CN102030844A - Olefin polymerization catalyst and polyethylene with ultralow branching coefficient and ultrahigh molecular weight - Google Patents

Olefin polymerization catalyst and polyethylene with ultralow branching coefficient and ultrahigh molecular weight Download PDF

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CN102030844A
CN102030844A CN2010105544738A CN201010554473A CN102030844A CN 102030844 A CN102030844 A CN 102030844A CN 2010105544738 A CN2010105544738 A CN 2010105544738A CN 201010554473 A CN201010554473 A CN 201010554473A CN 102030844 A CN102030844 A CN 102030844A
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alcohol
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CN102030844B (en
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唐勇
卫兵
李军方
孙秀丽
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JIUJIANG ZHONGKE XINXING NEW MATERIAL CO., LTD.
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention relates to two load-type non-metallocene polyolefin catalysts, preparation methods and applications thereof as well as polyethylene with ultralow branching coefficient and ultrahigh molecular weight. One load-type non-metallocene polyolefin catalyst is obtained by that one polydentate ligand and a transition metal compound loaded on a carrier are subjected to a chemical reaction with an in-situ load method, and the load-type non-metallocene polyolefin catalyst can be used for the homopolymerization of catalysis ethylene to obtain an easily-processed polyethylene resin with ultrahigh molecular weight. The other load-type non-metallocene polyolefin catalyst is formed by directly loading a metal coordination compound on a magnesium compound; during the homopolymerization/copolymerization of catalysis olefin, a small quantity of catalyst is consumed; the obtained ethylene copolymer and homopolymer has narrow molecular weight distribution, the parameter diameter of the comonomer and polymer is even distributed, and the polymer particles are spherical or are similar to a sphere. The polyethylene polymer with ultralow branching coefficient and ultrahigh molecular weight is characterized in that the branched chain number in every 100000 skeleton carbon atoms is 0-2, and the polydispersity index range of the polymer is 2-10.

Description

Olefin polymerization catalysis and ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE)
Technical field
The present invention relates to a class load type non-metallocene polyolefin catalyst, Preparation method and use.This load type non-metallocene polyolefin catalyst has the feature of single site catalysts.Under the effect of promotor, utilize that the copolymerization of equal polymerization that this catalyzer can catalyzed ethylene or ethene and alpha-olefin obtains that molecular weight distribution is narrower, size distribution evenly, particle diameter is spherical or subglobose olefin polymer.
The load type non-metallocene polyolefin catalyst that the present invention relates to can obtain a class polydentate ligand and the transistion metal compound generation chemical reaction that is carried on the carrier by original position load method.Under the effect of promotor, the ultrahigh molecular weight polyethylene(UHMWPE) that adopts this catalyst to obtain has narrow molecular weight distribution (1.6-3.0), bulk density height, size distribution evenly and the product feature that is easy to process.
The present invention relates to a kind of ultralow degree of branching ultrahigh-molecular ethylene polymer that is easy to process and uses thereof.
Background technology
Along with the fast development of polyolefin industry, the production of high-performance poly olefin material more and more is subjected to people's extensive attention.Present international research thinks that the production of high-performance poly olefin material mainly can realize by dual mode: 1) utilize the Ziegler-Natta catalyst of modification, rely on the improvement of chemical technique; 2) utilize novel single site catalysts to comprise metallocene catalyst and Nonmetallocene class catalyzer.
The catalyzer of single active center is because catalyst active center is identical, can reach the purpose of the polymkeric substance of preparation different molecular weight and molecular weight distribution by regulating the Primary Catalysts chemical structure as required, thereby obtain the polyvinyl resin PP Pipe Compound of high-performance and high added value.Existing single site catalysts patent is mostly based on metallocene catalyst, as US4871705, US5240894, EP0206794, EP685494, CN1307594, CN1130932, CN1053673, US5444145 etc., these new catalysts because exist the stability of Primary Catalysts lower, synthetic difficulty, be difficult for preserving, a large amount of expensive promotors of needs and problem such as be difficult on present polymerization technique device, turn round, cause its exploitation and application to be very restricted.
The non-metallocene catalyst that middle and later periods nineteen nineties occurs has reached even has surpassed metallocene catalyst at some aspect of performance.By the excellent property of the polyolefin products of such catalyzer manufacturing, and low cost of manufacture.The non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, carry out alkene easily and insert, even under higher polymeric reaction temperature, also can obtain the olefin polymer of higher molecular weight.
Patent CN200410066068.6, CN200510119401.X, CN200710162672.2, WO2009/052700A1, CN200610026765.8, CN200610026766.2 etc. disclose the preparation method of non-metallocene catalyst, but the structure of polymkeric substance can not be controlled effectively, the molecular weight distribution broad, the skewness of comonomer in polymer chain particularly, co-monomer content is on the low side, can't obtain the resin of high insertion rate, the needs in the time of can't satisfying preparation LLDPE synthesized high-performance polyolefin resin.ZL200710045131.1 has announced the non-luxuriant polyolefin catalyst of a class, but the ecosystem form of polymkeric substance comprise size and distribute uncontrollable, bulk density is low, make such catalyzer can't be directly used in industrial production, satisfy the requirement of industrial production and processing.
The multiple modes of employing such as patent CN1539855A, CN1539856A, CN1789291A, CN1789292A, CN1789290A, WO/2006/063501,200510119401.x are carried out load to patent ZL01126323.7, ZL02151294.9, the disclosed non-metallocene catalyst of ZL02110844.7, WO03/010207 and are obtained carried metallocene catalyst, owing to mainly exist between non-metallocene complexes that obtains and the carrier with the physical adsorption form, catalyst activity is lower, is unfavorable for the control of polymer beads form and the performance of non-metallocene catalyst performance.
It is sphere or class sphere that industrial packing, transportation, processing etc. require polymer beads, for the effective ecosystem pattern of controlled polymerization resin comprises particle diameter and distribution, polymericular weight and distribution thereof, improve ethene and copolymerization of copolymerization monomer performance, make catalyzer can be directly applied for industrialized unit, satisfy the demand of producing, be necessary to develop that a class is novel has single active center's character, with low cost, be easy to the supported polyolefin catalyst of suitability for industrialized production.
Ultrahigh molecular weight polyethylene(UHMWPE) has outstanding toughness, wear resistance (than 10 times of carbon steels), anti-stress cracking and ultralow-temperature flexibility, its shock-resistance, and wearability, chemical resistance are best in present all plastics; Its shock resistance and wear resistance are constant substantially in the time of subzero 269 degrees centigrade; Abrasive wear resistance is 6.6 times of carbon steel, 6 times of nylon 66.Another outstanding characteristics of ultrahigh molecular weight polyethylene(UHMWPE) are self lubricities, and its frictional coefficient is little, the frictional coefficient between only being equivalent to ice-ice.These outstanding performances make ultrahigh molecular weight polyethylene(UHMWPE) positive part replacement carbon steel, stainless steel, bronze etc. be used for fields such as weaving, papermaking, food machinery, transportation, pottery, coal.For example, the alternative metal pipe material of ultrahigh molecular weight polyethylene tubing, nylon tube, polyfluortetraethylene pipe, cement asbestos pipe etc. are widely used in industries such as metallurgy, mine, electric power, coal, building; Superhigh molecular weight polyethylene fibers with carbon fiber, aramid fiber and be called the world today's three big high-performance fibers, can be widely used in the manufacturing of national defence quartermaster equipment exhibition area, aerospace matrix material, the contour performance matrix material of deep-sea fishing trawlnet etc.
The extraordinary unordered entanglement of the molecule interchain of ultrahigh molecular weight polyethylene(UHMWPE) makes its molecule segment to the thermal motion delay of response, shows as melt viscosity up to 1 * 10 8Pas, mobile extreme difference, in addition critical shear rate extremely low, easily produce shortcomings such as melt fracture, make it be difficult to process with conventional processing of plastic technology, seriously restricted the application of ultrahigh molecular weight polyethylene(UHMWPE), therefore almost inventing simultaneously so far with HDPE, its year, consumption was far below common HDPE.
The preparation method of ultrahigh molecular weight polyethylene(UHMWPE) adopts Ziegler-Natta catalyst at present, and polymerization obtains under slurry polymerization conditions.As to adopt titanium chloride-alkyl aluminum chloride be catalyzer, and normal pressure or near normal pressure in alkane solvents makes vinyl polymerization obtain molecular mass at the ultrahigh molecular weight polyethylene(UHMWPE) of 150 myriagram/moles to 500 myriagram/moles under the 75-85 ℃ of condition.
Existing patent about ultrahigh molecular weight polyethylene(UHMWPE) mainly comprises by the molecular weight and the form of conditions such as catalyst cupport mode, cocatalyst component, polymerization technique control ultrahigh molecular weight polyethylene(UHMWPE), add other processing aid improves processing characteristics and invents special processing machine and optimize the processing that processing conditions is realized ultrahigh molecular weight polyethylene(UHMWPE), but usually has the partial loss of the original excellent properties of ultrahigh molecular weight polyethylene(UHMWPE) like this.
Patent ZL01113057.1, ZL02151294.9, WO03/010207A1, EP1426385A1, US7253133B2, US2005004331A1, ZL200710045131.1 discloses a kind of alkene homopolymerization/catalyst for copolymerization or catalyst system that has adopted non-metallocene catalyst, but this patent needs higher promotor (Ang Gui methylaluminoxane MAO often) consumption when olefinic polymerization, could obtain suitable olefin polymerizating activity, and it is short to exist active duration in the polymerization process, polymkeric substance glues still, the polymer beads poor morphology, problems such as size distribution is inhomogeneous can not directly be used for polymerization preparation and be suitable for industrial polyvinyl resin with super-high molecular weight.
ZL200610026766.2 discloses the non-luxuriant polyolefin catalyst of a kind of loading type, but have in polymerization process that polymer beads poor morphology, size distribution are inhomogeneous, polymer stacks density and molecular weight do not reach problems such as industrial production requirement, can't directly be used for satisfying the requirement that slurry polymerization processes is carried out industrial production polyvinyl resin with super-high molecular weight and downstream product processing.
Therefore, the manufacture method that still needs to develop a kind of ultrahigh molecular weight polyethylene(UHMWPE) that is easy to process in this area at present, the particle form of the ultrahigh molecular weight polyethylene(UHMWPE) of its manufacturing is good, technology is adjustable flexibly, satisfy the processing request of large-scale commercial production requirement and ultrahigh molecular weight polyethylene(UHMWPE), comprise demands such as high-level efficiency is extruded, spinning, pressed sheet.
As patent ZL94116488.8, CN200410054344.7, CN200410024103.8, CN200480006479.4, CN200580004355.7, CN00819563.3, CN200610116967.1, CN200710037051.1, CN200710121286.9, CN200580008557.9, CN200810051617.0, WO9011060A1, KR 20070025173A, KR 100274657B1, CN200710042468.7, ZL00819563.3, US6384163B1, ZL93103156.7, US544145, WO01/21668A1, WO03/059968A1 etc. provide the preparation method of ultrahigh molecular weight polyethylene(UHMWPE), but the processing characteristics of its product and the information of microtexture aspect all are not provided.
In addition, in catalyzed polymerization process, existing catalyst system can produce the β hydrogen in active centre and eliminate, the product that β hydrogen is eliminated adds the multipolymer that is shaped as to the insertion in new active centre and then produces certain long and short side chain [Amin S.B.et.al.J.am.Chem.Soc.2006,128,4506-4507; Amin S.B.et.al.J.am.Chem.Soc.2007,129,2938-2953; Li L.T.et.al.J.am.Chem.Soc.2002,124,12725-12741; Nele M.et.al.Macromol.Theory Simul.2002,11,939-943], in synthesizing super high molecular weight polyethylene process, β hydrogen can take place equally to be eliminated, therefore all have certain long branched chain structure in the existing ultrahigh molecular weight polyethylene(UHMWPE), the existence meeting of these side chains is very big to the melt viscosity influence of polymkeric substance, can produce material impact to the processibility of material.Because its distinctive high viscosity of ultrahigh molecular weight polyethylene(UHMWPE) and low critical shear rate, its processing often is to carry out under low shear rate, therefore the synthetic ultrahigh molecular weight polyethylene(UHMWPE) that contains ultralow long-chain branch, the melt viscosity of polymkeric substance is reduced, reduce the resistance in the polymer processing greatly, reduce power consumption of polymer processing, increase working (machining) efficiency.
Summary of the invention
The invention provides a class load type non-metallocene polyolefin catalyst, such polyolefin catalyst is made up of metal complexes and magnesium compound, solved that metal complexes comes off easily in the conventional load mode in polymerization process, problems such as sticking still, particle form can't effectively be controlled, the insertion rate of comonomer is low, synthetic weight of otefi pi polymer narrowly distributing (1.6-3.0);
The present invention also provides the preparation method of such load type non-metallocene polyolefin catalyst, such catalyzer is pretended firmly by forming between metal complexes and the magnesium compound, its preparation is simple, reaction conditions is gentle, with low cost, is very suitable for suitability for industrialized production.
The invention provides the purposes of such load type non-metallocene polyolefin catalyst, promptly this catalyzer and aluminum alkyls or alkylaluminoxane one are used from the polyolefine that catalysis in olefine polymerization prepares sphere or the spherical high density polyethylene(HDPE) of class, ultrahigh molecular weight polyethylene(UHMWPE), linear low density of polyethylene and functionalization;
The present invention provides another kind of load type non-metallocene polyolefin catalyst simultaneously;
The present invention also provides the preparation method of such load type non-metallocene polyolefin catalyst, promptly utilize a class polydentate ligand and the transistion metal compound effect that is carried on the carrier to obtain, solved non-metallocene complexes easy problem that causes polymkeric substance particle diameter skewness and sticking still that breaks away from polymerization process in the conventional load mode by the original position load technology; In such Preparation of catalysts process, do not need other any electron donors except that the Nonmetallocene polydentate ligand, do not need harsh reaction conditions and reaction requirement yet, the preparation method is simple, and is with low cost, is very suitable for suitability for industrialized production.
The invention provides a kind of ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE), its preparation method and application thereof.
