本研究以陰離子聚合法(Anionic Living Polymerization，ALP)搭配雙邊鋰離子起始劑(Difunctional t-BuLi Initiator)製備ABA三嵌段團鏈共聚物聚苯乙烯-聚異戊二烯-聚苯乙烯(PS-b-PI-b-PS，SIS)和聚異戊二烯-聚苯乙烯-聚異戊二烯(PI-b-PS-b-PI，ISI)。雙邊鋰離子起始劑是由叔丁基鋰(t-BuLi)和1,3-二異丙烯基苯(1,3-Diisopropenylbenzene，1,3-DIB)製備並經1H NMR、13C NMR、DEPT135、7Li NMR和GC-MS分析確認雙邊鋰離子起始劑的結構與純度。進一步聚合的ABA三嵌段團鏈共聚物根據1H NMR、13C NMR和2D HSQC分析的結果，SIS和ISI中PI的1,2-和3,4-addition (Vinyl group)結構含量在3.7%–94.6%範圍內，其含量取決於反應溫度和四氫呋喃(THF)的添加量。GPC量測獲得SIS和ISI的Mn和PDI分別在13,400–281,000 Da和1.09–1.24之間。DSC曲線上存在著PI和PS相的兩個玻璃化轉變溫度(Tg)，低Tg數值與嵌段共聚物中PI的Vinyl group含量有關；SIS三嵌段共聚物中的Vinyl group含量分別為6.9%和94.6%，另ISI三嵌段共聚物中的Vinyl group含量為6.6%和94.2%，其PI嵌段的相應Tg值分別為–64 ℃和12 ℃以及62 ℃和17 ℃。在相結構方面，藉由SAXS與TEM對嵌段共聚物自組裝結構分析結果顯示，當Vinyl group含量增加至84.1%而分子量約100,000 Da時，呈現Lamellae的層狀相分離結構，其中PI鏈段直徑為38 nm而PS鏈段為24 nm；隨著Vinyl group含量降低至8.0%時，PI鏈段直徑增加並且由層狀結構趨向圓形體結構直徑增加為95 nm。另分子量下降至約50,000 Da時亦有上述現象產生，Vinyl group達87.4%亦呈現Lamellae結構，PI鏈段直徑為25 nm，PS鏈段直徑為12 nm；隨著Vinyl group含量下降至8.4%時，PI結構呈現圓形體直徑增加為47 nm。
另外，本研究也成功地使用陰離子聚合與硫醇-己內醯胺活性自由基聚合(Mercaptan/ε-caprolactam living polymerization，MLP)複合式系統製備壓克力系列功能性團鏈共聚物，建立常溫製備聚甲基丙烯酸甲酯-聚異戊二烯-聚甲基丙烯酸甲酯(PMMA-b-PI-b-PMMA，MIM)三嵌段團鏈共聚物的方法。首先由ALP使用THF做為極性調節劑搭配雙邊鋰離子起始劑合成PI鏈段。接著將調控的異構化PI用硫醇端基官能化以形成α,ω-雙硫醇官能化的PI前體聚合物(α,ω-bismercaptan-functionalized PI precursor polymers，HSISH)，接著通過MLP在90 ℃下聚合成MIM三嵌段團鏈共聚物。經由GPC鑑定其Mn值為42,100–81,300 Da而PDI值為1.23–1.56，通過1H NMR、13C NMR、2D HSQC和GPEC分析PI鏈段的Vinyl group含量為8.9%–90.6%。此外，由DSC觀察到MIM聚合物出現兩個分別對應於PI鏈段與PMMA鏈段的高低溫Tg範圍，分別為–57.2 ℃至10.4 ℃，以及99.4 ℃至119.8 ℃。Instron的拉伸測試結果顯示，Vinyl group基團比例較高的MIM，具有較高的楊式模數；當Vinyl group降低時，楊式模數降低並且材料拉力強度變差，隨著Vinyl group的減少，MIM三嵌段共聚物的極限伸長率增加，並且韌性增加。由上述結果顯示，本研究提出一種新穎複合式活性聚合法成功的克服壓克力團鏈共聚合需極低溫聚合、須嚴格選擇反應起始劑以及須添加危險添加劑的缺點，為一具應用潛力的商業化新製程技術。

In this study, Anionic Living Polymerization (ALP) and difunctional t-BuLi initiator were used to prepare poly(styrene)-block-poly(isoprene)-block-poly(styrene) (PS-b-PI-b-PS, SIS) and poly(isoprene)-block-poly(styrene)-block-poly(isoprene) (PI-b-PS-b-PI, ISI) triblock copolymers. Difunctional t-BuLi initiator was prepared from tert-butyllithium (t-BuLi) and 1,3-diisopropenylbenzene (1,3-DIB), then it was analyzed from 1H NMR, 13C NMR, DEPT135, 7Li NMR, and GC-MS analysis to analyze the structure of difunctional t-BuLi initiator. According to the results of 1H NMR, 13C NMR, and 2D HSQC analysis, the content of 1,2- and 3,4-addition (Vinyl group) structures of PI in SIS and ISI are in the range of 3.7%-94.6%, and its content depends on the reaction temperature and the amount of tetrahydrofuran (THF) added. The Mn and PDI of SIS and ISI obtained by GPC are between 13,400–281,000 Da and 1.09–1.24, respectively. The presence of two glass transition temperatures (Tg) on the DSC curve indicates the phase separation of the PI and PS domains. The low Tg is attributed to the PI domain, which is related to the vinyl content in the block copolymer. For the vinyl content in the SIS triblock copolymer are 6.9% and 94.6%, the vinyl content in the ISI triblock copolymer are 6.6% and 94.2%, and the corresponding Tg values of the PI block are 64 ℃, 12 ℃ and 62 ℃, 17 ℃, respectively. By SAXS and TEM analysis of self-assembly situation, when the vinyl group content increases to 84.1% and the molecular weight is about 100,000 Da, the phase separation situation presents a Lamellae structure, in which the diameter of the PI segment is 38nm and the PS segment is 24nm. When the vinyl group is reduced to 8.0%, the diameter of the PI segment increases to 95 nm and the phase separation of the PI segment changes from the layered structure to the circular structure. The above phenomenon also occurs when the molecular weight drops to about 50,000 Da. When the vinyl group reaches 87.4%, the Lamellae structure is also present, the diameter of the PI segment is 25nm, and the diameter of the PS segment is 12nm; as the vinyl group content drops to 8.4%, the PI structure presents a circular body with an increase in diameter of 47 nm.
In addition, anionic living polymerization and mercaptan/ε-caprolactam living polymerization (MLP) compound system is used in the polymerization of acrylic series to prepare poly(methyl methacrylate)-block-poly(isoprene)-block-poly(methyl methacrylate) (PMMA-b-PI-b-PMMA, MIM) triblock copolymer. First, PI was synthesized by ALP using THF as a polarity modifier with difunctional t-BuLi Initiator. Next, the regulated isomerized PI is functionalized with thiol-end groups to form α, ω-bismercaptan-functionalized PI precursor polymers (HSISH), which is passed through MALDI-TOF mass spectrometry and GPC to identify its end-group structure. Then HSISH precursor was polymerized by MLP at 90°C to form a MIM triblock copolymer. The Mn value is 42,100–81,300 Da and the PDI value is 1.23–1.56 identified by GPC. The vinyl content is 8.9%–90.6% characterized by 1H NMR, 13C NMR, 2D HSQC analysis. Mn values with conversions and GPEC are used to further confirm that polymers were obtained by the MLP reaction. The Mn was found to be directly proportional to the conversion, irrespective of the vinyl-group content of the HSISH precursor, which is a characteristic feature of living polymerization. In addition, two Tgs of the MIM polymer were observed by DSC: 57.2 ℃ to 10.4 ℃, and 99.4 ℃ to 119.8 ℃, corresponding to the PI segment and the PMMA segment, respectively.
A tensile test was conducted in an Instron testing machine. The MIM with a higher proportion of vinyl groups has higher stiffness, indicating that the material is harder; when the vinyl group decreases, the stiffness decreases and the material becomes weaker. The decrease of the MIM triblock copolymer's ultimate elongation and toughness increase. The above results show that this study proposes a peculiar living free radical polymerization process that successfully overcomes the shortcomings of acrylic acid series’s copolymerization that requires extremely low temperature polymerization, strict selection of reaction initiators, and the need to add dangerous additives. This peculiar polymerization process provides an application potential for commercialization.

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