技术领域technical field
本发明属于聚乙醇酸制备领域，尤其涉及一种聚乙醇酸的制备方法和得到的聚乙醇酸。The invention belongs to the field of polyglycolic acid preparation, and in particular relates to a preparation method of polyglycolic acid and the obtained polyglycolic acid.
背景技术Background technique
聚乙醇酸(PGA)是线性脂肪族聚酯的一种，一般以乙交酯为原料制备得到高分子量的PGA，并通过调节分子量满足不同的应用需求。由于PGA具有绝佳的气体阻隔性，优良的机械加工性能，出色的生物降解性能，被广泛应用于医用材料(手术缝合线和药物缓释胶囊)、包装材料(瓶内膜)、膜材料(地膜)和工程塑料(石油领域)等。Polyglycolic acid (PGA) is a kind of linear aliphatic polyester. Generally, high molecular weight PGA is prepared from glycolide as raw material, and the molecular weight is adjusted to meet different application requirements. Because PGA has excellent gas barrier properties, excellent mechanical processing properties, and excellent biodegradation properties, it is widely used in medical materials (surgical sutures and drug sustained-release capsules), packaging materials (bottle inner film), film materials ( mulch) and engineering plastics (petroleum), etc.
聚乙醇酸可以通过乙醇酸的脱水缩聚来制备，但是该方法所制得的聚乙醇酸分子量一般不高。而为了制备高分子量的聚乙醇酸，更多的是采用乙交酯开环聚合的方法。Polyglycolic acid can be prepared by dehydration polycondensation of glycolic acid, but the molecular weight of polyglycolic acid prepared by this method is generally not high. In order to prepare high molecular weight polyglycolic acid, the method of ring-opening polymerization of glycolide is more commonly used.
聚乙醇酸的制备需要经历冗长的制备周期，致使其制造成本偏高，限制其进一步的应用。其中，乙交酯的纯化工艺耗时最长，并且耗费大量溶剂，是聚乙醇酸高成本的关键因素。这是由于聚乙醇酸的获得需要高纯度的乙交酯原料。The preparation of polyglycolic acid needs to go through a lengthy preparation cycle, resulting in high manufacturing cost and limiting its further application. Among them, the purification process of glycolide takes the longest time and consumes a lot of solvent, which is the key factor for the high cost of polyglycolic acid. This is because the acquisition of polyglycolic acid requires a high-purity glycolide raw material.
以专利CN1703439A为例，其要求乙交酯原料中水分含有率在50ppm以下，α-羟基羧酸含有率在100ppm以下，α-羟基羧酸低聚物含有率在1000ppm以下。Taking the patent CN1703439A as an example, it requires that the moisture content of the glycolide raw material is below 50 ppm, the content of α-hydroxycarboxylic acid is below 100 ppm, and the content of α-hydroxycarboxylic acid oligomer is below 1000 ppm.
因此，如何将高杂质含量的乙交酯直接聚合得到高黏度聚乙醇酸仍是需要解决的难题。Therefore, how to directly polymerize glycolide with high impurity content to obtain high-viscosity polyglycolic acid is still a difficult problem to be solved.
发明内容SUMMARY OF THE INVENTION
为了克服现有技术中存在的高杂质含量乙交酯无法通过直接聚合获得高分子量聚乙醇酸的问题，本发明提供了一种聚乙醇酸的制备方法，其中，在制备过程中引入酸酐类添加剂可以降低对原料乙交酯纯度的要求，得到高分子量聚乙醇酸(PGA)，降低成本的同时进一步拓宽了PGA的应用范围。In order to overcome the problem in the prior art that high-impurity content glycolide cannot be directly polymerized to obtain high-molecular-weight polyglycolic acid, the present invention provides a preparation method of polyglycolic acid, wherein an acid anhydride additive is introduced in the preparation process The requirement on the purity of the raw material glycolide can be reduced, high molecular weight polyglycolic acid (PGA) can be obtained, and the application range of PGA can be further broadened while reducing the cost.
