CN1437631A - 用于膨胀软质聚氨酯泡沫的阻燃剂混合物 - Google Patents
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Abstract
一种用于聚氨酯泡沫的阻燃剂和滴流余烬阻滞剂混合物,包括:(a)主要量的含(i)大量低聚卤化有机磷阻燃剂和(ii)少量单体卤化有机磷阻燃剂的混合物;(b)水溶性或醇溶性脲醛树脂;和(c)N,N-双(羟烷基)氨基甲基膦酸二烷基酯。
Description
发明背景
本发明涉及软质回弹性聚氨酯泡沫的改进,并特别地涉及当承受火时这样泡沫特性的改进。
本发明的主要目的是提供甚至当在曝露于强烈火源时仍具有显著增强的耐燃烧性的聚氨酯泡沫。软质回弹性聚氨酯泡沫是在一种或多种发泡剂、一种或多种表面活性剂和一种或多种催化剂存在下,通过多元醇和有机多异氰酸酯的反应制备的。
这些泡沫的用途包括地毯衬垫,包装,纺织品内衬,床垫,枕头,家具垫料,弹性垫,汽车防冲垫以及隔声和隔热材料。
当点燃时聚氨酯泡沫容易燃烧。人们已经向聚氨酯泡沫中加入各种阻燃剂,包括磷的卤化酯。这已经导致可燃性的一些改进,在低强度火源的点燃之后的燃烧程度降低了,泡沫甚至可以在小规模实验室测试中被制成自熄的。
然而,当燃烧的确发生时,泡沫会熔融并滴流燃烧着的余烬,而该余烬会点燃在附近的其它可燃材料,引起火的扩散。这类所谓的“自熄”泡沫一般除低强度火源外对其它火源是不耐燃的。人们已经将其它添加剂加入到聚氨酯泡沫中以协助克服此问题并使完成的泡沫在受火之后发生膨胀,或生成炭。
这类泡沫在燃烧期间产生较少的火焰、滴流余烬并产生可作为隔热屏障的炭,且因此减缓或防止火的扩展。
能够通过UL 94HF-1测试的软质回弹性聚氨酯泡沫的一种制造方法描述在G.Fesman的U.S.专利No.4,514,524中。在此专利中,采用如下物质的添加剂混合物处理聚醚多元醇基泡沫:一种聚酯多元醇,一种卤化阻燃剂(如磷酸三(1,3-二氯丙基)酯),和水溶性或醇溶性脲醛树脂。
那种在点燃和燃烧时形成燃烧着的余烬的倾向低的软质聚氨酯泡沫的生产方法将是有益的。对于许多应用,例如家具垫,软质聚醚氨酯泡沫比聚酯型聚氨酯泡沫更好。当要求高回弹性缓冲时,不能使用干炭软质聚酯型聚氨酯泡沫。因此,用户会优选可满足某些可燃性分级,例如Underwriter’s可燃性UL-94 HF-1分级的聚醚泡沫的干炭性能。此外,掺有聚酯树脂的聚氨酯缓冲泡沫的回弹性也是受关注之点。聚酯泡沫回弹性更差,而回弹性是缓冲垫舒适的重要因素。
制备能够满足UL-94 HF-1可燃性分级的软质聚醚氨酯泡沫将是有意义的。配制满足以上分级且回弹性较高的软质泡沫将是更有意义的。
本发明的其它目的和优点在说明书的全文中加以说明。
发明概述
根据本发明,现在已经发现了一种具有形成炭、或膨胀性能改进了的软质回弹性聚醚聚氨酯泡沫,及这样的泡沫的制备方法。通过聚醚多元醇和有机多异氰酸酯的反应而制备软质回弹性阻燃性且膨胀聚氨酯泡沫的该方法包括:向形成聚氨酯的反应物中加入至少一种发泡剂,至少一种表面活性剂,至少一种催化剂和阻燃、滴流余烬阻滞有效量的组合添加剂,而该组合添加剂包括:(i)一种卤化有机磷阻燃剂,它包含主要量的低聚物类型和少量单体类型;(ii)水溶性或醇溶性脲醛树脂;和(iii)N,N-双(羟烷基)氨基甲基膦酸二烷基酯。
本发明也包括用于增强聚氨酯泡沫阻燃性和滴流余烬阻滞性的包含上文所述的组分(i),(ii),和(iii)的组合物。
发明内容
本发明的方法可以由常规聚氨酯软质泡沫形成技术实施。根据本发明密度为每立方米约16至约48千克的聚氨酯泡沫由已知方法,如预聚物、准聚合物,或一步法系统制备。泡沫可以由间歇或连续方法制备。形成泡沫的混合物应当包括作为基础成分的:(A)多元醇(根据本发明宜是聚醚多元醇),(B)有机异氰酸酯,(C)发泡剂,(D)聚氨酯催化剂,(E)表面活性剂,和(F)如下物质的组合:卤化阻燃剂,它包含主要量的低聚物类型和少量单体类型,水溶性或醇溶性脲醛树脂添加剂,和N,N-双(羟烷基)氨基甲基膦酸二烷基酯。
优选的聚醚多元醇成分(A)可以选自任何可得到的并通常在本领域中用于制备软质醚类型聚氨酯泡沫的各种多羟基聚醚化合物。最通常的聚醚多元醇化合物,聚氧化烯聚醚多元醇,一般由烯化氧,如1,2-环氧丙烷,与多羟基引发剂或启始剂的反应而制备。多羟基引发剂或启始剂可以是,例如,甘油、三羟甲基甲烷、三羟甲基丙烷、三乙醇胺或聚乙二醇。
