RU2596186C2 - Non-metallocene catalyst applied on carrier, its production and use - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing non-metallocene catalyst applied on carrier. Method involves a step for bringing into contact non-metallocene ligand, chemical treatment agent, selecting from compound of IVB group metal and alkoxy-magnesium spherical carrier in the presence of a solvent for interaction. Alkoxy-magnesium spherical carrier has an average particle size from 100 to 2,000 microns. Non-metallocene ligand in the present method represents one or several agents selected from a group comprising compounds having the following structure

wherein the values A, B, D, E, G, R¹, R², R³, d, q are given in the patent formula. Invention also suggests non-metallocene catalyst for homopolymerization /copolymerisation of olefins, method of homopolymerization /copolymerisation of olefins, polyethylene and chlorinated polyethylene.

EFFECT: polyolefin, produced in accordance with this invention, is characterised by excellent morphology of particles, high bulk density and specific surface area, variant pore structure, required particle size distribution and molecular weight distribution, and is especially suitable as a starting substance for use in direct production of chlorinated polyolefin.

12 cl, 1 tbl, 32 ex

Description

FIELD OF THE INVENTION

The present invention relates to a non-metallocene catalyst supported on a carrier, its preparation and use in the homopolymerization / copolymerization of olefins. The present invention also relates to polyethylene obtained by this homopolymerization / copolymerization of an olefin, and the use of said polyethylene in the production of chlorinated polyethylene.

BACKGROUND OF THE INVENTION

Chlorinated Polyethylene (CPE) is a statistical polymer resulting from a substitution reaction between polyethylene and chlorine gas. CPEs may exhibit the properties of soft plastics, resilient plastics, rubber-like plastics, leather-like hard plastics, or flame retardant brittle resins, depending on the chlorine content of their molecule. This specific molecular structure provides CPE with superior characteristics of flexibility, weather resistance, ozone resistance, chemical resistance, frost resistance and fire resistance, and makes it widely applicable in industries such as the manufacture of plastic doors / windows, PVC pipes and layers, waterproof rolls, anti-corrosion coatings, wires / cables, rubber-polymer composites and the like.

Typically, chlorinated polyethylene is prepared using powdered polyethylene as a starting material. Powdered polyethylene can be easily obtained by polymerization or can be obtained by grinding polyethylene granules. The polymerization method can be carried out on an industrial scale with an acceptable cost, and it gradually becomes the dominant method for the production of the starting material for chlorinated polyethylene.

Chinese patents Nos. 200910180602.9 and 200910180605.2, respectively, disclose polyethylene, which was obtained by homopolymerization of ethylene or copolymerization of ethylene with an alpha-olefin in the presence of a non-metallocene catalyst supported on a carrier. Polyethylene is characterized by low performance characteristics of particle morphology, specific surface area, pore volume and pore size, and therefore it is not suitable for use as a starting material for the production of chlorinated polyethylene.

Chinese Patent No. 200710162667.1 discloses a magnesium compound supported on a non-metallocene catalyst carrier and preparation thereof, wherein a magnesium compound containing a non-metallocene ligand is directly contacted with a compound containing a catalytically active metal by an in-situ support method. The magnesium compound used here may be alkoxyl magnesium, however, in the aforementioned prior art, the identification of whether the form of alkoxyl magnesium has any effect on the polymerization activity of the obtained catalyst or bulk density of the obtained polymer, and, in addition, could not confirm the use of the resulting polymer as a starting material for the direct production of chlorinated polyethylene.

Thus, in the prior art there is still a need for polyethylene, which is particularly suitable for use as a starting material in the direct production of chlorinated polyethylene. And there is also a need for any other polyolefins that exhibit properties suitable for use in the direct production of the corresponding chlorinated polyolefin.

SUMMARY OF THE INVENTION

After an in-depth study of the prior art, the inventors of the present invention found that a supported non-metallocene catalyst conventionally used in the prior art results in the formation of a polyolefin that demonstrates performance characteristics that are completely unsuitable for use in the direct production of chlorinated polyolefin, and based on this fact, additionally found that if the polyolefin is obtained as a result of the use of the supported etallotsenovogo catalyst prepared in accordance with the particular method described problems mentioned above can be solved, thereby realizing the present invention.

In accordance with the invention, the described method for producing a supported non-metallic catalyst can be carried out in the absence of any proton donor (for example, those traditionally used in this field). In addition, the described method for producing a supported non-metallic catalyst can be carried out in the absence of any electron donor (for example, compounds like monoesters, di-esters, di-ethers, diketones and glycol esters traditionally used in the manufacture of Ziegler catalyst Natta or Ziegler catalyst). In addition, the described method for the production of a non-metallocene catalyst supported on a carrier can be carried out without the need for strict reaction requirements and reaction conditions. For these reasons, the described method is simple and suitable for industrial applications.

In particular, the present invention relates to the following aspects.

A method of producing a supported non-metallocene catalyst, comprising the step of bringing the non-metallocene ligand into contact with a chemical treatment agent selected from a Group IVB metal compound in the presence of an alkoxymagnesium spherical carrier, preferably comprising the step of contacting the non-metallocene ligand, a chemical treatment agent and an alkoxymagnesium spherical carrier the presence of a solvent.

In this method, in the presence of a solvent, the non-metallocene ligand is brought into contact with an alkoxymagnesium spherical carrier and then a chemical treatment agent is added for further contact.

Said alkoxymagnesium spherical support is represented by the formula Mg (OR _a ) (OR _b ), where R _a and R _b are the same or different from each other, and each is independently selected from straight chain or branched C ₁ -C ₁₈ alkyl, preferably each independently is selected from c ₁ -C ₁₀ alkyl, straight or branched chain, more preferably are each independently selected from c ₁ -C ₆ alkyl with straight or branched chain, more preferably are each independently selected from c ₁ -C ₄ alkyl, a straight or branched chain w, more preferably are each independently selected from C ₂ -C ₄ alkyl, a straight or branched chain, most preferably both are ethyl.

In the claimed method, alkoxymagnesium spherical carrier has a sphericity of from 1 to 3, preferably from 1 to 1.5, bulk density from 0.2 to 1.0 g / cm ³ , preferably from 0.25 to 0.7 g / cm ³ more preferably 0.3 to 0.5 g / cm ³ and an average particle size of 5 to 2000 microns, preferably 50 to 1500 microns, more preferably 100 to 1000 microns.

The non-metallocene ligand of the present method is one or more selected from the group consisting of compounds having the following structure,

preferably one or more selected from the group consisting of the following compound (A) and the following compound (B),

preferably one or more selected from the group consisting of the following compound (A-1), the following compound (A-2), the following compound (A-3), the following compound (A-4), the following compound (B-1), the following compound (B-2), the following compound (B-3) and the following compound (B-4),

in all the above formulas,

q represents 0 or 1;

d represents 0 or 1;

, -NR²³R²⁴, -N(O)R²⁵R²⁶,

, -PR²⁸R²⁹, -P(O)R³⁰OR³¹, сульфоновую группу, сульфоксидную группу и -Se(O)R³⁹, где каждый N, O, S, Se и P представляет собой координационный атом;A is selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom,

, -NR ²³ R ²⁴ , -N (O) R ²⁵ R ²⁶ ,

, —PR ²⁸ R ²⁹ , —P (O) R ³⁰ OR ³¹ , a sulfonic group, a sulfoxide group, and —Se (O) R ³⁹ , where each N, O, S, Se, and P represents a coordination atom;

B is selected from the group consisting of a nitrogen atom, a nitrogen-containing group, a phosphorus-containing group and a C ₁ -C ₃₀ hydrocarbyl;

D is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen-containing group, a phosphorus-containing group, a C ₁ -C ₃₀ hydrocarbyl, sulfonic group or sulfoxide group, where each N, O, S, Se and P represents a coordination atom;

E is selected from the group consisting of a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, and a cyano group, where N, O, S, Se, and P are each a coordination atom;

F is selected from the group consisting of a nitrogen atom, a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, where each N, O, S, Se and P represents a coordination atom;

G is selected from the group consisting of C ₁ -C ₃₀ hydrocarbyl, substituted C ₁ -C ₃₀ hydrocarbyl, and an inert functional group;

Y is selected from the group consisting of a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group and a phosphorus-containing group, where each N, O, S, Se and P represents a coordination atom;

Z is selected from the group consisting of a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, and a cyano group, where each N, O, S, Se, and P represents a coordination atom;

→ represents a single bond or double bond;

- represents a covalent bond or ionic bond;

each R ¹ -R ⁴ , R ⁶ -R ^{21 is} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl, substituted C ₁ -C ₃₀ hydrocarbyl and an inert functional group, each R ²² -R ³⁶ , R ³⁸ and R ^{39 is} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl, where these groups may be the same or different from each other, and any adjacent groups may form a bond or ring (preferably aromatic ring) with each other;

the inert functional group is selected from the group consisting of a halogen atom, an oxygen-containing group, a nitrogen-containing group, a silicon-containing group, a germanium-containing group, a sulfur-containing group, a tin-containing group, a C ₁ -C ₁₀ ester group and a nitro group,

R ^{5 is} selected from the group consisting of a lone electron pair on a nitrogen atom, a hydrogen atom, a C ₁ -C ₃₀ hydrocarbyl, a substituted C ₁ -C ₃₀ hydrocarbyl, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group and a phosphorus-containing group, provided that that when R ⁵ is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group, each N, O, S, P and Se in the R ⁵ group acts as a coordination atom; and

substituted C ₁ -C ₃₀ hydrocarbyl selected from C ₁ -C ₃₀ hydrocarbyl having one or more substituents selected from a halogen atom and a C ₁ -C ₃₀ alkyl group,

the non-metallocene ligand is more preferably one or more selected from the group consisting of the following compounds,

more preferably one or more selected from the group consisting of the following compounds,

In the present method, the halogen atom is selected from the group consisting of F, Cl, Br and I,

, -NR²³R²⁴, -T-NR²³R²⁴ и -N(O)R²⁵R²⁶,a nitrogen-containing group selected from the group consisting of

, -NR ²³ R ²⁴ , -T-NR ²³ R ²⁴ and -N (O) R ²⁵ R ²⁶ ,

, -PR²⁸R²⁹, -P(O)R³⁰R³¹ и -P(O)R³²(OR³³),phosphorus-containing group selected from the group containing

, -PR ²⁸ R ²⁹ , -P (O) R ³⁰ R ³¹ and -P (O) R ³² (OR ³³ ),

the oxygen-containing group is selected from the group consisting of hydroxy, —OR ³⁴ and —T-OR ³⁴ ,

a sulfur-containing group selected from the group consisting of —SR ³⁵ , —T — SR ³⁵ , —S (O) R ^36, and —T — SO ₂ R ³⁷ ,

a selenium-containing group is selected from the group consisting of —SeR ³⁸ , —T-SeR ³⁸ , —Se (O) R ^39, and —T-Se (O) R ³⁹ ,

group T is selected from the group consisting of C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl,

R ^{37 is} selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl,

C ₁ -C ₃₀ hydrocarbyl selected from the group consisting of C ₁ -C ₃₀ alkyl group, C ₇ -C ₃₀ alkylaryl group, C ₇ -C ₃₀ aralkyl group, cyclic C ₃ -C ₃₀ alkyl group, C ₂ -C ₃₀ alkenyl a group, a C ₂ -C ₃₀ alkynyl group, a C ₆ -C ₃₀ aryl group, a fused cyclic C ₈ -C ₃₀ group, and a C ₄ -C ₃₀ heterocyclic group, where the heterocyclic group contains from 1 to 3 heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom,

the silicone-containing group is selected from the group consisting of —SiR ⁴² R ⁴³ R ⁴⁴ and —T-SiR ⁴⁵ ,

a germanium-containing group is selected from the group consisting of —GeR ⁴⁶ R ⁴⁷ R ⁴⁸ and —T-GeR ⁴⁹ ,

a tin-containing group is selected from the group consisting of —SnR ⁵⁰ R ⁵¹ R ⁵² , —T-SnR ⁵³ and —T-Sn (O) R ⁵⁴ ,

each R ⁴² -R ^{54 is} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl, where these groups may be the same or different from each other, and any adjacent groups may form a bond or ring with each other and

group T is defined as described above.

In the method of the present invention, the molar ratio of alkoxy magnesium spherical support (Mg-based) to non-metallocene ligand is 1: 0.001-0.08, preferably 1: 0.005-0.06, more preferably 1: 0.01-0.04, and the molar ratio the alkoxy magnesium spherical support (Mg-based) to the chemical treatment agent (based on a metal of group IVB) is 1: 1-30, preferably 1: 2-20, more preferably 1: 4-10.

Said Group IVB metal compound is one or more selected from the group consisting of Group IVB metal halide compound, Group IVB metal alkyl halide compound, Group IVB metal alkoxy halide compound, preferably one or more Group IVB metal halide compounds, more preferably one or more, selected from the group consisting of TiCl ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , HfCl ₄ and HfBr ₄ , more preferably one or more selected from the group consisting of TiCl ₄ and ZrCl ₄ .

The invention relates to a supported non-metallocene catalyst obtained in accordance with the above method.

The invention relates to a method for homopolymerization / copolymerization of an olefin, where the supported non-metallocene catalyst according to the preceding aspect is used as the main catalyst, in combination with one or more selected from the group consisting of aluminoxane, alkylaluminum, halogenated alkylaluminum, fluoroborane, alkylboron and ammonium alkylboron salt as a cocatalyst, for homopolymerization or copolymerization of an olefin.

In said olefin homopolymerization / copolymerization process, a suspension polymerization procedure takes place, and under conditions of a total polymerization pressure of 0.2 to 2.0 MPa (preferably 0.5 to 1.5 MPa), the ratio of the partial pressure of hydrogen gas to ethylene is 0, 01-0.2: 1 (preferably 0.02-0.1: 1, most preferably 0.03-0.08: 1), polymerization temperatures from 60 to 100 ° C (preferably from 70 to 95 ° C, more preferably from 80 to 90 ° C), and the amount of optional comonomer from 0.5 to 10 g per 1 mg of basic catalyst (preferably from 1 to 5 g per 1 mg of the main catalyst), ethylene homopolymerizes or ethylene copolymerizes with at least one alpha olefin (s) selected from C ₃ -C ₁₂ alpha olefin (preferably C ₃ -C ₈ alpha olefin), to obtain polyethylene.

Also disclosed is a polyethylene having a repeating unit derived from ethylene and an optionally repeating unit derived from at least one alpha olefin (s) selected from C ₃ -C ₁₂ alpha olefin (preferably C ₃ -C ₈ alpha-olefin), a bulk density of from 0.33 to 0.50 g / cm ³ , preferably from 0.38 to 0.46 g / cm ³ , more preferably from 0.40 to 0.44 g / cm ³ , the content oligomers less than 2 g / l, the content of fine powder (less than 75 microns) less than 5 wt.%, melt index (at 190 ° C and a load of 2.16 kg) from 0, 02 to 5 g / 10 min, a molecular weight distribution of Mw / Mn from 2.5 to 20 (preferably from 4 to 10), a density of from 0.94 to 0.96 g / cm ³ , an average particle size of from 200 to 400 μm, specific surface area from 0.2 to 3.0 m ² / g, preferably from 1.0 to 3.0 m ² / g, more preferably from 1.5 to 3.0 m ² / g, pore volume from 0.001 to 0.15 cm ³ / g, preferably from 0.01 to 0.15 cm ³ / g, more preferably from 0.05 to 0.12 cm ³ / g, pore size from 10 to 80 nm, preferably from 20 up to 70 nm, more preferably from 20 to 60 nm, and relative to the total weight of 100 wt.% polyethylene, the content of repeating Vienna obtained from ethylene, from 95 to 100 wt.%, and the content of the repeating unit derived from at least one alpha-olefin (s), 0 to 5 wt.%.

Described chlorinated polyethylene obtained by chlorination of the above polyethylene obtained in accordance with the previously described methods.

The effect of this invention

The method for producing a non-metallocene catalyst supported by the invention is simple from the point of view of the technological method, applicable on an industrial scale and stable in relation to dynamic characteristics.

As a result of using a catalytic system consisting of a non-metallocene catalyst supported on a support prepared in accordance with the presented method and a cocatalyst, only a relatively small amount of cocatalyst (e.g. methylaluminoxane or triethylaluminium) is necessary to achieve a relatively high olefin polymerization activity, and when used in copolymerization, this catalytic system exhibits a significant comonomer effect, namely, under relatively the same conditions , The copolymerization activity is higher than that of the homopolymerization.

