CN114075373B - Modified polyglycolic acid composition, preparation method and application thereof - Google Patents
Modified polyglycolic acid composition, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of high polymer materials, and discloses a modified polyglycolic acid composition, a preparation method and application thereof. The modified polyglycolic acid composition comprises polyglycolic acid, a modifier and an antioxidant; the modifier is used in an amount of 0.5 to 5 parts by weight and the antioxidant is used in an amount of 0.1 to 1.5 parts by weight relative to 100 parts by weight of polyglycolic acid; the modifier has a structure shown in a formula I:
wherein R is H, C alkyl of 1-C6, phenyl or C1-C6 alkoxy, and n is an integer greater than 2. The modified polyglycolic acid composition has high thermal decomposition temperature, obviously improved stability at high temperature, improved melt viscosity and being favorable for processing and forming.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a modified polyglycolic acid composition, a preparation method and application thereof.
Background
Because the traditional high polymer material causes serious environmental problems in the process of using a large amount, the biodegradable high polymer material is receiving more and more attention. Polyglycolic acid (PGA) has excellent biodegradability, and the final degradation products are carbon dioxide and water, which are regarded as environmentally friendly green polymer materials. The PGA has good prospect in medical suture lines, tissue engineering, drug slow-release systems and other medical application fields, and is an important medical biodegradable polymer material. In addition, PGA can also be applied to the fields of agricultural biodegradable films, degradable packaging materials and the like.
The polymer material is generally molded and processed into a product at a temperature higher than the melting point. PGA has a melting point of about 220℃and a high molding temperature, and PGA is easily thermally degraded at a high temperature, resulting in a decrease in relative molecular mass and deterioration of properties. Therefore, there is increasing interest in how to increase the relative molecular mass and viscosity of PGA.
CN106566216a discloses a method for improving secondary processing stability of polyhydroxyacids. Uniformly mixing polyhydroxyacid (such as PGA, PLA) and bishydrazide material (0.05-1%); the obtained mixture is added into a double-screw extruder under the protection of inert gas for melt mixing and extrusion. The method ensures that the polyhydroxyacid subjected to secondary processing has higher molecular weight and mechanical property. However, the technology only inerts the catalyst by adding the dihydrazide substance to improve the processing heat stability, and the problem of low melt viscosity of the polyhydroxy acid is not solved. In the prior art, the polyglycolic acid has poor processing heat stability, is easy to thermally degrade, has low melt viscosity and cannot meet the actual demands.
Disclosure of Invention
The invention aims to overcome the problems of poor heat stability and easy degradation at high temperature in the process of polyglycolic acid processing in the prior art, and provides a modified polyglycolic acid composition, a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a modified polyglycolic acid composition, wherein the modified polyglycolic acid composition comprises polyglycolic acid, a modifier and an antioxidant;
the modifier is used in an amount of 0.5 to 5 parts by weight and the antioxidant is used in an amount of 0.1 to 1.5 parts by weight relative to 100 parts by weight of polyglycolic acid;
the modifier has a structure shown in a formula I:
wherein R is H, C alkyl of 1-C6, phenyl or C1-C6 alkoxy, and n is an integer greater than 2.
In a second aspect, the present invention provides a process for preparing a modified polyglycolic acid composition, wherein the process comprises the steps of:
(1) Respectively drying polyglycolic acid, a modifier and an antioxidant, and uniformly mixing to obtain a mixture;
(2) Carrying out melt blending extrusion on the mixture obtained in the step (1) through a double-screw extruder to obtain the modified polyglycolic acid composition;
the modifier has a structure shown in a formula I:
wherein R is H, C alkyl of 1-C6, phenyl or C1-C6 alkoxy, and n is an integer greater than 2.
In a third aspect, the present invention provides a modified polyglycolic acid composition produced by the above-described production process.
In a fourth aspect, the present invention provides the use of a modified polyglycolic acid composition as described above in a degradable material or barrier packaging material.
In a fifth aspect, the present invention provides the use of a modified polyglycolic acid composition as described above in the preparation of at least one of a film, a fiber and a sheet.
Through the technical scheme, the modified polyglycolic acid composition provided by the invention and the preparation method and application thereof have the following beneficial effects:
in the invention, the modified polyglycolic acid composition comprises the modifier with a specific structure, and the modifier can modify the polyglycolic acid, so that the melt viscosity of the polyglycolic acid is obviously improved, and meanwhile, the thermal degradation rate is effectively reduced.
Further, in the present invention, the modified polyglycolic acid composition further comprises an antioxidant, and the antioxidant is selected to be matched with the modifier, so that the thermal decomposition temperature of the modified polyglycolic acid composition can be further increased, the thermal degradation during melt extrusion can be reduced, and the thermal stability of the composition can be further improved.
Drawings
FIG. 1 is an infrared comparison of the modified polyglycolic acid composition of example 1 with the polyglycolic acid of comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a modified polyglycolic acid composition, wherein the modified polyglycolic acid composition comprises polyglycolic acid, an antioxidant and a modifier;
the modifier is used in an amount of 0.5 to 5 parts by weight and the antioxidant is used in an amount of 0.1 to 1.5 parts by weight relative to 100 parts by weight of polyglycolic acid;
the modifier has a structure shown in a formula I:
wherein R is H, C alkyl of 1-C6, phenyl or C1-C6 alkoxy, and n is an integer greater than 2.
In the invention, the modified polyglycolic acid composition comprises the modifier with the structure shown in the formula I and the antioxidant, and the modifier and the antioxidant are matched with each other to remarkably improve the processing heat stability of the polyglycolic acid. Specifically, the modifier can modify polyglycolic acid, and the modified polyglycolic acid composition has the characteristics of high thermal decomposition temperature and high melt viscosity. Further, in the formula I, R is methyl, ethyl, phenyl or methoxy, and n is an integer of 3-30.
In the modified polyglycolic acid composition, when the dosages of the polyglycolic acid, the modifier and the antioxidant meet the above limit, the modified polyglycolic acid composition has the advantages of high thermal stability and high melt viscosity. Further, the modified polyglycolic acid composition has more excellent properties, with respect to 100 parts by weight of polyglycolic acid, the amount of the modifier is 1 to 3 parts by weight, and the amount of the antioxidant is 0.5 to 1 part by weight.
According to the invention, the polyglycolic acid has a weight-average molecular weight of 5 to 30 ten thousand, preferably 10 to 15 ten thousand.
According to the present invention, the antioxidant is at least one selected from the group consisting of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants, preferably phosphite antioxidants.
More preferably, the antioxidant is selected from at least one of antioxidant 168, antioxidant 626, and antioxidant 9228.
According to the present invention, the 5% weight loss temperature of the polyglycolic acid and the 5% weight loss temperature of the modified polyglycolic acid composition are T1 and T2, respectively;
wherein T2-T1 is not less than 20 ℃, preferably T2-T1 is 20-40 ℃.
In the present invention, the weight loss temperature of 5 wt% means a temperature corresponding to 5 wt% of the weight loss of polyglycolic acid, and is measured by TG thermal weight loss method.
According to the present invention, the melt flow rates of the polyglycolic acid and the modified polyglycolic acid composition are MFR1 and MFR2, respectively, at 240 ℃ and a load of 2.16 kg;
wherein MFR 2. Ltoreq.40%. Times.MFR 1, preferably MFR2 is (10-25%) times.MFR 1.
In the present invention, the melt flow rate is measured according to the method GB/T3682-2000.
According to the present invention, the melt viscosity of the polyglycolic acid and modified polyglycolic acid compositions is η1 and η2, respectively, wherein η2 is ≡4η1, at 230 ℃, 2% strain and frequency of 0.1 rad/s.
In the present invention, the melt viscosity of the polyglycolic acid composition is measured using rotational rheology frequency sweep.
In a second aspect, the present invention provides a process for preparing a modified polyglycolic acid composition, wherein the process comprises the steps of:
(1) Respectively drying polyglycolic acid, a modifier and an antioxidant, and uniformly mixing to obtain a mixture;
(2) Carrying out melt blending extrusion on the mixture obtained in the step (1) through a double-screw extruder to obtain the modified polyglycolic acid composition;
the modifier has a structure shown in a formula I:
wherein R is H, C alkyl of 1-C6, phenyl or C1-C6 alkoxy, and n is an integer greater than 2.
According to the invention, the modifier containing polyglycolic acid, the modifier with the structure shown in the formula I and the antioxidant are subjected to melt blending extrusion in a double-screw extruder, so that the modifier containing a maleic anhydride structure can realize reactive extrusion modification on polyglycolic acid (PGA), and the modifier and PGA terminal group-OH are utilized to carry out nucleophilic substitution reaction, so that the esterification reaction condition is mild, and the reaction rate is high. Meanwhile, the prepared modified polyglycolic acid composition has higher molecular weight, better processability and thermal stability through adding an antioxidant for matching use.
According to the invention, the antioxidant is used in an amount of 0.1 to 1.5 parts by weight, preferably 0.5 to 1 part by weight, relative to 100 parts by weight of polyglycolic acid; the modifier is used in an amount of 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight.
According to the invention, the polyglycolic acid has a weight-average molecular weight of 5 to 30 ten thousand, preferably 10 to 15 ten thousand.
According to the invention, in formula I, R is methyl, ethyl, phenyl or methoxy and n is an integer from 3 to 30.
According to the invention, the drying conditions include: the drying temperature is 50-80deg.C, preferably 60-80deg.C; the drying time is 5-10 hours, preferably 5-8 hours.
In the present invention, the inventors have found that, when polyglycolic acid and an antioxidant are dried under the above-mentioned conditions, hydrolysis of a mixture containing polyglycolic acid and an antioxidant during extrusion due to moisture in the raw materials can be prevented
In the invention, the inventors have studied the condition of melt blending, and found that when the temperature is 220-250 ℃ and the screw rotation speed is 80-110r/min during melt blending extrusion, the degradation of polyglycolic acid during extrusion can be reduced, and the deterioration of the performance of the prepared polyglycolic acid composition is avoided. Further, when the melt blending extrusion is carried out, the temperature is 230-240 ℃, the screw speed is 90-100r/min, and the prepared polyglycolic acid composition has more excellent comprehensive properties.
In a third aspect, the present invention provides a modified polyglycolic acid composition produced by the above-described process.
In the present invention, the 5% weight loss temperature of the polyglycolic acid and the 5% weight loss temperature of the modified polyglycolic acid composition are T1 and T2, respectively;
wherein T2-T1 is not less than 20 ℃, preferably T2-T1 is 20-40 ℃.
In the present invention, the weight loss temperature of 5% by weight means a temperature corresponding to 5% by weight of polyglycolic acid, and is measured by TG thermogravimetric method.
In the present invention, the melt flow rates of the polyglycolic acid and the modified polyglycolic acid composition are MFR1 and MFR2, respectively, at 240 ℃ and a load of 2.16 kg;
wherein MFR 2. Ltoreq.40%. Times.MFR 1, preferably MFR2 is (10-25%) times.MFR 1.
In the present invention, the melt flow rate is measured according to the method GB/T3682-2000.
In the invention, the melt viscosity of the polyglycolic acid and modified polyglycolic acid composition is eta 1 and eta 2 respectively at 230 ℃, 2% strain and 0.1rad/s frequency, wherein eta 2 is more than or equal to 4 eta 1.
In the present invention, the melt viscosity of the polyglycolic acid composition is measured using rotational rheology frequency sweep.
In a fourth aspect the present invention provides the use of a modified polyglycolic acid composition as described above in a degradable material or barrier packaging material.
In a fifth aspect, the present invention provides the use of a modified polyglycolic acid composition as described above in the preparation of at least one of a film, a fiber and a sheet.
The present invention will be described in detail by examples. In the following examples of the present invention,
the 5 wt% weight loss temperature of polyglycolic acid was measured using TG thermal weight loss method;
the melt flow rate of polyglycolic acid was measured using the GB/T3682-2000 method;
the melt viscosity of polyglycolic acid is measured by rotational rheological frequency sweep (230 ℃, strain 2%, frequency 0.1-100 rad/s);
the infrared spectrograms of the modified polyglycolic acid composition and the polyglycolic acid are measured by a Fourier transform infrared spectrometer IRPrestine-21 of Shimadzu corporation of Japan, and specific test conditions are as follows: scanning range 4000-400cm -1 The number of scans was 32;
polyglycolic acid a, weight average molecular weight 14 ten thousand, commercially available;
polyglycolic acid B, weight average molecular weight 9 ten thousand, commercially available;
polyglycolic acid C, weight average molecular weight 4 ten thousand, commercially available;
modifier I, SMA1000, wherein R is phenyl, n is 27, and the weight average molecular weight Mw is 5500, purchased from Yushuo New Material technology Co., ltd;
modifier II, CAS number: 9006-26-2 wherein R is H, n is 3, and the weight average molecular weight Mw is 378, purchased from Shanghai Ding Feng chemical technology Co., ltd;
the other raw materials used in the examples and comparative examples are all commercially available.
Example 1
100 parts by weight of polyglycolic acid A, 3 parts by weight of modifier A and 1 part by weight of antioxidant (antioxidant 168) are dried for standby, wherein the drying temperature is 80 ℃, and the drying time is 6 hours; uniformly mixing the dried polyglycolic acid, the modifier and the antioxidant, and then carrying out melt blending extrusion granulation by a double-screw extruder at 240 ℃ and the rotating speed of 90r/min to obtain the modified polyglycolic acid composition A1.
The modified polyglycolic acid composition was tested to have a melt flow rate MFR2 of 14g/10min (down to 32% of the melt flow rate MFR1 of comparative example 1) and a 5% weight loss temperature T2 of 349 ℃ (27 ℃ above the 5% weight loss temperature T1 of comparative example 1). The melt viscosity η2 (230 ℃, strain 2%,0.1 rad/s) was 1500 Pa.s (increased to 5.7 times the melt viscosity η1 of comparative example 1).
The infrared spectrum of the modified polyglycolic acid composition is shown in FIG. 1, wherein in FIG. 1, 3512cm -1 is-OH characteristic peak, 720cm -1 Is a saturated hydrocarbon group CH 2 CH vibration peak of 720cm -1 Characteristic peak is an internal standard, and 3512cm is examined -1 Peak change, the infrared absorption peak area ratio is calculated to obtain the pre-reaction
Post-reaction->
Indicating that the hydroxyl end groups of polyglycolic acid are consumed by chemical reactions.
Example 2
100 parts by weight of polyglycolic acid A, 3 parts by weight of modifier B and 1 part by weight of antioxidant (antioxidant 168) are dried for standby, wherein the drying temperature is 80 ℃ and the drying time is 6 hours; uniformly mixing the dried polyglycolic acid, the modifier and the antioxidant, and then carrying out melt blending extrusion granulation by a double-screw extruder at 240 ℃ and the rotating speed of 90r/min to obtain the modified polyglycolic acid composition A2.
The melt flow rate MFR2 of the composition was tested to be 11g/10min (down to 25% of the melt flow rate MFR1 of comparative example 1) and the 5% weight loss temperature T2 to be 351 ℃ (29 ℃ above the 5% weight loss temperature T1 of comparative example 1). Melt viscosity η2 (230 ℃, strain 2%,0.1 rad/s) is 1610 Pa.s (increased to 6.2 times the melt viscosity η1 of comparative example 1).
Example 3
100 parts by weight of polyglycolic acid A, 5 parts by weight of modifier B and 0.1 part by weight of antioxidant (antioxidant 168) are dried for standby, wherein the drying temperature is 80 ℃ and the drying time is 6 hours; uniformly mixing the dried polyglycolic acid, the modifier and the antioxidant, and then carrying out melt blending extrusion granulation by a double-screw extruder at 240 ℃ and the rotating speed of 90r/min to obtain the modified polyglycolic acid composition A3.
The melt flow rate MFR2 of the composition was tested to be 10g/10min (down to 23% of the melt flow rate MFR1 of comparative example 1) and the 5% weight loss temperature T2 was 342℃which was 20℃higher than the 5% weight loss temperature T1 of comparative example 1. The melt viscosity η2 (230 ℃, strain 2%,0.1 rad/s) was 1690 Pa.s (up to 6.5 times the melt viscosity η1 of comparative example 1).
Example 4
100 parts by weight of polyglycolic acid A, 0.5 part by weight of modifier A and 1.5 parts by weight of antioxidant (antioxidant 168) are dried for standby, wherein the drying temperature is 80 ℃ and the drying time is 6 hours; uniformly mixing the dried polyglycolic acid, the modifier and the antioxidant, and then carrying out melt blending extrusion granulation by a double-screw extruder at 240 ℃ and the rotating speed of 90r/min to obtain the modified polyglycolic acid composition.
The melt flow rate MFR2 of the composition was tested to be 17g/10min (down to 38% of the melt flow rate MFR1 of comparative example 1) and the 5% weight loss temperature T2 was 355 ℃ (33 ℃ C. Higher than the 5% weight loss temperature T1 of comparative example 1). The melt viscosity η2 (230 ℃, strain 2%,0.1 rad/s) was 1050 Pa.s (increased to 4 times the melt viscosity η1 of comparative example 1).
Example 5
A modified polyglycolic acid composition was prepared as described in example 1, except that: polyglycolic acid B was used instead of polyglycolic acid a.
The melt flow rate MFR2 of the composition was tested to be 23g/10min (down to the melt flow rate MFR1 of comparative example 2 * 35% of (2)) The 5% weight loss temperature T2 was 344 ℃ (compared to the 5% weight loss temperature T1 of comparative example 2) * The temperature is increased by 29 ℃). Melt viscosity η2 (230 ℃, strain 2%,0.1 rad/s) is 800 Pa.s (increase to comparative example 2 melt viscosity η1 * 4.2 times) of (c).
Example 6
A modified polyglycolic acid composition was prepared as described in example 1, except that: the temperature of the melt blending extrusion was 230 ℃.
The melt flow rate MFR2 of the composition was tested to be 12.5g/10min (down to 28% of the melt flow rate MFR1 of comparative example 1) and the 5% weight loss temperature T2 was 347℃which is 25℃higher than the 5% weight loss temperature T1 of comparative example 1. Melt viscosity η2 (230 ℃, strain 2%,0.1 rad/s) is 1560 Pa.s (up to 6 times the melt viscosity η1 of comparative example 1).
Comparative example 1
100 parts by weight of polyglycolic acid A is dried for standby, the drying temperature is 80 ℃, and the drying time is 6 hours; and (3) carrying out melt extrusion granulation on the dried polyglycolic acid by a double-screw extruder at 240 ℃ and the rotating speed of 90 r/min.
The melt flow rate MFR1 of the polyglycolic acid was 44g/10min and the 5% by weight loss temperature T1 was 322 ℃. The melt viscosity η1 (230 ℃, strain 2%,0.1 rad/s) is 260 Pa.s.
Comparative example 2
Polyglycolic acid was prepared as in comparative example 1, except that: polyglycolic acid B was used instead of polyglycolic acid a.
Melt flow Rate MFR1 of polyglycolic acid tested * 65g/10min,5 wt% weight loss temperature T1 * At 315 ℃ and melt viscosity eta 1 * (230 ℃, strain 2%,0.1 rad/s) is 190 Pa.s.
Comparative example 3
100 parts by weight of polyglycolic acid A and 1 part by weight of an antioxidant (antioxidant 168) are dried for later use, wherein the drying temperature is 80 ℃ and the drying time is 6 hours; uniformly mixing the dried polyglycolic acid and the antioxidant, and then carrying out melt blending extrusion granulation by using a double-screw extruder at 240 ℃ and the rotating speed of 90r/min to obtain the modified polyglycolic acid composition.
The melt flow rate MFR2 of the composition was tested to be 27g/10min (down to 61% of the melt flow rate MFR1 of comparative example 1) and the 5% weight loss temperature T2 to be 357℃which is increased by 35℃over the 5% weight loss temperature T1 of comparative example 1. The melt viscosity η2 (230 ℃, strain 2%,0.1 rad/s) was 500 Pa.s (increased to 1.9 times the melt viscosity η1 of comparative example 1).
Comparative example 4
A modified polyglycolic acid composition was prepared as described in example 1, except that: no antioxidant is added.
The melt flow rate MFR2 of the composition was tested to be 19g/10min (down to 43% of the melt flow rate MFR1 of comparative example 1) and the 5% weight loss temperature T2 to be 339 ℃ (17 ℃ above the 5% weight loss temperature T1 of comparative example 1). The melt viscosity η2 (230 ℃, strain 2%,0.1 rad/s) was 900 Pa.s (3.5 times the melt viscosity η1 of comparative example 1).
Comparative example 5
A modified polyglycolic acid composition was prepared as described in example 1, except that: the amounts of antioxidant and modifier used were different from those of example 1.
The melt flow rate MFR2 of the composition was tested to be 30.8g/10min (down to 70% of the melt flow rate MFR1 of comparative example 1) and the 5% weight loss temperature T2 was 332℃which is 10℃higher than the 5% weight loss temperature T1 of comparative example 1. The melt viscosity η2 (230 ℃, strain 2%,0.1 rad/s) was 540 Pa.s (increased to 2 times the melt viscosity η1 of comparative example 1).
Table 1 (weight portions)
| Examples | Polyglycolic acid | Modifier I | Modifier II | Antioxidant | Melt blending extrusion |
| Example 1 | A/100 | 3 | 0 | 1 | 240℃/90r/min |
| Example 2 | A/100 | 0 | 3 | 1 | 240℃/90r/min |
| Example 3 | A/100 | 0 | 5 | 0.1 | 240℃/90r/min |
| Example 4 | A/100 | 0 | 0.5 | 1.5 | 240℃/90r/min |
| Example 5 | B/100 | 3 | 0 | 1 | 240℃/90r/min |
| Example 6 | A/100 | 3 | 0 | 1 | 230℃/90r/min |
| Comparative example 1 | A/100 | 0 | 0 | 0 | 240℃/90r/min |
| Comparative example 2 | B/100 | 0 | 0 | 0 | 240℃/90r/min |
| Comparative example 3 | A/100 | 0 | 0 | 1 | 240℃/90r/min |
| Comparative example 4 | A/100 | 3 | 0 | 0 | 240℃/90r/min |
| Comparative example 5 | A/100 | 0.2 | 0 | 0.3 | 240℃/90r/min |
As can be seen from the results in Table 1, the polyglycolic acid is modified by the combination of the modifier with a specific structure and the antioxidant, the heat stability of the modified polyglycolic acid is obviously improved, and the melt viscosity of the modified polyglycolic acid is also improved, so that the comprehensive performance of the polyglycolic acid composition is more excellent.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (20)
1. A modified polyglycolic acid composition, wherein the modified polyglycolic acid composition comprises polyglycolic acid, a modifier, and an antioxidant;
the modifier is used in an amount of 0.5 to 5 parts by weight and the antioxidant is used in an amount of 0.1 to 1.5 parts by weight relative to 100 parts by weight of polyglycolic acid;
the modifier has a structure shown in a formula I:
wherein R is H, C alkyl of 1-C6, phenyl or C1-C6 alkoxy, and n is an integer greater than 2.
2. The modified polyglycolic acid composition of claim 1, wherein in formula I, R is methyl, ethyl, phenyl, or methoxy, and n is an integer from 3 to 30.
3. The modified polyglycolic acid composition of claim 1 or 2, having a weight average molecular weight of 5-30 ten thousand.
4. The modified polyglycolic acid composition of claim 1 or 2, having a weight average molecular weight of 10-15 ten thousand.
5. The modified polyglycolic acid composition of claim 1 or 2, wherein the modifier is used in an amount of 1-3 parts by weight and the antioxidant is used in an amount of 0.5-1 parts by weight, relative to 100 parts by weight of polyglycolic acid;
and/or the antioxidant is selected from at least one of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants.
6. The modified polyglycolic acid composition of claim 1 or 2, wherein the antioxidant is selected from phosphite antioxidants.
7. The modified polyglycolic acid composition of claim 1 or 2, wherein the antioxidant is selected from at least one of antioxidant 168, antioxidant 626, and antioxidant 9228.
8. The modified polyglycolic acid composition of claim 1 or 2, wherein the polyglycolic acid has a 5 weight percent weight loss temperature and the modified polyglycolic acid composition has a 5 weight percent weight loss temperature of T1 and T2, respectively;
wherein T2-T1 is more than or equal to 20 ℃;
and/or, at 240 ℃ and under a load of 2.16kg, the melt flow rates of the polyglycolic acid and the modified polyglycolic acid composition are MFR1 and MFR2, respectively;
wherein MFR2 is less than or equal to 40% by MFR1;
and/or, the melt viscosity of the polyglycolic acid and modified polyglycolic acid compositions are η1 and η2, respectively, wherein η2 is greater than or equal to 4 η1, at 230 ℃, 2% strain and a frequency of 0.1 rad/s.
9. The modified polyglycolic acid composition of claim 8, wherein T2-T1 is 20-40 ℃;
and/or MFR2 is (10-25%). Times.MFR1.
10. A process for preparing a modified polyglycolic acid composition, wherein the process comprises the steps of:
(1) Respectively drying polyglycolic acid, a modifier and an antioxidant, and uniformly mixing to obtain a mixture;
(2) Carrying out melt blending extrusion on the mixture obtained in the step (1) through a double-screw extruder to obtain the modified polyglycolic acid composition;
the modifier has a structure shown in a formula I:
wherein R is H, C alkyl of 1-C6, phenyl or C1-C6 alkoxy, n is an integer greater than 2;
the antioxidant is used in an amount of 0.1 to 1.5 parts by weight relative to 100 parts by weight of polyglycolic acid; the modifier is used in an amount of 0.5 to 5 parts by weight.
11. The method of claim 10, wherein the polyglycolic acid has a weight average molecular weight of 5-30 ten thousand.
12. The method according to claim 10 or 11, wherein the antioxidant is used in an amount of 0.5 to 1 part by weight relative to 100 parts by weight of polyglycolic acid; the modifier is used in an amount of 1-3 parts by weight;
and/or, the polyglycolic acid has a weight average molecular weight of 10 to 15 ten thousand.
13. The method according to claim 10 or 11, wherein in formula I, R is methyl, ethyl, phenyl or methoxy, and n is an integer from 3 to 30.
14. The production method according to claim 10 or 11, wherein the drying conditions include: the drying temperature is 50-80 ℃; the drying time is 5-10h.
15. The production method according to claim 10 or 11, wherein the drying conditions include: the drying temperature is 60-80 ℃; the drying time is 5-8h.
16. The production method according to claim 10 or 11, wherein the conditions of melt blending extrusion include: the temperature is 220-250 ℃; the rotating speed of the screw is 80-110r/min.
17. The production method according to claim 10 or 11, wherein the conditions of melt blending extrusion include: the temperature is 230-240 ℃; the rotating speed of the screw is 90-100r/min.
18. A modified polyglycolic acid composition produced by the process of any one of claims 10-17.
19. Use of a modified polyglycolic acid composition of any one of claims 1-9 and claim 18 in a degradable material or barrier packaging material.
20. Use of the modified polyglycolic acid composition of any one of claims 1-9 and claim 18 in the preparation of at least one of a film, a fiber, and a sheet.
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| CN1059919A (en) * | 1990-09-11 | 1992-04-01 | 纳幕尔杜邦公司 | The film that contains polyhydroxy acid and a kind of compatilizer |
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