CN1458955A - 阻燃性聚烯烃树脂组合物 - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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Abstract
一种阻燃性聚烯烃树脂组合物,包括聚烯树脂和式1(式中,R为氢或甲基,A为-C(CH3)2-,-SO2-,-S-或者是-CH2-)的化合物以及1至30重量份的2,4,6-三(一,二或三溴化苯氧基)三嗪。
Description
技术领域
本发明涉及一种阻燃性聚烯烃树脂组合物,特别是涉及一种防止析出混合在其中的阻燃剂的树脂组合物。
背景技术
因为聚乙烯和聚丙烯等聚烯烃树脂具有非常好的耐水性、耐药品性、电绝缘性和机械强度,且容易加工成形,所以广泛应用于容器、机械部件、电器电子设备、汽车部件等各种领域。但是,仅由碳和氢组成的该树脂易于燃烧,当用于要求阻燃性的用途上时,必须配合阻燃剂进行阻燃化。
使用于上述用途中的阻燃剂通常是含有溴的有机化合物,然而,与聚烯烃树脂之间没有相容性,例如为符合UL-94V-0而含有必须量的溴系阻燃剂的成形品容易发生阻燃剂从树脂分离而析出到表面上的现象。其中,阻燃剂作为白色结晶或粉末而析出到表面上的现象叫做白化。析出和白化不仅损坏树脂成形品的外观,并且对使用成形部件的机械性能也产生不好的影响。
为了防止析出和白化提出,向聚丙烯树脂中加入2,2-双[4-(2,3-二溴代丙氧基)-3,5-二溴代苯基]丙烷而进行阻燃化时,加入三梨糖醇或木糖醇的亚苄基衍生物(特开平4-285 647)的方法和向聚烯树脂中加入含有苯乙烯等芳香族单体的树脂和有机卤素系阻燃剂(特开平10-182889)组合物的方法。但是,因为按照上述提案,与阻燃剂混合后加入的成分中不含溴,所以如果加入防止析出和白化所需的充足量,则组合物整体的溴含量降低,达不到所希望的阻燃水平。并且三梨糖醇或木糖醇的亚苄基衍生物在注射成形时还会出现铸型污染等其它问题。
发明内容
本发明提供一种包括A)聚烯树脂和对应每100重量份的聚烯烃树脂,1至40重量份的具有B)式1:(式中,R为氢或甲基,A为-C(CH3)2-,-SO2-,-S-或者是-CH2-)的溴代双酚醚衍生物以及1至30重量份的C)2,4,6-三(一,二或三溴化苯氧基)三嗪。
本发明中使用的B)组分和C)组分均含有溴,其本身即为阻燃剂。但是,将它们单独加入,加入量达到期望阻燃性水平必要量时,出现析出和白化,但如果把两者组合起来加入,即使加入量达到期望的阻燃性水平量,也几乎不发生析出和白化。
具体实施方式
本发明中使用的A)聚烯烃树脂是指乙烯、丙烯、丁烯、戊烯、异戊二烯、丁二烯等脂肪族不饱和烃的同聚物或者是共聚物。其典型例为聚丙烯、聚乙烯尤其是高密度聚乙烯以及乙烯-丙烯共聚物。
B)组分为结构式用式1表示的化合物。其中的具体例为2,2-双[4-(2,3-二溴代丙氧基)-3,5-二溴代苯基〕丙烷;2,2-双[4-(2,3-二溴-2-甲基丙氧基)-3,5-二溴代苯基〕丙烷;双[4-(2,3-二溴代丙氧基)-3,5-二溴代苯基〕砜;双[4-(2,3-二溴-2-甲基丙氧基)-3,5-二溴代苯基〕砜;双[4-(2,3-二溴代丙氧基)-3,5-二溴代苯基〕硫化物;双[4-(2,3-二溴-2-甲基丙氧基)-3,5-二溴代苯基〕硫化物;双[4-(2,3-二溴代丙氧基)-3,5-二溴代苯基〕甲烷;双[4-(2,3-二溴-2-甲基丙氧基)-3,5-二溴代苯基〕甲烷;以及它们的混合物,这些物质在市场上均有销售。否则,可以用氯丙烯或甲基氯丙烯,醚化对应的四溴双酚后,在烯丙基或甲基烯丙基的双键上加成溴而合成制得。
C)组分为在每个苯环上被≤3的溴取代的2,4,6-三溴代苯氧基三嗪。这些物质是通过反应对应三聚氰酰氯的一,二或三溴代苯酚而制得。三(2,4,6-三溴代苯氧基)三嗪、三(2,6-二溴代苯氧基)三嗪或者是它们的混合物为理想。
