CN113402773A - 一种无卤阻燃剂及其制备方法和应用 - Google Patents
一种无卤阻燃剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种无卤阻燃剂及其制备方法,该阻燃剂具有如式(1)所示的结构式,其是双(4‑羟苯基)苯膦氧化物与环氧氯丙烷进行取代反应得到。本发明还公开了上述无卤阻燃剂在阻燃聚酯材料,特别是阻燃聚酯薄膜制备中的应用。本发明的无卤阻燃剂将阻燃组份以偶联的形式引入聚酯结构中,可以有效避免阻燃组份在聚酯材料中长期使用后发生迁移甚至析出的情况,降低聚酯的端羧基含量,提高聚酯的分子量。本发明的阻燃组分通过磷提供阻燃作用,其主要通过热分解在聚合物表面形成磷酸和多磷酸的粘膜层,使聚合物达到难燃的目的;其无卤、无毒、低烟,不产生腐蚀性气体,抗紫外照射,符合环保的发展方向。
Description
技术领域
本发明涉及阻燃剂技术领域,尤其涉及一种无卤阻燃剂及其制备方法和应用。
背景技术
双向拉伸聚酯薄膜(BOPET)是以聚对苯二甲酸乙二醇酯为原料,采用多层共挤出法制成厚片,再经双向拉伸制成的薄膜材料。BOPET具有优异的机械性能,刚性、韧性高,热稳定性、气体阻隔性良好,高透光率,质量轻,价格低等优良特性,因而被广泛应用于各种包装材料、电气绝缘材料、印刷电路板等各个领域。
现有技术中,较为普遍的聚酯阻燃技术为共聚法和共混法。共聚法采用共聚型的阻燃剂与对苯二甲酸和乙二醇进行共聚,制备阻燃聚酯切片,再进行拉膜;但这种方法存在共聚成本高,工艺复杂,设备投资大等缺陷,同时分子链上阻燃剂分子的引入会改变聚酯基体玻璃化转变温度及熔点。共混法采用阻燃剂与聚酯切片进行共混、挤出做成阻燃母粒,然后阻燃母粒再与聚酯切片进行熔融挤出铸片,最后拉膜;通常共混阻燃虽能在一定程度上改善阻燃性能,但由于这些小分子化合物的阻燃剂添加量大,与树脂基材相容性差,使得聚酯材料的机械性能不稳定,长期使用会出现阻燃剂的迁移和析出,影响聚酯制品的外观和阻燃效果的持久性。
因此,开发一种既能使聚酯材料具有阻燃性能,又能避免对聚酯材料的机械性能以及稳定性产生不良影响的阻燃剂,具有十分重要的价值。
发明内容
基于背景技术存在的技术问题,本发明提出了一种无卤阻燃剂及其制备方法和应用。
本发明提出的一种无卤阻燃剂,其具有如式(1)所示的结构式:
优选地,所述的无卤阻燃剂的制备方法,包括:在有机溶剂和碱的存在下,将双(4-羟苯基)苯膦氧化物与环氧氯丙烷进行取代反应,即得。
优选地,所述双(4-羟苯基)苯膦氧化物与环氧氯丙烷的摩尔比为1:(2.5~3.5);优选地,所述双(4-羟苯基)苯膦氧化物与碱的摩尔比为1:(1~2);优选地,所述取代反应的反应温度为80~100℃,反应时间为6~8h;优选地,所述碱为氢氧化钠、氢氧化钾或其组合;优选地,所述有机溶剂为四氢呋喃、N,N-二甲基甲酰胺或其组合。
优选地,所述的无卤阻燃剂的制备方法包括:将双(4-羟苯基)苯膦氧化物和碱溶解于有机溶剂中,然后加入环氧氯丙烷,在碱性条件下进行取代反应,即得;优选地,溶解温度为50~80℃,溶解时间为1~3h。
所述的无卤阻燃剂的反应路线如下:
所述的无卤阻燃剂在阻燃聚酯材料制备中的应用,所述阻燃聚酯材料的原料包括含端羧基的聚酯树脂。
