CN105017625B

CN105017625B - A kind of ethylene-alpha-olefin copolymer, its manufacture method and its application

Info

Publication number: CN105017625B
Application number: CN201410149611.2A
Authority: CN
Inventors: 李传峰; 任鸿平; 易玉明; 汪文睿; 郭峰; 阚林; 柏基业; 杨爱武
Original assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Priority date: 2014-04-15
Filing date: 2014-04-15
Publication date: 2017-07-14
Anticipated expiration: 2034-04-15
Also published as: CN105017625A

Abstract

The present invention relates to a kind of ethylene-alpha-olefin copolymer, its manufacture method and its application in moulded products manufacture.The ethylene-alpha-olefin copolymer shows the processing characteristics and mechanical property of balancing good compared with prior art.

Description

A kind of ethene-alpha-olefin copolymer, its manufacture method and its application

Technical field

The present invention relates to a kind of ethylene copolymer.Specifically, the present invention relates to a kind of ethene-alpha-olefin copolymer, its Manufacture method and its application in moulded products manufacture.

Background technology

Polyolefin is the synthetic resin of yield maximum in the world, with boundless application market.Polyolefin is mainly wrapped Include polyethylene（PE）, polypropylene（PP）And the copolymer of the alpha-olefin such as ethene and propylene, 1- butylene, 1- hexenes and 1- octenes.

In general, the intensity of polyolefin such as polyethylene depends on its molecular weight, and molecular weight is higher, the intensity of material, Elasticity and environmental stress cracking resistance are higher, but the processing characteristics of the higher polyethylene of molecular weight can be deteriorated.Known to this It is to improve the molecular weight distribution of polymer to realize the balance of polymer rigid, toughness and processing characteristics three, i.e., in molecule The relatively low component of the molecular weight for increasing to improve processing characteristics in higher polyvinyl resin is measured, so that the molecular weight of polyethylene Bimodal distribution is presented.Double peak weight distributing polyethylene refer to molecular weight distribution in bimodal pattern linear polyethylene and ethene-α- The blend of olefin copolymer, including low molecule amount, lightly branched part and HMW, highly -branched degree two parts.Bimodal poly- second High molecular weight moieties can assign its good intensity, toughness and environmental stress cracking resistance in alkene（ESCR）, and low molecule amount Part can ensure the rigidity of polymer, while there is provided lubrication to improve the processing characteristics of resin.Due to bimodal polyethylene The processing characteristics and performance of material has been reached good balance, have become the weight of polyolefin synthetic resin high performance Want direction.Double-peak high-density polytene, makes the more difficult film of original production and processing and tubing have the development advanced by leaps and bounds, film Become easy processing, tensile strength is improved；Tubing also has breakthrough in processing characteristics and environmental stress cracking resistance.

Chinese patent 200810213620.8 discloses a kind of ethene-alpha-olefin copolymer.Because molecular weight distribution is narrow, The ethene-alpha-olefin copolymer is only used for manufacturing polyethylene crosslinking product, and is not suitable for manufacture rotomoulded articles and high-performance pipe Material.Moreover, in the manufacture method of the ethene-alpha-olefin copolymer disclosed in the Chinese patent, the catalysis of polymerization catalyst is lived Property can not be fully played, and copolymerization effect also has the leeway further improved.

Chinese patent 200810213619.5 discloses a kind of ultra-high molecular weight polyethylene.Because molecular weight is higher, this surpasses The processing characteristics of High molecular weight polyethylene is poor, can be only applied to the high abrasion goods such as extruding pipe material under sintering process molding and low speed, Application is smaller.

Therefore, current present situation is to be still required for a kind of ethene-alpha-olefin copolymer, and it has appropriate molecular weight point The characteristic such as cloth and oligomer, and take into account processing characteristics and mechanical property.Prior art is also required to a kind of ethene-alpha-olefin and is total to The manufacture method of polymers, it enables to the catalytic activity of polymerization catalyst more to be fully played, and copolymerization effect It is more notable.

The content of the invention

The present inventor has found by diligent research on the basis of existing technology, by using a kind of specific manufacturer Method manufactures the ethene-alpha-olefin copolymer, it is possible to solves foregoing problems, and this completes the present invention.

Specifically, the present invention relates to the content of following aspect.

1. a kind of ethene-alpha-olefin copolymer, it is characterised in that the monomeric unit with derived from ethylene is with being derived from Selected from C3-C12 alpha-olefins（It is preferred that C4-C8 alpha-olefins）At least one alpha-olefin monomeric unit, its heap density be 0.33 ~ 0.50g/cm³（It is preferred that 0.35 ~ 0.50g/cm³, more preferably 0.38 ~ 0.45g/cm³）, oligomer is less than 2g/L, micro- less than 75 It is 0.02 ~ 20g/10min that the fine powder content of rice, which is less than the melt index determined under the conditions of 3 weight %, 190 DEG C and 2.16 kilograms, is divided Son amount distribution Mw/Mn is 5 ~ 40, and density is 0.935-0.960g/cm³, average grain diameter is 200-1000 microns, and relative to The weight % of gross weight 100 of the ethene-alpha-olefin copolymer, the content of the monomeric unit of the derived from ethylene for 88 ~ 99.8 weight %, the content of the monomeric unit derived from the alpha-olefin is 0.2 ~ 12 weight %.

2. a kind of manufacture method of ethene-alpha-olefin copolymer, it is characterised in that comprise the following steps A and B or step Rapid A' and B'：

Step A：Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta, At least one in alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt（It is preferred that in aikyiaiurnirsoxan beta and alkyl aluminum At least one）As co-catalyst, make the co-catalyst in terms of aluminium or boron and the master in terms of central metal atom The mol ratio of catalyst reaches 1~1000：1, preferably 5~500：1, more preferably 10~100：1, polymerisation stagnation pressure 0.2 ~ 2.0MPa（It is preferred that 0.3 ~ 1.5MPa, most preferably 0.4-0.8MPa）, hydrogen and ethylene partial pressure compare 0.01-1：1（It is preferred that 0.02- 0.8：1, most preferably 0.03-0.5：1）With 20 ~ 120 DEG C of polymeric reaction temperature（It is preferred that 60 ~ 100 DEG C, more preferably 75 ~ 95 DEG C）Bar Under part, make ethylene homo, obtain A stage polymers, and

Step B：Using slurry polymerization process, in the presence of the A stage polymers, polymerisation stagnation pressure 0.1 ~ 2.0MPa（It is preferred that 0.2 ~ 1.0MPa, most preferably 0.3-0.6MPa）, hydrogen and ethylene partial pressure compare 0.01-0.5：1（It is preferred that 0.02- 0.4：1, most preferably 0.03-0.3：1）, 20 ~ 120 DEG C of polymeric reaction temperature（It is preferred that 60 ~ 100 DEG C, more preferably 75 ~ 95 DEG C）With altogether Polycondensation monomer addition is 0.01 ~ 0.3 gram/milligram major catalyst（It is preferred that 0.015 ~ 0.25 gram/milligram major catalyst, more preferably 0.02 ~ 0.2 gram/milligram major catalyst）Under conditions of, make ethene with being selected from C3-C12 alpha-olefins（It is preferred that C4-C8 alpha-olefins） At least one alpha-olefin copolymer, obtain the ethene-alpha-olefin copolymer；

Or

Step A'：Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from alumina At least one in alkane, alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt（It is preferred that aikyiaiurnirsoxan beta and alkyl aluminum In at least one）As co-catalyst, make the co-catalyst in terms of aluminium or boron with described in terms of central metal atom The mol ratio of major catalyst reaches 1~1000：1, preferably 5~500：1, more preferably 10~100：1, polymerisation stagnation pressure 0.1 ~ 2.0MPa（It is preferred that 0.2 ~ 1.0MPa, most preferably 0.3-0.6MPa）, hydrogen and ethylene partial pressure compare 0.01-0.5：1（It is preferred that 0.02- 0.4：1, most preferably 0.03-0.3：1）, 20 ~ 120 DEG C of polymeric reaction temperature（It is preferred that 60 ~ 100 DEG C, more preferably 75 ~ 95 DEG C）With altogether Polycondensation monomer addition is 0.01 ~ 0.3 gram/milligram major catalyst（It is preferred that 0.015 ~ 0.25 gram/milligram major catalyst, more preferably 0.02 ~ 0.2 gram/milligram major catalyst）Under conditions of, make ethene with being selected from C3-C12 alpha-olefins（It is preferred that C4-C8 alpha-olefins） At least one alpha-olefin copolymer, obtain A' stage polymers, and

Step B'：Using slurry polymerization process, in the presence of the A' stage polymers, polymerisation stagnation pressure 0.2 ~ 2.0MPa（It is preferred that 0.3 ~ 1.5MPa, most preferably 0.4-0.8MPa）, hydrogen and ethylene partial pressure compare 0.01-1：1（It is preferred that 0.02- 0.8：1, most preferably 0.03-0.5：1）With 20 ~ 120 DEG C of polymeric reaction temperature（It is preferred that 60 ~ 100 DEG C, more preferably 75 ~ 95 DEG C）Bar Make ethylene homo under part, obtain the ethene-alpha-olefin copolymer.

3. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the A stage polymers account for institute State the 0.1-90wt% of ethene-alpha-olefin copolymer gross mass, more preferably preferably 15-85wt%, 30-70wt%, or the A' ranks Section polymer accounts for the 10-99.9wt%, more preferably preferably 15-85wt%, 30- of the ethene-alpha-olefin copolymer gross mass 70wt%。

4. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the load type non-metallocene is urged Agent is manufactured by the preparation method comprised the following steps：

Magnesium compound and Nonmetallocene part is dissolved in the presence of an alcohol in solvent, obtain the step of magnesium compound solution Suddenly；

Porous carrier is set to be mixed with the magnesium compound solution, the step of obtaining mixed serum；

Precipitating reagent is added into the mixed serum or the mixed serum is dried, the step of obtaining complex carrier；

The complex carrier is contacted with the chemical treatments selected from IV B races metallic compound, obtain the support type non- The step of metallocene catalyst,

The preparation method, which is optionally additionally included in, to be made before the complex carrier contacts with the chemical treatments, with selected from Aikyiaiurnirsoxan beta, alkyl aluminum or the step of helping the chemical treatments pretreatment complex carrier of its any combination.

5. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the porous carrier is selected from alkene Homopolymer or copolymer, polyvinyl alcohol or its copolymer, cyclodextrin, polyester or copolyesters, polyamide or copolyamide, vinyl chloride Homopolymer or copolymer, Voncoat R 3310 or copolymer, methacrylate homopolymer or copolymer, styrene homopolymers Or copolymer, the partial cross-linked form of these homopolymers or copolymer, the A of the periodic table of elements II, III A, IV A or IV B races metal Refractory oxides or one kind or many in infusibility composite oxides, clay, molecular sieve, mica, montmorillonite, bentonite and diatomite Kind, it is preferably selected from partial cross-linked styrene polymer, silica, aluminum oxide, magnesia, oxidation sial, oxidation magnalium, two One or more in titanium oxide, molecular sieve and montmorillonite, are more preferably selected from silica, wherein the porous carrier is optionally passed through Cross thermal activation treatment and/or handled by the chemical activation of the IV B races metallic compound, the magnesium compound is selected from halogenation One or more in magnesium, Alkoxymagnesium halides, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium, are preferably selected From the one or more in magnesium halide, more preferably magnesium chloride.

6. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the solvent is selected from C_6-12Fragrance Hydrocarbon, halo C_6-12One or more in aromatic hydrocarbon, ester and ether, preferably C_6-12One or more in aromatic hydrocarbon and tetrahydrofuran, Most preferably tetrahydrofuran, one or more of the alcohol in fatty alcohol, aromatic alcohol and alicyclic ring alcohol, wherein the alcohol optionally quilt Selected from halogen atom or C_1-6The substituent substitution of alkoxy, the alcohol is preferably selected from the one or more in fatty alcohol, more preferably selected From the one or more in ethanol and butanol.

7. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the Nonmetallocene part is selected from One or more in compound with following chemical structural formula：

,

It is preferably selected from the compound with following chemical structural formula（A）And compound（B）In one or more：

With,

（A）（B）

It is more preferably selected from the compound with following chemical structural formula（A-1）To compound（A-4）And compound（B-1）Extremely Compound（B-4）In one or more：

、、

（A-1）（A-2）

、、

（A-3）（A-4）

、、

（B-1）（B-2）

With,

（B-3）（B-4）

In above all of chemical structural formula,

Q is 0 or 1；

D is 0 or 1；

A be selected from oxygen atom, sulphur atom, selenium atom,、-NR²³R²⁴、-N(O)R²⁵R²⁶、、-PR²⁸R²⁹、-P(O) R³⁰OR³¹, sulfuryl, sulfoxide group or-Se (O) R³⁹, wherein N, O, S, Se and P be respectively coordination atom；

B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C₁- C₃₀Alkyl；

D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C₁- C₃₀Alkyl, Sulfuryl or sulfoxide group, wherein N, O, S, Se and P are respectively coordination atom；

E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group, wherein N, O, S, Se Coordination atom is respectively with P；

F be selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are respectively coordination atom；

G is selected from C₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl or safing function group；

Y be selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P be each From for coordination atom；

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group, wherein N, O, S, Se Coordination atom is respectively with P；

Represent singly-bound or double bond；

- represent covalent bond or ionic bond；

R¹To R⁴、R⁶To R²¹It is each independently selected from hydrogen, C₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl or safing function Group, R²²To R³⁶、R³⁸And R³⁹It is each independently selected from hydrogen, C₁- C₃₀Alkyl or substituted C₁- C₃₀Alkyl, above-mentioned group is each other Between can be the same or different, wherein adjacent group can combine togather bonding or cyclization, be preferably formed as aromatic series Ring；

The safing function group be selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, containing sulfenyl Roll into a ball, containing tin group, C₁- C₁₀Ester group and nitro；

R⁵Lone pair electrons, hydrogen, C on nitrogen₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl, oxy radical, sulfur-containing group, Nitrogen-containing group, containing seleno group or phosphorus-containing groups；Work as R⁵For oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorous-containigroups groups During group, R⁵In N, O, S, P and Se can be coordinated as coordination with atom with the B races metallic atom of center IV；

The substituted C₁- C₃₀Alkyl, which is selected from, carries one or more halogens or C₁- C₃₀Alkyl is used as substituent C₁- C₃₀Alkyl,

The one kind or many of the Nonmetallocene part further preferably in the compound with following chemical structural formula Kind：

、、、、With,

The Nonmetallocene part is most preferably selected from the one or more in the compound with following chemical structural formula：

With。

8. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein,

The halogen is selected from F, Cl, Br or I；

The nitrogen-containing group is selected from、-NR²³R²⁴、-T-NR²³R²⁴Or-N (O) R²⁵R²⁶；

The phosphorus-containing groups are selected from、-PR²⁸R²⁹、-P(O)R³⁰R³¹Or-P (O) R³²(OR³³)；

The oxy radical is selected from hydroxyl ,-OR³⁴With-T-OR³⁴；

The sulfur-containing group is selected from-SR³⁵、-T-SR³⁵、-S(O)R³⁶Or-T-SO₂R³⁷；

The group containing seleno is selected from-SeR³⁸、-T-SeR³⁸、-Se(O)R³⁹Or-T-Se (O) R³⁹；

The group T is selected from C₁- C₃₀Alkyl or substituted C₁- C₃₀Alkyl；

The R³⁷Selected from hydrogen, C₁- C₃₀Alkyl or substituted C₁- C₃₀Alkyl；

The C₁- C₃₀Alkyl is selected from C₁- C₃₀Alkyl, C₇- C₃₀Alkaryl, C₇- C₃₀Aralkyl, C₃- C₃₀Ring-type alkane Base, C₂- C₃₀Alkenyl, C₂- C₃₀Alkynyl, C₆- C₃₀Aryl, C₈- C₃₀Condensed ring radical or C₄- C₃₀Heterocyclic radical, wherein the heterocycle Base contains the 1-3 hetero atoms for being selected from nitrogen-atoms, oxygen atom or sulphur atom；

The silicon-containing group is selected from-SiR⁴²R⁴³R⁴⁴Or-T-SiR⁴⁵；

The germanic group is selected from-GeR⁴⁶R⁴⁷R⁴⁸Or-T-GeR⁴⁹；

It is described to be selected from-SnR containing tin group⁵⁰R⁵¹R⁵²、-T-SnR⁵³Or-T-Sn (O) R⁵⁴；

The R⁴²To R⁵⁴It is each independently selected from hydrogen, foregoing C₁- C₃₀Alkyl or foregoing substituted C₁- C₃₀Alkyl, it is above-mentioned Group can be the same or different to each other, and wherein adjacent group can combine togather bonding or cyclization, and

The group T is as previously defined.

9. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the magnesium in terms of Mg elements Compound is 1 with the mol ratio of the Nonmetallocene part：0.0001-1, preferably 1：0.0002-0.4, more preferably 1：0.0008- 0.2, further preferred 1：The ratio of 0.001-0.1, the magnesium compound and the solvent is 1mol：75~400ml, preferably 1mol：150~300ml, more preferably 1mol：200~250ml, mole of the magnesium compound and the alcohol in terms of Mg elements Than for 1：0.02~4.00, preferably 1：0.05~3.00, more preferably 1：0.10~2.50, the magnesium in terms of magnesium compound solid Compound is 1 with the mass ratio of the porous carrier：0.1-20, preferably 1：0.5-10, the body of the precipitating reagent and the solvent Product is than being 1：0.2~5, preferably 1：0.5~2, more preferably 1：0.8~1.5, the complex carrier in terms of Mg elements with IVB The mol ratio of the chemical treatments of race's elemental metal is 1：0.01-1, preferably 1：0.01-0.50, more preferably 1：0.10- 0.30, and the complex carrier counted using Mg elements with to help the mol ratio of chemical treatments as 1 described in Al elements are counted：0- 1.0, preferably 1：0-0.5, more preferably 1：0.1-0.5.

10. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the precipitating reagent be selected from alkane, One or more in cycloalkane, halogenated alkane and halo cycloalkane, are preferably selected from pentane, hexane, heptane, octane, nonane, the last of the ten Heavenly stems Alkane, hexamethylene, pentamethylene, cycloheptane, cyclodecane, cyclononane, dichloromethane, dichloro hexane, two chloroheptanes, chloroform, three Chloroethanes, three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane, three NBBs, chloro ring Pentane, chlorocyclohexane, chloro cycloheptane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromo ring One or more in hexane, bromo cycloheptane, bromo cyclooctane, bromo cyclononane and bromo cyclodecane, further preferably choosing One or more from hexane, heptane, decane and hexamethylene, most preferably hexane.

11. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the IV B races metallic compound Selected from IV B races metal halide, IV B races metal alkyl compound, IV B races metal alkoxide, IV B races metal alkyl halogen One or more in compound and IV B races metal alkoxide halide, are preferably selected from one kind or many in IV B races metal halide Kind, it is more preferably selected from TiCl₄、TiBr₄、ZrCl₄、ZrBr₄、HfCl₄And HfBr₄In one or more, be most preferably selected from TiCl₄ And ZrCl₄In one or more, the aikyiaiurnirsoxan beta be selected from MAO, ethylaluminoxane, isobutyl aluminium alkoxide and positive fourth One or more in base aikyiaiurnirsoxan beta, are more preferably selected from the one or more in MAO and isobutyl aluminium alkoxide, and institute State alkyl aluminum and be selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminums, triisopentyl aluminium, three just One or more in amyl group aluminium, three hexyl aluminium, three isohesyl aluminium, diethylmethyl aluminium and dimethyl ethyl aluminium, are preferably selected from One or more in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, are most preferably selected from triethyl aluminum and three different One or more in butyl aluminium.

12. a kind of polymer composition, the ethene-alpha-olefin copolymer comprising any preceding aspect or by foregoing The ethene-alpha-olefin copolymer of the manufacture method manufacture of the ethene-alpha-olefin copolymer of either side, and antioxidant, optionally Also include the one or more in halogen-absorber and pigment.

13. a kind of moulded products, are manufactured by the polymer composition and shaping of melt-processed any preceding aspect.

Technique effect

According to the ethene-alpha-olefin copolymer of the present invention, compared with prior art, uniform particle sizes, molecular weight distribution is appropriate, Oligomer is low, and comonomer distribution is rationally and flexibly adjustable, thus shows the processing characteristics and mechanical property of balancing good Can, it is very suitable for the moulded products such as manufacture high performance pipe, rotomoulded articles, injection-molded item and film.

