CN109369958A - 一种有机修饰磷酸锆的制备方法及其应用 - Google Patents
一种有机修饰磷酸锆的制备方法及其应用 Download PDFInfo
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- 229910000166 zirconium phosphate Inorganic materials 0.000 title claims abstract description 56
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 title claims abstract description 56
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- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/321—Phosphates
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Abstract
本发明公开了一种有机物修饰磷酸锆的制备方法及其应用。本发明有机修饰磷酸锆的制备方法包括如下步骤：将苯基硅烷溶于异丙醇溶剂中，加入钛酸四丁酯，在55～75℃条件下，滴加哌啶醇异丙醇溶液，滴加完后再反应2h，反应产物经减压蒸馏得到苯基硅烷哌啶醇缩聚物；将1～30％的ɑ‑磷酸锆乙醇水溶液超声处理10～30min，加入苯基硅烷哌啶醇缩聚物，再超声处理10～30min，于25～35℃条件下，搅拌反应24～48h，离心除去清液，用乙醇清洗沉淀，55～70℃烘干，得到有机修饰磷酸锆。本发明的有机修饰磷酸锆作为PP，PC和SR的阻燃剂，添加量在0.5～5％；作为协效阻燃剂使用时，添加量0.5～1.5％最佳，阻燃效率高，添加量少，对材料性能影响小。
Description
技术领域
本发明涉及有机修饰无机物制备方法领域，具体涉及一种有机修饰磷酸锆的制备方法。
背景技术
近年来，材料的阻燃性能日益受到关注。提高材料的阻燃性能同时不损害材料的力学、光学等性能成为研究热点。目前市场上的无机阻燃剂如氢氧化物或氧化物添加量超过50wt％才能获得UL-94V-0的阻燃效果，添加量偏大，增加阻燃材料的生产成本，还会恶化材料的加工性能特别是力学性能。如何协调阻燃剂的添加量与复合材料的力学性能是制约阻燃剂应用的一个技术关键点。为了解决这一问题，提高阻燃剂的阻燃效率可以有效降低阻燃剂的添加量。研究表明，磷酸锆具有协同阻燃的效果，经过有机物修饰改性的磷酸锆，阻燃性能可以获得较大的提高。Wang Yuzhong等(Synthesis of organo-modifiedα-zirconium phosphate and its effect on the flame retardancy of IFR poly(lacticacid)systems.Polymer Degradation and Stability,2011,96:771-777)通过十八烷基二甲基叔胺修饰的磷酸锆复配聚磷酸铵阻燃聚乳酸，研究结果表明2％的磷酸锆与8％的聚磷酸铵复配使用可使材料的LOI达到37％，UL-94达到V-0级。
