CN114456333A - Poly (norbornene-b-vinyl norbornene) and preparation method thereof - Google Patents

Poly (norbornene-b-vinyl norbornene) and preparation method thereof Download PDF

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CN114456333A
CN114456333A CN202111613187.9A CN202111613187A CN114456333A CN 114456333 A CN114456333 A CN 114456333A CN 202111613187 A CN202111613187 A CN 202111613187A CN 114456333 A CN114456333 A CN 114456333A
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norbornene
cocatalyst
main catalyst
polymerization
alpha
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CN114456333B (en
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陈艳君
彭振博
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Ningbo Polytechnic
Henghe Materials and Science Technology Co Ltd
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Ningbo Polytechnic
Henghe Materials and Science Technology Co Ltd
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    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C08F4/00—Polymerisation catalysts
    • 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
    • C08F4/60—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 together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/7003—Bidentate ligand
    • C08F4/7004—Neutral ligand
    • C08F4/7006—NN
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a poly (norbornene-b-vinylnorbornene) and a method for preparing the same. The preparation method comprises the following steps: mixing a norbornene solution with an alpha-diimine nickel complex catalyst system to perform a first polymerization reaction, and then adding vinyl norbornene to perform a second polymerization reaction to obtain poly (norbornene-b-vinyl norbornene); the alpha-diimine nickel complex catalyst system comprises a main catalyst and a cocatalyst; the main catalyst is alpha-diimine nickel complex, and the structural formula is shown as formula I; the cocatalyst is alkyl aluminium halide and/or alkyl aluminoxane. According to the invention, a proper alpha-diimine nickel complex catalyst system is adopted for the first time to catalyze the active polymerization of Norbornene (NB) and Vinyl Norbornene (VNB), so that the block copolymer poly (norbornene-b-vinyl norbornene) is obtained, the insertion rate of VNB monomers is high, and the mass content can reach more than 20%.

Description

Poly (norbornene-b-vinyl norbornene) and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer material preparation, and particularly relates to poly (norbornene-b-vinyl norbornene) and a preparation method thereof.
Background
Norbornene has three polymerization modes, metathesis ring-opening polymerization, addition polymerization and cationic polymerization. The main chain of polynorbornene (VA-PNB) obtained by addition polymerization is fully saturated, the structural unit is norbornene with two rings, and the polynorbornene has excellent aging resistance, thermal stability and chemical stability. Since the norbornene structural unit is nonpolar, the application thereof is limited to some extent. Functional groups are introduced into the units of the norbornene structure, so that the VA-PNB is endowed with new functions, and the application range of the VA-PNB is expanded. The functionalized VA-PNB can be prepared by a plurality of methods, wherein the method of functionalizing the norbornene containing vinyl is an effective method for preparing the functionalized VA-PNB.
The block copolymer is a linear copolymer formed by alternately polymerizing different chain segments with different chemical structures. It can combine the excellent properties of various polymers to obtain functional polymer material with excellent performance. The molecular structure and the composition of the polymer can be designed, and polymer chain segments with different properties can form microphase separation structures, so that unique properties are generated. If the polynorbornene and the polar functionalized polynorbornene can be combined, the microphase separation of the polymer is promoted, and the polymer has potential application value in the aspect of gas selective permeation membranes. However, the prior art is only random copolymers of norbornene with polar norbornene and is not described as block copolymers of polynorbornene with polar functionalized norbornene, primarily because to achieve the synthesis of the block copolymer it is first necessary to achieve living polymerization of the two monomers. Coordination-active polymerization of polar monomers is difficult to achieve due to the catalytic action of the polar monomers on the catalyst.
Functionalized polynorbornenes can be prepared by functional modification of unreacted double bonds in the side chains of polyvinylnorbornene (VNB) or polyethylnorbornene (ENB). Because exocyclic double bonds in the ENB are internal double bonds and the reaction activity is poor, the VA-PVNB functionalization reaction is an efficient method for preparing the functionalized VA-PNB. The preparation of the block copolymer of VA-PNB and VA-PVNB and the functionalization modification of the VA-PVNB block can obtain the block copolymer of polynorbornene and polar functionalized polynorbornene, therefore, the preparation of the block copolymer of VA-PNB and VA-PVNB is the key for synthesizing the block copolymer of polynorbornene and polar functionalized polynorbornene. However, no reports are found in the prior art about the preparation of a block copolymer of VA-PNB and VA-PVNB, which can realize the living polymerization of NB and VNB.
