CN110982051B - 一种阻燃抗紫外pet及其制备方法 - Google Patents
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Abstract
本发明涉及高分子材料领域,尤其涉及一种阻燃抗紫外PET及其制备方法。本发明提供一种阻燃抗紫外PET,其分子结构上同时含有抗紫外老化和阻燃效果的结构,现有技术中对于这种兼具阻燃和抗老化性能的反应改性型PET鲜有报道,本发明所制备的阻燃抗紫外PET不仅具有良好的力学性能,其极限氧指数可达35%以上,紫外光照射老化试验后的PET熔融纺丝的断裂强度可达4.0cN/dtex以上,断裂伸长率可达30%以上。
Description
技术领域
本发明涉及聚酯材料领域,尤其涉及一种阻燃抗紫外PET及其制备方法。
背景技术
聚对苯二甲酸乙二醇脂(PET),属于高分子化合物,是由对苯二甲酸(PTA)和乙二醇缩聚得到,PET具有良好的物理性能,但其极限氧指数(LOI)为22%左右。
PET在服装、布料、床上用品等领域有着广泛的应用,然而PET本身具有易燃性,一旦发生火灾将给生命财产带来极大的损害,因此,提高PET的阻燃性能有着非常重要的意义。
目前,对PET阻燃改性的主要方法是对其添加阻燃剂进行共混,普遍存在着添加量大、相容性差、易析出等问题,特别是某些添加型阻燃剂可能导致PET的机械性能下降。鉴于此,研究者们对PET进行化学改性,希望得到本身就具有阻燃性能的PET,从而实现PET的本质阻燃。研究者们对PET进行化学改性主要从两个方面着手,(1)通过共聚、接枝等手段在聚合主链或者侧链引入磷、氮、硅和卤素等阻燃元素,获得本身具有阻燃性的聚合物;(2)设计一些主链含有特殊化学结构的聚合物,使材料自身具有耐高温、抗氧化、不易燃、阻燃功能持久等特点。例如四川大学王玉忠院士课题组设计公开了一种两端含有羟基的钠离子含磷单体DHPPQ-Na(Zhang Y,Chen L,Zhao J J,et al.A phosphorus-containing PETionomer:from ionic aggregates to flame retardance and restricted melt-dripping[J].Polymer Chemistry,2014,5(6):1982-1991.),具体公开了DHPPQ-Na与对苯二酸和乙二醇共聚,制备了含离子基团的共聚酯PETIn,相对于纯PET,PETIn的LOI由22%提高至31%,王玉忠院士课题组还公开了系列芳香结构单体(Guo D M,Chen X Q,Tang L,etal.PET-based copolyesters with bisphenol A or bisphenol F structural units:Their distinct differences in pyrolysis behaviours and flame-retardantperformances[J].Polymer Degradation and Stability,2015,120:158-168.),具体公开了系列芳香结构单体含苯乙炔、双酚A、芳基醚等结构,与对苯二酸和乙二醇共聚后都能明显提高PET的热稳定性,当共聚酯主链含Ar-O-Ar-O-Ar结构时,LOI可提高至34.1%,燃烧级别达到UL94 V-0级。
