CN104861120A - Preparation method of environment-friendly long-acting antibacterial polylactic acid material - Google Patents
Preparation method of environment-friendly long-acting antibacterial polylactic acid material Download PDFInfo
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- CN104861120A CN104861120A CN201510278437.6A CN201510278437A CN104861120A CN 104861120 A CN104861120 A CN 104861120A CN 201510278437 A CN201510278437 A CN 201510278437A CN 104861120 A CN104861120 A CN 104861120A
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Abstract
The invention provides a preparation method of an environment-friendly long-acting antibacterial polylactic acid material, which comprises the steps that an acrylamide substance is grafted to a polylactic acid molecular chain under an initiator existence condition by a radical graft polymerization method; and then amino is halogenated by a halogenating agent. In bacterium and virus killing processes of a halogen amide compound, an oxidation-state halogen atom is consumed, so that an N-X bond in an halogen amide molecule is converted into an N-H bond and the activity is lost, but the N-H bond can be oxidized into an N-C1 bond after simple rinsing of dilute-concentration bleaching liquid (with an active ingredient of hypochlorite), and a sterilization function is obtained again. Polylactic acid is grafted with acrylamide and then halogenation is performed, so that a product contains a halogen amide group, is high in antibacterial efficiency, is safe to a human body, has no toxic or side effect, is pollution-free, and can be completely applied to a food packing material and tableware.
Description
Technical field
The invention belongs to degradable macromolecule field of compound material, be specially a kind of preparation method of environment-friendly long-life antibiotic polylactic acid material.
Background technology
When people recognize the existence of environmental problem, explore the problem of preserving the ecological environment with regard to starting.The macromolecular material that poly(lactic acid) (PLA) is a kind of bio-based, to take lactic acid as monomer degrade through the new bio of chemosynthesis, have nontoxic, nonirritant, good biocompatibility, intensity are high and biodegradable and the feature such as absorption, free from environmental pollution, be biodegradable polymer the most rising at present.Poly(lactic acid) application mainly concentrates on the fields such as biodegradable fiber, degradable plastic product, medical material.Domestic and international in the ascendant with exploitation as the applied research of Biodegradable material to poly(lactic acid) at present, product innovation and new Application Areas continue to bring out.
The performance of the performance of poly(lactic acid) and conventional petroleum base plastics can be made suitable, with the polylactic acid based wide market preparing antimicrobial macromolecule material by adding functional agent.Poly(lactic acid) itself has good physico-chemical property, polylactic acid based anti-biotic material is subject to the extensive concern of scholars, its research also achieves certain achievement, but compared with traditional anti-biotic material, its research is still aobvious weak, especially poly(lactic acid) is as a kind of hydrophobic material, is unfavorable for the stripping release of hydrophilic antibiotic agent, and the stripping release how efficiently solving antiseptic-germicide is the problem in science that first research of polylactic acid based anti-biotic material need to solve.
Patent 102250456A proposes a kind of method preparing antibiotic polylactic acid material.This patent uses polylactic resin, ultrafine anti-bacterial powder, tensio-active agent first to prepare antibacterial matrices and jointly extrude with particles of polylactic acid, the antibacterial polylactic acid dinnerware that this invention provides, bacteriostasis rate keeps higher level, because use antimicrobial powder, thus antibacterial long-lasting in have much room for improvement.Patent 101215411 provides a kind of light degradation antibiotic polylactic acid material and preparation method.This patent poly(lactic acid), nano-TiO
2, coupling agent, the characteristic of the anti-biotic material prepared by catalyzer is that degradation rate is accelerated under ultraviolet light irradiation and natural condition, is by adding inorganic antiseptic equally, and not enough to some extent in long-lasting.
Summary of the invention
For solving an above existing difficult problem, the present invention proposes a kind of preparation method of environment-friendly long-life antibiotic polylactic acid material.By free yl graft polymerization method, acrylamide (PAM) class material is grafted on polylactic acid molecule chain under initiator existence condition, then with halogenating agent by amino halogenation.Halogen aminated compounds is in kill bacteria and viral process, oxidation state halogen atom is consumed and causes the N-X key in halogen amine molecule be transformed into N-H key and lose activity, but after the simple rinsing of sodium hypochlorite solution (effective constituent is hypochlorite) that over-richness is very rare, N-H key wherein can be oxidized to N-Cl key again and regain sterilizing function.
The object of the present invention is to provide a kind of technique simple, long-acting antibiotic polylactic acid material.This material Halogen amine key, the halogen positive ion that halogen amine key decomposes release kill bacteria can wait microorganism with virus.
The present invention proposes the method preparing antibiotic polylactic acid material, and concrete technical scheme is as follows:
Poly(lactic acid) dissolved in organic solvent, add the acrylamide monomers and initiator of wanting grafting under nitrogen protection, after continuing inflated with nitrogen, immersed by reaction flask in oil bath, the control reaction times carries out polyreaction.After having reacted, be slowly added drop-wise to by polymers soln in the distilled water constantly stirred, obtain white fibrous solid product, then use a large amount of deionized water and washed with diethylether, vacuum-drying to constant weight obtains PLA-g-PAM multipolymer.Again multipolymer is dissolved in organic solvent, is added drop-wise in halogenating agent solution, regulate pH to 7, stirred at ambient temperature is obtained by reacting halogen amine compound, and falls excessive halogen ion with deionized water rinsing, obtains antibacterial polylactic acid product after drying.
Described polylactic acid molecule amount is 2-30 ten thousand dalton.
Described organic solvent is the one in acetone, tetrahydrofuran (THF) (THF), methylene dichloride, trichloromethane.
Described acrylamide monomers is one or more in acrylamide, Methacrylamide, N methacrylamide, NIPA, N tert butyl acrylamide, methacrylic acid (N, N-dimethyl amine) ethyl ester methylamine etc.
Described initiator is organo-peroxide: one or more in benzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, tertbutyl peroxide.
Described halogenating agent is one or more in clorox, sodium hypobromite, phosphorus pentachloride, sulfur oxychloride.
Described graft reaction time controling is at 5-8h, and temperature controls at 60-80 DEG C.
The percentage of grafting of described graft reaction is between 0.5%-10%.
Beneficial effect: carry out halogenation again after poly(lactic acid) graft acrylamide of the present invention, containing halogen amine groups in product, antimicrobial efficiency is high, can not produce toxic side effect, environmentally safe to human-body safety, and its product can be applied on food packaging material and tableware completely.
Accompanying drawing explanation
Fig. 1 is reaction formula schematic diagram of the present invention.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail, but the present invention is not limited only to these embodiments.
Poly(lactic acid) in embodiment becomes (Suqian) composite material company limited to produce for permitting friend, trade mark SUPLA 155.
Embodiment 1:
3.0g PLA is dissolved in 40ml THF; stirring and dissolving, adds monomeric acrylamide and initiator benzoyl peroxide (BPO) under nitrogen protection, after continuing inflated with nitrogen 20min; reaction flask is immersed in oil bath; reaction 1h, after having reacted, is slowly added drop-wise in the distilled water constantly stirred by polymers soln; obtain white fibrous solid product; then use a large amount of deionized water and washed with diethylether, vacuum-drying to constant weight obtains PLA-g-PAM multipolymer, by formula Y=(m
1-m
0)/m
0× 100% calculates percentage of grafting (m
0for sample dry weight before grafting; m
1for sample dry weight after grafting), obtaining percentage of grafting is 5.8%.Be dissolved in by multipolymer in THF, instillation massfraction is in the chlorine bleach liquor of 0.03%, regulates pH to 7, stirred at ambient temperature reaction 20min, obtain halogen aminated compounds, product rinses removing free chlorine repeatedly by deionized water, and vacuum-drying obtains antibacterial polylactic acid to constant weight.Products obtained therefrom has long-acting anti-microbial effect repeatedly to intestinal bacteria and streptococcus aureus, and antibiotic rate is respectively 97% and 94%.
Embodiment 2:
3.0g PLA is dissolved in 40ml THF; stirring and dissolving, adds monomer NIPA and initiator B PO under nitrogen protection, after continuing inflated with nitrogen 20min; reaction flask is immersed in oil bath; reaction 1h, after having reacted, is slowly added drop-wise in the distilled water constantly stirred by polymers soln; obtain white fibrous solid product; then use a large amount of deionized water and washed with diethylether, vacuum-drying to constant weight obtains PLA-g-PAM multipolymer, by formula Y=(m
1-m
0)/m
0× 100% calculates percentage of grafting (m
0for sample dry weight before grafting; m
1for sample dry weight after grafting), obtaining percentage of grafting is 5.2%.Be dissolved in by multipolymer in THF, instillation massfraction is in the chlorine bleach liquor of 0.03%, regulates pH to 7, stirred at ambient temperature reaction 20min, obtain halogen aminated compounds, product rinses removing free chlorine repeatedly by deionized water, and vacuum-drying obtains antibacterial polylactic acid to constant weight.Products obtained therefrom has long-acting anti-microbial effect repeatedly to intestinal bacteria and streptococcus aureus, and antibiotic rate is respectively 93% and 91%.
Embodiment 3:
3.0g PLA is dissolved in 40ml THF; stirring and dissolving, adds monomer Methacrylamide and initiator DCP under nitrogen protection, after continuing inflated with nitrogen 20min; reaction flask is immersed in oil bath; reaction 1h, after having reacted, is slowly added drop-wise in the distilled water constantly stirred by polymers soln; obtain white fibrous solid product; then use a large amount of deionized water and washed with diethylether, vacuum-drying to constant weight obtains PLA-g-PAM multipolymer, by formula Y=(m
1-m
0)/m
0× 100% calculates percentage of grafting (m
0for sample dry weight before grafting; m
1for sample dry weight after grafting), obtaining percentage of grafting is 4.3%.Be dissolved in by multipolymer in THF, instillation massfraction is in the chlorine bleach liquor of 0.03%, regulates PH to 7, stirred at ambient temperature reaction 20min, obtain halogen aminated compounds, product rinses removing free chlorine repeatedly by deionized water, and vacuum-drying obtains antibacterial polylactic acid to constant weight.Products obtained therefrom has long-acting anti-microbial effect repeatedly to intestinal bacteria and streptococcus aureus, and antibiotic rate is respectively 92% and 90%.
Above-mentioned embodiment is only for example of the present invention is clearly described, and the restriction not to embodiment.For those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here exhaustive without the need to also giving all embodiments, and thus the apparent change of amplifying out or variation be still in protection scope of the present invention.
Claims (8)
1. a preparation method for environment-friendly long-life antibiotic polylactic acid material, is characterized in that, concrete technical scheme is as follows:
Poly(lactic acid) dissolved in organic solvent, add the acrylamide monomers and initiator of wanting grafting under nitrogen protection, after continuing inflated with nitrogen, immersed by reaction flask in oil bath, the control reaction times carries out polyreaction.After having reacted, be slowly added drop-wise to by polymers soln in the distilled water constantly stirred, obtain white fibrous solid product, then use a large amount of deionized water and washed with diethylether, vacuum-drying to constant weight obtains PLA-g-PAM multipolymer; Again multipolymer is dissolved in organic solvent, is added drop-wise in halogenating agent solution, regulate PH to 7, stirred at ambient temperature is obtained by reacting halogen amine compound, and falls excessive halogen ion with deionized water rinsing, obtains antibacterial polylactic acid product after drying.
2. the preparation method of a kind of environment-friendly long-life antibiotic polylactic acid material according to claim 1, is characterized in that, described polylactic acid molecule amount is 2-30 ten thousand dalton.
3. the preparation method of a kind of environment-friendly long-life antibiotic polylactic acid material according to claim 1, is characterized in that, described organic solvent is the one in acetone, tetrahydrofuran (THF), methylene dichloride, trichloromethane.
4. the preparation method of a kind of environment-friendly long-life antibiotic polylactic acid material according to claim 1, it is characterized in that, described acrylamide monomers is one or more in acrylamide, Methacrylamide, N methacrylamide, NIPA, N tert butyl acrylamide, methacrylic acid (N, N-dimethyl amine) ethyl ester methylamine etc.
5. the preparation method of a kind of environment-friendly long-life antibiotic polylactic acid material according to claim 1, it is characterized in that, described initiator is organo-peroxide: one or more in benzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, tertbutyl peroxide.
6. the preparation method of a kind of environment-friendly long-life antibiotic polylactic acid material according to claim 1, is characterized in that, described halogenating agent is one or more in clorox, sodium hypobromite, phosphorus pentachloride, sulfur oxychloride.
7. the preparation method of a kind of environment-friendly long-life antibiotic polylactic acid material according to claim 1, is characterized in that, described graft reaction time controling is at 5-8h, and temperature controls at 60-80 DEG C.
8. the preparation method of a kind of environment-friendly long-life antibiotic polylactic acid material according to claim 1, it is characterized in that, the percentage of grafting of described graft reaction is between 0.5%-10%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586668A (en) * | 2018-04-11 | 2018-09-28 | 天津大学 | High-toughness polypropylene and polylactic acid ion graft copolymer and preparation method thereof |
| CN111850832A (en) * | 2020-07-10 | 2020-10-30 | 杭州米娅纺织品有限公司 | Antibacterial low-resistance melt-blown non-woven fabric and preparation method thereof |
| CN111893642A (en) * | 2020-08-10 | 2020-11-06 | 四川大学 | Halamine polymer antibacterial and antiviral nanofiber membrane and preparation method thereof |
| CN112695521A (en) * | 2020-12-25 | 2021-04-23 | 安徽工程大学 | Halamine modified antibacterial mesoporous material and synthesis method thereof |
| CN113444197A (en) * | 2020-03-24 | 2021-09-28 | 合肥杰事杰新材料股份有限公司 | Halamine antibacterial agent and preparation method and application thereof |
| CN114177367A (en) * | 2021-09-30 | 2022-03-15 | 中山大学附属口腔医院 | Multifunctional guide bone regeneration composite membrane and preparation method and application thereof |
| CN114672060A (en) * | 2022-03-21 | 2022-06-28 | 中山大学附属第八医院（深圳福田） | Preparation method and application of direct photo-initiation modified polyether-ether-ketone |
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| CN101215411A (en) * | 2008-01-21 | 2008-07-09 | 南京大学 | Light degradation antibiotic polylactic acid material and preparation method thereof |
| CN102250456A (en) * | 2011-06-13 | 2011-11-23 | 武汉华丽环保科技有限公司 | Antibacterial polylactic acid dinnerware and preparation method thereof |
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2015
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| CN101215411A (en) * | 2008-01-21 | 2008-07-09 | 南京大学 | Light degradation antibiotic polylactic acid material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586668A (en) * | 2018-04-11 | 2018-09-28 | 天津大学 | High-toughness polypropylene and polylactic acid ion graft copolymer and preparation method thereof |
| CN108586668B (en) * | 2018-04-11 | 2020-07-21 | 天津大学 | High-toughness polypropylene and polylactic acid ion graft copolymer and preparation method thereof |
| CN113444197A (en) * | 2020-03-24 | 2021-09-28 | 合肥杰事杰新材料股份有限公司 | Halamine antibacterial agent and preparation method and application thereof |
| CN111850832A (en) * | 2020-07-10 | 2020-10-30 | 杭州米娅纺织品有限公司 | Antibacterial low-resistance melt-blown non-woven fabric and preparation method thereof |
| CN111893642A (en) * | 2020-08-10 | 2020-11-06 | 四川大学 | Halamine polymer antibacterial and antiviral nanofiber membrane and preparation method thereof |
| CN112695521A (en) * | 2020-12-25 | 2021-04-23 | 安徽工程大学 | Halamine modified antibacterial mesoporous material and synthesis method thereof |
| CN114177367A (en) * | 2021-09-30 | 2022-03-15 | 中山大学附属口腔医院 | Multifunctional guide bone regeneration composite membrane and preparation method and application thereof |
| CN114177367B (en) * | 2021-09-30 | 2023-02-07 | 中山大学附属口腔医院 | Multifunctional guide bone regeneration composite membrane and preparation method and application thereof |
| CN114672060A (en) * | 2022-03-21 | 2022-06-28 | 中山大学附属第八医院（深圳福田） | Preparation method and application of direct photo-initiation modified polyether-ether-ketone |
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