CN103865252A - Preparation method of water-based polyurethane nanosilver composite system with high-concentration nanosilver - Google Patents
Preparation method of water-based polyurethane nanosilver composite system with high-concentration nanosilver Download PDFInfo
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- CN103865252A CN103865252A CN201410096170.4A CN201410096170A CN103865252A CN 103865252 A CN103865252 A CN 103865252A CN 201410096170 A CN201410096170 A CN 201410096170A CN 103865252 A CN103865252 A CN 103865252A
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Abstract
The invention relates to a preparation method of a water-based polyurethane nanosilver composite system with high-concentration nanosilver. The composite system is obtained through the steps of synthesizing a hyperbranched waterborne polyurethane, next, generating nano-silver by virtue of in-situ reduction in the hyperbranched waterborne polyurethane, and then dialyzing the composite system until the pH is neutral, wherein the concentration of the nano-silver in the composite system can be over 50 micrograms per milliliter, the storage stability of the composite system is excellent, and therefore, the composite system can be stored for more than three months. The composite system is expected to further expand the application range of the nano-silver.
Description
Technical field
The invention belongs to the compound field of aqueous polyurethane/nano precious metal organic-inorganic, be specifically related to a kind of preparation method of aqueous polyurethane nano silver compound system of highly concentrated nano silver.
Background technology
Nanometer silver is as a kind of emerging functional materials, there is very stable physics and chemistry character, there is very excellent performance at aspects such as electronics, optics, antibacterial and catalysis, can be widely used in catalystic material, battery electrode material, optical material, anti-biotic material, coating etc.Silver ions is one of metal ion that bactericidal activity is the strongest, and it can destroy the respiratory function of bacterium and virus and make cell fission.Nanometer silver is the slowly-releasing process to Ag+ by surface atom, becomes one of the most potential anti-biotic material.
Aqueous polyurethane (WPU), for solvent borne polyurethane, is that urethane is water-soluble or be scattered in water and the dispersion that forms, also referred to as aqueous polyurethane or waterbased urethane.The research of aqueous polyurethane start from former West German Schlack of nineteen forty-two by vulcabond under the existence of emulsifying agent, be placed in water vigorous stirring and carry out emulsification, then add diamine compounds and carry out chain extension, successfully developed aqueous polyurethane.Aqueous polyurethane is free from environmental pollution, nontoxic, has a lot of excellent properties such as good wear resistance, snappiness and elasticity, and has inherited all ranges of application of solvent borne polyurethane, and aqueous polyurethane also has good physical and mechanical properties and biocompatibility simultaneously.
Hyperbranched polymer (HBP) is one of study hotspot in macromolecular material subject in recent years.Compared with traditional line polymer, because of its special dissaving structure, contain a large amount of end group groups and the low viscosity of bringing thus, without the feature such as chain entanglement, good solubility, cause people's interest widely, there is good application prospect in all many-sides such as nano material, luminescent material, coating, super branched polyurethane is because of the structure of himself, make its common advantage that has hyperbranched polymer and urethane resin concurrently, as many in: low viscosity, high resolution, active end group, performance easy-regulating etc.Thereby there is in a lot of fields a potential important application.
To aqueous polyurethane system, prepare aqueous polyurethane nano silver composite material by compound nanometer silver, the synthetic method of research water nano silver, by controlling grain size, distribution and the pattern of nanometer silver, the over-all properties of research matrix material.When nanometer silver is dispersed in organic polymer matrix compared with common polymer/inorganic filler systems, it be not simply adding of inorganic phase and organic phase and, but by nanometer particle and organic phase nanometer in sub-micrometer range in conjunction with forms between two-phase interface, exist more by force or a little less than chemical bond Van der Waals force hydrogen bond.Because very large interfacial area between nanometer silver and polymkeric substance and desirable interfacial adhesion can be eliminated itself and the unmatched problem of organism matrix thermal expansivity, can give full play to thus the excellent mechanical property high heat resistance of nanometer silver etc., simultaneously due to the rheological property of this type of nanocomposite melt and solution and Polymers Phase seemingly, therefore polytype forming process is had to adaptability widely.This matrix material has a wide range of applications at biologic medical, field of Environment Protection.
In recent years, the material of nanometer silver and the compound preparation of urethane has been obtained to some breakthroughs, as M. Akbarian etc. adds nanometer silver in the aqueous polyurethane coating system of two components to, the coating of preparation has better temperature tolerance (M. Akbarian, M.E. Olyaa, et al., The influence of nanosilver on thermal and antibacterial properties of a 2 K waterborne polyurethane coating. Progress in Organic Coatings, 2012,75 75:344-348.).Hsu has prepared the nanometer silver compound polyurethane material of polyester type, research is found not find that behavior (the Hsu S H of oxidative degradation appears in matrix material in the matrix material that adds nanometer silver, Chou C W. Enhanced biostability of polyurethane containing gold nano-particles. Polym. Degrad. Stabil., 2004,85 (1): 675-680.).Du jianzhong etc. utilizes the method for phase reversion to prepare the polymer nanocomposite silver system that polymer micelle is template, in this class compound system, the concentration of nanometer silver can reach 10-20 μ g/ml, nanometer silver reaches such concentration level some bacterium has been had to extraordinary bactericidal property, but in this class matrix material, the main two class problems that exist, one class is that dispersion and the size distribution of nanometer silver in polyurethane system of nanometer silver all do not reach desirable level, the non-constant width of size distribution of nanometer silver in general compound system, especially work the method that adopts mechanical-physical to mix, also limited to a certain extent the further application of this class matrix material, another kind of is that the effective concentration of nanometer silver is relatively low in compound system, at present in the MIC(of field of medical applications nanometer silver minimal inhibitory concentration) value concentrates on 6-30 μ g/ml, if the relative concentration of nanometer silver can further promote, the application of this class compound system has more wide prospect so.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of aqueous polyurethane nano silver compound system of highly concentrated nano silver, improve the relative concentration of the nanometer silver of existing aqueous polyurethane system, have larger space for the bactericidal properties and the over-all properties that improve this class matrix material, this class compound system material can be applied to biologic medical, pharmaceutical industries.
The preparation method of the aqueous polyurethane nano silver compound system of a kind of highly concentrated nano silver that the present invention proposes, concrete steps are as follows:
(1) will after the aliphatic isocyanates IPDI vacuum hydro-extraction of 33.3 weight part sulfonation water-soluble poly ester polyols and 11.1 weight parts, join in dimethyl formamide and stir, the mol ratio of control in dimethyl formamide-NCO:-OH is 3:1, then add 1, the sub-tin of octoate catalyst, 1 of dibutyltin dilaurate, be warming up to 80 ℃ of reaction 4h, add 10 weight parts to be dissolved in advance the hyper-branched polyester in dimethyl formamide, add the Diethylene Glycol of 4 quality weight parts, at 80 ℃, react 3h, cooling adds 2.3 weight part thionamic acid sodium, maintain 40 ℃ and react half an hour, cooling discharging, utilize homogenizer to add 139.3 weight part frozen water emulsifications, desolvation dimethyl formamide afterwards, obtain hyperbranched aqueous polyurethane emulsion,
(2) hyperbranched aqueous polyurethane in-situ reducing step (1) being obtained generates nanometer silver, be specially: the silver nitrate aqueous solution of 3-5ml is added in the 100ml hyperbranched aqueous polyurethane emulsion that step (1) obtains, in the process stirring, add sodium borohydride, wherein the mol ratio of Silver Nitrate and sodium borohydride is 1:3, the concentration of Silver Nitrate is 3mg/ml, solution colour gradually becomes brown, continue reaction 1 hour, it is neutral that gained composite emulsion is dialysed to pH in deionized water, obtains desired product.
In the present invention, described sulfonation water-soluble poly ester polyol adopts BY3301.
The concentration of the nanometer silver of the prepared compound system of the present invention exceedes 50 μ g/ml, and storage stability excellence, exceedes 3 months.
Embodiment
further illustrate the present invention below by embodiment, but the present invention is not limited to these embodiment.All umbers all represent by weight.
Testing method
Whether utilize the generation of ultraviolet-visible spectrophotometer and transmissioning electric mirror test nanometer silver, after three months, observing stability has layering.
Embodiment 1
Dimethyl formamide (DMF) (wherein-NCO:-OH=3:1 that stirs will be added after the aliphatic isocyanates IPDI vacuum hydro-extraction of 33.3 parts of sulfonation water-soluble poly ester polyol BY3301 and 11.1 parts, mol ratio), sub-tin (T-9) 1 of octoate catalyst, 1 of dibutyltin dilaurate (T-12), be warming up to 80 ℃ of reaction 4h, add 10 parts of hyper-branched polyester HyPer H202 that are dissolved in advance in DMF, add 4 parts of Diethylene Glycols (DEG), 80 ℃ of reaction 3h, cooling adds 2.3 parts of thionamic acid sodium (A95), maintain 40 ℃ and react half an hour, cooling discharging, utilize homogenizer to add 139.3 parts of frozen water emulsifications, desolvation DMF afterwards.
Get the hyperbranched aqueous polyurethane emulsion of 100ml, add silver nitrate solution 5ml(concentration 3mg/ml) stir.In the process stirring, add sodium borohydride (NaBH
4), wherein the mol ratio of Silver Nitrate and sodium borohydride is 1:3, solution colour gradually becomes brown, continues reaction 1 hour, and gained composite solution is dialysed to pH as neutral in deionized water.
Embodiment 2
Dimethyl formamide (DMF) (wherein-NCO:-OH=3:1 that stirs will be added after the aliphatic isocyanates IPDI vacuum hydro-extraction of 33.3 parts of sulfonation water-soluble poly ester polyol BY3301 and 11.1 parts, mol ratio), sub-tin (T-9) 1 of octoate catalyst, 1 of dibutyltin dilaurate (T-12), be warming up to 80 ℃ of reaction 4h, add 10 parts of hyper-branched polyester HyPer H202 that are dissolved in advance in DMF, add 4 parts of Diethylene Glycols (DEG), 80 ℃ of reaction 3h, cooling adds 2.3 parts of thionamic acid sodium (A95), maintain 40 ℃ and react half an hour, cooling discharging, utilize homogenizer to add 139.3 parts of frozen water emulsifications, desolvation DMF afterwards.
Get the hyperbranched aqueous polyurethane emulsion of 100ml, add silver nitrate solution 4ml(concentration 3mg/ml) stir.In the process stirring, add sodium borohydride NaBH
4, wherein the mol ratio of Silver Nitrate and sodium borohydride is 1:3, solution colour gradually becomes brown, continues reaction 1 hour, and gained composite emulsion is dialysed to pH as neutral in deionized water.Finally composite emulsion is sprayed on to corresponding substrate surface and obtains anion aqueous polyurethane nanometer silver compound coating.
Embodiment 3
Dimethyl formamide (DMF) (wherein-NCO:-OH=3:1 that stirs will be added after the aliphatic isocyanates IPDI vacuum hydro-extraction of 33.3 parts of sulfonation water-soluble poly ester polyol BY3301 and 11.1 parts, mol ratio), sub-tin (T-9) 1 of octoate catalyst, 1 of dibutyltin dilaurate (T-12), be warming up to 80 ℃ of reaction 4h, add 10 parts of hyper-branched polyester HyPer H202 that are dissolved in advance in DMF, add 4 parts of Diethylene Glycols (DEG), 80 ℃ of reaction 3h, cooling adds 2.3 parts of thionamic acid sodium (A95), maintain 40 ℃ and react half an hour, cooling discharging, utilize homogenizer to add 139.3 parts of frozen water emulsifications, desolvation DMF afterwards.
Get the sulfonate aqueous polyurethane emulsion of 100ml, add silver nitrate solution 3ml(concentration 3mg/ml) stir.In the process stirring, add sodium borohydride NaBH
4, wherein the mol ratio of Silver Nitrate and sodium borohydride is 1:3, solution colour gradually becomes brown, continues reaction 1 hour, and gained composite emulsion is dialysed to pH as neutral in deionized water.
Test result
| Embodiment | Uv-absorbing (nanometer silver) | Nanometer silver concentration (μ g/ml) | Storage stability (three months) |
| 1 | Have | 57 | Stable |
| 2 | Have | 76 | Stable |
| 3 | Have | 95 | Stable |
Claims (2)
1. a preparation method for the aqueous polyurethane nano of highly concentrated nano silver silver compound system, is characterized in that concrete steps are as follows:
(1) will after the aliphatic isocyanates IPDI vacuum hydro-extraction of 33.3 weight part sulfonation water-soluble poly ester polyols and 11.1 weight parts, join in dimethyl formamide and stir, the mol ratio of control in dimethyl formamide-NCO:-OH is 3:1, then add 1, the sub-tin of octoate catalyst, 1 of dibutyltin dilaurate, be warming up to 80 ℃ of reaction 4h, add 10 weight parts to be dissolved in advance the hyper-branched polyester in dimethyl formamide, add the Diethylene Glycol of 4 weight parts, at 80 ℃, react 3h, cooling adds 2.3 weight part thionamic acid sodium, maintain 40 ℃ and react half an hour, cooling discharging, utilize homogenizer to add 139.3 weight part frozen water emulsifications, desolvation dimethyl formamide afterwards, obtain hyperbranched aqueous polyurethane emulsion,
(2) hyperbranched aqueous polyurethane in-situ reducing step (1) being obtained generates nanometer silver, be specially: silver nitrate aqueous solution is added in the hyperbranched aqueous polyurethane emulsion that step (1) obtains, in the process stirring, add sodium borohydride, wherein the mol ratio of Silver Nitrate and sodium borohydride is 1:3, solution colour gradually becomes brown, continue reaction 1 hour, it is neutral that gained composite emulsion is dialysed to pH in deionized water, obtains desired product.
2. method according to claim 1, is characterized in that described sulfonation water-soluble poly ester polyol adopts BY3301.
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Cited By (10)
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| CN105780454A (en) * | 2016-04-21 | 2016-07-20 | 安徽皖翎羽绒制品有限公司 | Waterborne polyurethane coating agent containing superfine down feather fiber-nano silver microsphere |
| WO2017143980A1 (en) * | 2016-02-26 | 2017-08-31 | 陈汝霖 | Polyurethane material and preparation method thereof |
| CN108084794A (en) * | 2017-12-17 | 2018-05-29 | 江南大学 | The preparation method and application for the nano silver spray printing conductive ink that dissaving polymer is stablized |
| US10080822B1 (en) * | 2017-04-21 | 2018-09-25 | Rulin Chen | Use of polyurethane material in the preparation of latex product |
| CN108815583A (en) * | 2018-07-09 | 2018-11-16 | 南通大学 | A kind of super hydrophilic antibacterial ureter and preparation method thereof based on amino nano silver molecular brush |
| CN109135381A (en) * | 2018-07-20 | 2019-01-04 | 沙洲职业工学院 | A kind of dedicated silver-containing antibacterial solution of hydrophilic aluminum foil paint and preparation method thereof |
| CN110862503A (en) * | 2019-11-29 | 2020-03-06 | 佛山市瑞福物联科技有限公司 | Preparation method of conductive polyurethane prepolymer and conductive adhesive thereof |
| CN111333895A (en) * | 2020-04-24 | 2020-06-26 | 厦门长塑实业有限公司 | Transparent antibacterial high-temperature-resistant BOPA pre-coating film and preparation method thereof |
| CN112913854A (en) * | 2019-12-05 | 2021-06-08 | 上海沪正实业有限公司 | Preparation method of targeted nano silver particles |
| CN117186572A (en) * | 2023-09-12 | 2023-12-08 | 中绿新材料（江苏）有限公司 | Antibacterial fluororubber composite material for wearable equipment and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017143980A1 (en) * | 2016-02-26 | 2017-08-31 | 陈汝霖 | Polyurethane material and preparation method thereof |
| CN105780454A (en) * | 2016-04-21 | 2016-07-20 | 安徽皖翎羽绒制品有限公司 | Waterborne polyurethane coating agent containing superfine down feather fiber-nano silver microsphere |
| US10080822B1 (en) * | 2017-04-21 | 2018-09-25 | Rulin Chen | Use of polyurethane material in the preparation of latex product |
| CN108084794A (en) * | 2017-12-17 | 2018-05-29 | 江南大学 | The preparation method and application for the nano silver spray printing conductive ink that dissaving polymer is stablized |
| CN108815583A (en) * | 2018-07-09 | 2018-11-16 | 南通大学 | A kind of super hydrophilic antibacterial ureter and preparation method thereof based on amino nano silver molecular brush |
| CN109135381A (en) * | 2018-07-20 | 2019-01-04 | 沙洲职业工学院 | A kind of dedicated silver-containing antibacterial solution of hydrophilic aluminum foil paint and preparation method thereof |
| CN110862503A (en) * | 2019-11-29 | 2020-03-06 | 佛山市瑞福物联科技有限公司 | Preparation method of conductive polyurethane prepolymer and conductive adhesive thereof |
| CN110862503B (en) * | 2019-11-29 | 2022-02-11 | 佛山市瑞福物联科技有限公司 | Preparation method of conductive polyurethane prepolymer and conductive adhesive thereof |
| CN112913854A (en) * | 2019-12-05 | 2021-06-08 | 上海沪正实业有限公司 | Preparation method of targeted nano silver particles |
| CN112913854B (en) * | 2019-12-05 | 2022-04-01 | 上海沪正实业有限公司 | Preparation method of targeted nano silver particles |
| CN111333895A (en) * | 2020-04-24 | 2020-06-26 | 厦门长塑实业有限公司 | Transparent antibacterial high-temperature-resistant BOPA pre-coating film and preparation method thereof |
| CN111333895B (en) * | 2020-04-24 | 2022-04-29 | 厦门长塑实业有限公司 | Transparent antibacterial high-temperature-resistant BOPA pre-coating film and preparation method thereof |
| CN114524916A (en) * | 2020-04-24 | 2022-05-24 | 厦门长塑实业有限公司 | Bridging agent and preparation method thereof, and waterborne polyurethane mixed solution and preparation method thereof |
| CN114524916B (en) * | 2020-04-24 | 2023-12-01 | 福建长塑实业有限公司 | Bridging agent and preparation method thereof, aqueous polyurethane mixed solution and preparation method thereof |
| CN117186572A (en) * | 2023-09-12 | 2023-12-08 | 中绿新材料（江苏）有限公司 | Antibacterial fluororubber composite material for wearable equipment and preparation method thereof |
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