CN107325591A - A kind of preparation method of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes - Google Patents

A kind of preparation method of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes Download PDF

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Publication number
CN107325591A
CN107325591A CN201710596253.3A CN201710596253A CN107325591A CN 107325591 A CN107325591 A CN 107325591A CN 201710596253 A CN201710596253 A CN 201710596253A CN 107325591 A CN107325591 A CN 107325591A
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fire
fighting
cpvc
type antibacterial
copper type
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盛付林
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Anhui Sheng Hua Pipe Co Ltd
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Anhui Sheng Hua Pipe Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
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  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
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  • Pest Control & Pesticides (AREA)
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  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a kind of preparation method of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes, white carbon black carrier is prepared using sol-gal process, from Cu2+As antibacterial ion, neopelex prepares copper type antibacterial white cabon black as additive, and the addition of surfactant can reduce the surface tension of colloid, its reunion nucleation is prevented, so as to reduce particle size, increases surface area, increase its adsorbance to antibacterial ion, so as to save Cu2+Consumption, reduce cost, using identical metering antibacterial ion salting liquid in the case of, more Cu can be supported2+It is finally reached the purpose for improving sterilizing rate, then again to it with ion liquid modified processing, improve compatibility of the modified white carbon black in CPVC matrixes, so as to form uniform heat conduction network chain, it is used as fire-fighting CPVC water pipes filler and uses heat-resistant stability, antibacterial and the anti-wear performance for being remarkably improved CPVC water pipes.

Description

A kind of preparation method of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes
Technical field
The present invention relates to inorganic chemical industry Additive Production field, and in particular to a kind of high temperature resistant copper of fire-fighting CPVC water pipes The preparation method of type antibacterial white cabon black.
Background technology
It is well known that traditional fire-fighting is generally steel pipe, pipe of cement or multiple tube etc. with pipe, present Building Fire Fighting System is given Water pipe there is no pipe special, it is common to use be coating steel pipe.The major defect existed using coating steel pipe as fire extinguisher canvas hose It is the easy corrosion of coating steel pipe inwall, the iron rust when occurring fire alarm in pipe can block the shower nozzle in fire-fighting system, lose it Fire-extinguishing function concurrently, secondly need to process screw thread tubing wall thickening, big from great, power consumption, and installation difficulty is made troubles and increased to construction The shortcomings of built-loading, once substituted by plastic piping.But because most of plastic pipe is red label goods.
Chliorinated polyvinyl chloride (CPVC) is the further chlorination modified product of polyvinyl chloride (PVC), and its chlorinity is generally 65%-72% (volume fraction).CPVC in addition to many premium properties for having PVC concurrently, its corrosion resistance, heat resistance, Solubility, anti-flammability, mechanical strength etc. are greatly improved than PVC, and temperature is used for a long time up to 110 DEG C in maximum operation (service) temperature Spend for 95 DEG C, used as fire extinguisher canvas hose, it is impossible to the high temperature applied to explosive such as fire especially chemical plant for a long time Environment, and be chronically at wet environment and be easy to breed bacteria, thus need to resist existing fire extinguisher canvas hose with CPVC materials Bacterium, high-temperature stability are modified.
The content of the invention
It is an object of the invention to provide a kind of preparation side of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes Method, to overcome the deficiencies in the prior art.
The object of the present invention is achieved like this：
The preparation method of the high temperature resistant copper type antibacterial white cabon black of a kind of fire-fighting CPVC water pipes, it is characterised in that including following step Suddenly：
（1）The water glass solution, the sodium bicarbonate solution of 1/2 mass, surfactant of 1/2 preheated mass are slowly injected into To 90 DEG C of isothermal reactor high speed stirring a period of times, then rotating speed is turned down, remaining water glass solution and sodium acid carbonate is molten Liquid is added in reactor, and adjustment pH value is 5-6, continues to react a period of time；
（2）Toward step（1）Add copper-bath in reaction solution, control temperature is at 90-95 DEG C, isothermal reaction 2-3 hours, while hot Suction filtration is simultaneously washed to without Cu with ethanol2+, then filter cake is put into 120 DEG C of baking oven and dries 24h, ground 200 mesh sieve is produced Surfactant-modified copper type antibacterial white cabon black；
（3）A certain amount of ionic liquid and deionized water are stirred and evenly mixed, in being heated under 50 DEG C of water-baths and stirring 30min, added Step（2）The surfactant-modified copper type antibacterial white cabon black ultrasonic disperse 10-15min of gained, is warming up to 80 DEG C, continues to stir Reaction 3-4 hour up to liquefied mixture in the pasty state；
（4）By step（3）Pasty state reaction product, which is poured into pallet, to be uniformly dispersed, and 12h is dried in prior to 80 DEG C air dry ovens, then 24h, discharging are dried in 60 DEG C of vacuum drying chambers.
The step（1）Middle water glass solution: sodium bicarbonate solution: surfactant according to 1: 1.5: 0.5 volume matter Amount ratio is mixed, wherein described water glass solution concentration is 10-15wt%, sodium bicarbonate solution concentration is 6-8wt%, described Surfactant is neopelex.
The step（1）Middle water glass solution and sodium bicarbonate solution are placed in reactor is preheating to 70-90 DEG C, then The sodium bicarbonate solution surfactant of the water glass solution of 1/2 mass, 1/2 mass is slowly injected into 90 DEG C of isothermal reactors In, with 300-500r/min speed stirring reaction 20min, then with 200r/min speed by remaining water glass solution and carbonic acid Hydrogen sodium solution is added in reactor, and adjustment pH value is 5-6, continues to react 20min.
The step（2）Middle copper-bath concentration be 0.05-0.1mol/L, wherein described copper-bath and（Water The mixed solution of glass solution+sodium bicarbonate solution）Mixed according to volume ratio for 1: 4 ratio.
The step（3）In weigh 10g the deionized water of ionic liquid and 250mL stir and evenly mix, add 40g surfaces and live Property agent be modified copper type antibacterial white cabon black ultrasonic disperse 10-15min；Wherein described ionic liquid is 1- butyl -3- methyl miaows In azoles tetrafluoroborate, 1-butyl-3-methylimidazolium bromide, bromination N- butyl-pyridiniums, N- butyl-pyridinium tetrafluoroborates One or more mixtures with any ratio mixing.
The present invention has following beneficial effect：The present invention prepares white carbon black carrier using sol-gel process, from Cu2+Make For antibacterial ion, neopelex prepares copper type antibacterial white cabon black as additive, and the addition of surfactant can To reduce the surface tension of colloid, its reunion nucleation is prevented, so as to reduce particle size, increases surface area, increases it to antibacterial The adsorbance of ion, so as to save Cu2+Consumption, reduce cost, using identical metering antibacterial ion salting liquid situation Under, more Cu can be supported2+, the purpose for improving sterilizing rate is finally reached, then again to it with ion liquid modified processing, is carried High compatibility of the modified white carbon black in CPVC matrixes, so as to form uniform heat conduction network chain, is used as fire-fighting CPVC water Tube packing uses heat-resistant stability, antibacterial and the anti-wear performance for being remarkably improved CPVC water pipes.
Embodiment
A kind of preparation method of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes, it is characterised in that including with Lower step：
（1）The water glass solution, the sodium bicarbonate solution of 1/2 mass, surfactant of 1/2 preheated mass are slowly injected into To 90 DEG C of isothermal reactor high speed stirring a period of times, then rotating speed is turned down, remaining water glass solution and sodium acid carbonate is molten Liquid is added in reactor, and adjustment pH value is 5-6, continues to react a period of time；
（2）Toward step（1）Add copper-bath in reaction solution, control temperature is at 90-95 DEG C, isothermal reaction 2-3 hours, while hot Suction filtration is simultaneously washed to without Cu with ethanol2+, then filter cake is put into 120 DEG C of baking oven and dries 24h, ground 200 mesh sieve is produced Surfactant-modified copper type antibacterial white cabon black；
（3）A certain amount of ionic liquid and deionized water are stirred and evenly mixed, in being heated under 50 DEG C of water-baths and stirring 30min, added Step（2）The surfactant-modified copper type antibacterial white cabon black ultrasonic disperse 10-15min of gained, is warming up to 80 DEG C, continues to stir Reaction 3-4 hour up to liquefied mixture in the pasty state；
（4）By step（3）Pasty state reaction product, which is poured into pallet, to be uniformly dispersed, and 12h is dried in prior to 80 DEG C air dry ovens, then 24h, discharging are dried in 60 DEG C of vacuum drying chambers.
The step（1）Middle water glass solution: sodium bicarbonate solution: surfactant according to 1: 1.5: 0.5 volume matter Amount ratio is mixed, wherein described water glass solution concentration is 10-15wt%, sodium bicarbonate solution concentration is 6-8wt%, described Surfactant is neopelex.
The step（1）Middle water glass solution and sodium bicarbonate solution are placed in reactor is preheating to 70-90 DEG C, then The sodium bicarbonate solution surfactant of the water glass solution of 1/2 mass, 1/2 mass is slowly injected into 90 DEG C of isothermal reactors In, with 300-500r/min speed stirring reaction 20min, then with 200r/min speed by remaining water glass solution and carbonic acid Hydrogen sodium solution is added in reactor, and adjustment pH value is 5-6, continues to react 20min.
The step（2）Middle copper-bath concentration be 0.05-0.1mol/L, wherein described copper-bath and（Water The mixed solution of glass solution+sodium bicarbonate solution）Mixed according to volume ratio for 1: 4 ratio.
The step（3）In weigh 10g the deionized water of ionic liquid and 250mL stir and evenly mix, add 40g surfaces and live Property agent be modified copper type antibacterial white cabon black ultrasonic disperse 10-15min；Wherein described ionic liquid is 1- butyl -3- methyl miaows In azoles tetrafluoroborate, 1-butyl-3-methylimidazolium bromide, bromination N- butyl-pyridiniums, N- butyl-pyridinium tetrafluoroborates One or more mixtures with any ratio mixing.

Claims (5)

1. the preparation method of the high temperature resistant copper type antibacterial white cabon black of a kind of fire-fighting CPVC water pipes, it is characterised in that including following Step：
（1）The water glass solution, the sodium bicarbonate solution of 1/2 mass, surfactant of 1/2 preheated mass are slowly injected into To 90 DEG C of isothermal reactor high speed stirring a period of times, then rotating speed is turned down, remaining water glass solution and sodium acid carbonate is molten Liquid is added in reactor, and adjustment pH value is 5-6, continues to react a period of time；
（2）Toward step（1）Add copper-bath in reaction solution, control temperature is at 90-95 DEG C, isothermal reaction 2-3 hours, while hot Suction filtration is simultaneously washed to without Cu with ethanol2+, then filter cake is put into 120 DEG C of baking oven and dries 24h, ground 200 mesh sieve is produced Surfactant-modified copper type antibacterial white cabon black；
（3）A certain amount of ionic liquid and deionized water are stirred and evenly mixed, in being heated under 50 DEG C of water-baths and stirring 30min, added Step（2）The surfactant-modified copper type antibacterial white cabon black ultrasonic disperse 10-15min of gained, is warming up to 80 DEG C, continues to stir Reaction 3-4 hour up to liquefied mixture in the pasty state；
（4）By step（3）Pasty state reaction product, which is poured into pallet, to be uniformly dispersed, and 12h is dried in prior to 80 DEG C air dry ovens, then 24h, discharging are dried in 60 DEG C of vacuum drying chambers.
2. a kind of preparation method of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes according to claim 1, Characterized in that, the step（1）Middle water glass solution: sodium bicarbonate solution: surfactant according to 1: 1.5: 0.5 volume Mass ratio is mixed, wherein described water glass solution concentration is 10-15wt%, sodium bicarbonate solution concentration is 6-8wt%, described Surfactant be neopelex.
3. a kind of preparation method of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes according to claim 1, Characterized in that, the step（1）Middle water glass solution and sodium bicarbonate solution are placed in reactor is preheating to 70-90 DEG C, Then the sodium bicarbonate solution surfactant of the water glass solution of 1/2 mass, 1/2 mass is slowly injected into anti-to 90 DEG C of constant temperature Answer in device, with 300-500r/min speed stirring reaction 20min, then with 200r/min speed by remaining water glass solution and Sodium bicarbonate solution is added in reactor, and adjustment pH value is 5-6, continues to react 20min.
4. a kind of preparation method of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes according to claim 1, Characterized in that, the step（2）Middle copper-bath concentration be 0.05-0.1mol/L, wherein described copper-bath and （The mixed solution of water glass solution+sodium bicarbonate solution）Mixed according to volume ratio for 1: 4 ratio.
5. a kind of preparation method of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes according to claim 1, Characterized in that, the step（3）In weigh 10g the deionized water of ionic liquid and 250mL stir and evenly mix, add 40g tables The copper type antibacterial white cabon black ultrasonic disperse 10-15min that face activating agent is modified；Wherein described ionic liquid is 1- butyl -3- first Base tetrafluoroborate, 1-butyl-3-methylimidazolium bromide, bromination N- butyl-pyridiniums, N- butyl-pyridinium tetrafluoroborates In it is one or more with any mixtures than mixing.
CN201710596253.3A 2017-07-20 2017-07-20 A kind of preparation method of the high temperature resistant copper type antibacterial white cabon black of fire-fighting CPVC water pipes Pending CN107325591A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112778662A (en) * 2020-12-30 2021-05-11 界首市旭升塑胶制品有限公司 Process for improving performance of PVC rain shoes by using calcium carbonate whiskers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1535574A (en) * 2003-04-04 2004-10-13 鞍山科技大学 Antibacterial white cabon black and its preparation method
CN102258011A (en) * 2011-06-03 2011-11-30 中国农业大学 Bactericidal pesticide preparation by taking ionic liquid as cosolvent and preparation method thereof
CN106243460A (en) * 2016-08-26 2016-12-21 樊之雄 A kind of antibacterial high-strength plastic water supply pipe and preparation method thereof
CN106832673A (en) * 2017-02-27 2017-06-13 常州崇高纳米材料有限公司 A kind of PVC feed pipes with long acting antibiotic function and preparation method thereof
CN107668032A (en) * 2017-09-29 2018-02-09 唐山建华科技发展有限责任公司 Antibacterial white cabon black composite and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1535574A (en) * 2003-04-04 2004-10-13 鞍山科技大学 Antibacterial white cabon black and its preparation method
CN102258011A (en) * 2011-06-03 2011-11-30 中国农业大学 Bactericidal pesticide preparation by taking ionic liquid as cosolvent and preparation method thereof
CN106243460A (en) * 2016-08-26 2016-12-21 樊之雄 A kind of antibacterial high-strength plastic water supply pipe and preparation method thereof
CN106832673A (en) * 2017-02-27 2017-06-13 常州崇高纳米材料有限公司 A kind of PVC feed pipes with long acting antibiotic function and preparation method thereof
CN107668032A (en) * 2017-09-29 2018-02-09 唐山建华科技发展有限责任公司 Antibacterial white cabon black composite and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112778662A (en) * 2020-12-30 2021-05-11 界首市旭升塑胶制品有限公司 Process for improving performance of PVC rain shoes by using calcium carbonate whiskers

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