有机硅丙烯酸酯改性水性聚氨酯的合成与性能
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摘要
以异佛尔酮二异氰酸酯(IPDI)、g-氨丙基三乙氧基硅烷(KH550)、甲基丙烯酸甲酯(MMA)、g-(甲基丙烯酰氧基)丙基三甲氧基硅烷(KH570)为原料,分别合成了水性聚氨酯预聚体(WPU)、聚丙烯酸酯(PA)、有机硅改性的水性聚氨酯预聚体(Si WPU)和有机硅改性的聚丙烯酸酯(Si PA),然后以WPU、SiWPU、PA、Si PA为原料,采用互穿网络聚合法合成了有机硅-丙烯酸酯双重改性水性聚氨酯。通过测定吸水率和水接触角考察了PA、Si PA、Si WPU含量对胶膜耐水性能的影响并分析了反应机理。结果表明:SiWPU-40%-SiPA-37.5%〔40%为Si WPU的含量(以WPU和SiWPU总质量为基准,下同);37.5%为Si PA占膜总质量百分数〕胶膜吸水率从改性前样品WPU的37.8%降低至改性后的6.8%,接触角从56.8°增至86.4°,铅笔硬度从改性前的2B提升至H。热重分析显示,T_(max)(样品热分解速率最大时的温度)从改性前的340.2℃提升至412.4℃;TEM表明,改性后的乳胶粒形成了核壳结构;XRD和断面SEM显示,PA和有机硅改性均增加了聚合物的交联度。
Waterborne polyurethane prepolymer(WPU), polyacrylate(PA), silicone modified waterborne polyurethane prepolymer(SiWPU) and polyacrylate(SiPA) were synthesized using isophorone diisocyanate(IPDI), γ-aminopropyltriethoxysilane(KH550), methyl methacrylate(MMA) and γ-(methacryloyloxy)propyltrimethoxysilane(KH570) as main raw materials. Then, silicone acrylate double modified waterborne polyurethane(SiWPUA) emulsions were synthesized by interpenetrating network polymerization using WPU, SiWPU and SiPA as raw materials. The effects of PA addition amount, SiPA addition amount and SiWPU addition amount on the water resistance of the emulsion films were investigated by measuring water absorption rate and water contact angle and the mechanism was analyzed. The results showed that the water absorption rate of SiWPU-40%-SiPA-37.5%(40% is the content of SiWPU based on the total mass of WPU and SiWPU, the same below, and 37.5% is the mass fraction of SiPA in the system) film was reduced from 37.8% before modification to 6.8%, the contact angle was increased from 56.8° to 86.4°, and pencil hardness was increased from 2 B to H. Thermogravimetric analysis demonstrated that the Tmax(the temperature at which the decomposition reaction occurs) of SiWPU-40%-SiPA-37.5% was 412.4 ℃,higher than that of WPU(340.2 ℃). TEM results revealed that the modified latex particles had a core-shell structure. SEM of film section and XRD results showed that both PA and silicone modification increased the crosslinking degree of the polymer.
Waterborne polyurethane prepolymer(WPU), polyacrylate(PA), silicone modified waterborne polyurethane prepolymer(SiWPU) and polyacrylate(SiPA) were synthesized using isophorone diisocyanate(IPDI), γ-aminopropyltriethoxysilane(KH550), methyl methacrylate(MMA) and γ-(methacryloyloxy)propyltrimethoxysilane(KH570) as main raw materials. Then, silicone acrylate double modified waterborne polyurethane(SiWPUA) emulsions were synthesized by interpenetrating network polymerization using WPU, SiWPU and SiPA as raw materials. The effects of PA addition amount, SiPA addition amount and SiWPU addition amount on the water resistance of the emulsion films were investigated by measuring water absorption rate and water contact angle and the mechanism was analyzed. The results showed that the water absorption rate of SiWPU-40%-SiPA-37.5%(40% is the content of SiWPU based on the total mass of WPU and SiWPU, the same below, and 37.5% is the mass fraction of SiPA in the system) film was reduced from 37.8% before modification to 6.8%, the contact angle was increased from 56.8° to 86.4°, and pencil hardness was increased from 2 B to H. Thermogravimetric analysis demonstrated that the Tmax(the temperature at which the decomposition reaction occurs) of SiWPU-40%-SiPA-37.5% was 412.4 ℃,higher than that of WPU(340.2 ℃). TEM results revealed that the modified latex particles had a core-shell structure. SEM of film section and XRD results showed that both PA and silicone modification increased the crosslinking degree of the polymer.
引文
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[3]Chattopadhyay D K,Raju K V S N.Structural engineering of polyurethane coatings for high performance applications[J].Progress in Polymer Science,2007,32(3):352-418.
[4]Zheng G,Lu M,Rui X,et al.The effect of acrylate on structure and properties of waterborne polyurethane porous coated fabrics[J].Journal of Applied Polymer Science,2018,135(5):45783.
[5]Dave V J,Patel H S.Synthesis and characterization of interpenetrating polymer networks from transesterified castor oil based polyurethane and polystyrene[J].Journal of Saudi Chemical Society,2013,21(1):18-24.
[6]Chai S L,Jin M M,Tan H M.Comparative study between core-shell and interpenetrating network structure polyurethane/polyacrylate composite emulsions[J].European Polymer Journal,2008,44(10):3306-3313.
[7]Liao M,Sun D.Synthesis and characterization of ambienttemperature self-crosslinked waterborne polyurethanes with a novel diol chain extender bearing two ketone groups[J].Journal of Coatings Technology and Research,2016,13(4):667-676.
[8]Lai J,Ling H,Yeh J,et al.New self-curable,aqueous-based polyurethane system by an isophorone diisocyanate/uretedione aziridinyl derivative process[J].Journal of Applied Polymer Science,2004,94(3):845-859.
[9]Wu Y,Du Z,Wang H,et al.Synthesis of aqueous highly branched silica sol as underlying crosslinker for corrosion protection[J].Progress in Organic Coatings,2017,111:381-388.
[10]Shen Yiding(沈一丁),Liu Jingsong(刘敬松),Lai Xiaojuan(赖小娟).Synthesis and properties of waterborne polyurethane modified by organic silicon and acrylic ester[J].Fine Chemicals(精细化工),2009,26(10):953-956.
[11]Sardon H,Irusta L,Santamaria P,et al.Thermal and mechanical behaviour of self-curable waterborne hybrid polyurethanes functionalized with(3-aminopropyl)triethoxysilane(APTES)[J].Journal of Polymer Research,2012,19(9):9956-9958.
[12]Naghash H J,Abili B.Synthesis of a silicone containing allylic monomer and its uses in the waterborne polyurethane/vinyl acetateacrylic hybrid emulsion copolymers[J].Progress in Organic Coatings,2010,69(4):486-494.
[13]Zhang C,Zhang X,Dai J,et al.Synthesis and properties of PDMSmodified waterborne polyurethane-acrylic hybrid emulsion by solventfree method[J].Progress in Organic Coatings,2008,63(2):238-244.
[14]Zhang J,Li X,Shi X,et al.Synthesis of core-shell acrylicpolyurethane hybrid latex as binder of aqueous pigment inks for digital inkjet printing[J].Progress in Natural Science Materials International,2012,22(1):71-78.
[15]Wang Y,Qiu F,Xu B,et al.Preparation,mechanical properties and surface morphologies of waterborne fluorinated polyurethaneacrylate[J].Progress in Organic Coatings,2013,76(5):876-883.
[16]Raftopoulos K N,Janowski B,Apekis L,et al.Molecular mobility and crystallinity in polytetramethylene ether glycol in the bulk and as soft component in polyurethanes[J].European Polymer Journal,2011,47(11):2120-2133.
[17]Jiao L,Xiao H,Wang Q,et al.Thermal degradation characteristics of rigid polyurethane foam and the volatile products analysis with TG-FTIR-MS[J].Polymer Degradation&Stability,2013,98(12):2687-2696.
[18]Allauddin Shaik,Ramanuj Narayan,Raju K V S N.Synthesis and properties of siloxane-crosslinked polyurethane-urea/silica hybrid films from castor oil[J].Journal of Coatings Technology&Research,2014,11(3):397-407.
[19]Shin M,Lee Y,Rahman M,et al.Synthesis and properties of waterborne fluorinated polyurethane-acrylate using a solventemulsifier-free method[J].Polymer,2013,54(18):4873-4882.