CN116641257A - 一种阻燃纸及其制备方法 - Google Patents
一种阻燃纸及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种阻燃纸，该阻燃纸由打浆处理后的纸浆、磷氮系阻燃剂、阳离子剂、助留助滤体系，经浆内添加法制备得到。各原料通过混合均匀，抄造成形，压榨，干燥，得到阻燃纸。阳离子剂可以有效中和磷氮系阻燃剂的负电性，缓解磷氮系阻燃剂的水解，协同提高纸的阻燃效果。同时，施胶剂可以使纸张具有一定的抗水性，改善纸的印刷性能，提高纸的耐久性和强度，在潮湿环境下防止纸张中的阻燃剂水解，避免纸张产生机械强度降低和阻燃效果减弱的问题。
Description
技术领域
本发明涉及一种阻燃纸及其制备方法，属于特种纸制造领域。
背景技术
纤维素纸大多数是由植物纤维制成，具有天然可降解性、可回收性、质轻和成本低廉等优点，广泛应用于文化、包装、家装、纺织等领域。但它也有易燃、易受潮等缺点，一定程度上影响了它的基本性能和应用范围。
磷氮系阻燃剂是一种重要的无卤气源兼酸源阻燃剂，主要包括：聚磷酸铵(APP)、三聚氰胺聚磷酸盐(PNA)、磷酸铵盐等。磷氮系阻燃剂作为高效的膨胀型阻燃体系，具有磷氮含量高、热稳定性好、炭层紧密、发烟量低等优点，广泛应用于聚合物、涂料、木制品和各种纤维材料的阻燃改性。然而磷氮系阻燃剂吸湿性强，在潮湿环境下容易水解和迁移，使其阻燃性能下降。在浆内添加过程中，磷氮系阻燃剂发生水解，分子链上的铵根(NH4 +)部分电离，在水中表现出强负电性，对阻燃剂在浆内留着有很大的影响，即阻燃剂在浆内添加过程中易随水流失，阻燃效果不理想。
目前阻燃纸的制备通常采用浸渍法或涂布法，这些方法增加了生产操作环节，且无法实现纸张本征阻燃及其疏水性能。
发明内容
本发明所要解决的技术问题是提供一种通过阳离子剂和磷氮系阻燃剂协同作用，提高阻燃剂留着的阻燃纸及其制备方法。
为解决以上技术问题，本发明首先公开了一种阻燃纸，该阻燃纸由打浆处理后的纸浆、磷氮系阻燃剂、阳离子剂、助留助滤体系，经浆内添加法制备得到。
进一步地，该阻燃纸的制备原料中还包括施胶剂。
进一步地，所述施胶剂为烷基烯酮二聚体(AKD)、阳离子松香或阴离子松香的一种；所述烷基烯酮二聚体添加量为纸浆绝干纤维的0.05wt％-0.5wt％，阳离子松香或阴离子松香添加量为纸浆绝干纤维的0.5wt％-5.0wt％。
进一步地，所述磷氮系阻燃剂为聚磷酸铵(APP)、三聚氰胺聚磷酸盐(MPP)、三聚氰胺改性聚磷酸铵(MFAPP)或磷酸铵盐的一种，添加量为纸浆绝干纤维的15wt％-65wt％。
进一步地，所述阳离子剂为低分子量高阳电荷密度的有机聚合物，具体为聚二烯丙基二甲基氯化铵(PDDA)、聚乙烯亚胺(PEI)、聚酰胺环氧氯丙烷(PAE)或聚胺(聚EPI-DA)的一种或两种以上，添加量为纸浆绝干纤维的0.5wt％-5.0wt％。
进一步地，所述助留助滤体系为阳离子聚丙烯酰胺(CPAM)，添加量为纸浆绝干纤维的0.02wt％-0.1wt％。
进一步地，所述助留助滤体系为阳离子聚丙烯酰胺(CPAM)与膨润土微粒，阳离子聚丙烯酰胺(CPAM)添加量为纸浆绝干纤维的0.02wt％-0.1wt％，膨润土微粒添加量为纸浆绝干纤维的0.1wt％-0.4wt％。和膨润土微粒组合所得的助留助滤体系比单独使用阳离子聚丙烯酰胺时对阻燃剂的留着效果更好。
本发明还公开了一种前述阻燃纸的制备方法，纸浆打浆处理后，边搅拌边依次加入磷氮系阻燃剂、阳离子剂、助留助滤体系，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
进一步地，当制备原料含有施胶剂时，可以是：纸浆打浆处理后，边搅拌边依次加入施胶剂、磷氮系阻燃剂、阳离子剂、助留助滤体系，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
进一步地，当制备原料含有施胶剂时，还可以是：纸浆打浆处理后，边搅拌边依次加入磷氮系阻燃剂、施胶剂、阳离子剂、助留助滤体系，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
纸浆为本色针叶木硫酸盐浆或其他种类纸浆，如本色阔叶木硫酸盐浆、漂白针叶木硫酸盐浆、漂白阔叶木硫酸盐浆等，纸浆打浆度为15-65°SR。
阳离子剂是一种低分子量高阳电荷密度的有机聚合物，具有较强的正电性，可以有效中和磷氮系阻燃剂的负电性，缓解磷氮系阻燃剂的水解，协同提高纸的阻燃效果。同时，施胶剂可以使纸张具有一定的抗水性，改善纸的印刷性能，提高纸的耐久性和强度，在潮湿环境下防止纸张中的阻燃剂水解，避免纸张产生机械强度降低和阻燃效果减弱的问题。助留助滤系统可进一步提高磷氮系阻燃剂在浆中的留着率，不仅可以使纸张实现本征阻燃，提高阻燃性能，且配合施胶剂可以提高纸张疏水性能，还可以降低生产成本，易于工业化批量生产等特点。本发明浆内添加过程中可先添加施胶剂再添加磷氮系阻燃剂，也可以先添加磷氮系阻燃剂再添加施胶剂。其中先添加施胶剂，再添加磷氮系阻燃剂，有效提高了阻燃纸的疏水性，比先添加磷氮系阻燃剂的纸张Cobb值提高了36％。
附图说明
图1为在不同阳离子剂协同下聚磷酸铵(APP)添加量对纸张阻燃性能纸张LOI值的影响折线图；
图2为阳离子剂聚二烯丙基二甲基氯化铵(PDDA)添加量对纸张阻燃性能纸张LOI值的影响折线图；
图3为施胶剂烷基烯酮二聚体(AKD)添加量对纸与纸板表面吸水量纸张Cobb值的影响折线图。
具体实施方式
下面结合实施例对本发明做更进一步地解释。下列实施例仅用于说明本发明，但并不用来限定本发明的实施范围。
一、以下实施例1至3是说明在阳离子剂协同作用下，磷氮系阻燃剂添加量对纸张阻燃性能影响。
实施例1
将本色针叶木硫酸盐浆或其他种类纸浆打浆至32°SR，根据200g/m2纸张定量称取纸浆，在纸浆中依次加入25％APP悬浮液、5％PDDA、0.1％CPAM、0.2％膨润土微粒(所有用量均为相对于纸浆绝干纤维的质量百分比)，混合均匀，抄造成形，压榨，干燥，得到阻燃纸。
通过检测，本实施例1制备所得阻燃纸，当25％APP与5％PDDA协同作用，LOI值达到36.8％。
实施例2
将本色针叶木硫酸盐浆或其他种类纸浆打浆至32°SR，根据200g/m2纸张定量称取纸浆，在纸浆中依次加入30％APP悬浮液、5％PDDA、0.1％CPAM、0.2％膨润土微粒(所有用量均为相对于纸浆绝干纤维的质量百分比)，混合均匀，抄造成形，压榨，干燥，得到阻燃纸。
通过检测，本实施例2制备所得阻燃纸，当30％APP与5％PDDA协同作用，LOI值达到45.6％。
实施例3
将本色针叶木硫酸盐浆或其他种类纸浆打浆至32°SR，根据200g/m2纸张定量称取纸浆，在纸浆中依次加入35％APP悬浮液、5％PDDA、0.1％CPAM、0.2％膨润土微粒(所有用量均为相对于纸浆绝干纤维的质量百分比)，混合均匀，抄造成形，压榨，干燥，得到阻燃纸。
通过检测，本实施例3制备所得阻燃纸，当35％APP与5％PDDA协同作用，LOI值达到50.7％。
结论一：基于实施例1至3，以及图1得出，在阳离子剂和磷氮系阻燃剂的协同作用下，通过浆内制备所得阻燃纸具有良好的阻燃性能，阳离子剂用量一定时，随着磷氮系阻燃剂用量的增加，阻燃性能提高。
另外，经研究发现：在阳离子剂的协同下，阻燃剂用量在15-65％的范围内均有良好的阻燃效果，该范围内时，阻燃剂添加量愈高，阻燃效果愈好。从经济角度去考虑，当添加量在20％-40％之间时，可以保证阻燃纸在具有优良阻燃效果的同时，也具有很好的经济成本回收性，因此阻燃剂的最佳应用范围在20％-40％。
二、以下实施例4至5是说明施胶剂和磷氮系阻燃剂添加顺序对纸张阻燃性能和疏水性能影响。
实施例4
将本色针叶木硫酸盐浆或其他种类纸浆打浆至32°SR，根据200g/m2纸张定量称取纸浆，在纸浆中依次加入0.3％AKD、30％APP悬浮液、3％PDDA、0.1％CPAM、0.2％膨润土微粒(所有用量均为相对于纸浆绝干纤维的质量百分比)，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
通过检测，本实施例4制备所得疏水阻燃纸Cobb值为35g/m2，LOI值为40.2％。
实施例5
将本色针叶木硫酸盐浆或其他种类纸浆打浆至32°SR，根据200g/m2纸张定量称取纸浆，在纸浆中依次加入30％APP悬浮液、0.3％AKD、3％PDDA、0.1％CPAM、0.2％膨润土微粒(所有用量均为相对于纸浆绝干纤维的质量百分比)，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
通过检测，本实施例5制备疏水阻燃纸Cobb值为55g/m2，LOI值为39.2％。
结论二：基于实施例4至5得出，先添加施胶剂比先添加阻燃剂可以得到更好的阻燃效果和疏水效果。实施例4相对实施例5，其纸张Cobb值提高了36％。
三、以下实施例6至9是说明阳离子剂用量对纸张阻燃性能和疏水性能影响。
实施例6
将本色针叶木硫酸盐浆或其他种类纸浆打浆至32°SR，根据200g/m2纸张定量称取纸浆，在纸浆中依次加入0.3％AKD、30％APP悬浮液、0.1％CPAM、0.2％膨润土微粒(所有用量均为相对于纸浆绝干纤维的质量百分比)，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
通过检测，本实施例6制备所得疏水阻燃纸Cobb值为42g/m2，LOI值为32.2％。
实施例7
将本色针叶木硫酸盐浆或其他种类纸浆打浆至32°SR，根据200g/m2纸张定量称取纸浆，在纸浆中依次加入0.3％AKD、30％APP悬浮液、0.5％PDDA、0.1％CPAM、0.2％膨润土微粒(所有用量均为相对于纸浆绝干纤维的质量百分比)，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
通过检测，本实施例7制备所得疏水阻燃纸Cobb值为40g/m2，LOI值为33.6％。
实施例8
将本色针叶木硫酸盐浆或其他种类纸浆打浆至32°SR，根据200g/m2纸张定量称取纸浆，在纸浆中依次加入0.3％AKD、30％APP悬浮液、3％PDDA、0.1％CPAM、0.2％膨润土微粒(所有用量均为相对于纸浆绝干纤维的质量百分比)，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
通过检测，本实施例8制备所得疏水阻燃纸Cobb值为35g/m2，LOI值为40.2％。
实施例9
将本色针叶木硫酸盐浆或其他种类纸浆打浆至32°SR，根据200g/m2纸张定量称取纸浆，在纸浆中依次加入0.3％AKD、30％APP悬浮液、5％PDDA、0.1％CPAM、0.2％膨润土微粒(所有用量均为相对于纸浆绝干纤维的质量百分比)，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
通过检测，本实施例9制备所得疏水阻燃纸Cobb值为32g/m2，LOI值为43.9％，达到了难燃级别并兼具了良好的疏水性能。
结论三：基于实施例6至9得出，阳离子剂与阻燃剂有很好的协同阻燃的效果。而实验中发现：随着阳离子剂用量的增加，协同功效增加，但用量过高时，浆料呈高絮凝状态，虽然LOI值仍有极少量提高，但会对其他性能造成影响，比如纸张的均匀性、抗张强力等。
Claims (10)
1.一种阻燃纸，其特征在于：该阻燃纸由打浆处理后的纸浆、磷氮系阻燃剂、阳离子剂、助留助滤体系，经浆内添加法制备得到。
2.根据权利要求1所述阻燃纸，其特征在于：该阻燃纸的制备原料中还包括施胶剂。
3.根据权利要求2所述阻燃纸，其特征在于：所述施胶剂为烷基烯酮二聚体、阳离子松香或阴离子松香的一种；所述烷基烯酮二聚体添加量为纸浆绝干纤维的0.05wt％-0.5wt％，阳离子松香或阴离子松香添加量为纸浆绝干纤维的0.5wt％-5.0wt％。
4.根据权利要求1所述阻燃纸，其特征在于：所述磷氮系阻燃剂为聚磷酸铵、三聚氰胺聚磷酸盐、三聚氰胺改性聚磷酸铵或磷酸铵盐的一种或两种以上，添加量为纸浆绝干纤维的15wt％-65wt％。
5.根据权利要求1所述阻燃纸，其特征在于：所述阳离子剂为聚二烯丙基二甲基氯化铵、聚乙烯亚胺、聚酰胺环氧氯丙烷或聚胺的一种或两种以上，添加量为纸浆绝干纤维的0.5wt％-5.0wt％。
6.根据权利要求1所述阻燃纸，其特征在于：所述助留助滤体系为阳离子聚丙烯酰胺，添加量为纸浆绝干纤维的0.02wt％-0.1wt％。
7.根据权利要求1所述阻燃纸，其特征在于：所述助留助滤体系为阳离子聚丙烯酰胺与膨润土微粒，阳离子聚丙烯酰胺添加量为纸浆绝干纤维的0.02wt％-0.1wt％，膨润土微粒添加量为纸浆绝干纤维的0.1wt％-0.4wt％。
8.一种如权利要求1-7任意一项权利要求所述阻燃纸的制备方法，其特征在于：纸浆打浆处理后，边搅拌边依次加入磷氮系阻燃剂、阳离子剂、助留助滤体系，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
9.根据权利要求8所述阻燃纸的制备方法，其特征在于：当制备原料含有施胶剂时，纸浆打浆处理后，边搅拌边依次加入施胶剂、磷氮系阻燃剂、阳离子剂、助留助滤体系，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
10.根据权利要求8所述阻燃纸的制备方法，其特征在于：当制备原料含有施胶剂时，纸浆打浆处理后，边搅拌边依次加入磷氮系阻燃剂、施胶剂、阳离子剂、助留助滤体系，混合均匀，抄造成形，压榨，干燥，得到疏水阻燃纸。
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