CN112126152A - Polypropylene composite material with low-light-level diffusion effect and preparation method thereof - Google Patents
Polypropylene composite material with low-light-level diffusion effect and preparation method thereof Download PDFInfo
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- -1 Polypropylene Polymers 0.000 title claims abstract description 111
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 104
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 99
- 238000009792 diffusion process Methods 0.000 title claims abstract description 87
- 230000000694 effects Effects 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 83
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 48
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 46
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical class [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims abstract description 32
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 29
- 239000011521 glass Substances 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 26
- 239000011324 bead Substances 0.000 claims abstract description 24
- 238000002834 transmittance Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 241000588724 Escherichia coli Species 0.000 claims abstract description 14
- 241000191967 Staphylococcus aureus Species 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000155 melt Substances 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 10
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 10
- 239000000600 sorbitol Substances 0.000 claims description 10
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical group C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 claims description 6
- 229940087101 dibenzylidene sorbitol Drugs 0.000 claims description 6
- CTPBWPYKMGMLGS-CIAFKFPVSA-N (3s,4s,5s,6r)-1,8-bis(4-methylphenyl)octa-1,7-diene-2,3,4,5,6,7-hexol Chemical compound C1=CC(C)=CC=C1C=C(O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=C(C)C=C1 CTPBWPYKMGMLGS-CIAFKFPVSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 238000011179 visual inspection Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011152 fibreglass Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- 230000000295 complement effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HDUNAIVOFOKALD-RLCYQCIGSA-N (1s,2s)-1-[(4r)-2-(4-methylphenyl)-1,3-dioxolan-4-yl]-2-[(4s)-2-(4-methylphenyl)-1,3-dioxolan-4-yl]ethane-1,2-diol Chemical compound C1=CC(C)=CC=C1C1O[C@@H]([C@@H](O)[C@H](O)[C@H]2OC(OC2)C=2C=CC(C)=CC=2)CO1 HDUNAIVOFOKALD-RLCYQCIGSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 108091007643 Phosphate carriers Proteins 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a polypropylene composite material with a low-light-level diffusion effect and a preparation method thereof, wherein the method comprises the following steps of putting 100 parts by weight of homopolymerized polypropylene, 0.1-2 parts by weight of light diffusant 1, 0.1-2 parts by weight of light diffusant 2, 1-2 parts by weight of antioxidant and 1-2 parts by weight of modifier into a high-speed mixer for mixing; extruding and granulating the mixed raw materials to obtain the antibacterial polypropylene composite material with the low-light diffusion effect; the light diffusant 1 in the antibacterial polypropylene composite material with the micro-light diffusion effect is spherical glass beads with the refractive index of 1.50, and the light diffusant 2 is silver ion-substituted zirconium phosphate with a cubic structure and the refractive index of 1.83; the antibacterial polypropylene composite material with the low-light-level diffusion effect has the light transmittance of 89-91%, the haze of 17-25%, the escherichia coli antibacterial activity value of 4.0-6.0 and the staphylococcus aureus antibacterial activity value of 4.0-6.0.
Description
Technical Field
The invention belongs to the technical field of polypropylene composite materials, and relates to a polypropylene composite material with a low-light-level diffusion effect and a preparation method thereof.
Background
With the development of LED light sources, transparent decorative plates for LEDs are also developed rapidly, the traditional transparent plates are generally formed by directly injection molding transparent plastics such as PC (polycarbonate), PS (polystyrene) and the like, a layer of high-haze light diffusion plate workpiece needs to be made in the interior of the transparent decorative plates directly made of transparent plastic parts, and the dazzling effect caused by over concentration of point light sources is avoided. With the simplification and cost reduction of LED lamp design, the design of integrating the diffusion plate and the decorative plate is becoming more and more popular.
Due to the characteristics of organic matters, the plastic part is easy to breed bacteria, so that more troubles are brought in the actual use, and whether the material has excellent antibacterial property or not also becomes a reference point selected by consumers.
The polypropylene has the characteristics of low density, good transparency, easy processing, low cost, recoverability, excellent mechanical property and the like, and is widely applied to the industries of household appliances, food packaging and the like. However, no report has been made on the use of polypropylene materials in the field of micro-light diffusion and light diffusion materials having an antibacterial effect at the same time.
The prior art discloses a photodiffusion modified polypropylene material and a preparation method thereof, wherein the photodiffusion modified polypropylene material comprises the following components in percentage by weight: 98.5-99% of polypropylene, 0.3-0.8% of light diffusant, 0.05-0.5% of transparent modifier, 0.1-0.5% of antioxidant and 0.1-0.3% of light stabilizer, and the polypropylene material with the light diffusion effect is prepared. However, the light diffusion material with high haze prepared by the method does not have transparency and antibacterial effect.
Therefore, the research on the antibacterial polypropylene composite material with the low-light diffusion effect and high light transmittance is of great significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a polypropylene composite material with a low-light diffusion effect and a preparation method thereof;
one of the purposes is to provide a polypropylene composite material with a low-light diffusion effect, which comprises the following components in parts by weight: 100 parts of homopolymerized polypropylene, 0.1-2 parts of light diffusant 1, 0.1-2 parts of light diffusant 2, 1-2 parts of antioxidant and 1-2 parts of modifier, wherein the light diffusant 1 is spherical glass beads with a refractive index of 1.50, the light diffusant 2 is silver ion replacement zirconium phosphate with a cubic structure and a refractive index of 1.83, the modifier is a sorbitol transparent agent, the polypropylene composite material has the light transmittance of 89-91%, the haze of 17-25%, the escherichia coli activity resistance value of 4.0-6.0, and the staphylococcus aureus activity resistance value of 4.0-6.0.
The second purpose is to provide a preparation method of the polypropylene composite material with the micro-light diffusion effect, which comprises the following steps: according to parts by weight, firstly putting 100 parts of homo-polypropylene, 0.1-2 parts of light diffusant 1, 0.1-2 parts of light diffusant 2, 1-2 parts of antioxidant and 1-2 parts of modifier into a high-speed mixer for mixing, and then extruding and granulating the mixed raw materials to obtain the antibacterial polypropylene composite material with the shimmer diffusion effect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an antibacterial polypropylene composite material with a low-light diffusion effect comprises the following components in parts by weight:
the refractive index of the homopolymerized polypropylene is 1.54, the light diffusion agent 1 is spherical glass beads with the refractive index of 1.50, and the light diffusion agent 2 is silver ion replaced zirconium phosphate with a cubic structure and the refractive index of 1.83;
the antibacterial polypropylene composite material with the low-light-level diffusion effect has the light transmittance of 89-91%, the haze of 17-25%, the antibacterial activity value of escherichia coli of 4.0-6.0 and the antibacterial activity value of staphylococcus aureus of 4.0-6.0. Testing the light transmittance and the haze according to GB/T2410-2008; the antibacterial activity values of staphylococcus aureus and escherichia coli are tested according to ISO 22196-2011.
As a preferred technical scheme:
according to the antibacterial polypropylene composite material with the micro-light diffusion effect, the melt index of the homo-polypropylene at 230 ℃ under the test condition of 2.16kg is 8-12 g/10min, if the melt index is lower than 8g/10min, the viscosity of the material is too high, if the viscosity of the material is higher than 12g/10min, the number average molecular weight of the material is low, the two conditions can both have adverse effects on the dispersion of the light diffusant, and the agglomeration of the light diffusant and the modifier can be easily caused to influence the dispersion effect, so that the light diffusion effect is influenced.
The antibacterial polypropylene composite material with the micro-light diffusion effect is characterized in that the particle size of the spherical glass microspheres is 2-6 microns, and the particle size of the silver ion replacement zirconium phosphate salt with the cubic structure is 2-6 microns. The glass microspheres and the silver ion-substituted zirconium phosphate have too small particle sizes, so that agglomeration is easy to generate, and a uniform diffusion network cannot be formed.
The antibacterial polypropylene composite material with the micro-light diffusion effect is characterized in that the antioxidant is a compound of a phosphite antioxidant and a hindered phenol antioxidant in a mass ratio of 1: 0.3-3. The phosphite ester antioxidant and the hindered phenol antioxidant can capture and prevent the generation of heated free radicals in the material, and prevent the material from yellowing and degrading.
According to the antibacterial polypropylene composite material with the low-light-level diffusion effect, the transparent modifier is a sorbitol transparent agent, and the sorbitol transparent agent can enable the polypropylene composite material to be well crystallized so as to achieve an excellent transparent effect; .
The antibacterial polypropylene composite material with the micro-light diffusion effect is characterized in that the sorbitol clearing agent is dibenzylidene sorbitol, di (p-methylbenzylidene) sorbitol or (3, 4-dimethyl dibenzylidene) sorbitol.
The invention also provides a method for preparing the antibacterial polypropylene composite material with the micro-light diffusion effect, which comprises the following steps:
(1) putting 100 parts by weight of homo-polypropylene, 0.1-2 parts by weight of light diffusant 1, 0.1-2 parts by weight of light diffusant 2, 1-2 parts by weight of antioxidant and 1-2 parts by weight of transparent modifier into a high-speed mixer for mixing;
(2) and (2) extruding and granulating the raw materials mixed in the step (1) to obtain the antibacterial polypropylene composite material with the micro-light diffusion effect.
According to the method, the rotating speed of the high-speed mixer in the step (1) is 200-400 r/min, and the mixing time is 2-5 min.
In the method, the extrusion granulation in the step (2) is carried out in a double-screw extruder, the rotating speed of the double-screw extruder is 200-400 r/min, and the temperature is 180-220 ℃.
The mechanism of the invention is as follows:
the spherical glass beads are silicate components, are usually used as fillers in plastics to improve the mechanical property of the materials, increase the flowability of the fillers, increase the processability of the plastics, improve the surface leveling of the engineering plastics and solve the problem of glass fiber reinforced surface. The silver ion replaced zirconium phosphate is an antibacterial agent of common materials such as plastics, paint and the like, and the materials have better antibacterial effect when added.
According to the invention, by adding the spherical glass beads and silver ion-replaced zirconium phosphate for compound use, the light diffusion effect of the polypropylene composite material can be well improved and better light transmittance can be kept; this is because: the refractive index of polypropylene is 1.54, 1.50 spherical glass beads (light diffusion agent 1) and 1.83 silver ion replaced zirconium phosphate (light diffusion agent 2) are compounded, because the refractive indexes of the surfaces of the polypropylene, the light diffusant 1 and the light diffusant 2 are different from each other, and the refractive index of the light diffusant 1 is lower than that of the polypropylene, the refractive index of the light diffusion agent 2 is higher than that of polypropylene, so that on one hand, light is reflected on the surface of the spherical glass beads to play a role in diffusing the light, on the other hand, the silver ion replacement zirconium phosphate with a cubic structure added in the invention can well reflect the light on the surface of a cube, when the glass beads and the zirconium phosphate are compounded, the glass beads with the spherical structure and the silver ions with the cubic structure replace the zirconium phosphate to form a filling system which is uniformly dispersed with each other, so that a complementary structure can be formed, and the characteristics are as follows: when the light is reflected on the surface of the cubic structure, the reflected light can be further reflected through the spherical structure, and vice versa; the composite material is provided with a large number of substances with different structures and different refractive indexes, when light passes through one substance interface, the light can be reflected and refracted, meanwhile, when the reflected light passes through the other interface, the light can be reflected and refracted, and after numerous reflection and refraction processes, the light finally penetrates out of the composite material; when the difference of the refractive indexes is larger, the reflection angle is also larger; the spherical and cubic structures are complementary, and the light diffusion effect (i.e. haze improvement) can be greatly improved after multiple reflections. Meanwhile, the glass beads and the silver ion-substituted zirconium phosphate have small influence on the light transmittance, so that the material can still have a transparent effect under the condition of low addition amount, namely, the transparency is high.
The silver ion-substituted zirconium phosphate contains silver ions which have very excellent antibacterial effect, so that the product of the invention has very excellent antibacterial effect at the same time.
