CN103772972B - 二烷基次膦酸盐作为提高尼龙树脂组合物电性能和挠度的添加剂的用途 - Google Patents

二烷基次膦酸盐作为提高尼龙树脂组合物电性能和挠度的添加剂的用途 Download PDF

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CN103772972B
CN103772972B CN201410001037.6A CN201410001037A CN103772972B CN 103772972 B CN103772972 B CN 103772972B CN 201410001037 A CN201410001037 A CN 201410001037A CN 103772972 B CN103772972 B CN 103772972B
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nylon resin
resin composition
dialkylphosphinic salts
deflection
amount
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CN103772972A (zh
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陈林
孔蕾
卢昌利
李积德
李岩
柴生勇
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Zhuhai Wantong Chemical Co Ltd
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GUANGZHOU KINGSKY MATERIAL CO Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/53Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313Phosphinic compounds, e.g. R2=P(:O)OR'
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets

Abstract

本发明公开了一种二烷基次膦酸盐作为提高尼龙树脂组合物电性能和挠度的添加剂的用途,所述二烷基次膦酸盐的加入量占尼龙树脂组合物总重量的1~40%。本发明将二烷基次膦酸盐作为添加剂添加到尼龙树脂中,二烷基次膦酸盐可以提高尼龙树脂组合物的电性能,调整尼龙树脂组合物的挠度,所制备得到的尼龙树脂组合物的CTI值和挠度值有明显的提高,大大拓宽了二烷基次膦酸盐在市场中的应用范围。

Description

二烷基次膦酸盐作为提高尼龙树脂组合物电性能和挠度的添加剂的用途
技术领域
本发明涉及二烷基次膦酸盐的新用途,特别涉及二烷基次膦酸盐作为提高尼龙树脂组合物电性能和挠度的添加剂的用途。
背景技术
二烷基次膦酸盐含磷量高,热稳定性好、在加工中不引起聚合物的分解,也不影响塑料模制组合物。近年来研究表明,含有二烷基次膦酸盐的聚合物组合物呈现较高的阻燃性,如文献“次膦酸盐阻燃剂的合成及阻燃尼龙6研究”中报道了采用酸碱中和法合成二烷基次膦酸盐,同时研究了对PA6的阻燃性能。CN200480043753.5公开了一种无卤素阻燃热塑性模压组合物,它包含至少一种二烷基次膦酸盐作为无卤阻燃剂及至少一种基于聚酯的聚合物。
上述文献表明,二烷基次膦酸盐用在PA6,PET等改性塑料上,取得了很高的阻燃效果,添加入PET中,放热率和燃烧时产生的热量急剧减少,燃烧后的成炭量增加,阻燃性能达到UL94标准V-0级,并且通过实验比现在国内使用的PET阻燃剂,阻燃效果可提高60%。
目前,二烷基次膦酸盐被广泛应用为一种高效的阻燃剂,但是,二烷基次膦酸盐在提高提高尼龙树脂组合物电性能和挠度的应用的文献未见报道。
发明内容
本发明的目的在于提供一种二烷基次膦酸盐作为提高尼龙树脂组合物电性能和挠度的添加剂的用途。
本发明所述的二烷基次膦酸盐具有如下结构式(Ⅰ),
其中,R1,R2相同或不同,表示为H、乙基、丙基、丁基、戊基、环戊基、环己基或辛基,条件是两者不能同时为H;
M为Mg、Ca、Al、Sb、Sn、Ge、Ti、Zn、Fe、Zr或Sr;
m为2~4。
优选的,所述的二烷基次膦酸盐为二乙基次膦酸铝。
其中,所述二烷基次膦酸盐的加入量占尼龙树脂组合物总重量的1~40%。
优选的,所述二烷基次膦酸盐的加入量占尼龙树脂组合物总重量的5~30%。
更优选的,所述二烷基次膦酸盐的加入量占尼龙树脂组合物总重量的10~20%。
本发明所述的尼龙树脂包括PA6、PA66、PA10、PA12、PA11、PA610、PA6T、PA10T或PA9T中的一种或几种的混合。
本发明所述的二烷基次膦酸盐可以采用现有技术中常规的合成方法制备得到,如将次膦酸钠溶液与硫酸铝或硝酸铝溶液在加热及酸性条件下反应生成二烷基次膦酸盐。二烷基次膦酸盐中可以含有特别低含量的残余溶剂和调聚产物。
本发明所述的尼龙树脂组合物可通过已知方法制得,如将各组分预混,然后将混合均匀的物料置于双螺杆挤出机中,通过双螺杆机熔融、挤出,造粒即得。
本发明意外的发现,将二烷基次膦酸盐作为添加剂添加到尼龙树脂中,二烷基次膦酸盐可以提高尼龙树脂组合物的电性能和挠度,所制备得到的尼龙树脂组合物的CTI值和挠度值有明显提高,大大拓宽了二烷基次膦酸盐在市场中的应用范围。
具体实施方式
下面通过具体实施方式来进一步说明本发明,以下实施例为本发明较佳的实施方式,但本发明的实施方式并不受下述实施例的限制。
含有二烷基次膦酸铝的聚酯组合物的制备:
首先将各对比例/实施例(表1)中的各组分预混,然后将混合均匀的物料置于双螺杆挤出机中,通过双螺杆机在250℃条件下熔融挤出,造粒,即得。粒料在80℃、真空干燥箱中持续干燥4小时后,将所得干燥后粒料在230℃~300℃的温度下加工成试验用标准试样100*100*3mm的标准板,标准板按照GB4207-2004,IEC112-1979和ASTMD3638-77,的规定,在规定的环境中,±200C,湿度45-55%环境中存放48H,然后进行CTI测量。各例试样的性能测试数据见表1。
表1实施例1~9及对比例1~4中各组成的具体配比及其测试性能结果(wt%)
由上述实施例和对比例的结果比较可以看出,往尼龙树脂组合物中添加二乙基次膦酸铝,可以明显提高尼龙树脂组合物的CTI值和挠度值,所制备得到的尼龙树脂组合物具有高耐漏电起痕的特性,大大拓宽了二烷基次膦酸盐在市场中的应用范围。

Claims (2)

1.二烷基次膦酸盐单一组分作为提高尼龙树脂组合物电性能和挠度的添加剂的用途;所述二烷基次膦酸盐为二乙基次膦酸铝;所述二烷基次膦酸盐的加入量占尼龙树脂组合物总重量的10~20%。
2.根据权利要求1所述的二烷基次膦酸盐作为提高尼龙树脂组合物电性能和挠度的添加剂的用途,其特征在于,所述尼龙树脂包括PA6、PA66、PA10、PA12、PA11、PA610、PA6T、PA10T或PA9T中的一种或几种的混合。
CN201410001037.6A 2014-01-02 2014-01-02 二烷基次膦酸盐作为提高尼龙树脂组合物电性能和挠度的添加剂的用途 Active CN103772972B (zh)

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KR20200062336A (ko) 2017-10-17 2020-06-03 셀라니즈 세일즈 저머니 게엠베하 난연성 폴리아미드 조성물

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