CN115232297A - Polyglycolic acid/aliphatic polycarbonate triblock copolymer and preparation method thereof - Google Patents
Polyglycolic acid/aliphatic polycarbonate triblock copolymer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention belongs to the technical field of polyglycolic acid copolymerization, and particularly relates to a polyglycolic acid/aliphatic polycarbonate triblock copolymer and a preparation method thereof, wherein the preparation method comprises the following steps: (1) In an inert atmosphere, carrying out ester exchange reaction on a carbonic diester and aliphatic diol in the presence of a catalyst i; then, continuously performing tackifying reaction under the absolute pressure of 0.02-20 kPa to obtain prepolymer A of hydroxyl-terminated high molecular weight aliphatic carbonate; (2) In an inert atmosphere, mixing the obtained prepolymer A with glycolide, and carrying out ring-opening polycondensation reaction in the presence of a ring-opening polymerization catalyst to obtain the triblock copolymer with the structure shown in the formula I. The method of the invention can improve the processability of the copolymer material, adjust the degradation speed and improve the toughness of the copolymer material, and the obtained copolymer has high molecular weight, strong toughness and biodegradability.
Description
Technical Field
The invention belongs to the technical field of polyglycolic acid copolymerization, and particularly relates to a polyglycolic acid/aliphatic polycarbonate triblock copolymer and a preparation method thereof.
Background
Plastics are one of the most important materials in the modern chemical industry and are widely applied to various fields of life. The plastic is energy-intensive and emission-intensive in manufacturing, meanwhile, the plastic is low in recycling rate and large in environmental pollution, can be degraded in a natural environment state for hundreds of years, and not only occupies a large amount of land resources, but also pollutes water and air in the degradation process. Therefore, the development of biodegradable green plastics has received much attention, and the development of novel biodegradable plastics is also an important matter for the development of the plastic industry in future.
Polyglycolic acid (PGA) is a biodegradable high-crystallinity aliphatic polyester, and the final degradation products are water and carbon dioxide, which have excellent mechanical properties, gas barrier properties, and biocompatibility due to its excellent crystallization properties and segment structural characteristics, and thus is widely used in the biomedical and ecological fields. However, PGA also has disadvantages such as high product price, poor product toughness, high product processing difficulty, short product shelf life, high product density, etc., which limit large-scale production expansion and popularization, and need to be deeply studied and solved.
The aliphatic polycarbonate is also an important biodegradable high polymer material, has the characteristics of moderate biodegradation speed, good biocompatibility and excellent toughness, and is widely concerned by people; the structure is adjustable, the product color is good, the catalyst consumption is small, the polymerization process is simple, and the method has good industrial prospect. The thermodynamic properties and mechanical properties of the aliphatic polycarbonate and the PGA are naturally complementary, and the copolymerization modification of the PGA and the aliphatic polycarbonate is an effective way to solve the above problems of the PGA. At present, the industrialized PGA adopts a method of glycolide ring-opening polymerization, and the ring-opening copolymerization has the advantages of small catalyst consumption, excellent product thermal properties and high copolymer molecular weight, but also has the disadvantages of high raw material cost and few types, which limits the scale-up of the PGA and aliphatic polycarbonate to a certain extent, and can improve the performance of the PGA and aliphatic polycarbonate while effectively reducing the raw material cost.
However, due to the structural difference between the carbonate group and the glycolide, the glycolide is difficult to directly react with the polycarbonate through ring-opening polymerization to obtain a copolymer with high molecular weight, thereby greatly limiting the application of the method.
It is a worthy of research to solve the problem that the prior industrial production mode of polyglycolic acid is glycolide ring-opening polymerization, how to prepare a glycolic acid copolymer which has excellent performance and can be used independently can be matched with the prior industrial production mode to the maximum extent.
The invention aims to design and prepare a triblock polyglycolic acid/aliphatic polycarbonate copolymer, can effectively reduce the production cost and reduce the subsequent industrial amplification difficulty, and the preparation method is mainly used for preparing a high molecular weight polyglycolic acid/aliphatic polycarbonate triblock copolymer by firstly preparing a high molecular weight aliphatic polycarbonate prepolymer with modified terminal groups and then performing ring-opening polymerization with glycolide.
Disclosure of Invention
The invention aims to provide a polyglycolic acid/aliphatic polycarbonate triblock copolymer and a preparation method thereof, aiming at the defects of the prior art, the glycolide and the aliphatic polycarbonate prepolymer with high molecular weight are subjected to copolymerization modification to prepare the copolymer, the processability of the copolymer material is improved, the degradation speed of the material is adjusted, the toughness of the copolymer material is improved, and the defects of low melting point and poor mechanical property when the aliphatic polycarbonate is used alone are overcome; the method can effectively reduce the cost, so as to prepare the biodegradable high-performance polymer material.
In order to realize the purpose, the invention adopts the following technical scheme:
in a first aspect, a polyglycolic acid/aliphatic polycarbonate triblock copolymer is provided, the triblock copolymer has a structure shown in formula I, and comprises an aliphatic polycarbonate repeating unit structure located in a middle chain segment and a polyglycolic acid repeating unit structure located in two end chain segments (i.e., the chain segment located in the middle is the aliphatic polycarbonate repeating unit structure, and the chain segments located at two ends are the polyglycolic acid repeating unit structures):
in the formula:
p is an integer from 2 to 12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11),
m is an integer of 300 or more (e.g., 320, 340, 360, 400, 600, 800, 1000, 1500), for example, m can be 300 or more and 1000 or less,
n is an integer greater than or equal to 300 (e.g., 320, 340, 360, 400, 600, 800, 1000, 1500), for example, n can be greater than or equal to 300 and less than or equal to 1000,
q is an integer of 200 or more (e.g., 220, 240, 300, 400, 600, 800, 1000, 1500, 2000), for example, q may be 200 or more and 1500 or less.
In accordance with the polyglycolic acid/aliphatic polycarbonate triblock copolymers provided herein, in some embodiments, the mass fraction of polyglycolic acid repeating units is 5 to 95% (e.g., 6%, 8%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 92%) based on the total mass (e.g., 100 wt%) of the triblock copolymer; the aliphatic polycarbonate repeating unit has a mass fraction of 5 to 95% (e.g., 6%, 8%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 92%).
In some embodiments, the polyglycolic acid/aliphatic polycarbonate triblock copolymer has a melt index (at 230 ℃, 2.16kg temperature and pressure) of 5 to 50g/10min (e.g., 8g/10min, 12g/10min, 15g/10min, 20g/10min, 30g/10min, 40g/10min, 45g/10 min), preferably 10 to 35g/10min.
In a second aspect, there is provided a process for the preparation of a polyglycolic acid/aliphatic polycarbonate triblock copolymer as described above, comprising the steps of:
(1) In an inert atmosphere, carrying out ester exchange reaction on carbonic diester and aliphatic diol in the presence of a catalyst i; then, a certain degree of vacuum is established, the absolute pressure of the system is controlled to be 0.02kPa to 20kPa (for example, 0.04kPa, 0.08kPa, 0.15kPa, 0.2kPa, 0.4kPa, 0.6kPa, 0.8 kPa), preferably 0.1kPa to 1kPa, and the thickening reaction is continued for 1 to 10 hours (for example, 1.5 hours, 2.0 hours, 3 hours, 5 hours, 8 hours, 9 hours) under the conditions to obtain prepolymer A of the hydroxyl group-terminated high molecular weight aliphatic polycarbonate;
(2) The aliphatic polycarbonate prepolymer A thus obtained was mixed with glycolide in an inert atmosphere, and subjected to a ring-opening polycondensation reaction in the presence of a ring-opening polymerization catalyst to obtain a polyglycolic acid/aliphatic polycarbonate triblock copolymer.
According to the preparation method provided by the present invention, in some embodiments, the prepolymer A of high molecular weight aliphatic polycarbonate obtained in step (1) may have a structure represented by formula II:
wherein p is an integer from 2 to 12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10);
q is an integer of 200 or more (e.g., 220, 240, 300, 400, 600, 800, 1000, 1500, 2000), and for example, q may be 200 or more and 1500 or less.
According to the preparation method provided by the present invention, in some embodiments, the molecular weight of the prepolymer A of the high molecular weight aliphatic polycarbonate obtained in the step (1) may be 20k to 200k (e.g., 25k, 30k, 40k, 50k, 60k, 80k, 100k, 120k, 150k, 180 k). By controlling the pressure of the system within a certain range and/or controlling the time of the vacuum thickening reaction, prepolymer A of high molecular weight aliphatic polycarbonate can be obtained.
According to the production method provided by the present invention, in some embodiments, in step (1), the feeding molar ratio of the carbonic acid diester to the aliphatic diol is 2. In the present invention, the carbonic acid diester is polymerized as a monomer, and the amount of the carbonic acid diester added is large and can be adjusted within a large range of the amount (for example, the content of the aliphatic polycarbonate repeating units derived therefrom in the copolymer can be made 5 to 95%).
In some embodiments, in step (2), the charging mass ratio of the aliphatic polycarbonate prepolymer a to glycolide is 1.
The molecular weight of the polyglycolic acid/aliphatic polycarbonate triblock copolymer provided by the present invention can be obtained by theoretical calculation based on the molecular weight of the prepolymer (PBC segment) of the aliphatic polycarbonate in the copolymer and the charge ratio thereof in the ring-opening polymerization step. For example, the weight average molecular weight of the polyglycolic acid/aliphatic polycarbonate triblock copolymer may be in the range of 5.0 × 10 4 ～3.0×10 5 (e.g., 5.5X 10) 4 、6.0×10 4 、8.0×10 4 、1.2×10 5 、1.5×10 5 、2.0×10 5 、2.8×10 5 )。
According to the preparation method provided by the present invention, in some embodiments, the carbonic acid diester is selected from one or more of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ditolyl carbonate and dinaphthyl carbonate, preferably selected from one or more of dimethyl carbonate, diethyl carbonate and diphenyl carbonate.
In some embodiments, the aliphatic diol is selected from one or more of linear or branched aliphatic diols having 2 to 6 carbon atoms, preferably from one or more of 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol.
In some embodiments, the catalyst i in step (1) is selected from at least one of a metal acetylacetone complex, a titanium-based organic compound, an alkoxy metal compound, a metal acetate, a metal carbonate, a metal bicarbonate, a tin-based organic compound, a metal phosphite, a metal hydride, a metal hydroxide, a metal oxide, a tertiary amine, and a metal halide; the catalyst i, for example, may be selected from, but not limited to, one or more of lithium acetylacetonate, potassium acetylacetonate, magnesium acetylacetonate, zinc acetylacetonate, tetraethoxytitanium, tetraisopropyl titanate, tetrabutyl titanate, lithium methoxide, sodium methoxide, potassium methoxide, lithium acetate, sodium acetate, potassium acetate, zinc acetate, magnesium acetate, manganese acetate, potassium carbonate, sodium carbonate, magnesium carbonate, stannous chloride, stannic chloride, sodium phosphite, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, a silica/titanium dioxide complex, trimethylamine, triethylamine, calcium chloride, magnesium chloride, and zinc chloride.
In one embodiment, the ring-opening polymerization catalyst of step (2) is selected from one or more of an organometallic compound or oxide or complex of titanium, an organometallic compound or oxide or complex of tin, an organometallic compound or oxide or complex of zinc, an organometallic compound or oxide or complex of cobalt, or an organometallic compound or oxide or complex of bismuth; the ring-opening polymerization catalyst, for example, may be selected from, but is not limited to, one or more of titanium dioxide, a silica/titanium dioxide complex, titanium glycol, tetraisopropyl titanate, tetrabutyl titanate, dibutyltin dilaurate, stannous octoate, stannous chloride, dibutyltin oxide, zinc acetate, cobalt oxide, cobalt acetate, bismuth oxide, and bismuth acetate.
In the step (1), the system is heated to the initial reaction temperature, stirred and reacted for a period of time (for example, 1 to 5 hours) to perform the ester exchange reaction, and then the temperature is gradually raised to the final reaction temperature so as to completely evaporate the byproducts generated in the reaction in the system; then a certain vacuum degree is built up again and the tackifying reaction is continued for a period of time under the condition.
In one embodiment, the process conditions for the reaction of step (1) comprise:
the transesterification reaction is carried out under stirring and heating, and the initial reaction temperature is 70 to 160 ℃ (for example, 80 ℃, 95 ℃, 110 ℃, 120 ℃, 140 ℃, 155 ℃), preferably 90 to 150 ℃; the final reaction temperature is 160 to 210 ℃ (for example, 165 ℃, 180 ℃, 190 ℃, 205 ℃), preferably 170 to 200 ℃;
the total time of the transesterification reaction and the subsequent vacuum thickening reaction is 2 to 20 hours (for example, 2.5 hours, 5 hours, 8 hours, 10 hours, 14 hours, 16 hours, 18 hours), and preferably 3 to 12 hours.
In one embodiment, the process conditions for the ring-opening polycondensation reaction of step (2) comprise: the reaction temperature is 160 to 240 ℃ (for example, 165 ℃, 180 ℃, 200 ℃,210 ℃, 230 ℃), preferably 180 to 220 ℃; the reaction time is 0.5 to 24 hours (e.g., 1.5 hours, 2.5 hours, 5 hours, 8 hours, 10 hours, 14 hours, 16 hours, 18 hours, 22 hours), preferably 1 to 12 hours.
In one embodiment, in step (1), the amount of the catalyst i used is 10% by mass based on the mass of the aliphatic diol -7 % to 1% (e.g., 10) -6 ％、10 -5 ％、10 -4 ％、10 -3 ％、10 -2 %, 0.1%, 0.3%, 0.6%, 0.8%), preferably 10% -7 ％～0.4％。
In one embodiment, in step (2), the amount of said ring-opening polycondensation catalyst used is 10 parts of the theoretical yield-corresponding mass of the triblock copolymer prepared -7 % to 1% (e.g., 10) -6 ％、10 -5 ％、10 -4 ％、10 -3 ％、10 -2 ％、0.1％、0.2％、0.4％、0.6％、0.8％)。
According to the invention, aliphatic diol is selected to carry out hydroxyl end capping on carbonic diester to obtain a high molecular weight aliphatic polycarbonate prepolymer with modified end groups, and then the prepolymer is subjected to ring-opening polymerization with glycolide, so that the defect that the preparation of a high molecular weight copolymer by the ring-opening polymerization reaction of the glycolide and the polycarbonate is difficult to realize due to the structural difference between the carbonate group and the glycolide can be overcome, and the high molecular weight polyglycolic acid/aliphatic polycarbonate triblock copolymer is finally prepared. By adopting the reaction idea of the invention, the advantages of each component of the copolymer can be kept, so that the provided polyglycolic acid/aliphatic polycarbonate triblock copolymer has the advantages of high molecular weight, good toughness, biodegradability and low industrial amplification difficulty, the application range of the triblock copolymer is widened, and the triblock copolymer can be used for preparing polymer blends, films, packaging materials, medical materials, drug carriers and the like.
In the method, the high molecular weight polyglycolic acid/aliphatic polycarbonate triblock copolymer is prepared by ring-opening polymerization of the prepared end group modified high molecular weight aliphatic polycarbonate prepolymer and glycolide, no solvent is used in the process, the obtained product with safety, no toxicity, safety, environmental protection and excellent performance can be independently used as a material, has the advantages of high degree of engagement with an industrialized mode and low subsequent industrialization difficulty, and shows potential application prospects in the aspects of green packaging, biological materials, consumer products, building materials and the like.
Drawings
FIG. 1 shows a nuclear magnetic spectrum of a hydroxyl-terminated aliphatic polycarbonate prepolymer of high molecular weight obtained in example 5.
Note: a hydroxyl-terminated high molecular weight aliphatic polycarbonate prepolymer having a molecular weight calculated by the formula:
M＝116n+206；
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
< test methods >
Melt index: 5g of the polyglycolic acid/aliphatic polycarbonate triblock copolymer to be tested was placed in the cavity of a melt index tester and tested at 230 ℃ under 2.16kg temperature and pressure according to test standard GB/T3682-2000 (the copolymer could not be dissolved and its intrinsic viscosity or molecular weight could not be directly tested, so its melt index was tested for characterization).
Degradation rate: adding 10ml of water and 2g of a polymer sample to be detected into a closed container, and placing the container in a constant temperature and humidity box at 37 ℃ for 30 days; drying and weighing to obtain the mass of the undegraded product;
the degradation rate calculation method comprises the following steps: (2-undegraded mass)/2 x 100%.
Elongation at break: the tests were carried out on a universal tester (Instron 1122, UK) according to standard ISO527 (2012), with sample sizes of 80X 4X 2mm. During testing, the moving speed of the clamp beam is 20mm/min.
< sources of raw materials >
Dimethyl carbonate, annagi chemical Co., ltd;
1, 3-propanediol, beijing chemical company;
1, 4-butanediol, beijing Chemicals Inc.;
1, 5-pentanediol, beijing Chemicals Inc.;
sodium methoxide, saen chemical technology limited;
zinc acetate, available from welfare technologies;
magnesium hydroxide, available from carbofuran technologies;
potassium acetylacetonate, available from carbofuran technologies;
sodium carbonate, annagi chemical Co., ltd;
lithium methoxide, annagi chemical Co., ltd;
manganese acetate, annagiki chemical Co., ltd;
glycolide, beijing Yinaoka science and technology, inc.;
tetrabutyl titanate, ibyo enoki technologies ltd;
stannous chloride, ibjing enoki technologies ltd;
bismuth oxide, yinaoka technologies ltd, beijing;
cobalt acetate, inc, illinois technologies, beijing;
dibutyl tin dilaurate, beijing Yinaoka technologies, inc.;
dibutyl tin oxide, ibyo inoka technologies ltd;
tetraisopropyl titanate, sahn chemical technologies, ltd;
bismuth acetate, sahn chemical technologies, ltd.
Example 1
(1) In a 500mL glass flask, 153.0g (1.7 mol) of dimethyl carbonate, 90.0g (1.0 mol) of 1, 4-butanediol [ the molar ratio of dimethyl carbonate to 1,4 butanediol is 1.7 ] and 0.02g of sodium methoxide as a catalyst were added under a nitrogen atmosphere, and a reaction was carried out with stirring at 100 ℃ for 1 hour; then gradually raising the temperature to 180 ℃ so as to completely evaporate the byproduct methanol generated by the reaction; then gradually reducing the pressure of the system to 0.2kPa absolute, and continuing to react for 1.2 hours under the condition to obtain a prepolymer A of the aliphatic polycarbonate; calculating the molecular weight of 25k through nuclear magnetic characterization;
(2) Mixing the prepolymer A obtained in the step (1) with glycolide according to a mass ratio of 1;
the product was characterized by a melt index of 13g/10min, an elongation at break of 72% and a degradation of 77%.
Example 2
(1) In a 500mL glass flask, 135.0g (1.5 mol) of dimethyl carbonate, 90.0g (1.0 mol) of 1, 4-butanediol [ the molar ratio of dimethyl carbonate to 1, 4-butanediol is 1.5 ] and 0.12g of zinc acetate as a catalyst were charged under a nitrogen atmosphere, and a stirring reaction was carried out at 90 ℃ for 1.5 hours; then gradually raising the temperature to 190 ℃ so as to completely evaporate the byproduct methanol generated by the reaction; then gradually reducing the pressure of the system to 0.1kPa absolute, and continuing to react for 1.5 hours under the condition to obtain a prepolymer A of the aliphatic polycarbonate; calculating the molecular weight of 30k through nuclear magnetic characterization;
(2) Mixing the prepolymer A obtained in the step (1) with glycolide according to a mass ratio of 1;
the product was characterized by a melt index of 17g/10min, elongation at break of 121% and degradation of 68%.
Example 3
(1) In a 250mL glass flask, 90.0g (1.0 mol) of dimethyl carbonate, 90.0g (1.0 mol) of 1, 4-butanediol [ the molar ratio of dimethyl carbonate to 1, 4-butanediol is 1] and 0.063g of magnesium hydroxide as a catalyst were charged under a nitrogen atmosphere, and a stirring reaction was carried out at 90 ℃ for 1.2 hours; then gradually raising the temperature to 187 ℃ so as to completely evaporate the byproduct methanol generated by the reaction; then gradually reducing the pressure of the system to 0.15kPa absolute, and continuing to react for 2.2 hours under the condition to obtain a prepolymer A of the aliphatic polycarbonate; the molecular weight is calculated to be 39k through nuclear magnetic characterization;
(2) Mixing the prepolymer A obtained in the step (1) with glycolide according to a mass ratio of 1;
the product was characterized by a melt index of 21g/10min, elongation at break of 137% and degradation of 55%.
Example 4
(1) In a 250mL glass flask, 45.0g (0.5 mol) of dimethyl carbonate, 90.0g (1.0 mol) of 1, 4-butanediol [ molar ratio of dimethyl carbonate to 1,4 butanediol is 1] and 0.11g of catalyst potassium acetylacetonate were charged under a nitrogen atmosphere, and a stirring reaction was carried out at 85 ℃ for 1.5 hours; then gradually raising the temperature to 190 ℃ so as to completely evaporate the byproduct methanol generated by the reaction; then gradually reducing the pressure of the system to 0.12kPa, and continuously reacting for 6.5 hours under the condition to obtain a prepolymer A of the aliphatic polycarbonate; calculating the molecular weight of 94k through nuclear magnetic characterization;
(2) Mixing the prepolymer A obtained in the step (1) with glycolide according to a mass ratio of 1, adding the mixture into a 250mL glass flask, adding a ring-opening polycondensation catalyst of cobalt acetate (the dosage is 0.016wt% of the corresponding mass of the theoretical yield of the prepared triblock copolymer), and reacting at 215 ℃ for 2 hours in a nitrogen atmosphere to obtain a polyglycolic acid/aliphatic polycarbonate triblock copolymer;
the product was characterized by a melt index of 16g/10min, elongation at break of 146% and degradation of 51%.
Example 5
(1) In a 500mL glass flask, 45.0g (0.5 mol) of dimethyl carbonate, 114.0g (1.5 mol) of 1, 3-propanediol [ the molar ratio of dimethyl carbonate to 1, 3-propanediol is 1] and 0.2g of sodium carbonate as a catalyst were charged under a nitrogen atmosphere, and a stirring reaction was carried out at 90 ℃ for 1 hour; then gradually raising the temperature to 195 ℃ so as to completely evaporate the byproduct methanol generated by the reaction; then gradually reducing the pressure of the system to 0.2kPa absolute pressure, and continuing to react for 6 hours under the condition to obtain a prepolymer A of the aliphatic polycarbonate; by nuclear magnetic characterization, the molecular weight was calculated to be 90k as shown in fig. 1;
(2) Mixing the prepolymer A obtained in the step (1) with glycolide according to a mass ratio of 3, adding the mixture into a 250mL glass flask, adding dibutyltin dilaurate serving as a ring-opening polycondensation catalyst (the using amount is 0.02wt% of the corresponding mass of the theoretical yield of the prepared triblock copolymer), and reacting at 223 ℃ for 2.2 hours in a nitrogen atmosphere to obtain a polyglycolic acid/aliphatic polycarbonate triblock copolymer;
the product was characterized by a melt index of 26g/10min, elongation at break of 153% and degradation of 46%.
Example 6
(1) In a 500mL glass flask, 45.0g (0.5 mol) of dimethyl carbonate, 152.0g (2.0 mol) of 1, 3-propanediol [ the molar ratio of dimethyl carbonate to 1, 3-propanediol is 1] and 0.06g of lithium methoxide as a catalyst were charged under a nitrogen atmosphere, and a stirring reaction was carried out at 92 ℃ for 1.3 hours; then gradually raising the temperature to 195 ℃ so as to completely evaporate the byproduct methanol generated by the reaction; then gradually reducing the pressure of the system to 0.15kPa, and continuously reacting for 5 hours under the condition to obtain a prepolymer A of the aliphatic polycarbonate; calculating the molecular weight of 82k through nuclear magnetic characterization;
(2) Mixing the prepolymer A obtained in the step (1) with glycolide according to a mass ratio of 5;
the product was characterized by a melt index of 29g/10min, elongation at break of 208% and degradation of 35%.
Example 7
(1) In a 500mL glass flask, 45.0g (0.5 mol) of dimethyl carbonate, 260.0g (2.5 mol) of 1, 5-pentanediol [ the molar ratio of dimethyl carbonate to 1, 5-pentanediol is 1] and 0.1g of manganese acetate as a catalyst were charged under a nitrogen atmosphere, and a stirring reaction was carried out at 82 ℃ for 1.1 hours; then gradually raising the temperature to 190 ℃ so as to completely evaporate the byproduct methanol generated by the reaction; then gradually reducing the pressure of the system to 0.1kPa absolute, and continuing to react for 4 hours under the condition to obtain a prepolymer A of the aliphatic polycarbonate; calculating the molecular weight of 80k through nuclear magnetic characterization;
(2) Mixing the prepolymer A obtained in the step (1) with glycolide according to a mass ratio of 8, adding the mixture into a 250mL glass flask, adding a polycondensation catalyst of tetraisopropyl titanate (the dosage is 0.019wt% of the corresponding mass of the theoretical yield of the prepared triblock copolymer), and reacting at 226 ℃ for 2.3 hours in a nitrogen atmosphere to obtain a polyglycolic acid/aliphatic polycarbonate triblock copolymer;
the product was characterized by a melt index of 30g/10min, an elongation at break of 359% and a degradation of 28%.
Example 8
(1) In a 5L reactor, 450.0g (5 mol) of dimethyl carbonate, 2250.0g (25 mol) of 1, 4-butanediol [ molar ratio of dimethyl carbonate to 1, 4-butanediol is 1] and 0.67g of catalyst potassium acetylacetonate were charged under a nitrogen atmosphere, and a stirring reaction was carried out at 79 ℃ for 1.6 hours; then gradually raising the temperature to 195 ℃ so as to completely evaporate the byproduct methanol generated by the reaction; then gradually reducing the pressure of the system to 0.11kPa absolute, and continuing to react for 5.6 hours under the condition to obtain a prepolymer A of the aliphatic polycarbonate; calculating the molecular weight of the molecular weight material by nuclear magnetic characterization;
(2) Mixing the prepolymer A obtained in the step (1) with glycolide according to a mass ratio of 1, adding the mixture into a 5L reaction kettle, adding a ring-opening polycondensation catalyst bismuth acetate (the use amount is 0.023wt% of the corresponding mass of the theoretical yield of the prepared triblock copolymer), and reacting at 218 ℃ for 2.5 hours in a nitrogen atmosphere to obtain a polyglycolic acid/aliphatic polycarbonate triblock copolymer;
the product was characterized by a melt index of 19g/10min, elongation at break of 143% and degradation of 53%.
Comparative example 1
(1) In a 250mL glass flask, 116g (1.0 mol) of glycolide and 0.0202g (0.0001 mol) of 1, 12-dodecyl glycol are added under nitrogen atmosphere, stirring reaction is carried out for 15 minutes at 150 ℃, then 0.0081g of stannous octoate is added, the temperature is gradually raised to 230 ℃, ring-opening polymerization reaction is carried out for 30 minutes, and a polyglycolic acid product is obtained;
the product was characterized by a melt index of 11g/10min, an elongation at break of 3% and a degradation of 100%.
TABLE 1 results of product Properties test of each example and comparative example
According to the invention, the glycolide and the high molecular weight aliphatic polycarbonate prepolymer obtained after prepolymerization are subjected to copolymerization modification, so that the processability of the copolymer material can be improved, the degradation speed of the material can be adjusted, the toughness of the copolymer material can be improved, and the method can effectively reduce the cost. The experimental result shows that the invention firstly solves the problem that glycolide can not be directly polymerized with polycarbonate by ring opening, and successfully prepares the polyglycolic acid/aliphatic polycarbonate triblock copolymer with high molecular weight (low melt index); meanwhile, the molecular weight of the obtained prepolymer is correspondingly increased along with the prolonging of the vacuum tackifying reaction time, the degradation speed and toughness of the copolymer are obviously improved after the high molecular weight aliphatic polycarbonate is introduced, the degradation rate of the copolymer in the same time period is correspondingly reduced along with the increasing of the content of the aliphatic polycarbonate, the elongation at break is correspondingly increased, and the purpose of improving the degradation speed and toughness of the material is achieved.
While embodiments of the present invention have been described above, the above description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the spirit of the invention.
Claims (10)
1. A polyglycolic acid/aliphatic polycarbonate triblock copolymer is characterized in that the triblock copolymer has a structure shown as a formula I and comprises an aliphatic polycarbonate repeating unit structure positioned in a middle chain segment and a polyglycolic acid repeating unit structure positioned in two end chain segments:
wherein p is an integer of 2 to 12, m is an integer of 300 or more, n is an integer of 300 or more, and q is an integer of 200 or more.
2. The polyglycolic acid/aliphatic polycarbonate triblock copolymer according to claim 1, wherein the mass fraction of the polyglycolic acid repeating unit is 5 to 95% based on the total mass of the triblock copolymer; the mass fraction of the aliphatic polycarbonate repeating unit is 5 to 95%.
3. The polyglycolic acid/aliphatic polycarbonate triblock copolymer according to claim 1, which has a melt index of 5 to 50g/10min, preferably 10 to 35g/10min.
4. The process for preparing a polyglycolic acid/aliphatic polycarbonate triblock copolymer according to any one of claims 1 to 3, comprising the steps of:
(1) In an inert atmosphere, carrying out ester exchange reaction on a carbonic diester and aliphatic diol in the presence of a catalyst i; then establishing a certain vacuum degree, controlling the absolute pressure of the system to be 0.02 kPa-20 kPa, preferably 0.1 kPa-1 kPa, and continuously thickening and reacting for 1-10 hours under the condition to obtain prepolymer A of hydroxyl-terminated high molecular weight aliphatic polycarbonate;
(2) The prepolymer A of the aliphatic polycarbonate obtained as described above and glycolide were mixed in an inert atmosphere, and a ring-opening polycondensation reaction was carried out in the presence of a ring-opening polymerization catalyst to obtain a polyglycolic acid/aliphatic polycarbonate triblock copolymer.
5. The preparation method according to claim 4, wherein in the step (1), the feeding molar ratio of the carbonic acid diester to the aliphatic diol is 2; and/or
In the step (2), the feeding mass ratio of the aliphatic polycarbonate prepolymer a to glycolide is 1.
6. The method according to claim 4, wherein the carbonic acid diester is selected from one or more of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ditolyl carbonate, and dinaphthyl carbonate, preferably from one or more of dimethyl carbonate, diethyl carbonate, and diphenyl carbonate; and/or
The aliphatic diol is selected from one or more of linear or branched aliphatic diols with 2-6 carbon atoms, preferably from one or more of 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
7. The method according to claim 4, wherein the catalyst i in the step (1) is at least one selected from the group consisting of a metal acetylacetone complex, a titanium-based organic compound, an alkoxy metal compound, a metal acetate, a metal carbonate, a metal bicarbonate, a tin-based organic compound, a metal phosphite, a metal hydride, a metal hydroxide, a metal oxide, a tertiary amine, and a metal halide; preferably selected from one or more of lithium acetylacetonate, potassium acetylacetonate, magnesium acetylacetonate, zinc acetylacetonate, titanium tetraethoxide, tetraisopropyl titanate, tetrabutyl titanate, lithium methoxide, sodium methoxide, potassium methoxide, lithium acetate, sodium acetate, potassium acetate, zinc acetate, magnesium acetate, manganese acetate, potassium carbonate, sodium carbonate, magnesium carbonate, stannous chloride, tin chloride, sodium phosphite, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, a silica/titanium dioxide complex, trimethylamine, triethylamine, calcium chloride, magnesium chloride and zinc chloride; and/or
The ring-opening polymerization catalyst in the step (2) is selected from one or more of organic metal compound or oxide or complex of titanium, organic metal compound or oxide or complex of tin, organic metal compound or oxide or complex of zinc, organic metal compound or oxide or complex of cobalt or organic metal compound or oxide or complex of bismuth; preferably one or more selected from titanium dioxide, a silica/titanium dioxide composite, titanium glycol, tetraisopropyl titanate, tetrabutyl titanate, dibutyltin dilaurate, stannous octoate, stannous chloride, dibutyltin oxide, zinc acetate, cobalt oxide, cobalt acetate, bismuth oxide and bismuth acetate.
8. The preparation method according to claim 4, wherein the process conditions of the reaction of step (1) comprise:
the ester exchange reaction is carried out under the condition of heating and stirring, the initial reaction temperature is 70-160 ℃, and the optimal temperature is 90-150 ℃; the final reaction temperature is 160-210 ℃, and preferably 170-200 ℃;
the total time of the transesterification reaction and the subsequent vacuum-tackifying reaction is 2 to 20 hours, preferably 3 to 12 hours.
9. The production method according to claim 4, wherein the process conditions of the ring-opening polycondensation reaction of step (2) include: the reaction temperature is 160-240 ℃, preferably 180-220 ℃; the reaction time is 0.5 to 24 hours, preferably 1 to 12 hours.
10. The process according to claim 4, wherein in the step (1), the amount of the catalyst i used is 10% by mass based on the mass of the aliphatic diol -7 % to 1%, preferably 10% -7 Percent is 0.4 percent; and/or
In the step (2), the amount of the ring-opening polycondensation catalyst is 10 of the theoretical yield of the prepared triblock copolymer to the corresponding mass -7 ％～1％。
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