CN111171189B - High-temperature-resistant catalyst system and application thereof - Google Patents
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Abstract
The invention discloses a high temperature resistant catalyst system and application thereof, wherein the system comprises: (i) a procatalyst; (ii) A co-catalyst which is an alkyl modified and/or alkoxy modified aluminum reagent; and (iii) a boron activator which is a boron series and/or a borate; the structural formula of the main catalyst is shown as a formula I, wherein R 1 ，R 2 Each independently selected from one or more of alkyl, cycloalkyl, aryl, alkoxy, cycloalkyloxy and aryloxy modified oxygen, nitrogen, phosphorus or sulfur atoms, and the metal M is selected from one or more of titanium, zirconium and hafnium. The catalyst system is used for the copolymerization reaction of ethylene/alpha-olefin solution by adopting the main catalyst matched with the cocatalyst and the activator, shows high polymerization activity and copolymerization performance, and is particularly remarkable in high temperature tolerance.
Description
Technical Field
The invention relates to the field of polyolefin, in particular to a polyolefin elastomer (POE) high-temperature-resistant catalyst system, and also relates to application of the catalyst system.
Background
In the eighties of the last century, the Dow chemical company of America utilized a solution polymerization process to expand the LLDPE product category into plastomers, and then in 1993, the ethylene/alpha-olefin random copolymer elastomer POE made of Constrained Geometry metallocene Catalyst (CGC) was introduced, and the product covers three types of random copolymers of ethylene/1-butene, ethylene/1-hexene and ethylene/1-octene. For industrial applications ethylene/1-octene copolymer elastomers are the most tough, typically having an octene content of 15 to 45wt% and a crystallinity of less than 25%. Due to the single-active-center characteristic of the metallocene catalyst and the combination of the homogeneous phase characteristic of solution polymerization, the chain structure of the polymer can be more accurately regulated and controlled by the ethylene solution polymerization catalyzed by the single-active-center metallocene, and the polyolefin elastomer with narrow molecular weight distribution and uniform copolymer composition distribution is obtained. The polymer concentration can be 40wt% by adopting near-critical dispersion polymerization, but the technology is still in a research and pilot stage and has not been reported industrially. For the production of POE, although there are patents reporting POE produced by a slurry method, because the POE has a low melting point, is easy to swell in a solvent, and the product is easy to melt and agglomerate, no industrial example of POE produced by the slurry method exists at present. Therefore, the solution method will still be the main process technology for industrial production of POE.
The main factor for limiting the polymer concentration in the solution polymerization is that the temperature of the reaction system is not high enough, the root cause is the limited high temperature resistance of the catalyst, and the reaction temperature of the CGC catalyst for industrialization reported by Dow is only 140 ℃ (US 5064802).
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a high-temperature-resistant catalyst system and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high temperature resistant catalyst system, the system comprising:
(i) A main catalyst;
(ii) A cocatalyst which is an alkyl-modified or alkoxy-modified aluminum reagent; and
(iii) An activator which is a boron series and/or a borate;
the structural formula of the main catalyst is shown as the following formula I, wherein R 1 ，R 2 Each independently selected from one or more of alkyl, cycloalkyl, aryl, alkoxy, cycloalkyloxy and aryloxy modified oxygen, nitrogen, phosphorus or sulfur atoms, and the metal M is selected from one or more of titanium, zirconium and hafnium.
In a preferred embodiment, the R is a hydrogen atom 1 ，R 2 Each independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, naphthyl, anthryl and biphenylOne or more of yl, ethenyl, propenyl, cyclohexyl, butyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, tolyl, xylyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, phenoxy, methoxy, ethoxy, tolyloxy, dimethylamino, thiomethyl, o-methylphenyl, o-ethylphenyl, dimethylhydrazine, o-tert-butylphenyl, o-methoxyphenyl, 2,4-dimethylphenyl, 2,4-diisopropylphenyl, 2,4-dibutylphenyl, 2,6-diisopropylphenyl, 2,6-dimethylphenyl, and 2,6-diisopropylphenyl.
According to the catalyst system of the present invention, in a preferred embodiment, the metal M is preferably titanium and/or zirconium, more preferably zirconium; the cocatalyst is preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, methylaluminoxane and/or modified methylaluminoxane, and more preferably methylaluminoxane and/or modified methylaluminoxane; the activator is an alkyl and/or aryl group containing boron series and/or borate, preferably tris (pentafluorophenyl) boron and/or tetrakis (pentafluorophenyl) ammonium borate, more preferably tetrakis (pentafluorophenyl) ammonium borate.
