WO2015135348A1 - 一种本质阻燃硬质聚氨酯泡沫塑料 - Google Patents

一种本质阻燃硬质聚氨酯泡沫塑料 Download PDF

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WO2015135348A1
WO2015135348A1 PCT/CN2014/093079 CN2014093079W WO2015135348A1 WO 2015135348 A1 WO2015135348 A1 WO 2015135348A1 CN 2014093079 W CN2014093079 W CN 2014093079W WO 2015135348 A1 WO2015135348 A1 WO 2015135348A1
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rigid polyurethane
polyurethane foam
weight
retardant
parts
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PCT/CN2014/093079
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English (en)
French (fr)
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戴李宗
谢聪
罗伟昂
曾碧榕
许一婷
刘新瑜
何凯斌
李奇
李远源
陈显明
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厦门大学
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Priority to US15/125,378 priority Critical patent/US9718937B2/en
Publication of WO2015135348A1 publication Critical patent/WO2015135348A1/zh

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Definitions

  • the present invention relates to the flame retardancy of a foamed plastic, in particular a rigid polyurethane foam.
  • Polyurethane (PU) one of the six most important synthetic materials, is widely used in building energy conservation, home appliances, transportation (automobiles, subways, high-speed rail, etc.), new energy and other industries.
  • fire accidents have occurred in China, which has made the research on the flame retardancy of polyurethane rigid foams on the agenda. Therefore, how to further improve the flame retardant grade of polyurethane rigid foam without significantly affecting performance has become an urgent problem to be solved.
  • Chinese patent CN101962474A discloses an environmentally-friendly high flame-retardant rigid polyurethane foam, which is obtained by using a polymer polyol, a pentane, a flame retardant, a modified hollow microbead and a polyisocyanate in a foam stabilizer and/or a catalyst. The mixed reaction is obtained under the condition, and the vertical combustion reaches V-0 level, which can be well applied to the insulation of building exterior walls, pipelines and refrigeration equipment.
  • Chinese patent CN102875762A discloses a high flame retardant rigid polyurethane foam, which is compounded with a flame retardant and has a high flame retardant rigid polyurethane foam having an oxygen index of 30 or more.
  • the material has high flame retardancy, low smoke generation and high fire and heat insulation properties, which improves the safety in the use of rigid polyurethane foam.
  • the existing rigid polyurethane foam flame retardant technology is mostly concentrated on the additive type, which has low cost, quick effect and good application prospect.
  • An intrinsically fire-retardant rigid polyurethane foam the raw material of which comprises the following components by weight:
  • the reactive phosphorus-containing flame retardant is 9,10-dihydro-9-oxa-10-phosphaphenanthr-8-hydroxybenzyl alcohol (DOPO-HB), and the structural formula is:
  • the weight ratio of the polyether polyol to the reactive phosphorus-containing flame retardant is from 10 to 90:10 to 90.
  • the polyether polyol is a polyether polyol for a rigid foam polyurethane.
  • the amine catalyst is triethylenediamine.
  • the tertiary amine catalyst is 2,4,6-tris(dimethylaminomethyl)phenol.
  • the foam stabilizer is a silicon carbon bond type foam stabilizer.
  • the blowing agent is water.
  • the isocyanate has a viscosity of from 150 to 250 mPa ⁇ s and an NCO mass percentage of from 30.0% to 32.0%.
  • the organometallic catalyst is dibutyltin dilaurate.
  • the preparation method of the above-mentioned essential flame-retardant rigid polyurethane foam is as follows:
  • the mixed component B is added to the mixed component A, poured into a mold, foamed, aged, and subjected to a demolding process, and finally the intrinsic flame-retardant rigid polyurethane foam of the present invention is obtained.
  • the DOPO-HB of the present invention is a hydroxyl-terminated alcohol like the polyether polyol, which functions as a polyether polyol, and at the same time, a molecular chain between the hydroxyl active sites introduces a flame retardant element to form an elemental molecule.
