CN102731880A - Polyolefin resin containing reduced graphite oxide and its preparation method - Google Patents

Polyolefin resin containing reduced graphite oxide and its preparation method Download PDF

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CN102731880A
CN102731880A CN2011100909769A CN201110090976A CN102731880A CN 102731880 A CN102731880 A CN 102731880A CN 2011100909769 A CN2011100909769 A CN 2011100909769A CN 201110090976 A CN201110090976 A CN 201110090976A CN 102731880 A CN102731880 A CN 102731880A
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reduction
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magnesium
oxidation graphite
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黄英娟
董金勇
秦亚伟
王宁
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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The invention discloses a polyolefin resin containing reduced graphite oxide and its preparation method. The reduced graphite oxide-containing polyolefin resin comprises polyolefin and reduced graphite oxide. In the invention, an in situ polymerization method is employed to prepare the reduced graphite oxide-containing polyolefin resin. Specifically, an olefin polymerization catalyst (including a Ziegler-Natta catalyst, metallocene and non-metallocene catalysts, etc.) is loaded on a graphite oxide carrier to prepare a graphite oxide carrier catalyst of an aluminum-containing and/or magnesium-containing compound, and in the process graphite oxide is reduced to reduced graphite oxide. The carrier catalyst is employed to catalyze olefin polymerization for preparing electroconductive polyolefin resin through in situ polymerization. The method of the invention successfully introduces graphite oxide into the in a polyolefin matrix, and controls the content of graphite oxide in the polyolefin matrix to further control the electric conductivity of the polymer, thus satisfying the application of the polyolefin resin in different fields.

Description

Contain polyolefin resin of reduction-oxidation graphite and preparation method thereof
Technical field
The present invention relates to polyolefin resin and preparation method thereof, especially relate to a kind of polyolefin resin that contains reduction-oxidation graphite and preparation method thereof.
Background technology
Graphite oxide (GO) is to add the compound that water decomposition obtains after the powerful oxidation of the high graphite of crystallinity, can classify as the compound between graphite layers of covalent linkage.The preparation method of graphite oxide mainly is a chemical oxidization method, Brodie method for example, Staudenmaier method and hummers method etc.It has been generally acknowledged that on the Graphene reticulated structure of graphite oxide and contain epoxy, oxy radicals such as carbonyl, hydroxyl.Owing to this existence that contains the oxygen functional group, destroyed the reticulated structure of Graphene, influenced the transport passage of electronics and then influenced its electroconductibility, so the electroconductibility of graphite oxide is significantly less than the electroconductibility of Graphene.But graphite oxide is considered to the strategic starting point of mass preparation Graphene, and it can further use mechanical means, and like ultra-sonic dispersion in thermal expansion or the solvent, accurate two dimensional oxidation graphene suspension is stablized in preparation.Strengthen its composite performance through surface-treated then, and form Graphene, thereby realize that the nano level of Graphene in matrix disperses through reduction reaction.Graphene is that Geim of Univ Manchester UK in 2004 etc. find that after graphite peels a small amount of Graphene monolithic it has special characteristic electron.Realized in 2007 one flake graphite alkene is hung on the miniature support in air or in the vacuum, thereby broken traditional theory and tested the conclusion that is drawn.Graphene is except the electric property excellence, and the tensile modulus of Graphene (1.01TPa) is suitable with the single armed carbon nanotube with US (116GPa), its light weight, the big (2600m of thermal conductivity good (～5000W/ (mK)) and specific surface area 2/ g).Compare with carbon nanotube with the soccerballene of costliness, graphite oxide is cheap, and raw material is easy to get, and is expected to become the high quality filler of polymer nanocomposites.
Over nearly 10 years, a lot of about graphite oxide and multiple matrix compound report both at home and abroad, but graphite oxide whether monolithic layer is peeled off indeterminate.After 2004, along with the Graphene monolithic is proved at the stable existence under the conventional environment, and mechanically peel GO prepares the maturation utilization of graphite oxide technology, just truly realizes the nano combined of graphite oxide and polymkeric substance.The successful realization and the nano combined polymeric matrix of graphite oxide (perhaps Graphene) of report have PS (PS) at present; Polymethylmethacrylate (PMMA); Z 150PH (PVA), polycaprolactone (PCL) and some conductive polymers matrixes (polyaniline (PANI), polypyrrole (PPy) etc.) etc.Realize that polymeric matrix and the nano combined preparation method of graphite oxide have two kinds: direct graft process of polymkeric substance and in-situ monomer intercalation polymerization.The direct graft process of polymkeric substance is to utilize the effect of solvent or the polymer molecule insertion is had in the graphite oxide of laminate structure the formation nano composite material through physical actions such as mechanical shearings.This method is the traditional method of synthetic polymer nano composite material.Stankovich etc. (nature, 2006,442,282-286) in N ' dinethylformamide (DMF), PS is mixed with the ultrasonic isocyanate-modified graphite oxide of peeling off, add Hydrazine Hydrate 80 (H subsequently 2N-NH 2H 2O) to its chemical reduction, carry out injection molding hot pressing after desolventizing drying, made conductive graphene/vinylbenzene nano composite material.The electrical property of gained matrix material can be suitable with carbon nano tube compound material, and during the loading level volume(tric)fraction 0.1% of graphene film, the electric conductivity of matrix material can satisfy the antistatic standard (10 of film -6S/m), should value increase fast when loading level surpasses volume(tric)fraction 0.4%, 1% o'clock is 0.1S/m, and 2.5% o'clock is 1S/m.The blend in dimethylsulfoxide solvent of the graphite oxide of Z 150PH and esterification utilizes Hydrazine Hydrate 80 as reductive agent, has prepared Z 150PH/graphene nano matrix material.Document is arranged again, and (Macromolecules 2010,43, and 2357-2363) report reduces adding Hydrazine Hydrate 80 behind PVA and the GO solution blending, has prepared Z 150PH/graphene nano matrix material.When Graphene lamella content was 1.8vol%, its modulus is compared with pure Z 150PH had increased by 10 times.The oxygen functional group that contains of oxidized graphite flake layer is easy to the polar polymer interaction; (nature nanotechnology 2008 such as BrinSon; 3; 327-331) people's polymethylmethacrylate/functionalization graphene nano composite material that adopted Prepared by Solution Mixing Method, when the content of weighting material reaches 0.05wt%, its second-order transition temperature is compared with pure polymethylmethacrylate and has been improved nearly 30 degree.
The in-situ monomer intercalation polymerization be at present report prepare the less method of polymer/graphene (or graphite oxide) nano composite material.Exactly monomer solution and GO colloidal dispersion liquid are pre-mixed, monomer molecule is inserted the GO interlayer, drop into the initiator initiated polymerization then, make polyreaction see at the Graphene lamella and carry out, the reaction solution that obtains can obtain matrix material through handling.In the in-situ monomer intercalation polymerization process, because making, the expansion that the polyreaction heat release produces helps the spacing expansion between the oxidized graphite flake layer further peeling off, make that the dispersiveness of Graphene in matrix is more even.(Journal of Polymer Science part A:polymer chemistry 2010 such as Galland; 48; 692-698) people has reported that the graphite that MAO is handled joins in the ethylene polymerization still; As Primary Catalysts, MAO has prepared polyethylene/graphite alkene matrix material as the promotor catalyzed ethylene polymerization with bis cyclopentadienyl zirconium dichloride, and graphite is dispersed in the Vilaterm matrix with sheet form.The electroconductibility of not mentioned gained matrix material in the document.Domestic Zhejiang University (macromolecules, 2010,43,6716-6723) adopt the method for in-situ polymerization to prepare nylon-6/graphene nano matrix material.They are raw material with the graphite oxide, when nylon 6/poly closes, have realized the reduction of graphite oxide synchronously, but the mechanical property that just relates to the gained matrix material in the article does not relate to its electroconductibility.
Polyolefine is nonpolarity, is good electrical insulator, but friction or contact are charged easily, produces electrostatic and gathers, and processing products is caused bad influence with using.So big limitations polyolefinic range of application.The application at present prescription of antistatic polyolefine more widely is to add therein to prevent and eliminate polypropylene tape electrostatic additive, but this requirement to static inhibitor is relatively stricter.If in polyolefin substrate, introduce the weighting material of conduction, strengthen its electroconductibility, and then strengthen polyolefinic functionally and give its new performance, can expand polyolefinic range of application like this.
But to polyolefine, prepare its nano composite material the most effectively one of method be in-situ polymerization technology.This technology refers to olefin polymerization catalysis (is comprised Ziegler-Natta; Metallocene catalyst; Late transition metal catalyst and non cyclopentadienyl catalyst etc.) be carried on the carrier (graphite oxide or polynite), utilize this carried catalyst catalysis in olefine polymerization to prepare composite polyolefine material.Montmorillonite carrier catalyst olefinic polymerization that our seminar had once adopted the successful preparation of this method has obtained polyolefin/montmorillonite nano composite material, has applied for related patent U.S. Patent No. (application number: 200510009508.9,200910235504.0; 200910235506.X; 200910235507.4; 200910235505.5; 200910235503.6).Though graphite oxide and polynite are structurally similar, peeling off of oxidized graphite flake interlayer is more difficult than polynite, and the electroconductibility extreme difference of graphite oxide.So with the graphite oxide is raw material; The method of employing in-situ polymerization prepares the polyolefine/graphene nano matrix material of high conductivity, in this preparation process, can graphite oxide be reduced to Graphene it is scattered in the polyolefin substrate; And utilize the advantage of in-situ polymerization that graphite oxide or Graphene are dispersed in the polyolefin substrate; And the heat of polymerization that utilizes polyreaction to discharge is peeled off the Graphene lamella, and then it is functional to give polyolefine, promptly high electroconductibility; Can develop the high-performance poly olefin resin, this will be significant in practical application.
Summary of the invention
The purpose of this invention is to provide a kind of polyolefin resin that contains reduction-oxidation graphite and preparation method thereof.
A kind of polyolefin resin that contains reduction-oxidation graphite provided by the invention comprises polyolefine and reduction-oxidation graphite.
The polyolefin resin that contains reduction-oxidation graphite according to the invention is made up of said polyolefine and said reduction-oxidation graphite.
In the above-mentioned polyolefin resin that contains reduction-oxidation graphite, said polyolefine is selected from least a in Vilaterm, Vestolen PP 7052, ethylene-propylene copolymer, ethene and alpha-olefin copolymer and propylene and the alpha-olefin copolymer;
Said poly weight-average molecular weight is 10,000～1,000,000, specifically can be 13.7 ten thousand-420,000, preferred 10,000～500,000; Said polyacrylic weight average molecular weight range is 10,000～1,500,000, specifically can be 19.2 ten thousand-790,000,19.7 ten thousand-550,000,22.2 ten thousand-38.7 ten thousand or 26.7 ten thousand-38.6 ten thousand, preferred 10～800,000; The weight-average molecular weight of said ethylene-propylene copolymer is 10,000～1,000,000, preferred 100,000～700,000; The weight-average molecular weight of said ethene and alpha-olefin copolymer is 10,000～1,000,000, specifically can be 32.7 ten thousand-390,000, preferred 100,000～800,000; The weight-average molecular weight of said propylene and alpha-olefin copolymer is 10,000～1,500,000, specifically can be 200,000-530,000, preferred 100,000～800,000; Said terminal olefin is suc as formula shown in the I,
R-(CH＝CH)n-R’
(formula I)
Among the said formula I, R is H or (CH 2) N1CH 3, n 1Integer for 1-11; R ' is (CH 2) N2CH 3Or phenyl, n 2Integer for 1-11; Said terminal olefin is selected from least a in 1-butylene, 1-amylene, 1-hexene, 1-octene and the vinylbenzene;
The mol ratio of carbon and oxygen element is 6: 0.0001～2 in the said reduction-oxidation graphite; Specifically can be 6: 0.001-0.4,6: 0.001-0.2,6: 0.001-0.1,6: 0.01-0.4,6: 0.01-0.2,6: 0.01-0.1,6: 0.01-0.05,6: 0.01-0.03,6: 0.03-0.4,6: 0.03-0.2,6: 0.03-0.1,6: 0.03-0.05,6: 0.05-0.4,6: 0.05-0.2,6: 0.05-0.1,6: 0.1-0.4,6: 0.1-0.2,6: 0.1-0.4,6: 0.1-0.2 or 6: 0.2-0.4; Preferred 6: 0.0001～1; Said reduction-oxidation graphite and said polyolefinic weight ratio are 1: 3～1: 9999; Specifically can be 1: 13-999,1: 13-265,1: 13-199,1: 13-115,1: 13-128,1: 13-100,1: 13-84,1: 13-51,1: 13-49,1: 13-34,1: 13-24,1: 24-999,1: 24-265,1: 24-199,1: 24-115,1: 24-128,1: 24-100,1: 24-84,1: 24-51,1: 24-49,1: 24-34,1: 34-999,1: 34-265,1: 34-199,1: 34-115,1: 34-128,1: 34-100,1: 34-84,1: 34-51,1: 34-49,1: 49-999,1: 49-265,1: 49-199,1: 49-115,1: 49-128,1: 49-100,1: 49-84,1: 49-51,1: 100-999,1: 100-265,1: 100-199,1: 100-115,1: 100-128,1: 49-100,1: 84-100,1: 265-999,1: 199-999 or 1: 115-999, preferred 1: 4-1: 999;
The said electric conductivity that contains the polyolefin resin of reduction-oxidation graphite is 1.0 * 10 -8～9.9 * 10 2S/m specifically can be 6.6 * 10 -5S/m-6.9 * 10 -3S/m, 2.9 * 10 -6S/m-10.8S/m, 5.1 * 10 -7S/m-980S/m, 5.2 * 10 -5S/m-6.9S/m or 1.4 * 10 -4S/m-2.8 * 10 -2S/m.
The polyolefin resin that contains reduction-oxidation graphite according to the invention is to get according to following method preparation.
The preparation method who contains the polyolefin resin of reduction-oxidation graphite according to the invention; Comprise the steps: that with at least a in ethene and the propylene be polymerization single polymerization monomer; The olefin polymerization catalysis that is carrier with reduction-oxidation graphite provided by the invention is that catalyzer carries out polymerization, and reaction finishes and obtains the said polyolefin resin that contains reduction-oxidation graphite;
Said polymerization method is the method for slurry polymerization, mass polymerization or mass polymerization and vapour phase polymerization coupling.
