CN112608460B - Polyglycolic acid material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a polyglycolic acid material, a preparation method and application thereof, belonging to the technical field of high polymer materials. In the synthesis process of polyglycolic acid, hydrogen bond groups with self-assembly nucleation are introduced at the terminal groups of polyglycolic acid to obtain the terminal functional polyglycolic acid containing one or more hydrogen bond groups. In the process of temperature reduction or constant temperature, polyglycolic acid can generate self-nucleation through the action of hydrogen bonds among hydrogen bond groups, and the polyglycolic acid segment is induced to be rapidly crystallized to obtain the polyglycolic acid with high crystallinity. The novel polyglycolic acid has the characteristics of high crystallization temperature, high crystallization rate, short semicrystallization time and the like, can shorten the molding period, reduce the cost and improve the performance, and has simple preparation method, environmental protection and easy realization of industrialization. Can be widely applied to the fields of packaging, spinning, medical consumables, disposable plastic products or agriculture, and has wide prospect.
Description
Technical Field
The invention relates to a polyglycolic acid material and a preparation method and application thereof, belonging to the technical field of high polymer materials.
Background
The polyglycolic acid (PGA) material has the outstanding advantages of wide raw material source, light weight, good barrier property and the like, and has very wide application prospect in various fields. However, some inherent disadvantages of polyglycolic acid materials (such as brittleness of the materials, poor crystallization performance during molding, large grain size, etc.) limit the wider development and application of polyglycolic acid materials.
At present, the filler is the simplest and most effective method for improving the toughness and the crystallization performance of the polyglycolic acid material, but the added filler is easily dispersed unevenly in a matrix, is easy to agglomerate and has poor compatibility; when the addition amount is high, the mechanical property and the appearance of the product are influenced, and the application is greatly limited. The use of inorganic nucleating agents may also affect the fiber-forming properties of the polymer-containing, especially in the production of ultrafine fibers. The organic carboxylate forms crystal nucleus through the interaction with the terminal ester group containing polymer to induce the crystallization of the ester polymer, thereby increasing the crystallization rate of the polymer. However, the presence of organic carboxylate can cause the molecular weight of the ester polymer to be greatly reduced (degraded), thereby causing the mechanical property of the material to be reduced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a novel polyglycolic acid structure, a preparation method and application thereof.
The first purpose of the invention is to provide a polyglycolic acid material, and the preparation method of the polyglycolic acid material comprises the following steps:
(1) preparation of the hydroxyl-terminated intermediate: synthesizing an intermediate A containing terminal hydroxyl as shown in a formula (III) by reacting diethyl oxalate, an alcohol amine compound and a primary amine compound; or preparing a compound B shown in a formula (IV) by using diethyl oxalate and a diamine compound, and then reacting the compound B shown in the formula (IV) with an alcohol amine compound and a primary amine compound to synthesize an intermediate C containing a terminal hydroxyl group shown in a formula (V);
(2) preparing a polyglycolic acid material: polymerizing the intermediate A containing the terminal hydroxyl group obtained in the step (1) with glycolide to obtain a polyglycolic acid material; or polymerizing the intermediate C containing the terminal hydroxyl group obtained in the step (1) with glycolide to obtain a polyglycolic acid material;
wherein R is1An alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group, a phenyl group or a substituted phenyl group; r2Is a polyglycolic acid chain segment with 40-30000 carbon atoms; n and m are the same or different, and 2n and 2m are integers between 1 and 18.
In one embodiment of the present invention, the polyglycolic acid segment is- (O-CO-CH)2)x-OH, wherein the number of carbon atoms is 40-30000, namely x is 20-15000.
In one embodiment of the present invention, the alcohol amine compound is any one of alcohol amine compounds having 1 to 18 carbon atoms, and has a structure of: NH (NH)2-(CH2-CH2)m-OH; 2m is an integer of 1 to 18.2m is preferably 1 to 12; further, 2m is preferably 2 to 8.
In one embodiment, the alcohol amine compound is selected from any one or more of ethanolamine, propanolamine, butanolamine, hexanolamine, octanolamine, decanolamine, undecanolamine, and dodecanolamine.
