CN110229260B - Syndiotactic polymers of N-hydro-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene and their preparation and use - Google Patents

Syndiotactic polymers of N-hydro-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene and their preparation and use Download PDF

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CN110229260B
CN110229260B CN201910520931.7A CN201910520931A CN110229260B CN 110229260 B CN110229260 B CN 110229260B CN 201910520931 A CN201910520931 A CN 201910520931A CN 110229260 B CN110229260 B CN 110229260B
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崔冬梅
黄建铭
李世辉
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Changchun Institute of Applied Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F130/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention relates to a syndiotactic polymer of N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron hetero naphthalene and a preparation method and application thereof, belonging to the technical field of polymers. Solves the technical problems that the catalysis activity of the titanium metallocene catalyst is low and the prepared sPBN2VN has low molecular weight and is uncontrollable in the process of preparing sPBN2VN in the prior art. The structural formula of the sPBN2VN is shown as a formula (II), n is polymerization degree and is 100<n is less than or equal to 10000. in the preparation method of the polymer, the molecular weight and the molecular weight distribution of the polymerization reaction are controllable, the tacticity of the polymer is controllable, and the highest activity of the polymerization reaction can be 9.3 × 106g·mol‑1h‑1Can efficiently prepare a polymer having a number average molecular weight of 1.5 × 106The following sPBN2VN with various molecular weights.
Figure DDA0002096652600000011

Description

Syndiotactic polymers of N-hydro-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene and their preparation and use
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a syndiotactic polymer of N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene, and a preparation method and application thereof.
Background
Poisoning of metal catalysts by polar groups is an important challenge in preparing stereoregular polar polymers. The following methods are currently used to prepare polar polymers with stereoregularity: one is to design a catalyst with good resistance to polar monomers (angew. chem. int. ed.2015,54,5205; chem. commu., 2015,51, 4685; Macromolecules 2016,49, 781; chem. eur. j.,2017,23, 18151), and the other is to design a functionalized monomer with a reactive group (CN 201810317927). The title group of Rebekka S.Klausen, university of John Hopkins, USA, reports a monomer containing a BN aromatic ring, namely N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron hetero naphthalene (BN2VN), the structure of which is shown in formula (I); the free radical initiator Azobisisobutyronitrile (AIBN) can be used for initiating the free radical homopolymerization of the monomer and the free radical copolymerization of the monomer and styrene or vinyl naphthalene; the oxidation of PBN2VN-co-St copolymer with hydrogen peroxide under alkaline conditions gives a styrene-vinyl alcohol copolymer with a hydroxyl content dependent on the BN2VN content of its template polymer PBN2 VN-co-St. This group subsequently used a "titanocene" catalyst to prepare a syndiotactic polymer of N-hydro-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene (sPBN2VN), and the syndiotactic polyvinyl alcohol (sPVA) with maintained tacticity was obtained by oxidation after the polymerization. However, the catalytic activity of the catalyst is low in the catalytic process by using the titanium metallocene catalyst, and the molecular weight of the sPBN2VN prepared by the method is only 16.0kDa and is uncontrollable.
Figure BDA0002096652580000011
Disclosure of Invention
In view of the above, the present invention provides a syndiotactic polymer of N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boraphthalene, a preparation method thereof, and an application thereof, in order to solve the technical problems that in the prior art, a titanocene catalyst is used to prepare sPBN2VN, and the prepared sPBN2VN has low and uncontrollable molecular weight.
The technical scheme adopted by the invention for solving the technical problems is as follows.
The invention provides a syndiotactic polymer of N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron hetero naphthalene, the structural formula is shown as formula (II):
Figure BDA0002096652580000021
in the formula (II), n is the polymerization degree, and n is more than 100 and less than or equal to 10000.
