CN103221460A - 用于缆线的柔性加强件 - Google Patents

用于缆线的柔性加强件 Download PDF

Info

Publication number
CN103221460A
CN103221460A CN201180056279XA CN201180056279A CN103221460A CN 103221460 A CN103221460 A CN 103221460A CN 201180056279X A CN201180056279X A CN 201180056279XA CN 201180056279 A CN201180056279 A CN 201180056279A CN 103221460 A CN103221460 A CN 103221460A
Authority
CN
China
Prior art keywords
reinforcement
gpa
resin composition
modulus
fibers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201180056279XA
Other languages
English (en)
Other versions
CN103221460B (zh
Inventor
B.陈
B.I.乔德哈利
C.J.科米克
J.M.科根
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of CN103221460A publication Critical patent/CN103221460A/zh
Application granted granted Critical
Publication of CN103221460B publication Critical patent/CN103221460B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/081—Combinations of fibres of continuous or substantial length and short fibres
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/523—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement in the die
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • C08K7/02—Fibres or whiskers
    • 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
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4401—Optical cables
    • G02B6/4429—Means specially adapted for strengthening or protecting the cables
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4401—Optical cables
    • G02B6/4429—Means specially adapted for strengthening or protecting the cables
    • G02B6/4434—Central member to take up tensile loads
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • 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
    • 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
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

本发明涉及一种用在光缆中的纤维增强的塑料材料，其具有改进的柔韧性和高的拉伸强度。所述加强件组合物包含基于聚丙烯的热塑性树脂、模量大于80 GPa的连续纤维，和滑石。

Description

用于缆线的柔性加强件
相关申请的交叉引用
本申请要求2010年9月29日提交的申请序列号为61/387,581的美国临时专利申请的优先权，该临时专利申请的全部内容并入本文作为参考。
背景技术
1.技术领域
本发明涉及一种具有改进的柔韧性和高拉伸强度的纤维增强塑料材料，其用作光缆中的加强件。
2.相关技术描述
本发明涉及用于光纤缆线(FOC)的加强件的构造。由于不存在金属导体，光纤缆线依赖于包含加强件的设计来为纤维提供充分的保护，使其免于受到在安装过程中或之后在服务过程中的纵向和横向应力的破坏。加强件通常由纤维增强塑料(FRP)，也称为玻璃增强塑料(GRP)制得。
纤维增强塑料是由用纤维增强的聚合物基材制得的复合材料。纤维通常为玻璃(最普遍)、碳或芳族聚酰胺，而传统上聚合物通常为环氧树脂或乙烯基酯。
使用常规的树脂体系时，FRP非常坚硬。对直径2毫米(mm)的杆而言，FRP通常具有高于6x10-3Pa m4的弯曲劲度，导致光纤缆线很难弯曲。虽然高的弯曲劲度在一些户外应用(即，安装过程中有时需要将缆线“推”进小直径导管)中是有利的，但对于在那些缆线需要进入建筑物之内并且进行几次转向之后才能到达目的地的其它应用(户外/户内)而言，高弯曲劲度是非常不合乎需要的。为了增加缆线的柔韧性，不得不减小FRP的尺寸(这将降低缆线总的拉伸强度)或者改变缆线的设计。例如，一些缆线制造商就将传统的具有中心加强件的圆FOC光缆改变为一种扁平的“带状”缆线，该扁平的“带状”的缆线采用具有多根沿其宽度方向平行的FRP的平面几何形状(并非圆形)。在所述扁平缆线设计中使用的FRP具有相对较小的直径，但其总的拉伸强度等同于传统的圆缆线。与传统的具有中心加强件的圆缆线相比，扁平缆线的设计在一个轴(沿其宽度方向)上提供较高的柔韧性，同时保持缆线的总拉伸强度不变。然而改变缆线设计却会造成更高的制造复杂度。
发明内容
在一种实施方式中本发明为一种加强件，包含：(a)基于聚丙烯的热塑性树脂组合物和(b)具有高于80吉帕斯卡(GPa)模量的连续纤维。所述基于聚丙烯的热塑性树脂可另外包含增强填料，例如滑石(talc)。可利用所述组合物来制造线材和缆线具体是光纤缆线的加强件。
在一种实施方式中，本发明为制造加强件的方法，包含如下步骤：(a)加热基于聚丙烯的树脂组合物，该组合物任选包括填料，在挤出机,优选在双螺杆挤出机中进行，以形成熔融的填充复合物(compound)；(b)将连续纤维加入挤出机，以结合熔融的填充复合物来形成润湿的纤维填充的复合物束(bundle)；和(c)使润湿的纤维填充的复合物束通过模头(die)，形成加强件。
附图说明
图1是FRP拉伸模量相对于弯曲劲度的关系图。
优选实施方式的详细描述
定义
除非相反地指出，从上下文暗示或现有技术惯例，所有的份和百分比均基于重量，而且所有的测试方法是与本申请的提交日期同步的。针对美国专利实践的目的，任何涉及的专利、专利申请或公开的内容在此全部引入作为参考(或其等价的US同族也引入作为参考)，特别是关于本领域中的定义(不与本申请具体提供的任何定义不一致)和常识的披露。
本申请中的数字范围是近似值，因此除非另有所指，否则其可以包括该范围以外的值。数值范围包括以1个单位增加的从下限值到上限值的所有数值，条件是在任意较低值与任意较高值之间存在至少2个单位的间隔。例如，如果记载组成、物理或其它性质，如分子量等是100至1,000，则意味着明确地列举了所有的单个数值，如100、101、102等，以及所有的子范围，如100至144、155至170、197至200等。对于包含小于1的数值或者包含大于1的分数(例如1.1、1.5等)的范围，适当时将1个单位看作0.0001、0.001、0.01或0.1。对于包含小于10(例如1至5)的个位数的范围，通常将1个单位看作0.1。这些仅仅是具体所意指的内容的示例，并且所列举的最低值与最高值之间的数值的所有可能组合都被认为清楚记载在本申请中。本申请内的数字范围尤其提供了本发明组合物中各种组分的含量、工艺参数等。
“热塑性”材料是一种线性或支化的聚合物，其在受热时可被反复地软化并使得可流动，并且当冷却至室温时又返回至坚硬状态。在本发明的上下文中，使用ASTM D638-72方法，所述热塑性材料一般具有大于10,000psi(68.95 MPa)的弹性模量。另外，当受热至软化状态时，热塑性材料可被模塑或挤出成具有任何预定形状的制品。
“基于丙烯的聚合物”是指含有多数重量百分比的聚合的丙烯单体的聚合物(基于可聚合单体的总量)，并且任选含有至少一种可聚合的共单体。
根据ASTM D638测量断裂拉伸强度。
这里使用的“连续纤维”是在整根纱线的长度上都为连续的纤维。取决于纱线的尺寸，连续纤维的长度可在较大范围如5到30km内变化。
加强件
本发明所述的加强件包含热塑性树脂组合物和在所述加强件制造过程中作为增强材料的连续纤维。可行的纤维包括但并不局限于玻璃、芳族聚酰胺、聚酯、高分子量聚乙烯和碳纤维。本发明的纤维通常具有高于80GPa的模量，优选为80-90GPa。与在光纤缆线中采用的传统FRP相比，所述加强件在保持高拉伸强度的同时具有更高的柔韧性。加强件的柔韧性通过其弯曲劲度来表征，弯曲劲度通过有效的树脂配制物可在宽泛的范围内调整，例如，约0.1x10-3至约2.5x10-3Pa m4、0.1x10-3至约6.0x10-3Pa m4、3.0x10-3至6.5x10-3Pa m4和优选地3.26x10-3至约6.08x10-3Pa m4。所述加强件的FRP拉伸模量通常介于49GPa和59GPa之间。
树脂组合物
本发明采用含有基于聚丙烯的热塑性材料的组合物作为其树脂体系。表1显示出所述树脂体系的可行配制物。可以任选地在配制物中使用多种含量水平的滑石作为填料，来调整树脂的拉伸模量以及因此调整加强件的弯曲劲度。可性的填料包括但不限于滑石或其它增强填料。相对于树脂组合物的重量而言，滑石通常以0、15或30重量百分比存在。
表1
树脂组合物的配制物
Figure BDA00003235292000041
与使用不容易回收利用的热固性材料的传统FRP相比，通过使用热塑性体系，所述加强件可容易回收利用。另外，本发明的基于聚丙烯的树脂体系具有相对低的粘度，并且所述加强件可通过具有纤维拉挤直角机头(fiberpultrusion crosshead)的挤出机进行拉挤。这与常规的FRP制造方法相反，常规的方法本质上是传统的树脂浴和拉挤过程的在线固化类型。在拉挤直角机头的温度下所述树脂具有低粘度，能以更为高效的方式润湿纤维。另外，低粘度也将有助于除去在纤维束通过模头时附着在纤维上的过量树脂(以“回流”的形式)。在常规制造方法下制作定制的截面几何形状是困难并且昂贵的。然而，使用本发明，可更为高效地制作具有定制成形的截面几何形状的加强件，因为所述热塑性树脂具有相对低的粘度并可容易地成型为任何形状。另外，不需要对热塑性树脂进行固化。
此外，本发明的树脂组合物中也有利地采用多种任选组分。例如，可采用的添加剂包括抗氧化剂、UV稳定剂、增稠剂、杀菌剂、加工稳定剂、热稳定剂、胶粘剂树脂、着色剂、耦合剂、阻燃剂、脱模剂、抗静电剂、成核剂、填料或其任意组合。可将所述添加剂分散在聚合物基材中，该聚合物基材包括与所述聚丙烯树脂相同或不同的载体聚合物。
作为特定的实例，在一种实施方式中，预计将一种或多种抗氧化剂(例如来自Ciba的
Figure BDA00003235292000042
1010抗氧化剂，
Figure BDA00003235292000043
PS802抗氧化剂)和加工稳定剂(例如，活性亚磷酸盐，如三-(2,4-二叔丁基苯基)亚磷酸盐(来自Ciba的
Figure BDA00003235292000044
168))复合到树脂组合物中。也可包括偶合剂或粘合促进剂，例如来自Arkema的OREVACTMCA-100树脂。
制造方法
通过连续纤维拉挤制得FRP加强件的所述聚合物复合物可使用常规的复合方法制得，如间歇混合机(Banbury等)或连续混合机(FCM等)。在一种实施方式中，这样的复合物得以制备并分离为粒状中间物，以便随后用于所述拉挤过程。一些情况下也会有利的是，预复合一些成分，然后在所述拉挤过程中加入其它成分。另外还会有利的是，在拉挤过程中复合所有的成分。例如，拉挤过程中，在高温下熔融挤出所述聚合物复合物，以确保树脂完全熔化并达到适当低的粘度。然后将纤维加入挤出机并通过室内直角机头里的熔融树脂将纤维润湿，在此使用高压(高于2000psi)来确保纤维上有超过85%的树脂覆盖度的优良的纤维浸透性。然后将润湿的纤维/树脂束连续地拉出成型模头，并冷却以保持其形状。
在一种实施方式中，所述加强件通过加热聚丙烯树脂组合物得以形成，所述组合物包含增强填料以便形成熔融的填充复合物。将连续纤维加入挤出机，以使连续纤维与熔融的填充复合物相结合形成润湿的填充复合物束。使润湿的纤维填充的复合物束通过模头，形成所述加强件。
具体实施例
表2中可见实施例1、2和3的配制物。实施例中使用连续的E玻璃纤维，得自Owens Corning SE4121(模量=81-83GPa)。
表2
实施例的百分比组成
Figure BDA00003235292000051
ACHIEVE6936G1和线性低密度聚乙烯是所述树脂的流变改性剂，其用于优化所述复合物的粘度。用IRGANOX 1010、IRGAFOX 168和 IRGANOXPS 802作为抗氧化剂。用马来酸酐改性的聚丙烯作为粘合促进剂。实施例1-3中使用的聚丙烯是具有52 g/10min的MFR、0.9 g/cm3的密度和1.65 GPa的弯曲模量的均聚物。所述线性低密度聚乙烯具有10 g/10min的MFR、0.924g/cm3的密度和0.38 GPa的弯曲模量。
通过拉挤过程制得实施例1-3。首先将包含滑石的各树脂组分经主料斗加入挤出机。随着材料通过挤出机到达直角机头，进行在线混合，在直角机头处使用300°C的高温来确保树脂充分熔化并达到期望低的粘度。然后将玻璃纤维加入挤出机并通过室内直角机头里的熔融复合物将纤维润湿，在直角机头处使用高压(高于2000 psi)来确保优良的纤维浸透性。然后将润湿的纤维/树脂束以2ft/分钟的速率连续地拉过成型模头,并使之冷却以保持其形状。
表3显示实施例的性质，与用于FRP的已知的常规树脂相比较。
表3
实施例1-3和比较例1-10的树脂的模量、弯曲劲度和拉伸强度
根据测试标准ASTM D790测量树脂模量。
弯曲劲度根据测试标准ASTM D790进行测量(实施例1-3)或从组件的模量和加强件的尺寸中进行计算得到(比较例1-10)。
在本发明中加强件的一大优势是能够在保持高拉伸强度的同时改进柔韧性。对连续纤维(在长度方向上对齐)增强的加强件而言，其弯曲劲度基本上由树脂的弯曲模量来决定。表3中的比较例包括一些市售的、在现有FRP产品中使用的常用环氧乙烯基酯树脂。
Figure BDA00003235292000071
环氧乙烯基酯树脂由Ashland制得。为了比较的目的，考虑中的FRP为圆形并具有2mm的直径。
本发明的加强件提供了比目前使用的环氧乙烯基酯树脂更宽范围的弯曲劲度，同时拉伸模量保持不变。图1显示出就拉伸模量和弯曲劲度而言比较例的常规FRP和实施例1-3的加强件之间的对比。该图证明，使用不同的市售环氧乙烯基酯树脂，FRP的弯曲劲度可以变化，但限于距平均值小于15%的相对窄的范围内。另一方面，通过使用不同配制物，本发明的加强件提供了更宽范围的弯曲劲度。更为具体地，使用实施例1或2的配制物制得的加强件非常柔韧(弯曲劲度小于2.5x10-3Pa m4)，而使用实施例3的配制物制得的加强件具有与使用DERAKANE MOMENTUMTM640-900环氧乙烯基酯树脂制得的现有FRP(弯曲劲度接近于6x10-3Pa m4)相似的刚度。最重要的是，本发明的加强件达到所述柔韧性的同时并未牺牲拉伸模量；它基本上提供了与目前市场上的FRP相同的拉伸模量。
虽然以一些细节通过前面优选实施方式的说明描述了本发明，但此细节是为了主要目的说明。本领域技术人员可以进行多种变化和改变，而并不偏离如所附权利要求所述的本发明的精神和范围。

Claims (15)

1.一种加强件，包含：
(a)基于聚丙烯的热塑性树脂组合物；和
(b)模量大于80PGa的连续纤维。
2.如权利要求1所述的加强件，其中所述热塑性树脂组合物还包含增强填料。
3.如权利要求2所述的加强件，其中所述的增强填料为滑石。
4.如权利要求1所述的加强件，其中所述的连续纤维选自玻璃、芳族聚酰胺、聚酯、高分子量聚乙烯、和碳纤维。
5.如权利要求3所述的加强件，还包含：
(a)1wt%至30wt%的滑石，基于热塑性树脂组合物的重量；和
(b)模量为80Gpa至90GPa的连续纤维。
6.如权利要求1所述的加强件，其中所述热塑性树脂组合物还包含至少一种抗氧化剂、加工稳定剂、热稳定剂和粘合性树脂。
7.如权利要求1所述的加强件，具有对2mm直径的加强件而言小于2.5x10-3Pa m4并大于0.1x10-3Pa m4的弯曲劲度和大于49GPa的FRP拉伸模量。
8.如权利要求1所述的加强件，具有对2mm直径的加强件而言小于6.0x10-3Pa m4并大于0.1x10-3Pa m4的弯曲劲度。
9.如权利要求1所述的加强件，具有对2mm直径的加强件而言3.26x10-3Pam4至6.08x10-3Pa m4的弯曲劲度和大于49GPa的FRP拉伸模量。
10.如权利要求1所述的加强件，具有49GPa至59GPa FRP的拉伸模量。
11.一种包含如权利要求1所述的加强件的光纤缆线。
12.一种制造加强件的方法，包括以下步骤：
(a)加热包含增强填料的聚丙烯树脂组合物，以形成熔融的填充复合物；
(b)将连续纤维进料至挤出机，以与所述熔融的填充复合物组合形成润湿的填充的复合物束；和
(c)使所述润湿的纤维填充的复合物束经过模具，形成所述加强件。
13.如权利要求12所述的方法，其中所述连续纤维选自玻璃、芳族聚酰胺、聚酯、高分子量聚乙烯、和碳纤维。
14.如权利要求12所述的方法，其中所述的增强填料是滑石。
15.如权利要求12所述的方法，其中所述加强件包含：
(a)1wt%至30wt%的滑石，基于所述热塑性树脂组合物的重量；和
(b)连续玻璃纤维，其模量为80GPa至90GPa。
CN201180056279.XA 2010-09-29 2011-09-21 用于缆线的柔性加强件 Expired - Fee Related CN103221460B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US38758110P 2010-09-29 2010-09-29
US61/387,581 2010-09-29
PCT/US2011/052452 WO2012044498A1 (en) 2010-09-29 2011-09-21 Flexible strength members for wire cables

Publications (2)

Publication Number Publication Date
CN103221460A true CN103221460A (zh) 2013-07-24
CN103221460B CN103221460B (zh) 2015-11-25

Family

ID=44759781

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180056279.XA Expired - Fee Related CN103221460B (zh) 2010-09-29 2011-09-21 用于缆线的柔性加强件

Country Status (10)

Country Link
US (1) US8995810B2 (zh)
EP (1) EP2622005B1 (zh)
JP (1) JP5945274B2 (zh)
KR (1) KR101948331B1 (zh)
CN (1) CN103221460B (zh)
BR (1) BR112013006984A2 (zh)
CA (1) CA2812746C (zh)
MX (1) MX337207B (zh)
TW (1) TW201229599A (zh)
WO (1) WO2012044498A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103995329A (zh) * 2014-05-05 2014-08-20 浙江一舟电子科技股份有限公司 一种新型非金属层绞式矿用光缆
CN112731603A (zh) * 2020-12-23 2021-04-30 华为技术有限公司 光缆

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5945274B2 (ja) 2010-09-29 2016-07-05 ダウ グローバル テクノロジーズ エルエルシー ワイヤケーブルのための可撓性テンションメンバ
US20130273369A1 (en) * 2010-12-29 2013-10-17 Huajun Zhou Method of Making a Cable Strength Member
KR101911575B1 (ko) * 2014-05-23 2018-10-25 (주)엘지하우시스 연속섬유 강화 복합재 및 그의 제조방법

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1150482A (zh) * 1995-01-24 1997-05-21 阿尔卡特尔Na电缆系统公司 用于光缆中的聚丙烯聚乙烯共聚物缓冲管及其制造方法
US20040120664A1 (en) * 2002-12-19 2004-06-24 Alcatel Anti-rotational central strength member

Family Cites Families (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3517086A (en) * 1966-01-31 1970-06-23 Sumitomo Chemical Co Nucleated blend of polypropylene,polyethylene,and ethylene propylene copolymer
JPS5125580Y2 (zh) * 1971-11-18 1976-06-29
AU498247B2 (en) * 1974-12-27 1979-02-22 Itt Industries Inc Fire optic cable
US4413110A (en) 1981-04-30 1983-11-01 Allied Corporation High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore
US4581393A (en) 1983-02-22 1986-04-08 The Dow Chemical Company Glass fiber reinforced vinylized epoxy compositions with reduced fiber prominence
JPS6033520A (ja) 1983-08-05 1985-02-20 Ube Nitto Kasei Kk 繊維強化光ファイバ並びにその製造方法
US4643940A (en) 1984-08-06 1987-02-17 The Dow Chemical Company Low density fiber-reinforced plastic composites
EP0375896B1 (en) 1988-12-28 1994-06-01 Ube-Nitto Kasei Co. Ltd. Twisted FRP structure and process for manufacturing the same
JP2849418B2 (ja) 1989-11-28 1999-01-20 宇部日東化成株式会社 光ファイバテープ心線補強用テンションメンバー及びその製造方法
JP3167513B2 (ja) 1993-08-03 2001-05-21 三洋電機株式会社 非水電解液電池
JPH0821935A (ja) * 1994-07-05 1996-01-23 Toyobo Co Ltd 光ファイバー用テンションメンバー
US5756206A (en) * 1995-03-15 1998-05-26 Custom Composite Materials, Inc. Flexible low bulk pre-impregnated tow
US5561729A (en) 1995-05-15 1996-10-01 Siecor Corporation Communications cable including fiber reinforced plastic materials
US5891560A (en) 1997-07-02 1999-04-06 The Dow Chemical Company Fiber-reinforced composite and method of making same
JPH1183609A (ja) 1997-09-04 1999-03-26 Ishida Co Ltd 電子秤
US6239208B1 (en) * 1998-01-07 2001-05-29 H. B. Fuller Licensing & Financing, Inc. Flame retardant hot melt compositions
ES2361475T3 (es) * 1998-02-23 2011-06-17 Draka Comteq B.V. Componentes estructurales compuestos que contienen refuerzos de polímero cristalino líquido para cables de fibra óptica.
US6748146B2 (en) * 1999-05-28 2004-06-08 Corning Cable Systems Llc Communication cable having a soft housing
US6421486B1 (en) * 1999-07-01 2002-07-16 Fitel Usa Corp. Extruded buffer tubes comprising polyolefin resin based color concentrates for use in fiber optic cables
US6524702B1 (en) * 1999-08-12 2003-02-25 Dow Global Technologies Inc. Electrical devices having polymeric members
US6400873B1 (en) * 2000-03-31 2002-06-04 Corning Cable Systems Llc Fiber optic cable having a strength member
US7346244B2 (en) * 2001-03-23 2008-03-18 Draka Comteq B.V. Coated central strength member for fiber optic cables with reduced shrinkage
US7585563B2 (en) * 2001-05-01 2009-09-08 Ocv Intellectual Capital, Llc Fiber size, sized reinforcements, and articles reinforced with such reinforcements
US6553167B2 (en) * 2001-06-04 2003-04-22 Corning Cable Systems Llc Fiber optic cables having ultra-low shrinking filaments and methods of making the same
US6654525B2 (en) * 2001-10-10 2003-11-25 Alcatel Central strength member with reduced radial stiffness
US20030068145A1 (en) * 2001-10-10 2003-04-10 Alcatel Central strength member with reduced radial stiffness
US6707973B2 (en) * 2001-11-02 2004-03-16 Alcatel Buffer tube design for easy and reliable access in mid-span
JP3581869B2 (ja) * 2002-03-05 2004-10-27 隆行 近藤 繊維補強プラスチック成形体
US20040002559A1 (en) * 2002-04-10 2004-01-01 Malisa Troutman Flame retardant coatings
KR100926714B1 (ko) * 2002-05-10 2009-11-17 디아이씨 가부시끼가이샤 광섬유 피복용 수지 조성물 및 그것을 이용한 피복된광섬유 및 광섬유 유닛
US20050079779A1 (en) 2002-12-04 2005-04-14 Dow Global Technologies Inc. Reinforced polymer composites
JP2007072379A (ja) * 2005-09-09 2007-03-22 Hitachi Cable Ltd 光ファイバケーブル
JP2007091792A (ja) * 2005-09-27 2007-04-12 Toyobo Co Ltd 有機繊維強化ポリプロピレン樹脂組成物
DE102007009268B4 (de) * 2006-03-01 2014-09-25 Nippon Shokubai Co., Ltd. Thermoplastische Harzzusammensetzung und Herstellungsverfahren für diese
US20080118728A1 (en) 2006-10-20 2008-05-22 Dow Global Technologies Inc. Aqueous dispersions disposed on glass-based fibers and glass-containing substrates
US7603011B2 (en) * 2006-11-20 2009-10-13 Schlumberger Technology Corporation High strength-to-weight-ratio slickline and multiline cables
JP2008139582A (ja) 2006-12-01 2008-06-19 Toyobo Co Ltd 繊維コードテンションメンバー
JP2008138320A (ja) 2006-12-01 2008-06-19 Toyobo Co Ltd 繊維コードテンションメンバー
JP4950308B2 (ja) * 2007-02-15 2012-06-13 ダウ グローバル テクノロジーズ エルエルシー 熱可塑性プラスチック繊維濃縮物の製法および物品
US7847023B2 (en) * 2007-03-12 2010-12-07 Sabic Innovative Plastics Ip B.V. Polysiloxane/polyimide copolymer blends
US8013251B2 (en) * 2008-03-17 2011-09-06 Sabic Innovative Plastics Ip B.V. Electrical wire comprising an aromatic polyketone and polysiloxane/polyimide block copolymer composition
US8013076B2 (en) * 2008-03-17 2011-09-06 Sabic Innovative Plastics Ip B.V. Aromatic polyketone and polysiloxane/polyimide block copolymer composition
CN101597140B (zh) 2009-07-02 2011-01-05 重庆国际复合材料有限公司 一种高强度高模量玻璃纤维
CN102630236B (zh) * 2009-09-16 2015-08-12 联合碳化化学及塑料技术有限责任公司 交联的熔融成型的制品以及制备该制品的组合物
CA2799616A1 (en) * 2010-06-08 2011-12-15 Union Carbide Chemicals & Plastics Technology Llc Fiber-reinforced, thermoplastic tape as a strength member for wire and cable
EP2580616A1 (en) 2010-06-08 2013-04-17 Dow Global Technologies LLC Partially impregnated, fiber reinforced thermoplastic strength member
JP5945274B2 (ja) 2010-09-29 2016-07-05 ダウ グローバル テクノロジーズ エルエルシー ワイヤケーブルのための可撓性テンションメンバ
EP2646509B1 (en) 2010-12-03 2020-07-15 Teijin Aramid B.V. High molecular weight polyethylene
US20130273369A1 (en) * 2010-12-29 2013-10-17 Huajun Zhou Method of Making a Cable Strength Member

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1150482A (zh) * 1995-01-24 1997-05-21 阿尔卡特尔Na电缆系统公司 用于光缆中的聚丙烯聚乙烯共聚物缓冲管及其制造方法
US20040120664A1 (en) * 2002-12-19 2004-06-24 Alcatel Anti-rotational central strength member

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103995329A (zh) * 2014-05-05 2014-08-20 浙江一舟电子科技股份有限公司 一种新型非金属层绞式矿用光缆
CN112731603A (zh) * 2020-12-23 2021-04-30 华为技术有限公司 光缆
WO2022135075A1 (zh) * 2020-12-23 2022-06-30 华为技术有限公司 光缆

Also Published As

Publication number Publication date
WO2012044498A1 (en) 2012-04-05
US20130177282A1 (en) 2013-07-11
BR112013006984A2 (pt) 2020-09-29
EP2622005A1 (en) 2013-08-07
CA2812746C (en) 2017-08-29
MX337207B (es) 2016-02-17
MX2013003505A (es) 2013-05-20
JP5945274B2 (ja) 2016-07-05
US8995810B2 (en) 2015-03-31
KR20130124303A (ko) 2013-11-13
EP2622005B1 (en) 2018-07-04
KR101948331B1 (ko) 2019-02-14
JP2014500971A (ja) 2014-01-16
CA2812746A1 (en) 2012-04-05
CN103221460B (zh) 2015-11-25
TW201229599A (en) 2012-07-16

Similar Documents

Publication Publication Date Title
CN103221460B (zh) 用于缆线的柔性加强件
CN106221204B (zh) 玻纤增强聚酰胺组合物及其制备方法和应用
CN101535382A (zh) 有机纤维增强的复合树脂组合物及有机纤维增强的复合树脂成形品
CN101113240A (zh) 一种高导热聚苯硫醚复合材料及其制备方法
CN102492215A (zh) 一种耐磨玻纤增强聚丙烯复合物及其制备方法
KR101526742B1 (ko) 성형성이 우수한 탄소섬유 보강 폴리프로필렌 수지 조성물
CN105176079A (zh) 一种短切玻璃纤维增强尼龙改性材料及其制备方法
CN104194123B (zh) 聚丙烯腈纤维/高密度聚乙烯复合材料的制备方法
JP2013528135A (ja) ワイヤーおよびケーブルのための強度部材としての繊維強化熱可塑性樹脂テープ
CN104371229A (zh) 高浸润性高强度连续碳纤维增强聚偏氟乙烯复合材料及制法
KR101549663B1 (ko) 장섬유 강화 폴리프로필렌 수지 조성물 및 이를 이용하여 제조된 수지 성형품
CN115449153B (zh) 聚丙烯组合物、长纤增强聚丙烯复合材料及其制备方法和应用、制品
CN106232693A (zh) 纤维增强塑料组合物、由此形成的提高冲击性能的纤维增强复合材料
JP2002085109A (ja) 安全靴用先芯
KR102360985B1 (ko) 장섬유 강화 열가소성 수지 조성물 및 이를 이용하여 제조된 성형품
JP4956974B2 (ja) 導電性熱可塑性樹脂組成物及び成形品
EP3147312A1 (en) Continuous fiber reinforced composite and manufacturing method therefor
KR20200082391A (ko) 계면특성이 향상된 현무암 장섬유 강화 열가소성 복합소재 및 이의 제조방법
KR102672945B1 (ko) 장섬유 강화 복합재료 및 이로부터 형성된 성형품
CN111117068A (zh) 一种改性聚丙烯复合材料及其制备方法
KR20180038266A (ko) 장섬유 강화 사출 성형품 및 그 조성물
KR102020606B1 (ko) 내후성이 우수한 장섬유 강화 열가소성 수지 조성물 및 이를 포함하는 성형품
KR20140087913A (ko) 장섬유 강화 폴리아미드계 수지 조성물 및 이를 포함하는 성형품
KR20210038747A (ko) 폴리아미드 수지 조성물 및 이로부터 제조된 성형품
KR20170036193A (ko) 섬유 강화 복합재 및 이의 제조방법

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20151125

Termination date: 20200921