CN111647124A - 污水处理曝气用tpu膜片材料及其制备方法 - Google Patents
污水处理曝气用tpu膜片材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了污水处理曝气用TPU膜片材料及其制备方法,丙二酸、1,4丁二醇1,6己二醇、二苯基甲烷二异氰酸酯、抗氧剂1076、辅助抗氧剂168和扩链剂DDM;其中,二苯基甲烷二异氰酸酯:(1,6己二醇和1,4丁二醇)的摩尔比是2:(4‑6);(1,6己二醇和1,4丁二醇)与丙二酸的摩尔比例是(1‑1.3):1;1,6己二醇与1,4丁二醇的摩尔比是(8‑10):1。制备方法简单、成功率高、成本可控。有效的改进抗拉强度、断裂伸长率、抗扰裂性以及回弹性,同时提高其通过机械开孔后在污水中的通气量和氧传递效率。TPU膜片材料的的成品性能优越。通过这种方法适当的调整聚丙酸己二醇酯二醇的配比,提高了其制成污水处理用曝气膜片的强度和效率。
Description
技术领域
本发明涉及环保技术领域,特别是污水处理曝气用TPU膜片材料及其制备方法。
背景技术
TPU(Thermoplastic polyurethanes)名称为热塑性聚氨酯弹性体橡胶。主要分为聚酯型和聚醚型,它硬度范围宽(60A-85D)、耐磨、耐油,透明,弹性好,在日用品、体育用品、玩具、装饰材料等领域得到广泛应用,无卤阻燃TPU还可以代替软质PVC以满足越来越多领域的环保要求。
TPU薄膜是一种热可塑性弹性体,其实在TPU颗粒料的基础上,通过压延、流延、吹膜、涂覆等工艺制成薄膜。其具有无毒、可降解的好处。TPU薄膜的耐高温性及耐水性较差。
所谓弹性体是指玻璃化温度低于室温度,断裂伸长率>50%,外力撤除后复原性比较好的高分子材料。聚氨酯弹性体是弹性体中比较特殊的一大类,聚氨酯弹性体的硬度范围很宽,性能范围很宽,所以聚氨酯弹性体是介于橡胶和塑料的一类高分子材料。
可加热塑化,化学结构上没有或很少交联,其分子基本是线性的,然而却存在一定的物理交联。这类聚氨酯称为TPU。
TPU材料应用范围非常广泛,不同的组分会有不同的性能。
污水处理用曝气用TPU膜片,有良好的强度和韧性,膜片越薄阻力损失将越小,但是同时需要耐磨、抗老化、耐酸碱腐蚀以及抗拉伸。
对于污水处理用曝气用TPU膜片,不同的配比,硬度也不同,将对产品的使用寿命和性能参数产生影响。
发明内容
本发明的目的是提供污水处理曝气用TPU膜片材料及其制备方法,要解决现阶段曝气使用的膜片材料寿命短、制备复杂、成本高、韧性差、耐磨性差、抗老化性能有限、耐腐蚀性差的技术问题。
为实现上述目的,本发明采用如下技术方案:本发明一方面提供污水处理曝气用TPU膜片材料,所述膜片材料包括丙二酸、1,4丁二醇(BDO)、1,6己二醇(HDO)、二苯基甲烷二异氰酸酯(MDI)、抗氧剂1076、辅助抗氧剂168和扩链剂二氨基二苯甲烷(DDM);
其中,二苯基甲烷二异氰酸酯:(1,6己二醇和1,4丁二醇)的摩尔比是2:(4-6);
(1,6己二醇和1,4丁二醇)与丙二酸的摩尔比例是(1-1.3):1;1,6己二醇与1,4丁二醇的摩尔比是(8-10):1。
进一步,抗氧剂1076、辅助抗氧剂168和扩链剂DDM投加量分别为0.1-0.5%。
进一步,丙二酸:分子式为C3H4O4,结构式为:
进一步,1,4丁二醇的:分子式为C4H10O2,结构式为:
进一步,1,6己二醇分子式为C6H14O2,结构式为:
进一步,二苯基甲烷二异氰酸酯(MDI):分子式为C15H10N2O2,结构式为:
进一步,抗氧剂1076:β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇脂,分子式为C35H62O3,结构式为:
进一步,硬度为80-90。最佳范围为80-85。R值约为1.1-1.2(R值为塑性应变比,是材料在冲压成型时宽度上的应变值与厚度上的应变值之比,该值一般越大越好,R值越大。
本发明另一方面提供上述污水处理曝气用TPU膜片材料的制备方法,具体步骤如下:
步骤一,将丙二酸和HDO的混合均匀在熔体中反应,聚合形成的聚酯多元醇;
步骤二,将步骤一形成的聚酯多元醇中,引入纯MDI、BDO、抗氧剂1076和辅助抗氧剂168同时进行反应,冷却制成材料颗粒;
步骤三,将步骤二所得的材料颗粒,采用公知的方法通过不同直径的模头挤出制成不同直径、不同壁厚的薄壁管;
进一步,薄壁管的厚度为0.3-0.6mm;
进一步,薄壁管的管径为25-100mm。
步骤四,将步骤三所得的薄壁管,采用公知的塑料管开孔方法,按设定的规格开具一定密度的一字形孔,制成最终成品。
进一步,步骤一中反应温度为120-180℃,反应时间为10-100秒。
进一步,步骤2反应时间为10-300秒;将制成的颗粒111,通过管形塑料挤出机4,挤出制成管径65mm、壁厚0.5mm的薄壁管112;将薄壁管112,通过机械开孔设备5。
进一步,均匀开孔,单孔为一字形长条孔,长度1mm,开孔密度为3000-20000个/米。
本发明的有益效果体现在:
1,本发明提供的污水处理曝气用TPU膜片材料及其制备方法,制备方法简单、成功率高、成本可控。有效的改进抗拉强度、断裂伸长率、抗扰裂性以及回弹性,同时提高其通过机械开孔后在污水中的通气量和氧传递效率。
2,本发明提供的污水处理曝气用TPU膜片材料及其制备方法,TPU膜片材料的的成品性能优越。通过这种方法适当的调整聚丙酸己二醇酯二醇的配比,同时添加不同比例的抗氧剂1076以及辅助抗氧剂168,对TPU的性能的实际性能没有任何不利的改变,只是提高了其制成污水处理用曝气膜片的强度和效率。
3,挤出制成直径10-200mm不等的圆形桶状成品,最佳直径为25-100mm,壁厚0.2-1mm,最佳壁厚0.3-0.6mm。可以满足生产要求。采用塑料管开孔方法,在膜片上均匀开孔,单孔为一字形,单孔长度为0.3-2mm,最佳长度为0.8-1.2mm,开孔密度为1000-30000个/米,最佳开孔密度为3000-20000个/米。
本发明的其它特征和优点将在随后的说明书中阐述,并且部分地从说明书中变得显而易见,或者通过实施本发明而了解。本发明的主要目的和其它优点可通过在说明书中所特别指出的方案来实现和获得。
具体实施方式
以下通过实施例来详细说明本发明的技术方案,以下的实施例仅仅是示例性的,仅能用来解释和说明本发明的技术方案,而不能解释为对本发明技术方案的限制。
实施例1
TPU材料的合成工艺分为本体聚合和溶液聚合。在本体聚合中,又可按有无预反应分为预聚法和一步法。预聚法是将二异氰酸脂与大分子二醇先行反应一定时间,再加入扩链剂;一步法是将二异氰酸酯、大分子二醇和扩链剂等同时混合反应成TPU。溶液聚合是将二异氰酸酯先溶于溶剂中,再加入大分子二醇令其反应一定时间,最后加入扩链剂生成TPU。
本材料采用本体聚合中一步法将丙二酸、1,4丁二醇1,6己二醇、二苯基甲烷二异氰酸酯、抗氧剂1076和辅助抗氧剂168同时混合反应生成TPU。
本发明一方面提供污水处理曝气用TPU膜片材料,通过对材料组分的调整,采用丙二酸和HDO聚合形成的聚酯多元醇,即聚丙酸己二醇酯二醇,其显示改进抗拉强度、断裂伸长率、抗扰裂性以及回弹性,同时提高其通过机械开孔后在污水中的通气量和氧传递效率。
具体的,丙二酸、1,4丁二醇1,6己二醇、二苯基甲烷二异氰酸酯、抗氧剂1076、辅助抗氧剂168和扩链剂DDM;
其中,二苯基甲烷二异氰酸酯:(1,6己二醇和1,4丁二醇)的摩尔比是2:(4-6);
(1,6己二醇和1,4丁二醇)与丙二酸的摩尔比例是(1-1.3):1;
1,6己二醇与1,4丁二醇的摩尔比是(8-10):1。抗氧剂1076、辅助抗氧剂168和扩链剂DDM投加量分别为0.1-0.5%。
