CN113061203A - Catalyst and preparation method thereof, and preparation method of styrene monomer isotactic polymer - Google Patents

Catalyst and preparation method thereof, and preparation method of styrene monomer isotactic polymer Download PDF

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CN113061203A
CN113061203A CN202110290982.2A CN202110290982A CN113061203A CN 113061203 A CN113061203 A CN 113061203A CN 202110290982 A CN202110290982 A CN 202110290982A CN 113061203 A CN113061203 A CN 113061203A
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aluminum
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崔冬梅
李世辉
姜洋
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a catalyst and a preparation method thereof, and a preparation method of a styrene monomer isotactic polymer. The invention provides a rare earth catalyst with a chelating ligand having large steric hindrance and strong conjugation effect, wherein the large steric hindrance of the chelating ligand weakens the acting force of meta-position and para-position polar groups of a styrene monomer and a central metal of the rare earth catalyst, the poisoning effect of the polar groups on the catalyst is reduced, and simultaneously the strong conjugation effect of the chelating ligand strengthens the Lewis acidity of the central metal of the catalyst, so that the catalytic activity of the catalyst can be improved, and the selective polymerization of the styrene monomer modified by the meta-position and para-position polar groups is realized.

Description

Catalyst and preparation method thereof, and preparation method of styrene monomer isotactic polymer
Technical Field
The invention relates to the field of organic synthesis, in particular to a catalyst and a preparation method thereof, and a preparation method of a styrene monomer isotactic polymer.
Background
Styrenic polymers can be classified into isotactic, syndiotactic and atactic polymers according to their stereoregularity. Heretofore, catalytic systems capable of catalyzing the isotactic selectivity of styrenic monomers have been quite flexible. Specifically, the catalytic system capable of isotactic selective polymerization of nonpolar styrene monomers includes Ziegler-Natta catalysts, bisphenol ligand chelated titanium and zirconium catalysts, and bisindenyl rare earth catalysts. However, these catalytic systems are mainly used for the isotactic selective polymerization of styrene.
Recently, patent documents CN105440186A, non-patent documents angelw.chem.int.ed.2015, 54,5205-. However, for polar styrenic monomers having no polar substituent groups in the ortho position (where the polar styrenic monomer is a polar group without bulky protecting groups and aluminum alkyl protection), there has been no catalytic system to date that can polymerize them into isotactic polymers.
As can be seen, the non-metallocene rare earth catalyst reported in the prior literature can catalyze the isotactic selectivity polymerization of the styrene monomer with the polar group at the ortho position, but the non-metallocene rare earth catalyst has little catalytic activity on the styrene monomer without the polar group at the ortho position. Other catalytic systems with isotactic selectivity for the polymerization of styrene can only catalyze the isotactic selective polymerization of nonpolar styrene monomers or polar styrene protected by bulky groups at present, and are not suitable for the isotactic selective polymerization of polar styrene monomers without polar groups at ortho-position and polar groups at meta-position and/or para-position.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst and a preparation method thereof, and a preparation method of an isotactic polymer of a styrene monomer. The catalyst provided by the invention can catalyze styrene monomers with polar substituent groups at meta-position and/or para-position to perform isotactic selective polymerization, has higher catalytic activity, and can efficiently obtain styrene monomer isotactic polymers.
The invention provides a catalyst, which has a structure shown in a formula I:
Figure BDA0002982666060000021
wherein:
x is a monoanionic ligand selected from: C1-C16 alkyl, C4-C16 silyl, C2-C16 alkylamino, C4-C20 alkylsilamino, C6-C20 arylamine, substituted or unsubstituted C3-C10 allyl, C7-C20 arylmethylene, boron hydride, tetramethyl aluminum, hydrogen, chlorine, bromine or iodine;
l is a neutral lewis base chelating ligand selected from: tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether, pyridine or substituted pyridines; n represents the number of ligands and is an integer of 0-2;
RE is a rare earth element selected from: lanthanide, scandium or yttrium.
Preferably, the first and second liquid crystal materials are,
the alkyl of C1-C16 is selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, or n-octyl;
the silane group of C4-C16 is selected from: -CH2Si(CH3)3、-CH[Si(CH3)3]2、-CH2Si(CH3)2Ph or-CH2SiMe2C6H4OMe-o；
The alkyl amino of C2-C16 is selected from: -NMe2、-NEt2、-NnPr2、-NiPr2or-NnBu2；
The alkyl silamine group of C4-C20 is selected from: -N [ SiMe ]3]2or-N [ SiMe ]2H]2；
The arylamine group of C6-C20 is selected from: -CH2C6H4NMe2-o、-NHPh、-NHC6H4Me-p、-NHC6H4 iPr-p or-NHC6H4(iPr)2-2,6；
The substituted or unsubstituted C3-C10 allyl is selected from: -CH2CH＝CH2、-CH2C(Me)＝CH2、-(SiMe3)CHCH＝CH(SiMe3)；
The arylmethylene of C7-C20 is selected from: p-MeC6H4CH2-、p-EtC6H4CH2-、p-iPrC6H4CH2-、p-nPrC6H4CH2-、p-nBuC6H4CH2-or p-tBuC6H4CH2-；
The RE is selected from: scandium, yttrium, lanthanum, neodymium, gadolinium, dysprosium, holmium, erbium, ytterbium or lutetium.
Preferably, said X is selected from: trimethylsilylmethylene, bistrimethylsilylmethine, allyl, 2-methylallyl, 1, 3-bistrimethylsilylallyl, hexamethylsilylamino, tetramethylsilylamino, methyl, benzyl, 4-methylbenzyl, 2-N, N' -dimethylbenzyl, tetramethylaluminum, borohydride, hydrogen, chlorine or bromine;
the RE is selected from: yttrium, lanthanum, neodymium, gadolinium, dysprosium, holmium, erbium or ytterbium.
Preferably, said X is selected from: trimethylsilylidene, allyl, 2-methylallyl, hexamethyl-silylamine, tetramethylsilylamine, benzyl, 4-methylbenzyl, 2-N, N' -dimethylbenzyl, tetramethylaluminum-based, or hydrogen;
the RE is selected from: yttrium, lanthanum, neodymium, gadolinium, holmium, erbium or ytterbium.
Preferably, the compounds are selected from the group consisting of compounds represented by formula I-1 to formula I-8:
Figure BDA0002982666060000031
the invention also provides a preparation method of the catalyst in the technical scheme, which comprises the following steps:
a) ligand A and alkyl alkali metal reagent MR1Reacting to form an alkali metal salt B;
b) alkali metal salt B with rare earth halide RE (X')3Mixing the suspension and a monoanionic alkali metal reagent MX for reaction to form a catalyst shown as a formula I;
Figure BDA0002982666060000041
wherein:
the MR1In which M is an alkali metal, R1Is alkyl, hydrogen or amino;
the RE (X')3Wherein, X' is a halogen element;
the rare earth halide RE (X')3The solvent in the suspension is neutral Lewis base;
in MX, M is an alkali metal, and X is a monoanionic ligand.
The invention also provides a preparation method of the styrene monomer isotactic polymer, which comprises the following steps:
under the action of an isotactic selective polymerization catalyst, carrying out polymerization reaction on a styrene monomer shown in a formula II to form an isotactic polymer shown in a formula III;
Figure BDA0002982666060000042
wherein the content of the first and second substances,
r is a substituent group at meta position and/or para position on a benzene ring, m is the number of the substituent group R, and m is more than or equal to 1 and less than or equal to 3;
r is selected from: C1-C20 alkoxy, C6-C20 aryloxy, C1-C20 alkylthio, C1-C20 silyl, C1-C40 alkyl, C3-C20 siloxy, C2-C20 alkylamino, hydrogen, chlorine, bromine or iodine;
the isotactic selective polymerization catalyst comprises a main catalyst;
the main catalyst is the catalyst in the technical scheme.
Preferably, the styrenic monomer is selected from: styrene, p-methylstyrene, m-methylstyrene, 3, 5-dimethylstyrene, 4-alkylstyrene, p-methoxystyrene, p-methylthiostyrene, m-methoxystyrene, 3, 5-dimethoxystyrene, p-fluorostyrene, m-fluorostyrene, p-alkoxystyrene, 2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene, p-benzyloxystyrene, 4- (dimethylsilyl) styrene, 4- (trimethylsilyl) styrene, 4- (buten-1) ylstyrene, 4-allylstyrene, 4-phenylacetylenestyrene, 4-butylacetylenestyrene, 4-vinylbenzocyclobutene, 4- (trimethylsilylethynyl) styrene, 4-alkylthiostyrene, styrene, one or more of 4- (silyl) styrene, 4- (N ' N-dimethylamino) styrene, 4- (N ' N-diethylamino) styrene and 4- (N ' N-diphenylamino) styrene;
the isotactic polymerization catalyst further comprises a cocatalyst;
the cocatalyst comprises an organic boron salt and a main group metal alkyl compound;
the temperature of the polymerization reaction is 0-160 ℃, and the time is 1 min-100 h;
the molar ratio of the main catalyst to the organic boron salt to the main group metal alkyl compound is 1 to (0-1) to (0-1000);
the molar ratio of the main catalyst to the styrene monomer shown in the formula II is 1: 50-100000.
Preferably, the styrenic monomer is selected from the group consisting of styrene, p-methylstyrene, m-methylstyrene, 3, 5-dimethylstyrene, 4-alkylstyrene, p-methoxystyrene, p-methylthiostyrene, m-methoxystyrene, 3, 5-dimethoxystyrene, p-fluorostyrene, m-fluorostyrene, p-alkoxystyrene, 2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene, p-benzyloxystyrene, 4- (dimethylsilyl) styrene, 4- (trimethylsilyl) styrene, 4- (buten-1) ylstyrene, 4-allylstyrene, 4-phenylacetylene styrene, 4-butylacetylene styrene, 4-vinylbenzocyclobutene, 4- (trimethylsilylethynyl) styrene, m-methylstyrene, p-methoxystyrene, p-dimethylsilyl-styrene, p-methoxystyrene, 3, 5-dimethoxystyrene, p-fluorostyrene, m-fluorostyrene, p-alkoxystyrene, p-, One or more of 4-alkylthio styrene and 4- (silyl) styrene;
the organoboron salt is selected from: [ NHEt3][B(C6F5)4]、[Ph3C][B(C6F5)4]、[PhNMe2H][B(C6F5)4]、B(C6F5)3、1,4-(C6F5)2BC6F4B(C6F5)2And [ Ph3C]2[1,4-(C6F5)3BC6F4B(C6F5)3]One or more of the above;
the main group metal alkyl compound is selected from one or more of alkyl aluminum, alkyl magnesium and alkyl zinc.
Preferably, the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, triisopropyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, methylaluminoxane, dried aluminoxane and modified aluminoxane;
the alkyl zinc is diethyl zinc;
the alkyl magnesium is selected from one or more of diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium and dibutyl magnesium;
the molar ratio of the main catalyst to the organic boron salt to the main group metal alkyl compound is 1 to (0-1) to (0-500);
the molar ratio of the main catalyst to the styrene monomer shown in the formula II is 1: 100-80000.
The catalyst provided by the invention is a rare earth catalyst chelated by a ligand with large steric hindrance and strong conjugation effect, wherein the large steric hindrance of the chelating ligand weakens the acting force of a meta-position polar group and a para-position polar group of a styrene monomer and a central metal of the rare earth catalyst, the poisoning effect of the polar group on the catalyst is reduced, and meanwhile, the strong conjugation effect of the chelating ligand strengthens the Lewis acidity of the central metal of the catalyst, so that the catalytic activity of the catalyst can be improved, and the selective polymerization of the styrene monomer modified by the meta-position polar group and the para-position polar group is realized.
Experimental results show that the catalyst provided by the invention can realize the isotactic selective polymerization of styrene monomers modified by meta-position and para-position polar groups, specifically can catalyze the isotactic selective homopolymerization of the same styrene monomers, and can catalyze the isotactic selective copolymerization of different styrene monomers, the conversion rate of the styrene monomers reaches more than 85%, and the isotacticity mm of the prepared isotactic polymer is more than 98%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the catalyst of formula I-1 obtained in example 1;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of a polymer obtained in polymerization example 6;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of a polymer obtained in polymerization example 7;
FIG. 4 is a nuclear magnetic resonance carbon spectrum of a polymer obtained in polymerization example 8;
FIG. 5 is a nuclear magnetic resonance carbon spectrum of a polymer obtained in polymerization example 9;
FIG. 6 shows the NMR spectrum of the polymer obtained in polymerization example 10.
Detailed Description
The invention provides a catalyst, which has a structure shown in a formula I:
Figure BDA0002982666060000071
wherein:
x is a monoanionic ligand selected from: C1-C16 alkyl, C4-C16 silyl, C2-C16 alkylamino, C4-C20 alkylsilamino, C6-C20 arylamine, substituted or unsubstituted C3-C10 allyl, C7-C20 arylmethylene, boron hydride, tetramethyl aluminum, hydrogen, chlorine, bromine or iodine;
l is a neutral lewis base chelating ligand selected from: tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether, pyridine or substituted pyridines; n represents the number of ligands and is an integer of 0-2;
RE is a rare earth element selected from the lanthanide series, scandium or yttrium.
The catalyst provided by the invention is a rare earth catalyst chelated by a ligand with large steric hindrance and strong conjugation effect, wherein the large steric hindrance of the chelating ligand weakens the acting force of a meta-position polar group and a para-position polar group of a styrene monomer and a central metal of the rare earth catalyst, the poisoning effect of the polar group on the catalyst is reduced, and meanwhile, the strong conjugation effect of the chelating ligand strengthens the Lewis acidity of the central metal of the catalyst, so that the catalytic activity of the catalyst can be improved, and the selective polymerization of the styrene monomer modified by the meta-position polar group and the para-position polar group is realized. The catalyst of the formula I can catalyze the isotactic selectivity homopolymerization of the same styrene monomers and can catalyze the isotactic selectivity copolymerization of different styrene monomers. Moreover, the catalyst of the formula I provided by the invention can be used for independently catalyzing the polymerization of the styrene monomer, and can also be used for jointly catalyzing the isotactic selective polymerization of the styrene monomer under the coordination of other cocatalysts (organic boron salt and main group metal alkyl compound).
With respect to formula I:
x is a monoanionic ligand selected from: C1-C16 alkyl, C4-C16 silyl, C2-C16 alkylamino, C4-C20 alkylsilylamino, C6-C20 arylamino, substituted or unsubstituted C3-C10 allyl, and C7-C20 arylmethylene (namely ArCH)2-), borohydride, tetramethylaluminum, hydrogen, chlorine, bromine or iodine.
The alkyl of C1-C16 is preferably: methyl, ethyl, n-propyl, isopropyl, n-butyl, or n-octyl;
the silane group of C4-C16 is preferably: -CH2Si(CH3)3、-CH[Si(CH3)3]2、-CH2Si(CH3)2Ph or-CH2SiMe2C6H4OMe-o；
The alkylamino radical of C2-C16 is preferably: -NMe2、-NEt2、-NnPr2、-NiPr2or-NnBu2；
The alkyl silicon amino of C4-C20 is preferably: -N [ SiMe ]3]2or-N [ SiMe ]2H]2；
The arylamine group having C6-C20 is preferably: -CH2C6H4NMe2-o、-NHPh、-NHC6H4Me-p、-NHC6H4 iPr-p or-NHC6H4(iPr)2-2,6；
The substituted or unsubstituted allyl group having from C3 to C10 is preferably: -CH2CH＝CH2、-CH2C(Me)＝CH2、-(SiMe3)CHCH＝CH(SiMe3)；
The arylmethylene of C7-C20 is preferably: PhCH2-、p-MeC6H4CH2-、p-EtC6H4CH2-、p-iPrC6H4CH2-、p-nPrC6H4CH2-、p-nBuC6H4CH2-or p-tBuC6H4CH2-。
Wherein, the related groups are abbreviated as the groups conventional in the field, such as Me is methyl, Et is ethyl, Pr is propyl,iPr is isopropyl,nPr is n-propyl, Bu is butyl,nBu is n-butyl,tBu is tert-butyl, Ph is phenyl, and Ar is aryl.
More preferably, X is selected from: trimethylsilylmethylene (-CH)2Si(CH3)3) Bis-trimethylsilylmethine (-CH [ Si (CH))3)3]2) Allyl (-CH)2CH＝CH2) 2-methylallyl (-CH)2C(Me)＝CH2) 1, 3-bistrimethylsilylallyl (- (SiMe)3)CHCH＝CH(SiMe3) Hexamethyl-silamino (-N [ SiMe)3]2) Tetramethylsilylamine (-N [ SiMe) ]2H]2) Methyl (-CH)3) Benzyl (PhCH)2-), 4-methylbenzyl (p-MeC)6H4CH2-), 2-N, N' -dimethylbenzyl (-CH)2C6H4NMe2O), tetramethylaluminum base (AlMe)4-), Boron Hydride (BH)4-), hydrogen, chlorine or bromine.
Further preferably, X is selected from: trimethylsilylmethylene (-CH)2Si(CH3)3) Allyl (-CH)2CH＝CH2) 2-methylallyl (-CH)2C(Me)＝CH2) Hexamethyl-silamino (-N [ SiMe)3]2) Tetramethylsilylamine (-N [ SiMe) ]2H]2) Benzyl (PhCH)2-), 4-methylbenzyl (p-MeC)6H4CH2-), 2-N, N' -dimethylbenzyl (-CH)2C6H4NMe2O), tetramethylaluminum base (AlMe)4-), Boron Hydride (BH)4-), hydrogen, chlorine or bromine.
Most preferably, X is selected from: trimethylsilylmethylene (-CH)2Si(CH3)3) Allyl (-CH)2CH＝CH2) 2-methylallyl (-CH)2C(Me)＝CH2) Tetramethylsilylamine (-N [ SiMe) ]2H]2) Benzyl (PhCH)2-), 4-methylbenzyl (p-MeC)6H4CH2-), 2-N, N' -dimethylbenzyl (-CH)2C6H4NMe2-o) or hydrogen.
L is a neutral Lewis base chelating ligand and is coordinated to the rare earth metal RE in a coordination bond mode. The L is selected from: tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether, pyridine or substituted pyridines. Wherein n represents the number of the ligands L and is an integer of 0-2, inclusive. In some embodiments of the invention, the number of ligands, n, is 0 or 1.
RE is a rare earth element selected from the lanthanide series, scandium or yttrium. Preferably, RE is selected from: scandium, yttrium, lanthanum, neodymium, gadolinium, dysprosium, holmium, erbium, ytterbium or lutetium. More preferably, RE is selected from: yttrium, lanthanum, neodymium, gadolinium, dysprosium, holmium, erbium or ytterbium. Most preferably, RE is selected from: yttrium, lanthanum, neodymium, gadolinium, holmium, erbium or ytterbium.
More preferably, the catalyst of formula I is selected from the group consisting of compounds of formulae I-1 to I-8:
Figure BDA0002982666060000091
the invention also provides a preparation method of the catalyst in the technical scheme, which comprises the following steps:
a) ligand A and alkyl alkali metal reagent MR1Reacting to form an alkali metal salt B;
b) alkali metal salt B with rare earth halide RE (X')3Mixing the suspension and a monoanionic alkali metal reagent MX for reaction to form a catalyst shown as a formula I;
Figure BDA0002982666060000101
wherein:
the MR1In which M is an alkali metal, R1Is alkyl, hydrogen or amino;
the RE (X')3Wherein, X' is a halogen element;
the rare earth halide RE (X')3The solvent in the suspension is neutral Lewis base;
in MX, M is an alkali metal and X is the monoanionic ligand.
With respect to step a):
in the present invention, the source of the ligand a is not particularly limited, and may be a commercially available product or a preparation method well known to those skilled in the art.
In the present invention, the alkali metal alkyl reagent MR1In the formula, M is an alkali metal, preferably Li, Na or K; r1Is alkyl, hydrogen or amine. The alkyl alkali metal reagent MR1Preferably one or more of n-butyl lithium, sodium hydride, potassium hydride and benzyl potassium.
In the invention, the ligand A and alkyl alkali metal reagent MR1The molar ratio of (A) to (B) is preferably 1: 2.
In the present invention, the reaction is preferably carried out under an inert atmosphere. The inert gas for providing the inert atmosphere in the present invention is not particularly limited in kind, and may be any conventional inert gas known to those skilled in the art, such as nitrogen, argon or helium.
In the present invention, the reaction temperature is preferably 0 to 100 ℃, more preferably 0 to 60 ℃, and in some embodiments, the temperature is 0 ℃. The reaction time is preferably 10 to 600min, and more preferably 30 to 120 min.
In the present invention, the reaction is preferably carried out in a solvent medium, and in particular, the procedure of step a) is preferably as follows:
s1, dissolving the ligand A in a solvent to form a ligand solution;
s2, mixing the alkali metal alkyl reagent MR1Dissolving in a solvent to form an alkali metal alkyl solution;
s3, mixing the ligand solution with an alkyl alkali metal solution for reaction to form an alkali metal salt B;
here, the steps S1 and S2 are not limited in order.
In the step S1: the solvent is preferably one or more of tetrahydrofuran, toluene, diethyl ether, n-hexane and 1, 4-dioxane. The dosage ratio of the ligand A to the solvent is preferably 2mmol to (2-20) mL.
In the step S2: the solvent is preferably one or more of n-hexane, toluene, diethyl ether, 1, 4-dioxane and tetrahydrofuran. The alkyl alkali metal reagent MR1The dosage ratio of the solvent to the solvent is preferably 4mmol to (4-10) mL.
In the step S3: the mixing reaction is preferably at a temperature of 0-100 deg.C, more preferably 0-60 deg.C, and in some embodiments at a temperature of 0 deg.C. The reaction time is preferably 10 to 600min, and more preferably 30 to 120 min.
After the above reaction, alkali metal salt B is formed.
With respect to step b):
in the present invention, the rare earth halide RE (X')3The kind of the rare earth element RE is the same as RE described in formula I in the above technical scheme, and is not described herein again. X' is a halogen element. In some embodiments of the invention, the rare earth halide RE (X')3Comprises the following steps: YCl3、LuCl3、ErCl3、HoCl3、GdCl3、NdCl3、DyCl3Or LaBr3。
The rare earth halide RE (X')3The solvent in the solution is neutral Lewis base, the type of which is consistent with the neutral Lewis base ligand L in the formula I in the technical scheme, and the details are not repeated.
In the invention, in the single anion alkali metal reagent MX, M is an alkali metal, preferably Li, Na or K; x is a monoanionic ligand, the type of which is the same as X described in formula I in the above technical scheme, and the description is omitted.
In the present invention, the reaction is preferably carried out under an inert atmosphere. The inert gas for providing the inert atmosphere in the present invention is not particularly limited in kind, and may be any conventional inert gas known to those skilled in the art, such as nitrogen, argon or helium.
In the present invention, the process of step b) preferably comprises:
k1, dissolving alkali metal salt B in a solvent to obtain an alkali metal salt B solution;
k2, rare earth halide RE (X')3Mixing with neutral Lewis base to obtain rare earth halide RE (X')3Suspending liquid;
k3, dissolving the monoanionic alkali metal reagent MX in a solvent to obtain a monoanionic alkali metal reagent MX solution;
k4, mixing the alkali metal salt B solution with rare earth halide RE (X')3Mixing and reacting the suspension to obtain an intermediate solution;
k5, mixing the intermediate solution with a monoanionic alkali metal reagent MX solution for reaction to form the catalyst shown in the formula I;
wherein, the step K1, the step K2 and the step K3 are not limited in order.
In the step K1: the solvent is preferably one or more of tetrahydrofuran, toluene, diethyl ether, n-hexane and 1, 4-dioxane. The dosage ratio of the alkali metal salt B to the solvent is preferably 2mmol to (4-20) mL.
In the step K2: the kind of the neutral Lewis base is the same as the neutral Lewis base ligand L in the formula I in the technical scheme, and the description is omitted. The rare earth halide RE (X')3The dosage ratio of the neutral Lewis base and the neutral Lewis base is preferably 2mmol to (2-30) mL.
In the step K3: the solvent is preferably one or more of n-hexane, toluene, diethyl ether, 1, 4-dioxane and tetrahydrofuran. The dosage ratio of the monoanionic alkali metal reagent MX to the solvent is preferably 2mmol to (2-10) mL.
The present invention does not have a sequential limitation to the step K1, the step K2, and the step K3. In the subsequent reaction, it is preferable to control the alkali metal salt B and the rare earth halide RE (X')3The molar ratio of the monoanionic alkali metal reagent MX is 1: 1-1.5.
In the step K4: the mixing reaction is preferably carried out at a temperature of 0 to 100 ℃, more preferably 20 to 60 ℃, and in some embodiments, at a temperature of 0 ℃. The reaction time is preferably 10min to 12 hours, more preferably 5 hours.
In the step K5: the mixing temperature is preferably-30-100 ℃, and more preferably 0 ℃. After the mixing is finished, gradually raising the temperature to room temperature for continuous reaction; the room temperature can be 20-30 ℃. After the temperature is raised to the room temperature, the reaction is continued for 0.5 to 12 hours, and the preferable reaction time is 3 hours. The catalyst of formula I is generated in the system through the reaction. In the present invention, after the above reaction, the following post-treatment is preferably further performed: the solvent is evaporated in vacuum, extracted, filtered, concentrated and recrystallized, and the catalyst of formula I is obtained after the post-treatment.
The invention also provides a preparation method of the styrene monomer isotactic polymer, which comprises the following steps:
under the action of an isotactic selective polymerization catalyst, carrying out polymerization reaction on a styrene monomer shown in a formula II to form an isotactic polymer shown in a formula III;
Figure BDA0002982666060000131
wherein the content of the first and second substances,
r is a substituent group at meta position and/or para position on a benzene ring, m is the number of the substituent group R, and m is more than or equal to 1 and less than or equal to 3;
r is selected from: C1-C20 alkoxy, C6-C20 aryloxy, C1-C20 alkylthio, C1-C20 silyl, C1-C40 alkyl, C3-C20 siloxy, C2-C20 alkylamino, hydrogen, chlorine, bromine or iodine;
the isotactic selective polymerization catalyst comprises a main catalyst;
the main catalyst is the catalyst in the technical scheme.
In the styrene monomer shown in the formula II, R is a substituent group at meta position and/or para position on a benzene ring, m is the number of the substituent group R, and m is more than or equal to 1 and less than or equal to 3. The R is selected from: alkoxy of C1-C20, aryloxy of C6-C20, alkylthio of C1-C20, silyl of C1-C20, alkyl of C1-C40, alkylsiloxy of C3-C20, alkylamino of C2-C20, hydrogen, chlorine, bromine or iodine.
Preferably, the styrenic monomer of formula II is selected from the group consisting of: styrene, p-methylstyrene, m-methylstyrene, 3, 5-dimethylstyrene, 4-alkylstyrene, p-methoxystyrene, p-methylthiostyrene, m-methoxystyrene, 3, 5-dimethoxystyrene, p-fluorostyrene, m-fluorostyrene, p-alkoxystyrene, 2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene, p-benzyloxystyrene, 4- (dimethylsilyl) styrene, 4- (trimethylsilyl) styrene, 4- (buten-1) ylstyrene, 4-allylstyrene, 4-phenylacetylenestyrene, 4-butylacetylenestyrene, 4-vinylbenzocyclobutene, 4- (trimethylsilylethynyl) styrene, 4-alkylthiostyrene, styrene, 4- (silyl) styrene, 4- (N ' N-dimethylamino) styrene, 4- (N ' N-diethylamino) styrene and 4- (N ' N-diphenylamino) styrene.
More preferably, the styrenic monomer of formula II is selected from the group consisting of: styrene, p-methylstyrene, m-methylstyrene, 3, 5-dimethylstyrene, 4-alkylstyrene, p-methoxystyrene, p-methylthiostyrene, m-methoxystyrene, 3, 5-dimethoxystyrene, p-fluorostyrene, m-fluorostyrene, p-alkoxystyrene, 2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene, p-benzyloxystyrene, 4- (dimethylsilyl) styrene, 4- (trimethylsilyl) styrene, 4- (buten-1) ylstyrene, 4-allylstyrene, 4-phenylacetylene styrene, 4-butylacetylene styrene, 4-vinylbenzocyclobutene, 4- (trimethylsilylethynyl) styrene, 4-alkylthiostyrene and 4- (silyl) styrene.
In some embodiments of the present invention, the styrenic monomer of formula ii is selected from one or more of the following compounds:
Figure BDA0002982666060000141
in the invention, the catalyst of the formula I can catalyze the isotactic selectivity homopolymerization of the same styrene monomers and can catalyze the isotactic selectivity copolymerization of different styrene monomers. Thus, the styrenic monomers of formula II may be the same or different, i.e., may be selected from one or more of the compounds described above.
In the present invention, the isotactic selective polymerization catalyst comprises a main catalyst, and the main catalyst is the catalyst of formula i described in the above technical scheme, and is not described herein again. In the present invention, the molar ratio of the main catalyst to the styrene-based monomer represented by the formula II is preferably 1: 50 to 100000, more preferably 1: 100 to 80000, still more preferably 1: 100 to 80000, and most preferably 1: 2500 to 60000.
In the invention, the catalyst of the formula I can be used for catalyzing the polymerization of the styrene monomer independently, and can also be used for catalyzing the isotactic selective polymerization of the styrene monomer under the coordination of other cocatalysts. In the present invention, the co-catalyst preferably comprises an organoboron salt and a main group metal alkyl compound.
The organic boron salt is preferably an organic boron salt containing negative ions, B (C)6F5)3And 1,4- (C)6F5)2BC6F4B(C6F5)2One or more of the above; wherein in the organic boron salt containing negative ions, the negative ions are preferably [ B (C)6F5)4]–Or [1,4- (C)6F5)3BC6F4B(C6F5)3]2–. The organoboron salt is more preferably [ NHEt ]3][B(C6F5)4]、[Ph3C][B(C6F5)4]、[PhNMe2H][B(C6F5)4]、B(C6F5)3、1,4-(C6F5)2BC6F4B(C6F5)2And [ Ph3C]2[1,4-(C6F5)3BC6F4B(C6F5)3]One or more of them.
The main group metal alkyl compound is preferably one or more of alkyl aluminum, alkyl magnesium and alkyl zinc.
Wherein, the alkyl aluminum is preferably one or more of trimethyl aluminum, triethyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, triisopropyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, Methylaluminoxane (MAO), dried aluminoxane (DMAO) and modified aluminoxane (MMAO). More preferably one or more of trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisobutylaluminum, triisopropylaluminum, diethylaluminum hydride and diisobutylaluminum hydride. Most preferably one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, triisopropylaluminum, diethylaluminum hydride and diisobutylaluminum hydride.
The zinc alkyl is preferably diethyl zinc.
The alkyl magnesium is preferably one or more of diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium and dibutyl magnesium; more preferably dibutyl magnesium.
In the present invention, the molar ratio of the main catalyst, the organoboron salt, and the main group metal alkyl compound is preferably 1: (0 to 1): (0 to 1000).
In the present invention, the polymerization reaction may be bulk polymerization or polymerization in an organic solvent. When an organic solvent is used, the process is preferably as follows: firstly, dissolving the isotactic selective polymerization catalyst in an organic solvent, and then adding a styrene monomer shown in the formula II for reaction. In the invention, the organic solvent is preferably one or more of alkane solvents and aromatic solvents; more preferably one or more of saturated straight-chain alkane, saturated cyclane, aromatic hydrocarbon and halogenated aromatic hydrocarbon; most preferably one or more of n-hexane, decalin, cyclohexane, petroleum ether, benzene, toluene and xylene. The dosage ratio of the isotactic selectivity polymerization catalyst to the organic solvent is preferably 10 mu mol to (0.5-10) mL.
In the invention, the polymerization reaction temperature is preferably 0-160 ℃, more preferably 20-140 ℃, further preferably 40-120 ℃, and most preferably 60-120 ℃. The time for the polymerization reaction is preferably 1min to 100 hours, more preferably 1min to 72 hours, still more preferably 1min to 48 hours, and most preferably 2min to 12 hours. After polymerization, generating an isotactic polymer shown in a formula III;
Figure BDA0002982666060000151
wherein, R and m are the same as those described in formula II in the above technical scheme, and are not described herein again. n is1Is the degree of polymerization.
The invention firstly prepares the isotactic polystyrene functionalized by meta-position and/or para-position polar groups (except for isotactic polacrylstyrene protected by bulky groups) by the preparation method. The isotactic polymer obtained by the present invention has a number average molecular weight of 1000g/mol to 500X 104g/mol, preferably 2000g/mol to 200X 104g/mol, more preferably from 5000g/mol to 100X 104g/mol, most preferably 10000g/mol to 50X 104g/mol. The isotactic styrene monomer polymer prepared by the invention can be an isotactic homopolymer of styrene monomers and can also be an isotactic copolymer of different styrene monomers. Wherein, the content of each styrene monomer structural unit in the styrene monomer isotactic copolymer is selected from 0.1mol percent to 99mol percent. The isotacticity of the isotactic polymer prepared by the method is more than 98 percent. Stereoregularity refers to the mole percentage of stereoregular polymer to total polymer.
The invention also provides the styrene monomer isotactic polymer prepared by the preparation method in the technical scheme.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1: preparation of the catalyst of formula I-1
1. The synthetic route is as follows:
Figure BDA0002982666060000161
2. the synthesis process is as follows:
s1, dissolving 2mmol of ligand A in 10mL of tetrahydrofuran solvent under inert atmosphere to obtain a solution of the ligand A; then, an n-hexane solution of n-butyllithium (the n-butyllithium content is 4mmol, and the total volume of the solution is 2.5mL) was gradually added to the above-mentioned solution at 0 ℃ to react for 30min, thereby obtaining a ligand lithium salt reaction solution 1.
S2, under inert atmosphere, adding 2mmol YCl3Stirring with 10mmol of Tetrahydrofuran (THF) at room temperature (20 deg.C) for 4h to give YCl3The suspension of tetrahydrofuran (1).
S3, mixing the above ligand lithium salt reaction solution 1 and YCl at 0 deg.C3Mixing the tetrahydrofuran suspension and reacting for 5 hours; thereafter, an alkyl lithium LiCH was added to the system2SiMe3The n-hexane solution (the content of the alkyl lithium is 2mmol, and the total volume of the solution is 5mL) is gradually heated to room temperature (20 ℃) and continuously reacted for 6 hours; after the reaction is finished, removing all solvents in vacuum, extracting with toluene, filtering, concentrating, and finally recrystallizing at-30 ℃ to obtain the catalyst shown as the formula I-1, wherein the product yield is 75%, and the purity is>95％。
NMR hydrogen spectroscopy (400Hz, 25 ℃ C., CDCl) was performed on the product obtained in example 13) Referring to FIG. 1, FIG. 1 shows the NMR spectrum of the catalyst of formula I-1 obtained in example 1.
Example 2: preparation of the catalyst of formula I-2
The procedure was followed for the preparation of example 1, except that: subjecting the rare earth halide YCl in step S23Replacement by LuCl3The alkyl lithium LiCH obtained in step S32SiMe3Replacement by LiCH2Ph. The catalyst of formula I-2 was obtained in a yield of 72% and a purity of>95％。
Example 3: preparation of the catalyst of formula I-3
The procedure was followed for the preparation of example 1, except that: subjecting the rare earth halide YCl in step S23Replacement by ErCl3The alkyl lithium LiCH obtained in step S32SiMe3Is replaced by KCH2(C6H4)CH3. The catalyst of formula I-3 was obtained in a yield of 81% and a purity of>95％。
Example 4: preparation of the catalyst of formula I-4
The procedure was followed for the preparation of example 1, except that: subjecting the rare earth halide YCl in step S23Replacement by HoCl3. The catalyst of formula I-4 was obtained in 75% yield and with a purity of>95％。
Example 5: preparation of the catalyst of formula I-5
The procedure was followed for the preparation of example 1, except that: subjecting the rare earth halide YCl in step S23Replacement was with GdCl3. The catalyst of formula I-4 was obtained in a yield of 68% and a purity of>95％。
Example 6: preparation of the catalyst of formula I-6
The procedure was followed for the preparation of example 1, except that: subjecting the rare earth halide YCl in step S23Replacement by NdCl3. The catalyst of formula I-6 was obtained in 67% yield and purity>95％。
Example 7: preparation of the catalyst of formula I-7
The procedure was followed for the preparation of example 1, except that: subjecting the rare earth halide YCl in step S23Replacement by DyCl3. The catalyst of formula I-7 was obtained in a yield of 70% and a purity of>95％。
Example 8: preparation of the catalyst of formula I-8
The procedure was followed for the preparation of example 1, except that: subjecting the rare earth halide YCl in step S23Replacement by LaBr3The alkyl lithium LiCH obtained in step S32SiMe3Replacement by LiCH2(C6H4)N(CH3)2-o. The catalyst of formula I-8 was obtained in a yield of 64% and a purity of>95％。
The catalyst prepared in the embodiment 1-8 has the following structure:
Figure BDA0002982666060000181
polymerization example 1
Dissolving 10 mu mol of the catalyst shown in the formula I-1 in 0.5mL of toluene in a reaction bottle under an inert atmosphere, adding 10mmol of styrene monomer into the reaction bottle, and reacting for 15min in an oil bath at 80 ℃; then, ethanol acidified by hydrochloric acid is added to terminate the polymerization reaction; then, the obtained product was stirred in ethanol at room temperature (20 ℃) to obtain white solid powder, and then the solid product was collected by suction filtration using a Bush funnel and dried in a vacuum drying oven at 60 ℃ to a constant weight to obtain polystyrene.
The test shows that the conversion rate of styrene monomer is 100%, the isotacticity (mmmm) > 99%, and the molecular weight Mn＝6.74×104g/mol, molecular weight distribution Mw/Mn2.54, melting temperature Tm＝219℃。
Polymerization examples 2 to 16
The procedure of polymerization example 1 was followed except that the kind of the catalyst used, the kind of the monomer, the kind of [ St ]: RE ] (i.e., the molar ratio of the styrenic monomer to the catalyst of the formula I), the polymerization temperature and the polymerization time were varied, and the conditions were the same as those of polymerization example 1, specifically, see Table 1. The products of the polymerization examples were examined and the results are shown in Table 1.
The structure of the styrenic monomer used in each polymerization example is as follows:
Figure BDA0002982666060000182
TABLE 1 reaction conditions and product characteristics of polymerization examples 1 to 16
Figure BDA0002982666060000191
Note: the molecular weight and molecular weight distribution were measured by GPC, and the stereoselectivity was determined from the hydrogen and carbon nuclear magnetic resonance spectra of the polymer.
Wherein nuclear magnetism of the polymers obtained in polymerization examples 6 to 10Resonance carbon Spectroscopy detection (100Hz, 25 ℃, CDCl)3) The results are shown in FIGS. 2 to 6; wherein, FIG. 2 is a NMR spectrum of a polymer obtained in polymerization example 6, FIG. 3 is a NMR spectrum of a polymer obtained in polymerization example 7, FIG. 4 is a NMR spectrum of a polymer obtained in polymerization example 8, FIG. 5 is a NMR spectrum of a polymer obtained in polymerization example 9, and FIG. 6 is a NMR spectrum of a polymer obtained in polymerization example 10.
Polymerization example 17
Mu. mol of the catalyst of the formula I-6 and 100. mu. mol of AliBu in a reaction flask under an inert atmosphere3Dissolving in 5mL of toluene, adding 50mmol of styrene monomer into a reaction bottle, and reacting in an oil bath at 80 ℃ for 120 min; then, ethanol acidified by hydrochloric acid is added to terminate the polymerization reaction; then, after stirring the obtained product in ethanol at room temperature (20 ℃) to form white solid powder, the solid product was collected by suction filtration using a Bush funnel and dried in a vacuum drying oven at 60 ℃ to a constant weight to obtain polystyrene.
The test shows that the conversion rate of styrene monomer is 97%, the isotacticity (mmmm) > 99%, and the molecular weight Mn＝46.7×104g/mol, molecular weight distribution Mw/Mn＝2.45。
Polymerization example 18
Mu. mol of the catalyst of the formula I-6 and 100. mu. mol of AliBu in a reaction flask under an inert atmosphere3Dissolving in 5mL of toluene, adding 25mmol of styrene monomer and 25mmol of p-methoxy styrene monomer into a reaction bottle, and reacting in an oil bath at 80 ℃ for 240 min; then, ethanol acidified by hydrochloric acid is added to terminate the polymerization reaction; then, after stirring the resulting product in ethanol at room temperature (20 ℃) to a white solid powder, the solid product was collected by suction filtration using a Bush funnel and dried in a vacuum drying oven at 60 ℃ to a constant weight to obtain a polymer.
The conversion of the monomer was found to be 87%; the molar content of the p-methoxystyrene units is 43 mol%, the isotacticity mm is more than 99%, and the molecular weight Mn＝38.7×104g/mol, molecular weight distribution Mw/Mn＝2.11。
The resulting polymer has a structure substantially as shown in the following formula:
Figure BDA0002982666060000201
polymerization example 19
Mu. mol of the catalyst of the formula I-6 and 100. mu. mol of AliBu in a reaction flask under an inert atmosphere3Dissolving in 5mL of toluene, adding 25mmol of styrene monomer and 25mmol of p-methylthio styrene monomer into a reaction bottle, and reacting in an oil bath at 80 ℃ for 120 min; then, ethanol acidified by hydrochloric acid is added to terminate the polymerization reaction; then, after stirring the resulting product in ethanol at room temperature (20 ℃) to a white solid powder, the solid product was collected by suction filtration using a Bush funnel and dried in a vacuum drying oven at 60 ℃ to a constant weight to obtain a polymer.
The resulting product was subjected to nuclear magnetic resonance carbon spectrum detection (100Hz, 25 ℃ C., CDCl)3) Referring to FIG. 3, FIG. 3 is a nuclear magnetic resonance carbon spectrum of isotactic poly (p-methylthiostyrene) obtained in polymerization example 19.
The conversion rate of the monomer is 97% through testing; the mol content of the p-methylthiostyrene unit is 47 mol%, the isotacticity mm is more than 99%, and the molecular weight Mn＝40.7×104g/mol, molecular weight distribution Mw/Mn＝2.31。
Polymerization example 20
Mu. mol of the catalyst of the formula I-6 and 100. mu. mol of AliBu in a reaction flask under an inert atmosphere3Dissolving in 5mL of toluene, adding 25mmol of m-methoxy styrene monomer and 25mmol of p-methylthiostyrene monomer into a reaction bottle, and reacting in an oil bath at 80 ℃ for 480 min; then, ethanol acidified by hydrochloric acid is added to terminate the polymerization reaction; then, after stirring the resulting product in ethanol at room temperature (20 ℃) to a white solid powder, the solid product was collected by suction filtration using a Bush funnel and dried in a vacuum drying oven at 60 ℃ to a constant weight to obtain a polymer.
The obtained product was subjected to nuclear magnetic resonance carbon spectrum detection (100Hz, 25 c,CDCl3) Referring to FIG. 4, FIG. 4 is a nuclear magnetic resonance carbon spectrum of isotactic polymethoxystyrene obtained in polymerization example 20.
The monomer conversion rate is 89% through testing; the mol content of the p-methylthio styrene unit is 54 mol%, the isotacticity mm is more than 99%, and the molecular weight Mn＝38.7×104g/mol, molecular weight distribution Mw/Mn＝2.28。
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A catalyst having the structure of formula i:
Figure FDA0002982666050000011
wherein:
x is a monoanionic ligand selected from: C1-C16 alkyl, C4-C16 silyl, C2-C16 alkylamino, C4-C20 alkylsilamino, C6-C20 arylamine, substituted or unsubstituted C3-C10 allyl, C7-C20 arylmethylene, boron hydride, tetramethyl aluminum, hydrogen, chlorine, bromine or iodine;
l is a neutral lewis base chelating ligand selected from: tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether, pyridine or substituted pyridines; n represents the number of ligands and is an integer of 0-2;
RE is a rare earth element selected from: lanthanide, scandium or yttrium.
2. The catalyst according to claim 1,
the alkyl of C1-C16 is selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, or n-octyl;
the silane group of C4-C16 is selected from: -CH2Si(CH3)3、-CH[Si(CH3)3]2、-CH2Si(CH3)2Ph or-CH2SiMe2C6H4OMe-o；
The alkyl amino of C2-C16 is selected from: -NMe2、-NEt2、-NnPr2、-NiPr2or-NnBu2；
The alkyl silamine group of C4-C20 is selected from: -N [ SiMe ]3]2or-N [ SiMe ]2H]2；
The arylamine group of C6-C20 is selected from: -CH2C6H4NMe2-o、-NHPh、-NHC6H4Me-p、-NHC6H4 iPr-p or-NHC6H4(iPr)2-2,6；
The substituted or unsubstituted C3-C10 allyl is selected from: -CH2CH＝CH2、-CH2C(Me)＝CH2、-(SiMe3)CHCH＝CH(SiMe3)；
The arylmethylene of C7-C20 is selected from: p-MeC6H4CH2-、p-EtC6H4CH2-、p-iPrC6H4CH2-、p-nPrC6H4CH2-、p-nBuC6H4CH2-or p-tBuC6H4CH2-；
The RE is selected from: scandium, yttrium, lanthanum, neodymium, gadolinium, dysprosium, holmium, erbium, ytterbium or lutetium.
3. The catalyst according to claim 1, wherein X is selected from the group consisting of: trimethylsilylmethylene, bistrimethylsilylmethine, allyl, 2-methylallyl, 1, 3-bistrimethylsilylallyl, hexamethylsilylamino, tetramethylsilylamino, methyl, benzyl, 4-methylbenzyl, 2-N, N' -dimethylbenzyl, tetramethylaluminum, borohydride, hydrogen, chlorine or bromine;
the RE is selected from: yttrium, lanthanum, neodymium, gadolinium, dysprosium, holmium, erbium or ytterbium.
4. The catalyst according to claim 1, wherein X is selected from the group consisting of: trimethylsilylidene, allyl, 2-methylallyl, hexamethyl-silylamine, tetramethylsilylamine, benzyl, 4-methylbenzyl, 2-N, N' -dimethylbenzyl, tetramethylaluminum-based, or hydrogen;
the RE is selected from: yttrium, lanthanum, neodymium, gadolinium, holmium, erbium or ytterbium.
5. The catalyst of claim 1, selected from the group consisting of compounds of formula i-1 to formula i-8:
Figure FDA0002982666050000021
6. a method for preparing the catalyst according to any one of claims 1 to 5, comprising the steps of:
a) ligand A and alkyl alkali metal reagent MR1Reacting to form an alkali metal salt B;
b) alkali metal salt B with rare earth halide RE (X')3Mixing the suspension and a monoanionic alkali metal reagent MX for reaction to form a catalyst shown as a formula I;
Figure FDA0002982666050000031
wherein:
the MR1In which M is an alkali metal, R1Is alkyl, hydrogen or amino;
the RE (X')3Wherein, X' is a halogen element;
the rare earth halide RE (X')3The solvent in the suspension is neutral Lewis base;
in MX, M is an alkali metal, and X is a monoanionic ligand.
7. A method for preparing a styrene monomer isotactic polymer is characterized by comprising the following steps:
under the action of an isotactic selective polymerization catalyst, carrying out polymerization reaction on a styrene monomer shown in a formula II to form an isotactic polymer shown in a formula III;
Figure FDA0002982666050000032
wherein the content of the first and second substances,
r is a substituent group at meta position and/or para position on a benzene ring, m is the number of the substituent group R, and m is more than or equal to 1 and less than or equal to 3;
r is selected from: C1-C20 alkoxy, C6-C20 aryloxy, C1-C20 alkylthio, C1-C20 silyl, C1-C40 alkyl, C3-C20 siloxy, C2-C20 alkylamino, hydrogen, chlorine, bromine or iodine;
the isotactic selective polymerization catalyst comprises a main catalyst;
the main catalyst is the catalyst according to any one of claims 1 to 5.
8. The method according to claim 7, wherein the styrenic monomer is selected from the group consisting of: styrene, p-methylstyrene, m-methylstyrene, 3, 5-dimethylstyrene, 4-alkylstyrene, p-methoxystyrene, p-methylthiostyrene, m-methoxystyrene, 3, 5-dimethoxystyrene, p-fluorostyrene, m-fluorostyrene, p-alkoxystyrene, 2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene, p-benzyloxystyrene, 4- (dimethylsilyl) styrene, 4- (trimethylsilyl) styrene, 4- (buten-1) ylstyrene, 4-allylstyrene, 4-phenylacetylenestyrene, 4-butylacetylenestyrene, 4-vinylbenzocyclobutene, 4- (trimethylsilylethynyl) styrene, 4-alkylthiostyrene, styrene, one or more of 4- (silyl) styrene, 4- (N ' N-dimethylamino) styrene, 4- (N ' N-diethylamino) styrene and 4- (N ' N-diphenylamino) styrene;
the isotactic polymerization catalyst further comprises a cocatalyst;
the cocatalyst comprises an organic boron salt and a main group metal alkyl compound;
the temperature of the polymerization reaction is 0-160 ℃, and the time is 1 min-100 h;
the molar ratio of the main catalyst to the organic boron salt to the main group metal alkyl compound is 1 to (0-1) to (0-1000);
the molar ratio of the main catalyst to the styrene monomer shown in the formula II is 1: 50-100000.
9. The method according to claim 8, wherein the styrenic monomer is selected from the group consisting of styrene, p-methylstyrene, m-methylstyrene, 3, 5-dimethylstyrene, 4-alkylstyrene, p-methoxystyrene, p-methylthiostyrene, m-methoxystyrene, 3, 5-dimethoxystyrene, p-fluorostyrene, m-fluorostyrene, p-alkoxystyrene, 2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene, p-benzyloxystyrene, 4- (dimethylsilyl) styrene, 4- (trimethylsilyl) styrene, 4- (buten-1) ylstyrene, 4-allylstyrene, 4-phenylacetylenestyrene, 4-butylacetylenestyrene, 4-vinylbenzocyclobutene, and the like, One or more of 4- (trimethylsilylethynyl) styrene, 4-alkylthio styrene and 4- (silyl) styrene;
the organoboron salt is selected from: [ NHEt3][B(C6F5)4]、[Ph3C][B(C6F5)4]、[PhNMe2H][B(C6F5)4]、B(C6F5)3、1,4-(C6F5)2BC6F4B(C6F5)2And [ Ph3C]2[1,4-(C6F5)3BC6F4B(C6F5)3]One or more of the above;
the main group metal alkyl compound is selected from one or more of alkyl aluminum, alkyl magnesium and alkyl zinc.
10. The preparation method according to claim 8, wherein the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, triisopropyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, methyl aluminoxane, dried aluminoxane and modified aluminoxane;
the alkyl zinc is diethyl zinc;
the alkyl magnesium is selected from one or more of diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium and dibutyl magnesium;
the molar ratio of the main catalyst to the organic boron salt to the main group metal alkyl compound is 1 to (0-1) to (0-500);
the molar ratio of the main catalyst to the styrene monomer shown in the formula II is 1: 100-80000.
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