CN105017456B - A kind of ethylene-alpha-olefin copolymer, its manufacture method and its application - Google Patents

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 molecular weight polyethylene higher 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 Increase the relatively low component of the molecular weight for being used to improve processing characteristics in amount polyvinyl resin higher, 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-molecular-weight, 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-molecular-weight Part can ensure the rigidity of polymer, while there is provided lubrication improving the processing characteristics of resin.Due to bimodal polyethylene The processing characteristics of material and performance 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 manufacturing rotomoulded articles and high-performance pipe Material.And, in the manufacture method of the ethene-alpha-olefin copolymer disclosed in the Chinese patent, the catalysis of polymerization catalyst is lived Property cannot be fully played, copolymerization effect also has the leeway of further raising.

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, Range of 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 catalysis 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 monomeric unit with derived from ethylene with 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 The fine powder content of rice is less than 3 weight %, and the melt index determined under the conditions of 190 DEG C and 2.16 kilograms is 0.02 ~ 20g/10min, point 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 and be 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 and be 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 that the preparation method by comprising the following steps is manufactured：

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

To precipitating reagent or the drying magnesium compound solution is added in the magnesium compound solution, obtain magnesium compound and carry The step of body；

Make the magnesium compound carrier and following formula（X）Silicon compound and the chemical treatment selected from IV B races metallic compound The step of agent contact, acquisition load type non-metallocene catalyst,

Si(OR)_mX_4-mFormula（X）

Wherein, each R is identical or different, is each independently selected from C_1-8Straight or branched alkyl, preferably selects independently of one another From C_1-4Straight or branched alkyl, is preferably all ethyl；M is 0,1,2,3 or 4 integer；Each X is identical or different, each independent Ground is selected from halogen, preferably chlorine,

The preparation method is optionally additionally included in be made at the magnesium compound carrier and the silicon compound and the chemistry Before reason agent contact, the magnesium compound is pre-processed with selected from aikyiaiurnirsoxan beta, alkyl aluminum or its chemical treatments that help being combined The step of carrier.

5. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein 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, preferably select One or more from 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, the alcohol is selected from one or more in fatty alcohol, aromatic alcohol and alicyclic ring alcohol, wherein the alcohol optionally quilt Selected from halogen atom or C_1-6The substitution base substitution of alkoxy, the alcohol is preferably selected from one or more in fatty alcohol, more preferably selects One or more from 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 being 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 Group, containing tin group, C₁- C₁₀Ester group and nitro；

R⁵Selected from lone 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 as coordination atom；

The substituted C₁- C₃₀Alkyl is selected from and carries one or more halogens or C₁- C₃₀Alkyl is used as substitution base C₁- C₃₀Alkyl,

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

、、、、With,

The Nonmetallocene part is most preferably selected from 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 atom 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, the magnesium compound in terms of Mg elements and the alcohol mole Than being 1：0.02~4.00, preferably 1：0.05~3.00, more preferably 1：0.10~2.50, 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 magnesium compound carrier in terms of Mg elements with The mol ratio of the silicon compound of Si element meters is 1：0.01-1, preferably 1：0.01-0.50, more preferably 1：0.05-0.25, with The magnesium compound carrier of Mg element meters with the mol ratio of the chemical treatments of Group IVB elemental metal be 1： 0.01-1, preferably 1：0.01-0.50, more preferably 1：0.10-0.30, and the magnesium compound carrier in terms of Mg elements with The mol ratio that chemical treatments are helped described in Al element meters is 1：0-1.0, 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, it is 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.

The manufacture method of the ethene-alpha-olefin copolymer of 11. any preceding aspects, 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, it is preferably selected from the 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, it is more preferably selected from 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, it is preferably selected from One or more in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, it is most preferably selected from triethyl aluminum and three different One or more in butyl aluminium.

A kind of 12. polymer compositions, 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 one or more in halogen-absorber and pigment.

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

Technique effect

Ethene-alpha-olefin copolymer of the 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.

The manufacture method of ethene-alpha-olefin copolymer of the 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（The type of such as monomer and comonomer, molecular weight and molecular weight distribution, 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 ethene-alpha-olefin copolymer of the invention, it is possible to produce have excellent mechanical property and excellent concurrently Processing characteristics polymer composition, and show long-term use using the moulded products that the polymer composition is manufactured Can be excellent excellent with anti-cracking performance the features such as.

According to the present invention, by 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 processing characteristics higher, then can properly increase the ratio of homopolymerization section, and if necessary to mechanical property higher, then can be with Properly increase the ratio of copolymerization section.

Specific embodiment

Specific embodiment of the invention is described in detail below, it should be noted however that protection of the 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 scope, more than 3 carbon atoms hydrocarbon or hydrocarbon derivative group（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 It is n-propyl to solve, 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 each substitution base or clear and definite its valency of group of compound Key-like condition be monovalence, divalence, trivalent or tetravalence etc., those skilled in the art can according to these substitution base 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 selection in these substitution bases or group given a definition that is directed to from this specification The definition that valence link situation in the position or substitution situation is adapted to.

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

In the context of the present specification, in addition to the content for clearly stating, any matters or item do not mentioned are equal Directly be applicable it is known in the art those and any change need not be carried out.And, any implementation method described herein can be with Freely combined with one or more other embodiment described herein, the technical scheme or technological thought for being formed therefrom are regarded Be original disclosure of the invention or a part for original description, and be not considered as not disclosing herein or be expected 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 monomeric unit and the copolymer of the monomeric unit derived from least one alpha-olefin selected from C3-C12 alpha-olefins of ethene, It is preferred that having the monomeric unit and the monomer list derived from least one alpha-olefin selected from C4-C8 alpha-olefins of derived from ethylene The copolymer of unit.

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 the ratio needed for any.

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 goes out of centrifugation take out 1 liter of solvent, under the conditions of higher than solvent boiling point or closed vacuumize abundant drying Material gross mass remaining after solvent.Its content height mainly determined by catalyst performance and polymeric reaction condition, while With polymer solvent and filtering or centrifugation temperature it is relevant.

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 is measured divided by the gross mass of copolymer.

