WO2007134537A1 - Composés organiques contenant des hétéroatomes et leur utilisation dans un catalyseur ziegler-natta à centre d'activation unique - Google Patents

Composés organiques contenant des hétéroatomes et leur utilisation dans un catalyseur ziegler-natta à centre d'activation unique Download PDF

Info

Publication number
WO2007134537A1
WO2007134537A1 PCT/CN2007/001648 CN2007001648W WO2007134537A1 WO 2007134537 A1 WO2007134537 A1 WO 2007134537A1 CN 2007001648 W CN2007001648 W CN 2007001648W WO 2007134537 A1 WO2007134537 A1 WO 2007134537A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
hydrocarbon group
titanium
hetero atom
Prior art date
Application number
PCT/CN2007/001648
Other languages
English (en)
French (fr)
Inventor
Yong Tang
Xiaohong Yang
Bo Liu
Xiuli Sun
Zhi Ma
Yuan Gao
Cong Wang
Original Assignee
Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences filed Critical Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences
Priority to EP07721221.5A priority Critical patent/EP2039677B1/en
Priority to JP2009511322A priority patent/JP2009537573A/ja
Publication of WO2007134537A1 publication Critical patent/WO2007134537A1/zh
Priority to US12/275,882 priority patent/US20090137383A1/en
Priority to US14/028,130 priority patent/US20140073500A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/14—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/14—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated
    • C07C225/16—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/14—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated
    • C07C225/16—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
    • C07C225/18—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings the carbon skeleton containing also rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/37—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
    • C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/40—Nitrogen atoms attached in position 8
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the present invention relates to a class of organic compounds containing a hetero atom and their use in the preparation of a single active site of Ziegler-Natta (Z-NM cinderizer).
  • the catalyst is used in a promoter of ruthenium-based aluminum or ruthenium. Under the action of aluminoxane, it can catalyze the homopolymerization of ethylene or the copolymerization of ethylene and C 3 ⁇ C 18 oc-different hydrocarbon to obtain a structure-controlled olefin polymer, which belongs to the technical field of preparation and application of olefin polymerization catalysts.
  • Novel single site catalysts include metallocene catalysts and non-macrocatalysts; 2) utilize ZN catalysts or their improvements in chemical processes.
  • the single-site catalyst can obtain the narrow molecular weight distribution poly-hydrocarbon (about 2) due to the same catalyst active center, which can effectively realize the copolymerization of ethylene and other monomers, and can adjust the main catalyst chemical structure to prepare different polymerization structures as needed. To obtain a variety of high performance polyolefin materials.
  • Ziegler-Natta catalysts Compared with metallocene and non-metallocene catalysts with single active centers, Ziegler-Natta catalysts still dominate in industrial production, which is closely related to the stability, simple preparation and low cost of Ziegler-Natta catalysts.
  • Ziegler-Natta catalysts have a variety of active centers that make them undesirably catalyze the copolymerization of olefins and modulate polymer structures.
  • Patent US 5,459,116 reports the use of magnesium containing an ester having at least one hydroxyl group as an electron donor.
  • a titanium-containing solid catalyst prepared by reacting a solution with a titanium compound can produce a high bulk density polymer with high activity;
  • patents US 5,106,807 and 4,330,649 control the activity of the catalyst and the molecular weight of the polymer by adding an ester compound to the system;
  • CN1189487C (PCT /KR2000/001549) provides a preparation method for preparing narrow molecular weight distribution ethylene homopolymers and copolymers with a molecular weight distribution of 3.6-4.3;
  • Terano reports the use of ethylene/propylene/diene elastomer (EPDM) loading The phase Ziegler-Natta catalyst and the surface-functionalized silica-supported catalyst catalyze the polymerization of ethylene, and the polymers with different molecular weight distributions (1.6-30) are obtained by changing the promoter, which is the narrowest obtained with the Ziegler-Natta catalyst.
  • the object of the present invention is also to provide the use of the above hetero atom-containing organic compound as an electron donor in the preparation of a single active site Z-N catalyst.
  • the catalyst provided by the invention can actively catalyze the homopolymerization of ethylene and the copolymerization of ethylene and C 3 -C 18 ⁇ -olefin, and can well control the molecular weight and distribution of the polymer (PDI is 1.6 ⁇ 5.0), copolymerization
  • the monomers are uniformly distributed in the polymer molecular chain.
  • the present invention relates to a class of organic compounds containing a hetero atom which can be used as an electron donor in combination with a magnesium compound, a metal compound and a carrier for the preparation of a single active site of Ziegler-Natta ( Ziegler-Natta) catalyst; such a hetero atom-containing organic compound only needs to be refluxed in an organic solvent for 2 to 48 hours in a high yield, and the preparation is simple and the reaction conditions are mild.
  • a hetero atom-containing organic compound only needs to be refluxed in an organic solvent for 2 to 48 hours in a high yield, and the preparation is simple and the reaction conditions are mild.
  • the prepared single-activity center Ziegler-Natta catalyst can catalyze the homopolymerization of ethylene and the copolymerization of ethylene with C 3 ⁇ C 18 ⁇ -dilute hydrocarbons, and the homopolymerization activity of ethylene under the premise that ruthenium-based aluminum or the like is a cocatalyst.
  • ruthenium-based aluminum or the like is a cocatalyst.
  • the insertion rate of comonomers such as hexene can be greater than 2.0 mole %.
  • the polymer has a narrow molecular weight distribution (PDI of 1.6 to 5.0), resulting in a structure-controlled olefin polymer, which makes the catalyst promising for industrial applications.
  • the structural formula of the hetero atom-containing organic compound is as shown in the following I. In an organic solvent, it may be a mixture of two tautomers I and II:
  • the object of the present invention is also to provide the use of the above hetero atom-containing organic compound as an electron donor in the preparation of a single-site Z-N catalyst.
  • the catalyst provided by the present invention can catalyze the homopolymerization of ethylene and ethylene and 3 ⁇ 4 ⁇ .
  • the 0-olefin copolymerization of 18 well controls the molecular weight and distribution of the polymer (PDI is 1.6 to 5.0), and the comonomer is distributed in the molecular chain of the polymer.
  • the hetero atom-containing organic compound of the present invention has the following structural formula:
  • R 2 hydrogen, a hydrocarbon group of -C30, a substituted hydrocarbon group of -C 3 o, an aromatic hydrocarbon group of C 5 -C 5Q , or a substituted aromatic hydrocarbon group of C 5 -C 5 o, wherein the above groups are the same or different from each other, wherein the phase
  • the ortho groups are independent of each other, bond to each other, or form a ring, but do not form an aromatic ring;
  • R 3 , R 4 , R 5 , RRR 8 , R 9 hydrogen, a radical of -C ⁇ , a substituted hydrocarbyl group of dC 3 o , an aromatic hydrocarbon radical of C 5 -C 50 , or a substitution of C 5 -C 5()
  • An aromatic hydrocarbon group wherein the above groups are the same or different from each other, wherein adjacent groups are independent of each other, bond, or form a ring, especially an aromatic ring;
  • the aromatic hydrocarbon group means phenyl, naphthyl, anthracenyl, phenanthryl or other heteroaromatic hydrocarbon group;
  • the substituted hydrocarbon group or substituted aromatic hydrocarbon group means that the hydrocarbon group or the aromatic hydrocarbon group contains a hydrocarbon group, a silicon group, a halogen group, a carbonyl group, an ester group, an amide group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group. a group or a selenium-containing group;
  • the oxygen-containing group includes an alkoxy group -OR 1Q ; the sulfur-containing group includes -SR 11 or -S(0)R 12 ; the nitrogen-containing group includes -NR 13 R 14 or -N(0)R 15 R 16 ; The phosphorus-containing group includes -PR 17 R 18 or -P(0)R 19 R 2Q ; the selenium-containing group includes -SeR 21 or -Se(0)R 22 ;
  • the novel electron donor (ED) described in the above single-center Ziegle-Natta catalyst is a mixture of one or more of the above-mentioned chemical structure-containing hetero atom-containing organic compounds, preferably ED01, ED02, ED06 ⁇ ED11, ED13 ⁇ ED14, ED18, ED21 to ED28, ED33 to 36, and ED37 to ED44; more preferably ED01, ED06, ED09, ED13, ED14, ED18, ED21 to ED24, ED27 to ED28, ED33, ED35, ED37 to ED38o
  • the compound can be used as described in the literature (Hu W.-Q. et. al., Organometallics 2004, 23, 1684-1688; Wang, C. et. al. Macromol. Rapid Commun. 2005, 26, 1609-1614). synthesis.
  • the diketone compound ( ⁇ ) and the amine compound (IV) are refluxed for 2 to 48 hours in the presence of an organic solvent and the corresponding catalyst. After the reaction is completed, the solvent is removed under reduced pressure, and the solid is solidified by using a solid. The alcohol solvent is recrystallized to obtain the corresponding hetero atom-containing organic compound (Do
  • the catalyst is preferably an organic acid such as formic acid, acetic acid or p-toluenesulfonic acid;
  • the organic solvent is methanol, ethanol or absolute ethanol, preferably anhydrous ethanol;
  • the molar ratio of the diketone compound, the amine compound and the catalyst is 1 to 1.5 : 1: 0.01-0.1;
  • the diketone has the following structure (III):
  • the single active center Ziegle-Natta catalyst provided by the present invention comprises a magnesium compound, a carrier, a metal compound and the above hetero atom-containing organic compound, and has a catalytic active center metal content of 0.1 to 15% by mass.
  • the magnesium compound in the above single-site Ziegle-Natta catalyst is a magnesium halide, a mercapto magnesium, a decyloxy magnesium halide, an alkoxymagnesium, a magnesium halide alcoholate or a mixture thereof; preferably a magnesium halide or an alkyl magnesium.
  • the carrier described in the above single-site Ziegle-Natta catalyst is an inorganic material of an organic material, a metal oxide of Groups 2, 4, 13 and 14 which is A1 ⁇ 20 3 or SiO 2 . And an oxidizing mixture and a mixed oxide, or an oxidized material prepared by a high temperature hydrolysis process of a gaseous metal oxide or a silicon compound, or a clay, or a molecular sieve.
  • L is a halogen atom, a hydrocarbyl group of d-Cso and a substituted hydrocarbyl group of -C30, an oxygen-containing group, a nitrogen-containing group or a corresponding compound, and several L are the same, or different, independent of each other, bonded or ring-formed;
  • the halogen atom herein includes fluorine, chlorine, bromine or iodine;
  • the substituted hydrocarbon group means that the hydrocarbon group contains a hydrocarbon group, a silicon group, a halogen, a carbonyl group, an ester group, an amide group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group or a selenium-containing group;
  • the oxygen-containing group or the corresponding compound includes alkoxyfluorene-OR 23 , tetrahydrofuran or Et 2 0; the nitrogen-containing group includes -NR 24 R 25 or -N(0)R 26 R 27 ;
  • R 23 , R 24 , R 25 , R 26 , R 27 hydrogen, a substituted hydrocarbon group of -C30, a C 5 -C 5 o aromatic hydrocarbon group, or a C 5 -C 5 o substituted aromatic hydrocarbon group, wherein the above groups are The same or different, wherein R 24 and R 25 , R 26 and R 27 are each independently, bonded or ring-formed.
