UV固化丙烯酸酯胶粘剂的合成及性能研究

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸缩水甘油酯(GMA)和丙烯酸羟乙酯(HEA)为共聚单体,并以二缩三丙二醇二丙烯酸酯(TPGDA)为交联剂、十二烷基硫醇(NDM)为链转移剂和乙酸乙酯为极性溶剂,采用核/壳溶液聚合法合成了侧链含C=C的丙烯酸酯预聚体;然后以此为基体树脂、丙烯酸异冰片酯(IBOA)和三羟甲基丙烷二丙烯酸酯(TMPTA)为活性稀释剂、651为自由基光引发剂和碘鎓盐为阳离子光引发剂,制备了UV固化胶粘剂。研究结果表明:合成丙烯酸酯预聚体的最佳工艺条件是m(BA)∶m(MMA)∶m(GMA)∶m(TPGDA)∶m(HEA)=20∶60∶10∶4∶6、n(TPGDA)∶n(NDM)=2∶2、w(热引发剂)=3%和w(乙酸乙酯)≥70%(均相对于共聚单体总质量而言);自由基/阳离子混杂双重UV固化胶粘剂比单一自由基UV固化胶粘剂具有更大的附着力和耐酸碱性,此时前者的最佳配方中w(预聚体)=55%、w(651或碘鎓盐)=5%、w(IBOA)=15%、w(TMPTA)=12%和w(GMA)=8%(均相对于胶粘剂总物料质量而言)。     

Fabrication and characterization of electrolyte membranes based on organoclay/tripropyleneglycol diacrylate/poly(vinylidene fluoride) electrospun nanofiber composites

Utilizing polymer electrospinning technology, novel electrolyte membranes based on poly(vinylidene fluoride) (PVDF)/organomodified clay (OC)/tripropyleneglycol diacrylate (TPGDA) composite nanofibers with a diameter of 100–400 nm were fabricated for application in lithium batteries. Ultraviolet photo‐polymerization of electrospun PVDF/OC/TPGDA nanofibers generated chemically crosslinked TPGDA‐grafted PVDF/OC nanofibers exhibiting robust mechanical and electrochemical properties. The prepared fibrous PVDF/OC/TPGDA electrolytes were characterized in terms of morphology, crystallinity, electrochemical stability, ionic conductivity and cell cycleability. Based on differential scanning calorimetry analysis, the crystallinity of PVDF decreased by ca 10% on employing the OC and TPGDA. Compared with pure PVDF film‐based electrolyte membranes, the TPGDA‐ and OC‐modified PVDF electrolyte membranes exhibited improved mechanical properties and various electrochemical properties. The OC‐ and TPGDA‐modified microporous membranes are promising candidates for overcoming the drawbacks of the lower mechanical stability of fibrous‐type electrolytes with further improvement of electrochemical performance. Copyright © 2009 Society of Chemical Industry     

有机硅改性丙烯酸酯树脂的合成及其光固化动力学研究

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(n-BA)、二缩三丙二醇二丙烯酸酯(TPGDA)、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH-570)为单体,正十二烷基硫醇(NDM)为链转移剂,偶氮二异丁腈(AIBN)为引发剂,合成了一种可紫外光固化的丙烯酸酯树脂(UV-WZF)。通过FT-IR、DSC、TGA对其结构和性能进行了研究。讨论了KH-570的含量和TPGDA的含量对光固化膜的附着力、光固化速率的影响。结果表明:当硅烷偶联剂KH-570的用量为6%时,涂膜附着力良好;当TPGDA的用量为26%时,固化漆膜的光固化时间最短。采用实时红外光谱原位跟踪监测了该树脂的光固化动力学行为,结果表明:当光引发剂Darocur1173含量为树脂质量的5%时,体系的光固化速率最优,增大光强利于光固化。     

The effect of ionic liquid fragment on the performance of polymer electrolytes

An ionic liquid 1‐methyl‐3‐[2‐(methacryloyloxy)ethyl]imidazolium bis(trifluoromethane sulfonylimide) (MMEIm‐TFSI) was synthesized and polymerized. Composite polymer electrolytes based on polymeric MMEIm‐TFSI (PMMEIm‐TFSI) and poly[(methyl methacrylate)‐co‐(vinyl acetate)] (P(MMA‐VAc)) were prepared, with lithium bis(trifluoromethane sulfonylimide) (LiTFSI) as target ions (Li⁺). DSC/TGA analysis showed good flexibility and thermal stability of the composite electrolyte membranes. The AC impedance showed that the ionic conductivity of the electrolytes increased with PMMEIm‐TFSI up to a maximum value of 1.78 × 10^?4 S cm^?1 when the composition was 25 wt% P(MMA‐VAc)/75 wt% PMMEIm‐TFSI/30 wt% LiTFSI at 30 °C. The composite electrolyte membrane (transmittance ≥ 90%) can also be used as the ion‐conductive layer material for electrochromic devices, and revealed excellent colorization performance. Copyright © 2011 Society of Chemical Industry     