According to the present invention, the melt index of the ethene-alpha-olefin copolymer（190 DEG C, 2.16 kilograms）It is 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 are mobile phase, and 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 Determining reference standard GB/T 1033-86 is carried out（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 the manufacture method A of A and B 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, hydrogen and ethylene partial pressure is answered to 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 polymerisation stagnation pressure of step A 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 hydrogen and ethylene partial pressure of step A are than generally 0.01-1：1, preferably 0.02-0.8：1, Most preferably 0.03-0.5：1.

According to the present invention, the polymeric reaction temperature of step A 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 particularly Limit.As its specific embodiment, such as can enumerate and solvent for polymerization is added to slurry polymerization reactor（Such as gather Close autoclave）In, then in 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, obtain 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 polymerisation stagnation pressure of step B 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 hydrogen and ethylene partial pressure of step B are than general 0.01-0.5：1, preferably 0.02-0.4：1, Most preferably 0.03-0.3：1.

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

According to the present invention, the comonomer addition of step B 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 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 to divide to step B predetermined hydrogen Pressure, finally adjusting and be 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 ethene-alpha-olefin copolymer of the 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, then to disposable in the second reactor The comonomer of predetermined volume in step B is added, hydrogen to step B predetermined hydrogen partial pressure is added, finally persistently led 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 Ethene and the copolymerization of the comonomer, that is, obtain ethene-alpha-olefin copolymer of the 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 general to carry out 0.2 ~ 4 hour, preferably 0.5 ~ 2 hour, but is not limited to this.In fact, two The length of the respective polymerization reaction time of individual step can be according to the major catalyst for being used（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 specific 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 during the step B is carried out 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 for step B 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 root sometimes According to needing to supplement in right amount, to adjust the catalysis 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, the subsequent implementation of step B for convenience, before step B is carried out, can be by well known in the art 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 reactor of step A.

According to the present invention, after step B terminates, can be mixed from the reaction for being obtained according to method well known in the art 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 the manufacturer of A' and B' 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 polymerisation stagnation pressure of step A' 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 hydrogen and ethylene partial pressure of step A' are than 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 polymeric reaction temperature of step A' is generally 20 ~ 120 DEG C, preferably 60 ~ 100 DEG C, more preferably 75~95℃。

According to the present invention, the comonomer addition of step A' 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 especially Restriction.As its specific embodiment, such as can enumerate and solvent for polymerization is added to slurry polymerization reactor（Such as Polymerization autoclave）In, then to the major catalyst and co-catalyst that predetermined volume is added in the reactor, disposable addition 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 the predetermined polymeric reaction temperature of holding carries out the copolyreaction of ethene and comonomer, that is, the A' is obtained Stage polymer.

It is apparent that the specific 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 polymerisation stagnation pressure of step B' 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 hydrogen and ethylene partial pressure of step B' are than generally 0.01-1：1, preferably 0.02-0.8：1, Most preferably 0.03-0.5：1.

According to the present invention, the polymeric reaction temperature of step B' 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 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 To step B' predetermined hydrogen partial pressure, finally adjust and be continually fed into ethene makes polymerisation stagnation pressure to addition hydrogen in stating reactor The constant predetermined value in step B', while the polymeric reaction temperature for keeping step B' predetermined carries 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 Add hydrogen to step B' predetermined hydrogen partial pressure in the backward second reactor, 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' is general to carry out 2 ~ 8 hours, preferably 3 ~ 5 hours, but is not limited to this.In fact, two The length of the respective polymerization reaction time of individual step can be according to the major catalyst for being used（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 specific 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 Can also in right amount supplement as needed, to adjust the catalysis activity of the A' stage polymers, but be not required in that.

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, the subsequent implementation of step B' for convenience, before step B' is carried out, can be by known in this field 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 reactor of step A' Point.

According to the present invention, after step B' terminates, can be mixed from the reaction for being obtained according to method well known in the art 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 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 that method manufacture is prepared by the following procedure.

According to the present invention, the preparation method of the load type non-metallocene catalyst is comprised the following steps：Make magnesium compound Be dissolved in solvent in the presence of an alcohol with Nonmetallocene part, obtain magnesium compound solution the step of；To the magnesium compound The step of precipitating reagent or the drying magnesium compound solution, acquisition magnesium compound carrier are added in solution；With make the magnesium Compound carrier and formula（X）Silicon compound and the chemical treatments contact selected from IV B races metallic compound, obtain the support type The step of 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 It is dissolving magnesium compound solvent）In, so as to obtain the magnesium compound solution.

As the solvent, such as 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, it is also possible to be used in mixed way so that arbitrary ratio is various.

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 for obtaining.

As the alcohol, such as 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 Substitution base substitution.

As the C_1-30Fatty alcohol, such as can enumerate methyl alcohol, 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.

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

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 methyl alcohol, ethapon and three Mecorals etc. can be enumerated, its In preferred trichlorine methyl alcohol.

As the alcohol replaced by alkoxy, such as 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, it is also possible to various to be used in mixed way.When being used in the form of various mixing, 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, can by the magnesium compound and the Nonmetallocene part be added to by Dissolved in the mixed solvent that the solvent and the alcohol are formed, 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 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 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 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 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 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, it is also possible to various to be used in mixed way, and be not particularly limited.

When being used in the form of various mixing, between two kinds of magnesium compounds in the magnesium compound mixture mole 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 Polymerized hydrocarbon catalyst, does not contain cyclopentadienyl groups such as luxuriant ring, fluorenes ring or indenes ring or derivatives thereof in 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 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 coordinate bond with the central metal atom（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）By 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 used as chemical treatments in the present invention There is complexation reaction and form coordinate bond in IV B races metallic atom, be consequently formed the metallic atom centered on the IV B races metallic atom The complex of M（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；

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（-CN）, wherein N, O, S, Se and P are respectively coordination atom；

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 being 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.

R⁵Selected from lone 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 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）The complexation process of described group A, D, E, F, Y or Z and the central metal atom M is not disturbed, and

（2）Coordination ability with the central metal atom M is less than described A, D, E, F, Y and Z group, 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 of chemical structural formula 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 the heteroatomic C of group Z or Y₆- 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 substitution base 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 containing 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 contains 1-3 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 of the related group combined to it 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 to those skilled in the art obvious.

In the context of the present invention, the substituted C₁- C₃₀Alkyl is referred to one or more inert substituents C₁- C₃₀Alkyl.So-called inert substituent, refers to these substitution bases 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 substitution bases have no ability to or without machine Meeting（Such as influenceed by steric hindrance etc.）There is 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 R⁵⁴It is 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 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 various.

