CN1240760C - 有机磷阻燃剂、内酯稳定剂和磷酸酯相容剂的共混物 - Google Patents

有机磷阻燃剂、内酯稳定剂和磷酸酯相容剂的共混物 Download PDF

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CN1240760C
CN1240760C CNB018188273A CN01818827A CN1240760C CN 1240760 C CN1240760 C CN 1240760C CN B018188273 A CNB018188273 A CN B018188273A CN 01818827 A CN01818827 A CN 01818827A CN 1240760 C CN1240760 C CN 1240760C
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B·A·威廉斯
L·A·德克莱恩
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Abstract

一种适合掺入聚氨酯泡沫中的阻燃剂共混物包含磷含量不低于约10%的低聚有机磷阻燃剂，优选有机磷酸酯；苯并呋喃-2-酮稳定剂；和含有烷基和/或卤代烷基的单体磷酸酯，该单体磷酸酯用作低聚有机磷阻燃剂和苯并呋喃-2-酮稳定剂的加溶添加剂。

Description

有机磷阻燃剂、内酯稳定剂和磷酸酯相容剂的共混物
本发明涉及三种组分在阻燃添加剂配方中的组合，该组合在掺入聚氨酯泡沫中时导致该聚氨酯泡沫的变色(也称为“烧焦”)与仅使用该组合的两种有机磷组分时相比显著降低。此外，本发明涉及加溶性单体磷酸酯组分与有机磷阻燃剂(在某些实施方案中其可以为低聚磷酸酯)和苯并呋喃-2-酮(或“内酯”)稳定剂的组合的用途。该加溶组分的存在使仅一起使用有机磷阻燃剂和苯并呋喃-2-酮稳定剂时所观察到的当量溶液随时间的不稳定性得到延缓。加溶组分(例如来自Akzo Nobel Functional Chemicals的品牌PHOSFLEX TBEP)的其他优点是粘度在使用低聚有机磷阻燃剂时降低且与其他易燃性相容剂不同的是，阻燃性能并未受到明显程度的影响。本发明的溶液稳定性更好的组合物允许烧焦的降低，而烧焦例如通常在使用磷酸酯阻燃剂时在低密度聚氨酯软泡沫中发生。
本发明阻燃剂共混物的必要组分是有机磷阻燃剂，其与本发明的三组分阻燃剂共混物的其他两种组分相比以主要量存在。该有机磷添加剂在共混物中的量为该共混物重量的约60-98％，更优选约80-96％。
有机磷阻燃剂可以是常用类型的单体磷酸酯，其具有式O＝P(OR)3，其中R选自含有1至约8个，优选1至约6个碳原子的烷基和卤代烷基。该类阻燃剂的代表性实例包括磷酸三(二氯异丙基)酯、磷酸三(2-氯异丙基)酯和磷酸三(2-氯乙基)酯。
另外，该有机磷阻燃剂组分可以是低聚有机磷阻燃剂，优选具有不低于约5％重量的磷含量且在需要有机磷酸酯的优选实施方案中，其中具有至少三个磷酸酯单元(即至少两个磷酸酯重复单元和一个磷酸酯封端单元)。本文所用术语“低聚的”是指排除单体的或二聚的物质。该类代表性有机磷添加剂一般性地描述于T.A.Hardy的美国专利4,382,042中，优选非卤代类(例如，尤其是含有乙基的组合物)。这些优选的有机磷酸酯低聚物可以通过如下方式形成：使五氧化二磷与选定的磷酸三烷基酯(例如磷酸三乙酯)反应形成含有P-O-P键的多磷酸酯，然后使其与环氧化物(例如环氧乙烷)反应形成所需产物。该优选的低聚有机磷酸酯阻燃剂具有下式：
Figure C0181882700051
其中n(表示“重复”磷酸酯单元)基于数字平均可以为2至约20，优选2-约10，R选自烷基和羟烷基且R’为亚烷基。烷基和亚烷基通常含有约2至约10个碳原子。
本文所用的尤其优选的低聚磷酸酯包含乙基和亚乙基作为烷基和亚烷基部分，具有的羟基官能度不大于约30mg KOH/g，具有的酸值不大于约2.5mg KOH/g且具有的磷含量为约15-25％重量。在下文中将其称为“PEEOP”(或“多(乙基亚乙氧基)磷酸酯”)。
