CN103159983A - Novel beta-cyclodextrin host-guest complex antibacterial starch-base plastic and method for preparing same - Google Patents
Novel beta-cyclodextrin host-guest complex antibacterial starch-base plastic and method for preparing same Download PDFInfo
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- CN103159983A CN103159983A CN2013100798661A CN201310079866A CN103159983A CN 103159983 A CN103159983 A CN 103159983A CN 2013100798661 A CN2013100798661 A CN 2013100798661A CN 201310079866 A CN201310079866 A CN 201310079866A CN 103159983 A CN103159983 A CN 103159983A
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Abstract
The invention discloses a novel beta-cyclodextrin host-guest complex antibacterial starch-base plastic and a method for preparing the novel beta-cyclodextrin host-guest complex antibacterial starch-base plastic. The novel beta-cyclodextrin host-guest complex antibacterial starch-base plastic comprises the following components in percentage by weight: 95-99% of plastic raw material, 1-4% of antibacterial masterbatch, 0.2-0.5% of dispersant and 0.5-1% of antioxidant, wherein the antibacterial masterbatch is a beta-cyclodextrin host-guest complex which is prepared by modifying beta cyclodextrin by concentrated sulfuric acid to obtain a beta-cyclodextrin acidified by sulfuric acid, enabling the beta cyclodextrin acidified by sulfuric acid to react with water at high temperature and coating an antibacterial nanoparticle gel solution or organic antibacterial agent. The novel beta-cyclodextrin host-guest complex antibacterial starch-base plastic is prepared by mixing the plastic raw material and the antibacterial masterbatch, extruding, injecting and molding. The prepared novel beta-cyclodextrin host-guest complex antibacterial starch-base plastic is a biodegradable polymer, is environment-friendly and nontoxic, can be easily coated and designed due to the amphipathic characteristic of cyclodextrin, is simple in preparation process and has a long-lasting antibacterial effect.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to antibiotic starch plastics of a kind of novel beta-cyclodextrin host-guest inclusion thing and preparation method thereof.
Background technology
At present, plastics account for very consequence in daily life and industrial and agricultural production.Along with the extensively universal and application of plastics at daily necessities field, people are more and more higher to the requirement of plastics.The very difficult degraded voluntarily in physical environment due to energy scarcity and plastics can cause environmental pollution pressure.Therefore, reduce petroleum-based plastics petroleum-based plastics get that to replace biomass base material plastics are pendulum urgent need to solve the problems in face of government of all circles and scientific worker.
The starch plastics material more and more obtains the concern of society as a kind of Degradable environment protection plastic, the research of starch plastic obtains constantly going deep into and development.The plastics that contain starch or other derivatives during the Starch-base Degradable Plastic general reference forms.Plastics take the native starch or derivatives thereof as the co-mixing system major ingredient all belong to this type of.
Starch filled type starch plastics starch content therein is 7% ~ 30%, and due to the crisp and easy suction of starchiness, the starch that adds generally will be processed and plastics processing through surface hydrophobicity.Starch filled solution plastics belong to the plastic that crumbles, and its manufacturing process is all to add starch and various additive in the petroleum-based plastics resin, and reshaping processes.Full starch plastic starch content is more than 90%, and other components of interpolation are also degradable.It makes principle is to make the starch molecule allosteric and disordering, forms the thermoplastic starch with thermoplastic property, and its starch molecule configuration changes, but its chemical structure does not change.Be called again thermoplastic starch resin, these class plastics are the energy complete biodegradable after use, and generating at last carbonic acid gas and water is the main direction of recent domestic biodegradable starch-plastics research.Compare with oil and general plastic, starch plastics is owing to containing starch, and starch is biological material, and its chemical structure is poly-polysaccharide, and sugar is nutrition source biological, microorganism, and is therefore easier of various unwanted bacteria mould contaminations.Bacterium and mould are two kinds of main Types of microorganism, have characteristics of a great variety, that distribution is wide, vitality is vigorous.When envrionment conditions be relative humidity 65%, temperature between 20-30 ℃, pH value is under solutions of weak acidity, will absorb rapidly the growth of nourishing and generating, and causes material to go mouldy and destroys.The mycelium that forms during mould-growth is conductor, and material insulation property is descended.The metabolite that mould-growth produces contains organic acid and mycin, can make that being clamminess appears in product surface, variable color, the phenomenon such as become fragile, and also can make the people of these mould curd products of Long Term Contact go down with.Therefore, starch plastics is carried out antimicrobial treatment, prepare the health that antibiotic starch plastic will be conducive to starch plastics use, storage and the mankind.Traditional preparation antibiotic plastic is to add antiseptic-germicide in plastics. can kill within a certain period of time or suppress its breeding staining bacterium on plastics, keep self clean conditions, reduce the Bacterial cross between person to person, people and thing, thing and the thing that occurs because of the use plastics.But what adopt due to antiseptic-germicide and plastics is the method for blend, and its antibiotic time limit is shorter, and As time goes on, antibacterial effect reduces, and the anti-microbial property of prepared antibacterial plastic product can not be not fully exerted.