  • the absolute value of the total number of negative charges of all L in the structural formula (V) should be the same as the absolute value of the positive charge of the metal M in the structural formula to ensure the electrical neutrality of the metal compound;
  • M a transition metal atom of Group 4 to Group 6, preferably titanium, zirconium, chromium, vanadium.
  • the metal compound used in the above catalyst is selected from the group consisting of a titanium compound, a zirconium compound, a chromium compound or a vanadium compound; wherein the titanium compound is a complex of titanium tetrahalide, titanium tetrahalide tetrahydrofuran or diethyl ether, preferably TiCl 4 , TiCl 4 (THF) 2; or trihalo embankment group titanium, preferably Ti (OC3 ⁇ 4) d 3, Ti (OC 2 H 5) Cl 3 or Ti (OC 2 H 5) Br 3; or dihalo embankment group titanium, preferably Ti (OCH 3 ) 2 Cl 2 or Ti(OC 2 H 5 ) 2 Cl 2 ; or monohalogenated titanium oxy-oxide, preferably Ti(OCH 3 ) 3 Cl, or Ti(OC 2 3 ⁇ 4 ) 3 Cl ; or tetra-alkane Titanium oxide, tetraamine titanium or tetraalkyl titanium;
  • zirconium compound is preferably ZrC or tetraamine zirconium
  • the complex compound is preferably CrCl 3 or CrCl 3 (THF) 3;
  • the vanadium compound is preferably VC1 5 , VC1 3 (THF) 3 or VCl 3 (PMe 3 ) 2;
  • the above metal compound is TiCl 4 , TiCl 4 (THF) 2 , Ti(NEt 2 ) 4 , Ti(CH 2 Ph) 4 , ZrCl 4 , Zr(NM ) 4 , Zr(NEt 2 ) 4 , CrCl 3 , CrCl 3 (THF) 3 , VC1 3 or VC1 3 (THF) 3 ;
  • the above metal compound is most preferably TiCl 4 , TiCl 4 (THF) 2 , Ti(CH 2 Ph) 4 , ZrCl 4 , CrCl 3 , CrCl 3 (THF) 3 or VCl 3 (THF) 3o.
  • Organic Compounds of Atoms As a novel electron donor (ED), a single active center Ziegle-Natta catalyst can be prepared as follows:
  • the above step (1) is to treat the carrier under an inert gas atmosphere or under reduced pressure at 30 to 1000 ° C for 1 to 24 hours ;
  • the carrier is preferably silica having a particle diameter of 1 to 50 ⁇ m and a specific surface area of 100 to 300 m 2 / g, pore volume 0.5 ⁇ 3mL/g, average pore diameter 10 ⁇ 50nm.
  • the ratio of the magnesium compound to the tetrahydrofuran in the above step (2) is lg: 1 to 100 mL, preferably lg : 20 to 80 mL.
  • the mass ratio of the magnesium compound to the carrier in the above step (3) is 1: 0.1-20, preferably 1: 0.5-10; the molar ratio of the magnesium compound to the metal compound is 0.5 to 100: 1, j) 0.5-50: 1;
  • the molar ratio of the novel electron donor (ED) to the metal compound is 0.01 to 10:1, preferably 0.1 to 5:1; the reaction temperature is room temperature to 100 ° C, preferably 50 to 70 ° C; and the reaction time is 2 to 48 h. Preferably 4 to 241 ⁇ .
  • the inert hydrocarbon solvent used in the above step (3) is a C 5 -C 1G anthracene hydrocarbon or a C 6 -C 8 aromatic hydrocarbon selected from the group consisting of pentamidine, hexane, decane, heptane, octane or toluene, preferably Alkane or toluene.
  • the magnesium compound may be first reacted with the metal compound at room temperature to 100 ° C for 2 to 48 hours, and then reacted with the heat-treated carrier, and then reacted with the above-mentioned electron donor at room temperature to 100 ° C 2 to 48. After the solvent is removed by vacuum, it is washed with an alkane solvent and dried under vacuum to obtain a catalyst.
  • the magnesium compound may be first reacted with the carrier at room temperature to 100 ° C for 2 to 48 hours to obtain a composite carrier, and then the composite carrier carrier obtained is given The organic solvent of the electron and the metal compound is reacted at room temperature to 100 ° C for 2 to 48 hours, and after the same treatment, a catalyst is obtained.
  • the catalyst of the invention is suitable for ethylene homopolymerization, ethylene Ax-dilute hydrocarbon copolymerization and ethylene/cycloolefin copolymerization; and the use of alkyl aluminum, alkyl aluminoxane or a mixture thereof as a cocatalyst in the polymerization, suitable
  • the cocatalyst is selected from the group consisting of triethyl aluminum (AlEt 3 ), triisobutyl aluminum (Al(z'-Bu) 3 ), diethylaluminum dichloride (AlEt 2 Cl), and trihexyl aluminum (Al (-Hex) 3 ), methylaluminoxane (MAO), ethylaluminoxane (EAO), modified methylaluminoxane (MMAO) or a mixture thereof; preferably AlEt 3 , MMAO or a mixture thereof; suitable for polymerization
  • the Al/Ti molar ratio is 20 to
  • the above polymerization may be slurry polymerization or gas phase polymerization; wherein, the slurry polymerization conditions are a total polymerization pressure of 0.1 to 10.0 MPa, a hydrogen pressure of 0 to 1.0 MPa, a polymerization temperature of 80 to 120 ° C; and a slurry polymerization may be super
  • the medium used is a propylene complex, isobutane or hexane
  • the polymerization reactor is a stirred tank or a loop reactor
  • the gas phase polymerization condition is 1.0 to 10.0 MPa
  • the polymerization temperature is 40 to 100 °. C.
  • the polymerization can be carried out in a gas fluidized bed or a gas phase stirred tank.
  • the metal content of the supported catalyst was measured on an ICP-AES, OPTRMA-3000 inductively coupled plasma optical emission spectrometer.
  • the polymer 3 ⁇ 4-NMR spectrum was measured on a Varian XL-300 MHz NMR spectrometer using dichlorobenzene as a solvent at 110 °C.
  • the comonomer insertion rate was calculated according to the method of the literature (J C Randall, JMS-Rev. Maromol. Chem. Phys. 1989, C29 (2 & 3), 201-317).
  • Example 2 ED02: 1H NMR (300 MHz , CDC1 3 ): ⁇ (ppm) 13.02 (s, 1H), 7.94-7.91 (m, 2H), 7.44-6.98 (m, 9H), 6.45-6.42 (m, 1H), 5.96 (s, lH), 2.34 (s, 3H), 2.15 (s, 6H); 13 C NMR (75 MHz, CDCI3): 8 (ppm) 188.76, .162.72, 151.32, 151.06, 140.11, 131.22, 130.73, 128.99, 128.16, 127.36:
  • Example 3 ED05: l R NMR (300 MHz, CDC1 3 ): ⁇ (ppm) 12.82 (s, 1H), 7.88-7.85 (m, 2H), 7.44-6.86 (m, 11H), 5.87 (s, 1H), 2.13 (s, 3H); 13 C NMR (75 MHz, CDC1 3 ): ⁇ (ppm) 188.86, 162.13, 155.96, 150.53, 139.91, 132.63, 130.85, 130.38, 128.19, 127.07, 127.02, 126.89, 124.13 , 120.13, 119.69, 115.97, 94.68, 20.32.
  • Example 4 ED06: !H NMR (300 MHz, CDC1 3 ): ⁇ 12.82 (s, 1H), 7.88-7.84 (m, 2H), 7.42-7.38 (m, 5H), 7.10-6.84 (m, 6H) ), 5.86 (s, 1H), 3.72 (s, 3H), 2.09 (s, 3H).
  • Example 5 ED07: 1H NMR (300 MHz, CDCI3): ⁇ (ppm) 12.84 (s, 1H), 7.89-7.86 (m, 2H), 7.43-6.93 (m, 11H), 5.87 (s, 1H) , 2.15 (s, 3H), 1.28 (s, 9H).
  • Example 6 ED08: 1H NMR (300 MHz, CDC1 3 ): S (ppm) 12.91 (s, 1H), 7.85-7.79 (m, 5H), 7.42-7.26 (m, 11H), 5.85 (s, lH ), 2.17 (s, 3H); 13 C NMR (75 MHz, CDC1 3 ): ⁇ (ppm) 188.72, 162.35, 154.31, 151.14, 139.97, 134.14, 130.73, 130.29, 130.15, 129.91, 128.12, 127.69, 127.09, 127.04, 126.96, 126.82, 126.47, 124.77, 123.63, 119.78, 119.41, 114.20, 94.58, 20.37.
  • Example 7 ED09. 1H NMR (300 MHz, CDC1 3 ): ⁇ 12.82 (s, 1H), 7.95-7.91 (m, 2H), 7.41-7.14 (m, 7H), 5.92 (s, 1H), 3.64 (s, 3H), 2.06 (s, 3H)
  • Example 8 In a 100 mL eggplant flask, 1-phenyl-1,3-butanedione (10 mmol) was added, followed by methanol (15 mL), stirred and dissolved. The o-phenylthioaniline (10 mmol) was added, and finally formic acid (0.5 mL) was added, and the mixture was heated to reflux for 48 hr.
  • Example 12 to Example 15 The following examples are the synthesis of some electron donors (ED):
  • the electron donor (ED) was synthesized according to the method of Example 11, and a diketone compound and an amine compound of the corresponding structures were added, and the obtained
  • the structural characterization data of the electron body (ED) is as follows:
  • Example 13 ED18: 1H MR (300 MHz, CDC1 3 ): ⁇ 12.89 (s, 1H), 7.97-7.94 (m, 2H), 7.44-7.40 (m, 5H), 7.13-6.86 (m, 6H) , 5.91 (s, 1H), 3.80 (s, 3H), 1.99 (s, 3H); 13 C NMR (75 MHz, CDC1 3 ): 6 (ppm) 188.83, 162.59, 160.10, 139.92, 136.71, 136.21, 136.02 , 130.85, 128.51, 128.18, 127.17, 127.03, 125.96, 122.36, 115.06, 109.71, 94.10, 55.32, 20.12.
  • Example 14 ED21: ! H NMR (300 MHz, CDC1 3 ): ⁇ 12.86 (s, 1H), 7.95-7.92 (m, 2H), 7.48-7.20 (m, 7H), 5.95 (s, 1H), 2.00 (s, 3H); 13 C NMR (75 MHz, CDC1 3 ): ⁇ (ppm) 189.28, 162.20, 139.60, 138.08, 131.07, 130.53, 128.42, 128.25, 128.06, 127.61, 127.15, 94.40, 19.96.
  • Example 15 ED22.
  • the electron donor (ED) was synthesized according to the method of Example 16, and the corresponding structure of the diketone compound and the amine compound were added.
  • Example 22 The following electron donor (ED) was synthesized according to the method of Example 21, and the structural characterization data of the obtained electron donor (ED) was as follows:
  • Example 24 ED37: 1H NMR (300 MHz, CDC1 3 ): ⁇ 13.08 (s, 1H), 7.81-7.49 (m, 5H), 5.77 (s, 1H), 3.02 (t, 2H), 2.70 (t, 2H), 2.09 (s, 3H), 1.96 (t, 3H).
  • Example 26 ED 39: 1H NMR (300 MHz, CDC1 3 ): ⁇ 12.38 (s, 1H), 7.81-6.56 (m, 16H), 5.99 (s, 1H), 1.71 (t, 3H).
  • Example 27 ED40: 1H NMR (300 MHz, CDC1 3 ): ⁇ 12.38 (s, 1H), 7.81-7.49 (m, 5H), 7.44-7.22 (m, 5H), 6.75-6.14 (m, 3H) , 5.99 (s, 1H), 2.35 (s, 3H), 1.71 (s, 3H).
  • Example 28 ED41: 1H NMR (300 MHz, CDC1 3 ): ⁇ 12.89 (s, 1H), 7.97-7.64 (m, 5H), 7.44-7.22 (m, 5H), 6.66-6.24 (m, 3H) , 5.95 (s, 1H), 1.91 (s, 3H).
  • Example 30 ED43: 1H NMR (300 MHz, CDC1 3 ): ⁇ 12.38 (s, 1H), 8.80 (s, 1H), 7.94-6.84 (m, 10H), 5.97 (s, 1H), 1.73 (s , 3H).
  • the ES70 type silica gel (product of Ineos) was calcined under a nitrogen atmosphere.
  • the calcination conditions were as follows: treatment at 200 ° C for 2 h, then heating to 400 ° C for 4 h, and naturally cooling under a nitrogen atmosphere. Recorded as ES70 vector.
  • Anhydrous magnesium chloride (1.0 g) was added to tetrahydrofuran (hereinafter referred to as THF) (40 mL), and stirred at 60 ° C for 2 h; TiCl 4 (3.4 mmol) was added dropwise to the above solution, and reacted at 60 ° C for 4 h. Then, the above-mentioned heat-treated ES70 carrier (1.0 g) was added and reacted at 60 ° C for 4 h; finally, the electron donor (4.0 mmol) prepared above was added, and reacted at 60 ° C for 12 h.
  • THF tetrahydrofuran
  • Anhydrous magnesium chloride (1.5 g) was added to tetrahydrofuran (45 mL, hereinafter abbreviated as THF), and stirred at 60 ° C for 2 hours to completely dissolve magnesium chloride; silica gel (1.7 g) was added to the above solution, and the mixture was stirred for 1 hour.
  • n-hexane 40 mL was added at 60 ° C, and the mixture was allowed to cool to room temperature with stirring, allowed to stand, filtered, and dried under vacuum to a liquid powder to obtain a composite carrier.
  • Examples 33 to 69 The following examples are preparations of Ziegler-Natta catalysts containing novel electron donors, all prepared according to the method of Example 32, and the differences and metal content analysis results of Ziegler-Natta catalysts are listed in the table. 1 in. Table 1
  • Examples 70 to 74 The following examples are preparations of Ziegler-Natta catalysts containing novel electron donors, all prepared according to the method of Example 32, and the differences and metal content analysis results of Ziegler-Natta catalysts are listed in the table. 2 in.
  • Example 75 to Example 103 The following examples were carried out for ethylene slurry polymerization.
  • Co-monomer co-monomer example catalyst comonomer amount catalytic activity w PDI insertion rate
  • the mixture in the feed tank was pressed into the polymerization vessel with N 2 gas, and then the pressure in the autoclave was removed, and the temperature in the autoclave was raised to about 70 ° C, and ethylene gas was introduced (3 ⁇ 4 was first introduced into the polymerization).
  • the total pressure in the kettle reached 0.8 MPa.
  • the stirring speed was increased to 250 rpm and the water bath temperature was adjusted to 85 °C.
  • a certain amount of comonomer was added after 20 minutes from the start of the polymerization.
  • the ethylene was stopped, and the temperature in the autoclave was lowered to 50 ° C or less by circulating cooling water.
  • the gas in the system was vented and discharged, and dried to obtain a particulate polymer.