丙二酸:分子式为C3H4O4,结构式为:
进一步,1,4丁二醇的:分子式为C4H10O2,结构式为:
进一步,1,6己二醇分子式为C6H14O2,结构式为:
进一步,二苯基甲烷二异氰酸酯(MDI):分子式为C15H10N2O2,结构式为:
进一步,抗氧剂1076:β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇脂,分子式为C35H62O3,结构式为:
进一步,硬度为80-90。最佳范围为80-85。R值约为1.1-1.2(R值为塑性应变比,是材料在冲压成型时宽度上的应变值与厚度上的应变值之比,该值一般越大越好,R值越大。
本发明另一方面提供上述污水处理曝气用TPU膜片材料的制备方法,具体步骤如下:
步骤一,将丙二酸和HDO的混合均匀在熔体中反应,聚合形成的聚酯多元醇;反应温度为120-180℃,反应时间为10-100秒。
步骤二,将步骤一形成的聚酯多元醇中,引入纯MDI、BDO、抗氧剂1076和辅助抗氧剂168同时进行反应,冷却制成材料颗粒;反应时间为10-300秒;将制成的颗粒111,通过管形塑料挤出机4,挤出制成管径65mm、壁厚0.5mm的薄壁管112;
将薄壁管112,通过机械开孔设备5,均匀开孔,单孔为一字形长条孔,长度1mm,开孔密度10000个/米。
步骤三,将步骤二所得的材料颗粒,采用公知的方法通过不同直径的模头挤出制成不同直径、不同壁厚的薄壁管;
步骤四,将步骤三所得的薄壁管,采用公知的塑料管开孔方法,按设定的规格开具一定密度的一字形孔,制成最终成品。
实施例2:
纯MDI:(HDO+BDO)的摩尔比是2:4;
(HDO+BDO)与丙二酸的摩尔比例是1:1;
HDO与BDO的摩尔比是8:1。
抗氧剂1076投加量为0.1%;
辅助抗氧剂168投加量为0.1%;
挤出制成薄壁管112:管径65mm、壁厚0.4mm;
薄壁管112:均匀表面开孔,单孔为一字形长条孔,长度1mm,开孔密度10000个/米。
特性 | 单位 | 数值 | 检测方法 |
硬度 | 邵氏A | 80 | GB2411-80 |
密度 | g/cm<sup>3</sup> | 1.11 | GB/T1033.1-2008 |
最大拉伸强度 | kN | 550 | GB/T228.1-2010 |
最大断裂伸长率 | % | 450 | QB/T1130-1991 |
标准通气量 | Nm<sup>3</sup>/h | 1-10 | CJ/T475-2015HJ/T252-2006 |
6米水深氧利用率 | % | 45-55 | CJ/T475-2015HJ/T252-2006 |
实施例3:
纯MDI:(HDO+BDO)的摩尔比是2:5;
(HDO+BDO)与丙二酸的摩尔比例是1.2:1;
HDO与BDO的摩尔比是9:1。
抗氧剂1076投加量为0.1%;
辅助抗氧剂168投加量为0.1%;
挤出制成薄壁管112:管径65mm、壁厚0.4mm;
薄壁管112:均匀表面开孔,单孔为一字形长条孔,长度1mm,开孔密度10000个/米。
特性 | 单位 | 数值 | 检测方法 |
硬度 | 邵氏A | 85 | GB2411-80 |
密度 | g/cm<sup>3</sup> | 1.12 | GB/T1033.1-2008 |
拉伸强度 | kN | 580 | GB/T228.1-2010 |
断裂伸长率 | % | 500 | QB/T1130-1991 |
标准通气量 | Nm<sup>3</sup>/h | 1-10 | CJ/T475-2015HJ/T252-2006 |
6米水深氧利用率 | % | 45-55 | CJ/T475-2015HJ/T252-2006 |
实施例4:
纯MDI:(HDO+BDO)的摩尔比是2:6;
(HDO+BDO)与丙二酸的摩尔比例是1.3:1;
HDO与BDO的摩尔比是10:1。
抗氧剂1076投加量为0.1%;
辅助抗氧剂168投加量为0.1%;
挤出制成薄壁管112:管径65mm、壁厚0.4mm;
薄壁管112:均匀表面开孔,单孔为一字形长条孔,长度1mm,开孔密度10000个/米。
特性 | 单位 | 数值 | 检测方法 |
硬度 | 邵氏A | 88 | GB2411-80 |
密度 | g/cm<sup>3</sup> | 1.14 | GB/T1033.1-2008 |
拉伸强度 | kN | 620 | GB/T228.1-2010 |
断裂伸长率 | % | 520 | QB/T1130-1991 |
标准通气量 | Nm<sup>3</sup>/h | 1-10 | CJ/T475-2015HJ/T252-2006 |
6米水深氧利用率 | % | 45-55 | CJ/T475-2015HJ/T252-2006 |
由上述实施例2-4可以看出,本发明提供的制备方法简单、成功率高。有效的改进抗拉强度、断裂伸长率、抗扰裂性以及回弹性,同时提高其通过机械开孔后在污水中的通气量和氧传递效率。挤出制成直径10-200mm不等的圆形桶状成品,最佳直径为25-100mm,壁厚0.2-1mm,最佳壁厚0.3-0.6mm。可以满足生产要求。采用塑料管开孔方法,在膜片上均匀开孔,单孔为一字形,单孔长度为0.3-2mm,最佳长度为0.8-1.2mm,开孔密度为1000-30000个/米,最佳开孔密度为3000-20000个/米。
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所想到的变化或替换,都应涵盖在本发明的保护范围之内。
Claims (9)
1.污水处理曝气用TPU膜片材料,其特征在于:所述膜片材料包括丙二酸、1,4丁二醇、1,6己二醇、二苯基甲烷二异氰酸酯、抗氧剂1076、辅助抗氧剂168和扩链剂二氨基二苯甲烷;
其中,二苯基甲烷二异氰酸酯:(1,6己二醇和1,4丁二醇)的摩尔比是2:(4-6);
(1,6己二醇和1,4丁二醇)与丙二酸的摩尔比例是(1-1.3):1;
1,6己二醇与1,4丁二醇的摩尔比是(8-10):1。
2.如权利要求1所述的污水处理曝气用TPU膜片材料,其特征在于,抗氧剂1076、辅助抗氧剂168和扩链剂DDM投加量分别为0.1-0.5%。
3.如权利要求1所述的污水处理曝气用TPU膜片材料,其特征在于,硬度为80-90。
4.如权利要求1所述的污水处理曝气用TPU膜片材料,其特征在于,硬度为80-85。R值约为1.1-1.2(R值为塑性应变比,是材料在冲压成型时宽度上的应变值与厚度上的应变值之比,该值一般越大越好,R值越大。)
5.如权利要求1-4中任意一项所述的污水处理曝气用TPU膜片材料的制备方法,其特征在于,具体步骤如下:
步骤一,将丙二酸和HDO的混合均匀在熔体中反应,聚合形成的聚酯多元醇;
步骤二,将步骤一形成的聚酯多元醇中,引入纯MDI、BDO、抗氧剂1076和辅助抗氧剂168同时进行反应,冷却制成材料颗粒;
步骤三,将步骤二所得的材料颗粒,通过不同直径的模头挤出制成不同直径、不同壁厚的薄壁管;
步骤四,将步骤三所得的薄壁管,按设定的规格开具一定密度的一字形孔,制成最终成品。
6.如权利要求5中所述的制备方法,其特征在于,步骤一中反应温度为120-180℃,反应时间为10-100秒。
7.如权利要求5中所述的制备方法,其特征在于,成品表面均匀开孔,单孔为一字形长条孔,长度1mm,开孔密度为3000-20000个/米。
8.如权利要求5中所述的制备方法,其特征在于,薄壁管的厚度为0.3-0.6mm。
9.如权利要求5中所述的制备方法,其特征在于,薄壁管的管径为25-100mm。
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