酪素基无皂核壳复合乳液的合成、结构与性能研究
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摘要
随着全球石油资源的日益枯竭和非降解合成高分子材料造成的环境污染问题日益严重，可再生资源和环境友好型材料的开发和利用受到越来越多的关注，并已被列为国际前沿学科领域之一。酪素是来源广泛的可再生资源之一，具有独特的成膜特性（如成膜不连续，耐高温等），加之含有多种活性基团易于被改性，正在成为皮革、造纸、涂料、包装等领域应用最广泛的化工原料之一。在皮革工业领域，酪素作为水性涂饰材料之一，自被应用以来便一直占据着重要地位。尤其是随着人们对成品革的穿着及使用舒适度的要求不断提高，酪素类成膜材料由于其所形成涂层卫生性能优异而越来越受到青睐。但是，作为蛋白质，酪素涂层耐水性差和易脆裂等缺陷限制了其进一步应用。为了改善酪素成膜的缺陷，本研究提出在无皂乳液聚合体系中，对其进行一系列改性，工作主要包括以下几个方面：
（1）引入己内酰胺与酪素发生缩聚反应，考察了己内酰胺改性酪素（CA-CPL）的合成条件，包括pH调节剂、己内酰胺用量、反应温度、反应时间等条件对乳液性能、成膜性能及涂饰应用性能的影响规律；对所得乳胶粒的化学结构、微观形貌、粒径大小及分布与成膜微观形貌等进行了表征；并探讨了乳液的成膜机理。当采用三乙醇胺水溶液对酪素进行溶解，己内酰胺用量为35%，改性温度采用75℃，改性时间为3.0h时，CA-CPL乳液性能、成膜性能及涂饰革样的综合性能最优，改性后涂层的柔韧性有大幅提升；傅立叶红外光谱（FT-IR）、~(13)C-固体核磁（~(13)C-NMR）表征结果显示：成功获得己内酰胺与酪素的缩聚产物；透射电子显微镜（TEM）表征结果显示：与纯酪素相比，改性后乳胶粒粒径大幅减小，均一性明显提高；扫描电子显微镜（SEM）、原子力显微镜（AFM）与接触角测试结果表明：CA-CPL薄膜均一性优且具有较好的疏水性。
（2）通过物理共混法在CA-CPL中引入水性聚氨酯（WPU）制备了己内酰胺改性酪素/水性聚氨酯（CA-CPL/WPU）复合乳液；考察了WPU用量对CA-CPL/WPU复合乳液的微观结构、形貌、粒径大小、乳液性能、成膜性能及涂饰应用性能的影响规律，探讨了复合乳胶粒中组分之间的作用力；研究了复合乳液的成膜机理，并建立了相关模型；FT-IR、TEM与DLS测试结果显示：在复合材料中，CA-CPL与WPU组分之间存在较强的氢键作用力。这种作用力在很大程度上影响着乳胶粒的粒径大小及分布。SEM与接触角测试结果显示：当适当用量的WPU引入体系中时，WPU在体系中分散性较好，薄膜表面的疏水性有所增强。涂饰应用结果表明：当复合材料中含有适当用量的WPU时，涂层具有较为优异的柔韧性及疏水性，但是涂层的强度和透水汽性有所降低。
（3）采用CA-CPL为自乳化剂，在酪素基体中引入丙烯酸酯类单体制备核壳型己内酰胺-丙烯酸酯共改性酪素乳液；优化了在无皂乳液聚合过程中的合成条件，包括丙烯酸酯类单体用量、丙烯酸酯类单体配比、反应温度、反应时间等对核壳乳液的结构、性能及微观形貌的影响规律；考察了不同合成条件下所获乳液的性能、成膜性能及涂饰应用性能，结合对乳胶粒形貌、大小、结构等的表征结果，探讨了核壳乳胶粒的形成机理及成膜机理，并建立了相关模型。FT-IR测试结果显示：酪素与丙烯酸酯类单体成功发生了接枝共聚反应。TEM和DLS检测结果表明：己内酰胺-丙烯酸酯共改性酪素乳胶粒粒径大小在纳米级，粒径分布均一。SEM及AFM表征结果显示：己内酰胺-丙烯酸酯共改性酪素乳胶膜结构均一性优。TGA与接触角数据分别显示：和纯酪素相比，己内酰胺-丙烯酸酯共改性酪素热稳定性明显提升，其乳胶膜疏水性大幅提高。
（4）采用单原位法在己内酰胺-丙烯酸酯共改性酪素中引入市售的纳米二氧化硅（SiO_2）粒子，获得核壳结构规整的单原位酪素基SiO_2纳米复合乳液。考察了纳米SiO_2种类、纳米SiO_2用量及引发剂用量等合成条件对复合乳液性能及成膜性能的影响规律；探讨了单原位酪素基SiO_2纳米复合乳胶粒的形成机理及成膜机理，并建立了相关模型。当纳米SiO_2种类为表面含有双键的RNS-D，RNS-D用量为0.3%，引发剂用量为3%时，所制备的单原位酪素基SiO_2纳米复合乳液综合性能最佳；TEM表征结果显示：所得单原位酪素基SiO_2纳米复合乳胶粒呈规则球形，平均粒径为59.34nm，且分布较为均匀。接触角和展色性数据表明：所得复合乳胶膜具有较优的疏水性及展色性；涂饰应用结果显示：与不含SiO_2的己内酰胺-丙烯酸酯共改性酪素乳液相比，单原位酪素基SiO_2纳米复合乳液涂饰革样的抗张强度和卫生性能提高，但耐曲挠度有一定下降。
（5）为进一步提高酪素基SiO_2纳米复合乳液的稳定性及综合性能，采用纳米SiO_2的前驱体正硅酸乙酯（TEOS）代替单原位法中的市售纳米SiO_2粉体，同时引入硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH570），即采用双原位法制备了具有核壳结构的双原位酪素基SiO_2纳米复合乳液；考察了TEOS用量、KH570用量、TEOS及KH570加入方式、反应温度及反应时间等合成条件对复合乳液及成膜性能的影响规律；探讨了复合乳胶粒的形成机理及成膜机理，并建立了相关模型。同时，将双原位法获得的复合乳液与常规复配法获得的复合乳液进行了乳胶粒微观形貌、粒径大小及分布、成膜性能及应用性能的对比研究，并分析了双原位乳液及复配乳液的乳胶粒形成机理及成膜机理，探讨了双原位法制备酪素基SiO_2纳米复合乳液的优势之所在。采用双原位法制备的复合乳胶粒呈规则核壳型球状，粒径约为80nm左右，粒子大小分布均一，且SiO_2均匀包裹于壳层。与未引入SiO_2的己内酰胺-丙烯酸酯共改性酪素相比，采用双原位法制备的酪素基复合材料稳定性更优，粒径更小，且成膜耐热稳定性、耐水性及机械力学性能均有一定幅度提升。与常规复配法获得的复合乳液相比，采用双原位法获得的乳胶粒粒径更小，粒径分布更均一，乳胶粒稳定性更优，且双原位乳液能赋予涂饰革样更为优异的耐热稳定性、耐水性及机械力学性能。
（6）为拓展酪素基复合材料的应用领域，将采用双原位法制备的酪素基SiO_2纳米复合乳液成膜应用于布洛芬的负载与缓释性能研究；探讨了不同pH条件下酪素基复合薄膜的溶胀程度；分析了不同SiO_2含量对薄膜负载药物及缓释药物性能的影响规律；结合对复合薄膜在负载药物前后及释放药物前后宏观及微观形貌与化学结构的表征结果，建立了酪素基SiO_2纳米复合薄膜对药物的缓释机理模型。薄膜在不同pH条件下的溶胀度测试结果显示：酪素基复合薄膜具有pH响应性，随着接枝碱性的增强，薄膜的溶胀度逐渐增大。结合对药物、未载药薄膜及载药薄膜的微观形貌及结构表征结果，可以得到：SiO_2壳层的存在在很大程度上促进了薄膜对药物的负载及缓释性能。在酸性介质中，薄膜对药物的缓释性能最优，说明其具备成为一种胃环境中的载药材料的前景。
With the deficiency of global oil resources and the increasingly seriousenvironmental pollutions caused by non-degradable synthetic polymer materials,there is a good preference for developing and utilizing renewable resources andenvironmentally friendly materials, which has been listed as one of theinternational frontier disciplines. As a bio-based protein, casein is one of therenewable resources and has unique film-forming features, such as discontinuousproperty, high temperature resistant and so on. In addition, casein containsvarious active groups on its chains, so it can be easily modified. Consequently,casein-based film-forming material is becoming one of the most widely usedchemical materials in leather, paper making, paint and packaging fields. Inleather industry, casein has been chosen as one of the most dominant water-basedfinishing materials since it was used. With the increasing requirement for thewearing comfort of leather product, casein is attracting more and more attentionbecause of the unmatchable hygienic properties of its coatings. However, caseincoatings have serious defects such as poor water resistance and brittleness, whichlimits its further application. The aim of this study is to improve the defects ofcasein films in the soap-free emulsion polymerization system by a series ofmodification.
In detail, the main works in this study include the following parts:
(1) Caprolactam was firstly employed to modify casein throughpolycondensation reaction to prepare caprolactam modified casein (CA-CPL).Emulsion properties, film properties and finishing application results were takenas the main indexes to systematically optimize the reaction conditions, includingthe type of pH regulators, caprolactam usage, reaction temperature and reactiontime. Chemical structure, microstructure, particle size and particle distribution ofthe as-prepared CA-CPL were characterized by fourier transform infrared(FT-IR), solid-state13C-NMR, transmission electron microscopy (TEM), scanning electron microscopey (SEM), dynamic light scattering (DLS), atomicforce microscope (AFM) and contact angle measurement. Based on the aboveresults, the formation mechanism of the CA-CPL latexes and the film wereestablished. When casein was dissolved in triethanolamine solution, caprolactamusage was35%, modification temperature was75℃, modification time was3.0h, CA-CPL emulsion property and its film-forming performance were optimal.The introduction of CPL chains onto casein molecules gave relatively strongerhydrophobic and flexibility to the modified coatings. Characterization resultsverified the successful occurrence of polycondensation between caprolactam andcasein. In addition, the particle size of the CA-CPL decreased dramatically andthe size distribution became more even compared with those of neat casein.
(2) Waterborne polyurethane (WPU) was introduced into CA-CPL bymeans of physical blending and caprolactam modified casein/waterbornepolyurethane (CA-CPL/WPU) composite emulsion was prepared. Effects ofWPU usage on CA-CPL/WPU micro-structure, particle size and performancewere mainly investigated. Meanwhile, its application performances in leatherfinishing agent were measured. FT-IR, TEM and DLS characterizations wereconducted to investigate the structure, particle morphology and size distributionof CA-CPL/WPU. In order to find out the relation between the morphology andproperties of the composite, the interaction force between the components in thecomposite latex as well as the film forming mechanism were both discussed, andthe relevant models were established. The results showed that stronger hydrogenbonding interactions existed between CA-CPL and WPU components in thecomposite CA-CPL/WPU. This interaction affected the particle diameter sizeand its distribution to a large extent. SEM and contact angle results showed thatwhen the appropriate usage of WPU was introduced into the composite,dispersibility of WPU was good. Application results showed that when the usageof WPU was proper, the composite materials could endow coatings withexcellent flexibility and hydrophobicity. However, the strength and the watervapor permeability of the coatings decreased.
(3) CA-CPL was used as the self-emulsifier and acrylate monomers wereintroduced into casein system to obtain core-shell type caprolactam-acrylateco-modified casein latexes via soap-free emulsion polymerization process. Effects of reaction conditions including the usage and proportion of acrylicmonomers, reaction temperature, and reaction time on the grafting degree,microstructure and performance of the resultant emulsion were discussed. Theoptimal caprolactam-acrylate co-modified casein emulsion was applied in leatherfinishing, and the application performance was studied compared with that of asimilar commercial product. The mechanism models for core-shell latex particlesformation and its film-forming were established. FT-IR results showed that thecaprolactam-acrylate co-modified casein was successfully obtained via soap-freeemulsion polymerization. TEM and DLS results indicated that the as-preparedlatex particles were nanoscale in size with uniform distribution, bearing obviouscore-shell structures. SEM and AFM results exhibited the homogeneous anduniform structure of modified casein-based latex films. Contact angleaccompanying with TGA data showed that hydrophobicity and thermal stabilityimproved significantly after modification compared with those of neat casein.
(4) Single-in-situ method was adopted by introducing commerciallyavailable nano-silica (SiO_2) particles into caprolactam-acrylate co-modifiedcasein system to obtain core-shell structural casein-based SiO_2nanocompositelatexes. Effects of the variety of nano-SiO_2, the usage of nano-SiO_2, and usage ofthe initiator on the composite emulsion performance and film-forming propertieswere mainly discussed. The formation mechanism of the as-preparedcasein-based composite latexes and the composite films were also explored thusthe relevant models were established. When RNS-D was chosen as thenano-SiO_2, RNS-D usage was0.3%and initiator usage was3%, performancesof casein-based SiO_2composite emulsion prepared through single-in-situ methodreached best. TEM and DLS results showed that the modified casein emulsionparticles were spherical in shape, and their average particle size was59.34nmwith uniform size distribution. Contact angle and color developing data showedthat casein-based nano SiO_2composite had superior hydrophobicity andmatchable colors developing property. Application results showed that theintroduction of SiO_2could give improved tensile strength and sanitationproperties to the finished leather samples, however, the flexibility declined to acertain extent.
(5) To further improve the stability and comprehensive properties of the casein-based SiO_2composite, a method called double-in-situ was employed toprepare the casein-based SiO_2composite latexes. In the double-in-situ method,nano-SiO_2was introduced by adding the precursor ethylorthosilicate (TEOS)instead of directly using the nano-SiO_2powder, and silane coupling agentγ-Methacryloxypropyl trimethoxy silane (KH570) was used to enhance theinterfacial force between inorganic and organic phases, thus obtaining stablecore-shell structural casein-based SiO_2composite latexes. Effects of TEOS usage,KH570usage and their feeding style, reaction temperature and reaction time onthe composite performance were investigated. The mechanism models for latexformation and film formation were also established. To verify the performanceadvantages of casein-based silica composite prepared via double-in-situ method,the control emulsion of casein-based silica composite via physical blending wasprepared and its performance was tested. Contrastive analysis was conducted onthe emulsion prepared via double-in-situ and that prepared via physical blending.TEM and DLS results verified that the resultant double-in-situ casein-based SiO_2nano-composite latexes exhibited evident core-shell structure, and their particlesize was around80nm with uniform particle size distribution. From the SEMand XPS results, SiO_2particles were proved uniformly coated on the shell layerof the core-shell composite latexes. Compared with the composite latexesprepared via single-in-situ method, particles obtained via double-in-situ methodshowed better stability. Through comparison and contrast, it’s noted thatdouble-in-situ method was favor for obtaining more homogeneous particles withhigher stability, heat stability, water resistance and mechanical properties.
(6) The film formed from the as-prepared casein-based SiO_2composite viadouble-in-situ method was applied in ibuprofen delivery system. Beforemeasuring its drug-releasing behavior, swelling degree of the composite filmunder different pH conditions was tested. Effects of SiO_2content on the loadingand releasing properties was studied. The morphology and structure of the drug,drug-loaded film and drug-released film were also investigated through SEM,NMR and FT-IR. Based on the above results, slow-release mechanism model forcasein-based SiO_2nano composite film was propsed. The casein-basedcomposite films were proved pH responsive and the swelling degree of the filmunder different pH conditions followed the order in alkaline medium, neutral medium and acid medium. The loading and releasing behaviors results showedthat the existence of SiO_2layer largely contributed to the film's loading andreleasing performance due to its excellent adsorption ability with drug. In acidmedium, the casein-based film showed superiror controlled release behavior,which suggested that it has a potential application in the stomach sustainedrelease system.
（1）引入己内酰胺与酪素发生缩聚反应，考察了己内酰胺改性酪素（CA-CPL）的合成条件，包括pH调节剂、己内酰胺用量、反应温度、反应时间等条件对乳液性能、成膜性能及涂饰应用性能的影响规律；对所得乳胶粒的化学结构、微观形貌、粒径大小及分布与成膜微观形貌等进行了表征；并探讨了乳液的成膜机理。当采用三乙醇胺水溶液对酪素进行溶解，己内酰胺用量为35%，改性温度采用75℃，改性时间为3.0h时，CA-CPL乳液性能、成膜性能及涂饰革样的综合性能最优，改性后涂层的柔韧性有大幅提升；傅立叶红外光谱（FT-IR）、~(13)C-固体核磁（~(13)C-NMR）表征结果显示：成功获得己内酰胺与酪素的缩聚产物；透射电子显微镜（TEM）表征结果显示：与纯酪素相比，改性后乳胶粒粒径大幅减小，均一性明显提高；扫描电子显微镜（SEM）、原子力显微镜（AFM）与接触角测试结果表明：CA-CPL薄膜均一性优且具有较好的疏水性。
（2）通过物理共混法在CA-CPL中引入水性聚氨酯（WPU）制备了己内酰胺改性酪素/水性聚氨酯（CA-CPL/WPU）复合乳液；考察了WPU用量对CA-CPL/WPU复合乳液的微观结构、形貌、粒径大小、乳液性能、成膜性能及涂饰应用性能的影响规律，探讨了复合乳胶粒中组分之间的作用力；研究了复合乳液的成膜机理，并建立了相关模型；FT-IR、TEM与DLS测试结果显示：在复合材料中，CA-CPL与WPU组分之间存在较强的氢键作用力。这种作用力在很大程度上影响着乳胶粒的粒径大小及分布。SEM与接触角测试结果显示：当适当用量的WPU引入体系中时，WPU在体系中分散性较好，薄膜表面的疏水性有所增强。涂饰应用结果表明：当复合材料中含有适当用量的WPU时，涂层具有较为优异的柔韧性及疏水性，但是涂层的强度和透水汽性有所降低。
（3）采用CA-CPL为自乳化剂，在酪素基体中引入丙烯酸酯类单体制备核壳型己内酰胺-丙烯酸酯共改性酪素乳液；优化了在无皂乳液聚合过程中的合成条件，包括丙烯酸酯类单体用量、丙烯酸酯类单体配比、反应温度、反应时间等对核壳乳液的结构、性能及微观形貌的影响规律；考察了不同合成条件下所获乳液的性能、成膜性能及涂饰应用性能，结合对乳胶粒形貌、大小、结构等的表征结果，探讨了核壳乳胶粒的形成机理及成膜机理，并建立了相关模型。FT-IR测试结果显示：酪素与丙烯酸酯类单体成功发生了接枝共聚反应。TEM和DLS检测结果表明：己内酰胺-丙烯酸酯共改性酪素乳胶粒粒径大小在纳米级，粒径分布均一。SEM及AFM表征结果显示：己内酰胺-丙烯酸酯共改性酪素乳胶膜结构均一性优。TGA与接触角数据分别显示：和纯酪素相比，己内酰胺-丙烯酸酯共改性酪素热稳定性明显提升，其乳胶膜疏水性大幅提高。
（4）采用单原位法在己内酰胺-丙烯酸酯共改性酪素中引入市售的纳米二氧化硅（SiO_2）粒子，获得核壳结构规整的单原位酪素基SiO_2纳米复合乳液。考察了纳米SiO_2种类、纳米SiO_2用量及引发剂用量等合成条件对复合乳液性能及成膜性能的影响规律；探讨了单原位酪素基SiO_2纳米复合乳胶粒的形成机理及成膜机理，并建立了相关模型。当纳米SiO_2种类为表面含有双键的RNS-D，RNS-D用量为0.3%，引发剂用量为3%时，所制备的单原位酪素基SiO_2纳米复合乳液综合性能最佳；TEM表征结果显示：所得单原位酪素基SiO_2纳米复合乳胶粒呈规则球形，平均粒径为59.34nm，且分布较为均匀。接触角和展色性数据表明：所得复合乳胶膜具有较优的疏水性及展色性；涂饰应用结果显示：与不含SiO_2的己内酰胺-丙烯酸酯共改性酪素乳液相比，单原位酪素基SiO_2纳米复合乳液涂饰革样的抗张强度和卫生性能提高，但耐曲挠度有一定下降。
（5）为进一步提高酪素基SiO_2纳米复合乳液的稳定性及综合性能，采用纳米SiO_2的前驱体正硅酸乙酯（TEOS）代替单原位法中的市售纳米SiO_2粉体，同时引入硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH570），即采用双原位法制备了具有核壳结构的双原位酪素基SiO_2纳米复合乳液；考察了TEOS用量、KH570用量、TEOS及KH570加入方式、反应温度及反应时间等合成条件对复合乳液及成膜性能的影响规律；探讨了复合乳胶粒的形成机理及成膜机理，并建立了相关模型。同时，将双原位法获得的复合乳液与常规复配法获得的复合乳液进行了乳胶粒微观形貌、粒径大小及分布、成膜性能及应用性能的对比研究，并分析了双原位乳液及复配乳液的乳胶粒形成机理及成膜机理，探讨了双原位法制备酪素基SiO_2纳米复合乳液的优势之所在。采用双原位法制备的复合乳胶粒呈规则核壳型球状，粒径约为80nm左右，粒子大小分布均一，且SiO_2均匀包裹于壳层。与未引入SiO_2的己内酰胺-丙烯酸酯共改性酪素相比，采用双原位法制备的酪素基复合材料稳定性更优，粒径更小，且成膜耐热稳定性、耐水性及机械力学性能均有一定幅度提升。与常规复配法获得的复合乳液相比，采用双原位法获得的乳胶粒粒径更小，粒径分布更均一，乳胶粒稳定性更优，且双原位乳液能赋予涂饰革样更为优异的耐热稳定性、耐水性及机械力学性能。
（6）为拓展酪素基复合材料的应用领域，将采用双原位法制备的酪素基SiO_2纳米复合乳液成膜应用于布洛芬的负载与缓释性能研究；探讨了不同pH条件下酪素基复合薄膜的溶胀程度；分析了不同SiO_2含量对薄膜负载药物及缓释药物性能的影响规律；结合对复合薄膜在负载药物前后及释放药物前后宏观及微观形貌与化学结构的表征结果，建立了酪素基SiO_2纳米复合薄膜对药物的缓释机理模型。薄膜在不同pH条件下的溶胀度测试结果显示：酪素基复合薄膜具有pH响应性，随着接枝碱性的增强，薄膜的溶胀度逐渐增大。结合对药物、未载药薄膜及载药薄膜的微观形貌及结构表征结果，可以得到：SiO_2壳层的存在在很大程度上促进了薄膜对药物的负载及缓释性能。在酸性介质中，薄膜对药物的缓释性能最优，说明其具备成为一种胃环境中的载药材料的前景。
With the deficiency of global oil resources and the increasingly seriousenvironmental pollutions caused by non-degradable synthetic polymer materials,there is a good preference for developing and utilizing renewable resources andenvironmentally friendly materials, which has been listed as one of theinternational frontier disciplines. As a bio-based protein, casein is one of therenewable resources and has unique film-forming features, such as discontinuousproperty, high temperature resistant and so on. In addition, casein containsvarious active groups on its chains, so it can be easily modified. Consequently,casein-based film-forming material is becoming one of the most widely usedchemical materials in leather, paper making, paint and packaging fields. Inleather industry, casein has been chosen as one of the most dominant water-basedfinishing materials since it was used. With the increasing requirement for thewearing comfort of leather product, casein is attracting more and more attentionbecause of the unmatchable hygienic properties of its coatings. However, caseincoatings have serious defects such as poor water resistance and brittleness, whichlimits its further application. The aim of this study is to improve the defects ofcasein films in the soap-free emulsion polymerization system by a series ofmodification.
In detail, the main works in this study include the following parts:
(1) Caprolactam was firstly employed to modify casein throughpolycondensation reaction to prepare caprolactam modified casein (CA-CPL).Emulsion properties, film properties and finishing application results were takenas the main indexes to systematically optimize the reaction conditions, includingthe type of pH regulators, caprolactam usage, reaction temperature and reactiontime. Chemical structure, microstructure, particle size and particle distribution ofthe as-prepared CA-CPL were characterized by fourier transform infrared(FT-IR), solid-state13C-NMR, transmission electron microscopy (TEM), scanning electron microscopey (SEM), dynamic light scattering (DLS), atomicforce microscope (AFM) and contact angle measurement. Based on the aboveresults, the formation mechanism of the CA-CPL latexes and the film wereestablished. When casein was dissolved in triethanolamine solution, caprolactamusage was35%, modification temperature was75℃, modification time was3.0h, CA-CPL emulsion property and its film-forming performance were optimal.The introduction of CPL chains onto casein molecules gave relatively strongerhydrophobic and flexibility to the modified coatings. Characterization resultsverified the successful occurrence of polycondensation between caprolactam andcasein. In addition, the particle size of the CA-CPL decreased dramatically andthe size distribution became more even compared with those of neat casein.
(2) Waterborne polyurethane (WPU) was introduced into CA-CPL bymeans of physical blending and caprolactam modified casein/waterbornepolyurethane (CA-CPL/WPU) composite emulsion was prepared. Effects ofWPU usage on CA-CPL/WPU micro-structure, particle size and performancewere mainly investigated. Meanwhile, its application performances in leatherfinishing agent were measured. FT-IR, TEM and DLS characterizations wereconducted to investigate the structure, particle morphology and size distributionof CA-CPL/WPU. In order to find out the relation between the morphology andproperties of the composite, the interaction force between the components in thecomposite latex as well as the film forming mechanism were both discussed, andthe relevant models were established. The results showed that stronger hydrogenbonding interactions existed between CA-CPL and WPU components in thecomposite CA-CPL/WPU. This interaction affected the particle diameter sizeand its distribution to a large extent. SEM and contact angle results showed thatwhen the appropriate usage of WPU was introduced into the composite,dispersibility of WPU was good. Application results showed that when the usageof WPU was proper, the composite materials could endow coatings withexcellent flexibility and hydrophobicity. However, the strength and the watervapor permeability of the coatings decreased.
(3) CA-CPL was used as the self-emulsifier and acrylate monomers wereintroduced into casein system to obtain core-shell type caprolactam-acrylateco-modified casein latexes via soap-free emulsion polymerization process. Effects of reaction conditions including the usage and proportion of acrylicmonomers, reaction temperature, and reaction time on the grafting degree,microstructure and performance of the resultant emulsion were discussed. Theoptimal caprolactam-acrylate co-modified casein emulsion was applied in leatherfinishing, and the application performance was studied compared with that of asimilar commercial product. The mechanism models for core-shell latex particlesformation and its film-forming were established. FT-IR results showed that thecaprolactam-acrylate co-modified casein was successfully obtained via soap-freeemulsion polymerization. TEM and DLS results indicated that the as-preparedlatex particles were nanoscale in size with uniform distribution, bearing obviouscore-shell structures. SEM and AFM results exhibited the homogeneous anduniform structure of modified casein-based latex films. Contact angleaccompanying with TGA data showed that hydrophobicity and thermal stabilityimproved significantly after modification compared with those of neat casein.
(4) Single-in-situ method was adopted by introducing commerciallyavailable nano-silica (SiO_2) particles into caprolactam-acrylate co-modifiedcasein system to obtain core-shell structural casein-based SiO_2nanocompositelatexes. Effects of the variety of nano-SiO_2, the usage of nano-SiO_2, and usage ofthe initiator on the composite emulsion performance and film-forming propertieswere mainly discussed. The formation mechanism of the as-preparedcasein-based composite latexes and the composite films were also explored thusthe relevant models were established. When RNS-D was chosen as thenano-SiO_2, RNS-D usage was0.3%and initiator usage was3%, performancesof casein-based SiO_2composite emulsion prepared through single-in-situ methodreached best. TEM and DLS results showed that the modified casein emulsionparticles were spherical in shape, and their average particle size was59.34nmwith uniform size distribution. Contact angle and color developing data showedthat casein-based nano SiO_2composite had superior hydrophobicity andmatchable colors developing property. Application results showed that theintroduction of SiO_2could give improved tensile strength and sanitationproperties to the finished leather samples, however, the flexibility declined to acertain extent.
(5) To further improve the stability and comprehensive properties of the casein-based SiO_2composite, a method called double-in-situ was employed toprepare the casein-based SiO_2composite latexes. In the double-in-situ method,nano-SiO_2was introduced by adding the precursor ethylorthosilicate (TEOS)instead of directly using the nano-SiO_2powder, and silane coupling agentγ-Methacryloxypropyl trimethoxy silane (KH570) was used to enhance theinterfacial force between inorganic and organic phases, thus obtaining stablecore-shell structural casein-based SiO_2composite latexes. Effects of TEOS usage,KH570usage and their feeding style, reaction temperature and reaction time onthe composite performance were investigated. The mechanism models for latexformation and film formation were also established. To verify the performanceadvantages of casein-based silica composite prepared via double-in-situ method,the control emulsion of casein-based silica composite via physical blending wasprepared and its performance was tested. Contrastive analysis was conducted onthe emulsion prepared via double-in-situ and that prepared via physical blending.TEM and DLS results verified that the resultant double-in-situ casein-based SiO_2nano-composite latexes exhibited evident core-shell structure, and their particlesize was around80nm with uniform particle size distribution. From the SEMand XPS results, SiO_2particles were proved uniformly coated on the shell layerof the core-shell composite latexes. Compared with the composite latexesprepared via single-in-situ method, particles obtained via double-in-situ methodshowed better stability. Through comparison and contrast, it’s noted thatdouble-in-situ method was favor for obtaining more homogeneous particles withhigher stability, heat stability, water resistance and mechanical properties.
(6) The film formed from the as-prepared casein-based SiO_2composite viadouble-in-situ method was applied in ibuprofen delivery system. Beforemeasuring its drug-releasing behavior, swelling degree of the composite filmunder different pH conditions was tested. Effects of SiO_2content on the loadingand releasing properties was studied. The morphology and structure of the drug,drug-loaded film and drug-released film were also investigated through SEM,NMR and FT-IR. Based on the above results, slow-release mechanism model forcasein-based SiO_2nano composite film was propsed. The casein-basedcomposite films were proved pH responsive and the swelling degree of the filmunder different pH conditions followed the order in alkaline medium, neutral medium and acid medium. The loading and releasing behaviors results showedthat the existence of SiO_2layer largely contributed to the film's loading andreleasing performance due to its excellent adsorption ability with drug. In acidmedium, the casein-based film showed superiror controlled release behavior,which suggested that it has a potential application in the stomach sustainedrelease system.
引文
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