CN103554491A - Polyethyleneimine antibacterial functionalized polymer as well as preparation method and application thereof - Google Patents
Polyethyleneimine antibacterial functionalized polymer as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyethyleneimine antibacterial functionalized polymer as well as a preparation method and an application thereof. The preparation method comprises the following steps: reacting guanidine substances with macromolecular polyethyleneimine for 2-12 hours at 60-120 DEG C, controlling the pH value of the reaction, and dialyzing the reaction product to obtain a guanidinium polyethyleneimine solution; or placing guanidine substances and macromolecular polyethyleneimine in a microwave synthesizer, reacting for 10-60 minutes at 60-90 DEG C, controlling the pH value of the reaction, and dialyzing the reaction product to obtain a guanidinium polyethyleneimine solution; heating the guanidinium polyethyleneimine solution, adding an epoxy compound, reacting, and dialyzing the reaction product to obtain a antibacterial polymer solution. The polyethyleneimine antibacterial functionalized polymer as well as the preparation method and the application thereof disclosed by the invention have the following advantages that the preparation process is simple, the cost is low, and the antibacterial paper prepared from the polymer has good antibacterial performance, strength performance and the like, and capable of well meeting the antibacterial requirements of paper for daily use, paper for packaging and the like.
Description
Technical field
The present invention relates to a kind of antibacterial polymer, be specifically related to a kind of polymine antibacterial fluidized polymer and preparation method thereof and application in papermaking.
Background technology
Along with the raising of people's living standard, the enhancing of safety and Health consciousness, also more urgent to the pursuit of the antibacterial and mouldproof material of nontoxic, environmental protection, safety and sanitation and product.At present, for antibacterial and elimination harmful microbe sterilant, be mostly organic antibacterial agent (quaternary ammonium salt, pyridines, guanidine salt, halo alkanes etc.), natural polymer (chitosan and derivative thereof) and inorganic antiseptic (silver-series antibacterial agent etc.).At present the more polymer antibacterial agent of research is guanidine salt polymer, is the new type bactericide of a kind of wide spectrum, efficient, non-stimulated, good stability.
In recent years, guanidinesalt and derivative thereof are introduced in Polymer Structure, and resulting guanidinesalt family macromolecule antiseptic-germicide has wide spectrum, efficient anti-microbial property, and good is water-soluble, and, safety non-toxic non-stimulated to human body.The Antibacterial Mechanism of guanidinesalt family macromolecule: guanidine salt groups has a center of positive charge [N
+], under the impact of electric field, the metabolic function torpescence of enzyme in cytolemma, respiratory function is damaged; Can be by effects such as diffusions, the microorganism of adsorption zone negative charge, and destroy its cellularstructure and material energy metabolism, thus play the effect of sterilization.
At present, use guanidine salt polymer to have two kinds as the method for antiseptic-germicide: a kind of is simple blend, and a kind of is chemical bonding.When guanidine salt polymer simple blend is in the products such as resin, easily because it is soluble in water, make product lose long acting antibiotic.And the method for utilizing chemical bonding is grafted to guanidine salt groups and can avoids the pollution and the unabiding problem of goods antibacterial effect thereof that run off and cause because of antiseptic-germicide in matrix material, expanded it as the antibacterial modified dose of utilization at aspects such as plastics, fiber, coating, paper product.CN101747363 discloses a kind of preparation method of organic silicon guanidine salt disinfectant, and this organic silicon guanidine salt disinfectant is the antiseptic-germicide of the non-release type of unique bond, can persistent key be combined in material surface formation antibiotic layer.Utilize organosilicon and guanidine salt binding, not only can make up common guanidine class antiseptic-germicide and have poor heat resistance, the shortcoming such as easily in environment, separate out, can meet the demand of some high purity products simultaneously, thereby obtain novel antibacterial material safely and efficiently, also can be used as tourism portable sterilant, home textile sterilant and leather preservative etc.
Paper product be people produce and live in indispensable product, be widely used in daily life, and at present industrialized this series products does not have antibacterial.Present stage, aspect coating and paper product, the research of guanidine salt antiseptic-germicide is relative extensive.CN102561107A discloses a kind of antibacterial paper paint and preparation method thereof, and wherein antibiotic paint is comprised of chitosan biguanide hydrochloride, nano titanium oxide, carboxylic styrene butadiene latex etc.Concrete grammar is at normal temperatures and pressures, and through high speed dispersion, to prepare solid content be again 30% antibacterial paper paint to blending ingredients in sequence.Chinese invention patent application CN102587196A discloses a kind of method of preparing anti-bacteria paper based on interlayer self-assembling technique, it carries out alternating deposit by cationic polyelectrolyte chitosan biguanide hydrochloride and the negatively charged ion carboxymethyl cellulose with antibacterial on the surface of fiber, prepare the orderly self assembling multilayer ultrathin membrane of stratiform, when can give page good antimicrobial property, improve the strength property of page.Chinese invention patent application CN103012606 discloses treated starch of a kind of grafting Guanoctine oligopolymer and its preparation method and application.The method adopts chemical bond that Guanoctine oligopolymer is grafted on starch polymer chain, prepare high-efficiency broad spectrum antibacterial and mouldproof performance with natural pulp, synthon or binding agent blend, simultaneously to the safe and harmless paper of HUMAN HEALTH, textiles or binding agent, single its relative cost of guanidinesalt oligopolymer of comparing is lower, and antibiotic effective ingredient content is higher.But the method need to utilize coupling agent Guanoctine oligopolymer could be grafted on starch molecule, in paper making pulp, add the paper that this product only obtains having antibacterial and mouldproof performance, and the strength property of paper (especially wet epistasis energy) changes and is indefinite simultaneously.
Summary of the invention
In order to overcome the above-mentioned shortcoming and defect of prior art, the invention provides a kind of stronger antibacterial that has, and can improve polymine antibacterial fluidized polymer of paper strength and preparation method thereof.
Another object of the present invention is to provide the application of polymine antibacterial fluidized polymer in papermaking.
The present invention, by molecular designing, is grafted to the guanidine salt groups with antibacterial on polymine, has prepared the polyethyleneimine polymers with antibacterial.Simultaneously by epoxide to its further modification, reaction forms specific humidification epistasis group, realizes and increases the wet strong effect of paper.Due to the easy modification of polymine, have simultaneously and can be attached to well the first-class advantage of paper web, the antiseptic-germicide in compared to existing technology, the antibacterial polymer germ resistance of gained of the present invention effect stronger, that humidification is strong is also more obvious, therefore, practicality also obviously strengthens.
Object of the present invention is specifically achieved by following technical proposals:
A preparation method for polymine antibacterial fluidized polymer, comprises the following steps:
(1) guanidine class material and polyethyleneimine polymer are reacted to 2h～12h at 60 ℃～120 ℃, the pH value of controlling reaction is 2～7, by the reaction product 24～48h that dialyses, obtains guanidine salinization polymine solution; Or guanidine class material and polyethyleneimine polymer are placed in the microwave synthesizer that radiation power is 200～700W, at 60 ℃～90 ℃, react 10min～60min, the pH value of controlling reaction is 2～7, by the reaction product 24～48h that dialyses, obtains guanidine salinization polymine solution;
Described guanidine class material is cyanamide or guanidinesalt; Described guanidine class material Zhong ?NH
2reactive group and polyethyleneimine polymer Zhong ?NH
2the mol ratio of reactive group is 0.5～5:1; The molecular weight of described polyethyleneimine polymer is 1W～100W;
(2) described guanidine salinization polymine solution is heated up, add epoxy compounds in the time of 40～60 ℃, insulation reaction 2～12h, by the reaction product 24～48h that dialyses, obtains antibacterial polymer solution; Described epoxy compounds is a kind of in epoxy chloropropane, water-based bisphenol A type epoxy resin and glycerol glycidyl epoxy resin.
For further realizing the object of the invention, described guanidinesalt is one or more in hydrochloric acid guanidinesalt, nitric acid guanidinesalt, carbonic acid guanidinesalt and Guanidine Phosphates.Described cyanamide is cyanamide or Dyhard RU 100.The frequency of described microwave synthesizer is 100～1000W.
An antibacterial fluidized polymer, is made by above-mentioned preparation method.
The application of described polymine antibacterial fluidized polymer in papermaking: by with respect to oven dry stock mass percent, by the Xylo-Mucine of 1%～5% polymine antibacterial fluidized polymer and 1%～5% be sequentially added in eucalyptus pulp, stir after copy paper, the scraps of paper of copying first carry out mechanical expression, dry, after the balance 24h of thermostatic constant wet chamber, obtain having the antibiotic and page strong dual property of humidification.
Described drying process is dry 30min at 105 ℃ preferably
The invention provides the antiseptic-germicide that the polymine antibacterial fluidized polymer obtaining by above-mentioned reaction can be used as increasing dry, wet epistasis.
Compared with prior art, the present invention has the following advantages:
(1) polymine is a kind of cationic polyelectrolyte, primary, secondary, the tertiary amine groups of nearly 1:2:1 in high branched chain molecule, and its molecular weight is between hundreds of to ten ten thousand.Primary amine groups in structure and secondary amine all have stronger reactive behavior, therefore can carry out under proper condition number of chemical modification.Polymine is a kind of water soluble resin liquid simultaneously, when near-neutral pH, adds in paper pulp, can produce moderate wetting by force.The present invention combines guanidinesalt and the polymine with antibacterial, shows excellent anti-microbial property, can increase the strength property of page simultaneously.
(3) the present invention utilizes the synthetic polyethyleneimine polymers with antibacterial of microwave method, this has solved effectively by traditional method prepares the low problem of antibiotic wet strength agent process efficiency, has the significant advantage that generated time is short, efficiency is high, product anti-microbial effect is strong.
(2) the present invention combines guanidinesalt and polymine by the grafting mode of chemical bonding, makes product have lasting anti-microbial property.
(3) technique of the present invention is simple and easy to control, and the reaction times is short, makes excellent product performance, practical.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram before and after embodiment 5 polymine grafted guanidine salt oligopolymer.
Embodiment
Below in conjunction with example, the present invention is described in further detail, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
Get 10g polymine (molecular weight is 7W, and solid content is 50%) and 3.7g Guanidinium hydrochloride and be placed in 500ml there-necked flask, then add 150ml water, under magnetic agitation 300r/min, 80 ℃ of reactions, react 8h.Reaction finishes rear with dialysis tubing dialysis product 24h, every 2h, changes a deionized water.Product solution is warming up to 40 ℃, then adds 7.2g epoxy chloropropane and continue to be warming up to 60 ℃ of reaction 5h.Reaction finishes rear with dialysis tubing dialysis product 24h, and every a deionized water of 2h replacing, then dry 24h in 60 ℃ of vacuum drying ovens, obtains polymine antiseptic-germicide.
In with respect to oven dry stock mass percent, by the Xylo-Mucine of 2% antibacterial polymer and 1% be sequentially added in eucalyptus pulp, stir after copy paper, Substance is about 80g/m
2, the scraps of paper of copying first carry out mechanical expression, then after the dry 30min ， balance 24h of thermostatic constant wet chamber, obtain having the antibiotic and page strong dual property of humidification at 105 ℃, and performance is in Table 1 and table 2.
Embodiment 2
Get 10g polymine (molecular weight is 7W, and solid content is 50%) and 4.7g Guanidinium nitrate and be placed in 500ml there-necked flask, then add 150ml water, under magnetic agitation 300r/min, 90 ℃ of reactions, react 6h.Reaction finishes rear with dialysis tubing dialysis product 24h, every 2h, changes a deionized water.Product solution is warming up to 50 ℃, then adds 12g water-based bisphenol A type epoxy resin and continue to be warming up to 60 ℃ of reaction 4h.Reaction finishes rear with dialysis tubing dialysis product 24h, and every a deionized water of 2h replacing, then dry 24h in 60 ℃ of vacuum drying ovens, obtains polymine antiseptic-germicide.
In with respect to oven dry stock mass percent, by the Xylo-Mucine of 1% antibacterial polymer and 2% be sequentially added in slurry, stir after copy paper, Substance is about 80g/m
2, the scraps of paper of copying first carry out mechanical expression, then after the dry 30min ， balance 24h of thermostatic constant wet chamber, obtain having the antibiotic and page strong dual property of humidification at 105 ℃, and performance is in Table 1 and table 2.
Embodiment 3
Getting 10g polymine (molecular weight is 7W, and solid content is 50%) and 1.6g cyanamide and be placed in 500ml there-necked flask, then add 150ml water, is 700W at microwave irradiation power, and temperature is to react 25min under 80 ℃ of reaction conditionss.Reaction finishes rear with dialysis tubing dialysis product 24h, every 2h, changes a deionized water.Product solution is warming up to 40 ℃, then adds 15g water-based bisphenol A type epoxy resin and continue to be warming up to 60 ℃ of reaction 5h.Reaction finishes rear with dialysis tubing dialysis product 24h, and every a deionized water of 2h replacing, then dry 24h in 60 ℃ of vacuum drying ovens, obtains polymine antiseptic-germicide.
In with respect to oven dry stock mass percent, by the Xylo-Mucine of 2% antibacterial polymer and 3% be sequentially added in eucalyptus pulp, stir after copy paper, Substance is about 80g/m
2, the scraps of paper of copying first carry out mechanical expression, then after the dry 30min ， balance 24h of thermostatic constant wet chamber, obtain having the antibiotic and page strong dual property of humidification at 105 ℃, and performance is in Table 1 and table 2.
Embodiment 4
Getting 10g polymine (molecular weight is 7W, and solid content is 50%) and 3.2g Dyhard RU 100 and be placed in 500ml there-necked flask, then add 150ml water, is 700W at microwave irradiation power, and temperature is to react 15min under 90 ℃ of reactions.Reaction finishes rear with dialysis tubing dialysis product 24h, every 2h, changes a deionized water.Product solution is warming up to 50 ℃, then adds 5.4g epoxy chloropropane and continue to be warming up to 60 ℃ of reaction 4h.Reaction finishes rear with dialysis tubing dialysis product 24h, and every a deionized water of 2h replacing, then dry 24h in 60 ℃ of vacuum drying ovens, obtains polymine antiseptic-germicide.
In with respect to oven dry stock mass percent, by the Xylo-Mucine of 2% antibacterial polymer and 1% be sequentially added in slurry, stir after copy paper, Substance is about 80g/m
2, the scraps of paper of copying first carry out mechanical expression, then after the dry 30min ， balance 24h of thermostatic constant wet chamber, obtain having the antibiotic and page strong dual property of humidification at 105 ℃, and performance is in Table 1 and table 2.
Embodiment 5
(molecular weight is 7W to get 10g polymine, solid content is 50%) and 11g Guanidinium hydrochloride oligopolymer (the polyhexamethylene Guanidinium hydrochloride that solid content is 50%) be placed in 500ml there-necked flask, add again 150ml water, under magnetic agitation 300r/min, the reaction conditions of 100 ℃, react 4h.Reaction finishes rear with dialysis tubing dialysis product 24h, every 2h, changes a deionized water.Product solution is warming up to 60 ℃, then adds 5g glycerol glycidyl epoxy resin and continue 60 ℃ of reaction 3h of insulation.Reaction finishes with dialysis tubing dialysis product 24h, every 2h, to change a deionized water afterwards, and then dry 24h in 60 ℃ of vacuum drying ovens, obtains polymine antiseptic-germicide, and performance is in Table 1 and table 2.
As shown in Figure 1, known by the infrared spectra of contrast polymine and guanidinesalt grafting polyethylene imine, the infrared spectra of guanidinesalt grafting polyethylene imine product is at 1636cm
?1there is obvious absorption peak in place, what this absorption peak represented is the stretching vibration absorption peak of C=N in guanidine radicals, simultaneously at 1368cm
?1there is peak value in place, representative be C ?N stretching vibration absorption peak, this is all the charateristic avsorption band of guanidine compound, hence one can see that, and guanidine salt groups has been grafted on polyethyleneimine: amine molecule.Similar the present embodiment of situation of embodiment 1-4, does not provide one by one.
In with respect to oven dry stock mass percent, by the Xylo-Mucine of 1% antibacterial polymer and 1% be sequentially added in slurry, stir after copy paper, Substance is about 80g/m
2, the scraps of paper of copying first carry out mechanical expression, then after the dry 30min ， balance 24h of thermostatic constant wet chamber, obtain having the antibiotic and page strong dual property of humidification at 105 ℃.
Embodiment 1～5 prepares the antibacterial effect of polymine antiseptic-germicide in Table 1, and antibacterial effect is represented by the minimal inhibitory concentration (MIC value) of antibacterial polymer.
In order to contrast the performance variation of polymine antiseptic-germicide front and back page, especially the tensile strength of page and antibiotic rate, each embodiment has also prepared control sample, and its preparation process is except not adding polymine antiseptic-germicide, all the other conditions are with to prepare sample identical, and comparing result is in Table 2.Paper tensile strength is implemented by national standard (GB/T453 ?1989).Utilize shake flask test to survey the antibiotic rate of page sample, shake flask test is implemented by national standard (FZ/T01021 ?92).
The minimal inhibitory concentration of the polymine antiseptic-germicide sample of table 1 embodiment 1～5 preparation
| Sample name | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| MIC ①（ppm） | 62 | 62 | 62 | 31 | 15 |
| MIC ②（ppm） | 128 | 128 | 62 | 62 | 31 |
Note: MIC
1.antiseptic-germicide is to colibacillary minimal inhibitory concentration;
MIC
2.the minimal inhibitory concentration of antiseptic-germicide to streptococcus aureus.
The minimal inhibitory concentration that can be obtained polymine antiseptic-germicide sample by upper table 1 is all lower, illustrates that its fungistatic effect to intestinal bacteria and streptococcus aureus is remarkable.Wherein, minimal inhibitory concentration method is MIC method, means that sterilant suppresses the required Cmin of microorganism growth completely, so MIC value is less, shows that the sterilization effect of this sterilant is better.
Table 2 embodiment 1～5 prepares tensile strength and the antibacterial effect of page sample
As shown in Table 2, the antibiotic rate of the control sample of embodiment 1～5 is all 0%, be that sample does not all have anti-microbial property, but after having added polymine antiseptic-germicide, the antibacterial effect of the sample of embodiment 1～5 reaches more than 90%, paper strength also all increases, and especially the retention rate of wet tenacity has obviously improved.Illustrate that polymine antiseptic-germicide makes page have the good strong dual function of antibiotic and humidification.
Claims (7)
1. a preparation method for polymine antibacterial fluidized polymer, is characterized in that comprising the following steps:
(1) guanidine class material and polyethyleneimine polymer are reacted to 2h～12h at 60 ℃～120 ℃, the pH value of controlling reaction is 2～7, by the reaction product 24～48h that dialyses, obtains guanidine salinization polymine solution; Or guanidine class material and polyethyleneimine polymer are placed in the microwave synthesizer that radiation power is 200～700W, at 60 ℃～90 ℃, react 10min～60min, the pH value of controlling reaction is 2～7, by the reaction product 24～48h that dialyses, obtains guanidine salinization polymine solution;
Described guanidine class material is cyanamide or guanidinesalt; Described guanidine class material Zhong ?NH
2reactive group and polyethyleneimine polymer Zhong ?NH
2the mol ratio of reactive group is 0.5～5:1; The molecular weight of described polyethyleneimine polymer is 1W～100W;
(2) described guanidine salinization polymine solution is heated up, add epoxy compounds in the time of 40～60 ℃, insulation reaction 2～12h, by the reaction product 24～48h that dialyses, obtains antibacterial polymer solution; Described epoxy compounds is a kind of in epoxy chloropropane, water-based bisphenol A type epoxy resin and glycerol glycidyl epoxy resin.
2. the preparation method of polymine antibacterial fluidized polymer according to claim 1, is characterized in that: described guanidinesalt is one or more in hydrochloric acid guanidinesalt, nitric acid guanidinesalt, carbonic acid guanidinesalt and Guanidine Phosphates.
3. the preparation method of polymine antibacterial fluidized polymer according to claim 1, is characterized in that: described cyanamide is cyanamide or Dyhard RU 100.
4. the preparation method of polymine antibacterial fluidized polymer according to claim 1, is characterized in that: the frequency of described microwave synthesizer is 100～1000W.
5. a polymine antibacterial fluidized polymer, is characterized in that being that it is made by preparation method described in claim 1-4 any one.
6. the application of polymine antibacterial fluidized polymer claimed in claim 5 in papermaking, it is characterized in that: by with respect to oven dry stock mass percent, by the Xylo-Mucine of 1%～5% polymine antibacterial fluidized polymer and 1%～5% be sequentially added in eucalyptus pulp, stir after copy paper, the scraps of paper of copying first carry out mechanical expression, dry, after the balance 24h of thermostatic constant wet chamber, obtain having the antibiotic and page strong dual property of humidification.
7. the application of polymine antibacterial fluidized polymer according to claim 6 in papermaking, is characterized in that: described being dried as dry 30min at 105 ℃.
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| CN110614083A (en) * | 2019-09-23 | 2019-12-27 | 长安大学 | Polyethyleneimine modified sawdust heavy metal adsorbent and preparation method thereof |
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| CN112796160A (en) * | 2021-02-05 | 2021-05-14 | 上海万戈工贸发展有限公司 | Preparation method of chelated copper ion polymer and antibacterial barrier composite paper/paperboard thereof |
| CN115260646A (en) * | 2021-04-29 | 2022-11-01 | 中国石油化工股份有限公司 | Flame-retardant antibacterial thermoplastic resin composition and preparation method and application thereof |
| CN113981691A (en) * | 2021-10-26 | 2022-01-28 | 成都海蓉特种纺织品有限公司 | Special fabric with flame-retardant and antibacterial functions and preparation method and application thereof |
| CN114698641A (en) * | 2022-03-25 | 2022-07-05 | 石家庄学院 | Use of guanidine polymers grafted with polyethyleneimine |
| CN114698641B (en) * | 2022-03-25 | 2024-03-26 | 石家庄学院 | Use of guanidine polymers grafted with polyethyleneimine |
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