CN113773489B - Poly (amide-thioamide) polymer and synthetic method and application thereof - Google Patents

Poly (amide-thioamide) polymer and synthetic method and application thereof Download PDF

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CN113773489B
CN113773489B CN202111096123.6A CN202111096123A CN113773489B CN 113773489 B CN113773489 B CN 113773489B CN 202111096123 A CN202111096123 A CN 202111096123A CN 113773489 B CN113773489 B CN 113773489B
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thioamide
amide
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amine monomer
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CN113773489A (en
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唐本忠
胡蓉蓉
黎丰霆
秦安军
赵祖金
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South China University of Technology SCUT
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    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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Abstract

The invention provides a poly (amide-thioamide) polymer, a synthetic method and application thereof, belonging to the field of high molecular chemical materials. The polymer synthesis and sequence regulation method comprises the following steps: under the inert gas environment, adding a first bifunctional amine monomer, maleic anhydride and elemental sulfur into an organic solvent to react to obtain a reaction liquid, adding a second bifunctional amine monomer under the condition of needing sequence regulation and control to react, and then diluting, filtering and settling the reaction liquid to obtain the poly (amide-thioamide) or the sequence-controllable poly (amide-thioamide). The synthesis method can obtain poly (amide-thioamide) with clear and regular structure at high yield, and the obtained polymer has high molecular weight, thereby successfully realizing the high-efficiency synthesis of poly (amide-thioamide) with various structural types by multiple components by a one-pot method.

Description

Poly (amide-thioamide) polymer and synthetic method and application thereof
Technical Field
The invention relates to the technical field of high molecular chemical materials, in particular to a poly (amide-thioamide) polymer and a synthetic method and application thereof.
Background
The sulfur-containing polymer with the characteristics of self-repairing performance, metal ion coordination capacity, high refractive index, heteroatom structure, dynamic bond and the like has wide application prospect in the aspects of ion adsorption materials, optical materials, biological materials, degradable materials and the like. At present, few reports of poly (amide-thioamides) synthesis have been made. Most of the existing synthetic methods for sulfur-containing polymers have the problems of high raw material cost, difficult acquisition, harsh synthetic conditions, difficult operation, limited product structure, high monomer toxicity or high toxicity of byproducts and the like, so the sulfur-containing polymers have a larger distance from the actual industrial production.
In biological macromolecules, the achievement and differentiation of their functions often depends on the differences in their sequence structures. Therefore, the research on the sequence controllable polymer with the same sequence structure characteristics has prospective and guiding significance on the design, synthesis and application of the functional polymer material. On the other hand, the synthesis methods and examples of the sequence-controllable polymers are still few, and there are many limitations, such as high preparation cost and time cost, low yield and molecular weight, many synthesis steps, complex operation, limited synthesis structure, and the like. Therefore, the development of new methods for synthesizing sequence-controllable polymers to overcome these problems is of great importance both at the scientific level and in practical production.
Multicomponent polymerization (MCP) has the characteristics of mild reaction conditions, simple operation, various product structures and the like, and can effectively avoid many problems in the synthesis of sulfur-containing polymers. The development of the petroleum industry has led to an increase in the production and storage of elemental sulphur as a by-product year after year, however, elemental sulphur is easily oxidized to sulphur oxides during storage, which makes the storage of sulphur a great environmental problem. The multicomponent polymerization method can use low-cost elemental sulfur as a raw material to efficiently synthesize the sulfur-containing polymer, so that the cost is greatly reduced, and the multicomponent polymerization method is more environment-friendly. However, the sulfur-containing polymers obtained by the multicomponent polymerization method still have certain structural limitations, and the development of new reaction methods is still needed to expand the variety and structural diversity of the polymers and reduce the reaction cost.
Meanwhile, the multi-component Tandem Polymerization (multi-component Tandem Polymerization) method not only has various advantages of multi-component Polymerization, but also can control the reaction sequence and the structure of a reaction product by feeding the reaction step by step, thereby realizing the sequential control of the polymer by using a one-pot, two-step and three-component method. There are only a few examples of the synthesis of polymers with controllable sequences by multicomponent tandem polymerization, and the studies on the use of elemental sulfur as a raw material or the synthesis of sulfur-containing polymers have not been made before.