In one embodiment of the present invention, the primary amine compound has the structure: r1-NH2Wherein R is1Is an alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group, a phenyl group or a substituted phenyl group. The substituent is selected from halogen, C1-8 straight-chain or branched-chain alkyl, C1-8 straight-chain or branched-chain alkoxy. Further, R1Is alkyl or aryl primary amine with 1-8 carbon atoms.
In one embodiment, the primary amine compound is selected from any one or more of n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, and aniline.
In one embodiment of the present invention, the diamine compound has the structure: NH (NH)2-(CH2-CH2)n-NH2(ii) a 2n is an integer of 1 to 18. Further, 2n is preferably 2 to 8.
In one embodiment, the diamine compound is selected from any one or more of ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, butylenediamine, undecylenediamine, dodecylenediamine, tetradecanediamine, octadecenediamine.
In one embodiment, in both polymerization processes in the step (2), a catalyst is added to promote the polymerization, and the catalyst is at least one of tin catalysts. Stannous octoate and/or stannous iso-octoate are preferred.
In one embodiment, the method further comprises the process of: heating polyglycolic acid material to 1-50 deg.C above the melting temperature, maintaining the temperature for 0.05-5min, and cooling or treating at a constant temperature below the melting point to obtain polyglycolic acid material with high crystallinity.
In one embodiment, during the cooling process or the constant temperature process, polyglycolic acid can perform self-nucleation through hydrogen bonding between hydrogen bonding groups, and induce the polyglycolic acid segment to rapidly crystallize, thereby obtaining polyglycolic acid with high crystallinity.
In one embodiment, the cooling rate of the cooling process is 1-100 ℃/min.
In one embodiment, the constant temperature is 5 to 80 ℃ below the melting temperature of polyglycolic acid.
A second object of the present invention is to provide a polyglycolic acid material having a structure represented by formula (I) or formula (II):
wherein R is1An alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group, a phenyl group or a substituted phenyl group; r2Is a polyglycolic acid chain segment with 40-30000 carbon atoms; n and m are the same or different, and 2n and 2m are integers between 1 and 18.
In one embodiment, R1Preferably an alkyl group having 1 to 8 carbon atoms, a cyclic alkyl group, a phenyl group or a substituted phenyl group.
In one embodiment, 2n is preferably from 2 to 8; 2m is preferably 2 to 8.
In one embodiment, the polyglycolic acid material may be prepared by the above-described method.
In one embodiment, the polyglycolic acid material has a terminal functional group structure with one or more hydrogen bonding groups.
In one embodiment, the polyglycolic acid material of structure (I) may be prepared by the steps of:
(a1) reacting diethyl oxalate, an alcohol amine compound and a monoamine compound to synthesize an intermediate product A, wherein the chemical structure is as follows: r1-NH-C(O)-C(O)-NH-(CH2CH2)m-OH(III)；
(a2) Under the action of catalyst, the intermediate product A initiates the ring-opening polymerization of lactone monomer to obtain a novel polyglycolic acid with chemical structure (I),
wherein R is1An alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group, a phenyl group or a substituted phenyl group; r2Is a polyglycolic acid chain segment with 40-30000 carbon atoms; 2m is an integer of 1 to 18.
In one embodiment, the polyglycolic acid material of structure (II) can be prepared by the following steps:
(b1) reacting diethyl oxalate with diamine compound to synthesize an intermediate product B, wherein the chemical structure is as follows: c2H5O-C(O)-C(O)-NH-(CH2CH2)n-NH-C(O)-C(O)-OC2H5(IV)；
(b2) The intermediate product B, the alcohol amine compound and the monoamine compound react to synthesize a hydroxyl-terminated intermediate product C, and the chemical structure is as follows: r1-NH-C(O)-C(O)-NH-(CH2CH2)n-NH-C(O)-C(O)-NH-(CH2CH2)m-OH(V)；
(b3) Initiating the ring-opening polymerization of lactone monomer by the intermediate product C under the action of a catalyst to obtain a novel polyglycolic acid with a chemical structure of (II);
wherein R is1An alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group, a phenyl group or a substituted phenyl group; r2Is a polyglycolic acid chain segment with 40-30000 carbon atoms; n and m are the same or different, 2n and 2m are integers between 1 and 18;
the third purpose of the invention is to provide the application of the polyglycolic acid material.
In one embodiment, the application comprises application in the field of material packaging, textiles, medical consumables, plastics or agriculture.
Compared with the prior art, the invention has the following remarkable advantages:
(1) in the synthesis process of polyglycolic acid, hydrogen bond groups with self-assembly nucleation are introduced at the terminal groups of polyglycolic acid to obtain the terminal functional polyglycolic acid containing one or more hydrogen bond groups.
(2) Heating the end-functional polyglycolic acid containing one or more hydrogen bond groups to 1-50 ℃ above the melting temperature, keeping the temperature for 0.05-5min, and then cooling or keeping the temperature below the melting point; in the process of temperature reduction or constant temperature, polyglycolic acid can generate self-nucleation through the action of hydrogen bonds among hydrogen bond groups, and the polyglycolic acid segment is induced to be rapidly crystallized to obtain the polyglycolic acid with high crystallinity.
(3) The novel polyglycolic acid can induce polymer crystallization through hydrogen-terminated self-nucleation, can be rapidly crystallized at a high temperature, improves the crystallinity of the polyglycolic acid to 58.4 percent, and shortens the semi-crystallization time from 42.2min to within 8.5 min.
Drawings
FIG. 1 is nuclear magnetic hydrogen spectrum of intermediate product A of terminal functional group compound obtained in example 1 of the present invention;
FIG. 2 is the nuclear magnetic hydrogen spectrum of intermediate product B of the terminal functional group compound obtained in example 2 of the present invention;
FIG. 3 is nuclear magnetic hydrogen spectrum of end-functional compound intermediate product C obtained in example 2 of the present invention;
FIG. 4 is an infrared spectrum of a polyglycolic acid material obtained in example 1 of the present invention;
FIG. 5 is an infrared spectrum of a polyglycolic acid material obtained in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
Adding 15mL of diethyl oxalate, 200mL of ethanol, 9mL of ethanolamine and 6mL of n-propylamine into a 500mL three-neck flask, reacting at 50 ℃ for 24h, filtering to obtain a solid component, washing with ethanol for multiple times, and drying in a vacuum oven for 24h to obtain a terminal functional group compound intermediate product A: n is a radical of1- (2-hydroxyethyl) -N2-propyloxamide, i.e.:
according to the mass ratio of 100: 1 weighing glycolide and N1- (2-hydroxyethyl) -N2Propyl oxamide, 0.5 wt% stannous octoate was added, and melt reaction was carried out at 135 ℃ for 24 hours under vacuum reduced pressure atmosphere to obtain a white solid, which was dried to obtain a novel polyglycolic acid material (yield 86.8%).
FIG. 1 shows the nuclear magnetic hydrogen spectrum of intermediate A of the terminal-functional compound obtained in this example, with the following data:1h NMR (400MHz, DMSO). delta.8.65-8.50 (m,2H),4.76(t,1H),3.45(q,2H),3.21(q,2H),3.08(q,2H),1.54-1.40(m,2H), 0.87-0.77 (t, 3H). The obtained product was indeed proved to be an intermediate product represented by the above structural formula.
FIG. 4 is an infrared spectrum of the polyglycolic acid material obtained. Because the obtained polyglycolic acid material is insoluble in common deuterated reagents and cannot be characterized by nuclear magnetism, the obtained macromolecular product needs to be subjected to structural identification by combining infrared spectroscopy. To synthetic product N1- (2-hydroxyethyl) -N2Propyl oxamide, the obtained novel PGA material and pure PGA were subjected to total reflection infrared spectroscopy scans. Initiating monomer N1- (2-hydroxyethyl) -N2Propyl oxamide, at 3300cm-1The strong absorption peak is the N-H stretching vibration of the contained amide group and is 1650cm-1The strong absorption peak at the position corresponds to the C ═ O stretching vibration on the amide I band, and 1550--11320-1250cm-1The absorption peaks in between are amide II band and amide III band, respectively. PGA at 1750cm-1A significant ester carbonyl absorption peak occurs. The novel PGA material obtained in this example was found to be 1750cm-1Shows an ester carbonyl absorption peak at 1650cm-1The peak of C ═ O stretching vibration appears on the amide I band. The above results indicate that the novel PGA was successfully prepared.
The obtained polyglycolic acid material was characterized by its crystallization properties by DSC, and the results are shown in table 1.
Example 2
Adding 50mL of diethyl oxalate, 200mL of ethanol and 10mL of ethylenediamine into a 500mL three-neck flask, reacting for 24h at 50 ℃, filtering to obtain a solid component, washing with ethanol for multiple times, drying in a vacuum oven for 24h to obtain an intermediate product B, and mixing the intermediate product B, ethanolamine and n-propylamine according to a molar ratio of 10: 1: 1.1, slowly dripping the intermediate product B/chloroform solution into a tetrahydrofuran solution containing excessive ethanolamine and n-propylamine by using a constant-pressure dropping funnel, heating and stirring, refluxing for 24 hours to obtain a white suspension, and filtering, washing and drying to obtain a compound intermediate product C: n is a radical of1- (2-hydroxyethyl) -N2- (2- (2-oxo-2- (propylamino) acetylamino) ethyl) oxamide, i.e.:
according to the mass ratio of 100: 1 weighing glycolide and N1- (2-hydroxyethyl) -N2- (2- (2-oxo-2- (propylamino) acetylamino) ethyl) oxamide, 0.5 wt% stannous octoate was added, and the mixture was melted and reacted at 135 ℃ for 24 hours under vacuum and reduced pressure to obtain a white solid, which was dissolved, washed, precipitated and dried to obtain a novel degradable polyglycolic acid material (yield 75.8%).
FIG. 2 shows the nuclear magnetic hydrogen spectrum of intermediate product B obtained in this example, with the following data:1h NMR (400MHz, DMSO). delta.9.28-8.63 (t,2H),4.23(q,4H),3.30-3.06(q,4H),1.27(t, 6H). FIG. 3 is a nuclear magnetic hydrogen spectrum of end-functional compound intermediate C obtained in this example, with the following data:1h NMR (400MHz, TFAa) Δ 8.80(t,1H),8.24(t,1H),7.07-6.45(t,2H),4.53(q,2H),4.12(q,2H),3.89-3.68(q,4H),3.46(q,2H),1.57-1.41(m,2H),0.65-0.48(t, 3H). The product obtained was indeed the product represented by the above formula.
FIG. 5 is an infrared spectrum of the obtained polyglycolic acid-related material. To synthetic product N1- (2-hydroxyethyl) -N2Total reflection infrared spectrum scans of (2- (2-oxo-2- (propylamino) acetamido) ethyl) oxamide, the novel PGA material obtained and pure PGA were carried out. Initiating monomer N1- (2-hydroxyethyl) -N2- (2- (2-oxo-2- (propylamino) acetylamino) ethyl) oxamide at 3300cm-1The strong absorption peak is the N-H stretching vibration of the contained amide group and is 1650cm-1The strong absorption peak at the position corresponds to the C ═ O stretching vibration on the amide I band, and 1550--11320-1250cm-1The absorption peaks in between are amide II band and amide III band, respectively. PGA at 1750cm-1A significant ester carbonyl absorption peak occurs. The obtained novel PGA material is 1750cm-1Shows an ester carbonyl absorption peak at 1650cm-1The peak of C ═ O stretching vibration appears on the amide I band. The above results indicate the success of the novel PGA material.
The crystal properties of the obtained novel degradable polyglycolic acid were characterized by DSC, and the results are shown in table 1.
Comparative example 1
Referring to the examples, equal amount of glycolide was directly mixed with stannous isooctanoate (weighed as 0.5 wt%), and the mixture was melted and reacted at 135 ℃ for 24 hours under vacuum reduced pressure atmosphere to obtain white solid, which was dissolved, washed, precipitated and dried to obtain pure polyglycolic acid material. The crystal properties of the obtained pure polyglycolic acid were characterized by DSC, and the results are shown in Table 1.
Note that the glycolides used in examples 1-2 and comparative example 1 above were dried in vacuo at 60 ℃ for 12h before use. The diethyl oxalate, ethanolamine, ethylenediamine, n-propylamine, tetrahydrofuran, chloroform and stannous isooctanoate are all products of national medicine group chemical reagent company Limited, and the purity is analytical purity.
The polyglycolic acid materials obtained in examples 1-2 and comparative example 1 were subjected to the following crystallization treatments:
non-isothermal crystallization: heating from 0 deg.C to 270 deg.C at a heating rate of 10 deg.C/min, holding for 3min to eliminate thermal history, and cooling at a cooling rate of 10 deg.C/minAnd then the temperature is reduced to 0 ℃. The melting temperature (T) of the obtained polyglycolic acid was measured using a Differential Scanning Calorimeter (DSC)m) Crystallization temperature (T)c) And crystallinity. The test results obtained are listed in table 1.
Isothermal crystallization: the temperature is raised from 0 ℃ to 270 ℃ at a heating rate of 10 ℃/min, the temperature is kept for 3min to eliminate the thermal history, and then the temperature is reduced to 200 ℃ at a cooling rate of 100 ℃/min. The resulting polyglycolic acid was tested for the half-crystallization time (t) at this temperature using a Differential Scanning Calorimeter (DSC)1/2). The test results obtained are listed in table 1.
TABLE 1 Performance results for polyglycolic acid materials obtained in examples 1-2 and comparative example 1
As can be seen from the results in Table 1, the novel polyglycolic acid materials obtained in examples 1-2 can be rapidly crystallized at a higher temperature, the crystallinity of polyglycolic acid is increased from 50.4% to 58.4%, and the half-crystallization time is shortened from 42.2min to less than 5min, as compared with the pure polyglycolic acid obtained in comparative example 1.
The analysis of the results shows that the introduction of the terminal functional group can induce the polyglycolic acid to realize the intramolecular self-nucleation to promote the crystallization process, and the crystallization temperature and the crystallinity of the polyglycolic acid are obviously improved. The novel degradable polyglycolic acid can self-assemble for nucleation through the hydrogen bond action between terminal hydrogen bond groups, and induce the polyglycolic acid chain segment to rapidly crystallize, thus obtaining the polyglycolic acid with high crystallinity.
Example 3 investigation of the Effect of different primary amine Compounds on the polyglycolic acid materials prepared
Referring to example 1, n-propylamine was replaced with the primary amine compound shown in table 2, and other process conditions were unchanged to prepare the corresponding polyglycolic acid material.
The results of the properties of the obtained material are shown in table 2.
TABLE 2 Performance results for polyglycolic acid materials made with different primary amine compounds
Therefore, compared with the pure polyglycolic acid obtained in comparative example 1, the novel polyglycolic acid material obtained in example 3 can be rapidly crystallized at a higher temperature, the crystallinity of the polyglycolic acid is improved from 50.4% to 58.1%, and the semi-crystallization time is shortened from 42.2min to less than 5 min. On the other hand, the crystallinity of the novel polyglycolic acid materials obtained in examples 4 to 5 was increased from 50.4% to 52.4% and 51.4%, and the half-crystallization time was shortened from 42.2min to 7.3min and 22.1min, and from the above results, it was found that the effect of accelerating the crystallization of polyglycolic acid was reduced when the chain length of the amine was further increased.
Example 4 investigation of the effect of alcohol amine compounds of different chain lengths on the polyglycolic acid material produced
Referring to example 1, the ethanolamine was replaced with the alkanolamine compound shown in table 3, and other process conditions were unchanged to produce the corresponding polyglycolic acid material.
The results of the properties of the obtained material are shown in table 3.
TABLE 3 Performance results for polyglycolic acid materials made with different alcohol amine compounds
It can be seen that the novel polyglycolic acid materials obtained in examples 6 to 8 can be rapidly crystallized at a higher temperature, the crystallinity of polyglycolic acid is improved, and the half-crystallization time is reduced from 42.2min to 5.8, 4.2 and 18.2min, respectively, as compared with the pure polyglycolic acid obtained in comparative example 1. The alcohol amine compounds having different chain lengths have different influences on the crystallization effect of the produced polyglycolic acid material, and the acceleration effect on the polyglycolic acid crystallization decreases as the chain length increases, so that the optimal chain length range exists.
