CN114920866A - Preparation method of polyolefin thermoplastic elastomer - Google Patents
Preparation method of polyolefin thermoplastic elastomer Download PDFInfo
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Abstract
The invention discloses a preparation method of a polyolefin thermoplastic elastomer, and relates to a preparation method of a polyolefin thermoplastic elastomer by a cascade catalytic system. The catalyst combination comprises an oligomerizing agent, a copolymerizing agent and a co-catalyst, the process comprising the steps of: ethylene is used as a raw material, a cascade catalytic system is used in a single reactor, alpha-olefin (containing 1-octene, 1-hexene and the like) is prepared through oligomerization, and then a copolymerization catalyst is added to prepare the thermoplastic elastomer. The thermoplastic elastomer prepared by using the catalyst combination has the advantages of low density, narrow molecular weight distribution and excellent performance.
Description
Technical Field
The invention belongs to the field of ethylene polymerization, and relates to a preparation method of a polyolefin thermoplastic elastomer, a catalytic polymerization system for preparing the thermoplastic elastomer by cascade catalysis containing the catalyst combination, and a method for preparing the polyolefin thermoplastic elastomer by using the polymerization system.
Background
Polyolefin, i.e., an olefin polymer, is a high molecular material obtained by separately polymerizing or copolymerizing an α -olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc., and a cycloolefin, and is widely used in various fields such as daily use, agriculture, machinery, electronics and electricity. At present, the polyolefin industry in China has the problems that middle and low-end products are excessive, and high-end products are seriously dependent on import. Polyolefin elastomers and polyolefin plastomers are typical representatives of high-end products and now rely essentially exclusively on importation. Polyolefin elastomers and polyolefin plastomers differ primarily in the amount of copolymerized alpha-olefin monomer, which results in a difference in density. Generally, the polyolefin elastomer has a comonomer mass fraction of greater than 20%, the polyolefin plastomer has a comonomer mass fraction of less than 20%, and the plastomer has a higher density. The polyolefin elastomer is mainly used in the fields of modification, photovoltaic adhesive films and the like, while the plastomer has good melt strength, excellent bonding strength, tear resistance and transparency and is mainly applied in the field of film preparation.
The production process of polyolefin elastomer/plastomer is mainly solution polymerization process, and adopts copolymerization preparation of ethylene and alpha-olefin (1-octene, 1-butene are main) wherein the alpha-olefin occupies higher production cost in production raw materials and needs transportation and storage. 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 in-situ comonomer-high alpha-olefin, 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. The cascade catalysis in the published reports is mainly used for producing LLDPE, and the 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 CN113248643A discloses a method for preparing polyolefin elastomer, in which ethylene is used as a single raw material, two reactors are connected, ethylene is oligomerized in the first reactor to produce α -olefin (mainly 1-octene and 1-hexene), and then transferred to the second reactor, and polyolefin elastomer is produced under the action of copolymerization catalyst, and the polymerization process is relatively complicated.
The cascade catalysis can generate the alpha-olefin in situ, thereby saving the steps of separation, storage, transportation and the like of the alpha-olefin, simplifying the polymerization process and reducing the equipment investment and the polymerization cost. The polymer composition can be controlled by changing the polymerization process such as the type of catalyst, the ratio of the two catalysts, the prepolymerization time and the like. However, the matching of catalysts in the cascade catalysis process, the generation of a small amount of polymers in the oligomerization reaction process and the like still have challenges, and a good cascade catalysis system requires that the catalysts cannot interfere with each other and that a cocatalyst should be matched with the two catalysts.
Aiming at the problems, the invention provides a method for preparing a polyolefin thermoplastic elastomer by a single reactor, which has high polymerization activity and good catalyst compatibility, and the product has good application prospect in the field of film blowing.
Disclosure of Invention
The invention aims to provide a preparation method of a polyolefin thermoplastic elastomer, which takes ethylene as a raw material, uses a cascade catalytic system in a single reactor, and prepares the thermoplastic elastomer through oligomerization and copolymerization reaction in sequence. The oligomerization catalyst and the copolymerization catalyst have good compatibility, the cocatalyst and the two catalysts have good matching property, and the prepared thermoplastic elastomer has excellent market application prospect.
The invention provides a preparation method of a polyolefin elastomer, which comprises the following steps:
1) carrying out oligomerization on ethylene in a high-pressure reaction kettle in a solvent under the condition that the ethylene pressure is 1-6 MPa in the presence of an oligomerization catalyst and a cocatalyst to prepare alpha-olefin;
2) after the oligomerization reaction of step 1) is completed, a copolymerization catalyst and a cocatalyst are added to the reaction system, so that ethylene is copolymerized with the α -olefin obtained in step 1) to produce a polyolefin thermoplastic elastomer.
The oligomerization catalyst is a carbon-bridged diphosphine chromium complex represented by formula I,
wherein R is 1 、R 2 、R 3 、R 4 Each independently selected from aryl and its derivatives, R 5 Each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, ethenyl, propenyl, cyclopentyl, cyclohexyl, phenyl, preferably methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
Further, R 1 、R 2 、R 3 、R 4 Selected from the group consisting of phenyl, benzyl, biphenyl, naphthyl, anthracenyl, vinyl, propenyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, 2-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2, 4-diethylphenyl, 2, 6-diethylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2, 4-diisopropylphenyl, 2, 6-diisopropylphenyl, 2-butylphenyl, 4-butylphenyl, 2, 4-dibutylphenyl, 2, 6-dibutylphenyl, 4-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, 2-isopropylphenyl, 4-methoxyphenyl, 4-diethylphenyl, 4-isopropylphenyl, 4-dimethylphenyl, 4-ethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2, 4-ethylphenyl, 4-isopropylphenyl, or the like, O-ethoxyphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2- (trimethylsilyl) phenyl, 3- (trimethylsilyl) phenyl, 4- (trimethylsilyl) phenyl, 2- (tri-n-butylsilyl) phenyl, 3- (tri-n-butylsilyl) phenyl, 4- (tri-n-butylsilyl) phenyl.
The preparation method of the carbon-bridged diphosphine chromium complex comprises the following steps:
dissolving a compound shown as a formula II in a water-removing solvent under anhydrous and oxygen-free conditions to obtain a reaction solution I, wherein the structure of the compound shown as the formula II is as follows:
wherein R is 5 Each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, ethenyl, propenyl, cyclopentyl, cyclohexyl, phenyl, preferably methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
And (2) dropwise adding triethylamine into the reaction liquid I under stirring at the temperature of-10-0 ℃, continuously adding one or more compounds shown as the structure III into the reaction liquid I, stirring for reaction for 3-6h, continuously stirring for reaction for 6-24h at room temperature, and purifying the reaction liquid to obtain a product I, namely the PNNP ligand. The structure of the compound shown in formula III is shown as follows:
wherein R is 1 、R 2 Each independently selected from the group consisting of phenyl, benzyl, biphenyl, naphthyl, anthracenyl, ethenyl, propenyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, 2-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2, 4-diethylphenyl, 2, 6-diethylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2, 4-diisopropylphenyl, 2, 6-diisopropylphenyl, 2-butylphenyl, 4-butylphenyl, 2, 4-dibutylphenyl, 2, 6-dibutylphenyl, 4-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2- (trimethylsilyl) phenyl, 3- (trimethylsilyl) phenyl, 4- (trimethylsilyl) phenyl, 2- (tri-n-butylsilyl) phenyl, 3- (tri-n-butylsilyl) phenyl, 4- (tri-n-butylsilyl) phenyl.
Taking a proper amount of PNNP ligand and tetrahydrofuran chromium chloride, wherein the mass ratio of the tetrahydrofuran chromium chloride: PNNP ligand ═ 1: 1-1.2 is added into toluene and heated to 80 ℃ and stirred for 12h to generate blue powdery precipitate, and after cooling to room temperature, the toluene is filtered off. Washing the crude product twice with petroleum ether, and drying in vacuum to obtain the carbon-bridged diphosphine chromium complex I.
The copolymerization catalyst is a single-active-center metallocene catalyst or a post-metallocene catalyst, preferably dimethylsilyl (N-tert-butylamino) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilyl (N-tert-butylamino) (tetramethylcyclopentadienyl) titanium dimethyl, dimethylsilyl (N-tert-butylamino) (fluorenyl) titanium dichloride, (pentamethylcyclopentadienyl) trimethoxytitanium, diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride, dimethylsilylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride), meso-dimethylsilylbis (1-indenyl) zirconium dichloride, (bis (methylcyclopentadienyl) zirconium dichloride), (bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride, meso-metallocene catalyst, titanium dichloride, silicon dioxide, (cyclopentadienyl) (1, 2-dimethoxyethane) zirconium trichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, racemic dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride, diphenylmethylenecyclopentadiene (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride, di-p-tolylmethylenecyclopentadiene (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride, dimethylbis (propylcyclopentadienyl) hafnium, bis (n-butylcyclopentadienyl) hafnium dichloride.
The cocatalyst is at least one of alkyl aluminum, organic boron compound and alkyl aluminoxane, preferably one or more of methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum and tri (pentafluorophenyl) boron compound.
The reaction solvent is selected from aliphatic hydrocarbon solvent and/or aromatic hydrocarbon solvent; 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; the aromatic hydrocarbon solvent is preferably selected from one or more of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, dichlorotoluene;
the α -olefin comprises 1-octene, 1-hexene, etc.;
in the reaction, the mol ratio of the oligomerization catalyst to the copolymerization catalyst is 1: (0.05 to 10), preferably 1: (0.1-5); in the oligomerization reaction, the molar ratio of the oligomerization catalyst to the cocatalyst is 1 (100-1000); in the copolymerization reaction, when the cocatalyst contains aluminum, the molar ratio of the metal atom in the copolymerization catalyst to the aluminum in the cocatalyst is 1 (50-500), and when the cocatalyst contains boron, the molar ratio of the metal atom in the copolymerization catalyst to the boron in the cocatalyst is 1 (1-4).
The oligomerization reaction temperature is 30-80 ℃, and the oligomerization reaction time is 10-60 min; the copolymerization reaction temperature is 100-230 ℃, and the copolymerization reaction time is 5-15 min; the pressure intensity of the ethylene is 1MPa-6 MPa.
The invention also provides a method for terminating the polymerization reaction, wherein a quenching agent is added in the step 2) to terminate the reaction, and preferably, the dosage of the quenching agent is 0.5-5 times, preferably 1-3 times of that of the cocatalyst substance;
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, hexadecanol, and more preferably one or more of ethanol, 2-ethylhexanol, tetradecanol, and hexadecanol.
Finally, the present invention provides a polyolefin thermoplastic elastomer prepared by the above process, preferably having a melting point of 50 ℃ to 120 ℃, preferably 55 ℃ to 105 ℃; the weight-average molecular weight is 20000 to 180000, preferably 40000-160000; the molecular weight distribution index is less than or equal to 4, preferably 1.2-3.5.
The invention has the following beneficial effects:
1. in a single reactor, firstly, ethylene is mainly oligomerized into 1-octene and a small amount of 1-hexene under the action of an oligomerization catalyst and a cocatalyst, and then, ethylene is copolymerized with the generated 1-octene and a small amount of 1-hexene under the action of a copolymerization catalyst and a cocatalyst, thereby directly producing a polyolefin thermoplastic elastomer comprising a copolymer of ethylene and α -olefin from ethylene;
2. the preparation method of the polyolefin thermoplastic elastomer 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 oligomerization catalyst to the copolymerization catalyst;
3. the produced polyolefin thermoplastic elastomer has the advantages of low density, small molecular weight distribution index, excellent performance and good application prospect.
Detailed Description
The following specific examples are merely illustrative of the present invention, but these examples are only part of the present invention and do not limit the application of the present invention in other fields. The starting materials used in the examples are conventional in the art and the purity specifications used are either analytically or chemically pure.
Raw material source information:
2-methylimidazolidine: greater than or equal to 95%, Shanghai Shaoyuan reagent Limited
2-isopropylimidazolidine: shanghai Shao reagent Limited company with content of not less than 95%
2-tert-butylimidazolidine: shanghai Shao reagent Limited company with content of not less than 95%
2-cyclohexyl imidazolidine: greater than or equal to 95%, Shanghai Shaoyuan reagent Limited
Triethylamine: not less than 99.5% (GC), Shanghai Aladdin Biotechnology Limited
Diphenyl phosphine chloride: 97% of Alfa Ensa chemical Co., Ltd
4- (tri-n-butylsilyl) phenyl phosphine chloride: 97% Jiangsu Xinnoco catalyst Co., Ltd
Ethyl acetate: 99.9%%, Bailingwei science and technology Limited
Ethanol: analytical pure, national drug group chemical reagent Limited
MMAO-7 (modified methylaluminoxane): 7 wt% Al, Isopar E solvent, Nomoon chemical (Ningbo) Co., Ltd
MAO (methylaluminoxane), 10% strength by weight, toluene solvent, Nomoon chemical (Ningbo) Co., Ltd
iPr-PNP (CAS: 60981-68-20): more than 97%, Jiangsu Xinnoco catalyst Co., Ltd
Melting point test: the melting point (Tm) of the polymer was characterized by DSC with a Mettle DSC 1. About 5mg of sample is weighed into an aluminum sample dish and sealed with a cover. And (4) putting the prepared sample into the sample cell by using tweezers, and covering a furnace cover. The sample mass 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, comonomer insertion 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.
And (3) carrying out gas chromatography qualitative and quantitative analysis on each component in the oligomerization reaction liquid: the conditions of the GC analysis instrument used were as follows: the instrument model is as follows: shimadzu GC 2010; a chromatographic column: DB-5(30m 0.25mm 0.25 μm); column temperature procedure: the temperature was first maintained at 35 ℃ for 10min and then increased to 250 ℃ at a rate of 10 ℃/min, and maintained at this temperature for 10 min. Temperature of the detector: 300 ℃; carrier gas: 1 bar; air: 0.3 bar; fuel gas (H2): 0.3bar
The sample quality analysis was performed using an internal standard method. The following should be mentioned:
wherein m1 is the mass of a certain product, m is the mass of an internal standard substance, a1 is the peak area of the product detected in a gas chromatogram, and a is the peak area of the internal standard substance. k is a correction factor related to the substance to be measured and the detection condition.
Preparing an oligomerization catalyst:
(1) dissolving 100mmol of 2-methylimidazolidine in 200ml of dichloromethane under anhydrous and anaerobic conditions to obtain a reaction solution I; and (2) dropwise adding 220mmol of triethylamine into the reaction liquid I under stirring at-5 ℃, slowly adding 110mmol of diphenyl phosphine chloride into the reaction liquid I, adding the rest 110mmol of diphenyl phosphine chloride after the solution is stable and does not release heat continuously, reacting for 3 hours under stirring, removing the low-temperature constant-temperature reaction bath, and stirring for 12 hours at room temperature. And (3) purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, and the height-diameter ratio is 2), then recrystallizing at 78 ℃ (the solvent is ethanol, ethyl acetate is 5:1), and treating the reaction liquid to obtain a product, namely the PNNP ligand P1.
1mmol of PNNP ligand P1 and 1mmol of tetrahydrofuran chromium chloride are added into 100ml of toluene and heated to 80 ℃ to be stirred for 12 hours to generate blue powdery precipitate, and the blue powdery precipitate is cooled to room temperature and filtered off the toluene. The crude product is washed twice by petroleum ether (20ml) and dried in vacuum to obtain the carbon-bridged diphosphonic acid chromium complex L1
(2) Dissolving 100mmol of 2-isopropyl imidazolidine in 200ml of acetonitrile under anhydrous and anaerobic conditions to obtain a reaction solution I; and (2) dropwise adding 220mmol of triethylamine into the reaction liquid I under stirring at-5 ℃, slowly adding 110mmol of diphenyl phosphine chloride into the reaction liquid I, adding the rest 110mmol of diphenyl phosphine chloride after the solution is stable and does not release heat continuously, stirring for reacting for 3 hours, removing the low-temperature constant-temperature reaction bath, and stirring for 18 hours at room temperature. And (3) purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, and the height-diameter ratio is 2), then recrystallizing at 80 ℃ (the solvent is ethanol: ethyl acetate: 5:1), and treating the reaction liquid to obtain a product, namely the PNNP ligand P2. Reference L1 preparation to obtain the carbon-bridged diphosphine chromium complex L2
(3) Dissolving 100mmol of 2-tert-butyl imidazolidine in 200ml of dichloromethane under anhydrous and anaerobic conditions to obtain a reaction solution I; and (2) dropwise adding 220mmol of triethylamine into the reaction liquid I under stirring at-5 ℃, slowly adding 110mmol of a compound (diphenyl phosphine chloride) shown as the structure III into the reaction liquid I, adding the rest 110mmol of diphenyl phosphine chloride when the solution is stable and does not release heat continuously, reacting for 3 hours under stirring, removing the low-temperature constant-temperature reaction bath, and stirring for 18 hours at room temperature. The reaction solution is purified by column chromatography (tetrahydrofuran elution with an aspect ratio of 2), and then recrystallized at 80 ℃ (the solvent is ethanol: ethyl acetate: 5:1), and the reaction solution is treated to obtain the product PNNP ligand P3. Reference L1 catalyst was prepared to yield L3.
(4) Dissolving 100mmol of 2-cyclohexyl imidazolidine in 200ml of acetonitrile under anhydrous and anaerobic conditions to obtain a first reaction solution; and (2) dropwise adding 220mmol of triethylamine into the reaction liquid I under stirring at-5 ℃, slowly adding 110mmol of a compound (diphenyl phosphine chloride) shown as the structure III into the reaction liquid I, adding the rest 110mmol of diphenyl phosphine chloride when the solution is stable and does not release heat continuously, reacting for 3 hours under stirring, removing the low-temperature constant-temperature reaction bath, and stirring for 18 hours at room temperature. The reaction solution was purified by column chromatography (tetrahydrofuran elution, height/diameter ratio of 2), and then recrystallized at 80 ℃ (solvent ethanol: ethyl acetate: 5:1) to obtain PNNP ligand P4. Reference L1 catalyst was prepared as L4.
(5) L5 was prepared as described in L4, except that the compound of structure III added was 4- (tri-n-butylsilyl) phenyl phosphine chloride.
Example 1
Oligomerization catalyst: carbon-bridged diphosphine chromium complex L1.
Copolymerization catalyst: dimethylsilyl (N-tert-butylamino) (tetramethylcyclopentadienyl) dimethyl titanium (T1)
An oligomerization catalysis-assisting system: MMAO-7(7 wt% Al)
Copolymerization catalyst-assisted System: MMAO-7(7 wt% Al)
Polymerization experiment: heating a 300ml reaction kettle to 150 ℃, vacuumizing for 2h, replacing by 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 3MPa, 100ml of methylcyclohexane after water removal and oxygen removal and 300 mu mol of MMAO-7 are sequentially added into a reactor, stirred for 2min, added with 3 mu mol of oligomerization catalyst L1 and reacted for 25min (sampling GC test, oligomerization is mainly ethylene tetramerization reaction, and a small amount of ethylene trimerization reaction, the mol ratio of 1-octene to 1-hexene in the reaction liquid is 5.2: 1, then controlling the pressure of ethylene to be constant (discharging partial ethylene properly), raising the temperature of the reaction kettle to 100 ℃, adding 1 mu mol of copolymerization catalyst T1 and 60 mu mol of MMAO-7, continuing the reaction for 10min, after the reaction is finished, the polymerization solution was poured into 30% (by volume) hydrochloric acid/ethanol solution to terminate the reaction, washed with ethanol, vacuum dried to obtain polymer product, which was collected and dried to obtain 4.57g of polymer, the properties of which are shown in Table 2.
Example 2
Oligomerization catalyst: carbon-bridged bisphosphine chromium complex L2.
Copolymerization catalyst: dimethylsilyl (N-tert-butylamino) (tetramethylcyclopentadienyl) dimethyl titanium (T1)
An oligomerization catalysis-assisting system: MMAO-7(7 wt% Al)
Copolymerization cocatalyst system: MMAO-7(7 wt% Al)
Polymerization experiment: 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. Under the conditions that the reaction temperature is 65 ℃ and the ethylene pressure is 3MPa, 100ml of dehydrated and deoxidized normal hexane and 800 mu mol of MMAO-7 are sequentially added into a reactor, stirred for 2min, added with 3 mu mol of oligomerization catalyst L2 and reacted for 20min (sampling GC test, oligomerization is mainly ethylene tetramerization reaction, and a small amount of ethylene trimerization reaction, the mol ratio of 1-octene to 1-hexene in the reaction liquid is 5.5: 1, then controlling the ethylene pressure to be unchanged (properly discharging partial ethylene), raising the temperature of the reaction kettle to 150 ℃, adding 0.5 mu mol of copolymerization catalyst T1 and 70 mu mol of MMAO-7, continuing to react for 10min, after the reaction is finished, the polymerization solution was poured into 30% (by volume) hydrochloric acid/n-octanol solution to terminate the reaction, washed with ethanol, vacuum dried to obtain a polymer product, which was collected and dried to obtain 3.03g of a polymer having the properties shown in Table 2.
Example 3
Oligomerization catalyst: carbon-bridged bisphosphine chromium complex L3.
Copolymerization catalyst: dimethylsilyl (N-tert-butylamino) (tetramethylcyclopentadienyl) dimethyl titanium
Oligomerization catalysis-assisting system: MMAO-7(7 wt% Al)
Copolymerization cocatalyst system: MMAO-7(7 wt% Al)
Polymerization experiment: heating a 500ml reaction kettle to 130 ℃, vacuumizing for 3h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. Under the conditions that the reaction temperature is 75 ℃ and the ethylene pressure is 3MPa, 200ml of cyclohexane after water and oxygen removal and 550 mu mol of MMAO-7 are sequentially added into a reactor, the mixture is stirred for 2min, 3 mu mol of oligomerization catalyst L3 is added into the reactor to react for 20min (sampling GC test, oligomerization mainly is ethylene tetramerization reaction and a small amount of ethylene trimerization reaction, the molar ratio of 1-octene to 1-hexene in the reaction liquid is 3.9: 1, then the ethylene pressure is controlled not to be changed (partial ethylene is properly discharged), the temperature of a reaction kettle is raised to 130 ℃, 5 mu mol of copolymerization catalyst T1 and 100 mu mol of MMAO-7 are added into the reaction kettle to continue to react for 10min, after the reaction is finished, the polymerization liquid is poured into 30% (volume ratio) hydrochloric acid/2-ethyl hexanol solution to terminate the reaction, the reaction is washed by ethanol and dried in vacuum to obtain a polymer product, the product is collected and dried, 13.45g of a polymer was obtained. The properties of the polymers are shown in Table 2.
Example 4
Oligomerization catalyst: carbon-bridged diphosphine chromium complex L4.
Copolymerization catalyst: diphenylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride (Zr1)
An oligomerization catalysis-assisting system: MAO (10 wt% Al)
Copolymerization cocatalyst system: MMAO-7(7 wt% Al)
Polymerization experiment: heating a 300ml reaction kettle to 160 ℃, vacuumizing for 2h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. At the reaction temperature of 45 ℃ and the ethylene pressure of 3MPa, 100ml of methylcyclohexane after water removal and oxygen removal and 150 mu mol of MAO are sequentially added into a reactor, stirred for 2min, added with 3 mu mol of oligomerization catalyst L4 and reacted for 25min (sampling GC test, oligomerization is mainly ethylene tetramerization reaction, and a small amount of ethylene trimerization reaction, the molar ratio of 1-octene to 1-hexene in the reaction liquid is 4.8: 1, then controlling the ethylene pressure to be unchanged (properly discharging partial ethylene), raising the temperature of the reaction kettle to 160 ℃, adding 1 mu mol of copolymerization catalyst Zr1 and 300 mu mol of MMAO-7, continuing to react for 10min, after the reaction is finished, the polymerization solution was poured into 30% (by volume) hydrochloric acid/ethanol solution to terminate the reaction, washed with ethanol, vacuum dried to obtain polymer product, which was collected and dried to obtain 14.43g of polymer, the properties of which are shown in Table 2.
Example 5
Oligomerization catalyst: carbon-bridged bisphosphine chromium complex L5.
Copolymerization catalyst: diphenylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride (Zr1)
Oligomerization catalysis-assisting system: MMAO-3(7 wt% Al)
Copolymerization cocatalyst system: MMAO-7(7 wt% Al)
Polymerization experiment: heating a 300ml reaction kettle to 150 ℃, vacuumizing for 2h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. Under the conditions that the reaction temperature is 50 ℃ and the ethylene pressure is 3MPa, 100ml of Isopar E after water and oxygen removal and 900 mu mol of MMAO-7 are sequentially added into a reactor, stirred for 2min, added with 3 mu mol of oligomerization catalyst L5 and reacted for 20min (sampling GC test, oligomerization is mainly ethylene tetramerization reaction, and a small amount of ethylene trimerization reaction, the molar ratio of 1-octene to 1-hexene in the reaction liquid is 4.7: 1, then controlling the pressure of ethylene to be constant (discharging partial ethylene properly), raising the temperature of the reaction kettle to 180 ℃, adding 1 mu mol of copolymerization catalyst Zr1 and 60 mu mol of MMAO-7, continuing to react for 10min, after the reaction is finished, the polymerization solution was poured into 30% (by volume) hydrochloric acid/ethanol solution to terminate the reaction, washed with ethanol, vacuum dried to obtain polymer product, which was collected and dried to obtain 17.55g of polymer, the properties of which are shown in Table 2.
Example 6
Oligomerization catalyst: carbon-bridged diphosphorus chromium complex L5
Copolymerization catalyst: diphenylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride (Zr1)
An oligomerization catalysis-assisting system: MAO (10 wt% Al)
Copolymerization cocatalyst system: MMAO-7(7 wt% Al), [ Ph ] 3 C][B(C 6 F 5 ) 4 ]
Polymerization experiment: heating a 300ml reaction kettle to 150 ℃, vacuumizing for 2h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. At the reaction temperature of 50 ℃ and the ethylene pressure of 3MPa, 100ml of Isopar E after water and oxygen removal and 1500 mu mol of MAO are sequentially added into a reactor, stirred for 2min, added with 3 mu mol of oligomerization catalyst L5 for reaction for 20min (sampling GC test, oligomerization is mainly ethylene tetramerization reaction and a small amount of ethylene trimerization reaction, the molar ratio of 1-octene to 1-hexene in the reaction liquid is 4.5: 1, then the ethylene pressure is controlled to be constant (partial ethylene is properly discharged), the temperature of the reaction kettle is raised to 140 ℃, added with 1 mu mol of copolymerization catalyst Zr1 and 1 mu mol of [ Ph ] catalyst 3 C][B(C 6 F 5 ) 4 ]And 60 mu mol of MMAO-7, continuously reacting for 10min, after the reaction is finished, pouring the polymerization solution into 30% (volume ratio) hydrochloric acid/ethanol solution to terminate the reaction, washing by ethanol, drying in vacuum to obtain a polymer product, collecting the product and drying to obtain 9.26g of polymer. The properties of the polymer are shown in Table 2.
Example 7
Oligomerization catalyst: carbon-bridged diphosphorus chromium complex L5
Copolymerization catalyst: diphenylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride (Zr1)
An oligomerization catalysis-assisting system: MAO (10 wt% Al)
Copolymerization cocatalyst system: MMAO-7(7 wt% Al), [ Ph ] 3 C][B(C 6 F 5 ) 4 ]
Polymerization experiment: heating a 300ml reaction kettle to 150 ℃, vacuumizing for 2h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. Sequentially adding the mixture into a reactor under the conditions that the reaction temperature is 75 ℃ and the ethylene pressure is 3MPaAdding 100ml Isopar E after removing water and oxygen, 2000 mu mol MAO, stirring for 2min, adding 3 mu mol oligomerization catalyst L5 to react for 20min (sampling GC test, oligomerization is mainly ethylene tetramerization reaction, and a small amount of ethylene trimerization reaction, the molar ratio of 1-octene to 1-hexene in the reaction solution is 4.3: 1, then controlling the ethylene pressure to be constant (properly discharging partial ethylene), raising the temperature of the reaction kettle to 100 ℃, adding 3 mu mol copolymerization catalyst Zr1, 1 mu mol [ Ph ] of 3 C][B(C 6 F 5 ) 4 ]And 300 mu mol of MMAO-7, continuously reacting for 10min, after the reaction is finished, pouring the polymerization solution into 30% (volume ratio) hydrochloric acid/ethanol solution to terminate the reaction, washing by ethanol, drying in vacuum to obtain a polymer product, collecting the product and drying to obtain 17.02g of polymer. The properties of the polymers are shown in Table 2.
Example 8
Oligomerization catalyst: carbon-bridged chromium bisphosphonates complex L2
Copolymerization catalyst: diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride (Zr2)
An oligomerization catalysis-assisting system: MAO (10 wt% Al)
Copolymerization cocatalyst system: al (aluminum) i Bu 3 、[Ph 3 C][B(C 6 F 5 ) 4 ]
Polymerization experiment: heating a 300ml reaction kettle to 150 ℃, vacuumizing for 2h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. Under the conditions of reaction temperature of 60 ℃ and ethylene pressure of 4MPa, 100ml of Isopar E after water and oxygen removal and 500 mu mol of MMAO-7 are sequentially added into a reactor, stirred for 2min, added with 2 mu mol of oligomerization catalyst L2 for reaction for 40min (sampling GC test, oligomerization is mainly ethylene tetramerization reaction and a small amount of ethylene trimerization reaction, the molar ratio of 1-octene to 1-hexene in the reaction liquid is 5.6: 1, then the ethylene pressure is controlled to be constant (partial ethylene is properly discharged), the temperature of the reaction kettle is raised to 100 ℃, added with 1 mu mol of copolymerization catalyst Zr2 and 1 mu mol of [ Ph ] of 3 C][B(C 6 F 5 ) 4 ]And 500. mu. mol of Al i Bu 3 Continuing the reaction for 5min, after the reaction is finished, pouring the polymerization solution into 30% (volume ratio) hydrochloric acid/ethanol solution to terminate the reaction, washing with ethanolThe polymer product was washed and dried under vacuum to obtain 4.28g of a polymer. The properties of the polymers are shown in Table 2.
Example 9
Oligomerization catalyst: carbon-bridged chromium bisphosphonates complex L3
Copolymerization catalyst: dimethylsilylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride) (Zr3)
An oligomerization catalysis-assisting system: MAO (10 wt% Al)
Copolymerization cocatalyst system: MMAO-7(7 wt% Al), [ Ph ] 3 C][B(C 6 F 5 ) 4 ]
Polymerization experiment: heating a 300ml reaction kettle to 150 ℃, vacuumizing for 2h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. Under the conditions of reaction temperature of 55 ℃ and ethylene pressure of 1MPa, 100ml of Isopar E after water removal and oxygen removal and 900 mu mol of MAO are sequentially added into a reactor, stirred for 2min, added with 6 mu mol of oligomerization catalyst L3 and reacted for 30min (sampling GC test, oligomerization is mainly ethylene tetramerization reaction, and a small amount of ethylene trimerization reaction, the molar ratio of 1-octene to 1-hexene in the reaction liquid is 4.2: 1, then controlling the ethylene pressure to be constant (discharging partial ethylene properly), raising the temperature of the reaction kettle to 200 ℃, adding 1 mu mol of copolymerization catalyst Zr3 and 200 mu mol of MMAO-7(7 wt% Al), continuing to react for 5min, after the reaction is finished, the polymerization solution was poured into 30% (by volume) hydrochloric acid/ethanol solution to terminate the reaction, washed with ethanol, vacuum dried to obtain polymer product, which was collected and dried to obtain 9.82g of polymer, the properties of which are shown in Table 2.
Example 10
Oligomerization catalyst: carbon-bridged chromium bisphosphonates complex L4
Copolymerization catalyst: di-p-tolylene methylene cyclopentadiene (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride (Zr4)
An oligomerization catalysis-assisting system: MMAO-7(7 wt% Al)
Copolymerization catalyst-assisted System: MMAO-7(7 wt% Al)
Polymerization experiment: heating a 300ml reaction kettle to 150 ℃, vacuumizing for 2h, replacing by nitrogen, and replacing by ethylene when the temperature is cooled to room temperature. Under the conditions of reaction temperature of 65 ℃ and ethylene pressure of 5MPa, sequentially adding 100ml of Isopar E after water and oxygen removal and 600 mu mol of MMAO-7 into a reactor, stirring for 2min, adding 5 mu mol of oligomerization catalyst L4 into the reactor for reaction for 30min (sampling GC test, oligomerization is mainly ethylene tetramerization reaction and a small amount of ethylene trimerization reaction, the molar ratio of 1-octene to 1-hexene in reaction liquid is 5.3: 1), then controlling the ethylene pressure to be constant (properly discharging partial ethylene), raising the temperature of a reaction kettle to 150 ℃, adding 1 mu mol of copolymerization catalyst Zr4 and 150 mu mol of MMAO-7(7 wt% Al), continuing the reaction for 15min, after the reaction is finished, pouring the polymerization liquid into 30% (volume ratio) hydrochloric acid/ethanol solution for stopping the reaction, obtaining a polymer product through ethanol washing and vacuum drying, collecting the product and drying, 11.03g of a polymer was obtained. The properties of the polymer are shown in Table 2.
Comparative example 1:
the preparation method was the same as in example 1, except that an externally-purchased ligand iPr-PNP was used to obtain a catalyst carbon-bridged bisphosphine chromium complex La.
Polymerization experiments as in example 1 gave 3.19g of polymer. The comparison shows that when the carbon-bridged diphosphine chromium complex prepared by the conventional PNP system is used for preparing the polyolefin thermoplastic elastomer in a cascade manner, the octene selectivity in the oligomerization product is relatively low, and the insertion rate of the copolymerization product is lower.