Preparation and characterization of gel polymer electrolytes based on acrylonitrile-methoxy polyethylene glycol (350) monoacrylate-lithium acrylate terpolymers

The acrylonitrile (AN)-methoxy polyethylene glycol (350) monoacrylate (MPGA)-lithium acrylate (LiAc) copolymers (PAMGLiAc) was synthesized by emulsion polymerization. Phase inversion technique was used to prepare the PAMGLiAc microporous membrane. The gel polymer electrolytes (GPEs) with the PAMGLiAc were obtained by the copolymer microporous membrane soaking liquid electrolyte. The component and structure of the PAMGLiAc were characterized by IR, NMR and TGA/DSC measurement. The electrochemical characteristics of the PAMGLiAc gel electrolytes were investigated in terms of different composition. The ionic conductivity exceeded 2.0 × 10⁻³ S/cm at ambient temperature, and this system also showed good mechanical properties and a sufficient electrochemical stability with a decomposition voltage as much as 5 V vs. Li to allow far wider operation in the rechargeable lithium-ion polymer batteries.     

紫外光交联法制备全固态聚合物电解质

制约全固态聚合物电解质开发应用的瓶颈在于如何同时实现高离子电导率与高机械强度。采用可逆加成断裂链转移（RAFT）溶液聚合技术,以3-环己烯-1-亚甲基丙烯酸酯（CEA）为后交联单体,聚乙二醇甲醚丙烯酸酯（PEGMA）为导离子单体,制备了不同链结构的全固态聚合物电解质,再通过硫醇-烯烃之间的“点击化学”反应形成化学交联网络结构。所制备的三嵌段共聚物电解质具有独立的导离子中间嵌段,且交联单体位于分子链两端,从而能够同时满足离子电导率与机械强度的要求。该三嵌段共聚物电解质在60℃下的离子电导率为6.13×10^-5 S/cm,并应用于磷酸亚铁锂/锂（LiFePO₄/Li）全固态电池。所得电池在0.5 C下循环130圈后,放电比容量为139.1 mAh/g,容量保持率为97.8%,库仑效率高于99.0%,显示出良好的电化学性能。     

Ionically conductive polymer gel electrolytes prepared from vinyl acetate and methyl methacrylate for electric double layer capacitor

In order to obtain highly conductive polymer electrolytes for an electric double layer capacitor, three kinds of polymer gel electrolytes were prepared. Vinyl acetate (VAc) and methyl methacrylate (MMA) were copolymerized with divinyl adipate (DA) and ethylene glycol dimethacrylate (EGDMA), respectively, in propylene carbonate (PC) containing tetraethylammonium tetrafluoroborate (TEATFB) to form network polymer gel electrolytes. MMA was also copolymerized with butylene glycol DMA for comparison. The polymer gel electrolytes obtained were characterized by means of thermogravimetry, complex impedance analysis, and cyclic voltammetry for use in the electric double layer capacitor. The ionic conductivities of the polymer gel electrolytes were dependent on the TEATFB concentration, temperature, and crosslinking degree. The polymer gel electrolytes in the VAc‐DA system exhibited higher room temperature conductivities (10⁻² S/cm) than those in the MMA‐EGDMA system. Further, the polymer gel electrolytes in the VAc‐DA system showed good electrochemical stability windows ranging from −4.0 to 4.0 V versus Ag. Thermal analysis revealed that the polymer gel electrolytes in both systems were stable up to 150°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 12–18, 2000     

Preparation of networked polymer electrolytes by copolymerization of a methacrylate with an imidazolium salt structure and an ethyleneglycol dimethacrylate in the presence of lithium bis(trifluoromethanesulfonyl)imide

Ionic networked polymers containing ionic liquids were synthesized by radical copolymerization of 1-(2-methacryloyl)ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (Met-IL) and difunctional or trifunctional methacrylate cross-linkers, ethylene glycol dimethacrylate (EGDMA), or trimethylolpropane trimethacrylate (TMPTMA) in the presence of an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMImTFSI). For comparison, nonionic networked polymers containing the ionic liquid were prepared by radical copolymerization of methyl methacrylate (MMA) with EGDMA in the presence of EMImTFSI. Met-IL/EGDMA/EMImTFSI(50) showed higher ion conductivity and ionic liquid holding ability than the corresponding MMA/EGDMA/EMImTFSI(50), while Met-IL/TMPTMA/EMImTFSI(50) showed lower ionic conductivity with higher holding ability than MMA/EGDMA/EMImTFSI(50).     

Morphology and ionic conductivity of thermoplastic polyurethane electrolytes

Thermoplastic polyurethane (TPU) with a mixture of soft segments [poly(ethylene glycol) (PEG) and poly(tetramethylene glycol) (PTMG)], denoted TPU‐M, was prepared as an ion‐conducting polymer electrolyte. TPUs with PEG and PTMG as soft segments were also synthesized individually as polymer electrolytes. The changes in the morphology and ion conductivity of the phase‐segregated TPU‐based polymer electrolytes as a function of the lithium perchlorate concentration were determined with differential scanning calorimetry, Fourier transform infrared spectroscopy, alternating‐current impedance, and linear sweep voltammetry measurements. Both solid and gelatinous polymer electrolytes were characterized in this study. The effect of temperature on conductivity was studied. The conductivity changes revealed the combined influence of PTMG and PEG units in TPU‐M. The swelling characteristics in a liquid electrolyte and the dimensional stability were evaluated for the three TPUs. Because of its dimensional stability and ionic conductivity, the TPU system containing both PEG and PTMG as soft segments was found to be more suitable for electrolyte applications. A room‐temperature conductivity of approximately 1 × 10^?4 was found for TPU‐M containing 50 wt % liquid electrolyte. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1154–1167, 2004     

Synthesis and properties of methacrylate-based ionic networked polymers containing ionic liquids: comparison of ionic and nonionic networked polymers

Ionic networked polymers containing ionic liquids were synthesized by radical copolymerization of 1-(2-methacryloyl)ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (Met-IL) and difunctional or trifunctional methacrylate cross-linkers, ethylene glycol dimethacrylate (EGDMA), or trimethylolpropane trimethacrylate (TMPTMA) in the presence of an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMImTFSI). For comparison, nonionic networked polymers containing the ionic liquid were prepared by radical copolymerization of methyl methacrylate (MMA) with EGDMA in the presence of EMImTFSI. Met-IL/EGDMA/EMImTFSI(50) showed higher ion conductivity and ionic liquid holding ability than the corresponding MMA/EGDMA/EMImTFSI(50), while Met-IL/TMPTMA/EMImTFSI(50) showed lower ionic conductivity with higher holding ability than MMA/EGDMA/EMImTFSI(50).     

Novel amphiphilic polymer gel electrolytes based on (PEG‐b‐GMA)‐co‐MMA

Amphiphilic conetwork–structured copolymers containing different lengths of ethylene oxide (EO) chains as ionophilic units and methyl methacrylate (MMA) chains as ionophobic units were prepared by free radical copolymerization and characterized by FTIR and thermal analysis. Polymer gel electrolytes based on the copolymers complexed with liquid lithium electrolytes (dimethyl carbonate (DMC) : diethyl carbonate (DEC) : ethylene carbonate (EC) = 1 : 1 : 1 (W/W/W), LiPF₆ 1.0M) were characterized by differential scanning calorimetry and impedance spectroscopy. A maximum ion conductivity of 4.27 × 10^?4 S/cm at 25^oC was found for the polymer electrolyte based on (PEG2000‐b‐GMA)‐co‐MMA with long EO groups. Moreover, the effect of temperature on conductivity of the amphiphilic polymer electrolytes obeys the Arrhenius equation. The good room temperature conductivity of the polymer electrolytes is proposed to relate to the enhancement in the amorphous domain of the copolymers due to their amphiphilic conetwork structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Branched methyl methacrylate copolymer particles prepared by RAFT dispersion polymerization

Reversible addition–fragmentation chain transfer (RAFT) dispersion copolymerization of methyl methacrylate (MMA) and tripropylene glycol diacrylate (TPGDA) was carried out in ethanol/water in the present work. S-1-Dodecyl-S′-(α,α-dimethyl-α″-aceticacid) trithiocarbonate (TTC) was used as a chain transfer agent to inhibit the occurrence of gelation. Branched poly(methyl methacrylate) (PMMA) particles with a very narrow size distribution was prepared by a two-stage method: the addition of a RAFT agent and a TPGDA agent to the system followed the nucleation stage. The particles had an average diameter within 1.9–2.7 μm and size distribution of 1.12–1.24. Molecular weight, molecular weight distribution, compositions and structure of copolymer were investigated by GPC and 1H NMR characterization. The GPC curves showed a bimodal distribution, indicating that MMA homopolymer was synthesised during the nucleation stage. In addition, 1H-NMR proved that MMA and TPGDA branched copolymer was synthesised after the nucleation stage. TPGDA fraction in the copolymer was lower than that in the initial monomer. It was determined that the intrinsic viscosity of the copolymer decreased with conversion and the Mark–Houwink exponent α of copolymer was reduced from 0.643 to 0.548, which further confirmed the branched structure of the copolymer.     

BMIMBF_4/P(MMA-VBIMBr)凝胶型离子液体聚合物电解质的合成与性能

以甲基丙烯酸甲酯(MMA)和1-乙烯基-3-丁基咪唑溴盐(VBIMBr)为单体,通过自由基溶液聚合制备了无规共聚物聚(甲基丙烯酸甲酯-1-乙烯基-3-丁基咪唑溴盐)[P(MMA-VBIMBr)],并以此聚合物为基体,离子液体1-丁基-3-甲基咪唑四氟硼酸盐(BMIMBF4)为增塑剂,制备了BMIMBF4/P(MMA-VBIMBr)凝胶型离子液体聚合物电解质,采用红外光谱(FTIR)、X射线衍射(XRD)、扫描电镜(SEM)、热重分析(TG)和电化学交流阻抗(EIS)等方法对聚合物和聚合物电解质的性质进行了研究。结果表明,聚合物电解质膜具有优良的热稳定性和机械强度;当BMIMBF4/P(MMA-VBIMBr)质量配比为2时,离子电导率高达2.77×10-3S/cm(20℃),且离子电导率随着温度的升高而迅速增加,电导率-温度曲线符合Arrhenius方程。     

Synthesis and characterization of novel crosslinked polyurethane–acrylate electrolyte

Flexible, transparent, and crosslinked polymer films were synthesized by polymerization of PEG‐modified urethane acrylate using a simple method. A series of novel solid polymer electrolytes and gel electrolytes were prepared based on this type of polymer film. To understand the interactions among salt, solvent, and polymer, the swelling behaviors of the crosslinked polymer in pure propylene carbonate (PC) and liquid electrolyte solutions (LiClO₄/PC) were investigated. The results showed that the swelling rate in the electrolyte solution containing moderate LiClO₄ was greater than that in pure PC. Thermogravimetric analysis (TGA) also supported the interaction between the solvent and polymer. The morphology and crystallinity of the crosslinked polymer and polymer electrolytes were studied using atomic force microscopy (AFM) and wide‐angle X‐ray diffraction (WAXD) spectroscopy. The effects of the content of the electrolyte solution on the ionic conductivity of gel electrolytes were explored. The dependence of the conductivity on the amount of the electrolyte solution was nonlinear. With a different content of the plasticizer, the ionic conduction pathway of the polymer electrolytes would be changed. The best ionic conductivity of the gel electrolytes, which should have good mechanical properties, was 4 × 10^r?3 S cm^?1 at 25°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 340–348, 2003     

聚丙烯酸酯/聚硅氧烷乳胶粒核壳结构相反转及控制

采用乳液聚合法,以丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、八甲基环四硅氧烷(D4)为单体,甲基丙烯酰氧丙基三甲氧基硅烷(MATS)或甲基丙烯酸羟乙酯(HEMA)为偶联剂,十二烷基苯磺酸钠(SDBS)为乳化剂,过硫酸铵(APS)和十二烷基苯磺酸(DSBA)为复合引发剂,经乳液自由基与缩聚同步反应,制得具有核壳结构的聚丙烯酸酯(核)/聚硅氧烷(壳)共聚物乳液。考察了交联剂二缩三丙二醇双丙烯酸酯(TPGDA)对乳胶粒核壳结构的影响,结果表明不加交联剂的共聚乳液放置一定时间.乳胶粒核壳结构发生相反转,最终变成以聚硅氧烷为核、聚丙烯酸酯为壳的热力学稳定结构;加入交联剂可以有效控制乳胶粒核壳结构,乳液放置一定时间乳胶粒核壳结构不变。     

Poly(urethane acrylate)‐based gel polymer films for mechanically stable,transparent, and highly conductive polymer electrolyte applications

Polymer electrolytes are attractive for the applications in conventional electrochemical devices and emerging flexible devices. In this study, we developed a poly(urethane acrylate)‐based gel polymer electrolyte with excellent mechanical stability, optical transparency, and a high ionic conductivity. These polymer electrolytes showed excellent dimensional stability and an elastomer‐like behavior with a Shore A hardness in the range of 20–40. The optical transmittance values of these polymers films were over 80% in the visible range. Their ionic conductivities were controlled via changes in the concentration of the linker, dimethylol propionic acid (DMPA), and the lithium salt incorporated into the polymer. The maximum ionic conductivity reached 3.7 mS/cm at room temperature (～23 °C) when the DMPA/poly(ethylene glycol) molar ratio was 0.25, and the ionic conductivity was found to be proportional to the salt concentration. We believe that these polymer electrolytes will be useful in various electrochemical applications where flexibility, high ionic conductivity, and transparency in the electrolytes are necessary. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45009.     

The application of P(MMA-co-MAA)/PEG polyblend gel electrolyte in quasi-solid state dye-sensitized solar cell at higher temperature

A poly(methyl methacrylate-co-methacrylate acid)/poly(ethylene glycol) [P(MMA-co-MAA)/PEG] polyblend with viscoelasticity was synthesized by a copolymerizing reaction between methyl methacrylate (MMA) and methacrylate acid (MAA) using azobisisobutyronitrile (AIBN) as initiator in poly(ethylene glycol) (PEG) methanol solution. Then, a polyblend gel electrolyte was prepared by adding KI and I₂ to P(MMA-co-MAA)/PEG system. The influence of compositions of the polyblend gel electrolyte on the ionic conductivity and the effect of temperature on photoelectronic performance of quasi-solid state dye-sensitized solar cell (QS-DSSC) were discussed. It was found that the polyblend gel electrolyte was a good candidate as high-temperature electrolyte for QS-DSSCs. Under an optimized condition, the highest conductivity of the polyblend gel electrolyte was 2.70 mS/cm² at 30 °C. Based on the polyblend gel electrolyte, a light-to-electricity conversion efficiency of 4.85% for QS-DSSC was achieved under AM 1.5 simulated solar light illumination at 60 °C.     

New polymer electrolytes based on ether sulfate anions for lithium polymer batteries: Part II: Conductivity and transport properties of blended and cross-linked ionomers

Multifunctional ionomers based on poly(oxyethylene)-co-poly(epichlorohydrin) random copolymers were blended with poly(oxyethylene) or cross-linked through urethane curing. Their conductivities, transference numbers and electrochemical stability were investigated. The cross-linked materials exhibited good mechanical properties. Gelled by liquid organic electrolytes they provided conductivities very close to that of the liquid electrolyte. A thorough comparative investigation of the cationic transference numbers of cross-linked and uncross-linked ionomers was performed. From these data it may be assumed that the cell electrical polarization is enough to induce chain disentanglements, which result in a significant anionic transference number.     

聚乙二醇单甲醚甲基丙烯酸酯对水性上光油流平性能的影响

以聚乙二醇单甲醚甲基丙烯酸酯(MPEGMA)作为缔合型乳化剂,以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、苯乙烯(St)、丙烯酸羟乙酯(HEA)为单体,制备水性上光油.研究了MPEGMA相对分子质量与用量对乳液凝胶率、转化率、粒径、黏度、流平和涂层光泽的影响.结果表明:随着MPEGMA相对分子质量的增大,水性上光油的转化率、黏度、涂层光泽逐渐变大,凝胶率、粒径逐渐变小,流平性能提高.当MPEGMA的含量为2%左右时,所得水性上光油凝胶率、粒径较小,转化率、光泽较高,黏度适中,流平性能较好.     

丙烯酸酯三元共聚物酸掺杂改性聚苯胺的研究

选择丙烯酸 (AA)、丙烯酸丁酯 (BA)和甲基丙烯酸甲酯 (MMA)三元共聚物对聚苯胺 (PAn)进行改性 ,研究了BA的用量和引发剂浓度对PAn导电率的影响 ,对样品进行DSC、FTIR和SEM测试。结果表明 ,丙烯酸酯三元共聚物酸对PAn有良好的掺杂改性作用 ,当共聚单体 (AA -BA -MMA)组成为 10∶45∶45 (质量比 ) ,引发剂浓度为0 0 5 48mol·L-1时 ,可制得电导率达 1 42 1S·cm-1的导电PAn。