CN115850645A - A kind of aqueous polyurethane dispersion with high bio-based content for synthetic leather and preparation method thereof - Google Patents
A kind of aqueous polyurethane dispersion with high bio-based content for synthetic leather and preparation method thereofDownload PDFInfo
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Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及合成革用水性聚氨酯领域，特别涉及一种合成革用高生物基含量的水性聚氨酯分散液及其制备方法。The invention relates to the field of water-based polyurethane for synthetic leather, in particular to a water-based polyurethane dispersion with high bio-based content for synthetic leather and a preparation method thereof.
背景技术Background technique
近年来，我国合成革行业延续稳步增长态势，其中聚氨酯合成革由于具有真皮感强、与基材粘接性能优异、抗磨损和抗老化等优点，其市场份额正逐步扩大。目前，合成革用聚氨酯主要有水性聚氨酯、溶剂型聚氨酯和无溶剂型聚氨酯三大类，其中水性聚氨酯以水为分散介质，其制备工艺简单，分散液具有良好的储存稳定性，分散液形成的聚氨酯膜具有良好的耐溶剂和耐老化性等特点，符合当前绿色发展的生态理念。水性聚氨酯在合成革用聚氨酯树脂中占比逐年增加。In recent years, my country's synthetic leather industry has continued to grow steadily. Among them, polyurethane synthetic leather is gradually expanding its market share due to its advantages such as strong leather feel, excellent adhesion to substrates, wear resistance and anti-aging. At present, polyurethanes for synthetic leather mainly include water-based polyurethanes, solvent-based polyurethanes and solvent-free polyurethanes. Among them, water-based polyurethanes use water as the dispersion medium. The preparation process is simple, and the dispersion liquid has good storage stability. Polyurethane film has good solvent resistance and aging resistance, which is in line with the current ecological concept of green development. The proportion of waterborne polyurethane in polyurethane resin for synthetic leather is increasing year by year.
为减少石油资源依赖、降低碳排放，以生物基原料制备水性聚氨酯成为发展趋势。中国发明专利申请CN112724347A公开了一种生物基水性聚氨酯树脂及其制备方法和应用，中国发明专利CN114085356A公开了一种耐化学品、可生物降解合成革用面层聚氨酯树脂及其制备方法。但现有合成革用生物基聚氨酯生物基含量低，且使用有毒锡类催化剂，生物基聚氨酯分散体与膜性能不稳定。本发明采用多种生物基原料，大幅提高生物基水性聚氨酯中生物基含量，并以环保催化剂替代有毒锡类催化剂，同时保证合成革用高生物基含量水性聚氨酯性能稳定，水性聚氨酯分散液具有良好的储存稳定性，水性聚氨酯胶膜具有良好的力学性能。In order to reduce dependence on petroleum resources and reduce carbon emissions, the preparation of waterborne polyurethane from bio-based raw materials has become a development trend. Chinese invention patent application CN112724347A discloses a bio-based waterborne polyurethane resin and its preparation method and application, and Chinese invention patent CN114085356A discloses a chemical-resistant, biodegradable surface layer polyurethane resin for synthetic leather and its preparation method. However, the existing bio-based polyurethanes for synthetic leather have low bio-based content and use toxic tin catalysts, resulting in unstable performance of bio-based polyurethane dispersions and films. The invention adopts a variety of bio-based raw materials, greatly increases the bio-based content in bio-based water-based polyurethane, and replaces toxic tin catalysts with environmentally friendly catalysts, while ensuring stable performance of high-bio-based water-based polyurethane for synthetic leather, and the water-based polyurethane dispersion has good properties. Excellent storage stability, water-based polyurethane film has good mechanical properties.
发明内容Contents of the invention
本发明的目的在于提供一种合成革用高生物基含量的水性聚氨酯分散液及其制备方法。The object of the present invention is to provide a kind of aqueous polyurethane dispersion liquid with high bio-based content for synthetic leather and its preparation method.
本发明通过多种生物基原料制备水性聚氨酯，实现了生物基含量大于80％，并以环保催化剂替代有毒的锡类催化剂。选取含羧基侧链的L-赖氨酸与生物基三亚甲基碳酸酯共聚改性后的聚乳酸多元醇作为软段，以聚乳酸多元醇侧链中羧基为亲水基团，且通过聚乳酸多元醇中碳酸酯键与酯键的共同作用，赋予合成革用高生物基含量的水性聚氨酯分散液高稳定性，分散液形成的膜力学性能突出。The invention prepares water-based polyurethane through various bio-based raw materials, realizes that the bio-based content is greater than 80%, and replaces toxic tin catalysts with environmentally friendly catalysts. The polylactic acid polyol modified by copolymerization of L-lysine with carboxyl side chain and bio-based trimethylene carbonate was selected as the soft segment, and the carboxyl group in the side chain of polylactic acid polyol was used as the hydrophilic group, and the The combined effect of carbonate bond and ester bond in lactic acid polyol endows the water-based polyurethane dispersion with high bio-based content for synthetic leather with high stability, and the film formed by the dispersion has outstanding mechanical properties.
为实现上述目的及其他相关目的，本发明提供一种合成革用高生物基含量的水性聚氨酯分散液，由以下组分制备而成：In order to achieve the above object and other related objects, the present invention provides a water-based polyurethane dispersion with high bio-based content for synthetic leather, which is prepared from the following components:
在发明的一些实施方式中，所述生物基异氰酸酯为L-赖氨酸二异氰酸酯、1,5-戊二异氰酸酯或二聚酸二异氰酸酯中的一种或几种组合。In some embodiments of the invention, the bio-based isocyanate is one or a combination of L-lysine diisocyanate, 1,5-pentane diisocyanate or dimer acid diisocyanate.