本发明一方面在于提供一种聚乙醇酸的制备方法，具体体现在以下几个方面：One aspect of the present invention is to provide a preparation method of polyglycolic acid, which is embodied in the following aspects:
(1)一种聚乙醇酸的制备方法，包括：采用包括乙交酯、催化剂和酸酐类添加剂在内的原料进行反应得到聚乙醇酸。(1) A method for preparing polyglycolic acid, comprising: reacting raw materials including glycolide, catalyst and acid anhydride additives to obtain polyglycolic acid.
(2)根据上述(1)所述的制备方法，其中，所述乙交酯的酸值为1～200mol/t，优选为2-100mol/t；和/或，水含量为20～2000ppm，优选为50-1000ppm。(2) The preparation method according to the above (1), wherein the acid value of the glycolide is 1-200 mol/t, preferably 2-100 mol/t; and/or the water content is 20-2000 ppm, It is preferably 50-1000 ppm.
(3)根据上述(1)所述的制备方法，其中，所述催化剂选自辛酸亚锡、四苯基锡、锡酸四丁酯、氯化亚锡、氯化锡、氧化锌、二乙基锌、二水合乙酸锌、乳酸锡、乳酸铁、三氧化二锑、二氧化钛中的至少一种。(3) The preparation method according to the above (1), wherein the catalyst is selected from stannous octoate, tetraphenyltin, tetrabutyl stannate, stannous chloride, tin chloride, zinc oxide, diethyl At least one of base zinc, zinc acetate dihydrate, tin lactate, iron lactate, antimony trioxide and titanium dioxide.
(4)根据上述(1)所述的制备方法，其中，基于所述原料总重量为100％计，所述催化剂的用量为5～500ppm，优选为10～300ppm。(4) The preparation method according to the above (1), wherein the catalyst is used in an amount of 5 to 500 ppm, preferably 10 to 300 ppm, based on 100% of the total weight of the raw materials.
(5)根据上述(1)所述的制备方法，其中，所述酸酐类添加剂选自乙酸酐、丙酸酐、丁酸酐、丁二酸酐、马来酸酐、邻苯二甲酸酐中的至少一种。(5) The preparation method according to the above (1), wherein the acid anhydride additive is at least one selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, and phthalic anhydride .
(6)根据上述(5)所述的制备方法，其中，基于所述原料总重量为100％计，所述酸酐类添加剂的用量为50～10000ppm，优选为100-8000ppm。(6) The preparation method according to the above (5), wherein, based on 100% of the total weight of the raw materials, the amount of the acid anhydride additive is 50-10000 ppm, preferably 100-8000 ppm.
(7)根据上述(1)～(6)之一所述的制备方法，其中，所述反应如下进行：先进行预反应，然后升温进行后反应。(7) The preparation method according to any one of the above (1) to (6), wherein the reaction is performed as follows: a pre-reaction is performed first, and then the temperature is raised to perform a post-reaction.
(8)根据上述(7)所述的制备方法，其中，(8) The preparation method according to the above (7), wherein,
所述预反应的温度为85-180℃，时间为10min-10h；和/或，The temperature of the pre-reaction is 85-180°C, and the time is 10min-10h; and/or,
所述后反应的温度为130-230℃，时间为5min-2h。The temperature of the post-reaction is 130-230°C, and the time is 5min-2h.
(9)根据上述(7)所述的制备方法，其中，所述预反应和所述后反应均于第一反应器内进行；或者，在第一反应器内进行预反应，预反应结束后将物料转移至第二反应器内进行后反应。(9) The preparation method according to the above (7), wherein both the pre-reaction and the post-reaction are carried out in the first reactor; or, the pre-reaction is carried out in the first reactor, and after the pre-reaction is completed The material was transferred to the second reactor for post-reaction.
(10)根据上述(9)所述的制备方法，其中，(10) The preparation method according to the above (9), wherein,
所述第一反应器选自釜式反应器、静态反应器、螺杆挤出机中的至少一种；和/或，The first reactor is selected from at least one of a tank reactor, a static reactor, and a screw extruder; and/or,
所述第二反应器选自釜式反应器、静态反应器、螺杆挤出机中的至少一种。The second reactor is selected from at least one of a tank reactor, a static reactor, and a screw extruder.