In view of the above, it would be highly desirable to provide a poly (norbornene-b-vinylnorbornene) and a method for its preparation.
Disclosure of Invention
In order to solve the technical problem that a block copolymer of VA-PNB and VA-PVNB cannot be synthesized in the prior art, the invention provides poly (norbornene-b-vinyl norbornene) (abbreviated as P (NB-b-VNB)) and a preparation method thereof.
The present invention provides in a first aspect a process for the preparation of poly (norbornene-b-vinyl norbornene), the process comprising:
mixing a norbornene solution with an alpha-diimine nickel complex catalyst system to perform a first polymerization reaction, and then adding vinyl norbornene to perform a second polymerization reaction to obtain poly (norbornene-b-vinyl norbornene);
the alpha-diimine nickel complex catalyst system comprises a main catalyst and a cocatalyst;
the main catalyst is an alpha-diimine nickel complex, and the structural formula is shown as formula I:
Figure BDA0003436037920000021
in the formula I, R1Each independently hydrogen or methyl; r2、R3、R4、R5、R6Each independently selected from hydrogen and C1～C15Alkyl of (C)3～C15At least one of cycloalkyl and halogen of (a); each X is independently chlorine or bromine;
the cocatalyst is halogenated alkylaluminium and/or alkylaluminoxane.
Preferably, in formula I, R2、R3、R4、R5、R6Each independently selected from at least one of hydrogen, methyl, ethyl and isopropyl.
Preferably, the alkylaluminum halide has the formula RmAlX3-mWherein R is selected from C1～C10Alkyl of (C)3～C10Cycloalkyl of, C7～C10Aralkyl of (2), C6～C10R are identical or different, X is halogen, preferably Cl or Br, m is 1, 1.5, 2 or 3; and/or the alkylaluminoxane is selected from at least one of methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
Preferably, the molar ratio of nickel contained in the main catalyst to aluminum contained in the cocatalyst is 1: (50 to 3000), preferably 1: (80-2500), more preferably 1: (100 to 2300).
Preferably, the molar ratio of the main catalyst to the total amount of norbornene and vinyl norbornene in the polymerization system is (1-20): (1000 to 4000), more preferably (1 to 5): (1000 to 3000).
Preferably, the concentration of norbornene and/or vinylnorbornene contained in the polymerization system is independently 0.1 to 3.0mol/L, preferably 0.2 to 2.5mol/L, and more preferably 0.5 to 2.0 mol/L.
Preferably, the polymerization system is represented by C3～C10Saturated alkane of (C)3～C10Cycloalkane of (C)1～C5And C6～C15Preferably, at least one of propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, nonane, toluene, xylene, methylene chloride and 1,1,2, 2-tetrachloroethane is used as the solvent.
Preferably, the temperature of the first polymerization reaction and/or the second polymerization reaction is-10 ℃ to 80 ℃, preferably 0 ℃ to 70 ℃, and more preferably 5 ℃ to 60 ℃; and/or the time of the first polymerization reaction and/or the second polymerization reaction is 0.5 to 48 hours, preferably 1.0 to 36 hours, more preferably 1.5 to 24 hours, further preferably, the time of the first polymerization reaction is 4 to 8 hours, and the time of the second polymerization reaction is 10 to 24 hours.
Preferably, the norbornene solution is mixed with the alpha-diimine nickel complex catalyst system in one of the following ways:
(1) adding a main catalyst and a cocatalyst into the norbornene solution;
(2) adding a cocatalyst into the norbornene solution and then adding a main catalyst;
(3) simultaneously adding a main catalyst and a cocatalyst into the norbornene solution;
(4) the main catalyst and the cocatalyst are mixed in advance and then added into the norbornene solution.
