CN109265693A - A kind of antibacterial agent and the preparation method and application thereof based on hemicellulose - Google Patents
A kind of antibacterial agent and the preparation method and application thereof based on hemicellulose Download PDFInfo
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- CN109265693A CN109265693A CN201810841044.5A CN201810841044A CN109265693A CN 109265693 A CN109265693 A CN 109265693A CN 201810841044 A CN201810841044 A CN 201810841044A CN 109265693 A CN109265693 A CN 109265693A
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- CN
- China
- Prior art keywords
- preparation
- antibacterial agent
- guanidine hydrochloride
- xylan
- hemicellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
Abstract
The invention discloses a kind of antibacterial agent and the preparation method and application thereof based on hemicellulose.Method includes the following steps: cationic xylan is dissolved in ultrapure water, dissolved by heating in water-bath, lead to nitrogen, initiator is added, caused to be added after a certain period of time and make modified polyhexamethylene guanidine hydrochloride by oneself, cool down, purify after reaction, it is dry.The xylan grafting polyhexamethylene guanidine hydrochloride of purity is high is obtained after drying, xylan grafting polyhexamethylene guanidine hydrochloride has both xylan and polyhexamethylene guanidine hydrochloride performance, with preferable anti-microbial property, it is good to paper adsorption effect, effectively improve the paper anti-microbial property and mechanical performance of secondary stock.Preparation method of the invention has technique easy to operate, environmental-friendly characteristic.
Description
Technical field
The present invention relates to papermaking antibacterial agent fields, and in particular to a kind of papermaking antibacterial agent and its preparation based on hemicellulose
Method and application.
Background technique
Increasingly very high with people's living standard, people are increasing rapidly the attention rate and demand of antibacterial daily necessity
Add.Paper products cover the every aspect of people's life as a kind of common articles for daily use.Thus, the research and development of anti-bacteria paper with
Preparation is just concerned.
Antibacterial agent is the core component of anti-bacteria paper, and good antibacterial agent is related to the quality of anti-bacteria paper.Guanidine salt is a kind of common
Organic antibacterial agent, it is preferable to the antibacterial effect of bacterium, xylan be grafted polyhexamethylene guanidine hydrochloride, be that xylan changes through chemistry
Derivative after property, is made with polyhexamethylene guanidine hydrochloride high temperature graft copolymerization by xylan, has polyhexamethylene guanidine hydrochloride
Antibiotic property, and polyhexamethylene guanidine hydrochloride can form hydrogen bond with cellulose, have to size performance there are positively charged amino
The raising of effect, therefore can be applied to paper industry.The xylan grafting polyhexamethylene guanidine hydrochloride of this method preparation has ring
Border friendly, environmental pollution are small.
In recent years, biomass is cheap, renewable, nontoxic due to having many advantages, such as, the high value added utilization of biomass by
Extensive research, wherein the grafting, copolymerization and modification method of biomass is especially noticeable.Biomass passes through grafting, copolymerization and modification side
Method can assign the performance of its graft copolymer, improve its application range.By being grafted to biomass for particular functional group's grafting
Copolymerization includes the graft copolymerization of starch, the graft copolymerization of cellulose, the graft copolymerization of hemicellulose etc..It is connect using xylan
The disadvantages of branch polyhexamethylene guanidine hydrochloride replaces traditional papermaking antibacterial agent to greatly reduce production cost, environmental pollution, has
Technology and feasibility economically.
Summary of the invention
In order to solve the disadvantage that the above prior art and shortcoming, the purpose of the present invention is to provide one kind to be based on half fiber
Tie up the papermaking antibacterial agent and the preparation method and application thereof of element.Xylan grafting polyhexamethylene guanidine hydrochloride has both xylan and gathers
Hexa-methylene guanidine hydrochloride performance, antibiotic property is good, effectively improves the antibiotic property and paper mechanical performance of secondary stock.Preparation of the invention
Method has technique easy to operate, environment friendly.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of the antibacterial agent based on hemicellulose, includes the following steps:
Xylan graft copolymerization: weighing cationic xylan powder and be dissolved in ultrapure water, dissolve by heating in water-bath, leads to
Nitrogen exhausts air, and initiator is added and causes, adds polyhexamethylene guanidine hydrochloride, and product is cooled to room temperature after having reacted, and is mentioned
Pure, dry, obtained product is the Antibacterial Agent for Paper based on hemicellulose.
In the above method, it is ammonium ceric nitrate that the temperature of the water-bath, which is 40 DEG C~90 DEG C initiators, dosage is 1 ×
10-5~5 × 10-4Mol, initiation time are 5~20min.
In the above method, the preparation method of the cation xylan: 0.5g~4g xylan is dissolved in ultrapure water, is added
Enter the NaOH solution of 0.1g~1.2g, after the 10min~90min that alkalizes, 0.5g~8g 2,3- epoxypropyl trimethylammonium chloride is added dropwise
Ammonium, microwave reaction 10min~90min, purification of products, drying after reaction, obtained product are cationic xylan.
In the above method, the preparation method of the modified polyhexamethylene guanidine hydrochloride: by 0.1g~2g polyhexamethylene salt
Dimethyl sulfoxide stirring and dissolving is added in sour guanidine, according still further to the molar ratio of polyhexamethylene guanidine hydrochloride and glycidyl methacrylate
Glycidyl methacrylate is added in 1:4~4:1, reacts 1h~6h, purification, filtering, drying, and obtained product is modified poly- six
Methylene guanidine hydrochloride.
In the above method, the concentration of the polyhexamethylene guanidine hydrochloride in the solution is 0.01mol/L~0.40mol/L.
In the above method, the degree of substitution 0.10~0.60 of cationic xylan, molecular weight 20000~47000.
In the above method, the temperature that the cation xylan is reacted with polyhexamethylene guanidine hydrochloride is 40 DEG C~90 DEG C,
Time is 2h~8h.
In the above method, the method for purification is that dialysis needs 3~5 days, 3~6 water is changed daily, by the way that silver nitrate is added dropwise
Detect whether the presence there are also polyhexamethylene guanidine hydrochloride.
In the above method, the drying mode is freeze-drying, and drying time is 1~4 day.
A kind of antibacterial agent based on hemicellulose, grafting rate 5%~25%, molecular weight 100000~1000000.
A kind of antibacterial agent based on hemicellulose is applied in paper industry, and paper tensile index increases by 10.07%~
20.07%, paper tear index increases by 15.31%~25.31%, and paper burst index increases by 10.20%~30.20%, paper
It opens folding strength and increases by 27.78%~77.78%, paper anti-microbial property is that antibacterial circle diameter is 9~16mm.
Compared with prior art, the invention has the following advantages and beneficial effects:
(1) xylan prepared by the present invention is grafted polyhexamethylene guanidine hydrochloride, the characteristic with polyhexamethylene guanidine hydrochloride,
Also it can be used as papermaking antibacterial agent applied to paper industry with the performance of xylan simultaneously.
(2) during xylan grafting polyhexamethylene guanidine hydrochloride prepared by the present invention, reaction condition is mild, and operation is easy
Control, it is easy to accomplish industrialization.
Detailed description of the invention
Fig. 1 is the infared spectrum that xylan and xylan are grafted polyhexamethylene guanidine hydrochloride in embodiment 1.
Specific embodiment
Explanation is further explained to the present invention below in conjunction with implementation, embodiments of the present invention are not limited thereto.
Embodiment 1
(1) the self-control degree of substitution for weighing 0.5g is that 0.10 cationic xylan powder is dissolved in ultrapure water, in 60 DEG C of water-baths
It dissolves by heating, logical nitrogen exhausts air, is added 1 × 10-5Mol initiator ammonium ceric nitrate, obtains 2.5 × 10-4The nitric acid of mol/L
1 × 10 is added after 10min for cerium ammonium salt solution-4The polyhexamethylene guanidine hydrochloride solution of mol, in 60 DEG C of reaction 2h.
(2) reaction product of step (1) is cooled to room temperature, solution is poured into bag filter, freezed after dialysis 3 days dry
It is dry.The xylan that the grafting rate that purity is high is obtained after freeze-drying is 5% is grafted polyhexamethylene guanidine hydrochloride.
(3) product of step (2) is added to copy paper in paper pulp, paper performance of the paper copied relative to magma resists
Tensile index increases by 10.07%, and tear index increases by 15.31%, and burst index increases by 10.20%, and folding strength increases by 27.78%.
(4) paper that step (3) is copied is done to the Bactericidal test of Escherichia coli, antibacterial circle diameter reaches 9mm.
Embodiment 2
(1) the self-control degree of substitution for weighing 0.5g is that 0.35 cationic xylan powder is dissolved in ultrapure water, in 60 DEG C of water-baths
It dissolves by heating, logical nitrogen exhausts air, is added 1 × 10-4Molmol initiator ammonium ceric nitrate, obtains 2.5 × 10-3The nitre of mol/L
Sour cerium ammonium salt solution the polyhexamethylene guanidine hydrochloride of 0.0016mol is added after 10min, in 70 DEG C of reaction 4h.
(2) reaction product of step (1) is cooled to room temperature, solution is poured into bag filter, freezed after dialysis 4 days dry
It is dry.The xylan that the grafting rate that purity is high is obtained after freeze-drying is 15% is grafted polyhexamethylene guanidine hydrochloride.
(3) product of step (2) is added to copy paper in paper pulp, paper performance of the paper copied relative to magma resists
Tensile index increases by 15.07%, and tear index increases by 20.31%, and burst index increases by 20.20%, and folding strength increases by 47.78%.
(4) paper that step (3) is copied is done to the Bactericidal test of Escherichia coli, antibacterial circle diameter reaches 12mm.
Embodiment 3
(1) the cationic xylan powder that the self-control degree of substitution for weighing 0.5g is 0.60 is dissolved in ultrapure water, 60 DEG C of water-baths
Middle heating for dissolving, logical nitrogen exhaust air, are added 5 × 10-4Mol initiator ammonium ceric nitrate, obtains 1.25 × 10-3The nitre of mol/L
4 × 10 are added after 10min for sour cerium ammonium salt solution-2The polyhexamethylene guanidine hydrochloride of mol, in 80 DEG C of reaction 6h.
(2) reaction product of step (1) is cooled to room temperature, solution is poured into bag filter, freezed after dialysis 5 days dry
It is dry.The xylan that the grafting rate that purity is high is obtained after freeze-drying is 25% is grafted polyhexamethylene guanidine hydrochloride.
(3) product of step (2) is added to copy paper in paper pulp, paper performance of the paper copied relative to magma resists
Tensile index increases by 20.07%, and tear index increases by 25.31%, and burst index increases by 30.20%, and folding strength increases by 77.78%.
(4) paper that step (3) is copied is done to the Bactericidal test of Escherichia coli, antibacterial circle diameter reaches 16mm.
It can be seen from figure 1 that the xylan of embodiment 1 is in 3433,2918,1637,1464,1388,1044,985,897cm-1Place
There are absorption peak, 2918cm-1The absorption peak at place is the C-H stretching vibration absworption peak of alkane on xylan.It is infrared with xylan
Map is compared, and the infared spectrum of cationic xylan grafting poly (hexamethylene) is in 1637cm-1And 1383cm-1Absorption peak
Intensity is remarkably reinforced, and respectively corresponds the stretching vibration absworption peak of C=N and C-N.It demonstrates cationic xylan and has been grafted and gather
Hexa-methylene guanidine salt.The infared spectrum of xylan and xylan grafted polyacrylamide is consistent with Fig. 1 in other embodiments, explanation
Xylan prepared by the present invention is grafted polyhexamethylene guanidine hydrochloride, the characteristic with polyhexamethylene guanidine hydrochloride, while also having
The performance of xylan can be used as papermaking antibacterial agent applied to paper industry.
The elemental analysis of xylan and xylan grafting polyhexamethylene guanidine hydrochloride is as shown in table 1.
As seen from Table 1, the mass fraction of the N of xylan graft copolymer increases obvious, and available graft copolymer increases
Add the conclusion of the functional group of N, i.e., connects polyhexamethylene guanidine hydrochloride in graft copolymer.And as grafting rate increases, N's
Content continues growing.
Claims (10)
1. a kind of preparation method of the antibacterial agent based on hemicellulose, which comprises the steps of:
Xylan graft copolymerization: weighing cationic xylan powder and be dissolved in ultrapure water, dissolve by heating in water-bath, leads to nitrogen
Air is exhausted, initiator is added and causes, adds polyhexamethylene guanidine hydrochloride, product is cooled to room temperature after having reacted, and is purified, is done
It is dry, obtain the Antibacterial Agent for Paper based on hemicellulose.
2. the preparation method of the antibacterial agent based on hemicellulose according to claim 1, which is characterized in that the temperature of the water-bath
Degree is that 40 DEG C~90 DEG C initiators are ammonium ceric nitrate, and dosage is 1 × 10-5~5 × 10-4Mol, cause the time be 5 ~
20min。
3. the preparation method of the antibacterial agent based on hemicellulose according to claim 1, which is characterized in that the cation wood
The preparation method of glycan: 0.5g ~ 4g xylan is dissolved in ultrapure water, and the NaOH solution of 0.1g ~ 1.2g is added, and the 10min that alkalizes ~
After 90min, 0.5g ~ 8g 2 is added dropwise, 3- epoxypropyltrimethylchloride chloride, microwave reaction 10min ~ 90min, product mentions after reaction
It is pure, dry, obtain cationic xylan；
The preparation method of the modified polyhexamethylene guanidine hydrochloride: it is sub- that dimethyl is added in 0.1g ~ 2g polyhexamethylene guanidine hydrochloride
Methyl is added according still further to polyhexamethylene guanidine hydrochloride and molar ratio 1:4 ~ 4:1 of glycidyl methacrylate in sulfone stirring and dissolving
Glycidyl Acrylate, reacts 1h ~ 6h, and purification, filtering, drying obtain modified polyhexamethylene guanidine hydrochloride.
4. the preparation method of the antibacterial agent based on hemicellulose according to claim 1, which is characterized in that poly- six methylene
The concentration of base guanidine hydrochloride in the solution is 0.01mol/L~0.40mol/L.
5. the preparation method of the antibacterial agent based on hemicellulose according to claim 1, which is characterized in that cationic xylan
Degree of substitution 0.10 ~ 0.60, molecular weight 20000 ~ 47000.
6. the preparation method of the antibacterial agent based on hemicellulose according to claim 1, which is characterized in that the cation wood
The temperature that glycan is reacted with polyhexamethylene guanidine hydrochloride is 40 DEG C~90 DEG C, and the time is 2h~8h.
7. the preparation method of the antibacterial agent based on hemicellulose according to claim 1, which is characterized in that the method for purification
3~5 days are needed for dialysis, changes 3~6 water daily.
8. the preparation method of the antibacterial agent based on hemicellulose according to claim 1, which is characterized in that the drying mode
For freeze-drying, drying time is 1 ~ 4 day.
9. a kind of antibacterial agent based on hemicellulose as made from the described in any item preparation methods of claim 1-7, grafting
Rate 5% ~ 25%, molecular weight 100000 ~ 1000000.
10. a kind of antibacterial agent based on hemicellulose as claimed in claim 9 is applied in paper industry, paper tensile index increases
Adding 10.07% ~ 20.07%, paper tear index increases by 15.31% ~ 25.31%, and paper burst index increases by 10.20% ~ 30.20%,
Paper folding strength increases by 27.78% ~ 77.78%, and paper anti-microbial property is that antibacterial circle diameter is 9 ~ 16mm.
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| CN201810841044.5A CN109265693A (en) | 2018-07-27 | 2018-07-27 | A kind of antibacterial agent and the preparation method and application thereof based on hemicellulose |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098999A (en) * | 2005-01-05 | 2008-01-02 | 陶氏环球技术公司 | Enhanced efficacy of fungicides in paper and paperboard |
| CN101974108A (en) * | 2010-10-26 | 2011-02-16 | 华南理工大学 | Method for preparing cation type hemicelluloses |
| CN103214598A (en) * | 2013-04-25 | 2013-07-24 | 华南理工大学 | Quaternization xylan, preparation method via semi-dry process and application of quaternization xylan |
| CN103897199A (en) * | 2014-03-25 | 2014-07-02 | 曲阜师范大学 | Cellulose-based guanidine salt bacteriostatic functional material and preparation method thereof |
-
2018
- 2018-07-27 CN CN201810841044.5A patent/CN109265693A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098999A (en) * | 2005-01-05 | 2008-01-02 | 陶氏环球技术公司 | Enhanced efficacy of fungicides in paper and paperboard |
| CN101974108A (en) * | 2010-10-26 | 2011-02-16 | 华南理工大学 | Method for preparing cation type hemicelluloses |
| CN103214598A (en) * | 2013-04-25 | 2013-07-24 | 华南理工大学 | Quaternization xylan, preparation method via semi-dry process and application of quaternization xylan |
| CN103897199A (en) * | 2014-03-25 | 2014-07-02 | 曲阜师范大学 | Cellulose-based guanidine salt bacteriostatic functional material and preparation method thereof |
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Application publication date: 20190125 |