CN114470298A - Antibacterial nano silver/lignin polyurethane dressing and one-step preparation method thereof - Google Patents
Antibacterial nano silver/lignin polyurethane dressing and one-step preparation method thereof Download PDFInfo
- Publication number
- CN114470298A CN114470298A CN202111568116.1A CN202111568116A CN114470298A CN 114470298 A CN114470298 A CN 114470298A CN 202111568116 A CN202111568116 A CN 202111568116A CN 114470298 A CN114470298 A CN 114470298A
- Authority
- CN
- China
- Prior art keywords
- lignin
- silver
- polyurethane
- diisocyanate
- dressing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 102
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 73
- 239000004814 polyurethane Substances 0.000 title claims abstract description 73
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 26
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- 239000004088 foaming agent Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 40
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- -1 silver ions Chemical class 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 230000002421 anti-septic effect Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 231100000644 Toxic injury Toxicity 0.000 abstract description 3
- 230000029663 wound healing Effects 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- 241000588724 Escherichia coli Species 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 241000191967 Staphylococcus aureus Species 0.000 description 10
- 230000003385 bacteriostatic effect Effects 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000499 gel Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 231100000135 cytotoxicity Toxicity 0.000 description 2
- 230000003013 cytotoxicity Effects 0.000 description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000012970 tertiary amine catalyst Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
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- 229940057847 polyethylene glycol 600 Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
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- Engineering & Computer Science (AREA)
- Epidemiology (AREA)
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Abstract
The invention relates to the technical field of biomedical materials, in particular to an antibacterial nano silver/lignin polyurethane dressing and a method for preparing the dressing by a one-step method. In the dressing, lignin is uniformly distributed in polyurethane, nano-silver is uniformly loaded on the surface of the lignin polyurethane, and the loading amount of the nano-silver is 0.001-0.01%. The method for preparing the dressing by a one-step method comprises the following steps: the lignin polyol, the foaming agent and the diisocyanate are stirred, foamed and cured under the action of the catalyst to obtain the polyurethane foam material. The dressing adopts a simple one-step method, the liquefied lignin is mixed with the foaming agent, so that the nano-silver is obtained in the polyurethane synthesis process, the antibacterial performance of the polyurethane dressing is improved while the Ag content is reduced, the wound healing time can be shortened in the application, and the low-content nano-silver can reduce the toxic injury to normal cells of a human body, so that the safety and the reliability of the human body are improved.
Description
Technical Field
The invention relates to the technical field of biomedical materials, in particular to an antibacterial nano silver/lignin polyurethane dressing and a preparation method thereof.
Background
The lignin is an aromatic high molecular polymer, has high carbon content, high thermal stability, antibacterial activity, inoxidizability and low cytotoxicity, is a promising natural raw material in the field of biomedicine, and can be used as an antibacterial auxiliary material.
The polyurethane foam dressing has good flexibility, good moisture permeability and low cytotoxicity, can be used as a drug carrier, can absorb a large amount of exudates, and is almost completely permeable to oxygen and carbon dioxide. However, the preparation of polyurethane mainly depends on petrochemicals, and the use of natural lignin instead of petroleum resources is a feasible method for preparing environment-friendly medical polyurethane materials.
Metal antibacterial dressings have been widely studied in the biomedical field, in which silver nanoparticles (Ag NPs) have a broad-spectrum antibacterial property and can effectively kill bacteria, fungi, and viruses. The nano silver composite dressings are more in variety, but the nano silver composite dressings mostly have the problems of instability, good sterilization effect, high toxicity and the like.
