CN119264391A - A polyglycolide graft copolymer and its preparation method and application - Google Patents
A polyglycolide graft copolymer and its preparation method and application Download PDFInfo
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Abstract
The invention provides a polyglycolide graft copolymer, which has a structure shown in the following general formula, wherein R 1、R2、R3、R4、……、Rn‑3、Rn‑2、Rn‑1 and R n are respectively and independently selected from H orThe two substituents bound to the same carbon atom being not simultaneouslyAnd in R 1、R2、R3、R4、……、Rn‑3、Rn‑2、Rn‑1 and R n, the substituent isThe mole percentage is not less than 5%. The preparation method comprises the steps of polymerizing maleic anhydride and glycolide to obtain MA-GA, and polymerizing the MA-GA at a low temperature to obtain a copolymer with high molecular weight. The invention greatly improves the grafting efficiency, increases the molecular weight of the polymer, successfully introduces more maleic anhydride polar groups on the side chain of the polyglycolide through the grafting reaction, and improves the toughness and the elongation at break of the polyglycolide material.
Description
Technical Field
The invention relates to a glycolide ring-opening polymerization technology, in particular to a high molecular weight polyglycolide graft copolymer and a preparation method thereof, belonging to the field of high molecular material synthesis.
Background
The polyglycolide is a polymer material with good biocompatibility and biodegradability, compared with the traditional polymer material, the polyglycolide can be completely degraded in a human body without the participation of special enzymes, and degraded products can be absorbed and metabolized in the body to finally form carbon dioxide and water. Due to its excellent biocompatibility and biodegradability, the polyglycolide and its copolymer are widely used in degradable medical surgical suture, internal bone fracture fixator, controlled-release carrier of medicine, tissue engineering scaffold, etc.
There are mainly two methods for producing polyglycolic acid, one is polycondensation reaction of glycolic acid (direct polycondensation method is generally direct dehydration (dealcoholization) polycondensation of glycolic acid). The polymerization process of the method does not need to prepare and purify intermediate products such as dimer and the like, greatly reduces reaction procedures, has simpler operation, requires fewer instruments and equipment, and has low requirement on monomer purity. However, the disadvantages are also obvious that the equilibrium constant of the reaction is not large, the higher dehydration degree is difficult to achieve in the polymerization process, the molecular weight of the product is often lower, the molecular weight of the polyglycolide obtained by the method is only thousands, the physical and chemical properties of the polyglycolide can not meet the requirements, the mechanical strength of the polyglycolide can not meet the requirements of fracture bracket materials or surgical sutures far from due to the characteristic of easy decomposition of the polyglycolide, and in addition, the melt polycondensation reaction is often required to be carried out at a higher temperature, and the product is easy to be oxidized at a high temperature to cause discoloration. And the other is to heat and decompose the glycolic acid polycondensation polymer to obtain cyclic glycolide, and obtain high molecular weight polyglycolic acid with molecular weight of tens of thousands to hundreds of thousands by ring-opening polymerization of glycolide, so that the subsequent processing requirement can be met. The ring-opening polymerization of glycolide generally occurs under milder conditions, has some characteristics of active polymerization, is different from the conventional polycondensation reaction, has fewer side reactions, does not have the problem of equal proportion of raw materials, is easier to obtain a product with higher molecular weight, and meanwhile, the ring-opening polymerization of glycolide needs to be promoted by a suitable catalyst, otherwise, the relative molecular weight is difficult to increase.