近年来,由于大气层遭到破坏,到达地面的紫外线辐射量增多,长时间的紫外线照射会引起纺织品的褪色和老化,因此,抗紫外PET布料也越来越引起人们的关注,对PET布料进行紫外线屏蔽处理成为了切实的需要。但是目前制备具有抗紫外效果的PET纤维制品大都是在PET聚酯基体中添加抗紫外的粉体共混,抗紫外粉体的加入很可能会使得PET纤维的力学性能变差,例如中国发明专利CN 107987317 A公开了一种抗紫外PET纤维,其制备方法是在PET基体中加入抗紫外粉体、抗氧化剂等成分熔融共混,其所制备的抗紫外的PET纤维的UVA透过率≤0.6%,UVB透过率≤0.2%,UPF值≥50,但是PET纤维的拉伸强度仅为3.4-3.8cN/dtex,纤维伸长率仅为26.3-28.2%,力学性能有所损耗。
虽然通过化学改性的方法可以使得PET本身具有阻燃性,单纯的PET与抗紫外粉体熔融共混制得的复合材料具有抗紫外性能,但是目前关于化学改性方法制备本身兼具抗紫外和阻燃性能的PET鲜有报道。
发明内容
针对现有技术的不足,本发明要解决的技术问题是:如何通过化学改性的方法制备一种力学性能优异,本身兼具阻燃性和抗紫外性能的PET。本发明提供一种阻燃抗紫外PET,其分子结构上含有抗紫外线和阻燃效果的结构,具有较好的力学性能,比普通的阻燃PET具有更好的阻燃效果,在紫外线照射老化试验中具有优异的表现。
本发明解决其技术问题所采用的技术方案是:本发明提供一种阻燃抗紫外PET,其反应过程如下:
本发明的阻燃抗紫外PET制备方法如下:
步骤(1):丁二酸酐与间苯二酚单苯甲酸酯发生酯化反应,丁二酸酐与间苯二酚单苯甲酸酯的摩尔比为1.15:1,酯化反应温度为150-180℃,反应时间3h,催化剂I为浓硫酸、对甲苯磺酸、高氯酸、氯化锌、无水乙酸钠、吡啶、二甲基苯胺中的一种,催化剂的用量为醇酸总质量的0.032wt.%,反应结束后生成产物I;
步骤(2):产物I与阻燃剂Q发生酯化反应,产物I与X的质量比为1:0.53,酯化反应温度为200-230℃,反应时间3h,催化剂Ⅱ为浓硫酸、对甲苯磺酸、高氯酸、氯化锌、无水乙酸钠、吡啶、二甲基苯胺中的一种,催化剂的用量为产物I和阻燃剂Q总质量的0.032wt.%,反应结束后生成产物Ⅱ,其中Q的分子结构为
步骤(3):产物Ⅱ与氯乙醇发生反应,产物Ⅱ与氯乙醇的质量比为6:1,反应温度为95-100℃,反应时间为2h,催化剂Ⅲ为有机钠催化剂,催化剂Ⅲ的用量为产物Ⅱ和与氯乙醇总质量的0.02wt.%,反应结束后生成产物Ⅲ;
步骤(4):产物Ⅲ与对苯二甲酸、乙二醇在氮气保护下进行反应,氮气压力为0.02MPa,搅拌速度为35r/min,逐步升温至酯化温度230-235℃,待水的蒸出量达到理论值的90%,泄压至常压,酯化结束,对苯二甲酸与产物Ⅲ和乙二醇总量的摩尔比为1:1.4-1.6,产物Ⅲ与乙二醇的质量比为10-20:1,催化剂Ⅳ为锑系催化剂或有机锡类催化剂中的一种,稳定剂为磷酸、亚磷酸、亚磷酸酯中的一种,催化剂Ⅳ的用量为产物Ⅲ、对苯二甲酸和乙二醇总质量的0.0035wt.%,稳定剂的用量为产物Ⅲ、对苯二甲酸和乙二醇总质量的0.001wt.%;
预缩聚:40min内将真空度降为100Pa,缓慢升温至270℃;
缩聚:设定缩聚温度270℃,增大转速为60r/min,保持真空度为100Pa,待搅拌功率提高到21W时出料,即获得具有抗紫外和阻燃效果的目标产物阻燃抗紫外PET。
所述步骤(4)中的锑系催化剂为三氧化二锑、醋酸锑、乙二醇锑中的一种,有机锡类催化剂为二丁基锡二月桂酸酯、二(十二烷基硫)二丁基锡、二醋酸二丁基锡中的一种;
所述步骤(3)中的有机钠催化剂为柠檬酸三钠或十二烷基苯磺酸钠中的一种。
所述步骤(2)中阻燃剂Q的制备方法如下:
将氰尿酸(IA)加入到25g二甲基亚砜(DMSO)中并磁力搅拌,溶液温度加热到110-130℃,搅拌均匀后加入1,3-二氧杂环环戊酮(EC)、K2CO3、催化剂三乙胺,IA和EC在DMSO中的浓度为2mol/Kg,三乙胺在DMSO中的浓度为0.0288mol/Kg,K2CO3在DMSO中的浓度为0.0576mol/Kg,继续反应0.8h,反应结束后得到阻燃剂Q。
本发明的有益效果是:
(1)本发明所制备的PET本身具有阻燃和抗紫外老化的双重功能。
(2)本发明所制备的PET具有较好的阻燃效果,其极限氧指数可达35%以上。
(3)本发明所制备的PET具有较好的抗紫外老化的性能,紫外光照射老化试验后的PET熔融纺丝的断裂强度可达4.0cN/dtex以上,断裂伸长率可达30%以上。
附图说明
图1:是实施例1所制备产物Ⅲ的1HNMR谱图。
具体实施方式
现在结合实施例对本发明作进一步详细的说明。
实施例1
步骤(1)将氰尿酸IA加入到25g DMSO中并磁力搅拌,溶液温度加热到110℃,搅拌均匀后加入EC、K2CO3、催化剂三乙胺,IA和EC在DMSO中的浓度为2mol/Kg,三乙胺在DMSO中的浓度为0.0288mol/Kg,K2CO3在DMSO中的浓度为0.0576mol/Kg,继续反应0.8h,反应结束后得到阻燃剂Q。
步骤(2)丁二酸酐与间苯二酚单苯甲酸酯发生酯化反应,丁二酸酐与间苯二酚单苯甲酸酯的摩尔比为1.15:1,酯化反应温度为150℃,反应时间3h,催化剂为浓硫酸,催化剂的用量为醇酸总质量的0.032wt.%,反应结束后生成产物I;
步骤(3)产物I与阻燃剂Q发生酯化反应,产物I与阻燃剂Q的质量比为1:0.53,酯化反应温度为230℃,反应时间3h,催化剂为对甲苯磺酸,催化剂的用量为产物I和阻燃剂Q总质量的0.032wt.%,反应结束后生成产物Ⅱ;
步骤(4)产物Ⅱ与氯乙醇发生反应生成,产物Ⅱ与氯乙醇的质量比为6:1,反应温度为95℃,反应时间为2h,催化剂为柠檬酸三钠,催化剂的用量为产物Ⅱ和与氯乙醇总质量的0.02wt.%,反应结束后生成产物Ⅲ,图1是产物Ⅲ的1HNMR特征吸收谱图(CDCl3作溶剂):δ=7.46~8.15(苯环结构),δ=4.80~4.82(a,2H),δ=4.49~4.52(b,2H),δ=3.60~3.64(c,4H),δ=3.36~3.41(d,6H),δ=2.51~2.54(e,2H),δ=2.34~2.40(f,2H),δ=2.22~2.26(g,2H);
步骤(5)产物Ⅲ与对苯二甲酸、乙二醇、催化剂、稳定剂在氮气保护下进行反应,氮气压力为0.02MPa,搅拌速度为35r/min,逐步升温至酯化温度230℃,待水的蒸出量达到理论值的90%,泄压至常压,酯化结束,对苯二甲酸与产物Ⅲ和乙二醇总量的摩尔比为1:1.4-1.6,产物Ⅲ与乙二醇质量比为10:1,催化剂为乙二醇锑,稳定剂为磷酸,催化剂的用量为产物Ⅲ、对苯二甲酸和乙二醇总质量的0.0035wt.%,稳定剂的用量为产物Ⅲ、对苯二甲酸和乙二醇总质量的0.001wt.%;
预缩聚:40min内将真空度降为100Pa,缓慢升温至270℃;
缩聚:设定缩聚温度270℃,增大转速为60r/min,保持真空度为100Pa,待搅拌功率提高到21W时出料,即获得具有抗紫外和阻燃效果的目标产物阻燃抗紫外PET。
实施例2-13同实施例1,不同之处在于见表1和表2:
表1
表2
本法所制备的PET阻燃性能测试见表3:
表3
将本法所制备的PET熔融纺丝制备PET纤维,工艺参数:
纺丝温度:283℃,
侧吹风冷却风温:29℃;
侧吹风风速:0.4m/s;
卷绕纺丝速度:3750m/min;
牵伸倍率:3.5。
将本法所制备的PET纤维加工成薄型平纹织物,并按照GB/T18830-2002方法进行测试,性能测试见表4:
表4
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (5)
2.根据权利要求1所述的阻燃抗紫外PET的制备方法,其特征在于:由以下步骤制备:
步骤(1):丁二酸酐与间苯二酚单苯甲酸酯发生酯化反应,反应时间为3h,丁二酸酐与间苯二酚单苯甲酸酯的摩尔比为1.15:1,催化剂Ⅰ的用量为丁二酸酐和间苯二酚单苯甲酸酯总质量的0.032wt.%,酯化反应温度为150-180℃,反应结束后生成产物Ⅰ;
步骤(2):产物Ⅰ与阻燃剂Q发生酯化反应,反应时间为3h,产物Ⅰ与阻燃剂Q的质量比为1:0.53,催化剂Ⅱ的用量为产物Ⅰ和阻燃剂Q总质量的0.032wt.%,酯化反应温度为200-230℃,反应结束后生成产物Ⅱ,其中Q的分子结构为
步骤(3):产物Ⅱ与氯乙醇发生反应,反应时间为2h,产物Ⅱ与氯乙醇的质量比为6:1,催化剂Ⅲ的用量为产物Ⅱ和氯乙醇总质量的0.02wt.%,反应温度为95-100℃,反应结束后生成产物Ⅲ;
步骤(4):产物Ⅲ与对苯二甲酸、乙二醇、催化剂和稳定剂在氮气保护下进行反应,稳定剂的用量为产物Ⅲ、对苯二甲酸和乙二醇总质量的0.001wt.%,产物Ⅲ和乙二醇总量与对苯二甲酸的摩尔比为1.4-1.6:1,产物Ⅲ与乙二醇的质量比为1:1.5-2.5,催化剂Ⅳ的用量为产物Ⅲ、对苯二甲酸和乙二醇总质量的0.0035wt.%,氮气压力为0.02MPa,搅拌速度为35r/min,逐步升温至酯化温度230-235℃,待水的蒸出量达到理论值的90%,泄压至常压,酯化结束,
预缩聚:40min内将真空度降为100Pa,缓慢升温至270℃;
缩聚:设定缩聚温度270-275℃,增大转速为60r/min,保持真空度为100Pa,待搅拌功率提高到21W时出料,即获得具有抗紫外和阻燃效果的目标产物阻燃抗紫外PET;
步骤(1)中的催化剂Ⅰ为浓硫酸、对甲苯磺酸、高氯酸、氯化锌、无水乙酸钠、吡啶、二甲基苯胺中的一种;
步骤(2)中的催化剂Ⅱ为浓硫酸、对甲苯磺酸、高氯酸、氯化锌、无水乙酸钠、吡啶、二甲基苯胺中的一种;
步骤(3)中的催化剂Ⅲ为有机钠催化剂;
步骤(4)中的催化剂Ⅳ为锑系催化剂或有机锡类催化剂。
3.根据权利要求2所述的阻燃抗紫外PET的制备方法,其特征在于:
所述锑系催化剂为三氧化二锑、醋酸锑、乙二醇锑中的一种;
所述有机锡类催化剂为二丁基锡二月桂酸酯、二(十二烷基硫)二丁基锡、二醋酸二丁基锡中的一种;
所述有机钠催化剂为柠檬酸三钠或十二烷基苯磺酸钠中的一种。
4.根据权利要求2所述的阻燃抗紫外PET的制备方法,其特征在于:步骤(4)中反应的稳定剂为磷酸、亚磷酸、亚磷酸酯中的一种。
5.根据权利要求2所述的阻燃抗紫外PET的制备方法,其特征在于:所述步骤(2)中阻燃剂Q的制备方法如下:
将氰尿酸IA加入25gDMSO中并磁力搅拌,溶液温度加热到110-130℃,搅拌均匀后加入1,3-二氧杂环环戊酮EC、K2CO3、催化剂三乙胺,氰尿酸IA和1,3-二氧杂环环戊酮EC在DMSO中的浓度为2mol/Kg,三乙胺在DMSO中的浓度为0.0288mol/Kg,K2CO3在DMSO中的浓度为0.0576mol/Kg,继续反应0.8h,得到阻燃剂Q。
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