason for one of be that it is negative
Technique is carried, in the past 10 years, the preparation to this kind of catalyst both at home and abroad, the research of carrying method make some progress.
Mitsui Chemicals, Inc Fujita et al. provides a kind of olefin polymer in patent CN1699434A and contains this
The method of the resin combination of olefin polymer, the molecular weight of polyethylene obtained in patent is relatively low, weight average molecular weight 7000 with
Do not loaded down and.Mitsui Chemicals, Inc discloses benzene oxygen imine catalyst in the A1 of patent EP 1881014 and is used for second
The copolymerization process of alkene/propylene/5- vinyl -2- ENBs, but catalytic activity is relatively low.
Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences provides the seat of a kind of olefin-containing epoxide in patent CN1651472A
The Group IVB complex of husband's alkali is simultaneously applied to the method for vinyl polymerization.The patent is prepared in the salicylide of synthesis alkyl substitution
In, the RMgBr of excess is used as catalyst, but RMgBr is costly, and there is larger danger.In addition, patent
The complex provided is only used for ethene homogeneous polymerization and not loaded, and the co-catalyst used contains MAO or MMAO,
Industrial applications are difficult.
Reliance Industries company provides in A a kind of extensive in A, the CN 104053684 of patent US 2014/0221588
Synthesize the non-cryogenic technique of ultra-high molecular weight polyethylene (DUHMWPE) polymer of disentanglement.The process catalyst is containing fluorobenzene
Oxygen imine structure Titanium series catalyst, DUHMWPE can be obtained under the poly- MAO of co-catalyst using the catalyst.The said firm
A kind of benzene oxygen imine structure by unsymmetric ligand is also disclosed in patent US 20150005461A1, CN 104334590 A
The single site catalysts being fixed on inorganic matter carrier.By the catalyst under conditions of P-MAO does co-catalyst, ethene
Pressure is to carry out polymerisation under 7bar, can obtain ultra-high molecular weight polyethylene, but catalyst activity is relatively low.
LG Chemical Ltd. of South Korea discloses a kind of new support type hydridization cyclopentadienyl gold in the A of patent CN 102665909
Metal catalyst, it includes catalyst precarsor and the carrier for loading the catalyst precarsor.It is sub- that catalyst precarsor includes benzene oxygen
The metallic compound of amine, carrier used are in silica, silica-alumina and silica-magnesia
It is at least one.Vinyl polymerization is carried out with such catalyst, embodiment middle-molecular-weihydroxyethyl reaches as high as 670,000, but catalyst activity is inclined
It is low.
A kind of Zhejiang University's tandem catalysis ethene disclosed in the A of patent CN 104356269 prepares single distribution LLDPE side
Method, this method use tandem system (including the first catalyst, the second catalyst and co-catalyst), the single charging of ethene.Wherein
Second catalyst is the double benzene oxygen imines titanium catalysts of fluoro, in the presence of co-catalyst, can obtain 1.2 ten thousand~3,140,000 it is poly-
Ethene, but the polymerization activity of itself and undeclared catalyst.
Shanghai Organic Chemistry Institute, Chinese Academy of Sciences discloses a kind of tridentate ligand in the A of patent CN 102030844
Non-metallocene catalyst, its carrying method is first by metal and carrier function, then is reacted with part.Urged after overload
It is higher to change ethylene polymerization activity, can obtain the polyethylene of super high molecular weight, but in embodiment average grain diameter more than 200 μm.
Yangzi Petrochemical Co., Ltd provides a kind of non-metallocene olefin polymerization in patent CN 1962702A
The supported method of catalyst incipient impregnation.Catalyst precarsor and the A of patent CN 102030844 employed in the patent is a kind of
The non-metallocene catalyst of tridentate ligand is basically identical.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of support type benzene oxygen is sub-
Amine polyolefin catalyst and preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of support type benzene oxygen imines polyolefin catalyst, including catalyst precarsor and for loading the catalyst precarsor
Carrier, described catalyst precarsor has structure shown in formula (I) or formula (II)：
Wherein：
M is titanium, zirconium, hafnium or vanadium；
X1For one kind in C, Si and Ge；
X2And X3It is identical or different, represent the straight chained alkyl of 1~10 carbon atom, halogen atom, nitrogen-containing group, halogen group,
Oxy radical, phosphorus-containing groups, boron-containing compound or heterocyclic group；
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12It independently is alkyl, the halogen of hydrogen, 1~20 carbon atom
Plain, halogen group, oxy radical, phosphorus-containing groups, boron-containing compound, jeterocyclic chemistry group, aromatic group or alicyclic group；
R in formula (II)13、R14And R15For one kind in hydrogen, methyl, ethyl, isopropyl or the tert-butyl group；
The carrier for being used to load the catalyst precarsor includes silica, aluminum oxide, the alcohol adduct of magnesium halide, dioxy
Change one or more mixture such as titanium, montmorillonite, ion exchange resin and clay.
Preferably,
M is Zr or Ti elements；
X1For C or Si elements；
R1、R2And R3For the combination of methyl and phenyl；R5And R8For in hydrogen, methyl, ethyl, isopropyl, cumyl, methoxyl group
It is a kind of；
R4、R6、R7、R9、R10、R11、R12For one kind in hydrogen, methyl, halogen.
