CN111040474B - 一种导电钛白粉及制备方法 - Google Patents
一种导电钛白粉及制备方法 Download PDFInfo
- Publication number
- CN111040474B CN111040474B CN201911220294.8A CN201911220294A CN111040474B CN 111040474 B CN111040474 B CN 111040474B CN 201911220294 A CN201911220294 A CN 201911220294A CN 111040474 B CN111040474 B CN 111040474B
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- slurry
- conductive
- water
- ato
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic 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
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/3623—Grinding
-
- 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
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/363—Drying, calcination
-
- 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
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
-
- 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
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3669—Treatment with low-molecular organic 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
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3684—Treatment with organo-silicon 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
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
-
- 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
- C09C3/003—Flushing
-
- 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
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
-
- 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
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/043—Drying, calcination
-
- 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
- C09C3/063—Coating
-
- 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
- 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
- C09C3/10—Treatment with macromolecular organic 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
- C09C3/12—Treatment with organosilicon compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
本发明公开了一种导电钛白粉及制备方法,导电钛白粉包括二氧化钛基材和位于所述二氧化钛基材表面的包膜层,所述包膜层由内之外依次包括聚苯胺包膜层和ATO包膜层,所述ATO包膜层除掺杂Sb,还掺杂有C、N。本发明提供的导电钛白粉,同时具有PANI、ATO、TiO2的优点,还能实现导电性的大幅度提升,具有超导电性能。本发明还提供了一种导电钛白粉的制备方法,在聚苯胺包膜前先对二氧化钛进行高分子修饰,在包裹了聚苯胺膜层、ATO后,再经过后期煅烧及有机表面剂处理,为钛白粉的后期使用提供更好的润湿性和分散性,经此方法制备得到的钛白粉具有粒子细而均匀、高分散性、高耐候性和配方适用性。
Description
技术领域
本发明属于钛白粉制备技术领域,具体涉及一种导电钛白粉及制备方法。
背景技术
随着我国科学技术的不断进步,对新型材料的要求也愈发严格,为了满足特殊领域的使用要求,导电涂料的使用满足了多种复杂环境的要求,导电涂料的制备工艺目前已经相对成熟,但是对于提高导电涂料的导电性仍旧是一个急需改进的方向,因此超导电钛白粉的研究是很有必要的。近年来,市场上出现了一些新型的导电钛白粉,其合成工艺是通过钛白粉和氧化石墨烯进行混合,在实际应用过程中,此种钛白粉的光学性能较差,并且此种钛白粉的耐候性相对较差,无法实现长期有效的导电及防静电的要求,所以研发新型的超导电钛白粉是改善导电涂料的关键。
目前无机复合导电钛白粉的合成方法主要分为以下几种:1)、在钛白粉表面包覆导电层ATO(SnO2掺杂Sb);2)、钛白粉表面包覆FTO(SnO2掺杂F);3)、钛白粉表面包覆ITO(In2O3掺杂Sn)等,ATO包膜的方式是目前较为推崇的方式,兼具了ATO和TiO2的优点,既有一定的导电性,颜色较浅,还有较好的耐候性及耐温性,但是ATO包膜后的钛白粉导电性仍不能满足现代社会尤其是特殊领域的要求。
因此,有必要研发一种新型的导电钛白粉及其制备方法,以解决现有技术问题。
发明内容
本发明的目的就在于为解决现有技术的不足而提供一种导电钛白粉及制备方法。
本发明的目的是以下述技术方案实现的:
一种导电钛白粉,包括二氧化钛基材和位于所述二氧化钛基材表面的包膜层,所述包膜层由内之外依次包括聚苯胺包膜层和ATO包膜层,所述ATO包膜层除掺杂Sb,还掺杂有C、N。
优选的,所述聚苯胺包膜层是由加入苯胺单体和引发剂反应形成的;所述苯胺单体和引发剂的加入量分别为所述二氧化钛基材质量的3~20%、50~300%;所述ATO包膜层是由加入锡盐和锑盐反应,然后经过煅烧形成的,所述锡盐的加入量,以氧化锡计,为所述二氧化钛基材总量的0.1~3.0wt%,所述锑盐的加入量,以氧化锑计,为所述二氧化钛基材总量的0.1~0.5wt%。
如上所述的导电钛白粉的制备方法,包括以下步骤:
S1:制备二氧化钛基材料浆、预处理并对其中的二氧化钛进行高分子修饰;
S2:将所述步骤S1修饰后的二氧化钛首先进行聚苯胺包膜,再进行ATO包膜处理,得到包膜后的料浆;
S3:将所述步骤S2包膜后的料浆经过水洗、干燥、煅烧、制粉,得到所述导电钛白粉;在所述水洗、干燥、煅烧、制粉的任一阶段,还包括有机表面处理剂处理步骤。
优选的,所述步骤S1中用于高分子修饰的化合物为水溶性高分子聚合物,所述水溶性高分子聚合物为聚丙烯酰胺、聚丙烯酸、聚乙烯吡咯烷酮、聚乙烯醇、聚马来酸酐、聚季胺盐、或聚乙二醇中的一种或两种以上组合。
优选的,所述预处理步骤为:取二氧化钛基材料浆加入二氧化钛总量0.05~1wt%的分散剂进行砂磨,得到砂磨料浆。
所述高分子修饰步骤为:向所述预处理后的二氧化钛基材料浆中加入二氧化钛总量0.1~10wt%的水溶性高分子聚合物,pH调节为1~3,超声,得到高分子修饰的二氧化钛料浆。
