CN113881001B - Block copolymer and process for producing the same - Google Patents

Block copolymer and process for producing the same Download PDF

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CN113881001B
CN113881001B CN202010629012.6A CN202010629012A CN113881001B CN 113881001 B CN113881001 B CN 113881001B CN 202010629012 A CN202010629012 A CN 202010629012A CN 113881001 B CN113881001 B CN 113881001B
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block copolymer
radical initiator
monomer
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CN113881001A (en
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彭之皓
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • 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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

A block copolymer has the general formula (1) of a mediator-P 2 ‑P 1 X formula (1) having the chemical structural formulaWherein the mediator in the formula (1) and the formula (2) is a modulator which is a conjugated heptacyclic structure, P 1 Is a first polymer, which can be a conjugated or non-conjugated olefin monomer, R 1 Is P 1 N is P 1 The number of monomers is a positive integer in the range of 10 to 1500.P (P) 2 Is a second polymer, which is also a conjugated or non-conjugated olefin monomer with functional groups, R 2 Is P 2 M is P 2 The number of monomers in the block copolymer ranges from 10 to 1500, is a positive integer, and X is the terminal functional group of the block copolymer.

Description

Block copolymer and process for producing the same
Technical Field
The invention relates to the technical field of high polymer synthesis, in particular to a method for preparing a block copolymer without using a metal catalyst in the synthesis reaction process.
Background
Polyvinyl acetate is used as a mature industrial product and is widely applied to the fields of gluing, coating chemical industry, building decoration and the like, but the polyvinyl acetate material prepared in the prior industrial technology is often wide in molecular weight distribution and unsatisfactory in performance. As an important component in living radical polymerization, the reversible addition-fragmentation chain transfer (Reversible Addition-Fragmentation chain Transfer, RAFT) radical polymerization process has evolved rapidly over the last two decades. The polymerization method has the characteristics of mild conditions, wide application range of monomers and the like, and is widely applied to the synthesis of polymers with specific structures such as blocks, grafts, hyperbranched and stars. Notably, among other things, the regulator, or Chain Transfer Agent (CTA), plays a very important role in RAFT polymerization, with its activating and leaving groups having a direct impact on the reaction kinetics. The most common CTAs in RAFT polymerization are cumyl dithiobenzoate (cumyl dithiobenzoate, CDB) and methyl benzyl dithiobenzoate (l-phenylethyl dithiobenzoate, PEDB). In the regulation and control of some common monomers, such as styrene and methacrylate monomers, good regulation and control capability is shown. However, the range of monomers that can be regulated by such CTAs is limited and is not common to the regulation of other common monomers (e.g., vinyl acetate).
Polyvinyl alcohol is a material commonly used in industry for paints, contact lenses, polarizing films, and biomedical hydrogels, has extremely high industrial requirements, and can be used in products with high added value. It is known that the synthesis of polyvinyl alcohol block copolymers must be aided by regulators containing sulfur or heavy metals. However, sulfur and heavy metals are not only biologically toxic, but also present a pollution risk to the environment. In addition, sulfur-containing or heavy metal-containing regulators are expensive. All of the above problems limit the applicability of the polycondensed vinyl alcohol block copolymer.
In the prior art, the Diamond (Diamond) structure of three stars solves the display requirement of high PPI, and the pixel shape is a quadrilateral or rectangular structure, but still has a larger lifting space in terms of space utilization.
Disclosure of Invention
According to the shortcomings of the prior art, the main purpose of the present invention is to provide a method for polymerizing block copolymers by using a regulator (modulator), wherein the chemical structure of the regulator only contains carbon, hydrogen, oxygen or nitrogen atoms, so that the problems of biotoxicity and environmental pollution are not caused in the polymerization process of the block copolymers.
Another object of the present invention is that the regulator is a conjugated heptacyclic organic compound, and the molecular weight can be controlled and the molecular weight distribution can be narrower during the reaction by reacting the conjugated heptacyclic organic compound with the polymer to form a block copolymer.
In accordance with the above object, the present invention discloses a block copolymer having the general formula of formula (1) a mediator-P 2 -P 1 X, formula (1), of the formulaFormula (2), wherein the mediator in formula (1) and formula (2) is a modulator, P 1 Is a first polymer, P 2 Is a second polymer, R 1 Is a functional group, R, of a first polymer 2 Is a functional group of a second polymer, X is a terminal functional group of a block copolymer, which may be Or->n and m are respectively the number of monomers of the first polymer and the second polymer, and are positive integers, n and m are respectively 10-1,500, wherein the first polymer and the second polymer can be the same or different.
In a preferred embodiment of the block copolymers of the present invention, the modulator is a conjugated heptacyclic structure, the structural formula of which can be as follows:wherein Y may be halogen, hydrogen, OR, NR 2 、C 1 ～C 20 Alkyl, cycloalkyl, aromatic ring or aromatic hydrocarbon; the R may be hydrogen or C 1 ～C 20 Alkyl, cycloalkane, aromaA ring or an aromatic hydrocarbon.
In a preferred embodiment of the block copolymers of the present invention, the modulator is of a conjugated heptacyclic structure, which may be of the formulaWherein Y is 1 、Y 2 Y and Y 3 Can be halogen, hydrogen, OR, NR 2 Alkyl (C) 1 ～C 20 ) Cycloalkyl, aromatic ring or aromatic hydrocarbon, wherein R may be hydrogen, alkyl (C 1 ～C 20 ) Cycloalkane, aromatic ring or aromatic hydrocarbon, and Y 1 、Y 2 Y and Y 3 May be the same or different.
In a preferred embodiment of the block copolymer of the present invention, the first polymer and the second polymer may be conjugated or non-conjugated olefin monomers.
