CN114163791A - Modified polyglycolic acid composition, modified polyglycolic acid material, and preparation method and application thereof - Google Patents

Modified polyglycolic acid composition, modified polyglycolic acid material, and preparation method and application thereof Download PDF

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CN114163791A
CN114163791A CN202010836760.1A CN202010836760A CN114163791A CN 114163791 A CN114163791 A CN 114163791A CN 202010836760 A CN202010836760 A CN 202010836760A CN 114163791 A CN114163791 A CN 114163791A
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polyglycolic acid
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composition
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copolymer
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CN114163791B (en
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王荣
孙小杰
陈兰兰
梁文斌
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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National Institute of Clean and Low Carbon Energy
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    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract

The invention relates to the field of polyglycolic acid modification, and discloses a modified polyglycolic acid composition, a modified polyglycolic acid material, and a preparation method and application thereof. Note that the modified polyglycolic acid composition comprises polyglycolic acid, a toughening resin, and a modifier; the toughening resin is selected from at least one of polyethylene, polypropylene and polyolefin elastomer; the modifier is selected from at least one of amino grafted polyolefin, maleic anhydride polyolefin copolymer, maleic anhydride grafted polyolefin elastomer and epoxy compound. The invention selects proper toughening resin and adds the improver to improve the compatibility among the resins, improve the toughness of the PGA, prepare the high-toughness PGA material and solve the problem of toughening and modifying the PGA.

Description

Modified polyglycolic acid composition, modified polyglycolic acid material, and preparation method and application thereof
Technical Field
The invention relates to the field of polyglycolic acid modification, and in particular relates to a modified polyglycolic acid composition, a modified polyglycolic acid material, and a preparation method and application thereof.
Background
Polyglycolic acid (PGA for short) is an aliphatic polyester polymer material with the least carbon number of units, completely decomposable ester structure and fastest degradation speed, and has good performance advantages:
1) excellent gas barrier properties: the barrier property to oxygen and water vapor is 100 times that of PET and 1000 times that of PLA, and the barrier property of PGA to gas is not affected by the environmental temperature basically, so the PGA is an ideal barrier packaging material;
2) the mechanical property is excellent: the bending strength and tensile strength are higher than those of general resins such as PP, and even better than those of many engineering plastics such as: PC, PET, PA6 and the like can make up for the defect of poor mechanical strength of biodegradable materials;
3) the degradability is excellent: PGA has degradation properties similar to those of natural fibers and can be decomposed within one month. Can meet the requirement of material degradation.
Because of its performance advantages, PGA is a very environmentally friendly, ideal packaging material. However, PGA has disadvantages of high brittleness, low melt strength, etc., and thus, its processing application in the fields of films, etc. is severely restricted. CN1059919A discloses films comprising polyhydroxy acids and a compatibilizer, the present invention relates to certain compositions useful for making films comprising polyhydroxy acids (PHA) and a compatibilizer, and their preparation. It also relates to films comprising such compositions and other polymers, in particular consisting of 5-95% polyhydroxy acid and 5-75% compatibilizer. Wherein the polyhydroxy acids include: polyglycolic acid, polylactic acid, and polyglycolic acid/polylactic acid copolymers. The compatilizer comprises: ethylene/maleic anhydride graft copolymers or ethylene/ethylene oxide copolymers. In the invention, the toughening resin is polyethylene/polypropylene, the compatilizer is ethylene/maleic anhydride graft copolymer or ethylene/ethylene oxide copolymer, other elastomers and the like are not included, and compared with the elastomer, the toughness of the polyethylene/polypropylene is not high, so that the toughness is increased limitedly.
CN102131868A discloses a hydrolysis-resistant polyester composition, comprising a polyester, a first modifier and a second modifier; the first modifier includes a polymer incompatible with the polyhydroxyalkanoate and is not an acid-containing polymer or an acid-generating polymer, and specifically includes: ethylene copolymers, core-shell polymers, copolyetheresters, epoxidized oils, acrylonitrile styrene copolymers, styrene-containing polymers, aromatic polyesters, aliphatic-aromatic polyesters, ethylene propylene diene monomer rubbers, polyolefins, or combinations of two or more thereof; the second modifier comprises: a polycarbodiimide, a carbodiimide, a diimide compound, or a combination thereof. The second modifier is carboxyl end capping agent, mainly improves the hydrolysis resistance of the polyglycolic acid, and does not relate to a compatilizer. The two phases are still incompatible systems, and no improvement is made on mechanical properties.
Therefore, it is necessary to develop a tough PGA material by toughening and modifying PGA, but few studies have been made on toughening and modifying PGA at present, and the problems of toughness and compatibility of the material need to be solved.
Disclosure of Invention
The invention aims to overcome the problems of poor toughness and poor improver of the existing polyglycolic acid material, and provides a modified polyglycolic acid composition, a modified polyglycolic acid material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides in a first aspect a modified polyglycolic acid composition comprising polyglycolic acid, a toughening resin, and an improver; the toughening resin is selected from at least one of polyethylene, polypropylene and polyolefin elastomer; the modifier is selected from at least one of amino grafted polyolefin, maleic anhydride polyolefin copolymer, maleic anhydride grafted polyolefin elastomer and epoxy compound.
The second aspect of the present invention provides a method for preparing a modified polyglycolic acid material, comprising: the composition of the present invention is melt-extruded to obtain a modified polyglycolic acid material.
In a third aspect of the present invention, there is provided a modified polyglycolic acid material obtained by the production method of the present invention.
The fourth aspect of the invention provides an application of the material provided by the invention in films, lunch boxes, hollow containers and 3D printing.
According to the technical scheme, the proper toughening resin is selected and added with the improver to improve the compatibility among resins, improve the toughness of the PGA, prepare the high-toughness PGA material and solve the problem in toughening and modifying the PGA.
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FIG. 1 is an SEM image of a polyglycolic acid material prepared in comparative example 2;
FIG. 2 is an SEM photograph of a modified polyglycolic acid material prepared in example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides in a first aspect a modified polyglycolic acid composition comprising: polyglycolic acid, toughening resin and improver; the toughening resin is selected from at least one of polyethylene, polypropylene and polyolefin elastomer; the modifier is selected from at least one of amino grafted polyolefin, maleic anhydride polyolefin copolymer, maleic anhydride grafted polyolefin elastomer and epoxy compound.
In some embodiments of the present invention, the composition provides the following components in amounts such that polyglycolic acid is 40 to 95 parts by weight, the toughening resin is 5 to 60 parts by weight, and the modifier is 0.5 to 10 parts by weight. The composition of the composition can enable the polyglycolic acid material prepared further to have the performances of high toughness and high strength.
In some embodiments of the present invention, preferably, the polyglycolic acid is 50 to 80 parts by weight, the toughening resin is 20 to 50 parts by weight, and the modifier is 2 to 5 parts by weight.
In some embodiments of the invention, the polyglycolic acid is selected to provide a high mechanical strength effect. Preferably, the polyglycolic acid has a weight average molecular weight of 5 to 50 ten thousand, preferably 10 to 30 ten thousand. Preferably, the polyglycolic acid has a melt index of 20 to 100g/10min at 240 ℃ and a load of 2.16 kg. The polyglycolic acid is commercially available, for example, from Shanghai Pujing chemical technology, Inc.
In some embodiments of the present invention, preferably, the composition has a melt viscosity of 1000-. In the present invention, the melt viscosity of the composition is measured by a rheological method and the measurement is performed at 240 ℃, 2% strain and 0.05rad/s frequency. The composition may have better processability.
In the present invention, the above-mentioned relationship between the polyglycolic acid and the composition is satisfied, and the effects or effects of enhancing melt strength, improving processability and increasing toughness can be provided.
In some embodiments of the present invention, toughening with the toughening resin can improve the notched impact performance of the resulting modified polyglycolic acid material. Preferably, the polyethylene has a density of 0.9 to 0.96g/cm3The polyethylene has a melt index of 0.1 to 15g/10min at 190 ℃ and under a load of 2.16 kg.
Preferably, the polypropylene has a density of 0.9 to 0.96g/cm3The polypropylene has a melt index of 0.2 to 20g/10min at 230 ℃ and under a load of 2.16 kg.
Preferably, the polyolefin elastomer is at least one of an ethylene and alpha-olefin copolymer, a propylene-ethylene copolymer, and an ethylene-propylene-diene monomer rubber. The polyolefin elastomer has a density of 0.86-0.95g/cm3And a melt index at 230 ℃ and under a load of 2.16kg of 0.3 to 30g/10 min. Preferably, the polyolefin elastomer is an ethylene-octene copolymer, a polypropylene and polyethylene block copolymer. The toughening resins are commercially available, for example, China petrochemical polypropylene PP 8101 (density 0.90 g/cm)3And a melt index of 0.36g/10min at 230 ℃ and a load of 2.16 kg). Polyolefin elastomer POE8457 (density 0.87 g/cm)3And a melt index at 190 ℃ under a load of 2.16kg of 3.0g/10 min).
In some embodiments of the invention, the modifier is capable of providing a reaction with the two-phase component or increasing polarity to enhance the two-phase interfacial interaction, resulting in the technical effects of increased compatibility and increased toughness. Preferably, the amino-grafted polyolefin has the structure represented by formula 1:
Figure BDA0002639965210000051
wherein the content of the first and second substances,
Figure BDA0002639965210000052
the polymer chain is polyethylene, polypropylene or polyethylene elastomer; the graft ratio of the amino-grafted polyolefin is 0.2 to 2% by weight, and Et represents an ethyl group.
The graft ratio of the maleic anhydride-grafted polyolefin elastomer is 0.2 to 5 wt%. Commercially available, for example, dow GR216 (grafting ratio of 0.5 wt% to 1.0 wt%). The maleic anhydride grafted polyolefin elastomer meeting the performance parameters is selected, so that the modified polyglycolic acid material further obtained from the composition has high toughness.
The maleic anhydride polyolefin copolymer has the structure shown in formula 2:
Figure BDA0002639965210000053
wherein R is H, C1-C6Alkyl, phenyl or C1-C6An alkoxy group, and n is an integer of 2 or more.
In some embodiments of the present invention, preferably, the epoxy compound includes, but is not limited to, copolymers containing Glycidyl Methacrylate (GMA) groups; wherein the content of Glycidyl Methacrylate (GMA) groups is 0.5-20 wt%. Preferably, the epoxy compound is at least one selected from the group consisting of a styrene-acrylonitrile-glycidyl methacrylate copolymer, an ethylene-methyl acrylate-glycidyl methacrylate copolymer, an ethylene-ethyl acrylate-glycidyl methacrylate copolymer, a POE elastomer-glycidyl methacrylate copolymer, and a styrene-methacrylate-glycidyl methacrylate copolymer. Commercially available, for example, readily available SOG-02(POE-g-GMA, GMA content of 0.8-1.2 wt%).
In the invention, the improver can react with PGA in the composition to form a graft polymer, so as to increase the two-phase compatibility of the polyglycolic acid and the toughening resin. In some embodiments, the weight ratio of the toughening resin to the modifier is from 4 to 20:1, preferably from 4 to 10: 1. When the mutual dosage of the toughening resin and the improver is within the range, the toughening resin and the improver have better synergy, can provide better compatibility of two phases of the polyglycolic acid and the toughening resin, and enables the obtained modified polyglycolic acid material to have the balance of toughness and rigidity. The use amount of the toughening resin is too small, the toughness of the prepared material is increased limitedly, and the toughness is insufficient; the use of the toughening resin in too much amount may affect the final rigidity of the resulting material.
The second aspect of the present invention provides a method for preparing a modified polyglycolic acid material, comprising: the composition of the present invention is melt-extruded to obtain a modified polyglycolic acid material.
In a specific embodiment provided by the present invention, the preparation method may include:
1) drying polyglycolic acid, toughening resin and an improver for later use;
2) uniformly mixing the dried polyglycolic acid, the toughening resin and the improver according to the using amount of the components in the composition provided by the invention;
3) and (3) carrying out melt extrusion on the mixture obtained in the step (2), and pelletizing to obtain the modified polyglycolic acid.
In some embodiments of the present invention, preferably, the melt blending conditions comprise: the temperature is 225-250 ℃, preferably 235-240 ℃; the time is 4-10min, preferably 5-8 min; the extruder speed is 60-110rpm, preferably 80-100 rpm.
In the present invention, the inventors have studied the conditions of melt blending, and have found that when the modified 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 polyglycolic acid composition obtained can be avoided.
In a third aspect of the present invention, there is provided a modified polyglycolic acid material obtained by the production method of the present invention.
The modified polyglycolic acid material prepared by the invention has improved performance, and in some preferred embodiments, the notch impact strength of the modified polyglycolic acid material can be improved by more than 1.5 times compared with polyglycolic acid, and can reach more than or equal to 4kJ/m2And a flexural modulus of 1.5GPa or more and a flexural strength of 60MPa or more, and a material having a high rigidity-toughness balance is obtained.
The fourth aspect of the invention provides an application of the material provided by the invention in films, lunch boxes, hollow containers and 3D printing.
In the present invention, the melt index is measured in accordance with GB/T3682-2000.
The present invention will be described in detail below by way of examples. In the following examples, the modified polyglycolic acid material was observed by SEM, and a sample was quenched by liquid nitrogen cooling using Nova NanoSEM 450, and the cross section was observed after carbon spraying. The dispersion and particle condition of each component in the material were observed.
And (4) determining the notch impact strength of the sample according to GB/T1043-2008, testing at least 5 samples of the sample, and taking an average value.
The bending properties of the samples were determined according to GB/T1843-2008, and at least 5 samples were tested and averaged.
The melt viscosity of the sample was measured according to the rheological method at 240 ℃ under the condition of 2% strain and 0.05rad/s frequency.
Polyglycolic acid (PGA) is provided by Shanghai Pujing chemical technology Co., Ltd, and is marked as PGA-1 (melt index of 64.0g/10min, weight average molecular weight of 15 ten thousand); PGA-2 (melt index 45.0g/10min, weight average molecular weight 20 ten thousand); PGA-3 (melt index 85.0g/10min, weight average molecular weight 9 ten thousand).
Toughening resin 1: polyolefin elastomer: POE8457 (density 0.87 g/cm)3Melt index at 190 ℃ and load 2.16kg of 3.0g/10min) were purchased from dow chemistry;
and (3) toughening resin 2: polypropylene PP 8101 (density 0.90 g/cm)3Melt index at 230 ℃ and load of 2.16kg of 0.36g/10min), china petrochemicals;
improver 1: POE-g-MAH (maleic anhydride grafted polyolefin elastomer, GR216, graft 0.5 wt% -1.0 wt%) was purchased from Dow chemical
And (2) improver: POE-g-GMA (epoxy compound, SOG-02, GMA content 0.8-1.2% by weight) was purchased from Karaoka;
and (3) improver: the synthesis steps of the amino grafted polyolefin (PP-g-NHR) are as follows:
fully mixing 0.5-3 parts by weight of N-ethyl ethylenediamine liquid and 100 parts by weight of PP-g-MAH, adding the mixture into a double-screw extruder, extruding and granulating at the extrusion temperature of 200 ℃ and the rotation speed of 100rmp to obtain the amino grafted polypropylene PP-g-NHR. The graft ratio is 0.5 to 2% by weight.
In the following examples and comparative examples, polyglycolic acid, a toughening resin and a modifier were used after drying.
Example 1
Uniformly mixing 80 parts by weight of polyglycolic acid PGA-1, 20 parts by weight of polypropylene (PP 8101) and 5 parts by weight of improver 3 (amino grafted polypropylene, PP-g-NHR), 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 carrying out extrusion granulation to obtain the modified polyglycolic acid material.
The formulation of the composition and the test results are shown in table 1. The modified polyglycolic acid material thus obtained was observed by SEM, and the obtained photograph is shown in FIG. 2. As can be seen from fig. 2, the compatibility between polar PGA and non-polar PP makes the two-phase size smaller.
Example 2
Uniformly mixing 80 parts by weight of polyglycolic acid PGA-1, 20 parts by weight of POE8457 and 5 parts by weight of improver 3(PP-g-NHR), and then carrying out melt blending for 8min at 235 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 80rpm, and carrying out extrusion granulation to obtain the modified polyglycolic acid material.
The formulation of the composition and the test results are shown in table 1.
Example 3
Uniformly mixing 80 parts by weight of polyglycolic acid, 20 parts by weight of POE8457 and 2 parts by weight of improver 3(PP-g-NHR), and then carrying out melt blending for 8min at 235 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 80rpm, and carrying out extrusion granulation to obtain the modified polyglycolic acid material.
The formulation of the composition and the test results are shown in table 1.
Example 4
Uniformly mixing 65 parts by weight of polyglycolic acid PGA-1, 35 parts by weight of POE8457 and 5 parts by weight of improver 3(PP-g-NHR), and then carrying out melt blending for 8min at 235 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 80rpm, and carrying out extrusion granulation to obtain the modified polyglycolic acid material.
The formulation of the composition and the test results are shown in table 1.
Example 5
Uniformly mixing 50 parts by weight of polyglycolic acid PGA-1, 50 parts by weight of POE8457 and 5 parts by weight of improver 3(PP-g-NHR), and then carrying out melt blending for 8min at 235 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 80rpm, and carrying out extrusion granulation to obtain the modified 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-1, 20 parts by weight of POE8457 and 5 parts by weight of improver 1(POE-g-MAH), and then carrying out melt blending for 5min at 240 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 90rpm, and carrying out extrusion granulation to obtain the modified 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-1, 20 parts by weight of POE8457 and 5 parts by weight of improver 2(POE-g-GMA), 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 carrying out extrusion granulation to obtain the modified polyglycolic acid material.
The formulation of the composition and the preparation conditions are shown in table 1, and the test results are shown in table 2.
Example 8
Uniformly mixing 80 parts by weight of polyglycolic acid PGA-2, 20 parts by weight of POE8457 and 5 parts by weight of improver 3(PP-g-NHR), and then carrying out melt blending for 8min at 235 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 80rpm, and carrying out extrusion granulation to obtain the modified polyglycolic acid material.
The formulation of the composition and the test results are shown in table 1.
Example 9
Uniformly mixing 80 parts by weight of polyglycolic acid PGA-3, 20 parts by weight of POE8457 and 5 parts by weight of improver 3(PP-g-NHR), and then carrying out melt blending for 8min at 235 ℃ by using a double-screw extruder, wherein the rotating speed of the extruder is 80rpm, and carrying out extrusion granulation to obtain the modified 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 polyglycolic acid PGA-1 was melt-extruded at 240 ℃ for 6 minutes by means of a twin-screw extruder at a rotation speed of 100 rpm. The test results are shown in table 1.
Comparative example 2
100 parts by weight of polyglycolic acid PGA-1 and 5 parts by weight of modifier 3(PP-g-NHR) are uniformly mixed, and then are melted and blended for 6min by a double-screw extruder at the temperature of 240 ℃, and the rotating speed of the extruder is 100rpm for extrusion granulation. The formulation of the composition and the test results are shown in table 1.
Comparative example 3
Uniformly mixing 80 parts by weight of polyglycolic acid PGA-1 and 20 parts by weight of polypropylene (PP 8101), 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 carrying out extrusion granulation.
The formulation of the composition and the test results are shown in table 1. The polyglycolic acid material obtained was observed by SEM, and the photograph thereof was shown in FIG. 1. As can be seen from fig. 1, the blending between PGA and the toughening resin PP has a distinct phase separation structure and a large phase size.
Comparative example 4
80 parts by weight of polyglycolic acid PGA-1 and 20 parts by weight of POE8457 are uniformly mixed, and then are melted and blended for 6min at 240 ℃ by a double-screw extruder, and the rotating speed of the extruder is 100rpm for extrusion granulation. The formulation of the composition and the test results are shown in table 1.
Comparative example 5
65 parts by weight of polyglycolic acid PGA-1 and 35 parts by weight of POE8457 are uniformly mixed, and then the mixture is melted and blended for 6min at 240 ℃ by a double-screw extruder, and the rotating speed of the extruder is 100rpm for extrusion granulation. The formulation of the composition and the test results are shown in table 1.
Comparative example 6
50 parts by weight of polyglycolic acid PGA-1 and 50 parts by weight of POE8457 are uniformly mixed, and then are melted and blended for 6min at 240 ℃ by a double-screw extruder, and the rotating speed of the extruder is 100rpm for extrusion granulation. The formulation of the composition and the test results are shown in table 1.
TABLE 1
Figure BDA0002639965210000111
Figure BDA0002639965210000121
TABLE 1 (continuation)
Figure BDA0002639965210000122
Figure BDA0002639965210000131
It can be seen from the results of the examples, the comparative examples and the table 1 that the composition provided by the invention can be used for toughening and modifying PGA, and the obtained modified polyglycolic acid material has high notched impact strength, obviously improved material toughness and good bending property. For example, example 1 has improved melt viscosity, notched impact strength and flexural properties compared to comparative example 3, and examples 2, 3, 6-9 have improved melt viscosity, notched impact strength and flexural properties compared to comparative example 4, enabling better processability and balanced toughness and flexibility. Example 4 compared with comparative example 5, example 5 compared with comparative example 6, the modified polyglycolic acid material provided by the present invention has improved toughness and simultaneously has good bending properties. The comparative examples 1 and 2, which do not have a toughening resin and/or a modifier, do not achieve toughness improvement of polyglycolic acid.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A modified polyglycolic acid composition comprising: polyglycolic acid, toughening resin and improver; the toughening resin is selected from at least one of polyethylene, polypropylene and polyolefin elastomer; the modifier is selected from at least one of amino grafted polyolefin, maleic anhydride polyolefin copolymer, maleic anhydride grafted polyolefin elastomer and epoxy compound.
2. The composition of claim 1, wherein in the composition, the polyglycolic acid is 40 to 95 parts by weight, the toughening resin is 5 to 60 parts by weight, and the modifier is 0.5 to 10 parts by weight;
preferably, the polyglycolic acid is 50-80 parts by weight, the toughening resin is 20-50 parts by weight, and the modifier is 2-5 parts by weight.
3. A composition according to claim 1 or 2, wherein the polyglycolic acid has a weight average molecular weight in the range of 5 to 50 ten thousand, preferably 10 to 30 ten thousand.
4. The composition of any one of claims 1-3, wherein the composition has a melt viscosity of 1000-50000 Pa-s at 240 ℃.
5. The composition of any of claims 1-5, wherein the polyethylene has a density of 0.9 to 0.96g/cm3The melt index of the polyethylene at 190 ℃ and under the load of 2.16kg is 0.1-15g/10 min;
the density of the polypropylene is 0.9-0.96g/cm3The melt index of the polypropylene at 230 ℃ and under the load of 2.16kg is 0.2-20g/10 min;
the polyolefin elastomer is at least one of ethylene and alpha-olefin copolymer, propylene-ethylene copolymer and ethylene propylene diene monomer, preferably ethylene-octene copolymer, polypropylene and polyethylene block copolymer.
6. The composition of claim 1, wherein the amino-grafted polyolefin has a structure represented by formula 1:
Figure FDA0002639965200000021
wherein the content of the first and second substances,
Figure FDA0002639965200000022
the polymer chain is polyethylene, polypropylene or polyethylene elastomer; the grafting ratio of the amino grafted polyolefin is 0.2-2 wt%;
the grafting rate of the maleic anhydride grafted polyolefin elastomer is 0.2-5 wt%;
the maleic anhydride polyolefin copolymer has the structure shown in formula 2:
Figure FDA0002639965200000023
r is H, C1-C6Alkyl, phenyl or C1-C6An alkoxy group, n is an integer of 2 or more;
the epoxy compound comprises a copolymer containing glycidyl methacrylate groups, and preferably, the epoxy compound is at least one selected from the group consisting of a styrene-acrylonitrile-glycidyl methacrylate copolymer, an ethylene-methyl acrylate-glycidyl methacrylate copolymer, an ethylene-ethyl acrylate-glycidyl methacrylate copolymer, a POE elastomer-glycidyl methacrylate copolymer, and a styrene-methacrylate-glycidyl methacrylate copolymer.
7. A preparation method of a modified polyglycolic acid material comprises the following steps:
melt extruding the composition of any one of claims 1 to 6 to obtain a modified polyglycolic acid material.
8. The method of claim 7, wherein the melt extrusion conditions comprise: the temperature is 225-250 ℃, preferably 235-240 ℃; the time is 4-10min, preferably 5-8 min; the extruder speed is 60-110rpm, preferably 80-100 rpm.
9. A modified polyglycolic acid material prepared by the preparation method according to claim 7 or 8;
preferably, the notch impact strength of the modified polyglycolic acid material is more than or equal to 4kJ/m2And has a flexural modulus of 1.5GPa or more and a flexural strength of 60MPa or more.
10. Use of the material of claim 9 in films, lunch boxes, hollow containers, 3D printing.
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CN114934328A (en) * 2022-06-06 2022-08-23 广州明晖新材料有限公司 Corrosion-resistant nylon yarn and manufacturing method thereof
WO2024037580A1 (en) * 2022-08-19 2024-02-22 中国石油化工股份有限公司 Polymer composition and preparation method therefor, and product

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JP2020002189A (en) * 2018-06-25 2020-01-09 株式会社クレハ Method for producing polyglycolic acid resin composition

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CN103554869A (en) * 2013-10-24 2014-02-05 宁波康氏塑料科技有限公司 Polyolefin elastomer (POE) toughened polycarbonate composite material and preparation method thereof
JP2020002189A (en) * 2018-06-25 2020-01-09 株式会社クレハ Method for producing polyglycolic acid resin composition

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CN114934328A (en) * 2022-06-06 2022-08-23 广州明晖新材料有限公司 Corrosion-resistant nylon yarn and manufacturing method thereof
WO2024037580A1 (en) * 2022-08-19 2024-02-22 中国石油化工股份有限公司 Polymer composition and preparation method therefor, and product

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