兩性共聚物: 合成與應用

Abstract

本論文研究分為三個主體,這三個主題分別為共聚物分散劑合成應用於氧化石墨烯與環氧樹脂複合材料熱傳性、兩性離子分散劑的合成及應用於砂漿中氧化石墨烯的分散、兩性離子水膠/矽藻土複合材料的合成及應用於砂漿中。第一個主題為合成一種共聚物Poly (GMA-co-Eu)，選用甲基丙烯酸缩水甘油酯(Glycidyl methacrylate)和烯丙基甲氧基苯酚(Eugenol)為單體，偶氮二異丁腈(AIBN)為起始劑，經自由基反應利用不同單體比例和起始劑濃度聚合成共聚物分散劑P(GMA/Eu)。經由FTIR及NMR光譜分析確認其化學結構。利用Hummers法將石墨烯氧化成氧化石墨烯，並經由FTIR和RAMAN光譜確認。接著探討溶劑、共聚物添加量等對於氧化石墨烯/環氧樹脂(GO/Epoxy)複合材料的熱傳性影響影響。利用SEM觀察氧化石墨烯在環氧樹脂裡的分散性。比較添加不同PGE和PVP,TX100對於氧化石墨烯/環氧樹脂複合材料的熱傳性。實驗結果顯示利用Hummers法將石墨烯氧化成氧化石墨烯，並經由FTIR和Raman光譜確認。在合成的5個PGE中，以PGE3 (GMA/Eu=2, Mn=6.7×103)對GO的分散效果最好。在含6% PGE、10wt% GOA的GO/Epoxy複合材料K值為3.32 W/mK，相較於沒有添加分散劑含10wt% GOA的複合材料K值(=2.62 W/mK)提升了26%；在含6% PGE、20wt% GOA的GO/Epoxy複合材料K值為5.02 W/mK，相較於沒有添加分散劑含20wt% GOA的複合材料K值(=2.93 W/mK)提升了71%。添加PVP和TX100，也能促進GO的分散而提升所得GO/Epoxy複合材料的K值。添加相同劑量的5個PGE PGE所得的複合材料的K值都高於添加PVP者，顯示PGE對GO的分散效果優於PVP。第二個主題為合成一種兩性離子型羧酸型共聚物:丙烯醯胺-(1-(4-(3-((羧甲基)二甲基氨基)丙基氨基)-4-氧代丁-2-烯酸二鈉)) Poly(AM-co-CDP) (PAC)，首先使用馬來酸酐和N,N-二甲基-1，3-丙二胺，及氯醋酸鈉反應得到單體1-(4-(3-((羧甲基)二甲基氨基)丙基氨基)-4-氧代丁-2-烯酸二鈉)(CDP)，硫酸銨(APS)為起始劑，與丙烯醯胺(AM)經由自由基聚合反應合成得到兩性離子型共聚物Poly(AM-co-CDP)。使用FTIR和1H-NMR光譜鑑定其結構，利用GPC測定其分子量，將PAC加入含氧化石墨烯的人工孔隙溶液中，透過沉降體積、粒徑分布、界達電位與黏度實驗，探討PAC對於人工孔隙溶液中GO的分散效果。將PAC/GO添加在水泥砂漿中，測試砂漿試體的抗壓強度與抗彎強度並與商用氧化石墨烯GOB和商用分散劑PC比較。實驗結果顯示: 經由沉降體積、粒徑分布、界達電位和黏度實驗觀察，隨著PAC添加量的增加，GO人工孔隙溶液的黏度漸減，溶液中GO沉降速率減緩、GO粒徑變小、GO界達電位的負值變大，顯示此共聚物確實能促進GO的分散。在合成的PAC中以PAC23(AM/CDP=4, Mn=2.1×104)的表現最佳。相較於商用型羧酸分散劑PC，PAC有更佳的GO分散效果。隨著PAC添加量的增加，含GO的砂漿抗壓/抗彎強度亦增。添加10wt% PAC23、0.05 wt% GOA的28天齡期砂漿試體，有最大的抗壓和抗彎強度、分別為37.2 MPa和7.5 MPa，比未添加氧化石墨烯或分散劑的對照組試體提升了32.3%和111%。相較於PC，PAC更能提升砂漿的機械性質。在合成的數種PAC中以PAC23(AM/CDP=4, Mn=2.1×104)的表現最佳。第三個主題為製備兩種兩性離子型的吸水性水膠，使用丙烯醯胺、disodium 1-(4-(3-((carboxylatomethyl)dimethylammonio) propylamino)-4-oxobut-2-enoate)( 1-（4-（3-（（（羧甲基）二甲基銨）丙基氨基）-4-氧代丁-2-烯酸酯）二鈉）) (CDP)和矽藻土為單體，製備PAC和PACD兩種兩性離子型的吸水性水膠，使用FTIR作結構鑑定，探討單體比例、起始劑或交聯劑劑量和矽藻土含量對於水膠在各種水溶液下吸水率的影響。實驗評估將PACD複合水膠加到水泥砂漿中，作為自養護劑是否合宜，探討水膠和矽藻土量，對於水泥漿中對於水泥砂漿壓強度、內部濕度、乾縮量的影響。實驗結果顯示，PACD複合水膠，當AM/CDP= 4,APS=0.5 mle%,MBA=0.5 mole%,矽藻土15 wt%時的反應條件下，在純水中和孔隙溶液中的最大吸水率分別為362.4 g/g和115.4 g/g。添加矽藻土水膠的砂漿試體的內部濕度高於未添加矽藻土水膠的砂漿試體，後者則高於未添加水膠的砂漿試體。砂漿試體的內部濕度隨著添加的PACD水膠所含DE比例增加呈現先上升、達最大值後再下降的趨勢，其中以添加15 wt%DE的PACD3水膠的砂漿試體內部濕度為最高，其內部濕度到第22天方開始從100%往下降，到第28天的內部濕度仍有78.6%。添加矽藻土的砂漿試體的抗壓強度高於未添加矽藻土的砂漿試體，後者則高於未添加水膠的砂漿試體。砂漿試體的抗壓強度隨著添加的PACD複合水膠所含DE比例增加呈現先上升、達最大值後再下降的趨勢，其中以添加15 wt%DE的PACD3水膠的MD23砂漿試體抗壓強度為最高，在28天齡期的抗壓強度為39.8MPa，比未添加矽藻土的的PAC水膠的試體抗壓強度(34.5 MPa)提升了15%；比無添加水膠的試體抗壓強度(33.1 MPa)提升了20%。添加矽藻土的砂漿試體的乾縮量低於未添加矽藻土的砂漿試體，後者則低於未添加水膠的砂漿試體。砂漿試體的乾縮量隨著添加的PACD水膠所含DE比例增加呈現先下降、達最低值後再上升的趨勢，其中以添加15 wt%DE的PACD3水膠的砂漿試體乾縮量為最低。This study is divided into three main subjects:the synthesis of copolymer dispersantsapplied to the thermal conductivity of graphene oxide and epoxy resin composites, the synthesis amphoteric of dispersants and application in the dispersion of graphene oxide in mortar,synthesis amphoteric hydrogel/ diatomite composites and their application in mortar.The first topic is the synthesis of a copolymer.Poly(GMA-co-Eu) is synthesized by Glycidyl methacrylate and Eugenol as monomer,and and AIBN as initiator. The chemical structure was confirmed by FTIR and NMR analysis.Graphene was oxidized