The present invention relates to a class load type non-metallocene polyolefin catalyst.Described load type non-metallocene polyolefin catalyst is made up of magnesium compound and metal complexes, and the mol ratio of described magnesium compound and metal complexes is 10～10000: 1; For reaching more excellent effect, the mol ratio of magnesium compound and metal complexes is 10～2000: 1, the mol ratio of magnesium compound and metal complexes more preferably 10～1000: 1, most preferably more preferably 10～200: 1;
Recommend: described magnesium compound is the alcohol adduct of magnesium halide, wherein, alcohol content is counted 30%-70% with weight ratio, described alcohol is selected from the Fatty Alcohol(C12-C14 and C12-C18) of C1-C18 and (further recommends the Fatty Alcohol(C12-C14 and C12-C18) of C1-C10, especially recommend the Fatty Alcohol(C12-C14 and C12-C18) of C2-C10), at least a in the aromatic alcohol of C6-C10 and the alicyclic ring alcohol of C3-C10, described alcohol can be by the alkyl (further recommending the alkyl of C1-C5) of any C1-C10, the alkoxyl group of C1-C10 (further recommending the alkoxyl group of C1-C5), halogen atom replaces;
Described metal complexes has following molecular structure:
Figure BSA00000355523100051
Wherein:
: refer to coordinate bond;
R 21, R 22Or R 23Be selected from hydrogen separately arbitrarily, a kind ofly have 1 to 20 carbon atom side chain or have 6 to 15 carbon atoms fragrance alkyl, the optional position on the aryl radical can be substituted group individually or simultaneously and replace, and each substituted radical has 1 to 10 carbon atom or is halogen, R 21, R 22Or R 23Can be identical, also can be different;
For reaching more excellent result, R 21, R 22Or R 23It can be the aryl radical that has 1 to 10 carbon atom side chain or straight-chain alkyl or have 6 to 10 carbon atoms, optional position on the aryl radical can be substituted individually or simultaneously, and substituted radical can be side chain or the straight-chain alkyl, the alkoxyl group that contains 1 to 5 carbon atom that contain 1 to 5 carbon atom, contain amido, the halogen of 1 to 5 carbon atom or contain the side chain of 1 to 5 carbon atom or the fluorine-containing alkyl of straight chain; R 1, R 2Or R 3Phenyl, the naphthyl that also can preferably have 1 to 7 carbon atom side chain or straight-chain alkyl or replacement, optional position on the phenyl or naphthyl can be substituted individually or simultaneously, and substituted radical can be side chain or the straight-chain alkyl, the alkoxyl group that contains 1 to 4 carbon atom that contain 1 to 4 carbon atom, contain amido, the halogen of 1 to 4 carbon atom or contain the side chain of 1 to 5 carbon atom or the fluorine-containing alkyl of straight chain;
R 24Or R 25Can be selected from C separately arbitrarily 1-C 5Alkyl, C 2-C 5Thiazolinyl, C 2-C 5Alkynyl, C 4-C 10The heterocyclic radical, the C that contain nitrogen, oxygen, sulfur heteroatom 6-C 20Phenyl and have the phenyl of substituted radical, each substituted radical on the phenyl ring has 1 to 10 carbon atom or is halogen, substituted radical can be identical, also can be different, adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
Particularly, halogen is selected from fluorine, chlorine, bromine or iodine;
C 1-C 5Alkyl be selected from methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, neo-pentyl etc.; C 2-C 5Thiazolinyl be selected from vinyl, allyl group, propenyl, 1-butylene base, crotyl, 3-butenyl, 1-pentenyl, pentenyl, 3-pentenyl, 4-pentenyl etc.; C 2-C 5Alkynyl be selected from ethynyl, propargyl, proyl, ethyl acetylene base, 2-butyne base, 3-butynyl, 1-pentynyl, valerylene base, 3-pentynyl, 4-pentynyl etc.; C 4-C 10The heterocyclic radical that contains nitrogen, oxygen, sulfur heteroatom simultaneously is selected from 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 4-picolyl, 4-ethyl pyridinyl, 4-tert .-butylpyridine base, 2-thienyl, 3-thienyl etc.; C 6-C 20Phenyl and the phenyl with substituted radical be selected from phenyl, 2-aminomethyl phenyl, 2-ethylphenyl, 2,5-3,5-dimethylphenyl, 2,5-diethyl phenyl, 4-aminomethyl phenyl, 4-ethylphenyl, 4-tert-butyl-phenyl, 2,5-di-tert-butyl-phenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2,5-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl etc.;
R 24Or R 25: be hydrogen, a kind of side chain or straight-chain alkyl or aryl radical, each alkyl has 1 to 20 carbon atom, and each aryl radical has 6 to 15 carbon atoms, and the optional position on the aryl radical can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 10 carbon atom or is halogen, R 4Or R 5Can be identical, also can be different; For reaching more excellent result, R 4Or R 5Can select to have a kind of side chain or the straight-chain alkyl of 1 to 10 carbon atom, have 6 to 10 carbon atom aryl, optional position on the aryl can be substituted individually or simultaneously, and substituted radical can be side chain or the straight-chain alkyl, the alkoxyl group that contains 1 to 5 carbon atom that contain 1 to 5 carbon atom, contain amido, the halogen of 1 to 5 carbon atom or contain the side chain of 1 to 5 carbon atom or the fluorine-containing alkyl of straight chain; R 4Or R 5Also can be a kind of side chain or straight-chain alkyl with 1 to 4 carbon atom, the phenyl of phenyl, naphthyl or replacement, naphthyl, optional position on the phenyl or naphthyl can be substituted individually or simultaneously, and substituted radical can be side chain or the straight-chain alkyl, the alkoxyl group that contains 1 to 5 carbon atom that contain 1 to 5 carbon atom, contain amido, the halogen of 1 to 5 carbon atom or contain the side chain or the alkyl fluorine-containing, chlorine or bromine of 1 to 5 carbon atom;
Particularly, halogen is selected from fluorine, chlorine, bromine, iodine; C 1-C 5Alkyl be selected from methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, neo-pentyl etc.; C 6-C 20Phenyl and the phenyl with substituted radical be selected from phenyl, 2-aminomethyl phenyl, 2-ethylphenyl, 2,5-3,5-dimethylphenyl, 2,5-diethyl phenyl, 4-aminomethyl phenyl, 4-ethylphenyl, 4-tert-butyl-phenyl, 2,5-di-tert-butyl-phenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2,5-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl etc.;
Z: oxygen, sulphur, selenium or phosphorus, when Z is oxygen, sulphur or selenium atom, have only R 24Or R 25Existence is to satisfy the valence state needs of oxygen, sulphur or selenium;
M: the 4th group 4 transition metal atom comprises titanium, zirconium or hafnium;
Y: be selected from halogen, have 1 to 10 carbon atom alkyl, have the alkoxyl group of 1 to 10 carbon atom or have the amido (R of 1 to 10 carbon atom 26) 2N-, several X are identical or different, each other in key or Cheng Jian not; R wherein 26Refer to contain the alkyl of 1 to 4 carbon atom;
Described halogen refers to fluorine, chlorine, bromine or iodine.
M:1 or 2;
N:2 or 3;
In the structural formula all parts electronegative sum absolute value should with metal M in the structural formula positively charged absolute value identical, all parts comprise Y and polydentate ligand;
The preparation method of such load type non-metallocene polyolefin catalyst comprises the steps:
(1) one or more in magnesium compound and aluminum alkyls or the alkylalumoxane solution contact 1-24h in 0-100 ℃, carry out chemical activation, wherein contact the preferred 0-70 of temperature ℃; Described aluminum alkyls is meant trialkyl aluminium compound, preferred trimethyl aluminium, triethyl aluminum or triisobutyl aluminium; Recommend alcohol contained in described aluminum alkyls and the magnesium compound to be (1.5-0.8): 1 with molar ratio computing; In magnesium compound described in the recommendation step (1) and the alkyl aluminum solutions one or more contact 1-24 hour at 0-60 ℃; Aluminum alkyls or the used solvent of alkylalumoxane solution are the alkane of 5 to 10 carbon atoms, the naphthenic hydrocarbon of 5 to 10 carbon atoms or their mixed alkanes in the recommendation step (1);
(2) metal complexes is dissolved in the organic solvent, the magnesium compound after handling with step (1) is middle then contacts 1-24h in 0-100 ℃; Described organic solvent is meant can be with described all solvents of metal complexes dissolved, preferred fragrance varsol and halohydrocarbon or its mixed solvent, more preferably methylene dichloride and toluene; The mol ratio of recommending described magnesium compound and metal complexes is 10～10000: 1; The solution of the metal complexes described in the recommendation step (2) with handle after magnesium compound contact 1-24 hour at 0-60 ℃; The solvent of dissolution of metals title complex is mineral oil or different liquid hydrocarbons in the recommendation step (2), be selected from the alkane with 5 to 10 carbon atoms, aromatic hydrocarbon or both mixtures, perhaps above-mentioned alkane or the aromatic hydrocarbon that is replaced by halogen atom with 5 to 10 carbon atoms;
(3) the gained mixture is filtered, use organic solvent washing, final drying becomes flowable pressed powder; Described organic solvent is C 5-C 30Alkane, C 5-C 30Naphthenic hydrocarbon or mixed alkanes.
Pure content in the consumption of described aluminum alkyls and the carrier is 1.5-0.8 with mol ratio calculating: 1, and preferred 1.2-1.0: 1.
Described magnesium compound is the alcohol adduct of magnesium halide, preferably contain the spherical magnesium chloride of alcohol or contain the subsphaeroidal magnesium chloride of alcohol, the particle size range of magnesium compound between 10nm-1mm, between the preferred 10nm-100um, 10nm-50um most preferably.
The described subsphaeroidal magnesium chloride that contains the spherical magnesium chloride of alcohol or contain alcohol, its pure content is calculated by weight between 30%-70%, between the preferred 50%-60%.
Described alcohol is meant C 1-C 10Monobasic or polyvalent alcohol, its type can be a Fatty Alcohol(C12-C14 and C12-C18), one or more in alicyclic ring alcohol or the aromatic alcohol, preferred fat alcohol, described alcohol can be replaced by other heteroatoms.Described alcohol can be replaced by the alkoxy or halogen atom of the alkyl of any C1-C10, C1-C10.Wherein, Fatty Alcohol(C12-C14 and C12-C18) can be methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, amylalcohol, 2-methyl amyl alcohol, 2-ethylpentanol, hexanol etc., wherein preferred alcohol, butanols, amylalcohol; Aromatic alcohol can be phenylcarbinol, phenylethyl alcohol, methylbenzyl alcohol etc., wherein preferred phenylethyl alcohol; Alicyclic ring alcohol is such as hexalin, cyclopentanol and ring octanol etc., wherein preferred hexalin; The alcohol that alkyl replaces is such as methylcyclopentanol, ethyl cyclopentanol, propyl group cyclopentanol, methyl-cyclohexanol, ethyl cyclohexanol, propyl group hexalin, methyl ring octanol, ethyl ring octanol etc., wherein preferable methyl hexalin; The alcohol that halogen atom replaces is such as trichlorine methyl alcohol, ethapon and three Mecorals etc., wherein preferred trichlorine methyl alcohol; The alcohol that alkoxyl group replaces is such as glycol monoethyl ether, ethylene glycol one n-butyl ether and 1-butoxy-2-propyl alcohol etc., wherein preferred glycol monoethyl ether.In these alcohol, more preferably ethanol and butanols.
These alcohol can be used alone, and also can multiple mixing use.
The used solvent of described dissolving aluminum alkyls or alkylaluminoxane is C 5-C 30The mixture of alkane, naphthenic hydrocarbon or above-mentioned alkane and naphthenic hydrocarbon, preferred C 5-C 10Alkane, naphthenic hydrocarbon or mixed alkanes, hexane preferably.
The used solvent of described washing catalyst is C 5-C 30Alkane, naphthenic hydrocarbon or mixed alkanes, preferred C 5-C 8Alkane, naphthenic hydrocarbon or mixed alkanes, most preferably hexane, hexanaphthene and sherwood oil.
Above-mentioned loaded catalyst can be used for the equal polymerization of catalyzed ethylene and obtains sphere or class spheric high-density polyethylene resin, sphere or class spheric polyvinyl resin with super-high molecular weight under the promotor effect, and the copolymerization of ethene and the alpha-olefin copolymerization that obtains sphere or class spheric linear low density of polyethylene, ethene and the cycloolefin copolymerization that obtains the alpha-olefin of sphere or class spheric COC material, ethene and polar functionalities obtains the polyolefine material of functionalization.Wherein, alpha-olefin is meant C 3～ 18Terminal olefin, for example propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecylene, 1-vaccenic acid and its mixture etc.Cycloolefin is meant cyclic alkene, comprises cyclopentadiene, cycle pentadiene dimer, norbornylene etc.; The alpha-olefin of polar functionalities is meant that end contains the alpha-olefin of hydroxyl, ester group, carboxyl, amido isopolarity functional group.The polymer particle of preparation is spherical or subsphaeroidal, the polymer particle narrow diameter distribution, and particle size range is 100nm-1mm.Be particularly suitable for preparing the multipolymer of spherical polyethylene and alpha-olefin, cycloolefin, LLDPE for example, the COC material, the insertion rate of multipolymer is 0.5-10mol%.For example be used for preparing polymer particle and be spherical or subglobose polyethylene or polypropylene.
Slurry polymerization, endless tube polymerization, vapour phase polymerization or other forms of polymerization technique are adopted in polymerization.Recommend to be used from the slurry polymerization or the vapour phase polymerization of alkene with promotor one.
Polymerization is generally carried out in inert solvent, for example hydro carbons, cyclic hydrocar-bons or aromatic hydrocarbons.For helping reactor operation and polymerisate, inert solvent can use the hydro carbons less than 12 carbon, is exemplified below but is not limited in this, hexane, toluene, chlorobenzene and composition thereof.
Polymerization temperature maintains 0-200 ℃ (recommend 0 to 150 ℃, further recommend 20-150 ℃), for reaching good catalytic activity and throughput, can maintain 20 to 120 ℃.
Polymerization pressure can change in 0.1 to 50MPa, and operation can obtain reactor operating parameters and polymkeric substance preferably in 0.1 to 10MPa.
Recommending such load type non-metallocene polyolefin catalyst is 0.1-20MPa at polymerization pressure, polymerization temperature is 20-200 ℃, and hydrogen pressure is the copolymerization of alkene of copolymerization, alpha-olefin and band functional groups of alkene that is used for preparing copolymerization, ethene and the band functional groups of copolymerization, ethene and the cyclic olefin of ethene and alpha-olefin under the condition of 0-0.5Mpa.
Described promotor is an alkylaluminium cpd, alkylaluminoxane or weakly coordinating anion; The preferred AlEt of described alkylaluminium cpd 3, AlMe 3Or Al (i-Bu) 3Alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta, MMAO (methylaluminoxane of modification) etc.; Weakly coordinating anion is recommended boron fluothane or boron alkyl, preferred [B (3,5-(CF 3) 2C 6H 3) 4] -, -OSO 2CF 3Or ((3,5-(CF 3) 2) C 6H 3) 4B -Catalyzer and promotor can any order adding system carry out polymerization.The variable-scale of employed catalyzer of polymerization and promotor.Usually the mol ratio of catalyzer and promotor is 1: 1-5000, generally can be 1: 10-2000 be so that make catalytic activity, polymer property and production cost all maintain scope preferably.
In sum, a kind of supported olefin polymerization catalyst provided by the invention, the characteristics of this catalyzer are that metal complexes directly is carried on the magnesium compound.This non-metallocene catalyst and promotor aluminum alkyls or alkylaluminoxane combination and when being used for the homopolymerization of catalyzed alkene/copolymerization, only need fewer promotor consumption, just can with high reactivity, high monomer insertion rate obtain narrow molecular weight distribution (1.6-3.0), comonomer distribution evenly, the polymkeric substance particle diameter is evenly distributed, polymer particle is sphere or class spheric ethylene copolymer and homopolymer, the polymkeric substance of producing is easy to pipe-line transportation, is difficult for sticking still, is applicable to the industrialization operation and produces.
A class load type non-metallocene polyolefin catalyst of the present invention can also be made up of magnesium compound, porous support and metal complexes;
Wherein:
Described metal complexes is by ML 4Containing heteroatomic polydentate ligand original position with a class generates;
M is meant the 4th group 4 transition metal atom, recommends titanium, zirconium;
L is selected from halogen or has the alkyl of 1 to 10 carbon atom, and 4 L are identical or different;
Describedly contain heteroatomic polydentate ligand and have following molecular structure:
Figure BSA00000355523100111
R 1Be H, have the straight chain of 1 to 10 carbon atom or contain the alkyl (CH[C (CH for example of side chain 3) 3] 2), have the haloalkyl (CF for example of 1 to 4 carbon atom 3), have 2 to 10 carbon atoms thiazolinyl (recommendation has the thiazolinyl of 2 to 5 carbon atoms), have 2 to 10 carbon atoms alkynyl (recommendation has the alkynyl of 2 to 5 carbon atoms), have the phenyl or naphthyl that 4 to 10 carbon atoms contain heterocyclic radical, phenyl, the naphthyl of nitrogen, oxygen or sulphur atom and have substituted radical, optional position on phenyl ring or the naphthyl can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 5 carbon atom or is halogen, substituted radical can be identical, also can be different;
R 3Be to have H, the straight chain of 1 to 10 carbon atom or the alkyl that contains side chain (are recommended the straight chain of 2 to 10 carbon atoms or are contained the alkyl of side chain, methyl for example, hexyl etc., the further alkyl of recommending the straight chain of 1 to 6 carbon atom or containing side chain, especially recommend the straight chain of 2 to 5 carbon atoms or contain the alkyl of side chain), thiazolinyl (recommendation has the thiazolinyl of 2 to 5 carbon atoms) with 2 to 10 carbon atoms, alkynyl (recommendation has the alkynyl of 2 to 5 carbon atoms) with 2 to 10 carbon atoms, have 4 to 10 carbon atoms and contain nitrogen simultaneously, oxygen, the heterocyclic radical of sulfur heteroatom, phenyl, naphthyl and phenyl or naphthyl with substituted radical, on phenyl ring or the naphthyl the optional position can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 5 carbon atom or is halogen, substituted radical can be identical, also can be different, adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
R 2, R 4, R 5, R 6, R 7The alkyl that is hydrogen, has the straight chain of 1 to 10 carbon atom or contain side chain (is recommended the straight chain of 2 to 10 carbon atoms or is contained the alkyl of side chain, for example methyl, CH[C (CH 3) 3] 2Deng, the further alkyl of recommending the straight chain of 1 to 7 carbon atom or containing side chain, especially recommend the straight chain of 2 to 5 carbon atoms or contain the alkyl of side chain), thiazolinyl (recommendation has the thiazolinyl of 2 to 5 carbon atoms) with 2 to 10 carbon atoms, alkynyl (recommendation has the alkynyl of 2 to 5 carbon atoms) with 2 to 10 carbon atoms, phenyl or naphthyl and phenyl or naphthyl with substituted radical, on phenyl ring or the naphthyl the optional position can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 5 carbon atom or is halogen, substituted radical can be identical, also can be different, adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
R 8, R 9Be selected from arbitrarily: hydrogen, side chain or straight-chain alkyl, phenyl or naphthyl, have the phenyl or naphthyl of substituted radical with 1 to 20 carbon atom, optional position on phenyl ring or the naphthyl can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 15 carbon atom or is halogen, R 8Or R 9Can be identical, also can be different, adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
X is O, N, S, Se or P;
When X is O, S or Se, has only a substituent R on the X 8Perhaps R 9
Described halogen refers to fluorine, chlorine, bromine or iodine;
Described magnesium compound is alcohol adduct, the R of magnesium halide, magnesium halide 10 2Mg, (R 11O) 2Mg, (R 12O) MgCl or their mixture; Described R 10, R 11, R 12Be selected from C 1-C 30Alkyl, the C of replacement 1-C 30Alkyl, described substituting group is a halogen;
Described porous support is selected from the oxide compound of the 13rd, 14 group elements at interior inorganic oxide and oxidation mixture and mixed oxide, the oxidation material for preparing by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound, or organic high molecular polymer; Described silicon compound is a silicon-dioxide, molecular sieve or polynite; Described organic high molecular polymer is a polystyrene.
