WO2022135271A1 - 一种超柔软b1级低烟无卤阻燃护套料及其制备方法 - Google Patents

一种超柔软b1级低烟无卤阻燃护套料及其制备方法 Download PDF

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WO2022135271A1
WO2022135271A1 PCT/CN2021/138867 CN2021138867W WO2022135271A1 WO 2022135271 A1 WO2022135271 A1 WO 2022135271A1 CN 2021138867 W CN2021138867 W CN 2021138867W WO 2022135271 A1 WO2022135271 A1 WO 2022135271A1
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parts
soft
ultra
free flame
smoke halogen
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French (fr)
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梁家荣
黄险波
叶南飚
刘乐文
付晓
李计彪
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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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • 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
    • H01B3/307—Other macromolecular compounds
    • 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
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • 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
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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
    • 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

Definitions

  • the invention relates to the field of cable sheathing materials, and more particularly, to an ultra-soft B1-grade low-smoke halogen-free flame-retardant sheathing material and a preparation method thereof.
  • GB/T 31247 Class B1 flame retardant cables are mainly used in densely populated places such as airports, stations, rail transit, and large buildings. Compared with GB/T 19666 and GB/T 17651, GB/T 31247 B1 flame retardant has higher requirements for the heat release and smoke release properties of the sheath material, which is difficult to meet with traditional sheath materials.
  • Halogen-free flame retardant cable material is filled with a large amount of metal hydroxide, which makes the material generally hard, and the Shore A hardness is very large. It also does not meet the GB/T 31247 B1 standard.
  • a sheath material with relatively high flexibility is required.
  • some cables have limited laying space, such as offshore platforms. In order to save space and facilitate laying, This requires the cable to have a smaller bend radius. In order to obtain a small bending radius for the cable, on the one hand, the cable structure should be reasonably designed and easy to bend; The soft feature imparted to the cable facilitates laying during construction. Materials with high hardness are not conducive to construction.
  • the material is easy to soften and has poor temperature resistance.
  • burning in bundles (20 minutes of burning for high-grade bundled combustion) if the charring efficiency is not enough, the flammable mechanism inside the cable cannot be protected in time, which is easy to cause
  • the temperature of the box is too high (over 100°C), causing the sheath to fall off, resulting in failure of the flame retardant. Therefore, it is very difficult for the soft sheath material to reach the B1 level.
  • Chinese patent (CN104672743A) discloses an oil-resistant and corrosion-resistant super-soft cable sheath material and a preparation method thereof. Although it satisfies the super-soft performance, the flame retardant can not meet the B1-level flame retardant performance.
  • the present invention provides a super soft B1-level low-smoke halogen-free flame-retardant sheath material in order to overcome the above-mentioned defect of the prior art that both softness and B1-level flame retardancy cannot be satisfied at the same time.
  • Another object of the present invention is to provide a preparation method of the ultra-soft B1-grade low-smoke halogen-free flame retardant sheath material.
  • Another object of the present invention is to provide the ultra-soft B1-grade low-smoke halogen-free flame-retardant cable jacket.
  • An ultra-soft B1 grade low-smoke halogen-free flame retardant sheath material comprising the following components calculated by weight:
  • the content of styrene in the hydrogenated styrene-butadiene block copolymer is 20-40 wt%;
  • the aluminum hypophosphite is coated.
  • the present invention firstly adopts hydrogenated styrene-butadiene block copolymer with a styrene content of 20-40 wt% and rubber filler oil to reduce the hardness of the resin and greatly improves the softness of the material; wherein, hydrogenated styrene-butadiene-
  • the styrene content of the butadiene block copolymer has excellent softness when the content of styrene is 20-40%.
  • the distribution of the matrix resin is more uniform, and the softness is further improved; at the same time, the use of The excellent compatibility of polyphenylene ether, SEBS grafted maleic anhydride and hydrogenated styrene-butadiene block copolymer greatly improves the mechanical properties of the material; the coated aluminum hypophosphite, magnesium hydroxide and The compounding of smoke suppressant, on the one hand, reduces the content of magnesium hydroxide and improves the softness; The combination of magnesium hydroxide and aluminum hypophosphite can obtain a good flame retardant carbonization effect.
  • Aluminum hypophosphite is an acidic substance, and magnesium hydroxide is a weakly alkaline substance. The aluminum hypophosphite is coated to effectively avoid the reaction with magnesium hydroxide, resulting in flame retardant failure.
  • the aluminum hypophosphite is coated with melamine resin.
  • the content of methacrylic acid in the ethylene-methyl acrylate copolymer is 18-36 wt %.
  • the content of methacrylic acid is 18-36wt%, the resin has better tensile strength.
  • the molecular weight of the hydrogenated styrene-butadiene block copolymer is greater than or equal to 250,000. Increase the tensile strength of hydrogenated styrene-butadiene block copolymers.
  • the rubber filler oil is naphthenic rubber oil and paraffin-based rubber oil.
  • the content of styrene in the SEBS-grafted maleic anhydride is 20-40 wt%.
  • the styrene content is within 20-40wt%, it has better softness.
  • the graft ratio of the SEBS-grafted maleic anhydride is greater than or equal to 0.8%.
  • the determination of the grafting ratio can be performed by a conventional method, for example, an acid-base titration method.
  • the average particle size of the aluminum hypophosphite is less than or equal to 50 ⁇ m.
  • the average particle size is less than or equal to 50 ⁇ m, it has better flame retardant performance.
  • the average particle size of the magnesium hydroxide is less than or equal to 1.5 ⁇ m.
  • the average particle size is less than or equal to 1.5 ⁇ m, it has better flame retardant performance.
  • the surface of the magnesium hydroxide is coated with 3-aminopropyltriethoxysilane, and the coating rate is more than 80%
  • the smoke suppressant is a mixture of nano-montmorillonite, ammonium octamolybdate and zinc borate, wherein, by weight, 5-25 parts of nano-montmorillonite; 35-55 parts of ammonium octamolybdate; boric acid Zinc is 20 to 40 parts.
  • the molecular weight of the polyphenylene ether is 20000-60000, it is powder PPO, and the average particle size is between 20-100 ⁇ m.
  • the melt index of the ethylene-octene copolymer is 0.5-3 g/10min and the density is 0.87-0.895 g/cm 3 when tested at 190° C. under a load of 2.16 Kg.
  • the present invention also provides a preparation method of the ultra-soft B1-grade low-smoke halogen-free flame-retardant sheathing material, comprising the following steps:
  • step S2 the material after the drying of step S1 and ethylene-methyl acrylate copolymer, SEBS graft maleic anhydride, magnesium hydroxide, aluminum hypophosphite, smoke suppressant, antioxidant, lubricant are put into dense Mixing in a mill, mixing, cooling, discharging and granulation.
  • the temperature of the internal mixer is 145-160°C. Mixing time is not less than 10min.
  • the invention provides an ultra-soft B1 grade low-smoke halogen-free flame retardant cable sheath material, which adopts hydrogenated styrene-butadiene block copolymer with styrene content of 20-40 wt%, rubber filler oil and SEBS grafted horse
  • the acid anhydride is blended to reduce the hardness of the resin and greatly improve the softness of the material.
  • the maximum value of Shore A hardness of the sheath material is 79A, which meets B1 level flame retardancy, the light transmittance of the finished product is greater than or equal to 60%, the tensile strength and elongation at break meet the standard, and it can be applied to cables that require ultra-soft in a sheathed environment.
  • reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • Ethylene-methyl acrylate copolymer A the methacrylic acid content is 18wt%, and the TC 121 Molding brand of ExxonMobil is used;
  • Ethylene-methyl acrylate copolymer B the methacrylic acid content is 20wt%, and the 20MA08 brand of French Arkema is used;
  • Ethylene-methyl acrylate copolymer C the content of methacrylic acid is 24wt%, and the 24MA005 brand of French Arkema is used;
  • Ethylene-methyl acrylate copolymer D the content of methacrylic acid is 10wt%, and the SP1402 grade of Westlake Chemical in the United States is used;
  • Ethylene-methyl acrylate copolymer E the content of methacrylic acid is 31wt%, and the 29MA003 brand of French Arkema is used;
  • Hydrogenated styrene-butadiene block copolymer A the styrene content is 20wt%, the molecular weight is 300,000, and a commercially available product is used;
  • Hydrogenated styrene-butadiene block copolymer B1 the styrene content is 28wt%, the molecular weight is 300,000, and a commercially available product is used;
  • Hydrogenated styrene-butadiene block copolymer C the styrene content is 32wt%, the molecular weight is 300,000, and a commercially available product is used;
  • Hydrogenated styrene-butadiene block copolymer D the styrene content is 18wt%, the molecular weight is 300,000, and a commercially available product is used;
  • Hydrogenated styrene-butadiene block copolymer E the styrene content is 35wt%, the molecular weight is 300,000, and a commercially available product is used;
  • Hydrogenated styrene-butadiene block copolymer B2 the styrene content is 28wt%, the molecular weight is 250,000, and a commercially available product is used;
  • Hydrogenated styrene-butadiene block copolymer B3 the styrene content is 28wt%, the molecular weight is 150,000, and a commercially available product is used;
  • Hydrogenated styrene-butadiene block copolymer B4 the styrene content is 28wt%, the molecular weight is 350,000, and a commercially available product is used;
  • Hydrogenated styrene-butadiene block copolymer B5 the styrene content is 28wt%, the molecular weight is 450,000, and a commercially available product is used;
  • Rubber filler A KN4006 grade of PetroChina Karamay
  • Rubber filler oil B Maoming Petrochemical 32# white oil
  • SEBS grafted maleic anhydride A styrene content is 20wt%, molecular weight is 300,000, and grafting rate is 1%;
  • SEBS grafted maleic anhydride B styrene content of 28wt%, molecular weight of 300,000, grafting rate of 1%;
  • SEBS grafted maleic anhydride C styrene content is 33wt%, molecular weight is 300,000, and grafting rate is 1%;
  • SEBS grafted maleic anhydride D styrene content is 10wt%, molecular weight is 300,000, and grafting rate is 1%;
  • SEBS grafted maleic anhydride E styrene content is 40wt%, molecular weight is 300,000, and grafting rate is 1%;
  • a twin-screw with a length-to-diameter ratio of 48:1 is used, the initiator and maleic anhydride are fed in proportion to the side, and the processing temperature of the twin-screw extruder is 175-200° C. .
  • the commercially available molecular weight is 300,000, and SEBS of different styrene content grades is used for melt grafting;
  • Ethylene-octene copolymer POE 58750 from Dow Chemical is used, density: 0.870, melting index: 1g/10min under the condition of 190°C*2.16Kg;
  • Polyphenylene ether Bluestar Chemical LXR-045 grade
  • Magnesium Hydroxide adopts the magnesium hydroxide of Shandong Aifel Company with the grade of F5, and the average particle size is 1.5 ⁇ m;
  • Magnesium hydroxide coating in a high-speed mixer, heat magnesium hydroxide to 60°C, add 3-aminopropyltriethoxysilane in proportion; mix at high speed for 30 minutes;
  • Aluminum hypophosphite Lidao new material grade is M-116H, coated with melamine resin, and the average particle size is 10 ⁇ m;
  • Smoke suppressant 5 parts of nano-montmorillonite; 35 parts of ammonium octamolybdate; 40 parts of zinc borate;
  • Nano-montmorillonite was purchased from: Zhejiang Fenghong Co., Ltd. brand name is DK4;
  • Ammonium octamolybdate was purchased from: ammonium octamolybdate produced by Hubei Xinhongli Chemical Industry;
  • Zinc borate was purchased from: ZB-03 of Anhui Yishitong New Materials Co., Ltd.;
  • Antioxidant The combination of antioxidant 1010 and antioxidant 168 is used, and the mass ratio is 1:1;
  • step S2 the material after the drying of step S1 and ethylene-methyl acrylate copolymer, SEBS graft maleic anhydride, magnesium hydroxide, aluminum hypophosphite, smoke suppressant, antioxidant, lubricant are put into dense Mixing in a mill, mixing, cooling, discharging and granulation.
  • the temperature of the internal mixer is 145-160°C. Mixing time 15min.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Ethylene-methyl acrylate copolymer B 25 25 25 25 25 Ethylene-Octene Copolymer 25 25 25 25 25 Hydrogenated styrene-butadiene block copolymer B1 30 — — — — Hydrogenated styrene-butadiene block copolymer B2 — 30 — — — Hydrogenated styrene-butadiene block copolymer B3 — — 30 — — Hydrogenated styrene-butadiene block copolymer B4 — — 30 — Hydrogenated styrene-butadiene block copolymer B5 — — — — 30 SEBS grafted maleic anhydride B 4 4 4 4 4 Rubber filler oil A 8 8 8 8 8 polyphenylene ether 8 8 8 8 8 8 magnesium hydroxide 160 160 160 160 160 160 Aluminum hypophosphite 25 25 25 25
  • the Shore A hardness test method is tested by the method specified in GB 2411:
  • test method of the light transmittance of the finished product adopts the method specified in GB/T 17651-2008:
  • the hardness of the material is too high without the extended oil or the hydrogenated styrene-butadiene block copolymer; the hydrogenated styrene-butadiene block copolymer is insufficient, and the material hardness is too high; no When the hydrogenated styrene-butadiene block copolymer is grafted with maleic anhydride, the mechanical properties of the material cannot meet the requirements of the national standard; from the comparative example 3, if no aluminum hypophosphite is added, it needs to add more hydrogen Magnesium oxide can not meet the B1 level, and its Shore A hardness is relatively large.

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Abstract

本发明提供了一种超柔软B1级低烟无卤阻燃护套料及其制备方法。所述护套料包括如下按重量份计算的组分：乙烯-丙烯酸甲酯共聚物15～35份；乙烯-辛烯共聚物15～35份；氢化苯乙烯-丁二烯嵌段共聚物25～40份；橡胶填充油5～15份；SEBS接枝马来酸酐3～8份；聚苯醚3～8份；氢氧化镁120～170份；次磷酸铝10～35份；抑烟剂3～8份；抗氧剂1～3份；润滑剂1～3份；所述氢化苯乙烯-丁二烯嵌段共聚物中苯乙烯的含量为20～40wt％；所述次磷酸铝经过包覆处理。所述护套料的邵氏A硬度最大值为79A，满足B1级阻燃，成品透光率大于等于60％，具有符合标准的拉伸强度和断裂伸长率。能够应用于需要超柔软电缆护套的环境中。

Description

一种超柔软B1级低烟无卤阻燃护套料及其制备方法 技术领域
本发明涉及电缆护套料领域，更具体地，涉及一种超柔软B1级低烟无卤阻燃护套料及其制备方法。
背景技术
GB/T 31247 B1级阻燃电缆，主要应用于机场、车站、轨道交通、大型楼宇等人口密集场合。GB/T 31247 B1级阻燃相比于GB/T 19666和GB/T 17651，对护套材料的热释放和烟释放性能有更高的要求，传统护套材料较难满足，同时因为低烟无卤阻燃电缆料，采用大量金属氢氧化物填充，导致材料普遍偏硬，邵氏A硬度都非常大，若是做有卤阻燃的电缆料，第一是会引起环保问题，第二是也不符合GB/T 31247 B1标准。
对于建筑内部比较复杂的电缆线路，或者应用于需要柔软度较高的场景，就需要柔软度比较高的护套料，例如有些电缆的铺设空间有限，如海洋平台，为了节省空间，便于铺设，就要求电缆有较小的弯曲半径。为了使电缆获得较小的弯曲半径，一方面电缆结构要设计的合理，易于弯曲，另一方面电缆的护套层材料要柔软，能够大幅度弯曲。赋予电缆柔软的特点有助于施工时的铺设。硬度偏高的材料不利于施工。
但是硬度较低的材料，材料容易软化，耐温性能不好，在成束燃烧时(高等级成束燃烧需要燃烧20分钟)，如果成炭效率不够，无法及时保护电缆内部可燃机构，容易引起箱体温度过高(超过100℃)，导致护套脱落，从而阻燃失效。因此柔软护套料要达到B1级别非常困难。
中国专利(CN104672743A)公开了一种耐油耐腐蚀超柔软电缆护套料及其制备方法，虽然其满足了超柔软的性能，但是阻燃不能满足B1级阻燃性能。
发明内容
本发明为克服上述现有技术所述的不能同时满足柔软度和B1级阻燃的缺陷，提供一种超柔软B1级低烟无卤阻燃护套料。
本发明的另一目的在于提供所述超柔软B1级低烟无卤阻燃护套料的制备方法。
本发明的另一目的在于提供所述超柔软B1级低烟无卤阻燃的电缆护套。
为实现上述目的，本发明采用的技术方案是：
一种超柔软B1级低烟无卤阻燃护套料，包括如下按重量份计算的组分：
Figure PCTCN2021138867-appb-000001
所述氢化苯乙烯-丁二烯嵌段共聚物中苯乙烯的含量为20～40wt％；
所述次磷酸铝经过包覆处理。
本发明首先采用苯乙烯含量为20～40wt％的氢化苯乙烯-丁二烯嵌段共聚物、橡胶填充油共混来降低树脂的硬度，大大提高了材料的柔软性能；其中，氢化苯乙烯-丁二烯嵌段共聚物的苯乙烯含量在20～40％时具有极佳的柔软度，与橡胶填充油充分混合后使得在基体树脂分布的更均匀，进一步的提高了其柔软度；同时利用聚苯醚、SEBS接枝马来酸酐和氢化苯乙烯-丁二烯嵌段共聚物的优良相容性，大大提高了材料的力学性能；采用经过包覆处理的次磷酸铝、氢氧化镁和抑烟剂复配，一方面降低了氢氧化镁的含量，提高了柔软度，另一方面，能够提高阻燃还能抑制次磷酸铝带来的高烟含量。氢氧化镁和次磷酸铝搭配，可以获得很好的阻燃成炭效果。次磷酸铝为酸性物质，氢氧化镁为弱碱性物质，次磷酸铝经过包覆处理有效避免和氢氧化镁进行反应，导致阻燃失效。
所述次磷酸铝经过密胺树脂包覆。
优选地，所述乙烯-丙烯酸甲酯共聚物中甲基丙烯酸含量为18～36wt％。当甲基丙烯酸含量在18～36wt％，其树脂具有较好的拉伸强度。
优选地，所述氢化苯乙烯-丁二烯嵌段共聚物的分子量大于等于25万。提高 氢化苯乙烯-丁二烯嵌段共聚物的拉伸强度。
所述橡胶填充油为环烷基橡胶油、石蜡基橡胶油。
优选地，所述SEBS接枝马来酸酐中苯乙烯含量为20～40wt％。当苯乙烯含量在20～40wt％内时，具有较好的柔软度。
优选地，所述SEBS接枝马来酸酐的接枝率大于等于0.8％。
所述接枝率的测定采用常规的方法即可，例如采用酸碱滴定法。
优选地，所述次磷酸铝的平均粒径小于等于50μm。平均粒径小于等于50μm时具有较好的阻燃性能。
优选地，所述氢氧化镁的平均粒径小于等于1.5μm。平均粒径小于等于1.5μm时具有较好的阻燃性能。
所述氢氧化镁表面采用3-氨丙基三乙氧基硅烷包覆处理，包覆率＞80％
优选地，所述抑烟剂为纳米蒙脱土、八钼酸铵和硼酸锌的混合物，其中，按重量计，纳米蒙脱土5～25分；八钼酸铵为35～55份；硼酸锌为20～40份。
所述聚苯醚的分子量为20000-60000，为粉体PPO，平均粒径在20-100μm之间。
所述乙烯-辛烯共聚物的熔融指数在190℃，2.16Kg负重条件下测试为0.5～3g/10min，密度为0.87-0.895g/cm 3。
本发明还提供所述超柔软B1级低烟无卤阻燃护套料的制备方法，包括如下步骤：
S1.按比例将氢化苯乙烯-丁二烯嵌段共聚物和橡胶填充油先预混合，静置，再混合乙烯-辛烯共聚物、聚苯醚，经双螺杆挤出机挤出、造粒、烘干。
所述双螺杆挤出机的长径比L/D＝48，各区设定温度为160-200℃。
S2.将步骤S1的烘干后的物料和乙烯-丙烯酸甲酯共聚物、SEBS接枝马来酸酐、氢氧化镁、次磷酸铝、抑烟剂、抗氧剂、润滑剂按比例投入到密炼机中混炼，混炼、冷却、出料并进行造粒。
所述密炼机的温度为145～160℃。密炼时间不低于10min。
所述超柔软B1级低烟无卤阻燃护套料制备电缆护套中的应用。
与现有技术相比，本发明的有益效果是：
本发明提供一种超柔软B1级低烟无卤阻燃电缆护套料，采用苯乙烯含量为20～40wt％的氢化苯乙烯-丁二烯嵌段共聚物、橡胶填充油和SEBS接枝马来酸酐 共混来降低树脂的硬度，大大提高了材料的柔软性能。所述护套料的邵氏A硬度最大值为79A，满足B1级阻燃，成品透光率大于等于60％，具有符合标准的拉伸强度和断裂伸长率，能够应用于需要超柔软电缆护套的环境中。
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：
乙烯-丙烯酸甲酯共聚物A：甲基丙烯酸含量为18wt％，采用的是埃克森美孚的TC 121 Molding牌号；
乙烯-丙烯酸甲酯共聚物B：甲基丙烯酸含量为20wt％，采用的是法国阿科玛的的20MA08牌号；
乙烯-丙烯酸甲酯共聚物C：甲基丙烯酸含量为24wt％，采用的是法国阿科玛的的24MA005牌号；
乙烯-丙烯酸甲酯共聚物D：甲基丙烯酸含量为10wt％，采用的是美国西湖化工的SP1402牌号；
乙烯-丙烯酸甲酯共聚物E：甲基丙烯酸含量为31wt％，采用的是法国阿科玛的的29MA003牌号；
氢化苯乙烯-丁二烯嵌段共聚物A：苯乙烯含量20wt％，分子量为30万采用市售产品；
氢化苯乙烯-丁二烯嵌段共聚物B1：苯乙烯含量28wt％，分子量为30万采用市售产品；
氢化苯乙烯-丁二烯嵌段共聚物C：苯乙烯含量32wt％，分子量为30万采用市售产品；
氢化苯乙烯-丁二烯嵌段共聚物D：苯乙烯含量18wt％，分子量为30万采用市售产品；
氢化苯乙烯-丁二烯嵌段共聚物E：苯乙烯含量35wt％，分子量为30万采用市售产品；
氢化苯乙烯-丁二烯嵌段共聚物B2：苯乙烯含量28wt％，分子量为25万采 用市售产品；
氢化苯乙烯-丁二烯嵌段共聚物B3：苯乙烯含量28wt％，分子量为15万采用市售产品；
氢化苯乙烯-丁二烯嵌段共聚物B4：苯乙烯含量28wt％，分子量为35万采用市售产品；
氢化苯乙烯-丁二烯嵌段共聚物B5：苯乙烯含量28wt％，分子量为45万采用市售产品；
橡胶填充油A：采用中石油卡拉玛依的KN4006牌号；
橡胶填充油B：采用茂名石化32#白油；
SEBS接枝马来酸酐A：苯乙烯含量20wt％，分子量为30万，接枝率1％；
SEBS接枝马来酸酐B：苯乙烯含量28wt％，分子量为30万，接枝率1％；
SEBS接枝马来酸酐C：苯乙烯含量33wt％，分子量为30万，接枝率1％；
SEBS接枝马来酸酐D：苯乙烯含量10wt％，分子量为30万，接枝率1％；
SEBS接枝马来酸酐E：苯乙烯含量40wt％，分子量为30万，接枝率1％；
所述SEBS接枝马来酸酐的制备，采用长径比为48：1双螺杆，将引发剂和马来酸酐按比例在侧喂料喂料，双螺杆挤出机加工温度为175-200℃。选用市售分子量为30万，不同苯乙烯含量牌号SEBS进行熔融接枝；
乙烯-辛烯共聚物：采用的是陶氏化学的POE 58750，密度为：0.870，熔指：190℃*2.16Kg条件下为1g/10min；
聚苯醚：采用的蓝星化学LXR-045牌号；
氢氧化镁：氢氧化镁采用山东艾弗尔公司牌号为F5的氢氧化镁，平均粒径为1.5μm；
氢氧化镁包覆；在高混机中，将氢氧化镁加热到60℃，按比例加入3-氨丙基三乙氧基硅烷；高速混合30分钟；
次磷酸铝：力道新材牌号为M-116H，密胺树脂包覆，平均粒径为10μm；
抑烟剂：纳米蒙脱土5份；八钼酸铵为35份；硼酸锌为40份；
纳米蒙脱土购自：浙江丰虹股份有限公司牌号为DK4；
八钼酸铵购自：湖北鑫红利化工产八钼酸铵；
硼酸锌购自：安徽壹石通新材料股份有限公司的ZB-03；
抗氧剂：采用抗氧剂1010和抗氧剂168组合，质量比为1:1；
润滑剂：采用霍尼韦尔聚乙烯蜡AC-6A。
下面结合实施例和对比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超柔软B1级低烟无卤阻燃护套
料，按照表1～3的重量比称取各组分；具体步骤如下：
S1.按比例将氢化苯乙烯-丁二烯嵌段共聚物和橡胶填充油先预混合，静置，再混合乙烯-辛烯共聚物、聚苯醚，经双螺杆挤出机挤出、造粒、烘干。
所述双螺杆挤出机的长径比L/D＝48，各区设定温度为160-200℃。
S2.将步骤S1的烘干后的物料和乙烯-丙烯酸甲酯共聚物、SEBS接枝马来酸酐、氢氧化镁、次磷酸铝、抑烟剂、抗氧剂、润滑剂按比例投入到密炼机中混炼，混炼、冷却、出料并进行造粒。
所述密炼机的温度为145～160℃。密炼时间15min。
实施例1～5
表1实施例1～5的配方(份)
  实施例1 实施例2 实施例3 实施例4 实施例5
乙烯-丙烯酸甲酯共聚物B 25 25 25 25 25
乙烯-辛烯共聚物 25 25 25 25 25
氢化苯乙烯-丁二烯嵌段共聚物B1 30 — — — —
氢化苯乙烯-丁二烯嵌段共聚物B2 — 30 — — —
氢化苯乙烯-丁二烯嵌段共聚物B3 — — 30 — —
氢化苯乙烯-丁二烯嵌段共聚物B4 — — — 30 —
氢化苯乙烯-丁二烯嵌段共聚物B5 — — — — 30
SEBS接枝马来酸酐B 4 4 4 4 4
橡胶填充油A 8 8 8 8 8
聚苯醚 8 8 8 8 8
氢氧化镁 160 160 160 160 160
次磷酸铝 25 25 25 25 25
抑烟剂 4 4 4 4 4
抗氧剂 2 2 2 2 2
润滑剂 2 2 2 2 2
实施例6～12
表2实施例6～12的配方(份)
Figure PCTCN2021138867-appb-000002
实施例13～19
表3实施例13～19的配方(份)
Figure PCTCN2021138867-appb-000003
Figure PCTCN2021138867-appb-000004
对比例1～6
表4对比例1～6的配方(份)
  对比例1 对比例2 对比例3 对比例4 对比例5 对比例6
乙烯-丙烯酸甲酯共聚物B 25 25 25 25 25 25
乙烯-辛烯共聚物B 25 25 25 25 25 25
氢化苯乙烯-丁二烯嵌段共聚物B1 — 20 20 20 — —
氢化苯乙烯-丁二烯嵌段共聚物D — — — — 20 —
氢化苯乙烯-丁二烯嵌段共聚物E — — — — — 20
SEBS接枝马来酸酐B 4 — 4 4 4 4
橡胶填充油 8 8 8 — 8 8
聚苯醚 8 8 8 8 8 8
氢氧化镁 160 160 195 160 160 160
次磷酸铝 25 25 — 25 25 25
抑烟剂 4 4 4 4 4 4
抗氧剂 2 2 2 2 2 2
润滑剂 2 2 2 2 2 2
将上述实施例1～19和对比例1～6制备得到的超柔软B1级低烟无卤阻燃电缆护套料进行以下性能测试，测试所参照标准和方法如下：
根据GB/T 32129-2015低烟无卤材料标准和GB 31247-2014 B1阻燃等级标准的测试方法，
邵氏A硬度测试方法采用GB 2411规定方法测试：
成品透光率的测试方法采用GB/T 17651-2008规定方法测试：
表5各实施例和对比例的测试数据
Figure PCTCN2021138867-appb-000005
从实施例1～5看，氢化苯乙烯-丁二烯嵌段共聚物的分子量越高，材料的力学性能越好。
从实施例1和6～8看，氢化苯乙烯-丁二烯嵌段共聚物的苯乙烯含量越低，材料的硬度越低，柔软性能越好，但是拉伸强度也有所下降。
从实施例1和9～12看，SEBS接枝马来酸酐的苯乙烯含量越低，材料的硬度越低，柔软性能越好，
从实施例1和13～16看，乙烯-丙烯酸甲酯共聚物的甲基丙烯酸含量越高，材料的烟密度性能越好，同时力学也有提高，甲基丙烯酸含量不影响材料的柔软度。
从实施例17～19看，填充油含量越高，材料的硬度越低，但是材料的力学性能会有一定的下降。
从对比例1～6看，无填充油或者氢化苯乙烯-丁二烯嵌段共聚物情况下，材料硬度过高；氢化苯乙烯-丁二烯嵌段共聚物不足，材料硬度过高；无氢化苯乙烯-丁二烯嵌段共聚物接枝马来酸酐情况下，材料的力学性能不能满足国标要求；从对比例3看，若不加次磷酸铝条件下，其需要加入更多的氢氧化镁都不能满足B1级，且其邵氏A硬度的较大。
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. 一种超柔软B1级低烟无卤阻燃护套料，其特征在于，包括如下按重量份计算的组分：
    Figure PCTCN2021138867-appb-100001
    所述氢化苯乙烯-丁二烯嵌段共聚物中苯乙烯的含量为20～40wt％；
    所述次磷酸铝经过包覆处理。
  2. 根据权利要求1所述超柔软B1级低烟无卤阻燃护套料，其特征在于，所述乙烯-丙烯酸甲酯共聚物中甲基丙烯酸含量为18～36wt％。
  3. 根据权利要求1所述超柔软B1级低烟无卤阻燃护套料，其特征在于，所述氢化苯乙烯-丁二烯嵌段共聚物的分子量大于等于25万。
  4. 根据权利要求1所述超柔软B1级低烟无卤阻燃护套料，其特征在于，所述SEBS接枝马来酸酐中苯乙烯含量为20～40wt％。
  5. 根据权利要求1所述超柔软B1级低烟无卤阻燃护套料，其特征在于，所述SEBS接枝马来酸酐的接枝率大于等于0.8％。
  6. 根据权利要求1所述超柔软B1级低烟无卤阻燃护套料，其特征在于，所述次磷酸铝的平均粒径小于等于50μm。
  7. 根据权利要求1所述超柔软B1级低烟无卤阻燃护套料，其特征在于，所述氢氧化镁的平均粒径小于等于1.5μm。
  8. 根据权利要求1所述超柔软B1级低烟无卤阻燃护套料，其特征在于，所述抑烟剂为纳米蒙脱土、八钼酸铵和硼酸锌的混合物，其中，按重量计，纳米蒙 脱土5～25分；八钼酸铵为35～55份；硼酸锌为20～40份。
  9. 根据权利要求1～8任一项所述超柔软B1级低烟无卤阻燃护套料的制备方法，其特征在于，包括如下步骤：
    S1.按比例将氢化苯乙烯-丁二烯嵌段共聚物和橡胶填充油先预混合，静置，再混合乙烯-辛烯共聚物、聚苯醚，经双螺杆挤出机挤出、造粒、烘干。
    S2.将步骤S1的烘干后的物料和乙烯-丙烯酸甲酯共聚物、SEBS接枝马来酸酐、氢氧化镁、次磷酸铝、抑烟剂、抗氧剂、润滑剂按比例投入到密炼机中密炼、出料并进行造粒。
  10. 一种电缆护套，含有权利要求1～8任一项所述超柔软B1级低烟无卤阻燃护套料。
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