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, by the way that to the magnesium compound solution convection drying, a kind of consolidating for good fluidity can be obtained Body product, i.e., magnesium compound 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 metered precipitating reagent in the magnesium compound solution, make solid matter from this It is precipitated out in magnesium compound solution, is derived from magnesium compound 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 The chemical inertness liquid for spending simultaneously and then making it to be separated out in solid form from the solution.

According to the present invention, as the precipitating reagent, such as 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 being used for Dissolve the solid content solute（Such as magnesium compound）The solvent for for good solvent solvent, such as can enumerate C_5-12 Alkane, C_5-12Cycloalkane, halo C_1-10Alkane and halo C_5-12Cycloalkane.

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.

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

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..

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, it is also possible to be used in mixed way so that arbitrary ratio is various.

The feed postition of precipitating reagent can be added or dropwise addition for disposable, preferably disposable to add.In the precipitation process In, it is possible to use stir to promote the dispersion 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 be used to dissolve 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 what is 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.And, this sinks Shallow lake process is general it is also preferred that in normal temperature to less than any solvent and the temperature of the boiling point of precipitating reagent for being used（It is preferred that 20-80 DEG C, More preferably 40-60 DEG C）Under carry out 0.3-12 hours, but be not limited to this sometimes, and be substantially completely precipitated as with solid product It is accurate.

After precipitating completely, the solid product to being obtained is filtered, washed and dried.For the filtering, washing and Dry method is not particularly limited, and can as needed use those commonly used in the art.

As needed, the washing typically carries 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 dry temperature range is generally normal temperature to 140 DEG C.Drying time is generally 2-20 hours, but can also According to specifically used different for dissolving the solvent case of the magnesium compound.Such as, tetrahydrofuran conduct is being used During for the 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 the 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 making the magnesium compound carrier of foregoing acquisition and formula（X）Silicon compound and selected from IV B races gold Belong to the chemical treatments contact of compound, be derived from load type non-metallocene catalyst of the invention.

According to the present invention, reacted with the magnesium compound carrier by making the chemical treatments, caused at the chemistry There is complexation reaction in reason agent, with foregoing Nonmetallocene part contained on the magnesium compound carrier so as in the magnesium compound carrier The Nonmetallocene complex of upper in-situ preparation metallic atom centered on the Group IVB metallic atom（Supported reaction in situ）, This is of the invention one big feature.

Below to the formula（X）Silicon compound be specifically described.

Si(OR)_mX_4-mFormula（X）

Wherein, each R is identical or different, is each independently selected from C_1-8Straight or branched alkyl, such as methyl, ethyl, positive third It is base, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, different pungent Base etc.；

M is 0,1,2,3 or 4 integer；

Each X is identical or different, is each independently selected from halogen.

According to the present invention, as the halogen, such as fluorine, chlorine, bromine and iodine can be enumerated, wherein it is preferred that chlorine.

According to the present invention, each R is preferably identical or different, is each independently selected from C_1-4Straight or branched alkyl, preferably It is ethyl.

As the formula（X）Silicon compound, can enumerate but be not limited to compound in detail below：

Tetramethoxy-silicane, tetraethoxy-silicane, four positive propoxy silicon, tetraisopropoxide silicon, four n-butoxy silicon, four isobutyl oxygen Base silicon, four n-pentyloxy silicon, tetraisoamoxy-silicane, four n-octyloxy silicon, four different octyloxy silicon, a methoxy ethyl triethoxy silicane, Dimethoxy diethoxy silicon, the ethyoxyl silicon of trimethoxy one, the n-propyl epoxide silicon of a methoxyl group three, positive third oxygen of dimethoxy two Base silicon, the positive propoxy silicon of trimethoxy one, a methoxyl group triisopropyl epoxide silicon, dimethoxy diisopropoxy silicon, trimethoxy The isopropoxy silicon of base one, the normal-butyl epoxide silicon of a methoxyl group three, the n-butoxy silicon of dimethoxy two, the n-butoxy of trimethoxy one Silicon, a methoxyl group triisobutyl epoxide silicon, the isobutoxy silicon of dimethoxy two, the isobutoxy silicon of trimethoxy one, an ethyoxyl Three n-propyl epoxide silicon, the positive propoxy silicon of diethoxy two, the positive propoxy silicon of triethoxy one, an ethyoxyl triisopropyl epoxide Silicon, diethoxy diisopropoxy silicon, the isopropoxy silicon of triethoxy one, the normal-butyl epoxide silicon of an ethyoxyl three, diethoxy Two n-butoxy silicon, the n-butoxy silicon of triethoxy one, an ethyoxyl triisobutyl epoxide silicon, the isobutoxy of diethoxy two Four C such as silicon, the isobutoxy silicon of triethoxy one_1-8Straight or branched alkoxyl silicon, wherein it is preferred that tetramethoxy-silicane, tetraethoxy Silicon, tetraisobutoxy-silicane, more preferably tetraethoxy-silicane；

Trimethoxy chloro silicon, dimethoxy chloro silicon, a methoxyl group chloro silicon, triethoxy chloro silicon, diethoxy Chloro silicon, an ethyoxyl chloro silicon, three isobutoxy chloro silicon, two isobutoxy chloro silicon, an isobutoxy chloro silicon, front three Epoxide bromo silicon, dimethoxy bromo silicon, a methoxyl group bromo silicon, triethoxy bromo silicon, diethoxy bromo silicon, an ethoxy Bromide is for C such as silicon, three isobutoxy bromo silicon, two isobutoxy bromo silicon, an isobutoxy bromo silicon_1-8Straight or branched alkane Epoxide halo silicon, wherein it is preferred that trimethoxy chloro silicon, dimethoxy chloro silicon, triethoxy chloro silicon, diethoxy chloro Silicon, more preferably triethoxy chloro silicon；

The silicon tetrahalogens such as ocratation, silicon tetrachloride, silicon bromide, silicon tetraiodide, tribromo silicon chloride, trichlorine silicon bromide, Wherein preferred silicon tetrachloride.

These silicon compounds can be used alone one kind, or be applied in combination with arbitrary ratio various.

The chemical treatments are specifically described below.

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

As the Group IVB metallic compound, such as 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.

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, it is also possible to 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 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 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 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 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）.

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 various.

When the chemical treatments are at normal temperatures liquid, the chemistry directly can be carried out using the chemical treatments Treatment 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 the solution of the chemical treatments is prepared, to the solvent that is now used, 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 magnesium compound 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.

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

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 carrying out the chemical treatment reaction with the chemical treatments of scheduled volume.Such as preceding institute State, if chemical treatments are liquid, directly can carry out the treatment using chemical treatments, but it is also possible to adjusted Used after being made the solution of chemical treatments.

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, used as the ways of carrying out of the chemical treatment reaction, such as can enumerate makes the magnesium compound Carrier is with the silicon compound and the chemical treatments in solvent（Also referred to as chemical treatment solvent）In the presence of connect Tactile mode.

According to the present invention, to the chemical treatment, with solvent, there is no particular limitation, as long as it can dissolve the silication Compound and the chemical treatments, and do not destroy（Such as dissolve）The existing carrier structure of the magnesium compound 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.

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

According to the present invention, as the consumption of the chemical treatment solvent so that the magnesium compound carrier is relative to institute The ratio for stating chemical treatment solvent is 1g：1-100ml, preferably 1g：2-40ml, but this is not limited to sometimes.In addition, When using chemical treatments as a solution as previously described, the chemical treatment can be suitably reduced according to actual conditions with molten The consumption of agent, but be not particularly limited.

According to the present invention, as the consumption of the silicon compound so that the magnesium compound carrier in terms of Mg elements with The mol ratio of the silicon compound in terms of Si elements reaches 1：0.01-1, preferably 1：0.01-0.50, more preferably 1：0.05- 0.25。

According to the present invention, as the consumption of the chemical treatments so that the magnesium compound carrier in terms of Mg elements Mol ratio with the chemical treatments with Group IVB elemental metal reaches 1：0.01-1, preferably 1：0.01-0.50, it is more excellent Select 1：0.10-0.30.

It is known that when carrier is chemically treated using Group IVB metallic compound, can be immobilized a certain amount of on this carrier Group IVB metallic compound.The present inventor is had found by studying, and in the immobilized Group IVB metallic compound, is had quite A big part is rendered as inactive state, i.e. loaded catalyst of this part Group IVB metallic compound for final manufacture Olefinic polymerization catalysis activity without contribution.Therefore, the present inventor pass through further investigation revealed that, if used During Group IVB metallic compound chemical treatment carrier and with the foregoing specific silicon compound of the present invention, the nothing can be significantly decreased The ratio of active part significantly decreases the supported quantity of the Group IVB metallic compound on carrier, so as to correspondingly improve The load capacity of Nonmetallocene complex or the load percentage relative to Group IVB metallic compound.As a result, with without and with described in The situation of silicon compound is compared, and the present invention is when the silicon compound, and the support type that can significantly improve final acquisition is non- The olefinic polymerization catalysis activity of metallocene catalyst.In addition, present inventor has further discovered that, closed by and with the silication Thing, can also realize the polymer molecular weight distribution that narrows, and improve mechanical properties of polymer, and make comonomer in the polymer Sequence be distributed more regular function.These discoveries are in the art Promethean.

According to the present invention, to the magnesium compound carrier and the silicon compound and the engagement sequence of the chemical treatments There is no particular limitation, such as this three can contact simultaneously, it is also possible to is successively contacted according to arbitrary order.

According to one preferred embodiment of the invention, in the presence of the chemical treatment solvent, make the magnesium Compound carrier is first contacted with the silicon compound（First contact procedure）, then adding the chemical treatments is carried out further Contact（Second contact procedure）, thus carry out described chemical treatment reaction.

As the ways of carrying out of first contact procedure, such as can enumerate under agitation, the magnesium compound is carried Body and the silicon compound are added in the chemical treatment solvent simultaneously or successively, at 0-100 DEG C（It is preferred that 20-80 DEG C）Under after Continue the mode for stirring and reacting and formed slurry.To the reaction time now, there is no particular limitation, such as can enumerate 0-6h, preferably 0.5-4h.

After slurry is obtained as previously described, the slurry is set further to be contacted with the chemical treatments（The Two contact procedures）.

As the ways of carrying out of second contact procedure, such as can enumerate under agitation, be added in the slurry （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 the reaction time now, there is no particular limitation, such as can lift Go out 0.5-8h, preferably 1-4h.

After the chemical treatment reaction terminates, by being filtered, washed and dried, you can obtain by chemically treated product Thing（Load type non-metallocene catalyst of the invention）.

According to the present invention, described being 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 washing is general 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, the preparation method of the load type non-metallocene catalyst is additionally included in as needed, optionally to be made Before the magnesium compound carrier is contacted with the silicon compound and the chemical treatments, with selected from aikyiaiurnirsoxan beta, alkyl aluminum or The step of helping chemical treatments to pre-process the magnesium compound carrier of its any combination（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 Magnesium compound carrier is also referred to as magnesium compound 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 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 the arbitrary integer in the range of 1-50, any in the range of 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 various.

As the alkyl aluminum, such as 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 various.

According to the present invention, chemical treatments are helped as described, it is possible to use only the aikyiaiurnirsoxan beta, it is also possible to only with described Alkyl aluminum, but it is also possible to using the aikyiaiurnirsoxan beta and any mixture of the alkyl aluminum.And, 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 the solvent that is now used, there is no particular limitation, as long as it can dissolve this helps chemical treatments And do not destroy（Such as dissolve）The existing carrier structure of the magnesium compound 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.

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

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 helping the chemical treatments to carry out the pre-treatment step described in scheduled volume.

Method as the pre-treatment step is carried out, such as can enumerate, and prepare described help chemical treatments first Solution, then to intending with metered in the magnesium compound carrier for helping chemical treatments pretreatment（It is preferred that being added dropwise） It is described to help chemical treatment agent solution（Wherein containing helping chemical treatments described in scheduled volume）, or help chemical treatments to described The metered magnesium compound carrier, is consequently formed reaction mixture in solution.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 being filtered, washed and dried, the magnesium compound carrier by pre-processing is isolated from the reaction mixture.Then, use This by pretreatment magnesium compound carrier, according to exact same way is described before, carry out and silicon compound and chemistry The contact of inorganic agent.

