CN116732810A - 一种耐腐蚀防水纸浆模塑材料及其制备方法 - Google Patents
一种耐腐蚀防水纸浆模塑材料及其制备方法 Download PDFInfo
- Publication number
- CN116732810A CN116732810A CN202310920068.0A CN202310920068A CN116732810A CN 116732810 A CN116732810 A CN 116732810A CN 202310920068 A CN202310920068 A CN 202310920068A CN 116732810 A CN116732810 A CN 116732810A
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- Prior art keywords
- corrosion
- molding material
- resistant
- parts
- pulp molding
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
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- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- D—TEXTILES; PAPER
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
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- D—TEXTILES; PAPER
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- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/48—Metal or metallised fibres
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
- D21H17/26—Ethers thereof
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/35—Polyalkenes, e.g. polystyrene
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/12—Defoamers
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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Abstract
本发明涉及包装材料制备技术领域,具体涉及一种耐腐蚀防水纸浆模塑材料及其制备方法,包括如下重量份组分:60‑80份木浆纤维、5‑10份复合型耐腐蚀疏水纳米纤维、6‑12份高性能乳胶粉、1‑3份施胶剂、1‑3份湿强剂、1‑3份增强剂、8‑12份填料、0.1‑0.5份助留剂、0.3‑0.8份消泡剂。本发明中,通过在纸浆模塑材料基体中引入复合型耐腐蚀疏水纳米纤维,以及在其表面喷涂高性能乳胶粉,从而在纸浆模塑材料内部形成多层次的疏水层和防腐蚀层,以及在表面构建形成致密的多片层结构,利用形成的多结构疏水层以及防腐蚀层,可以更好的阻止外界酸碱物质的侵蚀,以及阻止表面水珠的形成,从而使得纸浆模塑材料具有优良的防腐蚀以及疏水特性,使其具有更好的使用性能。
Description
技术领域
本发明涉及包装材料制备技术领域,具体为一种耐腐蚀防水纸浆模塑材料及其制备方法。
背景技术
纸浆模塑材料是一种立体造纸技术,它以商品原浆为原料,在纸浆模塑机中经过特定形状的磨具塑造成型为一定形状的纸材料。纸浆模塑材料是近几年迅猛发展的新型包装材料,是各种塑料材料包装材料的潜在替代品。但是由于纸浆模塑材料的主要原料为植物纤维,吸水性强,容易吸水受潮,影响二次使用,因此常因受潮吸水而破坏纤维结构,导致机械性能大幅下降。
例如公告号为CN114990938A的发明专利公开了一种自清洁型超疏水纸浆模塑材料的制备方法,配置碳酸钠溶液和氯化钙溶液;将碳酸钠溶液和纸浆纤维、氯化钙溶液先后置于中速搅拌机反应一段时间;清洗纸浆纤维悬浮液后制备吸附有沉淀碳酸钙的纸浆纤维;将纸浆纤维混合物配置成纸浆纤维悬浮液,采用快速纸页成型技术抄造纸浆模塑材料;将配置的自清洁型超疏水改性混合溶液涂布在纸浆模塑材料上后于烘箱中进行非接触式干燥;通过在纸浆模塑材料表面涂布自清洁型超疏水改性混合溶液,虽然可以达到一定的疏水效果,但是在长期的使用过程中,涂层容易出现开裂,从而影响疏水效果,而且由于涂层不具有防腐蚀性,外界的酸碱物质容易对涂层造成侵蚀,破坏涂层的结构,从而造成纸浆模塑材料不具有长期有效的疏水效果。
发明内容
针对现有技术中存在的问题,本发明的目的在于提供一种耐腐蚀防水纸浆模塑材料及其制备方法。
为实现上述目的,本发明提供如下技术方案:
一种耐腐蚀防水纸浆模塑材料,包括如下重量份组分:60-80份木浆纤维、5-10份复合型耐腐蚀疏水纳米纤维、6-12份高性能乳胶粉、1-3份施胶剂、1-3份湿强剂、1-3份增强剂、8-12份填料、0.1-0.5份助留剂、0.3-0.8份消泡剂。
作为本发明的进一步优选方案,所述木浆纤维选自针叶木长纤维;
所述施胶剂选自阴离子分散松香胶、阳离子分散松香胶、烷基烯酮二聚体中的一种或多种的混合物;
所述消泡剂选自有机硅类、聚醚类、聚醚改性类、磷酸三丁酯类的一种或多种的混合物。
作为本发明的进一步优选方案,所述湿强剂选自脲醛树脂、三聚氰胺甲醛树脂、双醛淀粉、戊二醛和聚乙烯亚胺中的一种或多种的混合物;
所述驻留剂选自阳离子聚丙烯酰胺、阴离子聚丙烯酰胺、两性聚丙烯酰胺、聚乙烯亚胺中的一种或多种的混合物;
所述增强剂选自变性淀粉、聚丙烯酰胺、天然树胶、壳聚糖中的一种或多种的混合物;
所述填料选自滑石粉、碳酸钙、高岭土中的一种或多种的混合物。
作为本发明的进一步优选方案,所述复合型耐腐蚀疏水纳米纤维的制备方法如下:
1)将铜纤维置于容器中,依次用丙酮、超纯水以及无水乙醇反复清洗后,加入到足量的由过硫酸铵和氢氧化钠组成的混合液中,充分浸渍15-20min后取出,用超纯水充分清洗后烘干,得到预处理铜纤维;
2)将乙醇和蒸馏水加入到容器中,水浴加热至50-55℃,加硅烷偶联剂KH570,充分搅拌后,加入预处理铜纤维,反应4-6h后将产物取出,用乙醇和蒸馏水反复清洗后烘干,得到改性铜纤维,再将聚乙烯吡咯烷酮和甲醇加入到蒸馏水中,充分溶解后加入偶氮二异丁腈和苯乙烯,将改性铜纤维悬吊在溶液中,在氮气保护下,80-85℃反应6-8h,然后将改性铜纤维取出,用乙醇和蒸馏水反复清洗后烘干,即可得到复合型耐腐蚀疏水纳米纤维。
作为本发明的进一步优选方案,所述混合液,含有0.2-0.3mol/L的过硫酸铵以及0.1-0.2mol/L的氢氧化钠;
