CN112647358A - 一种磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂及其制备方法与应用 - Google Patents
一种磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂及其制备方法与应用 Download PDFInfo
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
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- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/6461—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
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- D21H19/00—Coated paper; Coating material
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- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
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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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/52—Cellulose; Derivatives thereof
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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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
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Abstract
本发明涉及防火涂料技术领域，具体涉及一种磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂及其制备方法与应用，所述覆膜剂的原料组成包括：3.0～7.0％微晶蜡、15.0～17.0％水溶性淀粉、10.0～15.0％填料、3.0‑5.0％羧甲基纤维素、60.0～65.0％磷硼杂链预聚物嵌段聚氨酯水性共聚物，该共聚物结构式如式(1)所示：
Description
技术领域
本发明涉及防火涂料技术领域，具体涉及一种磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂及其制备方法与应用。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
用于纸质包装品的纸张材料属于天然有机高分子材料，其主要成分为植物纤维素[通式为(C6H10O5)n]，由此决定了纸质包装箱具有吸水受潮和遇火易燃的特性。吸水受潮使纸品包装箱体强度降低，抗压能力降低，使用功能削弱甚至丧失，研究人员长期致力于纸品包装的抗水防潮科学研究和技术开发，取得了有效成果，包括纸板表面塑料覆膜法、防潮油涂膜法等防水防潮技术得到了推广应用，其中防潮油涂膜防潮法应用便捷，效果较好，防潮油涂膜防潮法是在纸箱制造的印刷工段之后，在箱板纸表面满版涂布防潮油，防潮油干燥固化后，在箱板纸表面形成一层致密牢固的抗水防潮保护膜，赋予纸质包装箱抗水防潮的性能，防潮油因当初使用植物油醇酸树脂为成膜物质而得名，目前随着环保意识增强和合成树脂新品种的涌现，防潮油的成膜树脂已被新型的水性合成树脂所代替，组成体系已由原先的有机溶剂体系发展为水性体系，防潮油之称已无法涵盖此类产品的全部内涵，应该确切的称此类产品为纸箱防潮涂膜剂。
纸张的燃点在130℃左右，极限氧指数(LOI)仅为15左右，由此决定了纸质包装箱属于易燃物，遇火易燃，在使用过程中存在火灾隐患,阻燃防火已经受到国内外科技工作者和工程技术人员的高度重视。研究表明，卤素、磷、硼、氮、硅等元素在有机材料燃烧过程具有优异的阻燃效果，含卤阻燃剂因在燃烧过程中生成高毒性气体而限用，P、B、N、Si等元素阻燃剂具有无卤低烟、环保高效的阻燃功能。将P、B、N、Si等元素通过分子设计与合成，合成具有本征阻燃功能的聚合物，是制备无卤低烟、长效阻燃高分子材料的有效途径。
文献1公开了一种植物纤维新型阻燃粘合剂及其制备方法，该粘合剂包括：磷酸三钠14份，硫酸镁溶液3075份，氢氧化钙15份，乳化剂14份，淀粉胶2080份，酚醛树脂1030份，酒石酸24份，硼酸13份，氧化镁105118份，二氧化硅25份和着色剂13份。这种粘合剂具有持久优异的防火性能、耐水性能和环保性能。
文献2公开了磷硅氮三元协同阻燃剂及其制备方法与应用，其通过使用有机硼催化剂，利用二苯基氧化膦及其衍生物与含有碳碳双键的硅氮烷发生加成反应而制备一类新型含磷、硅和氮的化合物。
文献3公开了一种防潮阻燃瓦楞纸箱的制备方法，其在瓦楞纸箱外侧面和内壁面均覆盖有防潮阻燃涂层，所述防潮阻燃涂层由树脂混料、乙醇水溶液、油脂品、氯化石蜡、防潮剂、防火剂及复合稳定剂组成。
目前，现有的一些纸箱防火技术具有以下特点：
①无机阻燃剂居多，有机阻燃剂较少。无机阻燃剂的优点在于价格低廉，品种较多，缺点在于比重大、用量多、耐水性差、迁移性大，导致纸质包装箱强度下降、抗压强度不高、耐水防潮性下降、使用安全性低等。有机物阻燃剂的优点在于阻燃效率高、比重小、耐水性好，不足之处在于品种少、价格较高、毒性大、含卤高烟、不耐有机质，因迁移造成包装物品和周围环境的污染，发生火灾时因含卤高烟会造成更大的环境污染。
②添加型阻燃剂居多，本征型阻燃剂较少。添加型阻燃剂是以具有阻燃功能的低分子化合物，直接添加于非阻燃粘合剂基料，在应用过程中其优点在于品种多、使用方便，其缺点在于稳定性差、耐久性不高。本征型阻燃剂是通过分子设计和合成，将具有阻燃功能的元素通过化学键的方式键接到成膜树脂高分子链结构中，得到本征阻燃聚合物，或以合成本征阻燃聚合物与非阻燃基料高分子共混，制备共混型纸箱防潮防火水性涂膜剂，其优点在于提高了阻燃元素的存在稳定性，达到环保长效的阻燃效果，其不足之处在于品种少、价格高、技术难度大。
现有技术文献：
文献1：中国专利，申请号为201810561651.6，名称为一种植物纤维新型阻燃粘合剂及其制备方法。
文献2：中国专利，申请号为201210479147.4，名称为磷硅氮三元协同阻燃剂及其制备方法与应用。
文献3：中国专利，申请号为201710836186.8，名称为一种防潮阻燃瓦楞纸箱的制备方法。
发明内容
本发明的目的是制备具有防潮、防火功能，并适合纸箱表面辊涂或喷涂的涂膜剂，且经该涂膜剂处理的布料具有低毒环保、低烟无卤、长效阻燃、防潮防火、高光美化和减摩耐磨的协效复合功能。
为此，本发明公开一种磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂及其制备方法与应用，其通过分子设计与合成将磷硼阻燃元素和亲水基团以化学键形式键接于聚合物分子结构之中，得到适用于纸箱表面辊涂或喷涂的涂膜剂。
为实现上述目的，本发明的技术方案如下所示：
在本发明的第一方面，公开一种磷硼杂链预聚物嵌段聚氨酯水性共聚物，其结构式如式(1)所示：
所述式(1)中，R包括-HCH2CH2OH、-(CH2CH2OH)2、-HCH2CH3、-(CH2CH3)2等中的任意一种。
在本发明的第二方面，公开所述磷硼杂链预聚物嵌段聚氨酯水性共聚物的制备方法，包括如下步骤：
(1)将有机溶剂、磷硼杂链预聚物液体、二月桂酸二丁基锡混合后在保护气氛与加热条件下保温，待体系温度均匀后加入甲苯二异氰酸酯和二羟甲基丙酸，并将体系升温后保温，分离溶剂。
(2)将体系降温后加入中和剂和水，搅拌后调整体系pH值，即得。
进一步地，步骤(1)中，所述有机溶剂包括二甲苯、甲苯、环己酮等中的任意一种，其添加量能够充分溶解各原料即可，本发明不做具体限定。
进一步地，步骤(1)中，所述磷硼杂链预聚物液体的粘度为2500～3000Cp(25℃)，可选地，采用水将所述磷硼杂链预聚物稀释成符合上述粘度要求的预聚物液体。
进一步地，所述共聚物的制备方法中，按质量百分数计，磷硼杂链预聚物(PDCP-DGB)、甲苯二异氰酸酯(TDI)、二羟甲基丙酸(DMPA)的添加比例依次序为：75～77％、15～18％、7～8％。
进一步地，步骤(1)中，所述二月桂酸二丁基锡与甲苯二异氰酸酯物质的量比为1:0.01～0.03。在本发明中，利用二月桂酸二丁基锡的催化作用，通过逐步加聚合成磷硼杂链预聚物聚氨酯嵌段共聚物。
进一步地，步骤(1)中，所述磷硼杂链预聚物的数均分子量为1500～2500、分布指数为1.1～1.2。
进一步地，步骤(1)中，所述保护气氛包括氮气、氩气等惰性气体，避免氧气对逐步加聚反应的阻聚效应。
进一步地，步骤(1)中，所述加热温度为60～65℃，加热方式为水浴加热，保温时间为20～35min。在一定温度下反应有助于加速反应速率，提高反应效率。
进一步地，步骤(1)中，所述体系升温后温度为70～75℃，进一步提高缩聚反应的反应程度，保温时间为1.5～2.5h。
进一步地，步骤(2)中，所述中和剂包括一乙醇胺、二乙醇胺、一乙胺、二乙胺等中的至少一种。在本发明中，所述中和剂的主要作用是与体系中的二羟甲基丙酸反应，进而将反应产物的pH值调节至合格。
进一步地，步骤(2)中，所述体系降温后温度为45～50℃。
进一步地，步骤(2)中，所述pH值保持在7.5～9.0范围内，以保持聚合物水性体系稳定。
在本发明的第三方面，公开一种磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂，按质量百分数计，其原料组成包括：3.0～7.0％微晶蜡、15.0～17.0％水溶性淀粉、10.0～15.0％填料、3.0-5.0％羧甲基纤维素、60.0～65.0％本发明所述磷硼杂链预聚物嵌段聚氨酯水性共聚物。
进一步地，所述填料主要作用是提高覆膜剂干燥固化后结构稳定性，包括纳米碳酸钙、滑石粉、膨润土、纳米凹凸棒土等中的至少一种。
进一步地，所述水溶性淀粉与磷硼杂链预聚物嵌段聚氨酯预聚物拼用作为阻燃纸箱覆膜剂的基料，包括变性淀粉等，例如：氧化淀粉、醚化淀粉等中的至少一种。
进一步地，所述覆膜剂的原料组成还包括助剂，可选地，所述助剂包括消泡剂，例如：聚甲基硅油、磷酸三丁酯等中的至少一种，其用量为覆膜剂配方总质量的1～3％。
进一步地，所述覆膜剂细度≤40μm，以便将覆膜剂均匀涂在纸张表面。
进一步地，所述覆膜剂的原料组成还包括水复合溶剂。可选地，所述水复合溶剂的添加量以调整覆膜剂粘度在80～120s(涂-4杯)之间为准。
进一步地，所述水复合溶剂为水、乙醇和乙二醇二甲醚的混合体系，可选地，所述水、乙醇和乙二醇二丁醚的体积比为3:1:2。
在本发明的第四方面，公开所述磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂的制备方法，包括：将所述微晶蜡、水溶性淀粉、填料、羧甲基纤维素、磷硼杂链预聚物嵌段聚氨酯水性共聚物混合均匀，磨细后再以水复合溶剂调节粘度，即得。