优选地,所述无卤阻燃剂占聚酯材料总质量的0.4~1.6%;优选地,所述阻燃聚酯材料的制备方法包括:将所述的无卤阻燃剂与含端羧基的聚酯树脂共混熔融挤出,使无卤阻燃剂中的环氧基团与聚酯树脂的端羧基发生偶联反应;优选地,熔融挤出的温度为270~285℃。
所述的无卤阻燃剂在阻燃聚酯薄膜制备中的应用,所述阻燃聚酯薄膜包括阻燃层,所述阻燃层的原料包括含端羧基的聚酯树脂和所述无卤阻燃剂;优选地,所述无卤阻燃剂的质量占阻燃层原料总质量的0.5~2%;优选地,所述阻燃层的厚度占薄膜厚度的40~100%,优选为60~90%。
其中,阻燃聚酯薄膜的制备方法包括将阻燃层的原料经过共混熔融挤出处理。
工业中使用的聚酯树脂通常是由多元醇和多元酸通过聚酯化反应合成的,由于反应的原料选择和工艺条件等原因,很多聚酯树脂产品中含有未反应的端羧基;尤其是对于用于薄膜制备的膜级聚酯切片,在实际生产中,由于生产工艺方法和参数控制,未酯化的对苯二甲酸的残存羧基和反应过程中的热降解、热氧化的降解等副反应引起切片中端羧基的产生,因此端羧基是膜级聚酯切片生产的一个重要的质量指标,其大小直接影响切片的热稳定性、色相和成膜品质。基于此,本发明所述无卤阻燃剂在阻燃聚酯材料,特别是阻燃聚酯薄膜制备中应用的阻燃作用机理为:当聚酯树脂中含有未反应的端羧基时,在熔融挤出时,端羧基易与所述无卤阻燃剂中的环氧基团发生反应,降低端羧基含量,提高聚酯分子量,同时将磷引入到大分子链上,达到阻燃效果。具体包括:
两分子PET的端羧基与一分子双环氧化合物反应时,发生两分子PET偶联反应,扩链增粘,使端羧基含量降低,反应式如下:
一个PET端羧基反应与一分子双环氧化合物反应时,得到环氧基团封端的PET分子,反应式如下:
一种阻燃双向拉伸聚酯薄膜,依次包括上表层、中间层和下表层,所述中间层为阻燃层,其原料按质量百分比计包括:膜级聚酯切片97.5~99.5%、所述的无卤阻燃剂0.5~2%、抗氧剂0~0.5%。
其中,膜级聚酯切片含端羧基。
优选地,所述抗氧剂为1010、抗氧剂168或其组合;优选地,所述抗氧剂由抗氧剂1010和抗氧剂168组成,其中抗氧剂1010和抗氧剂168的质量比为1:1。
优选地,所述中间层的厚度占聚酯薄膜厚度的40~100%,优选为60~90%;优选地,所述聚酯薄膜的厚度为9~23μm;优选地,所述上表层、下表层为抗粘连层,其原料按质量百分比计包括:膜级聚酯切片30~40%、抗粘母料60~70%;优选地,所述抗粘母料中含有3000~3300ppm的爽滑粒子;优选地,所述爽滑粒子为二氧化硅、高岭土、碳酸钙、硫酸钡、PMMA中的至少一种,其粒径为2.0~3.5μm。
一种所述的阻燃双向拉伸聚酯薄膜的制备方法,包括下述步骤:
S1、分别将上表层、中间层和下表层的原料共混,在不同的挤出机中熔融挤出,过滤得到上表层熔体、中间层熔体和下表层熔体,其中中间层的原料的熔融挤出温度275~280℃,上表层的原料和下表层的原料的熔融挤出温度为270~275℃;
S2、将所述上表层熔体、中间层熔体和下表层熔体由模头共挤出,流延到激冷辊上铸片,形成铸片,其中模头温度270~280℃,激冷辊温度为25~30℃;
S3、将所述铸片进行纵向拉伸得到纵拉片,其中纵向拉伸温度为108~115℃,纵向拉伸比为4.0~4.5;
S4、将所述纵拉片进行横向拉伸,然后退火定型、冷却,即得,其中横向拉伸温度为110~130℃,横向拉伸比为3.5~4.0,定型温度为235~245℃,冷却温度为80~100℃。
