CN111662403B - Cascade catalytic system and method for preparing LLDPE (Linear Low Density polyethylene) by using same - Google Patents
Cascade catalytic system and method for preparing LLDPE (Linear Low Density polyethylene) by using same Download PDFInfo
- Publication number
- CN111662403B CN111662403B CN202010675181.3A CN202010675181A CN111662403B CN 111662403 B CN111662403 B CN 111662403B CN 202010675181 A CN202010675181 A CN 202010675181A CN 111662403 B CN111662403 B CN 111662403B
- Authority
- CN
- China
- Prior art keywords
- group
- catalyst
- phenyl
- alkyl
- lldpe
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
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
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a catalyst combination for preparing LLDPE by cascade catalysis, a catalytic polymerization system for preparing LLDPE by cascade catalysis containing the catalyst combination, a method for preparing LLDPE by using the polymerization system, and LLDPE prepared by the method. The catalyst combination comprises a first catalyst, a second catalyst and a cocatalyst, wherein the first catalyst is a pyrrole phosphine metal complex represented by a formula I, the second catalyst is an arylamine ether metal complex represented by a formula II, and the cocatalyst is at least one selected from alkylaluminoxane, alkylaluminum or modified alkylaluminoxane. LLDPE prepared by the catalyst combination has higher molecular weight, narrow molecular weight distribution and excellent performance,
Description
Technical Field
The invention belongs to the field of ethylene polymerization, and relates to a catalyst combination for preparing LLDPE by cascade catalysis, a catalytic polymerization system for preparing LLDPE by cascade catalysis containing the catalyst combination, a method for preparing LLDPE by using the polymerization system, and LLDPE prepared by the method.
Background
Linear Low Density Polyethylene (LLDPE) is a class of vinyl copolymers with 1-butene, 1-hexene or 1-octene as comonomers. LLDPE has high mechanical strength and good processing property, and can be widely applied to the fields of films, pipes, molding and the like. At present, the mainstream LLDPE production process in China uses 1-butene as a comonomer, and 1-hexene and 1-octene are used as main comonomers in developed countries in Europe and America to produce LLDPE. Compared with 1-butene, the copolymer prepared by using higher alpha-olefin such as 1-hexene, 1-octene and the like as comonomer has more excellent performances in the aspects of tensile strength, impact resistance, tear resistance, environmental stress crack resistance and the like. There is a great need to develop a technique for preparing higher performance LLDPE.
The cascade catalysis technology is that ethylene is used as the only monomer material, oligomerization catalyst and copolymerization catalyst are added into a reactor, the oligomerization catalyst is used to prepare comonomer-high alpha-olefin in situ, and the copolymerization catalyst is used to copolymerize the alpha-olefin and ethylene, so as to prepare the ethylene/alpha-olefin copolymer. Compared with the traditional polymerization process, the process saves the cost of comonomer production, transportation and storage. Chinese patent application publication CN104356269A discloses a method for producing 1-hexene by chromium complex catalysis and producing LLDPE with narrow molecular weight distribution by copolymerization of titanium catalysts. Patent application publication WO200204119 discloses a process for the production of 1-hexene from Cr complexes containing P, followed by the addition of a copolymerization catalyst in cascade to produce LLDPE. Patent application publication WO2004056480 adopts homogeneous phase complex of Cr to catalyze ethylene tetramerization to prepare 1-octene, and then uses transition metal catalyst as copolymerization catalyst to prepare a copolymer using 1-octene as comonomer.
Although the literature reports a number of cascaded catalytic systems, most of them are not directed to the ethylene/alpha-olefin copolymer production unit and its polymerization conditions currently in industrial use. After the traditional copolymerization catalyst is added with a comonomer, the molecular weight of the polymer is obviously reduced, and the mechanical property of the polymer is influenced. In response to this problem, the combination of the metal complex of phenylpyrrole and the metal complex of arylamino ether proposed in the present invention can produce LLDPE of high molecular weight.
Disclosure of Invention
The invention aims to provide a catalyst combination for preparing LLDPE, a cascade catalytic system containing the combination, a method for preparing LLDPE by using the catalytic system and LLDPE prepared by the method.
According to a first aspect of the present invention there is provided a catalyst combination for the preparation of LLDPE by tandem catalysis comprising a first catalyst, a second catalyst and a cocatalyst,
wherein the first catalyst is a metal complex of a phenylphosphine represented by formula I,
wherein A is a metal selected from group VIB, preferably from chromium (III), molybdenum (V) or tungsten (V);
R 1 is halogen, acetylacetone or isooctanoate;
n is 3, 4 or 5, which is a value corresponding to the valence state of A;
R 2 and R 3 Each independently is substituted or unsubstituted C 6 ～C 14 An aryl group; preferably, said substituted C 6 ～C 14 Substituents in aryl groups being selected from C 1 ～C 6 Alkyl radical, C 1 ～C 6 Alkoxy, halogen, C 3 ～C 8 Cycloalkyl, silyl, or one or more C 1 ～C 6 One or more of alkyl substituted silane groups; more preferably, said substituted C 6 ～C 14 Substituents in aryl groups being selected from C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, halogen, C 3 ～C 6 Cycloalkyl, silyl, or one or more C 1 ～C 6 One or more of alkyl substituted silane groups; even more preferably, R 2 And R 3 Each independently selected from phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, o-methoxyphenyl, o-ethoxyphenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 2, 4-dimethylphenyl, 2, 4-diethylphenyl, 2, 4-diisopropylphenyl, 2, 4-dibutylphenyl, 2, 6-diiso-butylphenylPropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-dibutylphenyl, naphthyl, anthryl, biphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-silylphenyl, 4-silylphenyl, 2- (trimethylsilyl) phenyl, 4- (trimethylsilyl) phenyl, 2- (triethylsilyl) phenyl, 4- (triisopropylsilyl) phenyl, 4- (triisobutylsilyl) phenyl, 4- (tri-tert-butylsilyl) phenyl or 2- (tri-tert-butylsilyl) phenyl;
R 4 selected from hydrogen, C 1 ～C 6 Alkyl radical, C 3 ～C 8 Cycloalkyl, or substituted or unsubstituted C 6 ～C 14 An aryl group; preferably, said substituted C 6 ～C 14 Substituents in aryl groups being selected from C 1 ～C 6 Alkyl radical, C 1 ～C 6 Alkoxy, halogen or C 3 ～C 8 A cycloalkyl group; more preferably, said substituted C 6 ～C 14 Substituents in aryl groups being selected from C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, halogen, C 3 ～C 6 One or more of cycloalkyl or silyl; more preferably, R 4 Selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, o-methoxyphenyl, o-ethoxyphenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 2, 4-dimethylphenyl, 2, 4-diethylphenyl, 2, 4-diisopropylphenyl, 2, 4-dibutylphenyl, 2, 6-diisopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-dibutylphenyl, naphthyl, anthryl, Biphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-silylphenyl, 4-silylphenyl, 2- (trimethylsilyl) phenyl, 4- (trimethylsilyl) phenyl, 2- (triethylsilyl) phenyl, 4- (triisopropylsilyl) phenyl, 4- (tributylsilyl) phenyl, 4- (triisobutylsilyl) phenyl4- (tri-tert-butylsilyl) phenyl or 2- (tri-tert-butylsilyl) phenyl;
more preferably, the first catalyst is selected from any one of the following complexes:
the second catalyst is an arylamino ether metal complex represented by formula II
Wherein R is 1 To R 9 Each of which is the same or different and each is independently selected from hydrogen, C 1 ～C 10 Alkyl radical, C 1 ～C 10 Alkoxy radical, C 3 ～C 10 Cycloalkyl radical, C 3 ～C 10 Cycloalkyl oxy, C 6 ～C 14 Aryl or C 6 ～C 14 An aryloxy group;
m is a transition metal selected from group IVB, preferably selected from titanium, zirconium or hafnium,
x is halogen, preferably bromine or chlorine;
preferably, R 1 And R 5 Each independently is C 1 ～C 6 An alkyl group; more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
preferably, R 2 And R 4 Each independently is hydrogen or C 1 ～C 6 Alkyl, more preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
preferably, R 3 Each independently of the other is hydrogen, C 1 ～C 6 An alkyl group; more preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
preferably, R 6 To R 8 Each independently is hydrogen or C 1 ～C 6 Alkyl, more preferablyIs hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
preferably, R 9 Each independently is hydrogen or C 1 ～C 6 An alkyl group; more preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
Preferably, the second catalyst is any one selected from the following complexes:
preferably, the cocatalyst is at least one selected from alkylaluminoxane, alkylaluminum halide or modified alkylaluminoxane.