Description

一类含杂原子的有机化合物及其在单活性中心齐格勒-纳塔催化剂中的应用
技术领域 本发明为一类含杂原子的有机化合物及其在制备单活性中心的齐格勒 -纳塔 (Z-NM崔化剂 中的应用。 利用该催化剂， 在助催化剂垸基铝或垸基铝氧垸的作用下， 可以催化乙烯均聚合 或乙烯与 C3〜C18的 oc-稀烃共聚合得到结构可控的烯烃聚合物， 属于烯烃聚合催化剂制备及 应用技术领域。 背景技术 随着聚烯烃工业的快速发展， 高性能聚烯烃材料的生产越来越受到人们的广泛重视。 目 前国际上的研究认为， 高性能聚錄烃材料的生产主要可以通过两种方式实现： 1)利用新型的 单活性中心催化剂包括茂金属催化剂和非茂类催化剂； 2)利用 Z-N催化剂或其在化工工艺上 的改进。 单活性中心催化剂由于催化剂活性中心相同可以得到窄分子量分布聚錄烃 (2左右)， 能够有效实现乙烯与其他单体的共聚合， 而且可以根据需要通过调节主催化剂化学结构达到 制备结构不同的聚合物， 从而得到多种高性能聚烯烃材料。 但是这些新型催化剂存在主催化 剂的稳定性较低、 合成困难、 不易保存、 需要大量昂贵的助催化剂垸基铝氧垸以及必须进行 主催化剂的非均相化等问题， 使其开发与应用受到很大的限制。
相对于单活性中心的茂金属、 非茂金属催化剂而言， 目前工业生产中 Ziegler-Natta催化 剂仍然占据主导地位， 这与 Ziegler-Natta催化剂稳定、 制备简单、 成本低等密切相关。 但是 由于 Ziegler-Natta催化剂具有多种活性中心， 使其不能理想地催化烯烃共聚以及调控聚合物 结构。 近年来， 通过对 Ziegler-Natta催化剂及其化工工艺上的改进， 也逐渐可以生产性能优 良的聚烯烃材料， 例如： 专利 US 5,459,116报道通过使含有酯 (具有至少一个羟基作为给电子 体)的镁溶液与钛化合物反应制备的含钛固体催化剂可以高活性地生产高堆密度的聚合物；专 利 US 5,106,807和 4,330,649通过在体系中添加酯类化合物来控制催化剂的活性和聚合物的 分子量； CN1189487C(PCT/KR2000/001549)提供了一种制备窄分子量分布的乙烯均聚物和共 聚物的制备方法， 分子量分布为 3.6-4.3 ; Terano报道了利用乙烯 /丙烯 /二烯弹性体 (EPDM) 负载的均相 Ziegler-Natta催化剂和表面功能化的二氧化硅负载的催 剂催化乙烯聚合， 通过 改变助催化剂得到不同分子量分布的聚合物 (1.6-30)， 这是用 Ziegler-Natta催化剂所得到的最 窄的分子量分布 (Terano, M., Catalysis Commun. 2003， 4， 657-662; Macromol Chem. Phys. 1998， 199, 1765), 但会造成聚合物的活性或分子量显著下降。 发明目的
本发明的目的是提供一类含杂原子的有机化合物。
本发明的目的还提供上述含杂原子的有机化合物作为给电子体在制备单活性中心的 Z-N 催化剂中的应用。
本发明的目的还提供一类单活性中心的 Ziegle-Natta催化剂及其制备方法。
本发明提供的催化剂可以髙活性地催化乙烯的均聚合及乙稀与 C3〜C18的 α -烯烃共聚 合， 很好地控制聚合物的分子量及其分布 (PDI为 1.6〜5.0)， 共聚单体在聚合物分子链中分布 均匀。 发明概要 本发明涉及一类含杂原子的有机化合物， 这类含杂原子的有机化合物可以作为给电子体 与镁化合物、 金属化合物和载体一起用于制备单活性中心的齐格勒 -纳塔 (Ziegler-Natta)催化 剂； 这类含杂原子的有机化合物仅需要将相应的二酮类化合物和胺类化合物在有机溶剂中回 流 2—48小时即可以高产率得到， 制备简单， 反应条件温和。
所制备的单活性中心 Ziegler-Natta催化剂在垸基铝等为助催化剂的前提下可以高活性地 催化乙烯的均聚合及乙烯与 C3〜C18的 α—稀烃共聚合，乙烯均聚合活性最高达到 18000倍 (克 聚合物 /克催化剂）； 共聚单体如己烯的插入率可以大于 2.0摩尔％。 聚合物的分子量分布窄 (PDI为 1.6〜5.0)， 得到结构可控的烯烃聚合物， 这些特点使该催化剂有望用于工业应用。
所述的含杂原子的有机化合物的结构式如下 I所示， 在有机溶剂中它可以是两种互变异 构体 I和 II的混合物：
Figure imgf000004_0001
(I) (II) 发明内容 本发明的目的是提供一类含杂原子的有机化合物。
本发明的目的还提供上述含杂原子的有机化合物作为给电子体在制备单活性中心 Z-N 催化剂中的应用。
本发明的目的还提供一类单活性中心的 Ziegle-Natta催化剂及其制备方法。
本发明提供的催化剂可以髙活性地催化乙烯的均聚合及乙烯与 ¾〜。18的0 -烯烃共聚 合， 很好地控制聚合物的分子量及其分布 (PDI为 1.6〜5.0)， 共聚单体在聚合物分子链中分布 均勾。
本发明的含杂原子的有机化合物具有如下结构式：
Figure imgf000005_0001
R2: 氢、 -C30的烃基、 -C3o的取代烃基、 C5-C5Q的芳香烃基、 或 C5-C5o的取 代芳香烃基， 上述基团彼此间相同或不同， 其中相邻基团彼此独立、 相互成键、 或成环， 但是不形成芳香环；
R3、 R4、 R5、 R R R8、 R9:氢、 -C^的经基、 d-C3o的取代烃基、 C5-C50的芳 香烃基、或 C5-C5()的取代芳香烃基，上述基团彼此间相同或不同，其中相邻基团彼此独立、 成键、 或成环， 尤其是芳香环；
X: 0、 N、 S、 Se或 P;
当 X是 0、 S或 Se时， X上只有一个取代基 R8或 R9;
所述的芳香烃基是指苯基、 萘基、 蒽基、 菲基或其他杂芳香烃基；
所述的取代烃基或取代芳香烃基是指烃基或芳香烃基含有烃基、 硅基、 卤素、 羰基、 酯基、 酰胺基团、 含氧基团、 含硫基团、 含氮基团、 含磷基团或含硒基团；
含氧基团包括烷氧基 -OR1Q; 含硫基团包括 -SR11或 -S(0)R12; 含氮基团包括 -NR13R14 或 -N(0)R15R16; 含磷基团包括 -PR17R18或 -P(0)R19R2Q; 含硒基团包括 -SeR21或 -Se(0)R22;
R10、 R"、 R12、 R13、 R14 R15、 R16、 R17、 R18、 R19、 R20、 R21、 R22: Q-C^的取代 烃基、 C5-C5o的芳香烃基、 或 C5-C5o的取代芳香烃基， 上述基团彼此间相同或不同， 其中 R13和 RM、 R15和 R16、 R17和 R18、 R19和 R2Q可以彼此成键或成环， 尤其是芳香环； 本发明的含杂原子的有机化合物在有机溶剂中可以以如下的互变异构体存在-
Figure imgf000006_0001
^〜119如前所述。 为了有助于更清楚地了解上述化合物 (I)的结构， 下面举例说明， 需强调的是本发明绝不 仅限以下这些结构的化合物 -
Figure imgf000006_0002
ED13 ED14 ED15 ED16
Figure imgf000007_0001
ΟΡΟΆ όεαι
Figure imgf000007_0002
9£aa seaa
Figure imgf000007_0003
Ζ£ΟΆ icaa oeaa
Figure imgf000007_0004
9t a szaa
Figure imgf000007_0005
otaa eiaa
Figure imgf000007_0006
81?9ΐΟΟ/.ΟΟΖΝ3/Χ3«Ι 上述单中心 Ziegle-Natta催化剂中所述的新型给电子体 (ED)是上述化学结构式的含杂原子 的有机化合物中的一种或几种的混合物， 优选 ED01、 ED02、 ED06〜ED11、 ED13〜ED14、 ED18、 ED21〜ED28、 ED33〜36和 ED37~ED44;更优选 ED01、 ED06、 ED09、 ED13、 ED14、 ED18、 ED21〜ED24、 ED27〜ED28、 ED33、 ED35、 ED37~ED38o 上述含杂原子有机化合物可以利用文献 (Hu W.-Q. et. al.， Organometallics 2004, 23, 1684-1688； Wang, C. et. al. Macromol. Rapid Commun.2005， 26, 1609-1614)所述的方法合成。
本发明的方法是在有机溶剂中和相应的催化剂存在下， 将二酮化合物（ΙΠ)和胺类化合 物（IV) 回流反应 2~48 h， 反应完毕后减压除去溶剂后冷却析出固体， 用醇类溶剂进行重结 晶得到相应的含杂原子的有机化合物 (Do
反应式如下：
Figure imgf000008_0001
其中， 所述的催化剂优选甲酸、 乙酸、 对甲苯磺酸等有机酸； 所述的有机溶剂为甲醇、 乙醇或无水乙醇， 优选无水乙醇；
反应中， 二酮化合物、 胺类化合物和催化剂的摩尔比为 1〜1.5: 1： 0.01-0.1；
所述二酮具有下面的结构 (III):
Figure imgf000008_0002
(Mi) 所述的胺化合物具有下面的结构 (IV):
Figure imgf000009_0001
(IV)
上述 R1〜！9如前所述。 本发明提供的单活性中心的 Ziegle-Natta催化剂， 由镁化合物、载体、金属化合物以及上 述含杂原子的有机化合物组成， 催化活性中心金属含量为 0.1〜15质量％。 上述单活性中心的 Ziegle-Natta催化剂中的镁化合物为卤化镁、 垸基镁、 垸氧基卤化镁、 烷氧基镁， 卤化镁醇合物或它们的混合物； 优选卤化镁或烷基镁。 上述单活性中心的 Ziegle-Natta催化剂中所述的载体为有机材料、第 2、 4、 13和 14族金 属氧化物在内的无机氧化物， 所述无机氧化物为 A½03， 或 Si02， 以及氧化混合物和混合氧 化物， 或是由气态金属氧化物或硅化合物通过高温水解过程而制备的氧化材料， 或粘土， 或 分子筛。
上述催化剂中所用的金属化合物的结构如 (V)所示：
MLa (V)
其中：
a: 3、 4、 5或 6;
L:是卤原子、 d-Cso的烃基及 -C30的取代烃基、含氧基团、含氮基团或相应的化合物， 几个 L相同， 或不同， 彼此独立、 成键或成环；
这里的卤原子包括氟、 氯、 溴或碘；
取代烃基是指烃基含有烃基、 硅基、 卤素、 羰基、 酯基、 酰胺基团、 含氧基团、 含硫基 团、 含氮基团、 含磷基团或含硒基团；
含氧基团或相应化合物包括烷氧棊 -OR23、 四氢呋喃或 Et20; 含氮基团包括 -NR24R25或 -N(0)R26R27;
R23、 R24、 R25、 R26、 R27: 氢、 -C30的取代烃基、 C5-C5o的芳香烃基、 或 C5-C5o的取代 芳香烃基， 上述基团彼此间相同或不同， 其中 R24和 R25、 R26和 R27彼此独立、 成键或成环。 结构式 (V)中所有 L所带负电荷总数的绝对值应与结构式中金属 M所带正电荷的绝对值 相同以保证金属化合物的电中性；
M: 第四族到第六族的过渡金属原子， 优选钛、 锆、 铬、 钒。
上述催化剂中所用的金属化合物选自钛化合物、 锆化合物、 铬化合物或钒化合物； 其中钛化合物为四卤化钛、 四卤化钛的四氢呋喃或乙醚的络合物， 优选 TiCl4、 TiCl4(THF)2; 或三卤代垸氧基钛， 优选 Ti(OC¾)d3、 Ti(OC2H5)Cl3或 Ti(OC2H5)Br3 ； 或二卤 代垸氧基钛，优选 Ti(OCH3)2Cl2或 Ti(OC2H5)2Cl2; 或一卤代垸氧基钛，优选 Ti(OCH3)3Cl、或 Ti(OC2¾)3Cl ； 或四烷氧基钛， 四胺基钛或四烷基钛；
其中锆化合物优选 ZrC 或四胺基锆；
其中络化合物优选 CrCl3或 CrCl3(THF)3;
其中钒化合物优选 VC15、 VC13(THF)3或 VCl3(PMe3)2;
上述金属化合物更优选 TiCl4、 TiCl4(THF)2、 Ti(NEt2)4、 Ti(CH2Ph)4、 ZrCl4、 Zr(NM )4、 Zr(NEt2)4、 CrCl3、 CrCl3(THF)3、 VC13或 VC13(THF)3;
上述金属化合物最优选 TiCl4、 TiCl4(THF)2、 Ti(CH2Ph)4、 ZrCl4、 CrCl3、 CrCl3(THF)3或 VCl3(THF)3o 本发明所述一类含杂原子的有机化合物作为新型给电子体 (ED)， 可以用如下方法制备单 活性中心的 Ziegle-Natta催化剂：
(1)将作为载体的有机或无机固体或两者的复合物进行热处理；
(2)在室温〜 70° C条件下， 将镁化合物溶解于四氢呋喃中形成溶液；
(3)按照一定顺序向上述溶液 (2)中加入步骤 (1)中所述载体、 金属化合物以及新型给电子 体 (ED)， 在一定温度下反应一段时间， 经脱除溶剂、 用惰性烃类溶剂洗涤和干燥后制 得 Ziegle-Natta催化剂。
上述步骤 (1)是将载体在惰气气氛保护或减压条件下， 30〜1000°C处理 l〜24h; 载体优 选二氧化硅， 其粒径为 1〜50μπι， 比表面积 100〜300m2/g， 孔体积 0.5〜3mL/g， 平均孔径 10〜50nm。
上述步骤 (2)中镁化合物与四氢呋喃的比例为 l g: l~100mL, 优选 lg: 20〜80mL。
上述步骤 (3)中镁化合物与载体的质量比为 1 : 0.1-20, 优选 1: 0.5-10； 镁化合物与金 属化合物的摩尔比为 0.5〜100： 1， j) 0.5-50： 1； 新型给电子体 (ED)与金属化合物的摩尔 比为 0.01〜10： 1，优选 0.1~5： 1；反应温度为室温至 100° C，优选 50〜70°C;反应时间为 2〜 48h， 优选 4〜241ι。 上述步骤 (3)中所用的惰性烃溶剂为 C5〜C1G的垸烃或 C6〜C8的芳烃， 选自戊垸、 己烷、 癸烷、 庚烷、 辛烷或甲苯， 优选己烷或甲苯。