According to the present invention, described being filtered, washed and dried can be carried out using conventional method, and wherein washer solvent can be with Using with dissolving described in help chemical treatments when identical solvent used.As needed, the washing is general 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 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 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, 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, as the consumption of the solvent 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, as the consumption of the alcohol 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, as the consumption of the precipitating reagent 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, as the consumption of the silicon compound so that the magnesium compound carrier in terms of Mg elements with The mol ratio of the silicon compound counted with Si elements is 1：0.01-1, preferably 1：0.01-0.50, more preferably 1：0.05-0.25.

According to the present invention, as the consumption of the chemical treatments so that the magnesium compound carrier in terms of Mg elements Mol ratio with the chemical treatments with 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, as the consumption for helping chemical treatments so that the magnesium compound in terms of Mg elements is carried Body with the mol ratio that chemical treatments are helped described in Al elements are counted be 1：0-1.0, preferably 1：0-0.5, more preferably 1：0.1- 0.5。

Known to those skilled in the art to be, foregoing all of method and step is 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.And, Load type non-metallocene catalyst of the invention generally needs 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 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 the arbitrary integer in the range of 1-50, any in the range of 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.

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

As the alkyl aluminum, such as 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）, 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.

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

As the haloalkyl aluminium, such as 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 various.

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

In addition, according to the present invention, the co-catalyst can be used alone one kind, it is also possible to as needed arbitrarily comparing Example is applied in combination various foregoing co-catalysts, is not particularly limited.

According to the present invention, in foregoing manufacture method A and manufacture method B, as the solvent for polymerization, such as can be with Enumerate this area when slurry olefin polymerization is carried out 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 various.

According to the present invention, in described step A or step A', as the consumption of the solvent for polymerization, such as can be with 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 can also be similar to setting.

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 the step B or step B' State be also required to supplement co-catalyst when, the specific consumption of its co-catalyst can also be similar to setting.

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 for particularly pointing 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, it is not particularly limited, the description thereof will be omitted herein.

Ethene-alpha-olefin copolymer of the invention can be that the ethene-alpha-olefin manufactured by foregoing manufacture method A is total to Polymers A or the ethene-alpha-olefin copolymer B, or the ethene-alpha-olefin that are manufactured by foregoing manufacture method B The arbitrary proportion mixture of copolymer A and the ethene-alpha-olefin copolymer B.

Further, the invention further relates to a kind of polymer composition, it includes the foregoing ethene-alpha-olefin of the present invention and is total to 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 be by conventional conjunction Into or commercialization sale antioxidant, be not particularly limited.It is known that the antioxidant is usual by primary antioxidant and auxiliary Antioxidant constitute, but auxiliary anti-oxidant can not also be used sometimes and using only the primary antioxidant as the antioxidant.

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

According to the present invention, the primary antioxidant is selected from least one in hindered phenol compound and aromatic amine compounds. As the primary antioxidant, such as 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, it is also possible to which multiple combination is used.

According to the present invention, as the primary antioxidant, preferably hindered phenol compound, more preferably β-(4 hydroxyl -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- hydroxyls Phenyl) propionic acid] pentaerythritol ester（Article number：Antioxidant 1010）Or its combination, most preferably β-(4-hydroxyl-3,5-two Tert-butyl-phenyl) the positive octadecanol ester article number of propionic acid：Antioxidant 1076）.

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

As the phosphite ester kind antioxidant, such as 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, it is also possible to which multiple combination is used.

As the sulfur-bearing antioxidant, such as 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, it is also possible to which multiple combination 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）.

According to the present invention, as needed, polymer group can also manufactured comprising this area in the polymer composition 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, it is also possible to two kinds Or multiple combination is 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, can optionally comprising the one kind or many in pigment and halogen-absorber 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 and orange can be enumerated The color pigments such as pigment, wherein it is preferred that carbon black.These pigment can be used alone one kind, it is also possible to which multiple combination is used.Make Used time, gross weight with the polymer composition to count, 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 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 with the polymer composition to count, institute Content of the halogen-absorber in the polymer composition generally 0-0.5wt%, preferably 0-0.3wt% are stated, not especially 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 for using as needed（Especially pigment and/or halogen-absorber）, according to predetermined Usage ratio, mixes 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 can enumerate conventionally known in the art Any method, such as extrude, injection, 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 minutes, pressing time 1--20 minute, cool time 1-20 minutes, but it is 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 CNS GB 1636-79.

The oligomer of copolymer is determined：The filtrate center line gone out in filtering or centrifugation takes out 1 liter of solvent, is being higher than Under the conditions of solvent boiling point or closed vacuumizing 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 is measured divided by the gross mass of copolymer.

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, and from 4 Agilent PLgel Olexis type chromatographic columns, with 1,2,4- trichloro-benzenes are mobile phase, are 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 the pellet that will be obtained was through 70 DEG C of dryings 4 hours, 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 tubing of the mm of the diameter 63 and mm of nominal wall thickness about 5.8.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, record main frame electric current 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.Two kinds of polymerization activities difference numerically is anti- Reflect the copolymerization effect of the major catalyst.If activity increases after copolymerization, show that copolymerization effect is good, active increased amplitude is got over Greatly, then its copolymerization effect is more notable, and such as activity is reduced after copolymerization, then show that copolymerization effect is poor.

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 according to GB/T 1043-2008 in the type pendulum punching of Italian Ceast companies 7611 Hitting on instrument is carried out, and is 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 Testing on machine is carried out.

Full notch creep test（FNCT）Carried out according to ISO 16770, sampled from tubing, in German IPT companies 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 it is test(ing) medium to use the Arkopal N-110 of 2wt%, test stress is 4.0MPa.The record out-of-service time.

Embodiment 1

Magnesium compound uses anhydrous magnesium chloride, solvent to use tetrahydrofuran, alcohol to use n-butanol, silicon compound to use tetrem Epoxide silicon, the chemical treatments of Group IVB metallic compound use titanium tetrachloride, precipitating reagent to use hexane, Nonmetallocene part to adopt It is with structureCompound.