In a preferred embodiment of the block copolymer of the present invention, the monomers of the first and second polymers are(R＝C 1 ～C 10 Alkyl group of>(R＝C 1 ～C 10 Alkyl group of (2),(r=methyl, ethyl, propyl or isopropyl),Or->
According to the above object, the present invention also discloses a method for preparing a block copolymer, comprising the steps of: mixing the first Polymer (P) before hydrolysis 1 ') monomers, free radical initiator and modulator (mediator) to form a first intermediate, wherein the modulator, free radicalInitiator and first Polymer (P) before hydrolysis 1 ') is 1:20:1000 and the first intermediate has the structural formula of a mediator-P 1 ' -X, formula (3), wherein X is a terminal functional group of the first intermediate; the first intermediate is reacted with a second polymer (P) 2 ') to form a second intermediate, wherein the second intermediate has the formula of mediator-P 2 ’-P 1 ' X, formula (4), which may or may not be hydrolyzed, X being a terminal functional group of the second intermediate; and a second intermediate (mediator-P 2 ’-P 1 ' X) after hydrolysis to give a block copolymer, the block copolymer of which can be represented by the structural formula of a mediator-P 2 ’-P 1 X, formula (5) or mediator-P 2 -P 1 X, formula (6), the chemical structural formula of which can be represented asFormula (7), wherein P in formula (5) 2 ' is the second polymer P before hydrolysis 2 ' second Polymer P formed without hydrolysis upon hydrolysis reaction 2 ' and P in formula (6) 2 Representing the second polymer P before hydrolysis 2 ' second Polymer P formed after hydrolysis 2 And in formula (7), R 1 Is a first polymer (P 1 ) N is the number of monomers of the first polymer, is a positive integer, R 2 Is a second polymer (P 2 Or P 2 ') functional groups, m is the number of monomers of the second polymer, n, m are each a positive integer, n, m are each 10-1,500, X is the terminal functional group of the block copolymer, which may be +.>Or->In addition, the terminal functional group (X) of the first intermediate (shown in formula (3)), the terminal functional group (X) of the second intermediate (shown in formula (4)) and the terminal functional group (X) of the block copolymer (shown in formula(5) -formula (7) is the same terminal functional group and the average molecular weight of the block copolymer is 2,000 ～ 120,000, preferably 1,000 ～ 200,000.
In a preferred embodiment of the invention for preparing block copolymers, the free radical initiator may or may not be added when mixing the first intermediate with the monomers of the second polymer.
In preferred embodiments of the present invention for preparing block copolymers, the radical initiator may be an aqueous radical initiator (aqueous initiator) or an organic radical initiator (organic initiator).
In a preferred embodiment of the invention for preparing block copolymers, the aqueous free radical initiator may be(azobisis Ding Mi. Sup. Line hydrochloride, 2' -Azobis [2- (2-imidozolin-2-yl) propane ]]dihydrochloride) or +.>(4, 4'-Azobis (4-cyanovaleric acid), 4' -Azobis (4-cyanopentanoic acid)).
In a preferred embodiment of the invention for preparing block copolymers, the organic radical initiator may be(azobisisobutyronitrile, (2, 2' -azolbis (2-methylpropionrile), AIBN)),(1, 1'-azo (cyanocyclohexane), (1, 1' -Azobis (cyanocyclohexane), ABCN)), -j>(benzoyl peroxide (BPO)), or(diphenyl- (2, 4, 6-trimethylbenzoyl)) Phosphorus oxide, (2, 4, 6-trimethylphenyl) phosphine oxide, TPO).
In preferred embodiments of the present invention for preparing block copolymers, the ratio of free radical initiator to regulator (free radical initiator/regulator) may be from 0.5 to 50.
In a preferred embodiment of the present invention for preparing the block copolymer, the first polymer and the second polymer may be conjugated or non-conjugated olefin monomers.
In a preferred embodiment of the present invention for preparing the block copolymer, the monomers of the first polymer and the second polymer are(R＝C 1 ～C 10 Alkyl) and (I)>(R＝C 1 ～C 10 Alkyl group),Or->
In a preferred embodiment of the present invention for preparing block copolymers, the modulator is a conjugated heptacyclic structure, the structural formula of which can be as follows:wherein Y may be halogen, OR, NR 2 、C 1 ～C 20 Alkyl, cycloalkane, aromatic ring or aromatic hydrocarbon, wherein R may be hydrogen, C 1 ～C 20 Alkyl, cycloalkyl, aromatic ring or aromatic hydrocarbon.
In a preferred embodiment of the present invention for preparing block copolymers, the modulator is of a conjugated heptacyclic structure, the structural formula may beWherein Y is 1 、Y 2 Y and Y 3 Can be halogen, hydrogen, OR, NR 2 、C 1 ～C 20 Alkyl, cycloalkyl, aromatic ring or aromatic hydrocarbon; r mentioned above may be hydrogen, C 1 ～C 20 Alkyl, cycloalkane, aromatic ring or aromatic hydrocarbon, and Y 1 、Y 2 Y and Y 3 May be the same or different.
Drawings
FIG. 1 is a schematic diagram showing steps of a block copolymer preparation flow according to the disclosed technology.
FIG. 2A is a graph showing the conversion of a first intermediate versus time for a regulator Tralen, with different equivalents of free radical initiator, in accordance with the disclosed technique.
FIG. 2B is a graph showing the average molecular weight (M) of the modulator Tralen, a first intermediate, in accordance with the disclosed technique n ) And Polymer Dispersion Index (PDI) versus conversion.
FIG. 2C is a graph showing the average molecular weight (M) of the first intermediate under different equivalent free radical initiator conditions in accordance with the disclosed technique n ) A graph of relationship grown over time.
Fig. 3A is a graph showing the conversion of the first intermediate as a function of time for a regulator, tralen, vinyl acetate (VAc) as the monomer of the first polymer, and different equivalents of the monomer of the first polymer, in accordance with the disclosed technique.
FIG. 3B is a graph showing the average molecular weight (M) of the first intermediate under conditions where the modulator is Tralen and the monomer of the first polymer is Vinyl acetate (VAc) in different equivalents n ) And Polymer Dispersion Index (PDI) versus conversion.
FIG. 3C is a graph showing the average molecular weight (M) of the first intermediate under different equivalents of monomers of the first polymer in accordance with the disclosed technique n ) A graph of relationship grown over time.
FIG. 4A is a graph showing the conversion of a first intermediate after reaction versus time, showing the modulator as Tralen, the monomer of the first polymer as Acrylonitrile (AN), in accordance with the disclosed technology.
