CN110003641A - A kind of high-performance antibiosis composite material and preparation method - Google Patents
A kind of high-performance antibiosis composite material and preparation method Download PDFInfo
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- CN110003641A CN110003641A CN201811555958.1A CN201811555958A CN110003641A CN 110003641 A CN110003641 A CN 110003641A CN 201811555958 A CN201811555958 A CN 201811555958A CN 110003641 A CN110003641 A CN 110003641A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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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
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Invention discloses a kind of high-performance antibiosis composite material and preparation method, the high-performance antibiosis composite material is mainly prepared by following components according to parts by weight: 35~95 parts of polyphthalamide (PPA), ethylene-methyl methacrylate ethylene oxidic ester -5~50 parts of methyl acrylate (E-GMA-MA), 0.5-35 parts of nano-silver powder, 0.5-35 parts of nano-titanium dioxide, 5-15 parts of dispersing agent, 0.1~1.5 part of coupling agent, 0.5~1 part of antioxidant.PPA/E-GMA-MA thermostability engineering plastic alloy material is as skeleton selected in the present invention, antimicrobial composite material is assigned with excellent high temperature resistant, high intensity, the performance of high tenacity, and improve the restraining and sterilizing bacteria efficiency of antimicrobial composite material, the use scope for expanding composite material, allows to be widely used on the environmental unit components of high-temp resisting high-humidity resistings such as military project, nuclear power, high-speed rail tunnel bridge.
Description
Technical field
The present invention relates to functional engineering plastic materials field, specifically a kind of high-performance antibiosis composite material and its preparation
Method.
Background technique
Anti-biotic material refers to that itself has a kind of new function material killed or inhibit microbial function, leads in military project
There is extremely wide application prospect in the fields such as domain, medical field, civilian food packaging.With the expansion of the application range of plastics,
The application field of antibiotic plastic is further extended.Now, with the raising of the comprehensive performances such as high temperature resistant, high intensity, work
Engineering plastics are gradually applied to military project, high-speed rail highway, oil field, to meet by the substitute as conventional metals product
It loss of weight to product and corrosion-resistant etc. requires.But in use, especially in wet environment, frosting is easy
Cooperating microorganisms and algae will have a direct impact on the service performance of equipment and product when situation is serious.Currently, being directed to high temperature plastics material
The research and development of the anti-microbial property of material are also rarely reported.
Therefore, it still needs further improvement for existing plastic material.
Summary of the invention
The present invention is this compound in view of the above-mentioned problems, provide a kind of high-performance antibiosis composite material and preparation method
The comprehensive performance that material has excellent anti-microbial property, high temperature resistant, intensity high, does not have antibacterial to solve existing high performance material
The problem of performance.
Technical scheme is as follows:
The present invention provides a kind of high-performance antibiosis composite material, and the composite material is mainly by following components according to parts by weight
Number is prepared:
35~95 parts of polyphthalamide (PPA), ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate (E-
GMA-MA) 5~50 parts, 0.5-35 parts of silver powder, 0.5-35 parts of titanium dioxide, 5-15 parts of dispersing agent, 0.1~1.5 part of coupling agent,
0.5~1 part of antioxidant.
Nano-silver powder due to being nanoscale particle, due to its structural unit size between macroscopic material and microcosmic atom and
Between molecule, special skin effect, small-size effect, quantum size effect and macro quanta tunnel effect are shown, it can be with
It easily enters in microbial body, large specific surface area, expands the active position of particle surface, afterwards and carefully into cell membrane (wall)
The sulfydryl of volume oxygen metabolism enzyme intracellular combines, and inactivates respiratory enzyme, microorganism is choked to death since respiratory metabolism is blocked.
Nano-titanium dioxide is a kind of semiconductor material for having photo-catalysis function, has very high surface-active, when two
After photon excitation of the titanium oxide by certain energy, it may occur that light-catalyzed reaction simultaneously generates many active matters with strong oxidizing property
Matter (such as hydroxyl radical free radical, superoxipe ion, hydrogen peroxide), these active materials can be interior with microorganism (bacterium, fungi and virus)
Outer organic matter carries out redox reaction and plays the role of antibacterial sterilization to kill microorganism in a short time.
Above two antibacterial agent cooperates by different antibacterial bacteriostatic principles, high-performance is not only greatly improved
The antibacterial sterilization of antimicrobial composite material thought, and had expanded fungicidal spectrum wide, answer the high-performance antibiosis composite material can extensively
For various antibacterial sterilization fields, heat-resisting quantity is strong, and sustained anti-microbial effect is good.Also, nano-titanium dioxide and nano-silver powder tool
There is good dispersion performance, there is excellent compatibility with PPA and E-GMA-MA, with (the dispersing agent 5- of other compositions in formula
15 parts, 0.1~1.5 part of coupling agent) interaction under, these antibacterial agent ingredients and other organic principles are sufficiently mixed and close
It is combined together to form high temperature resistant, high intensity and high performance antimicrobial composite material.
Preferably, the number-average molecular weight of polyphthalamide is heat distortion temperature under 1.5 ten thousand~5.0 ten thousand, 1.80MPa
It (HDT) is 295-300 DEG C.The selection fine heat-resisting performance of this PPA, the good processing stability with E-GMA-MA have excellent
Compatibility can form the composite material of high-toughness high-strength.
Preferably, in ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate copolymer (E-GMA-MA), methyl-prop
The mass percent of olefin(e) acid ethylene oxidic ester is 3~20%, and the mass percent of methyl acrylate is 10~40%.This ratio
Terpolymer compatibilization effect is good, can sufficiently improve the melt-flow state of blend, forms homogeneous blend material.
Preferably, the average grain diameter 20nm-250nm of silver powder, specific surface area 0.5-50m2/g.The nano-silver powder of this partial size
Conducive in conjunction with antimicrobial surface, efficiently enter in microorganism, large specific surface area expands the active sites on silver powder particles surface
It sets, the higher bactericidal and bacteriostatic effect of high-performance antibiosis composite material of preparation can be assigned.
Preferably, the average grain diameter 15nm-120nm of nano-titanium dioxide, specific surface area 10-90m2/g.This partial size
The surface response area of titanium dioxide is big, conducive to the bactericidal performance for improving composite material.
Preferably, the composite dispersing agent that dispersing agent is made of phosphoric acid salt and stearmide, phosphoric acid salt and stearoyl
The mass ratio of amine is 1:5~4:1.This composite dispersing agent improve dispersibility of two kinds of nano antibacterial agents in above-mentioned resin,
Compatibility and high thermal stability.Stearoyl amine dispersing agent can provide initial stage dispersion effect and good with the compatibility of basis material
It is good, but resistance to heat differential；Phosphoric acid salt dispersing agent initial performances are unobvious, but heat-resist, provide long dispersion stability.Two types
Type dispersing agent complements each other, and plays synergistic effect.
Preferably, the phosphoric acid salt is polyphosphate sodium, calgon and the triethyl group hexyl for being 1:1:1 by mass ratio
The compound of phosphoric acid composition.Stearmide be by mass ratio the vinyl bis-stearamides of 1:1:1, glyceryl tristearate and
The compound of oleamide composition.The using effect of the dispersing agent of above-mentioned phosphoric acid salt and the compound no composition of stearmide is best.
Preferably, the coupling agent be by weight ratio be 1:1~1:3 phthalate ester coupling agent and zirconium ester coupling agent group
At purity is higher than 99.5%.The coupling agent of said ratio by system inorganic material and organic material be closely linked,
Farthest improve the adhesiveness and dispersibility of antimicrobial composite material.
Preferably, the antioxidant by weight ratio be 1:1.5:1 antioxidant 1010,168 and HP-136 form it is compound
Antioxidant.This composite antioxidant is the advantage of each antioxidant to be given full play to, to height using the synergistic effect between three kinds of antioxidant
Performance antimicrobial composite material provides excellent antioxygenic property, guarantees its stability, avoids it in processing, storage and transportation, use
In the process be oxidized degradation.
The present invention also provides a kind of preparation method of high-performance antibiosis composite material as described above, the preparation method packets
Include following steps:
S1, by the polyphthalamide of corrresponding quality number, ethylene-methyl methacrylate ethylene oxidic ester-acrylic acid first
Ester, coupling agent and antioxidant are added to high-speed mixer, mix 15-25min, and 300~1000rpm of revolving speed obtains material 1；
S2, by the nano-silver powder of corrresponding quality number, nano-titanium dioxide, dispersing agent is in high-speed mixer mixing 15-
25min, 300~1000rpm of revolving speed obtain material 2；
S3, respectively by material 1 from main spout, material 2 is added in parallel double-screw extruder from side spout and is made
Grain, prilling temperature are 310~350 DEG C, and screw speed is 200~600rpm, and using water ring pelletizing, cyclonic separation is dried to obtain height
Performance antimicrobial composite material.
The beneficial effects of the present invention are:
1. PPA/E-GMA-MA thermostability engineering plastic alloy material selected in the present invention assigns antibacterial as skeleton
Composite material expands the use scope of composite material with excellent high temperature resistant, high intensity, the performance of high tenacity, allows to wide
It is general to apply on the environmental unit component of the high-temp resisting high-humidity resistings such as military project, nuclear power, high-speed rail tunnel bridge.
