CN111592712A - 一种掺稀土有机配合物阻燃抗滴落转光膜及其制备方法 - Google Patents
一种掺稀土有机配合物阻燃抗滴落转光膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种掺稀土有机配合物的阻燃、抗滴落EVA转光薄膜及其制备方法。包括如下步骤：磷系阻燃剂、交联剂、抗滴落剂和稀土有机配合物转光剂经干燥后按一定的配比与EVA预混合后，炼塑机双辊开炼混合，混合温度为冷辊室温，混合时间为3～5min，挤出造粒后，冷却切粒、烘干，在将混合好的料在平板硫化仪上模压成型。本发明制备的EVA转光膜透光率可以达到92.9％，UL‑94测试等级可达V‑0级，极限氧指数可以达到30.6％，燃烧测试过程中几乎无滴落现象。
Description
技术领域
本发明属于阻燃高分子材料领域，具体涉及一种掺稀土有机配合物阻燃抗滴落EVA转光膜及其制备方法。
背景技术
乙烯-醋酸乙烯酯共聚物即EVA(ethylene-vinyl acetate copolymer)分子式是(C2H4)n.(C4H6O2)m具有透光率高，熔融温度低，熔体流动性好等优点，常被用作转光膜的基材。但是，EVA本身极易燃烧，其极限氧指数只有18％左右，并且由于EVA结构是线性的，含有大量脂肪族结构，导致EVA在高温时熔融黏度低，成炭能力弱，熔点大都在90℃以下，分解温度却在230℃以上，因此极易燃烧并且产生严重的滴落，引起二次燃烧会产生较大的环境污染和财产损失。
EVA在燃烧过程中，因为不能完全燃烧而出现氧化后加热熔融滴落的现象，大大提高了阻燃剂的使用量，而过多的阻燃剂的使用会降低材料的综合性能。如何解决EVA燃烧时熔融滴落的问题，减少阻燃剂的使用量，一直是广大科研和实践工作者关心的问题。
比较常见的抗滴落方法是添加聚四氟乙烯(PTFE)，其易纤维化从而起到抗滴落的作用。靳昕怡等(纺织学报，2018，v.39；No.389(08)：20-26.)针对磷系阻燃聚酯存在耐熔滴差的问题，采用自制膨胀型阻燃剂 (IFR)与聚四氟乙烯以不同的质量比配制成复合抑熔滴剂，将其与含磷阻燃聚酯(FRPET)切片通过熔融共混的方法制备阻燃抑熔滴聚酯共混物，1min内的熔滴数从46滴减少到21滴，700℃时的残炭量相对增加了68.8％。
还有常见的抗滴落剂如蒙脱土、石墨烯等，王虎等(阻燃抗滴落PET低熔点聚酯研究[C]//中国阻燃学术年会.2012.)使用含磷阻燃剂FR100和协效剂三氧化二锑解决PET聚酯的阻燃问题，但是由于熔融滴落严重，引燃脱脂棉使得阻燃等级降低，于是引入了有机化处理后的蒙脱土，阻燃等级从V-2升至V-0，无熔融滴落现象。魏科峰等(CN107245228A，2017-10-13.)用硅烷偶联剂改性石墨烯，然后将其共聚到PET 中，再与聚乙烯基硅氧烷和聚四氟乙烯熔融共混，即得到抗熔滴PET材料，极限氧指数达到33％以上，垂直燃烧等级达到V-0，几乎不存在熔滴现象。
还有学者添加其他的抗滴落剂，马萌等(合成纤维工业，2016，39(3)：21-25.)采用硼酸锌作为抗滴落剂，和磷系阻燃剂CEPTA复合阻燃PET时，材料燃烧残碳表面更加致密，热解残碳率最高为14.4％，抗滴落效果明显改善，可能与锌元素促进炭化降解和产生的三氧化二硼表面覆盖有关。
王玉忠等(CN108359084A，2018-08-03.)将含有苯酰亚胺结构的单体共聚到聚酯中，制备了一种基于苯酰亚胺结构的高温自交联共聚酯，在高温或者燃烧时会发生重排反应，从而发生交联抑制熔融滴落，引入1～30mol％的交联单体即可通过垂直燃烧V-0等级测试。
本发明从以往的文献中优选阻燃剂、抗滴落剂和交联剂，在保证EVA转光膜透光率的前提下，制备阻燃抗滴落EVA转光膜。
发明内容
本发明的目的在于提供一种环境友好、抗滴落、阻燃效果好、高透光率EVA转光膜的制备方法。
用炼塑机将上述提到的EVA、转光剂、阻燃剂、抗滴落剂和交联剂按比例双辊开炼混合，将混合好的料用平板硫化机模压成型，裁切得到所需规格的样条。
本发明所采用的技术方案具体步骤如下。
