WO2022246778A1 - Preparation method for special nano-modified polyethylene material for resisting aging - Google Patents

Preparation method for special nano-modified polyethylene material for resisting aging Download PDF

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WO2022246778A1
WO2022246778A1 PCT/CN2021/096576 CN2021096576W WO2022246778A1 WO 2022246778 A1 WO2022246778 A1 WO 2022246778A1 CN 2021096576 W CN2021096576 W CN 2021096576W WO 2022246778 A1 WO2022246778 A1 WO 2022246778A1
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nano
parts
composite nano
oxide powder
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蒋妙根
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蒋妙根
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the invention relates to a preparation method of a polyethylene anti-aging special material, in particular to a preparation method of a nano-modified polyethylene anti-aging special material.
  • HDPE is a milky white translucent waxy solid. It is a non-polar thermoplastic resin with high crystallinity. Compared with LDPE and LLDPE, HDPE has the smallest degree of branching, tightly packed molecules, and the highest density (0.941 ⁇ 0.965gPcm3 ), high crystallinity. HDPE has high rigidity and toughness, good mechanical properties and high service temperature.
  • HDPE Compared with LDPE, it has higher temperature resistance, oil resistance, steam permeability resistance and environmental stress crack resistance, electrical insulation, impact resistance and cold resistance are very good.
  • HDPE is better than LDPE in terms of strength and stiffness, and its toughness is higher than PVC and LDPE.
  • HDPE has extremely small water absorption, non-toxicity, excellent chemical stability, and the film has low permeability to water vapor and air.
  • HDPE is currently the third largest polyolefin variety in the world in terms of production capacity and demand, and it is mainly used for film, blow molding, and pipes.
  • HDPE was discovered as early as 1953, its development and application are far from reaching a mature level, and it is difficult to meet the performance requirements of some engineering fields.
  • a lot of research has been done on the high performance of HDPE in China, but compared with the world's leading level, there is still a big gap.
  • more than half of the domestic demand for HDPE is met through imports.
  • the demand for polymer materials with improved performance has increased rapidly in various industries such as industry, agriculture and military. Therefore, it is of great practical significance to develop high-grade HDPE products that meet the demand in domestic technology and production to replace imported products.
  • Filling modification is to improve the mechanical properties and thermal properties of the polymer or reduce the cost of the material at the same time by adding one or several materials into the polymer material.
  • the main materials used for filling and modifying polymer materials are inorganic mineral fillers and fiber materials. Most inorganic mineral fillers can not only improve the physical and mechanical properties of the material but also greatly reduce the production cost of the material; some fiber-filled materials can improve the mechanical properties and thermal properties of the polymer matrix at the same time.
  • the main methods of filling modification are in-situ polymerization and melt blending. With the continuous development of polymer filling modification technology, there are more and more types of inorganic particles used for plastic filling modification, which are applied to polyethylene modification. The types of fillers are also increasing.
  • Inorganic fillers can be divided into oxides, hydroxides, silicates, carbonates, sulfates, etc. according to their chemical composition. Some filler materials also have special functions such as electrical conductivity, magnetism, and flame retardancy. When they are used to modify polymers, they can not only improve the mechanical and thermal properties of the matrix material, but also endow the material with some unique special functions.
  • polymer nanocomposite material The material obtained by compounding the dispersion system of nano-scale ultrafine dispersed phase and polymer matrix is called polymer nanocomposite material, and most of these materials are obtained by compounding polymer and inorganic phase. In the 21st century, nanocomposites will rapidly develop into one of the most advanced composite materials.
  • Nano-inorganic powder filled polymer materials can improve the rigidity, hardness and wear resistance of polymer materials, while ordinary inorganic powder fillers filled with polymer materials will reduce the strength and toughness of polymer materials while enhancing these properties . Due to the small particle size and large specific surface area, nano-inorganic powder has a strong bonding force with the matrix in polymer composite materials, which can not only improve the rigidity and hardness of the material, but also play a role in toughening. Evenly adding nanoparticles to plastics can achieve the purpose of comprehensively improving the properties of reinforced plastics (increasing strength and elongation, improving wear resistance and improving material surface roughness, and improving anti-aging performance).
  • inorganic nanomaterials such as nano-CaCO3, ZnO, SiO2, TiO2, clay and high-density polyethylene for nanocomposite can obtain mechanical properties such as high hardness, high modulus, high scratch resistance or good heat resistance, Nano-inorganic powder filled polymer material with low air permeability and UV absorption properties.
  • the above-mentioned nanopowders either cannot comprehensively improve the performance of the high-density polyethylene material or have a strong catalytic degradation effect on the polyethylene material.
  • the uniform dispersion of inorganic nanoparticles in organic polymer matrices is also an urgent problem to be solved.
  • the purpose of the invention is to comprehensively improve the physical and chemical properties of polyethylene materials by selecting suitable surface-modified composite nano-oxides on the basis of the main components of high-density polyethylene. While improving the strength, toughness and impact resistance of polyethylene materials, it can also improve the aging performance of materials.
  • the technical scheme of the present invention is as follows: a preparation method of nano-modified polyethylene anti-aging special material, comprising the following steps:
  • the antioxidant is selected from ⁇ -(4-hydroxyphenyl-3,5-di-tert-butyl) n-octadecyl propionate, tetrakis[ ⁇ -(3,5-di-tert-butyl-4- hydroxyphenyl)propionate]pentaerythritol ester or mixtures thereof.
  • the carrier gas in step a preferably an inert carrier gas such as nitrogen, argon, etc.
  • the composite nano-oxide powder of the present invention is coated with SiO2, which can effectively reduce the catalytic degradation effect of the nano-powder on polyethylene materials.
  • the surface of the composite nano-oxide powder is modified by grafting polyethylene terephthalate. properties, improving the dispersion of composite nano-oxide powder in organic polymer matrix.
  • the polyethylene anti-aging special material of the present invention is improved by surface-modified composite nano-oxide powder, and has good mechanical strength, processing performance and anti-aging performance.
  • the notched impact strength is as high as 41kJ/m2 and the unnotched impact strength is as high as 64kJ/m2. More than m2, after 200h of accelerated aging by ultraviolet light, the unnotched impact strength can still be maintained above 57kJ/m2, and after 700h exposure to ultraviolet light, the unnotched impact strength can still be maintained above 45kJ/m2.
  • the initial raw materials TiCl4, Zn3(C6H5O7)2 ⁇ 2H2O, Mg(NO3)2 ⁇ 6H2O are weighed according to the general formula Ti0.7Mg0.3Zn0.15O1.85; the antioxidant is ⁇ -(4-hydroxyphenyl-3,5 - n-octadecyl di-tert-butyl)propionate.
  • Process step is with embodiment 1.
  • the initial raw materials TiCl4, Zn3(C6H5O7)2 ⁇ 2H2O, Mg(NO3)2 ⁇ 6H2O are weighed according to the general formula Ti0.6Mg0.3Zn0.1O1.6; Butyl-4-hydroxyphenyl) propionate] pentaerythritol ester.
  • Process step is with embodiment 1.
  • the antioxidant is n-octadecyl ⁇ -(4-hydroxyphenyl-3,5-di-tert-butyl)propionate.
  • Process step is the same as embodiment 1 step d).
  • the antioxidant is n-octadecyl ⁇ -(4-hydroxyphenyl-3,5-di-tert-butyl)propionate.
  • Process step is the same as embodiment 1 step d).

Abstract

A preparation method for a special nano-modified polyethylene material for resisting aging, wherein composite nano oxide powder is coated with the SiO2, such that the catalytic degradation effect of the nano powder on the polyethylene material can be effectively reduced, and the surface of the composite nano oxide powder is grafted and modified by polyethylene terephthalate, thereby improving the dispersity of the composite nano oxide powder in an organic polymer matrix. The special nano-modified polyethylene material for resisting aging is improved by surface-modified composite nano-oxide powder, and has good mechanical strength, processing performance and anti-aging performance, the notched impact strength is as high as 41 kJ/m 2, and the unnotched impact strength is as high as 64 kJ/m2, after the special polyethylene material is subjected to accelerated aging at ultraviolet rays for 200 h, the unnotched impact strength can still be kept 57 kJ/m2 or above, and after the special polyethylene material is exposed in the ultraviolet rays for 700 h, the unnotched impact strength can still be kept 45 kJ/m2 or above.

Description

一种纳米改性聚乙烯抗老化专用料的制备方法Preparation method of nano-modified polyethylene anti-aging special material 技术领域technical field
本发明涉及一种聚乙烯抗老化专用料的制备方法，尤其涉及一种纳米改性聚乙烯抗老化专用料的制备方法。The invention relates to a preparation method of a polyethylene anti-aging special material, in particular to a preparation method of a nano-modified polyethylene anti-aging special material.
背景技术Background technique
自1953年Ziegler使用TiCl4和AlEt3在低压下使乙烯聚合生成HDPE,迄今已有50多年，高密度聚乙烯的开发生产不断取得创新，因其综合性能优良，原料来源丰富，成本较低而不断开发出新的用途和市场。HDPE呈乳白色半透明的蜡状固体，是一种结晶度高、非极性的热塑性树脂，与LDPE、LLDPE比较，HDPE支链化程度最小，分子能紧密地堆砌,密度最大(0.941～0.965gPcm3)，结晶度高。HDPE有较高的刚性及韧性，良好的力学性能及较高的使用温度。与LDPE比较，有较高的耐温、耐油性、耐蒸汽渗透性及抗环境应力开裂性，电绝缘性和抗冲击性及耐寒性都很好。HDPE在强度和劲度方面比LDPE好，韧性比PVC、LDPE高。HDPE吸水性极微小，无毒，化学稳定性及佳,薄膜对水蒸汽、空气的渗透性小。HDPE目前是世界生产能力和需求量位居第三大类的聚烯烃品种,其主要用于薄膜、吹塑、管材等。Since 1953, Ziegler used TiCl4 and AlEt3 to polymerize ethylene to produce HDPE under low pressure. It has been more than 50 years so far. The development and production of high-density polyethylene has been continuously innovated because of its excellent comprehensive performance, abundant raw material sources, and low cost. Continuous development new uses and markets. HDPE is a milky white translucent waxy solid. It is a non-polar thermoplastic resin with high crystallinity. Compared with LDPE and LLDPE, HDPE has the smallest degree of branching, tightly packed molecules, and the highest density (0.941～0.965gPcm3 ), high crystallinity. HDPE has high rigidity and toughness, good mechanical properties and high service temperature. Compared with LDPE, it has higher temperature resistance, oil resistance, steam permeability resistance and environmental stress crack resistance, electrical insulation, impact resistance and cold resistance are very good. HDPE is better than LDPE in terms of strength and stiffness, and its toughness is higher than PVC and LDPE. HDPE has extremely small water absorption, non-toxicity, excellent chemical stability, and the film has low permeability to water vapor and air. HDPE is currently the third largest polyolefin variety in the world in terms of production capacity and demand, and it is mainly used for film, blow molding, and pipes.
HDPE虽然早在1953年就已经发现，但在其开发与应用方面还远没有达到成熟水平，难以满足一些工程领域对其性能的需求。国内对HDPE的高性能化进行了大量的研究，但与世界领先水平相比，依然具有较大差距。目前，国内超过半数的HDPE需求要通过进口来满足。近年来，工业、农业及军事等各行业对经过性能改进的高分子材料需求迅速增加。因此，在国内技术和生产中开发出满足需求的高档次HDPE产品替代进口产品具有非常重要的现实意义。Although HDPE was discovered as early as 1953, its development and application are far from reaching a mature level, and it is difficult to meet the performance requirements of some engineering fields. A lot of research has been done on the high performance of HDPE in China, but compared with the world's leading level, there is still a big gap. At present, more than half of the domestic demand for HDPE is met through imports. In recent years, the demand for polymer materials with improved performance has increased rapidly in various industries such as industry, agriculture and military. Therefore, it is of great practical significance to develop high-grade HDPE products that meet the demand in domestic technology and production to replace imported products.
填充改性是通过将某种或几种材料加入聚合物材料中来改善改聚合物的机械性能和热性能或同时降低材料的成本。用于聚合物材料填充改性的主要有无机矿物填料和纤维材料等。大部分无机矿物填料既能够提高材料的物理机械性能又可以大幅度降低材料的生产成本；一些纤维填充材料可以同时提高聚合物基体的机械性能和热性能。填充改性的主要方法有原位聚合法和熔融共混法等随着聚合物填充改性技术的不断发展，用于塑料填充改性的无机粒子种类越来越多，应用于聚乙烯改性的填料种类也在不断增加。无机填料按化学组成可以分为氧化物、氢氧化物、硅酸盐、碳酸盐、硫酸盐等。某些填充材料还具有导电性、磁性、阻燃性等特殊功能，将其对聚合物进行填充改性时，不仅能够改善基体材料的机械性能与热性能还能赋予材料一些独特的特殊功 能。Filling modification is to improve the mechanical properties and thermal properties of the polymer or reduce the cost of the material at the same time by adding one or several materials into the polymer material. The main materials used for filling and modifying polymer materials are inorganic mineral fillers and fiber materials. Most inorganic mineral fillers can not only improve the physical and mechanical properties of the material but also greatly reduce the production cost of the material; some fiber-filled materials can improve the mechanical properties and thermal properties of the polymer matrix at the same time. The main methods of filling modification are in-situ polymerization and melt blending. With the continuous development of polymer filling modification technology, there are more and more types of inorganic particles used for plastic filling modification, which are applied to polyethylene modification. The types of fillers are also increasing. Inorganic fillers can be divided into oxides, hydroxides, silicates, carbonates, sulfates, etc. according to their chemical composition. Some filler materials also have special functions such as electrical conductivity, magnetism, and flame retardancy. When they are used to modify polymers, they can not only improve the mechanical and thermal properties of the matrix material, but also endow the material with some unique special functions.
纳米级超微细分散相的分散体系与聚合物基体复合所得到的材料称为聚合物纳米复合材料，这类材料大多是由聚合物和无机相进行复合而得到的。在21世纪，纳米复合材料将迅速发展成为最先进的复合材料之一。The material obtained by compounding the dispersion system of nano-scale ultrafine dispersed phase and polymer matrix is called polymer nanocomposite material, and most of these materials are obtained by compounding polymer and inorganic phase. In the 21st century, nanocomposites will rapidly develop into one of the most advanced composite materials.
纳米无机粉体填充聚合物材料可以提高聚合物材料的刚性、硬度和耐磨性等性能，而普通的无机粉体填料填充聚合物材料在增强这些性能的同时都会降低聚合物材料的强度和韧性。纳米无机粉体由于粒径小、比表面积大，在聚合物复合材料中，与基体间有很强的结合力，这不仅能提高材料的刚性和硬度，还可以起到增韧的效果。把纳米颗粒均匀地添加到塑料中可达到全面改善增强塑料性能(提高强度和延伸率、提高耐磨性和改善材料表面粗糙度、提高抗老化性能)的目的。Nano-inorganic powder filled polymer materials can improve the rigidity, hardness and wear resistance of polymer materials, while ordinary inorganic powder fillers filled with polymer materials will reduce the strength and toughness of polymer materials while enhancing these properties . Due to the small particle size and large specific surface area, nano-inorganic powder has a strong bonding force with the matrix in polymer composite materials, which can not only improve the rigidity and hardness of the material, but also play a role in toughening. Evenly adding nanoparticles to plastics can achieve the purpose of comprehensively improving the properties of reinforced plastics (increasing strength and elongation, improving wear resistance and improving material surface roughness, and improving anti-aging performance).
已知利用无机纳米材料如纳米CaCO3、ZnO、SiO2、TiO2、粘土与高密度聚乙烯进行纳米复合可以获得具有高硬度、高模量、高耐划痕等机械性能或具有良好的耐热性能、低透气性、对紫外光的吸收性能的纳米无机粉体填充聚合物材料。但上述纳米粉体或者不能全面提升高密度聚乙烯材料的性能或者对聚乙烯材料具有很强的催化降解作用。此外，无机纳米颗粒在有机聚合物基体中的均匀分散也是亟需解决的问题。It is known that the use of inorganic nanomaterials such as nano-CaCO3, ZnO, SiO2, TiO2, clay and high-density polyethylene for nanocomposite can obtain mechanical properties such as high hardness, high modulus, high scratch resistance or good heat resistance, Nano-inorganic powder filled polymer material with low air permeability and UV absorption properties. However, the above-mentioned nanopowders either cannot comprehensively improve the performance of the high-density polyethylene material or have a strong catalytic degradation effect on the polyethylene material. In addition, the uniform dispersion of inorganic nanoparticles in organic polymer matrices is also an urgent problem to be solved.
发明内容Contents of the invention
本发明的目的是在高密度聚乙烯主要成分的基础上，通过选择合适的经过表面改性的复合纳米氧化物对聚乙烯材料的物理、化学性能进行综合改进。在提高聚乙烯材料材料强度、韧性、抗冲击性能的同时，改进材料的老化性能。The purpose of the invention is to comprehensively improve the physical and chemical properties of polyethylene materials by selecting suitable surface-modified composite nano-oxides on the basis of the main components of high-density polyethylene. While improving the strength, toughness and impact resistance of polyethylene materials, it can also improve the aging performance of materials.
本发明的技术方案如下：一种纳米改性聚乙烯抗老化专用料的制备方法，包括如下步骤：The technical scheme of the present invention is as follows: a preparation method of nano-modified polyethylene anti-aging special material, comprising the following steps:
a)采用TiCl4、Zn3(C6H5O7)2·2H2O、Mg(NO3)2·6H2O作为初始原料，按照通式TiaMgbZncOX称量，其中a＝0.6-0.7，b＝0.2-0.3，c＝0.1-0.15，X≥1.5；将TiCl4、Zn3(C6H5O7)2·2H2O、Mg(NO3)2·6H2O混合，加入去离子水配成溶液，溶液中金属离子的浓度为0.60-0.70mol/L；将上述溶液雾化为10微米粒径的液滴，在35-40L/min的载气流量下导入反应室中；采用500～700℃温度下脉动流加热的方法，在反应室中对雾化溶液进行热处理，脉冲频率60～130Hz；获得复合纳米氧化物粉体；a) TiCl4, Zn3(C6H5O7)2.2H2O, Mg(NO3)2.6H2O are used as initial raw materials, weighed according to the general formula TiaMgbZncOX, wherein a=0.6-0.7, b=0.2-0.3, c=0.1-0.15, X≥1.5; mix TiCl4, Zn3(C6H5O7)2 2H2O, Mg(NO3)2 6H2O, add deionized water to make a solution, the concentration of metal ions in the solution is 0.60-0.70mol/L; spray the above solution Turn into droplets with a particle size of 10 microns, and introduce them into the reaction chamber at a carrier gas flow rate of 35-40L/min; adopt the method of pulsating flow heating at a temperature of 500-700°C, and heat-treat the atomized solution in the reaction chamber. Pulse frequency 60~130Hz; obtain composite nano-oxide powder;
b)将5wt％复合纳米氧化物去离子水浆液超声分散30min，在搅拌下滴加0.05mol/L的Na2SiO3溶液，调节浆液的pH值至9.3，控制摩尔比SiO2/复合纳米氧化物＝1/1，用稀硫酸调节浆液的pH值至8.5，反应2.5h，过滤、干燥，获得SiO2包覆的复合纳米氧化物粉体；b) ultrasonically disperse 5 wt % composite nano oxide deionized water slurry for 30 min, add 0.05 mol/L Na2SiO3 solution dropwise under stirring, adjust the pH value of the slurry to 9.3, and control the molar ratio SiO2/composite nano oxide=1/ 1. Adjust the pH value of the slurry to 8.5 with dilute sulfuric acid, react for 2.5 hours, filter, and dry to obtain SiO2-coated composite nano-oxide powder;
c)按摩尔比为3：1：2.4称取SiO2包覆的复合纳米氧化物粉体、对苯二甲酸二甲酯和乙二醇；混合后加热至140℃，加入0.1摩尔％的醋酸镉作为催化剂，磁力搅拌，然后升温至200℃，反 应1h，再升温至220℃，反应1h；缓慢升温至270℃，同时抽真空，在真空状态下反应1h；用苯酚对反应产物进行洗涤，离心分离，80℃真空干燥6h，即得到表面改性的复合纳米氧化物粉体；c) Weigh SiO2-coated composite nano-oxide powder, dimethyl terephthalate and ethylene glycol at a molar ratio of 3:1:2.4; mix and heat to 140°C, add 0.1 mol% cadmium acetate As a catalyst, stir magnetically, then raise the temperature to 200°C, react for 1h, then raise the temperature to 220°C, react for 1h; slowly raise the temperature to 270°C, and vacuumize at the same time, and react in a vacuum state for 1h; wash the reaction product with phenol, centrifuge Separation and vacuum drying at 80°C for 6 hours to obtain a surface-modified composite nano-oxide powder;
d)按重量份称取高密度聚乙烯100～120份、乙丙橡胶15～30份、表面改性的复合纳米氧化物粉体5-15份、乙撑双硬脂酰胺8～14份、氯化聚乙烯0.5～0.9份、抗氧剂0.2-0.6份，然后投至混合器中混合10-40分钟；将混合好的物料投置于双螺杆挤出机中，熔融挤出，制得纳米改性聚乙烯抗老化专用料。d) Weigh 100-120 parts of high-density polyethylene, 15-30 parts of ethylene-propylene rubber, 5-15 parts of surface-modified composite nano-oxide powder, 8-14 parts of ethylene bisstearamide, 0.5-0.9 parts of chlorinated polyethylene, 0.2-0.6 parts of antioxidant, and then put them into a mixer and mix for 10-40 minutes; put the mixed materials into a twin-screw extruder, and melt and extrude them to obtain Nano-modified polyethylene anti-aging special material.
所述抗氧剂选自β-(4-羟基苯基-3，5-二叔丁基)丙酸正十八碳醇酯、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯或者它们的混合物。The antioxidant is selected from β-(4-hydroxyphenyl-3,5-di-tert-butyl) n-octadecyl propionate, tetrakis[β-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate]pentaerythritol ester or mixtures thereof.
步骤a)中的载气，优选惰性载气如氮气、氩气等。The carrier gas in step a), preferably an inert carrier gas such as nitrogen, argon, etc.
本发明复合纳米氧化物粉体经SiO2包覆，可以有效降低纳米粉体对聚乙烯材料的催化降解作用，同时，复合纳米氧化物粉体表面经聚对苯二甲酸乙二醇酯接枝改性，改善了复合纳米氧化物粉体在有机聚合物基体中的分散性。The composite nano-oxide powder of the present invention is coated with SiO2, which can effectively reduce the catalytic degradation effect of the nano-powder on polyethylene materials. At the same time, the surface of the composite nano-oxide powder is modified by grafting polyethylene terephthalate. properties, improving the dispersion of composite nano-oxide powder in organic polymer matrix.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明聚乙烯抗老化专用料经表面改性的复合纳米氧化物粉体改进，具有良好的机械强度、加工性能和抗老化性能，缺口冲击强度高达41kJ/m2以上，无缺口冲击强度高达64kJ/m2以上，经过200h紫外光线加速老化后，无缺口抗冲击强度依然能保持在57kJ/m2以上，在紫外光线中暴露700h后，无缺口抗冲击强度依然能保持在45kJ/m2以上。The polyethylene anti-aging special material of the present invention is improved by surface-modified composite nano-oxide powder, and has good mechanical strength, processing performance and anti-aging performance. The notched impact strength is as high as 41kJ/m2 and the unnotched impact strength is as high as 64kJ/m2. More than m2, after 200h of accelerated aging by ultraviolet light, the unnotched impact strength can still be maintained above 57kJ/m2, and after 700h exposure to ultraviolet light, the unnotched impact strength can still be maintained above 45kJ/m2.
具体实施方式Detailed ways
下面结合是实施例对本发明作进一步说明。Below in conjunction with embodiment the present invention is further described.
实施例1Example 1
a)采用TiCl4、Zn3(C6H5O7)2·2H2O、Mg(NO3)2·6H2O作为初始原料，按照通式Ti0.6Mg0.2Zn0.1O1.5称量；将TiCl4、Zn3(C6H5O7)2·2H2O、Mg(NO3)2·6H2O混合，加入去离子水配成溶液，溶液中金属离子的浓度为0.60-0.70mol/L；将上述溶液雾化为10微米粒径的液滴，在35-40L/min的载气流量下导入反应室中；采用500～700℃温度下脉动流加热的方法，在反应室中对雾化溶液进行热处理，脉冲频率60～130Hz；获得复合纳米氧化物粉体；a) Using TiCl4, Zn3(C6H5O7)2·2H2O, Mg(NO3)2·6H2O as initial raw materials, weighing according to the general formula Ti0.6Mg0.2Zn0.1O1.5; TiCl4, Zn3(C6H5O7)2·2H2O, Mix Mg(NO3)2·6H2O, add deionized water to form a solution, the concentration of metal ions in the solution is 0.60-0.70mol/L; atomize the above solution into droplets with a particle size of 10 microns, at 35-40L/ The carrier gas flow rate of min is introduced into the reaction chamber; the atomized solution is heat-treated in the reaction chamber by means of pulsating flow heating at a temperature of 500-700 °C, and the pulse frequency is 60-130 Hz; composite nano-oxide powder is obtained;
b)将5wt％复合纳米氧化物去离子水浆液超声分散30min，在搅拌下滴加0.05mol/L的Na2SiO3溶液，调节浆液的pH值至9.3，控制摩尔比SiO2/复合纳米氧化物＝1/1，用稀硫酸调节浆液的pH值至8.5，反应2.5h，过滤、干燥，获得SiO2包覆的复合纳米氧化物粉体；b) ultrasonically disperse 5 wt % composite nano oxide deionized water slurry for 30 min, add 0.05 mol/L Na2SiO3 solution dropwise under stirring, adjust the pH value of the slurry to 9.3, and control the molar ratio SiO2/composite nano oxide=1/ 1. Adjust the pH value of the slurry to 8.5 with dilute sulfuric acid, react for 2.5 hours, filter, and dry to obtain SiO2-coated composite nano-oxide powder;
c)按摩尔比为3：1：2.4称取SiO2包覆的复合纳米氧化物粉体、对苯二甲酸二甲酯和乙二醇； 混合后加热至140℃，加入0.1摩尔％的醋酸镉作为催化剂，磁力搅拌，然后升温至200℃，反应1h，再升温至220℃，反应1h；缓慢升温至270℃，同时抽真空，在真空状态下反应1h；用苯酚对反应产物进行洗涤，离心分离，80℃真空干燥6h，即得到表面改性的复合纳米氧化物粉体；c) Weigh the SiO2-coated composite nano-oxide powder, dimethyl terephthalate and ethylene glycol at a molar ratio of 3:1:2.4; mix and heat to 140°C, add 0.1 mol% cadmium acetate As a catalyst, stir magnetically, then raise the temperature to 200°C, react for 1h, then raise the temperature to 220°C, react for 1h; slowly raise the temperature to 270°C, and vacuumize at the same time, and react in a vacuum state for 1h; wash the reaction product with phenol, centrifuge Separation and vacuum drying at 80°C for 6 hours to obtain a surface-modified composite nano-oxide powder;
d)按重量份称取高密度聚乙烯100份、乙丙橡胶15份、表面改性的复合纳米氧化物粉体5份、乙撑双硬脂酰胺9份、氯化聚乙烯0.5份、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯0.2份，然后投至混合器中混合10-40分钟；将混合好的物料投置于双螺杆挤出机中，熔融挤出，制得纳米改性聚乙烯抗老化专用料。d) Weigh 100 parts of high-density polyethylene, 15 parts of ethylene-propylene rubber, 5 parts of surface-modified composite nano-oxide powder, 9 parts of ethylene bisstearamide, 0.5 part of chlorinated polyethylene, and four parts by weight. [β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] 0.2 parts of pentaerythritol ester, then put it into the mixer and mix it for 10-40 minutes; put the mixed material into the twin-screw extruder In the machine, it is melted and extruded to obtain a nano-modified polyethylene anti-aging special material.
实施例2Example 2
高密度聚乙烯115份，乙丙橡胶25份，表面改性的复合纳米氧化物粉体10份，乙撑双硬脂酰胺11份，氯化聚乙烯0.8份，抗氧剂0.4份。115 parts of high-density polyethylene, 25 parts of ethylene-propylene rubber, 10 parts of surface-modified composite nano-oxide powder, 11 parts of ethylene bis-stearamide, 0.8 parts of chlorinated polyethylene, and 0.4 parts of antioxidant.
初始原料TiCl4、Zn3(C6H5O7)2·2H2O、Mg(NO3)2·6H2O按通式Ti0.7Mg0.3Zn0.15O1.85称量；抗氧剂为β-(4-羟基苯基-3，5-二叔丁基)丙酸正十八碳醇酯。The initial raw materials TiCl4, Zn3(C6H5O7)2·2H2O, Mg(NO3)2·6H2O are weighed according to the general formula Ti0.7Mg0.3Zn0.15O1.85; the antioxidant is β-(4-hydroxyphenyl-3,5 - n-octadecyl di-tert-butyl)propionate.
工艺步骤同实施例1。Process step is with embodiment 1.
实施例3Example 3
高密度聚乙烯120份，乙丙橡胶25份，表面改性的复合纳米氧化物粉体15份，乙撑双硬脂酰胺12份，氯化聚乙烯0.9份，抗氧剂0.6份。120 parts of high-density polyethylene, 25 parts of ethylene-propylene rubber, 15 parts of surface-modified composite nano-oxide powder, 12 parts of ethylene bis-stearamide, 0.9 part of chlorinated polyethylene, and 0.6 part of antioxidant.
初始原料TiCl4、Zn3(C6H5O7)2·2H2O、Mg(NO3)2·6H2O按通式Ti0.6Mg0.3Zn0.1O1.6称量；抗氧剂选自四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯。The initial raw materials TiCl4, Zn3(C6H5O7)2·2H2O, Mg(NO3)2·6H2O are weighed according to the general formula Ti0.6Mg0.3Zn0.1O1.6; Butyl-4-hydroxyphenyl) propionate] pentaerythritol ester.
工艺步骤同实施例1。Process step is with embodiment 1.
比较例1Comparative example 1
高密度聚乙烯100份，乙丙橡胶15份，纳米二氧化钛2份，纳米氧化镁2份，纳米二氧化硅1份，乙撑双硬脂酰胺9份，氯化聚乙烯0.5份，抗氧剂0.2份。100 parts of high-density polyethylene, 15 parts of ethylene-propylene rubber, 2 parts of nano-titanium dioxide, 2 parts of nano-magnesia, 1 part of nano-silica, 9 parts of ethylene bis-stearamide, 0.5 parts of chlorinated polyethylene, antioxidant 0.2 parts.
抗氧剂为β-(4-羟基苯基-3，5-二叔丁基)丙酸正十八碳醇酯。The antioxidant is n-octadecyl β-(4-hydroxyphenyl-3,5-di-tert-butyl)propionate.
工艺步骤同实施例1步骤d)。Process step is the same as embodiment 1 step d).
比较例2Comparative example 2
高密度聚乙烯115份，乙丙橡胶25份，纳米二氧化钛5份，纳米氧化镁3份，纳米二氧化硅2份，乙撑双硬脂酰胺11份，氯化聚乙烯0.8份，抗氧剂0.4份。115 parts of high-density polyethylene, 25 parts of ethylene-propylene rubber, 5 parts of nano-titanium dioxide, 3 parts of nano-magnesium oxide, 2 parts of nano-silica, 11 parts of ethylene bis-stearamide, 0.8 parts of chlorinated polyethylene, antioxidant 0.4 parts.
抗氧剂为β-(4-羟基苯基-3，5-二叔丁基)丙酸正十八碳醇酯。The antioxidant is n-octadecyl β-(4-hydroxyphenyl-3,5-di-tert-butyl)propionate.
工艺步骤同实施例1步骤d)。Process step is the same as embodiment 1 step d).
上述实施例、比较例性能测试结果：Above-mentioned embodiment, comparative example performance test result:
注：各测试项目均按相关国家标准进行Note: All test items are carried out in accordance with relevant national standards
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (3)

  1. 一种纳米改性聚乙烯抗老化专用料的制备方法，包括如下步骤：A preparation method of nano-modified polyethylene anti-aging special material, comprising the steps of:
    a)采用TiCl4、Zn3(C6H5O7)2·2H2O、Mg(NO3)2·6H2O作为初始原料，按照通式TiaMgbZncOX称量，其中a＝0.6-0.7，b＝0.2-0.3，c＝0.1-0.15，X≥1.5；将TiCl4、Zn3(C6H5O7)2·2H2O、Mg(NO3)2·6H2O混合，加入去离子水配成溶液，溶液中金属离子的浓度为0.60-0.70mol/L；将上述溶液雾化为10微米粒径的液滴，在35-40L/min的载气流量下导入反应室中；采用500～700℃温度下脉动流加热的方法，在反应室中对雾化溶液进行热处理，脉冲频率60～130Hz；获得复合纳米氧化物粉体；a) TiCl4, Zn3(C6H5O7)2.2H2O, Mg(NO3)2.6H2O are used as initial raw materials, weighed according to the general formula TiaMgbZncOX, wherein a=0.6-0.7, b=0.2-0.3, c=0.1-0.15, X≥1.5; mix TiCl4, Zn3(C6H5O7)2 2H2O, Mg(NO3)2 6H2O, add deionized water to make a solution, the concentration of metal ions in the solution is 0.60-0.70mol/L; spray the above solution Turn into droplets with a particle size of 10 microns, and introduce them into the reaction chamber at a carrier gas flow rate of 35-40L/min; adopt the method of pulsating flow heating at a temperature of 500-700°C, and heat-treat the atomized solution in the reaction chamber. Pulse frequency 60~130Hz; obtain composite nano-oxide powder;
    b)将5wt％复合纳米氧化物去离子水浆液超声分散30min，在搅拌下滴加0.05mol/L的Na2SiO3溶液，调节浆液的pH值至9.3，控制摩尔比SiO2/复合纳米氧化物＝1/1，用稀硫酸调节浆液的pH值至8.5，反应2.5h，过滤、干燥，获得SiO2包覆的复合纳米氧化物粉体；b) ultrasonically disperse 5 wt % composite nano oxide deionized water slurry for 30 min, add 0.05 mol/L Na2SiO3 solution dropwise under stirring, adjust the pH value of the slurry to 9.3, and control the molar ratio SiO2/composite nano oxide=1/ 1. Adjust the pH value of the slurry to 8.5 with dilute sulfuric acid, react for 2.5 hours, filter, and dry to obtain SiO2-coated composite nano-oxide powder;
    c)按摩尔比为3：1：2.4称取SiO2包覆的复合纳米氧化物粉体、对苯二甲酸二甲酯和乙二醇；混合后加热至140℃，加入0.1摩尔％的醋酸镉作为催化剂，磁力搅拌，然后升温至200℃，反应1h，再升温至220℃，反应1h；缓慢升温至270℃，同时抽真空，在真空状态下反应1h；用苯酚对反应产物进行洗涤，离心分离，80℃真空干燥6h，即得到表面改性的复合纳米氧化物粉体；c) Weigh SiO2-coated composite nano-oxide powder, dimethyl terephthalate and ethylene glycol at a molar ratio of 3:1:2.4; mix and heat to 140°C, add 0.1 mol% cadmium acetate As a catalyst, stir magnetically, then raise the temperature to 200°C, react for 1h, then raise the temperature to 220°C, react for 1h; slowly raise the temperature to 270°C, and vacuumize at the same time, and react in a vacuum state for 1h; wash the reaction product with phenol, centrifuge Separation and vacuum drying at 80°C for 6 hours to obtain a surface-modified composite nano-oxide powder;
    d)按重量份称取高密度聚乙烯100～120份、乙丙橡胶15～30份、表面改性的复合纳米氧化物粉体5-15份、乙撑双硬脂酰胺8～14份、氯化聚乙烯0.5～0.9份、抗氧剂0.2-0.6份，然后投至混合器中混合10-40分钟；将混合好的物料投置于双螺杆挤出机中，熔融挤出，制得纳米改性聚乙烯抗老化专用料。d) Weigh 100-120 parts of high-density polyethylene, 15-30 parts of ethylene-propylene rubber, 5-15 parts of surface-modified composite nano-oxide powder, 8-14 parts of ethylene bisstearamide, 0.5-0.9 parts of chlorinated polyethylene, 0.2-0.6 parts of antioxidant, and then put them into a mixer and mix for 10-40 minutes; put the mixed materials into a twin-screw extruder, and melt and extrude them to obtain Nano-modified polyethylene anti-aging special material.
  2. 如权利要求1所述的纳米改性聚乙烯抗老化专用料的制备方法，其特征在于：步骤d)中的抗氧剂选自β-(4-羟基苯基-3，5-二叔丁基)丙酸正十八碳醇酯、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯或者它们的混合物。The preparation method of nano-modified polyethylene anti-aging special material as claimed in claim 1, characterized in that: the antioxidant in step d) is selected from β-(4-hydroxyphenyl-3,5-di-tert-butyl base) n-octadecyl propionate, tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol or a mixture thereof.
  3. 如权利要求1所述的纳米改性聚乙烯抗老化专用料的制备方法，其特征在于：步骤a)中的载气选自氮气、氩气。The preparation method of nano-modified polyethylene anti-aging special material according to claim 1, characterized in that: the carrier gas in step a) is selected from nitrogen and argon.
PCT/CN2021/096576 2021-05-28 2021-05-28 Preparation method for special nano-modified polyethylene material for resisting aging WO2022246778A1 (en)

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