硅烷化纳米SiO_2改性酚醛泡沫的性能表征
|
摘要
采用溶胶-凝胶法制备纳米SiO_2,并通过加入硅烷偶联剂1,1,3,3-四甲基二硅氧烷对纳米SiO_2进行硅烷化,用硅烷化后的纳米SiO_2制备改性酚醛树脂(PR1～PR6),将改性酚醛树脂制成相应的酚醛泡沫(PF1～PF6)。采用FT-IR、TGA/FT-IR和TGA等方法对酚醛树脂的性能进行表征和检测。测试结果表明:改性后的酚醛树脂成功引入硅烷化的纳米SiO_2,并与树脂发生了化学交联反应,形成Si—O—Si和Si—O;游离酚测试结果显示,随着纳米SiO_2含量的增加游离酚含量急剧下降,正硅酸四乙酯(TEOS)含量相同而硅烷偶联剂含量不同时对游离酚含量影响不大,当硅脂为3.22 g,硅烷偶联剂为2 g时与PR4组成时其效果最好;羟甲基含量检测结果显示随着纳米SiO_2含量的增加,羟甲基含量迅速增加至高值;机械性能测试显示,当硅脂质量分数为0.5%(以酚醛树脂的质量计),硅烷偶联剂为0.3%时,PF4的弯曲强度和抗压强度较PF1分别提高了73.3%和83.4%,较好地提高了泡沫的机械性能。
Nano-SiO_2 was prepared by sol-gel method. Then the silanization of nano-SiO_2 was carried out by adding silane coupling agent 1,1,3,3-tetramethyldisiloxane and obtained a silanized nano-SiO_2 that was used to modify phenolic resins(PR1-PR6). These modified phenolic resins were then converted into the corresponding phenolic foam(PF1-PF6). FT-IR, TGA/FT-IR and TGA were applied to investigated the properties of these modified phenolic resins. The test results showed that the modified phenolic resin has successfully incorporated silanized nano-silica via the chemical crosslinking reaction that formed Si—O—Si and Si—O bonds. Free phenol test results showed that with the increase of nano-silica content, the free phenol content drastically decreased. However, the same content of tetraethoxysilane(TEOS) with the different content of silane coupling agent had little effect on the free phenol content. When the silicone grease was 3.22 g and the silane coupling agent was 2 g, PR4 composition had the best performance. It was also found that with the increase of nano-silica content, the hydroxymethyl content rapidly increased to a high value. The mechanical properties test showed that when the mass fraction of silicone grease was 0.5%(calculated by the mass of phenolic resin,the same below)and the silane coupling agent was 0.3%, the flexural strength and compressive strength of PF4 were increased by 73.3% and 83.4% respectively, while compared with those of PF1, which resulted in the improve of the mechanical properties of the foam. In view of these test results, PF4 has exhibited the best modification effect and met the initial requirements.
Nano-SiO_2 was prepared by sol-gel method. Then the silanization of nano-SiO_2 was carried out by adding silane coupling agent 1,1,3,3-tetramethyldisiloxane and obtained a silanized nano-SiO_2 that was used to modify phenolic resins(PR1-PR6). These modified phenolic resins were then converted into the corresponding phenolic foam(PF1-PF6). FT-IR, TGA/FT-IR and TGA were applied to investigated the properties of these modified phenolic resins. The test results showed that the modified phenolic resin has successfully incorporated silanized nano-silica via the chemical crosslinking reaction that formed Si—O—Si and Si—O bonds. Free phenol test results showed that with the increase of nano-silica content, the free phenol content drastically decreased. However, the same content of tetraethoxysilane(TEOS) with the different content of silane coupling agent had little effect on the free phenol content. When the silicone grease was 3.22 g and the silane coupling agent was 2 g, PR4 composition had the best performance. It was also found that with the increase of nano-silica content, the hydroxymethyl content rapidly increased to a high value. The mechanical properties test showed that when the mass fraction of silicone grease was 0.5%(calculated by the mass of phenolic resin,the same below)and the silane coupling agent was 0.3%, the flexural strength and compressive strength of PF4 were increased by 73.3% and 83.4% respectively, while compared with those of PF1, which resulted in the improve of the mechanical properties of the foam. In view of these test results, PF4 has exhibited the best modification effect and met the initial requirements.
引文
[1]HIRANO K,ASAMI M.Phenolic resins-100 years of progress and their future[J].Reactive&Functional Polymers,2013,73(2):256-269.
[2]QI B,ZHENG C,LU H.Research and application of phenolic resin in the external thermal insulation and fire resistance composite system[J].Engineering Plastics Applications,2012,40(2):28-30.
[3]YANG C,ZHUANG Z H,YANG Z G.Pulverized polyurethane foam particlesreinforced rigid polyurethane foam and phenolic foam[J].Journal of Applied Polymer Science,2014,131(1):1-7[2018-03-01].https:∥doi.org/10.1002/app.39734.
[4]PILATO L.Phenolic resins:100 years and still going strong[J].Reactive&Functional Polymers,2013,73(2):270-277.
[5]SAZ-OROZCO B D,ALONSO M V,OLIET M,et al.Lignin particle-and wood flour-reinforced phenolic foams:Friability,thermal stability and effect of hygrothermal aging on mechanical properties and morphology[J].Composites Part B,2015,80:154-161.
[6]HERNANDEZPADRON G,ROJAS F,CASTANO V.Development and testing of anticorrosive SiO2/phenolic-formaldehydic resin coatings[J].Surface and Coatings Technology,2006,201(3):1207-1214.
[7]XU P J,JING X L.High carbon yield thermoset resin based on phenolic resin,hyperbranched polyborate,and paraformaldehyde[J].Polymer Advanced Technologies,2011,22(12):2592-2595.
[8]HU L H,ZHOU Y H,LIU R J,et al.Progress of bio-based phenolic foam[J].New Chemical Materials,2012,40(1):44-46.
[9]LIANG B C,LI X Y,HU L H,et al.Foaming resol resin modified with polyhydroxylated cardanol and its application to phenolic foams[J].Industrial Crops and Products,2016,80:194-196.
[10]ZHOU J,HU L H,LIANG B C.Preparation and characterization of novolac phenol-formaldehyde resins with enzymatic hydrolysis lignin.[J].Journal of the Taiwan Institute of Chemical Engineers,2015,54:178-182.
[11]HU L H,ZHOU Y H,LIU R J,et al.Synthesis of foaming resol resin modified with oxidatively degraded lignosulfonate[J].Industrial Crops and Products,2013,44:364-366.
[12]郭亚军,胡立红,张娜,等.纳米SiO2-木质素基酚醛泡沫的热稳定性及韧性表征[J].化工进展,2017,36(12):4569-4574.GUO Y J,HU L H,ZHANG N,et al.Characterization of thermal stability and toughness of nano-SiO2-lignin basedphenolic foam,[J]Chemical Industry and Engineering Progress,2017,36(12):4569-4574.
[13]HARAGUCHI K,USAMI Y,ONO Y.The preparation and characterization of hybrid materials composed of phenolic resin and silica[J].Journal of Materials Science,1998,33(13):3337-3344.
[14]PLUEDDEMANN E P.Silane Coupling Agents[M].2nd ed.New York:Plenum,1991:153-249.
[15]陈素芬,李波,刘一杨,等.三甲基硅烷化改性二氧化硅气凝胶[J].强激光与粒子束,2009,21(1):76-78.CHEN S F,LI B,LIU Y Y,et al.Trimethylsilyl substituent modification of silica aerogels[J].High Power Laser and Particle Beams,2009,21(1):76-78.
[16]崔旭,赵宝华,张立博,等.KH-560修饰纳米SiO2及其改性酚醛泡沫的制备和表征[J].化工新型材料,2015,43(11):101-104.CUI X,ZHAO B H,ZHANG L B,et al.Preparation and characterization of toughening phenolic foam with SiO2modified by coupling agent KH-560[J].New Chemical Materials,2015,43(11):101-104.
[17]赵容,任亚国,马家举.环氧基笼型倍半硅氧烷的合成研究[J].热固性树脂,2014,29(3):13-15.ZHAO R,REN Y G,MA J J.Synthesis of octa(γ-glycidyloxypropyl)octasilsesquioxane[J].Thermosetting Resin,2014,29(3):13-15.
[18]李亚坤,吴健伟,赵玉宇.仲氨基笼型倍半硅氧烷改性室温固化环氧树脂的研究[J].化学与粘合,2014,36(5):322-326.LI Y K,WU J W,ZHAO Y Y.The study on room temperature curing epoxy resin modified by SaPOSS[J].Chemistry and Bonding,2014,36(5):322-326.
[19]WANG M C,MATHEW L,XU C.Synthesis of phenol-formaldehyde resol resins using organosolv pine lignin[J].European Polymer Journal,2009,45(12):3380-3388.
[20]IBRAHIM M N M,ZAKARIA N,SIPAUT C S,et al.Chemical and thermal properties of lignins from oil palm biomass as a substitute for phenol in a phenol formaldehyde resin production[J].Carbohydrate Polymers,2011,86:112-119.
[21]WANG X,HU Y,SONG L,et al.Flame retardancy and thermal degradation mechanism of epoxy resin composites based on a DOPOsubstituted organophosphorus oligomer[J].Polymer,2010,51:2435-2445.
[22]TUDORACHI N,MUSTATA F.Thermal degradation and evolved gas analysis of some vegetable oils using TG/FT-IR/MS technique[J].Journal of Thermal Analysis and Calorimetry,2015,119(3):1703-1711.
[23]ZHANG W C,LI X M,YANG R J.Pyrolysis and fire behavior of epoxy resin composites based on a phosphorus-containing polyhedral oligomeric silsesquioxane(DOPO-POSS)[J].Polymer Degradation and Stability,2011,96(10):1821-1832.
[24]ZHANG X,LOONEY M G,SOLOMON D H,et al.The chemistry of novolac resins:3.13C and15N NMR studies of curing with hexamethylenetetramine[J].Polymer,1997,38(23):5835-5848.
[25]WANG J,JIANG H,HIANG N.Study on the pyrolysis of phenol-formaldehyde(PF)resin and modified PF resin[J].Thermochimica Acta,2009,496:136-142.
[26]STRE CKOVAM.MEDVECKyL’,FüZER J,et al.Design of novel soft magnetic composites based on Fe/resin modified with silica[J].Materials Letters.2013,101:37-40.
[2]QI B,ZHENG C,LU H.Research and application of phenolic resin in the external thermal insulation and fire resistance composite system[J].Engineering Plastics Applications,2012,40(2):28-30.
[3]YANG C,ZHUANG Z H,YANG Z G.Pulverized polyurethane foam particlesreinforced rigid polyurethane foam and phenolic foam[J].Journal of Applied Polymer Science,2014,131(1):1-7[2018-03-01].https:∥doi.org/10.1002/app.39734.
[4]PILATO L.Phenolic resins:100 years and still going strong[J].Reactive&Functional Polymers,2013,73(2):270-277.
[5]SAZ-OROZCO B D,ALONSO M V,OLIET M,et al.Lignin particle-and wood flour-reinforced phenolic foams:Friability,thermal stability and effect of hygrothermal aging on mechanical properties and morphology[J].Composites Part B,2015,80:154-161.
[6]HERNANDEZPADRON G,ROJAS F,CASTANO V.Development and testing of anticorrosive SiO2/phenolic-formaldehydic resin coatings[J].Surface and Coatings Technology,2006,201(3):1207-1214.
[7]XU P J,JING X L.High carbon yield thermoset resin based on phenolic resin,hyperbranched polyborate,and paraformaldehyde[J].Polymer Advanced Technologies,2011,22(12):2592-2595.
[8]HU L H,ZHOU Y H,LIU R J,et al.Progress of bio-based phenolic foam[J].New Chemical Materials,2012,40(1):44-46.
[9]LIANG B C,LI X Y,HU L H,et al.Foaming resol resin modified with polyhydroxylated cardanol and its application to phenolic foams[J].Industrial Crops and Products,2016,80:194-196.
[10]ZHOU J,HU L H,LIANG B C.Preparation and characterization of novolac phenol-formaldehyde resins with enzymatic hydrolysis lignin.[J].Journal of the Taiwan Institute of Chemical Engineers,2015,54:178-182.
[11]HU L H,ZHOU Y H,LIU R J,et al.Synthesis of foaming resol resin modified with oxidatively degraded lignosulfonate[J].Industrial Crops and Products,2013,44:364-366.
[12]郭亚军,胡立红,张娜,等.纳米SiO2-木质素基酚醛泡沫的热稳定性及韧性表征[J].化工进展,2017,36(12):4569-4574.GUO Y J,HU L H,ZHANG N,et al.Characterization of thermal stability and toughness of nano-SiO2-lignin basedphenolic foam,[J]Chemical Industry and Engineering Progress,2017,36(12):4569-4574.
[13]HARAGUCHI K,USAMI Y,ONO Y.The preparation and characterization of hybrid materials composed of phenolic resin and silica[J].Journal of Materials Science,1998,33(13):3337-3344.
[14]PLUEDDEMANN E P.Silane Coupling Agents[M].2nd ed.New York:Plenum,1991:153-249.
[15]陈素芬,李波,刘一杨,等.三甲基硅烷化改性二氧化硅气凝胶[J].强激光与粒子束,2009,21(1):76-78.CHEN S F,LI B,LIU Y Y,et al.Trimethylsilyl substituent modification of silica aerogels[J].High Power Laser and Particle Beams,2009,21(1):76-78.
[16]崔旭,赵宝华,张立博,等.KH-560修饰纳米SiO2及其改性酚醛泡沫的制备和表征[J].化工新型材料,2015,43(11):101-104.CUI X,ZHAO B H,ZHANG L B,et al.Preparation and characterization of toughening phenolic foam with SiO2modified by coupling agent KH-560[J].New Chemical Materials,2015,43(11):101-104.
[17]赵容,任亚国,马家举.环氧基笼型倍半硅氧烷的合成研究[J].热固性树脂,2014,29(3):13-15.ZHAO R,REN Y G,MA J J.Synthesis of octa(γ-glycidyloxypropyl)octasilsesquioxane[J].Thermosetting Resin,2014,29(3):13-15.
[18]李亚坤,吴健伟,赵玉宇.仲氨基笼型倍半硅氧烷改性室温固化环氧树脂的研究[J].化学与粘合,2014,36(5):322-326.LI Y K,WU J W,ZHAO Y Y.The study on room temperature curing epoxy resin modified by SaPOSS[J].Chemistry and Bonding,2014,36(5):322-326.
[19]WANG M C,MATHEW L,XU C.Synthesis of phenol-formaldehyde resol resins using organosolv pine lignin[J].European Polymer Journal,2009,45(12):3380-3388.
[20]IBRAHIM M N M,ZAKARIA N,SIPAUT C S,et al.Chemical and thermal properties of lignins from oil palm biomass as a substitute for phenol in a phenol formaldehyde resin production[J].Carbohydrate Polymers,2011,86:112-119.
[21]WANG X,HU Y,SONG L,et al.Flame retardancy and thermal degradation mechanism of epoxy resin composites based on a DOPOsubstituted organophosphorus oligomer[J].Polymer,2010,51:2435-2445.
[22]TUDORACHI N,MUSTATA F.Thermal degradation and evolved gas analysis of some vegetable oils using TG/FT-IR/MS technique[J].Journal of Thermal Analysis and Calorimetry,2015,119(3):1703-1711.
[23]ZHANG W C,LI X M,YANG R J.Pyrolysis and fire behavior of epoxy resin composites based on a phosphorus-containing polyhedral oligomeric silsesquioxane(DOPO-POSS)[J].Polymer Degradation and Stability,2011,96(10):1821-1832.
[24]ZHANG X,LOONEY M G,SOLOMON D H,et al.The chemistry of novolac resins:3.13C and15N NMR studies of curing with hexamethylenetetramine[J].Polymer,1997,38(23):5835-5848.
[25]WANG J,JIANG H,HIANG N.Study on the pyrolysis of phenol-formaldehyde(PF)resin and modified PF resin[J].Thermochimica Acta,2009,496:136-142.
[26]STRE CKOVAM.MEDVECKyL’,FüZER J,et al.Design of novel soft magnetic composites based on Fe/resin modified with silica[J].Materials Letters.2013,101:37-40.