CN108018742A - A kind of preparation method of highly conductive antibacterial water proof type conductive paper - Google Patents

A kind of preparation method of highly conductive antibacterial water proof type conductive paper Download PDF

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CN108018742A
CN108018742A CN201711357932.1A CN201711357932A CN108018742A CN 108018742 A CN108018742 A CN 108018742A CN 201711357932 A CN201711357932 A CN 201711357932A CN 108018742 A CN108018742 A CN 108018742A
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liquid
self
starch
parts
mixed
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李巧珍
杨明忠
张建初
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
    • C08B30/18—Dextrin, e.g. yellow canari, white dextrin, amylodextrin or maltodextrin; Methods of depolymerisation, e.g. by irradiation or mechanically
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/003—Crosslinking of starch
    • C08B31/006—Crosslinking of derivatives of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/02—Esters
    • C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/10—Phosphorus-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds

Abstract

The present invention relates to conductive paper technical field of material, and in particular to a kind of preparation method of highly conductive antibacterial water proof type conductive paper.The present invention is using birch wood pulp cellulose as matrix, self-control carries silver-colored carbon nanotubes, carbon fiber dispersion liquid and self-control cationic starch powder are as reinforcing agent, and it is aided with polyvinyl alcohol and tributyl phosphate etc. and highly conductive antibacterial water proof type conductive paper is prepared, first by the modified dispersed water of chopped carbon fiber, obtain carbon fiber dispersion liquid, silver nitrate solution is recycled to be modified carbon nanotubes, improve the antibiotic property of conductive paper, carbon nanotubes is depended on carbon fiber and matrix, form complete conductive network structure, so as to improve the electric conductivity of conductive paper, sweet potato starch is carried out by epoxychloropropane and succinic anhydride dual modified, crosslinking Treatment can limit the absorption of moisture, improve the water proofing property of conductive paper, it is with a wide range of applications.

Description

A kind of preparation method of highly conductive antibacterial water proof type conductive paper
Technical field
The present invention relates to conductive paper technical field of material, and in particular to a kind of highly conductive antibacterial water proof type conductive paper Preparation method.
Background technology
Conductive paper is a kind of functional paper with conductive characteristic, can be conducted by electronics and corona discharge is quiet to eliminate Electricity, after conductive layer reaches certain thickness or conductive compositions reach certain proportion, it is possible to used as electromagnetic shielding material.Lead Electric paper has the function of conduction, heat conduction, electromagnetic shielding, electromagnetic wave absorption etc., can be widely used in the antistatic of all kinds of instrument Packaging, Aeronautics and Astronautics, the ELECTROMAGNETIC RADIATION SHIELDING cover of precise electronic industry, and actuator, sensor and resistance to heater etc..
The preparation method of conductive paper mainly has two kinds：First, wet end manufacturing process, by conductive filler with physically or chemically side Method is deposited on fiber surface, and the fibre thin layer with certain electric conductivity is obtained by traditional wet end forming technique；Second, surface Coating method, using conductive filler as main material, is aided with the auxiliary agents such as adhesive, prepares electrically-conducting paint, existed by surface coating method Paper surface forms conductive coating, prepares conductive paper.Obviously, surface coating process can only assign paper surface electric conductivity, and wet Portion's manufacturing process can be with the more excellent conductive paper of processability.
Being presently used for assigning the filler of paper electric conductivity mainly includes：Carbon black, carbon fiber, carbon nanotubes, graphite, graphite The conducting polymer such as alkene and polyaniline, polythiophene, polypyrrole.In above conductive filler, carbon nanotubes is because of its unique knot Structure receives a lot of attention with excellent physical and chemical performance, has weight in nanometer technology, electronics, optics and material science and technical field Want application value.Particularly excellent electrical conduction, heat transfer and mechanical performance, makes carbon nanotubes have widely in many fields Application space.
But since the combination power of carbon nanotubes and natural fiber or chemical fibre is not strong, so causing conductive paper easy There is dry linting phenomenon, electric conductivity is not sufficiently stable.In addition, in the long-term use, since the primary raw material of conductive paper is fine Cellulose fiber, cellulose fibre can adsorb many microorganisms, and if these microorganism proper temperatures, will breed rapidly, For a long time the decomposition of conductive paper can be caused to be denatured.Cellulose fibre also has very strong hydrophily and relatively low tensile strength, makes Conductive paper water proofing property it is very poor and physical strength is relatively low.These shortcomings of cellulose fibre have seriously affected the use of conductive paper Value.
Therefore, developing a kind of conductive paper that can solve above-mentioned performance issue is highly desirable.
The content of the invention
The technical problems to be solved by the invention：For current common conductive paper, there are poorly conductive, antibiotic property are poor and anti- Water is poor, the defects of can not meet market demands, there is provided a kind of preparation method of highly conductive antibacterial water proof type conductive paper.
In order to solve the above technical problems, the present invention is using technical solution as described below：
A kind of preparation method of highly conductive antibacterial water proof type conductive paper, it is characterised in that specifically preparation process is：
（1）Weigh 8~10g lauryl sodium sulfate to be poured into the beaker with 95~105mL deionized waters, be placed in ultrasound Sonic oscillation in ripple separating apparatus, obtains self-control dispersion liquid；
（2）Weigh 24~32g carbon nanotubes and pour into ball milling in ball mill, obtain carbon nanotube powder, by carbon nanotube powder, nitre Sour silver solution and self-control dispersion liquid mixing are placed in beaker and stir, and obtain stirring liquid, the pH to 4 of stirring liquid is adjusted with salpeter solution ~6, then stirring liquid is put into unglazed greenhouse and is mixed, decompression filters, and removes filtrate, takes out filter residue, filter residue is put into Dried in baking oven, obtain self-control and carry silver-colored carbon nanotubes；
（3）Weigh 32~36g sweet potato starch and be added in the beaker with 80~100mL deionized waters and be mixed, formed sediment Paste mixing liquid, cooled to room temperature, the pH to 5~6 of gelatinized corn starch liquid is adjusted with hydrochloric acid, obtains starch mixed liquor, then mix to starch Close and 2~4g isoamylases enzymolysis added in liquid, filtering removes filter residue, and it is starch reaction liquid to obtain filtrate, by starch reaction liquid, The sodium hydroxide solution and epoxychloropropane mixing that mass fraction is 5% are placed in beaker and stir, and obtain being mixed liquid, then to The succinic anhydride of liquid quality 0.8% is mixed in addition in beaker, continues insulated and stirred, filters and obtains solids, natural air drying, Grinding discharging, obtains self-control cationic starch powder；
（4）Carboxymethyl cellulose, chopped carbon fiber and deionized water are mixed and are placed in sonic oscillation in ultrasonic wave separating apparatus, is obtained Carbon fiber dispersion liquid；
（5）Count in parts by weight, weigh 30~40 parts of birch wood pulp celluloses respectively, 16~20 parts of self-controls carry silver-colored carbon nanotubes, 8~ 10 parts of carbon fiber dispersion liquids and 20~30 parts of deionized water mixing are placed in mixer and stir, then add 6~8 parts of self-control cations Starch powder, 5~7 parts of deionized waters, 2~4 parts of polyvinyl alcohol and 1~3 part of tributyl phosphate, continue to keep rotating speed mixing to stir Mix, obtain mixed slurry, mixed slurry is poured into mould, and be put into extrusion forming in paper machine, cooled to room temperature, goes out Material, you can highly conductive antibacterial water proof type conductive paper is made.
Step（1）The sonic oscillation time is 16~20min.
Step（2）The rotational speed of ball-mill is 80~100r/min, and Ball-milling Time is 45~60min, carbon nanotube powder, The silver nitrate solution and the mass ratio of self-control dispersion liquid that mass fraction is 32% are 1：5：2, mixing time is 20~30min, nitric acid The mass fraction of solution is 24%, and the mixings time be 1~2h, and drying temperature is 90~100 DEG C, drying time is 30~ 40min。
Step（3）The whipping temp is 65~75 DEG C, and mixing time is 10~12min, and the mass fraction of hydrochloric acid is 15%, hydrolysis temperature is 35~40 DEG C, and enzymolysis time be 1~2h, starch reaction liquid, mass fraction for 5% sodium hydroxide solution Volume ratio with epoxychloropropane is 4：2：1, it is 40~55 DEG C that temperature, which is mixed, and the mixing time is 20~30min, after Continuous mixing time is 45~60min.
Step（4）The mass ratio of the carboxymethyl cellulose, chopped carbon fiber and deionized water is 1：2：4, ultrasound is shaken It is 100~120r/min to swing rotating speed, and the sonic oscillation time is 1~2h.
Step（5）The speed of agitator is 120~160r/min, and mixing time is 16~20min, continues mixing time For 35~45min, the size of mould is quantification of 24g/m2, thickness 0.2mm, extrusion temperature be 100~120 DEG C, extruding pressure Power is 0.6~0.8MPa.
Compared with other methods, advantageous effects are the present invention：
（1）Using birch wood pulp cellulose as matrix, self-control carries silver-colored carbon nanotubes, carbon fiber dispersion liquid and self-control cation and forms sediment the present invention Powder powder is aided with polyvinyl alcohol and tributyl phosphate etc. and highly conductive antibacterial water proof type conductive paper is prepared as reinforcing agent, Chopped carbon fiber is modified first with carboxymethyl cellulose, makes in the dispersed water of chopped carbon fiber, obtains carbon fiber Dispersion liquid, recycles silver nitrate solution to be modified carbon nanotubes, since most pathogen is unicellular microorganism, is Remain metabolic by protease, the silver ion in silver nitrate attracts to carry the mercapto of negative electrical charge in protease, and fast Speed is in connection, effectively pierces through cell membrane and cell membrane appearance, makes bacterial cell because of protein denaturation, and can not breathe, generation Thank and breed, until it is dead, the antibiotic property of conductive paper is improved, while silver ion also plays conductive work in sterilization process With in addition carbon nanotubes is depended on carbon fiber and matrix, and is filled between the hole of matrix, forms complete conductive network knot Structure, so as to improve the electric conductivity of conductive paper, the length of wherein carbon fiber is longer, there is preferable continuity in conductive paper, realizes The long-range continuity of conductive paper, the conductive network structure for being conducive to build is more complete, improve the electric conductivity of conductive paper；
（2）The present invention is dual modified to sweet potato starch progress by epoxychloropropane and succinic anhydride, in the effect of modified starch Under, the interface of formation some strength, esterification process can be substituted by hydroxyl between conductive paper fiber, and it is hydrophobic to impart starch Property, crosslinking Treatment increases intramolecule and intermolecular contact in the random site of starch granules, simultaneously because can increase shallow lake Crosslinked density in powder structure, so as to limit the absorption of moisture, improves the water proofing property of conductive paper, before having a wide range of applications Scape.
Embodiment
Weigh 8~10g lauryl sodium sulfate to pour into the beaker with 95~105mL deionized waters, be placed in ultrasound 16~20min of sonic oscillation in ripple separating apparatus, obtains self-control dispersion liquid；24~32g carbon nanotubes is weighed to pour into ball mill, Rotating speed is 45~60min of ball milling under conditions of 80~100r/min, obtains carbon nanotube powder, is in mass ratio 1：5：2 by carbon Nanotube powder, the silver nitrate solution that mass fraction is 32% and self-control dispersion liquid mixing are placed in 20~30min of stirring in beaker, Obtain stirring liquid, with mass fraction be 24% salpeter solution adjust stirring liquid pH to 4~6, then will stirring liquid be put into it is unglazed 1~2h is mixed in greenhouse, decompression filters, and removes filtrate, takes out filter residue, filter residue is put into baking oven, temperature for 90~ 30~40min is dried under conditions of 100 DEG C, self-control is obtained and carries silver-colored carbon nanotubes；Weigh 32~36g sweet potato starch and be added to and carry In the beaker of 80~100mL deionized waters, 10~12min is mixed at being 65~75 DEG C in temperature, obtains gelatinized corn starch liquid, from So it is cooled to room temperature, the pH to 5~6 of gelatinized corn starch liquid is adjusted with the hydrochloric acid that mass fraction is 15%, obtains starch mixed liquor, then to 2~4g isoamylases are added in starch mixed liquor, digest 1~2h at being 35~40 DEG C in temperature, filtering removes filter residue, filtered Liquid is starch reaction liquid, by starch reaction liquid, the sodium hydroxide solution that mass fraction is 5% and epoxychloropropane by volume For 4：2：1 mixing is placed in beaker, is stirred 20~30min at being 40~55 DEG C in temperature, is obtained that liquid is mixed, then to beaker The succinic anhydride of liquid quality 0.8% is mixed in middle addition, continues 45~60min of insulated and stirred, and suction filtration obtains solids, natural Air-dry, grinding discharging, obtains self-control cationic starch powder；It is 1 in mass ratio：2：4 by carboxymethyl cellulose, chopped carbon fiber It is placed in deionized water mixing in ultrasonic wave separating apparatus, 1~2h of sonic oscillation under conditions of rotating speed is 100~120r/min, Obtain carbon fiber dispersion liquid；Count in parts by weight, weigh 30~40 parts of birch wood pulp celluloses respectively, 16~20 parts of self-controls carry silver-colored carbon Nanotube, 8~10 parts of carbon fiber dispersion liquids and the mixing of 20~30 parts of deionized waters are placed in mixer, rotating speed for 120~ 16~20min is stirred under conditions of 160r/min, then adds 6~8 parts of self-control cationic starch powder, 5~7 parts of deionized waters, 2 ~4 parts of polyvinyl alcohol and 1~3 part of tributyl phosphate, continue to keep rotating speed that 35~45min is mixed, obtain mixed slurry, will Mixed slurry pours into quantification of 24g/m2, in mould that thickness is 0.2mm, and be put into paper machine, be 100~120 in temperature DEG C, pressure be 0.6~0.8MPa under extrusion forming, cooled to room temperature, discharging, you can be made highly conductive antibacterial water proof type lead Electric paper.
Example 1
Weigh 8g lauryl sodium sulfate to pour into the beaker with 95mL deionized waters, be placed in ultrasonic wave separating apparatus ultrasonic 16min is vibrated, obtains self-control dispersion liquid；Weigh 24g carbon nanotubes to pour into ball mill, under conditions of rotating speed is 80r/min Ball milling 45min, obtains carbon nanotube powder, is in mass ratio 1：5：2 by carbon nanotube powder, mass fraction be 32% nitric acid Silver-colored solution and self-control dispersion liquid mixing are placed in beaker and stir 20min, obtain stirring liquid, molten with the nitric acid that mass fraction is 24% Liquid adjusts the pH of stirring liquid to 4, then stirring liquid is put into unglazed greenhouse 1h is mixed, and decompression filters, and removes filtrate, takes Go out filter residue, filter residue is put into baking oven, 30min is dried under the conditions of at a temperature of 90 °C, obtain self-control and carry silver-colored carbon nanotubes；Claim Take 32g sweet potato starch to be added in the beaker with 80mL deionized waters, 10min is mixed at being 65 DEG C in temperature, obtains Gelatinized corn starch liquid, cooled to room temperature, the pH to 5 of gelatinized corn starch liquid is adjusted with the hydrochloric acid that mass fraction is 15%, obtains starch mixing Liquid, then 2g isoamylases are added into starch mixed liquor, 1h is digested at being 35 DEG C in temperature, filtering removes filter residue, obtains filtrate As starch reaction liquid, is by volume by sodium hydroxide solution and epoxychloropropane that starch reaction liquid, mass fraction are 5% 4：2：1 mixing is placed in beaker, and 20min is stirred at being 40 DEG C in temperature, obtains that liquid is mixed, then add mixing into beaker The succinic anhydride of liquid quality 0.8% is stirred, continues insulated and stirred 45min, suction filtration obtains solids, natural air drying, and grinding discharges, Obtain self-control cationic starch powder；It is 1 in mass ratio：2：4 mix carboxymethyl cellulose, chopped carbon fiber and deionized water It is placed in ultrasonic wave separating apparatus, the sonic oscillation 1h under conditions of rotating speed is 100r/min, obtains carbon fiber dispersion liquid；By weight Number meter, weighs 30 parts of birch wood pulp celluloses, 16 parts of self-controls carry silver-colored carbon nanotubes, 8 parts of carbon fiber dispersion liquids and 20 parts are gone respectively Ionized water mixing is placed in mixer, and 16min is stirred under conditions of rotating speed is 120r/min, then adds 6 parts of self-control cations Starch powder, 5 parts of deionized waters, 2 parts of polyvinyl alcohol and 1 part of tributyl phosphate, continue to keep rotating speed that 35min is mixed, obtain To mixed slurry, mixed slurry is poured into quantification of 24g/m2, in mould that thickness is 0.2mm, and be put into paper machine, in temperature It is extrusion forming under 0.6MPa to spend for 100 DEG C, pressure, and cooled to room temperature, discharges, you can highly conductive antibacterial water proof type is made Conductive paper.
Example 2
Weigh 9g lauryl sodium sulfate to pour into the beaker with 100mL deionized waters, be placed in surpassing in ultrasonic wave separating apparatus Sound oscillation 18min, obtains self-control dispersion liquid；Weigh 28g carbon nanotubes to pour into ball mill, in the condition that rotating speed is 90r/min Lower ball milling 53min, obtains carbon nanotube powder, is in mass ratio 1：5：2 by carbon nanotube powder, mass fraction be 32% nitre Sour silver solution and self-control dispersion liquid mixing are placed in beaker and stir 25min, obtain stirring liquid, with the nitric acid that mass fraction is 24% Solution adjusts the pH of stirring liquid to 5, then stirring liquid is put into unglazed greenhouse 1.5h is mixed, and decompression filters, and removes filter Liquid, takes out filter residue, filter residue is put into baking oven, and 35min is dried under conditions of being 95 DEG C in temperature, obtains self-control and carries silver-colored carbon nanometer Pipe；Weigh 34g sweet potato starch to be added in the beaker with 90mL deionized waters, 11min is mixed at being 70 DEG C in temperature, obtains To gelatinized corn starch liquid, cooled to room temperature, the pH to 5.5 of gelatinized corn starch liquid is adjusted with the hydrochloric acid that mass fraction is 15%, obtains starch Mixed liquor, then 3g isoamylases are added into starch mixed liquor, 1.5h is digested at being 38 DEG C in temperature, filtering removes filter residue, obtains It is starch reaction liquid to filtrate, starch reaction liquid, the sodium hydroxide solution that mass fraction is 5% and epoxychloropropane is pressed into body Product is than being 4：2：1 mixing is placed in beaker, is stirred 25min at being 48 DEG C in temperature, is obtained that liquid is mixed, then into beaker add Add the succinic anhydride that liquid quality 0.8% is mixed, continue insulated and stirred 53min, suction filtration obtains solids, natural air drying, grinding Discharging, obtains self-control cationic starch powder；It is 1 in mass ratio：2：4 by carboxymethyl cellulose, chopped carbon fiber and deionization Water mixing is placed in ultrasonic wave separating apparatus, and the sonic oscillation 1.5h under conditions of rotating speed is 110r/min, obtains carbon fiber and disperse Liquid；Count in parts by weight, weigh 35 parts of birch wood pulp celluloses respectively, 18 parts of self-controls carry silver-colored carbon nanotubes, 9 parts of carbon fiber dispersion liquids It is placed in 25 parts of deionized water mixing in mixer, stirs 18min under conditions of rotating speed is 140r/min, then add 7 parts certainly Cationic starch powder, 6 parts of deionized waters, 3 parts of polyvinyl alcohol and 2 parts of tributyl phosphates processed, continue to keep rotating speed to be mixed 40min, obtains mixed slurry, and mixed slurry is poured into quantification of 24g/m2, in mould that thickness is 0.2mm, and be put into papermaking In machine, the extrusion forming in the case where temperature is 110 DEG C, pressure is 0.7MPa, cooled to room temperature, discharging, you can be made highly conductive Antibacterial water proof type conductive paper.
Example 3
Weigh 10g lauryl sodium sulfate to pour into the beaker with 105mL deionized waters, be placed in surpassing in ultrasonic wave separating apparatus Sound oscillation 20min, obtains self-control dispersion liquid；Weigh 32g carbon nanotubes to pour into ball mill, in the condition that rotating speed is 100r/min Lower ball milling 60min, obtains carbon nanotube powder, is in mass ratio 1：5：2 by carbon nanotube powder, mass fraction be 32% nitre Sour silver solution and self-control dispersion liquid mixing are placed in beaker and stir 30min, obtain stirring liquid, with the nitric acid that mass fraction is 24% Solution adjusts the pH of stirring liquid to 6, then stirring liquid is put into unglazed greenhouse 2h is mixed, and decompression filters, and removes filtrate, Filter residue is taken out, filter residue is put into baking oven, 40min is dried under conditions of being 100 DEG C in temperature, self-control is obtained and carries silver-colored carbon nanometer Pipe；Weigh 36g sweet potato starch to be added in the beaker with 100mL deionized waters, be mixed at being 75 DEG C in temperature 12min, obtains gelatinized corn starch liquid, cooled to room temperature, the pH to 6 of gelatinized corn starch liquid is adjusted with the hydrochloric acid that mass fraction is 15%, is obtained To starch mixed liquor, then 4g isoamylases are added into starch mixed liquor, digest 2h at being 40 DEG C in temperature, filtering removes filter Slag, it is starch reaction liquid to obtain filtrate, by starch reaction liquid, the sodium hydroxide solution and epoxychloropropane that mass fraction is 5% It is 4 by volume：2：1 mixing is placed in beaker, is stirred 30min at being 55 DEG C in temperature, is obtained that liquid is mixed, then to beaker The succinic anhydride of liquid quality 0.8% is mixed in middle addition, continues insulated and stirred 60min, filters and obtains solids, natural air drying, Grinding discharging, obtains self-control cationic starch powder；It is 1 in mass ratio：2：4 by carboxymethyl cellulose, chopped carbon fiber and go Ionized water mixing is placed in ultrasonic wave separating apparatus, and the sonic oscillation 2h under conditions of rotating speed is 120r/min, obtains carbon fiber point Dispersion liquid；Count in parts by weight, weigh 40 parts of birch wood pulp celluloses respectively, 20 parts of self-controls carry silver-colored carbon nanotubes, 10 parts of carbon fibers point Dispersion liquid and 30 parts of deionized water mixing are placed in mixer, stir 20min under conditions of rotating speed is 160r/min, then add 8 Part self-control cationic starch powder, 7 parts of deionized waters, 4 parts of polyvinyl alcohol and 3 parts of tributyl phosphates, continue to keep rotating speed mixing 45min is stirred, mixed slurry is obtained, mixed slurry is poured into quantification of 24g/m2, in mould that thickness is 0.2mm, and be put into In paper machine, the extrusion forming in the case where temperature is 120 DEG C, pressure is 0.8MPa, cooled to room temperature, discharging, you can height is made Conductive antibacterial water proof type conductive paper.
Comparative example
With the conductive paper of company of Nanchang City production as a comparison case
Conductive paper in highly conductive antibacterial water proof type conductive paper produced by the present invention and comparative example is detected, testing result is such as Shown in table 1：
1st, electric conductivity is tested
Tested using conductivity measurement.
