含硅丙烯酸酯改性水性聚氨酯乳液的制备及性能研究
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摘要
以聚四亚甲基醚二醇(PTMEG-2000)、异佛尔酮二异氰酸酯(IPDI)、甲基丙烯酸羟乙酯(HEMA)、2,2-二羟甲基丙酸(DMPA)、1,4-丁二醇(BDO)为主料,合成了HEMA封端的水性聚氨酯(WPU)。引入甲基丙烯酸甲酯(MMA)、甲基丙烯酸羟丙酯(HPMA)、乙烯基三异丙氧基硅烷(AC-76)对WPU进行共聚改性。制备了系列丙烯酸类聚合物(PA)、PA/AC-76改性的PU漆膜。采用傅里叶变换红外光谱表征了漆膜的结构;利用铅笔划痕硬度仪、附着力试验仪、接触角测量仪等考察了PA用量、MMA与HPMA质量比、AC-76用量对漆膜力学性能、疏水性能的影响。结果表明:PA、AC-76与聚氨酯(PU)链段已发生了交联;改性后漆膜的力学性能、疏水性能都得到有效改善。当PA添加量为40%、硬软单体质量比m(MMA)∶m(HPMA)=5∶4、AC-76添加量为5. 41%时,漆膜综合性能最佳。
A waterborne polyurethane( WPU) was synthesized with polytetramethylene ether glycol( PTMEG-2000),isophorone diisocyanate( IPDI),hydroxyethyl methacrylate( HEMA),2,2-dimethylolpropionic acid( DMPA) and 1,4-butanediol( BDO),wherein hydroxyethyl methacrylate( HEMA) was used to block the-NCO terminal groups. Then,the WPU was modified by hydroxypropyl methacrylate( HPMA),methyl methacrylate( MMA),vinyl triisopropoxysilane( AC-76). A series of acrylic polymer( PA),PA/AC-76 modified PU films were prepared. The structure of the modified film was characterized by FT-IR. The effects of PA dosage,mass ratio of MMA and HPMA,addition of AC-76 on the mechanical properties,hydrophobic property of the film were investigated via pencil scratch hardness tester,adhesion tester and contact angle meter. The results showed that the PA,AC-76 and PU were cross-linked successfully. The mechanical properties and hydrophobic properties of the modified film were improved significantly. The optimal performance of the film was obtained under the following conditions: PA 40 wt%,ratio of MMA/HPMA 5 ∶4,AC-76 5. 41%.
A waterborne polyurethane( WPU) was synthesized with polytetramethylene ether glycol( PTMEG-2000),isophorone diisocyanate( IPDI),hydroxyethyl methacrylate( HEMA),2,2-dimethylolpropionic acid( DMPA) and 1,4-butanediol( BDO),wherein hydroxyethyl methacrylate( HEMA) was used to block the-NCO terminal groups. Then,the WPU was modified by hydroxypropyl methacrylate( HPMA),methyl methacrylate( MMA),vinyl triisopropoxysilane( AC-76). A series of acrylic polymer( PA),PA/AC-76 modified PU films were prepared. The structure of the modified film was characterized by FT-IR. The effects of PA dosage,mass ratio of MMA and HPMA,addition of AC-76 on the mechanical properties,hydrophobic property of the film were investigated via pencil scratch hardness tester,adhesion tester and contact angle meter. The results showed that the PA,AC-76 and PU were cross-linked successfully. The mechanical properties and hydrophobic properties of the modified film were improved significantly. The optimal performance of the film was obtained under the following conditions: PA 40 wt%,ratio of MMA/HPMA 5 ∶4,AC-76 5. 41%.
引文
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[19]丁长波.IPN型水性聚氨酯-丙烯酸酯复合乳液的制备及性能研究[D].西安:西安工程大学,2016.
[20]狄剑锋,刘裕文,纪凤龙.交联型有机硅改性聚氨酯丙烯酸酯乳液的合成及其性能[J].纺织学报,2016,37(1):75-80.
[21]胡国文,黄洪,傅和青,等.MMA/BA共聚物改性的水性聚氨酯的合成与表征[J].化工学报,2007,58(7):1851-1856.
[22]WANG G,DOU B,WANG J,et al.Adsorption properties of benzene and water vapor on hyper-cross-linked polymers[J].Rsc Advances,2013,3(43):20523-20531.
[23]FANG H,WANG H,SUN J,et al.Tailoring elastomeric properties of waterborne polyurethane by incorporation of polymethyl methacrylate with nanostructural heterogeneity[J].RSC Advances,2016,6(16):13589-13599.
[24]林晓琼,夏正斌,雷亮.聚丙烯涂饰用有机硅改性丙烯酸聚合物乳液的合成及表征[J].高分子材料科学与工程,2015,31(4):1-5.
[2]DU Y F,SHII P W,LI Q Y,et al.Effect of poly(sodium4-styrenesulfonate)modified carbon black on the dispersion and properties of waterborne polyurethane nanocomposites[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2014,454:1-7.
[3]LI W Y,CAO Y M,ZHOU X Q.Study on UV curable waterborne polyurethane modified by epoxy resin-[C]//Applied Mechanics and Materials.Trans Tech Publications,2013,249:842-848.
[4]JI X,ZHOU Y,ZHANG B,et al.Polydimethyl siloxane and castor oil comodified waterborne polyurethane[J].Isrn Polymer Science,2013,2013(7):1-10.
[5]TENG Y,YANG Z H,ZHOU X H,et al.Preparation and characterization of carboxylate/sulfonate composite WPU emulsion adhesive[J].Ciesc Journal,2015,66:4258-4267.
[6]LI J,ZHANG X,GOOCH J,et al.Photo-and p H-sensitive azo-containing cationic waterborne polyurethane[J].Polymer Bulletin,2015,72(4):881-895.
[7]OTTS D B,DUTTA S,ZHANG P,et al.Synthesis and phase separation during film formation of novel methyl methacrylate/n-butyl acrylate/methacrylic acid(MMA/BA/MAA)hybridurethane/acrylate colloidal dispersions[J].Polymer,2004,45:6235-6243.
[8]费贵强,杨小芳,王海花,等.不同软硬度比值下酮肼交联聚氨酯丙烯酸酯材料的原位聚合与性能[J].陕西科技大学学报,2017,35(5):104-110.
[9]刘新浩,李敏灵,吕婕,等.TMPMH扩链剂合成磺酸型水性聚氨酯的性能研究[J].聚氨酯工业,2017,32(1):19-22.
[10]LIN W T,LEE W J.Effects of the NCO/OH molar ratio and the silica contained on the properties of waterborne polyurethane resins[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2017,522:453-460.
[11]EL GHAFFAR M A A,SHERIF M H,EL-HABAB A T.Novel high solid content nano siliconated poly(Veo Va-acrylate)terpolymer latex for high performance latex paints[J].Chemical Engineering Journal,2016,301:285-298.
[12]YANG L,ZHAO T B,QU X L,et al.Synthesis of waterborne polyurethane modiifed by Nano-Si O2silicone and properties of the WPU coated RDX[J].中国炼油与石油化工:英文版,2015,19:39-45.
[13]张心亚,孙志娟,黎永津,等.有机硅氧烷改性丙烯酸酯乳液的聚合稳定性分析[J].涂料工业,2005,35(5):11-15.
[14]ZHONG X M,LIN J,WANG Z P,et al.Preparation of a crosslinked coating containing fluorinated water-dispersible polyurethane particles[J].Progress in Organic Coatings,2016,99:216-222.
[15]GONG J L,LIU G J,ZHANG G X,et al.Effect of polymeric emulsifier and ratio of soft/hard monomer on the property of acrylic emulsion as fabric stiffening agent[J].Advanced Materials Research,2013(821-822):287-294.
[16]PASCUAL B,GOI I,GURRUCHAGA M.Characterization of new acrylic bone cement based on methyl methacrylate/1-hydroxypropyl methacrylate monomer.[J].Journal of Biomedical Materials Research Part B Applied Biomaterials,2015,48(4):447-457.
[17]文秀芳,朱百福,程江,等.自交联型有机硅氧烷改性丙烯酸乳液的合成[J].高校化学工程学报,2004,18(3):308-313.
[18]林晓琼.聚丙烯涂饰用丙烯酸酯乳液的制备及性能研究[D].广州:华南理工大学,2015.
[19]丁长波.IPN型水性聚氨酯-丙烯酸酯复合乳液的制备及性能研究[D].西安:西安工程大学,2016.
[20]狄剑锋,刘裕文,纪凤龙.交联型有机硅改性聚氨酯丙烯酸酯乳液的合成及其性能[J].纺织学报,2016,37(1):75-80.
[21]胡国文,黄洪,傅和青,等.MMA/BA共聚物改性的水性聚氨酯的合成与表征[J].化工学报,2007,58(7):1851-1856.
[22]WANG G,DOU B,WANG J,et al.Adsorption properties of benzene and water vapor on hyper-cross-linked polymers[J].Rsc Advances,2013,3(43):20523-20531.
[23]FANG H,WANG H,SUN J,et al.Tailoring elastomeric properties of waterborne polyurethane by incorporation of polymethyl methacrylate with nanostructural heterogeneity[J].RSC Advances,2016,6(16):13589-13599.
[24]林晓琼,夏正斌,雷亮.聚丙烯涂饰用有机硅改性丙烯酸聚合物乳液的合成及表征[J].高分子材料科学与工程,2015,31(4):1-5.