Described catalyzer is formed: the mass ratio of porous support and magnesium compound is 1-3: 1;
The 4th family's metal content: 1-10wt%;
Titanium content is 1-10wt% in preference.
This Preparation of catalysts method comprises the steps: magnesium compound metallizing thing ML 4With the mol ratio is 0.5-5: 1, be dissolved in tetrahydrofuran (THF), and obtain the tetrahydrofuran solution of magnesium compound metallizing thing; In described solution, add porous support, obtain mixed serum; Add precipitation agent and make it precipitation in described mixed serum, filtration, washing, dry this throw out obtain complex carrier I; Continue to add metallic compound in complex carrier I, wherein the mol ratio of metallic compound and magnesium compound is 0.5-5: 1, pass through filtration, washing, drying then, and obtain complex carrier II; Add polydentate ligand in described complex carrier II, filtration, washing, drying obtain Nonmetallocene polyolefine catalyst.
Wherein, described is to be selected from the oxide compound of the 13rd, 14 family's elements at interior inorganic oxide and oxidation mixture and mixed oxide as porous support, the oxidation material for preparing by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound, comprise silica gel, polynite, aluminum oxide or clay, or molecular sieve etc.; Solid as carrier can also be an organic high molecular polymer, comprises polystyrene, polyethylene etc.The preferred silica gel of described carrier, its particle diameter are 1-100m, specific surface area 50-500m 2/ g, pore volume 0.4-3mL/g, mean pore size 5-50nm; Described the 13rd, 14 family's elements are aluminium and silicon for example.
Described magnesium compound is magnesium halide, alkyl magnesium, alkoxyl group magnesium halide, alkoxyl magnesium, or their mixture; Preferred magnesium chloride, alkoxyl group magnesium halide, alkoxyl magnesium, more preferably magnesium chloride, alkoxyl group magnesium halide;
Described metal complexes is by ML 4Containing heteroatomic polydentate ligand original position with a class generates;
M is meant the 4th group 4 transition metal atom, recommends titanium, zirconium;
L is selected from halogen or has the alkyl of 1 to 10 carbon atom, preferred halogen, and more preferably Cl, several L are identical or different;
Described halogen refers to fluorine, chlorine, bromine or iodine;
Particularly, described metallic compound is such as being selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, zirconium tetrachloride, tetrabormated zirconium, zirconium tetraiodide;
Preferred TiCl 4, zirconium tetrachloride;
The used solvent of washing catalyst is C for the used solvent of washing 5-C 30Alkane, naphthenic hydrocarbon or mixed alkanes, preferred hexane and sherwood oil;
Described load type non-metallocene polyolefin catalyst is made up of magnesium compound, porous support and metal complexes; Described metal complexes is by ML 4Containing heteroatomic polydentate ligand original position with a class generates; In the wherein said loaded catalyst: the mass ratio of porous support and magnesium compound is 1-3: 1; The 4th family's metal content: 1-10wt%; Titanium content is 1-10wt% in preference, and the recommendation titanium content is 1-6wt%.
Recommend: the temperature of reaction of described tetrahydrofuran (THF) dissolved magnesium compound and metallic compound is 30-80 ℃, and the reaction times is 1-24 hour; Described porous support is (1-3) with the ratio of the quality of magnesium compound: 1; The volume ratio of described precipitation agent and tetrahydrofuran (THF) is (0.5-3): 1.
The ratio of tetrahydrofuran (THF) and magnesium compound is 10-100 (mL): 1 gram, preferred 10-30mL tetrahydrofuran (THF)/gram magnesium compound;
The mass ratio 1 of magnesium compound and carrier: (0.1-20), preferred 1: (0.5-10), most preferably 1: (1-3);
The mol ratio of magnesium compound metallizing thing is (1-5): 1, preferred (1-3): 1, most preferably (1-2): 1;
The mol ratio of contained metallic compound in polydentate ligand and the carrier (for example titanium among the complex carrier II) is (1-1.2): 1.
Described Nonmetallocene polydentate ligand recommends to be selected from the compound with following structure:
Figure BSA00000355523100131
R 1Be thiazolinyl, alkynyl, the heterocyclic radical with 2 to 5 carbon atoms, aromatic group with 6 to 10 carbon atoms with 4 to 10 carbon atoms, optional position on the aromatic group can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 5 carbon atom or is halogen, substituted radical can be identical, also can be different; Described is the preferred substituted phenyl of aromatic group, the optional position can be had the group or the halogen replacement of 1 to 5 carbon atom individually or simultaneously on the phenyl, and the ortho position is had alkoxyl group, fluorine, the chlorine or bromine replacement of the alkyl of 1 to 4 carbon atom, 1 to 4 carbon atom on the preferred phenyl;
R 3Be H, have the straight chain of 1 to 5 carbon atom or contain side chain alkyl, thiazolinyl, alkynyl, have the aryl of 6 to 10 carbon atoms, optional position on the aromatic group can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 5 carbon atom or is halogen, substituted radical can be identical, also can be different; Described is the preferred substituted phenyl of aromatic group, and the optional position can be had the group or the halogen replacement of 1 to 5 carbon atom individually or simultaneously on the phenyl, and the ortho position is had alkyl, alkoxyl group, fluorine, the chlorine or bromine replacement of 1 to 4 carbon atom on the preferred phenyl;
R 2, R 4, R 5, R 6, R 7Be hydrogen, have the straight chain of 1 to 5 carbon atom or contain side chain alkyl, thiazolinyl, alkynyl, have the aromatic group of 6 to 10 carbon atoms, optional position on the aromatic group can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 5 carbon atom or is halogen, substituted radical can be identical, also can be different; Described is the preferred substituted phenyl of aromatic group, and the optional position can be had the group or the halogen replacement of 1 to 5 carbon atom on the phenyl, and the ortho position is had alkyl, alkoxyl group, fluorine, the chlorine or bromine replacement of 1 to 4 carbon atom on the preferred phenyl;
R 8, R 9: be hydrogen, have side chain or the straight-chain alkyl or the phenyl of 1 to 20 carbon atom or have the aromatic group of 7 to 15 carbon atoms that the optional position on the aryl can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 10 carbon atom or is halogen; R 8Or R 9Can be identical, also can be different; The side chain or straight-chain alkyl and the substituted phenyl that preferably have 1 to 10 carbon atom, the optional position can be had the group or the halogen replacement of 1 to 5 carbon atom individually or simultaneously on the phenyl, the side chain or straight-chain alkyl and the substituted phenyl that most preferably have 1 to 4 carbon atom, the ortho position is had alkyl, alkoxyl group, fluorine, the chlorine or bromine replacement of 1 to 4 carbon atom on the phenyl;
X is O, N, S, Se or P;
When X is O, S or Se, has only a substituent R on the X 8Perhaps R 9
Described magnesium compound is magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, the alcohol adduct of magnesium halide or their mixture;
Particularly, magnesium halide can be selected from magnesium chloride (MgCl 2), magnesium bromide (MgBr 2), magnesium iodide (MgI 2) and magnesium fluoride (MgF 2) etc., wherein preferred magnesium chloride.
The alkoxyl group magnesium halide can be selected from methoxyl group chlorination magnesium (Mg (OCH 3) Cl), oxyethyl group magnesium chloride (Mg (OC 2H 5) Cl), propoxy-magnesium chloride (Mg (OC 3H 7) Cl), n-butoxy magnesium chloride (Mg (OC 4H 9) Cl), isobutoxy magnesium chloride (Mg (i-OC 4H 9) Cl), methoxyl group magnesium bromide (Mg (OCH 3) Br), oxyethyl group magnesium bromide (Mg (OC 2H 5) Br), propoxy-magnesium bromide (Mg (OC 3H 7) Br), n-butoxy magnesium bromide (Mg (OC 4H 9) Br), isobutoxy magnesium bromide (Mg (i-OC 4H 9) Br), methoxyl group magnesium iodide (Mg (OCH 3) I), oxyethyl group magnesium iodide (Mg (OC 2H 5) I), propoxy-magnesium iodide (Mg (OC 3H 7) I), n-butoxy magnesium iodide (Mg (OC 4H 9) I) and isobutoxy magnesium iodide (Mg (i-OC 4H 9) I) etc., wherein preferred methoxyl group chlorination magnesium, oxyethyl group magnesium chloride and isobutoxy magnesium chloride.
Alkoxyl magnesium can be selected from magnesium methylate (Mg (OCH 3) 2), magnesium ethylate (Mg (OC 2H 5) 2), propoxy-magnesium (Mg (OC 3H 7) 2), butoxy magnesium (Mg (OC 4H 9) 2) and isobutoxy magnesium (Mg (i-OC 4H 9) 2) etc., wherein preferred magnesium ethylate and isobutoxy magnesium.
Alkyl magnesium can be selected from methyl magnesium (Mg (CH 3) 2), magnesium ethide (Mg (C 2H 5) 2), propyl group magnesium (Mg (C 3H 7) 2), normal-butyl magnesium (Mg (C 4H 9) 2) and isobutyl-magnesium (Mg (i-C 4H 9) 2) etc., wherein preferred magnesium ethide and normal-butyl magnesium.
Alkyl halide magnesium can be selected from methylmagnesium-chloride (Mg (CH 3) Cl), ethylmagnesium chloride (Mg (C 2H 5) Cl), propyl group magnesium chloride (Mg (C 3H 7) Cl), normal-butyl chlorination magnesium (Mg (C 4H 9) Cl), isobutyl-chlorination magnesium (Mg (i-C 4H 9) Cl), methyl-magnesium-bromide (Mg (CH 3) Br), ethylmagnesium bromide (Mg (C 2H 5) Br), propyl group magnesium bromide (Mg (C 3H 7) Br), normal-butyl bromination magnesium (Mg (C 4H 9) Br), isobutyl-bromination magnesium (Mg (i-C 4H 9) Br), methyl magnesium iodide (Mg (CH 3) I), ethyl magnesium iodide (Mg (C 2H 5) I), propyl group magnesium iodide (Mg (C 3H 7) I), normal-butyl iodate magnesium (Mg (C 4H 9) I) and isobutyl-iodate magnesium (Mg (i-C 4H 9) I) etc., wherein preferable methyl magnesium chloride, ethylmagnesium chloride and isobutyl-chlorination magnesium.
Alkyl alkoxy magnesium can be selected from methyl methoxy base magnesium (Mg (OCH 3) (CH 3)), methyl ethoxy magnesium (Mg (OC 2H 5) (CH 3)), methyl propoxy-magnesium (Mg (OC 3H 7) (CH 3)), methyl n-butoxy magnesium (Mg (OC 4H 9) (CH 3)), methyl isobutoxy magnesium (Mg (i-OC 4H 9) (CH 3)), ethyl magnesium methylate (Mg (OCH 3) (C 2H 5)), ethyl magnesium ethylate (Mg (OC 2H 5) (C 2H 5)), ethyl propoxy-magnesium (Mg (OC 3H 7) (C 2H 5)), ethyl n-butoxy magnesium (Mg (OC 4H 9) (C 2H 5)), ethyl isobutoxy magnesium (Mg (i-OC 4H 9) (C 2H 5)), propyl group magnesium methylate (Mg (OCH 3) (C 3H 7)), propyl group magnesium ethylate (Mg (OC 2H 5) (C 3H 7)), propyl group propoxy-magnesium (Mg (OC 3H 7) (C 3H 7)), propyl group n-butoxy magnesium (Mg (OC 4H 9) (C 3H 7)), propyl group isobutoxy magnesium (Mg (i-OC 4H 9) (C 3H 7)), normal-butyl magnesium methylate (Mg (OCH 3) (C 4H 9)), normal-butyl magnesium ethylate (Mg (OC 2H 5) (C 4H 9)), normal-butyl propoxy-magnesium (Mg (OC 3H 7) (C 4H 9)), normal-butyl n-butoxy magnesium (Mg (OC 4H 9) (C 4H 9)), normal-butyl isobutoxy magnesium (Mg (i-OC 4H 9) (C 4H 9)), isobutyl-magnesium methylate (Mg (OCH 3) (i-C 4H 9)), isobutyl-magnesium ethylate (Mg (OC 2H 5) (1-C 4H 9)), isobutyl-propoxy-magnesium (Mg (OC 3H 7) (i-C 4H 9)), isobutyl-n-butoxy magnesium (Mg (OC 4H 9) (i-C 4H 9)) and isobutyl-isobutoxy magnesium (Mg (i-OC 4H 9) (i-C 4H 9)) etc., wherein preferred butyl magnesium ethylate.
Employed all kinds of SOLVENTS all recommends strict anhydrous and oxygen-free to handle among the preparation method of load type non-metallocene polyolefin catalyst of the present invention, and all operations all is recommended under the condition of anhydrous and oxygen-free and carries out.
No matter which kind of mode of loading, above-mentioned load type non-metallocene polyolefin catalyst all can be used for preparing High molecular weight polyethylene and ultrahigh molecular weight polyethylene(UHMWPE).Preparation condition is recommended under the effect of promotor, and ethylene pressure is 0.1-20MPa, and polymerization temperature is 20-200 ℃, and polymerization time is 1-24h.Recommend described promotor trialkylaluminium, alkylaluminoxane; Described promotor is 1-3000 in aluminium element and described load type non-metallocene polyolefin catalyst in the mol ratio of titanium elements: 1.Further recommending described promotor is triethyl aluminum, is 15-200 in aluminium element triethyl aluminum and described load type non-metallocene polyolefin catalyst in the mol ratio of titanium elements: 1.Further recommending polymerization pressure is 0.1-5MPa, and polymerization temperature is 40-90 ℃.Described molecular weight of polyethylene is 500,000 to 1,000 ten thousand.
Load type non-metallocene polyolefin catalyst of the present invention is applicable to the incompatible preparation polyvinyl resin with super-high molecular weight of catalyzed ethylene homopolymerization; Needing with aluminum alkyls or alkylaluminoxane during polymerization is promotor, and suitable promotor comprises triethyl aluminum (AlEt 3), triisobutyl aluminium (Al (i-Bu) 3), aluminium diethyl monochloride (AlEt 2Cl), three hexyl aluminium (Al (n-Hex) 3) wait or their mixture preferred AlEt 3Al/Ti mol ratio suitable during polymerization is 10-3000: 1, and preferred 20-500: 1, more select 15-200: 1.
Nonmetallocene polyolefine catalyst can be used for slurry polymerization or vapour phase polymerization; Wherein, slurry polymerization conditions is 0.1-20MPa for polymerising ethylene pressure, and polymerization temperature is 20-200 ℃, and polymerization time is 1-24h; For reaching good effect, preferred 0.1-10.0MPa, polymerization temperature 50-120 ℃; More preferably 0.1-5MPa, polymerization temperature is 40-90 ℃.Slurry polymerization can carry out under overcritical or subcritical state, and the medium of employing is hexane or more higher alkane or white oil, and polymerization reactor is stirring tank or annular-pipe reactor; The vapour phase polymerization condition is that 1.0-10.0MPa, polymerization temperature are 40-100 ℃, and polymerization can be carried out in gas fluidized bed or gas phase stirring tank.