本发明第二方面在于提供利用本发明第一方面所述制备方法得到的聚乙醇酸。其中，所述聚乙醇酸的特性粘度大于0.7dL/g、优选大于0.9dL/g。The second aspect of the present invention is to provide polyglycolic acid obtained by the preparation method described in the first aspect of the present invention. Wherein, the intrinsic viscosity of the polyglycolic acid is greater than 0.7 dL/g, preferably greater than 0.9 dL/g.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行具体的描述，有必要在此指出的是以下实施例只用于对本发明的进一步说明，不能理解为对本发明保护范围的限制，本领域技术人员根据本发明内容对本发明做出的一些非本质的改进和调整仍属本发明的保护范围。The present invention will be specifically described below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention, and should not be construed as limitations on the protection scope of the present invention. Some non-essential improvements and adjustments made by the invention still belong to the protection scope of the present invention.
另外需要说明的是，在以下具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that, each specific technical feature described in the following specific implementation manner may be combined in any suitable manner under the circumstance that there is no contradiction. In order to avoid unnecessary repetition, the present invention will not describe various possible combinations.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，由此而形成的技术方案属于本说明书原始公开内容的一部分，同时也落入本发明的保护范围。In addition, the various embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, and the technical solutions formed thereby belong to a part of the original disclosure content of the present specification, and also fall into the present invention. scope of protection.
本发明的目的之一在于提供一种聚乙醇酸的制备方法，包括：采用包括乙交酯、催化剂和酸酐类添加剂在内的原料进行反应得到聚乙醇酸。One of the objectives of the present invention is to provide a method for preparing polyglycolic acid, which includes: reacting raw materials including glycolide, catalyst and acid anhydride additives to obtain polyglycolic acid.
在一种优选的实施方式中，所述乙交酯的酸值为1～200mol/t，水含量为20～2000ppm。In a preferred embodiment, the acid value of the glycolide is 1-200 mol/t, and the water content is 20-2000 ppm.
在进一步优选的实施方式中，所述乙交酯的酸值为2-100mol/t；水含量为50-1000ppm。In a further preferred embodiment, the acid value of the glycolide is 2-100 mol/t; the water content is 50-1000 ppm.
在一种优选的实施方式中，所述催化剂选自辛酸亚锡、四苯基锡、锡酸四丁酯、氯化亚锡、氯化锡、氧化锌、二乙基锌、二水合乙酸锌、乳酸锡、乳酸铁、三氧化二锑、二氧化钛中的至少一种。In a preferred embodiment, the catalyst is selected from stannous octoate, tetraphenyltin, tetrabutyl stannate, stannous chloride, tin chloride, zinc oxide, diethyl zinc, zinc acetate dihydrate , at least one of tin lactate, ferric lactate, antimony trioxide and titanium dioxide.
在进一步优选的实施方式中，基于所述原料总重量为100％计，所述催化剂的用量为5～500ppm，优选为10～300ppm。In a further preferred embodiment, based on 100% of the total weight of the raw materials, the catalyst is used in an amount of 5-500 ppm, preferably 10-300 ppm.
在一种优选的实施方式中，所述酸酐类添加剂选自乙酸酐、丙酸酐、丁酸酐、丁二酸酐、马来酸酐、邻苯二甲酸酐中的至少一种。In a preferred embodiment, the acid anhydride additive is selected from at least one of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, and phthalic anhydride.
在进一步优选的实施方式中，基于所述原料总重量为100％计，所述酸酐类添加剂的用量为50～10000ppm，优选为100-8000ppm。In a further preferred embodiment, based on 100% of the total weight of the raw materials, the acid anhydride additive is used in an amount of 50-10000 ppm, preferably 100-8000 ppm.
其中，所述酸酐类添加剂的用量可以为50ppm、80ppm、100ppm、200ppm、300ppm、400ppm、500ppm、600ppm、700ppm、800ppm、900ppm、1000ppm、1500ppm、2000ppm、2500ppm、3000ppm、3500ppm、4000ppm、4500ppm、5000ppm、5500ppm、6000ppm、6500ppm、7000ppm、7500ppm或8000ppm。Wherein, the dosage of the acid anhydride additives can be 50ppm, 80ppm, 100ppm, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm, 5000ppm , 5500ppm, 6000ppm, 6500ppm, 7000ppm, 7500ppm or 8000ppm.