The alkyl aluminoxane is selected from C 1 ～C 5 Alkylaluminoxane, preferably selected from methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isopropylaluminoxane or tert-butylaluminoxane;
the alkyl aluminum is C 1 ～C 5 An alkylaluminum, preferably selected from trimethylaluminum, triethylaluminum, tripropylaluminum or tributylaluminum;
the alkyl aluminum halide is preferably C 1 ～C 5 Alkylaluminum halides, more preferably diethylaluminum monochloride, ethylaluminum dichlorochloride or ethylaluminum sesquichloride;
the modified aluminoxane is selected from triisobutylaluminum or trioctylaluminum modified C 1 ～C 5 The alkylaluminoxane is preferably selected from triisobutylaluminum-modified methylaluminoxane, triisobutylaluminum-modified ethylaluminoxane, triisobutylaluminum-modified propylaluminoxane, trioctylaluminum-modified methylaluminoxane and trioctylaluminum-modified ethylaluminoxane.
Wherein the molar ratio of the first catalyst to the second catalyst to the cocatalyst is 1: (0.05-10): (10 to 2000), preferably 1: (0.1-5): (50-1000).
According to a second aspect of the present invention, there is provided a catalyst composition for the preparation of LLDPE by means of tandem catalysis, comprising:
the first catalyst, the second catalyst, and the co-catalyst.
According to a third aspect of the present invention, there is provided a catalytic polymerization system for the preparation of LLDPE with cascade catalysis, comprising:
a vinyl monomer;
the catalyst combination; and
a solvent, a water-soluble organic solvent,
wherein the molar ratio of the first catalyst, the second catalyst, the cocatalyst and the ethylene monomer in the catalyst composition is 1: (0.05-10): (10 to 2000), preferably 1: (0.1-5): (50-1000).
The solvent is selected from aliphatic hydrocarbon solvents and/or aromatic hydrocarbon solvents.
Preferably, the aliphatic hydrocarbon solvent is selected from one or more of n-butane, isobutane, n-pentane, cyclopentane, methylcyclopentane, methylenecyclopentane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, n-heptane, n-octane, n-nonane or Isopar E.
Preferably, the aromatic hydrocarbon solvent is selected from one or more of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, dichlorotoluene.
More preferably, the solvent is selected from toluene, cyclohexane, methylcyclohexane or Isopar E.
Preferably, the ethylene pressure is from 1MPa to 5 MPa.
Preferably, the ethylene is the only monomer charged to the polymerization system.
According to a fourth aspect of the present invention there is provided the use of the catalyst combination, the catalyst combination or the polymerization system in the preparation of LLDPE.
According to a fifth aspect of the present invention there is provided a process for the preparation of LLDPE comprising the steps of:
1) oligomerizing ethylene in a high-pressure reaction kettle in a solvent under the condition that the pressure intensity of ethylene is 1-5 MPa in the presence of the first catalyst and the cocatalyst;
2) after the oligomerization reaction of step 1) is completed, adding the second catalyst to the reaction system so that ethylene is copolymerized with the oligomer obtained in step 1) to produce LLDPE,
wherein the molar ratio of the first catalyst, the second catalyst and the cocatalyst is 1: (0.05-10): (10 to 2000), preferably 1: (0.1-5): (50-1000) of a first polymer,
and the ratio of the first catalyst to the solvent is 0.1-80 mu mol/100 ml; preferably 0.5 to 50. mu. mol/100 ml.
The solvent is selected from aliphatic hydrocarbon solvents and/or aromatic hydrocarbon solvents;
the aliphatic hydrocarbon solvent is preferably selected from one or more of n-butane, isobutane, n-pentane, cyclopentane, methylcyclopentane, methylenecyclopentane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, n-heptane, n-octane, n-nonane or Isopar E;
the aromatic hydrocarbon solvent is preferably selected from one or more of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, dichlorotoluene;
preferably, the reaction temperature of step 1) and step 2) is independently 50 ℃ to 100 ℃.
Preferably, a quencher is added to step 2) to terminate the reaction.
The amount of the quenching agent is 0.5-5 times, preferably 1-3 times of that of the cocatalyst substance.
The quenching agent is preferably an alcohol having 2 to 20 carbon atoms, more preferably one or more selected from the group consisting of ethanol, ethylene glycol, n-propanol, glycerol, n-butanol, 2-butanol, neopentyl alcohol, 1, 6-hexanediol, n-octanol, 2-ethylhexanol, benzyl alcohol, n-decanol, dodecanol, tetradecanol, and hexadecanol, preferably one or more selected from the group consisting of ethanol, 2-ethylhexanol, tetradecanol, and hexadecanol, and still more preferably one or more selected from the group consisting of ethanol, 2-ethylhexanol, tetradecanol, and hexadecanol.
According to a fifth aspect of the present invention there is provided an LLDPE made by the process of the invention, which has the following properties: the melting point is 90 to 135 ℃, preferably 95 to 128 ℃; the branching degree is 1-30 CH 3 C1000, preferably 1 to 25 CH 3 1000 carbon atoms; the weight average molecular weight is 20,000 to 3,000,000, preferably 50,000 to 600,000; the molecular weight distribution index is less than or equal to 3, preferably 1.2-2.9.
The invention has the following beneficial effects:
1. in a single reactor, firstly, under the action of a first catalyst and a cocatalyst, ethylene is mainly oligomerized into 1-octene and a small amount of 1-hexene, and then, under the action of a second catalyst and a cocatalyst, ethylene is copolymerized with the produced 1-octene and a small amount of 1-hexene, thereby directly producing LLDPE containing a copolymer of ethylene and alpha-olefin from ethylene as a raw material;
2. the preparation method of LLDPE is simple in process, and the molecular weight and the branching degree of the product can be adjusted by simply changing the reaction time and the ratio of the first catalyst to the second catalyst;
3. the produced LLDPE has higher molecular weight, small molecular weight distribution index, excellent performance and good application prospect.
Detailed Description
The first catalyst of the present invention can be prepared by the following method:
a) in an organic solvent under an inert atmosphere, reacting pyrrole with R 4 -CHO is dissolved in an organic solvent and trifluoroacetic acid is added thereto to produce a dipyrromethene solution;
b) adding excess n-butyllithium dropwise into the dipyrromethene solution obtained in step a) at-78 deg.C to room temperature, slowly heating to room temperature for reaction, filtering, and adding compound R into the solution at-78 deg.C 2 (R 3 ) PCl, and reacting at room temperature to obtain a ligand L;
c) dissolving the ligand L and the salt or the solvate of the salt of the metal A in an organic solvent, reacting at room temperature to obtain a first catalyst,
wherein, A, R 2 、R 3 And R 4 As defined above, the salt of metal a is preferably a halide salt, acetylacetonate or isooctanoate.
Wherein the organic solvent in step a) may be C 1 ～C 6 Alkane or halogenated C 1 ～C 6 An alkane.
Wherein the organic solvent in step c) may be methylcyclohexane.
The second catalyst of the present invention can be prepared by the following method:
in an ultra-dry organic solvent, a compound shown as a formula II-1 firstly reacts with a hydrogen-withdrawing reagent to generate sodium salt, and then the sodium salt reacts with a halide salt MX of a metal M 4 Carrying out complexation reaction to obtain the complex shown in the formula II.
Wherein R is 1 To R 9 And M and X are as defined above.
The organic solvent may be a solvent conventionally used in the art as long as it does not participate in the reaction, and is preferably selected from tetrahydrofuran, hexane, heptane, toluene, xylene, cyclopentane, cyclohexane, methylcyclohexane, chlorobenzene, or the like, and is preferably tetrahydrofuran.
The molar ratio of the compound represented by formula II-1 to the hydrogen abstraction reagent can be 1: (1.5-3), preferably 1: (1.8 to 2.5), more preferably 1: 2.
the reaction temperature of the compound shown in the formula II-1 and the hydrogen extraction reagent can be-78 ℃ to room temperature, and the reaction time can be 6-24 h, such as 6h, 12h or 24 h.
A compound of formula II-1 with MX 4 May be 1: (0.5 to 1.5), preferably 1: (0.8 to 1.2), more preferably 1: 1; the temperature of the complexation reaction can be-78 ℃ to room temperature, and the time can be 6-24 h, for example, 6h, 12h or 24 h.
The hydrogen-drawing reagent is selected from sodium hydride, potassium hydride, lithium hydride and lithium bis (trimethylsilyl) amideSodium bis (trimethylsilyl) amide, lithium diisopropylamide or C 1 ～C 6 Alkyl lithium, more preferably sodium hydride, potassium hydride or butyl lithium.
Wherein, the compound shown in the formula II-1 can be prepared by the following steps:
(i) at C 1 ～C 6 In the presence of an acid catalyst, carrying out an aldehyde-amine condensation reaction on a compound shown in a formula III and a compound shown in a formula IV under heating reflux to obtain a compound shown in a formula V;
(ii) in an organic solvent, in the presence of an adsorbent, carrying out nucleophilic substitution reaction on a compound shown as a formula V and a compound shown as a formula VI under heating reflux to obtain a compound shown as a formula VII;
(iii) at C 1 ～C 6 In the presence of a reducing agent, the compound shown in the formula VII is subjected to reduction reaction at room temperature to obtain the compound shown in the formula II.