The invention also provides a preparation method of the syndiotactic polymer of N hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron hetero naphthalene, which comprises the following steps:
under the protection of inert atmosphere, dissolving a rare earth metal complex, organic boron and organic aluminum in an organic solvent to obtain a catalyst solution;
dissolving an N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene monomer in an organic solvent, mixing with the catalyst solution obtained in the step one, reacting at-30-80 ℃ for 0.01-48 h, settling, and drying to obtain a syndiotactic polymer of the N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene;
the structural formula of the rare earth metal complex is A, B, C, D or E in the formula (IV):
Figure BDA0002096652580000031
in the formula (IV):
l n is a rare earth metal independently selected from scandium (Sc), yttrium (Y), lanthanum (L a), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (L u);
L1、L2、L3、L4and L5Are negative monovalent anions and are respectively and independently selected from cyclopentadienyl anions, cyclopentadienyl anion derivatives, indenyl anions, indenyl anion derivatives, fluorenyl anions or fluorenyl anion derivatives;
Lsis neutral Lewis base ligand and is independently selected from tetrahydrofuran, pyridine, diethyl ether, ethylene glycol dimethyl ether, 2, 6-dimethyl pyridine or pyrazine, and n represents LsN is 0, 1 or 2;
R1、R2、R3and R4Each independently selected from hydrogen, methyl, ethyl, isopropyl, methoxy or chlorine;
R5and R7Each independently selected from methylene, dimethylmethylene, dimethylsilylene or ethylene;
R6independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, 2, 6-dimethylphenyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-triisopropylphenyl or 2, 6-dichlorophenyl;
Riindependently selected from alkyl, silyl, aryl, silyl, alkylamino, allyl, benzyl, borohydride, chloride or bromide;
the molar ratio of the organic boron to the rare earth metal complex is (0.5-2.0): 1, and the organic boron contains [ BPh4]-Organic boron of [ B (C)6F5)4]-The organoboron or the neutral organoborane of (a);
the molar ratio of the organic aluminum to the rare earth metal complex is (0-1000): 1, and the organic aluminum is one or more of alkyl aluminum, hydrogenated alkyl aluminum, halogenated alkyl aluminum and aluminoxane;
the molar ratio of the N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron hetero-naphthalene monomer to the rare earth metal complex is (50-10000): 1.
Preferably, the inert atmosphere is an inert gas or nitrogen.
Preferably, the L n is independently selected from Sc, Y, L a, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, or L u;
the L1、L2、L3、L4And L5Each structural formula of (a) is independently selected from F, G or H in formula (V):
Figure BDA0002096652580000041
L1in the formula (V), R8And RsAre respectively and independently selected from hydrogen, alkyl of C1-C10, aryl of C6-C20 or silyl containing C1-C20;
L2、L3、L4and L5In the formula (V), R8Is represented by the structure B in the formula (IV) and L2Pyridyl directly linked, C structure shown and L3Directly linked R5Base, D structure shown and L4The structure of the directly connected N-heterocyclic carbene or the structure of the directly connected E is shown in the specification and L5Directly linked R7，RsAre respectively and independently selected from hydrogen, alkyl of C1-C10, aryl of C6-C20 or silyl containing C1-C20;
the R is1、R2、R3And R4Each independently selected from hydrogen, methyl or chlorine;
the R is5And R7Each independently selected from methylene or ethylene;
the R is6Independently selected from methyl, isopropyl, tert-butyl, 2, 6-dimethylphenyl or 2,4, 6-trimethylphenyl;
the R isiIndependently selected from-CH3、-CH2SiMe3、-CH(SiMe3)2、-CH2C6H4NMe2-o、 -N(SiMe3)2、-N(SiHMe2)2、1,3-C3H5、-CH2C6H5、-CH2C6H4CH3-p、-BH4-Cl or-Br.
Preferably, the structural formula of the rare earth metal complex is one of the following structures:
Figure BDA0002096652580000051
Figure BDA0002096652580000061
preferably, said compound contains [ BPh ]4]-With organoboron of [ NEt3H][BPh4]Or [ NBu ]3H][BPh4]Containing [ B (C)6F5)4]-With organoboron of [ NEt3H][B(C6F5)4]、[Ph3C][B(C6F5)4]Or [ PhNMe2H][B(C6F5)4]The neutral organoborane is triphenylboron or tris (pentafluorophenyl) boron.