1)EVA、磷系阻燃剂、转光剂、抗滴落剂和交联剂按比例采用炼塑机双辊开炼混合，混合温度为冷辊室温，混合时间为3～5min，挤出造粒后，冷却切粒、烘干。将混合好的料在平板硫化仪上模压成型，得到测试所需规格的样条。
在上述制备工艺中，所述EVA的是VA含量为1～15wt％的乙烯-醋酸乙烯酯的共聚物。
在上述制备工艺中，所述磷系阻燃剂为磷酸三甲苯酯(TCP)、磷酸甲苯二苯酯(CDP)、异丙基化磷酸三苯酯(IPPP)、双酚A双(二苯基磷酸酯)(BDP)和磷酸三苯酯(TPP)等中的一种：
在上述制备工艺中，所述转光剂为一系列稀土有机配合物Eu(TTA)3dpbt、Eu(SA)3phen、Eu(DBM)3phen 中的一种。
在上述制备工艺中，所述抗滴落剂为聚四氟乙烯、硼酸锌中的一种。
在上述制备工艺中，所述交联剂为过氧化二异丙苯(DCP)，2，5-二甲基-2，5-双-(叔丁基过氧化)己烷(DTBP)中的一种。
在上述制备工艺中，转光膜基材、阻燃剂、抗滴落剂、交联剂和转光剂的质量比＝92～97∶1～5∶0～2∶0～5∶1～3。
在上述制备工艺中，选用合适的模具，把混合材料样品倒入模具中，当平板硫化机温度上升到150～200 ℃时，将模具放入平板硫化机，8～20MPa下，热压400～600s，之后冷压300～500s，制成试样薄片。用标准尺寸裁刀在气动切片机上将薄片切成测试所需的样条，以待测试各项性能时使用。
与现有技术相比，本发明的有益效果为：
本发明通过添加交联剂和抗滴落剂，减少传统阻燃剂的用量，达到抗熔滴和阻燃的双重目的，并且保证薄膜的透光率达90％。本发明改善了EVA的阻燃性能，提供了一种环境友好、阻燃效果好、高透光率 EVA转光膜的制备方法。
附图说明
图1各实施例转光薄膜的极限氧指数和透光率
具体实施方式
下面结合实施例对本发明作详细说明。
实施例一
将EVA(9.2g)、磷系阻燃剂TCP(0.5g)和转光剂Eu(TTA)3dpbt(0.3g)采用炼塑机双辊开炼混合，混合温度为冷辊室温，混合时间为3min。按照相关标准选用合适的模具，把混合材料样品倒入模具中，当平板硫化机温度上升到150℃时，将模具放入平板硫化机，13MPa下，热压400s，之后冷压300s，制成试样薄片。用标准尺寸裁刀在气动切片机上将薄片切成测试所需的样条，以待测试各项性能时使用。
实施例二
将EVA(9.2g)、磷系阻燃剂CDP(0.2g)、抗滴落剂四氟乙烯(0.2g)、交联剂DCP(0.2g)和转光剂 Eu(TTA)3dpbt(0.2g)采用炼塑机双辊开炼混合，混合温度为冷辊室温，混合时间为3.5min。按照相关标准选用合适的模具，把混合材料样品倒入模具中，当平板硫化机温度上升到160℃时，将模具放入平板硫化机，15MPa下，热压450s，之后冷压350s，制成试样薄片。用标准尺寸裁刀在气动切片机上将薄片切成测试所需的样条，以待测试各项性能时使用。
实施例三
将EVA(9.4g)、磷系阻燃剂IPPP(0.3g)、抗滴落剂四氟乙烯(0.1g)、交联剂DTBP(0.1g)和转光剂Eu(SA)3phen(0.1g)采用炼塑机双辊开炼混合，混合温度为冷辊室温，混合时间为4min。按照相关标准选用合适的模具，把混合材料样品倒入模具中，当平板硫化机温度上升到170℃时，将模具放入平板硫化机，8MPa下，热压500s，之后冷压400s，制成试样薄片。用标准尺寸裁刀在气动切片机上将薄片切成测试所需的样条，以待测试各项性能时使用。
实施例四
将EVA(9.3g)、磷系阻燃剂BDP(0.2g)、抗滴落剂硼酸锌(0.1g)、交联剂DCP(0.2g)和转光剂 Eu(SA)3phen(0.2g)采用炼塑机双辊开炼混合，混合温度为冷辊室温，混合时间为4.5min。按照相关标准选用合适的模具，把混合材料样品倒入模具中，当平板硫化机温度上升到180℃时，将模具放入平板硫化机，13MPa下，热压550s，之后冷压450s，制成试样薄片。用标准尺寸裁刀在气动切片机上将薄片切成测试所需的样条，以待测试各项性能时使用。
实施例五