Summary of the invention
The purpose of this invention is to provide antibiotic starch plastics of a kind of novel beta-cyclodextrin host-guest inclusion thing and preparation method thereof.
For solving the problems of the technologies described above, the antibiotic starch plastics of novel beta-cyclodextrin host-guest inclusion thing that the present invention proposes, described antibiotic starch plastic is comprised of plastic raw materials, antibacterial plastic concentrate, dispersion agent and antioxidant, by weight percentage, plastic raw materials 95% ~ 99%, antibacterial plastic concentrate 1% ~ 4%, dispersion agent 0.2% ~ 0.5%, antioxidant 0.5% ~ 1%, described plastic raw materials are starch plastics.
In the present invention, described starch plastics be in full starch plastics, starch filled plastics or starch derivative plastics etc. any.
In the present invention, described dispersion agent is a kind of in zeolite, silica, wilkinite, sepiolite, diatomite or sodium stearate etc.
in the present invention, described antioxidant adopts MB (2 mercapto benzimidazole), MD-1024 (N, N'-is two, and [β (3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine), JX-1076 (β-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid), 702 (4,4''-methylene-bis (2, the 6-DI-tert-butylphenol compounds)), 168 (tricresyl phosphites (2, ester) or 1010 (four [β-(3 the 4-di-tert-butyl-phenyl), the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) etc. in one or more.
The preparation method of the antibiotic starch plastics of a kind of novel beta-cyclodextrin host-guest inclusion thing provided by the invention, concrete steps are as follows:
(1) preparation of antibacterial plastic concentrate, described antibacterial plastic concentrate is sulphur acidifying beta-cyclodextrin cross-linking starch, concrete preparation method is: at first the 30g-90g beta-cyclodextrin is joined in the vitriol oil of 100ml-200ml concentration 90%, at 0-10 ℃ of reaction 2-5h, excessive sulfuric acid filters and makes sulphur acidifying beta-cyclodextrin with the neutralization of 1N calcium carbonate.Sulphur acidifying beta-cyclodextrin is water-soluble, join to get the aqueous solution of 50g/L sulphur acidifying beta-cyclodextrin, and under ethylenediamine tetraacetic acid (EDTA) exists 120 ℃ of reaction 10-90min, add 3%-10% antimicrobial nano particle solution or organic antibacterial agent, have the molecular structure of hollow round table due to beta-cyclodextrin, belong to amphiphilic species, hydrophilic radical is contained in the outside---and hydrophilic, inner hydrophobic, thus the antibacterial plastic concentrate of beta-cyclodextrin host-guest inclusion thing can be obtained;
(2) with plastic raw materials, antibacterial plastic concentrate, dispersion agent and antioxidant join in agitator in proportion, then will mix and join fusion-grafting in twin screw extruder, namely obtain desired product.
In the present invention, described antimicrobial nano particle solution be in nano zine oxide, nano titanium oxide or nanometer silver any, described antiseptic-germicide be the guanidine class antiseptic-germicide such as polyhexamethylene guanidine, dichloro give birth to or N-tert-butyl acrylamide etc. in any.
