WO2022110657A1 - 一种易加工低收缩聚乙烯光缆护套料及其制备方法和应用 - Google Patents

一种易加工低收缩聚乙烯光缆护套料及其制备方法和应用 Download PDF

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WO2022110657A1
WO2022110657A1 PCT/CN2021/092751 CN2021092751W WO2022110657A1 WO 2022110657 A1 WO2022110657 A1 WO 2022110657A1 CN 2021092751 W CN2021092751 W CN 2021092751W WO 2022110657 A1 WO2022110657 A1 WO 2022110657A1
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optical cable
easy
shrinkage
cable sheath
sheath material
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French (fr)
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刘惠文
黄险波
叶南飚
付晓
陈锬
宋晓庆
李计彪
梁家荣
肖孟杰
邓建清
刘乐文
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Kingfa Science and Technology Co Ltd
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    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • 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
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • 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
    • C08L2207/066—LDPE (radical process)

Definitions

  • the invention relates to the field of optical cable sheathing materials, and more particularly, to an easy-to-process low-shrinkage polyethylene optical cable sheathing material and a preparation method and application thereof.
  • polyethylene materials that meet the requirements of the standard GB/T 15065 can meet the requirements, but for some special optical cables, such as aramid reinforced optical cables, air-blown micro-cables, etc., because the inner layer has no steel lining armor For protection, the post-shrinkage of the ordinary outer sheath will compress the inside of the optical cable, resulting in the deformation of the optical fiber and the attenuation of the optical signal.
  • Cid662501A discloses a low shrinkage polyethylene sheath material and its preparation method. Low shrinkage is achieved by using a combination of different ratios between low-melting index mPE resin and high-melting index mPE resin, but this method is difficult to process.
  • the invention provides an easy-to-process low-shrinkage polyethylene optical cable sheathing material.
  • Another object of the present invention is to provide a preparation method of the easy-to-process low-shrinkage polyethylene optical cable jacket material.
  • Another object of the present invention is to provide the application of the easy-to-process low-shrinkage polyethylene optical cable jacket material.
  • the technical scheme adopted in the present invention is:
  • An easy-to-process low-shrinkage polyethylene optical cable sheath material comprising the following components calculated by weight:
  • the invention adopts the compounding of polyolefin elastomer POP, nucleating agent and nano-silica, which not only reduces the shrinkage rate of the sheathing material, but also increases the limit processing rate of the sheathing material.
  • the crystallinity of the composite material is reduced by POP, and the mutual synergy of the nucleating agent and nano-silica makes the crystal of the composite material refined and homogenized, so the shrinkage rate of the sheath material is greatly reduced.
  • POP also has lower processing. Temperature, the material can be processed at a lower temperature, which can improve the extrusion rate of the material, and nano-silica can play the role of internal lubrication, and the combination of lubricants greatly increases the limit processing rate of the material.
  • the polyolefin elastomer POP is one of ethylene-hexene copolymer, ethylene-octene copolymer or ethylene-propylene-octene copolymer.
  • the POP density of the polyolefin elastomer is 0.890-0.905 g/cm 3 .
  • the polyolefin elastomer has a good shrinkage rate when the POP density is 0.890-0.905 g/cm 3 .
  • the average particle size of the nano-silica is less than or equal to 800 nm.
  • the average particle size of the nano-silica is larger than 800 nm, the limiting rate is reduced.
  • the nano-silicon dioxide is prepared by a high-temperature hydrolysis synthesis method of oxyhydrogen flame, and the nano-silica prepared by this method has good compatibility.
  • the nucleating agent is a dibenzylidene sorbitol nucleating agent, an aryl-substituted phosphate nucleating agent, an organophosphate metal salt nucleating agent or a phenyl acryloyloxybenzoate nucleating agent.
  • the high-density polyethylene HDPE has a melt index of 0.5-3 g/10min at 190° C. and 2.16 kg, and has a bimodal molecular weight distribution.
  • melt index of the high-density polyethylene is 0.5-3 g/10min, it has good low shrinkage rate and good processing performance, and when the molecular weight distribution is bimodal, it is easy to process.
  • the low-density polyethylene LDPE has a melt index of 1-5 g/10min at 190° C. and 2.16 kg, and the elongation at break is greater than or equal to 500%.
  • the linear low density polyethylene LLDPE has a melt index of 1-5 g/10min at 190° C. and 2.16 kg, a molecular weight distribution greater than 10, and an elongation at break greater than or equal to 600%.
  • the elongation at break is measured according to the measurement method of GB/T1040.3-2006.
  • the carbon black masterbatch is a masterbatch with a carbon black content greater than or equal to 48% and a carbon black dispersion degree of less than or equal to grade 3.
  • the antioxidant contains a primary antioxidant and a secondary antioxidant in a ratio of 1:1.
  • the lubricant is a compound of PE wax, zinc stearate and silicone, and the mass ratio of the three is 2:2:1.
  • the present invention also provides a preparation method of the easy-to-process low-shrinkage polyethylene optical cable sheath material, comprising the following steps:
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • nucleating agent nucleating agent and nano-silica
  • step S2 Mix the mixture material obtained in step S1 with antioxidant and lubricant uniformly in a mixer, and then extrude and pelletize it through a twin-screw extruder.
  • the invention provides an easy-to-process and low-shrinkage optical cable sheath material, which is compounded by polyolefin elastomer POP, a nucleating agent and nano-silica, which not only reduces the shrinkage rate of the sheath material, but also improves the material's durability.
  • the ultimate speed, the shrinkage rate is within 2.5%, the ultimate speed is greater than or equal to 1800s -1 , the tensile strength is greater than 27MPa, and the elongation at break is greater than or equal to 700%.
  • reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • HDPE melt index is 0.5g/10min at 190°C, 2.16kg, molecular weight distribution is bimodal; HDPE DGDZ2400, Sinopec;
  • LDPE melt index 2g/10min at 190°C, 2.16kg, elongation at break 800%, LDPE 2426H, CNOOC;
  • LLDPE melt index 2g/10min at 190°C, 2.16kg, molecular weight distribution greater than 10, elongation at break 750%, LLDPE 1002BU, ExxonMobil;
  • Polyolefin elastomer A1 ethylene-octene copolymer, density 0.900g/cm 3 , POE ENGAGE 7447, Dow Chemical;
  • Polyolefin elastomer B ethylene-hexene copolymer, density 0.900g/cm 3 , POE LC565, LG Chem;
  • Polyolefin elastomer C ethylene-propylene-octene copolymer, density 0.900g/cm 3 POE ENGAGE 8137, Dow Chemical;
  • Polyolefin elastomer D ethylene-butene copolymer, density 0.900 g/cm 3 POE7447, Dow Chemical.
  • Polyolefin elastomer A2 ethylene-octene copolymer, density 0.890g/cm 3 , SOLUMER 891 Mitsui Chemicals;
  • Polyolefin elastomer A3 ethylene-octene copolymer, density 0.905g/cm 3 , POE ENGAGE 8207, Dow Chemical;
  • Polyolefin elastomer A4 ethylene-octene copolymer, density 0.860g/cm 3 , POE XUS58705.00, Dow Chemical
  • Nucleating agent A Aryl-substituted phosphate nucleating agent; TMP-6, Milliken;
  • Nucleating agent B organophosphate metal salt nucleating agent; LICOMONT NAV101PWD, DuPont;
  • Nucleating agent C Dibenzylidene sorbitol nucleating agent; NAA-325, Milliken;
  • Nano silica A particle size is 600nm; TSP-H10, Nucolet;
  • Nano silica B particle size is 800nm; FN-865, Funing New Material;
  • Nano silica C particle size is 900nm; HDK H2000, Wacker, Germany;
  • Carbon black masterbatch KF2772, Cabot, carbon black content is 50%, carbon black dispersion degree is 2.5;
  • Antioxidants main antioxidant SONOX1010, auxiliary antioxidant SONOX168, BASF;
  • Lubricant The compound of PE wax, zinc stearate and silicone, the mass ratio of the three is 2:2:1.