FIG. 4B is a graph showing the average molecular weight (M) of the first intermediate after the reaction, showing the modulator as Tralen, the monomer of the first polymer as Acrylonitrile (AN), in accordance with the disclosed technique n ) And Polymer Dispersion Index (PDI) versus conversion.
FIG. 5A is a graph showing the conversion of a first intermediate after reaction versus time for a regulator Tralen and a first polymer of N-vinyl pyrrolidone (NVP) as monomers in accordance with the disclosed technology.
FIG. 5B is a graph showing the average molecular weight (M) of the first intermediate after reaction, showing the modulator as Tralen, the monomer of the first polymer as N-Vinylpyrrolidone (NVP) in accordance with the disclosed technique n ) And Polymer Dispersion Index (PDI) versus conversion.
FIG. 6A is a graph showing the conversion of a first intermediate versus time for a modulator that is Tropone under different equivalents of free radical initiator in accordance with the disclosed technology.
FIG. 6B is a graph showing that the modulator is Tropone, the monomer of the first polymer is Vinyl acetate (VAc), and the average molecular weight of the first intermediate after the reaction (M n ) And Polymer Dispersion Index (PDI) versus conversion.
FIG. 6C is a graph showing the average molecular weight (M) of the first intermediate under different equivalents of the radical initiator in accordance with the disclosed technique n ) A graph of relationship grown over time.
Fig. 7A is a graph showing the conversion of a first intermediate versus time for a modulator of Tropone, a monomer of a first polymer of different equivalents, and a monomer of the first polymer of Vinyl acetate (VAc), in accordance with the disclosed technology.
FIG. 7B is a graph showing that the modulator is Tropone, the monomer of the first polymer is different equivalent weight, and the monomer of the first polymer is Vinyl acetate (VAc), the average molecular weight of the first intermediate after the reaction (M n ) And Polymer Dispersion Index (PDI) versus conversion.
FIG. 7C is a graph showing the average molecular weight (M) of the first intermediate under different equivalents of monomers of the first polymer in accordance with the disclosed technique n ) A graph of relationship grown over time.
FIG. 8A is a graph showing the conversion of a first intermediate versus time when the modulator is Tropone and the monomer of the first polymer is Methacrylate (MA) in accordance with the disclosed technology.
FIG. 8B is a graph showing that the modulator is Tropone, the monomer of the first polymer is Methacrylate (MA), and the average molecular weight of the first intermediate after the reaction (M n ) And Polymer Dispersion Index (PDI) versus conversion.
FIG. 8C is a graph showing the average molecular weight (M) of the first intermediate according to the disclosed technique n ) A graph of relationship grown over time.
FIG. 9A is a graph showing the conversion of a first intermediate versus time for a Vinyl acetate (VAc) monomer as the modulator, and with different equivalents of free radical initiator, in accordance with the disclosed technology.
FIG. 9B is a graph showing that the modulator is Tropolone, the monomer of the first polymer is Vinyl acetate (VAc), and the average molecular weight of the first intermediate after the reaction (M n ) And Polymer Dispersion Index (PDI) versus conversion.
FIG. 9C is a graph showing the average molecular weight (M) of the first intermediate under different equivalents of the radical initiator in accordance with the disclosed technique n ) A graph of relationship grown over time.
FIG. 10A is a graph showing the conversion of a first intermediate versus time for a different equivalent of a monomer of a first polymer, with the modulator being Tropolone and the monomer of the first polymer being Vinyl acetate (VAc), in accordance with the disclosed technology.
FIG. 10B is a graph showing that the modulator is Tropolone, the monomer of the first polymer is Vinyl acetate (VAc), and the average molecular weight (M) of the first intermediate after the reaction is performed under the condition of different equivalents of the monomer of the first polymer n ) And Polymer Dispersion Index (PDI) versus conversion.
FIG. 10C is a graph showing the average molecular weight (M) of the first intermediate according to the disclosed technique n ) A graph of relationship grown over time.
FIG. 11A is a graph showing the conversion of a first intermediate versus time for a regulator of azobisis Ding Mi hydrochloride (2, 2' -azolins 2- (2-imidozolin-2-yl) propane) dihydrochloride) (also known as VA-044) and a first polymer of N-vinyl pyrrolidone (NVP) in accordance with the disclosed technology.
FIG. 11B is a schematic illustration of an azo-bis-Ding Mi-hydrochloride (2, 2' -azolbis [2- (2-imidozolin-2-yl) propane) as a modulator in accordance with the disclosed technique]Dihydrochloride (also known as VA-044), the monomer of the first polymer is N-vinyl pyrrolidone (NVP), the average molecular weight of the first intermediate after reaction (M n ) And Polymer Dispersion Index (PDI) versus conversion.
FIG. 11C is a graph showing the average molecular weight (M) of the first intermediate according to the disclosed technique n ) A graph of relationship grown over time.
FIG. 12A is a graph showing the conversion of a first intermediate after reaction with different equivalents of free radical initiator versus time for a regulator Binam-Tralen and a first polymer monomer Vinyl acetate (VAc) in accordance with the disclosed technique.
FIG. 12B is a graph showing that the modulator is Binam-Tralen, the monomer of the first polymer is Vinyl acetate (VAc), and the average molecular weight (M) of the first intermediate after reaction under different equivalents of free radical initiator n ) And Polymer Dispersion Index (PDI) versus conversion.
Detailed Description
So that the manner in which the above recited objects, features and advantages of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. The drawings referred to below are illustrative of features of the present invention and are not necessarily drawn to scale. The description of the embodiments related to the technology known to those skilled in the art will not be further described.
The invention mainly uses conjugated heptarings containing carbon, hydrogen, oxygen and nitrogen as regulators (modulators) to polymerize with olefin monomers (olefin monomers) to form block copolymers (block copolymers) containing polyolefin, in particular to polyvinyl alcohol block copolymers. The block copolymer in the present invention has the general formula (1): media-P 2 -P 1 X, formula (1), the chemical structural formula of which can be represented asFormula (2), wherein in formula (1) and formula (2), the mediator is a modulator, P 1 Is a first polymer, P 2 Is a second polymer, X is a terminal functional group of the block copolymer, which may be +.>Or->But is not limited to the above; r is R 1 Is a first polymer (P 1 ) N is the functional group of the first polymer (P 1 ) Is a positive integer, R 2 Is a second polymer (P 2 ) M is the functional group of the second polymer (P 2 ) Is a positive integer, in embodiments of the invention, the first polymer (P 1 ) With a second polymer (P 2 ) May be the same or different.
