CN109233286A - A kind of luffa/nano silver polymer composite material and preparation method - Google Patents
A kind of luffa/nano silver polymer composite material and preparation method Download PDFInfo
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/0806—Silver
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Abstract
The invention belongs to polymer composites technical fields, more particularly to luffa/nano silver polymer composite material preparation method, the described method includes: loofah fiber is successively pre-processed in alkaline solution and oxidant, it is then immersed in silver nitrate solution, pattern controlling agent and amine terminated polyether is added, pass through high temperature high pressure process, make silver nitrate, pattern controlling agent and amine terminated polyether enter inside loofah fiber in water heating kettle in the environment of high temperature and pressure in intensive micron duct arranged in parallel, make the silver nitrate reduction nano silver in micron duct by radiation treatment simultaneously, obtain nano silver modified loofah sponge fiber；It is sufficiently mixed nano silver modified loofah sponge fiber with high molecular polymer presoma；Heating, curing process, obtain luffa/nano silver modified synergic polymer composites, the conductive capability of the composite material 3~8 orders of magnitude higher than traditional C-base composte material, and flexibility is good, elasticity is good, have antibacterial action.
Description
Technical field
The invention belongs to polymer composites technical fields, and in particular to a kind of luffa/nano silver polymer is compound
Material and preparation method thereof.
Background technique
With the development of society, environment and resource scarcity problem become increasingly conspicuous, people seek into sight emphasis trend of purchasing
The comprehensive development and utilization research of this cheap and function admirable natural reproducible biomass resource, it is increasingly withered to can gradually get rid of
The fossil resources exhausted are restricted to brought by human lives, social production development.Miscellaneous biological material in nature
Not only have the characteristics that abundance, biodegradable and sustainable regeneration, but also usually all by nanometer to submicron-scale
Structural unit is self-assembly of multiple dimensioned labyrinth that is hard and soft and having, shows natural performance advantage and vdiverse in function
Property.Reserves are huge on earth for natural plant fiber material, are known as the material of height sustainable use, carry out such material
High-valued comprehensive utilization already becomes one of the research hotspot of domestic and international scientific research personnel.
Sponge gourd is the annual climber herbaceous plant of Curcurbitaceae Luffa, as a kind of emerging industrial crops, at home
There is extensive plantation in outer tropical and subtropical region.Luffa is that mature sponge gourd fruit removes the fiber obtained after crust and seed
The natural vascular tissue of endoplasmic reticular structure also known as sponge gourd sponge, plant sponge.In recent years, with the development of science and technology, luffa
Through scientific development, quietly become a kind of novel natural industrial material, in packaging, noise elimination, filtering, heat preservation, damping and anti-impact
The engineering fields such as buffer are hit to be applied.
Nano silver has excellent electric conductivity, catalytic, broad spectrum antibacterial and unique skin effect, bulk effect, amount
Sub- dimensional effect and macroscopical tunnel-effect, are widely used in catalysis material, low temperature superconducting material, biosensor, printed circuit,
The fields such as textile material antibiotic finish are a kind of new function materials of rapid development.The pattern of Argent grain has correlated performance
Spherical silver powder is compared in important influence, and flake nano silver is mostly line contact or face contact between particle when forming conductive path, is led
Electrical property improves, and is widely used in fields such as electrocondution slurry, conducting resinl, electromagnetic shieldings and capacitor, film are opened
One of main electrode materials of electronic components such as pass.
Summary of the invention
Invention broadly provides a kind of graphene/nano silver polymer composites and preparation method thereof, the composite woods
Material has excellent conducting function.Its technical solution is as follows:
Luffa possesses advantage of the natural fiber as composite material reinforced phase, as low-density, high intensity, reproducibility,
Degradability.In addition, can have the nano-silver loaded of conducting function in its network knot itself because it is with natural network structure
Prefabricated conductive network skeleton is formed on structure, then compound with polymeric matrix progress, there is answering for excellent conducting function to prepare
Condensation material.The surface physicochemical property of luffa, such as absorption, wetting, thermal stability, adhesion and chemical reactivity, to its institute
The integrated application performance of the composite material of preparation influences significant.In order to overcome poor compatibility etc. between luffa and macromolecule matrix
Deficiency needs to be modified processing to luffa surface.
A kind of preparation method of luffa/nano silver polymer composite material, comprising the following steps:
(1) by loofah fiber and alkaline solution mixed processing, the molar concentration of the alkaline solution is 0.001mol/L
~5mol/L, mixed processing time are 0.5~50h, and mixed processing temperature is 20~60 DEG C, is cleaned with deionized water to neutrality
It dries again afterwards, then by loofah fiber and oxidizing agent solution mixed processing, the molar concentration of the oxidizing agent solution is
0.001mol/L~5mol/L, mixed processing time are 0.5~50h, and mixed processing temperature is 20~60 DEG C, clear with deionized water
It is washed till neutrality to dry again later, obtains oxidation processes loofah fiber；Luffa is a kind of renewable resource of green, has and
The features such as source is abundant, biodegradable and sustainable regeneration, because it is with unique light porous space network and excellent
Comprehensive performance, so as in composite material carry nano silver skeleton, obtain excellent modified effect；
(2) hydrothermal reaction kettle is added in silver nitrate solution, then the loofah fiber immersion silver nitrate after oxidation processes is molten
In liquid, pattern controlling agent is added and there is the amine terminated polyether of reduction and peptizaiton simultaneously, hydrothermal reaction kettle is heated, nitre is made
Sour silver, pattern controlling agent and amine terminated polyether enter inside loofah fiber in the environment of high temperature and pressure in water heating kettle intensively puts down
In the micron duct of row arrangement, in order to overcome the capillary effect inside loofah fiber in micron duct, the present invention utilizes hydro-thermal
The high temperature and high pressure environment that reaction kettle generates under air-tight state makes sour silver, pattern controlling agent and amine terminated polyether enter luffa
In the intensive micron duct arranged in parallel of fibrous inside, do not need using micron syringe needle or ultra-fine syringe needle, with simple and effective
Advantage；Simultaneously through laser pulse, microwave, ultraviolet light, gamma-rays or plasma beam radiation treatment, make the silver nitrate in micron duct
It is reduced to nano silver, obtains nano silver modified loofah sponge fiber, present invention uses have reduction silver nitrate and dispersion institute simultaneously
The amine terminated polyether of the nano-Ag particles effect of generation, is combined into one reducing agent and stabilizer in conventional manufacturing process, letter
Production procedure is changed, while having reduced the use of chemical reagent, to improve production efficiency, has reduced composite material and prepared
Environmental pollution in journey；
(3) make nano silver modified loofah sponge fiber and liquid macroimolecule polymer precursor abundant under the action of ultrasonic wave
Mixing forms nano silver modified loofah sponge fiber/high molecular polymer precursor mixture；It is fine to heat nano silver modified loofah sponge
Then dimension/high molecular polymer precursor mixture carries out curing process, the temperature of heating is 48~85 DEG C, and curing time is
1.5~6h, solidification temperature are 85~155 DEG C, luffa/nano silver modified synergic polymer composites are obtained, liquid
The injection of high molecular polymer performed polymer makes it be fully infiltrated into nano silver equipped in the network mold of nano silver modified loofah sponge fiber
Modified loofah sponge network of fibers is not required to during mixing nano silver modified loofah sponge fiber and high molecular polymer presoma
Carry out mechanical stirring, it is only necessary to simple dipping filling processing, and be not in the problem of part is reunited, the reaction of formation
Mixed liquor uniformity is high.
Further, in step (1), the alkaline solution is sodium hydroxide solution, potassium hydroxide solution and hydrogen-oxygen
Change one of calcium solution or a variety of.
Further, in step (2), the oxidant is hydrogen peroxide, Peracetic acid, sodium dichromate, chromic acid, nitre
Acid, sulfuric acid, chloric acid, bromic acid peroxy-disulfuric acid, hypoiodous acid, acid iodide, potassium permanganate, ammonium persulfate, sodium hypochlorite, SODIUM PERCARBONATE, mistake
Boratex, potassium perborate, selenic acid and any one or more of mixture of telluric acid.
Further, in step (3), the concentration of the silver nitrate solution is 0.1~5g/L, solvent for use N, N-
Dimethylformamide or deionized water.Pattern controlling agent used is any one of sodium chloride, vulcanized sodium, iron chloride and copper chloride
Or a variety of mixtures, concentration are 0.000001~0.1mol/L.Amine terminated polyether used is Huntsman company
D-230, D-400 of JEFFAMINE series, D-2000, D-4000, ED-600, ED-900, ED-2003, EDR-148, T-403,
T-3000 and T-5000 any one or more of mixture, concentration are 0.01~5g/L, silver nitrate and loofah fiber
Mass ratio be 0.001~10:1, time in hydrothermal reaction kettle is 0.5~72h, and reaction temperature is 40~400 DEG C.
Further, in step (3), when laser pulse is handled, the wavelength of laser is 355~1064nm, laser intensity
For 0.0001~500J/ pulse, pulse width was 1 picosecond~100 nanoseconds, and pulse frequency is 1~100Hz；It is micro- when microwave treatment
Wave frequency rate is 20~20000MHZ, and the time is 0.1~400min, and microwave output power is 50W~50000W；When ultraviolet processing,
The wavelength of ultraviolet light is 100~400nm, and power is 50W~5000W, and the processing time is 0.1~400min；When gamma-rays processing,
Gamma-ray dosage is 0.01~1000Gy, and the processing time is 0.1~400min；When plasma beam processing, emit plasma beam
Current strength be 0.01~100A, the processing time be 0.1~400min.
Further, in step (3), the micron openings of obtained nano silver modified loofah sponge fiber surface or fibrous inside
Contain nano silver in road.The density of fiber is 0.05g/cm3~15g/cm3, conductivity is 0.001S/cm~100S/cm.Nanometer
The three-dimensional mutually lapping network structure that silver-colored modified loofah sponge fiber itself is made of cellulose, this structure is as support frame
The intensity and flexibility of composite material will be dramatically increased；Contained nano silver will in the micron duct of fiber surface or fibrous inside
Dramatically increase the conductive capability and antibacterial ability of composite material.Therefore, the luffa prepared/nano silver modified synergic polymer
Composite material can bear more bending and stretcher strain, be a kind of composite wood for having both excellent conductive capability and anti-microbial property
Material.
Further, in step (4), high molecular polymer presoma is silicon rubber presoma, polyurethane presoma, ring
Oxygen resin precursor, paraffin presoma, nylon monomer-cast nylon presoma, polymethyl methacrylate presoma, polyimide precursor,
Polystyrene presoma, natural emulsion presoma or polypropylene presoma.
Further, in step (3), nano silver modified loofah sponge fiber mixes laggard with high molecular polymer presoma
Row ultrasonic treatment and vacuumize process, ultrasonic temperature are 30~80 DEG C, and ultrasonic power is 100~6000W, and ultrasonic time is 0.5
~5h；Vacuum degree is 0.04~0.12atm, and vacuum processing time is 5~70min.Vacuum processing can remove reaction mixture
In bubble so that reaction mixture is fully infiltrated into nano silver modified loofah sponge network of fibers.
The polymer composites of above method preparation can be used as conducing composite material, elastic conductor or antimicrobial composite material
It uses.
Using the above scheme, the invention has the following advantages that
(1) high temperature and high pressure environment that the present invention is generated under air-tight state using hydrothermal reaction kettle, makes silver nitrate, pattern control
Preparation and amine terminated polyether enter in micron duct intensively arranged in parallel inside loofah fiber, do not need using micron syringe needle
Or ultra-fine syringe needle, have the advantages that simple and effective；
(2) when carrying out the radiation treatment of laser pulse or microwave or ultraviolet or gamma-rays or plasma beam to silver nitrate,
Silver nitrate is gone back using there is reduction silver nitrate simultaneously and disperse the amine terminated polyether of nano-Ag particles effect generated
Original is combined into one reducing agent and stabilizer in conventional manufacturing process, simplifies production procedure, while reducing chemical reagent
Use reduce the environmental pollution in composite material preparation process to improve production efficiency；
(3) nano silver modified loofah sponge fiber is three formed by pretreatment loofah fiber skeleton and nano silver hydridization
Mutual lapping network structure is tieed up, the electric conductivity of composite material, luffa obtained/nano silver modified synergic can be dramatically increased
The conductive capability of polymer composites 3~8 orders of magnitude higher than traditional polymer based conductive composite material；It furthermore can be further
Increase the flexibility and intensity of composite material, is so as to bear more bending and stretcher strain, manufactured composite material
The composite material that a kind of flexibility is good, intensity is high；
(4) present invention has the characteristics that easy to operate, at low cost and is easy to structure regulating, is expected to become large-scale production height
It is compound to can be widely applied to conducing composite material, elastic conductor and antibacterial for the universal method of performance conducting polymer composite material
Material Field.
Specific embodiment
Experimental method in following embodiment is conventional method unless otherwise required, related experiment reagent and material
Material is conventional biochemical reagent and material unless otherwise required.
Embodiment 1
One, the preparation of nano silver modified loofah sponge fiber
Luffa is cut into the block cylinder of 1cm*1cm*1cm, is put into beaker, is added the 1L's of preparation in beaker
The NaOH solution of 0.001mol/L places 50h at 50 DEG C.It is dried after being cleaned again with deionized water to neutrality；It is placed again into burning
Cup, the hydrogenperoxide steam generator of the 0.05mol/L of the 1L of preparation is added in beaker, places 10h at 30 DEG C.Deionized water is used again
It is dried after cleaning to neutrality, obtains pretreatment loofah fiber.
The silver nitrate solution of the 0.5g/L of addition 20mL into dry hydrothermal reaction kettle, the sodium chloride of 0.001g,
The ED-900 of 0.005g and above-mentioned pretreatment loofah fiber, place 10h at 180 DEG C, while carrying out microwave treatment and make nitre
Sour silver, sodium chloride and ED-900 enter in the micron duct inside loofah fiber, and microwave frequency 1000MHZ, power are
800W.It is taken out from hydrothermal reaction kettle, obtains nano silver modified loofah sponge fiber.
The nano silver modified loofah sponge fibre density of preparation is 0.19g/cm3, conductivity 0.11S/cm.
Two, luffa/nano silver polymer composite material preparation
1. the high molecular polymer presoma of the present embodiment is silicon rubber presoma, model Dowcorning's
Sylgard-184 (contains curing agent).Silicon rubber: α, ω-hydroxyl dimethyl silicone polymer (PDMS) technical grade, are by Jinan state
The production of Chemical Co., Ltd. of nation；Crosslinking agent (ethyl orthosilicate is analyzed pure) and catalyst (dibutyltindilaurylmercaptide cinnamic acid is analyzed pure)
It is to be produced by Co., Ltd of Shanghai Resin Factory.
2. silicon rubber presoma the preparation method is as follows: the mass ratio of silicon rubber and crosslinking agent, catalyst is 100:4:1,
Using petroleum ether as solvent, about 5 minutes are vigorously stirred after mixing to full and uniform, and in the ultrasound of power 600w, frequency 10000HZ
The lower dispersion 10min of effect makes it be uniformly dispersed, then vacuum degassing is steeped 10 minutes, and silicon rubber presoma is obtained.
3. luffa/nano silver modified synergic silicon rubber composite material preparation method: first by the modified sponge gourd of nano silver
Network fiber is placed in a mold, is then injected into silicon rubber presoma, is permeated it and is sufficiently infiltrated nano silver modified loofah sponge fibre
Dimension forms reaction mixture.In reaction mixture, the mass content of nano silver modified loofah sponge fiber is 1%, polyphosphazene polymer
The mass content for closing object presoma is 99%.Mix it uniformly by ultrasonic treatment reaction mixture.Supersonic frequency is
10000HZ, power 800W.Hereafter it is vacuum-treated again, vacuum degree 0.1atm used, vacuum processing time 60 minutes.Very
Vacancy reason makes the air bubble expansion in reaction mixture and emersion liquid level and removes, and reaction mixture is made more fully to penetrate into nanometer
In the gap of silver-colored modified loofah sponge fiber.By the homogeneous mixture of nano silver modified loofah sponge fiber and silicon rubber precursor solution
85 DEG C, and heat preservation solidification 6 hours are heated to, luffa/nano silver modified synergic silicon rubber composite material is obtained.
In luffa manufactured in the present embodiment/nano silver modified synergic silicon rubber composite material, loofah fiber quality contains
Amount about 1.4%, nano Silver quality content is about 0.12%, and the conductivity of composite material is about 0.17S/cm, is changed with nano silver
The conductivity of property loofah fiber is almost the same, six orders of magnitude higher than traditional polymer based conductive composite material.Composite material
To the sterilizing rates of Escherichia coli up to 80.8%.In addition, the tensile strength of pure silicone rubber is 0.31MPa, by method of the invention
Modified, tensile strength is promoted to 0.45MPa, higher than pure silicone rubber by 27%.
Luffa/nano silver modified synergic silicon rubber composite material has very excellent electricity as a kind of elastic conductor
With mechanical property and very high mechanical stability, when bending to 2.5mm radius of curvature, the resistance of composite material only rises 5%,
And resistance does not also change significantly after being subjected to 3,000 alternating bendings.When composite material is subjected to bigger deformation as being bent
To 0.4mm radius of curvature and 50% tensile deformation under resistance also only rise less than 20%, and can continue to bear high
Up to 70% stretcher strain.
Embodiment 2
One, the preparation of nano silver modified loofah sponge fiber
Luffa is cut into 1cm*0.5cm*0.5cm bulk cylinder, beaker is put into, is added the 1L's of preparation in beaker
The KOH solution of 5mol/L is placed 0.5h at 20 DEG C, then is dried after being cleaned with deionized water to neutrality；It is placed again into beaker,
The liquor natrii hypochloritis of the 0.03mol/L of the 1L of preparation is added in beaker, places 7h at 25 DEG C, then with deionized water clean to
It is dried after neutrality.Obtain pretreatment loofah fiber.
The silver nitrate solution of the 1.0g/L of 10mL, the vulcanized sodium of 0.003g, 0.01g are added into dry hydrothermal reaction kettle
D-2000 and above-mentioned pretreatment loofah fiber, 12h is placed at 150 DEG C, at the same carry out laser pulse processing make nitric acid
Silver, vulcanized sodium and D-2000 enter in the micron duct inside loofah fiber, and the wavelength of laser is 1064nm, and laser intensity is
0.5J/ pulse, pulse width are 10 nanoseconds, pulse frequency 10Hz.It is taken out from hydrothermal reaction kettle, vacuum drying is received
The silver-colored modified loofah sponge fiber of rice.
The nano silver modified loofah sponge fibre density of preparation is 0.31g/cm3, conductivity 0.44S/cm.
Two, luffa/nano silver polymer composite material preparation
1. the present embodiment high molecular polymer presoma is epoxy resin presoma, epoxy resin is epoxy resin 828, is
It is produced by Shanghai City Hongxin Chemical trade Co., Ltd, curing agent is diethylenetriamine, is limited by Chinese medicines group chemical reagent
Company's production.
2. epoxy resin presoma the preparation method is as follows: epoxy resin 828 and diethylenetriamine are mixed by the mass ratio of 2:1
About 10 minutes are vigorously stirred after conjunction to full and uniform, and power 400w, frequency 10000HZ ultrasonication under disperse 20min
It is made to be uniformly dispersed.Vacuum de-soak 20 minutes again obtain epoxy resin presoma.
3. luffa/nano silver modified synergic epoxy resin composite material preparation method: first by the nano silver of preparation
Modified loofah sponge fiber is placed in a mold, is then injected into epoxy resin presoma, so that it is permeated and is sufficiently infiltrated nano silver and is changed
Property loofah fiber, formed reaction mixture.In reaction mixture, the mass content of nano silver modified loofah sponge fiber is
5%, the mass content of high molecular polymer presoma is 95%.Mix it uniformly by ultrasonic treatment reaction mixture.
Supersonic frequency is 20000HZ, power 1500W.Hereafter it is vacuum-treated again, vacuum degree 0.06atm used, when vacuum processing
Between 30 minutes.Vacuum processing makes the air bubble expansion in reaction mixture and emersion liquid level and removes, and keeps reaction mixture more abundant
Penetrate into the gap of nano silver modified loofah sponge fiber.Nano silver modified loofah sponge fiber and epoxy resin presoma is molten
The homogeneous mixture of liquid is heated to 100 DEG C, and heat preservation solidification 1.5 hours, obtains luffa/nano silver modified synergic epoxy resin
Composite material.
Loofah fiber quality in luffa prepared by the present embodiment/nano silver modified synergic epoxy resin composite material
Content is about 3%, and nano Silver quality content is about 0.5%, and conductivity is about 2.3S/cm, with nano silver modified loofah sponge fiber
Conductivity it is almost the same, six orders of magnitude higher than Conventional nano silver-based composite material.Sterilization of the composite material to Escherichia coli
Rate is up to 73.2%.The tensile strength of pure epoxy resin is 23.55MPa, and luffa prepared by the present embodiment/nano silver collaboration changes
The tensile strength of property epoxy resin composite material is 35.04MPa, higher than pure epoxy resin by 36%.
Embodiment 3
One, the preparation of nano silver modified loofah sponge fiber
Luffa is ground into the staple fiber of 0.1~0.5mm long with pulverizer, is put into beaker, is added and prepares in beaker
1L 0.5mol/L calcium hydroxide solution, 5h is placed at 30 DEG C, then dry after being cleaned with deionized water to neutrality；Again
It is put into beaker, the peracetic acid soln of the 0.01mol/L of the 1L of preparation is added in beaker, 6h is placed at 25 DEG C, then spend
Ionized water is dried after cleaning to neutrality.Obtain pretreatment loofah fiber.
The silver nitrate solution of the 0.05g/L of addition 30mL into dry hydrothermal reaction kettle, the iron chloride of 0.001g,
The T-5000 of 0.02g and above-mentioned pretreatment loofah fiber, place 10h at 200 DEG C, at the same carry out gamma-rays processing make
Silver nitrate, iron chloride and T-5000 enter in the micron duct inside loofah fiber, and gamma-ray dosage is 200Gy.From water
It is taken out in thermal response kettle, vacuum drying, obtains nano silver modified loofah sponge fiber.
The nano silver modified loofah sponge fibre density of preparation is 0.14g/cm3, conductivity 1.7S/cm.
Two, luffa/nano silver polymer composite material preparation
1. the natural emulsion presoma that the present embodiment high molecular polymer presoma is 60%, natural emulsion, that is, natural rubber
Glue, natural rubber come from Xishuangbanna Jing Yang limited rubber responsible company, solid content 60%.
2. luffa/nano silver modified synergic natural emulsion composite material (i.e. luffa/nano silver modified synergic genuine milk
Glue condom products) preparation method: the modified loofah sponge staple fiber of preparation is mixed with natural emulsion, formed modified loofah sponge
Staple fiber natural emulsion mixture permeates it and sufficiently infiltrates modified loofah sponge staple fiber.Add 1% stably dispersing
Agent, 0.2% surfactant, 1% promotor, 0.8% anti-aging agent, 2% vulcanizing agent and 0.5% sulfurate activity
Agent, dispersion stabilizer are sodium laurate or F108, and surfactant is cetyl benzenesulfonic acid, and promotor is diethyl-dithio
Carbaminate, anti-aging agent 2,6- di-tert-butyl-4-methy phenol, vulcanizing agent are sulphur, and vulcanizing activator is zinc oxide.Change
Property luffa staple fiber and natural emulsion be sufficiently mixed uniformly after power 400w, frequency 10000HZ ultrasonication under disperse
20min makes it be uniformly dispersed.Hereafter it is vacuum-treated again, vacuum degree 0.06atm used, vacuum processing time 30 minutes.Very
Vacancy reason makes the air bubble expansion in natural emulsion and emersion liquid level and removes, and natural emulsion is made more fully to penetrate into modified sponge gourd
In the gap of network staple fiber, viscosity is 8mPas or so.Glue after will be compound stands 24 hours or so, cures it sufficiently,
Then heat drying after impregnated three times with condom mold is added in impregnator to be solidified to 100 DEG C, obtain luffa/
Nano silver modified synergic natural emulsion condom products.
Loofah fiber matter in luffa prepared by the present embodiment/nano silver modified synergic natural emulsion condom products
Measuring content is about 6%, and nano Silver quality content is about 0.7%, and luffa/nano silver modified synergic natural emulsion sheath
The tensile strength of product is higher than pure natural latex by 22%, (tensile strength of pure natural latex is 2.23MPa)；Than pure natural latex
Elongation at break it is high by 24%, the elongation at break of pure natural latex is 270%.Sheath is because containing loofah fiber and nanometer
Silver and cause the roughness on surface layer to increase, when in use can because friction increase due to generate more pleasant sensations.Contained by sheath
Luffa staple fiber and nano silver and human body have natural compatibility and sterilizing function, meanwhile, luffa/nano silver and latex
Compound action keep micropore less, substantially reduce AIDS virus, hepatitis B, hepatitis C virus, human papilloma virus it is saturating
Probability is crossed, luffa/nano silver modified synergic natural emulsion condom products condom thickness can reach 0.01~0.3mm, energy
Enough meet the requirement of condom.
