WO2013174250A1 - Composite d'oxyde cuivreux revêtu en surface d'oxyde de cuivre et procédé de préparation s'y rapportant - Google Patents

Composite d'oxyde cuivreux revêtu en surface d'oxyde de cuivre et procédé de préparation s'y rapportant Download PDF

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Publication number
WO2013174250A1
WO2013174250A1 PCT/CN2013/075970 CN2013075970W WO2013174250A1 WO 2013174250 A1 WO2013174250 A1 WO 2013174250A1 CN 2013075970 W CN2013075970 W CN 2013075970W WO 2013174250 A1 WO2013174250 A1 WO 2013174250A1
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WO
WIPO (PCT)
Prior art keywords
copper oxide
coated
copper
oxide
preparing
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Application number
PCT/CN2013/075970
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English (en)
Chinese (zh)
Inventor
覃东棉
刘华胜
朱刘
Original Assignee
广东先导稀材股份有限公司
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Application filed by 广东先导稀材股份有限公司 filed Critical 广东先导稀材股份有限公司
Publication of WO2013174250A1 publication Critical patent/WO2013174250A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other

Definitions

  • the invention relates to a synthetic material and a preparation method thereof, in particular to a composite material of copper oxide surface coated with copper oxide and a preparation method thereof. Background technique
  • the antifouling coating is mainly composed of a resin, an antifouling agent, a pigment filler, and an auxiliary agent, and an antifouling agent plays a decisive role.
  • Cuprous oxide is one of the oldest antifouling agents in use, and it has the advantages of safety and low cost.
  • the second is that the release rate of copper ions in seawater is faster (5.4 g/ Ml), the life expectancy of cuprous oxide antifouling paint is short.
  • U.S. Patent No. 5,707,438 discloses a method of oxidizing a copper oxide protective layer on the surface of cuprous oxide by a pyrometallurgical method to prevent the continued oxidation of cuprous oxide in the air and to control the oxidation of the cuprous oxide.
  • the rate of dissolution of copper in seawater due to the method of fire used in this patent, can cause oxidative inhomogeneities and uncontrollable thickness of the oxide layer.
  • Another object of the present invention is to provide a composite material of copper oxide surface coated with copper oxide and a preparation method thereof, which can realize controllable thickness of the coated copper oxide.
  • the present invention provides a method for preparing a composite material of copper oxide surface-coated copper oxide, comprising the steps of: dispersing a cuprous oxide powder in a fraction
  • the liquid and sodium hydroxide solution are added to the suspension to carry out the coating reaction, and the pH is maintained during the coating reaction.
  • the value is unchanged to form a reaction product, and the reaction product is coated with copper oxide on the surface of cuprous oxide.
  • the present invention provides a method for preparing a copper oxide surface-coated copper oxide composite material comprising the steps of: dispersing a cuprous oxide powder in a deionized water containing a dispersant; To prepare a suspension; at a predetermined temperature and a predetermined pH value, a copper salt solution and a sodium hydroxide solution are added to the suspension to carry out a coating reaction, and the pH is kept constant during the coating reaction to form a reaction.
  • the product is a composite material in which copper oxide is coated with copper oxide on the surface of the cuprous oxide; after the coating reaction, it is cooled to room temperature; and the reaction product is filtered, washed, and dried.
  • the present invention provides a composite material of copper oxide surface-coated copper oxide, which is coated with copper oxide on the surface of cuprous oxide according to the first invention of the present invention.
  • the preparation method of the material is prepared.
  • a layer of copper oxide is oxidized on the surface of the cuprous oxide.
  • the present invention employs a solution reaction method for surface coating to obtain a relatively uniform copper oxide coating layer.
  • a layer of copper oxide is oxidized on the surface of cuprous oxide.
  • the present invention adopts a solution reaction method for surface coating, and the thickness of the coating layer can be based on the coating agent. The amount of addition to control.
  • the composite material of the cuprous oxide surface coated with copper oxide obtained by the invention can prevent the conversion of cuprous oxide into copper oxide in air on the one hand, thereby losing the antifouling function; on the other hand, the cuprous oxide can be controlled The rate of release in seawater, the waste of cuprous oxide and its contamination of the water environment by the deposition of offshore and port terminals.
  • a method for preparing a composite material of copper oxide surface coated with copper oxide comprising the steps of: dispersing a cuprous oxide powder in deionized water containing a dispersing agent to prepare a suspension; at a predetermined temperature, a prescribed pH The copper salt solution and the sodium hydroxide solution are added to the suspension to carry out a coating reaction, and the pH is kept constant during the coating reaction to form a reaction product, and the reaction product is a cuprous oxide surface.
  • the particle size of the cuprous oxide powder is 50 ⁇ ! ⁇ 10 ⁇ m; cuprous oxide concentration is 50g / L ⁇ 500g / L o
  • the dispersing agent is selected from sodium dodecylbenzenesulfonate, sodium dodecyl sulfate or sodium heptaacetate or a mixture of them. 5 g/L ⁇ More preferably, the concentration of the dispersing agent is 0. 05 g / L ⁇ 0. 5 g / L.
  • the predetermined temperature range is from 70 ° C to 90 ° C
  • the pH range is from 8 to 10
  • the coating reaction is carried out.
  • the time is 0. 5 ⁇ 2h.
  • the copper salt solution is a copper sulfate solution. More preferably, the concentration of the copper sulfate solution is concentrated The degree is from 10 g/L to 100 g/L, and the amount of copper sulfate contained in the copper sulfate solution is 5% to 25% of the mass of the cuprous oxide powder.
  • the concentration of the sodium hydroxide solution is from 4 g / L to 16 g / L.
  • the thickness of the copper oxide coated on the surface of the cuprous oxide is 5 nm to 50 nm.
  • a copper salt solution and a sodium hydroxide solution are added to the suspension to carry out a magnetic stirring during the coating reaction.
  • the rate of magnetic stirring is 200 to 500 rpm.
  • the temperature at the time of drying is 50 °C.
  • Step 1 Add 100 ml of deionized water to a round bottom flask, add 0. 005 g of sodium dodecylbenzene sulfonate, stir and dissolve, add 5 g of 50 nm cuprous oxide powder, and ultrasonically disperse for 15 min to obtain stable dispersion. Cuprous oxide suspension;
  • the sodium hydroxide solution was slowly added dropwise to the suspension, and the pH was kept constant during the coating reaction.
  • the coating reaction time was 0.5 h, stirring was continued until cooling to room temperature, then filtered and washed at 50 ⁇ . Drying is performed to obtain a copper oxide-coated cuprous oxide powder.
  • the first step is to add 100ml of deionized water to the round bottom flask, and add 0. 05g Sodium sulphate, stirred and dissolved, then added 27. 5 g of 500 nm cuprous oxide powder, ultrasonic dispersion for 15 min to obtain a stable dispersion of cuprous oxide suspension;
  • Step 2 Transfer the above suspension to a magnetic stirrer, heat the suspension to 80 °C at 350 rpm, adjust the pH to 9, and use a peristaltic pump to apply 75 g/L of copper sulfate solution 75 ml and 12 g. /L sodium hydroxide solution is slowly added dropwise to the suspension, the pH value remains unchanged during the coating reaction, the coating reaction time is lh, stirring is continued until cooling to room temperature, then filtered and washed at 50 ° C Drying, copper oxide coated cuprous oxide powder is obtained. .
  • First step Add 100ml of deionized water to the round bottom flask, add 0. 0275g sodium hexametaphosphate, stir and dissolve, add 50g l 0m of cuprous oxide powder, and ultrasonically disperse for 15min to obtain stable dispersed oxide oxide. Copper suspension;
  • Step 2 Transfer the above suspension to a magnetic stirrer, heat the suspension to 90 °C at 500 rpm, adjust the pH to 10, and use a peristaltic pump to apply 125 g and 16 g of 100 g/L copper sulfate solution. /L sodium hydroxide solution was slowly added dropwise to the suspension, the pH value was kept constant during the coating reaction, the coating reaction time was 2 h, stirring was continued until cooling to room temperature, then filtered and washed with water and dried at 50 Torr. Dry, copper oxide coated cuprous oxide powder is obtained.
  • the detection result of Examples 1-3 was a focused beam ion technique.
  • the thickness of the copper oxide coated on the cuprous oxide powder was 5 nm in Example 1, 25 nm in Example 2, and 50 nm in Example 3.
  • the copper oxide-coated composite material of the cuprous oxide surface according to the present invention is obtained in accordance with the aforementioned preparation method.
  • the particle size of the cuprous oxide powder is 50 ⁇ ! ⁇ 10 ⁇ m
  • cuprous oxide coated with copper oxide Thickness is 5nm ⁇ 50nm c

