WO2018129782A1 - 一种母料组合物及其加工方法 - Google Patents

一种母料组合物及其加工方法 Download PDF

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WO2018129782A1
WO2018129782A1 PCT/CN2017/073335 CN2017073335W WO2018129782A1 WO 2018129782 A1 WO2018129782 A1 WO 2018129782A1 CN 2017073335 W CN2017073335 W CN 2017073335W WO 2018129782 A1 WO2018129782 A1 WO 2018129782A1
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branched polyethylene
parts
highly branched
mol
content
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PCT/CN2017/073335
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French (fr)
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徐涛
傅智盛
吴安洋
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杭州星庐科技有限公司
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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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of polymer materials, and particularly relates to a masterbatch composition and a processing method thereof.
  • carbon nanotubes and graphene provide a new choice for polymer modification. Compared with traditional fillers, carbon nanotubes have the advantages of extremely large aspect ratio, extremely high modulus of elasticity and flexural strength, resistance to strong alkali and strong acid, peculiar electrical conductivity and excellent thermal conductivity.
  • Graphene is a hexagonal ring-shaped body between carbon atoms. It is a two-dimensional space infinitely extending base surface composed of carbon atoms. Its unique physical, chemical and mechanical properties provide the development of new composite materials. A new power. The combination of carbon nanotubes or graphene with polymers is expected to produce a new class of high-performance, multi-functional materials.
  • Polyolefin materials such as polyethylene and polypropylene have the characteristics of high cost performance, good mechanical properties, stable thermal properties, large crystallographic adjustment range, excellent processing performance, good safety and stability, and can be recycled and reused.
  • the combination of carbon nanotubes or graphene with polyolefin materials can improve the mechanical properties, electrical properties and thermal properties of polyolefin materials.
  • the physical blending method can be further divided into a solution blending method and a melt blending method.
  • the physical blending method is simple and easy to process composite materials, but it is easy to mass-produce, but the dispersion of carbon nanotubes or graphene in polyolefin is not good.
  • In-situ polymerization is carried out by loading an olefin polymerization catalyst On the carbon nanotubes or graphene, the composite material is prepared by in-situ polymerization.
  • the carbon nanotubes or graphene in the composite prepared by this method are uniformly dispersed, but the method is too complicated.
  • the solution of the present invention is to provide a masterbatch composition comprising, by weight of 100 parts, 70 to 99 parts of highly branched polyethylene, and 1 to 30 parts of carbon nanotubes or graphene.
  • the highly branched polyethylene has a branching degree of 70 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 436,000, and a Mooney viscosity of ML (1+4) 125 ° C. It is 6 to 93.
  • a further technical solution is that when the degree of branching of the highly branched polyethylene is 70 to 130 branches/1000 carbons, the methyl content is 46.8 to 66.5 mol%, and the ethyl content is 7.2 to 18.3 mol%.
  • the propyl content is 4.6 to 8.3 mol%, the butyl content is 3.2 to 6.7 mol%, the pentyl content is 3.2 to 5.2 mol%, and the carbon number ⁇ 6 branching content is 12.1 to 15.3 mol%.
  • the invention also provides a method of processing a masterbatch composition comprising the steps of:
  • the mixed raw materials are fed into a twin-screw extrusion granulator, and the temperature is controlled at 90 to 160 ° C to carry out extrusion granulation, thereby obtaining a pelletized master batch composition.
