CN1194050C - 植物多酚类化合物的新用途 - Google Patents
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- CN1194050C CN1194050C CNB031375510A CN03137551A CN1194050C CN 1194050 C CN1194050 C CN 1194050C CN B031375510 A CNB031375510 A CN B031375510A CN 03137551 A CN03137551 A CN 03137551A CN 1194050 C CN1194050 C CN 1194050C
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Abstract
植物多酚类化合物的新用途,属于日用环保材料领域。本发明针对植物多酚独特的化学活性和生理活性,首次提出了将植物多酚类化合物作为挥发性有机物捕捉剂的应用和在制备室内有害气体吸附剂中的应用。本发明优点是:植物多酚可以作为与涂料和粘结剂基料的原料,不会影响涂料和粘结剂的性能,不会对涂料和粘结剂的色泽产生影响,并且在一定意义上还对涂料和粘结剂的性能有增效的作用。植物多酚是纯天然无毒提取物,使用时不会产生任何毒副作用,有很高的环保意义和很好的应用前景。植物多酚是地球上尚未被充分开发利用的、储量极为丰富的自然资源之一,本发明为植物深加工开辟了新的应用前景,为植物多酚开辟了新的研究方向。
Description
技术领域
本发明涉及植物多酚类化合物作为挥发性有机物捕捉剂以及室内有害气体等吸附剂的应用,属于日用环保材料领域。
背景技术
植物多酚类化合物广泛存在于自然界各种植物中,其含量仅次于纤维素和半纤维素,实际分布于植物的所有部分:表皮、木质部、根部、花、叶和果实中。植物多酚类化合物总数达数千种以上,包括单宁、木质素、黄酮类化合物等,因此其是一类结构复杂的物质,依照化学结构特征,可将植物多酚分为C6·Cl、C6·C2、C6·C3、C6·C2·C6、C6·C3·C6等类。C6代表一个芳香环,C2、C3分别代表脂肪族的二碳、三碳链,其分子量分布在几百至几千的范围之内。
植物多酚类化合物主要的来源是:森林副产物;茶属植物的株系及其杂交体;草本及植物性药材和水果、蔬菜等。
其中,森林副产物包括但不限于:落叶松、桉树、毛杨梅、黒荆树、山槐、槲树(皮)、黄华柳(絮)、漆树(心材)、柳杉(皮)、红根根皮、橡椀、刺梨、板栗(叶)、黄栌(叶)、栓皮栎(叶)、化香果等。
其中,茶属植物的株系及其杂交体中的植物多酚类化合物可来源但不限于:绿茶(如龙井、碧螺春等)、乌龙茶、青茶、白茶、红茶、黒茶等。
其中,草本及植物性药材和水果、蔬菜中的植物多酚类化合物可来源但不限于:大黄、芥草、贯众、方儿茶、地榆、麻黄、五倍子、桑椹、牡丹皮、仙鹤草、土茯苓、甘草、山茱萸、肉桂、槟榔(籽)、葡萄(皮、籽)、芦荟、油柑、银杏、苹果、黑加仑、蒲公英、何首乌、芒果、山楂、椰子、柿子、柠檬、梨、桃子、石榴、草莓、金橘、猕猴桃、杏、香蕉、岩白菜、胡萝卜、芹菜、黄瓜、豌豆、高粱、大麦等。
人类对植物多酚的认识和利用可以追溯到远古时代,最初将其用于鞣革,使生皮变成柔软、有良好透气和折叠性能的革,另外也被用作医药和染色。近年来,由于“回归自然”理念的兴起,人们重新热衷于天然产物的开发利用,植物多酚成为很多领域科学家共同关心的研究热点。随着对其抗氧化、捕捉自由基、衍生化反应等化学行为的了解,植物多酚类化合物越来越多的被用于食品、医药、化妆品等方面,而且对其研究日益发展拓宽,更多行业的科学家将开始涉足这类天然产物的研究。
植物鞣革的主要化学机理是植物多酚能在皮胶原纤维上产生多点氢键结合,在胶原纤维间产生交联,从而使胶原的热稳定性增加,生皮转变成为革。植物多酚中只有含有足够多的邻位酚羟基才能与胶原产生多点结合,其他的基团也参加反应,但不占主要地位,如羧基、醇羟基、醚氧基等。
植物多酚分子结构中的邻苯二酚或邻苯三酚中的邻位酚羟基很容易被氧化成醌类结构。因此酚类结构使其对活性氧等自由基具有很强的捕捉能力,例如多酚能与氧化反应产生的脂质自由基等结合,减少或阻止组织中氧化反应过程的进行,同时它可以与不饱和脂肪酸竞争性的与活性氧结合以终止脂质过氧化反应的进行。以茶多酚为例,其在水溶液中的自由基清除能力为ECG>EGCG>EGC>GA>EC=C;在脂中顺序为ECG=EGCG=EC=C>EGC>GA。在植物体内植物多酚可与维生素类抗氧化剂协同作用,抑制维生素的自氧化,具有增效剂的作用。
由于植物多酚上述特性,其在食品工业中有举足轻重的地位。首先植物多酚富含于茶叶、各种水果、蔬菜和谷物皮层中,具有抗诱变、抗癌、抗衰老、抗氧化和清除生物体内自由基等效果,大量食用对人类的健康非常有益;其次植物多酚作为一类天然的食品添可以加剂,不仅调节食物的味道,还可以起到一种高效、无毒、具有保健性的抗氧化和防腐作用;植物多酚已经作为营养元素和抗氧化剂在饮料、食用油、糕点、肉制品中得到广泛的应用。因此植物多酚有“第七营养素”的美誉。
在化妆品工业方面,植物多酚越来越多的被添加到化妆品、洗涤用品、牙膏、香水中,其具有的多种生物活性是人工合成品无法比拟的。植物多酚分子中的苯环结构在紫外区有很强的吸收,因此在化妆品工业中作为抗紫外添加剂的应用日趋受到重视。植物多酚对形成龋齿的细菌有强烈的抑制作用,还可消炎、除臭,已有将茶多酚作为添加剂用于牙膏和漱口水中。
植物多酚在上述领域的应用是其各种反应活性的综合的体现,而并非单一性质能达到的。正因为其具有多种反应活性,在一些尚未涉及的领域也有很大开发潜力。
当今,全世界涂料和粘结剂年产量约为2500万吨,并以3%的速度增加,按平均含溶剂40%计,全世界每年排放到大气中的溶剂约1000万吨,因此涂料和粘结剂中释放的挥发性有机物是大气中VOC的主要来源,并且有机物的释放也造成了资源的浪费。
涂料和粘结剂中的挥发性有机物(VOC)包括碳氢化合物、羰基化合物、有机酸、有机过氧化物、有机硫化物和有机卤化物等等,在光作用下能够与大气中氧化氮、硫化物发生光化学反应,形成难以散除、毒性很强的光化学烟雾;含氯的溶剂有可能释放出氯,破坏臭氧层,严重时臭氧产生空洞,导致高能紫外线过量到达地球表面,对人类的健康构成威胁。挥发性有机物对人类肌体的影响主要可分为如下三种:
a.气味和感官效应。包括感觉刺激和感觉干燥(如甲醛、甲苯二异氰酸酯等);
b.粘膜刺激和其他系统毒性导致的病态。刺激眼粘膜、鼻粘膜、呼吸道和皮肤等;还对中枢神经系统有抑制作用(如甲醛、甲苯二异氰酸酯等);
c.基因毒性和致癌性。目前很多挥发性有机物被证明是致癌物或可疑致癌物(如甲醛、苯系物、四氯乙烯、三氯乙烷、三氯乙烯等)。
当总挥发性有机化合物(TVOC)浓度小于0.2mg/m3时,不会产生刺激反应;大于3mg/m3时人体不适,产生病态反应;大于25mg/m3时,呈毒性反应。
另外,在现代办公和家居等室内环境中,臭氧(O3)污染愈来愈不容忽视。其一部分来自于汽车尾气污染导致的室外光化学反应;随着静电复印机、激光打印机、静电除尘器和臭氧杀菌消毒柜等产品的普及,它们引发的室内臭氧污染日益增加甚至超过前一污染源。作为强氧化剂,臭氧可强烈刺激机体粘膜组织,引起支气管和肺部组织发炎甚至水肿等病变,出现许多呼吸道疾病。持续暴露于被臭氧污染空气中,会损害肺部保护组织,导致肺结构不可恢复性病变,使人体对呼吸道感染和肺炎的免疫能力降低,严重时可导致死亡。此外,臭氧还可能与VOC、微生物和颗粒物等污染物联合作用,加重室内污染程度;臭氧会对室内纺织品、艺术品产生氧化腐蚀作用,导致其老化或褪色。因此,净化室内空气时,臭氧也是一项不容忽视的污染物。
目前,人们广泛关注的是涂料和粘结剂中甲醛的有效控制方法,市面上也较多的是针对甲醛的捕捉产品,这些产品采用过滤吸附的方法只能缓解一时的危害,不能有效遏制VOC的长期残留。
发明内容
本发明的目的是为了解决现有挥发性有机物捕捉产品的成本高、影响涂料性能,不能有效遏制VOC,并产生新污染的问题。本发明的另一个目的是为了消除室内有害气体及抑制病毒、细菌等微生物对于人体造成的危害。
本发明针对植物多酚独特的化学活性和生理活性,首次提出了将植物多酚类化合物作为挥发性有机物捕捉剂的应用和在制备室内有害气体吸附剂中的应用。
植物多酚化学反应特性主要有一下两方面:
1)大量酚羟基的存在,显示出很强的酚的特性和还原性。另外多酚与较之苯酚与甲醛的反应,植物多酚与甲醛反应的速度要快得多,其多个酚羟基的存在使羟基的邻位比多酚羟基的邻位活泼的多;酚的还原性使其很容易通过酚羟基的离解和自由基的途径被氧化。这种性质用作VOC捕捉剂,快速、高效,在环保领域有很好的应用前景。
2)生物多酚与蛋白质的结合反应是多酚最重要的化学性质,多酚的收敛性和对病毒、多种细菌、真菌、酵母菌的抑制能力,都与多酚-蛋白质结合有关,因此其对于室内空气中的细菌有一定抑制作用。
植物多酚对于挥发性有机物中的大多有毒物以及臭氧、氨气等有快速反应的性能,将其转化为无害物。如果将植物多酚填加到涂料和粘结剂中,即对涂料和粘结剂的功效有增效作用,又有效控制了游离状态的甲醛、甲苯二异氰酸酯、苯系物等有毒的挥发性物质。植物多酚本身无毒、无害,是一种理想的捕捉剂材料。各种不同植物提取的多酚类化合物均可用作VOC捕捉剂的原料,其功效视酚羟基等化学活性和生理活性基团的多少稍有差别。
另外,植物多酚对空气中的臭氧、氨气等有害气体以及病毒、多种细菌、真菌、酵母菌等都有吸附作用,可以给人们营造一个清新、自然的“气氛”,保护人们的身心健康。
本发明的优点是:
1)植物多酚可以作为与涂料和粘结剂基料的原料,不会影响涂料和粘结剂的性能,不会对涂料和粘结剂的色泽产生影响,并且在一定意义上还对涂料和粘结剂的性能有增效的作用。
2)植物多酚是纯天然无毒提取物,使用时不会产生任何毒副作用,有很高的环保意义和很好的应用前景。
3)植物多酚是地球上尚未被充分开发利用的、储量极为丰富的自然资源之一,本发明为植物深加工开辟了新的应用前景,为植物多酚开辟了新的研究方向。
具体实施方式
由于植物多酚独特的化学活性和生理活性,它对VOC中的大多有害物质及空气中的各种自由基、臭氧、氨气等污染物都有快速吸附转化的能力,并且不会引发二次污染,是理想的捕捉剂原料,本发明首次提出将植物多酚类化合物用作捕捉剂以及室内有害气体等吸附剂。
植物多酚类化合物作为捕捉剂应用时,以有以下两种使用方法。一种是与乳化剂等复配后直接作为填料加入涂料和胶粘剂中使用,这种方式捕捉效率高、用量少;另外一种是将其与乳化剂复配后加水作成喷剂,使用时均匀地喷射或涂刷在散发VOC的材料表面以及周围环境中,这种方式比较灵活,可以在任何时候使用。植物多酚作为室内有害气体等吸附剂应用时,将其与乳化剂复配后加水作成喷剂,使用时喷在周围环境中,可以在任何时候使用。
VOC捕捉剂以及室内有害气体等吸附剂的制备方法如下:
1)植物多酚类化合物的制备工艺:
不同原料的植物多酚类化合物提取方法基本一致,主要包括溶剂浸提、富集得到粗品,再用沉淀法或色谱法提纯等步骤得到的基本为无色的无定形粉末,一些可以形成无色晶体。
①将植物物料经植物粉碎机粉碎、过筛,制成粉末。采用3~6倍于植物粉末体积的45-80%(v/v)甲醇或丙酮水溶液作为提取液,水浴提取20分钟,过滤出溶液后,再加2~3倍45-80%(v/v)甲醇或丙酮水溶液提取20分钟,合并滤液;减压蒸馏除有机溶剂,得到浓缩液;浓缩液用一倍量的氯仿或石油醚萃取至无色;然后以1∶1的脂肪酸酯萃取;水浴减压蒸馏除脂肪酸酯,浓缩液真空干燥,得植物多酚类化合物的粗产品;
②将干燥后的粗提物溶于水中,用硫酸铝、氯化钙、氯化铝等进行沉淀反应,并用0.1mol/L3的碳酸氢钠溶液调整溶液的pH值至6.0左右,此时应有大量的沉淀析出,沉淀经一段时间的陈化,过滤,50-60℃热水洗涤后,用6mol/L3的盐酸溶液溶解;以的脂肪酸酯萃取酸化液5~8次,合并萃取液;减压蒸发浓缩、重结晶,得纯度较高的植物多酚类化合物。
2)VOC捕捉剂以及室内有害气体等吸附剂配制
VOC捕捉剂分为添加型和制剂型。
添加型VOC捕捉剂是将植物多酚类化合物和酯型非离子乳化剂,按照质量比(7~10)∶(0.7~1.0)混匀后制得。所采用的酯型非离子乳化剂分别为:甘油二酸酯(DG)、聚氧乙烯失水山梨醇单硬脂酸酯(Tween60)、聚氧乙烯失水山梨醇单油酸酯(Tween80)等。其中Tween60和Tween80可以混合加入也可单独加入;另外,当有不同使用要求时,可以加入增稠剂,如对于已含聚乙烯醇的乳胶漆等涂料就可以不用添加增稠剂,对于不含聚乙烯醇的涂料可以适当添加增稠剂,以改善对胶体的保护。增稠剂可采用聚乙烯醇。
制剂型VOC捕捉剂和室内有害气体等吸附剂是将植物多酚类化合物、酯型非离子乳化剂和水按质量比混匀,其中植物多酚类化合物:酯型非离子乳化剂:水为(3~10)∶(0.6~1.0);(85~95)。混合时,水温控制在40~50℃。所采用的酯型非离子乳化剂分别为:甘油单酸酯(MG)、聚氧乙烯失水山梨醇单硬脂酸酯(Tween60)、聚氧乙烯失水山梨醇单油酸酯(Tweeng0)等。其中Tween60和Tween80可以混合加入也可单独加入。
实施例一(添加型)
成分 质量份
植物多酚类化合物 7
DG 0.5
Tween60或Tween80 0.1~0.2
聚乙烯醇 0.1
本实施例适宜应用在不含聚乙烯醇的涂料中,作为VOC捕捉剂。本捕捉剂在涂料使用前作为填料加入,将其与涂料混匀后涂刷。
使用后,对添加本捕捉剂的涂料和粘结剂进行检测,其中游离甲醛的含量小于0.5%,游离异氰酸酯的含量是0.1%,溶剂型和水型涂料和粘结剂中总挥发性有机化合物的含量均低于200g/L。测试结果低于或达到国标规定的要求。涂料和粘结剂使用后对其挥发空间内的气体进行了检测,游离甲醛的含量为0.06mg/m3,游离异氰酸酯无检出,总挥发性有机化合物(TVOC)浓度小于0.25mg/m3,均低于或达到国标规定的要求。国标对室内空气中微量游离甲醛的限量是0.08mg/m3,微量游离异氰酸酯的限量是0.5%,TVOC浓度不能大于0.3mg/m3。
实施例二(制剂型)
成分 质量份
植物多酚类化合物 9
水 87
MG 0.7
Tween60或Tween80 0.3
本实施例适用于酚醛树脂胶粘剂。在胶粘剂使用后,将本捕捉剂喷在粘结剂使用部位、周围空气中和可能吸附VOC的介质上,封闭使用6小时后通风,即可达到捕捉效果。在空间15平方米的普通居室中,当粘结剂使用量为0.5公斤时,将本捕捉剂100克以雾状喷出,6小时后对其挥发空间的气体进行检测,其中游离甲醛的含量为0.07mg/m3,游离异氰酸酯无检出,总挥发性有机化合物(TVOC)浓度小于0.3mg/m3,均低于或达到国标规定的要求。国标对室内空气中微量游离甲醛的限量是0.08mg/m3,微量游离异氰酸酯的限量是0.5%,TVOC浓度不能大于0.3mg/m3。
其中,甲醛的测定采用国标GB/T 18204.26-2000规定的方法;异氰酸酯的测定采用GB18583-2001规定的方法;TVOC的测定采用GB 50325-2001规定的方法。
实施例三(其他气体等有害物质吸附剂)
成分 质量份
植物多酚类化合物 3
水 95
MG 0.5
在室内由于一些电子设备的使用或其他原因造成臭氧浓度过高时,可以将本吸附剂喷在空气中,十分钟即可消除臭氧及自由基造成的污染。并且其对空气中的病毒、多种细菌、真菌、酵母菌在一段时间内都有很强的抑制能力。
以上描述了本发明的应用,在不违背本发明的宗旨及范围的前提下,在一些技术细节上可能有些修改,但仍属于本发明保护的范围。
Claims (1)
1.植物多酚类化合物作为涂料中挥发性有机物捕捉剂的应用。
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EP1871850B1 (en) * | 2005-04-22 | 2018-06-27 | LG Chem, Ltd. | Functional uv paint, construction material using the same, and method of preparing the paint |
CN102304305B (zh) * | 2010-12-07 | 2013-12-18 | 中山市丽莎涂料有限公司 | 柿子皮提取物及其提取方法、以及含有柿子皮提取物的除甲醛涂料 |
CN103011700B (zh) * | 2011-09-26 | 2015-07-15 | 卢丹 | 一种墙体涂料组合物、其制备方法、用途以及包含其的墙体涂料 |
CN103393560A (zh) * | 2013-07-10 | 2013-11-20 | 温美苹 | 一种纯植物提取防龋抗菌消炎漱口水的配方 |
CN105331304B (zh) * | 2014-07-24 | 2019-04-12 | 3M创新有限公司 | 具有抗菌性的胶粘剂组合物、抗菌无纺布、清洁用品和制造抗菌无纺布的方法 |
CN104383655A (zh) * | 2014-10-29 | 2015-03-04 | 胡正义 | 一种除甲醛喷剂的制备方法及其喷剂 |
CN106752216A (zh) * | 2016-12-09 | 2017-05-31 | 河南同伟建材有限公司 | 一种具有耐擦洗功能的乳胶漆外加剂及其制备方法 |
CN107321328A (zh) * | 2017-07-12 | 2017-11-07 | 东莞市大森环境工程有限公司 | 一种voc吸附剂及其生产工艺 |
CN107876048A (zh) * | 2017-12-04 | 2018-04-06 | 安徽中弘科技发展有限公司 | 一种有效清除室内装修污染的光触媒制剂 |
CN110669233A (zh) * | 2018-07-03 | 2020-01-10 | 东北林业大学 | 一种抗氧化、抗紫外功能pva基食品包装膜的制备方法 |
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