啞鈴結(jié)構(gòu)含氟多嵌段共聚物的合成和抗乳化性能機理
發(fā)布時間：2018-12-15 04:56
【摘要】：分水性能是衡量抗乳化劑品質(zhì)的一項重要指標。據(jù)報道,具有超支化結(jié)構(gòu)的破乳劑具有較強的親水和滲透能力,這使得支鏈型破乳劑的破乳效果勝于直鏈型破乳劑;直鏈醚類破乳劑分離出的水色更清澈透明;另外,為了防止在破乳的過程中,抗乳化劑被分離出的水分帶走,在保證破乳效果的同時,應使其具有較強的油溶性和化學穩(wěn)定性。另外,含氟聚合物具有很高的化學惰性、熱穩(wěn)定性、優(yōu)越的耐候性和疏水疏油的特性,我們合成了一系列啞鈴結(jié)構(gòu)的含氟多嵌段共聚物(Fluorinated Multi-block Copolymers with Dumbbell-shaped Structure,FMCDSs),并對其抗乳化性能及機理進行了研究。本文的第一部分主要是FMCDSs的合成及結(jié)構(gòu)表征。通過陰離子開環(huán)聚合法合成了以聚乙二醇(PEG)為線性部分,聚縮水甘油醚(PG)為超支化部分的具有啞鈴結(jié)構(gòu)的超支化-線性-超支化聚醚(PG-b-PEG-b-PG)。以甲基丙烯酸三氟乙酯為氟化試劑,通過原子轉(zhuǎn)移自由基聚合(Atom transfer radical polymerization,ATRP)技術(shù),對PG-b-PEG-b-PG進行氟化改性,通過調(diào)節(jié)單體與引發(fā)劑的比例,得到了不同氟化程度的FMCDS-1、FMCDS-2、FMCDS-3。通過GPC、1HNMR、13CNMR、19FNMR等對其進行了結(jié)構(gòu)表征。本文的第二部分研究了FMCDSs在150SN基礎(chǔ)油-水體系的抗乳化性能及機理。研究發(fā)現(xiàn):較低氟化程度的FMCDS-1在質(zhì)量濃度為100 mg·L-1時在50秒內(nèi)實現(xiàn)150SN基礎(chǔ)油與水基本分離,FMCDS-2、FMCDS-3對應的最佳抗乳化性能的濃度分別為:200 mg·L-1、300 mg·L-1,對應的時間是分別是:53 s、101 s;界面張力不是影響其抗乳化性能的主要因素;含有FMCDSs的150SN基礎(chǔ)油-水體系為彈性體系;擴張彈性模量的變化與分水時間的變化趨勢基本一致,分水時間越短,抗乳化效果越好,擴張彈性模量越低;FMCDSs在油-水界面膜附近吸附聚集,降低了界面膜強度,使其難以形成穩(wěn)定的乳液,最終導致界面膜局部結(jié)構(gòu)損壞而實現(xiàn)破乳。
[Abstract]:Water partition is an important index to evaluate the quality of anti-emulsifier. It is reported that the demulsifier with hyperbranched structure has strong hydrophilic and permeable ability, which makes the demulsifying effect of branched-chain demulsifier better than that of straight-chain demulsifier, and the water color of straight chain ether demulsifier is clearer and transparent. In addition, in order to prevent the anti-emulsifier from being taken away by the separated moisture in the process of demulsification, the anti-emulsifier should have strong oil solubility and chemical stability while ensuring the demulsifying effect. In addition, fluorinated polymers have high chemical inertia, thermal stability, excellent weathering resistance and hydrophobic properties. We have synthesized a series of dumbbell structure fluorinated multiblock copolymers (Fluorinated Multi-block Copolymers with Dumbbell-shaped Structure,FMCDSs). The anti-emulsification property and mechanism were also studied. The first part of this paper is mainly about the synthesis and structure characterization of FMCDSs. Polyether (PG-b-PEG-b-PG) with dumbbell structure was synthesized by anion ring-opening polymerization with polyethylene glycol (PEG) as linear part and polyglycidyl ether (PG) as hyperbranched part. PG-b-PEG-b-PG was modified by atom transfer radical polymerization (Atom transfer radical polymerization,ATRP) with trifluoroethyl methacrylate as fluorination reagent, and the ratio of monomer to initiator was adjusted. FMCDS-1,FMCDS-2,FMCDS-3. with different fluorination degree was obtained. Its structure was characterized by GPC,1HNMR,13CNMR,19FNMR et al. In the second part of this paper, the emulsification resistance and mechanism of FMCDSs in 150SN base oil-water system were studied. It was found that FMCDS-1 with lower fluorination degree could achieve the basic separation of 150SN base oil and water within 50 seconds when the mass concentration was 100 mg L-1, FMCDS-2,. The optimum concentration of anti-emulsification property of FMCDS-3 is 200 mg L-1300 mg L -1, and the corresponding time is 53 s ~ 101s; The interfacial tension is not the main factor to influence the emulsion resistance, the 150SN base oil-water system containing FMCDSs is an elastic system. The change of dilated elastic modulus is basically consistent with that of water diversion time. The shorter the water separation time is, the better the anti-emulsification effect is, and the lower the expansion elastic modulus is. The adsorption and aggregation of FMCDSs near the oil-water interfacial membrane reduces the strength of the interfacial film and makes it difficult to form a stable emulsion which eventually leads to the destruction of the local structure of the interfacial membrane and the demulsification.
