CN103328572B - 阻燃型热塑性模塑复合物 - Google Patents
阻燃型热塑性模塑复合物 Download PDFInfo
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- CN103328572B CN103328572B CN201280005623.7A CN201280005623A CN103328572B CN 103328572 B CN103328572 B CN 103328572B CN 201280005623 A CN201280005623 A CN 201280005623A CN 103328572 B CN103328572 B CN 103328572B
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Abstract
热塑性模塑组合物包含a)30重量%至95重量%的至少一种脂族聚酰胺或共聚酰胺作为组分A,b)1重量%至30重量%的至少一种含有至少3个苯氧基磷腈单元的环状苯氧基磷腈作为组分B,c)1重量%至15重量%的红磷作为组分C,d)0.1重量%至20重量%的至少一种冲击改性聚合物作为组分D,e)0重量%至50重量%的玻璃纤维作为组分E,以及f)0重量%至30重量%的其它添加剂作为组分F,其中组分A至F的总量为100重量%。
Description
本发明涉及基于脂族聚酰胺的阻燃型热塑性模塑组合物,涉及制备该模塑组合物的方法,以及该模塑组合物用于制备模制品、纤维或箔片的用途,还涉及由该模塑组合物制备的模制品、纤维或箔片。
现有技术公开了环状苯氧基磷腈在阻燃型聚酰胺树脂组合物中的用途。EP-A-2100919涉及阻燃型聚酰胺树脂,该阻燃型聚酰胺树脂除聚酰胺树脂外还含有含磷的阻燃物质和玻璃纤维。该含磷的物质可选自三聚氰胺与磷酸的反应产物、(二)次膦酸盐,以及磷腈化合物,特别是环状苯氧基磷腈化合物。
US-A-2010/0261818涉及可用于电气应用的无卤素阻燃型聚酰胺组合物。所述聚酰胺树脂含有次膦酸盐、磷腈和任选选自特定氧化物的阻燃型协同化合物。苯氧基磷腈为可用的环状磷腈的实例。
先前已知的阻燃型聚酰胺组合物的阻燃效果还不足以适合所有的应用。特别地,某些的火焰时间仍然太长。
本发明的目的是提供阻燃型热塑性模塑组合物,所述模塑组合物包含聚酰胺,且其与先前已知的模塑组合物相比呈现降低的火焰时间且被分类为提供良好的防火性。
本发明通过包含下列物质的热塑性模塑组合物实现该目的:
a)30重量%至95重量%的至少一种脂族聚酰胺或共聚酰胺,作为组分A,
b)1重量%至30重量%的至少一种含有至少3个苯氧基磷腈单元的环状苯氧基磷腈,作为组分B,
c)1重量%至15重量%的红磷,作为组分C,
d)0.1重量%至20重量%的至少一种冲击改性聚合物,作为组分D,
e)0重量%至50重量%的玻璃纤维,作为组分E,以及
f)0重量%至30重量%的其它添加剂,作为组分F,
其中组分A至F的总量为100重量%。
已经发现在本发明中环状苯氧基磷腈与红磷的结合给出了降低的火焰时间但未改变防火等级。此处使用红磷与环状苯氧基磷腈的结合可显著改善聚酰胺组合物的阻燃效果。
对热塑性模塑组合物的各个组分描述如下。
组分A
30重量%至95重量%、优选45重量%至84.5重量%、特别是55重量%至69.5重量%的至少一种脂族聚酰胺或共聚酰胺用作组分A。在本发明的一个实施方案中,最小量可为59.5重量%。
通过初始单体的反应来制备用于本发明的聚酰胺,所述初始单体例如选自二羧酸和二元胺或二羧酸和二元胺的盐、氨基羧酸、氨基腈、内酰胺及其混合物。此处可使用任何所需的脂族聚酰胺初始单体。所述聚酰胺可为无定形的、结晶的或半晶质的。此外,这些聚酰胺可具有任何所需的合适的粘度及各自的分子量。特别合适的聚酰胺具有脂族、半晶质或半芳族或无定形的任何类型的结构。
这些聚酰胺的固有粘度通常为90至350ml/g,优选110至240ml/g,根据ISO307在25°C下在96重量%硫酸中以0.5重量%的溶液测定。
优选具有至少5000的分子量(重均)的半晶质和无定形树脂,其例如描述于以下美国专利中:2071250,2071251,2130523,2130948,2241322,2312966,2512606和3393210。这些实例为衍生自具有7至11个环单元的内酰胺的聚酰胺,例如聚己内酰胺和聚辛内酰胺,以及通过二羧酸与二元胺的反应所得的聚酰胺。
可使用的二羧酸为具有6至12、特别是6至10个碳原子的链烷二羧酸。此处可提及以下酸:己二酸、壬二酸、癸二酸和十二烷二酸(dodecanedioic acid)(=癸烷二羧酸(decanedicarboxylic acid))。
特别合适的二元胺为具有2至12、特别是6至8个碳原子的链烷二元胺,以及二(4-氨基环己基)甲烷或2,2-二(4-氨基环己基)丙烷。
优选的聚酰胺为聚己二酰己二胺(PA66)和聚癸二酰己二胺(PA610)、聚己内酰胺(PA6)以及尼龙-6/6,6共聚酰胺,特别是具有部分5重量%至95重量%的己内酰胺单元。特别优选PA6、PA66和尼龙-6/6,6共聚酰胺。
还可提及例如通过在高温下缩合1,4-二氨基丁烷与己二酸所得的聚酰胺(尼龙-4,6)。具有这种结构的聚酰胺的制备方法描述于例如EP-A38094、EP-A38582和EP-A39524中。
其它实例为可通过两个或更多个上述单体的共聚制得的聚酰胺以及多种聚酰胺以任何所需混合比的混合物。
以下非穷举清单包括了所述聚酰胺以及为了本发明目的的其它聚酰胺(单体列于括号内)
PA26(乙二胺,己二酸)
PA210(乙二胺,癸二酸)
PA46(四亚甲基二胺,己二酸)
PA66(六亚甲基二胺,己二酸)
PA69(六亚甲基二胺,壬二酸)
PA610(六亚甲基二胺,癸二酸)
PA612(六亚甲基二胺,癸烷二羧酸)
PA613(六亚甲基二胺,十一烷二羧酸)
PA1212(1,12-十二烷二胺,癸烷二羧酸)
PA1313(1,13-二氨基十三烷,十一烷二羧酸)
PA4(吡咯烷酮)
PA6(ε-己内酰胺)
PA7(乙醇内酰胺)
PA8(辛内酰胺)
PA9(9-氨基壬酸)
PA11(11-氨基十一烷酸)
PA12(十二内酰胺)
这些聚酰胺及其制备过程是已知的。关于其制备过程的细节本领域技术人员可从Ullmannsder Technischen Chemie[Ullmann’s Encyclopedia of Industrial Chemistry],4th edition,vol.19,pp.39-54,Verlag Chemie,Weinmann1980,以及Ullmann’s Encyclopedia ofIndustrial Chemistry,vol.A21,pp.179-206,VCH Verlag,Weinheim1992,以及Stoeckhert,Kunststofflexikon[Plastics Encyclopedia],pp.425-428,Hanser Verlag,Munich1992(关键词“Polyamide”[Polyamides]及其后页码)中获得。
特别优选使用尼龙-6或尼龙-6,6。
此外,本发明还可在聚酰胺中提供功能性化合物,其中这些功能性化合物可与羧基或氨基连接,例如具有至少一个羧基、羟基或氨基。其优选为:
具有支化效应的单体,其例如具有至少三个羧基或氨基,
可例如通过环氧基、羟基、异氰酸根合、氨基和/或羧基与羧基或氨基连接的单体,并且所述单体具有选自羟基、醚基、酯基、酰胺基、亚胺基、酰亚胺基、卤素基团、氰基和硝基,C-C双键或C-C三键的功能性基团,
或可与羧基和氨基连接的聚合物嵌段。
使用功能性化合物可在一个宽范围内根据需要调节所得的聚酰胺的性能特征。
例如,三丙酮二胺化合物可用作功能性单体。其优选涉及4-氨基-2,2,6,6-四甲基哌啶或4-氨基-1-烷基-2,2,6,6-四甲基哌啶,其中烷基具有1至18个碳原子或被苄基取代。三丙酮二胺化合物的存在量优选为0.03mol%至0.8mol%,特别优选0.06mol%至0.4mol%,均基于1mol的聚酰胺的酰氨基计。其它细节可参见DE-A-4413177。
还可使用通常用作调节剂的化合物作为其它功能性单体,实例为单羧酸和二羧酸。细节同样可参见DE-A-4413177。
组分B
1重量%至30重量%、优选1.5重量%至15重量%、特别是2.5重量%至7.5重量%的至少一种含有至少三个苯氧基磷腈单元的环状苯氧基磷腈用作组分B。合适的苯氧基磷腈描述于例如US2010/0261818的第[0051]至[0053]段。可特别提及式(I)。合适的环状苯氧基磷腈还描述于EP-A-2100919,特别是该文献的第[0034]至[0038]段。其可根据EP-A-2100919的第[0041]段所描述的制备。在本发明的一个实施方案中,环状苯氧基磷腈中的苯基可被C1-4-烷基部分取代。优选涉及未取代的苯基部分。对于环状磷腈的进一步描述可参考Chemie-Lexikon[chemical encyclopedia],9th edn.,关键词“Phosphazene”[Phosphazenes]。该制备过程例如通过环磷腈进行,所述环磷腈可由PCl5和NH4Cl获得,其中与苯酚的反应用于苯氧基在环磷腈中取代氯基。
环状苯氧基磷腈化合物可例如通过“Phosphorus-NitrogenCompounds”(Academic Press,1972),H.R.Allcock和“InorganicPolymers”(Prentice Hall International,Inc.,1992),J.E.Mark,H.R.Allcock and R.West中所描述的制备。
组分B优选为由具有三至四个苯氧基磷腈单元的环状苯氧基磷腈组成的混合物。此处含有三个苯氧基磷腈单元的环与含有四个苯氧基磷腈单元的环的重量比优选为约80:20。同样可存在更大的苯氧基磷腈单元的环,但是以少量存在。合适的环状苯氧基磷腈可以FP-100从Fushimi Pharmaceutical Co.,Ltd.获得。这是一种熔点110°C、含磷量13.4%以及含氮量6.0%的亚光白/淡黄色固体。具有三个苯氧基磷腈单元的环的比例为至少80重量%。
组分C
1重量%至15重量%、优选3重量%至9重量%、特别5重量%至7重量%、特别是约6.5重量%的红磷用作组分C。对红磷的描述,可参考Holleman Wiberg,Lehrbuch der anorganischen Chemie[Textbook ofinorganic chemistry],1985,p.624,section2.1.3.4。加入本发明模塑组合物中的红磷的形式可为粉末或色母粒,优选以聚酰胺的形式。红磷的密度为约2.2g/cm3。
组分D
0.1重量%至20重量%、优选1重量%至10重量%、特别是3重量%至8重量%、例如约6重量%的至少一种冲击改性聚合物用作组分D。其包含通常用来使组分A的聚酰胺耐冲击的冲击改性聚合物。其优选包含弹性体,例如天然橡胶或合成橡胶或其它弹性体。
可提及的有用的合成橡胶为三元乙丙橡胶(EPDM)、丁苯橡胶(SBR)、丁二烯橡胶(BR)、丁腈橡胶(NBR)、氯醇橡胶(ECO)和丙烯酸酯橡胶(ASA)。硅橡胶、聚氧化烯橡胶以及其它橡胶也是有用的。
可提及的热塑性弹性体为热塑性聚氨酯(TPU)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)和苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)。
还可使用共混聚合物形式的树脂,实例为氨基甲酸酯树脂、丙烯酸树脂、氟树脂、硅树脂、酰亚胺树脂、酰胺酰亚胺(amidimide)树脂、环氧树脂、脲醛树脂、醇酸树脂和三聚氰胺树脂。
还可使用共混聚合物形式的乙烯共聚物,例如由乙烯和1-辛烯、1-丁烯或丙烯组成的共聚物,如描述于WO2008/074687中。这些乙烯-α-链烯共聚物的摩尔质量优选为10000至500000g/mol,优选15000至400000g/mol(数均摩尔质量)。还可使用均聚烯烃,例如聚乙烯或聚丙烯。
合适的聚氨酯可参见EP-B-1984438、DE-A-102006045869和EP-A-2223904。
JP-A-2009-155436的第[0028]段列出了其它合适的热塑性树脂。
其它适合作为组分D的聚合物在EP-A-2100919的第[0044]段中提及。
特别优选使用乙烯和丙烯酸酯、丙烯酸和/或顺丁烯二酸酐的共聚物作为组分D。特别优选使用乙烯、丙烯酸正丁酯、丙烯酸和顺丁烯二酸酐的共聚物。合适的共聚物可以KR1270从BASF SE获得。
组分E
热塑性模塑组合物包含0重量%至50重量%的玻璃纤维作为组分E,并且如果存在玻璃纤维,其量为1重量%至50重量%、优选10重量%至35重量%、特别是20重量%至30重量%、例如约25重量%。此处任何所需的合适的玻璃纤维均可以短切玻璃的形式或以粗纱的形式使用。短切玻璃纤维的直径优选为约10μm。玻璃纤维可经表面处理,例如硅烷化。
组分F
本发明的热塑性模塑组合物可包含0重量%至30重量%的其它添加剂作为组分F。这些添加剂可包含其它填料、稳定剂、氧化抑制剂、防热分解和防紫外光分解的制剂、阻燃剂、润滑剂和脱模剂、着色剂(例如染料和颜料)、成核剂、增塑剂等。关于可能的添加剂的更详细描述可参考WO2008/074687的第31至37页。
组分F的存在量优选为0.1重量%至20重量%,其中组分F包含稳定剂和润滑剂。例如,氧化锌可用作稳定剂,硬脂酸钙可用作润滑剂。可使用用于聚酰胺模塑组合物的常规抗氧化剂,例如以商售的抗氧化剂。
其它可使用的填料为碳纤维、芳族聚酰胺纤维及其它填料例如石膏纤维、合成硅酸钙、高岭土、煅烧高岭土、硅灰石、滑石和白垩。
还可与阻燃剂组分B和C一起使用其它阻燃剂作为组分F的添加剂,实例为基于三嗪、金属水合物和硅酮的那些。基于三嗪的典型阻燃物质为三聚氰胺氰脲酸酯。
其它阻燃型添加剂物质可为金属化合物,例如氢氧化镁、氢氧化铝、硫酸锌、氧化铁、氧化硼和金属硼酸盐,还见EP-A-2100919的第[0046]至[0048]段。
另外的阻燃剂的实例为(二)次膦酸盐、其它磷腈化合物,以及三聚氰胺与磷酸的反应产物。三聚氰胺与磷酸的常规反应产物为三聚氰胺聚磷酸盐。合适的三聚氰胺聚磷酸盐、(二)次膦酸盐和次膦酸盐描述于例如EP-A-2100919的第[0023]至[0031]段。
其它协同阻燃物质描述于例如US2010/0261818的第[0064]至[0065]段。
在本发明的一个实施方案中,无其它阻燃剂与组分B和C一起使用。
通过混合组分A至F制备本发明的模塑组合物。为了此目的有利的是使用挤出机,实例为单螺杆挤出机或双螺杆挤出机,或使用其它传统塑化设备,例如Brabender混合机和Banbury混合机。
此处可自由选择各个组分的混合次序。优选使用含聚酰胺的色母粒形式的组分C。
本发明的模塑组合物在试样厚度为0.4mm和0.8mm时显著降低了火焰时间。其适于制备模塑品、纤维或箔片。
本发明还提供由上述热塑性模塑组合物制成的相应的模塑品、纤维或箔片。
以下实施例对本发明进行进一步的解释。
实施例
以下组分被用于本发明的组合物:
组分A:尼龙-6,6(来自BASF SE的A24)
组分B:环磷腈(来自Fushimi Co.的FB110)
组分C:在尼龙-6,6色母粒中的40%的红磷(来自Italmatch的Masteret-21440)
组分D:乙烯/丙烯酸正丁酯/丙烯酸/顺丁烯二酸酐共聚物(来自BASFSE的KR)
组分E:玻璃纤维(平均直径10μm的OCF1110)
组分F:稳定剂/润滑剂:50%的氧化锌、25%的硬脂酸钙、25%的98抗氧化剂
润滑剂:50%的硬脂酸十八烷醇酯、25%的硬脂酸锌、25%的硬脂酸钙
下表1对照了对比模塑组合物comp1(不含有环磷腈)的组成和本发明实施例2、3和4的发明模塑组合物的组成。
表1
混合过程使用螺杆转速370min-1、处理量28kg/h、外加压力200毫巴(绝压)的ZSK25F41挤出机。所述挤出机在280°C的温度下操作。
UL94燃烧试验的试样如EP-A-2100919中所述制备。制备出厚度为0.4mm和0.8mm的模制品。
所述模制品的机械性能根据以下标准测定:
拉伸弹性模量根据DIN EN ISO527-1/-2测定
断裂拉伸应力根据DIN EN ISO527-1/-2在5mm/min下测定
断裂拉伸应变根据DIN EN ISO527-1/-2在5mm/min下测定
沙尔皮(charpy)抗冲击性根据DIN EN ISO179在23°C下测定
下表2对照了机械研究和燃烧试验的结果。此处将两种不同的厚度0.4mm和0.8mm在2d,23°C和7d,70°C下进行燃烧试验。下表2对照了结果。
表2
从总续焰时间结果可以看出,环状苯氧基磷腈与红磷的结合可显著降低总续焰时间。
Claims (9)
1.一种热塑性模塑组合物,其包含
a)30重量%至95重量%的至少一种脂族聚酰胺或共聚酰胺,作为组分A,
b)1重量%至30重量%的至少一种含有至少3个苯氧基磷腈单元的环状苯氧基磷腈,作为组分B,
c)1重量%至15重量%的红磷,作为组分C,
d)0.1重量%至20重量%的至少一种冲击改性聚合物,作为组分D,其中使用乙烯与丙烯酸酯、丙烯酸和/或顺丁烯二酸酐的共聚物,
e)0重量%至50重量%的玻璃纤维,作为组分E,以及
f)0重量%至30重量%的其他添加剂,作为组分F,
其中组分A至F的总量为100重量%,
其中无其它阻燃剂与组分B和C一起使用。
2.根据权利要求1的热塑性模塑组合物,其中组分A为尼龙-6、尼龙-6,6或其掺合物。
3.根据权利要求1或2的热塑性模塑组合物,其中组分B为由具有3个和4个苯氧基磷腈单元的环状苯氧基磷腈组成的混合物。
4.根据权利要求1或2的热塑性模塑组合物,其中存在5重量%至50重量%的玻璃纤维作为组分E。
5.根据权利要求1或2的热塑性模塑组合物,其中存在0.1重量%至20重量%的组分F,其中组分F包含稳定剂和润滑剂。
6.通过混合组分A至F来制备权利要求1至3任一项的热塑性模塑组合物的方法。
7.根据权利要求6的方法,其中组分C以含聚酰胺的色母粒形式使用。
8.权利要求1至3任一项的热塑性模塑组合物用于制备模制品、纤维和箔片的用途。
9.由权利要求1至3任一项的热塑性模塑组合物制成的模制品、纤维或箔片。
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