在发明的一些实施方式中，所述生物基聚乳酸多元醇结构式为In some embodiments of the invention, the structural formula of the bio-based polylactic acid polyol is
其中，m、n、x、y的总和选自16～36之间的整数。Wherein, the sum of m, n, x and y is selected from integers between 16 and 36.
在发明的一些实施方式中，所述生物基聚乳酸多元醇是以结构中含羧基侧链的生物基小分子L-赖氨酸为引发剂，在有机催化剂1,8-二氮杂二环十一碳-7-烯作用下与L-丙交酯和生物基三亚甲基碳酸酯开环共聚制备而得。In some embodiments of the invention, the bio-based polylactic acid polyol is based on the bio-based small molecule L-lysine containing a carboxyl side chain in the structure as the initiator, and the organic catalyst 1,8-diazabicyclo It is prepared by ring-opening copolymerization of undec-7-ene with L-lactide and bio-based trimethylene carbonate.
在发明的一些实施方式中，所述生物基扩链剂为生物基乙二醇、生物基1,4-丁二醇、生物基2,3-丁二醇、生物基1,5-戊二醇或生物基异山梨醇中的一种或几种组合。In some embodiments of the invention, the bio-based chain extender is bio-based ethylene glycol, bio-based 1,4-butanediol, bio-based 2,3-butanediol, bio-based 1,5-pentanediol Alcohol or bio-based isosorbide or a combination of several.
在发明的一些实施方式中，所述环保催化剂为异辛酸锌、新十二酸铋或异辛酸铋中的一种或几种组合。In some embodiments of the invention, the environment-friendly catalyst is one or a combination of zinc isooctanoate, bismuth neododecanoate or bismuth isooctanoate.
在发明的一些实施方式中，所述生物基抗氧化剂为生物基甘草异黄酮或生物基3,4,5,7-四羟基黄酮中的一种或两种组合。In some embodiments of the invention, the bio-based antioxidant is one or a combination of bio-based licorice isoflavones or bio-based 3,4,5,7-tetrahydroxyflavones.
在发明的一些实施方式中，所述中和剂为三乙胺、碳酸氢钠、醋酸钠、焦磷酸钠或碳酸钠中的一种或几种组合。In some embodiments of the invention, the neutralizing agent is one or a combination of triethylamine, sodium bicarbonate, sodium acetate, sodium pyrophosphate or sodium carbonate.
在发明的一些实施方式中，所述后扩链剂为乙二胺、三乙烯二胺或异佛尔酮二胺中的一种或几种组合。In some embodiments of the invention, the post-chain extender is one or a combination of ethylenediamine, triethylenediamine or isophoronediamine.
本发明还提供一种制备上述合成革用高生物基含量的水性聚氨酯分散液的方法，包括如下步骤：The present invention also provides a method for preparing the aqueous polyurethane dispersion with high bio-based content for the above-mentioned synthetic leather, comprising the steps of:
在反应器中加入20.0～30.0质量份的生物基聚乳酸多元醇、10.0～15.0质量份的生物基异氰酸酯、1.0～2.5质量份的生物基扩链剂、0.5～1.0质量份的生物基抗氧化剂和0.5～1.0质量份的环保催化剂，在60℃～90℃下反应6h～9h，反应过程中加入丙酮调节反应体系粘度；Add 20.0-30.0 parts by mass of bio-based polylactic acid polyol, 10.0-15.0 parts by mass of bio-based isocyanate, 1.0-2.5 parts by mass of bio-based chain extender, and 0.5-1.0 parts by mass of bio-based antioxidant React with 0.5-1.0 parts by mass of an environmentally friendly catalyst at 60°C-90°C for 6h-9h, adding acetone during the reaction to adjust the viscosity of the reaction system;
将所述反应体系降温后，向所述反应体系中加入1.0～2.5质量份的中和剂进行中和，加入0.5～3.0质量份的后扩链剂和75.0～100.0质量份的去离子水，高速搅拌30min～40min，再脱除丙酮，获得合成革用高生物基含量的水性聚氨酯分散液。After cooling the reaction system, add 1.0-2.5 parts by mass of neutralizing agent to the reaction system for neutralization, add 0.5-3.0 parts by mass of post-chain extender and 75.0-100.0 parts by mass of deionized water, Stir at a high speed for 30 minutes to 40 minutes, and then remove acetone to obtain a water-based polyurethane dispersion with high bio-based content for synthetic leather.
综上所述，本发明提供一种合成革用高生物基含量的水性聚氨酯分散液及其制备方法，通过分子设计与配方优化，在大幅度提高了水性聚氨酯分散液的生物基组分含量的情况下，保证了高生物基含量水性聚氨酯分散液性能的稳定，使水性聚氨酯分散液在室温环境下具有良好的储存稳定性。同时保证了水性聚氨酯分散液形成的胶膜力学性能良好，适用于生产高性能、高生物基含量的聚氨酯合成革。In summary, the present invention provides a water-based polyurethane dispersion with high bio-based content for synthetic leather and a preparation method thereof. Through molecular design and formula optimization, the bio-based component content of the water-based polyurethane dispersion is greatly improved. Under certain circumstances, the stability of the performance of the high bio-based content waterborne polyurethane dispersion is guaranteed, so that the waterborne polyurethane dispersion has good storage stability at room temperature. At the same time, it ensures that the adhesive film formed by the water-based polyurethane dispersion has good mechanical properties, and is suitable for producing polyurethane synthetic leather with high performance and high bio-based content.
