本文關(guān)鍵詞：聚6-羥基己酸的水解反應(yīng)工藝研究　出處：《青島科技大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 聚6-羥基己酸 水解反應(yīng) 堿性條件 6-羥基己酸 絡(luò)合萃取法

【摘要】：聚6-羥基己酸因其優(yōu)良的生物降解性和生物相容性廣泛應(yīng)用于生物醫(yī)藥領(lǐng)域及組織工程的應(yīng)用研究。聚6-羥基己酸的最終降解產(chǎn)物為二氧化碳和水,對(duì)人體無毒無害;其良好的藥物通透性和力學(xué)性能,可作為藥物釋放載體材料,細(xì)胞、組織培養(yǎng)基架,完全可降解塑料手術(shù)縫合線等應(yīng)用于體內(nèi)。聚6-羥基己酸可與聚乙烯(PE)、聚丙烯(PP)、丙烯腈、丁二烯、苯乙烯三者的共聚物(ABS)、丙烯腈-苯乙烯共聚物(AS)、聚碳酸酯(PC)、聚氯乙烯(PVAC)、聚乙烯醇縮丁醛(PVB)、聚乙烯的醚類化合物(PVE)、尼龍(PA)、天然橡膠等高分子互容,可制備出多種性能優(yōu)良的共聚物或共混物。因此,近年來聚6-羥基己酸及其共聚物的研究備受研究者的青睞。作為生物可降解材料的代表,聚6-羥基己酸的需求量也將越來越大。隨著市場(chǎng)上對(duì)聚酯材料需求量的增多,廢棄的聚酯材料也將會(huì)帶來嚴(yán)重環(huán)境問題。盡管聚6-羥基己酸具有較好的生物可降解性,但是自然環(huán)境下的降解速度緩慢,也會(huì)造成資源的浪費(fèi)和環(huán)境污染。對(duì)于如今資源枯竭、能源短缺、環(huán)境污染等社會(huì)現(xiàn)實(shí)問題,我們應(yīng)該對(duì)廢棄的聚6-羥基己酸材料進(jìn)行合理的回收利用�；瘜W(xué)回收法可以將聚6-羥基己酸解聚成低分子量產(chǎn)物,重新將其作為聚合單體再次使用,讓聚酯材料發(fā)揮出它最大化的循環(huán)利用價(jià)值。本文探究了聚6-羥基己酸在氫氧化鈉、碳酸鈉、碳酸氫鈉三種不同堿度條件下水解反應(yīng)機(jī)理、優(yōu)化了工藝條件。在整個(gè)水解反應(yīng)系統(tǒng)中,選用乙二醇作溶劑。水解產(chǎn)物通過氣相色譜-質(zhì)譜聯(lián)用儀(GC-MS2010)定性,氣相色譜儀(GC2014C)定量。主要研究成果如下:1、氫氧化鈉堿度大,OH-濃度越大,親核基團(tuán)[OH-]直接進(jìn)攻聚6-羥基己酸的酯基結(jié)構(gòu),使酯基鍵發(fā)生斷裂反應(yīng),生成小分子的6-羥基己酸;反應(yīng)工藝條件緩和,在100℃的集熱式恒溫加熱磁力攪拌器中既可完全解聚。2、碳酸鈉、碳酸氫鈉堿度小,OH-濃度越小,在反應(yīng)初期親核基團(tuán)[-OCH2CH2OH]占主導(dǎo)地位,發(fā)生醇解反應(yīng)的概率大,整個(gè)反應(yīng)體系為醇解反應(yīng)與水解反應(yīng)相互促進(jìn)進(jìn)行;反應(yīng)工藝條件苛刻,須在180℃密閉高壓釜中完全解聚。3、探究出水解產(chǎn)物的分析方法:采用絡(luò)合萃取法萃取出水溶液中產(chǎn)物,排除水分對(duì)氣相色譜檢測(cè)的干擾。萃取劑選用三辛胺,在油水相比為1:1、25℃溫度條件下攪拌1h,水解產(chǎn)物的萃取率可達(dá)到97%以上。4、氫氧化鈉最優(yōu)化工藝條件:氫氧化鈉/聚6-羥基己酸摩爾比為4.4:1,乙二醇/聚6-羥基己酸摩爾比為6.5:1,催化劑0.1g,反應(yīng)溫度100℃,反應(yīng)時(shí)間2h條件下,聚6-羥基己酸解聚率達(dá)到96.06%,6-羥基己酸產(chǎn)率達(dá)到84.58%。5、碳酸鈉最優(yōu)化工藝條件:碳酸鈉/聚6-羥基己酸的摩爾比為1.3:1、乙二醇和聚6-羥基己酸的摩爾比為6:1,催化劑0.1g,反應(yīng)溫度為180℃,反應(yīng)時(shí)間為1h條件下,聚6-羥基己酸解聚率達(dá)到92.11%,6-羥基己酸產(chǎn)率達(dá)到78.13%。6、碳酸氫鈉最優(yōu)化工藝條件:碳酸氫鈉/聚6-羥基己酸摩爾比為1.1:1,乙二醇/聚6-羥基己酸摩爾比為3:1,催化劑0.1g,反應(yīng)溫度180℃-190℃,反應(yīng)時(shí)間1h條件下,聚6-羥基己酸解聚率達(dá)到98.53%,6-羥基己酸產(chǎn)率達(dá)到90.38%。7.在實(shí)驗(yàn)室研究的基礎(chǔ)上,進(jìn)行了聚6-羥基己酸在碳酸氫鈉水溶液中水解工藝的中試放大流程設(shè)計(jì),研究確定了工藝設(shè)計(jì)參數(shù),形成了整套工藝的工藝流程圖(PIDs)。8.利用危險(xiǎn)與可操作性分析(HAZOP)方法,對(duì)工藝過程的危險(xiǎn)因素進(jìn)行原因、后果和控制措施分析,提出了工藝裝置安全控制建議措施10條。
[Abstract]:Poly hydroxy 6- due to its excellent biodegradability and biocompatibility are widely used in the application of biomedicine and tissue engineering. The final degradation products of poly hydroxy 6- into carbon dioxide and water, non-toxic and harmless to the human body; its good permeability and mechanical properties, can be used as drug delivery carrier material, cell tissue culture, frame, totally biodegradable suture and in vivo applications. 6- and poly hydroxy polyethylene (PE), polypropylene (PP), acrylonitrile, butadiene, styrene copolymer of the three (ABS), acrylonitrile styrene copolymer (AS), polycarbonate (PC), polyvinyl chloride (PVAC). Polyvinyl butyral (PVB), ethers of polyethylene (PVE), nylon (PA), natural rubber and polymer compatibility, can produce a variety of excellent performance of the copolymers or blends. Therefore, in recent years, poly 6- hydroxy acid and its copolymer The study by researchers of all ages. As a representative of the biodegradable material, poly hydroxy 6- demand will be more and more big. With the increase of the amount of the market demand of polyester material, polyester waste will cause serious environmental problems. Although with good biodegradability of poly 6- hydroxy, but the degradation rate the natural