5g anhydrous magnesium chlorides are weighed, solvent, Nonmetallocene part is added and is completely dissolved under normal temperature after alcohol, obtain magnesium chemical combination Thing solution, adds precipitating reagent to be allowed to precipitate completely to magnesium compound solution, filters, and is washed 3 times using precipitating reagent, each precipitating reagent Consumption is 60ml, is vacuumized at being uniformly heated to 60 DEG C and is dried to obtain magnesium compound carrier.

Obtained magnesium compound carrier is added in hexane solvent, normal temperature is added dropwise silicon compound and 30 points in lower 10 minutes Group IVB chemical treatments are added dropwise in clock, after being then uniformly heated to 60 DEG C of isothermal reactions 2 hours, filtering, hexane solvent washing 3 times, each consumption is identical with the quantity of solvent for adding before, finally vacuumizes drying at 60 DEG C, obtains load type non-metallocene Catalyst.

Wherein proportioning is that magnesium compound is 1mol with solvent burden ratio：210ml；Magnesium compound is 1 with alcohol mol ratio:0.5； Magnesium compound is 1 with the mol ratio of Nonmetallocene part:0.08；Precipitating reagent is 1 with solvent volume proportioning：1；In terms of Mg elements Magnesium compound carrier is 1 with the mol ratio of the silicon compound counted with Si elements：0.1；Magnesium compound carrier in terms of Mg elements with Chemical treatments mol ratio with Group IVB elemental metal is 1：0.15.

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 magnesium compound carrier is contacted with the silicon compound and the chemical treatments, first pass through and help chemical treatments Triethyl aluminum processes magnesium compound carrier.

That is, magnesium compound carrier is added in hexane solvent, then is slowly added dropwise and helps chemical treatments triethyl aluminum（Concentration It is 0.88mol/L, hexane solution）, filtered after being stirred 2 hours at 60 DEG C, hexane is washed 3 times, each consumption with before add Quantity of solvent is identical, finally vacuumizes drying at 60 DEG C, the magnesium compound carrier for being pre-processed.Magnesium wherein in terms of Mg elements Compound carrier and the mol ratio for helping chemical treatments counted with Al elements are 1：0.2.

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

Embodiment 3

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

Before magnesium compound carrier is contacted with the silicon compound and the chemical treatments, first pass through and help chemical treatments MAO processes magnesium compound carrier.

That is, magnesium compound carrier is added in toluene solvant, then is slowly added dropwise and helps chemical treatments MAO（It is dense It is 10wt% to spend, toluene solution）, being filtered after being stirred 2 hours at 60 DEG C, toluene is washed 3 times, and each consumption is molten with what is added before Dosage is identical, finally vacuumizes drying at 100 DEG C, the magnesium compound carrier for being pre-processed.Magnesium wherein in terms of Mg elements Compound carrier and the mol ratio for helping chemical treatments counted with Al elements are 1：0.4.

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

Embodiment 4

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

Magnesium compound changes into magnesium ethide（Mg(C₂H₅)₂）, alcohol uses ethanol, solvent to change into toluene, and silicon compound is changed to Tetraisobutoxy-silicane, the chemical treatments of Group IVB metallic compound change into zirconium chloride（ZrCl₄）, precipitating reagent is changed to hexamethylene Alkane, Nonmetallocene part is used。

Wherein proportioning is that magnesium compound is 1mol with solvent burden ratio：150ml；Magnesium compound is 1 with alcohol mol ratio:1.64； Magnesium compound is 1 with the mol ratio of Nonmetallocene part:0.04；Precipitating reagent is 1 with solvent volume proportioning：2；In terms of Mg elements Magnesium compound carrier is 1 with the mol ratio of the silicon compound counted with Si elements：0.05, magnesium compound carrier in terms of Mg elements with Chemical treatments mol ratio with Group IVB elemental metal is 1：0.20.

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

Embodiment 5

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

Magnesium compound changes into anhydrous magnesium bromide（MgBr₂）, alcohol changes into trichlorine methyl alcohol, and Nonmetallocene part is used, solvent changes into ethylbenzene, and silicon compound is changed to triethoxy chloro silicon, Group IVB metallic compound Chemical treatments change into titanium tetrabromide（TiBr₄）.

It is dry to adding precipitating reagent and filtration washing drying steps to be changed in magnesium compound solution directly to be vacuumized at 110 DEG C It is dry to obtain magnesium compound carrier.

Wherein proportioning is that magnesium compound is 1mol with solvent burden ratio：250ml；Magnesium compound is 1 with alcohol mol ratio:1；Magnesium Compound is 1 with the mol ratio of Nonmetallocene part:0.2；Magnesium compound carrier in terms of Mg elements and the silicon in terms of Si elements The mol ratio of compound is 1：0.25, magnesium compound carrier in terms of Mg elements and the chemical treatment with Group IVB elemental metal Agent mol ratio is 1：0.30.

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

Embodiment 6

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

Magnesium compound changes into ethyoxyl magnesium chloride（MgCl(OC₂H₅)）, alcohol changes into 2-Ethylhexyl Alcohol, and Nonmetallocene is matched somebody with somebody Body is used, solvent changes into dimethylbenzene, and silicide is changed to silicon tetrachloride, Group IVB metallic compound Chemical treatments change into tetraethyl titanium（Ti(CH₃CH₂)₄）, precipitating reagent changes into decane.

Wherein proportioning is that magnesium compound is 1mol with solvent burden ratio：300ml；Magnesium compound is 1 with alcohol mol ratio:0.25； Magnesium compound is 1 with the mol ratio of Nonmetallocene part:0.05；Precipitating reagent is 1 with solvent volume proportioning：1.5；In terms of Mg elements Magnesium compound carrier and the mol ratio of silicon compound counted with Si elements be 1：0.14, the magnesium compound carrier in terms of Mg elements It is 1 with the chemical treatments mol ratio with Group IVB elemental metal：0.05.

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

Embodiment 7

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

Magnesium compound changes into magnesium ethylate（Mg (OC₂H₅)₂）, alcohol changes into benzyl carbinol, and Nonmetallocene part is used, solvent changes into diethylbenzene, and silicon compound is changed to tetramethoxy-silicane, Group IVB metal compound The chemical treatments of thing change into tetra-n-butyl titanium（Ti(C₄H₉)₄）, precipitating reagent changes into pentane.

