分子设计合成高折光指数的光学树脂（Ⅲ）：MMDMA的合成及？…

采用盐酸／硫脲法合成了２－巯基甲基－１，４－二硫杂环己烷，利用反滴碱液的低温相转移催化技术合成了２－甲基丙烯酰硫基甲基－１，４－二硫杂环己烷，讨论了ＭＭＤ合成过程中的结构变化，研究了ＭＭＤＭＡ的共聚性能，合成了折光指数高，色散能力低的新型光学树脂。     

TA-EG-GMA合成超支化碱溶性感光聚合物

通过1,2,4-偏苯三酸酐和乙二醇反应合成超支化聚合物,利用合成聚合物分子外围的羧基与甲基丙烯酸缩水甘油酯反应,在超支化聚合物分子外围引入反应性甲基丙烯酰氧基.研究了树脂组成对感光性和碱溶性的影响.结果表明:调整反应物料配比及反应性甲基丙烯酰氧基含量,可以获得较好的碱溶性和光固化性能.     

全氟辛酸甲基丙烯酰氧基乙酯单体的制备

全氟辛酸甲基丙烯酰氧基乙酯单体的制备;全氟辛酸;正交实验;酰氯化;酯化     

季戊四醇-偏苯三酸酐-环氧氯丙烷合成超支化聚合物

以季戊四醇为“中心核”,与1,2,4-偏苯三甲酸酐和环氧氯丙烷反应合成超支化碱溶性聚酯,利用合成聚合物分子外围的羧基与甲基丙烯酸缩水甘油酯反应,在超支化聚合物分子外围引入反应性甲基丙烯酰氧基.研究了树脂组成对感光性和碱溶性的影响.结果表明:通过调整分子外围的羧基及反应性甲基丙烯酰氧基含量,可以获得较好的碱溶性和光固化性能.     

烷酰氧基芳磺酸盐的合成研究

研究了以羧酸酐和羟基芳磺酸盐为主要原料,丙酮为溶剂、无水碳酸钠为缚酸剂的烷酰氧基芳磺酸盐的清洁合成工艺,制备了4-壬酰氧基苯磺酸钠(NOBS)、壬酰氧基尼文酸钠、4-甲基丙烯酰氧基苯磺酸钠、甲基丙烯酰氧基尼文酸钠等4个化合物.考察了合成反应的影响因素.结果表明,以对羟基苯磺酸钠和壬酸酐为原料合成4-壬酰氧基苯磺酸钠(N...     

桥链中含氮,硫杂原子的二酰胺型开链冠醚的合成

合成了四类桥链中含氮、硫杂原子的二酰胺型开链冠醚，目的是以之作为碱土金属、过渡金属和重金属离子的载体。１ａ～１ｃ和２ａ～２ｃ显将Ｎ，Ｎ－双（２－羟乙基）苯胺和２，６－双（羟甲基）吡啶分别在ＴＨＦ中与ＮａＨ和Ｎ－取代和Ｎ，Ｎ－二取代氯乙酰胺反应而制得；而３ａ～３ｂ和４ａ～４ｂ则是将２，６－双（氯甲基）吡啶和２，５－双（氯甲基）噻吩分别与巯基乙酸在碱溶液中反应制成双（亚甲硫乙酸），然后与ＳＯＣｌ＿２反应成二酰氯，最后胺化而成二酰胺。各化合物的结构均由元素分析、ＩＲ、￣１ＨＮＭＲ和ＭＳ所确证。     

正交实验法在 6-甲基丙烯酰氧基己磺酸钠合成中的应用

聚(6-甲基丙烯酰氧基)己磺酸钠(PSSHMA)是我们最近合成的、具有较好抗凝血性能的生物医用高分子材料.对具磺酸基聚合物的抗凝血性能的研究,报道尚少.我们用羟基己磺酸钠与甲基丙烯酸制备了新单体6-甲基丙烯酰氧基己磺酸钠(SSHMA) SSHMA的合成中仅氯化反应已有报道.本文用正交法对合成单体中的三步反应进行探索,找出了较好的反应条件,提高了产率.     