The invention has the beneficial effects as follows: antibacterial plastic product is Biodegradable high-molecular, and environment-protecting asepsis pollutes, and utilize the amphipathic of cyclodextrin can carry out simple coating design, and preparation technology is simple, and antibacterial effect is permanent.
Embodiment
The below is described in detail preferred embodiment of the present invention, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that protection scope of the present invention is made more clearly defines.
Embodiment 1
A kind of antibiotic plastic, comprise the following ingredients that mass percent forms: the starch filled PP95% of plastic raw materials, antibacterial plastic concentrate 4%, dispersion agent 0.2%, antioxidant 0.8%, the preparation method of the antibiotic starch plastic of the present embodiment comprises the following steps: wherein plastic raw materials is starch filled PP, antibacterial plastic concentrate is beta-cyclodextrin host-guest inclusion thing zinc oxide antibacterial plastic concentrate, dispersion agent is sodium stearate, and antioxidant is 1010.What wherein dispersion agent used can be in zeolite, silica, wilkinite, sepiolite, diatomite or sodium stearates etc. is a kind of.Described antioxidant can adopt a kind of in MD-1024, JX-1076,702,164 or 1010 etc.
(1): the step by common preparation pp filled with starch prepares thermoplastic starch;
(2): thermoplastic starch 20%, PP75%, dispersion agent 0.2%, antioxidant 0.8% and beta-cyclodextrin host-guest inclusion thing nano zine oxide antibacterial plastic concentrate 4% are mixed by weight percentage and join twin screw extruder extrude, extrusion temperature is arranged to 180 ℃, obtains antibiotic starch plastic after granulation.
Embodiment 2
Antibacterial plastic concentrate is beta-cyclodextrin host-guest inclusion thing nano titanium oxide, and other are filled a prescription with embodiment 1.
Embodiment 3
Antibacterial plastic concentrate is beta-cyclodextrin host-guest inclusion thing nanometer silver, and other are filled a prescription with embodiment 1.
Embodiment 4
Antibacterial plastic concentrate is beta-cyclodextrin host-guest inclusion thing polyhexamethylene guanidine, and other are filled a prescription with embodiment 1.
Embodiment 5
Antibacterial plastic concentrate is that beta-cyclodextrin host-guest inclusion thing dichloro is given birth to, and other are filled a prescription with embodiment 1.
The anti-microbial property of the antibiotic starch plastic of the embodiment of the present invention 1 to embodiment 5 preparation is as shown in table 1.
The anti-microbial property test of antibiotic starch plastic:
Anti-microbial property detects with reference to People's Republic of China (PRC) state light industry standard QB/T2591-2003, adopts film applicator coating.
Investigate the antibiotic rate of sample 24h, total number of bacterial colony is measured and is counted with reference to GB/T4789.2-2003.With the hot-forming antibiotic model of 50mm * 50mm of making of pellet.The calculating formula of antibiotic rate is as follows:
R(％?)?＝?(B-C)/B×100
Wherein R is antibiotic rate (%); B is blank sample average bacterial count recovered, the cfu/ sheet; C is antibiotic plastic sample average bacterial count recovered, the cfu/ sheet.
Table 1
The preparation technology of a kind of antibiotic plastic provided by the invention, its technique is simple, and made antibiotic plastic antibacterial effect is remarkable, and is lasting.
The above; it is only preferred embodiment of the present invention; be not that the present invention is imposed any restrictions, every any simple modification, change and equivalence of above embodiment being done according to the technology of the present invention essence changes, and all still belongs in the protection domain of technical solution of the present invention.
Claims (6)
1. antibiotic starch plastics of novel beta-cyclodextrin host-guest inclusion thing, it is characterized in that described antibiotic starch plastic is comprised of plastic raw materials, antibacterial plastic concentrate, dispersion agent and antioxidant, by weight percentage, plastic raw materials 95% ~ 99%, antibacterial plastic concentrate 1% ~ 4%, dispersion agent 0.2% ~ 0.5%, antioxidant 0.5% ~ 1%, described plastic raw materials are starch plastics.