Therefore, obtaining a method for synthesizing a sulfur-containing polymer with high efficiency and low cost by using a sulfur simple substance as a raw material is a technical problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a poly (amide-thioamide) polymer, a synthesis method and application thereof, wherein the poly (amide-thioamide) polymer is prepared by carrying out multicomponent polymerization or multicomponent tandem polymerization on elemental sulfur, a difunctional amine monomer and maleic anhydride.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a poly (amide-thioamide) polymer, the structure of which comprises the following structure:
Figure BDA0003264453950000021
wherein R is1，R2，R3Independently are alkylene, alkyleneoxy, arylene, alkylene-aryl-alkylene, arylene-alkylene-arylene, arylene- (X)h-one of arylene, arylene-Y-arylene, arylene-arylene, cycloalkylene, fused heterocyclic group in which one or more benzene rings are fused with a heterocyclic ring, group in which a plurality of benzene rings are combined with a nitrogen atom, group in which a plurality of benzene rings are combined with a vinylene group; wherein X is S or O, h is a natural number, Y is NH, C ═ O and-Si (Z)2-one of the above, Z is an alkyl group.
Further, the arylene group is a substituted or unsubstituted aryl group, and the substituent is an alkyl group.
Further, the poly (amide-thioamide) polymer comprises in its structure
Figure BDA0003264453950000022
Structure;
or comprises
Figure BDA0003264453950000031
Figure BDA0003264453950000032
Structure;
or comprises
Figure BDA0003264453950000033
Figure BDA0003264453950000034
Structure of the product。
The invention provides a method for synthesizing a poly (amide-thioamide) polymer, which comprises the following steps:
under the inert gas environment, adding difunctional amine monomer, maleic anhydride and elemental sulfur into an organic solvent to react to obtain reaction liquid, and diluting, filtering and settling the reaction liquid to obtain the poly (amide-thioamide) polymer.
Further, the molar ratio of the difunctional amine monomer to the maleic anhydride to the elemental sulfur is 1: 0.5-1.95: 1.5 to 6.
Further, the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-methylpiperidine, toluene, N-dimethylacetamide, tetrahydrofuran, 1, 4-dioxane and N-methylpyrrolidone.
Further, the difunctional amine monomer comprises the following compounds:
Figure BDA0003264453950000041
wherein n and k are integers of 1-20.
The invention provides a poly (amide-thioamide) polymer, wherein the polymer is a poly (amide-thioamide) polymer with controllable sequence, and the structural formula of the polymer is as follows:
Figure BDA0003264453950000042
wherein n is an integer of 2 to 500;
R1，R2，R3，R4，R5，R6independently are alkylene, alkyleneoxy, arylene, alkylene-aryl-alkylene, arylene-alkylene-arylene, arylene- (X)hArylene, arylene-Y-arylene, arylene-arylene, cycloalkylene, fused heterocyclic group in which one or more benzene rings are fused to a heterocyclic ring, group in which a plurality of benzene rings are combined with a nitrogen atom, group of a plurality of benzene rings and vinyleneOne of the groups of (a) and (b); wherein X is S or O, h is a natural number, Y is NH, C ═ O and-Si (Z)2-one of Z is alkyl;
further, the arylene group is a substituted or unsubstituted aryl group, and the substituent is an alkyl group.
Further, the structural formula of the sequence-controllable poly (amide-thioamide) polymer comprises the following structure:
Figure BDA0003264453950000051
the invention provides a method for synthesizing a poly (amide-thioamide) polymer, which comprises the following steps:
under the inert gas environment, adding a first bifunctional amine monomer, maleic anhydride and elemental sulfur into an organic solvent to react to obtain a reaction solution, adding a second bifunctional amine monomer into the reaction solution to react, and then diluting, filtering and settling the reaction solution to obtain the sequence-controllable poly (amide-thioamide) polymer.
Further, the molar ratio of the total amount of the difunctional amine monomer, the maleic anhydride and the elemental sulfur is 1.0: 0.5-1.95: 1.5 to 6, wherein the molar ratio of the first difunctional amine monomer to the second difunctional amine monomer is 1: 0.5 to 1.5.
Further, the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-methylpiperidine, toluene, N-dimethylacetamide, tetrahydrofuran, 1, 4-dioxane and N-methylpyrrolidone.
Further, the first difunctional amine monomer and the second difunctional amine monomer each comprise the following compounds:
Figure BDA0003264453950000061
(ii) a Wherein n and k are integers of 1-20.
The invention provides application of poly (amide-thioamide) polymer in the photoelectric field and the metal ion adsorption field.
