CN1729258A - 用于发泡型防火涂料的聚合物粘结剂 - Google Patents
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Abstract
一种在发泡型防火涂料中用于或用作聚合物粘结剂的共聚物，包括牛顿共聚物和网状共聚物的共混物，该牛顿和网状共聚物由取代苯乙烯和取代丙烯酸酯组成，至少包括对甲基苯乙烯(PMS)和丙烯酸2－乙基己酯(2EHA)。
Description
本发明涉及用于或用作阻燃剂涂料、更特别地提供优异防火性能的发泡型防火(intumescent)涂料用的聚合物粘结剂的共聚物。
发泡型防火涂料组合物是本领域公知的。发泡型防火涂料的突出特征在于可以采用具有相对低膜厚度的涂料形式，将它们施加在基材，如在金属、木材、塑料、石墨和其它材料上施加。在曝露于火、热量或火焰时，发泡型防火涂料在厚度方面进行相当地膨胀以产生炭(char)和炭泡沫的隔离层。
最通常使用的发泡型防火涂料包含分散在粘结剂基体中的四种基础组分，有时称为″反应性颜料″。反应性颜料包括
(1)无机酸或在100-250℃的温度下产生酸的材料，例如产生磷酸的多磷酸铵；
(2)碳源如富含碳的多羟基材料，也称为碳水合物，例如季戊四醇或二季戊四醇；
(3)有机胺或酰胺，例如三聚氰胺；和非必要地
(4)在分解时释放盐酸气体的卤代材料。
提出基础发泡机理以涉及碳质炭的形成，其由产生的酸与多羟基材料的脱水反应形成。胺可以参与炭形成，但主要描述为隔绝炭泡沫形成的发泡剂。由于隔绝炭停止着火和保留在基材上，它在严重着火条件下比不可燃类型涂料提供更好的着火和热保护。
许多专利和公开文献公开了包含一种或多种聚合物材料的发泡型组合物，该聚合物材料与含有磷酸酯的材料和碳化材料或产生碳的材料结合。
在专利EP 0 902 062中，发泡型防火涂料组合物可包括作为成膜粘结剂的乙烯基甲苯/丙烯酸酯共聚物或苯乙烯/丙烯酸酯聚合物。
在专利US 3 654 190中，发泡型防火涂料包含结合到氯化天然橡胶上用作炭形成剂的固体乙烯基甲苯/丁二烯共聚物。
在专利EP 0 342 001中，用于发泡型防火涂料的聚合物粘结剂包括由在数量上占优势的第一单体和少量的第二单体形成的共聚物，该第二单体是热不稳定共聚单体，它优选是单体醛如丙烯醛。
在国际专利WO 01/05886中，当允许组合物干燥时，可使用乳液形式的聚合物粘结剂以形成膜；聚合物粘结剂可以是苯乙烯/丙烯酸酯共聚物。
涂料工业寻找不仅仅满足阻燃性要求、而且也具有所需涂料性能的阻燃剂涂料。用于发泡型防火涂料形成的反应性颜料不足以和它们自身不能提供所需的涂料性能。例如，发泡型防火涂料必须提供常规涂料希望的所有性能特征和另外的阻燃性优点。在一种体系中引入阻燃性和良好的涂料性能两者不是很容易的。结合如用于配制发泡型防火涂料的添加剂通常可导致具有涂料性能和阻燃性能两者都差的配制剂。
发现粘结剂的化学和物理性能对发泡型防火涂料的机能起关键作用。一方面，粘结剂不能太快速软化或熔融，以致不能形成稳定的炭。另一方面，粘结剂的粘度与扩散和炭的形成相关。
因此需要提供用于发泡型防火涂料的聚合物粘结剂，该粘结剂在着火的早期阶段降低火焰扩展速度，在着火后期阶段有益于促进炭形成和发泡。
其表明结合用于发泡型防火涂料的粘结剂的线性聚合物和交联聚合物能优化炭的形成，增加涂料的隔绝性能。
另外本发明人发现共聚物包含苯乙烯越多，与磷的相互作用越为负面的。相反，共聚物包含对甲基苯乙烯(PMS)越多，与磷的相互作用越是正面的，因此提供良好的发泡。
他们进一步发现根据本发明的发泡型组合物的性能与共聚物与磷光体(phosphor)反应的能力、对甲基苯乙烯(PMS)和丙烯酸2-乙基己酯(2EHA)的存在相关。
因此本发明提供一种在发泡型防火涂料中用于或用作聚合物粘结剂的共聚物，该共聚物包括牛顿(newtonian)共聚物和网状共聚物的共混物，该牛顿和网状共聚物由取代苯乙烯和取代丙烯酸酯组成，至少包括对甲基苯乙烯(PMS)和丙烯酸2-乙基己酯(2EHA)。