上述步骤 (3)中可以是镁化合物先与金属化合物在室温〜 100° C反应 2〜48小时， 然后与 热处理后的载体作用， 再与上述给电子体在室温〜 100° C反应 2〜48小时， 真空除溶剂后用 烷烃类溶剂洗涤、真空干燥得到催化剂；也可以是镁化合物先与载体在室温〜 100° C反应 2〜 48小时得到复合载体， 然后得到的复合载体载体再与上述给电子体和金属化合物的有机溶剂 在室温〜 100° C反应 2〜48小时， 经过同样处理后得到催化剂。
本发明所述一类含有新型给电子体的 Ziegle-Natta烯烃聚合催化剂的制备方法过程中所 使用的各种溶剂均需要严格的除水除氧处理， 所有操作均在无水无氧的条件下进行， 在实施 例中不再另外说明。
本发明所述的催化剂适用于乙烯均聚合、乙稀 Ax-稀烃共聚合以及乙烯 /环烯烃共聚合；聚 合时需以烷基铝、 烷基铝氧垸或它们的混合物作为助催化剂， 适宜的助催化剂选自三乙基铝 (AlEt3)、三异丁基铝 (Al(z'-Bu)3)、 一氯二乙基铝 (AlEt2Cl)、三己基铝 (Al( -Hex)3)、 甲基铝氧烷 (MAO)、乙基铝氧烷 (EAO)、修饰的甲基铝氧烷 (MMAO)或它们的混合物；优选 AlEt3、 MMAO 或它们的混合物； 聚合时适宜的 Al/Ti摩尔比为 20〜1000， 优选 20〜500； 所述的 α-烯烃为 C3〜C2Q烯烃， 选自丙烯、 1-丁烯、 1-己婦、 1-庚烯、 4-甲基 -1-戊烯、 1-辛烯、 1-癸烯、 1-十一 炼、 1-十二烦、 1-十四烯、 1-十六炼、 1-十八烯； 所述的环烯烃为环戊烯、 环己烯、 降冰片烯 或有烷基取代的环戊烯、 环己烯、 降冰片烯； 所述的 a-烯烃或环烯烃上可以有羟基、 羰基、 酯基或胺基。
上述的聚合可为淤浆聚合或气相聚合； 其中， 淤浆聚合条件为聚合总压力为 0.1〜 10.0MPa、氢气压力为 0〜1.0MPa、聚合温度 80〜120° C; 淤桨聚合可在超临界或亚临界状态 下进行， 采用的介质为丙綜、 异丁烷或己烷， 聚合反应器为搅拌釜或环管反应器； 气相聚合 条件为 1.0〜10.0MPa、 聚合温度为 40〜100° C， 聚合可在气体流化床或气相搅拌釜中进行。
负载型催化剂中金属含量测定在 ICP-AES, OPTRMA-3000 电感耦合等离子体发射光谱 仪上进行。
聚合物分子量 （MW, M„) 分子量分布 用 Waters Alliance GPC2000.在 1,2,4 三氯苯（流速 l.OmL/min) 中 135。C下， 以聚苯乙烯为标样测定。
聚合物 ¾-NMR谱在 Varian XL-300 MHz核磁共振仪上以 二氯苯为溶剂，在 110°C 下测定。共单体插入率根据文献 ( J C Randall, JMS-Rev. Maromol. Chem. Phys. 1989, C29(2 & 3), 201-317) 的方法计算得到。
附图说明 图 1 : 实施例 9中化合物 ED14的单晶结构图；
图 2: 实施例 78中乙稀 /1-己烯共聚物的 13C NMR谱图 (己烯插入率 =1.04 mol-%)。
最佳实施例 下面的实施例将更好的说明本发明，但需强调的是本发明绝不仅限于这几个实施例所表 述内容。
实施例 1 新型给电子体 (ED)的合成：
Figure imgf000012_0001
ED01
在 100 mL茄形瓶中加入 1-苯基 -1,3-丁二酮（42.0 mmol), 加入无水乙醇（30 mL)， 搅 拌溶解后加入的 2-苯氧基苯胺 (40.0 mmol)， 最后加入冰醋酸（3 mL)， 加热回流 30 h后， 自然冷却并减压除去溶剂后置于冰箱。 过滤得到黄色固体， 用无水乙醇重结晶得到产物 ED01(5.534 g,产率 =42%)。 EDOl: 1H NMR (300 MHz, CDC13): δ (ppm) 12.82 (s， 1H)， 7.87-7.84 (m, 2H), 7.44-6.91 (m, 12H), 5.86 (s, 1H), 2.12 (s, 3H); 13C NMR (75 MHz, CDC13): δ (ppm) 188.83, 162.14, 155.35， 150.68, 139.91， 130.85， 130.29, 129.68, 128.52, 128.18, 127.06,127.01, 126.87, 124.03, 119.77， 119.53, 94.65, 20.34; 实施例 2〜实施例 Ί 以下实施例为一些给电子体 (ED)的合成：
按照实施例 1的方法， 加入相应结构的二酮化合物和胺类化合物合成给电子体 (ED)， 所 得给电子体 (ED)的结构表征数据如下： 实施例 2: ED02: 1H NMR (300 MHz, CDC13): δ (ppm) 13.02 (s, 1H), 7.94-7.91 (m, 2H), 7.44-6.98 (m, 9H), 6.45-6.42 (m, 1H), 5.96 (s,lH)， 2.34 (s,3H), 2.15 (s, 6H); 13C NMR (75 MHz, CDCI3): 8 (ppm) 188.76, .162.72, 151.32, 151.06, 140.11, 131.22, 130.73, 128.99, 128.16, 127.36:
127.09, 126.91, 126.44, 125.25, 121.29, 113.45, 94.43, 20.48, 16.32。 实施例 3: ED05: lR NMR (300 MHz, CDC13): δ (ppm) 12.82 (s， 1H)， 7.88-7.85 (m， 2H), 7.44-6.86 (m, 11H), 5.87 (s, 1H), 2.13 (s, 3H); 13C NMR (75 MHz, CDC13): δ (ppm) 188.86, 162.13, 155.96, 150.53, 139.91, 132.63, 130.85， 130.38, 128.19, 127.07, 127.02, 126.89, 124.13, 120.13, 119.69, 115.97， 94.68, 20.32。 实施例 4: ED06: !H NMR (300 MHz, CDC13): δ 12.82 (s, 1H), 7.88-7.84 (m, 2H), 7.42-7.38 (m, 5H), 7.10-6.84 (m, 6H), 5.86 (s, 1H), 3.72 (s, 3H), 2.09 (s, 3H)。 实施例 5: ED07: 1H NMR (300 MHz, CDCI3): δ (ppm) 12.84 (s, 1H), 7.89-7.86 (m, 2H), 7.43-6.93 (m, 11H), 5.87 (s, 1H), 2.15 (s, 3H), 1.28 (s， 9H)。 实施例 6: ED08: 1H NMR (300 MHz, CDC13): S (ppm) 12.91 (s， 1H), 7.85-7.79 (m, 5H), 7.42-7.26 (m， 11H), 5.85 (s,lH), 2.17 (s， 3H); 13C NMR (75 MHz, CDC13): δ (ppm) 188.72, 162.35, 154.31, 151.14， 139.97, 134.14, 130.73, 130.29, 130.15, 129.91, 128.12， 127.69, 127.09, 127.04, 126.96, 126.82, 126.47, 124.77, 123.63, 119.78, 119.41, 114.20, 94.58, 20.37。 实施例 7: ED09. 1H NMR (300 MHz, CDC13): δ 12.82 (s, 1H), 7.95-7.91 (m, 2H), 7.41-7.14 (m, 7H), 5.92 (s, 1H), 3.64 (s， 3H), 2.06 (s, 3H) 实施例 8 在 100 mL茄形瓶中加入 1-苯基 -1,3-丁二酮（lO mmol) , 再加入甲醇（15mL)， 搅拌溶解 后加入的邻苯硫基苯胺 （lO mmol), 最后加入甲酸（0.5mL)， 加热回流 48h后， 自然冷却并 减压除去溶剂后置于冰箱。过滤得到黄色固体，用无水乙醇重结晶得到产物 ED13(1.8156 g,产 率 =53%)。 1H NMR (300 MHz, CDC13): δ (ppm) 12.93 (s， 1H), 7.94-7.91 (m， 2H)， 7.47-7.38 (m, 5H), 7.31-7.15 (m, 7H), 5.85 (s， 1H), 1.97 (s, 3H); 13C NMR (75 MHz, CDC13): δ (ppm) δ 188.84, 162.06, 139.94, 137.78, 133.95, 133.52, 132.55, 131.20, 130.83, 129.25, 127.78, 127.22, 127.14, 126.99, 126.88, 94.32, 20.06,. IR: 3060, 1597, 1574, 1546, 1508, 1462, 1425， 1317, 1287， 1271, 1060, 760， 747, 732cm"1; LRMS-EI(m/z): 345 (M"), 91 (100); 元素 析 C22H19NOS:计算值 C,
76.49; H, 5.54; N, 4.05. 实测值： C, 76.64; H, 5.63; N, 3.77。 实施例 9 在 100 mL茄形瓶中加入 1-苯基 -1 ,3-丁二酮 （1.92 mmol)， 再加入无水乙醇（7 mL)， 搅 拌溶解后加入的 2-氨基 -2,6-二甲基苯硫醚（1.74 mmol)， 最后加入醋酸 (0.6mL), 加热回流 24h后， 自然冷却并减压除去溶剂后置于冰箱。 过滤得到黄色固体， 用无水乙醇重结晶得到 产物 ED14(0.4657 g,产率 =72%)。1H NMR (300 MHz, CDC13): δ 12.84 (s, 1H), 7.99-7.96 (m, 2H):
7.46- 7.43 (m, 3H), 7.25-7.01 (m, 6H), 6.46-6.43 (m, 1H), 5.99 (s, 1H), 2.40 (s, 6H), 2.06 (s," 3H); 13C NMR (75 MHz, CDC13): δ (ppm) 188.93, 163.21, 144.06, 139.91, 136.21, 135.14, 130.83, 129.45,129.17, 128.54, 128.15, 127.50, 127.15, 124.86, 124,76, 93.95, 21.68, 20.01; IR: 3450, 3060: 2920， 1599, 1577, 1550， 1461, 1317， 1284， 747cm"1; LRMS-EI(m/z): 373 (M""), 105 (100);元素分 析计算值 C24H23NOS: C， 77.18; H, 6.21 ; N, 3.75. 实测值： C, 77.44; H, 6.18; N, 3.34。 ED14的单 晶结构列于附录中图 1。 实施例 10
在 100 mL茄形瓶中加入 1-苯基 -1,3-丁二酮（1.16 mmol)， 再加入无水乙醇（7 mL)， 搅 拌溶解后加入的 2-氨基 -2,6-二异丙基基苯硫醚 ( 1.05 mmol), 最后力卩入甲酸（0.2mL)， 加热 回流 8h后， 自然冷却并减压除去溶剂后置于冰箱。过滤得到黄色固体， 用无水乙醇重结晶得 到产物 ED15(0.3203 g,产率 =71%)。 ED15: 1H NMR (300 MHz, CDC13): δ 12.82 (s, 1H), 8.00-7.97 (m, 2H), 7.48-7.01 (m, 9H), 6.40-6.37 (m, 2H), 6.02 (s, 1H), 2.08 (s, 3H), 1.15-1.12 (d, J= 7.2Hz, 12H); 13C NMR (75 MHz, CDC13): δ (ppm) 188.98, 154.22, 139.96, 138.55, 130.87, 130.45, 128.22, 127.57, 127.50, 127.20, 126.78, 125.34, 124.55, 124.24, 93.89, 31.66， 24.17, 19.96; IR: 3060, 2960, 1597,1557, 1461, 1319, 1284， 745cm"1; LRMS-EI(m/z): 430 (M4), 252 (100);元素 分析 C28H31NOS:计算值 C, 78.28; H,7.27; N, 3.26.实测值： C, 78.29; H, 7.51; N, 3.07。 实施例 11
在 100 mL茄形瓶中加入 1-苯基 -1,3-丁二酮（1.22 mmol)， 再加入无水乙醇（10 mL)， 搅 拌溶解后加入的 2-氨基 -2,6-二氯苯硫醚（1.11 mmol), 最后加入甲酸（0.5mL)， 加热回流 20 h后， 自然冷却并减压除去溶剂后置于冰箱。 过滤得到黄色固体， 用无水乙醇重结晶得到产 物 ED16(0.3363 g,产率 =73%)。 1H NMR (300 MHz, CDC13): δ 12.81 (s, 1H), 7.97-7.94 (m, 2H),