According to the manufacture method of the ethene-alpha-olefin copolymer of the present invention, compared with prior art, polymerization catalyst is urged Change activity more to be fully played, copolymerization effect is more notable, and technological parameter is flexibly adjustable, is conducive to producing knot Structure parameter（Type, molecular weight and the molecular weight distribution of such as monomer and comonomer, the content of comonomer and its distribution etc.） Comply with specific requirement or needs and the ethene-alpha-olefin copolymer of flexible customization of moulded products.

By using the ethene-alpha-olefin copolymer of the present invention, it is possible to produce have excellent mechanical property concurrently and excellent Processing characteristics polymer composition, and the moulded products manufactured using the polymer composition show long-term usability Can excellent and anti-cracking performance it is excellent the features such as.

According to the present invention, pass through two sections of polymerizations（Homopolymerization section+copolymerization section）Mode obtain the ethene-alpha-olefin copolymerization Thing, wherein homopolymerization section are conducive to improving processing characteristics, and copolymerization Duan Ze is conducive to improving mechanical property.Therefore, it is equal by regulation The relative scale of poly- section and copolymerization section, can neatly adjust the processing characteristics and mechanical property of product copolymer.Such as, if Need higher processing characteristics, then can properly increase the ratio of homopolymerization section, and if necessary to higher mechanical property, then can be with Properly increase the ratio of copolymerization section.

Embodiment

The embodiment to the present invention is described in detail below, it should be noted however that the protection of the present invention Scope is not limited to these specific embodiments, but determined by claims of annex.

Or the implication is beyond those skilled in the art's in the context of the present invention, unless otherwise defined explicitly, Understand hydrocarbon or hydrocarbon derivative group more than scope, 3 carbon atoms（Such as propyl group, propoxyl group, butyl, butane, butylene, butylene Base, hexane etc.）Identical implication during with titled with prefix " just " is respectively provided with when not titled with prefix " just ".Such as, propyl group is typically managed Solve as n-propyl, and butyl is generally understood as normal-butyl, unless otherwise clear and definite.

In this manual, in order to avoid statement is complicated, not for its clear and definite valency of each substituent or group of compound Key-like condition be monovalence, divalence, trivalent or tetravalence etc., those skilled in the art can be according to these substituents or group（Than As described in this specification or definition group G, D, B, A and F etc.）Location or institute on the structural formula of respective compound The substitution situation of performance specifically judges, and for being selected in these substituents or group given a definition that from this specification In the position or the definition for replacing the valence link situation of situation to be adapted to.

All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference. Unless otherwise defined, all technologies and scientific terminology used by this specification all have containing for those skilled in the art's routine understanding Justice.In case of conflict, the definition by this specification is defined.

When this specification with prefix " as well known to those skilled in the art ", " prior art " or its similar term exports material When material, material, method, step, device or part etc., object derived from the prefix is covered this area when the application is proposed and routinely made Those, but also include also being of little use at present, it will but become those art-recognized for suitable for similar purpose.

In the context of the present specification, in addition to the content clearly stated, any matters or item do not mentioned are equal Directly be applicable it is known in the art those without carry out it is any change.Moreover, any embodiment described herein can be with Freely combined with one or more other embodiments described herein, thus formed by technical scheme or technological thought regard For original disclosure of the invention or a part for original description, and be not considered as not disclosing or be expected herein it is new in Hold, unless those skilled in the art think that the combination is substantially irrational.

In the case where not clearly indicating, all percentages, number, ratio being previously mentioned in this specification etc. be all with On the basis of weight, unless do not met the conventional understanding of those skilled in the art when on the basis of weight.

According to the present invention, it is related to a kind of ethene-alpha-olefin copolymer.The ethene-alpha-olefin copolymer is that have to derive From the copolymer of the monomeric unit and the monomeric unit derived from least one alpha-olefin selected from C3-C12 alpha-olefins of ethene, It is preferred that the monomeric unit with derived from ethylene and the monomer list derived from least one alpha-olefin selected from C4-C8 alpha-olefins The copolymer of member.

According to the present invention, as the alpha-olefin, such as can enumerate propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- heptene, 1- octenes, 4-methyl-1-pentene, 1- laurylenes, 4- methyl isophthalic acids-hexene etc., preferably 1- butylene, 1- hexenes, 4- methyl-1-pentenes Alkene, 1- octenes, more preferably 1- hexenes, 4-methyl-1-pentene, 1- octenes.These alpha-olefins can be used alone, or can be by it In two or more be applied in combination with any required ratio.

It is total relative to the ethene-alpha-olefin copolymer in the ethene-alpha-olefin copolymer according to the present invention The weight % of weight 100, the content of the monomeric unit derived from the alpha-olefin is generally 0.2 ~ 12 weight %, preferably 1.0 ~ 10 weight %, more preferably 1.2 ~ 6 weight %.

According to the present invention, the heap density of the ethene-alpha-olefin copolymer is 0.33 ~ 0.50g/cm³, preferably 0.35 ~ 0.50g/cm³, more preferably 0.38 ~ 0.45g/cm³.The measure reference standard GB 1636-79 of the heap density are carried out（Unit is g/ cm³）.

According to the present invention, the oligomer of the ethene-alpha-olefin copolymer is less than 2g/L.Its method of testing is in mistake Filter or the filtrate center line that centrifuges out takes out 1 liter of solvent, under the conditions of higher than solvent boiling point or closed vacuumize abundant drying Remaining material gross mass after solvent.Its content height mainly determined by catalyst performance and polymeric reaction condition, while It is relevant with polymer solvent and filtering or centrifugation temperature.

According to the present invention, the fine powder of the ethene-alpha-olefin copolymer（Less than 75 microns）Content is less than 3 weight %.It is described Fine powder content uses sieve method, and the powder of the copolymer is passed through into 200 mesh（75 microns of aperture）Sieved through sieve, by fine powder after sieving Quality divided by the gross mass of copolymer are measured.

According to the present invention, the melt index of the ethene-alpha-olefin copolymer（190 DEG C, 2.16 kilograms）For 0.02 ~ 20g/ 10min.The measure reference standard GB T 3682-2000 of the melt index are carried out（Unit is g/10min）.

According to the present invention, the molecular weight distribution mw/mn of the ethene-alpha-olefin copolymer is 5 ~ 40.The molecular weight point Cloth Mw/Mn is measured using the GPC V2000 type gel chromatography analyzers of WATERS companies of the U.S., from 4 Agilent PLgel Olexis type chromatographic columns, with 1,2,4- trichloro-benzenes for mobile phase, temperature during measure is 150 DEG C.

According to the present invention, the density of the ethene-alpha-olefin copolymer is 0.935-0.960g/cm³.The survey of the density Determine reference standard GB/T 1033-86 progress（Unit is g/cm³）.

According to the present invention, the average grain diameter of the ethene-alpha-olefin copolymer is 200-1000 microns.The average grain diameter Analysis is carried out on Beckman Coulter LS230 type laser particle size analyzers, and its particle size determination scope is 0.04 ~ 2000 micro- Rice.

According to the present invention, the ethene-alpha-olefin copolymer can be entered by comprising the following steps A and B manufacture method A Row manufacture.

Specifically, the present invention relates to a kind of manufacture method A of ethene-alpha-olefin copolymer, it is characterised in that including with Lower step：

Step A：Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta, It is at least one as co-catalyst in alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, it is anti-in polymerization 0.2 ~ 2.0MPa of stagnation pressure is answered, hydrogen and ethylene partial pressure compare 0.01-1：1st, ethene is made under conditions of 20 ~ 120 DEG C of polymeric reaction temperature Homopolymerization, obtains A stage polymers.

According to the present invention, the step A polymerisation stagnation pressure is generally 0.2 ~ 2.0MPa, preferably 0.3 ~ 1.5MPa, most It is preferred that 0.4-0.8MPa.

According to the present invention, the step A hydrogen and ethylene partial pressure ratio is generally 0.01-1：1, preferably 0.02-0.8：1, Most preferably 0.03-0.5：1.

According to the present invention, the step A polymeric reaction temperature is generally 20 ~ 120 DEG C, preferably 60 ~ 100 DEG C, more preferably 75~95℃。

According to the present invention, the step A can be carried out according to conventionally known in the art any mode, not special Limit.As its embodiment, such as it can enumerate and solvent for polymerization is added to slurry polymerization reactor（Such as gather Close autoclave）In, then into the reactor add predetermined volume major catalyst and co-catalyst, add hydrogen to make a reservation for Hydrogen partial pressure, being finally continually fed into ethene makes polymerisation stagnation pressure constant in predetermined value, while keeping predetermined polymerisation Temperature carries out the homopolymerization of ethene, that is, obtains the A stage polymers.

Step B：Using slurry polymerization process, in the presence of the A stage polymers, polymerisation stagnation pressure 0.1 ~ 2.0MPa, hydrogen and ethylene partial pressure compare 0.01-0.5：1st, 20 ~ 120 DEG C of polymeric reaction temperature and comonomer addition be 0.01 ~ Under conditions of 0.3 gram/milligram major catalyst, make ethene and at least one alpha-olefin selected from C3-C12 alpha-olefins（Referred to as copolymerization Monomer）Copolymerization, obtains the ethene-alpha-olefin copolymer.

According to the present invention, the step B polymerisation stagnation pressure is generally 0.1 ~ 2.0MPa, preferably 0.2 ~ 1.0MPa, most It is preferred that 0.3-0.6MPa.

According to the present invention, the step B hydrogen and ethylene partial pressure ratio is generally 0.01-0.5：1, preferably 0.02-0.4： 1, most preferably 0.03-0.3：1.

According to the present invention, the step B polymeric reaction temperature is generally 20 ~ 120 DEG C, preferably 60 ~ 100 DEG C, more preferably 75~95℃。

According to the present invention, the step B comonomer addition is generally 0.01 ~ 0.3 gram/milligram major catalyst, excellent Select 0.015 ~ 0.25 gram/milligram major catalyst, more preferably 0.02 ~ 0.2 gram/milligram major catalyst.

As the non-limiting embodiment of the step B, such as it can enumerate after the step A terminates, The polymerization reaction mixture that the step that do not discharge A is obtained（Contain the A stage polymers）In the case of i.e. to step A reactor In it is disposable add the comonomer of predetermined volume in step B, then adjust and add hydrogen and divide to hydrogen predetermined step B Pressure, finally adjusting and being continually fed into ethene makes the constant predetermined value in step B of polymerisation stagnation pressure, while keeping step B to make a reservation for Polymeric reaction temperature carry out the copolymerization of ethene and the comonomer, that is, obtain the ethene-alpha-olefin copolymer of the present invention. Or, reactor of the polymerization reaction mixture that step A is obtained from step A（Now it is referred to as first reactor）In go out Material, is added to（Second）Slurry polymerization reactor（Such as polymerization autoclave）In, it is then disposable into the second reactor The comonomer of predetermined volume in step B is added, hydrogen is added to hydrogen partial pressure predetermined step B, finally persistently leads to Entering ethene makes the constant predetermined value in step B of polymerisation stagnation pressure, while keeping the predetermined polymeric reaction temperatures of step B to carry out The copolymerization of ethene and the comonomer, that is, obtain the ethene-alpha-olefin copolymer of the present invention.

According to the present invention, according to actual needs, the homopolymerization of the step A is typically carried out 2 ~ 8 hours, and preferably 3 ~ 5 is small When, the copolyreaction of the step B is typically carried out 0.2 ~ 4 hour, preferably 0.5 ~ 2 hour, but be not limited to this.In fact, two The length of the respective polymerization reaction time of individual step can be according to used major catalyst（Coordinate the co-catalyst）At each Charging situation of polymerization activity performance and each raw material in step etc. is accordingly adjusted, as long as making the A stage polymers account for institute State the 0.1-90wt% of ethene-alpha-olefin copolymer gross mass（It is preferred that 15-85wt%, more preferably 30-70wt%）.

It is apparent that these foregoing embodiments are exemplary, those skilled in the art can be using this Any mode known to field carries out the step B, and is not limited to foregoing concrete regulation, as long as the A ranks can be sufficiently reserved The activity of section polymer.In addition, the comonomer can also the step B progress during several times addition or Continuous addition, or the A stage polymers can also be separated afterwards again from the polymerization reaction mixture that step A is obtained It is preferred for step B, but not.

According to the present invention, the A stage polymers are due to containing the major catalyst and co-catalysis introduced by step A Agent, therefore show notable or effective olefin catalytic polymerization activity.In consideration of it, the step B is in the A stage polymers In the presence of when carrying out, without extra addition major catalyst.

In general, additionally adding co-catalyst also without as step A in step B, although root sometimes According to needing to supplement in right amount, to adjust the catalytic activity of the A stage polymers, but it is not required in that.

In general, also without extra addition solvent for polymerization in step B, although can also sometimes according to needs Appropriate supplement, but be not required in that.

As needed, step B subsequent implementation for convenience, can be by well known in the art before step B is carried out Method, removes the gas component of any presence from the polymerization reaction mixture that step A is obtained, and/or in step A After end, by means commonly known in the art, the gas component of any presence is removed from the step A reactor.

, can be mixed from the reaction obtained according to method well known in the art after step B terminates according to the present invention Desolvation etc. in compound and obtain powder, optionally further granulation and obtain pellet, be derived from solid-like（Particle or powder Shape）Ethene-alpha-olefin copolymer.These technologies be to those skilled in the art it is obvious or known, herein no longer Repeat.

According to the present invention, the ethene-alpha-olefin copolymer can also be by comprising the following steps A' and B' manufacturer Method B is manufactured.

Specifically, the present invention relates to a kind of manufacture method B of ethene-alpha-olefin copolymer, it is characterised in that including with Lower step：

Step A'：Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from alumina It is at least one as co-catalyst in alkane, alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, in polymerization 0.1 ~ 2.0MPa of reaction stagnation pressure, hydrogen and ethylene partial pressure compare 0.01-0.5：1st, 20 ~ 120 DEG C of polymeric reaction temperature and comonomer Addition be 0.01 ~ 0.3 gram/milligram major catalyst under conditions of, make ethene with selected from C3-C12 alpha-olefins at least one α- Alkene（Referred to as comonomer）Copolymerization, obtains A' stage polymers.

According to the present invention, the step A' polymerisation stagnation pressure is generally 0.1 ~ 2.0MPa, preferably 0.2 ~ 1.0MPa, most It is preferred that 0.3-0.6MPa.

According to the present invention, the step A' hydrogen and ethylene partial pressure ratio is generally 0.01-0.5：1, preferably 0.02-0.4： 1, most preferably 0.03-0.3：1.

According to the present invention, the step A' polymeric reaction temperature is generally 20 ~ 120 DEG C, preferably 60 ~ 100 DEG C, more preferably 75~95℃。

According to the present invention, the step A' comonomer addition is generally 0.01 ~ 0.3 gram/milligram major catalyst, excellent Select 0.015 ~ 0.25 gram/milligram major catalyst, more preferably 0.02 ~ 0.2 gram/milligram major catalyst.

According to the present invention, the step A' can be carried out according to conventionally known in the art any mode, not special Restriction.As its embodiment, such as it can enumerate and solvent for polymerization is added to slurry polymerization reactor（Such as Polymerization autoclave）In, the major catalyst and co-catalyst of predetermined volume are then added into the reactor, disposable add makes a reservation for The comonomer of consumption, adds hydrogen to predetermined hydrogen partial pressure, and being finally continually fed into ethene makes polymerisation stagnation pressure constant In predetermined value, while keeping predetermined polymeric reaction temperature to carry out the copolyreaction of ethene and comonomer, that is, the A' is obtained Stage polymer.

It is apparent that the embodiment is exemplary, those skilled in the art can use known in the art Any mode carry out the step A', and be not limited to foregoing concrete regulation.Such as, the comonomer can also be in the step Rapid A' is added or continuous addition several times during carrying out.

Step B'：Using slurry polymerization process, in the presence of the A' stage polymers, polymerisation stagnation pressure 0.2 ~ 2.0MPa, hydrogen and ethylene partial pressure compare 0.01-1：1st, ethylene homo is made under conditions of 20 ~ 120 DEG C of polymeric reaction temperature, so as to obtain Obtain ethene-alpha-olefin copolymer of the invention.

According to the present invention, the step B' polymerisation stagnation pressure is generally 0.2 ~ 2.0MPa, preferably 0.3 ~ 1.5MPa, most It is preferred that 0.4-0.8MPa.

According to the present invention, the step B' hydrogen and ethylene partial pressure ratio is generally 0.01-1：1, preferably 0.02-0.8：1, Most preferably 0.03-0.5：1.

According to the present invention, the step B' polymeric reaction temperature is generally 20 ~ 120 DEG C, preferably 60 ~ 100 DEG C, more preferably 75~95℃。

As the non-limiting embodiment of the step B', such as it can enumerate after the step A' terminates, The polymerization reaction mixture that the step that do not discharge A' is obtained（Contain the A' stage polymers）In the case of i.e. to step A' institute State and added in reactor hydrogen to hydrogen partial pressure predetermined step B', finally adjusting and being continually fed into ethene makes polymerisation stagnation pressure The constant predetermined value in step B', while keeping the predetermined polymeric reaction temperatures of step B' to carry out the homopolymerization of ethene, that is, obtains this The ethene-alpha-olefin copolymer of invention.Or, reactor of the polymerization reaction mixture that step A' is obtained from step A' （Now it is referred to as first reactor）Middle discharging, is added to（Second）Slurry polymerization reactor（Such as polymerization autoclave）In, so Hydrogen is added in the backward second reactor to hydrogen partial pressure predetermined step B', being finally continually fed into ethene makes polymerisation total The constant predetermined value in step B' is pressed, while keeping the predetermined polymeric reaction temperatures of step B' to carry out the homopolymerization of ethene, that is, is obtained Obtain ethene-alpha-olefin copolymer of the invention.

According to the present invention, according to actual needs, the copolyreaction of the step A' typically carries out 0.2 ~ 4 hour, preferably 0.5 ~ 2 hours, the homopolymerization of the step B' was typically carried out 2 ~ 8 hours, preferably 3 ~ 5 hours, but be not limited to this.In fact, two The length of the respective polymerization reaction time of individual step can be according to used major catalyst（Coordinate the co-catalyst）At each Charging situation of polymerization activity performance and each raw material in step etc. is accordingly adjusted, as long as making the A' stage polymers account for institute State the 10-99.9wt% of ethene-alpha-olefin copolymer gross mass（It is preferred that 15-85wt%, more preferably 30-70wt%）.

It is apparent that these foregoing embodiments are exemplary, those skilled in the art can be using this Any mode known to field carries out the step B', and is not limited to foregoing concrete regulation, as long as the A' can be sufficiently reserved The activity of stage polymer.In addition, the A' stage polymers can also from step ' A obtain polymerization reaction mixture In separate after be used further to step B', it is but not preferred.

According to the present invention, the A' stage polymers are due to containing the major catalyst and co-catalysis introduced by step A' Agent, therefore show notable or effective olefin catalytic polymerization activity.In consideration of it, the step B' is in the A' stage polymers In the presence of when carrying out, without extra addition major catalyst.

In general, additionally adding co-catalyst also without as step A' in step B', although sometimes It can also in right amount supplement, to adjust the catalytic activity of the A' stage polymers, but be not required in that as needed.

In general, also without extra addition solvent for polymerization in step B', although also may be used sometimes according to needs To supplement in right amount, but it is not required in that.

As needed, step B' subsequent implementation for convenience, can be by known in this field before step B' is carried out Method, the gas component of any presence is removed from the polymerization reaction mixture that step A' is obtained, and/or in step After rapid A' terminates, by means commonly known in the art, the gas group of any presence is removed from the step A' reactor Point.

, can be mixed from the reaction obtained according to method well known in the art after step B' terminates according to the present invention Desolvation etc. in compound and obtain powder, optionally further granulation and obtain pellet, be derived from solid-like（Particle or powder Shape）Ethene-alpha-olefin copolymer.These technologies be to those skilled in the art it is obvious or known, herein no longer Repeat.

According to the present invention, in foregoing manufacture method A and manufacture method B, the C3-C12 alpha-olefins more preferably C4- C8 alpha-olefins.As alpha-olefin used herein, such as it can enumerate propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- heptene, 1- Octene, 4-methyl-1-pentene, 1- laurylenes, 4- methyl isophthalic acids-hexene etc., preferably 1- butylene, 1- hexenes, 4-methyl-1-pentene, 1- octenes, more preferably 1- hexenes, 4-methyl-1-pentene, 1- octenes.These alpha-olefins can be used alone, or can be by them In two or more be applied in combination.