优选的,步骤S2中所述聚苯胺包膜是向所述高分子修饰后的二氧化钛料浆中加入苯胺单体,以及水溶性引发剂,超声,得到聚苯胺包膜的二氧化钛料浆;所述苯胺单体的加入量为所述二氧化钛基材料浆中二氧化钛总量的3~20wt%,所述水溶性引发剂的加入量为二氧化钛基材料浆中二氧化钛总量50~300wt%。
优选的,所述水溶性引发剂为无机盐类过硫酸盐、过氧化氢、水溶性偶氮引发剂的任一种或两种以上组合。
优选的,所述步骤S2进行ATO包膜的步骤为:将所述聚苯胺包膜的二氧化钛料浆升温至40~70℃,调节pH至1~3,均化后加入锡盐和锑盐,保持料浆的pH为1~3,均化;砂磨,然后调节pH至6.5~7.5,均化,得到ATO包膜后的二氧化钛料浆;锡盐的加入量,以氧化锡计,为二氧化钛总量的0.1~3.0wt%,锑盐的加入量,以氧化锑计,为二氧化钛总量的0.1~0.5wt%。
优选的,所述有机表面处理剂为多元醇或有机硅中的一种或多种,所述有机表面处理剂加入量为二氧化钛总量的0.01~1wt%。
优选的,所述煅烧温度为400~500℃,时间为1.5~3h。
本发明提供的导电钛白粉,在现有技术的ATO包膜层内还包覆聚苯胺(PANI),包覆聚苯胺不仅可以有效修复钛白粉颗粒表面的结构,还可以降低钛白粉颗粒表面的自由能,提高钛白粉的耐候性,使其使用范围更加广泛,使用性能更为优异;另外ATO包膜层经过C、N掺杂,可以有效的提高SnO2膜层的导电性,进一步优化了膜层结构,增强了钛白粉的耐候性,提升了产品的使用性能。因此,本发明提供的导电钛白粉,能同时具有PANI、ATO、TiO2的优点,还能实现导电性的大幅度提升,具有超导电性能。
本发明还提供了一种导电钛白粉的制备方法,在聚苯胺包膜前先对二氧化钛进行高分子修饰,可使料浆中钛白颗粒不易团聚,增强了钛白颗粒的单一性,提高了聚苯胺的包裹完整性和均匀性,在包裹了聚苯胺膜层后,聚苯胺本身优异的耐酸性和优异的导电性能,使制备得到的导电钛白粉的导电性能有了大幅度的提升,再者,包覆ATO后,再经过后期煅烧,使一部分聚苯胺和SnO2发生掺杂反应,使原本仅掺杂Sb的SnO2膜层,又掺杂了C、N,这样使得SnO2膜层的导电性也有所提升;而且,本申请还采用有机表面剂处理,为钛白粉的后期使用提供更好的润湿性和分散性,经此方法制备得到的钛白粉具有粒子细而均匀、高分散性、高耐候性和配方适用性。
附图说明
图1是对比标样和实施例1-4样品的耐候性对比图(测试方法为:醇酸氨基树脂测试体系,氙灯老化箱)
具体实施方案
为了更好的理解上述技术方案,下面将结合体的实施方式对上述技术方案做详细的说明。
本发明提供了一种导电钛白粉,包括二氧化钛基材和位于二氧化钛基材表面的包膜层,包膜层由内之外依次包括聚苯胺(PANI)包膜层和ATO包膜层,ATO包膜层掺杂除Sb,还掺杂有C、N。
聚苯胺是一种高分子化合物,具有特殊的电学、光学性质。在二氧化钛表面包覆聚苯胺不仅可以有效修复钛白粉颗粒表面的结构,还可以降低钛白粉颗粒表面的自由能,提高钛白粉的耐候性,使其使用范围更加广泛,使用性能更为优异;另外ATO包膜层经过C、N掺杂,可以有效的提高SnO2膜层的导电性,进一步优化了膜层结构,增强了钛白粉的耐候性,提升了产品的使用性能。因此,本发明提供的导电钛白粉能同时具有PANI、ATO、TiO2的优点,还能实现导电性的大幅度提升,具有超导电性能。
优选的,聚苯胺包膜层是由加入苯胺单体和引发剂反应形成的;苯胺单体和引发剂的加入量分别为二氧化钛基材质量的3~20%、50~300%,ATO包膜层是由加入锡盐和锑盐反应,然后经过煅烧形成的,锡盐的加入量,以氧化锡计,为二氧化钛基材总量的0.1~3.0wt%,锑盐的加入量,以氧化锑计,为二氧化钛基材总量的0.1~0.5wt%。所添加苯胺单体、引发剂、锡盐和锑盐加入量经试验优化而得,在此范围内,可以较低的成本取得包覆均匀、完整的膜层。
上述导电钛白粉的制备方法,包括以下步骤:
S1:制备二氧化钛基材料浆、预处理并对其中的二氧化钛进行高分子修饰;
S2:将步骤S1修饰后的二氧化钛首先进行聚苯胺包膜,再进行ATO包膜处理,得到包膜后的料浆;
S3:将步骤S2包膜后的料浆经过水洗、干燥、煅烧、制粉,得到导电钛白粉;在水洗、干燥、煅烧、制粉的任一阶段,还包括有机表面处理剂处理步骤。