本发明提供的阻燃剂通过聚酯端羧基反应引入到大分子链中,使薄膜具有阻燃性能,同时降低聚酯端羧基含量。解决了小分子阻燃剂的添加量大的问题,避免影响到聚酯薄膜的机械性能的稳定性。阻燃剂及阻燃聚酯薄膜制备方法工艺简单,易于操作。
本发明的有益效果如下:
本发明的无卤阻燃剂可以通过阻燃剂中环氧基团与PET分子的端羧基之间的反应,将阻燃组份磷元素以偶联的形式引入聚酯结构中,一方面,磷元素作为阻燃组分,其主要通过热分解在聚合物表面形成磷酸和多磷酸的粘膜层,可以使聚合物达到难燃的目的,无卤、无毒、低烟,不产生腐蚀性气体,抗紫外照射,符合环保的发展方向;另一方面,通过阻燃剂中环氧基团与PET分子的端羧基之间的反应将磷元素以偶联的形式引入聚酯结构中,可以有效避免阻燃组份在聚酯材料中长期使用后发生迁移甚至析出的情况,提高阻燃组分与聚酯的相容性,降低聚酯的端羧基含量,提高聚酯的分子量,从而可以改善聚酯材料的阻燃效果持久性、外观效果,并且使聚酯具有良好的机械性能。
附图说明
图1为实施例1制备的无卤阻燃剂的核磁共振谱图。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明。
下述实施例和对比例中,膜级聚酯切片产自仪征化纤,型号为FG620。
实施例1
一种无卤阻燃剂,其具有如式(1)所示的结构式:
其制备方法如下:将1mol双(4-羟苯基)苯膦氧化物加入到500mL四氢呋喃中,搅拌后加入1mol氢氧化钠,在60℃搅拌2h,再加入2.5mol环氧氯丙烷,缓慢升温到90℃反应7h,冷却至室温后,过滤、洗涤、干燥,得到式(1)所示的无卤阻燃剂,命名为4,4-二(4-(环氧丙基)苯基)苯基膦酸酯;其核磁共振谱图如图1所示。
实施例2
一种阻燃双向拉伸聚酯薄膜,依次包括上表层、中间层和下表层,中间层为阻燃层,其原料按质量百分比计包括:膜级聚酯切片99%、所述的无卤阻燃剂0.5%、抗氧剂0.5%。
其中,抗氧剂由抗氧剂1010和抗氧剂168组成,其中抗氧剂1010和抗氧剂168的质量比为1:1。
上表层、下表层为抗粘连层,其原料按质量百分比计包括:膜级聚酯切片35%、抗粘母料65%,其中抗粘母料中含有3300ppm的爽滑粒子,爽滑粒子为粒径为3.0μm的二氧化硅。
中间层的厚度为10μm,上表层的厚度为2.5μm,下表层的厚度为2.5μm。
制备阻燃双向拉伸聚酯薄膜:
S1、分别将上表层、中间层和下表层的原料共混,在不同的挤出机中熔融挤出,过滤得到上表层熔体、中间层熔体和下表层熔体,其中中间层的原料的熔融挤出温度275~280℃,上表层的原料和下表层的原料的熔融挤出温度为270~275℃;
S2、将所述上表层熔体、中间层熔体和下表层熔体由模头共挤出,流延到激冷辊上铸片,形成铸片,其中模头温度270~280℃,激冷辊温度为25~30℃;
S3、将所述铸片进行纵向拉伸得到纵拉片,其中纵向拉伸温度为108~115℃,纵向拉伸比为4.0~4.5;
S4、将所述纵拉片进行横向拉伸,然后退火定型、冷却,即得,其中横向拉伸温度为110~130℃,横向拉伸比为3.5~4.0,定型温度为235~245℃,冷却温度为80~100℃。
实施例3
实施例3与实施例2的区别仅为:中间层的原料不同,具体如下:
中间层为阻燃层,其原料按质量百分比计包括:膜级聚酯切片98.5%、所述的无卤阻燃剂1.0%、抗氧剂0.5%。
实施例4
实施例4与实施例2的区别仅为:中间层的原料不同,具体如下:
中间层为阻燃层,其原料按质量百分比计包括:膜级聚酯切片98%、所述的无卤阻燃剂1.5%、抗氧剂0.5%。
实施例5
实施例4与实施例2的区别仅为:中间层的原料不同,具体如下:
中间层为阻燃层,其原料按质量百分比计包括:膜级聚酯切片97.5%、所述的无卤阻燃剂2%、抗氧剂0.5%。
对比例1
对比例1与实施例2的区别仅为:中间层的原料不同,具体如下:
中间层的原料按质量百分比计包括:膜级聚酯切片99.5%、抗氧剂0.5%。
对比例2
对比例1与实施例2的区别仅为:中间层的原料不同,具体如下:
中间层的原料按质量百分比计包括:膜级聚酯切片99%、阻燃剂0.5%、抗氧剂0.5%,其中阻燃剂为双(4-羟苯基)苯膦氧化物。
对实施例2-5和对比例1-2制得的双向拉伸聚酯薄膜进行性能测试,测试结果见表1。
表1双向拉伸聚酯薄膜的性能测试结果
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
2.一种如权利要求1所述的无卤阻燃剂的制备方法,其特征在于,包括:在有机溶剂和碱的存在下,将双(4-羟苯基)苯膦氧化物与环氧氯丙烷进行取代反应,即得。
3.根据权利要求2所述的无卤阻燃剂的制备方法,其特征在于,所述双(4-羟苯基)苯膦氧化物与环氧氯丙烷的摩尔比为1:(2.5~3.5);优选地,所述双(4-羟苯基)苯膦氧化物与碱的摩尔比为1:(1~2);优选地,所述取代反应的反应温度为80~100℃,反应时间为6~8h;优选地,所述碱为氢氧化钠、氢氧化钾或其组合;优选地,所述有机溶剂为四氢呋喃、N,N-二甲基甲酰胺或其组合。
4.根据权利要求2或3所述的无卤阻燃剂的制备方法,其特征在于,包括:将双(4-羟苯基)苯膦氧化物和碱溶解于有机溶剂中,然后加入环氧氯丙烷,在碱性条件下进行取代反应,即得;优选地,溶解温度为50~80℃,溶解时间为1~3h。
5.权利要求1所述的无卤阻燃剂在阻燃聚酯材料制备中的应用,其特征在于,所述阻燃聚酯材料的原料包括含端羧基的聚酯树脂。
6.根据权利要求5所述的应用,其特征在于,所述无卤阻燃剂占聚酯材料总质量的0.4~1.6%;优选地,所述阻燃聚酯材料的制备方法包括:将所述的无卤阻燃剂与含端羧基的聚酯树脂共混熔融挤出。
7.权利要求1所述的无卤阻燃剂在阻燃聚酯薄膜制备中的应用,其特征在于,所述阻燃聚酯薄膜包括阻燃层,所述阻燃层的原料包括含端羧基的聚酯树脂和所述无卤阻燃剂;优选地,所述无卤阻燃剂的质量占阻燃层原料总质量的0.5~2%;优选地,所述阻燃层的厚度占薄膜厚度的40~100%,优选为60~90%。
8.一种阻燃双向拉伸聚酯薄膜,其特征在于,依次包括上表层、中间层和下表层,所述中间层为阻燃层,其原料按质量百分比计包括:膜级聚酯切片97.5~99.5%、权利要求1所述的无卤阻燃剂0.5~2%、抗氧剂0~0.5%。
9.根据权利要求8所述的阻燃双向拉伸聚酯薄膜,其特征在于,所述中间层的厚度占聚酯薄膜厚度的40~100%,优选为60~90%;优选地,所述聚酯薄膜的厚度为9~23μm;优选地,所述上表层、下表层为抗粘连层,其原料按质量百分比计包括:膜级聚酯切片30~40%、抗粘母料60~70%;优选地,所述抗粘母料中含有3000~3300ppm的爽滑粒子;优选地,所述爽滑粒子为二氧化硅、高岭土、碳酸钙、硫酸钡、PMMA中的至少一种,其粒径为2.0~3.5μm。
