CN108752734A - A kind of plastic foamed coiled material of degradable antimicrobial form and manufacturing method - Google Patents
A kind of plastic foamed coiled material of degradable antimicrobial form and manufacturing method Download PDFInfo
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- CN108752734A CN108752734A CN201810419760.4A CN201810419760A CN108752734A CN 108752734 A CN108752734 A CN 108752734A CN 201810419760 A CN201810419760 A CN 201810419760A CN 108752734 A CN108752734 A CN 108752734A
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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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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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
- C08J9/141—Hydrocarbons
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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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/03—Extrusion of the foamable blend
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Abstract
The invention discloses a kind of plastic foamed coiled materials of degradable antimicrobial form, belong to foam material field, it includes matrix and antibacterial functions filler, wherein, basic material is binary aliphatic alcohol acids polyester, or basic material is selected from polypropylene or polylactic acid, or basic material is selected from polyethylene, polyethylene terephthalate, polybutyl terapthalate or makrolon, its antibiotic functional material is selected from titanium dioxide, zinc oxide, calcium oxide and with it is one or more kinds of in magnesium oxide powder, ranging from 10 μm~0.01 μm of antibiotic functional material powder granule equivalent diameter, additive amount is the 0.1%~20% of foaming coiled gross mass, in structure, its abscess is hole-closing structure, its density≤0.1g/cm3.The present invention also provides preparation methods.Foaming coiled of the present invention can meet the needs of actual production and life, and preparation method is simple, be easy to industrialized production.
Description
Technical field
The invention belongs to foamed plastic field, more particularly, to a kind of plastic foamed coiled material of degradable antimicrobial form and
Manufacturing method.
Background technology
Plastic foam material is widely used in every field, such as buffering package, food containers, building heat preservation, sport buffering
Protection, the encapsulation of electronics and automobile component and waterproof etc..Although the application of plastics brings convenience, at present
Still there are a large amount of plastics effectively cannot recycle and degrade, very big burden is brought to living environment.
In addition, the fields such as food containers, food packaging and waterproof sealing, require to get over to the safe and healthy performance of material
Come higher.Consider for environmental protection and health, needs to develop one kind and having both degradation property and the plastic foamed product of anti-microbial property
Extremely preparation method.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides a kind of degradable antibacterial plastic hairs
Coiled material and method for manufacturing are steeped, it is intended that providing a kind of not only having had anti-microbial property but also degradable and free from environmental pollution
Foaming coiled, the needs of actual production and life can be met, meanwhile, additionally provide the preparation method of the product, preparation side
Method is simple, is easy to industrialized production.
To achieve the above object, according to one aspect of the present invention, it is plastic foamed to provide a kind of degradable antimicrobial form
Coiled material comprising matrix and antibacterial functions filler, wherein
Basic material is that binary aliphatic alcohol acids polyester or basic material are selected from polypropylene or polylactic acid, Huo Zheji
Body material is selected from polyethylene, polyethylene terephthalate, polybutyl terapthalate or makrolon, antibacterial functions material
Material is selected from one or more of titanium dioxide, zinc oxide, calcium oxide and magnesium oxide powder, antibiotic functional material powder granule
Ranging from 10 μm~0.01 μm of equivalent diameter, additive amount are the 0.1%~20% of foaming coiled gross mass, and in structure, abscess is
Hole-closing structure, entire foaming coiled density≤0.1g/cm3。
Further, the closed pore pore diameter range is at 10 μm~1000 μm.
Further, degradation property meets national standard GB/T 20197-2006 photodegradable plastics and thermal-oxidative degradation requirement.Tool
Body, under the conditions of heavy natural sunning, tension fracture elongation rate retention rate≤5%, and average weight-molecular mass rate of descent >=80%,
And after light degradation average weight-molecular mass < 10000 molecular percentage content >=20%, or
Under the conditions of being exposed to the sun in xenon lamp artificial accelerated aging case, tension fracture elongation rate retention rate≤5%, and opposite point of weight
Protonatomic mass rate of descent >=70%, and after light degradation average weight-molecular mass < 10000 molecular percentage content >=20%.
Further, anti-microbial property is according to 2003 standards of QB/T2591-：Staphylococcus aureus inhibiting rate 95%~
100%, escherichia coli inhibiting rate is 95%~100%, i.e., to staphylococcus aureus antibacterium rate 95%~100%,
It is 95%~100% to escherichia coli antibacterium rate.