2nd, biocidal property is tested
The fungistatic effect of paper is tested using vibration flask method.The example 1~3 and comparative example sample for taking 4 anticipatory remarks invention to prepare Product（Paper quality is 0.75g, and size is 10mm × 10mm）, be put into the conical flask of 250mL, be separately added into 70mLPBS and 5mL bacteria suspensions, are denoted as A, B, C, D.Conical flask is fixed on vibration shaking table, under the conditions of operative temperature is 20~25 DEG C, 2min is vibrated with 300r/min.1.0mLPBS is drawn, sample liquid before being vibrated as test group.Continue to draw 1.0mL samples after shaking 1h Liquid.Draw respectively with each 1.0mL of sample liquid after concussion before vibrating, with agar tilt-pour process close to plate, each liquid sample is inoculated with two and puts down Ware, overturns plate, puts 40h in 37 DEG C of incubators.Method according to regulation carries out viable bacteria culture and counts, and calculates bacteriostasis rate.
Bacteriostasis rate=（Average colony number after average colony number-sample vibration before sample vibration）Average colony before the vibration of/sample Number
3rd, waterproofing tests
Tested using contact angle measurement.
Table 1
Test event Example 1（A） Example 2（B） Example 3（C） Comparative example（D）
Electrical conductivity（S/m） 323.4 324.9 326.8 286.1
Resistivity（Ω·m） 2.9 2.7 2.6 18.5
Bacteriostasis rate（%） 93.6 94.4 95.9 70.2
Contact angle（°） 132 134 137 75
Cross direction tensile strength（kN/m2） 7.1 7.8 8.9 3.6
Machine direction tensile strength（kN/m2） 3.5 3.8 3.9 1.8
From the data in table 1, it can be seen that highly conductive antibacterial water proof type conductive paper produced by the present invention, good conductivity, antibiotic property are strong, waterproof It is good, reach energy saving purpose, hence it is evident that better than comparative example product.Therefore, there is wide prospect of the application.

Claims (6)

1. a kind of preparation method of highly conductive antibacterial water proof type conductive paper, it is characterised in that specifically preparation process is：
（1）Weigh 8~10g lauryl sodium sulfate to be poured into the beaker with 95~105mL deionized waters, be placed in ultrasound Sonic oscillation in ripple separating apparatus, obtains self-control dispersion liquid；
（2）Weigh 24~32g carbon nanotubes and pour into ball milling in ball mill, obtain carbon nanotube powder, by carbon nanotube powder, nitre Sour silver solution and self-control dispersion liquid mixing are placed in beaker and stir, and obtain stirring liquid, the pH to 4 of stirring liquid is adjusted with salpeter solution ~6, then stirring liquid is put into unglazed greenhouse and is mixed, decompression filters, and removes filtrate, takes out filter residue, filter residue is put into Dried in baking oven, obtain self-control and carry silver-colored carbon nanotubes；
（3）Weigh 32~36g sweet potato starch and be added in the beaker with 80~100mL deionized waters and be mixed, formed sediment Paste mixing liquid, cooled to room temperature, the pH to 5~6 of gelatinized corn starch liquid is adjusted with hydrochloric acid, obtains starch mixed liquor, then mix to starch Close and 2~4g isoamylases enzymolysis added in liquid, filtering removes filter residue, and it is starch reaction liquid to obtain filtrate, by starch reaction liquid, The sodium hydroxide solution and epoxychloropropane mixing that mass fraction is 5% are placed in beaker and stir, and obtain being mixed liquid, then to The succinic anhydride of liquid quality 0.8% is mixed in addition in beaker, continues insulated and stirred, filters and obtains solids, natural air drying, Grinding discharging, obtains self-control cationic starch powder；
（4）Carboxymethyl cellulose, chopped carbon fiber and deionized water are mixed and are placed in sonic oscillation in ultrasonic wave separating apparatus, is obtained Carbon fiber dispersion liquid；
（5）Count in parts by weight, weigh 30~40 parts of birch wood pulp celluloses respectively, 16~20 parts of self-controls carry silver-colored carbon nanotubes, 8~ 10 parts of carbon fiber dispersion liquids and 20~30 parts of deionized water mixing are placed in mixer and stir, then add 6~8 parts of self-control cations Starch powder, 5~7 parts of deionized waters, 2~4 parts of polyvinyl alcohol and 1~3 part of tributyl phosphate, continue to keep rotating speed mixing to stir Mix, obtain mixed slurry, mixed slurry is poured into mould, and be put into extrusion forming in paper machine, cooled to room temperature, goes out Material, you can highly conductive antibacterial water proof type conductive paper is made.
