CN105801816B - 一种制备可生物降解材料聚β-羟基丁酸酯的方法 - Google Patents
一种制备可生物降解材料聚β-羟基丁酸酯的方法 Download PDFInfo
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Abstract
本发明属于化学合成技术领域，具体公开了一种制备可生物降解材料聚β‑羟基丁酸酯的方法。所述方法为：将一定量的3‑羟基丁酸乙酯、催化剂和去离子水搅拌均匀，然后加热反应2～3.5h，即制得一定粘均分子量的聚β‑羟基丁酸酯。本发明方法在反应过程不需要引入氮气、氩气等惰性气体，操作简单便捷。根据本发明的技术方案，在加热状态下制备PHB的时间不超过4h，是其他传统方法的反应时间一半或更少。本发明制备方法显著缩短反应时间，简化制备工艺，降低生产成本。
Description
技术领域
本发明属于化学合成技术领域，具体涉及一种制备可生物降解材料聚β-羟基丁酸酯的方法。
背景技术
聚β-羟基丁酸酯(PHB)是一种脂肪族聚酯类化合物，具有良好得可生物降解性和生物相容性，是一种可完全生物降解的新型材料，其应用包括生产快餐盒、地膜及包装材料等一次性用品，更可应用于医学、光电子化学、精细化工等高新技术行业，在高新技术和高附加值领域市场广阔。
目前PHB主要采用生物发酵法制备，其产品价格高，制备的产品为多种化合物的大分子量的混聚物，因此大大限制了其推广应用。由于生物法制备PHB的周期长，成本高等缺点，有研究采用化学法制备PHB，以降低其生产成本，为工业化生产提供一个新的方向。
国外有报道采用PHB的单体β-丁内酯在一定条件下合成PHB的试验方法，“Anefficient synthesis of optically active 4-methyloxetan-2-one:asymmetrichydrogenation of diketene catalysed by binap–ruthenium(II)complexes[binap＝2,2′-bis(diphenylphosphino)-1,1′-binaphthyl][J].Ohta T,Miyake T,TakayaH.Journal of the Chemical Society,Chemical Communications.1992(23):1725-1726.”采用双烯酮在催化剂作用下进行非对称氢化可制得具有光学活性的β-丁内酯，制得的β-丁内酯在催化剂作用下开环聚合生成PHB；“Ring-Opening Polymerization ofOptically Activeβ-Butyrolactone Using Distannoxane Synthesis of HighMolecular Weight[J].Hori Y,Suzuki M,Yamaguchi A,et al.Macromolecules.1993(26):5533-5534.”以二锡氧烷为催化剂，用于β-丁内酯的开环聚合生成PHB。相关报道表明β-丁内酯是一种可致癌物质，不符合绿色环保的理念。
王加宁等人在专利(中国，授权公告号：CN1216090C)中采用乙醛为原料合成β-羟基丁醛，再氧化生成β-羟基丁酸，酯化后生成β-羟基丁酸乙酯；利用合成的β-羟基丁酸乙酯在催化剂钛酸异丙酯作用下，通入氮气保护，绝压1kPa-7Pa，反应温度150-170℃，反应时间20-30小时左右，合成聚合度为15.4、分子量为1382.4g/mol的PHB。
“聚羟基丁酸酯的化学合成及生物降解性[J].王加宁，杨合同，马沛生，等.化学工业与工程.2005(02):100-103.”在油浴加热下利用钛酸四丁酯催化3-羟基丁酸乙酯进行聚合，反应温度140-160℃，绝压为0.13×103kPa条件下反应30h后可得聚合度为12.2的PHB产物，摩尔质量为1095.2g/mol。“化学合成法制备聚3-羟基丁酸酯及其共聚物的研究[D].刘峻.天津大学,2006.”以3-羟基丁酸乙酯为原料，分别以草酸钛钾、钛酸四丁酯为催化剂在氩气保护下进行反应，反应温度为140℃，反应时间为8小时，产物颜色变深，并无明显聚合反应现象。
发明内容
为解决现有技术的缺点和不足之处，本发明的目的在于提供一种制备可生物降解材料聚β-羟基丁酸酯的方法，该方法聚合过程中无需氮气保护，无需抽真空，可简化反应条件、缩短反应时间，同时得到较高分子量的PHB产物。
本发明目的通过以下技术方案实现：
一种制备可生物降解材料聚β-羟基丁酸酯的方法，包括以下步骤：
将一定量的3-羟基丁酸乙酯、催化剂和水搅拌均匀，然后加热反应2～3.5h，制得粘均分子量为2830～55455.5g/mol的聚β-羟基丁酸酯。
本发明中所用催化剂为钛酸四丁酯，反应温度为140～160℃，优选为150～160℃，无需惰性气体保护、无需抽真空。
所述催化剂与3-羟基丁酸乙酯的体积比为1:3～1:6，催化剂与水的体积比为40:1～140:1。
所述加热的方式可以是煤、气、油浴、电等常规加热方式，本发明中优选采用电加热套。上述反应过程不需要引入氮气、氩气等惰性气体，反应不需要在密闭环境下进行，在常压下就可以进行，操作简单便捷。
本发明方法中少量水的引入主要是起到助催化作用，水使催化剂迅速而有效的分散、并与原料充分混合，利用水与催化剂形成“钛酸四丁酯/水”的共催化体系进行催化聚合反应；
本发明方法中不抽真空可少耗能、简化工艺操控难度，3-羟基丁酸乙酯常压下沸点为177℃，随着真空度的增加，其沸点会随之降低，在维持140～160℃的反应温度下，部分原料会蒸发而被抽出反应体系，影响产量。
与现有技术相比，本发明具有以下优点及有益效果：