It is noted that in the embodiment of the present invention, the terminal functional group (X) of the block copolymer is a compound that is heated, irradiated or sonicated to generate free radicals, and the generated free radical functional groups are the terminal functional groups of the block copolymer disclosed in the present invention, and different free radical initiators have different initiation modes, as shown in table 1:
table 1:
in one embodiment of the present invention, the modulator is a conjugated seven-ring structure, and the structural formula thereof can be as follows:(Binam-Tralen) wherein Y may be halogen, hydrogen, OR, NR 2 、C 1 ～C 20 Alkyl, cycloalkyl, aromatic ring or aromatic hydrocarbon; r mentioned above may be hydrogen, C 1 ～C 20 Alkyl, cycloalkyl, aromatic ring or aromatic hydrocarbon. In another embodiment, the modulator may be +>(Tralen) wherein Y 1 、Y 2 Y and Y 3 Can be halogen, hydrogen, OR, NR 2 、C 1 ～C 20 Alkyl, cycloalkyl, aromatic ring or aromatic hydrocarbon; r mentioned above may be hydrogen, C 1 ～C 20 Alkyl, cycloalkaneAn aromatic ring or hydrocarbon, and Y 1 、Y 2 Y and Y 3 May be the same or different. From the above, it can be seen that the chemical structure of the regulator used in the present invention contains only carbon, hydrogen, oxygen or nitrogen atoms, so that the problems of biotoxicity and environmental pollution are not caused during the polymerization reaction for forming the block copolymer, and the metal catalyst is not required for preparation, thereby improving the environmental friendliness of the block copolymer formed in the present invention.
In the present invention, the first polymer and the second polymer are conjugated or non-conjugated olefin monomers, wherein the monomers of the first polymer and the second polymer can be(R＝C 1 ～C 10 Alkyl) and (I)>(R＝C 1 ～C 10 Alkyl) and (I)> Or->In one embodiment of the present invention, the monomers of the first polymer and the monomers of the second polymer may be the same or different. Specifically, the first polymer may be polyvinyl acetate (Poly (vinyl acetate)) and polyvinyl alcohol (Poly (vinyl alcohol)), and the second polymer may be polystyrene, polymethyl acrylate, polymethyl methacrylate, polyvinylidene fluoride, polycaprolactone, polyglycolic acid, polyepichlorohydrin, polyvinylpyrrolidone, polyvinyl chloride, polyethylene glycol, polyacrylonitrile, polydimethyl acrylamide, and polyacrylic acid, but is not limited to the above-disclosed types.
In light of the foregoing, the present invention discloses the preparation of block copolymersThe method is as shown in the step flow chart of fig. 1. In fig. 1, step S1: mixing the first Polymer (P) before hydrolysis 1 ') monomers, free radical initiator and modulator to form a first intermediate, wherein the first intermediate has the structural formula of mediator-P 1 ' X, formula (3), X is the terminal functional group of the first intermediate, in which step the ratio of monomer, free radical initiator to regulator of the first polymer is 1:20:1000, in a preferred embodiment the ratio of free radical initiator to regulator (free radical initiator/regulator) may be from 0.5 to 50, the ratio of monomer of the first polymer being in the range of from 10 to 3000. In addition, in this step S1, the radical initiator may be an aqueous radical initiator (aqueous initiator) or an organic radical initiator (organic initiator), wherein the aqueous radical initiator may be(azobisis Ding Mi. Sup. Line hydrochloride, 2' -azobis [2- (2-imidozolin-2-yl) propane ]]dihydrochloride) or +.>(4, 4'-azobis (4-cyanovaleric acid), 4' -azobis (4-cyanopentanoic acid)); the organic radical initiator may be(azobisisobutyronitrile, (AIBN)), >(1, 1'-azo (cyanocyclohexane), (1, 1' -azobis (cyanocyclohexane), ABCN)), -j>(benzoyl peroxide (BPO)), or +.>(diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus, (diphenyl) (2, 4),6-trimethylbenzoyl)phosphine oxide，TPO))。
In the present invention, azobisisobutyronitrile (AIBN) is used as a radical initiator, and since azobisisobutyronitrile is frequently used as an initiator for polymerization of olefin polymer monomers such as vinyl acetate (vinyl acetate), acrylic acid ester, acrylonitrile or vinyl chloride, the advantage of using azobisisobutyronitrile as a radical initiator in the present invention is that: the decomposition temperature is 65-85 ℃, so that the method is applicable to most polymerization reactions, the primary decomposition rate of the azodiisobutyronitrile has small change for different solvents, and the azodiisobutyronitrile is not easy to attack by free radicals.
Step S2 follows: the first intermediate (mediator-P 1 ' -X) (formula (3)) and a second polymer (P) before hydrolysis 2 ') monomers are mixed and reacted to form a second intermediate, the structural formula of the second intermediate is a mediator-P 2 ’-P 1 ' -X, formula (4). Similarly, X in formula (4) is the terminal functional group of the second intermediate. In this step, the first intermediate (mediator-P 1 ' -X) (formula (3)) and a second polymer (P) before hydrolysis 2 The monomer of') may be mixed with a free radical initiator; in another embodiment, no radical initiator may be added. Finally, in step S3: the second intermediate (mediator-P 2 ’-P 1 ' X) (formula (4)) to obtain a block copolymer, it is to be noted herein that the hydrolysis reaction in step S3 means that the entire second intermediate is subjected to hydrolysis reaction, however, due to the second polymer (P) 2 The nature of the') does not necessarily allow hydrolysis, if the second polymer (P) 2 ') in the hydrolysis reaction of step S3, the second intermediate (mediator-P) 2 ’-P 1 ' -X) obtaining the mediator-P after hydrolysis 2 ’-P 1 -X, formula (5); if the second polymer (P) 2 ' hydrolysis occurs in the hydrolysis reaction of step S3, then the second intermediate (mediator-P) 2 ’-P 1 ' -X) obtaining the mediator-P after hydrolysis 2 -P 1 -X, formula (6), wherein P in formula (6) 2 Is a second polymer after hydrolysis, and the chemical structural formula of the final block copolymer can be expressed asFormula (7). The mediator of the above formulas (3) to (7) is a regulator, and the terminal functional group (X) of the above first intermediate (shown as formula (3)), the terminal functional group (X) of the second intermediate (shown as formula (4)) and the terminal functional group (X) of the block copolymer (shown as formula (5) -formula (7)) are the same terminal functional group, which may be- >Or->However, the present invention is not limited to the above, and the terminal functional group (X) is formed in the same manner as described above, and is not described in detail herein; r is R 1 Is a first polymer (P 1 ) N is the number of monomers of the first polymer, is a positive integer, R 2 Is a second polymer (P 2 Or P 2 ') and m is the number of monomers of the second polymer, which is a positive integer, in embodiments of the invention the first polymer (P 1 ) With a second polymer (P 2 ) May be the same or different. />
The method for forming the block copolymer of the present invention is described below based on the above-described procedure.
Example 1:
the regulating agent comprises: radical initiator: a monomer (VAc) of a first polymer, wherein the modulator is(Tralen), the radical initiator (X) is AIBN, and the monomer of the first polymer is VAc. Thus, the regulator (Tralen), the radical initiator (AIBN) and the first polymer (VAc) are mixed at a ratio of 1: x:1000 in a solvent-free and 60 deg.CIs reacted under the condition of mixing, and PVAc (corresponding to the first intermediate (mediator-P) described in the step S1 is obtained after the reaction 1 ' X) of the formula:
in this example, the free radical initiator (AIBN) was mixed with the regulator (tranen) and the first polymer (VAc) at different equivalent weights (50, 30, 20, 10) with the concentration of the monomer of the regulator (tranen) and the first polymer (VAc) fixed at 1: x:1000 (regulator: radical initiator: monomer of first polymer (VAc)) to obtain a graph of conversion of the first intermediate versus time as shown in fig. 2A. As can be seen in fig. 2A, the conversion grows linearly with time, and the shorter the sinking period, the faster the polymerization rate, when the AIBN proportion is higher; when the AIBN ratio is lowered, the sinking period becomes longer and the polymerization rate becomes slower. FIG. 2B shows the average molecular weight (M) n ) And Polymer Dispersion Index (PDI) versus conversion. In FIG. 2B, the average molecular weight grows linearly with conversion and conforms to the theoretical molecular weight during polymerization. FIG. 2C shows the average molecular weight (M) n ) The larger the average molecular weight (M) of the first intermediate is, therefore, at different ratios of free radical initiator n ) Slowly grows with time, and the signal peak moves towards the high molecular weight direction.
Example 2:
the regulating agent comprises: radical initiator: a monomer (VAc) of a first polymer wherein the modulator is(Tralen), AIBN as radical initiator and VAc as monomer of the first polymer, and the regulator (Tralen), AIBN as radical initiator and the first polymer (VAc) at a concentration of 10.85M were mixed at a ratio of 1:20: the ratio of y (regulator (Tralen): radical initiator (AIBN): monomer of the first polymer (VAc)) is reacted at 60℃in the absence of solventAfter the reaction, PVAc (corresponding to the first intermediate (mediator-P) described in the above step S1 can be obtained 1 ' X) as described in the previous example one. It is noted that the difference between the second embodiment and the first embodiment is that in the second embodiment, the equivalent weight of the monomer of the first polymer (VAc) is changed to 500, 1000, 2500, 4000, respectively, and thus the conversion of the first intermediate as shown in FIG. 3A and the time-dependent graph of the average molecular weight (M) of the first intermediate as shown in FIG. 3B can be obtained n ) And Polymer Dispersion Index (PDI) versus conversion. In FIG. 3A, the conversion rate grows linearly with time and the submergence period is similar. FIG. 3C shows the average molecular weight (M) n ) The larger the average molecular weight (M) of the first intermediate is, therefore, at different monomer ratios n ) Slowly grows with time, and the signal peak moves towards the high molecular weight direction.
Example 3:
the regulating agent comprises: radical initiator: the monomer (AN) of the first polymer, the regulator is(Tralen), the radical initiator (X) is AIBN, and the monomer of the first polymer is AN. In this example, a modulator (Tralen), a radical initiator (AIBN) and AN at a concentration of 5.08M are combined at 1:10:1000 The ratio of the regulator (Tralen) to the radical initiator (AIBN) to the monomer (AN) of the first polymer was reacted in the presence of Dimethylformamide (DMF) at 60℃to give PAN (corresponding to the first intermediate (mediator-P) in the above-mentioned step S1) 1 ' -X) the reaction scheme can be as follows:
from the above, a plot of the conversion of the first intermediate as represented in FIG. 4A versus time can be obtained, as represented in FIG. 4B, of the average molecular weight (M n ) And Polymer Dispersion Index (PDI) versus conversion. As can be obtained in fig. 4A, the conversion of the first intermediate increases with increasing reaction time, growing linearly. In fig. 4B, the average molecular weight of the first intermediate increases linearly with conversion in the presence of a modulator (tranen) and coincides with the theoretical molecular weight line.
Example 4:
the regulating agent comprises: radical initiator: monomer of first Polymer (NVP), modulator is(Tralen), the radical initiator (X) is AIBN, and the monomer of the first polymer is NVP. In this example, a modulator (Tralen), a radical initiator (AIBN) and NVP at a concentration of 9.36M were combined at 1:10:1000 The ratio of the regulator (Tralen) to the radical initiator (AIBN) to the monomer (NVP) of the first polymer was allowed to react at 60℃without solvent to give PNVP (corresponding to the first intermediate (mediator-P) in step S1 1 ' X) the reaction scheme may be as follows:
from the above reaction, a plot of the conversion of the first intermediate as shown in FIG. 5A versus time and the average molecular weight (M) of the first intermediate as shown in FIG. 5B can be obtained n ) And Polymer Dispersion Index (PDI) versus conversion. As can be seen in fig. 5A, the formation of the first intermediate has a significant submergence period during which the conversion is not significantly altered. After the submergence period, the conversion rate increases rapidly linearly with time. In fig. 5B, as the conversion of the first intermediate increases, its average molecular weight also increases and conforms to the theoretical molecular weight.
Example 5:
the regulating agent comprises: radical initiator: monomer (VAc) of the first polymer, modulator is(Tropone), the radical initiator (X) is AIBN and the monomer of the first polymer is VAc. Thus, the modulator (Tropone), the radical initiator (AIBN) and the first polymer (VAc) were mixed at 1: x:1000 in a solvent-free and 60 ℃ to obtain PVAc (corresponding to the first intermediate (mediator-P) in the step S1 1 ' X) of the formula:
under the condition that the monomer concentration of the regulator (Tropone) and the first polymer (VAc) is fixed, the free radical initiator (AIBN) with different equivalent weights (40, 20, 10) is respectively mixed with the regulator (Tropone) and the first polymer (VAc) according to the ratio of 1: x:1000 (control agent: radical initiator: monomer of first polymer (VAc)) to obtain a graph of conversion of the first intermediate with time as shown in fig. 6A. As can be seen in fig. 6A, the conversion grows linearly with time, and the shorter the sinking period, the faster the polymerization rate, when the AIBN proportion is higher; when the AIBN ratio is lowered, the sinking period becomes longer and the polymerization rate becomes slower. FIG. 6B shows the average molecular weight (M) n ) And Polymer Dispersion Index (PDI) versus conversion. In FIG. 6B, the average molecular weight during polymerization, although deviating from the theoretical molecular weight, grows linearly with the conversion. FIG. 6C shows that the smaller the molecular weight of the Elutation time, the larger the molecular weight of the first intermediate, and therefore the average molecular weight (M n ) Slowly grows with time, and the signal peak moves towards the high molecular weight direction.
Example 6:
the regulating agent comprises: radical initiator: a monomer (VAc) of a first polymer wherein the modulator is(Tropone) the free radical initiator is AIBN, firstThe monomer of the polymer was VAc, the modulator (Tropone), the radical initiator (AIBN) and the first polymer (VAc) at a concentration of 10.85M were combined at a ratio of 1:20: the ratio of y (regulator) to radical initiator (AIBN) to monomer (VAc) of the first polymer) is solvent-free and reacted at 60℃to give PVAc (corresponding to the first intermediate (mediator-P) described in step S1 1 ' X) as described above, except that the ratio of the equivalent of the monomer of the first polymer (VAc) is 300, 1000, 3000, respectively, and thus a plot of the conversion of the first intermediate as shown in FIG. 7A versus time and the average molecular weight (M) of the first intermediate as shown in FIG. 7B can be obtained as well n ) And Polymer Dispersion Index (PDI) versus conversion. In FIG. 7A, the conversion rate grows linearly with time and the submergence period is similar. In FIG. 7B, the average molecular weight, though deviating from the theoretical molecular weight, grows linearly with the conversion, and can reach as fast as one hundred thousand when the monomer ratio is increased; when the monomer proportion is reduced, the conversion rate can reach 65 percent. FIG. 7C shows that the time of the period of the time of the period is smaller average molecular weight (M) n ) The larger the average molecular weight (M) of the first intermediate is, therefore, at different monomer equivalent ratios n ) Slowly grows with time, and the signal peak moves towards the high molecular weight direction.
Example 7:
the regulating agent comprises: radical initiator: the Monomer (MA) of the first polymer, the regulator is(Tropone), the radical initiator (X) is AIBN and the monomer of the first polymer is MA. In this example, the modulator (Tropone), the radical initiator (AIBN) and MA at a concentration of 5.42M were combined at 1:20:1000 The ratio of the regulator (Tropone) to the radical initiator (AIBN) to the Monomer (MA) of the first polymer was reacted in the presence of Benzene (Benzene) as a solvent at 50℃to give PMA (corresponding to the first intermediate (mediator-P) in the above-mentioned step S1 1 ' X) the reaction scheme may be as follows:
from the above, a plot of the conversion of the first intermediate as shown in FIG. 8A versus time can be obtained, as shown in FIG. 8B, of the average molecular weight (M n ) And Polymer Dispersion Index (PDI) versus conversion. As can be seen in fig. 8A, the conversion of the first intermediate increases with increasing reaction time, growing linearly. In FIG. 8B, the average molecular weight of the first intermediate in the presence of a modulator (Tropone) is biased from the theoretical molecular weight but increases linearly with conversion. FIG. 8C shows the average molecular weight (M) n ) The larger the average molecular weight (M) n ) Slowly grows with time, and the signal peak moves towards the high molecular weight direction.
Example 8:
the regulating agent comprises: radical initiator: a monomer (VAc) of a first polymer, wherein the modulator is(Tropolone), the radical initiator (X) is AIBN and the monomer of the first polymer is VAc. Thus, the modulator (Tropolone), the radical initiator (AIBN) and the first polymer (VAc) were mixed at 1: x:1000 in a solvent-free and 60 ℃ to obtain PVAc (corresponding to the first intermediate (mediator-P) in the step S1 1 ' X) of the formula:
under the condition that the monomer concentration of the modulator (Tropolone) and the first polymer (VAc) is fixed, the free radical initiator (AIBN) with different equivalent weights (40, 20, 10) is respectively mixed with the modulator (Tropolone) and the first polymer (VAc) according to the ratio of 1: x:1000 (control agent: radical initiator: monomer of first Polymer (VAc)) A ratio of the first intermediate to the second intermediate as shown in fig. 9A. As can be seen in fig. 9A, the conversion grows linearly with time, and the shorter the sinking period, the faster the polymerization rate, when the AIBN proportion is higher; when the AIBN ratio is lowered, the sinking period becomes longer and the polymerization rate becomes slower. FIG. 9B shows the average molecular weight (M) n ) And Polymer Dispersion Index (PDI) versus conversion. In FIG. 9B, the average molecular weight during polymerization grew linearly with conversion, although it was deviated from the theoretical molecular weight. FIG. 9C shows that the smaller the molecular weight of the Elutation time, the larger the molecular weight of the first intermediate, and therefore the average molecular weight (M n ) Slowly grows with time, and the signal peak moves towards the high molecular weight direction.
Example 9:
the regulating agent comprises: radical initiator: a monomer (VAc) of a first polymer wherein the modulator is(Tropolone), radical initiator AIBN, monomer of first polymer VAc, regulator (Tropolone), radical initiator (AIBN) and first polymer (VAc) at 10.85M concentration, 1:20: the ratio of y (regulator) to free radical initiator (AIBN) to monomer (VAc) of the first polymer is carried out in the absence of solvent at 60℃to give PVAc (corresponding to the first intermediate (mediator-P) described in step S1 1 'X') was as before, except that this example 9 was a modification of the equivalent weight of the monomer of the first polymer (VAc) in the ratios of 300, 1000, 3000, respectively, and thus a plot of the conversion of the first intermediate as shown in FIG. 10A versus time and the average molecular weight (M) of the first intermediate as shown in FIG. 10B could also be obtained n ) And Polymer Dispersion Index (PDI) versus conversion. In fig. 10A, the conversion grows linearly with time. In FIG. 10B, the average molecular weight, which deviates from the theoretical molecular weight but grows linearly with the conversion, can reach 120,000 as the monomer ratio increases; when a sheet is The volume ratio is reduced, and the conversion rate can reach 55 percent. FIG. 10C shows that the smaller the time of the addition, the larger the molecular weight, and therefore the average molecular weight (M) of the first intermediate at different monomer ratios n ) Slowly grows with time, and the signal peak moves towards the high molecular weight direction.
Example 10:
the regulating agent comprises: radical initiator: monomer of first Polymer (NVP), modulator is(Tropolone), the radical initiator (X) is VA-044, and the monomer of the first polymer is NVP. In this example, a modulator (Tropolone), a radical initiator (VA-044) and NVP at a concentration of 4.68M were combined at 1:20:1000 The ratio of regulator (Tropolone): radical initiator (VA-044): monomer of first polymer (NVP)) was reacted at 40 ℃ in deionized water to obtain PNVP (equivalent to the first intermediate (mediator-P) described in the above step S1 1 ' X) the reaction scheme may be as follows:
from the above reaction, a plot of the conversion of the first intermediate as shown in FIG. 11A versus time and the average molecular weight (M) of the first intermediate as shown in FIG. 11B can be obtained n ) And Polymer Dispersion Index (PDI) versus conversion. As can be seen in fig. 11A, the formation of the first intermediate has a significant submergence period during which the conversion is not significantly altered. After the submergence period, the conversion rate increases rapidly linearly with time. In fig. 11B, as the conversion of the first intermediate increases, the average molecular weight thereof also increases, and at a high conversion, the average molecular weight starts to deviate from the theoretical molecular weight. FIG. 11C shows the average molecular weight (M) of the first intermediate as the time of the reaction increases n ) Slowly grows with time, and the signal peak moves towards the high molecular weight direction.
Example 11:
the regulating agent comprises: radical initiator: a monomer (VAc) of a first polymer, wherein the modulator is(Binam-Tralen), AIBN as radical initiator (X) and VAc as monomer of the first polymer. Thus, the regulator (Binam-Tralen), the monomer in the presence of the radical initiator (AIBN) in different concentrations and the first polymer (VAc) in a concentration of 10.85M, was used in a ratio of 1: x:1000 The ratio of (regulator (Binam-Tralen): radical initiator (AIBN): monomer of the first polymer (VAc)) was mixed and reacted at 60℃without solvent to obtain PVAc (corresponding to the first intermediate (mediator-P) in the above-mentioned step S1 1 ' X), wherein the ratio (X) of the free radical initiator is 40, 20, 10, respectively.
Thus, according to the above, a graph of the conversion of the first intermediate as shown in FIG. 12A versus time and the average molecular weight (M) of the first intermediate as shown in FIG. 12B can be obtained n ) And Polymer Dispersion Index (PDI) versus conversion. In FIG. 12A, the conversion grows linearly with time, and the shorter the sinking period, the faster the polymerization rate, when the AIBN ratio is higher. In fig. 12B, it can be observed that the average molecular weight of the first intermediate increases linearly with the conversion of the first intermediate, regardless of the ratio of the radical initiator, and matches the theoretical molecular weight line.
The conversion referred to in the present invention is the ratio of the monomer of the first polymer to the first intermediate by polymerization, and is the ratio of the conversion to the first intermediate by hydrogen nuclear magnetic resonance spectroscopy 1 H NMR spectroscopy) detection; the average molecular weight was measured using a gel permeation chromatograph (GPC, gelpermeation chromatography) with polystyrene as a standard. The theoretical molecular weight is calculated from the following formula:
M n，th ＝([monomer] 0 /[mediator] 0 )×(M.W.of monomer)×Conversion
in the above calculation formula, M n,th Is the theory ofMolecular weight, [ Monomer ]] 0 Initial concentration of monomer for first Polymer [ mediator ]] 0 The initial concentration of the regulator, the molecular weight of the monomer of which M.W.of monomer is the first polymer, and the Conversion of the monomer of which Conversion is the first polymer.
Next, the first intermediate (mediator-P) obtained in each of the above examples was obtained 1 The reaction of' -X) with the monomers of the second polymer (i.e.as in step S2) and hydrolysis gives the block copolymer (mediator-P) 2 -P 1 X or mediator-P 2 ’-P 1 X) taking example one, the first intermediate PVAc obtained in example one was mixed with the monomers of the second polymer, MA, and reacted to form a second intermediate having an average molecular weight of 28,000 and a polymer dispersion coefficient of 2.22. Namely, the reaction formula is as follows:
After the second intermediate is obtained, a hydrolysis reaction is performed again to obtain a block copolymer, i.e., PVA-b-PAA.
As can be seen from the above polymerization reaction, the present invention does not use any transition metal (or heavy metal) as a catalyst or control agent for the polymerization reaction, and does not contain sulfide, so that the block copolymer formed by the polymerization reaction has reduced biotoxicity, is also environmentally friendly, and reduces the risk of environmental pollution. Therefore, the properties of the block copolymer are more suitable for the basic materials in the biomedical fields such as surfactants, pigment dispersants, emulsifiers or drug carriers, and the block copolymer formed by the invention can also be applied to adhesives, stabilizers, dispersants, emulsifiers, photosensitizers, filling materials and the like.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the claims; while the foregoing is directed to embodiments and methods of the present invention, other and further embodiments and methods of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (12)

1. A block copolymer, characterized in that the block copolymer has the general formula of formula (1) a mediator-P 2 -P 1 X, formula (1), of the formulaWherein in the formula (1) and the formula (2), the mediator is a group having a conjugated heptacyclic structure containing carbon, hydrogen, oxygen and nitrogen, and P is a modulator 1 Is a first polymer, P 2 Is a second polymer, the first polymer and the second polymer are conjugated or non-conjugated olefin monomers having a functional group, X is a terminal functional group of the block copolymer, and R in the formula (2) 1 Is the functional group of the first polymer, n is the number of monomers of the first polymer, is a positive integer, R 2 M is the number of monomers of the second polymer, is a positive integer, n and m are each 10-1,500, wherein the monomers of the first polymer are different from the second polymer by->
Or is orR is C 1 -C 10 An alkyl group.
2. Such asThe block copolymer of claim 1, wherein the conjugated heptacyclic structure has the structural formula:wherein Y is halogen, hydrogen, OR, NR 2 、C 1 ～C 20 Alkyl, cycloalkyl, aromatic ring or aromatic hydrocarbon; r is hydrogen, C 1 ～C 20 Alkyl, cycloalkyl, aromatic ring or aromatic hydrocarbon.
3. The block copolymer of claim 1, wherein the conjugated heptacyclic structure has the formulaWherein Y is 1 、Y 2 Y and Y 3 Is halogen, hydrogen, OR, NR 2 、C 1 ～C 20 Alkyl, cycloalkane, aromatic ring or aromatic hydrocarbon, R is hydrogen, C 1 ～C 20 Alkyl, cycloalkane, aromatic ring or aromatic hydrocarbon, and Y 1 、Y 2 Y and Y 3 Are the same or different.
4. The block copolymer of claim 1, wherein the terminal functional groups of the block copolymer are represented as Or->Wherein the helix in said formula is a mediator-P in said formula (1) 2 -P 1 。
5. A process for producing a block copolymer, characterized in that the processThe method comprises mixing monomers of a first polymer before hydrolysis, a free radical initiator, and a regulator to form a first intermediate, wherein the ratio of the regulator, the free radical initiator, and the monomers of the first polymer before hydrolysis is 1:20:1000 and the structural formula of the first intermediate is a mediator-P 1 ' -X, formula (1), wherein X is a terminal functional group of the first intermediate;
mixing the first intermediate with a monomer of a second polymer prior to hydrolysis to form a second intermediate, wherein the second intermediate has the formula of mediator-P 2 ’-P 1 ' -X, formula (2); and
subjecting the second intermediate to hydrolysis reaction to obtain the block copolymer, wherein the block copolymer has a structural formula of a mediator-P 2 -P 1 -X, formula (3) or mediator-P 2 ’-P 1 -X, formula (4), wherein in the formula (3), the P 2 Is the second polymer P before the hydrolysis 2 ' formation of the hydrolyzed second Polymer P by the hydrolysis reaction 2 And in the formula (4), the P 2 ' is the second polymer P before the hydrolysis 2 ' the second Polymer P formed without hydrolysis 2 ' and the chemical structural formula is shown asIn the formulas (1) to (5), the mediator is a group having a conjugated heptacyclic structure containing carbon, hydrogen, oxygen and nitrogen, and the terminal functional group of the block copolymer is the same as the terminal functional group of the first intermediate and the terminal functional group of the second intermediate, which is a nitrile group, a cyanocyclohexyl group, a 4-cyanovalerate group, an imidazoline group, a benzoic acid group or a diphenylphosphine oxide group, and in the formula (5), the monomer of the first polymer before hydrolysis, the monomer of the second polymer before hydrolysis is a conjugated or non-conjugated olefin-based monomer having a functional group, R 1 Is a functional group of the first polymer, n is the first polymerIs a positive integer, R 2 For the second polymer (P 2 ) M is the number of monomers of the second polymer, n and m are each a positive integer of 10-1,500, the monomers of the first polymer and the monomers of the second polymer are-> Or->R is C 1 -C 10 An alkyl group; the terminal functional group of the block copolymer is +.> Or->Wherein the block copolymer has an average molecular weight of 2,000 ～ 120,000.
6. The method of claim 5, wherein the free radical initiator is added or not added when mixing the first intermediate with the monomer of the second polymer.
7. The method of claim 5 or 6, wherein the radical initiator is an aqueous radical initiator or an organic radical initiator.
8. The process of claim 7, wherein the aqueous radical initiator isOr->
9. The process according to claim 7, wherein the organic radical initiator isOr is or
10. The method according to claim 5, wherein the ratio of the radical initiator to the regulator is 0.5 to 50.
11. The method of claim 5, wherein the conjugated heptacyclic structure has the structural formula:wherein Y is halogen, OR, NR 2 、C 1 ～C 20 Alkyl, cycloalkane, aromatic ring or aromatic hydrocarbon, and R is hydrogen, C 1 ～C 20 Alkyl, cycloalkyl, aromatic ring or aromatic hydrocarbon.
12. The method of claim 5, wherein the conjugated heptacyclic structure has the formulaWherein Y is 1 、Y 2 Y and Y 3 Is halogen, hydrogen, OR, NR 2 、C 1 ～C 20 Alkyl, cycloalkyl, aromatic ring or aromatic hydrocarbon; the R is hydrogen or C 1 ～C 20 Alkyl, cycloalkane, aromatic ring or aromatic hydrocarbon, and Y 1 、Y 2 Y and Y 3 The same or different.
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