将EVA(9.7g)、磷系阻燃剂TPP(0.1g)、抗滴落剂硼酸锌(0.1g)和转光剂Eu(DBM)3phen(0.1g) 采用炼塑机双辊开炼混合，混合温度为冷辊室温，混合时间为5min。按照相关标准选用合适的模具，把混合材料样品倒入模具中，当平板硫化机温度上升到160℃时，将模具放入平板硫化机，20MPa下，热压600s，之后冷压500s，制成试样薄片。用标准尺寸裁刀在气动切片机上将薄片切成测试所需的样条，以待测试各项性能时使用。
实施例六
将EVA(9.4g)、磷系阻燃剂TCP(0.2g)、抗滴落剂四氟乙烯(0.1g)、交联剂DTBP(0.1g)和转光剂Eu(SA)3phen(0.2g)采用炼塑机双辊开炼混合，混合温度为冷辊室温，混合时间为4min。按照相关标准选用合适的模具，把混合材料样品倒入模具中，当平板硫化机温度上升到200℃时，将模具放入平板硫化机，12MPa下，热压400s，之后冷压300s，制成试样薄片。用标准尺寸裁刀在气动切片机上将薄片切成测试所需的样条，以待测试各项性能时使用。
测试方法
1.极限氧指数测试
按照ASTM D2863-09标准，用南京上元分析仪器有限公司的HC-2CZ氧指数测定仪对样条进行测试，将固定规格的样条放置于夹具上在不同氧浓度的条件下点燃，测量支持样条燃烧的最低氧浓度，氧气和氮气混合气体的流速为10L/min。
2.垂直燃烧试验
采用南京市江宁区分析仪器厂CZF-6型水平垂直燃烧测定仪，通过UL-94垂直燃烧实验测试制备好的 EVA样条的阻燃性能，垂直燃烧测试(UL-94)是在垂直悬挂在棉絮上方(用于识别滴落物)的测试样本上进行的，根据美国国家标准UL-94-2006进行定义。
3.透光率测试
选用紫外-可见分光光度计UV3600，把空气作为背景，将EVA胶膜贴于通光口上，遮住光路，测试材料在200～700nm光区内的透光率。
4.荧光性能测试
测试仪器为紫外-荧光分光光度计Varian，把裁剪好的样片贴于样品台上，在300～500nm紫外光区测试激发光谱，寻找最大激发峰的波长λex，再在λex波长激发下测定发射光谱，找出最大发射峰位置λem。
5.薄膜拉伸性能测定
参照国际标准ISO1184-1983《塑料薄膜拉伸性能的测定》，薄膜厚度0.2mm。
附表1 复合材料的性能测试数据
| 实施例一 | 实施例二 | 实施例三 | 实施例四 | 实施例五 | 实施例六 | |
| 氧指数LOI/％ | 20.1 | 30.6 | 29.1 | 28.6 | 28.2 | 29.0 |
| UL-94 | V-2 | V-0 | V-0 | V-0 | V-1 | V-0 |
| 是否存在熔滴 | 是 | 否 | 否 | 否 | 否 | 否 |
| 透光率/％ | 89.8 | 91.2 | 90.5 | 92.4 | 92.9 | 90.5 |
| 荧光强度 | 82.7 | 81.3 | 78.2 | 81.7 | 78.8 | 81.5 |
| 拉伸强度/Mp | 22.1 | 23.8 | 26.5 | 27.6 | 22.3 | 28.3 |
Claims (9)
1.一种掺稀土有机配合物阻燃抗滴落转光膜及其制备方法，其特征在于，包括如下步骤：
将转光薄膜基材、磷系阻燃剂、抗滴落剂、交联剂和转光剂按比例采用炼塑机双辊开炼混合，混合温度为冷辊室温，混合时间为3～5min，挤出造粒后，冷却切粒、烘干，将混合好的料在平板硫化仪上模压成型，裁切出测试所需规格的样条。
2.根据权利要求1所述的方法，其特征在于，转光薄膜的基材为乙烯-醋酸乙烯共聚物(EVA)，VA的含量为1～15％。
3.根据权利要求1所述的方法，其特征在于，所述的磷系阻燃剂为磷酸三甲苯酯(TCP)、磷酸甲苯二苯酯(CDP)、异丙基化磷酸三苯酯(IPPP)、双酚A双(二苯基磷酸酯)(BDP)和磷酸三苯酯(TPP)等中的一种或两种的混合物。
4.根据权利要求1所述的方法，其特征在于，抗滴落剂为聚四氟乙烯、硼酸锌中的一种。
5.根据权利要求1所述的方法，其特征在于，交联剂为过氧化二异丙苯(DCP)，2，5-二甲基-2，5-双-(叔丁基过氧化)己烷(DTBP)。