本发明也在另一方面提供包含以上聚合物粘结剂的发泡型阻燃剂涂料和形成这样涂料的方法。
网状共聚物选自触变共聚物或假塑性共聚物。
在本发明的意义中，牛顿共聚物表示当溶于溶剂时得到牛顿粘度表现的共聚物，即粘度不是剪切依赖性的；触变共聚物表示得到剪切稀化溶剂溶液，在静置时返回到它们的初始状态及时间依赖性的共聚物，假塑性共聚物是当溶于溶剂时得到剪切稀化溶液的共聚物。
发现在PMS和2EHA之间的比例应当为100/0-50/50，优选90/10，优选80/20和更优选75/25。
用作根据本发明的聚合物粘结剂的共聚物可进一步包含其它取代苯乙烯如对叔丁基苯乙烯(PTBS)和/或其它取代丙烯酸酯如甲基丙烯酸异丁酯(IBMA)。
合适的牛顿共聚物的例子包括商标为ELIOKEM的PlioliteVTAC-L、Pliolite VTAC-H、Plioway ECH、Plioway Ultra 200、PliowayEC1。
合适的网状共聚物的例子包括商标为ELIOKEM的Pliolite AC3H、Plioway ECL、Plioway Ultra G20、Plioway EC-T。
牛顿和网状共聚物由聚合制备，该聚合在本体中、在溶液中、在悬浮液中或在乳液中进行。最好的模式是采用常规乳液聚合。
聚合物粘结剂然后可以由常规技术，例如通过与如下物质混合而配制：常规反应性颜料体系、分散剂、增塑剂、防沫剂、增稠剂、氯化链烷烃(paraffin)溶剂和通常用于制备所需类型发泡型防火涂料的其它添加剂(蜡、填料、纤维、防沉淀剂等)。
根据本发明，形成该聚合物粘结剂的最好模式包括如下步骤：(a)在溶剂中或在水中溶解牛顿和/或网状共聚物，(b)非必要地加入氯化链烷烃，(c)均化混合物和加入添加剂。
根据本发明的发泡型防火涂料优选包含作为泡沫形成物质的磷酸和/或多磷酸的铵盐，更优选多磷酸铵。
根据本发明的发泡型防火涂料优选包含作为碳形成物质的碳氢化合物(carbohydride)，优选季戊四醇、二季戊四醇、三季戊四醇和/或季戊四醇的缩聚物。
根据本发明的发泡型防火涂料可包含卤素或不包含卤素。
根据本发明的发泡型防火涂料以可刷涂、可喷淋或可辊压的涂料材料的形式用于保护不同的表面，优选钢、木材、电缆和管子。
根据本发明的发泡型防火涂料可以是水基或溶剂基组合物。
根据本发明的发泡型防火涂料可用于屋顶中以防止着火和火焰扩散，用于不可燃基材，如建筑物中的结构钢、大梁等上的应用、容器、或贮存罐以保护它们以防止在着火中遇到非常高温度时软化。
给出如下实施例和附图以说明采用包含根据本发明的粘结剂的发泡型防火涂料配制剂的本发明。
附图简要说明
图1显示仅包含PMS/2EHA(75/25)、仅包含多磷酸铵(APP)，或包含两者的60/40混合物的牛顿共聚物的热稳定性(计算值和试验值)。
图2显示仅包含苯乙烯/丙烯酸类共聚物、仅包含多磷酸铵(APP)，或包含两者的60/40混合物的牛顿共聚物的热稳定性(计算值和试验值)。
图3显示仅包含PMS/2EHA(75/25)、仅包含多磷酸铵(APP)、或包含两者的60/40混合物的含有交联共聚物的共聚物的热稳定性(计算值和试验值)。
图4显示仅包含交联苯乙烯/丙烯酸共聚物、仅包含多磷酸铵(APP)、或包含两者的60/40混合物的共聚物的热稳定性(计算值和试验值)。
图5说明对于各种PMS/2EHA(50/50，75/25和100/0)共聚物和APP的60/40共混物，在TGA中理论和试验重量损失之间的差异(Δ(T)曲线)。
图6显示在含有采用牛顿或交联共聚物制备的发泡型防火涂料在铝板上的隔热，该共聚物仅包含PMS/2EHA(75/25)、或PMS/2EHA/丙烯酸类物或苯乙烯/丙烯酸类物。
图7说明在含有采用包含牛顿和交联聚合物的共混物的共聚物、或商业苯乙烯/丙烯酸类物共聚物制备的发泡型防火涂料在铝板上的隔热。
图8说明在采用实施例2的涂料1、涂料2或涂料4制备的发泡型防火涂料对35kW/m2的曝露之后，采用锥形量热计测量的热释放速率(RHR)的数值。
实施例1：聚合物粘结剂的热稳定性
1.1.
测量
各种组合物的热稳定性由热重量分析测量。
热重量分析(TGA)在10℃/min下在合成空气或氮气(流量：5×10-7m3/s，Air Liquide级)下，使用Setaram MTB 10-8微量天平进行。在每种情况下，使用的样品质量固定在10mg，将样品(粉末混合物)布置在开放玻璃状二氧化硅盘中。在整个温度范围内温度测量的精度是1.5℃。在试验和理论TGA曲线之间的重量差异曲线计算如下：
Mpoly(T)：共聚物的TGA曲线，
Madd(T)：APP的TGA曲线，
Mexp(T)：共聚物/APP的TGA曲线，
Mthe(T)：由共聚物和APP的TGA曲线之间的线性结合计算的TGA曲线，
Mthe(T)：xMpoly(T)+yMAPP(T)，
Δ(T)：重量差异的曲线
Δ(T)＝Mexp(T)-Mthe(T)。
Δ(T)曲线使得能够观察与添加剂存在有关的聚合物热稳定性的最终增加或降低。
1.2.
结果
TGA曲线在图1-5中说明。
当与苯乙烯/丙烯酸类物(S/A)共聚物(图2)比较时，PMS/2EHA共聚物的热稳定性增加(图1)。
采用交联共聚物获得相似的结果(图3和4)。
在理论和试验重量损失之间的差异(在采用各种比例的PMS/2EHA共聚物获得的图5中的Δ(T)曲线显示当取代苯乙烯(PMS)的水平增加时，稳定性增加。
实施例2：发泡涂料的制备
制备不同的组合物。不采用氯化链烷烃制备第一系列的涂料以显现聚合物粘结剂的本质对着火性能的影响。采用氯化链烷烃制备第二系列的涂料。
采用线性聚合物PMS/2EHA、交联的聚合物PMS/2EHA、线性S/A聚合物、交联的S/A聚合物或对比的商业S/A共聚物制备涂料。
将共聚物在高剪切下溶于溶剂，然后其中必要时加入氯化链烷烃，在均化之后以所述顺序分散颜料。
组合物说明见表1。
2.1.
没有氯化链烷烃的涂料：
涂料A1：牛顿PMS/2EHA(75/25)共聚物
涂料A2：牛顿交联的PMS/2EHA(75/25)共聚物
涂料B1：牛顿PMS/2EHA/丙烯酸类共聚物(50/14/36)
涂料B2：牛顿交联的PMS/2EHA/丙烯酸类共聚物(50/14/36)
涂料C1：牛顿苯乙烯/2EHA/丙烯酸类共聚物(50/14/36)
涂料C2：牛顿交联的苯乙烯/2EHA/丙烯酸类共聚物(50/15/36)。
2.2.
采用氯化链烷烃的涂料
组合物说明见表2。
实施例3：隔热的评价
3.1.
测量
由采用锥表量热计来测量耐火性以建立温度情况。通过测量承受35或75kW/m2热通量的涂敷基材的温度来测试发泡型防火涂料的绝缘性能。将100×100×4mm铝板用发泡型防火涂料涂敷(800g/m2)，在50℃下干燥48h。根据ASTM1356-90和ISO 5660在35或75kW/m2的热通量下，将样品曝露于Stanton Redcroft锥形量热计(50kW/m2对应于着火期间释放的热量：来自V Babrauskas，Fire and Mat(1984)，8(2)，81)。
热释放速率(RHR)表示对于给定样品表面的对时间的热流释放，使用氧消耗量热法测量。使用自己开发的软件计算数据(TCO，TCO2，TSV和THR)。
3.2.
结果
在图6和7中说明。
图6中的图显示当粘结剂由线性和交联的聚合物的结合物组成时(涂料A2，B2和C2)，隔热更好。当使用聚合物的此结合物时，在涂敷板背侧测量的温度显著低于采用线性聚合物作为唯一粘结剂的温度。当聚合物仅从PMS和2EHA制备(涂料A2)或结合到进一步的取代丙烯酸酯(B2)时，涂料是特别有效的。
图7显示在35kW/m2下曝露30分钟之后，当涂料采用牛顿和交联聚合物的结合物制备时，在板背侧的温度稳定在约310℃，即比采用对比S/A粘结剂测量的温度低约110℃。
实施例4：发泡型防火涂料的着火性能
采用含有氯化链烷烃的涂料测量，说明见图8。
所有的曲线看起来相似，及第一个主要的峰对应于发泡结构的形成，随后的第二个弱峰或平台对应于泡沫的降解和对应于残余物形成，该残余物在高温下稳定。
对于包括对比的商业苯乙烯/丙烯酸类共聚物的组合物，热释放速率(RHR)最大(200kW/m2)。对于包括取代苯乙烯/2EHA共聚物的组合物热释放速率较低，分别为对于PMS/2EHA共聚物的139kW/m2和对于测量PMS/PTBS/2EHA共聚物的54kW/m2。采用商业溶剂基的涂料Unitherm 38091获得的RHR用于对比，其为186kW/m2。
烟雾体积、CO和CO2释放和总热量释放在表2中给出，其中与Unitherm 38091相比，取代苯乙烯/2EHA聚合物(涂料1-3)的性能良好。
采用共聚物作为根据本发明的粘结剂获得的烟雾、CO和CO2释放的低数值说明对环境的保护。
Claims (10)
1.一种在发泡型防火涂料中用于或用作聚合物粘结剂的共聚物，包括牛顿共聚物和网状共聚物的共混物，该牛顿和网状共聚物由取代苯乙烯和取代丙烯酸酯组成，至少包括对甲基苯乙烯(PMS)和丙烯酸2-乙基己酯(2EHA)。
2.根据权利要求1所述的共聚物，其中网状共聚物选自触变共聚物或假塑性共聚物。
3.根据权利要求1或2所述的共聚物，其中对甲基苯乙烯和2EHA的比例是100/0-50/50，优选90/10，优选80/20和更优选75/25。
4.根据权利要求1-3任一所述的共聚物，进一步包括对叔丁基苯乙烯(PTBS)和/或甲基丙烯酸异丁酯(IBMA)。
5.根据权利要求1-4任一所述的共聚物，其中共混物的共聚物由乳液聚合获得。
6.一种包括权利要求1-5任一所述的共聚物的发泡型防火涂料。
7.根据权利要求6所述的发泡型防火涂料，进一步包括泡沫形成物质、碳形成物质和其它常规添加剂。
8.根据权利要求7所述的发泡型防火涂料，其中泡沫形成物质是磷酸的铵盐，碳形成物质选自季戊四醇、二季戊四醇、三季戊四醇或季戊四醇的缩聚物。
9.根据权利要求6-8任一所述的发泡型防火涂料，其是水基的或溶剂基的。
10.一种形成权利要求6-9任一所述的发泡型防火涂料的方法，包括如下步骤：(a)在溶剂中或在水中溶解牛顿和/或网状共聚物，(b)非必要地加入氯化链烷烃，(c)均化混合物和加入添加剂。
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| TWI391654B (zh) * | 2008-06-30 | 2013-04-01 | Univ Chung Hua | 耐火塗料產品分析技術與檢測方法 |
| JP2011105855A (ja) * | 2009-11-18 | 2011-06-02 | Nippon Paint Co Ltd | 水性発泡耐火塗料組成物 |
| DE102013205348A1 (de) | 2013-03-26 | 2014-10-02 | Hilti Aktiengesellschaft | Dämmschichtbildende Zusammensetzung und deren Verwendung |
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Family Cites Families (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2512435A (en) | 1947-04-11 | 1950-06-20 | Shell Dev | Emulsions |
| US2529460A (en) | 1949-04-30 | 1950-11-07 | Sharp & Dohme Inc | Emulsions containing resins |
| US3002923A (en) | 1957-03-29 | 1961-10-03 | Atlas Chem Ind | Water-in-oil emulsion drilling fluid |
| US2994660A (en) | 1957-05-27 | 1961-08-01 | Magnet Cove Barium Corp | Water-in-oil emulsion drilling fluid |
| US3284393A (en) | 1959-11-04 | 1966-11-08 | Dow Chemical Co | Water-in-oil emulsion polymerization process for polymerizing watersoluble monomers |
| US3316965A (en) | 1963-08-05 | 1967-05-02 | Union Oil Co | Material and process for treating subterranean formations |
| US3528914A (en) | 1966-12-14 | 1970-09-15 | Shell Oil Co | Drilling fluid and method for increasing drilling rate |
| US3711405A (en) | 1969-11-19 | 1973-01-16 | Union Oil Co | Low fluid loss well treating composition and method |
| US3624019A (en) | 1970-12-15 | 1971-11-30 | Nalco Chemical Co | Process for rapidly dissolving water-soluble polymers |
| US3733289A (en) * | 1971-08-24 | 1973-05-15 | Monsanto Co | Fire retardant coating composition |
| US4085802A (en) | 1977-01-17 | 1978-04-25 | Continental Oil Company | Use of thickened oil for sand control processes |
| US4168257A (en) | 1977-05-30 | 1979-09-18 | Shell Oil Company | Process for treating wells with viscous epoxy-resin-forming solutions |
| US4212312A (en) | 1978-08-28 | 1980-07-15 | Shell Oil Company | Fragmented polymers as friction reducers in pipeline transportation of products |
| US4794139A (en) * | 1986-09-22 | 1988-12-27 | The Goodyear Tire & Rubber Company | Thixotropic thickening agent for aqueous systems |
| US5086841A (en) | 1989-06-19 | 1992-02-11 | Nalco Chemical Company | Method of reducing circulation fluid loss using water absorbing polymer |
| US5250066A (en) * | 1990-03-19 | 1993-10-05 | Becton Dickinson And Company | Plastic pointed articles and method for their preparation |
| US5270416A (en) * | 1992-09-04 | 1993-12-14 | Ferro Corporation | Thermosetting glycidyl modified acrylic powder coatings |
| GB9319112D0 (en) | 1993-09-15 | 1993-11-03 | Allied Colloids Ltd | Stabilisation and use of heterogeneous liquid composition |
| US6169058B1 (en) | 1997-06-05 | 2001-01-02 | Bj Services Company | Compositions and methods for hydraulic fracturing |
| ES2205347T3 (es) * | 1997-09-11 | 2004-05-01 | Clariant Gmbh | Revestimiento intumescente resistente a condiciones tropicales. |
| CN1183445A (zh) * | 1997-12-25 | 1998-06-03 | 赵小鲁 | 水性膨胀型防火胶 |
| AU2094899A (en) * | 1997-12-31 | 1999-07-19 | Correct Solutions, Corp. | Correction fluid marker and formulation for fluid |
| WO2001005886A1 (en) * | 1999-07-19 | 2001-01-25 | W.R. Grace & Co.-Conn. | Thermally protective intumescent compositions |
| US6248699B1 (en) | 1999-07-29 | 2001-06-19 | Crompton Corporation | Gelling system for hydrocarbon fluids |
| US20060264562A1 (en) * | 1999-08-09 | 2006-11-23 | Sophie Duquesne | Polymer binder for intumescent coatings |
| JP2002146088A (ja) * | 2000-11-10 | 2002-05-22 | Kanegafuchi Chem Ind Co Ltd | スチレン系樹脂発泡体塗布物 |
| DE10061081A1 (de) * | 2000-12-08 | 2002-06-13 | Bayer Ag | Flammwidrige Polycarbonat-Blends |
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| ES2243675T3 (es) | 2005-12-01 |
| RU2302440C2 (ru) | 2007-07-10 |
| US7417091B2 (en) | 2008-08-26 |
| ATE300584T1 (de) | 2005-08-15 |
| EP1431353A1 (en) | 2004-06-23 |
| CA2510052C (en) | 2011-03-08 |
| JP4570963B2 (ja) | 2010-10-27 |
| BR0317602A (pt) | 2005-11-29 |
| DE60205264T2 (de) | 2006-06-01 |
| TR200502297T1 (tr) | 2006-02-21 |
| JP2006511655A (ja) | 2006-04-06 |
| US7288588B2 (en) | 2007-10-30 |
| US7105605B2 (en) | 2006-09-12 |
| US20040132910A1 (en) | 2004-07-08 |
| AU2003303656A1 (en) | 2004-07-29 |
| HK1085758A1 (en) | 2006-09-01 |
| MXPA05006736A (es) | 2006-02-17 |
| US20070010624A1 (en) | 2007-01-11 |
| CA2510052A1 (en) | 2004-07-22 |
| US20060241196A1 (en) | 2006-10-26 |
| EP1431353B1 (en) | 2005-07-27 |
| BRPI0317602B1 (pt) | 2015-05-19 |
| WO2004061020A1 (en) | 2004-07-22 |
| RU2005122947A (ru) | 2006-01-20 |
| DE60205264D1 (de) | 2005-09-01 |
| PT1431353E (pt) | 2005-11-30 |
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