α-甲基苯乙烯二聚体的合成及应用

以α-甲基苯乙烯（α-MS）为原料,分别高选择性地合成了-MS线性二聚体(Ⅰ)和α-MS环状二聚体(Ⅱ),并再以Ⅱ为原料,两步法合成了光引发剂KIP150（Ⅲ）。研究结果表明,以对甲苯磺酸为催化剂,在30 ℃下反应24h,产物Ⅰ收率88.0%,纯度大于99.8%;同样以对甲苯磺酸为催化剂,在100 ℃下反应7 h,产物Ⅱ收率98.0%,纯度大于99.8%;化合物Ⅱ经酰基化反应和羟基化反应即可得产物Ⅲ,总收率高于70.0%,纯度可达95.0%以上。实验中采用LC-MS、1H NMR、GC、HPLC等分析方法对各反应产物进行结构确定和纯度测定。     

二苯甲酮LED光引发剂的合成及性能研究

为了延长二苯甲酮光引发剂的吸收波长,使其与LED光源更好的匹配,本研究将苄氨基基团引入二苯甲酮结构,合成了3种4-双苄胺基二苯甲酮衍生物,其吸收波长延长至400 nm,与不同波长（365～405 nm）的LED光源能较好的匹配。利用实时红外对其光聚合动力学进行测试,通过电化学测试以及光降解测试等对其作用机理进行研究。结果表明：双苄胺基二苯甲酮衍生物是一类高效的LED光引发剂,其可作为单组分光引发剂引发1,6-己二醇二丙烯酸酯发生自由基聚合,双键转化率可达80%～83%。与碘鎓盐复配,引发阳离子聚合时环氧单体转化率可达45%,引发自由基-阳离子混杂光固化时双键转化率为69%～71%,环氧单体转化率为58%～61%,在自由基聚合及互穿网络聚合物结构光固化材料制备方面存在潜在应用价值。     

改性超支化聚合物的制备及其阻垢性能

通过对超支化聚合物末端基改性，合成2类具有抑制硫酸钙、碳酸钙垢的高效阻垢剂。采用EDA(乙二胺)、MA(丙烯酸甲酯)为原料，甲醇为溶剂，通过迈克尔加成和酰胺化反应，制备出PAMAM-2.0 G(2.0代超支化聚酰胺-胺),然后分别用HEDP(羟基乙叉二膦酸)和MAH(马来酸酐)对PAMAM-2.0 G进行改性，成功制备出PAMAM-PO₃H₂/PAMAM-COOH(端膦酸基/端羧基超支化聚酰胺-胺),并考察了不同环境状态下聚合物的阻垢性能。结果表明：PAMAM-PO₃H₂和PAMAM-COOH对CaSO₄垢的阻垢率均达到100%,对CaCO₃垢的阻垢率分别达到98.1%、88.7%,在80℃、pH>9时2种改性聚合物对钙垢的阻垢率均达到80%以上，且能够快速阻垢、阻垢性能稳定。通过分散性能测试和SEM分析发现，其阻垢机理主要与超支化的分子结构和端接的官能团有关。     

吡咯烷基-N-甲酸-丙烯酸乙二醇酯光聚合动力学的研究

采用实时红外技术对所合成的活性稀释剂吡咯烷基-N-甲酸-丙烯酸乙二醇酯的聚合动力学进行了测试.研究了光强、引发剂浓度及引发剂种类对其光聚合的影响.结果表明光强越强、引发剂浓度越大,聚合速率越高,但是反应的最终双键转化率基本不变,均能达到100%左右.引发剂种类对其光聚合的最终双键转化率的影响不是特别明显,但对聚合速率有一定的影响.     

苯胺绿分子印迹聚合物制备条件对识别能力的影响

本文研究了在以苯胺绿为模板分子,α-甲基丙烯酸( MMA)和2-乙烯基吡啶为功能单体,乙二醇二甲基丙烯酸酯( EGDMA)为交联剂,偶氮二异丁腈为引发剂,乙腈和四氧呋喃为溶剂分别在热引发和光引发的条件下合成以孔雀石绿为模板分子的印迹聚合物的实验过程中,通过选择不同配比的反应物,分析了各种合成条件对印迹聚合物识别能力的影...     