用于制备聚醚的烯化氧宜为含2-4个碳原子的那些,例如环氧乙烷、1,2-环氧丙烷、1,2-环氧丁烷、氧杂环丁烷和四氢呋喃。同样有用的是衍生自相应氧化芳亚烷基(例如单独的氧化苯乙烯或与烯化氧混合的氧化苯乙烯)的聚(芳亚烷基醚)多元醇。一般情况下,环氧丙烷,即,1,2-环氧丙烷,和1,2-环氧丙烷与环氧乙烷的混合物优选用于聚醚多元醇反应物的制备。实施本发明同样可用的多元醇的是所谓的接枝聚合物,即以一定的方式用丙烯腈和/或苯乙烯改性的聚醚多元醇,其中一些接枝到聚醚多元醇主链上(但不是接枝到官能基团、羟基上),而另一些以聚合物形式分散于多元醇中。
用于本发明的聚醚的分子量宜为约2000至约6000,且最优为约3000至约4500,其平均羟基官能度为约2至约3。市售聚醚的例子是F-3020牌号聚醚多元醇,Dow Chemical的产品。
然而如需要,组分(A)可包括聚醚多元醇和聚酯多元醇的组合(如在G.Fesman的U.S.专利No.4,514,524中描述的那样,该专利在此引入),或甚至不含聚醚多元醇的聚酯多元醇。
这样的非必要聚酯多元醇成分可以选自通常用于软质聚氨酯泡沫的制备的多元醇的一种或混合物。适于这些软质聚氨酯泡沫制备的典型的聚酯多元醇的分子量为500-5000,且羟基数为约15-约150。合适的多元醇包括从二醇和饱和多羧酸制备的线性聚合物聚酯。例如,可以通过二甘醇与己二酸的反应制备双官能聚酯多元醇。特别优选的聚酯多元醇是FOMREZ53牌号产品,来自Witco Corporation。
泡沫形成工艺的有机多异氰酸酯成分(B)可以选自用于这样目的的常规异氰酸酯。
异氰酸酯的异氰酸酯官能度宜为2-3。有用的异氰酸酯包括芳族、脂族、环脂族、杂环类型及其混合物。合适的有机异氰酸酯包括甲苯二异氰酸酯和苯二异氰酸酯,由于成本和可利用性优选是甲苯二异氰酸酯。
发泡剂成分(C)可包括单独的水或者水与其它常规发泡剂,如二氯甲烷、或沸点为约-30℃到60℃的碳氟化合物或烃的组合。
聚氨酯催化剂成分(D)选自通常用于这样目的材料。合适的催化剂包括胺如叔胺和金属化合物如辛酸亚锡、二月桂酸二丁基锡等。
用于本发明方法的表面活性剂成分(E)可以选自通常用于这样目的的表面活性剂。
尽管许多表面活性剂在本发明方法中可操作,已经发现如果使用硅氧烷表面活性剂,如Union Carbide Corporation TM L5810和L5740不可水解硅氧烷表面活性剂,可得到特别所需的均匀泡孔结构和外观。
本特定发明的阻燃剂和滴流余烬阻滞剂添加剂组合(F)包括卤化阻燃剂,它包含占主要量的低聚物种类和少量的单体种类,水溶性或醇溶性脲醛树脂和N,N-双(羟烷基)氨基甲基膦酸二烷基酯。
用于本发明方法和泡沫中的卤化阻燃剂成分包括占主要量的(如,约88重量%至约96重量%)卤化阻燃剂低聚物种类和少量(如,约12重量%至约4重量%)卤化阻燃剂低聚物种类。
例如,低聚物组分可包括氯化低聚物磷酸酯,如从Akzo NobelFunctional Chemicals LLC市售的FYROL 99牌号,而单体组分可以是磷酸三(卤烷基)酯,优选在烷基中含有1-4个碳原子的氯化单体磷酸酯,如来自Akzo Nobel Functional Chemicals LLC的FYROL FR-2牌号,为磷酸三(1,3-二氯丙基)酯。用于本发明的市售低聚物/单体阻燃剂添加剂的商标为FYROL EFF,购自Akzo Nobel Functional Chemicals LLC。它含有66重量%低聚物FYROL 99产品,32.5重量%单体FYROL FR-2产品,同时可含有非必要的但优选的抗焦烧配方(1重量%环氧树脂,可以ERL-4221牌号购得,和0.5重量%吩噻嗪,基于整个配制剂的重量)。
本发明的氨基树脂是液体水溶性或醇溶性未交联(非热固性)脲醛或脲醛衍生物预缩合物树脂,它与有机异氰酸酯无反应性(在泡沫形成条件下)。术语“水溶性或醇溶性脲醛树脂”在此说明书中用于描述这类必要成分。本发明的优选脲醛树脂是丁基化和甲基化脲醛树脂如CYMEL U-80和CYMEL65牌号树脂,为Cytec Industries Inc的产品。
