摘要
光聚合具有聚合速度快和聚合条件温和两个突出的优势。为此在过去的几十年间，得到迅速发展，并获得了广泛的应用。但是对于光聚合，尤其是广泛应用的自由基光聚合，聚合所产生的收缩一直是制约光聚合技术发展的一个最主要的问题。
由于的缺少研究光聚合体系收缩过程的实时表征方法，为此，本文建立了光聚合实时收缩的研究手段。进一步，研究了单体结构和光聚合组分对收缩过程的影响。在此基础上，发展了降低聚合收缩的新方法。具体来说，实现了快速的（甲基）丙烯酸酯单体的固态光聚合，并发现固态光聚合可以降低聚合收缩；也实现了硫醇-环氧/硫醇-丙烯酸酯的杂化光聚合，并证明了这种杂化光聚合在降低单纯丙烯酸酯体系收缩的有效性。主要工作如下：
1.建立了激光测量法，通过激光测量传感器可以实时监测光聚合的收缩过程，并证明了该方法的准确性，可重复性，并且可以广泛应用于各种粘度光聚合体系收缩的表征。由于可以有效的对各种光聚合体系的收缩过程加以表征，为此，该方法作为贯穿全文的实时收缩研究手段。
建立了同时表征光聚合收缩和模量变化的研究手段，通过带有光固化附件的动态热机械分析仪（Photo-DMA）可以同时检测光聚合过程中收缩的变化和储能模量的变化。该方法可以适用于高度粘稠的牙科复合材料的光聚合过程的检测。
2.研究了多种丙烯酸单体的光聚合收缩过程，发现双键浓度和双键转化率是影响收缩的重要因素。并且计算得到了丙烯酸酯体系双键的收缩因子为23.98mL/mol，即每摩尔双键聚合会产生23.98mL的收缩。研究了单体结构对收缩的影响，发现随着乙氧化程度提高，单体分子链长度增长，分子量提高，收缩速率和收缩率得到有效的降低，且双键转化率提高。而单纯降低官能度，并不一定能有效的降低双键浓度，因此，收缩率和收缩速率也并不一定能得到降低。另外，相对于丙烯酸酯官能团，甲基丙烯酸酯官能团具有更低的收缩率和收缩速率，但会降低双键转化率。
考察了丙烯酸酯光聚合体系各个组分包括低聚物，单体，引发剂对收缩过程的影响。光聚合体系的收缩率可以由各个组分的收缩率进行计算。由于低聚物分子量较大，具有较低的双键浓度，提高低聚物的含量可以有效降低聚合收缩和收缩速率。相较于低聚物，单体是光聚合体系产生收缩的重要来源，通过改变单体的结构，如采用乙氧化的单体可以降低整体的收缩。引发剂通过影响双键转化过程来影响收缩过程。
3.首次实现了丙烯酸十八酯（ODA）快速的固态固态条件下的自由基光聚合，与液态光聚合不同，固态条件下的自由基光聚合具有较好的抗氧气阻聚的性质。更为重要的是，由于固态条件下单体分子具有更紧密的排列，因此固态光聚合产生的收缩显著的低于液态条件下的光聚合。
首次实现了甲基丙烯酸十八酯（ODMA）快速的固态条件下的自由基光聚合。发现固态条件下（5oC和15oC）甚至具有远高于液态条件下（25oC和35oC）的双键转化率和聚合速率；且单官能ODMA单体固态光聚合的双键转化率和聚合速率超过了用来对比的一些常用单官能和双官能的液态甲基丙烯酸酯单体。这是因为单体的六方堆积方式提高了聚合活性。固态光聚合形成了侧链结晶的聚合物，且结晶侧链也为六方堆积方式；并且固态光聚合制得的聚合物的仍具有较高的分子量和更窄的分子量分布。更为重要的是，相较于直接进行液态光聚合，固态光聚合可以明显的降低收缩。
4.通过ITX增感的光产碱剂TBD HBPh4实现了长波长（320-500nm），快速的光引发的硫醇和环氧的点击化学反应。在此研究基础上，首次研究了ITX/TBD HBPh4引发的硫醇-环氧/硫醇-丙烯酸酯的杂化光聚合。由于结合了环氧和硫醇在降低收缩方面的优势，发现硫醇-环氧/硫醇-丙烯酸酯杂化体系的收缩远低于单纯丙烯酸酯体系的收缩。研究表明硫醇-环氧的收缩因子低于硫醇-丙烯酸酯的收缩因子，因此随着环氧-硫醇组分含量的提高，光聚合杂化体系的收缩得到了进一步降低。同时，随环氧-硫醇组分的提高，杂化体系中硫醇的转化率得到明显提高。此外，由于引入了刚性结构的环氧以及硫醇转化率的提高，杂化体系的热力学性能（包括储能模量，硬度，玻璃化转变温度）均随硫醇-环氧组分含量的提高而得到提升。
Photopolymerization has been widely accepted and is still growingdue to enormous advantages including high reaction rate and mildpolymerization condition, and temporal and spatial control of initiation.However, polymerization shrinkage is a major drawback for currentfree-radical photopolymerizable systems. Polymerization shrinkageinduces many problems and limitates the application of photocurablematerials. Herein, the new real-time method is developed to monitor theshrinkage process. The shrinkage process associated withphotopolymerization has been systematically investigated. In addition, forthe aim of decreasing the shrinkage, the novel solid-statephotopolymerization and hybrid photopolymerization has been relized,and we have proved these novel photopolymerization with low shrinkage.The main work is showed as the following.
