端羟基聚丁二烯型水性聚氨酯的制备、性能及交联改性

以3,6-二氧杂-1,8-辛烷二硫醇(BOODT)与异氰酸酯后扩链制备端羟基聚丁二烯(HTPB)型水性聚氨酯(WPUHS)分散液,再在紫外光照射下通过硫醇与双键的反应对水性聚氨酯分散液进行交联改性。研究了HTPB含量对分散液的稳定性、WPUHS的耐水性及力学性能的影响。结果表明:当HTPB含量约为4%时,分散液的粒径、WPUHS的耐水性及力学性能相对较好。同时探讨了交联改性中光引发剂种类及光照时间对胶膜交联密度及力学性能的影响,结果表明:安息香二甲醚为引发剂时,交联后胶膜的交联密度及力学性能较优;且光照时间为1 h时胶膜力学性能最优。     

紫外光辐照交联聚氯乙烯的研究

研究了聚氯乙烯(PVC)在增塑剂邻苯二甲酸二辛酯(DOP)存在的情况下,以二苯甲酮(BP)为光敏剂、三丙烯酸三羟甲基丙烷酯(TMPTA)为交联剂的紫外光辐照交联。实验证明:光敏剂对交联有着显著的影响;经过辐照,可大幅度提高PVC制品的硬度及拉伸强度。     

SBS与SBS/有机蒙脱土复合材料的光化学交联

通过测定交联体系凝胶含量的方法,考察了在紫外光辐照下,苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)进行光化学交联反应的影响因素,并研究了SBS/有机蒙脱土(OMMT)复合材料的光化学交联反应。结果表明,在N2气氛下,提高辐照温度有利于增加SBS交联体系的凝胶含量,且凝胶速率增长较快,辐照温度宜为130℃;与空气气氛比较,N2气氛对SBS的交联反应更有利;与引发剂二苯甲酮相比,安息香二甲醚(BDK)的引发效率高,BDK的最佳质量分数为1%;交联剂宜为异氰尿酸三烯丙酯,当其质量分数为1%时,SBS交联体系的凝胶含量达到最大值;与SBS交联体系相比,SBS/OMMT复合材料交联体系的凝胶速率明显下降。     

紫外光辐照交联EVA的制备及表征

采用紫外辐照技术制备了交联乙烯-L酸乙烯酯共聚物(XLEVA)。研究了实验温度、实验气氛、试样厚度及辐照时间等条件以及光引发剂、光交联剂的种类和浓度等因素对凝胶含量的影响。结果表明,辐照时间为2 min,温度为100℃时,交联效果较好,在此条件下,辐照氛围及试样厚度对交联反应影响不明显。二苯甲酮的引发效果优于安息香二甲醚,三羟甲基丙烷三丙烯酸酯的助交联效果最佳,两者的最佳含量均为1%,此时XLEVA的凝胶含量可达到86.48%。     

SBS的光交联研究

利用测凝胶含量的方法对SBS热塑性弹性体在紫外光辐照下的光交联反应进行了研究；并分析了光交联的影响因素。实验表明：采用安息香二甲醚（BDK）作为引发剂、三聚异氰酸三烯丙酯（TAIC）作为交联剂，能使SBS快速有效地发生交联，且凝胶含量达到90％以上。在此基础上，对不同的交联环境（空气、N2）、温度、样品厚度进行了对比，而且初步研究了蒙脱土（MMT）的加入对交联体系的影响。     

二苯基六氟砷酸碘鎓盐引发四氢呋喃的正离子光聚合

以二苯基六氟砷酸碘钅翁盐为引发剂,吖啶黄和安息香二甲醚为增感剂,在紫外光光照情况下,引发四氢呋喃(THF)进行了正离子聚合,讨论了吖啶黄和安息香二甲醚的增感机理,研究了二苯基六氟砷酸碘钅翁盐引发THF的后聚合反应。结果表明,在紫外光光照的情况下,二苯基六氟砷酸碘钅翁盐可以引发THF聚合,证明二苯基六氟砷酸碘钅翁盐是一种正离子光聚合引发剂;吖啶黄及安息香二甲醚对二苯基六氟砷酸碘钅翁盐引发THF聚合具有显著的增感作用;安息香二甲醚增感的二苯基六氟砷酸碘钅翁盐引发的THF后聚合具有明显的活性聚合趋势,转化率与特性黏数呈线性增长关系;通过紫外光引发聚合的方式可以制备相对分子质量分布为1·028、数均相对分子质量为1·004×104、转化率大于85%的聚四氢呋喃。     

紫外辐照交联对超高相对分子质量聚乙烯纤维凝胶含量的影响(英文)

通过浸渍的方法将交联剂和光敏剂引入超高相对分子质量聚乙烯纤维内部 ,然后将纤维置于紫外辐照装置中进行辐照交联。讨论了光照气氛、纤维状态、交联剂、浸渍溶剂及光照时间对纤维凝胶含量的影响。结果表明 :聚乙烯纤维的凝胶含量在空气中辐照交联较氮气中低 ,紧张状态下较非紧张状态下低 ,交联剂二丙烯基乙二醇三丙烯酸酯 ( TPGDA)较三羟基丙烷三丙烯酸酯 ( TMPTA)低 ,二甲苯溶液较丙酮溶液低 ,且凝胶含量随辐照时间的增加而增加。     

甲基丙烯酸镁助交联氯化聚乙烯橡胶耐老化性能的研究

研究甲基丙烯酸镁[Mg(MAA)2]助交联氯化聚乙烯橡胶(CM)的耐热空气、紫外光和臭氧老化性能,并与助交联剂TAIC助交联CM进行对比。结果表明,与采用助交联剂TAIC的CM硫化胶相比,采用助交联剂Mg(MAA)2的CM硫化胶热空气老化前后的拉伸性能和耐臭氧老化性能较好,耐紫外光老化性能相差不大。     

PE薄膜的交联改性

本文介绍了在紫外线照射和光敏剂作用下LDPE薄膜的光化学交联改性。薄膜的交联度随光照温度的提高而提高;交联度随光照时间的增加而增加,但光照5分钟后交联度随时间的变化不大;在本文的条件下,最高交联度可达84.46%。交联改性后薄膜的断裂伸长率下降。由于薄膜在光交联的同时也发生光降解反应,薄膜的拉伸强度也有所下降。随光照射时间和光照温度的增加,薄膜的透明度有所增加。通过交联后,薄膜的耐热性提高。该交联薄膜用作电线电缆的隔离膜和包扎膜,经过罐式硫化(155℃30min;165℃,30min)试验,其耐热性能和强度等均能满足要求。     

过氧化物交联HDPE材料的研究

研究了交联用高密度聚乙烯(HDPE)的种类、交联剂二叔丁基过氧化物(DTBP)、助交联剂T的用量对交联HDPE复合材料结构和性能的影响。选用辛烯为共聚单体和支化度(每1000C中的甲基数)为3.2的HDPE为原料树脂,主交联剂DTBP和助交联剂T的质量分数分别为0.15%,0.20%时,材料的各项性能符合交联HDPE管材的要求。     

Photocrosslinking of an ethylene–propylene–diene terpolymer and the characterization of its structure and mechanical properties

An ethylene–propylene–diene terpolymer (EPDM) was photocrosslinked under UV irradiation with benzil dimethyl ketal (BDK) as a photoinitiator and trimethylolpropane triacrylate (TMPTA) as a crosslinker. The efficiency of the photoinitiated crosslinking system EPDM–BDK–TMPTA, various factors affecting the crosslinking process (the photoinitiator and crosslinker and their concentrations, the irradiation time, the temperature, the atmosphere and UV‐light intensity, and the depth of the UV‐light penetration), and the mechanical properties of photocrosslinked EPDM were examined extensively through the determination of the gel contents, infrared spectra, and mechanical measurements. EPDM samples 3 mm thick were easily crosslinked with a gel content of about 90% after 30 s of UV irradiation under optimum conditions. The photoinitiating system of a suitable initiator combined with a multifunctional crosslinker such as BDK–TMPTA enhanced the efficiency of the photocrosslinking reaction, especially by increasing the initial rate of crosslinking. The gel content of photocrosslinked EPDM, which was determined by the content of diene in EPDM, the depth of the UV‐light penetration, and the light intensity, played a key role in increasing the mechanical properties of the photocrosslinked samples in this work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1837–1845, 2004     

Photocrosslinking of styrene–isoprene–styrene; effect of benzoin and ethylene glycol dimethacrylate on physical properties

Crosslinking reaction of polymer by ultraviolet (UV) irradiation has been important in industries. In this work, photocrosslinking of styrene–isoprene–styrene (SIS) triblock copolymer in the presence of benzoin photoinitiator and a dimethacrylate monomer as crosslinking agent was investigated. Curing of samples was initiated under UV irradiation. Benzoin was used as photoinitiator because it contains chromophore group that could absorb UV irradiation. Ethylene glycol dimethacrylate (EGDMA) was used as crosslinking agent, since it has alkene functional groups that could react with the alkene group of SIS. ATR-FTIR spectra of samples show that absorption band of double bond at 1500–1600?cm^?1 decreases after UV exposure. Increasing the concentration of benzoin (0.1–1?phr) and EGDMA (1–10?phr) leads to an increase in gel content and hardness, while swelling ratio decreases. After 5?min heating at 150?°C, about 20%wt of the unirradiated compound became insoluble, because heating of compound at 150?°C causes crosslinking reaction without any irradiation.     

Photocross-linking of low-density polyethylene. I. Kinetics and reaction parameters

The kinetic characteristics and the reaction conditions of photocross-linking of low-density polyethylene (LDPE) in the melt have been studied using benzophenone (BP) and its derivatives such as 4-chlorobenzophenone (4-CBP) as photoinitiator and triallyl cyanurate (TAC) as cross-linker. The efficiency of the photoinitiated cross-linking system LDPEBP-TAC and various factors affecting the cross-linking process, such as photoinitiator and cross-linker and their concentrations, irradiation time, temperature, and atmosphere, and UV light intensity were examined extensively by determining gel content, IR, and UV spectra. It has been found (i) that LDPE samples of 2–3 mm thickness are easily cross-linked to a gel content of about 70% with a UV-irradiation time of about 15 s under optimum conditions; (ii) that the photoinitiating system of a suitable initiator combined with a multifunctional cross-linker such as 4-CBP–TAC can enhance the efficiency of photocross-linking reactions, especially by increasing the initial rate of cross-linking; (iii) that photocross-linking of LDPE should be carried out in the melt, which increases the penetration of UV light by decreasing the scattering by crystallites, and (iv) that the rate of cross-linking is proportional to the square of the light intensity. An increase in light intensity can decrease the concentration of photoinitiator required to reach a certain rate of cross-linking. The photocross-linking of polyethylene is promising for industrial applications. © 1993 John Wiley & Sons, Inc.     

Photoinitiated crosslinking of ethylene‐vinyl acetate copolymers and characterization of related properties

Photoinitiated crosslinking of EVA in the presence of benzophenone (BP) as photoinitiator and triallyl isocyanurate (TAIC) as crosslinker and characterization of the related properties have been studied by gel determination, heat extension, DSC, DMTA, TGA, and mechanical measurements. The photoinitiated crosslinking efficiency of the EVA‐BP‐TAIC system and various factors affecting the crosslinking process, such as photoinitiator and crosslinker and their concentrations, irradiation temperature, and irradiation atmosphere were studied in detail and optimized by comparison of gel contents. The results show that the EVA samples with a thickness of 1 mm are readily crosslinked to a gel content of above 80% with 5 s UV‐irradiation under optimum conditions. The data from the heat extension and DSC show that the crosslinking density of photocrosslinked EVA increase and their crystallinities decrease with increasing the UV‐irradiation time. At the same time, photocrosslinking of EVA leads to a lowering of the melt temperature and a decrease of heat of fusion. The DMTA results show that photocrosslinking increases the amorphous phase and storage modulus of the crosslinked EVA, but does not change the glass transition temperature. The data from TGA and mechanical tests give evidence that the thermal stability and mechanical properties of photocrosslinked EVA samples are much better than those of the uncrosslinked EVA. POLYM. ENG. SCI., 47:1761–1767, 2007. © 2007 Society of Plastics Engineers     

The use of a recording dilatometer to study the photopolymerization of ethylene glycol dimethacrylate using the isobutyl ether of benzoin as photoinitiator

A simple recording dilatometer was adapted and used to determine or follow the rates of photopolymerization of ethylene glycol dimethacrylate with the isobutyl ether of benzoin as photoinitiator. The photopolymerization was recorded from 0% to 100% conversion of monomer to polymer, and the results from the dilatometer were compared with other methods (gravimetric, electrical resistance, and differential thermal analysis). The rates of photopolymerization were calculated as a function of initiator concentration, light intensity, and monomer concentration. Gel points could be directly determined along with the degree of conversion of monomer to polymer formation. The recording dilatometer can be used to measure rates of photopolymerization of ultraviolet crosslinking monomers, polymers, or coating systems.     

In situ study of photopolymerization by fourier transform infrared spectroscopy

The Fourier transform infrared (FTIR) in situ method was developed for the investigation of photopolymerization. Ultraviolet (UV) cure of a mixture of a cycloaliphatic epoxide, a 2-ethylhexyl acrylate, and photoinitiators, which forms simultaneous interpenetrating polymer network (IPN), was monitored while the sample was irradiated with UV light. Triphenylsulfonium salt and benzoin ether were used as photoinitiators. For the sake of comparison, similar experiments were performed for the epoxide with the triphenylsulfonium salt photoinitiator and the acrylate with the benzoin ether photoinitiator. The epoxy photopolymerization was monitored using an epoxy CH stretching band at 3005 cm^?1 and a ring vibration band at 790 cm^?1. The acrylic photopolymerization was monitored using a C?C stretching band at 1637 cm^?1. The epoxy conversion was less than 60% when the acrylic polymerization was completed in the IPN.     

Crosslinking of PVC formulations treated with UV light

Typical wire and cable formulations of plasticized Poly(vinyl chloride) were prepared with three different stabilizer systems: Ca/Zn (2:1 or 1:1) and dibasic lead phthalate. The mixtures contained trimethylolpropane trimethacrylate (TMPTMA) as crosslinking agent and a UV photoinitiator (Irgacure 819). Mixtures were dry‐blended, then roll‐milled and to finally hot‐pressed at 180°C to obtain sheets of 1 and 1.5 mm thickness. Small specimens (3 × 3 cm) were irradiated with UV light for up to 10 days while monitoring changes at different time intervals. The presence of TMPTMA in the samples, as expected, influenced the storage modulus (E′) and gel content percentage, specifically for the thinner samples. These results indicated that UV irradiation produced surface crosslinking. The samples with crosslinking agent also reached higher carbonyl index values. The Ca/Zn formulations showed higher mechanical properties with respect to the Pb ones, thus suggesting that during the stabilization period of the Ca/Zn mixtures, an effective crosslinking was promoted. Irregular behavior was observed during the last days of treatment for both types of formulations, thereby suggesting an optimum irradiation time for this procedure. J. VINYL. ADDIT. TECHNOL. 12:49–54, 2006. © 2006 Society of Plastics Engineers.     

丙烯酸酯单体紫外固化机理初探

本文选用了二缩三乙二醇双甲基丙烯酸酯为单体，安息香，安息香甲（乙、异丙）醚，二苯甲酮，α－羟甲基安息香甲醚、联苯酰二甲基缩酮，加入三乙胺和Ｎ，Ｎ－二甲基对甲苯胺等叔胺，在紫外照射下合，以红外光谱定量跟踪反应进行程度，实验结果表明，在单体中加入光引发剂后，紫外光照射时，聚合固化反应迅速进行，照射５分钟后反应程度达８６％～５０％，以安息香异丙醚得到的反应程度较高，加入叔胺后，降低了初始反应速度，但命名     

Adhesion properties of UV crosslinked polystyrene-block-polybutadiene-block-polystyrene copolymer and tackifier mixture

The peel and tack properties of mixtures of polystyrene-block-polybutadiene-block-polystyrene (SBS) and a tackifier were investigated after these were crosslinked by ultraviolet (UV) irradiation at various amounts of benzophenone (BP) as a photoinitiator and trimethylolpropane mercaptopropionate (TRIS) as a crosslinking agent.The degree of crosslinking of polybutadiene (PB) block in the SBS mixture was qualitatively estimated from the amount of gel fraction as well as the change in the glass transition temperature of the PB block. The crosslinking of the PB block was done within 3 min after UV irradiation and the peel strength of crosslinked specimens was as low as 45[percnt] of specimens without crosslinking. Nano-tack and bulk tack properties as well as the surface tension of mixtures were measured depending upon amounts of BP and TRIS.     

UV光固化环氧丙烯酸酯耐磨涂料的研究

以E51和E44环氧树脂和丙烯酸为原料,制备了UV固化环氧丙烯酸酯耐磨涂料。不同光引发剂、稀释剂和助剂等对UV固化环氧丙烯酸酯涂料固化性能均有影响。研究结果表明,用安息香乙醚与二苯甲酮(质量比为2∶1)的混合体系作为光引发剂的引发效率最高,最佳涂料配方:环氧丙烯酸酯∶丙烯酸丁酯∶安息香乙醚∶二苯甲酮∶滑石粉为70∶20∶4∶2∶4(质量比)。