由此可见，为了提高磷酸锆的阻燃性能，对其进行插层改性是一种有效的方法，CN105061761A公开了一种纳米磷酸锆修饰三嗪大分子成炭剂，与聚磷酸铵复配形成协同阻燃作用，有效改善材料的LOI，同时UL-94测试达到V-0级。CN104774474A利用乙烯基三乙氧基硅烷改性的五甲基哌啶醇对磷酸锆进行有机修饰，添加量4％至硅橡胶中可使LOI达到31，UL-94测试达到V-0级。该专利利用乙烯基三乙氧基硅烷作为有机改性剂，目的是为了在磷酸锆的结构引入双键链端，使得磷酸锆能更好地分散在硅橡胶中。
本发明在于进一步提高有机修饰磷酸锆阻燃剂的阻燃效果，促使聚合物在高温缺氧条件下通过催化交联成炭，提高材料的热稳定性。在保持阻燃效果不变的前提下，阻燃剂添加量远远低于目前膨胀型阻燃剂的添加量，同时，聚合物阻燃成分在燃烧时能产生稳定、致密的炭层，可进一步提高材料的氧指数和片层阻隔效应，同时有利于提高材料的力学性能。
发明内容
本发明的目的是提供一种有机修饰磷酸锆的制备方法，以克服现有技术存在的缺陷。
本发明的第二个目的在于提供一种有机修饰磷酸锆作为无卤阻燃剂或协效阻燃剂的应用，该有机修饰磷酸锆阻燃剂或协效阻燃剂阻燃效率高，添加量少，对材料性能影响小。
本发明的有机修饰磷酸锆的制备方法由以下步骤组成：将苯基硅烷溶于异丙醇溶剂中，加入钛酸四丁酯，在55～75℃条件下，滴加哌啶醇异丙醇溶液，滴加完后再反应2h，反应产物经减压蒸馏得到苯基硅烷哌啶醇缩聚物；将1～30％的ɑ-磷酸锆乙醇水溶液超声处理10～30min，加入苯基硅烷哌啶醇缩聚物，再超声处理10～30min，于25～35℃条件下，搅拌反应24～48h，离心除去清液，用乙醇清洗沉淀，55～70℃烘干，得到有机修饰磷酸锆。
本发明的苯基硅烷哌啶醇缩聚物由苯基硅烷与哌啶醇在催化作用下反应得到。
所述苯基硅烷为苯基三乙氧基硅烷，苯基三甲氧基硅烷或甲基苯基二甲氧基硅烷中的一种。
所述哌啶醇为五甲基哌啶醇或1-烯丙基-2,2,6,6-四甲基哌啶醇，其中，1-烯丙基-2,2,6,6-四甲基哌啶醇结构式如下所示：
苯基硅烷与哌啶醇的摩尔比为1.0:1.0～1.2，催化剂钛酸四丁酯用量为反应物苯基硅烷和哌啶醇总质量的0.1～0.5％，异丙醇总用量为反应物苯基硅烷和哌啶醇总质量的70～90％。
苯基硅烷哌啶醇缩聚物与ɑ-磷酸锆的质量比为4～6:1，反应介质为乙醇水溶液，水与乙醇的体积比为1:5～8。
本发明的有机修饰磷酸锆作为无卤阻燃剂或协效阻燃剂的应用，可单独作为PP，PC和SR的阻燃剂，添加量为0.5～5％；作为协效阻燃剂使用时，添加量为0.5～1.5％最佳。本发明制备的有机修饰磷酸锆作为阻燃剂使用，阻燃效率高，0.5～5％添加量即可改善材料的阻燃性能，提高材料的热稳定性、降低材料的燃烧速率；同时与PP，PC和SR具有很好的相容性，不会严重恶化材料的力学性能。
与现有技术相比，本发明所提供的有机修饰磷酸锆制备方法具有如下优点：
1.有机修饰磷酸锆的制备以异丙醇、乙醇和水作为分散介质，气味小、毒性低，符合环保要求。
2.有机修饰磷酸锆具有高效阻燃，热稳定性好等优点。通过在结构中引入插层难度大的苯环，可以增加材料的热稳定性；同时根据需要采用具有双键结构的有机物改性剂，可以与各种材料如聚丙烯等形成有效的键合，增强阻燃剂与材料的相容性，提高材料阻燃性能，且不损害材料的力学性能。
3.有机修饰磷酸锆具有自由基淬灭效果，可以改善材料的光稳定性，提高材料耐黄变特性。
4.有机修饰磷酸锆稳定性好，单独作为阻燃剂使用时，添加量低，成本低，因此应用前景广泛。
具体实施方式
下面通过实施例来对本发明进行详细说明，这些实施例仅能用来解释发明而不能用来解释对本发明的限制。
实施例1
将39.7g苯基三甲氧基硅烷搅拌溶于200mL异丙醇中，加入0.15g钛酸四丁酯，将温度升至55℃，缓慢滴加含34.3g五甲基哌啶醇与50mL异丙醇的溶液，滴加时间40min，滴加完后再反应2h，反应产物经减压旋转蒸发仪旋蒸除去异丙醇，得到苯基硅烷哌啶醇缩聚物1,2,2,6,6-五甲基-4-(苯基二甲氧基硅氧基)哌啶。
将10gα-磷酸锆、水与醇的体积比为1:7的1L乙醇水溶液超声处理10min，加入50g1,2,2,6,6-五甲基-4-(苯基二甲氧基硅)哌啶，超声处理20min，30℃条件下搅拌反应24h，反应结束后，经离心除去清液，用乙醇清洗沉淀3次，于65℃烘干得到有机修饰磷酸锆。
实施例2
将48.1g苯基三乙氧基硅烷搅拌溶于400mL异丙醇中，加入0.37g钛酸四丁酯，将温度升至65℃，缓慢滴加含43.3g 1-烯丙基-2,2,6,6-四甲基哌啶醇与50mL异丙醇的溶液，滴加时间40min，滴加完后再反应2h，反应产物经减压旋转蒸发仪旋蒸除去异丙醇，得到苯基硅烷哌啶醇缩聚物1-烯丙基-2,2,6,6-四甲基-4-(苯基二乙氧基硅氧基)哌啶。
将10gα-磷酸锆、水与醇的体积比为1:8的200mL乙醇水溶液超声处理10min，加入60g 1-烯丙基-2,2,6,6-四甲基-4-(苯基二乙氧基硅氧基)哌啶，超声处理20min，30℃条件下搅拌反应36h，反应结束后，经离心除去清液，用乙醇清洗沉淀3次，于65℃烘干得到有机修饰磷酸锆。
实施例3
将36.5g甲基苯基二甲氧基硅烷搅拌溶于500mL异丙醇中，加入0.36g钛酸四丁酯，将温度升至75℃，缓慢滴加含47.3g 1-烯丙基-2,2,6,6-四甲基哌啶醇与50mL异丙醇的溶液，滴加时间40min，滴加完后再反应2h，反应产物经减压旋转蒸发仪旋蒸除去异丙醇，得到苯基硅烷哌啶醇缩聚物1-烯丙基-2,2,6,6-四甲基-4-(甲基苯基乙氧基硅氧基)哌啶。
将10gα-磷酸锆、水与醇的体积比为1:5的33mL乙醇水溶液超声处理10min，加入40g 1-烯丙基-2,2,6,6-四甲基-4-(甲基苯基乙氧基硅氧基)哌啶，超声处理30min，30℃条件下搅拌反应48h，反应结束后，经离心除去清液，用乙醇清洗沉淀3次，于65℃烘干得到有机修饰磷酸锆。
实施例4
将36.5g甲基苯基二甲氧基硅烷搅拌溶于200mL异丙醇中，加入0.35g钛酸四丁酯，将温度升至70℃，缓慢滴加含34.3g五甲基哌啶醇与50mL异丙醇的溶液，滴加时间40min，滴加完后再反应2h，反应产物经减压旋转蒸发仪旋蒸除去异丙醇，得到苯基硅烷哌啶醇缩聚物1,2,2,6,6-五甲基-4-(甲基苯基甲氧基硅氧基)哌啶。
将10gα-磷酸锆、水与醇的体积比为1:8的100mL乙醇水溶液超声处理30min，加入50g 1,2,2,6,6-五甲基-4-(甲基苯基甲氧基硅氧基)哌啶，超声处理20min，30℃条件下搅拌反应48h，反应结束后，经离心除去清液，用乙醇清洗沉淀3次，于65℃烘干得到有机修饰磷酸锆。
