本申请为申请号200610049288.7、申请日2006年1月27日、发明名称“苯甲酸亚锡作为催化剂的用途”的分案申请。This application is a divisional application with application number 200610049288.7, application date January 27, 2006, and invention name "Use of stannous benzoate as a catalyst".
技术领域technical field
本发明涉及苯甲酸亚锡的用途，尤其涉及苯甲酸亚锡在催化剂领域的用途。The present invention relates to the purposes of stannous benzoate, relate in particular to the purposes of stannous benzoate in catalyst field.
背景技术Background technique
催化剂是指在化学反应中能够改变反应速率，而本身的质量和化学组成在反应前后均不发生改变的物质；在催化剂的作用下，可以大大降低反应温度，时间和压力。Catalyst refers to a substance that can change the reaction rate in a chemical reaction, but its quality and chemical composition do not change before and after the reaction; under the action of the catalyst, the reaction temperature, time and pressure can be greatly reduced.
乳酸或羟基乙酸在催化剂作用下，经脱水形成分子量在2000～10000的低聚物，随后直接在高温下裂解减压蒸馏得到粗丙交酯或粗乙交酯。常用的乳酸或羟基乙酸脱水低聚和高温裂解的催化剂有：AlCl3，FeCl3，FeCl2，BF3，BBr3，TiO2，TiCl4，TiBr4，SnSO4，SnBr4，辛酸亚锡等。使用这些催化剂易使乳酸低聚物或羟基乙酸低聚物在裂解反应器中结焦成块，很难清理，而且每反应一次要清理一次，消耗大量的人力和物力；此外得到的丙交酯或乙交酯颜色发黄，且收率比较低；Under the action of a catalyst, lactic acid or glycolic acid is dehydrated to form an oligomer with a molecular weight of 2,000 to 10,000, and then directly cracked at high temperature and distilled under reduced pressure to obtain crude lactide or crude glycolide. Commonly used catalysts for dehydration oligomerization and pyrolysis of lactic acid or glycolic acid include: AlCl3 , FeCl3 , FeCl2 , BF 3 , BBr3 , TiO2, TiCl4 , TiBr4 , SnSO4 , SnBr4 , stannous octoate, etc. . The use of these catalysts tends to cause lactic acid oligomers or glycolic acid oligomers to coke into blocks in the cracking reactor, which is difficult to clean up, and it is necessary to clean up once for each reaction, which consumes a lot of manpower and material resources; in addition, the obtained lactide or The color of glycolide turns yellow, and the yield is relatively low;
内酯和交酯的开环聚合通常采用的催化剂有异丙醇铝、辛酸亚锡以及有机稀土化合物等，其中使用最广泛是辛酸亚锡，它无毒、可合成高分子且光学纯度好的聚酯。但是它的催化反应活性不高，要求较长的聚合反应时间和较高的反应温度；因此需要开发一种高活性的聚合催化剂。The catalysts usually used for the ring-opening polymerization of lactones and lactides include aluminum isopropoxide, stannous octoate, and organic rare earth compounds, among which stannous octoate is the most widely used, which is non-toxic, can be synthesized into polymers, and has good optical purity. polyester. However, its catalytic activity is not high, requiring longer polymerization time and higher reaction temperature; therefore, it is necessary to develop a highly active polymerization catalyst.
发明内容Contents of the invention
本发明针对现有的催化剂在乳酸和羟基乙酸低聚速率慢，裂解反应过程中容易使产物在反应器中结焦成块，得到的产物颜色发黄，且收率比较低的缺点，故提供苯甲酸亚锡作为低聚和裂解催化剂的用途。The present invention aims at the shortcomings of the existing catalysts that the oligomerization rate of lactic acid and glycolic acid is slow, and the products are easily coked into blocks in the reactor during the cracking reaction process, the color of the obtained product is yellow, and the yield is relatively low, so it provides benzene Use of stannous formate as oligomerization and cracking catalyst.
本发明还针对现有催化剂催化交酯和环酯的开环聚合反应活性不高，要求较长的聚合反应时间和较高的反应温度，故提供苯甲酸亚锡作为高活性聚合催化剂的用途。The present invention also aims at the ring-opening polymerization activity of existing catalyst catalyzed lactide and cyclic ester is not high, requires longer polymerization reaction time and higher reaction temperature, so stannous benzoate is provided as the purposes of highly active polymerization catalyst.
实际上，本发明涉及苯甲酸亚锡作为乳酸脱水形成低聚乳酸的催化剂的用途。In fact, the present invention relates to the use of stannous benzoate as a catalyst for the dehydration of lactic acid to form oligomeric lactic acid.
作为优选：所述的乳酸为L-乳酸，D-乳酸，D，L-乳酸中的一种或多种混合。As a preference: the lactic acid is a mixture of one or more of L-lactic acid, D-lactic acid, D, L-lactic acid.
涉及苯甲酸亚锡作为低聚乳酸裂解生成丙交酯的催化剂的用途。It relates to the use of stannous benzoate as a catalyst for oligomeric lactic acid cracking to generate lactide.
涉及苯甲酸亚锡作为丙交酯均聚合生成聚乳酸的催化剂的用途。It relates to the use of stannous benzoate as a catalyst for the homopolymerization of lactide to generate polylactic acid.
作为优选，所述的丙交酯为L-丙交酯，D-丙交酯、内消旋D，L-丙交酯中的一种或多种混合；其中所述的均聚合方法为本体聚合或溶液聚合中的一种。Preferably, the lactide is a mixture of one or more of L-lactide, D-lactide, meso-D, L-lactide; wherein the homopolymerization method is bulk One of polymerization or solution polymerization.
苯甲酸亚锡作为乳酸脱水低聚和高温裂解的催化剂，反应活性高，丙交酯产率高。乳酸(88％水溶液)经过脱水酯化后得到聚合乳酸低聚物(分子量一般在1000～3000)加入苯甲酸亚锡作为催化剂(用量为0.1～0.2wt％)，可缩短乳酸脱水和低聚物在180～240℃裂解生成丙交酯的反应时间，一般可减少反应时间5～6小时。催化剂可重复使用，反应器内不结焦。作为丙交酯开环聚合反应催化剂，反应温度同辛酸亚锡相同，适用于丙交酯的本体聚合和溶液聚合，在本体聚合中聚合物中含有残留单体，在表征聚合物时，必须将残留单体除去；溶液聚合以甲苯为溶剂，以乙醇作为沉淀剂，将聚合物析出、干燥后称重可计算收率和对聚合物表征。本体聚合物可用核磁共振法测定转化率，但必须将聚合物用溶剂溶解后再用乙醇析出、干燥后才能对聚合物进行表征，如测定分子量等。产物为聚丙交酯也称为聚乳酸，具有生物可降解性。作为塑料，其性能与聚丙稀类似，通过改性可达到聚乙烯的使用性能，因此，广泛应用于各种塑料制品的制备。聚乳酸本身或通过物理改性适用于通常的挤出、注射、吹膜、发泡、吸塑等加工方法。可以制成纤维、膜、棒、块、板材等应用于纺织、包装等各种民用、工业应用和医疗特殊应用领域。As a catalyst for dehydration oligomerization and pyrolysis of lactic acid, stannous benzoate has high reactivity and high lactide yield. Lactic acid (88% aqueous solution) is dehydrated and esterified to obtain polymerized lactic acid oligomers (molecular weight is generally 1000-3000). Adding stannous benzoate as a catalyst (amount of 0.1-0.2wt%) can shorten the dehydration and oligomers of lactic acid. The reaction time of pyrolysis to generate lactide at 180-240°C can generally reduce the reaction time by 5-6 hours. The catalyst can be used repeatedly, and there is no coking in the reactor. As a lactide ring-opening polymerization catalyst, the reaction temperature is the same as that of stannous octoate. It is suitable for bulk polymerization and solution polymerization of lactide. In bulk polymerization, the polymer contains residual monomers. When characterizing the polymer, it must be Residual monomers are removed; solution polymerization uses toluene as a solvent and ethanol as a precipitating agent. The polymer is precipitated, dried and weighed to calculate the yield and characterize the polymer. The conversion rate of the bulk polymer can be determined by nuclear magnetic resonance, but the polymer must be dissolved in a solvent and then precipitated with ethanol and dried before the polymer can be characterized, such as the molecular weight. The product is polylactide, also known as polylactic acid, which is biodegradable. As a plastic, its performance is similar to that of polypropylene, and the performance of polyethylene can be achieved through modification. Therefore, it is widely used in the preparation of various plastic products. Polylactic acid itself or through physical modification is suitable for the usual processing methods such as extrusion, injection, film blowing, foaming, and blistering. It can be made into fibers, films, rods, blocks, plates, etc. to be used in various civil, industrial and medical special application fields such as textiles and packaging.
由于乳酸在α位上有一个甲基的存在，使得乳酸具有光学活性，因此乳酸存在左旋(L)、右旋(D)两种光学异构体和DL不同比例的混合体，其中L型和D型1：1的混合体称为D，L-乳酸。丙交酯(LA)是由两个分子的乳酸脱水环化组成的二聚体交酯，是经由乳酸脱水形成分子量低的聚乳酸，再经高温裂解减压蒸馏得到的。由于乳酸两种光学异构体的存在，导致丙交酯存在左旋—丙交酯(LLA)、右旋—丙交酯(DLA)和内消旋丙交酯(meso—DLLA)三种异构体和他们之间不同比例的混合体。50％的左旋—丙交酯和50％的右旋—丙交酯的混合体被称为外消旋丙交酯(racemic-DLLA)。Due to the existence of a methyl group on the α-position of lactic acid, lactic acid is optically active, so lactic acid has two optical isomers of left-handed (L) and right-handed (D) and a mixture of different proportions of DL, of which the L-type and The D-type 1:1 mixture is called D,L-lactic acid. Lactide (LA) is a dimer lactide formed by the dehydration and cyclization of two molecules of lactic acid. It is obtained by dehydrating lactic acid to form polylactic acid with a low molecular weight, and then undergoing high-temperature cracking and vacuum distillation. Due to the existence of two optical isomers of lactic acid, there are three isomerisms of L-lactide (LLA), D-lactide (DLA) and meso-lactide (meso-DLLA) in lactide. bodies and mixtures of different proportions between them. A mixture of 50% L-lactide and 50% D-lactide is called racemic-DLLA.
因此，本发明中所用乳酸可以为L-乳酸，D-乳酸，D，L-乳酸中的一种或多种混合。所得到的丙交酯为L-丙交酯，D-丙交酯、内消旋D，L-丙交酯中的一种或多种混合。通常L-乳酸，D-乳酸旋光纯度为95～99.5％。Therefore, the lactic acid used in the present invention can be one or more of L-lactic acid, D-lactic acid, D, L-lactic acid mixed. The obtained lactide is one or more mixtures of L-lactide, D-lactide and meso-D, L-lactide. Usually the optical purity of L-lactic acid and D-lactic acid is 95-99.5%.
此外，本发明还涉及苯甲酸亚锡作为羟基乙酸脱水生成低聚羟基乙酸的催化剂的用途。In addition, the present invention also relates to the use of stannous benzoate as a catalyst for the dehydration of glycolic acid to generate oligoglycolic acid.
还涉及苯甲酸亚锡作为低聚羟基乙酸裂解生成乙交酯的催化剂的用途。It also relates to the use of stannous benzoate as a catalyst for the cracking of oligoglycolic acid to generate glycolide.
还涉及苯甲酸亚锡作为乙交酯均聚合生成聚乙交酯的催化剂的用途。所述的均聚合为本体聚合或溶液聚合中的一种。It also relates to the use of stannous benzoate as a catalyst for the homopolymerization of glycolide to generate polyglycolide. The homopolymerization is one of bulk polymerization or solution polymerization.
还涉及苯甲酸亚锡作为乙交酯、丙交酯、ε-已内酯两者或三者之间的共聚合的催化剂的用途。It also relates to the use of stannous benzoate as a catalyst for the copolymerization of glycolide, lactide and ε-caprolactone or between the three.
作为优选，所述的丙交酯为L-丙交酯，D-丙交酯、D，L-丙交酯中的一种或多种混合；其中所述的共聚合方法为本体聚合或溶液聚合中的一种。Preferably, the lactide is a mixture of one or more of L-lactide, D-lactide, and D, L-lactide; wherein the copolymerization method is bulk polymerization or solution A type of aggregation.
苯甲酸亚锡作为羟基乙酸脱水低聚和高温裂解的催化剂，特点是催化剂用量低，反应活性高，乙交酯收率高，产品纯度高，颜色白，裂解温度低，可重复使用。作为乙交酯开环聚合反应催化剂，特点是聚合反应速度温和，产物熔融指数高，适用于溶液聚合或本体聚合。采用溶液聚合时，由于聚乙交酯不溶解于通常的有机溶剂，因此，发生聚合沉淀现象。聚乙交酯只溶于全氟异丙醇中。苯甲酸亚锡作为乙交酯、丙交酯、ε-已内酯之间两者或三者之间的共聚合催化剂，特点是聚合反应活性高，聚合物的分子量高，适用于本体聚合，另外，根据乙交酯的投料含量，如果聚合产物可以溶解在有机溶剂中，则可以采用溶液聚合。Stannous benzoate is used as a catalyst for dehydration oligomerization and pyrolysis of glycolic acid. It is characterized by low catalyst consumption, high reactivity, high yield of glycolide, high product purity, white color, low cracking temperature, and can be reused. As a catalyst for ring-opening polymerization of glycolide, it is characterized by mild polymerization reaction speed and high product melt index, and is suitable for solution polymerization or bulk polymerization. In the case of solution polymerization, since polyglycolide is insoluble in common organic solvents, polymerization precipitation occurs. Polyglycolide is only soluble in perfluoroisopropanol. Stannous benzoate is used as a copolymerization catalyst between glycolide, lactide, and ε-caprolactone or between the three, and is characterized by high polymerization activity and high molecular weight of the polymer, which is suitable for bulk polymerization. In addition, according to the feed content of glycolide, if the polymerization product can be dissolved in an organic solvent, solution polymerization can be used.
生物可降解聚酯的主链是由脂肪族结构单元通过易水解的酯键连接而成，在微生物或生物体酶或酸、碱的促进下水解，分子量降低，最终形成二氧化碳和水，同时有很好的组织相容性，被广泛应用于医疗外科手术缝线，骨折内固定、组织工程修复材料及药物控制释放体系等。The main chain of biodegradable polyester is composed of aliphatic structural units connected by easily hydrolyzed ester bonds. Under the promotion of microbial or biological enzymes or acid and alkali, the molecular weight is reduced, and finally carbon dioxide and water are formed. At the same time, there are With good tissue compatibility, it is widely used in medical and surgical sutures, internal fixation of fractures, tissue engineering repair materials and drug controlled release systems, etc.
聚羟基乙酸或称为聚乙交酯(PGA)是结构最简单的线性脂肪族聚酯，是体内可吸收高分子最早商品化的一个品种。由丙交酯(LA)和乙交酯(GA)开环聚合分别制得了高分子量得聚乳酸或称为聚丙交酯(PLA)和聚乙交酯(PGA)，由于其容易水解，且降解的产物为乳酸、羟基乙酸等都是机体代谢的中间产物，所以这类聚酯被优先考虑用作可降解的手术缝线而取代胶原。随后，环状酯类的开环聚合得到了广泛的研究。乙交酯和丙交酯共聚后可使降解速度比均聚合物提高10倍以上，并且通过改变乙交酯和丙交酯的组分比，可以有效地调节共聚物的降解速率。乙交酯和丙交酯的共聚物可作为抗癌药物控制释放体系基材制得新型缓释药物，同样，乙交酯、丙交酯同ε-已内酯单体的共聚物，也是很好的组织工程支架、手术缝合物、体内临时修复、药物缓释等功能材料。Polyglycolic acid or polyglycolide (PGA) is the linear aliphatic polyester with the simplest structure and the earliest commercialized variety of in vivo absorbable polymer. High molecular weight polylactic acid or polylactide (PLA) and polyglycolide (PGA) were prepared by ring-opening polymerization of lactide (LA) and glycolide (GA), respectively, because it is easily hydrolyzed and degraded The products of lactic acid, glycolic acid, etc. are intermediate products of body metabolism, so this kind of polyester is preferentially considered as a degradable surgical suture instead of collagen. Subsequently, the ring-opening polymerization of cyclic esters has been extensively studied. After the copolymerization of glycolide and lactide, the degradation rate can be increased by more than 10 times than that of the homopolymer, and the degradation rate of the copolymer can be effectively adjusted by changing the component ratio of glycolide and lactide. Copolymers of glycolide and lactide can be used as the base material of anticancer drug controlled release system to prepare new sustained release drugs. Similarly, copolymers of glycolide, lactide and ε-caprolactone monomer are also very Good functional materials such as tissue engineering scaffolds, surgical sutures, temporary repairs in vivo, drug sustained release, etc.
因此本发明具有以下优点：Therefore the present invention has the following advantages:
1、本发明涉及苯甲酸亚锡作为乳酸低聚和裂解的催化剂，具有催化剂用量低(仅为0.05～1wt％)，收率高(在85～95％)，产品纯度高，颜色白，裂解温度低，可重复使用的特点。1, the present invention relates to stannous benzoate as the catalyzer of lactic acid oligomerization and cracking, has catalyst consumption low (only 0.05～1wt%), yield height (at 85～95%), product purity height, color white, cracking Low temperature, reusable features.
2、本发明涉及苯甲酸亚锡作为丙交酯开环聚合的催化剂，具有聚合反应速度温和，产物分子量高，适合于溶液聚合和本体聚合的特点。2. The present invention relates to stannous benzoate as a catalyst for lactide ring-opening polymerization, which has the characteristics of mild polymerization reaction speed, high product molecular weight, and is suitable for solution polymerization and bulk polymerization.
3、本发明涉及苯甲酸亚锡作为羟基乙酸脱水低聚和高温裂解的催化剂，具有催化剂用量低，反应活性高，乙交酯收率高，产品纯度高，颜色白，裂解温度低，可重复使用的特点。3. The present invention relates to stannous benzoate as a catalyst for dehydration oligomerization and pyrolysis of glycolic acid, which has the advantages of low catalyst consumption, high reactivity, high yield of glycolide, high product purity, white color, low cracking temperature, and repeatability Features used.
4、本发明涉及的苯甲酸亚锡作为乙交酯开环聚合反应的催化剂，具有聚合反应速度温和，产物熔融指数高，适用于溶液聚合或本体聚合的特点。4. The stannous benzoate involved in the present invention is used as a catalyst for the ring-opening polymerization of glycolide, which has a mild polymerization reaction rate and a high melt index of the product, and is suitable for solution polymerization or bulk polymerization.
5、本发明涉及的苯甲酸亚锡作为乙交酯、丙交酯、ε-已内酯之间两者或三者之间的共聚合的催化剂，具有聚合反应活性高，聚合物的分子量高，适用于本体聚合或溶液聚合的特点。5. The stannous benzoate involved in the present invention is used as a catalyst for the copolymerization between glycolide, lactide, and ε-caprolactone, or among the three, and has high polymerization activity and high molecular weight of the polymer. , suitable for bulk polymerization or solution polymerization characteristics.
具体实施方式Detailed ways
下面通过具体实施例，对本发明的技术方案作进一步具体的说明；但本发明并不局限于这些实施例。The technical solutions of the present invention will be further specifically described below through specific examples; but the present invention is not limited to these examples.
实施例1Example 1
称取10Kg的L-乳酸水溶液(浓度为88wt％)放入10升三口烧瓶中，加入30g苯甲酸亚锡催化剂(0.3wt％)，减压，升温脱水，脱水温度控制在120～180℃，后期减压脱水，形成低聚物，在8小时反应完成。切换接受装置，在180～240℃减压裂解收集L-丙交酯，6h完成，得到粗L-丙交酯6.5Kg，产物收率92％，产物熔点为94℃。Take by weighing 10Kg of L-lactic acid aqueous solution (concentration is 88wt%) and put into 10 liters of there-necked flasks, add 30g stannous benzoate catalyst (0.3wt%), reduce pressure, heat up and dehydrate, dehydration temperature is controlled at 120～180 ℃, Dehydration under reduced pressure in the later stage forms oligomers, and the reaction is completed in 8 hours. Switch the receiving device, collect L-lactide by cracking under reduced pressure at 180-240°C, and complete in 6 hours to obtain 6.5Kg of crude L-lactide with a product yield of 92% and a melting point of 94°C.
实施例2Example 2
称取10Kg的L-乳酸水溶液(浓度为88wt％)放入10升三口烧瓶中，加入5g苯甲酸亚锡催化剂(0.05wt％)，减压，升温脱水，脱水温度控制在120～180℃，后期减压脱水，形成低聚物，在10小时反应完成。切换接受装置，在180～240℃减压裂解收集L-丙交酯，8h完成，得到粗L-丙交酯6.2Kg，产物收率88％，产物熔点为93℃。Take by weighing 10Kg of L-lactic acid aqueous solution (concentration is 88wt%) and put into 10 liters of three-necked flasks, add 5g stannous benzoate catalyst (0.05wt%), depressurize, heat up and dehydrate, dehydration temperature is controlled at 120～180 ℃, Dehydration under reduced pressure in the later stage forms oligomers, and the reaction is completed in 10 hours. Switch the receiving device, and collect L-lactide by cracking under reduced pressure at 180-240°C. After 8 hours, 6.2Kg of crude L-lactide is obtained, the product yield is 88%, and the melting point of the product is 93°C.
实施例3Example 3
称取10Kg的L-乳酸水溶液(浓度为88wt％)放入10升三口烧瓶中，加入100g苯甲酸亚锡催化剂(1wt％)，减压，升温脱水，脱水温度控制在120～180℃，后期减压脱水，形成低聚物，在7小时反应完成。切换接受装置，在180～240℃减压裂解收集L-丙交酯，5h完成，得到粗L-丙交酯6.6Kg，产物收率94％，产物熔点为94℃。Weigh 10Kg of L-lactic acid aqueous solution (concentration is 88wt%) and put it into a 10-liter three-necked flask, add 100g of stannous benzoate catalyst (1wt%), decompress, heat up and dehydrate, and the dehydration temperature is controlled at 120～180°C. Dehydration under reduced pressure resulted in the formation of oligomers, and the reaction was complete in 7 hours. Switch the receiving device, and collect L-lactide by cracking under reduced pressure at 180-240°C. After 5 hours, 6.6Kg of crude L-lactide is obtained, the product yield is 94%, and the melting point of the product is 94°C.
实施例4Example 4
称取1Kg的D-乳酸水溶液(浓度为88wt％)放入3升三口烧瓶中，加入3g苯甲酸亚锡催化剂(0.3wt％)，减压，升温脱水，脱水温度控制在120～180℃，后期减压脱水，形成低聚物，在8小时反应完成。切换接受装置，在180～240℃减压裂解收集L-丙交酯，6h完成，得到粗D-丙交酯0.64Kg，产物收率91％，产物熔点为94℃。Weigh 1Kg of D-lactic acid aqueous solution (concentration is 88wt%) and put it into a 3-liter three-necked flask, add 3g of stannous benzoate catalyst (0.3wt%), decompress, heat up and dehydrate, and the dehydration temperature is controlled at 120～180°C. Dehydration under reduced pressure in the later stage forms oligomers, and the reaction is completed in 8 hours. Switch the receiving device, and collect L-lactide by cracking under reduced pressure at 180-240°C. After 6 hours, 0.64Kg of crude D-lactide is obtained, the product yield is 91%, and the melting point of the product is 94°C.
实施例5Example 5
操作步骤同实施例1相同，其中将D，L—乳酸替换为L-乳酸。得到粗D，L—丙交酯6.1Kg，产物收率为87％，产物熔点为52℃。The operating steps are the same as in Example 1, wherein D, L-lactic acid is replaced by L-lactic acid. 6.1Kg of crude D,L-lactide was obtained, the product yield was 87%, and the melting point of the product was 52°C.
实施例6Example 6
将上述实施例中得到的丙交酯经过减压蒸馏或醋酸乙酯溶剂重结晶提纯得到聚合级丙交酯，其中聚合级D-丙交酯、聚合级L-丙交酯熔点为97～98℃，聚合级内消旋D，L—丙交酯熔点为52℃，聚合级外消旋D，L—丙交酯熔点为126～128℃。The lactide obtained in the above examples is purified by vacuum distillation or ethyl acetate solvent recrystallization to obtain polymer grade lactide, wherein the melting points of polymer grade D-lactide and polymer grade L-lactide are 97-98 °C, the melting point of polymer grade meso D, L-lactide is 52 °C, and the melting point of polymer grade racemic D, L-lactide is 126-128 °C.
在无水无氧的条件下，取聚合级L-丙交酯6.0Kg，加热到110℃融化后，加入到真空干燥过的10升反应釜内，然后，加入苯甲酸亚锡3g(0.05wt％)，开始阶段，反应釜温度控制在110～125℃搅拌进行聚合反应，大约4～6小时，体系黏度增大，停止搅拌，反应过程中不断放热，控制釜内温度。升高反应温度至130℃，继续反应48小时，然后开始升高反应温度至釜内温度为190℃，用氮气加压2.5Mpa，开始出料，通过拉条、水冷、切粒、收集粒料。得到的聚L-丙交酯的黏均分子量为7.7万，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融的指数是6.2g/10min。Under anhydrous and oxygen-free conditions, take 6.0Kg of polymer grade L-lactide, heat it to 110°C to melt, add it to a vacuum-dried 10-liter reactor, and then add 3g of stannous benzoate (0.05wt %), in the initial stage, the temperature of the reactor is controlled at 110-125°C and the polymerization reaction is carried out with stirring. After about 4-6 hours, the viscosity of the system increases, and the stirring is stopped. During the reaction process, heat is continuously released, and the temperature in the kettle is controlled. Raise the reaction temperature to 130°C, continue to react for 48 hours, then start to raise the reaction temperature to 190°C in the kettle, pressurize with nitrogen to 2.5Mpa, start discharging, and collect the pellets through stranding, water cooling, cutting and pelletizing . The obtained poly-L-lactide has a viscosity-average molecular weight of 77,000. At 190° C., a capillary diameter of 1.095 mm, and a pressure of 2.16 kg, the melting index of the product is 6.2 g/10 min.
实施例7Example 7
在无水无氧的条件下，取聚合级L-丙交酯6.0Kg，加热到110℃融化后，加入到真空干燥过的10升反应釜内，然后，加入苯甲酸亚锡0.6g(0.01wt％)，开始阶段，反应釜温度控制在110～125℃搅拌进行聚合反应，大约6～8小时，体系黏度增大，停止搅拌，反应过程中不断放热，控制釜内温度。升高反应温度至130℃，继续反应72小时，然后升高反应温度至釜内温度为190℃，用氮气加压2.5Mpa，开始出料，通过拉条、水冷、切粒、收集粒料。得到的聚L-丙交酯的黏均分子量为15.6万，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融的指数是3.6g/10min。Under anhydrous and oxygen-free conditions, take 6.0Kg of polymer grade L-lactide, heat it to 110°C to melt, add it to a vacuum-dried 10-liter reactor, and then add 0.6g of stannous benzoate (0.01 wt%), in the initial stage, the temperature of the reactor was controlled at 110-125°C and the polymerization reaction was carried out with stirring. After about 6-8 hours, the viscosity of the system increased, and the stirring was stopped. During the reaction process, heat was continuously released, and the temperature in the kettle was controlled. Raise the reaction temperature to 130°C, continue the reaction for 72 hours, then raise the reaction temperature to 190°C in the kettle, pressurize with nitrogen to 2.5Mpa, start discharging, and collect the pellets through stranding, water cooling, pelletizing. The obtained poly-L-lactide has a viscosity-average molecular weight of 156,000. At 190° C., a capillary diameter of 1.095 mm, and a pressure of 2.16 kg, the melting index of the product is 3.6 g/10 min.
实施例8Example 8
在无水无氧的条件下，取聚合级L-丙交酯6.0Kg，加热到110℃融化后，加入到真空干燥过的10升反应釜内，然后，加入苯甲酸亚锡6g(0.1wt％)，开始阶段，反应釜温度控制在110～125℃搅拌进行聚合反应，大约2～4小时，体系黏度增大，停止搅拌，反应过程中不断放热，控制釜内温度。升高反应温度至130℃，继续反应24小时，然后升高反应温度至釜内温度为180℃，用氮气加压2.5Mpa，开始出料，通过拉条、水冷、切粒、收集粒料。得到的聚L-丙交酯的黏均分子量为4.3万，在180℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融的指数是16.2g/10min。Under anhydrous and oxygen-free conditions, take 6.0Kg of polymer grade L-lactide, heat it to 110°C to melt, add it to a vacuum-dried 10-liter reactor, and then add 6g of stannous benzoate (0.1wt %), in the initial stage, the temperature of the reactor is controlled at 110-125°C and the polymerization reaction is carried out with stirring. After about 2-4 hours, the viscosity of the system increases, and the stirring is stopped. During the reaction process, heat is continuously released, and the temperature in the kettle is controlled. Raise the reaction temperature to 130°C, continue the reaction for 24 hours, then raise the reaction temperature to 180°C in the kettle, pressurize with nitrogen to 2.5Mpa, start discharging, and collect the pellets through stranding, water cooling, cutting and pelletizing. The obtained poly-L-lactide has a viscosity-average molecular weight of 43,000. At 180° C., a capillary diameter of 1.095 mm, and a pressure of 2.16 kg, the melting index of the product is 16.2 g/10 min.
实施例9Example 9
操作步骤同实施例7相同，用聚合级内消旋D，L-丙交酯替代聚合级L-丙交酯，得到的聚D，L-丙交酯的GPC数均分子量为7.4万，分子量分布为3.24，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融的指数是8.2g/10min。The operation steps are the same as in Example 7, and the polymer grade meso D, L-lactide is used to replace the polymer grade L-lactide. The GPC number average molecular weight of the obtained poly D, L-lactide is 74,000, and the molecular weight The distribution is 3.24, at 190°C, the capillary diameter is 1.095mm, and the melting index of the product is 8.2g/10min under a pressure of 2.16kg.
实施例10Example 10
在无水无氧的条件下，取苯甲酸亚锡0.03g(0.05wt％)，聚合级D-丙交酯60g，加入到150ml的玻璃反应瓶中，然后，开始阶段，用油浴控制反应温度在120～125℃，磁力搅拌进行聚合反应，大约6～8小时，体系黏度增大，停止搅拌，升高反应温度至130℃，继续反应72小时，聚合产物，加入氯仿溶解，用乙醇析出，经干燥得到聚D-丙交酯，其黏均分子量为14.8万，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融的指数是4.9g/10min。Under anhydrous and oxygen-free conditions, take 0.03g (0.05wt%) of stannous benzoate and 60g of polymer grade D-lactide, and add them to a 150ml glass reaction bottle, then, at the beginning stage, use an oil bath to control the reaction The temperature is 120-125°C, and magnetic stirring is carried out to carry out the polymerization reaction. After about 6-8 hours, the viscosity of the system increases, stop stirring, raise the reaction temperature to 130°C, and continue the reaction for 72 hours. The polymerization product is dissolved by adding chloroform and precipitated with ethanol. After drying, poly D-lactide was obtained. Its viscosity-average molecular weight was 148,000. At 190°C, the capillary diameter was 1.095mm, and the melting index of the product was 4.9g/10min under a pressure of 2.16kg.
实施例11Example 11
在无水无氧的条件下，取苯甲酸亚锡0.03g(0.05wt％)，聚合级D，L-丙交酯60g，加入到150ml的玻璃反应瓶中，然后，开始阶段，用油浴控制反应温度在130～150℃，磁力搅拌进行聚合反应，大约4～6小时，体系黏度增大，停止搅拌，升高反应温度至140℃，继续反应48小时，聚合产物，加入氯仿溶解，用乙醇析出，经干燥得到聚D，L-丙交酯，GPC数均分子量为8.3万，分子量分布为2.85，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融的指数是6.9g/10min。Under anhydrous and oxygen-free conditions, take 0.03g (0.05wt%) of stannous benzoate, polymer grade D, and 60g of L-lactide, and add them to a 150ml glass reaction bottle. Then, at the beginning stage, use an oil bath Control the reaction temperature at 130-150°C, and carry out the polymerization reaction with magnetic stirring. After about 4-6 hours, the viscosity of the system increases, stop stirring, raise the reaction temperature to 140°C, and continue the reaction for 48 hours. Add chloroform to dissolve the polymerization product, and use Ethanol was precipitated and dried to obtain poly-D, L-lactide. The GPC number-average molecular weight was 83,000, and the molecular weight distribution was 2.85. At 190°C, the capillary diameter was 1.095 mm, and the melting index of the product was 2.16 kg. 6.9g/10min.
实施例12Example 12
在无水无氧的条件下，取聚合级D-丙交酯20g和聚合级L-丙交酯80g，苯甲酸亚锡0.05g(0.05wt％)，加入到250ml的玻璃反应瓶中，然后，开始阶段，用油浴控制反应温度在120～125℃，磁力搅拌进行聚合反应，大约4～6小时，体系黏度增大，停止搅拌，升高反应温度至130℃，继续反应48小时，聚合产物，加入氯仿溶解，用乙醇析出，经干燥得到聚D，L-丙交酯，GPC数均分子量为7.6万，分子量分布为2.92，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融的指数是8.7g/10min。Under anhydrous and oxygen-free conditions, get polymer grade D-lactide 20g and polymer grade L-lactide 80g, stannous benzoate 0.05g (0.05wt%), join in the glass reaction bottle of 250ml, then , In the initial stage, use an oil bath to control the reaction temperature at 120-125°C, and carry out the polymerization reaction with magnetic stirring. After about 4-6 hours, the viscosity of the system increases, stop stirring, raise the reaction temperature to 130°C, continue the reaction for 48 hours, and polymerize The product was dissolved in chloroform, precipitated with ethanol, and dried to obtain poly-D, L-lactide. The GPC number-average molecular weight was 76,000, and the molecular weight distribution was 2.92. At 190°C, the capillary diameter was 1.095 mm, and the pressure was 2.16 kg. , the melting index of the product was 8.7 g/10 min.
实施例13Example 13
在无水无氧的条件下，取聚合级L-丙交酯2.0Kg，加热到110℃融化后，加入到真空干燥过的10升反应釜内，然后，加入含有苯甲酸亚锡1g(0.05wt％)的二甲苯溶剂5升，开始阶段，反应釜温度控制在120～125℃搅拌进行聚合反应，6小时后，体系黏度增大，反应过程中不断放热，然后，升高反应温度至130℃，继续反应72小时，聚合物的溶液收集到搪瓷桶内，用乙醇沉淀，经干燥得到的聚L-丙交酯的黏均分子量为15.5万，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融的指数是4.2g/10min。Under anhydrous and oxygen-free conditions, take 2.0Kg of polymer grade L-lactide, heat it to 110°C to melt, add it to a vacuum-dried 10-liter reactor, and then add 1g of stannous benzoate (0.05 wt%) xylene solvent 5 liters, in the initial stage, the reaction kettle temperature was controlled at 120～125 ℃ and carried out the polymerization reaction with stirring, after 6 hours, the viscosity of the system increased, exothermic constantly in the reaction process, then, raise the reaction temperature to 130°C, continue to react for 72 hours, the polymer solution is collected in an enamel barrel, precipitated with ethanol, and the viscosity-average molecular weight of the poly-L-lactide obtained after drying is 155,000. At 190°C, the capillary diameter is 1.095mm. The melting index of the product was 4.2 g/10 min under a pressure of 2.16 kg.
实施例14Example 14
将70wt％羟基乙酸水溶液6Kg放入到10升三口烧瓶中，再加入苯甲酸亚锡12g(0.2wt％)，用2h逐渐升高脱水温度至100℃，后期逐渐降低反应体系的压力。继续用2h升温至140℃。随着溶剂水的除去，羟基乙酸分子间脱水缩合开始，最后再用4h，体系温度升至180℃，低聚羟基乙酸的分子量为1500～8000。然后200～270℃裂解收集乙交酯，5h完成，粗产品为2.32Kg，收率72％，粗产物熔点为92℃。用乙酸乙酯两次重结晶，重结晶后产物为1.72Kg，产率为占粗产品74％，最终收率为54％，产物熔点为92～93℃。Put 6Kg of 70wt% glycolic acid aqueous solution into a 10-liter three-necked flask, then add 12g (0.2wt%) of stannous benzoate, and gradually increase the dehydration temperature to 100° C. in 2 hours, and gradually reduce the pressure of the reaction system in the later stage. Continue to heat up to 140°C with 2h. With the removal of solvent water, the dehydration condensation between glycolic acid molecules begins, and finally after another 4 hours, the temperature of the system rises to 180°C, and the molecular weight of oligomeric glycolic acid is 1500-8000. Then, the glycolide was cracked and collected at 200-270°C, and completed in 5 hours. The crude product was 2.32Kg, the yield was 72%, and the melting point of the crude product was 92°C. Recrystallize twice with ethyl acetate, the product after recrystallization is 1.72Kg, the yield is 74% of the crude product, the final yield is 54%, and the melting point of the product is 92-93°C.
实施例15Example 15
将70wt％羟基乙酸水溶液6Kg放入到10升三口烧瓶中，再加入苯甲酸亚锡3g(0.05wt％)，用2h逐渐升高脱水温度至100℃，后期逐渐降低反应体系的压力。继续用2h升温至140℃。随着溶剂水的除去，羟基乙酸分子间脱水缩合开始，最后再用6h，体系温度升至180℃，低聚羟基乙酸的分子量为1500～8000。然后200～270℃裂解收集乙交酯，6h完成，粗产品为2.23Kg，收率70％，粗产物熔点为91℃。Put 6Kg of 70wt% glycolic acid aqueous solution into a 10-liter three-necked flask, then add 3g (0.05wt%) of stannous benzoate, and gradually increase the dehydration temperature to 100° C. in 2 hours, and gradually reduce the pressure of the reaction system in the later stage. Continue to heat up to 140°C with 2h. With the removal of the solvent water, the dehydration condensation between glycolic acid molecules begins, and finally after another 6 hours, the temperature of the system rises to 180°C, and the molecular weight of the oligomeric glycolic acid is 1500-8000. Then, the glycolide was cracked and collected at 200-270°C, and completed in 6 hours. The crude product was 2.23Kg, the yield was 70%, and the melting point of the crude product was 91°C.
实施例16Example 16
将70wt％羟基乙酸水溶液6Kg放入到10升三口烧瓶中，再加入苯甲酸亚锡60g(1wt％)，用2h逐渐升高脱水温度至100℃，后期逐渐降低反应体系的压力，继续用2h升温至140℃。随着溶剂水的除去，羟基乙酸分子间脱水缩合开始，最后再用3h，体系温度升至180℃，低聚羟基乙酸的分子量为1500～8000。然后200～270℃裂解收集乙交酯，4h完成，粗产品为2.28Kg，收率71％，粗产物熔点为90℃。Put 6Kg of 70wt% glycolic acid aqueous solution into a 10-liter three-necked flask, then add 60g (1wt%) of stannous benzoate, gradually increase the dehydration temperature to 100°C in 2 hours, gradually reduce the pressure of the reaction system in the later stage, and continue to use 2 hours The temperature was raised to 140°C. With the removal of the solvent water, the dehydration condensation between the glycolic acid molecules begins, and finally after another 3 hours, the temperature of the system rises to 180°C, and the molecular weight of the oligomeric glycolic acid is 1500-8000. Then, the glycolide was cracked and collected at 200-270°C, and completed in 4 hours. The crude product was 2.28Kg, the yield was 71%, and the melting point of the crude product was 90°C.
实施例17Example 17
将上述实施例中得到的乙交酯经过醋酸乙酯溶剂重结晶提纯得到聚合级乙交酯，熔点为92～93℃。The glycolide obtained in the above examples was purified by recrystallization from an ethyl acetate solvent to obtain polymer grade glycolide with a melting point of 92-93°C.
在无水无氧的条件下，取聚合级乙交酯100g，苯甲酸亚锡0.05g(0.05wt％)，加入到真空干燥过的200ml反应瓶内，然后，开始反应温度控制在110～125℃搅拌进行本体聚合反应，大约2～4小时，体系黏度增大，停止搅拌，反应过程中不断放热，升高反应温度至130℃，继续反应48小时，由于聚乙交酯不能溶于一般溶剂中，将反应玻璃瓶用液氮冷却，开水炸瓶，取出乙交酯聚合物，采用液氮冷冻粉碎方法，制备颗粒母料，熔点在220～225℃，在230℃下熔融指数是9.2g/10min。Under anhydrous and oxygen-free conditions, take 100g of polymer grade glycolide and 0.05g (0.05wt%) of stannous benzoate, and add them to a vacuum-dried 200ml reaction bottle. Then, the reaction temperature is controlled at 110-125 Stir at ℃ to carry out bulk polymerization reaction, about 2 to 4 hours, the viscosity of the system increases, stop stirring, heat is released continuously during the reaction process, raise the reaction temperature to 130 ℃, continue to react for 48 hours, because polyglycolide is not soluble in general In the solvent, cool the reaction glass bottle with liquid nitrogen, fry the bottle with boiling water, take out the glycolide polymer, and use liquid nitrogen to freeze and pulverize the method to prepare the granule masterbatch. The melting point is 220-225 ° C, and the melting index at 230 ° C is 9.2 g/10min.
实施例18Example 18
在无水无氧的条件下，取聚合级乙交酯100g，苯甲酸亚锡0.01g(0.01wt％)，加入到真空干燥过的200ml反应瓶内，然后，开始反应温度控制在110～125℃搅拌进行本体聚合反应，大约4～6小时，体系黏度增大，停止搅拌，反应过程中不断放热，升高反应温度至130℃，继续反应72小时，由于聚乙交酯不能溶于一般溶剂中，将反应玻璃瓶用液氮冷却，开水炸瓶，取出乙交酯聚合物，采用液氮冷冻粉碎方法，制备颗粒母料，熔点在222～225℃，在230℃下熔融指数是5.1g/10min。Under the condition of anhydrous and oxygen-free, take polymer grade glycolide 100g, stannous benzoate 0.01g (0.01wt%), join in the vacuum-dried 200ml reaction bottle, then, start reaction temperature to be controlled at 110～125 Stir at ℃ to carry out bulk polymerization reaction, about 4 to 6 hours, the viscosity of the system increases, stop stirring, heat is released continuously during the reaction process, raise the reaction temperature to 130 ℃, continue to react for 72 hours, because polyglycolide is not soluble in general In the solvent, cool the reaction glass bottle with liquid nitrogen, fry the bottle with boiling water, take out the glycolide polymer, and use the method of liquid nitrogen freezing and crushing to prepare the master batch of particles. The melting point is 222-225 ° C, and the melting index at 230 ° C is 5.1 g/10min.
实施例19Example 19
在无水无氧的条件下，取聚合级乙交酯100g颗粒，苯甲酸亚锡0.1g(0.1wt％)，加入到真空干燥过的200ml反应瓶内，然后，开始反应温度控制在110～125℃搅拌进行本体聚合反应，大约2～4小时，体系黏度增大，停止搅拌，反应过程中不断放热，升高反应温度至130℃，继续反应48小时，由于聚乙交酯不能溶于一般溶剂中，将反应玻璃瓶用液氮冷却，开水炸瓶，取出乙交酯聚合物，采用液氮冷冻粉碎方法，制备颗粒母料，熔点在220～224℃，在230℃下熔融指数是14.6g/10min。Under anhydrous and oxygen-free conditions, get polymer grade glycolide 100g particles, stannous benzoate 0.1g (0.1wt%), join in the vacuum-dried 200ml reaction bottle, then, start reaction temperature to be controlled at 110～ Stir at 125°C for bulk polymerization, about 2 to 4 hours, the viscosity of the system increases, stop stirring, exotherm continues during the reaction, raise the reaction temperature to 130°C, continue to react for 48 hours, because polyglycolide cannot be dissolved in In a general solvent, cool the reaction glass bottle with liquid nitrogen, fry the bottle with boiling water, take out the glycolide polymer, and use liquid nitrogen to freeze and pulverize the method to prepare the granule masterbatch. The melting point is 220-224 ° C, and the melting index at 230 ° C is 14.6g/10min.
实施例20Example 20
在无水无氧的条件下，取精制过的ε-己内酯100g，苯甲酸亚锡0.025g(0.025wt％)，加入到真空干燥过的200ml反应瓶内，然后，开始反应温度控制在110～125℃搅拌进行本体聚合反应，大约4～6小时，体系黏度增大，停止搅拌，反应过程中不断放热，升高反应温度至130℃，继续反应72小时，聚合物(PCL)经氯仿溶解，再用乙醇沉淀，干燥后，聚合物的产率为96％，测定黏均分子量为8万，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是3.7g/10min。Under anhydrous and oxygen-free conditions, get refined ε-caprolactone 100g, stannous benzoate 0.025g (0.025wt%), join in the vacuum-dried 200ml reaction bottle, then, start reaction temperature to be controlled at Stir at 110-125°C to carry out bulk polymerization reaction, about 4-6 hours, the viscosity of the system increases, stop stirring, heat is released during the reaction process, raise the reaction temperature to 130°C, continue to react for 72 hours, the polymer (PCL) through Dissolved in chloroform, then precipitated with ethanol, and after drying, the yield of the polymer was 96%, and the measured viscosity-average molecular weight was 80,000. At 190°C, the capillary diameter was 1.095 mm, and the melt index of the product was 3.7 under a pressure of 2.16 kg. g/10min.
实施例21Example 21
在无水无氧的条件下，取聚合级乙交酯20g，L-丙交酯80g，苯甲酸亚锡0.03g(0.03wt％)，加入到真空干燥过的200ml反应瓶内，然后，开始反应温度控制在110～125℃搅拌进行本体聚合反应，大约2～4小时，体系黏度增大，停止搅拌，反应过程中不断放热，升高反应温度至130℃，继续反应72小时，将反应玻璃瓶用液氮冷却，开水炸瓶，取出乙交酯—丙交酯共聚物，采用液氮冷冻粉碎方法，制备颗粒母料。聚合物经氯仿溶解，再用乙醇沉淀，干燥后，聚合物的产率为95％，特性粘度为2.68，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是7.7g/10min。Under anhydrous and oxygen-free conditions, take 20 g of polymer grade glycolide, 80 g of L-lactide, and 0.03 g (0.03 wt%) of stannous benzoate, and add them to a vacuum-dried 200 ml reaction bottle, and then start Control the reaction temperature at 110-125°C and stir to carry out the bulk polymerization reaction. After about 2-4 hours, the viscosity of the system increases. Stop stirring. During the reaction process, heat is released continuously. Raise the reaction temperature to 130°C and continue the reaction for 72 hours. Cool the glass bottle with liquid nitrogen, fry the bottle with boiling water, take out the glycolide-lactide copolymer, and use the method of liquid nitrogen freezing and pulverization to prepare the granule masterbatch. The polymer was dissolved in chloroform, and then precipitated with ethanol. After drying, the yield of the polymer was 95%, and the intrinsic viscosity was 2.68. At 190° C., the capillary diameter was 1.095 mm, and the melt index of the product was 7.7 under a pressure of 2.16 kg. g/10min.
实施例22Example 22
操作步骤同实施例21，用D-丙交酯替代L-丙交酯，聚合物经氯仿溶解，再用乙醇沉淀，干燥后，聚合物的产率为96％，特性粘度为2.82，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是7.3g/10min。The operation steps are the same as in Example 21, and D-lactide is used instead of L-lactide. The polymer is dissolved in chloroform, and then precipitated with ethanol. After drying, the yield of the polymer is 96%, and the intrinsic viscosity is 2.82. At ℃, the capillary diameter is 1.095mm, and the melt index of the product is 7.3g/10min under the pressure of 2.16kg.
实施例23Example 23
操作步骤同实施例21，用内消旋D，L-丙交酯替代L-丙交酯，聚合物经氯仿溶解，再用乙醇沉淀，干燥后，聚合物的产率为94％，特性粘度为2.23，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是8.3g/10min。The operation steps are the same as in Example 21, with meso D, L-lactide instead of L-lactide, the polymer is dissolved in chloroform, and then precipitated with ethanol. After drying, the yield of the polymer is 94%, and the intrinsic viscosity is 94%. It is 2.23, and at 190°C, the capillary diameter is 1.095mm, and the melt index of the product is 8.3g/10min under the pressure of 2.16kg.
实施例24Example 24
操作步骤同实施例21，用外消旋D，L-丙交酯替代L-丙交酯，聚合物经氯仿溶解，再用乙醇沉淀，干燥后，聚合物的产率为95％，特性粘度为3.42，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是5.3g/10min。The operation steps are the same as in Example 21, with racemic D, L-lactide instead of L-lactide, the polymer is dissolved in chloroform, and then precipitated with ethanol. After drying, the yield of the polymer is 95%, and the intrinsic viscosity It is 3.42, and at 190°C, the capillary diameter is 1.095mm, and the melt index of the product is 5.3g/10min under the pressure of 2.16kg.
实施例25Example 25
在无水无氧的条件下，取聚合级乙交酯20g，ε-己内酯80g，苯甲酸亚锡0.03g(0.03wt％)，加入到真空干燥过的200ml反应瓶内，然后，开始反应温度控制在110～125℃搅拌进行本体聚合反应，大约4～6小时，体系黏度增大，停止搅拌，反应过程中不断放热，升高反应温度至130℃，继续反应72小时，聚合物经氯仿溶解，再用乙醇沉淀，干燥后，聚合物的产率为97％，测定特性粘度为3.73，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是4.9g/10min。Under anhydrous and oxygen-free conditions, get 20g of polymer grade glycolide, 80g of ε-caprolactone, 0.03g (0.03wt%) of stannous benzoate, and add them to a vacuum-dried 200ml reaction bottle, then start The reaction temperature is controlled at 110-125°C and stirred for bulk polymerization. After about 4-6 hours, the viscosity of the system increases. Stop stirring. Heat is released during the reaction process. Raise the reaction temperature to 130°C and continue to react for 72 hours. Dissolved in chloroform, then precipitated with ethanol, and after drying, the yield of the polymer was 97%, and the measured intrinsic viscosity was 3.73. At 190°C, the capillary diameter was 1.095 mm, and the melt index of the product was 4.9 g under a pressure of 2.16 kg. /10min.
实施例26Example 26
在无水无氧的条件下，取聚合级L-丙交酯50g，ε-己内酯50g，苯甲酸亚锡0.03g(0.03wt％)，加入到真空干燥过的200ml反应瓶内，然后，开始反应温度控制在110～125℃搅拌进行本体聚合反应，大约4～6小时，体系黏度增大，停止搅拌，反应过程中不断放热，升高反应温度至130℃，继续反应72小时，聚合物经氯仿溶解，再用乙醇沉淀，干燥后，聚合物的产率为96％，测定特性粘度为3.86，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是4.6g/10min。Under anhydrous and oxygen-free conditions, get polymer grade L-lactide 50g, ε-caprolactone 50g, stannous benzoate 0.03g (0.03wt%), join in the vacuum-dried 200ml reaction bottle, then , start the reaction temperature at 110-125°C and stir to carry out the bulk polymerization reaction, about 4-6 hours, the viscosity of the system increases, stop stirring, heat is released during the reaction process, raise the reaction temperature to 130°C, continue the reaction for 72 hours, The polymer is dissolved in chloroform, and then precipitated with ethanol. After drying, the productive rate of the polymer is 96%, and the measured intrinsic viscosity is 3.86. At 190°C, the capillary diameter is 1.095mm, and the melt index of the product is 4.6g/10min.
实施例27Example 27
在无水无氧的条件下，取聚合级乙交酯20g，聚合级L-丙交酯30g，ε-己内酯50g，苯甲酸亚锡0.03g(0.03wt％)，加入到真空干燥过的200ml反应瓶内，然后，开始反应温度控制在110～125℃搅拌进行本体聚合反应，大约4～6小时，体系黏度增大，停止搅拌，反应过程中不断放热，升高反应温度至130℃，继续反应72小时，聚合物经氯仿溶解，再用乙醇沉淀，干燥后，聚合物的产率为96％，测定特性粘度为2.36，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是7.7g/10min。Under anhydrous and oxygen-free conditions, take 20g of polymer grade glycolide, 30g of polymer grade L-lactide, 50g of ε-caprolactone, 0.03g (0.03wt%) of stannous benzoate, and add them to the vacuum-dried Then, control the reaction temperature at 110-125°C and stir for bulk polymerization. After about 4-6 hours, the viscosity of the system increases. Stop stirring. During the reaction, heat is released continuously. Raise the reaction temperature to 130°C ℃, continue the reaction for 72 hours, the polymer is dissolved in chloroform, and then precipitated with ethanol. After drying, the yield of the polymer is 96%, and the measured intrinsic viscosity is 2.36. At 190 ℃, the capillary diameter is 1.095mm, and the pressure of 2.16kg The melt index of the product was 7.7 g/10 min.
实施例28Example 28
在无水无氧的条件下，取聚合级乙交酯5g，聚合级L-丙交酯45g，苯甲酸亚锡0.015g(0.03wt％)，二甲苯溶剂50ml，加入到真空干燥过的200ml反应瓶内，进行溶液聚合。开始反应温度控制在120～125℃搅拌进行聚合反应，大约4～6小时，体系黏度增大，停止搅拌，升高反应温度至130℃，继续反应72小时，加入甲苯溶剂溶解取出聚合物溶液，再用乙醇沉淀，干燥后，聚合物的产率为94％，测定特性粘度为2.38，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是8.2g/10min。Under anhydrous and oxygen-free conditions, take polymer grade glycolide 5g, polymer grade L-lactide 45g, stannous benzoate 0.015g (0.03wt%), xylene solvent 50ml, add to vacuum-dried 200ml In the reaction bottle, solution polymerization is carried out. Start the reaction temperature at 120-125°C and stir to carry out the polymerization reaction. After about 4-6 hours, the viscosity of the system increases, stop stirring, raise the reaction temperature to 130°C, continue the reaction for 72 hours, add toluene solvent to dissolve and take out the polymer solution. Precipitate with ethanol again, after drying, the productive rate of polymer is 94%, and measuring intrinsic viscosity is 2.38, and at 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the melting index of product is 8.2g/10min.
实施例29Example 29
在无水无氧的条件下，取聚合级乙交酯5g，ε-己内酯45g，苯甲酸亚锡0.015g(0.03wt％)，二甲苯溶剂50ml，加入到真空干燥过的200ml反应瓶内，进行溶液聚合。开始反应温度控制在120～125℃搅拌进行聚合反应，大约4～6小时，体系黏度增大，停止搅拌，升高反应温度至130℃，继续反应72小时，加入甲苯溶剂溶解取出聚合物溶液，再用乙醇沉淀，干燥后，聚合物的产率为96％，测定特性粘度为3.45，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是5.3g/10min。Under anhydrous and oxygen-free conditions, take 5g of polymer grade glycolide, 45g of ε-caprolactone, 0.015g (0.03wt%) of stannous benzoate, and 50ml of xylene solvent, and add them to a vacuum-dried 200ml reaction bottle Inside, solution polymerization is carried out. Start the reaction temperature at 120-125°C and stir to carry out the polymerization reaction. After about 4-6 hours, the viscosity of the system increases, stop stirring, raise the reaction temperature to 130°C, continue the reaction for 72 hours, add toluene solvent to dissolve and take out the polymer solution. Precipitate with ethanol again, after drying, the productive rate of polymer is 96%, and measuring intrinsic viscosity is 3.45, and at 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the melting index of product is 5.3g/10min.