现有技术在聚乙醇酸制备中，如果要得到高分子量聚乙醇酸则需要高纯乙交酯，且现有技术中得到的聚乙醇酸中乙交酯残单较多。而本发明在聚合时加入酸酐类添加剂，可以减少乙交酯中杂质的影响，聚乙醇酸产品中残单含量也减少。In the preparation of polyglycolic acid in the prior art, if high molecular weight polyglycolic acid is to be obtained, high-purity glycolide is required, and the polyglycolic acid obtained in the prior art has many glycolide residues. In the present invention, acid anhydride additives are added during polymerization, so that the influence of impurities in glycolide can be reduced, and the content of residual monomers in the polyglycolic acid product is also reduced.
在一种优选的实施方式中，所述反应如下进行：先进行预反应，然后升温进行后反应。In a preferred embodiment, the reaction is carried out as follows: pre-reaction is carried out first, and then the temperature is raised to carry out post-reaction.
在进一步优选的实施方式中，所述预反应的温度为85-180℃，时间为10min-10h。In a further preferred embodiment, the temperature of the pre-reaction is 85-180°C, and the time is 10min-10h.
例如，所述预反应的温度可以为85℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃或180℃，预反应的时间可以为10min、20min、30min、40min、50min、1h、2h、3h、4h、5h、6h、7h、8h、9h或10h。For example, the temperature of the pre-reaction can be 85°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C, and the pre-reaction time can be 10min , 20min, 30min, 40min, 50min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.
在更进一步优选的实施方式中，所述后反应的温度为130-230℃，时间为5min-2h。In a further preferred embodiment, the temperature of the post-reaction is 130-230°C, and the time is 5min-2h.
例如，所述预反应的温度可以为130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃或230℃，预反应的时间为5min、10min、20min、30min、40min、50min、1h、1.5h或2h。For example, the temperature of the pre-reaction can be 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C or 230°C, and the pre-reaction time is 5 min, 10min, 20min, 30min, 40min, 50min, 1h, 1.5h or 2h.
在一种优选的实施方式中，所述预反应和所述后反应均于第一反应器内进行；或者，在第一反应器内进行预反应，预反应结束后将物料转移至第二反应器内进行后反应。In a preferred embodiment, both the pre-reaction and the post-reaction are carried out in the first reactor; or, the pre-reaction is carried out in the first reactor, and the material is transferred to the second reaction after the pre-reaction is over The post-reaction is carried out in the vessel.
在进一步优选的实施方式中，所述第一反应器选自釜式反应器、静态反应器、螺杆挤出机中的至少一种；和/或，所述第二反应器选自釜式反应器、静态反应器、螺杆挤出机中的至少一种。In a further preferred embodiment, the first reactor is selected from at least one of a tank reactor, a static reactor, and a screw extruder; and/or, the second reactor is selected from a tank reactor At least one of a reactor, a static reactor, and a screw extruder.
本发明目的之二在于提供利用本发明目的之一所述制备方法得到的聚乙醇酸。The second object of the present invention is to provide polyglycolic acid obtained by the preparation method described in one of the objects of the present invention.
在一种优选的实施方式中，所述聚乙醇酸的特性粘度大于0.7dL/g、优选大于0.9dL/g。In a preferred embodiment, the intrinsic viscosity of the polyglycolic acid is greater than 0.7 dL/g, preferably greater than 0.9 dL/g.
在本发明中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。在下文中，各个技术方案之间原则上可以相互组合而得到新的技术方案，这也应被视为在本文中具体公开。The endpoints of ranges and any values disclosed herein are not limited to the precise ranges or values, which are to be understood to encompass values proximate to those ranges or values. For ranges of values, the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein. In the following, in principle, various technical solutions can be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
与现有技术相比，本发明具有如下有益效果：现有技术中，高黏度聚乙醇酸(PGA)一般需要高纯度的乙交酯通过聚合得到。当乙交酯中的杂质，如乙醇酸二聚体、乙醇酸低聚物、残留溶剂、水等，会影响聚乙醇酸的聚合反应，难以获得有应用价值的高黏度PGA。同时，通过乙交酯提纯去除这些杂质费时费力，大大提高了原料成本。本发明针对这一现象，通过引入酸酐类添加剂将这些杂质中影响聚合的羟基官能团转换为对聚合影响小的羧基官能团，降低了对乙交酯纯度的要求，同时可以获得高黏度的PGA，降低成本的同时进一步拓宽了PGA的应用范围。Compared with the prior art, the present invention has the following beneficial effects: In the prior art, high-viscosity polyglycolic acid (PGA) generally requires high-purity glycolide to be obtained by polymerization. When impurities in glycolide, such as glycolic acid dimer, glycolic acid oligomer, residual solvent, water, etc., will affect the polymerization of polyglycolic acid, it is difficult to obtain high-viscosity PGA with application value. At the same time, it is time-consuming and laborious to remove these impurities through glycolide purification, which greatly increases the cost of raw materials. Aiming at this phenomenon, the present invention converts the hydroxyl functional groups that affect polymerization in these impurities into carboxyl functional groups that have little effect on polymerization by introducing acid anhydride additives, so as to reduce the requirement for the purity of glycolide, and at the same time, high viscosity PGA can be obtained. At the same time, the application scope of PGA is further broadened.
【实施例与对比例】[Example and Comparative Example]
实施例与对比例中采用的原料，如果没有特别限定，那么均是现有技术公开的，例如可直接购买获得或者根据现有技术公开的制备方法制得。The raw materials used in the examples and comparative examples, if not particularly limited, are disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.
【实施例1】[Example 1]
将酸值为2mol/t、水含量为100ppm的乙交酯和辛酸亚锡以及乙酸酐加入到釜式反应器内进行预反应，其中辛酸亚锡用量为100ppm，乙酸酐用量为100ppm，预反应温度为90℃，时间为2h。预反应结束后将物料转移至静态反应器进行后反应，反应温度为210℃，时间为8min，制得聚乙醇酸树脂的特性粘度为1.6dL/g。Glycolide and stannous octoate and acetic anhydride with acid value of 2mol/t and water content of 100ppm are added in the still reactor and carry out pre-reaction, wherein the stannous octoate consumption is 100ppm, and the acetic anhydride consumption is 100ppm, and the pre-reaction The temperature was 90°C and the time was 2h. After the pre-reaction, the material was transferred to a static reactor for post-reaction. The reaction temperature was 210° C. and the time was 8 minutes. The intrinsic viscosity of the obtained polyglycolic acid resin was 1.6 dL/g.
【实施例2】[Example 2]
将酸值为10mol/t、水含量为50ppm的乙交酯和四苯基锡以及丙酸酐加入到釜式反应器内进行预反应，其中四苯基锡用量为10ppm，丙酸酐用量为200ppm，预反应温度为85℃，时间为9h。预反应结束后将物料转移至静态反应器进行后反应，反应温度为140℃，时间为120min，制得聚乙醇酸树脂的特性粘度为1.0dL/g。With acid value of 10mol/t, water content is that glycolide and tetraphenyl tin and propionic anhydride of 50ppm join in the still reactor and carry out pre-reaction, and wherein tetraphenyl tin consumption is 10ppm, and propionic anhydride consumption is 200ppm, The pre-reaction temperature was 85°C and the time was 9h. After the pre-reaction, the material was transferred to a static reactor for post-reaction. The reaction temperature was 140° C. and the time was 120 min. The intrinsic viscosity of the obtained polyglycolic acid resin was 1.0 dL/g.
【实施例3】[Example 3]
将酸值为10mol/t、水含量为200ppm的乙交酯和氯化亚锡以及丁二酸酐加入到静态反应器内进行预反应，其中氯化亚锡用量为100ppm，丁二酸酐用量为300ppm，预反应温度为110℃，时间为45min。预反应结束后将物料转移至釜式反应器进行后反应，反应温度为180℃，时间为90min，制得聚乙醇酸树脂的特性粘度为1.1dL/g。Glycolide, stannous chloride and succinic anhydride with an acid value of 10 mol/t and a water content of 200 ppm are added to the static reactor for pre-reaction, wherein the stannous chloride consumption is 100 ppm, and the succinic anhydride consumption is 300 ppm , the pre-reaction temperature was 110 °C, and the time was 45 min. After the pre-reaction, the material was transferred to a kettle-type reactor for post-reaction, the reaction temperature was 180° C. and the time was 90 minutes, and the intrinsic viscosity of the obtained polyglycolic acid resin was 1.1 dL/g.