The polyglycolide has the defects of large brittleness, strong hydrophobicity, low toughness and the like, so that the polyglycolide material is difficult to directly prepare industrial products like general plastics such as polyethylene, polypropylene and the like, and the industrial products are required to be modified. At present, a relatively large number of methods are adopted to optimize the service performance of the polyglycolide and other plastics in a blending processing mode, and although the method is simple, the properties of the polyglycolide material are not changed fundamentally, and in addition, some researches are carried out by adding a plasticizer or a compatilizer into the polyglycolide material to improve the properties of the material, such as maleic anhydride is a better compatilizer, maleic anhydride is a polar monomer material, and the polarity and toughness of the polyglycolide material are improved by carrying out compatibilization modification on the polyglycolide by the maleic anhydride. At present, a relatively large number of methods are adopted at home and abroad to add maleic anhydride into the polyglycolide or the polyglycolide copolymer so as to improve the toughness of the polyglycolide or the polyglycolide copolymer, but the modification effect of the method is not obvious.
Chinese patent CN107840949A is prepared by mixing difunctional group-terminated polysiloxane oligomer with glycolide in the presence of an organic solvent, and copolymerizing under the action of a catalyst to obtain the polyglycolide-polysiloxane block copolymer, namely the organosilicon modified polyglycolide. Compared with the polyglycolide, the segmented copolymer has the characteristics of good flexibility, good impact resistance, good heat resistance and the like, can be applied to the technical field of 3D printing, can be quickly and efficiently manufactured into a product with a complex structure, is used in the fields of bioengineering and the like, improves the toughness of the polyglycolide in a copolymerization mode, but has small molecular weight and low strength. Chinese patent CN102634001A uses benzyl chloride as end-capping agent to carry out end-capping reaction on biodegradable polyester polyglycolide, and the end-capped biodegradable polyglycolide has obviously improved hydrolysis resistance and thermal stability compared with the polyglycolide which is not end-capped and modified, but only has polar groups connected to the end groups of the polyglycolide, so that the improvement effect is not obvious. Chinese patent CN107488343a adds maleic anhydride into the blend material of polyglycolide and other resins, and prepares the polyglycolide copolyester material by means of extrusion by a thermal reaction screw extruder, and maleic anhydride improves the compatibility between polyglycolide and other resins to a certain extent, but it is difficult to fundamentally change the thermodynamic properties of polyglycolide.
In summary, the existing technology for preparing and modifying the polyglycolide mainly has the following main problems that (1) the quality requirement on the raw materials of the glycolide monomer is high, and the free hydroxyl content (free acid and water) in the glycolide monomer seriously affects the polymerization degree of the polyglycolide. (2) The pure polyglycolide product has poor heat resistance and low toughness, and needs modification processing to be industrially applied. (3) By simply adding a plasticizer and a toughening agent into the polyglycolide material, the thermodynamic performance of the polyglycolide cannot be fundamentally improved (4) the graft or esterification reaction is carried out on the side chain or the terminal group of the macromolecular chain of the polyglycolide, and the reaction activity is low and the modification effect is poor.
Disclosure of Invention
Aiming at the defects, the invention provides the polyglycolide graft copolymer and the preparation method thereof, and the maleic anhydride graft polyglycolide copolymer material (MA-PGA) with higher molecular weight is prepared by adopting a reaction route different from the prior art, has high maleic anhydride grafting rate, has good toughness and heat resistance, is green and degradable, and is easy for industrial production.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
The technical object of the first aspect of the present invention is to provide a polyglycolide graft copolymer, which is a compound having the structure of formula I:
Wherein R 1、R2、R3、R4、……、Rn-3、Rn-2、Rn-1 and R n are each independently selected from H or The two substituents bound to the same carbon atom being not simultaneouslyAnd in R 1、R2、R3、R4、……、Rn-3、Rn-2、Rn-1 and R n, the substituent isThe molar percentage is not less than 5%, preferably 5% to 50%, more preferably 10% to 45%, most preferably 25% to 40%.
Further, the weight average molecular weight of the polyglycolide graft copolymer is 1.0X10 5-3.5×105, preferably 1.5X10 5-3×105.
Further, the copolymer has a right angle tear strength of not less than 250kN/m, preferably 260 to 290kN/m, an elongation at break of not less than 15%, preferably 18 to 30%, and a glass transition temperature of 60 to 70 ℃.
In the present invention, the right angle tear strength and elongation at break are measured by a universal mechanical test machine, the weight average molecular weight is measured by a gel chromatography method, and the glass transition temperature is measured by a differential scanning calorimeter method, which will be described in detail below.
The technical purpose of the second aspect of the invention is to provide a preparation method of a polyglycolide graft copolymer, which comprises the following steps:
(1) Mixing glycolide, maleic anhydride and an initiator for reaction to obtain maleic anhydride grafted glycolide (MA-GA), and purifying the product;
(2) Mixing the MA-GA obtained in the step (1) with a catalyst and an initiator, and performing low-temperature prepolymerization to obtain an MA-GA oligomer;
(3) Mixing the MA-GA oligomer obtained in the step (2) with an antioxidant, and performing high-temperature polymerization to obtain a maleic anhydride grafted polyglycolide copolymer material (MA-PGA).
Further, the initiator in the step (1) is dicumyl peroxide or 2, 5-dimethyl-2, 5-bis- (tert-butylperoxy) hexane, preferably dicumyl peroxide, and the initiator is added in an amount of 0.1-5%, preferably 0.5-2.0% of glycolide by weight.
Further, step (1) is a constant temperature reaction under inert gas flow, preferably nitrogen flow, and vacuum-pumping condition, wherein the reaction temperature is 50-150 ℃, preferably 80-120 ℃, the reaction pressure is 2-100kpa, preferably 20-60kpa, the reaction time is 0.5-10h, preferably 2-6h, the gas flow rate protected by the nitrogen flow is 0.5-6m/s, preferably 2-4m/s, and the maleic anhydride is 100-300%, preferably 150-200% of glycolide by weight of glycolide.
Further, the glycolide in step (1) has an optical purity of 99.0 to 99.6%, preferably 99.4 to 99.6%, and a commercially available L-glycolide can be used.
The main reaction occurring in step (1) is shown in the following formula:
further, the purification in the step (1) is to remove glycolide which does not participate in the grafting reaction by adopting a reduced pressure distillation mode, so as to obtain purified maleic anhydride grafted glycolide (MA-GA). Specifically, the reduced pressure distillation is carried out at a temperature of 100-200deg.C, preferably 120-150deg.C, a pressure of 0-100kpa, preferably 10-50kpa, and a time of 1-10h, preferably 2-6h.
Further, the catalyst in the step (2) is selected from one or more of stannous octoate, zinc lactate, trialkylaluminum, triisobutylaluminum and stannous chloride, preferably stannous octoate, and the initiator is selected from at least one of glycerol, xylitol, ethylene glycol and triphenylphosphine, preferably triphenylphosphine.
Further, in the step (2), the catalyst is added in an amount of 0.1 to 5% by weight, preferably 0.5 to 3% by weight, of MA-GA, and the initiator is added in an amount of 0.05 to 5.0% by weight, preferably 0.5 to 2% by weight, of MA-GA.
Further, the step (2) is a low temperature polymerization under inert gas flow, preferably nitrogen flow, and negative pressure, wherein the temperature of the polymerization reaction is 100-150 ℃, preferably 120-140 ℃, the reaction time is 2-15h, preferably 3-8h, the reaction pressure is 100-1000kpa, preferably 200-500kpa, and the gas flow rate of the nitrogen flow is 0.5-6m/s, preferably 2-4m/s.
Further, the antioxidant in the step (3) is one of phosphite esters, alkyl polyphenols and thiobisphenols, preferably triphenyl phosphite, and the antioxidant is added in an amount of 0.1% -5%, preferably 1-3% by weight of the MA-GA oligomer.
Further, the temperature of the polymerization reaction in step (3) is 150 to 250 ℃, preferably 160 to 200 ℃.
The main reaction processes of the steps (2) and (3) are shown as the following formula:
Further, the step (3) adopts a double-screw extruder to realize the reaction process, the MA-GA oligomer and the antioxidant are added into the double-screw extruder to carry out polymerization reaction, high-temperature reactive mixing extrusion granulation is carried out, and finally the maleic anhydride grafted polyglycolide copolymer material (MA-PGA) is obtained.
The technical purpose of the third aspect of the invention is to provide the application of the polyglycolide graft copolymer, wherein the polyglycolide graft copolymer is applied to the aspects of degradable medical surgical suture lines, fracture internal fixation, drug controlled release carriers, tissue engineering scaffolds and the like.
Compared with the prior art, the invention has the following advantages:
(1) Compared with the prior art, the invention provides a brand-new route for synthesizing the poly-glycolide graft copolymer, which comprises the steps of firstly polymerizing Maleic Anhydride (MA) and Glycolide (GA) to obtain a maleic anhydride-glycolide copolymer (MA-GA), then prepolymerizing MA-GA at low temperature to obtain an MA-GA oligomer, and finally polymerizing the MA-GA oligomer at high temperature to obtain the high molecular weight maleic anhydride graft poly-glycolide copolymer.
(2) The method of the invention has the advantages that the grafting reaction of maleic anhydride is carried out before the polymerization of the glycolide, the grafting efficiency is greatly improved, the molecular weight of the polymer is increased, more maleic anhydride polar groups are successfully introduced into the side chain of the polyglycolide through the grafting reaction, and the toughness and the elongation at break of the polyglycolide material are improved; by adopting the preparation method provided by the invention, the grafted copolymer with the grafting rate reaching 50% can be theoretically obtained, and the content of the grafting group in the grafted copolymer can be effectively regulated and controlled by regulating and controlling the raw material proportion, so that the performance of the grafted copolymer is regulated and controlled.
(3) As a large number of maleic anhydride ring structures are introduced on the side chains of the polyglycolide, the glass transition temperature of the polyglycolide material is improved, and the prepared graft modified polyglycolide copolymer material is green and full-biodegradation.
(4) The product of the invention, due to the retention of the hydroxyl end groups of the graft copolymer, enables it to be used for further modification through the functional group to further regulate the properties of the copolymer.
(5) The method adopts the mode of carrying out the bulk prepolymerization reaction of glycolide in a reaction kettle and coupling the copolymerization of a double-screw extruder, has simple reaction operation and is easy for industrial production.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. Reagents, materials, and instruments referred to in the examples below were obtained from a commercial source unless otherwise specified. The test and inspection methods in the following examples are all those known in the art unless otherwise specified. The following examples are provided to clearly and fully describe the technical aspects of the present invention, and it is apparent that the described examples are only some, but not all, examples of the present invention. All obvious variations or modifications brought forth by the invention are intended to fall within the scope of the invention.
The following are test methods relating to performance parameters in the examples:
(1) Grafting ratio of grafting group:
The grafting rate of the grafting group in the polylactic acid graft copolymer is determined by adopting a chemical titration method, and the method comprises the steps of weighing a certain mass of the polylactic acid graft copolymer, putting the polylactic acid graft copolymer into a conical flask, adding a certain amount of tetrahydrofuran to dissolve the polylactic acid graft copolymer, dripping a little thymol blue/DMF indicator, titrating with an excessive ethanol solution of 0.05mol/L potassium hydroxide, and back titrating with an HCl-isopropanol solution of 0.01 mol/L.
Grafting ratio ＝n2/n1×100％,n1＝(m0-m2)/M1,n2＝m2/M2, is grafting ratio ＝[(0.05VKOH-0.01VHCl)×2×M1]/[m0-(0.05VKOH-0.01VHCl)×2×M2];, wherein M 0 is the mass of the weighed polylactic acid grafted copolymer, the unit is g, M 2 is the total mass of grafted groups on a polylactic acid molecular chain, the total mass is calculated according to consumed KOH, n 1 is the polymerization degree of polylactic acid, namely the mass of lactic acid units, n 2 is the mass of grafted groups on the polylactic acid molecular chain, M 1 is the molar mass of lactic acid, M 2 is the molar mass of grafted groups, V KOH is the volume of an ethanol solution added with potassium hydroxide, the unit is mL, and V HCl is the volume of a titration consumed HCl-isopropanol solution.
(2) The right-angle tear strength and elongation at break are measured by a universal mechanical tester according to the GB/T1039-1992 standard.
(3) Glass transition temperature was measured by Differential Scanning Calorimeter (DSC) (DSC 204, germany relaxation resistance). The test condition comprises that the sample quantity is 5-10 mg, the temperature of the sample is firstly increased to 200 ℃ from room temperature at the temperature increasing rate of 10 ℃ per minute, the temperature is isothermal for 5 minutes to eliminate the heat history of the sample, then the sample is rapidly cooled to-20 ℃ and then is increased to 200 ℃ from-20 ℃ at the temperature increasing rate of 10 ℃ per minute, nitrogen is introduced as shielding gas in the whole test process, and the flow rate of the nitrogen is set to 50mL/min.
(4) The molecular weight of the polymer was measured by gel chromatography (GPC) and the molecular weight of the polylactic acid graft copolymer sample was characterized by gel permeation chromatography (GPC WATERS 1515,1515 system). The chromatographically pure THF was the mobile phase, the flow rate was 1.0ml/min, and the column temperature was 35 ℃. Prior to testing, samples were dissolved in THF at a concentration of 5mg/mL, filtered through a Polytetrafluoroethylene (PTFE) filter with a pore size of 0.22 μm, and injected and calibrated with a narrow distribution Polystyrene (PS) standard.
(5) And detecting the hydroxyl end group by adopting a phthalic anhydride method according to GB/T12008.3-2009 standard.
Example 1
(1) Adding glycolide and maleic anhydride into a reaction kettle, adding an initiator dicumyl peroxide, and carrying out constant-temperature reaction under the condition of nitrogen flow and vacuumizing to obtain maleic anhydride grafted glycolide. The grafting modification reaction temperature is 95 ℃, the reaction pressure is 35kpa, the reaction time is 2h, the gas flow rate protected by the nitrogen flow is 2m/s, the maleic anhydride is 140% of the glycolide and the dicumyl peroxide is 0.5% of the glycolide based on the weight of the glycolide.
(2) Removing the glycolide which does not participate in the grafting reaction in the step (1) by adopting a reduced pressure distillation mode to obtain purified maleic anhydride grafted glycolide (MA-GA), wherein the reduced pressure distillation temperature is 125 ℃, the pressure is 15kpa, and the time is 2h.
(3) And (2) under the action of a catalyst and an initiator, adding nitrogen flow and negative pressure, carrying out low-temperature prepolymerization on the maleic anhydride grafted glycolide (MA-GA) obtained in the step (2) to obtain an MA-GA oligomer, wherein the reaction temperature of the low-temperature prepolymerization is 130 ℃, the reaction time is 3 hours, the reaction pressure is 300kpa, the GAs flow rate protected by the nitrogen flow is 3m/s, the weight of the maleic anhydride grafted glycolide (MA-GA) is 0.5% of that of the catalyst stannous octoate, and the initiator triphenylphosphine is 0.2% of that of the MA-GA.
(4) Adding the MA-GA oligomer obtained in the step (3) into a double-screw extruder for polymerization reaction, adding an antioxidant, and carrying out high-temperature reactive mixing extrusion granulation to obtain the maleic anhydride grafted polyglycolide copolymer material (MA-PGA), wherein the weight of the antioxidant triphenyl phosphite is 0.5% of that of the MA-GA oligomer, and the reactive mixing extrusion granulation reaction extrusion temperature of the double-screw extruder is 180 ℃.
The performance characterization is that the right-angle tearing strength of the maleic anhydride grafted polyglycolide copolymer material is 262KN/m, the elongation at break is 18 percent, the glass transition temperature is 63 ℃, the molecular weight of the polymer is 1.82 multiplied by 10 5, and the maleic anhydride grafting rate of the polymer is 28.9 percent measured by a chemical titration method. The presence of terminal hydroxyl groups was measured by chemical titration.
Example 2
(1) Adding glycolide and maleic anhydride into a reaction kettle, adding an initiator dicumyl peroxide, and carrying out constant-temperature reaction under the condition of nitrogen flow and vacuumizing to obtain maleic anhydride grafted glycolide. The grafting modification reaction temperature is 100 ℃, the reaction pressure is 35kpa, the reaction time is 3h, the gas flow rate protected by the nitrogen flow is 2.5m/s, the maleic anhydride is 145% of the glycolide and the dicumyl peroxide is 0.6% of the glycolide based on the weight of the glycolide.
(2) Removing the glycolide which does not participate in the grafting reaction in the step (1) by adopting a reduced pressure distillation mode to obtain purified maleic anhydride grafted glycolide (MA-GA), wherein the reduced pressure distillation temperature is 130 ℃, the pressure is 15kpa, and the time is 2.5h.
(3) And (2) under the action of a catalyst and an initiator, adding nitrogen flow and negative pressure, carrying out low-temperature prepolymerization on the maleic anhydride grafted glycolide (MA-GA) obtained in the step (2) to obtain an MA-GA oligomer, wherein the reaction temperature of the low-temperature prepolymerization is 135 ℃, the reaction time is 4 hours, the reaction pressure is 350kpa, the GAs flow rate protected by the nitrogen flow is 3m/s, the weight of the maleic anhydride grafted glycolide (MA-GA) is 0.6% of that of the catalyst stannous octoate, and the initiator triphenylphosphine is 0.25% of that of the MA-GA.
(4) Adding the MA-GA oligomer obtained in the step (3) into a double-screw extruder for polymerization reaction, adding an antioxidant, and carrying out high-temperature reactive mixing extrusion granulation to obtain the maleic anhydride grafted polyglycolide copolymer material (MA-PGA), wherein the weight of the antioxidant triphenyl phosphite is 0.6% of that of the MA-GA oligomer, and the reactive mixing extrusion granulation reaction extrusion temperature of the double-screw extruder is 180 ℃.
The performance characterization is that the right-angle tearing strength of the maleic anhydride grafted polyglycolide copolymer material is 270KN/m, the breaking elongation is 21 percent, the glass transition temperature is 65 ℃, the molecular weight of the polymer is 2.05X10 5, and the maleic anhydride grafting rate of the polymer is 31.5 percent measured by a chemical titration method. The presence of terminal hydroxyl groups was measured by chemical titration.
Example 3
(1) Adding glycolide and maleic anhydride into a reaction kettle, adding an initiator dicumyl peroxide, and carrying out constant-temperature reaction under the condition of nitrogen flow and vacuumizing to obtain maleic anhydride grafted glycolide. The grafting modification reaction temperature is 100 ℃, the reaction pressure is 40kpa, the reaction time is 3h, the gas flow rate protected by nitrogen flow is 3m/s, and the maleic anhydride is 150% of the glycolide and the dicumyl peroxide is 0.65% of the glycolide based on the weight of the glycolide.
(2) Removing the glycolide which does not participate in the grafting reaction in the step (1) by adopting a reduced pressure distillation mode to obtain purified maleic anhydride grafted glycolide (MA-GA), wherein the reduced pressure distillation temperature is 130 ℃, the pressure is 20kpa, and the time is 3h.
(3) And (2) under the action of a catalyst and an initiator, adding nitrogen flow and negative pressure simultaneously, carrying out low-temperature prepolymerization to obtain an MA-GA oligomer, wherein the reaction temperature of the low-temperature prepolymerization is 135 ℃, the reaction time is 4.5h, the reaction pressure is 350kpa, the GAs flow rate protected by the nitrogen flow is 3.5m/s, the weight of the maleic anhydride grafted glycolide (MA-GA) is 0.65% of that of the MA-GA, and the weight of the catalyst stannous octoate is 0.3% of that of the MA-GA.
(4) Adding the MA-GA oligomer obtained in the step (3) into a double-screw extruder for polymerization reaction, adding an antioxidant, and carrying out high-temperature reactive mixing extrusion granulation to obtain the maleic anhydride grafted polyglycolide copolymer material (MA-PGA), wherein the weight of the antioxidant triphenyl phosphite is 0.6% of that of the MA-GA oligomer, and the reactive mixing extrusion granulation reaction extrusion temperature of the double-screw extruder is 185 ℃.
The performance characterization is that the right-angle tear strength of the maleic anhydride grafted polyglycolide copolymer material is 278KN/m, the elongation at break is 23%, the glass transition temperature is 68 ℃, the molecular weight of the polymer is 2.26 multiplied by 10 5, and the maleic anhydride grafting rate of the polymer is 35.7% measured by a chemical titration method. The presence of terminal hydroxyl groups was measured by chemical titration.
Example 4
(1) Adding glycolide and maleic anhydride into a reaction kettle, adding an initiator dicumyl peroxide, and carrying out constant-temperature reaction under the condition of nitrogen flow and vacuumizing to obtain maleic anhydride grafted glycolide. The grafting modification reaction temperature is 105 ℃, the reaction pressure is 45kpa, the reaction time is 3.5h, the gas flow rate protected by the nitrogen flow is 3m/s, the maleic anhydride is 155% of the glycolide and the dicumyl peroxide is 0.7% of the glycolide based on the weight of the glycolide.
(2) Removing the glycolide which does not participate in the grafting reaction in the step (1) by adopting a reduced pressure distillation mode to obtain purified maleic anhydride grafted glycolide (MA-GA), wherein the reduced pressure distillation temperature is 130 ℃, the pressure is 25kpa, and the time is 3.5h.
(3) And (2) under the action of a catalyst and an initiator, adding nitrogen flow and negative pressure simultaneously, carrying out low-temperature prepolymerization to obtain an MA-GA oligomer, wherein the reaction temperature of the low-temperature prepolymerization is 140 ℃, the reaction time is 4.5h, the reaction pressure is 350kpa, the GAs flow rate protected by the nitrogen flow is 3.5m/s, the weight of the maleic anhydride grafted glycolide (MA-GA) is 0.75% of that of the MA-GA, and the weight of the catalyst stannous octoate is 0.35% of that of the MA-GA.
(4) Adding the MA-GA oligomer obtained in the step (3) into a double-screw extruder for polymerization reaction, adding an antioxidant, and carrying out high-temperature reactive mixing extrusion granulation to obtain the maleic anhydride grafted polyglycolide copolymer material (MA-PGA), wherein the weight of the antioxidant triphenyl phosphite is 0.65% of that of the MA-GA oligomer, and the reactive mixing extrusion granulation reaction extrusion temperature of the double-screw extruder is 185 ℃.
The performance characterization is that the right-angle tearing strength of the maleic anhydride grafted polyglycolide copolymer material is measured to be 286KN/m, the breaking elongation is 26 percent, the glass transition temperature is 69 ℃, the molecular weight of the polymer is 2.51 multiplied by 10 5, and the maleic anhydride grafting rate of the polymer is measured to be 38.2 percent by a chemical titration method. The presence of terminal hydroxyl groups was measured by chemical titration.
Example 5
(1) Adding glycolide and maleic anhydride into a reaction kettle, adding an initiator dicumyl peroxide, and carrying out constant-temperature reaction under the condition of nitrogen flow and vacuumizing to obtain maleic anhydride grafted glycolide. The grafting modification reaction temperature is 110 ℃, the reaction pressure is 55kpa, the reaction time is 4h, the gas flow rate protected by nitrogen flow is 4m/s, the maleic anhydride is 160% of the glycolide and the dicumyl peroxide is 0.8% of the glycolide based on the weight of the glycolide.
(2) Removing the glycolide which does not participate in the grafting reaction in the step (1) by adopting a reduced pressure distillation mode to obtain purified maleic anhydride grafted glycolide (MA-GA), wherein the reduced pressure distillation temperature is 135 ℃, the pressure is 30kpa, and the time is 3.5h.
(3) And (2) under the action of a catalyst and an initiator, adding nitrogen flow and negative pressure, carrying out low-temperature prepolymerization on the maleic anhydride grafted glycolide (MA-GA) obtained in the step (2) to obtain an MA-GA oligomer, wherein the reaction temperature of the low-temperature prepolymerization is 140 ℃, the reaction time is 5h, the reaction pressure is 400kpa, the GAs flow rate protected by the nitrogen flow is 4m/s, the weight of the maleic anhydride grafted glycolide (MA-GA) is 0.8% of that of the catalyst stannous octoate, and the initiator triphenylphosphine is 0.4% of that of the MA-GA.
(4) Adding the MA-GA oligomer obtained in the step (3) into a double-screw extruder for polymerization reaction, adding an antioxidant, and carrying out high-temperature reactive mixing extrusion granulation to obtain the maleic anhydride grafted polyglycolide copolymer material (MA-PGA), wherein the weight of the antioxidant triphenyl phosphite is 0.7% of that of the MA-GA oligomer, and the reactive mixing extrusion granulation reaction extrusion temperature of the double-screw extruder is 190 ℃.
The performance characterization is that the right-angle tearing strength of the maleic anhydride grafted polyglycolide copolymer material is 272KN/m, the breaking elongation is 21.6 percent, the glass transition temperature is 66.5 ℃, the molecular weight of the polymer is 2.11 multiplied by 10 5, and the maleic anhydride grafting rate of the polymer is 32.3 percent by a chemical titration method. The presence of terminal hydroxyl groups was measured by chemical titration.
Comparative example 1
The copolymer is prepared by polymerizing glycolide and then grafting:
(1) Under the action of catalyst and initiator, glycolide is prepolymerized at low temperature under the condition of nitrogen flow and negative pressure to obtain oligomer. The reaction temperature of the low-temperature prepolymerization is 130 ℃, the reaction time is 3 hours, the reaction pressure is 300kPa, the flow rate of nitrogen flow is 3m/s, the adding amount of the catalyst stannous octoate is 0.5wt% of the using amount of glycolide based on the weight of glycolide, and the adding amount of the initiator triphenylphosphine is 0.2wt% of the using amount of glycolide.
(2) Adding the oligomer prepared in the step (1) into a double-screw extruder for polymerization, adding maleic anhydride and an antioxidant, performing high-temperature reactive mixing extrusion granulation, and finally obtaining a grafted polymer, wherein the addition amount of the maleic anhydride is 15wt% of the dosage of the oligomer (and the grafting rate is not improved even if the addition amount of the maleic anhydride is continuously increased according to the experiment of the inventor), the addition amount of the antioxidant triphenyl phosphite is 0.5wt% of the dosage of the oligomer, and the reactive mixing extrusion granulation reaction extrusion temperature of the double-screw extruder is 180 ℃.
The product performance is that the right-angle tear strength of the copolymer material is 182KN/m, the elongation at break is 9%, the glass transition temperature is 48 ℃, the molecular weight of the polymer is 1.68 multiplied by 10 5, the grafting rate of maleic anhydride of the polymer is 1.3% by a chemical titration method, and the existence of hydroxyl end groups cannot be detected by the chemical titration method.
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| CN202310813496.3A CN119264391A (en) | 2023-07-05 | 2023-07-05 | A polyglycolide graft copolymer and its preparation method and application |
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| CN202310813496.3A CN119264391A (en) | 2023-07-05 | 2023-07-05 | A polyglycolide graft copolymer and its preparation method and application |
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