7.47- 7.10 (m, 8H), 6.73-6.70 (m, 1H), 5.96 (s, 1H), 2.06 (s, 3H); 13C NMR (75 MHz, CDC13): δ (ppm) 189.00, 163.02, 141.70, 139.87， 136.02, 134.02, 130.86, 130.83, 130.29, 128.95, 128.17, 127.84, 127.57, 127.18, 126.83, 126.22, 94.16, 20.08; IR: 3420, 3060, 1600, 1578, 1553， 1426, 1317， 1283, 782, 750cm-1; LRMS-EI(m/z): 414 ( ), 105 (100);元素分析 C22H17C12N0S: 计算 值 C, 63.77; H, 4.14; N, 3.38. 实测值： C, 63.54; H, 4.04; N, 3.20。 实施例 12〜实施例 15 以下实施例为一些给电子体 (ED)的合成： . 按照实施例 11的方法合成给电子体 (ED)，加入相应结构的二酮化合物和胺类化合物，所 得给电子体 (ED)的结构表征数据如下： 实施例 12: ED17: 1H NMR (300 MHz, CDC13): δ 12.95 (s, 1H), 7.91-7.88 (m, 2H), 7.47-7.15 (m, 11H), 5.81 (s, 1H), 1.95 (s, 3H); 13C NMR (75 MHz, CDC13): δ (ppm) 189.00, 161.53, 139.83, 138.97, 136.57, 134.73, 132.99, 131.35， 130.89, 130.69, 130.08, 129.32, 128.44, 128.15, 127.39， 127.12, 126.99, 126.83， 94.59, 19.99。 实施例 13: ED18: 1H MR (300 MHz, CDC13): δ 12.89 (s, 1H), 7.97-7.94 (m, 2H)， 7.44-7.40 (m， 5H)， 7.13-6.86 (m, 6H), 5.91 (s， 1H), 3.80 (s， 3H)， 1.99 (s， 3H); 13C NMR (75 MHz, CDC13): 6 (ppm) 188.83, 162.59, 160.10， 139.92, 136.71， 136.21, 136.02, 130.85, 128.51, 128.18, 127.17, 127.03, 125.96, 122.36, 115.06, 109.71, 94.10， 55.32， 20.12。 实施例 14: ED21: !H NMR (300 MHz, CDC13): δ 12.86 (s, 1H), 7.95-7.92 (m, 2H), 7.48-7.20 (m, 7H), 5.95 (s, 1H), 2.00 (s, 3H); 13C NMR (75 MHz, CDC13): δ (ppm) 189.28, 162.20, 139.60, 138.08, 131.07, 130.53, 128.42, 128.25, 128.06, 127.61, 127.15, 94.40, 19.96。 实施例 15: ED22. 1H NMR (300 MHz, CDC13): δ 12.82 (s, 1H), 7.94-7.90 (m, 2H), 7.41-7.13 (m， 7H), 5.91 (s， 1H), 2.47 (s, 3H), 2.04 (s, 3H) 实施例 16
在 100 mL茄形瓶中加入苯甲酰丙酮 （5.54 mmol)， 再加入无水乙醇（5 mL)， 搅拌溶解 后加入的 2-氨基丙基苯硫醚（5.54 mmol), 最后加入甲酸（0.5mL)， 加热回流 36 h后， 自然 冷却并减压除去溶剂后置于冰箱。 过滤得到黄色固体， 用无水乙醇重结晶得到产物
ED23(1.7254 g,产率 =68%)。 1H NMR (300 MHz, CDC13): δ 12.86 (s, 1H), 7.96-7.94 (m, 2H)，
7.46-7.17 (m, 7H), 5.94 (s, 1H), 2.89-2.84 (t, J=7.2Hz, 2H), 2.04 (s, 3H), 1.71-1.64 (m, 2H)， 1.05-1.00 (t, J=7.5Hz, 3H). 13C NMR (75 MHz, CDC13): 188.83, 162.45, 139.97, 137.53, 134.23, 130.83, 128.83, 128.17, 127.19， 126.85, 126.75, 125.89, 94.21, 34.64, 22.28, 20.23, 13.52; IR: 3060, 2962, 1598, 1574, 1548, 1515， 1461, 1432, 1317, 1280, 1195, 1064, 754, 708cm"1; LRMS-EI(m/z): 311 (M+), 105 (100);元素分析 C19H21NOS:计算值 C, 73.27; H,6.80; N,4.50.实测值： C, 73.20; H, 6.81; N, 4.23. 实施例 17~实施例 20 以下实施例为一些给电子体 (ED)的合成：
按照实施例 16的方法合成给电子体 (ED)，加入相应结构的二酮化合物和胺类化合物，所 得给电子体 (ED)的结构表征数据如下： 实施例 17: ED24: 1H NMR (300 MHz, CDC13): δ 12.94 (s, 1H), 7.97-7.93 (m, 2H), 7.49-7.17 (m, 7H), 5.93 (s, 1H), 3.41-3.37 (m, 1H)， 2.07 (s, 3H), 1.31-1.29 (d, J=6Hz, 6H); 13C NMR (75 MHz, CDC13): δ (ppm) 188.67, 161.81, 139.95, 139.17, 132.57， 131.96, 130.75, 128.11, 127.10, 126.34, 126.20, 94.43, 37.50, 22.91, 20.34; IR: 3060, 2980, 1598, 1577, 1511, 1436, 1320, 1280, 758, 703, 673 cm ; L MS-EI(m/z): 311 ( ^), 105 (100);元素分析 C19H21NOS:计算值 C, 73.27; H, 6.80; N, 4.50.实测值： C, 73.19; H, 6.74; N, 4.14。 实施例 18: ED25: 1H NMR (300 MHz, CDC13): δ (ppm) 13.17 (s, 1H), 7.98-7.94 (m, 2H), 7.66-7.63 (m, 1H), 7.47-7.17 (m; 6H)， 5.93 (s， 1H), 2.14 (s, 3H)， 1.32 (s, 9H); 13C NMR (75 MHz, CDCI3): δ (ppm) 188.53, 160.52, 143.05, 139.82, 130.80, 129.64, 128.16, 127.20, 125.20, 125.02, 95.17, 47.86, 30.84, 20.82; IR: 3060, 2980, 1596， 1577, 1555, 1456, 1321, 1280, 759 cm"1; LRMS-EI(m/z): 325 (M"1"), 105 (100);元素分析 C2QH23NOS: 计算值 C， 73.81; H, 7.12; N, 4.30. 实测值： C, 73.73; H, 7.07; N, 3.95。 实施例 19: ED26: 1H NMR (300 MHz, CDC13): δ (ppm) 12.35 (s, 1H), 7.34-7.17 (m, 8H), 5.44 (s, 1H), 1.91 (s, 3H); 13C NMR (75 MHz, CDC13): δ (ppm) 176.53, 167.93, 136.39, 134.25, 132.97, 132.34, 131.83, 129.41, 128.30, 128.09, 127.70, 127.25, 115.47, 90.81 (t), 19.92; IR: 3155, 2925, 2852, 1620, 1590, 1565, 1467, 1439, 1428, 1292, 1241, 1062, 861， 753, 745, 734cm-1;元素 分析 C17H14F3NOS:计算值 C, 60.52; H， 4.18; N, 4.15.实测值： C, 60.68; H, 4.15; N, 3.95。 实施例 20: ED27: 1H NMR (300 MHz, CDCI3): δ (ppm) 12.91 (s, 1H), 7.99-6.41 (m, 18H), 6.08 (s, 1H); 13C NMR (75 MHz, CDC13): δ (ppm) 189.59, 160.50, 139.94, 139.68, 135.87, 134.50, 132.95, 131.91, 131.31, 129.61, 129.12, 128.91, 128.44, 128.27, 128.03, 127.53, 127.41, 127.36, 124.90, 124.46, 97.92; IR: 3051, 1545, 1480, 1438, 1330, 1282, 1207, 1050, 1022, 781, 754, 686cm-1;元素分析 C27H21NOS:计算值 C, 79.57; H, 5.19; N, 3.44. 实测值： C, 79.23; H, 5.18; N: 3.13。 实施例 21
在 100 mL茄形瓶中加入乙酰丙酮（lO imnol), 再加入甲醇 （15 mL)， 搅掙溶解后加入 的 2-苯硫基苯胺 （lO mmol), 最后加入甲酸（l mL)， 加热回流 24 h后， 自然冷却并减压除 去溶剂后置于冰箱。 过滤得到黄色固体， 用无水乙醇重结晶得到产物 ED28(1.8156 g,产率 =52.6%) 1H NMR (300 MHz, CDC13): δ (ppm) 12.34 (s, 1H), 7.35-7.26 (m, 5H)， 7.19-7.11 (m, 4H), 5.15 (s, 1H), 2.09 (s, 3H), 1.84 (s,3H); 13C NMR (75 MHz, CDC13): δ (ppm) 196.30, 159.95, 137.83, 133.68， 132.36, 131.14,, 129.20, 128.92, 127.71, 127.17, 126.85, 126.66, 126.33, 97:77,29.15,19.49. IR: 3058, 1575, 1500, 1462, 1439, 1377, 1355, 1275, 1186, 1063, 1024, 993, 921, 751, 691, 660cm'1; LRMS-EI(m/z): 283 (IV^), 174 (100);元素分析 C17H17NOS:计算值 C, 72.05; H, 6.05; N, 4.94.实测值： C, 72.09; H, 6.02; N, 4.78。 实施例 22~实施例 31 以下实施例为一些给电子体 (ED)的合成：
按照实施例 21的方法合成下述给电子体 (ED)， 所得给电子体 (ED)的结构表征数据如下： 实施例 22: ED33: 1H NMR (300 MHz, CDC13): δ (ppm) 12.90 (s, 1H), 7.93-7.14 (m, 19H), 5.81 (s, 1H), 1.94 (s, 3H 实施例 23: ED35: 1H NMR (300 MHz, CDC13): δ (ppm) 12.87 (s, 1H), 7.95-7.11 (m, 24H), 6.35 (s, 1H)。 实施例 24: ED37: 1H NMR (300 MHz, CDC13): δ 13.08 (s, 1H), 7.81-7.49 (m, 5H), 5.77 (s, 1H), 3.02 (t， 2H)， 2.70 (t, 2H)， 2.09 (s， 3H)， 1.96 (t, 3H)。 实施例 25: ED38: 1H NMR (300 MHz, CDC13): δ 13.28 (s, 1H), 7.81-7.49 (m， 5H), 5.77 (s, 1Η)， 3.02 (t, 2H), 2.88 (m, 1H), 2.70 (t, 2H), 1.95 (t, 3H), 1.25(d, 6H)。 实施例 26: ED39: 1H NMR (300 MHz, CDC13): δ 12.38 (s, 1H), 7.81-6.56 (m, 16H), 5.99 (s, 1H), 1.71 (t，3H)。 实施例 27: ED40: 1H NMR (300 MHz, CDC13): δ 12.38 (s, 1H), 7.81-7.49 (m, 5H), 7.44-7.22 (m, 5H), 6.75-6.14 (m, 3H), 5.99 (s， 1H), 2.35 (s， 3H), 1.71 (s, 3H)。 实施例 28: ED41: 1H NMR (300 MHz, CDC13): δ 12.89 (s, 1H), 7.97-7.64 (m, 5H), 7.44-7.22 (m， 5H), 6.66-6.24 (m, 3H), 5.95 (s, 1H), 1.91 (s, 3H)。 实施例 29: ED42: 1H NMR (300 MHz, CDC13): δ 12.38 (s, 1H), 9.77 (s, 1H), 7.81-7.49 (m, 5H), 7.33-6.98 (m, 5H), 6.61-6.21 (m, 4H), 5.99 (s, 1H), 1.71 (s, H)。 实施例 30: ED43: 1H NMR (300 MHz, CDC13): δ 12.38 (s, 1H), 8.80 (s, 1H), 7.94-6.84 (m, 10H), 5.97 (s, 1H), 1.73 (s, 3H)。 实施例 31: ED44: 1H NMR (300 MHz, CDC13): δ 12.40 (s, 1H), 7.98-6.39 (m, 12H), 5.95 (s, 1H), 1.75 (s, 3H
实施例 32 本发明单中心 Ziegle-Natta催化剂的制备：
(1)载体的热处理
取 ES70型硅胶 (Ineos公司产品)在氮气气氛下焙烧。 其焙烧条件为： 于 200° C处理 2h， 然后升温至 400° C处理 4h， 在氮气氛下自然冷却。 记为 ES70载体。
(2)载体型催化剂的制备
方法一：
将无水氯化镁（l.Og)加入到四氢呋喃 (以下简称 THF) (40mL)中， 在 60°C下搅拌 2h; 向上述溶液中滴加 TiCl4 (3.4 mmol), 在 60° C下反应 4h， 然后加入上述热处理后 ES70载体 ( l.Og)，在 60° C下反应 4h;最后加入上述制备的给电子体（4.0 mmol)，在 60° C下反应 12h。 反应结束后减压蒸除溶剂， 产物用己垸 (3x20mL)洗涤， 然后在减压下干燥得到流动性好的 Ziegler-Natta催化剂。 Ti含量： 3.20 wt- %。
方法二：
将无水氯化镁 ( 1.5g)加入到四氢呋喃 (45mL， 以下简称 THF)中， 在 60°C下搅拌 2h， 使氯化镁完全溶解； 向上述溶液中加入硅胶（1.7克）， 搅拌 1小时。在 60°C， 向上述体系中 加入正己烷（40 mL)， 搅拌下使自然冷却至室温， 静置， 过滤， 固体真空干燥至流动性粉末， 得复合载体。
向 TiCl4(THF)2 的 CH2C12 (2 mL)溶液中滴加给电子体 ED01的 CH2C12 (2 mL)溶液，并将 所得到的溶液滴加至上述复合载体（0.77克)， 搅拌使混合均勾， 然后在减压下干燥得到流动 性好的 Ziegler-Natta催化剂。
实施例 33〜实施例 69 以下实施例为含有新型给电子体的 Ziegler-Natta催化剂的制备，均按照实施例 32的方法 一制备， 不同之处及 Ziegler-Natta催化剂的金属含量分析结果列于表 1中。 表 1
无水氯化镁 THF TiCl4用 载体 给电子体 载体型催化剂中 实施例 催化剂编号 用量 用量 量 及其用量 及其用量 金属含量 (wt-%)
(g) (mL) (mmol) (g) (mmol) Ti
33 SC02 1.0 40 3.4 ES70(1.0) ED02(3.5) 4.61
34 SC03 1.0 40 3.4 ES757(1.0) ED02(3.5) 4.56
35 SC04 1.0 40 3.4 Grace955(1.0) ED02(3.5) -
36 SC05 1.2 50 3.4 ES70(1.0) ED05(3.5) 4.35
37 SC06 1.2 50 3.4 ES70(1.0) ED06(4.O) -
38 SC07 0.9 40 3.4 ES70X(1.0) ED07(6.8) 3.75
39 SC08 1.2 50 3.4 ES70Y(1.1) ED08(4.0) -
40 SC09 1.0 40 3.4 ES70(1.0) ED09(4.0) 4.65
41 SC11 1.0 40 3.4 ES70(1.0) ED13(4.1) 4.50
42 SC12 1.1 40 1.7 ES70(1.3) ED13(3.4) 1.68
43 SC13 0.5 20 3.4 ES70(1.0) ED13(4.1) 1.09
44 SC14 1.0 60 6.8 ES70(2.0) ED13(8.2) 5.65
45 SC15 1.0 40 3.0 ES70(1.0) ED13(1.5) 4.59
46 SC16 2.0 60 3.2 ES757(2.0) ED13(3.8) -
47 SC17 0.5 30 1.7 ES70(0.5) ED14(2.6) -
48 SC18 0.5 30 1.7 ES70(0.5) ED15(2.6) 4.45
49 SC19 0.5 30 1.7 ES70(0.5) ED16(2.6) - 50 SC20 0.5 30 1.7 ES70(0.5) ED17(2.6) 4.35
51 SC21 0.5 30 1.7 ES70(0.5) ED18(2.6) 4.37
52 SC22 0.5 30 1.7 ES70(0.5) ED21(2.6) 3.95
53 SC23 0.5 30 1.7 ES70(0.5) ED22(2.6) -
54 SC24 0.5 30 1.7 ES70(0.5) ED23(2.6) 4.43
55 SC25 0.5 30 1.7 ES70(0.5) ED24(2.6) -
56 SC26 0.5 30 1.7 ES70(0.5) ED25(2.6) 4.53
57 SC27 1.0 60 6.8 ES70(2.0) ED26(8.2) -
58 SC28 1.0 60 6.8 ES757(2.0) ED27(8.2) -
59 SC29 1.0 60 6.8 ES70(2.0) ED28(8.2) -
60 SC30 1.0 60 0.8 ES70(2.0) ED33(1.8) 0.82
表 1(续）
无水氯化镁 THF TiCl4用 载体 给电子体 载体型催化剂中 实施例 催化剂编号 用量 用量 量 及其用量 及其用量 金属含量 (wt-%)
(g) (mL) (mmol) (g) (mmol) Ti
61 SC31 0.5 60 0.8 ES757(3.0) ED35(1.6) 0.40
62 SC32 1.0 40 3.4 ES70(1.0) ED37(4.1) -
63 SC33 1.0 40 3.4 ES70(1.0) ED38(4.1) -
64 SC34 1.0 40 3.4 ES70(1.0) ED39(4.1) -
65 SC35 1.0 40 3.4 ES70(1.0) ED40(4.1) -
66 SC36 1.0 40 3.4 ES70(1.0) ED41(4.1) -
67 SC37 1.0 40 3.4 ES70(1.0) ED42(4.1) . 4.10
68 SC38 1.0 40 3.4 ES70(1.0) ED43(4.1) 3.67
69 SC39 1.0 40 3.4 ES70(1.0) ED44(4.1) -
实施例 70〜实施例 74 以下实施例为含有新型给电子体的 Ziegler-Natta催化剂的制备，均按照实施例 32的方法 一制备， 不同之处及 Ziegler-Natta催化剂的金属含量分析结果列于表 2中。
表 2
给电子体 载体型催化剂中
实施例 催化剂编号 金属化合物 及其用量 金属含量 (wt-%)
(mmol) M
70 SC40 TiCl4(THF)2 ED13(3.5) 4.42
71 SC41 ZrCl4 ED13(3.5) 3.36
72 SC42 CrCl3 ED27(3.5) - 73 SC43 CrCl3(THF)3 ED33(3.5) 3.41
74 SC44 VC13(THF)3 ED35(4.0) - 实施例 75〜实施例 103 以下实施例进行乙烯淤浆聚合
将 0.5L不锈钢搅拌聚合釜用 N2置换三次， 乙烯置换两次， 将 180mL己烷溶液 (200mL 己烷 +1.0 mLAlEt3(3.0M己烷溶液))加入釜内，开动搅拌 (转速 =150 rpm)，并用恒温水浴将釜内 温度预热到 60°C左右。在 N2保护下， 依次将一定量共单体 (乙烯均聚时不加)和 10mg催化剂 (用 20mL上述己垸溶液冲洗)加入到聚合釜中， 然后卸去釜内压力， 待釜内温度升至约 80。C， 通入乙烯气体， 使釜内压力达到 l.OMPa, 五分钟后， 将搅拌转速升至 250 rpm。 水浴温度调 至 85°C。 聚合 lh后停止通入乙烯， 用循环冷却水使釜内温度降至 50。C以下， 放空体系中的 气体并出料， 干燥后得到颗粒状聚合物。
具体实验条件、 催化活性 (g聚合物 /g催化剂)、 聚合物分子量^^!!^)、 聚合物分子量 分布 (PDI)以及聚合物堆密度 (g/cm3)等聚合结果数据列于表 3， 实施例 78的乙稀 /己烯共聚物 的 13C NMR谱图见附录图 2。 表 3
共单体 共单体 实施例 催化剂 共单体 用量 催化活性 w PDI 插入率
(g) (g聚合物 /g催化剂） (104 g mol) (mol-%)
75 SC01 - 0 1000 11.6 3.46
76 SC02 - 0 930 12.7 3.35 -
77 SC03 1-己烯 10 1500 10.8 3.52 2.05
78 SC04 1-己烯 20 1200 10.3 3.56 1.04
79 SC0S - 0 850 - - -
80 SC06 - 0 1100 - - -
81 SC07 - 0 1140 - - -
82 SC08 - 0 740 - - -
S3 SC09 1-己烯 10 1360 10.5 1.95
84 SC18 - 0 2000 16.7 2.45 -
85 SC19 - 0 900 18.5 3.25 -
86 SC20 - 0 3500 12.3 3.22 -
87 SC21 - 0 1500 19.4 3.07 -
88 SC22 1-己烯 10 1840 15.2 3.20 2.03
89 SC25 1-己烯 10 4200 14.5 3.41 1.68
90 SC26 1-己烯 10 3700 13.8 3.35 1.81 91 SC32 - 0 1660 14.0 3.56 -
92 SC33 - 0 1200 11.2 1.81 -
93 SC34 - 0 1500 1.3 3.20 -
94 SC35 - 0 1430 1.5 3.11 -
95 SC36 - 0 1700 10.3 3.69 -
96 SC37 - 0 2100 - - -
97 SC38 - 0 1500 - - -
98 SC39 - 0 1250 - - -
99 SC40 - 0 1650 - - -
100 son - 0 860 - - -
101 SC42 - 0 1120 - - -
102 SC43 - 0 1300 - - -
'103 SC44 - 0 1000 - - -
实施例 104〜实施例 121
以下实施例进行乙烯淤浆聚合
将 2L不锈钢搅拌聚合釜用 N2置换三次， 乙烯置换两次， 将 400g己垸加入釜内， 开动搅 拌 (转速 =150 rpm),并用超级恒温水浴进行水循环将釜内温度预热到 60°C左右。在 N2保护下， 将 30mg催化剂、 200 g己烷和 2.1 mLAlEt3(0.88M己烷溶液)加入到加料罐中， 充分振摇并将 加料罐连接在聚合体系上。 用 N2气将加料罐中的混合物压入聚合釜中， 然后卸去釜内压力， 待釜内温度升至约 70°C， 通入乙烯气体 (¾调聚合时先通入 ¾)， 使釜内总压力达到 0.8MPa， 五分钟后，将搅拌转速升至 250 rpm,水浴温度调至 85°C。在共聚合情况下，在聚合开始 20min 后， 加入一定量共聚单体。 聚合 2h后停止通入乙烯， 用循环冷却水使釜内温度降至 50°C以 下， 放空体系中的气体并出料， 干燥后得到颗粒状聚合物。
具体实验条件、 催化活性 (g聚合物 /g催化剂)、 聚合物分子量 Mw(g/mol)、 聚合物分子量 分布 (PDI)以及聚合物堆密度 (g/cm3)等聚合结果数据列于表 4。 表 4
共单体 共单体
实施例 催化剂 共单体 用量 催化活性 Mw PDI 插入率
(g) (g聚合物 /g催化剂） (lOVmol) (mol-%)
104 SC11 - 0 18000 30.2 2.18 -
105 SC11 1-丁烯 30 12500 31.5 2.65 0.15
106 SC11 1-丁烯 60 9500 - - 0.34
107 SC11 1-己烯 30 11000 19.8 3.66 0.61 108 sen 1-己烯 60 7400 - - -
109 SC12 - 0 5300 - - -
110 SC13 - 0 8600 - - -
111 SC15 - 0 12600 25.4 3.12 -
112 SC15 1-丁烯 30 10500 19.0 3.45 -
113 SC15 1-己烯 30 7200 - - -
114 SCIS 1-己烯 60 4700 17.6 3.19 0.26
115 SC17 - 0 16000 - - -
116 SC23 - 0 11600 38.4 2.05 -
117 SC24 1-己烯 30 12200 20.8 2.46 . 0.95
118 SC28 - 0 3400 - -
119 SC29 1-己烯 30 16300 21.5 2.32 0.87
120 SC30 - 0 10400 - - - 121 SC31 - 0 12000 - - -