B)组分的加入量是对应每100重量份的聚烯烃树脂为1至40重量份,C)组分的加入量是对应每100重量份的树脂为1至30重量份。阻燃性的水平依赖于两者的总量,而为了达到防止析出和白化的效果,B/C的比例必须在一定的范围之内。但是,因为大量阻燃剂的加入将引起含有其的树脂成形品的机械强度的下降,所以能够得到预期的阻燃效果的前提下应该避免加入过量。考虑上述因素,理想的是对应100重量份的树脂,使B)组分为3至25重量份,C)组分为5至20重量份。
本发明的阻燃性树脂组合物除了B)和C)组分之外,还可以含有任意的添加组分。这种添加组分例举为三氧化锑和溴代环氧树脂。三氧化锑被认知为提高有机卤系阻燃剂阻燃效果的阻燃助剂,当然可以用于本发明中。也可以代替三氧化锑使用其它的阻燃助剂。适合的三氧化锑的使用量为B)组分和C)组分总重量的0.1倍或者是等倍量。
与相同混合比例的B)组分和C)组分相比较,溴化环氧树脂有利于降低析出率,并且也有利于树脂组合物成形时的热稳定性。对应100重量份的树脂,其配合量为20重量份以下,特别合适的量为1至15重量份。
本发明的阻燃性树脂组合物可以含有有效地降低析出率的其它树脂组分。代表例为乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸烷基共聚物、乙烯-醋酸乙烯共聚物等烯烃与具有极性基团的乙烯单体的共聚物或者是乙烯-苯乙烯共聚物、乙烯-丙烯-苯乙烯共聚物、异戊二烯-苯乙烯共聚物、乙烯-异戊二烯-苯乙烯共聚物、加氢丁二烯-苯乙烯共聚物等烯烃和芳香族烃单体的共聚物,特别是嵌段共聚物。上述这些共聚物与混合水平相同的B)组分和C)组分相比,具有降低析出率的效果。但是,因为上述这些共聚物树脂自身不含有卤,如果配合过量,则不利于阻燃性,并且也不利于成型品的物性。因此,其配合量对应100重量份的聚烯烃树脂应为50重量份以下,例如3至30重量份是合适的。
同样,聚氯乙烯或聚氯丙烯等卤化聚烯烃也有效地降低析出率。其配合量对应100重量份的聚烯烃树脂应为50重量份以下,例如3至30重量份是合适的。
本发明的阻燃性聚烯烃树脂组合物,可以含有通常的聚烯烃树脂用添加剂。这些添加剂举例为防氧化剂、热稳定剂、紫外线吸收剂、紫外线稳定剂、颜料、填充剂、润滑剂、防滴液剂、晶核剂、防带电剂等,可以少量合用B)组分和C)组分以外的公知的阻燃剂。
本发明的树脂组合物可以通过常用的方法,混合聚烯烃树脂和添加组分而制得。即,向树脂中混合全部的添加组分或者事先混合一部分添加组分之后,混合其余的添加组分,用双轴挤压机、密闪式混炼机、热滚轧等,将混合物加热混炼,使其成为均匀的组合物,然后使用注射成形机或热压机等成形机,成形至期望的成形品。
实施例
下面,根据实施例和比较例说明本发明的具体例,但本发明并不限于下述实施例,以下如果没有特别的说明,[部]和[%],均以重量为基准。
实施例和比较例中使用了以下原料。A)聚烯烃树脂
A-1聚丙烯((株)dokyama制德山polyploME230)
A-2高密度聚乙烯(日本polygame(株)制nobatecHD HJ360)B)组分
B-12,2-双[4-(2,3-二溴代丙氧基)-3,5-二溴代苯基]丙烷(第一工业制药(株)制pirogadoSR-720)
B-2双[4-(2,3-二溴代丙氧基)-3,5-二溴代苯基]硫化物(丸菱油化(株)制nonnanPR-2)C)组分
C-1三(2,4,6-三溴化苯氧基)三嗪(第一工业制药(株)制pirogadoSR-245)
C-2三(2,6-二溴化苯氧基)三嗪D)溴化环氧树脂
D-1 四溴双酚A环氧低聚物(东都化成(株)制TB60)
D-2 四溴双酚A环氧低聚物(东都化成(株)制YDB-409)E)聚烯烃共聚物
E-1 乙烯-丙烯酸乙酯共聚物(日本unika(株)制NUC-6221、丙烯酸乙酯10wt%)
E-2 乙烯-乙酸乙烯共聚物(住友化学工业(株)制eibadeitoD4040、醋酸乙烯4.5wt%)
E-3乙烯-丙烯-苯乙烯共聚物((株)kolalai制septon2043,苯乙烯13wt%)F)卤代聚烯烃
卤代聚苯乙烯((株)dayiso制dayisolakoU-303,卤素含量30wt%)G)阻燃助剂
三氧化锑(第一工业制药(株)制pirogadoAN-800(T))H)防氧化剂(tsiba·speciality·chemicals制IRGANOX B225)
I)炭黑(涛和化学(株)制炭黑PPmastabatsiDB4008,炭
黑50wt%)
J)六溴环十二烷(第一工业制药(株)制pirogadoSR-105)试验片制作方法:
在热轧滚上190℃混炼15分钟原料,用热压机200℃压制3分钟后,用刀具切成一定尺寸的试验片。另外,为了容易析出,混炼时加入炭黑PPmastabatsi,将试验片着色成黑色。阻燃性实验:
基于UL-94垂直燃烧试验法进行。试验片长度为127mm,宽度为12.7mm,厚度为1.6mm。析出实验
将70×50×3.2mm的试验片在80℃下放置1小时进行析出实验。
各项的评价法以及基准如下。
目视:用肉眼确定试验前的状态。
没有析出的计为N,有少量析出的计为S,白化的计为W。
析出量:用丙酮擦拭试验前的试验片,测定重量计为Wi。在80℃下放置1周后的试验片,同样用丙酮擦拭,测定重量,并计为Wx。析出率按照下式计算。
析出率(%)=(Wi-Wx)/阻燃剂的加入量×100
白化性:用比色计ZE-3000(日本电色工业(株)制),测定析出试验后的试验片的用丙酮擦拭之前的白色度和用丙酮擦拭后的白色度,通过其差ΔE进行判断。ΔE≤5.0为没有析出,ΔE)5.0为有析出。
实施例1-12以及比较例1-2
由具有表1组成的树脂组合物制作试验片,测定阻燃性和析出,得到了表2中所示的结果。
表1-1
表1-2
表2-1
表2-2
实施例 | ||||||
配合(重量份) | 1 | 2 | 3 | 4 | 5 | 6 |
A)聚烯烃 | ||||||
A-1 | 100 | - | 100 | 100 | 100 | 100 |
A-2 | - | 100 | - | - | - | - |
B)阻燃剂 | ||||||
B-1 | 10 | - | 10 | 10 | 11 | 11 |
B-2 | - | 10 | - | - | - | - |
C)阻燃剂 | ||||||
C-1 | 4 | 4 | - | 4 | 5 | 5 |
C-2 | - | - | 4 | - | - | - |
D)溴代环氧树脂 | ||||||
D-1 | - | - | 4 | - | - | - |
D-2 | - | - | - | 4 | - | - |
E)烯烃共聚物 | ||||||
E-1 | - | - | - | - | 11 | - |
E-2 | - | - | - | - | - | 11 |
E-3 | - | - | - | - | - | - |
G)阻燃助剂 | 6 | 6 | 7 | 7 | 7 | 7 |
H)防氧化剂 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
I)炭黑mastabatsi | 5 | 5 | 5 | 5 | 5 | 5 |
实施例 | 比较例 | |||||||
配合(重量份) | 7 | 8 | 9 | 10 | 11 | 12 | 7 | 8 |
A)聚烯烃 | ||||||||
A-1 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
A-2 | - | - | - | - | - | - | ||
B)阻燃剂 | ||||||||
B-1 | 11 | 20 | 11 | 9 | 7 | 11 | 14 | - |
B-2 | - | - | - | - | 4 | - | ||
C)阻燃剂 | ||||||||
C-1 | 5 | 5 | 20 | 3 | 5 | 5 | - | 35 |
C-2 | - | - | - | - | - | - | ||
D)溴代环氧树脂 | ||||||||
D-1 | - | - | - | - | - | - | ||
D-2 | - | - | - | - | - | - | ||
E)烯烃共聚物 | ||||||||
E-1 | - | 11 | 11 | - | - | - | ||
E-2 | - | - | - | - | - | - | ||
E-3 | 11 | - | - | - | - | - | ||
F)卤代聚烯烃 | - | - | - | - | - | 11 | ||
G)阻燃助剂 | 7 | 7 | 7 | 7 | 6 | 7 | 6 | 15 |
H)防氧化剂 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
I)炭黑mastabatsi | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
J)六溴环十二烷 | - | - | - | 1 | - | - |
实施例 | ||||||
项目 | 1 | 2 | 3 | 4 | 5 | 6 |
阻燃性(UL-94) | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
析出试验: | ||||||
目视 | N | N | N | N | N | N |
析出率(%) | 1.9 | 1.8 | 1.7 | 1.7 | 1.4 | 0.9 |
白化 | 无 | 无 | 无 | 无 | 无 | 无 |
实施例 | 比较例 | |||||||
项目 | 7 | 8 | 9 | 10 | 11 | 12 | 7 | 8 |
阻燃性(UL-94) | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-2 |
析出试验 | ||||||||
目视 | N | N | N | N | N | N | W | S |
析出率(%) | 1.3 | 2.2 | 1.6 | 1.8 | 1.5 | 1.4 | 10.0 | 4.3 |
白化 | 无 | 无 | 无 | 无 | 无 | 无 | 有 | 有 |
由表1和表2的结果清楚地看出,组合B)组分和C)组分作为阻燃剂使用时,能够防止析出和白化。
Claims (7)
2、根据权利要求1所述的阻燃性聚烯烃树脂组合物,其特征在于,对应每100重量份的聚烯烃树脂还含有不多于20重量份的D)溴代环氧树脂。
3、根据权利要求2所述的阻燃性聚烯烃树脂组合物,其中,D)组分为四溴双酚A环氧低聚物。
4、根据权利要求1或2所述的阻燃性聚烯烃树脂组合物,其特征在于,对应每100重量份的聚烯烃树脂还含有不多于50重量份的E)烯烃和具有极性基团的单体的共聚物或者是烯烃和芳香烃单体的共聚物和/或F)卤代聚烯烃。
5、根据权利要求1至4任意一项所述的阻燃性聚烯烃树脂组合物,其中还含有B)组分和C)组分总量的0.1倍至等量的G)阻燃助剂。
6 、根据权利要求5所述的阻燃性聚烯烃树脂组合物,其中G)组分为三氧化锑。
7、根据权利要求1至6任意一项所述的阻燃性聚烯烃树脂组合物,其中,对应每100重量份的聚烯烃树脂混合3至25重量份的B)组分和5至20重量份的C)组分。
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