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention porte sur un composite d'oxyde cuivreux revêtu en surface d'oxyde de cuivre et sur le procédé de préparation s'y rapportant, la préparation comprenant les étapes consistant à : disperser une poudre d'oxyde cuivreux dans de l'eau désionisée contenant un dispersant pour préparer une suspension ; ajouter une solution de sel de cuivre et une solution d'hydroxyde de sodium dans la suspension pour effectuer une réaction d'enrobage à une température précisée et une valeur de pH précisée, pendant la réaction d'enrobage, la valeur de pH étant maintenue constante pour former un produit de la réaction, le produit de la réaction étant un composite d'oxyde cuivreux revêtu en surface d'oxyde de cuivre ; refroidir à température ambiante après la réaction d'enrobage ; filtrer, laver et sécher le produit de la réaction. Le composite est préparé par le procédé de préparation. Une couche de revêtement d'oxyde de cuivre uniforme peut être obtenue. L'épaisseur de la couche de revêtement peut être maîtrisée.
PCT/CN2013/075970 2012-05-21 2013-05-21 Composite d'oxyde cuivreux revêtu en surface d'oxyde de cuivre et procédé de préparation s'y rapportant WO2013174250A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201210161196.3 2012-05-21
CN201210161196.3A CN103421352B (zh) 2012-05-21 2012-05-21 氧化亚铜表面包覆氧化铜的复合材料的制备方法

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WO2013174250A1 true WO2013174250A1 (fr) 2013-11-28

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WO (1) WO2013174250A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105116030B (zh) * 2015-07-27 2017-11-03 中国海洋大学 一种Cu2O@CuO半核壳结构纳米复合材料及其制备方法
CN106041120B (zh) * 2016-06-28 2018-05-25 昆明理工大学 一种铜/氧化亚铜核壳结构纳米材料的制备方法
CN106929934B (zh) * 2017-03-15 2018-12-28 赵宝勤 一种复合纳米防污抗藻剂的制备方法
CN109926048B (zh) * 2019-04-09 2021-08-20 大连理工大学 一种单组分双活性位Cu2O-CuO纳米混相结构铜氧化物催化剂、制备方法与应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5707438A (en) * 1996-02-21 1998-01-13 American Chemet Corporation Composite cuprous oxide powder
JP2005154861A (ja) * 2003-11-27 2005-06-16 Mitsui Mining & Smelting Co Ltd 二層コート銅粉及びその二層コート銅粉の製造方法並びにその二層コート銅粉を用いた導電性ペースト
WO2009093609A1 (fr) * 2008-01-24 2009-07-30 Nippon Chemical Industrial Co., Ltd. Poudre enduite d'oxyde de cuivre (i) et son procédé de production
CN101560320A (zh) * 2009-05-14 2009-10-21 浙江理工大学 一种高分子微球表面包覆氧化铜的复合材料及其制备方法
WO2011010663A1 (fr) * 2009-07-22 2011-01-27 日本化学工業株式会社 Particules enduites d’un oxyde de cuivre, procédé d’obtention correspondant et matériau de revêtement antisalissure contenant lesdites particules
CN102250499A (zh) * 2011-05-16 2011-11-23 大连海事大学 一种松香包覆处理氧化亚铜的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102350499B (zh) * 2011-09-28 2013-05-08 河北工业大学 一种Cu/Cu2O核壳复合微球的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5707438A (en) * 1996-02-21 1998-01-13 American Chemet Corporation Composite cuprous oxide powder
JP2005154861A (ja) * 2003-11-27 2005-06-16 Mitsui Mining & Smelting Co Ltd 二層コート銅粉及びその二層コート銅粉の製造方法並びにその二層コート銅粉を用いた導電性ペースト
WO2009093609A1 (fr) * 2008-01-24 2009-07-30 Nippon Chemical Industrial Co., Ltd. Poudre enduite d'oxyde de cuivre (i) et son procédé de production
CN101560320A (zh) * 2009-05-14 2009-10-21 浙江理工大学 一种高分子微球表面包覆氧化铜的复合材料及其制备方法
WO2011010663A1 (fr) * 2009-07-22 2011-01-27 日本化学工業株式会社 Particules enduites d’un oxyde de cuivre, procédé d’obtention correspondant et matériau de revêtement antisalissure contenant lesdites particules
CN102250499A (zh) * 2011-05-16 2011-11-23 大连海事大学 一种松香包覆处理氧化亚铜的制备方法

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CN103421352A (zh) 2013-12-04
CN103421352B (zh) 2014-11-19

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