CN117866192A - Preparation method and application of polythioamide compound - Google Patents
Preparation method and application of polythioamide compound Download PDFInfo
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- CN117866192A CN117866192A CN202311663703.8A CN202311663703A CN117866192A CN 117866192 A CN117866192 A CN 117866192A CN 202311663703 A CN202311663703 A CN 202311663703A CN 117866192 A CN117866192 A CN 117866192A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- -1 amine compound Chemical class 0.000 claims abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 78
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 239000012452 mother liquor Substances 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- 239000010931 gold Substances 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 80
- 150000002500 ions Chemical class 0.000 abstract description 24
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 description 50
- 150000001412 amines Chemical class 0.000 description 21
- 230000009471 action Effects 0.000 description 18
- 239000003153 chemical reaction reagent Substances 0.000 description 18
- 238000009826 distribution Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 16
- RBZMSGOBSOCYHR-UHFFFAOYSA-N 1,4-bis(bromomethyl)benzene Chemical compound BrCC1=CC=C(CBr)C=C1 RBZMSGOBSOCYHR-UHFFFAOYSA-N 0.000 description 13
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- OXHOPZLBSSTTBU-UHFFFAOYSA-N 1,3-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC(CBr)=C1 OXHOPZLBSSTTBU-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 3
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- QUTSYCOAZVHGGT-UHFFFAOYSA-N 2,6-bis(bromomethyl)pyridine Chemical compound BrCC1=CC=CC(CBr)=N1 QUTSYCOAZVHGGT-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GHITVUOBZBZMND-UHFFFAOYSA-N 1,3,5-tris(bromomethyl)benzene Chemical compound BrCC1=CC(CBr)=CC(CBr)=C1 GHITVUOBZBZMND-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- RJZCPVOAAXABEZ-UHFFFAOYSA-N 1,4-bis(iodomethyl)benzene Chemical compound ICC1=CC=C(CI)C=C1 RJZCPVOAAXABEZ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a preparation method and application of a polythioamide compound. The preparation method of the polythioamide compound comprises the following steps: mixing elemental sulfur, a polybasic halogenated compound, a polybasic amine compound and an alkali compound in an organic solvent for polymerization reaction; thus obtaining the polythioamide compound. The preparation method has the advantages of easily available reaction raw materials, mild polymerization conditions, simple process and high polymerization efficiency. The polythioamide compound has potential application value in adsorbing noble metal ions and/or heavy metal ions.
Description
Technical Field
The invention relates to the technical field of polymer chemistry and materialics, in particular to a preparation method and application of a polythioamide compound.
Background
Polythioamides are attracting attention due to their excellent characteristics, such as luminescence properties and the like. However, the current synthesis methods of polythioamides are widely reported, but are limited due to the complicated preparation of raw materials or the high price. The currently reported synthesis methods have certain disadvantages, which seriously hamper the development and application of polythioamides. The synthesis method of the polythioamide is shown as a formula (I). Method A: in 1999, japanese scientists developed multicomponent polymerization of elemental sulfur, aromatic aldehydes, and fatty amines to produce polythioamides. Method B: in 2015, we report the multi-component polymerization of elemental sulfur, aromatic alkynes, and fatty amines to produce polythioamides. Method C: in 2017, chen Youming teaches the synthesis of polythioamides by three-component polymerization of elemental sulfur, benzylamine, and fatty amines, but the substrate utility of this approach is relatively limited. Method D: tang Benzhong the objective group is to prepare polythioamide efficiently by multi-component polymerization of phenylacetic acid monomers, elemental sulfur and diamine monomers. Method E: tang Benzhong the subject group uses pyridine-activated diyne as a monomer to prepare polythioamides at room temperature or 40 ℃. However, these methods for preparing polythioamides have a problem in that the monomers are expensive.
It is therefore highly desirable to explore new methods for preparing polythioamides, to develop more efficient and convenient polymerization systems, and to explore new uses of polythioamides. According to literature investigation, the simple substance sulfur is a simple, cheap and easily available raw material, and the simple substance sulfur is taken as the raw material, so that the simple substance sulfur has low cost and can be widely applied to industrial production, and particularly, the simple substance sulfur is used for synthesizing polymers at present and the polymers have excellent mechanical property and processability. From literature studies, the reactivity of halogenated hydrocarbons is as follows: 1, 4-bis (iodomethyl) benzene & gt 1, 4-bis (bromomethyl) benzene & gt 1, 4-bis (chloromethyl) benzene. Among the halogenated hydrocarbons, 1, 4-bis (bromomethyl) benzene is a relatively inexpensive commercial monomer, and thus, the use of elemental sulfur and some commercial monomers to achieve low-cost and large-scale preparation of polythioamides is expected to drive further development. ( Synthesis,1986 (11): 894-899; j Polym Sci Pol chem.2001,39,3739; macromolecules 2015,48,7747; macromolecules 2017,50,8505; am.chem.soc.2019,142, 978; chem. )
Disclosure of Invention
The invention aims to provide a preparation method and application of a polythioamide compound with easily available raw materials, simple process and high efficiency.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a polythioamide compound comprises the following steps:
mixing elemental sulfur, a polybasic halogenated compound, a polybasic amine compound and an alkali compound in an organic solvent for polymerization reaction; thus obtaining the polythioamide compound.
Further, the polyamine compound is at least one selected from diamine compounds, triamine compounds and quaternary amine compounds;
preferably, the polyamine compound is selected from at least one of the following structural formulas:
H 2 N-C k H 2k -NH 2
wherein k is an integer of 1 to 20;
further preferably, the polyamine compound is selected from at least one of the following structural formulas:
further, the polyhalogenated compound is selected from at least one of a binary halogenated compound, a ternary halogenated compound and a quaternary halogenated compound.
Preferably, the dihalo-compound is selected from at least one of the following structural formulas:
X-C k H 2k -X
wherein Ar is aryl, k is an integer of 1-20, and X is one of Cl, br and I.
Further preferred, the dihalo-compound is selected from at least one of the following structural formulas:
further, the alkali compound is selected from one or more of N-methylpiperidine, DBU (1, 8-diazabicyclo undec-7-ene) and sodium hydroxide;
preferably, the alkali compound is N-methylpiperidine and/or DBU.
Further, the organic solvent is N, N-dimethylformamide;
further, the concentration of the polyhalogenated compound in the organic solvent is 0.1 to 1mol/L. Preferably, the concentration of the polyhalogenated compound in the organic solvent is 0.5-1 mol/L; further preferably, the concentration of the polyhalogenated compound in the organic solvent is 0.5mol/L.
Further, the mole ratio of the elemental sulfur, the amino group in the polyamine compound, the carbon atom connected with halogen in the polyhalogenated compound and the alkali compound is 1-6: 1:1 to 6:2 to 6.
Further, the temperature of the polymerization reaction is 80-100 ℃, and the time of the polymerization reaction is 6-15 h; preferably, the temperature of the polymerization reaction is 90-100 ℃, and the time of the polymerization reaction is 14h.
And further, after the polymerization reaction, dissolving mother liquor after the polymerization reaction in the organic solvent 1, then adding the organic solvent into a precipitator, collecting precipitate and drying to obtain the polythioamide compound.
Preferably, the drying temperature is 20-30 ℃; further preferably, the drying temperature is 22-28 ℃; more preferably, the drying temperature is 25 ℃.
Preferably, the organic solvent 1 is one or more of N, N-dimethylformamide and dimethyl sulfoxide;
preferably, the precipitant is selected from one or more of methanol, n-hexane and ethanol. Further preferably, the precipitant is n-hexane and/or ethanol.
Further, the polythioamide compound comprises the following structural general formula:
wherein n is an integer between 2 and 400; r is R 1 Is alkyl, R 2 Is aryl, R 3 Is aryl or alkyl, R 4 Is aryl or alkyl, R 5 Is aryl or alkyl.
Preferably, the polythioamide compound specifically comprises the following structural formula:
wherein i, m and n are each independently integers of 2 to 400.
Further preferably, the polythioamide compound specifically comprises the following structural formula:
wherein i, m and n are integers of 2-400.
The polythioamide compound prepared by the preparation method is applied to noble metal ion and/or heavy metal ion adsorption.
Further, the noble metal ion is a gold ion.
Further, the application comprises the steps of:
firstly, adding polythioamide into a solution containing noble metal ions and/or heavy metal ions, stirring for reaction, and centrifuging.
Preferably, the solution containing noble metal ions and/or heavy metal ions is further added with 5wt% hydrochloric acid aqueous solution to obtain a mixed solution, and then added with polythioamide.
Preferably, the concentration of noble metal ions and/or heavy metal ions in the solution containing noble metal ions and/or heavy metal ions is 10 ug/L-1000 mg/L; 1mg to 10mg of polythioamide is added into each 1mL to 10mL of the mixed solution.