影响水性聚氨酯/丙烯酸酯光固化速度的因素

用甲苯二异氰酸酯、聚己二酸新戊二醇酯、二羟甲基丙酸合成水性聚氨酯,用含双键的甲基丙烯酸羟乙酯封端,制得质量分数为34%的水性聚氨酯/丙烯酸酯水分散液,分别用三种光引发剂固化.结果表明,其中2-羟基-2-甲基-苯丙酮适用于常温固化;1-[4-(2-羟乙氧基-苯基)]-2羟基-2-甲基-丙酮适用于高温条件.当以1-[4-(2-羟乙氧基-苯基)]-2羟基-2-甲基-丙酮为光引发剂,控制光固化温度为80℃,表面光照强度70mW/cm2,引发剂质量分数为4%时,涂膜凝胶化时间为55s,凝胶化程度为 83.4%.此时冲击强度大于50kgcm,吸水率4.69%,附着力1级,耐溶剂性达300次.     

POP合成中提高反应单体转化率的研究

以偶氮二异丁酸二甲酯（AIBME）为引发剂,采用三釜连续二步加入引发剂工艺合成聚合物聚醚多元醇（POP）,并与一步加入引发剂的两釜连续及三釜连续工艺进行了对比,讨论了三釜连续二步加入法工艺中第二釜中引发剂、溶解用单体和稀释用聚醚用量对反应单体转化率的影响。结果表明,三釜连续工艺较二釜连续工艺的单体转化率由96．04％提高至96．58％;三釜连续二步加料法工艺第二釜中加入30％的引发剂用量、1．8％的单体用量和10％的聚醚用量,合成的POP粘度为9150mPa·S,固体质量分数为44．80％,单体转化率可提高到98．15％。     

两亲性苯甲酰甲酸酯类光引发剂及其引发性能

以苯甲酰甲酸和三乙二醇为原料合成了一种水油两亲性光引发剂苯甲酰甲酸三乙二醇单酯（TGBF），并利用紫外-可见分光光度计、电子自旋共振仪及实时红外光谱仪等手段探究了TGBF的光吸收性能、光降解机理、水中溶解性以及引发光聚合的能力。研究结果表明，TGBF在300 nm以上波长的摩尔消光系数较低，但在405 nm LED光源照射下，能够发生分子内或者分子间的夺氢反应，并产生烷基自由基引发单体聚合。TGBF具有良好的水溶性，可高效地引发油性单体三丙二醇二丙烯酸酯（TPGDA）与水性单体聚乙二醇400二丙烯酸酯（PEG（400）DA）的聚合，最终双键转化率可达到80%以上。更重要的是，TGBF具有优异的引发油性单体TPGDA与水性单体深度聚合的能力，聚合深度分别达到5.6cm和6.5 cm以上,在深层LED光聚合领域表现出极大的应用潜力。     

光敏引发AM-DAC共聚物的合成研究

以丙烯酰胺（AM）和丙烯酰氧乙基三甲基氯化铵（DAC）为原料,在紫外光照射和水溶性复合光敏引发剂作用下,通过水溶液自由基共聚法合成了阳离子型聚丙烯酰胺共聚物（CPAM）。探讨了光敏引发合成过程中复合光敏引发剂用量、单体质量分数、单体配比及乙二胺四乙酸二钠（EDTA-2Na）用量等因素对聚合物相对分子质量、转化率、阳离子度、溶解时间等的影响。得出最佳反应条件为：单体质量分数20%,DAC与AM摩尔比为1∶9,复合光敏引发剂质量分数为0.05%,EDTA-2Na为单体质量的0.03%。运用红外光谱仪对聚合物的结构进行了分析表征。     

甲基丙烯酸高碳链混合醇酯合成及制备吸油树脂的研究

用正交试验法考察了甲基丙烯酸和高碳链混合醇直接酯化合成甲基丙烯酸混合醇酯的工艺条件。其酯化反应的工艺条件为：酸醇量比为1.2：1,w（催化剂）为1.5%,w（阻聚剂）为0.5%,反应温度130℃,反应时间4h,空气流速为0.16L/min。用甲基丙烯酸高碳链醇酯为单体,1,4-丁二醇二丙烯酸酯为交联剂,过氧化苯甲酰为引发剂,聚乙烯醇为分散剂,采用分散聚合法制备了具有吸油性能的甲基丙烯酸高碳链混合醇酯共聚树脂,并用均匀设计试验法优化了聚合合成工艺条件：w（交联剂）为1.2956%,w（引发剂）为1.0298%,w（分散剂）为0.2374%,反应温度88℃,该聚合物的吸油倍率最大值为16.0340g柴油/g树脂。     