本发明可以将含有低聚膦酸酯的物质用作组分(b)。基本纯净的膦酸酯和膦酸酯/磷酸酯组合物均可引入其中。它们具有如上面对低聚磷酸酯物质所述的相同结构，不同的是结构左侧上的内部(加括号的)RO-可以是R-且该式右侧上的端部-OR结构之一可以为-R。这类添加剂的代表性和市售实例是购自Akzo Nobel Chemicals Inc.的FYROL 51，其由甲基膦酸二甲基酯、五氧化二磷、乙二醇和环氧乙烷通过多步法制备。
产品“FYROLPNX”是用于本文的这类优选产品。它是具有下式的低聚磷酸酯(CAS#184538-58-7)：
Figure C0181882700052
其中n(表示“重复”磷酸酯单元)基于数字平均为约2至约20，R为乙基且R’为亚乙基。该优选的产品具有的磷含量为约19％重量且在25℃下的粘度为约2000mPa.s。
本发明阻燃剂共混物的第二种必要组分是美国专利5,869,565中所述的苯并呋喃-2-酮类稳定剂，该专利因其对该添加剂的说明而引入本文供参考。这类稳定剂的结构提供在下式中：
其中R1、R7、R8、R9和R10中的两个相互独立地为C1-C4烷基或C1-C4烷氧基，其他的为氢，或R7-R10为氢，或这些基团中至多两个各自独立地为甲基或甲氧基，且R1为-O-CHR3-CHR5-O-CO-R6，R2和R4各自独立地为氢或C1-C6烷基，R3为氢或C1-C4烷基，R5为氢、苯基或C1-C6烷基，且R6为C1-C4烷基。购自Ciba Specialty Chemicals的HP-136牌号产品是优选用于本文的物质且为(5，7-二叔丁基-3-(3，4-二甲基苯基)-3H-苯并呋喃-2-酮，其中R2和R4各自为叔丁基且R1、R7、R8、R9和R10中的两个各自为甲基。该稳定剂组分在本发明阻燃剂共混物中的存在量为该共混物重量的约0.05-1.0％，更优选为约0.2-0.5％。
本发明共混物的第三种必要组分是式O＝P-(OR)3的单体磷酸酯，其中R独立地选自在烷基、烷氧基烷基和/或卤代烷基中含有至多约8个碳原子的烷基、烷氧基烷基或卤代烷基。该组分的存在量为该共混物重量的约1-40％，更优选约1-20％。优选卤代(例如氯代)的取代基或烷氧基烷基，在取代基中碳原子数为1-4。可以选用的该类代表性化合物包括磷酸三丁氧基乙基酯、磷酸三(1，3-二氯异丙基)酯、磷酸三丁基酯、磷酸三(2-氯乙基)酯、磷酸三乙酯、磷酸三(2-氯异丙基)酯、异丙基化磷酸三芳基酯和叔丁基化磷酸三苯基酯混合物。尽管单体磷酸酯相容剂可以在可以对本发明主要组分选择的相同一般类型的有机磷化合物中选择(其通常为不与苯并-2-呋喃酮稳定剂形成相容性共混物的化合物)，但本发明也可选择该类中的不同化合物以使该阻燃剂共混物中存在三种组分。
前面描述的阻燃剂共混物可以至多约24重量份/100份多元醇的用量掺入常规聚氨酯泡沫(通常含有用于抑制烧焦的抗氧化剂)中以对这些泡沫提供所需程度的阻燃性和抗焦烧性。
本发明由下列实施例进一步描述。
实施例
下述体系1使用FYROL38作为内酯添加剂HP-136和FYROLPNX的加溶剂。体系2使用磷酸酯PHOSFLEXTBEP作为HP-136和FYROLPNX材料的加溶剂。
使用微波炉测试方法来测定试验泡沫的变色程度，使用1-5的数字评分来表达该泡沫中存在的烧焦程度。1表示没有变色的白色泡沫对照，而5表示非常深棕色的烧焦图案。该值由1增加到5表示变色增加。用上面两个体系中的任一体系(阻燃剂、加溶剂和内酯添加剂)制备的泡沫产生评分为1.5-2.0的泡沫，而没有使用HP-136内酯稳定剂的烧焦程度为2.5-3.0。公称密度为1.20pcf(磅/立方英尺)。该微波测试方法描述于Journal ofCellular Plastics(多孔塑料杂志)(1979年12月)中Reale和Jacobs的题为“聚氨酯泡沫烧焦的快速显示试验”的文章中。
下列实施例说明用于制备软泡沫的配方。
       表A-体系1
  Acro的聚醚多元醇(3000mw)   100.0   100.0
  体系1*   9.0
  FYROLPNX   (2.23)   5.00
  FYROL38(加溶剂)   (6.68)   ----
  Ciba的HP-136内酯   (0.09)   ----
  H2O   5.0   5.0
  OSi的Dabco 33LV/A-1(3∶1比例)   0.22   0.22
  OSi的聚硅氧烷表面活性剂L-620   1.0   1.0
  Air Products的辛酸亚锡T-10   0.30   0.30
  Bayer的甲苯二异氰酸酯TDI   60.0   60.0
  TDI指数   110   110
*体系1的三种组分(包括FYROL PNX、加溶剂和HP-136)在70℃下加热4小时。
      表A-1
  Acro的聚醚多元醇(3000mw)   100.0   100.0
  FYROLPNX   4.95   5.00
  Ciba的HP-136内酯   0.05   ----
  H2O   5.0   5.0
  OSi的Dabco 33LV/A-1(3∶1比例)   0.22   0.22
  OSi的聚硅氧烷表面活性剂L-620   1.0   1.0
  Air Products的辛酸亚锡T-10   0.30   0.30
  Bayer的甲苯二异氰酸酯TDI   60.0   60.0
  TDI指数   110   110
仅与HP-136混合的Fyrol PNX难以溶解且不能形成清澈的稳定溶液；因此必需本发明的相容剂或加溶剂以维持稳定溶液。
将上面表A所提到的配方组分混合，倾入一个(8.0”x8.0”x5.0”)盒子中并允许其自由增长。然后将泡沫置于GE PROFILE SENSOR微波炉中并加热120秒。从炉中取出泡沫。将其冷却到室温并保持2小时。垂直于增长方向将泡沫块切割成1英寸的片并检测其变色。
使用FYROL PNX低聚有机磷酸酯、内酯稳定剂(HP-136，其活性成分为5，7-二叔丁基-3-(3，4-二甲基苯基)-3H-苯并呋喃-2-酮)和磷酸酯FYROL 38—磷酸三[1，3-二氯异丙基]酯且具有抗氧化剂包装(如美国专利4,477,600所述)的体系1的性能示于表B中：
  表B-体系1
  样品   1   1A(两份)   2(对照)   3   4(对照)
 体系1   FYROLPNXFYROL38HP-136   FYROLPNXFYROL38HP-136   FYROLPNXFYROL38(不含HP-136)   FYROLPNXHP-136   FYROLPNX(不含HP-136)
 颜色评分   2.0   1.5   3   2   3
在表B所报告的操作中，FYROL PNX与磷酸酯的重量比为25∶75且9.0份指相对于100重量份用于制备泡沫的多元醇而言该组合的重量份。抗氧化剂(存在时)的重量百分数基于阻燃剂和加溶剂的重量为1.0％。在表B的操作3(其中Fyrol PNX仅与HP-136内酯混合)中，其难以溶解且没有形成清澈的稳定溶液。
下列实施例说明用于生产本发明软泡沫的配方。
使用体系2生产第二组泡沫，但使用色度计(即DR LANGE MicroColor装置)测量泡沫的烧焦特性。
    表C-体系2
  Shell的聚醚多元醇(3000mw)   100.0
  体系2*   8.0
  FYROLPNX   7.60
  FYROLTBEP(加溶剂)   0.38
  Ciba的HP-136内酯   0.02
  H2O   4.80
  OSi的Dabco 33LV/A-1 3∶1   0.24
  OSi的聚硅氧烷表面活性剂Dabco 5125   1.0
  Air Products的辛酸亚锡T-10   0.36
  Bayer的甲苯二异氰酸酯TDI   58.9
  TDI指数   110
使用FYROLPNX(低聚有机磷酸酯)、内酯稳定剂(HP-136，其活性成分为5，7-二叔丁基-3-(3，4-二甲基苯基)-3H-苯并呋喃-2-酮)和磷酸酯加溶剂PHOSFLEXT-BEP(磷酸三丁氧基乙基酯)的体系2的性能示于表D中：
表D-体系2
  样品   1   2
  体系2   FYROLPNXPHOSFLEXTBEP   FYROLPNXPHOSFLEXTBEP
  抗氧化剂   0.25％的HP-136   无
  色度计读数(b*)   *6.7   *23.7
b*＝泛黄度，数值越低表明泡沫越少着色。
在表D所报告的操作中，FYROL PNX与磷酸酯的重量比为95∶5且8.0份指相对于100重量份用于制备泡沫的多元醇而言该组合的重量份。HP-136牌号的抗氧化剂(在体系2中使用时)的重量百分数基于阻燃剂和加溶剂的重量为0.25％。
前述实施例仅用来对本发明进行举例说明，而不应被认为具有限制作用。所想要的保护范围在下列权利要求书中说明。

Claims (11)

1.一种阻燃剂组合物，其包含：60-98重量％的有机磷阻燃剂；苯并呋喃-2-酮稳定剂；和单体磷酸酯相容剂，其中有机磷阻燃剂为低聚有机磷阻燃剂，该低聚有机磷阻燃剂为其中含有至少三个磷酸酯单元的磷酸酯。
2.如权利要求1所要求的组合物，其中磷酸酯具有下式：
Figure C018188270002C1
其中n基于数字平均为2至20，R为乙基且R’为亚乙基。
3.如权利要求1所要求的组合物，其中苯并呋喃-2-酮稳定剂具有下式：
其中R1、R7、R8、R9和R10中的两个相互独立地为C1-C4烷基或C1-C4烷氧基，其他的为氢；或R7-R10为氢，或这些基团中至多两个各自独立地为甲基或甲氧基，且R1为-O-CHR3-CHR5-O-CO-R6；R2和R4各自独立地为氢或C1-C6烷基；R3为氢或C1-C4烷基；R5为氢、苯基或C1-C6烷基；且R6为C1-C4烷基。
4.如权利要求3所要求的组合物，其中苯并呋喃-2-酮稳定剂为5，7-二叔丁基-3-(3，4-二甲基苯基)-3H-苯并呋喃-2-酮。
5.如权利要求1所要求的组合物，其中单体磷酸酯相容剂具有式O＝P-(OR)3，其中R独立地选自在烷基、烷氧基烷基和/或卤代烷基中含有至多8个碳原子的烷基、烷氧基烷基或卤代烷基。
6.如权利要求1所要求的组合物，其包含：60-98％重量有机磷阻燃剂；0.05-1.0％重量苯并呋喃-2-酮稳定剂；和1-20％重量单体磷酸酯相容剂。
7.如权利要求6所要求的组合物，其中磷酸酯具有下式：
Figure C018188270003C1
其中n基于数字平均为2至20，R为乙基且R’为亚乙基。
8.如权利要求6所要求的组合物，其中苯并呋喃-2-酮稳定剂具有下式：
Figure C018188270003C2
其中R1、R7、R8、R9和R10中的两个相互独立地为C1-C4烷基或C1-C4烷氧基，其他的为氢；或R7-R10为氢，或这些基团中至多两个各自独立地为甲基或甲氧基，且R1为-O-CHR3-CHR5-O-CO-R6；R2和R4各自独立地为氢或C1-C6烷基；R3为氢或C1-C4烷基；R5为氢、苯基或C1-C6烷基；且R6为C1-C4烷基。
9.如权利要求8所要求的组合物，其中苯并呋喃-2-酮稳定剂为5，7-二叔丁基-3-(3，4-二甲基苯基)-3H-苯并呋喃-2-酮。
10.如权利要求6所要求的组合物，其中单体磷酸酯相容剂具有式O＝P-(OR)3，其中R独立地选自在烷基、烷氧基烷基和/或卤代烷基中含有至多8个碳原子的烷基、烷氧基烷基或卤代烷基。
11.一种阻燃的聚氨酯泡沫，包含权利要求1-10中任一项的组合物。
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