WO2023272565A1 - 一种用于透明塑料填充的复合硫酸钡填充母料及制备方法 - Google Patents

一种用于透明塑料填充的复合硫酸钡填充母料及制备方法 Download PDF

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WO2023272565A1
WO2023272565A1 PCT/CN2021/103453 CN2021103453W WO2023272565A1 WO 2023272565 A1 WO2023272565 A1 WO 2023272565A1 CN 2021103453 W CN2021103453 W CN 2021103453W WO 2023272565 A1 WO2023272565 A1 WO 2023272565A1
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barium sulfate
composite
graphene film
filling
transparent plastic
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PCT/CN2021/103453
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English (en)
French (fr)
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罗洋德
潘小阳
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浙江中邦塑胶股份有限公司
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Publication of WO2023272565A1 publication Critical patent/WO2023272565A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • the invention relates to the technical field of barium sulfate, in particular to a composite barium sulfate filler masterbatch used for filling transparent plastics and a preparation method thereof.
  • barium sulfate The mineral of barium sulfate is called barite. It is white amorphous powder. Stable in nature, hardly soluble in water, acid, alkali or organic solvents. 1. Barium sulfate is insoluble in water and acid, has stable chemical properties, has no magnetic toxicity, and has the ability to absorb X-rays and gamma rays. Barite is mainly produced in sedimentary layered deposits and low-temperature hydrothermal veins, and often coexists with quartz, dolomite, calcite, fluorite, galena, sphalerite, and chalcopyrite. 2.
  • barium carbonate barium chloride, barium sulfate, barium nitrate, barium hydroxide, barium oxide, barium peroxide, barium chromate, barium manganate, barium chlorate, lithopone, polysulfide barium etc.
  • Barium compounds have a wide range of uses: used as raw materials and fillers for rubber, plastics, pigments, paints, paper, textiles, paints, inks, welding rods; used as raw materials for barium-based grease, oil refining, beet sugar, and rayon; Used as insecticide, sterilizer, rodenticide, explosive, green fireworks, signal bomb, tracer bomb, indicator of medical X-ray imaging, etc.; also used in glass, ceramics, leather, electronics, building materials, metallurgy and other departments.
  • Metal barium can be used as a getter and binder for televisions and vacuum tubes. Alloys of barium with metals such as aluminum, magnesium, lead, and silver are used to make bearings. 3.
  • a sizing agent and a weighting agent for fabrics As a mordant for printing and dyeing, a sizing agent and a weighting agent for fabrics, a filler for papermaking, a filler for fireproof fabrics and tanning, a laxative for the pharmaceutical industry, and a raw material for the production of stomach medicine magnesium trisilicate, esophagus, gastrointestinal tract X-ray contrast diagnosis is used in the production of fresh yeast, monosodium glutamate and stabilizer of calcium hydrogen phosphate for toothpaste, and is also used in the preparation of plant hibernation prolonging agent. It is used in the preparation of crack-free plating solution in metal electroplating, as a conductive salt in nickel plating solution, and can also make the white surface of the plating layer soft. 4.
  • Functional filler masterbatch is a new product in recent years.
  • Barium sulfate is added to plastic film products because of its small powder particle size, high transparency, good gloss, good appearance and hue, and can improve plastic tensile force. It can replace most petrochemical products, reduce the amount of plastic used, maintain the transparency of the film, and at the same time reduce the cost of use and processing.
  • the strength and transparency of the barium sulfate masterbatch currently on the market are used in plastic films.
  • the invention provides a composite barium sulfate filler masterbatch used for filling transparent plastics.
  • the present invention proposes a composite barium sulfate filler masterbatch for filling transparent plastics.
  • a composite barium sulfate filler masterbatch for transparent plastic filling which is composed of the following ingredients in weight percent: stearic acid 1.4-2.0%, coupling agent 1.2-1.8%, low-density polyethylene 8-20%, polyethylene Wax 1.8-2.8%, template modifier 0.1-0.3% and barium sulfate balance.
  • the barium sulfate is a barium sulfate powder produced by a precipitation method with an average particle size of ⁇ 0.2 ⁇ m and a powder whiteness of ⁇ 98%.
  • the coupling agent is a silane coupling agent or an aluminate coupling agent.
  • the template modifier is a composite material of glass fiber wool and graphene film.
  • the preparation method of the template modifier comprises the following steps:
  • the pretreatment method of the pretreated graphene film is: bombarding the graphene film with a pulsed laser along the thickness direction.
  • the specific parameters are: laser wavelength 532nm, energy 200-300mJ, pulse width 4-6ns, focused beam spot 0.3-0.35mm, bombardment frequency 5-8Hz;
  • the spacing is the same, the width is ⁇ 0.05mm, and the width is the same as that of the processed graphene film; the graphene film moves in the vertical direction at a speed of 60-90m/s; the thickness of the graphene film is 900-1000 layers.
  • a method for preparing a composite barium sulfate filler masterbatch used for transparent plastic filling comprising the following steps: adding barium sulfate and a template modifier to a high-speed mixer with a rotation speed of 800-1500r/min, stirring at a high speed and heating to 120 -130°C, add polyethylene wax, low-density polyethylene, stearic acid, and coupling agent in sequence, mix well, melt and extrude in the extruder, and make granular masterbatch after granulation.
  • the temperature of each zone of the extruder is set at: 55 ⁇ 5°C, 80 ⁇ 5°C, 95 ⁇ 3°C, 120 ⁇ 2°C, 130 ⁇ 2°C, 155 ⁇ 2°C, 140 ⁇ 2°C , 160 ⁇ 2°C, the die head temperature is 165°C ⁇ 1°C.
  • the composite barium sulfate filler masterbatch used for transparent plastic filling of the present invention adds a template modifier on the basis of the traditional barium sulfate filler masterbatch, and the template modifier is glass fiber
  • the composite material of cotton and graphene film can not only significantly improve the strength of the material, but also effectively improve the order of the raw materials in the masterbatch, thereby improving its transparency after being applied to transparent plastic filling.
  • the specific principle is speculated as follows: template The modifier is cut into a filament with a length of 0.5-1.2mm and a width of ⁇ 0.1mm. It is a double-layer structure composed of glass fiber cotton and graphene film.
  • the outer surface of the glass fiber cotton side is relatively smooth, but the graphene Due to the pretreatment of pulsed laser bombardment of the film on one side of the film, there are a large number of uniformly arranged micropores on the surface of the film. These micropores are conducive to the uniform and fine arrangement of barium sulfate powder, so that it can be applied to transparent plastics to achieve better transparency.
  • a composite barium sulfate filler masterbatch for transparent plastic filling which is composed of the following ingredients in weight percent: 1.7% stearic acid, 1.5% coupling agent, 12% low-density polyethylene, 2.4% polyethylene wax, template modification Active agent 0.25% and the balance of barium sulfate.
  • the barium sulfate is a barium sulfate powder produced by a precipitation method with an average particle diameter of ⁇ 0.2 ⁇ m and a powder whiteness of ⁇ 98%.
  • the coupling agent is a silane coupling agent.
  • the template modifier is a composite material of glass fiber cotton and graphene film. The preparation method of described template modifier comprises the following steps:
  • the pretreatment method of the pretreated graphene film is: bombarding the graphene film with a pulsed laser along the thickness direction.
  • the specific parameters are: laser wavelength 532nm, energy 250mJ, pulse width 5ns, focused beam spot 0.32mm, bombardment frequency 7Hz; multiple laser beams are arranged linearly in the horizontal direction, the distance between adjacent laser beams is the same, and the width is ⁇ 0.05mm.
  • the width is the same as that of the processed graphene film; the graphene film moves in the vertical direction at a speed of 75m/s; the thickness of the graphene film is 950 layers.
  • a method for preparing a composite barium sulfate filler masterbatch for transparent plastic filling comprising the following steps: adding barium sulfate and a template modifier into a high-speed mixer with a rotation speed of 1200r/min, stirring at a high speed and heating to 125°C, Add polyethylene wax, low-density polyethylene, stearic acid, and coupling agent in sequence, mix evenly, melt and extrude in an extruder, and granulate to make granular masterbatch.
  • the temperature of each zone of the extruder is set at: 55 ⁇ 5°C, 80 ⁇ 5°C, 95 ⁇ 3°C, 120 ⁇ 2°C, 130 ⁇ 2°C, 155 ⁇ 2°C, 140 ⁇ 2°C, 160 ⁇ 2°C °C, the die head temperature is 165°C ⁇ 1°C.
  • a composite barium sulfate filler masterbatch for transparent plastic filling which is composed of the following ingredients in weight percent: 2.0% stearic acid, 1.2% coupling agent, 20% low-density polyethylene, 1.8% polyethylene wax, template modification Active agent 0.3% and the balance of barium sulfate.
  • the barium sulfate is a barium sulfate powder produced by a precipitation method with an average particle diameter of ⁇ 0.2 ⁇ m and a powder whiteness of ⁇ 98%.
  • the coupling agent is an aluminate coupling agent.
  • the template modifier is a composite material of glass fiber cotton and graphene film. The preparation method of described template modifier comprises the following steps:
  • the pretreatment method of the pretreated graphene film is: bombarding the graphene film with a pulsed laser along the thickness direction.
  • the specific parameters are: laser wavelength 532nm, energy 300mJ, pulse width 4ns, focused beam spot 0.35mm, bombardment frequency 5Hz; multiple laser beams are arranged linearly in the horizontal direction, the distance between adjacent laser beams is the same, and the width is ⁇ 0.05mm.
  • the width is the same as that of the processed graphene film; the graphene film moves in the vertical direction at a speed of 90m/s; the thickness of the graphene film is 900 layers.
  • a method for preparing a composite barium sulfate filler masterbatch for transparent plastic filling comprising the following steps: adding barium sulfate and a template modifier to a high-speed mixer with a rotation speed of 1500r/min, stirring at a high speed and heating to 120°C, Add polyethylene wax, low-density polyethylene, stearic acid, and coupling agent in sequence, mix evenly, melt and extrude in an extruder, and granulate to make granular masterbatch.
  • the temperature of each zone of the extruder is set at: 55 ⁇ 5°C, 80 ⁇ 5°C, 95 ⁇ 3°C, 120 ⁇ 2°C, 130 ⁇ 2°C, 155 ⁇ 2°C, 140 ⁇ 2°C, 160 ⁇ 2°C °C, the die head temperature is 165°C ⁇ 1°C.
  • a composite barium sulfate filler masterbatch for transparent plastic filling which is composed of the following components by weight percentage: 1.4% stearic acid, 1.8% coupling agent, 8% low-density polyethylene, 2.8% polyethylene wax, template modification Active agent 0.1% and the balance of barium sulfate.
  • the barium sulfate is a barium sulfate powder produced by a precipitation method with an average particle diameter of ⁇ 0.2 ⁇ m and a powder whiteness of ⁇ 98%.
  • the coupling agent is a silane coupling agent or an aluminate coupling agent.
  • the template modifier is a composite material of glass fiber cotton and graphene film. The preparation method of described template modifier comprises the following steps:
  • the pretreatment method of the pretreated graphene film is: bombarding the graphene film with a pulsed laser along the thickness direction.
  • the specific parameters are: laser wavelength 532nm, energy 200mJ, pulse width 6ns, focused beam spot 0.3mm, bombardment frequency 8Hz; multiple laser beams are arranged linearly in the horizontal direction, the distance between adjacent laser beams is the same, and the width is ⁇ 0.05mm.
  • the width is the same as that of the processed graphene film; the graphene film moves in the vertical direction at a speed of 60m/s; the thickness of the graphene film is 1000 layers.
  • a method for preparing a composite barium sulfate filler masterbatch for filling transparent plastics comprising the following steps: adding barium sulfate and a template modifier to a high-speed mixer with a rotation speed of 800r/min, stirring at a high speed and heating to 130°C, Add polyethylene wax, low-density polyethylene, stearic acid, and coupling agent in sequence, mix evenly, melt and extrude in an extruder, and granulate to make granular masterbatch.
  • the temperature of each zone of the extruder is set at: 55 ⁇ 5°C, 80 ⁇ 5°C, 95 ⁇ 3°C, 120 ⁇ 2°C, 130 ⁇ 2°C, 155 ⁇ 2°C, 140 ⁇ 2°C, 160 ⁇ 2°C °C, the die head temperature is 165°C ⁇ 1°C.
  • Example 1 The template modifier in Example 1 is replaced with a length of 0.5-1.2mm without electrostatic adsorption, and glass fiber cotton and graphene film filaments with a width ⁇ 0.1mm (that is, glass fiber is added respectively during the preparation process) Cotton filament and graphene film filament), all the other proportioning and preparation methods remain unchanged.
  • Example 1 The pretreated graphene film in Example 1 was replaced by a graphene film that had not been bombarded by pulsed laser, and the remaining proportions and preparation methods remained unchanged.
  • the composite barium sulfate filler masterbatch used for transparent plastic filling prepared by Examples 1-3 and Comparative Example 12 is mixed according to 20 parts of masterbatch and 80 parts of high-density polyethylene, and blown film is prepared on a film blowing machine to prepare a film sample.
  • the sample thickness is 0.020 mm.
  • the prepared film samples were tested for light transmittance and tensile properties, and the masterbatch samples were tested for melt index. The results are shown in Table 1.
  • Table 1 Composite barium sulfate filler masterbatch of the present invention and the detection result of film sample thereof;
  • the melt index is measured according to the method specified in GB/T36822000, wherein the test conditions include a temperature of 190°C and a load of 2.16kg; 2.
  • the light transmittance of the film is measured according to the method specified in GB/T2410-2008 , measured by a light transmittance-haze tester; 3.
  • the longitudinal tensile strength of the film is measured according to the method specified in GB/T1040.3-2006.
  • the composite barium sulfate filler masterbatch of the present invention after being applied to transparent plastic films, not only has good tensile strength, but also has very good light transmittance.

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Abstract

一种用于透明塑料填充的复合硫酸钡填充母料，由以下重量百分比的成分组成：硬脂酸1.4-2.0％，偶联剂1.2-1.8％，低密度聚乙烯8-20％，聚乙烯蜡1.8-2.8％，模板改性剂0.1-0.3％和硫酸钡余量。由于加入了由玻璃纤维棉和石墨烯薄膜的组成的模板改性剂，不但可以显著提升材料的强度，而且可以有效提升原料在母粒中的排列有序性，从而提升其应用于透明塑料填充后的透明度。具体原理推测如下：模板改性剂为玻璃纤维棉和石墨烯薄膜组成双层结构，石墨烯薄膜一侧表面有大量排列均匀的微孔，这些微孔有利于硫酸钡粉体均匀细致的排列，从而使其应用于透明塑料，达到更好的透明度。

Description

一种用于透明塑料填充的复合硫酸钡填充母料及制备方法 技术领域
本发明涉及硫酸钡技术领域，尤其涉及一种用于透明塑料填充的复合硫酸钡填充母料及制备方法。
背景技术
硫酸钡的矿产叫做重晶石。为白色无定型粉末。性质稳定，难溶于水、酸、碱或有机溶剂。1.硫酸钡不溶于水和酸，化学性质稳定，无磁性毒性，并有吸收X射线和伽马射线的性能。重晶石主要产于沉积层状矿床和低温热液矿脉中，常与石英、白云石、方解石、萤石、方铅矿、闪锌矿、黄铜矿等共生。2.主要用于石油和天然气钻井泥浆的加重剂，也是提取金属钡和制取各种钡化合物的重要矿物原料。工业上最重要的钡化合物有碳酸钡、氯化钡、硫酸钡、硝酸钡、氢氧化钡、氧化钡、过氧化钡、铬酸钡、锰酸钡、氯酸钡、锌钡白、多硫化钡等。钡化合物的用途十分广泛：用作橡胶、塑料、颜料、涂料、造纸、纺织品、油漆、油墨、焊条的原料及填料；用作钡基润滑脂、油料精制、甜菜制糖、人造丝的原料；用作杀虫剂、灭菌剂、灭鼠剂、炸药、绿色烟火、信号弹、曳光弹、医学X光照像的指示剂等；还用于玻璃、陶瓷、皮革、电子、建材、冶金等部门。金属钡可作电视和真空管的吸气剂、黏结剂。钡与铝、镁、铅、银等金属制作的合金用于制造轴承。3.作印染的媒染剂，织物的上浆剂、加重剂，造纸的填充剂，防火织物及制革的填充剂，医药工业的泻剂和生产胃药三硅酸镁的原料，食道、胃肠道X射线造影诊断于生产鲜酵母、味精和牙膏用磷酸氢钙的稳定剂，亦用于配制植物冬眠延长剂。在金属电镀中用于无裂纹镀液的配制，在镀镍液中作导电盐，还能使镀层白面柔软。4.用作胶黏剂、密封剂、橡 胶、塑料、油漆、油墨、白色颜料、绝缘带等的填充剂，可赋予橡胶、塑料制品以X射线不透过性，并可提高氯丁橡胶制品的耐燃性。纺织上可用作上浆剂。印相纸及铜版纸生产时用作表面涂布剂。电镀工业用作镀镍液的导电盐，可改善电镀液分散性。玻璃制造中用作澄清剂，具有增加光泽及消泡作用。也是制造搪瓷、陶瓷、颜料及其他钡盐等的原料及X射线透视肠胃造影剂等。
功能填充母料是近几年新兴的一种产品，硫酸钡因其粉体粒径小、透明度高、光泽度好、外观色相好、能提高塑料拉力，制备的母料添加到塑料薄膜制品中可以替代大部分石化产品，减少塑料的使用量，保持薄膜的透明度，同时又可以降低使用和加工成本，但是目前市场上的硫酸钡母料应用于塑料薄膜，其强度和透明度均有待提高，故本发明提出了一种用于透明塑料填充的复合硫酸钡填充母料。
发明内容
基于背景技术存在的技术问题，本发明提出了一种用于透明塑料填充的复合硫酸钡填充母料。
本发明的技术方案如下：
一种用于透明塑料填充的复合硫酸钡填充母料，由以下重量百分比的成分组成：硬脂酸1.4-2.0％，偶联剂1.2-1.8％，低密度聚乙烯8-20％，聚乙烯蜡1.8-2.8％，模板改性剂0.1-0.3％和硫酸钡余量。
优选的，所述的硫酸钡为平均粒径≤0.2μm，粉体白度≥98％的沉淀法生产的硫酸钡粉体。
优选的，所述的偶联剂为硅烷偶联剂或者铝酸酯偶联剂。
优选的，所述的模板改性剂为玻璃纤维棉和石墨烯薄膜的复合材料。
进一步优选的，所述的模板改性剂的制备方法，包括以下步骤：
A、将0.1-1μm直径的超细玻璃纤维在成型网上制成超细玻璃纤维棉；
B、采用静电吸附的方式将与经过预处理的石墨烯薄膜通过静电吸附的方式贴合到超细玻璃纤维棉上，形成复合膜；
C、将复合膜裁切成长度为0.5-1.2mm，宽度≤0.1mm的丝状物，即可。
进一步优选的，所述的经过预处理的石墨烯薄膜的预处理方法为：用脉冲激光沿厚度方向轰击石墨烯薄膜。具体的参数为：激光波长532nm，能量200-300mJ，脉冲宽度4-6ns，聚焦束斑0.3-0.35mm，轰击频率为5-8Hz；多束激光在水平方向成线性排列，相邻激光束的间距相同，宽度≤0.05mm，宽度与处理的石墨烯薄膜相同；石墨烯薄膜沿垂直方向运动，运动速度为60-90m/s；石墨烯薄膜厚度为900-1000层。
一种用于透明塑料填充的复合硫酸钡填充母料的制备方法，包括以下步骤：把硫酸钡和模板改性剂加入到转速为800-1500r/min的高混机内高速搅拌并加热到120-130℃，依次加入聚乙烯蜡、低密度聚乙烯、硬脂酸、偶联剂，混合均匀，在挤出机中熔融挤出，经过造粒而制成粒状母粒。
进一步优选的，所述的挤出机的各区温度设为：55±5℃，80±5℃，95±3℃，120±2℃，130±2℃，155±2℃，140±2℃，160±2℃，模头温度为165℃±1℃。
本发明的有益之处在于：本发明的用于透明塑料填充的复合硫酸钡填充母料，在传统的硫酸钡填充母料的基础上加入了模板改性剂，该模板改性剂为玻璃纤维棉和石墨烯薄膜的复合材料，不但可以显著提升材料的强度，而且可以有效提升原料在母粒中的排列有序性，从而提升其应用于透明塑料填充后的透明度，具体原理推测如下：模板改性剂为裁切成长度为0.5一1.2mm，宽度≤0.1mm的丝状物，其为玻璃纤维棉和石墨烯薄膜组成双层结构，玻璃纤维棉一侧外表面较为光滑，但石墨烯薄膜一侧由于进行了脉冲激光轰击薄膜的预处理，导致 薄膜表面有大量排列均匀的微孔，这些微孔有利于硫酸钡粉体均匀细致的排列，从而使其应用于透明塑料，达到更好的透明度。
具体实施方式
实施例1
一种用于透明塑料填充的复合硫酸钡填充母料，由以下重量百分比的成分组成：硬脂酸1.7％，偶联剂1.5％，低密度聚乙烯12％，聚乙烯蜡2.4％，模板改性剂0.25％和硫酸钡余量。
所述的硫酸钡为平均粒径≤0.2μm，粉体白度≥98％的沉淀法生产的硫酸钡粉体。所述的偶联剂为硅烷偶联剂。所述的模板改性剂为玻璃纤维棉和石墨烯薄膜的复合材料。所述的模板改性剂的制备方法，包括以下步骤：
A、将0.1-1μm直径的超细玻璃纤维在成型网上制成超细玻璃纤维棉；
B、采用静电吸附的方式将与经过预处理的石墨烯薄膜通过静电吸附的方式贴合到超细玻璃纤维棉上，形成复合膜；
C、将复合膜裁切成长度为0.5-1.2mm，宽度≤0.1mm的丝状物，即可。
所述的经过预处理的石墨烯薄膜的预处理方法为：用脉冲激光沿厚度方向轰击石墨烯薄膜。具体的参数为：激光波长532nm，能量250mJ，脉冲宽度5ns，聚焦束斑0.32mm，轰击频率为7Hz；多束激光在水平方向成线性排列，相邻激光束的间距相同，宽度≤0.05mm，宽度与处理的石墨烯薄膜相同；石墨烯薄膜沿垂直方向运动，运动速度为75m/s；石墨烯薄膜厚度为950层。
一种用于透明塑料填充的复合硫酸钡填充母料的制备方法，包括以下步骤：把硫酸钡和模板改性剂加入到转速为1200r/min的高混机内高速搅拌并加热到125℃，依次加入聚乙烯蜡、低密度聚乙烯、硬脂酸、偶联剂，混合均匀，在挤出机中熔融挤出，经过造粒而制成粒状母粒。
所述的挤出机的各区温度设为：55±5℃，80±5℃，95±3℃，120±2℃，130±2℃，155±2℃，140±2℃，160±2℃，模头温度为165℃±1℃。
实施例2
一种用于透明塑料填充的复合硫酸钡填充母料，由以下重量百分比的成分组成：硬脂酸2.0％，偶联剂1.2％，低密度聚乙烯20％，聚乙烯蜡1.8％，模板改性剂0.3％和硫酸钡余量。
所述的硫酸钡为平均粒径≤0.2μm，粉体白度≥98％的沉淀法生产的硫酸钡粉体。所述的偶联剂为铝酸酯偶联剂。所述的模板改性剂为玻璃纤维棉和石墨烯薄膜的复合材料。所述的模板改性剂的制备方法，包括以下步骤：
A、将0.1-1μm直径的超细玻璃纤维在成型网上制成超细玻璃纤维棉；
B、采用静电吸附的方式将与经过预处理的石墨烯薄膜通过静电吸附的方式贴合到超细玻璃纤维棉上，形成复合膜；
C、将复合膜裁切成长度为0.5-1.2mm，宽度≤0.1mm的丝状物，即可。
所述的经过预处理的石墨烯薄膜的预处理方法为：用脉冲激光沿厚度方向轰击石墨烯薄膜。具体的参数为：激光波长532nm，能量300mJ，脉冲宽度4ns，聚焦束斑0.35mm，轰击频率为5Hz；多束激光在水平方向成线性排列，相邻激光束的间距相同，宽度≤0.05mm，宽度与处理的石墨烯薄膜相同；石墨烯薄膜沿垂直方向运动，运动速度为90m/s；石墨烯薄膜厚度为900层。
一种用于透明塑料填充的复合硫酸钡填充母料的制备方法，包括以下步骤：把硫酸钡和模板改性剂加入到转速为1500r/min的高混机内高速搅拌并加热到120℃，依次加入聚乙烯蜡、低密度聚乙烯、硬脂酸、偶联剂，混合均匀，在挤出机中熔融挤出，经过造粒而制成粒状母粒。
所述的挤出机的各区温度设为：55±5℃，80±5℃，95±3℃，120±2℃， 130±2℃，155±2℃，140±2℃，160±2℃，模头温度为165℃±1℃。
实施例3
一种用于透明塑料填充的复合硫酸钡填充母料，由以下重量百分比的成分组成：硬脂酸1.4％，偶联剂1.8％，低密度聚乙烯8％，聚乙烯蜡2.8％，模板改性剂0.1％和硫酸钡余量。
所述的硫酸钡为平均粒径≤0.2μm，粉体白度≥98％的沉淀法生产的硫酸钡粉体。所述的偶联剂为硅烷偶联剂或者铝酸酯偶联剂。所述的模板改性剂为玻璃纤维棉和石墨烯薄膜的复合材料。所述的模板改性剂的制备方法，包括以下步骤：
A、将0.1-1μm直径的超细玻璃纤维在成型网上制成超细玻璃纤维棉；
B、采用静电吸附的方式将与经过预处理的石墨烯薄膜通过静电吸附的方式贴合到超细玻璃纤维棉上，形成复合膜；
C、将复合膜裁切成长度为0.5-1.2mm，宽度≤0.1mm的丝状物，即可。
所述的经过预处理的石墨烯薄膜的预处理方法为：用脉冲激光沿厚度方向轰击石墨烯薄膜。具体的参数为：激光波长532nm，能量200mJ，脉冲宽度6ns，聚焦束斑0.3mm，轰击频率为8Hz；多束激光在水平方向成线性排列，相邻激光束的间距相同，宽度≤0.05mm，宽度与处理的石墨烯薄膜相同；石墨烯薄膜沿垂直方向运动，运动速度为60m/s；石墨烯薄膜厚度为1000层。
一种用于透明塑料填充的复合硫酸钡填充母料的制备方法，包括以下步骤：把硫酸钡和模板改性剂加入到转速为800r/min的高混机内高速搅拌并加热到130℃，依次加入聚乙烯蜡、低密度聚乙烯、硬脂酸、偶联剂，混合均匀，在挤出机中熔融挤出，经过造粒而制成粒状母粒。
所述的挤出机的各区温度设为：55±5℃，80±5℃，95±3℃，120±2℃， 130±2℃，155±2℃，140±2℃，160±2℃，模头温度为165℃±1℃。
对比例1
将实施例1中的模板改性剂替换为未经静电吸附贴合的长度为0.5-1.2mm，宽度≤0.1mm的玻璃纤维棉和石墨烯薄膜丝状物(即制备过程中分别加入玻璃纤维棉丝状物和石墨烯薄膜丝状物)，其余配比和制备方法不变。
对比例2
将实施例1中的经过预处理的石墨烯薄膜替换为没有经过脉冲激光轰击的石墨烯薄膜，其余配比和制备方法不变。
以下对实施例1-3和对比例12制备的用于透明塑料填充的复合硫酸钡填充母料按照母料20份，高密度聚乙烯80份混合，在吹膜机上进行吹膜制备薄膜样品，样品厚度为0.020毫米。将制备的薄膜样品进行透光率和拉伸性能测试，母料样品进行熔融指数测试。结果如表1所示。
表1：本发明的复合硫酸钡填充母料及其薄膜样品的检测结果；
Figure PCTCN2021103453-appb-000001
备注：1、熔融指数按照GB/T36822000中规定的方法进行测定，其中，测试条件包括温度为190℃，载荷为2.16kg；2、薄膜透光率按GB/T2410-2008中规定的方法进行测定，采用透光率-雾度测定仪进行测定；3、薄膜纵向拉伸强 度按照GB/T1040.3-2006中规定的方法进行测定。
由以上测试数据可以知道，本发明的复合硫酸钡填充母料，应用于透明塑料薄膜后，不但具有良好的拉伸强度，而且具有非常好的透光率。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (8)

  1. 一种用于透明塑料填充的复合硫酸钡填充母料，其特征在于，由以下重量百分比的成分组成：硬脂酸1.4-2.0％，偶联剂1.2-1.8％，低密度聚乙烯8-20％，聚乙烯蜡1.8-2.8％，模板改性剂0.1-0.3％和硫酸钡余量。
  2. 如权利要求1所述的用于透明塑料填充的复合硫酸钡填充母料，其特征在于，所述的硫酸钡为平均粒径≤0.2μm，粉体白度≥98％的沉淀法生产的硫酸钡粉体。
  3. 如权利要求1所述的用于透明塑料填充的复合硫酸钡填充母料，其特征在于，所述的偶联剂为硅烷偶联剂或者铝酸酯偶联剂。
  4. 如权利要求1所述的用于透明塑料填充的复合硫酸钡填充母料，其特征在于，所述的模板改性剂为玻璃纤维棉和石墨烯薄膜的复合材料。
  5. 如权利要求1所述的用于透明塑料填充的复合硫酸钡填充母料，其特征在于，所述的模板改性剂的制备方法，包括以下步骤：
    A、将0.1-1μm直径的超细玻璃纤维在成型网上制成超细玻璃纤维棉；
    B、采用静电吸附的方式将与经过预处理的石墨烯薄膜通过静电吸附的方式贴合到超细玻璃纤维棉上，形成复合膜；
    C、将复合膜裁切成长度为0.5-1.2mm，宽度≤0.1mm的丝状物，即可。
  6. 如权利要求5所述的用于透明塑料填充的复合硫酸钡填充母料，其特征在于，所述的经过预处理的石墨烯薄膜的预处理方法为：用脉冲激光沿厚度方向轰击石墨烯薄膜。具体的参数为：激光波长532nm，能量200-300mJ，脉冲宽度4-6ns，聚焦束斑0.3-0.35mm，轰击频率为5-8Hz；多束激光在水平方向成线性排列，相邻激光束的间距相同，宽度≤0.05mm，宽度与处理的石墨烯薄膜相同；石墨烯薄膜沿垂直方向运动，运动速度为60-90m/s；石墨烯薄膜厚度为900-1000层。
  7. 如权利要求1-6任一所述的用于透明塑料填充的复合硫酸钡填充母料，其特征在于，其制备方法，包括以下步骤：把硫酸钡和模板改性剂加入到转速为800-1500r/min的高混机内高速搅拌并加热到120-130℃，依次加入聚乙烯蜡、低密度聚乙烯、硬脂酸、偶联剂，混合均匀，在挤出机中熔融挤出，经过造粒而制成粒状母粒。
  8. 如权利要求7所述的用于透明塑料填充的复合硫酸钡填充母料，其特征在于，所述的挤出机的各区温度设为：55±5℃，80±5℃，95±3℃，120±2℃，130±2℃，155±2℃，140±2℃，160±2℃，模头温度为165℃±1℃。
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