10.一种如权利要求8或9所述的阻燃双向拉伸聚酯薄膜的制备方法,其特征在于,包括下述步骤:
S1、分别将上表层、中间层和下表层的原料共混,在不同的挤出机中熔融挤出,过滤得到上表层熔体、中间层熔体和下表层熔体,其中中间层的原料的熔融挤出温度275~280℃,上表层的原料和下表层的原料的熔融挤出温度为270~275℃;
S2、将所述上表层熔体、中间层熔体和下表层熔体由模头共挤出,流延到激冷辊上铸片,形成铸片,其中模头温度270~280℃,激冷辊温度为25~30℃;
S3、将所述铸片进行纵向拉伸得到纵拉片,其中纵向拉伸温度为108~115℃,纵向拉伸比为4.0~4.5;
S4、将所述纵拉片进行横向拉伸,然后退火定型、冷却,即得,其中横向拉伸温度为110~130℃,横向拉伸比为3.5~4.0,定型温度为235~245℃,冷却温度为80~100℃。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102634064A (zh) * | 2012-04-10 | 2012-08-15 | 宁波长阳科技有限公司 | 一种含磷阻燃剂、阻燃聚酯薄膜及其制备方法 |
JP2013256554A (ja) * | 2012-06-11 | 2013-12-26 | Toyobo Co Ltd | 難燃性ポリエステルおよび難燃性ポリエステルフィルム |
CN104558601A (zh) * | 2015-01-09 | 2015-04-29 | 西北工业大学 | 一种含磷阻燃型氰酸酯树脂及其制备方法 |
CN105315625A (zh) * | 2014-06-25 | 2016-02-10 | 江苏裕兴薄膜科技股份有限公司 | 一种无卤阻燃聚酯薄膜及其制备方法 |
CN105479880A (zh) * | 2015-12-06 | 2016-04-13 | 安徽国风塑业股份有限公司 | 一种高耐击穿、阻燃双向拉伸聚酯薄膜及其制备方法 |
-
2021
- 2021-05-25 CN CN202110574139.7A patent/CN113402773A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102634064A (zh) * | 2012-04-10 | 2012-08-15 | 宁波长阳科技有限公司 | 一种含磷阻燃剂、阻燃聚酯薄膜及其制备方法 |
JP2013256554A (ja) * | 2012-06-11 | 2013-12-26 | Toyobo Co Ltd | 難燃性ポリエステルおよび難燃性ポリエステルフィルム |
CN105315625A (zh) * | 2014-06-25 | 2016-02-10 | 江苏裕兴薄膜科技股份有限公司 | 一种无卤阻燃聚酯薄膜及其制备方法 |
CN104558601A (zh) * | 2015-01-09 | 2015-04-29 | 西北工业大学 | 一种含磷阻燃型氰酸酯树脂及其制备方法 |
CN105479880A (zh) * | 2015-12-06 | 2016-04-13 | 安徽国风塑业股份有限公司 | 一种高耐击穿、阻燃双向拉伸聚酯薄膜及其制备方法 |
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