CN103788452A - Long-acting deoxidization antibacterial polyolefin plastic - Google Patents
Long-acting deoxidization antibacterial polyolefin plastic Download PDFInfo
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- CN103788452A CN103788452A CN201410016959.4A CN201410016959A CN103788452A CN 103788452 A CN103788452 A CN 103788452A CN 201410016959 A CN201410016959 A CN 201410016959A CN 103788452 A CN103788452 A CN 103788452A
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- deoxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The invention discloses long-acting deoxidization antibacterial polyolefin plastic. The long-acting deoxidization antibacterial polyolefin plastic is characterized by comprising the following components in parts by weight: 100 parts of polyethylene resin, 2-10 parts of bi-component deoxidizing agent, 0.2-2 parts of compound antibacterial agent, 1-5 parts of high molecular coupling agent, 3-8 parts of toughening agent, 0.2-1 part of dispersing agent and 0.01-0.2 part of antioxidant. The long-acting deoxidization antibacterial polyolefin plastic has long-term and efficient deoxidization performance, and can be directly applied to curtain coating or film blowing and bag making to perform deoxidized packaging.
Description
Technical field:
The present invention relates to field of polymer material preparing technology, especially a kind of functional plastic that is exclusively used in Deoxygen Packaging, this technology has permanent deoxidation efficiently, can be directly used in bag after curtain coating or Blown Film, carries out Deoxygen Packaging.
Background technology:
Oxygen is the main cause that causes food spoilage, therefore reduces the oxygen content in food pack, except slowing down the physiological metabolism of fresh provisions, can also suppress the growth of microorganism, aerobic bacteria etc.Deoxygen Packaging technology is a kind of novel method for packing occurring after vacuum and gas flush packaging.The object of this technological development is edible safety and the keeping quality in order to improve the food to oxygen sensitive.Deoxygen Packaging is a kind of novel method for packing occurring after vacuum packaging and gas flush packaging, and Deoxygen Packaging more effectively prevents than vacuum packaging and gas flush packaging or to delay aerobic microorganism caused putrid and deteriorated, has greatly extended the quality guaranteed period.By Deoxygen Packaging, can in food production process, reduce and even avoid adding the chemical additive such as sanitas and antioxidant, thereby make food safer, be of value to the healthy of people.
In recent years, some bad businessman is in order to improve effective period of food quality, pack by adding the modes such as excessive sanitas, oxidation inhibitor, use low cost packing inferior, grievous injury human consumer's interests.
Conventional Deoxygen Packaging is to pack by enclosing reductor parcel in packing bag the inside in the market, and the production technology of this reductor parcel is mainly monopolized by developed countries such as American-European and Japan, and price is very expensive, and packing cost is high.But this reductor parcel in use can cause breakage and contaminated food products also can often be eaten by mistake and the accident that meets accident by child.
In addition, because polyolefin plastics is easily polluted by various unwanted bacterias, in the situation that humidity is applicable, more easily breed bacterium.Can head it off by adding antiseptic-germicide modification.Conventional plastic antimicrobial agent organic antibacterial agent and inorganic antiseptic two classes at present.Organic antibacterial agent mainly contains ethers, phenol, biphenyl ethers, quaternary ammonium salt, thiazole compound etc., be characterized in that sterilization speed is fast, has a broad antifungal spectrum, but resistance toheat is poor, and antibacterial validity period is short.Inorganic antiseptic is mainly silver, zinc plasma and compound or complex compound, is characterized in good heat resistance, and has a broad antifungal spectrum is safe, and antibacterial validity period is long etc.But silver-series antibacterial agent colour stability is poor, meeting variable color in use procedure, and can not make antimicrobial component be uniformly dispersed, antibacterial effect can not be lasting.The composite mode of plan employing nanometer silver of the present invention and organosilicon antibacterial agent reaches the object of better anti-microbial property.
Summary of the invention:
The object of this invention is to provide one and there is permanent deoxidation efficiently, can be directly used in bag after curtain coating or Blown Film, carry out the long-acting deoxidation antimicrobial form polyolefin plastics of Deoxygen Packaging.
Object of the present invention is achieved through the following technical solutions.
A kind of long-acting deoxidation antimicrobial form polyolefin plastics, it is characterized in that: described long-acting deoxidation antimicrobial form polyolefin plastics comprises polyvinyl resin, two-pack reductor, composite bactericidal agent, polymer coupler, toughner, dispersion agent and oxidation inhibitor, and the component of its parts by weight is:
Polyvinyl resin: 100;
Two-pack reductor: 2～10;
Composite bactericidal agent: 0.2～2;
Polymer coupler: 1～5;
Toughner: 3～8;
Dispersion agent: 0.2～1;
Oxidation inhibitor: 0.01～0.2.
Described polyvinyl resin is the above mixture of the polyvinyl resin of ldpe resin or high-density polyethylene resin or linear low density polyethylene resin or metallocene catalysis or its two or the two.
Described two-pack reductor makes in the following way: by 100 parts of iron powders (particle diameter 5～20 μ m), 5 parts of copper sulfate (CuSO4), 5 parts of sodium-chlor (NaCl), 100 parts of sodium ascorbates (Vc sodium or SA), fully pulverize and be dry mixed evenly, then for subsequent use after 4 hours through 80 ℃ of vacuum-dryings.
It is composite that described composite bactericidal agent is that nanometer silver and organosilicon antibacterial agent carry out, and its particle diameter is 0.02～0.5 μ m, and process through coated on surface.
Described polymer coupler is the grafted maleic anhydride multipolymer of polyethylene (PE) or polyethylene elastomer (POE), terpolymer EP rubber (EPDM).
Described toughner is ethylene-octene copolymer or ethylene-butene copolymer, or the mixture of ethylene-octene copolymer and ethylene-butene copolymer.
Described dispersion agent is selected from polyethylene wax, or polypropylene sodium, or Zinic stearas, or one or more mixture in stearylamide dispersion agent.
Described oxidation inhibitor is one or more in antioxidant 1010, irgasfos 168, antioxidant 1076, oxidation inhibitor B215, antioxidant 2246 or antioxidant 264.
Advantage of the present invention:
The present invention adopts two-pack organic and inorganic deoxidation system, persistence and the high efficiency of deoxidation efficiency are guaranteed, organic deoxidant sodium ascorbate has deoxidation rapidly but the not high feature of persistence on the one hand, on the other hand, the deoxidation of modification iron powder is slow but of long duration, and by the ingenious combination of the two, can reach good deoxidation effect.In addition, also by copper sulfate (CuSO
4) and sodium-chlor (NaCl) iron powder is carried out to modification, CuSO
4interior Cu
2+and the Fe of oxidation of iron powder generation
2+or Fe
3+all effective catalysts of the deoxygenation of sodium ascorbate (SA) Deng transition metal ion.And iron powder is at water molecules and NaCl and CuSO
4multiple katalysis under cause oxidation of iron powder with produce Fe
2+, Fe
3+speed accelerate, and composite deoxidant system in generate Cu
2+, Fe
2+or Fe
3+further effectively promote again the oxidation of sodium ascorbate (SA) thereby produce synergy composite effect Deng transition metal ion.
The present invention adopts nanometer silver and organic silicon compound to make antiseptic-germicide, the inorganic complex antimicrobials of Nano Particle, has spectrum germ resistance, and mould staphylococcus aureus intestinal bacteria etc. are had to antibacterial effect, and anti-microbial activity is stronger, use less antiseptic-germicide just to there is good antibacterial effect.And on the mechanical property impact of resin seldom, nanometer silver also can promote polyolefinic nucleation and crystallization to the antiseptic-germicide adding simultaneously, improves the mechanical property of material.
The grafted maleic anhydride multipolymer of the alkene such as PE, POE or EPDM that the present invention adds, the bonding and coupling that improves polyolefine and infill system, thereby stretching, the shock strength of raising matrix material.
The fatty acid acyl amine dispersion agent that the present invention adds has increased the surface affinity of polyolefin carrier and antiseptic-germicide and reductor, antiseptic-germicide and reductor is disperseed more even, makes material product surface brighter and cleaner.
The present invention is by the use of coupling agent and dispersion agent and the preparation of antibacterial matrices, greatly improve the degree of scatter of antimicrobial particle in matrix resin, effectively reduce the holes phenomenon that polythene material occurs in blow-moulding process, finally realize formability and the efficient anti-microbial property of film.
The present invention adopts polyolefin elastomer ethylene-octene copolymer or ethylene-butene copolymer to do polyolefine toughener, has increased the shock resistance of material; Use nanometer silver and the agent of the composite making composite bactericidal of organosilicon antibacterial agent, make the quick and durable and safety of the anti-microbial property of material; The present invention uses dispersion agent, has increased the macromolecular surface affinity of polyolefine body and reductor and antiseptic-germicide, has improved the surface brightness of material and the dispersing uniformity of auxiliary agent.
Combination oxidation inhibitor of the present invention can prevent that polyolefine from affecting physical property at high temperature modified middle its colour changed into yellow and because of oxidation.
Above-mentioned supplementary material is dry mixed according to certain proportioning, fully mixes in rear input twin screw extruder and melt extrudes, and the cooling and pelletizing by tank, finally makes long-acting deoxidation antimicrobial form polyolefine functional plastics.
Carrying out twin screw while melt extruding granulation, it should be noted that, guaranteeing under the condition of the abundant melting of polyolefin resin, the extrusion temperature of twin screw granulating extruder reduces as far as possible, extrusion temperature is controlled at below 180 ℃ when take polyethylene as carrier, thereby reduces the thermal destruction of sodium ascorbate in reductor as far as possible.
The invention provides a kind of safe ready and have the polyolefine functional plastics of long-acting type deoxidation antibacterial effect.This functional plastics can be made packing bag by Blown Film, is blow molded into packing bottle, or is injection molded into other containers or device.Making packing bag or when bottle, can adopt separately material of the present invention directly to pack, or with other materials by extruding compound or being coated with compound mode and being combined into multilayer material, thereby ensure better the performance of material.One of them typically used example is as follows: wherein internal layer adopts ldpe resin to do heat-sealing bonding layer, middle layer adopts polyolefinic deoxygenation function plastics of the present invention, outer employing has compared with the material of high barrier as nylon (PA) or polyvinylidene dichloride (PVDC) or other barrier plastics, thereby while avoiding packing, oxygen infiltrates inner side by skin.
By adopting material of the present invention according to the made packing of aforesaid way, can remove oxygen residual in unlap and package handling can be removed in time a small amount of oxygen of slowly thoroughly coming in after completing, kill bacterium, slow down the Oxidation of Fat and Oils in simulated foods, extend the quality guaranteed period of food.Technique of the present invention is simple, stable and reliable for performance, and deoxidation is thorough, and safety non-toxic can be used for Food preservation.
Embodiment:
Below in conjunction with specific embodiment, the present invention is done further and described, but specific embodiment does not do any restriction to the present invention, other adopt the formula of the claims in the present invention defined all within this patent protection domain.
Embodiment 1:
Wherein twin screw granulating extruder extrusion temperature is between 110-180 ℃.Wherein two-pack reductor makes in the following way: by 100 parts of iron powders (particle diameter 5～20 μ m), 5 parts of copper sulfate (CuSO4), 5 parts of sodium-chlor (NaCl), 100 parts of sodium ascorbates (SA), fully pulverize and be dry mixed evenly, then for subsequent use after 4 hours through 80 ℃ of vacuum-dryings.Wherein composite bactericidal agent, employing particle diameter is that nanometer silver and the organosilicon of 0.02～0.5 μ m carries out composite according to 2:1.
Embodiment 2:
Wherein twin screw granulating extruder extrusion temperature is between 110-180 ℃.Wherein two-pack reductor makes in the following way: by 100 parts of iron powders (particle diameter 5～20 μ m), 5 parts of copper sulfate (CuSO4), 5 parts of sodium-chlor (NaCl), 100 parts of sodium ascorbates (SA), fully pulverize and be dry mixed evenly, then for subsequent use after 4 hours through 80 ℃ of vacuum-dryings.Wherein composite bactericidal agent, employing particle diameter is that nanometer silver and the organosilicon of 0.02～0.5 μ m carries out composite according to 2:1.
Embodiment 3:
Wherein twin screw granulating extruder extrusion temperature is between 110-180 ℃.Wherein two-pack reductor makes in the following way: by 100 parts of iron powders (particle diameter 5～20 μ m), 5 parts of copper sulfate (CuSO4), 5 parts of sodium-chlor (NaCl), 100 parts of sodium ascorbates (SA), fully pulverize and be dry mixed evenly, then for subsequent use after 4 hours through 80 ℃ of vacuum-dryings.Wherein composite bactericidal agent, employing particle diameter is that nanometer silver and the organosilicon of 0.02～0.5 μ m carries out composite according to 2:1.
Embodiment 4:
Wherein twin screw granulating extruder extrusion temperature is between 110-180 ℃.Wherein two-pack reductor makes in the following way: by 100 parts of iron powders (particle diameter 5～20 μ m), 5 parts of copper sulfate (CuSO4), 5 parts of sodium-chlor (NaCl), 100 parts of sodium ascorbates (SA), fully pulverize and be dry mixed evenly, then for subsequent use after 4 hours through 80 ℃ of vacuum-dryings.Wherein composite bactericidal agent, employing particle diameter is that nanometer silver and the organosilicon of 0.02～0.5 μ m carries out composite according to 2:1.
Claims (8)
1. a long-acting deoxidation antimicrobial form polyolefin plastics, it is characterized in that: described long-acting deoxidation antimicrobial form polyolefin plastics comprises polyvinyl resin, two-pack reductor, composite bactericidal agent, polymer coupler, toughner, dispersion agent and oxidation inhibitor, and the component of its parts by weight is:
Polyvinyl resin: 100;
Two-pack reductor: 2～10;
Composite bactericidal agent: 0.2～2;
Polymer coupler: 1～5;
Toughner: 3～8;
Dispersion agent: 0.2～1;
Oxidation inhibitor: 0.01～0.2.
2. long-acting deoxidation antimicrobial form polyolefin plastics according to claim 1, is characterized in that: described polyvinyl resin is the above mixture of the polyvinyl resin of ldpe resin or high-density polyethylene resin or linear low density polyethylene resin or metallocene catalysis or its two or the two.
3. long-acting deoxidation antimicrobial form polyolefin plastics according to claim 1, it is characterized in that: described two-pack reductor makes in the following way: by 100 parts of iron powders (particle diameter 5～20 μ m), 5 parts of copper sulfate (CuSO4), 5 parts of sodium-chlor (NaCl), 100 parts of sodium ascorbates (Vc sodium or SA), fully pulverize and be dry mixed evenly, then for subsequent use after 4 hours through 80 ℃ of vacuum-dryings.
4. long-acting deoxidation antimicrobial form polyolefin plastics according to claim 1, is characterized in that: it is composite that described composite bactericidal agent is that nanometer silver and organosilicon antibacterial agent carry out, and its particle diameter is 0.02～0.5 μ m, and process through coated on surface.
5. long-acting deoxidation antimicrobial form polyolefin plastics according to claim 1, is characterized in that: described polymer coupler is the grafted maleic anhydride multipolymer of polyethylene (PE) or polyethylene elastomer (POE), terpolymer EP rubber (EPDM).
6. long-acting deoxidation antimicrobial form polyolefin plastics according to claim 1, is characterized in that: described toughner is ethylene-octene copolymer or ethylene-butene copolymer, or the mixture of ethylene-octene copolymer and ethylene-butene copolymer.
7. long-acting deoxidation antimicrobial form polyolefin plastics according to claim 1, is characterized in that: described dispersion agent is selected from polyethylene wax, or polypropylene sodium, or Zinic stearas, or one or more mixture in stearylamide dispersion agent.
8. long-acting deoxidation antimicrobial form polyolefin plastics according to claim 1, is characterized in that: described oxidation inhibitor is one or more in antioxidant 1010, irgasfos 168, antioxidant 1076, oxidation inhibitor B215, antioxidant 2246 or antioxidant 264.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650450A (en) * | 2015-03-14 | 2015-05-27 | 李广起 | PE type economic breathable waterproof oxygen-absorbing antibacterial fruit and vegetable preservative film |
| CN106243439A (en) * | 2016-07-28 | 2016-12-21 | 张哲夫 | A kind of Tissuemat E modified poly ethylene and preparation method thereof |
| CN107540913A (en) * | 2017-08-28 | 2018-01-05 | 吴江市金鑫塑料厂 | A kind of environment-friendly antibacterial plastics |
| CN108892848A (en) * | 2018-07-10 | 2018-11-27 | 上海大汇塑业有限公司 | Agricultural curtain coating polyethylene film of one kind and the preparation method and application thereof |
| CN109233058A (en) * | 2018-09-04 | 2019-01-18 | 宁波爱克创威新材料科技有限公司 | A kind of elastic film of waterproof and breathable and preparation method thereof |
| CN109867840A (en) * | 2017-12-01 | 2019-06-11 | 天津市川浩塑料制品有限公司 | A kind of plastic grain and preparation method of anti-oxidant modification |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650450A (en) * | 2015-03-14 | 2015-05-27 | 李广起 | PE type economic breathable waterproof oxygen-absorbing antibacterial fruit and vegetable preservative film |
| CN106243439A (en) * | 2016-07-28 | 2016-12-21 | 张哲夫 | A kind of Tissuemat E modified poly ethylene and preparation method thereof |
| CN107540913A (en) * | 2017-08-28 | 2018-01-05 | 吴江市金鑫塑料厂 | A kind of environment-friendly antibacterial plastics |
| CN109867840A (en) * | 2017-12-01 | 2019-06-11 | 天津市川浩塑料制品有限公司 | A kind of plastic grain and preparation method of anti-oxidant modification |
| CN108892848A (en) * | 2018-07-10 | 2018-11-27 | 上海大汇塑业有限公司 | Agricultural curtain coating polyethylene film of one kind and the preparation method and application thereof |
| CN109233058A (en) * | 2018-09-04 | 2019-01-18 | 宁波爱克创威新材料科技有限公司 | A kind of elastic film of waterproof and breathable and preparation method thereof |
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Application publication date: 20140514 |