用于本发明泡沫的阻燃剂和滴流余烬阻滞剂添加剂混合物的量为能有效得到用户所需的阻燃剂和滴流余烬性能混合物的量。确定添加剂合适水平的有用标准是Underwriter’s Laboratoreies UL-94测试。通过UL-94测试的HF-1标准的聚氨酯泡沫样品被认为包含有效水平的用于本发明目的的添加剂。
卤化有机磷低聚物/单体阻燃剂、水溶性或醇溶性脲醛树脂和N,N-双(羟烷基)氨基甲基膦酸二烷基酯添加剂混合物的总重量典型地为泡沫配制成分或最终软质聚氨酯泡沫产物的约5-约50重量%。多元醇对卤化阻燃剂组分对水溶性或醇溶性脲醛树脂对N,N-双(羟烷基)氨基甲基膦酸二烷基酯的比例是约100∶22∶2.25∶0.75至约100∶14∶1.5∶0.5。优选二烷基中包含约1至约4个碳原子,如由二乙基或二异丙基示例。羟烷基优选是2-羟乙基。
本发明的添加剂混合物可以是适于加入到可形成泡沫的反应体系中以给软质回弹性聚氨酯泡沫产物赋予增强了的阻燃性和滴流余烬阻滞性的预混合贮存稳定组合物。此添加剂混合物的必要成分包括多元醇、卤化阻燃剂、水溶性或醇溶性未交联脲醛树脂和N,N-双(羟烷基)氨基甲基膦酸二烷基酯。然而,各种非必要成分可以加入到添加剂混合物中。例如,该混合物可含有聚醚多元醇。其它非必要的成分可以选自溶剂、稀释剂、着色剂、稳定剂、开孔剂、润滑剂、生物杀伤剂等。异氰酸酯泡沫反应物不可加入。
添加剂混合物在使用时可以在反应之前或同时以任何顺序与聚氨酯泡沫形成成分混合。
构成添加剂混合物的单个成分可以单独地计量入泡沫配制剂中,如在“一步法”方法中那样。
如下实施例描述本发明的各种实施方案。从本说明书的思考或在此公开的本发明实践而得出的其它实施方案对于本领域技术人员是显然的。说明书和实施例应视为仅作为示例,本发明的真实范围和精神由实施例之后的权利要求指示。
实施例
阻燃剂混合物:
用于如下实施例的阻燃剂混合物含有94.0重量%的FYROL EFF阻燃剂,5重量%来自Cytec Chemicals的CYMEL U-80树脂(丁基化脲醛树脂),和1重量%的FYROL 6阻燃剂(双(羟乙基)氨基甲基膦酸二乙基酯)。FYROL EFF产品是如下物质的混合物:66重量%的FRYOL 99阻燃剂(氯化低聚物磷酸酯-CAS#109640-81-5),32.5重量%的FYROL FR-2阻燃剂(磷酸三(1,3-二氯丙基-2)酯-CAS#13674-87-8),1重量%环氧树脂(ERL-4221牌号-CAS#2386-87-0),和0.5重量%吩噻嗪(CAS#92-84-2)。阻燃剂混合物规格: 分析
典型的外观 琥珀色%磷 10.93%%氯化物 30.55%酸值 0.2(最大)比重 1.41粘度(cps)25℃ 1400闪点 220°F成雾性能(110℃/6hr/38°) 83蒸气压(400) 105(参见如下)----ASTM D2879
温度(°F) | 150 | 200 | 250 | 300 | 350 | 400 |
蒸气压 | 0.18 | 0.90 | 3.6 | 12.8 | 38 | 105 |
使用典型的聚醚聚氨酯泡沫产生如下阻燃剂测试数据,该泡沫在每立方英尺1.8磅(pcf)的公称密度下测试。用于形成泡沫的配制剂有如下数据:一种聚醚多元醇,其羟基数目为56;水水平为3.55;胺水平为0.22,和NCO指数为110。本发明的阻燃剂使此聚醚聚氨酯泡沫满足UL-94 HF-1测试标准。聚氨酯应用配制剂:
UL-94 HF-测试标准
样品 | 1 | 2 | 3 | 4 |
多元醇F-3020Lyondell(Bayer) | 100.0 | 100.0 | 100.0 | 100.0 |
FR水平 | 8 | 10 | 15 | 17 |
H2O | 3.55 | 3.55 | 3.55 | 3.55 |
Dabco_-33LV/Niax_A-1=3.1比例CK Witco | 0.22 | 0.22 | 0.22 | 0.22 |
硅氧烷Niax_L-620 CKWitco | 0.80 | 0.80 | 0.80 | 0.80 |
辛酸亚锡T-10 Air Products | 0.25 | 0.25 | 0.25 | 0.25 |
二异氰酸甲苯酯-TDI | 47.10 | 47.10 | 47.10 | 47.10 |
TDI指数 | 110 | 110 | 110 | 110 |
白化时间(秒) | 7 | 7 | 7 | 6 |
起发时间(秒) | 105 | 129 | 129 | 110 |
