CN1168381A - 1-羧基-磷杂环戊烯氧化物和1-羟基磷杂环戊烷氧化物的盐，它们的制备方法和它们作为防火剂的用途 - Google Patents
1-羧基-磷杂环戊烯氧化物和1-羟基磷杂环戊烷氧化物的盐，它们的制备方法和它们作为防火剂的用途 Download PDFInfo
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Abstract
本发明的1-羟基二氢磷杂环戊烯氧化物和1-羟基磷杂环戊烷氧化物的盐适合于用作防火剂，尤其用于塑料，如聚酯或聚酰胺。在盐中，优选铝盐。
Description
本发明涉及1-羟基-二氢磷杂环戊烯氧化物和1-羟基磷杂环戊烷氧化物的盐，它们的制备方法和它们作为防火剂的用途。
在聚合物中添加含磷或含卤素化合物或其混合物的聚合物通常是防火的，某些聚合物在高温，例如250℃或更高温度下加工。由于许多已知的防火材料太易挥发或不足以耐热，基于该原因，它们不能用作防火材料。
用作聚酰胺模塑材料的阻燃添加剂的膦酸碱金属盐是已知的(DE-A1-2447727)，但它们易产生腐蚀。
本发明的任务是提出一种阻燃添加剂，其未显示已知阻燃添加剂的缺点。尤其是，阻燃添加剂可简单地和价格便宜地制备，具有好的阻燃效果，达到高的耐温度性。
本发明人惊奇地发现，1-羟基-二氢磷杂环戊烯氧化物和/或1-羟基磷杂环戊烷氧化物的盐在热塑材料，如聚酰胺或聚酯中具有杰出的阻燃效果。
因此，本发明是关于1-羟基-二氢磷杂环戊烯氧化物和/或1-羟基磷杂环戊烷氧化物的盐，它们的制备方法和它们作为防火剂的用途。
另外，本发明是关于模塑材料，其含有热塑塑料和至少一种1-羟基-二氢磷杂环戊烯氧化物和/或1-羟基磷杂环戊烷氧化物的盐。
优选的盐是如下式(Ia)或(Ib)的1-羟基二氢磷杂环戊烯氧化物的盐和式(II)的1-羟基磷杂环戊烷氧化物的盐：
其中，R1、R2、R3、R4表示氢或直链或支链烷基，优选直链或支链C1-C12烷基，尤其优选C1-C4烷基，尤其甲基和/或乙基；和M是周期表第二或第三主族或副族的元素，优选镁、钙、锌、铝；优选铝和n是整数1，2或3。
上述1-羟基-二氢磷杂环戊烯氧化物和1-羟基磷杂环戊烷氧化物的盐在下文中将概述为盐。
尤其适用于本发明目的的盐是例如：1-羟基-3-烷基-2，3-二氢-1H.-磷杂环戊烯-1-氧化物、1-羟基-3-甲基-2，5-二氢-1H-磷杂环戊烯-1-氧化物、1-羟基-2，3-二氢-1H-磷杂环戊烯-1-氧化物、1-羟基-2，5-二氢-1H-磷杂环戊烯-1-氧化物、1-羟基-二氢-1H-磷杂环戊烷-1-氧化物和1-羟基-3-甲基-二氢-1H-磷杂环戊烷-1-氧化物的碱土金属、镁、锌和铝盐以及这些盐的混合物。铝盐是尤其优选的。
盐可以通过在水溶液中由1-羟基二氢磷杂环戊烯氧化物和1-羟基磷杂环戊烷氧化物与相应的金属碳酸盐、金属氢氧化物或金属氧化物反应制备。为此，通常将1-羟基二氢磷杂环戊烯氧化物和/或1-羟基磷杂环戊烷氧化物溶解于水中，有利的是在搅拌下加入化学计算量的相应的金属氢氧化物、金属碳酸盐或金属氧化物。随后加热反应混合物至优选为30-150℃，尤其为70-110℃，再搅拌几小时。反应时间为几小时(至少10小时)至几天(1-7天)。反应完成后，反应混合物用常规方法(冷却、吸滤、洗涤、干燥等等)处理。
起始化合物是现有技术中已知的，并且(例如，1-羟基二氢磷杂环戊烯氧化物)可根据已知的方法，例如EP-A1-452755中描述的方法，(例如由1-氯-二氢磷杂环戊烯氧化物)得到。1-羟基磷杂环戊烷氧化物可通过1-氯-二氢磷杂环戊烯氧化物氢化制备。
本发明的盐通常是热稳定的，它们在加入热塑塑料过程中不分解聚合物，在加工过程中，不影响热塑性模塑材料的生产过程。盐在热塑塑料生产和加工条件下通常不挥发，它们显示出突出的阻燃效果。
优选的热塑塑料(本文也称为热塑性塑料或聚合物)是聚酰胺，例如，聚酰胺46或聚酰胺66，或聚酯，例如聚对苯二甲酸乙二酯(PET)或聚对苯二甲酸丁二酯(PBT)。
可加入本发明的聚酰胺和聚酯是例如在《Ullmann’s工业化学百科全书》，ed.Barbara Elvers，Vol.A21，Kapitel《聚酰胺》(S.179-205)和Kapitel《聚酯》(S.227-251)，VCH，Weinheim-Basel-Cambridge-New York 1992中描述，它们列为本文参考文献。
加入热塑性塑料的盐的量可在宽的范围内变化。通常基于聚合物使用量为按重量计5-30％，优选按重量计10-20％。最佳使用量取决于聚合物的性质和加入的盐的种类，可通过实验容易地确定。
盐可按照所用的聚合物的种类和所需的性质以不同物理形式使用。因此，例如，为获得在聚合物中的较好分散，盐可以研磨成细粉形式。根据需要，也可以使用不同盐的混合物。
盐可以下列方式掺入聚合物，在其中将两者混合，紧接着在复合聚集设备(例如螺杆挤出机)熔化聚合物，盐在聚合物熔化物中均化，熔化物作为束状物拉出，冷却和粒化。盐也可以直接计量加入聚集设备中。
也可以将阻燃添加剂混合入最终的聚合物粒状产物，和直接在压铸机中加工或先在挤出设备中熔融，造粒和干燥后加工。
阻燃添加剂也可以在聚合物的制备过程中加入，例如在聚酯缩聚过程中。
除了本发明的盐之外，聚合物配方还可以含有填料(例如，滑石、云母、硅灰石、白垩、玻璃球)、补强剂(例如，玻璃纤维、玻璃片、无机纤维、碳纤维)、炭黑、染料、颜料、稳定剂、UV-稳定剂、润滑剂和脱模助剂、亲核试剂(Nulleierungsmittel)、抗静电剂、增塑剂或其它添加剂。
尤其优选的是由含有聚酯、至少一种本发明的盐和玻璃纤维的模塑材料得到的模制件。由此模塑材料得到的模制件显示尤其有益的阻燃性质。
本发明的防火模塑材料通常适合用压铸机、挤出设备或压制设备制成模制体、薄膜、丝和纤维。
本发明的模塑材料，尤其是含有聚酯或聚酰胺和本发明的盐的模塑材料显示了高的防漏电性能(较高的CTI)。这些模塑材料尤其应用于：电子部件，如线圈、变压器、继电器、开关、插头、马达和马达部件(转子、轴承套等)、具有整体导体结构的立体部件(模压内连接装置＝MID)、基座(例如SIMM-基座)、电子和家用器具的机械部件，例如，齿轮、操纵杆、凸轮组、隔板、铰链、滑动轴承、电子部件和器具的罩、盖、外壳和涂层，例如电容器罩、继电器罩、电容器盖、电缆涂层。
因此本发明另一方面是含有至少一种1-羟基-二氢磷杂环戊烯氧化物或1-羟基磷杂环戊烷氧化物的盐的热塑性塑料的应用，尤其是用于制造模制件，尤其是电子部件、机械部件、插头、机箱、罩、盖、外壳和涂层。
盐也可以是清漆，例如防火清漆，特别是用于塑料的防火清漆，例如聚氧化亚甲基、聚酯或聚酰胺的组成部分。
因此，本发明还涉及1-羟基-二氢磷杂环戊烯氧化物和/或1-羟基磷杂环戊烷氧化物的盐作为清漆，尤其是防火清漆的组成部分的用途。
实施例1 盐的制备1.1 1-羟基-2，5-二氢-1H-磷杂环戊烯-1-氧化物的铝盐的制备
将105g(0.89mol)1-羟基-2，5-二氢-1H-磷杂环戊烯-1-氧化物溶解于250g水中，在搅拌下加入23.1g(0.297mol)氢氧化铝。加热至90℃，在该温度下搅拌24小时。随后，冷却、吸滤和用水洗涤。在150℃的真空干燥箱中干燥后，得到111.5g白色粉末，其至360℃不熔化。收率约理论值的100％。1.2 1-羟基-2，5-二氢-1H-磷杂环戊烯-1-氧化物和1-羟基-2，3-二氢-1H-磷杂环戊烯-1-氧化物的混合物的铝盐的制备
将90lg(7.63mol)摩尔比约为1∶1的1-羟基-2，5-二氢-1H-磷杂环戊烯-1-氧化物和1-羟基-2，3-二氢-1H-磷杂环戊烯-1-氧化物的混合物溶解于1800g水中，在搅拌下加入198.5g(2.54mol)氢氧化铝。加热至90℃，在该温度下搅拌50小时。随后，吸滤和在真空干燥箱中干燥，得到962g淡黄-白色粉末，其至360℃不熔化。收率约理论值的100％。1.3 1-羟基-1H-磷杂环戊烷-1-氧化物铝盐的制备
将60g1-羟基-1H-磷杂环戊烷-1-氧化物溶解于95ml水中，在85℃下搅拌，然后加入13g(0.167mol)氢氧化铝，在该温度下保持约20小时。随后，吸滤和干燥，得到58g白色粉末，其至360℃不熔化。收率约理论值的91％。1.4 1-羟基-3-甲基-2，5-二氢-1H-磷杂环戊烯-1-氧化物铝盐的制备
将25g(0.189mol)1-羟基-3-甲基-2，5-二氢-1H-磷杂环戊烯-1-氧化物溶解于50ml水中，与4.9g(0.063mol)氢氧化铝一起回流加热30小时。随后，吸滤和在140℃真空干燥箱中干燥4天，得到25g白色粉末，其至360℃不熔化。收率为约理论值的94％。2. 阻燃聚酯的制备和检测
将含磷化合物(盐)与聚合物混合，在商业上通用的双螺杆复合器中加工。在玻璃纤维增强的配方情况下向熔化物中计量加入对聚酯来说商业上通用的玻璃纤维。
复合时的熔体温度对于聚对苯二甲酸丁二酯(PBT)为约250℃，试样用压铸机根据ISO 7792-2制备。
用厚度为1.2mm的试样确定每种混合物的试样的火灾种类UL94(Underwriter Labortories)，根据ISO527确定抗拉强度和断裂伸长度。2.1 由PBT和1-羟基-2，5-二氢-1H-磷杂环戊烯-1-氧化物的铝盐(根据实施例1.1制备)制备不含其它添加剂的用30％玻璃纤维补强的化合物，注塑成试样，测出如下结果：