Has the advantages that:
(1) the polypropylene composite material with the low-light-level diffusion effect uses the homo-polypropylene with the melt index of 8-12 g/10min (230 ℃ C. times.2.16 kg), has excellent light transmittance due to high crystallinity and fine and large crystal nucleus, and has good processability, excellent impact property and good coating property on light diffusant powder;
(2) according to the polypropylene composite material with the low-light-level diffusion effect, the light diffusion effect is improved and the better light transmittance is kept through compounding of the glass beads and the silver ion replacement zirconium phosphate, the refractive index of polypropylene is 1.54, the spherical glass beads with the refractive index of 1.50 and the silver ion replacement zirconium phosphate with the refractive index of 1.83 are compounded, so that different refractive indexes are formed among materials, better diffusion and resin penetration of light can be well and synergistically achieved, and the good light transmittance and the low-light-level diffusion effect are achieved;
(3) according to the polypropylene composite material with the low-light diffusion effect, the excellent antibacterial effect of silver ions in zirconium phosphate is replaced by the silver ions, so that the excellent antibacterial property of a workpiece is realized;
(4) the product prepared from the polypropylene composite material with the low-light-level diffusion effect has a smooth surface, a workpiece is transparent and has a certain haze, the light diffusion effect and the antibacterial effect are achieved, the appearance is attractive, and the cost is low.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the teachings of the present invention, and such equivalents also fall within the scope of the appended claims.
The performance test method of the polypropylene composite material prepared by the invention comprises the following steps:
the composite material is injected into a polished plate with the thickness of 2mm, the light transmittance and the haze are tested according to GB/T2410-2008, and meanwhile, the 2mm plate is placed 1cm away from an LED point light source to visually observe the light source diffusion effect; the antibacterial activity values of Staphylococcus aureus and Escherichia coli were tested according to ISO 22196-2011.
The particle sizes referred to in the present invention are average particle sizes;
the silver ion-substituted zirconium phosphate with a cubic structure adopted in the invention is a cubic zirconium phosphate carrier JDGQP-003, and the manufacturer comprises: jin Dai nanometer technology (Xiamen) Inc.
Example 1
A preparation method of an antibacterial polypropylene composite material with a low-light diffusion effect comprises the following steps:
preparing raw materials: the composite material comprises homopolymerized polypropylene with a melt index of 8g/10min at 230 ℃ and under the test condition of 2.16kg, spherical glass beads (light diffusant 1) with the average particle size of 3 mu m and the refractive index of 1.50, silver ion replacement zirconium phosphate (light diffusant 2) with the particle size of 2 mu m and the refractive index of 1.83 and a cubic structure, a compound (antioxidant) of phosphite antioxidant and hindered phenol antioxidant in a mass ratio of 1:1, and dibenzylidene sorbitol (transparent modifier);
(1) putting 100 parts of homopolymerized polypropylene, 0.1 part of light diffusant 1, 0.1 part of light diffusant 2, 1 part of antioxidant and 1 part of transparent modifier into a high-speed mixer for mixing according to parts by weight; wherein the rotating speed of the high-speed mixer is 400 r/min, and the mixing time is 3 min;
(2) extruding and granulating the raw materials mixed in the step (1) in a double-screw extruder to obtain the antibacterial polypropylene composite material with the micro-light diffusion effect; wherein the rotating speed of the double-screw extruder is 400 r/min, and the temperature is 200 ℃;
the antibacterial polypropylene composite material with the micro-light diffusion effect has the light transmittance of 91%, the haze of 20%, the escherichia coli antibacterial activity value of 4 and the staphylococcus aureus antibacterial activity value of 4; visual inspection of a light source: and (4) softening.
Comparative example 1
A polypropylene composite material was prepared by the same procedure as in example 1 except that no light diffusing agent 2 was added in step (1) and the mass of the light diffusing agent 1 was the same as the sum of the masses of the light diffusing agents 1 and 2 of example 1, and the resulting composite material was subjected to the performance test, the test results of which are shown in Table 1.
Comparative example 2
A polypropylene composite material was prepared by the same procedure as in example 1 except that no light diffusing agent 1 was added in step (1) and the light diffusing agent 2 had the same mass as the sum of the light diffusing agents 1 and 2 of example 1, and the resulting composite material was subjected to the performance test, the test results of which are shown in Table 1.
Comparative example 3
A polypropylene composite material was prepared in substantially the same manner as in example 1 except that in step (1), glass beads were replaced with silica (spherical structure) having a refractive index of 1.6 or the like, and the resulting composite material was subjected to a performance test, the test results of which are shown in table 1.
Comparative example 4
A preparation method of a polypropylene composite material is basically the same as that of example 1, except that in the step (1), the homopolypropylene in the example 1 is replaced by the homopolypropylene with the melt index of 7g/10min and the like, and the prepared composite material is subjected to performance test, and the test results are shown in Table 1.
Comparative example 5
A preparation method of a polypropylene composite material is basically the same as that of example 1, except that in the step (1), homopolypropylene with the melt index of 13g/10min and the like is used for replacing the homopolypropylene in the example 1, and the prepared composite material is subjected to performance test, and the test results are shown in Table 1.
TABLE 1 Performance of comparative examples 1 to 5
As can be seen from comparison between comparative example 1 and example 1, the haze of the composite material prepared in comparative example 1 is lower, because when incident light is reflected on the surface of the glass beads with spherical structures, the light cannot form effective complementary reflection in the composite material, so that the haze is lower; and the composite material in comparative example 1 has no antibacterial property because silver ions are used for the antibacterial function in example 1, while silver ions are not used in comparative example 1; the visual observation result of the light source is dazzling, which more intuitively explains that the composite material has poor light diffusion effect.
As can be seen by comparing comparative example 2 with example 1, the haze of the composite material prepared in comparative example 2 is lower because incident light rays form fewer diffusion paths within the composite material after reflection at the surface of the cubic silver ion-substituted zirconium phosphate salt than do the simple spherical structures; the visual observation result of the light source is dazzling, which indicates that the composite material has poor light diffusion effect.
Comparing comparative example 3 with example 1, it can be seen that the light transmittance of the composite material prepared in comparative example 3 is much lower, because the silica has strong light shielding effect and light cannot be reflected from the composite material; the haze of the composite material in comparative example 3 was lower because a good diffusion synergy effect was achieved when a portion of the light diffuser had a lower refractive index than polypropylene and another portion of the light diffuser had a higher refractive index than polypropylene, the silica and silver ion-substituted zirconium phosphate in comparative example 3 had a higher refractive index than polypropylene, and such a synergy effect could not be achieved, and the light source visual observation was more glaring, indicating that the composite material had a poor light diffusion effect.
Comparing comparative examples 4 and 5 with example 1, it can be seen that the transmittance and haze of the composite materials prepared in comparative examples 4 and 5 are lower than those of example 1, because the melt index in comparative example 4 is low and the viscosity of the material is high, while the melt index in comparative example 5 is high and the number average molecular weight of the material is low, and when the viscosity of polypropylene is too high or too low, the uniform dispersion of the light diffusers 1 and 2 in the polypropylene melt during processing is not facilitated, so that the light diffusers 1 and 2 agglomerate, which affects the light diffusion effect and the light transmittance of the material; the antibacterial performance of the composite materials in the proportion 4 and the proportion 5 is obviously reduced because the viscosity of the material is too high, and the silver ion-substituted zirconium phosphate is unevenly distributed in the composite material, so that the uniform dispersion of the silver ions of the material is influenced, and the antibacterial performance is reduced; the visual observation result of the light source is more glaring, which indicates that the composite material has poor light diffusion effect.
Example 2
A preparation method of an antibacterial polypropylene composite material with a low-light diffusion effect comprises the following steps:
preparing raw materials: the glass fiber reinforced plastic composite material comprises homopolymerized polypropylene with a melt index of 9g/10min at 230 ℃ and under the test condition of 2.16kg, spherical glass beads (light diffusant 1) with the particle size of 4 mu m and the refractive index of 1.50, silver ion replacement zirconium phosphate (light diffusant 2) with the particle size of 3 mu m and the refractive index of 1.83 and with a cubic structure, and a compound (antioxidant) of phosphite antioxidant and hindered phenol antioxidant (antioxidant) bis (p-methylbenzylidene) sorbitol (transparent modifier) with the mass ratio of 1: 2;
(1) putting 100 parts of homopolymerized polypropylene, 2 parts of light diffusant 1, 2 parts of light diffusant 2, 2 parts of antioxidant and 2 parts of transparent modifier into a high-speed mixer for mixing according to parts by weight; wherein the rotating speed of the high-speed mixer is 300 revolutions per minute, and the mixing time is 2 min;
(2) extruding and granulating the raw materials mixed in the step (1) in a double-screw extruder to obtain the antibacterial polypropylene composite material with the micro-light diffusion effect; wherein the rotating speed of the double-screw extruder is 300 revolutions per minute, and the temperature is 190 ℃;
the antibacterial polypropylene composite material with the micro-light diffusion effect has the advantages that the light transmittance is 89%, the haze is 25%, the escherichia coli antibacterial activity value is 6, and the staphylococcus aureus antibacterial activity value is 6; visual inspection of a light source: and (4) softening.
Example 3
A preparation method of an antibacterial polypropylene composite material with a low-light diffusion effect comprises the following steps:
preparing raw materials: the glass fiber reinforced plastic composite material comprises homopolymerized polypropylene with a melt index of 11g/10min at 230 ℃ and under a test condition of 2.16kg, spherical glass beads (light diffusant 1) with a particle size of 5 mu m and a refractive index of 1.50, silver ion replacement zirconium phosphate (light diffusant 2) with a cubic structure with a particle size of 5 mu m and a refractive index of 1.83, and a compound (antioxidant) (3, 4-dimethyl dibenzylidene) sorbitol (transparent modifier) of phosphite antioxidant and hindered phenol antioxidant in a mass ratio of 1: 3;
(1) 100 parts of homopolymerized polypropylene, 1 part of light diffusant 1, 1 part of light diffusant 2, 1 part of antioxidant and 2 parts of transparent modifier are put into a high-speed mixer to be mixed according to parts by weight; wherein the rotating speed of the high-speed mixer is 350 r/min, and the mixing time is 5 min;
(2) extruding and granulating the raw materials mixed in the step (1) in a double-screw extruder to obtain the antibacterial polypropylene composite material with the micro-light diffusion effect; wherein the rotating speed of the double-screw extruder is 350 r/min, and the temperature is 180 ℃;
the antibacterial polypropylene composite material with the micro-light diffusion effect has the advantages that the light transmittance is 90%, the haze is 17%, the escherichia coli antibacterial activity value is 5, and the staphylococcus aureus antibacterial activity value is 5; visual inspection of a light source: and (4) softening.
Example 4
A preparation method of an antibacterial polypropylene composite material with a low-light diffusion effect comprises the following steps:
preparing raw materials: the glass fiber reinforced plastic composite material comprises homopolymerized polypropylene with a melt index of 12g/10min at 230 ℃ and under a test condition of 2.16kg, spherical glass beads (light diffusant 1) with the particle size of 2 mu m and the refractive index of 1.50, silver ion replacement zirconium phosphate (light diffusant 2) with the particle size of 2 mu m and the refractive index of 1.83 and a compound (antioxidant) of phosphite antioxidant and hindered phenol antioxidant in a mass ratio of 1:0.5, and dibenzylidene sorbitol (transparent modifier);
(1) putting 100 parts of homopolymerized polypropylene, 0.1 part of light diffusant 1, 0.1 part of light diffusant 2, 1 part of antioxidant and 1 part of transparent modifier into a high-speed mixer for mixing according to parts by weight; wherein the rotating speed of the high-speed mixer is 250 revolutions per minute, and the mixing time is 4 min;
(2) extruding and granulating the raw materials mixed in the step (1) in a double-screw extruder to obtain the antibacterial polypropylene composite material with the micro-light diffusion effect; wherein the rotating speed of the double-screw extruder is 250 r/min, and the temperature is 190 ℃;
the antibacterial polypropylene composite material with the low-light diffusion effect has the advantages that the light transmittance is 89%, the haze is 25%, the escherichia coli antibacterial activity value is 5.9, and the staphylococcus aureus antibacterial activity value is 6; visual inspection of a light source: and (4) softening.
Example 5
A preparation method of an antibacterial polypropylene composite material with a low-light diffusion effect comprises the following steps:
preparing raw materials: the glass fiber reinforced plastic composite material comprises homopolymerized polypropylene with a melt index of 8g/10min at 230 ℃ and under a test condition of 2.16kg, spherical glass beads (light diffusant 1) with the particle size of 5 mu m and the refractive index of 1.50, silver ion replacement zirconium phosphate (light diffusant 2) with the particle size of 4 mu m and the refractive index of 1.83 and with a cubic structure, and dibenzylidene sorbitol (transparent modifier) which is a compound (antioxidant) of phosphite antioxidants and hindered phenol antioxidants in a mass ratio of 1: 0.3;
(1) putting 100 parts of homopolymerized polypropylene, 2 parts of light diffusant 1, 2 parts of light diffusant 2, 2 parts of antioxidant and 2 parts of transparent modifier into a high-speed mixer for mixing according to parts by weight; wherein the rotating speed of the high-speed mixer is 200 revolutions per minute, and the mixing time is 2 min;
(2) extruding and granulating the raw materials mixed in the step (1) in a double-screw extruder to obtain the antibacterial polypropylene composite material with the micro-light diffusion effect; wherein the rotating speed of the double-screw extruder is 200 r/min, and the temperature is 195 ℃;
the antibacterial polypropylene composite material with the micro-light diffusion effect has the advantages that the light transmittance is 89%, the haze is 25%, the escherichia coli antibacterial activity value is 6, and the staphylococcus aureus antibacterial activity value is 6; visual inspection of a light source: and (4) softening.
Example 6
A preparation method of an antibacterial polypropylene composite material with a low-light diffusion effect comprises the following steps:
preparing raw materials: the glass fiber reinforced plastic composite material comprises homopolymerized polypropylene with a melt index of 9g/10min at 230 ℃ and under the test condition of 2.16kg, spherical glass beads (light diffusant 1) with the particle size of 6 mu m and the refractive index of 1.50, silver ion replacement zirconium phosphate (light diffusant 2) with the particle size of 6 mu m and the refractive index of 1.83 and a cubic structure of silver ion replacement zirconium phosphate, and a compound (antioxidant) of phosphite antioxidant and hindered phenol antioxidant (antioxidant) di (p-methylbenzylidene) sorbitol (transparent modifier) with the mass ratio of 1: 1.5;
(1) 100 parts of homopolymerized polypropylene, 1 part of light diffusant 1, 1 part of light diffusant 2, 1 part of antioxidant and 2 parts of transparent modifier are put into a high-speed mixer to be mixed according to parts by weight; wherein the rotating speed of the high-speed mixer is 400 r/min, and the mixing time is 3 min;
(2) extruding and granulating the raw materials mixed in the step (1) in a double-screw extruder to obtain the antibacterial polypropylene composite material with the micro-light diffusion effect; wherein the rotating speed of the double-screw extruder is 400 r/min, and the temperature is 205 ℃;
the antibacterial polypropylene composite material with the micro-light diffusion effect has the advantages that the light transmittance is 90%, the haze is 24%, the escherichia coli antibacterial activity value is 5.9, and the staphylococcus aureus antibacterial activity value is 5.9; visual inspection of a light source: and (4) softening.
Example 7
A preparation method of an antibacterial polypropylene composite material with a low-light diffusion effect comprises the following steps:
preparing raw materials: the glass fiber reinforced plastic composite material comprises homopolymerized polypropylene with a melt index of 10g/10min at 230 ℃ and under a test condition of 2.16kg, spherical glass beads (light diffusant 1) with the particle size of 4 mu m and the refractive index of 1.50, silver ion replacement zirconium phosphate (light diffusant 2) with the particle size of 3 mu m and the refractive index of 1.83 and with a cubic structure, and a compound (antioxidant) (3, 4-dimethyl dibenzylidene) sorbitol (transparent modifier) of phosphite antioxidant and hindered phenol antioxidant in a mass ratio of 1: 2.2;
(1) putting 100 parts of homopolymerized polypropylene, 0.1 part of light diffusant 1, 0.1 part of light diffusant 2, 1 part of antioxidant and 1 part of transparent modifier into a high-speed mixer for mixing according to parts by weight; wherein the rotating speed of the high-speed mixer is 330 revolutions per minute, and the mixing time is 4 min;
(2) extruding and granulating the raw materials mixed in the step (1) in a double-screw extruder to obtain the antibacterial polypropylene composite material with the micro-light diffusion effect; wherein the rotating speed of the double-screw extruder is 330 revolutions per minute, and the temperature is 220 ℃;
the antibacterial polypropylene composite material with the low-light-level diffusion effect has the light transmittance of 91%, the haze of 17%, the escherichia coli antibacterial activity value of 4.1 and the staphylococcus aureus antibacterial activity value of 4; visual inspection of a light source: and (4) softening.
Example 8
A preparation method of an antibacterial polypropylene composite material with a low-light diffusion effect comprises the following steps:
preparing raw materials: the composite material comprises homopolymerized polypropylene with a melt index of 10g/10min at 230 ℃ and under the test condition of 2.16kg, spherical glass beads (light diffusant 1) with the particle size of 2 mu m and the refractive index of 1.50, silver ion replacement zirconium phosphate (light diffusant 2) with the particle size of 2 mu m and the refractive index of 1.83 and a compound (antioxidant) dibenzylidene sorbitol (transparent modifier) of phosphite antioxidant and hindered phenol antioxidant in a mass ratio of 1: 2.7;
(1) putting 100 parts of homopolymerized polypropylene, 2 parts of light diffusant 1, 2 parts of light diffusant 2, 2 parts of antioxidant and 2 parts of transparent modifier into a high-speed mixer for mixing according to parts by weight; wherein the rotating speed of the high-speed mixer is 220 r/min, and the mixing time is 4 min;
(2) extruding and granulating the raw materials mixed in the step (1) in a double-screw extruder to obtain the antibacterial polypropylene composite material with the micro-light diffusion effect; wherein the rotating speed of the double-screw extruder is 220 r/min, and the temperature is 200 ℃;
the antibacterial polypropylene composite material with the micro-light diffusion effect has the advantages that the light transmittance is 89%, the haze is 24%, the escherichia coli antibacterial activity value is 5.2, and the staphylococcus aureus antibacterial activity value is 5.3; visual inspection of a light source: and (4) softening.
Claims (9)
1. An antibacterial polypropylene composite material with a low-light diffusion effect is characterized in that: the composition comprises the following components in parts by weight:
the refractive index of the homopolymerized polypropylene is 1.54, the light diffusion agent 1 is spherical glass beads with the refractive index of 1.50, and the light diffusion agent 2 is silver ion replaced zirconium phosphate with a cubic structure and the refractive index of 1.83;
the antibacterial polypropylene composite material with the low-light-level diffusion effect has the light transmittance of 89-91%, the haze of 17-25%, the antibacterial activity value of escherichia coli of 4.0-6.0 and the antibacterial activity value of staphylococcus aureus of 4.0-6.0.
2. The antibacterial polypropylene composite material with the micro light diffusion effect as claimed in claim 1, wherein the melt index of the homo-polypropylene under the test conditions of 230 ℃ and 2.16kg is 8-12 g/10 min.
3. The antibacterial polypropylene composite material with a micro light diffusion effect as claimed in claim 1, wherein the spherical glass beads have a particle size of 2-6 μm, and the silver ion-substituted zirconium phosphate salt with a cubic structure has a particle size of 2-6 μm.
4. The antibacterial polypropylene composite material with the micro-light diffusion effect as claimed in claim 1, wherein the antioxidant is a compound of a phosphite antioxidant and a hindered phenol antioxidant in a mass ratio of 1: 0.3-3.
5. The antibacterial polypropylene composite material with the effect of micro light diffusion according to claim 1, wherein the transparent modifier is a sorbitol transparent agent.
6. The antimicrobial polypropylene composite material with the effect of micro light diffusion according to claim 5, wherein the sorbitol clearing agent is dibenzylidene sorbitol, di (p-methylbenzylidene) sorbitol or (3, 4-dimethyl dibenzylidene) sorbitol.
7. The method for preparing the antibacterial polypropylene composite material with the micro-light diffusion effect as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) putting 100 parts by weight of homo-polypropylene, 0.1-2 parts by weight of light diffusant 1, 0.1-2 parts by weight of light diffusant 2, 1-2 parts by weight of antioxidant and 1-2 parts by weight of transparent modifier into a high-speed mixer for mixing;
(2) and (2) extruding and granulating the raw materials mixed in the step (1) to obtain the antibacterial polypropylene composite material with the micro-light diffusion effect.
8. The method according to claim 7, wherein the rotation speed of the high-speed mixer in the step (1) is 200-400 rpm, and the mixing time is 2-5 min.
9. The method as claimed in claim 8, wherein the extrusion granulation in the step (2) is performed in a twin-screw extruder, the rotation speed of the twin-screw extruder is 200-400 r/min, and the temperature is 180-220 ℃.
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Denomination of invention: A polypropylene composite material with low light diffusion effect and its preparation method Granted publication date: 20230905 Pledgee: Agricultural Bank of China Limited Shanghai Jinshan Sub-branch Pledgor: SHANGHAI SUNNY TECHNOLOGY Co.,Ltd. Registration number: Y2024310000570 |