CN114920866B - 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 cascade catalytic system for preparing the polyolefin thermoplastic elastomer. The catalyst combination comprises an oligomerization agent, a copolymerization agent, and a cocatalyst, the method comprising the steps of: ethylene is used as raw material, a cascade catalytic system is used in a single reactor, alpha-olefin (comprising 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 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 comprising the catalyst combination, and a method for preparing the polyolefin thermoplastic elastomer by using the polymerization system.
Background
Polyolefin, namely olefin polymer, is a polymer material obtained by polymerizing or copolymerizing ethylene, propylene, 1-butene, 1-hexene, 1-octene and other alpha-olefins and cycloolefins alone, 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 problem that medium-low end products are excessive and high end products are seriously dependent on import. Polyolefin elastomers and polyolefin plastomers are typical representatives in high end products and are currently substantially entirely imported. Polyolefin elastomers and polyolefin plastomers differ primarily in the amount of copolymerized alpha-olefin monomer, which results in a difference in density. Typically 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, and the plastomer has good melt strength, excellent bonding strength, tear resistance and transparency, and is mainly applied to the field of film preparation.
The polyolefin elastomer/plastomer is produced by copolymerization of ethylene and alpha-olefin (1-octene, 1-butene is the main material) and the production process is mainly solution polymerization process, wherein the alpha-olefin occupies higher production cost in the production raw material and needs transportation and storage. The cascade catalysis technology is that ethylene is used as the sole monomer material, oligomerization catalyst and copolymerization catalyst are added into a reactor, the oligomerization catalyst is used for in-situ preparation of comonomer-higher alpha-olefin, and the copolymerization catalyst is used for copolymerizing the alpha-olefin with ethylene, so as to obtain the ethylene/alpha-olefin copolymer. This process eliminates the cost of comonomer production, transportation, storage, as compared to conventional polymerization processes. The cascade catalysis in the published report is mainly used for producing LLDPE, and Chinese patent application publication CN104356269A discloses a method for producing LLDPE with narrow molecular weight distribution by adopting chromium complex to catalyze and produce 1-hexene and titanium series catalyst for copolymerization. Patent CN113248643a discloses a method for preparing a polyolefin elastomer, which uses ethylene as a single raw material, adopts two reactors connected, uses oligomerization reaction of ethylene in a first reactor to generate alpha-olefin (1-octene, 1-hexene is the main material), then transfers the alpha-olefin to a second reactor, and generates the polyolefin elastomer under the action of a copolymerization catalyst, and the polymerization process is relatively complex.
The cascade catalysis can generate alpha-olefin in situ, so that the steps of alpha-olefin separation, storage, transportation and the like are omitted, the polymerization process is simplified, and the equipment investment and the polymerization cost are reduced. The polymer composition can be controlled by changing the polymerization process such as the kind of catalyst, the ratio of the two catalysts, the prepolymerization time, etc. However, there are challenges in matching catalysts to each other in a cascade catalytic process, in generating a small amount of polymer in an oligomerization process, etc., and good cascade catalytic systems require that the catalysts cannot interfere with each other and that the cocatalyst should be matched with both catalysts.
Aiming at the problems, the invention provides a method for preparing 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 and prepares the thermoplastic elastomer by oligomerization and copolymerization reactions in sequence in a single reactor by using a cascade catalytic system. The oligomerization catalyst and the copolymerization catalyst have good compatibility, the cocatalyst has good matching property with the two catalysts, 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) In a high-pressure reaction kettle, under the condition that the ethylene pressure is 1-6 MPa, in a solvent, oligomerization is carried out on ethylene in the presence of an oligomerization catalyst and a cocatalyst to prepare alpha-olefin;
2) After the oligomerization 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 form a polyolefin thermoplastic elastomer.
The oligomerization catalyst is a carbon bridging biphosphine chromium complex represented by a formula I,
wherein R is 1 、R 2 、R 3 、R 4 Each independently selected from aryl and derivatives thereof, R 5 Each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, vinyl, propenyl, cyclopentyl, cyclohexyl, phenyl, preferably methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
Further, R 1 、R 2 、R 3 、R 4 Selected from 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-dibutylphenyl2, 6-dibutyl phenyl, 4-methoxy phenyl, o-methoxy phenyl, 4-ethoxy phenyl, o-ethoxy phenyl, 2-fluoro phenyl, 3-fluoro phenyl, 4-fluoro phenyl, 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 biphosphine chromium complex comprises the following steps:
under anhydrous and anaerobic conditions, dissolving a compound shown as a formula II in a water removal solvent to obtain a reaction liquid 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, t-butyl, vinyl, propenyl, cyclopentyl, cyclohexyl, phenyl, preferably methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
Dropwise adding triethylamine into the reaction liquid I under stirring at the temperature of-10-0 ℃, continuously adding one or more compounds shown as a structure III into the reaction liquid I, stirring and reacting for 3-6h, continuously stirring and reacting 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 of formula III is shown below:
wherein R is 1 、R 2 Each independently selected from 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-dimethylphenylDiisopropylphenyl, 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 according to the mass ratio: PNNP ligand = 1:1-1.2 is added to toluene and heated to 80℃and stirred for 12h, a blue powdery precipitate is formed, after cooling to room temperature, toluene is filtered off. Washing the crude product twice with petroleum ether, and vacuum drying to obtain the carbon-bridged biphosphine chromium complex I.
The copolymerization catalyst is a single-active-site metallocene catalyst or post-metallocene catalyst, preferably dimethylsilyl (N-tertiary butylamino) (tetramethyl cyclopentadienyl) titanium dichloride, dimethylsilyl (N-tertiary butylamino) (fluorenyl) titanium dichloride, (pentamethyl cyclopentadienyl) trimethoxy titanium, dibenzylidene (cyclopentadienyl) (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, (cyclopentadienyl) (1, 2-dimethoxyethane) zirconium trichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, racemic dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride, dibenzoylmethylene (2, 7-dimethyl cyclopentadienyl) bis (2-tert-butyl-1-indenyl) zirconium dichloride, racemic dimethylcyclopentadienyl (2-dimethyl fluorenyl) zirconium dichloride, p-dimethylcyclopentadienyl (2-dimethylfluorenyl) zirconium dichloride, bis (n-butylcyclopentadiene) 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 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 and dichlorotoluene;
the alpha-olefin comprises 1-octene, 1-hexene, etc.;
in the reaction, the molar ratio of the oligomerization catalyst to the copolymerization catalyst is 1: (0.05 to 10), preferably 1: (0.1 to 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 metal atoms in the copolymerization catalyst to aluminum in the cocatalyst is 1 (50-500), and when the cocatalyst contains boron, the molar ratio of metal atoms in the copolymerization catalyst to boron in the cocatalyst is 1 (1-4).
The oligomerization reaction temperature is 30-80 ℃ and the oligomerization reaction time is 10-60min; the copolymerization reaction temperature is 100-230 ℃ and the copolymerization reaction time is 5-15min; the pressure of ethylene is 1MPa-6MPa.
The present invention also provides a process for terminating a polymerisation reaction by adding to step 2) a quencher, preferably in an amount of from 0.5 to 5 times, preferably from 1 to 3 times the amount of the cocatalyst material;
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 and hexadecanol, and even 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 method, preferably having a melting point of 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 not more than 4, preferably 1.2 to 3.5.
The invention has the following beneficial effects:
1. in a single reactor, firstly, under the action of an oligomerization 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 copolymerization catalyst and a cocatalyst, ethylene is copolymerized with the generated 1-octene and a small amount of 1-hexene, so that a polyolefin thermoplastic elastomer containing a copolymer of ethylene and alpha-olefin is directly produced by taking ethylene as a raw material;
2. the process for preparing the polyolefin thermoplastic elastomer is simple, and the molecular weight and branching degree of the product can be adjusted by simply changing the reaction time and the proportion of the oligomerization catalyst and the copolymerization catalyst;
3. the produced polyolefin thermoplastic elastomer has the advantages of lower density, small molecular weight distribution index, excellent performance and good application prospect.
Detailed Description
The following specific examples are only illustrative of the present invention, but are merely a partial content of the present invention and are not intended to limit the application of the present invention to other fields. The starting materials used in the examples were all conventional in the art and the purity specifications used were analytically or chemically pure.
Raw material source information:
2-methylimidazolidine: more than or equal to 95 percent, shanghai Shaoshao far reagent Co., ltd
2-isopropylimidazolidine: more than or equal to 95 percent, shanghai Shaoshao far reagent Co., ltd
2-tert-butylimidazolidine: more than or equal to 95 percent, shanghai Shaoshao far reagent Co., ltd
2-cyclohexylimidazolidine: more than or equal to 95 percent, shanghai Shaoshao far reagent Co., ltd
Triethylamine: 99.5% (GC) or more, shanghai Ala Ding Shenghua technology Co., ltd
Diphenyl phosphine chloride: 97%, alfa Elisa (China) chemical Co., ltd
4- (tri-n-butylsilyl) phenyl phosphine chloride: 97%, jiangsu Xinnoco catalyst Co., ltd
Ethyl acetate: 99.9% >, of the technical Co.Ltd
Ethanol: analytically pure, national medicine group chemical reagent Co., ltd
MMAO-7 (modified methylaluminoxane): al, isopar E solvent, noron chemical Co., ltd at a concentration of 7wt%
MAO (methylaluminoxane) at a concentration of 10wt%, toluene solvent, noron chemical (Ningbo Co., ltd.)
iPr-PNP (CAS: 60981-68-20): > 97%, jiangsu Xinnoco catalyst Co., ltd
Melting point test: the melting point (Tm) of the polymer was characterized by DSC analysis using a Mettle DSC1 model. About 5mg of the sample was weighed into an aluminum sample dish, and the dish was capped and sealed. The prepared sample is put into a sample cell by forceps, and a furnace cover is covered. The quality of the sample is input into the control software, the temperature-raising program firstly raises the temperature from 40 ℃ to 160 ℃ at a temperature-raising rate of 10 ℃/min, and the temperature of 160 ℃ is kept constant for 5min to eliminate the heat history. Then cooling to 40 ℃ at a cooling rate of 10 ℃/min, and collecting a crystallization curve of the sample. 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 branching degree of the polymerization product. The instrument used was of the Agilent7870 type and equipped with two columns of PLgel-oxides type. About 7mg of the sample is weighed and placed in a 20mL sample bottle, 10mL of 1,2, 4-Trichlorobenzene (TCB) solution containing a small amount of antioxidant is added by a syringe, the solution is dissolved for 4 hours in a 160 ℃ environment in an oscillating way, then the solution of the dissolved sample is filtered into the sample bottle by a filter gun, and the sample is placed in a sample tray. The test temperature is 160 ℃, the solvent flow rate is 1.0mL/min, and the automatic sample injection test is started when the instrument runs stably. A molecular weight calibration curve was obtained using Polystyrene (PS) as a standard.
The components in the oligomerization reaction liquid are subjected to gas chromatography qualitative and quantitative analysis: the conditions of the GC analysis instrument used were as follows: instrument model: island GC2010; chromatographic column: DB-5 (30 m 0.25mm 0.25 μm); column temperature procedure: first at 35℃for 10min, then at a rate of 10℃per minute, to 250℃for 10min. Detector temperature: 300 ℃; carrier gas: 1bar; air: 0.3bar; gas (H2): 0.3bar
Sample mass analysis was performed using an internal standard method. Should:
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 the meteorological chromatograph, and a is the peak area of the internal standard substance. k is a correction factor related to the substance being tested and the detection conditions.
Preparation of oligomerization catalyst:
(1) Under anhydrous and anaerobic conditions, 100mmol of 2-methylimidazole is dissolved in 200ml of dichloromethane to obtain a reaction solution I; 220mmol of triethylamine is dropwise added into the reaction liquid I under stirring at the temperature of minus 5 ℃, 110mmol of diphenyl phosphine chloride is slowly added into the reaction liquid I, the solution is stable, the heat release is not continued, the rest 110mmol of diphenyl phosphine chloride is added, the reaction liquid is stirred for 3 hours, the low-temperature constant-temperature reaction bath is removed, and the reaction liquid is stirred for 12 hours at room temperature. The reaction solution was purified by column chromatography (tetrahydrofuran elution, height to diameter ratio of 2), then recrystallized at 78 ℃ (solvent ethanol: ethyl acetate=5:1), and the reaction solution was treated to obtain a product, namely PNNP ligand P1.
1mmol of PNNP ligand P1 and 1mmol of chromium tetrahydrofuran chloride were taken, added to 100ml of toluene and heated to 80℃and stirred for 12h, a blue powdery precipitate was formed, cooled to room temperature and toluene was filtered off. The crude product was washed twice with petroleum ether (20 ml) and dried in vacuo to give carbon-bridged biphosphine chromium complex L1
(2) Under anhydrous and anaerobic conditions, 100mmol of 2-isopropyl imidazolidine is dissolved in 200ml of acetonitrile to obtain a reaction solution I; 220mmol of triethylamine is dropwise added into the reaction liquid I under stirring at the temperature of minus 5 ℃, 110mmol of diphenyl phosphine chloride is slowly added into the reaction liquid I, the solution is stable, the heat release is not continued, the rest 110mmol of diphenyl phosphine chloride is added, the reaction liquid is stirred for 3 hours, the low-temperature constant-temperature reaction bath is removed, and the reaction liquid is stirred for 18 hours at room temperature. The reaction solution was purified by column chromatography (tetrahydrofuran elution, height to diameter ratio of 2), then recrystallized at 80 ℃ (solvent ethanol: ethyl acetate=5:1), and the reaction solution was treated to obtain a product, namely PNNP ligand P2. Preparation of reference L1 to give carbon-bridged bisphosphine chromium complex L2
(3) Under anhydrous and anaerobic conditions, 100mmol of 2-tertiary butyl imidazolidine is dissolved in 200ml of dichloromethane to obtain a reaction liquid I; 220mmol of triethylamine is dropwise added into the reaction solution I under stirring at the temperature of minus 5 ℃, 110mmol of a compound (diphenyl phosphine chloride) shown in a structure III is slowly added into the reaction solution I, the rest 110mmol of diphenyl phosphine chloride is added after the solution is stable and no heat release is continued, the low-temperature constant-temperature reaction bath is removed after stirring reaction is carried out for 3 hours, and stirring is carried out for 18 hours at room temperature. The reaction solution was purified by column chromatography (tetrahydrofuran elution, height to diameter ratio of 2), then recrystallized at 80 ℃ (solvent ethanol: ethyl acetate=5:1), and treated to obtain PNNP ligand P3 as a product. L3 was prepared with reference to the L1 catalyst.
(4) Under anhydrous and anaerobic conditions, 100mmol of 2-cyclohexylimidazolidine is dissolved in 200ml of acetonitrile to obtain a reaction solution I; 220mmol of triethylamine is dropwise added into the reaction solution I under stirring at the temperature of minus 5 ℃, 110mmol of a compound (diphenyl phosphine chloride) shown in a structure III is slowly added into the reaction solution I, the rest 110mmol of diphenyl phosphine chloride is added after the solution is stable and no heat release is continued, the low-temperature constant-temperature reaction bath is removed after stirring reaction is carried out for 3 hours, and stirring is carried out for 18 hours at room temperature. The reaction solution was purified by column chromatography (tetrahydrofuran elution, height to diameter ratio of 2), then recrystallized at 80 ℃ (solvent ethanol: ethyl acetate=5:1), and treated to obtain PNNP ligand P4 as a product. L4 was prepared with reference to the L1 catalyst.
(5) L5 is prepared as L4, except that the compound of structure III is 4- (tri-n-butylsilyl) phenylphosphine chloride.
Example 1
Oligomerization catalyst: carbon-bridged biphosphine chromium complex L1.
Copolymerization catalyst: dimethylsilyl (N-T-butylamino) (tetramethylcyclopentadienyl) dimethyl titanium (T1)
Oligomerization co-catalyst system: MMAO-7 (7 wt% Al)
Copolymerization-promoting system: MMAO-7 (7 wt% Al)
Polymerization experiment: the 300ml reactor was heated to 150℃and evacuated for 2h, replaced with nitrogen, and cooled to room temperature, and replaced with ethylene. Under the conditions of the reaction temperature of 55 ℃ and the ethylene pressure of 3MPa, 100ml of methyl cyclohexane after removing water and deoxidizing and 300 mu mol of MMAO-7 are sequentially added into a reactor, stirring is carried out for 2min, 3 mu mol of oligomerization catalyst L1 is added for reaction for 25min (sample GC test, oligomerization reaction is mainly ethylene tetramerization reaction, and a small amount of ethylene trimerization reaction is carried out, the mol ratio of 1-octene to 1-hexene in the reaction liquid is 5.2:1, then the ethylene pressure is controlled to be unchanged (partial ethylene is properly discharged), the temperature of the reaction kettle is increased to 100 ℃,1 mu mol of copolymerization catalyst T1 and 60 mu mol of MMAO-7 are added for continuous reaction for 10min, after the reaction is finished, the polymerization liquid is poured into 30% (volume ratio) hydrochloric acid/ethanol solution for termination reaction, and the polymer product is obtained by ethanol washing and vacuum drying, and 4.57g of polymer is obtained.
Example 2
Oligomerization catalyst: carbon-bridged biphosphine chromium complex L2.
Copolymerization catalyst: dimethylsilyl (N-T-butylamino) (tetramethylcyclopentadienyl) dimethyl titanium (T1)
Oligomerization co-catalyst system: MMAO-7 (7 wt% Al)
Copolymerization-promoting system: MMAO-7 (7 wt% Al)
Polymerization experiment: the 300ml reaction kettle is heated to 120 ℃, vacuumized for 3 hours, replaced by nitrogen, cooled to room temperature and replaced by ethylene. Under the conditions of the reaction temperature of 65 ℃ and the ethylene pressure of 3MPa, 100ml of dehydrated and deoxidized normal hexane and 800 mu mol of MMAO-7 are sequentially added into a reactor, stirring is carried out for 2min, 3 mu mol of oligomerization catalyst L2 is added for reaction for 20min (sample GC test, oligomerization reaction is mainly ethylene tetramerization reaction, and a small amount of ethylene trimerization reaction is carried out, the mol ratio of 1-octene to 1-hexene in the reaction liquid is 5.5:1, then the ethylene pressure is controlled to be unchanged (part of ethylene is properly excreted), the temperature of the reaction kettle is increased to 150 ℃, 0.5 mu mol of copolymerization catalyst T1 and 70 mu mol of MMAO-7 are added for continuous reaction for 10min, after the reaction is finished, the polymerization liquid is poured into 30% (volume ratio) hydrochloric acid/normal octanol solution for termination reaction, and the polymer product is obtained through ethanol washing and vacuum drying, and 3.03g of polymer is obtained.
Example 3
Oligomerization catalyst: carbon-bridged biphosphine chromium complex L3.
Copolymerization catalyst: dimethylsilyl (N-t-butylamino) (tetramethylcyclopentadienyl) dimethyl titanium
Oligomerization co-catalyst system: MMAO-7 (7 wt% Al)
Copolymerization-promoting system: MMAO-7 (7 wt% Al)
Polymerization experiment: the 500ml reactor was heated to 130℃and evacuated for 3h, replaced with nitrogen, and cooled to room temperature, and replaced with ethylene. Adding 200ml of cyclohexane after removal of water and oxygen and 550 mu mol of MMAO-7 into a reactor in sequence under the condition of the reaction temperature of 75 ℃ and the ethylene pressure of 3MPa, stirring for 2min, adding 3 mu mol of oligomerization catalyst L3 for reaction for 20min (sampling GC test, oligomerization reaction mainly comprises ethylene tetramerization reaction and a small amount of ethylene trimerization reaction, wherein the mol ratio of 1-octene to 1-hexene in the reaction liquid is 3.9:1, controlling the ethylene pressure to be unchanged (proper excretion of part of ethylene), heating the reaction kettle to 130 ℃, adding 5 mu mol of copolymerization catalyst T1 and 100 mu mol of MMAO-7, continuing to react for 10min, pouring the polymerization liquid into 30% (volume ratio) hydrochloric acid/2-ethylhexanol solution after the reaction is finished, washing by ethanol, drying in vacuum to obtain a polymer product, collecting the product and drying to obtain 13.45g of polymer.
Example 4
Oligomerization catalyst: carbon-bridged biphosphine chromium complex L4.
Copolymerization catalyst: diphenylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride (Zr 1)
Oligomerization co-catalyst system: MAO (10wt% Al)
Copolymerization-promoting system: MMAO-7 (7 wt% Al)
Polymerization experiment: the 300ml reactor was heated to 160℃and evacuated for 2h, replaced with nitrogen, and cooled to room temperature, and replaced with ethylene. Under the conditions of the reaction temperature of 45 ℃ and the ethylene pressure of 3MPa, 100ml of methyl cyclohexane after removing water and deoxidizing and 150 mu mol of MAO are sequentially added into a reactor, stirring is carried out for 2min, 3 mu mol of oligomerization catalyst L4 is added for reaction for 25min (sample GC test, oligomerization reaction is mainly ethylene tetramerization reaction, and a small amount of ethylene trimerization reaction is carried out, the mol ratio of 1-octene to 1-hexene in the reaction liquid is 4.8:1, then the ethylene pressure is controlled to be unchanged (partial ethylene is properly discharged), the temperature of the reaction kettle is increased to 160 ℃,1 mu mol of copolymerization catalyst Zr1 and 300 mu mol of MMAO-7 are added for continuous reaction for 10min, after the reaction is finished, the polymerization liquid is poured into 30% (volume ratio) hydrochloric acid/ethanol solution for termination reaction, and polymer products are obtained by ethanol washing and vacuum drying, and 14.43g of polymer are obtained.
Example 5
Oligomerization catalyst: carbon-bridged biphosphine chromium complex L5.
Copolymerization catalyst: diphenylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride (Zr 1)
Oligomerization co-catalyst system: MMAO-3 (7 wt% Al)
Copolymerization-promoting system: MMAO-7 (7 wt% Al)
Polymerization experiment: the 300ml reactor was heated to 150℃and evacuated for 2h, replaced with nitrogen, and cooled to room temperature, and replaced with ethylene. Adding 100ml of Isopar E and 900 mu mol of MMAO-7 after dehydration and deoxygenation into a reactor in sequence under the condition of 50 ℃ and 3MPa of ethylene pressure, stirring for 2min, adding 3 mu mol of oligomerization catalyst L5 for reaction for 20min (sampling GC test, oligomerization reaction mainly comprises 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 4.7:1, then controlling the ethylene pressure to be unchanged (proper excreting part of ethylene), heating 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, pouring the polymerization liquid into 30% (volume ratio) hydrochloric acid/ethanol solution to terminate the reaction after the reaction, washing by ethanol, vacuum drying to obtain a polymer product, collecting the product and drying to obtain 17.55g of polymer.
Example 6
Oligomerization catalyst: carbon-bridged biphosphine chromium complex L5
Copolymerization catalyst: diphenylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride (Zr 1)
Oligomerization co-catalyst system: MAO (10wt% Al)
Copolymerization-promoting system: MMAO-7 (7 wt% Al), [ Ph ] 3 C][B(C 6 F 5 ) 4 ]
Polymerization experiment: the 300ml reactor was heated to 150℃and evacuated for 2h, replaced with nitrogen, and cooled to room temperature, and replaced with ethylene. Adding 100ml of dehydrated and deoxidized Isopar E and 1500 mu mol of MAO into a reactor in sequence at the reaction temperature of 50 ℃ and the ethylene pressure of 3MPa, stirring for 2min, adding 3 mu mol of oligomerization catalyst L5, and reacting for 20min (sampling GC test, oligomerizationThe reaction mainly comprises ethylene tetramerization reaction and a small amount of ethylene trimerization reaction, wherein the mol ratio of 1-octene to 1-hexene in the reaction liquid is 4.5:1, then controlling the ethylene pressure to be unchanged (properly excreting part of ethylene), raising the temperature of the reaction kettle to 140 ℃, adding 1 mu mol of copolymerization catalyst Zr1 and 1 mu mol [ Ph ] 3 C][B(C 6 F 5 ) 4 ]And 60 mu mol MMAO-7, continuing the reaction for 10min, pouring the polymerization solution into 30% (volume ratio) hydrochloric acid/ethanol solution to terminate the reaction, washing with ethanol, vacuum drying to obtain polymer product, collecting the product and drying to obtain 9.26g polymer. The properties of the polymer are shown in Table 2.
Example 7
Oligomerization catalyst: carbon-bridged biphosphine chromium complex L5
Copolymerization catalyst: diphenylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride (Zr 1)
Oligomerization co-catalyst system: MAO (10wt% Al)
Copolymerization-promoting system: MMAO-7 (7 wt% Al), [ Ph ] 3 C][B(C 6 F 5 ) 4 ]
Polymerization experiment: the 300ml reactor was heated to 150℃and evacuated for 2h, replaced with nitrogen, and cooled to room temperature, and replaced with ethylene. Adding 100ml of Isopar E after removal of water and deoxidization and 2000 mu mol of MAO into a reactor in sequence at a reaction temperature of 75 ℃ and an ethylene pressure of 3MPa, stirring for 2min, adding 3 mu mol of oligomerization catalyst L5 for 20min (sample GC test, oligomerization reaction mainly comprises 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 4.3:1, then controlling the ethylene pressure to be unchanged (properly excreting part of ethylene), heating the reactor to 100 ℃, and adding 3 mu mol of copolymerization catalyst Zr1 and 1 mu mol [ Ph ] into the reactor 3 C][B(C 6 F 5 ) 4 ]And 300 mu mol of MMAO-7, continuing the reaction 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, and drying in vacuum to obtain a polymer product, collecting the product and drying to obtain 17.02g of polymer. The properties of the polymer are shown in Table 2.
Example 8
Oligomerization catalyst: carbon-bridged biphosphine chromium complex L2
Copolymerization catalyst: diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride (Zr 2)
Oligomerization co-catalyst system: MAO (10wt% Al)
Copolymerization-promoting system: al (Al) i Bu 3 、[Ph 3 C][B(C 6 F 5 ) 4 ]
Polymerization experiment: the 300ml reactor was heated to 150℃and evacuated for 2h, replaced with nitrogen, and cooled to room temperature, and replaced with ethylene. Adding 100ml of Isopar E after removal of water and deoxidization and 500 mu mol of MMAO-7 into a reactor in sequence under the condition of a reaction temperature of 60 ℃ and an ethylene pressure of 4MPa, stirring for 2min, adding 2 mu mol of oligomerization catalyst L2 for 40min (sampling GC test, oligomerization reaction is mainly ethylene tetramerization reaction, and a small amount of ethylene trimerization reaction, wherein the mol ratio of 1-octene to 1-hexene in the reaction solution is 5.6:1, controlling the ethylene pressure to be unchanged (properly discharging part of ethylene), heating the reactor to 100 ℃, and adding 1 mu mol of copolymerization catalyst Zr2 and 1 mu mol [ Ph ] into the reactor 3 C][B(C 6 F 5 ) 4 ]And 500. Mu. Mol of Al i Bu 3 And continuing the reaction for 5min, after the reaction is finished, pouring the polymerization solution into a 30% (volume ratio) hydrochloric acid/ethanol solution to terminate the reaction, washing with ethanol, and drying in vacuum to obtain a polymer product, collecting the product and drying to obtain 4.28g of polymer. The properties of the polymer are shown in Table 2.
Example 9
Oligomerization catalyst: carbon-bridged biphosphine chromium complex L3
Copolymerization catalyst: dimethyl disilylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride (Zr 3)
Oligomerization co-catalyst system: MAO (10wt% Al)
Copolymerization-promoting system: MMAO-7 (7 wt% Al), [ Ph ] 3 C][B(C 6 F 5 ) 4 ]
Polymerization experiment: the 300ml reactor was heated to 150℃and evacuated for 2h, replaced with nitrogen, and cooled to room temperature, and replaced with ethylene. Adding 100ml of Isopar E and 900 mu mol of MAO after removing water and deoxidizing into a reactor in sequence under the condition of the reaction temperature of 55 ℃ and the ethylene pressure of 1MPa, stirring for 2min, adding 6 mu mol of oligomerization catalyst L3 for reaction for 30min (sampling GC test, oligomerization reaction mainly comprises ethylene tetramerization reaction and a small amount of ethylene trimerization reaction, wherein the mol ratio of 1-octene to 1-hexene in the reaction liquid is 4.2:1, controlling the ethylene pressure to be unchanged (proper excretion of part of ethylene), heating the reaction kettle to 200 ℃, adding 1 mu mol of copolymerization catalyst Zr3 and 200 mu mol of MMAO-7 (7 wt% of Al), continuing to react for 5min, pouring the polymerization liquid into 30% (volume ratio) hydrochloric acid/ethanol solution for terminating reaction after the reaction, washing by ethanol, drying in vacuum to obtain a polymer product, collecting the product and drying to obtain 9.82g of polymer, wherein the performance of the polymer is shown in Table 2.
Example 10
Oligomerization catalyst: carbon-bridged biphosphine chromium complex L4
Copolymerization catalyst: di-p-toluene methylene cyclopentadiene (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride (Zr 4)
Oligomerization co-catalyst system: MMAO-7 (7 wt% Al)
Copolymerization-promoting system: MMAO-7 (7 wt% Al)
Polymerization experiment: the 300ml reactor was heated to 150℃and evacuated for 2h, replaced with nitrogen, and cooled to room temperature, and replaced with ethylene. Adding 100ml of Isopar E and 600 mu mol of MMAO-7 after dehydration and deoxygenation into a reactor in sequence under the condition of the reaction temperature of 65 ℃ and the ethylene pressure of 5MPa, stirring for 2min, adding 5 mu mol of oligomerization catalyst L4 for reaction for 30min (sampling GC test, oligomerization reaction 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 5.3:1), controlling the ethylene pressure to be unchanged (proper excreting part of ethylene), raising the temperature of the reaction kettle to 150 ℃, adding 1 mu mol of copolymerization catalyst Zr4 and 150 mu mol of MMAO-7 (7 wt% of Al), continuing the reaction for 15min, pouring the polymerization liquid into a hydrochloric acid/ethanol solution with the volume ratio of 30 percent for terminating the reaction, washing the reaction liquid with ethanol, drying the reaction liquid in vacuum to obtain a polymer product, and collecting the product and drying the product to obtain 11.03g of polymer. The properties of the polymer are shown in Table 2.
Comparative example 1:
the preparation method is as in example 1 by using an outsourcing ligand iPr-PNP to obtain a catalyst carbon-bridged biphosphine chromium complex La.
Polymerization experiments were as in example 1, yielding 3.19g of polymer. The comparison shows that the carbon bridged biphosphine chromium complex prepared by the existing PNP system is used for cascade preparation of polyolefin thermoplastic elastomer, the selectivity of octene in the oligomerization product is relatively low, and the insertion rate of the copolymerization product is lower.
Table 1: examples reaction conditions
TABLE 2
Claims (13)
1. A process for preparing a polyolefin elastomer comprising the steps of:
1) In a high-pressure reaction kettle, under the condition that the ethylene pressure is 1-6 MPa, in a solvent, oligomerization is carried out on ethylene in the presence of an oligomerization catalyst and a cocatalyst to prepare alpha-olefin;
2) After the oligomerization of step 1) is completed, adding a copolymerization catalyst and a cocatalyst into the reaction system to copolymerize ethylene with the alpha-olefin obtained in step 1) to form a polyolefin thermoplastic elastomer;
the oligomerization catalyst is a carbon bridging biphosphine chromium complex represented by a formula I,
wherein R is 1 、R 2 、R 3 、R 4 Each independently selected from aryl and derivatives thereof, R 5 Each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, vinyl, propenyl, cyclopentyl, cyclohexyl, phenyl.
2. The method of claim 1, wherein R 1 、R 2 、R 3 、R 4 Selected from 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, 2- (tri-n-butylsilyl) phenyl, 3- (tri-n-butylsilyl) phenyl, 4- (tri-n-butylsilyl) phenyl.
3. The process of claim 1 wherein the copolymerization catalyst is a single site metallocene catalyst or a post-metallocene catalyst.
4. The process according to claim 3, wherein the copolymerization catalyst is dimethylsilyl (N-t-butylamino) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilyl (N-t-butylamino) (fluorenyl) titanium dichloride, (pentamethylcyclopentadienyl) trimethoxytitanium, dibenzylidene (cyclopentadienyl) (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, (cyclopentadienyl) (1, 2-dimethoxyethane) zirconium trichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, racemic dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride, dibenzoylmethylene (2, 7-di-t-butylfluorenyl) bis (2-methyl-1-indenyl) zirconium dichloride, dibenzoylmethylene (2, 7-dimethylfluorenyl) zirconium dichloride, p-dimethylcyclopentadienyl (2-dimethylfluorenyl) zirconium dichloride Bis (n-butylcyclopentadiene) hafnium dichloride.
5. A process according to any one of claims 1 to 3, wherein the cocatalyst is at least one of an alkyl aluminium, an organoboron compound, an alkyl aluminoxane.
6. The process of claim 5 wherein the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tris (pentafluorophenyl) boron compound.
7. A process according to any one of claims 1 to 3, wherein the reaction solvent is selected from aliphatic hydrocarbon solvents and/or aromatic hydrocarbon solvents.
8. The process of claim 7, wherein 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 selected from one or more of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene and dichlorotoluene.
9. A process according to any one of claims 1 to 3, wherein the α -olefin comprises 1-octene, 1-hexene.
10. A process according to any one of claims 1 to 3, wherein the oligomerization catalyst and the copolymerization catalyst are present in a molar ratio of 1: (0.05-10); 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 metal atoms in the copolymerization catalyst to aluminum in the cocatalyst is 1 (50-500), and when the cocatalyst contains boron, the molar ratio of metal atoms in the copolymerization catalyst to boron in the cocatalyst is 1 (1-4).
11. A process according to any one of claims 1 to 3 wherein the oligomerization temperature is from 30 ℃ to 80 ℃ and the oligomerization time is from 10 to 60 minutes; the copolymerization reaction temperature is 100-230 ℃ and the copolymerization reaction time is 5-15min; the pressure of ethylene is 1MPa-6MPa.
12. A polyolefin thermoplastic elastomer prepared by the process according to any of claims 1 to 3, wherein the polyolefin thermoplastic elastomer has a melting point of 50 ℃ to 120 ℃; a weight average molecular weight of 20000 to 180000; the molecular weight distribution index is less than or equal to 4.
13. The polyolefin thermoplastic elastomer prepared by the process according to claim 12, wherein the polyolefin thermoplastic elastomer has a melting point of 55 ℃ to 105 ℃; the weight average molecular weight is 40000-160000; the molecular weight distribution index is 1.2-3.5.
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