CN106047215A - 一种纸板用防腐耐老化胶黏剂 - Google Patents
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Abstract
本发明公开了一种纸板用防腐耐老化胶黏剂,其原料按重量份包括:芳香族异氰酸酯25‑35份,聚丙二醇5‑15份,聚酯二醇15‑20份,糊化淀粉40‑60份,牛皮胶5‑15份,骨胶1‑6份,改性乳清蛋白复合微粒5‑15份,大豆蛋白质5‑15份,双(二辛基焦磷酸酰氧基)乙撑钛酸酯1‑2份,十二烷基磺酸钠1‑2份,戊唑醇0.5‑1.2份,茶多酚1‑2份,壳聚糖0.2‑1份,蓖麻油酸1‑5份,水20‑40份。本发明防腐、耐老化性好,韧性、热稳定性优异。
Description
技术领域
本发明涉及胶黏剂技术领域,尤其涉及一种纸板用防腐耐老化胶黏剂。
背景技术
水性胶黏剂是以水为分散介质,无嗅、无污染,是环境友好胶黏剂。但是随着石油等不可再生资源的枯竭,原油价格持续上涨,合成聚氨酯的生产成本日益增高。同时水性聚氨酯还存在内聚能低于极性基材,粘附力不强等问题。而淀粉富含极性基团,其分子结构与竹、木材中的纤维素结构极为相似,因此和木材、纸张等有着很强的粘附力,并且淀粉为绿色可再生资源,价格低廉。但防腐、耐老化性较差,韧性差,热稳定性不好,亟待解决。
发明内容
一种纸板用防腐耐老化胶黏剂,制品防腐、耐老化性好,韧性、热稳定性优异。
本发明提出的一种纸板用防腐耐老化胶黏剂,其原料按重量份包括:芳香族异氰酸酯25-35份,聚丙二醇5-15份,聚酯二醇15-20份,糊化淀粉40-60份,牛皮胶5-15份,骨胶1-6份,改性乳清蛋白复合微粒5-15份,大豆蛋白质5-15份,双(二辛基焦磷酸酰氧基)乙撑钛酸酯1-2份,十二烷基磺酸钠1-2份,戊唑醇0.5-1.2份,茶多酚1-2份,壳聚糖0.2-1份,蓖麻油酸1-5份,水20-40份。
优选地,改性乳清蛋白复合微粒采用如下工艺制备:按重量份将5-15份乳清蛋白、40-80份呈中性的磷酸盐缓冲液室温混合搅拌4-5h,冷却至2-3℃静置5-10h,升温至65-75℃水浴搅拌15-35min,以5-12℃/min的速度降温至室温,调节体系pH至7.2-7.4,加入0.002-0.005份转谷氨酰胺酶在40-46℃水浴震荡1-2h,灭活,调节体系pH至中性,搅拌状态下加入3-6份改性竹炭、2-5份高岭土、0.5-2.5份纳米二氧化硅,加入完全后继续搅拌15-35min,室温静置2-6h,得到改性乳清蛋白复合微粒。
优选地,改性竹炭采用如下工艺制备:按配比将15-25份竹炭粉碎,加入去离子水搅拌2-6天,过滤,干燥,得到第一预制料;将0.5-1.5份钛酸丁酯、5-15份无水乙醇混合搅拌20-40min,加入10-30份去离子水、2-6份1-1.8mol/L盐酸、0.5-1.2份六亚甲基四胺、0.15-0.3份戊唑醇络合硝酸银、2-8份聚丙二醇混合搅拌20-40min,加入第一预制料混合真空搅拌15-35min,真空度为0.15-0.25MPa,过滤,高温活化,干燥,得到改性竹炭。
优选地,改性乳清蛋白复合微粒、大豆蛋白质的重量比为8-13:11-13。
优选地,双(二辛基焦磷酸酰氧基)乙撑钛酸酯、十二烷基磺酸钠的重量比为1.4-1.6:1.2-1.5。
优选地,芳香族异氰酸酯、聚丙二醇、聚酯二醇,改性乳清蛋白复合微粒的重量比为28-32:8-11:16-18:8-13。
优选地,芳香族异氰酸酯、聚丙二醇、聚酯二醇、糊化淀粉的重量比为28-32:8-11:16-18:50-54。
优选地,大豆蛋白质、牛皮胶、骨胶的重量比为11-13:8-12:2-4。
优选地,改性乳清蛋白复合微粒、戊唑醇、茶多酚、壳聚糖的重量比为8-13:0.6-1:1.5-1.8:0.5-0.8。
优选地,所述的纸板用防腐耐老化胶黏剂,其原料按重量份包括:芳香族异氰酸酯28-32份,聚丙二醇8-11份,聚酯二醇16-18份,糊化淀粉50-54份,牛皮胶8-12份,骨胶2-4份,改性乳清蛋白复合微粒8-13份,大豆蛋白质11-13份,双(二辛基焦磷酸酰氧基)乙撑钛酸酯1.4-1.6份,十二烷基磺酸钠1.2-1.5份,戊唑醇0.6-1份,茶多酚1.5-1.8份,壳聚糖0.5-0.8份,蓖麻油酸2-4份,水30-35份。
本发明中,聚酯二醇、聚丙二醇与芳香族异氰酸酯反应后再与糊化淀粉交联,通过合理控制上述组分配比,制品黏度好,耐水性能优异,适于室外高湿条件下使用,另外聚酯二醇、聚丙二醇、芳香族异氰酸酯反应后生成的氨基、羧基与醛基活性基团,可与改性乳清蛋白复合微粒结合,结合力强,热稳定好,且防水性能进一步增强,进一步与十二烷基磺酸钠、双(二辛基焦磷酸酰氧基)乙撑钛酸酯作用,组分间相互间结合强度进一步增强,胶合强度极高;在改性乳清蛋白复合微粒中,乳清蛋白预处理后作为纳米级微粒载体,与加入的改性竹炭、高岭土、纳米二氧化硅相容性极好,粒径分布可控,成本低,在制品中的分散度极好,稳定性极高,且环保,废弃后易降解,不污染环境,其中的转谷氨酰胺酶可催化蛋白质上的氨基与羟酰胺基结合,热稳定性好,进一步与制品中大豆蛋白质配合作用,环保,韧性进一步增强,而改性乳清蛋白复合微粒中的改性竹炭以钛酸丁酯、无水乙醇、盐酸为主料,六亚甲基四胺为氮源,在戊唑醇络合硝酸银的作用下,氮元素与银离子共掺杂与第一预制料真空状态下结合,高温活化后,可有效改变第一预制料孔径尺寸与内部结构,杀菌抑菌效果极好,比表面积极大,且吸附性能极为优异,与戊唑醇、壳聚糖、茶多酚协同作用,结合力强,协同防腐效果极好,而大豆蛋白质具有良好的生物活性和生物可降解性,高湿条件下不易脱胶与断裂,与牛皮胶、骨胶作用可克服大豆蛋白质粘合强度低和耐水性差的缺点,且稳定性好,耐老化性能好,易于储存。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明。
实施例1
一种纸板用防腐耐老化胶黏剂,其原料按重量份包括:芳香族异氰酸酯25份,聚丙二醇15份,聚酯二醇15份,糊化淀粉60份,牛皮胶5份,骨胶6份,改性乳清蛋白复合微粒5份,大豆蛋白质15份,双(二辛基焦磷酸酰氧基)乙撑钛酸酯1份,十二烷基磺酸钠2份,戊唑醇0.5份,茶多酚2份,壳聚糖0.2份,蓖麻油酸5份,水20份。
实施例2
一种纸板用防腐耐老化胶黏剂,其原料按重量份包括:芳香族异氰酸酯35份,聚丙二醇5份,聚酯二醇20份,糊化淀粉40份,牛皮胶15份,骨胶1份,改性乳清蛋白复合微粒15份,大豆蛋白质5份,双(二辛基焦磷酸酰氧基)乙撑钛酸酯2份,十二烷基磺酸钠1份,戊唑醇1.2份,茶多酚1份,壳聚糖1份,蓖麻油酸1份,水40份。
实施例3
一种纸板用防腐耐老化胶黏剂,其原料按重量份包括:芳香族异氰酸酯32份,聚丙二醇8份,聚酯二醇18份,糊化淀粉50份,牛皮胶12份,骨胶2份,改性乳清蛋白复合微粒13份,大豆蛋白质11份,双(二辛基焦磷酸酰氧基)乙撑钛酸酯1.6份,十二烷基磺酸钠1.2份,戊唑醇1份,茶多酚1.5份,壳聚糖0.8份,蓖麻油酸2份,水35份。
改性乳清蛋白复合微粒采用如下工艺制备:按重量份将5份乳清蛋白、80份呈中性的磷酸盐缓冲液室温混合搅拌4h,冷却至3℃静置5h,升温至75℃水浴搅拌15min,以12℃/min的速度降温至室温,调节体系pH至7.2,加入0.005份转谷氨酰胺酶在40℃水浴震荡2h,灭活,调节体系pH至中性,搅拌状态下加入3份改性竹炭、5份高岭土、0.5份纳米二氧化硅,加入完全后继续搅拌35min,室温静置2h,得到改性乳清蛋白复合微粒。
改性竹炭采用如下工艺制备:按配比将25份竹炭粉碎,加入去离子水搅拌2天,过滤,干燥,得到第一预制料;将1.5份钛酸丁酯、5份无水乙醇混合搅拌40min,加入10份去离子水、6份1mol/L盐酸、1.2份六亚甲基四胺、0.15份戊唑醇络合硝酸银、8份聚丙二醇混合搅拌20min,加入第一预制料混合真空搅拌35min,真空度为0.15MPa,过滤,高温活化,干燥,得到改性竹炭。
实施例4
一种纸板用防腐耐老化胶黏剂,其原料按重量份包括:芳香族异氰酸酯28份,聚丙二醇11份,聚酯二醇16份,糊化淀粉54份,牛皮胶8份,骨胶4份,改性乳清蛋白复合微粒8份,大豆蛋白质13份,双(二辛基焦磷酸酰氧基)乙撑钛酸酯1.4份,十二烷基磺酸钠1.5份,戊唑醇0.6份,茶多酚1.8份,壳聚糖0.5份,蓖麻油酸4份,水30份。
改性乳清蛋白复合微粒采用如下工艺制备:按重量份将15份乳清蛋白、40份呈中性的磷酸盐缓冲液室温混合搅拌5h,冷却至2℃静置10h,升温至65℃水浴搅拌35min,以5℃/min的速度降温至室温,调节体系pH至7.4,加入0.002份转谷氨酰胺酶在46℃水浴震荡1h,灭活,调节体系pH至中性,搅拌状态下加入6份改性竹炭、2份高岭土、2.5份纳米二氧化硅,加入完全后继续搅拌15min,室温静置6h,得到改性乳清蛋白复合微粒。
改性竹炭采用如下工艺制备:按配比将15份竹炭粉碎,加入去离子水搅拌6天,过滤,干燥,得到第一预制料;将0.5份钛酸丁酯、15份无水乙醇混合搅拌20min,加入30份去离子水、2份1.8mol/L盐酸、0.5份六亚甲基四胺、0.3份戊唑醇络合硝酸银、2份聚丙二醇混合搅拌40min,加入第一预制料混合真空搅拌15min,真空度为0.25MPa,过滤,高温活化,干燥,得到改性竹炭。
实施例5
一种纸板用防腐耐老化胶黏剂,其原料按重量份包括:芳香族异氰酸酯31份,聚丙二醇10份,聚酯二醇17份,糊化淀粉52份,牛皮胶10份,骨胶3份,改性乳清蛋白复合微粒11份,大豆蛋白质12份,双(二辛基焦磷酸酰氧基)乙撑钛酸酯1.52份,十二烷基磺酸钠1.35份,戊唑醇0.8份,茶多酚1.6份,壳聚糖0.6份,蓖麻油酸3份,水33份。
改性乳清蛋白复合微粒采用如下工艺制备:按重量份将12份乳清蛋白、60份呈中性的磷酸盐缓冲液室温混合搅拌4.2h,冷却至2.2℃静置8h,升温至68℃水浴搅拌24min,以10℃/min的速度降温至室温,调节体系pH至7.3,加入0.0035份转谷氨酰胺酶在43℃水浴震荡1.5h,灭活,调节体系pH至中性,搅拌状态下加入4份改性竹炭、3份高岭土、2.2份纳米二氧化硅,加入完全后继续搅拌22min,室温静置5h,得到改性乳清蛋白复合微粒。
改性竹炭采用如下工艺制备:按配比将21份竹炭粉碎,加入去离子水搅拌4天,过滤,干燥,得到第一预制料;将1.2份钛酸丁酯、12份无水乙醇混合搅拌32min,加入22份去离子水、4份1.4mol/L盐酸、0.85份六亚甲基四胺、0.22份戊唑醇络合硝酸银、6份聚丙二醇混合搅拌32min,加入第一预制料混合真空搅拌30min,真空度为0.22MPa,过滤,高温活化,干燥,得到改性竹炭。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种纸板用防腐耐老化胶黏剂,其特征在于,其原料按重量份包括:芳香族异氰酸酯25-35份,聚丙二醇5-15份,聚酯二醇15-20份,糊化淀粉40-60份,牛皮胶5-15份,骨胶1-6份,改性乳清蛋白复合微粒5-15份,大豆蛋白质5-15份,双(二辛基焦磷酸酰氧基)乙撑钛酸酯1-2份,十二烷基磺酸钠1-2份,戊唑醇0.5-1.2份,茶多酚1-2份,壳聚糖0.2-1份,蓖麻油酸1-5份,水20-40份。
