CN1135251C - 发泡性聚苯乙烯粒子的制备工艺 - Google Patents
发泡性聚苯乙烯粒子的制备工艺 Download PDFInfo
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Abstract
本发明涉及了一种颗粒状发泡性苯乙烯聚合物的制备工艺，聚合物含有5-50wt%膨胀石墨和任选的2-20wt%磷化合物作为阻燃剂，该工艺是通过在阻燃剂存在下苯乙烯进行悬浮聚合反应实施的。
Description
技术领域
本发明涉及带有无卤素阻燃剂的颗粒状发泡性苯乙烯聚合物。
背景技术和发明内容
聚苯乙烯粒子发泡材料广泛地用于分隔建筑物和建筑部件。为此，它必须是经过阻燃整理的。使聚苯乙烯发泡材料阻燃常用的阻燃剂含有卤素。由于环保原因，发泡材料中卤素的使用应该减少。
因此，本发明的目的是提供一种发泡性聚苯乙烯粒子，它可加工成防火等级为B1和B2的发泡材料并且制备时可省去含卤素的阻燃剂。
这一目的是通过颗粒状发泡性苯乙烯聚合物的制备工艺达到的，是通过苯乙烯和任选的共聚单体一起在含水悬浮体中进行聚合反应，同时在聚合反应之前、期间或之后加入发泡剂，其中聚合反应是在5-50wt％膨胀石墨存在下进行的，基于单体计，其中膨胀石墨的密度为1.5-2.1g/cm3，按最大直径测量的平均粒度为20-2000μm。
本发明的另一目的是颗粒状发泡性苯乙烯聚合物，它含有均匀分布的5-50wt％的按最大直径测量的平均粒度为20～100μm，优选30-80μm的膨胀石墨，基于苯乙烯聚合物计，和膨胀石墨的密度为1.5-2.1g/cm3。
在文献中已描述过用于密实聚苯乙烯的膨胀石墨与红磷或含磷化合物结合作为阻燃剂。但在以前的试验中发现，可以用于密实聚苯乙烯的无卤素阻燃剂不能用于制备泡沫体，因为发泡工艺会受到强烈的干扰或者是发泡材料的热形状稳定性会大大下降。但意外的是，在本发明中情况不是如此。
US-A-3,574,644描述了加入膨胀石墨作为可燃材料，特别是发泡材料的阻燃剂，其中膨胀石墨的含量应为20-40wt％。该膨胀石墨可以在发泡之前引入到发泡性材料中，或者是将之在发泡之后用膨胀石墨涂覆。但未描述在膨胀石墨存在下由苯乙烯的聚合反应进行的发泡性聚苯乙烯粒子的制备。
JP-A 03 167 236描述了一种聚苯乙烯泡沫体，它含有膨胀石墨作为阻燃剂，其表面整个地涂有一种成膜树脂。这种涂层被表明是必需的，以避免膨胀石墨中一直存在的酸对加工机器的腐蚀；但它需要一个额外的复杂加工步骤。除膨胀石墨外，聚苯乙烯泡沫体还含有常见的阻燃剂，例如卤化的有机磷酸酯。聚苯乙烯泡沫体优选通过聚苯乙烯泡沫粒子与增粘剂和经涂覆的膨胀石墨相混合而制备。膨胀石墨的粒度优选应为30-120目，相当于直径大约120-540μm。当粒度小于150目(104μm)时，膨胀石墨的阻燃效果大大降低。
具体实施方式
由于有层状晶格结构，石墨能够形成特殊形式的填隙化合物。在这些所谓的晶格中间体中，外来原子或分子以化学计量比部分地进入到碳碳原子间隔中。例如含有硫酸作为外来分子的这些石墨化合物，也可以工业规模生产，被称作为膨胀石墨。这种膨胀石墨的密度为1.5-2.1g/cm3，平均粒度一般为20-2000μm，在本发明情况下优选为20-100μm和特别是30-80μm。
使用的磷化合物可以是无机或有机磷酸酯、亚磷酸酯或膦酸酯以及红磷。优选的磷化合物例如是磷酸二苯酯、磷酸三苯酯、磷酸二苯甲苯酯、多磷酸铵、磷酸间苯二酚二苯酯、蜜胺磷酸盐、苯基膦酸二甲酯或甲基膦酸二甲酯。
在本发明悬浮聚合反应中，优选仅使用苯乙烯作为单体。但最高到其重量的20％可以被其它烯属不饱和单体，如烷基苯乙烯、二乙烯基苯、丙烯腈、1，1-二苯醚或α-甲基苯乙烯所代替。
在悬浮聚合反应期间，可加入常规助剂，例如过氧化物引发剂、悬浮体稳定剂、发泡剂、链转移剂、发泡助剂、成核剂和软化剂。聚合反应中膨胀石墨的加入量为5-50wt％，优选8-30wt％；磷化合物的加入量为2-20wt％，优选3-10wt％；发泡剂的加入量为3-10wt％，均基于单体计。它们可在悬浮体聚合反应之前、期间或之后加入。合适的发泡剂是4-6个碳原子的脂族烃。有利地使用无机Pickering分散剂，例如焦磷酸镁或磷酸钙作为悬浮体稳定剂。已经表明，使用较小粒度，即平均直径为20-100μm、优选30-80μm的膨胀石墨时，与较粗的膨胀石墨粒子相比，悬浮体的稳定性有所改进，并且生成的粒子中内部水含量较低。
悬浮聚合反应中生成了平均直径0.2-2mm的珠状、基本圆形的粒子。它可以用常见的涂料组合物例如金属硬脂酸盐、甘油酯和细分散的硅酸盐涂覆。
除了通过本发明前面所述的悬浮聚合反应外，本发明的发泡性聚苯乙烯粒子也可通过苯乙烯聚合物熔体和发泡剂与平均粒度20-100μm的膨胀石墨，以及任选的磷化合物相混合、挤出、冷却和造粒而制备。也可以随后对含有膨胀石墨的苯乙烯聚合物颗粒进行浸渍。
发泡性聚苯乙烯粒子可被加工得到密度为5-100g/cm3和优选10-50g/cm3的聚苯乙烯泡沫体。为此，使发泡性粒子预发泡。这通常通过用水蒸汽在所谓的预发泡机中加热粒子实施。这样得到的预发泡粒子接着熔接在一起，形成成型制品。为此，将预发泡过的粒子填充到未气密性密封的模具中并施以蒸汽作用。冷却后，可取出成型制品。
实施例1
在18.0kg苯乙烯中溶解61.0g过氧化二枯基和20.2g过氧化二苯甲酰，以及加入900g苯基膦酸二甲酯(5wt％，基于苯乙烯计)。有机相在50L的搅拌容器中引入20.0L去离子水中。水相含有35.0g焦磷酸钠和70.0g硫酸镁(泻盐)。悬浮液快速加热到90℃和接着在4小时期间内加热到130℃。到达90℃1小时后计量加入1.8g乳化剂K30(Bayer股份公司)。再1小时后向反应混合物中加入悬浮在2.0kg苯乙烯中的2.7kg膨胀石墨(UCAR，Grafguard 160-80，平均粒度100μm)。再30分钟后计量加入1.60kg戊烷。最后在终温度130℃时完全聚合。滗析出所得的含发泡剂的聚苯乙烯珠粒，洗涤和干燥出内部水。按常用方法发泡成泡沫粒子，接着将其烧结成泡沫材料块或模制件
得到的泡沫材料块或模制件可满足防火等级B1和B2的要求。
实施例2
在14.4kg苯乙烯中溶解3.6kg聚苯乙烯(VPT，BASF股份公司)、61.0g过氧化二枯基和20.2g过氧化二苯甲酰，以及加入900g苯基膦酸二甲酯(5wt％，基于苯乙烯和聚苯乙烯计)。接着搅拌下悬浮2.7kg平均粒度为45μm的膨胀石墨。有机相在50L的搅拌容器中引入20.0L去离子水中。水相含有35.0g焦磷酸钠和70.0g硫酸镁(泻盐)。悬浮液快速加热到90℃和接着在4小时期间内加热到130℃。在达到90℃60分钟后加入1.8g乳化剂K30(Bayer股份公司)。再90分钟后计量加入1.60kg戊烷。最后在终温度130℃时完全聚合。滗析出所得的含发泡剂的聚苯乙烯珠粒，洗涤和干燥出内部水。按常用方法发泡成泡沫粒子，接着将其烧结成泡沫材料块或模制件。
如此得到的泡沫材料块或模制件可满足防火等级B1和B2的要求。
实施例3
聚苯乙烯以及15wt％膨胀石墨(平均粒度45μm)和5wt％红磷的混合物连续输送给螺杆内直径为53mm的挤出机中并熔融。经挤出机上的加入孔，向挤出机中连续压入6wt％的戊烷作为发泡剂并混入熔体中。熔体经过连到挤出机喷嘴板的压力下操作的水下造粒机造粒，得到珠状粒子。
经过水蒸汽的两次发泡，得到堆积密度15g/l的泡沫珠。这种泡沫粒子和由其制的发泡模制件满足了DIN4102的防火等级B1和B2的要求。
Claims (8)
1.制备颗粒状发泡性苯乙烯聚合物的工艺，是通过将苯乙烯和任选的共聚单体一起在水性悬浮体中进行聚合反应，在聚合反应之前、期间或之后加入发泡剂，其中聚合反应在5-50wt％膨胀石墨存在下进行，基于单体计，其中，膨胀石墨的密度为1.5-2.1g/cm3，按最大直径测量的平均粒度为20-2000μm。
2.按权利要求1的工艺，其特征在于，聚合反应时另外加入2-20wt％的红磷或磷化合物，基于单体计。
3.按权利要求2的工艺，其特征在于，磷化合物是有机或无机磷酸酯、亚磷酸酯或膦酸酯。
4.按权利要求2的工艺，其特征在于，磷化合物是磷酸三苯酯、磷酸二苯基甲苯酯、多磷酸铵、蜜胺磷酸盐、苯基膦酸二甲酯或磷酸二苯酯。
5.按权利要求1的工艺，其特征在于，膨胀石墨按最大直径测量的平均粒度为20-100μm。
6.颗粒状发泡性苯乙烯聚合物，含有5-50wt％均匀分布的膨胀石墨作为阻燃剂，基于苯乙烯聚合物计，其中膨胀石墨的密度为1.5-2.1g/cm3，其特征在于，膨胀石墨按最大直径测量的平均粒度为20-100μm。
7.按权利要求6的颗粒状发泡性苯乙烯聚合物，其特征在于，它还含有2-20wt％的磷化合物，基于苯乙烯聚合物计。
8.按权利要求6的发泡性聚苯乙烯粒子的用途，用于制备聚苯乙烯粒子发泡材料，它满足了防火等级B1和B2的要求。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19856758.8 | 1998-12-09 | ||
| DE19856758 | 1998-12-09 |
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| CNB998142522A Expired - Fee Related CN1135251C (zh) | 1998-12-09 | 1999-12-07 | 发泡性聚苯乙烯粒子的制备工艺 |
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| Country | Link |
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| US (1) | US6444714B1 (zh) |
| EP (1) | EP1137700B1 (zh) |
| JP (1) | JP2002531647A (zh) |
| KR (1) | KR100601233B1 (zh) |
| CN (1) | CN1135251C (zh) |
| AT (1) | ATE251196T1 (zh) |
| AU (1) | AU2537700A (zh) |
| CZ (1) | CZ296402B6 (zh) |
| DE (1) | DE59907232D1 (zh) |
| ES (1) | ES2211224T3 (zh) |
| NO (1) | NO326183B1 (zh) |
| PL (1) | PL196871B1 (zh) |
| RU (1) | RU2253658C2 (zh) |
| WO (1) | WO2000034342A2 (zh) |
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| US3574644A (en) * | 1965-03-22 | 1971-04-13 | Dow Chemical Co | Method of rendering normally flamable materials flame resistant |
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| US5760115A (en) | 1995-03-03 | 1998-06-02 | Tosoh Corporation | Fire-retardant polymer composition |
| GB9506836D0 (en) * | 1995-04-03 | 1995-05-24 | Metzeler Kay Ltd | Flame retardant flexible foam |
| DE19843327A1 (de) | 1998-09-22 | 2000-03-23 | Basf Ag | Teilchenförmige, expandierbare Styrolpolymerisate |
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1999
- 1999-12-07 AT AT99968341T patent/ATE251196T1/de active
- 1999-12-07 RU RU2001119050/04A patent/RU2253658C2/ru not_active IP Right Cessation
- 1999-12-07 CN CNB998142522A patent/CN1135251C/zh not_active Expired - Fee Related
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- 1999-12-07 AU AU25377/00A patent/AU2537700A/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| CZ20012048A3 (cs) | 2002-01-16 |
| NO20012839L (no) | 2001-06-08 |
| NO20012839D0 (no) | 2001-06-08 |
| KR20010080720A (ko) | 2001-08-22 |
| WO2000034342A3 (de) | 2000-10-19 |
| RU2253658C2 (ru) | 2005-06-10 |
| EP1137700B1 (de) | 2003-10-01 |
| AU2537700A (en) | 2000-06-26 |
| NO326183B1 (no) | 2008-10-13 |
| DE59907232D1 (de) | 2003-11-06 |
| PL196871B1 (pl) | 2008-02-29 |
| ATE251196T1 (de) | 2003-10-15 |
| PL349415A1 (en) | 2002-07-29 |
| ES2211224T3 (es) | 2004-07-01 |
| WO2000034342A2 (de) | 2000-06-15 |
| CN1329634A (zh) | 2002-01-02 |
| US6444714B1 (en) | 2002-09-03 |
| JP2002531647A (ja) | 2002-09-24 |
| CZ296402B6 (cs) | 2006-03-15 |
| KR100601233B1 (ko) | 2006-07-19 |
| EP1137700A2 (de) | 2001-10-04 |
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