CN116814054A - Polyglycolic acid toughening modified material, and preparation method and application thereof - Google Patents
Polyglycolic acid toughening modified material, and preparation method and application thereof Download PDFInfo
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- CN116814054A CN116814054A CN202210286887.XA CN202210286887A CN116814054A CN 116814054 A CN116814054 A CN 116814054A CN 202210286887 A CN202210286887 A CN 202210286887A CN 116814054 A CN116814054 A CN 116814054A
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 83
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 7
- -1 polybutylene succinate Polymers 0.000 claims abstract description 38
- 239000004631 polybutylene succinate Substances 0.000 claims abstract description 34
- 229920002961 polybutylene succinate Polymers 0.000 claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 23
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 23
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 5
- 150000001718 carbodiimides Chemical class 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 238000001746 injection moulding Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 241000628997 Flos Species 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 229920006237 degradable polymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- SENMPMXZMGNQAG-UHFFFAOYSA-N 3,4-dihydro-2,5-benzodioxocine-1,6-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC=C12 SENMPMXZMGNQAG-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention relates to the technical field of polyglycolic acid modification, and discloses a polyglycolic acid toughening modified material, a preparation method and application thereof. The polyglycolic acid toughening modified material is prepared from the following raw materials: 65-85 parts of polyglycolic acid, 15-30 parts of polybutylene succinate, 1-4 parts of modifier, 0.5-5 parts of compatilizer and 0.3-3 parts of antioxidant; wherein, in the polyglycolic acid toughening modified material, the average grain diameter of the polybutylene succinate is 100-900nm. The polyglycolic acid toughening modified material has high rigidity and high toughness, and has good application prospect in the fields of spinning fiber, thin-wall injection molding products and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyglycolic acid toughening modified material, a preparation method and application thereof.
Background
In recent years, the "white pollution" produced by disposable plastic products places a heavy burden on the ecological environment. Since the implementation of "plastic-limiting", biodegradable polyester materials that are renewable, degradable and biocompatible have been of great interest.
Among them, PGA (polyglycolic acid) is a biodegradable material having good biodegradability and biocompatibility, gas barrier property, and excellent mechanical strength. PGA, however, also has the disadvantages of high brittleness, low melt strength, easy decomposition, etc., which severely limit its application in the fields of spun fibers, thin-wall injection molded products, etc.
CN107987494a discloses a biodegradable polyethylene terephthalate blend comprising the following components in parts by weight: 50-70 parts of polyethylene terephthalate, 10-40 parts of polyglycolic acid, 5-10 parts of compatilizer, 0.1-0.5 part of antioxidant and 1-2 parts of hydrolysis resistance agent. Although the blend has good biodegradability, the ethylene glycol phthalate is taken as a main resin, the PGA is taken as a modified resin, and the related mechanical properties of the blend are not mentioned.
CN111154245a discloses a full-biodegradable dental floss rod handle and a preparation method thereof, wherein the material comprises 60-90 parts of polyglycolic acid; 5-30 parts of a toughening agent (one or more of polybutylene adipate terephthalate, polybutylene succinate, polycaprolactone, polyhydroxyalkanoate, polypropylene carbonate, acrylic acid ester degradable polymer and maleic anhydride grafted degradable polymer); 0.1-5 parts of nucleating agent; 0.1-2 parts of a lubricant; 0.1-1 part of compatilizer (silane coupling agent, aluminate, titanate) and 0.1-3 parts of antibacterial agent. The full-biodegradable dental floss rod handle has good biodegradability, but the dental floss rod has low requirements on mechanical properties, and the silane coupling agent, aluminate and titanate compatilizer have poor effect of improving the mechanical properties of materials.
Accordingly, there is a need to provide a biodegradable PGA material capable of having both high rigidity and high toughness.
Disclosure of Invention
The invention aims to solve the problems of high brittleness, low melt strength and high degradation speed of a PGA material, and provides a polyglycolic acid toughening modified material, a preparation method and application thereof.
In order to achieve the above purpose, the invention provides a polyglycolic acid toughening modified material, which is prepared from the following raw materials: 65-85 parts of polyglycolic acid, 15-30 parts of polybutylene succinate, 1-4 parts of modifier, 0.5-5 parts of compatilizer and 0.3-3 parts of antioxidant; wherein, in the polyglycolic acid toughening modified material, the average grain diameter of the polybutylene succinate is 100-900nm.
The second aspect of the invention provides a method for preparing a polyglycolic acid toughening modified material, the method comprising: and (3) carrying out melt blending and extrusion granulation on 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 compatilizer and 0.3-3 parts by weight of antioxidant to obtain the polyglycolic acid toughening modified material.
The third aspect of the invention provides an application of the polyglycolic acid toughening modified material prepared by the first aspect of the invention and/or the polyglycolic acid toughening modified material prepared by the method of the second aspect of the invention in spinning fibers and/or thin-wall injection molding products.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
1) According to the polyglycolic acid toughening modified material provided by the invention, polyglycolic acid is taken as base resin, and polyglycolic acid is modified by using polybutylene succinate, a modifier, a compatilizer and an antioxidant, and the synergistic effect among the components, especially the synergistic effect among specific content of polybutylene succinate and the compatilizer, is realized, so that the prepared polyglycolic acid toughening modified material of polybutylene succinate exists in a nano particle state, and thus the polyglycolic acid toughening modified material with high rigidity and high toughness is obtained;
2) According to the polyglycolic acid toughening modified material provided by the invention, the degradation speed of polyglycolic acid can be reduced by adding the modifier, the problem that the degradation speed of the polyglycolic acid material is too high can be effectively solved, and the stability of the polyglycolic acid toughening modified material is improved;
3) The polyglycolic acid toughening modified material provided by the invention has the advantages of simple preparation method, excellent mechanical comprehensive performance of the material, high rigidity and high toughness, good stability, complete biodegradation and capability of meeting the requirement of spinning fiber and thin-wall injection molding products on the mechanical performance of the material;
4) The polyglycolic acid toughening modified material provided by the invention can be applied to the fields of disposable injection molding products and packaging products, and can effectively solve the pollution problem of disposable products.
Drawings
FIG. 1 is a scanning electron microscope image of the polyglycolic acid toughening modified material obtained in example 3;
FIG. 2 is a scanning electron microscope image of the polyglycolic acid toughening modified material obtained in comparative example 2;
FIG. 3 is a scanning electron microscope image of the polyglycolic acid-toughened modified material obtained in comparative example 4.
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 invention provides a polyglycolic acid toughening modified material, which is prepared from the following raw materials: 65-85 parts of polyglycolic acid, 15-30 parts of polybutylene succinate, 1-4 parts of modifier, 0.5-5 parts of compatilizer and 0.3-3 parts of antioxidant; wherein, in the polyglycolic acid toughening modified material, the average grain diameter of the polybutylene succinate is 100-900nm.
In a preferred embodiment, the toughening modification material is prepared from the following raw materials: 78-82 parts of polyglycolic acid, 18-22 parts of polybutylene succinate, 2.5-3.5 parts of modifier, 1-1.5 parts of compatilizer and 1-1.5 parts of antioxidant.
In a preferred embodiment, the polyglycolic acid (PGA) has a weight average molecular weight of not less than 50000, preferably 100000 to 200000; the melt index at 240℃and under a load of 2.16kg is 2-100g/min, preferably 10-50g/10min.
In a preferred embodiment, the weight average molecular weight of the polybutylene succinate (PBS) is equal to or more than 50000, preferably 100000-150000; the melt index at 190℃and under a load of 2.16kg is 2-30g/min, preferably 2-10g/10min.
In a preferred embodiment, the modifier is a complex carbodiimide or a monomeric carbodiimide; further preferred are N, N '-dicyclohexylcarbodiimide and/or N, N' -diisopropylcarbodiimide.
In a preferred embodiment, the compatibilizing agent is selected from the group consisting of epoxy-based compounds and/or isocyanate-based compounds. The epoxy compound is not particularly limited, and epoxy compounds and isocyanate compounds commonly used in the art can be used in the present invention.
In a preferred embodiment, the epoxy compound is a copolymer containing glycidyl methacrylate groups selected from styrene-acrylonitrile-glycerol methacrylate copolymer and/or ethylene-methyl acrylate-glycerol methylpropionate copolymer.
In a preferred embodiment, the isocyanate-based compound is selected from one or more of toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, and polyisocyanate. Among them, the polyisocyanate is not particularly limited in the present invention, and polyisocyanates commonly used in the art can be used in the present invention.
In a preferred embodiment, the antioxidant is a phosphite antioxidant, further preferably one or more selected from the group consisting of antioxidant 168, antioxidant 626, and antioxidant 9228.
In a preferred embodiment, the average particle size of the polybutylene succinate in the polyglycolic acid toughening modified material of the polyglycolic acid toughening modified material is 350 to 450nm.
In a preferred embodiment, the polyglycolic acid toughening modification material has a notched impact strength of 5 to 12kJ/m 2 Preferably 8-10kJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Further preferably 9.5 to 9.7kJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The tensile strength is 50-75MPa, preferably 55-70MPa; further preferably 62-65MPa; the elongation at break is 120-180%, preferably 145-170%; further preferably 160-165%; the flexural modulus is 3800-5400MPa, preferably 4000-5200MPa; further preferably 4400 to 4500MPa.
The second aspect of the invention provides a method for preparing a polyglycolic acid toughening modified material, the method comprising: and (3) carrying out melt blending and extrusion granulation on 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 compatilizer and 0.3-3 parts by weight of antioxidant to obtain the polyglycolic acid toughening modified material.
In a preferred embodiment, the method comprises: 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 compatilizer and 1-1.5 parts by weight of antioxidant are subjected to melt blending and extrusion granulation to obtain the polyglycolic acid toughening modified material.
Wherein polyglycolic acid, polybutylene succinate, modifier, compatibilizer and antioxidant are as described in the first aspect of the invention.
In a preferred embodiment, the extrusion pelletization is performed in a twin screw extruder, and the conditions of melt blending include: the melt blending temperature is 225-240 ℃, preferably 235-240 ℃.
In a preferred embodiment, the extrusion granulation operating conditions include: the temperature of the feeding section is 180-210 ℃, the temperature of the plasticizing section is 200-230 ℃, the temperature of the homogenizing section is 220-235 ℃, the temperature of the extrusion die head is 225-235 ℃, and the pressure of the extrusion die head is 1-10MPa.
In a preferred embodiment, the method further comprises: the raw materials are dried prior to said extrusion granulation. Further preferably, the drying is preferably vacuum drying, the vacuum drying temperature is 60-80 ℃, and the vacuum drying time is 5-10h.
The third aspect of the invention provides an application of the polyglycolic acid toughening modified material prepared by the first aspect of the invention and/or the polyglycolic acid toughening modified material prepared by the method of the second aspect of the invention in spinning fibers and/or thin-wall injection molding products.
The present invention will be described in detail by examples. Wherein polyglycolic acid (PGA) used in examples and comparative examples was obtained from Shanghai Pu Jing, had a weight average molecular weight of 100000 to 150000, and a melt index of 27g/10min at 240℃under a load of 2.16 kg; PBS was purchased from Lanshan river, xinjiang, with a weight average molecular weight of 50000-150000 and a melt index of 12g/min at 190℃under a load of 2.16 kg.
And (3) a compatilizer: the epoxy compound is Pasteur ADR-4468 (GMA content 10 wt%, weight average molecular weight is 6680); the isocyanate compound is Polyisocyanate (PMDI), PM200 (viscosity 150-250mPa.s at 25deg.C, NCO content 30.2-32 wt% and functionality 2.6-2.7) prepared by Wanhua chemistry. The silane coupling agent is purchased from Qu Fuyi cis-chemical industry with the product brand KH-792.
The modifier is N, N' -dicyclohexylcarbodiimide and the antioxidant is antioxidant 168.
The materials prepared in examples and comparative examples were tested for their performance as follows:
(1) Notched impact strength: according to GB/T1843-2008 test, at least 5 samples are tested, and the average value is taken
(2) Tensile strength and elongation at break: the tensile properties of the injection molded bars were measured according to GB/T16421-1996, at least 5 samples were tested and averaged.
(3) Flexural modulus: at least 5 samples were tested according to GB/T1843-2008 test and averaged.
(4) Melt index: measured by the method of GB/T3682-2000.
(5) Particle size of polybutylene succinate: the sample bar is brittle broken by liquid nitrogen, then PBS is etched by chloroform, then SEM observation measurement is used, and the holes in the SEM picture are the particle size of the PBS.
Example 1
Polyglycolic acid is placed in a vacuum drying oven and dried for 5 hours at 80 ℃; putting the polybutylene succinate into a vacuum drying oven, and drying for 8 hours at 60 ℃;
uniformly mixing the dried polyglycolic acid, the dried polybutylene succinate, the modifier, the antioxidant and the compatilizer, and then putting the mixture into a double-screw extruder for melt blending and extrusion granulation to obtain the polyglycolic acid toughening modified material; wherein the melt blending temperature is 235 ℃, the temperature of a charging section in the extrusion granulating process is 225 ℃, the temperature of a plasticizing section is 230 ℃, the temperature of a homogenizing section is 235 ℃, the temperature of an extrusion die head is 230 ℃, and the rotating speed of a screw is 100rad/min.
The types and amounts of the raw materials in example 1 are shown in table 1, and the test results of the obtained polyglycolic acid toughening modified materials are shown in table 2.
Examples 2 to 4
Similar to example 1, except that the types and amounts of the raw materials in examples 2 to 4 are shown in Table 1, the results of the test of the obtained polyglycolic acid toughening modified material are shown in Table 2.
Comparative examples 1 to 6
Similar to example 1, the difference is that: the types and amounts of the raw materials in comparative examples 1 to 6 are shown in Table 1, and the test results of the obtained polyglycolic acid toughening modified materials are shown in Table 2.
TABLE 1
TABLE 2
As shown in Table 1, the polyglycolic acid toughening modified material prepared by the invention has excellent mechanical comprehensive properties, high rigidity and high toughness, good stability and complete biodegradation, and can meet the requirements of spinning fiber and thin-wall injection molding products on the mechanical properties of the material.
Fig. 1 is a scanning electron microscope image of the polyglycolic acid toughening modified material obtained in example 3, fig. 2 is a scanning electron microscope image of the polyglycolic acid toughening modified material obtained in comparative example 2, and fig. 1 is a scanning electron microscope image of the polyglycolic acid toughening modified material obtained in comparative example 4.
As can be seen from FIG. 1, in the polyglycolic acid toughening modified material provided by the invention, the average particle size of the polybutylene succinate is 410nm and is uniformly distributed.
As can be seen from FIG. 2, the average particle size of the polybutylene succinate particles in the obtained polyglycolic acid toughening modified material is larger than 2000nm and the distribution is uneven by changing the dosages of the polyglycolic acid and the polybutylene succinate.
As can be seen from FIG. 3, when no compatibilizing agent is added, the average particle size of the polybutylene succinate is 1800nm, and the particle size is also larger, which is disadvantageous to the mechanical properties of the polyglycolic acid toughening modified material.
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 (10)
1. The polyglycolic acid toughening modified material is characterized by being prepared from the following raw materials in parts by weight: 65-85 parts of polyglycolic acid, 15-30 parts of polybutylene succinate, 1-4 parts of modifier, 0.5-5 parts of compatilizer and 0.3-3 parts of antioxidant; wherein, in the polyglycolic acid toughening modified material, the average grain diameter of the polybutylene succinate is 100-900nm.
2. The toughening modification material according to claim 1, wherein the toughening modification material is prepared from raw materials comprising: 78-82 parts of polyglycolic acid, 18-22 parts of polybutylene succinate, 2.5-3.5 parts of modifier, 1-1.5 parts of compatilizer and 1-1.5 parts of antioxidant.
3. The toughening modified material according to claim 1 or 2, wherein the polyglycolic acid has a weight average molecular weight of not less than 50000, preferably 100000 to 200000; the melt index at 240℃and under a load of 2.16kg is 2-100g/min, preferably 10-50g/10min.
4. A toughening modified material according to any one of claims 1 to 3, wherein the weight average molecular weight of the polybutylene succinate is equal to or more than 50000, preferably 100000 to 150000; the melt index at 190℃and under a load of 2.16kg is 2-30g/min, preferably 2-10g/10min.
5. The toughening modified material according to any one of claims 1 to 4, wherein the modifier is a composite carbodiimide or a monomeric carbodiimide; further preferred are N, N '-dicyclohexylcarbodiimide and/or N, N' -diisopropylcarbodiimide.
6. The toughening modified material according to any one of claims 1 to 5, wherein the compatibilizer is selected from an epoxy compound and/or an isocyanate compound;
preferably, the epoxy compound is a copolymer containing glycidyl methacrylate groups, selected from styrene-acrylonitrile-glycerol methacrylate copolymer and/or ethylene-methyl acrylate-glycerol methacrylate copolymer;
preferably, the isocyanate compound is selected from one or more of toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate and polyisocyanate.
7. The toughening modified material according to any one of claims 1 to 6, wherein the antioxidant is a phosphite antioxidant, further preferably one or more selected from the group consisting of antioxidant 168, antioxidant 626, and antioxidant 9228.
8. The toughening modified material according to any one of claims 1 to 7, wherein in the polyglycolic acid toughening modified material, the average particle diameter of polybutylene succinate is 350 to 450nm;
preferably, the polyglycolic acid toughening modification material has a notched impact strength of 5 to 12kJ/m 2 Preferably 8-10kJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The tensile strength is 50-75MPa, preferably 55-70MPa; the elongation at break is 120-180%, preferably 145-170%; the flexural modulus is 3800-5400MPa, preferably 4000-5200MPa.
9. A method for preparing a polyglycolic acid toughening modified material, which is characterized by comprising the following steps: melting, blending and extruding to granulate 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 compatilizer and 0.3-3 parts by weight of antioxidant, so as to obtain the polyglycolic acid toughening modified material;
preferably, the extrusion pelletization is performed in a twin screw extruder, and the conditions of melt blending include: the melt blending temperature is 230-240 ℃, preferably 235-240 ℃;
preferably, the operating conditions of the extrusion granulation include: the temperature of the feeding section is 180-210 ℃, the temperature of the plasticizing section is 200-230 ℃, the temperature of the homogenizing section is 220-235 ℃, the temperature of the extrusion die head is 225-235 ℃, and the pressure of the extrusion die head is 1-10MPa.
10. Use of the polyglycolic acid toughening modified material according to any one of claims 1 to 8 and/or prepared by the method according to claim 9 in spinning fibers and/or thin-wall injection molded products.
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