含磷苯并噁嗪UV-LED固化防火涂层

为了获得低吸水率的防火涂层,合成了含磷苯并噁嗪,并将其用于制备环氧丙烯酸酯涂料,以LED-385 nm为光源对涂料进行光固化,研究了涂层的防火性能、附着力、铅笔硬度、耐酸碱性和耐水性。为了降低防火涂层中含磷元素的用量,同时保持涂层的防火性能,在上述体系中引入了盐酸多巴胺,并在此基础上探索了磷氮协同作用对涂层性能的影响。结果表明:2种含磷苯并噁嗪衍生物(DPOBH和DOPOBH)中,DPOBH对涂层防火性能、附着力和硬度的提升作用优于DOPOBH。添加3.7%DPOBH的涂层(EA/DPOBH3.7)的UL-94为V-0等级,硬度为B,附着力为1级,酸质量损失率仅为0.40%,碱质量损失率为2.13%,吸水率仅为0.82%。添加0.5%盐酸多巴胺所得涂层(EA/DPOBH3.5-N0.5)的UL-94为V-0等级,硬度为2H,附着力为1级,耐酸碱性提升。综上可知,在含磷苯并噁嗪环氧丙烯酸酯光固化涂层中磷氮协同作用可有效提升环氧丙烯酸酯涂层的防火性能和耐酸碱性能,降低吸水率。

在UV/H_(2)O_(2)去除对乙酰氨基酚工艺中Br^(-)的影响及其转化规律

Br^(-)是水和废水中常见的卤素离子,在高级氧化过程(advanced oxidation processes, AOPs)中通过形成不同种类的Br相关物种来发挥多种作用。在Br^(-)存在条件下,采用对乙酰氨基酚(acetaminophen, AAP)模拟废水进行UV/H_(2)O_(2)对其降解效能、机理以及Br^(-)转化规律的研究。结果表明,UV/H_(2)O_(2)降解AAP过程中,最佳去除率达到99.1%,但Br^(-)的加入抑制了AAP的降解和矿化,O~·_(2)和OH~·是UV/H_(2)O_(2)降解含Br^(-)的AAP模拟废水中主要活性物质,贡献率分别为45.5%和34.0%。当Br^(-)存在时,中性条件下,AAP降解速率最快,其一级动力学常数为0.048 4 min~(-1);其中活性溴物种(reactive bromide species, RBSs)对AAP降解的贡献率为14.1%。自由基浓度模拟结果表明,Br^(·-)_(2)可能在有机溴的形成过程中发挥着重要的作用。H_(2)O_(2)的直接还原作用导致Br^(-)转化率仅为18.0%。此外,由于溴自由基的加成,容易生成一些具有生态毒性的副产物,并通过分析溴代产物推测了AAP的降解路径。

UV/SO_(3)^(2-)工艺去除水体中溴酸盐的效果

紫外/亚硫酸盐(UV/SO_(3)^(2-))工艺是一种通过产生强还原性的活性自由基来降解污染物的高级还原工艺(ARPs)。文章研究了UV/SO_(3)^(2-)工艺降解溴酸盐(BrO_(3)^(-))的效能与机制。结果表明,UV/SO_(3)^(2-)工艺还原BrO_(3)^(-)符合拟一级动力学模型;增大UV光照强度、SO_(3)^(2-)投加量、溶液pH,去除溶液中的溶解氧(DO),可有效提高Br O_(3)^(-)的去除率;水体中的HCO_(3)^(-)、Cl^(-)和天然有机物会不同程度地抑制BrO_(3)^(-)的降解;自由基淬灭试验显示水合电子(eaq)是UV/SO_(3)^(2-)工艺降解BrO_(3)^(-)的主要活性物质,并由此推断出可能的BrO_(3)^(-)降解路径。

Synthesis of a Novel UV Curable Aqueous Dispersion Polyurethane PDHA-PEDA-PU and the Properties of Cured Film

A novel ultraviolet （UV） curable aqueous dispersion polyurethane PDHA-PEDA-PU was synthesized based on isophorone diisocyanate （IPDI）, polyester dihydric alcohol （PDHA）, dimethylol propionic acid （DMPA）, pentaerythritol diacrylate （PEDA）, 2-hydroxyethyl acrylate （HEA） and triethylamine （TEA）. Acrylate groups were incorporated in the side and end of PDHA-PEDA-PU chain. The C=C content in the chain can be controlled easily through the change of IPDI/PDHA/PEDA ratio. Fourier transform infrared spectroscopy （FTIR） was used to identify the structure of prepolymer, aqueous dispersion and cured polyurethane. The curing rule of the polyurethane for different C=C content has been investigated depending on the change of C=C content during the curing process. The hardness, thermal stability and scrub resistance to MEK of UV cured PDHA-PEDA-PU were also discussed for the samples with different C=C content.

Synthesis and Properties of UV-curable Hyperbranched Polyurethane and Its Application in the Negative-type Photoresist

UV-curable hyperbranched polyurethane （UV-HBPU） containing carboxyl groups was synthesized from isophorone diisocyanate （IPDI）, diethanolamine （DEOA）, polyethylene glycol （PEG-400）, hydroxyethyl acrylate （HEA）, and 2,2-his （hydroxymethyl） propionic acid （DMPA）. The UV-HBPU was used as a negative-type photoresist for a printed circuit board （PCB）. Fourier-transform infrared spectroscopy （FTIR） and proton nuclear magnetic resonance （1HNMR） spectroscopy of UV-HBPUs indicated that the synthesis was successful. Differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA） showed that the thermal stability of the UV-HBPUs decreased as the HEA content increased. The polymer exhibited excellent photoresist properties, and the resolution of circuits based on this negative-type photoresist reached 10 μm.

Synthesis of a Novel UV-curable Prepolymer Polypropyleneglycol Diglycidyl Ether Diacrylate

A novel UV-curable prepolymer polypropyleneglycol diglycidyl ether diacrylate （PPGGEA） was synthesized by utilizing polypropyleneglycol diglycidyl ether （PPGGE） and acrylic acid （AA） as starting materials, N, N-dimethylbenzylamine as catalyst and p-hydroxyanisole as inhibitor. The optimum synthetic conditions were in the following： the concentration of N, N-dimethylbenzylamine was 0.80 wt% of reactants, the concentration of p-hydroxyanisole was 0.3 wt% of reactants, the reaction temperature was 90-110 ~C, and the molar ratio of PPGGE to AA was 1：2.2. Meanwhile, 1-hydroxycyclohexyl phenyl ketone of a UV-cured initiator was added to the synthesized PPGGEA to prepare a kind of UV-cured coating. The mechanical properties of the UV-cured films were determined, giving 29.99 MPa of tensile strength, 834.27 MPa of the Young＇s modulus and 5.66% of elongation at tear.

Synthesis of a Novel UV-curable Prepolymer Hexanediol Diglycidyl Ether Diacrylate and Its Cured Film Tensile Property

A novel UV-curable prepolymer hexanediol diglycidyl ether diacrylate （HDGEA） was synthesized by utilizing hexanediol diglycidyl ether （HDGE） and acrylic acid （AA） as starting materials, N, N-dimethylbenzylamine as catalyst and p-hydroxyanisole as inhibitor. The optimal synthetic conditions were that the concentration of N, N-dimethylbenzylamine was 0.80 wt% of reactants, the concentration of p-hydroxyanisole was 0.3 wt% of reactants, the reaction temperature was 90-110 ℃, and the molar ratio of HDGE to AA was 1︰2.2. Meanwhile, 1-hydroxycyclohexyl phenyl ketone of a UV-curing initiator was added to the synthesized HDGEA to prepare a kind of UV-curing coating. The mechanical properties of the UV-cured films were determined, giving 31.87 MPa of tensile strength, 871.88 MPa of Young＇s modulus and 6.77% of elongation at tear.