  • the invention has the beneficial effects that the highly branched polyethylene is an ethylene homopolymer, is a high performance polyolefin product, has rubber elasticity at normal temperature, has small density, large bending and low temperature resistance. High impact performance and easy processing.
  • Ethylene is the cheapest and abundant source of olefin monomer.
  • the highly branched polyethylene prepared by homopolymerization is simple in process and low in production cost.
  • Highly branched polyethylene has good compatibility with carbon materials such as carbon nanotubes and graphene. Carbon materials can be uniformly dispersed in highly branched by physical blending, solution blending and melt blending.
  • polyethylene in addition, highly branched polyethylene and polyolefin materials (such as polyethylene, poly Propylene has the same composition, similar structure and good compatibility.
  • the carbon material is dispersed in the highly branched polyethylene to form a masterbatch, and then the masterbatch is added to the polyolefin material to prepare a composite material of the polyolefin and the carbon material.
  • the method is simple and easy, and mass production is easy.
  • the highly branched polyethylene used has the characteristics of a branching degree of 70 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 436,000, and a Mooney viscosity of ML (1+4) of 125 ° C of 6 to 93.
  • the degree of branching is measured by nuclear magnetic resonance spectroscopy, and the molar percentages of various branches are measured by nuclear magnetic carbon spectroscopy.
  • the masterbatch composition includes the following raw materials in parts by mass: 99 parts of highly branched polyethylene and 1 part of graphene.
  • the highly branched polyethylene used is numbered PER-5.
  • the processing method of the masterbatch composition specifically includes the following steps:
  • the mixed raw materials are fed into a twin-screw extrusion granulator, and the temperature is controlled at 160 ° C to carry out extrusion granulation, thereby obtaining a pelletized master batch composition.
  • the masterbatch composition includes the following raw materials in parts by mass: 95 parts of highly branched polyethylene and 5 parts of graphene.
  • the highly branched polyethylene used is numbered PER-2.
  • the processing method of the masterbatch composition specifically includes the following steps:
  • the mixed raw materials are fed into a twin-screw extrusion granulator, and the temperature is controlled at 90 ° C to carry out extrusion granulation, thereby obtaining a pelletized master batch composition.
  • the masterbatch composition includes the following raw materials in parts by mass: 90 parts of highly branched polyethylene and 10 parts of carbon nanotubes.
  • the highly branched polyethylene used is numbered PER-3.
  • the processing method of the masterbatch composition specifically includes the following steps:
  • the mixed raw materials are fed into a twin-screw extrusion granulator, and the temperature is controlled at 110 ° C to carry out extrusion granulation, thereby obtaining a pelletized master batch composition.
  • the masterbatch composition includes the following raw materials in parts by mass: 80 parts of highly branched polyethylene and 20 parts of carbon nanotubes.
  • the processing method of the masterbatch composition specifically includes the following steps:
  • the mixed raw materials are fed into a twin-screw extrusion granulator, and the temperature is controlled at 110 ° C to carry out extrusion granulation, thereby obtaining a pelletized master batch composition.
  • the masterbatch composition includes the following raw materials in parts by mass: 70 parts of highly branched polyethylene and 30 parts of carbon nanotubes.
  • the highly branched polyethylene used is numbered PER-4.
  • the processing method of the masterbatch composition specifically includes the following steps:
  • the mixed raw materials are fed into a twin-screw extrusion granulator, and the temperature is controlled at 110 ° C to carry out extrusion granulation, thereby obtaining a pelletized master batch composition.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

本发明涉及到一种包含支化聚乙烯的母料组合物及其加工方法，按重量份100份计，其包含：高度支化聚乙烯70～99份，碳纳米管或石墨烯1～30份，高度支化聚乙烯的支化度为70～130个支链/1000个碳，重均分子量为6.6万～43.6万、门尼粘度ML(1+4)125℃为6～93。其有益效果是，高度支化聚乙烯为乙烯均聚物，是一种高性能聚烯烃产品，在常温下呈橡胶弹性，具有密度小、弯曲大、低温抗冲击性能高、易加工等特点。

Description

一种母料组合物及其加工方法 技术领域
本发明属于高分子材料技术领域，具体涉及一种母料组合物及其加工方法。
背景技术
随着科学技术的不断发展，人们对聚合物材料应用性能的要求越来越高。既要求聚合物材料有出色的韧性，又要有较高的硬度；既希望聚合物耐高温，又希望它易成型加工；不仅性能出众，还要价格低廉。基于这些综合性能的要求，单一聚合物通常难以满足。于是，聚合物的复合改性越来越受到人们的重视。
碳纳米管和石墨烯的出现，为聚合物的改性提供了新的选择。与传统的填料相比，碳纳米管具有极大的长径比、极高的弹性模量和弯曲强度、耐强碱和强酸、奇特的导电性以及优良的导热性等优势。石墨烯是一种碳原子之间呈六角环形的片状体，是一层碳原子构成的一个二维空间无限延伸的基面，它独特的物理、化学和力学性能为新型复合材料的开发提供了新动力。将碳纳米管或石墨烯与聚合物复合，有望加工出一类高性能、多功能的新材料。
聚烯烃材料(如聚乙烯、聚丙烯)具有高性价比、力学性能好、热性能稳定、结晶性调节范围大、加工性能优良、安全稳定性好、可循环再利用等特点。用碳纳米管或石墨烯与聚烯烃材料复合，可提高聚烯烃材料的力学性能、电学性能和热性能等。
碳纳米管和石墨烯与聚烯烃复合材料的加工方法主要有两种：物理共混法和原位聚合法。物理共混法又可分为溶液共混法和熔体共混法。物理共混法加工复合材料简单易行，容易大规模生产，但碳纳米管或石墨烯在聚烯烃中的分散性不好。原位聚合法是将烯烃聚合催化剂负载在 碳纳米管或石墨烯上面，通过原位聚合制备出复合材料，此方法制备的复合材料中碳纳米管或石墨烯分散均匀，但是方法太复杂。
发明内容
本发明的目的是克服现有技术的不足，提供一种母料组合物及其加工方法。
为了解决技术问题，本发明的解决方案是提供一种母料组合物，按重量份100份计，其包括：高度支化聚乙烯70～99份，碳纳米管或石墨烯1～30份。
进一步的技术方案是，所述高度支化聚乙烯的支化度为70～130个支链/1000个碳，重均分子量为6.6万～43.6万、门尼粘度ML(1+4)125℃为6～93。
进一步的技术方案是，当所述高度支化聚乙烯的支化度70～130个支链/1000个碳时，其甲基含量为46.8～66.5mol％、乙基含量为7.2～18.3mol％、丙基含量为4.6～8.3mol％、丁基含量为3.2～6.7mol％、戊基含量为3.2～5.2mol％、碳数≥6支链含量为12.1～15.3mol％。
本发明还提供一种母料组合物的加工方法，其包括以下步骤：
(1)按所述配比将各原料组分加入混合机，在30～50转/分钟的转速下混合3～15分钟；
(2)将混合后的原料加入双螺杆挤压造粒机，温度控制在90～160℃，进行挤压造粒，即得颗粒状的母料组合物。
与现有技术相比，本发明的有益效果为：高度支化聚乙烯为乙烯均聚物，是一种高性能聚烯烃产品，在常温下呈橡胶弹性，具有密度小、弯曲大、低温抗冲击性能高、易加工等特点。乙烯是最便宜、来源非常丰富的烯烃单体，用它均聚制备的高度支化聚乙烯工艺简单，生产成本低。高度支化聚乙烯与碳材料，如碳纳米管和石墨烯的相容性很好，碳材料可以通过物理共混法，溶液共混法和熔体共混法可均匀地分散在高度支化聚乙烯中，另外，高度支化聚乙烯与聚烯烃材料(如聚乙烯、聚 丙烯)组成一样、结构相似，具有较好的相容性。先将碳材料分散在高度支化聚乙烯中做成母料，再将母料添加到聚烯烃材料中制备聚烯烃和碳材料的复合材料，该方法简单易行，容易实现大规模生产。
具体实施方式
下面给出实施例以对本发明做进一步说明，但不是用来限制本发明的范围，该领域的技术熟练人员根据发明内容对本发明做出的一些非本质的改进和调整仍属于本发明的保护范围。
所用高度支化聚乙烯特征为：支化度为70～130个支链/1000个碳、重均分子量为6.6万～43.6万，门尼粘度ML(1+4)125℃为6～93。其中，支化度通过核磁氢谱测得，各种支链摩尔百分含量通过核磁碳谱测得。
具体如下表：
Figure PCTCN2017073335-appb-000001
实施例1：
母料组合物，包括按照质量份数计的如下原料：高度支化聚乙烯99份、石墨烯1份。
其中，采用的高度支化聚乙烯编号为PER-5。
该母料组合物的加工方法具体包括以下步骤：
(1)按所述配比将各原料组分加入混合机，在30转/分钟的转速下混合15分钟；
(2)将混合后的原料加入双螺杆挤压造粒机，温度控制在160℃，进行挤压造粒，即得颗粒状的母料组合物。
实施例2：
母料组合物，包括按照质量份数计的如下原料：高度支化聚乙烯95份、石墨烯5份。
其中，采用的高度支化聚乙烯编号为PER-2。
该母料组合物的加工方法具体包括以下步骤：
(1)按所述配比将各原料组分加入混合机，在50转/分钟的转速下混合3分钟；
(2)将混合后的原料加入双螺杆挤压造粒机，温度控制在90℃，进行挤压造粒，即得颗粒状的母料组合物。
实施例3：
母料组合物，包括按照质量份数计的如下原料：高度支化聚乙烯90份、碳纳米管10份。
其中，采用的高度支化聚乙烯编号为PER-3。
该母料组合物的加工方法具体包括以下步骤：
(1)按所述配比将各原料组分加入混合机，在40转/分钟的转速下混合8分钟；
(2)将混合后的原料加入双螺杆挤压造粒机，温度控制在110℃，进行挤压造粒，即得颗粒状的母料组合物。
实施例4：
母料组合物，包括按照质量份数计的如下原料：高度支化聚乙烯80份、碳纳米管20份。
其中，其中，采用30份编号为PER-1的高度支化聚乙烯和50份编号为PER-6的高度支化聚乙烯。
该母料组合物的加工方法具体包括以下步骤：
(1)按所述配比将各原料组分加入混合机，在40转/分钟的转速下混合8分钟；
(2)将混合后的原料加入双螺杆挤压造粒机，温度控制在110℃，进行挤压造粒，即得颗粒状的母料组合物。
实施例5：
母料组合物，包括按照质量份数计的如下原料：高度支化聚乙烯70份、碳纳米管30份。
其中，采用的高度支化聚乙烯编号为PER-4。
该母料组合物的加工方法具体包括以下步骤：
(1)按所述配比将各原料组分加入混合机，在40转/分钟的转速下混合8分钟；
(2)将混合后的原料加入双螺杆挤压造粒机，温度控制在110℃，进行挤压造粒，即得颗粒状的母料组合物。

Claims (4)

  1. 一种母料组合物，其特征在于，按重量份100份计，其包括：高度支化聚乙烯70～99份；碳纳米管或石墨烯1～30份。
  2. 根据权利要求1所述的母料组合物，其特征在于，所述高度支化聚乙烯的支化度为70～130个支链/1000个碳，重均分子量为6.6万～43.6万、门尼粘度ML(1+4)125℃为6～93。
  3. 根据权利要求2所述的母料组合物，其特征在于，当所述高度支化聚乙烯的支化度70～130个支链/1000个碳时，其甲基含量为46.8～66.5mol％、乙基含量为7.2～18.3mol％、丙基含量为4.6～8.3mol％、丁基含量为3.2～6.7mol％、戊基含量为3.2～5.2mol％、碳数≥6支链含量为12.1～15.3mol％。
  4. 一种包含权利要求1～3中任一所述母料组合物的加工方法，其特征在于，包括以下步骤：
    (1)按所述配比将各原料组分加入混合机，在30～50转/分钟的转速下混合3～15分钟；
    (2)将混合后的原料加入双螺杆挤压造粒机，温度控制在90～160℃，进行挤压造粒，即得颗粒状的母料组合物。
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