CN114075377B - Toughening type polyglycolic acid composition, toughening type polyglycolic acid material, and preparation method and application thereof - Google Patents
Toughening type polyglycolic acid composition, toughening type polyglycolic acid material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of polyglycolic acid modification, and discloses a toughened polyglycolic acid composition, a toughened polyglycolic acid material, a preparation method and application thereof. The toughened polyglycolic acid composition comprises: 40-90 parts by weight of polyglycolic acid, 10-60 parts by weight of polyurethane and 0.5-10 parts by weight of isocyanate compound; wherein the polyglycolic acid has a weight average molecular weight of 5 to 30 ten thousand. The toughened polyglycolic acid material provided by the invention can be obviously improved in toughness, and the notch impact strength is improved by more than 1.7 times.
Description
Technical Field
The invention relates to the field of polyglycolic acid modification, in particular to a toughened polyglycolic acid composition, a toughened polyglycolic acid material, a preparation method and application thereof.
Background
Polyglycolic acid (abbreviated as PGA) is an aliphatic polyester-based polymer material having the highest degradation rate. Polyglycolic acid has outstanding biocompatibility, excellent mechanical properties and barrier properties. The modified release type biodegradable polymer has been widely applied to high added value products such as medical absorbable surgical suture lines, drug release control, simulation of human tissue materials, biodegradable polymer stents and the like. However, PGA has very high rigidity and brittleness, which makes the product less flexible and easy to damage, and severely restricts the processing application in many fields, so that it is necessary to toughen and modify the PGA and improve the flexibility.
CN108059806A discloses a biodegradable 3D printing PLA/TPU material, which comprises 40-60 parts of PLA, 15-30 parts of polyurethane, 5-20 parts of thermoplastic starch, 1-5 parts of cross-linking agent, 2-10 parts of inorganic filler and 0.5-1.0 part of stabilizer. The PLA/TPU material has excellent toughness, can be used for 3D printing materials, and has better mechanical properties.
CN110358097a discloses a PLA-based compatibilizer and a preparation method thereof. The method comprises the following steps: 65-96 parts of PLA, 5-40 parts of TPU, 2-35 parts of Glycidyl Methacrylate (GMA) and 0.1-2.0 parts of diisopropyl peroxide (DCP). The prepared PLA-based compatibilizer solves the problem of compatibility of PLA and TPU, and improves the comprehensive performance of the material.
Unlike PLA, polyglycolic acid is required to develop a toughening modification study on how to solve the brittle defect of polyglycolic acid.
Disclosure of Invention
The invention aims to solve the problem of poor toughness of polyglycolic acid materials in the prior art and provides a toughening type polyglycolic acid composition, a toughening type polyglycolic acid material, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a toughened polyglycolic acid composition comprising: 40-90 parts by weight of polyglycolic acid, 10-60 parts by weight of polyurethane and 0.5-10 parts by weight of isocyanate compound; wherein the polyglycolic acid has a weight average molecular weight of 5 to 30 ten thousand.
The second aspect of the invention provides a method for preparing a toughened polyglycolic acid material, comprising: the composition of the invention is melt blended to obtain the toughened polyglycolic acid material.
The third aspect of the invention provides a toughened polyglycolic acid material prepared by the preparation method of the invention.
In a fourth aspect, the invention provides an application of the material in film blowing, blow molding, plastic sucking and 3D printing.
Through the technical scheme, the toughened polyglycolic acid composition provided by the invention can reduce the phase dispersion size of the polyurethane elastomer (TPU) in the PGA in the toughened polyglycolic acid material by virtue of the contained components, so that the toughness of the toughened polyglycolic acid material is greatly improved, and the notch impact strength is improved by more than 1.7 times. Meanwhile, due to the high rigidity of the PGA and the TPU, the bending strength of the toughened polyglycolic acid material is more than 1GPa, and the toughened polyglycolic acid material has the balance of high rigidity and toughness.
Drawings
FIG. 1 is a TEM image of the toughened polyglycolic acid material prepared in example 1 of the present invention;
fig. 2 is a TEM image of the toughened polyglycolic acid material prepared in comparative example 3.
Description of the reference numerals
1、TPU；2、PGA-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 toughened polyglycolic acid composition comprising: 40-90 parts by weight of polyglycolic acid, 10-60 parts by weight of polyurethane and 0.5-10 parts by weight of isocyanate compound; wherein the weight average molecular weight of the polyglycolic acid is 5 ten thousand to 30 ten thousand.
In the composition provided by the invention, the polyurethane and the isocyanate compound are matched with each other in a limited amount, so that the toughness of polyglycolic acid can be improved. Preferably, in some embodiments, the polyglycolic acid is 40-80 parts by weight, the polyurethane is 20-60 parts by weight, and the isocyanate-based compound is 2-5 parts by weight. The composition can enable the further prepared toughened polyglycolic acid material to have high toughness, high strength, biocompatibility and degradability.
In some embodiments of the present invention, preferably, the polyglycolic acid has a weight average molecular weight of 5 ten thousand to 25 ten thousand, more preferably 9 ten thousand to 20 ten thousand. The selection of polyglycolic acid having a weight average molecular weight within this range of values can provide the final toughened polyglycolic acid material with high strength. The polyglycolic acid is commercially available, for example, from Shanghai Pu Jing chemical technology Co., ltd.
In some embodiments of the present invention, the isocyanate-based compound is capable of increasing the compatibility between polyglycolic acid and polyurethane in cooperation with the polyurethane component, thereby improving the technical effect of toughness and strength of the material ultimately produced from the composition. Preferably, the weight ratio of the polyurethane to the isocyanate compound is 2-50:1, preferably 4-25:1. the consumption of polyurethane is too small, and the toughness of the prepared material is increased limited and is insufficient; excessive amounts of polyurethane can affect the final rigidity of the resulting material.
In some embodiments of the present invention, preferably, the isocyanate-based compound is selected from a diisocyanate-based compound and/or a diisocyanate prepolymer; preferably, the isocyanate compound is at least one selected from toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate (MDI), lysine diisocyanate and Polyisocyanate (PMDI); more preferably, at least one selected from toluene-2, 4-diisocyanate, diphenylmethane diisocyanate and polyisocyanate. Wherein the viscosity (25 ℃) of the polyisocyanate is 150-250 mPa.s and the functionality is 2.6-2.7. The polyisocyanates are commercially available, for example, from the chemical production of PM200 (viscosity (25 ℃) of 150 to 250 mPa.s and functionality of 2.6 to 2.7).
In some embodiments of the invention, the addition of the polyurethane to the composition can synergistically improve the notched impact properties of the polyglycolic acid with the isocyanate-based compound, resulting in a toughened polyglycolic acid material that can have high strength. Preferably, the hardness of the polyurethane is 60A-60D, and the density of the polyurethane is 1.1-1.25g/cm 3 . Preferably, the polyurethane is selected from polyester polyurethane or polyether polyurethane, preferably from polyester polyurethane. Commercially available, for example, basoff B80A11 (hardness 80A, density 1.19 g/cm) 3 ). The hardness (Shore A) of the polyurethane was determined in accordance with ISO 868.
The second aspect of the invention provides a method for preparing a toughened polyglycolic acid material, comprising: the composition of the invention is melt blended to obtain the toughened polyglycolic acid material.
Specifically, 1) polyglycolic acid and polyurethane are dried at a drying temperature of 50-80 ℃ for 4-10 hours to remove water;
2) Uniformly mixing the dry polyglycolic acid, polyurethane and isocyanate compounds according to the composition provided by the invention;
3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder for melt blending.
In some embodiments of the present invention, preferably, the melt blending conditions include: the temperature is 225-245 ℃, preferably 235-240 ℃; the time is 4-10min, preferably 5-8min; the extruder speed is 60-110rpm, preferably 80-100rpm.
