无溶剂含氟聚氨酯丙烯酸酯表面施胶剂的合成及性能

以丙烯酸单体为溶剂,利用聚己内酯二元醇(PCL1000)、异佛尔酮二异氰酸酯(IPDI)、2,2-二羟甲基丁酸(DMBA)、三羟甲基丙烷(TMP)合成水性聚氨酯丙烯酸酯(WPUA),WPUA中引入十三氟辛醇(FOH),制备无VOC溶剂自交联含氟聚氨酯丙烯酸酯(WFPUA)复合乳液。加入后扩链剂乙二胺基乙磺酸钠(AAS)可提高预聚体自乳化能力,降低乳胶粒粒径,提升WFPUA稳定性。研究了表面施胶后纸张的表面形态、防水防油、耐破度、撕裂度及抗张强度等性能。结果表明:聚合物在施胶后纸张表面纤维上成膜,纸张表面空隙减少;纸张与水和二碘甲烷接触角达到136.1°和105.3°;施胶后纸张耐破度达到266 k Pa,撕裂度达到732 m N,干湿抗张强度指数达到5.1 N·m/g和53 N·m/g,可以很好地运用到特种纸的制备中。     

光固化环氧全氟辛酸酯聚氨酯的研究

以环氧树脂、全氟辛酸、聚乙二醇、异佛尔酮二异氰酸酯(IPDI)和甲基丙烯酸羟乙酯为原料,通过四步反应合成了一种新型的可光固化的聚氨酯大分子单体。利用1H-NMR、IR、接触角、XPS、DSC、TGA、TEM等分析测试手段对单体的结构以及含氟聚合物的表面特性,热性能和断面形貌进行了研究。接触角和XPS的结果表明由于含氟聚合物中的全氟链段容易向表面迁移,使得固化膜表面对H2O和CH2I2的接触角可以达到108.9°和92.3°,具有低的表面自由能,能够有效地改善涂膜的耐水、耐油等性能;热性能以及断面形态分析发现该聚合物表现出较好的热性能和柔韧性。     

活性纳米TiO2改性含氟聚丙烯酸酯复合乳液的性能及应用

以纳米TiO2 (Nano-TiO2)、-甲基丙烯酰氧乙基三甲氧基硅烷(KH570)、全氟辛基乙基丙烯酸酯（FM）等为主要原料,通过KH570改性纳米TiO2后,与丙烯基单体共聚制得了活性纳米TiO2改性含氟聚丙烯酸酯复合乳液。通过红外光谱（FT-IR）、原子力显微镜（AFM）及接触角测量仪等手段研究了共聚物的结构及性能。结果表明：改性纳米TiO2、含氟单体均成功引入到聚丙烯酸酯共聚物中;乳胶粒呈球形分布,表面光滑且呈单分散状态,平均粒径为184nm;与丙烯酸酯聚合物相比,改性后涂膜的粗糙度提高,有利于防水防油性能的提升。氟硅单体的加入使涂膜的接触角大大增加,对水和二碘甲烷的接触角分别为125°及110°, 复合乳液用作表面施胶剂对纸张进行测试后,纸张对水接触角为147°,对二碘甲烷接触角为133°,纸张防水防油性随着氟单体的引入而显著增加。     

阳离子含氟聚氨酯乳液的制备及应用性能

以异佛尔酮二异氰酸酯(IPDI)、聚醚二元醇(PTMG1000)、三羟甲基丙烷(TMP)、N-甲基二乙醇胺(MDEA)和全氟烷基醇(FOH)为主要原料合成了阳离子水性含氟聚氨酯(WFPU)。利用FT-IR、TG分析了含氟聚氨酯的结构及热性能,通过透射电子显微镜(TEM)分析了乳液粒子形貌,通过测定表面张力、接触角分析了WFPU的表面性能。检测了涂膜浸水行为及耐蚀性能。结果表明:含氟单体和聚氨酯发生了聚合反应。TG结果表明WCPU的耐热性得到提高。TEM照片显示WFPU乳液粒子呈规则的球形,粒子分布较为均一。表面张力和接触角测试表明含氟聚氨酯具有低表面能。WFPU涂膜具有较高的防水性及优异的耐蚀性能。     

环氧改性蓖麻油基WPUA纸张施胶剂的研究

以蓖麻油和IPDI(异佛尔酮二异氰酸酯)溶于St(苯乙烯)、BA(丙烯酸丁酯)中制备聚氨酯预聚体,再以MDEA(N-甲基-二乙醇胺)和BDO(1,4-丁二醇)扩链,后用环氧树脂E-44为改性剂,制得EWPUA(环氧树脂改性蓖麻油基阳离子型水性聚氨酯-丙烯酸酯)复合乳液。研究结果表明:环氧基成功地引入到聚合物分子链中;当w(E-44)=4%时,EWPUA乳液具有优异的表面施胶性能。以w(EWPUA)=1%进行表面施胶,纸张施胶度达54 s,抗张强度增加至33.4 N/mm~2,耐破度由89 kPa增加至166 kPa,接触角由82°增加至128°,拉伸强度由5.08 MPa增加至8.86 MPa。     

钛氟聚丙烯酸酯乳液的性能及应用

以纳米TiO_2(nano-TiO_2)、γ-甲基丙烯酰氧乙基三甲氧基硅烷(KH570)、全氟辛基乙基丙烯酸酯(FM)为主要原料,通过KH570改性纳米TiO_2后,与丙烯基单体共聚制得活性纳米TiO_2改性含氟聚丙烯酸酯复合乳液。通过FTIR、AFM及接触角测量仪表征共聚物的结构,测定了其性能。结果表明:改性纳米TiO_2、含氟单体均成功引入到聚丙烯酸酯共聚物中;乳胶粒呈球形分布,表面光滑且呈单分散状态,平均粒径为184 nm;与丙烯酸酯聚合物相比,改性后涂膜的粗糙度提高,有利于防水防油性能的提升。氟硅单体的加入使涂膜的接触角增大,对水和二碘甲烷的接触角分别为125°及110°,复合乳液用作表面施胶剂对纸张进行测试后,纸张对水接触角为147°,对二碘甲烷接触角为133°,纸张防水防油性随着氟单体的引入而显著增加。     

荧光水性聚氨酯纸张表面施胶剂的制备及应用

以自制5,7-二羟基-4-甲基香豆素(DHMC)为水性聚氨酯荧光增白改性剂,制备了一系列荧光水性聚氨酯(FWPU)乳液,采用FTIR、~1H NMR、DLS和荧光光谱等对荧光水性聚氨酯进行了结构表征和性能测试。将制备得到的荧光水性聚氨酯应用于纸张表面施胶,研究探讨了荧光水性聚氨酯乳液对纸张表面施胶性能的影响。FTIR、~1H NMR分析表明,DHMC已被引入到FWPU分子链中;当w(DHMC)=0.6%时,FWPU乳液粒径为86.17nm,荧光强度最强为40220.44 a.u.(1 a.u.=27.2114 e V)。FWPU乳液具有良好的纸张表面施胶性能,纸张施胶度51.92 s,白度77.93%。     

含氟乳液型纸张施胶剂的合成及作用机理

以苯乙烯(St)、丙烯酸丁酯(BA)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)、全氟烷基乙基丙烯酸酯(FEA)为共聚单体,异丙醇(IPA)为溶剂,偶氮二异丁腈(AIBN)作油溶性引发剂,利用无皂乳液聚合法制备出全氟丙烯酸酯无皂乳液。系统研究了含氟乳液用作表面施胶剂的用量对纸张性能的影响和表面施胶的作用机理,并通过红外光谱(FT-IR)、热重分析(TGA)、差示扫描量热法(DSC)对其进行了表征。结果表明:当m(St)∶m(BA)∶m(FEA)∶m(DMC)=3∶3∶2∶1.2,含氟量达到22%时,纸张的防水防油性较佳,表面强度、抗张强度、耐折度和耐破度等物理性能分别提高了45.2%、9.3%、22.2%和7.8%。     

