CN111234213A - Pi-conjugated polymer with main chain containing tetrazine ring and synthesis method thereof - Google Patents
Pi-conjugated polymer with main chain containing tetrazine ring and synthesis method thereof Download PDFInfo
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- CN111234213A CN111234213A CN202010079365.3A CN202010079365A CN111234213A CN 111234213 A CN111234213 A CN 111234213A CN 202010079365 A CN202010079365 A CN 202010079365A CN 111234213 A CN111234213 A CN 111234213A
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Abstract
The invention discloses a pi-conjugated polymer with a main chain containing a tetrazine ring and a synthesis method thereof. The triazine ring-containing pi-conjugated polymer has a push-pull electronic structure, is selected from at least one polymer shown in a general formula I, and has the advantages of regular structure and high molecular weight. The invention provides a simple, convenient, efficient and simple-to-operate method for synthesizing a pi-conjugated polymer with a tetrazine ring-containing main chain and a push-pull electronic structure from hydrazine hydrate and a monomer with a general formula II for the first time.
Description
Technical Field
The invention belongs to the field of preparation of organic high molecular compounds, and particularly relates to a pi-conjugated polymer with a tetrazine ring-containing main chain and a push-pull electronic structure and a synthesis method thereof.
Background
The synthesis history of tetrazine has been hundreds of years, and the derivative thereof has wide application in the fields of organic synthesis, energetic materials, life science, pesticides, ion recognition and the like. One of the most studied isomers is 1, 2, 4, 5-tetrazine, which is an electron deficient aromatic system possessing four nitrogen atoms. Wherein, R, R' can be H, halogen, alkyl, alkoxy, alkyl mercapto, alkyl amino, alkynyl, aryl, heteroaryl, etc.
1, 2, 4, 5-tetrazines of the formula III
The earliest tetrazine syntheses were the Pinner synthesis (Gilles, c.; Pierre, a., s-Tetrazines as building Blocks for New Functional Molecules and molecular materials chem. rev.2010, 110, 3299-. However, this method also has some significant disadvantages such as narrow substrate range, which is only suitable for the synthesis of aromatic tetrazines, and very low yield of aliphatic tetrazines.
Method for synthesizing Pinner
The synthesis of tetrazines has been greatly developed in recent years. In 2012, new k. Devara i topic group found that 1, 2, 4, 5-tetrazine (Yang, j.; Karver, m.r.; Li, w.; Sahu, s.; Devara j, n.k., Metal-catalyst done-site synthesis of tetrazines direct free aliphatic nitriles and hydrazine. angew. int. em. ed.2012, 51(21), 5222-) could be synthesized in one pot using nitriles as raw materials while using Metal salts (e.g., nickel and zinc triflate, etc.) as catalysts. The Pierre Audebert project group reported a simple, efficient and Metal-Free method of synthesizing 3-Monosubstituted asymmetric 1, 2, 4, 5-Tetrazines in 2018 (Qu, Y.; Sauvage, F.X.; Clavier, G.; Miomandre, F.; Audebert, P., Metal-Free synthetic approach to 3-Monosubstituted asymmetry measurement 1, 2, 4, 5-Tetrazines Useful for bioinformatic reactions, Angew.Chem.Ed.2018, 57(37), 12057-12061.). They found that methylene chloride is a new formamidine replacement reagent. It can exhibit excellent reactivity and selectivity during the formation of the tetrazine ring, resulting in mild synthesis conditions and high yield. In 2019, the Hao xing Wu project group discovered a new organic catalytic method for synthesizing asymmetric tetrazine (Mao, W.; Shi, W.; Li, J.; Su, D.; Wang, X.; Zhang, L.; Pan, L.; Wu, X.; Wu H.; organic catalytic and Scalable Syntheses of asymmetric 1, 2, 4, 5-tetrazine by thio-Containing precursors, Angew. chem. int. Ed.2019, 58, 1106-1109.). They have found that tetrazines can be readily prepared in the presence of thiol-containing organic catalysts such as 3-mercaptopropionic acid and glutathione.
However, no document reports that nitrile monomers are directly utilized to synthesize the pi-conjugated polymer with the tetrazine ring-containing main chain and the push-pull electronic structure. Due to the superiority of the tetrazine polymer structure, the main chain has complete alternating arrangement of electron donating groups and electron deficient groups, a very good conjugated system and a pi-pi stacking effect, and the functional application of the tetrazine polymer can be obviously designed by changing the structure of side chain end groups, such as chains with different lengths and structures to influence the orientation and arrangement of the polymer.
