CN105001419A - Alkyne, sulfur and amine multi-component polymerization method for preparing poly-thioamide - Google Patents
Alkyne, sulfur and amine multi-component polymerization method for preparing poly-thioamide Download PDFInfo
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- CN105001419A CN105001419A CN201510317858.5A CN201510317858A CN105001419A CN 105001419 A CN105001419 A CN 105001419A CN 201510317858 A CN201510317858 A CN 201510317858A CN 105001419 A CN105001419 A CN 105001419A
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Abstract
The invention belongs to the technical field of preparing a sulfur-containing organic polymer, and discloses an alkyne, sulfur and amine multi-component polymerization method for preparing poly-thioamide. The method includes the steps that under the condition of inert gas shielding, primary amine monomers containing aromatic groups or aromatic derivatives, terminal diyne monomers containing aromatic groups or aromatic derivatives and elemental sulfur are added into solvent to be dissolved, heated to the temperature of 50 DEG C-120 DEG C so as to react fully, and then cooled to the room temperature, precipitant is added into a reaction mother solution for precipitation, and a precipitate is collected and dried until the weight is constant to obtain the poly-thioamide. The poly-thioamide has a structural general formula shown as the formula (1), wherein n is an integer ranging from two to two hundred, and Ar1 and Ar2 are the same or different aromatic groups or aromatic derivatives. The poly-thioamide has the special photoelectric property and potential application value in biological and chemical fluorescence detection fields.
Description
Technical field
The invention belongs to sulfur-bearing organic polymer preparing technical field, be specifically related to a kind of polycomponent polymerization process of alkynes, sulphur and the amine of preparing poly-thioamides.
Background technology
In polymer molecule, introduce haloid element (except fluorine), heavy metal ion, phenyl ring and condensed ring, sulphur, phosphorus atom can improve specific refractory power effectively, wherein polymkeric substance is not only made to have higher refractive index adding of element sulphur, also contribute to the dispersion reducing material, this base polymer is easy to prepare in addition, environmental stability is good, therefore causes the extensive concern of scientists.At present, in polymkeric substance, element sulphur is normally introduced with forms such as thioether bond, thioester bond, thiocarbamate, sulfuryl and epithios, commonly use the extremely unpleasant multi-thiol of smell, polyisothiocyanates and dithiocarbonic anhydride in the reaction, expensive, long reaction time, strongly limit the production application of sulfur-bearing height refractive power polymkeric substance.Therefore, develop a kind of more green, more simply, more efficient novel method is very necessary to synthesize sulfur-bearing height refractive power polymkeric substance.
Desirable polyreaction is from the raw material be cheaply easy to get, prepares required polymkeric substance by simple efficient, environmental friendliness, high atom utilization reaction.In recent years, scientists attempts directly utilizing elementary sulfur to prepare sulfur-containing polymer, in this process, avoid the micromolecular uses of other sulfur-bearings such as mercaptan, economic environmental protection, simply efficient, the production application for further genralrlization sulfur-bearing height refractive power polymkeric substance is significant.
The reaction of current synthesis sulfur-containing polymer is varied, but directly synthesizing poly-thioamides using elementary sulfur as reactant does not but report.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the present invention is to provide a kind of polycomponent polymerization process of alkynes, sulphur and the amine of preparing poly-thioamides.
Another object of the present invention is to the poly-thioamides providing a class to utilize aforesaid method to prepare.
The object of the invention is achieved through the following technical solutions:
Prepare a polycomponent polymerization process for the alkynes of poly-thioamides, sulphur and amine, comprise following preparation process:
(1) under protection of inert gas, the primary amine monomer containing aromatic base or aryl derivative, the end diyne monomer containing aromatic base or aryl derivative and elemental sulfur are added in solvent and dissolves, be warming up to 50 ~ 120 DEG C of fully reactions;
(2) be cooled to room temperature after completion of the reaction, joined in precipitation agent by reaction mother liquor and precipitate, collecting precipitation thing, is dried to constant weight, obtains poly-thioamides.