全氟烷基丙烯酸酯对全氟丙烯酸酯乳液性能的影响

在十八烷基三甲基氯化铵(1831)和含氟乳化剂N,N-二甲基-N'-(2-三氟甲基-1-五氟乙基)(FS)的复合乳化作用下,以全氟烷基丙烯酸酯(FM)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、甲基丙烯酸二甲基胺基乙酯(DM)为反应单体,以过硫酸钾(KPS)为引发剂,制备了全氟烷基聚丙烯酸酯乳液(FPE)。通过红外光谱(IR)、热失重分析(TG)对聚合物的结构和热稳定性进行了表征,并用接触角、原子力显微镜(AFM)分析了乳液的防水性能,表明FM成功地接枝到了聚合物上,随着含氟量的增加,分解温度达351.5℃;在含氟量达到w(FM)=12%时,水接触角达127°;采用Z粒度仪以及透射电镜(TEM)对共聚物外观形貌进行了表征,结果表明,乳胶粒的形态呈球形,呈单分散,平均乳液粒径为220 nm。     

全氟丁基丙烯酸酯拒水剂的合成及其应用

以短碳链含氟单体N-甲基全氟丁基磺酰胺基乙基丙烯酸酯(C4氟酯)、甲基丙烯酸十八烷基酯（SMA）、甲基丙烯酸甲酯(MMA)和偏二氯乙烯(VDC)为聚合单体,采用半连续种子乳液聚合法制备了短碳链全氟丁基丙烯酸酯（PC4FA）共聚物乳液,并将其应用于织物整理上。采用FTIR、XPS表征了共聚物的结构和表面元素组成,利用AFM、SEM观察了短碳链全氟丁基丙烯酸酯拒水剂整理前后棉织物的表面形态变化。考察了拒水剂中含氟单体用量、拒水剂质量分数、焙烘温度和焙烘时间对织物拒水效果的影响。优化的整理工艺为：拒水剂中含氟单体质量分数为51.02%,拒水剂质量分数1.8%,焙烘温度180℃,焙烘时间5min。经该工艺整理后的棉织物对水的接触角可达142.5°,拒水等级为100分。     

全氟丙烯酸酯共聚物无皂乳液的制备与膜表面性能

以全氟烷基乙基丙烯酸酯(FM)、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸十八酯(ODA)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)为主要原料,以偶氮二异丁腈(AIBN)和过硫酸钾(KPS)为引发剂,以丙烯酸羟乙酯(HEA)为交联剂,制备了水性阳离子全氟丙烯酸酯无皂乳液。并通过接触角、原子力显微镜(AFM)、热重分析(TG)、红外光谱分析(IR)和扫描电子显微镜(SEM)等进行了表征。经过w(FM)=50%的乳液整理过的纯棉布纤维对水和液体石蜡的接触角分别为138°和125°;w(FM)=50%时,乳胶膜的表面自由能为19.01 mJ/m2;该乳胶膜表面结构呈现荷叶效应。     

Fluorinated polyacrylates containing amino side chains for the surface modification of waterborne epoxy resin

Fluorinated polyacrylates containing amino side chains (FACAs) were synthesized to improve the water repellency of waterborne epoxy resin. First, FACA was prepared by a two-step process. Then, a phase-inversion emulsion technique, taking FACA as the reactive surface additives, was employed to prepare waterborne epoxy resin. The effect of the fluorinated content and the length of the fluorine side chain on the surface, thermal, and bulk properties of the waterborne epoxy resin were investigated. It was observed that moderate increase of the fluorinated content or the length of the fluorine side chain improved the contact angle and thermal properties while the mechanical property was not deteriorated. A small amount of fluoride (0.07 wt %) in the EA-F1/3-1 sample can dramatically increase the water contact angle from 72.63° to 95.31° due to the strong tendency of the macromonomers to migrate toward the outmost layer, resulting in enrichment of fluorine atoms on the surface. X-ray photoelectron spectroscopy results revealed that for a given weight of the two macromonomers, F atomic concentration of the copolymer modified by longer fluorinated side chains was higher than that modified by short fluorinated side chains. From the present investigation, FACA successfully improved the surface property of waterborne epoxy resin and showed a prominent potential application in large-scale industrialization. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47091.     

有机硅协同改性含氟聚氨酯

采用细乳液法结合超声分散技术制备出水性聚氨酯（WPU）、含氟水性聚氨酯（FPAPU）和KH570、羟基硅油协同改性的氟硅水性聚氨酯乳液（SiFPAPU）。通过红外光谱（FTIR）、粒度分布（PSA）、接触角（CA）、表面能分析、原子力显微镜（AFM）、扫描电镜（SEM）、热失重（TG）、拉伸试验表征了WPU、FPAPU、SiFPAPU复合乳液表面性能、热稳定性和力学性能。结果表明随着有机硅协同组分加入,SiFPAPU乳液粒径降低为44.0nm,但粒径分布变宽;成膜后,水相和油相（CH₂I₂）接触角分别达到122.6°、92.5°,表面能降低为11.82mJ/m²,乳胶膜表面平整均一,断面出现明显分层。同时SiFPAPU热稳定性增强,拉伸强度较未改性聚氨酯提高126.1%。     

含氟聚氨酯树脂的制备及性能研究

制备了具有优异拒水、拒油和易去污功能的含氟聚氨酯树脂。方法:通过自制的含氟烷基侧链的含氟二元醇扩链剂(PFDOL)、聚四氢呋喃(PTMEG)、二羟甲基丙酸(DMPA)和二苯基甲烷二异氰酸酯(MD I)等原料,采用两步法制备了含氟聚氨酯树脂。结果:采用傅里叶变换衰减全反射红外光谱(ATR-FTIR)和核磁共振氢谱(1H-NMR)表征了产物的结构。经产物处理后的棉布和皮革对水的静态接触角可以分别达到145°和128°。处理后皮革的拒水性可达10级,拒油性可达8级。同时研究了PFDOL和DMPA含量对产品拒水、拒油和易去污性能的影响,发现DMPA含量为9.73%时,样品仍具有优异的拒水、拒油性能,为制备阴离子型水性含氟聚氨酯提供了基础;DMPA含量为7.2%,F含量为19.2%时,样品具有较好的易去污性能。制备的含氟聚氨酯树脂可应用于纺织品的拒水、柜油整理和易去污整理,具备工业化生产的可能。     

三嗪基含氟扩链剂改性水性聚氨酯的合成

利用三聚氰氯（CC）、八氟戊醇（OFP）和乙醇胺（MEA）间的反应先合成了三嗪基含氟扩链剂CC-F，在此基础上制备出系列三嗪基含氟扩链剂改性水性聚氨酯CC-FPUF。利用FTIR和1HNMR对其结构进行表征，并用DLS、XRD、XPS、SEM、WCA和电子万能试验机探究了CC-FPUF制备中所用CC-F的含量(以CC-F、IPDI、CMA-1044、DMPA、S104、TMP和TEA的总质量为基准，下同）对CC-FPUF的乳液粒径、聚合物形态、胶膜形貌、表面元素组成、疏水性能和力学性能的影响。结果表明，随着CC-F含量的增加，CC-FPUF的乳液粒径、胶膜疏水性能和胶膜拉伸强度均有所增加。当CC-F的含量达到8%（CC-FPUF-8）时，胶膜的水接触角最高达到125.8°，相比不含氟的水性聚氨酯（PU）和CC-FPUF-0（CC-F的含量为0）分别增加了60.9°和34.1°；此时胶膜的拉伸强度最大，相比CC-FPUF-0增加了24.47 MPa。胶膜CC-FPUF-8表现出优异的疏水性能和良好的力学性能。     

聚硅氧烷改性水性聚氨酯的合成及其表面性能

以聚氧化丙烯二醇(PPG)、双羟基亲水性聚硅氧烷多元醇(UC3667)为软段,异佛尔酮二异氰酸酯(IPDI)、1,4-丁二醇(BDO)、二羟甲基丙酸(DMPA)、乙二胺(EDA)为硬段,制备了一系列聚硅氧烷改性水性聚氨酯(WPUs)。用DLS和FTIR表征了水性聚氨酯乳液粒径和膜结构。通过热重分析、拉伸测试、接触角测试、XPS对水性聚氨酯胶膜的性能进了测定。结果表明:随着聚硅氧烷加入量的增多,水性聚氨酯膜拉伸强度先增大后减小;且聚硅氧烷的加入提高了水性聚氨酯膜的热稳定性、断裂伸长率、接触角,降低了水性聚氨酯膜的表面能。当聚硅氧烷质量分数为5.0%时,胶膜表面的硅迁移量达到饱和,表面能为27.27 mJ/m~2。     

Preparation and performance of waterborne UV‐curable polyurethane containing long fluorinated side chains

Novel waterborne UV‐curable polyurethane containing long fluorinated side chains (WUVFPU) was prepared and the fluorinated component was incorporated by two novel fluorinated macromolecular diols (FDO) with different chain length as chain extender. FDO was synthesized via free radical polymerization of hexafluorobutyl methacrylate (HFBMA) using 1‐thioglycerol (TG) as chain transfer agent. Extremely low dosage of FDO incorporated could change the surface property significantly. The influence of both the content and chain length of FDO on the surface energy, surface composition and morphology were investigated by contact angle measurement, XPS and AFM. Surface energy significantly decreased at extremely low concentration of FDO. The hydrophobicity was enhanced with increasing both the content and the chain length of FDO. XPS and AFM results revealed the enhancing hydrophobicity was attributed to the enrichment of F atoms and rougher surface morphology. Gel content, pencil hardness, adhesion, and optical transmittance tests were employed to investigate the coating properties of the UV‐cured films. The preparation and investigation of WUVFPU might provide better understanding of the influence of fluorinated chain length on the properties of polyurethane for theory. Moreover, it might provide a facile and effective route to prepare polyurethane materials with low surface energy for engineering and industry. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44506.     

Modified cellulose nanocrystals enhancement to mechanical properties and water resistance of vegetable oil-based waterborne polyurethane

Environmentally friendly and lightweight silylated cellulose nanocrystal (SCNCs)/waterborne polyurethane (WPU) composite films that exhibit excellent mechanical properties and water resistance were prepared. The cellulose nanocrystals (CNCs) of the filamentous structure were surface-modified by γ-aminopropyltriethoxysilane (APTES) and then introduced into a castor oil-based aqueous polyurethane (WPU) matrix by in situ polymerization. The morphology and silylation degree of CNCs were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and Fourier infrared transform spectroscopy at different APTES concentrations. The results showed that the surface of the nanocellulose crystal has the best silylation morphology and thermal stability with incorporation of 6 wt % APTES. The thermal stability, mechanical properties, surface morphology, and water resistance of the nanocomposites were investigated by TGA, tensile test, SEM and optical contact angle, water absorption test, and mechanical property test after immersed in water. It was found that the effective introduction of modified CNCs resulted in a significant increase in tensile strength at high levels, and the thermal stability and hydrophobicity of the material were improved simultaneously, reaching the percolation threshold at a 0.50 wt % SCNCs as determined theoretically. This study provided an approach to the design and development of surface-modified CNCs/vegetable oil-based polymer composites by using an appropriate concentration of silane coupling agent to modify CNCs and improve the compatibility between nanocellulose and vegetable oil-based polymer matrices. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48228.     

Polyphosphazene nanotube and modified waterborne polyurethane prepared by in situ polymerization

Novel hybrid inorganic/organic poly[cyclotriphosphazene-co-(hexafluoroisopropylidene)] nanotubes (PZTs) were synthesized through nucleophilic substitution using one-step method. The surface of PZTs contains hydroxyl and fluorine groups with a ratio of approximately 1:3, which imparts many functional properties to the nanotubes. The introduction of the active hydroxyl groups increased the chemical bond crosslinking between the nanotubes and the matrix resin. The introduction of fluorine atom provided the hydrophobicity and abrasion resistance properties. The water contact angle of PZTs is 140.3°. Chemical reaction occurred between WPU and PZTs to form covalent bonds through in situ polymerization. The water contact angle and thermal stability of waterborne polyurethane (WPU)/PZTs increased with the increasing nanotube content. When the nanotube content was 1.0 wt%, the maximum tensile strength of the composites was 3.36 MPa and the maximum elongation-at-break was 446.8%. The nanotubes showed toughening and strengthening characteristics. When 1.0 wt% PZTs were incorporated, the friction coefficient and abrasion loss of the composites reached a minimum value. The addition of nanotubes could increase surface hardness and crosslinking degree, absorb the coating heat of friction, and reduce the adhesive wear of polymer and the wear amount. The introduction of fluorine atoms could form a chemical transfer membrane and reduce the friction coefficient. Polyphosphazene nanotubes showed excellent modification properties in the waterborne polyurethane system.