Initiator‐fragment incorporation radical polymerization of ethylene glycol dimethacrylate in the presence of 1,1‐diphenylethylene: synthesis and characterization of soluble hyperbranched polymer nanoparticles

The polymerization of ethylene glycol dimethacrylate (EGDMA) as crosslinker was carried out at 70 and 80 °C in benzene using dimethyl 2,2′‐azobisisobutyrate (MAIB) as initiator at concentrations as high as 0.50–0.70 mol l^?1 in the presence of 1,1‐diphenylethylene (DPE), where the concentrations of EGDMA and DPE were 0.50–0.70 and 0.25–0.50 mol l^?1, respectively. The polymerization proceeded homogeneously, without gelation, to give soluble polymers. The yield and molecular weight of the resulting polymers increased with time. The homogeneous polymerization system involved ESR‐observable DPE‐derived radicals of considerably high concentration (3.6–5.3 × 10^?5 mol l^?1). The methoxycarbonylpropyl groups as MAIB‐fragments were incorporated as a main constituent (35–50 mol%) into the polymers (initiator‐fragment incorporation radical polymerization). The polymers also contained DPE units (15 mol%) and EGDMA units with double bonds (10–25 mol%) and without double bonds (20 mol%). Results from gel permeation chromatography (GPC)–multiangle laser light scattering (MALLS), transmission electron microscopy (TEM) and viscometric measurements revealed that the individual polymer molecules were formed as hyperbranched nanoparticles. Copyright © 2004 Society of Chemical Industry     

Initiator‐fragment incorporation radical polymerization of diallyl phthalate: Kinetics,formation of hyperbranched polymer,and iridescent porous film thereof

Diallyl phthalate (DAP) was polymerized in toluene using dimethyl 2,2′‐azobisisobutyrate (MAIB) of high concentrations (0.1–0.9 mol/L) as initiator. The polymerization of DAP of 1.50 mol/L with MAIB of 0.50 mol/L proceeded homogeneously at 80°C without gelation to give soluble polymers in a high yield of 93%. Kinetic results of the homogeneous polymerization at 80°C suggest significant contributions of the degradative chain transfer and the primary radical termination as shown by the rate equation, R_p = k [MAIB]^0.8[DAP]^1.0 (R_p = polymerization rate). The polymer formed in the polymerization of DAP (1.30 mol/L) with MAIB (0.50 mol/L) at 80°C for 8 h consisted of the DAP units with (17 mol %) and without (47 mol %) double bond and the methoxycarbonylpropyl group (36 mol %) as MAIB‐fragment. The large fraction of the incorporated initiator‐fragment as terminal group indicates that the polymer has a hyperbranched structure. The film cast from a solution of the hyperbranched poly(DAP) in tetrahydrofuran showed an iridescent color. The confocal scanning laser microscope image of the film revealed that the iridescent film contained the pores of about 1 μm arranged in an ordered array. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 408–415, 2006     

Synthesis and characterization of soluble hyperbranched polymer via initiator‐fragment incorporation radical polymerization of divinylbenzene with dimethyl 2,2′‐azobisisobutyrate

The homopolymerization of divinylbenzene (DVB) as an excellent crosslinker (0.20 mol/L) with dimethyl 2,2′‐azobisisobutyrate (MAIB) proceeded homogeneously without any gelation at 80°C in benzene when the MAIB concentrations as high as 0.30–0.50 mol/L were used, yielding soluble polymers. In the polymerization at the concentrations of [DVB] = 0.20 mol/L and [MAIB] = 0.50 mol/L, the polymer yield increased with time and leveled off over 90 min. The molecular weight and molecular weight distribution increased with polymer yield. The vinyl groups of DVB were observed to be almost completely consumed in about 80 min, by FT near‐IR spectroscopic analysis. The homogeneous polymerization system involved ESR‐observable polymer radical, the concentration of which increased with time up to 3.4 × 10^?5 mol/L. The polymer formed in the polymerization for 2 h consisted of 46 mol % of DVB unit and 54 mol % of the methoxycarbonylpropyl group as MAIB fragment, indicating that an initiator‐fragment incorporation radical polymerization proceeds in the present polymerization. The polymer was soluble in benzene, tetrahydrofuran, ethyl acetate, chloroform, acetone, and N,N‐dimethylformamide, while it was insoluble in n‐hexane, acetonitrile, dimethyl sulfoxide, methanol, and water. The results of the multiangle laser light scattering and viscometric measurements revealed that the individual polymer molecules were formed as hyperbranched polymer nanoparticles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 664–670, 2006     

Soluble hyperbranched copolymer via initiator-fragment incorporation radical copolymerization using a trivinyl monomer

The initiator-fragment incorporation radical polymerization was extended to a copolymerization system of a trivinyl monomer. The copolymerization of trimethylolpropane trimethacrylate (TMPTM) as a trivinyl monomer with α-methylstyrene (MSt) was examined at 70 and 80 °C in toluene using dimethyl 2,2′-azobisisobutyrate (MAIB) of high concentrations as initiator. When the concentrations of TMPTM, MSt and MAIB were 0.30, 0.60 and 0.50 mol/l, the copolymerization proceeded homogeneously without gelation at 80 °C to yield soluble hyperbranched copolymer in a yield of 65%. The copolymer formed for 8 h consisted of 37 mol% of the TMPTM unit, 42 mol% of the MSt unit and 21 mol% of the methoxycarbonylpropyl group as initiator-fragment, where 22% of the vinyl groups of the incorporated TMPTM units remained unreacted. The copolymer showed an upper critical solution temperature (32 °C on cooling) in a tetrahydrofuran(THF)-water [44:10 (wt/wt)]. Reflecting the hyperbranched structure, the viscosity of a copolymer solution in toluene was very low. The porous film was prepared directly by casting a THF solution of the hyperbranched copolymer on a cover glass. The copolymer molecules are radially arranged on the surface layer of the spherical pores as showed by polarized optical microscope imaging.     

Formation of soluble hyperbranched polymer through the initiator-fragment incorporation radical copolymerization of ethylene glycol dimethacrylate with N-methylmethacrylamide

The copolymerization of ethylene glycol dimethacrylate (EGDMA) as a divinyl monomer with N-methylmethacrylamide (NMMAm) as a water-soluble monomer was carried out at 70 and 80 °C in N,N-dimethylformamide (DMF) using dimethyl 2,2′-azobisisobutyrate (MAIB) of high concentrations as initiator. When the concentrations of EGDMA, NMMAm and MAIB were 0.15, 0.50 and 0.35 mol/l, the copolymerization proceeded homogeneously with no gelation at 80 °C to give soluble copolymer in a yield of 50%. EGDMA was polymerized more rapidly than NMMAm as shown by Fourier-transform near infrared spectroscopy. The copolymer formed for 8 h consisted of 20 mol% of EGDMA unit, 47 mol% of NMMA unit and 33 mol% of methoxycarbonylpropyl group unit as MAIB-fragment. The copolymer formed at 80 °C for 30 min showed an upper critical solution temperature (34 °C on cooling) in methanol. The intrinsic viscosity of the copolymer formed for 2 h was very low (0.11 dl/g) at 30 °C in DMF despite high weight-average molecular weight [3.1×l0⁶ by multi-angle laser light scattering (MALLS)]. The copolymer exhibited a very low second virial coefficient (4.2×l0⁻⁶) as determined at 25 °C in DMF by MALLS. The individual copolymer molecules were observed as nanoparticles of 7-20 nm diameter by a transmission electron microscope. These results show that the resulting copolymers are of hyperbranched structure.     

Effect of nitrobenzene on initiator-fragment incorporation radical polymerization of divinylbenzene with dimethyl 2,2′-azobisisobutyrate

The polymerization of divinylbenzene (DVB) with dimethyl 2,2′-azobisisobutyrate (MAIB) was conducted at 70 and 80 °C in benzene in the presence of nitrobenzene (NB) as a retarder. When the concentrations of DVB, MAIB, and NB were 0.45, 0.50, and 0.50 mol/l, respectively, the polymerization proceeded without any gelation to yield soluble polymers. The polymer yield (up to 65%) and the molecular weight (M_n=1.5-4.2×l0⁴ at 70 °C and 1.3-3.9×l0⁴ at 80 °C) increased with time. The polymer formed in the polymerization at 80 °C for 4 h consisted of the DVB units with (4 mol%) and without double bond (41 mol%), methoxycarbonylpropyl group as MAIB-fragment (48 mol%), and NB unit (7 mol%). Incorporation of such a large number of the initiator-fragments as terminal groups in a polymer molecule indicates that the polymer is of a hyperbranched structure. The polymer showed an upper critical solution temperature (40 °C on cooling) in an acetone-water [14:1 (v/v)] mixture. The results of MALLS and viscometric measurements and TEM observation supported that the polymers formed in the present polymerization have a hyperbranched structure. The polymerization system at 70 °C involved an ESR-observable nitroxide radical formed by the addition of polymer radical to the nitro group of NB. The polymerization was kinetically investigated in dioxane. The initial polymerization rate (R_p) at 70 °C was expressed by R_p=k[MAIB]^0.5[DVB]^0.9[NB]^−0.4. The kinetic results were explained on the basis of the reversible addition of polymer radical to NB and the termination between the polymer radical and the nitroxide radical. The overall activation energy of the polymerization was 27.8 kcal/mol.     

高固含量核壳型丙烯酸酯乳液的制备与性能研究

以甲基丙烯酸甲酯为硬单体,丙烯酸丁酯(BA)为软单体,采用半连续种子乳液聚合方法合成了具有核壳结构的高固含量(不挥发物质量分数≥50%)丙烯酸酯乳液。采用红外光谱(FT-IR)、激光粒度仪(LPA)、透射电镜(TEM)等检测手段对产物进行了表征,同时考察了乳化剂的用量及复配比、引发剂、交联剂以及核单体中软单体含量对乳液性能的影响。结果表明:软﹑硬单体发生了共聚反应;乳液粒径分布较窄,核层聚合时适当加入少量BA,乳液的稳定性能明显提高,复合乳化剂m(SDS)∶m(OP-10)为2∶1且质量分数为3%,引发剂KPS质量分数为0.5%,交联剂EGDMA质量分数为2%时可制得性能较好的乳液。     

Preparation of hyperbranched polymers through ATRP of in situ formed AB* monomer

The self‐condensing vinyl polymerization of an AB* monomer formed in situ by atom transfer radical addition from divinylbenzene (DVB) and (1‐bromoethyl)benzene (BEB) using atom transfer radical polymerization technique was studied. The catalyst concentration has a dramatic effect on polymerization. To study the polymerization mechanism and to achieve high molecular weight polymer, the polymerization was carried out in bulk with a catalyst to monomer ratio, 2,2′‐bipyridine to DVB, of 0.2 at 90°C. Proton nuclear magnetic resonance (¹H NMR) spectroscopy and size‐exclusion chromatography coupled with multiangle laser light scattering were used to analyze the polymerization aliquots and the obtained polymer. The intrinsic viscosities of the prepared polymers were also measured. Experimental results, from the comparison of the apparent molecular weights measured by size‐exclusion chromatography with the absolute values measured by multiangle laser light scattering as well as viscosity measurements, indicate the existence of hyperbranched structures in the prepared polymers. In sharp contrast to hyperbranched polymers from AB* monomer preprepared, hyperbranched ploy(divinylbenzene) prepared at equimolar amount of DVB and BEB has numerous residual pendant vinyl groups rather than only one double bond at its focal point. The hyperbranched polymers show relatively narrow molecular weight distribution (2.13–3.77) and exhibit excellent solubility in common organic solvents such as acetone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 850–856, 2006     

Study on ultrasonic induced encapsulating emulsion polymerization in the presence of nanoparticles

In this paper, the ultrasonic induced encapsulating emulsion polymerization technique was used to prepare polymer/inorganic nanoparticle composites. The main affecting factors in ultrasonic induced encapsulating emulsion polymerization were studied systematically. The experimental results suggested that the pH value, the type of monomers, the type, content, and surface properties of nanoparticles, the type and concentration of surfactant have great influence on the ultrasonic induced encapsulating emulsion polymerization and the obtained latex stability. If selecting cationic emulsifier (such as cetyl trimethylammonium bromide), low water soluble monomer (such as n‐butyl acrylate and styrene), and hydrophobic nano silica, the inorganic nanoparticles could be encapsulated by polymers through ultrasonic irradiation successfully under alkalescent condition, forming a novel polymer/inorganic nanoparticles composite. The mechanism of ultrasonic induced encapsulating emulsion polymerization and the composite latex stabilization are proposed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1130–1139, 2001     

细乳液聚合最新研究进展

随着高分子合成技术的迅速发展,乳液聚合法的发展创新趋势较为明显,其聚合过程对商品聚合物的生产至关重要,所制备出的聚合物乳液可直接用作水性涂料和胶粘剂等。文中具体介绍了细乳液聚合体系的设计方法、聚合过程及稳定机理,重点综述了近年来细乳液聚合在高固含量细乳液制备、纳米复合材料制备（荧光聚合物纳米粒子、有机 /无机纳米复合材料）及聚合物空心球或微球制备等方面的研究进展。