Preferably, the organoaluminum is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-methylphenylaluminum, tribenzylaluminum, ethyldibenzylaluminum, ethyldi-p-methylphenylaluminum, diethylbenzylaluminum, dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dipentylaluminum hydride, dihexylaluminum hydride, dicyclohexylaluminum hydride, dioctylaluminum hydride, diphenylaluminum hydride, di-p-methylphenylaluminum hydride, dibenzylaluminum hydride, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, one or more of diisobutylaluminum chloride, dipentylaluminum chloride, dihexylaluminum chloride, dicyclohexylaluminum chloride, dioctylaluminum chloride, diphenylaluminum chloride, di-p-tolylaluminum chloride, dibenzylaluminum chloride, ethylbenzylaluminum chloride, ethyl-p-tolylaluminum chloride, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, and n-butylaluminoxane.
Preferably, in the first step and the second step, the organic solvent is one or more of saturated alkane, naphthenic hydrocarbon, aromatic hydrocarbon and halogenated aromatic hydrocarbon.
The invention also provides the application of the syndiotactic polymer of the N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron heteronaphthalene in preparing syndiotactic syndiotacticity polyvinyl alcohol, which comprises the following steps:
oxidizing the syndiotactic polymer of N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron hetero naphthalene under alkaline condition to obtain syndiotactic isotactic polyvinyl alcohol.
The invention also provides syndiotactic regular polyvinyl alcohol, the structural formula is shown as the formula (III):
Figure BDA0002096652580000071
in the formula (III), n is the polymerization degree, and n is more than 100 and less than or equal to 10000.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of sPBN2VN provided by the invention is to synthesize sPBN2VN by a coordination polymerization method catalyzed by rare earth metal complex for the first time, and the molecular weight distribution of the polymerization reaction can be regulatedThe tacticity of the polymer is controllable, and the activity of the polymerization reaction can reach as high as 9.3 × 106g·mol-1h-1。
The preparation method of sPBN2VN provided by the invention can efficiently prepare the sPBN2VN with the number average molecular weight of 1.5 × 106The following sPBN2VN with various molecular weights.
The sPBN2VN provided by the invention can prepare syndiotactic regular polyvinyl alcohol by oxidizing with hydrogen peroxide under alkaline conditions.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without inventive efforts.
FIG. 1 is a process flow diagram of BN2VN → sPBN2VN → sPVA according to the invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of sPBN2VN prepared in example 1 of the present invention (1H NMR)；
FIG. 3 is a nuclear magnetic carbon spectrum of sPBN2VN prepared in example 1 of the present invention (13C NMR) graph.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention in conjunction with the detailed description, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and not to limit the scope of the claims.
The invention provides a method for preparing a polymer sPBN2VN with high syndiotacticity and controllable molecular weight by utilizing a rare earth metal complex to catalyze a BN2VN syndiotacticity selective coordination polymerization method, which is shown as a first step process flow in figure 1 and specifically comprises the following steps:
under the protection of inert atmosphere, dissolving a rare earth metal complex, organic boron and organic aluminum in an organic solvent, and uniformly mixing to obtain a catalyst solution;
and step two, dissolving a BN2VN monomer in an organic solvent, adding the catalyst solution obtained in the step one, uniformly mixing, reacting for 0.01-48 h at-30-80 ℃, settling, and drying to obtain the sPBN2 VN.
In the above technical scheme, the structural formula of the rare earth metal complex is A, B, C, D or E in formula (IV):
Figure BDA0002096652580000091
(IV) in the following steps:
l n is a rare earth metal independently selected from scandium (Sc), yttrium (Y), lanthanum (L a), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (L u), preferably Sc, Y, L a, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, or L u, more preferably Sc, Y, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, L u, and particularly preferably Sc, Y, Nd, Dy, Ho, or L u.
