CN106459565A - 聚合物组合物和热收缩性制品 - Google Patents

聚合物组合物和热收缩性制品 Download PDF

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CN106459565A
CN106459565A CN201580028226.5A CN201580028226A CN106459565A CN 106459565 A CN106459565 A CN 106459565A CN 201580028226 A CN201580028226 A CN 201580028226A CN 106459565 A CN106459565 A CN 106459565A
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S.库鲁普
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Tyco Electronics UK Ltd
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Abstract

本发明涉及聚合物组合物和热收缩性制品，所述热收缩性制品例如用作电绝缘管。根据本发明的聚合物组合物包括基于聚酯的热塑性弹性体和乙烯丙烯酸类弹性体的共混物。此外，所述配方包括基于有机磷的阻燃剂。本发明还涉及由这样聚合物组合物的形成的热收缩性制品。

Description

聚合物组合物和热收缩性制品
本发明涉及聚合物组合物和热收缩性制品，所述热收缩性制品例如用作电绝缘管。
尺寸能恢复的制品例如能热恢复的管是公知的。这样的制品经常用于在拼接线上面提供电和环境绝缘，或者保护电缆的其中存在破裂的区域处于绝缘。为了提供足够的恢复性和柔性，所述制品通常包括聚合物。对于许多应用而言，必要的是，所述聚合物是阻燃的以使在火灾情况下的损害的风险最小化。这样的阻燃性可通过使用包含卤素的聚合物例如含氟聚合物、或者通过将经卤化的材料例如经溴化的或经卤化的化合物如十溴二苯基乙烷添加至非卤化的聚合物例如聚烯烃如聚乙烯、乙烯共聚物或者聚酯而实现。具有这样的阻燃性的聚合物型化合物(聚合物配混物，polymeric compound)是有用的，因为它们在从火焰移开时自熄。然而，它们却具有缺点，因为它们可经历连续的燃烧而产生大量的烟，或者它们可热分解，从而释放腐蚀性气体例如卤化氢，其对人员或者敏感的电子设备可为有害的。
已经尝试将不含卤素的阻燃剂引入到聚合物树脂中以克服以上缺点。不含卤素的阻燃剂例如三水合氧化铝(ATH)必须以相对大的浓度使用以向所得组合物提供充分有用的阻燃性。然而，当将大的浓度的不含卤素的阻燃剂添加到聚合物树脂时，所得树脂组合物在挤出时呈现出降低的物理性质，尤其是在拉伸强度和伸长率方面，以及大幅降低的老化性质和电性质。另外，这些组合物难以挤出和膨胀成管、尤其是薄壁管。
当所述组合物以管的形式使用时，进行大量与产品有关的火焰试验。对于军事和航空航天应用而言特别重要的是IEC 60684-3-271、VG 95343-5 D型、SAE-AS-I-23053/16，其包含若干不同的方面，包括物理性质即拉伸强度和伸长率的测量，和管在暴露于火焰时的性能的测量。根据VG 95343-5 D型、燃烧行为试验编号5.12.1.1，使一段长度尺寸为约150mm的热收缩管在长度为约200mm的金属芯轴上收缩，该金属芯轴的直径(四舍五入为最近的整mm)必须比该自由收缩的管的内径大10％。然后根据规定的试验方法，将试样标记和放置在燃烧室中，标记所述试样的位置、火焰的施加点等。火焰的施加持续时间为60秒。为了通过该火焰试验，在已经将试验火焰移开之后，燃烧必须对于D型产品在15秒内和对于L型产品在30秒内自动熄灭。
还合乎需要的是，所述管具有对于在升高的温度下例如在150℃下持续使用3000小时而言足够的性能。当所述管用于军事应用时，这样的高温性能是特别重要的。
由其中阻燃剂包括十溴二苯基乙烷的共聚酯/乙烯丙烯酸类共聚物共混物制成的包含卤素的管是已知的。常规的经卤化的管的实例为可得自TE Connectivity的DR25TM管。虽然这样的管具有可接受的物理性质和可燃性性质，但是对于一些市场，需要不含卤素的材料，其具有聚合物材料的高的化学耐受性、低的重量以及出色的拉伸和伸长性质。
因此，存在提供较高温度等级的、高度化学耐受性的、阻燃的聚合物组合物的需要，其特别可用作热收缩性管。特别地，应达到150℃的温度等级并且同时所述聚合物组合物应不含卤素。
该目的通过独立权利要求的主题而得以解决。有利实施方式为从属权利要求的主题。
本发明基于如下理念：通过在作为基于聚酯的热塑性弹性体和乙烯丙烯酸类弹性体的共混物的基体中使用基于有机磷的阻燃剂，可实现轻质、不含卤素、仍然高强度的热收缩性产品。特别地，通过使用根据本发明的聚合物组合物，可达到150℃(150C)等级。该聚合物组合物特别适合用于制造热收缩性管和模塑零件(部件)、非热收缩性电缆外壳(jacket)、电线和光缆护套(sheathing)。
根据本发明的有利实施方式，所述基于聚酯的热塑性弹性体包括聚对苯二甲酸丁二醇酯与聚亚烷基醚二醇的共聚物。市售的合适的热塑性弹性体的实例为HYTREL-4056。该具体材料呈现出机械、物理和化学性质的独特组合并且特别地提供杰出的回弹性、柔性、高的耐挠曲疲劳性和耐机械损伤性的优点。
根据本发明，所述聚合物基体为所述基于聚酯的热塑性弹性体和乙烯丙烯酸类弹性体的共混物。可表明的是，为了提供最终产品的足够高的柔性，将基于聚酯的热塑性弹性体与纯粹的弹性体共混导致具有杰出性能的材料。通过在宽的溶剂和温度范围内具有优异的耐溶剂性并且同时提供良好的热老化性质的乙烯丙烯酸类弹性体可实现特别有说服力的结果。
这样的乙烯丙烯酸类弹性体可例如以注册商标VAMAC购得。
仔细地选择所述基于聚酯的热塑性弹性体和所述乙烯丙烯酸类弹性体之间的比率以实现改善的耐溶剂性、高的柔性、减少的热老化和低温性质。特别地，热塑性弹性体的量可在整个组合物的30重量％-40重量％之间选择，而所述乙烯丙烯酸类弹性体为整个组合物的约15重量％-25重量％。
根据第一有利实例，所述基于聚酯的热塑性弹性体占36重量％并且所述乙烯丙烯酸类弹性体为19重量％。
第二有利配方包含35重量％的所述基于聚酯的热塑性弹性体和19重量％的所述乙烯丙烯酸类弹性体。
为了降低最终产品的可燃性，将阻燃剂添加至所述弹性体基体。
传统的经卤化的阻燃剂为例如与三氧化二锑组合的溴化合物。溴化合物在燃烧时、以及在加工、再循环或处置期间可产生有毒物质，并且对人和环境产生严重问题。因此，已知使用金属氢氧化物作为不含卤素的阻燃剂并且为了满足VG(VG 95343-5 L型)的可燃性要求，需要在35重量％和60重量％之间的比较高百分数的负载。可表明，这样的高的负载对最终产品的机械性质具有有害影响。
本发明提供替代的、更有效的不含卤素且无毒的阻燃剂，由于其在聚合物基体中比较低的剂量，其对机械性质和电性质具有最小的影响。发现二烷基次膦酸的金属盐、特别是二烷基次膦酸铝是与根据本发明的基于聚酯的热塑性弹性体和乙烯丙烯酸类弹性体的共混物相容的。这样的次膦酸金属盐例如描述于公布的国际申请WO 2011/043260A1中。
二烷基次膦酸铝的关键性质例如高的磷含量、良好的热稳定性、低的密度和非常低的对水分的亲和性已经使得该材料成为用于开发根据本发明的轻质、不含卤素、阻燃且耐流动的热收缩配方的良好选择。
在本案中，通过添加18-22重量％的二烷基次膦酸铝，所述基于聚酯的热塑性弹性体和乙烯丙烯酸类弹性体的共混物的低温柔性受到影响。因此，可添加增塑剂以改善该共混物的低温柔性。例如，可以5-6重量％的负载添加聚己二酸酯(polyester adipate)以显著地改善在-55℃到-75℃之间的范围内的低温性质。可有利地与根据本发明的配方一起使用的增塑剂的实例为PLASTHALL P-650。
由于聚酯弹性体对于水分敏感并且需要稳定剂来防止水解降解，因此可向所述配方添加抗水解剂以保护所述聚酯弹性体免于水解降解。例如，作为芳族聚合物型碳二亚胺的抗水解剂Stabaxol P可有效地用于防止水解降解。
可向所述配方添加热稳定剂以改善所述配方的热老化性质。根据进一步有利实施方式，可向所述配方添加辐射交联剂。这样的辐射交联剂在暴露于辐射(例如来自高能电子束的辐射)时促进聚合物交联。所述辐射交联促进剂可选自常规用于促进聚合物的交联的那些，包括氰尿酸三烯丙酯(TAC)、异氰尿酸三烯丙酯(TAIC)、偏苯三甲酸三烯丙酯、均苯三甲酸三烯丙酯、均苯四甲酸四烯丙酯、1,1,3,-三甲基-5-羧基-3-(4-羧基苯基)茚的二烯丙基酯、三羟甲基丙烷偏苯三甲酸酯(TMPTM)、季戊四醇三甲基丙烯酸酯、异氰尿酸三(2-丙烯酰氧乙基酯)、偏苯三甲酸三(2-甲基丙烯酰氧乙基酯)等。
在下文中，将说明根据本发明的配方的两个具体实施方式。然而，对于本领域技术人员来说，清楚的是，在不背离本发明的总的原理的情况下，可从所给百分比进行若干偏离。
表1总结了根据本发明的第一零卤素配方。
表1
通过该具体配方，提供轻质、150℃等级的、不含卤素的、阻燃的能交联的聚合物组合物用于制造热收缩性产品。特别地，由该高度化学耐受性的、轻质的、并且具有出色的拉伸和伸长性质的配方可制造非卤化的热收缩性管。
将所述有机次膦酸铝熔融混合到基于聚酯弹性体的体系中，该基于聚酯弹性体的体系另外包含若干种抗氧化剂和加工助剂以得到更好的热老化性质和改善的加工性。可表明，18-21重量％的有机次膦酸铝足以满足VG95343-5 D型规范的可燃性要求。虽然可使用更高的百分比例如25％，但是这可能使聚合物的机械性质恶化。
在一些应用条件下，可要求，将消烟剂添加至根据本发明的组合物。在以下作为表2显示的实施方式中，阻烟剂FireBrake产生令人满意的结果。根据本发明，该物质是以大约5重量％的负载添加的。
下表2总结了另外包含消烟剂的根据本发明的组合物的实例。
表2
根据本发明，使用阻燃剂Exolit 1240或Exolit OP 935作为二烷基次膦酸铝。根据本发明，Exolit 1240和Exolit OP 935在满足VG 95343-5D型燃烧行为方面产生了最佳结果。
总之，根据本发明的配方提供阻燃的、不含卤素的、轻质聚合物配方，其满足VG95343-5 D型的要求，包括在升高的温度(23℃-100℃)下的流体耐受性、从-55/-75℃到150℃的使用温度范围、和良好的柔性。该配方可用于热收缩性管或者用于电缆外壳。

Claims (15)

1.热收缩性制品，其由辐射交联的聚合物组合物制成，所述聚合物组合物包括：
基于整个组合物的30-40重量％的基于聚酯的热塑性弹性体，
基于整个组合物的15-25重量％的乙烯丙烯酸类弹性体，和
基于有机磷的阻燃剂，
其中所述基于有机磷的阻燃剂包括二烷基次膦酸的金属盐。
2.根据权利要求1的热收缩性制品，其中所述基于聚酯的热塑性弹性体包括聚对苯二甲酸丁二醇酯与聚亚烷基醚二醇的共聚物。
3.根据权利要求1或2的热收缩性制品，其中所述金属盐为二乙基次膦酸铝。
4.根据权利要求1、2或3的热收缩性制品，其中所述乙烯丙烯酸类弹性体包括乙烯、丙烯酸甲酯、和固化位点单体的三元共聚物。
5.根据前述权利要求之一的热收缩性制品，其中所述聚合物组合物进一步包括抗水解剂和/或稳定剂。
6.根据权利要求5的热收缩性制品，其中所述抗水解和稳定剂包括芳族聚合物型碳二亚胺和/或芳族胺型抗氧化剂。
7.根据前述权利要求之一的热收缩性制品，其中所述聚合物组合物进一步包括增塑剂。
8.根据权利要求7的热收缩性制品，其中所述增塑剂包括聚己二酸酯。
9.根据前述权利要求任一项的热收缩性制品，其中所述聚合物组合物包括辐射交联促进剂，所述辐射交联促进剂选自常规用于促进聚合物的交联的那些，包括氰尿酸三烯丙酯(TAC)、异氰尿酸三烯丙酯(TAIC)、偏苯三甲酸三烯丙酯、均苯三甲酸三烯丙酯、均苯四甲酸四烯丙酯、1,1,3,-三甲基-5-羧基-3-(4-羧基苯基)茚的二烯丙基酯、三羟甲基丙烷偏苯三甲酸酯(TMPTM)、季戊四醇三甲基丙烯酸酯、异氰尿酸三(2-丙烯酰氧乙基酯)、偏苯三甲酸三(2-甲基丙烯酰氧乙基酯)和其组合。
10.根据前述权利要求之一的热收缩性制品，其中所述聚合物组合物进一步包括消烟剂。
11.根据权利要求10的聚合物组合物，其中所述消烟剂包括硼酸锌。
12.根据前述权利要求之一的热收缩性制品，其中所述基于有机磷的阻燃剂为整个组合物的15重量％-25重量％。
13.根据前述权利要求任一项的热收缩性制品，其为管或模塑零件的形式。
14.根据权利要求13的热收缩性制品，其形成为电绝缘管。
15.电缆、电线或者光缆，其具有根据权利要求14的电绝缘管的护套或外壳。
CN201580028226.5A 2014-05-28 2015-04-23 聚合物组合物和热收缩性制品 Pending CN106459565A (zh)

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