Further, the wide cut of foaming coiled is 10mm~2000mm, and thickness is 0.1mm~50mm.
Further, polyethylene, polyethylene terephthalate, polybutyl terapthalate are selected from for basic material
With makrolon, in preparation process, basic material first passes through foaming using irradiation, to realize the pre- degradation of basic material,
Irradiation dose is 102Gy~106Gy。
A kind of the degradable plastic foamed volume of antimicrobial form as described above is prepared it is another aspect of this invention to provide that providing
The method of material carries out continous way extrusion foaming using second order tandem extrusion system, and second order tandem extrusion system is by a twin-screw
Extruder and a single screw extrusion machine are composed in series, and double screw extruder feed end is furnished with the first automatic feeding system and second
Automatic feeding system, to ensure that various raw materials are strictly put in proportion into extrusion system, foaming agent injection unit includes foaming agent storage
Tank and injection pump composition are deposited, foaming agent injection unit is connected to double screw extruder by pipe special and special service valve comprising such as
Lower step：
S1：Second order tandem extrusion system is preheated to set temperature；
S2：Start second order tandem extrusion system, material is filled in respectively in mechanical feed unit, and starts and start to feed
Material；
S3：Material after head discharging, starts foaming agent injection unit, is adjusted to setting via second order tandem extrusion system
After pressure, foaming agent is injected double screw extruder by valve opening, and foaming agent is abundant with molten polymer in double screw extruder
Mixing, is delivered to single screw extrusion machine and cools down, and be then delivered to head, is squeezed out to external normal pressure under the pressure of setting
Environment foams and is molded.
Further, further include step S4, step S4 is：
S4：It requires to make foamed polymer material reach degradation, the coiled material of foaming is carried out using irradiation technique
The pre- degradation of irradiation, irradiation dose 102Gy~106Gy。
Further, in step S4, the irradiation bomb of irradiation technique is electron accelerator, cobalt source, ultraviolet emission device, matter
Son or heavy ion avcceleration are one such or a variety of.Form of radiation includes electron beam, ultraviolet rays, X-ray and gamma ray.
Further, in step S3, foaming agent is physical blowing agent, including carbon dioxide, nitrogen, propane, butane and its
Isomer, pentane and its isomer, pentamethylene, hexane and its isomer, hexamethylene and hydrogenation fluothane hydro carbons.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect：
The plastic foamed web qualities of degradable antimicrobial form prepared by the present invention is light, anti-microbial property is good, degradable, will not be dirty
Environment is contaminated, existing nondegradable plastic product can be replaced, there is very huge application prospect, and preparation method letter
It is single, it is easy to promote and apply in the industrial production.
Description of the drawings
Fig. 1 is to prepare the degradable low-density foamed coiled plastic material equipment with anti-microbial property of the present invention；
Fig. 2 is to prepare the degradable low-density foamed coiled plastic material method flow signal with anti-microbial property of the present invention
Figure.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
The present invention's provides the degradable plastic foamed coiled material of antimicrobial form and method for manufacturing.Wherein, it is realization material
Degradation property, present invention employs multiple technologies solution, including plastic basis material selection, irradiation or both share.
Specifically, the selection about plastic basis material, of the invention uses resin for polypropylene, polylactic acid, polyethylene, easily drop
Solve polyester (binary aliphatic alcohol acids polyester), polyethylene terephthalate, polybutyl terapthalate and makrolon
Resin is one such or various kinds of resin blend.Wherein, polypropylene, polylactic acid and binary aliphatic alcohol acids polyester this
A little base materials, exposure is degradable in the natural environment, the foaming product equally characteristic with natural degradation.
And for polyethylene and general purpose polyester class (polyethylene terephthalate, polybutyl terapthalate and poly- carbon
Acid esters) polyolefin-based substrates of not degradable base material and aforementioned selection cannot still meet state after foaming forming technique
Mark what GB/T 20197-2006 photodegradable plastics and thermal-oxidative degradation technology required, the present invention by the way of first foaming and irradiating afterwards,
It is degraded in advance to foamed substrate, principle is as follows：
Wherein, the structural unit in X, Y representation polymer, by taking polypropylene as an example, X is representedY is representedAlso, a+b=n.
Since the present invention is using physical foaming process, after foaming and molding, molecular structure does not occur base material substantially
Variation, therefore degradation speed under field conditions (factors) is very slow, it is difficult to meet degradation and requires.The material production of foaming will be completed
Product are exposed to via irradiation apparatus under strong radiation parameter, and high-energy irradiation (hv) can be such that the covalent bond in polymer molecular chain sends out
Raw free radical formula fracture.In general, this irradiation technique is carried out under air conditions, therefore, the macromolecular radical of fracture holds
It easily is combined into peroxy radical with the oxygen in air, is then reacted with other macromolecular chains, or forms peroxide cross-linked structure or chain
It is blocked after transfer or dewatering coupling terminates.By experiment and production, the present invention obtains rule and is：The drop of irradiation dose and material
Solve speed positive correlation.Using this rule, irradiation dose (10 is adjusted2Gy~106Gy), you can the degradation for meeting foamed products is wanted
It asks.
In general, the anti-microbial property of antibacterial plastic is related to the deployment conditions of antiseptic in the material, currently, antibacterial is moulded
Material product is mainly unexpanded various proximate matters, material be blended be molded during, volume change is little, antiseptic particle it
Between spacing it is smaller.
In expanded material process, each component also has foaming process in addition to being blended in equipment outside mouth mold, material
Volume expansion can make the spacing between blending particle become larger, this can cause anti-microbial property to be deteriorated.Antiseptic is in foaming process
In, the physical blowing process of especially non-crosslinked formula, raw material selection, dispersion effect and final products antibacterial effect, and
Have no relevant report.
To realize the anti-microbial property of expanded material, the present invention is using the filling-modified technical solution of base material antibacterial.Specifically,
In extrusion foaming composition of raw materials, the functional stuffing containing antibacterial functions is added, such as titanium dioxide, zinc oxide, calcium oxide and oxygen
Change the one or more of magnesium powder body (powder granule equivalent diameter range is at 10 μm~0.01 μm), and the mass percent added
0.1%~20%.
Height is made for continous way extrusion foaming, using the method for continuous extrusion foaming in the production and processing method that the present invention uses
Foaming coiled is convenient to subsequent material deep processing and application.
Fig. 1 is to prepare the degradable low-density foamed coiled plastic material equipment with anti-microbial property of the present invention, can by figure
Know, extrusion equipment is second order tandem extrusion system.Main part is squeezed by a double screw extruder 3 and a single screw rod
Go out machine 4 to be composed in series；3 feed end of double screw extruder is furnished with the first mechanical feed unit 1 and the second mechanical feed unit 2, protects
It demonstrate,proves various raw materials and is strictly put in proportion into extrusion system；Foaming agent injected system is made of foaming agent holding vessel 5 and injection pump 6；
Foaming agent injected system is connected to double screw extruder 3 by pipe special and valve.
It is required to make foamed polymer material reach degradation, after the present invention carries out molded material using irradiation technique
Processing.Specifically, the product of continuous physical foaming processing will be completed, carry out continuous irradiation processing, irradiation bomb can be electronics
Accelerator, cobalt source, ultraviolet emission device, proton or heavy ion avcceleration is one such or multiple combinations.It is preferred that electronics adds
Fast device carries out irradiation processing, because it has the advantages such as efficient, safety, low stain, controllability are good.
Fig. 2 is to prepare the degradable low-density foamed coiled plastic material method flow signal with anti-microbial property of the present invention
Figure, with reference to Fig. 2 present invention be described in more detail methods, as seen from the figure comprising following steps：
S1：Second order tandem extrusion system is preheated to set temperature；
S2：Start second order tandem extrusion system, material is filled in respectively in mechanical feed unit, and starts and start to feed
Material；
S3：Material after head discharging, starts foaming agent injection unit, is adjusted to setting via second order tandem extrusion system
After pressure, foaming agent is injected double screw extruder 3 by valve opening, and foaming agent fills in double screw extruder 3 with molten polymer
Divide mixing, be delivered to single screw extrusion machine 4 and cool down, and be then delivered to head, is squeezed out to outside under the pressure of setting
Atmospheric pressure environment foams and is molded.
More specific embodiment is as follows：
Embodiment 1：
The first step：Extrusion system booting preheating, each warm area of double screw extruder temperature are set in 140 DEG C~190 DEG C models
It encloses, single screw extrusion machine set temperature is after 135 DEG C~150 DEG C temperature are stablized, by polypropylene (trade mark WB140) and zinc oxide
(0.01 μm of minimum grain size) puts into automatic feeding device (weightlessness claims), by weight 95:5 ratios set mechanical feed.Discharge port
After discharging, gas injection system is opened, by supercritical CO2Extrusion system is injected, pressure setting range foams in 7.5MPa~20MPa.
After in stable condition, start continuous winding.
Second step：The foaming coiled that the first step is completed unreels and continues through electron accelerator and carry out irradiating pre- degradation, spoke
It is 4 ╳ 10 according to dosage5Gy。
Embodiment 2：
The first step：Extrusion system booting preheating, each warm area of double screw extruder temperature are set in 180 DEG C~200 DEG C models
It encloses, single screw extrusion machine set temperature is after 175 DEG C~190 DEG C temperature are stablized, by polylactic acid (trade mark 2003D) and titanium dioxide
Titanium (1 μm of average grain diameter) puts into automatic feeding device (weightlessness claims), by weight 90:10 ratios set mechanical feed.Discharge port
After discharging, gas injection system is opened, by overcritical N2Extrusion system is injected, pressure setting range is in 7.5MPa~20MPa. foaming shapes
After state is stablized, start continuous winding.
Second step：The foaming coiled that the first step is completed unreels and continues through electron accelerator and carry out irradiating pre- degradation, spoke
It is 10 according to dosage4Gy。
Embodiment 3：
The first step：Extrusion system booting preheating, each warm area of double screw extruder temperature are set in 200 DEG C~290 DEG C models
It encloses, single screw extrusion machine set temperature is after 200 DEG C~230 DEG C temperature are stablized, by polyethylene terephthalate's (chain extender
It is modified) and zinc oxide (1 μm of average grain diameter) input automatic feeding device (weightlessness claims), by weight 80:The setting of 20 ratios is automatic
Feeding.After discharge hole for discharge, open gas injection system, by overcritical pentane inject extrusion system, pressure setting range 1MPa~
After 10MPa. foamed states are stablized, start continuous winding.
Second step：The foaming coiled that the first step is completed unreels and continues through cobalt source irradiation devices and carry out irradiating pre- degradation,
Irradiation dose is 106Gy。
Embodiment 4
In the present embodiment, basic material is binary aliphatic alcohol acids polyester, and antibiotic functional material is selected from titanium dioxide,
Ranging from 10 μm of antibiotic functional material powder granule equivalent diameter, additive amount are the 0.1% of foaming coiled gross mass, in structure,
Its abscess is hole-closing structure, density≤0.1g/cm3.The closed pore pore diameter range is at 900 μm~1000 μm.Its degradation property
Meet national standard GB/T 20197-2006 photodegradable plastics and thermal-oxidative degradation requirement.Its anti-microbial property is according to QB/T2591-2003
Standard：Staphylococcus aureus inhibiting rate 85%~100%, escherichia coli inhibiting rate 90%~100%.Foaming coiled
Wide cut is 1000mm, thickness 0.5mm.
In preparation method, continous way extrusion foaming, second order tandem extrusion system are carried out using second order tandem extrusion system
It is composed in series by a double screw extruder 3 and a single screw extrusion machine 4,3 feed end of double screw extruder is furnished with first certainly
1 and second automatic feeding system 2 of dynamic feed system, to ensure that various raw materials are strictly put in proportion into extrusion system, foaming agent note
It includes that foaming agent holding vessel 5 and injection pump 6 form to enter unit, and foaming agent injection unit is connected to by pipe special and special service valve
Double screw extruder 3 comprising following steps：
S1：Second order tandem extrusion system is preheated to set temperature；
S2：Start second order tandem extrusion system, material is filled in respectively in mechanical feed unit, and starts and start to feed
Material；
S3：Material after head discharging, starts foaming agent injection unit, is adjusted to setting via second order tandem extrusion system
After pressure, foaming agent is injected double screw extruder 3 by valve opening, and foaming agent fills in double screw extruder 3 with molten polymer
Divide mixing, be delivered to single screw extrusion machine 4 and cool down, and be then delivered to head, is squeezed out to outside under the pressure of setting
Atmospheric pressure environment foams and is molded.
In step S3, foaming agent is physical blowing agent, specially carbon dioxide.
Embodiment 5
In the present embodiment, basic material is polypropylene, and antibiotic functional material is zinc oxide, antibiotic functional material powder
Ranging from 2 μm~0.01 μm of equivalent diameter of grain, additive amount are the 20% of foaming coiled gross mass, and in structure, abscess is closed pore
Structure, density≤0.1g/cm3.The closed pore pore diameter range is at 10 μm~100 μm.Its degradation property meets national standard GB/T
20197-2006 photodegradable plastics and thermal-oxidative degradation requirement.Its anti-microbial property is according to 2003 standards of QB/T2591-：Golden yellow Portugal
Grape coccus inhibiting rate 95%~100%, escherichia coli inhibiting rate 95%~100%.The wide cut of foaming coiled is
2000mm, thickness 0.1mm.
In preparation method, continous way extrusion foaming, second order tandem extrusion system are carried out using second order tandem extrusion system
It is composed in series by a double screw extruder 3 and a single screw extrusion machine 4,3 feed end of double screw extruder is furnished with first certainly
1 and second automatic feeding system 2 of dynamic feed system, to ensure that various raw materials are strictly put in proportion into extrusion system, foaming agent note
It includes that foaming agent holding vessel 5 and injection pump 6 form to enter unit, and foaming agent injection unit is connected to by pipe special and special service valve
Double screw extruder 3 comprising following steps：
S1：Second order tandem extrusion system is preheated to set temperature；
S2：Start second order tandem extrusion system, material is filled in respectively in mechanical feed unit, and starts and start to feed
Material；
S3：Material after head discharging, starts foaming agent injection unit, is adjusted to setting via second order tandem extrusion system
After pressure, foaming agent is injected double screw extruder 3 by valve opening, and foaming agent fills in double screw extruder 3 with molten polymer
Divide mixing, be delivered to single screw extrusion machine 4 and cool down, and be then delivered to head, is squeezed out to outside under the pressure of setting
Atmospheric pressure environment foams and is molded.
In step S3, foaming agent is physical blowing agent nitrogen.
S4：It requires to make foamed polymer material reach degradation, the coiled material of foaming is carried out using irradiation technique
The pre- degradation of irradiation, irradiation dose 102Gy.In step S4, the irradiation bomb of irradiation technique is electron accelerator.Form of radiation includes
Electron beam.
Embodiment 6
In the present embodiment, basic material is polyethylene, and antibiotic functional material is calcium oxide, antibiotic functional material powder
Ranging from 3 μm~2.5 μm of equivalent diameter of grain, additive amount are the 12% of foaming coiled gross mass, and in structure, abscess is closed pore
Structure, density≤0.1g/cm3.The closed pore pore diameter range is at 800 μm~1000 μm.Its degradation property meets national standard GB/T
20197-2006 photodegradable plastics and thermal-oxidative degradation requirement.Its anti-microbial property is according to 2003 standards of QB/T2591-：Golden yellow Portugal
Grape coccus inhibiting rate 80%~100%, escherichia coli inhibiting rate 80%~100%.The wide cut of foaming coiled is
1500mm, thickness 25mm.
In preparation method, continous way extrusion foaming, second order tandem extrusion system are carried out using second order tandem extrusion system
It is composed in series by a double screw extruder 3 and a single screw extrusion machine 4,3 feed end of double screw extruder is furnished with first certainly
1 and second automatic feeding system 2 of dynamic feed system, to ensure that various raw materials are strictly put in proportion into extrusion system, foaming agent note
It includes that foaming agent holding vessel 5 and injection pump 6 form to enter unit, and foaming agent injection unit is connected to by pipe special and special service valve
Double screw extruder 3 comprising following steps：
S1：Second order tandem extrusion system is preheated to set temperature；
S2：Start second order tandem extrusion system, material is filled in respectively in mechanical feed unit, and starts and start to feed
Material；
S3：Material after head discharging, starts foaming agent injection unit, is adjusted to setting via second order tandem extrusion system
After pressure, foaming agent is injected double screw extruder 3 by valve opening, and foaming agent fills in double screw extruder 3 with molten polymer
Divide mixing, be delivered to single screw extrusion machine 4 and cool down, and be then delivered to head, is squeezed out to outside under the pressure of setting
Atmospheric pressure environment foams and is molded.
In step S3, foaming agent is physical blowing agent propane.
S4：It requires to make foamed polymer material reach degradation, the coiled material of foaming is carried out using irradiation technique
The pre- degradation of irradiation, irradiation dose 106Gy.In step S4, the irradiation bomb of irradiation technique is ultraviolet emission device.Form of radiation
For ultraviolet rays.
Embodiment 7
In the present embodiment, basic material is polyethylene terephthalate, and antibiotic functional material is magnesium oxide powder, is resisted
Ranging from 10 μm~8 μm of bacterium functional material powder granule equivalent diameter, additive amount are the 8% of foaming coiled gross mass, in structure,
Its abscess is hole-closing structure, density≤0.1g/cm3.The closed pore pore diameter range is at 10 μm~200 μm.Its degradation property is full
Sufficient national standard GB/T 20197-2006 photodegradable plastics and thermal-oxidative degradation requirement.Its anti-microbial property is marked according to QB/T2591-2003
It is accurate：Staphylococcus aureus inhibiting rate 95%~100%, escherichia coli inhibiting rate 95%~100%.
The wide cut of foaming coiled is 800mm, thickness 30mm.
In preparation method, continous way extrusion foaming, second order tandem extrusion system are carried out using second order tandem extrusion system
It is composed in series by a double screw extruder 3 and a single screw extrusion machine 4,3 feed end of double screw extruder is furnished with first certainly
1 and second automatic feeding system 2 of dynamic feed system, to ensure that various raw materials are strictly put in proportion into extrusion system, foaming agent note
It includes that foaming agent holding vessel 5 and injection pump 6 form to enter unit, and foaming agent injection unit is connected to by pipe special and special service valve
Double screw extruder 3 comprising following steps：
S1：Second order tandem extrusion system is preheated to set temperature；
S2：Start second order tandem extrusion system, material is filled in respectively in mechanical feed unit, and starts and start to feed
Material；
S3：Material after head discharging, starts foaming agent injection unit, is adjusted to setting via second order tandem extrusion system
After pressure, foaming agent is injected double screw extruder 3 by valve opening, and foaming agent fills in double screw extruder 3 with molten polymer
Divide mixing, be delivered to single screw extrusion machine 4 and cool down, and be then delivered to head, is squeezed out to outside under the pressure of setting
Atmospheric pressure environment foams and is molded.
In step S3, foaming agent is physical blowing agent pentane and its isomer.
S4：It requires to make foamed polymer material reach degradation, the coiled material of foaming is carried out using irradiation technique
The pre- degradation of irradiation, irradiation dose 103Gy.In step S4, the irradiation bomb of irradiation technique is cobalt source.Form of radiation be X-ray and
Gamma ray.
Embodiment 8
In the present embodiment, basic material is polylactic acid, and antibiotic functional material is titanium dioxide, antibiotic functional material powder
Ranging from 1 μm~0.01 μm of particle equivalent diameter, additive amount are the 12% of foaming coiled gross mass, and in structure, abscess is to close
Pore structure, density≤0.1g/cm3.The closed pore pore diameter range is at 10 μm~100 μm.Its degradation property meets national standard GB/T
20197-2006 photodegradable plastics and thermal-oxidative degradation requirement.Its anti-microbial property is according to 2003 standards of QB/T2591-：Golden yellow Portugal
Grape coccus inhibiting rate 80%~98%, escherichia coli inhibiting rate 89%~98%.The wide cut of foaming coiled is 120mm,
Thickness is 15mm.
In preparation method, continous way extrusion foaming, second order tandem extrusion system are carried out using second order tandem extrusion system
It is composed in series by a double screw extruder 3 and a single screw extrusion machine 4,3 feed end of double screw extruder is furnished with first certainly
1 and second automatic feeding system 2 of dynamic feed system, to ensure that various raw materials are strictly put in proportion into extrusion system, foaming agent note
It includes that foaming agent holding vessel 5 and injection pump 6 form to enter unit, and foaming agent injection unit is connected to by pipe special and special service valve
Double screw extruder 3 comprising following steps：
S1：Second order tandem extrusion system is preheated to set temperature；
S2：Start second order tandem extrusion system, material is filled in respectively in mechanical feed unit, and starts and start to feed
Material；
S3：Material after head discharging, starts foaming agent injection unit, is adjusted to setting via second order tandem extrusion system
After pressure, foaming agent is injected double screw extruder 3 by valve opening, and foaming agent fills in double screw extruder 3 with molten polymer
Divide mixing, be delivered to single screw extrusion machine 4 and cool down, and be then delivered to head, is squeezed out to outside under the pressure of setting
Atmospheric pressure environment foams and is molded.
In step S3, foaming agent is physical blowing agent pentamethylene.
S4：It requires to make foamed polymer material reach degradation, the coiled material of foaming is carried out using irradiation technique
The pre- degradation of irradiation, irradiation dose 105Gy.In step S4, the irradiation bomb of irradiation technique is ion accelerator.Form of radiation gamma
Ray.
Embodiment 9
In the present embodiment, basic material is fat makrolon, and antibiotic functional material is calcium oxide, antibiotic functional material powder
Ranging from 3 μm~0.01 μm of body particle equivalent diameter, additive amount are the 19%~20% of foaming coiled gross mass, in structure,
Abscess is hole-closing structure, density≤0.1g/cm3.The closed pore pore diameter range is at 200 μm~600 μm.Its degradation property meets
National standard GB/T 20197-2006 photodegradable plastics and thermal-oxidative degradation requirement.Its anti-microbial property is according to 2003 standards of QB/T2591-：
Staphylococcus aureus inhibiting rate 100%, escherichia coli inhibiting rate 100%.The wide cut of foaming coiled is 800mm, thick
Degree is 5mm.
In preparation method, continous way extrusion foaming, second order tandem extrusion system are carried out using second order tandem extrusion system
It is composed in series by a double screw extruder 3 and a single screw extrusion machine 4,3 feed end of double screw extruder is furnished with first certainly
1 and second automatic feeding system 2 of dynamic feed system, to ensure that various raw materials are strictly put in proportion into extrusion system, foaming agent note
It includes that foaming agent holding vessel 5 and injection pump 6 form to enter unit, and foaming agent injection unit is connected to by pipe special and special service valve
Double screw extruder 3 comprising following steps：
S1：Second order tandem extrusion system is preheated to set temperature；
S2：Start second order tandem extrusion system, material is filled in respectively in mechanical feed unit, and starts and start to feed
Material；
S3：Material after head discharging, starts foaming agent injection unit, is adjusted to setting via second order tandem extrusion system
After pressure, foaming agent is injected double screw extruder 3 by valve opening, and foaming agent fills in double screw extruder 3 with molten polymer
Divide mixing, be delivered to single screw extrusion machine 4 and cool down, and be then delivered to head, is squeezed out to outside under the pressure of setting
Atmospheric pressure environment foams and is molded.
In step S3, foaming agent is that physical blowing agent hydrogenates fluothane hydro carbons.
S4：It requires to make foamed polymer material reach degradation, the coiled material of foaming is carried out using irradiation technique
The pre- degradation of irradiation, irradiation dose 105Gy.In step S4, the irradiation bomb of irradiation technique is proton precessional magnetometer.Form of radiation is gal
Horse ray.
Generally speaking, the invention discloses a kind of degradable low-density foamed coiled plastic material with anti-microbial property and
Its manufacturing method.Material degradation performance meets GB/T 20197-2006 photodegradable plastics and the requirement of thermal-oxidative degradation technology；To golden yellow
Color staphylococcus inhibiting rate 10%~100%, to escherichia coli inhibiting rate 10%~100%；The density of material is less than
0.1g/cm3The relevant technologies that the present invention uses include continuous extrusion physical blowing and industrial irradiation, are suitble to industrialized production.This
The material lustration class of disclosure of the invention is high and very environmentally friendly, is suitble in necks such as packaging, food, electronics, automobile and medical treatment
Domain promotes and applies.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of plastic foamed coiled material of degradable antimicrobial form, which is characterized in that it includes matrix and antibacterial functions filler,
In,
Basic material is binary aliphatic alcohol acids polyester, or
Basic material is selected from polypropylene or polylactic acid, or
Basic material is selected from polyethylene, polyethylene terephthalate, polybutyl terapthalate or makrolon,
Antibiotic functional material is selected from one or more of titanium dioxide, zinc oxide, calcium oxide and magnesium oxide powder,
Ranging from 10 μm~0.01 μm of antibiotic functional material powder granule equivalent diameter, additive amount are foaming coiled gross mass
0.1%~20%,
In structure, abscess is hole-closing structure, foaming coiled density≤0.1g/cm3。
2. a kind of plastic foamed coiled material of degradable antimicrobial form as described in claim 1, which is characterized in that the closed pore aperture
Range is at 10 μm~1000 μm.
3. a kind of plastic foamed coiled material of degradable antimicrobial form as claimed in claim 2, which is characterized in that its degradation property is full
Foot is following to be required：
Under the conditions of heavy natural sunning, tension fracture elongation rate retention rate≤5%, and average weight-molecular mass rate of descent >=80%,
And after light degradation average weight-molecular mass < 10000 molecular percentage content >=20%, or
Under the conditions of being exposed to the sun in xenon lamp artificial accelerated aging case, tension fracture elongation rate retention rate≤5%, and the equal average molecular matter of weight
Measure rate of descent >=70%, and after light degradation average weight-molecular mass < 10000 molecular percentage content >=20%.
4. a kind of plastic foamed coiled material of degradable antimicrobial form as claimed in claim 3, which is characterized in that its anti-microbial property
For：It is 95%~100% to staphylococcus aureus antibacterium rate, is 95%~100% to escherichia coli antibacterium rate.
5. a kind of plastic foamed coiled material of degradable antimicrobial form as claimed in claim 4, which is characterized in that the width of foaming coiled
Width is 10mm~2000mm, and thickness is 0.1mm~50mm.
6. a kind of plastic foamed coiled material of degradable antimicrobial form as claimed in claim 5, which is characterized in that for basic material
Selected from polyethylene, polyethylene terephthalate, polybutyl terapthalate and makrolon, in preparation process, matrix
Material first passes through foaming using irradiation, to realize the pre- degradation of basic material, irradiation dose 102Gy~106Gy。
7. a kind of method of the plastic foamed coiled material of degradable antimicrobial form prepared as described in one of claim 1-6, feature
It is, continous way extrusion foaming is carried out using second order tandem extrusion system, second order tandem extrusion system is by a twin-screw extrusion
Machine (3) and a single screw extrusion machine (4) are composed in series, and double screw extruder (3) feed end is furnished with the first automatic feeding system
(1) and the second automatic feeding system (2), to ensure that various raw materials are strictly put in proportion into extrusion system, foaming agent injection unit
It is formed including foaming agent holding vessel (5) and injection pump (6), foaming agent injection unit is connected to double spiral shells by pipe special and special service valve
Bar extruder (3) comprising following steps：
S1：Second order tandem extrusion system is preheated to set temperature；
S2：Start second order tandem extrusion system, material is filled in respectively in mechanical feed unit, and start beginning feeding；
S3：Material after head discharging, starts foaming agent injection unit, is adjusted to setting pressure via second order tandem extrusion system
Afterwards, valve opening fills foaming agent injection double screw extruder (3), foaming agent in double screw extruder (3) with molten polymer
Divide mixing, be delivered to single screw extrusion machine (4) and cool down, and be then delivered to head, is squeezed out to outer under the pressure of setting
Portion's atmospheric pressure environment foams and is molded.
8. the method for claim 7, which is characterized in that it further includes step S4, and step S4 is：
S4：It requires to make foamed polymer material reach degradation, the coiled material of foaming is irradiated using irradiation technique
Pre- degradation, irradiation dose 102Gy~106Gy。
9. method as claimed in claim 8, which is characterized in that in step S4, the form of radiation of irradiation technique include electron beam,
Ultraviolet rays, X-ray and gamma ray.
10. method as claimed in claim 9, which is characterized in that in step S3, foaming agent is physical blowing agent, including dioxy
Change carbon, nitrogen, propane, butane and its isomer, pentane and its isomer, pentamethylene, hexane and its isomerism
Body, hexamethylene and hydrogenation fluothane hydro carbons.
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