2.2 由PBT和1-羟基-3-羟基-2，5-二氢-1H-磷杂环戊烯-1-氧化物的铝盐(根据实施例1.4制备)制备不含其它添加剂的用30％玻璃纤维补强的化合物，注塑成试样(0.8mm)，测出如下结果：
| 铝盐浓度％ | 火灾种类UL94 | 抗拉强度N/mm2 | 断裂伸长度％ |
| 20 | V-0 | 116 | 1.9 |
| 17.5 | V-1 | 119 | 1.9 |
| 15 | V-2 | 131 | 2.1 |
| 12.5 | V-2 | 134 | 2.5 |
UL94 V-0(0.8mm)
铝盐浓度％ 火灾种类UL94
20％ V-0
Claims (9)
1.如下式(Ia)或(Ib)的1-羟基二氢磷杂环戊烯氧化物和式(II)的1-羟基磷杂环戊烷氧化物的盐：其中，R1、R2、R3、R4表示氢或直链或支链烷基，优选直链或支链C1-C12烷基，尤其优选C1-C4烷基，尤其甲基、乙基；和M是周期表第二或第三主族或副族的元素，特别是镁、钙、锌、铝；和n是整数1，2或3。
2.权利要求1的盐的制备方法，其中将在水溶液中的1-羟基二氢磷杂环戊烯氧化物和/或1-羟基磷杂环戊烷氧化物与金属碳酸盐、金属氢氧化物或金属氧化物反应，其中金属是周期表第二或第三主族或副族的金属。
3.根据权利要求2的方法，其特征在于反应在30-150℃下并在搅拌下进行。
4.模塑材料，其含有热塑塑料和至少一种权利要求1的盐。
5.根据权利要求4的模塑材料，其特征在于模塑材料含有基于聚合物的重量计5-30％的盐。
6.权利要求1的盐作为用于热塑塑料，特别是聚酯或聚酰胺的防火剂或阻燃剂的用途。
7.根据权利要求6的用途，其特征在于加入钙或铝盐。
8.权利要求4的模塑材料在制造模制件，尤其是电子部件、机械部件、插头、机箱、罩、盖、外壳和涂层中的用途。
9.权利要求1的盐作为清漆的，尤其是防火清漆的组成部分的用途。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19608011A DE19608011A1 (de) | 1996-03-04 | 1996-03-04 | Salze von 1-Hydroxy-dihydrophospholoxiden und 1-Hydroxy-phospholanoxiden und ihre Verwendung als Flammschutzmittel |
| DE19608011.8 | 1996-03-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1168381A true CN1168381A (zh) | 1997-12-24 |
Family
ID=7786994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97110012A Pending CN1168381A (zh) | 1996-03-04 | 1997-02-28 | 1-羧基-磷杂环戊烯氧化物和1-羟基磷杂环戊烷氧化物的盐，它们的制备方法和它们作为防火剂的用途 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6087423A (zh) |
| EP (1) | EP0794191B1 (zh) |
| JP (1) | JPH09278784A (zh) |
| KR (1) | KR970065547A (zh) |
| CN (1) | CN1168381A (zh) |
| BR (1) | BR9701157A (zh) |
| DE (2) | DE19608011A1 (zh) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19708726A1 (de) | 1997-03-04 | 1998-09-10 | Hoechst Ag | Flammgeschützte Polymerformmassen |
| DE19708725A1 (de) | 1997-03-04 | 1998-09-10 | Hoechst Ag | Aluminiumsalze von Alkyl-hydroxymethylphosphinsäuren |
| DE19708724A1 (de) | 1997-03-04 | 1998-09-10 | Hoechst Ag | Aluminiumsalze von Alkyl-1-alkoxyethylphosphinsäuren |
| DE19720977A1 (de) | 1997-05-20 | 1998-11-26 | Hoechst Ag | Verfahren zur Herstellung von Aluminiumsalzen cyclischer Phosphinsäuren |
| MY117653A (en) | 1997-06-13 | 2004-07-31 | Polyplastics Co | Flame-retardant thermoplastic polyester resin composition |
| DE19734246A1 (de) * | 1997-08-07 | 1999-02-11 | Hoechst Ag | Verfahren zur Herstellung von Aluminiumsalzen cyclischer Phosphinsäuren |
| DE19737727A1 (de) * | 1997-08-29 | 1999-07-08 | Clariant Gmbh | Synergistische Flammschutzmittel-Kombination für Kunststoffe |
| DE19903709A1 (de) * | 1999-01-30 | 2000-08-10 | Clariant Gmbh | Flammschutzmittel-Kombination für thermoplastische Polymere II |
| TR200201863T2 (tr) * | 2000-01-21 | 2002-11-21 | Ticona Gmbh | Motorlu araçların motor bölmesinde termoplastik malzemeleri yapı elemanlarının üretimi. |
| DE10305548A1 (de) * | 2003-02-10 | 2004-08-26 | Basf Ag | Flammgeschützte Kunststoffformteile |
| KR100803193B1 (ko) * | 2005-08-24 | 2008-02-14 | 삼성에스디아이 주식회사 | 유기전해액 및 이를 채용한 리튬 전지 |
| JP5243006B2 (ja) * | 2006-12-04 | 2013-07-24 | 三菱エンジニアリングプラスチックス株式会社 | 難燃性ポリアミド樹脂組成物および成形品 |
| JP5468944B2 (ja) | 2010-03-12 | 2014-04-09 | 矢崎総業株式会社 | 押出しフレキシブルフラットケーブル |
| KR101309156B1 (ko) | 2011-03-24 | 2013-09-17 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지 |
| US10093801B2 (en) | 2013-12-12 | 2018-10-09 | Italmatch Chemicals S.P.A. | Halogen-free flame retardant polyamide moulding compositions with increased glow wire and fire resistance |
| KR20180081736A (ko) | 2015-11-13 | 2018-07-17 | 아이씨엘-아이피 아메리카 아이엔씨. | 폴리우레탄 및 폴리이소시아누레이트 포움용 반응성 난연제 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE700042A (zh) * | 1966-06-18 | 1967-12-01 | ||
| DE2252258A1 (de) * | 1972-10-25 | 1974-05-09 | Hoechst Ag | Schwerentflammbare thermoplastische polyester |
| DE2447727A1 (de) * | 1974-10-07 | 1976-04-08 | Hoechst Ag | Schwerentflammbare polyamidformmassen |
| GB1585085A (en) * | 1976-06-21 | 1981-02-25 | Ici Ltd | Polyamide compositions |
| US4208322A (en) * | 1978-04-13 | 1980-06-17 | Pennwalt Corporation | Polyester-polyamide resins flame retarded by poly(metal phosphinate)s |
| US4180495A (en) * | 1978-04-13 | 1979-12-25 | Pennwalt Corporation | Polyester resins flame retarded by poly(metal phosphinate)s |
| US4221874A (en) * | 1978-06-07 | 1980-09-09 | Monsanto Company | Phospholane oxide containing polymers |
| IT1157253B (it) * | 1982-02-09 | 1987-02-11 | Saffa Spa | Procedimento per rendere autoestinguenti, mediante fosforo rosso, materiali termoplastici sintetici e prodotti cosi' ottenuti |
| DE4012489A1 (de) | 1990-04-19 | 1991-10-24 | Bayer Ag | Verfahren zur herstellung von 1-halogen-1-oxophospholenen |
| DE4430932A1 (de) * | 1994-08-31 | 1996-03-07 | Hoechst Ag | Flammgeschützte Polyesterformmasse |
| DE19608006A1 (de) * | 1996-03-04 | 1997-09-11 | Hoechst Ag | Salze von phosphonigen Säuren und deren Verwendung als Flammschutzmittel in Kunststoffen |
| DE19645125A1 (de) * | 1996-11-04 | 1998-05-14 | Hoechst Ag | Verfahren zur Herstellung von Aluminiumsalzen organischer Phosphorsäuren |
-
1996
- 1996-03-04 DE DE19608011A patent/DE19608011A1/de not_active Withdrawn
-
1997
- 1997-02-20 DE DE59710003T patent/DE59710003D1/de not_active Expired - Fee Related
- 1997-02-20 EP EP97102722A patent/EP0794191B1/de not_active Expired - Lifetime
- 1997-02-28 CN CN97110012A patent/CN1168381A/zh active Pending
- 1997-03-03 BR BR9701157A patent/BR9701157A/pt not_active Application Discontinuation
- 1997-03-03 US US08/810,656 patent/US6087423A/en not_active Expired - Fee Related
- 1997-03-04 JP JP9048865A patent/JPH09278784A/ja active Pending
- 1997-03-04 KR KR1019970006966A patent/KR970065547A/ko not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09278784A (ja) | 1997-10-28 |
| KR970065547A (ko) | 1997-10-13 |
| DE59710003D1 (de) | 2003-06-12 |
| US6087423A (en) | 2000-07-11 |
| DE19608011A1 (de) | 1997-09-11 |
| EP0794191A1 (de) | 1997-09-10 |
| EP0794191B1 (de) | 2003-05-07 |
| BR9701157A (pt) | 1998-12-15 |
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