The present invention provides, in a second aspect, a poly (norbornene-b-vinylnorbornene) prepared by the method of the present invention according to the first aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the method of the present invention can obtain a norbornene and vinylnorbornene block copolymer P (NB-b-VNB).
(2) The invention adopts a proper alpha-diimine nickel complex catalyst system to catalyze the active polymerization of Norbornene (NB) and Vinyl Norbornene (VNB) for the first time, and obtains the gel-free P (NB-b-VNB).
(3) The P (NB-b-VNB) obtained by the invention has higher molecular weight and narrower molecular weight distribution.
(4) The P (NB-b-VNB) obtained by the present invention has no crosslinked product.
(5) The P (NB-b-VNB) obtained by the invention can be further subjected to click chemistry reaction of mercaptoalkene, namely, mercaptan containing different functional groups is reacted with side chain vinyl to obtain block polynorbornene functionalized by different functional groups, and poly (norbornene-b-polar functionalized norbornene) (abbreviated as P (NB-b-XNB)) is obtained.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The present invention provides in a first aspect a process for the preparation of poly (norbornene-b-vinylnorbornene) (abbreviated as P (NB-b-VNB)), said process comprising: mixing a norbornene solution (containing norbornene) with an alpha-diimine nickel complex catalyst system to perform a first polymerization reaction, polymerizing for a period of time, after the norbornene monomer (NB monomer) completely reacts, adding Vinyl Norbornene (VNB) to perform a second polymerization reaction, and obtaining a poly (norbornene-b-vinyl norbornene) block copolymer;
the alpha-diimine nickel complex catalyst system comprises a main catalyst and a cocatalyst;
the main catalyst is an alpha-diimine nickel complex, and the structural formula is shown as formula I:
Figure BDA0003436037920000051
in the formula I, R1Each independently hydrogen or methyl; r2、R3、R4、R5、R6Each independently selected from hydrogen and C1～C15Alkyl of (C)3～C15At least one of cycloalkyl and halogen of (a); each X is independently chlorine or bromine; the cocatalyst is halogenated alkylaluminium and/or alkylaluminoxane.
The source of the α -diimine nickel complex is not particularly limited, and for example, the α -diimine nickel complex may be synthesized by a conventional method, for example, using dialdehyde or diketone as a raw material, reacting with aniline of different substituents to synthesize α -diimine, and reacting the α -diimine with nickel salt to obtain the α -diimine nickel complex.
The invention provides a method for preparing a block copolymer of NB and VNB, namely poly (norbornene-b-vinyl norbornene), by catalyzing active polymerization of NB and VNB by using an alpha-diimine nickel complex catalyst system (abbreviated as Ni catalyst), so that gel-free poly (norbornene-b-VNB) with a clear structure and a vinyl-containing side chain is obtained, and the reaction formula is shown as follows.
Figure BDA0003436037920000061
Although a-diimine nickel complexes are frequently reported to be applied to olefin polymerization as main catalysts, such as chinese patent applications CN104804030A, CN104892681A, CN109134302A, etc., and the types of olefin monomers in these patent applications are also extended to the categories of Norbornene (NB), vinyl-containing norbornene, etc., in the specific applications in these existing reports, only a-diimine nickel complex is used as a main catalyst to catalyze the addition polymerization of norbornene and ethylidene norbornene, and the molecular weight distribution index of the synthesized polymer is large and generally not less than 2, and no reports related to the copolymerization of norbornene and vinyl norbornene by using a-diimine nickel complex as a main catalyst are found, especially in block copolymerization. The reason for this is that although the nickel-based catalyst of alpha-diimine nickel complex has higher catalytic activity in catalyzing the preparation of VA-PNB or VA-PENB by the addition polymerization of norbornene or ethylidene norbornene, but is different from norbornene only containing intra-ring double bond and ethylidene norbornene basically not influencing polymerization because the exocyclic double bond is an endo double bond, the reaction activity is poor, the vinyl norbornene has special structure, it has two active double bonds, wherein vinyl (exocyclic double bond) can affect coordination and insertion of cycloolefine in coordination polymerization process, the use of the existing general alpha-diimine nickel complex nickel-based catalyst can reduce catalytic activity, monomer conversion rate, VNB monomer insertion rate or molecular weight of the obtained polymer, or vinyl groups also participate in the polymerization reaction to form a gel, and the molecular weight distribution index of the obtained polymer is large.