【实施例4】[Example 4]
将酸值为50mol/t、水含量为200ppm的乙交酯和氯化锡以及丁酸酐加入到静态反应器内进行预反应，其中氯化锡用量为50ppm，丁酸酐用量为2000ppm，预反应温度为130℃，时间为30min。预反应结束后将物料转移至螺杆挤出机进行后反应，反应温度为220℃，时间为10min，制得聚乙醇酸树脂的特性粘度为1.3dL/g。With acid value of 50mol/t, water content is that glycolide and tin chloride and butyric anhydride of 200ppm are joined in static reactor and carry out pre-reaction, wherein tin chloride consumption is 50ppm, butyric anhydride consumption is 2000ppm, pre-reaction temperature It is 130 ℃, the time is 30min. After the pre-reaction, the material was transferred to a screw extruder for post-reaction. The reaction temperature was 220° C. and the time was 10 min. The intrinsic viscosity of the obtained polyglycolic acid resin was 1.3 dL/g.
【实施例5】[Example 5]
将酸值为50mol/t、水含量为800ppm的乙交酯和二乙基锌以及马来酸酐加入到釜式反应器内进行预反应，其中二乙基锌用量为300ppm，马来酸酐用量为4000ppm，预反应温度为150℃，时间为15min。预反应结束后将物料转移至螺杆挤出机进行后反应，反应温度为225℃，时间为15min，制得聚乙醇酸树脂的特性粘度为1.1dL/g。With acid value of 50mol/t, water content is that glycolide and diethylzinc and maleic anhydride of 800ppm are added in the still reactor and carry out pre-reaction, wherein the diethylzinc consumption is 300ppm, and the maleic anhydride consumption is 4000ppm, the pre-reaction temperature is 150°C, and the time is 15min. After the pre-reaction, the material was transferred to a screw extruder for post-reaction. The reaction temperature was 225° C. and the time was 15 minutes. The intrinsic viscosity of the obtained polyglycolic acid resin was 1.1 dL/g.
【实施例6】[Example 6]
将酸值为70mol/t、水含量为900ppm的乙交酯和乳酸锡以及邻苯二甲酸酐加入到螺杆挤出机内进行预反应，其中乳酸锡用量为200ppm，邻苯二甲酸酐用量为6000ppm，预反应温度为170℃，时间为10min。预反应结束后将物料转移至螺杆挤出机进行后反应，反应温度为215℃，时间为30min，制得聚乙醇酸树脂的特性粘度为0.9dL/g。Glycolide with acid value of 70mol/t and water content of 900ppm and tin lactate and phthalic anhydride are added in the screw extruder to carry out pre-reaction, wherein the tin lactate consumption is 200ppm, and the phthalic anhydride consumption is 6000ppm, the pre-reaction temperature is 170°C, and the time is 10min. After the pre-reaction, the material was transferred to a screw extruder for post-reaction. The reaction temperature was 215° C. and the time was 30 minutes. The intrinsic viscosity of the obtained polyglycolic acid resin was 0.9 dL/g.
【实施例7】[Example 7]
将酸值为70mol/t、水含量为200ppm的乙交酯和二氧化钛以及乙酸酐加入到螺杆挤出机内进行预反应，其中二氧化钛用量为100ppm，乙酸酐用量为5500ppm，预反应温度为120℃，时间为5h。预反应结束后将物料转移至釜式反应器进行后反应，反应温度为200℃，时间为60min，制得聚乙醇酸树脂的特性粘度为1.1dL/g，。Glycolide, titanium dioxide and acetic anhydride with an acid value of 70 mol/t and a water content of 200 ppm are added to the screw extruder for pre-reaction, wherein the titanium dioxide consumption is 100 ppm, the acetic anhydride consumption is 5500 ppm, and the pre-reaction temperature is 120 ℃ , the time is 5h. After the pre-reaction, the material was transferred to a kettle type reactor for post-reaction, the reaction temperature was 200° C., the time was 60 min, and the intrinsic viscosity of the obtained polyglycolic acid resin was 1.1 dL/g.
【实施例8】[Example 8]
将酸值为90mol/t、水含量为100ppm的乙交酯和乳酸铁以及丙酸酐加入到釜式反应器内进行预反应，其中乳酸铁用量为20ppm，丙酸酐用量为8000ppm，预反应温度为100℃，时间为4h。预反应结束后将物料转移至螺杆挤出机进行后反应，反应温度为190℃，时间为20min，制得聚乙醇酸树脂的特性粘度为1.5dL/g。With acid value of 90mol/t, water content is that glycolide and ferric lactate and propionic anhydride of 100ppm join in the still reactor and carry out pre-reaction, wherein ferric lactate consumption is 20ppm, and propionic anhydride consumption is 8000ppm, and the pre-reaction temperature is 100°C for 4h. After the pre-reaction, the material was transferred to a screw extruder for post-reaction. The reaction temperature was 190° C. and the time was 20 minutes. The intrinsic viscosity of the obtained polyglycolic acid resin was 1.5 dL/g.
【实施例9】[Example 9]
将酸值为90mol/t、水含量为400ppm的乙交酯和三氧化二锑以及丁酸酐，加入到螺杆挤出机内进行预反应，其中三氧化二锑用量为250ppm，丁酸酐用量为8000ppm，预反应温度为110℃，时间为7h。预反应结束后将物料转移至静态反应器进行后反应，反应温度为230℃，时间为6min，制得聚乙醇酸树脂的特性粘度为1.4dL/g。Glycolide, antimony trioxide and butyric anhydride with an acid value of 90 mol/t and a water content of 400 ppm were added to the screw extruder for pre-reaction, wherein the amount of antimony trioxide was 250 ppm, and the amount of butyric anhydride was 8000 ppm , the pre-reaction temperature was 110°C, and the time was 7h. After the pre-reaction, the material was transferred to a static reactor for post-reaction. The reaction temperature was 230° C. and the time was 6 min. The intrinsic viscosity of the obtained polyglycolic acid resin was 1.4 dL/g.
【比较例1】[Comparative Example 1]
将酸值为2mol/t、水含量为100ppm的乙交酯和辛酸亚锡加入到釜式反应器内进行预反应，其中辛酸亚锡用量为100ppm，预反应温度为90℃，时间为2h。预反应结束后将物料转移至静态反应器进行后反应，反应温度为210℃，时间为8min，制得聚乙醇酸树脂的特性粘度为1.2dL/g。Glycolide and stannous octoate with an acid value of 2 mol/t and a water content of 100 ppm were added to the tank reactor for pre-reaction, wherein the amount of stannous octoate was 100 ppm, the pre-reaction temperature was 90 °C, and the time was 2 h. After the pre-reaction, the material was transferred to a static reactor for post-reaction. The reaction temperature was 210° C. and the time was 8 minutes. The intrinsic viscosity of the obtained polyglycolic acid resin was 1.2 dL/g.
【比较例2】[Comparative Example 2]
将酸值为90mol/t、水含量为400ppm的乙交酯和三氧化二锑，加入到螺杆挤出机内进行预反应，其中三氧化二锑用量为250ppm，预反应温度为110℃，时间为7h。预反应结束后将物料转移至静态反应器进行后反应，反应温度为230℃，时间为6min，制得聚乙醇酸树脂的特性粘度为0.7dL/g。Glycolide and antimony trioxide with an acid value of 90 mol/t and a water content of 400 ppm were added to the screw extruder for pre-reaction, wherein the amount of antimony trioxide was 250 ppm, and the pre-reaction temperature was 110° C. for 7h. After the pre-reaction, the material was transferred to a static reactor for post-reaction. The reaction temperature was 230° C. and the time was 6 min. The intrinsic viscosity of the obtained polyglycolic acid resin was 0.7 dL/g.