在本发明的第五方面，公开所述磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂在纸箱产品等的制备中的应用。
相较于现有技术，本发明具有以下有益效果：
(1)通过分子设计与合成，本发明将磷硼阻燃元素和亲水基团以化学键形式键接于聚氨酯分子结构之中，得到磷硼杂链预聚物嵌段聚氨酯水性共聚物，因为磷硼元素在聚合物分子链中，只要聚合物分子链未降解为小分子，聚合物阻燃性能、防水特性长期有效；同时分子链中无卤素元素、高温分解过程氧化生成磷酸盐、硼酸盐乃至磷硼氧化物，具有低烟无卤的特点。
(2)本发明以所述硼杂链羟端基预聚物嵌段聚氨酯共聚物为基料制备纸箱表面辊涂或喷涂的涂膜剂，该涂膜剂在纸箱表面干燥固化的膜层材料具有低毒环保、低烟无卤、长效阻燃、防潮防火、高光美化和减摩耐磨的协效复合功能。实验结果显示，采用该涂膜剂对瓦楞箱板进行表面辊涂覆膜后，瓦楞箱纸板阻燃性能达到了GB/T14656-2009标准规定的阻燃级别，THR≤40MJ/m2，吸水性≤10g/m2。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。
除非另行定义，文中所使用的所有专业与科学用语与本领域熟练人员所熟悉的意义相同。本发明所使用的试剂或原料均可通过常规途径购买获得，如无特殊说明，本发明所使用的试剂或原料均按照本领域常规方式使用或者按照产品说明书使用。
此外，任何与所记载内容相似或均等的方法及材料皆可应用于本发明方法中。本发明中所述的较佳实施方法与材料仅作示范之用，现根据具体实施例对本发明进一步说明。
下列实施例中，所述磷硼杂链预聚物数均分子量为1500～2500、分布指数为1.1～1.2。也可以采用其他现有的方法合成或者采用市售产品。
下列实施例中，磷硼杂链预聚物嵌段聚氨酯水性共聚物的合成路线如式(2)所示：
第一实施例
1、磷硼杂链预聚物嵌段聚氨酯水性共聚物的制备，包括如下步骤：
(1)在具有机械搅拌、氮气保护、冷凝回流、水浴加热和控温装置的四口烧瓶中，加入50ml二甲苯、100g PDCP-DGB、与TDI物质的量比为1:0.01的二月桂酸二丁基锡。
(2)开搅拌、通氮气，将步骤(1)的反应体系水浴加热至60±1℃，保温体系均匀后，30min内滴加21.5g TDI和9.5g DMPA，保持体系温度75±1℃，保温2h，分离回收上层二甲苯。
(3)将步骤(2)的反应体系降温至45±1℃，然后加入一乙醇胺和50ml水，继续搅拌1h，调整pH＝9.0，再以水将产物粘度调节至2500Cp(25℃)，即得磷硼杂链预聚物嵌段聚氨酯水性共聚物树脂液。
2、一种磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂的制备，包括如下步骤：
S1、称取60g本实施例制备的磷硼杂链预聚物嵌段聚氨酯水性共聚物树脂液、微晶蜡7.0g、氧化淀粉15.0g、纳米碳酸钙15.0g、羧甲基纤维素3.0g，加入混合容器中搅拌混合，加入20ml水复合溶剂(水、乙醇和乙二醇二丁醚的体积比为3:1:2的混合物)搅匀，将得到的混合液倾入砂磨机中，启动砂磨机，保持转速5000r/min、冷却水温≤30℃，研磨30min；
S2、以细度刮板仪检测研磨至细度≤40μm后，加入1g磷酸三丁脂和水复合溶剂(水、乙醇和乙二醇二丁醚的体积比为3:1:2的混合物)，继续研磨5min，将覆膜剂的粘度调节至粘度在120s(涂-4杯)，停砂磨机，过滤出料，得到磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂。
第二实施例
1、磷硼杂链预聚物嵌段聚氨酯水性共聚物的制备，包括如下步骤：
(1)在具有机械搅拌、氮气保护、冷凝回流、水浴加热和控温装置的四口烧瓶中，加入100ml二甲苯、100g PDCP-DGB、与TDI物质的量比为1:0.02的二月桂酸二丁基锡。
(2)开搅拌、通氮气，将步骤(1)的反应体系水浴加热至65±1℃，保温体系均匀后，30min内滴加21.5g TDI和10.5g DMPA，保持体系温度70±1℃，保温2.5h，分离回收上层二甲苯。
(3)将步骤(2)的反应体系降温至45±1℃，然后加入一乙醇胺和150ml水，继续搅拌1h，调整pH＝8.0，再以水将产物粘度调节至3000Cp(25℃)，即得磷硼杂链预聚物嵌段聚氨酯水性共聚物树脂液。
2、一种磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂的制备，包括如下步骤：
S1、称取65g本实施例制备的磷硼杂链预聚物嵌段聚氨酯水性共聚物树脂液、微晶蜡3g、氧化淀粉17g、纳米碳酸钙10g、羧甲基纤维素5g，加入混合容器中搅拌混合，加入20ml水复合溶剂(水、乙醇和乙二醇二丁醚的体积比为3:1:2的混合物)搅匀，将得到的混合液倾入砂磨机中，启动砂磨机，保持转速5000r/min、冷却水温≤30℃，研磨30min；
S2、以细度刮板仪检测研磨至细度≤40μm后，加入2g磷酸三丁脂和水复合溶剂(水、乙醇和乙二醇二丁醚的体积比为3:1:2的混合物)，继续研磨5min，将覆膜剂的粘度调节至粘度在120s(涂-4杯)，停砂磨机，过滤出料，得到磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂。
第三实施例
1、磷硼杂链预聚物嵌段聚氨酯水性共聚物的制备，包括如下步骤：
(1)在具有机械搅拌、氮气保护、冷凝回流、水浴加热和控温装置的四口烧瓶中，加入150ml二甲苯、100g PDCP-DGB、与TDI物质的量比为1:0.03的二月桂酸二丁基锡。
(2)开搅拌、通氮气，将步骤(1)的反应体系水浴加热至60±1℃，保温体系均匀后，30min内滴加20.5g TDI和9.5g DMPA，保持体系温度75±1℃，保温1.5h，分离回收上层二甲苯。
(3)将步骤(2)的反应体系降温至50±1℃，然后加入一乙胺和150ml水，继续搅拌1h，调整pH＝7.5，再以水将产物粘度调节至3500Cp(25℃)，即得磷硼杂链预聚物嵌段聚氨酯水性共聚物树脂液。
2、一种磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂的制备，包括如下步骤：
S1、称取63g本实施例制备的磷硼杂链预聚物嵌段聚氨酯水性共聚物树脂液、微晶蜡4g、氧化淀粉16g、纳米碳酸钙12g、羧甲基纤维素5g，加入混合容器中搅拌混合，加入30ml水复合溶剂(水、乙醇和乙二醇二丁醚的体积比为3:1:2的混合物)搅匀，将得到的混合液倾入砂磨机中，启动砂磨机，保持转速5000r/min、冷却水温≤30℃，研磨30min；
S2、以细度刮板仪检测研磨至细度≤40μm后，加入3g磷酸三丁脂和水复合溶剂(水、乙醇和乙二醇二丁醚的体积比为3:1:2的混合物)，继续研磨5min，将覆膜剂的粘度调节至粘度在80s(涂-4杯)，停砂磨机，过滤出料，得到磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂。
性能测试
对上述实施例利用磷硼杂链预聚物聚氨酯嵌段共聚物制备的涂膜剂的性能进行测试，具体如下：
首先，选取市售五层瓦楞箱纸板，以实施例制备的水性涂膜剂均匀辊涂瓦楞向纸板表面，于恒温干燥箱中102±3℃干燥2h。
然后，根据《阻燃纸和纸板燃烧性能试验方法》(GB/T14656—2009)制样和测试，根据ISO5660-1和ASTMD2863-97标准箱板进行锥形量热仪和极限氧指数(LOI)测定，瓦楞箱纸板各项性能指标结果见表1。
表1
由表1可见，瓦楞箱纸板阻燃性能达到了GB/T14656-2009标准规定的阻燃级别，同时，相比于普通的瓦楞箱板，经过本发明实施例处理的瓦楞箱板的吸水性(防潮性能)得到了显著的改善。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂，其特征在于，按质量百分数计，其原料组成包括：3.0～7.0％微晶蜡、15.0～17.0％水溶性淀粉、10.0～15.0％填料、3.0-5.0％羧甲基纤维素、60.0～65.0％磷硼杂链预聚物嵌段聚氨酯水性共聚物；
所述磷硼杂链预聚物嵌段聚氨酯水性共聚物的制备方法包括步骤：
(1)将有机溶剂、磷硼杂链预聚物液体、二月桂酸二丁基锡混合后在保护气氛与加热条件下保温，待体系温度均匀后加入甲苯二异氰酸酯和二羟甲基丙酸，并将体系升温后保温，分离溶剂；
(2)将体系降温后加入中和剂和水，搅拌后调整体系pH值，即得。
2.根据权利要求1所述的覆膜剂，其特征在于，所述填料包括纳米碳酸钙、滑石粉、膨润土、纳米凹凸棒土中的至少一种；
或者，所述水溶性淀粉包括变性淀粉，优选为氧化淀粉、醚化淀粉中的至少一种；或者，所述覆膜剂细度≤40μm。
3.根据权利要求1所述的覆膜剂，其特征在于，所述覆膜剂的原料组成还包括助剂，优选地，所述助剂包括消泡剂，更优选为聚甲基硅油、磷酸三丁酯中的至少一种，其用量为覆膜剂配方总质量的1～3％。
4.根据权利要求1所述的覆膜剂，其特征在于，所述覆膜剂的原料组成还包括水复合溶剂；
优选地，所述水复合溶剂的添加量以调整覆膜剂粘度在80～120s之间为准；
优选地，所述水复合溶剂为水、乙醇和乙二醇二甲醚的混合体系，优选为所述水、乙醇和乙二醇二丁醚的体积比为3:1:2；
优选地，所述溶剂包括二甲苯、甲苯、环己酮中的任意一种。
5.根据权利要求1述的覆膜剂，其特征在于，步骤(1)中，步骤(1)中，所述磷硼杂链预聚物液体的粘度为25℃下2500～3000Cp，优选为用水将所述磷硼杂链预聚物稀释成符合上述粘度要求的预聚物液体；
或者，按质量百分数计，所述磷硼杂链预聚物、甲苯二异氰酸酯、二羟甲基丙酸的添加比例依次序为：75～77％、15～18％、7～8％；
或者，步骤(1)中，所述二月桂酸二丁基锡与甲苯二异氰酸酯物质的量比为1:0.01～0.03；
或者，步骤(1)中，所述磷硼杂链预聚物的数均分子量为1500～2500、分布指数为1.1～1.2。
6.根据权利要求1所述的覆膜剂，其特征在于，步骤(1)中，所述保护气氛包括氮气或氩气等惰性气体；
或者，步骤(1)中，所述加热温度为60～65℃，加热方式为水浴加热，保温时间为20～35min；
或者，步骤(1)中，所述体系升温后温度为70～75℃，保温时间为1.5～2.5h；
或者，步骤(2)中，所述中和剂包括一乙醇胺、二乙醇胺、一乙胺、二乙胺中的至少一种；
或者，步骤(2)中，所述体系降温后温度为45～50℃；
或者，步骤(2)中，所述pH值保持在7.5～9.0范围内。
7.根据权利要求1-6任一项所述的覆膜剂，其特征在于，所述共聚物结构式如式(1)所示：
8.根据权利要求7所述的覆膜剂，其特征在于，所述式(1)中，所述式(1)中，R包括-HCH2CH2OH、-(CH2CH2OH)2、-HCH2CH3、-(CH2CH3)2中的任意一种。
9.权利要求1-8任一项所述的磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂的制备方法，其特征在于，包括：将所述微晶蜡、水溶性淀粉、填料、羧甲基纤维素、磷硼杂链预聚物嵌段聚氨酯水性共聚物混合均匀，磨细后再以水复合溶剂调节粘度，即得。
10.权利要求1-8任一项所述的磷硼杂链预聚物嵌段聚氨酯水性防潮阻燃纸箱覆膜剂和/或权利要求9所述的制备方法得到的覆膜剂在纸箱产品的制备中的应用。
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Application publication date: 20210413 |