The invention has the beneficial effects that:
(1) the synthesis method of the present invention allows the synthesis of poly (amide-thioamides), which has been rarely reported previously. Meanwhile, the invention can realize the one-step conversion from elemental sulfur to pure alkyl chain polythioamide without a benzene ring structure, which is rarely reported before.
(2) The monomers used in the synthesis method are all simple organic matters which are industrially produced in large quantities and can be obtained at low cost through commercial purchase, thereby realizing the mass production of the polymer by the polymerization method.
(3) The synthetic method can synthesize the sequence-controllable poly (amide-thioamide) with the characteristics of high yield (95%) and high molecular weight (17300g/mol), realize the direct conversion from elemental sulfur to the sequence-controllable sulfur-containing polymer, and realize the low-cost synthesis of the sequence-controllable sulfur-containing polymer.
(4) The synthesis method can obtain poly (amide-thioamide) with a clear and regular structure at high yield (95%), and the obtained polymer has high molecular weight (86900g/mol), so that poly (amide-thioamide) with various structural varieties can be synthesized efficiently by multiple components by a one-pot method.
(5) The poly (amide-thioamide) provided by the invention has the property of emitting light under ultraviolet excitation, and has potential application in the photoelectric field. Meanwhile, the thioamide group contained in the polymer is found to have a function of adsorbing metal ions. The function of the polymer for adsorbing metal ions and the luminescence property show that the polymer can be applied to the fields of heavy metal ion removal and ion monitoring.
Drawings
FIG. 1 is a comparison of nuclear magnetic resonance hydrogen spectra in deuterated dimethylsulfoxide of poly (amide-thioamide) P1 (FIG. 1D) prepared in example 1 of the present invention and a model polymer represented by formula (9) (FIG. 1C) prepared accordingly, as well as P-xylylenediamine (FIG. 1B) and maleic anhydride (FIG. 1A) employed;
FIG. 2 is a graph comparing the nuclear magnetic resonance carbon spectra in deuterated dimethyl sulfoxide of poly (amide-thioamide) P1 (FIG. 2D) prepared in example 1 of the present invention and a model polymer represented by formula (9) (FIG. 2C) prepared accordingly, and also of P-xylylenediamine (FIG. 2B) and maleic anhydride (FIG. 2A) used;
FIG. 3 is a dimethylsulfoxide solution (5X 10 concentration) of poly (amide-thioamide) P1 prepared in example 1 of the invention-4mol/L) (FIG. 3A) and fluorescence emission spectrum (FIG. 3B);
FIG. 4 shows the NMR spectrum of poly (amide-thioamide) P4 in deuterated DMSO prepared in example 4 of the present invention.
Detailed Description
The present invention provides a poly (amide-thioamide) polymer having the structure comprising:
Figure BDA0003264453950000071
wherein R is1，R2，R3Independently are alkylene, alkyleneoxy, arylene, alkylene-aryl-alkylene, arylene-alkylene-arylene, arylene- (X)h-one of arylene, arylene-Y-arylene, arylene-arylene, cycloalkylene, fused heterocyclic group in which one or more benzene rings are fused with a heterocyclic ring, group in which a plurality of benzene rings are combined with a nitrogen atom, group in which a plurality of benzene rings are combined with a vinylene group; wherein X is S or O, h is a natural number, Y is NH, C ═ O and-Si (Z)2-one of the above, Z is an alkyl group.
In the present invention, the arylene group is a substituted or unsubstituted aryl group, and the substituent is an alkyl group.
In the present invention, the poly (amide-thioamide) polymer comprises in its structure
Figure BDA0003264453950000081
Structure;
or comprises
Figure BDA0003264453950000082
Figure BDA0003264453950000083
Structure;
or comprises
Figure BDA0003264453950000084
Figure BDA0003264453950000085
And (5) structure.
The invention provides a method for synthesizing a poly (amide-thioamide) polymer, which comprises the following steps:
under the inert gas environment, adding difunctional amine monomer, maleic anhydride and elemental sulfur into an organic solvent to react to obtain reaction liquid, and diluting, filtering and settling the reaction liquid to obtain the poly (amide-thioamide) polymer.
In the invention, the molar ratio of the difunctional amine monomer to the maleic anhydride to the elemental sulfur is 1: 0.5-1.95: 1.5-6, preferably 1: 0.8-1.8: 2.0 to 5, and more preferably 1: 1.0: 3.5.
in the present invention, the difunctional amine monomer comprises the following compounds:
Figure BDA0003264453950000091
wherein n and k are integers of 1-20.