According to the present invention, in foregoing manufacture method A and manufacture method B, it is catalyzed as the load type non-metallocene Agent, preferably uses the load type non-metallocene catalyst manufactured by following preparation method.

According to the present invention, the preparation method of the load type non-metallocene catalyst comprises the following steps：Make magnesium compound It is dissolved in the presence of an alcohol in solvent with Nonmetallocene part, the step of obtaining magnesium compound solution；Make porous carrier and institute State magnesium compound solution mixing, the step of obtaining mixed serum；Precipitating reagent is added into the mixed serum or is dried described Mixed serum, the step of obtaining complex carrier；With the chemical treatments for making the complex carrier with being selected from IV B races metallic compound Contact, the step of obtaining the load type non-metallocene catalyst.

Below to obtaining magnesium compound solution the step of, is specifically described.

According to the step, magnesium compound and Nonmetallocene part is set to be dissolved in appropriate solvent in the presence of an alcohol（Also referred to as For dissolving magnesium compound solvent）In, so as to obtain the magnesium compound solution.

As the solvent, such as it can enumerate C_6-12Aromatic hydrocarbon, halo C_6-12Aromatic hydrocarbon, ester and ether equal solvent.Specific ratio Can such as enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene, bromo ethylbenzene, Ethyl acetate and tetrahydrofuran etc..Wherein, preferably C_6-12Aromatic hydrocarbon and tetrahydrofuran, most preferably tetrahydrofuran.

These solvents can be used alone one kind, can also be used in mixed way so that arbitrary ratio is a variety of.

According to the present invention, term " alcohol " refers to hydrocarbon chain（Such as C_1-30Hydrocarbon）On at least one hydrogen atom be optionally substituted by a hydroxyl group And the compound obtained.

As the alcohol, such as it can enumerate C_1-30Fatty alcohol（It is preferred that C_1-30Aliphatic monobasic alcohol）、C_6-30Aromatic alcohol（It is excellent Select C_6-30Aromatic monoalcohols）And C_4-30Alicyclic ring alcohol（It is preferred that C_4-30Alicyclic monohydric alcohol）, wherein it is preferred that C_1-30Aliphatic monobasic alcohol Or C_2-8Aliphatic monobasic alcohol, more preferably ethanol and butanol.In addition, the alcohol can optionally be selected from halogen atom or C_1-6Alkoxy Substituent substitution.

It is used as the C_1-30Fatty alcohol, such as can enumerate methanol, ethanol, propyl alcohol, 2- propyl alcohol, butanol, amylalcohol, 2- methyl Amylalcohol, 2- ethylpentanols, 2- hexyls butanol, hexanol and 2-Ethylhexyl Alcohol etc., wherein preferred alcohol, butanol and 2-Ethylhexyl Alcohol.

It is used as the C_6-30Aromatic alcohol, such as can enumerate phenmethylol, benzyl carbinol and methylbenzyl alcohol etc., wherein it is preferred that benzene Ethanol.

It is used as the C_4-30Alicyclic ring alcohol, such as can enumerate cyclohexanol, cyclopentanol, Lotka-Volterra circle system, methylcyclopentanol, ethyl ring Amylalcohol, propyl group cyclopentanol, methyl cyclohexanol, ethyl cyclohexanol, cyclohexyl alcohol, methyl Lotka-Volterra circle system, ethyl Lotka-Volterra circle system and propyl group Lotka-Volterra circle system etc., wherein it is preferred that cyclohexanol and methyl cyclohexanol.

As the alcohol replaced by halogen atom, such as trichlorine methanol, ethapon and three Mecorals etc. can be enumerated, its In preferred trichlorine methanol.

As the alcohol replaced by alkoxy, such as it can enumerate glycol-ether, ethylene glycol-n-butyl ether and 1- fourths Epoxide -2- propyl alcohol etc., wherein it is preferred that glycol-ether.

These alcohol can be used alone one kind, a variety of can also be used in mixed way.In the form of a variety of mixing in use, institute The ratio stated between any two kinds of alcohol in alcohol mixture can be arbitrarily determined, and be not particularly limited.

In order to prepare the magnesium compound solution, the magnesium compound and the Nonmetallocene part can be added to by Dissolved in the solvent and the mixed solvent of alcohol formation, or by the magnesium compound and the Nonmetallocene part It is added in the solvent, and subsequently or simultaneously addition alcohol is dissolved, but it is not limited to this.

To the preparation time of the magnesium compound solution（During the dissolving of i.e. described magnesium compound and the Nonmetallocene part Between）There is no particular limitation, but generally 0.5~24h, preferably 4~24h.In the preparation process, it is possible to use stir to promote Enter the dissolving of the magnesium compound and the Nonmetallocene part.The stirring can use any form, such as agitating paddle（Rotating speed Generally 10~1000 revs/min）Deng.As needed, dissolving can be promoted by appropriate heating sometimes.

The magnesium compound is specifically described below.

According to the present invention, term " magnesium compound " uses the common concept in this area, refers to poly- as load-type alkene Close the conventional use of organic or inorganic solid water-free magnesium-containing compound of carrier of catalyst.

According to the present invention, as the magnesium compound, such as can enumerate magnesium halide, Alkoxymagnesium halides, alkoxyl magnesium, Alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium.

Specifically, as the magnesium halide, such as magnesium chloride can be enumerated（MgCl₂）, magnesium bromide（MgBr₂）, magnesium iodide （MgI₂）And magnesium fluoride（MgF₂）Deng wherein it is preferred that magnesium chloride.

As the Alkoxymagnesium halides, such as it can enumerate methoxy magnesium chloride（Mg(OCH₃)Cl）, ethyoxyl chlorination Magnesium（Mg(OC₂H₅)Cl）, propoxyl group magnesium chloride（Mg(OC₃H₇)Cl）, n-butoxy magnesium chloride（Mg(OC₄H₉)Cl）, isobutoxy Magnesium chloride（Mg(i-OC₄H₉)Cl）, methoxyl group magnesium bromide（Mg(OCH₃)Br）, ethyoxyl magnesium bromide（Mg(OC₂H₅)Br）, propoxyl group Magnesium bromide（Mg(OC₃H₇)Br）, n-butoxy magnesium bromide（Mg(OC₄H₉)Br）, isobutoxy magnesium bromide（Mg(i-OC₄H₉)Br）、 Methoxyl group magnesium iodide（Mg(OCH₃)I）, ethyoxyl magnesium iodide（Mg(OC₂H₅)I）, propoxyl group magnesium iodide（Mg(OC₃H₇)I）, positive fourth Epoxide magnesium iodide（Mg(OC₄H₉)I）With isobutoxy magnesium iodide（Mg(i-OC₄H₉)I）Deng wherein it is preferred that methoxy magnesium chloride, second Epoxide magnesium chloride and isobutoxy magnesium chloride.

As the alkoxyl magnesium, such as it can enumerate magnesium methoxide（Mg(OCH₃)₂）, magnesium ethylate（Mg(OC₂H₅)₂）、 Propoxyl group magnesium（Mg(OC₃H₇)₂）, butoxy magnesium（Mg(OC₄H₉)₂）, isobutoxy magnesium（Mg(i-OC₄H₉)₂）With 2- ethyl hexyl oxies Magnesium（Mg(OCH₂CH(C₂H₅)C₄H)₂）Deng wherein it is preferred that magnesium ethylate and isobutoxy magnesium.

As the alkyl magnesium, such as it can enumerate methyl magnesium（Mg(CH₃)₂）, magnesium ethide（Mg(C₂H₅)₂）, propyl group magnesium（Mg (C₃H₇)₂）, normal-butyl magnesium（Mg(C₄H₉)₂）With isobutyl group magnesium（Mg(i-C₄H₉)₂）Deng wherein it is preferred that magnesium ethide and normal-butyl magnesium.

As the alkyl halide magnesium, such as it can enumerate methyl-magnesium-chloride（Mg(CH₃)Cl）, ethylmagnesium chloride（Mg (C₂H₅)Cl）, propyl group magnesium chloride（Mg(C₃H₇)Cl）, n-butylmagnesium chloride magnesium（Mg(C₄H₉)Cl）, isobutyl group magnesium chloride（Mg(i- C₄H₉)Cl）, methyl-magnesium-bromide（Mg(CH₃)Br）, ethylmagnesium bromide（Mg(C₂H₅)Br）, propyl group magnesium bromide（Mg(C₃H₇)Br）, just Butyl magnesium bromide（Mg(C₄H₉)Br）, selenium alkynide（Mg(i-C₄H₉)Br）, methylpyridinium iodide magnesium（Mg(CH₃)I）, ethyl phosphonium iodide Magnesium（Mg(C₂H₅)I）, propyl group magnesium iodide（Mg(C₃H₇)I）, normal-butyl magnesium iodide（Mg(C₄H₉)I）With isobutyl group magnesium iodide（Mg(i- C₄H₉)I）Deng wherein it is preferred that methyl-magnesium-chloride, ethylmagnesium chloride and isobutyl group magnesium chloride.

As the alkyl alkoxy magnesium, such as it can enumerate methyl methoxy base magnesium（Mg(OCH₃)(CH₃)）, methylethoxy Base magnesium（Mg(OC₂H₅)(CH₃)）, methyl propoxyl group magnesium（Mg(OC₃H₇)(CH₃)）, methyl n-butoxy magnesium（Mg(OC₄H₉) (CH₃)）, methyl tert-butyl epoxide magnesium（Mg(i-OC₄H₉)(CH₃)）, ethyl magnesium methoxide（Mg(OCH₃)(C₂H₅)）, ethyl ethyoxyl Magnesium（Mg(OC₂H₅)(C₂H₅)）, ethylpropoxy magnesium（Mg(OC₃H₇)(C₂H₅)）, ethyl n-butoxy magnesium（Mg(OC₄H₉) (C₂H₅)）, ethyl isobutyl epoxide magnesium（Mg(i-OC₄H₉)(C₂H₅)）, propylmethoxy magnesium（Mg(OCH₃)(C₃H₇)）, propyl group ethoxy Base magnesium（Mg(OC₂H₅)(C₃H₇)）, propyl group propoxyl group magnesium（Mg(OC₃H₇)(C₃H₇)）, propyl group n-butoxy magnesium（Mg(OC₄H₉) (C₃H₇)）, propyl group isobutoxy magnesium（Mg(i-OC₄H₉)(C₃H₇)）, normal-butyl magnesium methoxide（Mg(OCH₃)(C₄H₉)）, normal-butyl Magnesium ethylate（Mg(OC₂H₅)(C₄H₉)）, normal-butyl propoxyl group magnesium（Mg(OC₃H₇)(C₄H₉)）, normal-butyl n-butoxy magnesium（Mg (OC₄H₉)(C₄H₉)）, normal-butyl isobutoxy magnesium（Mg(i-OC₄H₉)(C₄H₉)）, isobutyl group magnesium methoxide（Mg(OCH₃)(i- C₄H₉)）, isobutyl group magnesium ethylate（Mg(OC₂H₅) (i-C₄H₉)）, isobutyl group propoxyl group magnesium（Mg(OC₃H₇) (i-C₄H₉)）, it is different Butyl n-butoxy magnesium（Mg(OC₄H₉) (i-C₄H₉)）With isobutyl group isobutoxy magnesium（Mg(i-OC₄H₉) (i-C₄H₉)）Deng it In preferred butyl magnesium ethylate.

These magnesium compounds can be used alone one kind, a variety of can also be used in mixed way, is not particularly limited.

In the form of a variety of mixing in use, mole between two kinds of magnesium compounds in the magnesium compound mixture Frequently as being 0.25~4：1, preferably 0.5~3：1, more preferably 1~2：1.

According to the present invention, term " Nonmetallocene complex " is a kind of single centre alkene for metallocene catalyst Do not contain cyclopentadienyl groups such as luxuriant ring, fluorenes ring or indenes ring or derivatives thereof in polymerized hydrocarbon catalyst, structure, and with co-catalysis Agent（Such as those described below）The metallo-organic compound of olefinic polymerization catalysis activity is can show that during combination（Therefore institute State Nonmetallocene complex and be also sometimes referred to as non-metallocene olefin polymerization complex）.The compound is former comprising central metal Son and at least one multidentate ligand combined with the central metal atom with coordinate bond（It is preferred that tridentate ligand or more tooth is matched somebody with somebody Body）, and term " Nonmetallocene part " is foregoing multidentate ligand.

According to the present invention, the Nonmetallocene part is selected from the compound with following chemical structural formula：

。

According to the present invention, group A, D and E in the compound（Coordination group）Pass through the coordination atom contained by it （The hetero atoms such as such as N, O, S, Se and P）With contained by the IV B races metallic compound that is used in the present invention as chemical treatments IV B races metallic atom occurs complexation reaction and forms coordinate bond, is consequently formed the metallic atom centered on the IV B races metallic atom M complex（Nonmetallocene complex i.e. of the present invention）.

In one more specifically embodiment, the Nonmetallocene part is selected from the change with following chemical structural formula Compound（A）And compound（B）：

With

（A）（B）.

In one more specifically embodiment, the Nonmetallocene part is selected from the change with following chemical structural formula Compound（A-1）To compound（A-4）And compound（B-1）To compound（B-4）：

、、

（A-1）（A-2）

、、

（A-3）（A-4）

、、

（B-1）（B-2）

With

（B-3）（B-4）.

In all of above chemical structural formula,

Q is 0 or 1；

D is 0 or 1；

E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group（-CN）, wherein N, O, S, Se and P are respectively coordination atom；

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group（-CN）, such as can be with Enumerate-NR²³R²⁴、-N(O)R²⁵R²⁶、-PR²⁸R²⁹、-P(O)R³⁰R³¹、-OR³⁴、-SR³⁵、-S(O)R³⁶、-SeR³⁸Or-Se (O) R³⁹, Wherein N, O, S, Se and P are respectively coordination atom；

Represent singly-bound or double bond；

- represent covalent bond or ionic bond.

R¹To R⁴、R⁶To R³⁶、R³⁸And R³⁹It is each independently selected from hydrogen, C₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl（Wherein It is preferred that halohydrocarbyl, such as-CH₂Cl and-CH₂CH₂Cl）Or safing function group.Above-mentioned group to each other can be with identical With difference, wherein adjacent group such as R¹With R², R⁶With R⁷, R⁷With R⁸, R⁸With R⁹, R¹³With R¹⁴, R¹⁴With R¹⁵, R¹⁵With R¹⁶, R¹⁸With R¹⁹, R¹⁹With R²⁰, R²⁰With R²¹, R²³With R²⁴, or R²⁵With R²⁶Etc. can combine togather bonding or cyclization, it is preferably formed as Aromatic ring, such as unsubstituted phenyl ring or by 1-4 C₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl（Wherein preferred halogenated hydrocarbons Base, such as-CH₂Cl and-CH₂CH₂Cl）Or the phenyl ring of safing function substituent group.

R⁵Lone pair electrons, hydrogen, C on nitrogen₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl, oxy radical, sulfur-containing group, Nitrogen-containing group, containing seleno group or phosphorus-containing groups.Work as R⁵For oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorous-containigroups groups During group, R⁵In N, O, S, P and Se can be used as coordination atom（It is coordinated with the central metal atom M）.

In the context of the present invention, the safing function group can such as be enumerated selected from halogen, oxy radical, contained Nitrogen groups, silicon-containing group, germanic group, sulfur-containing group, containing tin group, C₁- C₁₀Ester group or nitro（-NO₂）At least one Deng, but do not include C generally₁- C₃₀Alkyl and the C of substitution₁- C₃₀Alkyl.

In the context of the present invention, limited by the chemical constitution of multidentate ligand of the present invention, the safing function Group has the characteristics that：

（1）Described group A, D, E, F, Y or Z and the central metal atom M complexation process are not disturbed, and

（2）It is less than described A, D, E, F, Y and Z group with the coordination ability of the central metal atom M, and does not replace this The coordination of a little groups and the central metal atom M.

It is as the case may be, any adjacent two or more in foregoing all chemical structural formulas according to the present invention Group, such as R²¹With group Z, or R¹³With group Y, can combine togather cyclization, be preferably formed as comprising coming from institute State group Z or Y heteroatomic C₆- C₃₀Heteroaromatic, such as pyridine ring etc., wherein the heteroaromatic is optionally by 1 Or it is multiple selected from C₁- C₃₀Alkyl, the C of substitution₁- C₃₀The substituent substitution of alkyl and safing function group.

In the context of the present invention,

The halogen is selected from F, Cl, Br or I.The nitrogen-containing group is selected from、-NR²³R²⁴、-T-NR²³R²⁴Or-N (O) R²⁵R²⁶.The phosphorus-containing groups are selected from、-PR²⁸R²⁹、-P(O)R³⁰R³¹Or-P (O) R³²(OR³³).The oxy radical is selected from Hydroxyl ,-OR³⁴With-T-OR³⁴.The sulfur-containing group is selected from-SR³⁵、-T-SR³⁵、-S(O)R³⁶Or-T-SO₂R³⁷.It is described to contain seleno Group is selected from-SeR³⁸、-T-SeR³⁸、-Se(O)R³⁹Or-T-Se (O) R³⁹.The group T is selected from C₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl or safing function group.The R³⁷Selected from hydrogen, C₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl or safing function Group.

In the context of the present invention, the C₁- C₃₀Alkyl is selected from C₁- C₃₀Alkyl（It is preferred that C₁- C₆Alkyl, such as it is different Butyl）、C₇- C₃₀Alkaryl（Such as tolyl, xylyl, diisobutyl phenyl etc.）、C₇- C₃₀Aralkyl（Such as benzyl Base）、C₃- C₃₀Cyclic alkyl, C₂- C₃₀Alkenyl, C₂- C₃₀Alkynyl, C₆- C₃₀Aryl（Such as phenyl, naphthyl, anthryl etc.）、 C₈- C₃₀Condensed ring radical or C₄- C₃₀Heterocyclic radical, wherein the heterocyclic radical, which contains 1-3, is selected from nitrogen-atoms, oxygen atom or sulphur atom Hetero atom, such as pyridine radicals, pyrrole radicals, furyl or thienyl etc..

It is in the context of the present invention, described according to the concrete condition to its related group combined according to the present invention C₁- C₃₀Alkyl is sometimes referred to as C₁- C₃₀Hydrocarbon diyl（Divalent group, or referred to as C₁- C₃₀Alkylene）Or C₁- C₃₀The base of hydrocarbon three （Trivalent radical）, this is obvious to those skilled in the art.

In the context of the present invention, the substituted C₁- C₃₀Alkyl refers to carrying one or more inert substituents C₁- C₃₀Alkyl.So-called inert substituent, refers to these substituents to aforementioned coordinative group（Refer to foregoing group A, D, E, F, Y and Z, or also optionally include R⁵）With central metal atom M（I.e. foregoing IV B races metallic atom）Complexation process do not have There is substantial interference；In other words, limited by the chemical constitution of part of the present invention, these substituents have no ability to or without machine Meeting（Such as influenceed by steric hindrance etc.）Occur complexation reaction with the IV B races metallic atom and form coordinate bond.In general, The inert substituent is selected from halogen or C₁- C₃₀Alkyl（It is preferred that C₁- C₆Alkyl, such as isobutyl group）.

In the context of the present invention, the silicon-containing group is selected from-SiR⁴²R⁴³R⁴⁴Or-T-SiR⁴⁵；The germanic group choosing From-GeR⁴⁶R⁴⁷R⁴⁸Or-T-GeR⁴⁹；It is described to be selected from-SnR containing tin group⁵⁰R⁵¹R⁵²、-T-SnR⁵³Or-T-Sn (O) R⁵⁴；And institute State R⁴²To R⁵⁴Be each independently selected from hydrogen, foregoing C₁- C₃₀Alkyl, foregoing substituted C₁- C₃₀Alkyl or foregoing inertia Functional groups, above-mentioned group be can be the same or different to each other, and wherein adjacent group can be combined togather into Key or cyclization.Wherein group T is as defined above.

As the Nonmetallocene part, such as it can enumerate following compound：

、、

With。

The Nonmetallocene part is preferably selected from following compound：

、、

、 With

。

The Nonmetallocene part is further preferably selected from following compound：

、、、、With。

The Nonmetallocene part is more preferably selected from following compound：

With。

These Nonmetallocene parts can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.