In the present invention, the inventors have studied the conditions of melt blending and found that when the toughened polyglycolic acid composition is melt blended under the above conditions, degradation of polyglycolic acid during extrusion can be avoided, and deterioration of the properties of the obtained polyglycolic acid composition can be avoided.
The third aspect of the invention provides a toughened polyglycolic acid material prepared by the preparation method of the invention.
The toughened polyglycolic acid material prepared by the invention can have improved performance, and in preferred embodiments, the toughened polyglycolic acid material has a flexural modulus of greater than or equal to 1GPa and a notched impact strength of greater than or equal to 7kJ/m 2 . The toughened polyglycolic acid material is capable of having a balance of high rigidity and toughness.
In a fourth aspect, the invention provides an application of the material in film blowing, blow molding, plastic sucking and 3D printing.
The present invention will be described in detail by examples. In the following examples, the resulting toughened polyglycolic acid material was subjected to TEM observation, and the dispersion and particle status of each component in the material was observed after the sample was subjected to ultra-thin section treatment using a JME ARM200F spherical aberration correcting transmission electron microscope.
Determining the notched impact strength of a sample according to GB/T1043-2008, testing at least 5 samples, and taking an average value;
measuring bending property of samples according to GB/T1843-2008, testing at least 5 samples, and taking average value;
polyglycolic acid (PGA) was purchased from Shanghai Pu Jing chemical technology Co., ltd and designated as PGA-1 (15 ten thousand weight average molecular weight); PGA-2 (weight average molecular weight 20 ten thousand); PGA-3 (9 ten thousand weight average molecular weight);
polyester polyurethane TPU was purchased from Basoff, B80A11 (hardness 80A, density 1.19 g/cm) 3 )；
Diphenylmethane diisocyanate (MDI) was purchased from enokak;
polyisocyanates (PMDI) were purchased from Wanhua chemistry, PM200 (25 ℃ C., mPas: 150-250, functionality 2.6-2.7).
In the following examples and comparative examples, polyglycolic acid and TPU were used after drying.
Example 1
Uniformly mixing 80 parts by weight of polyglycolic acid PGA-1, 20 parts by weight of TPU (B80A 11) and 5 parts by weight of MDI, and then carrying out melt blending for 6min at 240 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 100rpm, and extruding and granulating to obtain the toughened polyglycolic acid material.
The formulation of the composition and the test results are shown in Table 1. TEM observation is carried out on the obtained toughened polyglycolic acid material, and the obtained photo is shown in figure 1. It can be seen from fig. 1 that the TPU indicated by reference numeral 1 is dispersed in PGA-1 indicated by reference numeral 2 with smaller particle size and the two-phase interface compatibility is significantly improved.
Example 2
50 parts by weight of polyglycolic acid PGA-1, 50 parts by weight of TPU (B80A 11) and 2 parts by weight of MDI are uniformly mixed, and then melt-blended for 8 minutes by a double screw extruder at 235 ℃, and extrusion granulation is carried out at the speed of 80rpm, so that the toughened polyglycolic acid material is obtained.
The formulation of the composition and the test results are shown in Table 1.
Example 3
50 parts by weight of polyglycolic acid PGA-1, 50 parts by weight of TPU (B80A 11) and 5 parts by weight of MDI are uniformly mixed, and then melt-blended for 5 minutes by a twin-screw extruder at 240 ℃, and extrusion granulation is carried out at the extruder rotating speed of 90rpm, so that the toughened polyglycolic acid material is obtained.
The formulation of the composition and the test results are shown in Table 1.
Example 4
Uniformly mixing 40 parts by weight of polyglycolic acid PGA-1, 60 parts by weight of TPU (B80A 11) and 5 parts by weight of MDI, and then carrying out melt blending for 6min at 240 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 100rpm, and extruding and granulating to obtain the toughened polyglycolic acid material.
The formulation of the composition and the test results are shown in Table 1.