两性P（DMC／AM／AA）纸张增强剂的合成和应用

研究了聚（甲基丙烯酰氧基乙基三甲基氯化铵－∞－丙烯酰胺－∞－丙烯酸）（Ｐ（ＤＭＣ／ＡＭ／ＡＡ））纸张增强剂的合成，结构和性能，这种两性聚丙烯酰胺和纸纤维能够用过离子键和配位络合作用，形成比较均一的交联网络，使纸张干强度和撕裂度明显增加，滤水时间显著缩短。     

1，3－双－（介晶基）－1，1，3，3－四甲基二硅氧烷的合成和相变研究

合成了１６种１，３－双－（介晶基）－１，１，３．３－四甲基二硅氧烷（Ⅱ_（ａ，ｂ），Ⅲ_（ａ─ｇ），Ⅲ_ｊ，Ⅳ_（ａ─ｆ）．其化学结构用￣１ＮＭＲ、ＩＲ、ＵＶ和元素分析表征。通过ＤＳＣ和偏光显微镜研究了它们的相行为，除Ⅱ_（ａ，ｂ）、Ⅲ_ｄ和Ⅳ_ｄ外，其余都呈现液晶相变。用Ｘ衍射分析研究了１，３－双－（４－甲基偶氮苯氧甲基）－１，１，３，３－四甲基二硅氧烷（Ⅱ_ａ）的晶体结构。讨论了这些新型硅氧烷化合物的比学结构对液晶相变行为的影响。     

（R）－N－（γ－烃基－δ－酮己酰基）四氢噻唑－2－硫酮－4－羧酸乙酯的合成及其同（R，S）－α－苯乙胺的反应

γ－甲基－δ－酮己酸，γ－异丙基－δ－酮己酸在碘化Ｎ－甲基－２－氯吡啶盐存在下分别同（Ｒ）－四氢噻唑－２－硫酮－４－羧酸乙酯反应，得到光学活性的（Ｒ）－Ｎ－（γ－甲基－δ－酮己酰基）四氢噻唑－２－硫酮－４－羧酸乙酯（１ａ）及光学活性的（Ｒ）－Ｎ－（γ－异丙基－δ－酮己酰基）四氢噻唑－２－硫酮－４－羧酸乙酯（１ｂ）。１ａ，１ｂ分别同（Ｒ，Ｓ）－α－苯乙胺反应得到光学活性的酰胺２ａ，２ｂ，同时使（Ｒ，Ｓ）－α－苯乙胺拆分，得到光学活性的α－苯乙胺。     

SYNTHESIS AND PROPERTIES OF TRANSPARENT THIODIGLYCOL DIMETHACRYLATE COPOLYMER RESINS

The title compound, thiodiglycol dimethacrylate (TDGDMA), was synthesized from thiodiglycol and methacryloyl chloride by phase transfer catalysis reaction, and its structure was confirmed by FTIR and 1H-NMR analyses. TDGDMA possesses good polymerizability to produce a homopolymer resin with excellent transparency (T%, 90), moderate refractivity (nd20, 1.55), lower dispersivity (Abbe‘s number, 50.6) and higher glass transition temperature (Tg, I19℃). Through copolymerization with styrene (St) or styrene-4,4‘-bismethacryloyloxydiphenylsulfone (BPSDMA), many properties of the copolymer such as refractive index, Abbe‘s number, strength, onset wavelength in the UV region and density were significantly modified. A copolymer resin with balanced properties between refractive index and dispersion was produced at the weight ratio of TDGDMA:St:BPSDMA (25:50:25), where nd20 and Abbe‘s number are 1.5815 and 36.5, respectively.     

