Polyglycolic acid toughened modified material, its preparation method and application

Abstract

The present application relates to polyglycolic acid modification technical field, disclose a kind of polyglycolic acid toughening modified material and its preparation method and application.Polyglycolic acid toughening modified material is prepared from raw materials including the following components:65-85 parts by weight of polyglycolic acid, 15-30 parts by weight of polybutylene succinate, 1-4 parts by weight of modifier, 0.5-5 parts by weight of compatibilizer, 0.3-3 parts by weight of antioxidant;Wherein, the average particle size of polybutylene succinate in the polyglycolic acid toughening modified material is 100-900nm.Polyglycolic acid toughening modified material in the present application has high rigidity and high toughness, and has good application prospect in the field of spinning fiber and thin-wall injection molding products.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a polyglycolic acid toughened modified material, its preparation method, and its application. Background Technology

[0002] In recent years, the "white pollution" caused by single-use plastic products has placed a heavy burden on the ecological environment. Since the implementation of the "plastic restriction order," renewable, degradable, and biocompatible biodegradable polyester materials have received much attention.

[0003] PGA (polyglycolic acid) is a biodegradable material with good biodegradability and biocompatibility, gas barrier properties, and excellent mechanical strength. However, PGA also has disadvantages such as high brittleness, low melt strength, and easy decomposition, which severely limit its application in fields such as spun fibers and thin-walled injection molded products.

[0004] CN107987494A discloses a biodegradable polyethylene terephthalate (PET) blend comprising the following components in parts by weight: 50-70 parts PET, 10-40 parts polyglycolic acid (PGA), 5-10 parts compatibilizer, 0.1-0.5 parts antioxidant, and 1-2 parts anti-hydrolysis agent. While this blend exhibits good biodegradability, it uses PET as the main resin and adds a small amount of PGA as a modifying resin, without mentioning the blend's mechanical properties.

[0005] CN111154245A discloses a fully biodegradable dental floss pick handle and its preparation method. The materials include 60-90 parts of polyglycolic acid; 5-30 parts of a toughening agent (one or more of polybutylene adipate, polybutylene succinate, polycaprolactone, polyhydroxyalkanoates, polypropylene carbonate, acrylate biodegradable polymers, and maleic anhydride-grafted biodegradable polymers); 0.1-5 parts of a nucleating agent; 0.1-2 parts of a lubricant; 0.1-1 parts of a compatibilizer (silane coupling agent, aluminate, titanate); and 0.1-3 parts of an antibacterial agent. This fully biodegradable dental floss pick handle exhibits good biodegradability; however, dental floss picks do not require high mechanical properties, and the silane coupling agent, aluminate, and titanate compatibilizer do not significantly improve the material's mechanical properties.

[0006] Therefore, there is an urgent need to provide a biodegradable PGA material that can combine high rigidity and high toughness. Summary of the Invention

[0007] The purpose of this invention is to solve the problems of high brittleness, low melt strength, and excessively rapid degradation of PGA materials, and to provide a toughened modified polyglycolic acid material, its preparation method, and its application.

[0008] To achieve the above objectives, the present invention provides a polyglycolic acid toughening modified material, wherein the toughening modified material is prepared from raw materials comprising the following components: 65-85 parts by weight of polyglycolic acid, 15-30 parts by weight of polybutylene succinate, 1-4 parts by weight of modifier, 0.5-5 parts by weight of compatibilizer, and 0.3-3 parts by weight of antioxidant; wherein, in the polyglycolic acid toughening modified material, the average particle size of polybutylene succinate is 100-900 nm.

[0009] A second aspect of the present invention provides a method for preparing a polyglycolic acid toughened modified material, the method comprising: melt-blending and extruding granulation of 65-85 parts by weight of polyglycolic acid, 15-30 parts by weight of polybutylene succinate, 1-4 parts by weight of modifier, 0.5-5 parts by weight of compatibilizer, and 0.3-3 parts by weight of antioxidant to obtain the polyglycolic acid toughened modified material.

