CN115340654B - 一种钢筋混凝土防护用聚脲弹性体及其制备方法 - Google Patents

一种钢筋混凝土防护用聚脲弹性体及其制备方法 Download PDF

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CN115340654B
CN115340654B CN202211218705.1A CN202211218705A CN115340654B CN 115340654 B CN115340654 B CN 115340654B CN 202211218705 A CN202211218705 A CN 202211218705A CN 115340654 B CN115340654 B CN 115340654B
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史兰香
张冀男
刘斯婕
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Hubei Kaiyao Hong Energy Saving Materials Co ltd
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Abstract

本发明提供一种钢筋混凝土防护用聚脲弹性体及其制备方法，其由氨基聚醚、新型多异氰酸酯和新型扩链剂共聚得到。本发明提供的聚脲弹性体具有良好的抗菌、防腐蚀、防老化性能，能应用于陆地、海洋建筑工程防止钢筋混凝土结构腐蚀、老化和抗菌，提高其安全性和耐久性。

Description

一种钢筋混凝土防护用聚脲弹性体及其制备方法
技术领域
本发明涉及钢筋混凝土防护用聚脲弹性体技术领域，具体涉及一种钢筋混凝土防护用聚脲弹性体及其制备方法。
背景技术
钢筋混凝土的主体结构在其使用的过程中，由于自身的老化、腐蚀、辐射、各种自然灾害和其它人为的损伤等环境因素的综合影响，会导致建筑的腐蚀和破坏，引发混凝土钢筋锈蚀，严重影响整个建筑结构的服役年限，一旦出现质量问题，则会造成巨大的损失。
聚脲弹性体密度小、压缩强度大、导热系数小、吸水率低，分子中除了含有大量的脲键外，还含有氨酯键、酯键、醚键、缩二脲键、氢键等，具有优良的抗断裂性、耐磨性、柔韧性和耐腐蚀性，因此，聚脲弹性体在混凝土防护、钢结构防腐、建筑防水等领域广泛应用。
CN201310385340.6公开了一种制备耐腐蚀抗菌防腐聚脲复合涂层的方法，主要通过在B组分中添加纳米硫氰酸亚铜等抗菌剂制备金属或混凝土表面的防腐抗菌保护涂层，该聚脲涂层的抗菌能力、耐腐蚀性和抗磨性较好。但这种抗菌剂以物理方式添加，没有通过化学键连接在基料高分子上，分散不均匀，抗菌效果较差。目前，多功能聚脲弹性体深受欢迎，但种类较少，因此，开发具有优良力学性能、防腐性能和抗菌性能的多功能聚脲弹性体非常必要。
发明内容
本发明的目的在于提供一种钢筋混凝土防护用聚脲弹性体及其制备方法，用于解决现有技术中聚脲弹性体抗冲击力、附着力、抗菌、防腐蚀、防老化等性能不佳的问题。
为实现上述目的及其它相关目的，本发明第一方面提供一种钢筋混凝土防护用聚脲弹性体，包括A组份和B组分，所述A组分为预聚物；所述B组分包括以下重量份材料：扩链剂20-30重量份，氨基聚醚72-140重量份，助剂5-10重量份；
所述预聚物由氨基聚醚D400与多异氰酸酯反应制备；
所述多异氰酸酯的结构式为：
Figure 212979DEST_PATH_IMAGE001
所述扩链剂结构式为：
Figure 130119DEST_PATH_IMAGE002
所述氨基聚醚为氨基聚醚D2000、氨基聚醚ED600、氨基聚醚ED900及它们的混合物；
所述助剂为流平剂、消泡剂等，流平剂为有机硅聚醚类共聚物，消泡剂为有机硅类消泡剂。
本发明第二方面提供一种上述钢筋混凝土防护用聚脲弹性体的制备方法，包括如下步骤：
A组分的制备：在N2氛围下，以干燥的DMF为溶剂，加入干燥的氨基聚醚D400， 10-15℃下，加入多异氰酸酯，固含量为70%左右，搅拌反应，测定预聚物-NCO含量12-14.7%，出料，即得预聚物A组分；
B组分的制备：在N2氛围下，将氨基聚醚溶于干燥的DMF中，按原料配比加入扩链剂和助剂，搅拌均匀，出料，得到B组分；
聚脲弹性体的制备：将A组分加入B组分中，搅匀，倒入聚四氟乙烯模具中，50-60℃干燥24-36h，0.1MPa真空下80℃干燥1h，110℃挥发DMF至恒重，得到聚脲弹性体。
本发明第三方面提供所述的多异氰酸酯和扩链剂的制备方法，包括如下步骤：
所述多异氰酸酯的制备方法：
Figure 972173DEST_PATH_IMAGE003
；
所述扩链剂的制备方法：
Figure 367382DEST_PATH_IMAGE004
。
本发明第四方面提供所述的一种钢筋混凝土防护用聚脲弹性体在陆地、海洋建筑工程的钢筋混凝土抗菌、防腐蚀、防老化中的应用。
本发明的钢筋混凝土防护用聚脲弹性体及其制备方法，具有以下有益效果：本发明制备了一种新型聚脲弹性体，其喷涂在钢筋混凝土表面，达到了良好的钢筋混凝土防腐蚀效果，能大幅度提高钢筋混凝土的力学能力和耐久性，能很好的满足钢筋混凝土的防护需求；同时，苯酚基团的引入使聚脲弹性体具有了抗菌、防老化性能。制备的新型多异氰酸酯的苯异氰酸酯基以脲基与乙基磷酰胺连接，克服了使用甲苯二异氰酸酯单体产生的毒性、高蒸汽压和低闪点等缺点，环境友好；制备的新型扩链剂分子中含有苯酚基团，一方面能催化聚脲产品中残存的游离-NCO自聚，降低产品中游离-NCO的含量，提高弹性体的各项力学性能；二方面，苯酚基团可使细菌、微生物的蛋白质凝固沉淀而凋亡，赋予聚脲弹性体具有抗菌性能；三方面，苯酚基团具有良好的抗氧化活性，能保护聚脲弹性体，减缓其老化。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易的了解本发明的其它优点与功效。本发明还可以通过另外不同的具体实施方式加以实施和应用，本说明书中的各项细节也可以基于不同观点和应用，在没有背离本发明的精神下进行各种修饰和改变。
实施例1
多异氰酸酯1的制备：
高压釜中，加入26g (0.1mol)异环磷酰胺、200 mL饱和甲醇/氨溶液，64℃反应6h，冷至室温，减压蒸干，纯化，制得P-[N,N-双-（β-氨乙基）]-1-氧-3-氮-2-磷杂环己烷-P-氧化物，收率87.9%。元素分析（C7H19N4O2P）理论值：C, 37.83; H, 8.62; N, 25.21; P,13.94。实测值：C, 37.81; H, 8.63; N, 25.22; P, 13.91。
将22.2g (0.1mol)P-[N,N-双-（β-氨乙基）]-1-氧-3-氮-2-磷杂环己烷-P-氧化物加入60mL干燥的甲苯中，搅拌，控温在10-15℃，滴加34.8g (0.2mol)甲苯二异氰酸酯/40mL甲苯溶液，保温反应1h，减压蒸除甲苯，纯化，制得多异氰酸酯1，收率87.7%。元素分析（C25H31N8O6P）理论值：C, 52.63; H, 5.48; N, 19.64; P, 5.43。实测值：C, 52.60; H,5.46; N, 19.63; P, 5.43。
扩链剂1的制备：
在N2氛围下，将6g (0.1mol)乙二胺和6.3g (0.2mol)多聚甲醛溶于30mL乙醇中，搅拌，加入21.6g (0.2mol) 4-甲基苯酚，回流4h，减压蒸干，再加入10mL无水乙醇，搅拌，通入过量的氯化氢气体，反应1h，过滤，得到N，N’-二（2-羟基-5-甲苄基）乙二胺盐酸盐。将该盐酸盐溶于水，加21.2g (0.6mol) Na2CO3溶液，搅拌，析出固体，过滤，纯化，制得扩链剂1，收率63.3%。1HNMR(400MHz, CDCl3) 6.98 (dd, J=8.2, 1.8Hz, 2H), 6.83-6.68 (m, 4H),5.07 (s, 2H), 3.96 (s, 4H), 2.84 (m, 4H), 2.25 (s, 6H), 2.03 (s, 2H)。
A组分的制备：在N2氛围下，干燥的DMF溶剂中，加入35重量份干燥的氨基聚醚D400，15℃下，再加入50重量份多异氰酸酯1，固含量70%，搅拌反应，采用IS014896-2009方法测得预聚物-NCO的含量为12.2%，出料，得预聚物A组分；
B组分的制备：在N2氛围下，将72重量份氨基聚醚600溶于干燥的DMF中，加入30重量份扩链剂1，10重量份助剂，固含量70%，搅拌均匀，出料，得到B组分；
聚脲弹性体的制备：将A组分加入B组分中，搅匀，倒入聚四氟乙烯模具中，50-60℃干燥24-36h，0.1MPa真空下80℃干燥1h，110℃挥发DMF至恒重，得到聚脲弹性体。
实施例2
多异氰酸酯2的制备：
操作与实施例1相同，不同之处，用26g (0.1mol)环磷酰胺代替26g (0.1mol)异环磷酰胺，制得多异氰酸酯2，收率86.8%。元素分析（C25H31N8O6P）理论值：C, 52.63; H, 5.48;N, 19.64; P, 5.43。实测值：C, 52.61; H, 5.46; N, 19.61; P, 5.42。
扩链剂2的制备：
操作与实施例1相同，不同之处，用21.0g (0.1mol)双（4-氨基环己基）甲烷代替6g(0.1mol)乙二胺，制得扩链剂2，收率65.1%。1HNMR(400MHz, CDCl3) 6.98 (dd, J=8.2,1.8Hz, 2H), 6.83-6.68 (m, 4H), 5.05 (s, 2H), 3.94 (s, 4H), 2.57 (m, 2H), 2.26(s, 6H), 2.03 (s, 2H), 1.64-1.52 (m, 8H), 1.43 (m, 2H), 1.39-1.27 (m, 8H),1.21(m, 2H)。
A组分的制备：在N2氛围下，以干燥的DMF为溶剂，加入33重量份干燥的氨基聚醚D400，10℃下，再加入47重量份多异氰酸酯2，固含量70%，搅拌反应，采用IS014896-2009方法测得预聚物-NCO的含量为14.7%，出料，得预聚物A组分；
B组分的制备：在N2氛围下，将97重量份氨基聚醚ED900溶于干燥的DMF中，加入28重量份扩链剂2，7重量份助剂，固含量70%，搅拌均匀，出料，得到B组分；
聚脲弹性体的制备：将A组分加入B组分中，搅匀，倒入聚四氟乙烯模具中，50-60℃干燥24-36h，0.1MPa真空下80℃干燥1h，110℃挥发DMF至恒重，得到聚脲弹性体。
实施例3
将39.6g (0.66mol)乙二胺加入100 mL无水甲苯中，冷却至0℃，慢慢加入15.2g(0.1mol)POCl3，室温反应3h，饱和食盐水洗涤，干燥，减压蒸干，纯化，制得N,N,N-三（β-氨乙基）磷酰胺，收率91.2%。元素分析（C6H21N6OP）理论值：C, 32.14; H, 9.44; N, 37.48;P, 13.81。实测值：C, 32.11; H, 9.42; N, 37.49; P, 13.80。
将22.4g (0.1mol)N,N,N-三（β-氨乙基）磷酰胺加入60mL干燥的甲苯中，搅拌，控温在12℃，滴加52.2g (0.3mol)甲苯二异氰酸酯/60mL甲苯溶液，保温反应，减压蒸除甲苯，纯化，制得多异氰酸酯3，收率88.2%。元素分析（C33H39N12O7P）理论值：C, 53.08; H, 5.26;N, 22.51; P, 4.15。实测值：C, 53.05; H, 5.27; N, 22.50; P, 4.16。
A组分的制备：在N2氛围下，以干燥的DMF为溶剂，加入35重量份干燥的氨基聚醚D400，10-15℃下，再加入44重量份多异氰酸酯3，固含量70%，搅拌反应，采用IS014896-2009方法测得预聚物-NCO的含量为13.6%，出料，即得预聚物A组分；
B组分的制备：在N2氛围下，将97.3重量份氨基聚醚ED900溶于干燥的DMF中，加入21.1重量份扩链剂2，8重量份助剂，固含量70%，搅拌均匀，出料，得到B组分；
聚脲弹性体的制备：将A组分加入B组分中，搅匀，倒入聚四氟乙烯模具中，50-60℃干燥24-36h，0.1MPa真空下80℃干燥1h，110℃挥发DMF至恒重，得到聚脲弹性体。
实施例4
A组分的制备：在N2氛围下，以干燥的DMF为溶剂，加入32重量份干燥的氨基聚醚D400，10℃下，再加入40重量份多异氰酸酯3，固含量70%，搅拌反应，采用IS014896-2009方法测得预聚物-NCO的含量为14.1%，出料，即得预聚物A组分；
B组分的制备：在N2氛围下，将91重量份氨基聚醚ED900和47重量份氨基聚醚ED2000溶于干燥的DMF中，加入20重量份扩链剂2，10重量份助剂，固含量70%，搅拌均匀，出料，得到B组分；
聚脲弹性体的制备：将A组分加入B组分中，搅匀，倒入聚四氟乙烯模具中，50-60℃干燥24-36h，0.1MPa真空下80℃干燥1h，110℃挥发DMF至恒重，得到聚脲弹性体。
对比例1
本对比例1与实施例2相同，不同之处，用甲苯二异氰酸酯代替多异氰酸酯2。
对比例2
本对比例2与实施例2相同，不同之处，用双（4-氨基环己基）甲烷代替扩链剂2。
实施例5
对实施例1-4、对比例1-2制备的聚脲弹性体进行性能测试。参照GB/T528-2009方法，将聚脲弹性体胶片制成标准样条，测定材料的拉伸强度和断裂伸长率，拉伸速率50mm/min；硬度按 GB/T531.1-2008 的规定进行测试；耐碱性参照 GB/T9265-2009《建筑涂料涂层耐碱性的测定》方法测试；耐盐雾试验参考1991 - GB/T1771 《色漆和清漆耐中性盐雾性能的测定》方法测试；耐老化试验按照JG/T335-2011《混凝土结构防护用成膜型保护涂料》方法测试，同时可以结合 GB / T 1766 2008《色漆和清漆涂层老化的评级方法》标准来确定等级。耐碱性、耐盐雾、耐老化程度共分0-5级，数值越大，代表破坏程度越大，0级指无破坏，5级指严重破坏。
抑菌实验测试：选择海洋中常见的交替假单胞菌Pseudoalteromonas sp和霍乱弧菌Vibrio sp作为抑菌标本，培养后，分别接种于实施例1-4，对比例1-2样品中，样品浓度1.2mg/mL，于37℃、200rpm/min震荡培养24h，用蛋白核酸分析仪测定OD600，以培养基的吸光值计算材料的抗菌率。
Figure 306388DEST_PATH_IMAGE005
上述实施例仅例示性说明发明的原理及其功效，而非用于限制本发明。举凡所属领域的中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (4)

1.一种钢筋混凝土防护用聚脲弹性体，其特征在于，包括A组分和B组分，所述A组分为预聚物；所述B组分包括以下重量份材料：扩链剂20-30份，氨基聚醚72-140份，助剂5-10份；
所述预聚物由氨基聚醚D400与多异氰酸酯反应制备；
所述多异氰酸酯的结构式为：
Figure FDA0004254412230000011
所述扩链剂结构式为：
Figure FDA0004254412230000012
B组分中，所述氨基聚醚为氨基聚醚D2000、氨基聚醚ED600、氨基聚醚ED900及它们的混合物；
所述助剂为流平剂和消泡剂，所述流平剂为有机硅聚醚类共聚物，所述消泡剂为有机硅类消泡剂。
2.根据权利要求1所述的一种钢筋混凝土防护用聚脲弹性体的制备方法，其特征在于，包括如下步骤：
A组分的制备：在N2氛围下，以干燥的DMF为溶剂，加入干燥的氨基聚醚D400，10-15℃下，加入多异氰酸酯，固含量为70％左右，搅拌反应，测得预聚物-NCO含量12-14.7％，出料，即得预聚物A组分；
B组分的制备：在N2氛围下，将氨基聚醚溶于干燥的DMF中，按原料配比加入扩链剂和助剂，搅拌均匀，出料，得到B组分；
聚脲弹性体的制备：将A组分加入B组分中，搅匀，倒入聚四氟乙烯模具中，50-60℃干燥24-36h，0.1MPa真空下80℃干燥1h，110℃挥发DMF至恒重，得到聚脲弹性体。
3.根据权利要求2所述的一种钢筋混凝土防护用聚脲弹性体的制备方法，其特征在于，所述多异氰酸酯的制备方法如下：
Figure FDA0004254412230000021
所述扩链剂的制备方法如下：
Figure FDA0004254412230000022
4.根据权利要求1所述的一种钢筋混凝土防护用聚脲弹性体，其特征在于，所述聚脲弹性体在陆地、海洋建筑工程的钢筋混凝土防腐蚀、防老化、抗菌中的应用。
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