Solubilization of oligosaccharides into chloroform by their incorporation into polystyrene as pendant groups

Solubilization of hydrophilic saccharide chains into organic solvents has been attempted by incorporating saccharide-substituted styrene unit into polystyrene main chain. Lactose-, maltopentaose, and amylose-substituted styrene monomers were copolymerized with styrene. Resulting chloroform-soluble copolymers were characterized, and structural formation was investigated. Copolymers of lactose-substituted styrene and maltopentaose-substituted styrene with styrene were dissolved into chloroform. The chloroform-soluble polymers contained about 12 disaccharide lactose chains or 1.7 maltopentaose chains as the pendant groups in one polystyrene molecule. Chloroform-insoluble methyl orange was dissolved into chloroform with the help of chloroform-soluble polystyrene having some saccharide chains. On the other hand, when an amylose-substituted styrene unit was inserted in a polystyrene chain, the resulting polymer became insoluble into chloroform. Amylose polysaccharide of DP_n = ∼24 was not dissolved into chloroform by this method.     

固体核磁共振法测定硫化丁苯橡胶中的苯乙烯

采用魔角旋转固体核磁碳谱法(MAS–~(13)CNMR)测定硫化丁苯橡胶中的苯乙烯含量。通过固体核磁碳谱解析,对丁苯橡胶中苯乙烯、1,2-乙烯基、1,4-丁二烯的特征峰进行归属分析,以固体核磁外标法定量。对已知苯乙烯含量的标准样品进行测定,绘制校正曲线,结果显示理论苯乙烯含量与固体核磁法计算结果成良好的线性关系,线性相关系数(r~2)为0.97。经标准曲线校正后的苯乙烯含量接近于真实值,计算结果的相对误差小于5%,测定结果的相对标准偏差为0.31%(n=6)。该方法适用于单一胶种的硫化丁苯橡胶中苯乙烯含量的检测。     

Graft Photopolymerization of Styrene to Wheat Gluten Protein in Dimethyl Sulfoxide

To determine the suitability of dimethyl sulfoxide (DMSO) as a solvent for photo polymerization, solutions of wheat gluten protein (0.28-0.93% by weight) and styrene (4.13-12.65% by weight) in DMSO were irradiated by a 200.W high-pressure mercury arc lamp from 3 min up to 1 hr. Graft copolymers of gluten styrene resulted that contained styrene residues ranging from 2 to 23% by weight. When gluten protein was photolyzed in DMSO alone, a significant amount of sulfur from the solvent was incorporated; however, styrene successfully competed with the solvent for free radical sites. The rate of grafting was directly related to both the concentration of gluten and of styrene. Also, the ratio of grafted polystyrene to gluten in the graft polymer indicated that the grafts were composed of small units of polystyrene.     

对甲苯磺酸/活性炭/双氧水体系选择氧化苯乙烯生成苯甲醛(英文)

以双氧水为氧化剂,研究了对甲苯磺酸和活性炭体系选择氧化苯乙烯生成苯甲醛反应性能。考察了反应时间、温度、催化剂用量、苯乙烯和双氧水摩尔比等对苯乙烯选择氧化性能的影响.结果表明,对甲苯磺酸和活性炭的用量和用量比是一个重要因素,但对甲苯磺酸的酸性对氧化反应活性影响不大.对甲苯磺酸和双氧水相互作用,经非自由基过程氧化苯乙烯.通过分解双氧水产生氢氧自由基,活性炭显著提高对甲苯磺酸和双氧水体系氧化苯乙烯活性.在惰性或还原气氛中高温处理活性炭能降低其表面含氧基团数量,增加碱性,有效分解双氧水,产生相对较多的OH自由基.与未处理的活性炭相比,高温处理的活性炭进一步提高了对甲苯磺酸和双氧水体系氧化苯乙烯活性,但降低了苯甲醛选择性.经磺化,在活性炭表面引入的–SO_3H基团比含氧基团(–OH,–COOH)更有效与双氧水作用氧化苯乙烯.     

Micro-composite systems by in-situ formation of liquid crystal polymers in commodity polymers

In-situ formation of polyimide was carried out in solution of copolymers derived from styrene and 4-vinylpyridine. The in-situ formed polyamic acid formed a strong hydrogen-bonding with pyridine moiety of the copolymers, resulting in homogeneous solutions. Cast films obtained from the solutions were clear and transparent without phase separations, and mechanical properties of the films were much stronger than those of films from the original copolymers. In-situ polymerization of acrylamide in poly(styrene) was carried out by anionic polymerization to form Nylon 3 which was dispersed in poly(styrene) as fine particles, and mechanical properties of the poly (styrene) were greatly improved.     

Microwave‐Assisted Free Radical Polymerizations and Copolymerizations of Styrene and Methyl Methacrylate

Summary: Radical homopolymerizations and copolymerizations of styrene were performed in toluene and N,N‐dimethylformamide (DMF) as solvents using different initiators with and without microwave irradiation. Only the homopolymerization of styrene under microwave irradiation in DMF with DtBP showed significantly enhanced styrene conversion whereas other initiators resulted in no or only slight increase of styrene conversion under microwave irradiation. In any case, DMF was required to gain in styrene conversion under microwave irradiation. Significantly higher monomer conversions were observed under otherwise comparable conditions in the copolymerization of styrene and methyl methacrylate (MMA) in DMF. Microwave‐induced selectivity of monomers was not observed in copolymerizations.

Yield of styrene polymerizations under varying reaction conditions initiated by DtBP.     

Cationic graft copolymerization of styrene onto chlorinated butyl rubber

The graft copolymerization of styrene onto chlorinated butyl rubber (Cl-IIR) with stannic chloride as cationic catalyst was studied in cyclohexane, and the rate of polymerization, per cent grafting and grafting efficiency were obtained. Polymerization was carried out in a sealed tube. The product was precipitated in methanol and dried. The increase in weight of Cl-IIR used was regarded as styrene conversion, and the increase in weight after extraction by boiling acetone as the weight of grafted styrene. Grafting was confirmed by fractional dissolution and infrared spectra. The rate of polymerization of styrene was proportional to concentrations of styrene, Cl-IIR and SnCl₄. The per cent grafting increased with styrene and SnCl₄ concentration, but was constant with Cl-IIR concentration. It also increased with time and with halogen content in the polymer. The addition of a polar solvent such as nitrobenzene greatly promoted the grafting reaction and the per cent grafting was 200%.     

N-对位取代苯基马来酰亚胺与苯乙烯溶液共聚动力学的研究

以DMF为溶剂 ,采用膨胀计法对N 对位取代苯基马来酰亚胺与苯乙烯的溶液共聚动力学作了系统研究 .其中N 苯基马来酰亚胺与苯乙烯的均相溶液聚合 ,聚合速率方程为Rp=k[I]1/ 2 [M ].同时还测定了四种N 对位取代苯基马来酰亚胺与苯乙烯在DMF中的共聚表观活化能 ,并由此证明四种单体的共聚活性及CTC络合物的存在     

GC-MS identification of styrene and oligomers in polystyrene plastic for milk packaging. Headspace and solution injection technique

Twenty compounds have been determined by GC-MS in polystyrene used for milk packaging. The major components identified in milk were styrene and its dimer at concentrations of 13 and 43 mg/kg, respectively. The detection limit for styrene by the equilibrium headspace method was 0.29 mg/kg. Another method used to determine the concentration of styrene and its dimer in milk was the use of acetone to precipitate the proteins and extract both the fat and the residues from the plastic packaging. The solution obtained was then directly injected into the GC. The detection limits were found to be 0.16 mg/kg for styrene and 0.28 mg/kg for the dimer. The solution injection method thus proved to be much more sensitive.