Claims

权利要求
1、 一类含杂原子的有机化合物， 其结构式如下所示:
Figure imgf000024_0001
R2: 氢、 CrC3o的烃基、 -C30的取代径基、 C5-C5()的芳香烃基、 或 C5-C5o的取 代芳香烃基， 上述基团彼此间相同或不同， 其中相邻基团彼此独立、 相互成键、 或成环， 条件是 R1和 R2彼此不形成芳香环；
R3、 R4、 R5、 R6、 R7、 R8、 R9:氢、 d-C^的烃基、 C ^的取代烃基、 C5-C50的芳香 烃基、 或 C5-C5()的取代芳香烃基， 上述基团彼此间相同或不同， 其中相邻基团彼此独立、 成键或成环；
X： 0、 N、 S、 Se或 P;
当 X是 0、 S或 Se时， X上只有一个取代基 R8或 R9;
所述的芳香烃基是指苯基、 萘基、 蒽基、 菲基或其他杂芳香烃基；
所述的取代烃基或取代芳香烃基是指烃基或芳香烃基含有烃基、 硅基、 卤素、 羰基、 酯基、 酰胺基团、 含氧基团、 含硫基团、 ¾含氮基团、 含磷基团或含硒基团；
含氧基团包括垸氧基 -ORie; 含硫基团包括 -SR11或 -S(0)R12; 含氮基团包括 -NR13R14 或 -N(0)R15R16; 含磷基团包括 -PR17R18或 -P(0)R19R2Q; 含硒基团包括 -SeR21或 -Se(0)R22;
R10、 R"、 R12、 R13、 R14、 R15、 R16、 R17、 R18、 R19、 R20、 R21、 R22: -Cso的取代 烃基、 C5-C5o的芳香'烃基、 或 C5-C5Q的取代芳香烃基， 上述基团彼此间相同或不同， 其中 R13和 R14、 R15和 R16、 R17和 R18、 R19和 R2Q可以彼此成键或成环。
2、 如权利要求 1 所述的含杂原子的有机化合物， 其特征是该化合物在有机溶剂中可以以 如下的互变异构体存在-
Figure imgf000024_0002
其中， R^R9如权利要求 1所述。
3、 如权利要求 1所述的含杂原子的有机化合物， 其特征是具有如下的结构式:
Figure imgf000024_0003
Figure imgf000025_0001
ED 13 ED14 ED15 ED16
Figure imgf000025_0002
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000026_0003
、一种如权利要求 1所述的含杂原子的有机化合物， 其特征是该化合物的合成方法为：在 有机溶剂中和催化剂存在下， 将二酮化合物和胺类化合物回流反应 2~48 h, 得到含杂原 子的有机化合物;所述的二酮化合物、胺类化合物和催化剂的摩尔比为 1~1.5： 1 : 0.01 0.1 ; 所述二酮具有如下的结构式：
Figure imgf000026_0004
所述的胺化合物具有如下的结构式:
Figure imgf000026_0005
R^R9如前所述；
所述的催化剂为甲酸、 乙酸或对甲苯磺酸。
、一种如权利要求 1所述的含杂原子的有机化合物的用途，其特征是该化合物可以作为给 电子体用于制备单活性中心齐格勒-纳塔催化剂。
、 如权利要求 5所述的一类含杂原子的有机化合物的用途， 其特征是所述单活性中心齐 格勒-纳塔催化剂是由镁化合物、 载体、 金属化合物以及上述的含杂原子的有机化合物 制备得到； 所述的镁化合物与载体的质量比为 1: 0.1〜20； 镁化合物与金属化合物的摩 尔比为 0.5〜100: 1 ; 含杂原子的有机化合物与金属化合物的摩尔比为 0.01〜10: 1； 催 化活性中心金属含量为 0.1〜15质量％；
所述的镁化合物为卤化镁、 垸基镁、 烷氧基卤化镁、 垸氧基镁， 卤化镁醇合物或它们 的混合物；
所述的载体为有机材料、 第 2、 4、 13和 14族金属氧化物在内的无机氧化物； 所述无机氧化物为 A1203， 或 Si02， 以及氧化混合物和混合氧化物， 或是由气态金属氧 化物或硅化合物通过高温水解过程而制备的氧化材料， 粘土或分子筛；
所述的金属化合物的分子式如下：
MLa
其中：
a: 3或 4;
L: 是卤原子、 -C30的烃基或 CH^o的取代烃基、 含氧基团、 含氮基团或相应的 化合物， 几个 L相同， 或不同， 彼此独立、 成键或成环；
这里的卤原子包括氟、 氯、 溴或碘；
取代烃基是指含有烃基、 硅基、 卤素、 羰基、 酯基、 酰胺基团、 含氧基团、 含硫基 团、 含氮基团、 含磯基团或含硒基团的烃基；
含氧基团或相应化合物包括烷氧基 -OR23、四氢呋喃或 Et20; 含氮基团包括 -NR24R25 或 -N(0)R26R27;
R23、 R24、 R25、 R26、 R27: 氢、 -C^的取代烃基、 C5-C5o的芳香烃基或 C5-C5D的取 代芳香烃基， 上述基团彼此间相同或不同， 其中 R24和 R25、 R26和 R27彼此独立、 成键 或成环。
结构式中所有 L所带负电荷总数的绝对值应与结构式中金属 M所带正电荷的绝对 值相同以保证金属化合物的电中性；
M: 第四族到第六族的过渡金属原子， 优选钛、 锆、 铬或钒。
7、 如权利要求 6所述的一类含杂原子的有机化合物的用途， 其特征是所述的金属化合物 选自钛化合物、 锆化合物、 铬化合物或钒化合物；
其中钛化合物为四卤化钛、 四卤化钛的四氢呋喃或乙醚的络合物、 三卤代烷氧基钛、 二卤代垸氧基钛、 一卤代烷氧基钛、 四烷氧基钛、 四胺基钛或四烷基钛；
锆化合物优选 ZrCl4或四胺基锆；
铬化合物优选 CrCl3或 CrCl3(THF)3 ;
钒化合物优选 VC15、 VC13(THF)3或 VCl3(PMe3)2; 所述的 THF是四氢呋喃。
8、 如权利要求 7所述的一类含杂原子的有机化合物的用途， 其特征在于所述的钛化合物 优选自 TiCl4或 TiCl4(THF)2 ; 所述的三卤代垸氧基钛优选自 Ti(OC¾)Cl3或 Ti(OC2H5)Cl3； 所述的二卤代烷氧基钛优选自 Ti(OCH3)2Cl2、 Ti(OC2H5)2Cl2、 Ti(OC2H5)Br2或 Ti(0( -C4H9))2Cl2 ; 所述的一卤代烷氧基钛优选自 Ti(OC¾)3Cl、 Ti(OCH3)3Br, Ti(OC2H5： bCl或 Ti(OC2H5)3Br; 所述的四烷氧基钛优选自 Ti(OCH3)4、 Ti(OC2¾)4、 ^(。(^！^或！^^^^!^)^， 所述的 THF是四氢呋喃。 、 如权利要求 6所述的一类含杂原子的有机化合物的用途， 其特征在于所述的金属化合 物更优选 TiCl4、 TiCl4(THF)2、 Ti(0( -C4H9))4、 Ti(NEt2)4、 Ti(CH2Ph)4、 ZrCl4、 Zr( Me2)4、 Zr(NEt2)4、 CrCl3、 CrCl3(THF)3、 VC13或 VC13(THF)3。
0、 如权利要求 6所述的一类含杂原子的有机化合物的用途， 其特征在于所述的载体优选 02。
1、 如权利要求 6所述的一类含杂原子的有机化合物的用途， 其特征是用如下方法制备单 活性中心的齐格勒 -纳塔催化剂：
(1) 将作为载体的有机或无机固体或两者的复合物在惰气气氛保护或减压条件下， 30〜
1000° C处理 1〜24小时进行热处理；
(2) 在室温〜 70°C条件下， 将镁化合物溶解于四氢呋喃中形成溶液， 镁化合物与四氢 呋喃的比例为 1 g: 10~100mL;
(3) 向上述溶液中加入将步骤 (1)中所述载体、金属化合物以及所述的含杂原子的有机化 合物体， 在室温〜 100° C反应 2〜48小时， 所述的镁化合物与载体的质量比为 1 : 0.1〜20； 镁化合物与金属化合物的摩尔比为 0.5〜100： 1； 新型给电子体与金属化 合物的摩尔比为 0.01〜10: 1。
、 如权利要求 11所述的一类含杂原子的有机化合物的用途， 其特征在于步骤 (3)中镁化 合物先与金属化合物在室温〜 100QC反应 2〜48小时， 然后与热处理后的载体作用， 再与上述给电子体在在室温〜 100°C反应 2〜48小时， 处理后得到催化剂。
、 如权利要求 11所述的一类含杂原子的有机化合物的用途， 其特征在于步骤 (3)中镁化 合物先与载体在室温〜 100° C反应 2〜48小时得到复合载体， 然后得到的复合载体再 与上述给电子体和金属化合物的有机溶剂在室温〜 100° C反应 2〜48小时， 处理后得 到催化剂。
、按照权利要求 6所述的一类含杂原子的有机化合物的用途，其特征是用于乙烯均聚合、 乙烯 /α-烯烃共聚合以及乙烯 /环烯烃共聚合。
、 按照权利要求 14所述的一类含杂原子的有机化合物的用途， 其特征是聚合时需以烷 基铝、 烷基铝氧烷或它们的混合物为助催化剂， 所述的助催化剂选自三乙基铝、 三异 丁基铝、 一氯二乙基铝、三己基铝、 甲基铝氧烷、 乙基铝氧烷、 修饰的甲基铝氧垸或 它们的混合物； 聚合时适宜的 ΑΙ/Ti摩尔比为 20〜1000； 所述的 a-烯烃为 C3〜C20烯 烃， 选自丙烯、 1-丁烯、 1-己稀、 1-庚烯、 4-甲基 -1-戊熾、 1-辛烯、 1-癸烯、 1-十一烯、 1-十二烯、 1-十四烯、 1-十六烯或 1-十八熾； 所述的环烯烃为环戊烯、 环己烯、 降冰 片烯或有烷基取代的环戊烯、 环己烯或降冰片烯； 所述的 ct-烯烃或环烯烃上可以有羟 基、 羰基、 酯基或胺基。
、 如权利要求 14所述的一类含杂原子的有机化合物的用途， 其特征是所述的聚合是淤 浆聚合或气相聚合。
、 如权利要求 16所述的一类含杂原子的有机化合物的用途， 其特征是所述的淤浆聚合 在超临界或亚临界状态下进行， 条件为聚合总压力为 0.1〜10.0MPa、 氢气压力为 0〜
1.0MPa、 聚合温度 80〜120°C， 采用的介质为丙烷、 异丁烷或己垸， 聚合反应器为搅 拌釜或环管反应器； 气相聚合条件为 1.0〜10.0MPa、 聚合温度为 40〜100° C， 聚合在 气体流化床或气相搅拌釜中进行。
PCT/CN2007/001648 2006-05-22 2007-05-21 Composés organiques contenant des hétéroatomes et leur utilisation dans un catalyseur ziegler-natta à centre d'activation unique WO2007134537A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP07721221.5A EP2039677B1 (en) 2006-05-22 2007-05-21 Organic compounds containing heteroatoms and their use in ziegler-natta catalyst with single activation center
JP2009511322A JP2009537573A (ja) 2006-05-22 2007-05-21 ヘテロ原子を含む有機金属化合物および単一活性部位のチーグラー−ナッタ型触媒を製造される用途
US12/275,882 US20090137383A1 (en) 2006-05-22 2008-11-21 class of organic compounds containing heteroatom and its applications in preparing single-site ziegler-natta catalyst
US14/028,130 US20140073500A1 (en) 2006-05-22 2013-09-16 Class of organic compounds containing heteroatom and its applications in preparing single-site ziegler-natta catalyst

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB2006100267662A CN100569734C (zh) 2006-05-22 2006-05-22 一类含杂原子的有机化合物及其在齐格勒-纳塔催化剂中的应用
CN200610026766.2 2006-05-22

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/275,882 Continuation-In-Part US20090137383A1 (en) 2006-05-22 2008-11-21 class of organic compounds containing heteroatom and its applications in preparing single-site ziegler-natta catalyst

Publications (1)

Publication Number Publication Date
WO2007134537A1 true WO2007134537A1 (fr) 2007-11-29

Family

ID=37582573

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2007/001648 WO2007134537A1 (fr) 2006-05-22 2007-05-21 Composés organiques contenant des hétéroatomes et leur utilisation dans un catalyseur ziegler-natta à centre d'activation unique

Country Status (5)

Country Link
US (2) US20090137383A1 (zh)
EP (1) EP2039677B1 (zh)
JP (1) JP2009537573A (zh)
CN (1) CN100569734C (zh)
WO (1) WO2007134537A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8193288B2 (en) 2007-10-16 2012-06-05 Sinopec Yangzi Petro-Chemical Ltd. Supported nonmetallocene catalyst and preparation thereof
JP2013506038A (ja) * 2009-10-26 2013-02-21 中国石油化工股▲ふん▼有限公司 担持型非メタロセン触媒、その製造方法およびその使用
US8716416B2 (en) 2007-10-16 2014-05-06 Sinopec Yangzi Petrochemical Company Ltd. Magnesium-compound supported nonmetallocene catalyst and preparation thereof

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100569734C (zh) * 2006-05-22 2009-12-16 中国科学院上海有机化学研究所 一类含杂原子的有机化合物及其在齐格勒-纳塔催化剂中的应用
CN101412768B (zh) * 2007-10-16 2012-05-30 中国石化扬子石油化工有限公司 一种镁化合物负载型非茂金属催化剂及其制备方法
EP2495261B1 (en) 2009-10-26 2020-08-26 China Petroleum & Chemical Corporation Supported non-metallocene catalyst, manufacturing method and application thereof
JP5670466B2 (ja) * 2009-11-13 2015-02-18 中国石油化工股▲ふん▼有限公司 担持型非メタロセン触媒、その製造方法およびその使用
WO2011057468A1 (zh) * 2009-11-13 2011-05-19 中国石油化工股份有限公司 负载型非茂金属催化剂、其制备方法及其应用
CN101798362B (zh) * 2010-02-10 2012-07-11 中国科学院上海有机化学研究所 一类具有单活性中心性质的齐格勒-纳塔烯烃聚合催化剂
CN102030844B (zh) * 2010-09-14 2014-07-23 中国科学院上海有机化学研究所 烯烃聚合催化剂及超低支化度超高分子量聚乙烯
US11282975B2 (en) * 2012-02-29 2022-03-22 Mitsui Chemicals Tohcello, Inc. Sheet set for encapsulating solar battery
US10076117B2 (en) * 2014-08-28 2018-09-18 Rotam Agrochem International Company Limited Pesticide formulation comprising a water soluble active ingredient and a penetration enhancer and use of the same
CN105440194A (zh) * 2014-09-16 2016-03-30 中国科学院上海有机化学研究所 聚乙烯粉料、交联聚乙烯管材、其原料组合物及制备方法
WO2016128812A1 (en) * 2014-11-25 2016-08-18 Versalis S.P.A. Phosphinic vanadium complex, catalytic system comprising said phosphinic vanadium complex and process for the (co) polymerization of conjugated dienes
BR112018077454A2 (pt) * 2016-06-30 2019-04-02 Dow Global Technologies Llc composições de procatalisador úteis para baixa incorporação de comonômero e processo para preparar as mesmas

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4330649A (en) 1979-06-18 1982-05-18 Mitsui Petrochemical Industries, Ltd. Process for producing olefin polymers or copolymers
US5106807A (en) 1990-01-10 1992-04-21 Himont Incorporated Components and catalysts for the polymerization of olefins
US5459116A (en) 1993-05-07 1995-10-17 Samsung General Chemicals Co., Ltd. Highly active catalyst for the polymerization of olefins and method for the preparation of the same
JP2001172273A (ja) * 1999-12-14 2001-06-26 Sumitomo Chem Co Ltd ジイミノ置換ジフェニレン誘導体およびその製造法
CN1189487C (zh) 2000-05-31 2005-02-16 三星阿托菲纳株式会社 乙烯均聚物和共聚物的制备方法
CN1884253A (zh) * 2006-05-22 2006-12-27 中国科学院上海有机化学研究所 一类含杂原子的有机化合物及其在齐格勒－纳塔催化剂中的应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1603724A (en) * 1977-05-25 1981-11-25 Montedison Spa Components and catalysts for the polymerisation of alpha-olefins
US4759926A (en) * 1982-05-05 1988-07-26 Johnson & Johnson Baby Products Sunscreen compositions
DE19637370A1 (de) * 1996-09-13 1998-03-19 Basf Ag Bei ihrer Herstellung modifizierte Ziegler-Natta-Katalysatorsysteme
US6531424B2 (en) * 1999-12-17 2003-03-11 E. I. Du Pont De Nemours And Company Polymerization of olefins
EP1229055A1 (en) * 2001-02-06 2002-08-07 BP Chemicals S.N.C. Process for the gas-phase (co)-polymerisation of olefins in a fluidised bed reactor
EP1426385B1 (en) * 2001-07-23 2012-08-22 Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences Catalyst for polymerization or copolymerization of olefins, preparation and use of the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4330649A (en) 1979-06-18 1982-05-18 Mitsui Petrochemical Industries, Ltd. Process for producing olefin polymers or copolymers
US5106807A (en) 1990-01-10 1992-04-21 Himont Incorporated Components and catalysts for the polymerization of olefins
US5459116A (en) 1993-05-07 1995-10-17 Samsung General Chemicals Co., Ltd. Highly active catalyst for the polymerization of olefins and method for the preparation of the same
JP2001172273A (ja) * 1999-12-14 2001-06-26 Sumitomo Chem Co Ltd ジイミノ置換ジフェニレン誘導体およびその製造法
CN1189487C (zh) 2000-05-31 2005-02-16 三星阿托菲纳株式会社 乙烯均聚物和共聚物的制备方法
CN1884253A (zh) * 2006-05-22 2006-12-27 中国科学院上海有机化学研究所 一类含杂原子的有机化合物及其在齐格勒－纳塔催化剂中的应用

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 138:347859, URAEV A.I. ET AL.: "Synthesis and structures of nickel(II) complexes with thioether-containing beta-aminovinyl ketones" *
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 144:123449, VLASENKO V.G. ET AL.: "XAFS study of Cu(II), Ni(II) and Co(II) beta-aminovinylketone complexes" *
HU W.-Q., ORGANOMETALLICS, vol. 23, 2004, pages 1684 - 1688
J. C. RANDALL, JMS-REV. MAROMOL. CHEM. PHYS., vol. C29, no. 2, 3, 1989, pages 201 - 317
KORSHUNOV O.Y. ET AL.: "Nickel(II) and cobalt(II) chelates with N-naphthyl- and n-quinolyl-beta-aminovinyl ketones", ZHURNAL NEORGANICHESKOI KHIMII, vol. 45, no. 9, 2000, pages 1491 - 1497, XP008092047 *
PHYSICA SCRIPTA, T (2005), T115 (12TH X-RAY ABSORPTION FINE STRUCTURE INTERNATIONAL CONFERENCE (XAFS12), 2003, pages 362 - 364 *
QU G. ET AL.: "Study on internal electron donors in catalyst for propylene polymerization", LIAONING CHEMICAL INDUSTRY, vol. 35, no. 1, January 2006 (2006-01-01), pages 44 - 47, XP008090834 *
RUSSIAN CHEMICAL BULLETIN (TRANSLATION OF IZVESTIYA AKADEMII NAUK, SERIYA KHIMICHESKAYA), vol. 51, no. 10, 2002, pages 1924 - 1927 *
See also references of EP2039677A4
WANG, C., MACROMOL. RAPID COMMUN., vol. 26, 2005, pages 1609 - 1614
ZHANG Z. ET AL.: "A general and efficient method for the preparation of beta-enamio ketones and esters catalyzed by indium tribromide", ADVANCED SYNTHESIS & CATALYSIS, vol. 348, no. 1 + 2, January 2006 (2006-01-01), pages 184 - 190, XP002431139 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8193288B2 (en) 2007-10-16 2012-06-05 Sinopec Yangzi Petro-Chemical Ltd. Supported nonmetallocene catalyst and preparation thereof
US8716416B2 (en) 2007-10-16 2014-05-06 Sinopec Yangzi Petrochemical Company Ltd. Magnesium-compound supported nonmetallocene catalyst and preparation thereof
JP2013506038A (ja) * 2009-10-26 2013-02-21 中国石油化工股▲ふん▼有限公司 担持型非メタロセン触媒、その製造方法およびその使用
US8981023B2 (en) 2009-10-26 2015-03-17 China Petroleum & Chemical Corp. Supported nonmetallocene catalyst, preparation and use thereof

Also Published As

Publication number Publication date
CN1884253A (zh) 2006-12-27
EP2039677B1 (en) 2014-04-23
CN100569734C (zh) 2009-12-16
US20140073500A1 (en) 2014-03-13
JP2009537573A (ja) 2009-10-29
US20090137383A1 (en) 2009-05-28
EP2039677A1 (en) 2009-03-25
EP2039677A4 (en) 2009-07-29

Similar Documents

Publication Publication Date Title
WO2007134537A1 (fr) Composés organiques contenant des hétéroatomes et leur utilisation dans un catalyseur ziegler-natta à centre d'activation unique
JP5346469B2 (ja) 担持非メタロセンオレフィン重合触媒、その調製方法及び使用方法
JP6236155B2 (ja) メタロセン化合物、これを含む触媒組成物およびこれを用いるオレフィン系重合体の製造方法
CN114127130A (zh) 催化剂体系的改进制备
KR102107084B1 (ko) 혼성 담지 메탈로센 촉매의 제조방법, 상기 제조방법으로 제조된 혼성 담지 메탈로센 촉매, 및 이를 이용하는 폴리올레핀의 제조방법
JP5480147B2 (ja) 担持非メタロセン触媒およびその製造方法
JP3237711B2 (ja) エチレンの（共）重合用触媒の固体成分
CN108264591B (zh) 一种烯烃聚合催化剂的主催化剂及其制备方法、烯烃聚合催化剂
US20080027191A1 (en) Catalyst For Ethylene Polymerization, Preparation Thereof, And Method For Controlling The Polymerization Kinetic Behavior Of Said Catalyst
US6583242B2 (en) Supported olefin polymerization catalysts
JP5670466B2 (ja) 担持型非メタロセン触媒、その製造方法およびその使用
EP2129695A1 (en) A supported catalyst for the preparation of (co)polymers ethylenically unsaturated monomers
CN111471074B (zh) 一种取代茚基金属配合物、其制备方法和应用
WO2002048207A1 (fr) Catalyseur spherique pour (co)polymerisation d'ethylene, sa preparation et son utilisation
EP2029636A2 (en) Olefin polymerization process
CZ281952B6 (cs) Pevná složka katalyzátoru pro (ko) polymeraci ethylenu
JP5670465B2 (ja) 担持型非メタロセン触媒、その製造方法およびその使用
JP2002506094A (ja) 高活性オレフィン重合触媒
RU2809186C1 (ru) Компонент катализатора для полимеризации или сополимеризации олефинов, способ его получения и его применение
EP4029872B1 (en) Transition metal compound, method for preparing the same, and catalyst composition comprising the same
CN117561285A (zh) 溶胀剂在多阶段聚烯烃生产中的用途
CN117924554A (zh) 一种杂双金属催化剂及其催化剂体系的制备方法及应用
US20080027192A1 (en) Process for Preparing Catalyst Systems Comprising Late Transition Metals
CN111212845A (zh) 聚烯烃催化剂及利用它的聚烯烃制造方法
CN117561287A (zh) 1-己烯在多阶段聚烯烃生产中的利用

Legal Events

Date Code Title Description
DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07721221

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2009511322

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2007721221

Country of ref document: EP