According to the present invention, the Nonmetallocene part is not usually used as electronic donor compound in this area Diether compounds.

The Nonmetallocene part can be manufactured according to any method well known by persons skilled in the art.On its system The particular content of method is made, such as can be found in WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 Deng this specification introduces the full text of these documents as reference with regard to this.

According to the present invention, porous carrier is mixed with the magnesium compound solution, obtain mixed serum.

The porous carrier is specifically described below.

According to the present invention, as the porous carrier, such as it can enumerate this area and be urged in manufacture load type olefin polymerization During agent as carrier those conventional use of organic or inorganic porosu solids.

Specifically, as the Porous-Organic solid, such as olefin homo or copolymer, polyvinyl alcohol can be enumerated Or its copolymer, cyclodextrin,（Altogether）Polyester,（Altogether）Polyamide, ryuron or copolymer, Voncoat R 3310 or common Polymers, methacrylate homopolymer or copolymer, and styrene homopolymers or copolymer etc., and these homopolymers or common The partial cross-linked form of polymers, wherein it is preferred that partial cross-linked（The such as degree of cross linking is at least 2% but less than 100%）Styrene polymerization Thing.

According to yet other embodiments, carry and such as select preferably on the surface of the Porous-Organic solid It is mono-substituted from hydroxyl, primary amino radical, secondary amino group, sulfonic group, carboxyl, amide groups, the mono-substituted amide groups of N-, sulfoamido, N- The active function groups of any one or more in sulfoamido, sulfydryl, acylimino and hydrazide group, wherein it is preferred that carboxyl and hydroxyl At least one in base.

According to an embodiment of the invention, using it is preceding the Porous-Organic solid is carried out thermal activation treatment and/or Chemical activation processing.

According to the present invention, the Porous-Organic solid can only carry out thermal activation treatment before use, or before use It can also only carry out chemical activation processing, or according to arbitrary built-up sequence successively can carry out the thermal activation using preceding Processing and chemical activation processing, are not particularly limited.

The thermal activation treatment can be carried out in usual way.To described such as at reduced pressure conditions or under inert atmosphere Porous-Organic solid is heated.Inert atmosphere mentioned here refers to only contain extremely micro in gas or not contained Component that can be with the Porous-Organic solid reaction.As the inert atmosphere, such as it can enumerate nitrogen or rare gas gas Atmosphere, preferably nitrogen atmosphere.Due to the poor heat resistance of Porous-Organic solid, therefore the thermal activation process is described organic more not destroy The structure of hole solid in itself and it basic composition is premise.Usually, the temperature of the thermal activation be 50~400 DEG C, preferably 100~ 250 DEG C, and the thermal activation time is 1~24h, preferably 2~12h.

After thermal activation/chemical activation processing, malleation is saved backup the Porous-Organic solid needs under an inert atmosphere.

As the inorganic porous solids, such as it can enumerate the difficulty of the A of the periodic table of elements II, III A, IVA or Group IVB metal Molten oxide（Such as silica（Also known as silica or silica gel）, aluminum oxide, magnesia, titanium oxide, zirconium oxide or thorium oxide Deng）, or these metals any infusibility composite oxides（Such as oxidation sial, oxidation magnalium, titanium oxide silicon, titanium oxide magnesium With titanium oxide aluminium etc.）, and clay, molecular sieve（Such as ZSM-5 and MCM-41）, mica, montmorillonite, bentonite and diatomite Deng.As the inorganic porous solids, it can also enumerate and pyrohydrolysis is passed through by gaseous metal halide or gaseous silicon compound And the oxide generated, such as the silica gel obtained by silicon tetrachloride pyrohydrolysis, or obtained by alchlor pyrohydrolysis Aluminum oxide etc..

It is used as the inorganic porous solids, preferably silica, aluminum oxide, magnesia, oxidation sial, oxidation magnalium, oxygen Change titanium silicon, titanium dioxide, molecular sieve and montmorillonite etc., particularly preferred silica.

According to the present invention, suitable silica can be manufactured by conventional method, or can be arbitrary commercially available Commercial product, such as can enumerate the Grace 955, Grace 948, Grace SP9-351, Grace of Grace companies SP9-485, Grace SP9-10046, Davsion Syloid 245 and ES70 of Aerosil812, Ineos company, ES70X, ES70Y, ES70W, ES757, EP10X and EP11, and Pq Corp. CS-2133 and MS-3040.

According to yet other embodiments, with hydroxyl etc. preferably on the surface of the inorganic porous solids Active function groups.

According to the present invention, in one embodiment, thermal activation treatment is being carried out to the inorganic porous solids before And/or chemical activation processing.

According to the present invention, the inorganic porous solids can only carry out thermal activation treatment before use, or before use It can also only carry out chemical activation processing, or according to arbitrary built-up sequence successively can carry out the thermal activation using preceding Processing and chemical activation processing, are not particularly limited.

The thermal activation treatment can be carried out in usual way, such as to described at reduced pressure conditions or under inert atmosphere Inorganic porous solids are heated.Inert atmosphere mentioned here refers to only contain extremely micro in gas or not contained The component that can be reacted with the inorganic porous solids.As the inert atmosphere, such as it can enumerate nitrogen or rare gas gas Atmosphere, preferably nitrogen atmosphere.Usually, the temperature of the thermal activation be 200-800 DEG C, preferably 400~700 DEG C, most preferably 400~ 650 DEG C, the heat time is such as 0.5~24h, most preferably preferably 2~12h, 4~8h.

After thermal activation/chemical activation processing, malleation is saved backup the inorganic porous solids needs under an inert atmosphere.

According to the present invention, at the chemical activation that the Porous-Organic solid or the inorganic porous solids are carried out Reason can be carried out in usual way.Such as, it can enumerate using chemical activating agent come to the Porous-Organic solid or institute State the method that inorganic porous solids carry out chemical activation processing.

The chemical activating agent is specifically described first below.

According to the present invention, the chemical activating agent is used as using Group IVB metallic compound.

As the Group IVB metallic compound, such as it can enumerate selected from Group IVB metal halide, Group IVB metal alkyl Compound, Group IVB metal alkoxide, Group IVB metal alkyl halides and Group IVB metal alkoxide halide are at least It is a kind of.

It is used as the Group IVB metal halide, the Group IVB metal alkyl compound, the Group IVB metal alkoxide Compound, the Group IVB metal alkyl halides and the Group IVB metal alkoxide halide, such as can enumerate below formula The compound of structure：

M(OR¹)_mX_nR² _4-m-n

Wherein：

M is 0,1,2,3 or 4；

N is 0,1,2,3 or 4；

M is Group IVB metal, such as titanium, zirconium and hafnium etc. in the periodic table of elements；

X is halogen, such as F, Cl, Br and I etc.；And

R¹And R²It is each independently selected from C₁-₁₀Alkyl, such as methyl, ethyl, propyl group, normal-butyl, isobutyl group etc., R¹And R² Can be with identical, can also be different.

Specifically, as the Group IVB metal halide, such as titanium tetrafluoride can be enumerated（TiF₄）, titanium tetrachloride （TiCl₄）, titanium tetrabromide（TiBr₄）, titanium tetra iodide（TiI₄）；

Zirconium tetrafluoride（ZrF₄）, zirconium chloride（ZrCl₄）, tetrabormated zirconium（ZrBr₄）, zirconium tetraiodide（ZrI₄）；

Tetrafluoride hafnium（HfF₄）, hafnium tetrachloride（HfCl₄）, hafnium（HfBr₄）, tetraiodide hafnium（HfI₄）.

As the Group IVB metal alkyl compound, such as it can enumerate tetramethyl titanium（Ti(CH₃)₄）, tetraethyl titanium（Ti (CH₃CH₂)₄）, four isobutyl group titaniums（Ti(i-C₄H₉)₄）, tetra-n-butyl titanium（Ti(C₄H₉)₄）, triethyl methyl titanium（Ti(CH₃) (CH₃CH₂)₃）, diethyl-dimethyl titanium（Ti(CH₃)₂(CH₃CH₂)₂）, trimethylethyl titanium（Ti(CH₃)₃(CH₃CH₂)）, it is three different Butyl methyl titanium（Ti(CH₃)(i-C₄H₉)₃）, diisobutyl dimethyl titanium（Ti(CH₃)₂(i-C₄H₉)₂）, trimethyl isobutyl group titanium （Ti(CH₃)₃(i-C₄H₉)）, triisobutyl ethyl titanium（Ti(CH₃CH₂)(i-C₄H₉)₃）, diisobutyl diethyl titanium（Ti (CH₃CH₂)₂(i-C₄H₉)₂）, triethyl group isobutyl group titanium（Ti(CH₃CH₂)₃(i-C₄H₉)）, three normal-butyl methyltitaniums（Ti(CH₃) (C₄H₉)₃）, di-n-butyl dimethyl titanium（Ti(CH₃)₂(C₄H₉)₂）, trimethyl normal-butyl titanium（Ti(CH₃)₃(C₄H₉)）, three positive fourths Ylmethyl titanium（Ti(CH₃CH₂)(C₄H₉)₃）, di-n-butyl diethyl titanium（Ti(CH₃CH₂)₂(C₄H₉)₂）, triethyl group normal-butyl titanium （Ti(CH₃CH₂)₃(C₄H₉)）Deng；

Tetramethyl zirconium（Zr(CH₃)₄）, tetraethyl zirconium（Zr(CH₃CH₂)₄）, four isobutyl group zirconiums（Zr(i-C₄H₉)₄）, four positive fourths Base zirconium（Zr(C₄H₉)₄）, triethyl methyl zirconium（Zr(CH₃)(CH₃CH₂)₃）, diethyl-dimethyl zirconium（Zr(CH₃)₂(CH₃CH₂)₂）、 Trimethylethyl zirconium（Zr(CH₃)₃(CH₃CH₂)）, triisobutyl methylcyclopentadienyl zirconium（Zr(CH₃)(i-C₄H₉)₃）, diisobutyl zirconium dimethyl （Zr(CH₃)₂(i-C₄H₉)₂）, trimethyl isobutyl group zirconium（Zr(CH₃)₃(i-C₄H₉)）, triisobutyl ethyl zirconium（Zr(CH₃CH₂)(i- C₄H₉)₃）, diisobutyl diethyl zirconium（Zr(CH₃CH₂)₂(i-C₄H₉)₂）, triethyl group isobutyl group zirconium（Zr(CH₃CH₂)₃(i- C₄H₉)）, three normal-butyl methylcyclopentadienyl zirconiums（Zr(CH₃)(C₄H₉)₃）, di-n-butyl zirconium dimethyl（Zr(CH₃)₂(C₄H₉)₂）, trimethyl just Butyl zirconium（Zr(CH₃)₃(C₄H₉)）, three normal-butyl methylcyclopentadienyl zirconiums（Zr(CH₃CH₂)(C₄H₉)₃）, di-n-butyl diethyl zirconium（Zr (CH₃CH₂)₂(C₄H₉)₂）, triethyl group normal-butyl zirconium（Zr(CH₃CH₂)₃(C₄H₉)）Deng；

Tetramethyl hafnium（Hf(CH₃)₄）, tetraethyl hafnium（Hf(CH₃CH₂)₄）, four isobutyl group hafniums（Hf(i-C₄H₉)₄）, four positive fourths Base hafnium（Hf(C₄H₉)₄）, triethyl methyl hafnium（Hf(CH₃)(CH₃CH₂)₃）, diethyl-dimethyl hafnium（Hf(CH₃)₂(CH₃CH₂)₂）、 Trimethylethyl hafnium（Hf(CH₃)₃(CH₃CH₂)）, triisobutyl methylcyclopentadienyl hafnium（Hf(CH₃)(i-C₄H₉)₃）, diisobutyl dimethyl hafnium （Hf(CH₃)₂(i-C₄H₉)₂）, trimethyl isobutyl group hafnium（Hf(CH₃)₃(i-C₄H₉)）, triisobutyl ethyl hafnium（Hf(CH₃CH₂)(i- C₄H₉)₃）, diisobutyl diethyl hafnium（Hf(CH₃CH₂)₂(i-C₄H₉)₂）, triethyl group isobutyl group hafnium（Hf(CH₃CH₂)₃(i- C₄H₉)）, three normal-butyl methylcyclopentadienyl hafniums（Hf(CH₃)(C₄H₉)₃）, di-n-butyl dimethyl hafnium（Hf(CH₃)₂(C₄H₉)₂）, trimethyl just Butyl hafnium（Hf(CH₃)₃(C₄H₉)）, three normal-butyl methylcyclopentadienyl hafniums（Hf(CH₃CH₂)(C₄H₉)₃）, di-n-butyl diethyl hafnium（Hf (CH₃CH₂)₂(C₄H₉)₂）, triethyl group normal-butyl hafnium（Hf(CH₃CH₂)₃(C₄H₉)）Deng.

As the Group IVB metal alkoxide, such as it can enumerate titanium tetramethoxide（Ti(OCH₃)₄）, four ethoxies Base titanium（Ti(OCH₃CH₂)₄）, four isobutoxy titaniums（Ti(i-OC₄H₉)₄）, four titanium n-butoxides（Ti(OC₄H₉)₄）, triethoxy Methoxyl group titanium（Ti(OCH₃)(OCH₃CH₂)₃）, diethoxy dimethoxy titanium（Ti(OCH₃)₂(OCH₃CH₂)₂）, trimethoxy second Epoxide titanium（Ti(OCH₃)₃(OCH₃CH₂)）, three isobutoxy methoxyl group titaniums（Ti(OCH₃)(i-OC₄H₉)₃）, two isobutoxy diformazans Epoxide titanium（Ti(OCH₃)₂(i-OC₄H₉)₂）, trimethoxy isobutoxy titanium（Ti(OCH₃)₃(i-OC₄H₉)）, three isobutoxy second Epoxide titanium（Ti(OCH₃CH₂)(i-OC₄H₉)₃）, two isobutoxy diethoxy titaniums（Ti(OCH₃CH₂)₂(i-OC₄H₉)₂）, three ethoxies Base isobutoxy titanium（Ti(OCH₃CH₂)₃(i-OC₄H₉)）, three n-butoxy methoxyl group titaniums（Ti(OCH₃)(OC₄H₉)₃）, two positive fourths Epoxide dimethoxy titanium（Ti(OCH₃)₂(OC₄H₉)₂）, trimethoxy titanium n-butoxide（Ti(OCH₃)₃(OC₄H₉)）, three positive fourth oxygen Ylmethoxy titanium（Ti(OCH₃CH₂)(OC₄H₉)₃）, two n-butoxy diethoxy titaniums（Ti(OCH₃CH₂)₂(OC₄H₉)₂）, three ethoxies Base titanium n-butoxide（Ti(OCH₃CH₂)₃(OC₄H₉)）Deng；

Tetramethoxy zirconium（Zr(OCH₃)₄）, tetraethoxy zirconium（Zr(OCH₃CH₂)₄）, four isobutoxy zirconiums（Zr(i-OC₄H₉ )₄）, four n-butoxy zirconiums（Zr(OC₄H₉)₄）, triethoxy methoxyl group zirconium（Zr(OCH₃)(OCH₃CH₂)₃）, diethoxy dimethoxy Base zirconium（Zr(OCH₃)₂(OCH₃CH₂)₂）, trimethoxy ethyoxyl zirconium（Zr(OCH₃)₃(OCH₃CH₂)）, three isobutoxy methoxyl groups Zirconium（Zr(OCH₃)(i-OC₄H₉)₃）, two isobutoxy dimethoxy zirconiums（Zr(OCH₃)₂(i-OC₄H₉)₂）, trimethoxy isobutyl oxygen Base zirconium（Zr(OCH₃)₃(i-C₄H₉)）, three isobutoxy ethyoxyl zirconiums（Zr(OCH₃CH₂)(i-OC₄H₉)₃）, two isobutoxy diethyls Epoxide zirconium（Zr(OCH₃CH₂)₂(i-OC₄H₉)₂）, triethoxy isobutoxy zirconium（Zr(OCH₃CH₂)₃(i-OC₄H₉)）, three positive fourth oxygen Ylmethoxy zirconium（Zr(OCH₃)(OC₄H₉)₃）, two n-butoxy dimethoxy zirconiums（Zr(OCH₃)₂(OC₄H₉)₂）, trimethoxy just Butoxy zirconium（Zr(OCH₃)₃(OC₄H₉)）, three n-butoxy methoxyl group zirconiums（Zr(OCH₃CH₂)(OC₄H₉)₃）, two n-butoxies two Ethyoxyl zirconium（Zr(OCH₃CH₂)₂(OC₄H₉)₂）, triethoxy n-butoxy zirconium（Zr(OCH₃CH₂)₃(OC₄H₉)）Deng；

Tetramethoxy hafnium（Hf(OCH₃)₄）, tetraethoxy hafnium（Hf(OCH₃CH₂)₄）, four isobutoxy hafniums（Hf(i-OC₄H₉ )₄）, four n-butoxy hafniums（Hf(OC₄H₉)₄）, triethoxy methoxyl group hafnium（Hf(OCH₃)(OCH₃CH₂)₃）, diethoxy dimethoxy Base hafnium（Hf(OCH₃)₂(OCH₃CH₂)₂）, trimethoxy ethyoxyl hafnium（Hf(OCH₃)₃(OCH₃CH₂)）, three isobutoxy methoxyl groups Hafnium（Hf(OCH₃)(i-OC₄H₉)₃）, two isobutoxy dimethoxy hafniums（Hf(OCH₃)₂(i-OC₄H₉)₂）, trimethoxy isobutyl oxygen Base hafnium（Hf(OCH₃)₃(i-OC₄H₉)）, three isobutoxy ethyoxyl hafniums（Hf(OCH₃CH₂)(i-OC₄H₉)₃）, two isobutoxies two Ethyoxyl hafnium（Hf(OCH₃CH₂)₂(i-OC₄H₉)₂）, triethoxy isobutoxy hafnium（Hf(OCH₃CH₂)₃(i-C₄H₉)）, three positive fourths Oxymethoxy hafnium（Hf(OCH₃)(OC₄H₉)₃）, two n-butoxy dimethoxy hafniums（Hf(OCH₃)₂(OC₄H₉)₂）, trimethoxy N-butoxy hafnium（Hf(OCH₃)₃(OC₄H₉)）, three n-butoxy methoxyl group hafniums（Hf(OCH₃CH₂)(OC₄H₉)₃）, two n-butoxies Diethoxy hafnium（Hf(OCH₃CH₂)₂(OC₄H₉)₂）, triethoxy n-butoxy hafnium（Hf(OCH₃CH₂)₃(OC₄H₉)）Deng.

