CN101473847B - Composite anti-bacteria agent as well as preparation method and use thereof - Google Patents
Composite anti-bacteria agent as well as preparation method and use thereof Download PDFInfo
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- CN101473847B CN101473847B CN 200910036823 CN200910036823A CN101473847B CN 101473847 B CN101473847 B CN 101473847B CN 200910036823 CN200910036823 CN 200910036823 CN 200910036823 A CN200910036823 A CN 200910036823A CN 101473847 B CN101473847 B CN 101473847B
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Abstract
The invention discloses a compound antibacterial agent formed by complexing chitin derivative, medical stone and metal ions, wherein, the metal ions comprise Ca<2+>, Zn<2+>, Cu<2+>, Ba<2+> and Al<3+>. The invention also provides a preparation method for the compound antibacterial agent, and the method comprises the following steps: the chitin derivative aqueous solution with the weight percentage of 1 percent to 10 percent is prepared, then the medical stone with the mass ratio of 1:1 to 1.5 is added for mixing according to the chitin derivative aqueous solution, then the saturated metal ion solution with the weight percentage of 20 percent is added for filtering after complexing, and then the filter residues are dried. The invention also provides an application of the compound antibacterial agent in the preparation of the fresh-keeping antibiotic plastics, i.e., the compound antibacterial agent is used for preparing the master batch. The invention has the advantages that the price ofthe raw material of the compound antibacterial agent is low, the method for preparing the master batch is simple, the produced preservative film has good fresh-keeping effect, bacteria resistant effect and good mold-proof effect, and the invention is easy for the popularization and the application of the industrial production.
Description
Technical field
The present invention relates to a kind of complex antimicrobials and its preparation method and application, especially a kind of complex antimicrobials for the preparation of the anti-bacterial refreshing plastics and its preparation method and application.
Background technology
China is world-class vegetables and fruits big producing country and sells big country, yet vegetables and fruits have the vegetables and fruits loss about 30% in storage, transportation and sales process, whenever be only this loss just up to 75,000,000,000 yuan, and the economic benefit that has had a strong impact on China increases.Trace it to its cause packaging material improper use or lacking packing is to cause the rot major reason of loss of vegetables and fruits.Common plastic film is used for packing, and oxygen permeability is relatively poor, when carrying out the packing of the fresh food such as vegetables and fruits with it, causes easily CO in the packing container
2Excessive concentration O
2Concentration excessively low, make food carry out anaerobic respiration, be absorbed in disorder and putrid and deteriorated, because respiration and transpiration produce moisture, form moist environment simultaneously, caused growing, breed of bacterium, accelerated the rotten rotten of vegetables and fruits.
At present, domestic relevant antimicrobial preservative film development is generally adopted and is added carrying silver antimicrobials in plastics preparation anti-bacterial refreshing master batch, the packing that is used for food, but because carrying silver antimicrobials is on the high side, and add easy oxidation stain in man-hour, so the production of the method large-scale industrialization has been subject to larger restriction.Prior art is used the antibacterial agent that the derivative by the natural polymer chitin makes in addition: water miscible carboxymethyl chitin, shitosan itself have good antibacterial and mouldproof effect, yet the processing temperature that surpasses 100 ℃ can make it decompose carbonization, its dry product of while also can't become fine powder and join in the plastics, because it at high temperature decomposes carbonization easily, be subjected to the impact of processing conditions, can only adopt at present the method for filming to add, industrial production is subject to larger limitation, also fails to be applied in the large-scale industrial production.
Summary of the invention
Technical problem to be solved by this invention is the difficulty that overcomes prior art, and purpose is to provide a kind of effectively antibiotic complex antimicrobials with preventing that vegetables and fruits are rotten, that cost is low, resistant to elevated temperatures, can take full advantage of chitin derivativ.
Another object of the present invention provides a kind of preparation method of simple efficient above-mentioned complex antimicrobials.