Wherein, Said slurry polymerization comprises the steps: under the vacuum state; Said polymerization single polymerization monomer is charged in the reaction kettle; Then with organic solvent, promotor and said be that the olefin polymerization catalysis of carrier mixes and carries out polyreaction with reduction-oxidation graphite, reaction finishes and obtains the said polyolefin resin that contains reduction-oxidation graphite after the drying;
In the said slurry phase polymerisation process, the consumption of said organic solvent is 0.01～0.80 with the ratio of reaction kettle volume, specifically can be 0.1-0.2,0.1-0.4,0.2-0.4,0.2-0.5 or 0.4-0.5, preferred 0.1～0.5; Said is that the olefin polymerization catalysis of carrier and the amount ratio of said organic solvent are 1 * 10 with the graphite oxide -4～20g: 1L; Specifically can be 0.1-4g: 1L, 0.1-1g: 1L, 0.1-0.8g: 1L, 0.1-0.6g: 1L, 0.1-0.4g: 1L, 0.1-0.2g: 1L, 0.2-4g: 1L, 0.2-1g: 1L, 0.2-0.8g: 1L, 0.2-0.6g: 1L, 0.2-0.4g: 1L, 0.4-4g: 1L, 0.4-1g: 1L, 0.6-4g: 1L, 0.6-1g: 1L or 0.8-4g: 1L, preferred 0.5～5g: 1L; Said promotor is 1.4-5.5mmol: 0.02-2g with the amount ratio that is the olefin polymerization catalysis of carrier with reduction-oxidation graphite; Specifically can be 1.4-5mmol: 0.02-2g, 1.4-2.8mmol: 0.02-2g, 2.8-5.5mmol: 0.02-2g, 5-5.5mmol: 0.02-2g, 1.4-5mmol: 0.04-2g, 1.4-2.8mmol: 0.04-2g, 2.8-5.5mmol: 0.04-2g, 5-5.5mmol: 0.04-2g, 1.4-5mmol: 0.05-2g, 1.4-2.8mmol: 0.05-2g, 2.8-5.5mmol: 0.05-2g, 5-5.5mmol: 0.05-2g, 1.4-5mmol: 0.1-2g, 1.4-2.8mmol: 0.1-2g, 2.8-5.5mmol: 0.1-2g or 5-5.5mmol: 0.1-2g, preferred 1.4-1.8mmol: 0.1g; In the said reactions step, temperature is 0～120 ℃, and preferred 40～80 ℃, more preferably 70 ℃, pressure is 0.1～1.0MPa, preferred 0.1～0.7MPa, and more preferably 0.5MPa, the time is 0.01～10 hour, preferred 0.1～2 hour, more preferably 0.5 hour; In the said drying step, temperature is 40～70 ℃, and preferred 60 ℃, the time is 0.5-48 hour, and preferred 12～24 hours, vacuum tightness was 0.01MPa-0.1MPa, preferred 0.01MPa;
Said slurry phase polymerisation process also comprised the steps: before said polymerization procedure, in reaction system, added at least a in comonomer and the external electron donor, and wherein, said comonomer is a terminal olefin shown in the formula I;
R-(CH＝CH)n-R’
(formula I)
Among the said formula I, R is H or (CH 2) N1CH 3, n 1Integer for 1-11; R ' is (CH 2) N2CH 3Or phenyl, n 2Integer for 1-11; Said terminal olefin is selected from least a in 1-butylene, 1-amylene, 1-hexene, 1-octene and the vinylbenzene; The concentration of said comonomer in said organic solvent is 0～10mol/L, specifically can be 0.06-1.16mol/L, 0.06-0.17mol/L or 0.17-1.16mol/L, preferred 0～1mol/L, and the concentration of said comonomer is not 0; Said external electron donor is dimethyl diphenyl silane, dimethyldimethoxysil,ne, trimethylammonium methoxy silane, methyltrimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane or tetrahydrotoluene dimethoxy silane; The mol ratio of said external electron donor and said promotor is 0: 1～1: 1000, specifically can be 1: 10-20,1: 10-18 or 1: 18-20, and preferred 1: 10～1: 100, the mole dosage of said external electron donor was not 0;
Said mass polymerization comprise the steps: with propylene liquid, external electron donor, promotor and said be that the olefin polymerization catalysis of carrier mixes and carries out polyreaction with reduction-oxidation graphite, reaction finishes and obtains the said polyolefin resin that contains reduction-oxidation graphite; Said external electron donor is dimethyl diphenyl silane, dimethyldimethoxysil,ne, trimethylammonium methoxy silane, methyltrimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane or tetrahydrotoluene dimethoxy silane; In the said bulk polymerization; The quality of said propylene liquid and the volume ratio of reaction kettle are 0.01～0.70g: 1ml; Specifically can be 0.10-0.15g: 1ml, 0.15-0.25g: 1ml, 0.25-0.50g: 1ml, 0.15-0.50g: 1ml, 0.25-0.4g: 1ml, 0.15-0.4g: 1ml or 0.4-0.5g: 1ml, preferred 0.10～0.50g: 1ml; Said is that the weight consumption of olefin polymerization catalysis and propylene liquid of carrier is than 1 * 10 with reduction-oxidation graphite -6～1 * 10 -2, specifically can be 0.002-0.005: 1,0.002-0.004: 1,0.0024-0.005: 1,0.0024-0.004: 1,0.002-0.0024: 1 or 0.004-0.005: 1, preferred 1 * 10 -4～1 * 10 -1Said promotor and said be that the amount ratio of the olefin polymerization catalysis of carrier is 0.025-0.3mol: 0.7-2.0g with reduction-oxidation graphite; Specifically can be 0.025-0.15mol: 0.8-2.0g, 0.025-0.25mol: 0.8-2.0g, 0.025-0.3: mol: 0.8-2.0g, 0.15-0.25mol: 0.8-2.0g, 0.25-0.3mol: 0.8-2.0g, 0.15-0.25mol: 0.7-2.0g, 0.25-0.3mol: 0.8-2.0g, 0.15-0.25mol: 0.7-0.8g, 0.25-0.3mol: 0.7-0.8g, preferred 0.25mol: 0.8g; The molar ratio of said external electron donor and said promotor is 0: 1～1: 1000, preferred 1: 10～1: 100, and more preferably 1: 10; In the said reactions step, temperature is 40～80 ℃, and preferred 60-70 ℃, more preferably 60 ℃, the time is 0.01～10.0 hour, specifically can be 0.2-0.3 hour, 0.2-2 hour or 0.3-2 hour, preferred 0.1～2 hour;
Said mass polymerization also comprises the steps: before said polymerization procedure, in reaction system, to add hydrogen; The weight consumption of said hydrogen and propylene liquid specifically can be 0.000125-0.001,0.000125-0.0003 or 0.0003-0.001 than 0～0.01, and is preferred 0～0.001, and the weight of said hydrogen is not 0;
Said mass polymerization and the method for vapour phase polymerization coupling comprise the steps: with propylene liquid, hydrogen, promotor and said be to be warming up to 50～80 ℃ after the olefin polymerization catalysis of carrier mixes in reaction kettle with reduction-oxidation graphite; React after 0.01～10.0 hour; Emptying; To be that 0.001: 1～100: 1 the gas mixture of being made up of ethene and propylene is passed in the said reaction kettle with volume ratio then; After 0.05～10.0 hour, obtain the said polyolefin resin that contains reduction-oxidation graphite in 40-90 ℃ of reaction; In the method for said mass polymerization and vapour phase polymerization coupling, the volume ratio of said propylene liquid and reaction kettle is 0.01～0.70, preferred 0.05～0.5; The weight consumption of said hydrogen and propylene liquid is than 0～0.01, and is preferred 0.000001～0.001, and the weight of said hydrogen is not 0; Said is that the weight consumption of olefin polymerization catalysis and propylene of carrier is than 1 * 10 with reduction-oxidation graphite -6～1 * 10 -2, preferred 1 * 10 -4～1 * 10 -1Said promotor and said be that the molar ratio of the olefin polymerization catalysis of carrier is 1～10000 with reduction-oxidation graphite, preferred 100～3000; In said two reactions step, the reaction times preferably is 0.1～2 hour; The method of said mass polymerization and vapour phase polymerization coupling also comprise the steps: said with propylene liquid, hydrogen, promotor and said be that the olefin polymerization catalysis of carrier before the mixing step, adds external electron donor in reaction kettle in reaction system with reduction-oxidation graphite; Said external electron donor is dimethyl diphenyl silane, dimethyldimethoxysil,ne, trimethylammonium methoxy silane, methyltrimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane or tetrahydrotoluene dimethoxy silane; The molar ratio of said external electron donor and said promotor is 0: 1～1: 1000, specifically can be 1: 10-20,1: 10-18 or 1: 18-20, and preferred 1: 10～1: 100, the mole dosage of said external electron donor was not 0;
In the method for said slurry polymerization, mass polymerization and said mass polymerization and vapour phase polymerization coupling; It is at least a in 6～9 the naphthenic hydrocarbon that said organic solvent all is selected from the total number of carbon atoms is 5～10 alkane, the total number of carbon atoms is 6-9 aromatic hydrocarbon and the total number of carbon atoms, at least a in preferred hexane, heptane, decane, toluene, YLENE and the hexanaphthene; The general structure of said promotor is Al (OR ') nR 3-n, n is the integer of 0-3, it is in 2～10 the alkyl any one that R and R ' all are selected from the total number of carbon atoms, preferred trimethylaluminium, triethyl aluminum, triisobutyl aluminium or MAO.
According to the invention is the olefin polymerization catalysis of carrier with reduction-oxidation graphite, comprises following component: reduction-oxidation graphite, metallic compound and olefin polymer catalyst; Wherein, said metallic compound is selected from least a in magnesium-containing compound and the aluminum contained compound; Said olefin polymer catalyst is selected from least a in Ziegler-Natta catalyst, metallocene catalyst and the non-metallocene catalyst.
Above-mentioned olefin polymerization catalysis also can only be made up of said components.Wherein, said magnesium-containing compound is that molecular formula is MgX 2Magnesium halide or general structure be the Grignard reagent of RMgX; Said MgX 2In, X is fluorine, chlorine, bromine or iodine, preferred X is a chlorine; Among the said RMgX, R is selected from any one in the alkyl that the total number of carbon atoms is 1-10, and preferable methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, X are fluorine, chlorine, bromine or iodine;
Said aluminum contained compound is Al (OR ') nR 3-n, said Al (OR ') nR 3-nIn, n is the integer of 0-3, R and R ' all are selected from any one in the alkyl that the total number of carbon atoms is 2-10, the preferred trimethylaluminium of said aluminum contained compound, triethyl aluminum, triisobutyl aluminium or MAO;
In the said olefin polymer catalyst, the used titanium tetrahalide of said Ziegler-Natta catalyst is TiCl 4, TiBr 4Or TiI 4, used titan-alkoxide is Ti (OEt) Cl 3, Ti (OEt) 2Cl 2, Ti (OEt) 3Cl, Ti (OEt) 4Or Ti (OBu) 4The general structure of said metallocene catalyst is suc as formula shown in the II:
(Cp I-B e-Cp II)MR 1 aR 2 b
(formula II)
Among the said formula II, M is selected from least a in Ti, Zr, Hf, V, Fe, Y, Sc and the lanthanide series metal; Said Cp IAnd Cp IIRepresent cyclopentadienyl moiety or contain substituent cyclopentadienyl moiety, said substituting group is selected from least a in the aromatic base that alkyl that the total number of carbon atoms is 1-6, naphthenic base that the total number of carbon atoms is 3-18 and the total number of carbon atoms be 6-18; Said R 1And R 2All be selected from H, halogen atom, the total number of carbon atoms and be 1-8 alkyl, the total number of carbon atoms and be the alkoxyl group of 1-8, aryl that the total number of carbon atoms is 6-20, substituted the total number of carbon atoms of alkyl that the total number of carbon atoms is 1-15 and be the aryl of 6-20, acyloxy, allyl group and the total number of carbon atoms that the total number of carbon atoms is 1-8 and be in the siloyl group of 1-15 any one; Said B represents alkyl bridge or siloyl group bridge, and is preferred-C (R 3R 4)-or-Si (R 3R 4)-; R 3And R 4All be selected from H, the total number of carbon atoms and be in the alkyl of 1-4 and the aryl that the total number of carbon atoms is 6-10 any one; E is 1,2 or 3, and a is the integer of 1-4, preferred 1 or 2; B is the integer of 1-4, preferred 1 or 2; The preferred Et of said metallocene catalyst (Ind) 2ZrCl 2, Me 2C (Cp) is ZrCl (Flu) 2, Et (H 4Ind) 2ZrCl 2, Me 2Si (Ind) 2ZrCl 2, Me 2Si (2-Me-4-Ph-Ind) 2ZrCl 2, Me 2Si (Me 4Cp) 2ZrCl 2, Me 2Si (Flu) 2ZrCl 2, Me 2Si (2-Me-4-Naph-Ind) 2ZrCl 2Or Ph 2Si (Ind) 2ZrCl 2, wherein, Me is a methyl, and Ph is a phenyl, and Cp is a cyclopentadienyl moiety, and Ind is an indenyl, H 4Ind is 4,5,6, and 7-tetrahydro-indenes, Flu are fluorenyl, and Naph is a naphthyl;
The general structure of said non-metallocene catalyst is shown in formula III:
Figure BDA0000054899670000071
(formula III)
In the said formula III, M is selected from least a among Zr, Ti, V and the Hf, R 1, R 2And R 3All be selected from H, halogen atom, the total number of carbon atoms and be the alkyl of 1-8, alkoxyl group that the total number of carbon atoms is 1-8, aryl that the total number of carbon atoms is 6-20, the substituted aryl of alkyl that the total number of carbon atoms is 1-6, aryl that the total number of carbon atoms is the cycloalkyl substituted of 3-18, the substituted aryl of aromatic base that the total number of carbon atoms is 6-18, acyloxy, allyl group and the total number of carbon atoms that the total number of carbon atoms is 1-8 and be in the siloyl group of 1-15 any one; X is fluorine, chlorine, bromine or iodine, and n is 1 or 2; Said non-metallocene catalyst is preferably two [N-(3-tertiary butyl salicylidene) anilino] zirconium dichloride, two [N-(3-methyl salicylidene) anilino] zirconium dichloride, two [N-(3-sec.-propyl salicylidene) anilino] zirconium dichloride or two [N-(3-adamantyl-5-methyl salicylidene) anilino] zirconium dichloride;
The ratio of said reduction-oxidation graphite and said olefin polymer catalyst is 1g: 0.001mol～10mol; Specifically can be 1g: 0.066-0.61mol, 1g: 0.066-0.455mol, 1g: 0.066-0.364mol, 1g: 0.066-0.3mol, 1g: 0.3-0.61mol, 1g: 0.3-0.455mol, 1g: 0.3-0.364mol, 1g: 0.364-0.61mol, 1g: 0.364-0.455mol or 1g: 0.455-0.61mol; Preferred 1g: 0.01mol～0.1mol; Said olefin polymerization catalysis is the mole number calculating by the metal active site; The mol ratio of said metallic compound and olefin polymerization catalysis is 0.0001～10000; Specifically can be 0.021-0.55,0.021-0.22,0.021-0.055,0.021-0.046,0.021-0.025,0.025-0.55,0.025-0.22,0.025-0.055,0.025-0.046,0.046-0.55,0.046-0.22,0.046-0.055,0.055-0.55,0.055-0.22 or 0.22-0.55, preferred 0.01～2000.
What the invention described above provided is that carrier and metallic compound are that the olefin polymerization catalysis of said magnesium-containing compound or the mixture be made up of said magnesium-containing compound and said aluminum contained compound also comprises internal electron donor with reduction-oxidation graphite; Said internal electron donor is selected from 9; At least a in 9-two (methoxymethyl) fluorenes (also being the fluorenes diether), diethyl succinate, Tabutrex, Witcizer 300, diisobutyl phthalate, dimixo-octyl phthalate, ethyl benzoate, ethyl anisate and the ethyl p-ethoxybenzoate, at least a in preferred diisobutyl phthalate and the Witcizer 300; In said internal electron donor and the said olefin polymerization catalysis in the magnesium-containing compound mol ratio of magnesium elements be 0.05～0.6; Specifically can be 0.1-0.36,0.1-0.3,0.1-0.25,0.1-0.15,0.15-0.4,0.15-0.36,0.15-0.3,0.15-0.25,0.25-0.4,0.25-0.36,0.25-0.3,0.3-0.4,0.3-0.36 or 0.36-0.4, preferred 0.1～0.4.
According to the invention is that the olefin polymerization catalysis of carrier is to get according to following method preparation with reduction-oxidation graphite.
Metallic compound according to the invention be magnesium-containing compound be the method for the olefin polymerization catalysis of carrier with the graphite oxide, be following method a or method b;
Wherein, said method a comprises the steps:
1) graphite oxide and said magnesium-containing compound are reacted in organic solvent, reaction finishes and obtains the carrier of said magnesium-containing compound after the drying;
2) carrier with said titanium tetrahalide or titan-alkoxide and said step 1) gained magnesium-containing compound reacts, reaction finish obtain after the drying said metallic compound be magnesium-containing compound be the olefin polymerization catalysis of carrier with reduction-oxidation graphite;
Said method b comprises the steps:
1) graphite oxide and said magnesium-containing compound are reacted in organic solvent, reaction finishes and obtains the carrier of said magnesium-containing compound after the drying;
2) with the carrier of said titanium tetrahalide or titan-alkoxide and said step 1) gained magnesium-containing compound after-20 ℃ of following isothermal reaction 0.1-2 hours; Be warming up to 80～130 ℃ of isothermal reaction 1-4 hours; Reaction adds said titanium tetrahalide or titan-alkoxide after finishing again after 80～130 ℃ of following isothermal reaction 1-4 hours, and what obtain said metallic compound and be magnesium-containing compound is the olefin polymerization catalysis of carrier with reduction-oxidation graphite.