Preferably, the synthesis of described catalyst precarsor comprises the following steps：
(1) salicylaldehyde derivatives are prepared：By the derivative of phenol, paraformaldehyde, organic catalyst and triethylamine according to rubbing
You compare 0.01-1:0.02-6:0.01-1:0.02-6 is added in reaction bulb, using acetonitrile as solvent, is heated to reflux 1-24h, is made
Described salicylaldehyde derivatives, wherein, organic catalyst is magnesium halide；
(2) part of catalyst precarsor is prepared：The salicylaldehyde derivatives and primary amine or imines that are obtained in step (1) are massaged
Your proportioning is 0.1-1:0.15-2.0 is added in reaction bulb, using absolute ethyl alcohol as solvent, obtains schiff bases through processing after reaction, i.e.,
For the part of catalyst precarsor；
(3) catalyst precarsor is prepared：By the part obtained in step (2) with first being reacted with n-BuLi, by concentration, filter
Lithium salts is removed, then catalyst precarsor is obtained with the tetrahydrofuran complex reaction of chlorination metal.
Preferably, described carrier be grain diameter be 10-500 μm, 50~500m of specific surface area2/ g silica,
Or by particle diameter it is 1-100 μm, specific surface area 10-100m2The particle diameter that/g magnesium chloride granules alcohol obtains after closing is 5-50 μm of halogen
Change the alcohol adduct of magnesium.
It is further preferred that the alcohol of the alcohol adduct of magnesium halide is the fatty alcohol or alicyclic ring alcohol of 1 to 10 carbon atom, element M g
Mol ratio with alcohol is 1:1-5.
The preparation method of described benzene oxygen imines polyolefin catalyst, comprises the following steps：
(a) catalyst precarsor is dissolved with organic solvent, after dissolving, adds activating substance and activated, or do not enter
Row activation, obtains catalyst precursor solution；
(b) carrier of processing before passing through is added in catalyst precursor solution, stirring contact, catalyst precarsor is supported on
On carrier, then by post processing, described catalyst is obtained.
Preferably,
In step (a), described organic solvent be dichloromethane, chloroform, toluene, tetrahydrofuran, linear paraffin and
One or more in alicyclic, described activating substance are alkyl aluminum, aluminum alkoxide or boride；
In step (b), described stirring Contact Temperature is controlled between 0~80 DEG C, and stirring time of contact is 0.5~48h；
The means of support pretreatment include heat treatment and/or chemical treatment：
The means of support pretreatment include heat treatment and/or chemical treatment, and described heat treatment is calcining, and calcining heat is
150~600 DEG C, calcination time is 2~48h, preferably 300 DEG C~400 DEG C processing 10h, and described chemical treatment is, by carrier with
A kind of 1~72h of contact in organic solvent in the activators such as alkyl aluminum, aluminum alkoxide, boride, organosilicon, reaction temperature
For -20~80 DEG C, 2-24h is preferably contacted, temperature control is at 0 DEG C~60 DEG C.
Preferably, the post processing in step (b) includes reactant is the processing step such as filtered to, washed, dried.
The application of described benzene oxygen imines polyolefin catalyst, the catalyst are catalyzed second in the presence of co-catalyst
Alkene polymerize.
Preferably, described co-catalyst is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, methyl
One or more mixtures in aikyiaiurnirsoxan beta and organic boride, preferably triethyl aluminum or triisobutyl aluminium, polymerization temperature are
30~90 DEG C, preferably 40 DEG C~80 DEG C；
The reaction of catalyzed ethylene polymerization can be including n-hexane, normal heptane, 120# solvent naphthas, 90# solvent naphthas, dichloromethane
Boiling point including alkane, toluene or dimethylbenzene is to be carried out in 30~150 DEG C of organic solvent, preferably n-hexane or normal heptane.
Preferably, when the catalyst is used to be catalyzed ethylene homo, macromolecule of the molecular weight 200,000-1,000 ten thousand can be obtained
Weight northylen, its average grain diameter can<180 μm, 40 mesh sieving rates can reach 99%, and catalytic activity is urged up to 30000g polyethylene/g
Agent.
The application of described benzene oxygen imines polyolefin catalyst, the catalyst can also be catalyzed propylene homo, person's ethene
With linear alkene copolymerization and the copolymerization of ethene and ENB of the carbon number 3~8.
Part and the atom of metal center coordination are N, O in benzene oxygen imine catalyst precursor in the present invention, through Overheating Treatment
Silica, by being chemically treated the carrier surface such as chlorination magnesium alcoholate also containing the O atom for being available for coordination.Suitable carrier
Processing method can make carrier close with the O atom coordination ability of part, and when catalyst precarsor and carrier function, carrier depends on its O
Atom participates in metal center coordination, and catalyst load is more firm, and then catalytic activity is substantially improved.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
Benzene oxygen imines polyolefin catalyst precursor, there is structure shown in formula (I) or formula (II)：
Wherein：
M is titanium, zirconium, hafnium or vanadium；
X1For one kind in C, Si and Ge；
X2And X3It is identical or different, represent the straight chained alkyl of 1~10 carbon atom, halogen atom, nitrogen-containing group, halogen group,
Oxy radical, phosphorus-containing groups, boron-containing compound or heterocyclic group；
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12It independently is alkyl, the halogen of hydrogen, 1~20 carbon atom
Plain, halogen group, oxy radical, phosphorus-containing groups, boron-containing compound, jeterocyclic chemistry group, aromatic group or alicyclic group.
R in formula (II)13、R14And R15For one kind in hydrogen, methyl, ethyl, isopropyl or the tert-butyl group.
The synthesis of the catalyst precarsor comprises the following steps：
(1) salicylaldehyde derivatives are prepared：By the derivative of phenol, paraformaldehyde, organic catalyst and triethylamine according to rubbing
You compare 0.01-1:0.02-6:0.01-1:0.02-6 is added in reaction bulb, using acetonitrile as solvent, is heated to reflux 1-24h, is made
Described salicylaldehyde derivatives, wherein, organic catalyst is magnesium halide；
(2) part of catalyst precarsor is prepared：The salicylaldehyde derivatives, primary amine or imines that are obtained in step (1) are massaged
Your proportioning is 0.1-1:0.15-2.0 is added in reaction bulb, using absolute ethyl alcohol as solvent, obtains schiff bases through processing after reaction, i.e.,
For the part of catalyst precarsor；
(3) catalyst precarsor is prepared：By the part obtained in step (2) with first being reacted with n-BuLi, by concentration, filter
Lithium salts is removed, then catalyst precarsor is obtained with the tetrahydrofuran complex reaction of chlorination metal.