Polyvinyl resin with super-high molecular weight narrow molecular weight distribution (1.5-3.8), the ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight of the present invention's preparation are 1,500,000 to 1,000 ten thousand.The polymkeric substance particle diameter is evenly distributed, distinguishing feature is to be easy to processing, can be used for panel, filter core, small-bore, bigbore ultrahigh molecular weight polyethylene tubing such as extrudes at goods, particularly for example machine-shaping smoothly under the situation of common high density polyethylene(HDPE) of any industrial auxiliary agent can not added, for example extrude pure superelevation tubing, dry method or wet-spinning etc., molecular weight of polyethylene less degradation before and after processing, for example, the molecular weight of 2,500,000 pure superelevation polyvinyl resin extruding pipe material can reach 1,850,000, and its goods wear resisting property obviously is better than similar polyvinyl resin with super-high molecular weight product on the market; And for example the molecular weight that obtains fiber by 3,500,000 resin spinning can reach 1,800,000.
The polythene working property of the resulting molecular weight that is easy to process 500,000 to 1,000 ten thousand is outstanding under above-mentioned catalyst action, studies show that its excellent processing characteristics comes from it and the different specific molecule structure of like product in the market, promptly this quasi-polyethylene has the ultralow degree of branching.
The present invention has formulated this ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE), and containing the side chain number in the polyethylene in per 100000 carbon atoms is 0-2; Further be recommended as 0-1.
The molecular weight ranges of described ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) is recommended as 50 myriagram/moles to 1000 myriagram/moles, further recommend 150 myriagram/moles to 1000 myriagram/moles, further recommend 150 myriagram/moles to 700 myriagram/moles, especially recommend 150 myriagram/moles to 500 myriagram/moles.The dispersed index range of polymkeric substance is recommended as 2-10, further is recommended as 2-6, especially is recommended as 3-6.The bulk density scope is recommended as 0.20-0.52.
The preparation method of ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) of the present invention is as follows:
With above-mentioned catalyzer and alkylaluminium cpd is that the heterogeneous catalysis system that promotor is formed contacts with ethene, is that 0.3 to 10Mpa, 0 to 100 ℃ of scope internal reactions obtained in 1-18 hour at ethylene pressure.The mol ratio of catalyzer and promotor is 1: 1-5000, generally can be 1: during 10-2000 polymerization 2-6 hour so that make catalytic activity, polymer property and production cost all maintain scope preferably, preferred 1: 20～500.
Polymerization is generally carried out in inert organic solvents, and for example hydro carbons, cyclic hydrocar-bons or aromatic hydrocarbons also can be carried out in halogenated solvent, and as ethylene dichloride, chlorobenzene, for helping the reactor operation, inert organic solvents can use the hydro carbons less than 12 carbon.Be exemplified below but be not limited in this, propane, Trimethylmethane, Skellysolve A, 2-methylbutane, normal hexane, hexanaphthene, toluene, chlorobenzene, ethylene dichloride and composition thereof.
Polymerization temperature maintains 0 to 100 ℃, for reaching good catalytic activity and throughput, can maintain 50 to 90 ℃.
Polymerization pressure is operated in 0.3 to 3MPa can obtain reactor operating parameters and polymkeric substance preferably.
Promotor is an alkylaluminium cpd, alkylaluminoxane or weakly coordinating anion; Described alkylaluminium cpd is preferable over AlEt 3, AlMe 3Or Al (i-Bu) 3, AlEt 2Cl, alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta, MMAO (methylaluminoxane of modification) etc.; Weakly coordinating anion be preferable over [B (and 3,5-(CF 3) 2C 6H 3) 4] -, -OSO 2CF 3Or ((3,5-(CF 3) 2) C 6H 3) 4B -Catalyzer and promotor can any order adding system carry out polymerization, preferred AlEt 3The variable-scale of employed catalyzer of polymerization and promotor, common described polymerization time is 1-18 hour, the mol ratio of catalyzer and promotor is 1: 1-5000, generally can be 1: during 10-2000 polymerization 2-6 hour so that make catalytic activity, polymer property and production cost all maintain scope preferably, preferred 1: 20～500.
The ultralow branching ultrahigh molecular weight polyethylene(UHMWPE) of the present invention's initiative, under the close situation of the pure ultra-high molecular mass polyethylene sample of selling on molecular weight and molecular weight distribution parameter and the market, has lower melt viscosity, have outstanding processing characteristics, can be used for preparing tubing, bar, sheet material, filter core/millipore filtration or high-strength high-modulus fibre.
Analyze and the sign confirmation, ultralow branching ultrahigh molecular weight polyethylene(UHMWPE) provided by the invention, containing the side chain number in the polymkeric substance in per 100000 skeleton carbon atoms is 0-2.
When adopting described ultralow degree of branching ultrahigh molecular weight polyethylene to be equipped with tubing, bar, sheet material, filter core/millipore filtration or high-strength high-modulus fibre, extruded velocity is other same molecular amount ultrahigh molecular weight polyethylene(UHMWPE) under same processing conditions more than 2 times or 2 times, and common 2-5 doubly.
But described ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) in gel spinning prepares the preparation process of high-strength and high-modulus ultrahigh molecular weight polyethylene fibre, have screw pressure low, after spin the high characteristics of ultra-drawing multiple in the process.
The intensity of described high-strength high-modulus fibre can reach 35cN/dtex, for example 30-35cN/dtex; Modulus can reach 1600cN/dtex, for example 1000-1600cN/dtex.
Ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) of the present invention can adopt on the existing processing ultrahigh molecular weight polyethylene(UHMWPE) extrusion device and extrude under the situation of not adding processing aid; Described processing aid refers to reduce the softening agent of melt viscosity, relative low-molecular weight polymer or liquid crystal polymer, but does not comprise carbon black, silica gel or aluminum oxide enhancing mineral filler; Described relative low-molecular weight polymer is meant the common high density polyethylene(HDPE) of molecular weight at 5-30 myriagram/mole.
The ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) that the present invention formulated can be used for following product and purposes.
Wear-resistant tubing (is applicable to various high corrosion, the solid particulate of high wearing and tearing, powder, solidliquid mixture, the conveying of liquids and gases is as acid solution, alkali lye, coal water slurry, power plant's ash, the conveying of mud etc.), wearable plate is (as trim packing, glasswork's leak liner, the mine interior lining panel, heat power plant's coal bunker lining), various wear-resisting bars, film, profiled material (generally is used for machinery, vehicle, weaving, communication device, the wear-resisting part of food-processing platform), (generally be used for medicine separates various millipore filtrations, battery separator, water treatment etc.), and high-strength high-modulus fibre (ultrahigh molecular weight polyethylene(UHMWPE) is widely used in national defence troops and needs, aerospace, safety precaution, sports equipment, oceanographic engineering etc.) etc.
Description of drawings
Fig. 1 sells in market the pyrocarbon spectrum of ultrahigh molecular weight polyethylene(UHMWPE) P4 (M3 that second auxiliary factory, Beijing produces); Its side chain number is 7 ± 0.5/100000 carbon;
Fig. 2 sells in market the pyrocarbon spectrum of ultrahigh molecular weight polyethylene(UHMWPE) P6 (the Ticona company of import produce 4150); Its side chain number is 5.2 ± 0.5/100000 carbon;
Fig. 3 utilizes the pyrocarbon spectrum of the ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) P1 that the Primary Catalysts of load produces; The side chain number is less than 1 in 100000 carbon;
Figure on the right of among the accompanying drawing 1-3 is that the figure on the left side amplifies 3072 times figure.
The SEM picture of the catalytic ethylene homo of Fig. 4 loaded catalyst C1;
Specific implementation method
The following examples will better illustrate the present invention, but what need emphasize is that the present invention never only limits to content that this several embodiment explains.
Following examples have shown not ipsilateral of the present invention.Given embodiment comprises Preparation of catalysts, converging operation, polymerizing condition, polymerisate and the goods course of processing.
Titanium in the loaded catalyst (Ti) assay carries out on the OPTRMA-3000 inductive coupling plasma emission spectrograph at ICP-AES.
Polymkeric substance 13C-NMR composes on Varian XL-400MHz nuclear magnetic resonance analyser with D 4-o-dichlorobenzene is a solvent, measures down at 110 ℃.Monomer insertion rate is according to document (J C Randall, JMS-Rev.Maromol.Chem.Phys.1989, C29 (2﹠amp altogether; 3), method 201-317) calculates.
Size-grade distribution adopts Malvern S type particle-size analyzer, does dispersion agent with normal hexane.Polymericular weight (M η) measure according to the ASTM4020-01a method, its typical curve is:
M v＝5.37×10 4×[η] 1.37，
Wherein [η] is intrinsic viscosity, and unit is dL/g.Molecular weight distribution (PDI=M w/ M n) utilize Waters Alliance GPC2000 1,2, in 4 trichlorobenzene (flow velocity 1.0mL/min) under 135 ℃, be equipped with Wyatt company 18 angle high-temperature laser light scattering detectors to measure, ultra-high molecular weight dedicated columns with 20um, under flow velocity 0.5mL/min, obtain for the standard specimen determination and analysis with the polystyrene.
It is to utilize that ultrahigh molecular weight polyethylene(UHMWPE) is measured micro-branching content 13The C-NMR spectrum obtains.Polymkeric substance 13The C-NMR spectrum is measured down for 140 ℃ on the rotary attachment of evil spirit angle, the wide chamber of Bruker DSX-300MHz band high temperature, and each sample measurement added up the time greater than 16 hours, to satisfy measuring accuracy greater than 0.5 side chain/100000 carbon.
Part contains the synthetic method reference of the tridentate ligand of [ONX]: patent CN200610026766.2, and 01126323.7,02110844.7, Hu W.et.al., Organometallics 2004,23,1684-1688; Wang, C.et.al.Macromol.Rapid Commun.2005,26,1609-1614
(second auxiliary factory, Beijing produces M3 and is designated as P4 to have used a kind of home-made ultrahigh molecular weight polyethylene(UHMWPE) in the processing and implementation example, polymericular weight is 340 myriagram/moles, specifying information can obtain from Second Factory of Auxiliary Agent of Orient Petrochemical Industry Co., Ltd., Be website), (the production GUR4022 of Ticona company is designated as P5 and 4150 and is designated as P6 the ultrahigh molecular weight polyethylene(UHMWPE) of two kinds of imports, product information can obtain in its company's site), wherein P4 and P5 product are found and product P 1-1 by analysis, and viscosity-average molecular weight, the median size of P2-1 are approaching.
Embodiment 1
Synthesizing of ligand L 1
In the reaction flask of 100mL, add 3.06g (10.0mmol) 2-methyl isophthalic acid, 3-two (rubigan) propanedione, 1.47g (10.0mmol) 2-ethyl-3-thiomethyl butylamine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, be heated to backflow 12h after, stopped reaction, make to be chilled to room temperature ,-30 ℃ freezing, promptly obtains product, with cold washing with alcohol for several times, obtain yellow crystals L11.13g (26%) after the drying.Ultimate analysis: actual measurement (calculated value): C:63.23 (63.30); H:6.43 (6.24); N:3.32 (3.21); S:7.37 (7.35).
Figure BSA00000355523100201
Embodiment 2
Synthesizing of ligand L 2
In the reaction flask of 100mL, add 2.36g (10.0mmol) 2-methyl isophthalic acid-propenyl-3-(2-chloro-phenyl-) propanedione, 1.73g (10.0mmol) α-sulphur sec.-propyl hexahydroaniline, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, after being heated to backflow 12h, stopped reaction makes to be chilled to room temperature,-30 ℃ freezing, promptly obtain product, with cold washing with alcohol for several times, obtain yellow crystals L21.17g (30%) after the drying.Ultimate analysis: actual measurement (calculated value): C:67.23 (67.41); H:7.94 (7.71); N:3.62 (3.57); S:8.27 (8.18).
Figure BSA00000355523100211
Embodiment 3
Synthesizing of ligand L 3
In the reaction flask of 100mL, add 3.4g (10.0mmol) 2-methyl isophthalic acid-rubigan-3-p-trifluoromethyl phenyl propanedione, 1.73g (10.0mmol) α-thiopropyl hexahydroaniline, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, after being heated to backflow 12h, stopped reaction makes to be chilled to room temperature,-30 ℃ freezing, promptly obtain product, with cold washing with alcohol for several times, obtain yellow crystals L31.73g (35%) after the drying.Ultimate analysis: actual measurement (calculated value): C:62.83 (62.96); H:6.14 (5.89); N:2.94 (2.82); S:6.31 (6.46).
Figure BSA00000355523100212
Embodiment 4
Synthesizing of ligand L 4
In the reaction flask of 100mL, add 2.28g (10.0mmol) 4-methyl isophthalic acid-trimethyl silicon based-3, the 5-acetyl caproyl, 2.68g (10.0mmol) N-phenyl-1-normal-butyl-2-phenylethylenediamine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, be heated to backflow 12h after, stopped reaction, make to be chilled to room temperature ,-30 ℃ freezing, promptly obtains product, with cold washing with alcohol for several times, obtain yellow crystals L41.2g (25%) after the drying.Ultimate analysis: actual measurement (calculated value): C:75.38 (75.26); H:9.84 (9.68); N:6.06 (5.85).
Figure BSA00000355523100221
Embodiment 5
Synthesizing of ligand L 5
In the reaction flask of 100mL, add 2.68g (10.0mmol) 2-methyl isophthalic acid-Chloro-O-Phenyl-1, the 3-diacetylmethane, 3.13g (10.0mmol) 4-amino-5-sulphur sec.-propyl-5-is to the bromophenyl amylene, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, be heated to backflow 12h after, stopped reaction, make to be chilled to room temperature ,-30 ℃ freezing, promptly obtains product, with cold washing with alcohol for several times, obtain yellow crystals L53.2g (56%) after the drying.Ultimate analysis: actual measurement (calculated value): C:55.83 (55.23); H:5.74 (5.53); N:2.56 (2.48); S:5.31 (5.67).
Figure BSA00000355523100222
Embodiment 6
Synthesizing of ligand L 6
In the reaction flask of 100mL, add 3.56g (10.0mmol) 2-methyl isophthalic acid-Alpha-Naphthyl-3-p-trifluoromethyl phenyl propanedione, 1.67g (10.0mmol) 2-thiopropyl aniline, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, after being heated to backflow 12h, stopped reaction makes to be chilled to room temperature,-30 ℃ freezing, promptly obtain product, with cold washing with alcohol for several times, obtain yellow crystals L62.3g (45%) after the drying.Ultimate analysis: actual measurement (calculated value): C:71.38 (71.27); H:5.54 (5.18); N:2.96 (2.77); S:6.31 (6.34).
Figure BSA00000355523100231
Embodiment 7
Synthesizing of ligand L 7
In the reaction flask of 100mL, add 2.05g (10.0mmol) 2-methyl isophthalic acid-(4-pyridyl)-1, the 3-hexanedione, 2.52g (10.0mmol) 4,5-two chloro-2-semidines, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, after being heated to backflow 12h, stopped reaction makes to be chilled to room temperature,-30 ℃ freezing, promptly obtain product, with cold washing with alcohol for several times, obtain yellow crystals L72.2g (51%) after the drying.Ultimate analysis: actual measurement (calculated value): C:65.83 (65.46); H:5.37 (5.26); N:9.26 (9.54).
Figure BSA00000355523100232
Embodiment 8
Synthesizing of ligand L 8
In the reaction flask of 100mL, add 4.18g (10.0mmol) 2-methyl isophthalic acid, 3-pentafluorophenyl group propanedione, 1.95g (10.0mmol) 3-sec.-propyl-3-phenyl-ethyl amine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, be heated to backflow 12h after, stopped reaction, make to be chilled to room temperature ,-30 ℃ freezing, promptly obtains product, with cold washing with alcohol for several times, obtain yellow crystals L80.89g (15%) after the drying.Ultimate analysis: actual measurement (calculated value): C:54.83 (54.46); H:3.47 (3.22); N:2.84 (2.35); S:5.31 (5.38).
Figure BSA00000355523100241
Embodiment 9
Synthesizing of ligand L 9
In the reaction flask of 100mL, add 2.96g (10.0mmol) 2-methyl isophthalic acid-(α-Fu Nan base)-3-p-trifluoromethyl phenyl propanedione, 1.43g (10.0mmol) 3-thiopropyl-4-amino-ethyl acetylene, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, after being heated to backflow 12h, stopped reaction makes to be chilled to room temperature,-30 ℃ freezing, promptly obtain product, with cold washing with alcohol for several times, obtain yellow crystals L91.1g (25%) after the drying.Ultimate analysis: actual measurement (calculated value): C:62.57 (62.69); H:5.38 (5.26); N:3.54 (3.32); S:7.83 (7.61).
Figure BSA00000355523100242
Embodiment 10
Synthesizing of ligand L 10
In the reaction flask of 100mL, add 2.30g (10.0mmol) 2,4-dimethyl-5-(2, the 6-3,5-dimethylphenyl)-and 1-amylene-3,5-diketone, 2.77g (10.0mmol) 2-diphenylphosphine base aniline, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, be heated to backflow 12h after, stopped reaction, make to be chilled to room temperature ,-30 ℃ freezing, promptly obtains product, with cold washing with alcohol for several times, obtain yellow crystals L10 1.5g (30%) after the drying.Ultimate analysis: actual measurement (calculated value): C:80.57 (80.96); H:6.72 (6.59); N:2.54 (2.86).
Embodiment 11
Synthesizing of ligand L 11
In the reaction flask of 100mL, add the adjacent oxygen aminomethyl phenyl of 2.30g (10.0mmol) 5-methyl-6--1-hexin-4, the 6-diketone, 1.59g (10.0mmol) 2-thiopropyl cyclopentamine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, be heated to backflow 12h after, stopped reaction, make to be chilled to room temperature ,-30 ℃ freezing, promptly obtains product, with cold washing with alcohol for several times, obtain yellow crystals L110.37 (10%) after the drying.Ultimate analysis: actual measurement (calculated value): C:71.27 (71.12); H:8.07 (7.87); N:3.94 (3.77); S:8.81 (8.63).
Figure BSA00000355523100252
Embodiment 12
Synthesizing of ligand L 12
In the reaction flask of 100mL, add 3.3g (10.0mmol) 2-methyl isophthalic acid-rubigan-3-to the isopropyl phenyl propanedione, the adjacent chlorine sulfur phenenyl of 1.87g (10.0mmol) 2-ethamine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, after being heated to backflow 12h, stopped reaction makes to be chilled to room temperature,-30 ℃ freezing, promptly obtain product, with cold washing with alcohol for several times, obtain yellow crystals L120.75g (15%) after the drying.Ultimate analysis: actual measurement (calculated value): C:64.89 (64.80); H:5.78 (5.44); N:2.96 (2.80); S:6.52 (6.41).
Figure BSA00000355523100261
Embodiment 13
(1) thermal treatment of carrier
Get ES70 type silica gel (Pq Corp.'s product) roasting under nitrogen atmosphere.Its roasting condition is: in 200 ℃ of processing 2h, be warming up to 400 ℃ then and handle 2h, handle 4h, naturally cooling under nitrogen atmosphere at 600 ℃ again.Be designated as the ES70 carrier.
(2) preparation of complex carrier I
Add THF 30mL in the 2g Magnesium Chloride Anhydrous, stir 10min; Drip titanium tetrachloride 0.8mL, be warming up to 70 ℃ after adding, stirred 2 hours, be clear solution; Add the ES70 carrier 2g of thermal activation, stirred 2 hours; Drip hexane 30mL, solid is all separated out; Suction filtration, hexane are washed 1 time, obtain complex carrier I.
(3) preparation of complex carrier II
In above-mentioned complex carrier I, add hexane 30mL; Drip titanium tetrachloride 0.8mL, stirred 2 hours; Suction filtration is washed once with the 30mL hexane; Suction filtration, decompressing and extracting obtains complex carrier II, and titanium content is 4.1%.
(4) preparation of Nonmetallocene polyolefine catalyst
Get complex carrier II 2.0g, add and carrier equal-volume toluene, slowly drip the polydentate ligand L1 solution 5mL (concentration is 0.184g/mL) of dilution with toluene, suction filtration, hexane are given a baby a bath on the third day after its birth inferior, and drying obtains Nonmetallocene polyolefine catalyst, is designated as CAT1.
Embodiment 14
Substantially the same manner as Example 13, obtained corresponding carry type non-metallocene calalyst for polymerization of olefine CAT2-CAT10 with following polydentate ligand L2-L10 respectively.
Embodiment 15
The preparation of title complex A1
In the reaction flask of 100mL, add 2.82g (10.0mmol) 1-(2, the 6-3,5-dimethylphenyl)-3-(2-p-methoxy-phenyl) propanedione, 0.91g (10.0mmol) 2-thiomethyl ethamine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, be heated to backflow 12h after, stopped reaction, make to be chilled to room temperature ,-30 ℃ freezing, promptly obtains product, with cold washing with alcohol for several times, obtain yellow crystals L1 1.9g (56%) after the drying.Ultimate analysis: actual measurement (calculated value): C:80.02 (70.95); H:8.14 (7.09); N:3.96 (3.94); S:8.52 (8.45).
Figure BSA00000355523100271
10mL tetrahydrofuran solution with 710mg (2.0mmol) ligand L 1 under-78 ℃ is added dropwise in the 10mL tetrahydrofuran (THF) of 79mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Vacuum desolventizes, and adds 40mL toluene, under the room temperature this negative solution is dropped to TiCl 4In the 10mL toluene solution of 379mg (2.0mmol), dropwise, continue under the room temperature and stir 12h.Centrifugal, supernatant liquor removes to desolvate and promptly obtains thick product, obtains title complex A1 with the toluene recrystallization.Ultimate analysis: actual measurement (calculated value): C:49.57 (49.58); H:4.78 (4.76); N:2.74 (2.77); S:8.13 (8.35).
Figure BSA00000355523100272
Embodiment 16
The preparation of title complex A2
In the reaction flask of 100mL; add 4.04g (10.0mmol) penta fluoro benzene formyl radical penta fluoro benzene ethyl ketone, 0.91g (10.0mmol) 2-thiomethyl ethamine, 0.5mL Glacial acetic acid; the 30mL dehydrated alcohol; after being heated to backflow 12h, stopped reaction makes to be chilled to room temperature;-30 ℃ freezing; promptly obtain product, with cold washing with alcohol for several times, obtain yellow crystals L23.6g (76%) after the drying.Ultimate analysis: actual measurement (calculated value): C:45.57 (45.29); H:1.93 (1.90); N:2.94 (2.93); S:6.87 (6.72).
10mL tetrahydrofuran solution with 954mg (2.0mmol) ligand L 2 under-78 ℃ is added dropwise in the 10mL tetrahydrofuran (THF) of 79mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Vacuum desolventizes, and adds 40mL toluene, under the room temperature this negative solution is dropped to TiCl 4In the 10mL toluene solution of 379mg (2.0mmol), dropwise, continue under the room temperature and stir 12h.Centrifugal, supernatant liquor removes to desolvate and promptly obtains thick product, obtains title complex A2 with the toluene recrystallization.Ultimate analysis: actual measurement (calculated value): C:34.57 (34.29); H:1.43 (1.28); N:2.14 (2.22); S:5.87 (5.09).
Figure BSA00000355523100282
Embodiment 17
The preparation of title complex A3
In the reaction flask of 100mL, add 3.6g (10.0mmol) p-trifluoromethyl phenyl to trifluoromethyl acetophenone, 1.19g (10.0mmol) 2-thiopropyl ethamine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, after being heated to backflow 12h, stopped reaction makes to be chilled to room temperature,-30 ℃ freezing, promptly obtain product, with cold washing with alcohol for several times, obtain yellow crystals L33.2g (70%) after the drying.Ultimate analysis: actual measurement (calculated value): C:57.43 (57.26); H:4.72 (4.59); N:3.14 (3.04); S:6.87 (6.95).
Figure BSA00000355523100291
10mL tetrahydrofuran solution with 720mg (2.0mmol) ligand L 3 under-78 ℃ is added dropwise in the 10mL tetrahydrofuran (THF) of 79mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Vacuum desolventizes, and adds 40mL toluene, under the room temperature this negative solution is dropped to TiCl 4In the 10mL toluene solution of 379mg (2.0mmol), dropwise, continue under the room temperature and stir 12h.Centrifugal, supernatant liquor removes to desolvate and promptly obtains thick product, obtains title complex A3 with the toluene recrystallization.Ultimate analysis: actual measurement (calculated value): C:43.57 (42.99); H:3.43 (3.28); N:2.52 (2.28); S:5.47 (5.22).
Figure BSA00000355523100292
Embodiment 18
The preparation of title complex A4
In the reaction flask of 100mL, add 1.9g (10.0mmol) 6-(4-pyridyl)-4,6-diketone-2-hexene, 1.2g (10.0mmol) 2-thiopropyl ethamine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, be heated to backflow 12h after, stopped reaction, make to be chilled to room temperature ,-30 ℃ freezing, promptly obtains product, with cold washing with alcohol for several times, obtain yellow crystals L40.73g (25%) after the drying.Ultimate analysis: actual measurement (calculated value): C:68.19 (68.17); H:7.77 (7.64); N:9.72 (9.65).
Figure BSA00000355523100301
10mL tetrahydrofuran solution with 580mg (2.0mmol) ligand L 4 under-78 ℃ is added dropwise in the 10mL tetrahydrofuran (THF) of 79mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Vacuum desolventizes, and adds 40mL toluene, under the room temperature this negative solution is dropped to TiCl 4In the 10mL toluene solution of 379mg (2.0mmol), dropwise, continue under the room temperature and stir 12h.Centrifugal, supernatant liquor removes to desolvate and promptly obtains thick product, obtains title complex A4. ultimate analysis with the toluene recrystallization: actual measurement (calculated value): C:43.12 (43.32); H:4.84 (4.77); N:6.32 (6.31).
Figure BSA00000355523100302
Embodiment 19
The preparation of title complex A5
In the reaction flask of 100mL, add 2.86g (10.0mmol) 1-(2,6-di-n-butyl phenyl)-3-(2-bromophenyl) propanedione, 1.19g (10.0mmol) 2-phosphorus propyl group ethamine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, be heated to backflow 12h after, stopped reaction, make to be chilled to room temperature ,-30 ℃ freezing, promptly obtains product, with cold washing with alcohol for several times, obtain yellow crystals L50.97g (30%) after the drying.Ultimate analysis: actual measurement (calculated value): C:68.15 (68.11); H:7.84 (7.61); N:2.76 (2.71); Br:15.34 (15.47).
Figure BSA00000355523100311
10mL tetrahydrofuran solution with 774mg (2.0mmol) ligand L 5 under-78 ℃ is added dropwise in the 10mL tetrahydrofuran (THF) of 79mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Vacuum desolventizes, and adds 40mL toluene, under the room temperature this negative solution is dropped to TiCl 4In the 10mL toluene solution of 379mg (2.0mmol), dropwise, continue under the room temperature and stir 12h.Centrifugal, supernatant liquor removes to desolvate and promptly obtains thick product, obtains title complex A5. ultimate analysis with the toluene recrystallization: actual measurement (calculated value): C:52.99 (52.45); H:5.84 (5.66); N:2.62 (2.18), Br:24.90 (24.92).
Embodiment 20
The preparation of title complex A6
In the reaction flask of 100mL, add 1.82g (10.0mmol) uncle 2-fourth carbonyl pimelinketone, 2.0g (10.0mmol) 2-selenium phenyl base ethamine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, after being heated to backflow 12h, stopped reaction makes to be chilled to room temperature,-30 ℃ freezing, promptly obtain product, with cold washing with alcohol for several times, obtain yellow crystals L60.55g (15%) after the drying.Ultimate analysis: actual measurement (calculated value): C:62.85 (62.63); H:7.84 (7.47); N:4.17 (3.84).
Figure BSA00000355523100321
10mL tetrahydrofuran solution with 730mg (2.0mmol) ligand L 6 under-78 ℃ is added dropwise in the 10mL tetrahydrofuran (THF) of 79mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Vacuum desolventizes, and adds 40mL toluene, under the room temperature this negative solution is dropped to TiCl 4In the 10mL toluene solution of 379mg (2.0mmol), dropwise, continue under the room temperature and stir 12h.Centrifugal, supernatant liquor removes to desolvate and promptly obtains thick product, obtains title complex A6. ultimate analysis with the toluene recrystallization: actual measurement (calculated value): C:44.13 (44.09); H:5.12 (5.06); N:2.88 (2.71).
Figure BSA00000355523100322
Embodiment 21
The preparation of title complex A7
In the reaction flask of 100mL, add 2.38g (10.0mmol) 6-(2-naphthyl)-4,6-diketone-2-hexene, 2.29g (10.0mmol) 2-diphenylphosphine base ethamine, 0.5mL Glacial acetic acid, the 30mL dehydrated alcohol, be heated to backflow 12h after, stopped reaction, make to be chilled to room temperature ,-30 ℃ freezing, promptly obtains product, with cold washing with alcohol for several times, obtain yellow crystals L7 2.38g (53%) after the drying.Ultimate analysis: actual measurement (calculated value): C:80.29 (80.16); H:6.52 (6.28); N:3.47 (3.12).
10mL tetrahydrofuran solution with 898mg (2.0mmol) ligand L 7 under-78 ℃ is added dropwise in the 10mL tetrahydrofuran (THF) of 79mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Vacuum desolventizes, and adds 40mL toluene, under the room temperature this negative solution is dropped to TiCl 4In the 10mL toluene solution of 379mg (2.0mmol), dropwise, continue under the room temperature and stir 12h.Centrifugal, supernatant liquor removes to desolvate and promptly obtains thick product, obtains title complex A7. ultimate analysis with the toluene recrystallization: actual measurement (calculated value): C:59.83 (59.78); H:4.65 (4.52); N:2.66 (2.32).
Figure BSA00000355523100331
Embodiment 22
The preparation of title complex A8
40mL tetrahydrofuran solution with 564mg (2.0mmol) ligand L 1 under-78 ℃ is added dropwise in the 15mL tetrahydrofuran (THF) of 80mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Under 50 ℃ this negative solution is dropped to ZrCl 4Among the 15mL THF of 2THF 755mg (2.0mmol), dropwise, continue to reflux to stir and spend the night.Vacuum desolventizes, and adds methylene dichloride 20mL and makes dissolving fully, and centrifugal, supernatant concentration adds a small amount of hexane, freezingly obtains thick product, obtains title complex A8 with the dichloromethane/hexane recrystallization.Ultimate analysis: actual measurement (calculated value): C:46.02 (45.69); H:4.47 (4.38); N:2.66 (2.54); S:5.85 (5.81).
Embodiment 23
The preparation of title complex A9
40mL tetrahydrofuran solution with 730mg (2.0mmol) ligand L 6 under-78 ℃ is added dropwise in the 15mL tetrahydrofuran (THF) of 80mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Under 50 ℃ this negative solution is dropped to ZrCl 4Among the 15mL THF of 2THF 755mg (2.0mmol), dropwise, continue to reflux to stir and spend the night.Vacuum desolventizes, and adds methylene dichloride 20mL and makes dissolving fully, and centrifugal, supernatant concentration adds a small amount of hexane, freezingly obtains thick product, obtains title complex A9 with the dichloromethane/hexane recrystallization.Ultimate analysis: actual measurement (calculated value): C:40.71 (40.68); H:4.83 (4.67); N:2.64 (2.50).
Embodiment 24
The preparation of title complex A10
40mL tetrahydrofuran solution with 1030mg (2.0mmol) ligand L 5 under-78 ℃ is added dropwise in the 15mL tetrahydrofuran (THF) of 80mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Under 50 ℃ this negative solution is dropped to ZrCl 4Among the 15mL THF of 2THF 755mg (2.0mmol), dropwise, continue to reflux to stir and spend the night.Vacuum desolventizes, and adds methylene dichloride 20mL and makes dissolving fully, and centrifugal, supernatant concentration adds a small amount of hexane, freezingly obtains thick product, obtains title complex A10550mg (35%) with the dichloromethane/hexane recrystallization.Ultimate analysis: actual measurement (calculated value): C:42.39 (42.52); H:4.65 (4.59); N:1.80 (1.77).