L1、L2、L3、L4And L5Each is a negative monovalent anion independently selected from cyclopentadienyl anion, cyclopentadienyl anion derivative, indenyl anion derivative, fluorenyl anion or fluorenyl anion derivative, preferably cyclopentadienyl, indenyl or fluorenyl, more preferably L1、L2、 L3、L4And L5Each independently selected from F, G or H in formula (V):
Figure BDA0002096652580000092
L1in the formula (V), R8And RsEach independently selected from hydrogen, C1-C10 alkyl, C6-C20 aryl, and C1-C20-containing silyl, preferably hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, or trimethylsilyl, more preferably hydrogen, methyl, tert-butyl, phenyl, or trimethylsilyl;
L2、L3、L4and L5In the formula (V), R8Is represented by the structure B in the formula (IV) and L2Pyridyl directly linked, C structure shown and L3Directly linked R5Base, D structure shown and L4The structure of the directly connected N-heterocyclic carbene or the structure of the directly connected E is shown in the specification and L5Directly linked R7；RsIndependently selected from hydrogen, C1-C10 alkyl, C6-C20 aryl, and C1-C20 silane groups, preferably hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, or trimethylsilyl groups, more preferably hydrogen, methyl, tert-butyl, phenyl, or trimethylsilyl groups.
R1、R2、R3And R4Each independently selected from hydrogen, methyl, ethyl, isopropyl, methoxy or chlorine, preferably hydrogen, methyl or chlorine. Preferably, R1、R2、R3、R4Each independently selected from hydrogen, methyl or chlorine.
R5And R7Each independently selected from the group consisting of methylene, dimethylmethylene, dimethylsilylene and ethylene, preferably methylene or ethylene.
R6Independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, 2, 6-dimethylphenyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-triisopropylphenyl or 2, 6-dichlorophenyl, preferably methyl, isopropyl, tert-butyl, 2, 6-dimethylphenyl, 2,4, 6-trimethylphenyl, more preferably methyl, isopropyl, tert-butyl or 2,4, 6-trimethylphenyl.
RiIndependently selected from alkyl, silyl, aryl, silyl, alkylamino, allyl, benzyl, borohydride, chloride or bromide, preferably-CH3、-CH2SiMe3、-CH(SiMe3)2、-CH2C6H4NMe2-o、-N(SiMe3)2、 -N(SiHMe2)2、1,3-C3H5、-CH2C6H5、-CH2C6H4CH3-p、-BH4-Cl, -Br; more preferably-CH2SiMe3、-CH2C6H4NMe2-o、1,3-C3H5、-BH4or-Cl.
LsIs a neutral Lewis base ligand independently selected from the group consisting of tetrahydrofuran, pyridine, diethyl ether, ethylene glycol dimethyl ether, 2, 6-lutidine or pyrazine, n represents the number of Lewis bases and is 0, 1 or 2, and when n is 0, there is no neutral Lewis base ligand L in formula (IV)s。
The rare earth metal complexes in the above technical schemes are synthesized according to the prior art, and those skilled in the art can synthesize the complexes according to the related technical data. According to the preferred combination of the present invention, we prefer the following rare earth metal complexes as catalysts to prepare the catalytic system for catalyzing the syndiotactic selective polymerization experiment of BN2VN, preferably the rare earth metal complexes are only used as examples to illustrate the general structure of the rare earth metal complexes and are not meant to limit the scope of the present invention, and some simple modified structures which are in accordance with the formulas (IV), (V) and (VI) are also within the scope of the present invention.
In the technical scheme, the molar ratio of the organic boron to the rare earth metal complex is (0.5-2.0): 1, and the organic boron contains [ BPh [4]-Organic boron of [ B (C)6F5)4]-The organoboron or the neutral organoborane of (a); preferably, containing [ BPh4]-With organoboron of [ NEt3H][BPh4]Or [ NBu ]3H][BPh4]Containing [ B (C)6F5)4]-With organoboron of [ NEt3H][B(C6F5)4]、[Ph3C][B(C6F5)4]Or [ PhNMe2H][B(C6F5)4]The neutral organoborane is triphenylboron or tris (pentafluorophenyl) boron.
