CN112724912A - 一种耐蒸煮水性聚氨酯胶黏剂及其制备方法 - Google Patents
一种耐蒸煮水性聚氨酯胶黏剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种耐蒸煮水性聚氨酯胶黏剂及其制备方法,本发明的耐蒸煮水性聚氨酯胶黏剂是由有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体、润湿剂、流平剂、消泡剂、水性固化剂复配而成。该耐蒸煮水性聚氨酯胶黏剂具有无毒、不燃、使用安全、不污染环境、粘接强度高、耐蒸煮性能好等优点,可用于软包装材料的塑塑复合、铝塑复合、纸塑复合等领域。
Description
技术领域
本发明涉及一种水性聚氨酯及其制备方法,尤其涉及一种耐蒸煮水性聚氨酯胶黏剂及其制备方法。
背景技术
耐蒸煮聚氨酯胶黏剂是随着食品包装业的发展而兴起的,国内最早采用溶剂型耐蒸煮聚氨酯胶黏剂,是用于榨菜包装袋的复合。由于耐蒸煮包装袋有质轻、剥离强度高、卫生性好、方便、易贮存、易拆等优点,所以使耐蒸煮聚氨酯胶黏剂的使用范围扩展到一些电子产品、军事产品、农药、医药,甚至纺织服装业产品的包装材料、合成材料的复合。
近年来,保护地球环境舆论压力与日俱增。有机溶剂易燃易爆、易挥发、气味大、使用时造成空气污染,用溶剂型聚氨酯材料生产的食品包装产品具有或多或少的毒性隐患。水性聚氨酯材料以水为基本介质,具有不燃、气味小、不污染环境、节能、操作加工方便等优点,已受到人们的重视。虽然我国现阶段食品包装行业还是以使用溶剂型聚氨酯材料为主,但水性聚氨酯材料代替溶剂型聚氨酯材料已经是大势所趋。耐蒸煮水性聚氨酯胶黏剂作为胶黏剂应用于复合薄膜包装,特别是包装材料上,越来越得到国内外的重视。
耐蒸煮水性聚氨酯胶黏剂,除了需保持聚氨酯的粘接强度高以外,针对耐蒸煮水性聚氨酯胶黏剂以水为分散介质的特点,还需提出一些特殊的要求,如要求耐蒸煮水性聚氨酯胶黏剂高固含量、低粘度,好的耐水性、流平性、耐黄变性、低易氧化物等。
申请号为201310656434.2的发明专利报导了一种耐高温蒸煮复合软包装膜用胶黏剂,首先使用γ-氨丙基三乙氧基硅烷对纳米SiO2进行表面接枝改性;加入多异氰酸酯和低聚物多元醇,再加入亲水性扩链剂反应得到聚氨酯预聚体;用改性纳米SiO2对聚氨酯预聚体改性;加入含羟基丙烯酸酯封端;冷却后进行中和分散,得改性水性聚氨酯杂合分散体;以分散体作为种子乳液和高分子乳化剂,加入含氟丙烯酸酯及引发剂,通过种子乳液聚合制备多重改性水性聚氨酯复合乳液;向该复合乳液加入增稠剂和消泡剂,得到多重改性水性聚氨酯复合胶黏剂。但由于耐高温蒸煮胶黏剂除了需要耐水性能高以外,还需要具有足够高的内聚强度,单纯通过丙烯酸酯单体与纳米SiO2复合改性难以满足实际使用要求。
发明内容
本发明所要解决的技术问题是为了克服溶剂型聚氨酯胶黏剂毒性较大、易燃、使用安全性差、污染环境等问题而提出一种复合薄膜包装用的耐蒸煮水性聚氨酯胶黏剂,本发明的另一目的还提供了上述耐蒸煮水性聚氨酯胶黏剂的制备方法。
本发明的具体技术方案为:一种耐蒸煮水性聚氨酯胶黏剂,其特征在由100质量份有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体、0.01-0.3质量份润湿剂、0.01-0.3质量份流平剂、0.01-0.5质量份消泡剂、3-10份水性固化剂复配而成。
其中所述的有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体其主要性能指标为:固含量为40-50%,粘度为20-100mPa.s。本发明还需加入流平剂,降低耐蒸煮水性聚氨酯胶黏剂的表面张力,在包装材料上有好的流平性;所述的流平剂为市售的聚有机硅氧烷、聚醚改性的聚有机硅氧烷或含氟表面活性剂;所用的消泡剂为水性有机硅消泡剂。;所述的润湿剂为聚氧乙烯烷基酚醚,聚氧乙烯脂肪醇醚,聚氧乙烯聚氧丙烯嵌段共聚物中一种。所述的水性固化剂为水分散性型多异氰酸酯固化剂、氮丙啶固化剂、碳化二亚胺中一种。
本发明还提供了上述耐蒸煮水性聚氨酯胶黏剂的制备方法,其具体步骤如下:
(1)有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体的制备;
在容器中首先加入聚醚多元醇、10-40%聚醚多元醇质量的有机硅树脂,在100-110℃下抽真空脱水1-2h,降温至30-60℃加入按官能团物质的量之比为-NCO/-OH=1.5-2的芳香族二异氰酸酯,在70-90℃下反应1-3h,然后加入含有亲水基团的化合物和低分子多元醇扩链剂,以上原料按官能团摩尔比-NCO/-OH=1.1-1.5,在预聚物质量0.05-0.3%催化剂作用下进行反应,反应温度70-90℃,反应时间2-4h,在反应过程中通过加入丙酮控制反应物粘度在3000-5000mPa.s,制得端基以异氰酸酯基团为主、羧基含量为0.7-2.0%的聚氨酯预聚物;
将上述制得的聚氨酯预聚物降温至30-50℃,加入三乙胺将其中的羧酸根中和成盐,中和度80-110%;
预聚物出料至分散器中,加入过量NCO物质的量的40-80%的低分子脂肪胺类扩链剂反应10-30分钟,在搅拌下加入去离子水进行分散,蒸出丙酮,即制得水性聚氨酯分散体;
升温至70-80℃后保温0.5h,在3~4h内滴加10-50%水性聚氨酯分散体固体质量的不饱和单体与0.1-0.5%不饱和单体质量的偶氮二异丁腈(AIBN)溶液,滴完后保温2-4h,降温,出料,得到有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体,主要性能指标为:固含量为40-50%,粘度为20-200mPa.s。
(2)将上述制得的有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体100质量份,加入0.01-0.3质量份润湿剂、0.01-0.3质量份流平剂、0.01-0.5质量份消泡剂、3-10份水性固化剂,搅拌,使各种助剂与水性聚氨酯分散体混合均匀,即制得耐蒸煮水性聚氨酯胶黏剂。
其中所述的聚醚多元醇分子量在200-6000之间,优选1000-2000。所述的含有亲水基团的化合物为二羟甲基丙酸、二羟甲基丁酸中一种。所述的芳香族二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中一种。所述的低分子多元醇扩链剂为三羟甲基丙烷、甘油、三乙醇胺中一种。所述的低分子脂肪胺类扩链剂为乙二胺、二亚乙烯三胺、三亚乙烯四胺、四亚乙烯五胺中一种。所述的催化剂为二月桂酸二丁基锡、辛酸亚锡中一种。所述的不饱和单体为甲基丙烯酸甲酯、甲基丙烯酸酯乙酯与丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯中一种或几种的混合。
有益效果:
1、与目前市场上广泛使用的溶剂型聚氨酯胶黏剂相比,本发明的耐蒸煮水性聚氨酯胶黏剂具有耐黄变、无毒、不燃、使用安全、不污染环境等优点。
2、本发明综合考虑了复合薄膜表观对耐蒸煮水性聚氨酯胶黏剂的要求,通过加入润湿剂、流平剂、水性消泡剂,改善了复合薄膜的粘合强度和表观。
3、本发明综合考虑了复合薄膜耐过热水性能对耐蒸煮水性聚氨酯胶黏剂的要求,通过采用耐水性较好的聚醚多元醇为基体合成水性聚氨酯,配合有机硅树脂、丙烯酸酯单体对水性聚氨酯进行多重改性,并加入水性固化剂增加水性聚氨酯的交联密度,提高了水性聚氨酯成膜后的耐过热水性能,使其达到了目前市场上广泛使用的溶剂型聚氨酯胶黏剂的耐蒸煮要求。
具体实施方法
下面就本发明举例说明,但不是对本发明的限制。其中例1-4为有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体的制备,例5-8为耐蒸煮水性聚氨酯胶黏剂的制备。
实施例1
在装有搅拌器、温度计、回流冷凝器的反应器中,加入聚醚多元醇(分子量为2000)40g、有机硅树脂4g,100℃下抽真空脱水2h,降温至60℃加入甲苯二异氰酸酯17g,升温至70℃,反应3h,加入二羟甲基丙酸3g,三乙醇胺0.6g,二月桂酸二丁基锡0.12g,在搅拌下继续反应4h,得到预聚体,在反应过程中通过加入丙酮控制反应物粘度在3000-5000mPa.s,然后降温至35℃左右,加入2g三乙胺使预聚体中和成盐;出料至分散器中,加入0.7g乙二胺扩链反应20分钟,在剪切下加入去离子水117g乳化,蒸出丙酮;然后升温至70℃后保温0.5h,在3h内滴加甲基丙烯酸甲酯6g、丙烯酸乙酯6.7g与0.13g AIBN配置而成的溶液,滴完后保温2h,降温,出料,得到有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体。其性能如下:固含量:41%;PH值:6.8;粘度:22mPa.s。
实施例2
在装有搅拌器、温度计、回流冷凝器的反应器中,加入聚醚多元醇(分子量为1600)40g、有机硅树脂8g,105℃下抽真空脱水1.5h,降温至60℃加入二苯基甲烷二异氰酸酯20g,升温至80℃,反应2h,加入二羟甲基丙酸4g,三羟甲基丙烷0.5g,辛酸亚锡0.10g,在搅拌下继续反应4h,得到预聚体,在反应过程中通过加入丙酮控制反应物粘度在3000-5000mPa.s,然后降温至50℃左右,加入3g三乙胺使预聚体中和成盐;出料至分散器中,加入0.5g二亚乙烯三胺扩链反应30分钟,在剪切下加入去离子水105g乳化,蒸出丙酮;然后升温至75℃后保温0.5h,在4h内滴加甲基丙烯酸乙酯8g、丙烯酸丁酯5.5g与0.16g AIBN配置而成的溶液,滴完后保温4h,降温,出料,得到有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体。其性能如下:固含量:46%;PH值:7.1;粘度:95mPa.s。
实施例3
在装有搅拌器、温度计、回流冷凝器的反应器中,加入聚醚多元醇(分子量为1000)40g、有机硅树脂12g,110℃下抽真空脱水1h,降温至60℃加入二苯基甲烷二异氰酸酯10g、甲苯二异氰酸酯11g,升温至90℃,反应1h,加入二羟甲基丁酸4.5g,甘油0.6g,二月桂酸二丁基锡0.16g,在搅拌下继续反应3h,得到预聚体,在反应过程中通过加入丙酮控制反应物粘度在3000-5000mPa.s,然后降温至35℃左右,加入3.2g三乙胺使预聚体中和成盐;出料至分散器中,加入0.9g三亚乙烯四胺扩链反应30分钟,在剪切下加入去离子水101g乳化,蒸出丙酮;然后升温至90℃后保温0.5h,在3h内滴加甲基丙烯酸甲酯5g、丙烯酸异辛酯13.5g与0.19g AIBN配置而成的溶液,滴完后保温4h,降温,出料,得到有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体。其性能如下:固含量:50%;PH值:6.8;粘度:199mPa.s。
实施例4
在装有搅拌器、温度计、回流冷凝器的反应器中,加入聚醚多元醇(分子量为2000)40g、有机硅树脂16g,109℃下抽真空脱水1h,降温至60℃加入甲苯二异氰酸酯22g,升温至80℃,反应3h,加入二羟甲基丙酸5g,三乙醇胺0.4g,二月桂酸二丁基锡0.12g,在搅拌下继续反应4h,得到预聚体,在反应过程中通过加入丙酮控制反应物粘度在3000-5000mPa.s,然后降温至35℃左右,加入4g三乙胺使预聚体中和成盐;出料至分散器中,加入0.9g乙二胺扩链反应20分钟,在剪切下加入去离子水120g乳化,蒸出丙酮;然后升温至70℃后保温0.5h,在3h内滴加甲基丙烯酸甲酯8g、丙烯酸丁酯3.7g、丙烯酸异辛酯4.9g与0.22g AIBN配置而成的溶液,滴完后保温2h,降温,出料,得到有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体。其性能如下:固含量:47%;PH值:7.3;粘度:110mPa.s。
实施例5
在装有调速搅拌器的分散器中,加入100g由实施例1所制备的有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体,慢慢加入0.3g聚氧乙烯烷基酚醚润湿剂、0.19g含氟表面活性剂、0.18g水性有机硅消泡剂、3g水分散性型多异氰酸酯水性固化剂,搅拌均匀后得到耐蒸煮水性聚氨酯胶黏剂。复合基材分别为BOPP膜、BOPET薄膜,将上述制得耐蒸煮水性聚氨酯胶黏剂的均匀地涂覆在BOPET薄膜上,在80℃下烘干水份,热压得到复合薄膜,在50℃下熟化8h,测得T剥离强度为13.3N/15mm,121℃蒸煮不开裂。
实施例6
操作同实施例5,其中100g有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体为实施例2所制备,加入0.3g聚氧乙烯脂肪醇醚润湿剂、0.012g聚有机硅氧烷表面活性剂、0.013g水性有机硅消泡剂、5g氮丙啶水性固化剂,制得复合薄膜后测得T剥离强度为12.5N/15mm,121℃蒸煮不开裂。
实施例7
操作同实施例5,其中100g有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体为实施例3所制备,加入0.3g聚氧乙烯聚氧丙烯嵌段共聚物润湿剂、0.08g聚醚改性的聚有机硅氧烷表面活性剂、0.12g水性有机硅消泡剂、10g碳化二亚胺水性固化剂,制得复合薄膜后测得T剥离强度为13.7N/15mm,121℃蒸煮不开裂。
实施例8
操作同实施例5,其中100g有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体为实施例4所制备,加入0.3g聚氧乙烯烷基酚醚润湿剂、0.18g聚有机硅氧烷表面活性剂、0.12g水性有机硅消泡剂、7g水分散性型多异氰酸酯水性固化剂,制得复合薄膜后测得T剥离强度为11.6N/15mm,121℃蒸煮不开裂。
Claims (9)
1.一种耐蒸煮水性聚氨酯胶黏剂,其特征在于是由100质量份有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体、0.01-0.3质量份润湿剂、0.01-0.3质量份流平剂、0.01-0.5质量份消泡剂、3-10份水性固化剂复配而成,有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体主要性能指标为:固含量为40-50%,粘度为20-100mPa.s,所述的流平剂为聚有机硅氧烷、聚醚改性的聚有机硅氧烷或含氟表面活性剂;所述的消泡剂为水性有机硅消泡剂;所述的润湿剂为聚氧乙烯烷基酚醚,聚氧乙烯脂肪醇醚,聚氧乙烯聚氧丙烯嵌段共聚物中一种;所述的水性固化剂为水分散性型多异氰酸酯固化剂、氮丙啶固化剂、碳化二亚胺中一种。
2.一种如权利要求1所述耐蒸煮水性聚氨酯胶黏剂的制备方法,其具体步骤如下:
(1)、有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体的制备;
在容器中首先加入聚醚多元醇、10-40%聚醚多元醇质量的有机硅树脂,在100-110℃下抽真空脱水1-2h,降温至30-60℃加入按官能团物质的量之比为-NCO/-OH=1.5-2的芳香族二异氰酸酯,在70-90℃下反应1-3h,然后加入含有亲水基团的化合物和低分子多元醇扩链剂,以上原料按官能团摩尔比-NCO/-OH=1.1-1.5,在预聚物质量0.05-0.3%催化剂作用下进行反应,反应温度70-90℃,反应时间2-4h,在反应过程中通过加入丙酮控制反应物粘度在3000-5000mPa.s,制得端基以异氰酸酯基团为主、羧基含量为0.7-2.0%的聚氨酯预聚物;
将上述制得的聚氨酯预聚物降温至30-50℃,加入三乙胺将其中的羧酸根中和成盐,中和度80-110%;
预聚物出料至分散器中,加入过量NCO物质的量的40-80%的低分子脂肪胺类扩链剂反应10-30分钟,在搅拌下加入去离子水进行分散,蒸出丙酮,即制得水性聚氨酯分散体;
升温至70-80℃后保温0.5h,在3~4h内滴加10-50%水性聚氨酯分散体固体质量的不饱和单体与0.1-0.5%不饱和单体质量的偶氮二异丁腈(AIBN)溶液,滴完后保温2-4h,降温,出料,得到有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体,主要性能指标为:固含量为40-50%,粘度为20-200mPa.s;
(2)、将上述制得的有机硅树脂与丙烯酸酯单体改性水性聚氨酯分散体100质量份,加入0.01-0.3质量份润湿剂、0.01-0.3质量份流平剂、0.01-0.5质量份消泡剂、3-10份水性固化剂,搅拌,使各种助剂混合均匀,即制得耐蒸煮水性聚氨酯胶黏剂。
3.根据权利要求2所述的制备方法,其特征在于聚醚多元醇分子量在200-6000之间,优选1000-2000。
4.根据权利要求2所述的制备方法,其特征在于芳香族二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯中一种或几种的混合。
5.根据权利要求2所述的制备方法,其特征在于含有亲水基团的化合物为二羟甲基丙酸、二羟甲基丁酸中一种。
6.根据权利要求2所述的制备方法,其特征在于低分子多元醇扩链剂为三羟甲基丙烷、甘油、三乙醇胺中一种。
7.根据权利要求2所述的制备方法,其特征在于低分子脂肪胺类扩链剂为乙二胺、二亚乙烯三胺、三亚乙烯四胺、四亚乙烯五胺中一种。
8.根据权利要求2所述的制备方法,其特征在于所述的催化剂为二月桂酸二丁基锡、辛酸亚锡中一种。
9.根据权利要求3所述的制备方法,其特征在于所述的不饱和单体为甲基丙烯酸甲酯、甲基丙烯酸酯乙酯与丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯中一种或几种的混合。
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