As the Group IVB metal alkyl halides, such as it can enumerate trimethyl ammonia chloride titanium（TiCl(CH₃)₃）, three second Base titanium chloride（TiCl(CH₃CH₂)₃）, triisobutyl titanium chloride（TiCl(i-C₄H₉)₃）, three n-butylmagnesium chloride titaniums（TiCl (C₄H₉)₃）, dimethyl titanium chloride（TiCl₂(CH₃)₂）, diethyl titanium chloride（TiCl₂(CH₃CH₂)₂）, diisobutyl dichloro Change titanium（TiCl₂(i-C₄H₉)₂）, three n-butylmagnesium chloride titaniums（TiCl(C₄H₉)₃）, methyl titanium trichloride（Ti(CH₃)Cl₃）, ethyl three Titanium chloride（Ti(CH₃CH₂)Cl₃）, isobutyl group titanium trichloride（Ti(i-C₄H₉)Cl₃）, normal-butyl titanium trichloride（Ti(C₄H₉)Cl₃）；

Trimethyl titanium bromide（TiBr(CH₃)₃）, triethyl group titanium bromide（TiBr(CH₃CH₂)₃）, triisobutyl titanium bromide （TiBr(i-C₄H₉)₃）, three normal-butyl titanium bromides（TiBr(C₄H₉)₃）, dimethyl dibrominated titanium（TiBr₂(CH₃)₂）, diethyl two Titanium bromide（TiBr₂(CH₃CH₂)₂）, diisobutyl dibrominated titanium（TiBr₂(i-C₄H₉)₂）, three normal-butyl titanium bromides（TiBr (C₄H₉)₃）, methyl titanium tribromide（Ti(CH₃)Br₃）, ethyl titanium tribromide（Ti(CH₃CH₂)Br₃）, isobutyl group titanium tribromide（Ti (i-C₄H₉)Br₃）, normal-butyl titanium tribromide（Ti(C₄H₉)Br₃）；

Trimethyl ammonia chloride zirconium（ZrCl(CH₃)₃）, triethyl group zirconium chloride（ZrCl(CH₃CH₂)₃）, triisobutyl zirconium chloride （ZrCl(i-C₄H₉)₃）, three n-butylmagnesium chloride zirconiums（ZrCl(C₄H₉)₃）, dimethyl zirconium dichloride（ZrCl₂(CH₃)₂）, diethyl two Zirconium chloride（ZrCl₂(CH₃CH₂)₂）, diisobutyl zirconium dichloride（ZrCl₂(i-C₄H₉)₂）, three n-butylmagnesium chloride zirconiums（ZrCl (C₄H₉)₃）, methyl tri-chlorination zirconium（Zr(CH₃)Cl₃）, ethyl tri-chlorination zirconium（Zr(CH₃CH₂)Cl₃）, isobutyl group tri-chlorination zirconium（Zr (i-C₄H₉)Cl₃）, normal-butyl tri-chlorination zirconium（Zr(C₄H₉)Cl₃）；

Trimethyl zirconium bromide（ZrBr(CH₃)₃）, triethyl group zirconium bromide（ZrBr(CH₃CH₂)₃）, triisobutyl zirconium bromide （ZrBr(i-C₄H₉)₃）, three normal-butyl zirconium bromides（ZrBr(C₄H₉)₃）, dimethyl dibrominated zirconium（ZrBr₂(CH₃)₂）, diethyl two Zirconium bromide（ZrBr₂(CH₃CH₂)₂）, diisobutyl dibrominated zirconium（ZrBr₂(i-C₄H₉)₂）, three normal-butyl zirconium bromides（ZrBr (C₄H₉)₃）, methyl tribromide zirconium（Zr(CH₃)Br₃）, ethyl tribromide zirconium（Zr(CH₃CH₂)Br₃）, isobutyl group tribromide zirconium（Zr (i-C₄H₉)Br₃）, normal-butyl tribromide zirconium（Zr(C₄H₉)Br₃）；

Trimethyl ammonia chloride hafnium（HfCl(CH₃)₃）, triethyl group hafnium chloride（HfCl(CH₃CH₂)₃）, triisobutyl hafnium chloride （HfCl(i-C₄H₉)₃）, three n-butylmagnesium chloride hafniums（HfCl(C₄H₉)₃）, dimethyl hafnium dichloride（HfCl₂(CH₃)₂）, diethyl two Hafnium chloride（HfCl₂(CH₃CH₂)₂）, diisobutyl hafnium dichloride（HfCl₂(i-C₄H₉)₂）, three n-butylmagnesium chloride hafniums（HfCl (C₄H₉)₃）, methyl tri-chlorination hafnium（Hf(CH₃)Cl₃）, ethyl tri-chlorination hafnium（Hf(CH₃CH₂)Cl₃）, isobutyl group tri-chlorination hafnium（Hf (i-C₄H₉)Cl₃）, normal-butyl tri-chlorination hafnium（Hf(C₄H₉)Cl₃）；

Trimethyl bromination hafnium（HfBr(CH₃)₃）, triethyl group bromination hafnium（HfBr(CH₃CH₂)₃）, triisobutyl bromination hafnium （HfBr(i-C₄H₉)₃）, three normal-butyl bromination hafniums（HfBr(C₄H₉)₃）, dimethyl dibrominated hafnium（HfBr₂(CH₃)₂）, diethyl two Bromination hafnium（HfBr₂(CH₃CH₂)₂）, diisobutyl dibrominated hafnium（HfBr₂(i-C₄H₉)₂）, three normal-butyl bromination hafniums（HfBr (C₄H₉)₃）, methyl tribromide hafnium（Hf(CH₃)Br₃）, ethyl tribromide hafnium（Hf(CH₃CH₂)Br₃）, isobutyl group tribromide hafnium（Hf (i-C₄H₉)Br₃）, normal-butyl tribromide hafnium（Hf(C₄H₉)Br₃）.

As the Group IVB metal alkoxide halide, such as it can enumerate trimethoxy titanium chloride（TiCl(OCH₃)₃）、 Triethoxy titanium chloride（TiCl(OCH₃CH₂)₃）, three isobutoxy titanium chlorides（TiCl(i-OC₄H₉)₃）, three n-butoxy chlorinations Titanium（TiCl(OC₄H₉)₃）, dimethoxy titanium chloride（TiCl₂(OCH₃)₂）, diethoxy titanium chloride（TiCl₂ (OCH₃CH₂)₂）, two isobutoxy titanium chloride（TiCl₂(i-OC₄H₉)₂）, three n-Butoxyl titanium-chlorides（TiCl(OC₄H₉)₃）、 Methoxytitanium trichloride（Ti(OCH₃)Cl₃）, ethyoxyl titanium trichloride（Ti(OCH₃CH₂)Cl₃）, isobutoxy titanium trichloride（Ti (i-C₄H₉)Cl₃）, nbutoxytitanium trichloride（Ti(OC₄H₉)Cl₃）；

Trimethoxy titanium bromide（TiBr(OCH₃)₃）, triethoxy titanium bromide（TiBr(OCH₃CH₂)₃）, three isobutoxy bromines Change titanium（TiBr(i-OC₄H₉)₃）, three n-butoxy titanium bromides（TiBr(OC₄H₉)₃）, dimethoxy dibrominated titanium（TiBr₂ (OCH₃)₂）, diethoxy dibrominated titanium（TiBr₂(OCH₃CH₂)₂）, two isobutoxy dibrominated titaniums（TiBr₂(i-OC₄H₉)₂）、 Three n-butoxy titanium bromides（TiBr(OC₄H₉)₃）, methoxyl group titanium tribromide（Ti(OCH₃)Br₃）, ethyoxyl titanium tribromide（Ti (OCH₃CH₂)Br₃）, isobutoxy titanium tribromide（Ti(i-C₄H₉)Br₃）, n-butoxy titanium tribromide（Ti(OC₄H₉)Br₃）；

Trimethoxy zirconium chloride（ZrCl(OCH₃)₃）, triethoxy zirconium chloride（ZrCl(OCH₃CH₂)₃）, three isobutoxy chlorine Change zirconium（ZrCl(i-OC₄H₉)₃）, three n-butoxy zirconium chlorides（ZrCl(OC₄H₉)₃）, dimethoxy zirconium dichloride（ZrCl₂ (OCH₃)₂）, diethoxy zirconium dichloride（ZrCl₂(OCH₃CH₂)₂）, two isobutoxy zirconium dichlorides（ZrCl₂(i-OC₄H₉)₂）、 Three n-butoxy zirconium chlorides（ZrCl(OC₄H₉)₃）, methoxyl group tri-chlorination zirconium（Zr(OCH₃)Cl₃）, ethyoxyl tri-chlorination zirconium（Zr (OCH₃CH₂)Cl₃）, isobutoxy tri-chlorination zirconium（Zr(i-C₄H₉)Cl₃）, n-butoxy tri-chlorination zirconium（Zr(OC₄H₉)Cl₃）；

Trimethoxy zirconium bromide（ZrBr(OCH₃)₃）, triethoxy zirconium bromide（ZrBr(OCH₃CH₂)₃）, three isobutoxy bromines Change zirconium（ZrBr(i-OC₄H₉)₃）, three n-butoxy zirconium bromides（ZrBr(OC₄H₉)₃）, dimethoxy dibrominated zirconium（ZrBr₂ (OCH₃)₂）, diethoxy dibrominated zirconium（ZrBr₂(OCH₃CH₂)₂）, two isobutoxy dibrominated zirconiums（ZrBr₂(i-OC₄H₉)₂）、 Three n-butoxy zirconium bromides（ZrBr(OC₄H₉)₃）, methoxyl group tribromide zirconium（Zr(OCH₃)Br₃）, ethyoxyl tribromide zirconium（Zr (OCH₃CH₂)Br₃）, isobutoxy tribromide zirconium（Zr(i-C₄H₉)Br₃）, n-butoxy tribromide zirconium（Zr(OC₄H₉)Br₃）；

Trimethoxy hafnium chloride（HfCl(OCH₃)₃）, triethoxy hafnium chloride（HfCl(OCH₃CH₂)₃）, three isobutoxy chlorine Change hafnium（HfCl(i-OC₄H₉)₃）, three n-butoxy hafnium chlorides（HfCl(OC₄H₉)₃）, dimethoxy hafnium dichloride（HfCl₂ (OCH₃)₂）, diethoxy hafnium dichloride（HfCl₂(OCH₃CH₂)₂）, two isobutoxy hafnium dichlorides（HfCl₂(i-OC₄H₉)₂）、 Three n-butoxy hafnium chlorides（HfCl(OC₄H₉)₃）, methoxyl group tri-chlorination hafnium（Hf(OCH₃)Cl₃）, ethyoxyl tri-chlorination hafnium（Hf (OCH₃CH₂)Cl₃）, isobutoxy tri-chlorination hafnium（Hf(i-C₄H₉)Cl₃）, n-butoxy tri-chlorination hafnium（Hf(OC₄H₉)Cl₃）；

Trimethoxy bromination hafnium（HfBr(OCH₃)₃）, triethoxy bromination hafnium（HfBr(OCH₃CH₂)₃）, three isobutoxy bromines Change hafnium（HfBr(i-OC₄H₉)₃）, three n-butoxy bromination hafniums（HfBr(OC₄H₉)₃）, dimethoxy dibrominated hafnium（HfBr₂ (OCH₃)₂）, diethoxy dibrominated hafnium（HfBr₂(OCH₃CH₂)₂）, two isobutoxy dibrominated hafniums（HfBr₂(i-OC₄H₉)₂）、 Three n-butoxy bromination hafniums（HfBr(OC₄H₉)₃）, methoxyl group tribromide hafnium（Hf(OCH₃)Br₃）, ethyoxyl tribromide hafnium（Hf (OCH₃CH₂)Br₃）, isobutoxy tribromide hafnium（Hf(i-C₄H₉)Br₃）, n-butoxy tribromide hafnium（Hf(OC₄H₉)Br₃）.

It is used as the Group IVB metallic compound, preferably described Group IVB metal halide, more preferably TiCl₄、TiBr₄、 ZrCl₄、ZrBr₄、HfCl₄And HfBr₄, most preferably TiCl₄And ZrCl₄。

These Group IVB metallic compounds can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.

, can be by having what the chemical activating agent to be utilized was activated when the chemical activating agent is at normal temperatures liquid The mode that the chemical activating agent of scheduled volume is directly added dropwise in Porous-Organic solid or inorganic porous solids uses the chemistry Activator.

When the chemical activating agent at normal temperatures be solid-state when, in order to measure with it is easy to operate for the sake of, preferably with solution Form uses the chemical activating agent.Certainly, when the chemical activating agent is at normal temperatures liquid, also may be used sometimes according to needs To use the chemical activating agent as a solution, it is not particularly limited.

When preparing the solution of the chemical activating agent, to now used solvent, there is no particular limitation, as long as its The chemical activating agent can be dissolved.

Specifically, C can be enumerated_5-12Alkane, C_5-12Cycloalkane, halo C_5-12Alkane, halo C_5-12Cycloalkane, C_6-12Virtue Hydrocarbon or halo C_6-12Aromatic hydrocarbons etc., such as can enumerate pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, ring Pentane, hexamethylene, cycloheptane, cyclooctane, toluene, ethylbenzene, dimethylbenzene, chloro-pentane, chloro-hexane, chloro heptane, chloro are pungent Alkane, chloro nonane, chloro decane, chloro hendecane, chlorinated dodecane, chlorocyclohexane, chlorotoluene, chloro ethylbenzene and chloro Dimethylbenzene etc., wherein it is preferred that pentane, hexane, decane, hexamethylene and toluene, most preferably hexane and toluene.

These solvents can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.

In addition, to concentration of the chemical activating agent in its solution, there is no particular limitation, can be appropriate as needed Selection, as long as it can realize the chemical activating agent with scheduled volume to implement the chemical activation.As it was previously stated, such as Fruit chemical activating agent is liquid, directly can carry out the activation using chemical activating agent, but it is also possible to be modulated into Used after chemical activation agent solution.

It is expedient to, molar concentration of the chemical activating agent in its solution is usually set to 0.01 ~ 1.0mol/L, but It is not limited to this.

It as the method for carrying out the chemical activation, such as can enumerate, be solid-state in chemical activating agent（Such as four chlorinations Zirconium）In the case of, the solution of the chemical activating agent is prepared first, then to Porous-Organic solid or inorganic porous to be activated Added in solid（It is preferred that being added dropwise）The solution of the chemical activating agent containing scheduled volume, to carry out chemical activation reaction. It is liquid in chemical activating agent（Such as titanium tetrachloride）In the case of, directly the chemical activating agent of scheduled volume can be added （It is preferred that being added dropwise）In Porous-Organic solid to be activated or inorganic porous solids, to carry out chemical activation reaction, or should Chemical activating agent is prepared into after solution, is added into Porous-Organic solid to be activated or inorganic porous solids（It is preferred that being added dropwise） The solution of the chemical activating agent containing scheduled volume, to carry out chemical activation reaction.

In general, at -30 ~ 60 DEG C（It is preferred that -20 ~ 30 DEG C）Reaction temperature under react the chemical activation（It is necessary When by stirring）Carry out 0.5~24 hour, preferably 1~8 hour, more preferably 2~6 hours.

After chemical activation reaction terminates, by being filtered, washed and dried, you can obtain by the organic many of chemical activation Hole solid or inorganic porous solids.

According to the present invention, described be filtered, washed and dried can be carried out using conventional method, and wherein washer solvent can be with Identical solvent used during using with dissolving the chemical activating agent.As needed, the washing typically carries out 1~8 time, preferably 2 ~6 times, most preferably 2~4 times.

The drying can be carried out using conventional method, such as under inert gas seasoning, boulton process or vacuum Heat drying method, preferably inert gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum seasoning.It is described dry Dry temperature range is generally normal temperature to 140 DEG C, and drying time is generally 2-20 hours, but is not limited to this.

According to the present invention, be used as the consumption of the chemical activating agent so that the porous carrier with Group IVB metallic element The ratio of the chemical activating agent of meter is 1g：1-100mmol, preferably 1g：2-50mmol, more preferably 1g：10-25mmol.

According to the present invention, to the surface area of the porous carrier, there is no particular limitation, but generally 10~1000m²/g （BET method is determined）, preferably 100~600m²/g；The pore volume of the porous carrier（Determination of nitrogen adsorption）Generally 0.1~4cm³/ G, preferably 0.2~2cm³/ g, and its average grain diameter（Laser particle analyzer is determined）It is preferred that 1~500mm, more preferably 1~100mm.

According to the present invention, the porous carrier can be arbitrary form, such as micropowder, granular, spherical, aggregation or Other forms.

According to the present invention, by making the porous carrier（Optionally pass through thermal activation and/or chemical activation）With the magnesium Polymer solution is mixed, and is derived from mixed serum.

According to the present invention, the mixed process of the porous carrier and the magnesium compound solution can use usual way Carry out, there is no particular limitation.It can such as enumerate, under the preparation temperature of normal temperature to the magnesium compound solution, to described The metered porous carrier in magnesium compound solution, or the metered magnesium compound is molten into the porous carrier Liquid, mixes 0.1~8h, preferably 0.5~4h, optimal 1~2h（If necessary by stirring）.

Now, the mixed serum obtained is a kind of system of pulpous state.Although not necessarily, equal in order to ensure system Even property, the mixed serum is preferred after preparation to carry out certain time（2~48h, preferably 4~24h, most preferably 6~18h）It is closed Stand.

According to the present invention, by the way that to the mixed serum convection drying, a kind of solid production of good fluidity can be obtained Thing, i.e. complex carrier of the invention.

Now, the convection drying can be carried out using conventional method, such as dry, vacuum atmosphere under inert gas atmosphere Heat drying etc. under lower drying or vacuum atmosphere, wherein it is preferred that heat drying under vacuum atmosphere.Drying temperature is generally 30 ~ 160 DEG C, preferably 60 ~ 130 DEG C, drying time is generally 2~24h, but is not limited to this sometimes.

Or, according to the present invention, by the metered precipitating reagent into the mixed serum, make solid matter from the mixing It is precipitated out in slurries, is derived from complex carrier.

The precipitating reagent is specifically described below.

According to the present invention, term " precipitating reagent " uses the common concept in this area, refers to that solid content solute can be reduced （Than magnesium compound as mentioned, porous carrier, Nonmetallocene part or Nonmetallocene complex etc.）Dissolving in its solution Spend the chemical inertness liquid for simultaneously and then making it be separated out in solid form from the solution.

According to the present invention, as the precipitating reagent, such as it can enumerate for solid content solute to be precipitated（It is such as described Magnesium compound, porous carrier, Nonmetallocene part or Nonmetallocene complex etc.）For be poor solvent, and for for Dissolve the solid content solute（Such as magnesium compound）The solvent for be good solvent solvent, such as can enumerate C_5-12 Alkane, C_5-12Cycloalkane, halo C_1-10Alkane and halo C_5-12Cycloalkane.

It is used as the C_5-12Alkane, such as can enumerate pentane, hexane, heptane, octane, nonane and decane etc., wherein excellent Select hexane, heptane and decane, most preferably hexane.

It is used as the C_5-12Cycloalkane, such as can enumerate hexamethylene, pentamethylene, cycloheptane, cyclodecane and cyclononane etc., Most preferably hexamethylene.

It is used as the halo C_1-10Alkane, such as can enumerate dichloromethane, dichloro hexane, two chloroheptanes, chloroform, Trichloroethanes, three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane and three NBBs etc..

It is used as the halo C_5-12Cycloalkane, such as can enumerate chlorocyclopentane, chlorocyclohexane, chloro cycloheptane, Chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo cycloheptane, bromo cyclooctane, Bromo cyclononane and bromo cyclodecane etc..

These precipitating reagents can be used alone one kind, can also be used in mixed way so that arbitrary ratio is a variety of.

The feed postition of precipitating reagent can be added or be added dropwise to be disposable, preferably disposable to add.In the precipitation process In, it is possible to use stir to promote the scattered of precipitating reagent, and be conducive to the final precipitation of solid product.The stirring can use any Form（Such as agitating paddle）, and rotating speed is generally 10~1000 revs/min etc..

To the consumption of the precipitating reagent, there is no particular limitation, but it is general by volume, the precipitating reagent dissolves with being used for The ratio of the solvent of the magnesium compound is 1：0.2~5, preferably 1：0.5~2, more preferably 1：0.8~1.5.

To the temperature of the precipitating reagent, also there is no particular limitation, but generally preferably normal temperature is to any molten less than used The temperature of the boiling point of agent and precipitating reagent（It is preferred that 20-80 DEG C, more preferably 40-60 DEG C）, but this is not limited to sometimes.Moreover, this is heavy Shallow lake process is general it is also preferred that in the temperature of normal temperature to the boiling point of any solvent and precipitating reagent less than used in（It is preferred that 20-80 DEG C, More preferably 40-60 DEG C）Lower progress 0.3-12 hours, but this is not limited to sometimes, and be substantially completely precipitated as with solid product It is accurate.

Completely after precipitation, the solid product obtained is filtered, washed and dried.For it is described filtering, washing and Dry method is not particularly limited, and those commonly used in the art can be used as needed.

As needed, the washing is general is carried out 1 ~ 6 time, preferably 3 ~ 4 times.Wherein, washer solvent is preferably used and sunk Shallow lake agent identical solvent, but it is also possible to different.

The drying can be carried out using conventional method, such as under inert gas seasoning, boulton process or vacuum Heat drying method, preferably inert gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum seasoning.

The temperature range of the drying is generally normal temperature to 140 DEG C.Drying time is generally 2-20 hours, but can also It is different according to the specifically used solvent case for being used to dissolve the magnesium compound.Such as, tetrahydrofuran conduct is being used During solvent for dissolving the magnesium compound, drying temperature is generally 80 DEG C or so, is dried under vacuum 2 ~ 12 hours, And when using toluene as solvent for dissolving the magnesium compound, drying temperature is generally 100 DEG C or so, under vacuo Dry 4 ~ 24 hours.

According to the present invention, by the complex carrier and the chemical treatments selected from IV B races metallic compound that make foregoing acquisition Contact, is derived from the load type non-metallocene catalyst of the present invention.

According to the present invention, reacted by making the chemical treatments with the complex carrier, cause the chemical treatments Occur complexation reaction with foregoing Nonmetallocene part contained on the complex carrier, thus on the complex carrier in-situ preparation with The Nonmetallocene complex of metallic atom centered on the Group IVB metallic atom（Supported reaction in situ）, this is of the invention One big feature.

The chemical treatments are specifically described below.

According to the present invention, the chemical treatments are used as using Group IVB metallic compound.

M(OR¹)_mX_nR² _4-m-n

Wherein：

M is 0,1,2,3 or 4；

N is 0,1,2,3 or 4；

X is halogen, such as F, Cl, Br and I etc.；And

When the chemical treatments are at normal temperatures liquid, the chemistry directly can be carried out using the chemical treatments Processing reaction.When the chemical treatments at normal temperatures be solid-state when, in order to measure with it is easy to operate for the sake of, preferably with solution Form uses the chemical treatments.Certainly, when the chemical treatments are at normal temperatures liquid, also may be used sometimes according to needs To use the chemical treatments as a solution, it is not particularly limited.

When preparing the solution of the chemical treatments, to now used solvent, there is no particular limitation, as long as its The chemical treatments can be dissolved and do not destroyed（Such as dissolve）The existing carrier structure of the complex carrier.

Specifically, C can be enumerated_5-12Alkane, C_5-12Cycloalkane, halo C_5-12Alkane and halo C_5-12Cycloalkane etc., than Pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, pentamethylene, hexamethylene, cycloheptane, ring can such as be enumerated Octane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro hendecane, chloro ten Dioxane and chlorocyclohexane etc., wherein it is preferred that pentane, hexane, decane and hexamethylene, most preferably hexane.

In addition, to concentration of the chemical treatments in its solution, there is no particular limitation, can be appropriate as needed Selection, as long as it can realize with the chemical treatments of scheduled volume to carry out the chemical treatment reaction.Such as preceding institute State, if chemical treatments are liquid, directly can carry out the processing using chemical treatments, but it is also possible to adjusted Used after the solution that chemical treatments are made.

In general, molar concentration of the chemical treatments in its solution is usually set to 0.01 ~ 1.0mol/L, but It is not limited to this.

According to the present invention, as the ways of carrying out of the chemical treatment reaction, such as can enumerate makes the complex carrier With the chemical treatments in solvent（Also referred to as chemical treatment solvent）In the presence of the mode that is contacted.

According to the present invention, to the chemical treatment, with solvent, there is no particular limitation, as long as it can dissolve the chemistry Inorganic agent, and do not destroy（Such as dissolve）The existing carrier structure of the complex carrier.

Specifically, as the chemical treatment solvent, C can be enumerated_5-12Alkane, C_5-12Cycloalkane, halo C_5-12Alkane Hydrocarbon and halo C_5-12Cycloalkane etc., such as can enumerate pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, Pentamethylene, hexamethylene, cycloheptane, cyclooctane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro Decane, chloro hendecane, chlorinated dodecane and chlorocyclohexane etc., wherein it is preferred that pentane, hexane, decane and hexamethylene, optimal Select hexane.

According to the present invention, the consumption of the chemical treatment solvent is used as so that the complex carrier is relative to describedization It is 1g with the ratio of solvent to learn processing：1-100ml, preferably 1g：2-40ml, but this is not limited to sometimes.In addition, before such as It is described as a solution use chemical treatments when, the chemical treatment solvent can be suitably reduced according to actual conditions Consumption, but be not particularly limited.

According to the present invention, be used as the consumption of the chemical treatments so that the complex carrier in terms of Mg elements with The mol ratio of the chemical treatments of Group IVB elemental metal reaches 1：0.01-1, preferably 1：0.01-0.50, more preferably 1： 0.10-0.30。

According to one embodiment of the present invention, in the presence of the chemical treatment solvent, make the complex carrier with The chemical treatments contact, thus carries out described chemical treatment reaction.

It as the ways of carrying out of the contact, such as can enumerate under agitation, add into the chemical treatment solvent Enter the complex carrier, subsequently or simultaneously add（It is preferred that being added dropwise）The solution of the chemical treatments or the chemical treatments, And after the addition terminates, at 0-100 DEG C（It is preferred that 20-80 DEG C）The lower mode for continuing to stir and react.To reaction now Time, there is no particular limitation, such as can enumerate 0.5-8h, preferably 1-4h.

After the chemical treatment reaction terminates, by being filtered, washed and dried, you can obtain and pass through chemically treated production Thing（The load type non-metallocene catalyst of the present invention）.

According to the present invention, described be filtered, washed and dried can be carried out using conventional method, and wherein washer solvent can be with Using with chemical treatment solvent identical solvent.As needed, the general progress of the washing 1~8 time, preferably 2~6 times, Most preferably 2~4 times.

According to the present invention, as needed, be optionally additionally included in makes the preparation method of the load type non-metallocene catalyst Before the complex carrier is contacted with the chemical treatments, chemistry is helped with selected from aikyiaiurnirsoxan beta, alkyl aluminum or its any combination The step of inorganic agent pre-processes the complex carrier（Pre-treatment step）.

In the context of the present specification, unless specifically stated otherwise it is or substantially unreasonable, without exception by by the pretreatment Complex carrier is also referred to as complex carrier.

Chemical treatments are helped to be specifically described to described below.

According to the present invention, chemical treatments are helped as described, such as can enumerate aikyiaiurnirsoxan beta and alkyl aluminum.

As the aikyiaiurnirsoxan beta, such as it can enumerate following formulas（I）Shown linear alumoxanes：(R)(R)Al-(Al (R)-O)_n- O-Al (R) (R), and following formulas（II）Shown Cyclic aluminoxane：-(Al(R)-O-)_n+2-。

（I）（II）

In aforementioned formula, group R is same to each other or different to each other（It is preferred that identical）, it is each independently selected from C₁-C₈Alkyl, it is excellent Select methyl, ethyl and isobutyl group, most preferable；N is any in the range of the arbitrary integer in the range of 1-50, preferably 10~30 Integer.

As the aikyiaiurnirsoxan beta, preferably MAO, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, Further preferred MAO and isobutyl aluminium alkoxide.

These aikyiaiurnirsoxan betas can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.

As the alkyl aluminum, such as it can enumerate the compound shown in below formula：

Al(R)₃

Wherein, group R is same to each other or different to each other（It is preferred that identical）, and it is each independently selected from C₁-C₈Alkyl, preferably first Base, ethyl and isobutyl group, most preferable.

Specifically, as the alkyl aluminum, such as trimethyl aluminium can be enumerated（Al(CH₃)₃）, triethyl aluminum（Al (CH₃CH₂)₃）, tri-n-n-propyl aluminum（Al(C₃H₇)₃）, triisopropylaluminiuand（Al(i-C₃H₇)₃）, triisobutyl aluminium（Al(i-C₄H₉)₃）、 Three n-butylaluminums（Al(C₄H₉)₃）, triisopentyl aluminium（Al(i-C₅H₁₁)₃）, three n-pentyl aluminium（Al(C₅H₁₁)₃）, tri-n-hexyl aluminum （Al(C₆H₁₃)₃）, three isohesyl aluminium（Al(i-C₆H₁₃)₃）, diethylmethyl aluminium（Al(CH₃)(CH₃CH₂)₂）And dimethyl ethyl Aluminium（Al(CH₃CH₂)(CH₃)₂）Deng wherein it is preferred that trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, most preferably three Aluminium ethide and triisobutyl aluminium.

These alkyl aluminums can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.

According to the present invention, chemical treatments are helped as described, it is possible to use only the aikyiaiurnirsoxan beta, can also be only with described Alkyl aluminum, but it is also possible to using the aikyiaiurnirsoxan beta and any mixture of the alkyl aluminum.Moreover, to each component in the mixture Ratio there is no particular limitation, can arbitrarily select as needed.

It is described to help what chemical treatments were usually used as a solution according to the present invention.Chemistry is being helped described in preparation During the solution of inorganic agent, to now used solvent, there is no particular limitation, as long as it, which can dissolve this, helps chemical treatments And do not destroy（Such as dissolve）The existing carrier structure of the complex carrier.

In addition, to the concentration for helping chemical treatments in its solution, there is no particular limitation, can fit as needed Work as selection, as long as it can realize to help chemical treatments to carry out the pre-treatment step described in scheduled volume.

It as the method for carrying out the pre-treatment step, such as can enumerate, prepare described help chemical treatments first Solution, then to intending with metered in the complex carrier for helping chemical treatments pretreatment（It is preferred that being added dropwise）It is described Help chemical treatment agent solution（Wherein containing helping chemical treatments described in scheduled volume）, or to described help chemical treatment agent solution In the metered complex carrier, be consequently formed reaction mixture.Now, reaction temperature is generally -40 ~ 60 DEG C, preferably -30 ~ 30 DEG C, the reaction time is generally 1 ~ 8h, most preferably preferably 2 ~ 6h, 3 ~ 4h（If necessary by stirring）.Then, by filtering, washing Wash and dry, the complex carrier by pretreatment is isolated from the reaction mixture.Then, using answering that the process is pre-processed Carrier is closed, according to describing exact same way before, the contact with chemical treatments is carried out.

According to the present invention, described be filtered, washed and dried can be carried out using conventional method, and wherein washer solvent can be with Identical solvent used during using with helping chemical treatments described in dissolving.As needed, the general progress of the washing 1~8 time, preferably 2~6 times, most preferably 2~4 times.The drying can be carried out using conventional method, such as inert gas seasoning, vacuum drying Method or heating under vacuum seasoning, preferably inert gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum Seasoning.The temperature range of the drying is generally normal temperature to 140 DEG C, and drying time is generally 2-20 hours, but is not limited to This.

According to the present invention, be used as the consumption of the Nonmetallocene part so that the magnesium compound in terms of Mg elements with The mol ratio of the Nonmetallocene part is 1：0.0001-1, preferably 1：0.0002-0.4, more preferably 1：0.0008-0.2, enters one Step preferably 1：0.001-0.1.

According to the present invention, the consumption of the solvent is used as so that the ratio of the magnesium compound and the solvent is 1mol： 75~400ml, preferably 1mol：150~300ml, more preferably 1mol：200~250ml.

According to the present invention, the consumption of the alcohol is used as so that the magnesium compound in terms of Mg elements rubs with the alcohol You are than being 1：0.02~4.00, preferably 1：0.05~3.00, more preferably 1：0.10~2.50.

According to the present invention, the consumption of the porous carrier is used as so that the magnesium compound in terms of magnesium compound solid Mass ratio with the porous carrier is 1：0.1-20, preferably 1：0.5-10.

According to the present invention, the consumption of the precipitating reagent is used as so that the precipitating reagent is 1 with the volume ratio of the solvent： 0.2~5, preferably 1：0.5~2, more preferably 1：0.8~1.5.

According to the present invention, be used as the consumption of the chemical treatments so that the complex carrier in terms of Mg elements with The mol ratio of the chemical treatments of Group IVB elemental metal is 1：0.01-1, preferably 1：0.01-0.50, more preferably 1： 0.10-0.30。

According to the present invention, be used as the consumption for helping chemical treatments so that the complex carrier in terms of Mg elements with To help the mol ratio of chemical treatments as 1 described in Al elements are counted：0-1.0, preferably 1：0-0.5, more preferably 1：0.1-0.5.

Known to those skilled in the art to be, foregoing all method and steps are preferably in the bar of substantially anhydrous and oxygen-free Carried out under part.Substantially anhydrous and oxygen-free mentioned here refers to the content of system reclaimed water and oxygen continuously less than 100ppm.Moreover, The load type non-metallocene catalyst of the present invention usually requires pressure-fired inert gas in confined conditions after preparation（Such as nitrogen Gas, argon gas, helium etc.）In the presence of save backup.

According to the present invention, in foregoing manufacture method A and manufacture method B, the co-catalyst is selected from aikyiaiurnirsoxan beta, alkane At least one in base aluminium, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, is preferably selected from aikyiaiurnirsoxan beta and alkyl aluminum In at least one.

As the aikyiaiurnirsoxan beta, such as it can enumerate formula (R) (R) Al- (Al (R)-O)_nLine shown in-O-Al (R) (R) Type aikyiaiurnirsoxan beta, or formula-(Al (R)-O-)_n+2- shown Cyclic aluminoxane.

In aforementioned formula, group R is same to each other or different to each other（It is preferred that identical）, it is each independently selected from C₁-C₈Alkyl, it is excellent Select methyl, ethyl and isobutyl group, most preferable.N is any in the range of the arbitrary integer in the range of 1-50, preferably 10~30 Integer.

As the aikyiaiurnirsoxan beta, preferably MAO, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, Further preferred MAO and isobutyl aluminium alkoxide, and most preferable aikyiaiurnirsoxan beta.

Al(R)₃

Specifically, as the alkyl aluminum, such as trimethyl aluminium can be enumerated（Al(CH₃)₃）, triethyl aluminum（Al (CH₃CH₂)₃）, tri-n-n-propyl aluminum（Al(C₃H₇)₃）, triisobutyl aluminium（Al(i-C₄H₉)₃）, three n-butylaluminums（Al(C₄H₉)₃）, three Isopentyl aluminium（Al(i-C₅H₁₁)₃）, three n-pentyl aluminium（Al(C₅H₁₁)₃）, tri-n-hexyl aluminum（Al(C₆H₁₃)₃）, three isohesyl aluminium （Al(i-C₆H₁₃)₃）, diethylmethyl aluminium（Al(CH₃)(CH₃CH₂)₂）With dimethyl ethyl aluminium（Al(CH₃CH₂)(CH₃)₂）Deng, Wherein preferred trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum and triisobutyl aluminium, further preferred triethyl aluminum and triisobutyl Aluminium, and most preferably triethyl aluminum.

As the haloalkyl aluminium, such as it can enumerate the compound shown in below formula：

Al(R)_nX_3-n

Wherein, group R is same to each other or different to each other（It is preferred that identical）, and it is each independently selected from C₁-C₈Alkyl, preferably first Base, ethyl and isobutyl group, most preferable.Group X is halogen, preferably chlorine.N is 1 or 2.

Specifically, as the haloalkyl aluminium, such as a Chlorodimethyl aluminium can be enumerated（Al(CH₃)₂Cl）, dichloro Aluminium methyl（Al(CH₃)Cl₂））, aluminium diethyl monochloride（Al(CH₃CH₂)₂Cl）, ethyl aluminum dichloride（Al(CH₃CH₂)Cl₂）, a chlorine two Propyl group aluminium（Al(C₃H₇)₂Cl）, two chloropropyl aluminium（Al(C₃H₇)Cl₂））, a chlorine di-n-butyl aluminium（Al(C₄H₉)₂Cl）, dichloro just Butyl aluminium（Al(C₄H₉)Cl₂）, a chloro-di-isobutyl aluminum（Al(i-C₄H₉)₂Cl）, dichloro aluminium isobutyl（Al(i-C₄H₉)Cl₂）, one The n-pentyl aluminium of chlorine two（Al(C₅H₁₁)₂Cl）, dichloro n-pentyl aluminium（Al(C₅H₁₁)Cl₂）, a chlorine diisoamyl aluminium（Al(i-C₅H₁₁)₂Cl）, dichloro isopentyl aluminium（Al(i-C₅H₁₁)Cl₂）, a chlorine di-n-hexyl aluminium（Al(C₆H₁₃)₂Cl）, dichloro n-hexyl aluminium（Al (C₆H₁₃)Cl₂）, the isohesyl aluminium of a chlorine two（Al(i-C₆H₁₃)₂Cl）, dichloro isohesyl aluminium（Al(i-C₆H₁₃)Cl₂）、

Chloromethyl aluminium ethide（Al(CH₃) (CH₃CH₂)Cl）, chloromethyl propyl group aluminium（Al(CH₃) (C₃H₇)Cl）, one Chloromethyl n-butylaluminum（Al(CH₃) (C₄H₉)Cl）, chloromethyl aluminium isobutyl（Al(CH₃) (i-C₄H₉)Cl）, a chloroethyl Propyl group aluminium（Al(CH₂CH₃) (C₃H₇)Cl）, a chloroethyl n-butylaluminum（AlCH₂CH₃)(C₄H₉)Cl）, chloromethyl aluminium isobutyl （AlCH₂CH₃)(i-C₄H₉)Cl）Deng, wherein it is preferred that aluminium diethyl monochloride, ethyl aluminum dichloride, a chlorine di-n-butyl aluminium, dichloro just Butyl aluminium, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl, a chlorine di-n-hexyl aluminium, dichloro n-hexyl aluminium, further preferred chlorine two Aluminium ethide, ethyl aluminum dichloride and a chlorine di-n-hexyl aluminium, and most preferably aluminium diethyl monochloride.

These haloalkyl aluminium can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.

, can be directly using commonly used in the art as the boron fluothane, the boron alkyl and the boron alkyl ammonium salt Those, be not particularly limited.

In addition, according to the present invention, the co-catalyst can be used alone one kind, can also arbitrarily it compare as needed A variety of foregoing co-catalysts are applied in combination in example, are not particularly limited.

,, such as can be with as the solvent for polymerization in foregoing manufacture method A and manufacture method B according to the present invention Enumerate this area carry out slurry olefin polymerization when it is conventional use of those, be not particularly limited.Specifically, as institute Solvent for polymerization is stated, such as can enumerate C_4-10Alkane（Such as butane, pentane, hexane, heptane, octane, nonane or decane etc.）、 Halo C_1-10Alkane（Such as dichloromethane）、C_6-12Cycloalkane（Hexamethylene, cycloheptane, cyclooctane, cyclononane or cyclodecane）、 C_6-20Aromatic hydrocarbon（Such as toluene and dimethylbenzene）Deng.Wherein, pentane, hexane, heptane or hexamethylene are preferably used as described poly- Share solvent, most preferably hexane.

These solvent for polymerization can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.

,, such as can be with as the consumption of the solvent for polymerization in described step A or step A' according to the present invention Enumerate 10 ~ 400 liters of solvent for polymerization/gram major catalyst, preferably 20 ~ 200 liters solvent for polymerization/gram major catalysts, more preferably 50 ~ 150 liters of solvent for polymerization/gram major catalysts, but this is not limited to sometimes.The step B or step B' are also required to mend as previously described When filling solvent for polymerization, the specific consumption of its solvent for polymerization similar can also be set.

According to the present invention, in described step A or step A', as the consumption of the co-catalyst, it is general cause with The mol ratio of the co-catalyst of aluminium or boron meter and the major catalyst in terms of the central metal atom reaches 1~ 1000：1, preferably 5~500：1, more preferably 10~100：1, but this is not limited to sometimes.For example preceding institute of step B or step B' State be also required to supplement co-catalyst when, the specific consumption of its co-catalyst similar can also be set.

In the manufacture method A and manufacture method B that state before this invention, material point can be easy to as needed using stirring Dissipate or reaction is uniform, this can be carried out according to well known to a person skilled in the art mode.

For the manufacture method A and manufacture method B of foregoing ethene-alpha-olefin copolymer of the present invention, except this In specification beyond the foregoing content particularly pointed out, other technology contents do not explained（Such as slurry polymerization process ways of carrying out, stir Mix mode, polymerization type of reactor, monomer feed mode, master/co-catalyst feeding manner, copolymer product discharge method Deng）, those conventionally known in the art can be directly applicable, are not particularly limited, the description thereof will be omitted herein.

The ethene-alpha-olefin copolymer of the present invention can be total to by the ethene-alpha-olefin of foregoing manufacture method A manufactures The polymers A or ethene-alpha-olefin copolymer B or the ethene-alpha-olefin manufactured by foregoing manufacture method B Copolymer A and the arbitrary proportion mixture of the ethene-alpha-olefin copolymer B.

Further, the invention further relates to a kind of polymer composition, it is total to comprising the foregoing ethene-alpha-olefin of the present invention Polymers and antioxidant.

According to the present invention, as the antioxidant, such as can enumerate it is known in the art it is any can by it is conventional close Into or commercialization sale antioxidant, be not particularly limited.It is known that the antioxidant is usual by primary antioxidant and auxiliary Antioxidant is constituted, but can also be used as the antioxidant using only the primary antioxidant without using auxiliary anti-oxidant sometimes.

According to the present invention, the gross weight using the polymer composition is counts, and the antioxidant is in the combination of polymers Content in thing is generally 0.05-1.0wt%, preferably 0.1-0.5wt%, is not particularly limited.In addition, the auxiliary anti-oxidant 0~6 is generally with the mass ratio of the antioxidant：1, preferably 0.5~3：1, it is not particularly limited.

