WO2020056950A1 - 提高聚烯烃热变形温度的方法及由其得到的聚烯烃复合材料和应用 - Google Patents

提高聚烯烃热变形温度的方法及由其得到的聚烯烃复合材料和应用 Download PDF

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WO2020056950A1
WO2020056950A1 PCT/CN2018/121404 CN2018121404W WO2020056950A1 WO 2020056950 A1 WO2020056950 A1 WO 2020056950A1 CN 2018121404 W CN2018121404 W CN 2018121404W WO 2020056950 A1 WO2020056950 A1 WO 2020056950A1
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polyolefin
hydrogen phosphate
zirconium hydrogen
polar
composite material
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French (fr)
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孙大陟
李涛
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Southern University of Science and Technology
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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
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Definitions

  • the present application belongs to the technical field of modification, and relates to a method for increasing the thermal deformation temperature of polyolefin, and a polyolefin composite material and application obtained by the method.
  • Polyolefins are polymerized or co-polymerized by ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene and some cyclic olefins.
  • ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene and some cyclic olefins.
  • ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene and some cyclic olefins.
  • PE polyethylene
  • PP polymer Propylene
  • CN105440547A discloses a high-strength heat-resistant polyethylene pipe whose raw materials include the following components by weight parts: 50-75 parts of vinyl silane grafted high-density polyethylene, linear low-density polymer 10-25 parts of ethylene, 5-15 parts of titanium-containing silicone resin, 5-12 parts of maleic anhydride grafted polyphenylene ether, 2-12 parts of polyphenyl diphenylsulfone ester, and t-butanol peroxide 0.2-1 Parts, 2-10 parts of ferric tetroxide, 2-5 parts of barium sulfate, 1-5 parts of aluminum hydroxide, 5-15 parts of modified nano titanium dioxide, 2-5 parts of calcium silicate whiskers, and
  • CN106146756A discloses a simple graphene-grafted polyolefin method, in which a modified graphene oxide is used to modify the polyolefin so that it has a functional group, which can be well applied.
  • the modification method is too complicated. Not suitable for large-scale industrial production.
  • nanomaterials can significantly improve the properties of polymers, which has also become a current research hotspot.
  • Commonly used inorganic nano fillers are represented by montmorillonite (MMT), as additives to polymer materials, widely used in polymer materials industry; one-dimensional materials represented by carbon nanotubes and two-dimensional materials represented by graphene
  • MMT montmorillonite
  • the dimensional nanomaterials also have good applications in reinforcing resins, but because of the absence of polar groups and the lack of functional groups in non-polar polyolefins, the inorganic nanofillers represented by montmorillonite are not very good. Dispersed in polyolefin materials, and has little effect on the improvement of polyolefin heat resistance. The same problem exists for carbon nanotubes and graphene. Since non-polar polyolefin materials do not contain polar groups, nano fillers The dispersibility in the matrix is not good, and it does little to improve its heat resistance.
  • the purpose of the present application is to provide a method for increasing the thermal deformation temperature of polyolefin, and a polyolefin composite material and application obtained by the method.
  • the present application provides a method for increasing the thermal deformation temperature of a non-polar polyolefin, using zirconium hydrogen phosphate to increase the thermal deformation temperature of a non-polar polyolefin.
  • non-polar polyolefins do not contain polar groups
  • nano-fillers that can improve the heat resistance of polymers will have an agglomeration effect in the resin matrix, causing stress concentration or defects in the matrix.
  • the effect or effect of improving the heat resistance performance in the matrix is extremely insignificant.
  • the present application finds that the addition of zirconium hydrogen phosphate, which is more uniform in size, more complete in crystal form, and larger in aspect ratio, to non-polar polyolefins significantly increases its heat distortion temperature and heat resistance.
  • the non-polar polyolefin is a linear low density polyethylene, a high density polyethylene, or a polypropylene.
  • non-polar polyolefin linear low density polyethylene (LLDPE), high density polyethylene (HDPE) or polypropylene (PP)
  • LLDPE linear low density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • the method includes blending zirconium hydrogen phosphate with a polyolefin.