Table 1: conditions of the reactions of the examples
TABLE 2
Claims (9)
1. A method of preparing a polyolefin elastomer comprising the steps of:
1) carrying out oligomerization on ethylene in a high-pressure reaction kettle in a solvent under the condition that the ethylene pressure is 1-6 MPa in the presence of an oligomerization catalyst and a cocatalyst to prepare alpha-olefin;
2) after the oligomerization reaction of step 1) is completed, a copolymerization catalyst and a cocatalyst are added to the reaction system, so that ethylene is copolymerized with the α -olefin obtained in step 1) to produce a polyolefin thermoplastic elastomer.
The oligomerization catalyst is a carbon-bridged diphosphorus chromium complex represented by a formula I,
wherein R is 1 、R 2 、R 3 、R 4 Each independently selected from aryl and its derivatives, R 5 Each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, ethenyl, propenyl, cyclopentyl, cyclohexyl, phenyl, preferably methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
2. The method of claim 1, wherein R is 1 、R 2 、R 3 、R 4 Selected from the group consisting of phenyl, benzyl, biphenyl, naphthyl, anthracenyl, vinyl, propenyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, 2-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2, 4-diethylphenyl, 2, 6-diethylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2, 4-diisopropylphenyl, 2, 6-diisopropylphenyl, 2-butylphenyl, 4-butylphenyl, 2, 4-dibutylphenyl, 2, 6-dibutylphenyl, 4-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, 2-isopropylphenyl, 4-methoxyphenyl, 4-diethylphenyl, 4-isopropylphenyl, 4-dimethylphenyl, 4-ethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2, 4-ethylphenyl, 4-isopropylphenyl, or the like, O-ethoxyphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2- (trimethylsilyl) phenyl group, 3- (trimethylsilyl) phenyl group, 4- (trimethylsilyl) phenyl group, 2- (tri-n-butylsilyl) phenyl group,3- (tri-n-butylsilyl) phenyl, 4- (tri-n-butylsilyl) phenyl.
3. The process according to claim 1 or 2, wherein the copolymerization catalyst is a single-site metallocene catalyst or a post-metallocene catalyst, preferably dimethylsilyl (N-tert-butylamino) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilyl (N-tert-butylamino) (tetramethylcyclopentadienyl) dimethyl titanium, dimethylsilyl (N-tert-butylamino) (fluorenyl) titanium dichloride, (pentamethylcyclopentadienyl) trimethoxytitanium, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride), meso-dimethylsilylbis (1-indenyl) zirconium dichloride, (bis (methylcyclopentadienyl) zirconium dichloride), a metallocene catalyst or a post-metallocene catalyst, (bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (1, 2-dimethoxyethane) zirconium trichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, racemic dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride, diphenylmethylenecyclopentadiene (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride, di-p-tolylmethylenecyclopentadiene (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride, dimethylbis (propylcyclopentadienyl) hafnium, bis (n-butylcyclopentadienyl) hafnium dichloride.
4. A method according to any one of claims 1 to 3, wherein the cocatalyst is at least one member selected from the group consisting of alkylaluminums, organoboron compounds, alkylaluminoxanes, preferably one or more members selected from the group consisting of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, and tris (pentafluorophenyl) boron compound.
5. The process according to any one of claims 1 to 4, wherein the reaction 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; the aromatic hydrocarbon solvent is preferably selected from one or more of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, dichlorotoluene.
6. The process according to any one of claims 1 to 5, wherein the α -olefin comprises 1-octene, 1-hexene.
7. The process according to any one of claims 1 to 6, wherein the molar ratio of the oligomerization catalyst to the copolymerization catalyst is 1: (0.05 to 10), preferably 1: (0.1-5); in the oligomerization reaction, the molar ratio of the oligomerization catalyst to the cocatalyst is 1 (100-1000); in the copolymerization reaction, when the cocatalyst contains aluminum, the molar ratio of the metal atom in the copolymerization catalyst to the aluminum in the cocatalyst is 1 (50-500), and when the cocatalyst contains boron, the molar ratio of the metal atom in the copolymerization catalyst to the boron in the cocatalyst is 1 (1-4).
8. The process according to any one of claims 1 to 7, wherein the oligomerization reaction temperature is 30 ℃ to 80 ℃ and the oligomerization reaction time is 10 to 60 min; the copolymerization reaction temperature is 100-230 ℃, and the copolymerization reaction time is 5-15 min; the pressure intensity of the ethylene is 1MPa-6 MPa.
9. The polyolefin thermoplastic elastomer prepared by the preparation method according to any one of claims 1 to 8, wherein the melting point of the polyolefin thermoplastic elastomer is 50 ℃ to 120 ℃, preferably 55 ℃ to 105 ℃; the weight-average molecular weight is 20000 to 180000, preferably 40000 to 160000; the molecular weight distribution index is less than or equal to 4, preferably 1.2-3.5.
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