CN105040509A - Nano chitosan base quaternary alkyl ammonium starch ether compound antibacterial paper, preparation and application thereof - Google Patents
Nano chitosan base quaternary alkyl ammonium starch ether compound antibacterial paper, preparation and application thereof Download PDFInfo
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Abstract
The invention discloses nano chitosan base quaternary alkyl ammonium starch ether compound antibacterial paper, preparation and application thereof. The preparation method comprises the following steps: carrying out acid dissolution on chitosan, and mixing with a TPP solution to obtain nano chitosan; pasting a quaternary alkyl ammonium starch ether solution to obtain a quaternary alkyl ammonium starch ether pasting liquid; adding the nano chitosan into the quaternary alkyl ammonium starch ether pasting liquid to prepare a nano chitosan base quaternary alkyl ammonium starch ether compound papermaking dry strength agent with an antibacterial property, and adding the solution into paper pulp for papermaking. According to the preparation method, the nano chitosan is added into the quaternary alkyl ammonium starch ether pasting liquid, so that the nano chitosan can better give play to the antibacterial property; quaternary alkyl ammonium starch ether is added, so that the physical strength of the bacterial paper is remarkably improved; the nano chitosan base quaternary alkyl ammonium starch ether compound antibacterial paper is good in antibacterial property and excellent in physical property, and can be well applied to various fields like paper for daily use, food wrap paper and medicated paper.
Description
Technical field
The invention belongs to technical field of preparation of specialty paper, be specifically related to a kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper and preparation method thereof and application.
Background technology
Along with the progress that society is at full speed, the requirement of people to quality of life is more and more higher, and traditional manufacturing industry is badly in need of improving or transition, with better in the face of such opportunities and challenges.Anti-bacteria paper refers to the paper with anti-microbial property, is also people's a kind of base substances in life, packaging for foodstuff and medical in etc. field be all widely used.The anti-biotic material that current anti-bacteria paper uses belongs to single inorganic antibacterial material more, and it exists very large defect in paper strength, safety and environmental protection etc., and microorganism can be made to produce drug resistance problems.
In the age that this global microbial plague event frequently occurs, paper-making industry, as a traditional manufacturing industry, is necessary that a kind of novel anti-biotic material of exploitation goes to produce a kind of novel anti-bacteria paper to prevent the frequent generation of microorganism event.Wherein Nano chitosan because anti-microbial property is excellent, good to human body compatibility, have no stimulation, without side effect, be a kind of well anti-biotic material.
But the application of Nano chitosan in papermaking is little, and how better Nano chitosan to be applied to papermaking, be the problem demanding prompt solution that Nano chitosan is applied in field of papermaking.Therefore, we are necessary to develop a kind of novel security, durability, high temperature resistant better composite papermaking additive for the production of good anti-bacterial effect, novel antibacterial paper that paper strength is high.
Summary of the invention
For solving the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper.
Another object of the present invention is the Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper providing above-mentioned preparation method to obtain.
Another object of the present invention is the application providing above-mentioned Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper, comprises the following steps:
(1) to be chitosan solution and the concentration of 2 ~ 4mg/mL by concentration be sodium phosphate trimer (TPP) solution of 2 ~ 4mg/mL is by (30 ~ 50): after the volume ratio of (15 ~ 25) mixes, pH is adjusted to 5 ~ 7, then carry out sonic oscillation process, obtain Nano chitosan dispersion liquid;
(2) the papermaking dry-strengthening agent quaternary alkyl ammonium starch ether solution of a certain amount of mass concentration 3 ~ 5% is got, gelatinization 20 ~ 30min in also constantly stirring for 85 ~ 95 DEG C when, finally add a certain amount of water and mass concentration is adjusted to 0.3 ~ 1%, thus obtain quaternary alkyl ammonium starch ether dextrin solution; The Nano chitosan dispersion liquid that step (1) is obtained mixes with quaternary alkyl ammonium starch ether dextrin solution, stirs and obtains having the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent of anti-microbial property;
(3) bleached wood pulp is pulled an oar, then the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent with anti-microbial property getting a certain amount of step (2) obtained joins in slurry, stir, then manufacture paper with pulp and obtain described Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper.
Chitosan solution described in step (1) is dissolved in by shitosan in 1 ~ 3% acetic acid solution obtaining, and wherein the Solute mass of shitosan and acetic acid solution is than being 1:(2.5 ~ 15).
Chitosan solution described in step (1) 0.45 μm of filtering with microporous membrane, described sodium phosphate trimer (TPP) solution 0.22 μm of filtering with microporous membrane, and then the chitosan solution after filtering is mixed with sodium phosphate trimer (TPP) solution.
By pH being adjusted to 5 ~ 7 by NaOH solution in step (1), described NaOH solution concentration is preferably 1 ~ 4mol/L.
Shitosan described in step (1) and the ultrasonic process of sodium phosphate trimer mixed liquor, the power output 70W of sonic oscillation, ice-water bath sonic oscillation 10 ~ 30s, circulate 10 ~ 20 times, interval time 5s.
The mass ratio of the quaternary alkyl ammonium starch ether in the quaternary alkyl ammonium starch ether dextrin solution described in step (2) and the shitosan in Nano chitosan dispersion liquid is 1:(10 ~ 30).
Making beating described in step (3) refers to and utilizes beater to pull an oar to bleached wood pulp, and last beating degree is 40 ~ 44 ° of SR.
Bleached wood pulp described in step (3) is 1:(50 ~ 100 with the mass ratio of the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent with anti-microbial property).
The Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper that above-mentioned preparation method obtains.
Above-mentioned Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper is in the application in paper for daily use, food wrapper and pharmaceutical paper field.
Compared with prior art, the present invention has the following advantages and beneficial effect:
The present invention adopts Nano chitosan as antiseptic, and it has very large advantage in security, durability, environmental protection etc.The present invention joins Nano chitosan in quaternary alkyl ammonium starch ether, Nano chitosan can better play antibacterial effect, quaternary alkyl ammonium starch ether can also improve paper strength significantly simultaneously, and the Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper of gained not only has good antibiotic property and has excellent physical property.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.In preparation method of the present invention, each initiation material can be buied from market.
Embodiment 1
(1) get 5g shitosan to be dissolved in 3% acetic acid solution and to be made into 4mg/mL chitosan solution, with 0.45 μm of filtering with microporous membrane; By 4mg/mL sodium phosphate trimer (TPP) solution 0.22 μm of filtering with microporous membrane.Get after above-mentioned chitosan solution 30mL mixes with TPP solution 15mL, regulate pH to be 6 with 2mol/LNaOH solution, then carry out sonic oscillation (power output 70W, ice-water bath sonic oscillation 10s, circulate 20 times, interval time 5s), finally obtain Nano chitosan dispersion liquid;
(2) bleached wood pulp is pulled an oar, then Nano chitosan dispersion liquid is added to (mass ratio of Nano chitosan and bleached wood pulp is 1:100) in slurry, stir, then manufactured paper with pulp by sheet forming apparatus, obtain Nano chitosan anti-bacteria paper.
The Nano chitosan anti-bacteria paper inhibition zone size of above-mentioned preparation is as shown in table 1, and the tensile strength of anti-bacteria paper, tearing strength, folding strength are as shown in table 2.
Embodiment 2
A kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper, its preparation method is as follows:
(1) get 5g shitosan to be dissolved in 2% acetic acid solution and to be made into 4mg/mL chitosan solution, with 0.45 μm of filtering with microporous membrane; By 4mg/mL sodium phosphate trimer (TPP) solution 0.22 μm of filtering with microporous membrane.Get after above-mentioned chitosan solution 30mL mixes with TPP solution 20mL, regulate pH to be 5 with 2mol/LNaOH solution, then carry out sonic oscillation (power output 70W, ice-water bath sonic oscillation 20s, circulate 15 times, interval time 5s), finally obtain Nano chitosan dispersion liquid;
(2) getting 30mL mass concentration is 4% quaternary alkyl ammonium starch ether solution, then the water bath with thermostatic control of 95 DEG C is put into, when constantly stirring, gelatinization 20min, finally injects certain distilled water and mass concentration is adjusted to 0.3%, thus obtain quaternary alkyl ammonium starch ether dextrin solution; The Nano chitosan dispersion liquid that step (1) is obtained mixes with quaternary alkyl ammonium starch ether dextrin solution, stirs and obtains having the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent of anti-microbial property;
(3) bleached wood pulp is pulled an oar, then add Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent and join (mass ratio of Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent and bleached wood pulp is 1:100) in slurry, stir, manufactured paper with pulp by sheet forming apparatus again, obtain described Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper.
The chitin crystal bar base nano silver composite antibacterial paper inhibition zone size of above-mentioned preparation is as shown in table 1, and the tensile strength of anti-bacteria paper, tearing strength, folding strength are as shown in table 2.
Embodiment 3
A kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper, its preparation method is as follows:
(1) get 5g shitosan to be dissolved in 2% acetic acid solution and to be made into 3mg/mL chitosan solution, with 0.45 μm of filtering with microporous membrane; By 2mg/mL sodium phosphate trimer (TPP) solution 0.22 μm of filtering with microporous membrane.Get after above-mentioned chitosan solution 40mL mixes with TPP solution 20mL, regulate pH to be 6 with 1mol/LNaOH solution, then carry out sonic oscillation (power output 70W, ice-water bath sonic oscillation 30s, circulate 10 times, interval time 5s), finally obtain Nano chitosan dispersion liquid;
(2) getting 60mL mass concentration is 3% quaternary alkyl ammonium starch ether solution, then the water bath with thermostatic control of 85 DEG C is put into, when constantly stirring, gelatinization 30min, finally injects certain distilled water and mass concentration is adjusted to 1%, thus obtain quaternary alkyl ammonium starch ether dextrin solution; The Nano chitosan dispersion liquid that step (1) is obtained mixes with quaternary alkyl ammonium starch ether dextrin solution, stirs and obtains having the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent of anti-microbial property;
(3) bleached wood pulp is pulled an oar, then add Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent and join (mass ratio of Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent and bleached wood pulp is 1.5:100) in slurry, stir, manufactured paper with pulp by sheet forming apparatus again, obtain described Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper.
The chitin crystal bar base nano silver composite antibacterial paper inhibition zone size of above-mentioned preparation is as shown in table 1, and the tensile strength of anti-bacteria paper, tearing strength, folding strength are as shown in table 2.
Embodiment 4
A kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper, its preparation method is as follows:
(1) get 5g shitosan to be dissolved in 1% acetic acid solution and to be made into 2mg/mL chitosan solution, with 0.45 μm of filtering with microporous membrane; By 2mg/mL sodium phosphate trimer (TPP) solution 0.22 μm of filtering with microporous membrane.Get after above-mentioned chitosan solution 50mL mixes with TPP solution 25mL, regulate pH to be 7 with 3mol/LNaOH solution, then carry out sonic oscillation (power output 70W, ice-water bath sonic oscillation 15s, circulate 18 times, interval time 5s), finally obtain Nano chitosan dispersion liquid;
(2) the quaternary alkyl ammonium starch ether solution that a certain amount of 40mL mass concentration is 5% is got, put into the water bath with thermostatic control of 90 DEG C, the gelatinization 25min when constantly stirring, finally inject certain distilled water and mass concentration is adjusted to 0.5%, thus obtain quaternary alkyl ammonium starch ether dextrin solution; The Nano chitosan dispersion liquid that step (1) is obtained mixes with quaternary alkyl ammonium starch ether dextrin solution, stirs and obtains having the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent of anti-microbial property;
(3) bleached wood pulp is pulled an oar, Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent is joined (mass ratio of Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent and bleached wood pulp is 2:100) in slurry, stir, manufactured paper with pulp by sheet forming apparatus again, obtain described Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper.
The chitin crystal bar base nano silver composite antibacterial paper inhibition zone size of above-mentioned preparation is as shown in table 1, and the tensile strength of anti-bacteria paper, tearing strength, folding strength are as shown in table 2.
Embodiment 5
A kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper, its preparation method is as follows:
(1) get 5g shitosan to be dissolved in 3% acetic acid solution and to be made into 3mg/mL chitosan solution, with 0.45 μm of filtering with microporous membrane; By 3mg/mL sodium phosphate trimer (TPP) solution 0.22 μm of filtering with microporous membrane.Get after above-mentioned chitosan solution 40mL mixes with TPP solution 20mL, regulate pH to be 6 with 1mol/LNaOH solution, then carry out sonic oscillation (power output 70W, ice-water bath sonic oscillation 20s, circulate 15 times, interval time 5s), finally obtain Nano chitosan dispersion liquid;
(2) the quaternary alkyl ammonium starch ether solution that 100mL mass concentration is 3% is got, put into the water bath with thermostatic control of 85 DEG C, when constantly stirring, gelatinization 20min, finally injects certain distilled water and mass concentration is adjusted to 0.8%, thus obtain quaternary alkyl ammonium starch ether dextrin solution; The Nano chitosan dispersion liquid that step (1) is obtained mixes with quaternary alkyl ammonium starch ether dextrin solution, stirs and obtains having the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent of anti-microbial property;
(3) bleached wood pulp is pulled an oar, then Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent is joined (mass ratio of Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent and bleached wood pulp is 2:100) in slurry, stir, manufactured paper with pulp by sheet forming apparatus again, obtain described Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper.
The chitin crystal bar base nano silver composite antibacterial paper inhibition zone size of above-mentioned preparation is as shown in table 1, and the tensile strength of anti-bacteria paper, tearing strength, folding strength are as shown in table 2.
Embodiment 6
A kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper, its preparation method is as follows:
(1) get 5g shitosan to be dissolved in 2% acetic acid solution and to be made into 4mg/mL chitosan solution, with 0.45 μm of filtering with microporous membrane; By 4mg/mL sodium phosphate trimer (TPP) solution 0.22 μm of filtering with microporous membrane.Get after above-mentioned chitosan solution 40mL mixes with TPP solution 30mL, regulate pH to be 6 with 4mol/LNaOH solution, then carry out sonic oscillation (power output 70W, ice-water bath sonic oscillation 25s, circulate 12 times, interval time 5s), finally obtain Nano chitosan dispersion liquid;
(2) the quaternary alkyl ammonium starch ether solution that 120mL mass concentration is 4% is got, put into the water bath with thermostatic control of 90 DEG C, when constantly stirring, gelatinization 25min, finally injects certain distilled water and mass concentration is adjusted to 0.5%, thus obtain quaternary alkyl ammonium starch ether dextrin solution; The Nano chitosan dispersion liquid that step (1) is obtained mixes with quaternary alkyl ammonium starch ether dextrin solution, stirs and obtains having the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent of anti-microbial property;
(3) bleached wood pulp is pulled an oar, then Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent is joined (mass ratio of Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent and bleached wood pulp is 1:100) in slurry, stir, manufactured paper with pulp by sheet forming apparatus again, obtain described Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper.
The chitin crystal bar base nano silver composite antibacterial paper inhibition zone size of above-mentioned preparation is as shown in table 1, and the tensile strength of anti-bacteria paper, tearing strength, folding strength are as shown in table 2.
Embodiment 7
Anti-bacteria paper bacteriostasis property and paper physical strength character detect:
Anti-bacteria paper obtained in above-described embodiment 1-6 is measured inhibition zone size, and method is standard method CLSI, and namely anti-bacteria paper and blank body paper are cut into formed objects disk respectively, in agar medium, cultivate 24h, and temperature is 37 DEG C, and bacterial classification is Escherichia coli.Rear measurement sample periphery clear area diameter, clear area is antibacterial district, does not have growth, and the results are shown in Table 1.
The inhibition zone size of the various anti-bacteria paper of table 1
As can be seen from Table 1, embodiments of the invention are adopted to add the antibacterial effect of the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent of quaternary alkyl ammonium starch ether than the good anti-bacterial effect not adding quaternary alkyl ammonium starch ether; Along with the minimizing of Nano chitosan amount, antibacterial circle diameter diminishes.
By anti-bacteria paper equilibrium water conten 24h obtained in above-described embodiment 1-6, detect paper indices with testers such as tensile strength instrument, tearability instrument, folding strength instrument, result is as shown in table 2.
Table 2 paper performance detects
As can be seen from Table 2, adopt the addition of embodiments of the invention quaternary ammonium alkyl chitosan more, every physical strength index of anti-bacteria paper is better.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper, is characterized in that, comprise the following steps:
(1) to be chitosan solution and the concentration of 2 ~ 4mg/mL by concentration the be sodium tripolyphosphate solution of 2 ~ 4mg/mL is by (30 ~ 50): after the volume ratio of (15 ~ 25) mixes, pH is adjusted to 5 ~ 7, then carry out sonic oscillation process, obtain Nano chitosan dispersion liquid;
(2) the papermaking dry-strengthening agent quaternary alkyl ammonium starch ether solution of a certain amount of mass concentration 3 ~ 5% is got, gelatinization 20 ~ 30min in also constantly stirring for 85 ~ 95 DEG C when, finally add water and mass concentration is adjusted to 0.3 ~ 1%, obtain quaternary alkyl ammonium starch ether dextrin solution; The Nano chitosan dispersion liquid that step (1) is obtained mixes with quaternary alkyl ammonium starch ether dextrin solution, stirs and obtains having the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent of anti-microbial property;
(3) bleached wood pulp is pulled an oar, then the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent with anti-microbial property getting a certain amount of step (2) obtained joins in slurry, stir, then manufacture paper with pulp and obtain described Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper.
2. the preparation method of a kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper according to claim 1, it is characterized in that, chitosan solution described in step (1) is dissolved in by shitosan in 1 ~ 3% acetic acid solution obtaining, and wherein the Solute mass of shitosan and acetic acid solution is than being 1:(2.5 ~ 15).
3. the preparation method of a kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper according to claim 1, it is characterized in that, chitosan solution described in step (1) 0.45 μm of filtering with microporous membrane, described sodium tripolyphosphate solution 0.22 μm of filtering with microporous membrane, and then the chitosan solution after filtering is mixed with sodium tripolyphosphate solution.
4. the preparation method of a kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper according to claim 1, it is characterized in that, pH is adjusted to 5 ~ 7 by NaOH solution in (1) by step.
5. the preparation method of a kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper according to claim 1, it is characterized in that, the power output 70W of the sonic oscillation described in step (1), ice-water bath sonic oscillation 10 ~ 30s, circulate 10 ~ 20 times, interval time 5s.
6. the preparation method of a kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper according to claim 1, it is characterized in that, the mass ratio of the quaternary alkyl ammonium starch ether in the quaternary alkyl ammonium starch ether dextrin solution described in step (2) and the shitosan in Nano chitosan dispersion liquid is 1:(10 ~ 30).
7. the preparation method of a kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper according to claim 1, it is characterized in that, making beating described in step (3) refers to and utilizes beater to pull an oar to bleached wood pulp, and last beating degree is 40 ~ 44 ° of SR.
8. the preparation method of a kind of Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper according to claim 1, it is characterized in that, the bleached wood pulp described in step (3) is 1:(50 ~ 100 with the mass ratio of the Nano chitosan base quaternary alkyl ammonium starch ether composite papermaking dry strength agent with anti-microbial property).
9. the Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper obtained by preparation method described in any one of claim 1 to 8.
10. Nano chitosan base quaternary alkyl ammonium starch ether composite antibacterial paper according to claim 9 is in the application in paper for daily use, food wrapper and pharmaceutical paper field.
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| CN108442178A (en) * | 2018-05-07 | 2018-08-24 | 句容市兴武包装有限公司 | A kind of high-efficiency antimicrobial paper for daily use and preparation method thereof |
| CN113152140A (en) * | 2021-04-13 | 2021-07-23 | 苏州大学 | Antibacterial paper based on nano-micro heterojunction structure and preparation method thereof |
| CN113638264A (en) * | 2021-07-16 | 2021-11-12 | 江门市高力依科技实业有限公司 | Papermaking dry strength agent and preparation method and application thereof |
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