CN105001419B - 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
- Publication number
- CN105001419B CN105001419B CN201510317858.5A CN201510317858A CN105001419B CN 105001419 B CN105001419 B CN 105001419B CN 201510317858 A CN201510317858 A CN 201510317858A CN 105001419 B CN105001419 B CN 105001419B
- Authority
- CN
- China
- Prior art keywords
- poly
- amine
- thioamides
- added
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 C**NCc1ccc(CNC(Cc2ccc(CC(C(C)C)=S)cc2)=S)cc1 Chemical compound C**NCc1ccc(CNC(Cc2ccc(CC(C(C)C)=S)cc2)=S)cc1 0.000 description 1
- CKEVGNUTTFYTTI-UHFFFAOYSA-N CNCc1ccc(CN)cc1 Chemical compound CNCc1ccc(CN)cc1 CKEVGNUTTFYTTI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
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, and in particular to a kind of alkynes for preparing poly- thioamides
The multicomponent polymerization of hydrocarbon, sulphur and amine.
Background technology
Halogen (fluorine removal), heavy metal ion, phenyl ring and condensed ring, sulphur, phosphorus atoms are introduced in polymer molecule can be had
Effect ground improves refractive index, and the addition of wherein element sulphur not only makes polymer have higher refraction index, additionally aids reduction material
The dispersion of material, in addition this kind of polymer preparation is convenient, and environmental stability is good, therefore causes the extensive concern of scientists.Mesh
Before, element sulphur typically draws in forms such as thioether bond, thioester bond, thiocarbamate, sulfuryl and epithios in polymer
Enter, multi-thiol, polyisothiocyanates and the carbon disulfide of the extremely difficult news of smell is commonly used in the reaction, it is expensive, during reaction
Between it is long, strongly limit the production application of the high refractive power polymer of sulfur-bearing.Therefore, develop it is a kind of it is more green, simpler,
More efficient new method is come to synthesize the high refractive power polymer of sulfur-bearing be very necessary.
Preferably polymerisation is from the beginning of cheap and easily-available raw material, to be utilized by simple efficient, environmental friendliness, high atom
The reaction of rate is come the polymer needed for preparing.In recent years, scientists are attempted directly preparing sulfur-containing polymer using elementary sulfur,
The use of other sulfur-bearing small molecules such as mercaptan is avoided during this, it is economic and environment-friendly, simple efficient, for further genralrlization contains
The production application of the high refractive power polymer of sulphur is significant.
The reaction of current synthesis sulfur-containing polymer is varied, but directly using elementary sulfur as reactant synthesizing polysulfide
But do not report for acid amides.
The content of the invention
In order to solve the shortcoming and defect part of above prior art, the primary and foremost purpose of the present invention is to provide one kind to prepare
The multicomponent polymerization of the alkynes, sulphur and amine of poly- thioamides.
Another object of the present invention is to provide the poly- thioamides that a class is prepared using said method.
The object of the invention is achieved through the following technical solutions：
The multicomponent polymerization of a kind of alkynes for preparing poly- thioamides, sulphur and amine, including following preparation process：
(1) under inert gas shielding, by the primary amine monomer containing aromatic radical or aryl derivative, containing aromatic radical or fragrance
The end diine hydrocarbon monomer of radical derivative and elemental sulfur are added in solvent and dissolved, and are warming up to 50～120 DEG C of fully reactions；
(2) room temperature is cooled to after completion of the reaction, reaction mother liquor is added in precipitating reagent and is precipitated, collect sediment,
It is dried to constant weight, obtains poly- thioamides.
The preferred sublimed sulfur of elemental sulfur described in step (1)；The preferred pyridine of described solvent.
The preferred methyl alcohol of precipitating reagent described in step (2).
It is described that reaction mother liquor is added to into mode in precipitating reagent to be added dropwise, and reaction mother liquor in precipitating reagent is added to it
It is front to be first diluted with dimethyl formamide solution.
Reaction equation involved by above-mentioned polymerization is as follows：
The poly- thioamides that one class is prepared using said method, the poly- thioamides has the knot shown in formula (1)
Structure formula：
Wherein, n is 2～200 integer；Ar1、Ar2For same or different aromatic radical or aryl derivative；It is described
The structural formula of aromatic radical or aryl derivative preferably shown in following any one of a～n：
Wherein, p is 1～20 integer, and R ' and R 〞 are hydrogen that is identical or differing, alkyl or alkoxyl.
The preparation method and resulting product of the present invention has the advantage that and beneficial effect：
(1) polymerized monomer used by polymerization of the present invention is cheap and easily-available, and polymer yield is high, and molecular weight is high,
Atom economy is high, and refraction index is higher, and film forming is preferable；
(2) polymerization of the present invention does not need any catalyst, directly using elementary sulfur as reactant, by three
The poly- thioamides of component reaction one-step synthesis；
(3) poly- thioamides prepared by the present invention contains atypia chromophore and has special photoelectric properties, in biology
There is potential using value with chemiluminescence detection field.
Description of the drawings
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-magnetism spectrum
Figure；
Fig. 2 is birdsing of the same feather flock together thermogravimetric curve figure of the thioamides in nitrogen atmosphere of obtaining of the embodiment of the present invention 1；
Fig. 3 is the refractive index curve chart for birdsing of the same feather flock together thioamides that the embodiment of the present invention 1 is obtained；
Fig. 4 be the embodiment of the present invention 1 obtain one birds of the same feather flock together thioamides variable concentrations under photoluminescence curve map.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
A kind of multicomponent polymerization of the alkynes for preparing poly- thioamides, sulphur and amine of the present embodiment, it is concrete to prepare step
It is rapid as follows：
(1) under inert gas shielding, by 68mg p dimethylamines, 94.5mg1,4- diacetylene-benzenes and 64mg sublimed sulfurs
It is added in 0.5mL pyridines and dissolves, be warming up to 50～60 DEG C, 24h is reacted under agitation；
(2) room temperature is cooled to after completion of the reaction, with 1mL dimethyl formamide solution diluting reaction mother liquors, then is added dropwise
Precipitated in 20mL methyl alcohol, collected sediment, be dried to constant weight, obtained 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：
Hydrogen spectrum nuclear magnetic spectrogram of the poly- thioamides of the present embodiment in deuterated dimethyl sulfoxide is as shown in Figure 1.Can from Fig. 1
Find out, the solvent peak and water peak of deuterated dimethyl sulfoxide are located at respectively 2.5 and 3.3ppm, the solvent dimethylformamide peak of residual
Positioned at 2.73,2.89 and 7.95ppm；The appearance of hydrogen atom in polymer is in addition.
Thermogravimetric curve figure of the poly- thioamides of the present embodiment in nitrogen atmosphere is as shown in Figure 2.Fig. 2 shows gained polymerization
Thing has preferable heat endurance, and heat decomposition temperature when weightless 5% is 284 DEG C.
It is as shown in Figure 3 that the poly- thioamides of the present embodiment makes the refractive index curve chart after film.Fig. 3 results show gained
Polymer has higher refractive index, and the refractive index at 630nm is up to 1.72, than general polymeric material such as polystyrene
It is much higher with polymethyl methacrylate etc..
Photoluminescence curve map of the poly- thioamides of the present embodiment under variable concentrations is as shown in Figure 4.Fig. 4 shows, is somebody's turn to do
The polymeric material of non-conjugated structure has preferable fluorescent emission, and as showing for fluorescent emission red shift occurs in the increase of concentration
As.
Embodiment 2
A kind of multicomponent polymerization of the alkynes for preparing poly- thioamides, sulphur and amine of the present embodiment, it is concrete to prepare step
It is rapid as follows：
(1) under inert gas shielding, by 68mg p dimethylamines, 285mg diacetylenes tetraphenylethylene and 64mg liters
Magnificent sulphur is added in 0.5mL pyridines and dissolves, and is warming up to 100～120 DEG C, and 4h is reacted under agitation；
(2) room temperature is cooled to after completion of the reaction, with 1mL dimethyl formamide solution diluting reaction mother liquors, then is added dropwise
Precipitated in 20mL methyl alcohol, collected sediment, be dried to constant weight, obtained poly- thioamides.
The diacetylene tetraphenylethylene of the present embodiment is according to side disclosed in document [Polym.Chem.2012,3,1481]
It is prepared by method.
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 preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any Spirit Essences and the changes, modification, replacement made under principle without departing from the present invention, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (5)
1. the multicomponent polymerization of a kind of alkynes for preparing poly- thioamides, sulphur and amine, it is characterised in that including following preparation
Step：
(1) under inert gas shielding, spread out by the primary amine monomer containing aromatic radical or aryl derivative, containing aromatic radical or aromatic radical
Biological end diine hydrocarbon monomer and elemental sulfur is added in solvent and dissolves, and is warming up to 50～120 DEG C of fully reactions；
(2) room temperature is cooled to after completion of the reaction, reaction mother liquor is added in precipitating reagent and is precipitated, collect sediment, be dried
To constant weight, poly- thioamides is obtained.
2. the multicomponent polymerization of a kind of alkynes for preparing poly- thioamides according to claim 1, sulphur and amine, it is special
Levy and be：Described elemental sulfur refers to sublimed sulfur.
3. the multicomponent polymerization of a kind of alkynes for preparing poly- thioamides according to claim 1, sulphur and amine, it is special
Levy and be：Described solvent refers to pyridine.
4. the multicomponent polymerization of a kind of alkynes for preparing poly- thioamides according to claim 1, sulphur and amine, it is special
Levy and be：Described precipitating reagent refers to methyl alcohol.
5. the multicomponent polymerization of a kind of alkynes for preparing poly- thioamides according to claim 1, sulphur and amine, it is special
Levy and be：The reaction mother liquor is added to the mode in precipitating reagent to be added dropwise, and reaction mother liquor is before being added in precipitating reagent
First it is diluted with dimethyl formamide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510317858.5A CN105001419B (en) | 2015-06-11 | 2015-06-11 | Alkyne, sulfur and amine multi-component polymerization method for preparing poly-thioamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510317858.5A CN105001419B (en) | 2015-06-11 | 2015-06-11 | Alkyne, sulfur and amine multi-component polymerization method for preparing poly-thioamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105001419A CN105001419A (en) | 2015-10-28 |
| CN105001419B true CN105001419B (en) | 2017-04-19 |
Family
ID=54374305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510317858.5A Active CN105001419B (en) | 2015-06-11 | 2015-06-11 | Alkyne, sulfur and amine multi-component polymerization method for preparing poly-thioamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105001419B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820335B (en) * | 2016-03-31 | 2018-09-14 | 华南理工大学 | A kind of polyene aminated compounds and preparation method thereof |
| CN106243351B (en) * | 2016-07-28 | 2019-01-15 | 华南理工大学 | No metal catalytic multicomponent polymerization preparation sequence controllable linear/hyper-branched polymer and method and application |
| 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 |
| CN107236128A (en) * | 2017-06-21 | 2017-10-10 | 华南理工大学 | The multicomponent polymerization of a kind of isonitrile, sulphur and amine prepares the method for polythiourea and the application of the polythiourea |
| CN107619477B (en) * | 2017-09-22 | 2020-06-30 | 中山大学 | Polythioamide and preparation method and application thereof |
| CN109535424B (en) * | 2018-10-22 | 2020-09-22 | 华南理工大学 | Polythioamide compound and preparation method and application thereof |
| CN110183675B (en) * | 2019-05-13 | 2022-03-29 | 华南理工大学 | Hyperbranched polythioamide compound and preparation method and application thereof |
| CN115124715B (en) * | 2021-03-29 | 2023-09-26 | 华南理工大学 | Preparation method of pyridyl polythioamide |
| CN115466388B (en) * | 2022-09-16 | 2023-09-08 | 华南理工大学 | Polythiourea compound and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5114704B2 (en) * | 2006-04-27 | 2013-01-09 | 国立大学法人富山大学 | Method for separating metal and method for recovering metal |
| CN101679616B (en) * | 2007-06-11 | 2012-08-08 | 香港科技大学 | Synthesis of acylarylenes and hyperbranched poly(acylarylene)s by metal-free cyclotrimerization of alkynes |
| CN101503398B (en) * | 2009-03-17 | 2012-03-21 | 成都金桨高新材料有限公司 | Novel sulfide or sulfone containing dianhydride, and preparation and use thereof |
-
2015
- 2015-06-11 CN CN201510317858.5A patent/CN105001419B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105001419A (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105001419B (en) | Alkyne, sulfur and amine multi-component polymerization method for preparing poly-thioamide | |
| CN108570149B (en) | Method for preparing polythiourea by multicomponent polymerization of isonitrile, sulfur and amine and application of polythiourea | |
| CN109553778B (en) | Method for preparing polyselenuride/polyselenocylamide by multicomponent polymerization of elemental selenium, isonitrile/alkyne and amine | |
| Nakabayashi et al. | RAFT polymerization of S-vinyl sulfide derivatives and synthesis of block copolymers having two distinct optoelectronic functionalities | |
| CN106893015A (en) | A kind of method that photoinduction organic catalysis prepare polymer under minute yardstick | |
| CN110407714A (en) | Hindered phenol and the compound difunctional antioxidant of amide groups intramolecular and its synthetic method | |
| CN110483773B (en) | Polyvinyl thioether ester and preparation method and application thereof | |
| CN104045778B (en) | Preparation method of star-like hybrid material with UCST and polyhedral oligomeric silsesquioxane (POSS) as core | |
| CN109535424B (en) | Polythioamide compound and preparation method and application thereof | |
| CN109161017B (en) | Multi-component polymerization method based on alkyne and sulfonyl azide, sulfonyl-containing polymer and application | |
| CN107325284B (en) | Hyperbranched polyphenyl triazole formate as well as preparation method and application thereof | |
| CN109400888B (en) | Water-soluble star polymer based on beta-cyclodextrin as core and preparation method thereof | |
| CN111690133B (en) | Polyalkenyl dithiocarbamate compound and preparation method thereof | |
| CN100360609C (en) | Method for preparing transparent hybridization material of polymetal oxygen cluster / polymer | |
| CN104558541B (en) | Conjugated polymer polymer based on acetylenic ketone intermediate and preparation method and application | |
| CN109942733A (en) | A kind of method that continuous flow moves synthetic polymer | |
| Zhang et al. | Polysiloxane-based hyperbranched fluorescent materials prepared by thiol-ene “click” chemistry as potential cellular imaging polymers | |
| CN102617770B (en) | Preparation method of linkage polymer based on cucurbituril [6] | |
| CN110357992A (en) | A kind of fluoropolymer-containing preparation method of super high molecular weight | |
| CN106243351A (en) | Controlled linear/the hyper-branched polymer of sequence and method and application are prepared in the polymerization of multicomponent without metal catalytic | |
| CN103275701A (en) | Dendritic molecule-modified fluorescent quantum dots, and preparation method and application thereof | |
| CN106279677B (en) | Rich in heteroatomic phosphine amidine quasi polymer and prepares the multicomponent polymerization of the polymer and apply | |
| CN106008995B (en) | A kind of preparation method of the hyperbranched poly thioether based on lipoic acid | |
| CN107434851B (en) | Preparation method of photosensitive hydrogel | |
| CN110845391B (en) | N, N-bis (2-phthaloyl) ethyl-acrylamide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |