CN105646984B - A kind of antibacterial polyethylene Pao Droplets and preparation method thereof - Google Patents
A kind of antibacterial polyethylene Pao Droplets and preparation method thereof Download PDFInfo
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- 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
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- 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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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
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- 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
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- 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
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- C08K2201/003—Additives being defined by their diameter
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- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Abstract
The present invention relates to a kind of antibacterial polyethylene foam, its preparation method is further related to.The antibacterial polyethylene foam by polyvinyl resin 65~80%, inorganic nano antiseptic 0.5~4%, foaming agent 7~20%, help foaming antishrinking agent 3~9%, the inorganic material nucleator 0.5~2% containing micropore to form.The antibacterial polyethylene foam is antiseptic from nano zine oxide or nano cupric oxide, and reach the purpose of long-acting bacteriostatic by the slow releasing function containing microporous inorganic material, its preparation method uses the dispersant for helping foaming antishrinking agent as inorganic nano antiseptic, nano material is ground on constant temperature grinder and is uniformly dispersed, then injected again with constant displacement pump on process equipment under hot melt state, solves the scattered hardly possible of nano material well, the problem of particle agglomeration, what is obtained is that a kind of anti-microbial property is excellent, fracture tensile strength and elongation at break properties significantly improve, the fine and closely woven uniform Ju Yi Xi Pao Droplets of abscess.
Description
Technical field
The present invention relates to a kind of antibacterial polyethylene foam, its preparation method is further related to.
Background technology
Polyethylene（PE）As the bulk product of petrochemical industry, there are wide material sources, cost is cheap, widely used
Feature.Use polyethylene（PE）Ju Yi Xi Pao Droplets with foaming agent production are hole-closing structure products, also known as EPE pearl cottons,
It is a kind of packaging material of novel environment friendly.Product has moistureproof water proof, shockproof, sound insulation, insulation, plasticity is good, toughness is strong, follows
Many advantages, such as ring reproduces, environmentally friendly, crashworthiness power is strong.It is the preferable substitute of traditional shock-resistant packaging material.Especially meet plastics production
The national industrial policies of product minimizing.It is widely used in automobile cushion, boudoir, electronic apparatus, instrument and meter, computer, sound equipment, doctor
Treat the top grades such as apparatus, industry control cabinet, hardware and lamp decoration, handicraft, glass, ceramics, household electrical appliances, spraying, furniture family property, drinks and resin
The packaging of the multiple products such as frangible gift wrap, hardware, toy, melon and fruit, the inner packing of leather shoes, commodity, and express delivery
Packaging.
Traditional Ju Yi Xi Pao Droplets do not have the function of antibacterial and mouldproof.Therefore, this area research staff have developed in recent years
The various Ju Yi Xi Pao Droplets with antibacterial functions, such as the mould proof Ju Yi Xi Pao Droplets modelings of China Patent Publication No. CN1401695A antibacterials
Material, it is the addition antibacterial and mouldproof masterbatch in polyvinyl resin, butane, monoglyceride, talcum powder, is directly squeezed raw material using extruder
Go out foaming and setting and prepare.A kind of antibacterial polypropylene foaming plastics of China Patent Publication No. CN102286176A and its preparation side
Method, by each component including matrix resin, complex antimicrobials and CBA, nucleator, antioxidant, dispersant by described
Content is well mixed, and after melt blending is granulated, is foamed and is made in moulding press, complex antimicrobials therein are water-soluble silicic acid
Salt.A kind of anti-bacterial polythene foamed plastics of China Patent Publication No. 101967244A and preparation method thereof, by matrix material, silver-plated
Fiber, crosslinking agent, foaming agent and blowing promotor are prepared through melt blending and moulded from foam, and described matrix material is poly- second
Alkene and ethene-vinyl acetate co-polymer two kinds of polymer.
The problems such as antibacterial effect is bad, the antibacterial term of validity is short be present in above-mentioned antibacterial polypropylene foaming plastic antibacterial effect.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of antibacterial polyethylene Pao Droplets, and gained Ju Yi Xi Pao Droplets tools are extremely strong
Antibacterial and antimildew function.The polyethylene contains inorganic nano antiseptic, and passes through the sustained release of the inorganic material containing micropore
Effect reaches the purpose of long-acting bacteriostatic, can be widely used in the antibacterial and mouldproof productions such as antibiotic plastic product, food fresh keeping packaging product
Product field.
Another technical problem to be solved by this invention is to provide the preparation method of the antibacterial polyethylene foam, this method
Using foaming antishrinking agent is helped as the dispersant of inorganic nano antiseptic, nano material is ground on constant temperature grinder and is divided
Dissipate uniform, then injected again with constant displacement pump on process equipment under hot melt state, solve well nano material it is scattered it is difficult,
The problem of particle agglomeration, obtain be a kind of excellent anti-microbial property, fracture tensile strength and elongation at break properties significantly improve,
The fine and closely woven uniform Ju Yi Xi Pao Droplets of abscess.
The technical problems to be solved by the invention are achieved by the following technical programs：
A kind of antibacterial polyethylene Pao Droplets, are made up of the component of following mass percent：It is polyvinyl resin 65~80%, inorganic
Nano antibacterial agent 0.5~4%, foaming agent 7~20%, help foaming antishrinking agent 3~9%, the inorganic material nucleator containing micropore
0.5~2%.
Preferably, the melt index of the polyethylene be every 10 minutes 1~3 gram, melt index examination criteria is ASTM D
1238。
Preferably, the inorganic nano antiseptic is nano zine oxide, at least one of nano cupric oxide.
Preferably, the foaming agent is butane, at least one of dimethyl ether.
Preferably, it is described to help foaming antishrinking agent as single stearic acid glycerine lipoprotein, Tissuemat E, OPE, EVA waxes
At least one.
Preferably, the inorganic material nucleator containing micropore is talcum powder, calcium carbonate crystal whisker, calcium sulfate crystal whiskers and carbon
At least one of SiClx whisker.
Preferably, above-mentioned antibacterial polyethylene Pao Droplets are made up of the composition of following percentage by weight：Polyvinyl resin 68~
78%th, inorganic nano antiseptic 1~3%, foaming agent 12~18%, help foaming antishrinking agent 4~8%, the inorganic material containing micropore
Expect nucleator 0.8~1.5%.
Preferably, above-mentioned antibacterial polyethylene Pao Droplets are made up of the composition of following percentage by weight：Polyvinyl resin 75%, nothing
Machine nano antibacterial agent 2%, foaming agent 15%, help foaming antishrinking agent 7%, the inorganic material nucleator 1% containing micropore.
Above-mentioned antibacterial polyethylene Pao Droplets preparation method is by step：
（1）To help foaming antishrinking agent be heated to 70~100 DEG C of grinding distribution agent as inorganic nano antiseptic, by than
Example with inorganic nano antiseptic on thermostatic type grinder inorganic nano antiseptic grind 1~3 hour into particle diameter be 20~
100nm nano material, obtain containing the antibacterial plastic concentrate for helping foaming antishrinking agent；
（2）It will be blended under the polyvinyl resin of a part, the inorganic material nucleator containing micropore in a mixer normal temperature
15~30 minutes；
（3）By step（2）Obtained blend is extruded with double screw extruder at 140~160 DEG C, pelletizing obtains function
Masterbatch；
（4）By step（3）Obtained functional master batch by a certain percentage with step（2）Remaining polyvinyl resin is in blender
Middle blending 15~30 minutes；
（5）By step（1）What is obtained is helping foaming antishrinking agent constant displacement pump containing the antibacterial plastic concentrate for helping foaming antishrinking agent
Storage cylinder in be heated to 70~100 DEG C in case being injected into by a certain percentage in the extruder of next step；
（6）By step（4）Obtained blend is used with foaming agent injection pump and helps foaming antishrinking agent with containing
140~160 DEG C are heated in the separate unit screw extruder of antibacterial plastic concentrate injection constant displacement pump and inlet and carries out extrusion operation, separately will
Foaming agent injection pump injects from extruder blowing agent injection port, while by step（5）Containing for obtaining helps foaming antishrinking agent
Antibacterial plastic concentrate help foaming antishrinking agent constant displacement pump in quantitatively inject, extrusion obtain Ju Yi Xi Pao Droplets sheet materials.
Preferably, step（1）With（5）Heating-up temperature is 80 DEG C, and milling time is 2 hours, the particle diameter of gained nano material
For 53nm；Step（2）With（4）The blending time is 20min；Step（6）Heating-up temperature is 150 DEG C.
The present invention has the advantages that：
The present invention uses inorganic nano antiseptic（Nano zine oxide, nano cupric oxide）It is nano oxidized as antimicrobial component
Zinc, cupric oxide are particle of the particle diameter between 1~100 nm, and there are speciality, these speciality such as particle is small, specific surface area is big to make it
Show different from common micro zinc oxide, the premium properties of micron cupric oxide, they are easier to discharge metal ion, utilize
The antibacterial ability of metal ion, and reach by the slow releasing function containing microporous inorganic material the purpose of long-acting bacteriostatic, can be wide
It is general to be used for rubber product, plastic product, food packaging items, cosmetics and medicine and other fields.
In the preparation method of antibacterial polyethylene foam of the present invention, foaming antishrinking agent is helped to be received as inorganic using in component
The grinding distribution agent of nano antibacterial agent, first inorganic nano antiseptic disperse again with other component melts extrusion moldings, overcome
The problem of nano material scattered difficult, particle agglomeration, what is obtained is that a kind of excellent anti-microbial property, fracture tensile strength and fracture are stretched
Long rate performance significantly improves, the fine and closely woven uniform poly- second alkene bubble Droplets of abscess.
Brief description of the drawings
Fig. 1 is the nano zine oxide of the German ZEISS EVO18 type ESEMs of the antibacterial polyethylene foam of embodiment 1
50000 times of pictures.
Fig. 2 be the antibacterial polyethylene foam of embodiment 1 LA960WET particle size analyzers measure the equal footpath 53.2nm of nano zine oxide and
Distribution map.
Embodiment
The present invention will be described in detail with reference to the accompanying drawings and examples.
Embodiment 1
A kind of antibacterial polyethylene Pao Droplets, are made up of the composition of following percentage by weight：Polyvinyl resin 75%, inorganic nano
Antiseptic 1%, foaming agent 16%, help foaming antishrinking agent 7%, the inorganic material nucleator 1% containing micropore.
Wherein, the melt index of polyvinyl resin be every 10 minutes 1~3 gram.Melt index examination criteria is ASTM D
1238.Inorganic nano antiseptic is nano zine oxide.Foaming agent is two kinds of butane, dimethyl ether collaboration selections.Help foaming anti-shrink
Agent is single stearic acid glycerine lipoprotein, Tissuemat E, OPE, the one of which of EVA waxes；Inorganic material containing micropore into
Core agent is the one of which of talcum powder, calcium carbonate crystal whisker, calcium sulfate crystal whiskers and silicon carbide whisker.
Embodiment 2
A kind of antibacterial polyethylene Pao Droplets, are made up of the composition of following percentage by weight：Polyvinyl resin 74%, inorganic nano
Antiseptic 2%, foaming agent 16%, help foaming antishrinking agent 7%, the inorganic material nucleator 1% containing micropore.
Wherein, the melt index of polyvinyl resin be every 10 minutes 1~3 gram.Melt index examination criteria is ASTM D
1238.Inorganic nano antiseptic is nano cupric oxide.Foaming agent is butane.Help foaming antishrinking agent be single stearic acid glycerine lipoprotein and
Tissuemat E；Inorganic material nucleator containing micropore is calcium carbonate crystal whisker.
Embodiment 3
A kind of antibacterial polyethylene Pao Droplets, are made up of the composition of following percentage by weight：Polyvinyl resin 73%, inorganic nano
Antiseptic 3%, foaming agent 16%, help foaming antishrinking agent 7%, the inorganic material nucleator 1% containing micropore.
Wherein, the melt index of polyvinyl resin be every 10 minutes 1~3 gram.Melt index examination criteria is ASTM D
1238.Inorganic nano antiseptic is the mixture of nano zine oxide and nano cupric oxide.Foaming agent is dimethyl ether.Help the anti-receipts of foaming
Contracting agent is the mixture of OPE and EVA waxes；Inorganic material nucleator containing micropore is talcum powder.
The preparation process of above-described embodiment is：
（1）To help foaming antishrinking agent be heated to 80 DEG C of grinding distribution agent as nano zine oxide in proportion with nano oxygen
Change zinc grinds nano zine oxide into average grain diameter for 53nm nano material to turn into for 2 hours on thermostatic type grinder to be contained
Help the antibacterial plastic concentrate of foaming antishrinking agent；
（2）, polyvinyl resin, the inorganic material nucleator containing micropore of a part be blended under normal temperature in a mixer
20 minutes；
（3）, by step（2）Obtained blend is extruded with double screw extruder at 140~160 DEG C, pelletizing obtains grain
Expect for functional master batch；
（4）, by step（3）Obtained functional master batch, it is blended 20 points in a mixer with polyethylene raw material by a certain percentage
Clock；
（5）, by step（1）What is obtained is helping foaming antishrinking agent constant displacement pump containing the antibacterial plastic concentrate for helping foaming antishrinking agent
Storage cylinder in be heated to 80 DEG C in case being injected into by a certain percentage in the extruder of next step；
（6）, by step（4）The antibacterial plastic concentrate of foaming antishrinking agent is used with foaming agent injection pump and helped to obtained blend
150 DEG C are heated in the separate unit screw extruder of injection constant displacement pump and inlet and carries out extrusion operation, separately inject foaming agent
Pump injects from extruder blowing agent injection port, while by step（5）What is obtained exists containing the antibacterial plastic concentrate for helping foaming antishrinking agent
Help in foaming antishrinking agent constant displacement pump and quantitatively inject, extrusion obtains Ju Yi Xi Pao Droplets sheet materials.
The polyethylene foam piece performance of embodiment 1 ~ 3 is as shown in the table：
| Ju Yi Xi Pao Droplets performances | Embodiment 1 | Embodiment 2 | Embodiment 3 | Selection standard or instrument |
| Inorganic nano antiseptic dosage（%） | 1 | 2 | 3 | —— |
| Electronic Speculum surveys average grain diameter（nm） | 53 | 53 | 53 | LA960WET particle size analyzers |
| Escherichia coli antibiotic rate（%） | 94 | 99.5 | 99.9 | ISO22196-2011 standards |
| Fracture tensile strength（MPa） | 8.12 | 8.56 | 8.82 | CPQ-WD-10 testing machines |
| Elongation at break（%） | 175 | 186 | 192 | CPQ-WD-10 testing machines |
The Particle Size of Nanometer ZnO tables of data that LA960WET particle size analyzers measure embodiment 1 is as shown in the table：
By the testing result of embodiment 1 to 3, and the Fig. 1 of embodiment 1 German ZEISS EVO18 type ESEMs
50000 times of pictures of nano zine oxide, Fig. 2 LA960WET particle size analyzers measure the equal footpath 53.2nm of nano zine oxide and distribution map can be with
Find out, gained antibacterial polyethylene Pao Droplets Escherichia coli antibiotic rate is with nano zine oxide dosage（%）Increase and increase, it is broken
Tensile strength（MPa）With elongation at break（%）Also with nano zine oxide dosage（%）Increase and increase.
Embodiment described above only expresses embodiments of the present invention, and its description is more specific and detailed, but can not
Therefore the limitation to the scope of the claims of the present invention is interpreted as, as long as the skill obtained using the form of equivalent substitution or equivalent transformation
Art scheme, it all should fall within the scope and spirit of the invention.
Claims (9)
1. a kind of antibacterial polyethylene Pao Droplets, it is characterised in that be made up of the component of following mass percent：Polyvinyl resin 65
~80%, inorganic nano antiseptic 0.5~4%, foaming agent 7~20%, help foaming antishrinking agent 3~9%, containing the inorganic of micropore
Material nucleator 0.5~2%；
Described antibacterial polyethylene Pao Droplets preparation method is：
（1）To help foaming antishrinking agent be heated to 70~100 DEG C of grinding distribution agent as inorganic nano antiseptic, in proportion with
Inorganic nano antiseptic on thermostatic type grinder inorganic nano antiseptic grind 1~3 hour into particle diameter be 20~100nm
Nano material, obtain containing help foaming antishrinking agent antibacterial plastic concentrate；
（2）15~30 will be blended under a part of polyvinyl resin, the inorganic material nucleator containing micropore in a mixer normal temperature
Minute；
（3）By step（2）Obtained blend is extruded with double screw extruder at 140~160 DEG C, pelletizing obtains function mother
Material；
（4）By step（3）Obtained functional master batch by a certain percentage with step（2）Remaining polyvinyl resin is common in a mixer
It is mixed 15~30 minutes；
（5）By step（1）What is obtained is helping the storage of foaming antishrinking agent constant displacement pump containing the antibacterial plastic concentrate for helping foaming antishrinking agent
70~100 DEG C are heated in cylinder in case being injected into by a certain percentage in the extruder of next step；
（6）By step（4）Obtained blend is used with foaming agent injection pump and with containing the antibacterial for helping foaming antishrinking agent
140~160 DEG C, which are heated to, in the separate unit screw extruder of masterbatch injection constant displacement pump and inlet carries out extrusion operation, separately will foaming
Agent injection pump injects from extruder blowing agent injection port, while by step（5）Containing for obtaining helps the anti-of foaming antishrinking agent
Starter material quantitatively injects in foaming antishrinking agent constant displacement pump is helped, and extrusion obtains Ju Yi Xi Pao Droplets sheet materials；
In above-mentioned preparation process, foaming anti-shrink machine is helped to be ground to nano material on constant temperature grinder and be uniformly dispersed, so
Injected again with constant displacement pump on process equipment under hot melt state afterwards.
2. antibacterial polyethylene Pao Droplets according to claim 1, it is characterised in that the melt index of the polyethylene is every 10
1~3 gram of minute.
3. antibacterial polyethylene Pao Droplets according to claim 1, it is characterised in that：The inorganic nano antiseptic is nano oxygen
Change zinc, at least one of nano cupric oxide.
4. antibacterial polyethylene Pao Droplets according to claim 1, it is characterised in that：The foaming agent is butane, dimethyl ether
It is at least one.
5. antibacterial polyethylene Pao Droplets according to claim 1, it is characterised in that：It is described to help foaming antishrinking agent as single tristearin
Acid glyceride, Tissuemat E, at least one of EVA waxes.
6. antibacterial polyethylene Pao Droplets according to claim 1, it is characterised in that：The inorganic material nucleation containing micropore
Agent is at least one of talcum powder, calcium carbonate crystal whisker, calcium sulfate crystal whiskers and silicon carbide whisker.
7. the antibacterial polyethylene Pao Droplets according to any one of claim 1 ~ 6, it is characterised in that：Polyvinyl resin 68~
78%th, inorganic nano antiseptic 1~3%, foaming agent 12~18%, help foaming antishrinking agent 4~8%, the inorganic material containing micropore
Expect nucleator 0.8~1.5%.
8. the antibacterial polyethylene Pao Droplets according to any one of claim 1 ~ 6, it is characterised in that：By following percentage by weight
Composition forms：Polyvinyl resin 75%, inorganic nano antiseptic 2%, foaming agent 15%, help foaming antishrinking agent 7%, contain micropore
Inorganic material nucleator 1%.
9. antibacterial polyethylene Pao Droplets according to claim 1, it is characterised in that：Step（1）With（5）Heating-up temperature is 80
DEG C, milling time is 2 hours, and the particle diameter of gained nano material is 53nm；Step（2）With（4）The blending time is 20min；Step
（6）Heating-up temperature is 150 DEG C.
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| CN109021360B (en) * | 2018-08-01 | 2021-03-05 | 福州市长乐区三互信息科技有限公司 | Antibacterial automobile cushion and preparation method thereof |
| CN115895114A (en) * | 2022-11-23 | 2023-04-04 | 青岛润兴塑料新材料有限公司 | Anti-shrinkage degerming master batch for PP (polypropylene) and preparation method thereof |
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