The difunctional amine monomer is preferably:
Figure BDA0003264453950000092
the difunctional amine monomer is further preferably:
Figure BDA0003264453950000101
in the present invention, the inert gas is preferably nitrogen and/or argon, and more preferably nitrogen.
In the present invention, the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-methylpiperidine, toluene, N-dimethylacetamide, tetrahydrofuran, 1, 4-dioxane, and N-methylpyrrolidone, and preferably one or more of dimethyl sulfoxide, N-dimethylformamide, and N-methylpiperidine.
In the invention, the settling agent used for settling comprises one or more of methanol, brine and ammonium chloride solution, and preferably methanol.
In the present invention, the concentration of the bifunctional amine monomer in the solvent is 0.1 to 2.0mol/L, preferably 0.5 to 1.5mol/L, and more preferably 1.0 mol/L.
In the invention, the reaction temperature is 40-100 ℃, and the reaction time is 4-16 h; preferably, the reaction temperature is 50-90 ℃, and the reaction time is 5-15 h; further preferably, the reaction temperature is 60-80 ℃, and the reaction time is 8-12 h.
The invention provides a poly (amide-thioamide) polymer, wherein the polymer is a poly (amide-thioamide) polymer with controllable sequence, and the structural formula of the polymer is as follows:
Figure BDA0003264453950000102
wherein n is an integer of 2 to 500;
R1，R2，R3，R4，R5，R6independently are alkylene, alkyleneoxy, arylene, alkylene-aryl-alkylene, arylene-alkylene-arylene, arylene- (X)h-one of arylene, arylene-Y-arylene, arylene-arylene, cycloalkylene, fused heterocyclic group in which one or more benzene rings are fused with a heterocyclic ring, group in which a plurality of benzene rings are combined with a nitrogen atom, group in which a plurality of benzene rings are combined with a vinylene group; wherein X is S or O, h is a natural number, Y is NH, C ═ O and-Si (Z)2-one of the above, Z is an alkyl group.
In the present invention, the arylene group is a substituted or unsubstituted aryl group, and the substituent is an alkyl group.
In the present invention, the structural formula of the sequence-controllable poly (amide-thioamide) polymer is preferably:
Figure BDA0003264453950000111
the invention provides a method for synthesizing a poly (amide-thioamide) polymer, which comprises the following steps:
under the inert gas environment, adding a first bifunctional amine monomer, maleic anhydride and elemental sulfur into an organic solvent to react to obtain a reaction solution, adding a second bifunctional amine monomer into the reaction solution to react, and then diluting, filtering and settling the reaction solution to obtain the sequence-controllable poly (amide-thioamide) polymer.
In the present invention, the reaction equation for synthesizing a sequence-controllable poly (amide-thioamide) polymer is:
Figure BDA0003264453950000112
in the invention, the molar ratio of the total amount of the difunctional amine monomer, the maleic anhydride and the elemental sulfur is 1.0: 0.5-1.95: 1.5-6, preferably 1.0: 0.8-1.8: 2.0 to 5.0, and more preferably 1.0: 1.0: 2.5.
in the present invention, the molar ratio of the first difunctional amine monomer to the second difunctional amine monomer is 1: 0.5 to 1.5, preferably 1: 1.
in the present invention, the first difunctional amine monomer and the second difunctional amine monomer each comprise the following compounds:
Figure BDA0003264453950000121
(ii) a Wherein the content of the first and second substances,n and k are integers of 1-20.
The first difunctional amine monomer and the second difunctional amine monomer are preferably:
Figure BDA0003264453950000122
the first difunctional amine monomer and the second difunctional amine monomer are further preferably:
Figure BDA0003264453950000131
in the present invention, the inert gas is preferably nitrogen and/or argon, and more preferably nitrogen.
In the present invention, the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-methylpiperidine, toluene, N-dimethylacetamide, tetrahydrofuran, 1, 4-dioxane, and N-methylpyrrolidone, and preferably one or more of dimethyl sulfoxide, N-dimethylformamide, and N-methylpiperidine.
In the invention, the settling agent used for settling comprises one or more of methanol, brine and ammonium chloride solution, and preferably methanol.
