CN102165001A - 阻燃热塑性弹性体 - Google Patents
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Abstract
揭示了阻燃并且基本上不含卤素的热塑性弹性体(TPE)。该TPE是共聚聚酯(COPE)。采用两种基本上不含卤素的阻燃剂(HFFR):有机次膦酸酯和三聚氰胺聚磷酸酯。该配混物可用于电线和电缆绝缘。
Description
优先权要求
本申请要求于2008年9月30.日提交的美国临时专利申请序列第61/101,512号(代理机构案卷号12008021)的优先权,该专利申请通过参考结合于此。
发明领域
本发明涉及显示弹性同时保留热塑性,也是阻燃的热塑性弹性体聚合物配混物。
发明背景
聚合物领域已经取得飞速发展,使材料科学从19世纪的木材和金属改变为20世纪中期使用热固性聚合物,再改变为20世纪后期使用热塑性聚合物。
热塑性弹性体结合了诸如硫化橡胶等热固性聚合物的高弹性与热塑性聚合物的加工特性的优点。
在一些应用中,出于安全原因,热塑性弹性体应是阻燃的。对于基本上非卤素阻燃剂的(HFFR)的热塑性弹性体(TPE)存在客户需求。
据报道,目前尚没有使交流电(AC)电缆同时符合以下标准的HFFR技术:(a)挠性接近聚氯乙烯(PVC)和(b)遵照保险业实验所(Underwriter′sLaboratory)(UL)62高要求,例如对于绝缘和护套的VW-1,150℃形变,热骤变测试,拉伸/伸长以及在100℃和121℃7天热老化。
采用基于卤素的阻燃剂的共聚聚酯(COPE)热塑性弹性体配混物已经市售多年。但本领域力图避免使用卤化阻燃剂。
专利公开WO/2006/121549报道了在热塑性聚氨酯(TPU)的情况下使用HFFR有机次膦酸酯、有机磷酸酯和无机磷酸盐。
发明内容
使用优于TPU的COPE作为基材或者用于电线和电缆绝缘料的优点在于,在相同的硬度/挠性下基于COPE的电缆比相同硬度的TPU基电缆具有更好的耐温性。换言之,为了符合UL 62 150℃热要求,COPE电缆比TPU电缆明显更具挠性。为具有与PVC(一种卤化化合物)相当的挠性,重要的是使用硬度不高于肖氏硬度33D,优选不高于肖氏硬度30D的COPE。软COPE具有较低的拉伸,因此更难以配制软COPE以符合电缆拉伸/VW-1要求。
本领域需要的是在电线和电缆绝缘应用中使用的通过UL 62 VW-1焰色试验的HFFR COPE TPE配混物。
在本发明中,已发现有机次膦酸酯和三聚氰胺聚磷酸酯的组合作为阻燃剂是COPE非常有效的HFFR,以在本发明中实现通过UL 62 VW-1焰色试验。可任选地加入有机磷酸酯以改善硬度和粘度。
在本发明中,“HFFR”表示在本发明配混物的任意成分中不包括任何卤素部分,但并不能控制该成分中可能存在的痕量杂质。换言之,HFFR表示基本上不含卤素的阻燃剂。
不幸的是,HFFR对于TPE通常经历的加工条件非常敏感。因此,在HFFR TPE的形成过程中本领域普通技术人员几乎不能预测,不论TPE是TPU、COPE或是苯乙烯类嵌段共聚物(SBC)。
本发明通过以下方式解决了该问题:采用有机次膦酸酯和三聚氰胺聚磷酸酯的组合作为阻燃剂,并且任选地还包含有机磷酸酯来配制HFFR COPETPE,以实现本发明配混物通过UL 62 VW-1焰色试验。
本发明的一方面是基本上不含卤素的热塑性弹性体配混物,其包含(a)含共聚聚酯的热塑性弹性体;(b)含有机次膦酸酯的阻燃剂;和(c)含三聚氰胺聚磷酸酯的阻燃剂。任选地,也可使用含有机磷酸酯的阻燃剂。
本发明的另一方面是由该配混物制得的塑料制品,具体是用于电线和电缆产品的绝缘层。
参考以下实施方式,本发明的特征将变得显而易见。
发明实施方式
含共聚聚酯的TPE
本发明的TPE基于共聚聚酯,常常与增塑剂、抗氧化剂、热稳定剂以及一种或多种次要聚合物配混。
任何共聚聚酯TPE都可用于本发明。可根据其适合用作电线和电缆产品的绝缘层的物理性质来选择共聚聚酯TPE。
共聚聚酯TPE的非限制性例子包括:杜邦公司(DuPont)的Hytrel牌TPE;DSM公司的Arnite牌TPE;LG化学品公司(LG Chemicals)的Keyflex牌TPE;和SK化学品公司(SK Chemicals)的Skypel牌TPE。这些产品的分销商包括维持网站提供进一步信息的生产商。
基本不含卤素的阻燃剂
已发现两种不同类型的HFFR阻燃剂尤其适合耐受COPE TPE配混过程中采用的加工条件并且还实现通过UL 62 VW-1焰色试验。
有机次膦酸酯阻燃剂
第一类阻燃剂是有机次膦酸酯。具体说,发现来自德国克莱瑞特有限公司(Clariant GmbH)的Exolit OP牌阻燃剂在本发明配混物中很好地发挥作用。目前优选Exolit OP 1230和1311牌阻燃剂。
三聚氰胺聚磷酸酯阻燃剂
第二类阻燃剂是三聚氰胺聚磷酸酯。可以从希巴公司(Ciba)以Melapur200品牌购得。
任选的有机磷酸酯阻燃剂
可用于本发明TPE的任选的第三类HFFR是有机磷酸酯,例如美国纽约州阿得斯雷的休普莱斯特公司(Supresta of Ardsley,NY,USA)的Phosflex 390磷酸异癸基二苯基酯。该磷酸异癸基二苯基酯已揭示可用作聚氯乙烯的阻燃增塑剂,但意外地发现可用于本发明的COPE TPE中。
任选的添加剂
本发明的TPE配混物可包括常规塑料添加剂,其用量足以使配混物具有所需的加工性或使用性能特性。添加剂的量不应造成浪费或对配混物的加工或使用性能有害。热塑性材料配混领域的技术人员无需过多的实验,仅需参考一些论述(例如塑料添加剂数据库(Plastics Additives Database)(2004),来自塑料设计库(Plastics Design Library)(www.williamandrew.com)),就能够从不同类型的添加剂选出所需添加剂,以将其包含在本发明的配混物中。
任选的添加剂的非限制性例子包括:粘合促进剂;杀生物剂(抗菌剂、杀真菌剂和防霉剂)、消雾剂;抗静电剂;粘合剂、起泡剂和发泡剂;分散剂;填料和增量剂;消烟剂;可膨胀结焦剂(expandable char former);抗冲改性剂;引发剂;润滑剂;云母;颜料、着色剂和染料;增塑剂;加工助剂;其它聚合物;脱模剂;硅烷、钛酸盐/酯和锆酸盐/酯;滑爽剂和防粘连剂;稳定剂;硬脂酸盐/酯;紫外光吸收剂;粘度调节剂;蜡;和它们的组合。
表1显示了本发明的HFFR-TPE中各成分的可接受的、合乎需要的和优选的范围。
加工
在选择了合适的成分以后,本发明配混物的制备是不复杂的。本发明的配混物可以间歇或连续操作的方式制得。
以连续工艺进行的混合操作通常在挤出机中进行,该挤出机的温度提高到足以使聚合物基质熔融,所有添加剂可以在进料喉加入,或者在下游通过注射或侧进料机加入。挤出机速度可以为约50-500转/分钟(rpm),优选约为100-300rpm。通常,将挤出机的出料制成粒料,供以后挤出或模塑成聚合物制品。
以间歇工艺进行的混合操作通常在班拍里(Banbury)混炼机中进行,该混炼机的温度也提高到足以使聚合物基质熔融,以使配混物组分均匀。混合速度为60-1000rpm,混合温度为环境温度至提高的温度。此外,将混炼机的出料切碎为更小的尺寸,供以后挤出或模塑成聚合物制品。
随后的挤出或模塑技术是热塑性聚合物工程领域技术人员众所周知的。不需要过多的实验,仅仅需要参考″挤出、最后的加工指南和手册(Extrusion,The Definitive Processing Guide and Handbook)″;″模塑部件收缩和翘曲手册(Handbook of Molded Part Shrinkage and Warpage)″;″专业模塑技术(Specialized Molding Techniques)″;″旋转模塑技术(Rotational MoldingTechnology)″和″模具、工具和模头修理焊接手册(Handbook of Mold,Tool andDie Repair Welding)″(均由塑料设计库(Plastics Design Library)发布(www.williamandrew.com))之类的文献,本领域技术人员使用本发明的配混物就能制得具有任何想得到的形状和外观的制品。
本发明的实用性
根据本发明,含HFFR的特定组合的COPE TPE在电线和电缆绝缘料和外层中具有出乎意料的用途,因为这些配混物能够通过严格的保险业实验所(UL)62高要求,例如绝缘和护套的VW-1,150℃变形,热骤变测试,拉伸/伸长以及在100℃和121℃的7天热老化。增加抗氧化性、热稳定性以及那些各自的功能添加剂产生的基本上不含卤素的阻燃性使得本发明的HFFRCOPE TPE是一种优良的配混物,用于模塑为在封闭空间中使用时,包括看起来几乎总是隐藏的电线和电缆中使用时需要阻燃的塑料制品。在汽车客厢和飞机乘客舱中使用是可使世界各地的人们受益的本发明配混物用作电线和电缆绝缘层的许多方面中的两方面。
实施例
表2显示了本发明的两个实施例,它们的配方以及成分来源。在所有区段均在约193℃下操作并且以300rpm旋转的双螺杆挤出机中制备这两个实施例的样品。通过进料喉下游的侧进料机加入阻燃剂成分。两个实施例的结果均得到肖氏A硬度86(ASTM D2240,10秒延迟)的粒料。
上述测试显示,虽然实施例1的绝缘层配方没有通过老化拉伸强度和伸长测试,但实施例2的护套层配方通过了该测试。本领域技术人员可利用这些数据来重新配制也能够通过UL 62测试的绝缘层。
非常重要的是,实施例1的绝缘层和实施例2的护套层在所有方面均通过VW-1焰色试验。
本发明不限于上述实施方式。以下是权利要求书。
Claims (10)
1.一种基本上不含卤素的热塑性弹性体配混物,其包含:
(a)含共聚聚酯的热塑性弹性体;
(b)含有机次膦酸酯的阻燃剂;和
(c)含三聚氰胺聚磷酸酯的阻燃剂。
2.如权利要求1所述的配混物,所述配混物还包含含有机磷酸酯的阻燃剂。
3.如权利要求1或2所述的配混物,所述配混物还包含粘合促进剂;杀生物剂;消雾剂;抗静电剂;粘合剂、起泡剂和发泡剂;分散剂;填料和增量剂;防火剂、阻燃剂和消烟剂;抗冲改性剂;引发剂;润滑剂;云母;颜料、着色剂和染料;增塑剂;额外的加工助剂;脱模剂;硅烷、钛酸盐/酯和锆酸盐/酯;滑爽剂和防粘连剂;稳定剂;硬脂酸盐/酯;紫外光吸收剂;粘度调节剂;蜡;和它们的组合。
4.如权利要求1-3中任一项所述的配混物,其特征在于,所述成分的重量百分比包括:
5.如权利要求4所述的配混物,其特征在于,所述成分的重量百分比包括:
6.一种热塑性制品,其包含权利要求1-5中任一项所述的配混物。
7.如权利要求6所述的制品,所述制品是电线和电缆绝缘料的形式。
8.如权利要求7所述的制品,其特征在于,所述绝缘料是护套层、绝缘层或两者。
9.一种由权利要求1-5中任一项所述的配混物绝缘的电线。
10.一种由权利要求1-5中任一项所述的配混物绝缘的电缆。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US10151208P | 2008-09-30 | 2008-09-30 | |
US61/101,512 | 2008-09-30 | ||
PCT/US2009/058440 WO2010039616A2 (en) | 2008-09-30 | 2009-09-25 | Flame retardant thermoplastic elastomers |
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CN102165001A true CN102165001A (zh) | 2011-08-24 |
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CN2009801393715A Pending CN102165001A (zh) | 2008-09-30 | 2009-09-25 | 阻燃热塑性弹性体 |
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US (1) | US20110180300A1 (zh) |
EP (1) | EP2334731A4 (zh) |
CN (1) | CN102165001A (zh) |
WO (1) | WO2010039616A2 (zh) |
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WO2012024280A1 (en) * | 2010-08-17 | 2012-02-23 | E. I. Du Pont De Nemours And Company | Heat stable halogen-free flame retardant copolyester thermoplastic elastomer compositions |
WO2012079243A1 (en) | 2010-12-17 | 2012-06-21 | Dow Global Technologies Llc | Halogen-free, flame retardant composition for wire and cable applications |
US8781278B2 (en) | 2011-03-02 | 2014-07-15 | E I Du Pont De Nemours And Company | Low smoke halogen free flame retardant thermoplastic elastomer compositions containing zeolites |
US9332802B2 (en) | 2011-12-30 | 2016-05-10 | Ticona Llc | Molded polymer articles for use in low temperatures having a low rigidity factor |
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Also Published As
Publication number | Publication date |
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US20110180300A1 (en) | 2011-07-28 |
EP2334731A4 (en) | 2013-05-22 |
WO2010039616A2 (en) | 2010-04-08 |
WO2010039616A3 (en) | 2010-07-01 |
EP2334731A2 (en) | 2011-06-22 |
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