CN103910844B - 一种无卤低烟阻燃型硬质聚氨酯泡沫材料及其制备方法 - Google Patents
一种无卤低烟阻燃型硬质聚氨酯泡沫材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及硬质聚氨酯泡沫材料制备技术领域，具体为一种无卤低烟阻燃型硬质聚氨酯泡沫材料及其制备方法，该硬质聚氨酯泡沫材料具有如下组分：聚醚多元醇100份；聚磷酸铵50-70份；羟基锡酸锌2-10份；发泡剂20-25份；均泡剂2-5份；催化剂1.1-1.5份；水1.1-1.5份；异氰酸酯130-150份。采用本发明的将聚磷酸铵、羟基锡酸锌和聚醚多元醇预先在行星球磨机中进行研磨分散的技术方案，可有效提高了聚磷酸铵在聚醚中的分散稳定性，所得的组合白料在一周内不会出现分层现象，粉末阻燃剂可均匀的分散在聚醚中，不沉降、不凝聚，所得的硬质聚氨酯泡沫具有在高温下结构不坍塌、不融滴、产生烟量小的优点。
Description
技术领域
本发明涉及硬质聚氨酯泡沫材料制备技术领域，具体为一种无卤低烟阻燃型硬质聚氨酯泡沫材料及其制备方法。
背景技术
硬质聚氨酯泡沫塑料是一种性能优良的保温材料和结构材料，其最大优点是质轻、隔热保温性好、与其他材料粘结性强、具有较高的压缩强度和较好的尺寸稳定性，可广泛应用于需要隔热保温的领域。然而，采用现有技术制备得到的硬质聚氨酯泡沫塑料自身存在易燃性、燃烧时容易熔融滴落并释放出HCN、CO等有毒气体及氧指数较低的问题，因而限制了其在制冷、采暖保温等建筑材料领域的使用。国家标准GB8624-2012《建筑材料及制品燃烧性能分级》已规定用于外墙保温等领域的硬质聚氨酯泡沫必须达到B2级要求，对氧指数(LOI)的要求是高于或等于26vol％。
聚氨酯发泡时的原料一般为双组份，包括俗称的黑料和白料，其中黑料是指异氰酸酯化合物。由于异氰酸酯基团对水分等极为敏感，所以黑料中一般不加入其他组份。白料又称组合聚醚，通常是以聚酯或聚醚多元醇为主体，加入发泡剂、均泡剂、催化剂、阻燃剂等复配而成，由于组分较多，尤其当加入较多的阻燃剂时，白料的稳定性是配制过程中的一个重要技术问题。
目前，硬质聚氨酯泡沫材料的阻燃主要通过两种途径来实现，一种是采用分子结构中含有阻燃成分的反应型阻燃剂，其反应性一般是指含有可与异氰酸酯反应的基团，如含有卤素或磷元素的多元醇。这种反应型阻燃剂往往需要较特殊的方法合成，种类少，成本高，在一般的聚氨酯泡沫中使用不具有性价比优势。另外一种是采用含卤、磷、氮、铝、硼等阻燃元素的有机或无机添加型阻燃剂，这是目前市场上最常用的阻燃方法。中国专利CN10291134A公开了B1级高阻燃低发烟硬质聚氨酯泡沫，该聚氨酯泡沫是采用磷酸(2-氯乙基)三酯(TCEP)、磷酸(2-氯丙基)三酯(TCPP)、磷酸(二氯丙基)三酯(TDCP)中的一种或几种对体系进行阻燃。据文献(建筑用高阻燃型硬质聚氨酯泡沫塑料的研制.聚氨酯工业2003，18(2)：31-33)报道，采用三(2-氯乙基)磷酸酯(TCEP)和甲基膦酸二甲酯(DMMP)作为阻燃剂制备建筑用硬质PUF，氧指数可达到32vol％，达到了国标GB8624-1997建筑材料燃烧性能分级方法中的B1级，满足建筑用材料的阻燃要求。中国专利CN102993931A公开了一种聚氨酯漆用复合阻燃剂，具体为间苯二酚双(二苯基磷酸酯)、磷酸三(β-氯乙基)酯、
双酚A双(二苯基磷酸酯)以15/5/30加入到聚氨酯漆中，可使其具备阻燃防火功能。虽然含有卤素的阻燃剂阻燃效率高，但在燃烧后容易释放出有毒的卤化物烟雾，对处于火场中的人员安全造成严重威胁，这使得卤素类阻燃剂的应用越来越受限制，其使用量正在逐渐减少，而采用低烟无卤的阻燃剂是发展趋势。文献(Flameretardancyinthermoplasticpolyurethaneelastomers(TPU)withmicaandaluminumtrihydrate(ATH).PolymerDegradationandStability2000，69(3)：257-260)研究了ATH对聚氨酯泡沫塑料阻燃性能的影响，研究结果表明，氢氧化铝可以明显改善PUF的阻燃性能，当ATH含量为70～80％时，经过UL-94测试，PUF可以达到V-0级，但是高密度氢氧化铝的加入会极大影响白料的稳定性、降低PUF拉伸强度和抗磨损性。清洁、无卤型是阻燃剂发展的特点。文献(Rolesoforganically-modifiedmontmorilloniteandphosphorousflameretardantduringthecombustionofrigidpolyurethanefoam.PolymerDegradationandStability2014，1-8)报道，采用聚磷酸铵、磷酸三苯酯、有机蒙脱土进行复配对硬质聚氨酯进行阻燃，当含有5％的有机蒙脱土、8％聚磷酸铵、4％磷酸三苯酯时，所得聚氨酯具有最长的持续燃烧时间，最慢的热释放速率和最低的烟总释放量，但其氧指数低于26。
