CN104551006A - New method for preparing high thermal stability nanometer silver particles - Google Patents
New method for preparing high thermal stability nanometer silver particles Download PDFInfo
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- CN104551006A CN104551006A CN201510013740.3A CN201510013740A CN104551006A CN 104551006 A CN104551006 A CN 104551006A CN 201510013740 A CN201510013740 A CN 201510013740A CN 104551006 A CN104551006 A CN 104551006A
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Abstract
The invention relates to a new method for preparing high thermal stability nanometer silver particles. The new method for preparing the high thermal stability nanometer silver particles is characterized by including following steps: 1) using a reversible addition fragmentation chain transfer (RAFT) method to aggregate styrene (S) firstly, aggregate chloro-alpha-methylstyrene (CMS) then, and compound segmented copolymer PS-b-PCMS-b-PS which contains three sulphur ester groups in the middle, wherein a polymerization degree of a PS chain segment is 94, and a polymerization degree of PCMS is 39; 2) using the segmented copolymer PS-b-PCMS-b-PS as a stabilizer, reducing silver nitrate in situ so as to obtain nanometer silver particles protected by a segmented copolymer brush, wherein a molar ratio between the segmented copolymer PS-b-PCMS-b-PS and the silver nitrate is 1:32-1:16, a molar ratio between sodium borohydride and the silver nitrate is 1.1:1-2:1, and stirring speed is 720-1000r/min; 3) using quadrol as a cross-linking agent so as to obtain nanometer silver particles protected by a PCMS cross-linking shell layer and a PS brush, wherein the usage amount of the quadrol is 10-12.5 times of a molar number of a CMS structural unit of a PCMS chain segment. The target objects which are the high thermal stability nanometer silver particles and obtained through the new method for preparing the high thermal stability nanometer silver particles are even in particle diameter dispersion, good in compatibility with polymers, and good in thermal stability, and can not cause an aggregation phenomenon after being heated under temperature of 110 degree centigrade for 18h.
Description
Technical field
The present invention relates to a kind of novel method preparing high thermal stability nano silver particles, belong to the preparing technical field of metal nano material.
Background technology
In recent years, metal nanoparticle, especially gold and silver-colored, attracted great research interest due to the potential application in nanoelectronic, nanocomposite optical, catalysis, biology and the field such as biomedical.Containing the stable metal nanoparticle of sulfydryl polymer brush owing to forming the various and especially attracting concern of processing characteristics that is polymkeric substance excellence.
Most polymers brush is connected to the surface of metal nanoparticle by Au-S or Ag-S key, and Au-S or Ag-S key resolution lower (if Au-S is ~ 40Kcal/mol, Ag-S is lower).Have a strong impact on the stability of the polymer layer that surfaces of metal nanoparticles connects, especially at relatively high temperatures (>60 DEG C).Therefore, under the processing temperature of higher polymkeric substance, Au-S or Ag-S key can rupture, thus may cause reassembling of nanoparticle, and then affects its dispersiveness in polymeric matrix, affects the performance of matrix material.
The present invention prepares the nano silver particles of the crosslinked poly-p-chloromethyl styrene shell (PCMS) of novel high thermal stability and polystyrene (PS) brush duplicate protection.Crosslinked shell makes nano silver particles have stronger resistivity to chemical reagent, and have higher thermostability, even if still can be uniformly dispersed under the processing temperature of polymkeric substance, unlikely gathering, polystyrene brush makes nanoparticle and polymkeric substance have good consistency.