At present, the nano silver/lignin polyurethane dressing needs to adopt a simple preparation method, and the silver content is reduced without adding chemical organic matters, so that the nano silver/lignin polyurethane dressing is relatively difficult, the silver content is higher, about 0.1-1%, and the cost is higher. For example, Chinese patent (publication No. CN107312315B) discloses a lignin/silver composite antibacterial agent and discloses the application of the antibacterial agent in polyurethane. According to the scheme, silver ions are adsorbed by using carboxylic acid negative electricity functional groups introduced into alkali lignin, and the silver ions are reduced into silver nanoparticles by using reducing functional groups such as phenolic hydroxyl groups, so that the lignin/silver composite antibacterial agent is obtained first and then added into polyurethane. The method is relatively complex, and the addition amount of the antibacterial agent is relatively large, and the weight of the antibacterial agent accounts for 0.5-3% of that of the polyurethane.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide the antibacterial nano silver/lignin polyurethane dressing which is free of chemical organic matters, reduces the content of silver ions, reduces the production cost and ensures the sterilization effect.
The above object of the present invention is achieved by the following technical solutions: an antibacterial nano silver/lignin polyurethane dressing, lignin is uniformly distributed in polyurethane, nano silver is uniformly loaded on the surface of the lignin polyurethane, and the loading capacity of the nano silver is 0.001% -0.01%.
Preferably, the nano silver is spherical particles with the diameter of 10nm-80 nm.
The second purpose of the invention is to provide a one-step method for preparing the antibacterial nano silver/lignin polyurethane dressing, which comprises the following steps: the lignin polyol, the foaming agent and the diisocyanate are stirred, foamed and cured under the action of a catalyst to prepare the polyurethane foam material.
According to the invention, the lignin polyol reacts with isocyanate to generate a carbamate bond, meanwhile, the foaming agent is added, the phenolic hydroxyl group reserved in the lignin structure is used as a reducing agent, and silver ions are reduced to nano silver in situ in the process of gelling while generating gas, so that the nano silver-loaded lignin polyurethane material is obtained.
Preferably, the components comprise, by weight, 15-30 parts of lignin polyol, 0.15-0.3 part of catalyst, 0.05-0.09 part of foaming agent and 10-20 parts of diisocyanate.
Preferably, the lignin polyol is prepared by the following method: performing liquefaction reaction on 20-40 parts by weight of lignin, 100 parts by weight of polyol and 3.0-6.0 parts by weight of concentrated sulfuric acid to obtain the lignin polyol, wherein the temperature of the liquefaction reaction is 120-150 ℃, and the time is 0.5-2 hours. During the liquefaction of lignin, the structure of lignin polyol can be directly influenced by the change of the catalyst and the reaction condition. The reaction degree is not enough, so that the hydroxyl content of the lignin polyol is changed, and the subsequent polyurethane synthesis reaction is influenced; however, if the excessive reaction causes the lignin to generate a crosslinking and blocking phenomenon, an uneven solution is formed, and the synthesis failure of the polyurethane is directly influenced.
Further preferably, the lignin comprises one or more of alkali lignin, lignosulfonate, enzymatic lignin, organic solvent lignin and Kraft lignin. More preferably, the lignin is organosolv lignin. Compared with other organic solvent lignin, the organic solvent lignin has moderate molecular weight and distribution, rich active groups and easy modification.
Further preferably, the polyhydric alcohol comprises one or more of polyethylene glycol 400, polyethylene glycol 600, polytetrahydrofuran 400, polytetrahydrofuran 600, ethylene glycol, propylene glycol, butanediol and glycerol. More preferably, the polyol is a mixture of polyethylene glycol 400 and glycerol, and the mass ratio of the polyethylene glycol 400 to the glycerol is 4: 1. compared with other organic solvent lignin, the mixture of polyethylene glycol 400 and glycerol not only has higher reaction activity with the organic solvent lignin and isocyanate, but also has moderate molecular weight, and is beneficial to preparing the high-resilience lignin-based polyurethane foam material.
Further preferably, the temperature of the liquefaction reaction is 130-140 ℃ and the time is 0.8-1.2 h. The reaction temperature is low, the reaction degree is low, and the hydroxyl in the lignin structure is not completely reacted; at high reaction temperatures, a re-coagulation reaction occurs, and lumps appear in the polyol. Similarly, if the reaction time is short, the reaction is incomplete, and if the reaction time is long, lumps appear. Further preferably, the temperature of the liquefaction reaction is 140 ℃ and the reaction time is 1 hour.
Preferably, the foaming agent is a solution containing 0.1-8.0mol/L silver ions. The antibacterial performance of the polyurethane dressing can be regulated and controlled by controlling the concentration of the foaming agent.
Preferably, the foaming agent is one or more of silver nitrate aqueous solution, silver acetate aqueous solution and silver sulfate aqueous solution.
Preferably, the diisocyanate comprises one or more of isophorone diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, 1, 5-naphthalene diisocyanate and toluene diisocyanate.
Preferably, the catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, pyridine, triethylamine, triethylenediamine and tetrabutyl titanate. More preferably, the catalyst is dibutyltin dilaurate. The organotin catalyst contributes to the gel reaction and is not favorable for gas generation. When the catalyst is dibutyltin dilaurate, the gel reaction can be balanced with the gas generation rate. The reaction of water in the foaming agent and isocyanate is violent, the strength of the wall of the foam hole is improved in the early foaming period of the product polyurea, and meanwhile, favorable conditions are provided for the stability of bubbles generated by carbon dioxide. In contrast, tertiary amine catalysts favor gas generation over catalysis of the gel reaction. The tertiary amine catalyst generates gas before the gel in the reaction process, and the foam grows and then is faded due to no gel.
Preferably, the preparation method of the antibacterial nano silver/lignin polyurethane dressing specifically comprises the following steps: and (2) stirring and mixing lignin polyol, a catalyst and a foaming agent, and then stirring, foaming and curing diisocyanate to obtain the antibacterial nano silver/lignin polyurethane dressing.
More preferably, the stirring speed before adding the diisocyanate is 300-800r/min, and still more preferably 500-800 r/min. Further preferably, the stirring speed after the addition of the diisocyanate is 8000-13000r/min, and still more preferably 10000-12000 r/min. Before the diisocyanate is added, the stirring speed is not too high or too low, the stirring is not uniform at low speed, the stirring is overheated at high speed, the subsequent reaction is affected, and the reaction rate is not uniform. After the diisocyanate is added, if the stirring speed is low, the components are not uniformly dispersed, the reaction is insufficient, the rate of gas generation is slow, and as a result, the product is hard and the structure is in a closed-cell state.
Compared with the prior art, the invention has the following beneficial effects:
1. the antibacterial nano silver/lignin polyurethane dressing disclosed by the invention has the advantages that the Ag content is reduced, the cost is reduced, the antibacterial performance of the polyurethane dressing is improved, the wound healing time can be shortened in application, and the low-content nano silver can reduce the toxic injury to normal cells of a human body, so that the safety and reliability of the human body are improved.
2. The antibacterial nano-silver/lignin polyurethane dressing adopts a simple one-step method, and the liquefied lignin is mixed with the foaming agent, so that nano-silver is obtained in the polyurethane synthesis process. Phenolic hydroxyl in the lignin structure is used as a reducing agent and a blocking agent, and silver ions are directly reduced into nano silver particles under the condition of not adding other chemical organic matters. The raw materials are green and environment-friendly, the antibacterial effect of the obtained dressing is obviously improved, the antibacterial rate to escherichia coli within 1 hour is 18.3% -99.8%, and the antibacterial rate to staphylococcus aureus within 4 hours is 47.8% -100%.
Drawings
FIG. 1 is a transmission electron microscope image of the antibacterial nano silver/lignin polyurethane dressing in example 1 of the present invention.
FIG. 2 is a transmission electron microscope image of the antibacterial nano silver/lignin polyurethane dressing in example 2 of the present invention.
FIG. 3 is a transmission electron microscope image of the antibacterial nano silver/lignin polyurethane dressing in example 2 of the present invention.
FIG. 4 is a graph showing the antibacterial effect of the antibacterial nano silver/lignin polyurethane dressings of examples 1 to 4 and comparative example 1 on the agar plate of E.coli with time.
Fig. 5 is a graph showing the antibacterial effect of the antibacterial nanosilver/lignin polyurethane dressings of examples 1 to 4 and comparative example 1 on the agar plate of staphylococcus aureus as a function of time.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
Example 1
According to the weight parts, 30 parts of enzymatic hydrolysis lignin, 80 parts of polyethylene glycol 400, 20 parts of glycerol and 4.5 parts of 98% sulfuric acid are respectively weighed and placed in a three-neck flask, mechanical stirring is carried out under the protection of nitrogen, heating is carried out at 140 ℃ for reaction for 1 hour, and lignin polyol is obtained through dewatering for later use.
According to the weight parts, 20 parts of the prepared lignin polyol, 0.2 part of dibutyltin dilaurate and 0.06 part of silver nitrate aqueous solution with the concentration of 0.1mol/L are taken as foaming agents, stirred and mixed for 7min at the speed of 800r/min, 13.5 parts of hexamethylene diisocyanate are added, stirred and mixed for 60s at the speed of 12000r/min, the mixture is quickly poured into a mold, and the mold is stood for foaming, curing and demolding are carried out at the room temperature, so that the antibacterial nano silver/lignin polyurethane dressing (marked as dressing 1) is obtained.
The transmission electron microscope image of the nano-silver/lignin polyurethane dressing prepared in this example is shown in fig. 1, the appearance and size of the nano-silver are characterized, the nano-silver is uniformly loaded on the surface of the lignin polyurethane, the loading amount of the nano-silver is 0.002% of that of the polyurethane, and the size of the nano-silver particles in the transmission electron microscope is about 30 nm.
The bacteriostatic effect of the nano silver/lignin polyurethane dressing (dressing 1) prepared in the example on escherichia coli is shown in dressing 1 in fig. 2, and the bacteriostatic rates at 1 hour, 2 hours, 4 hours and 8 hours sequentially reach 18.3%, 51.6%, 65.6% and 96.2%.
The bacteriostatic effect of the nano silver/lignin polyurethane dressing (dressing 1) prepared in the embodiment on staphylococcus aureus is shown in dressing 1 in fig. 3, and the bacteriostatic rates in 1 hour, 2 hours, 4 hours and 8 hours are 27.3%, 28.4%, 47.8% and 81.5% in sequence.
Example 2
The difference from example 1 is only that this example replaces 0.1mol/L silver nitrate aqueous solution with 1mol/L silver nitrate aqueous solution to obtain an antibacterial nano silver/lignin polyurethane dressing (labeled as dressing 2), and the transmission electron microscope image of the nano silver/lignin polyurethane dressing prepared by this example is shown in FIG. 2, and the nano silver loading accounts for 0.01% of the polyurethane.
The antibacterial performance of the antibacterial nano silver/lignin polyurethane dressing (marked as dressing 2) prepared in the embodiment is tested by the same method as that of the dressing 1, and the antibacterial effect on escherichia coli is shown as the dressing 2 in fig. 2, wherein the antibacterial rates of the dressing 2 on escherichia coli in 1 hour, 2 hours, 4 hours and 8 hours sequentially reach 98.6%, 99.7%, 100% and 100%; the bacteriostatic effect on staphylococcus aureus is shown in dressing 2 in fig. 3, and the bacteriostatic rates in 1 hour, 2 hours, 4 hours and 8 hours sequentially reach 1.8%, 19.3%, 72.5% and 98.8%.
Example 3
The difference from example 1 is only that this example replaces 0.1mol/L silver nitrate aqueous solution with 7.5mol/L silver nitrate aqueous solution to obtain an antibacterial nano silver/lignin polyurethane dressing (labeled as dressing 3), and the transmission electron microscope image of the nano silver/lignin polyurethane dressing prepared by this example is shown in FIG. 3, and the nano silver loading amount is 0.09% of the polyurethane.
The antibacterial performance of the antibacterial nano silver/lignin polyurethane dressing (marked as dressing 3) prepared in the embodiment is tested by the same method as that in the embodiment 1, and the antibacterial effect of the auxiliary material 3 on escherichia coli is shown in the dressing 3 in fig. 2, wherein the antibacterial rates of the auxiliary material 3 on escherichia coli in 1 hour, 2 hours, 4 hours and 8 hours sequentially reach 99.8%, 100%, 100% and 100%; the bacteriostatic effect on staphylococcus aureus is shown in dressing 3 in fig. 3, and the bacteriostatic rates on staphylococcus aureus in 1 hour, 2 hours, 4 hours and 8 hours sequentially reach 11.5%, 45.1%, 99.0% and 100%.
Example 4
The only difference from example 1 is that this example replaces 20 parts lignin polyol with 15 parts to give an antibacterial nanosilver/lignin polyurethane dressing (labeled dressing 4).
The antibacterial performance of the antibacterial nano silver/lignin polyurethane dressing (marked as dressing 4) prepared in the embodiment is tested by the same method as that of the dressing 1, and the antibacterial effect of the auxiliary material 4 on escherichia coli is shown in the dressing 4 in fig. 2, wherein the antibacterial rates of the auxiliary material 4 on the escherichia coli in 1 hour, 2 hours, 4 hours and 8 hours sequentially reach 32.5%, 38.7%, 59.3% and 80.1%; the bacteriostatic effect on staphylococcus aureus is shown in dressing 4 in fig. 3, and the bacteriostatic rates on staphylococcus aureus in 1 hour, 2 hours, 4 hours and 8 hours sequentially reach 13.8%, 13.4%, 16.7% and 43.2%.
Example 5
The only difference from example 1 is that the lignin polyol in this example was prepared by the following method: 30 parts by weight of enzymatic hydrolysis lignin, 80 parts by weight of polyethylene glycol 400, 20 parts by weight of glycerol and 5.0 parts by weight of concentrated sulfuric acid are reacted for 1.5 hours at 130 ℃. During the liquefaction of lignin, the structure of lignin polyol can be directly influenced by the change of the catalyst and the reaction condition. The reaction degree is not enough, so that the hydroxyl content of lignin polyol is changed, the content of the obtained nano silver is reduced, and the antibacterial effect is weakened; excessive reaction causes the lignin to generate a crosslinking and caking phenomenon, so that an uneven solution is formed, the synthesis failure of polyurethane is directly influenced, and the mechanical property is weakened. The final mechanical properties and antibacterial properties of the dressing in this example are slightly reduced compared to example 1.
Example 6
The only difference from example 1 is that this example replaces 20 parts lignin polyol with 30 parts lignin polyol. The content of lignin polyol is increased, the content of hydroxyl in reactants is increased, the mixing ratio of cyanate to hydroxyl in the reaction is reduced, the reaction speed of foaming is reduced, the structure of cells is not uniform, and the size tends to be reduced, so the dressing in the embodiment has inferior antibacterial performance to the dressing in the embodiment 1.
Example 7
The only difference from example 1 is that this example replaces 13.5 parts of hexamethylene diisocyanate by 20 parts. In the polyurethane reaction process, the mixing ratio of isocyanate and hydroxyl is increased, the reaction generates an excessively high crosslinking density, the internal stress between polyurethane chains is enhanced, and the phenomenon of shrinkage of polyurethane foam occurs, so the mechanical property of the dressing in the embodiment is inferior to that of the dressing in the embodiment 1.
Example 8
The only difference from example 1 is that this example replaces dibutyltin dilaurate with triethylenediamine. The tin catalyst can balance the gel reaction rate and the gas generation rate, and on the contrary, the tertiary amine catalyst has higher catalytic efficiency on isocyanate and water, thereby breaking the balance between the gel reaction rate and the gas generation rate; the structure of the material is damaged, a uniform cell structure cannot be formed, the nano silver is loaded unevenly, and the antibacterial performance of the dressing in the embodiment is not as stable as that in the embodiment 1.
Example 9
The only difference from example 1 is that this example replaces 60s of 12000r/min mixing after the addition of the diisocyanate with 30s of 6000r/min mixing. Under the conditions of short time and low rotating speed, the reactants are still in a viscous state, the reactants are difficult to disperse uniformly, local overheating of the reactants is caused, part of the reaction starts and coagulates into solid, and after a period of time, the other part of the reaction starts. The foam produced is of uneven shade, non-uniform cell structure and size, and still has a portion of unreacted viscous liquid. The performance of the dressing in this example was therefore inferior to the dressing in example 1.
Example 10
The only difference from example 1 is that this example replaces 0.06 parts of 0.1mol/L silver nitrate solution with 0.1 parts of 0.1mol/L silver nitrate solution as the foaming agent. The volume of the silver nitrate solution with equal concentration is increased, on one hand, the content of the nano silver loaded in the polyurethane material is directly influenced by the amount of silver ions, so that the nano silver is increased; on the other hand, the content of water determines the reaction degree of the isocyanate to form polyurea, so when the adding amount of water is increased, more carbon dioxide gas is generated in the reaction process, so that the cell size of the polyurethane material is increased, and the structure of the material is embrittled after the cell size is increased, the mechanical property of the dressing in the embodiment is damaged, which is not the same as that of the dressing in the embodiment 1.
Comparative example 1
The only difference from example 1 is that this comparative example 1 replaces the aqueous silver nitrate solution with acetone. Water is used as a chemical foaming agent to participate in the reaction of polyurethane, and the product polyurea in the reaction process improves the strength of the wall of the bubble in the early foaming stage and provides favorable conditions for the stability of the bubble. In contrast, acetone, as a physical blowing agent, does not participate in chemical reactions, and when the reaction temperature is lower than its boiling point, the gel speed is relatively fast and greater than the gas generation speed. Thus, the gas in the cell cannot impact the cell walls, thereby forming a predominantly closed cell foam.
The antibacterial effects of the antibacterial nanosilver/lignin polyurethane dressings of examples 1 to 4 (dressings 1 to 4, respectively) and comparative example 1 (control group in the drawing) on escherichia coli and staphylococcus aureus with time are shown in fig. 4 and 5, respectively.
From fig. 4 and 5, the antibacterial nano silver/lignin polyurethane dressing of the invention has better improved antibacterial effects on escherichia coli and staphylococcus aureus. The dressing adopts a simple one-step method, the liquefied lignin is mixed with the foaming agent, so that the nano-silver is obtained in the polyurethane synthesis process, the antibacterial performance of the polyurethane dressing is improved while the Ag content is reduced, the wound healing time can be shortened in application, and the low-content nano-silver can reduce the toxic injury to normal cells of a human body, so that the safety and reliability of the human body are improved.
The above description is illustrative of the present invention and is not to be construed as limiting thereof, as numerous modifications and variations therein are possible to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The antibacterial nano-silver/lignin polyurethane dressing is characterized in that lignin is uniformly distributed in polyurethane, nano-silver is uniformly loaded on the surface of the lignin polyurethane, and the loading amount of the nano-silver is 0.001% -0.01%.
2. The antiseptic nano silver/lignin polyurethane dressing of claim 1, wherein the nano silver is spherical particle with diameter of 10nm-80 nm.
3. The one-step method for preparing the antibacterial nano silver/lignin polyurethane dressing according to claim 1, is characterized by comprising the following steps: the lignin polyol, the foaming agent and the diisocyanate are stirred, foamed and cured under the action of the catalyst to obtain the polyurethane foam material.
4. The one-step method for preparing the antibacterial nano silver/lignin polyurethane dressing according to claim 3 is characterized in that, by weight, 15-30 parts of lignin polyol, 0.15-0.3 part of catalyst, 0.05-0.09 part of foaming agent and 10-20 parts of diisocyanate are adopted.
5. The one-step method for preparing the antibacterial nano silver/lignin polyurethane dressing according to the claim 3 or 4, wherein the lignin polyol is prepared by the following steps: performing liquefaction reaction on 20-40 parts by weight of lignin, 100 parts by weight of polyol and 3.0-6.0 parts by weight of concentrated sulfuric acid to obtain the lignin polyol, wherein the temperature of the liquefaction reaction is 120-150 ℃, and the time is 0.5-2 hours.
6. The one-step method for preparing the antibacterial nano silver/lignin polyurethane dressing according to claim 3, wherein the foaming agent is an aqueous solution containing 0.1-8.0mol/L silver ions.
7. The one-step method for preparing the antibacterial nano silver/lignin polyurethane dressing according to claim 3 or 6, wherein the foaming agent is one or more of a silver nitrate aqueous solution, a silver acetate aqueous solution and a silver sulfate aqueous solution.
8. The one-step method for preparing the antibacterial nano silver/lignin polyurethane dressing according to claim 3, wherein the diisocyanate comprises one or more of isophorone diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, 1, 5-naphthalene diisocyanate and toluene diisocyanate.
9. The one-step method for preparing the antibacterial nano silver/lignin polyurethane dressing according to claim 3, wherein the catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, pyridine, triethylamine, triethylenediamine and tetrabutyl titanate.
10. The one-step method for preparing antibacterial nano silver/lignin polyurethane dressing according to claim 3, wherein the stirring speed before adding diisocyanate is 800r/min and the stirring speed after adding diisocyanate is 13000r/min and 8000-.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114794149A (en) * | 2022-06-07 | 2022-07-29 | 西南交通大学 | Nano lignin antibacterial material and preparation method and application thereof |
| CN115282320A (en) * | 2022-10-09 | 2022-11-04 | 佳利士江苏新材料科技有限公司 | Bacteria-resistant PU film medical dressing and processing technology thereof |
| CN117599260A (en) * | 2024-01-23 | 2024-02-27 | 四川大学 | Medical polyurethane foam with anti-inflammatory function and preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696261A (en) * | 2009-10-29 | 2010-04-21 | 华南理工大学 | Lignin polyurethane and preparation method thereof |
| CN107312315A (en) * | 2017-05-11 | 2017-11-03 | 华南理工大学 | A kind of lignin/silver complex antimicrobials and its preparation method and application |
| CN112934206A (en) * | 2021-04-09 | 2021-06-11 | 中国科学院宁波材料技术与工程研究所 | Modified lignin polyurethane adsorbent and preparation method thereof |
-
2021
- 2021-12-21 CN CN202111568116.1A patent/CN114470298A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696261A (en) * | 2009-10-29 | 2010-04-21 | 华南理工大学 | Lignin polyurethane and preparation method thereof |
| CN107312315A (en) * | 2017-05-11 | 2017-11-03 | 华南理工大学 | A kind of lignin/silver complex antimicrobials and its preparation method and application |
| CN112934206A (en) * | 2021-04-09 | 2021-06-11 | 中国科学院宁波材料技术与工程研究所 | Modified lignin polyurethane adsorbent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "《典型无机功能材料及应用研究》", 31 January 2021, 吉林科学技术出版社, pages: 173 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114794149A (en) * | 2022-06-07 | 2022-07-29 | 西南交通大学 | Nano lignin antibacterial material and preparation method and application thereof |
| CN114794149B (en) * | 2022-06-07 | 2022-09-20 | 西南交通大学 | Nano lignin antibacterial material and preparation method and application thereof |
| CN115282320A (en) * | 2022-10-09 | 2022-11-04 | 佳利士江苏新材料科技有限公司 | Bacteria-resistant PU film medical dressing and processing technology thereof |
| CN117599260A (en) * | 2024-01-23 | 2024-02-27 | 四川大学 | Medical polyurethane foam with anti-inflammatory function and preparation and application thereof |
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