A further object of the invention provides the application of above-mentioned complex antimicrobials.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of complex antimicrobials is formed by chitin derivativ, medical stone and complexing of metal ion, and described metal ion is Ca
2+, Zn
2+, Cu
2+, Ba
2+, Al
3+
Described chitin derivativ is selected from carboxymethyl chitin, carboxyethyl chitin, carboxymethyl ethyl chitin, carboxylic propyl group chitin, carboxylic butyl chitin, CMC, carboxyetbyl chitosan, carboxymethyl ethyl chitosan or carboxylic butyl shitosan.
Complex antimicrobials of the present invention adopts water miscible chitin derivativ, itself has good antibacterial and mouldproof effect, yet the processing temperature above 100 ℃ can make it decompose carbonization, and its dry product of while also can't become fine powder and join in the plastics.For overcoming this shortcoming, the present invention has introduced medical stone in the middle of component, medical stone itself also has stronger bacteriostasis efficacy, and the processing temperature that can improve medical stone with the method for complexation of metal ions to be adapting to the processing temperature of plastics, and can become fine powder and join in the plastics.The present invention utilizes medical stone as the carrier of antibacterial agent, in water slurry, add metal ion, make free metal ion and the metal ion in the medical stone and water-solubility chitin derivative form controlled part complex compound and be attached on the medical stone, drying is pulverized and is made complex antimicrobials, overcome carboxymethyl chitin, CMC is limited by processing temperature, be difficult to join the shortcoming in the plastics, kept simultaneously the characteristics of both original antibacterial and mouldproofs.
The preparation method of above-mentioned complex antimicrobials is:
The preparation weight percent concentration is 1%～10% the chitin derivativ aqueous solution, again by the chitin derivativ aqueous solution: medical stone quality ratio is 1: 1～1.5 adding medical stones, mixing, then add an amount of weight ratio concentration and be 15～30% saturated metal ion solution, filter filter residue and drying and get final product after the complexing.
The metal ion generation complex reaction that dissociates in the metal ion of complex antimicrobials employing chitin derivativ of the present invention and interpolation and the medical stone, the high efficiency of additive capability that keeps simultaneously medical stone, through the double action of chemistry with physics, obtain at last the pressed powder with antibacterial and mouldproof for the preparation of vinyon.
The present invention also provides the application of above-mentioned complex antimicrobials in the fresh-keeping antibiotic plastic of preparation.
Described application in the fresh-keeping antibiotic plastic of preparation is for the preparation of master batch with described complex antimicrobials.
Describedly with complex antimicrobials for the preparation of master batch such as preferred version be: with 20～50 weight portion complex antimicrobials, 50～80 weight portion low density polyethylene (LDPE) (LDPE) 1F7B, 5～10 weight portion SiO
2, 2～5 weight portion KMnO
4, 0.1～0.5 weight portion Arlacel-20,1～2 weight portion fusing point is 50～80 ℃ paraffin, makes the material of kneading; The material of kneading makes master batch through extruding pelletization; Extrusion temperature is: 130 ℃～170 ℃.
The above-mentioned master batch that makes can further be made various plastics as required.
Compared with prior art, except above-mentioned beneficial effect, the present invention also has following beneficial effect:
Complex antimicrobials raw material chitin derivativ of the present invention is natural prodcuts, cost is low, the price of other raw materials is also cheaper, the complex antimicrobials preparation method is simple, and the antibacterial agent that makes can be high temperature resistant, improves processing temperature in preparation process, can under the process conditions of plastic shaping, still keep good antibacterial effect, with the plastic blend moulding, also be outstanding feature of the present invention, have not yet to see the relevant report that relates to this aspect.
Complex antimicrobials of the present invention is applied to prepare plastic package material, has fresh-keeping antibiotic effect, has suppressed the metabolic process of bacterium, has prolonged the pot-life of the fresh food such as vegetables and fruits, has kept local flavor and the nutritive value of food, and this all is very important.
The metal ion generation complex reaction that dissociates in the metal ion of complex antimicrobials employing chitin derivativ of the present invention and interpolation and the medical stone, the high efficiency of additive capability that keeps simultaneously medical stone, through the double action of chemistry with physics, obtain at last the pressed powder with antibacterial and mouldproof for the preparation of vinyon, be applied to prepare the anti-bacterial refreshing plastic master batch, also can further make as required more various plastics.The method that complex antimicrobials of the present invention is applied to prepare master batch is simple, and its fresh-keeping antibacterial and mouldproof of the preservative film of production is effective, is easy to industrial applying.
Embodiment
Below further specify technical scheme of the present invention by specific embodiment, all umbers are weight portion.
The preparation of embodiment 1 medical stone/methylol chitin compound antibacterial powder
Measure the 1L deionized water, add the methylol chitin of 30g sheet, be heated to 80 ℃ while stir, it is dissolved fully, become clear, viscous solution after the cooling.Mentioned solution and mixed being incorporated in the miniature high-speed agitator of 1kg2500 purpose medical stone are stirred.Adding the 400g weight percent concentration is 20%CaCl
2Solution is treated its slowly complexing.Then filtering solution, residual filter residue placed 100 ℃ of oven dry after, the Powdered medical stone of crushing screening/methylol chitin complex antimicrobials.
Embodiment 2
Preparation complex antimicrobials: measure the 1L deionized water, add the methylol chitin of 10g sheet, be heated to 80 ℃ while stir, it is dissolved fully, become clear, viscous solution after the cooling.Mentioned solution and mixed being incorporated in the miniature high-speed agitator of 1kg2500 purpose medical stone are stirred.Adding the 400g weight percent concentration is 25%CuCl
2Solution is treated its slowly complexing.Then filtering solution, residual filter residue placed 100 ℃ of oven dry after, the Powdered medical stone of crushing screening/methylol chitin complex antimicrobials.
Preparation master batch: with 30 parts of the complex antimicrobials that make, 65 parts of LDPE 1F7B, SiO
25 parts, KMnO
42 parts, 0.5 part of Arlacel-20,2 parts in paraffin (50～80 ℃ of fusing points) is kneaded into the mud shape, discharging in homogenizer; What make kneads material in the dual-screw-stem machine of φ 25, and extruding pelletization makes fresh-keeping antibacterial matrices.The Temperature Setting of extruder is: 130,150,160,170, and 170 ℃; Rotating speed 40r/min.
The check master batch antibacterial effect: make with 6 parts of fresh-keeping antibacterial matrices, after 100 parts of mixing of LDPE, in extruding the blown film unit (the same double screw extruder adds the blown film device), temperature design 140,170,180,185,185 ℃.It is the film of 20 μ m that blown film becomes thickness, through food hygiene, antibiotic relevant mark with mildew-resistant evaluation test (GB9687-1998, GB/T2591-2003, ASTM G21-96).Obtain following result:
(1) GB9687-1998: meet used for packing foods products of polyethylene for food packaging sanitary standard.
(2) GB/T2591-2003: bacteriostasis rate 79.3%
(3) ASTM G21-96: 0-is without mildew for the mildew-resistant grade
Embodiment 3
Preparation complex antimicrobials: measure the 1L deionized water, add the methylol chitin of 100g sheet, be heated to 80 ℃ while stir, it is dissolved fully, become clear, viscous solution after the cooling.Mentioned solution and mixed being incorporated in the miniature high-speed agitator of 1.5kg 2500 purpose medical stones are stirred.Adding the 300g weight percent concentration is 15%AlCl
3Solution is treated its slowly complexing.Then filtering solution, residual filter residue placed 100 ℃ of oven dry after, the Powdered medical stone of crushing screening/methylol chitin complex antimicrobials.
The preparation master batch: the medical stone that makes/methylol chitin compound antibacterial powder, get equally 30 parts, 65 parts of LDPE1F7B, SiO
25 parts, KMnO
43 parts, 0.5 part of Arlacel-20,2 parts in paraffin (50～80 ℃ of fusing points) is kneaded into the mud shape, discharging in homogenizer; What make kneads material in the dual-screw-stem machine of φ 25, and extruding pelletization makes fresh-keeping antibacterial matrices.The Temperature Setting of extruder is: 130,150,160,170, and 170 ℃; Rotating speed 40r/min.
The antibacterial effect of check master batch: the master batch that makes under the condition of embodiment 2 with the LDPE blowfilm shaping, through food hygiene, the antibiotic relevant result who marks evaluation test (GB9687-1998, GB/T2591-2003, ASTM G21-96) with mildew-resistant be:
(1) GB9687-1998: meet used for packing foods products of polyethylene for food packaging sanitary standard.
(2) GB/T2591-2003: bacteriostasis rate 84.1%
(3) ASTM G21-96: 0-is without mildew for the mildew-resistant grade
Embodiment 4
Preparation master batch: get 20 parts of the complex antimicrobials that embodiment 1 makes, 50 parts of LDPE 1F7B, SiO
27 parts, KMnO
45 parts, 0.1 part of Arlacel-20,1 part in paraffin (50～80 ℃ of fusing points) is kneaded into the mud shape, discharging in homogenizer; What make kneads material in the dual-screw-stem machine of φ 25, and extruding pelletization makes fresh-keeping antibacterial matrices.The Temperature Setting of extruder is: 130,150,160,170, and 170 ℃; Rotating speed 40r/min.
The antibacterial effect of check master batch: the master batch that makes under the condition of embodiment 2 with the LDPE blowfilm shaping, through food hygiene, the antibiotic relevant result who marks evaluation test (GB9687-1998, GB/T2591-2003, ASTM G21-96) with mildew-resistant be:
(1) GB9687-1998: meet used for packing foods products of polyethylene for food packaging sanitary standard.
(2) GB/T2591-2003: bacteriostasis rate 85.6%
(3) ASTM G21-96: 0-is without mildew for the mildew-resistant grade
Embodiment 5
Preparation complex antimicrobials: measure the 1L deionized water, add the methylol chitin of 80g sheet, be heated to 80 ℃ while stir, it is dissolved fully, become clear, viscous solution after the cooling.Mentioned solution and mixed being incorporated in the miniature high-speed agitator of 1.5kg 2500 purpose medical stones are stirred.Adding the 500g weight percent concentration is 30%ZnCl
2Solution is treated its slowly complexing.Then filtering solution, residual filter residue placed 100 ℃ of oven dry after, the Powdered medical stone of crushing screening/methylol chitin complex antimicrobials.
The preparation master batch: the medical stone that makes/methylol chitin compound antibacterial powder is got 50 parts, 80 parts of LDPE 1F7B, SiO
210 parts, KMnO
45 parts, 0.3 part of Arlacel-20,1 part in paraffin (50～80 ℃ of fusing points) is kneaded into the mud shape, discharging in homogenizer; What make kneads material in the dual-screw-stem machine of φ 25, and extruding pelletization makes fresh-keeping antibacterial matrices.The Temperature Setting of extruder is: 130,150,160,170, and 170 ℃; Rotating speed 40r/min.
The antibacterial effect of check master batch: the master batch that makes under the condition of embodiment 2 with the LDPE blowfilm shaping, through food hygiene, the antibiotic relevant result who marks evaluation test (GB9687-1998, GB/T2591-2003, ASTM G21-96) with mildew-resistant be:
(1) GB9687-1998: meet used for packing foods products of polyethylene for food packaging sanitary standard.
(2) GB/T2591-2003: bacteriostasis rate 80.9%
(3) ASTM G21-96: 0-is without mildew for the mildew-resistant grade
Embodiment 6
Method and proportioning with reference to embodiment 1 change complexation of metal ions solution into BaCl
2Make compound antibacterial powder, and then use and embodiment 2 identical methods make master batch, again through identical with embodiment 2 condition and LDPE blowfilm shaping, through food hygiene, the antibiotic relevant result who marks evaluation test (GB9687-1998, GB/T2591-2003, ASTM G21-96) with mildew-resistant be:
(1) GB9687-1998: meet used for packing foods products of polyethylene for food packaging sanitary standard.
(2) GB/T2591-2003: bacteriostasis rate 86.5%
(3) ASTM G21-96: 0-is without mildew for the mildew-resistant grade
Claims (4)
1. a complex antimicrobials is formed by chitin derivativ, medical stone and complexing of metal ion, and described metal ion is Al
3+, it is characterized in that described complex antimicrobials is the antibacterial agent that is prepared from as follows: measure the 1L deionized water, add the methylol chitin of 100g sheet, be heated to 80 ℃ while stir, it is dissolved fully, become clear, viscous solution after the cooling; Mentioned solution and mixed being incorporated in the miniature high-speed agitator of 1.5kg2500 purpose medical stone are stirred; Adding the 300g weight percent concentration is 15%AlCl
3Solution is treated its slowly complexing; Then filtering solution, residual filter residue placed 100 ℃ of oven dry after, the Powdered medical stone of crushing screening/methylol chitin complex antimicrobials.
2. the application of complex antimicrobials claimed in claim 1 in the fresh-keeping antibiotic plastic of preparation.
3. application as claimed in claim 2 is characterized in that described application in the fresh-keeping antibiotic plastic of preparation is for the preparation of master batch with described complex antimicrobials.
4. application as claimed in claim 3 is characterized in that describedly with complex antimicrobials for the preparation of master batch being: with 20～50 weight portion complex antimicrobials, and 50～80 weight portion low density polyethylene (LDPE) 1F7B, 5～10 weight portion SiO
2, 2～5 weight portion KMnO
4, 0.1～0.5 weight portion Arlacel-20,1～2 weight portion fusing point is 50～80 ℃ paraffin, makes the material of kneading; The material of kneading makes master batch through extruding pelletization; Extrusion temperature is: 130 ℃～170 ℃.
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| CN101473847B true CN101473847B (en) | 2013-01-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011488A (en) * | 2017-05-16 | 2017-08-04 | 马嘉 | A kind of preparation and application of NEW TYPE OF COMPOSITE antiseptic and its master batch |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408628A (en) * | 2011-09-21 | 2012-04-11 | 浙江金海环境技术股份有限公司 | Chitin-containing polymer master batch, air filter screen monofilament, and preparation method and application thereof |
| CN103271413A (en) * | 2013-05-08 | 2013-09-04 | 南京年吉冷冻食品有限公司 | Novel bean curd preservative compounding method |
| CN103734872A (en) * | 2013-12-25 | 2014-04-23 | 吴江华诚复合材料科技有限公司 | Compounding method for novel bean curd preservative |
| CN111378200B (en) * | 2020-04-22 | 2021-05-18 | 武汉大学 | Carboxymethyl chitin porous granular material, preparation method and application |
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| CN1294144A (en) * | 2000-11-14 | 2001-05-09 | 上海博纳科技发展有限公司 | Mother particles of antibacterial plastics and its application in preparing antibacterial plastic products |
| CN1685829A (en) * | 2005-04-30 | 2005-10-26 | 武汉大学 | Preparation method of chitin/zinc compound bactericide |
| CN1709062A (en) * | 2005-06-10 | 2005-12-21 | 中国乐凯胶片集团公司 | Medical stone inorganic antibacterial agent and its preparing method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294144A (en) * | 2000-11-14 | 2001-05-09 | 上海博纳科技发展有限公司 | Mother particles of antibacterial plastics and its application in preparing antibacterial plastic products |
| CN1685829A (en) * | 2005-04-30 | 2005-10-26 | 武汉大学 | Preparation method of chitin/zinc compound bactericide |
| CN1709062A (en) * | 2005-06-10 | 2005-12-21 | 中国乐凯胶片集团公司 | Medical stone inorganic antibacterial agent and its preparing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011488A (en) * | 2017-05-16 | 2017-08-04 | 马嘉 | A kind of preparation and application of NEW TYPE OF COMPOSITE antiseptic and its master batch |
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| CN101473847A (en) | 2009-07-08 |
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