to graphene oxide (GO) using Hummers method.Structure was confirmed using FTIR and Raman.Then, the influence of solvent and copolymer addition amount on the thermal conductivity of GO/Epoxy composite was discussed.Using SEM to observe the dispersion of GO in epoxy.Compare adding different PGE and thermal conductivity of PVP, TX100 for GO/Epoxy composites.The results indicated that graphene is oxidized to GO by Hummers method. Using FTIRand Raman confirmed.Among the five synthes-ized PGEs,PGE3 (GMA/Eu=2, Mn=6.7×103) has the best dispersion effect.The K value of the GO/Epoxy composite containing 6% PGE and 10wt% GO is 3.32 W/mK,which is 26% higher than that of the composite containing 10wt% GOA(=2.62 W/mK) without dispersant added.The K value of the GO/Epoxy composite containing.6% PGE and 20wt% GOA is 5.02 W/mK, which is 71% higher than that of the composite ontaining 20wt% GOA (=2.93 W/mK) without dispersant.The K values of the GO/Epoxy composites obtained by adding the samedose of PGE are higher than thosewith PVP. The second topic is the synthesis of an amphoteric copolmer,poly-(acrylamide-co-1-(4(3-((carboxylatomethyl)- dimethyl-ammonio)propylamino)-4-oxobut-2-enoate)(PAC), was synthesized and evaluated as dispersion agent for GO in cement. PAC was prepared from acrylaide1-(4-(3-((carboxylate-methyl)-dimethyl ammonio)propylamino)-4-oxobut2enoate )(CDP).The chemical structure were confirmed by FTIR and NMR spectral analysis. The dispersion effects of PAC were examinedby measuring the sedimentation and viscosity of GO in pore solutions, and by analyzing the particle size. The results indicated that PAC was indeed effective in dispersing the nanoparticles, for the resulting suspensions were more stabilized and less viscous, and contained GO with smaller particle sizes.The dispersing ability of the prepared polymer appeared to be better than a commercial polycarboxylate-based superplasticizer.The viscosity of 2.65 mPa·s and the addition of 10wt% PAC23 and 0.05 wt% GOA to the cement mortar had 28-day compressive strength of 32.3 Mpa and flexural strength of 7.5Mpa.The third topic uses AM,CDP and diatomite as monomers to prepare two amphoteric hydrogels PAC and PACD.The chemical structure was confirmed by FTIR spectral analysis.The parameters what could be effected experment are monomer ratio,initiator and crosslinker dosage,and diatomaceous earth (DE) content. Then measure hydrogel water absorbency in water and pore solution.We estimate is it reasonable which PACD hydrogel add into mortar as self-curing reagent.We explored the effects of hydrogel and diatomite content on the compressive strength,internal humidity and dry shrinkage of cement mortar in cement paste. The results indicated that when in the optimum recipe,PACD hydrogel water absor-bency is 362.4 g/g in water,in pore solution is 115.4 g/g.When weadd PACD3 hydro-gel into mortar as self-curing reagent, the optimum dosage is 0.2 wt%,in this condi-tion, improve performance in compressive strength,internal humidity and dry shrink-age are better than control group without hydrogel present.