In the above-mentioned step (i),
said C is 1 ～C 6 The alcohol of (b) is an alcohol having 1 to 6 carbon atoms, and examples thereof are, for example, methanol, ethanol and isopropanol;
the acid catalyst is organic acid or inorganic acid, preferably C 1 ～C 6 An organic acid or an inorganic acid of (2), and examples of the acid catalyst are, for example, formic acid, acetic acid, propionic acid or hydrochloric acid;
the reaction time can be 6-12 h, for example 6h, 10h or 12h,
in addition, the obtained product can be separated by, for example, an alkaline alumina chromatographic column, and the separated eluent can be composed of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate can be 50: 1.
in the above-mentioned step (ii), the step (iii),
the organic solvent is preferably an aliphatic ketone or an aliphatic nitrile compound, more preferably acetone or acetonitrile, the adsorbent is preferably a carbonate, more preferably an alkali metal carbonate, for example, cesium carbonate or potassium carbonate;
the reaction time can be 6-12 h, for example, 6h, 10h or 12 h;
the obtained product can be separated by, for example, an alkaline alumina chromatographic column, and the separated eluent can be composed of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate can be 100: 1.
in the above-mentioned step (iii),
said C is 1 ～C 6 The alcohol of (b) is an alcohol having 1 to 6 carbon atoms, and examples thereof are, for example, methanol, ethanol and isopropanol; the reducing agent is preferably a negative hydrogen compound, preferably sodium borohydride or lithium aluminum hydride;
the reaction temperature is 25 ℃, and the reaction time can be 6-12 h, specifically 6h, 10h or 12 h;
the obtained product can be separated by means of, for example, an alkaline alumina chromatographic column, and the separated eluent can be composed of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate can be 50: 1.
the following specific examples are merely illustrative of the present invention and are not to be construed as limiting the invention.
Raw material source information:
triethylamine: not less than 99.5% (GC), Shanghai Aladdin Biotechnology Limited;
diphenyl phosphine chloride: 97%, Alfa Angsa (China) Chemicals, Inc.;
pyrrole: 98%, Bailingwei Tech Co., Ltd;
2-pyrrolecarboxaldehyde: 98%, Bailingwei Tech Co., Ltd;
n-butyl lithium: 1.6M hexane solution, Shanghai Alatin Biotech, Inc.;
isobutyraldehyde: 98%, alfa aesar (china) chemicals ltd;
methylcyclohexane: waterless grade, not less than 99%, Shanghai Aladdin Biotechnology Limited;
acetone: greater than or equal to 98%, Shanghai Allatin Biotechnology Limited;
salicylaldehyde: 98%, Shanghai Aladdin Biotechnology, Inc.;
tetrahydrofuran: 99%, alfa aesar (china) chemicals ltd;
sodium hydride: 60%, Shanghai Aladdin Biotechnology, Inc.;
cesium carbonate: 99%, welibbean technologies ltd;
dibromopropane: 97%, Bailingwei Tech Co Ltd;
methanol: 99.5%, welfare technologies ltd;
2, 6-dimethylaniline: 99%, welibbean technologies ltd;
2, 6-diisopropylaniline: 99%, welibbean technologies ltd;
2,4, 6-trimethylaniline: 99%, welibbean technologies ltd;
2,4, 6-tri-tert-butylaniline: 99%, lark technologies ltd;
4-ethylaniline: 99%, welibbean technologies ltd;
4- (tri-n-butylsilyl) phenyl phosphine chloride: 97%, Jiangsu Xinnoco catalyst Co., Ltd;
ethyl acetate: 99.9%, welfare technologies ltd;
ethanol: analytical purity, chemical reagents of national drug group limited;
tetrahydrofuran chromium chloride: 98%, lark technologies ltd;
molybdenum chloride (M.deg.C.. l) 5 ): 99.6%, alfa aesar (china) chemicals ltd;
tungsten chloride (WCl) 5 ): 99.9%, Shanghai Aladdin Biotechnology, Inc.;
ZrCl 4 : 99.5%, welength technologies ltd;
TiCl 4 : 99.9%, Shanghai Aladdin Biotechnology, Inc.;
HfCl 4 ：99.5%, Shanghai Aladdin Biotechnology, Inc.
Melting point test: the melting point (Tm) of the polymer was characterized by DSC with a Mettle DSC 1. About 5mg of the sample is weighed into an aluminum sample dish and sealed with a lid. And (4) putting the prepared sample into the sample cell by using tweezers, and covering a furnace cover. The quality of the sample is input into the control software, the temperature rise program firstly raises the temperature from 40 ℃ to 160 ℃ at the temperature rise rate of 10 ℃/min, and the temperature is kept at 160 ℃ for 5min to eliminate the thermal history. Then the temperature is reduced to 40 ℃ at the cooling rate of 10 ℃/min, and the crystallization curve of the sample is collected. And finally heating to 160 ℃ at a heating rate of 10 ℃/min, collecting a hot melting curve of the sample, and recording the enthalpy change and the melting point in the process.
Weight average molecular weight, degree of branching and molecular weight distribution index test: GPC-IR was used to determine the molecular weight, molecular weight distribution and degree of branching of the polymer product. The apparatus used was an Agilent7870 equipped with two columns of PLgel-oxides type. Weighing about 7mg of sample, placing the sample in a 20mL sample bottle, adding 10mL 1,2, 4-Trichlorobenzene (TCB) solution containing a small amount of antioxidant by using a syringe, dissolving the solution for 4 hours by shaking at 160 ℃, then filtering the solution in which the sample is dissolved into a sample introduction bottle by using a filter gun, and placing the sample introduction bottle into a sample introduction plate. The test temperature is 160 ℃, the flow rate of the solvent is 1.0mL/min, and when the instrument runs stably, the automatic sample injection test is started. A molecular weight calibration curve was obtained using Polystyrene (PS) as a standard.
First, preparation of the first catalyst
Preparation of examples 1 to 1
Dissolving pyrrole (1mol) and 2-pyrrole formaldehyde (1mol) in 100ml of pentane solution, slowly dropwise adding phosphorus oxychloride (0.2mol) at room temperature, reacting for 1-2 h, filtering to obtain a dipyrrole positive ion salt insoluble in the pentane solution, and dissolving the ion salt in Ca (OH) 2 And (4) violently shaking the suspension in the pentane solution for 5-10 min to obtain the pentane solution of dipyrromethene. Dropwise adding excessive n-butyllithium (3mol) into a dipyrromethene pentane solution at-78 ℃, slowly heating to room temperature, stirring for 2-3 h, filtering, adding diphenyl phosphine chloride (2.5mol) into the solution at-78 ℃, stirring for 2-3 h, standing overnight at room temperature, and carrying out column chromatography layer extractionAfter purification, recrystallization gives the ligand L 1 。 1 H NMR(400MHz，CDCl 3 ) 3.80 to 4.0(m, 1H)7.24 to 7.35(m, 20H)7.0 to 7.10(m, 2H) and 5.8 to 6.1(m, 4H). In the warp of N 2 A replacement Schlenk glass bottle was charged with dehydrated methylcyclohexane (200mL), tetrahydrofuran chromium chloride (100. mu. mol), and ligand L 1 (120 mu mol) and stirring for 15min to obtain a first catalyst I-a homogeneous solution.
Preparation examples 1 to 2
Dissolving trimethylacetaldehyde (2mol) and pyrrole (4.5mol) in 100mL of dichloromethane solution at room temperature, adding dichloromethane solution dissolved with trifluoroacetic acid (20mL) into the solution under the condition of argon, stirring for 3-4 h to generate dipyrromethene solution, dropwise adding excessive n-butyl lithium (3mol) into the dipyrromethene solution at-78 ℃, slowly heating to room temperature, stirring for 2-3 h, filtering, adding diphenyl phosphine chloride (2.5mol) into the solution at-78 ℃, stirring for 2-3 h, standing overnight at room temperature, purifying a chromatography layer, and recrystallizing to obtain a ligand L 2 。 1 H NMR(400MHz，CDCl 3 ) 3.68 to 3.80(m, 1H)7.24 to 7.35(m, 20H)70.0 to 7.10(m, 2H), 5.8 to 6.1(m, 4H), 0.95(s, 9H). In the warp of N 2 A replacement Schlenk glass bottle was charged with dehydrated toluene (200mL), tetrahydrofuran chromium chloride (100. mu. mol) and ligand L 2 (120 mu mol) and stirring for 12min to obtain a first catalyst I-b homogeneous solution.
