基于TMPME与BTEA的可紫外光固化水性聚氨酯的光固化动力学及涂膜性能

采用两种不同结构的含双键二元醇三羟甲基丙烷单烯丙基醚(TMPME)与2-(3-(((2,2-二(羟甲基)丁氧基)酰胺基)甲基)-3,5,5-三甲基环己基氨基甲酰氧)丙烯酸乙酯(BTEA)作为扩链剂在分子侧链上引入可UV固化的双键,分别制备出双键含量相同的可UV固化的水性聚氨酯TMPME-PU和BTEA-PU。红外光谱(FT-IR)测试分析证实了TMPME-PU和BTEA-PU的结构。实验发现,具有较长支链BTEA-PU的双键活动性高,固化后双键转化率可达89%。与TMPME-PU相比,BTEA-PU固化膜具有较高的交联密度,更好的耐水和耐溶剂性。UV固化使两种乳胶膜由软、韧性的弹性体变成了硬、韧性的塑性体,且BTEA-PU固化膜具有良好的韧性特征。     

可UV固化脲-异丁醛-甲醛树脂的合成与表征

以异佛尔酮二异氰酸酯(IPDI)、丙烯酸羟乙酯(HEA)改性脲-异丁醛-甲醛树脂(UIFR),通过两步法合成了一种含碳碳双键可紫外光(UV)固化的脲-异丁醛-甲醛树脂(UVUIF)。研究了反应温度和催化剂用量对反应的影响。适宜的反应条件为:第一步反应温度70℃,催化剂用量0.10wt%;第二步反应温度60℃。通过红外光谱分析,证明了合成的UVUIF结构中已引入了光敏性的碳碳双键。经UV辐射固化后,固化膜仍具有较好的热稳定性、硬度和附着力。     

环氧丙烯酸酯涂料的UV固化研究

采用傅里叶红外光谱,对以γ-缩水甘油醚氧丙基三甲氧基硅烷与丙烯酸为主要原料所制备的低黏度环氧丙烯酸酯涂料的UV固化过程进行了定量分析。结果表明,环氧丙烯酸酯的UV固化反应是打开CC双键的自由基聚合反应,双键转化率的高低决定了涂膜的固化程度与硬度。随着固化时间的延长,环氧丙烯酸酯中CC双键的交联反应先快后慢,所得涂膜的硬度相应增加;固化时间为96s时,CC双键的转化率达到最高,涂膜的铅笔硬度为H;进一步延长固化时间,涂膜的硬度不再增加。     

UV固化超支化聚磷酸酯的制备与性能研究

以三(2-羟乙基)异氰脲酸酯和三氯氧磷制备第一代超支化聚磷酸酯,再以异佛尔酮二异氰酸酯(IPDI)及丙烯酸羟乙酯(HEA)的加成产物(IPDI-HEA)对超支化聚磷酸酯的羟基进行改性,通过控制改性程度,制备了—CC—双键含量不同的可UV固化超支化聚磷酸酯HPUA-1,研究了影响UV固化膜力学性能的影响因素。结果表明:固化后的HPUA附着力为0级,冲击强度50kg·cm,柔韧性为1mm,固化膜硬度和玻璃化转变温度随—CC—双键改性程度的增加而增加。     

溶剂负载摩擦法评价UV胶印油墨印品固化程度

目的 UV油墨固化程度是印品质量的关键影响因素,开发新型UV油墨固化程度评价方法,用以准确、直观地判断墨层固化程度,指导印刷工艺条件优化。方法 通过调控墨层的UV固化光能量,制备系列不同固化程度的胶印印品,以间歇红外法测定墨层的双键转化率定量分析固化交联反应的程度,进一步以墨层在不同溶剂下的摩擦次数建立墨层固化等级的评价方法。结果 不同UV固化能量下的样品,具有不同的双键转换率,依据不同比例的乙醇与水混合溶剂下的印品耐磨次数可以判定出印品的固化程度。结论 采用溶剂负载摩擦法主观经验判定依赖性低,可实现对UV油墨印品的整体油墨固化程度进行判定,具有良好的生产应用价值。     

光固化树脂部分（20051099～20051107）

20051099 具有良好耐污性的抗反射膜的制备方法 题述膜不易被指纹或杂质弄脏，易于大量生产，可用于平板显示设备，制备步骤如下：1）制备涂料液，即混和UV固化树脂组分（包括UV固化丙烯酸-聚氨酯基树脂、光聚合引发剂及溶剂）、二氧化硅分散体组分（包括丙烯酸基树脂、SiO2粒子、分散剂及溶剂）及稀释荆；2）将涂料液涂于基片上，使涂层干燥，在UV下曝露固化并在其上涂覆氟基硅烷偶联剂形成含氟涂层。（CA137：7599）     