所述乙醇、蒸馏水、硅烷偶联剂KH570、预处理铜纤维的用量比例为(90-120)mL:(10-15)mL:(1-3)g:(5-10)g;
所述聚乙烯吡咯烷酮、甲醇、蒸馏水、偶氮二异丁腈、苯乙烯、改性铜纤维的用量比例为(1-3)g:(40-50)mL:(120-160)mL:(0.9-1.2)g:(10-15)mL:(5-10)g。
作为本发明的进一步优选方案,所述高性能乳胶粉的配制方法如下:
1)将硝酸铜和硝酸镍一起加入到去离子水中,充分搅拌溶解后,加入尿素,混匀后转移至反应釜中,密封后在110-120℃下反应24-28h,待反应结束后自然冷却至室温,将产物离心分离后用无水乙醇反复清洗,烘干后置于马弗炉中,在空气气氛中升温至450-500℃并恒温煅烧2-5h,得到复合纳米材料;
2)将蛭石加入到盐酸溶液中,在50-60℃下震荡8-10h,经离心分离后反复水洗,烘干后研磨过筛,得到二氧化硅纳米片层,然后将二氧化硅纳米片层与复合纳米材料放入球磨机中,以乙醇作为溶剂,采用湿法球磨1-3h,将得到的产物经筛分后烘干,得到复合型纳米片层;
3)将1-3g复合型纳米片层加入到30-50mL蒸馏水中,在60-70℃下超声震荡1-2h,然后与40-60mL含有0.2-0.5g溴化十二烷基吡啶的水溶液混合,继续超声震荡3-5h,待反应完全后进行离心分离,经去离子水反复清洗后烘干,得到改性复合型纳米片层;
4)按重量份数计,将0.1-0.3份十二烷基苯磺酸钠、0.5-0.8份纤维素醚、0.2-0.5份凹凸棒土、0.5-1.2份二苯乙醇酮、1-2份三硬脂酸铝、20-26份改性复合型纳米片层和28-36份乙烯/醋酸乙烯共聚胶粉过筛后送入搅拌机中,充分搅拌均匀即可得到高性能乳胶粉。
作为本发明的进一步优选方案,所述硝酸铜、硝酸镍、去离子水、尿素的用量比例为(18-23)g:(5-8)g:(500-800)mL:(6-10)g;
所述恒温煅烧的升温速率为3-5℃/min。
作为本发明的进一步优选方案,所述蛭石和盐酸溶液的用量比例为(10-30)g:(400-600)mL;
所述盐酸溶液的浓度为2-3mol/L;
所述二氧化硅纳米片层与复合纳米材料的质量比为1:(5-8)。
一种耐腐蚀防水纸浆模塑材料的制备方法,具体包括如下步骤:
1)将木浆纤维加入水中配置成悬浮液,进行散浆10-20min,然后加入复合型耐腐蚀疏水纳米纤维,充分混合后依次加入施胶剂、湿强剂、增强剂、填料、驻留剂以及消泡剂,其中每种组分加入后混合15-25min,再加入下一个组分;
2)将上述浆料用水稀释成浆液,利用成型机成型,其中成型机的上、下模具温度分别为130-180℃,热压时间为150-200s,得到的半成品纸浆模塑材料,再将高性能乳胶粉用清水搅拌后均匀在喷涂在半成品纸浆模塑材料的表面,经烘干后即可。
作为本发明的进一步优选方案,所述悬浮液的浓度为3-7wt%;
所述浆液的质量浓度为3-5‰;
所述喷涂的涂层厚度为100-150μm。
与现有技术相比,本发明的有益效果是:
本发明中,以铜纤维作为基底,原位生长氢氧化铜纳米线阵列,使其表面产生大量羟基,再经硅烷偶联剂KH570处理后,再以苯乙烯为聚合单体,表面原位聚合得到具有超疏水性能的网膜,从而得到具有强耐腐蚀以及强疏水性能的复合型耐腐蚀疏水纳米纤维,通过将该复合型耐腐蚀疏水纳米纤维作为添加剂加入到木浆纤维中,纳米纤维与纳米纤维之间,纳米纤维与木浆纤维之间,以及木浆纤维与木浆纤维之间,均会相互缠绕交联,形成多层次的交联网络,并且由于纳米纤维具有的耐腐蚀以及疏水特性,从而可以形成多层次的疏水层以及防腐蚀层,可以阻隔水分以及酸碱类物质对纸浆模塑材料的侵蚀,从而可以实现防腐蚀以及疏水效果。
为了进一步增强纸浆模塑材料的防腐蚀效果,本发明中,以硝酸铜和硝酸镍作为铜源和镍源,经水热法合成前驱体物质,并通过马弗炉煅烧获得具有多片层结构的复合纳米材料,再通过简单的酸处理蛭石,得到具有更好孔隙度以及更大比表面积的二氧化硅纳米片层,通过将复合纳米材料与二氧化硅纳米片层进行湿法球磨,利用二者的片层结构的相互嵌插堆叠,可以形成具有更多片层结构的复合型纳米片层,其具有的更多片层结构可以更好的分层次对外界物质的侵入产生阻隔效应,阻止物质对纸浆模塑材料的侵蚀,而且由于二氧化硅纳米片层具有一定的孔隙度,使得形成的复合型纳米片层具有一定的孔隙,该孔隙结构有利于纸浆模塑材料基体中纳米纤维表面原位生长的纳米线可以更好的嵌入,从而使得复合型纳米片层通过纳米线嵌入到孔隙结构中作为连接点,可以更好的附着在纸浆模塑材料表面,构建形成致密的多片层结构,从而可以起到更好的防腐蚀效果。
本发明中,通过在纸浆模塑材料基体中引入复合型耐腐蚀疏水纳米纤维,以及在其表面喷涂高性能乳胶粉,从而在纸浆模塑材料内部形成多层次的疏水层和防腐蚀层,以及在表面构建形成致密的多片层结构,利用形成的多结构疏水层以及防腐蚀层,可以更好的阻止外界酸碱物质的侵蚀,以及阻止表面水珠的形成,从而使得纸浆模塑材料具有优良的防腐蚀以及疏水特性,使其具有更好的使用性能。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
本发明实施例中,木浆纤维选用针叶木长纤维,施胶剂选用阴离子分散松香胶,消泡剂选用有机硅类消泡剂,湿强剂选用脲醛树脂,驻留剂选用阳离子聚丙烯酰胺,增强剂选用聚丙烯酰胺,填料选用碳酸钙。
实施例1
一种耐腐蚀防水纸浆模塑材料,包括如下重量份组分:60份木浆纤维、5份复合型耐腐蚀疏水纳米纤维、6份高性能乳胶粉、1份施胶剂、1份湿强剂、1份增强剂、8份填料、0.1份助留剂、0.3份消泡剂;
该纸浆模塑材料的制备方法,具体包括如下步骤:
1)将木浆纤维加入水中,配置成质量浓度为3wt%的悬浮液,进行散浆10min,然后加入复合型耐腐蚀疏水纳米纤维,充分混合后依次加入施胶剂、湿强剂、增强剂、填料、驻留剂以及消泡剂,其中每种组分加入后混合15min,再加入下一个组分;
2)将上述浆料用水稀释成质量浓度为3‰的浆液,利用成型机成型,其中成型机的上、下模具温度分别为130℃,热压时间为150s,得到的半成品纸浆模塑材料,再将高性能乳胶粉用清水搅拌后均匀在喷涂在半成品纸浆模塑材料的表面,涂层厚度为100μm,经烘干后即可。
其中,复合型耐腐蚀疏水纳米纤维的制备方法如下:
1)将铜纤维置于容器中,依次用丙酮、超纯水以及无水乙醇反复清洗后,加入到足量的由过硫酸铵和氢氧化钠组成的混合液中,其中混合液中含有0.2mol/L的过硫酸铵以及0.1mol/L的氢氧化钠,充分浸渍15min后取出,用超纯水充分清洗后烘干,得到预处理铜纤维;
2)将90mL乙醇和10mL蒸馏水加入到容器中,水浴加热至50℃,加1g硅烷偶联剂KH570,充分搅拌后,加入5g预处理铜纤维,反应4h后将产物取出,用乙醇和蒸馏水反复清洗后烘干,得到改性铜纤维,再将1g聚乙烯吡咯烷酮和40mL甲醇加入到120mL蒸馏水中,充分溶解后加入0.9g偶氮二异丁腈和10mL苯乙烯,将5g改性铜纤维悬吊在溶液中,在氮气保护下,80℃反应6h,然后将改性铜纤维取出,用乙醇和蒸馏水反复清洗后烘干,即可得到复合型耐腐蚀疏水纳米纤维。
其中,高性能乳胶粉的配制方法如下:
1)将18g硝酸铜和5g硝酸镍一起加入到500mL去离子水中,充分搅拌溶解后,加入6g尿素,混匀后转移至反应釜中,密封后在110℃下反应24h,待反应结束后自然冷却至室温,将产物离心分离后用无水乙醇反复清洗,烘干后置于马弗炉中,在空气气氛中,以3℃/min升温至450℃并恒温煅烧2h,得到复合纳米材料;
2)将10g蛭石加入到400mL浓度为2mol/L的盐酸溶液中,在50℃下,以200r/min震荡8h,经离心分离后反复水洗,烘干后研磨过筛,得到二氧化硅纳米片层,然后按照质量比为1:5,将二氧化硅纳米片层与复合纳米材料放入球磨机中,以乙醇作为溶剂,200r/min条件下,采用湿法球磨1h,将得到的产物经筛分后烘干,得到复合型纳米片层;
3)将1g复合型纳米片层加入到30mL蒸馏水中,在60℃下超声震荡1h,然后与40mL含有0.2g溴化十二烷基吡啶的水溶液混合,继续超声震荡3h,待反应完全后进行离心分离,经去离子水反复清洗后烘干,得到改性复合型纳米片层;
4)按重量份数计,将0.1份十二烷基苯磺酸钠、0.5份纤维素醚、0.2份凹凸棒土、0.5份二苯乙醇酮、1份三硬脂酸铝、20份改性复合型纳米片层和28份乙烯/醋酸乙烯共聚胶粉过筛后送入搅拌机中,充分搅拌均匀即可得到高性能乳胶粉。
实施例2
一种耐腐蚀防水纸浆模塑材料,包括如下重量份组分:70份木浆纤维、8份复合型耐腐蚀疏水纳米纤维、10份高性能乳胶粉、2份施胶剂、2份湿强剂、2份增强剂、10份填料、0.3份助留剂、0.5份消泡剂;
该纸浆模塑材料的制备方法,具体包括如下步骤:
1)将木浆纤维加入水中,配置成质量浓度为5wt%的悬浮液,进行散浆15min,然后加入复合型耐腐蚀疏水纳米纤维,充分混合后依次加入施胶剂、湿强剂、增强剂、填料、驻留剂以及消泡剂,其中每种组分加入后混合20min,再加入下一个组分;
2)将上述浆料用水稀释成质量浓度为4‰的浆液,利用成型机成型,其中成型机的上、下模具温度分别为150℃,热压时间为180s,得到的半成品纸浆模塑材料,再将高性能乳胶粉用清水搅拌后均匀在喷涂在半成品纸浆模塑材料的表面,涂层厚度为120μm,经烘干后即可。
其中,复合型耐腐蚀疏水纳米纤维的制备方法如下:
1)将铜纤维置于容器中,依次用丙酮、超纯水以及无水乙醇反复清洗后,加入到足量的由过硫酸铵和氢氧化钠组成的混合液中,其中混合液中含有0.25mol/L的过硫酸铵以及0.15mol/L的氢氧化钠,充分浸渍20min后取出,用超纯水充分清洗后烘干,得到预处理铜纤维;
2)将100mL乙醇和12mL蒸馏水加入到容器中,水浴加热至52℃,加2g硅烷偶联剂KH570,充分搅拌后,加入8g预处理铜纤维,反应5h后将产物取出,用乙醇和蒸馏水反复清洗后烘干,得到改性铜纤维,再将2g聚乙烯吡咯烷酮和45mL甲醇加入到150mL蒸馏水中,充分溶解后加入1g偶氮二异丁腈和13mL苯乙烯,将7g改性铜纤维悬吊在溶液中,在氮气保护下,82℃反应7h,然后将改性铜纤维取出,用乙醇和蒸馏水反复清洗后烘干,即可得到复合型耐腐蚀疏水纳米纤维。
其中,高性能乳胶粉的配制方法如下:
1)将20g硝酸铜和7g硝酸镍一起加入到700mL去离子水中,充分搅拌溶解后,加入8g尿素,混匀后转移至反应釜中,密封后在115℃下反应26h,待反应结束后自然冷却至室温,将产物离心分离后用无水乙醇反复清洗,烘干后置于马弗炉中,在空气气氛中,以4℃/min升温至470℃并恒温煅烧3h,得到复合纳米材料;
2)将20g蛭石加入到500mL浓度为2.5mol/L的盐酸溶液中,在55℃下,以250r/min震荡9h,经离心分离后反复水洗,烘干后研磨过筛,得到二氧化硅纳米片层,然后按照质量比为1:7,将二氧化硅纳米片层与复合纳米材料放入球磨机中,以乙醇作为溶剂,250r/min条件下,采用湿法球磨2h,将得到的产物经筛分后烘干,得到复合型纳米片层;
3)将2g复合型纳米片层加入到40mL蒸馏水中,在65℃下超声震荡2h,然后与50mL含有0.3g溴化十二烷基吡啶的水溶液混合,继续超声震荡4h,待反应完全后进行离心分离,经去离子水反复清洗后烘干,得到改性复合型纳米片层;
4)按重量份数计,将0.2份十二烷基苯磺酸钠、0.7份纤维素醚、0.4份凹凸棒土、0.8份二苯乙醇酮、1.5份三硬脂酸铝、25份改性复合型纳米片层和32份乙烯/醋酸乙烯共聚胶粉过筛后送入搅拌机中,充分搅拌均匀即可得到高性能乳胶粉。
实施例3
一种耐腐蚀防水纸浆模塑材料,包括如下重量份组分:80份木浆纤维、10份复合型耐腐蚀疏水纳米纤维、12份高性能乳胶粉、3份施胶剂、3份湿强剂、3份增强剂、12份填料、0.5份助留剂、0.8份消泡剂;
该纸浆模塑材料的制备方法,具体包括如下步骤:
1)将木浆纤维加入水中,配置成质量浓度为7wt%的悬浮液,进行散浆20min,然后加入复合型耐腐蚀疏水纳米纤维,充分混合后依次加入施胶剂、湿强剂、增强剂、填料、驻留剂以及消泡剂,其中每种组分加入后混合25min,再加入下一个组分;
2)将上述浆料用水稀释成质量浓度为5‰的浆液,利用成型机成型,其中成型机的上、下模具温度分别为180℃,热压时间为200s,得到的半成品纸浆模塑材料,再将高性能乳胶粉用清水搅拌后均匀在喷涂在半成品纸浆模塑材料的表面,涂层厚度为150μm,经烘干后即可。
其中,复合型耐腐蚀疏水纳米纤维的制备方法如下:
1)将铜纤维置于容器中,依次用丙酮、超纯水以及无水乙醇反复清洗后,加入到足量的由过硫酸铵和氢氧化钠组成的混合液中,其中混合液中含有0.3mol/L的过硫酸铵以及0.2mol/L的氢氧化钠,充分浸渍20min后取出,用超纯水充分清洗后烘干,得到预处理铜纤维;
2)将120mL乙醇和15mL蒸馏水加入到容器中,水浴加热至55℃,加3g硅烷偶联剂KH570,充分搅拌后,加入10g预处理铜纤维,反应6h后将产物取出,用乙醇和蒸馏水反复清洗后烘干,得到改性铜纤维,再将3g聚乙烯吡咯烷酮和50mL甲醇加入到160mL蒸馏水中,充分溶解后加入1.2g偶氮二异丁腈和15mL苯乙烯,将10g改性铜纤维悬吊在溶液中,在氮气保护下,85℃反应8h,然后将改性铜纤维取出,用乙醇和蒸馏水反复清洗后烘干,即可得到复合型耐腐蚀疏水纳米纤维。
其中,高性能乳胶粉的配制方法如下:
1)将23g硝酸铜和8g硝酸镍一起加入到800mL去离子水中,充分搅拌溶解后,加入10g尿素,混匀后转移至反应釜中,密封后在120℃下反应28h,待反应结束后自然冷却至室温,将产物离心分离后用无水乙醇反复清洗,烘干后置于马弗炉中,在空气气氛中,以5℃/min升温至500℃并恒温煅烧5h,得到复合纳米材料;
2)将30g蛭石加入到600mL浓度为3mol/L的盐酸溶液中,在60℃下,以300r/min震荡10h,经离心分离后反复水洗,烘干后研磨过筛,得到二氧化硅纳米片层,然后按照质量比为1:8,将二氧化硅纳米片层与复合纳米材料放入球磨机中,以乙醇作为溶剂,300r/min条件下,采用湿法球磨3h,将得到的产物经筛分后烘干,得到复合型纳米片层;
3)将3g复合型纳米片层加入到50mL蒸馏水中,在70℃下超声震荡2h,然后与60mL含有0.5g溴化十二烷基吡啶的水溶液混合,继续超声震荡5h,待反应完全后进行离心分离,经去离子水反复清洗后烘干,得到改性复合型纳米片层;
4)按重量份数计,将0.3份十二烷基苯磺酸钠、0.8份纤维素醚、0.5份凹凸棒土、1.2份二苯乙醇酮、2份三硬脂酸铝、26份改性复合型纳米片层和36份乙烯/醋酸乙烯共聚胶粉过筛后送入搅拌机中,充分搅拌均匀即可得到高性能乳胶粉。
对比例1:本对比例与实施例1基本相同,不同之处在于,不含有复合型耐腐蚀疏水纳米纤维。
对比例2:本对比例与实施例1基本相同,不同之处在于,使用预处理铜纤维替代复合型耐腐蚀疏水纳米纤维。
对比例3:本对比例与实施例1基本相同,不同之处在于,不含有高性能乳胶粉。
对比例4:本对比例与实施例1基本相同,不同之处在于,高性能乳胶粉的配制中,不含有复合纳米材料。
对比例5:本对比例与实施例1基本相同,不同之处在于,高性能乳胶粉的配制中,不含有二氧化硅纳米片层。
测试实验:
将实施例1-3和对比例1-5提供的纸浆模塑材料试样,采用JIC-1湿润角测量仪进行水接触角测试,并且在室温下,将纸浆模塑材料试样依次浸入到浓酸液以及浓碱液中,分别浸渍240h,观察纸浆模塑材料试样的变化情况,记录结果如表1所示。
表1
通过表1可知,本发明中的纸浆模塑材料,可以很好的阻止外界酸碱物质的侵蚀,以及阻止表面水珠的形成,从而使得纸浆模塑材料具有优良的防腐蚀以及疏水特性。
以上公开的本发明优选实施例只是用于帮助阐述本发明。优选实施例并没有详尽叙述所有的细节,也不限制该发明仅为所述的具体实施方式。显然,根据本说明书的内容,可作很多的修改和变化。本说明书选取并具体描述这些实施例,是为了更好地解释本发明的原理和实际应用,从而使所属技术领域技术人员能很好地理解和利用本发明。本发明仅受权利要求书及其全部范围和等效物的限制。
Claims (10)
1.一种耐腐蚀防水纸浆模塑材料,其特征在于,包括如下重量份组分:60-80份木浆纤维、5-10份复合型耐腐蚀疏水纳米纤维、6-12份高性能乳胶粉、1-3份施胶剂、1-3份湿强剂、1-3份增强剂、8-12份填料、0.1-0.5份助留剂、0.3-0.8份消泡剂。
2.根据权利要求1所述的一种耐腐蚀防水纸浆模塑材料,其特征在于,所述木浆纤维选自针叶木长纤维;
所述施胶剂选自阴离子分散松香胶、阳离子分散松香胶、烷基烯酮二聚体中的一种或多种的混合物;
所述消泡剂选自有机硅类、聚醚类、聚醚改性类、磷酸三丁酯类的一种或多种的混合物。
3.根据权利要求1所述的一种耐腐蚀防水纸浆模塑材料,其特征在于,所述湿强剂选自脲醛树脂、三聚氰胺甲醛树脂、双醛淀粉、戊二醛和聚乙烯亚胺中的一种或多种的混合物;
所述驻留剂选自阳离子聚丙烯酰胺、阴离子聚丙烯酰胺、两性聚丙烯酰胺、聚乙烯亚胺中的一种或多种的混合物;
所述增强剂选自变性淀粉、聚丙烯酰胺、天然树胶、壳聚糖中的一种或多种的混合物;
所述填料选自滑石粉、碳酸钙、高岭土中的一种或多种的混合物。
4.根据权利要求1所述的一种耐腐蚀防水纸浆模塑材料,其特征在于,所述复合型耐腐蚀疏水纳米纤维的制备方法如下:
1)将铜纤维置于容器中,依次用丙酮、超纯水以及无水乙醇反复清洗后,加入到足量的由过硫酸铵和氢氧化钠组成的混合液中,充分浸渍15-20min后取出,用超纯水充分清洗后烘干,得到预处理铜纤维;
2)将乙醇和蒸馏水加入到容器中,水浴加热至50-55℃,加硅烷偶联剂KH570,充分搅拌后,加入预处理铜纤维,反应4-6h后将产物取出,用乙醇和蒸馏水反复清洗后烘干,得到改性铜纤维,再将聚乙烯吡咯烷酮和甲醇加入到蒸馏水中,充分溶解后加入偶氮二异丁腈和苯乙烯,将改性铜纤维悬吊在溶液中,在氮气保护下,80-85℃反应6-8h,然后将改性铜纤维取出,用乙醇和蒸馏水反复清洗后烘干,即可得到复合型耐腐蚀疏水纳米纤维。
5.根据权利要求4所述的一种耐腐蚀防水纸浆模塑材料,其特征在于,所述混合液,含有0.2-0.3mol/L的过硫酸铵以及0.1-0.2mol/L的氢氧化钠;
所述乙醇、蒸馏水、硅烷偶联剂KH570、预处理铜纤维的用量比例为(90-120)mL:(10-15)mL:(1-3)g:(5-10)g;
所述聚乙烯吡咯烷酮、甲醇、蒸馏水、偶氮二异丁腈、苯乙烯、改性铜纤维的用量比例为(1-3)g:(40-50)mL:(120-160)mL:(0.9-1.2)g:(10-15)mL:(5-10)g。
6.根据权利要求1所述的一种耐腐蚀防水纸浆模塑材料,其特征在于,所述高性能乳胶粉的配制方法如下:
1)将硝酸铜和硝酸镍一起加入到去离子水中,充分搅拌溶解后,加入尿素,混匀后转移至反应釜中,密封后在110-120℃下反应24-28h,待反应结束后自然冷却至室温,将产物离心分离后用无水乙醇反复清洗,烘干后置于马弗炉中,在空气气氛中升温至450-500℃并恒温煅烧2-5h,得到复合纳米材料;
2)将蛭石加入到盐酸溶液中,在50-60℃下震荡8-10h,经离心分离后反复水洗,烘干后研磨过筛,得到二氧化硅纳米片层,然后将二氧化硅纳米片层与复合纳米材料放入球磨机中,以乙醇作为溶剂,采用湿法球磨1-3h,将得到的产物经筛分后烘干,得到复合型纳米片层;
3)将1-3g复合型纳米片层加入到30-50mL蒸馏水中,在60-70℃下超声震荡1-2h,然后与40-60mL含有0.2-0.5g溴化十二烷基吡啶的水溶液混合,继续超声震荡3-5h,待反应完全后进行离心分离,经去离子水反复清洗后烘干,得到改性复合型纳米片层;
4)按重量份数计,将0.1-0.3份十二烷基苯磺酸钠、0.5-0.8份纤维素醚、0.2-0.5份凹凸棒土、0.5-1.2份二苯乙醇酮、1-2份三硬脂酸铝、20-26份改性复合型纳米片层和28-36份乙烯/醋酸乙烯共聚胶粉过筛后送入搅拌机中,充分搅拌均匀即可得到高性能乳胶粉。
7.根据权利要求6所述的一种耐腐蚀防水纸浆模塑材料,其特征在于,所述硝酸铜、硝酸镍、去离子水、尿素的用量比例为(18-23)g:(5-8)g:(500-800)mL:(6-10)g;
所述恒温煅烧的升温速率为3-5℃/min。
8.根据权利要求6所述的一种耐腐蚀防水纸浆模塑材料,其特征在于,所述蛭石和盐酸溶液的用量比例为(10-30)g:(400-600)mL;
所述盐酸溶液的浓度为2-3mol/L;
所述二氧化硅纳米片层与复合纳米材料的质量比为1:(5-8)。
9.根据权利要求1-8任意一项所述的一种耐腐蚀防水纸浆模塑材料的制备方法,其特征在于,具体包括如下步骤:
1)将木浆纤维加入水中配置成悬浮液,进行散浆10-20min,然后加入复合型耐腐蚀疏水纳米纤维,充分混合后依次加入施胶剂、湿强剂、增强剂、填料、驻留剂以及消泡剂,其中每种组分加入后混合15-25min,再加入下一个组分;
2)将上述浆料用水稀释成浆液,利用成型机成型,其中成型机的上、下模具温度分别为130-180℃,热压时间为150-200s,得到的半成品纸浆模塑材料,再将高性能乳胶粉用清水搅拌后均匀在喷涂在半成品纸浆模塑材料的表面,经烘干后即可。
10.根据权利要求9所述的一种耐腐蚀防水纸浆模塑材料的制备方法,其特征在于,所述悬浮液的浓度为3-7wt%;
所述浆液的质量浓度为3-5‰;
所述喷涂的涂层厚度为100-150μm。
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