根据本发明的技术方案，在加热状态下制备PHB的时间不超过4h，是其他传统方法的反应时间一半或更少，并且本发明的方法制备得到的PHB的分子量高于现有技术制备的PHB的分子量。本发明制备方法显著缩短反应时间，简化制备工艺，降低生产成本。
附图说明
图1为本发明实施例中的实验反应装置，其中：1-电加热套，2-圆底烧瓶，3-温度计，4-冷凝管，5-接收瓶。
图2为实施例1-5制得的聚β-羟基丁酸酯的红外图谱。
图3为对比例1制得的产物的红外图谱。
图4为对比例2制得的产物的红外图谱。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
将30mL 3-羟基丁酸乙酯置于250mL圆底烧瓶中，加入10mL质量浓度为98％的钛酸四丁酯，滴加0.11mL去离子水。将烧瓶置于电加热套加热，160℃左右下反应2.5h，得产物聚β-羟基丁酸酯。经检测，制得的产物样品量为4.0257g，产物粘均分子量为55455.5g/mol。
实施例2
将30mL 3-羟基丁酸乙酯置于250mL圆底烧瓶中，加入10mL质量浓度为98％的钛酸四丁酯，滴加0.25mL去离子水。将烧瓶置于电加热套加热，150℃左右下反应2.5h，得产物聚β-羟基丁酸酯。经检测，制得的产物样品量为6.7267g，产物粘均分子量为30506.4g/mol。
实施例3
将45mL 3-羟基丁酸乙酯置于250mL圆底烧瓶中，加入15mL质量浓度为98％的钛酸四丁酯，滴加0.11mL去离子水。将烧瓶置于电加热套加热，155℃左右下反应3.5h，得产物聚β-羟基丁酸酯。经检测，制得的产物样品量为3.0805g，产物粘均分子量为25449.3g/mol。
实施例4
将30mL 3-羟基丁酸乙酯置于250mL圆底烧瓶中，加入10mL质量浓度为98％的钛酸四丁酯，滴加0.2mL去离子水。将烧瓶置于电加热套加热，160℃左右下反应2h，得产物聚β-羟基丁酸酯。经检测，制得的产物样品量为5.0055g，产物粘均分子量为18651.8g/mol。
实施例5
将30mL 3-羟基丁酸乙酯置于250mL圆底烧瓶中，加入5mL质量浓度为98％的钛酸四丁酯，滴加0.11mL去离子水。将烧瓶置于电加热套加热，160℃左右下反应2h，得产物聚β-羟基丁酸酯。经检测，制得的产物样品量为0.1029g，产物粘均分子量为2830.8g/mol。
对比例1
将30mL 3-羟基丁酸乙酯置于250mL圆底烧瓶中，加入8mL质量浓度为98％的钛酸四丁酯。将烧瓶置于电加热套加热，160℃左右下反应2h，得到固体产物。经检测，制得的产物样品量为0.1519g。
对比例2
将30mL 3-羟基丁酸乙酯置于250mL圆底烧瓶中，加入10mL质量浓度为98％的钛酸四丁酯。将烧瓶置于电加热套加热，160℃左右下反应2h，得到固体产物。经检测，制得的产物样品量为0.2189g。
用傅立叶红外光谱仪对上述实施例和对比例制得的产物进行扫描，通过扫描后红外谱图显示的特征峰值来判断产物是否具有PHB应有的官能团，从而判断产物是否为PHB。实施例1-5的产物的红外图谱见图2，对比例1、2的产物的红外图谱见图3和图4。图2中聚合产物在1740cm-1附近有强的>C＝O伸缩振动峰，在1103cm-1、1136cm-1和1184cm-1处有C-O-C伸缩振动峰，说明聚合产物中有-COO-的存在；在1446cm-1、2938cm-1和2982cm-1处分别有-CH3、-CH2和-CH的弯曲振动峰和伸缩振动峰；在3431cm-1左右出现的较强的-OH的吸收峰；综上分析可判断产物具有PHB所具备的全部特征官能团；而在图3和图4中除了在3450cm-1左右出现-OH的较强的吸收峰外，其余吸收峰均不明显。可见，在对比例1和2中制得的产物的红外谱图显示，与前述实施例1-5的产物谱图有差异，判断对比例1和2制得的产物与PHB在特征官能团方面存在一定差异。
另外，在测粘均分子量的时候，两个对比例中制备的产物也不溶于溶剂，因此无法测定产物粘均分子量。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (2)
1.一种制备可生物降解材料聚β-羟基丁酸酯的方法，其特征在于，包括以下步骤：在常压下，将一定量的3-羟基丁酸乙酯、催化剂和去离子水搅拌均匀，然后在140～160℃反应2～3.5h，制得粘均分子量为2830～55455.5g/mol的聚β-羟基丁酸酯；所述催化剂为钛酸四丁酯；所述催化剂与3-羟基丁酸乙酯的体积比为1:3～1:6，催化剂与水的体积比为40:1～140:1。
2.根据权利要求1所述的制备可生物降解材料聚β-羟基丁酸酯的方法，其特征在于，所述反应的温度为150～160℃。
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| CN103483562A (zh) * | 2013-09-26 | 2014-01-01 | 南京年吉冷冻食品有限公司 | 一种聚羟基丁酸酯的化学合成方法 |
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| CN103467715A (zh) * | 2013-09-26 | 2013-12-25 | 南京年吉冷冻食品有限公司 | 可生物降解的聚羟基丁酸酯共聚混合物的合成方法 |
| CN103483562A (zh) * | 2013-09-26 | 2014-01-01 | 南京年吉冷冻食品有限公司 | 一种聚羟基丁酸酯的化学合成方法 |
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