聚磷酸铵是一种性能优良的阻燃剂，其含磷量和含氮量都较高，它们之间又存在P-N协同效应，它的热稳定性较好(分解温度高于250℃)，能与其它阻燃剂进行复配提高阻燃性，发烟量低，毒性小，可使聚氨酯材料具有优良的阻燃效果。但聚磷酸铵与多元醇相容性差，容易沉降，影响聚醚组合料的稳定性，所以限制了APP在聚氨酯泡沫行业的应用。
另外，聚氨酯泡沫塑料在燃烧时都会产生大量的烟雾，其中包括剧毒的氰化氢气体，因此其阻燃改性过程中，抑烟也是一个重要的要求。一些过渡金属化合物可以作为抑烟剂使用，羟基锡酸锌是近年发展起来的一种新型阻燃抑烟剂，具有无毒的特点，符合当今绿色阻燃剂的要求，所以研究界对它们的研究较多，其有望成为三氧化二锑的替代品。羟基锡酸锌分解后产生的SnO，SnO2可以与聚合物燃烧过程中产生的高活性自由基(如H·，OH·，RO·)反应而使之失活，与Sb2O3相比，羟基锡酸锌可减少聚氨酯材料燃烧时的烟、CO2及CO的生成量，且低毒、安全、用量低。
据文献(ZinccompoundsasflameretardantsandsmokesuppressantsforrigidPVC.Plast.Rub.AndComp，2003，32：413-419)报道，将羟基锡酸锌和硼酸锌分别加入到硬质PVC中研究了它们的阻燃和抑烟性能，结果表明，添加3份羟基锡酸锌后，所得硬质PVC就有极好的阻燃和抑烟性能，并显著增加了引燃时间。中国专利CN102515185A公开了羟基锡酸锌-坡缕石粘土复合物及其制备和作为阻燃剂的应用，提供了一种羟基锡酸锌-坡缕石粘土复合物，该复合物具有高阻燃性能和高抑烟性能，用于制备阻燃聚氯乙烯材料时，可得到阻燃性能、抑烟性能及力学性能良好的高分子材料，具体参数为：氧指数不小于34、水平燃烧达到HB-a级、垂直燃烧达到UL94V-0级、在无焰条件下烟密度不大于286。
综上所述，提供一种阻燃性能较好、配方较为稳定、泡沫材料氧指数较高、燃烧时的烟释放量较低的无卤低烟阻燃型硬质聚氨酯泡沫材料及其制备方法是当前要研究的问题。
发明内容
本发明要解决的技术问题是：针对现有技术中存在的聚磷酸铵白料的稳定性问题，同时为进一步提高聚氨酯泡沫的阻燃性，降低其烟释放量，提供一种无卤低烟阻燃型硬质聚氨酯泡沫材料及其制备方法。
本发明解决其技术问题所采用的技术方案是：一种无卤低烟阻燃型硬质聚氨酯泡沫材料，按重量份计，该材料具有如下组分：
聚醚多元醇100份；聚磷酸铵50-70份；羟基锡酸锌2-10份；发泡剂20-25份；均泡剂2-5份；催化剂1.1-1.5份；水1.1-1.5份；异氰酸酯130-150份；
其中，发泡剂为一氟二氯乙烷或戊烷中的一种或两种的组合，均泡剂为有机硅类均泡剂，催化剂为叔胺类催化剂。
进一步，所述聚醚多元醇羟值在400-550mgKOH/g之间，聚磷酸铵聚合度在1000-1500之间，异氰酸酯的官能度在2.5-3.5之间。
进一步，均泡剂优选硅油8805，催化剂为N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、三乙胺、N,N-二甲基苄胺中的一种、两种或多种的组合。
一种无卤低烟阻燃型硬质聚氨酯泡沫材料的制备方法，该制备方法具有如下步骤：
(1)按重量份计，称取聚醚多元醇100份、聚磷酸铵50-70份、羟基锡酸锌2-10份、发泡剂20-25份、均泡剂2-5份、催化剂1.1-1.5份、水1.1-1.5份和异氰酸酯130-150份；
(2)将步骤(1)称取的聚磷酸铵、羟基锡酸锌和聚醚多元醇混合后放入转速为430r/min的球磨机中，球磨1h，得阻燃聚醚；
(3)向步骤(2)所得的阻燃聚醚中依次添加发泡剂、均泡剂、催化剂和水，控制物料温度在20-40℃，在环境温度为20-40℃、转速为2000r/min的条件下，搅拌20s；然后快速倒入异氰酸酯，在转速为2000r/min的条件下，搅拌7-10s后倒入模具中，迅速将模具盖好，模具压力为5-20N/m2，30-40min后出模。
有益效果：采用本发明的将聚磷酸铵、羟基锡酸锌和聚醚多元醇预先在行星球磨机中进行研磨分散的技术方案，可有效提高聚磷酸铵在聚醚中的分散稳定性，所得的组合白料较为稳定，在一周内不会出现分层现象，粉末阻燃剂可均匀的分散在聚醚中，不沉降、不凝聚，所得的硬质聚氨酯泡沫配方较为稳定、阻燃性能较好、泡沫材料氧指数较高、具有在高温下结构不坍塌、不融滴、产生烟量较低的优点。
附图说明
下面结合附图和实施例对本发明进一步说明；
图1本发明制备步骤的工艺流程图；
图2是对比例1、对比例4和实施例4的热释放速率(HRR)图；
图3是对比例1、对比例4和实施例4的烟释放速率(SRR)图。
具体实施方式
下面结合具体实施例对本发明做进一步说明，但本发明不局限于下述实施例。以下对比例和实施例所采用的聚磷酸铵是杭州捷尔斯生产的JLS-APP，聚合度n>1000；异氰酸酯是烟台万华的PM200；聚醚多元醇是洛阳保温材料厂的430，羟值为430mgKOH/g，均泡剂为硅油8805，发泡剂141b，催化剂pc-8。
一种无卤低烟阻燃型硬质聚氨酯泡沫材料的制备方法，其制备步骤的工艺流程如图1所示，制备方法的具体步骤如下：
(1)按重量份计，称取聚醚多元醇、聚磷酸铵、羟基锡酸锌、发泡剂、均泡剂、催化剂、水和异氰酸酯，对比例和实施例的配方如表1所示。
表1无卤低烟阻燃型硬质聚氨酯泡沫材料配方
| 原料编号 | 对例1 | 对例2 | 对例3 | 对例4 | 实例1 | 实例2 | 实例3 | 实例4 |
| 430 | 100g | 100g | 100g | 100g | 100g | 100g | 100g | 100g |
| PM200 | 130g | 130g | 150g | 130g | 150g | 130g | 130g | 130g |
| APP | 0g | 50g | 60g | 70g | 60g | 65g | 70g | 70g |
| ZnSn(OH)6 | 0g | 0g | 0g | 0g | 2g | 5g | 5g | 10g |
| 发泡剂 | 20g | 25g | 20g | 20g | 25g | 20g | 20g | 20g |
| 催化剂 | 1.1g | 1.5g | 1.1g | 1.5g | 1.5g | 1.1g | 1.1g | 1.1g |
| 均泡剂 | 2g | 2g | 2g | 5g | 5g | 2g | 2g | 2g |
| 水 | 1.1g | 1.5g | 1.1g | 1.5g | 1.5g | 1.1g | 1.1g | 1.1g |
(2)将步骤(1)称取的聚磷酸铵、羟基锡酸锌和聚醚多元醇混合后放入转速为430r/min的球磨机中，球磨1h，得阻燃聚醚；
(3)向步骤(2)所得的阻燃聚醚中依次添加发泡剂、均泡剂、催化剂和水，控制物料温度在20-40℃，在环境温度为25℃、转速为2000r/min的条件下，搅拌20s；然后快速倒入异氰酸酯，在转速为2000r/min的条件下，搅拌7-10s后倒入模具中，迅速将模具盖好，30min后出模，得到无卤低烟阻燃型硬质聚氨酯泡沫材料。
将上述四例对比例和四例实施例所得的泡沫材料，进行相关性能测试，测试结果如下表2所示。
表2无卤低烟阻燃型硬质聚氨酯泡沫材料性能测试结果
| 测试项目 | 对例1 | 对例2 | 对例3 | 对例4 |
| 压缩强度(MPa) | 0.18 | 0.18 | 0.19 | 0.19 |
| LOI(％) | 19 | 24 | 25 | 26 |
| peak1-HRR(kw/m2)a | 179.60 | 无测定 | 无测定 | 108.31 |
| peak2-HRR(kw/m2)a | / | 无测定 | 无测定 | 150.48 |
| t peak1-HRR(s)a | 50 | 无测定 | 无测定 | 35 |
| t peak2-HRR(s)a | / | 无测定 | 无测定 | 150 |
| peak-SPR(m2/s)a | 0.047 | 无测定 | 无测定 | 0.035 |
表2(续)
| 测试项目 | 实例1 | 实例2 | 实例3 | 实例4 |
| 压缩强度(MPa) | 0.19 | 0.20 | 0.18 | 0.18 |
| LOI(％) | 25 | 26 | 26.5 | 27 |
| peak1-HRR(kw/m2)a | 无测定 | 无测定 | 无测定 | 90.23 |
| peak2-HRR(kw/m2)a | 无测定 | 无测定 | 无测定 | 100.18 |
| t peak1-HRR(s)a | 无测定 | 无测定 | 无测定 | 25 |
| t peak2-HRR(s)a | 无测定 | 无测定 | 无测定 | 185 |
| peak-SPR(m2/s)a | 无测定 | 无测定 | 无测定 | 0.033 |
其中，peak1-HRR和peak2-HRR分别代表图2中各曲线热释放速率的第一个和第二个峰值；tpeak1-HRR和tpeak2-HRR分别代表图2中各曲线的热释放速率的第一个峰和第二个峰出现的时间；peak-SPR代表图3中各曲线的烟释放速率峰值。
由表2及图2、图3中各曲线的数据可知，对比例1、对比例4和实施例4各自的HRR和SPR曲线非常相似，这表明热和烟是同步释放的。实施例4的HRR曲线出现两个峰，第一峰的出现归功于保护碳层的形成，当完整坚固的碳层形成时，出现第二峰，而且，第二个峰与第一个峰出现的时间间距也比较长(25s/185s)。相比于对比例4,实施例4的peak2-HRR的值(100.18kw/m2)有非常明显的减少，peak2-HRR出现的时间(185s)变得更长，相比于对比例4的(150.48kw/m2，150s)。上述结果表明，实施例4的组分配方具有非常好的阻燃效果，且加了羟基锡酸锌后有明显的抑烟效果。
Claims (4)
1.一种无卤低烟阻燃型硬质聚氨酯泡沫材料，其特征是：按重量份计，该材料具有如下组分：
聚醚多元醇100份；聚磷酸铵50-70份；羟基锡酸锌2-10份；发泡剂20-25份；均泡剂2-5份；催化剂1.1-1.5份；水1.1-1.5份；异氰酸酯130-150份；
其中，发泡剂为一氟二氯乙烷或戊烷中的一种或两种的组合，均泡剂为有机硅类均泡剂，催化剂为叔胺类催化剂；所述聚醚多元醇羟值在400-550mgKOH/g之间，聚磷酸铵聚合度在1000-1500之间；
该材料是制备方法具有如下步骤：
(1)按重量份计，称取聚醚多元醇100份、聚磷酸铵50-70份、羟基锡酸锌2-10份、发泡剂20-25份、均泡剂2-5份、催化剂1.1-1.5份、水1.1-1.5份和异氰酸酯130-150份；
(2)将步骤(1)称取的聚磷酸铵、羟基锡酸锌和聚醚多元醇混合后放入转速为430r/min的球磨机中，球磨1h，得阻燃聚醚；
(3)向步骤(2)所得的阻燃聚醚中依次添加发泡剂、均泡剂、催化剂和水，控制物料温度在20-40℃，在环境温度为20-40℃、转速为2000r/min的条件下，搅拌20s；然后快速倒入异氰酸酯，在转速为2000r/min的条件下，搅拌7-10s后倒入模具中，迅速将模具盖好，模具压力为5-20N/m2，30-40min后出模。
2.根据权利要求1所述的无卤低烟阻燃型硬质聚氨酯泡沫材料，其特征是：所述异氰酸酯的官能度在2.5-3.5之间。
3.根据权利要求1所述的无卤低烟阻燃型硬质聚氨酯泡沫材料，其特征是：所述均泡剂为硅油8805。
4.根据权利要求1所述的无卤低烟阻燃型硬质聚氨酯泡沫材料，其特征是：所述催化剂为N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、三乙胺、N,N-二甲基苄胺中的一种、两种或多种的组合。
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| CN114174366A (zh) * | 2019-07-12 | 2022-03-11 | 陶氏环球技术有限责任公司 | 具有改进的燃烧性能的聚氨酯泡沫 |
| CN111961330A (zh) * | 2020-08-30 | 2020-11-20 | 宁波耀众模塑科技有限公司 | 一种基于磷类阻燃剂材料的聚氨酯发泡产品生产配方 |
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