  • Such compounds not only have the flame retardant properties of inorganic substances, but also have the elasticity and plasticity of organic substances;
  • the foam of the present invention introduces a DOPO group having excellent flame retardancy into a polyurethane network in the form of a covalent bond, thereby overcoming the disadvantages of poor compatibility between the conventional additive flame retardant and the PU matrix and easy migration after standing for a long time. Compared with the added flame retardant, the added amount thereof is greatly reduced, and the advantage of the reactive flame retardant is exerted;
  • the foam of the invention avoids the rubber-like "blooming" phenomenon, and the active chain containing the flame-retardant element is introduced into the main chain and the side chain of the polyurethane, and is permanently modified without significantly affecting the performance of the matrix resin. Improve the flame retardant properties of polyurethane.
  • 1 is a 1 H nuclear magnetic resonance spectrum of a reactive phosphorus-containing flame retardant DOPO-HB used in the present invention
  • Figure 2 is a 31 P nuclear magnetic resonance spectrum of the reactive phosphorus-containing flame retardant DOPO-HB used in the present invention.
  • the polyether polyol for the rigid foam type polyurethane in the following examples was selected from a sucrose polyether polyol having a hydroxyl value of 441 mgKOH/g.
  • the isocyanate used was an isocyanate of the type PM-100 produced by Yantai Wanhua Polyurethane Co., Ltd., and its viscosity was 150-250 mPa ⁇ s, and the NCO mass percentage was 30.0%-32.0%.
  • This example is a comparative example in which no reactive phosphorus-containing flame retardant is added.
  • sucrose polyether polyol 3.5g triethylenediamine, 2.5g silicon carbon bond type foam stabilizer, 2.5g 2,4,6-tris(dimethylaminomethyl)phenol and 1.5g water
  • B material 150g PM-100 and 0.1g dibutyltin dilaurate
  • stir and mix at room temperature 2500r/min.
  • the mixture was observed to be whitish, it was poured into a self-made mold and freely foamed. After foaming, it was aged for 48 hours, and the mold was released to obtain a rigid polyurethane foam. Its oxygen index is 17.0 (GB/T 2406.1 ⁇ 2008).
  • sucrose polyether polyol 10g DOPO-HB, 2.5g triethylenediamine, 0.8g silicon carbon bond type foam stabilizer, 0.8g 2,4,6-tris(dimethylaminomethyl)phenol and 0.5 g of water was mixed with high-speed stirring to form a compound A, and B material (135 g of PM-100 and 0.05 g of dibutyltin dilaurate) was quickly added, and the mixture was uniformly stirred at a high temperature of 2500 r/min at room temperature. When the mixture was observed to be whitish, it was poured into a self-made mold and freely foamed. After foaming, it was aged for 48 hours, and the mold was released to obtain a rigid polyurethane foam. Its oxygen index is 18.0 (GB/T 2406.1 ⁇ 2008).
  • sucrose polyether polyol 20g DOPO-HB, 3.0g triethylenediamine, 1.7g silicon carbon bond type foam stabilizer, 1.7g 2,4,6-tris(dimethylaminomethyl)phenol and 1.0 g of water was mixed with high-speed stirring to form a compound A, and B material (142 g of PM-100 and 0.08 g of dibutyltin dilaurate) was quickly added, and the mixture was uniformly stirred at room temperature at 2500 r/min. When the mixture was observed to be whitish, it was poured into a self-made mold and freely foamed. After foaming, it was aged for 48 hours, and the mold was released to obtain a rigid polyurethane foam. Its oxygen index is 19.5 (GB/T 2406.1 ⁇ 2008).
  • the preparation method of the intrinsically fire-retardant rigid polyurethane foam is the same as in the first embodiment.
  • a series of flame retardant polyurethanes with different phosphorus contents were prepared, as shown in the following table:
  • the DOPO-HB in the present invention is a hydroxyl-terminated alcohol like the polyether polyol, which functions as a polyether polyol, and at the same time, a molecular chain between the hydroxyl active sites introduces a flame retardant element to form an elemental molecule, which
  • the compounds not only have the flame retardant properties of inorganic substances, but also have the elasticity and plasticity of organic substances.

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Abstract

本发明公开了一种本质阻燃硬质聚氨酯泡沫塑料，其原料包括如下重量份的组分：聚醚多元醇和反应型含磷阻燃剂100～105重量份、胺类催化剂2.5～3.5重量份、叔胺类催化剂0.8～2.5重量份、匀泡剂0.8～2.5重量份、发泡剂0.5～1.5重量份、异氰酸酯135～150重量份和有机金属催化剂0.05～0.1重量份；其中所述反应型含磷阻燃剂为9,10-二氢-9-氧杂-10-磷杂菲基-4-羟基苯甲醇。本发明的泡沫塑料避免了类似橡胶的"喷霜"现象，将含有阻燃元素活性单体引入聚氨酯的主链、侧链进行改性，在不明显影响基体树脂的性能情况下，永久提高聚氨酯的阻燃性能。

Description

一种本质阻燃硬质聚氨酯泡沫塑料 技术领域
本发明涉及一种泡沫塑料，特别是硬质聚氨酯泡沫塑料的阻燃。
背景技术
聚氨酯(PU)，作为最重要的六大合成材料之一，广泛应用于建筑节能、家电、交通运输(汽车、地铁、高铁等)、新能源等产业。近年来，我国接连发生火灾事故，这使得聚氨酯硬质泡沫的阻燃研究提上日程。因此，在不明显影响性能的情况下如何进一步提高聚氨酯硬泡的阻燃等级成为我们亟需解决的问题。
中国专利CN101962474A公开了一种环保型高阻燃性硬质聚氨酯泡沫，即采用聚合物多元醇、戊烷、阻燃剂、改性空心微珠和多异氰酸酯在匀泡剂和/或催化剂存在的条件下混和反应获得，垂直燃烧达到V‐0级，可以较好地应用于建筑外墙、管道和冷藏设备保温方面。中国专利CN102875762A公开了一种高阻燃性硬质聚氨酯泡沫，添加了复配的阻燃剂，制得了氧指数在30以上的高阻燃硬质聚氨酯泡沫塑料。该材料具有较高的阻燃性、低发烟性以及高耐火隔热性能，提高了硬质聚氨酯泡沫使用中的安全性。综上，现有硬质聚氨酯泡沫阻燃技术大多集中在添加型方式上，这种方法成本低，见效快，具有很好的应用前景。
但是，采用添加型阻燃方式也会带来一些不可避免的问题：(1)为达到阻燃效果，添加量较大；(2)与聚氨酯基体树脂相容性差，长期贮存或使用时添加剂会迁移到材料表面，发生类似橡胶的“喷霜”现象。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种本质阻燃硬质聚氨酯泡沫塑料。
本发明的具体技术方案如下：
一种本质阻燃硬质聚氨酯泡沫塑料，其原料包括如下重量份的组分：
Figure PCTCN2014093079-appb-000001
其中所述反应型含磷阻燃剂为9,10‐二氢‐9‐氧杂‐10‐磷杂菲基‐4‐羟基苯甲醇(DOPO‐HB)，结构式为：
Figure PCTCN2014093079-appb-000002
其制备方法参考文献(Ying Ling Liu.Flame‐retardant epoxy resins from novel phosphorus‐containing novolac[J].Polymer(2001),42(8),3445‐3454.)
制备DOPO‐HB的反应式如下：
Figure PCTCN2014093079-appb-000003
在本发明的一个优选实施方案中，所述聚醚多元醇与所述反应型含磷阻燃剂的重量比为10～90:10～90。
在本发明的一个优选实施方案中，所述聚醚多元醇为硬泡类聚氨酯用聚醚多元醇。
在本发明的一个优选实施方案中，所述胺类催化剂为三亚乙基二胺。
在本发明的一个优选实施方案中，所述叔胺类催化剂为2，4，6‐三(二甲氨基甲基)苯酚。
在本发明的一个优选实施方案中，所述匀泡剂为硅碳键型匀泡剂。
在本发明的一个优选实施方案中，所述发泡剂为水。
在本发明的一个优选实施方案中，所述异氰酸酯的粘度为150～250mPa·s，NCO质量百分数含量为30.0％～32.0％。
在本发明的一个优选实施方案中，所述有机金属催化剂为二月桂酸二丁基锡。
上述本质阻燃硬质聚氨酯泡沫塑料的制备方法如下：
1)将反应型含磷阻燃剂、聚醚多元醇、胺类催化剂、匀泡剂、叔胺类催化剂、发泡剂混合，得到混合组分A；
2)将异氰酸酯与有机金属催化剂混合，得到混合组分B；
3)将混合组分B加入混合组份A中，倒入模具，进行发泡，熟化，脱模工序后，最终制得本发明的本质阻燃硬质聚氨酯泡沫塑料。
通过改变聚醚多元醇与DOPO‐HB的用量比，可制备出一系列磷含量不同的阻燃硬质聚氨酯泡沫塑料。
本发明的有益效果是：
1、本发明中的DOPO‐HB与聚醚多元醇一样以羟基封端的醇类，它能充当聚醚多元醇的功能，同时，羟基活性点之间的分子链引入阻燃元素形成了元素分子，这类化合物不仅具有无机物的阻燃性能，同时也具有有机物的弹性和塑性；
2、本发明的泡沫塑料将阻燃性能优异的DOPO基团以共价键形式引入聚氨酯网络中，克服了传统添加型阻燃剂与PU基体相容性差、久置后易迁移的缺点，同时，相对于添加型阻燃剂，其添加量大大降低，发挥了反应型阻燃剂的优势；
3、本发明的泡沫塑料避免了类似橡胶的“喷霜”现象，将含有阻燃元素活性单体引入聚氨酯的主链、侧链进行改性，在不明显影响基体树脂的性能情况下，永久提高聚氨酯的阻燃性能。
附图说明
图1为本发明所用的反应型含磷阻燃剂DOPO‐HB的1H核磁共振谱图；
图2为本发明所用的反应型含磷阻燃剂DOPO‐HB的31P核磁共振谱图。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
下述实施例中的DOPO‐HB的1H和31P核磁共振谱图分别如图1和图2所示。(DMSO/TMS,δ(ppm)，氢谱中数字为各化学环境中氢的积分面积)。1H NMR(ppm,DMSO‐d6),δ＝4.97～5.18(1H,Hb),6.11～6.27(1H,Ha),6.64～8.22(12H,Ar‐H),9.39～9.43(1H,Hc).31P NMR(ppm,DMSO‐d6),δ＝31.0.
下述实施例中的硬泡类聚氨酯用聚醚多元醇选用羟值441mgKOH/g的蔗糖聚醚多元醇。所用异氰酸酯为烟台万华聚氨酯股份有限公司生产的牌号为PM‐100的异氰酸酯，其粘度为150～250mPa·s，NCO质量百分数含量为30.0％～32.0％。
实施例1：
该实施例为不添加反应型含磷阻燃剂的对比实施例
称取105g蔗糖聚醚多元醇、3.5g三亚乙基二胺、2.5g硅碳键型匀泡剂、2.5g 2，4，6‐三(二甲氨基甲基)苯酚和1.5g水，用高速搅拌下混合均匀组成A料，快速加入B材料(150g PM‐100和0.1g二月桂酸二丁基锡)，室温2500r/min下高速搅拌混合均匀。观察到混合料发白时，即倒入自制模具中自由发泡，发泡完后熟化48h，脱模即得到硬质聚氨酯泡沫塑料。其氧指数为17.0(GB/T 2406.1‐2008)。
实施例2：
称取90g蔗糖聚醚多元醇、10g DOPO‐HB、2.5g三亚乙基二胺、0.8g硅碳键型匀泡剂、0.8g 2，4，6‐三(二甲氨基甲基)苯酚和0.5g水，用高速搅拌下混合均匀组成A料，快速加入B材料(135g PM‐100和0.05g二月桂酸二丁基锡)，室温2500r/min下高速搅拌混合均匀。观察到混合料发白时，即倒入自制模具中自由发泡，发泡完后熟化48h，脱模即得到硬质聚氨酯泡沫塑料。其氧指数为18.0(GB/T 2406.1‐2008)。
实施例3：
称取80g蔗糖聚醚多元醇、20g DOPO‐HB、3.0g三亚乙基二胺、1.7g硅碳键型匀泡剂、1.7g 2，4，6‐三(二甲氨基甲基)苯酚和1.0g水，用高速搅拌下混合均匀组成A料，快速加入B材料(142g PM‐100和0.08g二月桂酸二丁基锡)，室温2500r/min下高速搅拌混合均匀。观察到混合料发白时，即倒入自制模具中自由发泡，发泡完后熟化48h，脱模即得到硬质聚氨酯泡沫塑料。其氧指数为19.5(GB/T 2406.1‐2008)。
实施例4‐10：
本质阻燃硬质聚氨酯泡沫塑料的制备方法同实施例1。改变蔗糖聚醚多元醇和DOPO‐HB的配比，制备得到一系列磷含量不同的阻燃聚氨酯，配比如下表所示：
Figure PCTCN2014093079-appb-000004
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
工业实用性
本发明中的DOPO‐HB与聚醚多元醇一样以羟基封端的醇类，它能充当聚醚多元醇的功能，同时，羟基活性点之间的分子链引入阻燃元素形成了元素分子，这类化合物不仅具有无机物的阻燃性能，同时也具有有机物的弹性和塑性。

Claims (9)

  1. 一种本质阻燃硬质聚氨酯泡沫塑料，其特征在于：其原料包括如下重量份的组分：
    Figure PCTCN2014093079-appb-100001
    其中所述反应型含磷阻燃剂为9,10‐二氢‐9‐氧杂‐10‐磷杂菲基‐4‐羟基苯甲醇。
  2. 如权利要求1所述的一种本质阻燃硬质聚氨酯泡沫塑料，其特征在于：所述聚醚多元醇与所述反应型含磷阻燃剂的重量比为10～90:10～90。
  3. 如权利要求1所述的一种本质阻燃硬质聚氨酯泡沫塑料，其特征在于：所述聚醚多元醇为硬泡类聚氨酯用聚醚多元醇。
  4. 如权利要求1所述的一种本质阻燃硬质聚氨酯泡沫塑料，其特征在于：所述胺类催化剂为三亚乙基二胺。
  5. 如权利要求1所述的一种本质阻燃硬质聚氨酯泡沫塑料，其特征在于：所述叔胺类催化剂为2，4，6‐三(二甲氨基甲基)苯酚。
  6. 如权利要求1所述的一种本质阻燃硬质聚氨酯泡沫塑料，其特征在于：所述匀泡剂为硅碳键型匀泡剂。
  7. 如权利要求1所述的一种本质阻燃硬质聚氨酯泡沫塑料，其特征在于：所述发泡剂为水。
  8. 如权利要求1所述的一种本质阻燃硬质聚氨酯泡沫塑料，其特征在于：所述异氰酸酯的粘度为150～250mPa·s，NCO质量百分数含量为30.0％～32.0％。
  9. 如权利要求1所述的一种本质阻燃硬质聚氨酯泡沫塑料，其特征在于：所述有机金属催化剂为二月桂酸二丁基锡。
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