In the technical scheme, the molar ratio of the organic aluminum to the rare earth metal complex is (0-1000) 1, and the organic aluminum is one or more of alkyl aluminum, hydrogenated alkyl aluminum, halogenated alkyl aluminum and aluminoxane; preferred organoaluminum compounds are trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-methylphenylaluminum, tribenzylaluminum, ethyldibenzylaluminum, ethyldi-p-methylphenylaluminum, diethylbenzylaluminum, dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dipentylaluminum hydride, dihexylaluminum hydride, dicyclohexylaluminum hydride, dioctylaluminum hydride, diphenylaluminum hydride, di-p-methylphenylaluminum hydride, dibenzylaluminum hydride, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, One or more of dipentylaluminum chloride, dihexylaluminum chloride, dicyclohexylaluminum chloride, dioctylaluminum chloride, diphenylaluminum chloride, di-p-tolylaluminum chloride, dibenzylaluminum chloride, ethylbenzylaluminum chloride, ethyl-p-tolylaluminum chloride, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, and n-butylaluminoxane.
In the technical scheme, in the second step, the molar ratio of the BN2VN monomer to the rare earth metal complex is (50-10000): 1.
In the above technical solution, in the first step and the second step, the organic solvent is preferably one or more of saturated alkane, cycloalkane, aromatic hydrocarbon, and halogenated aromatic hydrocarbon, and more preferably, the organic solvent is one or more of n-hexane, cyclohexane, n-heptane, n-octane, petroleum ether, decalin, benzene, toluene, xylene, trimethylbenzene, fluorobenzene, chlorobenzene, dichlorobenzene, and trichlorobenzene.
In the technical scheme, the container used in the second step is subjected to anhydrous and anaerobic treatment in advance.
The invention also provides a syndiotactic polymer of N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene, the syndiotactic syndiotacticity of the polymer is more than 90%, and the structural formula is shown as the formula (II):
Figure BDA0002096652580000121
in the formula (II), n is the polymerization degree, and n is more than 100 and less than or equal to 10000.
The invention also provides an application of the syndiotactic polymer of the N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron hetero naphthalene in preparing syndiotactic syndiotacticity polyvinyl alcohol, as shown in a second step process flow in figure 1, comprising the following steps:
sPBN2VN was oxidized under alkaline conditions to give syndiotactic regular polyvinyl alcohol (ref. Angew. chem. int. Ed.2018,57,1673)).
The structural formula of the syndiotactic regular polyvinyl alcohol is shown as the formula (III):
Figure BDA0002096652580000122
in the formula (III), n is the polymerization degree, and n is more than 100 and less than or equal to 10000.
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
Under the anhydrous and oxygen-free conditions, the rare earth metal complex 1Sc(3.5mg,10μmol)、 [Ph3C][B(C6F5)4](9.2mg, 10. mu. mol) and AliBu3(0.2m L, 0.5 mol/L) and adding anhydrous and anaerobic treated fresh toluene to dilute to 0.5m L, stirring for 1min to mix them uniformly and react sufficiently to obtain a catalyst solution, adding the catalyst solution to 0.5m L solution dissolved with 0.31g (2mmol) of BN2VN monomer at 25 ℃, wherein the concentration of the solution polymerization monomer is 2 mol/L, stirring at high speed for 30min, adding 1m L volume fraction of 10% hydrochloric acid/ethanol solution to terminate the polymerization reaction, then pouring the reaction solution into 100m L methanol containing stabilizer (BHT) to settle, drying the obtained polymer in a vacuum oven at 40 ℃ for 48h to obtain 0.31g of net weight (yield 100%) (nuclear magnetic hydrogen spectrum of the obtained polymer), (yield 100%) (1H NMR and nuclear magnetic carbon Spectroscopy: (13C NMR) as shown in fig. 2 and 3, respectively, it was found that syndiotactic polymer sPBN2VN of N-hydro-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene was successfully prepared.
In example 1The rare earth metal complex is 1ScThe organic solvent is toluene, and the organic boron is [ Ph3C][B(C6F5)4]The organic aluminum is AliBu3. The other reaction examples were conducted in the same manner as in example 1, and the specific raw material ratios, reaction conditions and polymerization results are shown in Table 1.
TABLE 1 catalysis of syndiotactic selective coordination polymerization of BN2VN by rare earth metal complexes
Figure BDA0002096652580000131
Figure BDA0002096652580000141
Figure BDA0002096652580000151
In Table 1, the organoboron column, A represents B (C)6F5)3B represents [ Ph ]3C][B(C6F5)4]C represents [ NEt ]3H][B(C6F5)4]D represents [ PhNMe2H][B(C6F5)4]The catalyst comprises an organic aluminum column, a column I, an organic solvent column, a column II, a column III, a column.
The types and proportions of the rare earth metal complex, the organoboron and the organoaluminum as described in the above examples, and the solvent used may be any combination as defined in the above technical schemes, and are not listed.
From the polymerization data of examples 1-74, it can be found that the monomer can be converted by 100% when the catalyst solution provided by the invention is used for catalyzing the polymerization reaction of BN2VN, and the number average molecular weight of the obtained polymer is 0.68 × 104～150.3×104Within this range, the molecular weight distribution is narrow. The rare earth catalytic system can be highsPBN2VN having syndiotactic stereoregularity is prepared by selectively catalyzing the polymerization of BN2VN and oxidizing the polymer under basic conditions according to the literature method (Angew. chem. int. Ed.2018,57,1673). The specific method is that 620mg (4mmol) of the polymer is dissolved in 150m L tetrahydrofuran, a sodium hydroxide solution of 6 mol/L is added to 20m L, then a 30% hydrogen peroxide solution of 25m L is slowly dropped, the mixture is stirred at room temperature for 30min and then heated to 60 ℃ to reflux for 24h, the tetrahydrofuran is removed under reduced pressure, the reaction liquid drops are stirred and settled in 100m L distilled water, then filtered by a sand core funnel, the filter cake is washed by methanol for several times and then dried in a vacuum oven at 40 ℃ for 24 h.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Obvious variations or modifications of this invention are within the scope of the invention as claimed.

Claims (10)

  1. A syndiotactic polymer of N-hydro-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene, characterized by the structural formula shown in formula (II):
    Figure FDA0002539706720000011
    in the formula (II), n is the polymerization degree, and n is more than 100 and less than or equal to 10000;
    the preparation method of the syndiotactic polymer of the N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron heteronaphthalene comprises the following steps:
    under the protection of inert atmosphere, dissolving a rare earth metal complex, organic boron and organic aluminum in an organic solvent to obtain a catalyst solution;
    dissolving an N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene monomer in an organic solvent, mixing with the catalyst solution obtained in the step one, reacting at-30-80 ℃ for 0.01-48 h, settling, and drying to obtain a syndiotactic polymer of the N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene;
    the structural formula of the rare earth metal complex is A, B, C, D or E in the formula (IV):
    Figure FDA0002539706720000012
    in the formula (IV):
    l n is a rare earth metal independently selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium;
    L1、L2、L3、L4and L5Are negative monovalent anions and are respectively and independently selected from cyclopentadienyl anions, cyclopentadienyl anion derivatives, indenyl anions, indenyl anion derivatives, fluorenyl anions or fluorenyl anion derivatives;
    Lsis neutral Lewis base ligand and is independently selected from tetrahydrofuran, pyridine, diethyl ether, ethylene glycol dimethyl ether, 2, 6-dimethyl pyridine or pyrazine, and n represents LsN is 0, 1 or 2;
    R1、R2、R3and R4Each independently selected from hydrogen, methyl, ethyl, isopropyl, methoxy or chlorine;
    R5and R7Each independently selected from methylene, dimethylmethylene, dimethylsilylene or ethylene;
    R6independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, 2, 6-dimethylphenyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-triisopropylphenyl or 2, 6-dichlorophenyl;
    Riindependently selected from alkyl, silyl, aryl, silyl, alkylamino, allyl, benzyl, borohydride, chloride or bromide;
    the molar ratio of the organic boron to the rare earth metal complex is (0.5-2.0): 1, and the organic boron contains [ BPh4]-Organic boron of [ B (C)6F5)4]-The organoboron or the neutral organoborane of (a);
    the molar ratio of the organic aluminum to the rare earth metal complex is (0-1000), 1, wherein the organic aluminum is one or more of alkyl aluminum, alkyl aluminum hydride, halogenated alkyl aluminum, aluminoxane, tricyclohexyl aluminum, triphenyl aluminum, tri-p-methylphenyl aluminum, tribenzyl aluminum, ethyl dibenzyl aluminum, ethyl di-p-methylphenyl aluminum, diethyl benzyl aluminum, dicyclohexyl aluminum hydride, diphenyl aluminum hydride, di-p-methylphenyl aluminum hydride, dibenzyl aluminum hydride, dicyclohexyl aluminum chloride, diphenyl aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, ethyl benzyl aluminum chloride and ethyl p-tolyl aluminum chloride;
    the molar ratio of the N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron hetero-naphthalene monomer to the rare earth metal complex is (50-10000): 1.