In the step 1) of said method a and method b; It is that alkane, the total number of carbon atoms of 5～10 are that aromatic hydrocarbon, the total number of carbon atoms of 6～9 are that naphthenic hydrocarbon, the total number of carbon atoms of 6～9 are at least a in 2～12 ether and the THF that said organic solvent all is selected from the total number of carbon atoms, at least a in preferred hexane, heptane, decane, ether, positive propyl ether, butyl ether, isopropyl ether, isoamyl ether, toluene, YLENE and the hexanaphthene; The amount ratio of said graphite oxide and said organic solvent is 0.01～250g: 1L; Specifically can be 1-250g: 1L, 1-60g: 1L, 1-40g: 1L, 1-10g: 1L, 1-4g: 1L, 4-250g: 1L, 4-60g: 1L, 4-40g: 1L, 4-10g: 1L, 10-250g: 1L, 10-60g: 1L, 10-40g: 1L, 40-250g: 1L, 40-60g: 1L or 60-250g: 1L, preferred 1～30g: 1L; Said graphite oxide and said molecular formula are MgX 2The amount ratio of magnesium halide be 2-3g: 2-4g specifically can be 2-2.5g: 2-2.2g or 2.5-3g: 2-4g; Said graphite oxide and said general structure are that the amount ratio of the Grignard reagent of RMgX is 1.2-5g: 5-90g specifically can be 1.2-3g: 32-90g or 3-5g: 5-90g;
In the step 1) reactions step of said method a and method b; Temperature is 0～120 ℃; Specifically can be 40-110 ℃, 40-80 ℃, 40-70 ℃, 40-60 ℃, 60-110 ℃, 60-70 ℃, 60-80 ℃, 70-110 ℃, 70-80 ℃ or 80-110 ℃; Preferred 80～90 ℃; Time is 0.1～120 hour, specifically can be 4-48 hour, 4-24 hour, 4-20 hour, 5-48 hour, 5-24 hour, 5-20 hour, 20-48 hour, 20-24 hour or 24-48 hour, preferred 12～48 hours; This reactions step can divide a step or two steps to carry out; All between 0-120 ℃, the total reaction time of two steps is 0.1-120 hour to per step temperature of reaction, when reacting in two steps; Can carry out according to following step: after 4 hours, be warming up to 120 ℃ of reactions 6-10 hour again prior to 20 ℃ of reactions; In the said drying step, temperature is 40～100 ℃, and preferred 50～70 ℃, vacuum tightness is 0.1～0.01MPa, preferred 0.05～0.01MPa, and more preferably 0.01MPa, the time is 1-72 hour, specifically can be 12-15 hour, preferred 10～24 hours;
The step 2 of said method a and said method b) in, said titan-alkoxide is Ti (OEt) Cl 3, Ti (OEt) 2Cl 2, Ti (OEt) 3Cl, Ti (OEt) 4Or Ti (OBu) 4The carrier of said step 1) gained magnesium-containing compound and the amount ratio of said titanium tetrahalide or titan-alkoxide are 10～1000g: 1L; Specifically can be 10-30g: 1L, 7.5-30g: 1L, 12.5-30g: 1L, 10-12.5g: 1L, 7.5-12.5g: 1L, 7.5-10g: 1L or 10-30g: 1L; Each add-on is 15～200g: 1L specifically can be 15-25g: 1L, 15-20g: 1L or 20-25g: 1L;
The step 2 of said method a) in the reactions step, temperature is 0～120 ℃, and preferred 50～80 ℃, the time is 0.1～72 hour, specifically can be 4-10 hour, preferred 10～48 hours; In the said drying step, temperature is 0～100 ℃, and preferred 50～70 ℃, more preferably 60 ℃, vacuum tightness is 0.1～0.01MPa, preferred 0.05～0.01MPa, and more preferably 0.01MPa, the time is 1-72 hour, specifically can be 20-24 hour, preferred 10～24 hours.
Said method b also comprises the steps: in said step 2) reaction system after 0.1～2.0 hour step of-20 ℃ of following isothermal reactions, before being warming up to 1～4 hour step of 80～130 ℃ of isothermal reactions, in reaction system, add auxiliary agent; Said auxiliary agent is the internal electron donor compound; Preferred diether and/or carbonate; More preferably 9; At least a in 9-two (methoxymethyl) fluorenes, diethyl succinate, Tabutrex, Witcizer 300, diisobutyl phthalate, dimixo-octyl phthalate, ethyl benzoate, ethyl anisate and the ethyl p-ethoxybenzoate, most preferably at least a in diisobutyl phthalate and the Witcizer 300; The quality amount ratio of the carrier of said auxiliary agent and said step 1) gained magnesium-containing compound is 1: 1-100 specifically can be 1: 1.25-15,1: 1.25-3 or 1: 3-15, preferred 1: 1-10.
The above-mentioned metallic compound of preparation provided by the invention be aluminum contained compound be the method for the olefin polymerization catalysis of carrier with reduction-oxidation graphite, comprise the steps:
1) graphite oxide is scattered in the organic solvent adds aluminum contained compound behind the mixing and react, the reaction after drying that finishes obtains the activatory carrier;
2) said olefin polymerization catalysis and said aluminum contained compound are reacted in varsol, obtain the activatory catalyst solution;
3) with said step 2) the activatory carrier for preparing of the activatory catalyst solution for preparing and said step 1) reacts, and the reduction-oxidation graphite that obtains said metallic compound after the drying and be said aluminum contained compound is the olefin polymerization catalysis of carrier.
In the said step 1) of this method; It is that alkane, the total number of carbon atoms of 5～10 are that aromatic hydrocarbon, the total number of carbon atoms of 6～9 are at least a in 6～9 the naphthenic hydrocarbon that said organic solvent is selected from the total number of carbon atoms, at least a in preferred hexane, heptane, decane and the toluene; The amount ratio of said graphite oxide and said organic solvent is 0.01g: 1L～40g: 1L, preferred 2g: 1L～10g: 1L; The amount ratio 1g of said graphite oxide and said aluminum contained compound: 0.25mol～1g: 100mol, preferred 1g: 1mol～1g: 20mol; In the said reactions step, temperature is 0～120 ℃, and preferred 50～90 ℃, more preferably 60 ℃, the time is 0.1～120 hour, specifically can be 5-10 hour, 5-8 hour or 8-10 hour, preferred 10～24 hours; In the said drying step, temperature is 40～100 ℃, preferred 50～70 ℃, and more preferably 60 ℃; Vacuum tightness is 0.1～0.01MPa, preferred 0.05～0.01MPa, more preferably 0.01MPa; Time is 1-72 hour, specifically can be 15-25 hour, 15-20 hour or 20-25 hour, preferred 10～24 hours;
Said step 2) in, it is at least a in 5～10 alkane and the aromatic hydrocarbon that said varsol is selected from carbonatoms, at least a in preferred hexane, heptane, decane and the toluene; The amount ratio of said olefin polymerization catalysis, said aluminum contained compound and said varsol is 0.01-20mol: 1-5000mol: 1L; Specifically can be 0.02-20mol: 40-200mol: 1L, 0.02-3mol: 40-200mol: 1L, 3-20mol: 40-200mol: 1L, 0.02-20mol: 150-200mol: 1L, 0.02-3mol: 150-200mol: 1L, 3-20mol: 150-200mol: 1L, 3-20mol: 40-150mol: 1L, 0.02-3mol: 40-150mol: 1L or 3-20mol: 40-150mol: 1L, preferred 1mol: 100-500mol: 1L; In the said reactions step, temperature is 0～90 ℃, and preferred 40～90 ℃, more preferably 0 ℃, the time is 0.1～12 hour, preferred 2～12 hours, and more preferably 4 hours;
In the said step 3); Said step 1) gained activatory carrier and said step 2) amount ratio of gained activatory catalyst solution is 1-1.5g: 0.01-1mol; Specifically can be 1-1.5g: 0.01-0.15mol or 1-1.5g: 0.015-1mol, the mole dosage of said step 1) gained activatory carrier is pressed the Sauerstoffatom mole dosage and is calculated; In the said reactions step, temperature is 0～110 ℃, and preferred 40～90 ℃, more preferably 60 ℃, the time is 0.1～48 hour, specifically can be 15-18 hour, preferred 2～12 hours; In the said drying step, temperature is 50～90 ℃, and preferred 60～80 ℃, more preferably 60-70 ℃, the time is 2～48 hours, specifically can be 20-48 hour, 20-40 hour or 40-48 hour, and vacuum tightness is 0.1～0.01MPa, preferred 0.01MPa.
The above-mentioned metallic compound of preparation provided by the invention be magnesium-containing compound and aluminum contained compound be the method for the olefin polymerization catalysis of carrier with reduction-oxidation graphite, comprise the steps:
1) graphite oxide and said magnesium-containing compound are reacted in organic solvent, react the carrier that the after drying that finishes obtains said magnesium-containing compound;
2) with the carrier of said titanium tetrahalide or titan-alkoxide and the said magnesium-containing compound of said step 1) gained in-20 ℃ of following isothermal reactions after 0.1～2.0 hour; Be warming up to 80～130 ℃ of isothermal reactions 1.0～4.0 hours; Reaction adds said titanium tetrahalide or titan-alkoxide after finishing again in 80～130 ℃ of following isothermal reactions 1.0～4.0 hours, and the reduction-oxidation graphite that obtains said metallic compound and be magnesium-containing compound is the olefin polymerization catalysis of carrier;
3) with said step 2) the gained metallic compound is that the reduction-oxidation graphite of magnesium-containing compound is that the olefin polymerization catalysis and the said aluminum contained compound of carrier reacts in varsol, obtains the activatory carrier;
4) said transistion metal compound and said aluminum contained compound are reacted in varsol, obtain the activatory catalyst solution;
5) said step 3) gained activatory carrier and said step 4) gained activatory catalyst solution are reacted, the reaction finish obtain said metallic compound be said magnesium-containing compound and said aluminum contained compound be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.
In the step 1) of aforesaid method; It is that alkane, the total number of carbon atoms of 5～10 are that aromatic hydrocarbon, the total number of carbon atoms of 6～9 are that 6～9 naphthenic hydrocarbon, carbonatoms are at least a in 2～12 ether and the THF that said organic solvent is selected from carbonatoms, at least a in preferred hexane, heptane, decane, ether, positive propyl ether, butyl ether, isopropyl ether, isoamyl ether, toluene, YLENE and the hexanaphthene; Said molecular formula is MgX 2Magnesium halide and the quality amount ratio of said graphite oxide be 1-20: 1, preferred 1-3: 1, more preferably 1.3: 1; Said general structure is that the Grignard reagent of RMgX and the molar ratio of said graphite oxide are 1: 1～20: 1; Wherein, the mole dosage of said graphite oxide is pressed the mole dosage calculating of Sauerstoffatom; The amount ratio of said graphite oxide and said organic solvent is 0.01～100g: 1L, preferred 1.0～30g: 1L, more preferably 5g: 1L; In the said reactions step, temperature is 30～150 ℃, and preferred 80～130 ℃, the time is 1.0～20.0 hours, preferred 2～4 hours;
Said step 2) in, said titan-alkoxide is Ti (OEt) Cl 3, Ti (OEt) 2Cl 2, Ti (OEt) 3Cl, Ti (OEt) 4Or Ti (OBu) 4The carrier of said step 1) gained magnesium-containing compound and the amount ratio of said titanium tetrahalide or titan-alkoxide are 10～1000g: 1L, specifically can be 4.8-8g: 1L, 4.8-6g: 1L or 6-8g: 1L, preferred 50～200g: 1L, and each add-on is 8g: 1L;
In said step 3) and the step 4), it is at least a in 5～10 alkane and the aromatic hydrocarbon that said varsol all is selected from carbonatoms, at least a in all preferred hexane, heptane, decane and the toluene;
In the said step 3); Said step 2) the gained metallic compound is that the reduction-oxidation graphite of magnesium-containing compound is that the olefin polymerization catalysis of carrier and the amount ratio of said varsol are 1～500g: 1L; Preferred 10～200g: 1L; More preferably 10g: 1L, said step 2) the gained metallic compound is that the reduction-oxidation graphite of magnesium-containing compound is that the olefin polymerization catalysis of carrier and the amount ratio of said aluminum contained compound are 1g: 0.05mol;
In the said step 4), the amount ratio of said transistion metal compound and said varsol is 0.2-4mol: 1L, specifically can be 0.2-2mol: 1L or 2-4mol: 1L; The molar ratio of said aluminum contained compound and said transistion metal compound is 0.01～5000, specifically can be 10-300,10-15 or 15-300, preferred 100～500;
In said step 3) and the step 4) reactions step, temperature is 0～120 ℃, preferably is 60～90 ℃, and the time is 1～20 hour, preferably is 2～12 hours, more preferably 4-10 hour;
In the said step 5), it is 1～500g/L that said step 3) prepares the concentration of gained activatory carrier in said varsol, preferred 10～200g/L, more preferably 20g/L; The amount ratio of said step 3) gained activatory carrier and said step 4) gained activatory catalyst solution is 1g: 0.01-0.2mol; Specifically can be 1g: 0.01-0.1mol or 1g: 0.1-0.2mol, the mole dosage of said step 3) gained activatory carrier is pressed the molar weight of Sauerstoffatom and is calculated; In the said reactions step, temperature is 0～120 ℃, specifically can be 70-90 ℃, and preferred 60～80 ℃, the time is 1～10 hour, preferred 4～6 hours, and more preferably 4 hours.
Aforesaid method also comprises the steps: in said step 2) reaction system after 0.1～2.0 hour step of-20 ℃ of following isothermal reactions, said be warming up to 1.0～4.0 hours step of 80～130 ℃ of isothermal reactions before, in reaction system, add auxiliary agent; Said auxiliary agent is the internal electron donor compound; Preferred diether and/or carbonate; Preferred 9; At least a in 9-two (methoxymethyl) fluorenes, diethyl succinate, Tabutrex, Witcizer 300, diisobutyl phthalate, dimixo-octyl phthalate, ethyl benzoate, ethyl anisate and the ethyl p-ethoxybenzoate, most preferably at least a in diisobutyl phthalate and the Witcizer 300; The amount ratio of the carrier of said auxiliary agent and said step 1) gained magnesium-containing compound is 0.1-0.3g: 1.2g, specifically can be 0.2-0.3g: 1.2g or 0.1-0.2g: 1.2g.
The present invention adopts the situ aggregation method preparation to contain the polyolefin resin of reduction-oxidation graphite; Be about to olefin polymerization catalysis and (comprise Ziegler-Natta catalyst; Metallocene and non-metallocene catalyst etc.) be carried on the graphite oxide carrier; Prepared the graphite oxide carried catalyst that contains aluminium and/or magnesium-containing compound, graphite oxide is reduced to reduction-oxidation graphite in this loading process.Utilize this carried catalyst catalysis in olefine polymerization, in-situ polymerization preparation conduction polyolefin resin.Have following characteristic:
1. this method has solved the problem of graphite oxide and compatible polyolefin property difference, and successful is incorporated into graphite oxide in the polyolefin substrate;
2. in the graphite oxide carried catalyst preparation that contains aluminium and/or magnesium-containing compound or its catalysis in olefine polymerization, realized that graphite oxide is reduced to reduction-oxidation graphite, and then utilized the heat that discharges when reacting the reduction-oxidation graphite flake layer to be peeled off and it is uniformly distributed in the polyolefin substrate;
3. through the content of regulation and control graphite oxide in polyolefin substrate and then the electric conductivity of regulation and control polymkeric substance, satisfy the application of polyolefin resin in different field.