[0010] A third aspect of the present invention provides the application of the polyglycolic acid toughening modified material described in the first aspect of the present invention and / or the polyglycolic acid toughening modified material prepared by the method described in the second aspect of the present invention in spun fibers and / or thin-walled injection molded products.

[0011] The beneficial technical effects achieved by the present invention through the above technical solution are as follows:

[0012] 1) The present invention provides a toughened modified polyglycolic acid material, which uses polyglycolic acid as the base resin and modifies polybutylene succinate, modifier, compatibilizer and antioxidant. The synergistic effect between the components, especially the synergistic effect between a specific content of polybutylene succinate and compatibilizer, makes the polybutylene succinate exist in the nanoparticle state in the prepared toughened modified polyglycolic acid material, thereby obtaining a toughened modified polyglycolic acid material with both high rigidity and high toughness.

[0013] 2) The present invention provides a toughened modified polyglycolic acid material, which can reduce the degradation rate of polyglycolic acid by adding a modifier, effectively solving the problem of excessively fast degradation of polyglycolic acid material and improving the stability of the toughened modified polyglycolic acid material;

[0014] 3) The polyglycolic acid toughening modified material provided by the present invention has a simple preparation method, excellent comprehensive mechanical properties, high rigidity and high toughness, good stability, and is completely biodegradable, which can meet the requirements of spun fibers and thin-walled injection molded products for material mechanical properties.

[0015] 4) The polyglycolic acid toughening modified material provided by this invention can also be applied to the field of disposable injection molded products and packaging products, which can effectively solve the pollution problem of disposable products. Attached Figure Description

[0016] Figure 1 This is a scanning electron microscope image of the polyglycolic acid toughened modified material obtained in Example 3;

[0017] Figure 2 This is a scanning electron microscope image of the polyglycolic acid toughened modified material obtained in Comparative Example 2;

[0018] Figure 3 The image shows a scanning electron microscope (SEM) image of the polyglycolic acid toughened modified material obtained in Comparative Example 4. Detailed Implementation

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] A first aspect of the present invention provides a polyglycolic acid toughening modified material, the toughening modified material being prepared from raw materials comprising the following components: 65-85 parts by weight of polyglycolic acid, 15-30 parts by weight of polybutylene succinate, 1-4 parts by weight of modifier, 0.5-5 parts by weight of compatibilizer, and 0.3-3 parts by weight of antioxidant; wherein, in the polyglycolic acid toughening modified material, the average particle size of polybutylene succinate is 100-900 nm.

[0021] In a preferred embodiment, the toughening modified material is prepared from raw materials comprising the following components: 78-82 parts by weight of polyglycolic acid, 18-22 parts by weight of polybutylene succinate, 2.5-3.5 parts by weight of modifier, 1-1.5 parts by weight of compatibilizer, and 1-1.5 parts by weight of antioxidant.

[0022] In a preferred embodiment, the polyglycolic acid (PGA) has a weight-average molecular weight ≥ 50,000, preferably 100,000-200,000; and a melt index of 2-100 g / min at 240°C and 2.16 kg load, preferably 10-50 g / 10 min.

[0023] In a preferred embodiment, the polybutylene succinate (PBS) has a weight-average molecular weight ≥ 50,000, preferably 100,000-150,000; and a melt index of 2-30 g / min at 190°C and 2.16 kg load, preferably 2-10 g / 10 min.

[0024] In a preferred embodiment, the modifier is a composite carbodiimide or a monomeric carbodiimide; more preferably, it is N,N'-dicyclohexylcarbodiimide and / or N,N'-diisopropylcarbodiimide.

[0025] In a preferred embodiment, the compatibilizer is selected from epoxy compounds and / or isocyanate compounds. However, this invention does not specifically limit the epoxy compounds; commonly used epoxy compounds and isocyanate compounds in the art can be used in this invention.

[0026] In a preferred embodiment, the epoxy compound is a copolymer containing glycidyl methacrylate groups, selected from styrene-acrylonitrile-glyceryl methacrylate copolymer and / or ethylene-methyl acrylate-glyceryl methacrylate copolymer.

[0027] In a preferred embodiment, the isocyanate compound is selected from one or more of toluene-2,4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, and polyisocyanates. The present invention does not specifically limit the polyisocyanate; commonly used polyisocyanates in the art can be used in this invention.

[0028] In a preferred embodiment, the antioxidant is a phosphite antioxidant, and more preferably one or more selected from antioxidant 168, antioxidant 626, and antioxidant 9228.

[0029] In a preferred embodiment, the polyglycolic acid toughening modified material contains polybutane succinate with an average particle size of 350-450 nm.

[0030] In a preferred embodiment, the notched impact strength of the polyglycolic acid toughened modified material is 5-12 kJ / m. 2 Preferably 8-10 kJ / m 2 Further preferably, it is 9.5-9.7 kJ / m 2 The tensile strength is 50-75 MPa, preferably 55-70 MPa; more preferably 62-65 MPa; the elongation at break is 120-180%, preferably 145-170%; more preferably 160-165%; the flexural modulus is 3800-5400 MPa, preferably 4000-5200 MPa; more preferably 4400-4500 MPa.

[0031] A second aspect of the present invention provides a method for preparing a polyglycolic acid toughened modified material, the method comprising: melt-blending and extruding granulation of 65-85 parts by weight of polyglycolic acid, 15-30 parts by weight of polybutylene succinate, 1-4 parts by weight of modifier, 0.5-5 parts by weight of compatibilizer, and 0.3-3 parts by weight of antioxidant to obtain the polyglycolic acid toughened modified material.

[0032] In a preferred embodiment, the method comprises: melt-blending and extruding granulation of 78-82 parts by weight of polyglycolic acid, 18-22 parts by weight of polybutylene succinate, 2.5-3.5 parts by weight of modifier, 1-1.5 parts by weight of compatibilizer, and 1-1.5 parts by weight of antioxidant to obtain the polyglycolic acid toughened modified material.

[0033] Polyglycolic acid, polybutylene succinate, modifier, compatibilizer and antioxidant are as described in the first aspect of this invention.

[0034] In a preferred embodiment, the extrusion granulation is carried out in a twin-screw extruder, and the melt blending conditions include a melt blending temperature of 225-240°C, preferably 235-240°C.

[0035] In a preferred embodiment, the operating conditions for the extrusion granulation include: a feeding section temperature of 180-210°C, a plasticizing section temperature of 200-230°C, a homogenizing section temperature of 220-235°C, an extrusion die temperature of 225-235°C, and an extrusion die pressure of 1-10 MPa.

[0036] In a preferred embodiment, the method further includes drying the raw material before extrusion granulation. More preferably, the drying is vacuum drying at a temperature of 60-80°C for 5-10 hours.

[0037] A third aspect of the present invention provides the application of the polyglycolic acid toughening modified material described in the first aspect of the present invention and / or the polyglycolic acid toughening modified material prepared by the method described in the second aspect of the present invention in spun fibers and / or thin-walled injection molded products.

[0038] The present invention will be described in detail below through examples. In the examples and comparative examples, the polyglycolic acid (PGA) used was purchased from Shanghai Pujing, with a weight-average molecular weight of 100,000-150,000 and a melt index of 27 g / 10 min at 240°C and a load of 2.16 kg; the PBS was purchased from Tunhe, Lanshan, Xinjiang, with a weight-average molecular weight of 50,000-150,000 and a melt index of 12 g / min at 190°C and a load of 2.16 kg.

[0039] Compatibilizers: Epoxy compounds were BASF ADR-4468 (GMA content 10 wt%, weight average molecular weight approximately 6680); isocyanate compounds were polyisocyanate (PMDI), specifically PM200 produced by Wanhua Chemical (viscosity at 25℃ 150-250 mPa·s, -NCO content 30.2-32 wt%, functionality 2.6-2.7). Silane coupling agent was purchased from Qufu Yishun Chemical, product brand KH-792.

[0040] The modifier is N,N'-dicyclohexylcarbodiimide, and the antioxidant is antioxidant 168.