6.根据权利要求1所述的方法，其特征在于，转光剂为一系列含铕(Eu)稀土有机配合物中的一种，如Eu(TTA)3dpbt、Eu(SA)3phen、Eu(DBM)3phen等，其中TTA为α-噻吩基甲酰三氟丙酮，SA为水杨酸，phen为邻菲罗啉，DBM为二苯甲酰甲烷，dpbt为2-(N，N-二乙基苯胺-4-基)-4，6-二(3，5-二甲基吡唑-1-基)-1，3，5-三嗪。
7.根据权利要求4所述的稀土有机配合物转光剂，其特征在于，Eu(TTA)3dpbt在紫外光区200～400nm范围内有较好的吸收，Eu(SA)3phen在紫外光区300～330nm范围内有较好的吸收，Eu(DBM)3phen在紫外光区250～400nm范围内有较好的吸收。
8.根据权利要求1所述的一种掺稀土有机配合物阻燃抗滴落转光膜的制备方法，其特征在于，包括如下步骤：
1)将转光膜基材、磷系阻燃剂和转光剂按比例采用炼塑机双辊开炼混合，混合温度为冷辊室温，混合时间为3～5min。
2)按照相关标准选用合适的模具，把混合材料样品倒入模具中，当平板硫化机温度上升到100～200℃时，将模具放入平板硫化机，8～20MPa下，热压400～600s，之后冷压300～500s，制成试样薄片。用标准尺寸裁刀在气动切片机上将薄片切成测试所需的样条，以待测试各项性能时使用。
9.根据权利要求1所述的方法，其特征在于，在上述反应中，转光膜基材、阻燃剂、抗滴落剂、交联剂和转光剂的质量比＝92～97∶1～5∶0～2∶0～5∶1～3。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006298974A (ja) * | 2005-04-15 | 2006-11-02 | National Institute Of Advanced Industrial & Technology | エチレン−酢酸ビニル共重合体組成物 |
| CN102559079A (zh) * | 2012-01-09 | 2012-07-11 | 苏州泰科尼光伏材料有限公司 | 一种用于太阳能电池封装的eva胶膜 |
| CN103739926A (zh) * | 2013-12-31 | 2014-04-23 | 杭州索康博能源科技有限公司 | 一种荧光性eva胶膜 |
| CN104108215A (zh) * | 2014-06-30 | 2014-10-22 | 安徽巢湖南方膜业有限责任公司 | 一种高转光率农用大棚膜及其制备方法 |
-
2020
- 2020-06-09 CN CN202010521801.8A patent/CN111592712A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006298974A (ja) * | 2005-04-15 | 2006-11-02 | National Institute Of Advanced Industrial & Technology | エチレン−酢酸ビニル共重合体組成物 |
| CN102559079A (zh) * | 2012-01-09 | 2012-07-11 | 苏州泰科尼光伏材料有限公司 | 一种用于太阳能电池封装的eva胶膜 |
| CN103739926A (zh) * | 2013-12-31 | 2014-04-23 | 杭州索康博能源科技有限公司 | 一种荧光性eva胶膜 |
| CN104108215A (zh) * | 2014-06-30 | 2014-10-22 | 安徽巢湖南方膜业有限责任公司 | 一种高转光率农用大棚膜及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 董劲: "Eu配合物/EVA复合膜的制备及在晶体硅太阳能电池中的应用研究", 《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅱ辑》 * |
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