本文選題：羧基功能化離子液體 + α-蒎烯��； 參考：《青島科技大學(xué)》2017年碩士論文

【摘要】：在天然生物質(zhì)資源松脂松節(jié)油的高值化利用中,α-蒎烯水合制備松油醇的反應(yīng)具有重要的工業(yè)價(jià)值與研究意義。為了摒棄傳統(tǒng)礦物酸催化產(chǎn)生大量廢酸廢水、控制條件嚴(yán)苛、產(chǎn)物處理繁瑣等弊端,本文基于“環(huán)境友好催化”的理念,兼顧反應(yīng)的有效性與分離的簡(jiǎn)易性,結(jié)合α-蒎烯一步水合法合成α-松油醇的反應(yīng)體系特性,將羧基官能團(tuán)(-COOH)引入離子液體結(jié)構(gòu)加以修飾以優(yōu)化其在α-蒎烯水合反應(yīng)中的催化性能,同時(shí)以雜多酸陰離子調(diào)變其酸性,設(shè)計(jì)合成了多種兼具離子液體與雜多酸鹽結(jié)構(gòu)特征的羧基功能化離子液體催化劑。并且將其應(yīng)用于α-蒎烯一步水合法合成α-松油醇的反應(yīng)中,開發(fā)出三個(gè)富有新意的綠色催化工藝路線。采用核磁共振譜(~1HNMR)、傅里葉紅外變換光譜(FT-IR)等方法對(duì)羧基功能化離子液體催化劑的結(jié)構(gòu)進(jìn)行了表征,用熱重分析法(TGA)測(cè)試了其穩(wěn)定性,并用正丁胺(n-BuNH_2)電位滴定方法測(cè)試了所合離子液體催化劑的酸強(qiáng)度與酸量,分別測(cè)試了各種催化劑在水/α-蒎烯中的溶解性,考察了催化劑的陰/陽離子部分對(duì)其酸性和溶解性能等理化性質(zhì)的影響,探討了催化劑的構(gòu)效關(guān)系規(guī)律。將設(shè)計(jì)合成的一系列烷基咪唑類羧基功能化離子液體催化劑應(yīng)用于催化α-蒎烯的水合反應(yīng)中,實(shí)驗(yàn)結(jié)果表明,羧基及鹵素基團(tuán)的引入提高了松油醇的選擇性,具有較高酸強(qiáng)度的羧酸功能化雜多酸式鹽類催化劑[N-C_(14),N’-(CO_2H)_2-C_2H_2-I m-Br]_2HPW_(12)O_(40)催化效果較好。在催化劑用量0.25 mmol,水用量0.30 mol,α-蒎烯用量0.06 mol,70°C反應(yīng)8 h的條件下,α-蒎烯轉(zhuǎn)化率達(dá)89.4%,α-松油醇的選擇性為30.1%,水合產(chǎn)物的總選擇性達(dá)38.7%。且反應(yīng)結(jié)束后靜置,催化劑不溶于水相和油相,經(jīng)過簡(jiǎn)單的傾析分離即可實(shí)現(xiàn)催化劑的回收再利用,并且表現(xiàn)出一定的重復(fù)使用性能。將羧基官能團(tuán)引入到以苯并咪唑?yàn)橛袡C(jī)陽離子母體環(huán)的離子液體結(jié)構(gòu)中以合成多種苯并咪唑類的羧基功能化離子液體,并通過調(diào)控母體環(huán)上的烷基鏈長(zhǎng)和結(jié)構(gòu)以調(diào)變其催化性能,并且應(yīng)用于α-蒎烯的水合反應(yīng),研究結(jié)果表明,短烷基鏈長(zhǎng)的[C_6H_4-CH(Et)N_2-C_2H_3-(CO_2H)_2]H_2PW_(12)O_(40)具有較好的催化效果,α-蒎烯轉(zhuǎn)化率達(dá)95.2%,α-松油醇的選擇性為24.8%,水合產(chǎn)物的總選擇性達(dá)31.6%。此外,該催化劑具有良好的重復(fù)使用性,在循環(huán)利用5次后仍保持較高的催化活性�；讦�-蒎烯水合反應(yīng)中水油兩相互不相溶的特性,本文還設(shè)計(jì)合成了同時(shí)具有表面活性和酸性的十八胺聚醚型羧基功能化離子液體催化劑。以鹵代羧酸為羧基供體,磷鎢酸/硫酸為陰離子酸式基團(tuán),合成了一系列不同聚合度n(離子液體結(jié)構(gòu)中亞乙氧基單元的個(gè)數(shù))的羧基功能化離子液體催化劑。發(fā)現(xiàn)該類催化劑表現(xiàn)出一定的表面活性作用,反應(yīng)體系在反應(yīng)溫度(80°C)下呈微乳相,增加了底物分子間的有效碰撞幾率,獲得較高的轉(zhuǎn)化率,但在反應(yīng)結(jié)束后催化劑自分離性較差。催化劑[AC1870-CH_2COOH]H_2PW_(12)O_(40)在無輔助催化劑的條件下,達(dá)到68.1%的轉(zhuǎn)化率和25.5%的α-松油醇選擇性。為聚醚型羧酸功能化離子液體催化α-蒎烯的水合反應(yīng)提供了依據(jù)。本文旨在探尋無需氯乙酸等有機(jī)酸輔助催化的α-蒎烯水合反應(yīng)清潔化催化體系,為生物質(zhì)松節(jié)油資源的環(huán)境友好催化工藝提供了新思路。
[Abstract]:In the high value utilization of natural biomass pines and turpentine, the reaction of alpha pinene hydration to produce pine oleol has important industrial value and research significance. In order to abandon the traditional mineral acid catalysis to produce a large amount of waste acid waste water, the control conditions are harsh, the product is tedious and so on. Based on the concept of "environmental friendly catalysis", this paper is based on the concept of "environmental friendly catalysis" The effectiveness of the reaction and the simplicity of the separation are combined with the reaction system characteristics of alpha pinene one step water method to synthesize alpha pinyl alcohol. Carboxyl functional group (-COOH) is introduced into the ionic liquid structure to optimize its catalytic performance in the hydration reaction of alpha pinene. At the same time, the acidity is modulated with heteropoly anions, and a variety of concurrently is designed and synthesized. The carboxyl functionalized ionic liquid catalyst with the structural characteristics of ionic liquids and heteropoly salts was used in the reaction of alpha pinene one step water to synthesize alpha pinicol. Three new green catalytic process routes were developed. The function of carboxyl group by nuclear magnetic resonance spectroscopy (~1HNMR), Fu Li Ye Hongwai transform spectroscopy (FT-IR) and other methods The structure of the ionic liquid catalyst was characterized. The stability was measured by TG (TGA). The acid strength and acid content of the ionic liquid catalyst were measured by n-BuNH_2 potentiometric titration. The solubility of various catalysts in water / alpha pinene was tested, and the anion / cation part of the catalyst was investigated. A series of alkyl imidazole carboxylic functionalized ionic liquids were used to catalyze the hydration reaction of alpha pinene. The experimental results showed that the introduction of carboxyl and halogen groups increased the selectivity of the olefinol. [N-C_ (14), N '- (CO_2H) _2-C_2H_2-I m-Br]_2HPW_ (12) O_ (40) catalyzed by carboxylic acid with high acid strength, with 0.25 mmol, 0.30 mol, 0.06 mol for alpha pinene and 8 h for 70 - C reaction, the conversion of alpha pinene is 89.4%, and the selectivity of alpha pinyl alcohol is 30.1%, hydration is 30.1%. The total selectivity of the product is 38.7%. and the catalyst is stationary after the end of the reaction. The catalyst is insoluble in the water and oil phases. After a simple dipping separation, the catalyst can be reused and reused, and a certain reuse performance is shown. A variety of benzimidazole carboxylic functionalized ionic liquids are used to modulate their catalytic properties by regulating the length and structure of the alkyl chain on the parent ring, and applied to the hydration reaction of alpha pinene. The results show that the short alkyl chain long [C_6H_4-CH (Et) N_2-C_2H_3- (CO_2H) _2]H_2PW_ (12) O_ (40) has a better catalytic effect and the conversion of alpha pinene. The conversion rate is 95.2%, the selectivity of alpha pininol is 24.8%, the total selectivity of the hydrated product is 31.6%.. The catalyst has good reusability and remains high catalytic activity after 5 cycles. Based on the insoluble specificity of water oil two in the hydration reaction of alpha pinene, this paper also designs and syntheses the surface activity at the same time. With the acidic eighteen amine polyether carboxylic functionalized ionic liquid catalyst, a series of carboxyl functionalized ionic liquid catalysts with different degrees of polymerization, n (number of central ethoxy units in ionic liquids), were synthesized with halogenated carboxylic acids as carboxyl donors and phosphotungstic acid / sulfuric acid as anionic group. The reaction system is microemulsion at the reaction temperature (80 C), increasing the effective collision probability between the substrate molecules and obtaining a higher conversion rate, but the catalyst has a poor self separability after the reaction. The catalyst [AC1870-CH_2COOH]H_2PW_ (12) O_ (40) reaches 68.1% conversion and 25.5% under the condition of no auxiliary catalyst. The selectivity of alpha pinool provides a basis for the hydration of alpha pinene catalyzed by polyether carboxylic acid functional ionic liquids. The purpose of this paper is to explore a clean catalytic system for the hydration of alpha pinene without the aid of organic acids such as chloroacetic acid, which provides a new idea for the friendly catalytic process of the environment of biomass turpentine.

【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.3

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本文編號(hào)：1894665