  2. 2. A process for the preparation of syndiotactic polymers of N-h-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene as defined in claim 1, comprising the steps of:
    under the protection of inert atmosphere, dissolving a rare earth metal complex, organic boron and organic aluminum in an organic solvent to obtain a catalyst solution;
    dissolving an N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene monomer in an organic solvent, mixing with the catalyst solution obtained in the step one, reacting at-30-80 ℃ for 0.01-48 h, settling, and drying to obtain a syndiotactic polymer of the N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene;
    the structural formula of the rare earth metal complex is A, B, C, D or E in the formula (IV):
    Figure FDA0002539706720000031
    in the formula (IV):
    l n is a rare earth metal independently selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium;
    L1、L2、L3、L4and L5Are negative monovalent anions and are respectively and independently selected from cyclopentadienyl anions, cyclopentadienyl anion derivatives, indenyl anions, indenyl anion derivatives, fluorenyl anions or fluorenyl anion derivatives;
    Lsis neutral Lewis base ligand and is independently selected from tetrahydrofuran, pyridine, diethyl ether, ethylene glycol dimethyl ether, 2, 6-dimethyl pyridine or pyrazine, and n represents LsN is 0, 1 or 2;
    R1、R2、R3and R4Each independently selected from hydrogen, methyl, ethyl, isopropyl, methoxy or chlorine;
    R5and R7Each independently selected from methylene, dimethylmethylene, dimethylsilylene or ethylene;
    R6independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, 2, 6-dimethylphenyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-triisopropylphenyl or 2, 6-dichlorophenyl;
    Riindependently selected from alkyl, silyl, aryl, silyl, alkylamino, allyl, benzyl, borohydride, chloride or bromide;
    the molar ratio of the organic boron to the rare earth metal complex is (0.5-2.0): 1, and the organic boron contains [ BPh4]-Organic boron of [ B (C)6F5)4]-The organoboron or the neutral organoborane of (a);
    the molar ratio of the organic aluminum to the rare earth metal complex is (0-1000), 1, wherein the organic aluminum is one or more of alkyl aluminum, alkyl aluminum hydride, halogenated alkyl aluminum, aluminoxane, tricyclohexyl aluminum, triphenyl aluminum, tri-p-methylphenyl aluminum, tribenzyl aluminum, ethyl dibenzyl aluminum, ethyl di-p-methylphenyl aluminum, diethyl benzyl aluminum, dicyclohexyl aluminum hydride, diphenyl aluminum hydride, di-p-methylphenyl aluminum hydride, dibenzyl aluminum hydride, dicyclohexyl aluminum chloride, diphenyl aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, ethyl benzyl aluminum chloride and ethyl p-tolyl aluminum chloride;
    the molar ratio of the N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron hetero-naphthalene monomer to the rare earth metal complex is (50-10000): 1.
  3. 3. The method of claim 2 wherein the inert atmosphere is an inert gas or nitrogen.
  4. 4. The process for preparing syndiotactic polymers of N-H-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene according to claim 2,
    l n is independently selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, or lutetium;
    the L1、L2、L3、L4And L5Each structural formula of (a) is independently selected from F, G or H in formula (V):
    Figure FDA0002539706720000041
    L1in the formula (V), R8And RsAre respectively and independently selected from hydrogen, alkyl of C1-C10, aryl of C6-C20 or silyl containing C1-C20;
    L2、L3、L4and L5In the formula (V), R8Is represented by the structure B in the formula (IV) and L2Pyridyl directly linked, C structure shown and L3Directly linked R5Base, D structure shown and L4The structure of the directly connected N-heterocyclic carbene or the structure of the directly connected E is shown in the specification and L5Directly linked R7，RsAre respectively and independently selected from hydrogen, alkyl of C1-C10, aryl of C6-C20 or silyl containing C1-C20;
    the R is1、R2、R3And R4Each independently selected from hydrogen, methyl or chlorine;
    the R is5And R7Each independently selected from methylene or ethylene;
    the R is6Independently selected from methyl, isopropyl, tert-butyl, 2, 6-dimethylphenyl or 2,4, 6-trimethylphenyl;
    the R isiIndependently selected from-CH3、-CH2SiMe3、-CH(SiMe3)2、-CH2C6H4NMe2-o、-N(SiMe3)2、-N(SiHMe2)2、1,3-C3H5、-CH2C6H5、-CH2C6H4CH3-p、-BH4-Cl or-Br.
  5. 5. The method of claim 2 wherein the rare earth metal complex has the formula of one of the following structures:
    Figure FDA0002539706720000051
    Figure FDA0002539706720000061
    Figure FDA0002539706720000071
  6. 6. the method of claim 2, wherein the syndiotactic polymer comprising [ BPh ] is produced from N-H-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene4]-With organoboron of [ NEt3H][BPh4]Or [ NBu ]3H][BPh4]Containing [ B (C)6F5)4]-With organoboron of [ NEt3H][B(C6F5)4]、[Ph3C][B(C6F5)4]Or [ PhNMe2H][B(C6F5)4]Neutral organoborane is triphenylBoron or tris (pentafluorophenyl) boron.
  7. 7. The process according to claim 2 for preparing syndiotactic polymers of N-H-B-vinyl-1, 2-dihydro-1-aza-2-boraphthalene, wherein the organoaluminum is trimethylaluminum, triethylaluminum, tri-N-propylaluminum, triisopropylaluminum, tri-N-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-methylphenylaluminum, tribenzylaluminum, ethyldibenzylaluminum, ethyldi-p-methylphenylaluminum, diethylbenzylaluminum, dimethylaluminum hydride, diethylaluminum hydride, di-N-propylaluminum hydride, diisopropylaluminum hydride, di-N-butylaluminum hydride, diisobutylaluminum hydride, dipentylaluminum hydride, dihexylaluminum hydride, dicyclohexylaluminum hydride, dioctylaluminum hydride, One or more of diphenylaluminum hydride, di-p-methylphenylaluminum hydride, dibenzylaluminum hydride, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, dipentylaluminum chloride, dihexylaluminum chloride, dicyclohexylaluminum chloride, dioctylaluminum chloride, diphenylaluminum chloride, di-p-tolylaluminum chloride, dibenzylaluminum chloride, ethylbenzylaluminum chloride, ethyl-p-tolylaluminum chloride, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, and n-butylaluminoxane.
  8. 8. The method of claim 2, wherein the organic solvent in the first and second steps is one or more of saturated alkane, cycloalkane, aromatic hydrocarbon, and halogenated aromatic hydrocarbon.
  9. 9. Use of a syndiotactic polymer of N-hydro-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene according to claim 1 in the preparation of syndiotactic polyvinyl alcohol comprising the steps of:
    oxidizing the syndiotactic polymer of N-hydrogen-B-vinyl-1, 2-dihydro-1-aza-2-boron hetero naphthalene under alkaline condition to obtain syndiotactic isotactic polyvinyl alcohol.
  10. 10. Syndiotactic polyvinyl alcohol prepared by oxidation of syndiotactic polymer of N-hydro-B-vinyl-1, 2-dihydro-1-aza-2-boranaphthalene according to claim 1 under basic conditions, characterized by the structural formula shown in formula (III):
    Figure FDA0002539706720000081
    in the formula (III), n is the polymerization degree, and n is more than 100 and less than or equal to 10000.
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