2.根据权利要求1所述的纸板用防腐耐老化胶黏剂,其特征在于,改性乳清蛋白复合微粒采用如下工艺制备:按重量份将5-15份乳清蛋白、40-80份呈中性的磷酸盐缓冲液室温混合搅拌4-5h,冷却至2-3℃静置5-10h,升温至65-75℃水浴搅拌15-35min,以5-12℃/min的速度降温至室温,调节体系pH至7.2-7.4,加入0.002-0.005份转谷氨酰胺酶在40-46℃水浴震荡1-2h,灭活,调节体系pH至中性,搅拌状态下加入3-6份改性竹炭、2-5份高岭土、0.5-2.5份纳米二氧化硅,加入完全后继续搅拌15-35min,室温静置2-6h,得到改性乳清蛋白复合微粒。
3.根据权利要求1或2所述的纸板用防腐耐老化胶黏剂,其特征在于,改性竹炭采用如下工艺制备:按配比将15-25份竹炭粉碎,加入去离子水搅拌2-6天,过滤,干燥,得到第一预制料;将0.5-1.5份钛酸丁酯、5-15份无水乙醇混合搅拌20-40min,加入10-30份去离子水、2-6份1-1.8mol/L盐酸、0.5-1.2份六亚甲基四胺、0.15-0.3份戊唑醇络合硝酸银、2-8份聚丙二醇混合搅拌20-40min,加入第一预制料混合真空搅拌15-35min,真空度为0.15-0.25MPa,过滤,高温活化,干燥,得到改性竹炭。
4.根据权利要求1-3任一项所述的纸板用防腐耐老化胶黏剂,其特征在于,改性乳清蛋白复合微粒、大豆蛋白质的重量比为8-13:11-13。
5.根据权利要求1-4任一项所述的纸板用防腐耐老化胶黏剂,其特征在于,双(二辛基焦磷酸酰氧基)乙撑钛酸酯、十二烷基磺酸钠的重量比为1.4-1.6:1.2-1.5。
6.根据权利要求1-5任一项所述的纸板用防腐耐老化胶黏剂,其特征在于,芳香族异氰酸酯、聚丙二醇、聚酯二醇,改性乳清蛋白复合微粒的重量比为28-32:8-11:16-18:8-13。
7.根据权利要求1-6任一项所述的纸板用防腐耐老化胶黏剂,其特征在于,芳香族异氰酸酯、聚丙二醇、聚酯二醇、糊化淀粉的重量比为28-32:8-11:16-18:50-54。
8.根据权利要求1-7任一项所述的纸板用防腐耐老化胶黏剂,其特征在于,大豆蛋白质、牛皮胶、骨胶的重量比为11-13:8-12:2-4。
9.根据权利要求1-8任一项所述的纸板用防腐耐老化胶黏剂,其特征在于,改性乳清蛋白复合微粒、戊唑醇、茶多酚、壳聚糖的重量比为8-13:0.6-1:1.5-1.8:0.5-0.8。
10.根据权利要求1-9任一项所述的纸板用防腐耐老化胶黏剂,其特征在于,其原料按重量份包括:芳香族异氰酸酯28-32份,聚丙二醇8-11份,聚酯二醇16-18份,糊化淀粉50-54份,牛皮胶8-12份,骨胶2-4份,改性乳清蛋白复合微粒8-13份,大豆蛋白质11-13份,双(二辛基焦磷酸酰氧基)乙撑钛酸酯1.4-1.6份,十二烷基磺酸钠1.2-1.5份,戊唑醇0.6-1份,茶多酚1.5-1.8份,壳聚糖0.5-0.8份,蓖麻油酸2-4份,水30-35份。
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