CN110467716A - 一种松香基hdi型抑菌聚氨酯的制备方法 - Google Patents
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Abstract
本发明公开了一种松香基HDI型抑菌聚氨酯的制备方法。以松香作原料,通过对其结构中双键与羧基改性,合成得到丙烯酸松香GMA酯化物(RAG),在丙酮作溶剂的情况下,首先RAG与六亚甲基二异氰酸酯反应生成预聚体,再与亲水性扩链剂N‑甲基二乙醇胺和有机硅1,3‑双(3‑氨丙基)‑1,1,3,3‑四甲基二硅氧烷进行扩链反应,成功制备了松香基HDI型水性聚氨酯乳液。通过平板菌落计数法测定松香基HDI型水性聚氨酯的抑菌活性,其对金黄色葡萄球菌的抑菌率在95%以上,对大肠杆菌的抑菌率在99%以上,说明制备得到的松香基HDI型水性聚氨酯具有优异的抑菌性,有望在医疗卫生、生物工程、食品包装等领域得到广泛的应用。
Description
技术领域
本发明涉及一种以松香为原料制备抑菌聚氨酯的方法。
技术背景
聚氨酯(PU)是由羟基多元醇和异氰酸酯以及小分子扩链剂反应制备的一种合成树脂,具有良好的力学性能,作为一种新兴的有机高分子材料被广泛用于油漆、涂料、胶黏剂、皮革涂饰剂、油墨等方面,成为世界六大合成材料之一。目前用于合成PU的原料如聚酯多元醇、异氰酸酯、扩链剂等大多都来自于不可再生的石油化工原料。近年来,随着石油资源的不断减少和环保要求的日益提高,急需寻找天然无害、廉价易得、可再生、无污染的原料可以部分或全部取代聚酯多元醇或聚醚多元醇来制备聚氨酯。松香是一种丰富的天然可再生林产资源,不仅廉价易得,其结构中的双键与羧基为其改性提供了前提,而且松香的分子结构为内聚能较高、空间位阻较大的三元环菲结构,较高的内聚能可赋予PU优异的耐热性能,较大的空间效应可限制链段运动,从而赋予线性聚氨酯媲美多官能度PU的力学强度。
聚氨酯材料也可用在医疗卫生、食品包装等领域,但在使用或存放过程中,在一定的温湿度条件下,其表面极易生长或繁殖细菌,从而传播疾病,对人们的生命健康造成巨大威胁。如何将抗菌剂和聚氨酯结合,制备出性能优异、绿色可持续发展的聚氨酯弹性体并赋予其抗菌性能具有重大的科学意义和应用价值。抗菌性聚氨酯在玩具、家具、汽车、医疗卫生、食品包装、基底基材等领域具有极大的应用空间。本发明以丙烯酸松香GMA二元醇(RAG)和六亚甲基二异氰酸酯(HDI)为单体,与亲水性扩链剂N-甲基二乙醇胺(MDEA)和有机硅1,3-双(3-氨丙基)-1,1,3,3-四甲基二硅氧烷(APTMDS)进行扩链反应,通过预聚法合成了具有抑菌性的松香基HDI型水性聚氨酯乳液,并以金黄色葡萄球菌、大肠杆菌分别作为革兰氏阳性菌和革兰氏阴性菌的代表菌种,通过平板菌落计数法对制备的聚氨酯乳液进行抑菌性能的测试,抑菌率均达95%以上,证明其具有优良的抑菌性能。
发明内容
本发明的目的是提供一种以松香为原料制备松香基抑菌性聚氨酯的方法。
本发明的具体步骤如下:
将100.0质量份丙烯酸松香GMA酯化物(RAG)用300-500质量份分析纯的丙酮溶解,加入0.70-0.75质量份化学纯二月桂酸二丁基锡(DBTDL),分散均匀后转移至装有搅拌棒、回流冷凝管、温度计和氮气保护装置的反应釜中,在300~500r·min-1下进行搅拌,水浴加热至40~50℃后,加入40.0~60.0质量份纯度99%的六亚甲基二异氰酸酯(HDI)进行反应,待-NCO含量降至理论值时,加入12.0~16.0质量份纯度99%的亲水性扩链剂N-甲基二乙醇胺(MDEA),反应至-NCO降为理论值,降温至25℃,加入0.0~8.0质量份纯度98%的1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷(APTMDS)反应30分钟,再加入6.0~8.0质量份分析纯的冰乙酸中和20~30分钟,加入20~40mL去离子水,在1200~1500r·min-1的转速下乳化10~20分钟,经减压蒸馏除去丙酮,得到固含量为15-25%松香基HDI型水性聚氨酯乳液。利用平板菌落计数法测试聚氨酯的抑菌活性。
所述丙烯酸松香GMA酯化物(RAG)制备方法为:
(1)将100.0质量份松香加入到装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中,加热熔化后在400r·min-1下进行搅拌,加热至230℃后,开始缓慢滴加28.60质量份化学纯丙烯酸,持续1小时,滴加完毕后使其在230℃下继续反应2小时,待温度降至200℃出料,得到丙烯酸松香加成物;
(2)在反应釜中将100.0质量份步骤(1)所得丙烯酸松香加成物溶解于176.0质量份分析纯甲苯中,加入76.0质量份纯度97%甲基丙烯酸缩水甘油酯,0.5质量份分析纯三乙胺和0.40质量份分析纯1,4-对苯二酚,升温至120℃,反应4小时后结束,测酸值为4.0mgKOH·g-1,减压蒸馏除去甲苯,即得丙烯酸松香GMA酯化物(RAG),测固体质量百分比为92%。
本发明最显著的特点是以天然可再生资源松香为原料,通过对其结构中的双键与羧基进行改性,合成了一种新型的松香基二元醇,可以作为制备水性聚氨酯的单体,所得松香基HDI型水性聚氨酯乳液经测试对金黄色葡萄球菌和大肠杆菌具有良好的抑菌性,有望在医疗卫生、生物工程、食品包装等领域得到广泛的应用。
具体实施方式
丙烯酸松香GMA酯化物(RAG)制备方法为:
(1)将100.0质量份松香加入到装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中,加热熔化后在400r·min-1下进行搅拌,加热至230℃后,开始缓慢滴加28.60质量份化学纯丙烯酸,持续1小时,滴加完毕后使其在230℃下继续反应2小时,待温度降至200℃出料,得到丙烯酸松香加成物;
(2)在反应釜中将100.0质量份步骤(1)所得丙烯酸松香加成物溶解于176.0质量份分析纯甲苯中,加入76.0质量份纯度97%甲基丙烯酸缩水甘油酯,0.5质量份分析纯三乙胺和0.40质量份分析纯1,4-对苯二酚,升温至120℃,反应4小时后结束,测酸值为4.0mgKOH·g-1,减压蒸馏除去甲苯,即得丙烯酸松香GMA酯化物(RAG),测固体质量百分比为92%。
实施例1:
将100.0质量份丙烯酸松香GMA酯化物(RAG)用320质量份分析纯丙酮溶解,加入0.7质量份化学纯二月桂酸二丁基锡(DBTDL),分散均匀后转移至装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中,在400r·min-1下进行搅拌,水浴加热至45℃后,加入48.62质量份纯度99%的六亚甲基二异氰酸酯(HDI)进行反应,待-NCO含量降至理论值时,加入12.9质量份纯度99%的亲水性扩链剂N-甲基二乙醇胺(MDEA),反应至-NCO含量降为理论值,降低反应温度至25℃,加入2.97质量份纯度98%的1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷(APTMDS)反应30分钟,再加入6.0质量份分析纯冰乙酸中和20分钟,加入30mL去离子水,在1300r·min-1的转速下乳化15分钟,最后经减压蒸馏除去丙酮,得到固含量为19%松香基HDI型抑菌型水性聚氨酯乳液。通过平板菌落计数法对聚氨酯乳液进行抗菌性能测试,结果对金黄色葡萄球菌(ATCC 6538)的抑菌率为97.78%,对大肠杆菌(ATCC11229)的抑菌率为99.99%。
实施例2:
将100.0质量份丙烯酸松香GMA酯化物(RAG)用325质量份分析纯丙酮溶解,加入0.7质量份化学纯二月桂酸二丁基锡(DBTDL),分散均匀后转移至装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中,在400r·min-1下进行搅拌,水浴加热至45℃后,加入48.62质量份纯度99%的六亚甲基二异氰酸酯(HDI)进行反应,待-NCO含量降至理论值时,加入12.9质量份纯度99%的亲水性扩链剂N-甲基二乙醇胺(MDEA),反应至-NCO含量降为理论值,降低反应温度至25℃,加入7.4质量份纯度98%的1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷(APTMDS)反应30分钟,再加入6.0质量份分析纯冰乙酸中和20分钟,加入30mL去离子水,在1300r·min-1的转速下25℃乳化15分钟,经减压蒸馏除去丙酮,得到固含量为20%松香基HDI型抑菌水性聚氨酯乳液。通过平板菌落计数法对聚氨酯乳液进行抗菌性能测试,结果对金黄色葡萄球菌(ATCC 6538)的抑菌率为99.69%,对大肠杆菌(ATCC 11229)的抑菌率为99.99%。
实施例3:
将100.0质量份丙烯酸松香GMA酯化物(RAG)用348质量份分析纯丙酮溶解,加入0.7质量份化学纯二月桂酸二丁基锡(DBTDL),分散均匀后转移至装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中,在400r·min-1下进行搅拌,水浴加热至45℃后,加入48.62质量份纯度99%的六亚甲基二异氰酸酯(HDI)进行反应,待-NCO含量降至理论值时,加入12.91质量份纯度99%的亲水性扩链剂N-甲基二乙醇胺(MDEA),反应至-NCO含量降为理论值,降低反应温度至25℃,加入8.0质量份分析纯冰乙酸中和20分钟,加入30mL去离子水,在1300r·min-1的转速下25℃乳化15分钟,经减压蒸馏除去丙酮,得到固含量为19%松香基HDI型抑菌水性聚氨酯乳液。通过平板菌落计数法对聚氨酯乳液进行抗菌性能测试,结果对金黄色葡萄球菌(ATCC 6538)的抑菌率为95.52%,对大肠杆菌(ATCC 11229)的抑菌率为99.89%。
实施例4:
将100.0质量份丙烯酸松香GMA酯化物(RAG)用357质量份分析纯丙酮溶解,加入0.7质量份化学纯二月桂酸二丁基锡(DBTDL),分散均匀后转移至装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中,在400r·min-1下进行搅拌,水浴加热至45℃后,加入48.62质量份纯度99%的六亚甲基二异氰酸酯(HDI)进行反应,待-NCO含量降至理论值时,加入16.3质量份纯度99%的亲水性扩链剂N-甲基二乙醇胺(MDEA),反应至-NCO含量降为理论值,降低反应温度至25℃,加入8.0质量份冰乙酸中和20分钟,加入30mL去离子水,在1300r·min-1的转速下25℃乳化15分钟,经减压蒸馏除去丙酮,得到固含量为22%松香基HDI型抑菌水性聚氨酯乳液。通过平板菌落计数法对聚氨酯乳液进行抗菌性能测试,结果对金黄色葡萄球菌(ATCC 6538)的抑菌率为98.79%,对大肠杆菌(ATCC 11229)的抑菌率为99.99%。
Claims (1)
1.一种松香基HDI型抑菌聚氨酯的制备方法,其特征在于具体步骤为:
将100.0质量份丙烯酸松香GMA酯化物即RAG用300-500质量份分析纯丙酮溶解,加入0.70-0.75质量份化学纯二月桂酸二丁基锡,分散均匀后转移至装有搅拌棒、回流冷凝管、温度计和氮气保护装置的反应釜中,在300~500 r·min-1下进行搅拌,水浴加热至40~50℃后,加入40.0~60.0质量份纯度99%的六亚甲基二异氰酸酯进行反应,待-NCO含量降至理论值时,加入12.0~16.0质量份纯度99%的亲水性扩链剂N-甲基二乙醇胺,反应至-NCO降为理论值,降温至25℃,加入0.0~8.0质量份纯度98%的1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷反应30分钟,再加入6.0~8.0质量份分析纯的冰乙酸中和20~30分钟,加入20~40mL去离子水,在1200~1500 r•min-1的转速下乳化10~20 分钟,经减压蒸馏除去丙酮,得到固含量为15-25%松香基HDI型水性聚氨酯乳液;利用平板菌落计数法测试聚氨酯的抑菌活性;
所述丙烯酸松香GMA酯化物即RAG制备方法为:
(1)将100.0质量份松香加入到装有搅拌棒、回流冷凝管、温度计、氮气保护装置的反应釜中,加热熔化后在400 r·min-1下进行搅拌,加热至230℃后,开始缓慢滴加28.60质量份化学纯丙烯酸,持续1小时,滴加完毕后使其在230℃下继续反应2小时,待温度降至200℃出料,得到丙烯酸松香加成物;
(2)在反应釜中将100.0质量份步骤(1)所得丙烯酸松香加成物溶解于176.0质量份分析纯甲苯中,加入76.0质量份纯度97%甲基丙烯酸缩水甘油酯,0.5质量份分析纯三乙胺和0.40质量份分析纯1,4-对苯二酚,升温至120℃,反应4小时后结束,测酸值为4.0mgKOH·g-1,减压蒸馏除去甲苯,即得丙烯酸松香GMA酯化物即RAG,测固体质量百分比为92%。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105646822A (zh) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | 一种松香基ipdi型聚氨酯预聚体的制备方法 |
CN105646831A (zh) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | 一种松香基脂肪族聚氨酯预聚体的制备方法 |
CN109265727A (zh) * | 2018-08-14 | 2019-01-25 | 桂林理工大学 | 一种松香基hdi型聚氨酯分子印迹微球的制备方法 |
CN109369951A (zh) * | 2018-08-14 | 2019-02-22 | 桂林理工大学 | 一种松香基ipdi型聚氨酯分子印迹微球的制备方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105646822A (zh) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | 一种松香基ipdi型聚氨酯预聚体的制备方法 |
CN105646831A (zh) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | 一种松香基脂肪族聚氨酯预聚体的制备方法 |
CN109265727A (zh) * | 2018-08-14 | 2019-01-25 | 桂林理工大学 | 一种松香基hdi型聚氨酯分子印迹微球的制备方法 |
CN109369951A (zh) * | 2018-08-14 | 2019-02-22 | 桂林理工大学 | 一种松香基ipdi型聚氨酯分子印迹微球的制备方法 |
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