environment is slow, will cause the waste of resources and environmental pollution. For now, the depletion of resources, energy shortages, environmental pollution and other social problems, we should from the poly 6- 3-hydroxyhexanoate material reasonable recycling. Can be poly hydroxy 6- depolymerized into low molecular weight products chemical recycling method. Again as the monomer used again, let play the polyester material recycling value of its maximum. This paper explores the poly hydroxy 6- in sodium hydroxide, sodium carbonate, carbonate The hydrolysis mechanism of sodium hydrogen three different alkalinity conditions, optimize the process conditions in the system. The hydrolysis reaction, using glycol as solvent. Hydrolysis products by gas chromatography-mass spectrometry (GC-MS2010) qualitative and quantitative gas chromatography (GC2014C). The main results are as follows: 1, sodium hydroxide alkalinity large, the greater the concentration of OH-, ester structure of the nucleophile [OH-] poly hydroxy 6- direct attack, the ester bond cleavage reaction, 6- 3-hydroxyhexanoate generation of small molecules; mild reaction conditions, the heat set 100 degrees constant temperature type magnetic force stirrer can completely depolymerized.2, sodium carbonate sodium bicarbonate alkalinity, small, OH- concentration is small, in the initial stage of the nucleophile [-OCH2CH2OH] dominates the probability of occurrence of the alcoholysis reaction, the reaction system for alcoholysis reaction and hydrolysis reaction and promote each other; reaction process conditions, must be 180 C sealed autoclave completely depolymerized.3, explore the analysis method of hydrolysis products: extract the product in aqueous solution by complex extraction method, to eliminate the interference of water on gas chromatography. Using three extractant octyl amine, in oil and water compared to the temperature of 1:1,25 DEG C under stirring 1H, extraction hydrolysis rate more than 97%.4, the optimum technical conditions: sodium hydroxide NaOH / poly hydroxy 6- molar ratio of 4.4:1, ethylene glycol / poly hydroxy 6- molar ratio of 6.5:1, catalyst 0.1g, reaction temperature 100 C, reaction time 2h, poly 6- hydroxy acid depolymerization rate has reached 96.06%, 6- hydroxy yield 84.58%.5, sodium carbonate the optimal process conditions: the molar ratio of sodium carbonate / poly 6- hydroxy is 1.3:1, ethylene glycol and poly hydroxy 6- molar ratio was 6:1, catalyst 0.1g, reaction temperature 180 C, reaction time is 1H, 6- poly hydroxy has The acid depolymerization rate reached 92.11%, 6- 3-hydroxyhexanoate yield reached 78.13%.6, the optimum technical conditions: sodium bicarbonate sodium bicarbonate / poly hydroxy 6- molar ratio of 1.1:1, ethylene glycol / poly hydroxy 6- molar ratio of 3:1, catalyst 0.1g, reaction temperature is 180 DEG -190 DEG C, the reaction time under the conditions of 1H, poly 6- 3-hydroxyhexanoate depolymerization rate reached 98.53%. 6- 3-hydroxyhexanoate yield 90.38%.7. on the basis of laboratory research, the poly hydroxy 6- in aqueous solution of sodium bicarbonate in the hydrolysis process of the scale-up process design, research to determine the design parameters of the process, forming a set of process flow diagram (PIDs) process hazard and operability analysis (HAZOP) method using.8. and risk factors on the process of the cause, consequence analysis and control measures, put forward process safety control measures 10.

【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)】：TQ323.4;R318.08

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 劉志德;張?chǎng)?王咪咪;張東;;微波作用下碳酸鹽對(duì)催化PET水解的研究[J];遼寧化工;2016年03期

2 李夢(mèng)娟;黃艷紅;余天石;陳世明;葛明橋;;乙二醇解聚廢棄聚酯纖維制備偶氮分散染料[J];材料導(dǎo)報(bào);2014年24期

3 張哲琦;牟德華;李艷;;優(yōu)化GC檢測(cè)2,4,6-三氯苯甲醚的萃取條件[J];食品工業(yè)科技;2014年24期

4 劉艷;;用三辛胺和磷酸三丁酯萃取、銨溶液反萃取鉬的研究[J];濕法冶金;2014年03期

5 陳飛飛;任曉莉;劉青松;秦剛;楊鋒;;鋅鋁混合氧化物催化降解廢棄PET聚酯的研究[J];武漢紡織大學(xué)學(xué)報(bào);2013年06期

6 王興原;陳紀(jì)忠;;不同醇解聚聚對(duì)苯二甲酸乙二醇酯的反應(yīng)特性[J];浙江大學(xué)學(xué)報(bào)(工學(xué)版);2013年05期

7 陳潁潁;沈劍;何潮洪;;三辛胺絡(luò)合萃取分離一氯乙酸和二氯乙酸[J];化工學(xué)報(bào);2013年02期

8 鄭海建;余天石;葛明橋;;丙三醇降解廢棄聚酯工藝條件的研究[J];材料導(dǎo)報(bào);2012年S1期

9 王先鋒;馬宏瑞;王立璇;;廢水中三辛胺對(duì)酸性染料的絡(luò)合萃取[J];皮革科學(xué)與工程;2012年01期

10 余天石;俞捷;葛明橋;;丙三醇醇解聚酯產(chǎn)物的測(cè)試與表征[J];紡織學(xué)報(bào);2012年01期

相關(guān)會(huì)議論文 前1條

1 賈旭宏;李軍;金央;周X;羅建洪;王保明;;三辛胺萃取分離硝酸和磷酸的研究[A];中國(guó)化學(xué)會(huì)第28屆學(xué)術(shù)年會(huì)第19分會(huì)場(chǎng)摘要集[C];2012年

相關(guān)碩士學(xué)位論文 前10條

1 鐘玲;PET微波解聚及其非等溫動(dòng)力學(xué)研究[D];溫州大學(xué);2015年

2 王姣姣;ε-己內(nèi)酯改性雙季戊四醇六丙烯酸酯合成工藝的改進(jìn)[D];鄭州大學(xué);2014年

3 殷海洪;EDTA合成母液中羥基乙酸的絡(luò)合萃取分離[D];華東理工大學(xué);2014年

4 鄭海建;丙三醇解聚廢棄聚酯制備納米復(fù)合固化劑[D];江南大學(xué);2013年

5 楊學(xué)群;聚乳酸和聚己內(nèi)酯的水解反應(yīng)研究[D];青島科技大學(xué);2013年

6 高靜;聚對(duì)苯二甲酸丙二醇酯在亞臨界水中的解聚研究[D];浙江工業(yè)大學(xué);2012年

7 唐清華;微波輻射下PET水解過程中分子量的變化與解聚機(jī)理研究[D];溫州大學(xué);2012年

8 王媚嫻;超/亞臨界水中聚對(duì)苯二甲酸乙二醇酯解聚研究[D];浙江工業(yè)大學(xué);2010年

9 賈延華;微波環(huán)境下催化解聚PET的動(dòng)力學(xué)研究[D];溫州大學(xué);2010年

10 張現(xiàn)剛;超/亞臨界水中聚碳酸酯/聚對(duì)苯二甲酸乙二醇酯催化解聚研究[D];浙江工業(yè)大學(xué);2009年

，

本文編號(hào)：1397438