CN107216592A - A kind of preparation method of the CPVC tubing with photocatalytic self-cleaning function - Google Patents

A kind of preparation method of the CPVC tubing with photocatalytic self-cleaning function Download PDF

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Publication number
CN107216592A
CN107216592A CN201710596632.2A CN201710596632A CN107216592A CN 107216592 A CN107216592 A CN 107216592A CN 201710596632 A CN201710596632 A CN 201710596632A CN 107216592 A CN107216592 A CN 107216592A
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cpvc
tubing
preparation
cleaning function
area
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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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Priority to CN201710596632.2A priority Critical patent/CN107216592A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
    • C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of preparation method of the CPVC tubing with photocatalytic self-cleaning function, present invention material first pass through normal temperature complexing control Hydrolyze method directly it is synthetically prepared go out strontium doping nano titanium oxide, the Sr of doping2+It is wrapped in outside nano-titania particle and plays a part of similar addition emulsion, has part not form the Sr of Sr O keys2+Mix nano titanium oxide substitution Ti4+, change its microstructure, cause photo-generated carrier increase in photocatalytic process, improve the photocatalysis performance of CPVC tubing；Maleic anhydride and CPVC are also carried out graft modification by the present invention using solid-state grafting simultaneously, maleic anhydride instead of the unstable active site in CPVC, so as to improve the combination property of CPVC tubing, there are a variety of functions such as antibiotic property, self-cleaning and ultraviolet absorption ability using the CPVC tubing obtained by the present invention.

Description

A kind of preparation method of the CPVC tubing with photocatalytic self-cleaning function
Technical field
The present invention relates to CPVC tubing production fields, and in particular to a kind of CPVC tubing with photocatalytic self-cleaning function Preparation method.
Background technology
Chliorinated polyvinyl chloride (CPVC) is the further chlorination modified product of polyvinyl chloride (PVC), and polyvinyl chloride resin passes through chlorine After change, the scrambling increase of strand arrangement, polarity increase increases the dissolubility of resin, chemical stability increase, so that Improve the performance of the corrosion of the heat resistance and acid and alkali resistance, salt, oxidant of material etc., be widely used in building, chemical industry, metallurgy, The fields such as shipbuilding, electrical equipment, weaving.But the self-cleaning property and stain resistant of CPVC pipelines are also to evaluate in actual use One important technology index of its cost performance, the quality of the performance directly affects durability, cleaning dimension that CPVC pipelines are used The convenience and the length in flight-line service cycle of shield.
Nano-TiO2Because of its unique photocatalysis characteristic, and also there are the excellent properties such as nontoxic and intensive ultraviolet absorption.Cause This, by nano-titanium dioxide modified, and is added in CPVC raw pipeline materials, can assign CPVC pipelines with antibiotic property, A variety of functions such as self-cleaning and ultraviolet absorption ability.
However, pure nano TiO 2 greater band gap, its Detitanium-ore-type is 3.2eV, rutile-type is 3.0 eV, can only absorb ripple The long ultraviolet light (only about account for sunshine 4%) less than 400nm, the relatively low visible ray of big energy (constitutes about sunshine 43%) it can not be utilized；In addition during charge transfer, a part of light induced electron can be combined again with hole, cause its efficiency Reduction, seriously constrains TiO2The practical application of photocatalytic effect.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the CPVC tubing with photocatalytic self-cleaning function, with gram Take the deficiencies in the prior art.
The object of the present invention is achieved like this：
A kind of preparation method of the CPVC tubing with photocatalytic self-cleaning function, it is characterised in that comprise the following steps：
（1）The titanium tetrachloride for weighing certain volume is slowly dropped into distilled water, is stood 30 min and is clarified to solution, obtains homogeneous titanium Compound solution；
（2）A certain amount of Sr (OH) is added into above-mentioned solution2•8H2O, regulation pH=7 paper produce a large amount of white precipitates, filter, Washing, drying, air-flow crushing sieving, obtain strontium doping nano titanium oxide；
（3）CPVC is put into and is swelled at room temperature in acetone soln 6-8 hours, maleic anhydride, ammonium persulfate ultrasound shake is added Swing and stir 1-2 hours, suction filtration products therefrom constant temperature drying obtains modified by maleic acid anhydride graft CPVC；
（4）A certain amount of modified by maleic acid anhydride graft CPVC is weighed, is put into high-speed mixer, when being warming up to 60-70 DEG C, plus Enter step（2）Extruding pelletization in obtained strontium doping nano titanium oxide mixing 10-20min, input double screw extruder, must change Property CPVC resin granular materials；
（5）By step（4）Modified CPVC resin granular materials are added in banbury, are passed through nitrogen, with 50r/min rotating speeds, are entered in 160 DEG C Row banburying；
（6）By step（5）The modification CPVC resin granular materials that banburying is completed, which are delivered in double screw extruder, is extruded into CPVC tubing, and And by all CPVC tubing at 125 DEG C, carry out the annealing of 36 hours；
（7）Finally by electron accelerator to step（6）Product carry out cross-linking radiation, discharging.
The step（1）11 mL titanium tetrachlorides are weighed to be slowly dropped into 125mL distilled water.
The step（2）Middle addition 0.52gSr (OH)2•8H2O, pH=7 is adjusted with 1: 1 ammoniacal liquor.
The step（3）The condition of middle graft process is：The maleic anhydride of CPVC, 15-20 parts by weight of 100 parts by weight, The ammonium persulfate of 2-3 parts by weight, reaction temperature is 75-80 DEG C, and wherein CPVC and acetone soln are mixed according to mass volume ratio 2: 5 It is swelled.
The step（4）The addition of middle strontium doping nano titanium oxide is the 8- of modified by maleic acid anhydride graft CPVC consumptions 10%；Each area's temperature of described double screw extruder is an area：170-175 DEG C, 2nd area：175-180 DEG C, 3rd area：180-185℃； Extruder rotating speed 500-600r/min.
The step（6）Middle each area's temperature of double screw extruder is an area：160-165 DEG C, 2nd area：165-170 DEG C, three Area：170-175℃；Extruder rotating speed 500-600r/min.
Step（7）Described in electron accelerator electron energy and beam intensity be respectively 5MeV, 200 μ A, close rate 100kGy/s。
The present invention has following beneficial effect：The present invention material first pass through normal temperature be complexed-control Hydrolyze method directly it is synthetically prepared go out Strontium doping nano titanium oxide, the Sr of doping2+It is wrapped in the work that similar addition emulsion is played outside nano-titania particle With there is part not form the Sr of Sr-O keys2+Mix nano titanium oxide substitution Ti4+, change its microstructure, cause photocatalysis During photo-generated carrier increase, improve the photocatalysis performance of CPVC tubing；The present invention will also using solid-state grafting simultaneously Maleic anhydride carries out graft modification with CPVC, and maleic anhydride instead of the unstable active site in CPVC, so as to improve The combination property of CPVC tubing, has antibiotic property, self-cleaning and ultraviolet absorption ability etc. using the CPVC tubing obtained by the present invention A variety of functions.
Embodiment
A kind of preparation method of the CPVC tubing with photocatalytic self-cleaning function, it is characterised in that comprise the following steps：
（1）The titanium tetrachloride for weighing certain volume is slowly dropped into distilled water, is stood 30 min and is clarified to solution, obtains homogeneous titanium Compound solution；
（2）A certain amount of Sr (OH) is added into above-mentioned solution2•8H2O, regulation pH=7 paper produce a large amount of white precipitates, filter, Washing, drying, air-flow crushing sieving, obtain strontium doping nano titanium oxide；
（3）CPVC is put into and is swelled at room temperature in acetone soln 6-8 hours, maleic anhydride, ammonium persulfate ultrasound shake is added Swing and stir 1-2 hours, suction filtration products therefrom constant temperature drying obtains modified by maleic acid anhydride graft CPVC；
（4）A certain amount of modified by maleic acid anhydride graft CPVC is weighed, is put into high-speed mixer, when being warming up to 60-70 DEG C, plus Enter step（2）Extruding pelletization in obtained strontium doping nano titanium oxide mixing 10-20min, input double screw extruder, must change Property CPVC resin granular materials；
（5）By step（4）Modified CPVC resin granular materials are added in banbury, are passed through nitrogen, with 50r/min rotating speeds, are entered in 160 DEG C Row banburying；
（6）By step（5）The modification CPVC resin granular materials that banburying is completed, which are delivered in double screw extruder, is extruded into CPVC tubing, and And by all CPVC tubing at 125 DEG C, carry out the annealing of 36 hours；
（7）Finally by electron accelerator to step（6）Product carry out cross-linking radiation, discharging.
The step（1）11 mL titanium tetrachlorides are weighed to be slowly dropped into 125mL distilled water.
The step（2）Middle addition 0.52gSr (OH)2•8H2O, pH=7 is adjusted with 1: 1 ammoniacal liquor.
The step（3）The condition of middle graft process is：The maleic anhydride of CPVC, 15-20 parts by weight of 100 parts by weight, The ammonium persulfate of 2-3 parts by weight, reaction temperature is 75-80 DEG C, and wherein CPVC and acetone soln are mixed according to mass volume ratio 2: 5 It is swelled.
The step（4）The addition of middle strontium doping nano titanium oxide is the 8- of modified by maleic acid anhydride graft CPVC consumptions 10%；Each area's temperature of described double screw extruder is an area：170-175 DEG C, 2nd area：175-180 DEG C, 3rd area：180-185℃； Extruder rotating speed 500-600r/min.
The step（6）Middle each area's temperature of double screw extruder is an area：160-165 DEG C, 2nd area：165-170 DEG C, three Area：170-175℃；Extruder rotating speed 500-600r/min.
Step（7）Described in electron accelerator electron energy and beam intensity be respectively 5MeV, 200 μ A, close rate 100kGy/s。

Claims (7)

1. a kind of preparation method of the CPVC tubing with photocatalytic self-cleaning function, it is characterised in that comprise the following steps：
（1）The titanium tetrachloride for weighing certain volume is slowly dropped into distilled water, is stood 30 min and is clarified to solution, obtains homogeneous titanium Compound solution；
（2）A certain amount of Sr (OH) is added into above-mentioned solution2•8H2O, regulation pH=7 paper produce a large amount of white precipitates, filter, Washing, drying, air-flow crushing sieving, obtain strontium doping nano titanium oxide；
（3）CPVC is put into and is swelled at room temperature in acetone soln 6-8 hours, maleic anhydride, ammonium persulfate ultrasound shake is added Swing and stir 1-2 hours, suction filtration products therefrom constant temperature drying obtains modified by maleic acid anhydride graft CPVC；
（4）A certain amount of modified by maleic acid anhydride graft CPVC is weighed, is put into high-speed mixer, when being warming up to 60-70 DEG C, plus Enter step（2）Extruding pelletization in obtained strontium doping nano titanium oxide mixing 10-20min, input double screw extruder, must change Property CPVC resin granular materials；
（5）By step（4）Modified CPVC resin granular materials are added in banbury, are passed through nitrogen, with 50r/min rotating speeds, are entered in 160 DEG C Row banburying；
（6）By step（5）The modification CPVC resin granular materials that banburying is completed, which are delivered in double screw extruder, is extruded into CPVC tubing, and And by all CPVC tubing at 125 DEG C, carry out the annealing of 36 hours；
（7）Finally by electron accelerator to step（6）Product carry out cross-linking radiation, discharging.
2. a kind of preparation method of CPVC tubing with photocatalytic self-cleaning function according to claim 1, its feature It is, the step（1）11 mL titanium tetrachlorides are weighed to be slowly dropped into 125mL distilled water.
3. a kind of preparation method of CPVC tubing with photocatalytic self-cleaning function according to claim 1, its feature It is, the step（2）Middle addition 0.52gSr (OH)2•8H2O, pH=7 is adjusted with 1: 1 ammoniacal liquor.
4. a kind of preparation method of CPVC tubing with photocatalytic self-cleaning function according to claim 1, its feature It is, the step（3）The condition of middle graft process is：Maleic anhydride, the 2-3 of CPVC, 15-20 parts by weight of 100 parts by weight The ammonium persulfate of parts by weight, reaction temperature is 75-80 DEG C, and wherein CPVC and acetone soln mix molten according to mass volume ratio 2: 5 It is swollen.
5. a kind of preparation method of CPVC tubing with photocatalytic self-cleaning function according to claim 1, its feature It is, the step（4）The addition of middle strontium doping nano titanium oxide is the 8- of modified by maleic acid anhydride graft CPVC consumptions 10%；Each area's temperature of described double screw extruder is an area：170-175 DEG C, 2nd area：175-180 DEG C, 3rd area：180-185℃； Extruder rotating speed 500-600r/min.
6. a kind of preparation method of CPVC tubing with photocatalytic self-cleaning function according to claim 1, its feature It is, the step（6）Middle each area's temperature of double screw extruder is an area：160-165 DEG C, 2nd area：165-170 DEG C, 3rd area： 170-175℃；Extruder rotating speed 500-600r/min.
7. a kind of preparation method of CPVC tubing with photocatalytic self-cleaning function according to claim 1, its feature It is, step（7）Described in electron accelerator electron energy and beam intensity be respectively 5MeV, 200 μ A, close rate 100kGy/s。
CN201710596632.2A 2017-07-20 2017-07-20 A kind of preparation method of the CPVC tubing with photocatalytic self-cleaning function Pending CN107216592A (en)

