巯基硅氧烷改性星形聚氨酯-丙烯酸酯乳液的制备与性能
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摘要
采用二聚酸二异氰酸酯(DDI)、γ-巯基丙基三甲氧基硅烷(Prop S-SH)、甲基丙烯酸羟乙酯(HEMA)为原料,合成出线型含硅聚氨酯低聚物;以聚己内酯三元醇(PCL 3091)化合物为核心,异佛尔酮二异氰酸酯(IPDI)、磺酸型聚酯二元醇(BY 3301)、季戊四醇三丙烯酸酯(PETA)为原料,合成出支臂状磺酸型聚氨酯低聚物;将2种不同低聚物与丙烯酸酯类单体进行共聚,制备出巯基硅氧烷改性星形聚氨酯-丙烯酸酯乳液。通过红外光谱、扫描电镜、热重分析和水接触角等对材料进行表征,并探究了Prop S-SH用量对胶膜耐水性、热性能以及力学性能的影响。结果表明,当Prop S-SH质量分数为8%时,乳液粒径平均为117 nm,膜表面有明显的凸起现象,光泽度为37°±1. 2°,胶膜吸水率为5. 1%±0. 2%,水接触角为105. 6°±0. 5°,此时胶膜的综合性能最佳,其拉伸强度为(19. 1±0. 4) MPa,邵氏硬度为(51±0. 6) HA,热失重在10%和50%的分解温度分别为306. 9℃和386. 0℃。与未改性胶膜相比,耐水性和耐热性均有显著提高。
A linear silicon modified polyurethane oligomer was prepared from dimer acid diisocyanate( DDI),( 3-mercaptopropyl) trimethoxysilane( PropS-SH) and hydroxyethyl methacrylate( HEMA). Using polycaprolactone three alcohol( PCL3091) as core,isocyanate( IPDI),sulfonated polyester diol( BY3301) and pentaerythritol three acrylates( PETA) as raw material,arm shaped sulfonic acid type polyurethane oligomers were prepared. Two kinds of oligomers were copolymerized with acrylic monomers to prepare silicone modified crosslinking polyurethane acrylate emulsion. The structure and properties of polymer were characterized by FT-IR,SEM,TG and water contact angle measurement; and effects of the Props-SH contents on the water resistance,mechanical properties and thermal properties of the film were studied. The results show that when the PropS-SH mass fraction is 8%,the emulsion particle size is averaged at 117 nm,the surface of the film has obvious protruding phenomenon and the glossiness is 37° ± 1. 2°; the film absorption rate is 5. 1% ± 0. 2% and the water contact angle is 105. 6° ± 0. 5°,the comprehensive performance of the film is the best,the tensile strength is( 19. 1 ± 0. 4) MPa,and the shore hardness is( 51 ± 0. 6) HA,the decomposition temperatures at10% and 50% mass loss are 306. 9 ℃ and 386. 0 ℃ respectively,and the water resistance and heat resistance are improved significantly compared with the unmodified film.
A linear silicon modified polyurethane oligomer was prepared from dimer acid diisocyanate( DDI),( 3-mercaptopropyl) trimethoxysilane( PropS-SH) and hydroxyethyl methacrylate( HEMA). Using polycaprolactone three alcohol( PCL3091) as core,isocyanate( IPDI),sulfonated polyester diol( BY3301) and pentaerythritol three acrylates( PETA) as raw material,arm shaped sulfonic acid type polyurethane oligomers were prepared. Two kinds of oligomers were copolymerized with acrylic monomers to prepare silicone modified crosslinking polyurethane acrylate emulsion. The structure and properties of polymer were characterized by FT-IR,SEM,TG and water contact angle measurement; and effects of the Props-SH contents on the water resistance,mechanical properties and thermal properties of the film were studied. The results show that when the PropS-SH mass fraction is 8%,the emulsion particle size is averaged at 117 nm,the surface of the film has obvious protruding phenomenon and the glossiness is 37° ± 1. 2°; the film absorption rate is 5. 1% ± 0. 2% and the water contact angle is 105. 6° ± 0. 5°,the comprehensive performance of the film is the best,the tensile strength is( 19. 1 ± 0. 4) MPa,and the shore hardness is( 51 ± 0. 6) HA,the decomposition temperatures at10% and 50% mass loss are 306. 9 ℃ and 386. 0 ℃ respectively,and the water resistance and heat resistance are improved significantly compared with the unmodified film.
引文
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[3] Li B,Xin X,Liu H,et al. Synthesis and properties of polyurethaneacrylate hybrid emulsion via monomer dilution method and emulsification method[J]. Prog. Org. Coat.,2017,112:263-269.
[4] Yuan C,Wang M,Li H,et al. Preparation and properties of UV-curable waterborne polyurethane-acrylate emulsion[J]. J. Appl. Polym.Sci.,2017,134:45208.
[5]黄家健,周闯,周健,等.蓖麻油基UV固化聚氨酯丙烯酸酯的合成及固化膜性能[J].高分子材料科学与工程,2016,32(4):23-29.Huang J J,Zhou C,Zhou J,et al. Synthesis of castor oil-based UVcurable PUA and properties of the cured film[J]. Polymer Materials Science&Engineering,2016,32(4):23-29.
[6] Llorente O,Fernández-Berridi M J,González A,et al. Study of the crosslinking process of waterborne UV curable polyurethane acrylates[J]. Prog. Org. Coat.,2016,99:437-442.
[7] Ma L,Song L,Li F,et al. Preparation and properties of poly(propylene carbonate)-based waterborne polyurethane-acrylate composite emulsion[J]. Colloid Polym. Sci., 2017, 295:2299-2307.
[8] Yong Q,Nian F,Liao B,et al. Synthesis and characterization of solvent-free waterborne polyurethane dispersion with both sulfonic and carboxylic hydrophilic chain-extending agents for matt coating applications[J]. RSC Adv.,2015,5:107413-107420.
[9]闰彦玲,杨建军,吴庆云,等.乙二胺化氧化石墨烯改性超支化聚氨酯-含丙烯酸酯复合乳液的制备与表征[J].高分子材料科学与工程,2017,33(9):112-119.Run Y L,Yang J J,Wu Q Y,et al. Preparation of poly(ethylenediamined graphene oxide/acrylate)-waterborne hyperbranched polyurethane hybrid latexes[J]. Polymer Materials Science&Engineering,2017,33(9):112-119.
[10]杨红光,杨建军,吴庆云,等.含硅聚氨酯改性水性环氧固化剂的制备与性能[J].精细化工,2017,34(5):582-587.Yang H G,Yang J J,Wu Q Y,et al. Preparation and Properties of waterborne epoxy curing agent modified by polyurethane contained silicon[J]. Fine Chemicais,2017,34(5):582-587.
[11] Sow C,Riedl B,Blanchet P. UV-waterborne polyurethane-acrylate nanocomposite coatings containing alumina and silica nanoparticles for wood:mechanical,optical,and thermal properties assessment[J]. J. Coat. Technol. Res.,2011,8:211-221.
[12] Wan S,Li Y,Peng J,et al. Synergistic toughening of graphene oxide-molybdenum disulfide-thermoplastic polyurethane ternary artificial nacre[J]. ACS Nano,2015,9:708-714.