The invention discovers that only a very small amount of alpha-diimine nickel complexes can be used for catalyzing addition polymerization of VNB, but unsuitable alpha-diimine nickel complexes cannot ensure that active polymerization is realized during the polymerization of NB and VNB, so that block copolymer poly (norbornene-b-vinyl norbornene) which does not contain gel (cross-linking product), has high VNB monomer insertion rate, higher molecular weight and smaller molecular weight distribution index (the molecular weight distribution index is not more than 1.3) is obtained, and a lot of alpha-diimine nickel complexes are difficult to synthesize and have high catalyst cost; the invention firstly adopts a proper alpha-diimine nickel complex catalyst system to catalyze the active polymerization of Norbornene (NB) and Vinyl Norbornene (VNB) and simultaneously obtains poly (norbornene-b-vinyl norbornene) which does not contain gel (crosslinked product) and has higher molecular weight and smaller molecular weight distribution index (the molecular weight distribution index is not more than 1.3).
According to some preferred embodiments, in formula I, R2、R3、R4、R5、R6Each independently selected from at least one of hydrogen, methyl, ethyl and isopropyl.
According to some preferred embodiments, the alkylaluminum halide has the formula RmAlX3-mWherein R is selected from C1～C10Alkyl of (C)3～C10Cycloalkyl of, C7～C10Aralkyl of (2), C6～C10R are identical or different, X is halogen, preferably Cl or Br, m is 1, 1.5, 2 or 3; in some specific embodiments, the alkylaluminum halide is ethylaluminum sesquichloride and/or diethylaluminum chloride; and/or the alkylaluminoxane is selected from at least one of methylaluminoxane, ethylaluminoxane and isobutylaluminoxane; in some embodiments, the alkylaluminoxane is methylaluminoxane.
According to some preferred embodiments, the alpha-diimine nickel complex has any one of the structures shown below, but is not limited to the following structure.
Figure BDA0003436037920000071
According to some preferred embodiments, the alpha-diimine nickel complex has any one of the structures shown below:
Figure BDA0003436037920000081
the cocatalyst is at least one of aluminum sesquiethyl chloride, diethyl aluminum chloride and methylaluminoxane; it has been found that although the promoters selected for use in the present invention are of the type commonly used for nickel-based promoters, for purposes of the present invention, only when formula I is employedaOr of the formula IbWhen the alpha-diimine nickel complex is used in combination with at least one of aluminum sesquiethyl chloride, aluminum diethyl chloride and methylaluminoxane, the poly (norbornene-b-vinylnorbornene) which does not contain gel (crosslinked product), has a small molecular weight distribution index and a high insertion rate of VNB monomer can be obtained, and if the formula I is adopted, the poly (norbornene-b-vinylnorbornene) with the small molecular weight distribution index and the high insertion rate of VNB monomeraOr of the formula IbWhen the alpha-diimine nickel complex is combined with a cocatalyst such as tert-butyl aluminum modified methylaluminoxane, tri-n-hexyl aluminum and the like, living polymerization cannot be realized, and a block copolymer cannot be formed.
According to some preferred embodiments, the molar ratio of nickel contained in the main catalyst to aluminum contained in the cocatalyst is 1: (50 to 3000), preferably 1: (80-2500), more preferably 1: (100-2300) (e.g., 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, 1:1100, 1:1200, 1:1300, 1:1400, 1:1500, 1:1600, 1:1700, 1:1800, 1:1900, 1:2000, 1:2100, 1:2200, or 1: 2300).