Disclosure of Invention
To this end, the present invention provides the following aspects of the invention:
<1> a n-conjugated polymer having a main chain containing a tetrazine ring, which has a push-pull electron structure and has a structure represented by the following general formula I,
wherein Ar1, Ar2 or Ar3 are the same or different from each other and each independently is a carbon atom number of C4-C12The heteroaryl group of (a), the heteroatom of the heteroaryl group being selected from at least one of sulfur, oxygen and nitrogen; r1、R2、R3Are identical or different from each other and are each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C with hetero atoms being sulfur, oxygen or nitrogen6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl or substituted or unsubstitutedC of (A)1～C24A sulfinyl group; and R is4And R5Are the same or different from each other, and are independently selected from at least one of amino, cyano, amidino and amidinohydrazino groups.
m is an integer greater than 1; n is an integer equal to or greater than 0; p is an integer equal to or greater than 0.
<2>, the pi-conjugated polymer having a main chain containing a tetrazine ring according to <1>, wherein Ar1, Ar2 or Ar3 are independently selected from phenyl, naphthyl, biphenyl or thienyl.
<3>, the pi-conjugated polymer having a main chain containing a tetrazine ring according to the foregoing, which is a polymer represented by the general formula IA, IB, IC, ID, IE or IF:
wherein R is5、R6、R7、R8Each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl, substituted or unsubstituted C1～C24A sulfinyl group;
the end group R is selected from at least one of amino, cyano, amidino and amidinohydrazino;
n is an integer of 1 or more;
n1 is an integer of 1 or more;
m is an integer of 1 or more.
<4> the n-conjugated polymer having a main chain containing a tetrazine ring according to the foregoing, wherein a monomer of the n-conjugated polymer having a push-pull electron structure having a main chain containing a tetrazine ring but containing two cyano groups is synthesized, and has a structure represented by the following formula II:
X1，X2each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl, substituted or unsubstituted C1～C24Sulfinyl group, Ar4 is C4-C12The heteroaryl group, wherein the heteroatom of the heteroaryl group is selected from one of sulfur, oxygen and nitrogen.
<5> the n-conjugated polymer having a main chain containing a tetrazine ring according to the foregoing, wherein the monomer having the structure represented by the general formula II is selected from the group consisting of:
wherein R is5Each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl, substituted or unsubstituted C1～C24A sulfinyl group; n1 is an integer of 1 or more.
<6>, a method for producing a n-conjugated polymer having a main chain containing a tetrazine ring as described in any one of the above, which comprises:
1) dissolving a monomer with a structure shown in a general formula II in hydrazine hydrate;
2) dissolving a compound containing metal ions in hydrazine hydrate;
3) dissolving a solubilizer of the polymer in hydrazine hydrate;
4) reacting the reaction mixture at 60-150 ℃ for 0.5-48 hours to obtain the pi-conjugated polymer with the main chain containing dihydrotetrazine ring and having a push-pull electronic structure;
5) oxidizing the pi-conjugated polymer with a push-pull electronic structure and a main chain containing dihydrotetrazine ring to obtain the pi-conjugated polymer with the push-pull electronic structure and the main chain containing tetrazine ring,
wherein the sequence of the steps 1), 2) and 3) can be combined at will, the steps 1) and 2) can also be operated simultaneously, and the metal ion compound in the step 2) is a divalent magnesium salt, a divalent nickel salt, monovalent and divalent copper salts, a divalent zinc salt or a mixture thereof.
<7>, the method according to the preceding items, wherein the solubilizing agent in step 3) is selected from dimethyl sulfoxide, N-dimethylformamide or a mixture thereof.
<8>, the method according to the preceding items, wherein the molar ratio of the solubilizing agent to hydrazine hydrate in step 3) is between 1: 10 and 10: 1.
<9> the method according to the preceding items, wherein the molar ratio of the metal ion compound to hydrazine hydrate in step 2) is between 1: 10 and 10: 1.
<10> the method according to the previous items, wherein the molar ratio of the monomer of the structure represented by the general formula II to hydrazine hydrate is between 1: 100 and 100: 1.
Drawings
Fig. 1 shows the structural formula of a pi-conjugated polymer having a push-pull electron structure whose main chain contains a tetrazine ring according to example 1 of the present invention and a Nuclear Magnetic Resonance (NMR) carbon spectrum.
Fig. 2 shows an ultraviolet absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 1 of the present invention.
Fig. 3 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 1 of the present invention.
FIG. 4(a) shows calibration of a polystyrene calibration curve; fig. 4(b) shows a calibration curve for polystyrene, where calibration curve: a is 20.57932 ± 0.06758; b is 1.23316 +/-0.00739, so that the obtained pi-conjugated polymer with a tetrazine ring-containing main chain and a push-pull electronic structure (the weight average molecular weight of the terephthalonitrile tetrazine polymer is calculated to be more than or equal to 6500); FIG. 4(c) shows the molecular weight measured by gel permeation chromatography in the π -conjugated polymer with push-pull electronic structure having a main chain containing a tetrazine ring according to example 1 of the present invention.
FIG. 5 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 2 of the present invention.
FIG. 6 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 3 of the present invention.
FIG. 7 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 4 of the present invention.
FIG. 8 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 5 of the present invention.
Fig. 9 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 6 of the present invention.
FIG. 10 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 7 of the present invention.
FIG. 11 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 8 of the present invention.
FIG. 12 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 9 of the present invention.
Fig. 13 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 10 of the present invention.
FIG. 14 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 11 of the present invention.
FIG. 15 shows an infrared absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring according to example 12 of the present invention.
FIG. 16 shows an ultraviolet absorption spectrum of a tetrazine structure in a pi-conjugated polymer having a push-pull electron structure whose main chain contains a tetrazine ring according to comparative example 1 of the present invention.
FIG. 17 shows ultraviolet absorption spectra of tetrazine structures in pi-conjugated polymers having a push-pull electronic structure whose main chains contain tetrazine rings according to examples 16 to 17 of the present invention.
Detailed Description
The invention relates to a pi-conjugated polymer with a tetrazine ring-containing main chain and a push-pull electronic structure and a synthetic method thereof.
The term "having a push-pull electron structure" refers to a charge-rich conjugated structure and an electron-poor conjugated structure in a polymer chain link which are arranged at intervals.
In one aspect, the present invention provides (also sometimes referred to as a class of) pi-conjugated polymers having a tetrazine ring in the main chain, which have a push-pull electronic structure, the structure of the conjugated polymer having a structure represented by the formula:
wherein Ar1, Ar2 or Ar3 are the same or different from each other and are C as the number of carbon atoms4-C12The hetero atom of the heteroaryl group is selected from at least one of sulfur, oxygen and nitrogen, and examples thereof include phenyl, naphthyl, biphenyl, thienyl, terphenyl, and the like. R1，R2，R3Are identical or different from each other and are each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C with hetero atoms being sulfur, oxygen or nitrogen6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C2～C24Alkenyloxy, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl, substituted or unsubstituted C1～C24A sulfinyl group. R4, R5Is a terminal group formed by copolymerization or homopolymerization of a corresponding monomer, and can be one of amino, cyano, amidino or amidinohydrazino. m is an integer greater than 1; n is an integer equal to or greater than 0; p is an integer equal to or greater than 0. The selection range of m can be approximately in the range of 1-1000, for example, 10-800, 20-100, 100-700, 200-500, nThe selection range can be approximately in the range of 0-1000, for example, 10-800, 20-100, 100-700, 200-500, and the selection range of p can be approximately in the range of 0-10, for example, 1-8, 2-7, 3-5. (because the molecular weight measured by GPC exceeds the range of GPC column, the molecular weight of polymer at least exceeds 12.3 ten thousand, m is selected from 1-1000, n is selected from 0-1000, p is the number of aromatic rings contained in monomer, and the selected range is referred to 0-10.)
In the present disclosure, the "substituted or unsubstituted C1～C36The alkyl group "may be a linear or branched alkyl group, and the number of carbon atoms thereof is preferably C1-C18More preferably C1-C8Still more preferably C1-C4Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, decyl group, nonyl group, dodecyl group, octadecyl group, docosyl group, hexadecanyl group, and the like.
In the present disclosure, the "substituted or unsubstituted C2～C24The alkenyl group "may be a straight-chain or branched alkenyl group, and the number of carbon atoms thereof is preferably C2-C18More preferably C2-C12Still more preferably C2-C8Specific examples thereof include vinyl, propenyl, isopropenyl, butenyl, tert-butenyl, hexenyl, heptenyl, octenyl, hexylene, decenyl, nonenyl, dodecenyl, octadecenyl, tetracosenyl, and the like.
In the present disclosure, the "substituted or unsubstituted C6～C36Aryl "may be a monocyclic or fused ring aryl group, and the number of carbon atoms thereof is preferably C6-C24More preferably C6-C18Still more preferably C6-C12Specific examples thereof include phenyl, biphenyl, terphenyl, naphthalene, triphenyl, and the like.
In the present disclosure, the "substituted or unsubstituted C6～C36Heteroaryl "may be a monocyclic or fused ring aryl group, preferably having the number of carbon atoms of C6-C24More preferably C6-C18Still more preferably C6-C12Specific examples thereof include thienyl, furyl, imidazolyl, pyrazolyl, and the like.
In the present disclosure, the "substituted or unsubstituted C1～C24The alkoxy group "may be a linear or branched alkoxy group, and the number of carbon atoms thereof is preferably C1-C1sMore preferably C1-C12Still more preferably C1-C8Specific examples thereof include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, tert-butoxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, nonyloxy group, dodecyloxy group, octadecyloxy group, tetracosyloxy group, and the like.
In the present disclosure, the "substituted or unsubstituted C1～C24The alkylthio group "may be a straight or branched alkylthio group, and the number of carbon atoms thereof is preferably C1-C18More preferably C1-C12Still more preferably C1-C8Specific examples thereof include methylthio, ethylthio, propylthio, isopropylthio, butylthio, tert-butylthio, hexylthio, heptylthio, octylthio, decylthio, nonylthio, dodecylthio, octadecylthio, tetracosylthio, and the like.
In the present disclosure, the "substituted or unsubstituted C6～C24The aryloxy group "may be a monocyclic or condensed ring aryloxy group having preferably C as the carbon atom number6-C20More preferably C6-C14Still more preferably C6-C10Specific examples thereof include phenoxy group, biphenyloxy group, terphenyloxy group, naphthyloxy group, triphenyloxy group, and the like.
In the present disclosure, the "substituted or unsubstituted C2～C24Alkoxycarbonyl "may be a linear or branched alkoxycarbonyl group, the number of carbon atoms of which is preferably C2-C18More preferably C2-C12Still more preferably C2-C6Specific examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonylT-butoxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, nonyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, tetracosyloxycarbonyl, etc.
In the present disclosure, the "substituted or unsubstituted C2～C24The ester group "may be a linear or branched ester group, and the number of carbon atoms thereof is preferably C2-C18More preferably C2-C12Still more preferably C2-C6Specific examples thereof include carbomethoxy group, carbethoxy group, propisocarbonyl group, isopropylester group, butylester group, tert-butylester group, hexylester group, heptylester group, octylester group, decylester group, nonylester group, dodecylester group, octadecylester group, tetracosylate group, and the like.
In the present disclosure, the "substituted or unsubstituted C2～C24The amide group "may be a linear or branched amide group, and the number of carbon atoms thereof is preferably C2-C18More preferably C2-C12Still more preferably C2-C6Specific examples thereof include carboxamido, acetamido, propionamido, isopropamide, butyramido, tert-butyramido, caproyl, enanthamido, caprylamido, capriamido, nonanamido, dodecanamido, octadecanamido, tetracosanamido, and the like.
In the present disclosure, the "substituted or unsubstituted C1～C24The sulfonyl group "may be a linear or branched sulfonyl group, and the number of carbon atoms thereof is preferably C1-C18More preferably C1-C12Still more preferably C1-C6Specific examples thereof include methanesulfonyl, ethanesulfonyl, propanesulfonyl, isopropylsulfonyl, butanesulfonyl, tert-butanesulfonyl, hexanesulfonyl, heptanesulfonyl, octanesulfonyl, decanesulfonyl, nonanesulfonyl, dodecanesulfonyl, octadecanosulfonyl, icosanesulfonyl, and the like.
In the present disclosure, the "substituted or unsubstituted C1～C24The sulfinyl group "may be a straight-chain or branched sulfinyl group having preferably C1-C18More preferably, it isC1-C12Still more preferably C1-C6Specific examples thereof include methanesulfinyl, ethanesulfinyl, propanesulfinyl, isopropylsulfinyl, butanesulfinyl, tert-butanesulfinyl, hexanesulfonyl, heptanesulfinyl, octanesulfinyl, decanesulfonyl, nonanesulfonyl, dodecanesulfonyl, octadecanoylsulfinyl, icosanesulfonyl, and the like.
Specifically, the pi-conjugated polymer with a tetrazine ring in the main chain and a push-pull electronic structure can be a polymer shown in the following general formula IA, IB, IC, ID, IE or IF:
wherein R is5、R6、R7、R8Each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl, substituted or unsubstituted C1～C24A sulfinyl group.
The end groups R are respectively selected from end groups formed by copolymerization or homopolymerization of corresponding monomers, and can be one of amino, cyano, amidino or amidino hydrazine groups;
n is an integer of 1 or more;
n1 is an integer of 1 or more;
m is an integer of 1 or more.
The invention relates to a pi-conjugated polymer with a tetrazine ring-containing main chain and a push-pull electronic structure, wherein a copolymer with m, n and p having a series of values can be easily synthesized by controlling the proportion of different monomer components in the conjugated polymer.
In the present invention, the monomers which can be used for synthesizing the above-mentioned kind of pi-conjugated polymers having a main chain containing a tetrazine ring and having a push-pull electron structure have structural features represented by the following formula:
wherein Ar4 is C4-C12The hetero atom of the heteroaryl group is selected from one of sulfur, oxygen and nitrogen, and examples thereof are phenyl, naphthyl, biphenyl, thienyl, terphenyl and the like. X1And X2Each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C2～C24Alkenyloxy, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl, substituted or unsubstituted C1～C24A sulfinyl group.
Wherein, said "substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C2～C24Alkenyloxy, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl, substituted or unsubstituted C1～C24Each substituent in sulfinyl "has the meaning as described above.
In a second aspect, the present invention provides a method for synthesizing a pi-conjugated polymer having a structure of formula I according to the first aspect directly from monomers having structural features of formula II as described above, wherein the method comprises:
1) dissolving a monomer with a structure shown in a general formula II in hydrazine hydrate;
2) dissolving a compound containing metal ions in hydrazine hydrate;
3) dissolving a solubilizer of the polymer in hydrazine hydrate;
4) reacting the reaction mixture at 60-150 ℃, preferably 70-120 ℃, more preferably 80-90 ℃ for 0.5-48 hours to obtain the pi-conjugated polymer with the tetrazine ring in the main chain and the push-pull electronic structure;
5) the pi-conjugated polymer with the main chain containing dihydrotetrazine ring and the push-pull electronic structure is oxidized to obtain the pi-conjugated polymer with the main chain containing tetrazine ring and the push-pull electronic structure.
In the above preparation method, the order of steps 1), 2), 3) may be arbitrarily combined, and the steps 1) and 2) may be simultaneously performed.
Herein, the term "hydrazine hydrate" refers to hydrazine hydrate, which is commercially available or can be obtained synthetically by methods known in the art.
In the present context, the metal ion in the term "metal ion-containing compound" means magnesium, nickel, copper, zinc and the like, preferably a divalent magnesium salt, a divalent nickel salt, monovalent and divalent copper salts, a divalent zinc salt or a mixture thereof, and the like, and usually a halide salt, a sulfate salt, an acetate salt and the like. In the present invention, the metal ion compound functions as a catalyst in the polycondensation reaction.
In the above preparation method, the solubilizer plays a role in allowing the structural monomer represented by the general formula II and the metal ion compound to be completely dissolved in hydrazine hydrate, thereby enabling a homogeneous reaction to be formed. Applicants predict that solubilizers that are inert to the reaction and that perform this function can be used in the present invention. Thus, the solubilizing agent described in step 3) of the above-mentioned production method is inert dimethylsulfoxide, N-dimethylformamide or a mixture thereof.
In the above preparation process, the molar ratio of the reactive monomer such as the structural monomer represented by the formula II to hydrazine hydrate is in the range of 1: 100 to 100: 1, preferably 10: 1 to 1: 100, most preferably 1: 5.
In the above preparation method, the molar ratio of the metal ion compound to hydrazine hydrate is in the range of 10: 1 to 1: 10, most preferably 1: 1.
In the above production method, the "oxidation process" means oxidation in the usual sense. For example, specific examples thereof include: oxidation processes using oxidizing agents, such as a mixture of sodium nitrite and acetic acid, or direct air oxidation.
The applicant believes without being bound by any theory that the present invention enables the direct use of dinitrile monomers and hydrazine hydrate to synthesize a pi-conjugated polymer having a tetrazine ring in the main chain with a push-pull electron structure because the present application uses a co-solvent such as dimethylsulfoxide, N-dimethylformamide or a mixture thereof to allow the reaction to proceed in a homogeneous phase and thus to increase the reaction temperature, allowing the current reaction to proceed at 60 to 150 c, which is typical in the prior art and is not more than 60 c. The inventor finds through experiments that the chain length can be increased after the solubilizer is adopted, and the molecular weight of the polymer is increased. The molecular weight of the t-conjugated polymer having a push-pull electronic structure with a tetrazine ring in the main chain obtained by the present inventors may be in the range of about 6500-123000, and for example, the lower limit may be 7000, 7500, 8000 or others.
Innovation and industrial application prospect of the invention
At present, no literature reports that a pi-conjugated polymer containing a tetrazine ring in the main chain is directly synthesized. The invention provides a design and a synthesis method of a pi-conjugated polymer with a main chain containing a tetrazine ring. The invention relates to a tetra-oxazine ring-containing pi-conjugated polymer with a push-pull electronic structure, which is selected from at least one polymer shown as a general formula I, has the advantages of regular structure and high molecular weight, and provides a simple, convenient, high-efficiency and simple-operation method for synthesizing a main chain tetra-oxazine ring-containing pi-conjugated polymer by hydrazine hydrate and a monomer shown as a general formula II for the first time. The synthesis method has the advantages of low cost of raw materials, simple operation and stable property, and the prepared pi-conjugated polymer with the main chain containing the tetrazine ring can be widely applied to the field of organic electronics and is expected to generate great social value and economic value.
The invention is further illustrated by the following specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way.
Examples
The raw material "hydrazine hydrate" was purchased from sahn chemical technology (shanghai) ltd.
Example 1: and (3) synthesizing a pi-conjugated polymer with a tetrazine ring-containing main chain and a push-pull electronic structure.
Adding hydrazine hydrate (60mmol, 3mL) into a 10mL reaction bottle, dissolving terephthalonitrile (1.5g, 12mmol) in the hydrazine hydrate, simultaneously dissolving magnesium chloride (5.7g, 60mmol) in the hydrazine hydrate, adding a proper amount of dimethyl sulfoxide into the system, heating at 100 ℃ for 24 hours to obtain a pi-conjugated polymer with a push-pull electronic structure and a dihydrotetrazine ring in a main chain, dissolving the conjugated polymer with the dihydrotetrazine ring in a sodium nitrite (1.65g, 1mol/L, 24mL) solution under the ice bath condition, and slowly adding dilute vinegar into the systemOxidizing with acid (1mol/L, 24mL) to obtain the terephthalonitrile tetrazine polymer. Chemical shift of carbon atom at chemical shift 161.29 in the solid-state nuclear magnetic carbon spectrum of fig. 1 is the chemical shift of C ═ N of the tetrazine ring; in FIG. 2, the absorption band of 500-600 nm of the ultraviolet absorption spectrum is the transition absorption from the non-bond orbit of the tetrazine ring to the pi-reverse bond orbit; the infrared absorption spectrum in FIG. 3 shows a characteristic absorption peak (about 1390 cm) of the tetrazine ring-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described.
Example 2:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that magnesium sulfate was used instead of magnesium chloride. The characteristic absorption peak of the tetrazine ring can be obviously observed in an infrared characterization map (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. The structural characterization of the polymer is shown in figure 5.
Example 3:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that nickel chloride was used instead of magnesium chloride. The characteristic absorption peak of the tetrazine ring can be obviously observed in an infrared characterization map (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. The structural characterization of the polymer is shown in figure 6.
Example 4:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that copper chloride was used instead of magnesium chloride. The characteristic absorption peak of the tetrazine ring can be obviously observed in an infrared characterization map (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. The structural characterization of the polymer is shown in figure 7.
Example 5:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that zinc chloride was used instead of magnesium chloride. The tetrazine ring being clearly observable in an infrared characterization spectrumCharacteristic absorption peak (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. The structural characterization of the polymer is shown in figure 8.
Example 6: a pi-conjugated polymer having a push-pull electronic structure with a tetrazine ring in the main chain was prepared in the same manner as in example 1, except that the monomer 4, 4' -biphenylcarbonitrile having a structure represented by the formula II was used instead of terephthalonitrile. The characteristic absorption peak of the tetrazine ring can be obviously observed in an infrared characterization map (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. The structural characterization of the polymer is shown in figure 9.
Example 7:
a pi-conjugated polymer having a push-pull electronic structure with a tetrazine ring in the main chain was prepared in the same manner as in example 1, except that the monomer 2, 5-dicyanothiophene of the structure shown in formula II was used instead of terephthalonitrile. The characteristic absorption peak of the tetrazine ring can be obviously observed in an infrared characterization map (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. The structural characterization of the polymer is shown in figure 10.
Example 8:
a pi-conjugated polymer having a push-pull electron structure having a tetrazine ring in its main chain was prepared in the same manner as in example 1, except that 1, 4-dibutoxy-2, 5-dicyanobenzene, a monomer having a structure represented by formula II, was used instead of terephthalonitrile. The characteristic absorption peak of the tetrazine ring can be obviously observed in an infrared characterization map (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. The structural characterization of the polymer is shown in figure 11.
Example 9:
a pi-conjugated polymer having a push-pull electron structure having a tetrazine ring in the main chain was prepared in the same manner as in example 1, except that 1, 4-dihexyloxy-2, 5-dicyanobenzene, a monomer having a structure represented by formula II, was used instead of terephthalonitrile. The characteristic absorption peak of the tetrazine ring can be obviously observed in an infrared characterization map (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. PolymerisationThe structural characterization of the article is shown in FIG. 12.
Example 10:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that heating at 60 c was used instead of heating only at 100 c. The characteristic absorption peak of the tetrazine ring can be obviously observed in an infrared characterization map (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. The structural characterization of the polymer is shown in figure 13.
Example 11:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that heating at 150 c was used instead of heating only at 100 c. The characteristic absorption peak of the tetrazine ring can be obviously observed in an infrared characterization map (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. By comparing the different temperatures of 60 ℃, 100 ℃ and 150 ℃, we can find that 100 ℃ is the optimal reaction temperature. The structural characterization of the polymer is shown in figure 14.
Example 12:
a pi-conjugated polymer having a push-pull electronic structure with a tetrazine ring-containing main chain was prepared in the same manner as in example 1, except that one or more of N, N-dimethylformamide and the like, which are similar to the inert solvent stable at high temperature, were added to the system instead of adding a proper amount of dimethyl sulfoxide to the system. The characteristic absorption peak of the tetrazine ring can be obviously observed in an infrared characterization map (about 1390 cm)-1) The synthesis of a conjugated polymer having a tetrazine ring structure in the main chain is described. The structural characterization of the polymer is shown in figure 15.
Comparative example 1:
a pi-conjugated polymer having a push-pull electronic structure with a tetrazine ring in its main chain was prepared in the same manner as in example 1, except that one or more solubilizers in a high-temperature stable inert solvent like N, N-dimethylformamide and the like were not added to the system. The polymer prepared is shown in figure 16. According to the literature, the tetrazine ring has obvious absorption at 500-600 nm, and under the same concentration, the characteristic absorption of the tetrazine ring of the tetrazine polymer obtained in comparative example 1 can be obviously reduced through an ultraviolet absorption spectrum, which shows that the chain length of the polymer is shorter due to no addition of the solubilizer, and the molecular weight of the tetrazine polymer synthesized without the addition of the solubilizer is lower than 6000 according to the estimation of Lambert beer law.
Example 13:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that the equivalent ratio of the monomer having a structure represented by the general formula II to hydrazine hydrate was "100: 1" instead of the equivalent ratio of only the monomer having a structure represented by the general formula II of "1: 5" being dissolved in hydrazine hydrate. Since the molecular weight of the polymer of the polycondensation reaction is greatly influenced by the ratio of the amounts of substances between the two monomers, the actual yield is greatly different due to the difference in the ratio of the monomers. When the theoretical yield is closer to the actual yield, the more regular structure is shown, and the chain length of the polymer is long, the molecular weight is higher, so the actual yield is not influenced by the end group. When the polymer molecular chain was long, the influence of the terminal group on the whole molecular weight was negligible, so that the theoretical yield was calculated as the ratio of the amount of the mer of terephthalonitrile tetrazine polymer/the amount of the material of terephthalonitrile monomer was 156/128-1.22. Specific results are shown in table 1.
Example 14:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that the equivalent ratio of the monomer having a structure represented by the general formula II to hydrazine hydrate was "10: 1" instead of the equivalent ratio of only the monomer having a structure represented by the general formula II of "1: 5" was dissolved in hydrazine hydrate. Specific results for the polymers prepared are shown in table 1.
Example 15:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that the equivalent ratio of the monomer having a structure represented by the general formula II to hydrazine hydrate was "1: 100" instead of the equivalent ratio of only the monomer having a structure represented by the general formula II of "1: 5" being dissolved in hydrazine hydrate. Specific results for the polymers prepared are shown in table 1.
Table 1: the difference between the actual and theoretical yields of the tetrazine polymers obtained in examples 13 to 15
| Category of implementation | Mass of centrifugal tube | After freeze drying | Quality of | Actual yield | Effect measurement |
| Example 1 | 11.6326g | 13.4432g | 1.8106g | 1.18 | Closest to theoretical yield |
| Example 13 | 11.5441g | 12.8790g | 1.3349g | 0.87 | Maximum deviation |
| Example 14 | 11.3847g | 12.8578g | 1.4731g | 0.96 | Deviation from moderate |
| Example 15 | 11.6326g | 13.2437g | 1.6111g | 1.05 | Deviation minimum |
From the data in Table 1, we can see that the optimum reactant molar ratio of the monomer of the structure shown in formula II to hydrazine hydrate is "1: 5", and the reactant molar ratio of the monomer of the structure shown in formula II to hydrazine hydrate is in the range of "1: 100" to "100: 1", preferably "10: 1" to "1: 100".
Example 16:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that magnesium chloride was dissolved in hydrazine hydrate in an equivalent ratio of magnesium chloride to hydrazine hydrate of "10: 1" instead of magnesium chloride in an equivalent ratio of only "1: 1". Specific results of the polymers prepared are shown in table 2 and fig. 17.
Example 17:
a pi-conjugated polymer having a push-pull electronic structure whose main chain contains a tetrazine ring was prepared in the same manner as in example 1, except that magnesium chloride was dissolved in hydrazine hydrate in an equivalent ratio of magnesium chloride to hydrazine hydrate of "1: 10" instead of magnesium chloride in an equivalent ratio of only "1: 1". Specific results of the polymers prepared are shown in table 2 and fig. 17.
Table 2: the difference between the actual and theoretical yields of the tetrazine polymers obtained in examples 16 to 17
| Category of implementation | Mass of centrifugal tube | After freeze drying | Quality of | Actual yield | Effect measurement |
| Example 1 | 11.6326g | 13.4432g | 1.8106g | 1.18 | Closest to theoretical yield |
| Example 16 | 11.7460g | 13.3878g | 1.6418g | 1.07 | The next step of deviation |
| Example 17 | 11.5739g | 13.0776g | 1.5037g | 0.98 | Maximum deviation |
From the data in Table 2, we can find that the optimum reactant molar ratio of magnesium chloride to hydrazine hydrate is "1: 1", and the reactant molar ratio of magnesium chloride to hydrazine hydrate preferably ranges from "1: 10" to "10: 1".
Although the invention disclosed in the present application has been described in detail, other embodiments that can be modified or substituted by equivalents by those skilled in the art without departing from the inventive concept disclosed herein are also encompassed by the present invention.
Claims (10)
1. A pi-conjugated polymer with a main chain containing a tetrazine ring has a push-pull electron structure and a structure shown in a general formula I,
wherein Ar1, Ar2 or Ar3 are the same or different from each other and each independently is a carbon atom number of C4-C12The heteroaryl group of (a), the heteroatom of the heteroaryl group being selected from at least one of sulfur, oxygen and nitrogen; r1、R2、R3Are identical or different from each other and are each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C with hetero atoms being sulfur, oxygen or nitrogen6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl or substituted or unsubstituted C1～C24A sulfinyl group; and R is4And R5Are the same or different from each other, and are independently selected from at least one of amino, cyano, amidino and amidinohydrazino groups.
m is an integer greater than 1; n is an integer equal to or greater than 0; p is an integer equal to or greater than 0.
2. The pi-conjugated polymer having a main chain containing a tetrazine ring according to claim 1, wherein the Ar1, Ar2 or Ar3 is independently selected from phenyl, naphthyl, biphenyl or thienyl.
3. The n-conjugated polymer having a main chain containing a tetrazine ring according to claim 1, which is a polymer represented by general formula IA, IB, IC, ID, IE or IF:
wherein R is5、R6、R7、R8Each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl, substituted or unsubstituted C1～C24A sulfinyl group;
the end group R is selected from at least one of amino, cyano, amidino and amidinohydrazino;
n is an integer of 1 or more;
n1 is an integer of 1 or more;
m is an integer having a length equal to 1.
4. The pi-conjugated polymer having a main chain containing a tetrazine ring according to claim 1, wherein the pi-conjugated polymer having a push-pull electron structure having a main chain containing a tetrazine ring is synthesized but contains two cyano groups, and has a structure represented by the following general formula II:
X1，X2each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl, substituted or unsubstituted C1～C24Sulfinyl group, Ar4 is C4-C12The heteroaryl group, wherein the heteroatom of the heteroaryl group is selected from one of sulfur, oxygen and nitrogen.
5. The pi-conjugated polymer having a main chain containing a tetrazine ring according to claim 1, wherein the monomer having the structure represented by the general formula II is selected from the group consisting of:
wherein R is5Each independently selected from hydrogen, substituted or unsubstituted C1～C36Alkyl, substituted or unsubstituted C2～C24Alkenyl, substituted or unsubstituted C6～C36Aryl, substituted or unsubstituted C6～C36Heteroaryl, substituted or unsubstituted C1～C24Alkoxy, substituted or unsubstituted C1～C24Alkylthio, substituted or unsubstituted C6～C24Aryloxy, substituted or unsubstituted C2～C24Alkoxycarbonyl, substituted or unsubstituted C2～C24Ester group, substituted or unsubstituted C2～C24Amido, substituted or unsubstituted C1～C24Sulfonyl, substituted or unsubstituted C1～C24A sulfinyl group; n1 is an integer of 1 or more.
6. A method for producing a n-conjugated polymer having a main chain containing a tetrazine ring as described in any one of claims 1 to 5, the method comprising:
1) dissolving a monomer with a structure shown in a general formula II in hydrazine hydrate;
2) dissolving a compound containing metal ions in hydrazine hydrate;
3) dissolving a solubilizer of the polymer in hydrazine hydrate;
4) reacting the reaction mixture at 60-150 ℃ for 0.5-48 hours to obtain the pi-conjugated polymer with the main chain containing dihydrotetrazine ring and having a push-pull electronic structure;
5) oxidizing the pi-conjugated polymer with a push-pull electronic structure and a main chain containing dihydrotetrazine ring to obtain the pi-conjugated polymer with the push-pull electronic structure and the main chain containing tetrazine ring,
wherein the sequence of the steps 1), 2) and 3) can be combined at will, the steps 1) and 2) can also be operated simultaneously, and the metal ion compound in the step 2) is a divalent magnesium salt, a divalent nickel salt, monovalent and divalent copper salts, a divalent zinc salt or a mixture thereof.
7. The process according to claim 6, wherein the solubilizing agent in step 3) is selected from dimethyl sulfoxide, N-dimethylformamide or a mixture thereof.
8. The process according to claim 6, wherein the molar ratio of the solubilizing agent to hydrazine hydrate in step 3) is between 1: 10 and 10: 1.
9. The process of claim 6, wherein the molar ratio of the metal ion compound to hydrazine hydrate in step 2) is between 1: 10 and 10: 1.
10. The method of claim 6, wherein the molar ratio of the monomer of the structure represented by the general formula II to hydrazine hydrate is between 1: 100 and 100: 1.
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| CN112142958A (en) * | 2020-09-27 | 2020-12-29 | 中国科学院上海高等研究院 | Tetrazine aromatic skeleton polymer, functional derivative and synthetic method thereof |
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| CN112142958A (en) * | 2020-09-27 | 2020-12-29 | 中国科学院上海高等研究院 | Tetrazine aromatic skeleton polymer, functional derivative and synthetic method thereof |
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