In the invention, the reaction temperature of the first difunctional amine monomer, maleic anhydride and elemental sulfur is 20-30 ℃, the reaction time is 10-20 min, preferably 25 ℃, and the reaction time is 15 min.
In the invention, a second difunctional amine monomer is added into the reaction liquid for reaction at the temperature of 40-100 ℃ for 4-16 h; preferably, the reaction temperature is 50-90 ℃, and the reaction time is 5-15 h; further preferably, the reaction temperature is 60-80 ℃, and the reaction time is 8-12 h.
The invention provides application of poly (amide-thioamide) polymer in the photoelectric field and the metal ion adsorption field.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The reaction equation for polymer P1 is shown below:
Figure BDA0003264453950000132
wherein P1 contains
Figure BDA0003264453950000141
Figure BDA0003264453950000142
And (5) structure.
The polymer was synthesized as follows:
in a nitrogen-filled reactor, dimethylsulfoxide, N-dimethylformamide and N-methylpiperidine were mixed in the following ratio of 1: 3: 0.1, and then adding the mixture into a reactor with a molar ratio of 1: 1: 2.5 of p-xylylenediamine, maleic anhydride and sublimed sulfur, and stirred at normal temperature for 15 minutes, then the temperature was raised to 90 c, and stirred for 16 hours.
After the reaction is finished, adding dimethyl sulfoxide to dilute the reaction solution, and cooling to room temperature. Thereafter, the reaction solution was passed through a glass dropper equipped with cotton at a rate of 2 drops per second, the residual sulfur was filtered, and then 100mL of a precipitant methanol was added to the filtrate. And filtering the polymer precipitated from the methanol, and drying the polymer to the normal temperature at the temperature of 45 ℃ in a vacuum environment to obtain the target product poly (amide-thioamide). The product yield of this example was 86%, the weight average molecular weight was 46700g/mol, and the weight average molecular weight/number average molecular weight was 2.27.
The chemicals used in this example are commercially available, with p-xylylenediamine from Annaiji, maleic anhydride from TCI, and sublimed sulfur from Alfaesar.
As an aid to the analysis of the polymer obtained in example 1, Compound 9 was synthesized according to the method disclosed in the literature (Advanced Catalyst & Synthesis.2019,361, 2864-2869). The obtained amide-thioamide compound has hydrogen spectrum nuclear magnetic spectrum in deuterated dimethyl sulfoxide as shown in figure 1(C), and carbon spectrum nuclear magnetic spectrum in deuterated dimethyl sulfoxide as shown in figure 2 (C).
Figure BDA0003264453950000143
The nuclear magnetic spectrum of poly (amide-thioamide) P1 in deuterated dimethyl sulfoxide in this example is shown in FIG. 1 (D). Nuclear magnetic spectrum analysis was performed on figure 1. It can be found that, except for the solvent peak at 2.50ppm and the water peak at 3.33ppm, which are exhibited by deuterated dimethyl sulfoxide, peaks which are all exhibited by hydrogen atoms contained in poly (amide-thioamide) appear in other nuclear magnetic spectrograms. Wherein, at 10.57ppm, is a characteristic peak on the hydrogen atom of-NH-in the thioamide group; the peak at 8.56ppm is characteristic for the hydrogen atom of-NH-in the amide group, and the peak at 3.64ppm is characteristic for the methylene group between the amide group and the thioamide group. The two peaks at 4.76ppm and 4.27ppm are the peaks of the hydrogen atom of the methylene group adjacent to the thioamide group and the amide group, respectively, and the two peaks at these are the peaks of the hydrogen atom on the benzene ring. The analysis results obtained above are all matched with the peaks of the nuclear magnetic spectrum of the molded polymer in the formula (9), and provide evidence for the structural characterization of the poly (amide-thioamide).
The carbon spectrum nuclear magnetic spectrum of poly (amide-thioamide) P1 in deuterated dimethyl sulfoxide in the example is shown in the attached figure 2 (D). When the nmr of fig. 2 was analyzed, it was found that, except for the solvent peak at 39.52ppm, which is shown by deuterated dimethyl sulfoxide, all peaks shown in nmr spectra are peaks shown by carbon atoms contained in poly (amide-thioamide). Wherein, at 196.00ppm is the characteristic peak on the carbon atom of-C ═ S in the thioamide group; the peak at 166.76ppm is characteristic for the carbon atom of-C ═ O in the amide group, and the peak at 51.90ppm is characteristic for the methylene group between the amide group and thioamide group. The two peaks at 48.36ppm and 42.05ppm are the peaks at the carbon atom of the methylene group adjacent to the thioamide group and the amide group, respectively, and the peaks at 137.69ppm, 135.85ppm, 127.70ppm and 127.22ppm are the peaks at the carbon atom of the benzene ring. The analysis results obtained above are all matched with the peaks of the nuclear magnetic spectrum of the model compound in the formula (9), and provide evidence for the structural characterization of the poly (amide-thioamide).
The characterization data for the poly (amide-thioamide) s provided in this example are shown below:
poly (amide-thioamide) P1, orange solid, 86% yield. The weight average molecular weight was 46700g/mol, and the weight average molecular weight/number average molecular weight was 2.27. The infrared spectral data are as follows (lithium bromide flakes): v (cm)-1):3246,3051,2922,1654,1530,1521,1417,1334,1237,1182,1112,1081,1019,971,919,844,805,763,696,592,550,469. The nuclear magnetic data are as follows:1H NMR(500MHz,DMSO-d6),δ(TMS,ppm):10.57(d,1H,-NH-),8.56(d,1H,-NH-),7.34-7.27(d,2H),7.27-7.20(d,2H),4.76(d,2H),4.27(d,2H),3.64(s,1H).13C NMR(125MHz,DMSO-d6),δ(TMS,ppm):194.38(C＝S),165.91(C＝O),53.16,51.90,47.28,30.82,28.93。
example 2
The reaction equation for polymer P2 is shown below:
Figure BDA0003264453950000161
wherein P2 includes
Figure BDA0003264453950000162
Figure BDA0003264453950000163
And (5) structure.
The polymer was synthesized as follows:
in an argon-filled reactor, dimethylsulfoxide, N-dimethylformamide and N-methylpiperidine were reacted in a ratio of 1: 3: 0.1, and then adding the mixture into a reactor with a molar ratio of 1: 1: 2.5, dissolving the 4,4' -diaminodiphenylmethane, maleic anhydride and sublimed sulfur, stirring for 15 minutes at normal temperature, heating to 90 ℃, and stirring for 6 hours;
after the reaction is finished, dimethyl sulfoxide is quickly added into the reaction solution to dilute the reaction solution, and the temperature is reduced to room temperature. Thereafter, the reaction solution was passed through a glass dropper equipped with cotton at a rate of 1 drop per second, the residual sulfur was filtered, and then 100mL of a precipitant methanol was added to the filtrate. And filtering the polymer precipitated from the methanol, and drying the polymer to normal temperature at the temperature of 45 ℃ in a vacuum environment to obtain the target product poly (amide-thioamide). The product yield of this example was 95%, the weight average molecular weight was 18700g/mol, and the weight average molecular weight/number average molecular weight was 1.35.
The chemicals used in this example are commercially available, with N, N-dimethylformamide from Annaiji, maleic anhydride from TCI, and sublimed sulfur from Alfaesar.
The characterization data for the poly (amide-thioamide) s provided in this example are shown below:
poly (amide-thioamide) P2, brown solid, 95% yield. The weight average molecular weight was 18700g/mol, and the weight average molecular weight/number average molecular weight was 1.35. The infrared spectral data are as follows (lithium bromide flakes): v (cm)-1):3272,3026,2909,1902,1668,1598,1510,1404,1311,1243,1179,1109,1016,952,917,852,813,775,727,659,630,499. The nuclear magnetic data are as follows:1H NMR(400MHz,DMSO-d6),δ(TMS,ppm):11.75(s,1H,-NH-),10.14(s,1H,-NH-),7.78(d,2H),7.58-7.48(d,2H),7.33-7.07(d,4H),4.00-3.80(s,s,4H).13C NMR(125MHz,DMSO-d6),δ(TMS,ppm):194.23(C＝S),165.37(C＝O),129.15,128.91,128.72,128.45,122.91,122.79,119.25,54.82,53.77,42.70,40.43。
example 3
The reaction equation for polymer P3 is shown below:
Figure BDA0003264453950000171
wherein P3 contains
Figure BDA0003264453950000172
Figure BDA0003264453950000173
And (5) structure.
The polymer was synthesized as follows:
in an argon-filled reactor, dimethylsulfoxide, N-dimethylformamide and N-methylpiperidine were reacted in a ratio of 1: 3: 0.1, and then adding the mixture into a reactor with a molar ratio of 1: 1: 2.5 of 1, 3-bis (4-piperidyl) propane, maleic anhydride and sublimed sulfur, stirring for 15 minutes at normal temperature, heating to 90 ℃, and stirring for 12 hours;
after the reaction is finished, adding dimethyl sulfoxide to dilute the reaction solution, and cooling to room temperature. Thereafter, the reaction solution was passed through a glass dropper equipped with cotton at a rate of 2 drops per second, the residual sulfur was filtered, and then 100mL of a precipitant methanol was added to the filtrate. And filtering the polymer precipitated from the methanol, and drying the polymer to normal temperature at the temperature of 45 ℃ in a vacuum environment to obtain the target product poly (amide-thioamide). The product yield of this example was 86%, the weight average molecular weight was 7700g/mol, and the weight average molecular weight/number average molecular weight was 1.22.
The chemicals used in this example are commercially available, with 1, 3-bis (4-piperidinyl) propane and maleic anhydride from TCI and sublimed sulfur from alfa-esha.
The characterization data for the poly (amide-thioamide) s provided in this example are shown below:
poly (amide-thioamide) P3, black solid, 94% yield. The weight average molecular weight was 7700g/mol, and the weight average molecular weight/number average molecular weight was 1.22. The infrared spectral data are as follows (lithium bromide flakes): v (cm)-1):2992,2921,2845,1635,1500,1443,1367,1304,1266,1200,1156,1122,1093,1021,954,858,801,764,728,706,654,612,536. The nuclear magnetic data are as follows:1H NMR(400MHz,DMSO-d6),δ(TMS,ppm):5.33(d,1H),4.32(d,1H),4.09(s,2H),3.84(d,1H),2.97(m,3H),1.76(m,2H),1.65(m,2H),1.45(m,2H),1.29(m,2H),1.19(m,4H),1.07(m,2H),0.90(m,2H).13C NMR(125MHz,DMSO-d6),δ(TMS,ppm):192.97(C＝S),164.89(C＝O),50.60,49.82,49.79,48.83,48.59,45.65,43.35,41.56,35.99,35.57,35.13,34.44,32.75,32.32,31.61,31.35,28.47,22.98。
example 4
The reaction equation for polymer P4 is shown below:
Figure BDA0003264453950000181
the polymer was synthesized as follows:
in a reactor filled with inert gas, dimethyl sulfoxide, N-dimethylformamide and N-methylpiperidine were reacted in a ratio of 1: 3: 0.1, and then adding the mixture into a reactor with a molar ratio of 1: 1.95: 5 of p-xylylenediamine, maleic anhydride and sublimed sulfur, and stirred at room temperature for 15 minutes, then 1, 3-bis (4-piperidyl) propane in an amount equimolar to p-xylylenediamine was added, the temperature was raised to 80 ℃, and stirred for 16 hours.
After the reaction is finished, adding dimethyl sulfoxide to dilute the reaction solution, and cooling to room temperature. Thereafter, the reaction solution was passed through a glass dropper equipped with cotton at a rate of 2 drops per second, and the residual sulfur was filtered, after which 120mL of a solution having a volume ratio of 2: 1 with ammonium chloride solution. And filtering the polymer precipitated from the settling agent, and drying the polymer to normal temperature at the temperature of 45 ℃ in a vacuum environment to obtain the target product poly (amide-thioamide). The product yield of this example was 88%, the weight average molecular weight was 17300g/mol, and the weight average molecular weight/number average molecular weight was 1.56.
The chemicals used in this example are commercially available, with p-xylylenediamine from Annelagi, maleic anhydride and 1, 3-bis (4-piperidinyl) propane from TCI, and sublimed sulfur from Alfaesar.
The poly (amide-thioamide) obtained in this example is shown below as P4.
Figure BDA0003264453950000191
The characterization data for the poly (amide-thioamide) s provided in this example are shown below:
poly (amide-thioamide) P4, brown solid, 95% yield. The weight average molecular weight was 17300g/mol, and the weight average molecular weight/number average molecular weight was 1.56. The infrared spectral data are as follows (lithium bromide flakes): v (cm)-1):3307,3048,3025,2922,2850,1666,1501,1445,1357,1324,1276,1236,1120,1091,1019,948,921,844,804,753,679,617,536,475. The nuclear magnetic data are as follows:1H NMR(400MHz,DMSO-d6),δ(TMS,ppm):8.44(t,2H,-NH-),7.21(d,4H),5.34(d,2H),4.24(d,d,6H),3.92(s,4H),3.22(m,2H),3.01(m,2H),1.75(m,2H),1.70(m,2H),1.59(m,2H),1.29(m,2H),1.19(m,6H),1.07(m,2H).13C NMR(125MHz,DMSO-d6),δ(TMS,ppm):192.56(C＝S),166.21(C＝O),137.78,127.20,50.90,50.72,49.96,43.37,41.98,35.55,34.47,32.51,31.36,28.52,23.22。
from the above examples, it can be seen that the present invention provides a poly (amide-thioamide) polymer, and methods of synthesis and use thereof. The multi-component series polymerization method has the advantages of multi-component polymerization, and can control the reaction sequence and the structure of a reaction product by feeding the reaction step by step, so that the sequence regulation and control of the polymer are realized by a one-pot, two-step and three-component method. The research of synthesizing polymers with controllable sequences by utilizing a multi-component tandem polymerization method and using elemental sulfur as a raw material or synthesizing sulfur-containing polymers has not been reported in the prior art. The present invention not only achieves the above-described studies, but also yields high yields (95%) of structurally defined and regular poly (amide-thioamide) polymers. The polymer has the property of emitting light under ultraviolet excitation, and has potential application in the photoelectric field. Meanwhile, the thioamide group contained in the polymer is found to have a function of adsorbing metal ions. The polymer has the function of adsorbing metal ions and the luminescence property, which shows that the polymer can be applied to the fields of heavy ion removal and ion monitoring.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. A poly (amide-thioamide) polymer characterized by a structure comprising
Figure FDA0003577383710000011
Figure FDA0003577383710000012
Structure;
or comprises
Figure FDA0003577383710000013
Figure FDA0003577383710000014
Structure;
or comprises
Figure FDA0003577383710000015
Figure FDA0003577383710000016
And (5) structure.
2. A method of synthesizing a poly (amide-thioamide) polymer as described in claim 1, comprising the steps of:
under the inert gas environment, adding difunctional amine monomer, maleic anhydride and elemental sulfur into an organic solvent to react to obtain reaction liquid, and diluting, filtering and settling the reaction liquid to obtain the poly (amide-thioamide).
3. The method of claim 2, wherein the molar ratio of difunctional amine monomer, maleic anhydride and elemental sulfur is 1: 0.5-1.95: 1.5 to 6;
the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-methylpiperidine, toluene, N-dimethylacetamide, tetrahydrofuran, 1, 4-dioxane and N-methylpyrrolidone.
4. The method of synthesis of claim 3, wherein the difunctional amine monomer comprises the following compounds:
Figure FDA0003577383710000021
2HN-CkH2k-NH2
Figure FDA0003577383710000022
Figure FDA0003577383710000023
wherein n and k are integers of 1-20.
5. A poly (amide-thioamide) polymer, wherein said polymer is a sequence-controllable poly (amide-thioamide) polymer, said polymer having the formula:
Figure FDA0003577383710000024
wherein n is an integer of 2 to 500.
6. The method of synthesizing a poly (amide-thioamide) polymer of claim 5, comprising the steps of:
under the inert gas environment, adding a first bifunctional amine monomer, maleic anhydride and elemental sulfur into an organic solvent to react to obtain a reaction solution, adding a second bifunctional amine monomer into the reaction solution to react, and then diluting, filtering and settling the reaction solution to obtain the sequence-controllable poly (amide-thioamide) polymer.
7. The method of claim 6, wherein the molar ratio of the total amount of difunctional amine monomer, maleic anhydride and elemental sulfur is 1.0: 0.5-1.95: 1.5 to 6, wherein the molar ratio of the first difunctional amine monomer to the second difunctional amine monomer is 1: 0.5 to 1.5;
the first difunctional amine monomer and the second difunctional amine monomer each comprise the following compounds:
Figure FDA0003577383710000031
2HN-CkH2k-NH2
Figure FDA0003577383710000032
Figure FDA0003577383710000033
wherein n and k are integers of 1-20;
the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-methylpiperidine, toluene, N-dimethylacetamide, tetrahydrofuran, 1, 4-dioxane and N-methylpyrrolidone.
8. Use of the poly (amide-thioamide) polymer according to claim 1 or 5 in the fields of optoelectronics and metal ion adsorption.
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