A kind of 2. preparation method of highly conductive antibacterial water proof type conductive paper according to claim 1, it is characterised in that：Step （1）The sonic oscillation time is 16~20min.
A kind of 3. preparation method of highly conductive antibacterial water proof type conductive paper according to claim 1, it is characterised in that：Step （2）The rotational speed of ball-mill is 80~100r/min, and Ball-milling Time is 45~60min, and carbon nanotube powder, mass fraction are 32% silver nitrate solution and the mass ratio of self-control dispersion liquid are 1：5：2, mixing time is 20~30min, the quality of salpeter solution Fraction is 24%, and the mixing time is 1~2h, and drying temperature is 90~100 DEG C, and drying time is 30~40min.
A kind of 4. preparation method of highly conductive antibacterial water proof type conductive paper according to claim 1, it is characterised in that：Step （3）The whipping temp is 65~75 DEG C, and mixing time is 10~12min, and the mass fraction of hydrochloric acid is 15%, hydrolysis temperature For 35~40 DEG C, enzymolysis time is 1~2h, starch reaction liquid, the sodium hydroxide solution and epoxychloropropane that mass fraction is 5% Volume ratio be 4：2：1, it is 40~55 DEG C that temperature, which is mixed, and the mixing time is 20~30min, continues mixing time and is 45~60min.
A kind of 5. preparation method of highly conductive antibacterial water proof type conductive paper according to claim 1, it is characterised in that：Step （4）The mass ratio of the carboxymethyl cellulose, chopped carbon fiber and deionized water is 1：2：4, sonic oscillation rotating speed for 100~ 120r/min, sonic oscillation time are 1~2h.
A kind of 6. preparation method of highly conductive antibacterial water proof type conductive paper according to claim 1, it is characterised in that：Step （5）The speed of agitator is 120~160r/min, and mixing time is 16~20min, and continuation mixing time is 35~45min, The size of mould is quantification of 24g/m2, thickness 0.2mm, extrusion temperature is 100~120 DEG C, squeeze pressure for 0.6~ 0.8MPa。
CN201711357932.1A 2017-12-17 2017-12-17 A kind of preparation method of highly conductive antibacterial water proof type conductive paper Pending CN108018742A (en)

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CN108797175A (en) * 2018-05-30 2018-11-13 郭迎庆 A kind of preparation method of antibacterial waterproof conductive paper
CN109645603A (en) * 2018-12-04 2019-04-19 广州甚多服装有限公司 A kind of antibacterial thermal insulating polyurethane composite material and its preparation process
CN110284371A (en) * 2019-06-26 2019-09-27 安徽顺彤包装材料有限公司 A kind of environment-friendly high is every wrapping paper and preparation method thereof
JP2020127351A (en) * 2019-02-05 2020-08-20 国立大学法人横浜国立大学 Actuator
CN112414294A (en) * 2020-12-01 2021-02-26 大连理工大学 Hydrogel and carbon material-based high-sensitivity sandwich layer strain sensor and preparation method thereof
CN112458790A (en) * 2020-12-08 2021-03-09 马鞍山市康辉纸箱纸品有限公司 Processing technology for improving antibacterial property of antibacterial packaging carton of vegetable essential oils

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CN112458790A (en) * 2020-12-08 2021-03-09 马鞍山市康辉纸箱纸品有限公司 Processing technology for improving antibacterial property of antibacterial packaging carton of vegetable essential oils

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Application publication date: 20180511