CN117304446A - 一种水性聚氨酯上浆剂及其制备方法 - Google Patents
一种水性聚氨酯上浆剂及其制备方法 Download PDFInfo
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- CN117304446A CN117304446A CN202311470386.8A CN202311470386A CN117304446A CN 117304446 A CN117304446 A CN 117304446A CN 202311470386 A CN202311470386 A CN 202311470386A CN 117304446 A CN117304446 A CN 117304446A
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- Prior art keywords
- sizing agent
- aqueous polyurethane
- diluent
- polyurethane sizing
- polyol
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/3206—Polyhydroxy compounds aliphatic
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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
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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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- Health & Medical Sciences (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及水性聚氨酯技术领域,更具体的说是涉及一种水性聚氨酯上浆剂及其制备方法。解决现有水性聚氨酯上浆剂合成过程不环保、剧毒催化剂难以去除、上浆剂产品应用局限性大的问题,主要方案包括对多元醇进行减压蒸馏,得到脱水处理的多元醇;在氮气保护氛围中,将得到的脱水多元醇在45‑50℃温度下混合均匀,缓慢滴加稀释剂稀释后的异佛尔酮二异氰酸酯,保持45‑50℃下反应2‑3h;缓慢滴加稀释剂溶解的扩链剂,在45℃下反应1.5h;冷却至40℃,滴加稀释剂溶解的交联剂,反应40min;降至20℃后,加入封端剂,反应30min后,加入中和剂,室温搅拌30min;加入去离子水,在2000rpm下搅拌至完全乳化,减压蒸馏去除稀释剂,得到水性聚氨酯上浆剂。
Description
技术领域
本发明涉及水性聚氨酯技术领域,更具体的说是涉及一种水性聚氨酯上浆剂及其制备方法。
背景技术
玄武岩纤维以天然火山喷出岩为原料,经1500~1700℃高温熔融后快速拉制而成的连续纤维,具有力学性能突出、耐温性优异、化学性能稳定、生产绿色环保、不含致癌物质等的优点,是国家重点发展的关键战略材料,也是优先发展的先进材料和高端产业之一。玄武岩纤维织物在许多领域具有潜在的应用前景,近年来,针对玄武岩纤维增强树脂基复合材料的研究与应用范围日益广泛,在航空航天、节能与新能源汽车、风电、军事工业等领域被广泛应用。
然而,玄武岩纤维在后续的加工过程中会发生磨损,产生毛丝,不仅会影响后续工艺的顺利进行,而且可能会导致玄武岩纤维的整体性能的下降,因此需要对纤维进行上浆处理。合适的上浆剂不仅能够提高玄武岩纤维的集束性,改善其工艺性能,而且能够作为玄武岩纤维与基体树脂之间的过渡粘接层,改善其与树脂基体间的化学结合作用,提高复合材料的界面性能。随着环境保护的要求越来越高,市场上水性上浆剂的占比逐渐增加。
水性上浆剂是在溶剂型的基础上进行优化制备过程,以水替代原有机溶剂,可避免因有机溶剂的挥发造成的种种弊端,上浆剂产品绿色环保、无污染、成本低,具有非常广阔的市场前景。依据“相似互容”理论,选择与基体树脂分子结构相同或相似的聚合物作为上浆剂,能够更加显著的提升界面相互作用以获得综合性能突出的复合材料。现有技术中所使用的水性上浆剂包括环氧上浆剂、聚氨酯上浆剂、聚乙烯上浆剂和聚芳醚酮上浆剂等。水性环氧树脂体系一般分为单组分环氧树脂体系和双组份环氧树脂体系,单组分不含固化剂,体系烘干后得到的纤维触摸时易粘手,性能差。双组份体系含有固化剂或交联剂,烘干后的上浆剂树脂容易发生过度固化,上浆后的碳纤维过硬,易于折断,纺丝过程中容易出现问题,且后固化时间长,效率低。
聚氨酯是一类由二异氰酸酯或多异氰酸酯类单体与二羟基或多羟基化合物通过分子聚合而成的一类高分子材料,具有耐磨性好、硬度范围宽、强力高、伸长率高等优点,以乳液、树脂等形式广泛应用于纺织、国防领域。非异氰酸酯聚氨酯通过多元环碳酸酯预聚物与多元胺的共聚反应制备,不但避免传统毒性较大的异氰酸酯的使用,而且由于其主链结构具有灵活的可设计性,并存在分子内氢键,可灵活可控的调整体系的结构特性,使之适应不同的应用领域。近年来,将水性聚氨酯树脂作为上浆剂应用于纤维增强尼龙树脂复合材料制备中,取得了较好的应用效果。然而,聚氨酯本身存在一些不可避免的缺陷,如:耐热性、不耐老化黄变和合成中使用的剧毒催化剂不能完全除去等极大地限制了聚氨酯的应用。此外,聚氨酯乳液的合成大多添加外乳化剂,乳化剂的存在会影响乳液的储存稳定性。
因此,目前对水性聚氨酯树脂上浆剂的研究仍在不断进行。CN113929850A公开了一种通过偶联剂和扩链剂作用提升聚氨酯交联度的方法获得硬度、耐磨性和韧性较好的水性聚氨酯上浆剂。然而,合成中采用了剧毒的二月桂酸二丁基锡、辛酸亚锡或二乙酸二丁基锡中的任意一种或至少两种组合作为催化剂,给安全生产带来巨大安全隐患,同时,剧毒催化剂难以完全去除,会极大地限制上浆剂的应用。
CN115897244A公开了一种高固含量的生物基水性聚氨酯上浆剂的制备方法,利用阴离子基团和非离子亲水链段对亲水性的协同增强作用,获得了高固含量且分散性突出的上浆剂产品。然而,生物基聚氨酯在合成中需要将原料溶解于丙酮、N,N-二甲基甲酰胺、四氢呋喃等溶剂中,通过溶剂反应获得生物基聚氨酯,后经旋转蒸发除去溶剂,这会极大增大生产成本同时增加环保压力。
CN116643217A公开了一种碳纤维用自乳化水性聚氨酯上浆剂的制备方法,通过自制的水性聚氨酯与硅烷偶联剂共混获得一种与基体树脂间具有突出界面结合作用的上浆剂产品。然而,自制的水性聚氨酯在制备中,需要通过溶液反应首先制备多巴胺改性的环氧大豆油,再将相应原料溶解于N,N-二甲基甲酰胺溶剂中,在催化剂三苯基膦、四丁基溴化铵或N,N-二甲基苄胺等的催化作用下,获得聚氨酯上浆剂产物。过程中反复采用溶液反应进行合成并采用减压蒸馏操作去除溶剂,给生产带来极大的成本压力和环保压力。此外,催化剂的应用也会极大限制上浆剂的应用。
发明内容
本发明的目的在于解决现有水性聚氨酯上浆剂合成过程不环保、剧毒催化剂难以去除、上浆剂产品应用局限性大的问题,简化水性聚氨酯的合成工艺、提高生产效率,同时可为高性能纤维提供一种新的水性上浆剂,丰富高性能纤维增强聚合物基复合材料的种类,拓展其应用领域。
为了实现上述目的本发明采用以下技术手段:
本发明提供了一种水性聚氨酯上浆剂及其制备方法,包括以下步骤:
步骤1、对多元醇进行减压蒸馏,减压蒸馏真空压力范围为-0.06--0.08MPa,蒸馏结束后降低温度至45-60℃,得到脱水处理的多元醇;。
步骤2、在氮气保护氛围中,将步骤1得到的脱水多元醇在45-50℃温度下混合均匀,缓慢滴加稀释剂稀释后的异佛尔酮二异氰酸酯,保持45-50℃下反应2-3h;
步骤3、缓慢滴加稀释剂溶解的扩链剂多酚单宁酸,在45℃下反应1.5h;
步骤4、冷却至40℃,滴加稀释剂溶解的交联剂三羟甲基丙烷,反应40min;
步骤5、降至20℃后,加入封端剂亚硫酸氢钠,反应30min后,加入中和剂三乙胺,室温搅拌30min;
步骤6、加入去离子水,在2000rpm下搅拌至完全乳化,减压蒸馏去除稀释剂,得到水性聚氨酯上浆剂。
上述技术方案中,多元醇包含聚乙二醇及丙三醇,聚乙二醇与丙三醇的摩尔数之比为1∶0.5-1.5。
3.根据权利要求1所述的一种水性聚氨酯上浆剂及其制备方法,其特征在于,稀释剂为丙酮。
上述技术方案中,稀释剂与异佛尔酮二异氰酸酯的重量比为1∶4-7。
上述技术方案中,多元醇与异佛尔酮二异氰酸酯的用量按照多元醇中羟基基团与异氰酸根的摩尔比为1∶1.9-2.5。
上述技术方案中,异氰酸根与多酚单宁酸中羟基基团摩尔比为1∶0.6-0.7。
上述技术方案中,异氰酸根与三羟甲基丙烷中羟基基团摩尔比为1∶0.09-0.11。
上述技术方案中,多酚单宁酸与三羟甲基丙烷与稀释剂的重量比均为1∶0.2-0.3。
上述技术方案中,异氰酸根与亚硫酸氢钠中氢摩尔比为1∶0.19-0.31。
上述技术方案中,三乙胺与扩链剂摩尔比为1∶1。
因为本发明采用上述技术手段,因此具备以下有益效果:
1)通过优选特定结构的多元醇,通过多种多元醇的共聚合反应,构筑具有超支化结构的聚氨酯分子,一方面提高聚氨酯在水中的分散性,另一方面增加聚氨酯分子结构中的活性基团,通过提高其交联度以改善上浆剂的成膜性和结构性能;
2)利用多种多元醇自身的低粘度和共聚合反应活性差异,调节聚氨酯分子合成速率,避免有机溶剂的使用和毒性催化剂的引入,可极大地简化工艺过程、降低生产成本和环保压力、拓展水性聚氨酯材料的应用领域;
3)利用生物基多酚单宁酸的高反应活性和高亲水性,将其作为扩链剂引入聚氨酯分子主链中,制备具有强亲水特性的支化结构聚氨酯,再结合自乳化工艺制备水性聚氨酯产品,乳液稳定性高;
4)用于玄武岩纤维表面上浆处理,可获得表面平滑性高、硬挺度适中的改性纤维,可有效改善玄武岩纤维增强复合材料的界面结合作用。综上,本发明提供的工艺方法简单、效率高,产品应用领域广泛,对于高性能纤维表面处理及其复合材料的应用开发具有重要意义。
5)本发明技术方案是采用常规的小分子原料,利用生物质单宁酸的扩链作用,获得分子链长且有超支化形态的聚氨酯树脂分子,后利用交联剂的交联作用实现聚氨酯长分子链的链接,获得稳定性好成膜性好的水性聚氨酯材料,并可用于玄武岩纤维的表面处理。
具体实施方式
以下将对本发明的实施例给出详细的说明。尽管本发明将结合一些具体实施方式进行阐述和说明,但需要注意的是本发明并不仅仅只局限于这些实施方式。相反,对本发明进行的修改或者等同替换,均应涵盖在本发明的权利要求范围当中。
另外,为了更好的说明本发明,在下文的具体实施方式中给出了众多的具体细节。本领域技术人员将理解,没有这些具体细节,本发明同样可以实施。
本发明提供一种水性聚氨酯上浆剂及其制备方法,包括以下步骤:
(1)在100-120℃下对多元醇进行减压蒸馏,减压蒸馏真空压力范围为-0.06--0.08MPa,蒸馏结束后降低温度至45-60℃,得到脱水处理的多元醇;
为方便本领域技术人员更好理解本发明的技术构思,以及发明目的,进一步的对上述技术方案所解决的技术问题和效果,做如下详细的说明:
其中,减压蒸馏温度范围为100℃-120℃,低于此温度水分蒸馏去除不彻底影响后续反应,高于此温度易导致多元醇结构破坏,并增加能耗。减压蒸馏真空压力范围为-0.06--0.08MPa,低于此真空压力对真空设备要求较高,增加设备成本,高于此压力蒸馏脱水效率降低,增加生产成本。蒸馏结束后降低温度至45-60℃,降低能耗,防止原料在高温环境下被破坏,降温低于此温度耗时长降低生产效率,高于此温度不便于对聚合物多元醇的处理,存在安全隐患。
进一步的,其中,多元醇包含聚乙二醇400/600/800及丙三醇,选择聚乙二醇和丙三醇,是因为两者都表现较好的亲水性,作为聚氨酯主链结构可使得树脂体系表现出良好的水溶特性,其次,丙三醇的多羟基结构利用形成支化的聚氨酯主链,提升分子链中的活性官能团含量,可进一步改善上浆剂产品的稳定性和结构强度。
进一步的,在氮气保护氛围中,将得到的脱水多元醇在45-50℃温度下混合均匀,缓慢滴加稀释剂稀释后的异佛尔酮二异氰酸酯,保持45-50℃下反应2-3h。后缓慢滴加稀释剂溶解的多酚单宁酸,在45℃下反应1.5h。冷却至40℃,滴加稀释剂溶解的三羟甲基丙烷,反应40min。降至20℃后,加入亚硫酸氢钠,反应30min后,加入三乙胺,室温搅拌30min。最后,加入去离子水,在2000rpm下搅拌至完全乳化,减压蒸馏去除丙酮,得到水性聚氨酯上浆剂。
进一步的,聚乙二醇与丙三醇的摩尔数之比为1∶0.5-1.5,高于此比例,支化结构聚氨酯的占比较低,不足以显著提升树脂体系的水溶稳定性和提升上浆剂的结构性能;低于此比例,制备的聚氨酯体系中主链分子量较小、活性官能团含量过高,易导致上浆剂成膜性差。
进一步的,稀释剂为丙酮。稀释剂与异佛尔酮二异氰酸酯的重量比为1∶4-7,使用稀释剂的原因是控制异佛尔酮二异氰酸酯与多元醇的反应速率,高于此比例,稀释剂用量大造成资源浪费同时不利于环保生产,低于此比例,不足以调控反应速率,反应速率高易导致产物结构不可控影响产物性能。
进一步的,反应温度和反应时间的选择,高于此温度或长于此时间,易导致反应剧烈进行不可控,或造成能耗增加,低于此温度或短于时间,易导致反应无法进行或反应程度低,无法获得目标产物。
进一步的,多元醇与异佛尔酮二异氰酸酯的用量按照多元醇中羟基基团与异氰酸根的摩尔数之比(R值)确定,羟基基团与异氰酸根的摩尔比为1:1.9-2.5。高于此比例,多元醇无法充分反应,导致产物中出现油状物,低于此比例,游离异氰酸根较多,导致后续扩链和交联反应时反应剧烈,易形成较多短分子链的硬段结构,导致产物成膜性差,无法实现纤维表面上浆改性的目标。
进一步的,扩链剂为多酚单宁酸,用量根据如下规则确定,理论剩余异氰酸根与多酚单宁酸中羟基基团摩尔比为1:0.6-0.7,高于此比例,扩链程度低,会导致聚氨酯产物中软段结构占比少,导致产物柔韧性不佳,低于此比例,扩链程度高,反应过程体系粘度大,同时分子量急剧升高导致水溶性下降,无法获得水性聚氨酯上浆剂。三羟甲基丙烷作为交联剂,用量根据如下规则确定,理论剩余异氰酸根与三羟甲基丙烷中羟基基团摩尔比为1:0.09-0.11,高于此比例,交联程度弱,聚氨酯分子链间相互作用力弱,易导致聚氨酯材料结构强度差,低于此比例,交联剂过量,易导致聚氨酯分子结构中硬段短链组分增多,导致材料刚性大而柔韧性不佳。多酚单宁酸与三羟甲基丙烷与稀释剂的重量比均为1:0.2-0.3,高于此比例溶解性不佳,导致加料不顺畅,低于此比例稀释剂用量大导致能源浪费增加环保压力。
进一步的,亚硫酸氢钠为封端剂,用量根据如下规则确定,理论剩余异氰酸根与亚硫酸氢钠中氢摩尔比为1:0.19-0.31,高于此比例,封端不彻底,裸露的端基异氰酸根会与水发生进一步反应,导致水性聚氨酯变性,低于此比例,封端剂过量,导致产物中杂质含量大,影响后续上浆剂的使用效果。
进一步的,三乙胺为中和剂,用量根据如下规则确定,三乙胺与扩链剂摩尔比为1:1。
进一步的,去离子水为溶剂,用量按如下规则确定,去离子水与多元醇、异佛尔酮二异氰酸酯、扩链剂、交联剂、封端剂和中和剂的总质量之比为1∶0.4-0.45,高于此比例,水性聚氨酯固含量低,会增加运输和后续干燥成本,低于此比例,上浆剂体系贮存稳定性不可控,产品易沉降分层,影响使用。
以下的实施例在于详细说明本发明,只是本发明的较佳实施例,并非限制本发明。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1-5
实施例1-5公开了一种水性聚氨酯上浆剂及其制备方法,包括以下步骤:
(1)在100-120℃下对多元醇进行减压蒸馏,减压蒸馏真空压力范围为-0.06--0.08MPa,蒸馏结束后降低温度至45-60℃,得到脱水处理的多元醇;
(2)在氮气保护氛围中,将步骤(1)得到的脱水多元醇在45-50℃温度下混合均匀,缓慢滴加稀释剂稀释后的异佛尔酮二异氰酸酯,保持45-50℃下反应2-3h。后缓慢滴加稀释剂溶解的多酚单宁酸,在45℃下反应1.5h。冷却至40℃,滴加稀释剂溶解的三羟甲基丙烷,反应40min。降至20℃后,加入亚硫酸氢钠,反应30min后,加入三乙胺,室温搅拌30min。最后,加入去离子水,在2200rpm下搅拌至完全乳化,减压蒸馏去除丙酮,得到水性聚氨酯上浆剂。
对比实施例1-4
对比实施例1-4分别从多元醇的相对比例、异氰酸根比例(R值)及扩链剂用量三方面作对比验证。
实施例1-5及对比实施例1-3的原料用量以及工艺参数见表1。
表1实施例1-5及对比实施例1-3的原料用量以及工艺参数:
为了考察本发明方法制备的水性聚氨酯上浆剂的稳定性、平均粒径及对玄武岩纤维表面处理后纤维硬挺度,对实施例1-5及对比例1-3所得样品进行了测试。
玄武岩纤维为13μm的合股纱。
具体测定方法如下:
(1)稳定性:将制备的水性乳液置于25ml刻度的比色管中,室温下静置,观测其沉淀、分层情况。
(2)粒径:采用动态光散射仪(Zetasizer Nano ZS-90,Malvern)表征上浆剂粒径。将上浆剂稀释至浓度为0.1mg/L样品溶液,取4ml样品溶液至石英皿,每个样品测试三次。
(3)硬挺度:根据GB 7690.4-2013《增强材料纱线试验方法第4部分:硬挺度的测试》测试无捻粗砂硬挺度的测试方法,测试纤维束的硬挺度,试样长为(500+5)mm,试样纤维束均衡悬挂于钩子上30s左右,读出纱线在标尺处的两端距离,每个试样测试10次,求其平均值。
表2实施例1-5及对比例1-4所制备复合材料的性能测试结果
通过表2可以看出来,制备的水性聚氨酯上浆剂具有以下优点:①水溶性和储存稳定性好,粒径分布均匀,14天内上浆剂状态不发生变化,呈无色透明状。其中,随着R值的增大,水性上浆剂的透明性逐渐减弱,主要是因为游离的异氰酸根与扩链剂和交联剂反应形成小分子刚性链段,使得聚氨酯分子乳液分散粒径增大,乳液体系透明性下降。对比例1结果表明,聚乙二醇与丙三醇的相对比例对体系粒径影响较为明显,主要是因为随着聚乙二醇相对含量的增加,线性分子链增多,分子链间缠结聚集导致乳液粒径增大明显,最终导致乳液状态变为半透明;对比例2及对比例3中结果说明,R值和扩链剂的用量对平均粒径和稳定性影响不明显,体系均表现出良好的透明性和稳定性。②对玄武岩纤维进行表面上浆处理后,纤维的硬挺度在88-101范围内,软硬适中,避免了纤维过软和过硬导致的定型差和弯折性差的问题;对比例1中处理后纤维的硬挺度下降主要是因为水性聚氨酯上浆剂分子链段中长链软段占比高导致上浆剂成膜后刚性不足;对比例2中下降是因为R值低导致的交联反应后刚性硬段含量低,上浆剂成膜后表现出明显的柔软特性;对比例3中硬挺度下降是因为扩链剂用量少导致的扩链程度低,使得体系中线性长链含量高,交联密度低,导致作为上浆剂使用时刚性不足,使得处理后的纤维刚挺度不够。因此,通过本发明获得的水性聚氨酯上浆剂的性质可通过分子结构调整灵活调控,并可用于玄武岩纤维上浆剂,对其刚挺度进行调控。
Claims (10)
1.一种水性聚氨酯上浆剂的制备方法,其特征在于,包括以下步骤:
步骤1、对多元醇进行减压蒸馏,减压蒸馏真空压力范围为-0.06--0.08MPa,蒸馏结束后降低温度至45-60℃,得到脱水处理的多元醇;
步骤2、在氮气保护氛围中,将步骤1得到的脱水多元醇在45-50℃温度下混合均匀,缓慢滴加稀释剂稀释后的异佛尔酮二异氰酸酯,保持45-50℃下反应2-3h;
步骤3、缓慢滴加稀释剂溶解的扩链剂多酚单宁酸,在45℃下反应1.5h;
步骤4、冷却至40℃,滴加稀释剂溶解的交联剂三羟甲基丙烷,反应40min;
步骤5、降至20℃后,加入封端剂亚硫酸氢钠,反应30min后,加入中和剂三乙胺,室温搅拌30min;
步骤6、加入去离子水,在2000rpm下搅拌至完全乳化,减压蒸馏去除稀释剂,得到水性聚氨酯上浆剂。
2.根据权利要求1所述的一种水性聚氨酯上浆剂的制备方法,其特征在于,多元醇包含聚乙二醇及丙三醇,聚乙二醇与丙三醇的摩尔数之比为1∶0.5-1.5。
3.根据权利要求1所述的一种水性聚氨酯上浆剂及其制备方法,其特征在于,稀释剂为丙酮。
4.根据权利要求3所述的一种水性聚氨酯上浆剂的制备方法,其特征在于,稀释剂与异佛尔酮二异氰酸酯的重量比为1∶4-7。
5.根据权利要求3所述的一种水性聚氨酯上浆剂的制备方法,其特征在于,多元醇与异佛尔酮二异氰酸酯的用量按照多元醇中羟基基团与异氰酸根的摩尔比为1∶1.9-2.5。
6.根据权利要求5所述的一种水性聚氨酯上浆剂的制备方法,其特征在于,异氰酸根与多酚单宁酸中羟基基团摩尔比为1∶0.6-0.7。
7.根据权利要求1所述的一种水性聚氨酯上浆剂的制备方法,其特征在于,异氰酸根与三羟甲基丙烷中羟基基团摩尔比为1∶0.09-0.11。
8.根据权利要求1所述的一种水性聚氨酯上浆剂的制备方法,其特征在于,多酚单宁酸与三羟甲基丙烷与稀释剂的重量比均为1∶0.2-0.3。
9.根据权利要求1所述的一种水性聚氨酯上浆剂的制备方法,其特征在于,异氰酸根与亚硫酸氢钠中氢摩尔比为1∶0.19-0.31。
10.一种水性聚氨酯上浆剂,其特征在于,通过权利要求1-9任一所述的一种水性聚氨酯上浆剂的制备方法获得。
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