[0041] The performance testing methods for the materials prepared in the examples and comparative examples are as follows:

[0042] (1) Notched impact strength: According to GB / T 1843-2008, at least 5 samples should be tested and the average value should be taken.

[0043] (2) Tensile strength and elongation at break: The tensile properties of injection molded small specimens were tested according to GB / T 16421-1996. At least 5 specimens were tested and the average value was taken.

[0044] (3) Flexural modulus: According to GB / T 1843-2008, at least 5 samples should be tested and the average value should be taken.

[0045] (4) Melt index: Measured using the GB / T 3682-2000 method.

[0046] (5) Particle size of polybutylene succinate: The sample was broken by liquid nitrogen, and then PBS was etched with chloroform. After that, SEM was used to observe and measure the particle size of PBS. The holes in the SEM image are the particle size of PBS.

[0047] Example 1

[0048] Polyglycolic acid was placed in a vacuum drying oven and dried at 80°C for 5 hours; polybutylene succinate was placed in a vacuum drying oven and dried at 60°C for 8 hours.

[0049] After being thoroughly mixed with dried polyglycolic acid, dried polybutylene succinate, modifier, antioxidant, and compatibilizer, the mixture was placed in a twin-screw extruder for melt blending and extrusion granulation to obtain a toughened modified polyglycolic acid material. The melt blending temperature was 235℃, the feeding section temperature during extrusion granulation was 225℃, the plasticizing section temperature was 230℃, the homogenizing section temperature was 235℃, the extrusion die temperature was 230℃, and the screw speed was 100 rad / min.

[0050] The types and amounts of raw materials used in Example 1 are shown in Table 1, and the test results of the obtained polyglycolic acid toughened modified material are shown in Table 2.

[0051] Examples 2-4

[0052] Similar to Example 1, the difference lies in the types and amounts of raw materials used in Examples 2-4, as shown in Table 1, and the test results of the obtained polyglycolic acid toughened modified materials, as shown in Table 2.

[0053] Comparative Examples 1-6

[0054] Similar to Example 1, the difference is that the types and amounts of raw materials used in Comparative Examples 1-6 are shown in Table 1, and the test results of the obtained polyglycolic acid toughened modified materials are shown in Table 2.

[0055] Table 1

[0056]

[0057]

[0058] Table 2

[0059]

[0060] As shown in Table 1, the polyglycolic acid toughened modified material prepared in this invention has excellent comprehensive mechanical properties, with both high rigidity and high toughness, good stability, and is completely biodegradable, which can meet the requirements of spun fibers and thin-walled injection molded products for material mechanical properties.

[0061] in, Figure 1 This is a scanning electron microscope image of the polyglycolic acid toughened modified material obtained in Example 3. Figure 2 The image shows a scanning electron microscope (SEM) image of the polyglycolic acid toughened modified material obtained in Comparative Example 2. Figure 1 The image shows a scanning electron microscope (SEM) image of the polyglycolic acid toughened modified material obtained in Comparative Example 4.

[0062] Depend on Figure 1 It is known that in the polyglycolic acid toughening modified material provided by the present invention, the average particle size of polybutane succinate is 410 nm and it is uniformly distributed.

[0063] Depend on Figure 2 It can be seen that by changing the amount of polyglycolic acid and polybutylene succinate, the average particle size of polybutylene succinate particles in the obtained polyglycolic acid toughened modified material is greater than 2000 nm and the distribution is uneven.

[0064] Depend on Figure 3 It can be seen that without the addition of compatibilizer, the average particle size of polybutylene succinate is 1800 nm, which is also relatively large and is detrimental to the mechanical properties of polyglycolic acid toughened modified materials.

[0065] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A polyglycolic acid toughened modified material, characterized in that, The toughening modified material is prepared from raw materials comprising the following components: 65-85 parts by weight of polyglycolic acid, 15-30 parts by weight of polybutylene succinate, 1-4 parts by weight of modifier, 0.5-5 parts by weight of compatibilizer, and 0.3-3 parts by weight of antioxidant; wherein, in the polyglycolic acid toughening modified material, the average particle size of polybutylene succinate is 190-900 nm; The polyglycolic acid has a weight-average molecular weight ≥ 50,000; and a melt index of 2-100 g / min at 240℃ and 2.16 kg load. The polybutane succinate has a weight-average molecular weight ≥ 50,000; and a melt flow index of 2-30 g / min at 190℃ and 2.16 kg load. The modifier is a composite carbodiimide or a monomeric carbodiimide; The compatibilizer is selected from epoxy compounds and / or isocyanate compounds; the epoxy compound is a copolymer containing glycidyl methacrylate groups.

2. The toughened modified material according to claim 1, wherein, The toughening modified material is prepared from raw materials comprising the following components: 78-82 parts by weight of polyglycolic acid, 18-22 parts by weight of polybutylene succinate, 2.5-3.5 parts by weight of modifier, 1-1.5 parts by weight of compatibilizer, and 1-1.5 parts by weight of antioxidant.

3. The toughened modified material according to claim 1 or 2, wherein, The polyglycolic acid has a weight-average molecular weight of 100,000-200,000 and a melt index of 10-50 g / 10 min at 240 °C and 2.16 kg load.

4. The toughened modified material according to claim 1 or 2, wherein, The polybutane succinate has a weight-average molecular weight of 100,000-150,000 and a melt index of 2-10 g / 10 min at 190 °C and 2.16 kg load.

5. The toughened modified material according to claim 1 or 2, wherein, The modifier is N,N'-dicyclohexylcarbodiimide and / or N,N'-diisopropylcarbodiimide.

6. The toughened modified material according to claim 1 or 2, wherein, The epoxy compounds are selected from styrene-acrylonitrile-glyceryl methacrylate copolymer and / or ethylene-methyl acrylate-glyceryl methacrylate copolymer.

7. The toughened modified material according to claim 1 or 2, wherein, The isocyanate compound is selected from one or more of toluene-2,4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, and polyisocyanate.

8. The toughened modified material according to claim 1 or 2, wherein, The antioxidant is a phosphite antioxidant.

9. The toughened modified material according to claim 8, wherein, The antioxidant is selected from one or more of antioxidant 168, antioxidant 626 and antioxidant 9228.

10. The toughened modified material according to claim 1 or 2, wherein, In the polyglycolic acid toughened modified material, the average particle size of polybutane succinate is 350-450 nm.

11. The toughened modified material according to claim 1 or 2, wherein, The notched impact strength of the polyglycolic acid toughened modified material is 5-12 kJ / m. 2 The tensile strength is 50-75 MPa; the elongation at break is 120-180%; and the flexural modulus is 3800-5400 MPa.

12. The toughened modified material according to claim 11, wherein, The notched impact strength of the polyglycolic acid toughened modified material is 8-10 kJ / m. 2 The tensile strength is 55-70 MPa; the elongation at break is 145-170%; and the flexural modulus is 4000-5200 MPa.

13. A method for preparing the polyglycolic acid toughened modified material according to any one of claims 1-12, characterized in that, The method includes: melt-blending and extruding granulation of 65-85 parts by weight of polyglycolic acid, 15-30 parts by weight of polybutylene succinate, 1-4 parts by weight of modifier, 0.5-5 parts by weight of compatibilizer, and 0.3-3 parts by weight of antioxidant to obtain the polyglycolic acid toughened modified material.

14. The method according to claim 13, wherein, The extrusion granulation is carried out in a twin-screw extruder, and the melt blending conditions include a melt blending temperature of 230-240°C.

15. The method according to claim 14, wherein, The extrusion granulation is carried out in a twin-screw extruder, and the melt blending conditions include a melt blending temperature of 235-240℃.

16. The method according to claim 13, wherein, The operating conditions for extrusion granulation include: a feeding section temperature of 180-210℃, a plasticizing section temperature of 200-230℃, a homogenizing section temperature of 220-235℃, an extrusion die temperature of 225-235℃, and an extrusion die pressure of 1-10MPa.

17. The use of the polyglycolic acid toughening modified material according to any one of claims 1-12 in spun fibers and / or thin-walled injection molded products.

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