Preparation examples 1 to 3
The trimethylacetaldehyde in example 1-2 was changed to isobutyraldehyde without changing other conditions to obtain ligand L 3 。 1 H NMR(400MHz，CDCl 3 ):3.80～4.0(m，1H)7.24～7.35(m，20H)7.0～7.10(m，2H)，5.8～6.1(m，4H)，0.95(s，6H)，2.40～2.50(m, 1H). In the warp of N 2 A replacement Schlenk glass bottle was charged with dehydrated Isopar E (200ml), tetrahydrofuran chromium chloride (100. mu. mol) and ligand L 3 (120 mu mol) and stirring for 10min to obtain a first catalyst I-c homogeneous phase solution.
Preparation examples 1 to 4
The diphenylphosphine chloride obtained in example 1-2 was replaced with bis (4- (tri-n-butylsilyl) phenyl) phosphine chloride under otherwise unchanged conditions to obtain a ligand L 4 。 1 H NMR(400MHz，CDCl 3 ) 7.36 to 7.40(m, 16H)5.85 to 7.02(m, 6H)0.90 to 1.45(m, 117H) 4.03(m, 1H). In the warp N 2 A replacement Schlenk glass bottle was charged with dehydrated toluene (200ml), molybdenum chloride MoCl 5 (100. mu. mol) and a ligand L 4 (120 mu mol) and stirring for 10min to obtain a first catalyst I-d homogeneous phase solution.
Preparation examples 1 to 5
Using the ligands L prepared in preparation examples 1 to 3 3 . In the warp of N 2 A replacement Schlenk glass bottle was charged with dehydrated toluene (200ml), tungsten chloride WCl 5 (100. mu. mol) and a ligand L 3 (120 mu mol) and stirring for 10min to obtain a first catalyst I-e homogeneous solution.
Preparation of the second catalyst
The synthesis of the complex in the following examples was carried out according to the following reaction equation:
preparation example 2-1
(1) Preparation of the Compound of formula A1 (R) 1 ＝R 5 ＝Me；R 2 ＝R 3 ＝R 4 ＝H)
3-t-butylsalicylaldehyde (3.56g,20mmol) and 2, 6-dimethylaniline (2.43g,20mmol) were added to a 100-mL round-bottomed flask, 50mL of anhydrous methanol and 0.10mL of formic acid were added, the mixture was refluxed for 6 hours, and the reaction solution was concentrated and subjected to basic alumina column chromatography (petroleum ether: ethyl acetate ═ 50: 1(v/v)) to obtain 4.82g of a product with a yield of 85.6%. 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.78(s,1H,-CH＝N-),7.35(d,J＝8.0Hz,1H),7.16–7.14(m,4H),6.88(t,J＝8.0Hz,1H),5.74(s,1H,-OH),2.25(s,6H),1.40(s,9H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.0,155.8,152.2,137.1,129.9,129.1,128.0,127.3,126.0,120.0,117.1,34.1,31.6,18.6.Anal.Calcd for C 19 H 23 NO(281.40):C,81.10；H,8.24；N,4.98.Found:C,80.83；H,8.61；N,4.74。
(2) Preparation of a Compound of formula B1 (R) 1 ＝R 5 ＝Me；R 2 ＝R 3 ＝R 4 ＝H)
Under a nitrogen atmosphere, 2.81g A1 (10mmol) was dissolved in 30mL of acetone, 1.39g of 1, 3-dibromopropane (5mmol, 0.5eq.) was added, 1.63g of cesium carbonate (5mmol, 0.5eq.) was added, and the mixture was refluxed for 10 hours. The solid was removed by filtration, and the filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate: 100: 1(v/v)) to give 2.19g of the product in a yield of 72.5%. 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.78(s,2H,-CH＝N-),7.52(d,J＝8.0Hz,2H),7.32(d,J＝8.0Hz,2H),7.14–7.12(m,6H),7.00(t,J＝8.0Hz,2H),4.29(t,J＝8.0Hz,4H),2.27–2.25(m,2H),2.21(s,12H),1.40(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.0,152.2,135.6,129.1,127.3,126.0,119.0,115.6,65.3,34.4,31.6,29.0,18.6.Anal.Calcd for C 41 H 50 N 2 O 2 (602.86):C,81.69；H,8.36；N,4.65.Found:C,81.53；H,8.61；N,4.54。
(3) Preparation of the Compound of formula C1 (R) 1 ＝R 5 ＝Me；R 2 ＝R 3 ＝R 4 ＝H)
The compound (3mmol) 1.81g B1 was dissolved in 20mL of anhydrous methanol, 0.23g of sodium borohydride (6mmol, 2.0eq.) was slowly added, the reaction was carried out at room temperature for 6 hours, 5mL of water was added to quench the reaction, the solvent was dried by spinning, extraction was carried out with ethyl acetate, drying was carried out with anhydrous sodium sulfate, and the filtrate was concentrated and then purified by silica gel column chromatography (petroleum ether: ethyl acetate 50: 1(v/v)) to obtain 1.68g of the product with a yield of 92.5%. 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.28(d,J＝8.0Hz,2H),7.16(t,J＝8.0Hz,2H),7.08(d,J＝8.0Hz,2H),6.99(d,J＝8.0Hz,4H),6.88(t,J＝8.0Hz,2H),6.35(s,2H,-NH),4.45(s,4H),4.29(t,J＝8.0Hz,4H),2.27–2.25(m,2H),2.12(s,12H),1.40(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ148.4,145.2,143.7,128.9,128.3,127.0,125.8,124.4,119.7,65.6,52.1,34.7,31.6,29.0,17.9.Anal.Calcd for C 41 H 54 N 2 O 2 (606.90):C,81.14；H,8.97；N,4.62.Found:C,81.00；H,9.11；N,4.44。
(4) Preparation of a Compound of formula D1 (M ═ Zr; R 1 ＝R 5 ＝Me；R 2 ＝R 3 ＝R 4 ＝H)
Adding NaH (0.05g, 2mmol) into a tetrahydrofuran solution of C1(0.61g, 1mmol) at the temperature of minus 78 ℃ under the protection of nitrogen, slowly returning the system to the room temperature, reacting for 6 hours, cooling the system to the temperature of minus 78 ℃, adding zirconium tetrachloride (0.23g, 1mmol), slowly returning to the room temperature, continuing to react for 12 hours, filtering, washing and drying to obtain 0.45g of a product, namely the complex Zr1, wherein the yield is 58.5%. 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.28(d,J＝8.0Hz,2H),7.16(t,J＝8.0Hz,2H),7.08(d,J＝8.0Hz,2H),6.99(d,J＝8.0Hz,4H),6.88(t,J＝8.0Hz,2H),4.32(s,4H),3.92(t,J＝8.0Hz,4H),2.15–2.13(m,2H),2.11(s,12H),1.40(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ148.4,144.9,143.7,128.3,127.0,126.1,125.8,124.4,119.7,68.3,37.0,34.7,31.6,30.2,17.9.Anal.Calcd for C 41 H 52 Cl 2 N 2 O 2 Zr(767.00):C,64.20；H,6.83；N,3.65.Found:C,64.02；H,6.61；N,3.48。
Preparation examples 2 to 2
(1) Preparation of the Compound of formula A2 (R) 1 ＝R 5 ＝ i Pr；R 2 ＝R 3 ＝R 4 ＝H)
Experimental procedure the same preparation as in preparation example 2-1(1), 3-tert-butylsalicylaldehyde (3.56g,20mmol) and 2, 6-diisopropylaniline (3.55g,20mmol) were reacted to give 5.66g of product in 83.8% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.78(s,1H,-CH＝N-),7.38–7.35(m,2H),7.15–7.12(m,3H),6.88(t,J＝8.0Hz,1H),5.74(s,1H,-OH),2.78–2.75(m,2H),1.40(s,9H),1.18(d,J＝8.0Hz,12H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.0,155.8,146.4,137.1,135.7,129.9,128.0,122.3,121.3,120.0,117.1,34.1,31.6,28.9,23.3.Anal.Calcd for C 23 H 31 NO(337.51):C,81.85；H,9.26；N,4.15.Found:C,81.53；H,9.55；N,4.01。
(2) Preparation of a Compound of formula B2 (R) 1 ＝R 5 ＝ i Pr；R 2 ＝R 3 ＝R 4 ＝H)
Experimental procedure the compound of preparation example 2-1(2), A2 (3.38g, 10mmol) was reacted with 1, 3-dibromopropane (1.39g,5mmol, 0.5eq.) to give 2.44g of product in 68.3% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):8.78(s,2H,-CH＝N-),7.52(d,J＝8.0Hz,2H),7.38(t,J＝8.0Hz,2H),7.32(d,J＝8.0Hz,2H),7.12(d,J＝8.0Hz,4H),7.00(t,J＝8.0Hz,2H),4.29(t,J＝8.0Hz,4H),2.78–2.75(m,4H),2.27–2.25(m,2H),1.40(s,18H),1.18(d,J＝8.0Hz,24H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.0,155.8,146.4,135.6,129.1,127.2,122.3,121.3,119.0,115.6,65.3,34.4,31.6,28.9,23.3.Anal.Calcd for C 49 H 66 N 2 O 2 (715.08):C,82.30；H,9.30；N,3.92.Found:C,82.03；H,9.55；N,3.71。
(3) Preparation of the Compound of formula C2 (R) 1 ＝R 5 ＝ i Pr；R 2 ＝R 3 ＝R 4 ＝H)
Experimental procedure the compound of preparation example 2-1(3), B2 (2.15g, 3mmol) was reacted with sodium borohydride (0.23g,6mmol, 2.0eq.) to give 2.06g,the yield was 95.3%. 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.28(d,J＝8.0Hz,2H),7.16(t,J＝8.0Hz,2H),7.12(d,J＝8.0Hz,4H),7.08(d,J＝8.0Hz,2H),6.95(t,J＝8.0Hz,2H),6.35(s,2H,-NH),4.45(s,4H),4.29(t,J＝8.0Hz,4H),2.89–2.87(m,4H),2.27–2.25(m,2H),1.40(s,18H),1.18(d,J＝8.0Hz,24H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ148.4,143.7,139.4,130.9,127.0,125.8,124.4,124.1,119.7,65.6,52.1,34.7,31.6,29.0,23.3.Anal.Calcd for C 49 H 70 N 2 O 2 (719.11):C,81.84；H,9.81；N,3.90.Found:C,81.63；H,10.05；N,3.73。
(4) Preparation of a Compound of formula D2 (M ═ Zr; R 1 ＝R 5 ＝ i Pr；R 2 ＝R 3 ＝R 4 ＝H)
The same procedures as those conducted in preparation example 2-1(4) were conducted except that a C2 compound (0.72g, 1mmol) was used in place of the C1 compound, and the hydrogen abstraction reaction and the complexation reaction were all carried out at-30 ℃ to give 0.49g of the product, i.e., complex Zr2, in 55.3% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.28(d,J＝8.0Hz,2H),7.16(t,J＝8.0Hz,2H),7.12(d,J＝8.0Hz,4H),7.08(d,J＝8.0Hz,2H),6.95(t,J＝8.0Hz,2H),4.32(s,4H),3.92(t,J＝8.0Hz,4H),2.89–2.87(m,4H),2.15–2.13(m,2H),1.40(s,18H),1.18(d,J＝8.0Hz,24H). 13 CNMR(CDCl 3 ,100MHz,TMS):δ148.4,143.7,139.1,133.2,127.0,125.8,124.4,124.1,119.7,68.3,37.0,34.7,31.6,30.0,28.7,23.3.Anal.Calcd for C 49 H 68 Cl 2 N 2 O 2 Zr(879.22):C,66.94；H,7.80；N,3.19.Found:C,66.73；H,7.98；N,3.03。
Preparation examples 2 to 3
(1) Preparation of the Compound of formula A3 (R) 1 ＝R 3 ＝R 5 ＝Me；R 2 ＝R 4 ＝H)
Experimental procedure As in preparation example 2-1(1), 3-tert-butylsalicylaldehyde (3.56g,20mmol) was reacted with 2,4, 6-trimethylaniline (2.71g,20mmol) to give 4.85g of product in 82.1% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.78(s,1H,-CH＝N-),7.35(d,J＝8.0Hz,1H),7.15(d,J＝8.0Hz,1H),6.98–6.96(m,3H),5.74(s,1H,-OH),2.34(s,6H),2.18(s,3H),1.40(s,9H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.0,155.8,149.2,137.1,129.9,128.2,128.0,125.4,120.0,117.1,34.1,31.6,21.9,18.9.Anal.Calcd for C 20 H 25 NO(295.43):C,81.31；H,8.53；N,4.74.Found:C,81.00；H,8.82；N,4.51。
(2) Preparation of the Compound (R) of formula B3 1 ＝R 3 ＝R 5 ＝Me；R 2 ＝R 4 ＝H)
Experimental procedure the compound of preparation example 2-1(2), A3 (2.95g, 10mmol) was reacted with 1, 3-dibromopropane (1.39g,5mmol, 0.5eq.) to give 2.23g of product in 70.6% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):8.78(s,2H,-CH＝N-),7.52(d,J＝8.0Hz,2H),7.32(d,J＝8.0Hz,2H),7.00(t,J＝8.0Hz,2H),6.86(s,4H),4.29(t,J＝8.0Hz,4H),2.27–2.25(m,2H),2.34(s,12H),2.18(s,6H),1.40(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.0,152.2,149.2,135.6,129.1,128.2,127.9,127.2,125.4,119.0,115.6,65.3,34.4,31.6,21.9,18.9.Anal.Calcd for C 43 H 54 N 2 O 2 (630.92):C,81.86；H,8.63；N,4.44.Found:C,81.63；H,8.85；N,4.31。
(3) Preparation of the Compound of formula C3 (R) 1 ＝R 3 ＝R 5 ＝Me；R 2 ＝R 4 ＝H)
The experimental procedure was the same as in preparation example 2-1(3), compound B3 (1.89g, 3mmol) was reacted with sodium borohydride (0.23g,6mmol, 2.0eq.) to give 1.78g of product in 93.4% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.28(d,J＝8.0Hz,2H),7.16(t,J＝8.0Hz,2H),7.08(d,J＝8.0Hz,2H),6.71(s,4H),6.35(s,2H,-NH),4.45(s,4H),4.29(t,J＝8.0Hz,4H),2.27–2.25(m,2H),2.21(s,6H),2.12(s,12H),1.40(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ148.4,143.7,142.2,129.2,128.7,127.0,126.0,125.8,124.4,119.7,65.6,52.1,34.7,31.6,29.0,21.9,18.2.Anal.Calcd for C 43 H 58 N 2 O 2 (634.95):C,81.34；H,9.21；N,4.41.Found:C,81.03；H,9.55；N,4.35。
(4) System for makingPreparing a compound represented by formula D3 (M ═ Zr; R 1 ＝R 3 ＝R 5 ＝Me；R 2 ＝R 4 ＝H)
The same procedures as in preparation example 2-1(4) were carried out except that a C3 compound (0.63g, 1mmol) was used in place of the C1 compound, and the temperatures of the hydrogen abstraction reaction and the complexation reaction were both at room temperature, to give 0.42g of the product, i.e., complex Zr3, in 52.6% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.28(d,J＝8.0Hz,2H),7.16(t,J＝8.0Hz,2H),7.08(d,J＝8.0Hz,2H),6.71(s,4H),4.32(s,4H),3.92(t,J＝8.0Hz,4H),2.26(s,6H),2.15–2.13(m,2H),2.11(s,12H),1.40(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ148.4,143.7,141.9,129.2,128.7,127.0,126.0,125.8,124.4,119.7,68.3,37.0,34.7,31.6,30.2,29.0,21.9,18.2.Anal.Calcd for C 43 H 56 Cl 2 N 2 O 2 Zr(795.06):C,64.96；H,7.10；N,3.52.Found:C,64.83；H,7.35；N,3.35。
Preparation examples 2 to 4
(1) Preparation of the Compound of formula A4 (R) 1 ＝R 3 ＝R 5 ＝ t Bu；R 2 ＝R 4 ＝H)
Experimental procedure As in preparation example 2-1(1), 3-tert-butylsalicylaldehyde (3.56g,20mmol) was reacted with 2,4, 6-tri-tert-butylaniline (5.23g,20mmol) to give 6.80g of product in 80.6% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.78(s,1H,-CH＝N-),7.35(d,J＝8.0Hz,1H),7.25(s,2H),7.15(d,J＝8.0Hz,1H),6.88(t,J＝8.0Hz,1H),5.74(s,1H,-OH),1.40(s,9H),1.38(s,18H),1.31(s,9H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.0,155.8,141.1,140.4,137.1,132.2,129.9,128.0,122.3,120.0,117.1,36.3,34.8,34.1,31.6,31.3.Anal.Calcd for C 29 H 43 NO(421.67):C,82.60；H,10.28；N,3.32.Found:C,82.46；H,10.62；N,3.01。
(2) Preparation of a Compound of formula B4 (R) 1 ＝R 3 ＝R 5 ＝ t Bu；R 2 ＝R 4 ＝H)
Experimental procedure was as in preparation example 2-1(2), A4 compound (4.22g, 10mmol) and 1, 3-dibromopropaneAlkane (1.39g,5mmol, 0.5eq.) was reacted to give 2.91g of product in 65.8% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):8.78(s,2H,-CH＝N-),7.52(d,J＝8.0Hz,2H),7.32(d,J＝8.0Hz,2H),7.25(s,4H),7.00(t,J＝8.0Hz,2H),4.29(t,J＝8.0Hz,4H),2.27–2.25(m,2H),1.40(s,18H),1.38(s,36H),1.31(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.0,152.2,141.1,140.4,135.6,132.2,129.1,127.2,122.3,119.0,115.6,65.3,36.3,34.8,34.4,31.6,31.3,29.0.Anal.Calcd for C 61 H 90 N 2 O 2 (883.40):C,82.94；H,10.27；N,3.17.Found:C,82.63；H,10.55；N,3.01。
(3) Preparation of the Compound of formula C4 (R) 1 ＝R 3 ＝R 5 ＝ t Bu；R 2 ＝R 4 ＝H)
Experimental procedure the compound of preparation example 2-1(3), B4 (2.65g, 3mmol) was reacted with sodium borohydride (0.23g,6mmol, 2.0eq.) to give 2.58g of product in 96.8% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.28(d,J＝8.0Hz,2H),7.19(s,4H),7.16(t,J＝8.0Hz,2H),7.08(d,J＝8.0Hz,2H),6.35(s,2H,-NH),4.45(s,4H),4.29(t,J＝8.0Hz,4H),2.27–2.25(m,2H),1.40(s,18H),1.37(s,36H),1.31(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ148.7,148.4,143.7,134.1,131.9,127.0,125.8,125.3,124.4,119.7,65.6,52.1,37.3,34.7,31.6,31.3,29.0.Anal.Calcd for C 61 H 94 N 2 O 2 (887.44):C,82.56；H,10.68；N,3.16.Found:C,82.33；H,10.85；N,3.07。.
(4) Preparation of a Compound of formula D4 (M ═ Zr; R 1 ＝R 3 ＝R 5 ＝ t Bu；R 2 ＝R 4 ＝H)
The same procedures as those conducted in preparation example 2-1(4) were carried out except that a C4 compound (0.89g, 1mmol) was used in place of the C1 compound, and the temperatures of the hydrogen abstraction reaction and the complexation reaction were all-20 ℃ to give 0.51g of a product, i.e., complex Zr4, in 48.8% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.28(d,J＝8.0Hz,2H),7.19(s,4H),7.16(t,J＝8.0Hz,2H),7.08(d,J＝8.0Hz,2H),4.32(s,4H),3.92(t,J＝8.0Hz,4H),2.15–2.13(m,2H),1.40(s,18H),1.37(s,36H),1.31(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ148.7,148.4,143.7,133.8,131.9,127.0,125.8,125.3,124.4,119.7,68.3,37.0,34.7,31.6,31.3,30.2.Anal.Calcd for C 61 H 92 Cl 2 N 2 O 2 Zr(1047.54):C,69.94；H,8.85；N,2.67.Found:C,69.76；H,9.02；N,2.54。
Preparation examples 2 to 4
Preparation of a Compound of formula D1 (M ═ Ti; R 1 ＝R 5 ＝Me；R 2 ＝R 3 ＝R 4 ＝H)
The same procedures as in preparation example 2-1(4) were carried out except that titanium tetrachloride (0.19g, 1mmol) was used instead of zirconium tetrachloride (0.23g, 1mmol), to give 0.37g of a product which was complex Ti1 in a yield of 51.1%. 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.29(d,J＝8.0Hz,2H),7.15(t,J＝8.0Hz,2H),7.09(d,J＝8.0Hz,2H),6.99(d,J＝8.0Hz,4H),6.90(t,J＝8.0Hz,2H),4.33(s,4H),3.91(t,J＝8.0Hz,4H),2.16–2.13(m,2H),2.10(s,12H),1.42(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ149.9,144.0,143.1,128.0,127.8,125.1,125.1,124.2,119.75,68.1,37.2,34.5,31.1,30.0,17.8.Anal.Calcdfor C 41 H 52 Cl 2 N 2 O 2 Ti(723.65):C,68.05；H,7.24；N,3.87.Found:C,67.82；H,7.51；N,3.68。
Preparation examples 2 to 5
Preparation of a Compound of formula D1 (M ═ Hf; R 1 ＝R 5 ＝Me；R 2 ＝R 3 ＝R 4 ＝H)
The same procedures as in preparation examples 2-1(4) were carried out except that hafnium tetrachloride (0.32g, 1mmol) was used instead of zirconium tetrachloride (0.23g, 1mmol), to give 0.41g of a product, i.e., complex Hf1 in 47.8% yield. 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.27(d,J＝8.0Hz,2H),7.15(t,J＝8.0Hz,2H),7.07(d,J＝8.0Hz,2H),6.98(d,J＝8.0Hz,4H),6.89(t,J＝8.0Hz,2H),4.33(s,4H),3.90(t,J＝8.0Hz,4H),2.15–2.12(m,2H),2.12(s,12H),1.39(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ147.4,144.0,143.2,128.1,127.1,126.5,125.1,124.2,119.5,68.1,37.2,34.5,31.5,30.0,17.8.Anal.Calcd for C 41 H 52 Cl 2 N 2 O 2 Hf(854.27):C,57.65；H,6.14；N,3.28.Found:C,57.43；H,5.95；N,3.02。
Example 1
Polymerization experiment: heating a 300ml reaction kettle to 130 ℃, vacuumizing for 2h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. At the reaction temperature of 75 ℃ and the ethylene pressure of 3MPa, 100ml of methylcyclohexane subjected to water and oxygen removal and 600 mu mol of MAO are sequentially added into a reactor, the mixture is stirred for 2min, 3 mu mol of a first catalyst I-a is added for reaction for 20min (sampling GC test, oligomerization is mainly ethylene tetramerization reaction, a small amount of ethylene trimerization reaction is carried out, the molar ratio of 1-octene to 1-hexene in a reaction liquid is 4.8: 1), 3.5 mu mol of a second catalyst Zr1 is added, the reaction is continued for 10min, the reaction is stopped, 700 mu mol of ethanol is added after pressure relief, a product is collected and dried, and 30.09g of LLDPE is obtained. The properties of the polymers are shown in Table 2.
Examples 2 to 7
The polymerization reactions in examples 2 to 7 were carried out in the same manner as in example 1 except for following the conditions shown in table 1. The properties of the resulting polymer are shown in Table 2.
Example 8
Heating a 300ml reaction kettle to 120 ℃, vacuumizing for 3 hours, replacing by adopting nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. At the reaction temperature of 60 ℃ and under the condition of the ethylene pressure of 4MPa, sequentially adding 100ml of toluene after water and oxygen removal and 500 mu mol of MMAO into a reactor, stirring for 1min, adding 2 mu mol of a first catalyst I-b, reacting for 40min, then adding 4 mu mol of a second catalyst Zr2, continuing to react for 50min, stopping the reaction, decompressing, adding 1500 mu mol of 2-ethylhexanol, collecting the product and drying to obtain 48.72g of LLDPE. The properties of the resulting polymer are shown in Table 2.
Example 9
Polymerization experiment: heating a 500ml reaction kettle to 150 ℃, vacuumizing for 1h, replacing by adopting nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. Under the conditions that the reaction temperature is 55 ℃ and the ethylene pressure is 1MPa, 200ml of Isopar E after water and oxygen removal and 900 mu mol of MAO are sequentially added into a reactor, the mixture is stirred for 5min, 6 mu mol of first catalyst I-c is added for reaction for 30min, then 9 mu mol of second catalyst Zr3 is added for continuous reaction for 60min, the reaction is stopped, 2500 mu mol of tetradecanol is added after pressure relief, the product is collected and dried, and 63.77g of LLDPE is obtained. The properties of the resulting polymer are shown in Table 2.
Example 10
Polymerization experiment: heating a 500ml reaction kettle to 125 ℃, vacuumizing for 2.5h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. Under the conditions that the reaction temperature is 65 ℃ and the ethylene pressure is 5MPa, 200ml of cyclohexane which is subjected to water removal and oxygen removal and 600 mu mol of MMAO are sequentially added into a reactor, the mixture is stirred for 5min, 5 mu mol of first catalyst I-c is added for reaction for 10min, then 10 mu mol of second catalyst Zr3 is added, the reaction is continued for 70min, the reaction is stopped, 900 mu mol of hexadecanol is added after pressure relief, products are collected and dried, and 91.23g of LLDPE is obtained. The properties of the resulting polymer are shown in Table 2.
Example 11
Polymerization experiment: heating a 300ml reaction kettle to 140 ℃, vacuumizing for 2h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. At the reaction temperature of 65 ℃ and the ethylene pressure of 1MPa, 200ml of Isopar E after water and oxygen removal and 6000 mu mol of MAO are sequentially added into a reactor, stirred for 3min, added with 9 mu mol of a first catalyst I-c to react for 15min, then added with 15 mu mol of a second catalyst Zr4 to continue to react for 90min, the reaction is stopped, 1800 mu mol of ethanol is added after pressure relief, and products are collected and dried to obtain 23.19g of LLDPE. The properties of the polymers are shown in Table 2.
Examples 12 to 13
Polymerization was carried out in the same manner as in example 1 except that the conditions shown in table 1 were followed. The properties of the polymers are shown in Table 2.
Table 1: reaction conditions
TABLE 2
As a whole, as the amount of the second catalyst added increases, the molecular weight of the polymer increases and the molecular weight distribution becomes narrower. As the ethylene pressure is increased, the amount of 1-octene produced is increased, the amount of polymer produced is increased, and the molecular weight distribution of the polymer is broadened. The activity of the MMAO adjuvant is superior to that of the adjuvant MAO.
Claims (36)
1. A catalyst system for preparing LLDPE by cascade catalysis comprises a first catalyst, a second catalyst and a cocatalyst,
wherein the first catalyst is a metal complex of a phenylphosphine represented by formula I,
wherein A is a metal selected from group VIB;
R 1 is halogen, acetylacetonate or isooctanoate;
n is 3, 4 or 5, which is a value corresponding to the valence state of A;
R 2 and R 3 Each independently is substituted or unsubstituted C 6 ～C 14 An aryl group;
R 4 selected from hydrogen, C 1 ～C 6 Alkyl radical, C 3 ～C 8 Cycloalkyl, or substituted or unsubstituted C 6 ～C 14 An aryl group;
the second catalyst is an arylamino ether metal complex represented by formula II,
wherein R is 1 To R 9 Each of which is the same or different and each is independently selected from hydrogen, C 1 ～C 10 Alkyl radical, C 1 ～C 10 Alkoxy radical, C 3 ～C 10 Cycloalkyl, C 3 ～C 10 Cycloalkyl oxy, C 6 ～C 14 Aryl or C 6 ～C 14 An aryloxy group;
m is a transition metal selected from group IVB,
x is halogen;
the cocatalyst is at least one selected from alkyl aluminoxane, alkyl aluminum halide or modified alkyl aluminoxane.
2. The catalyst system of claim 1, wherein,
a is selected from chromium (III), molybdenum (V) or tungsten (V),
R 2 and R 3 Each independently being substituted C 6 ～C 14 Aryl, said substituted C 6 ～C 14 Substituents in aryl groups being selected from C 1 ～C 6 Alkyl radical, C 1 ～C 6 Alkoxy, halogen, C 3 ～C 8 Cycloalkyl, silyl, or one or more C 1 ～C 6 One or more alkyl-substituted silane groups.
3. The catalyst system of claim 1, wherein,
R 2 and R 3 Each independently being substituted C 6 ～C 14 Aryl, said substituted C 6 ～C 14 Substituents in aryl groups being selected from C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, halogen, C 3 ～C 6 Cycloalkyl, silyl, or one or more C 1 ～C 6 One or more alkyl-substituted silane groups.
4. The catalyst system of claim 1, wherein,
R 2 and R 3 Each independently selected from phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl,4-methoxyphenyl group, 4-ethoxyphenyl group, o-methoxyphenyl group, o-ethoxyphenyl group, 2-methylphenyl group, 2-ethylphenyl group, 2-isopropylphenyl group, 2, 4-dimethylphenyl group, 2, 4-diethylphenyl group, 2, 4-diisopropylphenyl group, 2, 4-dibutylphenyl group, 2, 6-diisopropylphenyl group, 2, 6-dimethylphenyl group, 2, 6-diethylphenyl group, 2, 6-dibutylphenyl group, naphthyl group, anthryl group, biphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-silylphenyl group, 4-silylphenyl group, 2- (trimethylsilyl) phenyl group, 4- (trimethylsilyl) phenyl group, 2- (triethylsilyl) phenyl group, o-ethoxyphenyl group, 2-methylphenyl group, 2-ethylphenyl group, 2-isopropylphenyl group, 2, 4-dimethylphenyl group, 2, 6-dimethylphenyl group, biphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-silylphenyl group, 4-silylphenyl group, 2- (trimethylsilyl) phenyl group, 4- (triethylsilyl) phenyl group, o-methyl group, and the like, 4- (triethylsilyl) phenyl, 4- (triisopropylsilyl) phenyl, 4- (tributylsilyl) phenyl, 4- (triisobutylsilyl) phenyl, 4- (tri-tert-butylsilyl) phenyl, or 2- (tri-tert-butylsilyl) phenyl.
5. The catalyst system of claim 1, wherein,
R 4 selected from substituted C 6 ～C 14 Aryl, said substituted C 6 ～C 14 Substituents in aryl groups being selected from C 1 ～C 6 Alkyl radical, C 1 ～C 6 Alkoxy, halogen or C 3 ～C 8 A cycloalkyl group.
6. The catalyst system of claim 1, wherein,
R 4 selected from substituted C 6 ～C 14 Aryl, said substituted C 6 ～C 14 Substituents in aryl groups being selected from C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, halogen, C 3 ～C 6 Cycloalkyl, silyl or C 1 ～C 6 One or more of alkylsilyl groups.
7. The catalyst system of claim 1, wherein,
R 4 selected from hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylPhenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, o-methoxyphenyl, o-ethoxyphenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, 2, 4-dimethylphenyl, 2, 4-diethylphenyl, 2, 4-diisopropylphenyl, 2, 4-dibutylphenyl, 2, 6-diisopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-dibutylphenyl, naphthyl, anthryl, biphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-silylphenyl, 4-silylphenyl, 2- (trimethylsilyl) phenyl, 4- (trimethylsilyl) phenyl, 2- (triethylsilyl) phenyl, 4- (triisopropylsilyl) phenyl, 4- (tributylsilyl) phenyl, 4- (triisobutylsilyl) phenyl, 4- (tri-tert-butylsilyl) phenyl, or 2- (tri-tert-butylsilyl) phenyl.
8. The catalyst system of claim 1, wherein,
m is selected from titanium, zirconium or hafnium;
x is bromine or chlorine.
9. The catalyst system of claim 1, wherein,
R 1 and R 5 Each independently is C 1 ～C 6 An alkyl group.
10. The catalyst system of claim 1, wherein,
R 2 and R 4 Each independently is hydrogen or C 1 ～C 6 An alkyl group.
11. The catalyst system of claim 1, wherein,
R 3 each independently is hydrogen, C 1 ～C 6 An alkyl group.
12. The catalyst system of claim 1, wherein,
R 6 to R 8 Each independently is hydrogen or C 1 ～C 6 An alkyl group.
13. The catalyst system of claim 1, wherein,
R 9 each independently is hydrogen or C 1 ～C 6 An alkyl group.
14. The catalyst system of claim 1, wherein,
R 1 and R 5 Each independently is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl;
R 2 and R 4 Each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl;
R 3 each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl;
R 6 to R 8 Each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; and
R 9 each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
15. The catalyst system of claim 1, wherein,
the molar ratio of the first catalyst to the second catalyst to the cocatalyst is 1: (0.05-10): (10-2000).
16. The catalyst system of claim 1, wherein,
the molar ratio of the first catalyst to the second catalyst to the cocatalyst is 1: (0.1-5): (50-1000).
17. The catalyst system of claim 1, wherein,
the first catalyst is selected from any one of the following complexes:
the second catalyst is any one of the following complexes:
18. the catalyst system of any one of claims 1 to 17, wherein,
the alkylaluminoxane is C 1 ～C 5 Alkylaluminoxane;
the alkyl aluminum is C 1 ～C 5 An aluminum alkyl;
the alkyl aluminum halide is C 1 ～C 5 An alkyl aluminum halide;
the modified aluminoxane is selected from triisobutylaluminum or trioctylaluminum modified C 1 ～C 5 An alkylaluminoxane.
19. The catalyst system of claim 18,
the alkylaluminoxane is selected from methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isopropylaluminoxane or tert-butylaluminoxane;
the alkyl aluminum is selected from trimethyl aluminum, triethyl aluminum, tripropyl aluminum or tributyl aluminum;
the alkyl aluminum halide is diethyl aluminum monochloride, ethyl aluminum dichloride or ethyl aluminum sesquichloride;
the modified aluminoxane is selected from triisobutylaluminum modified methylaluminoxane, triisobutylaluminum modified ethylaluminoxane, triisobutylaluminum modified propylaluminoxane, trioctylaluminum modified methylaluminoxane and trioctylaluminum modified ethylaluminoxane.
20. A catalytic polymerization system for the preparation of LLDPE with tandem catalysis, comprising:
the catalyst system of any one of claims 1 to 19;
a vinyl monomer; and
a solvent.
21. The catalytic polymerization system of claim 20, wherein,
the solvent is selected from aliphatic hydrocarbon solvents and/or aromatic hydrocarbon solvents, and
the pressure intensity of the ethylene is 1 MPa-5 MPa.
22. The catalytic polymerization system of claim 21, wherein,
the aliphatic hydrocarbon solvent is selected from one or more of n-butane, isobutane, n-pentane, cyclopentane, methylcyclopentane, methylene cyclopentane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, n-heptane, n-octane, n-nonane or Isopar E; and
the aromatic hydrocarbon solvent is selected from one or more of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene or dichlorotoluene.
23. Use of a catalyst system according to any one of claims 1 to 19 or a catalytic polymer system according to any one of claims 20 to 22 in the preparation of LLDPE.
24. A process for the preparation of LLDPE comprising the steps of:
1) oligomerizing ethylene in a high pressure reactor at an ethylene pressure of 1 to 5MPa in a solvent in the presence of the first catalyst and cocatalyst of any one of claims 1 to 19;
2) after the oligomerization reaction of step 1) is completed, adding the second catalyst of any one of claims 1 to 19 to the reaction system so that ethylene is copolymerized with the oligomer obtained in step 1) to produce LLDPE,
wherein the molar ratio of the first catalyst, the second catalyst and the cocatalyst is 1: (0.05-10): (10-2000) of a first polymer,
the ratio of the first catalyst to the solvent is 0.1-80 mu mol/100 ml.
25. The process of claim 24, wherein the molar ratio of the first catalyst, second catalyst, and co-catalyst is 1: (0.1-5): (50-1000).
26. The method of claim 24, wherein the ratio of the first catalyst to the solvent is 0.5 to 50 μmol/100 ml.
27. The process according to claim 24, wherein the solvent is selected from an aliphatic hydrocarbon solvent and/or an aromatic hydrocarbon solvent.
28. The method of claim 24, wherein,
the aliphatic hydrocarbon solvent is selected from one or more of n-butane, isobutane, n-pentane, cyclopentane, methylcyclopentane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, n-heptane, n-octane, n-nonane or Isopar E;
the aromatic hydrocarbon solvent is selected from one or more of toluene, xylene, monochlorobenzene, dichlorobenzene or dichlorotoluene;
the reaction temperatures of step 1) and step 2) are independently 50 ℃ to 100 ℃.
29. The process of any one of claims 24 to 28, wherein a quencher is added to step 2) to terminate the reaction.
30. The method of claim 29, wherein,
the amount of the quenching agent is 0.5-5 times of the amount of the cocatalyst substance;
the quencher is an alcohol having 2 to 20 carbon atoms.
31. The method of claim 29, wherein,
the amount of the quenching agent is 1-3 times of the amount of the cocatalyst substance.
32. The method of claim 29, wherein,
the quenching agent is selected from one or more of ethanol, ethylene glycol, n-propanol, glycerol, n-butanol, 2-butanol, neopentyl alcohol, 1, 6-hexanediol, n-octanol, 2-ethylhexanol, benzyl alcohol, n-decanol, dodecanol, tetradecanol or hexadecanol.
33. The method of claim 29, wherein,
the quenching agent is selected from one or more of ethanol, 2-ethylhexanol, tetradecanol and hexadecanol.
34. An LLDPE prepared by the process of any one of claims 24 to 33.
35. The LLDPE of claim 34, wherein,
the LLDPE has a melting point of 90 ℃ to 135 ℃;
the branching degree is 1-30 CH 3 1000 carbon atoms;
a weight average molecular weight of 20,000 to 3,000,000;
the molecular weight distribution index is less than or equal to 3.
36. The LLDPE of claim 34, wherein,
the LLDPE has a melting point of 95 ℃ to 128 ℃;
the branching degree is 1-25 CH 3 1000 carbon atoms;
the weight average molecular weight is 50,000-600,000;
the molecular weight distribution index is 1.2-2.9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010675181.3A CN111662403B (en) | 2020-07-14 | 2020-07-14 | Cascade catalytic system and method for preparing LLDPE (Linear Low Density polyethylene) by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010675181.3A CN111662403B (en) | 2020-07-14 | 2020-07-14 | Cascade catalytic system and method for preparing LLDPE (Linear Low Density polyethylene) by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111662403A CN111662403A (en) | 2020-09-15 |
| CN111662403B true CN111662403B (en) | 2022-08-05 |
Family
ID=72392651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010675181.3A Active CN111662403B (en) | 2020-07-14 | 2020-07-14 | Cascade catalytic system and method for preparing LLDPE (Linear Low Density polyethylene) by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111662403B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113321674B (en) * | 2021-06-28 | 2022-12-02 | 山东京博石油化工有限公司 | [ NOON ] tetradentate ligand fourth subgroup metal complex and application thereof |
| CN115926034A (en) * | 2022-11-28 | 2023-04-07 | 浙江石油化工有限公司 | Preparation method of high-strength waterproof polyethylene film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727367A (en) * | 2005-07-27 | 2006-02-01 | 大庆石油学院 | Catalyst system of ethane copolymerization in situ for producing linear polyethylene in low density |
| CN101490095A (en) * | 2006-05-17 | 2009-07-22 | 陶氏环球技术公司 | High efficiency solution polymerization process |
| CN111282596A (en) * | 2018-12-06 | 2020-06-16 | 万华化学集团股份有限公司 | Ethylene oligomerization high-selectivity catalyst system and application thereof |
| CN111285893A (en) * | 2020-03-11 | 2020-06-16 | 万华化学集团股份有限公司 | Ligand, preparation method thereof, ethylene oligomerization catalyst and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017127705A1 (en) * | 2016-01-21 | 2017-07-27 | California Institute Of Technology | Co-supported catalysts for the tandem trimerization and polymerization of ethylene to produce linear low density polyethylene |
-
2020
- 2020-07-14 CN CN202010675181.3A patent/CN111662403B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727367A (en) * | 2005-07-27 | 2006-02-01 | 大庆石油学院 | Catalyst system of ethane copolymerization in situ for producing linear polyethylene in low density |
| CN101490095A (en) * | 2006-05-17 | 2009-07-22 | 陶氏环球技术公司 | High efficiency solution polymerization process |
| CN111282596A (en) * | 2018-12-06 | 2020-06-16 | 万华化学集团股份有限公司 | Ethylene oligomerization high-selectivity catalyst system and application thereof |
| CN111285893A (en) * | 2020-03-11 | 2020-06-16 | 万华化学集团股份有限公司 | Ligand, preparation method thereof, ethylene oligomerization catalyst and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111662403A (en) | 2020-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106062012B (en) | Support type mixed catalyst and the method for preparing the polymer based on alkene using it | |
| CN106488923B (en) | Ligand compound, transistion metal compound and the carbon monoxide-olefin polymeric comprising the transistion metal compound | |
| CN111662403B (en) | Cascade catalytic system and method for preparing LLDPE (Linear Low Density polyethylene) by using same | |
| Jing et al. | Synthesis and characterization of aminopyridine iron (II) chloride catalysts for isoprene polymerization: Sterically controlled monomer enchainment | |
| Nomura et al. | Synthesis and structural analysis of (imido) vanadium dichloride complexes containing 2-(2′-benz-imidazolyl) pyridine ligands: Effect of Al cocatalyst for efficient ethylene (co) polymerization | |
| CA2285302A1 (en) | Group 11 transition metal amine catalysts for olefin polymerization | |
| CN101245084B (en) | Phosphine-substituted vinyl-containing metallocene catalyst, and preparation method and application thereof | |
| CN113402554B (en) | PNSiNP ligand and preparation method thereof, ethylene oligomerization catalyst and application thereof | |
| CN111747977B (en) | Arylamine ether metal complexes, and preparation method and application thereof | |
| KR101262333B1 (en) | Post-metallocene complexes based on bis(naphtoxy)pyridine and bis(naphtoxy)thiophene ligands for the polymerisation of ethylene and alpha-olefins | |
| CN111715296B (en) | Ethylene tetramerization catalytic system, preparation method and application thereof | |
| US6730757B2 (en) | Sulfur-containing and sulfur-nitrogen-containing catalysts for polymerization of olefins and polar monomers | |
| KR100440480B1 (en) | Catalyst for olefin polymerization and method for preparing polyolefins | |
| CN111689997A (en) | Metal complex, preparation method and application thereof | |
| CN114616255A (en) | Biphenol polymerization catalyst | |
| CN111848662B (en) | Coordination compound containing IVB group metal, preparation method and application | |
| CN113501850B (en) | Bridged nitrogen-containing heterocyclic metallocene compound, and preparation method and application thereof | |
| CN114920866B (en) | Preparation method of polyolefin thermoplastic elastomer | |
| CA2415856A1 (en) | Late transition metal complexes, their use as catalysts and polymers therefrom | |
| US20050004334A1 (en) | Multi-dentate late transition metal catalyst complexes and polymerization methods using those complexes | |
| US7034093B2 (en) | Catalysts for olefin polymerization | |
| KR100431444B1 (en) | Catalyst for olefin polymerization and method for preparing polyolefins | |
| CN118005828A (en) | Transition metal catalyst and preparation and application thereof | |
| US6774078B1 (en) | Olefin polymerization catalysts based on annulated cyclopentadienyl ligands | |
| CA3218067A1 (en) | Branched olefin polymer, preparation method therefor and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |