CN108084949A - 一种纳米改性双组分无溶剂软包装粘合剂及其制备方法 - Google Patents
一种纳米改性双组分无溶剂软包装粘合剂及其制备方法 Download PDFInfo
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Abstract
本发明提供一种纳米改性双组分无溶剂软包装粘合剂及其制备方法,该粘合剂中A组分包括蓖麻油或者棕榈油植物油基多元醇、己二醇、聚醚多元醇、添加剂和氧化石墨烯预处理的纳米级钛白粉,B组分包括MDI、TPU、聚丙二醇、聚醚多元醇和木质素胺改性二苯基甲烷二异氰酸酯,本发明将A组分和B组分分别在反应釜中反应得到,由于存在蓖麻油代替部分聚醚多元醇或者聚酯多元醇,粘合剂中挥发物质和游离物质少,绿色安全,并添加预处理的纳米二氧化钛和添加剂,反应温和高效,赋予粘合剂抗紫外性能,此外在反应过程中依据MDI中活性NCO基团和多元醇的OH基团的反应成链长短及时调节反应温度,得到粘合性能优异的无溶剂软包装粘合剂。
Description
技术领域
本发明属于软包装复合材料粘合剂技术领域,具体涉及一种纳米改性双组分无溶剂软包装粘合剂及其制备方法。
背景技术
软包装是包装行业的一个重要组成部分,软包装复合薄膜通常由数层不同材质的薄膜复合而成,自近年来,随着经济的发展和消费市场的升级,便利,安全,廉价,卫生,快捷成为消费市场的主流方向。各种软包装适应了这一趋势正在高速的发展,其适用范围非常广泛,囊括了块状,颗粒,粉末,凝胶,真空及液体等不同形态,覆盖了医药,保健品,医疗器械,五金,玩具,文具,食品,农药,含气饮料,卫生用品以及服装纺织等行业。
采用干式法制备的软包装复合薄膜的性能除了与塑料薄膜和铝箔基材的性能有关外,还与复合所用的粘合剂有很大的关系。传统的粘合剂主要分为溶剂型,水基型及单组份固化型,但是难以满足市场日益更新的需求。无溶剂型粘合剂具有污染小,易操作的优点,但是目前无溶剂型粘合剂大多依赖进口,为了摆脱这一现状,食品级聚氨酯粘合剂成为国内研究者研究的热点。
中国专利CN 1288221C公开的一种无溶剂高强度聚氨酯粘结密封胶及其制备方法,该聚氨酯粘结密封胶的组分有端羟基聚醚、异氰酸酯、增塑剂、无机填料、有机填料、催化剂和抗氧剂,其中端羟基聚醚为端羟基三元聚氧化丙烯醚、端羟基聚四氢呋喃醚、聚氧化丙烯-蓖麻油多元醇共聚醚或者聚四氢呋喃-氧化丙烯共聚醚,异氰酸酯为甲苯二异氰酸酯、1,5-萘二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己二异氰酸酯中的两种混合物,增塑剂为邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、邻苯二甲酸二壬酯或者邻苯二甲酸二易癸酯,无机填料为乙炔炭黑、钛白粉、碳酸钙、滑石粉、4A分子筛、硫酸铝、氧化镁、有机膨润土或气相法白炭黑,有机填料为酚醛树脂、丙烯酸酯齐聚物、聚乙烯齐聚物、苯乙烯齐聚物、环氧树脂、PVC糊树脂或萜烯树脂,催化剂为辛酸亚锡、二月桂酸二丁基锡、三乙烯二胺、N-甲基吗啉或者三乙醇胺。该方法制备的无溶剂型聚氨酯粘合剂的固体含量高、柔韧性好、拉伸强度高。该方法制备的聚氨酯密封胶因避免使用有毒溶剂,通过无机填料和有机填料改性,赋予密封胶强度高,柔韧性好,拉伸强度高,抗紫外线稳定性好的性能,但是会产生挥发物质和有毒副产物,不能在软包装粘合剂中使用。中国专利CN 102844398B公开的双组份无溶剂聚氨酯粘合剂,该聚氨酯粘合剂包括第一组分和第二组分,第一组分包括第一植物油基多元醇、第二植物油基多元醇和聚异氰酸酯,第二组分包括第一植物油基多元醇和多元醇,其中第一植物油基多元醇选自蓖麻油基多元醇和大豆油基多元醇,第二植物油基多元醇选自亚麻油基多元醇或者桐油基多元醇,聚异氰酸酯包括4,4’-二苯基亚甲基二异氰酸酯,多元醇包括丙二醇,此外聚氨酯粘合剂中含包括抗氧化剂、偶联剂和有机酸添加剂。该方法制备的无溶剂聚氨酯粘合剂中将植物油改性多元醇或者其他聚酯/聚醚多元醇与二异氰酸酯反应获得,避免了迁移异氰酸酯基团与水分迁移生成的芳香胺的含量,使粘合剂中不包含任何挥发性或者可迁移性物质,保证安装材料的绿色安全性能。由上述现有技术可知,通过用植物油代替聚酯多元醇或者聚醚多元醇可提高聚氨酯粘合剂的绿色安全性能,为制备多功能的绿色软包装粘合剂扩宽了研究思路。
发明内容
本发明要解决的技术问题是提供一种纳米改性双组分无溶剂软包装粘合剂及其制备方法,包括A组分和B组分,A组分包括蓖麻油或者棕榈油植物油基多元醇、己二醇、聚醚多元醇、添加剂和氧化石墨烯预处理的纳米级钛白粉,B组分包括MDI、TPU、聚丙二醇、聚醚多元醇和木质素胺改性二苯基甲烷二异氰酸酯,本发明制备的粘合剂中粘合强度高,固化时间快,挥发物质和游离物质少,绿色安全,反应温和高效,抗紫外性能优异,提高了软包装粘合剂的功能性,降低了软包装薄膜的生产成本。
为解决上述技术问题,本发明的技术方案是:
一种纳米改性双组分无溶剂软包装粘合剂,其特征在于,所述纳米改性双组分无溶剂软包装粘合剂及其制备方法包括A组分和B组分,所述A组分包括蓖麻油或者棕榈油植物油基多元醇、己二醇、聚醚多元醇、添加剂和纳米改性材料,所述B组分包括MDI、TPU、聚丙二醇、聚醚多元醇和改性二苯基甲烷二异氰酸酯,所述添加剂为硅烷偶联剂、气相白炭黑、聚酯树脂或者稳定剂中的一种或者几种,所述纳米材料为氧化石墨烯预处理的纳米级钛白粉,所述改性二苯基甲烷二异氰酸酯为木质素胺改性二苯基甲烷二异氰酸酯。
作为上述技术方案的优选,所述A组分的成分,按重量份计,包括蓖麻油或者棕榈油植物油基多元醇50份、己二醇20份、聚醚多元醇25份、添加剂3份和纳米改性材料2份,总量为100份。
作为上述技术方案的优选,所述B组分的成分,按重量份计,包括MDI 40份、TPU 5份、聚丙二醇10份、聚醚多元醇30份和改性二苯基甲烷二异氰酸酯15份。
作为上述技术方案的优选,所述聚醚多元醇为分子量为2000-2500的聚丙二醇,羟基为370-400。
作为上述技术方案的优选,所述MDI为4,4’-二苯基甲烷二异氰酸酯,2,4’-二苯基甲烷二异氰酸酯和2,2’-二苯基甲烷二异氰酸酯中的一种或其混合物。
作为上述技术方案的优选,所述氧化石墨烯预处理的纳米级钛白粉的制备方法为:将钛的前驱体加入到乙二醇水溶液中,加入氧化石墨烯溶液混合均匀,在110-120℃下加热反应1-2h,降至室温后,加入聚氨酯泡沫吸附,离心,洗涤干燥,研磨,得到氧化石墨烯预处理的纳米级钛白粉。
作为上述技术方案的优选,所述改性二苯基甲烷二异氰酸酯的制备方法为:将木质素胺与异氰酸酯作为主要原料,在反应釜中,在有机金属类催化剂的作用下,加热加压反应得到木质素胺改性二苯基甲烷二异氰酸酯。
本发明还提供一种纳米改性双组分无溶剂软包装粘合剂,其特征在于,所述纳米改性双组分无溶剂软包装粘合剂的制备方法,包括以下步骤:
(1)A组分的制备:对反应釜进行气密性检查,用氮气置换干燥除水,调节温度至10℃,按重量份计,依次投入蓖麻油或者棕榈油植物油基多元醇,己二醇,聚醚多元醇,加热至80-100℃搅拌30min,加入预处理的纳米级钛白粉,真空高速搅拌1h,再加入添加剂并升温至60℃,高速搅拌至均匀,低速搅拌并降至室温,出料,得到纳米改性的A组分;
(2)B组分的制备:对反应釜进行气密性检查,用氮气置换干燥除水,调节温度至60℃,先加入聚丙二醇,加热至100℃,抽真空30min,降温至80℃-90℃投入MDI并搅拌20min,然后加入聚醚多元醇,升温至100℃,搅拌40min,再降温至60℃,投入MDI,升温至80℃,充分搅拌30min,最后加入15份的改性二苯基甲烷二异氰酸酯和TPU,升温至65℃搅拌60min,出料,得到木质素胺改性的B组分;
(3)将步骤(1)制备的纳米改性的A组分与步骤(2)制备的木质素胺改性的B组分组成纳米改性双组分无溶剂软包装粘合剂。
作为上述技术方案的优选,预处理的纳米级钛白粉与添加剂的质量比为1:1。
作为上述技术方案的优选,所述步骤(2)中,MDI可用TDI代替。
与现有技术相比,本发明具有以下有益效果:
(1)本发明制备的纳米改性双组分无溶剂软包装粘合剂包括A组分和B组分,A组分包括该粘合剂中A组分包括蓖麻油或者棕榈油植物油基多元醇、己二醇、聚醚多元醇、添加剂和氧化石墨烯预处理的纳米级钛白粉,其中,A组分中由于存在蓖麻油代替部分聚醚多元醇或者聚酯多元醇,提高聚氨酯的内交联程度,减少粘合剂中挥发物质和游离物质,在提高粘合剂的粘合性能的基础上,保证了软包装粘合剂的绿色安全,此外添加入氧化石墨烯预处理的纳米二氧化钛,该纳米材料是利用乙二醇改性纳米二氧化钛将氧化石墨烯附着在纳米二氧化钛表面,再将附着氧化石墨烯的纳米二氧化钛吸附于聚氨酯泡沫的孔洞中,由于聚氨酯泡沫与聚氨酯粘合剂具有相容性,因此,有利于氧化石墨烯和纳米二氧化钛均匀的分散于聚氨酯粘合剂中,利用纳米二氧化钛赋予聚氨酯粘合剂抗菌杀菌、防霉除臭、抗紫外线的功能,利用氧化石墨烯提高聚氨酯粘合剂的耐候性,进一步提高聚氨酯粘合剂的机械强度,利用聚氨酯泡沫载体提高纳米二氧化钛和氧化石墨烯的含量及分散性。此外将改性的纳米二氧化钛与添加剂联合作用,可以提高反应效率,降低反应温度,因此本发明制备的聚氨酯粘合剂除了具有优异的粘性,还具有抗菌杀菌、防霉除臭、抗紫外线、耐老化的功能,因此本发明制备的聚氨酯粘合剂可代替部分软包装薄膜材料的功能性,降低软包装材料的成本,且保鲜性能更佳。
(2)本发明制备的纳米改性双组分无溶剂软包装粘合剂包括A组分和B组分,B组分包括MDI、TPU、聚丙二醇、聚醚多元醇和木质素胺改性二苯基甲烷二异氰酸酯,B组分在反应釜的反应过程中依据MDI中活性NCO基团和多元醇的OH基团的反应成链长短及时调节反应温度,制备的无溶剂软包装粘合剂粘合强度高,固化时间快,木质素胺改性二苯基甲烷二异氰酸酯的芳香环和侧链上均含有羟基可以与异氰酸酯反应生产聚氨酯,在反应过程中木质素胺不仅作为交联剂也作为硬链段,更有利于提高聚氨酯的粘度和机械强度。
(3)本发明制备的纳米改性双组分无溶剂软包装粘合剂性能稳定,不含游离的有害物质,耐候性优异,耐老化性好,且具有抗菌杀菌、防霉除臭、抗紫外线的功能,因此不仅满足了软包装领域的使用需求,且可替代部分薄膜的作用,简化了软包装的工艺,降低了材料成本和生产成本,机械性和功能性俱佳,经济效益好,具有很好的市场竞争力。
具体实施方式
下面将结合具体实施例来详细说明本发明,在此本发明的示意性实施例以及说明用来解释本发明,但并不作为对本发明的限定。
实施例1:
A组分物料制备:50份蓖麻油,20份己二醇,25份聚醚多元醇,3份添加剂,2份纳米改性材料。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为10℃。将A组分物料按照顺序依次投入蓖麻油(45份),己二醇,聚醚多元醇,加热搅拌30min。将氧化石墨烯预处理的纳米钛白粉(金红石型)与蓖麻油5份,添加剂,气相白炭黑低温(5℃)高速分散,转速3000RPM保持30mi n后,投入反应釜搅拌并升温至60℃,保持高速搅拌。低速搅拌,降温,出料制得组分A物料。
B组分制备:40份MDI,5份TPU,10份聚丙二醇(分子量400),30份聚醚多元醇(分子量2000-2500),15份木质素胺改性二苯基甲烷二异氰酸酯。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为60℃;反应釜投料依次为聚丙二醇(分子量400),加热维持100℃,抽真空30min。降温80℃-90℃投入MDI20份并搅拌20min。投入聚醚多元醇(分子量2000-2500)控制温度100℃,搅拌40min。降温至60℃,投入MDI20份,维持温度80℃充分搅拌30min。投入15份木质素胺改性二苯基甲烷二异氰酸酯和TPU,维持温度65℃,60min。
实施例2:
A组分物料制备:50份蓖麻油,20份己二醇,25份聚醚多元醇,3份添加剂,2份纳米改性材料。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为10℃。将A组分物料按照顺序依次投入蓖麻油(45份),己二醇,聚醚多元醇,加热搅拌30min。将氧化石墨烯预处理的纳米钛白粉(金红石型)与高分子量非晶型饱和聚酯树脂1:1捏合分散,气相白炭黑随后加入共同捏合30min,投入反应釜搅拌并升温至90℃,保持高速搅拌。低速搅拌,降温,出料制得组分A物料。
B组分制备:40份MDI,5份TPU,10份聚丙二醇(分子量400),30份聚醚多元醇(分子量2000-2500),15份木质素胺改性二苯基甲烷二异氰酸酯。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为60℃;反应釜投料依次为聚丙二醇(分子量400),加热维持100℃,抽真空30min。降温80℃-90℃投入MDI20份并搅拌20min。投入聚醚多元醇(分子量2000-2500)控制温度100℃,搅拌40min。降温至60℃,投入MDI20份,维持温度80℃充分搅拌30min。投入15份木质素胺改性二苯基甲烷二异氰酸酯和TPU,维持温度65℃,60min。
实施例3:
A组分物料制备:50份蓖麻油,20份己二醇,25份聚醚多元醇,3份添加剂,2份纳米改性材料。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为10℃。将A组分物料按照顺序依次投入蓖麻油(45份),己二醇,聚醚多元醇,加热搅拌30min。将氧化石墨烯预处理的纳米钛白粉(金红石型)与高分子量非晶型饱和聚酯树脂1:1捏合分散,气相白炭黑随后加入共同捏合30min,投入反应釜搅拌并升温至90℃,保持高速搅拌。低速搅拌,降温,出料制得组分A物料。
B组分制备:40份MDI,5份TPU,10份聚丙二醇(分子量400),30份聚醚多元醇(分子量2000-2500),15份木质素胺改性二苯基甲烷二异氰酸酯。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为60℃;反应釜投料依次为聚丙二醇(分子量400),加热维持100℃,抽真空30min。降温80℃-90℃投入TDI28份并搅拌25min。投入聚醚多元醇(分子量2000-2500)控制温度100℃,搅拌40min。降温至60℃,投入TDI28份,维持温度80℃充分搅拌35min。投入15份木质素胺改性二苯基甲烷二异氰酸酯和TPU,维持温度65℃,60min。
实施例4:
A组分物料制备:50份蓖麻油,20份己二醇,25份聚醚多元醇,3份添加剂,2份纳米改性材料。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为10℃。将A组分物料按照顺序依次投入蓖麻油(45份),己二醇,聚醚多元醇,加热搅拌30min。将氧化石墨烯预处理的纳米钛白粉(金红石型)与高分子量非晶型饱和聚酯树脂1:1捏合分散,气相白炭黑随后加入共同捏合30min,投入反应釜搅拌并升温至90℃,保持高速搅拌。低速搅拌,降温,出料制得组分A物料。
B组分制备:40份MDI,5份TPU,10份聚丙二醇(分子量400),30份聚醚多元醇(分子量2000-2500),15份木质素胺改性二苯基甲烷二异氰酸酯。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为60℃;反应釜投料依次为聚丙二醇(分子量400),加热维持100℃,抽真空30min。降温80℃-90℃投入2,4MDI20份并搅拌20min。投入聚醚多元醇(分子量2000-2500)控制温度100℃,搅拌40min。降温至60℃,投入2,4MDI20份,维持温度80℃充分搅拌30min。投入15份木质素胺改性二苯基甲烷二异氰酸酯和TPU,维持温度65℃,60min。
实施例5:
A组分物料制备:50份蓖麻油,20份己二醇,25份聚醚多元醇,3份添加剂,2份纳米改性材料。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为10℃。将A组分物料按照顺序依次投入棕榈油多元醇(45份),己二醇,聚醚多元醇,加热搅拌30min。将氧化石墨烯预处理的纳米钛白粉(金红石型)与高分子量非晶型饱和聚酯树脂1:1捏合分散,气相白炭黑随后加入共同捏合30min,投入反应釜搅拌并升温至90℃,保持高速搅拌。低速搅拌,降温,出料制得组分A物料。
B组分制备:40份MDI,5份TPU,10份聚丙二醇(分子量400),30份聚醚多元醇(分子量2000-2500),15份木质素胺改性二苯基甲烷二异氰酸酯。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为60℃;反应釜投料依次为聚丙二醇(分子量400),加热维持100℃,抽真空30min。降温80℃-90℃投入2,4MDI20份并搅拌20min。投入聚醚多元醇(分子量2000-2500)控制温度100℃,搅拌40min。降温至60℃,投入2,4MDI20份,维持温度80℃充分搅拌30min。投入15份木质素胺改性二苯基甲烷二异氰酸酯和TPU,维持温度65℃,60min。
实施例6:
A组分物料制备:50份蓖麻油,20份己二醇,25份聚醚多元醇,3份添加剂,2份纳米改性材料。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为10℃。将A组分物料按照顺序依次投入蓖麻油(45份),己二醇,聚醚多元醇,加热搅拌30min。将氧化石墨烯预处理的纳米钛白粉(金红石型)与蓖麻油5份,添加剂,气相白炭黑低温(5℃)高速分散,转速3000RPM保持30mi n后,投入反应釜搅拌并升温至60℃,保持高速搅拌。低速搅拌,降温,出料制得组分A物料。
B组分制备:40份MDI,5份TPU,10份聚丙二醇(分子量400),30份聚醚多元醇(分子量2000-2500),15份木质素胺改性二苯基甲烷二异氰酸酯。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为60℃;反应釜投料依次为聚丙二醇(分子量400),加热维持100℃,抽真空30min。降温80℃-90℃投入4,4MDI20份并搅拌20min。投入聚醚多元醇(分子量2000-2500)控制温度100℃,搅拌40min。降温至60℃,投入4,4MDI20份,维持温度80℃充分搅拌30min。投入15份木质素胺改性二苯基甲烷二异氰酸酯和TPU,维持温度65℃,60min。
实施例7:
A组分物料制备:50份蓖麻油,20份己二醇,25份聚醚多元醇,3份添加剂,2份纳米改性材料。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为10℃。将A组分物料按照顺序依次投入蓖麻油(45份),己二醇,聚醚多元醇,加热搅拌30min。将氧化石墨烯预处理的纳米钛白粉(金红石型)与蓖麻油5份,添加剂,气相白炭黑低温(5℃)高速分散,转速3000RPM保持30mi n后,投入反应釜搅拌并升温至60℃,保持高速搅拌。低速搅拌,降温,出料制得组分A物料。
B组分制备:40份MDI,5份TPU,10份聚丙二醇(分子量400),30份聚醚多元醇(分子量2000-2500),15份木质素胺改性二苯基甲烷二异氰酸酯。对反应釜进行气密性检查,用氮气置换干燥除水,并控制温度为60℃;反应釜投料依次为聚丙二醇(分子量400),加热维持100℃,抽真空30min。降温80℃-90℃投入2,2MDI20份并搅拌20min。投入聚醚多元醇(分子量2000-2500)控制温度100℃,搅拌40min。降温至60℃,投入2,2MDI20份,维持温度80℃充分搅拌30min。投入15份木质素胺改性二苯基甲烷二异氰酸酯和TPU,维持温度65℃,60min。
实施例1-7中氧化石墨烯预处理的纳米级钛白粉的制备方法为:将钛的前驱体加入到乙二醇水溶液中,加入氧化石墨烯溶液混合均匀,在110-120℃下加热反应1-2h,降至室温后,加入聚氨酯泡沫吸附,离心,洗涤干燥,研磨,得到氧化石墨烯预处理的纳米级钛白粉。
实施例1-7中改性二苯基甲烷二异氰酸酯的制备方法为:将木质素胺与异氰酸酯作为主要原料,在反应釜中,在有机金属类催化剂的作用下,加热加压反应得到木质素胺改性二苯基甲烷二异氰酸酯。
经检测,实施例1-7制备的AB组分混合作为粘合剂制备的PE薄膜的粘度、老化、蒸煮、抗紫外、外观、固化、抗菌的结果如下所示:
由上表可见,本发明制备的粘合剂制备的PE薄膜粘度高,耐老化、耐蒸煮和抗菌性能优异,UV阻隔效果明显,满足软包装薄膜粘合剂的使用要求。
上述实施例仅例示性说明本发明的原理及其功效,而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下,对上述实施例进行修饰或改变。因此,举凡所属技术领域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 (10)
1.一种纳米改性双组分无溶剂软包装粘合剂,其特征在于,所述纳米改性双组分无溶剂软包装粘合剂及其制备方法包括A组分和B组分,所述A组分包括蓖麻油或者棕榈油植物油基多元醇、己二醇、聚醚多元醇、添加剂和纳米改性材料,所述B组分包括MDI、TPU、聚丙二醇、聚醚多元醇和改性二苯基甲烷二异氰酸酯,所述添加剂为硅烷偶联剂、气相白炭黑、聚酯树脂或者稳定剂中的一种或者几种,所述纳米材料为氧化石墨烯预处理的纳米级钛白粉,所述改性二苯基甲烷二异氰酸酯为木质素胺改性二苯基甲烷二异氰酸酯。
2.根据权利要求1所述的一种纳米改性双组分无溶剂软包装粘合剂,其特征在于,所述A组分的成分,按重量份计,包括蓖麻油或者棕榈油植物油基多元醇50份、己二醇20份、聚醚多元醇25份、添加剂3份和纳米改性材料2份,总量为100份。
3.根据权利要求1所述的一种纳米改性双组分无溶剂软包装粘合剂,其特征在于,所述B组分的成分,按重量份计,包括MDI 40份、TPU 5份、聚丙二醇10份、聚醚多元醇30份和改性二苯基甲烷二异氰酸酯15份。
4.根据权利要求1-3所述的任意一种纳米改性双组分无溶剂软包装粘合剂,其特征在于,所述聚醚多元醇为分子量为2000-2500的聚丙二醇,羟基为370-400。
5.根据权利要求1或者3所述的一种纳米改性双组分无溶剂软包装粘合剂,其特征在于,所述MDI为4,4’-二苯基甲烷二异氰酸酯,2,4’-二苯基甲烷二异氰酸酯和2,2’-二苯基甲烷二异氰酸酯中的一种或其混合物。
6.根据权利要求1或者3所述的一种纳米改性双组分无溶剂软包装粘合剂,其特征在于,所述氧化石墨烯预处理的纳米级钛白粉的制备方法为:将钛的前驱体加入到乙二醇水溶液中,加入氧化石墨烯溶液混合均匀,在110-120℃下加热反应1-2h,降至室温后,加入聚氨酯泡沫吸附,离心,洗涤干燥,研磨,得到氧化石墨烯预处理的纳米级钛白粉。
7.根据权利要求1或者3所述的一种纳米改性双组分无溶剂软包装粘合剂,其特征在于,所述改性二苯基甲烷二异氰酸酯的制备方法为:将木质素胺与异氰酸酯作为主要原料,在反应釜中,在有机金属类催化剂的作用下,加热加压反应得到木质素胺改性二苯基甲烷二异氰酸酯。
8.根据权利要求1-7所述的任一一种纳米改性双组分无溶剂软包装粘合剂,其特征在于,所述纳米改性双组分无溶剂软包装粘合剂的制备方法,包括以下步骤:
(1)A组分的制备:对反应釜进行气密性检查,用氮气置换干燥除水,调节温度至10℃,按重量份计,依次投入蓖麻油或者棕榈油植物油基多元醇,己二醇,聚醚多元醇,加热至80-100℃搅拌30min,加入预处理的纳米级钛白粉,真空高速搅拌1h,再加入添加剂并升温至60℃,高速搅拌至均匀,低速搅拌并降至室温,出料,得到纳米改性的A组分;
(2)B组分的制备:对反应釜进行气密性检查,用氮气置换干燥除水,调节温度至60℃,先加入聚丙二醇,加热至100℃,抽真空30min,降温至80℃-90℃投入MDI并搅拌20min,然后加入聚醚多元醇,升温至100℃,搅拌40min,再降温至60℃,投入MDI,升温至80℃,充分搅拌30min,最后加入15份的改性二苯基甲烷二异氰酸酯和TPU,升温至65℃搅拌60min,出料,得到木质素胺改性的B组分;
(3)将步骤(1)制备的纳米改性的A组分与步骤(2)制备的木质素胺改性的B组分组成纳米改性双组分无溶剂软包装粘合剂。
9.根据权利要求8所述的一种纳米改性双组分无溶剂软包装粘合剂,其特征在于:预处理的纳米级钛白粉与添加剂的质量比为1:1。
10.根据权利要求8所述的一种纳米改性双组分无溶剂软包装粘合剂,其特征在于:所述步骤(2)中,MDI可用TDI代替。
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