Embodiment 1
Salicylaldehyde derivatives S1 synthesis：
In 100mL eggplant-shape bottles, 4- methyl -2- cumyl phenols (2.26g, 0.01mol), anhydrous MgCl are added2(1.90g,
0.02mol), triethylamine (3.03g, 0.03mol), paraformaldehyde (1.20g, 0.04mol) and 50mL acetonitriles, are heated to reflux stirring
Reaction, TLC tracking reaction process, room temperature is down to after 2 hours after completion of the reaction.Hydrochloric acid is added into reaction solution, is stirred, layering,
Aqueous phase is extracted with ethyl acetate, merge organic phase, and use saturated common salt water washing, anhydrous sodium sulfate drying, filter, be spin-dried for, post
Chromatograph (n-hexane:Ethyl acetate=25:1) purify, obtain yellow solid 2.11g, yield 83.2%.Elementary analysis (%)
C17H18O2, survey (calculated value)：C, 80.10 (80.31)；H, 7.02 (7.09).The structure of salicylaldehyde derivatives is as shown in formula S1：
Embodiment 2
The synthesis of the ligand L 1 of catalyst precarsor：
In 100mL eggplant-shape bottles add salicylaldehyde derivatives S1 (2.54g, 0.01mol), 2- methyl cyclohexylamines (1.36g,
0.012mol) ethanol is removed, separates out solid 3.21g, yield with 30mL absolute ethyl alcohols, heating reflux reaction, after completion of the reaction rotation
92%.Elementary analysis (%) C24H31NO, survey (calculated value)：C, 81.87 (82.40)；H, 8.71 (8.87)；N, 3.95
(4.01).The structure of the part of catalyst precarsor is as shown in formula L1：
Embodiment 3
Catalyst precarsor Zr1 synthesis：
Roasting 250mL three-necked flasks and 50mL constant pressure funnels are taken out, under argon gas protection, ligand L 1 is added into there-necked flask
(3.49g, 0.01mol) and the anhydrous THF of 30mL, -20 DEG C are cooled to, n-BuLi (6.6mL, 0.01mol) solution is added dropwise, drips off
It is warming up to 25 DEG C afterwards to react 20 hours, reaction solution is faint yellow, there is purple fluorescence.1.88g zirconium chloride tetrahydrofurans are taken afterwards
Complex compound (0.0105mol) is dissolved in 30mL tetrahydrofurans, and under ice-water bath, the lithium salt solution of ligand L 1 is added into zirconium chloride
In the solution of tetrahydrofuran complex, 25 DEG C are reacted 24 hours.Removing tetrahydrofuran is vacuumized, obtains yellow blister solid, it
40mL dichloromethane is added afterwards in yellow solid, is filtered after being sufficiently stirred, is obtained yellow solution, vacuumizes removing dichloromethane
Alkane, n-hexane is added, substantial amounts of yellow solid is separated out, is filtrated to get yellow solid 1.93g, yield 44.9%.Elementary analysis
(%) C48H60N2O2Cl2Zr, survey (calculated value)：C, 65.89 (67.05)；H, 6.86 (6.98)；N, 3.20 (3.26).Catalysis
The structure of agent precursor is as shown in formula Zr1：
Embodiment 4
Salicylaldehyde derivatives S2 synthesis：
By 2,4- dicumyl phenols, anhydrous MgCl2, triethylamine, paraformaldehyde by mol ratio be 1:2:3:4 is molten in acetonitrile
Heating reflux reaction in agent.The salicylaldehyde derivatives common 13.0g of S2, yield 75.6% is made with embodiment 1 in preparation method.Element
Analyze (%) C25H26O2, survey (calculated value)：C, 83.11 (83.68)；H, 7.20 (7.25).Structure is as shown in formula S2：
Embodiment 5
The synthesis of the ligand L 2 of catalyst precarsor：
It is 1 that salicylaldehyde derivatives S2,2- methyl cyclohexylamine are pressed into mol ratio:1.2 add in 100mL eggplant-shape bottles, with second
Alcohol is solvent, heating reflux reaction.Preparation method is the same as embodiment 2, the 2 common 16.8g of ligand L of obtained catalyst precarsor, yield
92.8%.Elementary analysis (%) C32H39NO, survey (calculated value)：C, 84.12 (84.66)；H, 7.18 (7.25)；N, 3.01
(3.09).The ligand structure of catalyst precarsor is as shown in formula L2：
Embodiment 6
Catalyst precarsor Zr2 synthesis：
Argon gas protection under, by the ligand L 2 of catalyst precarsor, n-BuLi, zirconium chloride tetrahydrofuran complex by mole
Match as 1:1:1.05 reacted.The catalyst precarsor common 8.7g of Zr2, yield 45.8% is made with embodiment 3 in preparation method.