Figure BSA00000355523100342
Embodiment 25
The preparation of title complex A11
40mL tetrahydrofuran solution with 1030mg (2.0mmol) ligand L 5 under-78 ℃ is added dropwise in the 15mL tetrahydrofuran (THF) of 80mg (2.0mmol) KH, continues under the room temperature and stirs 2h.Under 50 ℃ this negative solution is dropped to HfCl 4Among the 15mL THF of 2THF 929mg (2.0mmol), dropwise, continue to reflux to stir and spend the night.Vacuum desolventizes, and adds methylene dichloride 20mL and makes dissolving fully, and centrifugal, supernatant concentration adds a small amount of hexane, freezingly obtains thick product, obtains title complex A10438mg (25%) with the dichloromethane/hexane recrystallization.Ultimate analysis: actual measurement (calculated value): C:38.32 (38.29); H:4.45 (4.13); N:1.60 (1.59).
Figure BSA00000355523100351
Embodiment 26
(1) chemical treatment of magnesium compound
Get spherical magnesium chloride alcohol adduct 10.0g, wherein ethanol content 52%, volume average particle size D[4,3] be 48um, add the 50mL hexane, slowly drip triethyl aluminum 18mL under nitrogen atmosphere, after dripping, mechanical stirring (100 rev/mins of rotating speeds) continues reaction 2h, suction filtration, with 50mL hexane wash twice, drying under reduced pressure obtains the spherical magnesium chloride of activatory, is designated as SMC-1.
(2) preparation of catalyzer 1
0.1g metal complexes A1 is joined in the 10mL methylene dichloride, after treating to dissolve fully, join among the spherical magnesium chloride SMC-11.0g that chemical activation crosses, mechanical stirring 2h under the nitrogen atmosphere (100 rev/mins of rotating speeds), decompressing and extracting, with 50mL hexane wash twice, drying under reduced pressure obtains the carry type non-metallocene calalyst for polymerization of olefine C1 of good fluidity.
Embodiment 27
(1) chemical treatment of magnesium compound
Get spherical magnesium chloride alcohol adduct 10.0g, wherein butanol content 52%, volume average particle size D[4,3] be 60um, add the 50mL hexane, slowly drip triethyl aluminum 9.5mL under nitrogen atmosphere, after dripping, mechanical stirring (100 rev/mins of rotating speeds) continues reaction 2h, suction filtration, with 50mL hexane wash twice, drying under reduced pressure obtains the spherical magnesium chloride of activatory, is designated as SMC-2.
(2) preparation of catalyzer 2
0.1g metal complexes A1 is joined in the 10mL methylene dichloride, after treating to dissolve fully, join among the spherical magnesium chloride SMC-21.0g that chemical activation crosses, mechanical stirring 2h under the nitrogen atmosphere (100 rev/mins of rotating speeds), decompressing and extracting, with 50mL hexane wash twice, drying under reduced pressure obtains the carry type non-metallocene calalyst for polymerization of olefine C2 of good fluidity.
Embodiment 28
(1) chemical treatment of magnesium compound
Get spherical magnesium chloride alcohol adduct 10.0g, wherein phenylcarbinol content 60%, volume average particle size D[4,3] be 60um, add the 50mL hexane, slowly drip triethyl aluminum 7.6mL under nitrogen atmosphere, after dripping, mechanical stirring (100 rev/mins of rotating speeds) continues reaction 2h, suction filtration, with 50mL hexane wash twice, drying under reduced pressure obtains the spherical magnesium chloride of activatory, is designated as SMC-3.
(2) preparation of catalyzer 3
0.1g metal complexes A1 is joined in the 10mL methylene dichloride, after treating to dissolve fully, join among the spherical magnesium chloride SMC-31.0g that chemical activation crosses, mechanical stirring 2h under the nitrogen atmosphere (100 rev/mins of rotating speeds), decompressing and extracting, with 50mL hexane wash twice, drying under reduced pressure obtains the carry type non-metallocene calalyst for polymerization of olefine C3 of good fluidity.
Embodiment 29
(1) chemical treatment of magnesium compound
Get spherical magnesium chloride alcohol adduct 10.0g, wherein phenylethyl alcohol content 60%, volume average particle size D[4,3] be 60um, add the 50mL hexane, slowly drip triisobutyl aluminium 12.5mL under nitrogen atmosphere, after dripping, mechanical stirring (100 rev/mins of rotating speeds) continues reaction 2h, suction filtration, with 50mL hexane wash twice, drying under reduced pressure obtains the spherical magnesium chloride of activatory, is designated as SMC-4.
(2) preparation of catalyzer 4
0.1g metal complexes A1 is joined in the 10mL methylene dichloride, after treating to dissolve fully, join among the spherical magnesium chloride SMC-41.0g that chemical activation crosses, mechanical stirring 2h under the nitrogen atmosphere (100 rev/mins of rotating speeds), decompressing and extracting, with 50mL hexane wash twice, drying under reduced pressure obtains the carry type non-metallocene calalyst for polymerization of olefine C4 of good fluidity.
Embodiment 30
Substantially the same manner as Example 26, obtained corresponding carry type non-metallocene calalyst for polymerization of olefine C5-C13 with metal complexes A2-A10 respectively.
Embodiment 31
Substantially the same manner as Example 26, but made following change:
A1 is dissolved in the 10mL methylene dichloride with the 0.15g metal complexes.
Embodiment 32
Substantially the same manner as Example 26, but made following change:
A1 is dissolved in the 10mL methylene dichloride with the 0.2g metal complexes.
Embodiment 33
Substantially the same manner as Example 26, but made following change:
The amount of triethyl aluminum changes 22mL into.
Embodiment 34
Substantially the same manner as Example 26, but made following change:
The amount of triethyl aluminum changes 27mL into.
Embodiment 35 catalyzer D1's is synthetic
Part D:
The 1.0g Magnesium Chloride Anhydrous is joined in the 40mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir 2h down at 60 ℃; Drip the TiCl of 3.4mmol 4, react 4h down at 60 ℃, add the part D of the above-mentioned preparation of 3.4mmol then, react 12h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer D1 to product then with hexane.Ti content: 6.40wt%, Mg content: 7.48wt%, N content: 1.94%, Ti: N ratio 1: 1.
Embodiment 36 catalyzer D2's is synthetic
The 1.0g Magnesium Chloride Anhydrous is joined in the 80mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir down 3h, and add the Ti title complex that the part D of 4.0mmol obtains, at 60 ℃ of reaction 24h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer D2 to product then with hexane.Ti content: 8.0wt-%, Mg content: 6.4wt-%, N content: 2.44%, Ti: N ratio 1: 1.
Embodiment 37 catalyzer E1's is synthetic
Part E:
Figure BSA00000355523100381
The 1.0g Magnesium Chloride Anhydrous is joined in the 80mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir down 3h, and add the Ti title complex that the part E of 4.0mmol obtains, at 60 ℃ of reaction 24h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer E1 to product then with hexane.Ti content: 6.1wt-%, Mg content: 6.88wt-%, N content: 1.86%, Ti: N ratio 1: 1.
Embodiment 38 catalyzer F1's is synthetic
Part F:
Figure BSA00000355523100382
The 1.0g Magnesium Chloride Anhydrous is joined in the 80mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir down 3h, and add the Ti title complex that the part F of 4.0mmol obtains, at 60 ℃ of reaction 24h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer F1 to product then with hexane.Ti content: 5.96wt-%, Mg content: 6.48wt-%, N content: 1.78%, Ti: N ratio 1: 1.
Synthesizing of embodiment 39 catalyst I 1
Ligand i:
The 1.0g Magnesium Chloride Anhydrous is joined in the 80mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir down 3h, and add the Ti title complex that the ligand i of 4.0mmol obtains, at 60 ℃ of reaction 24h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyst I 1 to product then with hexane.Ti content: 5.9wt-%, Mg content: 6.28wt-%, N content: 1.14%, Ti: N ratio 1: 1.
Embodiment 40 catalyzer J1's is synthetic
Part J:
Figure BSA00000355523100391
The 1.0g Magnesium Chloride Anhydrous is joined in the 80mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir down 3h, and add the Ti title complex that the part J of 4.0mmol obtains, at 60 ℃ of reaction 24h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer J1 to product then with hexane.Ti content: 6.4wt-%, Mg content: 7.48wt-%, N content: 3.88%, Ti: N ratio 1: 1.
Embodiment 41 catalyzer K1's is synthetic
Part K:
The 1.0g Magnesium Chloride Anhydrous is joined in the 80mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir down 3h, and add the Ti title complex that the part K of 4.0mmol obtains, at 60 ℃ of reaction 24h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer K1 to product then with hexane.Ti content: 6.44wt-%, Mg content: 7.5wt-%, N content: 1.96%, Ti: N ratio 1: 1.
Embodiment 42 catalyzer L1's is synthetic
Ligand L:
Figure BSA00000355523100393
The 1.0g Magnesium Chloride Anhydrous is joined in the 80mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir down 3h, and add the Ti title complex that the ligand L of 4.0mmol obtains, at 60 ℃ of reaction 24h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer L1 to product then with hexane.Ti content: 6.3wt-%, Mg content: 7.48wt-%, N content: 1.94%, Ti: N ratio 1: 1.
Embodiment 43 catalyzer M1's is synthetic
Part M:
Figure BSA00000355523100401
The 1.0g Magnesium Chloride Anhydrous is joined in the 80mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir down 3h, and add the Ti title complex that the part M of 4.0mmol obtains, at 60 ℃ of reaction 24h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyzer M1 to product then with hexane.Ti content: 6.5wt-%, Mg content: 7.68wt-%, N content: 1.98%, Ti: N ratio 1: 1.
Synthesizing of embodiment 44 catalyst ns 1
Part N:
Figure BSA00000355523100402
The 1.0g Magnesium Chloride Anhydrous is joined in the 80mL tetrahydrofuran (THF) (hereinafter to be referred as THF), stir down 3h, and add the Ti title complex that the part N of 4.0mmol obtains, at 60 ℃ of reaction 24h down at 60 ℃.Reaction removes solvent under reduced pressure after finishing, and (3 * 20mL) washings, drying under reduced pressure obtains catalyst n 1 to product then with hexane.Ti content: 7.04wt-%, Mg content: 7.8wt-%, N content: 2.04%, Ti: N ratio 1: 1.
Embodiment 45 ethene slurry polymerizations
The 2.0L stainless steel is stirred polymeric kettle N 2Replace three times, ethene displacement twice just contains AlEt 31.0L hexane solution (0.15M) add in the still, start stirring (rotating speed=200rpm), and temperature in the kettle is preheating to about 60 ℃ with water bath with thermostatic control.At N 2Protection down; to successively-quantitatively monomer (not having other common monomers during ethylene homo) and 20mg catalyzer (with the above-mentioned hexane solution flushing of 0.2L) join in the polymeric kettle altogether; shed the still internal pressure then; treat that temperature in the kettle rises to about 80 ℃; feed 0.2MPa hydrogen, feed ethylene gas again, make the still internal pressure reach 0.8MPa; after five minutes, mixing speed is risen to 300rpm.Bath temperature transfers to 85 ℃.Stop to feed ethene behind the polymerization 2h, with recirculated cooling water temperature in the kettle is reduced to below 50 ℃, gas in the emptying system and discharging obtain granulated polymer after the drying.
Concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M w(g/mol), molecular weight distribution polymerization result data such as (PDI) are listed in table 1.
Table 1
Figure BSA00000355523100411
Embodiment 46 preparation ultrahigh molecular weight polyethylene(UHMWPE)s
The 2.0L stainless steel is stirred polymeric kettle N 2Replace three times, ethene displacement twice will contain AlEt 30.8L hexane solution (0.015M) add in the still, start stirring (rotating speed=200rpm), and temperature in the kettle is preheating to about 50 ℃ with water bath with thermostatic control.At N 2Protection joins 20mg catalyzer (with the above-mentioned hexane solution flushing of 0.2L) in the polymeric kettle down, sheds the still internal pressure then; treat that temperature in the kettle rises to about 60 ℃, feed ethylene gas again, make the still internal pressure reach 0.5MPa; after five minutes, mixing speed is risen to 300rpm.Bath temperature transfers to 70 ℃.Stop to feed ethene behind the polymerization 1h, with recirculated cooling water temperature in the kettle is reduced to below 50 ℃, gas in the emptying system and discharging obtain granulated polymer after the drying.
Concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M w(g/mol), molecular weight distribution polymerization result data such as (PDI) are listed in table 2.
Table 2
Figure BSA00000355523100421
Embodiment 47 preparation ultrahigh molecular weight polyethylene(UHMWPE)s
The 2.0L stainless steel is stirred polymeric kettle N 2Replace three times, ethene displacement twice will contain AlEt 30.8L hexane solution (0.015M) add in the still, start stirring (rotating speed=200rpm), and temperature in the kettle is preheating to about 50 ℃ with water bath with thermostatic control.At N 2Protection joins 20mg catalyzer (with the above-mentioned hexane solution flushing of 0.2L) in the polymeric kettle down, sheds the still internal pressure then; treat that temperature in the kettle rises to about 60 ℃, feed ethylene gas again, make the still internal pressure reach 0.8MPa; after five minutes, mixing speed is risen to 300rpm.Bath temperature transfers to 70 ℃.Stop to feed ethene behind the polymerization 1h, with recirculated cooling water temperature in the kettle is reduced to below 50 ℃, gas in the emptying system and discharging obtain granulated polymer after the drying.
Concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M w(g/mol), molecular weight distribution polymerization result data such as (PDI) are listed in table 3.
Table 3
Figure BSA00000355523100431
Embodiment 48 preparation ultrahigh molecular weight polyethylene(UHMWPE)s
The 2.0L stainless steel is stirred polymeric kettle N 2Replace three times, ethene displacement twice just contains AlEt 30.8L hexane solution (0.015M) add in the still, start stirring (rotating speed=200rpm), and temperature in the kettle is preheating to about 50 ℃ with water bath with thermostatic control.At N 2Protection joins 20mg catalyzer (with the above-mentioned hexane solution flushing of 0.2L) in the polymeric kettle down, sheds the still internal pressure then; treat that temperature in the kettle rises to about 60 ℃, feed ethylene gas again, make the still internal pressure reach 1.2MPa; after five minutes, mixing speed is risen to 300rpm.Bath temperature transfers to 70 ℃.Stop to feed ethene behind the polymerization 1h, with recirculated cooling water temperature in the kettle is reduced to below 50 ℃, gas in the emptying system and discharging obtain granulated polymer after the drying.
Concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M w(g/mol), molecular weight distribution polymerization result data such as (PDI) are listed in table 4.
Table 4
Figure BSA00000355523100441
Embodiment 49 catalyzer C1 ethene slurry polymerizations are produced ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE)
The 0.5L stainless steel is stirred polymeric kettle N 2Replace three times, ethene displacement twice, the 180mL hexane solution that will contain promotor adds in the still, and (rotating speed=150rpm) is at N to start stirring 2Protection down; catalyzer D1 (with the above-mentioned hexane solution flushing of 20mL) joins in the polymeric kettle with it is as shown in the table; shed the still internal pressure then; treat the temperature in the kettle temperature that rises to that it is as shown in the table; feed ethylene gas; make the still internal pressure polymerization pressure that reaches that it is as shown in the table, after five minutes, mixing speed is risen to 250rpm.Stop to feed ethene behind the polymerization 1h, treat temperature in the kettle and room temperature differ be no more than 20 the degree, gas in the emptying system and discharging obtain granulated polymer after the drying.
Polymerization result data such as concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M η (g/mol), molecular weight distribution (PDI), branching content are listed in table 5.
Table 5
Figure BSA00000355523100451
The ethene slurry polymerization is produced ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) under the different polymerization times of embodiment 50 catalyzer D1
The 2L stainless steel is stirred polymeric kettle N 2Replace three times, ethene displacement twice, the 1.2L hexane solution that will contain the promotor triethyl aluminum adds in the still, and (rotating speed=150rpm) is at N to start stirring 2Protection down; catalyzer D1 (with the above-mentioned hexane solution flushing of 20mL) joins in the polymeric kettle with it is as shown in the table; shed the still internal pressure then; treat the temperature in the kettle temperature that rises to that it is as shown in the table; feed ethylene gas; make the still internal pressure polymerization pressure that reaches that it is as shown in the table, after five minutes, mixing speed is risen to 250rpm.Polymerization stops to feed ethene after as the time as described in showing, and treats that temperature in the kettle and room temperature differ to be no more than 20 degree, and gas in the emptying system and discharging obtain granulated polymer after the drying.
Polymerization result data such as concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M η (g/mol), molecular weight distribution (PDI), branching content are listed in table 6.