Example 5
Uniformly mixing 80 parts by weight of polyglycolic acid PGA-1, 20 parts by weight of TPU (B80A 11) and 5 parts by weight of PMDI (PM 200), and then melt-blending for 6min at 240 ℃ by using a twin-screw extruder, wherein the rotating speed of the extruder is 100rpm, and extruding and granulating to obtain the toughened polyglycolic acid material.
The formulation of the composition and the test results are shown in Table 1.
Example 6
Uniformly mixing 80 parts by weight of polyglycolic acid PGA-3, 20 parts by weight of TPU (B80A 11) and 5 parts by weight of MDI, and then carrying out melt blending for 6min at 240 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 100rpm, and extruding and granulating to obtain the toughened polyglycolic acid material.
The formulation of the composition and the test results are shown in Table 1.
Example 7
Uniformly mixing 80 parts by weight of polyglycolic acid PGA-2, 20 parts by weight of TPU (B80A 11) and 5 parts by weight of MDI, and then carrying out melt blending for 6min at 240 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 100rpm, and extruding and granulating to obtain the toughened polyglycolic acid material.
The formulation of the composition and the test results are shown in Table 1.
Comparative example 1
100 parts by weight of PGA-1 was melt-extruded and pelletized by a twin screw extruder at 240℃for 6 minutes at a rotational speed of 100rpm. The test results are shown in Table 1.
Comparative example 2
100 parts by weight of PGA-1 polyglycolic acid and 5 parts by weight of MDI were uniformly mixed, and then melt-blended at 240℃for 6 minutes by means of a twin-screw extruder, and extrusion granulation was carried out at a rotational speed of 100rpm. The formulation of the composition and the test results are shown in Table 1.
Comparative example 3
80 parts by weight of polyglycolic acid PGA-1 and 20 parts by weight of TPU were uniformly mixed, and then melt-blended at 240℃for 6 minutes by means of a twin-screw extruder, and extrusion granulation was carried out at a rotational speed of 100rpm. The formulation of the composition and the test results are shown in Table 1. TEM observation is carried out on the obtained toughened polyglycolic acid material, and the obtained photo is shown in figure 2. As can be seen from fig. 2, the TPU denoted by reference numeral 1 has poor compatibility with the PGA-1 denoted by reference numeral 2, and has a phase separation phenomenon, and the TPU has a large phase size in the PGA.
Comparative example 4
50 parts by weight of polyglycolic acid PGA-1 and 50 parts by weight of TPU were uniformly mixed, and then melt-blended at 240℃for 6 minutes by means of a twin-screw extruder, and extrusion granulation was carried out at a rotational speed of 100rpm. The formulation of the composition and the test results are shown in Table 1.
Comparative example 5
40 parts by weight of polyglycolic acid PGA-1 and 60 parts by weight of TPU were uniformly mixed, and then melt-blended at 240℃for 6 minutes by means of a twin-screw extruder, and extrusion granulation was carried out at a rotational speed of 100rpm. The formulation of the composition and the test results are shown in Table 1.
TABLE 1
Note that: * B80A11
As can be seen from the results of examples, comparative examples and Table 1, the toughened polyglycolic acid material prepared by the composition provided by the present invention has improved toughness by the synergistic combination of polyurethane and isocyanate compound, and the notched impact strength of the material is greater than that of the material of comparative examples, and the bending data has significantly better effect than the corresponding composition without the addition of the compatilizer. For example, examples 1, 5 to 7 can have balanced notched impact strength and bending properties compared to comparative example 3, and are all better than comparative example 3. Likewise, the compositions provided in examples 2 and 3 compared to comparative example 4 and example 4 compared to comparative example 5 provide toughened polyglycolic acid materials having improved toughness and flexural properties, improved PGA stiffness, and at the same time, better flexibility. Comparative examples 1 and 2, which do not have polyurethane and/or isocyanate-based compounds, do not improve the toughness of the resulting materials.