在料浆中先对二氧化钛进行高分子修饰,使得钛白颗粒不易团聚,增强了钛白粉颗粒的单一性,提高了聚苯胺的包裹完整性和均匀性;在包裹了聚苯胺膜层后,聚苯胺本身优异的耐酸性和优异的导电性性能,可使该导电钛白粉的导电性能有了大幅度的提升,再者,后期的煅烧过程,使一部分聚苯胺和SnO2发生掺杂反应,使原本仅掺杂Sb的SnO2膜层,又掺杂了C、N,这样使得SnO2膜层的导电性也有所提升,可见增加聚苯胺膜层是一举多得的方法。再加上采用有机表面处理剂处理,为钛白粉的后期使用提供更好的润湿性和分散性。
优选的,步骤S1用于高分子修饰的化合物为水溶性高分子聚合物,水溶性高分子聚合物可选用聚丙烯酰胺、聚丙烯酸、聚乙烯吡咯烷酮、聚乙烯醇、聚马来酸酐、聚季胺盐或聚乙二醇中的一种或两种以上组合。
优选的,步骤S1预处理步骤为:取二氧化钛料浆加入二氧化钛总量0.05~1wt%的分散剂进行砂磨,得到砂磨料浆。
优选的,高分子修饰步骤为:向预处理后的砂磨料浆中加入二氧化钛总量0.1~10wt%的水溶性高分子聚合物,pH调节为1~3,超声辅助反应10~30min,得到高分子修饰的二氧化钛料浆,超声作用下反应更加完全。二氧化钛基材料浆可采用未包覆的钛白粉经粉碎、湿磨制得;进一步优选的,未经包覆的钛白粉的粒子大小为0.250~0.350μm;加入高分子聚合物前将砂磨料浆稀释到浓度为200~350g/L,在适宜浓度下会获得更好的高分子修饰效果。
优选的,步骤S2聚苯胺包膜是向高分子修饰后的二氧化钛料浆加入苯胺单体,以及水溶性引发剂,超声辅助反应,得到聚苯胺包膜的二氧化钛料浆;苯胺单体的加入量为二氧化钛料浆中二氧化钛总量的3~20wt%,水溶性引发剂的加入量为二氧化钛料浆中二氧化钛总量的50~300wt%。在水溶性引发剂作用下,苯胺单体可发生原位聚合反应,形成聚苯胺包覆层;进一步优选的,水溶性引发剂可选用无机盐类过硫酸盐、过氧化氢或水溶性偶氮引发剂的任一种或两种以上组合。苯胺单体和水溶性引发剂优选依次加入,首先加入苯胺单体,加入时间为10~20min,然后搅拌均化4~12h,再加入水溶性引发剂,在超声辅助下反应30min~4h,使反应完全。
优选的,步骤S2进行ATO包膜的步骤为:将聚苯胺包膜的二氧化钛料浆升温至60℃,调节pH至1~3,10~25min调好,然后均化20~40min后加入锡盐和锑盐,保持料浆的pH为1~3,均化20~40min;砂磨,然后调节pH至6.5~7.5,均化30~120min,得到ATO包膜后的二氧化钛料浆,锡盐的加入量,以氧化锡计,为二氧化钛总量的0.1~3.0wt%,锑盐的加入量,以氧化锑计,为二氧化钛总量的0.1~0.5wt%。锡盐和锑盐优选采用氯化锡盐酸溶液、氯化锑盐酸溶液加入,氯化锡盐酸溶液浓度为40-200g/L,氯化锑盐酸溶液的浓度为20~160g/L。最后调节pH至6.5~7.5,可以为后续的钛白粉应用提供中性的环境,便于应用。
上述步骤中调节pH可以使料浆、包膜更为稳定,防止水洗触变,为后期应用提供前瞻处理,对料浆进行砂磨,可以优化产品的粒径及粒径分布,包膜后进行砂磨可以使因包膜团聚在一起的颗粒重新打开,进一步优化产品的粒径及粒径分布。包膜过程中进行均化的作用为可稳定包膜效果,使得包膜具有完整性和均一性。
上述步骤中pH调节可采用稀碱液或稀酸液;稀碱液可采用浓度为190~300g/L的稀NaOH或氨水溶液;稀酸液可采用浓度为140~160g/L的稀硫酸、稀盐酸或稀磷酸。
优选的,有机表面处理剂为多元醇或有机硅中的一种或多种,有机表面处理剂加入量为二氧化钛总量的0.01~1wt%。
优选的,煅烧温度为400~500℃,时间为1.5~3h。在此煅烧温度和时间内,煅烧完全,C、N掺杂性能好。
实施例1
一种导电钛白粉的制备方法,包括以下步骤:
S1:取未经包覆的钛白粉经粉碎、湿磨、砂磨(湿磨后粒径为0.390μm,粒径分布1.55)(在砂磨前的料浆中加入1%六偏磷酸钠作为分散剂)、稀释后,料浆浓度为200g/L,料浆pH为7;高分子链PVP修饰钛白粉颗粒,在料浆中添加8wt%的高分子聚合物,保持温度为常温状态,开启搅拌和超声,超声开启10min后关闭;
S2:用稀酸(浓度90g/L)将料浆的pH调为2,15min调好,均化15min。在钛白粉料浆中加入10%的苯胺单体,在室温下搅拌均化6h,随后在料浆中加入引发单体聚合的引发剂过硫酸铵,该过程需要超声辅助,持续1h。然后将体系温度升高到60℃后,均化10min,在料浆中加入0.8%的氯化锡(以SnO2计)盐酸溶液和0.1%的氯化锑(以Sb2O3计)盐酸溶液(氯化锡盐酸溶液浓度为40g/L和氯化锑盐酸溶液浓度为25g/L),使其两者与NaOH溶液(浓度175g/L)并流至钛白粉料浆中,保持料浆pH不变,均化60min,将均化完成的料浆再过一遍砂磨机,进行一遍砂磨;用氢氧化钠调节料浆pH为6.5,均化2h;
S3:对包膜后料浆进行水洗,水洗至电导率<100μs/cm、闪蒸、450℃下煅烧2h、汽粉,汽粉时加入0.3%TMP,得到产品导电钛白粉B。
实施例2
一种导电钛白粉的制备方法,包括以下步骤:
S1未经包覆的钛白粉经粉碎、湿磨、砂磨(在砂磨前的料浆中加入1%六偏磷酸钠作为分散剂)、稀释后,料浆浓度为200g/L,料浆pH为7;高分子链PVP修饰钛白粉颗粒,在料浆中添加8wt%的高分子聚合物,保持温度为常温状态,开启搅拌和超声,超声开启10min后关闭;
S2用稀酸将料浆的pH调为2,15min调好,均化15min。在钛白粉料浆中加入15%的苯胺单体,在室温下搅拌均化6h,随后在料浆中加入引发单体聚合的引发剂过硫酸铵,该过程需要超声辅助,持续2h。然后将体系温度升高到60℃后,均化10min,在料浆中加入0.8%的氯化锡(以SnO2计)盐酸溶液和0.1%的氯化锑(以Sb2O3计)盐酸溶液,使其两者与NaOH溶液并流至钛白粉料浆中,保持料浆pH不变,均化60min,将均化完成的料浆再过一遍砂磨机,进行一遍砂磨;用氢氧化钠调节料浆pH为6.5,均化2h;
S3对包膜后料浆进行水洗,水洗至电导率<100μs/cm、闪蒸、420℃下煅烧2.5h、汽粉。汽粉时加入0.4%TMP,其他条件同实施例1,得到产品导电钛白粉C。
实施例3
一种导电钛白粉的制备方法,包括以下步骤:
S1未经包覆的钛白粉经粉碎、湿磨、砂磨(在砂磨前的料浆中加入1%六偏磷酸钠作为分散剂)、稀释后,料浆浓度为300g/L,料浆pH为7;高分子链PVP修饰钛白粉颗粒,在料浆中添加8wt%的高分子聚合物,保持温度为常温状态,开启搅拌和超声,超声开启10min后关闭;
S2用稀酸将料浆的pH调为2,15min调好,均化15min。在钛白粉料浆中加入15%的苯胺单体,在室温下搅拌均化6h,随后在料浆中加入引发单体聚合的引发剂过硫酸铵,该过程需要超声辅助,持续3h。然后将体系温度升高到60℃后,均化10min,在料浆中加入0.8%的氯化锡(以SnO2计)盐酸溶液和0.1%的氯化锑(以Sb2O3计)盐酸溶液,使其两者与NaOH溶液并流至钛白粉料浆中,保持料浆pH不变,均化60min,将均化完成的料浆再过一遍砂磨机,进行一遍砂磨;用氢氧化钠调节料浆pH为6.5,均化2h;
S3对包膜后料浆进行水洗,水洗至电导率<100μs/cm、闪蒸、500℃下煅烧1.5h、汽粉。汽粉时加入0.5%TMP,其他条件同实施例1,得到产品导电钛白粉D。
实施例4
一种导电钛白粉的制备方法,包括以下步骤:
S1未经包覆的钛白粉经粉碎、湿磨、砂磨(在砂磨前的料浆中加入1%六偏磷酸钠作为分散剂)、稀释后,料浆浓度为300g/L,料浆pH为7;高分子链PVP修饰钛白粉颗粒,在料浆中添加8wt%的高分子聚合物,保持温度为常温状态,开启搅拌和超声,超声开启10min后关闭;
S2用稀酸将料浆的pH调为2,15min调好,均化15min。在钛白粉料浆中加入20%的苯胺单体,在室温下搅拌均化6h,随后在料浆中加入引发单体聚合的引发剂过硫酸铵,该过程需要超声辅助,持续4h。然后将体系温度升高到60℃后,均化10min,在料浆中加入0.8%的氯化锡(以SnO2计)盐酸溶液和0.1%的氯化锑(以Sb2O3计)盐酸溶液,使其两者与NaOH溶液并流至钛白粉料浆中,保持料浆pH不变,均化60min,将均化完成的料浆再过一遍砂磨机,进行一遍砂磨;用氢氧化钠调节料浆pH为6.5,均化2h;
S3对包膜后料浆进行水洗,水洗至电导率<100μs/cm、闪蒸、400℃下煅烧2h、汽粉。汽粉时加入0.5%TMP,其他条件同实施例1,得到产品导电钛白粉E。
实施例1-4产品与对比产品(钛白粉A为通用进口导电钛白粉)在防静电涂料中的应用对比
1.导电钛白粉的物化性能对比
表1
2.涂料及漆膜性能对比(漆膜电阻率测试方法:GB/T 16906-1997,耐冲击性测试方法:GB/T 1732-1993,明度L*测试方法:GB/T11186.2-1989,遮盖力测试方法:GB/T5211.17-1988)
表2
从表1、表2及图1可知,经过在ATO包膜基础上增加了聚苯胺包膜,不仅修复了钛白粉表面本身的缺陷,而且还可以运用聚苯胺本身优异的电化学性能对导电钛白粉的导电性能大幅度提升,再者还可以对SnO2包膜的C、N掺杂之后,本发明提供的钛白粉不仅实现了比进口钛白粉更好的导电性,而且其光泽度、吸油量、遮盖力等数据均有相应的提高,由此可见,本发明提供的导电钛白粉不仅可以有效优化钛白粉的导电性及各项物化指标,还能大幅度提升导电钛白粉的耐候性。
尽管已描述了本发明的优选实施例,但本领域内的技术人员一旦得知了基本创造性概念,则可对这些实施例作出另外的变更和修改。所以,所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。显然,本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内,则本发明也意图包含这些改动和变型在内。
Claims (4)
1.一种导电钛白粉的制备方法,其特征在于,所述导电钛白粉包括二氧化钛基材和位于所述二氧化钛基材表面的包膜层,所述包膜层由内之外依次包括聚苯胺包膜层和ATO包膜层,所述ATO包膜层除掺杂Sb,还掺杂有C、N;
所述导电钛白粉的制备方法包括以下步骤:
S1:制备二氧化钛基材料浆、预处理并对其中的二氧化钛进行高分子修饰;所述预处理步骤为:取二氧化钛基材料浆加入二氧化钛总量0.05~1wt%的分散剂进行砂磨,得到砂磨料浆;所述高分子修饰步骤为:向所述预处理后的二氧化钛基材料浆中加入二氧化钛总量0.1~10 wt %的水溶性高分子聚合物,pH调节为1~3,超声,得到高分子修饰的二氧化钛料浆;
S2:将所述步骤S1修饰后的二氧化钛首先加入苯胺单体和水溶性引发剂反应,超声,进行聚苯胺包膜,将所述聚苯胺包膜的二氧化钛料浆升温至40~70℃,调节pH至1~3,均化后加入锡盐和锑盐,保持料浆的pH为1~3,均化;砂磨,然后调节pH至6.5~7.5,均化,得到ATO包膜后的二氧化钛料浆;所述苯胺单体的加入量为所述二氧化钛基材料浆中二氧化钛总量的3~20wt%,所述水溶性引发剂的加入量为二氧化钛基材料浆中二氧化钛总量50~300wt%;锡盐的加入量,以氧化锡计,为二氧化钛总量的0.1~3.0wt%,锑盐的加入量,以氧化锑计,为二氧化钛总量的0.1~0.5wt%;
S3:将所述步骤S2包膜后的料浆经过水洗、干燥、煅烧、制粉,得到所述导电钛白粉;在所述水洗、干燥、煅烧、制粉的任一阶段,还包括有机表面处理剂处理步骤;所述煅烧温度为400~500℃,煅烧时间为1.5~3h,经过所述煅烧,使ATO包膜层除掺杂Sb,还掺杂有C、N。
2.如权利要求1所述的导电钛白粉的制备方法,其特征在于,
所述步骤S1中用于高分子修饰的化合物为水溶性高分子聚合物,所述水溶性高分子聚合物为聚丙烯酰胺、聚丙烯酸、聚乙烯吡咯烷酮、聚乙烯醇、聚马来酸酐、聚季胺盐、或聚乙二醇中的一种或两种以上组合。
3.如权利要求1所述的导电钛白粉的制备方法,其特征在于,
所述水溶性引发剂为无机盐类过硫酸盐、过氧化氢或水溶性偶氮引发剂的任一种或两种以上组合。
4.如权利要求1所述的导电钛白粉的制备方法,其特征在于,
所述有机表面处理剂为多元醇或有机硅中的一种或多种,所述有机表面处理剂加入量为二氧化钛总量的0.01~1 wt %。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911220294.8A CN111040474B (zh) | 2019-12-03 | 2019-12-03 | 一种导电钛白粉及制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911220294.8A CN111040474B (zh) | 2019-12-03 | 2019-12-03 | 一种导电钛白粉及制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111040474A CN111040474A (zh) | 2020-04-21 |
CN111040474B true CN111040474B (zh) | 2022-03-18 |
Family
ID=70233374
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911220294.8A Active CN111040474B (zh) | 2019-12-03 | 2019-12-03 | 一种导电钛白粉及制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111040474B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114192191B (zh) * | 2021-12-31 | 2024-02-06 | 河南佰利联新材料有限公司 | 一种高光催化活性钛白粉及其制备方法 |
CN116970332A (zh) * | 2023-08-01 | 2023-10-31 | 浙江利邦电器有限公司 | 一种墙壁开关用表面喷漆工艺 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1385862A (zh) * | 2001-05-15 | 2002-12-18 | 上海博纳维来新材料有限公司 | 一种浅色超细导电粉的制备方法 |
CN1821315A (zh) * | 2006-01-24 | 2006-08-23 | 南京航空航天大学 | 聚苯胺包覆纳米TiO2及聚苯胺包覆TiO2晶须及其制备方法 |
CN105271389A (zh) * | 2015-10-15 | 2016-01-27 | 锦州钛业有限公司 | 一种导电二氧化钛粉体的制备方法 |
CN110003687A (zh) * | 2019-04-26 | 2019-07-12 | 龙蟒佰利联集团股份有限公司 | 一种高光泽户外涂料专用钛白粉的制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080194736A1 (en) * | 2007-02-13 | 2008-08-14 | Minqiu Lu | PVC nanocomposite manufacturing technology and applications |
-
2019
- 2019-12-03 CN CN201911220294.8A patent/CN111040474B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1385862A (zh) * | 2001-05-15 | 2002-12-18 | 上海博纳维来新材料有限公司 | 一种浅色超细导电粉的制备方法 |
CN1821315A (zh) * | 2006-01-24 | 2006-08-23 | 南京航空航天大学 | 聚苯胺包覆纳米TiO2及聚苯胺包覆TiO2晶须及其制备方法 |
CN105271389A (zh) * | 2015-10-15 | 2016-01-27 | 锦州钛业有限公司 | 一种导电二氧化钛粉体的制备方法 |
CN110003687A (zh) * | 2019-04-26 | 2019-07-12 | 龙蟒佰利联集团股份有限公司 | 一种高光泽户外涂料专用钛白粉的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN111040474A (zh) | 2020-04-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111040474B (zh) | 一种导电钛白粉及制备方法 | |
CN103219090B (zh) | 一种纳米银包覆高分子微球复合导电银浆的制备方法 | |
CN103192074A (zh) | 一种高分散型银粉和薄膜电池用导电银浆 | |
CN103073941B (zh) | 一种二氧化钒粉体浆料及其制备方法 | |
WO2016188114A1 (zh) | 一种原位合成聚3, 4-乙撑二氧噻吩/纳米金属银透明导电涂层的方法 | |
Qiu et al. | Preparation of poly (3, 4‐ethylenedioxythiophene)/poly (styrene sulfonate)(PEDT/PSS) composite and its applications in anti‐static coating | |
CN110698947A (zh) | 一种绝缘抗静电高反射水性涂料的制备方法 | |
Yu et al. | Preparation of titanium dioxide/poly (methyl methacrylate‐co‐n‐butyl acrylate‐co‐methacrylic acid) hybrid composite particles via emulsion polymerization | |
CN108124323A (zh) | 电热膜浆料及利用电热膜浆料制备电热膜的方法 | |
CN105778089A (zh) | 一种无机粒子改性磁性复合材料及其制备方法 | |
Shreepathi et al. | Spectroelectrochemistry and Preresonance Raman Spectroscopy of Polyaniline− Dodecylbenzenesulfonic Acid Colloidal Dispersions | |
WO2014024735A1 (ja) | インク組成物、インク組成物の製造方法、透明導電膜及び透明導電膜の製造方法 | |
CN105331054A (zh) | 一种复合导电薄膜 | |
CN101306834A (zh) | 高隔热性纳米复合材料及其隔热制品的制备方法 | |
Sun et al. | Dispersion of antimony doped tin oxide nanopowders for preparing transparent thermal insulation water-based coatings | |
CN111117431B (zh) | 一种水性环氧阻燃涂料及其制备方法 | |
JP5289077B2 (ja) | 針状酸化錫微粉末およびその製造方法 | |
CN109031812A (zh) | 一种手写板专用柔性透明导电膜及基于其的柔性手写膜 | |
KR20150088551A (ko) | 알칼리금속산화물이 도핑된 텅스텐산화물 복합체, 투명전도성 조성물, 코팅필름 및 이를 포함하는 광학소자 | |
CN113861549A (zh) | 一种EVA/聚吡咯/MXene复合材料及其制备方法与应用 | |
Saravanan et al. | Application of polyaniline/clay combination to cellulosic paper as an approach to conductivity development | |
CN113402772A (zh) | 一种抗静电防辐射的ato纳米粉体材料 | |
CN107903664B (zh) | 一种无机浅色导电二氧化钛粉体的制备方法 | |
CN104479117A (zh) | 一种原位聚合法制备智能温控聚酯切片的方法 | |
Cho et al. | Electrophoretic Display of surface modified TiO 2 driven by Poly (3, 4-ethylenedioxythiophene) Electrode |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |