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
- Publication number
- CN105801816B CN105801816B CN201610188698.3A CN201610188698A CN105801816B CN 105801816 B CN105801816 B CN 105801816B CN 201610188698 A CN201610188698 A CN 201610188698A CN 105801816 B CN105801816 B CN 105801816B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- present
- product
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 10
- 239000002253 acid Substances 0.000 title claims description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract 2
- 229910021641 deionized water Inorganic materials 0.000 claims abstract 2
- OMSUIQOIVADKIM-UHFFFAOYSA-N ethyl 3-hydroxybutyrate Chemical compound CCOC(=O)CC(C)O OMSUIQOIVADKIM-UHFFFAOYSA-N 0.000 claims description 23
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910052786 argon Inorganic materials 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 229920000331 Polyhydroxybutyrate Polymers 0.000 abstract 3
- 229920001397 Poly-beta-hydroxybutyrate Polymers 0.000 abstract 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 34
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005485 electric heating Methods 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 1
- QLACRIKFZRFWRU-UHFFFAOYSA-N [4-oxo-4-(4-oxobutan-2-yloxy)butan-2-yl] 3-hydroxybutanoate Chemical compound CC(O)CC(=O)OC(C)CC(=O)OC(C)CC=O QLACRIKFZRFWRU-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 1
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
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℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610188698.3A CN105801816B (zh) | 2016-03-28 | 2016-03-28 | 一种制备可生物降解材料聚β-羟基丁酸酯的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610188698.3A CN105801816B (zh) | 2016-03-28 | 2016-03-28 | 一种制备可生物降解材料聚β-羟基丁酸酯的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105801816A CN105801816A (zh) | 2016-07-27 |
| CN105801816B true CN105801816B (zh) | 2018-07-13 |
Family
ID=56454170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610188698.3A Expired - Fee Related CN105801816B (zh) | 2016-03-28 | 2016-03-28 | 一种制备可生物降解材料聚β-羟基丁酸酯的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801816B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961322B (zh) * | 2020-08-21 | 2022-02-22 | 青岛科技大学 | 聚（4-羟基丁酸酯）生物可降解包装薄膜及其制备方法 |
| CN113773474B (zh) * | 2021-10-21 | 2022-11-29 | 辽宁科信生物科技有限公司 | 聚β-羟基丁酸酯的合成方法 |
| CN114947046B (zh) * | 2022-05-12 | 2023-06-16 | 华南理工大学 | 聚3-羟基丁酸酯作为面粉或面制品添加剂的应用 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855483A (en) * | 1988-02-18 | 1989-08-08 | General Electric Company | Method for preparing polysalicylates |
| 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 |
-
2016
- 2016-03-28 CN CN201610188698.3A patent/CN105801816B/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855483A (en) * | 1988-02-18 | 1989-08-08 | General Electric Company | Method for preparing polysalicylates |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 聚羟基丁酸酯的化学合成及生物降解性;王加宁等;《化学工业与工程》;20050331;第22卷(第2期);第101页右栏第1段到第102页左栏第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105801816A (zh) | 2016-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Quinzler et al. | Linear semicrystalline polyesters from fatty acids by complete feedstock molecule utilization | |
| CN105801816B (zh) | 一种制备可生物降解材料聚β-羟基丁酸酯的方法 | |
| Terzopoulou et al. | Decomposition mechanism of polyesters based on 2, 5-furandicarboxylic acid and aliphatic diols with medium and long chain methylene groups | |
| CN107188802B (zh) | 应用双酸型离子液体催化醇解聚3-羟基丁酸酯的方法 | |
| EP3421459B1 (en) | Method for synthesizing lactide by means of catalysis of lactic acid | |
| Vilela et al. | Polymers and copolymers from fatty acid-based monomers | |
| Jose et al. | Thermoplastic polyesters and co-polyesters derived from vegetable oil: synthesis and optimization of melt polycondensation for medium and long chain poly (ω-hydroxyfatty acid) s and their ester derivatives | |
| JP2009538972A (ja) | ポリアミドブロックコポリマーの製造 | |
| CN106188507B (zh) | 一种高分子量环状聚乳酸的合成方法 | |
| CN112898464B (zh) | 极性聚烯烃材料及其制备方法和应用 | |
| Li et al. | Stereoselective ring-opening polymerization of rac-lactide by bulky chiral and achiral N-heterocyclic carbenes | |
| CN107353414B (zh) | 超支化聚己内酯及其制备方法 | |
| CN113461926A (zh) | 一种聚β-羟基脂肪酸酯的化学合成方法 | |
| CN109810744B (zh) | 一种酸性聚合离子液体催化制备生物润滑油的方法 | |
| CN111925400A (zh) | 一种氧化还原响应性金属卟啉配合物、其制备方法和聚乳酸的制备方法 | |
| CN110396180B (zh) | 一种利用甜菜碱精密制备脂肪族聚酯的方法 | |
| CN109280158B (zh) | 利用d-丙交酯开环聚合生产聚d-乳酸的方法 | |
| CN105820318B (zh) | 一种常压微波辐射制备可生物降解材料聚β-羟基丁酸酯的方法 | |
| Nishida et al. | Catalytic double ring-opening polyaddition of spiro orthoester with acid chloride for shrinkage-controlled molding | |
| Hamaide et al. | Heterogeneous catalysis for ring opening anionic oligomerisation | |
| CN112898497B (zh) | 一种聚乳酸基大分子单体及其制备方法和应用 | |
| CN108164690A (zh) | 一种制备聚酯的方法 | |
| Liu et al. | Post-polymerization modification of poly (vinyl ether) s: a Ru-catalyzed oxidative synthesis of poly (vinyl ester) s and poly (propenyl ester) s | |
| CN115703720A (zh) | 一种螺环Salen配体、Salen催化剂及制备方法及其在开环聚合中的应用 | |
| CN1117786C (zh) | 一种用于合成高吸水性树脂的改性脂肪型超支化聚酯的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 510530 No. 18, Rui Lu, Luogang District, Guangdong, Guangzhou Co-patentee after: COLLEGE OF MUNICIPAL WORKS & CONSTRUCTION, GUANGZHOU University Patentee after: SOUTH CHINA INSTITUTE OF ENVIRONMENTAL SCIENCES. MEE Address before: Tianhe District West Village Guangzhou city Guangdong province 510655 No. seven compound Co-patentee before: COLLEGE OF MUNICIPAL WORKS & CONSTRUCTION, GUANGZHOU University Patentee before: South China Institute of Environmental Sciences. MEP |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180713 |