Description of drawings
Fig. 1 is the transmission electron microscope photo figure of the prepared acrylic resin of embodiment 1;
Fig. 2 is the stereoscan photograph figure of the prepared acrylic resin of embodiment 1;
Fig. 3 is the transmission electron microscope photo figure of the prepared ethylene-propylene copolymer resin of embodiment 1;
Fig. 4 is the stereoscan photograph figure of the prepared ethylene-propylene copolymer resin of embodiment 1.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to following examples.Experimental technique among the following embodiment like no specified otherwise, is ordinary method.
Below specific embodiment just a kind of graphite oxide of invention be that preparation method and the performance of this material of the conduction polyolefine material of weighting material made explanations.But these embodiment do not limit the scope of the invention, also should not be construed as have only condition provided by the invention, parameter or numerical value could embodiment of the present invention.The present invention focuses on that to adopt graphite oxide be this method of different alkene polymerizing catalyst catalysis in olefine polymerization of carrier and the electroconductibility of this polyolefine material is regulated and control; And other structural parameter of polymkeric substance are characterized, like melting point polymer, degree of isotacticity, molecular weight.The fusing point of polymkeric substance is through DSC (DSC) test, and molecular weight is through gel permeation chromatograph (GPC) test, and degree of isotacticity calculates through ebullient heptane extracting gained residuum.
Embodiment 1
1) utilizing method b to prepare metallic compound is the olefin polymerization catalysis of carrier for magnesium-containing compound with reduction-oxidation graphite
With 2.2g Magnesium Chloride Anhydrous MgCl 2Be scattered in the 50ml decane with the 6.0ml isooctyl alcohol, be heated to 130 ℃, form clear solution,, obtain the magnesium chloride alcohol adduct in 130 ℃ of reactions 2.0 hours; Above-mentioned magnesium chloride alcohol adduct is added dropwise in the suspension-s of 50ml organic solvent decane of the 2.0g graphite oxide that is scattered here and there; The mol ratio of C in the graphite oxide: O: H is: 6: 2.33: 1.2; With this mixed solution in 60 ℃ of isothermal reactions 5.0 hours; Filtering liquid then, the solid that leaches is with decane washing 3 times, and vacuum-drying obtains the carrier of magnesium-containing compound under 60 ℃, 0.01MPa after 12 hours;
The carrier 1.5g that in-20 ℃ 100ml titanium tetrachloride, adds the gained magnesium-containing compound; And, slowly be warming up to 120 ℃ in-20 ℃ of isothermal reactions 2.0 hours, add 0.5g internal electron donor compound diisobutyl phthalate; Afterwards in 120 ℃ of isothermal reactions 2.0 hours; Filtering liquid after reaction is accomplished adds the 100ml titanium tetrachloride once more, in 120 ℃ of isothermal reactions after 2.0 hours; With hexane wash 3～6 times, under 60 ℃, 0.01MPa vacuum-drying obtain after 12 hours metallic compound provided by the invention be the magnesium-containing compound magnesium chloride be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.This catalyzer is made up of reduction-oxidation graphite, metallic compound magnesium chloride, internal electron donor compound diisobutyl phthalate and olefin polymer catalyst Ziegler-Natta catalyst titanium tetrachloride; Wherein, The ratio of reduction-oxidation graphite and olefin polymer catalyst titanium tetrachloride is 1g: 0.61mol; The mol ratio of metallic compound magnesium chloride and olefin polymer catalyst titanium tetrachloride is 0.025, in internal electron donor diisobutyl phthalate and the olefin polymerization catalysis in the magnesium-containing compound magnesium chloride mol ratio of magnesium elements be 0.15.
2) utilize the method for slurry polymerization to prepare acrylic resin:
Under the vacuum state; Propylene monomer is charged in the 450ml reaction kettle, add 100ml organic solvent hexane successively, contain the n-heptane solution 3.0ml of 5.5mmol promotor triethyl aluminum, the n-heptane solution 6.0ml that contains 0.55mmol external electron donor dimethoxydiphenylsilane and 0.05 gram step 1) gained graphite oxide carried catalyst, the still internal pressure is constant in 0.5MPa; Temperature of reaction is 70 ℃; Polymerization reaction time 0.5 hour adds acidifying ethanol after polymerization is accomplished and stops polyreaction, respectively washs three times with deionized water and ethanol; Vacuum-drying is 24 hours under 60 ℃, 0.01MPa, obtains the graphite-filled acrylic resin of 5.8 gram reduction-oxidations provided by the invention; Reduction-oxidation graphite and polyacrylic weight ratio are 1: 115, and the mol ratio of carbon and oxygen element is 6: 1 in the reduction-oxidation graphite.Polyacrylic weight-average molecular weight is 26.7 ten thousand, and its MWD is 3.5, and fusing point is 162 ℃, and degree of isotacticity is 95.6%.Find out that from transmission electron microscope reduction-oxidation graphite is scattered in the polypropylene matrix with the form of limellar stripping, sees Fig. 1; Find out that from ESEM the reduction-oxidation graphite flake layer is dispersed in the polypropylene matrix, sees Fig. 2; Test its electroconductibility, its electric conductivity is 6.6 * 10 -5S/m.
This catalyzer also can be used to prepare the ethylene-propylene copolymer resin, specifically can prepare according to the method for following slurry polymerization:
Under the vacuum state; Propylene and ethene gas mixture are charged into (mol ratio of propylene and ethene is 1: 1) in the 450ml reaction kettle; Add 100ml organic solvent hexane successively, contain the heptane 1.0ml of 1.8mmol promotor triethyl aluminum, the n-heptane solution 1.0ml that contains 0.10mmol external electron donor dimethyl diphenyl silane and 0.1 gram step 1) gained graphite oxide carried catalyst; Still internal pressure 0.5MPa, temperature of reaction is 60 ℃, polyreaction 2.0 hours; Add acidifying ethanol after polymerization is accomplished and stop polyreaction; With deionized water and washing with alcohol, vacuum-drying obtained the ethylene-propylene copolymer that 7.0 grams graphite oxide provided by the invention is filled after 14 hours under 60 ℃, 0.01MPa; The weight ratio of reduction-oxidation graphite and ethylene-propylene copolymer is 1: 70, and the mol ratio of carbon and oxygen element is 6: 1 in the reduction-oxidation graphite.
The weight-average molecular weight of ethylene-propylene copolymer is 18.7 ten thousand, and its MWD is 3.2, and fusing point is 141 ℃, and degree of isotacticity is 98.6%.Find out that from transmission electron microscope reduction-oxidation graphite is scattered in the polypropylene matrix with the form of limellar stripping, sees Fig. 3; Find out that from ESEM the reduction-oxidation graphite flake layer is dispersed in the polypropylene matrix, sees Fig. 4; Test its electroconductibility, its electric conductivity is 1.8 * 10 -4S/m.
This catalyzer also can be used to prepare alloy in the Vestolen PP 7052 still, specifically can prepare according to the method for following mass polymerization and vapour phase polymerization coupling:
250 gram propylene liquids are added in the 2L reaction kettle; Add 0.25mol promotor triethyl aluminum, 0.0025mol external electron donor dimethyl diphenyl silane and 0.8 gram step 1) gained graphite oxide carried catalyst and hydrogen 0.2g under 30 ℃ successively; Be warming up to 70 ℃; Reacted 0.2 hour, the polymkeric substance that obtains directly carries out next step reaction.With propylene emptying residual in the reaction kettle in the above-mentioned steps and be cooled to 50 ℃, feed the gas mixture of 20g ethene and 60g propylene again, be warming up to 90 ℃, feed hydrogen 0.01g, react 0.1 hour, obtain the interior alloy of Vestolen PP 7052 still that 62 grams contain reduction-oxidation graphite; Weight ratio in reduction-oxidation graphite and the polypropylene alloy is 1: 76, and the mol ratio of carbon and oxygen element is 6: 1 in the reduction-oxidation graphite.
The weight-average molecular weight of alloy is 16.7 ten thousand in the Vestolen PP 7052 still, and its MWD is 4.1, and fusing point is 160 ℃, and the degree of isotacticity of polypropylene matrix is 97% in the material.From transmission and ESEM, can find out that reduction-oxidation graphite is dispersed in the polypropylene alloy matrix with sheet form; The electric conductivity of this resin is 5.2 * 10 -5S/m.
Embodiment 2
1) utilizing method b to prepare metallic compound is the olefin polymerization catalysis of carrier for magnesium-containing compound with reduction-oxidation graphite
With 4.0g Magnesium Chloride Anhydrous MgCl 2Be scattered in the 50ml decane with 12.5ml ethanol, be heated to 110 ℃, form clear solution, reacted 2.0 hours down, obtain the alcohol adduct of magnesium chloride in 110 ℃; The alcohol adduct of above-mentioned magnesium chloride is added dropwise in the suspension-s of 3.0g graphite oxide and 50ml organic solvent decane; Wherein the mol ratio of C in the graphite oxide: O: H is: 6: 3.7: 2.83; In 110 ℃ of following isothermal reactions 4.0 hours, filtering liquid then, the solid that leaches is with decane washing 3 times; 70 ℃, 0.01MPa obtains the carrier of magnesium-containing compound down after dry 15 hours.
In-20 ℃ 100ml titanium tetrachloride, add the carrier of 2.5 gram magnesium-containing compounds, and, slowly be warming up to 80 ℃ in-20 ℃ of following isothermal reactions 1.0 hours; Add 2.0 gram internal electron donors 9,9-two (methoxymethyl) fluorenes (also being the fluorenes diether) is afterwards in 120 ℃ of following isothermal reactions 1.5 hours; Filtering liquid after reaction is accomplished; Add the 100ml titanium tetrachloride once more, in 120 ℃ of following isothermal reactions after 3.0 hours, with hexane wash 3～6 times; 60 ℃, 0.01MPa obtain after dry 24 hours metallic compound provided by the invention be the magnesium-containing compound magnesium chloride be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.This catalyzer is by reduction-oxidation graphite, magnesium-containing compound magnesium chloride, internal electron donor 9, and 9-two (methoxymethyl) fluorenes and olefin polymer catalyst Ziegler-Natta catalyst titanium tetrachloride are formed; Wherein, The ratio of reduction-oxidation graphite and olefin polymer catalyst titanium tetrachloride is 1g: 0.364mol; The mol ratio of metallic compound magnesium chloride and olefin polymer catalyst titanium tetrachloride is 0.046; Internal electron donor 9, in 9-two (methoxymethyl) fluorenes and the olefin polymerization catalysis in the magnesium-containing compound magnesium chloride mol ratio of magnesium elements be 0.30.
2) utilize the method for mass polymerization to prepare Vestolen PP 7052:
500 gram propylene liquids are added in the 2L reaction kettle; Add 0.025mol promotor triethyl aluminum, 0.0025mol external electron donor dimethyl diphenyl silane, 0.005 gram hydrogen and 1.2 gram step 1) gained graphite oxide carried catalysts successively, temperature of reaction is 70 ℃, polyreaction 2 hours; After polymerization is accomplished; With gas emptying in the reaction kettle, discharging obtains 320 grams acrylic resin provided by the invention; Reduction-oxidation graphite and polyacrylic weight ratio are 1: 265, and wherein, the mol ratio of carbon and oxygen is 6: 0.2 in the reduction-oxidation graphite.
Polyacrylic weight-average molecular weight is 38.6 ten thousand, and its MWD is 3.1, and fusing point is 162 ℃, and degree of isotacticity is 98%.From ESEM and transmission electron microscope picture, can find out that graphite oxide is dispersed in the polypropylene matrix with sheet form, its electric conductivity is 8.1 * 10 -5S/m.
Embodiment 3
1) utilizing method b to prepare metallic compound is the olefin polymerization catalysis of carrier for magnesium-containing compound with reduction-oxidation graphite
With 2.0g Magnesium Chloride Anhydrous MgCl 2Be scattered in the 50ml decane with the 2.8ml isooctyl alcohol, be heated to 130 ℃, form clear solution, in 130 ℃ of reactions 4.0 hours; Above-mentioned magnesium chloride alcohol adduct is added dropwise in the suspension-s of 10ml organic solvent decane of 2.5 gram graphite oxides; Wherein the mol ratio of C in the graphite oxide: O: H is 6: 2.5: 1.5; In 50 ℃ of isothermal reactions 10.0 hours; Filtering liquid then, the solid that leaches is with decane washing 3 times, and 50 ℃, 0.01MPa obtain the carrier of magnesium-containing compound down after dry 20 hours.
The carrier that in-20 ℃ 100ml titanium tetrachloride, adds 2.0 gram magnesium-containing compounds; And after 1.0 hours, slowly be warming up to 60 ℃ in-20 ℃ of isothermal reactions, add 0.13g internal electron donor ethyl benzoate; Afterwards in 90 ℃ of isothermal reactions 1.0 hours; Filtering liquid after reaction is accomplished adds the 100ml titanium tetrachloride, once more in 90 ℃ of isothermal reactions 2.0 hours.At last, with hexane wash 3～6 times, 60 ℃, 0.01MPa obtain after dry 24 hours down metallic compound provided by the invention be the magnesium-containing compound magnesium chloride be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.This catalyzer is made up of reduction-oxidation graphite, magnesium-containing compound magnesium chloride, internal electron donor ethyl benzoate and olefin polymer catalyst Ziegler-Natta catalyst titanium tetrachloride; Wherein, The ratio of reduction-oxidation graphite and olefin polymer catalyst titanium tetrachloride is 1g: 0.455mol; The mol ratio of metallic compound magnesium chloride and olefin polymer catalyst titanium tetrachloride is 0.021, in internal electron donor and the olefin polymerization catalysis in the magnesium-containing compound magnesium chloride mol ratio of magnesium elements be 0.36.
2) utilize the method for slurry polymerization to prepare polyvinyl resin:
Under the vacuum state; Ethylene gas is charged in the 1000ml reaction kettle, add 100ml organic solvent hexane successively, contain the heptane 1.0ml and the 0.1 gram step 1) gained graphite oxide carried catalyst of 1.8mmol promotor triethyl aluminum, still internal pressure 0.3MPa; Temperature of reaction is 60 ℃; Polyreaction 1.0 hours adds acidifying ethanol after polymerization is accomplished and stops polyreaction, with deionized water and washing with alcohol; Vacuum-drying is 2 hours under 60 ℃, 0.01MPa, obtains 5.2 grams polyvinyl resin provided by the invention; Reduction-oxidation graphite and poly weight ratio are 1: 51, and wherein, the mol ratio of carbon and oxygen is 6: 0.4 in the reduction-oxidation graphite.
Poly weight-average molecular weight is 13.7 ten thousand, and its MWD is 3.2, and fusing point is 134 ℃.From transmission and ESEM, can find out that reduction-oxidation graphite is dispersed in the Vilaterm matrix with sheet form; The electric conductivity of this resin is 6.9 * 10 -3S/m.
Embodiment 4
1) utilizing method a to prepare metallic compound is the olefin polymerization catalysis of carrier for magnesium-containing compound with reduction-oxidation graphite
5.0 gram graphite oxides are scattered in the 500ml ether, will contain 0.05molC then 4H 9The 50ml diethyl ether solution of MgCl is added dropwise in the suspension-s of graphite oxide; Wherein the mol ratio of C in the graphite oxide: O: H is 6: 3: 2,, washs 5 times with ether after 20 hours in 40 ℃ of constant temperature back flow reaction; 60 ℃, 0.01MPa obtains the carrier of magnesium-containing compound down after dry 15 hours.
The carrier of 3.0 gram gained magnesium-containing compounds is scattered in the 100ml titanium tetrachloride, slowly is warming up to 20 ℃, add 0.15g internal electron donor Witcizer 300; React after 4 hours; Slowly be warming up to 120 ℃, reacted 6 hours, filter; It is magnesium-containing compound C that hexane wash 3～6 times, 60 ℃, 0.01MPa obtain metallic compound provided by the invention after dry 20 hours down 4H 9MgCl's is the olefin polymerization catalysis of carrier with reduction-oxidation graphite.This catalyzer is by reduction-oxidation graphite, magnesium-containing compound C 4H 9MgCl, olefin polymer catalyst Ziegler-Natta catalyst titanium tetrachloride and internal electron donor Witcizer 300 are formed; Wherein, the ratio of reduction-oxidation graphite and olefin polymer catalyst titanium tetrachloride is 1g: 0.30mol, contains magnesium metallic compound C 4H 9The mol ratio of MgCl and olefin polymer catalyst titanium tetrachloride is 0.055, magnesium-containing compound C in internal electron donor and the olefin polymerization catalysis 4H 9The mol ratio of magnesium elements is 0.25 among the MgCl.