In coordination polymerization, the cocatalyst can eliminate impurities in a polymerization system besides reacting with the main catalyst to form an active center, so that the amount of the cocatalyst needs to be ensured within a certain range to enable the catalyst system to have activity, and in the present invention, it is preferable that the molar ratio of nickel contained in the main catalyst to aluminum contained in the cocatalyst is 1: (50 to 3000); the present inventors have found that increasing the amount of the co-catalyst component has less effect on the catalytic activity but increases the catalyst cost.
In the present invention, the main catalyst may be used as it is, or may be diluted with a diluent selected from aromatic hydrocarbons and/or halogenated hydrocarbons. In the polymerization system of the invention, the invention discovers that the polymerization conversion rate can be improved by increasing the dosage of the main catalyst; the addition of a proper amount of the main catalyst is necessary in the invention, if the dosage of the main catalyst is too small, the number of active centers is small, the polymerization conversion rate is low, and the monomer utilization rate is low; if the amount of the main catalyst is too large, the catalyst utilization efficiency is low, and the catalyst cost is increased.
According to some preferred embodiments, the molar ratio of the main catalyst to the total amount of norbornene and vinylnorbornene contained in the polymerization system is (1 to 20): (1000 to 4000), more preferably (1 to 5): (1000 to 3000).
According to some preferred embodiments, the norbornene and/or vinylnorbornene are contained in the polymerization system at a concentration of independently 0.1 to 3.0mol/L, preferably 0.2 to 2.5mol/L, and more preferably 0.5 to 2.0mol/L (e.g., 0.5, 1, 1.5, or 2 mol/L).
According to some preferred embodiments, the polymerization system is represented by C3～C10Saturated alkane of (C)3～C10Cycloalkane of (C)1～C5And C6～C15Preferably, at least one of propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, nonane, toluene, xylene, methylene chloride and 1,1,2, 2-tetrachloroethane is used as the solvent; in the present invention, the solvent of the polymerization system is also the solvent used for the norbornene solution.
According to some preferred embodiments, the temperature of the first polymerization reaction and/or the second polymerization reaction is from-10 ℃ to 80 ℃, preferably from 0 ℃ to 70 ℃, more preferably from 5 ℃ to 60 ℃ (e.g., 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, or 60 ℃); and/or the time of the first polymerization reaction and/or the second polymerization reaction is 0.5 to 48 hours, preferably 1.0 to 36 hours, more preferably 1.5 to 24 hours (e.g., 1.5, 2, 5, 8, 10, 12, 15, 18, 20, or 24 hours), and further preferably the time of the first polymerization reaction is 4 to 8 hours (e.g., 4, 5, 6, 7, or 8 hours), and the time of the second polymerization reaction is 10 to 24 hours (e.g., 10, 12, 14, 16, 18, 20, 22, or 24 hours).
After reacting for a certain time at a second polymerization temperature, terminating the polymerization reaction by using water, methanol, ethanol and other substances; specifically, for example, the polymerization solution obtained after the polymerization reaction is treated with a hydrochloric acid ethanol solution or an aqueous solution containing NaOH to precipitate a polymer, the solvent is removed, and then the polymer is separated and dried to a constant weight, so that the poly (norbornene-b-vinylnorbornene) of the present invention can be obtained.
In the polymerization process, the main catalyst and the cocatalyst can be used in a mixed way or can be used independently.
According to some preferred embodiments, the norbornene solution is mixed with the alpha-diimine nickel complex catalyst system in one of the following ways:
(1) adding a main catalyst and a cocatalyst into the norbornene solution;
(2) adding a cocatalyst into the norbornene solution and then adding a main catalyst;
(3) simultaneously adding a main catalyst and a cocatalyst into the norbornene solution;
(4) the main catalyst and the cocatalyst are mixed in advance and then added into the norbornene solution.
The present invention provides in a second aspect a poly (norbornene-b-vinyl norbornene) prepared by the method of the first aspect of the present invention; the poly (norbornene-b-vinyl norbornene) prepared by the method does not contain gel, and the mass content of the vinyl norbornene structural unit is more than 20%.
The P (NB-b-VNB) obtained in the present invention can be further reacted with a mercaptoalkene by click chemistry reaction, i.e., by reacting a thiol HS-X containing a different functional group (e.g., 3-mercapto-1-propanol, 3-mercapto-1, 2-propanediol, 2-mercaptoethanol, 2-mercaptoacetic acid, ethyl 2-mercaptoacetate, 3-mercaptopropionic acid, or ethyl 3-mercaptopropionate) with a side chain vinyl group to obtain a block polynorbornene functionalized with a different functional group, and poly (norbornene-b-polar functionalized norbornene) (abbreviated as P (NB-b-XNB)) can be obtained.
Figure BDA0003436037920000101
The specific process may be, for example: (a) preparing the poly (norbornene-b-vinyl norbornene) into a polymer solution, and then adding an initiator and a thiol reagent into the polymer solution to perform a thiol-ene free radical addition reaction (namely, a thiol-ene click chemical reaction) to obtain a reaction product solution; the polymer solution may be, for example, toluene and/or tetrahydrofuran as a solvent; the polymer solution may contain poly (norbornene-b-vinylnorbornene) at a concentration of, for example, 0.03 to 0.08 g/mL; (b) precipitating the reaction product solution in ethanol, and then filtering (i.e. separating out the polymer by filtering) and drying to obtain a poly (norbornene-b-polar functionalized norbornene) block copolymer; the initiator is selected from azo initiators or organic peroxide initiators, preferably at least one selected from azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, benzoyl peroxide and methyl ethyl ketone peroxide; the thiol reagent is thiol containing different functional groups (thiol HS-X containing X group), preferably at least one selected from 3-mercapto-1-propanol, 3-mercapto-1, 2-propanediol, 2-mercaptoethanol, 2-mercaptoacetic acid, ethyl 2-mercaptoacetate, 3-mercaptopropionate and ethyl 3-mercaptopropionate; and/or the temperature of the mercapto-ene free radical addition reaction is 20 to 100 ℃ (e.g., 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃), and the time of the mercapto-ene free radical addition reaction is 1 to 10 hours (e.g., 1,2, 3, 4, 5, 6, 7, 8, 9 or 10 hours).
The invention will be further illustrated by way of example, but the scope of protection is not limited to these examples. The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
The invention adopts a gel permeation chromatograph, takes polystyrene as a standard sample, and measures the molecular weight and the molecular weight distribution of the polymer.
Example 1
To a toluene solution (10mL) containing NB (0.5mol/L) was added the following formula I in sequence at 10 deg.CaThe main catalyst (0.01mmol) and the cocatalyst of aluminum sesquiethylate were used in such an amount that the molar ratio of Al contained in the aluminum sesquiethylate to Ni contained in the main catalyst was 200, and even if the molar ratio of Al/Ni was 200, a sample was taken 5 hours after the polymerization reaction and was characterized, and it was found that NB had been completely converted into PNB, the weight average molecular weight of PNB (Mw) It was 49000g/mol, molecular weight distribution index (M)w/Mn) Is 1.1. Adding VNB 5mmol into the polymerization system, polymerizing for 12 hr, adding 5% hydrochloric acid ethanol solution to terminate reaction, drying the obtained polymer at 40 deg.C to constant weight to obtain 0.95g block copolymer P (NB-b-VNB), and weight average molecular weight (M) of P (NB-b-VNB)w) 92000g/mol, molecular weight distribution index (M)w/Mn) Is 1.2; the mass fraction of NB structural units and the mass fraction of VNB structural units in the block copolymer P (NB-b-VNB) were 49.5% and 50.5%, respectively. The product was gel free as measured by gel content.
Figure BDA0003436037920000121
Example 2
To a dichloromethane solution (10mL) containing NB (0.5mol/L) was added the cocatalyst methylaluminoxane and, for exampleFormula IbThe main catalyst (0.015mmol main catalyst) is shown, the amount of the methylaluminoxane is such that the molar ratio of Al contained in the methylaluminoxane to Ni contained in the main catalyst is 1500, even if the molar ratio of Al/Ni is 1500, after 5 hours of polymerization, a sample is taken for characterization, and it is found that NB has been completely converted into PNB, the weight average molecular weight (M) of PNBw) 33000g/mol, molecular weight distribution index (M)w/Mn) Is 1.1. Adding VNB 15mmol into the polymerization system, polymerizing for 12 hr, adding 5% hydrochloric acid ethanol solution to terminate reaction, drying the obtained polymer at 40 deg.C to constant weight to obtain 1.4g block copolymer P (NB-b-VNB), and weight average molecular weight (M) of P (NB-b-VNB)w) 89000g/mol, molecular weight distribution index (M)w/Mn) Is 1.3; the mass fraction of NB structural units in the block copolymer P (NB-b-VNB) was 34%, and the mass fraction of VNB structural units was 66%. The product was gel free as measured by gel content.
Figure BDA0003436037920000122
Example 3
The following formula IbThe main catalyst (0.01mmol) and a cocatalyst of aluminum sesquiethyl chloride were mixed together (the amount of aluminum sesquiethyl chloride was such that the molar ratio of Al contained in the aluminum sesquiethyl chloride to Ni contained in the main catalyst was 800, i.e., the Al/Ni molar ratio was 800), and 1mL of methylene chloride was added to obtain an α -diimine nickel complex catalyst system solution. After 6 hours of polymerization at 50 ℃ by adding the above solution of the alpha-nickel diimine complex catalyst system to a solution of NB (1.0mol/L) in n-hexane (10mL), samples were taken for characterization to find that NB had been completely converted into PNB and that the weight average molecular weight (M) of PNB wasw) 96000g/mol, molecular weight distribution index (M)w/Mn) Is 1.1. Adding VNB 5mmol into the polymerization system, polymerizing for 12 hr, adding 5% hydrochloric acid ethanol solution to terminate reaction, drying the obtained polymer at 40 deg.C to constant weight to obtain 1.29g block copolymer P (NB-b-VNB), and weight average molecular weight of P (NB-b-VNB)(Mw) 128000g/mol, molecular weight distribution index (M)w/Mn) Is 1.2; the mass fraction of NB structural units and the mass fraction of VNB structural units in the block copolymer P (NB-b-VNB) were 73% and 27%, respectively. The product was gel free as measured by gel content.
Figure BDA0003436037920000131
Example 4
To a dichloromethane solution (10mL) containing NB (1.0mol/L) was added diethyl aluminum chloride and the following formula I in that order at 30 deg.CaAs a result of taking a sample and characterizing it after 6 hours of polymerization reaction, it was found that NB had been completely converted into PNB and that the weight-average molecular weight of PNB (M was the weight-average molecular weight of M)w) 97000g/mol, molecular weight distribution index (M)w/Mn) Is 1.1. Adding VNB 10mmol into the polymerization system, polymerizing for 18 hr, adding 5% ethanol hydrochloride solution to terminate the reaction, drying the obtained polymer at 40 deg.C to constant weight to obtain 1.75g block copolymer P (NB-b-VNB), and weight average molecular weight (M) of P (NB-b-VNB)w) At 168000g/mol, molecular weight distribution index (M)w/Mn) Is 1.2; the mass fraction of NB structural units in the block copolymer P (NB-b-VNB) was 54%, and the mass fraction of VNB structural units was 46%. The product was gel free as measured by gel content.
Figure BDA0003436037920000141
Comparative example 1
This comparative example is essentially the same as inventive example 4, except that:
this comparative example was conducted using t-butylaluminum-modified methylaluminoxane as a cocatalyst in place of the diethylaluminum chloride of example 4 of the present invention.
The invention discovers that the alpha-diimine nickel complex catalyst system formed in the comparative example can not realize active polymerization and can not obtain a block copolymer.
Comparative example 2
This comparative example is essentially the same as inventive example 4, except that:
this comparative example uses the supported alpha-nickel diimine complex I1' 4Ni synthesized in CN104804030A in place of the formula I in example 4 of the inventionaThe alpha-diimine nickel complex is used as a main catalyst for experiments.
The invention discovers that the alpha-diimine nickel complex catalyst system formed in the comparative example can not realize active polymerization and can not obtain a block copolymer.
Comparative example 3
This comparative example is essentially the same as inventive example 4, except that:
this comparative example uses NiI1, synthesized in CN109134302A, instead of the formula I of the invention in example 4aThe alpha-diimine nickel complex is used as a main catalyst for experiments.
The invention discovers that the alpha-diimine nickel complex catalyst system formed in the comparative example can not realize active polymerization and can not obtain a block copolymer.
The invention has not been described in detail and is in part known to those of skill in the art.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A method for preparing poly (norbornene-b-vinyl norbornene), the method comprising:
mixing a norbornene solution with an alpha-diimine nickel complex catalyst system to perform a first polymerization reaction, and then adding vinyl norbornene to perform a second polymerization reaction to obtain poly (norbornene-b-vinyl norbornene);
the alpha-diimine nickel complex catalyst system comprises a main catalyst and a cocatalyst;
the main catalyst is an alpha-diimine nickel complex, and the structural formula is shown as formula I:
Figure FDA0003436037910000011
in the formula I, R1Each independently hydrogen or methyl; r is2、R3、R4、R5、R6Each independently selected from hydrogen and C1～C15Alkyl of (C)3～C15At least one of cycloalkyl and halogen of (a); each X is independently chlorine or bromine;
the cocatalyst is halogenated alkylaluminium and/or alkylaluminoxane.
2. The method of claim 1, wherein:
in the formula I, R2、R3、R4、R5、R6Each independently selected from at least one of hydrogen, methyl, ethyl and isopropyl.
3. The method of claim 1, wherein:
the alkylaluminum halide has the general formula RmAlX3-mWherein R is selected from C1～C10Alkyl of (C)3～C10Cycloalkyl of, C7～C10Aralkyl of (2), C6～C10R are identical or different, X is halogen, preferably Cl or Br, m is 1, 1.5, 2 or 3; and/or
The alkylaluminoxane is at least one selected from methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
4. The method of claim 1, wherein:
the molar ratio of nickel contained in the main catalyst to aluminum contained in the cocatalyst is 1: (50 to 3000), preferably 1: (80-2500), more preferably 1: (100 to 2300).
5. The method of claim 1, wherein:
the molar ratio of the main catalyst to the total amount of norbornene and vinyl norbornene in the polymerization system is (1-20): (1000 to 4000), more preferably (1 to 5): (1000 to 3000).
6. The method of claim 1, wherein:
the concentration of norbornene and/or vinylnorbornene contained in the polymerization system is independently 0.1 to 3.0mol/L, preferably 0.2 to 2.5mol/L, and more preferably 0.5 to 2.0 mol/L.
7. The method of claim 1, wherein:
polymerization system with C3～C10Saturated alkane of (C)3～C10Cycloalkane of (C)1～C5And C6～C15Preferably, at least one of propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, nonane, toluene, xylene, methylene chloride and 1,1,2, 2-tetrachloroethane is used as the solvent.
8. The method of claim 1, wherein:
the temperature of the first polymerization reaction and/or the second polymerization reaction is-10 ℃ to 80 ℃, preferably 0 ℃ to 70 ℃, and more preferably 5 ℃ to 60 ℃; and/or
The time of the first polymerization reaction and/or the second polymerization reaction is 0.5 to 48 hours, preferably 1.0 to 36 hours, more preferably 1.5 to 24 hours, and further preferably the time of the first polymerization reaction is 4 to 8 hours, and the time of the second polymerization reaction is 10 to 24 hours.
9. The method of claim 1, wherein the norbornene solution is mixed with the alpha-diimine nickel complex catalyst system in one of the following ways:
(1) adding a main catalyst and a cocatalyst into the norbornene solution;
(2) adding a cocatalyst into the norbornene solution and then adding a main catalyst;
(3) simultaneously adding a main catalyst and a cocatalyst into the norbornene solution;
(4) the main catalyst and the cocatalyst are mixed in advance and then added into the norbornene solution.
10. Poly (norbornene-b-vinyl norbornene) prepared by the method of any one of claims 1 to 9.
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