According to the catalyst system of the present invention, in a preferred embodiment, the molar ratio of the main catalyst to the cocatalyst is 1:1-1000, preferably 1:1-10; the molar ratio of the main catalyst to the activator is 1:1-100, preferably 1:1-10, and more preferably, the molar ratio of the main catalyst, the cocatalyst and the activator is 1.
According to the catalyst system of the present invention, in a preferred embodiment, the main catalyst is formed by complexing a salt compound of a metal M and a ligand L, wherein the ligand L comprises ligands L1 to L4, and the structural formula of the ligand L is as follows:
according to the catalyst system of the present invention, in a preferred embodiment, the salt-like compound of the metal M is selected from one or more of titanium chloride, zirconium chloride and hafnium chloride; one or more of titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride are preferred.
According to the catalyst system of the present invention, in a preferred embodiment, the preparation method of the main catalyst comprises: dissolving a ligand L in an organic solvent, adding butyl lithium to react for 1-3 hours at room temperature, washing the obtained solid after the solvent is drained, dissolving the solid in the organic solvent, adding a salt compound of metal M, heating to 110-130 ℃, carrying out reflux reaction for 5-10 hours, draining the solvent after the reaction is finished, and washing the product to obtain a main catalyst product;
preferably, the organic solvent is selected from one or more of toluene, benzene or dichloromethane.
According to the catalyst system of the present invention, in a preferred embodiment, the preparation method of the main catalyst comprises: dissolving the ligand L in toluene, adding butyl lithium, reacting at room temperature for 1-3 hours, draining the solvent, adding dry n-hexane, and washing away unreacted ligand and residual n-butyl lithium. And (3) draining the normal hexane, dissolving the solid in a dry toluene solvent, adding a salt compound of metal M, heating to 120 ℃, carrying out reflux reaction for 5-10 hours, draining the solvent after the reaction is finished, and washing the product to obtain the main catalyst product.
The second aspect of the present invention provides the use of a catalyst system as described above for the preparation of a catalysed polyolefin elastomer (POE), in particular for the preparation of a polyolefin elastomer by copolymerisation of ethylene and octene in a high temperature solution process, in particular for the preparation of a polyolefin elastomer by copolymerisation of ethylene and octene.
The third aspect of the present invention provides a method for synthesizing a polyolefin elastomer by using the catalyst system described above, comprising raising the temperature of octene, cocatalyst and activator dissolved in a reaction solvent to 140-220 ℃ under the protection of inert gas, then introducing ethylene to raise the pressure to 1-5MPa, then pressing the main catalyst dissolved in the reaction solvent with ethylene at a pressure higher than 0.5-1MPa of the reaction system to form a reaction system, cooling the reaction system to 70-90 ℃ after the reaction is finished, evacuating ethylene, then discharging the reaction solution into a device filled with water, washing and filtering, collecting the polymer, and vacuum drying at 40-60 ℃ to obtain the polyolefin elastomer.
According to the synthesis method of the present invention, in a preferred embodiment, the reaction solvent is one or more of aliphatic hydrocarbon compound and aromatic hydrocarbon compound, wherein the aliphatic hydrocarbon compound is one or more of n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclohexane and methylcyclohexane; the aromatic hydrocarbon compound is one or more of toluene and xylene.
According to the synthesis method of the invention, in a preferred embodiment, the octene is preferably 1-octene, and the volume proportion of 1-octene in the total reaction system is 15-25%, preferably 20%; the concentration of the 1-octene is 0.96mol/L-1.60mol/L, and is preferably 1.27mol/L.
The letter "M, L" is used herein merely as a reference number for convenience of description and reference hereinafter, and has no particular technical connotation.
"a plurality" of "one or more" as described herein means "two or more".
The technical scheme provided by the invention has the following beneficial effects: the invention provides a reaction system consisting of a high-temperature-resistant main catalyst, a cocatalyst, an activator and an organic solvent, which is high in high-temperature resistance, catalytic activity and 1-octene insertion rate. The high temperature resistance, activity and high comonomer insertion rate of the catalytic system are mainly based on a special ligand structure, namely a ligand spiro structure and heteroatom functional groups modified on the spiro structure form a catalytic pocket for olefin copolymerization. The size of the catalytic pocket opening is a determining factor that affects whether the catalyst is resistant to high temperatures and also a critical factor that affects the rate of comonomer insertion. Since the deactivation of olefin copolymerization catalysts at high temperature is caused by the entry of co-catalysts (e.g., MAO) into the catalytic pocket, attacking the metal active sites. The effect of the catalyst on comonomer insertion is whether the size of the catalytic pocket favors insertion of the comonomer (e.g., octene). The opening size of the spiral catalytic pocket can meet the requirement of high-efficiency insertion of octene, and can effectively prevent the main catalyst from entering under the high-temperature condition. The high temperature resistance (up to 200 ℃) of the catalytic system can greatly reduce the cost of a POE continuous device in terms of solvent and energy consumption.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative of the present invention only and are not intended to limit the scope of the present invention.
The following examples 1-6 are examples of the preparation of the procatalyst in the catalyst system.
Example 1
In a glove box, ligand L1 (1 mmol) was dissolved in 10ml of dry toluene, and then n-butyllithium (2 mmol) was added and reacted at room temperature for 1 hour. After the solvent was drained, 10ml of dry n-hexane was added to wash out unreacted ligand and the remaining n-butyllithium. The n-hexane was dried by suction, the solid was dissolved in 10ml of dry toluene, zirconium tetrachloride (1 mmol) was added, and heating and refluxing were carried out at 120 ℃ for 5 hours. After the reaction is finished, the solvent is drained, and the main catalyst M1 is obtained by recrystallization with a toluene and n-hexane system, wherein the characterization result is as follows:
1 H NMR(400MHz,CDCl 3 )7.24-7.35(m,4H),6.75-6.84(m,2H),3.12-3.25(m,4H),1.76-1.88(m,2H),1.55-168(m,4H)，0.95(s,18H)。
example 2
In a glove box, ligand L2 (1 mmol) was dissolved in 10ml of dry toluene, followed by addition of n-butyllithium (2 mmol) and reaction at room temperature for 1 hour. After the solvent was drained, 10ml of dry n-hexane was added to wash out unreacted ligand and the remaining n-butyllithium. The n-hexane was dried by suction, the solid was dissolved in 10ml of dry toluene, zirconium tetrachloride (1 mmol) was added, and heating and refluxing were carried out at 120 ℃ for 5 hours. After the reaction is finished, the solvent is drained, and M2 is obtained by recrystallization with a toluene and n-hexane system, and the characterization result is as follows:
1 H NMR(400MHz,CDCl 3 )7.34-7.47(m,4H),6.65-6.75(m,2H),3.10-3.18(m,4H),2.35-2.45(m,2H),1.72-1.80(m,2H),0.98(d,J＝6.2HZ,12H)。
example 3
In a glove box, ligand L3 (1 mmol) was dissolved in 10ml of dry toluene, followed by addition of n-butyllithium (2 mmol) and reaction at room temperature for 3 hours. After the solvent was drained, 10ml of dry n-hexane was added to wash out unreacted ligand and the remaining n-butyllithium. The n-hexane was dried by suction, the solid was dissolved in 10ml of dry toluene, and then zirconium tetrachloride (1 mmol) was added thereto, and the mixture was heated under reflux at 110 ℃ for 10 hours. After the reaction is finished, the solvent is drained, and M3 is obtained by recrystallization with a toluene and n-hexane system, and the characterization result is as follows:
1 H NMR(400MHz,CDCl 3 )7.46-7.58(m,4H),7.13-7.22(m,6H),6.95-7.02(m,4H),3.65-3.73(m,4H),3.44-3.51(m,4H),3.15-3.22(m,4H),2.35-2.44(m,2H),2.23-2.34(m,2H),0.98(s,18H)。
example 4
In a glove box, ligand L4 (1 mmol) was dissolved in 10ml of dry toluene, followed by addition of n-butyllithium (2 mmol) and reaction at room temperature for 2 hours. After the solvent was drained, 10ml of dry n-hexane was added to wash out unreacted ligand and the remaining n-butyllithium. The n-hexane was dried by suction, the solid was dissolved in 10ml of dry toluene, and then zirconium tetrachloride (1 mmol) was added, and heating and refluxing were carried out at 130 ℃ for 8 hours. After the reaction is finished, the solvent is drained, and M4 is obtained by recrystallization with a toluene and n-hexane system, and the characterization result is as follows:
1 H NMR(400MHz,CDCl 3 )7.46-7.58(m,4H),7.13-7.22(m,6H),6.95-7.02(m,4H),6.43-6.55(m,2H),5.35(s,2H),3.10-3.18(m,4H),1.72-1.80(m,2H)。
in the following examples 5-25, the main catalyst prepared in the above examples 1-4, and the cocatalyst and activator were used together as a catalyst system for ethylene/α -olefin solution copolymerization in a 2L stainless steel batch reactor with magnetic stirring, specifically comprising the following steps:
under the protection of nitrogen, sequentially adding 1000mL of reaction solvent, octene, activator and cocatalyst solution (specifically selected in each embodiment) into a reaction kettle, then heating to the reaction temperature of 90 ℃ (preheating temperature, self-heat release of the reaction), introducing ethylene gas, and maintaining the pressure in the kettle to be stable at the required polymerization pressure; then, the main catalyst solution was pressed into the reactor with ethylene under a pressure of 0.5MPa higher than the pressure in the reactor to start the polymerization reaction. After the polymerization reaction, ethylene was turned off, the reaction vessel was cooled to 80 ℃ and then unreacted ethylene was discharged, and the reaction solution was discharged into 1L of pure water, washed and filtered, and the polymer was collected and vacuum-dried at 50 ℃ to constant weight and weighed. The amounts of reagents, temperature and pressure settings for this process are shown in Table 1.
TABLE 1
Wherein A is tris (pentafluorophenyl) boron and B is N, N-dimethyl-N, N-ditallowaylammonium tetrakis (pentafluorophenyl) borate.
Polymer molecular weight (Mw) and molecular weight distribution (PDI) were determined using high temperature gel permeation chromatography (PL-GPC 220);
1,2,4-trichlorobenzene as the mobile phase, polystyrene standards were used at 150 ℃ with standard concentration of 0.1mg/mL, solvent flow rate of 1.0mL/min, using parameters K =59.1, α =0.69, and sample parameters K =14.1, α =0.70.
The melting point (Tm) of the polymer is determined using a differential scanning calorimeter (METTLER, DSC-1). The test procedure was: taking 5.0-7.0 mg of polymer sample, heating to 160 ℃ at the speed of 30 ℃/min, maintaining for 5min to eliminate thermal history, then cooling to-100 ℃ at the speed of 10 ℃/min, keeping the temperature for 3min, heating to 160 ℃ again at the same speed, obtaining crystallization peak temperature by using a cooling curve, and calculating the melting point of the polymer by using the curve of the second heating process.
Comonomer insertion in ethylene/alpha-olefin copolymers was measured by 13C-NMR (Bruker ADVANCE III M). The polymer was formulated in a solution of deuterated 1,2 o-dichlorobenzene at about 100mg/mL at 130 ℃. The instrument parameters are pulse angle 30 degrees, whole decoupling is carried out, pulse delay time is 3s, and a sample is continuously scanned more than 3000 times to obtain a high-temperature nuclear magnetic spectrum. The carbon spectrum of the copolymer is assigned by adopting an ASTM D5017-96 method, and the sequence distribution and the average comonomer composition of the copolymer are calculated. The above methods are common general knowledge in the art, and are not described in detail. The polymer characterization results are shown in table 2.
TABLE 2
Wherein the polymer production method in comparative example 1 is described in reference a: US6506857, 2003; example 27
Comparative example 2 Polymer preparation methods reference b macromolecules, 1997, 30, 3164-3168;
the polymer preparation method in comparative example 3 is described in reference c, macromol. Chem. Phys.1996, 197, 3091-3098.
The catalyst used in comparative example 1,2,3 is a conventional single metallocene structured catalyst.
From the data in tables 1 and 2, it can be seen that the catalyst system not only has high temperature resistance (reaction temperature can reach 200 ℃), but also has high catalytic activity and 1-octene insertion rate.
In addition, compared with M1-M3, in the catalyst M4, except for a special space environment provided by a spiro ring, an aromatic ring modified on a heteroatom plays a key role in regulating and controlling the size of a catalytic pocket, so that the M4 catalyst has better catalytic performance at high temperature. And when the proportion of MMAO is high, catalytic centers are attacked at high temperature, resulting in a decrease in catalyst activity.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (20)
1. A high temperature resistant catalyst system, characterized in that the system comprises:
(i) A main catalyst;
(ii) A co-catalyst which is an alkyl modified and/or alkoxy modified aluminum reagent; and
(iii) A boron activator which is a boron series and/or borate;
the structural formula of the main catalyst is shown as a formula I, wherein R 1 ，R 2 Each independently selected from one or more of alkyl, cycloalkyl, aryl, alkoxy, cycloalkyloxy, aryloxy-modified oxygen, nitrogen, phosphorus or sulfur atoms, the metal M being selected from one or more of titanium, zirconium and hafnium;
2. the refractory catalyst system of claim 1, wherein R is 1 ，R 2 Each independently selected from one or more of modified oxygen, nitrogen, phosphorus or sulfur atoms in methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, naphthyl, anthracenyl, biphenyl, cyclohexyl, butyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, tolyl, xylyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, phenoxy, methoxy, ethoxy, tolyloxy, o-ethylphenyl, o-tert-butylphenyl, o-methoxyphenyl, 2,4-dimethylphenyl, 2,4-diisopropylphenyl, 2,4-dibutylphenyl, 2,6-diisopropylphenyl, 2,6-dimethylphenyl, and 2,6-diisopropylphenyl.
3. The refractory catalyst system as recited in claim 1, wherein R is 1 ，R 2 Is dimethylamino or thiomethyl.
4. The refractory catalyst system as recited in claim 1 or 2, wherein the metal M is titanium and/or zirconium; the cocatalyst is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, methylaluminoxane and/or modified methylaluminoxane; the activator is boron series and/or borate containing alkyl and/or aryl.
5. The refractory catalyst system as recited in claim 4, wherein the metal M is zirconium; the cocatalyst is methylaluminoxane and/or modified methylaluminoxane; the activating agent is tri (pentafluoro-phenyl) boron and/or tetra (pentafluoro-phenyl) ammonium borate.
6. The refractory catalyst system of claim 5, wherein the activator is ammonium tetrakis (pentafluorophenyl) borate.
7. The high temperature resistant catalyst system of claim 1 or 2, wherein the molar ratio of the main catalyst to the cocatalyst is 1:1-1000; the molar ratio of the main catalyst to the activator is 1:1-100.
8. The high temperature resistant catalyst system of claim 7, wherein the molar ratio of the main catalyst to the cocatalyst is 1:1-10; the molar ratio of the main catalyst to the activator is 1:1-10.
9. The high temperature resistant catalyst system of claim 8, wherein the molar ratio of the main catalyst, the cocatalyst and the activator is 1.
10. The high temperature resistant catalyst system of claim 1 or 2, wherein the main catalyst is formed by complexing a salt compound of a metal M and a ligand L, wherein the ligand L comprises ligands L1 to L2, and the structural formula of the ligand L is as follows:
11. the refractory catalyst system as recited in claim 10, wherein the salt-based compound of the metal M is selected from one or more of titanium chloride, zirconium chloride and hafnium chloride.
12. The refractory catalyst system as recited in claim 11, wherein the salt-based compound of metal M is selected from one or more of titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.
13. The refractory catalyst system as recited in claim 10, wherein the preparation method of the procatalyst comprises: dissolving a ligand L in an organic solvent, adding butyl lithium, reacting at room temperature for 1-3 hours, draining the solvent, washing the obtained solid, dissolving the solid in the organic solvent, adding a salt compound of metal M, heating to 110-130 ℃, refluxing and reacting for 5-10 hours, draining the solvent after the reaction is finished, and washing the product to obtain a main catalyst product;
the organic solvent is selected from one or more of toluene, benzene or dichloromethane.
14. Use of a catalyst system according to any one of claims 1 to 13 for the preparation of a catalysed polyolefin elastomer.
15. Use of a catalyst system according to claim 14 for catalyzing ethylene/alpha-olefin solution copolymerizations.
16. Use of the catalyst system according to claim 15 for the preparation of polyolefin elastomers by the copolymerization of ethylene and octene in a high temperature solution process.
17. The method for synthesizing a polyolefin elastomer with a catalyst system according to any one of claims 1 to 13, comprising raising the temperature of octene, cocatalyst and activator dissolved in a reaction solvent to 140 to 200 ℃ under the protection of inert gas, then introducing ethylene to 1 to 5MPa, then pressing the main catalyst dissolved in the reaction solvent with ethylene at a pressure higher than 0.5 to 1MPa to form a reaction system, cooling the reaction system to 70 to 90 ℃ after the reaction is finished, evacuating ethylene, then discharging the reaction solution into a device containing water, washing and filtering, collecting the polymer and vacuum-drying at a temperature of 40 to 60 ℃ to obtain the polyolefin elastomer.
18. The method of synthesizing polyolefin elastomer according to claim 17, wherein the reaction solvent is one or more of aliphatic hydrocarbon compound and aromatic hydrocarbon compound, wherein the aliphatic hydrocarbon compound is one or more of n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclohexane and methylcyclohexane; the aromatic hydrocarbon compound is one or more of toluene and xylene.
19. The process for synthesizing polyolefin elastomer according to claim 18, wherein the octene is 1-octene, and the volume proportion of the 1-octene in the reaction system is 15-25%; the concentration of the 1-octene is 0.96mol/L-1.60mol/L.
20. The process for synthesizing polyolefin elastomer according to claim 19, wherein the 1-octene accounts for 20% of the volume of the reaction system; the concentration of the 1-octene is 1.27mol/L.
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| CN111171189A (en) | 2020-05-19 |
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