CN106009644B - 羟基磷灰石在减弱红磷阻燃剂在尼龙中产生异味的应用 - Google Patents
羟基磷灰石在减弱红磷阻燃剂在尼龙中产生异味的应用 Download PDFInfo
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本发明公开羟基磷灰石在减弱红磷阻燃剂在尼龙中产生异味的应用，将羟基磷灰石添加到红磷阻燃的尼龙6中，使红磷阻燃尼龙6在加工过程中释放的毒性气体磷化氢释放量减少，具有一定的吸附储存气体作用；且这种添加剂不会影响添加红磷所提高的阻燃性能。
Description
技术领域
本发明属于尼龙6阻燃技术领域，更加具体的说，涉及一种减弱红磷阻燃剂在尼龙6中产生异味的方法，即羟基磷灰石在减弱红磷阻燃剂在尼龙6中产生异味的应用。
背景技术
红磷是一种阻燃性能优良的无卤阻燃添加剂，其有效含磷量高，阻燃效果明显，与其他阻燃剂相比达到相同阻燃等级的添加量少，例如，以7.5％红磷阻燃的聚酰胺氧指数可达35％，而15％溴系阻燃剂阻燃的聚酰胺氧指数仅达28％，因此对制品的物理、力学性能影响较小，对制品的抗电弧性能有所改善，且价格低廉，目前在国内阻燃剂方面应用广泛，可广泛用于阻燃聚烯烃、聚苯乙烯、聚酯、聚氨酯、尼龙、聚碳酸酯、聚甲醛、环氧树脂、橡胶、纺织品等。红磷阻燃主要是在凝聚相起作用，其阻燃机理是在燃烧时红磷先被氧化，吸水后产生磷酸，磷酸可进一步脱水生产偏磷酸，进而聚合生成聚偏磷酸，这种可燃性碳化物形成玻璃状物质覆盖于聚合物表面，抑制燃烧，从而达到阻燃作用。但其对制品的着色性和在储存、运输、加工中易释放出有毒气体磷化氢这两大缺点，一直是人们关注的焦点，尤其是后者，磷化氢的生产使得空气质量变差，且对人体有危害作用，车间空气中有害物质硫化氢的最高容许浓度10mg/m3(摘自TJ36—79)。关于着色性和储存不稳定性，对红磷进行表面包覆处理能有效解决这类问题，但对于有毒气体的释放抑制，仍然没有有效的解决方法。
现阶段人们对红磷阻燃尼龙(如尼龙6)过程中异味的产生，一般认为是红磷在尼龙体系中生成了磷化氢(具有臭味，有毒)并扩散到空气中导致的。在去除红磷阻燃尼龙体系的异味方面，目前人们主要通过添加香料遮住臭味或者添加多孔物质进行有限吸附以消除异味，但这些方法没有或者难以彻底有效地解决异味问题，实际效果欠佳。也有部分文献报道尝试绕开红磷阻燃剂的使用，如通过开发反应性阻燃剂等新型阻燃剂来替代红磷，进而解决阻燃体系的异味问题，但由于价格等原因该方法的普及度并不高。基于磷化氢生成的环节来阻止其生成反应的发生，进而避免磷化氢的产生，由此彻底解决异味问题，这应当是解决红磷阻燃尼龙材料异味问题的重要途径，但这方面的相关文献报道很少见。
发明内容
本发明的目的在于克服现有技术的不足，在不影响红磷阻燃剂对尼龙6阻燃效果的前提下，添加一种添加剂，这种添加剂可在红磷阻燃尼龙6热加工(如加工温度为240—260℃)条件阻止产生的磷化氢释放出来，消除或减弱在尼龙6中添加红磷阻燃剂后的异味，满足一些对空气质量要求较高的使用环境的条件。
本发明的技术目的通过下述技术方案予以实现：
羟基磷灰石在减弱红磷阻燃剂在尼龙中产生异味的应用，羟基磷灰石的用量大于零且小于等于尼龙和红磷阻燃剂质量之和的5％，优选2—4％。
在上述技术方案中，羟基磷灰石直接用熔融共混的方式加入到红磷阻燃尼龙材料中，通过熔融共混使混合均匀时，采用双螺杆挤出造粒或密炼机密炼。
在上述技术方案中，添加红磷阻燃剂和羟基磷灰石的尼龙材料的热成型加工温度为240—260摄氏度。
在上述技术方案中，尼龙为尼龙6。
在上述技术方案中，羟基磷灰石为纳米级羟基磷灰石团聚少、粒度均匀、形态规则，变现为50nm长度的棒状排列而成的多孔性物质。
与现有技术相比，本发明在不影响红磷阻燃剂阻燃效果的前提下，采用一种多孔状无机物羟基磷灰石作为除味剂，这种除味剂可在红磷阻燃尼龙6热加工过程中对产生的磷化氢有毒气体产生吸附和储存作用，进而消除尼龙6中添加红磷阻燃剂后的异味，在尼龙6的加工过程中，可通过简单混料的方式完成添加剂的添加，使生产出来的产品可满足一些对空气质量要求较高的使用环境的要求。
附图说明
图1是本发明实施例中羟基磷灰石的扫描电镜照片。
图2是本发明实施例中羟基磷灰石的透射电镜照片。
图3是本发明实施例中羟基磷灰石的XRD谱图。
具体实施方式
下面结合具体实施例进一步说明本发明的技术方案。
首先，制备羟基磷灰石(Zhang W,Chai Y,Cao N,et al.Synthesis andcharacterization of selenium substituted hydroxyapatite via a hydrothermalprocedure[J].Materials Letters,2014,134:123-125)：
(1)配制反应溶液，用pH＝10的稀氨水作溶剂，Ca(NO3)2·4H2O物质的量浓度为0.6680mol/L，体积为30.00mL。配置30ml，0.399mol/L的(NH4)2HPO4溶液。
(2)在快速磁力搅拌下将(NH4)2HPO4溶液缓慢滴入Ca(NO3)2·4H2O溶液中，反应过程中滴加氨水维持溶液的pH＝10，并在室温下继续搅拌100min。
(3)将溶液倒入100mL的水热反应釜中，确保反应釜锁紧后放入烘箱，在160℃下保温36h后，自然冷却至室温。
(4)减压抽滤，分离，用去离子水反复洗涤至上清液的pH＝7，产品在100℃的烘箱中干燥24h，研磨。
采用北京大学仪器厂生产的型号为BDX 3300的X射线衍射仪，选用波长的铜靶CuKα为射线源，管电压和管电流分别为30KV和30mA，步进式扫描，扫面范围2θ＝10–60°，步宽为0.02°，步长为0.3s。制备的纳米级羟基磷灰石团聚少、粒度均匀、形态规则，羟基磷灰石变现为50nm长度的棒状排列而成的多孔性物质，如图1和图2所示，且表现出良好晶型，如图3所示。
称取450g尼龙6，50g红磷在挤出机中混合，并通过注塑机得到0％添加剂的样条；称取450g尼龙6，50g红磷，5g制备的羟基磷灰石在挤出机中混合，并通过注塑机得到1％添加剂的样条；称取450g尼龙6，50g红磷，10g制备的羟基磷灰石在挤出机中混合，并通过注塑机得到2％添加剂的样条；同理得到羟基磷灰石为3％，4％的样条，上述实验中尼龙6的加工温度为240—260摄氏度。
按照UL 94阻燃检测标准对添加了添加剂的阻燃样条进行的阻燃测试(垂直燃烧测试仪GB/T5455)，结果如下表所示，添加剂的使用不降低红磷阻燃剂对尼龙材料的阻燃效果，观察不到对阻燃效果的负面影响。
样品的阻燃数据
| 测试样品 | 0％添加剂 | 1％添加剂 | 2％添加剂 | 3％添加剂 | 4％添加剂 |
| 阻燃等级 | V1 | V1 | V1 | V1 | V1 |
测试添加剂的使用对红磷阻燃尼龙材料的各项力学性能的影响，添加剂使用不显示对这些力学性能的负面影响。
(1)拉伸及弯曲测试：将样品制成尺寸为长为150mm，宽为25mm，厚度为2mm的哑铃型样条，用作测试拉伸力学性能，制成长为100mm，宽为20mm,厚为2mm的矩形样条，用作测试弯曲力学性能，拉伸和弯曲力学性能的测试标准分别依据ISO 527-1和ISO178，测试仪器为万能拉力试验机SMT-5000。拉伸测试的样品标距为20mm，测试速度为15mm/min，传感器的大小为50kN。弯曲测试的样品厚度为2mm，测试速度为1mm/min，传感器的型号为50kN。
(2)缺口冲击测试：选用的是悬臂梁冲击测试，测试标准依据GB1043国家标准，测试用机为摆锤式冲击试验机TZ5274A。将样品制成长为100mm，宽为20mm，厚度为4.24mm的矩形样条，样条的缺口深度为1.48mm。
样品的物理性能数据
除味剂用量(羟基磷灰石用量)与红磷在阻燃体系中的用量相关，并随着除味剂相对红磷用量的提高，除味效果逐步改善。如在红磷阻燃剂的添加比例为尼龙6的5％时，添加剂用量为尼龙和红磷总质量的1％，2％，3％，4％时，除味效果随着添加量增加有显著提高。
除味剂的吸附除味效果明显，如通过在恒温煅烧装置中于阻燃尼龙材料通常采用的加工温度250℃下，在测试过程中不含添加剂的试样会产生明显的白烟，而含有添加剂1％、2％、3％及4％的试样则无明显白烟现象。另将收集到的气体部分缓慢通入双氧水溶液，充分吸收后用1mol/L的氢氧化钠水溶液进行酸碱滴定，以酚酞做指示剂，得到产生的磷化氢的量，结果显示，有添加剂的组分释放的磷化氢明显要比无添加的要少，且添加剂含量越多，产生的磷化氢越少，具体数值如下表所示。这说明添加剂的使用对体系中的磷或其化合物有吸附固定的效果，能在高温甚至起火等条件下减少由于红磷阻燃尼龙6材料中所含有红磷阻燃剂引起的空气环境恶化。
250℃下各组分的磷化氢释放量
以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。
Claims (2)
1.羟基磷灰石在减弱红磷阻燃剂在尼龙中产生异味的应用，其特征在于，羟基磷灰石的用量大于零且小于等于尼龙和红磷阻燃剂质量之和的5％，羟基磷灰石为纳米级羟基磷灰石，羟基磷灰石直接用熔融共混的方式加入到红磷阻燃剂和尼龙材料中并混合均匀；纳米级羟基磷灰石粒度均匀，为50nm长度的棒状排列而成的多孔性物质；尼龙为尼龙6；添加红磷阻燃剂和羟基磷灰石的尼龙材料的热成型加工温度为240—260摄氏度。
2.根据权利要求1所述的羟基磷灰石在减弱红磷阻燃剂在尼龙中产生异味的应用，其特征在于，羟基磷灰石的用量为尼龙和红磷阻燃剂质量之和的2—4％。
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