CN1986622A - Nano chitosan quaternary ammonium salt/organic rectorite composite material and its preparing method - Google Patents
Nano chitosan quaternary ammonium salt/organic rectorite composite material and its preparing method Download PDFInfo
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- CN1986622A CN1986622A CN 200610125560 CN200610125560A CN1986622A CN 1986622 A CN1986622 A CN 1986622A CN 200610125560 CN200610125560 CN 200610125560 CN 200610125560 A CN200610125560 A CN 200610125560A CN 1986622 A CN1986622 A CN 1986622A
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- quaternary ammonium
- ammonium salt
- chitosan quaternary
- rectorite
- organic rectorite
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Abstract
The present invention discloses a kind of nanometer chitosan quaternary ammonium salt/organic rectorite composite material combining both natural antiseptic and inorganic antiseptic and its preparation process. The composite material comprising chitosan quaternary ammonium salt and organic rectorite basically is prepared through intercalating chitosan quaternary ammonium salt into clay layers. Its preparation process includes cation exchanging between natural rectorite and modifier to obtain organic rectorite, dropping chitosan quaternary ammonium salt solution into organic rectorite suspension under stirring, and final freeze drying to obtain the nanometer chitosan quaternary ammonium salt/organic rectorite composite material. The composite material has greatly raised antiseptic performance and expanded application range.
Description
Technical field
The present invention relates to a kind of nano chitosan quaternary ammonium salt/organic rectorite composite material that is used as antiseptic-germicide and preparation method thereof.
Background technology
In recent years, the global microorganism disaster event frequency that causes by microorganism and mutation thereof the life that takes place frequently.Effectively prevent microbial growth, breed, spread and propagate, using the long acting antibiotic material is the simplest, safety and effective means.Inorganic antiseptic has efficiently, wide spectrum, long-term antibacterial performance, and good heat resistance, safe.But the easy variable color of inorganic antiseptic has limited its widespread use in material.Organic antibacterial agent has excellent specific properties such as sterilization speed is fast, antibacterial efficacy is high, colour stability is good, particularly natural organic antibacterial agent safety in utilization is very high, nontoxic, non-stimulated to human body, but the processing characteristics extreme difference of natural antibacterial agent, easy decomposition failure under the high temperature, thus its application is restricted.If inorganic and organic antibacterial agent combines, will improve the scope of application of antiseptic-germicide greatly.
Summary of the invention
The purpose of this invention is to provide a kind of energy and be used as nano chitosan quaternary ammonium salt/organic rectorite composite material of antiseptic-germicide and preparation method thereof, the advantage of chitosan quaternary ammonium salt natural antibacterial agent is combined with the advantage of rectorite leng inorganic antiseptic, to solve the problem that existing antiseptic-germicide exists in application.The anti-microbial property of this nano chitosan quaternary ammonium salt/organic rectorite composite material is more excellent than pure chitosan quaternary ammonium salt and organic rectorite, under acidity, neutrality even meta-alkalescence condition, stronger germ resistance is arranged all, have excellent heat resisting and good processing properties simultaneously.
The technical solution adopted in the present invention is: nano chitosan quaternary ammonium salt/organic rectorite composite material is made up of chitosan quaternary ammonium salt and organic rectorite, two kinds of shared total weight percent of raw material are respectively chitosan quaternary ammonium salt 50～80%, organic rectorite 20～50%, wherein organic rectorite is process tetradecyl dimethyl benzyl ammonium, cetyl trimethylammonium bromide or the resulting rectorite leng that organises of two bromination tetradecyl dimethyl ethyl ammonium modifications, and the chitosan quaternary ammonium salt intercalation is in the organic rectorite interlayer.The interlamellar spacing of this nano chitosan quaternary ammonium salt/organic rectorite composite material is between 4.48～4.8nm.
The preparation method of nano chitosan quaternary ammonium salt/organic rectorite composite material provided by the invention may further comprise the steps: will make the suspension of 1～2%w/v through tetradecyl dimethyl benzyl ammonium, cetyl trimethylammonium bromide or the resulting organic rectorite of two bromination tetradecyl dimethyl ethyl ammonium modifications, stirring also is heated to 70～80 ℃, is 1.1 * 10 with molecular weight
5～1.5 * 10
5Substitution value is the aqueous solution that 75～95% chitosan quaternary ammonium salt is made into 0.5～1%w/v, fully stir the back with chitosan quaternary ammonium salt: the organic rectorite weight ratio is that 1: 1～4: 1 ratio is added drop-wise to chitosan quaternary ammonium salt in the organic rectorite suspension and reacts, and reaction is finished postlyophilization and promptly got nano chitosan quaternary ammonium salt/organic rectorite composite material.
Wherein the preparation process of organic rectorite is earlier rectorite leng to be dispersed in the suspension that is made for 1～2%w/v in the distilled water, behind the homodisperse, high-speed stirring obtains stable rectorite leng suspension, again with tetradecyl dimethyl benzyl ammonium, cetyl trimethylammonium bromide or two bromination tetradecyl dimethyl ethyl ammonium are made into the aqueous solution of 1～2%w/v, with with the rectorite leng weight ratio be that 1: 1.5～1: 3 ratio splashes in the rectorite leng suspension that is heated to 85～90 ℃, constant temperature is to sufficient reacting, suction filtration, and use the distilled water repetitive scrubbing, until detecting no bromide anion with Silver Nitrate, under 85～90 ℃, be dried to constant weight, obtain organic rectorite.
As shown from the above technical solution, the present invention is by the direct intercalation of macromole solution, at first properties-correcting agent being inserted into accurate two-dimentional silicate rectorite leng lamella chien shih clay layer struts, weaken the reactive force of rectorite leng sheet interlayer, thereby strengthen the affinity between chitosan quaternary ammonium salt macromolecular chain and rectorite leng, rely on the chitosan quaternary ammonium salt macromolecular chain with the interaction between the properties-correcting agent organic group then, and the shearing force that stirs is inserted into the silicate lamella with macromolecular chain lamella is further strutted, make clay reach the homodisperse of nanoscale, obtain high molecular polymer/salt/organic rectorite nano composite material.
Chitosan quaternary ammonium salt is a kind of soluble derivative of chitosan, can be by chitosan and propylene oxide-trimethyl ammonium chloride prepared in reaction, and it all has germ resistance under acidity, neutrality even meta-alkalescence condition.After its intercalation entered organic rectorite, because clay layer combines to the advantage of the restraining and sterilizing bacteria effect of the absorption fixed action of bacterium and chitosan quaternary ammonium salt and the synergetic antibacterial effect of chitosan quaternary ammonium salt and organic rectorite, this composite nano germicide has more excellent anti-microbial property.Minimum inhibitory concentration is less than 0.00313% (w/v), and its anti-microbial property is directly proportional with the content and the interlamellar spacing of rectorite leng.Simultaneously, because the mica layer of high heat resistance reaches homodisperse in the chitosan quaternary ammonium salt matrix in the organic rectorite, the resistance toheat of nano chitosan quaternary ammonium salt/organic rectorite composite material improves a lot than chitosan quaternary ammonium salt, thereby processing characteristics improves, and has widened the scope of application of this complex antimicrobials.This complex antimicrobials will become the important directions of this field development from now on.
Embodiment
Embodiment 1: rectorite leng is dispersed in the suspension of making 1% (w/v) in the distilled water, and behind the homodisperse, high-speed stirring 30min obtains stable rectorite leng suspension.Tetradecyl dimethyl benzyl ammonium is made into 1% (w/v) aqueous solution, with with the rectorite leng weight ratio be that 1: 1.5 ratio is dripped in the rectorite leng suspension that is heated to 85 ℃, constant temperature 5h, suction filtration, and repeatedly wash with distilled water, until detecting no bromide anion with Silver Nitrate, under 85 ℃, be dried to constant weight, obtain organic rectorite.The 0.1g organic rectorite is made the aqueous solution of 1% (w/v), stir and be heated to 70 ℃, getting molecular weight again is 1.1 * 10
5～1.5 * 10
5, substitution value is that 75～95% chitosan quaternary ammonium salt 0.1g makes 0.5% (w/v) aqueous solution, is added drop-wise in the above-mentioned solution after stirring 3h, behind the reaction 2d, promptly gets nano chitosan quaternary ammonium salt/organic rectorite composite material after the lyophilize.The shared total weight percent of each component of this matrix material is respectively chitosan quaternary ammonium salt 50%, organic rectorite 50%.
Embodiment 2: rectorite leng is dispersed in the suspension of making 1.5% (w/v) in the distilled water, and behind the homodisperse, high-speed stirring 35min obtains stable rectorite leng suspension.Cetyl trimethylammonium bromide is made into 1.5% (w/v) aqueous solution, with with the rectorite leng weight ratio be that 1: 2 ratio is dripped in the rectorite leng suspension that is heated to 87 ℃, constant temperature 6h, suction filtration, and repeatedly wash with distilled water, until detecting no bromide anion with Silver Nitrate, under 87 ℃, be dried to constant weight, obtain organic rectorite.The 0.1g organic rectorite is made the aqueous solution of 1.5% (w/v), stir and be heated to 75 ℃, getting molecular weight again is 1.1 * 10
5～1.5 * 10
5, substitution value is that 75～95% chitosan quaternary ammonium salt 0.2g makes 0.75% (w/v) aqueous solution, is added drop-wise in the above-mentioned solution after stirring 3.5h, behind the reaction 2.5d, promptly gets nano chitosan quaternary ammonium salt/organic rectorite composite material after the lyophilize.The shared total weight percent of each component of this matrix material is respectively chitosan quaternary ammonium salt 66.7%, organic rectorite 33.3%.
Embodiment 3: rectorite leng is dispersed in the suspension of making 2% (w/v) in the distilled water, and behind the homodisperse, high-speed stirring 30min obtains stable rectorite leng suspension.Two bromination tetradecyl dimethyl ethyl ammoniums are made into 2% (w/v) aqueous solution, with with the rectorite leng weight ratio be that 1: 3 ratio is dripped in the rectorite leng suspension that is heated to 90 ℃, constant temperature 6.5h, suction filtration, and repeatedly wash with distilled water, until detecting no bromide anion with Silver Nitrate, under 90 ℃, be dried to constant weight, obtain organic rectorite.The 0.1g organic rectorite is made the aqueous solution of 2% (w/v), stir and be heated to 80 ℃, getting molecular weight again is 1.1 * 10
5～1.5 * 10
5, substitution value is that 75～95% chitosan quaternary ammonium salt 0.4g makes 1.0% (w/v) aqueous solution, is added drop-wise in the above-mentioned solution after stirring 4h, behind the reaction 3d, promptly gets nano chitosan quaternary ammonium salt/organic rectorite composite material after the lyophilize.The shared total weight percent of each component of this matrix material is respectively chitosan quaternary ammonium salt 80%, organic rectorite 20%.
Under PH=5.4, neutrality and PH=8.0 condition, embodiment is carried out anti-microbial property test, test result see the following form 1 (PH=5.4), table 2 (neutrality), table 3 (PH=8.0).Anti-microbial property is represented with minimum inhibitory concentration % (w/v).
Table 1
| Sample | Streptococcus aureus | Subtilis | Intestinal bacteria | Pseudomonas aeruginosa | Aspergillus niger |
| Organic rectorite chitosan quaternary ammonium salt embodiment 1 embodiment 2 embodiment 3 | 0.05 0.05 ＜0.00313 ＜0.00313 ＜0.00313 | 0.05 0.05 ＜0.00313 ＜0.00313 0.00625 | 0.1 0.1 0.0125 0.0125 0.025 | 0.1 0.1 0.1 0.1 0.1 | 0.0125 0.1 0.00625 0.00625 0.0125 |
Table 2
| Sample | Streptococcus aureus | Subtilis | Intestinal bacteria | Pseudomonas aeruginosa | Aspergillus niger |
| Organic rectorite chitosan quaternary ammonium salt embodiment 1 embodiment 2 embodiment 3 | 0.05 0.1 ＜0.00313 ＜0.0031 3 ＜0.00313 | 0.05 0.1 0.00313 0.00313 0.00625 | 0.1 0.1 0.025 0.025 0.05 | 0.1 - 0.1 0.1 0.1 | 0.0125 - 0.00625 0.00625 0.0125 |
Table 3
| Sample | Streptococcus aureus | Subtilis | Intestinal bacteria | Pseudomonas aeruginosa | Aspergillus niger |
| Organic rectorite chitosan quaternary ammonium salt embodiment 1 embodiment 2 embodiment 3 | 0.05 0.1 ＜0.00313 ＜0.00313 ＜0.00313 | 0.05 0.1 0.00313 0.00625 0.00625 | 0.1 0.1 0.05 0.05 0.1 | 0.1 - 0.1 0.1 0.1 | 0.0125 - 0.0125 0.0125 0.0125 |
Claims (5)
1, a kind of nano chitosan quaternary ammonium salt/organic rectorite composite material, its composition comprises chitosan quaternary ammonium salt and organic rectorite, form shared total weight percent for two kinds and be respectively chitosan quaternary ammonium salt 50～80%, organic rectorite 20～50%, wherein organic rectorite is process tetradecyl dimethyl benzyl ammonium, cetyl trimethylammonium bromide or the resulting rectorite leng that organises of two bromination tetradecyl dimethyl ethyl ammonium modifications, and the chitosan quaternary ammonium salt intercalation is in the organic rectorite interlayer.
2, nano chitosan quaternary ammonium salt/organic rectorite composite material according to claim 1 is characterized in that: the interlamellar spacing of nano chitosan quaternary ammonium salt/organic rectorite composite material is between 4.48～4.8nm.
3, nano chitosan quaternary ammonium salt/organic rectorite composite material according to claim 1 is characterized in that: used chitosan quaternary ammonium salt is the water-soluble thing that spreads out of chitosan, and its molecular weight is 1.1 * 10
5～1.5 * 10
5, substitution value is 75～95%.
4, the preparation method of the described nano chitosan quaternary ammonium salt/organic rectorite composite material of a kind of claim 1, it is characterized in that adopting following steps: will make the suspension of 1～2%w/v through tetradecyl dimethyl benzyl ammonium, cetyl trimethylammonium bromide or the resulting organic rectorite of two bromination tetradecyl dimethyl ethyl ammonium modifications, stirring also is heated to 70～80 ℃, is 1.1 * 10 with molecular weight
5～1.5 * 10
5Substitution value is the aqueous solution that 75～95% chitosan quaternary ammonium salt is made into 0.5～1%w/v, fully stir the back with chitosan quaternary ammonium salt: the organic rectorite weight ratio is that 1: 1～4: 1 ratio is added drop-wise to chitosan quaternary ammonium salt in the organic rectorite suspension and reacts, and reaction is finished postlyophilization and promptly got nano chitosan quaternary ammonium salt/organic rectorite composite material.
5, the preparation method of nano chitosan quaternary ammonium salt/organic rectorite composite material according to claim 4, it is characterized in that: the preparation process of organic rectorite is earlier rectorite leng to be dispersed in the suspension that is made for 1～2%w/v in the distilled water, behind the homodisperse, high-speed stirring obtains stable rectorite leng suspension, again with tetradecyl dimethyl benzyl ammonium, cetyl trimethylammonium bromide or two bromination tetradecyl dimethyl ethyl ammonium are made into the aqueous solution of 1～2%w/v, with with the rectorite leng weight ratio be that 1: 1.5～1: 3 ratio splashes in the rectorite leng suspension that is heated to 85～90 ℃, constant temperature is to sufficient reacting, suction filtration, and use the distilled water repetitive scrubbing, until detecting no bromide anion with Silver Nitrate, under 85～90 ℃, be dried to constant weight, obtain organic rectorite.
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| CN108102152B (en) * | 2017-12-14 | 2020-07-28 | 华南理工大学 | Hectorite immobilized nano-silver/chitosan antibacterial composite film for food packaging and preparation method and application thereof |
| CN108273475B (en) * | 2018-02-22 | 2021-04-06 | 湖北钟祥名流累托石开发有限公司 | Application of long-chain alkyl quaternary ammonium salt/rectorite composite material, mycotoxin adsorption material and preparation method thereof |
| CN108273475A (en) * | 2018-02-22 | 2018-07-13 | 湖北钟祥名流累托石开发有限公司 | The purposes of long chain alkyl ammonium salt/rectorite compound material, mycotoxin adsorption material and preparation method thereof |
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