According to the present invention, at least one of the primary antioxidant in hindered phenol compound and aromatic amine compounds. As the primary antioxidant, such as it can enumerate：

2,6- di-tert-butyl methyl phenols（Article number：Antioxidant BHT）,

β-(4- hydroxyl -3,5- di-tert-butyl-phenyls) positive octadecanol ester of propionic acid（Article number：Antioxidant 1076）,

Styrene phenol（Article number：Antioxidant SP）,

2,4,6- tri-butyl-phenols（Article number：Antioxidant 246）,

DBPC 2,6 ditertiary butyl p cresol（Article number：Antioxidant BHA）,

Tert-butylhydroquinone (article number：Antioxidant TBHQ),

3,5- di-tert-butyl-4-hydroxyl benzyl diethyl phosphates（Article number：Antioxidant 1222）,

β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid isooctanol ester（Article number：Antioxidant 1135）,

2,2' methylene bis (4- methyl-6-tert-butylphenols)（Article number：Antioxidant 2246）,

2,2'- thiobis (4- methyl-6-tert-butylphenols)（Article number：Antioxidant 2246 S）,

4,4'- thiobis (3 methy 6 tert butyl phenol)（Article number：Antioxidant 300）,

1,3,5- trimethyl -2,4,6- tri-（3,5- di-tert-butyl-4-hydroxyl benzyls）Benzene（Article number：Antioxidant 330）,

4,4- thiobis（2- methyl-6-tert-butylphenols）（Article number：Antioxidant 736）,

4,4' methylene bis (2,6 di t butyl phenol)（Article number：Antioxidant 4426）,

4,4'- butylidenes-bis- (6- tert-butyl-m-cresols),

Four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters（Article number：Antioxidant 1010）,

2,4- bis--(n-octylthiomethylene) -6- methyl-phenols（Antioxidant 1520）,

2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate]（Article number：Antioxidant 1035）,

4- [(the pungent sulfenyl -1,3,5- triazines -2- bases of 4,6- bis-) amino] -2,6- two (1,1- Methylethyls) phenol （Article number：Antioxidant 565）,

[[3,5- bis- (1,1- dimethyl ethyls) -4- hydroxy phenyls] methyl] butylmalonic acid two (1,2,2,6, 6- pentamethyl -4- piperidyls) ester,

3- (1,1- dimethyl ethyls)-β-[3- (1,1- dimethyl ethyls) -4- hydroxyphenyls] -4- hydroxy-betas-methylbenzene first Acid -1,2- ethylidene esters,

[[3- (1,1- the dimethylethyls) -2- hydroxy-5-methyls phenyl]-octahydro -4,7- methylene -1H- indenes of 2,6- bis- Base] -4- methylphenols, 4,4'- thiobis (5- methyl -2-TBP),

1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone（Article number：Antioxidant 1790）,

1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) -1,3,5- triazines -2,4,6 [1H, 3H, 5H] triketone （Article number：Antioxidant 3114）,

1,3,5- trimethyls -2,4,6- three (3,5 di-tert-butyl-4-hydroxyl benzyl) benzene（Article number：Antioxidant 330）,

N, N'-1,6- hexylidene two [(1,1- the dimethyl ethyls) -4- hydroxyls of 3,5- bis- hydrocinnamamide]（Article number： Antioxidant 1098）,

1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane（Article number：Antioxidant CA）、

Two [3- (1,1- dimethyl ethyls) -4- hydroxy-5-methyl bases benzenpropanoic acid] three polyethylene glycol（Article number：Antioxidant 245）,

3,5- bis- (1,1- dimethyl ethyls) -4- hydroxy-benzenepropanoic acid -1,6- dihexyl esters（Article number：Antioxidant 259）, and

Ethyl -3,5- di-t-butyl -4- hydroxybenzylphosphonic acid ester calcium salts（Article number：Antioxidant 1425）.

According to the present invention, these primary antioxidants can be used alone one kind, can also multiple combinations use.

According to the present invention, as the primary antioxidant, preferably hindered phenol compound, more preferably β-(4 hydroxyls-3,5- Di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid（Article number：Antioxidant 1076）, four [β-(3,5- di-t-butyl -4- hydroxy benzenes Base) propionic acid] pentaerythritol ester（Article number：Antioxidant 1010）Or its combination, the most preferably β-(uncle of 4-hydroxyl-3,5-two Butyl phenyl) the positive octadecanol ester article number of propionic acid：Antioxidant 1076）.

According to the present invention, the one kind or many of the auxiliary anti-oxidant in phosphite ester kind antioxidant and sulfur-bearing antioxidant Kind.

As the phosphite ester kind antioxidant, such as it can enumerate：

Three nonylated phenyl phosphite esters（Article number：Antioxidant TNP P）,

(2,4- di-tert-butyl-phenyls) tris phosphite（Article number：Irgasfos 168）,

Four (2,4- di-tert-butylphenols) -4,4'- xenyl diphosphites (article numbers：Antioxidant P-EPQ),

Distearyl pentaerythritol diphosphite（Article number：Antioxidant 618）,

Pentaerythritol bis-phosphite two (2,4- di-tert-butyl phenyl) ester (antioxidant 626), and

Double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate (article numbers：Antioxidant PEP-36).

According to the present invention, these phosphite ester kind antioxidants can be used alone one kind, can also multiple combinations use.

As the sulfur-bearing antioxidant, such as it can enumerate：

Thio-2 acid 2 stearyl ester（DSTDP）,

Dilauryl thiodipropionate（DLTDP）,

Double 14 esters of thio-2 acid（DMTDP）,

Double 13 esters of thio-2 acid（DTDTP）,

Pentaerythrite four（3- lauryl thiopropionates）（Article number：Antioxidant 412S）, and

Two (octadecyl) disulphide.

According to the present invention, these sulfur-bearing antioxidant can be used alone one kind, can also multiple combinations use.

It is used as the auxiliary anti-oxidant, preferably (2,4- di-tert-butyl-phenyl) tris phosphite（Article number：Irgasfos 168）、 Thio-2 acid 2 stearyl ester（DSTDP）, dilauryl thiodipropionate（DLTDP）Or its combination, most preferably thio dipropyl Sour distearyl alcohol ester（DSTDP）.

, as needed, can also be comprising this area in manufacture polymer group in the polymer composition according to the present invention Conventional use of various additives during compound, such as age resister, fire retardant, processing aid, anti-blocking agent, lubricant, the demoulding Agent, plasticizer, antistatic additive, pigment, halogen-absorber and filler etc..These additives can be used alone, can also be two kinds Or multiple combinations are used, it is not particularly limited.In addition, the consumption of the additive can use the conventional use of this area Amount, there is no particular limitation, will not be repeated here.

Especially, one kind or many in pigment and halogen-absorber can be optionally included in polymer composition of the invention Kind.

According to the present invention, as the pigment, such as the black pigments such as carbon black or yellow uitramarine can be enumerated and orange The color pigments such as pigment, wherein it is preferred that carbon black.These pigment can be used alone one kind, can also multiple combinations use.Make Used time, gross weight using the polymer composition is counts, content one of the black pigment in the polymer composition As be 15-65wt%, and content of the color pigment in the polymer composition is generally 2.0-5.0wt%, not It is special to limit.

According to the present invention, as the halogen-absorber, such as it can enumerate any halogen commonly used in the art and inhale Agent is received, such as can further enumerate calcium stearate or zinc stearate etc..Gross weight using the polymer composition is counts, institute Content of the halogen-absorber in the polymer composition generally 0-0.5wt%, preferably 0-0.3wt% are stated, it is not special Restriction.

According to the present invention, in order to manufacture the polymer composition, by by the ethene-alpha-olefin copolymer, described Antioxidant and the foregoing various additives used as needed（Especially pigment and/or halogen-absorber）, according to predetermined Usage ratio, is mixed according to method well known in the art（Such as melting mixing）To uniform, it is not particularly limited.

According to a further embodiment of the invention, it is related to a kind of moulded products, it is by this hair of melt-processed Bright foregoing polymer composition is simultaneously molded with.As the forming method, such as it can enumerate conventionally known in the art Any method, such as extrude, be molded, rotational moulding and molded etc., wherein it is preferred that single or double screw extrusion molding.As described The condition of molding of single or double screw extrusion molding, there is no particular limitation, can directly be applicable those commonly used in the art, Such as can be extruder barrel temperature at 150 DEG C -220 DEG C, die head temperature is in 200 DEG C -220 DEG C, hauling speed 80-150cm/ Min, preferably 100-120cm/min, but it is not limited to this.Or, as the example of the rotation molding, such as can enumerate by Polymer composition is put into rotational moulding container, the method that rotational moulding is carried out at 150-300 DEG C of mould temperature, now molding cycle condition For：Heat time 5-30 minute, time 1--20 minute, cool time 1-20 minute are flattened, but be not limited to this.

According to the present invention, the form to the moulded products is not particularly limited, such as can enumerate film, sheet material, appearance Device（Bucket, disk, bottle etc.）, tubing, section bar etc., wherein it is preferred that tubing, bucket and film, most preferably tubing.

Embodiment

The present invention is illustrated using embodiment in further detail below, but the present invention is not limited to these embodiments.

The heap density of copolymer（Unit is g/cm³）Determine：Carried out with reference to chinese national standard GB 1636-79.

The oligomer of copolymer is determined：Take out 1 liter of solvent in the filtrate center line that filters or centrifuge out, higher than Under the conditions of solvent boiling point or closed vacuumize fully dries remaining material gross mass after solvent.

The fine powder of copolymer（Less than 75 microns）Assay：Using sieve method, the powder of the copolymer is passed through into 200 mesh （75 microns of aperture）Sieved through sieve, fine powder quality after sieving divided by the gross mass of copolymer are measured.

The melt index of copolymer（190℃；Load is 2.16 kilograms, or if any clear and definite, load is 5 kilograms）Determine：Ginseng The quasi- GB T 3682-2000 of sighting target are carried out（Unit is g/10min）.

The molecular weight distribution mw/mn of copolymer is determined：Using the GPC V2000 types gel chromatography point of WATERS companies of the U.S. Analyzer is measured, from 4 Agilent PLgel Olexis type chromatographic columns, with 1,2,4- trichloro-benzenes for mobile phase, is determined When temperature be 150 DEG C.

The density measurement of copolymer：Reference standard GB/T 1033-86 are carried out（Unit is g/cm³）.

The average grain diameter of copolymer is determined：Carried out on Beckman Coulter LS230 type laser particle size analyzers, its Particle size determination scope is 0.04 ~ 2000 micron.

The processing characteristics evaluation of copolymer：By copolymer and antioxidant 1010（Four [β-(3,5- di-t-butyl -4- hydroxyls Phenyl) propionic acid] pentaerythritol ester）, irgasfos 168（(2,4- di-tert-butyl-phenyls) tris phosphite）With calcium stearate according to matter The ratio than 100/0.1/0.2/0.1 is measured to be well mixed.The well mixed material is passed through into parallel equidirectional two-screw extruder （Nanjing Rhea extrusion machinery equipment Co., Ltd CTE-35 types）Simultaneously pelletizing obtains corresponding pellet for melting extrusion, water-bath cooling. Each section of temperature setting of double screw extruder be：185℃-200℃-215℃-225℃-225℃-225℃-230℃-230℃- 220℃-220℃（Head）.After obtained pellet is dried 4 hours through 70 DEG C, double screw extruder is added to（Crouse Ma Fei OD20-63mm）In, in -240 DEG C -235 DEG C of extrusion temperature 190 DEG C -210 DEG C -220 DEG C -230 DEG C（Die head）And extrusion linear speed Continuously extruded under conditions of about 1 m/min, obtain the mm of the diameter 63 and mm of nominal wall thickness about 5.8 tubing.Squeezed in the twin-screw The reading for going out the main frame ammeter of machine reaches stable state（Reading changes within positive and negative 0.1A）Afterwards, the main frame electric current of record now （Unit is A）.Main frame electric current is smaller, then the processing characteristics for evaluating the copolymer is better.

The polymerization activity of major catalyst is determined：After polymerisation terminates, by the polymerizate in reactor（Ethene- Alpha olefin copolymer）Filter and dry, then weigh the quality of the polymerizate, with the polymerizate quality divided by master used The ratio of the quality of catalyst represents its polymerization activity（Unit is kg polymer/g catalyst or kg polymer/gCat）.

Metallic element in major catalyst（Such as Ti and Mg）Assay：Using ICP-AES methods.

The assay of Nonmetallocene part or complex in major catalyst：Using elemental microanalysis method.

The evaluation of major catalyst copolymerization effect：Major catalyst is divided into equal two parts, in identical polymeric reaction condition Under, separately carry out closing and exist the ethene of comonomer and being total to for comonomer in the absence of the ethylene homo of comonomer Polymerization, and the polymerization activity of the major catalyst in the case of two kinds is determined respectively.The difference of two kinds of polymerization activities numerically is anti- Reflect the copolymerization effect of the major catalyst.If activity increase, shows that copolymerization effect is good, active increased amplitude is got over after copolymerization Greatly, then its copolymerization effect is more notable, and activity reduction, then show that copolymerization effect is poor after such as copolymerization.

The environmental stress cracking resistance of polymer（ESCR）It is public in Britain Rayran according to GB/T 1842-2008 standards Carried out on the RR/ESC resisting environmental stress and cracking instrument of department.

Plastics simply supported beam notch impact strength is rushed according to GB/T 1043-2008 in the Italian type pendulum of Ceast companies 7611 Hit on instrument and carry out, determined at 0 DEG C of v-notch sample.

Tensile yield strength is tensile property according to Instron5965 types omnipotent examination in the U.S.'s obtained by GB/T 1040-2006 Test on machine and carry out.

Full notch creep test（FNCT）Carried out, sampled from tubing, in German IPT companies according to ISO 16770 Tested on the full notch creep test machine of V1598-0006 types.The notch depth 1.6mm in the face of sample 4.Test temperature is 80 DEG C, And the use of 2wt% Arkopal N-110 is test(ing) medium, test stress is 4.0MPa.Record the out-of-service time.

Embodiment 1

Magnesium compound uses anhydrous magnesium chloride, Nonmetallocene part use structure for Compound, solvent uses tetrahydrofuran, and alcohol uses ethanol, and porous carrier uses silica, i.e. silica gel, model Ineos The ES757 of company, 4h is persistently calcined under 600 DEG C, nitrogen atmosphere first by silica gel and thermal activation.Group IVB chemical treatments are adopted Use titanium tetrachloride（TiCl₄）.

5 grams of magnesium compounds are weighed, are added to after solvent, alcohol and Nonmetallocene part is added, is completely dissolved at normal temperatures Magnesium compound solution is obtained, porous carrier is then added, after stirring 2 hours, mixed serum is obtained, is then uniformly heated to 90 DEG C, drying is directly vacuumized, complex carrier is obtained.

Obtained complex carrier is added in hexane solvent, normal temperature is added dropwise to Group IVB chemical treatments in lower 30 minutes, Then after being uniformly heated to 60 DEG C of isothermal reactions 2 hours, filtering, hexane solvent is washed 3 times, each consumption with add before it is molten Dosage is identical, finally vacuumizes drying at 60 DEG C, obtains load type non-metallocene catalyst.

Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:2；In terms of Mg elements, magnesium compound and non-cyclopentadienyl gold The mol ratio of metal ligand is 1:0.08；It is 1 with alcohol mol ratio:2；Proportioning with solvent hexane is 1mol:210ml；With Mg members The complex carrier of element meter is 1 with chemical treatments mol ratio:0.20.

Load type non-metallocene catalyst is designated as CAT-1.

Embodiment 2

It is substantially the same manner as Example 1, but be with the following changes：

Before complex carrier is contacted with the chemical treatments, first pass through and help the compound load of chemical treatments triethyl aluminum processing Body.

That is, complex carrier is added in hexane solvent, then is slowly added dropwise and helps chemical treatments triethyl aluminum（Concentration is 0.88mol/L, hexane solution）, stirring is filtered after 2 hours at 60 DEG C, and hexane is washed 3 times, each consumption with add before it is molten Dosage is identical, finally vacuumizes drying at 60 DEG C, obtains load type non-metallocene catalyst.It is compound wherein in terms of Mg elements Carrier using what Al elements were counted with helping the mol ratio of chemical treatments as 1：0.2.

Load type non-metallocene catalyst is designated as CAT-2.

Embodiment 3

Before chemical treatments contact described in complex carrier, first pass through and help the compound load of chemical treatments MAO processing Body.

That is, modification complex carrier is added in toluene solvant, then is slowly added dropwise and helps chemical treatments MAO（It is dense Spend for 10wt%, toluene solution）, stirring is filtered after 2 hours at 60 DEG C, and toluene is washed 3 times, each consumption with add before it is molten Dosage is identical, finally vacuumizes drying at 100 DEG C, obtains load type non-metallocene catalyst.Wherein answering in terms of Mg elements Close carrier and help the mol ratio of chemical treatments as 1 using what Al elements were counted：0.4.

Load type non-metallocene catalyst is designated as CAT-3.

Embodiment 4

Magnesium compound is changed to isobutoxy magnesium chloride（Mg(i-OC₄H₉)Cl）, alcohol is changed to n-butanol, and solvent changes into toluene, Nonmetallocene part is used, porous carrier changes into TiO₂, held under 400 DEG C, nitrogen atmosphere Continuous roasting 4h and thermal activation.Mixed serum changes into addition precipitating reagent hexane and is allowed to complete precipitation, filters and is washed with precipitating reagent Three times, 60 DEG C vacuumize drying.Chemical treatments are changed to zirconium chloride（ZrCl4）.

Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:1；In terms of Mg elements, magnesium compound and non-cyclopentadienyl gold The mol ratio of metal ligand is 1:0.04；It is 1 with alcohol mol ratio:1；Proportioning with solvent is 1mol:150ml；In terms of Mg elements Complex carrier and chemical treatments mol ratio be 1:0.30.The volume ratio of precipitating reagent and solvent is 1：1.

Load type non-metallocene catalyst is designated as CAT-4.

Embodiment 5

Magnesium compound changes into anhydrous magnesium bromide（MgBr₂）, alcohol changes into 2-Ethylhexyl Alcohol, and solvent changes into tetrahydrochysene furan Mutter, Nonmetallocene part is used, porous carrier uses alundum (Al2O3).By alundum (Al2O3) 700 DEG C, be persistently calcined 6h under nitrogen atmosphere.Chemical treatments are changed to titanium tetrabromide（TiBr₄）, mixed serum changed at 105 DEG C Directly vacuumize drying.

Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:5；In terms of Mg elements, magnesium compound and non-cyclopentadienyl gold The mol ratio of metal ligand is 1:0.2；It is 1 with alcohol mol ratio:0.7；Proportioning with solvent is 1mol:280ml；In terms of Mg elements Complex carrier and chemical treatments mol ratio be 1:0.10.

Load type non-metallocene catalyst is designated as CAT-5.

Embodiment 6

Magnesium compound changes into magnesium ethylate（Mg(OC₂H₅)₂）, solvent changes into dimethylbenzene, and Nonmetallocene part is used, porous carrier is using silica-magnesia mixed oxide（Mass ratio 1：1）.By titanium dioxide Silicon-magnesia mixed oxide is persistently calcined 4h under 600 DEG C, argon gas atmosphere.

Alcohol is changed to trichlorine methanol.The chemical treatments of Group IVB metallic compound change into tetraethyl titanium（Ti(CH₃CH₂)₄）, Mixed serum changes into addition precipitating reagent hexamethylene and is allowed to complete precipitation, filters and 80 DEG C are washed after three times with precipitating reagent and vacuumize Dry.

Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:10；In terms of Mg elements, magnesium compound and non-cyclopentadienyl gold The mol ratio of metal ligand is 1:0.05；It is 1 with alcohol mol ratio:0.7；Proportioning with solvent is 1mol:200ml；With Mg elements The complex carrier of meter is 1 with chemical treatments mol ratio:0.15；The volume ratio of precipitating reagent and solvent is 1：1.5.

Load type non-metallocene catalyst is designated as CAT-6.

Embodiment 7

Magnesium compound changes into magnesium ethide（Mg(C₂H₅)₂）, solvent changes into diethylbenzene, and alcohol changes into benzyl carbinol, non-cyclopentadienyl gold Metal ligand is used, porous carrier uses montmorillonite.By montmorillonite in 400 DEG C, nitrogen atmosphere Persistently it is calcined 8h down.The chemical treatments of Group IVB metallic compound change into tetra-n-butyl titanium（Ti(C₄H₉)₄）, mixed serum changes It is changed into directly vacuumizing drying at 130 DEG C.

Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:3；In terms of Mg elements, magnesium compound and non-cyclopentadienyl gold The mol ratio of metal ligand is 1:0.4；It is 1 with alcohol mol ratio:1.5；Complex carrier in terms of Mg elements rubs with chemical treatments You are than being 1:0.50；Magnesium compound is 1mol with solvent burden ratio：400ml.

Load type non-metallocene catalyst is designated as CAT-7.

Embodiment 8

Magnesium compound changes into ethylmagnesium chloride（Mg(C₂H₅)Cl）, alcohol is changed to cyclohexanol, and solvent changes into hexamethylene, many Hole carrier is using partial cross-linked（The degree of cross linking is 30%）Polystyrene.The polystyrene is persistently dried under 85 DEG C, nitrogen atmosphere Dry 12h.Nonmetallocene part is used, the chemical treatments of Group IVB metallic compound change into three Isobutoxy titanium chloride（TiCl(i-OC₄H₉)₃）.

Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:0.5；In terms of Mg elements, magnesium compound and non-cyclopentadienyl The mol ratio of metal ligand is 1:0.01；It is 1 with alcohol mol ratio:2.5；Proportioning with solvent hexane is 1mol:210ml；With The complex carrier of Mg element meters is 1 with chemical treatments mol ratio:0.20.

Load type non-metallocene catalyst is designated as CAT-8.

Reference example A

Magnesium compound uses anhydrous magnesium chloride, and the first solvent uses tetrahydrofuran, and alcohol uses ethanol, and porous carrier uses two Silica, i.e. silica gel, the ES757 of model Ineos companies, 4h is persistently calcined under 600 DEG C, nitrogen atmosphere first by silica gel and Thermal activation.Group IVB chemical treatments use titanium tetrachloride（TiCl₄）, the second solvent uses dichloromethane, Nonmetallocene complex Use structure forCompound.

5 grams of magnesium compounds are weighed, are added to after the first solvent, alcohol is added, is completely dissolved obtains magnesium chemical combination at normal temperatures Thing solution, then adds porous carrier, after stirring 2 hours, obtains the first mixed serum, is then uniformly heated to 90 DEG C, directly Drying is vacuumized, complex carrier is obtained.

Obtained complex carrier is added in hexane solvent, normal temperature is added dropwise to Group IVB chemical treatments in lower 30 minutes, Then after being uniformly heated to 60 DEG C of isothermal reactions 2 hours, filtering, hexane solvent is washed 3 times, each consumption with add before it is molten Dosage is identical, finally vacuumizes drying at 60 DEG C, obtains modifying complex carrier.

At room temperature, Nonmetallocene complex is added in the second solvent, then adds modification complex carrier, stirring 4 Hour, then closed standing directly vacuumize drying after 12 hours under normal temperature, obtain load type non-metallocene catalyst.

Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:2；It is 1 with alcohol mol ratio in terms of Mg elements: 2；Proportioning with the first solvent is 1mol:210ml；The complex carrier in terms of Mg elements with Group IVB elemental metal The mol ratio of the chemical treatments is 1:0.20；The complex carrier and the Nonmetallocene complex in terms of Mg elements Mol ratio is 1:0.08；Nonmetallocene complex is 0.1 grams per milliliter relative to the ratio of second solvent.

Load type non-metallocene catalyst is designated as CAT-A.

Reference example B

The complex carrier and the mol ratio of the Nonmetallocene part counted using Mg elements is 1:0.04；

Load type non-metallocene catalyst is designated as CAT-B.

Reference example C

The complex carrier and the mol ratio of the Nonmetallocene part counted using Mg elements is 1:0.16；

Load type non-metallocene catalyst is designated as CAT-C.

Reference example D

Nonmetallocene part is added without in catalyst preparation process；

Load type non-metallocene catalyst is designated as CAT-D.

Application Example

By obtained load type non-metallocene catalyst CAT-1~8, CAT-A~D in the embodiment of the present invention respectively following Under the conditions of carry out the homopolymerization and copolymerization of ethene in accordance with the following methods：

Polymerizing condition is：5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents polymerize stagnation pressure 0.8MPa, gather Close 85 DEG C of temperature；First stage：Hydrogen and ethylene gas ratio according to setting add a certain amount of hydrogen, and a certain amount of hexene- 1, being continually fed into ethene makes polymerization stagnation pressure constant in 0.8MPa, reacts the gas phase that reactor is laid down after the reaction time for reaching setting Composition, the first stage stopping of reaction；Second stage：Second stage hydrogen and ethylene gas ratio according to setting add a certain amount of Hydrogen, a certain amount of hexene -1, being continually fed into ethene makes polymerization stagnation pressure constant in 0.8MPa, and reaction reaches the reaction time of setting Stop reaction, the second stage stopping of reaction afterwards.After reaction terminates, gas reactor is vented, kettle interpolymer is released, claimed after drying Measure quality.The concrete condition and polymerization evaluation result of the polymerisation are as shown in table 1.

The polymer uniform particle sizes prepared from table 1, the method provided with the present invention, molecular weight distribution is appropriate, oligomeric Thing content is low, and fine powder content is low.

By sequence number in table 11 and 5,6 result of the test data, the consumption of alpha-olefin is increased or decreased, can flexibly be adjusted Save the content of comonomer in polymer.

The result of the test data of sequence number 1 and 3,4,5,6 are understood in contrast table 1, by changing two stage of reaction reaction gases Atmosphere is constituted and the reaction time, can adjust containing for comonomer in reactivity, polymer molecular weight and its distribution and polymer Amount, so as to illustrate that preparing polymer using the method that the present invention is provided has bigger adjustable range.

Sequence number 7,8 is sequence number 1 in the experimental result that one-part form homopolymerization and copolymerization are carried out using CAT-1, contrast table 1 in table 1 Result of the test data with 7,8 understand that the polymer obtained using two-stage method polymerization methodses has broader molecular weight distribution, therefore The processing characteristics of polymer is more preferable.

Pass through sequence number 1 in contrast table 1 and the result of the test data of comparative example sequence number 21 and 22, catalyst preparation process In with the increase of Nonmetallocene part addition, the polymerization activity of catalyst and thus obtained polymer stacks density are Increase, polymer molecular weight distribution narrow, thus explanation, which introduces Nonmetallocene part, can improve catalyst activity and polymer Heap density, the effect of the polymer molecular weight that narrows distribution.

By sequence number 1 in contrast table 1 and the result of the test data of comparative example sequence number 23, in catalyst preparation process not Introduce Nonmetallocene part, thus obtained catalyst belongs to Ziegler-Natta type dynamics model catalyst, polymerization activity and Polymer stacks density is relatively low, polymer molecular weight wider distribution.

Rotation molding embodiment

Polymer P E-10 or PE-20, each with relative to the polymer be 0.2wt% antioxidant 2,6- di-t-butyls P-methyl phenol（Article number：Antioxidant BHT）Polymeric compositions are formed after uniform mixing.The polymer composition is added to rolling Molding machine（The swing rotational molding machine of Yantai Fangda Rotational Molding Co., Ltd.）Middle carry out rotation molding.Condition of molding includes：Mould and The temperature of its materials inside heating hot-air is 280 DEG C, the flow velocity about 10m/s of air inlet hot-air, mold rotation speed For 10 rpm, molding time is 15min.Obtainφ1000mm × 1000mm drum product, its wall thickness about 10mm.Test the circle The resisting environmental stress and cracking time of bucket product（ESCR）And tensile yield strength, concrete outcome is as shown in table 2.

The rotation molding effect list of table 2.

Sequence number	Polymer	Resisting environmental stress and cracking time ESCR（F₅₀/h）	Tensile yield strength（MPa）
				1	PE-10	2800	20.3
2	PE-20	2200	17.5

From the data of table 2, polymer made according to the present invention（PE-10）, with gathering that art methods are manufactured Compound（PE-20）Compare,（Product）Environmental stress cracking resistance is more excellent, and（Product）Tensile yield strength is higher.

Tube forming embodiment

Polymer P E-9 or PE-18, each and antioxidant 1010（Four [β-(3,5- di-tert-butyl-hydroxy phenyls) third Acid] pentaerythritol ester）, irgasfos 168（(2,4- di-tert-butyl-phenyls) tris phosphite）With calcium stearate according to mass ratio 100/0.1/0.2/0.1 ratio is well mixed.The well mixed material is passed through into parallel equidirectional two-screw extruder（Nanjing Rhea extrusion machinery equipment Co., Ltd CTE-35 types）Simultaneously pelletizing obtains corresponding pellet for melting extrusion, water-bath cooling.Twin-screw Each section of temperature setting of extruder be：185℃-200℃-215℃-225℃-225℃-225℃-230℃-230℃-220℃- 220℃（Head）.

After obtained pellet is dried 4 hours through 70 DEG C, polyvinyl piping materials extruder is added to（Crouse horse phenanthrene OD20- 63mm）In, in -240 DEG C -235 DEG C of extrusion temperature 190 DEG C -210 DEG C -220 DEG C -230 DEG C（Die head）With about 1 meter of extrusion linear speed/ Continuously extruded under conditions of minute, obtain the mm of the diameter 63 and mm of nominal wall thickness about 5.8 tubing.During record steady extruding The main frame electric current of extruder, and test simply supported beam notch impact strength and the FNCT out-of-service times of the tubing（For characterizing tubing Long-Term Properties）, concrete outcome is as shown in table 3.

The tube forming effect list of table 3.

Sequence number	Polymer	Main frame electric current（A）	Simply supported beam notch impact strength（J/m²）	The FNCT out-of-service times（h）
					1	PE-9	25.2±0.1	19.1	5400
2	PE-18	27.4±0.1	17.3	4900

From the data of table 3, polymer made according to the present invention（PE-9）, with polymerizeing that art methods are manufactured （PE-18）Thing is compared, under equal processing conditions, and main frame electric current is lower, is indicated above its processing characteristics more preferably, and（Pipe Material）Simply supported beam notch impact strength is higher,（Tubing）Long-Term Properties are more preferably.

Although the embodiment in conjunction with the embodiments to the present invention is described in detail above, need to refer to Go out, protection scope of the present invention is not limited to these specific embodiments, but by claims of annex Lai It is determined that.Those skilled in the art can be carried out in the range of the technological thought and purport of the present invention is not departed to these embodiments Appropriate change, and the embodiment after these changes is obviously also included within protection scope of the present invention.

Claims

1. a kind of manufacture method of ethene-alpha-olefin copolymer, it is characterised in that comprise the following steps A and B or step A' and B'：

Step A：Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta, alkyl At least one in aluminium, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt makes in terms of aluminium or boron as co-catalyst The mol ratio of the co-catalyst and the major catalyst in terms of central metal atom reach 1~1000：1, it is anti-in polymerization 0.2 ~ 2.0MPa of stagnation pressure is answered, hydrogen and ethylene partial pressure compare 0.01-1：1 and 20 ~ 120 DEG C of polymeric reaction temperature under conditions of, make second Polyamino alkenyl, obtains A stage polymers, and

Step B：Using slurry polymerization process, in the presence of the A stage polymers, 0.1 ~ 2.0MPa of polymerisation stagnation pressure, Hydrogen and ethylene partial pressure compare 0.01-0.5：1st, 20 ~ 120 DEG C of polymeric reaction temperature and comonomer addition be 0.01 ~ 0.3 gram/ Under conditions of milligram major catalyst, make ethene and at least one alpha-olefin copolymer selected from C3-C12 alpha-olefins, obtain the second Alkene-alpha olefin copolymer；

Or

Step A'：Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta, alkane At least one in base aluminium, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt makes with aluminium or boron as co-catalyst The mol ratio of the co-catalyst of meter and the major catalyst in terms of central metal atom reaches 1~1000：1, in polymerization 0.1 ~ 2.0MPa of reaction stagnation pressure, hydrogen and ethylene partial pressure compare 0.01-0.5：1st, 20 ~ 120 DEG C of polymeric reaction temperature and comonomer Addition be 0.01 ~ 0.3 gram/milligram major catalyst under conditions of, make ethene with selected from C3-C12 alpha-olefins at least one α- Olefin-copolymerization, obtains A' stage polymers, and

Step B'：Using slurry polymerization process, in the presence of the A' stage polymers, polymerisation stagnation pressure 0.2 ~ 2.0MPa, hydrogen and ethylene partial pressure compare 0.01-1：1 and 20 ~ 120 DEG C of polymeric reaction temperature under conditions of make ethylene homo, obtain The ethene-alpha-olefin copolymer,

Wherein described load type non-metallocene catalyst is manufactured by the preparation method comprised the following steps：

Magnesium compound and Nonmetallocene part is set to be dissolved in the presence of an alcohol in solvent, the step of obtaining magnesium compound solution；

The complex carrier is contacted with the chemical treatments selected from IV B races metallic compound, obtain the non-cyclopentadienyl gold of the support type The step of metal catalyst,

The preparation method, which is optionally additionally included in, to be made before the complex carrier contacts with the chemical treatments, with selected from alumina Alkane, alkyl aluminum or the step of helping the chemical treatments pretreatment complex carrier of its any combination,

One or more of the wherein described Nonmetallocene part in the compound with following chemical structural formula：

,

In chemical structural formula more than,

Q is 0 or 1；

D is 0 or 1；

D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C₁- C₃₀Alkyl, sulfuryl Or sulfoxide group, wherein N, O, S, Se and P be respectively coordination atom；

E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group, and wherein N, O, S, Se and P is each From for coordination atom；

Represent singly-bound or double bond；

- represent covalent bond or ionic bond；

R¹To R³It is each independently selected from hydrogen, C₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl or safing function group, R²²To R³³ And R³⁹It is each independently selected from hydrogen, C₁- C₃₀Alkyl or substituted C₁- C₃₀Alkyl, above-mentioned group to each other can be with identical With difference, wherein adjacent group can combine togather bonding or cyclization,

The substituted C₁- C₃₀Alkyl, which is selected from, carries one or more halogens or C₁- C₃₀Alkyl as substituent foregoing C₁- C₃₀Alkyl；

The safing function group be selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, Containing tin group, C₁- C₁₀Ester group and nitro,

The halogen is selected from F, Cl, Br or I；

The oxy radical is selected from-OR³⁴With-T-OR³⁴；

The C₁- C₃₀Alkyl is selected from C₁- C₃₀Alkyl, C₇- C₃₀Alkaryl, C₇- C₃₀Aralkyl, C₃- C₃₀Cyclic alkyl, C₂- C₃₀Alkenyl, C₂- C₃₀Alkynyl, C₆- C₃₀Aryl or C₈- C₃₀Condensed ring radical；

Wherein, the silicon-containing group is selected from-SiR⁴²R⁴³R⁴⁴Or-T-SiR⁴⁵；The germanic group is selected from-GeR⁴⁶R⁴⁷R⁴⁸Or-T- GeR⁴⁹；It is described to be selected from-SnR containing tin group⁵⁰R⁵¹R⁵²、-T-SnR⁵³Or-T-Sn (O) R⁵⁴；

The R³⁴To R³⁶、R³⁸And R⁴²To R⁵⁴It is each independently selected from hydrogen, foregoing C₁- C₃₀Alkyl or foregoing substituted C₁- C₃₀Hydrocarbon Base, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather bonding or cyclization, And

The group T is as previously defined.

2. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein：

Step A：Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta and alkane It is at least one as co-catalyst in base aluminium, make the co-catalyst in terms of aluminium and the master in terms of central metal atom The mol ratio of catalyst reaches 10~100：1, in polymerisation stagnation pressure 0.4-0.8MPa, hydrogen and ethylene partial pressure compare 0.03- 0.5：1 and 75 ~ 95 DEG C of polymeric reaction temperature under conditions of, make ethylene homo, obtain A stage polymers, and

Step B：Using slurry polymerization process, in the presence of the A stage polymers, polymerisation stagnation pressure 0.3-0.6MPa, Hydrogen and ethylene partial pressure compare 0.03-0.3：1st, 75 ~ 95 DEG C of polymeric reaction temperature and comonomer addition are 0.02 ~ 0.2 gram/milli Under conditions of gram major catalyst, make ethene and at least one alpha-olefin copolymer selected from C4-C8 alpha-olefins, obtain the ethene- Alpha olefin copolymer；

Or

Step A'：Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta and alkane It is at least one as co-catalyst in base aluminium, make the co-catalyst in terms of aluminium and the master in terms of central metal atom The mol ratio of catalyst reaches 10~100：1, compare 0.03- in polymerisation stagnation pressure 0.3-0.6MPa, hydrogen and ethylene partial pressure 0.3：1st, under conditions of 75 ~ 95 DEG C of polymeric reaction temperature and comonomer addition are 0.02 ~ 0.2 gram/milligram major catalyst, make Ethene and at least one alpha-olefin copolymer selected from C4-C8 alpha-olefins, obtain A' stage polymers, and

Step B'：Using slurry polymerization process, in the presence of the A' stage polymers, in polymerisation stagnation pressure 0.4- 0.8MPa, hydrogen and ethylene partial pressure compare 0.03-0.5：1 and 75 ~ 95 DEG C of polymeric reaction temperature under conditions of make ethylene homo, obtain The ethene-alpha-olefin copolymer.

3. the manufacture method of the ethene-alpha-olefin copolymer of claim 1 or 2, wherein the A stage polymers account for the second The 0.1-90wt% of alkene-alpha olefin copolymer gross mass, or the A' stage polymers account for the ethene-alpha-olefin copolymer The 10-99.9wt% of gross mass.

4. the manufacture method of the ethene-alpha-olefin copolymer of claim 3, wherein the A stage polymers account for the ethene-α- The 30-70wt% of olefin copolymer gross mass, or the A' stage polymers account for the ethene-alpha-olefin copolymer gross mass 30-70wt%.

5. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the porous carrier is selected from partial cross-linked benzene In ethene polymers, silica, aluminum oxide, magnesia, oxidation sial, oxidation magnalium, titanium dioxide, molecular sieve and montmorillonite One or more, wherein the porous carrier is optionally by thermal activation treatment and/or by the IV B races metallic compound Chemical activation processing, one or more of the magnesium compound in magnesium halide.

6. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the solvent is selected from C_6-12Aromatic hydrocarbon, halo C_6-12One or more in aromatic hydrocarbon, ester and ether, the one kind or many of the alcohol in fatty alcohol, aromatic alcohol and alicyclic ring alcohol Kind, wherein the alcohol is optionally selected from halogen atom or C_1-6The substituent substitution of alkoxy.

7. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the Nonmetallocene part is selected from as follows The compound of chemical structural formula（A）And compound（B）In one or more：

With,

（A）（B）

In above all of chemical structural formula,

F is selected from nitrogen-containing group or phosphorus-containing groups, and wherein N and P are respectively coordination atom.

8. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the Nonmetallocene part is selected from as follows One or more in the compound of chemical structural formula：

、、、、With。

9. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the Nonmetallocene part is selected from as follows One or more in the compound of chemical structural formula：

With。

10. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the magnesium compound in terms of Mg elements with The mol ratio of the Nonmetallocene part is 1：The ratio of 0.0001-1, the magnesium compound and the solvent is 1mol：75~ 400ml, the magnesium compound and the mol ratio of the alcohol counted using Mg elements is 1：0.02~4.00, in terms of magnesium compound solid The mass ratio of the magnesium compound and the porous carrier be 1：0.1-20, the volume ratio of the precipitating reagent and the solvent is 1：0.2~5, the complex carrier in terms of Mg elements and the mol ratio with the chemical treatments of Group IVB elemental metal For 1：0.01-1, and mol ratio of the complex carrier with helping chemical treatments described in terms of Al elements in terms of Mg elements For 1：0-1.0.

11. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the precipitating reagent be selected from alkane, cycloalkane, One or more in halogenated alkane and halo cycloalkane.

12. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the IV B races metallic compound is selected from IV B One or more in race's metal halide, the aikyiaiurnirsoxan beta be selected from MAO, ethylaluminoxane, isobutyl aluminium alkoxide and One or more in normal-butyl aikyiaiurnirsoxan beta, and the alkyl aluminum is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, three isobutyls Base aluminium, three n-butylaluminums, triisopentyl aluminium, three n-pentyl aluminium, three hexyl aluminium, three isohesyl aluminium, diethylmethyl aluminium and diformazan One or more in base aluminium ethide.