2, the antibacterial agent nano-silver powder and nano titanium dioxide anti-bacterial agent that the present invention selects two kinds of high surface activities are as multiple
Antibacterial agent is closed, antimicrobial composite material is significantly improved using the synergistic effect of the two based on the different antibacterial antivirus principle of the two
Restraining and sterilizing bacteria efficiency expands antimicrobial spectrum (expanding antibacterial object range), makes it to Pseudomonas aeruginosa, Escherichia coli, golden yellow grape
Coccus, salmonella and Aspergillus etc. have very strong sterilizing ability；Also, above-mentioned compound disinfectant is easily dispersed, high temperature resistant
Property it is strong, with PPA, E-GMA-MA have excellent compatibility, with formula in other compositions interaction after, these antibacterial agents
Ingredient and other organic principles are sufficiently mixed and are closely linked to form high temperature resistant, high intensity and high performance antibacterial composite wood
Material.
3, the preparation method of high-performance antibiosis composite material provided by the invention is simple, and short preparation period is easy to extensive
Production, reduces the production cost of high-performance antibiosis composite material.
Specific embodiment
Following part is that the present invention will be further described for specific embodiment, but following implementation is only to this hair
Bright is explained further, and does not represent the scope of the present invention and is only limitted to this, all equivalence replacements done with thinking of the invention,
In protection scope of the present invention, for explaining only the invention, and it is not considered as limiting the invention.
Embodiment 1
1. by 75 parts of polyphthalamide (PPA), ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate (E-
GMA-MA) 8 parts, 0.6 part of coupling agent, 0.8 part of antioxidant obtains in high-speed mixer mixing 20min, 300~1000rpm of revolving speed
Material 1；
2. 6 parts of nano-titanium dioxide, 5 parts of dispersing agent in high-speed mixer mixing 20min, revolving speed by 6 parts of nano-silver powder
600rpm obtains material 2；
3. material 2 is added in parallel double-screw extruder from side spout and is granulated by material 1 from main spout, it is granulated temperature
Degree is 330 DEG C, screw speed 500rpm, and using water ring pelletizing, cyclonic separation is dried to obtain high-performance antibiosis composite material.
Embodiment 2
1. by 80 parts of polyphthalamide (PPA), ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate (E-
GMA-MA) 8 parts, 0.6 part of coupling agent, 0.8 part of antioxidant obtains in high-speed mixer mixing 20min, 300~1000rpm of revolving speed
Material 1；
2. 3.5 parts of nano-titanium dioxide, 5 parts of dispersing agent, in high-speed mixer mixing 20min, turn by 3.5 parts of nano-silver powder
Fast 600rpm obtains material 2；
3. material 2 is added in parallel double-screw extruder from side spout and is granulated by material 1 from main spout, it is granulated temperature
Degree is 330 DEG C, screw speed 500rpm, and using water ring pelletizing, cyclonic separation is dried to obtain high-performance antibiosis composite material.
Embodiment 3
1. 45 parts of polyphthalamide (PPA), ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate (E-
GMA-MA) 43 parts, 0.6 part of coupling agent, 0.8 part of antioxidant obtains in high-speed mixer mixing 20min, 300~1000rpm of revolving speed
To material 1；
2. 25 parts of nano-titanium dioxide, 5 parts of dispersing agent, in high-speed mixer mixing 20min, turn by 25 parts of nano-silver powder
Fast 600rpm obtains material 2；
3. material 2 is added in parallel double-screw extruder from side spout and is granulated by material 1 from main spout, it is granulated temperature
Degree is 330 DEG C, screw speed 500rpm, and using water ring pelletizing, cyclonic separation is dried to obtain high-performance antibiosis composite material.
Reference examples
1. 0.6 part of coupling agent, 0.8 part of antioxidant mixes in high-speed mixer by 90 parts of polyphthalamide (PPA)
20min, revolving speed 500rpm obtain material 1；
2. 4 parts of dispersing agent obtain material 2 in high-speed mixer mixing 20min, revolving speed 600rpm by 6 parts of nano-silver powder；
3. material 2 is added in parallel double-screw extruder from side spout and is granulated by material 1 from main spout, it is granulated temperature
Degree is 330 DEG C, and screw speed 500rpm, using water ring pelletizing, cyclonic separation is dried to obtain antimicrobial composite material.
4 performance test of embodiment
Antimicrobial composite material prepared by embodiment 1-3, comparative example is subjected to properties in accordance with the following methods respectively respectively
Test:
Measuring mechanical property is tested according to following national standard:
Tensile property testing standard: GB1040-79；
Bending property testing standard: GB1042-79；
Impact property testing standard: GB1043-79；
Frosting Anti-microbial Performance Tests method: GB/T 31402-2015, above-mentioned material test result is as follows table institute
Show:
From the point of view of 1~embodiment of embodiment, 3 performance, high-performance antibiosis composite material has high intensity and impact resistance tough
Property, while there is excellent antibacterial effect (bacteriostasis rate bacterium is higher than 95%).Single PPA material is not taken in reference examples, not plus E-
Tough declines after GMA-MA, and antibacterial effect can not show a candle to embodiment 1-3, and company standard requirement is not achieved.Obviously, originally
The high comprehensive performance of the high-performance antibiosis composite material provided is invented, tough is improved, and is had excellent
Anti-microbial property.
The present invention is described by way of example above, but the present invention is not limited to above-mentioned specific embodiment, all to be based on
Any changes or modifications that the present invention is done are fallen within the scope of the claimed invention.
Claims (10)
1. a kind of high-performance antibiosis composite material, which is characterized in that be mainly prepared according to parts by weight by following components:
35~95 parts of polyphthalamide (PPA), ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate (E-GMA-
MA) 5~50 parts, 0.5-35 parts of nano-silver powder, 0.5-35 parts of nano-titanium dioxide, 5-15 parts of dispersing agent, coupling agent 0.1~1.5
Part, 0.5~1 part of antioxidant.
2. high-performance antibiosis composite material according to claim 1, which is characterized in that the number of polyphthalamide is divided equally
Son amount is that heat distortion temperature (HDT) is 295-300 DEG C under 1.5 ten thousand~5.0 ten thousand, 1.80MPa.
3. high-performance antibiosis composite material according to claim 1, which is characterized in that ethylene-methyl methacrylate shrinks sweet
In grease-methyl acrylate copolymer, the mass percent of glycidyl methacrylate is 3~20%, methyl acrylate
Mass percent be 10~40%.
4. high-performance antibiosis composite material according to claim 1, which is characterized in that the average grain diameter of nano-silver powder
20nm-350nm, specific surface area 0.5-50m2/g。
5. high-performance antibiosis composite material according to claim 1, which is characterized in that the average grain diameter of nano-titanium dioxide
15nm-150nm, specific surface area 10-90m2/g。
6. high-performance antibiosis composite material according to claim 1, which is characterized in that dispersing agent is by phosphoric acid salt and hard
The mass ratio of the composite dispersing agent of acyl amine composition, phosphoric acid salt and stearmide is 1:5~4:1.
7. high-performance antibiosis composite material according to claim 6, which is characterized in that the phosphoric acid salt includes polyphosphoric acid
Any one of sodium, calgon and triethyl group hexyl phosphoric acid or several compounds；Stearmide includes vinyl
Any one of bis-stearamides, glyceryl monostearate, glyceryl tristearate, oleamide are several compound
Object.
8. high-performance antibiosis composite material according to claim 1, which is characterized in that the coupling agent is to be by weight ratio
The phthalate ester coupling agent and zirconium ester coupling agent of 1:1~1:3 forms, and purity is higher than 99.5%.
9. high-performance antibiosis composite material according to claim 1, which is characterized in that the antioxidant is 1 by weight ratio:
The antioxidant 1010 of 1.5:1,168 and HP-136 composition.
10. a kind of preparation method of high-performance antibiosis composite material according to claim 1 to 9, feature exist
In, comprising the following steps:
S1, by the polyphthalamide of corrresponding quality number, ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate, idol
Connection agent and antioxidant are added to high-speed mixer, mix 15-25min, and 300~1000rpm of revolving speed obtains material 1；
S2, by the nano-silver powder, nano-titanium dioxide and dispersing agent of corrresponding quality number in high-speed mixer mixing 15-25min,
300~1000rpm of revolving speed obtains material 2；
S3, respectively by material 1 from main spout, material 2 is added in parallel double-screw extruder from side spout and is granulated, and makes
Grain temperature is 310~350 DEG C, and screw speed is 200~600rpm, and using water ring pelletizing, cyclonic separation is dried to obtain high-performance
Antimicrobial composite material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337064A (en) * | 2021-06-17 | 2021-09-03 | 广东川奥高新科技有限公司 | Antibacterial wear-resistant runway floor composite material and preparation method thereof |
| CN113429658A (en) * | 2021-07-09 | 2021-09-24 | 深圳市自然梦家具有限公司 | Elastic mattress material, preparation method thereof and mattress |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113337064A (en) * | 2021-06-17 | 2021-09-03 | 广东川奥高新科技有限公司 | Antibacterial wear-resistant runway floor composite material and preparation method thereof |
| CN113337064B (en) * | 2021-06-17 | 2022-06-10 | 广东川奥高新科技有限公司 | Antibacterial wear-resistant runway floor composite material and preparation method thereof |
| CN113429658A (en) * | 2021-07-09 | 2021-09-24 | 深圳市自然梦家具有限公司 | Elastic mattress material, preparation method thereof and mattress |
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Application publication date: 20190712 |