空气流(pcf) | 4.5 | 4.4 | 4.5 | 4.3 |
FR粘度:25℃/10rpm/SPDL 211400cps | ||||
UL-94 HF-1完全燃烧/棉点燃 | 失败是/是 | 失败是/否 | 通过否/否 | 通过否/否 |
分级
聚氨酯应用数据结果:
标准条件 | HF-1 | HF-2 | HBF |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 4/5是≤2sec.1/5是≤10sec.≤30sec.否<60mm | 4/5是≤2sec.1/5是≤10sec.≤30sec.是<60mm | 没有任何试样在100mm跨度上燃烧超过每分钟40mm或在燃烧或炽热达到125mm量表标志之前每个试样停止燃烧BR(燃烧速率)=mm/min |
备注:4/5-一套五个试样中的四个1/5-一套五个试样中的一个 |
样品1的UL 94HF-1/HF-2和HBF可燃性测试结果
样品2的UL 94HF-1/HF-2和HBF可燃性测试结果
样品3的UL 94HF-1/HF-2和HBF可燃性测试结果
样品4的UL 94HF-1/HF-2和HBF可燃性测试结果
标准条件 | 结果 | HF-1标准 | HF-2标准 | HBF标准 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 20秒2秒是/是30毫米 | 否 | 否 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 30秒0是/是20毫米 | 否 | 否 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 21秒2秒是/是40毫米 | 否 | 否 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 13秒0是/是25毫米 | 否 | 否 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 29秒3秒是/是20毫米 | 否 | 否 | 是 |
结果 | HF-1标准 | HF-2标准 | HBF标准 | |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 20秒4秒是/否19毫米 | 否 | 否 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 29秒15秒是/否25毫米 | 否 | 否 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 40秒13秒是/否50毫米 | 否 | 否 | 是 |
完全燃烧时间每个单个试样的余辉时间 | 20秒20秒 | 否 | 否 | 是 |
由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 是/否15毫米 | |||
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 40秒18秒是/否45毫米 | 否 | 否 | 是 |
结果 | HF-1标准 | HF-2标准 | HBF标准 | |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 2秒10秒否/否3毫米 | 是 | 是 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 2秒10秒否/否4毫米 | 是 | 是 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 6秒0否/否2毫米 | 是 | 是 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 2秒0秒否/否5毫米 | 是 | 是 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 1秒10秒否/否5毫米 | 是 | 是 | 是 |
样品 | 结果 | HF-1标准 | HF-2标准 | HBF标准 | |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 4 | 1秒5秒否/否1毫米 | 是 | 是 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 4 | 2秒0秒否/否5毫米 | 是 | 是 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 4 | 1秒0秒否/否1毫米 | 是 | 是 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 4 | 2秒0秒否/否2毫米 | 是 | 是 | 是 |
完全燃烧时间每个单个试样的余辉时间由燃烧粒子或液滴而点燃烧的棉指示物每个单个试样的损害长度 | 4 | 6秒0秒否/否6毫米 | 是 | 是 | 是 |
应当根据五个试样测试结果将材料分级为HF-1,HF-2或HBF。如果一套五个中仅有一个试样不满足要求,则按照相同的条件测试另一套五个试样。
下表给出包含各种阻燃剂,包括本发明混合物(它编码为“ULM”)的聚氨酯泡沫配方:
成分 | 量(PHP) |
Caradol SC56.02聚醚多元醇(Shell) | 100 |
测试的阻燃剂 | 见下表 |
水 | 5.00 |
Dabco BL-11胺催化剂 | 0.06 |
Dabco 33-LV胺催化剂 | 0.18 |
Tegostab B3640表面活性剂/稳定剂 | 1.20 |
Dabco T-9辛酸亚锡 | 0.18 |
甲苯二异氰酸酯-80/20指数(110) | 62.70 |
下表显示含有阻燃剂如本发明的混合物(“ULM”),磷酸三(三氯乙基)酯(“FR-2”),或蜜胺(“APP”)的一系列聚氨酯泡沫的U-94HF测试结果:
No. | 阻燃剂 | 催化剂调节 | 总燃烧距离(cm) | 从2.5cm的燃烧时间(秒) | 燃烧速度(cm/min) | 分级 | 空气流(升/min) |
1/21/32/22/32/43/23/33/46/26/36/47/27/37/4 | 空白15ULM20ULM15FR-210FR-215FR-210APP | 0.10BL110.3033LV0.22BL110.3033LV | 12.7512.54.555.543.53.511111410129.5 | 3333912161066586076606258 | 18.618.113.112.311.18.89.69.68.88.59.07.59.27.2 | 失败HF-1HF-1HF-1HF-1HF-1HF-1HBFHBFHBFHBFHBFHBF | 157142164230219 |
下表提供在老化(在25℃下四小时)之后所示泡沫配方的UL-94HF测试结果:
No. | 阻燃剂 | 总燃烧距离(cm) | 从2.5cm的燃烧时间(sec) | 燃烧速度(cm/min) | 分级 | 空气流(升/min) | 密度(kg/m3) |
1/21/31/41/52/22/32/42/53/23/33/43/54/24/34/44/55/25/35/45/56/26/36/46/5 | 15FR-25蜜胺15FR-210蜜胺20FR-25蜜胺20FR-210蜜胺20FR-215蜜胺15FR-25APP422 | 75.57.59.54.576.554.54.755.755.754.54.54.55.54.544.54.58.251010.7510.75 | 363537461529272312182623131814211112141137577057 | 7.45.18.09.17.89.28.86.49.87.47.48.49.06.58.48.510.77.38.410.79.37.97.08.6 | HBFHF-1HBFHBFHF-1HBFHBFHF-1HF-1HF-1HF-1/HBFHF-1/HBFHF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HBFHBFHBFHBF | 181184189186190184 | 24.425.8 |
7=具有差泡孔结构的差泡沫8/28/38/48/59=具有非常差泡孔结构和收缩的非常差泡沫10=未制备(假定为非常差的泡沫)11/111/211/712/212/312/412/513/213/313/413/213/313/413/5 | 20FR-25APP42220ULM25ULM30ULM | 66.757844.54.753.544.254.53.754.2543.53.53.753.75 | 48606064151423912111011101287910 | 4.34.24.55.15.88.45.86.47.39.311.86.610.37.37.28.28.17.3 | HBFHBFHBFHBFHF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1 | 184160159175 | 26.325.3 |
下表提供在老化之前(在70℃下7日)所示泡沫配方的L-94HF测试结果:
No. | 阻燃剂 | 总燃烧距离(cm) | 从2.5cm的燃烧时间(秒) | 燃烧速度(cm/min) | 分级 |
1/21/31/41/52/22/32/42/53/23/33/43/54/24/34/44/55/25/35/45/56/26/36/46/5 | 15FR-25蜜胺15FR-210蜜胺20FR-25蜜胺20FR-210蜜胺20FR-215蜜胺15FR-25APP422 | 6775.556.56.56.54.555.5554.54.5545.544.58.598.510.5 | 293542232225283315172118201315181222101452455561 | 7.27.66.47.76.79.58.57.27.88.78.58.27.49.07.88.27.38.18.88.46.98.66.57.8 | HBFHBFHBFHF-1HBFHBFHBFHBFHF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HBFHBFHBFHBF |
7=具有差泡孔结构的差泡沫8/28/38/48/59=具有非常差泡孔结构和收缩的非常差泡沫10=未制备(假定为非常差的泡沫)11/311/411/511/211/311/411/512/212/312/412/5 | 20FR-25APP42220ULM20ULM25ULM | 4.55.754.55.54.5454.54.54.754.543.544 | 13171223141010151313131271110 | 9.011.39.87.78.48.814.87.89.010.29.07.38.28.08.8 | HF-1HBF/HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1HF-1 |
下表显示含磷酸三(三氯乙基)酯(“FR-2”)和蜜胺(“APP”)的混合物的一系列聚氨酯泡沫的U-94HF测试结果:
No. | FR数量 | 催化剂调节 | 总燃烧距离(cm) | 从2.5cm的燃烧时间(秒) | 燃烧速度(cm/min) | 分级 | 密度(kg/m3) | 空气流(升/min) |
9/29/39/49A/29A/39A/49B/29B/39B/410A/210A/310A/410B/210B/310B/4 | 20FR-210APP20FR-210APP20FR-210APP20FR-215APP20FR-215APP | 0.22BL110.3033LV0.40BL110.3033LV0.40BL110.5033LV0.40BL110.3033LV0.40BL110.4033LV | 788.575.756.55.755.256.256.255.756.255.54.756.25 | 394345232129241928382931211634 | 6.97.67.911.69.28.28.09.38.05.96.67.28.58.36.5 | HBFHBFHBFHBFHF-1HBFHF-1HF-1HBFHBFHF-1HBFHF-1HF-1HBF | 30.627.628.831.230.9 | 220212186212209 |
以上内容仅用于例示本发明的某些实施方案,而不应当认为这些内容是限制性的。所需的保护范围由以下权利要求给出。
Claims (8)
1.一种用于聚氨酯泡沫的阻燃剂和滴流余烬阻滞剂混合物,该混合物含有:
(a)主要量的含(i)大量低聚卤化有机磷阻燃剂和(ii)少量单体卤化有机磷阻燃剂的混合物;
(b)水溶性或醇溶性脲醛树脂;和
(c)N,N-双(羟烷基)氨基甲基膦酸二烷基酯。
2.权利要求1的混合物,其中低聚卤化有机磷阻燃剂是氯化低聚磷酸酯。
3.权利要求1的混合物,其中单体卤化有机磷阻燃剂是氯化单体含烷基磷酸酯,其中在烷基中含有1-4个碳原子。
4.权利要求1的混合物,其中水溶性或醇溶性脲醛树脂选自丁基化和甲基化脲醛树脂。
5.权利要求1的混合物,其中所述N,N-双(羟烷基)氨基甲基膦酸二烷基酯在其烷基中含约1至约4个碳原子,而其中羟烷基是2-羟乙基。
6.权利要求1的混合物,其中低聚卤化有机磷阻燃剂是氯化低聚磷酸酯,单体卤化有机磷阻燃剂是氯化单体含烷基磷酸酯,其中在烷基中含有1-4个碳原子,水溶性或醇溶性脲醛树脂选自丁基化和甲基化脲醛树脂,且N,N-双(羟烷基)氨基甲基膦酸二烷基酯在烷基中含约1至约4个碳原子,而其中羟烷基是2-羟乙基。
7.权利要求6的混合物,其中单体卤化有机磷阻燃剂是磷酸三(1,3-二氯丙基)酯,水溶性或醇溶生脲醛树脂是丁基化脲醛树脂,且N,N-双(羟烷基)氨基甲基膦酸二烷基酯是N,N-双(羟乙基)氨基甲基膦酸二乙基酯。
8.一种聚氨酯泡沫,其中含有权利要求1-7任意一项的混合物。
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JP (1) | JP2004501255A (zh) |
CN (1) | CN1437631A (zh) |
AU (1) | AU2001270064A1 (zh) |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101092535B (zh) * | 2007-07-24 | 2010-08-18 | 海洋化工研究院 | 喷涂阻燃柔性聚脲组合物及其应用 |
CN101248130B (zh) * | 2005-05-27 | 2011-11-09 | 苏普雷斯塔有限责任公司 | 阻燃软质聚氨酯泡沫 |
CN103497557A (zh) * | 2013-09-24 | 2014-01-08 | 北京工商大学 | 一种阻燃硬质聚氨酯泡沫 |
CN104017164A (zh) * | 2014-06-24 | 2014-09-03 | 北京理工大学 | 一种温敏智能型防水透湿和阻燃水性聚氨酯涂层剂及其制备方法 |
CN106117491A (zh) * | 2016-07-25 | 2016-11-16 | 重庆钱珑新科技有限公司 | 聚氨酯全水基有机发泡材料及其制备方法 |
Families Citing this family (4)
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ATE439399T1 (de) * | 2004-05-13 | 2009-08-15 | Basf Se | Flammschutzmittel |
DE102004056913A1 (de) * | 2004-11-25 | 2006-06-01 | Aik Flammadur Brandschutz Gmbh | Mittel und Verfahren zur Herstellung eines Brandschutzelementes sowie Brandschutzelement |
CN102149762B (zh) | 2008-08-27 | 2013-07-31 | 巴斯夫欧洲公司 | 具有聚合物分散剂的阻燃组合物 |
EP2848640A1 (de) * | 2013-09-13 | 2015-03-18 | LANXESS Deutschland GmbH | Phosphorsäureester-Zubereitungen mit verringerter Hygroskopie |
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US4374207A (en) * | 1980-10-24 | 1983-02-15 | G.F.C. Foam Corporation | Intumescent flexible polyurethane foam |
US4407981A (en) * | 1980-12-19 | 1983-10-04 | Stauffer Chemical Company | Flame retardant mixture for polyurethanes |
US4433071A (en) * | 1982-12-14 | 1984-02-21 | Stauffer Chemical Company | Flame and dripping ember retardant flexible polyurethane foams |
US4514524A (en) * | 1984-07-13 | 1985-04-30 | Stauffer Chemical Company | Intumescent flexible polyurethane foam |
US4654105A (en) * | 1985-01-25 | 1987-03-31 | Stauffer Chemical Company | Process for producing laminated polyether urethane foam |
US4880844A (en) * | 1988-05-27 | 1989-11-14 | Akzo America Inc. | Flame laminatable polyether urethane foam |
JP2755509B2 (ja) * | 1991-10-16 | 1998-05-20 | 大八化学工業株式会社 | ポリウレタン用難燃性組成物 |
US5371166A (en) * | 1993-12-22 | 1994-12-06 | The B. F. Goodrich Company | Polyurethane composition for use as a dispersing binder |
JP2000119658A (ja) * | 1998-10-09 | 2000-04-25 | Constructora Fuego Cero Sa De Cv | 可燃性物質に発火回避性または難燃性を与える組成物 |
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2001
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- 2001-06-22 CN CN01811553A patent/CN1437631A/zh active Pending
- 2001-06-22 JP JP2002504355A patent/JP2004501255A/ja active Pending
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101248130B (zh) * | 2005-05-27 | 2011-11-09 | 苏普雷斯塔有限责任公司 | 阻燃软质聚氨酯泡沫 |
CN101092535B (zh) * | 2007-07-24 | 2010-08-18 | 海洋化工研究院 | 喷涂阻燃柔性聚脲组合物及其应用 |
CN103497557A (zh) * | 2013-09-24 | 2014-01-08 | 北京工商大学 | 一种阻燃硬质聚氨酯泡沫 |
CN104017164A (zh) * | 2014-06-24 | 2014-09-03 | 北京理工大学 | 一种温敏智能型防水透湿和阻燃水性聚氨酯涂层剂及其制备方法 |
CN106117491A (zh) * | 2016-07-25 | 2016-11-16 | 重庆钱珑新科技有限公司 | 聚氨酯全水基有机发泡材料及其制备方法 |
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JP2004501255A (ja) | 2004-01-15 |
AU2001270064A1 (en) | 2002-01-02 |
EP1297062A1 (en) | 2003-04-02 |
WO2001098401A1 (en) | 2001-12-27 |
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