WO2023193293A1 - 用于生产电缆中聚碳酸酯骨架的组合物及骨架的制造方法 - Google Patents

用于生产电缆中聚碳酸酯骨架的组合物及骨架的制造方法 Download PDF

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WO2023193293A1
WO2023193293A1 PCT/CN2022/087622 CN2022087622W WO2023193293A1 WO 2023193293 A1 WO2023193293 A1 WO 2023193293A1 CN 2022087622 W CN2022087622 W CN 2022087622W WO 2023193293 A1 WO2023193293 A1 WO 2023193293A1
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parts
composition
skeleton
agent
producing polycarbonate
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French (fr)
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代康
郭志宏
钱熙文
唐青
郭雪雅
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江苏俊知技术有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to the technical field of communication cable materials, in particular to a composition for producing a polycarbonate skeleton in data cables and a method for manufacturing the skeleton.
  • the operating frequency of symmetrical data cables specified by standards such as YD/T 838 "Twisted Pair/Star Pair Symmetrical Cables for Digital Communications" has been increased to 2000MHz.
  • the key indicators that affect the high-frequency signal transmission performance of cables are the crosstalk and transmission attenuation of the wire pairs. These two properties directly affect the signal-to-noise ratio of the signal and determine the bandwidth of the transmitted signal. For this reason, a skeleton is usually introduced into the core structure of the data cable to separate each wire pair in the cable (usually a cable has 4 wire pairs) to improve the crosstalk attenuation between the wire pairs.
  • Such a skeleton is usually in the shape of a cross, such as the structure that has been widely used in the industry and shown in patent documents such as CN101556843A and CN105575512B. For this reason, the skeleton should have a certain strength and not be easily deformed, so as to maintain the stability of the position of the line pair.
  • data cable skeletons generally use polyolefin materials that are consistent with the wire-pair insulation materials (such as high-density polyethylene, linear low-density polyethylene, and polypropylene), and are extruded using a single-screw extruder to form a solid-structure skeleton.
  • wire-pair insulation materials such as high-density polyethylene, linear low-density polyethylene, and polypropylene
  • the processed skeleton has the characteristics of high elongation at break and can meet the transmission performance requirements of Category 6e data cables.
  • the above materials and solid structures have the following disadvantages:
  • the skeleton is not flame retardant, which increases the difficulty of cable flame retardancy. Therefore, sheath materials with good flame retardancy must be used and the thickness of the sheath must be increased, which greatly increases the cost of cable materials;
  • the skeleton is not strong enough and is easy to deform. For this reason, two measures have to be taken to compensate. One is to increase the thickness of the skeleton, but this has a negative impact on the cable transmission attenuation and flame retardancy, and causes the cable size to change. Large, increase the cable installation cost in the cable manufacturing and integrated wiring process; the second is to reduce the twisting pitch of the wire pairs, but this will lead to a reduction in the efficiency of the wire pair twisting process and also increase the cable manufacturing cost.
  • the technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a composition for producing polycarbonate skeletons in cables and a method for manufacturing the skeletons.
  • composition for producing polycarbonate skeleton in cables including the following raw materials in parts by weight:
  • composition for producing polycarbonate skeleton in cables also includes a nucleating agent, the weight part of which is 0.2 to 1.0 parts.
  • the polycarbonate has a melt mass flow rate of 3 to 15 g/10 min.
  • the weight part of the polyethylene terephthalate recycled material is 8.0 to 12.0 parts.
  • the flame retardant is tris(2,4-dibromophenyl)phosphate halogenated phosphate composite flame retardant, and its weight part is 10 to 20.0 parts;
  • the flame retardant is a brominated polymer flame retardant, and its weight part is 3.0 to 12.0 parts.
  • the weight part of the tris(2,4-dibromophenyl)phosphate halogenated phosphate composite flame retardant is 12.0 to 15.0 parts; the brominated polymer flame retardant is brominated polystyrene , its weight part is 5.0 to 7.5 parts.
  • the anti-drip agent is polytetrafluoroethylene powder, SJ-D100S anti-drip agent or DF-S10 anti-drip agent, and its weight part is 0.3 to 0.6 parts.
  • the chemical foaming agent is a high-temperature foaming agent or a low-temperature foaming agent.
  • the extrusion foaming temperature is ⁇ 260°C
  • the chemical foaming agent is a high-temperature foaming agent; when the extrusion foaming temperature is ⁇ 260°C
  • low-temperature foaming agent is used.
  • the lubricant is talc powder or calcium stearate, and its weight part is 1.0 to 4.0 parts;
  • the lubricant is a small molecule polymer, and its weight part is 0.2 to 0.5 parts.
  • a method for manufacturing a skeleton, using the above-mentioned composition for producing polycarbonate skeletons in cables as raw materials to produce the skeleton specifically including the following steps:
  • Extrusion foaming Feed the compound material mixed in S1 into the feeding port of the co-rotating twin-screw extruder.
  • the length-to-diameter ratio of the twin-screw extruder is ⁇ 30.
  • the twin-screw extruder starts from extrusion. From the barrel to the machine head, the extrusion temperature gradually increases, and the extrusion temperature is 260 to 290°C.
  • the data cable core is made into a "cross-shaped" skeleton by extrusion foaming.
  • the beneficial effects of the invention are: the invention has reasonable design and is easy to operate.
  • the polycarbonate skeleton in the data cable core produced by the invention has the characteristics of flame retardancy and high strength, improves the transmission performance of the data cable, and at the same time has low production cost.
  • Figure 1 is a schematic structural diagram of the skeleton in the present invention.
  • a composition for producing polycarbonate skeleton in cables including the following raw materials in parts by weight:
  • composition for producing polycarbonate skeleton in cables also includes a nucleating agent, the weight part of which is 0.2 to 1.0 parts.
  • Polycarbonate is selected with medium melt viscosity. Its melt mass flow rate (300°C/1.2kg) is tested according to the GB/T 3682.1-2018 standard. It is suitable to be (3 ⁇ 15)g/10min, preferably ( 5 ⁇ 12)g/10min. Melt viscosity is usually proportional to melt strength. Therefore, low melt viscosity often results in rupture of foam cells, rough and poor appearance of the skeleton, and reduced skeleton strength. Too high melt viscosity leads to low extrusion efficiency, so extrusion molding has to be improved. molding temperature, but this is not conducive to foaming. PC can choose 1300-10NP from South Korea's LG Chemical Company, FG-60 from Sinopec Yizheng Chemical Fiber Co., Ltd., PC 201-15 from South Korea's Dow Polycarbonate Co., Ltd. and other products.
  • PET film waste can be added to the plastic crusher, broken into small pieces, dried in a hopper at (70 ⁇ 90)°C for 4 hours, and then directly added to the skeleton mixture material, or re-granulated. Then add it in the form of pellets.
  • PET and PC have complementary effects in terms of performance. For example, PET has poor flame retardancy and produces droplets when burning, while PC itself has certain flame retardancy. Its flame retardant rating can reach UL94V-2 and can self-extinguish. The carbon rate is high; after PC extrusion, some internal stress will remain, which may cause cracking under long-term bending stress, while PET can improve its flexibility.
  • the flame retardant is tris(2,4-dibromophenyl) phosphate (TDBPPE) halogenated phosphate composite flame retardant.
  • TDBPPE tris(2,4-dibromophenyl) phosphate
  • the added weight of the flame retardant is 10 to 20.0 parts, preferably For 12.0 to 15.0 parts, you can choose PX-220 from Zhejiang Wansheng Technology Co., Ltd.;
  • the flame retardant is a brominated polymer flame retardant, and brominated polystyrene (BPS) flame retardant can be used.
  • BPS brominated polystyrene
  • the amount of BPS added is 3.0 to 12.0 parts, preferably 5.0 to 12.0 parts. 7.5 parts; BPS can choose BPS-301 product of Shenyang Zhengxing Materials Co., Ltd.
  • the amount of anti-drip agent added is 0.3 to 0.6 parts by weight.
  • the anti-drip agent can further improve the shell-forming properties of the skeleton when burning, avoid the occurrence of burning droplets, and thus improve the flame retardant performance of the cable.
  • Anti-drip agents can be polytetrafluoroethylene (PTFE) powder produced by Shanghai Luju Polymer Company, SJ-D100S anti-drip agent from Jiashan Shenjia Technology Co., Ltd., and DF-S10 anti-drip agent from Guangzhou Baojiu Chemical Technology Co., Ltd. Dropping agent, etc.
  • the skeleton foam structure will reduce the impact of the skeleton on the cable centerline on transmission attenuation. For this reason, 0.3 to 3.0 parts by weight of chemical foaming agent should be added to every 100 parts by weight of PC.
  • the selected chemical foaming agent should decompose and release gas at a higher temperature. If it is too low, the foaming agent will decompose prematurely in the feeding section of the machine chamber, and part of the gas will It leaks out from the feeding port and reduces the foaming degree, causing waste of foaming agent and uneven foaming degree.
  • the temperature of the twin-screw extruder is set from the first barrel (feeding section) to the machine head (260 ⁇ 310)°C, that is, when the temperature of the machine chamber in the rear section near the feeding port is relatively high, use a mold suitable for high-temperature foaming.
  • Barium azodicarboxylate and barium azodicarboxylate are used as foaming agents; other special foaming agents sold on the market can also be used, such as OnCapPolyFoam chemical foaming agent from Polyone Company in the United States and foaming agent from Shanghai Jieshangjie Chemical Co., Ltd. Agent LDM 10070S.
  • the extrusion foaming temperature of the skeleton mixture can be controlled below 260°C, for example, the temperature from the feed port to the extruder head gradually increases from 230°C to 255°C, azodicarbonamide (AC) is used as the chemical foaming agent .
  • AC azodicarbonamide
  • nucleating agent added to the matrix composition will help achieve uniformly sized foam cells.
  • the residue after the decomposition of the chemical foaming agent can be used as a nucleating agent for foaming, but it is often not enough. Therefore, for every 100 parts by weight of PC, add 0.2 to 1 part of nucleating agent as a supplement, preferably 0.4 to 0.6
  • the optional nucleating agent is P250 product from Brueggemann of Germany. When PTFE powder is selected as the anti-drip agent, the PTFE powder acts as a nucleating agent during the extrusion foaming process, so no additional nucleating agent is needed.
  • a processing lubricant is added to the skeleton composition.
  • PC For every 100 parts by weight of PC, add 1 to 4 parts by weight of talc or calcium stearate. You can choose calcium stearate from Shanghai Aoke Chemicals Co., Ltd. You can also add 0.2 to 0.5 parts by weight of small molecule polymer to every 100 parts by weight of PC, and use the fatty acid ester A lubricant from Italian Hair Base Company.
  • the advantage is that the addition amount is low, does not affect foaming, and is beneficial to improve The strength of the skeleton.
  • a method for manufacturing a skeleton, using the above-mentioned composition for producing polycarbonate skeletons in cables as raw materials to produce the skeleton specifically including the following steps:
  • the high mechanical strength makes the skeleton less likely to deform when the cable is subjected to external forces and during use, thereby avoiding the degradation of cable crosstalk performance; adopting GB/T 2406 -The oxygen index obtained by the 2009 standard test is not less than 30; the flame retardant performance obtained by the test according to GB/2408-2008 reaches the vertical V-0 level (sample thickness is 3mm); after the sample is tested and passed, each component can be determined parts by weight;
  • the foaming degree of the skeleton can be adjusted.
  • the decomposition temperature and machine head temperature cannot be higher than the maximum temperature of the barrel by more than 5°C, and the foaming degree can be improved.
  • the mass per unit length of the skeleton obtained by foam extrusion is 15% to 30% lower than that of the unfoamed skeleton, and the transmission attenuation of the line pair at 500MHz is reduced by an average of 2%.
  • a composition for producing polycarbonate skeleton in cable cores including the following raw materials in parts by weight:
  • PET return material 8.0 parts
  • Flame retardant TDBPPE 12.0 parts, PX-220 from Zhejiang Wansheng Technology Co., Ltd.;
  • Anti-drip agent and nucleating agent PTFE powder, 0.4 parts, produced by Shanghai Luju Polymer Company;
  • Chemical foaming agent 1.5 parts, foaming agent from Shanghai Jieshangjie Chemical Co., Ltd.;
  • Lubricant 0.2 parts, fatty acid ester A from Italian Fatty Company.
  • a composition for producing polycarbonate skeleton in cable cores including the following raw materials in parts by weight:
  • PC 100.0 parts, PC 201-15 of Korea Dow Polycarbonate Co., Ltd.;
  • PET recycled material 10.0 parts
  • BPS flame retardant 8.0 parts, BPS–301 from Shenyang Zhengxing Materials Co., Ltd.;
  • Anti-drip agent 1.0 parts, DF-S10 anti-drip agent from Guangzhou Baojiu Chemical Technology Co., Ltd.;
  • Barium azodicarboxylate chemical foaming agent 1.5 parts;
  • Lubricant 0.5 parts, calcium stearate from Shanghai Aoke Chemicals Co., Ltd.
  • a composition for producing polycarbonate skeleton in cable cores including the following raw materials in parts by weight:
  • PC 100.0 parts, PC 201-15 of Korea Dow Polycarbonate Co., Ltd.;
  • PET recycled material 10.0 parts
  • BPS flame retardant 8.0 parts, BPS–301 from Shenyang Zhengxing Materials Co., Ltd.;
  • Anti-drip agent 1.0 parts, DF-S10 anti-drip agent from Guangzhou Baojiu Chemical Technology Co., Ltd.;
  • Lubricant 0.5 parts, calcium stearate from Shanghai Aoke Chemicals Co., Ltd.
  • This invention takes HSYV-6 4 ⁇ 2 ⁇ 0.57 cable as an example, as shown in Figure 1.
  • the size of the skeleton can be reduced. Its diameter D is 5.0 mm, and its thickness t is 0.5 mm.
  • Polycarbonate cross-shaped skeleton is used to produce data cables.
  • the maximum pair twisting pitch of the four wire pairs is controlled below 16mm, the minimum wire pair twisting pitch is controlled below 11mm, and the average twisting pitch of the four wire pairs An increase of 15%, in other words, the stranding production efficiency is increased by 15%; the cable PVC sheath can be made of ordinary flame-retardant PVC sheath material with a combustion performance reaching the vertical V-1 level and an oxygen index of not less than 28.
  • the thickness of the sleeve is reduced from 0.75mm to 0.63mm, and the outer diameter of the cable is reduced from 7.0mm to 6.5mm.
  • the minimum value of the line-pair near-end crosstalk attenuation power sum (PS NEXT) is 38.0dB
  • the equal-level far-end crosstalk attenuation power sum (PS ACR-F) is minimum 19.3dB/100m
  • attenuation is 31.0dB/100m.
  • the diameter D of the skeleton is 5.3mm, and the thickness t is 0.7mm.
  • the maximum wire pair twisting pitch of the four wire pairs must be controlled below 14mm, and the minimum wire pair twisting pitch must be controlled below 9mm.
  • the key to the cable obtained in this way is at the frequency of 250MHz.
  • the transmission performance can only maintain the following levels: the line pair near-end crosstalk attenuation power sum (PS NEXT) is 36.5dB, the equal-level far-end crosstalk attenuation power sum (PS EL FEXT) is 18.0dB/100m, and the attenuation is 32.1dB /100m, just meets the standard requirements; in order to make the cable flame retardant level reach the vertical flame spread test of a single insulated wire and cable in the combustion test, the cable polyvinyl chloride (PVC) sheath must use flame retardant properties to reach vertical V-0 Highly flame-retardant PVC sheath material with grade and oxygen index not less than 38, and the sheath thickness is 0.75mm. The final outer diameter of the cable is 7.0mm.
  • PVC polyvinyl chloride
  • the crosstalk performance and attenuation performance of the present invention are significantly improved compared with the traditional cross-shaped skeleton cable.
  • Comparative Example 1 uses a solid extrusion process to obtain a polycarbonate skeleton.
  • the skeleton size, wire pair twisting pitch, sheath thickness, etc. are the same as those of the cables produced in Example 2 and Example 1. It can be seen that the cable crosstalk performance is basically the same. There is no change, that is, there is a significant improvement compared with the traditional skeleton; however, there is no significant improvement in cable attenuation. This shows that chemical foaming of the skeleton can not only reduce the weight of the cable and save materials, but also improve the attenuation of the cable.

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Abstract

本发明涉及一种用于生产电缆中聚碳酸酯骨架的组合物及骨架的制造方法。这种用于生产电缆缆芯中聚碳酸酯骨架的组合物，包括如下重量份的原料：聚碳酸酯100.0份，聚对苯二甲酸乙二酯再生料5.0～20.0份，阻燃剂3.0～20.0份，抗滴落剂0.2～1.0份，化学发泡剂0.3～3.0份和润滑剂0.2～4.0份。本发明设计合理，操作简便，制得的数据电缆缆芯中聚碳酸酯骨架具有阻燃性和高强度的特点，提高了数据电缆的传输性能，同时生产成本低。

Description

用于生产电缆中聚碳酸酯骨架的组合物及骨架的制造方法 技术领域
本发明涉及通信电缆材料技术领域，尤其是一种用于生产数据电缆中聚碳酸酯骨架的组合物及骨架的制造方法。
背景技术
由YD/T 838《数字通信用对绞/星绞对称电缆》等标准规定的对称数据缆，其工作频率已升至2000MHz。影响电缆高频信号传输性能的关键指标有线对的串音和传输衰减，这两项性能直接影响信号的信噪比，决定了传输信号的带宽。为此，通常在数据缆的缆芯结构中引入将缆中各个线对(通常一根电缆有4个线对)分隔开来的骨架，以此提高线对之间的串音衰减。这样的骨架通常为十字形，例如早在业界普遍采用、CN101556843A和CN105575512B等专利文献中展示的结构。为此骨架应具有一定的强度，不会轻易变形，以此保持线对位置的稳定。
此外，由于对称电缆线对信号电磁场具有开放的特点，因此骨架所用材料的介电性能也将对线对的传输衰减性能产生影响。
另一方面，由于数据缆多为室内使用，而且有些场合对电缆安全性极为敏感，因此对数据缆的阻燃性也提出了越来越严格的要求。
目前，数据缆骨架普遍采用与线对绝缘料一致的聚烯烃材料(如高密度聚乙烯、线性低密度聚乙烯、聚丙烯)，采用单螺杆挤塑机挤塑加工制成实心结构的骨架。其加工技术成熟，生产效率高，加工的骨架具有断裂伸长率高的特点，能满足超六类数据缆的传输性能要求。然而，上述材料和实心结构却具有如下 缺点：
(1)、骨架不具有阻燃性，增加了电缆阻燃的难度，为此不得不采用阻燃性好的护套料，并且提高护套厚度，这大幅度增加了电缆材料成本；
(2)、骨架强度不够，易于变形，为此不得不采用两条措施加以弥补，其一是加大骨架厚度，但这对电缆传输衰减和阻燃性带来负面影响，并导致电缆尺寸变大，增加了电缆制造和综合布线过程中的电缆安装成本；其二是降低线对的绞合节距，但这样将导致线对绞合工序效率降低，也加大了电缆制造成本。
发明内容
本发明要解决的技术问题是：克服现有技术中之不足，提供用于生产电缆中聚碳酸酯骨架的组合物及骨架的制造方法。
本发明解决其技术问题所采用的技术方案是：一种用于生产电缆中聚碳酸酯骨架的组合物，包括如下重量份的原料：
Figure PCTCN2022087622-appb-000001
进一步地，所述用于生产电缆中聚碳酸酯骨架的组合物还包括成核剂，其重量份为0.2～1.0份。
进一步地，所述聚碳酸酯的熔体质量流动速率为3～15g/10min。
进一步地，所述聚对苯二甲酸乙二酯再生料的重量份为8.0～12.0份。
进一步地，所述阻燃剂为磷酸三(2,4-二溴苯基)酯卤代磷酸酯复合阻燃剂，其重量份为10～20.0份；
或者，所述阻燃剂为溴系高分子阻燃剂，其重量份为3.0～12.0份。
进一步地，所述磷酸三(2,4-二溴苯基)酯卤代磷酸酯复合阻燃剂的重量份为12.0～15.0份；所述溴系高分子阻燃剂为溴化聚苯乙烯，其重量份为5.0～7.5份。
进一步地，所述抗滴落剂为聚四氟乙烯粉末、SJ-D100S抗滴落剂或DF-S10抗滴落剂，其重量份为0.3～0.6份。
进一步地，所述化学发泡剂为高温发泡剂或低温发泡剂，当挤塑发泡温度≥260℃时，化学发泡剂采用高温发泡剂；当挤塑发泡温度＜260℃时，化学发泡剂采用低温发泡剂。
进一步地，所述润滑剂为滑石粉或硬脂酸钙，其重量份为1.0～4.0份；
或者，所述润滑剂为小分子聚合物，其重量份为0.2～0.5份。
一种骨架的制造方法，采用上述用于生产电缆中聚碳酸酯骨架的组合物作为原料来生产骨架，具体包括如下步骤：
S1、称取原料，根据所述重量份称取原料，加入高速混合机充分搅拌均匀制成混合料，搅拌时间为5～20min，每次混合料总重量≥50kg；
S2、挤塑发泡，将S1中配混好的组合料喂入同向啮合双螺杆挤塑机的加料口，双螺杆挤塑机长径比≥30，该双螺杆挤塑机从挤塑机筒到机头，挤塑温度逐渐升高，挤塑温度为260～290℃，挤塑发泡制成数据缆缆芯“十字形”骨架。
本发明的有益效果是：本发明设计合理，操作简便，制得的数据电缆缆芯中聚碳酸酯骨架具有阻燃性和高强度的特点，提高了数据电缆的传输性能，同时生产成本低。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1是本发明中骨架的结构示意图。
具体实施方式
现在结合附图和优选实施例对本发明作进一步详细的说明。这些附图均为简化的示意图，仅以示意方式说明本发明的基本结构，因此其仅显示与本发明有关的构成。
一种用于生产电缆中聚碳酸酯骨架的组合物，包括如下重量份的原料：
Figure PCTCN2022087622-appb-000002
这种用于生产电缆中聚碳酸酯骨架的组合物还包括成核剂，其重量份为0.2～1.0份。
聚碳酸酯选用熔融粘度中等的聚碳酸酯，按GB/T 3682.1-2018标准测试其熔体质量流动速率(300℃/1.2kg)，以(3～15)g/10min为宜，优选为(5～12)g/10min。熔融粘度通常与熔体强度正比，因此熔融粘度低往往造成发泡泡孔破裂、骨架外观粗糙且外形变差和骨架强度降低；而熔融粘度过高导致挤塑效率低下，为此不得不提高挤塑温度，但这不利于发泡。PC可选用韩国LG化学公司的1300-10NP、中国石化仪征化纤股份有限公司的FG-60、韩国陶氏聚碳酸酯有 限公司的PC 201-15等产品。
每100重量份PC中，聚对苯二甲酸乙二酯再生料的加入重量份为8.0～12.0份。电线电缆厂广泛使用PET聚酯薄膜，用于电缆缆芯绝缘、耐热和绕包成形，生产中产生的PET薄膜废料较多，通常作为塑料垃圾卖掉。为了降低骨架材料成本，可将PET薄膜废料加入塑料破碎机，打碎为小片，将其在(70～90)℃的料斗中干燥4小时后直接加入骨架混合物材料中，或将其重新造粒后以粒料形式加入。PET和PC在性能上有互补效应，例如，PET阻燃性差，燃烧时发生熔滴，而PC本身具有一定的阻燃性，其阻燃等级可达到UL94V-2级，且能自熄，成炭率高；PC挤塑后会残留一部分内应力，在长期弯曲应力作用下可能发生开裂，而PET可以改善其柔韧性。
阻燃剂为磷酸三(2,4-二溴苯基)酯(TDBPPE)卤代磷酸酯复合阻燃剂，每100重量份PC中，阻燃剂的加入重量份为10～20.0份,优选12.0～15.0份,可选用浙江万盛科技有限公司的PX-220；
或者，阻燃剂为溴系高分子阻燃剂，可选用溴化聚苯乙烯(BPS)阻燃剂，每100重量份PC中，BPS的加入重量份为3.0～12.0份,优选为5.0～7.5份；BPS可选用沈阳正兴材料有限公司的BPS-301产品。
每100重量份PC中，抗滴落剂的加入重量份为0.3～0.6份，抗滴落剂可以进一步提高骨架燃烧时的成壳性，避免其发生燃烧熔滴现象，从而提高电缆阻燃性能。抗滴落剂可选用上海鲁聚聚合物公司出品的聚四氟乙烯(PTFE)粉末、嘉善申嘉科技有限公司的SJ-D100S抗滴落剂和广州宝久化工科技有限公司的DF-S10抗滴落剂等。
骨架发泡结构将使得骨架对电缆中线对传输衰减的影响降低，为此每100重量份PC中，加入0.3～3.0重量份的化学发泡剂。
在选用化学发泡剂时，应考虑到与挤塑发泡温度相匹配。当挤塑发泡温度超过260℃，则所选择的化学发泡剂应在较高温度下才分解释放出气体，过低将造成发泡剂在机膛加料段就过早分解，一部分气体将从加料口漏泄出去，降低发泡度，造成发泡剂浪费和发泡度不均匀。当双螺杆挤塑机从第一节筒体(加料段)到机头，温度设置为(260～310)℃，即靠近加料口的后段机膛温度较高时，采用适合高温发泡的偶氮二甲酸钡和偶氮二羧酸钡作为发泡剂；也可选用市场上销售的其它专用发泡剂，如美国Polyone公司OnCapPolyFoam化学发泡剂、上海杰上杰化学有限公司的发泡剂LDM 10070S。
当骨架混合物挤塑发泡温度可以控制在260℃以下，例如从加料口到挤塑机头的温度从230℃～255℃逐渐升高，采用偶氮二甲酰胺(AC)作为化学发泡剂。
骨架组合物中加入成核剂将有助于获得尺寸均匀的发泡泡孔。化学发泡剂分解后的残留物可以作为发泡的成核剂，但往往还不够，为此在每100重量份PC中，加入0.2～1份的成核剂作为补充，优选为0.4～0.6份，可选用的成核剂有德国布吕格曼公司的P250产品。当选择PTFE粉末作为抗滴落剂时，PTFE粉末在挤塑发泡过程中则起到成核剂的作用，因此可以不再加入额外的成核剂。
为了提高挤塑效率，在骨架组合物中加入加工润滑剂。每100重量份PC中，加入1～4重量份的滑石粉或硬脂酸钙，可选用上海奥科化学品有限公司的硬脂酸钙。也可在每100重量份PC中加入0.2～0.5重量份的小分子聚合物，选用意大利发基公司的脂肪酸酯A润滑剂，其好处是加入量低，不影响发泡，并且有利于提高骨架的强度。
一种骨架的制造方法，采用上述用于生产电缆中聚碳酸酯骨架的组合物作为原料来生产骨架，具体包括如下步骤：
S1、制备试样，将上述各组分混合均匀后的共混物加入塑料样品制备用注 塑机，按标准中规定的试验用样条尺寸要求，注塑得到塑料试样；按ISO 527：1996标准进行测试得到的拉伸强度不小于45MPa，拉伸模量不小于1900MPa，高的机械强度使得骨架在电缆受到外力和使用过程中不容易变形，从而避免电缆串音性能下降；采用GB/T 2406-2009标准测试得到的氧指数不低于30；按GB/2408-2008进行测试得到的阻燃性能达到垂直V-0级别(试样厚度为3mm)；样品检测合格后，可确定各组分的重量份；
S2、称取原料，根据S1中确定的各组分重量份来称取原料，加入高速混合机充分搅拌均匀制成混合料，搅拌时间为5～20min，每次混合料总重量≥50kg；根据加入料的多少酌情决定搅拌时间，即加入料越多，搅拌时间越长；
S3、挤塑发泡，将S2中配混好的组合料喂入同向啮合双螺杆挤塑机的加料口，双螺杆挤塑机长径比为35～40，该双螺杆挤塑机从挤塑机筒到机头，挤塑温度逐渐升高，挤塑温度为260～290℃，挤塑发泡制成数据缆缆芯“十字形”骨架。选用双螺杆挤塑机的好处是可以降低挤塑温度，防止化学发泡剂在机膛加料段过早分解，同时保持熔体塑化质量。
通过控制化学发泡剂加入比例和挤塑温度，可以调整骨架的发泡度，发泡度越高，其密度越低。加入的化学发泡剂越多，且挤塑温度分配适当，包括在机筒加料段温度不能高于化学发泡剂分解释放出气体的温度、机筒塑料熔融段温度要高于化学发泡剂分解温度、机头温度不能高于机筒最高温度5℃以上，发泡度可以得到提高。发泡挤塑得到的骨架单位长度的质量比未发泡骨架降低15％～30，线对在500MHz的传输衰减平均降低了2％。
实施例1
一种用于生产电缆缆芯中聚碳酸酯骨架的组合物，包括如下重量份的原料：
PC：100.0份，中国石化仪征化纤股份有限公司的FG-60；
PET回料：8.0份；
阻燃剂TDBPPE：12.0份，浙江万盛科技有限公司的PX-220；
抗滴落剂兼成核剂：PTFE粉末，0.4份，上海鲁聚聚合物公司出品；
化学发泡剂：1.5份，上海杰上杰化学有限公司的发泡剂；
润滑剂：0.2份，意大利发基公司的脂肪酸酯A。
实施例2
一种用于生产电缆缆芯中聚碳酸酯骨架的组合物，包括如下重量份的原料：
PC：100.0份，韩国陶氏聚碳酸酯有限公司的PC 201-15；
PET回料：10.0份；
BPS阻燃剂：8.0份，沈阳正兴材料有限公司的BPS–301；
抗滴落剂：1.0份，广州宝久化工科技有限公司的DF-S10抗滴落剂；
偶氮二甲酸钡化学发泡剂：1.5份；
成核剂：0.5份，德国布吕格曼公司的P250；
润滑剂：0.5份，上海奥科化学品有限公司的硬脂酸钙。
对比例1
一种用于生产电缆缆芯中聚碳酸酯骨架的组合物，包括如下重量份的原料：
PC：100.0份，韩国陶氏聚碳酸酯有限公司的PC 201-15；
PET回料：10.0份；
BPS阻燃剂：8.0份，沈阳正兴材料有限公司的BPS–301；
抗滴落剂：1.0份，广州宝久化工科技有限公司的DF-S10抗滴落剂；
润滑剂：0.5份，上海奥科化学品有限公司的硬脂酸钙。
本发明以HSYV-6 4×2×0.57电缆为例，如图1所示。采用上述实施例1或实施例2制得的十字形聚碳酸酯料骨架，可减小骨架尺寸，其直径D为5.0mm， 厚度t为0.5mm。用聚碳酸酯十字形骨架生产数据缆，4个线对的最大线对绞合节距控制在16mm以下，最小线对绞合节距控制在11mm以下,4个线对的平均绞合节距提高了15％，换言之，绞合生产效率因此提高15％；电缆聚氯乙烯护套采用燃烧性能达到垂直V-1级别、氧指数不低于28的普通阻燃PVC护套料即可，护套厚度从0.75mm降低为0.63mm，电缆外径从7.0mm降低为6.5mm。在电缆性能测试中，电缆在频率250MHz上，线对近端串音衰减功率和(PS NEXT)最小值为38.0dB，等电平远端串音衰减功率和(PS ACR-F)最小值为19.3dB/100m，衰减为31.0dB/100m。
传统十字型骨架(材料为本色高密度聚乙烯，实心结构)中，其骨架直径D为5.3mm，厚度t为0.7mm。在电缆弯曲试验中，能观察到骨架明显变形，4个被隔开的线对彼此间的距离发生变化。为了满足电缆串音性能合格，不得不将4个线对的最大线对绞合节距控制在14mm以下，最小线对绞合节距控制在9mm以下，这样得到的电缆在频率250MHz上的关键传输性能方可维持以下水平：线对近端串音衰减功率和(PS NEXT)为36.5dB，等电平远端串音衰减功率和(PS EL FEXT)为18.0dB/100m，衰减为32.1dB/100m，刚好满足标准要求；而为了使得电缆阻燃水平达到在燃烧试验中通过单根绝缘电线电缆火焰垂直蔓延试验，电缆聚氯乙烯(PVC)护套必须采用阻燃性能达到垂直V-0级别、氧指数不低于38的高阻燃PVC护套料，且护套厚度为0.75mm。最后得到的电缆外径为7.0mm。
因此，本发明与传统十字形骨架电缆相比，其串音性能和衰减性能较传统十字形骨架电缆有明显改善。
对比例1采用实心挤塑工艺得到聚碳酸酯骨架，骨架尺寸、线对绞合节距、护套厚度等和实施例2、实施例1生产的电缆相同，则可看到电缆串音性能基本 不变，即与传统骨架相比有明显改善；但电缆衰减并无明显改进。这说明骨架化学发泡不但可降低电缆重量并节约材料，对电缆衰减也有一定的改善作用。
以上说明书中描述的只是本发明的具体实施方式，各种举例说明不对本发明的实质内容构成限制，所属技术领域的普通技术人员在阅读了说明书后可以对以前所述的具体实施方式做修改或变形，而不背离发明的实质和范围。

Claims (10)

  1. 一种用于生产电缆中聚碳酸酯骨架的组合物，其特征在于：包括如下重量份的原料：
    Figure PCTCN2022087622-appb-100001
  2. 根据权利要求1所述的用于生产电缆中聚碳酸酯骨架的组合物，其特征在于：所述用于生产电缆缆芯中聚碳酸酯骨架的组合物还包括成核剂，其重量份为0.2～1.0份。
  3. 根据权利要求1所述的用于生产电缆中聚碳酸酯骨架的组合物，其特征在于：所述聚碳酸酯的熔体质量流动速率为3～15g/10min。
  4. 根据权利要求1所述的用于生产电缆中聚碳酸酯骨架的组合物，其特征在于：所述聚对苯二甲酸乙二酯再生料的重量份为8.0～12.0份。
  5. 根据权利要求1所述的用于生产电缆中聚碳酸酯骨架的组合物，其特征在于：所述阻燃剂为磷酸三(2,4-二溴苯基)酯卤代磷酸酯复合阻燃剂，其重量份为10～20.0份；
    或者，所述阻燃剂为溴系高分子阻燃剂，其重量份为3.0～12.0份。
  6. 根据权利要求5所述的用于生产电缆中聚碳酸酯骨架的组合物，其特征在于：所述磷酸三(2,4-二溴苯基)酯卤代磷酸酯复合阻燃剂的重量份为12.0～15.0份；所述溴系高分子阻燃剂为溴化聚苯乙烯，其重量份为5.0～7.5份。
  7. 根据权利要求1所述的用于生产电缆中聚碳酸酯骨架的组合物，其特征 在于：所述抗滴落剂为聚四氟乙烯粉末、SJ-D100S抗滴落剂或DF-S10抗滴落剂，其重量份为0.3～0.6份。
  8. 根据权利要求1所述的用于生产电缆中聚碳酸酯骨架的组合物，其特征在于：所述化学发泡剂为高温发泡剂或低温发泡剂，当挤塑发泡温度≥260℃时，化学发泡剂采用高温发泡剂；当挤塑发泡温度＜260℃时，化学发泡剂采用低温发泡剂。
  9. 根据权利要求1所述的用于生产电缆中聚碳酸酯骨架的组合物，其特征在于：所述润滑剂为滑石粉或硬脂酸钙，其重量份为1.0～4.0份；
    或者，所述润滑剂为小分子聚合物，其重量份为0.2～0.5份。
  10. 一种骨架的制造方法，其特征在于：采用如权利要求1～9任一项所述用于生产电缆中聚碳酸酯骨架的组合物作为原料来生产骨架，具体包括如下步骤：
    S1、称取原料，根据所述重量份称取原料，加入高速混合机充分搅拌均匀制成混合料，搅拌时间为5～20min，每次混合料总重量≥50kg；
    S2、挤塑发泡，将S1中配混好的组合料喂入同向啮合双螺杆挤塑机的加料口，双螺杆挤塑机长径比≥30，该双螺杆挤塑机从挤塑机筒到机头，挤塑温度逐渐升高，挤塑温度为260～290℃，挤塑发泡制成数据缆缆芯“十字形”骨架。
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5556903A (en) * 1988-03-18 1996-09-17 Fmc Corporation Polybrominated phenylphosphate flame retardent for engineering thermoplastic compositions
CN101914276A (zh) * 2010-08-12 2010-12-15 东莞市信诺橡塑工业有限公司 聚碳酸酯组合物及其制备方法
CN102863771A (zh) * 2012-09-26 2013-01-09 上海锦湖日丽塑料有限公司 一种轻量化的聚碳酸酯组合物及其制备方法
CN104403186A (zh) * 2014-11-14 2015-03-11 宁波一舟塑胶有限公司 一种复合协效阻燃抑烟的低烟无卤骨架料
CN104558913A (zh) * 2013-10-22 2015-04-29 宁夏金黄河塑业有限责任公司 一种聚乙烯骨架式半空气绝缘层、高阻燃pvc电缆护套
CN108061951A (zh) * 2018-01-12 2018-05-22 西安西古光通信有限公司 一种骨架式光纤带光缆
CN113462140A (zh) * 2021-05-31 2021-10-01 武汉金发科技有限公司 一种阻燃聚碳酸酯复合材料及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004182938A (ja) * 2002-12-05 2004-07-02 Nippon Polyester Co Ltd ポリエステル／ポリカーボネート樹脂組成物から形成されてなる発泡体及び発泡微粒子
CN1773633B (zh) * 2005-11-08 2010-04-14 四川爱通电子线缆制造有限责任公司 一种电缆发泡方法
WO2018159483A1 (ja) * 2017-02-28 2018-09-07 三井化学株式会社 導電性樹脂組成物、その製造方法およびそれから得られる成形体
CN113897045B (zh) * 2021-10-14 2023-05-09 金发科技股份有限公司 一种阻燃聚碳酸酯合金组合物及其制备方法和应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5556903A (en) * 1988-03-18 1996-09-17 Fmc Corporation Polybrominated phenylphosphate flame retardent for engineering thermoplastic compositions
CN101914276A (zh) * 2010-08-12 2010-12-15 东莞市信诺橡塑工业有限公司 聚碳酸酯组合物及其制备方法
CN102863771A (zh) * 2012-09-26 2013-01-09 上海锦湖日丽塑料有限公司 一种轻量化的聚碳酸酯组合物及其制备方法
CN104558913A (zh) * 2013-10-22 2015-04-29 宁夏金黄河塑业有限责任公司 一种聚乙烯骨架式半空气绝缘层、高阻燃pvc电缆护套
CN104403186A (zh) * 2014-11-14 2015-03-11 宁波一舟塑胶有限公司 一种复合协效阻燃抑烟的低烟无卤骨架料
CN108061951A (zh) * 2018-01-12 2018-05-22 西安西古光通信有限公司 一种骨架式光纤带光缆
CN113462140A (zh) * 2021-05-31 2021-10-01 武汉金发科技有限公司 一种阻燃聚碳酸酯复合材料及其制备方法

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