基于D-A反应的光固化自修复聚氨酯涂料及其性能研究

以对苯基亚甲基双马来酰亚胺(BMI)和糠醇(FA)为反应单体,通过Diels-Alder反应制备得到带羟基的改性DA单体,再以不同分子量的聚碳酸酯二元醇(PCDL)、异佛尔酮异氰酸酯(IPDI)、改性DA单体为反应单体,得到聚氨酯预聚物,然后与甲基丙烯酸羟乙酯(HEMA)反应得到光固化自修复聚氨酯。利用傅立叶红外光谱(FT-IR)、核磁共振氢谱(1 HNMR)等表征了树脂的结构,同时考察了树脂的光固化性能。再以聚氨酯树脂为基体树脂,通过配方设计制备了光固化自修复凃料。通过超景深显微镜和热重分析仪(TGA)对涂料的基本性能、自修复性能、热性能进行了测试,结果表明:随着PCDL分子量的增加,涂层的硬度有所下降,而DA单体的引入赋予涂层自修复性能的同时可以提高涂料的硬度。     

含羧基嵌段的离聚体的合成及其性能研究

合成了羧基有序分布和羧基无序分布的两类光固化水性聚氨酯丙烯酸酯 (PUA)的离聚物 ,研究了其光固化反应动力学 ,并测定其预聚物分散液的性能和固化膜的性能。     

三官能度甲基丙烯酰氧基单体的合成与性能研究

用甲基丙烯酰氯分别与二乙醇胺和三乙醇胺反应合成了两种三官能度甲基丙烯酰氧基单体.以实时红外光谱(RT-IR)法研究了两种单体的光聚合动力学性质,考察了不同单体、不同引发剂和引发剂浓度、不同光强对聚合性能的影响,并采用动态力学分析仪(DMA)测试了光固化后材料的力学性能.结果表明,随着引发剂浓度的增大,单体转化率、最大反应速率都增大,随着光强的增大,单体转化率、最大反应速率都降低.与二苯甲酮(BP)相比,2-羟基-2-甲基-1-苯基丙酮(1173)对两种单体具有较好的引发效果.两种单体加入三缩四乙二醇双甲基丙烯酸酯(SR209)中后,对体系光固化后的产物力学性能有不同影响.     

一类高折射率光固化有机硅树脂的性能研究

光固化有机硅材料兼具光固化的高效、能耗低和环保以及有机硅树脂优异的耐温、耐候性和电绝缘性能,因此,在LED等电子器件封装方面受到广泛关注.本文研究了自制的3种含丙烯酸酯基团的光固化苯基有机硅预聚物KDS-10、KMDS-03和KMS-03的光固化特性、光学性能和热稳定性能.结果表明,这些有机硅预聚物的折光指数随苯环含量的增加而增高,苯环含量从22.3%到37.7%,折光指数相应从1.496到1.542;3种预聚物与多种丙烯酸酯相容性好,用双官能的TPGDA作稀释剂,固化反应速率最快,丙烯酸酯基团的转化率也最高;光引发剂TPO引发的光固化反应速率和转化率均最高;高折射率有机硅预聚物KDS-10光固化后的薄膜具有优异的光学性能,在550 nm处的透过率为92.54%;玻璃化转变温度约为-17.41℃,起始分解温度为385℃.     

混杂光固化体系的原理及应用

混杂光固化或双重固化是指在同一体系中采用两种或两种以上不同类型的聚合反应来使体系固化的方法,它是原位改性高分子的一种新方法.混杂光固化体系包括自由基-阳离子混杂光固化体系、自由基-缩聚混杂体系和自由基-自由基混杂体系等.本文综述了混杂光固化体系的原理及其应用.     

巯基/(甲基)丙烯酸(甲基)烯丙酯光固化特性

通过对羧酸盐法改进后合成同时含有高活性的丙烯酸酯型C=C和低自由基活性的烯丙基型C=C的烯类单体(甲基)丙烯酸(甲基)烯丙酯,以实现(甲基)丙烯酸酯类紫外光固化与巯/烯光聚合结合在二元体系中;并以1173为光引发剂,利用实时红外(RT-IR)跟踪此类烯烃与三羟甲基丙烷三(3-巯基丙酸酯)(TMMP)光固化过程,探究烯烃结构、光强和引发剂用量对含有两类碳碳双键的烯类单体与巯基化合物二元体系的光固化行为的影响.研究发现,这类二元巯-烯光聚合反应中均有(甲基)丙烯酸酯双键的反应活性最大,(甲基)烯丙基次之,巯基的反应活性最小;甲基取代在烯烃的不同C=C上,对巯-烯光固化特性影响不同,甲基取代在烯丙基C=C上比甲基取代在丙烯酸基C=C上对巯-烯光固化行为影响更大;巯基最终转化率随甲基取代基数目增多而减少;丙烯酸甲基烯丙酯体系中两类双键(丙烯酸型/甲基烯丙基型)反应活性几乎相同且均具有高的转化率.     

紫外光固化超支化聚硅氧烷的合成及其光固化动力学研究

利用γ-甲基丙烯酰氧基丙基三甲基硅氧烷的受控水解反应即A2-B3单体对法来制备超支化聚硅氧烷,并对合成出的聚合物通过FT-IR、1H-NMR和多角度激光光散射技术(MALLS)进行了表征.结果表明,所得聚合物具有超支化结构且分子中含有大量活性官能团,从而可以实现紫外光引发固化.通过等温差示光量热实验(DPC)研究了聚合物结构、引发剂用量、光强度和聚合温度对聚合物光固化行为的影响规律,并得到了其中一种聚合物的光固化动力学参数,光固化反应总级数约为3,表观活化能为16.9kJ/mol.     

超支化烯丙基聚硅氮烷-巯基化合物体系紫外光固化研究

采用等温差示光量热扫描技术(DPC)研究了超支化烯丙基聚硅氮烷-巯基化合物体系的紫外光固化.对比了超支化聚合物-巯基化合物体系、二官能烯丙基硅氮烷-巯基化合物体系和超支化自聚体系的紫外光固化特性,结果表明超支化-巯基化合物体系可在引发剂浓度低(0.1wt%)、辐照强度低(5mW/cm2)的情况下迅速发生光固化反应;与超支化自聚反应相比固化速率高、双键转化率高;而与低官能-巯基化合物体系相比,由于超支化分子结构的独特性,导致固化速率快,双键转化率偏低.对引发剂浓度、辐照强度和反应温度对固化行为的影响表明,在引发剂浓度不超过0.5wt%和辐照强度不大于30.50mW/cm2时,反应速率分别与引发剂浓度和辐照强度的1/2次方成线性关系.运用带扩散因子的自催化固化动力学模型研究了不同温度下的固化行为,计算出特定条件下的光固化动力学参数,表观总反应级数约为8.76,表观活化能为13.97kJ/mol.     

单宁酸改性制备光敏碳纳米管及UV光固化AESO复合膜的制备

本文以单宁酸（TA）和甲基丙烯酸缩水甘油酯（GMA）为原料，通过开环反应制备出含有双键的光敏单宁酸（pTA），并通过π-π非共价键作用使其吸附到碳纳米管上，得到pTA修饰后的具有良好分散性的光敏碳纳米管（pTA/MWCNTs）。再将该pTA/MWCNTs作为填料添加到环氧大豆油丙烯酸酯（AESO）中，通过UV光固化得到AESO-pTA/MWCNTs复合膜。利用pTA对MWCNTs进行改性，提高了MWCNTs的分散性，同时引入双键，使得pTA/MWCNTs能够参与到光固化过程中，提高了碳纳米管与AESO基质间的界面粘结力，对AESO起到了比较好的增强作用。本文还研究了pTA/MWCNTs的加入对AESO复合涂料光固化动力学及涂膜性能的影响，结果表明该pTA/MWCNTs的掺入提高了光固化AESO复合膜的力学性能，当掺入量为0.8%时，对膜的增强效果最好，与纯AESO比较，其拉伸模量提高了390%，拉伸强度提高了110%。     

荧烷染料/二芳基碘鎓盐同步光生色和光聚合体系

荧烷染料(FR)和二芳基碘盐(On⁺X^-)组成的体系,在光作用下,通过激发态的荧烷染料与碘盐之间发生电子转移反应,生成开环结构的荧烷染料有色体,伴随发生盐的光解反应,生成活性引发自由基碎片。该体系不仅可有效地引发烯类单体的聚合反应,也可同步发生光生色作用,产生较高的色密度。进一步研究了二芳基碘盐的取代基不同碳链长度和不同对离子及浓度诸因素,在光固化体系中对生色反应的影响。同时FR/On⁺X^-体系引发光交联形成的有色薄膜具有良好的色稳定性。     

光固化3D打印及其在齿科行业中的应用

光固化3D打印是最早出现的3D打印技术,经过30多年的发展,先后发展出液态树脂固化或光固化（stereolithography,SLA）、数字光处理（digital light processing,DLP）、液晶显示（liquid crystal display,LCD）、连续无分层液体界面提取技术（layerless continuous liquid interface production,CLIP）、双光子3D打印（two-photon polymerization,TPP）、全息3D打印技术等多种打印技术。光固化3D打印技术具有精度高、成型速度快等特点,因此在许多领域都有良好的应用,且前景广阔。在众多领域中,齿科领域个性化特征明显,对打印材料精度要求高,是目前光固化3D打印最有应用潜力和高附加值的领域。本文综述了光固化3D打印技术的种类、原理和技术的优缺点,并简述了光固化3D打印在齿科领域的应用。     

Reaction kinetics and network characterization of UV-curing polyester acrylate inorganic/organic hybrids

Polyester acrylate inorganic/organic hybrids were prepared using a sol-gel precursor, coupling agent, and reactive diluent. The hybrids were cured via a UV-free radical initiator. Design of experiments (DOE) was utilized to investigate reaction kinetics and complex variable interactions. The effects of the silicate groups on the free radical photo-curing reaction kinetics were investigated utilizing a time-resolved Fourier transform infrared (FT-IR) spectroscopy and a differential scanning calorimeter equipped with a photocalorimetric accessory (photo-DSC). Microgel and inorganic network formation during the UV-initiated free radical crosslinking reactions was suggested to describe the complex gel-point behavior. It was proposed that the formation of the inorganic silicate groups retarded the organic crosslinking reactions. The UV-cured inorganic/organic hybrid films exhibited more homogeneous film morphology compared to the organic counterparts. In the hybrid films, a core-shell like inorganic/organic particle morphology was observed. The UV-crosslinked organic phase forms the core, whereas, the inorganic silicate forms the surrounding shell.     

基于原位体积加成制备导电线路的研究

本文提出一种制备导电电路的方法。以纳米铜为导电填料，以光固化树脂为连接剂，制备含铜光固化油墨，利用丝网印刷方法获得含有纳米铜的图案，利用铜与银盐间的置换反应，将铜纳米粒子图案通过原位体积加成转化为导电银图案。研究结果表明，铜图案不具有导电性，而置换反应生成的银图案具有导电性，且导电能力受铜含量、银盐浓度、光照时间、浸泡反应时间等因素影响，本实验中获得的最高电导率为1.25×10⁵ S/m，导电线路具有良好的耐弯曲、耐疲劳性能，同时兼具优异的可修复性能，为导电线路的制备提供了常温下简单有效、成本低廉的实现方法，具有重要的参考价值。     

Photo-stability of photo-cured organic coatings: Part III—Photo-degradation of organic coatings photo-cured with alkoxyacetophenone and hydroxy alkylacetophenone photo-initiators

Photo-degradation studies of polystyrene (as model) and coating resins were made with three different photo-fragmenting initiators: 2,2-dimethoxy-2-phenylacetophenone, 1-[4-(2-propyl)-phenyl]-2-hydroxy-2-methyl-propanone-1 and 1-benzoyl-1-hydroxy-cyclohexane. Addition of the initiators to a benzene solution of polystyrene gave a rapid decrease in molecular weight when the solutions were uv irradiated. The degradation rate was increased by the presence of oxygen. Irradiation of polystyrene films, containing the same initiators, showed similar effects. In addition, the polymer became partially crosslinked. Addition of a free radical scavenger decreased the degradation rate. Both photo-oxidation rate and yellowing rate were affected by the concentration and the reactivity of the radicals. Photo-oxidation during photo-curing of a coating occurs in a thin surface layer. This is due to a combination of free radicals formed by the uv irradiation and the oxygen present. Oxidation during the photo-curing of a urethane resin corresponds to more than 50% of the total surface oxidation measured with ESCA.     

Kinetic investigation of photopolymerization initiated by oligomeric photolatent base

Macrophotoinitiators often show polymer effect and photolatent bases make molecular amplification reaction. A main-chain oligomer containing α-aminoalkylphenone chromophore (OAK) had been synthesized with the characteristics of both photoinitiators and photolatent base hybrid structure. In order to determine whether such an effect or reaction exists in photopolymerization initiated by OAK, we used photo-differential scanning calorimeter to analyze the kinetic behavior. The experimental rate constants at different conversions were obtained by Arrhenius equation at different temperatures, the theoretic rate constants were simultaneously calculated with the use of phenomenological model. The results showed that the model correctly predicts the rate constant at the early stage, but underestimates it later. The comparative experiment between OAK and polymeric α-hydroxyalkylphenone photoinitiator (KIP150) shows that the molecular proliferation reaction caused by OAK significantly increases the experimental rate constant in the high-crosslinked stages of the polymerization. The photolatent base would be expected to provide one possible pathway in tackling photo-curing of opaque/thick material.     

Facile and robust strategy to antireflective photo-curing coating through self-wrinkling

We reported a facile and bio-inspired strategy for obtaining antireflective(AR) coating through polymerization-induced self-wrinkling. Upon irradiation of light, the complex wrinkle micro-patterns with different morphologies were generated spontaneously on the surface of coating during photo-crosslinking, which enables the photo-curing coating can decrease reflection. The resulting photo-curing coating exhibits a high transmittance over 90% and low reflection below 5%～8%, with an efficiency antireflection of 4%～7% compared to the flat blank coating. The successful application of these AR coatings with wrinkles pattern to encapsulate the thin film solar cells results in appreciable photovoltaic performance improvement of more than 4%～8%, which benefits from the decrease of the light reflection and increase of optical paths in the photoactive layer by the introduction of wrinkling pattern.Furthermore, the efficiency improvements of the solar cells are more obvious, with a remarkable increase of 8.5%, at oblique light incident angle than that with vertical light incident angle     

环氧液晶弹性体材料的制备与力学性能研究

传统的液晶弹性体材料多采用丙烯酸酯类或聚硅氧烷类分子,通过自由基聚合制备.然而由于自由基聚合易被氧气阻聚,固化过程收缩率高且内应力大,传统液晶弹性体材料的力学性能并不是很优异.为解决这一问题,本文合成了带有环氧基团的液晶单体和交联剂,使用碘鎓盐作为引发剂,通过光引发阳离子反应,用原位聚合交联法制备了环氧液晶弹性体材料.光引发阳离子聚合和传统自由基聚合相比,不受氧气影响且弹性体固化时体积收缩率小.对制备出的液晶弹性体材料的晶相和力学等性能进行探究和表征,发现其比传统的丙烯酸酯类或者聚硅氧烷类液晶弹性体材料具有更优异的力学性能,在清亮点以上,其弹性模量达到了0.92 MPa.     

Combining photo-cleavable and hydrogen-abstracting groups in quinoxaline with thioether bond as hybrid photoinitiator

We synthesized four diphenylquinoxaline derivatives(SQs) with phenyl-thioether units, which combine photo-cleavable and hydrogen-abstracting groups in one molecule. The photochemistry and photopolymerization of SQs were investigated. SQs possess suitable UV-vis absorption in the range of 350-400 nm with high extinction coefficients. UV-vis and HPLC-MS spectra revealed that C–S bond in phenyl-thioether group of SQs can be broken by irradiation of UV-light. Photolysis and photopolymerization experiments showed that SQs can be used as photo-cleavable photointiators,their photoinitiating efficiency can be enhanced by hydrogen donor. As photo-cleavable photoinitiators,SQs could initiate hexamethylene diacrylate(HDDA) very efficiently with the double bond conversion(DBC) of 80%. In the presence of ethyl-4-(dimethylamino) benzoate(EDB) as coinitiator, photoinitiator systems initiated photopolymerization of commercial acrylate monomers with higher double bond conversion than 90%. These characteristics make SQs potential photoinitiators in photo-curing field.     

Phase equilibria and photopolymerisation-induced phase transitions of mesogenic diacrylate monomer and low molecular mass liquid crystal mixture

Experimental phase diagrams of binary mesogenic mixtures of reactive mesogenic diacrylate (RM257) monomer and low molar mass liquid crystals (E7) were determined by means of differential scanning calorimetry and optical microscopy. The combined free energy densities of Flory–Huggins for liquid–liquid demixing, Maier–Saupe for nematic ordering, and phase field free energy for crystal solidification was proposed to describe the phase diagrams of the starting E7/RM257 mixtures. The phase diagram thus constructed is an ideal mixing type, exhibiting a narrow loop of isotropic + nematic (I + N) coexistence region followed by the crystal + nematic (Cr1 + N) region in descending order of temperature. Of particular interest is the permanent fixation of the mesophase structures upon photopolymerisation of neat RM257 in the corresponding nematic and crystalline phases. Upon photopolymerisation of a low RM257 content mixture in both isotropic and nematic states, the nematic–isotropic transition of E7 was found to persist. The permanent structural anchoring is seen upon photo-curing of the 90/10 RM257/E7 mixture in the crystalline state.