CN114478995A - 一种高韧性蓖麻油基互穿网络型聚合物路面材料及其制备方法 - Google Patents
一种高韧性蓖麻油基互穿网络型聚合物路面材料及其制备方法 Download PDFInfo
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Abstract
一种高韧性蓖麻油基互穿网络型聚合物路面材料及其制备方法，将蓖麻油制备得到含柔性链断的活性预聚体，然后将制得的蓖麻油基活性预聚体与环氧和胺类固化剂进行交联固化反应，得到高韧性蓖麻油基互穿网络型聚合物路面材料。本发明制备的聚合物网络中包含聚氨酯和聚合环氧两种不同的交联结构，体系中融合了柔性的植物油脂肪链段和韧性脂肪环环氧结构，并选用特殊的胺固化体系，可赋予制备的聚合物优异的韧性、相容性和耐候性，且同时保证聚合物材料优良的机械强度和断裂伸长率。高韧性蓖麻油基互穿网络型聚合物路面材料原料主要采用可再生的蓖麻油为主要原料，来源丰富。产品具有良好的相容性，本技术发明制备工艺简单方便，具有一定的应用前景。
Description
技术领域
本发明属于功能型热固性聚合物路面材料制备技术领域，具体涉及一种高韧性蓖麻油基互穿网络型聚合物路面材料及其制备方法。
背景技术
针对正交异性钢箱梁桥面铺装的特点和使用要求，通过对铺装材料、结构组合以及施工工艺进行了长期的理论研究和工程实践，基本上形成了三种不同的钢桥面铺装材料类型：(1)以水泥为胶结料的混凝土材料。(2)以沥青为胶结料的混凝土材料。(3)以耐候性高分子有机聚合物为胶结料的材料。
水泥基材料刚度和自重都较大，且水泥材料干、温缩裂缝的问题难以避免，限制了其在大跨径钢桥面铺装中的广泛应用，常用于小跨径桥梁或旧桥补强工程。
沥青混凝土在钢桥面的研究已经很多，具有丰富的理论和实践经验。沥青基材料是目前在钢桥面应用最多、最广泛的铺装材料。但沥青混凝土应用于中国大跨径钢箱梁桥铺装层时，凸显出高温性能不足的缺点，容易行车车辙、拥包、推移等永久变形破坏。
环氧沥青混凝土虽然解决了铺装层的高温稳定性问题，但铺装层的开裂现象却依然存在，往往经过两至三年较为正常使用的阶段，铺装层便要进入频繁的维修养护阶段，并最终被铣刨重铺。
相比之下，高分子聚合物铺装材料用于钢桥面铺装具有很多优异的性质。聚合物是由小分子单体通过聚合反应形成化学键连接成三维交联网络结构。通过合理选择原材料种类并采用专有高分子合成技术，可以大幅度改变产品形态及其性能，从而得到从柔软到坚硬的最终产品。和传统沥青混凝土桥面铺装相比，高分子聚合物桥面铺装主要具有以下优点：质量较轻，可明显减少桥梁负重；高粘接强度、拉伸强度、弯曲强度和弹性恢复率，能够承受大流量重负荷的反复疲劳作用；良好的不透水性，有效保护钢桥面板免受锈蚀；耐腐蚀性好，能够有效抵抗融雪剂、酸碱类物质和各种油污的侵蚀；可以进行模块化、工厂化生产，有效控制施工质量、缩短施工工期；常温下施工，避免高温加热对桥体造成破坏；维修养护快捷、方便。
目前，钢桥面铺装层采用聚合物铺装形式在我国仍处于探索和试验阶段，未有成功的案例可以借鉴，尤其是缺乏高耐候性能的聚合物铺装材料。另一方面，随着国内经济的发展和人们生活水平的不断提高，人们对材料使用健康、环保等方面的意识逐渐增强，对各类型产品的环保和综合性能提高研究提出了诸多新课题。常规形状记忆聚合物的制备几乎均采用石化资源为原料，环境污染和资源匮乏问题日益严重。开发利用安全、环保和节能的聚合物铺装材料是未来的主要发展方向之一。蓖麻油是我国最常见的一种油料作物，广泛分布在全国各地，其来源丰富。蓖麻油中含有大量羟基、酯基和双键，可以发生多种化学反应，如酯交换，脱水，热解、环氧化、加成反应等。在涂料、塑料、聚氨酯及橡胶等领域有着广泛应用。
本技术采用天然的蓖麻油制备出一种全新的高韧性蓖麻油基互穿网络型聚合物路面材料，尽可能降低使用毒性较大的苯类石化产品。本技术成果制备的此类聚合物具有原料来源丰富，环境友好，极具有广阔的市场应用前景。不仅可解决钢桥面铺装层结构面临的难题，同时为开启我国钢桥面及高速公路道面铺装生物基新材料应用的先河。
发明内容
解决的技术问题：本发明提供了高韧性蓖麻油基互穿网络型聚合物路面材料及其制备方法，以蓖麻油为原料，将蓖麻油经一系列反应制备得到含柔性链断的活性预聚体；然后将制得的蓖麻油基活性预聚体与环氧和特殊胺类固化剂进行交联固化反应，得到高韧性蓖麻油基互穿网络型聚合物路面材料。在这项发明中，聚合物网络体系中包含脂肪酸碳链的柔性聚氨酯结构和韧性环氧结构聚氨酯两种不同的交联结构，并选用特殊的胺固化体系，可赋予制备的聚合物优异的韧性、相容性和耐候性，且同时保证聚合物材料的优良力学性能。
技术方案：一种高韧性蓖麻油基互穿网络型聚合物路面材料的制备方法，由以下步骤制得：第一步：将蓖麻油和小分子多元醇按照摩尔比1：2.1-2.5加入到反应器中，然后加入蓖麻油质量0.5％的催化剂，220℃保温2-3小时，降温后得到中间产物1；第二步：预聚体制备得到中间产物1与聚醚多元醇和二异氰酸酯混合均匀，中间产物1与聚醚多元醇400控制在质量比为1:1，二异氰酸酯加入量确保控制总异氰酸根数为总羟基数的1.05-1.15，升温至30～50℃，加入占反应物总质量0.5％～0.6％的催化剂，反应2～3h后降温至室温，得到中间产物异氰酸根封端的蓖麻油基预聚体；第三步：将得到的蓖麻油基预聚体放入固化容器中，并加入脂环族环氧树脂—双(7-氧杂双环[4.1.0]3-庚甲基)己二酸酯，且所加入环氧树脂的质量为第二步所得到蓖麻油基预聚体质量的70％，然后加入蓖麻油基预聚体质量30％的3,3'-二氯-4,4'-二氨基二苯甲烷，60-80℃预混合搅拌均匀，然后升温至120℃，反应为2.0-3.0h，即得到高韧性蓖麻油基互穿网络型聚合物路面材料。
上述小分子多元醇为乙二醇和1，3-丙二醇中的任意一种。
上述聚醚多元醇为聚丙二醇1000和聚丙二醇2000中的任意一种。
上述催化剂为钛酸四丁酯、对甲基苯磺酸和二丁基氧化锡中的任意一种。
上述二异氰酸酯为异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)中的任意一种。
上述方法制得的高韧性蓖麻油基互穿网络型聚合物路面材料。
有益效果：①本发明提供的产品的聚合物网络体系中包含脂肪酸碳链的柔性聚氨酯结构和韧性环氧结构聚氨酯两种不同的交联结构，并选用特殊的胺固化体系，可赋予制备的聚合物优异的韧性、相容性和耐候性，且同时保证聚合物材料的优良机械强度和断裂伸长率。②相比现在技术水平，其强度和延展性能更加优越，可满足大跨度桥梁和常规高架桥路面的铺装要求。③本技术制备高韧性蓖麻油基互穿网络型聚合物路面材料原料主要采用可再生的蓖麻油为主要原料，来源丰富，降低了对化石资源的依赖，顺应了绿色环保与可持续发展的要求。
附图说明
图1为蓖麻油基预聚体的红外分析图，曲线1和曲线2分别对应中间产物1和制备得到的-NCO基团封端的聚氨酯预聚体，曲线1和曲线2上1690cm-1附近的宽峰证实了预聚体体系中C＝O的存在，3334cm-1附近的宽峰归因于N-H的伸缩振动，未见明显的羟基吸收峰，表明的-OH与过量的-NCO反应完全。曲线2预聚体红外谱图在2250cm-1附近出现了相对较弱的-NCO的特征吸收峰，表明异氰酸根封端的蓖麻油基预聚体成功制备。
具体实施方式
以下结合实施例对本发明的进一步说明：
实施例1
将一定质量的蓖麻油和乙二醇按照摩尔比1：2.1加入到反应器中，然后加入蓖麻油质量0.5％的钛酸四丁酯，220℃保温2小时，降温后得到中间产物1。预聚体制备得到中间产物1与一定质量的聚丙二醇1000和异佛尔酮二异氰酸酯(IPDI)混合均匀，中间产物1与聚醚多元醇400控制在质量比为1：1，二异氰酸酯加入量确保控制总异氰酸根数为总羟基数的1.05，升温至30℃，加入占反应物总质量0.5％的催化剂，反应2h后降温至室温，得到中间产物异氰酸根封端的蓖麻油基预聚体。将得到的蓖麻油基预聚体放入固化容器中，并加入一定质量的脂环族环氧树脂—双(7-氧杂双环[4.1.0]3-庚甲基)己二酸酯，且所加入环氧树脂的质量数为第二步所得到蓖麻油基预聚体质量的70％，然后加入蓖麻油基预聚体质量30％的3,3'-二氯-4,4'-二氨基二苯甲烷，60℃预混合搅拌均匀，然后升温至120℃，反应为2.0h，即得到高韧性蓖麻油基互穿网络型聚合物路面材料。
实施例2