Summary of the invention
The object of this invention is to provide a kind of can solving the problem and prepare the novel method that high thermal stability is cross-linked poly-p-chloromethyl styrene shell and the coated nano silver particles of polystyrene brush.Its technology contents is:
The present invention relates to a kind of novel method preparing high thermal stability nano silver particles, it is characterized by employing following steps: 1) with dibenzyl trithio ester (DBTTC) for chain-transfer agent, adopt RAFT method (RAFT) first polymerizing styrene (S), repolymerization p-chloromethyl styrene (CMS), synthetic mesophase is containing the segmented copolymer PS-b-PCMS-b-PS of trithio ester group, wherein the polymerization degree of PS segment is 94, the PCMS polymerization degree is 39; 2) with segmented copolymer PS-b-PCMS-b-PS for stablizer, employing sodium borohydride is reductive agent, and DMF (DMF) is solvent, in-situ reducing Silver Nitrate, obtain the nano silver particles of segmented copolymer brush protection, wherein, the mol ratio of polymer P S-b-PCMS-b-PS and Silver Nitrate is 1:32 ~ 1:16, the mol ratio of sodium borohydride and Silver Nitrate is 1.1:1 ~ 2:1, stirring velocity is 720 ~ 1000 revs/min, and temperature of reaction is ice bath, and the reaction times is 3 hours; 3) be linking agent with quadrol, obtain the nano silver particles of crosslinked PCMS shell and the protection of PS brush, wherein the consumption of quadrol is 10 ~ 12.5 times of PCMS segment CMS structural unit mole number.The target compound particle size dispersion that the present invention obtains is even, good with polymer compatibility, Heat stability is good, heats 18 hours without clustering phenomena at 110 DEG C.
Compared with prior art, its advantage is in the present invention:
1, the nano silver particles particle size dispersion adopting this method to obtain is even, good with polymer compatibility;
2, Heat stability is good, heats 18 hours without clustering phenomena at 110 DEG C.
Accompanying drawing explanation
Fig. 1 is the GPC spectrogram of the segmented copolymer PS-b-PCMS-b-PS obtained in the embodiment of the present invention 1;
Fig. 2 is the nuclear magnetic spectrogram of the segmented copolymer PS-b-PCMS-b-PS obtained in the embodiment of the present invention 1;
Fig. 3 is that the nano silver particles of crosslinked PCMS shell and the protection of PS brush in the embodiment of the present invention 1 is schemed at the TEM of 110 DEG C of heating after 18 hours, and illustration is size distribution column diagram.
Embodiment
Embodiment 1, adopts following steps:
(1) preparation of segmented copolymer PS-b-PCMS-b-PS: take vinylbenzene 20 g and chain-transfer agent DBTTC 0.458g, be placed in eggplant shaped reaction bottle, logical high-purity argon gas 30 minutes, seals in argon atmospher.Magnetic agitation, 110 DEG C are reacted 24 hours.Ice bath cooling stops, and with the dilution of 8mL tetrahydrofuran (THF), is dropwise added dropwise in the ethanol of 5 times of volumes and precipitates, suction filtration, products therefrom by tetrahydrofuran (THF)/dissolve with ethanol/precipitation three times, then filters again, 50 DEG C of vacuum-drying 24 hours, obtains polystyrene macromolecular chain-transfer agent PS-CTA.Take dry PS-CTA 1.00 g and be placed in eggplant shaped reaction bottle, add initiator A IBN 5mg, monomer CMS 1 mL, dry tetrahydrofuran (THF) 5mL, logical dry argon gas 30 minutes, confined reaction bottle, magnetic agitation, 90 DEG C are reacted 24 hours.Ice bath cooling stops, and is dropwise added dropwise in the dehydrated alcohol of 5 times of volumes and precipitates, suction filtration, and products therefrom, again by tetrahydrofuran (THF)/anhydrous alcohol solution/precipitation three times, then filters, and 50 DEG C of vacuum-drying 24 hours, obtains segmented copolymer PS-b-PCMS-b-PS.
(2) preparation of the nano silver particles of segmented copolymer brush protection: take 0.05g segmented copolymer PS-b-PCMS-b-PS, be placed in clean Erlenmeyer flask.Add Silver Nitrate 0.017g, the DMF DMF of 10mL, ultrasonic dissolution, ice bath cools 20 minutes.Take 0.0042g sodium borohydride, ultrasonic dissolution is in 3mLDMF.Controlling stirring velocity is 1000 revs/min, dropwise drops in silver nitrate solution by sodium borohydride solution, dropwises continuation ice bath and reacts 3 hours.
(3) preparation of the nano silver particles of crosslinked PCMS shell and the protection of polystyrene brush: get Nano silver solution 10mL, add 0.1mL quadrol, room temperature magnetic agitation 3 days.
Fig. 1 is the GPC spectrogram of the segmented copolymer PS-b-PCMS-b-PS obtained in embodiment 1, and eluent is THF, and flow velocity is 1mL/min, and detector is refractive index detector; Fig. 2 is the nuclear magnetic spectrogram of the segmented copolymer PS-b-PCMS-b-PS obtained in embodiment 1, and deuterochloroform is solvent.Test is known, the segmented copolymer of gained consist of PS
47-b-PCMS
39-PS
47, number-average molecular weight is 15900, and molecular weight distributing index is 1.37.Fig. 3 is that PCMS is cross-linked the nano silver particles of shell and the protection of PS brush at the TEM figure of 110 DEG C of heating after 18 hours, and illustration is size distribution column diagram.As seen from the figure, nano silver particles is spherical, is uniformly dispersed, and median size is 11.9 ± 2.7 nm.
Embodiment 2, adopts following steps:
(1) preparation of segmented copolymer PS-b-PCMS-b-PS: take vinylbenzene 20 g and chain-transfer agent DBTTC 0.458g, be placed in eggplant shaped reaction bottle, logical high-purity argon gas 30 minutes, seals in argon atmospher.Magnetic agitation, 110 DEG C are reacted 24 hours.Ice bath cooling stops, and with the dilution of 8mL tetrahydrofuran (THF), is dropwise added dropwise in the ethanol of 5 times of volumes and precipitates, suction filtration, products therefrom by tetrahydrofuran (THF)/dissolve with ethanol/precipitation three times, then filters again, 50 DEG C of vacuum-drying 24 hours, obtains polystyrene macromolecular chain-transfer agent PS-CTA.Take dry PS-CTA 1.00 g and be placed in eggplant shaped reaction bottle, add initiator A IBN 5mg, monomer CMS 1 mL, dry tetrahydrofuran (THF) 5mL, logical dry argon gas 30 minutes, confined reaction bottle, magnetic agitation, 90 DEG C are reacted 24 hours.Ice bath cooling stops, and is dropwise added dropwise in the dehydrated alcohol of 5 times of volumes and precipitates, suction filtration, and products therefrom, again by tetrahydrofuran (THF)/anhydrous alcohol solution/precipitation three times, then filters, and 50 DEG C of vacuum-drying 24 hours, obtains segmented copolymer PS-b-PCMS-b-PS.
(2) preparation of the nano silver particles of segmented copolymer brush protection: take 0.10g segmented copolymer PS-b-PCMS-b-PS, be placed in clean Erlenmeyer flask.Add Silver Nitrate 0.017g, the DMF DMF of 10mL, ultrasonic dissolution, ice bath cools 20 minutes.Take 0.0076g sodium borohydride, ultrasonic dissolution is in 3mLDMF.Controlling stirring velocity is 720 revs/min, dropwise drops in silver nitrate solution by sodium borohydride solution, dropwises continuation ice bath and reacts 3 hours.
(3) preparation of the nano silver particles of crosslinked PCMS shell and the protection of polystyrene brush: get Nano silver solution 10mL, add 0.08mL quadrol, room temperature magnetic agitation 3 days.
Claims (4)
1. the present invention relates to a kind of novel method preparing high thermal stability nano silver particles, it is characterized by employing following steps: 1) with dibenzyl trithio ester (DBTTC) for chain-transfer agent, adopt RAFT method (RAFT) first polymerizing styrene (S), repolymerization p-chloromethyl styrene (CMS), synthetic mesophase is containing the segmented copolymer PS-b-PCMS-b-PS of trithio ester group, wherein the polymerization degree of PS segment is 94, the PCMS polymerization degree is 39; 2) with segmented copolymer PS-b-PCMS-b-PS for stablizer, employing sodium borohydride is reductive agent, and DMF (DMF) is solvent, in-situ reducing Silver Nitrate, obtain the nano silver particles of segmented copolymer brush protection, wherein, the mol ratio of polymer P S-b-PCMS-b-PS and Silver Nitrate is 1:32 ~ 1:16, the mol ratio of sodium borohydride and Silver Nitrate is 1.1:1 ~ 2:1, stirring velocity is 720 ~ 1000 revs/min, and temperature of reaction is ice bath, and the reaction times is 3 hours; 3) be linking agent with quadrol; obtain the nano silver particles of crosslinked PCMS shell and the protection of PS brush; wherein the consumption of quadrol is 10 ~ 12.5 times of PCMS segment CMS structural unit mole number; the target compound particle size dispersion that the present invention obtains is even; good with polymer compatibility; Heat stability is good, heats 18 hours without clustering phenomena at 110 DEG C.
2. a kind of novel method preparing high thermal stability nano silver particles according to claim 1, it is characterized in that: in step 1), first in high-purity argon atmosphere, take DBTTC as chain-transfer agent, bulk thermal polymerization vinylbenzene, polymerization temperature is 110 DEG C, magnetic agitation confined reaction 24 hours, ice bath cooling termination reaction, with tetrahydrofuran (THF) dilution, is precipitation agent precipitation with the ethanol of 5 times of volumes, suction filtration, dissolution precipitation three times repeatedly, obtains polystyrene macromolecular chain-transfer agent PS-CTA, vacuum-drying 24 hours; Then be chain-transfer agent with PS-CTA, Diisopropyl azodicarboxylate AIBN is initiator, and dry tetrahydrofuran is solvent, polymerization CMS monomer, and polymerization temperature is 90 DEG C, argon atmospher protection confined reaction 24 hours, ice bath cooling termination reaction; With the dehydrated alcohol of 5 times of volumes be precipitation agent precipitation, suction filtration, dissolution precipitation three times, obtains segmented copolymer PS-b-PCMS-b-PS repeatedly, and vacuum-drying 24 hours, is kept in moisture eliminator.
3. a kind of novel method preparing high thermal stability nano silver particles according to claim 1, it is characterized in that: step 2) in, with segmented copolymer PS-b-PCMS-b-PS for stablizer, employing sodium borohydride is reductive agent, N, dinethylformamide (DMF) is solvent, in-situ reducing Silver Nitrate, obtain the nano silver particles of segmented copolymer brush protection, wherein, the mol ratio of polymer P S-b-PCMS-b-PS and Silver Nitrate is 1:20 ~ 1:10, the mol ratio of sodium borohydride and Silver Nitrate is 1.1:1 ~ 2:1, stirring velocity is 720 ~ 1000 revs/min, temperature of reaction is ice bath, reaction times is 3 hours.
4. a kind of novel method preparing high thermal stability nano silver particles according to claim 1; it is characterized in that: in step 3); be linking agent with quadrol; make PCMS segment normal temperature crosslinked; obtain the nano silver particles of crosslinked PCMS shell and the protection of PS brush, wherein the consumption of quadrol is 12.5 times of PCMS segmented structure unit mole number.
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Cited By (4)
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| CN105665747A (en) * | 2016-04-22 | 2016-06-15 | 广东南海启明光大科技有限公司 | Preparation method of oily nano silver particles |
| CN111375784A (en) * | 2020-05-21 | 2020-07-07 | 宁夏师范学院 | Method for preparing stable nano-silver gel |
| CN113493568A (en) * | 2020-03-18 | 2021-10-12 | 北京大学深圳研究生院 | High-molecular noble metal nano composite material and preparation method thereof |
| CN115351288A (en) * | 2022-08-23 | 2022-11-18 | 西北工业大学 | Gold nanoflower and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105665747A (en) * | 2016-04-22 | 2016-06-15 | 广东南海启明光大科技有限公司 | Preparation method of oily nano silver particles |
| CN113493568A (en) * | 2020-03-18 | 2021-10-12 | 北京大学深圳研究生院 | High-molecular noble metal nano composite material and preparation method thereof |
| CN111375784A (en) * | 2020-05-21 | 2020-07-07 | 宁夏师范学院 | Method for preparing stable nano-silver gel |
| CN111375784B (en) * | 2020-05-21 | 2022-07-12 | 宁夏师范学院 | Method for preparing stable nano-silver gel |
| CN115351288A (en) * | 2022-08-23 | 2022-11-18 | 西北工业大学 | Gold nanoflower and preparation method and application thereof |
| CN115351288B (en) * | 2022-08-23 | 2023-06-23 | 西北工业大学 | Gold nanoflowers and preparation method and application thereof |
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Application publication date: 20150429 |