Embodiment 4
One, the preparation of nano silver modified loofah sponge fiber
Luffa is cut into 1cm*1cm*3cm strip cylinder, beaker is put into, is added the 1L's of preparation in beaker
The NaOH solution of 0.05mol/L is placed 10h at 30 DEG C, then is dried after being cleaned with deionized water to neutrality；It is placed again into burning
Cup, the potassium perborate solution of the 0.04mol/L of the 1L of preparation is added in beaker, 8h is placed at 45 DEG C, then use deionized water
It is dried after cleaning to neutrality.Obtain pretreatment loofah fiber.
The silver nitrate solution of the 2.0g/L of 50mL, the copper chloride of 0.008g, 0.02g are added into dry hydrothermal reaction kettle
EDR-148 and above-mentioned pretreatment loofah fiber, 10h is placed at 160 DEG C, at the same carry out plasma beam processing make nitre
Sour silver, copper chloride and EDR-148 enter in the micron duct inside loofah fiber, when plasma beam is handled, emit plasma
The current strength of beam is 10A.It is taken out from hydrothermal reaction kettle, vacuum drying, obtains nano silver modified loofah sponge fiber.
The nano silver modified loofah sponge fibre density of preparation is 0.39g/cm3, conductivity 11S/cm.
Two, luffa/nano silver polymer composite material preparation
1. the present embodiment high molecular polymer presoma is polymethyl methacrylate presoma, polymethyl methacrylate
Presoma the preparation method is as follows: acetone mixes with polymethyl methacrylate according to mass ratio 1:2 after, it is small to be vigorously stirred about 15
Up to full and uniform, and power 600w, frequency 10000HZ ultrasonication under disperse 40min, so that it is uniformly dispersed.Then
Vacuum de-soak 30 minutes, obtain polymethyl methacrylate presoma.
2. luffa/nano silver modified synergic composite material of polymethyl methacrylate preparation method: by receiving for preparation
The silver-colored modified loofah sponge fiber of rice is placed in a mold, and is injected polymethyl methacrylate presoma, permeate it and sufficiently soaked
Moisten nano silver modified loofah sponge fiber.Nano silver modified loofah sponge fiber and polymethyl methacrylate presoma are sufficiently mixed
Further it is mixed uniformly by ultrasonic treatment after even.Supersonic frequency is 20000HZ, power 1500W.Hereafter it carries out again true
Vacancy reason, vacuum degree 0.06atm used, vacuum processing time 30 minutes.It is vacuum-treated the air bubble expansion made in polymer solution
And emersion liquid level and remove, penetrate into polymer solution more fully in the gap of nano silver modified loofah sponge fiber.It will receive
The homogeneous mixture of the silver-colored modified loofah sponge fiber of rice and polymethyl methacrylate precursor solution is heated to 48 DEG C, fills acetone
Divide volatilization, is again heated to 155 DEG C and heat preservation solidification 1.5 hours, obtains luffa/carbon black modified synergic polymethyl methacrylate
Composite material.
Luffa in luffa prepared by the present embodiment/nano silver modified synergic composite material of polymethyl methacrylate
Fiber quality content is about 5.6%, and nano Silver quality content is about 0.6%, and conductivity is about 0.9S/cm, modified with nano silver
The conductivity of loofah fiber is almost the same, six orders of magnitude higher than Conventional nano silver-based composite material.Composite material is to large intestine
The sterilizing rate of bacillus is up to 66.2%.In addition, the tensile strength of pure polymethyl methacrylate is 30.60MPa, the present embodiment is made
Standby luffa/nano silver modified synergic composite material of polymethyl methacrylate tensile strength is 38.22MPa, more poly- than pure
Methyl methacrylate is high by 18.1%.
Embodiment 5
One, the preparation of nano silver modified loofah sponge fiber
The nano silver modified loofah sponge fiber is in the same manner as in Example 1.
Two, luffa/nano silver polymer composite material preparation
1. the present embodiment high molecular polymer presoma is 6 presoma of nylon monomer-cast nylon, 6 presoma of nylon monomer-cast nylon is by China
The caprolactam of Ba Ling branch company of petrochemical industry limited liability company production.
2. luffa/6 composite material of nano silver modified synergic nylon monomer-cast nylon preparation method: the nano silver of preparation is modified
Loofah fiber is placed in a mold and is preheated to 170 DEG C.Caprolactam in another reaction kettle is warming up to 130 DEG C, decompression
Moisture is distilled off；Then 0.20g sodium hydroxide is added in reaction kettle, carries out vacuum distillation water removal again, is warming up to 140
DEG C, removal vacuum, and it is rapidly added 0.8g toluene di-isocyanate(TDI) activator, it stirs evenly, injection is put into advance rapidly receives
In 170 DEG C of mold of the silver-colored modified loofah sponge fiber of rice, nano silver modified loofah sponge fiber/caprolactam mixture is formed, is made
It permeates and sufficiently infiltrates nano silver modified loofah sponge fiber.Hereafter it is vacuum-treated again, vacuum degree 0.06atm used, very
It manages the time 5 minutes in vacancy.Vacuum processing makes the air bubble expansion in caprolactam and emersion liquid level and removes, and fills caprolactam more
That divides penetrates into the gap of nano silver modified loofah sponge fiber.It polymerization reaction 60 minutes, is demoulded after natural cooling.Obtain sponge gourd
Network/6 composite material of nano silver modified synergic nylon monomer-cast nylon.
Loofah fiber matter in luffa prepared by the present embodiment/6 composite material of nano silver modified synergic nylon monomer-cast nylon
Measuring content is about 2.5%, and nano Silver quality content is about 0.2%, and conductivity quality is about 0.03S/cm, with the modified silk of nano silver
The conductivity (0.04S/cm) of melon network fiber is almost the same, six orders of magnitude higher than conventional nano silver base nylon 6 composite material.It is multiple
Condensation material is to the sterilizing rates of Escherichia coli up to 53.0%.And the tensile strength of composite material is higher than pure nylon monomer-cast nylon by 15%, and it is (pure
The tensile strength of nylon monomer-cast nylon is 80.5MPa).
Embodiment 6
One, the preparation of nano silver modified loofah sponge fiber
The nano silver modified loofah sponge fiber is in the same manner as in Example 4.
Two, luffa/nano silver polymer composite material preparation
1. the natural emulsion presoma that the present embodiment high molecular polymer presoma is 60%, natural emulsion, that is, natural rubber
Glue, natural rubber come from Xishuangbanna Jing Yang limited rubber responsible company, solid content 60%.
2. luffa/nano silver modified synergic natural emulsion composite material (i.e. luffa/nano silver modified synergic genuine milk
Glue condom products) preparation method: by the nano silver modified loofah sponge fiber grinds of preparation, when grinding, uses milling apparatus
Grinding 6 hours.Mixed again with natural emulsion, formed modified loofah sponge staple fiber natural emulsion mixture, make its permeate and it is abundant
Infiltrate modified loofah sponge staple fiber.Add 1% dispersion stabilizer, 0.2% surfactant, 1% promotor,
0.8% anti-aging agent, 2% vulcanizing agent and 0.5% vulcanizing activator, dispersion stabilizer be sodium laurate or F108, table
Face activating agent is cetyl benzenesulfonic acid, and promotor is zinc diethyl dithiocarbamate, anti-aging agent 2,6- di-t-butyl-
4- methylphenol, vulcanizing agent are sulphur, and vulcanizing activator is zinc oxide.Modified loofah sponge staple fiber is sufficiently mixed with natural emulsion
Uniformly after power 400w, frequency 10000HZ ultrasonication under dispersion 20min so that it is uniformly dispersed.And further by micro-
Wave carries out irradiation reduction, microwave frequency 1000MHZ, power 800W.Hereafter it is vacuum-treated again, vacuum degree used
0.06atm, vacuum processing time 30 minutes.Vacuum processing makes the air bubble expansion in natural emulsion and emersion liquid level and removes, and makes
Natural emulsion more fully penetrates into the gap of modified loofah sponge staple fiber, and viscosity is 8mPas or so.Glue after will be compound
Liquid stands 24 hours or so, cures it sufficiently, is then added in impregnator impregnated with condom mold and heat afterwards three times
Dry to 100 DEG C are solidified, and luffa/nano silver modified synergic natural emulsion condom products are obtained.
Loofah fiber matter in luffa prepared by the present embodiment/nano silver modified synergic natural emulsion condom products
Measuring content is about 9%, and nano Silver quality content is about 2%, and luffa/nano silver modified synergic natural emulsion sheath produces
The tensile strength of product is higher than pure natural latex by 25%, (tensile strength of pure natural latex is 2.23MPa)；Than pure natural latex
Elongation at break is high by 29% (elongation at break of pure natural latex is 270%).Sheath is because containing loofah fiber and nanometer
Silver and cause the roughness on surface layer to increase, when in use can because friction increase due to generate more pleasant sensations.Contained by sheath
Luffa staple fiber and nano silver and human body have natural compatibility and sterilizing function, meanwhile, luffa/nano silver and latex
Compound action keep micropore less, substantially reduce AIDS virus, hepatitis B, hepatitis C virus, human papilloma virus it is saturating
Probability is crossed, luffa/nano silver modified synergic natural emulsion condom products condom thickness can reach 0.05~0.5mm, energy
Enough meet the requirement of condom.
It will be apparent to those skilled in the art that can make various other according to the above description of the technical scheme and ideas
Corresponding change and deformation, and all these changes and deformation all should belong to the protection scope of the claims in the present invention
Within.
Claims (10)
1. a kind of luffa/nano silver polymer composite material preparation method, it is characterised in that: the following steps are included:
(1) luffa is mixed with alkaline solution, is dried after being washed to neutrality, obtain pretreatment loofah fiber；
(2) pretreatment loofah fiber is mixed with oxidant, is dried after being washed to neutrality, it is fine obtains oxidation processes luffa
Dimension；
(3) oxidation processes loofah fiber is immersed in silver nitrate solution, pattern controlling agent and amine terminated polyether is added, to mixing
Object heating, while to mixture radiation treatment, obtain nano modification loofah fiber；
(4) it is sufficiently mixed nano modification loofah fiber with high molecular polymer presoma under ultrasonic wave effect, formation is received
Rice modified loofah sponge fiber/high molecular polymer precursor mixture, heats the mixture, carries out curing process, obtains silk
Melon network/nano silver modified synergic polymer composites.
2. luffa according to claim 1/nano silver polymer composite material preparation method, it is characterised in that: step
Suddenly the molar concentration of (1) neutral and alkali solution is 0.001-5mol/L, and incorporation time 0.5-50h, mixed processing temperature is 20-60
DEG C, the alkaline solution is selected from one or more of sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide solution.
3. luffa according to claim 1/nano silver polymer composite material preparation method, it is characterised in that: step
Suddenly the molar concentration of oxidation solution is 0.001-5mol/L in (2), and incorporation time 0.5-50h, mixed processing temperature is 20-60
DEG C, the oxidant be selected from hydrogen peroxide, Peracetic acid, sodium dichromate, chromic acid, nitric acid, sulfuric acid, chloric acid, bromic acid peroxy-disulfuric acid,
Hypoiodous acid, acid iodide, potassium permanganate, ammonium persulfate, sodium hypochlorite, SODIUM PERCARBONATE, sodium perborate, potassium perborate, selenic acid and telluric acid
One or more of.
4. luffa according to claim 1/nano silver polymer composite material preparation method, it is characterised in that: step
Suddenly pattern controlling agent described in (2) is selected from one of sodium chloride, vulcanized sodium, iron chloride and copper chloride or a variety of, pattern control
The concentration of agent is 0.000001-0.1mol/L；The amine terminated polyether be Huntsman company JEFFAMINE series D-230,
One in D-400, D-2000, D-4000, ED-600, ED-900, ED-2003, EDR-148, T-403, T-3000 and T-5000
Kind is several, and the concentration of the amine terminated polyether is 0.01-5g/L.
5. luffa according to claim 1/nano silver polymer composite material preparation method, it is characterised in that: step
Suddenly the mass ratio of silver nitrate and loofah fiber is 0.001-10:1 in (3), and heating temperature is 40-400 DEG C, and heating time is
0.5-72h。
6. luffa according to claim 1/nano silver polymer composite material preparation method, it is characterised in that: step
Suddenly radiation treatment is laser pulse, microwave, ultraviolet light, gamma-rays or plasma beam radiation treatment in (3)；The wavelength of laser is
355-1064nm, intensity are 0.0001-500J/ pulse, and pulse width is 1 picosecond of -100 nanosecond, pulse frequency 1-100Hz；
The microwave frequency of microwave treatment is 20-20000MHZ, time 0.1-400min, microwave output power 50-50000W；It is ultraviolet
The wavelength of line is 100-400nm, and power 50-5000W, the processing time is 0.1-400min；Gamma-ray dosage is 0.01-
1000Gy, processing time are 0.1-400min；The current strength for emitting plasma beam is 0.01-100A, and the processing time is 0.1-
400min。
7. luffa according to claim 1/nano silver polymer composite material preparation method, it is characterised in that: step
Suddenly the nano modification loofah fiber surface or internal micron duct that (3) obtain have included nano silver, and the density of fiber is 0.05-
15g/cm3, conductivity 0.001-100S/cm.
8. luffa according to claim 1/nano silver polymer composite material preparation method, it is characterised in that: step
Suddenly high molecular polymer presoma described in (4) is silicon rubber presoma, polyurethane presoma, epoxy resin presoma, paraffin
Presoma, nylon monomer-cast nylon presoma, polymethyl methacrylate presoma, polyimide precursor, polystyrene presoma, day
Right latex presoma or polypropylene presoma.
9. luffa according to claim 1/nano silver polymer composite material preparation method, it is characterised in that: step
Suddenly it is ultrasonically treated and is taken out after nano modification loofah fiber is mixed with high molecular polymer presoma in (4), before heating and is true
Vacancy reason, ultrasonic temperature is 30~80 DEG C, and ultrasonic power is 100~6000W, and ultrasonic time is 0.5~5h；Vacuum degree is 0.04
~0.12atm, vacuum processing time are 5~70min；The temperature for heating the mixture is 48~85 DEG C, and curing time is 1.5
~6h, solidification temperature are 85~155 DEG C.
10. a kind of polymer composites prepared by any one of claim 1-9 the method, it is characterised in that: described poly-
Compound composite material can be used as conducing composite material or antimicrobial composite material.
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