CN104592629B - A kind of preparation method of Cu/ZnO composite antibacterial PP master batch - Google Patents
A kind of preparation method of Cu/ZnO composite antibacterial PP master batch Download PDFInfo
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- CN104592629B CN104592629B CN201510005735.8A CN201510005735A CN104592629B CN 104592629 B CN104592629 B CN 104592629B CN 201510005735 A CN201510005735 A CN 201510005735A CN 104592629 B CN104592629 B CN 104592629B
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- antibacterial
- complex antimicrobials
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- antioxidant
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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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
Abstract
Invention broadly provides the preparation method of a kind of Cu/ZnO composite antibacterial PP master batch.Described antibacterial matrices includes following blend components: matrix resin, complex antimicrobials, lubricant, composite antioxidant；Wherein mass ratio shared by complex antimicrobials is 10～30 wt%, and lubricant agent usage amount is 1～5 wt%, and composite antioxidant usage amount is 0.05～0.2 wt%.The method technique is simple, and cost is relatively low, and made antibacterial matrices is for polyacrylic antibacterial modified, and on antibacterial, fungus is respectively provided with higher antibiotic rate and the mechanical property on resin itself does not has much impacts, has good market prospect.
Description
Technical field
The present invention relates to a kind of preparation method for macromolecule composite functional material, especially one has composite antibacterial
The preparation method of the polypropylene agglomerate of function.
Background technology
Polypropylene is by a kind of thermoplastic resin of propylene polymerization, according to methyl arrangement position, is divided into isotactic poly-third
Alkene, random polypropylene and syndiotactic polypropylene three kinds.Polyacrylic degree of crystallinity is high, compound with regular structure, thus has excellent mechanical property
Can, simultaneously it also have nontoxic, tasteless, density is little etc. a little, intensity, rigidity, hardness, thermostability are superior to low-pressure polyethylene.
Therefore polypropylene gradually replaces the latter has had more application in fields such as household electrical appliance, plastic pipe, high materials thoroughly.
Along with the development of society, people are to the concern all the more of life and health field, and polypropylene is widely used in people
Daily life, such as water tumbler, cutlery box, water pipe etc., the most polyacrylic antibacterial modified emphasis becoming current modifying plastics.
The most conventional antibacterial is divided into inorganic antiseptic, organic antibacterial agent and natural antibacterial agent.Inorganic antiseptic is usual
Refer to the inorganic matter such as silver, copper, zinc, mainly utilize its oxidation activity and dissociated ion to kill mushroom, wherein silver system substance germicide energy
Power is the strongest, but there is silver ion and have micro-toxicity and the problem such as activity is the strongest, easy to change, and copper system material is to fungus lethality relatively
By force, to antibacterial then almost without effect, zinc system then anti-microbial property only on；The principal item of organic antibacterial agent have vanillin and
Ethyl vanillin aldehyde compound, but there is the problems such as safety the unknown, poor, the easy hydrolysis of thermostability in organic antibacterial agent；Natural
Antibacterial mostlys come from the extraction of the natural plants such as mustard, chitin, Wasabia japonic (Euterma Wasabi), but has that bactericidal effect is limited, poor stability
Etc. problem.
Polyacrylic method of modifying generally has graft modification, modification by copolymerization, cross-linking modified and blending and modifying.Wherein it is blended and changes
Property is to be mixed under the effect of thermodynamics and mechanical force with polypropylene by other pellets, polyacrylic functional to increase.
Therefore the anti-microbial property of master batch is increased by blend method, simple and effective, the most with low cost, become current enterprise
Common method.
Summary of the invention
The problem existed for current inorganic antiseptic, the invention provides a kind of Cu/ZnO composite antibacterial PP master batch
Preparation method.
A kind of preparation method of Cu/ZnO composite antibacterial PP master batch, it is characterised in that described antibacterial matrices include with
Under blend components: matrix resin, complex antimicrobials, lubricant, composite antioxidant；It is first according to be placed in two kinds of antibacterial
In high speed mixer, it is mixed to prepare complex antimicrobials, takes out standby；Again by deployed to matrix resin, lubricant, composite antioxidant
It is placed in high mixer and is stirred until homogeneous；The complex antimicrobials prepared before addition, more second highest mix to above-mentioned substance uniform, take out also
Using double screw extruder melt blending to prepare antibacterial matrices, this master batch can be used for blank polypropylene chip.
A kind of preparation method of Cu/ZnO composite antibacterial PP master batch, it is characterised in that: described matrix resin is isotactic poly-third
At least one in alkene, random polypropylene, syndiotactic polypropylene, usage amount is 70～85 wt% of antibacterial matrices quality.
Described complex antimicrobials be mainly composed of Nanometer Copper and nano zine oxide, particle diameter is 40～600 nm, used
Cu and ZnO is Cu:ZnO=1:1～4 according to mass ratio, uses high speed mixer to be mixed with as composite antibacterial two kinds of powder body
Agent, the usage amount of complex antimicrobials is 10～30 wt% of antibacterial matrices quality.
Described lubricant is liquid paraffin, and usage amount is 1～5 wt% for antibacterial matrices quality.
Described composite antioxidant composition is antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] Ji Wusi
Alcohol ester and antioxidant three [2,4-di-tert-butyl-phenyl] phosphite ester, two kinds of composition proportion are four [β-(3,5-bis-uncles in mass ratio
Butyl-4-hydroxy phenyl) propanoic acid] pentaerythritol ester: three [2,4-di-tert-butyl-phenyl] phosphite ester=1:1～3 carries out mixing and adjusts
Joining for composite antioxidant, its usage amount is 0.05～0.2 wt% of antibacterial matrices quality.
First resin matrix, lubricant, composite antioxidant are carried out mixed at high speed, then complex antimicrobials is added height
Mixed, the mixture that proportioning is good according to the above ratio carries out melt blending, can prepare described antibacterial matrices.
This master batch consumption in polypropylene chip is 5～15 wt%.
This method has taken into account Cu and ZnO advantage in terms of antibacterial and mouldproof, avoids many industry, especially food simultaneously
The query of packaging industry series material antibacterial to Ag, preparation method is simple, with low cost, favorably by industrialized production, prepared
Polypropylene agglomerate has preferable broad-spectrum antimicrobial effect.
Beneficial effect
(1) present invention uses melt-blending process to be modified, convenient and swift, and the suitability is strong.
(2) present invention uses Cu/ZnO composite antibacterial, has good spectrum antibacterial anti-mold effect, and with low cost.
(3) the polypropylene antibacterial plate obtained by antibacterial matrices prepared by the present invention, good mechanical properties, wherein bend and draw
Stretch intensity to rise.
Accompanying drawing explanation
Fig. 1 is the SEM photograph of Nanometer Copper in embodiment 1.
Fig. 2 is the SEM photograph of nano zine oxide in embodiment 1.
Fig. 3 is the SEM photograph of PP antibacterial matrices section in embodiment 3.
Detailed description of the invention
Embodiment 1:
Take 700 g isotactic polypropylene, 0.25 g antioxidant 1010,0.25g irgasfos 168 and 50 g liquid paraffin, put into
High mixer mixes, and takes out standby.Take Nanometer Copper and each 125 g of nano zine oxide carry out mixed at high speed, to be mixed uniformly after,
Compound before is added, continues to be mixed to prepare antimicrobial mixtures, prepare antibacterial PP master batch by double screw extruder.Take this
Antibacterial matrices 50 g, blank PP cut into slices 950 g, by double screw extruder melt blending, and with high speed cold cut machine pelletizing, prepared
Antibacterial PP cuts into slices, and is designated as #1.
Table 1 is PP master batch twin screw extrusion process table, and Fig. 1 is the SEM photograph of Nanometer Copper, and Fig. 2 is nano zine oxide
SEM photograph.
Embodiment 2:
800 g isotactic polypropylene, 0.3 g antioxidant 1010,0.6g irgasfos 168 and 25 g liquid paraffin, put into high mixed
Machine mixes, and takes out standby.Take Nanometer Copper 50 g and nano zine oxide 125 g and carry out mixed at high speed, to be mixed uniformly after, will
Compound before adds, and continues to be mixed to prepare antimicrobial mixtures, prepares antibacterial PP master batch by double screw extruder.Take this to resist
Starter grain 120 g, blank PP cut into slices 880 g, by double screw extruder melt blending, and with high speed cold cut machine pelletizing, prepared
Antibacterial PP cuts into slices, and is designated as #2.
Table 2 is the EDS analytical data of PP antibacterial matrices.
Embodiment 3:
850 g isotactic polypropylene, 0.5 g antioxidant 1010,1.5g irgasfos 168 and 10 g liquid paraffin, put into high mixed
Machine mixes, and takes out standby.Take Nanometer Copper 27.6 g and nano zine oxide 138 g and carry out mixed at high speed, to be mixed uniformly after,
Compound before is added, continues to be mixed to prepare antimicrobial mixtures, prepare antibacterial PP master batch by double screw extruder.Take this
Antibacterial matrices 100 g, blank PP cut into slices 900 g, by double screw extruder melt blending, and with high speed cold cut machine pelletizing, make
Obtain antibacterial PP section, be designated as #3.
Fig. 3 is the SEM photograph of PP master batch section.
Embodiment 4:
Each 100 g of sample #1, #2, #3 in Example 1, carry out being molded into batten and sheet material by injection machine.Pass through
Batten tests its mechanical property, and it is 50 mm*50 mm that sheet material is cut out according to GB, and the model of thickness 2 mm carries out antibacterial test.
Method of testing is with reference to GB GBT 21510-2008 nano inorganic material anti-microbial property method of testing, with blank PE plate for comparison
Sample, cleans PE plate with model #1, #2, #3, sterilizes, is dried standing and gnotobasis, take 0.2 ml bacteria suspension and drop in sample table
Face, the polyethylene film thick with 0.1 mm covers on it, keeps relative humidity 90% at 37 DEG C, cultivates 18～24 h.Sample is taken
Go out, use PBS bacterium solution to be rinsed, be configured to certain Concentraton gradient, use sterile agar plate to carry out cultivating 18～24 h,
Observe antibacterial effect.
Table 3 is the mechanical experimental results of antibacterial PP batten, and table 4 is the anti-microbial property test result of antibacterial PP model.
Twin screw extrusion process table in table 1 embodiment 1～3
The EDS analytical data of PP antibacterial matrices in table 2 embodiment 2
The mechanical property parameters of PP batten in table 3 embodiment 4
The anti-microbial property test result of PP model in table 4 embodiment 4
Claims (1)
1. the preparation method of a Cu/ZnO composite antibacterial PP master batch, it is characterised in that described antibacterial matrices includes following
Blend components: matrix resin, complex antimicrobials, lubricant, composite antioxidant；It is first according to two kinds of antibacterial are placed in height
In speed batch mixer, it is mixed to prepare complex antimicrobials, takes out standby；Again by matrix resin, lubricant, composite antioxidant is deployed puts
It is stirred until homogeneous in high mixer；The complex antimicrobials prepared before addition, more second highest mix to above-mentioned substance uniform, take out and adopt
Preparing antibacterial matrices with double screw extruder melt blending, this master batch can be used for blank polypropylene chip；
Described matrix resin is at least one in isotactic polypropylene, random polypropylene, syndiotactic polypropylene, and usage amount is antibacterial mother
70～85 wt% of grain quality；
Described complex antimicrobials be mainly composed of Nanometer Copper and nano zine oxide, particle diameter be 40～600 nm, Cu used and
ZnO is Cu:ZnO=1:1～4 according to mass ratio, and two kinds of powder body use high speed mixers be mixed with as complex antimicrobials, multiple
Close 10～30 wt% that usage amount is antibacterial matrices quality of antibacterial；
Described lubricant is liquid paraffin, and usage amount is 1～5 wt% of antibacterial matrices quality；
Described composite antioxidant composition is antioxidant four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester
With antioxidant three [2,4-di-tert-butyl-phenyl] phosphite ester, two kinds of composition proportion are four [β-(3,5-bis-tertiary fourths in mass ratio
Base-4-hydroxy phenyl) propanoic acid] pentaerythritol ester: three [2,4-di-tert-butyl-phenyl] phosphite ester=1:1～3 carries out mixing preparation
For composite antioxidant, its usage amount is 0.05～0.2 wt% of antibacterial matrices quality；
First resin matrix, lubricant, composite antioxidant are carried out mixed at high speed, then added by complex antimicrobials high mixed, press
The mixture that aforementioned proportion proportioning is good carries out melt blending, can prepare described antibacterial matrices；
This master batch consumption in polypropylene chip is 5～15 wt%.