将实施例1-4所得的有机修饰磷酸锆作为阻燃剂或协效阻燃剂分别添加至PP，PC和SR中，进行阻燃性能分析、力学性能分析。评判有机修饰磷酸锆对材料阻燃性能和力学性能的影响。其中，极限氧指数(LOI)按GB/T 2406-2009标准进行；垂直燃烧(UL-94)按照ASTMD635进行。拉伸强度按照GB/T528-2009测定，测试速度为50mm/min；弯曲强度按照GB/T9341-2008的标准进行，测试速度为2mm/min。
将实施例1-4得到的有机修饰磷酸锆5份、PP 95份在密炼机上于180℃熔融共混，混炼均匀后均匀出片，在万能制样机上制备各种标样，进行阻燃性能、力学性能和热稳定性测试，测试结果如表1所示。
表1PP的阻燃性能和力学性能
将实施例1-4得到的有机修饰磷酸锆3份、PC 97份预混后用双螺杆挤出、造粒，螺杆转速为85r/min。用注塑机制得各种测试标准样条，进行阻燃性能、力学性能测试和热稳定性，测试结果如表2所示。
表2PC的阻燃性能和力学性能
将实施例1-4得到的有机修饰磷酸锆1份、APP19份，SR 96份在开炼机上于室温条件下混炼均匀，放置24h，于120℃平板硫化机上硫化，在万能制样机上制备各种标样，进行阻燃性能、力学性能测试和热稳定性，测试结果如表3所示。
表3SR的阻燃性能和力学性能
将实施例1-4得到的有机修饰磷酸锆0.5份、APP19.5份，PP80份在密炼机上于熔融共混，混炼均匀后均匀出片，在万能制样机上制备各种标样，进行阻燃性能、力学性能和热稳定性测试，测试结果如表4所示。
表4PP的阻燃性能和力学性能
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种有机修饰磷酸锆的制备方法，其特征在于由以下步骤组成：将苯基硅烷溶于异丙醇溶剂中，加入钛酸四丁酯，在55～75℃条件下，滴加哌啶醇异丙醇溶液，滴加完后再反应2h，反应产物经减压蒸馏得到苯基硅烷哌啶醇缩聚物；将1～30％的ɑ-磷酸锆乙醇水溶液超声处理10～30min，加入苯基硅烷哌啶醇缩聚物，再超声处理10～30min，于25～35℃条件下，搅拌反应24～48h，离心除去清液，用乙醇清洗沉淀，55～70℃烘干，得到有机修饰磷酸锆。
2.根据权利要求1所述的有机修饰磷酸锆的制备方法，其特征在于所述苯基硅烷为苯基三乙氧基硅烷、苯基三甲氧基硅烷或甲基苯基二甲氧基硅烷中的一种。
3.根据权利要求1所述的有机修饰磷酸锆的制备方法，其特征在于所述哌啶醇为五甲基哌啶醇或1-烯丙基-2,2,6,6-四甲基哌啶醇。
4.根据权利要求1所述的有机修饰磷酸锆的制备方法，其特征在于所述苯基硅烷与哌啶醇的摩尔比为1.0:1.0～1.2。
5.根据权利要求1所述的有机修饰磷酸锆的制备方法，其特征在于所述钛酸四丁酯用量为反应物苯基硅烷和哌啶醇总质量的0.1～0.5％。
6.根据权利要求1所述的有机修饰磷酸锆的制备方法，其特征在于所述异丙醇总用量为反应物苯基硅烷和哌啶醇总质量的70～90％。
7.根据权利要求1所述的有机修饰磷酸锆的制备方法，其特征在于所述苯基硅烷哌啶醇缩聚物与ɑ-磷酸锆的质量比为4～6:1。
8.根据权利要求1所述的有机修饰磷酸锆的制备方法，其特征在于所述反应介质为乙醇水溶液，水与乙醇的体积比为1:5～8。
9.权利要求1所述的有机修饰磷酸锆的应用，其特征在于作为PP，PC和SR的阻燃剂使用，添加量为0.5～5％。
10.权利要求1所述的有机修饰磷酸锆的应用，其特征在于作为PP，PC和SR的协效阻燃剂使用，添加量为0.5～1.5％。
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