Wherein proportioning is that magnesium compound is 1mol with solvent burden ratio：400ml；Magnesium compound is 1 with alcohol mol ratio:2.5； Magnesium compound is 1 with the mol ratio of Nonmetallocene part:0.4；Precipitating reagent is 1 with solvent volume proportioning：0.5；In terms of Mg elements Magnesium compound carrier and the mol ratio of silicon compound counted with Si elements be 1：0.45, the magnesium compound carrier in terms of Mg elements It is 1 with the chemical treatments mol ratio with Group IVB elemental metal：0.50.

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

Embodiment 8

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

Magnesium compound changes into methyl-magnesium-chloride（Mg(CH₃)Cl）, alcohol is changed to cyclohexanol, and Nonmetallocene part is used, it is 1 according to mol ratio that silicon compound is changed to by tetraethoxy-silicane and silicon tetrachloride：1 mixture, Solvent changes into chlorotoluene.

Wherein proportioning is that magnesium compound is 1 with alcohol mol ratio:3.0；Magnesium compound is with the mol ratio of Nonmetallocene part 1:0.01；The magnesium compound carrier and the mol ratio of the silicon compound counted with Si elements counted with Mg elements are 1：0.02, with Mg units Element meter magnesium compound carrier with the chemical treatments mol ratio of Group IVB elemental metal be 1：0.10.

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

Comparative example A

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

Magnesium compound carrier is processed without silicon compound in load type non-metallocene catalyst preparation process, but directly Group IVB chemical treatments are added dropwise to be processed；

Catalyst is designated as CAT-A.

Comparative example B

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

The magnesium compound carrier and the mol ratio of the silicon compound counted with Si elements counted with Mg elements are 1：0.05.

Catalyst is designated as CAT-B.

Comparative example C

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

The magnesium compound carrier and the mol ratio of the silicon compound counted with Si elements counted with Mg elements are 1：0.20.

Catalyst is designated as CAT-C.

Comparative example D

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

Nonmetallocene part is added without in magnesium compound solution preparation process；

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 vinyl polymerization in accordance with the following methods：

Polymerizing condition is：5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, be polymerized stagnation pressure 0.8MPa, gathers Close 85 DEG C of temperature；First stage：According to hydrogen and ethylene gas ratio a certain amount of hydrogen of addition of setting, a certain amount of hexene- 1, being continually fed into ethene makes polymerization stagnation pressure constant in 0.8MPa, and the gas phase of reactor is laid down after the reaction time that reaction reaches 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, releases kettle interpolymer, claimed after drying Amount 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, α in polymer- The insertion rate of alkene is accordingly improved or reduced, such that it is able to the content of comonomer in flexible modulation polymer.

The result of the test data of sequence number 1 and 3,4,5,6 understand 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 the method provided using the present invention is prepared polymer and has bigger adjustable range.

Sequence number 7,8 is the experimental result that one-part form homopolymerization and copolymerization are carried out using CAT-1 in table 1, sequence number 1 in contrast 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.

By sequence number 1 in contrast table 1 and the result of the test data of comparative example sequence number 18, it is not added with catalyst preparation process Enter silicon compound, the active and thus obtained polymer stacks density of polymerization catalyst is reduced, polymer molecular weight distribution broadens.

By 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 increased with the increase of silicon compound addition, the polymerization activity of catalyst and thus obtained polymer stacks density Plus, thus polymer molecular weight distribution narrow is illustrated present invention introduces silicon compound with invalid in effectively reduction catalyst Active metallic content, while catalyst activity and polymer stacks density are improved, 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 Nonmetallocene complex is introduced, thus obtained catalyst belongs to Ziegler-Natta type dynamics model catalyst, polymerization activity It is relatively low with polymer stacks density, polymer molecular weight wider distribution.

Rotation molding embodiment

Polymer P E-10 or PE-20, each with relative to the polymer for 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.）In 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 It is 10 rpm, molding time is 15min.ObtainφThe drum product of 1000mm × 1000mm, 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		Tensile yield strength（MPa）
				1	PE-10	3100	18.2
2	PE-20	2400	16.8

From the data of table 2, polymer made according to the present invention（PE-10）, it is poly- with what art methods were 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-19, 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 the pellet that will be obtained was through 70 DEG C of dryings 4 hours, 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 tubing of the mm of the diameter 63 and mm of nominal wall thickness about 5.8.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）		The FNCT out-of-service times（h）
					1	PE-9	24.8±0.1	21.7	6500
2	PE-19	27.2±0.1	20.4	5500

From the data of table 3, polymer made according to the present invention（PE-9）, with being polymerized that art methods are manufactured （PE-19）Thing is compared, and under equal processing conditions, 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 be described in detail to specific embodiment of the invention above in conjunction with the embodiments, however it is necessary that referring to Go out, protection scope of the present invention is not limited to these specific embodiments, but come by claims of annex It is determined that.Those skilled in the art these implementation methods are carried out in the range of technological thought of the invention and purport that can not depart from Appropriate change, and the implementation method after these changes is obviously also included within protection scope of the present invention.

Claims (17)

1. a kind of ethene-alpha-olefin copolymer, it is characterised in that monomeric unit with derived from ethylene with derived from being selected from The monomeric unit of at least one alpha-olefin of C3-C12 alpha-olefins, its heap density is 0.33 ~ 0.50g/cm³, oligomer is small In 2g/L, the fine powder content less than 75 microns is less than 3 weight %, and the melt index determined under the conditions of 190 DEG C and 2.16 kilograms is 0.02 ~ 20g/10min, molecular weight 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 list of the derived from ethylene The content of body unit is 88 ~ 99.8 weight %, and the content of the monomeric unit derived from the alpha-olefin is 0.2 ~ 12 weight %.

2. the ethene-alpha-olefin copolymer of claim 1, its have the monomeric unit of derived from ethylene with derived from selected from C4- The monomeric unit of at least one alpha-olefin of C8 alpha-olefins.

3. 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 co-catalyst reach 1~1000 with the mol ratio of the major catalyst in terms of central metal atom：1, it is anti-in polymerization 0.2 ~ 2.0MPa of stagnation pressure, hydrogen and ethylene partial pressure is answered to 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 co-catalyst of meter reaches 1~1000 with the mol ratio of the major catalyst in terms of central metal atom：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 that the preparation method by comprising the following steps is manufactured：

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

To precipitating reagent or the drying magnesium compound solution is added in the magnesium compound solution, magnesium compound carrier is obtained Step；

Make the magnesium compound carrier and following formula（X）Silicon compound and connect selected from the chemical treatments of IV B races metallic compound Touch, obtain the load type non-metallocene catalyst the step of,

Si(OR)_mX_4-mFormula（X）

Wherein, each R is identical or different, is each independently selected from C_1-4Straight or branched alkyl；M is 0,1,2,3 or 4 integer； Each X is identical or different, is each independently selected from halogen,

The preparation method is optionally additionally included in makes the magnesium compound carrier with the silicon compound and the chemical treatments Before contact, the magnesium compound carrier is pre-processed with selected from aikyiaiurnirsoxan beta, alkyl aluminum or its chemical treatments that help being combined The step of,

Wherein described Nonmetallocene part is selected from one or more in the compound with following chemical structural formula：

,

In chemical structural formula more than,

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 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 being coordination atom；

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

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 is selected from and carries one or more halogens or C₁- C₃₀Alkyl is used as the foregoing C for replacing base₁- 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 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-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- C₃₀Cyclic alkyl, C₂- C₃₀Alkenyl, C₂- C₃₀Alkynyl, C₆- C₃₀Aryl, C₈- C₃₀Condensed ring radical or C₄- C₃₀Heterocyclic radical, wherein the heterocyclic radical contains 1- 3 hetero atoms selected from nitrogen-atoms, oxygen atom or sulphur atom；

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.

4. the manufacture method of the ethene-alpha-olefin copolymer of claim 3, 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 or boron and the institute in terms of central metal atom The mol ratio for stating major catalyst reaches 10~100：1, in polymerisation stagnation pressure 0.4-0.8MPa, hydrogen and ethylene partial pressure ratio 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 or boron and the institute in terms of central metal atom The mol ratio for stating major catalyst reaches 10~100：1, in polymerisation stagnation pressure 0.3-0.6MPa, hydrogen and ethylene partial pressure ratio 0.03-0.3：1st, 75 ~ 95 DEG C of polymeric reaction temperature and comonomer addition are the condition of 0.02 ~ 0.2 gram/milligram major catalyst Under, make ethene and at least one alpha-olefin copolymer selected from C4-C8 alpha-olefins, A' stage polymers are obtained, 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.

5. the manufacture method of the ethene-alpha-olefin copolymer of claim 3 or 4, 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.

6. the manufacture method of the ethene-alpha-olefin copolymer of claim 5, 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%.

7. the manufacture method of the ethene-alpha-olefin copolymer of claim 3, wherein the magnesium compound is selected from magnesium halide Plant or various.

8. the manufacture method of the ethene-alpha-olefin copolymer of claim 3, wherein the solvent is selected from C_6-12Aromatic hydrocarbon, halo C_6-12One or more in aromatic hydrocarbon, ester and ether, the alcohol is selected from the one kind or many in fatty alcohol, aromatic alcohol and alicyclic ring alcohol Kind, wherein the alcohol is optionally selected from halogen atom or C_1-6The substitution base substitution of alkoxy.

9. the manufacture method of the ethene-alpha-olefin copolymer of claim 3, wherein the Nonmetallocene part be selected from have it is 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 is respectively coordination atom.

10. the manufacture method of the ethene-alpha-olefin copolymer of claim 9, wherein the Nonmetallocene part is selected from having such as The compound of lower chemical structural formula（A-1）To compound（A-4）And compound（B-1）To compound（B-4）In one kind or many Kind：

、 、

（A-1）（A-2）

、 、

（A-3）（A-4）

、 、

（B-1）（B-2）

With,

（B-3）（B-4）

In above all of chemical structural formula,

Y is selected from-NR²³R²⁴、-N(O)R²⁵R²⁶、-PR²⁸R²⁹、-OR³⁴、-SR³⁵、-S(O)R³⁶、-SeR³⁸Or-Se (O) R³⁹, 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, and wherein N, O, S, Se and P is each From being coordination atom；

R⁴、R⁶To R²¹It is each independently selected from hydrogen, C₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl or safing function group, 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

R⁵Selected from lone pair electrons, hydrogen, C on nitrogen₁- C₃₀Alkyl, the C of substitution₁- C₃₀Alkyl, oxy radical, sulfur-containing group, nitrogenous base Roll into a ball, rolled into a ball or phosphorus-containing groups containing seleno；Work as R⁵For oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or during phosphorus-containing groups, R⁵ In N, O, S, P and Se can be coordinated with atom and the B races metallic atom of center IV as coordination.

The manufacture method of the ethene-alpha-olefin copolymer of 11. claims 3, wherein the Nonmetallocene part is selected from having such as One or more in the compound of lower chemical structural formula：

、、、 、With。

The manufacture method of the ethene-alpha-olefin copolymer of 12. claims 3, wherein the Nonmetallocene part is selected from having such as One or more in the compound of lower chemical structural formula：

With。

The manufacture method of the ethene-alpha-olefin copolymer of 13. claims 3, 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 with Mg elements are 1：0.02~4.00, the precipitating reagent with it is described The volume ratio of solvent is 1：0.2~5, the magnesium compound carrier in terms of Mg elements and the silicon compound in terms of Si elements Mol ratio be 1：0.01-1, the magnesium compound carrier in terms of Mg elements and the chemistry with Group IVB elemental metal The mol ratio of inorganic agent is 1：0.01-1, and the magnesium compound carrier in terms of Mg elements with terms of Al elements described in help The mol ratio of chemical treatments is 1：0-1.0.

The manufacture method of the ethene-alpha-olefin copolymer of 14. claims 3, wherein the precipitating reagent be selected from alkane, cycloalkane, One or more in halogenated alkane and halo cycloalkane.

The manufacture method of the ethene-alpha-olefin copolymer of 15. claims 3, 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.

A kind of 16. polymer compositions, the ethene-alpha-olefin copolymer comprising claim 1 or 2 or by claim 3- The ethene-alpha-olefin copolymer of the manufacture method manufacture of the ethene-alpha-olefin copolymer of 15 any one, and antioxidant, optionally Also include one or more in halogen-absorber and pigment.

A kind of 17. moulded products, are manufactured by the polymer composition and shaping of melt-processed claim 16.