2. the antibiotic starch plastics of novel beta-cyclodextrin host-guest inclusion thing according to claim 1, it is characterized in that described starch plastics be in full starch plastics, starch filled plastics or starch derivative plastics etc. any.
3. the antibiotic starch plastics of novel beta-cyclodextrin host-guest inclusion thing according to claim 1 is characterized in that described dispersion agent is a kind of in zeolite, silica, wilkinite, sepiolite, diatomite or sodium stearate etc.
4. the antibiotic starch plastics of novel beta-cyclodextrin host-guest inclusion thing according to claim 1, it is characterized in that described antioxidant adopts 2 mercapto benzimidazole, N, N'-is two, and [β (3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, β-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, 4,4''-methylene-bis (2, the 6-DI-tert-butylphenol compounds), tricresyl phosphite (2, ester) or four [β-(3 the 4-di-tert-butyl-phenyl), the 5-di-tert-butyl-hydroxy phenyl) propionic acid] one or more in pentaerythritol ester.
5. the preparation method of the antibiotic starch plastics of novel beta-cyclodextrin host-guest inclusion thing as claimed in claim 1 is characterized in that concrete steps are as follows:
(1) preparation of antibacterial plastic concentrate, described antibacterial plastic concentrate is sulphur acidifying beta-cyclodextrin cross-linking starch, concrete preparation method is: at first the 30g-90g beta-cyclodextrin is joined in the vitriol oil of 100ml-200ml concentration 90%, at 0-10 ℃ of reaction 2-5h, excessive sulfuric acid filters and makes sulphur acidifying beta-cyclodextrin with the neutralization of 1N calcium carbonate; Sulphur acidifying beta-cyclodextrin is water-soluble, join to get the aqueous solution of 50g/L sulphur acidifying beta-cyclodextrin, and under ethylenediamine tetraacetic acid (EDTA) exists 120 ℃ of reaction 10-90min, add 3%-10% antimicrobial nano particle solution or organic antibacterial agent, have the molecular structure of hollow round table due to beta-cyclodextrin, belong to amphiphilic species, hydrophilic radical is contained in the outside---and hydrophilic, inner hydrophobic can obtain the antibacterial plastic concentrate of beta-cyclodextrin host-guest inclusion thing;
(2) with plastic raw materials, antibacterial plastic concentrate, dispersion agent and antioxidant join in agitator in proportion, then will mix and join fusion-grafting in twin screw extruder, namely obtain desired product.
6. method according to claim 5, it is characterized in that described antimicrobial nano particle solution be in nano zine oxide, nano titanium oxide or nanometer silver any, described antiseptic-germicide be the guanidine class antiseptic-germicide such as polyhexamethylene guanidine, dichloro give birth to or N-tert-butyl acrylamide in any.
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Cited By (6)
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| CN103497275A (en) * | 2013-08-09 | 2014-01-08 | 华北电力大学（保定） | Anti-bacterium antivirus guanidine salt star-shaped polymer, preparation method and applications thereof |
| CN105778023A (en) * | 2016-03-17 | 2016-07-20 | 南通瑞特建筑材料有限公司 | Polycarboxylic acid water reducing agent and method for preparing same |
| US9505851B2 (en) | 2014-07-22 | 2016-11-29 | Ting-Hung SU | Antifungal composite and method for manufacturing the same |
| CN107189107A (en) * | 2017-06-21 | 2017-09-22 | 芜湖蓝天工程塑胶有限公司 | Nano Ag antibacterial fiber cellulosic material and its preparation method and application |
| CN112300533A (en) * | 2020-11-14 | 2021-02-02 | 百草边大生物科技(青岛)有限公司 | Novel wormwood ABS plastic applied to children toys |
| CN114574868A (en) * | 2022-03-01 | 2022-06-03 | 深圳市新骏翔科技有限公司 | Water-based metal cleaning agent and preparation method thereof |
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Application publication date: 20130619 |