CN106478923B - 一种环保型聚氨酯塑胶跑道铺装维修材料 - Google Patents

一种环保型聚氨酯塑胶跑道铺装维修材料 Download PDF

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CN106478923B
CN106478923B CN201610136755.3A CN201610136755A CN106478923B CN 106478923 B CN106478923 B CN 106478923B CN 201610136755 A CN201610136755 A CN 201610136755A CN 106478923 B CN106478923 B CN 106478923B
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CN106478923A (zh
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郑华林
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Beijing Newkors Technology Co ltd
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Abstract

本发明提供一种环保型聚氨酯塑胶跑道铺装维修材料，主要由大豆多元醇、聚四氢呋喃多元醇、填料、颜料、改性剂、增塑剂、异氰酸酯和潜固剂按照不同的重量份数制备而成。本发明不含溶剂，具有100％固含量，环保无毒、施工方便、具有良好的柔韧性和优良的力学性能、低温性能和抗老化性能，铺装在塑胶跑道和球场表面或浇筑在塑胶跑道和球场破损处后，能够与塑胶跑道内部、表面或空气中的水发生湿固化反应，避免因塑胶材料内或环境中含水量高而引起的材料固化不完全，固化后鼓泡、强度低等现象，可广泛用于各种气候条件下运动场地的铺设、维修、翻新等。

Description

一种环保型聚氨酯塑胶跑道铺装维修材料
技术领域
本发明涉及高分子复合材料领域，特别涉及一种环保型聚氨酯塑胶跑道铺装维修材料。
背景技术
塑胶跑道一般使用聚氨酯弹性体制造，由于频繁使用以及紫外线、雨雪、冰寒等恶劣气候的影响，塑胶跑道在长时间使用后容易出现老化、起皮、破损及防滑层磨平等问题，无法继续起到增加运动摩擦力、减震、防挫伤的功能，容易造成运动者运动损伤，因此频繁使用的室外塑胶跑道在使用5-8年后应揭掉原有的塑胶跑道后重新进行铺设，此种方式不仅造成极大材料和人力浪费，而且容易对原地基材料造成破坏。如果利用现有聚氨酯弹性体材料进行修补，因为塑胶跑道内部存在大量孔隙，孔隙内容易积存水分，修补的聚氨酯弹性体固化后容易出现发泡、固化不完全导致的材料发粘及固化后强度低等问题，同时现有聚氨酯弹性体中大多含有TDI、DOP、DBP及有机溶剂等易挥发的有毒物质，严重危害施工人员和运动人员的身体健康。
发明内容
为了解决上述技术问题，本发明提供一种环保型聚氨酯塑胶跑道铺装维修材料，主要由下列重量份的原料制备而成：
由于聚四氢呋喃多元醇主链中含有大量醚键，而C-O键的内旋转比C-C更加容易，因此聚四氢呋喃多元醇比一般的大分子多元醇的玻璃化转变温度更低，具有更好的柔顺性，环保型聚氨酯塑胶跑道铺装维修材料中使用聚四氢呋喃多元醇作为“软段”可以获得优良的弹性和低温性能。大豆多元醇与聚四氢呋喃多元醇混合使用，可使环保型聚氨酯塑胶跑道铺装维修材料在保持良好的柔韧性和低温性能的同时具有较高的强度。在上述体系中提高环保型聚氨酯塑胶跑道铺装维修材料中的硬段含量，将异氰酸酯的用量提高至15-25份，可以同时提高环保型聚氨酯塑胶跑道铺装维修材料的强度。
由大豆多元醇、聚四氢呋喃多元醇和异氰酸酯生成的聚氨酯预聚体中含有过量的异氰根(NCO)基团，容易和水反应释放出二氧化碳气体，从而使得环保型聚氨酯塑胶跑道铺装维修材料中带有大量的气泡影响力学性能。在聚氨酯预聚体加入潜固剂，与水接触时，潜固剂可以优先与水发生水解反应释放活性成分,此活性成分含羟基或仲胺基等活泼基团，可以与异氰根(NCO)迅速交联固化，整个固化过程无气泡生成，弹性体表面和内部不生成气泡。
在聚氨酯预聚体中加入增塑剂可以降低聚氨酯预聚体的粘度，提高流动性，改善加工和施工性能。
所述颜料可以选择公知的各种适宜的颜料，包括无机颜料如氧化铁红等，或有机颜料如酞菁绿等。
作为本发明的一个优选方案，所述大豆多元醇的数均分子量为3000-4500。
作为本发明的一个优选方案，所述聚四氢呋喃多元醇的数均分子量为1500-2500。
作为本发明的一个优选方案，所述填料为滑石粉、碳酸钙、蒙脱土或高岭土中的一种或多种。
作为本发明的一个优选方案，所述改性剂芳纶纤维粉末、纳米碳纤维或它们的混合物。
作为上述优选方案的进一步改进，所述芳纶纤维粉末和纳米碳纤维的混合物中两者的重量份数比为1：1。
芳纶纤维粉末和纳米碳纤维的混合物可以增加环保型聚氨酯塑胶跑道铺装维修材料的耐磨性、耐疲劳性、耐腐蚀性、耐热性、导热性和抗紫外线性能，延长材料使用寿命。芳纶纤维粉末和纳米碳纤维按照重量份数为1:1的比例混合使用在提高环保型聚氨酯塑胶跑道铺装维修材料力学性能和抗老化性能上的作用更明显。
作为本发明的一个优选方案，所述的增塑剂是二乙二醇二苯甲酸酯、柠檬酸三丁酯或它们的混合物。
作为本发明的一个优选方案，所述的异氰酸酯为二苯甲烷-4，4`-二异氰酸酯(MDI)、聚醚改性MDI、碳化二亚胺改性MDI或多亚甲基多苯基异氰酸酯(PAPI)中的一种。
异氰酸酯选用MDI、改性MDI或PAPI代替TDI，降低环保型聚氨酯塑胶跑道铺装维修材料的毒性，防止挥发物污染环境，危害人体健康。
作为本发明的一个优选方案，所述的潜固剂为重量份数比是1:1.5的7-乙基双环噁唑烷和二烯丙基胺的混合物。
潜固剂选择7-乙基双环噁唑烷与二烯丙基胺以1:1.5的比例添加，比单独添加7-乙基双环噁唑烷或二烯丙基胺或者添加其他种类潜固剂对防止材料中产生气泡的效果更好。
本发明还提供环保型聚氨酯塑胶跑道铺装维修材料的制备方法，所述制备方法包括下列步骤：
(1)将大豆多元醇、聚四氢呋喃多元醇、填料、颜料、改性剂、增塑剂加热至100-150℃，抽真空1.5-2h；
(2)将步骤(1)所得物料冷却至50-60℃，加入异氰酸酯，保温6-8h；
(3)将步骤(2)所得物料冷却至25-35℃，加入潜固剂，保温1-2h，抽真空1-2h，制得环保型聚氨酯塑胶跑道铺装维修材料。
由于聚氨酯预聚体含有丰富的异氰根(NCO)基团，体系中即使含有少量水也会容易导致产生脲交联，需要进行抽真空处理除去水份。进行抽真空除水除气还可以保持良好的储存稳定性。
本发明不含溶剂，具有100％固含量，环保无毒、施工方便、具有良好的柔韧性和优良的力学性能、低温性能和抗老化性能，铺装在塑胶跑道和球场表面或浇筑在塑胶跑道和球场破损处后，能够与塑胶跑道内部、表面或空气中的水发生湿固化反应，避免因塑胶材料内或环境中含水量高而引起的材料固化不完全，固化后鼓泡、强度低等现象，可广泛用于各种气候条件下运动场地的铺设、维修、翻新等。
具体实施方式
实施例1：
一种环保型聚氨酯塑胶跑道铺装维修材料，该材料主要由下列重量配比的原料制备而成：
该材料的制备方法：
(1)将大豆多元醇、聚四氢呋喃多元醇、滑石粉、颜料、芳纶纤维粉末、二乙二醇二苯甲酸酯加热至100℃，抽真空1.5h；
(2)将步骤(1)所得物料冷却至50℃，加入MDI，保温6h；
(3)将步骤(2)所得物料冷却至25℃，加入7-乙基双环噁唑烷和二烯丙基胺，保温1h，抽真空1h，制得环保型聚氨酯塑胶跑道铺装维修材料。
实施例2：
一种环保型聚氨酯塑胶跑道铺装维修材料，该材料主要由下列重量配比的原料制备而成：
大豆多元醇的数均分子量为3000
聚四氢呋喃多元醇的数均分子量为1500；
该材料的制备方法：
(1)将大豆多元醇、聚四氢呋喃多元醇、碳酸钙、蒙脱土、颜料、纳米碳纤维、二乙二醇二苯甲酸酯、柠檬酸三丁酯加热至125℃，抽真空2h；
(2)将步骤(1)所得物料冷却至55℃，加入聚醚改性MDI，保温7h；
(3)将步骤(2)所得物料冷却至30℃，加入7-乙基双环噁唑烷和二烯丙基胺，保温1.5h，抽真空1.5h，制得环保型聚氨酯塑胶跑道铺装维修材料。
实施例3：
一种环保型聚氨酯塑胶跑道铺装维修材料，该材料主要由下列重量配比的原料制备而成：
大豆多元醇的数均分子量为4500
聚四氢呋喃多元醇的数均分子量为2500；
该材料的制备方法：
(1)将大豆多元醇、聚四氢呋喃多元醇、碳酸钙、蒙脱土、颜料、芳纶纤维粉末、纳米碳纤维、二乙二醇二苯甲酸酯、柠檬酸三丁酯加热至125℃，抽真空2h；
(2)将步骤(1)所得物料冷却至55℃，加入碳化二亚胺改性MDI，保温7h；
(3)将步骤(2)所得物料冷却至30℃，加入7-乙基双环噁唑烷和二烯丙基胺，保温1.5h，抽真空1.5h，制得环保型聚氨酯塑胶跑道铺装维修材料。
实施例4：
一种环保型聚氨酯塑胶跑道铺装维修材料，该材料主要由下列重量配比的原料制备而成：
大豆多元醇的数均分子量为4000
聚四氢呋喃多元醇的数均分子量为2000；
该材料的制备方法：
(1)将大豆多元醇、聚四氢呋喃多元醇、滑石粉、高岭土、颜料、芳纶纤维粉末、纳米碳纤维、柠檬酸三丁酯加热至150℃，抽真空2h；
(2)将步骤(1)所得物料冷却至60℃，加入PAP I，保温8h；
(3)将步骤(2)所得物料冷却至35℃，加入7-乙基双环噁唑烷和二烯丙基胺，保温2h，抽真空2h，制得环保型聚氨酯塑胶跑道铺装维修材料。
性能分析
1.大豆多元醇(醇A)、聚四氢呋喃多元醇(醇B)、异氰酸酯添加比例、潜固剂对环保型聚氨酯塑胶跑道铺装维修材料性能的影响分析
试验1-7对环保型聚氨酯塑胶跑道铺装维修材料制备工艺中选用多元醇的种类、异氰酸酯的添加比例以及潜固剂的使用及种类选择对环保型聚氨酯塑胶跑道铺装维修材料常温力学性能和低温性能进行考察，其余原料种类及重量份数、制备工艺参见实施例3；对比例1的原料种类、重量份数及制备工艺参见CN102838868B，对比例2的原料种类、重量份数及制备工艺参见CN1450121A，考察结果见表1。
表1聚氨酯材料固化后性能对比表
由上述试验结果可知：与试验1-4和对比例相比，试验5-7使用大豆油多元醇与聚四氢呋喃多元醇按照一定的比例作为“软段”制备环保型聚氨酯塑胶跑道铺装维修材料，可有效提高扯断伸长率和拉伸强度，降低低温脆化温度，获得同时具备较好的强度、柔韧性和低温性能的环保型聚氨酯塑胶跑道铺装维修材料。试验4提高了反应体系中聚四氢呋喃多元醇的添加比例，导致生成的聚氨酯材料虽然柔韧性较好，但拉伸强度大幅度降低。
与试验5相比，试验7使用大豆油多元醇和聚四氢呋喃多元醇作为“软段”制备聚氨酯弹性体时，提高“硬段”异氰酸酯的添加比例，可以在保持聚氨酯弹性体良好的柔韧性和低温性能的同时，有效提高材料强度，获得常温力学性能和低温性能均优良的环保型聚氨酯塑胶跑道铺装维修材料。
聚合反应体系中加入潜固剂，可以防止环保型聚氨酯塑胶跑道铺装维修材料在湿固化过程中生成大量气泡影响美观及材料力学性能，进而可提高环保型聚氨酯塑胶跑道铺装维修材料各项力学性能。潜固剂选择7-乙基双环噁唑烷与二烯丙基胺以1:1.5的比例添加，比单独添加7-乙基双环噁唑烷或二烯丙基胺或者添加其他种类潜固剂对防止材料中产生气泡的效果更好。
2.改性剂对环保型聚氨酯塑胶跑道铺装维修材料性能的影响分析
试验8-11对使用芳纶纤维粉末和纳米碳纤维作为改性剂对环保型聚氨酯塑胶跑道铺装维修材料性能的影响进行考察，试验中其余原料种类及重量份数、制备工艺参见实施例3；对比例1的原料种类、重量份数及制备工艺参见CN102838868B，对比例2的原料种类、重量份数及制备工艺参见CN1450121A，考察结果见表2。
表2改性剂对环保型聚氨酯塑胶跑道铺装维修材料性能的影响
由上述试验结果可知，试验11的力学性能优于试验8-10和对比例，尤其是经过180天老化后，试验11的力学性能的降低比例明显低于试验8-10和对比例，说明在环保型聚氨酯塑胶跑道铺装维修材料中加入芳纶纤维粉末和纳米碳纤维进行改性，可以提高环保型聚氨酯塑胶跑道铺装维修材料的力学性能和老化性能；试验11的力学性能和180天老化后的力学性能均优于试验9和试验10，说明芳纶纤维粉末和纳米碳纤维按照1:1的比例添加对聚氨酯的力学性能和老化性能的改善效果更佳。

Claims (6)

1.一种环保型聚氨酯塑胶跑道铺装维修材料，其特征在于，所述材料主要由下列重量份的原料制备而成：
所述改性剂为重量份数比为1:1的芳纶纤维粉末和纳米碳纤维；
所述的异氰酸酯为二苯甲烷-4，4`-二异氰酸酯、聚醚改性MDI、碳化二亚胺改性MDI或多亚甲基多苯基异氰酸酯中的一种；
所述的潜固剂为重量份数比是1:1.5的7-乙基双环噁唑烷和二烯丙基胺的混合物。
2.根据权利要求1所述的一种环保型聚氨酯塑胶跑道铺装维修材料，其特征在于，所述大豆多元醇的数均分子量为3000-4500。
3.根据权利要求1所述的一种环保型聚氨酯塑胶跑道铺装维修材料，其特征在于，所述聚四氢呋喃多元醇的数均分子量为1500-2500。
4.根据权利要求1所述的一种环保型聚氨酯塑胶跑道铺装维修材料，其特征在于，所述填料为滑石粉、碳酸钙、蒙脱土或高岭土中的一种或多种。
5.根据权利要求1所述的一种环保型聚氨酯塑胶跑道铺装维修材料，其特征在于，所述的增塑剂是二乙二醇二苯甲酸酯、柠檬酸三丁酯或它们的混合物。
6.根据权利要求1所述的一种环保型聚氨酯塑胶跑道铺装维修材料的制备方法，其特征在于，所述制备方法包括下列步骤：
(1)将大豆多元醇、聚四氢呋喃多元醇、填料、颜料、改性剂、增塑剂加热至100-150℃，抽真空1.5-2h；
(2)将步骤(1)所得物料冷却至50-60℃，加入异氰酸酯，保温6-8h；
(3)将步骤(2)所得物料冷却至25-35℃，加入潜固剂，保温1-2h，抽真空1-2h，制得环保型聚氨酯塑胶跑道铺装维修材料。
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