2) utilize the method for slurry polymerization to prepare acrylic resin:
Under the vacuum state; Propylene monomer is charged in the 500ml reaction kettle, add 200ml organic solvent hexane successively, contain the n-heptane solution 1.5ml of 5.0mmol promotor triethyl aluminum, the n-heptane solution 3.0ml that contains 0.25mmol external electron donor dimethoxydiphenylsilane and 0.10 gram step 1) gained graphite oxide carried catalyst, still internal pressure 0.3MPa; Temperature of reaction is 40 ℃; Polymerization reaction time 0.5 hour adds acidifying ethanol after polymerization is accomplished and stops polyreaction, respectively washs three times with deionized water and ethanol; Vacuum-drying is 17 hours under 60 ℃, 0.01MPa, obtains the acrylic resin that 2.5 grams contain reduction-oxidation graphite; Reduction-oxidation graphite and polyacrylic weight ratio are 1: 24, and wherein, the mol ratio of carbon and oxygen is 6: 0.001 in the reduction-oxidation graphite.
Polyacrylic weight-average molecular weight is 19.2 ten thousand, and its MWD is 3.7, and fusing point is 162 ℃, and degree of isotacticity is 88.1%.Find out that from transmission electron microscope reduction-oxidation graphite is scattered in the polypropylene matrix with the form of limellar stripping, from ESEM, finds out, the reduction-oxidation graphite flake layer is dispersed in the polypropylene matrix, tests its electroconductibility, and its electric conductivity is 6.2S/m.
Embodiment 5
1) utilizing method a to prepare metallic compound is the olefin polymerization catalysis of carrier for magnesium-containing compound with reduction-oxidation graphite
1.2 gram graphite oxides are scattered in the 1200ml THF, and wherein the mol ratio of C in the graphite oxide: O: H is 6: 3.5: 2.5, will contain 0.2molC then 4H 9The 50ml tetrahydrofuran solution of MgBr is added dropwise in the suspension-s of graphite oxide, and in 80 ℃ of constant temperature back flow reaction after 48 hours, with THF washing 5 times, after the hexane wash 2 times, 60 ℃, 0.01MPa obtain the carrier of magnesium-containing compound after dry 25 hours.
The carrier of 1.0 gram gained magnesium-containing compounds is scattered in the 100ml titanium tetrachloride, slowly is warming up to 20 ℃, add 0.5g internal electron donor 9; 9-two (methoxymethyl) fluorenes reacted after 4 hours, was warmed up to 120 ℃; Reacted 10 hours; Filter, hexane wash 3～6 times, it is magnesium-containing compound C that 60 ℃, 0.01MPa obtain metallic compound provided by the invention after dry 16 hours down 4H 9MgBr's is the olefin polymerization catalysis of carrier with reduction-oxidation graphite.This catalyzer is by reduction-oxidation graphite, magnesium-containing compound C 4H 9MgBr, olefin polymer catalyst Ziegler-Natta catalyst titanium tetrachloride and internal electron donor 9,9-two (methoxymethyl) fluorenes is formed; Wherein, the ratio of reduction-oxidation graphite and olefin polymer catalyst titanium tetrachloride is 1.0g: 0.91mol, contains magnesium metallic compound C 4H 9The mol ratio of MgBr and olefin polymer catalyst titanium tetrachloride is 0.22, magnesium-containing compound C in internal electron donor and the olefin polymerization catalysis 4H 9The mol ratio of magnesium elements is 0.4 among the MgBr.
2) utilize the method for slurry polymerization to prepare Vestolen PP 7052:
Under the vacuum state; Propylene monomer is charged in the 500ml reaction kettle, add 50ml organic solvent hexane successively, contain the n-heptane solution 1.0ml of 1.8mmol promotor triethyl aluminum, the n-heptane solution 1.0ml that contains 0.18mmol external electron donor dimethoxydiphenylsilane and 0.04 gram step 1) gained graphite oxide carried catalyst, the constant reaction pressure in the still is at 0.8MPa; Temperature of reaction is 50 ℃; Polymerization reaction time 0.5 hour adds acidifying ethanol after polymerization is accomplished and stops polyreaction, respectively washs three times with deionized water and ethanol; Vacuum-drying is 12 hours under 60 ℃, 0.01MPa, obtains the acrylic resin that 1.0 grams contain reduction-oxidation graphite; Reduction-oxidation graphite and polyacrylic weight ratio are 1: 24, and wherein, the mol ratio of carbon and oxygen is 6: 0.0001 in the reduction-oxidation graphite.
Polyacrylic weight-average molecular weight is 19.7 ten thousand, and its MWD is 3.3, and fusing point is 162 ℃, and degree of isotacticity is 86.5%.Find out that from transmission electron microscope and ESEM reduction-oxidation graphite is dispersed in the polypropylene matrix with the form of limellar stripping, the electric conductivity of this matrix material is 10.8S/m.
Embodiment 6-11
1) step 1 is with embodiment 5 steps 1;
2) step 2 is with embodiment 5 steps 2), only according to the replacement of making following reaction conditions shown in the table 1, the performances such as electroconductibility of gained polypropylene material are all listed in the table 1.
The performance tabulation of table 1, reaction conditions and gained polypropylene material
Figure BDA0000054899670000181
Visible by table 1, through changing the electroconductibility of the adjustable polypropylene material of polymerizing condition, increase the content of reduction-oxidation graphite in polypropylene matrix, help increasing the electroconductibility of this matrix material.
Embodiment 12
1) utilizing method b to prepare metallic compound is the olefin polymerization catalysis of carrier for magnesium-containing compound with reduction-oxidation graphite
3.0 gram graphite oxides are scattered in the 750ml THF, and wherein the mol ratio of C in the graphite oxide: O: H is 6: 3: 2, will contain 0.5molC then 2H 4The 50ml diethyl ether solution of MgI is added dropwise in the suspension-s of graphite oxide, and after 24 hours, with THF washing 5 times, 60 ℃, 0.05MPa obtains the carrier of magnesium-containing compound after dry 18 hours in 70 ℃ of constant temperature back flow reaction.
The carrier of the said magnesium-containing compound of 2.0 grams is scattered in-20 ℃ the 100ml titanium tetrachloride; Slowly be warming up to 120 ℃ of reactions after 1.0 hours; Filter, and then add the 100ml titanium tetrachloride, in 100 ℃ of reactions after 4 hours; With hexane wash 3～6 times, it is magnesium-containing compound C that 70 ℃, 0.04MPa obtain metallic compound provided by the invention after dry 20 hours down 2H 4MgI's is the olefin polymerization catalysis of carrier with reduction-oxidation graphite.This catalyzer by reduction-oxidation graphite, contain magnesium metallic compound C 2H 4MgI and olefin polymer catalyst Ziegler-Natta catalyst titanium tetrachloride are formed; The ratio of reduction-oxidation graphite and olefin polymer catalyst titanium tetrachloride is 1g: 0.455mol, contains magnesium metallic compound C 2H 4The mol ratio of MgI and olefin polymer catalyst titanium tetrachloride is 0.55.
2) utilize the method for slurry polymerization to prepare acrylic resin:
Under the vacuum state, propylene gas is charged in the 450ml reaction kettle, add 100ml organic solvent hexane successively; The heptane 1.0ml and the 0.02 gram step 1) gained graphite oxide carried catalyst that contain 1.8mmol promotor triethyl aluminum; The still internal pressure is constant in 0.7MPa, and temperature of reaction is 40 ℃, polyreaction 1.0 hours; Add acidifying ethanol after polymerization is accomplished and stop polyreaction; With deionized water and washing with alcohol, vacuum-drying is 24 hours under 60 ℃, 0.01MPa, obtains 3.8 grams conducting polypropylene resin provided by the invention; The weight ratio of reduction-oxidation graphite and multipolymer is 1: 199, and wherein, the mol ratio of carbon and oxygen is 6: 0.001 in the reduction-oxidation graphite.
Polyacrylic weight-average molecular weight is 22.7 ten thousand, and fusing point is 161 ℃, and degree of isotacticity is 91%.From transmission and ESEM, can find out that reduction-oxidation graphite is dispersed in the polypropylene matrix with sheet form; The electric conductivity of this matrix material is 8.1 * 10 -6S/m.
Embodiment 13
1) 1.8 gram graphite oxides is scattered in the 300ml organic solvent toluene; Wherein the mol ratio of C in the graphite oxide: O: H is 6: 2.5: 2; Add the toluene solution 30ml that contains the 5mol MAO then; In 60 ℃ of down reactions 10 hours, use toluene wash then 5 times, 40 ℃, 0.01MPa obtain the activatory carrier after dry 15 hours down;
With 1mol olefin polymer catalyst transistion metal compound Et (Ind) 2ZrCl 2Be added among the toluene solution 50ml that contains the 10mol MAO, reacted 4.0 hours down, obtain activatory catalyst solution 1mol in 0 ℃.
Then gained activatory catalyst solution 1mol is added dropwise to the 50ml toluene suspension that contains 1.5 gram gained activatory carriers; 60 ℃ were reacted 15 hours; After reaction is accomplished; With toluene wash 5 times, 70 ℃, 0.01MPa obtain after dry 20 hours down metallic compound provided by the invention be the aluminum contained compound MAO be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.This catalyzer is by by reduction-oxidation graphite, aluminiferous metals compound MAO and olefin polymer catalyst Et (Ind) 2ZrCl 2Form; Reduction-oxidation graphite and olefin polymer catalyst Et (Ind) 2ZrCl 2Ratio be 1g: 0.066mol, aluminiferous metals compound MAO and olefin polymer catalyst Et (Ind) 2ZrCl 2Mol ratio be 100.
2) utilize the method for slurry polymerization to prepare ethene and 1-octene copolymer:
Under the vacuum state, ethylene gas is charged in the 450ml reaction kettle, add 225ml organic solvent toluene, 2.0ml (0.0128mol) 1-octene copolymer monomer successively; The toluene solution 1.0ml and the 0.10 gram step 1) gained graphite oxide carried catalyst that contain 1.4mmol promotor MAO; Constant reaction pressure in the still is at 0.4MPa, and temperature of reaction is 60 ℃, and polyreaction is after 1 hour; Add acidifying ethanol and stop polyreaction; With deionized water and washing with alcohol, vacuum-drying is 24 hours under 60 ℃, 0.01MPa, obtains 3.5 gram ethene and 1-octene copolymers; The weight ratio of reduction-oxidation graphite and multipolymer 1: 34, wherein, the mol ratio of carbon and oxygen is 6: 0.01 in the reduction-oxidation graphite.
The weight-average molecular weight of ethene and 1-octene copolymer is 32.7 ten thousand, and fusing point is 125 ℃.From transmission and ESEM, can find out that reduction-oxidation graphite is dispersed in ethene and the 1-octene copolymer matrix with sheet form; The electric conductivity of this matrix material is 6.9S/m.
Embodiment 14-18
Step 1 is with embodiment 13 steps 1.
Step 2 is with embodiment 13 steps 2, its difference be polymerizing condition according to replacing shown in the table 2, obtain the ethene and the 1-octene copolymer of different reduction-oxidation content of graphite provided by the invention, the performances such as electroconductibility of this ethene and 1-octene copolymer are seen table 2.
Table 2, polymerizing condition and ethene and the tabulation of 1-octene copolymer performance
Figure BDA0000054899670000201
Visible by table 2, the fusing point of multipolymer changes along with the variation of 1-octene consumption.Ethene is relevant with the content of reduction-oxidation graphite in polymer matrices with the electric conductivity of 1-octene copolymer, along with the increase electric conductivity rising of reduction-oxidation content of graphite.
Embodiment 19
1) 2.1 gram graphite oxides is scattered in the 300ml heptane; Wherein the mol ratio of C in the graphite oxide: O: H is 6: 2.33: 1.5; Add the n-heptane solution 40ml that contains the 2mol triisobutyl aluminium then; In 60 ℃ of reactions after 8 hours, with heptane wash 4 times, 60 ℃, 0.01MPa drying obtained the activatory carrier after 25 hours.
With 0.15mol olefin polymerization catalysis transistion metal compound Et (Ind) 2ZrCl 2Be added among the toluene solution 50ml that contains the 7.5mol MAO, reacted 4.0 hours down, obtain activatory catalyst solution 0.15mol in 0 ℃.
Then gained activatory catalyst solution 0.15mol is added dropwise to the 50ml toluene suspension that contains 1.5 gram gained activatory carriers, 60 ℃ were reacted 15 hours.After reaction is accomplished, with toluene wash 3 times, 70 ℃, 0.01MPa down drying obtain after 48 hours metallic compound provided by the invention be the aluminum contained compound MAO be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.This catalyzer is by by reduction-oxidation graphite, aluminiferous metals compound MAO and olefin polymer catalyst Et (Ind) 2ZrCl 2Form reduction-oxidation graphite and olefin polymer catalyst Et (Ind) 2ZrCl 2Ratio be 1g: 0.1mol, aluminiferous metals compound MAO and olefin polymer catalyst Et (Ind) 2ZrCl 2Mol ratio be 500.
2) utilize the method for slurry polymerization to prepare acrylic resin:
Under the vacuum state, propylene gas is charged in the 450ml reaction kettle, add 100ml organic solvent heptane, 14.5ml (0.116mol) 1-hexene co-monomer successively; The toluene solution 2.0ml and the 0.06 gram step 1) gained graphite oxide carried catalyst that contain 2.8mmol promotor MAO; The still internal pressure is constant in 0.55MPa, and temperature of reaction is 60 ℃, and polyreaction is after 0.5 hour; Add acidifying ethanol and stop polyreaction; With deionized water and washing with alcohol, vacuum-drying is 24 hours under 60 ℃, 0.01MPa, obtains 5.1 grams acrylic resin provided by the invention; The weight ratio of reduction-oxidation graphite and multipolymer is 1: 84, wherein the mol ratio 6: 0.05 of carbon and oxygen in the reduction-oxidation graphite.
Polyacrylic weight-average molecular weight is 530,000, and fusing point is 124 ℃.From transmission and ESEM, can find out that reduction-oxidation graphite is dispersed in propylene and the 1-hexene copolymer matrix with sheet form; The electric conductivity of this matrix material is 8.1 * 10 -5S/m.
Embodiment 20
1) 1.2 gram graphite oxides is scattered in the 600ml hexane; Wherein the mol ratio of C in the graphite oxide: O: H is 6: 2.8: 2.3; Add the n-heptane solution 40ml contain the 1.2mol triethyl aluminum then, in 60 ℃ of reactions after 5 hours, with hexane wash 5 times; 60 ℃, 0.01MPa obtains the activatory carrier after dry 20 hours down.
With 0.01mol olefin polymerization catalysis transistion metal compound Me 2C (Cp) is ZrCl (Flu) 2Be added among the toluene solution 50ml that contains the 2.0mol MAO, reacted 4.0 hours down, obtain activatory catalyst solution 0.01mol in 0 ℃.
Then gained activatory catalyst solution 0.01mol is added dropwise to the 50ml heptane suspension-s that contains 1.0 gram gained activatory carriers, 60 ℃ were reacted 18 hours.After reaction is accomplished, with heptane wash 5 times, 60 ℃, 0.01MPa down drying obtain after 40 hours metallic compound provided by the invention be the aluminum contained compound MAO be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.This catalyzer is by reduction-oxidation graphite, aluminiferous metals compound and olefin polymer catalyst (metallocene catalyst) Me 2C (Cp) is ZrCl (Flu) 2Form reduction-oxidation graphite and olefin polymer catalyst Me 2C (Cp) is ZrCl (Flu) 2Ratio be 1g: 0.01mol, aluminiferous metals compound and olefin polymer catalyst Me 2C (Cp) is ZrCl (Flu) 2Mol ratio be 200.
2) utilize the method for slurry polymerization to prepare polyvinyl resin:
Under the vacuum state, ethylene gas is charged in the 450ml reaction kettle, add 100ml organic solvent toluene successively; Contain the toluene solution 1.0ml and the 0.05 gram step 1) gained graphite oxide carried catalyst of 1.4mmol promotor MAO, the still internal pressure is constant in 0.5MPa, and temperature of reaction is 80 ℃; After the polyreaction 0.5 hour, add acidifying ethanol and stop polyreaction, with deionized water and washing with alcohol; Vacuum-drying is 24 hours under 60 ℃, 0.01MPa, obtains 2.5 gram Vilaterm; Reduction-oxidation graphite and poly weight ratio are 1: 49, wherein the mol ratio 6: 1 of carbon and oxygen in the reduction-oxidation graphite.
Poly weight-average molecular weight is 420,000, and fusing point is 130 ℃.From transmission and ESEM, can find out that reduction-oxidation graphite is dispersed in the Vilaterm matrix with sheet form; The electric conductivity of this resin is 4.7 * 10 -3S/m.
Embodiment 21
1) with embodiment 20 steps 1, its difference: 0.01mol transistion metal compound two [N-(3-tertiary butyl salicylidene) anilino] zirconium dichloride is added among the toluene solution 50ml that contains the 2.0mol MAO.The reduction-oxidation graphite that obtains metallic compound provided by the invention and be aluminum contained compound is the olefin polymerization catalysis of carrier.This catalyzer is made up of reduction-oxidation graphite, aluminiferous metals compound MAO and olefin polymer catalyst two [N-(3-tertiary butyl salicylidene) anilino] zirconium dichloride; Wherein, The ratio of reduction-oxidation graphite and olefin polymer catalyst two [N-(3-tertiary butyl salicylidene) anilino] zirconium dichloride is 1g: 0.01mol, and the mol ratio of aluminiferous metals compound MAO and olefin polymer catalyst (non-metallocene catalyst) two [N-(3-tertiary butyl salicylidene) anilino] zirconium dichloride is 200.
2) utilize the method for slurry polymerization to prepare ethene and styrol copolymer:
Under the vacuum state, ethylene gas is charged in the 450ml reaction kettle, add 50ml organic solvent hexane, the styrene copolymerized monomer of 1.0ml (0.0087mol) successively; The toluene solution 1.0ml and the 0.20 gram step 1) gained graphite oxide carried catalyst that contain 1.4mmol promotor MAO; The still internal pressure is constant in 0.5MPa, and temperature of reaction is 60 ℃, and polyreaction is after 1 hour; Add acidifying ethanol and stop polyreaction; With deionized water and washing with alcohol, vacuum-drying is 24 hours under 60 ℃, 0.01MPa, obtains 2.8 gram ethene and styrol copolymers; The weight ratio of reduction-oxidation graphite and ethene and styrol copolymer is 1: 13, wherein the mol ratio 6: 1 of carbon and oxygen in the reduction-oxidation graphite.
The weight-average molecular weight of ethene and styrol copolymer is 390,000, and fusing point is 126 ℃.From transmission and ESEM, can find out that reduction-oxidation graphite is dispersed in ethene and the styrol copolymer matrix with sheet form; The electric conductivity of this resin is 7.9 * 10 -4S/m.
Embodiment 22
1) with 2.0g Magnesium Chloride Anhydrous MgCl 2Be scattered in the 20ml decane with the 5.5ml isooctyl alcohol, be heated to 110 ℃, form clear solution, in 110 ℃ of reactions 4.0 hours.Above-mentioned magnesium chloride alcohol adduct is added dropwise in the suspension-s of 300ml decane of 1.5g graphite oxide; Wherein the mol ratio of C in the graphite oxide: O: H is 6: 2.5: 2.1; In 90 ℃ of isothermal reactions 12 hours; Filtering liquid then, the solid that leaches is with decane washing 3 times, and 50 ℃, 0.01MPa obtain the carrier of magnesium-containing compound down after dry 20 hours.
The carrier that in-20 ℃ 150ml titanium tetrachloride, adds 1.2 gram gained magnesium-containing compounds, and in-20 ℃ of following isothermal reactions 1 hour.Slowly be warming up to 110 ℃, add 0.1g internal electron donor diisobutyl phthalate, then in 110 ℃ of isothermal reactions 2 hours, filtering liquid after reaction is accomplished adds the 50ml titanium tetrachloride, once more in 120 ℃ of isothermal reactions 2 hours.At last, with hexane wash 3～6 times, 50 ℃, 0.01MPa obtain metallic compound down after dry 24 hours be that the reduction-oxidation graphite of magnesium-containing compound is the olefin polymerization catalysis of carrier.
With 1.0 gram gained metallic compounds is that the reduction-oxidation graphite of magnesium-containing compound is that the olefin polymerization catalysis of carrier is scattered in the 100ml toluene; Add the toluene solution 30ml that contains the 0.05mol MAO then; In 90 ℃ of reactions 10 hours; Use toluene wash then 5 times, 50 ℃, 0.01MPa obtains the activatory carrier after dry 24 hours down.
With 0.01mol olefin polymerization catalysis transistion metal compound rac-Me 2Si (2-Me-4-PhInd) 2ZrCl 2(be added among the toluene solution 50ml that contains the 3.0mol MAO,, obtain activatory catalyst solution 0.01mol in 0 ℃ of reaction 4 hours.
Gained activatory catalyst solution 0.01mol is added dropwise to the 50ml toluene suspension that contains 1.0 gram gained activatory carriers, in 90 ℃ of reactions 4 hours.After reaction is accomplished, with toluene wash 5 times, 60 ℃, 0.01MPa down drying obtain after 24 hours metallic compound provided by the invention be aluminum contained compound and magnesium-containing compound be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.
This catalyzer by reduction-oxidation graphite, contain magnesium and aluminiferous metals compound and olefin polymerization catalysis thing catalyzer titanium tetrachloride and rac-Me 2Si (2-Me-4-PhInd) 2ZrCl 2Form, reduction-oxidation graphite and olefin polymer catalyst titanium tetrachloride be 1g: 0.38mol, reduction-oxidation graphite and olefin polymer catalyst rac-Me 2Si (2-Me-4-PhInd) 2ZrCl 2Be 1g: 0.01mol, the mol ratio that contains magnesium metallic compound and olefin polymerization catalysis thing catalyzer titanium tetrachloride is 0.046, aluminiferous metals compound and olefin polymer catalyst rac-Me 2Si (2-Me-4-PhInd) 2ZrCl 2Mol ratio be 300.
2) utilize the method for mass polymerization to prepare polypropylene alloy:
200 gram propylene liquids are added in the 2L reaction kettle; What add 0.25mol promotor triethyl aluminum, 0.025mol external electron donor dimethyl diphenyl silane and 0.8 gram step 1) gained metallic compound under 30 ℃ successively and be aluminum contained compound and magnesium-containing compound is the olefin polymerization catalysis and the hydrogen 0.2g of carrier with reduction-oxidation graphite; Be warming up to 60 ℃; Reacted 0.2 hour, the polymkeric substance that obtains directly carries out next step reaction.
With propylene emptying residual in the reaction kettle in the above-mentioned steps and be cooled to 50 ℃; Feed the gas mixture of 20g ethene and 60g propylene again, feed hydrogen 0.03g, be warming up to 60 ℃; Reacted 0.5 hour, and finally obtained the interior alloy of multiphase copolymer Vestolen PP 7052 still that 78 grams contain reduction-oxidation graphite; The content of reduction-oxidation graphite in the polypropylene alloy matrix is 1.0wt%, and wherein the mol ratio of carbon and oxygen element is 6: 0.03 in the reduction-oxidation graphite.
The weight-average molecular weight of polypropylene alloy is 790,000, and fusing point is 161 ℃, and degree of isotacticity is 96.1%.From scanning and transmission electron microscope photo figure, can find out that graphite oxide is dispersed in the polypropylene alloy matrix with the form of limellar stripping; The electric conductivity of this polypropylene alloy is 7.5 * 10 -4S/m.
Embodiment 23
1) with 2.0g Magnesium Chloride Anhydrous MgCl 2Be scattered in the 20ml decane with 5.5ml ethanol, be heated to 110 ℃, form clear solution, in 110 ℃ of reactions 4.0 hours.Above-mentioned magnesium chloride alcohol adduct is added dropwise in the suspension-s of 300ml decane of 1.5g graphite oxide; Wherein the mol ratio of C in the graphite oxide: O: H is 6: 3.2: 1.9; In 90 ℃ of isothermal reactions 12 hours, filtering liquid then, the solid that leaches is with decane washing 3 times; 50 ℃, 0.01MPa obtains the carrier of magnesium-containing compound down after dry 30 hours.
The carrier that in-20 ℃ 150ml titanium tetrachloride, adds 1.2g gained magnesium-containing compound, and in-20 ℃ of following isothermal reactions 1 hour.Slowly be warming up to 110 ℃, add 0.3g internal electron donor fluorenes diether, then in 110 ℃ of isothermal reactions 2 hours, filtering liquid after reaction is accomplished adds the 50ml titanium tetrachloride, once more in 120 ℃ of isothermal reactions 2 hours.At last; With hexane wash 3～6 times; 60 ℃; 0.01MPa obtaining the reduction-oxidation graphite of magnesium-containing compound after following dry 20 hours is the olefin polymerization catalysis of carrier, in the olefin polymerization catalysis of internal electron donor fluorenes diether and gained reduction-oxidation graphite carrier in the magnesium chloride mol ratio of magnesium elements be 0.1.
With the reduction-oxidation graphite of 1.0 gram gained magnesium-containing compounds is that the olefin polymerization catalysis of carrier is scattered in the 100ml toluene; Add the toluene solution 30ml that contains the 0.05mol MAO then; In 90 ℃ of reactions 10 hours; Use toluene wash then 5 times, 60 ℃, 0.01MPa obtains the activatory carrier after dry 20 hours down.
With 0.1mol transistion metal compound Et (Ind) 2ZrCl 2Be added among the toluene solution 50ml that contains the 1.0mol MAO,, obtain activatory catalyst solution 0.1mol in 0 ℃ of reaction 4 hours.
Gained activatory catalyst solution 0.1mol is added dropwise to the 50ml heptane suspension-s that contains 1.0 gram gained activatory carriers, in 70 ℃ of reactions 4 hours.After reaction is accomplished, with heptane wash 5 times, 60 ℃, 0.01MPa down drying obtain after 20 hours metallic compound provided by the invention be aluminum contained compound and magnesium-containing compound be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.
This catalyzer by reduction-oxidation graphite, contain magnesium and aluminiferous metals compound and olefin polymerization catalysis thing catalyzer titanium tetrachloride and Et (Ind) 2ZrCl 2Form, reduction-oxidation graphite and olefin polymer catalyst titanium tetrachloride be 1g: 0.38mol, reduction-oxidation graphite and olefin polymer catalyst Et (Ind) 2ZrCl 2Be 1g: 0.1mol, the mol ratio that contains magnesium metallic compound and olefin polymerization catalysis thing catalyzer titanium tetrachloride is 0.046, aluminiferous metals compound and olefin polymer catalyst Et (Ind) 2ZrCl 2Mol ratio be 100.
2) utilize the method for mass polymerization to prepare polypropylene alloy:
300 gram propylene liquids are added in the 2L reaction kettle; What add 0.30mol promotor triethyl aluminum, 0.030mol external electron donor dimethyl diphenyl silane and 0.7 gram step 1) gained metallic compound under 30 ℃ successively and be aluminum contained compound and magnesium-containing compound is the olefin polymerization catalysis and the hydrogen 0.1g of carrier with reduction-oxidation graphite; Be warming up to 60 ℃; Reacted 0.2 hour, the polymkeric substance that obtains directly carries out next step reaction.
With propylene emptying residual in the reaction kettle in the above-mentioned steps and be cooled to 50 ℃; Feed the gas mixture of 10g ethene and 60g propylene again, feed hydrogen 0.03g, be warming up to 90 ℃; Reacted 0.5 hour, and finally obtained the interior alloy of multiphase copolymer Vestolen PP 7052 still that 90 grams contain reduction-oxidation graphite; The content of reduction-oxidation graphite in the polypropylene alloy matrix is 0.78wt%, and wherein the mol ratio of carbon and oxygen is 6: 0.1 in the reduction-oxidation graphite.
The weight-average molecular weight of polypropylene alloy is 38.7 * 10 4G/mol, its MWD is 3.9, and fusing point is 162 ℃, and degree of isotacticity is 98.1%.From scanning and transmission electron microscope photo figure, can find out that graphite oxide is dispersed in the polypropylene alloy matrix with the form of limellar stripping; The electric conductivity of this polypropylene alloy is 1.4 * 10 -4S/m.
Embodiment 24
1) with 2.0g Magnesium Chloride Anhydrous MgCl 2Be scattered in the 20ml decane with the 5.5ml isooctyl alcohol, be heated to 110 ℃, form clear solution, in 110 ℃ of reactions 4.0 hours.Above-mentioned magnesium chloride alcohol adduct is added dropwise in the suspension-s of 300ml organic solvent decane of 1.5g graphite oxide; Wherein the mol ratio of C in the graphite oxide: O: H is 6: 2.8: 2.1; In 90 ℃ of isothermal reactions 12 hours, filtering liquid then, the solid that leaches is with decane washing 3 times; 50 ℃, 0.01MPa obtains the carrier of magnesium-containing compound down after dry 24 hours.
The carrier that in-20 ℃ 150ml titanium tetrachloride, adds 1.2g gained magnesium-containing compound, and in-20 ℃ of following isothermal reactions 1 hour.Slowly be warming up to 110 ℃, add 0.2g internal electron donor Witcizer 300, then in 110 ℃ of isothermal reactions 2 hours, filtering liquid after reaction is accomplished adds the 100ml titanium tetrachloride, once more in 120 ℃ of isothermal reactions 2 hours.At last; With hexane wash 3～6 times; 70 ℃, 0.01MPa obtains down magnesium-containing compound after dry 44 hours reduction-oxidation graphite is the olefin polymerization catalysis of carrier, in internal electron donor Witcizer 300 and the olefin polymerization catalysis in the magnesium chloride mol ratio of magnesium elements be 0.08.
With the reduction-oxidation graphite of 1.0 gram magnesium-containing compounds is that the olefin polymerization catalysis of carrier is scattered in the 100ml toluene; Add the toluene solution 30ml that contains the 0.05mol MAO then; In 90 ℃ of reactions 10 hours; Use toluene wash then 5 times, 60 ℃, 0.01MPa obtains the activatory carrier after dry 10 hours down.
With 0.20mol olefin polymerization catalysis transistion metal compound Me 2C (Cp) is ZrCl (Flu) 2Be added among the toluene solution 50ml that contains the 3.0mol MAO,, obtain activatory catalyst solution 0.2mol in 0 ℃ of reaction 4 hours.
This activatory catalyst solution 0.2mol is added dropwise to the 50ml toluene suspension that contains 1.0 gram gained activatory carriers, in 90 ℃ of reactions 4 hours.After reaction is accomplished, with toluene wash 5 times, 60 ℃, 0.01MPa down drying obtain after 10 hours metallic compound provided by the invention be aluminum contained compound and magnesium-containing compound be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.
This catalyzer by reduction-oxidation graphite, contain magnesium and aluminiferous metals compound and olefin polymerization catalysis thing catalyzer titanium tetrachloride and Me 2C (Cp) is ZrCl (Flu) 2Form, reduction-oxidation graphite and olefin polymer catalyst titanium tetrachloride be 1g: 1.51mol, reduction-oxidation graphite and olefin polymer catalyst Me 2C (Cp) is ZrCl (Flu) 2Be 1g: 0.2mol, the mol ratio that contains magnesium metallic compound and olefin polymerization catalysis thing catalyzer titanium tetrachloride is 0.023, aluminiferous metals compound and olefin polymer catalyst Et (Ind) 2ZrCl 2Mol ratio be 150.
2) utilize the method for mass polymerization to prepare polypropylene alloy:
400 gram propylene liquids are added in the 2L reaction kettle; What add 0.15mol promotor triethyl aluminum, 0.015mol external electron donor dimethyl diphenyl silane and 2.0 gram step 1) gained metallic compounds under 30 ℃ successively and be aluminum contained compound and magnesium-containing compound is the olefin polymerization catalysis and the hydrogen 0.05g of carrier with reduction-oxidation graphite; Be warming up to 60 ℃; Reacted 0.3 hour, the polymkeric substance that obtains directly carries out next step reaction.
With propylene emptying residual in the reaction kettle in the above-mentioned steps and be cooled to 50 ℃; Feed the gas mixture of 10g ethene and 50g propylene again, feed hydrogen 0.05g, be warming up to 75 ℃; Reacted 0.2 hour, and finally obtained the interior alloy of multiphase copolymer Vestolen PP 7052 still that 102 grams contain reduction-oxidation graphite; The weight ratio of reduction-oxidation graphite and polypropylene alloy is 1: 50, and wherein carbon and oxygen mol ratio are 6: 0.05 in the reduction-oxidation graphite.
The weight-average molecular weight of polypropylene alloy is 550,000, and fusing point is 162 ℃, and degree of isotacticity is 98.8%.From scanning and transmission electron microscope photo figure, can find out that reduction-oxidation graphite is dispersed in the polypropylene alloy matrix with the form of limellar stripping; The electric conductivity of this polypropylene alloy is 2.8 * 10 -2S/m.

Claims (19)

1. a polyolefin resin that contains reduction-oxidation graphite comprises polyolefine and reduction-oxidation graphite.
2. resin according to claim 2 is characterized in that: the said polyolefin resin that contains reduction-oxidation graphite is made up of said polyolefine and said reduction-oxidation graphite.
3. resin according to claim 1 and 2 is characterized in that: said polyolefine is selected from least a in Vilaterm, Vestolen PP 7052, ethylene-propylene copolymer, ethene and alpha-olefin copolymer and propylene and the alpha-olefin copolymer;
Said poly weight-average molecular weight is 10,000～1,000,000, preferred 10,000～500,000; Said polyacrylic weight average molecular weight range is 10,000～1,500,000, preferred 10～800,000; The weight-average molecular weight of said ethylene-propylene copolymer is 10,000～1,000,000, preferred 100,000～700,000; The weight-average molecular weight of said ethene and alpha-olefin copolymer is 10,000～1,000,000, preferred 100,000～800,000; The weight-average molecular weight of said propylene and alpha-olefin copolymer is 10,000～1,500,000, preferred 100,000～800,000; Said terminal olefin is selected from least a in 1-butylene, 1-amylene, 1-hexene, 1-octene and the vinylbenzene;
The mol ratio of carbon and oxygen element is 6: 0.0001～2 in the said reduction-oxidation graphite, preferred 6: 0.0001～1, and said reduction-oxidation graphite and said polyolefinic weight ratio are 1: 3～1: 9999, preferred 1: 4-1: 999;
The said electric conductivity that contains the polyolefin resin of reduction-oxidation graphite is 1.0 * 10 -8～9.9 * 10 2S/m.
4. according to the arbitrary described resin of claim 1-3, it is characterized in that: the said polyolefin resin that contains reduction-oxidation graphite is according to claim 5 or the preparation of 6 said methods and get.
5. one kind prepares the arbitrary said method that contains the polyolefin resin of reduction-oxidation graphite of claim 1-4; Comprise the steps: that with at least a in ethene and the propylene be polymerization single polymerization monomer; The olefin polymerization catalysis that is carrier with the arbitrary said reduction-oxidation graphite of claim 7-11 is that catalyzer carries out polymerization, and reaction finishes and obtains the said polyolefin resin that contains reduction-oxidation graphite;
Said polymerization method is the method for slurry polymerization, mass polymerization or mass polymerization and vapour phase polymerization coupling.
6. method according to claim 5; It is characterized in that: said slurry polymerization comprises the steps: under the vacuum state; Said polymerization single polymerization monomer is charged in the reaction kettle; Then with organic solvent, promotor and said be that the olefin polymerization catalysis of carrier mixes and carries out polyreaction with reduction-oxidation graphite, reaction finishes and obtains the said polyolefin resin that contains reduction-oxidation graphite after the drying;
In the said slurry phase polymerisation process, the consumption of said organic solvent is 0.01～0.80 with the ratio of reaction kettle volume, preferred 0.1～0.5; Said is that the olefin polymerization catalysis of carrier and the amount ratio of said organic solvent are 1 * 10 with the graphite oxide -4～20g: 1L, preferred 0.5～5g: 1L; Said promotor is 1.4-5.5mmol: 0.02-2g with the amount ratio that is the olefin polymerization catalysis of carrier with reduction-oxidation graphite, preferred 1.4-1.8mmol: 0.1g; In the said reactions step, temperature is 0～120 ℃, and preferred 40～80 ℃, more preferably 70 ℃, pressure is 0.1～1.0MPa, preferred 0.1～0.7MPa, and more preferably 0.5MPa, the time is 0.01～10 hour, preferred 0.1～2 hour, more preferably 0.5 hour; In the said drying step, temperature is 40～70 ℃, and preferred 60 ℃, the time is 0.5-48 hour, and preferred 12～24 hours, vacuum tightness was 0.01MPa-0.1MPa, preferred 0.01MPa;
Said slurry phase polymerisation process also comprised the steps: before said polymerization procedure, in reaction system, added at least a in comonomer and the external electron donor, and wherein, said comonomer is a terminal olefin shown in the formula I;
R-(CH＝CH)n-R’
(formula I)
Among the said formula I, R is H or (CH 2) N1CH 3, n 1Integer for 1-11; R ' is (CH 2) N2CH 3Or phenyl, n 2Integer for 1-11; Said terminal olefin is selected from least a in 1-butylene, 1-amylene, 1-hexene, 1-octene and the vinylbenzene; The concentration of said comonomer in said organic solvent is 0～10mol/L, preferred 0～1mol/L, and the concentration of said comonomer is not 0; Said external electron donor is dimethyl diphenyl silane, dimethyldimethoxysil,ne, trimethylammonium methoxy silane, methyltrimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane or tetrahydrotoluene dimethoxy silane; The mol ratio of said external electron donor and said promotor is 0: 1～1: 1000, and preferred 1: 10～1: 100, the mole dosage of said external electron donor was not 0;
Said mass polymerization comprise the steps: with propylene liquid, external electron donor, promotor and said be that the olefin polymerization catalysis of carrier mixes and carries out polyreaction with reduction-oxidation graphite, reaction finishes and obtains the said polyolefin resin that contains reduction-oxidation graphite; Said external electron donor is dimethyl diphenyl silane, dimethyldimethoxysil,ne, trimethylammonium methoxy silane, methyltrimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane or tetrahydrotoluene dimethoxy silane; In the said bulk polymerization, the quality of said propylene liquid and the volume ratio of reaction kettle are 0.01～0.70g: 1ml, preferred 0.10～0.50g: 1ml; Said is that the weight consumption of olefin polymerization catalysis and propylene liquid of carrier is than 1 * 10 with reduction-oxidation graphite -6～1 * 10 -2, preferred 1 * 10 -4～1 * 10 -1Said promotor and said be that the amount ratio of the olefin polymerization catalysis of carrier is 0.025-0.3mol: 0.7-2.0g with reduction-oxidation graphite, preferred 0.25mol: 0.8g; The molar ratio of said external electron donor and said promotor is 0: 1～1: 1000, preferred 1: 10～1: 100, and more preferably 1: 10; In the said reactions step, temperature is 40～80 ℃, and preferred 60-70 ℃, more preferably 60 ℃, the time is 0.01～10.0 hour, preferred 0.1～2 hour;
Said mass polymerization also comprises the steps: before said polymerization procedure, in reaction system, to add hydrogen; The weight consumption of said hydrogen and propylene liquid is than 0～0.01, and is preferred 0～0.001, and the weight of said hydrogen is not 0;
Said mass polymerization and the method for vapour phase polymerization coupling comprise the steps: with propylene liquid, hydrogen, promotor and said be to be warming up to 50～80 ℃ after the olefin polymerization catalysis of carrier mixes in reaction kettle with reduction-oxidation graphite; React after 0.01～10.0 hour; Emptying; To be that 0.001: 1～100: 1 the gas mixture of being made up of ethene and propylene is passed in the said reaction kettle with volume ratio then; After 0.05～10.0 hour, obtain the said polyolefin resin that contains reduction-oxidation graphite in 40-90 ℃ of reaction; In the method for said mass polymerization and vapour phase polymerization coupling, the volume ratio of said propylene liquid and reaction kettle is 0.01～0.70, preferred 0.05～0.5; The weight consumption of said hydrogen and propylene liquid is than 0～0.01, and is preferred 0.000001～0.001, and the weight of said hydrogen is not 0; Said is that the weight consumption of olefin polymerization catalysis and propylene of carrier is than 1 * 10 with reduction-oxidation graphite -6～1 * 10 -2, preferred 1 * 10 -4～1 * 10 -1Said promotor and said be that the molar ratio of the olefin polymerization catalysis of carrier is 1～10000 with reduction-oxidation graphite, preferred 100～3000; In said two reactions step, the reaction times preferably is 0.1～2 hour; The method of said mass polymerization and vapour phase polymerization coupling also comprise the steps: said with propylene liquid, hydrogen, promotor and said be that the olefin polymerization catalysis of carrier before the mixing step, adds external electron donor in reaction kettle in reaction system with reduction-oxidation graphite; Said external electron donor is dimethyl diphenyl silane, dimethyldimethoxysil,ne, trimethylammonium methoxy silane, methyltrimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane or tetrahydrotoluene dimethoxy silane; The molar ratio of said external electron donor and said promotor is 0: 1～1: 1000, and preferred 1: 10～1: 100, the mole dosage of said external electron donor was not 0;
In the method for said slurry polymerization, mass polymerization and said mass polymerization and vapour phase polymerization coupling; It is at least a in 6～9 the naphthenic hydrocarbon that said organic solvent all is selected from the total number of carbon atoms is 5～10 alkane, the total number of carbon atoms is 6-9 aromatic hydrocarbon and the total number of carbon atoms, at least a in preferred hexane, heptane, decane, toluene, YLENE and the hexanaphthene; The general structure of said promotor is Al (OR ') nR 3-n, n is the integer of 0-3, it is in 2～10 the alkyl any one that R and R ' all are selected from the total number of carbon atoms, preferred trimethylaluminium, triethyl aluminum, triisobutyl aluminium or MAO.
7. one kind is the olefin polymerization catalysis of carrier with reduction-oxidation graphite, comprises following component: reduction-oxidation graphite, metallic compound and olefin polymer catalyst; Wherein, said metallic compound is selected from least a in magnesium-containing compound and the aluminum contained compound; Said olefin polymer catalyst is selected from least a in Ziegler-Natta catalyst, metallocene catalyst and the non-metallocene catalyst.
8. catalyzer according to claim 7 is characterized in that: said is that the olefin polymerization catalysis of carrier is made up of said reduction-oxidation graphite, said metallic compound and said olefin polymer catalyst with reduction-oxidation graphite.
9. according to claim 7 or 8 described catalyzer, it is characterized in that: said magnesium-containing compound is that molecular formula is MgX 2Magnesium halide or general structure be the Grignard reagent of RMgX; Said MgX 2In, X is fluorine, chlorine, bromine or iodine, preferred X is a chlorine; Among the said RMgX, R is selected from any one in the alkyl that the total number of carbon atoms is 1-10, and preferable methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, X are fluorine, chlorine, bromine or iodine;
Said aluminum contained compound is Al (OR ') nR 3-n, said Al (OR ') nR 3-nIn, n is the integer of 0-3, R and R ' all are selected from any one in the alkyl that the total number of carbon atoms is 2-10, the preferred trimethylaluminium of said aluminum contained compound, triethyl aluminum, triisobutyl aluminium or MAO;
In the said olefin polymer catalyst, the used titanium tetrahalide of said Ziegler-Natta catalyst is TiCl 4, TiBr 4Or TiI 4, used titan-alkoxide is Ti (OEt) Cl 3, Ti (OEt) 2Cl 2, Ti (OEt) 3Cl, Ti (OEt) 4Or Ti (OBu) 4The general structure of said metallocene catalyst is suc as formula shown in the II:
(Cp I-B e-Cp II)MR 1 aR 2 b
(formula II)
Among the said formula II, M is selected from least a in Ti, Zr, Hf, V, Fe, Y, Sc and the lanthanide series metal; Said Cp IAnd Cp IIRepresent cyclopentadienyl moiety or contain substituent cyclopentadienyl moiety, said substituting group is selected from least a in the aromatic base that alkyl that the total number of carbon atoms is 1-6, naphthenic base that the total number of carbon atoms is 3-18 and the total number of carbon atoms be 6-18; Said R 1And R 2All be selected from H, halogen atom, the total number of carbon atoms and be 1-8 alkyl, the total number of carbon atoms and be the alkoxyl group of 1-8, aryl that the total number of carbon atoms is 6-20, substituted the total number of carbon atoms of alkyl that the total number of carbon atoms is 1-15 and be the aryl of 6-20, acyloxy, allyl group and the total number of carbon atoms that the total number of carbon atoms is 1-8 and be in the siloyl group of 1-15 any one; Said B represents alkyl bridge or siloyl group bridge, and is preferred-C (R 3R 4)-or-Si (R 3R 4)-; R 3And R 4All be selected from H, the total number of carbon atoms and be in the alkyl of 1-4 and the aryl that the total number of carbon atoms is 6-10 any one; E is 1,2 or 3, and a is the integer of 1-4, preferred 1 or 2; B is the integer of 1-4, preferred 1 or 2; The preferred Et of said metallocene catalyst (Ind) 2ZrCl 2, Me 2C (Cp) is ZrCl (Flu) 2, Et (H 4Ind) 2ZrCl 2, Me 2Si (Ind) 2ZrCl 2, Me 2Si (2-Me-4-Ph-Ind) 2ZrCl 2, Me 2Si (Me 4Cp) 2ZrCl 2, Me 2Si (Flu) 2ZrCl 2, Me 2Si (2-Me-4-Naph-Ind) 2ZrCl 2Or Ph 2Si (Ind) 2ZrCl 2, wherein, Me is a methyl, and Ph is a phenyl, and Cp is a cyclopentadienyl moiety, and Ind is an indenyl, H 4Ind is 4,5,6, and 7-tetrahydro-indenes, Flu are fluorenyl, and Naph is a naphthyl;
The general structure of said non-metallocene catalyst is shown in formula III:
Figure FDA0000054899660000041
(formula III)
In the said formula III, M is selected from least a among Zr, Ti, V and the Hf, R 1, R 2And R 3All be selected from H, halogen atom, the total number of carbon atoms and be the alkyl of 1-8, alkoxyl group that the total number of carbon atoms is 1-8, aryl that the total number of carbon atoms is 6-20, the substituted aryl of alkyl that the total number of carbon atoms is 1-6, aryl that the total number of carbon atoms is the cycloalkyl substituted of 3-18, the substituted aryl of aromatic base that the total number of carbon atoms is 6-18, acyloxy, allyl group and the total number of carbon atoms that the total number of carbon atoms is 1-8 and be in the siloyl group of 1-15 any one; X is fluorine, chlorine, bromine or iodine, and n is 1 or 2; Said non-metallocene catalyst is preferably two [N-(3-tertiary butyl salicylidene) anilino] zirconium dichloride, two [N-(3-methyl salicylidene) anilino] zirconium dichloride, two [N-(3-sec.-propyl salicylidene) anilino] zirconium dichloride or two [N-(3-adamantyl-5-methyl salicylidene) anilino] zirconium dichloride;
The ratio of said reduction-oxidation graphite and said olefin polymer catalyst is 1g: 0.001mol～10mol; Preferred 1g: 0.01mol～0.1mol; Said olefin polymerization catalysis is the mole number calculating by the metal active site; The mol ratio of said metallic compound and olefin polymerization catalysis is 0.0001～10000, preferred 0.01～2000.
10. according to the arbitrary described catalyzer of claim 7-9, it is characterized in that: said is that carrier and metallic compound are that the olefin polymerization catalysis of said magnesium-containing compound or the mixture be made up of said magnesium-containing compound and said aluminum contained compound also comprises internal electron donor with reduction-oxidation graphite; Said internal electron donor is selected from 9; At least a in 9-two (methoxymethyl) fluorenes, diethyl succinate, Tabutrex, Witcizer 300, diisobutyl phthalate, dimixo-octyl phthalate, ethyl benzoate, ethyl anisate and the ethyl p-ethoxybenzoate, at least a in preferred diisobutyl phthalate and the Witcizer 300; In said internal electron donor and the said olefin polymerization catalysis in the magnesium-containing compound mol ratio of magnesium elements be 0.05～0.6, preferred 0.1～0.4.
11. according to the arbitrary described catalyzer of claim 7-10, it is characterized in that: said is that the olefin polymerization catalysis of carrier is to get according to the arbitrary said method preparation of claim 12-14 with reduction-oxidation graphite.
12. one kind prepare metallic compound described in the claim 7-10 be magnesium-containing compound be the method for the olefin polymerization catalysis of carrier with reduction-oxidation graphite, be following method a or method b;
Wherein, said method a comprises the steps:
1) graphite oxide and said magnesium-containing compound are reacted in organic solvent, reaction finishes and obtains the carrier of said magnesium-containing compound after the drying;
2) carrier with said titanium tetrahalide or titan-alkoxide and said step 1) gained magnesium-containing compound reacts, reaction finish obtain after the drying said metallic compound be magnesium-containing compound be the olefin polymerization catalysis of carrier with reduction-oxidation graphite;
Said method b comprises the steps:
1) graphite oxide and said magnesium-containing compound are reacted in organic solvent, reaction finishes and obtains the carrier of said magnesium-containing compound after the drying;
2) with the carrier of said titanium tetrahalide or titan-alkoxide and said step 1) gained magnesium-containing compound after-20 ℃ of following isothermal reaction 0.1-2 hours; Be warming up to 80～130 ℃ of isothermal reaction 1-4 hours; Reaction adds said titanium tetrahalide or titan-alkoxide after finishing again after 80～130 ℃ of following isothermal reaction 1-4 hours, and what obtain said metallic compound and be magnesium-containing compound is the olefin polymerization catalysis of carrier with reduction-oxidation graphite.
13. method according to claim 12; It is characterized in that: in the step 1) of said method a and method b; It is that alkane, the total number of carbon atoms of 5～10 are that aromatic hydrocarbon, the total number of carbon atoms of 6～9 are that naphthenic hydrocarbon, the total number of carbon atoms of 6～9 are at least a in 2～12 ether and the THF that said organic solvent all is selected from the total number of carbon atoms, at least a in preferred hexane, heptane, decane, ether, positive propyl ether, butyl ether, isopropyl ether, isoamyl ether, toluene, YLENE and the hexanaphthene;
The amount ratio of said graphite oxide and said organic solvent is 0.01～250g: 1L, preferred 1～30g: 1L; Said graphite oxide and said molecular formula are MgX 2The amount ratio of magnesium halide be 2-3g: 2-4g; Said graphite oxide and said general structure are that the amount ratio of the Grignard reagent of RMgX is 1.2-5g: 5-90g;
In the step 1) reactions step of said method a and method b, temperature is 0～120 ℃, and preferred 80～90 ℃, the time is 0.1～120 hour, preferred 12～48 hours; In the said drying step, temperature is 40～100 ℃, and preferred 50～70 ℃, vacuum tightness is 0.1～0.01MPa, preferred 0.05～0.01MPa, and more preferably 0.01MPa, the time is 1-72 hour, preferred 10～24 hours;
The step 2 of said method a and said method b) in, said titan-alkoxide is Ti (OEt) Cl 3, Ti (OEt) 2Cl 2, Ti (OEt) 3Cl, Ti (OEt) 4Or Ti (OBu) 4The carrier of said step 1) gained magnesium-containing compound and the amount ratio of said titanium tetrahalide or titan-alkoxide are 10～1000g: 1L, and each add-on is 15～200g: 1L;
The step 2 of said method a) in the reactions step, temperature is 0～120 ℃, and preferred 50～80 ℃, the time is 0.1～72 hour, preferred 10～48 hours; In the said drying step, temperature is 0～100 ℃, and preferred 50～70 ℃, more preferably 60 ℃, vacuum tightness is 0.1～0.01MPa, preferred 0.05～0.01MPa, and more preferably 0.01MPa, the time is 1-72 hour, preferred 10～24 hours.
14. according to claim 12 or 13 described methods; It is characterized in that: said method b also comprises the steps: in said step 2) reaction system is after 0.1～2.0 hour step of-20 ℃ of following isothermal reactions; Before being warming up to 1～4 hour step of 80～130 ℃ of isothermal reactions, in reaction system, add auxiliary agent; Said auxiliary agent is the internal electron donor compound; Preferred diether and/or carbonate; More preferably 9; At least a in 9-two (methoxymethyl) fluorenes, diethyl succinate, Tabutrex, Witcizer 300, diisobutyl phthalate, dimixo-octyl phthalate, ethyl benzoate, ethyl anisate and the ethyl p-ethoxybenzoate, most preferably at least a in diisobutyl phthalate and the Witcizer 300; The quality amount ratio of the carrier of said auxiliary agent and said step 1) gained magnesium-containing compound is 1: 1-100, preferred 1: 1-10.
15. one kind prepare metallic compound described in the claim 7-10 be aluminum contained compound be the method for the olefin polymerization catalysis of carrier with reduction-oxidation graphite, comprise the steps:
1) graphite oxide is scattered in the organic solvent adds aluminum contained compound behind the mixing and react, the reaction after drying that finishes obtains the activatory carrier;
2) said olefin polymerization catalysis and said aluminum contained compound are reacted in varsol, obtain the activatory catalyst solution;
3) with said step 2) the activatory carrier for preparing of the activatory catalyst solution for preparing and said step 1) reacts, and the reduction-oxidation graphite that obtains said metallic compound after the drying and be said aluminum contained compound is the olefin polymerization catalysis of carrier.
16. method according to claim 15; It is characterized in that: in the said step 1); It is that alkane, the total number of carbon atoms of 5～10 are that aromatic hydrocarbon, the total number of carbon atoms of 6～9 are at least a in 6～9 the naphthenic hydrocarbon that said organic solvent is selected from the total number of carbon atoms, at least a in preferred hexane, heptane, decane and the toluene; The amount ratio of said graphite oxide and said organic solvent is 0.01g: 1L～40g: 1L, preferred 2g: 1L～10g: 1L; The amount ratio 1g of said graphite oxide and said aluminum contained compound: 0.25mol～1g: 100mol, preferred 1g: 1mol～1g: 20mol; In the said reactions step, temperature is 0～120 ℃, and preferred 50～90 ℃, more preferably 60 ℃, the time is 0.1～120 hour, preferred 10～24 hours; In the said drying step, temperature is 40～100 ℃, and preferred 50～70 ℃, more preferably 60 ℃, vacuum tightness is 0.1～0.01MPa, preferred 0.05～0.01MPa, and more preferably 0.01MPa, the time is 1-72 hour, preferred 10～24 hours;
Said step 2) in, it is at least a in 5～10 alkane and the aromatic hydrocarbon that said varsol is selected from carbonatoms, at least a in preferred hexane, heptane, decane and the toluene; The amount ratio of said olefin polymerization catalysis, said aluminum contained compound and said varsol is 0.01-20mol: 1-5000mol: 1L, preferred 1mol: 100-500mol: 1L; In the said reactions step, temperature is 0～90 ℃, and preferred 40～90 ℃, more preferably 0 ℃, the time is 0.1～12 hour, preferred 2～12 hours, and more preferably 4 hours;
In the said step 3), said step 1) gained activatory carrier and said step 2) amount ratio of gained activatory catalyst solution is 1-1.5g: 0.01-1mol, the mole dosage of said step 1) gained activatory carrier is pressed the Sauerstoffatom mole dosage and is calculated; In the said reactions step, temperature is 0～110 ℃, and preferred 40～90 ℃, more preferably 60 ℃, the time is 0.1～48 hour, preferred 2～12 hours; In the said drying step, temperature is 50～90 ℃, and preferred 60～80 ℃, more preferably 60-70 ℃, the time is 2～48 hours, and vacuum tightness is 0.1～0.01MPa, preferred 0.01MPa.
17. one kind prepare the arbitrary said metallic compound of claim 7-10 be magnesium-containing compound and aluminum contained compound be the method for the olefin polymerization catalysis of carrier with reduction-oxidation graphite, comprise the steps:
1) graphite oxide and said magnesium-containing compound are reacted in organic solvent, react the carrier that the after drying that finishes obtains said magnesium-containing compound;
2) with the carrier of said titanium tetrahalide or titan-alkoxide and the said magnesium-containing compound of said step 1) gained in-20 ℃ of following isothermal reactions after 0.1～2.0 hour; Be warming up to 80～130 ℃ of isothermal reactions 1.0～4.0 hours; Reaction adds said titanium tetrahalide or titan-alkoxide after finishing again in 80～130 ℃ of following isothermal reactions 1.0～4.0 hours, and the reduction-oxidation graphite that obtains said metallic compound and be magnesium-containing compound is the olefin polymerization catalysis of carrier;
3) with said step 2) the gained metallic compound is that the reduction-oxidation graphite of magnesium-containing compound is that the olefin polymerization catalysis and the said aluminum contained compound of carrier reacts in varsol, obtains the activatory carrier;
4) said transistion metal compound and said aluminum contained compound are reacted in varsol, obtain the activatory catalyst solution;
5) said step 3) gained activatory carrier and said step 4) gained activatory catalyst solution are reacted, the reaction finish obtain said metallic compound be said magnesium-containing compound and said aluminum contained compound be the olefin polymerization catalysis of carrier with reduction-oxidation graphite.
18. method according to claim 17; It is characterized in that: in the said step 1); It is that alkane, the total number of carbon atoms of 5～10 are that aromatic hydrocarbon, the total number of carbon atoms of 6～9 are that 6～9 naphthenic hydrocarbon, carbonatoms are at least a in 2～12 ether and the THF that said organic solvent is selected from carbonatoms, at least a in preferred hexane, heptane, decane, ether, positive propyl ether, butyl ether, isopropyl ether, isoamyl ether, toluene, YLENE and the hexanaphthene; Said molecular formula is MgX 2Magnesium halide and the quality amount ratio of said graphite oxide be 1-20: 1, preferred 1-3: 1, more preferably 1.3: 1; Said general structure is that the Grignard reagent of RMgX and the molar ratio of said graphite oxide are 1: 1～20: 1; Wherein, the mole dosage of said graphite oxide is pressed the mole dosage calculating of Sauerstoffatom; The amount ratio of said graphite oxide and said organic solvent is 0.01～100g: 1L, preferred 1.0～30g: 1L, more preferably 5g: 1L; In the said reactions step, temperature is 30～150 ℃, and preferred 80～130 ℃, the time is 1.0～20.0 hours, preferred 2～4 hours;
Said step 2) in, said titan-alkoxide is Ti (OEt) Cl 3, Ti (OEt) 2Cl 2, Ti (OEt) 3Cl, Ti (OEt) 4Or Ti (OBu) 4The carrier of said step 1) gained magnesium-containing compound and the amount ratio of said titanium tetrahalide or titan-alkoxide are 10～1000g: 1L, preferred 50～200g: 1L, and each add-on is 8g: 1L;
In said step 3) and the step 4), it is at least a in 5～10 alkane and the aromatic hydrocarbon that said varsol all is selected from carbonatoms, at least a in all preferred hexane, heptane, decane and the toluene;
In the said step 3); Said step 2) the gained metallic compound is that the reduction-oxidation graphite of magnesium-containing compound is that the olefin polymerization catalysis of carrier and the amount ratio of said varsol are 1～500g: 1L; Preferred 10～200g: 1L; More preferably 10g: 1L, said step 2) the gained metallic compound is that the reduction-oxidation graphite of magnesium-containing compound is that the olefin polymerization catalysis of carrier and the amount ratio of said aluminum contained compound are 1g: 0.05mol;
In the said step 4), the amount ratio of said transistion metal compound and said varsol is 0.2-4mol: 1L; The molar ratio of said aluminum contained compound and said transistion metal compound is 0.01～5000, preferred 100～500;
In said step 3) and the step 4) reactions step, temperature is 0～120 ℃, preferably is 60～90 ℃, and the time is 1～20 hour, preferably is 2～12 hours, more preferably 4-10 hour;
In the said step 5), it is 1～500g/L that said step 3) prepares the concentration of gained activatory carrier in said varsol, preferred 10～200g/L, more preferably 20g/L; The amount ratio of said step 3) gained activatory carrier and said step 4) gained activatory catalyst solution is 1g: 0.01-0.2mol, and the mole dosage of said step 3) gained activatory carrier is pressed the molar weight of Sauerstoffatom and calculated; In the said reactions step, temperature is 0～120 ℃, and preferred 60～80 ℃, the time is 1～10 hour, preferred 4～6 hours, and more preferably 4 hours.
19. according to claim 17 or 18 described methods; It is characterized in that: said method also comprises the steps: in said step 2) reaction system is after 0.1～2.0 hour step of-20 ℃ of following isothermal reactions; Said be warming up to 1.0～4.0 hours step of 80～130 ℃ of isothermal reactions before, in reaction system, add auxiliary agent; Said auxiliary agent is the internal electron donor compound; Preferred diether and/or carbonate; Preferred 9; At least a in 9-two (methoxymethyl) fluorenes, diethyl succinate, Tabutrex, Witcizer 300, diisobutyl phthalate, dimixo-octyl phthalate, ethyl benzoate, ethyl anisate and the ethyl p-ethoxybenzoate, most preferably at least a in diisobutyl phthalate and the Witcizer 300; The amount ratio of the carrier of said auxiliary agent and said step 1) gained magnesium-containing compound is 0.1-0.3g: 1.2g.
CN2011100909769A 2011-04-12 2011-04-12 Polyolefin resin containing reduced graphite oxide and its preparation method Pending CN102731880A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103172772A (en) * 2013-03-04 2013-06-26 河南科技大学 Method for preparing UHMWPE (ultrahigh molecular weight polyethylene) graphene material by ionic liquid assisted polymerization filling
CN103980608A (en) * 2014-04-30 2014-08-13 中国科学院化学研究所 Polypropylene nanocomposite material capable of being used for 3D printing, and preparation method and application thereof
CN106220774A (en) * 2016-08-31 2016-12-14 齐齐哈尔大学 A kind of preparation method of polystyrene/graphene nano composite material
CN106810630A (en) * 2015-12-02 2017-06-09 中国石油天然气股份有限公司 A kind of preparation method of Graphene/PP composite material
US10150850B2 (en) 2014-11-05 2018-12-11 King Fahd University Of Petroleum And Minerals High-density polyethylene-graphene nanocomposites and methods thereof

Non-Patent Citations (1)

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Title
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CN103172772A (en) * 2013-03-04 2013-06-26 河南科技大学 Method for preparing UHMWPE (ultrahigh molecular weight polyethylene) graphene material by ionic liquid assisted polymerization filling
CN103980608A (en) * 2014-04-30 2014-08-13 中国科学院化学研究所 Polypropylene nanocomposite material capable of being used for 3D printing, and preparation method and application thereof
CN103980608B (en) * 2014-04-30 2015-07-08 中国科学院化学研究所 Polypropylene nanocomposite material capable of being used for 3D printing, and preparation method and application thereof
US10150850B2 (en) 2014-11-05 2018-12-11 King Fahd University Of Petroleum And Minerals High-density polyethylene-graphene nanocomposites and methods thereof
CN106810630A (en) * 2015-12-02 2017-06-09 中国石油天然气股份有限公司 A kind of preparation method of Graphene/PP composite material
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