附图说明Description of drawings
图1为实施例中合成革用高生物基含量的水性聚氨酯分散液的制备方法流程示意图。Fig. 1 is a schematic flow chart of the preparation method of the aqueous polyurethane dispersion with high bio-based content for synthetic leather in the embodiment.
图2为实施例中高生物基含量水性聚氨酯分散液制备高生物基含量聚氨酯合成革的流程示意图。Fig. 2 is a schematic flow chart of preparing high bio-based content polyurethane synthetic leather from the high bio-based content aqueous polyurethane dispersion in the embodiment.
具体实施方式Detailed ways
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。Embodiments of the present invention are described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation modes, and various modifications or changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of the present invention.
应当理解的是，本发明能够以不同形式实施，而不应当解释为局限于这里提出的实施例。相反地，提供这些实施例将使公开彻底和完全，并且将本发明的范围完全地传递给本领域技术人员。如没有特别说明，以下实施例所示的“％”和“份”分别是指“质量％”和“质量份”。It should be understood that the invention can be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Unless otherwise specified, "%" and "part" shown in the following examples mean "mass%" and "mass part", respectively.
本发明提供的一种合成革用高生物基含量的水性聚氨酯分散液，生物基含量在80％～95％之间。通过本发明获得的高生物基含量的水性聚氨酯分散液制备得到的合成革，满足家具用水性聚氨酯合成革、服装用聚氨酯合成革和汽车装饰用皮革等领域用合成革的性能要求，能够广泛应用在家具、服装、汽车装饰等领域。The invention provides an aqueous polyurethane dispersion with high bio-based content for synthetic leather, and the bio-based content is between 80% and 95%. The synthetic leather prepared by the water-based polyurethane dispersion with high bio-based content obtained in the present invention can meet the performance requirements of synthetic leather used in the fields of water-based polyurethane synthetic leather for furniture, polyurethane synthetic leather for clothing, and leather for automotive decoration, and can be widely used In furniture, clothing, car decoration and other fields.
在本发明实施例中，合成革用高生物基含量的水性聚氨酯分散液包括生物基异氰酸酯和生物基聚乳酸多元醇等原料。其中，生物基异氰酸酯的含量例如为10.0～15.0质量份，生物基异氰酸酯例如为L-赖氨酸二异氰酸酯、1,5-戊二异氰酸酯或二聚酸二异氰酸酯中的一种或几种混合。生物基聚乳酸多元醇的含量例如为20.0～30.0质量份，生物基聚乳酸多元醇例如是引发剂在有机催化剂的作用下与L-丙交酯和生物基三亚甲基碳酸酯开环共聚制备获得。其中，引发剂例如为结构中含羧基侧链的生物基小分子，又例如为L-赖氨酸，有机催化剂例如为1,8-二氮杂二环十一碳-7-烯。在本发明实施例中，生物基聚乳酸多元醇例如具有如下的结构式，In the embodiment of the present invention, the aqueous polyurethane dispersion with high bio-based content for synthetic leather includes raw materials such as bio-based isocyanate and bio-based polylactic acid polyol. Wherein, the content of bio-based isocyanate is, for example, 10.0-15.0 parts by mass, and the bio-based isocyanate is, for example, one or a mixture of L-lysine diisocyanate, 1,5-pentane diisocyanate or dimer acid diisocyanate. The content of bio-based polylactic acid polyol is, for example, 20.0-30.0 parts by mass. Bio-based polylactic acid polyol is prepared by ring-opening copolymerization with L-lactide and bio-based trimethylene carbonate under the action of an organic catalyst, for example. get. Wherein, the initiator is, for example, a bio-based small molecule containing a carboxyl side chain in its structure, such as L-lysine, and the organic catalyst is, for example, 1,8-diazabicycloundec-7-ene. In the embodiment of the present invention, the bio-based polylactic acid polyol has the following structural formula, for example,
其中，结构式中m、n、x、y的总和例如为选自16～36之间的整数。L-赖氨酸向聚氨酯分子链中引入羧基基团，羧基作为阴离子亲水基团，中和之后为聚氨酯链提供质子化的亲水单元，实现聚氨酯在水中的自乳化，无需通过添加亲水扩链剂来实现聚氨酯的亲水性。使制备的水性聚氨酯分散液粒径低于100nm，室温环境下可稳定贮存6个月。Wherein, the sum of m, n, x, and y in the structural formula is, for example, an integer selected from 16-36. L-lysine introduces a carboxyl group into the polyurethane molecular chain, and the carboxyl group acts as an anionic hydrophilic group. After neutralization, it provides a protonated hydrophilic unit for the polyurethane chain to realize self-emulsification of polyurethane in water without adding hydrophilic Chain extenders to achieve the hydrophilicity of polyurethane. The particle size of the prepared aqueous polyurethane dispersion is lower than 100nm, and it can be stored stably for 6 months at room temperature.
在本发明实施例中，在水性聚氨酯分散液中，合成革用高生物基含量的水性聚氨酯分散液还包括生物基扩链剂、环保催化剂、生物基抗氧化剂、中和剂、后扩链剂和去离子水等原料。其中，生物基扩链剂的含量例如为1.0～2.5质量份，又例如为1.0、2.0或2.5质量份。生物基扩链剂例如为生物基乙二醇、生物基1,4-丁二醇、生物基2,3-丁二醇、生物基1,5-戊二醇或生物基异山梨醇中的一种或多种。又例如为生物基乙二醇、生物基2,3-丁二醇或生物基1,4-丁二醇。In the embodiment of the present invention, in the water-based polyurethane dispersion, the water-based polyurethane dispersion with high bio-based content for synthetic leather also includes a bio-based chain extender, an environmental catalyst, a bio-based antioxidant, a neutralizing agent, and a post-chain extender and deionized water and other raw materials. Wherein, the content of the bio-based chain extender is, for example, 1.0-2.5 parts by mass, and for example, 1.0, 2.0 or 2.5 parts by mass. Bio-based chain extenders such as bio-based ethylene glycol, bio-based 1,4-butanediol, bio-based 2,3-butanediol, bio-based 1,5-pentanediol or bio-based isosorbide one or more. Another example is bio-based ethylene glycol, bio-based 2,3-butanediol or bio-based 1,4-butanediol.
在本发明实施例中，在水性聚氨酯分散液中，环保催化剂的含量例如为0.5～1.0质量份，又例如为0.5、0.6或1.0质量份。环保催化剂例如为异辛酸锌、新十二酸铋或异辛酸铋中的一种，又例如为新十二酸铋或异辛酸锌。生物基抗氧化剂的含量例如为0.5～1.0质量份，又例如为0.5、0.7或1.0质量份。生物基抗氧化剂例如为生物基甘草异黄酮或生物基3,4,5,7-四羟基黄酮中的一种，在本实施例中，生物基抗氧化剂例如为生物基甘草异黄酮或生物基3,4,5,7-四羟基黄酮。In the embodiment of the present invention, the content of the environmentally friendly catalyst in the aqueous polyurethane dispersion is, for example, 0.5-1.0 parts by mass, and for example, 0.5, 0.6 or 1.0 parts by mass. The environment-friendly catalyst is, for example, one of zinc isooctanoate, bismuth neododecanoate or bismuth isooctanoate, and another example is bismuth neododecanoate or zinc isooctanoate. The content of the bio-based antioxidant is, for example, 0.5-1.0 parts by mass, and for example, 0.5, 0.7 or 1.0 parts by mass. The bio-based antioxidant is, for example, one of bio-based licorice isoflavone or bio-based 3,4,5,7-tetrahydroxyflavone. In this embodiment, the bio-based antioxidant is, for example, bio-based licorice isoflavone or bio-based 3,4,5,7-Tetrahydroxyflavone.
在本发明实施例中，在水性聚氨酯分散液中，中和剂的含量例如为1.0～2.5质量份，又例如为1.0、1.3或2.5质量份。中和剂例如为三乙胺、碳酸氢钠、醋酸钠、焦磷酸钠或碳酸钠中的一种或几种，又例如为三乙胺、碳酸钠或焦磷酸钠。后扩链剂的含量例如为0.5～3.0质量份，又例如为0.5、1.5或3.0质量份。后扩链剂为乙二胺、三乙烯二胺或异佛尔酮二胺中的一种或几种，又例如为乙二胺、三乙烯二胺或异佛尔酮二胺。在水性聚氨酯分散液中，去离子水的含量例如为75.0～100.0质量份，又例如为75.0、90.0或100.0质量份。In an embodiment of the present invention, in the aqueous polyurethane dispersion, the content of the neutralizing agent is, for example, 1.0-2.5 parts by mass, or for example, 1.0, 1.3 or 2.5 parts by mass. The neutralizing agent is, for example, one or more of triethylamine, sodium bicarbonate, sodium acetate, sodium pyrophosphate or sodium carbonate, and another example is triethylamine, sodium carbonate or sodium pyrophosphate. The content of the post-chain extender is, for example, 0.5-3.0 parts by mass, and for example, 0.5, 1.5 or 3.0 parts by mass. The post-chain extender is one or more of ethylenediamine, triethylenediamine or isophoronediamine, for example, ethylenediamine, triethylenediamine or isophoronediamine. In the aqueous polyurethane dispersion, the content of deionized water is, for example, 75.0-100.0 parts by mass, and for example, 75.0, 90.0 or 100.0 parts by mass.
如图1所示，本发明提供一种合成革用高生物基含量的水性聚氨酯分散液的制备方法，制备方法包括步骤S10～S20。As shown in FIG. 1 , the present invention provides a method for preparing an aqueous polyurethane dispersion with high bio-based content for synthetic leather. The preparation method includes steps S10-S20.
步骤S10、在反应器中加入例如20.0～30.0质量份的生物基聚乳酸多元醇、10.0～15.0质量份的生物基异氰酸酯、1.0～2.5质量份的生物基扩链剂、0.5～1.0质量份的生物基抗氧化剂和0.5～1.0质量份的环保催化剂，在例如60℃～90℃下反应，反应时间例如为6h～9h，反应过程中加入丙酮调节反应体系粘度；Step S10, adding, for example, 20.0-30.0 parts by mass of bio-based polylactic acid polyol, 10.0-15.0 parts by mass of bio-based isocyanate, 1.0-2.5 parts by mass of bio-based chain extender, 0.5-1.0 parts by mass of Bio-based antioxidants and 0.5-1.0 parts by mass of environmentally friendly catalysts are reacted at, for example, 60°C to 90°C, and the reaction time is, for example, 6h to 9h, and acetone is added during the reaction to adjust the viscosity of the reaction system;
步骤S20、将步骤S10中的反应体系降温，降温后，向反应体系中加入例如1.0～2.5质量份的中和剂中和，之后加入例如0.5～3.0质量份的后扩链剂和75.0～100.0质量份的去离子水，高速搅拌，搅拌时间例如为30min～40min，脱除丙酮，获得合成革用高生物基含量的水性聚氨酯分散液。Step S20, cool down the reaction system in step S10. After cooling down, add, for example, 1.0-2.5 parts by mass of a neutralizing agent to the reaction system for neutralization, and then add, for example, 0.5-3.0 parts by mass of a post-chain extender and 75.0-100.0 parts by mass of Parts by mass of deionized water are stirred at a high speed for 30 min to 40 min, for example, to remove acetone to obtain a water-based polyurethane dispersion with high bio-based content for synthetic leather.
如图1所示，在本发明实施例中，在步骤S10中，生物基聚乳酸多元醇的数均分子量例如为2000g/mol，生物基聚乳酸多元醇在与生物基异氰酸酯反应前，在预设的温度和真空度条件下进行减压脱水反应，预设温度例如为105℃、真空度例如大于0.085MPa，减压脱水反应的时间例如为1h。As shown in Figure 1, in the embodiment of the present invention, in step S10, the number-average molecular weight of the bio-based polylactic acid polyol is, for example, 2000 g/mol. Before the bio-based polylactic acid polyol reacts with the bio-based isocyanate, The vacuum dehydration reaction is carried out under the conditions of the set temperature and vacuum degree. The preset temperature is, for example, 105° C., the vacuum degree is, for example, greater than 0.085 MPa, and the time for the decompression dehydration reaction is, for example, 1 h.
如图1所示，在本发明实施例中，在步骤S10中，反应容器中，将例如20.0～30.0质量份减压脱水反应后的生物基聚乳酸多元醇降温至例如90℃，之后加入例如10.0～15.0质量份的生物基异氰酸酯反应，反应时间例如为2h～3h，降温至例如60℃，再加入例如1.0～2.5质量份的生物基扩链剂、0.5～1.0质量份的生物基抗氧化剂和0.5～1.0质量份的环保催化剂，之后升温至例如80℃，恒温反应，反应时间例如为4h～6h，反应过程中加入丙酮调节反应体系粘度。As shown in Figure 1, in the embodiment of the present invention, in step S10, in the reaction vessel, for example, 20.0 to 30.0 parts by mass of bio-based polylactic acid polyol after dehydration under reduced pressure is cooled to, for example, 90°C, and then, for example, 10.0-15.0 parts by mass of bio-based isocyanate is reacted, the reaction time is, for example, 2h-3h, the temperature is lowered to, for example, 60°C, and then, for example, 1.0-2.5 parts by mass of bio-based chain extender and 0.5-1.0 parts by mass of bio-based antioxidant are added and 0.5-1.0 parts by mass of an environmentally-friendly catalyst, and then heat up to, for example, 80° C., and react at a constant temperature. The reaction time is, for example, 4 hours to 6 hours. During the reaction, acetone is added to adjust the viscosity of the reaction system.
如图1所示，在本发明实施例中，在步骤S20中，将步骤S10中的反应体系降温至例如40℃，向反应体系中加入例如1.0～2.5质量份的中和剂，中和反应例如10min～20min后，加入例如0.5～3.0质量份的后扩链剂和75.0～100.0质量份的去离子水，高速搅拌，搅拌时间例如为30min～40min，完成乳化。反应结束后，静置、脱除丙酮，例如使用减压蒸馏法脱除丙酮，得到高生物基含量的水性聚氨酯分散液。As shown in Figure 1, in the embodiment of the present invention, in step S20, the temperature of the reaction system in step S10 is lowered to, for example, 40°C, and 1.0 to 2.5 parts by mass of a neutralizing agent is added to the reaction system to neutralize the reaction For example, after 10 minutes to 20 minutes, add, for example, 0.5 to 3.0 parts by mass of post-chain extender and 75.0 to 100.0 parts by mass of deionized water, and stir at a high speed for, for example, 30 minutes to 40 minutes to complete the emulsification. After the reaction is finished, let stand to remove acetone, for example, use a vacuum distillation method to remove acetone to obtain a water-based polyurethane dispersion with high bio-based content.
在本发明实施例中，还提供一种高生物基含量水性聚氨酯合成革的制备方法，制备方法包括步骤S11～S12。In the embodiment of the present invention, a method for preparing water-based polyurethane synthetic leather with high bio-based content is also provided, and the preparation method includes steps S11-S12.
步骤S11、将高生物基含量的水性聚氨酯分散液涂覆在离型纸上，涂覆量例如为500g/m2，在120℃烘箱中烘干形成连续均匀的聚氨酯薄膜。Step S11 , coating the water-based polyurethane dispersion with high bio-based content on the release paper, the coating amount is eg 500g/m2 , and drying in an oven at 120°C to form a continuous and uniform polyurethane film.
步骤S12、在所得聚氨酯薄膜上刮涂氨基树脂粘结剂，与非织造布贴合，利用剥离装置将离型纸剥离，得到高生物基含量的水性聚氨酯合成革。Step S12 , scrape-coat amino resin adhesive on the obtained polyurethane film, bond it with nonwoven fabric, and peel off the release paper with a peeling device to obtain water-based polyurethane synthetic leather with high bio-based content.
在本发明实施例中，测试实施例1～3中高生物基含量的水性聚氨酯分散液的粒径和离心加速沉降情况，离心速度例如为3000r/min，离心时间例如为15min。测试实施例1～3中高生物基含量的水性聚氨酯分散液形成薄膜的拉伸强度和断裂伸长率。同时，测试实施例1～3中高生物基含量的水性聚氨酯合成革的厚度、视密度、耐摩擦色牢度、耐磨性和耐折牢度等物理性能。In the embodiment of the present invention, the particle size and centrifugation accelerated sedimentation of the aqueous polyurethane dispersion with high bio-based content in Examples 1-3 are tested, the centrifugation speed is, for example, 3000r/min, and the centrifugation time is, for example, 15min. The tensile strength and elongation at break of the films formed from the aqueous polyurethane dispersions with high biobased content in Examples 1-3 were tested. At the same time, physical properties such as thickness, apparent density, color fastness to rubbing, abrasion resistance and folding fastness of the water-based polyurethane synthetic leather with high bio-based content in Examples 1 to 3 were tested.
以下将引入具体的实施例对本发明进行更为详细的阐述。The following specific examples will be introduced to illustrate the present invention in more detail.
实施例1Example 1
制备合成革用高生物基含量的水性聚氨酯分散液。Preparation of high biobased aqueous polyurethane dispersions for synthetic leather.
步骤S10、在反应器中加入20.0质量份的数均分子量为2000g/mol的聚乳酸二元醇，在温度为105℃、真空度大于0.085MPa的条件下，减压脱水反应1h。降温至90℃，向反应器中加入10.0份的1,5-戊二异氰酸酯，恒温反应2h后。降温至60℃，向反应器中加入1.0份的生物基乙二醇、0.5份的生物基甘草异黄酮和0.5份的环保催化剂新十二酸铋，再升温至80℃，恒温反应4h。在反应过程中，加入丙酮调节体系黏度。Step S10, adding 20.0 parts by mass of polylactic acid diol with a number average molecular weight of 2000 g/mol into the reactor, and dehydrating under reduced pressure for 1 h at a temperature of 105° C. and a vacuum greater than 0.085 MPa. Lower the temperature to 90°C, add 10.0 parts of 1,5-pentanediisocyanate into the reactor, and react at constant temperature for 2 hours. Cool down to 60°C, add 1.0 parts of bio-based ethylene glycol, 0.5 parts of bio-based licorice isoflavones and 0.5 parts of environmentally friendly catalyst bismuth neododecanoate into the reactor, then raise the temperature to 80°C, and react at constant temperature for 4 hours. During the reaction, acetone was added to adjust the viscosity of the system.
步骤S20、将步骤S10中的反应体系降温至40℃，向反应器中加入1.0份的中和剂三乙胺，反应10min，再加入0.5份的后扩链剂乙二胺和75.0份的去离子水，高速搅拌30min，完成乳化反应。结束后，静置后脱除丙酮，得到高生物基含量的水性聚氨酯分散液。Step S20, cool down the reaction system in step S10 to 40°C, add 1.0 parts of neutralizing agent triethylamine to the reactor, react for 10 minutes, then add 0.5 parts of post-chain extender ethylenediamine and 75.0 parts of Ionized water, stirred at high speed for 30 minutes, to complete the emulsification reaction. After the end, the acetone is removed after standing to obtain a water-based polyurethane dispersion with high bio-based content.
制备高生物基含量水性聚氨酯合成革。Preparation of waterborne polyurethane synthetic leather with high biobased content.
步骤S11：将步骤S20中制备的高生物基含量的水性聚氨酯分散液涂覆在离型纸上，涂覆量为500g/m2，在120℃烘箱中烘干，形成连续均匀的聚氨酯薄膜。Step S11: coating the aqueous polyurethane dispersion with high bio-based content prepared in step S20 on release paper with a coating amount of 500 g/m2 , and drying in an oven at 120° C. to form a continuous and uniform polyurethane film.
步骤S12：在步骤S12中制备的聚氨酯薄膜上刮涂氨基树脂粘结剂，与非织造布贴合，利用剥离装置将离型纸剥离，得到高生物基含量的水性聚氨酯合成革。Step S12: Scrape-coat amino resin adhesive on the polyurethane film prepared in step S12, bond it with non-woven fabric, and peel off the release paper with a peeling device to obtain water-based polyurethane synthetic leather with high bio-based content.
实施例2Example 2
制备合成革用高生物基含量的水性聚氨酯分散液。Preparation of high biobased aqueous polyurethane dispersions for synthetic leather.
步骤S10、在反应器中加入25.0质量份的数均分子量为2000g/mol的聚乳酸二元醇，在温度为105℃、真空度大于0.085MPa的条件下，减压脱水反应1h。降温至90℃，向反应器中加入12.0份的L-赖氨酸二异氰酸酯，恒温反应3h后。降温至60℃，向反应器中加入2.0份的生物基2,3-丁二醇、0.7份的生物基3,4,5,7-四羟基黄酮和0.6份的环保催化剂异辛酸锌，再升温至80℃恒温反应5h。反应过程中，加入丙酮调节体系黏度。Step S10, adding 25.0 parts by mass of polylactic acid diol with a number average molecular weight of 2000 g/mol into the reactor, and dehydrating under reduced pressure for 1 h at a temperature of 105° C. and a vacuum greater than 0.085 MPa. The temperature was lowered to 90° C., and 12.0 parts of L-lysine diisocyanate was added to the reactor, and then reacted at constant temperature for 3 hours. Cool down to 60°C, add 2.0 parts of bio-based 2,3-butanediol, 0.7 parts of bio-based 3,4,5,7-tetrahydroxyflavone and 0.6 parts of environmental catalyst zinc isooctanoate to the reactor, and then The temperature was raised to 80°C for constant temperature reaction for 5h. During the reaction, acetone was added to adjust the viscosity of the system.
步骤S20、将步骤S10中的反应体系降温至40℃，向反应器中加入1.3份的中和剂碳酸钠，反应15min，后加入1.5份的后扩链剂三乙烯二胺和90.0份的去离子水，高速搅拌35min，完成乳化反应。结束后，静置后脱除丙酮，得到高生物基含量的水性聚氨酯分散液。Step S20, cooling the reaction system in step S10 to 40°C, adding 1.3 parts of neutralizing agent sodium carbonate to the reactor, reacting for 15 minutes, and then adding 1.5 parts of post-chain extender triethylenediamine and 90.0 parts of Ionized water, stirred at high speed for 35 minutes, to complete the emulsification reaction. After the end, the acetone is removed after standing to obtain a water-based polyurethane dispersion with high bio-based content.
制备高生物基含量水性聚氨酯合成革。Preparation of waterborne polyurethane synthetic leather with high biobased content.
步骤S11：将步骤S20中制备的高生物基含量的水性聚氨酯分散液涂覆在离型纸上，涂覆量为500g/m2，在120℃烘箱中烘干，形成连续均匀的聚氨酯薄膜。Step S11: coating the aqueous polyurethane dispersion with high bio-based content prepared in step S20 on release paper with a coating amount of 500 g/m2 , and drying in an oven at 120° C. to form a continuous and uniform polyurethane film.
步骤S12：在步骤S12中制备的聚氨酯薄膜上刮涂氨基树脂粘结剂，与非织造布贴合，利用剥离装置将离型纸剥离，得到高生物基含量的水性聚氨酯合成革。Step S12: Scrape-coat amino resin adhesive on the polyurethane film prepared in step S12, bond it with non-woven fabric, and peel off the release paper with a peeling device to obtain water-based polyurethane synthetic leather with high bio-based content.
实施例3Example 3
制备合成革用高生物基含量的水性聚氨酯分散液。Preparation of high biobased aqueous polyurethane dispersions for synthetic leather.
步骤S10、在反应器中加入30.0质量份的数均分子量为2000g/mol的聚乳酸二元醇，在温度为105℃、真空度大于0.085MPa的条件下，减压脱水反应1h。降温至90℃，向反应器中加入15.0份的二聚酸二异氰酸酯，恒温反应3h后。降温至60℃，向反应器中加入2.5份的生物基1,4-丁二醇、1.0份的生物基3,4,5,7-四羟基黄酮和1.0份的环保催化剂异辛酸锌，再升温至80℃，恒温反应6h。反应过程中，加入丙酮调节体系黏度。Step S10, adding 30.0 parts by mass of polylactic acid diol with a number average molecular weight of 2000 g/mol into the reactor, and dehydrating under reduced pressure for 1 h at a temperature of 105° C. and a vacuum greater than 0.085 MPa. The temperature was lowered to 90° C., and 15.0 parts of dimer acid diisocyanate was added to the reactor, and then reacted at constant temperature for 3 hours. Cool down to 60°C, add 2.5 parts of bio-based 1,4-butanediol, 1.0 parts of bio-based 3,4,5,7-tetrahydroxyflavone and 1.0 parts of environmental catalyst zinc isooctanoate into the reactor, and then The temperature was raised to 80°C, and the reaction was carried out at constant temperature for 6h. During the reaction, acetone was added to adjust the viscosity of the system.
步骤S20、将步骤S10中的反应体系降温至40℃，向反应器中加入2.5份的中和剂焦磷酸钠，反应20min，再加入3.0份的后扩链剂异佛尔酮二胺和100.0份的去离子水，高速搅拌40min，完成乳化反应。结束后，静置后脱除丙酮，得到高生物基含量的水性聚氨酯分散液。Step S20, cool down the reaction system in step S10 to 40°C, add 2.5 parts of neutralizing agent sodium pyrophosphate to the reactor, react for 20 minutes, then add 3.0 parts of post-chain extender isophoronediamine and 100.0 part of deionized water, and stirred at high speed for 40 minutes to complete the emulsification reaction. After the end, the acetone is removed after standing to obtain a water-based polyurethane dispersion with high bio-based content.
制备高生物基含量水性聚氨酯合成革。Preparation of waterborne polyurethane synthetic leather with high biobased content.
步骤S11：将步骤S20中制备的高生物基含量的水性聚氨酯分散液涂覆在离型纸上，涂覆量为500g/m2，在120℃烘箱中烘干，形成连续均匀的聚氨酯薄膜。Step S11: coating the aqueous polyurethane dispersion with high bio-based content prepared in step S20 on release paper with a coating amount of 500 g/m2 , and drying in an oven at 120° C. to form a continuous and uniform polyurethane film.
步骤S12：在步骤S12中制备的聚氨酯薄膜上刮涂氨基树脂粘结剂，与非织造布贴合，利用剥离装置将离型纸剥离，得到高生物基含量的水性聚氨酯合成革。Step S12: Scrape-coat amino resin adhesive on the polyurethane film prepared in step S12, bond it with non-woven fabric, and peel off the release paper with a peeling device to obtain water-based polyurethane synthetic leather with high bio-based content.
实施例1～3制得的高生物基含量的水性聚氨酯分散液和高生物基含量的水性聚氨酯胶膜的性能数据，如表1所示。The performance data of the water-based polyurethane dispersion liquid with high bio-based content and the water-based polyurethane film with high bio-based content prepared in Examples 1-3 are shown in Table 1.
表1实施例1～3制得的高生物基含量的水性聚氨酯分散液、水性聚氨酯胶膜的性能数据The performance data of the water-based polyurethane dispersion liquid and the water-based polyurethane adhesive film of the high bio-based content that table 1 embodiment 1～3 makes
实施例1～3制得高生物基含量的水性聚氨酯合成革的性能数据，如表2所示。The performance data of the water-based polyurethane synthetic leather with high bio-based content obtained in Examples 1-3 are shown in Table 2.
表2实施例1～3制得高生物基含量的水性聚氨酯合成革的性能Table 2 embodiment 1～3 makes the performance of the waterborne polyurethane synthetic leather of high bio-based content
由表1可见，实施例1～3所制备的合成革用高生物基含量的水性聚氨酯性能稳定，水性聚氨酯分散液的粒径低于100nm，室温环境下可稳定贮存6个月。且实施例1～3所制备的合成革用高生物基含量的水性聚氨酯胶膜中生物基组分含量大于80％，同时拉伸强度和断裂伸长率等力学性能优异。It can be seen from Table 1 that the water-based polyurethane with high bio-based content for synthetic leather prepared in Examples 1-3 has stable properties, the particle size of the water-based polyurethane dispersion is less than 100 nm, and it can be stored stably for 6 months at room temperature. And the content of bio-based components in the water-based polyurethane film with high bio-based content for synthetic leather prepared in Examples 1-3 is greater than 80%, and meanwhile the mechanical properties such as tensile strength and elongation at break are excellent.
由表2可见，将实施例1～3中制得高生物基含量的水性聚氨酯制备成合成革，测试合成革的厚度、视密度、耐摩擦色牢度、耐磨性和耐折牢度等方面性能。制备的合成革满足不同领域用合成革的性能要求，用实施例1获得的水性聚氨酯制备得到的合成革满足家具用水性聚氨酯合成革的性能要求，用实施例2获得的水性聚氨酯制备得到的合成革满足服装用水性聚氨酯合成革的性能要求，用实施例3获得的水性聚氨酯制备得到的合成革满足汽车装饰用水性聚氨酯合成革的性能要求，弥补了市场上高生物基含量的材料在合成革方向应用上的不足。As can be seen from Table 2, the water-based polyurethane with high bio-based content obtained in Examples 1-3 was prepared into synthetic leather, and the thickness, apparent density, color fastness to rubbing, abrasion resistance and folding fastness of the synthetic leather were tested. aspect performance. The prepared synthetic leather meets the performance requirements of synthetic leather in different fields, the synthetic leather prepared with the water-based polyurethane obtained in Example 1 meets the performance requirements of the water-based polyurethane synthetic leather for furniture, and the synthetic leather prepared with the water-based polyurethane obtained in Example 2 The leather satisfies the performance requirements of the water-based polyurethane synthetic leather for clothing, and the synthetic leather prepared by the water-based polyurethane obtained in Example 3 meets the performance requirements of the water-based polyurethane synthetic leather for automotive decoration, and makes up for the high bio-based content of materials on the market. Inadequate application of directions.
综上所述，本发明提供一种合成革用高生物基含量的水性聚氨酯分散液及其制备方法，通过分子设计与配方优化，获得一种合成革用高生物基含量的水性聚氨酯分散液。通过多种生物基原料制备水性聚氨酯，实现了生物基含量大于80％，并以环保催化剂替代有毒的锡类催化剂。选取含羧基侧链的L-赖氨酸与生物基三亚甲基碳酸酯共聚改性后的聚乳酸多元醇作为软段，以聚乳酸多元醇侧链中羧基为亲水基团，且通过聚乳酸多元醇中碳酸酯键与酯键的共同作用，赋予合成革用高生物基含量水性聚氨酯分散液高的稳定性，分散液形成的膜力学性能突出。In summary, the present invention provides an aqueous polyurethane dispersion with high bio-based content for synthetic leather and a preparation method thereof. Through molecular design and formula optimization, an aqueous polyurethane dispersion with high bio-based content for synthetic leather is obtained. The water-based polyurethane is prepared by using a variety of bio-based raw materials to achieve a bio-based content of more than 80%, and an environmentally friendly catalyst is used to replace the toxic tin catalyst. The polylactic acid polyol modified by copolymerization of L-lysine with carboxyl side chain and bio-based trimethylene carbonate was selected as the soft segment, and the carboxyl group in the side chain of polylactic acid polyol was used as the hydrophilic group, and the The joint effect of carbonate bond and ester bond in lactic acid polyol endows the high bio-based content aqueous polyurethane dispersion for synthetic leather with high stability, and the film formed by the dispersion has outstanding mechanical properties.
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。The preferred embodiments of the invention disclosed above are only to help illustrate the invention. The preferred embodiments are not exhaustive in all detail, nor are the inventions limited to specific embodiments described. Obviously, many modifications and variations can be made based on the contents of this specification. This description selects and specifically describes these embodiments in order to better explain the principle and practical application of the present invention, so that those skilled in the art can well understand and utilize the present invention. The invention is to be limited only by the claims, along with their full scope and equivalents.
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