Elementary analysis (%) C64H76N2O2Cl2Zr, survey (calculated value)：C, 71.78 (71.96)；H, 7.24 (7.12)；N,2.69
(2.62).Catalyst precarsor structure is as shown in formula Zr2：
Embodiment 7
Salicylaldehyde derivatives S3 synthesis
By 2-TBP, anhydrous MgCl2, triethylamine, paraformaldehyde by mol ratio be 1:2:2.5:5 add three mouthfuls
In flask, the heating reflux reaction in acetonitrile solvent.Preparation method is made the salicylaldehyde derivatives common 5.2g of S3, received with embodiment 1
Rate 73.6%.Elementary analysis (%) C11H14O2, survey (calculated value)：C, 74.25 (74.16)；H, 7.84 (7.87).Salicylide spreads out
Biology is as shown in formula S3：
Embodiment 8
The synthesis of the ligand L 3 of catalyst precarsor
It is 1 that salicylaldehyde derivatives S3,2- methyl cyclohexylamine are pressed into mol ratio:1.3 add in 100mL eggplant-shape bottles, with second
Alcohol is solvent, heating reflux reaction.Preparation method is the same as embodiment 2, the 3 common 6.8g of ligand L of obtained catalyst precarsor, yield
95.7%.Elementary analysis (%) C18H27NO, survey (calculated value)：C, 78.95 (79.01)；H, 9.92 (9.88)；N, 5.20
(5.12).The ligand structure of catalyst precarsor is as shown in formula L3：
Embodiment 9
Catalyst precarsor Zr3 synthesis：
Under argon gas protection, it is 1 that ligand L 2, n-BuLi, zirconium chloride tetrahydrofuran complex are pressed into mol ratio:1:
1.1 are reacted.The catalyst precarsor common 8.7g of Zr3, yield 45.8% is made with embodiment 3 in preparation method.Elementary analysis (%)
C36H52N2O2Cl2Zr, survey (calculated value)：C, 60.98 (61.12)；H, 7.34 (7.36)；N,3.89(3.96).Before catalyst
Body structure is as shown in formula Zr3：
Embodiment 10
Chlorine substituted salicylic aldehydes derivative S4 synthesis：
In 100mL eggplant-shape bottles, 3- tert-butyl groups salicylide (8.91g, 0.05mol), N- bromo-succinimides are added
(7.34g, 0.055mol) and 60mL acetic acid, 120 DEG C of heating reflux reactions, reaction solution are changed into red from yellow, reacted after 5 hours
Finish, add ethyl acetate extraction, with saturated common salt water washing organic phase, anhydrous sodium sulfate drying, filtering, column chromatography (just oneself
Alkane:Ethyl acetate=20:1) purify, then with obtaining yellow solid 4.71g, yield 44.3% after ethyl alcohol recrystallization.Elementary analysis
(%) C11H13ClO2, survey (calculated value)：C, 62.12 (62.06)；H, 6.08 (6.11).Chlorine substituted salicylic aldehydes derivative such as formula
Shown in S4：
Embodiment 11
The synthesis of the ligand L 4 of catalyst precarsor：
It is 1 that salicylaldehyde derivatives S4,2- methyl cyclohexylamine are pressed into mol ratio:1.5 add in 100mL eggplant-shape bottles, with second
Alcohol is solvent, heating reflux reaction.Preparation method is the same as embodiment 2, the 4 common 2.8g of ligand L of obtained catalyst precarsor, yield
95.1%.Elementary analysis (%) C18H26ClNO, survey (calculated value)：C, 70.18 (70.15)；H, 8.46 (8.44)；N, 4.50
(4.55).The part of catalyst precarsor is as shown in formula L4：
Embodiment 12
Catalyst precarsor Zr4 synthesis
Argon gas protection under, by the ligand L 2 of catalyst precarsor, n-BuLi, zirconium chloride tetrahydrofuran complex by mole
Match as 1:1:1.2 are reacted.The catalyst precarsor common 1.0g of Zr4, yield 45.8% is made with embodiment 3 in preparation method.Member
Element analysis (%) C36H50N2O2Cl4Zr, survey (calculated value)：C, 55.61 (55.68)；H, 6.18 (6.44)；N, 3.69
(3.61).Catalyst precarsor structure is as shown in formula Zr4：
Embodiment 13
The synthesis of the ligand L 5 of catalyst precarsor：
It is 1 that salicylaldehyde derivatives S2, cyclohexylamine are pressed into mol ratio:1.5 add in 100mL eggplant-shape bottles, using ethanol to be molten
Agent, heating reflux reaction.Preparation method is the same as embodiment 2, the 5 common 5.3g of ligand L of obtained catalyst precarsor, yield 98.3%.Member
Element analysis (%) C31H31NO, survey (calculated value)：C, 85.70 (85.79)；H, 7.10 (7.15)；N, 3.19 (3.23).Catalysis
The ligand structure of agent precursor is as shown in formula L5：
Embodiment 14
Catalyst precarsor Zr5 synthesis：
Under argon gas protection, it is 1 that ligand L 5, n-BuLi, zirconium chloride tetrahydrofuran complex are pressed into mol ratio:1:
1.1 are reacted.The catalyst precarsor common 1.9g of Zr5, yield 40.7% is made with embodiment 3 in preparation method.Elementary analysis (%)
C62H60N2O2Cl2Zr, survey (calculated value)：C, 72.40 (72.43)；H, 5.80 (5.84)；N, 2.79 (2.73).Before catalyst
Body structure is as shown in formula Zr5：
Embodiment 15
Salicylaldehyde derivatives S6 synthesis：
By 2- (1- phenylethyls) -4- chlorophenols, anhydrous MgCl2, triethylamine, paraformaldehyde in parts by weight 1:2:3:3.5
Add in three-necked flask, using acetonitrile as solvent, be heated to reflux stirring reaction.Preparation method is made salicylide and derived with embodiment 1
The common 5.0g of thing S6, yield 71.6%.Elementary analysis (%) C15H13ClO2, survey (calculated value)：C, 69.12 (69.04)；H, 4.95
