AB型顺式聚对苯撑苯并二唑新单体的合成与应用研究

合成了AB型顺式聚对苯撑苯并二(噁)唑(PBO)新单体:5-氨基-6-羟基-2-(对甲氧羰基苯基)苯并(噁)唑(MAB)和5-氨基-6-羟基-2-(对羧基苯基)苯并(噁)唑(ABA),阐述了AB型新单体的分子结构特征,并测定了抗氧化及热分解性能,探索了新单体在自缩聚反应制备PBO树脂中的应用.结果表明:采用以4-氨基-6硝基间苯二酚盐酸盐和对苯二甲酸单甲酯为原料,依次经酰氯化、缩环合、加氢还原及其碱性水解的合成路线,可分别成功地获得纯度98%的MAB和 99%的ABA,它们在高温均缩聚的应用中无需抗氧剂即可方便制得PBO树脂.最后为进一步提升PBO材料的性能,以新的思路提出PBO改性等方面的研究途径.     

PDMDAAC共聚改性用反应性单体的合成及表征

该文合成了3种具有反应性功能的单体,为获得聚二甲基二烯丙基氯化铵(PDMDAAC)改性固色剂提供基础;以二烯丙基甲基胺、二烯丙基胺、三烯丙基胺及环氧氯丙烷为原料,分别合成了(3-氯-2-羟丙基)甲基二烯丙基氯化铵(CHMDAAC)、N,N-二烯丙基-3-羟基杂氮环丁烷氯化铵(DHAC)及(3-氯-2-羟丙基)三烯丙基氯化铵(CHTAAC)等反应性功能单体,对其结构进行了分析表征,并考察了其与基准单体二甲基二烯丙基氯化铵(DMDAAC)的共聚反应性。结果表明,所得单体具有预期结构,其收率为70%～95%,且与基准单体DMDAAC间可发生有效共聚;可用于合成新的棉织物活性染料无醛固色剂用反应性PDMDAAC共聚改性聚合物。     

界面缩聚法制备主链液晶离聚物及其表征

采用界面缩聚的方法,以异山梨醇为刚性基元、柔性基元癸二酰氯、离子基元灿烂黄为主要原料,合成了热致性主链液晶离聚物.通过傅立叶转换红外光谱(FT-IR))对其结构进行了表征,采用偏光显微镜(POM)、示差扫描量热仪(DSC)和广角X射线(X-ray)等手段对其液晶性能进行了表征.结果表明:该离聚物为近晶A型热致液晶,随着离子基元的加入及含量的变化对液晶性和液晶类型都没有影响.     

新型热稳定剂马来海松酸镧的合成及应用研究

以马来海松酸和乙酸镧为原料,采用溶剂法合成了马来海松酸镧(MPALa)。研究了原料物质的量比、温度和时间对产物的影响,并利用傅里叶红外光谱仪、扫描电镜(带能谱仪)和X射线衍射仪对产物进行分析和表征。另外,通过刚果红试纸法和热烘箱老化法研究了MPALa作为热稳定剂对聚氯乙烯(PVC)热稳定性的影响。结果表明:马来海松酸中的—COO-与La3+发生了化学键合,生成了非晶态的MPALa。最佳反应条件为马来海松酸和乙酸镧的物质的量比n马来海松酸:n乙酸镧=1:1.8、反应温度60℃、反应时间6 h,产率可达95%以上。此外,MPALa具有较好的热稳定效果,是一种环保型PVC热稳定剂。     

HNC-1新型光敏剂的合成与表征

合成了一种光敏剂2-三氯甲基-5-[β-(2-苯并呋喃)乙烯基]-1，3，4-噁二唑(HNC-1)。并用紫外光谱、红外光谱、核磁共振(氢、碳)谱，对产物进行了结构表征。     

丙交酯单体的回收和表征

为减少在提纯粗丙交酯时的大量耗损,采用不同方法对粗丙交酯在重结晶过程中产生的乙酸乙酯母液进行回收,并比较了各种方法的回收率。最后用紫外光谱和红外光谱对回收的丙交酯进行表征,测试结果表明产物为环状丙交酯结构,采用辛酸亚锡作催化剂是一种高产率的回收方法。     

新型非离子型自乳化水性环氧树脂固化剂的合成与表征

采用十八胺与乙二醇二缩水甘油醚反应,制得一种两端为环氧基,中间氮原子上接有长疏水烷基链的功能性双环氧基化合物,再用脂三乙烯四胺对该化合物进行封端,制得一种非离子型水性环氧固化剂.研究表明:由于该固化剂具有疏水效果的长烷基链和亲水效果的羟基、胺基、醚键,从而使得该固化剂具有表面活性剂的结构.因此相对其他水性固化剂来讲,该固化剂不仅仅不需要采用中和剂就具有亲水性,且其对环氧树脂有良好的乳化效果.该固化剂与液体环氧树脂所制备的双组分室温固化涂膜性能优良,具有优异的铅笔硬度、耐冲击性和耐化学性.同时该固化剂含有较长的柔性烷基链,所以固化后的环氧树脂将有较好的柔韧性.     

活性稀释剂苄基缩水甘油醚丙烯酸酯的合成及性能表征

本文以苄基缩水甘油醚和丙烯酸为原料合成活性稀释剂苄基缩水甘油醚丙烯酸酯(BGEA),研究了反应温度、催化剂和阻聚剂用量对反应的影响.结果表明最佳的反应条件为:反应温度110℃左右,催化剂N,N’-二甲基苄胺质量分数为0.9%,阻聚剂对甲氧基苯酚质量分数为0.2%.后将BGEA作为稀释剂加入到双酚A型环氧丙烯酸树脂中配制成光固化涂料,利用TG、AFM等表征手段对光固化膜的热性能、表面形貌及物理机械性能进行研究.     

新型氨基硫脲类Schiff碱配体的合成及结构表征

用 0 .0 5mol烯丙基异硫氰酸酯和 9.5mL质量分数为 5 0 %的水合肼溶液反应 ,制得 6 3g新的烃基取代的氨基硫脲类化合物——— 4 烯丙基氨基硫脲 (Ⅰ)白色晶体。首先用 0 0 1mol联乙酰分别与 0 0 2mol化合物Ⅰ及 0 0 2mol氨基硫脲缩合 ,合成了收率为 71%的联乙酰双缩 ( 4 烯丙基氨基硫脲 ) (Ⅱ)和收率为 70 %的联乙酰双缩氨基硫脲 (Ⅲ)两种新的含硫脲基Schiff碱。其次用 10mmol环己酮与 10mmol化合物Ⅰ在 30mL无水乙醇中 ,电磁搅拌 ,回流反应 2h ,合成出 1 8g环己酮缩烯丙基氨基硫脲 (Ⅳ )淡黄色晶体。最后将 0 0 1mol化合物Ⅰ分别与 0 0 0 5mol水合茚三酮及 1 0g乙二醛缩合 ,合成了两种新的含硫脲基的双Schiff碱型配体——— 1 6g茚三酮二缩 ( 4 烯丙基氨基硫脲 ) (Ⅴ)桔红色晶体和 1 2g乙二醛二缩 ( 4 烯丙基氨基硫脲 ) (Ⅵ )浅黄色粉末。对所合成的 5种新的含硫脲基Schiff碱配体 ,通过元素分析 ,IR ,1HNMR和MS表征了它们的结构。初步测试了它们对部分金属离子的配位性能。该合成方法具有操作简便、反应条件温和、产率高等优点     

甲醛异丁烯热缩合合成3-甲基-3-丁烯-1-醇的研究

以甲醇为溶剂,甲醛溶液和异丁烯为原料,通过Ene反应在无催化剂条件下合成了3-甲基-3-丁烯-1-醇(MBOH),系统考察了反应温度、反应压力、物料配比和反应时间对MBOH收率的影响。结果表明:一定温度是保证该反应进行的前提,当反应温度超过498 K后,MBOH的收率下降;反应压力对反应起促进作用,压力越大,MBOH的收率越高。在n(异丁烯)∶n(甲醛)=9∶1,反应温度为498 K,压力为11.0 MPa的最佳反应条件下,反应6 h后MBOH的收率可达59.24%。     

新型IT-SOFC阴极材料的合成和表征

以La（NO3）3·6142O、Ni（N03）2·6H2O和Co（NO3）2·6H2O为原料,尿素为燃料,采用凝胶低温燃烧技术合成L％Ni0．7C00．304粉体,利用各种分析方法粉体进行研究。X射线衍射分析表明：适当提高尿索在凝胶中的含量,燃烧后得到的粉体晶粒尺寸显著减小,未经燃烧的粉体中除含有La2Ni0.7Co0．3O4外,还有h2O3、CoO、La2cO5等杂质相。扫描电镜观察发现,随着锻烧温度的提高,La2NiO．7C00．304粉体的粒径有所增大,且远小于在相同锻烧条件下用固相反应法制备的La2Ni0.7Co0．304。采用低温燃烧法能够合成具有单一相结构的La2Ni0．7Co0．3O4粉体。     

Characterization of Acid-Neutralizing Basic Monomers in Co-Solvent Systems by NMR

Metabolic activity of the oral microbiota leads to acidification of the microenvironment and promotes demineralization of tooth structure at the margin of composite restorations. The pathogenic impact of the biofilm at the margin of the composite restoration could be reduced by engineering novel dentin adhesives that neutralize the acidic microenvironment. Integrating basic moieties into methacrylate derivatives has the potential to buffer against acid-induced degradation, and we are investigating basic monomers for this purpose. These monomers must be compatible with existing formulations, which are hydrophobic and marginally miscible with water. As such, co-solvent systems may be required to enable analysis of monomer function and chemical properties. Here the authors present an approach for examining the neutralizing capacity of basic methacrylate monomers in a water/ethanol co-solvent system using nuclear magnetic resonance (NMR) spectroscopy. NMR is an excellent tool for monitoring the impact of co-solvent effects on pKa and buffering capacity of basic monomers because chemical shift is extremely sensitive to small changes that most other methods cannot detect. Because lactic acid (LA) is produced by oral bacteria and is prevalent in this microenvironment, it was used to analyze the effectiveness of basic monomers to neutralize acid. The ¹³C chemical shift of the carbonyl in LA was monitored as a function of ethanol and monomer concentration and each was correlated with pH to determine the functional buffering range. This study shows that the buffering capacity of even very poorly water-soluble monomers can be analyzed using NMR.     

新型有机金属骨架化合物的合成与表征

以1,10-邻菲罗啉为原料,与溴反应生成3,8-二溴-1,10-菲罗啉,然后用浓硫酸和浓硝酸的混合溶液氧化成3,8-二溴-1,10-菲罗啉-5,6-二酮。各中间体和目标产物经MS和1H NMR表征确认。     

Synthesis and Thermal Characterization of Novel Fluorene-Based Polysiloxane Derivatives

Three novel poly(tetramethylsilfluorenylenesiloxane) derivatives having different substituent at 9-position of fluorenylene moiety, i.e. dimethyl (P1), spirocyclohexyl (P2), and spirofluorenyl (P3) substituents, were obtained by polycondensation of novel three disilanol monomers, i.e. 2,7-bis(dimethylhydroxysilyl)-9,9-dimethyl- fluorene (M1), 2’,7’-bis(dimethylhydroxysilyl)-spiro(cyclohexane-1,9’-fluorene) (M2), 2,7-bis(dimethylhydroxysilyl)-9,9’-spirobifluorene (M3), respectively. P1–P3 exhibited the good solubility in common organic solvents, such as tetrahydrofuran (THF), chloroform, dichloromethane, and toluene. It was suggested from the differential scanning calorimetry (DSC) and the X-ray diffraction analysis that P1 exhibited the crystallinity whereas P2 and P3 were amorphous polymers. The glass transition temperature (T _g) determined by DSC and the temperature at 5% weight loss (T _d5) determined by thermogravimetry (TG) were dependent on the substituent at 9-position on fluorene; both orders of T _g and T _d5 were P3 > P2 > P1, indicating the bulkiness of substituent at 9-position of fluorene resulted in the good thermal stability. It is noteworthy that amorphous P3 exhibiting very high T _g of 156 °C and T _d5 of 535 °C is a new heat-resistant polysiloxane derivative as well as a promising candidate for blue-light-emitting materials.     

一种新型聚氯乙烯用锌基热稳定剂的合成及性能研究

以N1,N3-双(水杨醛)缩二乙烯三胺(H2L)和二水合乙酸锌为原料合成了一种含锌产物Zn-I(Zn3(HL)2Ac4,HAc=乙酸)。静态老化和脱氯化氢实验研究表明:在延缓聚氯乙烯(PVC)试样初期变色和锌烧方面,Zn-I和硬脂酸钙(Ca St2)的复合体系较硬脂酸锌(Zn St2)和Ca St2体系具有明显的优势。并且,在含Ca St2/含锌组分质量比从1.5/0到0/1.5范围内,随着Zn-I在复合体系中的质量份比例升高,PVC试样锌烧时间变短的趋势相比于Zn St2明显较缓。热分析动力学计算结果表明:随着Zn-I质量份比例升高,PVC样品的热分解活化能提高。     

功能单体改性苯丙乳液的合成研究

采用甲基丙烯酸脲杂环和反应型有机硅为功能单体、过硫酸钾为引发剂,对苯丙乳液进行改性及合成研究;并对实验工艺、乳化剂的配比、引发剂的浓度、不同功能单体对苯丙乳液性能的影响进行讨论分析。结果表明,当十二烷基苯磺酸钠：辛基酚聚氧乙烯醚质量比为2：1时,过硫酸钾含量为单体总量的0．6％时,可以合成性能优良的改性苯丙乳液。     

Synthesis and Characterization of Polyamides Derived From Cyano-Containing 1,4-Bis(4-aminophenoxy)benzene Monomers

Summary A series of potentially electroactive aromatic-aliphatic polyamides based upon 3,6-bis(2-cyano-4-aminophenoxy)phthalonitrile (1) was synthesized in N,N-dimethylacetamide to yield polymers with intrinsic viscosities of 0.66-1.04 dL/g. One polyamide was synthesized using 1,4-bis(2-cyano-4-aminophenoxy)benzene (2) to compare to 1. There appears to be an odd-even effect of methylene spacer length upon the mechanical properties and glass transition temperature, with an even number of methylene groups yielding the larger values. Thermogravimetric analysis in air and nitrogen showed that these polymers had similar 5% weight losses in both atmospheres, which indicated that oxygen is not involved in the initial degradation of these polymers.     

Synthesis and Characterization of Cardo Bisbenzoxazines and their Thermal Polymerization

Bisbenzoxazines of bisphenol-C (BCO) and phenolphthalein (PHO) were synthesized by condensing 0.05 mol bisphenol-C/phenolphthalein, 0.2 mol formaldehyde, and 0.1 mol aniline. Both BCO and PHO were thermally polymerized via ring-opening polymerization. The resultant cross-linked polymers (PBCO and PPHO) were characterized by solubility, Infrared (IR), Nuclear Magnetic Resonance (NMR), Differential Scanning Calorimetry (DSC), and Thermogravimetric Analysis (TGA). The bisoxazines and their polymers followed two-step degradation. Both BCO and PHO undergo selective ring-opening polymerization over the temperature range 100–150°C and are thermally stable up to about 250°C. The % residue at 550°C is substantially higher for PHO samples (56–67%) than BCO samples (20–25%), indicating the highly thermally stable nature of PHO. A ring transformation reaction is also supported by DSC. New thermosetting materials may be useful for specific applications to be exploited.     

气相缩合法合成苯基三氯硅烷

以三氯氢硅和氯苯为原料,采用气相缩合法合成苯基三氯硅烷,探讨了反应温度、反应压力、反应空时和原料配比对苯基三氯硅烷收率和选择性的影响。结果表明,气相缩合法合成苯基三氯硅烷较好的工艺条件为反应温度600℃,反应压力不低于0.4 MPa(绝压),反应空时120～180 s,原料氯苯(C6H5Cl)和三氯氢硅(SiHCl3)物质的量之比为1.5～2.5。其中,当反应温度为600℃,反应压力为0.4 MPa(绝压),反应空时为120 s,C6H5Cl和SiHCl3物质的量之比为2.5时,苯基三氯硅烷收率和选择性均为73.33%。     

Synthesis and Characterization of Polyimides Derived From Cyano-Containing 1,4-Bis(4-aminophenoxy)benzene Monomers

Summary A series of three new cyano-containing diamines based upon 1,4-bis(4-aminophenoxy)benzene was synthesized and polymerized with six different dianhydrides to yield 18 different polyimides. Due to the high dipole moment of the cyano group, it was believed that these polymers would display differing degrees of electroactivity depending upon the degree and position of cyano substitution. The type of dianhydride bridging group and length are also factors that affect the electroactivity of polyimides. Polyimides based upon 1,4-bis(4-aminophenoxy)benzene were used as reference materials by which the respective cyano-containing analogs were compared. As the degree of cyano group substitution increased, the glass transition temperature increased. As cyano substitution increased, the polymer chain flexibility decreased due to hindered rotation about the phenyl-ether-phenyl linkages in the diamine portion of the polymer. The tensile moduli ranged from 2.97 to 4.57 GPa and ultimate tensile strengths from 79 to 156 MPa, which are typical values of aromatic polyimides.