  • step S2 The mixed material obtained in step S1, antioxidant and lubricant are mixed uniformly at a rotating speed of 1000rpm in a mixer, extruded and pelletized through a twin-screw extruder, and the twin-screw length-diameter ratio (L/D) is obtained. It is 48: 1, and the temperature of each zone is 180-200 °C.
  • Example 16 Example 17 Example 18 Example 19 HDPE 20 20 20 20 LDPE 30 30 30 30 30 LLDPE 50 50 50 50 50 Polyolefin Elastomer A1 5 5 5 5 5 5 5 Nucleating agent A 1 1 — — Nucleating agent B — — 1 — Nucleating agent C — — — 1 Nano Silica A — — 0.5 0.5 Nano Silica B 0.5 — — — Nano silica C — 0.5 — — Carbon black masterbatch 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Antioxid
  • Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 HDPE 20 20 20 20 20 LDPE 30 30 30 30 30 LLDPE 50 50 50 50 50 50 50 50 50 Polyolefin Elastomer A1 — 5 5 1 20 Nucleating agent A 1 1 — 1 1 Nano Silica A 0.5 — — 0.5 0.5
  • the shrinkage rate is measured according to the measuring method of GB/T 2951.3-1997;
  • Example 1 27.8 788 2.4 2000
  • Example 2 28.7 754 2.37 2100
  • Example 3 27.9 767 2.3 1900
  • Example 4 30.1 802 2.21 2200
  • Example 5 28.1 721 2.31 2100
  • Example 6 29.2 799 2.30 2000
  • Example 8 30.1 802 2.34 2200
  • Example 9 28.09 756 2.23 2300
  • Example 10 30.2 799 2.13 2400
  • Example 11 31.1 781 2.44 2000
  • Example 12 28.3 712 2.3 2000
  • Example 13 27.1 700 2.5 1800
  • Example 14 29.6 744 2.15 2000
  • Example 15 32.1 732 2.33 2000
  • Example 16 28.7 765 2.45 2200
  • Example 17 28.7 753 2.4 2000
  • Example 18 28.4 756 2.45 1800
  • Example 19 28.9 732 2.21 2100
  • Example 20 28.8 700 2.2 2000 Comparative Example 1 25.8 578 2.79 1400 Comparative Example 2 27.0 678 2.81 1300 Comparative Example 3 26.6 688 3.1 1200 Comparative Example 4 27.6 651 2.89 1900 Comparative Example 5 20.1 777 2.36 900
  • the nucleating agent destroys the large crystals of PE and reduces the shrinkage.
  • nano-silica has obvious effects of reducing shrinkage and increasing the limit rate.
  • nano-silica destroys the regular arrangement of PE molecules and reduces the shrinkage rate.
  • the intermolecular lubricating effect improves the extrusion effect.
  • Example 13 It can be seen from Example 13 that the effect of selecting ethylene-butene copolymer as the polyolefin elastomer is worse than that of Examples 2 and 11-12.
