CN116478321B - Crystalline ethylene-styrene monomer random copolymer and preparation method thereof - Google Patents
Crystalline ethylene-styrene monomer random copolymer and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种结晶性乙烯‑苯乙烯类单体无规共聚物及其制备方法，属于烯烃聚合物制备技术领域。本发明使用桥联双茂稀土化合物与助催化剂有机硼盐和主族烷基试剂相结合，作为催化体系催化乙烯与苯乙烯类单体无规共聚合，使对乙烯与苯乙烯类单体共聚合呈现低催化活性或无催化活性的桥联双茂稀土化合物对乙烯与苯乙烯类单体共聚合展现出高催化活性、并对乙烯聚合具有优先选择性，制备得到含有聚乙烯链段的结晶性乙烯‑苯乙烯类单体无规共聚物，且该共聚物为低苯乙烯含量，具体的含有2.0mol％～20.0mol％的苯乙烯。
The invention discloses a crystalline ethylene-styrene monomer random copolymer and a preparation method thereof, and belongs to the technical field of olefin polymer preparation. The present invention uses a bridged bisocene rare earth compound in combination with a cocatalyst organic boron salt and a main group alkyl reagent as a catalytic system to catalyze the random copolymerization of ethylene and styrene monomers, so that the bridged bisocene rare earth compound having low catalytic activity or no catalytic activity for the copolymerization of ethylene and styrene monomers exhibits high catalytic activity for the copolymerization of ethylene and styrene monomers and has preferential selectivity for ethylene polymerization, and a crystalline ethylene-styrene monomer random copolymer containing a polyethylene segment is prepared, and the copolymer has a low styrene content, specifically containing 2.0 mol% to 20.0 mol% of styrene.
Description
Technical Field
The invention relates to a crystalline ethylene-styrene monomer random copolymer and a preparation method thereof, belonging to the technical field of olefin polymer preparation.
Background
Ethylene, styrene and its derivatives are two types of monomers with very large property differences, and the free radical polymerization method and the traditional Ziegler-Natta catalyst system can not be utilized for copolymerization to prepare the copolymer of ethylene-styrene monomers. The invention of a single-site catalytic system makes it possible to copolymerize these two types of monomers. However, only a few single site catalytic systems have been able to effectively catalyze the copolymerization of ethylene with styrenic monomers to date. For example, nomura et al in Japan found that using a titanium metal complex chelated with a cyclopentadienyl and non-cyclopentadienyl ligand to catalyze the random copolymerization of ethylene and styrene, a sequential random ethylene-styrene copolymer was produced in which the styrene continuous building block was stereospecifically random (Macromolecules 2000,33,8122;Macromolecules 2002,35,5388;Dalton Trans.,2007,1802;J.Am.Chem.Soc.2005,127,9364;Macromolecules 2006,39,5266). Dow chemical company using a constrained geometry titanium catalyst for the copolymerization of ethylene and styrene, producing a non-crystalline quasi-random ethylene-styrene copolymer (EP 0416815A2,1991). Hou Zhaomin and the like catalyze random copolymerization of styrene and ethylene by using a single scandium metal catalytic system to prepare the ethylene-styrene sequence random copolymer containing syndiotactic stereoregular polystyrene chain segments. (J.am.chem.Soc.2004, 126, 13910). ZL 20171012863. X reports that a rare earth catalyst with limited geometric configuration is adopted to catalyze the copolymerization of ethylene and styrene to prepare a quasi-random ethylene-styrene copolymer. Organometallics 2013,32,1445 catalyze the copolymerization of ethylene and styrene using fluorenyl scandium dialkyls to prepare ethylene-styrene copolymers containing syndiotactic polystyrene segments. Carpentier et al used a bridged dual metallocene rare earth allyl catalyst to catalyze the copolymerization of ethylene and styrene to prepare a syndiotactic ethylene-styrene copolymer (Chem.Eur.J.2007, 13,5548,CN200580013508.4) having a high styrene content. However, it is still a challenging task to control the styrene monomer content of the ethylene-styrene copolymer to a reasonable level that preserves the crystallinity of the polyethylene while also containing a proportion of styrene monomer structural units.
