【作者】 王峥；

【导师】 鲁在君；

【作者基本信息】 山东大学 ， 有机化学， 2020， 博士

【摘要】 苯并噁嗪树脂是一种新型的高性能热固性树脂。它具有优异的热性能、力学性能、阻燃性能、尺寸稳定性和灵活的分子设计性,并且已经在航空航天、运输、电子制造等领域得到应用。然而,目前开发的苯并噁嗪树脂大部分都是疏水性的,这限制了它在亲水性环境的应用,如表面活性剂、聚电解质等。因此,开发具有亲水性甚至是水溶性的苯并噁嗪树脂对拓宽它的应用领域具有十分重要的意义。本论文以开发含离子基团的功能性苯并噁嗪树脂为目标,通过从分子水平上引入离子基团,分别合成了两种阴离子型的苯并噁嗪表面活性剂和三种含磺酸基团、季铵基团、两性离子基团的交联聚苯并噁嗪薄膜,并对它们的合成与性能展开了系统的研究。本论文的主要内容和研究结果如下:第一部分:含羧酸基团的生物基苯并噁嗪表面活性剂以可再生的甘氨酸和腰果酚为原料经曼尼希反应(Mannich reaction)合成了生物基苯并噁嗪表面活性剂(Ca-g)。以Ca-g作为乳化剂制备了苯乙烯乳液和聚苯乙烯(PS)乳胶液。另外,我们还研究了 Ca-g的体外细胞毒性和它的甘油三酯乳液。结果表明:Ca-g表面活性剂可以高效地稳定苯乙烯乳液。仅加入浓度为1.7 w/v%的Ca-g就可以稳定苯乙烯体积比为90%的高内相乳液(HIPE)。更有趣的是,这些HIPE表现出了 pH敏感性。HIPE易于在pH=9.0-12.0的范围内形成。进一步,通过HIPE聚合制备了 PS乳胶粒。Ca-g对Hela细胞系表现出较低的毒性。基于Ca-g的O/W型甘油三酯乳液具有较好的储存稳定性和离心稳定性。这种基于氨基酸的生物基表面活性剂可能在日用清洁产品、化妆品领域有潜在的用途。第二部分:含磺酸基团的苯并噁嗪表面活性剂及其水性苯并噁嗪树脂以对羟基苯磺酸钠、正十二胺为原料经曼尼希反应合成了一种含磺酸基团的苯并噁嗪表面活性剂(SBZ)。用SBZ表面活性剂乳化疏水性的苯并噁嗪树脂(BZ),得到了一系列水性苯并噁嗪树脂(WBR)乳液。研究了 SBZ浓度和分散相体积比对WBR乳液行为的影响。进一步,通过直接将分散相体积比为50%的WBR乳液固化制备了聚苯并噁嗪薄膜。结果表明:SBZ具有较强的乳化能力。加入较低浓度的SBZ(2 w/v%),就可以得到高固含量(50-80 vol%)并且稳定的WBR乳液。WBR乳液固化后得到了具有柔韧性的透明聚苯并噁嗪薄膜。SBZ表面活性剂在开环聚合后融入到聚苯并噁嗪树脂的交联网络结构中。薄膜的拉伸强度和断裂伸长率分别为7.4 MPa和9.2%。它表现出优异的耐热性,玻璃化转变温度达到288℃。本工作为开发耐高温的环境友好型涂料提供了新的策略。第三部分:用于质子交换膜的含磺酸基团的苯并噁嗪树脂以对甲酚、苯胺和多聚甲醛为原料经曼尼希反应和开环聚合反应得到了苯并噁嗪齐聚物(PBZ)。随后,PBZ经磺化反应、离子交换反应成功得到了含磺酸基团的苯并噁嗪齐聚物(H-SPBZ)。最后,将H-SPBZ与双环苯并噁嗪单体共聚得到了含磺酸基团的聚苯并噁嗪交联膜(SPM)。详细研究了 SPM的导电性、甲醇渗透性、尺寸稳定性、氧化稳定性、耐热性和力学性能。结果表明:苯并噁嗪齐聚物的线性分子结构提高了成膜性,制得了 8 cm × 7 cm × 170μm尺寸的膜。所得SPM-15膜具有良好的力学性能。它的拉伸强度和断裂伸长率分别为9.6MPa和8.5%。SPM-15膜的导电率为25 mS/cm(80℃和100%相对湿度)。它的甲醇渗透性为 0.49 × 10-6 cm2/s,是 Nafion-117 膜的五分之一(2.37 × 10-6 cm2/s)。SPM-15膜表现出较强的氧化稳定性。经80℃的芬顿试剂(3 wt%H2O2+3 ppm FeSO4)处理后,失重率仅为1.3%,这与Nafion-117膜的氧化稳定性(1.5%)相当。SPM-15膜具有较高的尺寸稳定性,它在80℃的吸水率和溶胀度分别为12.8%和2.8%。另外,SPM-15膜还具有较好的耐热性。本工作为开发耐高温、高阻醇性的新型质子交换膜提供了新思路。第四部分:用于阴离子交换膜的含季铵基团的苯并噁嗪树脂以双酚A、4,4’-二氨基二苯甲烷、大麦芽碱和多聚甲醛为原料经曼尼希反应、季铵化反应以及离子交换得到了含季铵基团的主链型苯并噁嗪齐聚物(QBZ)。进一步,采用溶液浇铸法升温固化制得了含季铵基团的聚苯并噁嗪(PQBZ)交联膜。系统研究了 PQBZ膜的导电性能、甲醇渗透性、尺寸稳定性、碱稳定性、氧化稳定性、耐热性和力学性能。结果表明:主链型分子结构提高了它的成膜性,可以制备出尺寸为10 cm × 8 cm × 100 μm的膜。PQBZ膜的拉伸强度和断裂伸长率分别为11.9 MPa和12.8%。PQBZ840膜表现出较高的导电率58.5 mS/cm(80 ℃和100%相对湿度)。它的甲醇渗透性为2.7 × 10-8 cm2/s,比Nafion-117膜(2.37× 10-6 cm2/s)低两个数量级。PQBZ840膜表现出较好的碱稳定性和氧化稳定性,经1.0 mol/LKOH在60℃处理400小时导电率仍保留75.4%。经芬顿试剂(30%H2O2+30ppm FeSO4)在68℃加速氧化72小时后,PQBZ840膜的失重率为17.6%,远低于热塑性阴离子交换膜AMI-7001的失重率(42%)。与其他的报道的阴离子交换膜相比,PQBZ840膜还表现出了较好的尺寸稳定、较高的耐热性和力学性能。总之,这种新型聚苯并噁嗪薄膜表现出用于碱性甲醇燃料电池阴离子交换膜的较大潜力。第五部分:用于防污涂料的含两性离子基团的苯并噁嗪树脂以大麦芽碱、双酚A、4,4’-二氨基二苯甲烷和多聚甲醛为原料经曼尼希反应、季铵化反应合成了含磺基甜菜碱的苯并噁嗪单体和主链型苯并噁嗪齐聚物。进一步,采用溶液浇铸法经升温聚合得到了含磺基甜菜碱的聚苯并噁嗪交联膜。详细研究了聚苯并噁嗪交联膜的表面亲水性、防污性能、力学性能和热性能。结果表明:利用苯并噁嗪树脂的侧链叔胺基团与1,3-丙烷磺酸内酯反应简单、高效地将两性离子基团(磺基甜菜碱)引入到苯并噁嗪树脂中。含磺基甜菜碱的聚苯并噁嗪交联膜PSHM表现出了良好的亲水性,其静态接触角为74.8°。经PSHM功能化的表面具有优异防污性能,其蛋白吸附量减少98%。PSHM膜具有较好的力学性能,粘结强度和铅笔硬度分别为1级和6H。另外,它还表现出了优异的耐热性,玻璃化转变温度和热失重5%的温度分别为218℃和269℃。本工作提供了一种简单、高效的制备交联聚甜菜碱的方法,由此方法制备的PSHM在耐高温的防污涂料领域有应用潜力。更多还原