实施例30Example 30
在无水无氧的条件下，取聚合级L-丙交酯25g，ε-己内酯25g，苯甲酸亚锡0.015g(0.03wt％)，二甲苯溶剂50ml，加入到真空干燥过的200ml反应瓶内，进行溶液聚合。开始反应温度控制在120～125℃搅拌进行聚合反应，大约4～6小时，体系黏度增大，停止搅拌，升高反应温度至130℃，继续反应72小时，加入甲苯溶剂溶解取出聚合物溶液，再用乙醇沉淀，干燥后，聚合物的产率为96％，测定特性粘度为2.26，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是8.3g/10min。Under anhydrous and oxygen-free conditions, take 25g of polymer grade L-lactide, 25g of ε-caprolactone, 0.015g of stannous benzoate (0.03wt%), and 50ml of xylene solvent, and add them to 200ml of vacuum-dried In the reaction bottle, solution polymerization is carried out. Start the reaction temperature at 120-125°C and stir to carry out the polymerization reaction. After about 4-6 hours, the viscosity of the system increases, stop stirring, raise the reaction temperature to 130°C, continue the reaction for 72 hours, add toluene solvent to dissolve and take out the polymer solution. Precipitate with ethanol again, after drying, the productive rate of polymer is 96%, and measuring intrinsic viscosity is 2.26, and at 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the melting index of product is 8.3g/10min.
实施例31Example 31
在无水无氧的条件下，取聚合级乙交酯10g，聚合级L-丙交酯15g，ε-己内酯25g，苯甲酸亚锡0.015g(0.03wt％)，二甲苯溶剂50ml加入到真空干燥过的200ml反应瓶内，抽空封管进行溶液聚合。开始反应温度控制在120～125℃搅拌进行聚合反应，大约4～6小时，体系黏度增大，停止搅拌，升高反应温度至130℃，继续反应72小时，加入甲苯溶剂溶解取出聚合物溶液，再用乙醇沉淀，干燥后，聚合物的产率为96％，测定特性粘度为2.48，在190℃下，毛细管直径1.095mm，2.16kg的压力下，产物的熔融指数是9.6g/10min。Under anhydrous and oxygen-free conditions, take polymer grade glycolide 10g, polymer grade L-lactide 15g, ε-caprolactone 25g, stannous benzoate 0.015g (0.03wt%), xylene solvent 50ml add Into a vacuum-dried 200ml reaction bottle, evacuate and seal the tube for solution polymerization. Start the reaction temperature at 120-125°C and stir to carry out the polymerization reaction. After about 4-6 hours, the viscosity of the system increases, stop stirring, raise the reaction temperature to 130°C, continue the reaction for 72 hours, add toluene solvent to dissolve and take out the polymer solution. Precipitate with ethanol again, after drying, the productive rate of polymer is 96%, and measuring intrinsic viscosity is 2.48, and at 190 ℃, capillary diameter 1.095mm, under the pressure of 2.16kg, the melting index of product is 9.6g/10min.
本发明中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。The specific embodiments described in the present invention are only to illustrate the spirit of the present invention. Those skilled in the art to which the present invention belongs can make various modifications or supplements to the described specific embodiments or adopt similar methods to replace them, but they will not deviate from the spirit of the present invention or go beyond the definition of the appended claims range.
尽管对本发明已作出了详细的说明并引证了一些具体实例，但是对本领域熟练技术人员来说，只要不离开本发明的精神和范围可作各种变化或修正是显然的。Although the invention has been described in detail and specific examples have been cited, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810181997XACN101492532B (en) | 2006-01-27 | 2006-01-27 | Use of stannous benzoate as catalyst |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810181997XACN101492532B (en) | 2006-01-27 | 2006-01-27 | Use of stannous benzoate as catalyst |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100492887ADivisionCN100518937C (en) | 2006-01-27 | 2006-01-27 | Use of stannous benzoate as catalyst |
| Publication Number | Publication Date |
|---|---|
| CN101492532A CN101492532A (en) | 2009-07-29 |
| CN101492532Btrue CN101492532B (en) | 2012-05-16 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810181997XAActiveCN101492532B (en) | 2006-01-27 | 2006-01-27 | Use of stannous benzoate as catalyst |
| Country | Link |
|---|---|
| CN (1) | CN101492532B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3792010A (en)* | 1972-03-27 | 1974-02-12 | Ethicon Inc | Plasticized polyester sutures |
| US5616620A (en)* | 1993-01-20 | 1997-04-01 | Karl Thomae Gmbh | Amino acid derivatives, pharmaceutical compositions containing these compounds and their use in the treatment of obesity |
| CN1237594A (en)* | 1998-06-03 | 1999-12-08 | 中国科学院化学研究所 | Biodegradable high polymer and its preparation method |
| JP2003160534A (en)* | 2001-11-26 | 2003-06-03 | New Japan Chem Co Ltd | Method for producing polyethylene glycol dibenzoic acid ester |
| CN1701083A (en)* | 2002-02-06 | 2005-11-23 | 聚合物器官股份有限公司 | Dl-lactide-epsilon-coprolactone copolymers |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3792010A (en)* | 1972-03-27 | 1974-02-12 | Ethicon Inc | Plasticized polyester sutures |
| US5616620A (en)* | 1993-01-20 | 1997-04-01 | Karl Thomae Gmbh | Amino acid derivatives, pharmaceutical compositions containing these compounds and their use in the treatment of obesity |
| CN1237594A (en)* | 1998-06-03 | 1999-12-08 | 中国科学院化学研究所 | Biodegradable high polymer and its preparation method |
| JP2003160534A (en)* | 2001-11-26 | 2003-06-03 | New Japan Chem Co Ltd | Method for producing polyethylene glycol dibenzoic acid ester |
| CN1701083A (en)* | 2002-02-06 | 2005-11-23 | 聚合物器官股份有限公司 | Dl-lactide-epsilon-coprolactone copolymers |
| Publication number | Publication date |
|---|---|
| CN101492532A (en) | 2009-07-29 |
| Publication | Publication Date | Title |
|---|---|---|
| CN110283305B (en) | Preparation method of biodegradable high polymer material poly (glycolide-lactide) for medical use | |
| CN103304786B (en) | The method of polyhydroxy acid with high molecular weight is prepared in a kind of serialization | |
| CN100518937C (en) | Use of stannous benzoate as catalyst | |
| CN101492441B (en) | Uses of benzoic acid stannous as catalyst | |
| CN111087580B (en) | Process for preparing polyglycolic acid | |
| CN108285528B (en) | A kind of preparation method of ultra-high molecular weight medical polylactic acid | |
| JP5763402B2 (en) | Biodegradable aliphatic polyester particles and method for producing the same | |
| CN107141457B (en) | Method for preparing polylactone by ring opening | |
| CN105131259B (en) | Biological guanidine compound system catalytic fusion solid phase synthesizes high-molecular-weight poly alpha-hydroxy acid | |
| CN107868076A (en) | The preparation of low impurity content glycolide | |
| CN108610473A (en) | A kind of method of synthesizing polylactic acid | |
| CN113527652B (en) | Method for catalyzing lactide ring-opening polymerization by Lewis acid-base pair | |
| US9062159B2 (en) | Poly(lactic-co-glycolic acid) synthesized via copolycondensation catalyzed by biomass creatinine | |
| CN114369232A (en) | A kind of renewable and degradable thermoplastic elastomer and preparation method thereof | |
| CN101492532B (en) | Use of stannous benzoate as catalyst | |
| CN100400565C (en) | A method for preparing biodegradable copolymers by ring-opening polymerization | |
| CN105418900A (en) | Preparation methods of butylene succinate and polylactic acid segmented copolymer | |
| Fang et al. | Synthesis of Poly (L‐lactide) via Solvothermal Method | |
| JP7116169B2 (en) | Lactic acid-glycolic acid copolymer and method for producing the same | |
| CN113717362B (en) | Suspension polymerization preparation method of injectable lactide-glycolide copolymer | |
| CN113087890B (en) | Environment-friendly high-yield preparation method of aliphatic polycarbonate with zero catalyst addition | |
| CN115298243B (en) | Method for producing aliphatic polyester, aliphatic polyester resin, and aliphatic polyester resin composition | |
| CN116375996A (en) | A kind of preparation method of medical polycaprolactone | |
| CN113024791A (en) | Preparation method of ultra-high molecular weight aliphatic polycarbonate | |
| CN110563695B (en) | Preparation method of mixture of glycolide and lactide |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |