原位交联羽毛角蛋白杂化膜的制备与性能表征

以羽毛角蛋白粉(FK)、甘油和γ-(2,3-环氧丙氧)丙基三甲氧基硅烷(KH560)为原料,采用浇铸法制备了原位交联的羽毛角蛋白杂化膜。借助FITR、TG、SEM和接触角测试仪等手段对羽毛角蛋白杂化膜的结构和性能进行了分析和表征,同时考察了KH560用量对其力学性能、热稳定性、疏水性的影响。结果表明:在碱性加热条件下,KH560上的环氧基与羽毛角蛋白上的氨基发生了加成反应以及KH560上Si—O—CH3水解成Si—OH,然后缩合形成Si—O—Si网络结构,从而增强了羽毛角蛋白之间的相互作用力,有效地改善了羽毛角蛋白膜的力学性能、热稳定性和疏水性。     

改性倍半硅氧烷杂化膜的制备及光学性能研究

采用溶胶凝胶法,选用γ-(2,3-环氧丙氧)丙基三甲氧基硅烷(KH560)为原料,制备多面体低聚倍半硅氧烷杂化膜(POSS),并在合成过程中分别引入正硅酸乙酯和磷酸,考察改性前后杂化膜光学性能及热稳定性的影响。结果表明:用正硅酸乙酯改性的POSS,比未改性前的POSS可见光透明性升高,折射率降低,热稳定性提高;用磷酸改性后的POSS,透明性降低,折射率上升,热稳定性明显下降。     

有机-无机杂化改性水性丙烯酸铁红漆的制备及其性能研究

通过溶胶-凝胶法,以正硅酸乙酯(TEOS)为原料,通过γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)制备环氧基改性硅溶胶。将改性后的硅溶胶应用到丙烯酸铁红漆中。用红外光谱、热质分析、接触角及电化学测试对制备的涂层进行性能测试。实验结果发现:加入0.5%的环氧改性硅溶胶的丙烯酸铁红漆与未改性的相比,其热稳定性、疏水性及耐腐蚀性有很大的提高。     

新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征

桐油与甘油在甲醇钠为催化剂的条件下发生醇解反应得到桐油醇解产物（GTO）,GTO经环氧化得到环氧化桐油醇解产物（EGTO）,EGTO与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）发生开环反应生成新型含磷阻燃型桐油基多元醇（PTOP）。PTOP部分取代聚醚多元醇（PPG4110）与异氰酸酯及助剂反应,通过一步法制备聚氨酯硬泡（RPUF）。采用万能试验机、热导率测定仪、热重分析仪和锥形量热仪分别考察RPUF的力学性能、热稳定性和燃烧行为。结果表明：随着PTOP替代石油基多元醇的比率增大,RPUF的压缩强度、密度、热导率先增大后减小,热稳定性提高,极限氧指数（LOI）由18.1%提高至26.0%,而总放热量先减小后增大,这主要是由于PTOP结构中的DOPO基团具有阻燃作用而PTOP结构中含有的桐油基脂肪链易于燃烧且热释放量较大。以上结果表明PTOP部分取代PPG4110制备的RPUF具有良好的阻燃性能和热稳定性。     

有机-无机杂化膜的制备及其在传感器中的应用

有机-无机杂化膜具有成本低、成膜性好、强度及韧性佳、热稳定性较高、孔隙率和亲水-疏水平衡可调的优点,是一类很有发展前景、并具有巨大潜在应用价值的新型膜材料。对近年来有机-无机杂化膜的基材选择、杂化方式、制备方法及成膜工艺进行了概述,并简要介绍了传感膜的制备方法及其在传感器中的应用。     

碳纳米管的表面修饰及其对环氧树脂热性能的影响研究

先后利用Fenton试剂和缩水甘油氧丙基硅烷偶联剂(KH560)对碳纳米管（CNTs）进行表面修饰,制备了不同种类的环氧树脂(EP)/CNTs复合材料并对其性能进行了研究。结果表明：CNTs经过Fenton试剂处理后,其表面成功引入羟基,进一步用KH560修饰后成功地引入了环氧基官能团。Fenton试剂的组成可以有效控制羟基基团的数目,并进一步决定环氧基官能团的数目。单独采用Fenton试剂处理或Fenton试剂和KH560共同处理都可以改善CNTs的分散性能,提高EP/CNTs复合材料的玻璃化温度（Tg）和热稳定性能,但后者的处理效果更好。     

邻甲酚醛环氧/改性凹凸棒土复合材料的制备

采用硅烷偶联剂KH560对提纯后的凹凸棒土(AT)进行改性,得到有机化凹凸棒土,并对其进行FTIR和TG表征,结果表明,KH560对凹凸棒土起到了良好的修饰改性作用。采用熔融复合法制备了AT质量分数为0～5%的邻甲酚醛环氧/凹凸棒土纳米复合材料(ECN/(KH560-AT)x),对其进行了扫描电镜(SEM)分析、动态力学分析(DMA)和热重分析以及力学性能测试。结果表明,KH560-AT的加入使复合材料断裂由脆性断裂向韧性断裂转变。ECN/KH560-AT复合材料的拉伸强度、冲击强度和Tg可比纯ECN分别高出54.12%、78.95%和37.5℃,KH560-AT的加入明显提高了复合材料的力学性能和耐热性。     

低介电常数聚酰亚胺/多金属氧酸盐复合薄膜的制备及其性能

以带环氧官能团的3-环氧丙氧基三甲基硅烷(KH560)作为改性剂在酸性MeCN/H2O混合溶液中和多金属氧酸盐K8SiW11O39进行反应,制得了硅烷改性的多金属氧酸盐有机杂化物SiW11KH560,红外光谱、XPS等分析结果表明KH560与K8SiW11O39发生了反应。将改性后的K8SiW11O39添加到均苯四甲酸酐-二苯醚二胺的聚酰胺酸溶液中,热酰亚胺化制备了聚酰亚胺/多金属氧酸盐复合薄膜。EDS能谱分析表明多金属氧酸盐颗粒在聚酰亚胺基体中呈均匀分布,当复合薄膜中多金属氧酸盐有机杂化物SiW11KH560含量达到20%(wt)时,复合薄膜的介电常数从3.29降低至2.9。此外,随着SiW11KH560添加量的增加,复合薄膜的储能模量也显著提高,而复合薄膜的热性能没有受到严重影响。     

TiO_2/MPMS-SSO光学保护膜的制备与性能研究

以正硅酸乙酯、钛酸丁酯、甲基丙烯酰氧基倍半硅氧烷（MPMS-SSO）、γ-环氧丙氧丙基三甲氧基硅烷为原料,通过溶胶-凝胶法制备了Si-Ti杂化涂料、甲基丙烯酰氧基倍半硅氧烷（MPMS-SSO）涂料、甲基丙烯酰氧基倍半硅氧烷与钛酸丁酯杂化的MPMS-SSO-Ti涂料,并在PMMA上成膜。用FT-IR、UV-VIS、动态摩擦减重测试和TG/DSC等对薄膜的结构、透光率、机械性能和热性能进行表征,并分析了Si-Ti、MPMS-SSO和MPMS-SSO-Ti 3种涂料对PMMA膜的影响。结果表明：Si-Ti、MPMS-SSO、MPMS-SSO-Ti光学保护膜在保持PMMA基片透光率基本不变的同时,有效地提高了耐磨性;MPMS-SSO薄膜的耐磨效果最好,MPMS-SSO膜次之,Si-Ti膜最次。从表面应力、预滑动摩擦力和动摩擦力3个方面分析有机无机杂化膜耐磨性能,能够有效解释涂覆Si-Ti、MPMS-SSO、MPMS-SSO-Ti涂料耐磨性依次提高的事实。Si-Ti、MPMS-SSO、MPMS-SSO-Ti薄膜热稳定性良好,其中MPMS-SSO-Ti薄膜耐热性最好。分析表明,微观上具有规整网络结构的倍半硅氧烷与TiO2杂化对提高薄膜的耐磨性能和热稳定性起着重要作用。     

DOPO改性高岭土PP复合材料的阻燃性能研究

通过γ-(2,3-环氧丙氧)丙基三甲氧基硅烷(KH560)改性9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物(DOPO)得到中间体DOPO-KH560,然后在醇水溶剂中与高岭土(Kaol)反应,得到最终产物(DOPO-KH560-Kaol)。通过熔融共混挤出将DOPO-KH560-Kaol添加到膨胀阻燃聚丙烯体系中,进一步改善其阻燃性能。通过极限氧指数仪等测试PP复合材料的阻燃性能和力学性能。结果表明,在不损害力学性能的前提下,添加质量分数1.0%DOPO-KH560-Kaol可有效改善PP复合材料的阻燃性能。     

KH560改性水性硝化纤维乳液的制备及性能

以硝化纤维(NC)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)等为主要原料,制得自乳化型水性硝化纤维乳液,再加入可水解自交联的硅烷偶联剂KH560,其分子中的环氧基与羧基反应,从而制备出KH560改性水性硝化纤维乳液。通过傅里叶变换红外光谱(FT-IR)、透射电子显微镜(TEM)、热重分析(TGA)法等测试手段,研究了KH560和DMPA的含量对乳液及其涂膜性能的影响。结果表明:当w(KH560)=7%,w(DMPA)=3.5%时,改性后的乳液具有良好的稳定性,涂膜的耐水性、耐乙醇性、热性能、力学性能均得到明显改善。     

Preparation and properties of modified graphene oxide incorporated waterborne polyurethane acrylate

In this study, a new modifier (KPG) was prepared by modifying graphene oxide with γ‐glycidoxypropyl trimethoxysilane (KH560) and polydimethylsiloxane (PDMS). KPG was in turn added to aqueous urethane acrylate for the fabrication of waterborne polyurethane polyacrylate emulsion modified with KH560‐PDMS composite (KPG/WPUA). Textural characterizations of the KPG/WPUA coating were achieved via Fourier transform infrared, SEM, TGA and AFM techniques, which revealed that the KPG/WPUA film possessed a smooth surface. The synthesized KPG/WPUA films were tested for mechanical properties, hydrophobicity and acid/water corrosion performance which suggested their highly hydrophobic surface. KPG/WPUA with 0.1% KPG showed a contact angle of 118.35°, 30.35° higher than that of pristine WPUA. The KPG/WPUA film exhibited higher thermal stability, i.e. a 5% weight loss temperature of 305 °C, which was 30 °C higher than that of pristine WPUA film. The Young's modulus and elongation at break of the KPG/WPUA film were 34.1 MPa and 74.88% respectively, which were higher than that of WPUA film. Furthermore, KPG/WPUA films exhibited greater resistance (without obvious blistering and the white spotting phenomenon) to H₂O₂, HCl and water corrosion than pristine WPUA. The superior performance of KPG/WPUA films was attributed to the network chain structure formed upon the introduction of KPG into WPUA. The outstanding performance of KPG/WPUA films in terms of mechanical properties, thermal stability and high resistance to acidic and water corrosion makes them interesting alternative contenders for target applications. © 2019 Society of Chemical Industry     

Effects of surface modification on properties of nanocapsules for self-healing materials

Abstract

Urea formaldehyde (UF) nanocapsules used as self-healing materials were prepared by interfacial polymerisation method using modified aliphatic amine (HB-1618) and UF resin as core and shell materials respectively. Silane coupling agent KH560 was used to modify the surface of UF nanocapsules. Fourier transform infrared spectra (FTIR) results indicated the core materials had been successfully encapsulated in UF shell; moreover, physical or chemical combinations were observed between the surface of nanocapsules and KH560. The analyses of thermal stability and mechanical properties revealed that addition of KH560 significantly improved the thermal stability, tensile strength and elastic property. Scanning electron microscope (SEM) results indicated that the addition of KH560 led to an excellent interfacial adhesion between the surface of nanocapsules and resin matrix, thus improving the ability of self-healing, beneficial for high levels of healing efficiency in the matrix materials.     

硅烷偶联剂改性阳离子水性聚氨酯的研究

以硅烷偶联剂γ-氨丙基三乙氧基硅烷(KH550)为封端剂对阳离子型水性聚氨酯进行杂化改性,并以KH550和γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)为原料合成新型偶联剂D,对聚氨酯进行复合改性,分别合成了纳米SiO2/PU杂化材料和纳米SiO2/PU复合材料.通过FT-IR、粒径分析、AFM对样品的结构进行表征,并对样品的力学性能和耐水性、耐溶剂性进行测试.结果表明:两种体系均生成了二氧化硅相,二氧化硅相在杂化体系中的分散性好于其在复合体系中的分散性.对提高产品性能而言,化学封端改性比物理共混改性更有效.     

PE-LD/硅烷偶联剂改性石墨烯复合薄膜的制备及性能表征

将硅烷偶联剂KH-560接枝到氧化石墨烯上制得KH-560改性氧化石墨烯（KGO）,通过水合肼还原得到KH 560改性石墨烯（KG）,最后将KG和石墨烯（G）分别与低密度聚乙烯（PE-LD）熔融共混、中空吹塑成PE LD/KG复合薄膜和PE-LD/G复合薄膜。对样品的结构、形貌、光学性能、阻透性能、热性能和力学性能等进行表征。结果表明,KH-560成功接枝到KG上;KG无序度增加,KG的层间距比G增加约80 %;KG在PE-LD中分散均匀,团聚较少;G对复合薄膜的光学性能和阻透性能的增强效果优于KG;而KG对复合薄膜的热性能和力学性能的改善明显优于G;当KG的含量为0.5 %（质量分数,下同）时,PE-LD/KG复合薄膜的结晶度和弹性模量分别比纯PE-LD薄膜提高了8.4 %和63.9 %。     

KH560改性双组分室温固化环氧结构胶的制备与性能

将γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)与环氧树脂(EP)预反应,采用黏度计、万能电子材料试验机、红外光谱、差示扫描量热仪,考查了KH560含量对EP/改性聚酰胺室温固化环氧结构胶性能的影响。结果表明,KH560含量从0增加至9质量份(每100份EP中加入量)时,胶体拉伸强度从51 MPa降低至36.5 MPa;压缩强度从79.7 MPa降低至53 MPa;粘接强度从8.7 MPa增至11.7 MPa。同时,固化物的热稳定性也有一定程度提高,未改性及9份KH560改性的EP固化物50%热失重的温度分别为382.1℃与403.6℃。     

增容剂对PVDF/PUR-T复合材料的性能影响

采用流延成膜法制备了硅烷偶联剂KH–560和端氨基液体丁腈橡胶(ATBN)协同改性的聚偏氟乙烯(PVDF)/聚醚型热塑性聚氨酯弹性体(PUR–T)复合材料,初步探讨了单一增容剂(KH–560或ATBN)含量、复配增容剂含量与比例及成膜温度等条件对PVDF/PUR–T复合材料力学性能的影响,深入研究了复合材料的结晶性能、热稳定性能和亲/疏水性能。结果表明,与单一增容剂相比,复配增容剂的引入明显提高了复合材料的力学性能,并且当复配增容剂添加量为10%,复配比KH–560/ATBN=3/1,成膜温度为50℃时,其与PVDF/PUR–T基体间的界面粘结性明显得到改善,改性后复合材料断裂伸长率达到273%。PUR–T与复配增容剂的加入抑制了PVDF的结晶,复合材料的结晶度降低,但仍具有良好的热稳定性能,且疏水性得到提高。     

Crosslinked polyurethane–epoxy hybrid emulsion with core–shell structure

An epoxy resin was used to prepare crosslinked polyurethane hybrid emulsion through the blocked NCO prepolymer mixing process. Due to their hydrophobicity, the amine chain extender, blocked –NCO, and epoxy are located inside the emulsion particles. Thus, the crosslinking reaction occurs mostly in the interior of the particles. In this way, the crosslinking density of the resin is increased without the use of solidifying agents or heating during film formation, and the stability of the emulsions remains uninfluenced. The effects of the type of amine chain extender and the type, dosage, and addition mode of the epoxy resin were studied in terms of mechanical properties and swelling properties in water and toluene of the cast films. Additionally, the stability of the single-pack hybrid emulsion was studied. The results showed that the sample prepared with diethylene triamine had good stability, chemical resistance, and high mechanical strength. The modulus and water resistance of the films increased with the epoxy resin content, which could reach 20 wt%. The type of amine chain extender affected the stability of the emulsions significantly. The molar ratio of NH/NCO at 1:1 led to the best film performance. The optimal temperature of the chain-extension reaction was approximately 80°C. The hybrid emulsions could be stored for at least 6 months without apparent performance changes.     

Preparation and properties of fluorinated silicon two‐component polyurethane hydrophobic coatings

A polyurethane (PU) hydrophobic coating was prepared by the two‐component method, polycarbonate diol and isophorone diisocyanate becoming a two‐phase composition. The PU films with hydrophobic surface were prepared by establishing a rough structure on the surface of silica (SiO₂) modified with silane coupling agents (γ‐(2,3‐epoxypropoxy)propytrimethoxysilane (KH560) and (heptadecafluoro‐1,1,2,2‐tetradecyl)trimethoxysilane (FAS)). First, the surface of SiO₂ was covered by a layer of hydrophobic methyl and fluorocarbon (C–F) groups. Then, the SiO₂ and modified SiO₂ were obtained by the introduction of KH560 and FAS with the silanol reaction by ultrasonic stirring. The effect of SiO₂ and modified SiO₂ on the structure and hydrophobic properties of PU was investigated by a series of test instruments. The results showed that the introduction of SiO₂ and modified SiO₂ was beneficial for increasing the roughness of the PU coating surface; the roughness of FAS/SiO₂‐PU could reach up to 14.790 nm, four times better than pure PU. A hydrophobic modified PU coating with water contact angle 123° was fabricated by using the hydrophobic C–F group FAS as a low surface energy material and establishing a micro rough structure on the surface of PU. Moreover, PU modified with KH560 and FAS can reduce the glass transition temperature (T_g) of soft segments, resulting in improvement of micro‐phase separation. © 2020 Society of Chemical Industry