【Abstract】 Benzoxazine resins are a new class of high-performance thermosetting resins.It has excellent heat-resistance,mechanical property,flame retardancy,dimensional stability and high molecular design flexibility.It has been used in aerospace,transportation,electronics manufacturing,and other fields.However,most of the currently developed benzoxazine resins are hydrophobic,which limits their application in hydrophilic environments,such as surfactants,polyelectrolyte membranes.Therefore,the development of hydrophilic and even water-soluble benzoxazine resins is very meaningful to extend its application field.In this dissertation,we aim to develop functional benzoxazine resins containing ionic groups.By introducing ionic groups at the molecular level,two kinds of anionic benzoxazine surfactants and three kinds of cross-linked polybenzoxazine films containing sulfonic acid group,quaternary ammonium group,and zwitterionic group were synthesized,respectively.Synthesis and properties of these benzoxazine resins were systematically studied.The main contents and results of this dissertation are shown as follows:Part Ⅰ:carboxyl group-containing benzoxazine surfactant based on biomassA novel bio-based benzoxazine surfactant(Ca-g)was synthesized via a Mannich reaction using renewable glycine and cardanol as raw materials.Styrene containing emulsions and polystyrene(PS)latex were prepared based on Ca-g surfactant.In addition,the in vitro cytotoxicity of Ca-g and its triglceride emulsion were also investigated.These results showed that Ca-g surfactant exhibited high efficiency for stabilizing styrene emulsions.An addition of only 1.7 w/v%stabilized the high internal phase emulsion(HIPE)with styrene volume fraction up to 90%.More interestingly,HIPE exhibited a pH-sensitive property and was easily formed at pH values from 9.0 to 12.0.Furthermore,polystyrene latex particles were obtained via HIPE polymerization.Ca-g showed lower cytotoxicity against the Hela cell line.A stable triglceride-in-water emulsion stabilized by Ca-g was prepared.The bio-based Ca-g surfactant may have potential use in cosmetics and daily cleaning products.Part Ⅱ:sulfonic acid group-containing benzoxazine surfactant and its waterborne benzoxaizne resinsA sulfonic acid group-containing benzoxazine surfactant(SBZ)was synthesized via a Mannich reaction using sodium 4-hydroxybenzenesulfonate and n-dodecylamine as raw materials.SBZ surfactant was used to emulsify the hydrophobic benzoxazine resin(BZ).A series of waterborne benzoxazine resin(WBR)emulsions were prepared.The effects of SBZ concentration and oil-water ratio on the behavior of WBR emulsions were studied.Furthermore,polybenzoxazine film was prepared by curing a WBR emulsion with 50 vol%BZ.The results showed that SBZ had a strong emulsifying capacity.The lower concentration of SBZ(2 w/v%)stabilized high solid content(50-80 vol%)and stable WBR emulsions.After curing the WBR emulsion,a transparent and flexible polybenzoxazine film was fabricated.The SBZ surfactants were incorporated into the benzoxazine resin matrix after ring-opening polymerization.The tensile strength and elongation at break of the film were 7.4 MPa and 9.2%,respectively.The film exhibited excellent heat resistance with a glass transition temperature of 288℃.This work provides a new strategy for the development of high heat-resistant and environmentally friendly waterborne benzoxazine coatings.Part Ⅲ:sulfonic acid group-containing benzoxazine resin for proton exchange membraneA benzoxazine oligomer(PBZ)was synthesized through Mannich reaction and ring-opening polymerization using p-cresol,aniline and paraformaldehyde as raw materials.Subsequently,sulfonic acid group-containing benzoxazine oligomer(H-SPBZ)was obtained through sulfonation of PBZ and followed by ion exchange reaction.Finally,cross-linked polybenzoxazine membranes(SPM)containing sulfonic acid group were fabricated by copolymerizing H-SPBZ with bisbenzoxazine monomer.Properties of SPM membranes including conductivity,methanol permeability,oxidative stability,dimensional stability,heat resistance,and mechanical property were studied in detail.The results showed that the linear type molecular design of benzoxazine oligomer improved the film-forming property.A membrane with a size of 8 cm × 7 cm × 170 μm was fabricated.SPM-15 membrane had good mechanical property.Its tensile strength and elongation at break were 9.6 MPa and 8.5%,respectively.Its conductivity was 25 mS/cm at 80℃ and 100%relative humidity.Its methanol permeability was 0.49 × 10-6 cm2/s,which was about one fifth of the value of Nafion-117 membrane(2.37 × 10-6 cm2/s).The membrane exhibited good oxidation stability.After treatment in Fenton’s reagent(3 wt%H2O2+3 ppm FeSO4)at 80℃,the weight loss percent of SPM-15 membrane was 1.3%,which was comparable to that of Nafion-117 membrane(1.5%).The SPM-15 membrane also presented better dimensional stability.The water uptake and swelling ratio at 80℃ were 12.8%and 2.8%,respectively.In addition,SPM-15 membrane had good heat resistance.This work provides a new idea for the development of high heat-resistant and alcohol resistant proton exchange membrane.Part Ⅳ:quaternary ammonium group-containing benzoxazine resin for anion exchange membraneNovel quaternary ammonium group-containing main-chain benzoxazine oligomers(QBZs)were synthesized via Mannich reaction,quaternization,and ion exchange reaction using bisphenol A,4,4’-diaminodiphenyl methane,hordenine,and paraformaldehyde as raw materials.Furthermore,the cross-linked polybenzoxazine(PQBZ)membranes containing quaternary ammonium were fabricated using solution casting and programmed temperature curing methods.Properties of PQBZ membranes including conductivity,methanol permeability,dimensional stability,alkaline stability,oxidative stability,heat resistance,and mechanical property were systematically studied.The results showed that the main-chain type molecular design of QBZ improved the film-forming property.A large membrane with a size of 10 cm × 8 cm ×100 μm was prepared.The tensile strength and the elongation at break of PQBZ membrane were 11.9 MPa and 12.8%,respectively.The PQBZ840 membrane exhibited a higher hydroxide conductivity of 58.5 mS/cm at 80℃ and 100%relative humidity.It showed a very low methanol permeability of 2.7 × 10-8 cm2/s,which was near two orders of magnitude lower than that of Nafion-117 membrane(2.37 × 10-6 cm2/s).The membrane had good alkaline stability and oxidation stability.After 400 hours of treatment in 1.0 M KOH at 60℃,75.4%of hydroxide conductivity was retained.After 72 hours of treatment in Fenton’s reagent(30%H2O2+30 ppm FeSO4)at 68 ℃,the weight loss percent of PQBZ840 membrane was 17.6%,which was much less than that of AMI-7001 anion exchange membrane(42%).Compared with other reported anion exchange membranes,the PQBZ840 membrane also presented better dimensional stability,higher heat resistance,and mechanical property.Overall,this novel polybenzoxazine membrane shows great potential for anion exchange membrane in alkaline methanol fuel cell.Part V:zwitterionic group-containing benzoxazine resin for antifouling coatingSulfobetaine group-containing benzoxazine monomer and main-chain benzoxazine oligomer were synthesized via Mannich reaction and quaternization using hordenine,bisphenol A,4,4’-diaminodiphenyl methane,and paraformaldehyde as raw materials.Furthermore,the cross-linked polybenzoxazine membranes containing sulfobetaine group were fabricated using solution casting and programmed temperature curing methods.Properties of the cross-linked polybenzoxazine membranes including surface hydrophilicity,antifouling property,mechanical property,and thermal stability were studied in detail.The results showed that the reaction of the tertiary amine group in the side chain of benzoxazine monomer(or main-chain benzoxazine oligomer)with 1,3-propane sultone can easily and efficiently introduce zwitterionic group(sulfobetaine)into benzoxazine resin.The sulfobetaine group-containing PSHM membrane exhibited good hydrophilicity with a static contact angle of 74.8°.The PSHM functionalized surface showed excellent antifouling property,which reduced protein adsorption by 98%compared to the bare surface.It presented good mechanical properties.The adhesion strength and pencil hardness were grade 1 and 6 H,respectively.In addition,it had good heat-resistant property.Its glass transition temperature and the temperature of 5%weight loss were 218℃ and 269℃,respectively.This work provides a simple and efficient method for preparing cross-linked polysulfobetaines.The PSHM prepared by this method has potential application in the field of high heat-resistant antifouling coatings.更多还原