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CN201710596632.2A CN107216592A (en) 2017-07-20 2017-07-20 A kind of preparation method of the CPVC tubing with photocatalytic self-cleaning function

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1472169A (en) * 2003-06-30 2004-02-04 山东省国腾功能陶瓷材料有限公司 Technology for preparing high-purity nanometer strontium titanate powder
CN101070442A (en) * 2007-06-06 2007-11-14 长兴科技(上海)有限公司 Composite material and composition containing same
CN103073830A (en) * 2013-02-16 2013-05-01 哈尔滨中大型材科技股份有限公司 Preparation method of maleic anhydride grafted chlorinated polyvinyl chloride composite material
CN103319664A (en) * 2013-07-10 2013-09-25 哈尔滨理工大学 Method for preparing solid-phase maleic anhydride (MAH) grafted chlorinated polyvinyl chloride (CPVC)
WO2015122180A1 (en) * 2014-02-14 2015-08-20 富士フイルム株式会社 Manufacturing method for strontium titanate fine particles
CN105618030A (en) * 2015-12-23 2016-06-01 东南大学 Preparation method for efficient photocatalyst SrTiO3/Bi2WO6 and application of photocatalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1472169A (en) * 2003-06-30 2004-02-04 山东省国腾功能陶瓷材料有限公司 Technology for preparing high-purity nanometer strontium titanate powder
CN101070442A (en) * 2007-06-06 2007-11-14 长兴科技(上海)有限公司 Composite material and composition containing same
CN103073830A (en) * 2013-02-16 2013-05-01 哈尔滨中大型材科技股份有限公司 Preparation method of maleic anhydride grafted chlorinated polyvinyl chloride composite material
CN103319664A (en) * 2013-07-10 2013-09-25 哈尔滨理工大学 Method for preparing solid-phase maleic anhydride (MAH) grafted chlorinated polyvinyl chloride (CPVC)
WO2015122180A1 (en) * 2014-02-14 2015-08-20 富士フイルム株式会社 Manufacturing method for strontium titanate fine particles
CN105618030A (en) * 2015-12-23 2016-06-01 东南大学 Preparation method for efficient photocatalyst SrTiO3/Bi2WO6 and application of photocatalyst

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