CN107793063B - 一种利用废弃的pet聚酯材料制备的再生高聚物水性乳液 - Google Patents

一种利用废弃的pet聚酯材料制备的再生高聚物水性乳液 Download PDF

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CN107793063B
CN107793063B CN201611213371.3A CN201611213371A CN107793063B CN 107793063 B CN107793063 B CN 107793063B CN 201611213371 A CN201611213371 A CN 201611213371A CN 107793063 B CN107793063 B CN 107793063B
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李素芳
王聪聪
王俊梅
方盼
李娴
吴世杰
宋肖
李桃凡
田承宇
何德强
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Abstract

本发明公开了一种利用废弃的PET聚酯材料制备的再生高聚物水性乳液，其含有如下重量份的组分：聚氨酯改性聚合物乳液A 60—95；聚氨酯改性聚合物乳液B 5—40。本发明利用废弃的PET聚酯，通过化学降解与改性，获得了一种用于混凝土防渗抗裂的再生乳液，不仅废物利用，改善环境污染，而且可以降低生产成本，具有很大的环保和经济意义。

Description

一种利用废弃的PET聚酯材料制备的再生高聚物水性乳液
技术领域
本发明属于高分子材料领域，具体涉及一种利用废弃的PET聚酯材料制备的再生高聚物水性乳液,用于混凝土防裂抗渗。
背景技术
PET聚酯是聚对苯二甲酸乙二酯这种热塑性树脂材料的简称，具有高强度、高透明性、价格低廉、易于加工成型等优点，广泛用于合成纤维、饮料瓶、薄膜等方面，消费量巨大，每年有大量的废弃PET聚酯材料产生。废弃PET聚酯具有极强的化学惰性，不能被直接降解，造成了很严重的环境污染。
现代混凝土防裂抗渗的方法是往新拌混凝土中添加高分子材料外加剂，高分子材料在混凝土中形成立体网状结构，不仅可消除混凝土内部的毛细孔缝，增加混凝土的密实度，而且改善混凝土固结体的结微观结构，增强混凝土的粘接和抗压等力学性能，提高混凝土的耐久性和密封防水抗渗的效果。目前使用的聚合物一般为合成橡胶乳液，如氯丁胶乳(CR)、丁苯胶乳(SBR)、丁腈胶乳(NBR)；或热塑性树脂乳液，如聚丙烯酸酯类乳液(PAE)、聚乙酸乙烯乳液(PVAC)等。
发明内容
本发明旨在克服现有技术的不足，提供一种利用废弃的PET聚酯材料制备的再生高聚物水性乳液，用于混凝土防渗抗裂，以实现废物利用。
为了达到上述目的，本发明提供的技术方案为：
所述利用废弃的PET聚酯材料制备的再生高聚物水性乳液含有如下重量份的组分：聚氨酯改性聚合物乳液A 60—95；聚氨酯改性聚合物乳液B 5—40；
所述聚氨酯改性聚合物乳液A由如下重量份的组分经过废弃PET聚酯降解、再经预聚、扩链、中和以及乳化等步骤改性加工后制备而成：
废弃PET聚酯材料20—40；乙二醇30—60；醋酸锌0.4—1.2；异佛尔酮二异氰酸酯25—39；2，2-二羟甲基丙酸2.4—3.6；三羟甲基丙烷1.0—4.5；1，4-丁二醇1.0—1.5；三乙胺1.0—2.7；丙酮20—30；水76—105；
所述聚氨酯改性聚合物乳液B由如下重量份的组分制备而成：
废弃PET聚酯降解产物10—30；环氧树脂E-44 6—10；异佛尔酮二异氰酸酯24—28，优选26；2,2-二羟甲基丙酸2.2—2.6，优选2.4；三羟甲基丙烷2.8—3.2，优选3.0；1,4-丁二醇1.3—1.7，优选1.5；三乙胺1.5—2.0，优选1.8；水70—80，优选78。
优选地，所述再生高聚物水性乳液含有如下重量份的组分：聚氨酯改性聚合物乳液A 85—90；聚氨酯改性聚合物乳液B 10—15。
优选地，所述聚氨酯改性聚合物乳液A的主要结构式如式Ⅰ所示：
Figure BDA0001190005050000021
其中，聚合度n的取值范围为10-25,R为：
Figure BDA0001190005050000022
所述R中的R1和R2分别为：
Figure BDA0001190005050000023
所述R2中的聚合度m的取值为1、2或3；
所述聚氨酯改性聚合物乳液A的主要结构式如式Ⅱ所示：
Figure BDA0001190005050000024
其中，n'取值为0～3。
优选地，所述再生高聚物水性乳液中的固体质量百分比含量为20—40％。
本发明所述利用废弃的PET聚酯材料制备的再生高聚物水性乳液用于混凝土的防裂抗渗，可涂覆于已固结混凝土的表面，也可加入新拌合的混凝土中。
下面对本发明作进一步说明：