(4.99).Salicylaldehyde derivatives structure is as shown in formula S6：
Embodiment 16
The synthesis of the ligand L 6 of catalyst precarsor：
It is 1 that salicylaldehyde derivatives S6, cyclohexylamine are pressed into mol ratio:1.2 add in 100mL eggplant-shape bottles, using ethanol to be molten
Agent, heating reflux reaction.Preparation method is the same as embodiment 2, the 6 common 7.3g of ligand L of obtained catalyst precarsor, yield 95.9%.Member
Element analysis (%) C31H31NO, survey (calculated value)：C, 73.75 (73.71)；H, 7.06 (7.02)；N, 4.11 (4.09).Catalysis
The ligand structure of agent precursor is as shown in formula L6：
Embodiment 17
Catalyst precarsor Zr6 synthesis：
Argon gas protection under, by the ligand L 6 of catalyst precarsor, n-BuLi, zirconium chloride tetrahydrofuran complex by mole
Match as 1:1:1.1 are reacted.The catalyst precarsor common 3.9g of Zr6, yield 45.7% is made with embodiment 3 in preparation method.Member
Element analysis (%) C42H46N2O2Cl4Zr, survey (calculated value)：C, 59.79 (59.73)；H, 5.41 (5.45)；N, 3.29
(3.32).The structure of catalyst precarsor is as shown in formula Zr6：
Embodiment 18
Catalyst precarsor Ti1 synthesis：
Preparation method changes zirconium chloride tetrahydrofuran complex into titanium tetrachloride tetrahydrofuran complex with embodiment 3,
The catalyst precarsor common 4.5g of Ti1, yield 45.1% is made.Elementary analysis (%) C48H60N2O2Cl2Ti, survey (calculated value)：C,
70.55(70.59)；H, 7.29 (7.35)；N, 3.39 (3.43).Catalyst precarsor structure is as shown in formula Ti1：
Embodiment 19
Catalyst precarsor Ti2 synthesis：
Preparation method changes zirconium chloride tetrahydrofuran complex the complexing of into titanium tetrachloride tetrahydrofuran with embodiment 14
Thing, the catalyst precarsor common 5.0g of Ti2, yield 39.6% is made.Elementary analysis (%) C62H60N2O2Cl2Ti, survey (calculated value)：
C, 75.57 (75.59)；H, 6.07 (6.10)；N, 2.89 (2.84).Catalyst precarsor structure is as shown in formula Ti2：
Embodiment 20
The synthesis of the ligand L 7 of catalyst precarsor：
3- triethyl group silicon substrate -5- tert-butyl groups salicylides and cyclohexylamine are reacted with embodiment 2, catalysis are made by preparation method
The 7 common 6.3g of ligand L of agent precursor, yield 97.9%.Elementary analysis (%) C23H39NOSi, survey (calculated value)：C, 73.78
(73.86)；H, 10.39 (10.44)；N, 7.45 (7.49).The ligand structure of catalyst precarsor is as shown in formula L7：
Embodiment 21
Catalyst precarsor Ti3 synthesis：
Preparation method changes zirconium chloride tetrahydrofuran complex into titanium tetrachloride tetrahydrofuran complex with embodiment 3,
The catalyst precarsor common 2.0g of Ti3, yield 35.7% is made.Elementary analysis (%) C46H76N2O2Si2Cl2Ti, survey (calculated value)：
C, 63.82 (63.86)；H, 8.72 (8.79)；N, 3.15 (3.24).Catalyst precarsor structure is as shown in formula Ti3：
Embodiment 22
The synthesis of the ligand L 8 of catalyst precarsor：
5- methoxyl groups -3- cumyls salicylide and 2-aminotoluene are reacted with embodiment 2, catalyst are made by preparation method
The 8 common 11.3g of ligand L of precursor, yield 98.9%.Elementary analysis (%) C24H25NO2, survey (calculated value)：C, 80.16
(80.11)；H, 6.89 (6.95).The part of catalyst precarsor is as shown in formula L8：
Embodiment 23
Catalyst precarsor Ti4 synthesis：
Preparation method changes zirconium chloride tetrahydrofuran complex into titanium tetrachloride tetrahydrofuran complex with embodiment 3,
The catalyst precarsor common 4.3g of Ti4, yield 29.7% is made.Elementary analysis (%) C48H48N2O2Cl2Ti, survey (calculated value)：C,
68.82(68.90)；H, 5.71 (5.74)；N, 3.42 (3.35).Catalyst precarsor is as shown in formula Ti4：
The pre-treatment of carrier：
Carrier include silica, aluminum oxide, the alcohol adduct of magnesium halide, titanium dioxide, montmorillonite, ion exchange resin and
One or more mixture such as clay.
The pre-treatment means of carrier of the present invention include heat treatment and/or chemical treatment：
The means of support pretreatment include heat treatment and/or chemical treatment, and described heat treatment is calcining, and calcining heat is
150~600 DEG C, calcination time is 2~48h, preferably 300 DEG C~400 DEG C processing 10h, and described chemical treatment is, by carrier with
A kind of 1~72h of contact in organic solvent in the activators such as alkyl aluminum, aluminum alkoxide, boride, organosilicon, reaction temperature
For -20~80 DEG C, 2-24h is preferably contacted, temperature control is at 0 DEG C~60 DEG C.
Preferred vector of the present invention be grain diameter be 10-500 μm, 50~500m of specific surface area2/ g silica, or by
Particle diameter is 1-100 μm, specific surface area 10-100m2The particle diameter that/g magnesium chloride granules alcohol obtains after closing is 5-50 μm of magnesium halide
Alcohol adduct.
Preferably, the alcohol of the alcohol adduct of magnesium halide is the fatty alcohol or alicyclic ring alcohol of 1 to 10 carbon atom to the present invention, element M g
Mol ratio with alcohol is 1:1-1:5.