Table 6
Figure BSA00000355523100461
Embodiment 51 different catalysts ethene slurry polymerizations are produced ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE)
The 0.5L stainless steel is stirred polymeric kettle N 2Replace three times, ethene displacement twice just contains AlEt 3180mL hexane solution (0.015M) add in the still, start stirring (rotating speed=150rpm), and temperature in the kettle is preheating to about 60 ℃ with water bath with thermostatic control.At N 2Protection joins 10mg catalyzer (with the above-mentioned hexane solution flushing of 20mL) in the polymeric kettle down, sheds the still internal pressure then; treat that temperature in the kettle rises to about 65 ℃, feed ethylene gas, make the still internal pressure reach 0.8MPa; after five minutes, mixing speed is risen to 250rpm.Bath temperature transfers to 70 ℃.Stop to feed ethene behind the polymerization 1h, with recirculated cooling water temperature in the kettle is reduced to below 50 ℃, gas in the emptying system and discharging obtain granulated polymer after the drying.
Concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M w(g/mol), molecular weight distribution polymerization result data such as (PDI) are listed in table 7.
Table 7
Figure BSA00000355523100471
Embodiment 52 catalyzer ethene slurry polymerizations are produced ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE)
The 0.5L stainless steel is stirred polymeric kettle N 2Replace three times, ethene displacement twice just contains AlEt 3180mL different solvents solution (0.015M is as shown in table 3) add in the still, start stirring (rotating speed=150rpm), and temperature in the kettle is preheating to about 60 ℃ with water bath with thermostatic control.At N 2Protection joins 10mg catalyzer (with the above-mentioned solution flushing of 20mL) in the polymeric kettle down, sheds the still internal pressure then, treats that temperature in the kettle rises to about 65 ℃, feeds ethylene gas, makes the still internal pressure reach 0.8MPa, after five minutes, mixing speed is risen to 250rpm.Bath temperature transfers to 70 ℃.Stop to feed ethene behind the polymerization 1h, with recirculated cooling water temperature in the kettle is reduced to below 50 ℃, gas in the emptying system and discharging obtain granulated polymer after the drying.
Concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M w(g/mol), molecular weight distribution polymerization result data such as (PDI) are listed in table 8.
Table 8
Figure BSA00000355523100481
Embodiment 535M 3Device ethene slurry polymerization is produced ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE)
5M 3After nitrogen blows 1 hour in the reactor, add 2.5 tons of hexanes, in hexane, add the AlEt of 0.5L 3Stirred 40 minutes, and be warmed up to 60 ℃, get 60 gram catalyzer M1 simultaneously, mix with the 50L hexane and stir the AlEt that adds 0.5L down 3Behind the activated catalyst 20 minutes, with nitrogen catalyst solution is pressed into reactor, feed ethene pressure simultaneously to 0.6MPa, be warmed up to 75 ℃, after the polyreaction four hours, stop to feed ethene, vacuum-drying is removed hexane and is obtained 1.2 tons of granular polymers (catalytic activity: 20000g polymkeric substance/g catalyzer, polymkeric substance is designated as P0).Polymers analysis results viscosity-average molecular weight 310 myriagram/moles, M w/ M nBe 3.9,700 microns of median sizes, bulk density 0.39, branching content is less than 1 in per 100000 carbon.
Embodiment 54 10M 3Device ethene slurry polymerization is produced different degree of branching ultrahigh molecular weight polyethylene(UHMWPE) 10M 3After nitrogen blows 1 hour in the reactor, add 5 tons of paraffin oils, in paraffin oil, add the AlEt of 1L 3Stirred 40 minutes, and be warmed up to 80 ℃, get 100 gram catalyzer simultaneously, mix with the 50L paraffin oil and stir the AlEt that adds 1L down 3Behind the activated catalyst 20 minutes, with nitrogen catalyst solution is pressed into reactor, feeds ethene simultaneously to pressure as shown in table 4, polyreaction is after it is as shown in the table time, puts into dry still and removes the paraffin oil drying and obtain granular polymer.
Concrete experiment condition, catalytic activity (g polymkeric substance/g catalyzer), polymericular weight M w(g/mol), molecular weight distribution polymerization result data such as (PDI) are listed in table 9.
Table 9
Figure BSA00000355523100491
Get the polymer P 1-1 (149 microns of median sizes) of different-grain diameter, P1-2 (430 microns of median sizes); P2-1 (141 microns of median sizes), P2-2 (400 microns of median sizes); P3-1 (152 microns of median sizes), P3-2 (410 microns of median sizes) is used for back processing and implementation example.
Embodiment 55 different degree of branching ultrahigh molecular weight polyethylene are equipped with filter core
With ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) sample P 1 and ultrahigh molecular weight polyethylene(UHMWPE) sample P 4 respectively with the curing that after heating while puffing, cools again of 4% sodium bicarbonate, acetone, phenol, obtain the ultra-high molecular mass polyethylene micropore material as filter element, wherein be the filter core L1 that raw material makes with P1, original resistance is 1.3KPa (flow 18Kg/h), and original filtering efficiency is 96%; And be the filter core L2 that raw material makes with P4, original resistance is 1.5KPa (flow 18Kg/h), original filtering efficiency is 94%.The relative L2 of mean pore size that finds L1 by analysis is slightly high, but pore size distribution is narrow.
Embodiment 56 screw extrusion press UHSJ-45-UHSJ-200 go up and produce superhigh molecular weight polyethylene pipe
Utilize commercially available single screw rod ultrahigh molecular weight polyethylene(UHMWPE) forcing machine UHSJ-45-UHSJ-200, when the screw rod top temperature is 210 ℃ in the presence of 0.1% weight carbon black, P1, it is 210 millimeters tubing that P2, P3 and P4 can both extrude internal diameter smoothly, under the situation of power of motor and head pressure operation, the highest extruded velocity of P1 is P4 2.8 times of the highest extruded velocity, P2 is 3.4 times of P4, and P3 is 2.2 times of P4, and P1, P2 extruding pipe material surface ratio P3, P4 extruding pipe material are smooth.When reducing each temperature control section temperature, and when top temperature reduced to 180 ℃, P1 can extrude ganoid tubing smoothly, and P4 can't extrude.
Embodiment 57
The molecular weight contrast of the tubing of under top temperature 210 degree, extruding by polymer P 3, P4
Figure BSA00000355523100501
The ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) single screw extrusion machine of embodiment 58 variable grain sizes is produced superhigh molecular weight polyethylene pipe and sheet material
Utilize commercially available single screw rod ultrahigh molecular weight polyethylene(UHMWPE) forcing machine UHSJ-45-UHSJ-200, when the screw rod top temperature is 210 ℃ in the presence of 0.1% weight carbon black, it is 430 millimeters tubing that P1-1 and P1-2 can both extrude internal diameter smoothly, under the situation of power of motor and head pressure operation, P1-1 is suitable with the highest extruded velocity of P1-2, and the surface is smoother all.After very moment mould place takes opening cutting and roll extrusion, can the production wide cut 1350 millimeters sheet material.
Embodiment 59
The ultrahigh molecular weight polyethylene tubing performance abrasion loss rate (taking the ISO-15527 standard testing) of embodiment 58 preparation and commercially available tubing contrast, by the abrasion loss rate of the tubing of embodiment 57 preparations far below product sold on the market, concrete outcome such as table 10
Table 10
Figure BSA00000355523100511
Embodiment 60 screw extrusion presss are produced superhigh molecular weight polyethylene pipe
Under single screw rod ultrahigh molecular weight polyethylene(UHMWPE) forcing machine and corresponding processing condition, polymer P 1 is not adding any auxiliary agent, or only add external plasticizer (0.5% Zinc Stearate), or add weighting material (0.1% carbon black and 1% nanometer silica gel) and external plasticizer simultaneously, or equal extruding pipe material smoothly under the standard recipe condition of adding weighting material, external plasticizer and internal plasticizer (30% common high density polyethylene(HDPE)), and extrude extruded velocity under the standard recipe far above P4, P5, P6; And P4, P5, P6 is under similarity condition, weighting material, external plasticizer and internal plasticizer lack equally all can not be extruded, can only under standard recipe, extrude, extruding pipe material performance such as table 10: wherein tensile strength and elongation at break are taked the GB/T1040.2-2006 standard testing, and the ISO-15527 standard testing is taked in the mortar abrasion.
Table 10 ultrahigh molecular weight polyethylene(UHMWPE) extruding pipe material The performance test results relatively
Figure BSA00000355523100521
The high-strength superhigh molecular weight polyethylene fibers of embodiment 61 dry production
Polymer P 0 is carried out the high-strength superhigh molecular weight polyethylene fibers of dry production to be researched and produced line and carries out spinning research, carry out the spinning experiment with reference to DSM1600 dawn and DSM800 dawn condition, show sample good spinnability as a result, lessly lousiness occurs and twine the rod phenomenon, the screw rod top hole pressure is more on the low side than other polymer raw material, after spin in the process drafting multiple than using the polymer raw material height, the drawing-off multiplying power can improve 60%, the finished fiber softness, bright in color, the intensity of finished product is the highest can to reach 35cN/dtex., and modulus is the highest can to reach 1500cN/dtex.
The high-strength superhigh molecular weight polyethylene fibers of embodiment 62 wet production
Polymer P 1 is carried out the high-strength superhigh molecular weight polyethylene fibers of wet production to be researched and produced line and carries out spinning research, ripe spinning condition with reference to its P4 carries out the spinning experiment, the result shows good spinnability, the screw rod top hole pressure is lower than P4, after spin in the process drafting multiple than using the P4 height, the drawing-off multiplying power can improve 40%, the finished fiber softness, bright in color, the intensity of finished product is the highest can to reach 35cN/dtex., and modulus is the highest can to reach 1600cN/dtex.

Claims (32)

1. a class load type non-metallocene polyolefin catalyst is characterized in that described load type non-metallocene polyolefin catalyst is made up of magnesium compound and metal complexes, and the mol ratio of described magnesium compound and metal complexes is 10～10000: 1;
Described magnesium compound is the alcohol adduct of magnesium halide, wherein, alcohol content is counted 30%-70% with weight ratio, described alcohol is selected from the Fatty Alcohol(C12-C14 and C12-C18) of C1-C18, at least a in the aromatic alcohol of C6-C10 and the alicyclic ring alcohol of C3-C10, described alcohol by or not by the alkyl of C1-C10 arbitrarily, the alkoxyl group of C1-C10, halogen atom replaces;
Described metal complexes has following molecular structure:
Figure FSA00000355523000011
Wherein:
: refer to coordinate bond;
R 21, R 22Or R 23It is identical or different group, be selected from arbitrarily separately: hydrogen, a kind of alkyl with 1 to 20 carbon atom side chain or straight chain, have 6 to 15 carbon atom fragrance alkyl, optional position on the aryl radical can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 10 carbon atom or is halogen, R 21, R 22Or R 23Can be identical, also can be different;
R 24Or R 25Be selected from arbitrarily separately: hydrogen, a kind of side chain or straight-chain alkyl or aryl radical, each alkyl has 1 to 20 carbon atom, each aryl radical has 6 to 15 carbon atoms, optional position on the aryl radical can be substituted group individually or simultaneously and replace, and each substituted radical has 1 to 10 carbon atom or is halogen; R 24Or R 25It is identical or different group;
Z: oxygen, sulphur, selenium or phosphorus; When Z is oxygen, sulphur or selenium atom, has only R 24Or R 25Existence is to satisfy the valence state needs of oxygen, sulphur or selenium;
M: the 4th group 4 transition metal atom comprises titanium, zirconium or hafnium;
Y: be selected from halogen, have the alkyl of 1 to 10 carbon atom, alkoxyl group or amido (R with 1 to 10 carbon atom 26) 2N-, n X is identical or different, each other in key or Cheng Jian not; R wherein 26Refer to contain the alkyl of 1 to 4 carbon atom;
Described halogen refers to fluorine, chlorine, bromine or iodine;
M:1 or 2;
N:2 or 3.
2. a class load type non-metallocene polyolefin catalyst as claimed in claim 1, it is characterized in that described load type non-metallocene polyolefin catalyst is made up of magnesium compound and metal complexes, the mol ratio of described magnesium compound and metal complexes is 10～2000: 1;
Described magnesium compound is the alcohol adduct of magnesium chloride, and wherein, pure content is counted 30%-70% with weight ratio, described alcohol is selected from a kind of the have alcohol of 1 to 10 carbon atom or the mixture of multiple alcohol, described alcohol can be by the alkyl of any C1-C5, the alkoxyl group of C1-C5, and halogen atom replaces;
Described metal complexes has following molecular structure:
Wherein:
: refer to coordinate bond;
R 21, R 22Or R 23It is identical or different group, be selected from arbitrarily separately: hydrogen, a kind of aryl radical that has 1 to 10 carbon atom side chain or straight-chain alkyl or have 6 to 10 carbon atoms, optional position on the aryl radical can be substituted individually or simultaneously, substituted radical can be side chain or the straight-chain alkyl, the alkoxyl group that contains 1 to 5 carbon atom that contain 1 to 5 carbon atom, contain amido, the halogen of 1 to 5 carbon atom or contain the side chain of 1 to 5 carbon atom or the fluorine-containing alkyl of straight chain, R 21, R 22Or R 23Can be identical, also can be different;
R 24Or R 25Be selected from arbitrarily separately: be hydrogen, a kind of side chain or straight-chain alkyl or aryl, each alkyl has 1 to 20 carbon atom, each aryl has 6 to 10 carbon atoms, optional position on the aryl is substituted individually or simultaneously or is not substituted, and substituted radical can be the side chain or the straight-chain alkyl that contain 1 to 5 carbon atom, contain alkoxyl group, the halogen of 1 to 5 carbon atom or contain the side chain of 1 to 5 carbon atom or the fluorine-containing alkyl of straight chain; R 24Or R 25It is identical or different group;
Z: oxygen, sulphur, selenium or phosphorus, when Z is oxygen, sulphur or selenium atom, have only R 24Or R 25Existence is to satisfy the valence state needs of oxygen, sulphur or selenium atom;
M: the 4th group 4 transition metal atom comprises titanium, zirconium or hafnium;
Y: be selected from halogen;
m：1；
N:2 or 3;
Described halogen refers to fluorine, chlorine, bromine or iodine.
3. the preparation method of a class load type non-metallocene polyolefin catalyst as claimed in claim 1, its feature obtains as follows:
(1) magnesium compound as claimed in claim 1 is contacted 1-24 hour with aluminum alkyls or alkylalumoxane solution in 0-100 ℃; Described aluminum alkyls is selected from one or more mixture of trimethyl aluminium, triethyl aluminum, aluminium isobutyl; Contained alcohol is 1.5-0.8 with the molar ratio computing in described aluminum alkyls and the magnesium compound: 1;
(2) metal complexes as claimed in claim 1 is dissolved in the organic solvent, the magnesium compound after resulting solution and the middle processing of step (1) is contacted 1-24 hour in 0-100 ℃; Described organic solvent is meant can be with described all solvents of metal complexes dissolved; The mol ratio of described magnesium compound and metal complexes is 10～10000: 1;
(3) (2) gained mixture is filtered, use organic solvent washing, final drying becomes flowable pressed powder; Described organic solvent is the alkane of C5-C30, naphthenic hydrocarbon or the mixed alkanes of C5-C30.
4. preparation method as claimed in claim 3 is characterized in that in the magnesium compound described in the step (1) and the alkyl aluminum solutions one or more contact 1-24 hour at 0-60 ℃.
5. preparation method as claimed in claim 3, the solution that it is characterized in that the metal complexes described in the step (2) with handle after magnesium compound contact 1-24 hour at 0-60 ℃.
6. preparation method as claimed in claim 3, it is characterized in that the magnesium compound described in the step (1) is the subsphaeroidal magnesium chloride that contains the spherical magnesium chloride of alcohol or contain alcohol, alcohol content is counted 30%-70% with weight ratio, described alcohol is selected from a kind of alcohol or multiple mixture with alcohol of 1 to 10 carbon atom with 1 to 10 carbon atom, and described alcohol is by the alcohol of the alkoxy or halogen atom of the alkyl of any C1-C10, C1-C10 replacement.
7. preparation method as claimed in claim 3 is characterized in that the consumption of aluminum alkyls described in the step (1) or alkylaluminoxane and the pure content in the magnesium compound are 1.5-1.0 with mol ratio calculating: 1.
8. preparation method as claimed in claim 3 is characterized in that middle aluminum alkyls of step (1) or the used solvent of alkylalumoxane solution are the alkane of 5 to 10 carbon atoms, the naphthenic hydrocarbon of 5 to 10 carbon atoms or their mixed alkanes.
9. preparation method as claimed in claim 3, the solvent that it is characterized in that dissolution of metals title complex in the step (2) is mineral oil or different liquid hydrocarbons, be selected from the alkane with 5 to 10 carbon atoms, aromatic hydrocarbon or both mixtures, perhaps above-mentioned alkane or the aromatic hydrocarbon that is replaced by halogen atom with 5 to 10 carbon atoms.
10. the purposes of a load type non-metallocene polyolefin catalyst as claimed in claim 1 or 2 is characterized in that such load type non-metallocene polyolefin catalyst is used for the slurry polymerization or the vapour phase polymerization of alkene under the promotor effect; Described promotor is an alkylaluminium cpd, alkylaluminoxane, boron fluothane or boron alkyl.
11. the purposes of load type non-metallocene polyolefin catalyst as claimed in claim 10, it is characterized in that such load type non-metallocene polyolefin catalyst is used for preparing polymer particle and is spherical or subglobose polyethylene or polypropylene, polymer particle narrow diameter distribution, particle size range are 100nm-1mm.
12. the purposes of load type non-metallocene polyolefin catalyst as claimed in claim 10, it is characterized in that such load type non-metallocene polyolefin catalyst is 0.1-20MPa at polymerization pressure, polymerization temperature is 20-200 ℃, and hydrogen pressure is the copolymerization of alkene of copolymerization, alpha-olefin and band functional groups of alkene that is used for preparing copolymerization, ethene and the band functional groups of copolymerization, ethene and the cyclic olefin of ethene and alpha-olefin under the condition of 0-0.5Mpa.
13. the purposes of load type non-metallocene polyolefin catalyst as claimed in claim 10, it is characterized in that described promotor be meant triethyl aluminum, methylaluminoxane, modification methylaluminoxane, [B (and 3,5-(CF 3) 2C 6H 3) 4] -,-OSO 2CF 3Or ((3,5-(CF 3) 2) C 6H 3) 4B -
14. a class load type non-metallocene polyolefin catalyst is characterized in that described load type non-metallocene polyolefin catalyst is made up of magnesium compound, porous support and metal complexes;
Wherein:
Described metal complexes is by ML 4Containing heteroatomic polydentate ligand original position with a class generates;
M is meant the 4th group 4 transition metal atom, comprises titanium, zirconium, hafnium;
L is selected from halogen or has the alkyl of 1 to 10 carbon atom, and 4 L are identical or different;
Describedly contain heteroatomic polydentate ligand and have following molecular structure:
Figure FSA00000355523000041
R 1Be H, have the straight chain of 1 to 10 carbon atom or contain side chain alkyl, have 1 to 4 carbon atom haloalkyl, have 2 to 10 carbon atoms thiazolinyl, have 2 to 10 carbon atoms alkynyl, have the phenyl or naphthyl that 4 to 10 carbon atoms contain heterocyclic radical, phenyl, the naphthyl of nitrogen, oxygen or sulphur atom simultaneously and have substituted radical, optional position on phenyl ring or the naphthyl can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 5 carbon atom or is halogen, and substituted radical is identical or different group;
R 3Be H, have the straight chain of 1 to 10 carbon atom or contain side chain alkyl, have 2 to 10 carbon atoms thiazolinyl, have 2 to 10 carbon atoms alkynyl, have the phenyl or naphthyl that 4 to 10 carbon atoms contain heterocyclic radical, phenyl, the naphthyl of nitrogen, oxygen, sulfur heteroatom simultaneously and have substituted radical, on phenyl ring or the naphthyl the optional position be substituted or be not substituted group individually or simultaneously and replace, each substituted radical has 1 to 5 carbon atom or is halogen, substituted radical is identical or different group, and adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
R 2, R 4, R 5, R 6, R 7It is identical or different group, be selected from following group separately arbitrarily: hydrogen, have the straight chain of 1 to 10 carbon atom or contain side chain alkyl, have 2 to 10 carbon atoms thiazolinyl, have alkynyl, the phenyl or naphthyl of 2 to 10 carbon atoms and have the phenyl or naphthyl of substituted radical, optional position on phenyl ring or the naphthyl can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 5 carbon atom or is halogen, substituted radical can be identical, also can be different, adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
R 8, R 9Be selected from following group separately arbitrarily: hydrogen, side chain or straight-chain alkyl, phenyl or naphthyl, have the phenyl or naphthyl of substituted radical with 1 to 20 carbon atom, optional position on phenyl ring or the naphthyl can be substituted group and replace, each substituted radical has 1 to 15 carbon atom or is halogen, R 8Or R 9Be identical or different group, adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
X is O, N, S, Se or P;
When X is O, S or Se, has only a substituent R on the X 8Perhaps R 9
Described halogen refers to fluorine, chlorine, bromine or iodine;
Described magnesium compound is alcohol adduct, the R of magnesium halide, magnesium halide 10 2Mg, (R 11O) 2Mg, (R 12O) MgCl or their mixture; Described R 10, R 11, R 12Be selected from the alkyl or the safing function group of C1-C30 of alkyl, the replacement of C1-C30, described substituting group is a halogen;
Described porous support is selected from the oxide compound of the 13rd, 14 group elements at interior inorganic oxide and oxidation mixture and mixed oxide, the oxidation material for preparing by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound, or organic high molecular polymer; Described silicon compound is a silicon-dioxide, molecular sieve or polynite; Described organic high molecular polymer is a polystyrene.
15. load type non-metallocene polyolefin catalyst as claimed in claim 14 is characterized in that described load type non-metallocene polyolefin catalyst is made up of magnesium compound, porous support and metal complexes;
Wherein:
Described metal complexes is by ML 4Containing heteroatomic polydentate ligand original position with a class generates;
M is meant the 4th group 4 transition metal atom;
L is selected from halogen, and 4 L are identical or different;
Described halogen refers to fluorine, chlorine, bromine or iodine;
Described polydentate ligand has following molecular structure:
Figure FSA00000355523000061
R 1Be thiazolinyl, alkynyl with 2 to 5 carbon atoms with 2 to 5 carbon atoms, have 4 to 10 carbon atoms contain nitrogen, oxygen or sulphur heterocyclic radical, phenyl or naphthyl, have the phenyl or naphthyl of substituted radical, on phenyl ring or the naphthyl the optional position can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 4 carbon atom or is halogen, and substituted radical is identical or different group;
R 3Be H, have the straight chain of 1 to 6 carbon atom or contain side chain alkyl, have 2 to 5 carbon atoms thiazolinyl, have 2 to 5 carbon atoms alkynyl, phenyl or naphthyl, have the phenyl or naphthyl of substituted radical, on phenyl ring or the naphthyl the optional position can be substituted group individually or simultaneously and replace, each substituted radical has 1 to 4 carbon atom or is halogen, and substituted radical is identical or different group;
R 2, R 4, R 5, R 6, R 7It is identical or different group, be selected from H separately arbitrarily, have the straight chain of 1 to 7 carbon atom or contain side chain alkyl, have 2 to 5 carbon atoms thiazolinyl, have 2 to 5 carbon atoms alkynyl, phenyl or naphthyl, have the phenyl or naphthyl of substituted radical, on phenyl ring or the naphthyl the optional position be substituted or be not substituted group individually or simultaneously and replace, each substituted radical on the phenyl ring has 1 to 4 carbon atom or is halogen, substituted radical is identical or different group, and adjacent group becomes ring or Cheng Jiancheng ring not each other in key;
R 8, R 9It is identical or different group, be selected from arbitrarily separately: be side chain or straight-chain alkyl or the phenyl or naphthyl with 1 to 20 carbon atom, phenyl or naphthyl with substituted radical, on phenyl ring or the naphthyl the optional position can be substituted group individually or simultaneously and replace, each substituted radical on the phenyl ring has 1 to 10 carbon atom or is halogen, substituted radical is identical or different group, and adjacent group becomes ring or Cheng Jiancheng ring not each other in key; R 8Or R 9Can be identical, also can be different;
X is O, N, S, Se or P;
When X is O, S or Se, has only a substituent R on the X 8Perhaps R 9
Described magnesium compound is alcohol adduct, the R of magnesium halide, magnesium halide 10 2Mg, (R 11O) 2Mg, R 12OMgCl or their mixture; Described R 10, R 11, R 12Be selected from the alkyl of C1-C30 of alkyl, the replacement of C1-C30;
Described porous support is selected from the oxide compound of the 13rd, 14 group elements at interior inorganic oxide and oxidation mixture and mixed oxide.
16. load type non-metallocene polyolefin catalyst as claimed in claim 14 is characterized in that described load type non-metallocene polyolefin catalyst is made up of magnesium compound, porous support and metal complexes; Described metal complexes is by ML 4Containing heteroatomic polydentate ligand original position with a class generates;
In the wherein said loaded catalyst: the mass ratio of porous support and magnesium compound is 1-3: 1;
The 4th family's metal content: 1-10wt%;
Titanium content is 1-10wt% in preference.
17. the preparation method of a class load type non-metallocene polyolefin catalyst as claimed in claim 14 is characterized in that described load type non-metallocene polyolefin catalyst obtains by following steps:
(1) with magnesium compound metallizing thing ML 4With the mol ratio is 0.5-5: 1 is dissolved in tetrahydrofuran (THF), obtains the tetrahydrofuran solution of magnesium compound metallizing thing, and wherein M, L are as described in the claim 14;
(2) in the solution described in the step (1), add porous support, obtain mixed serum;
(3) add precipitation agent in the mixed serum that forms in step (2) and make it precipitation, filtration, washing, dry this throw out obtain complex carrier I,
(4) in complex carrier I, continue to add metallic compound ML 4, wherein the mol ratio of metallic compound and magnesium compound is 0.5-5: 1, pass through filtration, washing, drying then, and obtain complex carrier II;
(5) add the polydentate ligand described in the claim 1 in described complex carrier II, filtration, washing, drying obtain Nonmetallocene polyolefine catalyst;
Described magnesium compound is alcohol adduct, the R of magnesium halide, magnesium halide 10 2Mg, (R 11O) 2Mg, R 12OMgCl or their mixture; Described R 10, R 11, R 12Be selected from the alkyl of C1-C30 of alkyl, the replacement of C1-C30;
Described porous support is selected from the oxide compound of the 13rd, 14 group elements at interior inorganic oxide and oxidation mixture and mixed oxide, polyethylene or styrene polymer; Preferred silicon compound, described silicon compound is one or more in silicon-dioxide, aluminum oxide, molecular sieve, the polynite;
Described precipitation agent is mineral oil or different liquid hydrocarbons, is selected from the mixed alkanes of alkane, naphthenic hydrocarbon or above-mentioned alkane from C5-C30;
The mol ratio of magnesium compound metallizing thing is 1-5: 1;
The mol ratio of titanium content is 1-1.2 among described polydentate ligand and the complex carrier II: 1;
The used solvent of described washing is the alkane of C5-C30, naphthenic hydrocarbon or mixed alkanes;
The temperature of reaction of described tetrahydrofuran (THF) dissolved magnesium compound and metallic compound is 30-80 ℃, and the reaction times is 1-24 hour;
Described porous support is 1-3 with the ratio of the quality of magnesium compound: 1;
The volume ratio of described precipitation agent and tetrahydrofuran (THF) is 0.5-3: 1.
18. the purposes as claim 10 and 14 described load type non-metallocene polyolefin catalysts is characterized in that described load type non-metallocene polyolefin catalyst is used to prepare ultrahigh molecular weight polyethylene(UHMWPE).
19. the purposes of a class load type non-metallocene polyolefin catalyst as claimed in claim 14, it is characterized in that described preparation ultrahigh molecular weight polyethylene(UHMWPE) is under the effect of promotor, ethylene pressure is 0.1-20MPa, and polymerization temperature is 20-200 ℃, and polymerization time is 1-24h;
Described promotor is meant trialkylaluminium, alkylaluminoxane;
Described promotor is 1-3000 in aluminium element and described load type non-metallocene polyolefin catalyst in the mol ratio of titanium elements: 1.
20. the purposes of a class load type non-metallocene polyolefin catalyst as claimed in claim 19, it is characterized in that described promotor is a triethyl aluminum, is 15-200 in aluminium element triethyl aluminum and described load type non-metallocene polyolefin catalyst in the mol ratio of titanium elements: 1.
21. the purposes of a class load type non-metallocene polyolefin catalyst as claimed in claim 19 is characterized in that polymerization pressure is 0.1-5MPa, polymerization temperature is 40-90 ℃.
22. a ultrahigh molecular weight polyethylene(UHMWPE) is characterized in that described ultrahigh molecular weight polyethylene(UHMWPE) has the ultralow degree of branching.
23. a ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE), it is characterized in that containing in per 100000 skeleton carbon atoms the side chain number is 0-2.
24. ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) as claimed in claim 23 is characterized in that described poly dispersed index range is 2-10.
25. ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) as claimed in claim 23, it is characterized in that described poly molecular weight ranges is that 50 myriagram/moles are to 1000 myriagram/moles, poly dispersed index range is 2-6, and the bulk density scope is 0.20-0.52.
26. ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) as claimed in claim 24, it is characterized in that described poly molecular weight ranges is that 150 myriagram/moles are to 700 myriagram/moles, poly dispersed index range is 2-6, and the bulk density scope is 0.20-0.52.
27. ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) as claimed in claim 23 is characterized in that under the situation of not adding processing aid, can extrude on existing processing ultrahigh molecular weight polyethylene(UHMWPE) extrusion device; Described processing aid refers to reduce the softening agent of melt viscosity, relative low-molecular weight polymer or liquid crystal polymer, but does not comprise carbon black, silica gel or aluminum oxide enhancing mineral filler; Described relative low-molecular weight polymer is meant the common high density polyethylene(HDPE) of molecular weight at 5-30 myriagram/mole.
28. ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) as claimed in claim 27, when it is characterized in that adopting described ultralow degree of branching ultrahigh molecular weight polyethylene to be equipped with tubing, bar, sheet material, filter core/millipore filtration or high-strength high-modulus fibre, extruded velocity be other same molecular amount ultrahigh molecular weight polyethylene(UHMWPE) under same processing conditions more than 2 times or 2 times.
29. ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) as claimed in claim 23, but it is characterized in that in gel spinning prepares the preparation process of high-strength and high-modulus ultrahigh molecular weight polyethylene fibre, having screw pressure low, after spin the high characteristics of ultra-drawing multiple in the process.
30. the purposes of a ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) as claimed in claim 23 is characterized in that being used to prepare tubing, bar, sheet material, filter core filter membrane, millipore filtration or high-strength high-modulus fibre.
31. the purposes of ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) as claimed in claim 30 is characterized in that the intensity of described high-strength high-modulus fibre reaches 35cN/dtex., modulus can reach 1600cN/dtex.
32. the purposes of ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE) as claimed in claim 30, the molecular weight that it is characterized in that described tubing, bar, sheet material, filter core filter membrane, millipore filtration or high-strength high-modulus fibre goods are that 50 myriagram/moles are to 500 myriagram/moles.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1359396A (en) * 1999-07-15 2002-07-17 陶氏化学公司 High density ethylene homopolymers and blend compositions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1197500B1 (en) * 2000-01-26 2011-05-18 Mitsui Chemicals, Inc. Olefin triblock copolymers and production processes thereof
CN1256351C (en) * 2001-07-23 2006-05-17 中国科学院上海有机化学研究所 Catalyst for polymerization and copolymerization of olefine and its synthesis and use
CN100569734C (en) * 2006-05-22 2009-12-16 中国科学院上海有机化学研究所 One class contains heteroatomic organic compound and the application in Ziegler-Natta catalyst thereof
CN1887924B (en) * 2006-07-14 2010-05-12 中国科学院上海有机化学研究所 Use of non-metallocene polyolefin catalyst in synthesizing ethylene/polar monomer copolymer
CN101654492B (en) * 2008-08-21 2012-06-20 中国石化扬子石油化工有限公司 Super-high molecular polyethylene and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1359396A (en) * 1999-07-15 2002-07-17 陶氏化学公司 High density ethylene homopolymers and blend compositions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DARIUSZ M. BIELIN"SKI TE. AL: "Ion bombardment of polyethylene-influence of polymer structure", 《VACUUM》 *
MASARU MATSUO ET. AL: "Phase Separation of Several Kinds of Polyethylene Solution under the Gelation/Crystallization Process", 《MACROMOLECULES》 *

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