1. The laser reflection method is developed to measure the real-timeshrinkage. The accuracy, repeatability of this method has been wellproved. This method could be widely used for different photo-curablesystem.
The photo-DMA method is developed to simultaneously measure thereal-time shrinkage and modulus development. This method could beused for the photo-curable dental composites.
2. Various acrylate monomers are used to investigate thephotopolymerization shrinkage process. The concentration of doublebonds and degree of double bond conversion are key factors to infleuncethe shrinkage process. The shrinkage factor of acrylate, which iscalculated from the curve of maximum shrinkage versus theconcentration of double bonds, is23.98ml/mol, which means15.72mL of shrinkage produced by every mole of double bond polymerized. Theinfluence of chemical structure on the shrinkage process has beenevaluated. With increase of the molecular length by rising the degree ofethoxylation, the shrinkage rate and percentage shrinkage has beendecreased. Decrease of the functionality accompanied with the reducingof the molecular weight, the concentration of double bonds may be notdecreased, so percentage shrinkage may be not reduced by decreasing thefunctionality. Methacrylate could decrease the shrinkage rate andpercentage shrinkage, but unfortunately reduced the degree of conversion.
The compositional effect on shrinkage process of phtocurableformulation has been evaluated. The final shrinkage of fomulation can becalculated according to the contribution of monomers and oligomers.Because the oligomer has the higher molecular weight than monomer,shrinkage rate and final shrinkage could be easily decreased by increasingthe weight percentage of oligomers. Using ethoxylated monomers candecrease the shrinkage rate and percentage shrinkage. Photo-initiator candecrease the percentage shrinkage and shrinkage rate when lowconcentration of photo-initiator is used. It is due to the decrease ofconversion, and concentration of photo-initiator has no significantinfluence on the maximum shrinkage.
3. The free-radical solid-state photopolymerization of octadecylacrylate has been achieved without polymerization kinetics beendeteriorative influenced by mobility restriction. The XRD, DSC, andreal-time FTIR proved that similarity of hexagonal packing between themonomers and polymers facilitates the photopolymerization in the solidstate. Unlike the normal liquid-state photopolymerization, the solid-statephotopolymerization is insensitive to the oxygen due to the fact that thediffusion of oxygen into the sample has been slow down. Moreimportantly, due to the more compact packing of monomers, theshrinkage of solid-state photopolymerization is obviously low (1%).
The rapid free-radical solid-state photopolymerization of octadecylmethacrylate has been achieved with the increasing the polymerizationreactivity of methacrylate. The polymerization rate and double bondconversion in the solid state (5oC and15oC) is higher than those in the liquid state (25oC and35oC). The polymerization rate of crystallineoctadecyl methacrylate significantly exceeds that of highly functionaldimethacrylates (EGDAB and DEGDMA). Based on DSC, XRD andreal-time FTIR results, octadecyl methacrylate polymerized in the solidstate without destroying the hexagonal packing of crystalline long alkylchains, and the the hexagonal packing of long alkyl chains are preservedas the hexagonal packing of long alkyl side-chains of polymers. GPCshows that the molecular weight of polymers is still high, and themolecular weight distribution is significantly decreased by solid-statephotopolymerization. We inferred that the crystalline structure, in whichmethacrylic double bonds are concentrated, facilitated rapid minimallyactivated propagation and suppressed bimolecular termination. Moreimportantly, because obvious shrinkage occurs before polymerization dueto crystallization, the shrinkage of solid-state photopolymerizationwithout transition of liquid to solid is obviously low(1%).
4. The rapid photopolymerization of hybrid thiol-epoxy/thiol-acylatesystem has been achieved. ITX/TBD HBPh4photoinitiating system thatgenerated both free radical and strong base (TBD) upon UV exposure(320-500nm), could induced the relatively fast and essentiallyquantitative thiol-epoxy click reaction, radical-mediated thiol-acrylatereaction and thiol-acrylate Micheal addition reaction. The results showthat hybrid systems have much lower polymerization shrinkage comparedwith single acrylate system, and polymerization shrinkage decreases withincreasing the percentage weight of thiol-epoxy. Besides, the mechanicalproperty and hardness of thiol-acylate system has been improved bythiol-epoxy reaction. With rising the percentage weight of thiol-epoxy,the store modulus, the glass transition temperature, and hardness hassignificantly increased.
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