Embodiment 24
Carrier magnesium chloride C1 preparation：
MgCl2(10 μm of grain diameter) is dehydrated 5h at 300 DEG C.Into 250ml flasks, the MgCl being heat-treated is added2
5g, toluene 80ml, ethanol 3.7g, 140 DEG C of stirring 2h.Filtering, vacuum are drained, and obtain magnesium chloride ethanol alcohol adduct solid powder.
Under the conditions of ice-water bath, 3g magnesium chloride ethanol alcohol adduct, 50ml n-hexanes, the stirring of 5ml triethyl aluminums are added into 100ml flasks
2h, filtering, washs 20ml × 3 time, vacuum is drained to obtain the common 2.5g of mobility dust carrier C1 with n-hexane.
Embodiment 25
Carrier magnesium chloride C2 preparation：
Preparation method is the same as embodiment 23, MgCl2Grain diameter selects 20 μm.By reaction, 2 common 2.4g of support C is obtained.
Embodiment 26
Carrier magnesium chloride C3 preparation：
Ethanol consumption is changed to 7.2g by preparation method with embodiment 23.By reaction, 3 common 2.8g of support C is obtained.
Embodiment 27
Carrier magnesium chloride C4 preparation：
Triethyl aluminum is changed to triisobutyl aluminium by preparation method with embodiment 25.By reaction, it is common to obtain support C 4
2.9g。
Embodiment 28
Carrier silicas C5 preparation：
A certain amount of silica (Grace 955) is weighed, is placed on 400 DEG C, N23h is calcined under atmosphere, it is close after cooling
Envelope preserves.Silica, 1ml triethyl aluminums, the 20ml n-hexanes added into 100ml flasks after 1g heat treatments, is stirred at room temperature
2h.20ml × 3 time are washed with n-hexane, vacuum is drained to obtain the common C5 1.2g of mobility dust carrier.
Embodiment 29
Carrier silicas C6 preparation：
Triethyl aluminum is changed to MAO, by reaction, finally obtains support C 6 by preparation method with embodiment 27
1.3g。
The preparation method of benzene oxygen imines polyolefin catalyst, comprises the following steps：
(a) catalyst precarsor is dissolved with organic solvent, after dissolving, adds activating substance and activated, can also
Without activation, so as to obtain catalyst precursor solution；
(b) carrier of processing before passing through is added in catalyst precursor solution, stirring contact, catalyst precarsor is supported on
On carrier, then by post processing, described catalyst is obtained.
In step (a), described organic solvent be dichloromethane, chloroform, toluene, tetrahydrofuran, linear paraffin and
One or more in alicyclic, described activating substance are alkyl aluminum, aluminum alkoxide or boride；
In step (b), described stirring Contact Temperature is controlled between 0~80 DEG C, and stirring time of contact is 0.5~48h；
Embodiment 30
Support type benzene oxygen imines polyolefin catalyst Zr1-C1-1 preparation：
Into 100ml flasks, add catalyst precarsor Zr1 toluene solution (100mg Zr1, toluene 2ml), 20ml just oneself
Alkane, 0.1ml triethyl aluminums, 1g support Cs 1, stir 10h at room temperature.Filtering, washs 20ml × 3 time, vacuum is drained, and is obtained with toluene
Obtain the common 1.05g of support type benzene oxygen imines polyolefin catalyst Zr1-C1-1 powder.ICP is determined, and Zr contents are 1.1%.
Embodiment 31
Support type benzene oxygen imines polyolefin catalyst Zr1-C1-2 preparation：
Preparation method is added without triethyl aluminum with embodiment 29 in loading process.After reaction, vacuum obtains after draining
The common 1.01g of Zr1-C1-2 powder.ICP is determined, and Zr contents are 0.7%.
Embodiment 32
Support type benzene oxygen imines polyolefin catalyst Zr2-C2-1 preparation：
Catalyst precarsor Zr1 (toluene solution) is changed to Zr2 (tetrahydrofuran solution), carried by preparation method with embodiment 29
Body C1 is changed to support C 2.After reaction, vacuum obtains the common 1.01g of Zr2-C2-1 powder after draining.ICP is determined, and Zr contents are
0.8%.
Embodiment 33
Support type benzene oxygen imines polyolefin catalyst Zr2-C5-2 preparation：
Into 100ml flasks, add catalyst precarsor Zr2 toluene solution (100mg Zr2, toluene 2ml), 20ml just oneself
Alkane, 0.1ml MAO, 1g support Cs 5, stir 10h at room temperature.Filtering, washs 20ml × 3 time, vacuum is drained, and is born with toluene
The common 1.05g of load type benzene oxygen imines polyolefin catalyst Zr2-C5-2 powder.ICP is determined, and Zr contents are 0.9%.
Embodiment 34
Support type benzene oxygen imines polyolefin catalyst Zr3-C3-1 preparation：
Catalyst precarsor Zr1 is changed to Zr3, support C 1 is changed to C3 by preparation method with embodiment 29.After reaction, vacuum is taken out
The common 1.00g of Zr3-C3-1 powder is obtained after dry.ICP is determined, and Zr contents are 1.1%.
Embodiment 35
Support type benzene oxygen imines polyolefin catalyst Zr4-C6-1 preparation：
Catalyst precarsor Zr1 is changed to Zr4, support C 1 is changed to C6 by preparation method with embodiment 29.After reaction, vacuum is taken out
The common 0.98g of Zr4-C6-1 powder is obtained after dry.ICP is determined, and Zr contents are 1.0%.
Embodiment 36
Support type benzene oxygen imines polyolefin catalyst Ti1-C2-1 preparation：
Catalyst precarsor Zr1 is changed to Ti1, support C 1 is changed to C2 by preparation method with embodiment 29.After reaction, vacuum is taken out
The common 1.08g of Ti1-C2-1 powder is obtained after dry.ICP is determined, and Ti contents are 2.5%.
Embodiment 37
Support type benzene oxygen imines polyolefin catalyst Ti2-C1-1 preparation：
Catalyst precarsor Zr1 is changed to Ti2 by preparation method with embodiment 29.After reaction, vacuum obtains Ti2- after draining
The common 0.97g of C1-1 powder.ICP is determined, and Ti contents are 1.0%.
Embodiment 38
Support type benzene oxygen imines polyolefin catalyst Ti3-C5-1 preparation：
Catalyst precarsor Zr1 is changed to Ti3, support C 1 is changed to C5 by preparation method with embodiment 29.After reaction, vacuum is taken out
The common 1.07g of Ti3-C5-1 powder is obtained after dry.ICP is determined, and Ti contents are 1.2%.
Embodiment 39
Support type benzene oxygen imines polyolefin catalyst Ti4-C6-1 preparation：
Catalyst precarsor Zr1 is changed to Ti4, support C 1 is changed to C6 by preparation method with embodiment 29.After reaction, vacuum is taken out
The common 1.04g of Ti4-C6-1 powder is obtained after dry.ICP is determined, and Ti contents are 2.0%.
The catalyst is in the presence of co-catalyst, catalyzed ethylene polymerization：Co-catalyst therein is trimethyl aluminium, three second
One or more mixtures in base aluminium, triisobutyl aluminium, aluminium diethyl monochloride, MAO and organic boride, it is excellent
Triethyl aluminum or triisobutyl aluminium are selected, polymerization temperature is 30~90 DEG C, preferably 40 DEG C~80 DEG C；The reaction of catalyzed ethylene polymerization can
It is 30 in the boiling point including n-hexane, normal heptane, 120# solvent naphthas, 90# solvent naphthas, dichloromethane, toluene or dimethylbenzene
Carried out in~150 DEG C of organic solvent, preferably n-hexane or normal heptane.
Embodiment 40
Support type benzene oxygen imines polyolefin catalyst is used to prepare High molecular weight polyethylene：
Ethene pressure polymerization reaction unit is the stainless steel cauldron that 2L is furnished with water cycle temperature control, first application of vacuum at 80 DEG C
Reactor 2 hours, is filled with nitrogen, adds 1L solvents and 20mg catalyst and co-catalyst in a nitrogen atmosphere, and then ethene is put
Change 3 times, adjustment air intake valve makes constant ethylene pressure carry out polymerisation at 1MPa pressure, 70 DEG C.After reaction terminates, do
It is dry to weighing after constant weight, measurement heap density (BD) simultaneously calculates catalyst activity.The results are shown in Table 1.
Table 1
Embodiment 41
Support type benzene oxygen imines polyolefin catalyst Zr2-C2-1 is used to prepare ethylene-hexene co-polymers：
Ethylene copolymer pressure polymerization reaction unit is the stainless steel cauldron that 2L is furnished with water cycle temperature control, true at first 80 DEG C
Vacancy reason reactor 2 hours, is filled with nitrogen, sequentially adds 1L n-hexanes, 40g 1- hexenes, 1ml triethyl groups in a nitrogen atmosphere
Aluminium, 20mg catalyst Z r2-C2-1, then ethene replace 3 times, adjustment air intake valve makes constant ethylene pressure in 1MPa pressure,
Polymerisation 4h is carried out at 70 DEG C.After reaction terminates, weighed after drying to constant weight, obtain 210g ethylene-hexene co-polymers, catalysis
Activity is 10500g ethylene copolymers/g catalyst, and viscosity average molecular weigh is 1,310,000 g/mol, and comonomer insertion rate is 15%.
Embodiment 42
Support type benzene oxygen imines polyolefin catalyst Ti3-C5-1 is used to prepare ethylene-norbornene copolymer：
Ethylene copolymer pressure polymerization reaction unit is the stainless steel cauldron that 2L is furnished with water cycle temperature control, true at first 80 DEG C
Vacancy reason reactor 2 hours, is filled with nitrogen, sequentially adds 1L n-hexanes, 40g ENBs, 1ml triethyl groups in a nitrogen atmosphere
Aluminium, 20mg catalyst Ti3-C5-1, then ethene replace 3 times, adjustment air intake valve makes constant ethylene pressure in 1MPa pressure,
Polymerisation 4h is carried out at 70 DEG C.After reaction terminates, weighed after drying to constant weight, obtain 110g ethylene-norbornene copolymers,
Catalytic activity is 5500g ethylene copolymers/g catalyst, and viscosity average molecular weigh is 2,770,000 g/mol, and comonomer insertion rate is
14%.
Embodiment 43
Support type benzene oxygen imines polyolefin catalyst Zr4-C6-1 is used to prepare polypropylene：
Propylene pressure polymerization reaction unit is the stainless steel cauldron that 2L is furnished with water cycle temperature control, first application of vacuum at 80 DEG C
Reactor 2 hours, is filled with nitrogen, sequentially adds 1L n-hexanes, 1ml triethyl aluminums, 20mg catalyst Ti3- in a nitrogen atmosphere
C5-1, then propylene replace 3 times, adjustment air intake valve makes propylene pressure constant in 0.5MPa pressure, is polymerize at 70 DEG C
React 4h.After reaction terminates, weighed after drying to constant weight, obtain 60g polypropylene, catalytic activity is 3000g polypropylene/g catalysis
Agent, viscosity average molecular weigh are 350,000 g/mol.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel do not depart from improvement that scope made and modification all should be the present invention's according to the announcement of the present invention
Within protection domain.
Claims (10)
1. a kind of support type benzene oxygen imines polyolefin catalyst, it is characterised in that including catalyst precarsor and for loading this
The carrier of catalyst precarsor, described catalyst precarsor have structure shown in formula (I) or formula (II)：
Wherein：
M is titanium, zirconium, hafnium or vanadium；
X1For one kind in C, Si and Ge；
X2And X3It is identical or different, represent the straight chained alkyl of 1~10 carbon atom, halogen atom, nitrogen-containing group, halogen group, oxygen-containing
Group, phosphorus-containing groups, boron-containing compound or heterocyclic group；
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12It independently is hydrogen, the alkyl of 1~20 carbon atom, halogen, contains
Halogen group, oxy radical, phosphorus-containing groups, boron-containing compound, jeterocyclic chemistry group, aromatic group or alicyclic group；
R in formula (II)13、R14And R15For one kind in hydrogen, methyl, ethyl, isopropyl or the tert-butyl group；
The described carrier for being used to load the catalyst precarsor includes silica, aluminum oxide, the alcohol adduct of magnesium halide, titanium dioxide
One or more mixture such as titanium, montmorillonite, ion exchange resin and clay.
2. support type benzene oxygen imines polyolefin catalyst according to claim 1, it is characterised in that
M is Zr or Ti elements；
X1For C or Si elements；
R1、R2And R3For the combination of methyl and phenyl；R5And R8For one in hydrogen, methyl, ethyl, isopropyl, cumyl, methoxyl group
Kind；
R4、R6、R7、R9、R10、R11、R12For one kind in hydrogen, methyl, halogen.
3. support type benzene oxygen imines polyolefin catalyst according to claim 1, it is characterised in that described catalyst
The synthesis of precursor comprises the following steps：
(1) salicylaldehyde derivatives are prepared：By the derivative of phenol, paraformaldehyde, organic catalyst and triethylamine according to mol ratio
0.01-1:0.02-6:0.01-1:0.02-6 is added in reaction bulb, using acetonitrile as solvent, is heated to reflux 1-24h, is made described
Salicylaldehyde derivatives, wherein, organic catalyst is magnesium halide；
(2) part of catalyst precarsor is prepared：By the salicylaldehyde derivatives obtained in step (1) and primary amine or imines by mole matching somebody with somebody
Than for 0.1-1:0.15-2.0 is added in reaction bulb, using absolute ethyl alcohol as solvent, is obtained schiff bases through processing after reaction, is as urged
The part of agent precursor；
(3) catalyst precarsor is prepared：The part obtained in step (2) is first reacted with n-BuLi, by concentration, filters off lithium
Salt, then reacted with the tetrahydrofuran complex of chlorination metal, obtain described catalyst precarsor.
4. support type benzene oxygen imines polyolefin catalyst according to claim 1, it is characterised in that described carrier is
Grain diameter is 10-500 μm, 50~500m of specific surface area2/ g silica, or by particle diameter be 1-100 μm, specific surface area
10-100m2The particle diameter that/g magnesium chloride granules alcohol obtains after closing is the alcohol adduct of 5-50 μm of magnesium halide.
5. the preparation method of the support type benzene oxygen imines polyolefin catalyst as described in Claims 1 to 4 is any, its feature exist
In comprising the following steps：
(a) catalyst precarsor is dissolved with organic solvent, after dissolving, adds activating substance and activated, or without work
Change, obtain catalyst precursor solution；
(b) carrier of processing before passing through is added in catalyst precursor solution, stirring contact, catalyst precarsor is supported on carrier
On, then by post processing, obtain described loaded catalyst.
6. the preparation method of benzene oxygen imines polyolefin catalyst as claimed in claim 5, it is characterised in that
In step (a), described organic solvent is dichloromethane, chloroform, toluene, tetrahydrofuran, linear paraffin and alicyclic ring
One or more in hydrocarbon, described activating substance are alkyl aluminum, aluminum alkoxide or boride；
In step (b), described stirring Contact Temperature is controlled between 0~80 DEG C, and stirring time of contact is 0.5~48h；
The means of support pretreatment include heat treatment and/or chemical treatment：
The means of support pretreatment include heat treatment and/or chemical treatment, and described heat treatment is calcines, calcining heat 150
~600 DEG C, calcination time is 2~48h, and described chemical treatment is, by carrier with including alkyl aluminum, aluminum alkoxide, boride
Or a kind of 1~72h of contact in organic solvent in the activator including organosilicon, reaction temperature is -20~80 DEG C.
7. the application of benzene oxygen imines polyolefin catalyst as claimed in claim 1, it is characterised in that the catalyst is urged helping
In the presence of agent, catalyzed ethylene polymerization.
8. the application of benzene oxygen imines polyolefin catalyst according to claim 7, it is characterised in that described co-catalysis
Agent is one kind in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, MAO and organic boride
Or a variety of mixtures, polymerization temperature are 30~90 DEG C；
The reaction of catalyzed ethylene polymerization can be including n-hexane, normal heptane, 120# solvent naphthas, 90# solvent naphthas, dichloromethane, first
Boiling point including benzene or dimethylbenzene is to be carried out in 30~150 DEG C of organic solvent.
9. the application of benzene oxygen imines polyolefin catalyst according to claim 7, it is characterised in that when the catalyst is used
When ethylene homo is catalyzed, High molecular weight polyethylene of the molecular weight 200,000-1,000 ten thousand can be obtained, its average grain diameter can<180μ
M, 40 mesh sieving rates can reach 99%, and catalytic activity is up to 30000g polyethylene/g catalyst.
10. the application of benzene oxygen imines polyolefin catalyst as claimed in claim 1, it is characterised in that the catalyst is used for
It is catalyzed the linear alkene copolymerization and the copolymerization of ethene and ENB of propylene homo, ethene and carbon number 3~8.
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| CN110339860B (en) * | 2019-07-29 | 2022-03-01 | 湖北工程学院 | Crosslinked norbornene copolymer composite carbon black three-dimensional network supported platinum nano-catalyst and preparation method and application thereof |
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