【學位授予單位】：山西大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O631.11
本文編號：2380021
[Abstract]:Water partition is an important index to evaluate the quality of anti-emulsifier. It is reported that the demulsifier with hyperbranched structure has strong hydrophilic and permeable ability, which makes the demulsifying effect of branched-chain demulsifier better than that of straight-chain demulsifier, and the water color of straight chain ether demulsifier is clearer and transparent. In addition, in order to prevent the anti-emulsifier from being taken away by the separated moisture in the process of demulsification, the anti-emulsifier should have strong oil solubility and chemical stability while ensuring the demulsifying effect. In addition, fluorinated polymers have high chemical inertia, thermal stability, excellent weathering resistance and hydrophobic properties. We have synthesized a series of dumbbell structure fluorinated multiblock copolymers (Fluorinated Multi-block Copolymers with Dumbbell-shaped Structure,FMCDSs). The anti-emulsification property and mechanism were also studied. The first part of this paper is mainly about the synthesis and structure characterization of FMCDSs. Polyether (PG-b-PEG-b-PG) with dumbbell structure was synthesized by anion ring-opening polymerization with polyethylene glycol (PEG) as linear part and polyglycidyl ether (PG) as hyperbranched part. PG-b-PEG-b-PG was modified by atom transfer radical polymerization (Atom transfer radical polymerization,ATRP) with trifluoroethyl methacrylate as fluorination reagent, and the ratio of monomer to initiator was adjusted. FMCDS-1,FMCDS-2,FMCDS-3. with different fluorination degree was obtained. Its structure was characterized by GPC,1HNMR,13CNMR,19FNMR et al. In the second part of this paper, the emulsification resistance and mechanism of FMCDSs in 150SN base oil-water system were studied. It was found that FMCDS-1 with lower fluorination degree could achieve the basic separation of 150SN base oil and water within 50 seconds when the mass concentration was 100 mg L-1, FMCDS-2,. The optimum concentration of anti-emulsification property of FMCDS-3 is 200 mg L-1300 mg L -1, and the corresponding time is 53 s ~ 101s; The interfacial tension is not the main factor to influence the emulsion resistance, the 150SN base oil-water system containing FMCDSs is an elastic system. The change of dilated elastic modulus is basically consistent with that of water diversion time. The shorter the water separation time is, the better the anti-emulsification effect is, and the lower the expansion elastic modulus is. The adsorption and aggregation of FMCDSs near the oil-water interfacial membrane reduces the strength of the interfacial film and makes it difficult to form a stable emulsion which eventually leads to the destruction of the local structure of the interfacial membrane and the demulsification.
【學位授予單位】：山西大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O631.11
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，本文編號：2380021
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