Further preferably, the concentration of noble metal ions and/or heavy metal ions in the solution containing noble metal ions and/or heavy metal ions is 5mg/L to 1000mg/L; 10mg of polythioamide are added per 1mL of solution containing noble metal ions and/or heavy metal ions.
Preferably, the stirring speed of the stirring reaction is 800rpm, and the stirring reaction time is 1min-60min.
Preferably, the centrifugation rate of the centrifugation is 8000rpm.
Preferably, the centrifugation time of the centrifugation is 10min.
Further, the structure of the polythioamide is as follows:
wherein n is 2 to 300.
The invention has the beneficial effects that:
(1) The preparation method has the advantages of easily available reaction raw materials, direct commercial purchase and low price; the reaction process is simple, and the product yield is high;
(2) The simple substance sulfur and dihalogenated hydrocarbon have low cost, and the method not only can introduce sulfur elements into the polymer in a simple and convenient way, but also provides a method for developing and utilizing abundant simple substance sulfur resources;
(3) The polythioamide has low price, and the synthesis is simple, convenient and efficient;
(4) The preparation method has stronger group tolerance, and can introduce various functional groups into the monomer;
(5) The polythioamide compound prepared by the invention has better coordination capability with gold ions, and has potential application value in ion adsorption; especially, the gold enrichment efficiency is high, and the sensitivity is high.
Drawings
FIG. 1 is a chart showing the comparison of nuclear magnetic resonance hydrogen spectra of the polythioamide compound prepared in example 1 of the present invention and its corresponding monomers and model compounds in deuterated DMSO;
FIG. 2 is a chart showing the nuclear magnetic resonance carbon spectrum of the polythioamide compound prepared in example 1 of the present invention and the corresponding monomer and model compound thereof in deuterated DMSO;
FIG. 3 is an infrared absorption spectrum of the polythioamide compound prepared in example 1 of the present invention and its corresponding monomer and model compound; wherein in fig. 1,2 and 3 a is 1, 4-bis (bromomethyl) benzene, B is 1, 6-hexamethylenediamine, C is a monomer of a polythioamide compound P1, D is a polythioamide compound P1;
FIG. 4 is a graph showing the thermal weight loss of the polythioamide compound prepared in example 1 of the present invention;
FIG. 5 is a DSC graph of the polythioamide compound prepared in example 1 of the present invention.
Detailed Description
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
A polythioamide compound has a structural formula shown as P1:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as the formula (II):
wherein monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M2 is 1, 4-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M3 is 1, 6-hexamethylenediamine, which is commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M2 and (1 mmol,116.2 mg) of M3, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P1.
The yield of the polythioamide compound P1 was 91%, the weight average molecular weight was 11300, and the molecular weight distribution was 1.55, as determined and analyzed. The nuclear magnetic resonance spectrum hydrogen spectrum comparison diagram (representing solvent peak) of the polythioamide compound and the corresponding monomer is shown in fig. 1, the nuclear magnetic resonance carbon spectrum comparison diagram is shown in fig. 2, the characteristic peak corresponding to the hydrogen atom on the polythioamide compound-NH at the chemical shift of 10.34ppm in fig. 1, and the characteristic peak corresponding to the carbon atom on the polythioamide compound C=S at the chemical shift of 196.53ppm in fig. 2, so that the polymer can be determined to be the polythioamide compound. In addition, FIG. 3 is an infrared absorption spectrum of the polythioamide compound prepared in example 1 of the present invention and its corresponding monomers and model compounds. The generation of the c=s peak can also be observed from fig. 3. Fig. 4 shows the thermal weight loss curve of P1, and as can be seen from fig. 4, the temperature corresponding to 5% of the weight loss is 268 ℃, and the thermal stability is good. The DSC curve of P1 is shown in FIG. 5, and the glass transition temperature of P1 is 126 ℃ and is far lower than the thermal decomposition temperature of the compound, so that the thermal processing performance of the compound is ensured.
Example 2
A polythioamide compound has a structural formula shown as P2:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as the formula (III):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M2 is 1, 4-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M4 is 1, 8-octanediamine commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M2 and (1 mmol,144.3 mg) of M4, 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were successively added by syringe, the temperature was raised to 90℃and stirring was carried out at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P2.
The yield of the polythioamide compound P2 was 89%, the weight average molecular weight was 12500, and the molecular weight distribution was 1.45, as determined and analyzed.
Example 3
A polythioamide compound has a structural formula shown as P3:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as a formula (IV):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M2 is 1, 4-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M5 is 1, 4-xylylenediamine is commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M2 and (1 mmol,136.2 mg) of M5, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P3.
The yield of the polythioamide compound P3 was 96%, the weight average molecular weight was 14500, and the molecular weight distribution was 1.91 as determined and analyzed.
Example 4
A polythioamide compound has a structural formula shown as P4:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as a formula (five):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M2 is 1, 4-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M6 is trans-1, 4-cyclohexanediamine commercially available, in this example from TCI company. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M2 and (1 mmol,114.2 mg) of M6, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P4.
The yield of the polythioamide compound P4 was 67%, the weight-average molecular weight was 11200, and the molecular weight distribution was 1.64, as determined and analyzed.
Example 5
A polythioamide compound has a structural formula shown as P5:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as a formula (six):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M2 is 1, 4-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M7 is 1, 8-diamino-3, 6-dioxaoctane, which is commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M2 and (1 mmol,148.2 mg) of M7, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P5.
The yield of the polythioamide compound P5 was 97%, the weight average molecular weight was 11400, and the molecular weight distribution was 1.74, as determined and analyzed.
Example 6
A polythioamide compound has a structural formula shown as P6:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as a formula (seventh):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M2 is 1, 4-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M8 is 4,4' -diaminodicyclohexylmethane available commercially, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M2 and (1 mmol,210.4 mg) of M8, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P6.
The yield of the polythioamide compound P6 was 63%, the weight-average molecular weight was 11100, and the molecular weight distribution was 1.70, as determined and analyzed.
Example 7
A polythioamide compound has a structural formula shown as P7:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as the formula (eight):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M2 is 1, 4-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M6 is 4,4' -diaminodiphenylmethane commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M2 and (1 mmol,198.3 mg) of M6, 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were successively added by syringe, the temperature was raised to 90℃and stirring was carried out at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P7.
The yield of the polythioamide compound P7 was 85%, the weight average molecular weight was 6600, and the molecular weight distribution was 1.26, as determined and analyzed.
Example 8
A polythioamide compound has a structural formula shown as P8:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as a formula (nine):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M2 is 1, 4-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M10 is p-phenylenediamine, commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M2 and (1 mmol,108.1 mg) of M10, 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirring was carried out at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P8.
The yield of the polythioamide compound P8 was 81%, the weight-average molecular weight was 6100, and the molecular weight distribution was 1.27, as determined and analyzed.
Example 9
A polythioamide compound has a structural formula shown as P9:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as the formula (ten):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M2 is 1, 4-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M11 is 4,4' -diaminodiphenyl ether commercially available, in this example from TCI company. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M2 and (1 mmol,200.2 mg) of M11, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P9.
The yield of the polythioamide compound P9 was 91%, the weight average molecular weight was 5900, and the molecular weight distribution was 1.26, as determined and analyzed.
Example 10
A polythioamide compound has a structural formula shown as P10:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as formula (eleven):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M2 is 1, 4-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M12 is 4, 4-diaminodiphenyl sulfide commercially available, in this example from TCI company. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M2 and (1 mmol,216.3 mg) of M12, 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirring was carried out at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P10.
The yield of the polythioamide compound P10 was 66%, the weight average molecular weight was 8100, and the molecular weight distribution was 1.55, as determined and analyzed.
Example 11
A polythioamide compound has a structural formula shown as P11:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as formula (twelve):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M13 is 1, 3-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M3 is 1, 6-hexamethylenediamine, which is commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M13 and (1 mmol,116.2 mg) of M3, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P11.
The yield of the polythioamide compound P11 was 89%, the weight average molecular weight was 11100, and the molecular weight distribution was 1.68, as determined and analyzed.
Example 12
A polythioamide compound has a structural formula shown as P12:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as formula (thirteen):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M13 is 1, 3-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M5 is 1, 4-xylylenediamine is commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M13 and (1 mmol,136.2 mg) of M5, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P12.
The yield of the polythioamide compound P12 was 84%, the weight-average molecular weight was 12100, and the molecular weight distribution was 1.38, as determined and analyzed.
Example 13
A polythioamide compound has a structural formula shown as P13:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as formula (fourteen):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M13 is 1, 3-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M4 is 1, 8-octanediamine commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M13 and (1 mmol,144.3 mg) of M4, 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were successively added by syringe, the temperature was raised to 90℃and stirring was carried out at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P13.
The yield of the polythioamide compound P13 was 78%, the weight average molecular weight was 16900, and the molecular weight distribution was 2.01, as determined and analyzed.
Example 14
A polythioamide compound has a structural formula shown as P14:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as formula (fifteen):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M13 is 1, 3-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M10 is 1, 4-phenylenediamine commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M13 and (1 mmol,108.1 mg) of M10, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P14.
The yield of the polythioamide compound P14 was 58%, the weight-average molecular weight was 6900, and the molecular weight distribution was 2.01, as determined and analyzed.
Example 15
A polythioamide compound has a structural formula shown as P15:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as formula (sixteen):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M13 is 1, 3-bis (bromomethyl) benzene, commercially available, in this example from Annaiji corporation. M9 is 4,4' -diaminodiphenylmethane commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,264 mg) of M13 and (1 mmol,198.3 mg) of M9, 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were successively added by syringe, the temperature was raised to 90℃and stirring was carried out at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P15.
The yield of the polythioamide compound P15 was 58%, the weight-average molecular weight was 7000, and the molecular weight distribution was 1.33, as determined and analyzed.
Example 16
A polythioamide compound has a structural formula shown as P16:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as formula (seventeen):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M14 is 2, 6-bis (bromomethyl) pyridine, commercially available, in this example from Annaiji corporation. M3 is 1, 6-hexamethylenediamine, which is commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,265 mg) of M14 and (1 mmol,116.2 mg) of M3, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P16.
The yield of the polythioamide compound P16 was 78%, the weight average molecular weight was 15100, and the molecular weight distribution was 1.94, as determined and analyzed.
Example 17
A polythioamide compound has a structural formula shown as P17:
the polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as (eighteen):
monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. M14 is 2, 6-bis (bromomethyl) pyridine, commercially available, in this example from Annaiji corporation. M4 is 1, 8-octanediamine commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,265 mg) of M14 and (1 mmol,144.3 mg) of M4, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were sequentially added by syringe, the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours while keeping the temperature constant; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P17.
The yield of the polythioamide compound P17 was 78%, the weight-average molecular weight was 9100, and the molecular weight distribution was 1.34, as determined and analyzed.
Example 18
A hyperbranched polythioamide compound has a structural formula shown as P18
The polythioamide compound is prepared by directly reacting elemental sulfur, a bromo-compound and amine under the action of N-methylpiperidine, and the reaction equation is shown as a formula (nineteen):
wherein monomer M1 is elemental sulfur, commercially available, in this example from Guangzhou reagent plant. Monomer M15 is 1,3, 5-tris (bromomethyl) benzene, commercially available, in this example from Michael company. M3 is 1, 6-hexamethylenediamine, which is commercially available, in this example from Annaiji corporation. N-methylpiperidine in this example was purchased from Annaiji Inc.
The preparation method of the polythioamide compound comprises the following steps:
into a 10ml polymerization tube were charged 96mg (3 mmol) of monomer M1, (1 mmol,356.9 mg) of M15 and (1.5 mmol,174.3 mg) of M3, and 2mLN, N-dimethylformamide and 1 mLN-methylpiperidine were added in this order by syringe, and the temperature was raised to 90℃and stirred at a rate of 360rpm for 8 hours; after the reaction, the reaction mother liquor is dissolved in 2ml of LDMSO, then the reaction mother liquor is dripped into methanol, and then the mixture is stood still, filtered and dried at 20 ℃ to obtain the polythioamide compound P18.
The yield of the polythioamide compound P18 was 60%, the weight-average molecular weight was 14200, and the molecular weight distribution was 1.64, as determined and analyzed.
According to the embodiment, the preparation method of the polythioamide compound is provided, raw materials are easy to obtain, the method can be directly purchased commercially, the price is low, the reaction condition is mild, the process is simple, and the yield is high.
Gold standard solution (1000 mg/L) was diluted with 5wt% HCl to 100mg/L, which was divided into several 10mL, 0,0.5,1,3,5, 10mg of polythioamide compound P1, P11, P3 or P12 was added, respectively, and the reaction system was stirred at room temperature for 1h. Centrifuging the solution on a centrifugal machine with the rotating speed of 8000r/min for 10min, and filtering the supernatant through a filter membrane to obtain the final solution to be measured. The supernatant was tested for atomic absorption spectrum and the extraction yield of gold from the gold-containing solution was calculated as shown in table 1.
TABLE 1 Effect of polymer dosage on gold extraction efficiency (initial gold concentration of 1mg/10 ml)
A gold standard solution (1000 mg/L) was diluted to 100mg/L with 5wt% HCl, divided into several 10mL, 10mg of the polythioamide compound P1, P11, P3 or P12 was added, respectively, and stirred at room temperature for 1,2,5, 10, 20, 30, 40 and 60min, respectively. Centrifuging the solution on a centrifugal machine with the rotating speed of 8000r/min for 10min, and filtering the supernatant through a filter membrane to obtain the final solution to be measured. The supernatant was then tested for atomic absorption spectroscopy by AAS and the extraction yield of gold from the gold-containing solution was calculated as shown in table 2.
TABLE 2 influence of reaction time on gold extraction efficiency (initial gold concentration of 1mg/10 ml)
A gold standard solution (1000 mg/L) was diluted with 5wt% HCl to 100mg/L,50mg/L,10mg/L,1mg/L,0.1mg/L,0.01mg/L, 10mL of gold-containing solution was taken, and 300, 150, 30,3,0.3, and 0.03. Mu.L of DMF solution of the polythioamide compound P3 or P12 were added, respectively, at a concentration of 33.3mg/mL. The reaction system was stirred at room temperature for 1h, the solution was centrifuged on a centrifuge at 8000r/min for 10min, the atomic absorption spectrum of the supernatant was tested, and the extraction yield of gold from the gold-containing solution was calculated as shown in Table 3.
TABLE 3 Effect of initial ion concentration on gold extraction efficiency
Vp (uL): volume of DMF solution added to the polymer
From tables 1 to 3, it can be seen that the polythioamide compound prepared by the application has excellent adsorption effect on noble metal ions, namely gold ions, and can be used for extracting/removing noble metal ions/heavy metal ions.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the polythioamide compound is characterized by comprising the following steps of:
mixing elemental sulfur, a polybasic halogenated compound, a polybasic amine compound and an alkali compound in an organic solvent for polymerization reaction; thus obtaining the polythioamide compound.
2. The method according to claim 1, wherein the polyamine compound is at least one selected from the group consisting of a diamine compound, a triamine compound, and a tetramine compound;
the multi-halogenated compound is at least one selected from the group consisting of a binary halogenated compound, a ternary halogenated compound and a quaternary halogenated compound.
3. The method of claim 2, wherein the polyamine compound is selected from at least one of the following structural formulas:
wherein k is an integer of 1 to 20;
the dihalo-compound is selected from at least one of the following structural formulas:
X-C k H 2k -X
wherein Ar is aryl, k is an integer of 1-20, and X is one of Cl, br and I.
4. The preparation method according to claim 1, wherein the alkali compound is selected from one or more of N-methylpiperidine, DBU and sodium hydroxide;
the organic solvent is N, N-dimethylformamide;
the concentration of the multi-halogenated compound in the organic solvent is 0.1-1 mol/L.
5. The method according to claim 1, wherein the molar ratio of the elemental sulfur, the amino group in the polyamine compound, the halogen-bonded carbon atom in the polyhalogenated compound, and the alkali compound is 1 to 6:1:1 to 6:2 to 6;
the temperature of the polymerization reaction is 80-100 ℃, and the time of the polymerization reaction is 6-15 h.
6. The preparation method according to claim 1, wherein the mother liquor after polymerization is dissolved in an organic solvent 1 after polymerization, then added into a precipitant, and the precipitate is collected and dried to obtain the polythioamide compound;
the drying temperature is 20-30 ℃; the organic solvent 1 is one or more of N, N-dimethylformamide and dimethyl sulfoxide; the precipitant is selected from one or more of methanol, n-hexane and ethanol.
7. The method of claim 1, wherein the polythioamide comprises the following structural formula:
wherein n is an integer between 2 and 400; r is R 1 Is alkyl, R 2 Is aryl, R 3 Is aryl or alkyl, R 4 Is aryl or alkyl, R 5 Is aryl or alkyl.
8. The preparation method according to claim 7, wherein the polythioamide compound specifically comprises the following structural formula:
wherein i, m and n are each independently integers of 2 to 400.
9. Use of the polythioamide compound prepared by the preparation method of any one of claims 1-8 in noble metal ion and/or heavy metal ion adsorption.
10. The use according to claim 9, wherein the noble metal ion is a gold ion.
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