In accordance with the present invention, the polyolefin (especially polyethylene) obtained according to the presented olefin homopolymerization / copolymerization method is characterized by excellent particle morphology, high bulk density and specific surface area, variant pore structure, desired particle size distribution and molecular weight distribution, and It is especially suitable for use as a starting material in the direct production of a chlorinated polyolefin.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be described in detail below with reference to specific embodiments. However, it is known that the scope of the claims of the present invention should not be construed as being limited by these specific embodiments, but rather is determined by the appended claims.

With reference to the present description of the invention, unless otherwise indicated or determined by a person skilled in the art as an unreasonable hydrocarbon or hydrocarbon derivative having 3 or more carbon atoms (e.g. propyl, propoxy, butyl, butane, butene, butenyl, hexane and the like ), when “normal” or “n-” appears without the prefix, as a rule, refers to its corresponding n-isomer. For example, propyl typically means n-propyl, while butane usually means n-butane.

With reference to this description of the invention, for ease of understanding of this description, a group or substituent group in a compound is usually defined, but its valency is not specified, namely whether it is monovalent, divalent, trivalent, tetravalent or otherwise. However, it is not difficult for a person skilled in the art to define it, given the position or substitution conditions of said group or substituent group in said compound.

In accordance with the present invention, firstly, a method for producing a non-metallocene catalyst supported on a carrier is disclosed, comprising the step of bringing the non-metallocene ligand into contact with a chemical treatment agent selected from a Group IVB metal compound in the presence of an alkoxy magnesium spherical carrier (hereinafter referred to as “Contacting stage”).

In accordance with one significant aspect of the present invention, when a nonmetallocene ligand comes into contact with a chemical treatment agent in the presence of an alkoxymagnesium spherical carrier (as a carrier), a coordination reaction occurs between them to form a nonmetallocene complex that receives an IVB metal atom derived from a chemical agent processing as a central metal atom, and at the same time, a nonmetallocene complex generated in this way directly or immediately loaded on or in a carrier (hereinafter, referred to herein as a support reaction in-situ).

The alkoxymagnesium spherical carrier is further described as follows.

In accordance with the present invention, the alkoxymagnesium of which the alkoxymagnesium spherical carrier is composed is usually represented by the formula Mg (OR _a ) (OR _b ). In this formula, R _a and R _b are the same or different from each other, and each is independently selected from straight chain or branched C ₁ -C ₁₈ alkyl, preferably each is independently selected from straight and branched C ₁ -C ₁₀ alkyl , more preferably, each is independently selected from straight chain or branched C ₁ -C ₆ alkyl, in addition, preferably each is independently selected from straight or branched C ₁ -C ₄ alkyl, more preferably each is independently selected from C ₂ -C ₄ alkyl with n unbranched or branched chain.

In accordance with the present invention, dimethoxy magnesium (Mg (OCH ₃ ) ₂ ), diethoxy magnesium (Mg (OC ₂ H ₅ ) ₂ ), dipropoxy magnesium (Mg (OC ₃ H ₇ ) ₂ ), dibutoximagnesium may be mentioned as alkoxy magnesium. (Mg (OC ₄ H ₉ ) ₂ ), diisobutoximagnesium (Mg (i-OC ₄ H ₉ ) ₂ ), di (2-ethylhexyloxy) magnesium, ethoxypropoxymagnesium (Mg (OC ₂ H ₅ ) (OC ₃ H ₇ )), ethoxybutoximagnesium (Mg (OC ₂ H ₅ ) (OC ₄ H ₉ )), and the like, preferably diethoxy magnesium (Mg (OC ₂ H ₅ ) ₂ ).

The alkoxymagnesium or alkoxymagnesium spherical carrier can be used of the same type or as a mixture of two or more types in any ratio between them, without any restrictions.

According to the present invention, an alkoxymagnesium spherical carrier can be obtained by any standard technology, or it can be commercially available without any limitation.

In accordance with the present invention, in most cases, an alkoxymagnesium spherical carrier has a sphericity of 1 to 3 (measured using a laser particle size analyzer, where the sphericity is calculated as the result of dividing the measured longest spherical carrier size by the measured shortest spherical size carrier), preferably from 1 to 1.5.

In accordance with the present invention, in most cases, the alkoxy magnesium spherical carrier has a bulk density (measured in accordance with Chinese State Standard GB1636-79) from 0.2 to 1.0 g / cm ³ , preferably from 0.25 to 0.7 g / cm ³ , more preferably 0.3 to 0.5 g / cm ³ .

In accordance with the present invention, in most cases, the alkoxymagnesium spherical carrier has an average particle size (measured on a laser particle size analyzer) of from 5 to 2000 μm, preferably from 50 to 1500 μm, more preferably from 100 to 1000 μm.

In accordance with the present invention, the term "non-metallocene complex" means a catalyst with a single center of polymerization on a metal for the polymerization of an olefin and is completely different from a metallocene complex, an organic metal compound that does not contain cyclopentadienyl or any of its derivatives (for example, a metallocene ring, fluorene ring or indene ring), and is capable of exhibiting catalytic activity for the polymerization of an olefin when used in conjunction with cocatalization torus similar specific description in the present specification, which is hereinafter also called "non-metallocene complex to olefin polymerization." The compound contains a central metal atom and at least one multi-toothed ligand (preferably three or more toothed ligand) bonded to the central metal atom via coordination bond. The term "non-metallocene ligand" corresponds to the above multi-tooth ligand.

In accordance with the present invention, the non-metallocene ligand is selected from compounds having the following structure,

According to the present invention, groups A, D and E (coordination groups) in the compound form a coordination bond by coordination reaction with a Group IVB metal atom contained in a Group IVB metal compound used as a chemical treatment agent through coordination atoms (e.g., heteroatoms such as N, O, S, Se and P) contained in these groups, resulting in the formation of a complex (for example, non-metallocene complex in accordance with the present invention) having the specified metal atom s IVB as the central metal atom M.

According to another embodiment of the present invention, the non-metallocene ligand is selected from the following compound (A) and the following compound (B),

In accordance with another embodiment of the present invention, the non-metallocene ligand is selected from the following compound (A-1), the following compound (A-2), the following compound (A-3), the following compound (A-4), the following compound (B -1), the following compound (B-2), the following compound (B-3) and the following compound (B-4),

in all the above formulas,

q is 0 or 1.

d represents 0 or 1.

, -NR²³R²⁴, -N(O)R²⁵R²⁶,

, -PR²⁸R²⁹, -P(O)R³⁰OR³¹, сульфоновую группу, сульфоксидную группу и -Se(O)R³⁹, где каждый N, O, S, Se и P представляет собой координационный атом.A is selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom,

, -NR ²³ R ²⁴ , -N (O) R ²⁵ R ²⁶ ,

, -PR ²⁸ R ²⁹ , -P (O) R ³⁰ OR ³¹ , a sulfonic group, a sulfoxide group and -Se (O) R ³⁹ , where each N, O, S, Se and P represents a coordination atom.

B is selected from the group containing a nitrogen atom, a nitrogen containing group, a phosphorus containing group, and a C ₁ -C ₃₀ hydrocarbyl.

D is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen-containing group, a phosphorus-containing group, a C ₁ -C ₃₀ hydrocarbyl, a sulfonic group and a sulfoxide group, where each N, O, S, Se and P represents a coordination atom.

E is selected from the group containing a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group and a cyano group (—CN), where each N, O, S, Se and P represents a coordination atom.

F is selected from the group consisting of a nitrogen atom, a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group and a phosphorus-containing group, where each N, O, S, Se and P represents a coordination atom.

G is selected from the group consisting of C ₁ -C ₃₀ hydrocarbyl, substituted C ₁ -C ₃₀ hydrocarbyl, and an inert functional group.

Y is selected from the group containing a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, and a phosphorus-containing group, where each N, O, S, Se, and P represents a coordination atom.

Z is selected from the group containing a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group and a cyano group (-CN), for example, -NR ²³ R ²⁴ , -N (O) R ²⁵ R ²⁶ , -PR ²⁸ R ²⁹ , -P (O) R ³⁰ R ³¹ , -OR ³⁴ , -SR ³⁵ , -S (O) R ³⁶ , -SeR ³⁸ or -Se (O) R ³⁹ , where each N, O, S, Se and P represents a coordination atom.

→ stands for single bond or double bond.

- denotes a covalent bond or ionic bond.

Each R ¹ -R ⁴ , R ⁶ -R ^{21 is} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl, substituted C ₁ -C ₃₀ hydrocarbyl (preferably halogenated hydrocarbyl, for example, -CH ₂ Cl and -CH ₂ CH ₂ Cl) and an inert functional group. Each R ²² -R ³⁶ , R ³⁸ and R ^{39 is} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl, substituted C ₁ -C ₃₀ hydrocarbyl (preferably halogenated hydrocarbyl, for example, -CH ₂ Cl and -CH ₂ CH ₂ Cl). These groups may be the same or different from each other, and any adjacent groups (for example, R ¹ and R ² , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , R ²⁰ and R ²¹ , R ²³ and R ²⁴ , or R ²⁵ and R ²⁶ ) can form a bond or ring (preferably an aromatic ring for example, an unsubstituted benzene ring or a benzene ring substituted by one to four C ₁ -C ₃₀ hydrocarbyls or substituted C ₁ -C ₃₀ hydrocarbyls (preferably halogenated hydrocarbyl, for example, -CH ₂ Cl and -CH ₂ CH ₂ Cl)) together.

R ^{5 is} selected from the group consisting of a lone electron pair on a nitrogen atom, a hydrogen atom, a C ₁ -C ₃₀ hydrocarbyl, a substituted C ₁ -C ₃₀ hydrocarbyl, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group, and a phosphorus-containing group, provided that that when R ⁵ is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group, each N, O, S, P and Se in the R ⁵ group can act as a coordination atom (to coordinate with the central atom ohm metal M).

In the context of this invention, as an inert functional group, one or more selected from the group consisting of a halogen atom, an oxygen-containing group, a nitrogen-containing group, a silicone-containing group, a germanium-containing group, a sulfur-containing group, a tin-containing group, a C ₁ -C ₁₀ ester can be given a group and a nitro group (—NO ₂ ), while C ₁ –C ₃₀ hydrocarbyl or substituted C ₁ –C ₃₀ hydrocarbyl are generally excluded.

In the context of this invention, limited by the specific structure of the presented non-metallocene ligand, an inert functional group is characterized in that:

(1) it does not interfere with the coordination method between the above group A, D, E, F, Y or Z and the central metal atom M, and

(2) its ability to form a coordination bond with the central metal atom M is inferior to the ability of the above group A, D, E, F, Y or Z to form a coordination bond with the central metal atom M, and will not shift the formed coordination between the central metal atom M and any of these groups are A, D, E, F, Y, and Z.

In accordance with the present invention, in all the above formulas, if necessary, any two or more adjacent groups (for example, R ²¹ and group Z, or R ¹³ and group Y) can form a ring with each other, preferably aromatic C ₆ -C ₃₀ a hetero ring containing a heteroatom derived from the group Z or Y, for example, a pyridine ring, where the aromatic hetero ring is optionally substituted with one or more substituents selected from the group consisting of C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl.

In the context of this invention, a halogen atom is selected from the group consisting of F, Cl, Br and I.

, -NR²³R²⁴, -T-NR²³R²⁴ и -N(O)R²⁵R²⁶.In the context of the present invention, a nitrogen-containing group is selected from the group consisting of

, -NR ²³ R ²⁴ , -T-NR ²³ R ²⁴ and -N (O) R ²⁵ R ²⁶ .

, -PR²⁸R²⁹, -P(O)R³⁰R³¹ и -P(O)R³²(OR³³).In the context of this invention, a phosphorus-containing group is selected from the group consisting of

, -PR ²⁸ R ²⁹ , -P (O) R ³⁰ R ³¹ and -P (O) R ³² (OR ³³ ).

In the context of the present invention, the oxygen-containing group is selected from the group consisting of hydroxy, —OR ³⁴ and —T-OR ³⁴ .

In the context of the present invention, the sulfur-containing group is selected from the group consisting of —SR ³⁵ , —T-SR ³⁵ , —S (O) R ^36, and —T-SO ₂ R ³⁷ .

In the context of this invention, a selenium-containing group is selected from the group consisting of —SeR ³⁸ , —T-SeR ³⁸ , —Se (O) R ^39, and -T-Se (O) R ³⁹ .

In the context of this invention, group T is selected from the group consisting of C ₁ -C ₃₀ hydrocarbyl or substituted C ₁ -C ₃₀ hydrocarbyl.

In the context of the present invention, R ^{37 is} selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl.

In the context of the present invention, a C ₁ -C ₃₀ hydrocarbyl is selected from the group consisting of a C ₁ -C ₃₀ alkyl group (e.g., a C ₁ -C ₆ alkyl group, e.g. an isobutyl group), a C ₇ -C ₃₀ alkylaryl group (e.g. tolyl, xylyl, diisobutylphenyl), C ₇ -C ₃₀ aralkyl group (e.g. benzyl), cyclic C ₃ -C ₃₀ alkyl group, C ₂ -C ₃₀ alkenyl group, C ₂ -C ₃₀ alkynyl group, C ₆ -C ₃₀ an aryl group (e.g., phenyl, naphthyl, anthracyl), a fused cyclic C ₈ -C ₃₀ group and a C ₄ -C ₃₀ heterocyclic group, where the heterocyclic group contains from 1 up to 3 heteroatoms selected from the group containing a nitrogen atom, an oxygen atom and a sulfur atom, including, for example, a pyridyl group, a pyrrolyl group, a furanyl group and a thienyl group.

In the context of this invention, depending on the nature of the corresponding groups to which C ₁ -C ₃₀ hydrocarbyl is bound, it will be apparent to one skilled in the art that by C ₁ -C ₃₀ hydrocarbyl may be meant C ₁ -C ₃₀ hydrocarbyl-diyl (divalent group , or called a C ₁ -C ₃₀ hydrocarbylene group) or a C ₁ -C ₃₀ hydrocarbon-triyl (trivalent group).

In the context of the present invention, by substituted C ₁ -C ₃₀ hydrocarbyl is meant the above C ₁ -C ₃₀ hydrocarbyl having one or more inert substituents. By inert is meant that these inert substituents will not substantially interfere with the coordination method between the above coordination groups (namely, the above groups A, D, E, F, Y and Z, or in addition, if applicable, R ⁵ ) and a central metal atom M (namely, the above Group IVB metal atom). In other words, limited by the specific chemical structure of the present non-metallocene ligand, these substituents are not capable, or are not able (due, for example, to spatial difficulties) to coordinate with the Group IVB metal atom to form a coordination bond. Typically, an inert substituent refers to the above halogen atom or a C ₁ -C ₃₀ alkyl group (for example, a C ₁ -C ₆ alkyl group, for example, an isobutyl group).

In the context of the present invention, the silicone-containing group is selected from the group consisting of —SiR ⁴² R ⁴³ R ⁴⁴ and —T-SiR ^{45; the} germanium-containing group is selected from the group consisting of —GeR ⁴⁶ R ⁴⁷ R ⁴⁸ and —T-GeR ⁴⁹ , the tin containing group is selected from a group containing —SnR ⁵⁰ R ⁵¹ R ⁵² , —T-SnR ⁵³ and —T-Sn (O) R ⁵⁴ . Each R ⁴² -R ^{54 is} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl, or substituted C ₁ -C ₃₀ hydrocarbyl, where these groups may be identical or may differ from each other, and any adjacent groups may form a bond or ring with each other. Group T is defined as described above.

The following compounds may be further given as an example of a non-metallocene ligand.

The following compounds may be further given as an example of a non-metallocene ligand.

The following compounds may be further given as an example of a non-metallocene ligand.

The following compounds may be further given as an example of a non-metallocene ligand.

Nonmetallocene ligands of the same type can be used or as a mixture of two or more types with any ratio between them.

In accordance with the present invention, these non-metallocene ligands do not correspond to the diester compound commonly used in the art as an electron donor compound.

In accordance with the present invention, a non-metallocene ligand can be obtained by a person skilled in the art in accordance with any method known in the art. For detailed information about this method, you can refer, for example, to WO03 / 010207 or Chinese patents Nos. ZL01126323.7 and ZL02110844.7. All references cited are hereby incorporated by reference in their entirety.