Preparation and Properties of Aqueous SCNTs Dispersion based on A UV-curable Polymeric Dispersant

A novel photosensitive copolymer P（SS-co-AA-g-GMA）（PSAG） was synthesized and utilized to noncovalently functionalize pristine single-walled carbon nanotubes（SCNTs）. PSAG was highly effective for the solubilization of SCNTs in water and validated by UV-vis absorption spectra experiments, resulting in homogeneous and stable PSAG-SCNT aqueous dispersion. The microstructure of SCNTs was observed through Raman spectroscopy and transmission electron microscopy. In addition, compared with the two common polymeric dispersants of Triton X-100 and PSS, PSAG demonstrated more effective performances for dispersing SCNTs under identical conditions. Furthermore, the photosensitive PSAG-SCNTs can be crosslinked after UV irradiation, leading to significant improvement in the water resistance of SCNT films. UV-cured films can be transferred to plastic wrap to form a flexible film with high electrical conductivity.

A Photosensitive Copolymer for UV-curable Electrodeposition Coatings

A series of photosensitive random copolymers （UPDHES） were prepared by introducing acrylate groups onto the side chain of the copolymer backbone of N, N-domethyl amimethyl methacrylate （DMAEMA）, 2-hydroxypropyl acrylate （HEA）, 2-ethylhexyl acrylate （EHA）, and styrene （St） （PDHES）. The molecular structure of UPDHES was characterized by FTIR, 1HNMR and GPC. The photopolymerization kinetics of UPDHES with different C=C content was investigated using real time FTIR in which it was found that the UPDHES system had notable photosensitivity. The effect of C=C content on the properties of cured films were studied by evaluating various film properties such as thermal stability, glass transition temperature and tensile properties. The thermal degradation of cured films was investigated via thermogravimetric analysis/infrared spectrometry （TGA-IR）. Thus a series of UV-curable electrodeposition coatings with good photosensitivity and mechanical properties were prepared from a low-cost photosensitive random copolymer.

Synthesis of a Novel UV-Curable Diluent Benzyl Glycidyl Ether Acrylate and Its Application

A novel UV-curable diluent benzyl glycidyl ether acrylate(BGEA) was synthesized by utilizing benzyl glycidyl ether(BGE) and acrylic acid(AA) as starting materials,N,N-dimethylbenzylamine as catalyst and p-hydroxyanisole as inhibitor.The optimum synthetic conditions were that the concentration of N,N-dimethylbenzylamine was 0.90% of reactants by weight,the concentration of p-hydroxyanisole was 0.20% of reactants by weight,the reaction temperature was 90-100℃,and the molar ratio of BGE to AA was 1.00:1.10.The experiment shows that BGEA is a kind of good diluent.The mechanical properties of the UV-cured films with BGEA as diluent to prepare UV-curing coating were superior to that of the UV-cured films with butyl acrylate as diluent to prepare UV-curing coating.

Preparation of UV-curable Nano-silver Antimicrobial Agent and Its Application in Non-woven Fabric

Nano-silver and waterborne polyurethane(WPU)composite emulsion was synthesized.The average diameter of silver nanoparticles(SNPs)was about 20 nm,and the average diameter of WPU was 101.32 nm.The anti-bacteria finishing of a polypropylene non-woven fabric(NWF)was carried out by ultraviolet finishing technology and the double dipping twin-roll method.The standard AATCC100 was used to test the antimicrobial activity of the samples.The results showed that the antimicrobial rates of Klebsiella pneumoniae(K.pneumoniae)and Staphylococcus aureus(S.aureus)were above 90%,which indicated that the NWF finishing had good antimicrobial activity.In addition,the thermal stability,mechanical properties,whiteness and contact angle of antimicrobial finishing nonwovens were characterized.The results showed that the performance of antimicrobial nonwovens was stable at 300℃.The breaking strength was better than that of untreated nonwovens,and the contact angle reached 119.1°.

Synthesis of a novel UV-curable prepolymer neopentyl glycol diglycidyl ether diacrylate and its cured film tensile property

A novel UV-curable prepolymer neopentyl glycol diglycidyl ether diacrylate (NPGGEA) was synthesized by using neopentyl glycol diglycidyl ether (NPGGE) and acrylic acid (AA) as starting materials, N, N-dimethylbenzylamine as catalyst and p-hydroxyanisole as inhibitor. The optimum synthetic conditions were taken as follows: The concentration of N,N-dimethylbenzylamine, 0.80% of reactants; the concentration of p-hydroxyanisole, 0.3% of reactants; the reaction temperature, 90-110 ; the molar ratio of NPGGE to AA, 1:2.2. Meanwhile, 1-hydroxycyclohexyl phenyl ketone of a UV-cured initiator was added to the synthesized NPGGEA to prepare a kind of UV-cured coating. Mechanical properties of the UV-cured films were determined, giving 28.75 MPa of tensile strength, 923.82 MPa of Young’s modulus and 5.51% of elongation at tear.

Synthesis of A Novel UV-curable Oligmer 1,4-cyclohexanedimethanol Glycidyl Ether Acrylate and Study on Its UV-curing Properties

A novel UV-curable oligmer 1,4-cyclohexanedimethanol glycidyl ether acrylate（CHDMGEA） was synthesized by utilizing 1,4-cyclohexanedimethanol glycidyl ether（CHDMGE） and acrylic acid（AA） as starting materials, triphenyl phosphine as catalyst and p-hydroxyanisole as inhibitor. The optimum synthetic conditions were that the concentration of triphenyl phosphine was 0.90% of reactants by weight, the concentration of p-hydroxyanisole was 0.20% of reactants by weight, the reaction temperature was 90-100 ℃, and the molar ratio of CHDMGE to AA was 0.5：1.1. The experimental results show that CHDMGEA is a kind of good UV-curable oligmer. The impact resistance of the UV-cured films with CHDMGEA as oligmer to prepare UV-curing coating was superior to that of the UV-cured films with bisphenol A diglycidyl ether diacrylate（BPGEA） as oligmer to prepare UV-curing coating.

UV引发硫醇-烯反应制备OLED屏封装用八乙烯基倍半硅氧烷/聚氨酯丙烯酸酯液态光学胶

有机发光器件(OLED)是新一代显示屏,其中用于显示屏组件间粘接的液态光学透明胶(LOCA)是OLED的关键材料之一,高折射率、高导热性及高稳定性的LOCA对OLED性能尤为重要。文中采用八乙烯基倍半硅氧烷(OvPOSS)作为增强填料、三羟甲基丙烷三(3-巯基丙酸酯)(TTMP)作为交联剂,通过简单的UV引发硫醇-烯反应将OvPOSS接枝到具有良好黏附性和光学性能的聚氨酯丙烯酸酯(PUA)树脂中,制备出高透明性高折射率的LOCA。研究表明,制备的LOCA在365 nm UV照射20 s内即可固化,相比商用UV胶几分钟的固化时间,固化速度更快、能耗更低;当OvPOSS的质量分数为7%时,相比纯的PUA,折射率提高到1.525以上,热分解温度(T_(d5%))比纯PUA提高了30℃,玻璃化转变温度提高了5.3℃,导热系数从0.0609 W/(m·K)提高到0.1710 W/(m·K),粘接强度从3.16 MPa提高到3.48 MPa,室温日照1440 h后仍可达到99%以上的可见光透过率,水中浸渍3600 h后吸水率仅为0.52%,低于目前文献中的0.70%(24 h),在光电器件封装中具有较大应用前景。

参与UV固化交联反应的有机硅聚氨酯改性Irgacure-2959大分子UV引发剂的制备与性能

针对小分子紫外光(UV)引发剂存在的有一定毒性、有气味、易黄变及易从UV固化材料中迁移出来等缺点,以及为解决UV固化在工业生产中难以避免的氧阻聚现象,遴选生物相容性良好的小分子UV引发剂2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮(Irgacure-2959)、生物基原料蓖麻油、羟烃基硅油、异佛尔酮二异氰酸酯和甲基丙烯酸羟丙酯为原料,设计合成了可参与UV固化交联反应的有机硅改性大分子UV引发剂.随后,用其引发丙烯酸酯基聚氨酯预聚物UV固化,制备了高透明UV固化材料.研究结果表明,所得UV引发剂用量(质量分数)为3%,固化时间为70 s时,制备的UV固化材料铅笔硬度可达2H~4H,透光率可达80%,拉伸强度26.4 MPa,断裂伸长率从18%增加至42%.小分子UV引发剂Irgacure-2959的迁移率为7.2%,用其制备的UV固化材料经UV老化4 min就显著变黄;而所得参与UV固化交联反应的有机硅改性大分子UV固化引发剂的迁移率低至2.1%,所制备的UV固化材料经UV老化14 min才略微变黄.因此,研制参与UV固化交联反应的有机硅改性大分子UV引发剂是降低UV引发剂迁移率、改善UV固化材料的耐UV辐射性能和柔韧性的有效途径.

高卤染料废水采用UV/SO_(3)^(2-)工艺减毒过程中的中间产物及其毒性变化规律研究

染料废水含有大量难降解有机污染物,其中的有机卤代物通常具有较大的毒性和生态风险,但这类物质在常规的生物处理和化学处理工艺中的去除效果不佳。针对染料废水的脱卤困境,研究采用UV/SO_(3)^(2-)高级还原工艺对染料废水进行还原脱卤。在初始pH为8.5,SO_(3)^(2-)投加量为40 mmol·L^(-1)的条件下,废水中52.2%的可吸附有机卤素(adsorbable organic halogens,AOX)可以在反应开始6 h后被去除,更高的初始pH和更大的SO_(3)^(2-)投加量均有利于提升AOX的去除率。中间体的定性和半定量研究揭示了染料废水中部分氯代苯胺类物质的还原脱卤路径,发现苯胺很可能是这些物质还原脱卤的主要产物。废水中有机物的平均预测毒性揭示了还原过程中废水急性毒性的变化趋势。这一趋势与T_(3)发光杆菌和小球藻的急性毒性评价结果一致。此外,染料废水的AOX浓度与T_(3)发光杆菌的发光抑制率呈现正相关关系,而且染料废水经过还原脱卤后,尽管水中盐含量有所增加,其EC_(50)由1.26 mg·L^(-1)增加到5.94 mg·L^(-1),这也证明了还原脱卤过程可以降低出水的急性毒性。因此,UV/SO_(3)^(2-)过程可以通过对水中有机卤代物的还原脱卤降低出水中的AOX,降低废水急性毒性和生态风险。

Synthesis and properties of UV curable polyurethane acrylates based on two different hydroxyethyl acrylates

Two kinds of UV curable polyurethane acrylate oligomers(PUPA and PUCA) were synthesized via the addition reaction between isophorone diisocyanate(IPDI) and polyethylene glycol monoacrylate(PEA6) or polycaprolactone modified hydroxyethyl acrylate(PCLA2).The structures of PUPA and PUCA were characterized by Fourier transform infrared spectroscopy(FT-IR),1H nuclear magnetic resonance(1H NMR),gel permeation chromatography(GPC) and differential scanning calorimeter(DSC),and the thermal stability and dynamic mechanical thermal properties of their cured films were measured by thermogravimetric analysis(TGA) and dynamic mechanical analysis(DMA),respectively.The viscosity of the oligomers and mechanical properties of the cured films were also studied.The results show that both oligomers have narrow molecular weight distribution.The viscosity of PUPA is 2.310 Pa.s at 25 °C,while that of PUCA is up to 3.980 Pa.s.The UV cured PUPA and PUCA films have homogeneous phase structure,and the PUCA film shows higher glass transition temperature and storage modulus.Furthermore,the PUCA film possesses better mechanical properties than PUPA,while the latter shows better alkali resistance.

UV固化超支化聚氨酯木器涂料的制备及性能研究

传统UV固化聚氨酯树脂以端双键封端,极性基团少,降低了涂层在木材表面的附着力。采用两步法将一种多羟基的超支化结构引入由不同异氰酸酯制备的聚氨酯体系中并封端,合成了含有多羟基超支化结构的紫外光固化聚氨酯木器涂料。采用凝胶渗透色谱仪(GPC)、核磁共振波谱仪(NMR)、傅立叶变换红外光谱仪(FT-IR)、热重分析仪(TG)、动态热机械分析仪(DMA)等测试表征方法,研究了紫外光固化聚氨酯树脂及木器涂料的各项性能。结果表明:—NCO与—OH物质的量比为1∶8的多羟基超支化异氰酸酯制备成功并引入到聚氨酯中,其中以六甲撑基二异氰酸酯为主体聚氨酯的拉伸强度达到34.69 MPa,弹性模量达到10.64 MPa,玻璃化转变温度为102.02℃,漆膜附着力为0级。此方法为具有高强度、高附着力的UV固化型聚氨酯木器涂料提供了创新解决方案。

MODIFIED ULTRAVIOLET-CURABLE WATER DISPERSIBLE POLYURETHANE-ACRYLATES

Three kinds of UV-curable self-emulsified polyurethane-acrylate (PUA) prepolymer, i.e., conventional, chain extended and grafted PUAs, were prepared. The relatively small particle size of the PUA dispersions indicates that the PUA prepolymers exhibit sufficient aqueous dispersibility. The PUA prepolymers can substantially lower the interfacial tension of water. Chain-extended PUA dispersions exhibit pseudoplastic behavior and thixotropy to a greater extent than do their conventional counterpart. The chain-extended and grafted PUA photocure to higher conversion than do the conventional PU equivalent. The results of DSC measurement suggest that there exists phase mixing between the hard and the soft segment phases for the PUAs based on PEG 400 that is the comparatively short soft segment in the prepolymer. For the PUA prepolymers based on PEG having higher M-n values, chain-extending and grafting could impede the phase separation between the hard and the soft segment domains. The adhesion, impact strength and flexibility of the photocured films were tested.

高效液相色谱-串联质谱法测定塑料食品接触材料中受阻胺光稳定剂UV4050的迁移量

以水、4%(体积分数)乙酸溶液、异辛烷以及体积分数分别为10%,20%,50%,95%的乙醇溶液作食品模拟物,按照GB 5009.156-2016和GB 31604.1-2015的规定进行迁移试验。除异辛烷外的其余6种食品模拟物的浸泡液直接进样分析;取异辛烷浸泡液10 mL,加入10 mL 40%(体积分数)甲醇溶液,振摇1 min,静置30 min,取下层甲醇溶液,过0.22μm有机滤膜,滤液上机测定。色谱分析采用ACQUITY UPLC BEH C18色谱柱作固定相,含0.1%(体积分数)甲酸的50%(体积分数)甲醇溶液作流动相进行等度洗脱分离。质谱分析采用电喷雾离子源正离子(ESI+)和多反应监测(MRM)模式进行检测。结果显示,不同食品模拟物中受阻胺光稳定剂UV4050的质量浓度在5~200μg·L^(-1)内和对应的峰面积呈线性关系,测定下限(10S/N)为0.6~2.4μg·L^(-1)。按照标准加入法进行回收试验,回收率为88.1%~109%,测定值的相对标准偏差(n=6)为0.90%~8.9%,并成功用于实际塑料食品接触材料样品的分析。