  • the present application provides a polyolefin composite including a non-polar polyolefin and zirconium hydrogen phosphate.
  • zirconium hydrogen phosphate is used as a heat resistance enhancer.
  • the present application provides a polyolefin composite material with a high thermal deformation temperature.
  • the zirconium hydrogen phosphate has a significant improvement in heat resistance of non-polar polyolefin.
  • the mass ratio of the non-polar polyolefin and zirconium hydrogen phosphate is (20-50): 1, for example, 25: 1, 30: 1, 35: 1, 40: 1, 45: 1, and the like.
  • the non-polar polyolefin is a linear low density polyethylene, a high density polyethylene, or a polypropylene.
  • the thermal deformation temperature of the polyolefin composite material provided in this application is 18-50% higher than the thermal deformation temperature of the corresponding polyolefin.
  • the mass ratio of zirconium hydrogen phosphate to polyolefin is 1:20
  • the thermal deformation temperature of the polyolefin composite is 26-50% higher than that of pure LLDPE
  • the thermal deformation temperature of the polyolefin composite is 20-23% higher than that of pure HDPE.
  • the non-polar polyolefin is PP
  • the thermal deformation temperature of the polyolefin composite is higher than that of pure HDPE.
  • the heat distortion temperature of PP is 18-20% higher.
  • Dynamic thermal mechanical analysis was used to test its thermal deformation temperature.
  • the mass ratio of zirconium hydrogen phosphate to polyolefin was 1:10, and when the non-polar polyolefin was LLDPE, the heat of the polyolefin composite at 1.82 MPa
  • the deformation temperature is 17 ° C higher than that of pure LLDPE, and the thermal deformation temperature of LLDPE is increased by 50%.
  • the thermal deformation temperature at 0.45MPa is 16 ° C higher than that of pure LLDPE, and the thermal deformation temperature of LLDPE is increased by 27.6%.
  • the thermal deformation temperature of the polyolefin composite at 1.82 MPa is 10 ° C higher than that of pure HDPE, and the thermal deformation temperature of HDPE increases by 22.2%; the thermal deformation temperature at 0.45 MPa is higher than that of pure HDPE.
  • the HDPE is 13 ° C higher and the heat distortion temperature of HDPE increases by 20%.
  • the thermal deformation temperature of the polyolefin composite at 1.82 MPa is 13 ° C higher than that of pure PP.
  • the thermal deformation temperature of PP increases by 18.6%, and the thermal deformation temperature at 0.45 MPa is higher than that of pure PP.
  • the PP was 16 ° C higher, and the heat distortion temperature of PP increased by 18.8%.
  • the zirconium hydrogen phosphate is ⁇ -zirconium hydrogen phosphate.
  • the diameter of the zirconium hydrogen phosphate is 2-10 ⁇ m, for example, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, and the like.
  • the polyolefin composite material further includes graphene.
  • the mass ratio of the graphene to the polyolefin is 1: (100-500), such as 1: 200, 1: 300, 1: 400, and the like.
  • zirconium hydrogen phosphate nanosheets have a large surface area, there are more hydroxyl groups (electron-donating groups), and they can interact with large ⁇ bonds of graphene, so that graphene sheets can be improved in non-polar polyolefin substrates. Dispersion.
  • the present application provides a method for preparing a polyolefin composite material as described in the second aspect, which comprises: blending a non-polar polyolefin, zirconium hydrogen phosphate, and optionally graphene, and then injection molding Molding to obtain the polyolefin composite material.
  • the injection temperature is 160-180 ° C, such as 165 ° C, 170 ° C, 175 ° C, and the like.
  • the injection pressure is 580-600 bar, such as 585 bar, 590 bar, 595 bar, and the like.
  • the injection time is 2-8s, such as 3s, 4s, 5s, 6s, 7s, and the like.
  • the temperature of the mold for injection molding is 60-70 ° C, such as 62 ° C, 65 ° C, 68 ° C, and the like.
  • the present application provides the application of the polyolefin composite material according to the second aspect in automotive plastics.
  • PE polystyrene
  • PP composite materials are used in automotive plastics, such as automotive roof sandwiches, automotive fuel tanks, and engine intake ducts. While improving the safety performance of automobiles, they can replace metal parts to reduce the weight of the entire vehicle and save production cost.
  • non-polar polyolefins do not contain polar groups, conventional fillers that can improve the heat resistance of polymers cannot exhibit their effects of improving heat resistance in non-polar polyolefin matrices, or their effects are extremely low. obvious.
  • zirconium hydrogen phosphate can also increase the dispersibility of graphene in a non-polar polyolefin matrix
  • the thermal deformation temperature of the polyolefin composite material provided in this application is 18-50% higher than the thermal deformation temperature of the corresponding polyolefin.
  • the thermal deformation temperature of the polyolefin composite is 26-50% higher than that of LLDPE;
  • the thermal deformation temperature of the polyolefin composite is higher than HDPE
  • the heat distortion temperature is 20-23% higher;
  • the non-polar polyolefin is PP, the heat distortion temperature of the polyolefin composite is 18-20% higher than the heat distortion temperature of PP.
  • graphene is added to the matrix, the thermal deformation temperature of the finally obtained polyolefin composite is higher.
  • FIG. 1 is a SEM image of a polyolefin composite material provided in Example 1 of the present application.
  • FIG. 2 is a SEM image of the polyolefin composite material provided in Example 2 of the present application.
  • FIG. 3 is a SEM image of the polyolefin composite material provided in Example 3 of the present application.
  • FIG. 4 is a SEM image of the polyolefin composite material provided in Example 4 of the present application.
  • FIG. 5 is a SEM image of the polyolefin composite material provided in Example 5 of the present application.
  • FIG. 6 is a SEM image of the polyolefin composite material provided in Example 6 of the present application.
  • FIG. 7 is a SEM image of the polyolefin composite material provided in Comparative Example 7 of the present application.
  • the ruler with a scale is 10 ⁇ m.
  • a polyolefin composite material is composed of LLDPE and zirconium hydrogen phosphate, wherein the mass ratio of LLDPE and zirconium hydrogen phosphate is 20: 1.
  • the preparation method is: blending LLDPE and zirconium hydrogen phosphate, and then injection molding;
  • the injection conditions are: injection temperature of 165 ° C, injection pressure of 580bar, injection time of 2s, mold temperature of 60 ° C, and dwell time of 10s.
  • Embodiment 1 The difference from Embodiment 1 is only that in this embodiment, LLDPE is replaced with HDPE (Embodiment 2) and PP (Embodiment 3).
  • Embodiment 1 The difference from Embodiment 1 is only that in this embodiment, graphene is also included, and the mass ratio of graphene to polyolefin is 1: 100.
  • Embodiment 2 The difference from Embodiment 2 is only that in this embodiment, graphene is also included, and the mass ratio of graphene to polyolefin is 1: 500.
  • Embodiment 3 The difference from Embodiment 3 is only that in this embodiment, graphene is also included, and the mass ratio of graphene to polyolefin is 1: 300.
  • a polyolefin composite material is composed of LLDPE and zirconium hydrogen phosphate, wherein the mass ratio of LLDPE and zirconium hydrogen phosphate is 50: 1.
  • the preparation method is: blending LLDPE and zirconium hydrogen phosphate, and then injection molding;
  • the injection conditions are: injection temperature of 170 ° C, injection pressure of 590bar, injection time of 4s, mold temperature of 70 ° C, and dwell time of 10s.
  • a polyolefin composite material is composed of HDPE and zirconium hydrogen phosphate, wherein the mass ratio of HDPE and zirconium hydrogen phosphate is 35: 1.
  • the preparation method is: blending HDPE and zirconium hydrogen phosphate, and then injection molding;
  • the injection conditions are: injection temperature of 180 ° C, injection pressure of 600 bar, injection time of 8s, mold temperature of 65 ° C, and dwell time of 10s.
  • a polyolefin is LLDPE (Comparative Example 1), HDPE (Comparative Example 2), and PP (Comparative Example 3) in the examples.
  • Example 1 The only difference from Example 1 is that the zirconium hydrogen phosphate was replaced with an equivalent amount of montmorillonite.
  • Example 2 The only difference from Example 2 is that zirconium hydrogen phosphate was replaced with an equivalent amount of nano-silica.
  • Example 3 The only difference from Example 3 is that zirconium hydrogen phosphate was replaced with an equivalent amount of nano-carbon fiber.
  • Example 4 The difference from Example 4 is only that zirconium hydrogen phosphate is not included in this comparative example.
  • Example 5 The difference from Example 5 is only that zirconium hydrogen phosphate is not included in this comparative example.
  • Example 6 The difference from Example 6 is only that zirconium hydrogen phosphate is not included in this comparative example.
  • Dispersibility Use SEM to observe whether the filler is uniformly dispersed in the polyolefin matrix
  • FIG. 1-3 is an SEM image of the polyolefin composite material provided in Example 1-3 of the present application.
  • “ ⁇ 5000” in the figure represents a magnification of 5000 times.
  • zirconium hydrogen phosphate is uniformly dispersed in the polyolefin matrix.
  • the zirconium hydrogen phosphate nanosheets are regularly arranged along the injection direction, and the structure is regular.
  • FIG. 4-6 is a SEM image of the polyolefin composite material provided in Example 4-6 of the present application
  • FIG. 7 is a SEM image of the polyolefin composite material provided in Comparative Example 7 of the present application. There is agglomeration in the polyolefin matrix.
  • zirconium hydrogen phosphate can improve the dispersibility of graphene in the matrix. It is speculated that the possible reason is that the zirconium hydrogen phosphate nanosheets have a large surface area, Polyhydroxy groups (electron-donating groups) can interact with large ⁇ bonds of graphene, thereby improving the dispersibility of graphene sheets in a non-polar polyolefin matrix.
  • Thermal deformation temperature The thermal deformation temperature of the material under the pressure of 1.82 MPa and 0.45 MPa is tested using DMA, respectively.
  • zirconium hydrogen phosphate can significantly increase the heat distortion temperature of non-polar polyolefins and better increase its heat resistance. It can be seen from the comparison between Examples 1-3 and Comparative Examples 4-9 that the conventional nano fillers that can increase the heat resistance of polymers are not suitable for non-polar polyolefins, and the effect of increasing the heat resistance of non-polar polyolefins Poor, and the filler has agglomeration in the polyolefin matrix, which will affect other properties of the polyolefin matrix. It can be seen from the comparison between Examples 4-6 and Comparative Examples 7-9 that zirconium hydrogen phosphate can increase the dispersibility of graphene in non-polar polyolefins.

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Abstract

本文公开了一种提高聚烯烃热变形温度的方法及由其得到的聚烯烃复合材料和应用，使用磷酸氢锆来提高非极性聚烯烃的热变形温度。本申请发现，将磷酸氢锆加入到非极性聚烯烃中，可以显著提高其热变形温度，增加其耐热性。

Description

提高聚烯烃热变形温度的方法及由其得到的聚烯烃复合材料和应用 技术领域
本申请属于改性技术领域，涉及一种提高聚烯烃热变形温度的方法及由其得到的聚烯烃复合材料和应用。
背景技术
聚烯烃是由乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、4-甲基-1-戊烯等α-烯烃以及某些环烯烃单独聚合或共聚合而得到的一类热塑性树脂的总称，由于原料丰富、价格低廉、容易加工成型、综合性能优良，因此是一类产量最大，应用十分广泛的高分子材料，其中以聚乙烯(PE)和聚丙烯(PP)最为重要。但是这类材料的耐热性能较差，限制了它在某些高温环境下的应用。
目前大多数的技术是利用共混或接枝改性等来增强聚烯烃的耐热性能，有机共混为将其和热稳定性较好的有机高分子(比如聚苯醚、聚苯乙烯等)共混来提升耐热性能，CN105440547A公开了一种高强耐热聚乙烯管材，其原料按重量份数包括如下组分：乙烯基硅烷接枝高密度聚乙烯50-75份、线性低密度聚乙烯10-25份、含钛有机硅树脂5-15份、马来酸酐接枝聚苯醚5-12份、聚苯基磷酸二苯砜酯2-12份、过氧化叔丁醇0.2-1份、四氧化三铁2-10份、硫酸钡2-5份、氢氧化铝1-5份、改性纳米二氧化钛5-15份、硅酸钙晶须2-5份、纳米碳纤维3-10份、聚环氧乙烷0.2-1.5份、甘油单硬脂酸酯0.3-1.5份、乙撑双硬脂酰胺0.2-1.2份、抗氧剂0.5-2份，其耐热性好，强度高，但是成分太复杂，对聚乙烯的加工性能产生非常大影响，并且增加了生产成本。CN106146756A公开了一种简易的石墨烯接枝聚烯烃的方法，其中，利用还原氧化石墨烯对聚烯烃进行改性，使其带有功能基团，可以很好的应用，改性方法过于复杂，不适合大 规模工业化生产。
另外，纳米材料能明显改善聚合物的性能，也成为当前的研究热点。常用的无机纳米填料以蒙脱土(MMT)为代表，作为聚合物高分子材料的添加剂，广泛应用于高分子材料行业；以碳纳米管为代表的一维材料和以石墨烯为代表的二维纳米材料在增强树脂方面也有较好地应用，但是由于非极性聚烯烃中不存在极性基团，也缺乏功能基团，使得以蒙脱土为代表的无机纳米填料并不能很好的分散在聚烯烃材料中，且对聚烯烃耐热性的提高影响十分小，对于碳纳米管和石墨烯也存在于同样的问题，由于非极性聚烯烃材料不含有极性基团，纳米填料在基体中的分散性不好，并且对其耐热性的提高帮助很小。
目前需要开发一种可提高非极性聚烯烃分子耐热性的方法，以解决聚烯烃耐热性能较差的问题，来拓展聚烯烃的应用。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的范围。
本申请的目的在于提供一种提高聚烯烃热变形温度的方法及由其得到的聚烯烃复合材料和应用。
为达到此申请目的，本申请采用以下技术方案：
第一方面，本申请提供了一种提高非极性聚烯烃热变形温度的方法，使用磷酸氢锆来提高非极性聚烯烃的热变形温度。
非极性聚烯烃因其不含有极性基团，常规可以提高聚合物耐热性能的纳米填料会在树脂基体中发生团聚效应，造成基体中产生应力集中或者缺陷，无法在非极性聚烯烃基体中发挥其提高耐热性能的效果或者效果极其不明显。本申请发现，将尺寸更均一、晶型更完整、纵横比更大的磷酸氢锆加入到非极性聚 烯烃中，显著提高其热变形温度，提高其耐热性能。
在本申请中，所述非极性聚烯烃为线性低密度聚乙烯、高密度聚乙烯或聚丙烯。
本申请发现当非极性聚烯烃为线性低密度聚乙烯(LLDPE)、高密度聚乙烯(HDPE)或聚丙烯(PP)时，磷酸氢锆对其耐热性能的增强效果较为显著，可大幅度提升其热变形温度。
可选地，所述方法包括：将磷酸氢锆与聚烯烃共混。
第二方面，本申请提供了一种聚烯烃复合材料，所述聚烯烃复合材料包括非极性聚烯烃和磷酸氢锆。
在本申请中，磷酸氢锆是作为耐热性增强剂使用。
本申请提供了一种具有较高热变形温度的聚烯烃复合材料，磷酸氢锆对非极性聚烯烃的耐热性能提升较为明显。
可选地，所述非极性聚烯烃和磷酸氢锆的质量比为(20-50)∶1，例如25∶1、30∶1、35∶1、40∶1、45∶1等。
可选地，所述非极性聚烯烃为线性低密度聚乙烯、高密度聚乙烯或聚丙烯。
本申请提供的聚烯烃复合材料的热变形温度比与之对应的聚烯烃的热变形温度高18-50％。当磷酸氢锆与聚烯烃的质量比为1∶20时，当非极性聚烯烃为LLDPE时，聚烯烃复合材料的热变形温度比纯的LLDPE的热变形温度高26-50％；当非极性聚烯烃为HDPE时，聚烯烃复合材料的热变形温度比纯的HDPE的热变形温度高20-23％；当非极性聚烯烃为PP时，聚烯烃复合材料的热变形温度比纯的PP的热变形温度高18-20％。
以动态热机械分析(DMA)测试其热变形温度，当磷酸氢锆与聚烯烃的质量比为1∶10时，当非极性聚烯烃为LLDPE时，聚烯烃复合材料在1.82MPa下 的热变形温度比纯的LLDPE高17℃，LLDPE的热变形温度增加了50％；在0.45MPa下的热变形温度比纯的LLDPE高16℃，LLDPE的热变形温度增加了27.6％。当非极性聚烯烃为HDPE时，聚烯烃复合材料在1.82MPa下的热变形温度比纯的HDPE高10℃，HDPE的热变形温度增加了22.2％；在0.45MPa下的热变形温度比纯的HDPE高13℃，HDPE的热变形温度增加了20％。当非极性聚烯烃为PP时，聚烯烃复合材料在1.82MPa下的热变形温度比纯的PP高13℃，PP的热变形温度增加了18.6％，在0.45MPa下的热变形温度比纯的PP高16℃，PP的热变形温度增加了18.8％。
可选地，所述磷酸氢锆为α-磷酸氢锆。
可选地，所述磷酸氢锆的直径为2-10μm，例如3μm、4μm、5μm、6μm、7μm、8μm、9μm等。
可选地，所述聚烯烃复合材料还包括石墨烯。
可选地，所述石墨烯与聚烯烃的质量比为1∶(100-500)，例如1∶200、1∶300、1∶400等。
在本申请中，磷酸氢锆纳米片具有很大的表面积，存在较多羟基(给电子基)，可以与石墨烯的大π键相互作用，从而可以提高石墨烯片在非极性聚烯烃基体中的分散性。
第三方面，本申请提供了如第二方面所述的聚烯烃复合材料的制备方法，所述制备方法包括：将非极性聚烯烃、磷酸氢锆和任选的石墨烯共混，然后注塑成型，得到所述聚烯烃复合材料。
可选地，所述注塑的温度为160-180℃，例如165℃、170℃、175℃等。
可选地，所述注塑的压力为580-600bar，例如585bar、590bar、595bar等。
可选地，所述注塑的时间为2-8s，例如3s、4s、5s、6s、7s等。
可选地，所述注塑用的模具温度为60-70℃，例如62℃、65℃、68℃等。
第四方面，本申请提供了根据第二方面所述的聚烯烃复合材料在车用塑料中的应用。
将PE、PP复合材料应用于车用塑料中，例如汽车车顶夹层、汽车油箱箱体和发动机进气管道等，在提升汽车的安全性能的同时可以替代金属零部件降低整车重量，节约生产成本。
相对于相关技术，本申请具有以下有益效果：
(1)非极性聚烯烃因其不含有极性基团，使得常规可以提升聚合物耐热性能的填料均无法在非极性聚烯烃基体中发挥其提高耐热性能的效果或者效果极其不明显。本申请发现，将磷酸氢锆加入到非极性聚烯烃中，可以显著提高其热变形温度，提高其耐热性能；
(2)在本申请中，磷酸氢锆还可以增加石墨烯在非极性聚烯烃基体中的分散性；
(3)本申请提供的聚烯烃复合材料的热变形温度比与之对应的聚烯烃的热变形温度高18-50％。当非极性聚烯烃为LLDPE时，聚烯烃复合材料的热变形温度比LLDPE的热变形温度高26-50％；当非极性聚烯烃为HDPE时，聚烯烃复合材料的热变形温度比HDPE的热变形温度高20-23％；当非极性聚烯烃为PP时，聚烯烃复合材料的热变形温度比PP的热变形温度高18-20％。当在基体中加入石墨烯时，最后得到的聚烯烃复合材料的热变形温度更高。
在阅读和了解了详细描述和附图后，可以明白其他方面。
附图说明
图1是本申请实施例1提供的聚烯烃复合材料的SEM图。
图2是本申请实施例2提供的聚烯烃复合材料的SEM图。
图3是本申请实施例3提供的聚烯烃复合材料的SEM图。
图4是本申请实施例4提供的聚烯烃复合材料的SEM图。
图5是本申请实施例5提供的聚烯烃复合材料的SEM图。
图6是本申请实施例6提供的聚烯烃复合材料的SEM图。
图7是本申请对比例7提供的聚烯烃复合材料的SEM图。
图1-图7中，附图标尺均为10μm。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1
一种聚烯烃复合材料，由LLDPE和磷酸氢锆组成，其中，LLDPE和磷酸氢锆的质量比为20∶1。
制备方法为：将LLDPE和磷酸氢锆共混，然后注塑成型；
其中，注塑条件为：注射温度165℃，注射压力580bar，注射时间2s，模具温度60℃，保压时间10s。
实施例2-3
与实施例1的区别仅在于，在本实施例中，将LLDPE替换为HDPE(实施例2)、PP(实施例3)。
实施例4
与实施例1的区别仅在于，在本实施例中，还包括石墨烯，石墨烯与聚烯烃的质量比为1∶100。
实施例5
与实施例2的区别仅在于，在本实施例中，还包括石墨烯，石墨烯与聚烯烃的质量比为1∶500。
实施例6
与实施例3的区别仅在于，在本实施例中，还包括石墨烯，石墨烯与聚烯烃的质量比为1∶300。
实施例7
一种聚烯烃复合材料，由LLDPE和磷酸氢锆组成，其中，LLDPE和磷酸氢锆的质量比为50∶1。
制备方法为：将LLDPE和磷酸氢锆共混，然后注塑成型；
其中，注塑条件为：注射温度170℃，注射压力590bar，注射时间4s，模具温度70℃，保压时间10s。
实施例8
一种聚烯烃复合材料，由HDPE和磷酸氢锆组成，其中，HDPE和磷酸氢锆的质量比为35∶1。
制备方法为：将HDPE和磷酸氢锆共混，然后注塑成型；
其中，注塑条件为：注射温度180℃，注射压力600bar，注射时间8s，模具温度65℃，保压时间10s。
对比例1-3
一种聚烯烃，为实施例中的LLDPE(对比例1)、HDPE(对比例2)、PP(对比例3)。
对比例4
与实施例1的区别仅在于，将磷酸氢锆替换为等量的蒙脱土。
对比例5
与实施例2的区别仅在于，将磷酸氢锆替换为等量的纳米二氧化硅。
对比例6
与实施例3的区别仅在于，将磷酸氢锆替换为等量的纳米碳纤维。
对比例7
与实施例4的区别仅在于，本对比例中不包括磷酸氢锆。
对比例8
与实施例5的区别仅在于，本对比例中不包括磷酸氢锆。
对比例9
与实施例6的区别仅在于，本对比例中不包括磷酸氢锆。
性能测试：
对实施例1-8和对比例1-9提供的材料进行性能测试，先将样品在90℃真空烘箱内退火1h，然后进行测试，方法如下：
(1)分散性：利用SEM观察填料在聚烯烃基体中是否均匀分散；
其中，图1-3本申请实施例1-3提供的聚烯烃复合材料的SEM图，图中的“×5000”表示放大5000倍，由图可知，磷酸氢锆均匀地分散在聚烯烃基体内，且磷酸氢锆纳米片沿注塑方向规则排列，结构规整。图4-6为本申请实施例4-6提供的聚烯烃复合材料的SEM图，图7为本申请对比例7提供的聚烯烃复合材料的SEM图，由图7可以看出，石墨烯在聚烯烃基体中有团聚现象；由图4和图7的对比可知，磷酸氢锆可以提高石墨烯在基体中的分散性，推测可能的原因是磷酸氢锆纳米片具有很大的表面积，存在较多羟基(给电子基)，可以与石 墨烯的大π键相互作用，从而提高了石墨烯片在非极性聚烯烃基体中的分散性。
对其余实施例和对比例的表征结果见表1。
(2)热变形温度：利用DMA分别测试材料在1.82MPa、0.45MPa压力下的热变形温度。
对实施例1-8和对比例1-9的性能测试结果见表1：
表1
Figure PCTCN2018121404-appb-000001
Figure PCTCN2018121404-appb-000002
由实施例1-3和对比例1-3的对比可知，磷酸氢锆可以较为显著的提高非极性聚烯烃的热变形温度，较好的增加其耐热性能。由实施例1-3和对比例4-9的对比可知，常规的可以增加高分子耐热性能的纳米填料并不适用于非极性聚烯烃，对非极性聚烯烃耐热性能的增加效果较差，并且填料在聚烯烃基体中有团聚的现象，反而会影响聚烯烃基体的其他性能。由实施例4-6和对比例7-9的对比可知，磷酸氢锆可以增加石墨烯在非极性聚烯烃中的分散性。
申请人声明，本申请通过上述实施例来说明本申请的提高聚烯烃热变形温度的方法及由其得到的聚烯烃复合材料和应用，但本申请并不局限于上述实施例，即不意味着本申请必须依赖上述实施例才能实施。

Claims (10)

  1. 一种提高非极性聚烯烃热变形温度的方法，其中，使用磷酸氢锆来提高非极性聚烯烃的热变形温度。
  2. 根据权利要求1所述的方法，其中，所述非极性聚烯烃为线性低密度聚乙烯、高密度聚乙烯或聚丙烯中的任意一种或至少两种的组合。
  3. 根据权利要求1或2所述的方法，其中，所述方法包括：将磷酸氢锆与非极性聚烯烃共混；
    可选地，所述磷酸氢锆包括磷酸氢锆纳米片。
  4. 一种聚烯烃复合材料，其中，所述聚烯烃复合材料包括非极性聚烯烃和磷酸氢锆。
  5. 根据权利要求4所述的聚烯烃复合材料，其中，所述非极性聚烯烃和磷酸氢锆的质量比为(20-50)∶1。
  6. 根据权利要求4或5所述的聚烯烃复合材料，其中，所述磷酸氢锆包括磷酸氢锆纳米片；
    可选地，所述非极性聚烯烃为线性低密度聚乙烯、高密度聚乙烯或聚丙烯中的任意一种或至少两种的组合；
    可选地，所述磷酸氢锆包括α-磷酸氢锆；
    可选地，所述磷酸氢锆的直径为2-10μm。
  7. 根据权利要求4-6中的任一项所述的聚烯烃复合材料，其中，所述聚烯烃复合材料还包括石墨烯；
    可选地，所述石墨烯与聚烯烃的质量比为1∶(100-500)。
  8. 根据权利要求4-7中的任一项所述的聚烯烃复合材料的制备方法，其中，所述制备方法包括：将非极性聚烯烃、磷酸氢锆和任选的石墨烯共混，然后注塑成型，得到所述聚烯烃复合材料。
  9. 根据权利要求8所述的制备方法，其中，所述注塑的温度为160-180℃；
    可选地，所述注塑的压力为580-600bar；
    可选地，所述注塑的时间为2-8s；
    可选地，所述注塑用的模具温度为60-70℃。
  10. 根据权利要求4-7中的任一项所述的聚烯烃复合材料在车用塑料中的应用。
PCT/CN2018/121404 2018-09-20 2018-12-17 提高聚烯烃热变形温度的方法及由其得到的聚烯烃复合材料和应用 Ceased WO2020056950A1 (zh)

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