According to the present invention, with respect to the amount of non-metallocene ligand used, it is preferable that the molar ratio of the alkoxy magnesium spherical support (Mg based) to the non-metallocene ligand is 1: 0.001-0.08, preferably 1: 0.005-0.06, more preferably 1: 0.01-0.04.

The chemical treatment agent is further described as follows.

In accordance with the present invention, a Group IVB metal compound is used as a chemical treatment agent.

As a Group IVB metal compound, an example is a Group IVB metal halide compound, a Group IVB alkyl halide metal compound and a Group IVB metal alkoxyhalide compound.

As a halide compound of a Group IVB metal, an alkyl halide compound of a Group IVB metal, and an alkoxyhalide compound of a Group IVB metal, an example is a compound having the following general formula.

M (OR ¹ ) _m X _n R ² _4-mn

Where,

m represents 0, 1, 2 or 3,

n represents 0, 1, 2, 3 or 4,

M represents a Group IVB metal in the periodic table of elements, for example, titanium, zirconium, hafnium and the like,

X represents a halogen atom, for example, F, Cl, Br and I, and

each R ¹ and R ^{2 is} independently selected from the group consisting of C ₁ -C ₁₀ alkyl, for example methyl, ethyl, propyl, n-butyl, isobutyl and the like, R ¹ and R ² may be identical to each other or different from each other friend.

In particular, an example of a Group IVB metal halide compound is, for example, titanium tetrafluoride (TiF ₄ ), titanium tetrachloride (TiCl ₄ ), titanium tetrabromide (TiBr ₄ ), titanium tetraiodide (TiI ₄ ), zirconium tetrafluoride (ZrF ₄ ), tetrachloride zirconium (ZrCl ₄ ), zirconium tetrabromide (ZrBr ₄ ), zirconium tetraiodide (ZrI ₄ ), hafnium tetrafluoride (HfF ₄ ), hafnium tetrachloride (HfCl ₄ ), hafnium tetrabromide (HfBr ₄ ), hafnium tetraiodide (HfI ₄ ).

An example of an alkyl halide compound of a Group IVB metal is trimethylchlorotitan (TiCl (CH ₃ ) ₃ ), triethyl chlorotitan (TiCl (CH ₃ CH ₂ ) ₃ ), triisobutyl chlorotitan (TiCl (iC ₄ H ₉ ) ₃ ), tri-n-butyl chlorotitan (TiCl ( C ₄ H ₉ ) ₃ ), dimethyldichloro titanium (TiCl ₂ (CH ₃ ) ₂ ), diethyl dichloro titanium (TiCl ₂ (CH ₃ CH ₂ ) ₂ ), diisobutyl dichloro titan (TiCl ₂ (iC ₄ H ₉ ) ₂ ), tri-n-butyl chlorotitan (TiCl (C ₄ H ₉ ) ₃ ), methyl trichloro-titan (Ti (CH ₃ ) Cl ₃ ), ethyl trichloro-titan (Ti (CH ₃ CH ₂ ) Cl ₃ ), isobutyl trichloro-titan (Ti (iC ₄ H ₉ ) Cl ₃ ), n- butyl trichlorotitan (Ti (C ₄ H ₉ ) Cl ₃ ),

trimethyl bromo titanium (TiBr (CH ₃ ) ₃ ), triethyl bromo titanium (TiBr (CH ₃ CH ₂ ) ₃ ), triisobutyl bromo titanium (TiBr (iC ₄ H ₉ ) ₃ ), tri-n-butyl bromo titanium (TiBr (C ₄ H ₉ ) ₃ ), dimethyldibromotitanium (TiBr ₂ (CH ₃ ) ₂ ), diethyl dibromtitanium (TiBr ₂ (CH ₃ CH ₂ ) ₂ ), diisobutyl dibromotitan (TiBr ₂ (iC ₄ H ₉ ) ₂ ), tri-n-butyl bromotitan (TiBr (C ₄ H ₉ ) ₃ ), methyltribromtitanium (Ti (CH ₃ ) Br ₃ ), ethyl tribromtitanium (Ti (CH ₃ CH ₂ ) Br ₃ ), isobutyl tribromtitan (Ti (iC ₄ H ₉ ) Br ₃ ), n-butyl tribromtitan (Ti (C ₄ H ₉ ) Br ₃ ),

trimethylchlorosirconium (ZrCl (CH ₃ ) ₃ ), triethyl chlorozirconium (ZrCl (CH ₃ CH ₂ ) ₃ ), triisobutylchlorosirconium (ZrCl (iC ₄ H ₉ ) ₃ ), tri-n-butylchlorosirconium (ZrCl (C ₄ H ₉ ) ₃ ), dimethyldichlorozirconium (ZrCl ₂ (CH ₃ ) ₂ ), diethyl dichlorozirconium (ZrCl ₂ (CH ₃ CH ₂ ) ₂ ), diisobutyl dichlorozirconium (ZrCl ₂ (iC ₄ H ₉ ) ₂ ), tri-n-butyl chlorozirconium (ZrCl (C ₄ H ₉ ) ₃ ), methyl trichlorozirconium (Zr (CH ₃ ) Cl ₃ ), ethyl trichlorozirconium (Zr (CH ₃ CH ₂ ) Cl ₃ ), isobutyl trichlorozirconium (Zr (iC ₄ H ₉ ) Cl ₃ ), n-butyl trichlorozirconium (Zr (C ₄ H ₉ ) Cl ₃ ),

trimethyl bromozirconium (ZrBr (CH ₃ ) ₃ ), triethyl bromozirconium (ZrBr (CH ₃ CH ₂ ) ₃ ), triisobutyl bromozirconium (ZrBr (iC ₄ H ₉ ) ₃ ), tri-n-butyl bromozirconium (ZrBr (C ₄ H ₉ ) ₃ ), dimethyldibromozirconium (ZrBr ₂ (CH ₃ ) ₂ ), diethyl dibromozirconium (ZrBr ₂ (CH ₃ CH ₂ ) ₂ ), diisobutyl dibromozirconium (ZrBr ₂ (iC ₄ H ₉ ) ₂ ), tri-n-butyl bromozirconium (ZrBr) (C ₄ H ₉ br) ₃ ), methyl tribromirzirconium (Zr (CH ₃ ) Br ₃ ), ethyl tribromirzirconium (Zr (CH ₃ CH ₂ ) Br ₃ ), isobutyl tribromirzirconium (Zr (iC ₄ H ₉ ) Br ₃ ), n-butyl tribromirzirconium (Zr (C ₄ H ₉ ) Br ₃ ),

trimethylchloro-hafnium (HfCl (CH ₃ ) ₃ ), triethyl-chloro-hafnium (HfCl (CH ₃ CH ₂ ) ₃ ), triisobutyl-chloro-hafnium (HfCl (iC ₄ H ₉ ) ₃ ), tri-n-butyl-chloro-hafnium (HfCl (C ₄ H ₉ ) ₃ ), dimethyldichloro-hafnium (HfCl ₂ (CH ₃ ) ₂ ), diethyl-dichloro-hafnium (HfCl ₂ (CH ₃ CH ₂ ) ₂ ), diisobutyl-dichloro-hafnium (HfCl ₂ (iC ₄ H ₉ ) ₂ ), tri-n-butylchloro-hafnium (HfCl (C ₄ H ₉ ) ₃ ), methyl trichloro-hafnium (Hf (CH ₃ ) Cl ₃ ), ethyl trichloro-hafnium (Hf (CH ₃ CH ₂ ) Cl ₃ ), isobutyl trichloro-hafnium (Hf (iC ₄ H ₉ ) Cl ₃ ), n-butyl trichloro-hafnium (Hf (C ₄ H ₉ ) Cl ₃ ),

trimethyl bromo hafnium (HfBr (CH ₃ ) ₃ ), triethyl bromo hafnium (HfBr (CH ₃ CH ₂ ) ₃ ), triisobutyl bromo hafnium (HfBr (iC ₄ H ₉ ) ₃ ), tri-n-butyl bromo hafnium (HfBr (C ₄ H ₉ ) ₃ ), dimethyl dibromo hafnium (HfBr ₂ (CH ₃ ) ₂ ), diethyl dibromo hafnium (HfBr ₂ (CH ₃ CH ₂ ) ₂ ), diisobutyl dibromo hafnium (HfBr ₂ (iC ₄ H ₉ ) ₂ ), tri-n-butyl bromo hafnium (HfBr (C ₄ H ₉ ) ₃ ), methyltribromahafnium (Hf (CH ₃ ) Br ₃ ), ethyl tribromahafnium (Hf (CH ₃ CH ₂ ) Br ₃ ), isobutyl tribromafnium (Hf (iC ₄ H ₉ ) Br ₃ ), n-butyl tribromhafnium (Hf (C ₄ H ₉ ) Br ₃ ).

An example of an alkoxyhaloid compound of a Group IVB metal is trimethoxychlorotitan (TiCl (OCH ₃ ) ₃ ), triethoxychlortitanium (TiCl (OCH ₃ CH ₂ ) ₃ ), triisobutoxychlortitane (TiCl (i-OC ₄ H ₉ ) ₃ ), tri-n-butoxychlortitane ( TiCl (OC ₄ H ₉ ) ₃ ), dimethoxy dichloro titanium (TiCl ₂ (OCH ₃ ) ₂ ), diethoxy dichloro titanium (TiCl ₂ (OCH ₃ CH ₂ ) ₂ ) diisobutoxy dichloro titanium (TiCl ₂ (i-OC ₄ H ₉ ) ₂ ), three -n-butoxychlortitanium (TiCl (OC ₄ H ₉ ) ₃ ), methoxytrichlorotitan (Ti (OCH ₃ ) Cl ₃ ), ethoxytrichlorotitanium (Ti (OCH ₃ CH ₂ ) Cl ₃ ), isobutoxytrichlorotitan (Ti (iC ₄ H ₉ ) Cl ₃ ), n-butoxytrichlorotitan (Ti (OC ₄ H ₉ ) Cl ₃ ),

trimethoxybromo titanium (TiBr (OCH ₃ ) ₃ ), triethoxy bromo titanium (TiBr (OCH ₃ CH ₂ ) ₃ ), triisobutoxy bromo titanium (TiBr (i-OC ₄ H ₉ ) ₃ ), tri-n-butoxybromo titanium (TiBr (OC ₄ H ₉ ) ₃ ), dimethoxy dibromo titanium (TiBr ₂ (OCH ₃ ) ₂ ), diethoxy dibromo titanium (TiBr ₂ (OCH ₃ CH ₂ ) ₂ ), diisobutoxy dibromo titanium (TiBr ₂ (i-OC ₄ H ₉ ) ₂ ), tri-n-butoxy bromo titanium (TiBr (OC ₄ H ₉ ) ₃ ), methoxytribromtitanium (Ti (OCH ₃ ) Br ₃ ), ethoxytribromtitanium (Ti (OCH ₃ CH ₂ ) Br ₃ ), isobutoxytribromtitan (Ti (iC ₄ H ₉ ) Br ₃ ), n-butoxytribromtitan (Ti ( OC ₄ H ₉ ) Br ₃ ),

trimethoxychloro zirconium (ZrCl (OCH ₃ ) ₃ ), triethoxychloro zirconium (ZrCl (OCH ₃ CH ₂ ) ₃ ), triisobutoxychloro zirconium (ZrCl (i-OC ₄ H ₉ ) ₃ ), tri-n-butoxychloro zirconium (ZrCl (OC ₄ H ₉ ) ₃ ), dimethoxy dichlorozirconium (ZrCl ₂ (OCH ₃ ) ₂ ), diethoxy dichlorozirconium (ZrCl ₂ (OCH ₃ CH ₂ ) ₂ ), diisobutoxy dichlorozirconium (ZrCl ₂ (i-OC ₄ H ₉ ) ₂ ), tri-n-butoxychlorosirconium (ZrCl (OC ₄ H ₉ ) ₃ ), methoxy trichloro zirconium (Zr (OCH ₃ ) Cl ₃ ), ethoxy trichloro zirconium (Zr (OCH ₃ CH ₂ ) Cl ₃ ), isobutoxy trichloro zirconium (Zr (iC ₄ H ₉ ) Cl ₃ ), n-butoxy trichloro zirconium (Zr ( OC ₄ H ₉ ) Cl ₃ ),

trimethoxybromozirconium (ZrBr (OCH ₃ ) ₃ ), triethoxybromozirconium (ZrBr (OCH ₃ CH ₂ ) ₃ ), triisobutoxybromozirconium (ZrBr (i-OC ₄ H ₉ ) ₃ ), tri-n-butoxybromozirconium (ZrBr (OC ₄ H _{9 3} ) ), dimethoxybromozirconium (ZrBr ₂ (OCH ₃ ) ₂ ), diethoxybromozirconium (ZrBr ₂ (OCH ₃ CH ₂ ) ₂ ), diisobutoxybromozirconium (ZrBr ₂ (i-OC ₄ H ₉ ) ₂ ), tri-n-butoxybromozirconium (ZrBr OC ₄ H ₉ ) ₃ ), methoxytribromirzirconium (Zr (OCH ₃ ) Br ₃ ), ethoxytribromirzirconium (Zr (OCH ₃ CH ₂ ) Br ₃ ), isobutoxytribromirzirconium (Zr (iC ₄ H ₉ ) Br ₃ ), n-butoxytribromirzirconium (Zr ( OC ₄ H ₉ ) Br ₃ ),

trimethoxychloro-hafnium (HfCl (OCH ₃ ) ₃ ), triethoxy-chloro-hafnium (HfCl (OCH ₃ CH ₂ ) ₃ ), triisobutoxy-chloro-hafnium (HfCl (i-OC ₄ H ₉ ) ₃ ), tri-n-butoxy-chloro-hafnium (HfCl (OC ₄ H ₉ ) ₃ ), dimethoxydichloro-hafnium (HfCl ₂ (OCH ₃ ) ₂ ), diethoxydichloro-hafnium (HfCl ₂ (OCH ₃ CH ₂ ) ₂ ), diisobutoxydichloro-hafnium (HfCl ₂ (i-OC ₄ H ₉ ) ₂ ), tri-n-butoxy-chloro-hafnium (HfCl (OC ₄ H ₉ ) ₃ ), methoxy trichloro-hafnium (Hf (OCH ₃ ) Cl ₃ ), ethoxy trichloro-hafnium (Hf (OCH ₃ CH ₂ ) Cl ₃ ), isobutoxy-trichloro-hafnium (Hf (iC ₄ H ₉ ) Cl ₃ ), n-butoxy-trichloro-hafnium (Hf ( OC ₄ H ₉ ) Cl ₃ ),

trimethoxy bromo hafnium (HfBr (OCH ₃ ) ₃ ), triethoxy bromo hafnium (HfBr (OCH ₃ CH ₂ ) ₃ ), triisobutoxy bromo hafnium (HfBr (i-OC ₄ H ₉ ) ₃ ), tri-n-butoxy bromo hafnium (HfBr (OC ₄ H ₉ ) ₃ ), dimethoxy dibromo hafnium (HfBr ₂ (OCH ₃ ) ₂ ), diethoxy dibromo hafnium (HfBr ₂ (OCH ₃ CH ₂ ) ₂ ), diisobutoxy dibromo hafnium (HfBr ₂ (i-OC ₄ H ₉ ) ₂ ), tri-n-butoxy bromo hafnium (HfBr (OC ₄ H ₉ ) ₃ ), methoxytribromafafnium (Hf (OCH ₃ ) Br ₃ ), ethoxytribromafafnium (Hf (OCH ₃ CH ₂ ) Br ₃ ), isobutoxytribromafnium (Hf (iC ₄ H ₉ ) Br ₃ ), n-butoxytribromafafnium (Hf ( OC ₄ H ₉ ) Br ₃ ).

As a Group IVB metal compound, preference is given to a Group IVB metal halide compound such as TiCl ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , HfCl ₄ and HfBr ₄ , for example TiCl ₄ and ZrCl ₄ .

The Group IVB metal compound can be used of the same type, or as a mixture of two or more types in any ratio between them.

When the chemical treatment agent is presented as a liquid at normal temperature, the chemical treatment agent can be used as such. When the chemical treatment agent is presented as a solid at normal temperature, it is preferable to use the specified chemical treatment agent in the form of a solution to facilitate measurement and processing. Of course, in the case where the chemical treatment agent is presented in the form of a liquid at normal temperature, said chemical treatment agent can also be used, if necessary, in the form of a solution, without any restrictions.

When preparing a solution of a chemical treatment agent, there are no restrictions on the solvent used (hereinafter referred to as the “solvent for dissolving the chemical treatment agent”), provided that the solvent is capable of dissolving the chemical treatment agent and does not alter (eg, dissolve) the formed structure of the alkoxymagnesium spherical support carrier.

In particular, as a solvent for dissolving the chemical treatment agent, an example is C _5-12 alkane, cyclic C _5-12 alkane, halogenated C _5-12 alkane and halogenated cyclic C _5-12 alkane, for example, pentane, hexane, heptane, octane , nonane, decane, undecane, dodecane, cyclohexane, cyclopentane, cycloheptane, cyclooctane, chloropentane, chlorhexane, chlorheptane, chloroctane, chlorononane, chlorodecane, chlorordecane, chlorodecane, chlorinated cyclohexane and the like, most preferably pentane, preferably pentane de can

The solvent can be used of the same type or as a mixture of two or more types in any ratio between them.

In addition, there is no limitation on the concentration of the chemical treatment agent in the solution, which can be determined as necessary, as long as it is sufficient for the solution to deliver a given amount of chemical treatment agent for the reaction. In accordance with the foregoing, if the chemical treatment agent is a liquid, it is convenient to use the specified chemical treatment agent as such for processing, although it is also acceptable to convert it into a solution form before use. Typically, the molar concentration of the chemical treatment agent in its solution is, but without limitation, from 0.01 to 1.0 mol / L.

According to the present invention, with respect to the amount of chemical treatment agent used, it is preferable that the molar ratio of the alkoxy magnesium spherical support (Mg based) to the chemical treatment agent (based on Group IVB metal) is 1: 1-30, preferably 1: 2-20 more preferably 1: 4-10.

According to the present invention, an example of a method for carrying out the contacting step can be a method for contacting a nonmetallocene ligand, a chemical treatment agent, and an alkoxymagnesium spherical carrier in the presence of a solvent (hereinafter referred to as the “contacting solvent”).

In accordance with the present invention, in the present description there is no restriction on the solvent used for contacting until the solvent is capable of dissolving the nonmetallocene ligand and chemical treatment agent and does not change (for example, dissolves) the formed support structure of the alkoxy magnesium carrier.

In particular, an example of a contacting solvent may be C _5-12 alkane, cyclic C _5-12 alkane, halogenated C _5-12 alkane and halogenated cyclic C _5-12 alkane, for example, pentane, hexane, heptane, octane, nonane, decane Undecane, Dodecane, Cyclohexane, Cyclopentane, Cycloheptane, Cyclooctane, Chloropentane, Chlorhexane, Chlorheptane, Chloroctane, Chlorononane, Chlorodecane, Chlorodecane, Chlorodecane, Chlorinated Cyclohexane and the like, most preferably Pentane, Hexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, Dexane, DeCANe

The solvent for contacting can be used of the same type or as a mixture of two or more types in any ratio between them.

In accordance with the present invention, since a certain amount of solvent for contacting will be used, it is preferred that the ratio of alkoxy magnesium spherical support to solvent for contacting is 1 mol: 75-8000 ml, preferably 1 mol: 150-6000 ml, more preferably 1 mol: 200 -4000 ml.

In accordance with the present invention, there are no restrictions on the contacting sequence of the non-metallocene ligand, chemical treatment agent and alkoxymagnesium spherical carrier, an example is the simultaneous contacting of three or alternating contacting in any sequence.

According to a preferred embodiment of the present invention, in the presence of a contacting solvent, the nonmetallocene ligand comes into contact with an alkoxymagnesium spherical carrier (hereinafter referred to as the “first contacting step” in the present invention), and then a chemical treatment agent is added for further contacting (hereinafter in the present description referred to as the "second contacting step").

As a method for carrying out the first contacting step, the following two embodiments can be exemplified.

According to a first embodiment, the nonmetallocene ligand is first dissolved in a contacting solvent to form a solution. Dissolution can be carried out, as a rule, at normal temperature for the time necessary for sufficient dissolution of the non-metallocene ligand. During dissolution of the non-metallocene ligand, stirring can be used if necessary (for example, at a stirring speed of 100 to 1000 rpm). Then, with stirring (for example, at a stirring speed of 100 to 1000 rpm), an alkoxy magnesium spherical carrier is introduced into the solution thus obtained, and stirring (for example, at a stirring speed of 100 to 1000 rpm) continues at a temperature of 50 to 150 ° C (preferably 60 to 130 ° C) until a suspension is formed. There is no restriction on the duration of mixing until a homogeneous suspension can be obtained, this can be, for example, from 5 to 120 minutes, preferably from 15 to 60 minutes.

Alternatively, in accordance with the second embodiment, with stirring (for example, at a stirring speed of from 100 to 1000 rpm), at a temperature of from 50 to 150 ° C (preferably from 60 to 130 ° C), an alkoxy magnesium spherical carrier can be introduced into the solvent for contacting, or the solvent for contacting can be introduced into an alkoxymagnesium spherical carrier, at the same time or then a nonmetallocene ligand is introduced, and stirring (for example, at a stirring speed of 100 to 1000 rpm) continues while same temperature until a suspension forms. There is no restriction on the duration of mixing until a homogeneous suspension can be obtained, this can be, for example, from 5 to 120 minutes, preferably from 15 to 60 minutes.

After receiving the suspension, as described above, the suspension comes into contact with a chemical treatment agent (namely, the second stage of contacting), and then receive supported on a non-metallocene catalyst of the invention.

As a method for carrying out the second contacting step, an example is that, with stirring (for example, at a stirring speed of 100 to 1000 rpm), at a temperature of 50 to 150 ° C (preferably 80 to 130 ° C), a chemical treatment agent or a chemical treatment agent solution, is introduced (preferably continuously) into the suspension. Administration lasts from 0.5 to 8 hours, preferably from 1 to 6 hours, most preferably from 2 to 5 hours. After completion of this introduction, stirring is continued at a temperature of from 50 to 150 ° C (preferably from 80 to 150 ° C) for 0.1 to 24 hours, preferably 1 to 6 hours, so as to obtain a reaction mixture.

After completion of the second contacting step, the reaction mixture is filtered, washed and dried so as to obtain a non-metallocene catalyst of the invention supported on a carrier.

In accordance with the present invention, filtering, washing and drying can be carried out in a generally known manner. If necessary, washing can be carried out, as a rule, from 1 to 8 times, preferably from 2 to 6 times, most preferably from 2 to 4 times. In this case, the solvent for washing may be the same as the solvent for contacting.

Drying can be carried out in accordance with standard technology, for example, drying under an inert gas atmosphere, drying under vacuum or drying under vacuum under heating, preferably drying under inert gas or drying under vacuum under heating, most preferably drying under vacuum at heating up. Drying is usually carried out at a temperature in the range from normal temperature to 140 ° C, lasting, as a rule, from 2 to 20 hours, but not limited to.

It is known that any of the above methods and steps are preferably carried out essentially under anhydrous and oxygen-free conditions. Essentially anhydrous and oxygen-free conditions imply that the content of water and oxygen in the system in question is constantly monitored at less than 100 ppm. Further, the supported non-metallocene catalyst of the invention, after preparation, is usually stored in an inert gas atmosphere (for example, nitrogen gas, gaseous Ar or gaseous He) in an airtight condition under slightly elevated pressure until use.

In one embodiment, the invention relates to a supported non-metallocene catalyst prepared in accordance with the above method, also referred to as a supported non-metallocene catalyst for olefin polymerization.

In yet another embodiment, the invention relates to an olefin homopolymerization / copolymerization process, wherein a non-metallocene supported catalyst of the invention is used as a catalyst for the polymerization of olefin, homopolymerization or copolymerization of olefin (s) and produce a polyolefin as a product.

With regard to the method of homopolymerization / copolymerization of an olefin according to the invention, one can directly turn to the prior art for any substantial materials or information that has not been described in detail and specifically hereinafter, for example, about a polymerization reactor, the amount of olefin (olefins), the method of introduction catalyst or olefin, eliminating the need for a description of this in detail in the present description below.

According to the presented olefin homopolymerization / copolymerization method, a non-metallocene catalyst of the invention supported on a carrier is used as the main catalyst, and one or more selected from the group consisting of aluminoxane, alkylaluminum, halogenated alkylaluminum, fluoroborane, boralkyl and ammonium salt of boralkyl are used as a cocatalyst for homopolymerization or copolymerization of an olefin.

As a method for adding a basic catalyst and cocatalyst to the polymerization system, an example is a method in which the main catalyst is added before the cocatalyst or vice versa, or the main catalyst and cocatalyst are brought into contact with each other by mixing and then added together or added separately, but simultaneously . An example of how to add the main catalyst and cocatalyst separately can be the situation when the main catalyst and cocatalyst are added one after another to the same feed line or to multi-wire feed lines. In the case where the main catalyst and cocatalyst are introduced separately, but at the same time, multi-channel feed lines are needed. For continuous polymerization, a method of simultaneously and continuously adding raw materials to multi-channel feed lines is preferred, while for periodic polymerization, a method of mixing the main catalyst and cocatalyst with each other and then adding them together to the same feed line, or adding to the line, is preferred supplying the cocatalyst feed and then adding the main catalyst to the same feed line.

There are no restrictions on how to homopolymerize / copolymerize the olefin, and any standard techniques known to those skilled in the art can be used, for example, a slurry method, a tank method or a gas phase method, preferably a slurry method.

In accordance with the present invention, an example of an olefin used is a C ₂ -C ₁₀ monoolefin, diolefin, cyclic olefin and other ethylenically unsaturated compounds.

In particular, an example of a C ₂ -C ₁₀ monoolefin is ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-undecene, 1-dodecene and styrene. An example of a cyclic olefin is 1-cyclopentene and norbornene. An example of a diolefin is 1,4-butadiene, 2,5-pentadiene, 1,6-hexadiene, norbornadiene and 1,7-octadiene. An example of another ethylenically unsaturated compound is vinyl acetate and (meth) acrylate.

In accordance with the present invention, homopolymerization or copolymerization can be carried out in a period of time, usually from 1 to 15 hours, preferably from 2 to 6 hours, more preferably from 2 to 4 hours, but not limited to.

In accordance with the present invention, homopolymerization refers to the polymerization of one type of olefin, copolymerization refers to the polymerization between two or more of the above olefins.

In accordance with the present invention, the cocatalyst is selected from the group consisting of aluminoxane, alkylaluminum, halogenated alkylaluminum, fluoroborane, boralkyl and the ammonium salt of boralkyl, for example, aluminoxane and alkylaluminium.

An example of an aluminoxane is a linear aluminoxane ((R) (R) Al- (Al (R) -O) _n -O-Al (R) (R)) having the following formula (I-1) and a cyclic aluminoxane (- ( Al (R) —O—) _{n + 2} -) having the following formula (II-1).

where R are identical or different from each other, preferably identical to each other, and each is independently selected from the group consisting of C ₁ -C ₈ alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl, n is an integer from 1 to 50 preferably from 10 to 30.

In particular, aluminoxane may preferably be selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane, preferably methylaluminoxane (MAO) and isobutylaluminoxane (IBAO), most preferably methylaluminoxane (MAO).

Aluminoxane can be used of the same type or as a mixture of two or more types in any ratio between them.

An example of an aluminum alkyl is a compound having the following general formula (III-1):

Al (R) ₃ (III-1)

where R are identical or different from each other, preferably identical to each other, and each independently selected from the group consisting of C ₁ -C ₈ alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl.

In particular, alkylaluminum may be selected from the group consisting of trimethylaluminum (Al (CH ₃ ) ₃ ), triethylaluminum (Al (CH ₃ CH ₂ ) ₃ ), tripropylaluminum (Al (C ₃ H ₇ ) ₃ ), triisobutylaluminum (Al (iC ₄ H ₉ ) ₃ ), tri-n-butylaluminum (Al (C ₄ H ₉ ) ₃ ), triisoamylaluminum (Al (iC ₅ H ₁₁ ) ₃ ), tri-n-amylaluminum (Al (C ₅ H ₁₁ ) ₃ ) , trihexyl aluminum (Al (C ₆ H ₁₃ ) ₃ ), triisohexyl aluminum (Al (iC ₆ H ₁₃ ) ₃ ), diethyl methyl aluminum (Al (CH ₃ ) (CH ₃ CH ₂ ) ₂ ) and ethyldimethyl aluminum (Al (CH ₃ CH ₂ ) (CH _{3) 2),} and the like, where preference is given trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, more pref sim ilar triethylaluminum and triisobutylaluminum, triethylaluminum is most preferred.

Alkyl aluminum can be used of the same type or as a mixture of two or more types in any ratio between them.

An example of a halogenated alkylaluminum is a compound having the following general formula:

Al (R) _n X _3-n

where R are identical or different from each other, preferably identical to each other, and each independently selected from the group consisting of C ₁ -C ₈ alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl, X is halogen, preferably Cl, n represents 1 or 2.

In particular, halogenated alkylaluminum may be selected from the group consisting of monochlorodimethylaluminum (Al (CH ₃ ) ₂ Cl), dichloromethylaluminum (Al (CH ₃ ) Cl ₂ )), monochlorodiethylaluminum (Al (CH ₃ CH ₂ ) ₂ Cl), dichloroethylaluminum ( Al (CH ₃ CH ₂ ) Cl ₂ ), monochlorodipropyl aluminum (Al (C ₃ H ₇ ) ₂ Cl), dichloropropyl aluminum (Al (C ₃ H ₇ ) Cl ₂ )), monochloro-di-n-butyl aluminum (Al (C ₄ H ₉ ) ₂ Cl), dichloro-n-butylaluminum (Al (C ₄ H ₉ ) Cl ₂ ), monochlorodiisobutylaluminum (Al (iC ₄ H ₉ ) ₂ Cl), dichloroisobutylaluminum (Al (iC ₄ H ₉ ) Cl ₂ ), monochloro-di-n-pentylaluminum (Al (C ₅ H ₁₁ ) ₂ Cl), dichloro-n-pentylaluminium (Al (C ₅ H ₁₁ ) Cl ₂ ), monochlorodiisopentyl aluminum (Al (iC ₅ H ₁₁ ) ₂ Cl), dichloroisopentylaluminum (Al (iC ₅ H ₁₁ ) Cl ₂ ), monochloro-di-n-hexylaluminium (Al (C ₆ H ₁₃ ) ₂ Cl), dichloro-n-hexylaluminium (Al (C ₆ H ₁₃ ) Cl ₂ ), monochloro-diisohexyl aluminum (Al (iC ₆ H ₁₃ ) ₂ Cl), dichloroisohexyl aluminum (Al (iC ₆ H ₁₃ ) Cl ₂ ), monochloromethylethyl aluminum (Al (CH ₃ ) (CH ₂ CH ₃ ) Cl), monochloromethylpropylaluminum (Al (CH ₃ ) (C ₃ H ₇ ) Cl), monochloromethyl-n-butylaluminum (Al (CH ₃ ) (C ₄ H ₉ ) Cl), monochloromethylisobutylaluminum (Al (CH ₃ ) ( iC ₄ H ₉ ) Cl), monochloroethyl propylaluminium (Al (CH ₂ CH ₃ ) (C ₃ H ₇ ) Cl), monochloroethyl n-butylaluminum (AlCH ₂ CH ₃ ) (C ₄ H ₉ ) Cl), monochloromethyl isobutylaluminum (AlCH ₂ CH ₃₎ (iC ₄ H ₉₎ Cl), Preferred specifically monochlorodiethylaluminum, dichloroethylaluminum, monochloro-di-n-butylaluminum, dichloro-n-butylaluminum, monochlorodiisobutylaluminum, dichloroisobutylaluminum, monochloro-di-n-hexylaluminum, dichloro-n-hexyl-aluminum, preferably dichloro-n-hexyl-aluminum, preferably most preferably monochlorodiethylaluminum.

Halogenated alkylaluminum can be used of the same type or as a mixture of two or more types in any ratio between them.

An example of fluoroborane, alkylboron and ammonium salt of alkylboron are those commonly used in the art, but without any limitation.

In addition, in accordance with the present invention, the cocatalyst, if necessary, can be used of the same type or as a mixture of two or more types of the above cocatalysts in any ratio between them, but without any restrictions.

In accordance with the present invention, depending on how the olefin is homopolymerized / copolymerized (for example, by suspension polymerization), a polymerization solvent may be involved.

As a solvent for the polymerization, a commonly used solvent for homopolymerization / copolymerization of olefin can be used, but without any limitation.

As a solvent for the polymerization, C _4-10 alkane (e.g., butane, pentane, hexane, heptane, octane, nonane, or decane), halogenated C _1-10 alkane (e.g. dichloromethane), cyclic C _6-12 alkane ( for example, cyclohexane, cycloheptane, cyclooctane, cyclononan or cyclodecane), an aromatic C _6-20 hydrocarbon (e.g. toluene or xylon), and the like. Hexane, pentane, heptane or cyclohexane are preferred, with hexane being most preferred.

The polymerization solvent can be used of the same type or as a mixture of two or more types in any ratio between them.

In accordance with the present invention, the total polymerization pressure at which olefin homopolymerization / copolymerization occurs is usually from 0.1 to 10 MPa, preferably between 0.1 and 4 MPa, most preferably between 0.5 and 1.5 MPa, but without any restrictions at the same time. In accordance with the present invention, the polymerization temperature at which olefin homopolymerization / copolymerization occurs is usually from 10 ° C to 200 ° C, preferably from 40 ° C to 100 ° C, more preferably from 80 ° C to 95 ° C, but without any limitation.

In addition, in accordance with the present invention, olefin homopolymerization / copolymerization can be carried out in the presence or absence of hydrogen gas. If present, the partial pressure of gaseous hydrogen can, as a rule, be from 0.01 to 1 MPa, preferably from 0.05 to 0.2 MPa, but without any limitation.

According to the olefin homopolymerization / copolymerization method of the present invention, the molar ratio of the cocatalyst (based on Al or B) to the supported non-metallocene catalyst (based on the central metal atom M) of the invention is usually from 1 to 1000: 1, preferably from 10 up to 500: 1, more preferably from 15 to 300: 1, but without any limitation.

In accordance with the present invention, the polyolefin obtained in accordance with the presented olefin homopolymerization / copolymerization method is characterized by excellent particle morphology, high bulk density and specific surface area, variant pore structure, the desired particle size distribution and molecular weight distribution, can be easily chlorinated and therefore, it can be used directly to produce a chlorinated polyolefin.

In accordance with the present invention, homopolymerization of ethylene or copolymerization of ethylene with at least one alpha olefin (s) (hereinafter referred to as “comonomer”) selected from C ₃ to C ₁₂ alpha olefins is further preferred. As a C ₃ -C ₁₂ alpha olefin, a C ₃ -C ₈ alpha olefin is more preferred. An example of an alpha olefin used herein is propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-dodecene or 4-methyl-1-hexene, preferably propylene, 1-butene, 1-hexene, 1-octene or 4-methyl-1-pentene, more preferably propylene, 1-hexene, 1-octene or 4-methyl-1-pentene. The alpha olefin can be used of the same type or as a mixture of one or more types.

In accordance with the present invention, if present, the comonomer can be used in an amount of from 0.5 to 10 g per 1 mg of the main catalyst, preferably from 1 to 5 g per 1 mg of the main catalyst.

In accordance with the present invention, when the above homopolymerization of ethylene or copolymerization of ethylene with a comonomer is carried out, a suspension polymerization procedure is preferred under conditions of a total polymerization pressure of from 0.2 to 2.0 MPa, preferably from 0.5 to 1.5 MPa, at the ratio of the partial pressure of gaseous hydrogen to ethylene is 0.01-0.2: 1, preferably 0.02-0.1: 1, most preferably 0.03-0.08: 1, and the polymerization temperature is from 60 to 100 ° C, preferably 70 to 95 ° C, more preferably 80 to 90 C.

In accordance with the present invention, polyethylene obtained in accordance with the above homopolymerization of ethylene or copolymerization of ethylene with a comonomer has a repeating unit derived from ethylene, and optionally a repeating unit derived from at least one alpha olefin (s), where, relative the total mass of 100 wt.% this polyethylene, the content of the repeating unit derived from ethylene is from 95 to 100 wt.%, and the content of the repeating unit obtained from at least one alpha olefin (- s), is from 0 to 5 wt.%.

In accordance with the present invention, the polyethylene has a bulk density of from 0.33 to 0.50 g / cm ³ , preferably from 0.38 to 0.46 g / cm ³ , more preferably from 0.40 to 0.44 g / cm ³ .

In accordance with the present invention, polyethylene has an oligomer content of less than 2 g / l.

In accordance with the present invention, the polyethylene has a fine powder content (less than 75 microns) of less than 5 wt.%.

In accordance with the present invention, polyethylene has a melt index (at 190 ° C. and a load of 2.16 kg) from 0.02 to 5 g / 10 min.

In accordance with the present invention, the polyethylene has a molecular weight distribution of Mw / Mn from 2.5 to 20, preferably from 4 to 10.

In accordance with the present invention, the polyethylene has a density of from 0.94 to 0.96 g / cm ³ .

In accordance with the present invention, polyethylene has an average particle size of from 200 to 400 microns.

In accordance with the present invention, the polyethylene has a specific surface area of from 0.2 to 3.0 m ² / g, preferably from 1.0 to 3.0 m ² / g, more preferably from 1.5 to 3.0 m ² / g.

In accordance with the present invention, the polyethylene has a pore volume of from 0.001 to 0.15 cm ³ / g, preferably from 0.01 to 0.15 cm ³ / g, more preferably from 0.05 to 0.12 cm ³ / g.

In accordance with the present invention, the polyethylene has a pore size of from 10 to 80 nm, preferably from 20 to 70 nm, more preferably from 20 to 60 nm.

In accordance with the present invention, the aforementioned polyolefin or polyethylene can be directly chlorinated by any chlorination method known in the art as a starting material to produce the corresponding chlorinated polyolefin, in particular chlorinated polyethylene. An example of a chlorination method is a solvent chlorination method, a suspension chlorination method, a solid phase chlorination method, a suspension chlorination method is preferred. An example of a method for chlorinating in suspension is a method for chlorinating in suspension in an acid phase, a method for chlorinating in suspension in an aqueous phase, or a method for chlorinating in suspension in a solution. These methods can be carried out by any method known in the art, a detailed description is not included.

In accordance with the present invention, chlorination can result in a chlorinated polyolefin (in particular, chlorinated polyethylene) having a chlorine content of 30-70 wt.%. A chlorinated polyolefin (in particular polyethylene) is characterized by a relatively low Mooney viscosity (e.g., 60 or less) and relatively high tensile strength (e.g., 10 MPa or more).

Examples

The present invention is further illustrated by the following examples, but without limitation.

The bulk density of the polymer was evaluated in accordance with the state standard of China GB 1636-79 (units: g / cm ³ ).

The particle size distribution was evaluated using a laser particle size analyzer (model LS230, Beckman Coulter company, USA), with a size measurement range from 0.04 to 2000.00 μm. The content of fine powder (less than 75 microns) of the polymer was obtained automatically from the analyzer.

The specific surface area, pore volume, and pore size of the polymer were measured using the five control point method on a physical absorption analyzer (model ASAP2010, Micromeritics company, USA) with nitrogen gas as an adsorption medium and at a temperature of liquid nitrogen (77 K).

The oligomer content of the polymer was prepared as follows.

About 10 g of polymer powder was weighed as a sample and placed in a paper container with a known weight. Then, the sample and the paper container were together placed in an extractor containing n-heptane, and then the extractor was placed in a thermostatic oil bath. The extraction was carried out at 80 ± 2 ° C for 6 hours. After extraction was completed, a paper container with any polymer residue in it was placed in a vacuum oven and dried at 90 ° C until the weight became constant, and then placed in a silica gel drying chamber, cooled in it for 30 minutes and then weighed ( accurate to 0.1 mg). The oligomer content was calculated in accordance with the following formula.

In this formula, X represents the oligomer content,%; m ₁ represents the mass of the sample before extraction, g; m ₂ represents the mass of the sample after extraction and drying, g

The measurement was repeated twice, and the oligomer content in the polymer was finally presented as the average of these two measurements with a deviation of not more than 5%.

The polymer melt index (at 190 ° C. and a load of 2.16 kg) was measured in accordance with ASTM D 1238.

The density of the polymer was measured using the density gradient method in accordance with the state standard of China GB / T1033.2-2010.

The content of Group IVB metal (e.g., Ti) and the content of the Mg element in the non-metallocene catalyst supported on the carrier were determined by ICP-AES (atomic emission spectrometry with inductively coupled plasma), while the content of the non-metallocene ligand was determined by elemental analysis.

The polymerization activity of the catalyst was calculated as follows.

Upon completion of the polymerization, the polymer product in the reactor was filtered and dried, and then weighed to obtain its mass (by weight). Then, the polymerization activity of the catalyst was expressed as the value obtained by dividing the mass of the polymer product by the mass (by weight) of the nonmetallocene catalyst supported on the carrier (units: kg of polymer per 1 g of CAT).

The molecular weights Mw, Mn and molecular weight distribution (Mw / Mn) of the polymer were determined at a test temperature of 150 ° C. using a GPC V2000 gel permeation chromatography apparatus (manufactured by WATERS Co., USA), using 1.2 as a solvent. 4-trichlorobenzene.

A sample of chlorinated polyethylene was obtained in accordance with the state standard of China HG / T2704-2002.

The chlorine content of chlorinated polyethylene was measured in accordance with Chinese State Standard GB / T7139-2002 (Method B).

The Mooney viscosity of chlorinated polyethylene was measured in accordance with Chinese State Standard GB / T1232.1-2000, with a preheat time of 1 min, a rotation time of 4 min, and a test temperature of 125 ° C.

The tensile strength of chlorinated polyethylene was measured in accordance with Chinese State Standard GB / T528-2009 using a Type I dumbbell cutter.

Example I

Example I-1

The alkoxy magnesium spherical support was a diethoxy magnesium spherical support (having a sphericity of 1.42, bulk density of 0.32 g / cm ³ and an average particle size of 420 μm), the contacting solvent was n-octane, the chemical treatment agent was titanium tetrachloride, nonmetallocene the ligand has a structure

A diethoxy magnesium spherical support (5 g) and a nonmetallocene ligand were weighed, n-heptane was added to them and stirred at 300 rpm for 30 min, heated to 90 ° C to obtain a homogeneous dispersion. Then titanium tetrachloride was added dropwise to the dispersion over 2 hours, after completion of the addition, the reaction was continued with stirring at 90 ° C for 6 hours, filtered, washed with hexane 3 times (60 ml each time) and finally dried in vacuum at normal temperature to obtain supported on a non-metallocene catalyst.

In this example, the ratio of diethoxy magnesium spherical support to n-heptane was 1 mol: 1000 ml, the molar ratio of diethoxy magnesium spherical support to a nonmetallocene ligand was 1: 0.01, the molar ratio of diethoxy magnesium spherical support to titanium tetrachloride was 1: 2.1.

The nonmetallocene catalyst thus obtained supported on a carrier is called CAT-1.

Example I-2

Essentially the same as in Example I-1, except for the following changes:

растворитель для контактирования был изменен на гептан, агент химической обработки был изменен на тетрахлорид циркония (ZrCl₄), температура реакции была изменена на 85°C, по окончании добавления реакцию продолжали при перемешивании при 85°C в течение 10 часов.Non-metallocene carrier has been changed to

the contacting solvent was changed to heptane, the chemical treatment agent was changed to zirconium tetrachloride (ZrCl ₄ ), the reaction temperature was changed to 85 ° C, after completion of the addition, the reaction was continued with stirring at 85 ° C for 10 hours.

In this example, the ratio of the alkoxy magnesium spherical carrier to the solvent for contacting was 1 mol: 1500 ml, the molar ratio of the alkoxy magnesium spherical carrier to the nonmetallocene ligand was 1: 0.015, the molar ratio of the alkoxy magnesium spherical carrier to the chemical treatment agent was 1: 3.

The nonmetallocene catalyst thus obtained supported on a carrier is called CAT-2.

Example I-3

Essentially the same as in Example I-1, except for the following changes:

, растворитель для контактирования был изменен на этилбензол, температура реакции была изменена на 95°C, по окончании добавления реакцию продолжали при перемешивании при 95°C в течение 4 часов.The alkoxy-magnesium spherical support was changed to dipropoxy-magnesium spherical support (Mg (OPr) ₂ ) (having a sphericity of 1.83, bulk density of 0.40 g / cm ³ and an average particle size of 530 μm), the non-metallocene support was

, the contacting solvent was changed to ethylbenzene, the reaction temperature was changed to 95 ° C, and upon completion of the addition, the reaction was continued with stirring at 95 ° C for 4 hours.

In this example, the ratio of the alkoxy magnesium spherical support to the solvent for contacting was 1 mol: 2000 ml, the molar ratio of the alkoxy magnesium spherical support to the nonmetallocene ligand was 1: 0.02, and the molar ratio of the alkoxy magnesium spherical support to the chemical treatment agent was 1: 5.

The nonmetallocene catalyst thus obtained supported on a carrier is called CAT-3.

Example I-4

Essentially the same as in Example I-1, except for the following changes:

растворитель для контактирования был изменен на декан, агентом химической обработки был этокситрихлортитан (Ti(OCH₂CH₃)Cl₃), температура реакции была изменена на 100°C, по окончании добавления реакцию продолжали при перемешивании при 100°C в течение 3 часов.The alkoxymagnesium spherical support was changed to dibutoximagnesium spherical support (Mg (OC ₄ H ₉ ) ₂ ) (having a sphericity of 2.07, bulk density of 0.62 g / cm ³ and an average particle size of 630 μm), the nonmetallocene ligand was

the contacting solvent was changed to decane, the chemical treatment agent was ethoxytrichlorotitan (Ti (OCH ₂ CH ₃ ) Cl ₃ ), the reaction temperature was changed to 100 ° C, and after the addition was complete, the reaction was continued with stirring at 100 ° C for 3 hours.

In this example, the ratio of the alkoxy magnesium spherical support to the solvent for contacting was 1 mol: 3500 ml, the molar ratio of the alkoxy magnesium spherical support to the nonmetallocene ligand was 1: 0.02, the molar ratio of the alkoxy magnesium spherical support to the chemical treatment agent was 1:10.

The nonmetallocene catalyst thus obtained supported on a carrier is called CAT-4.

Example I-5

Essentially the same as in Example I-1, except for the following changes:

растворитель для контактирования был изменен на декан, агентом химической обработки был этокситрихлортитан (Ti(OCH₂CH₃)Cl₃), температура реакции была изменена на 110°C, по окончании добавления реакцию продолжали при перемешивании при 110°C в течение 8 часов.The alkoxy magnesium spherical support was changed to dimethoxy magnesium spherical support (Mg (OCH ₃ ) ₂ ) (having a sphericity of 2.2, a bulk density of 0.25 g / cm ³ and an average particle size of 275 μm), the nonmetallocene ligand was

the contacting solvent was changed to decane, the chemical treatment agent was ethoxytrichlorotitan (Ti (OCH ₂ CH ₃ ) Cl ₃ ), the reaction temperature was changed to 110 ° C, and after the addition was complete, the reaction was continued with stirring at 110 ° C for 8 hours.

In this example, the ratio of the alkoxy magnesium spherical support to the solvent for contacting was 1 mol: 4000 ml, the molar ratio of the alkoxy magnesium spherical support to the nonmetallocene ligand was 1: 0.03, the molar ratio of the alkoxy magnesium spherical support to the chemical treatment agent was 1:14.

The nonmetallocene catalyst thus obtained supported on a carrier is called CAT-5.

Example I-6

Essentially the same as in Example I-1, except for the following changes:

растворитель для контактирования был изменен на 2-этилоктан, агентом химической обработки был этилтрихлортитан (Ti(CH₂CH₃)Cl₃), температура реакции была изменена на 120°C, по окончании добавления реакцию продолжали при перемешивании при 120^oC в течение 16 часов.The nonmetallocene ligand was

the contacting solvent was changed to 2-ethylloctane, the chemical processing agent was ethyl trichlorotitanium (Ti (CH ₂ CH ₃ ) Cl ₃ ), the reaction temperature was changed to 120 ° C, and after the addition was complete, the reaction was continued with stirring at 120 ^° C for 16 hours.

In this example, the ratio of the alkoxy magnesium spherical support to the solvent for contacting was 1 mol: 6000 ml, the molar ratio of the alkoxy magnesium spherical support to the nonmetallocene ligand was 1: 0.05, and the molar ratio of the alkoxy magnesium spherical support to the chemical treatment agent was 1: 8.

The nonmetallocene catalyst thus obtained supported on a carrier is called CAT-6.

Example I-7

Essentially the same as in Example I-1, except for the following changes:

, растворитель для контактирования был изменен на метилэтилбензол, агент химической обработки был изменен на метокситрибромтитан (Ti(OCH₃)Br₃), температура реакции была изменена на 120°C, по окончании добавления реакцию продолжали при перемешивании при 120°C в течение 25 часов.The alkoxy magnesium spherical support was changed to ethoxypropoxy magnesium spherical support (Mg (OEt) (OPr)) (having a sphericity of 1.3, a bulk density of 0.52 g / cm ³ and an average particle size of 350 μm), the nonmetallocene ligand was

, the contacting solvent was changed to methylethylbenzene, the chemical treatment agent was changed to methoxytribromtitanium (Ti (OCH ₃ ) Br ₃ ), the reaction temperature was changed to 120 ° C, after completion of the addition, the reaction was continued with stirring at 120 ° C for 25 hours .

In this example, the ratio of the alkoxy magnesium spherical carrier to the solvent for contacting was 1 mol: 8000 ml, the molar ratio of the alkoxy magnesium spherical carrier to the nonmetallocene ligand was 1: 0.06, the molar ratio of the alkoxy magnesium spherical carrier to the chemical treatment agent was 1: 3.5.

The nonmetallocene catalyst thus obtained supported on a carrier is called CAT-7.

Comparative Example I-A

Essentially the same as in Example I-1, except for the following changes:

A nonmetallocene ligand was not added.

The catalyst thus obtained is called CAT-A.

Comparative Example I-B

Essentially the same as in Example I-1, except for the following changes:

The molar ratio of alkoxymagnesium spherical carrier to non-metallocene ligand was changed to 1: 0.02.

The catalyst thus obtained is called CAT-B.

Comparative Example I-C

Essentially the same as in Example I-1, except for the following changes:

The molar ratio of alkoxymagnesium spherical carrier to non-metallocene ligand was changed to 1: 0.04.

The catalyst thus obtained is called CAT-C.

Comparative Example I-D

Essentially the same as in Example I-1, except for the following changes:

The molar ratio of alkoxymagnesium spherical support to chemical treatment agent was changed to 1: 4.

The catalyst thus obtained is called CAT-D.

Comparative Example I-E

Essentially the same as in Example I-1, except for the following changes:

The reaction temperature was changed to 100 ° C.

The catalyst thus obtained is called CAT-E.

Comparative Example I-F

The magnesium compound was anhydrous MgCl ₂ , the solvent for dissolving the magnesium compound and the nonmetallocene ligand was tetrahydrofuran, and titanium tetrachloride was the chemical treatment agent. Nonmetallocene ligand has the structure

Anhydrous MgCl ₂ (5 g) and a nonmetallocene ligand were weighed, tetrahydrofuran was added to them at normal temperature for complete dissolution, after stirring for 2 hours, hexane was added as a precipitating agent, filtered, washed with hexane 2 times (60 ml each time), dried with uniform heating at 60 ° C under vacuum to obtain a modified carrier.

60 ml of hexane was added to the modified carrier, then titanium tetrachloride was added dropwise with stirring over 30 minutes, after which the reaction was continued with stirring at 60 ° C for 4 hours, filtered, washed with hexane 2 times (60 ml each time ), and finally dried in vacuum at normal temperature to obtain a non-metallocene catalyst supported on a carrier.

In this example, the ratio of MgCl ₂ to tetrahydrofuran was 1 mol: 210 ml, the molar ratio of MgCl ₂ to non-metallocene ligand was 1: 0.01, the ratio by volume of precipitating agent to tetrahydrofuran was 1: 1, the molar ratio of MgCl ₂ to titanium tetrachloride was 1 : 0.15.

The nonmetallocene catalyst thus obtained supported on a carrier is called CAT-F.

Comparative Example I-G

Essentially the same as in Example I-1, except for the following changes:

растворяли в дихлорметане, и затем добавляли туда твердое вещество, полученное в Примере I-1, реакцию продолжали при перемешивании при нормальной температуре в течение 2 часов, а затем высушивали в вакууме для получения катализатора.A nonmetallocene ligand was not added during preparation. Preferably, the non-metallocene complex having the structure

dissolved in dichloromethane, and then the solid obtained in Example I-1 was added thereto, the reaction was continued with stirring at normal temperature for 2 hours, and then dried in vacuum to obtain a catalyst.

In this example, the molar ratio of diethoxy magnesium spherical carrier to non-metallocene complex was 1: 0.01, the amount of dichloromethane used was 5 ml.

The nonmetallocene catalyst thus obtained supported on a carrier is called CAT-G.

Example I-8 (Application Example)

The catalysts CAT-1 to CAT-7 and CAT-A to CAT-G obtained in the above Examples I-1 to I-7 and Comparative Examples IA to IF were used for homopolymerization or copolymerization of ethylene under the following conditions in accordance with with the following methods, respectively.

Homopolymerization: autoclave for polymerization (5 L), suspension polymerization method, hexane (2.5 L) as solvent, total polymerization pressure 0.8 MPa, polymerization temperature 85 ° C, partial pressure of hydrogen gas 0.2 MPa, polymerization time 2 hours.

In particular, 2.5 L of hexane was added to the autoclave for polymerization, and the stirrer was started. Then, a mixture of a test catalyst (50 mg) and a cocatalyst (triethyl aluminum) was added, where the molar ratio of the cocatalyst (based on Al) to the test catalyst (based on the central metal atom) was 100: 1. Then, hydrogen gas was supplied there to 0.2 MPa, and ethylene was continuously fed at the end to maintain the total polymerization pressure constant at 0.8 MPa. Upon completion of the polymerization, the inner contents of the autoclave were released into the surrounding atmosphere, and the resulting polymer product was taken out of the autoclave and weighed (mass) after drying. Details of the polymerization reaction and polymerization characteristics are presented in the following Table I-1.

Copolymerization: autoclave for polymerization (5 L), suspension polymerization method, hexane (2.5 L) as solvent, total polymerization pressure 0.8 MPa, polymerization temperature 85 ° C, hydrogen gas partial pressure 0.2 MPa, polymerization time 2 hours.

In particular, 2.5 L of hexane was added to the autoclave for polymerization, and the stirrer was started. Then, a mixture of a test catalyst (50 mg) and a cocatalyst (triethyl aluminum) was added, where the molar ratio of the cocatalyst (based on Al) to the test catalyst (based on the central metal atom) was 100: 1. Then, butene-1 (10 g) was added thereto as a comonomer all at once, and then hydrogen gas was supplied up to 0.2 MPa, and ethylene was continuously fed at the end to keep the total polymerization pressure constant 0.8 MPa. Upon completion of the polymerization, the inner contents of the autoclave were released into the surrounding atmosphere, and the resulting polymer product was taken out of the autoclave and weighed (mass) after drying. Details of the polymerization reaction and polymerization characteristics are presented in the following Table I-1.

Table I-1
Olefin polymerization results obtained with non-metallocene catalysts supported on a carrier Experiment No. Catalyst No. Type of Catalyst Activity (kg PE / g Cat) Bulk density (g / cm ³ ) Molecular weight distribution Specific Surface Area (m ² g ^-1 ) Pore Size (nm) one CAT-1 Homopolymerization 6.2 0.38 3.62 1,57 47.43 2 CAT-1 Copolymerization 7.1 0.38 3.85 7.46 50.87 3 CAT-2 Homopolymerization 7.4 0.37 3,58 1.49 48.32 four CAT-2 Copolymerization 9,4 0.37 3.74 1.84 48.26 5 CAT-3 Homopolymerization 8.7 0.37 3.63 1.77 49.35 6 CAT-3 Copolymerization 11.3 0.39 3.83 1.92 52.06 7 CAT-4 Copolymerization 25,2 0.39 5.21 - - 8 CAT-5 Copolymerization 17.8 0.36 4.62 - -

9 CAT-6 Copolymerization 12.5 0.37 12.55 - - 10 CAT-7 Copolymerization 5,4 0.36 21,42 - - eleven CAT-A Copolymerization 6.8 0.38 4.65 1.32 47.26 12 CAT-B Copolymerization 7.7 0.40 3.73 1.66 51.74 13 CAT-C Copolymerization 8.2 0.39 3.57 1.65 51.37 fourteen CAT-D Copolymerization 12.5 0.41 4.20 1,62 46.29 fifteen CAT-E Copolymerization 8.0 0.37 4.37 1.73 47.92 16 CAT-F Copolymerization 21.1 0.32 3.02 0.48 28.25 17 CAT-G Copolymerization 4.3 0.36 2.85 0.25 21.74

When comparing experiment No. 1 with experiment No. 2, experiment No. 3 with experiment No. 4, experiment No. 5 with experiment No. 6 in Table I-1, it becomes clear that, during copolymerization, the activity of the catalyst increases significantly, which means that supported on the carrier the non-metallocene catalyst of the invention exhibits a significant comonomer effect.

When comparing experiment No. 1 with experiments No. 11-13 in Table I-1, it is obvious that the activity of the catalyst increases or decreases with an increase or decrease in the amount of non-metallocene ligand introduced into the catalyst, while the molecular weight distribution of the polymer narrows or expands. , respectively. This fact indicates that the nonmetallocene ligand exhibits a function of narrowing the molecular weight distribution of the polymer. When comparing experiment No. 1 with experiment No. 14 in Table I-1, it becomes apparent that the activity of the catalyst increases with increasing amount of chemical treatment agent introduced into the catalyst. When comparing experiment No. 1 with experiment No. 15 in Table I-1, it becomes apparent that the activity of the catalyst changes with a change in the reaction temperature, and the molecular weight distribution of the polymer expands with increasing reaction temperature. In view of this, it is not difficult for a person skilled in the art in accordance with the present invention to produce various catalysts in terms of activity and performance of the resulting polymer by changing the non-metallocene ligand used or the reaction temperature.

When comparing experiments No. 1-15 with experiment No. 16 in Table I-1, it is obvious that the polymer produced in accordance with the present invention has a relatively high bulk density, a relatively high specific surface area, and a relatively large pore size.

When comparing experiment No. 2 with experiment No. 17 in Table I-1, it is obvious that the non-metallocene catalyst supported on the support obtained in accordance with the present invention exhibits a relatively higher catalytic activity for the polymerization of olefin and leads to the formation of a polymer having a relatively higher bulk density, relatively higher specific surface area, relatively larger pore size and more suitable molecular weight distribution, compared to deposited m to the carrier with a non-metallocene catalyst obtained by directly attaching the non-metallocene complex to the carrier, which makes the polymer obtained in accordance with the present invention more suitable for use in the preparation of chlorinated polyethylene by the chlorination method.

Chlorination Example

Chlorination was carried out in accordance with the method of chlorination in suspension with an aqueous phase. In particular, to 3500 kg of water with stirring, 10 kg of dispersing agent (sodium polymethacrylate), 1.2 kg of suspension stabilizer (ethylene oxide-propylene oxide copolymer), 0.7 kg of emulsifying agent (polyvinylpyrrolidone) were successively added, and then 550 kg of polymer were added, obtained in accordance with the present invention, after heating to 35-45 ° C, from 2.5 to 3 kg of catalyst (benzoperoxide) was added thereto, after heating under sealed conditions to 60 ° C, chlorine gas was supplied in three stages. In the first stage, in relation to 100 mass parts of the polymer, from 170 to 195 mass parts of gaseous chlorine were supplied, with a chlorination temperature of 75 to 80 ° C, a chlorination pressure <0.2 MPa and a chlorination duration of 45 to 60 minutes. In the second stage, in relation to 100 parts by mass of the polymer, 260 to 290 parts by mass of chlorine gas were supplied, with a chlorination temperature of 100 to 110 ° C., a chlorination pressure <0.3 MPa and a chlorination duration of 1.5 to 2.5 hours. In the third stage, in relation to 100 mass parts of the polymer, 150 to 165 mass parts of chlorine gas were supplied, with a chlorination temperature of 125 to 132 ° C, a chlorination pressure <0.4 MPa and a chlorination duration of 95 to 105 minutes. At the final stage, a suspension of chlorinated polyethylene was obtained, then filtered, compressed, neutralized, washed with water, separated by centrifugation and dried, and chlorinated polyethylene having a chlorine content of 33-37 wt.% Was obtained.

The polymer used in this chlorination example was a polymer obtained in accordance with experiment No. 2 in Table I-1, and a chlorinated polyethylene having a chlorine content of 35.1 wt.%, Which exhibits a Mooney viscosity of 59, VOC content, was obtained. (volatile organic compounds) 0.24 wt.%, melting enthalpy <2 J / g, Shore hardness 49 A, tensile strength 12.2 MPa, and elongation at break 776%.

Example II

Homopolymerization or copolymerization of ethylene provided in the following Examples and Comparative Examples was carried out in accordance with the following method.

Homopolymerization: autoclave for polymerization (5 L), suspension polymerization method, hexane (2.5 L) as solvent, total polymerization pressure 0.8 MPa, polymerization temperature 85 ° C, polymerization time 2 hours.

In particular, 2.5 L of hexane was added to the autoclave for polymerization, and the stirrer was started. Then, a mixture of a test catalyst (50 mg) and a cocatalyst (triethyl aluminum) was added, where the molar ratio of the cocatalyst (based on Al) to the test catalyst (based on the central metal atom) was 100: 1. Then, hydrogen gas was supplied there until a specified partial pressure was reached, and ethylene was continuously fed at the end to maintain the total polymerization pressure constant at 0.8 MPa. Upon completion of the polymerization, the inner contents of the autoclave were released into the surrounding atmosphere, and the resulting polymer product was taken out of the autoclave and weighed (mass) after drying.

Copolymerization: autoclave for polymerization (5 L), suspension polymerization method, hexane (2.5 L) as solvent, total polymerization pressure 0.8 MPa, polymerization temperature 85 ° C, polymerization time 2 hours.

In particular, 2.5 L of hexane was added to the autoclave for polymerization, and the stirrer was started. Then, a mixture of a test catalyst (50 mg) and a cocatalyst (triethyl aluminum) was added, where the molar ratio of the cocatalyst (based on Al) to the test catalyst (based on the central metal atom) was 100: 1. Then, butene-1 (10 g) was added thereto as a comonomer all at once, and then hydrogen gas was supplied until the specified partial pressure was reached, and ethylene was continuously fed at the end to keep the total polymerization pressure constant at 0.8 MPa. Upon completion of the polymerization, the inner contents of the autoclave were released into the surrounding atmosphere, and the resulting polymer product was taken out of the autoclave and weighed (mass) after drying.

Example II-1

The alkoxy magnesium spherical support was diethoxy magnesium spherical support (having a sphericity of 1.42, bulk density of 0.32 g / cm ³ and an average particle size of 420 μm), the contacting solvent was n-octane, the chemical treatment agent was titanium tetrachloride, the nonmetallocene ligand has the structure

A diethoxy magnesium spherical support (5 g) and a nonmetallocene ligand were weighed, n-heptane was added thereto and stirred at 300 rpm for 30 minutes, heated to 90 ° C to obtain a homogeneous dispersion. Then, titanium tetrachloride was continuously added dropwise to this dispersion over 2 hours, after completion of the addition, the reaction was continued with stirring at 90 ° C for 6 hours, filtered, washed with hexane 3 times (60 ml each time) and finally dried in vacuum at normal temperature to obtain supported on a non-metallocene catalyst.

In this example, the ratio of diethoxy magnesium spherical support to n-heptane was 1 mol: 1000 ml, the molar ratio of diethoxy magnesium spherical support to a nonmetallocene ligand was 1: 0.01, the molar ratio of diethoxy magnesium spherical support to titanium tetrachloride was 1: 2.1.

For homopolymerization of ethylene, a non-metallocene catalyst supported on a carrier was used, with a partial pressure of gaseous hydrogen of 0.2 MPa, showing the activity of the catalyst 6.2 kg PE / g Cat, the polymer had the following characteristics: bulk density 0.38 g / cm ³ , content oligomer 1.7 g / l, fine powder content (less than 75 μm) 4.6 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.84 g / 10 min, molecular weight distribution (Mw / Mn) 3.62, density 0.961 g / cm ³ , average particle size 350 μm, specific area surface 1.57 m ² / g, pore volume 0.00355 cm ³ / g, pore size 47.43 nm, the content of the repeating unit originating from ethylene, 100 wt.%.

Example II-2

Essentially the same as in Example II-1, except for the following changes:

растворитель для контактирования был изменен на гептан, агент химической обработки был изменен на тетрахлорид циркония (ZrCl₄), температура реакции была изменена на 85°C, по окончании добавления реакцию продолжали при перемешивании при 85°C в течение 10 часов.The nonmetallocene ligand was

the contacting solvent was changed to heptane, the chemical treatment agent was changed to zirconium tetrachloride (ZrCl ₄ ), the reaction temperature was changed to 85 ° C, after completion of the addition, the reaction was continued with stirring at 85 ° C for 10 hours.

In this example, the ratio of the alkoxy magnesium spherical carrier to the solvent for contacting was 1 mol: 1500 ml, the molar ratio of the alkoxy magnesium spherical carrier to the nonmetallocene ligand was 1: 0.015, the molar ratio of the alkoxy magnesium spherical carrier to the chemical treatment agent was 1: 3.

For the homopolymerization of ethylene, a non-metallocene catalyst supported on a carrier was used, with a partial pressure of hydrogen gas of 0.15 MPa, showing a catalyst activity of 9.8 kg PE / g Cat, polymer performance was as follows: bulk density 0.38 g / cm ³ , content oligomer 1.3 g / l, fine powder content (less than 75 μm) 3.4 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.26 g / 10 min, molecular weight distribution (Mw / Mn) 3,86, density 0.958 g / cm ^3, an average particle size of 362 microns, specific surface area surface of 1.73 m ² / g, pore volume of 0.0038 cm ³ / g, pore size of 49.46 nm, the content of the repeating unit derived from ethylene, 98.5 wt.%, the content of repeating units derived from butene-1 1.5 wt.%.

Example II-3

Essentially the same as in Example II-1, except for the following changes:

растворитель для контактирования был изменен на этилбензол, температура реакции была изменена на 95°C, по окончании добавления реакцию продолжали при перемешивании при 95°C в течение 4 часов.The alkoxy-magnesium spherical support was changed to dipropoxy-magnesium spherical support (Mg (OPr) ₂ ) (having a sphericity of 1.83, bulk density of 0.40 g / cm ³ and an average particle size of 530 μm), the nonmetallocene ligand was

the contacting solvent was changed to ethylbenzene, the reaction temperature was changed to 95 ° C, after completion of the addition, the reaction was continued with stirring at 95 ° C for 4 hours.

In this example, the ratio of the alkoxy magnesium spherical support to the solvent for contacting was 1 mol: 2000 ml, the molar ratio of the alkoxy magnesium spherical support to the nonmetallocene ligand was 1: 0.02, and the molar ratio of the alkoxy magnesium spherical support to the chemical treatment agent was 1: 5.

For the homopolymerization of ethylene, a nonmetallocene catalyst supported on a carrier was used, with a partial pressure of hydrogen gas of 0.10 MPa, showing a catalyst activity of 13.5 kg PE / g Cat, polymer performance was as follows: bulk density 0.39 g / cm ³ , content oligomer 0.7 g / l, fine powder content (less than 75 μm) 3.2 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.15 g / 10 min, molecular weight distribution (Mw / Mn) 3.83, density 0.955 g / cm ³ , average particle size 348 μm, specific area l surface 1.94 m ² / g, pore volume 0.0046 cm ³ / g, pore size 52.18 nm, the content of the repeating unit derived from ethylene, 99.2 wt.%, the content of the repeating unit originating from butene- 1, 0.8 wt.%.

Example II-4

Essentially the same as in Example II-1, except for the following changes:

растворитель для контактирования был изменен на декан, агентом химической обработки был этокситрихлортитан (Ti(OCH₂CH₃)Cl₃), температура реакции была изменена на 100°C, по окончании добавления реакцию продолжали при перемешивании при 100°C в течение 3 часов.The alkoxymagnesium spherical support was changed to dibutoximagnesium spherical support (Mg (OC ₄ H ₉ ) ₂ ) (having a sphericity of 2.07, bulk density of 0.62 g / cm ³ and an average particle size of 630 μm), the nonmetallocene ligand was

the contacting solvent was changed to decane, the chemical treatment agent was ethoxytrichlorotitan (Ti (OCH ₂ CH ₃ ) Cl ₃ ), the reaction temperature was changed to 100 ° C, and after the addition was complete, the reaction was continued with stirring at 100 ° C for 3 hours.

In this example, the ratio of the alkoxy magnesium spherical support to the solvent for contacting was 1 mol: 3500 ml, the molar ratio of the alkoxy magnesium spherical support to the nonmetallocene ligand was 1: 0.02, the molar ratio of the alkoxy magnesium spherical support to the chemical treatment agent was 1:10.

For homopolymerization of ethylene, a non-metallocene catalyst supported on a carrier was used, with a partial pressure of gaseous hydrogen of 0.05 MPa, showing a catalyst activity of 32.8 kg PE / g Cat, polymer performance was as follows: bulk density 0.39 g / cm ³ , content oligomer 0.3 g / l, fine powder content (less than 75 μm) 2.1 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.02 g / 10 min, molecular weight distribution (Mw / Mn) 4.02, density 0.953 g / cm ³ , average particle size 376 μm, specific area l surface 1.76 m ² / g, pore volume 0.00236 cm ³ / g, pore size 49.17 nm, the content of the repeating unit derived from ethylene, 99.7 wt.%, the content of the repeating unit originating from butene- 1, 0.3 wt.%.

Example II-5

Essentially the same as in Example II-1, except for the following changes:

, растворитель для контактирования был изменен на декан, агентом химической обработки был этокситрихлортитан (Ti(OCH₂CH₃)Cl₃), температура реакции была изменена на 110°C, по окончании добавления реакцию продолжали при перемешивании при 110^oC в течение 8 часов.The alkoxy magnesium spherical support was changed to dimethoxy magnesium spherical support (Mg (OCH ₃ ) ₂ ) (having a sphericity of 2.2, a bulk density of 0.25 g / cm ³ and an average particle size of 275 μm), the nonmetallocene ligand was

, the contacting solvent was changed to decane, the chemical treatment agent was ethoxytrichlorotitanium (Ti (OCH ₂ CH ₃ ) Cl ₃ ), the reaction temperature was changed to 110 ° C, and after the addition was complete, the reaction was continued with stirring at 110 ^° C for 8 hours .

In this example, the ratio of the alkoxy magnesium spherical support to the solvent for contacting was 1 mol: 4000 ml, the molar ratio of the alkoxy magnesium spherical support to the nonmetallocene ligand was 1: 0.03, the molar ratio of the alkoxy magnesium spherical support to the chemical treatment agent was 1:14.

For homopolymerization of ethylene, a non-metallocene catalyst supported on a carrier was used, with a partial pressure of hydrogen gas of 0.20 MPa, showing a catalyst activity of 27.6 kg PE / g Cat, polymer performance was as follows: bulk density 0.38 g / cm ³ , content oligomer 0.8 g / l, fine powder content (less than 75 microns) 3.7 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.75 g / 10 min, molecular weight distribution (Mw / Mn) 3.52, density 0.958 g / cm ³ , average particle size 402 μm, specific area l surface 1.45 m ² / g, pore volume 0.0037 cm ³ / g, pore size 55.62 nm, the content of the repeating unit derived from ethylene, 99.5 wt.%, the content of the repeating unit originating from butene- 1, 0.5 wt.%.

Example II-6

Essentially the same as in Example II-1, except for the following changes:

растворитель для контактирования был изменен на 2-этилоктан, агентом химической обработки был этилтрихлортитан (Ti(CH₂CH₃)Cl₃), температура реакции была изменена на 120°C, по окончании добавления реакцию продолжали при перемешивании при 120°C в течение 16 часов.The nonmetallocene ligand was

the contacting solvent was changed to 2-ethylloctane, the chemical processing agent was ethyl trichlorotitanium (Ti (CH ₂ CH ₃ ) Cl ₃ ), the reaction temperature was changed to 120 ° C, and after the addition was complete, the reaction was continued with stirring at 120 ° C for 16 hours.

In this example, the ratio of the alkoxy magnesium spherical support to the solvent for contacting was 1 mol: 6000 ml, the molar ratio of the alkoxy magnesium spherical support to the nonmetallocene ligand was 1: 0.05, and the molar ratio of the alkoxy magnesium spherical support to the chemical treatment agent was 1: 8.

For the homopolymerization of ethylene, a nonmetallocene catalyst supported on a carrier was used, with a partial pressure of hydrogen gas of 0.2 MPa, showing catalyst activity of 17.4 kg PE / g Cat, polymer performance was as follows: bulk density 0.38 g / cm ³ , content oligomer 1.5 g / l, fine powder content (less than 75 μm) 4.1 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.67 g / 10 min, molecular weight distribution (Mw / Mn) 3,40, density 0.961 g / cm ^3, an average particle size of 372 microns, specific surface area surface of 1.52 m ² / g, a pore volume of 0.00326 cm ³ / g, a pore size of 49.28 nm, the content of the repeating unit derived from ethylene, 100 wt.%.

Example II-7

Essentially the same as in Example II-1, except for the following changes:

растворитель для контактирования был изменен на метилэтилбензол, агент химической обработки был изменен на метокситрибромтитан (Ti(OCH₃)Br₃), температура реакции была изменена на 120°C, по окончании добавления реакцию продолжали при перемешивании при 120°C в течение 25 часов.The alkoxy magnesium spherical carrier was changed to ethoxypropoxy magnesium spherical carrier (Mg (OEt) (OPr)) (having a sphericity of 1.3, a bulk density of 0.52 g / cm ³ and an average particle size of 350 μm or more), the nonmetallocene ligand was

the contacting solvent was changed to methylethylbenzene, the chemical treatment agent was changed to methoxytribromtitanium (Ti (OCH ₃ ) Br ₃ ), the reaction temperature was changed to 120 ° C, and upon completion of the addition, the reaction was continued with stirring at 120 ° C for 25 hours.

In this example, the ratio of the alkoxy magnesium spherical carrier to the solvent for contacting was 1 mol: 8000 ml, the molar ratio of the alkoxy magnesium spherical carrier to the nonmetallocene ligand was 1: 0.06, the molar ratio of the alkoxy magnesium spherical carrier to the chemical treatment agent was 1: 3.5.

For homopolymerization of ethylene, a non-metallocene catalyst supported on a carrier was used, with a partial pressure of gaseous hydrogen of 0.2 MPa, showing a catalyst activity of 9.4 kg PE / g Cat, polymer performance was as follows: bulk density 0.37 g / cm ³ , content oligomer 1.2 g / l, fine powder content (less than 75 μm) 3.7 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.45 g / 10 min, molecular weight distribution (Mw / Mn) 3.31, density 0.961 g / cm ³ , average particle size 380 microns, specific area the surface of 1.55 m ² / g, pore volume of 0.00295 cm ³ / g, pore size of 50.26 nm, the content of the repeating unit derived from ethylene, 100 wt.%.

Comparative Example II-A

Essentially the same as in Example II-1, except for the following changes:

A nonmetallocene ligand was not added.

The catalyst used for homopolymerization of ethylene showed a catalyst activity of 5.5 kg PE / g Cat, polymer performance was as follows: bulk density 0.38 g / cm ³ , oligomer content 1.9 g / l, fine powder content (less than 75 μm) 5.2 wt.%, Melt index (at 190 ° C and a load of 2.16 kg) 1.04 g / 10 min, molecular weight distribution (Mw / Mn) 4.21, density 0.961 g / cm ³ , the average particle size is 316 μm, the specific surface area is 1.35 m ² / g, the pore volume is 0.00326 cm ³ / g, the pore size is 47.23 nm, the content of the repeating unit, coming from ethylene, 100 wt.%.

Comparative Example II-B

Essentially the same as in Example II-1, except for the following changes:

The molar ratio of alkoxymagnesium spherical carrier to non-metallocene ligand was changed to 1: 0.02.

For homopolymerization of ethylene, a non-metallocene catalyst supported on a carrier was used, demonstrating catalyst activity of 7.4 kg PE / g Cat, polymer performance was as follows: bulk density 0.38 g / cm ³ , oligomer content 1.4 g / l, fine content powder (less than 75 microns) 4.1 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.77 g / 10 min, molecular weight distribution (Mw / Mn) 3.47, density 0.961 g / cm ³ , average particle size 356 μm, specific surface area 1.54 m ² / g, pore volume 0.00348 cm ³ / g, pore size 48.6 5 nm, the content of the repeating unit derived from ethylene, 100 wt.%.

Comparative Example II-C

Essentially the same as in Example II-1, except for the following changes:

The molar ratio of alkoxymagnesium spherical carrier to non-metallocene ligand was changed to 1: 0.04.

For the homopolymerization of ethylene, a non-metallocene supported catalyst supported on the catalyst showed an activity of 7.8 kg PE / g Cat, polymer performance was as follows: bulk density 0.38 g / cm ³ , oligomer content 1.0 g / l, fine content powder (less than 75 microns) 3.8 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.68 g / 10 min, molecular weight distribution (Mw / Mn) 3.24, density 0.961 g / cm ³ , average particle size 352 μm, specific surface area 1.54 m ² / g, pore volume 0.00327 cm ³ / g, pore size 49.3 2 nm, the content of the repeating unit derived from ethylene, 100 wt.%.

Comparative Example II-D

Essentially the same as in Example II-1, except for the following changes:

The molar ratio of alkoxymagnesium spherical support to chemical treatment agent was changed to 1: 4.

For the homopolymerization of ethylene, a nonmetallocene supported catalyst supported on the catalyst showed an activity of 9.7 kg PE / g Cat, polymer performance was as follows: bulk density 0.39 g / cm ³ , oligomer content 2.2 g / l, fine content powder (less than 75 microns) 4.5 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 1.05 / 10 min, molecular weight distribution (Mw / Mn) 3.85, density 0.961 g / cm ^3, average particle size of 363 microns, a specific surface area of 1.47 m ² / g, a pore volume of 0.00284 cm ³ / g, a pore size of 45.63 m, the content of the repeating unit derived from ethylene, 100 wt.%.

Comparative Example II-E

Essentially the same as in Example II-1, except for the following changes:

The reaction temperature was changed to 100 ° C.

For homopolymerization of ethylene, a non-metallocene catalyst supported on a carrier was used, showing a catalyst activity of 6.1 kg PE / g Cat, polymer performance was as follows: bulk density 0.38 g / cm ³ , oligomer content 1.7 g / l, fine content powder (less than 75 microns) 4.7 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.91 g / 10 min, molecular weight distribution (Mw / Mn) 4.12, density 0.961 g / cm ³ , average particle size 350 μm, specific surface area 1.84 m ² / g, pore volume 0.00394 cm ³ / g, pore size 51.3 2 nm, the content of the repeating unit derived from ethylene, 100 wt.%.

Comparative Example II-F

Essentially the same as in Example II-1, except for the following changes:

For homopolymerization of ethylene, a non-metallocene catalyst supported on a carrier was used, with a partial pressure of gaseous hydrogen of 0.2 MPa, showing a catalyst activity of 7.1 kg PE / g Cat, polymer performance was as follows: bulk density 0.38 g / cm ³ , content oligomer 17 g / l, fine powder content (less than 75 μm) 4.8 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 0.95 g / 10 min, molecular weight distribution (Mw / Mn) 3,85, density 0.958 g / cm ^3, an average particle size of 354 microns, a specific surface area overhnosti from 1.94 m ² / g, pore volume of 0.0040 cm ³ / g, a pore size of 50.22 nm, the content of the repeating unit derived from ethylene, 98.7 wt.%, the content of the repeating unit derived from butena- 1, 1.3 wt.%.

Comparative Example II-G

This magnesium compound was anhydrous MgCl ₂ , the solvent for dissolving the magnesium compound and nonmetallocene ligand was tetrahydrofuran, and titanium tetrachloride was the chemical treatment agent. Nonmetallocene ligand has the structure

Anhydrous MgCl ₂ (5 g) and a nonmetallocene ligand were weighed, tetrahydrofuran was added at room temperature to dissolve them completely, after stirring for 2 hours, they were added to hexane as a precipitating agent, filtered, washed with hexane 2 times (60 ml each time) , dried under uniform heating at 60 ° C under vacuum to obtain a modified carrier.

To this modified carrier was added 60 ml of hexane, then, with stirring, titanium tetrachloride was added dropwise over 30 minutes, after which the reaction was continued with stirring at 60 ° C for 4 hours, filtered, washed with hexane 2 times (60 ml each time), and finally dried in vacuum at normal temperature to obtain a non-metallocene catalyst supported on a carrier.

In this example, the ratio of MgCl ₂ to tetrahydrofuran was 1 mol: 210 ml, the molar ratio of MgCl ₂ to non-metallocene ligand was 1: 0.01, the ratio by volume of precipitating agent to tetrahydrofuran was 1: 1, the molar ratio of MgCl ₂ to titanium tetrachloride was 1 : 0.15.

The catalyst used for homopolymerization of ethylene with a partial pressure of gaseous hydrogen of 0.2 MPa shows a catalyst activity of 16.5 kg PE / g Cat, polymer performance was as follows: bulk density 0.32 g / cm ³ , oligomer content 3.4 g / l, fine powder content (less than 75 microns) 5.7 wt.%, melt index (at 190 ° C and a load of 2.16 kg) 1.05 g / 10 min, molecular weight distribution (Mw / Mn ) 3.1, density 0.961 g / cm ³ , average particle size 285 μm, specific surface area 0.52 m ² / g, pore volume 0.0021 cm ³ / g, pa pore size 32.31 nm, the content of the repeating unit derived from ethylene, 100 wt.%.

When comparing Example II-1 with Comparative Examples II-A to II-C, it is obvious that the activity of the catalyst increases or decreases with an increase or decrease in the amount of non-metallocene ligand introduced into the catalyst, while the molecular weight distribution of the polymer narrows or expands. , respectively. This fact indicates that the nonmetallocene ligand exhibits a function of narrowing the molecular weight distribution of the polymer. When comparing Example II-1 with Comparative Example II-D, it is obvious that the activity of the catalyst increases with increasing amount of chemical treatment agent introduced into the catalyst. When comparing Example II-1 with Comparative Example II-E, it becomes apparent that the activity of the catalyst changes with a change in the reaction temperature, and the molecular weight distribution of the polymer expands with increasing reaction temperature. In view of this, it is not difficult for a person skilled in the art in accordance with the present invention to produce various catalysts in terms of activity and performance of the resulting polymer by changing the non-metallocene ligand used or the reaction temperature.

When comparing Example II-1 with Comparative Example II-F, it becomes clear that during copolymerization, the activity of the catalyst increases significantly, which means that the non-metallocene catalyst of the invention supported on a carrier exhibits a significant comonomer effect.

When comparing Example II-1 with Comparative Example II-G, it is obvious that the polymer obtained in accordance with the present invention has a relatively high bulk density, a relatively large specific surface area and a relatively large pore volume.

Example II-4 (Applicability Example)

Chlorination was carried out in accordance with the method of chlorination in suspension with an aqueous phase. In particular, to 3500 kg of water, with stirring, 10 kg of dispersing agent (sodium polymethacrylate), 1.2 kg of suspension stabilizer (copolymer of ethylene oxide and propylene oxide), 0.7 kg of emulsifying substance (polyvinylpyrrolidone) were successively added, and then 550 kg polymer, obtained in accordance with the present invention, after heating to 35-45 ° C, 2.5 to 3 kg of catalyst (benzoperoxide) was added thereto, after heating under airtight conditions to 60 ° C, chlorine gas was supplied in three stages. In the first stage, in relation to 100 mass parts of the polymer, from 170 to 195 mass parts of gaseous chlorine were supplied, with a chlorination temperature of 75 to 80 ° C, a chlorination pressure <0.2 MPa and a chlorination duration of 45 to 60 minutes. In the second stage, in relation to 100 parts by mass of the polymer, 260 to 290 parts by mass of chlorine gas were supplied, with a chlorination temperature of 100 to 110 ° C., a chlorination pressure <0.3 MPa and a chlorination duration of 1.5 to 2.5 hours. In the third stage, in relation to 100 mass parts of the polymer, 150 to 165 mass parts of chlorine gas were supplied, with a chlorination temperature of 125 to 132 ° C, a chlorination pressure <0.4 MPa and a chlorination duration of 95 to 105 minutes. At the final stage, a suspension of chlorinated polyethylene was obtained, then filtered, compressed, neutralized, washed with water, separated by centrifugation and dried, and chlorinated polyethylene was obtained.

The polymer used here was the polyethylene obtained in accordance with Example II-1, and a chlorinated polyethylene was obtained having a chlorine content of 34.7 wt.%, Which exhibits a Mooney viscosity of 84, the VOC content (volatile organic compounds) of 0.24 wt.%, melting enthalpy <2 J / g, Shore hardness 54A, tensile strength 10.3 MPa, and elongation at break 790%.

One skilled in the art will appreciate that various modifications and changes can be made to the present invention without departing from the spirit and or scope of the present invention. Thus, it is understood that the present invention provides for modifications and changes of the present invention, in the event that they fall within the range of the claims and their analogues.

Claims (12)

1. A method of producing a non-metallocene catalyst supported on a carrier, comprising the step of contacting a non-metallocene ligand, a chemical treatment agent selected from a compound of Group IVB, and an alkoxymagnesium spherical carrier in the presence of an interaction solvent, wherein the alkoxymagnesium spherical carrier has an average particle size of from 100 to 2000 μm, and the nonmetallocene ligand of the present method is one or more selected from the group consisting of compounds having the following structure py

preferably one or more selected from the group consisting of the following compound (A) and the following compound (B),

and

more preferably one or more selected from the group consisting of the following compound (A-1), the following compound (A-2), the following compound (A-3), the following compound (A-4), the following compound (B-1) , the following compound (B-2), the following compound (B-3) and the following compound (B-4),

and

in all the above formulas, q represents 0 or 1, d represents 0 or 1, A is selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom,

, -NR ²³ R ²⁴ , -N (O) R ²⁵ R ²⁶ ,

, -PR ²⁸ R ²⁹ , -P (O) R ³⁰ OR ³¹ , sulfonic group, sulfoxide group and -Se (O) R ³⁹ , where each of N, O, S, Se and P represents a coordination atom;
In selected from the group consisting of a nitrogen atom, a nitrogen-containing group, a phosphorus-containing group and a C ₁ -C ₃₀ hydrocarbyl;
D is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen-containing group, a phosphorus-containing group, a C ₁ -C ₃₀ hydrocarbyl, sulfonic group or sulfoxide group, where each of N, O, S, Se and P represents a coordination atom;
E is selected from the group consisting of a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, and a cyano group, where each of N, O, S, Se, and P represents a coordination atom;
F is selected from the group consisting of a nitrogen atom, a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, where each of N, O, S, Se and P represents a coordination atom;
G is selected from the group consisting of C ₁ -C ₃₀ hydrocarbyl, substituted C ₁ -C ₃₀ hydrocarbyl, and an inert functional group;
Y is selected from the group consisting of a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, and a phosphorus-containing group, where each of N, O, S, Se, and P represents a coordination atom;
Z is selected from the group consisting of a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, and a cyano group, where each of N, O, S, Se, and P represents a coordination atom;

represents a single bond or double bond;
- represents a covalent bond or ionic bond;
each R ¹ -R ⁴ , R ⁶ -R ^{21 is} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl, substituted C ₁ -C ₃₀ hydrocarbyl, and an inert functional group, each of R ²² -R ³¹ , and R ^{39 are} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl, where these groups may be the same or different from each other, and any adjacent groups may form a bond or ring (preferably aromatic ring) with each other;
the inert functional group is selected from the group consisting of a halogen atom, an oxygen-containing group, a nitrogen-containing group, a silicon-containing group, a germanium-containing group, a sulfur-containing group, a tin-containing group, a C ₁ -C ₁₀ ester group and a nitro group,
R ^{5 is} selected from the group consisting of a lone electron pair on a nitrogen atom, a hydrogen atom, a C ₁ -C ₃₀ hydrocarbyl, a substituted C ₁ -C ₃₀ hydrocarbyl, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group and a phosphorus-containing group, provided that when R ⁵ is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group, each of N, O, S, P and Se in the R ⁵ group acts as a coordination atom; and
substituted C ₁ -C ₃₀ hydrocarbyl selected from C ₁ -C ₃₀ hydrocarbyl having one or more substituents selected from a halogen atom and a C ₁ -C ₃₀ alkyl group,
the non-metallocene ligand is more preferably one or more selected from the group consisting of the following compounds

,

,

,

,

and

,
more preferably one or more selected from the group consisting of the following compounds

and

. 2. The method according to claim 1, where in the presence of a solvent, the nonmetallocene ligand is brought into contact with an alkoxymagnesium spherical carrier and then a chemical treatment agent is added for further contact. 3. The method according to claim 1, where alkoxymagnesium is represented by the formula Mg (OR _a ) (OR _b ), where R _a and R _b are the same or different from each other, and each is independently selected from straight chain C ₁ -C ₁₈ alkyl or branched chain, preferably each independently selected from straight chain or branched C ₁ -C ₁₀ alkyl, further preferably each independently selected from straight chain or branched C ₁ -C ₆ alkyl, further preferably each independently selected from C ₁ -C ₄ straight or branched chain alkyl s, more preferably each is independently selected from straight chain or branched C ₂ -C ₄ alkyl, most preferably both are ethyl. 4. The method according to claim 1, where the alkoxymagnesium spherical carrier has a sphericity of from 1 to 3, preferably from 1 to 1.5, bulk density from 0.2 to 1.0 g / cm ³ , preferably from 0.25 to 0, 7 g / cm ³ , more preferably 0.3 to 0.5 g / cm ³ , and an average particle size of 100 to 1500 μm, preferably 100 to 1000 μm. 5. The method according to claim 1, where
a halogen atom selected from the group consisting of F, Cl, Br and I,
a nitrogen-containing group selected from the group consisting of

, -NR ²³ R ²⁴ , -T-NR ²³ R ²⁴ and -N (O) R ²⁵ R ²⁶ ,
a phosphorus-containing group selected from the group consisting of

, -PR ²⁸ R ²⁹ , -P (O) R ³⁰ R ³¹ and -P (O) R ³² (OR ³³ ),
the oxygen-containing group is selected from the group consisting of hydroxy, -OR ³⁴ and -T-OR ³⁴ ,
a sulfur-containing group selected from the group consisting of —SR ³⁵ , —T — SR ³⁵ , —S (O) R ^36, and —T — SO ₂ R ³⁷ ,
a selenium-containing group is selected from the group consisting of —SeR ³⁸ , —T-SeR ³⁸ , —Se (O) R ^39, and -T-Se (O) R ³⁹ ,
group T is selected from the group consisting of C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl,
each of R ³² -R ³⁶ , and R ^{38 are} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl, and these groups may be the same or different from each other, and any adjacent groups may form a bond or ring (preferably an aromatic ring) with each other;
R ^{37 is} selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl,
C ₁ -C ₃₀ hydrocarbyl is selected from the group consisting of C ₁ -C ₃₀ alkyl group, C ₇ -C ₃₀ alkylaryl group, C ₇ -C ₃₀ aralkyl group, cyclic C ₃ -C ₃₀ alkyl group, C ₂ -C ₃₀ alkenyl group, C ₂ -C ₃₀ alkynyl group, C ₆ -C ₃₀ aryl group, fused cyclic C ₈ -C ₃₀ group and C ₄ -C ₃₀ heterocyclic group, where the heterocyclic group contains from 1 to 3 heteroatoms selected from the group, consisting of a nitrogen atom, an oxygen atom and a sulfur atom,
the silicon-containing group is selected from the group consisting of —SiR ⁴² R ⁴³ R ⁴⁴ and —T-SiR ⁴⁵ ,
a germanium-containing group is selected from the group consisting of —GeR ⁴⁶ R ⁴⁷ R ⁴⁸ and —T-GeR ⁴⁹ ,
a tin-containing group is selected from the group consisting of —SnR ⁵⁰ R ⁵¹ R ⁵² , —T-SnR ⁵³ and —T-Sn (O) R ⁵⁴ ,
each of R ⁴² -R ^{54 is} independently selected from the group consisting of a hydrogen atom, C ₁ -C ₃₀ hydrocarbyl and substituted C ₁ -C ₃₀ hydrocarbyl, where these groups may be identical or different from each other, and any adjacent groups may form bond or ring to each other, and
group T is defined as described above. 6. The method according to claim 1, where the molar ratio of alkoxymagnesium spherical carrier (Mg-based) to non-metallocene ligand is 1: 0.001-0.08, preferably 1: 0.005-0.06, more preferably 1: 0.01-0, 04, and the molar ratio of the alkoxy magnesium spherical support (Mg-based) to the chemical treatment agent (based on a metal of group IVB) is 1: 1-30, preferably 1: 2-20, more preferably 1: 4-10. 7. The method according to claim 1, where the compound of the metal of Group IVB is one or more compounds selected from the group consisting of a halide compound of a metal of Group IVB, an alkyl halide compound of a metal of Group IVB and an alkoxyhalide compound of a metal of Group IVB, preferably one or more halide metal compounds groups IVB, more preferably one or more compounds selected from the group consisting of TiCl _4, TiBr _4, ZrCl _4, ZrBr _4, HfCl _4, HfBr _4, and more preferably one or more compounds selected from the group consisting of TiCl ₄ ZrCl _4. 8. Non-metallocene catalyst for the homopolymerization / copolymerization of olefins, supported on a carrier obtained in accordance with the method according to any one of claims 1 to 7. 9. A method for homopolymerization / copolymerization of an olefin, comprising the step of homopolymerization / copolymerization of an olefin in the presence of a non-metallocene catalyst supported in accordance with claim 8 as a main catalyst in combination with one or more cocatalysts selected from the group consisting of aluminoxane, aluminum alkyl, halogenated aluminum alkyl, fluoroborane, boralkyl and ammonium salt of boralkyl. 10. The method of homopolymerization / copolymerization of olefin according to claim 9, where the suspension polymerization procedure takes place, and under conditions of a total polymerization pressure of 0.2 to 2.0 MPa (preferably 0.5 to 1.5 MPa), the partial pressure ratio hydrogen gas to ethylene 0.01-0.2: 1 (preferably 0.02-0.1: 1, most preferably 0.03-0.08: 1), polymerization temperatures from 60 to 100 ° C (preferably from 70 up to 95 ° C, more preferably from 80 to 90 ° C) and the amount of optional comonomer from 0.5 to 10 g per 1 mg of basic catalyst (preferably about 1 to 5 g per 1 mg of a basic catalyst) is carried out homopolymerization of ethylene or copolymerization of ethylene with at least one alpha-olefin (s) selected from C ₃ -C ₁₂ alpha-olefin (preferably C ₃ -C ₈ alpha-olefin ), to obtain polyethylene. 11. The polyethylene obtained according to the method of homopolymerization / copolymerization according to claim 9, characterized by the presence of a repeating unit derived from ethylene, and an optional repeating unit derived from at least one alpha olefin (s) selected from C ₃ -C ₁₂ alpha olefin (preferably C ₃ -C ₈ alpha olefin), bulk density from 0.33 to 0.50 g / cm ³ , preferably from 0.38 to 0.46 g / cm ³ , more preferably from 0, 40 to 0.44 g / cm ^3, an oligomer content less than 2 g / l, content of fine powder (less than 75 microns) of less than Th 5 wt.%, Melt index (at 190 ° C and a load of 2.16 kg) from 0.02 to 5 g / 10 min, a molecular weight distribution of Mw / Mn from 2.5 to 20 (preferably from 4 to 10) , with a density of from 0.94 to 0.96 g / cm ³ , an average particle size of from 200 to 400 microns, a specific surface area of from 0.2 to 3.0 m ² / g, preferably from 1.0 to 3.0 m ² / g, more preferably 1.5 to 3.0 m ² / g, pore volume 0.001 to 0.15 cm ³ / g, preferably 0.01 to 0.15 cm ³ / g, more preferably 0 , 05 to 0.12 cm ³ / g, pore size from 10 to 80 nm, preferably from 20 to 70 nm, more preferably from 20 to 60 nm, and with respect to the total m Assy 100 wt.% polyethylene, the content of the repeating unit derived from ethylene, from 95 to 100 wt.%, and the content of the repeating unit originating from at least one alpha olefin (s) from 0 to 5 wt.%. 12. Chlorinated polyethylene obtained by chlorination of polyethylene according to claim 11 or by chlorination of polyethylene obtained in accordance with the method according to claim 9.