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 (16)
1. A toughened polyglycolic acid composition comprising: 40-90 parts by weight of polyglycolic acid, 10-60 parts by weight of polyurethane and 0.5-10 parts by weight of isocyanate compound; wherein the weight average molecular weight of the polyglycolic acid is 15 ten thousand to 25 ten thousand;
the weight ratio of the polyurethane to the isocyanate compound is 2-50:1, a step of;
the isocyanate compound is selected from diisocyanate compound and/or diisocyanate prepolymer.
2. The composition according to claim 1, wherein the polyglycolic acid is 40 to 80 parts by weight, the polyurethane is 20 to 60 parts by weight, and the isocyanate compound is 2 to 5 parts by weight.
3. The composition according to claim 1 or 2, wherein the weight ratio of polyurethane to isocyanate compound is 4-25:1.
4. the composition according to claim 1 or 2, wherein the isocyanate-based compound is selected from at least one of toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, and polyisocyanate.
5. The composition according to claim 4, wherein the isocyanate-based compound is at least one selected from the group consisting of toluene-2, 4-diisocyanate, diphenylmethane diisocyanate and polyisocyanate.
6. The composition according to claim 3, wherein the isocyanate-based compound is at least one selected from the group consisting of toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, and polyisocyanate.
7. The composition according to claim 6, wherein the isocyanate-based compound is at least one selected from toluene-2, 4-diisocyanate, diphenylmethane diisocyanate and polyisocyanate.
8. The composition of any of claims 1, 2 or 5-7, wherein the polyurethane has a hardness of 60A-60D and a density of 1.1-1.25g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The polyurethane is selected from polyester polyurethane or polyether polyurethane.
9. The composition of claim 3 wherein the polyurethane has a hardness of 60A-60D and a density of 1.1-1.25g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The polyurethane is selected from polyester polyurethane or polyether polyurethane.
10. The composition of claim 4 wherein the polyurethane has a hardness of 60A-60D and a density of 1.1-1.25g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The polyurethane is selected from polyester polyurethane or polyether polyurethane.
11. A method of preparing a toughened polyglycolic acid material, comprising:
melt blending the composition of any one of claims 1-10 to obtain a toughened polyglycolic acid material.
12. The method of preparation of claim 11, wherein the melt blending conditions comprise: the temperature is 225-245 ℃; the time is 4-10min; the extruder speed was 60-110rpm.
13. The method of preparation of claim 12, wherein the melt blending conditions comprise: the temperature is 235-240 ℃; the time is 5-8min; the extruder speed was 80-100rpm.
14. A toughened polyglycolic acid material produced by the method of any of claims 11-13.
15. The toughened polyglycolic acid material of claim 14, wherein the toughened polyglycolic acid material has a flexural modulus of ≡1GPa and notched impact strength of ≡7kJ/m 2 。
16. Use of a material according to any one of claims 1-15 in blown film, blow molding, suction molding, 3D printing.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030957A (en) * | 2012-12-25 | 2013-04-10 | 深圳大学 | Material based on polyhydroxyalkanoate and preparation method and application of material |
| CN104130365A (en) * | 2014-07-22 | 2014-11-05 | 南京林业大学 | Linear polyurethane elastomer toughener toughening biopolyester PHA, and preparation method and application thereof |
| CN107189386A (en) * | 2017-07-06 | 2017-09-22 | 太原工业学院 | The preparation method of star-like polyurethane elastomer plasticizing polylactic acid compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030957A (en) * | 2012-12-25 | 2013-04-10 | 深圳大学 | Material based on polyhydroxyalkanoate and preparation method and application of material |
| CN104130365A (en) * | 2014-07-22 | 2014-11-05 | 南京林业大学 | Linear polyurethane elastomer toughener toughening biopolyester PHA, and preparation method and application thereof |
| CN107189386A (en) * | 2017-07-06 | 2017-09-22 | 太原工业学院 | The preparation method of star-like polyurethane elastomer plasticizing polylactic acid compound |
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