CN115595008A - Conductive micro powder for polymer-based PTC (Positive temperature coefficient) material, preparation method of conductive micro powder and PTC self-temperature-control coating - Google Patents

Conductive micro powder for polymer-based PTC (Positive temperature coefficient) material, preparation method of conductive micro powder and PTC self-temperature-control coating Download PDF

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CN115595008A
CN115595008A CN202211153557.XA CN202211153557A CN115595008A CN 115595008 A CN115595008 A CN 115595008A CN 202211153557 A CN202211153557 A CN 202211153557A CN 115595008 A CN115595008 A CN 115595008A
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crystalline organic
ptc
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王明科
张忠厚
韩琳
程伟伟
王亚男
任可可
林宝德
陈荣源
张赛
温阳
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Zhengzhou Light Industry Technology Research Institute Co ltd
Henan Puliteke New Material Co ltd
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    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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Abstract

The invention relates to conductive micro powder for a polymer-based PTC material, a preparation method thereof and a PTC self-temperature-control coating, belonging to the technical field of polymer-based PTC materials. The conductive micro powder comprises a solid filler for a polymer-based PTC material and a crystalline organic substance layer coated on the surface of the solid filler for the polymer-based PTC material; the solid filler for the polymer-based PTC material comprises a conductive carbon material; the main component of the crystalline organic matter layer is a crystalline organic matter, and the mass ratio of the conductive carbon material to the crystalline organic matter is 10-120; the grain diameter of the conductive micro powder is less than or equal to 80 mu m. The conductive micro powder can obviously inhibit the NTC phenomenon of the polymer-based PTC material and improve the safety of the polymer-based PTC material.

Description

一种用于聚合物基PTC材料的导电微粉及其制备方法、PTC自 控温涂料A kind of conductive micropowder for polymer base PTC material and preparation method thereof, PTC self-contained Temperature Control Coating

技术领域technical field

本发明涉及一种用于聚合物基PTC材料的导电微粉及其制备方法、PTC自控温涂料,属于聚合物基PTC材料技术领域。The invention relates to a conductive micropowder for polymer-based PTC materials, a preparation method thereof, and a PTC self-temperature-control coating, belonging to the technical field of polymer-based PTC materials.

背景技术Background technique

PTC(positive temperature coefficient)材料,即正温度系数材料,电阻会随温度的升高呈现非线性变化,并且沿着特定的变换曲线进行自我调节,在特定温度范围内电阻率可跃迁多个数量级,完成由导电材料或半导电材料向绝缘材料的转变。这种特殊的温度响应能力赋予其一种开关响应特性,在智能家居、电热传感、保温建筑、新能源锂电等领域均有着广泛的应用。其中,PTC材料又被划分为陶瓷基PTC材料和聚合物基PTC材料两大类。陶瓷基PTC材料主要依赖于不同温度下材料晶界势垒的改变诱发电阻率的增大或减小,通常情况下采用添加不同类型和比例的施主元素、受主元素完成对其电阻率大小及PTC特性的调控,目前基于陶瓷基的PTC材料技术已经趋于完善,市面上已经可以较为广泛的见到系列控温产品。PTC (positive temperature coefficient) material, that is, positive temperature coefficient material, the resistance will show a nonlinear change with the increase of temperature, and it will self-regulate along a specific transformation curve. The resistivity can jump by multiple orders of magnitude in a specific temperature range. Complete the transition from conductive or semiconductive materials to insulating materials. This special temperature response ability gives it a switch response characteristic, which has a wide range of applications in smart home, electrothermal sensing, thermal insulation buildings, new energy lithium batteries and other fields. Among them, PTC materials are divided into two categories: ceramic-based PTC materials and polymer-based PTC materials. Ceramic-based PTC materials mainly depend on the increase or decrease of resistivity induced by the change of material grain boundary barrier at different temperatures. Usually, different types and proportions of donor elements and acceptor elements are added to complete the resistivity and The control of PTC characteristics, the current PTC material technology based on ceramic base has been perfected, and a series of temperature control products can be seen in the market.

聚合物PTC材料相比陶瓷基PTC材料具有原料易得、价格便宜、质量轻、易于加工制备、室温电阻率低等优点,同时又兼具高分子材料的许多优异性能,因此日益受到人们的广泛关注。聚合物基PTC材料的自控温特性来自于树脂基体的热膨胀所引发的导电网络破坏,聚合物基PTC材料的使用温度受聚合物基体的玻璃化温度和熔点影响。市面上常见的聚合物基PTC材料,主要是在聚合物中填充一定量的炭系导电填料形成的复合材料,以中低温电热系列产品为主,控温温度一般≤80℃,高温多为陶瓷基PTC材料,无法被制成涂料,在很多场合应用受限。另外,从目前工业化的产品来看,大多数PTC自控温元器件往往以立体块状存在且质地坚硬,极大的限制了其在复杂或狭小区域的应用。而PTC涂料具有使用灵活的特点,可以摆脱使用环境对PTC材料的限制。例如,文献号为CN108912990A的中国发明专利申请公开了一种水性PTC纳米碳电热涂料,由导电碳材料、聚合物微粉、助剂、水性粘结树脂及水组成,其基本组成及重量百分比为:导电碳材料1-20%、聚合物微粉2-15%、助剂1-10%、水性粘结树脂10-30%,余量为水;其中聚合物微粉为结晶型的热塑性聚合物粉末,粒径200纳米-5微米,或是聚乙烯、聚丙烯、尼龙、聚对苯二甲酸乙酯、聚对苯二甲酸丁酯、聚甲醛的任意一种及组合。该水性PTC纳米碳电热涂料利用结晶型热塑性聚合物热循环中的结晶-软化转变,带动纳米碳导电网络的变化,从而改变涂层内部的电阻,获得正温度电阻(PTC)效应,实现对电加热涂料功率的调控,获得安全高效的电加热涂层。但其采用导电碳材料和聚合物微粉在制备时涂料时独立加入体系,PTC强度最高仅能达到5,在电压不稳或局部温度冲高时很容易发生热失控,这对于其使用安全性是不利的;并且该PTC电热涂料中以结晶-软化转变作为调控导电网络的主要因素,温度趋于聚合物软化点或熔点时,彼此连通的聚合物分子发生热变形,分子链运动剧烈,温度降低后彼此连通的聚合物收缩回复性及空间排布的回复性都会受到影响,这对其长期使用下的室温电阻回复性是不利的,后期容易出现室温电阻增大等问题,影响其使用寿命。Compared with ceramic-based PTC materials, polymer PTC materials have the advantages of easy availability of raw materials, cheap price, light weight, easy processing and preparation, and low room temperature resistivity. At the same time, they also have many excellent properties of polymer materials, so they are increasingly popular. focus on. The self-temperature control characteristic of polymer-based PTC materials comes from the destruction of the conductive network caused by the thermal expansion of the resin matrix, and the service temperature of polymer-based PTC materials is affected by the glass transition temperature and melting point of the polymer matrix. The common polymer-based PTC materials on the market are mainly composite materials formed by filling a certain amount of carbon-based conductive fillers in the polymer. They are mainly medium and low temperature electric heating series products. The temperature control temperature is generally ≤80°C, and the high temperature is mostly ceramics. PTC-based materials cannot be made into coatings, and their applications are limited in many occasions. In addition, judging from the current industrialized products, most PTC self-temperature-controlling components often exist in three-dimensional blocks and are hard in texture, which greatly limits their application in complex or narrow areas. The PTC coating has the characteristics of flexible use, which can get rid of the restrictions of the use environment on PTC materials. For example, the Chinese invention patent application with document number CN108912990A discloses a water-based PTC nano-carbon electrothermal coating, which is composed of conductive carbon material, polymer powder, additives, water-based adhesive resin and water. The basic composition and weight percentage are: Conductive carbon material 1-20%, polymer micropowder 2-15%, additive 1-10%, water-based binder resin 10-30%, and the balance is water; the polymer micropowder is crystalline thermoplastic polymer powder, The particle size is 200 nanometers to 5 microns, or any one or combination of polyethylene, polypropylene, nylon, polyethylene terephthalate, polybutylene terephthalate, and polyoxymethylene. The water-based PTC nano-carbon electrothermal coating utilizes the crystallization-softening transition in the thermal cycle of crystalline thermoplastic polymers to drive the change of the nano-carbon conductive network, thereby changing the internal resistance of the coating, obtaining the positive temperature resistance (PTC) effect, and realizing the electric resistance. The regulation of heating paint power can obtain safe and efficient electric heating coating. However, it uses conductive carbon material and polymer micropowder to add to the system independently during the preparation of the coating. The highest PTC strength can only reach 5. When the voltage is unstable or the local temperature rises, thermal runaway is easy to occur, which is very important for its safety. Unfavorable; and in the PTC electrothermal coating, the crystallization-softening transition is used as the main factor to regulate the conductive network. When the temperature tends to the softening point or melting point of the polymer, the polymer molecules connected to each other undergo thermal deformation, the molecular chain moves violently, and the temperature drops The shrinkage recovery and spatial arrangement recovery of polymers that are connected to each other will be affected, which is not good for the room temperature resistance recovery under long-term use, and problems such as room temperature resistance increase will easily occur in the later period, which will affect its service life.

发明内容Contents of the invention

本发明的目的是提供一种用于聚合物基PTC材料的导电微粉,能够解决PTC电热涂料容易发生热失控以及长期使用容易出现室温电阻增大的问题。The purpose of the present invention is to provide a conductive micropowder used in polymer-based PTC materials, which can solve the problems that PTC electrothermal coatings are prone to thermal runaway and long-term use is prone to increase in room temperature resistance.

本发明同时提供了一种用于聚合物基PTC材料的导电微粉的制备方法。The invention also provides a method for preparing conductive micropowder used in polymer-based PTC materials.

本发明还提供了一种PTC自控温涂料,具有优良的高温稳定性。The invention also provides a PTC self-temperature-control coating, which has excellent high-temperature stability.

为了实现以上目的,本发明的用于聚合物基PTC材料的导电微粉所采用的技术方案是:In order to achieve the above object, the technical scheme adopted for the conductive micropowder of the polymer-based PTC material of the present invention is:

一种用于聚合物基PTC材料的导电微粉,包括聚合物基PTC材料用固体填料和包覆在所述聚合物基PTC材料用固体填料表面的结晶性有机物层;所述聚合物基PTC材料用固体填料包括导电碳材;所述结晶性有机物层的主要成分为结晶性有机物,导电碳材与结晶性有机物的质量之比为10~120:10~50;所述导电微粉的粒径≤80μm。A conductive micropowder for a polymer-based PTC material, comprising a solid filler for a polymer-based PTC material and a crystalline organic layer coated on the surface of the solid filler for a polymer-based PTC material; the polymer-based PTC material The solid filler includes conductive carbon material; the main component of the crystalline organic layer is crystalline organic matter, and the mass ratio of conductive carbon material to crystalline organic matter is 10-120:10-50; the particle size of the conductive fine powder is ≤ 80 μm.

本发明的用于聚合物基PTC材料的导电微粉,在导电碳材表面包覆结晶性有机物,一方面可以使导电碳材处于“粒粒分明”的状态,这很好的限制导电碳材的团聚,同时导电碳材表面的结晶性有机物与基体树脂具有极佳的相容性,能够促进导电碳材在涂料中的均匀分散;另一方面,由于结晶性有机物的阻隔作用,能够使导电碳材以“孤岛”形式分布于树脂体系中。室温状态下,不同类型的碳材料彼此之间形成丰富致密的导电网络,赋予PTC材料出色的室温电阻率和电热特性。The conductive micropowder for polymer-based PTC materials of the present invention coats crystalline organic matter on the surface of the conductive carbon material. Reunion, and the crystalline organic matter on the surface of the conductive carbon material has excellent compatibility with the matrix resin, which can promote the uniform dispersion of the conductive carbon material in the coating; on the other hand, due to the barrier effect of the crystalline organic matter, it can make the conductive carbon material The materials are distributed in the resin system in the form of "islands". At room temperature, different types of carbon materials form a rich and dense conductive network with each other, endowing PTC materials with excellent room temperature resistivity and electrothermal properties.

此外,由于本发明的导电微粉中导电碳材和结晶性有机物的特殊结构关系,能够显著抑制聚合物基PTC材料的NTC现象,提高聚合物基PTC材料的安全性,这是由于包覆结构使得结晶性有机物以“孤岛”形式存在,大多数情况下独立的分布于树脂基体中,仅有少量粘结;因此即便温度局部冲高,熔融的结晶性有机物也会被基体树脂牢牢的固定在其狭小的空间内,抑制导电碳材重排构成新的导电网络,进而有效抑制了聚合物基PTC材料的NTC现象,改善其电学回复性。同时,因为结晶性有机物包覆于导电碳材表面,轻微的膨胀便可迫使彼此相邻的碳材料分离,从而引发导电网络的破坏,为其提供较高的PTC强度。In addition, due to the special structural relationship between the conductive carbon material and the crystalline organic matter in the conductive micropowder of the present invention, the NTC phenomenon of the polymer-based PTC material can be significantly suppressed, and the safety of the polymer-based PTC material can be improved. This is because the coating structure makes The crystalline organic matter exists in the form of "islands", and in most cases, it is independently distributed in the resin matrix, with only a small amount of bonding; therefore, even if the temperature is locally increased, the molten crystalline organic matter will be firmly fixed by the matrix resin. In its narrow space, it inhibits the rearrangement of conductive carbon materials to form a new conductive network, thereby effectively inhibiting the NTC phenomenon of polymer-based PTC materials and improving their electrical recovery. At the same time, because the crystalline organic matter is coated on the surface of the conductive carbon material, a slight expansion can force the adjacent carbon materials to separate, thereby causing the destruction of the conductive network and providing it with a higher PTC strength.

进一步地,所述结晶性有机物的熔点为T,40℃≤T<80℃或T≥80℃;40℃≤T<80℃时,所述结晶性有机物为结晶聚合物和/或非聚合物型结晶性有机物;T≥80℃时,所述结晶性有机物为结晶聚合物。Further, the melting point of the crystalline organic matter is T, 40°C≤T<80°C or T≥80°C; when 40°C≤T<80°C, the crystalline organic matter is a crystalline polymer and/or a non-polymer Type crystalline organic matter; when T≥80°C, the crystalline organic matter is a crystalline polymer.

进一步地,40℃≤T<80℃,所述结晶聚合物为聚乙二醇(PEG)、乙烯-醋酸乙烯共聚物(EVA)、氧化聚乙烯蜡(OPE)、聚己内酯(PCL)中的一种或任意合,所述非聚合物型结晶性有机物为棕榈酸、月桂酸、12-羟基硬脂酸中的一种或任意组合;或80℃≤T≤120℃,所述结晶聚合物为聚乙烯(PE)、聚乙烯蜡(PEW)、聚丙烯(PP)、乙烯-醋酸乙烯共聚物(EVA)、乙烯-丙烯酸甲酯共聚物(EMA)、乙烯-丙烯酸共聚物(EAA)、聚氧化乙烯(PEO)、聚氯乙烯(PVC)、氯化聚乙烯(CPE)中的一种或任意组合。Further, 40°C≤T<80°C, the crystalline polymer is polyethylene glycol (PEG), ethylene-vinyl acetate copolymer (EVA), oxidized polyethylene wax (OPE), polycaprolactone (PCL) One or any combination of these, the non-polymer crystalline organic matter is one or any combination of palmitic acid, lauric acid, and 12-hydroxystearic acid; or 80°C≤T≤120°C, the crystallization The polymers are polyethylene (PE), polyethylene wax (PEW), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-acrylic acid copolymer (EAA) ), polyethylene oxide (PEO), polyvinyl chloride (PVC), chlorinated polyethylene (CPE), or any combination.

进一步地,导电碳材与结晶性有机物的质量之比为42~57:50,例如为45~56.7:50或42.8~52.5:50。Further, the mass ratio of the conductive carbon material to the crystalline organic matter is 42-57:50, for example, 45-56.7:50 or 42.8-52.5:50.

进一步地,所述导电碳材为石墨烯类二维碳材、超导炭黑和碳纤维;石墨烯类二维碳材、超导炭黑、碳纤维和结晶性有机物的质量之比为5~30:5~40:0~50:10~50,优选为16~30:11~20:5~15:50,例如为16.6~30:13.3~20:5~13.4:50或17.1~25:11.4~13.4:8.3~14.3:50。所述石墨烯类二维碳材的片径为300nm-15μm;所述超导炭黑的粒径为35-300nm;所述碳纤维的单丝直径为1-10μm,长径比为2-15:1。Further, the conductive carbon material is graphene-based two-dimensional carbon material, superconducting carbon black and carbon fiber; the mass ratio of graphene-based two-dimensional carbon material, superconducting carbon black, carbon fiber and crystalline organic matter is 5-30 :5~40:0~50:10~50, preferably 16~30:11~20:5~15:50, such as 16.6~30:13.3~20:5~13.4:50 or 17.1~25:11.4 ~13.4:8.3~14.3:50. The sheet diameter of the graphene-like two-dimensional carbon material is 300nm-15μm; the particle size of the superconducting carbon black is 35-300nm; the monofilament diameter of the carbon fiber is 1-10μm, and the aspect ratio is 2-15 :1.

进一步地,所述导电微粉的粒径≤75μm。所述导电微粉的平均粒径为10~30μm,例如为21~28μm。Further, the particle size of the conductive fine powder is ≤75 μm. The average particle size of the conductive fine powder is 10-30 μm, for example, 21-28 μm.

进一步地,所述石墨烯类二维碳材为单层石墨烯、多层石墨烯、氧化石墨烯中的一种或任意组合;所述超导炭黑为乙炔炭黑和/或科琴黑。Further, the graphene-like two-dimensional carbon material is one or any combination of single-layer graphene, multilayer graphene, and graphene oxide; the superconducting carbon black is acetylene carbon black and/or Ketjen black .

进一步地,所述聚合物基PTC材料用固体填料还包括无机导热填料;无机导热填料与结晶性有机物的质量之比为5~30:10~50,优选为13~20:50,例如为13.3~20:50或14.2~20:50。Further, the solid filler for the polymer-based PTC material also includes an inorganic thermally conductive filler; the mass ratio of the inorganic thermally conductive filler to the crystalline organic matter is 5-30:10-50, preferably 13-20:50, for example, 13.3 ~20:50 or 14.2~20:50.

本发明的用于聚合物基PTC材料的导电微粉的制备方法所采用的技术方案为:The technical scheme adopted in the preparation method of the conductive micropowder for polymer-based PTC material of the present invention is:

一种用于聚合物基PTC材料的导电微粉的制备方法,包括以下步骤:将混合浆料干燥成固体,然后破碎成微粉;所述混合浆料是将聚合物基PTC材料用固体填料分散在结晶性有机物乳液中得到;所述聚合物基PTC材料用固体填料包括导电碳材;所述导电碳材与结晶性有机物乳液中结晶性有机物的质量之比为10~120:10~50;所述导电微粉的粒径≤80μm。A method for preparing conductive micropowder for polymer-based PTC materials, comprising the steps of: drying the mixed slurry into solids, and then crushing into micropowder; the mixed slurry is to disperse the polymer-based PTC materials with solid fillers Obtained from a crystalline organic matter emulsion; the solid filler for the polymer-based PTC material includes a conductive carbon material; the mass ratio of the conductive carbon material to the crystalline organic matter in the crystalline organic matter emulsion is 10-120:10-50; The particle size of the conductive micropowder is ≤80 μm.

本发明的用于聚合物基PTC材料导电微粉的制备方法,可以提高聚合物基PTC材料用固体填料在制备的导电微粉中的分散均匀程度。The preparation method for the polymer-based PTC material conductive micropowder of the present invention can improve the degree of uniform dispersion of the solid filler for the polymer-based PTC material in the prepared conductive micropowder.

进一步地,所述导电微粉的粒径≤75μm。所述导电微粉的平均粒径为10~30μm,例如为21~28μm。Further, the particle size of the conductive fine powder is ≤75 μm. The average particle size of the conductive fine powder is 10-30 μm, for example, 21-28 μm.

进一步地,所述导电碳材与结晶性有机物乳液中结晶性有机物的质量之比为27~34:30~35。Further, the mass ratio of the conductive carbon material to the crystalline organic matter in the crystalline organic matter emulsion is 27-34:30-35.

进一步地,所述结晶性有机物的熔点为T,40℃≤T<80℃或T≥80℃;40℃≤T<80℃时,所述结晶性有机物为结晶聚合物和/或非聚合物型结晶性有机物;T≥80℃时,所述结晶性有机物为结晶聚合物。Further, the melting point of the crystalline organic matter is T, 40°C≤T<80°C or T≥80°C; when 40°C≤T<80°C, the crystalline organic matter is a crystalline polymer and/or a non-polymer Type crystalline organic matter; when T≥80°C, the crystalline organic matter is a crystalline polymer.

进一步地,40℃≤T<80℃,所述结晶聚合物为聚乙二醇、乙烯-醋酸乙烯共聚物、氧化聚乙烯蜡、聚己内酯中的一种或任意合,所述非聚合物型结晶性有机物为棕榈酸、月桂酸、12-羟基硬脂酸中的一种或任意组合;或80℃≤T≤120℃,所述结晶聚合物为聚乙烯、聚乙烯蜡、聚丙烯、乙烯-醋酸乙烯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物、聚氧化乙烯、聚氯乙烯、氯化聚乙烯中的一种或任意组合。例如,乙烯-醋酸乙烯共聚物中VA含量为28%或40%。例如结晶聚合物为熔点58-63℃的聚乙二醇、熔点70℃的乙烯-醋酸乙烯共聚物或熔点60-65℃的硬脂酸,又如结晶聚合物为熔点100-105℃的聚乙烯蜡、熔点85-90℃的聚氧化乙烯或熔点95℃的乙烯-醋酸乙烯共聚物。Further, when 40°C≤T<80°C, the crystalline polymer is one or any combination of polyethylene glycol, ethylene-vinyl acetate copolymer, oxidized polyethylene wax, and polycaprolactone, and the non-polymeric The physical form of crystalline organic matter is one or any combination of palmitic acid, lauric acid, and 12-hydroxystearic acid; or 80°C≤T≤120°C, and the crystalline polymer is polyethylene, polyethylene wax, polypropylene , ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, polyethylene oxide, polyvinyl chloride, chlorinated polyethylene, or any combination thereof. For example, VA content in ethylene-vinyl acetate copolymer is 28% or 40%. For example, the crystalline polymer is polyethylene glycol with a melting point of 58-63°C, ethylene-vinyl acetate copolymer with a melting point of 70°C, or stearic acid with a melting point of 60-65°C; Ethylene wax, polyethylene oxide with a melting point of 85-90°C or ethylene-vinyl acetate copolymer with a melting point of 95°C.

进一步地,所述导电碳材由以下重量份数的组分组成:石墨烯类二维碳材5~30份、超导炭黑5~40份、碳纤维0~50份,也就是说:所述导电碳材由石墨烯二维碳材、超导炭黑和碳纤维组成,石墨烯二维碳材、超导炭黑和碳纤维的质量之比为5~30:5~40:0~50。进一步地,石墨烯二维碳材、超导炭黑和碳纤维的质量之比为16~30:11~20:5~15:50,例如为16.6~30:13.3~20:5~13.4:50或17.1~25:11.4~13.4:8.3~14.3:50。所述石墨烯类二维碳材与结晶性有机物的质量之比为5~30:10~50,优选为16~30:50,例如为16.6~30:50或17.1~25:50。Further, the conductive carbon material is composed of the following components in parts by weight: 5-30 parts of graphene-based two-dimensional carbon material, 5-40 parts of superconducting carbon black, and 0-50 parts of carbon fiber, that is to say: The conductive carbon material is composed of graphene two-dimensional carbon material, superconducting carbon black and carbon fiber, and the mass ratio of graphene two-dimensional carbon material, superconducting carbon black and carbon fiber is 5-30:5-40:0-50. Further, the mass ratio of graphene two-dimensional carbon material, superconducting carbon black and carbon fiber is 16-30:11-20:5-15:50, for example, 16.6-30:13.3-20:5-13.4:50 Or 17.1~25:11.4~13.4:8.3~14.3:50. The mass ratio of the graphene-based two-dimensional carbon material to the crystalline organic matter is 5-30:10-50, preferably 16-30:50, such as 16.6-30:50 or 17.1-25:50.

进一步地,所述石墨烯类二维碳材的片径为300nm-15μm,优选为0.5~8μm,例如为0.5~3μm、0.8~5μm或5~8μm;所述超导炭黑的粒径为30-300nm,优选为30~240nm,例如为30~45nm、45~70nm或200~240nm;所述碳纤维的单丝直径为1-10μm,例如为2.6μm、5μm或6.5μm,长径比为2-15:1。Further, the sheet diameter of the graphene-based two-dimensional carbon material is 300nm-15μm, preferably 0.5-8μm, such as 0.5-3μm, 0.8-5μm or 5-8μm; the particle size of the superconducting carbon black is 30-300nm, preferably 30-240nm, such as 30-45nm, 45-70nm or 200-240nm; the monofilament diameter of the carbon fiber is 1-10μm, such as 2.6μm, 5μm or 6.5μm, and the aspect ratio is 2-15:1.

进一步地,所述超导炭黑为乙炔炭黑和/或科琴黑;所述石墨烯类二维碳材为单层石墨烯、多层石墨烯、氧化石墨烯中的一种或任意组合。Further, the superconducting carbon black is acetylene black and/or Ketjen black; the graphene-like two-dimensional carbon material is one or any combination of single-layer graphene, multi-layer graphene, and graphene oxide .

进一步地,所述结晶性有机物乳液是将结晶有机物分散在水中形成;所述结晶性有机物乳液的制备方法包括以下步骤:将结晶性有机物、乳化剂和分散剂加热至结晶性有机物熔点以上熔融混匀,然后加水在设定压力和设定温度下进行分散乳化,即得。水在所述设定压力下的沸点不低于结晶性有机物的熔点,且所述设定温度不高于水在所述设定压力下的沸点。Further, the crystalline organic matter emulsion is formed by dispersing the crystalline organic matter in water; the preparation method of the crystalline organic matter emulsion includes the following steps: heating the crystalline organic matter, emulsifier and dispersant to a temperature above the melting point of the crystalline organic matter and melting and mixing Mix well, then add water to disperse and emulsify under the set pressure and set temperature. The boiling point of water under the set pressure is not lower than the melting point of crystalline organic matter, and the set temperature is not higher than the boiling point of water under the set pressure.

进一步地,所述乳化剂为阴离子型乳化剂和/或非离子型乳化剂;所述阴离子型乳化剂为烷基硫酸盐、烷基磺酸盐、烷基苯磺酸盐中的一种或任意组合;所述烷基硫酸盐为十二烷基硫酸钠;所述烷基磺酸盐为十二烷基磺酸钠;所述烷基苯磺酸盐为十二烷基苯磺酸钠;所述非离子型乳化剂为烷基酚聚氧乙烯醚乳化剂、失水山梨醇脂肪酸酯乳化剂、聚氧乙烯失水山梨醇脂肪酸酯乳化剂中的一种或任意组合;所述烷基酚聚氧乙烯醚乳化剂为OP-6、OP-7、OP-8、OP-9中的一种或任意组合;所述失水山梨醇脂肪酸酯乳化剂为Span 40、Span60、Span 80中的一种或任意组合;所述聚氧乙烯失水山梨醇脂肪酸酯乳化剂为Tween-20、Tween-40、Tween-60中的一种或任意组合。Further, the emulsifier is an anionic emulsifier and/or a nonionic emulsifier; the anionic emulsifier is one of alkyl sulfate, alkyl sulfonate, alkylbenzene sulfonate or Any combination; the alkylsulfate is sodium dodecylsulfate; the alkylsulfonate is sodium dodecylsulfonate; the alkylbenzenesulfonate is sodium dodecylbenzenesulfonate The nonionic emulsifier is one or any combination of alkylphenol polyoxyethylene ether emulsifier, sorbitan fatty acid ester emulsifier, polyoxyethylene sorbitan fatty acid ester emulsifier; The alkylphenol polyoxyethylene ether emulsifier is one or any combination of OP-6, OP-7, OP-8, OP-9; the sorbitan fatty acid ester emulsifier is Span 40, Span60 , Span 80 or any combination; the polyoxyethylene sorbitan fatty acid ester emulsifier is one or any combination of Tween-20, Tween-40, Tween-60.

进一步地,所述分散剂为脂肪酸类分散剂、脂肪族酰胺类分散剂、甘油酯类分散剂中的一种或任意组合;所述脂肪酸类分散剂为肉豆蔻酸、棕榈酸、硬脂酸中的一种或任意组合;所述脂肪族酰胺类分散剂为硬脂酸酰胺、芥酸酰胺、油酸酰胺、油酸二乙醇酰胺、乙烯基双硬脂酰胺中的一种或任意组合;所述甘油酯类分散剂为辛癸酸甘油酯、二油酸甘油酯、硬脂酸单甘油酯中的一种或任意组合。Further, the dispersant is one or any combination of fatty acid dispersant, aliphatic amide dispersant, glyceride dispersant; the fatty acid dispersant is myristic acid, palmitic acid, stearic acid One of or any combination of; the aliphatic amide dispersant is one or any combination of stearic acid amide, erucamide, oleic acid amide, oleic acid diethanolamide, vinylbisstearamide; The glyceride dispersant is one or any combination of glyceryl caprate, glyceryl dioleate, and monoglyceride stearate.

进一步地,所述聚合物基PTC材料用固体填料还包括无机导热填料,所述无机导热填料与结晶性有机物乳液中结晶性有机物的质量之比为5~30:10~50,优选为13~20:50,例如为13.3~20:50或14.2~20:50;所述无机导热填料的粒径为50nm~5μm,优选为1.3~5μm,例如为1.3~1.5μm或3~5μm。Further, the solid filler for the polymer-based PTC material also includes an inorganic thermally conductive filler, and the mass ratio of the inorganic thermally conductive filler to the crystalline organic compound in the crystalline organic compound emulsion is 5-30:10-50, preferably 13-50 20:50, for example 13.3-20:50 or 14.2-20:50; the particle size of the inorganic thermally conductive filler is 50nm-5μm, preferably 1.3-5μm, for example 1.3-1.5μm or 3-5μm.

可以理解的是,所述无机导热填料为半导体填料和/或非导电填料。所述无机导热填料具有规则的晶体结构。进一步地,所述无机导热填料选自碳化硅、二氧化硅、氮化硼、氮化铝中的一种或任意组合。It can be understood that the inorganic thermally conductive filler is a semiconductor filler and/or a non-conductive filler. The inorganic thermally conductive filler has a regular crystal structure. Further, the inorganic thermally conductive filler is selected from one or any combination of silicon carbide, silicon dioxide, boron nitride, and aluminum nitride.

本发明的PTC自控温涂料所采用的技术方案为:The technical scheme adopted by the PTC self-temperature-control coating of the present invention is:

一种PTC自控温涂料,包括树脂乳液和分散在树脂乳液中的导电微粉和添加剂;所述导电微粉为上述用于聚合物基PTC材料的导电微粉或上述用于聚合物基PTC材料的导电微粉的制备方法制得的用于聚合物基PTC材料的导电微粉。A PTC self-temperature-controlling paint, comprising resin emulsion and conductive micropowder and additives dispersed in the resin emulsion; said conductive micropowder is the above-mentioned conductive micropowder for polymer-based PTC materials or the above-mentioned conductive micropowder for polymer-based PTC materials The preparation method of the micropowder is the conductive micropowder used for polymer-based PTC materials.

本发明的PTC自控温涂料,相较于常见的低温PTC自控温涂料,属于高温段PTC自控温涂料,涂覆后形成的电热膜具有良好的电学回复性、发热稳定性以及低的室温电阻,并具有优良的高低温稳定性,即便长期使用也不会出现热老化,自控温效果好,使用安全性高,具有广阔的应用前景。本发明的PTC自控温涂料,制备工艺简单,仅需将各原料混匀即可,施工工艺灵活、易于印刷为多种形状,具有良好的可定制属性。The PTC self-temperature control coating of the present invention, compared with the common low-temperature PTC self-temperature control coating, belongs to the high-temperature segment PTC self-temperature control coating, and the electrothermal film formed after coating has good electrical recovery, heat generation stability and low Room temperature resistance, and has excellent high and low temperature stability, no thermal aging even if used for a long time, good self-temperature control effect, high safety in use, and has broad application prospects. The PTC self-temperature-controlling paint of the present invention has a simple preparation process, and only needs to mix the raw materials. The construction process is flexible, easy to print into various shapes, and has good customizable properties.

尤其是导电微粉中结晶聚合物的熔点为80~120℃,所述结晶聚合物为聚乙烯、聚乙烯蜡、聚丙烯、乙烯-醋酸乙烯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物、聚氧化乙烯、聚氯乙烯、氯化聚乙烯中的一种或任意组合时,本发明的PTC自控温涂料在75-110℃之间具有良好自控温特性,填补了市售PTC材料温度区间上的空白。In particular, the melting point of the crystalline polymer in the conductive micropowder is 80-120°C, and the crystalline polymer is polyethylene, polyethylene wax, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid When one or any combination of copolymers, polyethylene oxide, polyvinyl chloride, and chlorinated polyethylene, the PTC self-temperature-controlling coating of the present invention has good self-temperature-controlling properties between 75-110°C, filling the market Blank on the PTC material temperature range.

进一步地,所述树脂乳液中固形物与导电微粉中结晶性有机物的质量之比为30~60:10~50,优选为45~60:30~35。Further, the mass ratio of the solid matter in the resin emulsion to the crystalline organic matter in the conductive fine powder is 30-60:10-50, preferably 45-60:30-35.

可以理解的是,本发明的树脂乳液为水性树脂乳液,树脂乳液中树脂为热塑性聚合物时,树脂在PTC自控温涂料固化后形成的聚合物的熔点或软化点高于导电微粉中结晶性有机物的熔点;树脂乳液中的树脂为热固性聚合物时,树脂在PTC自控温涂料固化后形成的聚合物的热变形温度不低于导电微粉中结晶性有机物的熔点。进一步地,所述树脂乳液为聚氨酯乳液、丙烯酸乳液、丙烯酸酯乳液、有机硅乳液、环氧树脂乳液中的一种或任意组合;所述树脂乳液的固含量为30~60%。例如,所述丙烯酸酯乳液为硅丙乳液、苯丙乳液、纯丙乳液中的任意一种或任意组合。进一步地,水性树脂乳液既可以为单组分水性树脂乳液,也可以为双组分水性树脂乳液。可以理解的是,单组分水性树脂乳液为自交联水性树脂乳液。例如环氧树脂乳液、聚氨酯乳液可以为双组分,也可以为单组分。It can be understood that the resin emulsion of the present invention is an aqueous resin emulsion, and when the resin in the resin emulsion is a thermoplastic polymer, the melting point or softening point of the polymer formed by the resin after the PTC self-temperature control coating is cured is higher than that of the conductive micropowder. The melting point of the organic matter; when the resin in the resin emulsion is a thermosetting polymer, the heat distortion temperature of the polymer formed by the resin after the PTC self-temperature control coating is cured is not lower than the melting point of the crystalline organic matter in the conductive micropowder. Further, the resin emulsion is one or any combination of polyurethane emulsion, acrylic emulsion, acrylate emulsion, silicone emulsion, and epoxy resin emulsion; the solid content of the resin emulsion is 30-60%. For example, the acrylate emulsion is any one or any combination of silicone-acrylic emulsion, styrene-acrylic emulsion, and pure acrylic emulsion. Further, the water-based resin emulsion can be either a one-component water-based resin emulsion or a two-component water-based resin emulsion. It can be understood that the one-component water-based resin emulsion is a self-crosslinking water-based resin emulsion. For example, epoxy resin emulsion and polyurethane emulsion can be two-component or one-component.

进一步地,所述添加剂包括消泡剂和流平剂;所述消泡剂、流平剂和树脂乳液质量之比为3~50:3~50:1000,优选为5~50:5~50:1000。Further, the additive includes a defoamer and a leveling agent; the mass ratio of the defoamer, leveling agent and resin emulsion is 3-50:3-50:1000, preferably 5-50:5-50 :1000.

进一步地,所述消泡剂为有机硅型消泡剂和/或聚醚改性有机硅型消泡剂;所述流平剂为丙烯酸类流平剂、丙烯酸酯类流平剂、有机硅流平剂中的一种或任意组合;所述丙烯酸类流平剂的主要成分为丙烯酸均聚物和/或丙烯酸共聚物,丙烯酸均聚物和丙烯酸共聚物的分子量均为6000~20000;所述有机硅流平剂的主要成分为聚二甲基硅氧烷和/或聚醚改性聚二甲基硅氧烷;所述有机硅型消泡剂的主要成分为聚二甲基硅氧烷,所述聚醚改性有机硅型消泡剂为氨基聚醚有机硅消泡剂、烷氧基聚醚有机硅消泡剂、羟基聚醚有机硅消泡剂中的一种或任意组合。Further, the defoamer is a silicone type defoamer and/or a polyether modified silicone type defoamer; the leveling agent is an acrylic leveling agent, an acrylic leveling agent, a silicone One or any combination of leveling agents; the main component of the acrylic leveling agent is acrylic acid homopolymer and/or acrylic acid copolymer, and the molecular weight of acrylic acid homopolymer and acrylic acid copolymer is 6000~20000; The main component of the silicone leveling agent is polydimethylsiloxane and/or polyether modified polydimethylsiloxane; the main component of the silicone type defoamer is polydimethylsiloxane alkane, the polyether modified silicone defoamer is one or any combination of aminopolyether silicone defoamer, alkoxy polyether silicone defoamer, hydroxyl polyether silicone defoamer .

进一步地,所述消泡剂为BYK-024有机硅消泡剂、BYK-067A有机硅消泡剂、BYK-028有机硅消泡剂中的一种或任意组合,所述流平剂为BYK-349有机硅流平剂、BYK-380丙烯酸流平剂、BYK-333聚醚改性有机硅流平剂中的一种或任意组合。Further, the defoamer is one or any combination of BYK-024 silicone defoamer, BYK-067A silicone defoamer, BYK-028 silicone defoamer, and the leveling agent is BYK - One or any combination of 349 silicone leveling agent, BYK-380 acrylic leveling agent, BYK-333 polyether modified silicone leveling agent.

附图说明Description of drawings

图1为实验例1中采用实施例13~15以及对比例1~2的PTC自控温涂料制得的电热膜的性能测试结果图;Fig. 1 is the performance test result figure of the electrothermal film that adopts embodiment 13~15 and the PTC self-temperature control coating of comparative example 1~2 to make in experimental example 1;

图2为实验例2中采用实施例16~18以及对比例2~3的PTC自控温涂料制得的电热膜的性能测试结果图。Fig. 2 is a graph showing the performance test results of the electrothermal film prepared by using the PTC self-temperature-controlling coatings of Examples 16-18 and Comparative Examples 2-3 in Experimental Example 2.

具体实施方式detailed description

以下结合具体实施方式对本发明的技术方案作进一步的说明。The technical solution of the present invention will be further described below in combination with specific embodiments.

实施例1Example 1

本实施例的用于聚合物基PTC材料的导电微粉,包括聚合物基PTC材料用固体填料和包覆在聚合物基PTC材料用固体填料表面的结晶性有机物层;聚合物基PTC材料用固体填料为石墨类二维碳材、超导炭黑、碳纤维和氮化铝,石墨烯类二维碳材、超导炭黑、碳纤维和氮化铝的质量比为150:100:30:100,石墨烯类二维碳材为多层石墨烯,片径5-8μm,超导炭黑为科琴黑,粒径35-70nm;碳纤维的单丝直径为6.5μm,长径比为2-15:1;氮化铝的粒径为3-5μm;结晶性有机物层的主要成分为聚氧化乙烯,熔点为85-90℃;石墨类二维碳材与聚氧化乙烯的质量比为150:300;导电微粉的粒径≤75μm,平均粒径为26μm。The conductive micropowder that is used for polymer-based PTC material of the present embodiment comprises the solid filler of polymer-based PTC material and the crystalline organic layer that is coated on the surface of solid filler for polymer-based PTC material; The polymer-based PTC material is solid The filler is graphite-like two-dimensional carbon material, superconducting carbon black, carbon fiber and aluminum nitride, and the mass ratio of graphene-like two-dimensional carbon material, superconducting carbon black, carbon fiber and aluminum nitride is 150:100:30:100. The graphene-like two-dimensional carbon material is multi-layer graphene, with a sheet diameter of 5-8 μm, and the superconducting carbon black is Ketjen Black, with a particle size of 35-70 nm; the single filament diameter of carbon fiber is 6.5 μm, and the aspect ratio is 2-15 : 1; the particle size of aluminum nitride is 3-5 μm; the main component of the crystalline organic layer is polyethylene oxide, and the melting point is 85-90 ° C; the mass ratio of graphite-like two-dimensional carbon material to polyethylene oxide is 150:300 ; The particle size of the conductive micropowder is ≤75 μm, and the average particle size is 26 μm.

本实施例的用于聚合物基PTC材料的导电微粉可以采用实施例7的方法进行制备。The conductive micropowder used in the polymer-based PTC material of this example can be prepared by the method of Example 7.

实施例2Example 2

本实施例的用于聚合物基PTC材料的导电微粉,包括聚合物基PTC材料用固体填料和包覆在聚合物基PTC材料用固体填料表面的结晶性有机物层;聚合物基PTC材料用固体填料为石墨类二维碳材、超导炭黑、碳纤维和碳化硅,石墨烯类二维碳材、超导炭黑、碳纤维和氮化铝的质量比为100:120:50:80,石墨烯类二维碳材为多层氧化石墨烯,片径为0.8-5μm,超导炭黑为乙炔炭黑,粒径30-45nm;碳纤维的单丝直径为5μm,长径比为2-15:1;碳化硅的粒径为1.3-1.5μm;结晶性有机物层主要成分为聚乙烯蜡,熔点为100-105℃;石墨类二维碳材与聚乙烯蜡的质量比为100:300;导电微粉的粒径≤75μm,平均粒径为25μm。The conductive micropowder that is used for polymer-based PTC material of the present embodiment comprises the solid filler of polymer-based PTC material and the crystalline organic layer that is coated on the surface of solid filler for polymer-based PTC material; The polymer-based PTC material is solid The filler is graphite-like two-dimensional carbon material, superconducting carbon black, carbon fiber and silicon carbide, the mass ratio of graphene-like two-dimensional carbon material, superconducting carbon black, carbon fiber and aluminum nitride is 100:120:50:80, graphite The alkene-based two-dimensional carbon material is multilayer graphene oxide with a sheet diameter of 0.8-5 μm, and the superconducting carbon black is acetylene carbon black with a particle size of 30-45 nm; the monofilament diameter of carbon fiber is 5 μm, and the aspect ratio is 2-15 : 1; the particle size of silicon carbide is 1.3-1.5 μm; the main component of the crystalline organic layer is polyethylene wax, and the melting point is 100-105 ° C; the mass ratio of graphite two-dimensional carbon material to polyethylene wax is 100:300; The particle size of the conductive fine powder is ≤75 μm, and the average particle size is 25 μm.

本实施例的用于聚合物基PTC材料的导电微粉可以采用实施例8的制备方法进行制备。The conductive fine powder used in the polymer-based PTC material of this example can be prepared by the preparation method of Example 8.

实施例3Example 3

本实施例的用于聚合物基PTC材料的导电微粉,包括聚合物基PTC材料用固体填料和包覆在聚合物基PTC材料用固体填料表面的结晶性有机物层;聚合物基PTC材料用固体填料为石墨类二维碳材、超导炭黑、碳纤维和碳化硅,石墨烯类二维碳材、超导炭黑、碳纤维和氮化铝的质量比为180:80:80:120,石墨烯类二维碳材为多层石墨烯,片径0.5-3μm,超导炭黑为乙炔炭黑,粒径200-240nm;碳纤维的单丝直径为2.6μm,长径比为2-15:1;氮化铝的粒径为3-5μm;结晶性有机物层主要成分为乙烯-醋酸乙烯共聚物(VA含量28%),熔点为95℃;石墨类二维碳材与乙烯-醋酸乙烯共聚物的质量比为180:300;导电微粉的粒径≤75μm,平均粒径为21μm。The conductive micropowder that is used for polymer-based PTC material of the present embodiment comprises the solid filler of polymer-based PTC material and the crystalline organic layer that is coated on the surface of solid filler for polymer-based PTC material; The polymer-based PTC material is solid The filler is graphite-like two-dimensional carbon material, superconducting carbon black, carbon fiber and silicon carbide, the mass ratio of graphene-like two-dimensional carbon material, superconducting carbon black, carbon fiber and aluminum nitride is 180:80:80:120, graphite The olefinic two-dimensional carbon material is multi-layer graphene, with a sheet diameter of 0.5-3μm, and the superconducting carbon black is acetylene carbon black, with a particle size of 200-240nm; the single filament diameter of carbon fiber is 2.6μm, and the aspect ratio is 2-15: 1. The particle size of aluminum nitride is 3-5μm; the main component of the crystalline organic layer is ethylene-vinyl acetate copolymer (VA content 28%), and the melting point is 95°C; graphite-based two-dimensional carbon material and ethylene-vinyl acetate copolymer The mass ratio of the powder is 180:300; the particle size of the conductive micropowder is ≤75 μm, and the average particle size is 21 μm.

本实施例的用于聚合物基PTC材料的导电微粉可以采用实施例9的制备方法进行制备。The conductive micropowder used in the polymer-based PTC material of this example can be prepared by the preparation method of Example 9.

实施例4Example 4

本实施例的用于聚合物基PTC材料的导电微粉,包括聚合物基PTC材料用固体填料和包覆在聚合物基PTC材料用固体填料表面的结晶性有机物层;聚合物基PTC材料用固体填料为石墨烯类二维碳材、超导炭黑、碳纤维和碳化硅,石墨烯类二维碳材、超导炭黑、碳纤维和碳化硅的质量之比为150:80:50:110;石墨烯类二维碳材为多层石墨烯,片径5-8μm;超导炭黑为乙炔炭黑,粒径30-45nm;碳纤维的单丝直径为6.5μm,长径比为2-15:1;碳化硅的粒径为1.3-1.5μm;结晶性有机物层由聚乙二醇20000、OP-6、Span80和辛癸酸甘油酯组成,聚乙二醇熔点58-63℃;聚乙二醇和石墨烯类二维碳材的质量之比300:150。本实施例的导电微粉的粒径≤75μm,平均粒径为28μm。The conductive micropowder that is used for polymer-based PTC material of the present embodiment comprises the solid filler of polymer-based PTC material and the crystalline organic layer that is coated on the surface of solid filler for polymer-based PTC material; The polymer-based PTC material is solid The filler is graphene-like two-dimensional carbon material, superconducting carbon black, carbon fiber and silicon carbide, and the mass ratio of graphene-like two-dimensional carbon material, superconducting carbon black, carbon fiber and silicon carbide is 150:80:50:110; The graphene-like two-dimensional carbon material is multilayer graphene, with a sheet diameter of 5-8μm; the superconducting carbon black is acetylene carbon black, with a particle size of 30-45nm; the single filament diameter of carbon fiber is 6.5μm, and the aspect ratio is 2-15 : 1; the particle size of silicon carbide is 1.3-1.5 μm; the crystalline organic layer is composed of polyethylene glycol 20000, OP-6, Span80 and glyceryl caprylate, and the melting point of polyethylene glycol is 58-63 ° C; polyethylene glycol The mass ratio of diol and graphene-based two-dimensional carbon material is 300:150. The particle size of the conductive fine powder in this embodiment is ≤75 μm, and the average particle size is 28 μm.

本实施例的用于聚合物基PTC材料的导电微粉可以采用实施例10的制备方法进行制备。The conductive fine powder used in the polymer-based PTC material of this embodiment can be prepared by the preparation method of Embodiment 10.

实施例5Example 5

本实施例的用于聚合物基PTC材料的导电微粉,包括聚合物基PTC材料用固体填料和包覆在聚合物基PTC材料用固体填料表面的结晶性有机物层;聚合物基PTC材料用固体填料为石墨烯类二维碳材、超导炭黑和碳纤维,石墨烯类二维碳材、超导炭黑和碳纤维的质量之比为130:100:85:120;石墨烯类二维碳材为多层氧化石墨烯,片径为0.8-5μm,超导炭黑为科琴黑,粒径35-70nm;碳纤维的单丝直径为5μm,长径比为2-15:1;碳化硅的粒径为1.3-1.5μm;结晶性有机物层由乙烯-醋酸乙烯共聚物(VA含量40%)、十二烷基硫酸钠、OP-10和油酸胺组成,乙烯-醋酸乙烯共聚物的熔点为70℃;乙烯-醋酸乙烯共聚物与石墨烯类二维碳材的质量之比为300:130。本实施例的导电微粉的粒径≤75μm,平均粒径为21μm。The conductive micropowder that is used for polymer-based PTC material of the present embodiment comprises the solid filler of polymer-based PTC material and the crystalline organic layer that is coated on the surface of solid filler for polymer-based PTC material; The polymer-based PTC material is solid The filler is graphene-like two-dimensional carbon material, superconducting carbon black and carbon fiber, and the mass ratio of graphene-like two-dimensional carbon material, superconducting carbon black and carbon fiber is 130:100:85:120; graphene-like two-dimensional carbon The material is multilayer graphene oxide with a sheet diameter of 0.8-5μm, the superconducting carbon black is Ketjen black with a particle size of 35-70nm; the monofilament diameter of carbon fiber is 5μm, and the aspect ratio is 2-15:1; silicon carbide The particle size is 1.3-1.5μm; the crystalline organic layer is composed of ethylene-vinyl acetate copolymer (40% VA content), sodium lauryl sulfate, OP-10 and oleic acid amine, and the ethylene-vinyl acetate copolymer The melting point is 70°C; the mass ratio of ethylene-vinyl acetate copolymer to graphene-like two-dimensional carbon material is 300:130. The particle size of the conductive fine powder in this embodiment is ≤75 μm, and the average particle size is 21 μm.

本实施例的用于聚合物基PTC材料的导电微粉可以采用实施例11的制备方法进行制备。The conductive micropowder used in the polymer-based PTC material of this example can be prepared by the preparation method of Example 11.

实施例6Example 6

本实施例的用于聚合物基PTC材料的导电微粉,包括聚合物基PTC材料用固体填料和包覆在聚合物基PTC材料用固体填料表面的结晶性有机物层;聚合物基PTC材料用固体填料为石墨烯类二维碳材、超导炭黑、碳纤维和氮化铝,石墨烯类二维碳材、超导炭黑、碳纤维和碳化硅的质量之比为120:80:100:100;石墨烯类二维碳材为多层石墨烯,片径0.5-3μm,超导炭黑为乙炔炭黑,粒径30-45nm;碳纤维的单丝直径为2.6μm,长径比为2-15:1;氮化铝的粒径为3-5μm;结晶性有机物层由硬脂酸、聚乙烯醇和硬脂酸单甘油酯组成,硬脂酸熔点60-65℃;硬脂酸与石墨烯类二维碳材的质量之比为350:120。本实施例的导电微粉的粒径≤75μm,平均粒径为27μm。The conductive micropowder that is used for polymer-based PTC material of the present embodiment comprises the solid filler of polymer-based PTC material and the crystalline organic layer that is coated on the surface of solid filler for polymer-based PTC material; The polymer-based PTC material is solid The filler is graphene-like two-dimensional carbon material, superconducting carbon black, carbon fiber and aluminum nitride, and the mass ratio of graphene-like two-dimensional carbon material, superconducting carbon black, carbon fiber and silicon carbide is 120:80:100:100 ; The graphene-like two-dimensional carbon material is multi-layer graphene, with a sheet diameter of 0.5-3 μm, and the superconducting carbon black is acetylene carbon black, with a particle size of 30-45 nm; the single filament diameter of carbon fiber is 2.6 μm, and the aspect ratio is 2- 15:1; the particle size of aluminum nitride is 3-5μm; the crystalline organic layer is composed of stearic acid, polyvinyl alcohol and monoglyceride stearate, and the melting point of stearic acid is 60-65°C; stearic acid and graphene The mass ratio of the quasi-two-dimensional carbon material is 350:120. The particle size of the conductive fine powder in this embodiment is ≤75 μm, and the average particle size is 27 μm.

本实施例的用于聚合物基PTC材料的导电微粉可以采用实施例12的制备方法进行制备。The conductive micropowder used in the polymer-based PTC material of this example can be prepared by the preparation method of Example 12.

实施例7Example 7

本实施例的用于聚合物基PTC材料的导电微粉的制备方法,包括以下步骤:The preparation method of the conductive micropowder that is used for polymer-based PTC material of the present embodiment, comprises the following steps:

1)称取300g聚氧化乙烯、54g聚乙烯醇、30g硬脂酸单甘油酯置于反应釜中,升温至105℃使聚氧化乙烯完全熔融,并搅拌均匀;所采用的聚氧化乙烯的熔点为85-90℃;1) Weigh 300g of polyethylene oxide, 54g of polyvinyl alcohol, and 30g of monoglyceride stearate in a reactor, heat up to 105°C to completely melt the polyethylene oxide, and stir evenly; the melting point of the polyethylene oxide used is 85-90°C;

然后取100℃的去离子水500mL缓慢加入温度维持在105℃的反应釜中,再将反应釜加压3-6MPa,随后在105℃以600r/min的转速高速分散0.5h,使聚氧乙烯完全乳化,得到结晶聚合物乳液;Then take 500mL of deionized water at 100°C and slowly add it into the reaction kettle maintained at 105°C, pressurize the reaction kettle to 3-6MPa, and then disperse at 105°C at a speed of 600r/min for 0.5h at a high speed to make polyoxyethylene Complete emulsification to obtain a crystalline polymer emulsion;

2)继续将反应釜的温度维持在105℃,向反应釜中加入150g石墨烯类二维碳材、100g超导炭黑、30g碳纤维、100g氮化铝,然后在105℃下继续分散1h混合均匀,得到混合浆料;所采用石墨烯类二维碳材为多层石墨烯,片径5-8μm;超导炭黑为科琴黑,粒径为35-70nm;碳纤维的单丝直径为6.5μm,长径比为2-15:1;氮化铝的粒径为3-5μm;2) Continue to maintain the temperature of the reactor at 105°C, add 150g of graphene-based two-dimensional carbon material, 100g of superconducting carbon black, 30g of carbon fiber, and 100g of aluminum nitride into the reactor, and then continue to disperse and mix at 105°C for 1 hour Evenly, mixed slurry is obtained; the graphene-like two-dimensional carbon material used is multi-layer graphene, with a sheet diameter of 5-8 μm; the superconducting carbon black is Ketjen black, with a particle size of 35-70nm; 6.5μm, the aspect ratio is 2-15:1; the particle size of aluminum nitride is 3-5μm;

将混合浆料缓慢冷却至室温,真空冻干得到冻干物;对冻干物进行冷冻研磨,研磨结束后采用200目筛网对研磨物过筛4遍,即得到用于聚合物基PTC材料的导电微粉,其粒径≤75μm,平均粒径为26μm。Slowly cool the mixed slurry to room temperature, vacuum freeze-dry to obtain a freeze-dried product; freeze-dried the freeze-dried product, and use a 200-mesh sieve to sieve the ground product 4 times after grinding to obtain a polymer-based PTC material. Conductive fine powder with a particle size of ≤75 μm and an average particle size of 26 μm.

实施例8Example 8

本实施例的用于聚合物基PTC材料的导电微粉的制备方法,包括以下步骤:The preparation method of the conductive micropowder that is used for polymer-based PTC material of the present embodiment, comprises the following steps:

1)称取300g聚乙烯蜡、50g OP-6、4g Span80、30g乙烯基双硬脂酰胺置于反应釜中,升温至115℃使聚乙烯蜡完全熔融,并搅拌均匀;所采用的聚乙烯蜡的熔点为100-105℃;1) Weigh 300g of polyethylene wax, 50g of OP-6, 4g of Span80, and 30g of vinyl bisstearamide in a reaction kettle, heat up to 115°C to completely melt the polyethylene wax, and stir evenly; the polyethylene The melting point of wax is 100-105°C;

然后取100℃的去离子水500mL缓慢加入温度维持在的115℃的反应釜中,再向反应釜加压3-6MPa,随后在115℃以750r/min的转速高速分散0.5h,使聚乙烯蜡完全乳化,得到结晶聚合物乳液;Then take 500mL of deionized water at 100°C and slowly add it into the reactor at 115°C maintained at a temperature of 115°C, pressurize the reactor at 3-6MPa, and then disperse at 115°C at a speed of 750r/min for 0.5h at a high speed to make polyethylene The wax is completely emulsified to obtain a crystalline polymer emulsion;

2)继续将反应釜的温度维持在115℃,向反应釜中加入100g石墨烯类二维碳材、120g超导炭黑、50g碳纤维、80g碳化硅,然后在115℃下继续分散1h混合均匀,得到混合浆料;所采用的石墨烯类二维碳材为多层氧化石墨烯,片径为0.8~5μm;超导炭黑为乙炔炭黑,粒径为30-45nm;碳纤维的单丝直径为5μm,长径比为2-15:1;碳化硅的粒径为1.3~1.5μm;2) Continue to maintain the temperature of the reactor at 115°C, add 100g of graphene-based two-dimensional carbon material, 120g of superconducting carbon black, 50g of carbon fiber, and 80g of silicon carbide into the reactor, and then continue to disperse at 115°C for 1 hour and mix well , to obtain a mixed slurry; the graphene-based two-dimensional carbon material used is multilayer graphene oxide, with a sheet diameter of 0.8-5 μm; the superconducting carbon black is acetylene carbon black, with a particle size of 30-45 nm; the monofilament of carbon fiber The diameter is 5 μm, and the aspect ratio is 2-15:1; the particle size of silicon carbide is 1.3-1.5 μm;

将混合浆料缓慢冷却至室温,真空冻干得到冻干物;对冻干物进行冷冻研磨,研磨结束后采用200目筛网对研磨物过筛4遍,即得到用于聚合物基PTC材料的导电微粉,平均粒径为25μm。Slowly cool the mixed slurry to room temperature, vacuum freeze-dry to obtain a freeze-dried product; freeze-dried the freeze-dried product, and use a 200-mesh sieve to sieve the ground product 4 times after grinding to obtain a polymer-based PTC material. Conductive fine powder with an average particle size of 25 μm.

实施例9Example 9

本实施例的用于聚合物PCT材料的导电微粉的制备方法,包括以下步骤:The preparation method of the conductive micropowder that is used for polymer PCT material of the present embodiment, comprises the following steps:

1)称取300g乙烯-醋酸乙烯共聚物(VA含量28%)、40g十二烷基硫酸钠、20g OP-10、30g硬脂酸酰胺置于反应釜中,升温至100℃使乙烯-醋酸乙烯共聚物完全熔融,并搅拌均匀;所采用的乙烯-醋酸乙烯共聚物的熔点为95℃;1) Weigh 300g of ethylene-vinyl acetate copolymer (VA content 28%), 40g of sodium lauryl sulfate, 20g of OP-10, and 30g of stearic acid amide in a reaction kettle, and heat up to 100°C to make ethylene-acetic acid The ethylene copolymer is completely melted and stirred evenly; the melting point of the ethylene-vinyl acetate copolymer used is 95°C;

然后取100℃的去离子水500mL缓慢加入反应釜中,再将反应釜加压3-6MPa,随后在100℃以700r/min的转速高速分散0.5h,使乙烯-醋酸乙烯共聚物完全乳化,得到结晶聚合物乳液;Then take 500mL of deionized water at 100°C and slowly add it into the reactor, pressurize the reactor to 3-6MPa, and then disperse at 100°C at a speed of 700r/min for 0.5h at a high speed to completely emulsify the ethylene-vinyl acetate copolymer. obtaining a crystalline polymer emulsion;

2)继续将反应釜的温度维持在100℃,向反应釜中加入180g石墨烯、80g超导炭黑、80g碳纤维、120g氮化铝,然后在100℃下继续分散1h混合均匀,得到混合浆料;所采用的石墨烯为多层石墨烯,片径为0.5-3μm;超导炭黑为乙炔炭黑,粒径为200-240nm;碳纤维的单丝直径为2.6μm,长径比为2-15:1;氮化铝的粒径为3-5μm;2) Continue to maintain the temperature of the reactor at 100°C, add 180g of graphene, 80g of superconducting carbon black, 80g of carbon fiber, and 120g of aluminum nitride into the reactor, and then continue to disperse at 100°C for 1 hour and mix evenly to obtain a mixed slurry material; the graphene used is multilayer graphene with a sheet diameter of 0.5-3μm; the superconducting carbon black is acetylene carbon black with a particle size of 200-240nm; the monofilament diameter of carbon fiber is 2.6μm, and the aspect ratio is 2 -15:1; the particle size of aluminum nitride is 3-5μm;

将混合浆料缓慢冷却至室温,真空冻干得到冻干物;对冻干物进行冷冻研磨,研磨结束后采用200目筛网对研磨物过筛4遍,即得到用于聚合物基PTC材料的导电微粉,平均粒径为21μm。Slowly cool the mixed slurry to room temperature, vacuum freeze-dry to obtain a freeze-dried product; freeze-dried the freeze-dried product, and use a 200-mesh sieve to sieve the ground product 4 times after grinding to obtain a polymer-based PTC material. Conductive fine powder with an average particle size of 21 μm.

实施例10Example 10

本实施例的用于聚合物基PTC材料的导电微粉的制备方法,包括以下步骤:The preparation method of the conductive micropowder that is used for polymer-based PTC material of the present embodiment, comprises the following steps:

1)称取300g聚乙二醇、50g OP-6、4g Span80、30g辛癸酸甘油酯置于反应釜中,升温至85℃使聚乙二醇完全熔融,并搅拌均匀;聚乙二醇熔点为58-63℃;1) Weigh 300g of polyethylene glycol, 50g of OP-6, 4g of Span80, and 30g of caprylic capric acid glyceride in a reaction kettle, heat up to 85°C to completely melt the polyethylene glycol, and stir evenly; polyethylene glycol The melting point is 58-63°C;

然后取85℃去离子水500mL缓慢加入温度维持在85℃的反应釜中,然后在85℃下以700r/min的转速高速分散0.5h,使聚乙二醇完全乳化,得到结晶聚合物乳液;Then take 500mL of 85°C deionized water and slowly add it into the reaction kettle maintained at 85°C, and then disperse at a high speed of 700r/min at 85°C for 0.5h to completely emulsify the polyethylene glycol to obtain a crystalline polymer emulsion;

2)继续将反应釜的温度维持在85℃,向反应釜中加入150g石墨烯类二维碳材、80g超导炭黑、50g碳纤维、110g碳化硅,然后在85℃下继续分散1h混合均匀,得到混合浆料;所采用的石墨烯类二维碳材为多层石墨烯,片径5-8μm,超导炭黑为乙炔炭黑,粒径30-45nm;碳纤维的单丝直径为6.5μm,长径比为2-15:1;碳化硅的粒径为1.3-1.5μm;2) Continue to maintain the temperature of the reactor at 85°C, add 150g of graphene-based two-dimensional carbon material, 80g of superconducting carbon black, 50g of carbon fiber, and 110g of silicon carbide into the reactor, and then continue to disperse at 85°C for 1 hour and mix well , to obtain a mixed slurry; the graphene-like two-dimensional carbon material used is multilayer graphene with a sheet diameter of 5-8 μm, and the superconducting carbon black is acetylene carbon black with a particle size of 30-45nm; the single filament diameter of the carbon fiber is 6.5 μm, the aspect ratio is 2-15:1; the particle size of silicon carbide is 1.3-1.5μm;

将混合浆料缓慢冷却至室温,真空冻干得到冻干物;对冻干物进行冷冻研磨,研磨结束后采用200目筛网对研磨物过筛4遍,即得到用于聚合物基PTC材料的导电微粉,平均粒径为28μm。Slowly cool the mixed slurry to room temperature, vacuum freeze-dry to obtain a freeze-dried product; freeze-dried the freeze-dried product, and use a 200-mesh sieve to sieve the ground product 4 times after grinding to obtain a polymer-based PTC material. Conductive fine powder with an average particle size of 28 μm.

实施例11Example 11

本实施例的用于聚合物基PTC材料的导电微粉的制备方法,包括以下步骤:The preparation method of the conductive micropowder that is used for polymer-based PTC material of the present embodiment, comprises the following steps:

1)称取300g乙烯-醋酸乙烯共聚物(VA含量40%)、30g十二烷基硫酸钠、18g OP-10、40g油酸胺置于反应釜中,升温至90℃使乙烯-醋酸乙烯共聚物完全熔融,并搅拌均匀;乙烯-醋酸乙烯共聚物(VA含量40%)的熔点为70℃;1) Weigh 300g of ethylene-vinyl acetate copolymer (40% VA content), 30g of sodium lauryl sulfate, 18g of OP-10, and 40g of oleic acid amine and place it in a reaction kettle, heat up to 90°C to make ethylene-vinyl acetate The copolymer is completely melted and stirred evenly; the melting point of ethylene-vinyl acetate copolymer (40% VA content) is 70°C;

然后取90℃去离子水500mL缓慢加入反应釜中,随后在90℃下以750r/min的转速高速分散0.5h,使乙烯-醋酸乙烯共聚物完全乳化,得到结晶聚合物乳液;Then take 500mL of deionized water at 90°C and slowly add it into the reaction kettle, and then disperse at a high speed of 750r/min at 90°C for 0.5h to completely emulsify the ethylene-vinyl acetate copolymer to obtain a crystalline polymer emulsion;

2)继续将反应釜的温度维持在90℃,向反应釜中加入130g石墨烯类二维碳材、100g超导炭黑、85g碳纤维、120g碳化硅,然后在90℃下继续分散1h混合均匀,得到混合浆料;所采用的石墨烯类二维碳材为多层氧化石墨烯,片径为0.8-5μm;超导炭黑为科琴黑,粒径35-70nm;碳纤维的单丝直径为5μm,长径比为2-15:1;碳化硅的粒径为1.3-1.5μm;2) Continue to maintain the temperature of the reactor at 90°C, add 130g of graphene-based two-dimensional carbon material, 100g of superconducting carbon black, 85g of carbon fiber, and 120g of silicon carbide into the reactor, and then continue to disperse at 90°C for 1 hour and mix well , to obtain a mixed slurry; the graphene-like two-dimensional carbon material used is multilayer graphene oxide, with a sheet diameter of 0.8-5 μm; the superconducting carbon black is Ketjen black, with a particle size of 35-70nm; the monofilament diameter of the carbon fiber 5μm, the aspect ratio is 2-15:1; the particle size of silicon carbide is 1.3-1.5μm;

将混合浆料缓慢冷却至室温,真空冻干得到冻干物;对冻干物进行冷冻研磨,研磨结束后采用200目筛网对研磨物过筛4遍,即得到用于聚合物基PTC材料的导电微粉,平均粒径为21μm。Slowly cool the mixed slurry to room temperature, vacuum freeze-dry to obtain a freeze-dried product; freeze-dried the freeze-dried product, and use a 200-mesh sieve to sieve the ground product 4 times after grinding to obtain a polymer-based PTC material. Conductive fine powder with an average particle size of 21 μm.

实施例12Example 12

本实施例的用于聚合物基PTC材料的导电微粉的制备方法,包括以下步骤:The preparation method of the conductive micropowder that is used for polymer-based PTC material of the present embodiment, comprises the following steps:

1)称取350g硬脂酸、50g聚乙烯醇、30g硬脂酸单甘油酯置于反应釜中,升温至80℃使硬脂酸完全熔融,并搅拌均匀;硬脂酸的熔点为60-65℃;1) Weigh 350g of stearic acid, 50g of polyvinyl alcohol, and 30g of monoglyceride stearate in a reaction kettle, heat up to 80°C to completely melt the stearic acid, and stir evenly; the melting point of stearic acid is 60- 65°C;

然后取85℃去离子水500mL缓慢加入反应釜中,在80℃下以600r/min的转速高速分散0.5h,使硬脂酸完全乳化;Then take 500mL of deionized water at 85°C and slowly add it into the reaction kettle, and disperse at a high speed of 600r/min at 80°C for 0.5h to completely emulsify the stearic acid;

2)待乳化完全后,向反应釜中加入120g石墨烯类二维碳材、80g超导炭黑、100g碳纤维、100g氮化铝,高温状态下继续分散1h,得到混合浆料;所采用的石墨烯类二维碳材为多层石墨烯,片径0.5-3μm;超导炭黑为乙炔炭黑,粒径30-45nm;碳纤维的单丝直径为2.6μm,长径比为2-15:1;氮化铝的粒径为3-5μm;2) After the emulsification is complete, add 120g of graphene-based two-dimensional carbon material, 80g of superconducting carbon black, 100g of carbon fiber, and 100g of aluminum nitride into the reactor, and continue to disperse for 1 hour at a high temperature to obtain a mixed slurry; The graphene-like two-dimensional carbon material is multilayer graphene, with a sheet diameter of 0.5-3μm; the superconducting carbon black is acetylene carbon black, with a particle size of 30-45nm; the single filament diameter of carbon fiber is 2.6μm, and the aspect ratio is 2-15 : 1; the particle size of aluminum nitride is 3-5 μm;

将混合浆料缓慢冷却至室温,真空冻干得到冻干物;对冻干物进行冷冻研磨,研磨结束后采用200目筛网对研磨物过筛4遍,即得到用于聚合物基PTC材料的导电微粉,平均粒径为27μm。Slowly cool the mixed slurry to room temperature, vacuum freeze-dry to obtain a freeze-dried product; freeze-dried the freeze-dried product, and use a 200-mesh sieve to sieve the ground product 4 times after grinding to obtain a polymer-based PTC material. Conductive fine powder with an average particle size of 27μm.

实施例13Example 13

本实施例的PTC自控温涂料,由树脂乳液、导电微粉、BYK-024有机硅消泡剂、BYK-349有机硅流平剂和其他助剂组成;树脂乳液为陶氏YS-3018水性聚氨酯分散体,固含量为45%,树脂乳液在PTC自控温涂料固化后形成的聚合物的软化点>90℃。导电微粉为实施例7中制备的用于聚合物基PTC材料的导电微粉,其他助剂为德中N-2496水性增稠剂和江苏飞亚化学KY616-3受阻酚类抗氧剂;聚氨酯乳液、导电微粉中所含聚氧化乙烯、BYK-024有机硅消泡剂、BYK-349有机硅流平剂、其他助剂的质量之比为1000:300:30:30:10。The PTC self-temperature control coating of this embodiment is composed of resin emulsion, conductive micropowder, BYK-024 silicone defoamer, BYK-349 silicone leveling agent and other additives; the resin emulsion is Dow YS-3018 waterborne polyurethane The dispersion has a solid content of 45%, and the softening point of the polymer formed after the resin emulsion is cured after the PTC self-temperature control coating is greater than 90°C. The conductive micropowder is the conductive micropowder used for polymer-based PTC materials prepared in Example 7, and other additives are Dezhong N-2496 water-based thickener and Jiangsu Feiya Chemical KY616-3 hindered phenolic antioxidant; polyurethane emulsion , The mass ratio of polyethylene oxide, BYK-024 silicone defoamer, BYK-349 silicone leveling agent, and other additives contained in the conductive micropowder is 1000:300:30:30:10.

本实施例的PTC自控温涂料的制备方法,包括以下步骤:将导电微粉加入到树脂乳液中,然后再加入BYK-024有机硅消泡剂、BYK-349有机硅流平剂及其它助剂,在室温分散0.5h混匀,得到PTC自控温涂料。The preparation method of the PTC self-temperature control coating in this embodiment includes the following steps: adding conductive fine powder to the resin emulsion, and then adding BYK-024 silicone defoamer, BYK-349 silicone leveling agent and other additives , Disperse and mix at room temperature for 0.5h to obtain a PTC self-temperature-controlling coating.

实施例14Example 14

本实施例的PTC自控温涂料,由树脂乳液、导电微粉、BYK-067A有机硅消泡剂、BYK-380丙烯酸流平剂及其它助剂;树脂乳液为青岛古道化学8912硅丙乳液,固含量为45%,树脂乳液在PTC自控温涂料固化后形成的聚合物的软化点为>105℃,导电微粉为实施例8的制备方法制得的用于聚合物基PTC材料的导电微粉,其他助剂为德中N-2496水性增稠剂和江苏飞亚化学KY616-3受阻酚类抗氧剂;丙烯酸乳液、导电微粉中聚乙烯蜡、BYK-067A有机硅消泡剂、BYK-380丙烯酸流平剂、其它助剂的质量之比为1000:300:20:20:10。The PTC self-temperature control coating of the present embodiment is made of resin emulsion, conductive micropowder, BYK-067A organic silicon defoamer, BYK-380 acrylic leveling agent and other auxiliary agents; the resin emulsion is Qingdao Gudao Chemical 8912 silicon acrylic emulsion, solid The content is 45%, the softening point of the polymer formed by the resin emulsion after the PTC self-temperature control coating is cured is> 105 ° C, and the conductive fine powder is the conductive fine powder for polymer-based PTC materials prepared by the preparation method of Example 8, Other additives are Dezhong N-2496 water-based thickener and Jiangsu Feiya Chemical KY616-3 hindered phenolic antioxidant; acrylic emulsion, polyethylene wax in conductive micropowder, BYK-067A silicone defoamer, BYK-380 The mass ratio of acrylic leveling agent to other additives is 1000:300:20:20:10.

本实施例的PTC自控温涂料的制备方法,包括以下步骤:将导电微粉加入到树脂乳液中,然后再加入BYK-067A有机硅消泡剂、BYK-380丙烯酸流平剂及其它助剂,在室温分散0.5h混匀,得到PTC自控温涂料。The preparation method of the PTC self-temperature-control coating in this embodiment includes the following steps: adding conductive fine powder to the resin emulsion, and then adding BYK-067A silicone defoamer, BYK-380 acrylic leveling agent and other additives, Disperse and mix at room temperature for 0.5h to obtain a PTC self-temperature-controlling coating.

实施例15Example 15

本实施例的PTC自控温涂料由树脂乳液、导电微粉、BYK-028有机硅消泡剂、BYK-333聚醚改性有机硅流平剂及其它助剂组成;树脂乳液为陶氏RSN-8016有机硅树脂,固含量为60%,树脂乳液在PTC自控温涂料固化后形成的聚合物的软化点为>95℃,导电微粉为实施例9的制备方法制得的用于聚合物基PTC材料的导电微粉,其他助剂为德中N-2447有机硅增稠剂、江苏飞亚化学KY616-3受阻酚类抗氧剂;有机硅乳液、导电微粉中乙烯-醋酸乙烯共聚物、BYK-028有机硅消泡剂、BYK-333聚醚改性有机硅流平剂、其它助剂的质量之比为1000:300:15:15:10。The PTC self-temperature control coating in this embodiment is composed of resin emulsion, conductive micropowder, BYK-028 silicone defoamer, BYK-333 polyether modified silicone leveling agent and other additives; the resin emulsion is Dow RSN- 8016 silicone resin, the solid content is 60%, the softening point of the polymer formed by the resin emulsion after the PTC self-temperature control coating is cured is >95°C, and the conductive micropowder is prepared by the preparation method of Example 9 for polymer-based Conductive micropowder of PTC materials, other additives are Dezhong N-2447 silicone thickener, Jiangsu Feiya chemical KY616-3 hindered phenolic antioxidant; silicone emulsion, ethylene-vinyl acetate copolymer in conductive micropowder, BYK The mass ratio of -028 silicone defoamer, BYK-333 polyether modified silicone leveling agent and other additives is 1000:300:15:15:10.

本实施例的PTC自控温涂料的制备方法,包括以下步骤:将导电微粉加入到树脂乳液中,然后再加入BYK-028有机硅消泡剂、BYK-333聚醚改性有机硅流平剂及其它助剂,在室温分散0.5h混匀,得到PTC自控温涂料。The preparation method of the PTC self-temperature control coating in this embodiment includes the following steps: adding conductive micropowder to the resin emulsion, and then adding BYK-028 silicone defoamer and BYK-333 polyether modified silicone leveling agent And other additives, disperse and mix at room temperature for 0.5h to get PTC self-temperature control coating.

实施例16Example 16

本实施例的PTC自控温涂料由树脂乳液、导电微粉、BYK-024有机硅消泡剂、BYK-349有机硅流平剂及其他助剂组成;所采用的树脂乳液为陶氏易韧达TM2468A纯丙烯酸乳液,固含量为50.5%,树脂乳液在PTC自控温涂料固化后形成的聚合物的软化点>80℃;所采用的导电微粉为实施例10制得的用于聚合物基PTC材料的导电微粉,所采用的其他助剂为德中N-2496水性增稠剂和江苏飞亚化学KY616-3受阻酚类抗氧剂;丙烯酸乳液、导电微粉中聚乙二醇20000、BYK-024有机硅消泡剂、BYK-349有机硅流平剂及其他助剂的质量之比为1000:300:3:3:10。The PTC self-temperature control coating in this embodiment is composed of resin emulsion, conductive micropowder, BYK-024 organic silicon defoamer, BYK-349 organic silicon leveling agent and other additives; the resin emulsion used is Dow Easy Tough TM2468A pure acrylic emulsion, with a solid content of 50.5%, the softening point of the polymer formed by the resin emulsion after the PTC self-temperature control coating is cured > 80°C; the conductive powder used is the polymer-based PTC prepared in Example 10 Conductive micropowder of materials, other additives used are Dezhong N-2496 water-based thickener and Jiangsu Feiya chemical KY616-3 hindered phenolic antioxidant; acrylic emulsion, polyethylene glycol 20000 in conductive micropowder, BYK- The mass ratio of 024 silicone defoamer, BYK-349 silicone leveling agent and other additives is 1000:300:3:3:10.

本实施例的PTC自控温涂料的制备方法,包括以下步骤:将导电微粉加入树脂乳液中,然后再加入BYK-024有机硅消泡剂、BYK-349有机硅流平剂及其它助剂,在室温分散0.5h混匀,得到PTC自控温涂料。The preparation method of the PTC self-temperature control coating in this embodiment includes the following steps: adding conductive fine powder into the resin emulsion, and then adding BYK-024 silicone defoamer, BYK-349 silicone leveling agent and other additives, Disperse and mix at room temperature for 0.5h to obtain a PTC self-temperature-controlling coating.

实施例17Example 17

本实施例的PTC自控温涂料由树脂乳液、导电微粉、BYK-067A有机硅消泡剂、BYK-380丙烯酸流平剂及其他助剂组成;所采用的树脂乳液为陶氏易韧达TM2468A纯丙烯酸乳液,固含量为50.5%,树脂乳液在PTC自控温涂料固化后形成的聚合物的软化点>80℃;所采用的导电微粉为实施例11中制得的用于聚合物基PTC材料的导电微粉;所采用的其他助剂为德中N-2496水性增稠剂和江苏飞亚化学KY616-3受阻酚类抗氧剂;丙烯酸乳液、导电微粉中乙烯-醋酸乙烯共聚物、BYK-067A有机硅消泡剂、BYK-380丙烯酸流平剂、其他助剂的质量之比为1000:300:4:3.5:10。The PTC self-temperature-controlling paint in this embodiment is composed of resin emulsion, conductive micropowder, BYK-067A silicone defoamer, BYK-380 acrylic leveling agent and other additives; the resin emulsion used is Dow Yida TM2468A Pure acrylic emulsion, the solid content is 50.5%, the softening point of the polymer formed by the resin emulsion after the PTC self-temperature control coating is cured> 80 ℃; Conductive micropowder of materials; other additives used are Dezhong N-2496 water-based thickener and Jiangsu Feiya Chemical KY616-3 hindered phenolic antioxidant; acrylic emulsion, ethylene-vinyl acetate copolymer in conductive micropowder, BYK The mass ratio of -067A silicone defoamer, BYK-380 acrylic leveling agent and other additives is 1000:300:4:3.5:10.

本实施例的PTC自控温涂料的制备方法,包括以下步骤:将导电微粉加入树脂乳液中,然后再加入BYK-067A有机硅消泡剂、BYK-380丙烯酸流平剂及其它助剂,在室温分散0.5h混匀,得到PTC自控温涂料。The preparation method of the PTC self-temperature control coating of this embodiment includes the following steps: adding conductive fine powder into the resin emulsion, and then adding BYK-067A silicone defoamer, BYK-380 acrylic leveling agent and other additives, Disperse and mix at room temperature for 0.5h to obtain a PTC self-temperature-controlling coating.

实施例18Example 18

本实施例的PTC自控温涂料由树脂乳液、导电微粉、BYK-028有机硅消泡剂、BYK-333聚醚改性有机硅流平剂及其他助剂组成;所采用的树脂乳液为广州佳壕化工科技JH7506有机硅树脂,固含量为50%,树脂乳液在PTC自控温涂料固化后形成的聚合物的软化点>65℃;所采用的导电微粉为实施例12中制备的用于聚合物基PTC材料的导电微粉;所采用的其他助剂为德中N-2447有机硅增稠剂、江苏飞亚化学KY616-3受阻酚类抗氧剂;有机硅乳液、导电微粉中硬脂酸、BYK-028有机硅消泡剂、BYK-333聚醚改性有机硅流平剂及其他助剂的质量之比为1000:350:5:3:10。The PTC self-temperature control coating in this embodiment is composed of resin emulsion, conductive micropowder, BYK-028 silicone defoamer, BYK-333 polyether modified silicone leveling agent and other additives; the resin emulsion used is Guangzhou Jiahao Chemical Technology JH7506 silicone resin, the solid content is 50%, the softening point of the polymer formed after the resin emulsion is cured by the PTC self-temperature control coating is >65°C; the conductive micropowder used is prepared in Example 12 for Conductive micropowder of polymer-based PTC materials; other additives used are Dezhong N-2447 silicone thickener, Jiangsu Feiya Chemical KY616-3 hindered phenolic antioxidant; silicone emulsion, stearin in conductive micropowder The mass ratio of acid, BYK-028 silicone defoamer, BYK-333 polyether modified silicone leveling agent and other additives is 1000:350:5:3:10.

本实施例的PTC自控温涂料的制备方法,包括以下步骤:将导电微粉加入树脂乳液中,然后再加入BYK-028有机硅消泡剂、BYK-333聚醚改性有机硅流平剂及其它助剂,在室温分散0.5h混匀,得到PTC自控温涂料。The preparation method of the PTC self-temperature control coating of this embodiment includes the following steps: adding conductive micropowder to the resin emulsion, and then adding BYK-028 silicone defoamer, BYK-333 polyether modified silicone leveling agent and For other additives, disperse and mix at room temperature for 0.5h to obtain a PTC self-temperature-controlling coating.

对比例1Comparative example 1

本对比例的导电微粉的制备方法,包括以下步骤:The preparation method of the conductive micropowder of this comparative example comprises the following steps:

1)称取300g热塑性聚氨酯弹性体橡胶(TPU)、30g十二烷基磺酸钠、20g OP-10、30g辛癸酸甘油酯置于反应釜中,升温至115℃使TPU完全熔融,并搅拌均匀;所采用的TPU的熔点为98℃;1) Weigh 300g of thermoplastic polyurethane elastomer rubber (TPU), 30g of sodium dodecylsulfonate, 20g of OP-10, and 30g of glyceryl caprylate and place it in a reaction kettle, heat up to 115°C to completely melt the TPU, and Stir evenly; the melting point of the TPU used is 98°C;

取100℃的去离子水500mL缓慢加入温度维持在115℃的反应釜中,再将反应釜加压3-6MPa,随后在115℃以600r/min的转速高速分散0.5h,使TPU完全乳化;Take 500mL of deionized water at 100°C and slowly add it into the reaction kettle maintained at 115°C, then pressurize the reaction kettle to 3-6MPa, and then disperse at 115°C at a speed of 600r/min for 0.5h at a high speed to completely emulsify the TPU;

2)继续将反应度的温度维持在115℃,向反应釜中加入150g石墨烯类二维碳材、100g超导炭黑、50g碳纤维、100g碳化硅,然后在115℃下继续分散1h混合均匀,得到混合浆料;石墨烯类二维碳材为多层氧化石墨烯,石墨烯片径为0.8-5μm,超导炭黑为乙炔炭黑,粒径为30-45nm;碳纤维的单丝直径为5μm,长径比为2-15:1;碳化硅的粒径为1.3-1.5μm;2) Continue to maintain the reaction temperature at 115°C, add 150g of graphene-based two-dimensional carbon material, 100g of superconducting carbon black, 50g of carbon fiber, and 100g of silicon carbide into the reactor, and then continue to disperse at 115°C for 1 hour and mix well , to obtain a mixed slurry; the graphene-like two-dimensional carbon material is multilayer graphene oxide, and the graphene sheet diameter is 0.8-5 μm, and the superconducting carbon black is acetylene carbon black, and the particle diameter is 30-45nm; the monofilament diameter of the carbon fiber 5μm, the aspect ratio is 2-15:1; the particle size of silicon carbide is 1.3-1.5μm;

将混合浆料缓慢冷却至室温,然后真空冻干,得到冻干物;研磨结束后采用200目筛网对研磨物过筛4遍,即得到用于聚合物基PTC材料的导电微粉,平均粒径为24μm。Slowly cool the mixed slurry to room temperature, and then vacuum freeze-dry to obtain a freeze-dried product; after grinding, use a 200-mesh screen to sieve the ground product 4 times to obtain conductive micropowder for polymer-based PTC materials, with an average particle size of The diameter is 24 μm.

对比例2Comparative example 2

本对比例的导电微粉的制备方法,包括以下步骤:The preparation method of the conductive micropowder of this comparative example comprises the following steps:

1)称取300g热塑性聚氨酯弹性体橡胶(TPU)、30g十二烷基磺酸钠、20g OP-10、30g辛癸酸甘油酯置于反应釜中,升温至80℃使TPU完全熔融,并搅拌均匀;所采用的TPU的熔点为60℃;1) Weigh 300g of thermoplastic polyurethane elastomer rubber (TPU), 30g of sodium dodecylsulfonate, 20g of OP-10, and 30g of glyceryl caprylate and place it in a reaction kettle, heat up to 80°C to completely melt the TPU, and Stir evenly; the melting point of the TPU used is 60°C;

取85℃的去离子水500mL缓慢加入温度维持在115℃的反应釜中,再将反应釜加压3-6MPa,随后在115℃以600r/min的转速高速分散0.5h,使TPU完全乳化;Take 500mL of deionized water at 85°C and slowly add it into the reaction kettle maintained at 115°C, then pressurize the reaction kettle to 3-6MPa, and then disperse at 115°C at a speed of 600r/min for 0.5h at a high speed to completely emulsify the TPU;

2)继续将反应度的温度维持在85℃,向反应釜中加入150g石墨烯类二维碳材、80g超导炭黑、50g碳纤维、110g碳化硅,然后在85℃下继续分散1h混合均匀,得到混合浆料;石墨烯类二维碳材为多层石墨烯,片径5-8μm,超导炭黑为乙炔炭黑,粒径30-45nm;碳纤维的单丝直径为6.5μm,长径比为2-15:1;碳化硅的粒径为1.3-1.5μm;2) Continue to maintain the reaction temperature at 85°C, add 150g of graphene-based two-dimensional carbon material, 80g of superconducting carbon black, 50g of carbon fiber, and 110g of silicon carbide into the reactor, and then continue to disperse at 85°C for 1 hour and mix well , to obtain a mixed slurry; the graphene-like two-dimensional carbon material is multilayer graphene, with a sheet diameter of 5-8 μm, and the superconducting carbon black is acetylene carbon black, with a particle diameter of 30-45 nm; the single filament diameter of the carbon fiber is 6.5 μm, and the length The diameter ratio is 2-15:1; the particle size of silicon carbide is 1.3-1.5μm;

将混合浆料缓慢冷却至室温,然后真空冻干,得到冻干物;研磨结束后采用200目筛网对研磨物过筛4遍,即得到用于聚合物基PTC材料的导电微粉,平均粒径为28μm;Slowly cool the mixed slurry to room temperature, and then vacuum freeze-dry to obtain a freeze-dried product; after grinding, use a 200-mesh screen to sieve the ground product 4 times to obtain conductive micropowder for polymer-based PTC materials, with an average particle size of The diameter is 28μm;

对比例3Comparative example 3

本对比例的PCT自控温涂料与实施例14的PTC自控温涂料的区别仅在于:本对比例采用的导电微粉为对比例1中制备的导电微粉。The only difference between the PCT self-temperature-controlling paint in this comparative example and the PTC self-temperature-controlling paint in Example 14 is that the conductive fine powder used in this comparative example is the conductive fine powder prepared in Comparative Example 1.

对比例4Comparative example 4

本对比例的PCT自控温涂料与实施例13的PTC自控温涂料的区别仅在于:本对比例采用的导电微粉为替换由石墨烯类二维碳材、超导炭黑、碳纤维和氮化铝组成的填料,石墨烯类二维碳材、超导炭黑、碳纤维和氮化铝的质量之比为150:100:30:100;所采用的石墨烯类二维碳材、超导炭黑、碳纤维和氮化铝同实施例7。The difference between the PCT self-temperature-controlling coating of this comparative example and the PTC self-temperature-controlling coating of Example 13 is only that: the conductive micropowder adopted in this comparative example is replaced by graphene-like two-dimensional carbon material, superconducting carbon black, carbon fiber and nitrogen The filler composed of aluminum oxide, the mass ratio of graphene-like two-dimensional carbon material, superconducting carbon black, carbon fiber and aluminum nitride is 150:100:30:100; the graphene-like two-dimensional carbon material, superconducting Carbon black, carbon fiber and aluminum nitride are the same as in Example 7.

对比例5Comparative example 5

本对比例的PCT自控温涂料与实施例17的PTC自控温涂料的区别仅在于:本对比例采用的导电微粉为对比例2中制备的导电微粉。The only difference between the PCT self-temperature-controlling paint in this comparative example and the PTC self-temperature-controlling paint in Example 17 is that the conductive fine powder used in this comparative example is the conductive fine powder prepared in Comparative Example 2.

实验例1Experimental example 1

分别将实施例13~15以及对比例1~2的PTC自控温涂料采用丝网印刷的方式制的规格为长×宽×厚为115mm×45.75mm×30μm的电热膜,在两侧面(115mm×30μm面)涂上导电银浆,对其进行室温-110℃的阻温测试及多次通电测试,得到相关数据如图1以及表1所示。The specifications of the PTC self-temperature-controlling coatings of Examples 13 to 15 and Comparative Examples 1 to 2 are made by screen printing respectively, and the length * width * thickness is an electrothermal film of 115mm * 45.75mm * 30 μm, on both sides (115mm ×30μm surface) was coated with conductive silver paste, and subjected to a temperature resistance test at room temperature -110°C and multiple power-on tests, and the relevant data were obtained as shown in Figure 1 and Table 1.

表1阻温测试以及多次通电测试的测试结果Table 1 Test results of resistance temperature test and multiple power-on tests

Figure BDA0003857319910000151
Figure BDA0003857319910000151

Figure BDA0003857319910000161
Figure BDA0003857319910000161

实验例2Experimental example 2

分别将实施例16~18以及对比例2~3的PTC自控温涂料采用丝网印刷的方式制成规格为长×宽×厚为115mm×45.75mm×30μm的电热膜,两侧面(115mm×30μm面)涂上导电银浆,对其进行室温-70℃的阻温测试及多次通电测试,得到相关数据如图2以及表2所示。The PTC self-temperature-controlling coatings of Examples 16-18 and Comparative Examples 2-3 were made into an electrothermal film with specifications of length × width × thickness 115mm × 45.75mm × 30 μm by screen printing, and the two sides (115mm × 30μm surface) was coated with conductive silver paste, and subjected to a temperature resistance test at room temperature -70°C and multiple power-on tests, and the relevant data were obtained as shown in Figure 2 and Table 2.

表2阻温测试以及多次通电测试的测试结果Table 2 Test results of temperature resistance test and multiple power-on tests

Figure BDA0003857319910000162
Figure BDA0003857319910000162

Claims (19)

1.一种用于聚合物基PTC材料的导电微粉,其特征在于:包括聚合物基PTC材料用固体填料和包覆在所述聚合物基PTC材料用固体填料表面的结晶性有机物层;所述聚合物基PTC材料用固体填料包括导电碳材;所述结晶性有机物层的主要成分为结晶性有机物,导电碳材与结晶性有机物的质量之比为10~120:10~50;所述导电微粉的粒径≤80μm。1. A conductive micropowder for polymer-based PTC material, characterized in that: comprise a polymer-based PTC material solid filler and a crystalline organic layer coated on the polymer-based PTC material solid filler surface; The solid filler for the polymer-based PTC material includes a conductive carbon material; the main component of the crystalline organic layer is a crystalline organic material, and the mass ratio of the conductive carbon material to the crystalline organic material is 10-120:10-50; The particle size of the conductive fine powder is ≤80μm. 2.根据权利要求1所述的用于聚合物基PTC材料的导电微粉,其特征在于:所述结晶性有机物的熔点为T,40℃≤T<80℃或T≥80℃;40℃≤T<80℃时,所述结晶性有机物为结晶聚合物和/或非聚合物型结晶性有机物;T≥80℃时,所述结晶性有机物为结晶聚合物。2. The conductive micropowder for polymer-based PTC materials according to claim 1, characterized in that: the melting point of the crystalline organic matter is T, 40°C≤T<80°C or T≥80°C; 40°C≤ When T<80°C, the crystalline organic matter is a crystalline polymer and/or non-polymer crystalline organic matter; when T≥80°C, the crystalline organic matter is a crystalline polymer. 3.根据权利要求2所述的用于聚合物基PTC材料的导电微粉,其特征在于:40℃≤T<80℃,所述结晶聚合物为聚乙二醇、乙烯-醋酸乙烯共聚物、氧化聚乙烯蜡、聚己内酯中的一种或任意合,所述非聚合物型结晶性有机物为棕榈酸、月桂酸、12-羟基硬脂酸中的一种或任意组合;3. The conductive micropowder for polymer-based PTC materials according to claim 2, characterized in that: 40°C≤T<80°C, the crystalline polymer is polyethylene glycol, ethylene-vinyl acetate copolymer, One or any combination of oxidized polyethylene wax and polycaprolactone, and the non-polymer crystalline organic matter is one or any combination of palmitic acid, lauric acid, and 12-hydroxystearic acid; 或80℃≤T≤120℃,所述结晶聚合物为聚乙烯、聚乙烯蜡、聚丙烯、乙烯-醋酸乙烯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物、聚氧化乙烯、聚氯乙烯、氯化聚乙烯中的一种或任意组合。or 80°C≤T≤120°C, the crystalline polymer is polyethylene, polyethylene wax, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, polyethylene oxide, One or any combination of polyvinyl chloride and chlorinated polyethylene. 4.根据权利要求1所述的用于聚合物基PTC材料的导电微粉,其特征在于:所述导电碳材为石墨烯类二维碳材、超导炭黑和碳纤维;石墨烯类二维碳材、超导炭黑、碳纤维和结晶性有机物的质量之比为5~30:5~40:0~50:10~50;所述石墨烯类二维碳材的片径为300nm-15μm;所述超导炭黑的粒径为35-300nm;所述碳纤维的单丝直径为1-10μm,长径比为2-15:1;所述导电微粉的平均粒径为10~30μm。4. the conductive micropowder for polymer base PTC material according to claim 1, is characterized in that: described conductive carbon material is graphene class two-dimensional carbon material, superconducting carbon black and carbon fiber; Graphene class two-dimensional carbon material The mass ratio of carbon material, superconducting carbon black, carbon fiber and crystalline organic matter is 5-30:5-40:0-50:10-50; the sheet diameter of the graphene-like two-dimensional carbon material is 300nm-15μm The particle size of the superconducting carbon black is 35-300nm; the monofilament diameter of the carbon fiber is 1-10μm, and the aspect ratio is 2-15:1; the average particle size of the conductive micropowder is 10-30μm. 5.根据权利要求4所述的用于聚合物基PTC材料的导电微粉,其特征在于:所述石墨烯类二维碳材为单层石墨烯、多层石墨烯、氧化石墨烯中的一种或任意组合;所述超导炭黑为乙炔炭黑和/或科琴黑。5. the conductive micropowder for polymer-based PTC material according to claim 4, characterized in that: said graphene-like two-dimensional carbon material is one of single-layer graphene, multilayer graphene, graphene oxide One or any combination; the superconducting carbon black is acetylene black and/or Ketjen black. 6.根据权利要求1~4中任意一项所述的用于聚合物基PTC材料的导电微粉,其特征在于:所述聚合物基PTC材料用固体填料还包括无机导热填料;无机导热填料与结晶性有机物的质量之比为5~30:10~50。6. The conductive micropowder for polymer-based PTC material according to any one of claims 1 to 4, characterized in that: the solid filler for the polymer-based PTC material also includes an inorganic heat-conducting filler; the inorganic heat-conducting filler and The mass ratio of crystalline organic matter is 5-30:10-50. 7.一种用于聚合物基PTC材料的导电微粉的制备方法,其特征在于:包括以下步骤:将混合浆料干燥成固体,然后破碎成微粉;7. A preparation method for conductive micropowder of polymer-based PTC material, characterized in that: comprising the steps of: drying the mixed slurry into solid, and then breaking into micropowder; 所述混合浆料是将聚合物基PTC材料用固体填料分散在结晶性有机物乳液中得到;所述聚合物基PTC材料用固体填料包括导电碳材;所述导电碳材与结晶性有机物乳液中结晶性有机物的质量之比为10~120:10~50;所述导电微粉的粒径≤80μm。The mixed slurry is obtained by dispersing the solid filler for the polymer-based PTC material in the crystalline organic emulsion; the solid filler for the polymer-based PTC material includes a conductive carbon material; the conductive carbon material and the crystalline organic emulsion The mass ratio of the crystalline organic matter is 10-120:10-50; the particle diameter of the conductive fine powder is ≤80 μm. 8.根据权利要求7所述的用于聚合物基PTC材料的导电微粉的制备方法,其特征在于:所述结晶性有机物的熔点为T,40℃≤T<80℃或T≥80℃;40℃≤T<80℃时,所述结晶性有机物为结晶聚合物和/或非聚合物型结晶性有机物;T≥80℃时,所述结晶性有机物为结晶聚合物。8. The method for preparing conductive micropowder for polymer-based PTC materials according to claim 7, characterized in that: the melting point of the crystalline organic matter is T, 40°C≤T<80°C or T≥80°C; When 40°C≤T<80°C, the crystalline organic matter is a crystalline polymer and/or non-polymer crystalline organic matter; when T≥80°C, the crystalline organic matter is a crystalline polymer. 9.根据权利要求8所述的用于聚合物基PTC材料的导电微粉的制备方法,其特征在于:40℃≤T<80℃,所述结晶聚合物为聚乙二醇、乙烯-醋酸乙烯共聚物、氧化聚乙烯蜡、聚己内酯中的一种或任意合,所述非聚合物型结晶性有机物为棕榈酸、月桂酸、12-羟基硬脂酸中的一种或任意组合;9. The method for preparing conductive micropowder for polymer-based PTC materials according to claim 8, characterized in that: 40°C≤T<80°C, the crystalline polymer is polyethylene glycol, ethylene-vinyl acetate One or any combination of copolymer, oxidized polyethylene wax, and polycaprolactone, and the non-polymer crystalline organic compound is one or any combination of palmitic acid, lauric acid, and 12-hydroxystearic acid; 或80℃≤T≤120℃,所述结晶聚合物为聚乙烯、聚乙烯蜡、聚丙烯、乙烯-醋酸乙烯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物、聚氧化乙烯、聚氯乙烯、氯化聚乙烯中的一种或任意组合。or 80°C≤T≤120°C, the crystalline polymer is polyethylene, polyethylene wax, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, polyethylene oxide, One or any combination of polyvinyl chloride and chlorinated polyethylene. 10.根据权利要求7所述的用于聚合物基PTC材料的导电微粉的制备方法,其特征在于:所述导电碳材由以下重量份数的组分组成:石墨烯类二维碳材5~30份、超导炭黑5~40份、碳纤维0~50份;所述石墨烯类二维碳材与结晶性有机物的质量之比为5~30:10~50;所述石墨烯类二维碳材的片径为300nm-15μm;所述超导炭黑的粒径为30-300nm;所述碳纤维的单丝直径为1-10μm,长径比2-15:1;所述导电微粉的平均粒径为10~30μm。10. the preparation method of the conductive micropowder that is used for polymer base PTC material according to claim 7, is characterized in that: described conductive carbon material is made up of the component of following parts by weight: graphene class two-dimensional carbon material 5 ~30 parts, 5~40 parts of superconducting carbon black, 0~50 parts of carbon fiber; the mass ratio of the graphene-based two-dimensional carbon material to the crystalline organic matter is 5~30:10~50; the graphene-based The sheet diameter of the two-dimensional carbon material is 300nm-15μm; the particle size of the superconducting carbon black is 30-300nm; the monofilament diameter of the carbon fiber is 1-10μm, and the aspect ratio is 2-15:1; the conductive The average particle diameter of the fine powder is 10-30 μm. 11.根据权利要求10所述的用于聚合物基PTC材料的导电微粉的制备方法,其特征在于:所述超导炭黑为乙炔炭黑和/或科琴黑;所述石墨烯类二维碳材为单层石墨烯、多层石墨烯、氧化石墨烯中的一种或任意组合。11. the preparation method of the conductive micropowder that is used for polymer base PTC material according to claim 10, is characterized in that: described superconducting carbon black is acetylene carbon black and/or ketjen black; The dimensional carbon material is one or any combination of single-layer graphene, multi-layer graphene, and graphene oxide. 12.根据权利要求7所述的用于聚合物基PTC材料的导电微粉的制备方法,其特征在于:所述结晶性有机物乳液是将结晶性有机物分散在水中形成;所述结晶性有机物乳液的制备方法包括以下步骤:将结晶性有机物、乳化剂和分散剂加热至结晶性有机物熔点以上熔融混匀,然后加水在设定压力和设定温度下进行分散乳化,即得;水在所述设定压力下的沸点不低于结晶性有机物的熔点,且所述设定温度不高于水在所述设定压力下的沸点。12. the preparation method of the conductive micropowder that is used for polymer base PTC material according to claim 7, is characterized in that: described crystalline organic matter emulsion is that crystalline organic matter is dispersed in water and forms; The crystalline organic matter emulsion The preparation method comprises the following steps: heating the crystalline organic matter, emulsifier and dispersant to above the melting point of the crystalline organic matter, melting and mixing, and then adding water to disperse and emulsify at a set pressure and set temperature to obtain; The boiling point under constant pressure is not lower than the melting point of crystalline organic matter, and the set temperature is not higher than the boiling point of water under the set pressure. 13.根据权利要求12所述的用于聚合物基PTC材料的导电微粉的制备方法,其特征在于:所述乳化剂为阴离子型乳化剂和/或非离子型乳化剂;所述阴离子型乳化剂为烷基硫酸盐、烷基磺酸盐、烷基苯磺酸盐中的一种或任意组合;所述非离子型乳化剂为烷基酚聚氧乙烯醚乳化剂、失水山梨醇脂肪酸酯乳化剂、聚氧乙烯失水山梨醇脂肪酸酯乳化剂中的一种或任意组合;所述分散剂为脂肪酸类分散剂、脂肪族酰胺类分散剂、甘油酯类分散剂中的一种或任意组合。13. the preparation method of the conductive micropowder that is used for polymer base PTC material according to claim 12, is characterized in that: described emulsifying agent is anionic emulsifying agent and/or nonionic emulsifying agent; Described anionic emulsifying agent The agent is one or any combination of alkyl sulfate, alkyl sulfonate, alkylbenzene sulfonate; the nonionic emulsifier is alkylphenol polyoxyethylene ether emulsifier, sorbitan fat One or any combination of ester emulsifiers, polyoxyethylene sorbitan fatty acid ester emulsifiers; the dispersant is one of fatty acid dispersants, aliphatic amide dispersants, and glyceride dispersants species or any combination. 14.根据权利要求7所述的用于聚合物基PTC材料的导电微粉的制备方法,其特征在于:所述聚合物基PTC材料用固体填料还包括无机导热填料,所述无机导热填料与结晶性有机物乳液中结晶性有机物的质量之比为5~30:10~50;所述无机导热填料的粒径为50nm~5μm。14. the preparation method of the conductive micropowder that is used for polymer-based PTC material according to claim 7, is characterized in that: described polymer-based PTC material solid filler also comprises inorganic heat-conducting filler, and described inorganic heat-conducting filler and crystallization The mass ratio of the crystalline organic matter in the latex organic matter emulsion is 5-30:10-50; the particle diameter of the inorganic heat-conducting filler is 50 nm-5 μm. 15.根据权利要求14所述的用于聚合物基PTC材料的导电微粉的制备方法,其特征在于:所述无机导热填料选自碳化硅、二氧化硅、氮化硼、氮化铝中的一种或任意组合。15. the preparation method of the conductive micropowder that is used for polymer-based PTC material according to claim 14, is characterized in that: described inorganic heat-conducting filler is selected from silicon carbide, silicon dioxide, boron nitride, aluminum nitride One or any combination. 16.一种PTC自控温涂料,其特征在于:包括树脂乳液和分散在树脂乳液中的导电微粉和添加剂;所述导电微粉为权利要求1~6中任意一项所述的用于聚合物基PTC材料的导电微粉或如权利要求7~15中任意一项所述的制备方法制得的用于聚合物基PTC材料的导电微粉。16. A PTC self-temperature-controlling coating, characterized in that: it includes resin emulsion and conductive micropowder and additives dispersed in the resin emulsion; Conductive micropowder of PTC-based materials or conductive micropowder for polymer-based PTC materials prepared by the preparation method according to any one of claims 7-15. 17.根据权利要求16所述的PTC自控温涂料,其特征在于:所述树脂乳液中固形物与导电微粉中结晶性有机物的质量之比为30~60:10~50。17. The PTC self-temperature-controlling paint according to claim 16, characterized in that: the mass ratio of the solid matter in the resin emulsion to the crystalline organic matter in the conductive fine powder is 30-60:10-50. 18.根据权利要求16所述的PTC自控温涂料,其特征在于:所述树脂乳液为聚氨酯乳液、丙烯酸乳液、丙烯酸酯乳液、有机硅乳液、环氧树脂乳液中的一种或任意组合;所述树脂乳液的固含量为30~60%。18. The PTC self-temperature control coating according to claim 16, characterized in that: the resin emulsion is one or any combination of polyurethane emulsion, acrylic emulsion, acrylate emulsion, silicone emulsion, epoxy resin emulsion; The solid content of the resin emulsion is 30-60%. 19.根据权利要求16所述的PTC自控温涂料,其特征在于:所述添加剂包括消泡剂和流平剂;所述消泡剂、流平剂和树脂乳液质量之比为3~50:3~50:1000;所述消泡剂为有机硅型消泡剂和/或聚醚改性有机硅型消泡剂;所述流平剂为丙烯酸类流平剂、丙烯酸酯类流平剂、有机硅流平剂中的一种或任意组合。19. The PTC self-temperature control coating according to claim 16, characterized in that: the additives include defoamers and leveling agents; the mass ratio of the defoamers, leveling agents and resin emulsions is 3 to 50 :3~50:1000; the defoamer is a silicone type defoamer and/or polyether modified silicone type defoamer; the leveling agent is an acrylic leveling agent, an acrylic leveling agent One or any combination of agent, silicone leveling agent.
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