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| CN201510005735.8A CN104592629B (en) | 2015-01-05 | 2015-01-05 | A kind of preparation method of Cu/ZnO composite antibacterial PP master batch |
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| CN201510005735.8A CN104592629B (en) | 2015-01-05 | 2015-01-05 | A kind of preparation method of Cu/ZnO composite antibacterial PP master batch |
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| CN104592629B true CN104592629B (en) | 2016-09-21 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330962A (en) * | 2015-11-17 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of super-tough antibacterial masterbatch with high concentration |
| CN110128750A (en) * | 2019-05-21 | 2019-08-16 | 合肥市丽红塑胶材料有限公司 | A kind of nano-antibacterial composite plastic plasticising master batch |
| CN113336979A (en) * | 2020-03-02 | 2021-09-03 | 无菌时代复合新材料(苏州)有限公司 | Antibacterial masterbatch containing high-dispersity inorganic antibacterial agent and preparation method thereof |
| CN111621090A (en) * | 2020-05-20 | 2020-09-04 | 博富科技股份有限公司 | Master batch with algae inhibiting function and preparation method thereof |
| CN111518407A (en) * | 2020-05-21 | 2020-08-11 | 乾帛新材料科技（上海）有限公司 | Copper antibacterial masterbatch |
| CN115197498B (en) * | 2021-04-09 | 2023-10-27 | 天津科技大学 | Antibacterial polypropylene plastic plate and preparation method thereof |
| CN113292786B (en) * | 2021-04-23 | 2022-08-19 | 金发科技股份有限公司 | Antibacterial low-odor master batch and preparation method and application thereof |
| CN113321868A (en) * | 2021-05-20 | 2021-08-31 | 中国纺织科学研究院有限公司 | White copper-based antibacterial master batch for fibers and preparation method thereof |
| TWI817565B (en) * | 2021-06-23 | 2023-10-01 | 新和興業股份有限公司 | An organic-inorganic hybrid material for preventing oxidation of copper or silver, its preparing method and application thereof |
| CN113318517A (en) * | 2021-06-25 | 2021-08-31 | 杭州富氧环境科技有限公司 | Negative oxygen ion material with antibacterial function for air purification and production method thereof |
| TWI817605B (en) * | 2021-07-19 | 2023-10-01 | 新和興業股份有限公司 | An antibacterial plastic masterbatches, its preparing method and application thereof |
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Patent Citations (3)
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| CN102336957A (en) * | 2010-07-29 | 2012-02-01 | 上海亿金纳米科技有限公司 | Method for preparing functional chips for manufacturing antibacterial fibers and plastics |
| CN103627088A (en) * | 2013-12-02 | 2014-03-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Reinforced and toughened anti-bacterial polypropylene composition and preparation method thereof |
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