CN101255254B - Antibacterial polypropylene pipes and antibacterial composite master batch as well as manufacturing method thereof - Google Patents

Antibacterial polypropylene pipes and antibacterial composite master batch as well as manufacturing method thereof Download PDF

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Publication number
CN101255254B
CN101255254B CN2008100612801A CN200810061280A CN101255254B CN 101255254 B CN101255254 B CN 101255254B CN 2008100612801 A CN2008100612801 A CN 2008100612801A CN 200810061280 A CN200810061280 A CN 200810061280A CN 101255254 B CN101255254 B CN 101255254B
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China
Prior art keywords
master batch
composite master
particle
tio
coupling agent
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Expired - Fee Related
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CN2008100612801A
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Chinese (zh)
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CN101255254A (en
Inventor
潘刚
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ZHEJIANG GAOFENG HOLDING GROUP CO Ltd
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ZHEJIANG GAOFENG HOLDING GROUP CO Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

Abstract

The invention provides an antibiotic polypropylene tube and antibiotic composite masterbatch thereof and preparation methods, comprising: nm Zno particle, nm TiO<SUB>2</SUB> particle, Ag-carrying SiO<SUB>2</SUB> antibiotic particle covered by TiO<SUB>2</SUB>, coupling agent, wax dispersant and polypropylene resin. The antibiotic efficiency of the tube can be above 99% because of the masterbatch being I level and the antibiotic persistence is increased from 10-15 years to about 50 years compared with the general polypropylene tube and the antibiotic range can be greatly increased.

Description

Antibacterial polypropylene pipe material and its antibacterial composite master batch and their manufacture method
Technical field
The invention belongs to the antibacterial polypropylene pipe material field, specifically, relate to a kind of nano compound agglomerate that is used for antibacterial polypropylene pipe material, comprise the polypropylene pipe of this composite master batch and their manufacture method.
Background technology
At present, plastics occupy more and more important position in daily life and industrial and agricultural production, for the Application Areas that makes plastics more extensive, people are by adding inorganic components or organic composition in the plastic master batch of plastics, so that make plastics have functions such as antibiotic, quiet antistatic or uvioresistant.But when adding organic composition merely, because the organic composition timeliness is short, decomposition temperature is low, and decomposing volatile is big in the course of processing, can pollute environment.Therefore need in plastics, add inorganic components to remedy above-mentioned defective, for example Chinese patent CN1385473A discloses a kind of modified nano zinc oxide composite master batch, it adds properties-correcting agent in inorganic nano zinc oxide generative process, properties-correcting agent can be titanium dioxide, Silver Nitrate and coupling agent etc., though this plastic master batch has also improved the germ resistance of plastics to a certain extent, effect is not desirable especially.Chinese patent CN1663390A discloses a kind of inorganic material clad silver loaded nanometer SiO 2Antiseptic-germicide, its antiseptic-germicide surface-coated has TiO 2Though this antiseptic-germicide has better whiteness, germ resistance also improves, and antibacterial effect neither be desirable especially.Easily grow mushroom and go mouldy and cause influencing the problem of water quality because of moving the throw out that produces all the year round in order to solve water pipe, be necessary to develop a kind of nano antibacterial pipe material with good sterilization antibacterial effect.
Summary of the invention
It is undesirable that the object of the invention is to overcome in the prior art antibacterial effect, the persistent inadequately drawback of germ resistance and a kind of antibacterial polypropylene pipe material with excellent anti-bacterium capability and antibiotic life-span is provided and makes the antibacterial matrices that uses, this master batch is that the applicant passes through comprehensive inorganic nano-particle and TiO 2The Ag-carrying nano antibiotic agent that coats is made up and is groped to finish through a large amount of experiments, found that the anti-microbial property that above-mentioned composite master batch can beat all raising polypropylene pipe.
The composite master batch that is used for antibacterial polypropylene pipe material of the present invention by weight percentage, comprising:
The nano-ZnO particle: (5%-20%),
Nano-TiO 2Particle: (5%-20%),
TiO 2Year silver-colored SiO that coats 2Antimicrobial particle: (5%-20%),
Coupling agent: 0.05-2%,
Wax class dispersion agent 5%-8%,
Surplus is an acrylic resin.
Further, by weight percentage, preferred described master batch comprises:
The nano-ZnO particle: (10%-20%),
Nano-TiO 2Particle: (10%-20%),
TiO 2Year silver-colored SiO that coats 2Antimicrobial particle: (8%-15%),
Coupling agent: 0.1-1%,
Wax class dispersion agent 5%-8%,
Surplus is an acrylic resin.
Further, described master batch is after each compositions in weight percentage mixes in high-speed mixer, to be melt extruded by plastics extruder, and pelletizing forms.
Further, described coupling agent is silane coupling agent, titanate coupling agent and/or aluminate coupling agent.
Further, described wax class dispersion agent is polyester wax or polyethylene wax or ethylene copolymer wax.
The manufacture method that is used for the composite master batch of antibacterial polypropylene pipe material of the present invention comprises: carry out the weighing of each component by above-mentioned composite master batch; Each component of weighing is stirred in stirrer for mixing, and enter into plastics extruder, melt extrude under 150-200 ℃, cooling back pelletizing obtains the composite antibiosis master batch.
Antibacterial polypropylene pipe material of the present invention in the gross weight of tubing, wherein includes the above-mentioned composite master batch of 5%-15%, preferred 10%-15%.
Antibacterial polypropylene pipe material of the present invention, by wherein adding antibacterial composite master batch, the antibiotic rate of tubing is reached more than 99%, be I level level, compare with plain polypropylene tubing, antibiotic persistence is brought up to about 50 years from 10-15, has unexpectedly improved 3-5 doubly, and antibacterial range obviously increases simultaneously,, the Glan formula positive negative to Glan formula (Gram), intestinal bacteria, Pseudomonas aeruginosa, streptococcus aureus and various fungi and mould all have significant germ resistance.
Embodiment
Below by specific embodiment the present invention is further described.
Raw material nano ZnO particle of the present invention, nano-TiO 2Particle, coupling agent and wax class dispersion agent are all commercially available, preferred nano-ZnO particle, nano-TiO 2The particle diameter of particle is between the 30-50nm.Raw material TiO 2Year silver-colored SiO that coats 2Antimicrobial particle is according to the disclosed method preparation of CN1663390A, the wherein TiO that is coated 2Bed thickness 5-15nm.
Embodiment 1:
ZnO particle and nano-TiO with particle diameter 40nm 2Particle takes by weighing 20% of composite master batch gross weight, TiO respectively 2Year silver-colored SiO that coats 2Antimicrobial particle, silane coupling agent, wax class dispersion agent take by weighing 15%, 0.05%, 4.5% polyethylene wax (lower molecular weight) of composite master batch gross weight respectively, they were stirred 2 minutes with 200r/min at normal temperatures, heated 2 hours down at 110 ℃ then, make the anti-microbial activity powder;
0.5% polyethylene wax (lower molecular weight) of 39.95% acrylic resin, the above-mentioned anti-microbial activity powder of making and composite master batch gross weight of composite master batch gross weight was mixed 2 minutes in mixing machine, and under 130 ℃, heated 2 hours, then, add the twin screw extruder melt blending, 180 ℃ of processing temperatures, rotating speed 120rpm/ branch, shear-mixed is extruded pelletizing and is made antibacterial composite master batch.
Embodiment 2:
ZnO particle and nano-TiO with particle diameter 30nm 2Particle takes by weighing 5% of composite master batch gross weight, TiO respectively 2Year silver-colored SiO that coats 2Antimicrobial particle, silane coupling agent, wax class dispersion agent take by weighing 5%, 0.1%, 5.5% polyethylene wax (lower molecular weight) of composite master batch gross weight respectively, they were stirred 3 minutes with 200r/min at normal temperatures, heated 2 hours down at 110 ℃ then, make the anti-microbial activity powder;
0.5% polyethylene wax (lower molecular weight) of 78.9% acrylic resin, the above-mentioned anti-microbial activity powder of making and composite master batch gross weight of composite master batch gross weight was mixed 2 minutes in mixing machine, and under 130 ℃, heated 2 hours, then, add the twin screw extruder melt blending, 200 ℃ of processing temperatures, rotating speed 120rpm/ branch, shear-mixed is extruded pelletizing and is made antibacterial composite master batch.
Embodiment 3:
ZnO particle and nano-TiO with particle diameter 50nm 2Particle takes by weighing 10%, 15% of composite master batch gross weight, TiO respectively 2Year silver-colored SiO that coats 2Antimicrobial particle, silane coupling agent, wax class dispersion agent take by weighing 15%, 0.1%, 7.5% polyethylene wax (lower molecular weight) of composite master batch gross weight respectively, they were stirred 3 minutes with 200r/min at normal temperatures, heated 2 hours down at 110 ℃ then, make the anti-microbial activity powder;
0.5% polyethylene wax (lower molecular weight) of 51.9% acrylic resin, the above-mentioned anti-microbial activity powder of making and composite master batch gross weight of composite master batch gross weight was mixed 2 minutes in mixing machine, and under 130 ℃, heated 2 hours, then, add the twin screw extruder melt blending, 200 ℃ of processing temperatures, rotating speed 120rpm/ branch, shear-mixed is extruded pelletizing and is made antibacterial composite master batch.
Embodiment 4:
ZnO particle and nano-TiO with particle diameter 50nm 2Particle takes by weighing 10%, 10% of composite master batch gross weight, TiO respectively 2Year silver-colored SiO that coats 2Antimicrobial particle, silane coupling agent, wax class dispersion agent take by weighing 10%, 0.1%, 4.5% polyethylene wax (lower molecular weight) of composite master batch gross weight respectively, they were stirred 3 minutes with 200r/min at normal temperatures, heated 2 hours down at 110 ℃ then, make the anti-microbial activity powder;
0.5% polyethylene wax (lower molecular weight) of 64.9% acrylic resin, the above-mentioned anti-microbial activity powder of making and composite master batch gross weight of composite master batch gross weight was mixed 2 minutes in mixing machine, and under 130 ℃, heated 2 hours, then, add the twin screw extruder melt blending, 180 ℃ of processing temperatures, rotating speed 120rpm/ branch, shear-mixed is extruded pelletizing and is made antibacterial composite master batch.
Embodiment 5:
In the gross weight of polypropylene pipe, take by weighing the antibacterial composite master batch and the acrylic resin of the embodiment 1-4 preparation of 10%-15%, and through conventional preformed, extrude, typing, vacuum sizing, cooling prepare polypropylene pipe.Polypropylene pipe and polypropylene pipe of the present invention by the contrast prior art, the data that can obtain providing in the table 1, wherein antibiotic rate records by method described in the QB/T 2591-2003 " antibiotic plastic: anti-microbial property test method and antibacterial effect ", antibiotic persistence adopts JC/T939-2004 " antibiotic plastic pipe antibacterium performance for building " method to obtain, and antibacterial range obtains by QB/T2591-2003 " antibiotic plastic: anti-microbial property test method and antibacterial effect ".
The polypropylene pipe of table 1 prior art and polypropylene pipe anti-microbial property of the present invention
Common antibacterial pipe material The antibacterial pipe material of this prescription
Antibiotic rate 60％-80％ The I level, 〉=99%
Antibiotic persistence 10-15 Reach 50 years
Antibacterial range Intestinal bacteria, Pseudomonas aeruginosa, streptococcus aureus Glan formula (Gram) is negative, the Glan formula positive, intestinal bacteria, Pseudomonas aeruginosa, streptococcus aureus and various fungi and mould
Although above the specific embodiment of the present invention has been given to describe in detail and explanation; but should indicatedly be; we can carry out various equivalences to above-mentioned embodiment according to conception of the present invention and change and modification; when the function that it produced does not exceed spiritual that specification sheets and accompanying drawing contain yet, all should be within protection scope of the present invention.

Claims (8)

1. composite master batch that is used for antibacterial polypropylene pipe material, by weight percentage, its composition is:
Nano-ZnO particle: 5%-20%,
Nano-TiO 2Particle: 5%-20%,
TiO 2Year silver-colored SiO that coats 2Antimicrobial particle: 5%-20%,
Coupling agent: 0.05-2%,
Wax class dispersion agent 5%-8%,
Surplus is an acrylic resin.
2. composite master batch as claimed in claim 1, wherein in weight percent, its composition is:
Nano-ZnO particle: 10%-20%,
Nano-TiO 2Particle: 10%-20%,
TiO 2Year silver-colored SiO that coats 2Antimicrobial particle: 8%-15%,
Coupling agent: 0.1-1%,
Wax class dispersion agent 5%-8%,
Surplus is an acrylic resin.
3. composite master batch as claimed in claim 1 or 2 is characterized in that, master batch is after each compositions in weight percentage mixes in high-speed mixer, to be melt extruded by plastics extruder, and pelletizing forms.
4. composite master batch as claimed in claim 1 or 2 is characterized in that, described coupling agent is silane coupling agent, titanate coupling agent and/or aluminate coupling agent.
5. composite master batch as claimed in claim 1 or 2 is characterized in that, described wax class dispersion agent is polyester wax or polyethylene wax.
6. the manufacture method as each described composite master batch of claim 1-5 comprises: carry out the weighing of each component by above-mentioned composite master batch; Each component of weighing is stirred in stirrer for mixing, and enter into plastics extruder, melt extrude under 150-200 ℃, cooling back pelletizing obtains the composite antibiosis master batch.
7. an antibacterial polypropylene pipe material in the gross weight of tubing, wherein includes each described composite master batch of 5%-15% such as claim 1-5.
8. polypropylene pipe as claimed in claim 7 wherein includes the described composite master batch of 10%-15%.
CN2008100612801A 2008-03-28 2008-03-28 Antibacterial polypropylene pipes and antibacterial composite master batch as well as manufacturing method thereof Expired - Fee Related CN101255254B (en)

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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012002933A1 (en) * 2010-06-29 2012-01-05 Empire Technology Development Llc Coating materials for bisphenol a-containing polymers
CN102807705A (en) * 2012-03-30 2012-12-05 上海心尔新材料科技股份有限公司 Sulfur antibacterial masterbatch and manufacturing method thereof
CN103144392B (en) * 2013-02-27 2015-07-01 金发科技股份有限公司 Photostable antimicrobial polypropylene material product and preparation method thereof
CN103571055A (en) * 2013-10-30 2014-02-12 芜湖纽麦特新材料有限公司 Antibacterial plastic master batch, and preparation method and antibacterial plastic thereof
CN103601953A (en) * 2013-11-08 2014-02-26 苏州新颖新材料科技股份有限公司 Plant-source bacteriostatic composite thin film and preparation method thereof
CN107929902A (en) * 2016-03-21 2018-04-20 周中南 Trachea cannula tube core and preparation method thereof
CN106317640A (en) * 2016-08-23 2017-01-11 柳州市国正机电物资有限责任公司 Preparation method of nano antibacterial pipe
CN107163374A (en) * 2017-05-08 2017-09-15 安徽国登管业科技有限公司 A kind of preparation method of antibiotic polypropylene master batch
CN109096601A (en) * 2018-07-03 2018-12-28 广东康百文创科技有限公司 A kind of preparation method of acidproof flame-proof antibiotic crystalline p p sheet
CN109097906A (en) * 2018-08-06 2018-12-28 梧州市兴能农业科技有限公司 Antibacterial acoustical cotton for automobile
CN110922661B (en) * 2019-11-27 2021-12-17 华南理工大学 Inorganic nano antibacterial plastic, preparation method thereof and application thereof in water supply pipe
CN113306218A (en) * 2021-05-27 2021-08-27 四川森普管材股份有限公司 Double-layer antibacterial tube and preparation method thereof

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