  • the shrinkage rate of the material is extremely high, and the limit rate is very low. This is because PE has strong elasticity in the melt state and is easy to shrink. , and its crystallinity is high, and the shrinkage rate is further increased.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

本发明公开了一种易加工低收缩聚乙烯光缆护套料及其制备方法和应用，所述护套料包括按如下重量份计算的组分：高密度聚乙烯HDPE 20～50份；低密度聚乙烯LDPE 20～30份；线性低密度聚乙烯LLDPE50～70份；聚烯烃弹性体POP2～10份；成核剂1～5份；纳米氧化硅0.5～2份；炭黑母粒3～6份；抗氧剂1～2份；润滑剂0.5～2份。该组合物不仅具有低收缩，且加工性能良好，收缩率在2.5％以内，极限速率大于1800s -1，拉伸强度大于27MPa，断裂伸长率大于等于700％。

Description

一种易加工低收缩聚乙烯光缆护套料及其制备方法和应用 技术领域
本发明涉及光缆护套材料领域，更具体地，涉及一种易加工低收缩聚乙烯光缆护套料及其制备方法和应用。
背景技术
随着国内和国际通信行业的蓬勃发展，光缆行业也随之高速发展，其表面护套层所用的护套料用量急增，随之材料的要求也越来越高、越来越规范，如拉伸强度、伸长率、炭黑含量、环境应力开裂等物性都是国内外标准严格要求管控的性能指标，同时随着光缆生产设备的更新换代和产能提升的要求，光缆加工越来越趋向于高速加工、低温加工，这就要求护套材料在兼具性能的前提下还必须保证易加工。
对于普通的铠装光缆，符合标准GB/T 15065要求的聚乙烯材料即可满足要求，但对于部分特殊光缆，如芳纶增强光缆、气吹微缆等，由于其内层没有钢衬铠装保护，普通外护套的后收缩会压迫光缆内部，导致光纤形变，产生光信号衰减。
中国专利(CN111662501A)公开了一种低收缩聚乙烯护套料及其制备方法。通过采用低熔指mPE树脂和高熔指mPE树脂之间不同配比的组合来实现低收缩，但是该方法的加工难度大。
因此，开发一种易加工、低收缩聚乙烯护套料尤为迫切。
发明内容
本发明为克服现有的光缆护套料收缩率高、生产效率低的缺陷，提供一种易加工低收缩聚乙烯光缆护套料。
本发明的另一目的在于提供所述易加工低收缩聚乙烯光缆护套料的制备方法。
本发明的另一目的在于提供所述易加工低收缩聚乙烯光缆护套料的应用。
为解决上述技术问题，本发明采用的技术方案是：
一种易加工低收缩聚乙烯光缆护套料，包括如下按重量份计算的组分：
Figure PCTCN2021092751-appb-000001
Figure PCTCN2021092751-appb-000002
本发明采用聚烯烃弹性体POP、成核剂和纳米二氧化硅复配，不仅降低了护套料的收缩率，而且还提高了护套料的极限加工速率。其中通过POP降低复合材料的结晶度，成核剂和纳米二氧化硅的互相协同使得复合材料晶体细化和均匀化，因此护套料的收缩率大大降低，另外，POP还具有较低的加工温度，材料在较低温度下即可加工，能够提高材料挤出速率、纳米二氧化硅能起到内润滑的作用，搭配润滑剂使得材料的极限加工速率大大提升。
优选地，所述聚烯烃弹性体POP为乙烯-己烯共聚物、乙烯-辛烯共聚物或乙烯-丙烯-辛烯共聚物中一种。
优选地，所述聚烯烃弹性体POP密度为0.890～0.905g/cm 3。
所述聚烯烃弹性体POP密度在0.890～0.905g/cm 3时具有良好的收缩率。
优选地，所述纳米二氧化硅的平均粒径为小于等于800nm。
所述纳米二氧化硅的平均粒径若大于800nm，极限速率降低。
所述纳米二氧化硅通过氢氧火焰高温水解合成法制备得到，通过该方法制备得到的纳米二氧化硅具有良好的相容性。
优选地，所述成核剂为二苄叉山梨醇成核剂、芳基取代磷酸盐成核剂、有机磷酸金属盐成核剂或丙烯酰氧苯甲酸苯酯成核剂。
优选地，所述高密度聚乙烯HDPE在190℃，2.16kg条件下熔融指数为0.5～3g/10min，分子量分布为双峰分布。
所述高密度聚乙烯的熔融指数在0.5～3g/10min时具有良好的低收缩率和较好的加工性能，分子量分布为双峰分布时易于加工。
优选地，所述低密度聚乙烯LDPE在190℃，2.16kg条件下熔融指数为1～5g/10min，断裂伸长率大于等于500％。
优选地，所述线性低密度聚乙烯LLDPE在190℃，2.16kg条件下熔融指数为1～5g/10min，分子量分布大于10，断裂伸长率大于等于600％。
所述断裂伸长率根据GB/T1040.3-2006的测定方法进行测定。
所述炭黑母粒为炭黑含量大于等于48％，炭黑分散度小于等于3级的母粒。
所述抗氧剂含有主抗氧剂和辅抗氧剂，其比例为1:1。
所述润滑剂为PE蜡、硬脂酸锌和硅酮的复配物，三者的质量比为2:2:1。
本发明还提供所述易加工低收缩聚乙烯光缆护套料的制备方法，包括如下步骤：
S1.将高密度聚乙烯HDPE、低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、聚烯烃弹性体、成核剂和纳米二氧化硅投入到混合机中混合均匀，得到预混物；
S2.将步骤S1得到的混合物料和抗氧剂、润滑剂在混合机中混合均匀，通过双螺杆挤出机挤出、造粒得到。
所述易加工低收缩聚乙烯光缆护套料在制备线缆护套料中的应用。
与现有技术相比，本发明的有益效果是：
本发明提供了一种易加工低收缩的光缆护套料，采用聚烯烃弹性体POP、成核剂和纳米二氧化硅复配，不仅降低了护套料的收缩率，而且还提高了材料的极限速率，收缩率在2.5％以内，极限速率大于等于1800s -1，拉伸强度大于27MPa，断裂伸长率大于等于700％。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，但本发明的实施方式不限于此。
本发明所采用的试剂、方法和设备，如无特殊说明，均为本技术领域常规试剂、方法和设备。
以下实施例及对比例中采用的原料如下：
HDPE：在190℃，2.16kg条件下熔融指数为0.5g/10min，分子量分布为双峰分布；HDPE DGDZ2400，中石化；
LDPE：在190℃，2.16kg条件下熔融指数为2g/10min，断裂伸长率800％，LDPE 2426H，中海油；
LLDPE：在190℃，2.16kg条件下熔融指数为2g/10min，分子量分布大于 10，断裂伸长率750％，LLDPE 1002BU，埃克森美孚；
聚烯烃弹性体A1：乙烯-辛烯共聚物，密度0.900g/cm 3，POE ENGAGE 7447，陶氏化学；
聚烯烃弹性体B：乙烯-己烯共聚物，密度0.900g/cm 3，POE LC565，LG化学；
聚烯烃弹性体C：乙烯-丙烯-辛烯共聚物，密度0.900g/cm 3POE ENGAGE 8137，陶氏化学；
聚烯烃弹性体D：乙烯-丁烯共聚物，密度0.900g/cm 3POE7447，陶氏化学。
聚烯烃弹性体A2：乙烯-辛烯共聚物，密度0.890g/cm 3，SOLUMER 891三井化学；
聚烯烃弹性体A3：乙烯-辛烯共聚物，密度0.905g/cm 3，POE ENGAGE 8207，陶氏化学；
聚烯烃弹性体A4：乙烯-辛烯共聚物，密度0.860g/cm 3，POE XUS58705.00，陶氏化学
成核剂A：芳基取代磷酸盐成核剂；TMP-6，美利肯；
成核剂B：有机磷酸金属盐成核剂；LICOMONT NAV101PWD，杜邦；
成核剂C：二苄叉山梨醇成核剂；NAA-325，美利肯；
纳米二氧化硅A:粒径为600nm；TSP-H10，Nucolet公司；
纳米二氧化硅B:粒径为800nm；FN-865，福宁新材料；
纳米二氧化硅C:粒径为900nm；HDK H2000，德国瓦克；
炭黑母粒：KF2772，卡博特，炭黑含量为50％，炭黑分散度2.5级；
抗氧剂：主抗氧剂SONOX1010、辅助抗氧剂SONOX168，巴斯夫；
润滑剂：PE蜡、硬脂酸锌和硅酮的复配物，三者的质量比为2:2:1。
下面结合实施例来详细说明本发明。
下面实施例和对比例均通过以下方法制备光缆护套料，按照表1-表5的重量比称取各组分；具体步骤如下：
S1.将HDPE、LDPE、LLDPE、聚烯烃弹性体、成核剂和纳米二氧化硅投入到混合机中以2000-3000rpm的转速混合均匀，得到预混物；
S2.将步骤S1得到的混合物料和抗氧剂、润滑剂在混合机中以1000rpm的转速混合均匀，通过双螺杆挤出机挤出、造粒得到，双螺杆长径比(L/D)为48： 1，各区温度为180-200℃。
表1实施例1～7的配方
Figure PCTCN2021092751-appb-000003
表2实施例8～16的配方
Figure PCTCN2021092751-appb-000004
Figure PCTCN2021092751-appb-000005
表3实施例16～19的配方
  实施例16 实施例17 实施例18 实施例19
HDPE 20 20 20 20
LDPE 30 30 30 30
LLDPE 50 50 50 50
聚烯烃弹性体A1 5 5 5 5
成核剂A 1 1 — —
成核剂B — — 1 —
成核剂C — — — 1
纳米二氧化硅A — — 0.5 0.5
纳米二氧化硅B 0.5 — — —
纳米二氧化硅C — 0.5 — —
炭黑母粒 5 5 5 5
抗氧剂 1 1 1 1
润滑剂 1 1 1 1
表4对比例1～5的配方
  对比例1 对比例2 对比例3 对比例4 对比例5
HDPE 20 20 20 20 20
LDPE 30 30 30 30 30
LLDPE 50 50 50 50 50
聚烯烃弹性体A1 — 5 5 1 20
成核剂A 1 1 — 1 1
纳米二氧化硅A 0.5 — — 0.5 0.5
炭黑母粒 5 5 5 5 5
抗氧剂 1 1 1 1 1
润滑剂 1 1 1 1 1
各实施例和对比例制备的护套料均通过如下方法测试
1.拉伸强度和断裂伸长率根据GB/T 1040.3-2006的测定方法进行测定；
2.收缩率按照GB/T 2951.3-1997的测定方法进行测定；
3.极限剪切速率使用高福特毛细管流变仪测试，长径比为20:1，口模为90°直角口模。并定义：“极限速率”为190℃时，毛细管挤出出现熔体破裂时的剪切速率，其数值越大代表材料能达到更高的加工速率。
表5各实施例和对比例的数据
  拉伸强度/MPa 断裂伸长率/％ 收缩率/％ 极限速率/S -1
实施例1 27.8 788 2.4 2000
实施例2 28.7 754 2.37 2100
实施例3 27.9 767 2.3 1900
实施例4 30.1 802 2.21 2200
实施例5 28.1 721 2.31 2100
实施例6 29.2 799 2.30 2000
实施例7 27.9 767 2.12 2100
实施例8 30.1 802 2.34 2200
实施例9 28.09 756 2.23 2300
实施例10 30.2 799 2.13 2400
实施例11 31.1 781 2.44 2000
实施例12 28.3 712 2.3 2000
实施例13 27.1 700 2.5 1800
实施例14 29.6 744 2.15 2000
实施例15 32.1 732 2.33 2000
实施例16 28.7 765 2.45 2200
实施例17 28.7 753 2.4 2000
实施例18 28.4 756 2.45 1800
实施例19 28.9 732 2.21 2100
实施例20 28.8 700 2.2 2000
对比例1 25.8 578 2.79 1400
对比例2 27.0 678 2.81 1300
对比例3 26.6 688 3.1 1200
对比例4 27.6 651 2.89 1900
对比例5 20.1 777 2.36 900
从实施例1～4看，弹性体含量越高，收缩率越低：弹性体为非晶体，与PE分子互溶时降低了其结晶度，收缩率降低。
从实施例2和5～7看，成核剂越多，收缩率越低，成核剂破坏了PE的大晶体，降低了收缩。
从实施例2和8～10看，纳米二氧化硅有较明显的降低收缩和提高极限速率的效果，纳米二氧化硅一方面破坏PE分子的规整排列，降低了收缩率，另一方面在PE分子间起到润滑作用，提高了挤出效果。
从实施例2和11～12看，选择不同类型的聚烯烃树脂，其收缩率和极限速率变化不大。
从实施例13看，选择乙烯-丁烯共聚物作为聚烯烃弹性体，其效果要差于实施2和11～12。
从实施例2和14～16看，选择聚烯烃弹性体的密度在0.86～0.905g/cm 3范围时，各材料性能均较好，其中密度为0.86g/cm 3时效果要差于其他密度的聚烯烃弹性体。
从实施例2和17～18看，纳米二氧化硅粒径越小，材料收缩率降低越多，极限速率越高，这是因为粒径小，单位重量的二氧化硅的颗粒数更多，更容易分散在PE分子链中，效果更好。
从实施例2和19～20看，选择不同类型的成核剂，其收缩率和极限速率变化不大，不同类型的成核剂对材料的结晶度影响不大，其收缩率相差不大。
从对比例1～3看，没有成核剂、纳米二氧化硅和弹性体的支撑，材料的收缩率极高，且极限速率很低，这是由于PE在熔体状态弹性较强，容易收缩，且其结晶度高，收缩率进一步增大。
从对比例4和5看，弹性体太少，材料收缩率太大，达不到要求，而弹性体太多，材料拉伸强度下降严重，且由于材料弹性太强，极限速率下降。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种易加工低收缩聚乙烯光缆护套料，其特征在于，包括如下按重量份计算的组分：
    Figure PCTCN2021092751-appb-100001
  2. 如权利要求1所述易加工低收缩聚乙烯光缆护套料，其特征在于，所述聚烯烃弹性体POP为乙烯-己烯共聚物、乙烯-辛烯共聚物或乙烯-丙烯-辛烯共聚物中一种。
  3. 如权利要求2所述易加工低收缩聚乙烯光缆护套料，其特征在于，所述聚烯烃弹性体POP的密度为0.890～0.905g/cm 3。
  4. 如权利要求1所述易加工低收缩聚乙烯光缆护套料，其特征在于，所述纳米二氧化硅的平均粒径为小于等于800nm。
  5. 如权利要求1所述易加工低收缩聚乙烯光缆护套料，其特征在于，所述成核剂为二苄叉山梨醇成核剂、芳基取代磷酸盐成核剂、有机磷酸金属盐成核剂或丙烯酰氧苯甲酸苯酯成核剂中的一种。
  6. 如权利要求1所述易加工低收缩聚乙烯光缆护套料，其特征在于，所述高密度聚乙烯HDPE在190℃，2.16kg条件下熔融指数为0.5～3g/10min，分子量分布为双峰分布。
  7. 如权利要求1所述易加工低收缩聚乙烯光缆护套料，其特征在于，所述低密度聚乙烯LDPE在190℃，2.16kg条件下熔融指数为1～5g/10min，断裂伸长率大于等于500％。
  8. 如权利要求1所述易加工低收缩聚乙烯光缆护套料，其特征在于，所述线性低密度聚乙烯LLDPE在190℃，2.16kg条件下熔融指数为1～5g/10min，分 子量分布大于10，断裂伸长率大于等于600％。
  9. 如权利要求1～8任一项所述易加工低收缩聚乙烯光缆护套料的制备方法，其特征在于，包括如下步骤：
    S1.将高密度聚乙烯HDPE、低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、聚烯烃弹性体、炭黑母粒、成核剂和纳米二氧化硅投入到混合机中混合均匀，得到预混物；
    S2.将步骤S1得到的混合物料和抗氧剂、润滑剂在混合机中混合均匀，通过双螺杆挤出机挤出、造粒得到。
  10. 权利要求1～8中任一项所述易加工低收缩聚乙烯光缆护套料在制备光缆护套中的应用。
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