The preferred sublimed sulphur of elemental sulfur described in step (1); The preferred pyridine of described solvent.
Precipitation agent particular methanol described in step (2).
The described mode joined by reaction mother liquor in precipitation agent is dropping, and reaction mother liquor first diluted with dimethyl formamide solution before joining in precipitation agent.
Reaction equation involved by above-mentioned polymerization process is as follows:
The poly-thioamides that one class utilizes aforesaid method to prepare, described poly-thioamides has the general structure shown in formula (1):
Wherein, n is the integer of 2 ~ 200; Ar
1, Ar
2for identical or different aromatic base or aryl derivative; Described aromatic base or the structural formula shown in the preferred following any one of a ~ n of aryl derivative:
Wherein, p is the integer of 1 ~ 20, and R ' and R 〞 is identical or not identical hydrogen, alkyl or alkoxyl group.
Preparation method of the present invention and the product tool obtained have the following advantages and beneficial effect:
(1) polymerization single polymerization monomer that polymerization process of the present invention is used is cheaply easy to get, and polymer yield is high, and molecular weight is high, and Atom economy is high, and refractive index is higher, and film-forming properties is better;
(2) polymerization process of the present invention is without any need for catalyzer, directly using elementary sulfur as reactant, gathers thioamides by three components reaction one-step synthesis;
(3) the poly-thioamides that prepared by the present invention contains atypia chromophore and has special photoelectric properties, has potential using value in biological and chemical fluoroscopic examination field.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 obtain one birds of the same feather flock together thioamides in deuterated dimethyl sulfoxide hydrogen spectrum nuclear magnetic spectrogram;
Fig. 2 is birdsing of the same feather flock together the thermogravimetric curve figure of thioamides in nitrogen atmosphere of obtaining of the embodiment of the present invention 1;
Fig. 3 is the refractive index curve chart of birdsing of the same feather flock together thioamides that the embodiment of the present invention 1 obtains;
Fig. 4 be the embodiment of the present invention 1 obtain one birds of the same feather flock together thioamides different concns under photoluminescence graphic representation.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The present embodiment a kind of prepares the polycomponent polymerization process of the alkynes of poly-thioamides, sulphur and amine, and concrete preparation process is as follows:
(1) under protection of inert gas, 68mg p dimethylamine, 94.5mg1,4-diacetylene-benzene and 64mg sublimed sulphur are joined in 0.5mL pyridine and dissolves, be warming up to 50 ~ 60 DEG C, under agitation react 24h;
(2) be cooled to room temperature after completion of the reaction, with 1mL dimethyl formamide solution diluting reaction mother liquor, then be added dropwise in 20mL methyl alcohol and precipitate, collecting precipitation thing, is dried to constant weight, obtains poly-thioamides.
The poly-thioamides of the present embodiment has the structural formula shown in P1:
Reaction equation involved by the present embodiment is as follows:
The hydrogen of poly-thioamides in deuterated dimethyl sulfoxide of the present embodiment composes nuclear magnetic spectrogram as shown in Figure 1.As can be seen from Figure 1, the solvent peak of deuterated dimethyl sulfoxide and Shui Feng lay respectively at 2.5 and 3.3ppm, and residual solvent dimethylformamide peak is positioned at 2.73, and 2.89 and 7.95ppm; What be hydrogen atom in polymkeric substance in addition goes out peak.
The poly-thioamides of the present embodiment thermogravimetric curve figure in nitrogen atmosphere as shown in Figure 2.Fig. 2 shows that resulting polymers has good thermostability, and heat decomposition temperature when weightless 5% is 284 DEG C.
The poly-thioamides of the present embodiment makes the refractive index curve chart after film as shown in Figure 3.Fig. 3 result shows that resulting polymers has higher specific refractory power, and the specific refractory power at 630nm place is up to 1.72, as more much higher in polystyrene and polymethylmethacrylate etc. than general polymer materials.
The poly-thioamides of the present embodiment photoluminescence graphic representation under different concns as shown in Figure 4.Fig. 4 shows, the polymer materials of this non-conjugated structure has good fluorescent emission, and occurs the phenomenon of fluorescent emission red shift along with the increase of concentration.