将一定质量的蓖麻油和1，3-丙二醇按照摩尔比1：2.5加入到反应器中，然后加入蓖麻油质量0.5％的对甲基苯磺酸，220℃保温3小时，降温后得到中间产物1。预聚体制备得到中间产物1与一定质量的聚丙二醇2000和六亚甲基二异氰酸酯(HDI)混合均匀，中间产物1与聚醚多元醇400控制在质量比为1：1，二异氰酸酯加入量确保控制总异氰酸根数为总羟基数的1.15，升温至50℃，加入占反应物总质量0.6％的催化剂，反应3h后降温至室温，得到中间产物异氰酸根封端的蓖麻油基预聚体。将得到的蓖麻油基预聚体放入固化容器中，并加入一定质量的脂环族环氧树脂—双(7-氧杂双环[4.1.0]3-庚甲基)己二酸酯，且所加入环氧树脂的质量数为第二步所得到蓖麻油基预聚体质量的70％，然后加入蓖麻油基预聚体质量30％的3,3'-二氯-4,4'-二氨基二苯甲烷，80℃预混合搅拌均匀，然后升温至120℃，反应为3.0h，即得到高韧性蓖麻油基互穿网络型聚合物路面材料。
实施例3
将一定质量的蓖麻油和1，3-丙二醇按照摩尔比1：2.4加入到反应器中，然后加入蓖麻油质量0.5％的二丁基氧化锡，220℃保温2.5小时，降温后得到中间产物1。预聚体制备得到中间产物1与一定质量的聚丙二醇1000和异佛尔酮二异氰酸酯(IPDI)混合均匀，中间产物1与聚醚多元醇400控制在质量比为1：1，二异氰酸酯加入量确保控制总异氰酸根数为总羟基数的1.10，升温至40℃，加入占反应物总质量0.6％的催化剂，反应2.5h后降温至室温，得到中间产物异氰酸根封端的蓖麻油基预聚体。将得到的蓖麻油基预聚体放入固化容器中，并加入一定质量的脂环族环氧树脂—双(7-氧杂双环[4.1.0]3-庚甲基)己二酸酯，且所加入环氧树脂的质量数为第二步所得到蓖麻油基预聚体质量的70％，然后加入蓖麻油基预聚体质量30％的3,3'-二氯-4,4'-二氨基二苯甲烷，70℃预混合搅拌均匀，然后升温至120℃，反应为2.5h，即得到高韧性蓖麻油基互穿网络型聚合物路面材料。
比较例：
将实施例1、实施例3制备的聚合物路面材料进行力学性能测试，测定结果如表1中所述。
表1随机取各实验组的性能对比
注：聚合物正拉粘接强度(钢板)、拉伸强度参照GB/T 1040.3-2006测试，冲击强度参照GB/T1451-2005进行测试。
Claims (6)
1.一种高韧性蓖麻油基互穿网络型聚合物路面材料的制备方法，其特征在于由以下步骤制得：第一步： 将蓖麻油和小分子多元醇按照摩尔比1：2.1-2.5加入到反应器中，然后加入蓖麻油质量0.5%的催化剂，220℃保温 2-3 小时，降温后得到中间产物1；第二步：预聚体制备得到中间产物1与聚醚多元醇和二异氰酸酯混合均匀，中间产物1与聚醚多元醇400控制在质量比为1:1，二异氰酸酯加入量确保控制总异氰酸根数为总羟基数的1.05-1.15，升温至30~50℃，加入占反应物总质量0.5%~0.6%的催化剂，反应2~3h后降温至室温，得到中间产物异氰酸根封端的蓖麻油基预聚体；第三步：将得到的蓖麻油基预聚体放入固化容器中，并加入脂环族环氧树脂—双(7-氧杂双环[4.1.0]3-庚甲基)己二酸酯，且所加入环氧树脂的质量为第二步所得到蓖麻油基预聚体质量的70%，然后加入蓖麻油基预聚体质量30%的3,3'-二氯-4,4'-二氨基二苯甲烷，60-80℃预混合搅拌均匀，然后升温至120℃，反应为2.0-3.0h，即得到高韧性蓖麻油基互穿网络型聚合物路面材料。
2.根据权利要求1所述一种高韧性蓖麻油基互穿网络型聚合物路面材料的制备方法，其特征在于，所述小分子多元醇为乙二醇和1，3-丙二醇中的任意一种。
3.根据权利要求1所述一种高韧性蓖麻油基互穿网络型聚合物路面材料的制备方法，其特征在于，所述聚醚多元醇为聚丙二醇1000和聚丙二醇2000中的任意一种。
4.根据权利要求1所述一种高韧性蓖麻油基互穿网络型聚合物路面材料的制备方法，其特征在于，所述催化剂为钛酸四丁酯、对甲基苯磺酸和二丁基氧化锡中的任意一种。
5.根据权利要求1所述一种高韧性蓖麻油基互穿网络型聚合物路面材料的制备方法，其特征在于，所述二异氰酸酯为异佛尔酮二异氰酸酯（IPDI）和六亚甲基二异氰酸酯（HDI）中的任意一种。
6.权利要求1-5任一所述方法制得的高韧性蓖麻油基互穿网络型聚合物路面材料。
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