聚乙二醇二丙烯酸酯齐聚物的合成及其红外激光固化性能研究

使用3种方法合成了具有不同分子量的聚乙二醇二丙烯酸酯（PEGDA）齐聚物,包括：聚乙二醇（PEG）与丙烯酸反应,聚乙二醇与丙烯酰氯反应,聚乙二醇钠与丙烯酰氯反应,并在此基础上对3种合成方法进行比较。研究了聚乙二醇二丙烯酸酯齐聚物的红外激光固化反应,利用红外分析测定双键转化率,发现随着齐聚物分子量增大,激光固化后的双键转化率有所上升。     

美国FDA批准UV固化可以直接用于食品包装

美国食品及药物管理局（FDA）近日发布关于食品接触通告（FCA）722,表明允许在食品外包装上可以直接使用UV固化和电子束固化包装。FCA772通告明确指出,UV固化和电子束固化可以作为涂布或是涂布的成分（其中包括油墨）在外包装上使用,范围包括：聚脂材料、纸张、纸板、金属上的涂布及不干胶成分。     

美国FDA批准UV固化可以直接用于食品包装

美国食品及药物管理局（FDA）近日发布关于食品接触通告（FCA）722,表明充许在食品外包装上可以直接使用UV固化和电子束固化包装。FCA772通告明确指出,UV固化和电子束固化可以作为涂布或是涂布的成分（其中包括油墨）在外包装上使用,范围包括：聚酯材料、纸张、纸板、金属上的涂布以及不干胶成分。     

超支化预聚物在特种UV固化胶中的应用研究

以乙二胺(EDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)为主要原料,合成外围带有8个双键的超支化预聚物,用红外光谱进行了表征.将超支化预聚物与不同官能度单体配成特种UV固化胶,测定了粘度、透过率、折射率随固化胶成分的变化.结果表明,由于超支化预聚物与一般线性预聚物结构不同,UV固化胶黏度较低,且随着单体含量的增加,黏度下降平缓;在400～1500hm的可见及红外光区,UV固化胶的光透过率较高,均大于95%;UV固化胶折射率随预聚物含量的增加而增加,最高达1.572.用超支化预聚物制备的特种UV固化胶有望在光学器件中得到应用.     

新型可紫外光固化水性聚氨酯的制备与表征

以异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇Pol-1256、二羟甲基丙酸(DMPA)为主要原料,采用预聚体法制备了水性聚氨酯预聚体,然后用自制的扩链剂对该预聚体进行扩链,并用丙烯酸羟乙酯(HEA)对扩链后的预聚体进行封端,最后中和乳化,制备了高紫外光(UV)固化基团含量的可UV固化水性聚氨酯乳液。采用FTIR对产物的结构进行了鉴定,利用旋转流变仪对分散体的流变性能进行了表征,通过TGA分析了UV固化膜的耐热性能,并对其拉伸性能进行了测试。研究结果表明:所制扩链剂符合预期结构特征,所得产物符合可UV固化的水性聚氨酯结构特征;乳液呈现出剪切变稀的特征,属于假塑性流体;UV固化膜具有良好的耐热性能,同时具有较高的断裂伸长率和良好的拉伸强度。     

Properties of polymer networks prepared by blending polyester urethane acrylate with acrylated epoxidized soybean oil

Polyurethane network films were prepared using polyester urethane acrylate (PUA) having terminal double-bond functional groups and acrylated epoxidized soybean oil (AESO). PUA elastomers were prepared by reacting polyester diol with diisocyanates, hexamethylene diamine, and acrylic acid. PUA/AESO network blends are synthesized by a simultaneous thermal polymerization process. The physical and thermal properties of the polymer networks obtained from the blend of AESO and polyester urethane urea acrylate were studied using FTIR-ATR, the thermal degradation behavior was studied by thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and tensile properties measurements being applied. The measurements were compared to the results for elastomers made from the PUA. The weight ratios of PUA/AESO affected the thermal and mechanical properties. With an increase in AESO content, the glass-transition temperature of the networks decreased from 40 to −4.8 °C, tensile strength increased from 1.7 to 9.8 MPa, and elongation at break decreased from 470 to 70%.     

氟与端羟基聚丁二烯复合改性UV固化多臂型聚氨酯的合成与性能

采用甲基丙烯酸十二氟庚酯(DFHMA)和二乙醇胺(DEOA)自制含氟二元醇;以异佛尔酮二异氰酸酯(IPDI)、聚碳酸酯二元醇(PCDL)、端羟基聚丁二烯(HTPB)、含氟二元醇、季戊四醇三丙烯酸酯(PETA)为主要原料合成—NCO半封端线型聚氨酯;将双季戊四醇(Di-PE)加入聚氨酯体系,制备了氟与端羟基聚丁二烯复合改性UV固化多臂型聚氨酯。通过红外光谱和核磁共振对聚合物进行表征,并研究了不同含氟二元醇及端羟基聚丁二烯添加量对涂膜水接触角、吸水率、热稳定性、硬度、力学性能等的影响。测试结果表明,含氟二元醇和端羟基聚丁二烯的引入使涂膜的水接触角增加,吸水率大幅降低,热稳定性增强,硬度提高。当含氟二元醇质量分数为8%,端羟基聚丁二烯质量分数为20%时,涂膜的综合性能最佳。     

pH Sensitive graft copolymers for zero order drug release: a mechanistic analysis

Aliphatic polyesters containing pendent unsaturation were synthesized by the polycondensation of a diol, dicarboxylic acid and glycidyl methacrylate. Grafting methacrylic acid (MAA) resulted in graft copolymers containing polyester backbone and MAA grafts. Depending on composition, the polymers swelled extensively and eroded or dissolved at near neutral pH but remained in collapsed state at acidic pH. Three representative drugs differing in solubility, viz., Diltiazem hydrochloride (DH), Indomethacin (IM) and Verapamil hydrochloride (VH) were released at constant rate from tablets made by compressing spray-dried microparticles. The release of DH at constant rate has been attributed to increase in diffusion coefficient of the drug from the swollen layer of matrix. The release of IM and VH at constant rate was governed by erosion and was enhanced in matrices which undergo dissolution. The release rate was enhanced with increasing MAA content and the frequency of grafts along the polyester backbone. Once a day dosage forms for drugs differing in solubility have been developed using a single polymer matrix which is easy to manufacture.     

Synthesis, Characterization, and Cytotoxicity Analysis of a Biodegradable Polyurethane

A polyester urethane was synthesized for use in a biodegradable scaffold. The polyurethane was synthesized in a two-step process: first, ester diol was synthesized from lactic acid and polyethylene glycol 400 (PEG 400), then it was polymerized with toluene diisocyanate using dibutyl tin dilaurate (DBTDL) as a catalyst to form a polyester urethane. Polyester urethane has tensile strength of 51-59 MPa and elongation at fracture of 369-439%. FTIR and XRD were used to confirm the formation and structure of the polymer. Hydrolytic degradation was studied in different alkali solutions and in saline water. In order to assess the cellular response of this material, cytotoxicity analysis was carried out against the cell line.     

Pultruded fibre reinforced polyurethane composites I. process feasibility and morphology

A feasibility study on the pultrusion of a fibre reinforced polyurethane (PU) composite has been conducted by using a proprietary method. The blocked NCO-terminated PU prepolymer synthesized in this study was prepared from -caprolactam blocked prepolymer blended with toluene di-isocyanate (TDI-80) and branched polyester. From the investigations of gel permeation chromatography, IR and ¹H nuclear magnetic resonance spectra and viscosity, the molecular weight, degree of blocked reaction and viscosity of the blocked PU prepolymer were obtained. From the mono-n-butylamine back-titration (wet) method, the equivalent weight and NCO content of unblocked NCO-terminated PU prepolymer were determined. A long pot life of blocked NCO-terminated PU prepolymer with various chain extenders, such as cycloaliphatic diamine, aromatic diamine and 1,4-butane diol, was observed in the impregnation temperature range (55–70°C). A high reactivity of prepolymer was found from Brookfield viscometer measurements at elevated temperature. From a morphological study of scanning electron micrographs, it was confirmed that the wetting of fibres by blocked PU resin was complete, and the fibre bundles were evenly distributed in the PU matrices.     

Layer-by-layer deposition of green synthesised silver nanoparticles on polyester air filters and its antimicrobial activity

Silver nanoparticles stabilised with anionic polymeric polyelectrolytes were successfully synthesised by high-energy UV reduction. Three types of polyelectrolytes were used including poly(methacrylic acid) (PMA), poly(acrylic acid) (PAA) and poly(4-styrenesulphonic acid-co-maleic acid) (CoPSS). The formation of the prepared solutions exhibited surface plasmon resonance at the wavelength of 475, 730 and 408 nm by using PMA, PAA and CoPSS as the stabilising agents. UV–visible spectrophotometer, transmission electron microscope (TEM) and zeta potential analyser were employed to characterise the formation of the prepared solutions. The silver nanoparticles stabilised with anionic polyelectrolytes were immobilised on polyester air filters using a layer-by-layer technique. This is the sequential dipping of polyester air filters in a dilute solution of cationic poly(diallyldimethylammonium chloride) and anionic polymeric polyelectrolytes capped silver. The surface topography of the polyester air filters were measured by field emission scanning electron microscope. Results showed that silver nanoparticles had the highest surface coverage on the polyester air filters probably because it is a good bonding candidate and insures strong film growth. The multilayers polyester air filters coated silver nanoparticles were tested against the gram positive pathogen Staphylococcus aureus. The deposition of silver nanoparticles onto the polyester air filters resulted in 92.18%, 84.32% and 71.19% of bacteria removal using PMA, PAA and CoPSS as the stabilising agent.     

Effect of block ratio and strain amplitude on thermal,structural, and shape memory properties of segmented polycaprolactone-based polyurethanes

In this work, the effects of changing molecular weight of polyol (2000, 3000, and 4000) and block ratio as well as deformation amplitude on thermal, structural, and shape memory properties of polyester urethanes based on diphenylmethane diisocyanate, polycaprolactone diol, and 1,4-butanediol were investigated. Fourier transform infrared spectroscopy was used to check the accomplishment of the polyurethanes synthesis. Thermal, structural, and shape memory properties of synthesized SMPUs were measured using differential scanning calorimetry, wide angle X-ray diffraction, and tensile cyclic tests, respectively. It was found that as the crystallinity of soft segments increased, the ability of the samples in fixation of temporary shape was higher. On the other hand, the shape recovery was dominated by the hard segment content and there was a minimum critical HSC for the samples to show appropriate shape memory effects.     

Study of the structure–property relationships in a high impact and shape memory polyester by the stereoisomer selection of the cyclobutane diol monomer

The diol and dicarboxylic acid in polyester synthesis are significant independent variables that relate directly to the structure–property-dependent variables of polyesters. The choice of the stereoisomers of the diol in the polyester synthesis can significantly alter the mechanical and thermal performance. Terephthalate polyesters prepared from the proper ratio of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO) and 1,3-propanediol have superior impact resistance when compared to ballistics grade polycarbonate. In addition these polymers exhibit very strong self-healing behavior that is activated by heat. These copolymers were all produced with a mixture of cis and trans isomers with a ratio of 43/57, respectively. This study reports research conducted to determine the structure–property relationships that can be attributed to the stereoisomers of the CBDO monomer. The polyester prepared with 99 % cis (CBDO) monomer has significantly improved mechanical and thermal performance when compared with the polyester prepared with a 43:57 mixture of cis and trans isomers or 100 % trans isomer. Thermal gravimetric analysis and differential scanning calorimetry demonstrated that the cis CBDO polymer exhibit a much higher T _g (99 °C for cis and 69 °C for the trans 84.5 °C for the mixed polymer) and better thermal stability than the trans form of the polymer (onset of decomposition of trans at 345 and 360 °C for cis). Dynamic mechanical analysis and the Notched Izod demonstrated that the cis form of the polymer was much tougher than the trans form. Wide angle X-ray diffraction showed that the trans form was semicrystalline and the cis form was amorphous. The Notched Izod impact was 1070 J/m for the cis CBDO-based copolymer with the trans form having an impact factor of 841 J/m with the mixed polymer exhibiting an intermediate value of 944 J/M. Molecular modeling supports the experimental evidence that the choice of stereoisomers for the diol significantly influences the molecular architecture of the polyesters. The molecular architecture of polyesters in addition to polar attraction and molecular weight variables provides a dramatic increase in mechanical and thermal performance.     

Synthesis procedure and the fracture toughness of highly cross-linked resins

Experimental values of the plane strain fracture toughness of cross-linked unsaturated polyester resins are presented. It is demonstrated that these values depend not only on nominal resin composition (e.g. nature of diol, or molar ratio, R, of unsaturated to saturated acid) but also on the conditions under which polycondensation occurs. It is necessary to define rather precisely the molar ratio of total diol to total acid, and also to assess the efficiency of diol utilization. These considerations become more important as R increases. Also, as the value of R increases, toughness falls. When samples are immersed in hot water, a reduction in toughness is found. The effect of crack-tip radius on apparent toughness values is more marked with a resin of low than of high cross-link density.