Example 5 investigation of the Effect of different chain length diamine Compounds on the polyglycolic acid materials prepared
Referring to example 1, the corresponding polyglycolic acid material was prepared by replacing ethylenediamine with the diamine compound shown in table 4 and keeping the other process conditions unchanged.
The results of the properties of the obtained material are shown in table 4.
TABLE 4 Performance results for polyglycolic acid materials made with different diamine compounds
It can be seen that the novel polyglycolic acid materials obtained in examples 9 to 11 can be rapidly crystallized at a higher temperature, the crystallinity of polyglycolic acid is improved, and the half-crystallization time is reduced from 42.2min to 8.5, 5.3, and 27.2min, respectively, as compared with the pure polyglycolic acid obtained in comparative example 1. Diamine compounds of different chain lengths have different effects on the crystallization effect of the polyglycolic acid material produced, and as the chain length increases, there is an optimum chain length.
Those skilled in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (10)
1. A polyglycolic acid material is characterized in that the preparation method thereof comprises the following steps:
(1) preparation of the hydroxyl-terminated intermediate: synthesizing an intermediate A containing terminal hydroxyl as shown in a formula (III) by reacting diethyl oxalate, an alcohol amine compound and a primary amine compound; or preparing a compound B shown in a formula (IV) by using diethyl oxalate and a diamine compound, and then reacting the compound B shown in the formula (IV) with an alcohol amine compound and a primary amine compound to synthesize an intermediate C containing a terminal hydroxyl group shown in a formula (V);
(2) preparing a polyglycolic acid material: polymerizing the intermediate A containing the terminal hydroxyl group obtained in the step (1) with glycolide to obtain a polyglycolic acid material; or polymerizing the intermediate C containing the terminal hydroxyl group obtained in the step (1) with glycolide to obtain a polyglycolic acid material;
wherein R is1An alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group, a phenyl group or a substituted phenyl group; n and m are the same or different, and 2 times of n and 2 times of m are integers between 1 and 18.
2. The polyglycolic acid material according to claim 1, wherein the alcohol amine compound is any one of alcohol amine compounds having 1 to 18 carbon atoms, and has the structure: NH (NH)2-(CH2-CH2)m-OH; and m is an integer of 1-18 times.
3. A polyglycolic acid material according to claim 1, where the alcohol amine compound is selected from any one or more of ethanolamine, propanolamine, butanolamine, hexanolamine, octanolamine, decanolamine, undecanolamine, dodecanolamine.
4. A polyglycolic acid material according to claim 1, wherein the substituents on said substituted phenyl groups are selected from halogen, C1-8 straight or branched chain alkyl, C1-8 straight or branched chain alkoxy.
5. A polyglycolic acid material according to claim 1, wherein the diamine compound has the structure: NH (NH)2-(CH2-CH2)n-NH2(ii) a And n is an integer of 1 to 18 times.
6. The polyglycolic acid material according to claim 1, wherein a catalyst is added to promote polymerization during both polymerization processes in step (2), and the catalyst is at least one of tin catalysts.
7. The polyglycolic acid material according to claim 1, wherein the preparation method further comprises the following processes: heating the polymerized polyglycolic acid material to 1-50 ℃ above the melting temperature, keeping the temperature for 0.05-5min, and then cooling or keeping the temperature below the melting point.
8. A polyglycolic acid material according to any one of claims 1 to 7, having a structure as shown in (I) or (II):
wherein R is1An alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group, a phenyl group or a substituted phenyl group; r2Is a polyglycolic acid chain segment with 40-30000 carbon atoms; n and m are the same or different, and 2 times of n and 2 times of m are integers between 1 and 18.
9. Use of a polyglycolic acid material according to any one of claims 1 to 8 for the preparation of a plastic article.
10. Use of a polyglycolic acid material according to any one of claims 1 to 8 in packaging, textile, medical consumables or agricultural fields.
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