Embodiment 2
The present embodiment a kind of prepares the polycomponent polymerization process of the alkynes of poly-thioamides, sulphur and amine, and concrete preparation process is as follows:
(1) under protection of inert gas, 68mg p dimethylamine, 285mg diacetylene tetraphenylethylene and 64mg sublimed sulphur are joined in 0.5mL pyridine and dissolves, be warming up to 100 ~ 120 DEG C, under agitation react 4h;
(2) be cooled to room temperature after completion of the reaction, with 1mL dimethyl formamide solution diluting reaction mother liquor, then be added dropwise in 20mL methyl alcohol and precipitate, collecting precipitation thing, is dried to constant weight, obtains poly-thioamides.
The diacetylene tetraphenylethylene of the present embodiment is according to the disclosed method preparation of document [Polym.Chem.2012,3,1481].
The poly-thioamides of the present embodiment has the structural formula shown in P2:
Reaction equation involved by the present embodiment is as follows:
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. prepare a polycomponent polymerization process for the alkynes of poly-thioamides, sulphur and amine, it is characterized in that comprising following preparation process:
(1) under protection of inert gas, the primary amine monomer containing aromatic base or aryl derivative, the end diyne monomer containing aromatic base or aryl derivative and elemental sulfur are joined in solvent and dissolves, be warming up to 50 ~ 120 DEG C of fully reactions;
(2) be cooled to room temperature after completion of the reaction, joined in precipitation agent by reaction mother liquor and precipitate, collecting precipitation thing, is dried to constant weight, obtains poly-thioamides.
2. the polycomponent polymerization process of a kind of alkynes, sulphur and the amine of preparing poly-thioamides according to claim 1, is characterized in that: described elemental sulfur refers to sublimed sulphur.
3. the polycomponent polymerization process of a kind of alkynes, sulphur and the amine of preparing poly-thioamides according to claim 1, is characterized in that: described solvent refers to pyridine.
4. the polycomponent polymerization process of a kind of alkynes, sulphur and the amine of preparing poly-thioamides according to claim 1, is characterized in that: described precipitation agent refers to methyl alcohol.
5. the polycomponent polymerization process of a kind of alkynes, sulphur and the amine of preparing poly-thioamides according to claim 1, it is characterized in that: the mode that described reaction mother liquor joins in precipitation agent is dropping, and reaction mother liquor first diluted with dimethyl formamide solution before joining in precipitation agent.
6. the poly-thioamides that prepared by the method described in any one of Claims 1 to 5 of a class, is characterized in that: described poly-thioamides has the general structure shown in formula (1):
Wherein, n is the integer of 2 ~ 200; Ar
1, Ar
2for identical or different aromatic base or aryl derivative.
7. according to claim 6 one birdss of the same feather flock together thioamides, it is characterized in that: the structural formula shown in described aromatic base or aryl derivative have any one of following a ~ n:
Wherein, p is the integer of 1 ~ 20, and R ' and R 〞 is identical or not identical hydrogen, alkyl or alkoxyl group.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820335A (en) * | 2016-03-31 | 2016-08-03 | 华南理工大学 | Polyene amino compound and preparation method thereof |
| CN106243351A (en) * | 2016-07-28 | 2016-12-21 | 华南理工大学 | Controlled linear/the hyper-branched polymer of sequence and method and application are prepared in the polymerization of multicomponent without metal catalytic |
| CN106279677A (en) * | 2016-08-09 | 2017-01-04 | 华南理工大学 | Rich in heteroatomic phosphine amidine base polymer and multicomponent polymerization and the application of preparing this polymer |
| CN107619477A (en) * | 2017-09-22 | 2018-01-23 | 中山大学 | A kind of poly- thioamides and its preparation method and application |
| CN108570149A (en) * | 2017-06-21 | 2018-09-25 | 华南理工大学 | A kind of multicomponent polymerization of isonitrile, sulphur and amine prepares the method for polythiourea and the application of the polythiourea |
| CN109535424A (en) * | 2018-10-22 | 2019-03-29 | 华南理工大学 | A kind of poly- thioamide analog compound and its preparation method and application |
| CN110183675A (en) * | 2019-05-13 | 2019-08-30 | 华南理工大学 | A kind of hyperbranched poly thioamide analog compound and its preparation method and application |
| CN115124715A (en) * | 2021-03-29 | 2022-09-30 | 华南理工大学 | Preparation method of pyridyl polythioamide |
| CN115466388A (en) * | 2022-09-16 | 2022-12-13 | 华南理工大学 | Polythiourea compound and preparation method thereof |
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| CN101503398A (en) * | 2009-03-17 | 2009-08-12 | 成都金桨高新材料有限公司 | Novel sulfide or sulfone containing dianhydride, and preparation and use thereof |
| CN101679616A (en) * | 2007-06-11 | 2010-03-24 | 香港科技大学 | Synthesis of acylarylenes and hyperbranched poly(acylarylene)s by metal-free cyclotrimerization of alkynes |
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| JP2007297653A (en) * | 2006-04-27 | 2007-11-15 | Tokyo Institute Of Technology | Metal separation method and metal recovery method |
| CN101679616A (en) * | 2007-06-11 | 2010-03-24 | 香港科技大学 | Synthesis of acylarylenes and hyperbranched poly(acylarylene)s by metal-free cyclotrimerization of alkynes |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820335A (en) * | 2016-03-31 | 2016-08-03 | 华南理工大学 | Polyene amino compound and preparation method thereof |
| CN106243351A (en) * | 2016-07-28 | 2016-12-21 | 华南理工大学 | Controlled linear/the hyper-branched polymer of sequence and method and application are prepared in the polymerization of multicomponent without metal catalytic |
| CN106279677B (en) * | 2016-08-09 | 2019-05-14 | 华南理工大学 | Rich in heteroatomic phosphine amidine quasi polymer and prepares the multicomponent polymerization of the polymer and apply |
| CN106279677A (en) * | 2016-08-09 | 2017-01-04 | 华南理工大学 | Rich in heteroatomic phosphine amidine base polymer and multicomponent polymerization and the application of preparing this polymer |
| CN108570149A (en) * | 2017-06-21 | 2018-09-25 | 华南理工大学 | A kind of multicomponent polymerization of isonitrile, sulphur and amine prepares the method for polythiourea and the application of the polythiourea |
| CN108570149B (en) * | 2017-06-21 | 2020-05-22 | 华南理工大学 | Method for preparing polythiourea by multicomponent polymerization of isonitrile, sulfur and amine and application of polythiourea |
| CN107619477A (en) * | 2017-09-22 | 2018-01-23 | 中山大学 | A kind of poly- thioamides and its preparation method and application |
| CN107619477B (en) * | 2017-09-22 | 2020-06-30 | 中山大学 | Polythioamide and preparation method and application thereof |
| CN109535424A (en) * | 2018-10-22 | 2019-03-29 | 华南理工大学 | A kind of poly- thioamide analog compound and its preparation method and application |
| CN110183675A (en) * | 2019-05-13 | 2019-08-30 | 华南理工大学 | A kind of hyperbranched poly thioamide analog compound and its preparation method and application |
| CN110183675B (en) * | 2019-05-13 | 2022-03-29 | 华南理工大学 | Hyperbranched polythioamide compound and preparation method and application thereof |
| CN115124715A (en) * | 2021-03-29 | 2022-09-30 | 华南理工大学 | Preparation method of pyridyl polythioamide |
| CN115124715B (en) * | 2021-03-29 | 2023-09-26 | 华南理工大学 | Preparation method of pyridyl polythioamide |
| CN115466388A (en) * | 2022-09-16 | 2022-12-13 | 华南理工大学 | Polythiourea compound and preparation method thereof |
| CN115466388B (en) * | 2022-09-16 | 2023-09-08 | 华南理工大学 | Polythiourea compound and preparation method thereof |
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