【比较例3】[Comparative Example 3]
将酸值为10mol/t、水含量为200ppm的乙交酯和氯化亚锡加入到静态反应器内进行预反应，其中氯化亚锡用量为100ppm，预反应温度为110℃，时间为45min。预反应结束后将物料转移至釜式反应器进行后反应，反应温度为180℃，时间为90min，制得聚乙醇酸树脂的特性粘度为0.85dL/g。Glycolide and stannous chloride with an acid value of 10 mol/t and a water content of 200 ppm were added to the static reactor for pre-reaction, wherein the stannous chloride consumption was 100 ppm, and the pre-reaction temperature was 110 ° C and the time was 45 min . After the pre-reaction, the material was transferred to a kettle-type reactor for post-reaction, the reaction temperature was 180° C. and the time was 90 minutes, and the intrinsic viscosity of the obtained polyglycolic acid resin was 0.85 dL/g.
【比较例4】[Comparative Example 4]
将酸值为2mol/t、水含量为100ppm的乙交酯和辛酸亚锡以及乙酸酐加入到釜式反应器内进行预反应，其中辛酸亚锡用量为100ppm，乙酸酐用量为50ppm，预反应温度为90℃，时间为2h。预反应结束后将物料转移至静态反应器进行后反应，反应温度为210℃，时间为8min，制得聚乙醇酸树脂的特性粘度为1.3dL/g。With acid value of 2mol/t, water content is that glycolide and stannous octoate and acetic anhydride that 100ppm are added in the still reactor and carry out pre-reaction, wherein stannous octoate consumption is 100ppm, and acetic anhydride consumption is 50ppm, pre-reaction The temperature was 90°C and the time was 2h. After the pre-reaction, the material was transferred to a static reactor for post-reaction. The reaction temperature was 210° C. and the time was 8 minutes. The intrinsic viscosity of the obtained polyglycolic acid resin was 1.3 dL/g.
【比较例5】[Comparative Example 5]
将酸值为2mol/t、水含量为100ppm的乙交酯和辛酸亚锡以及乙酸酐加入到釜式反应器内进行预反应，其中辛酸亚锡用量为100ppm，乙酸酐用量为10000ppm，预反应温度为90℃，时间为2h。预反应结束后将物料转移至静态反应器进行后反应，反应温度为210℃，时间为8min，制得聚乙醇酸树脂的特性粘度为2.0dL/g，粘度过高不适合后续加工。With acid value of 2mol/t, water content is that glycolide and stannous octoate and acetic anhydride of 100ppm are joined in the kettle type reactor and carry out pre-reaction, wherein stannous octoate consumption is 100ppm, acetic anhydride consumption is 10000ppm, pre-reaction The temperature was 90°C and the time was 2h. After the pre-reaction, the material was transferred to a static reactor for post-reaction. The reaction temperature was 210° C. and the time was 8 minutes. The intrinsic viscosity of the obtained polyglycolic acid resin was 2.0 dL/g, which was too high for subsequent processing.
以上结合具体实施方式和范例性实例对本发明进行了详细说明，不过这些说明并不能理解为对本发明的限制。本领域技术人员理解，在不偏离本发明精神和范围的情况下，可以对本发明技术方案及其实施方式进行多种等价替换、修饰或改进，这些均落入本发明的范围内。本发明的保护范围以所附权利要求为准。The present invention has been described in detail above in conjunction with specific embodiments and exemplary examples, but these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, various equivalent replacements, modifications or improvements can be made to the technical solutions of the present invention and the embodiments thereof, which all fall within the scope of the present invention. The scope of protection of the present invention is determined by the appended claims.
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| CN202110434161.1ACN115232292B (en) | 2021-04-22 | 2021-04-22 | A method for preparing polyglycolic acid and the obtained polyglycolic acid |
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| CN202110434161.1ACN115232292B (en) | 2021-04-22 | 2021-04-22 | A method for preparing polyglycolic acid and the obtained polyglycolic acid |
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| CN202110434161.1AActiveCN115232292B (en) | 2021-04-22 | 2021-04-22 | A method for preparing polyglycolic acid and the obtained polyglycolic acid |
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