Disclosure of Invention
The invention provides a catalytic system which can efficiently prepare an ethylene-styrene monomer random copolymer containing crystalline polyethylene chain segments and can control the content of the styrene monomer in the ethylene-styrene copolymer to be in a range of 2.0mol% to 20.0 mol%.
The technical method comprises the following steps:
The invention provides a preparation method of a crystalline ethylene-styrene monomer random copolymer, which comprises the steps of catalyzing ethylene and a styrene monomer to be copolymerized by a catalytic system consisting of a bridged dual-metallocene rare earth metal compound, an organic boron salt and a main group alkyl reagent under the condition of no water and no oxygen and in the presence of an organic solvent, wherein the obtained copolymer contains 2.0-20.0 mol% of styrene and is a crystalline ethylene-styrene monomer copolymer containing polyethylene chain segments.
Further defined, the bridged dual metallocene rare earth compound has the general formula (Flu-R-Cp) LnR '(Lewis base) n, wherein Flu is a substituted or unsubstituted fluorenyl group, cp is a substituted or unsubstituted cyclopentadienyl group, ln is scandium, yttrium, or any rare earth element other than promethium from lanthanum to lutetium, R is a bridging group between Flu and Cp, R' is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, a silane group, an amine group, and a boronate group, a tetramethyl aluminum group, the Lewis base is a neutral coordinating solvent molecule, and n is an integer of 0 to 2.
Further defined, flu is fluorenyl, 2, 7-di-tert-butylfluorenyl or 3, 6-di-tert-butylfluorenyl.
Still further defined, cp is cyclopentadiene, methylcyclopentadienyl, ethylcyclopentadienyl, n-butylcyclopentadienyl, n-octylcyclopentadienyl or trimethylsilylcyclopentadienyl.
Still further defined, R is Me 2C,Me2Si,MeHSi、Et2 Si or PhMeSi.
Further, R' is an alkyl group having 1 to 16 carbon atoms, a silane group having 4 to 16 carbon atoms, an amine group having 2 to 16 carbon atoms, a silane group having 4 to 20 carbon atoms, an arylamine group having 6 to 20 carbon atoms, an allyl group having 3 to 10 carbon atoms, a benzyl group having 7 to 20 carbon atoms, a borohydride group, a tetramethylaluminum group, or hydrogen.
Further, R' is an alkyl group having 1 to 10 carbon atoms, a silane group having 4 to 12 carbon atoms, an amine group having 2 to 10 carbon atoms, a silane group having 4 to 12 carbon atoms, an arylamine group having 6 to 16 carbon atoms, an allyl group having 3 to 9 carbon atoms, or a benzyl group having 7 to 12 carbon atoms.
Still further defined, R 'is trimethylsilyl, bis-trimethylsilyl, allyl, 2-methallyl, 1, 3-ditrimethylsilylallyl, hexamethylsilylamino, tetramethylsilylamino, methyl, benzyl, 4-methylbenzyl, or 2-N, N' -dimethylbenzyl.
Further defined, ln is scandium, yttrium, lutetium, neodymium, gadolinium, holmium, thulium, erbium, ytterbium, or lanthanum.
Still further defined, the lewis base is tetrahydrofuran, diethyl ether, pyridine or dimethyl diethyl ether.
Still further defined, n is 0 or 1.
Further defined, the bridged dual metallocene rare earth compound has the structure:
Further defined, the organoboron salt is an organic compound containing the boron anion [ B (C 6F5)4 ] -.
Further defined, the organoboron salt is one or a mixture of [PhNMe2H][B(C6F5)4]、[Ph3C][B(C6F5)4]、[N(C18H37)2Me][B(C6F5)4].
Further defined, the main group alkyl reagent is an alumoxane, an alkyl aluminum, an alkyl zinc or an alkyl magnesium.
Further defined, the main group alkyl reagent is one or more of trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisobutylaluminum, triisopropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, MAO, DMAO, MMAO, diethylzinc, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, butylethylmagnesium.
Further defined, the styrenic monomer is one or a mixture of styrene, p-methylstyrene, p-ethylstyrene, p-isopropylstyrene, p-tert-butylstyrene, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, preferably styrene, p-methylstyrene, p-ethylstyrene, p-isopropylstyrene, p-tert-butylstyrene, preferably styrene, p-methylstyrene.
Further defined as the molar ratio of the bridged biscyclopentadienyl rare earth metal compound, the organoboron salt and the main group alkyl reagent is 1 (0.1-1.1): 1-1000.
Further defined, the molar ratio of the bridged biscyclopentadienyl rare earth metal compound, the organoboron salt and the main group alkyl reagent is 1:1 (10-500).
Further defined, the molar ratio of the bridged biscyclopentadienyl rare earth metal compound, the organoboron salt and the main group alkyl reagent is 1:1 (20-100).
Further, the molar ratio of the styrene monomer to the bridged biscyclopentadienyl rare earth metal compound is (1000-100000): 1.
Further defined is a molar ratio of styrenic monomer to bridged biscyclopentadienyl rare earth metal compound of (4000 to 60000): 1.
The preparation process includes dissolving bridged double metallocene RE metal compound and organic boron salt in toluene, adding toluene solution with styrene monomer and main group alkyl reagent and saturated with ethylene at certain temperature, maintaining constant ethylene pressure, maintaining temperature for reaction for certain period, adding ethanol solution to terminate reaction, depositing the reaction solution into ethanol containing small amount of hydrochloric acid and stabilizer, and drying the polymer in vacuum drying oven to obtain crystalline ethylene-styrene monomer random copolymer.
Further defined, the polymerization temperature is 20-200 ℃ and the time is 0.17-24 h.
Further defined is a polymerization temperature of 50 to 150 ℃.
Further defined as a polymerization temperature of 60 to 120 DEG C
Further limiting, wherein the polymerization time is 0.5-10 h.
Further defined, the polymerization time is 1 to 6 hours.
Further defined, the polymerization time is 2-4 hours.
Further defined, the ethylene pressure is 0.1-10 MPa.
Further defined, the ethylene pressure is 0.2 to 6MPa.
Further defined is an ethylene pressure of 0.4 to 1MPa.
Further limited, the concentration of the styrene monomer in the reaction system is 1-90 g/100mL
Further limited, the concentration of the styrene monomer in the reaction system is 10-62 g/100mL.
Compared with the prior art, the invention has the following beneficial effects:
The invention uses the combination of the bridged double-metallocene rare earth compound, the cocatalyst organic boron salt and the main group alkyl reagent as a catalytic system to catalyze the random copolymerization of ethylene and styrene monomers, so that the bridged double-metallocene rare earth compound which has low catalytic activity or no catalytic activity for the copolymerization of ethylene and styrene monomers shows high catalytic activity for the copolymerization of ethylene and styrene monomers and has preferential selectivity for the polymerization of ethylene, and the crystalline ethylene-styrene monomer random copolymer containing polyethylene chain segments is prepared, and has low styrene content and contains 2.0mol% to 20.0mol% of styrene.
Drawings
FIG. 1 is a DSC profile of the polymer prepared in example 1;
FIG. 2 is a DSC profile of the polymerization prepared in example 2;
FIG. 3 is a DSC profile of the polymerization prepared in example 4;
FIG. 4 is a hydrogen nuclear magnetic resonance spectrum of the polymerization prepared in example 2;
FIG. 5 is a hydrogen nuclear magnetic resonance spectrum of the polymerization prepared in example 4.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The following examples used compound 1 and compound 3 to synthesize bridged biscyclopentadienyl rare earth compounds using the method described in document chem. Eur. J.2007,13,5548, the specific preparation method is as follows:
preparation of Compound 1
The bis-metallocene ligand 2mmol of Cp-SiMe 2 -Flu was dissolved in 20mL of diethyl ether solvent, then 4mmol of n-butyllithium hexane solution was added dropwise in ice water bath, and then reacted at room temperature for 4 hours. After that, the reaction solution was rapidly poured into an ether suspension of ScCl 3(THF)3 at-20 ℃, and the reaction was continued with stirring at room temperature for 12 hours. Finally, the mixture was filtered through a glass sand funnel, and the filtrate was collected, pumped down and recrystallized in toluene to give the product (Cp-SiMe 2 -Flu) ScCl (THF). Subsequently, an n-hexane solution containing 1.5mmol of LiCH 2SiMe3 was added dropwise to a toluene solution of 1.5mmol (Cp-SiMe 2 -Flu) ScCl (THF) at room temperature, and after stirring at room temperature for 2 hours, glass sand was filtered, the filtrate was collected, the solvent used was removed in vacuo, and then the solid product was redissolved with n-hexane, concentrated and recrystallized at-30℃to give pale yellow compound 1. The yield was 56%.
Preparation of Compound 3
The Cp-CMe 2 -Flu of the double metallocene ligand 2mmol was dissolved in 20mL diethyl ether solvent, then 4mmol of n-butyllithium hexane solution was added dropwise in ice water bath, and then reacted at room temperature for 4 hours. After that, the reaction solution was rapidly poured into an ether suspension of ScCl 3(THF)3 at-20 ℃, and the reaction was continued with stirring at room temperature for 12 hours. Finally, the mixture was filtered through a glass sand funnel, and the filtrate was collected, pumped down, and recrystallized from toluene to give the product (Cp-CMe 2 -Flu) ScCl (THF). Subsequently, 1.5mmol of KCH 2 Ph as a red solid was added to a toluene solution of 1.5mmol (Cp-SiMe 2 -Flu) ScCl (THF) in portions at room temperature, stirred at room temperature for 2 hours, filtered with glass sand, and the filtrate was collected and concentrated in vacuo and recrystallized at-30℃to give yellow compound 3. The yield was 62%.
Example 1
Compounds 1 (10. Mu. Mol) and [ Ph 3C][B(C6F5)4 ] (abbreviated as A, 10. Mu. Mol) were added to a toluene solution (2 mL) under anhydrous and anaerobic conditions, and to a toluene solution (10 mL) charged with styrene monomer (10 mmol) and Ai iBu3 (0.2 mmol) and saturated with ethylene at 60 ℃. Then, the ethylene pressure was kept constant at 4bar, and after 10 minutes of reaction, a small amount of ethanol solution was added to terminate the polymerization. The reaction solution was then poured into ethanol (100 mL) containing a small amount of hydrochloric acid and stabilizer BHT to settle. Finally, the resulting polymer was dried in a 50 ℃ vacuum oven for 48 hours to give a net weight of 0.62g of polymer M n＝1600,Mw/Mn＝1.57,Tm = 116, as shown in table 1 below, and the DSC profile of the polymer is shown in figure 1.
Example 2
This example differs from example 1 in that the styrene monomer was 20mmol, the reaction time was 20min, and the rest of the procedure and the parameter settings were the same as those of example 1, and the characteristics of the obtained polymer are shown in Table 1 below, and the DSC spectrum of the polymer is shown in FIG. 2.
Example 3
This example differs from example 1 in that the styrene monomer was 20mmol, the toluene solution saturated with ethylene was 20mL, the reaction time was 20min, and the remaining procedures and parameter settings were the same as those of example 1, and the characteristics of the resulting polymer were as shown in Table 1 below.
Example 4
This example differs from example 1 in that the styrene monomer was 40mmol, the reaction time was 30min, and the rest of the procedure and the parameter settings were the same as those of example 1, and the characteristics of the obtained polymer are shown in Table 1 below, and the DSC spectrum of the polymer is shown in FIG. 4.
Example 5
This example differs from example 1 in that the styrene monomer was 50mmol, the reaction time was 120min, and the rest of the procedure and the parameter settings were the same as in example 1, and the characteristics of the obtained polymer are shown in Table 1 below.
Example 6
This example differs from example 1 in that Ai iBu3 is 0.5mmol, styrene monomer is 100mmol, toluene solution saturated with ethylene is 30mL, reaction temperature is 120 ℃ and reaction time is 60min, and the remaining operation procedure and parameter settings are the same as in example 1, and the characteristics of the resulting polymer are shown in Table 1 below.
Example 7
This example differs from example 1 in that Ai iBu3 is 1mmol, styrene monomer is 600mmol, toluene solution saturated with ethylene is 100mL, 10bar ethylene pressure is maintained, reaction temperature is 70 ℃, reaction time is 240min, and the remaining operation and parameter settings are the same as example 1, and the characteristics of the resulting polymer are shown in Table 1 below.
Example 8
This example thus differs from example 1 in that compound 3 was used in place of compound 1 and the procedure and parameter settings were the same as in example 1 and the characteristics of the resulting polymer are shown in Table 1 below.
TABLE 1
Comparative example 1
Rare earth compound 1 (10. Mu. Mol) was added to a toluene solution (2 mL) under anhydrous and anaerobic conditions, and at 60℃to a toluene solution (10 mL) filled with styrene (10 mmol) monomer and saturated with ethylene. Then, after maintaining the ethylene pressure of 4bar for 10 minutes, a small amount of ethanol solution was added to terminate the polymerization. The reaction solution was then poured into ethanol (100 ml) containing a small amount of hydrochloric acid and stabilizer BHT to settle. The resulting polymer was dried in a 50 ℃ vacuum oven for 48 hours to give a net weight of 1.04g of polymer, tested without styrene building block insertion, T m = 130 ℃.
Comparative example 2
Rare earth compound 1 (10. Mu. Mol) was added to a toluene solution (2 mL) under anhydrous and anaerobic conditions, then to a toluene solution (10 mL) containing styrene (3 mmol), and after 10min at 60℃a small amount of ethanol solution was added to terminate the polymerization. The reaction solution was then poured into ethanol (100 mL) containing a small amount of hydrochloric acid and stabilizer BHT to settle without separating any polymer.
Comparative example 3
Rare earth compound 1 (10. Mu. Mol) and Ai iBu3 (0.2 mmol) were added to a toluene solution (2 mL) under anhydrous and anaerobic conditions, then to a toluene solution (10 mL) containing styrene (3 mmol), and after 10min at 60℃a small amount of ethanol solution was added to terminate the polymerization. The reaction solution was then poured into ethanol (100 mL) containing a small amount of hydrochloric acid and stabilizer BHT to settle without separating any polymer.
As can be seen from comparative examples 1 and 1 to 3, the combination of the bridged biscyclopentadienyl rare earth compound, the cocatalyst organoboron salt and the main group alkyl reagent is used as a catalytic system for catalyzing the random copolymerization of ethylene and styrene monomers, so that the bridged biscyclopentadienyl rare earth compound with low catalytic activity or no catalytic activity for the copolymerization of ethylene and styrene monomers shows high catalytic activity for the copolymerization of ethylene and styrene monomers, and the copolymerization of ethylene and styrene monomers is realized.
Analysis of the DSC spectra of the polymers prepared in the above examples shows that, as shown in FIGS. 1 to 3, the melting point of the copolymer is between 106 ℃ and 123 ℃ and belongs to the crystal melting peak of the long polyethylene segment. No He Rongrong peak was observed around 270 ℃, indicating that no syndiotactic polystyrene long segments were present.
Analysis of the nuclear magnetic resonance hydrogen spectrum of the polymer prepared in the above example shows that, as shown in fig. 4 and 5, the formants with chemical shifts of 6.5 to 7.5ppm are formants of hydrogen on benzene rings of styrene structural units in the copolymer as shown in fig. 4 and 5. The formants with chemical shift of 0.95-1.92 ppm are signal peaks of main chain alkane hydrogen.
The molar content of styrene structural units in the copolymer= (I 6.5-7.5/5)/[(I6.5-7.5/5)+(I0.95-1.92-3(I6.5-7.5/5)/4) ].
It should be noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the technical solution described in the above-mentioned embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of each embodiment of the present invention.
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