关于聚氨酯改性聚合物乳液A的具体制备过程如下：将废弃聚酯PET，加入乙二醇和0.4％PET质量份的醋酸锌，混合搅拌，控制反应温度为180-200℃，通入氮气，反应2-4小时。冷却后过滤得到白色晶体的降解产物。将降解产物、2，2-二羟甲基丙酸加入到反应釜中混合，加热至80-90℃，加入异佛尔酮二异氰酸酯，搅拌反应3-4h。降温至60-70℃，加入三羟甲基丙烷和1，4-丁二醇，继续反应2-3h。然后在40-50℃下加入三乙胺，反应10-20min。反应物冷却至室温后，加入余量蒸馏水，通过搅拌制得白色水性乳液。所得白色水性乳液的乳粒呈球形，粒径约为20至100nm左右。图1为该聚氨酯改性聚合物乳液A的透射扫描电子显微镜图。
关于聚氨酯改性聚合物乳液B的具体制备过程如下：将废弃PET塑料的降解产物和用N-甲基吡咯烷酮(NMP)溶解的亲水扩链剂2，2-二羟甲基丙酸(DMPA)混合，升温至120℃，熔融后降温至90℃，加入异氟尔酮二异氰酸酯(IPDI)，90℃反应1h后，加入催化剂二月桂酸二丁基锡，继续反应至聚氨酯预聚体的-NCO含量达到理论值后冷却至70℃。再将加入1，4-丁二醇、环氧树脂和用N-甲基吡咯烷酮(NMP)溶解的内交联剂三羟甲基丙烷，在70℃下反应2h。之后调节体系温度至40℃，加入计量好的中和剂三乙胺(TEA)，搅拌混合后冷却至室温，加入蒸馏水，搅拌乳化30min，制得聚氨酯改性聚合物B。图2聚氨酯改性聚合物乳液B的电镜图。
本发明涉及的再生聚合物混合乳液成膜后具有具有好的柔韧性好和附着力以及优异的耐磨性、耐候性。可直接涂覆在已固结混凝土表面成膜。图2为再生聚合物固结膜，柔软透明，可耐200℃以下的高温。附着力为零级，具有优异的附着性能。断裂伸长率大于400％。
本发明涉及的再生聚合物乳液可直接加入到新拌合的混凝土中，图3为未掺入和已掺入本再生聚合物乳液的水泥固结后的断面扫描电镜图。掺入本乳液后混凝土结构致密度明显提高。当混凝土的聚灰比为0.1时，固结后水泥体的抗折强度可提高50％以上。这是因为高聚物在水泥体系中既填充了微孔隙又相互交缠形成互穿网络体系，增强了水泥的力学性能。同时乳液颗粒在水泥浆体中形成薄膜，增加了水泥水化产物之间的粘结力，减少因收缩产生的微裂纹，并使微裂纹的尺寸降低，因而可明显提高力学性能，提高抗渗性。
总之，本发明利用废弃的PET聚酯，通过化学降解与改性，获得了一种用于混凝土防渗抗裂的再生乳液，不仅废物利用，改善环境污染，而且可以降低生产成本，具有很大的环保和经济意义。
附图说明
图1和图2分布为聚氨酯改性聚合物乳液A和B的透射扫描电子显微镜图；
图3为再生聚合物固结膜；
图4为未掺入和已掺入本再生聚合物乳液的水泥固结后的断面扫描电镜图。
具体实施方式
实施例1
所述利用废弃的PET聚酯材料制备的再生高聚物水性乳液含有如下重量份的组分：聚氨酯改性聚合物乳液A 60—95；聚氨酯改性聚合物乳液B 5—40；
所述聚氨酯改性聚合物乳液A由如下重量份的组分经过废弃PET聚酯降解、再经预聚、扩链、中和以及乳化等步骤改性加工后制备而成：
废弃PET聚酯材料20；乙二醇40；醋酸锌0.4；异佛尔酮二异氰酸酯26；2，2-二羟甲基丙酸2.4；三羟甲基丙烷3.0；1，4-丁二醇1.2；三乙胺1.8；丙酮20；水76；
所述聚氨酯改性聚合物乳液B由如下重量份的组分制备而成：
废弃PET聚酯降解产物10；环氧树脂E-44 6；异佛尔酮二异氰酸酯26；2,2-二羟甲基丙酸2.4；三羟甲基丙烷3.0；1,4-丁二醇1.5；三乙胺1.8；水78。
实施例2
所述利用废弃的PET聚酯材料制备的再生高聚物水性乳液含有如下重量份的组分：聚氨酯改性聚合物乳液A 85—90；聚氨酯改性聚合物乳液B 10—15；
所述聚氨酯改性聚合物乳液A由如下重量份的组分经过废弃PET聚酯降解、再经预聚、扩链、中和以及乳化等步骤改性加工后制备而成：
废弃PET聚酯材料30；乙二醇60；醋酸锌1.2；异佛尔酮二异氰酸酯39；2，2-二羟甲基丙酸3.6；三羟甲基丙烷4.5；1，4-丁二醇1.2；三乙胺12.7；丙酮30；水105；
所述聚氨酯改性聚合物乳液B由如下重量份的组分制备而成：
废弃PET聚酯降解产物20；环氧树脂E-44 8；异佛尔酮二异氰酸酯26；2,2-二羟甲基丙酸2.4；三羟甲基丙烷3.0；1,4-丁二醇1.5；三乙胺1.8；水78。
实施例3
所述利用废弃的PET聚酯材料制备的再生高聚物水性乳液含有如下重量份的组分：聚氨酯改性聚合物乳液A 85—90；聚氨酯改性聚合物乳液B 10—15；
所述聚氨酯改性聚合物乳液A由如下重量份的组分经过废弃PET聚酯降解、再经预聚、扩链、中和以及乳化等步骤改性加工后制备而成：
废弃PET聚酯材料20；乙二醇60；异醋酸锌1.0；佛尔酮二异氰酸酯26；2，2-二羟甲基丙酸2.4；三羟甲基丙烷3.0；1，4-丁二醇1.5；三乙胺1.8；丙酮20；水78；
所述聚氨酯改性聚合物乳液B由如下重量份的组分制备而成：
废弃PET聚酯降解产物30；环氧树脂E-44 10；异佛尔酮二异氰酸酯26；2,2-二羟甲基丙酸2.4；三羟甲基丙烷3.0；1,4-丁二醇1.5；三乙胺1.8；水78。

Claims (2)

1.一种用于混凝土基材表面的利用废弃的PET聚酯材料制备的再生高聚物水性乳液，其特征在于：
所述再生高聚物水性乳液含有如下重量份的组分：聚氨酯改性聚合物乳液A 60—95；聚氨酯改性聚合物乳液B 5—40；
所述聚氨酯改性聚合物乳液A由如下重量份的组分制备而成：废弃PET聚酯材料20—40；乙二醇30—60；醋酸锌0.4—1.2；异佛尔酮二异氰酸酯25—39；2，2-二羟甲基丙酸2.4—3.6；三羟甲基丙烷1.0—4.5；1，4-丁二醇1.0—1.5；三乙胺1.0—2.7；丙酮20—30；水76—105；
所述聚氨酯改性聚合物乳液B由如下重量份的组分制备而成：废弃PET聚酯降解产物10—30；环氧树脂E-44 6—10；异佛尔酮二异氰酸酯24—28；2,2-二羟甲基丙酸2.2—2.6；三羟甲基丙烷2.8—3.2；1,4-丁二醇1.3—1.7；三乙胺1.5—2.0；水70—80;
所述再生高聚物水性乳液中的固体质量百分比含量为20—40％；
所述聚氨酯改性聚合物乳液A的主要结构式如式Ⅰ所示：
Figure DEST_PATH_IMAGE001
其中，聚合度n的取值范围为10-25,R为：
Figure 794033DEST_PATH_IMAGE002
所述R中的R1和R2分别为：
Figure DEST_PATH_IMAGE003
所述R2中的聚合度m的取值为1、2或3；
所述聚氨酯改性聚合物乳液B的主要结构式如式Ⅱ所示：
Figure 976753DEST_PATH_IMAGE004
其中，n'取值为0～3，n'不为零；
所述聚氨酯改性聚合物乳液A的乳粒呈球形，粒径为20至100nm。
2.如权利要求1所述的再生高聚物水性乳液，其特征在于，所述再生高聚物水性乳液含有如下重量份的组分：聚氨酯改性聚合物乳液A 85—90；聚氨酯改性聚合物乳液B 10—15。
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